NO 2 oxidation reactivity and burning mode of diesel particulates

DOE PAGES

Strzelec, Andrea; Vander Wal, Randy L.; Thompson, Thomas N.; ...

2016-03-24

The NO 2 oxidation kinetics and burning mode for diesel particulate from light-duty and medium-duty engines fueled with either ultra low sulfur diesel or soy methyl ester biodiesel blends have been investigated and are shown to be significantly different from oxidation by O 2. Oxidation kinetics were measured using a flow-through packed bed microreactor for temperature programmed reactions and isothermal differential pulsed oxidation reactions. The burning mode was evaluated using the same reactor system for flowing BET specific surface area measurements and HR-TEM with fringe analysis to evaluate the nanostructure of the nascent and partially oxidized particulates. The low activationmore » energy measured, specific surface area progression with extent of oxidation, HR-TEM images and difference plots of fringe length and tortuosity paint a consistent picture of higher reactivity for NO 2, which reacts indiscriminately immediately upon contact with the surface, leading to the Zone I or shrinking core type oxidation. In comparison, O 2 oxidation is shown to have relatively lower reactivity, preferentially attacking highly curved lamella, which are more reactive due to bond strain, and short lamella, which have a higher proportion of more reactive edge sites. Furthermore, this preferential oxidation leads to Zone II type oxidation, where solid phase diffusion of oxygen via pores contributes significantly to slowing the overall oxidation rate, by comparison.« less

Oxidation behavior and area specific resistance of La, Cu and B alloyed Fe-22Cr ferritic steels for solid oxide fuel cell interconnects

NASA Astrophysics Data System (ADS)

Swaminathan, Srinivasan; Ko, Yoon Seok; Lee, Young-Su; Kim, Dong-Ik

2017-11-01

Two Fe-22 wt% Cr ferritic stainless steels containing varying concentrations of La (0.14 or 0.52 wt%), Cu (0.17 or 1.74 wt%) and B (48 or 109 ppm) are investigated with respect to oxidation behavior and high temperature area specific resistance (ASR) of the surface oxide scales. To determine the oxidation resistance of developed steels, continuous isothermal oxidation is carried out at 800 °C in air, for 2000 h, and their thermally grown oxide scale is characterized using dynamic SIMS, SEM/EDX, XRD and GI-XRD techniques. To assess their electrical performance, the ASR measurement by four-point probe method is conducted at 800 °C in air, for 400 h. In higher La content steel, the La-oxides at the scale/alloy interface promotes the oxygen transport which resulted in sub-surface oxidation of Mn, Cr, Ti and Al. Moreover, the inward growth of oxides contributes to increase of Fe-Cr alloy protrusions within the scale, which reduced the ASR. In contrast, sub-surface oxidation is reduced in high Cu-alloyed steel by segregated Cu at the scale/alloy interface. Thus, addition of Cu is effective to oxidation resistance and also to better electrical performance. However, no obvious impact of B on the scale sequence and/or ASR is observed.

Surface engineering on CeO2 nanorods by chemical redox etching and their enhanced catalytic activity for CO oxidation

NASA Astrophysics Data System (ADS)

Gao, Wei; Zhang, Zhiyun; Li, Jing; Ma, Yuanyuan; Qu, Yongquan

2015-07-01

Controllable surface properties of nanocerias are desired for various catalytic processes. There is a lack of efficient approaches to adjust the surface properties of ceria to date. Herein, a redox chemical etching method was developed to controllably engineer the surface properties of ceria nanorods. Ascorbic acid and hydrogen peroxide were used to perform the redox chemical etching process, resulting in a rough surface and/or pores on the surface of ceria nanorods. Increasing the etching cycles induced a steady increase of the specific surface area, oxygen vacancies and surface Ce3+ fractions. As a result, the etched nanorods delivered enhanced catalytic activity for CO oxidation, compared to the non-etched ceria nanorods. Our method provides a novel and facile approach to continuously adjust the surface properties of ceria for practical applications.Controllable surface properties of nanocerias are desired for various catalytic processes. There is a lack of efficient approaches to adjust the surface properties of ceria to date. Herein, a redox chemical etching method was developed to controllably engineer the surface properties of ceria nanorods. Ascorbic acid and hydrogen peroxide were used to perform the redox chemical etching process, resulting in a rough surface and/or pores on the surface of ceria nanorods. Increasing the etching cycles induced a steady increase of the specific surface area, oxygen vacancies and surface Ce3+ fractions. As a result, the etched nanorods delivered enhanced catalytic activity for CO oxidation, compared to the non-etched ceria nanorods. Our method provides a novel and facile approach to continuously adjust the surface properties of ceria for practical applications. Electronic supplementary information (ESI) available: Diameter distributions of as-prepared and etched samples, optical images, specific catalytic data of CO oxidation and comparison of CO oxidation. See DOI: 10.1039/c5nr01846c

Nitrogen-doped hierarchical porous carbon with high surface area derived from graphene oxide/pitch oxide composite for supercapacitors.

PubMed

Ma, Yuan; Ma, Chang; Sheng, Jie; Zhang, Haixia; Wang, Ranran; Xie, Zhenyu; Shi, Jingli

2016-01-01

A nitrogen-doped hierarchical porous carbon has been prepared through one-step KOH activation of pitch oxide/graphene oxide composite. At a low weight ratio of KOH/composite (1:1), the as-prepared carbon possesses high specific surface area, rich nitrogen and oxygen, appropriate mesopore/micropore ratio and considerable small-sized mesopores. The addition of graphene oxide plays a key role in forming 4 nm mesopores. The sample PO-GO-16 presents the characteristics of large surface area (2196 m(2) g(-1)), high mesoporosity (47.6%), as well as rich nitrogen (1.52 at.%) and oxygen (6.9 at.%). As a result, PO-GO-16 electrode shows an outstanding capacitive behavior: high capacitance (296 F g(-1)) and ultrahigh-rate performance (192 F g(-1) at 10 A g(-1)) in 6 M KOH aqueous electrolyte. The balanced structure characteristic, low-cost and high performance, make the porous carbon a promising electrode material for supercapacitors. Copyright © 2015 Elsevier Inc. All rights reserved.

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.

Polypyrrole/titanium oxide nanotube arrays composites as an active material for supercapacitors.

PubMed

Kim, Min Seok; Park, Jong Hyeok

2011-05-01

The authors present the first reported use of vertically oriented titanium oxide nanotube/polypyrrole (PPy) nanocomposites to increase the specific capacitance of TiO2 based energy storage devices. To increase their electrical storage capacity, titanium oxide nanotubes were coated with PPy and their morphologies were characterized. The incorporation of PPy increased the specific capacitance of the titanium oxide nanotube based supercapacitor system, due to their increased surface area and additional pseudo-capacitance.

Enhancement of the antimicrobial properties of orthorhombic molybdenum trioxide by thermal induced fracturing of the hydrates.

PubMed

Shafaei, Shahram; Van Opdenbosch, Daniel; Fey, Tobias; Koch, Marcus; Kraus, Tobias; Guggenbichler, Josef Peter; Zollfrank, Cordt

2016-01-01

The oxides of the transition metal molybdenum exhibit excellent antimicrobial properties. We present the preparation of molybdenum trioxide dihydrate (MoO3 × 2H2O) by an acidification method and demonstrate the thermal phase development and morphological evolution during and after calcination from 25 °C to 600 °C. The thermal dehydration of the material was found to proceed in two steps. Microbiological roll-on tests using Staphylococcus aureus, Escherichia coli and Pseudomonas aeruginosa were performed and exceptional antimicrobial activities were determined for anhydrous samples with orthorhombic lattice symmetry and a large specific surface area. The increase in the specific surface area is due to crack formation and to the loss of the hydrate water after calcination at 300 °C. The results support the proposed antimicrobial mechanism for transition metal oxides, which based on a local acidity increase as a consequence of the augmented specific surface area. Copyright © 2015 Elsevier B.V. All rights reserved.

Electrochemical capacitor

DOEpatents

Anderson, Marc A.; Liu, Kuo -Chuan; Mohr, Charles M.

1999-10-05

An inexpensive porous metal oxide material having high surface area, good conductivity and high specific capacitance is advantageously used in an electrochemical capacitor. The materials are formed in a sol-gel process which affords control over the properties of the resultant metal oxide materials.

Architecture engineering of supercapacitor electrode materials

NASA Astrophysics Data System (ADS)

Chen, Kunfeng; Li, Gong; Xue, Dongfeng

2016-02-01

The biggest challenge for today’s supercapacitor systems readily possessing high power density is their low energy density. Their electrode materials with controllable structure, specific surface area, electronic conductivity, and oxidation state, have long been highlighted. Architecture engineering of functional electrode materials toward powerful supercapacitor systems is becoming a big fashion in the community. The construction of ion-accessible tunnel structures can microscopically increase the specific capacitance and materials utilization; stiff 3D structures with high specific surface area can macroscopically assure high specific capacitance. Many exciting findings in electrode materials mainly focus on the construction of ice-folded graphene paper, in situ functionalized graphene, in situ crystallizing colloidal ionic particles and polymorphic metal oxides. This feature paper highlights some recent architecture engineering strategies toward high-energy supercapacitor electrode systems, including electric double-layer capacitance (EDLC) and pseudocapacitance.

The mechanisms of pyrite oxidation and leaching: A fundamental perspective

NASA Astrophysics Data System (ADS)

Chandra, A. P.; Gerson, A. R.

2010-09-01

Pyrite is the earth's most abundant sulfide mineral. Its frequent undesirable association with minerals of economic value such as sphalerite, chalcopyrite and galena, and precious metals such as gold necessitates costly separation processes such as leaching and flotation. Additionally pyrite oxidation is a major contributor to the environmental problem of acid rock drainage. The surface oxidation reactions of pyrite are therefore important both economically and environmentally. Significant variations in electrical properties resulting from lattice substitution of minor and trace elements into the lattice structure exist between pyrite from different geographical locations. Furthermore the presence of low coordination surface sites as a result of conchoidal fracture causes a reduction in the band gap at the surface compared to the bulk thus adding further electrochemical variability. Given the now general acceptance after decades of research that electrochemistry dominates the oxidation process, the geographical location, elemental composition and semi-conductor type (n or p) of pyrite are important considerations. Aqueous pyrite oxidation results in the production of sulfate and ferrous iron. However other products such as elemental sulfur, polysulfides, hydrogen sulfide, ferric hydroxide, iron oxide and iron(III) oxyhydroxide may also form. Intermediate species such as thiosulfate, sulfite and polythionates are also proposed to occur. Oxidation and leach rates are generally influenced by solution Eh, pH, oxidant type and concentration, hydrodynamics, grain size and surface area in relation to solution volume, temperature and pressure. Of these, solution Eh is most critical as expected for an electrochemically controlled process, and directly correlates with surface area normalised rates. Studies using mixed mineral systems further indicate the importance of electrochemical processes during the oxidation process. Spatially resolved surface characterisation of fresh and reacted pyrite surfaces is needed to identify site specific chemical processes. Scanning photoelectron microscopy (SPEM) and photoemission electron microscopy (PEEM) are two synchrotron based surface spectromicroscopic and microspectroscopic techniques that use XPS- and XANES-imaging to correlate chemistry with topography at a submicron scale. Recent data collected with these two techniques suggests that species are heterogeneously distributed on the surface and oxidation to be highly site specific.

High-surface-area nitrogen-doped reduced graphene oxide for electric double-layer capacitors

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

Youn, Hee-Chang; Bak, Seong-Min; Kim, Myeong-Seong

A two-step method consisting of solid-state microwave irradiation and heat treatment under NH₃ gas was used to prepare nitrogen-doped reduced graphene oxide (N-RGO) with a high specific surface area (1007m²g⁻¹), high electrical conductivity (1532S m⁻¹), and low oxygen content (1.5 wt%) for electric double-layer capacitor applications. The specific capacitance of N-RGO was 291 Fg⁻¹ at a current density of 1 A g⁻¹, and a capacitance of 261 F g⁻¹ was retained at 50 A g⁻¹, indicating a very good rate capability. N-RGO also showed excellent cycling stability, preserving 96% of the initial specific capacitance after 100,000 cycles. Near-edge X-ray absorptionmore » fine-structure spectroscopy evidenced the recover of π-conjugation in the carbon networks with the removal of oxygenated groups and revealed the chemical bonding of the nitrogen atoms in N-RGO. The good electrochemical performance of N-RGO is attributed to its high surface area, high electrical conductivity, and low oxygen content.« less

High-surface-area nitrogen-doped reduced graphene oxide for electric double-layer capacitors

DOE PAGES

Youn, Hee-Chang; Bak, Seong-Min; Kim, Myeong-Seong; ...

2015-06-08

A two-step method consisting of solid-state microwave irradiation and heat treatment under NH₃ gas was used to prepare nitrogen-doped reduced graphene oxide (N-RGO) with a high specific surface area (1007m²g⁻¹), high electrical conductivity (1532S m⁻¹), and low oxygen content (1.5 wt%) for electric double-layer capacitor applications. The specific capacitance of N-RGO was 291 Fg⁻¹ at a current density of 1 A g⁻¹, and a capacitance of 261 F g⁻¹ was retained at 50 A g⁻¹, indicating a very good rate capability. N-RGO also showed excellent cycling stability, preserving 96% of the initial specific capacitance after 100,000 cycles. Near-edge X-ray absorptionmore » fine-structure spectroscopy evidenced the recover of π-conjugation in the carbon networks with the removal of oxygenated groups and revealed the chemical bonding of the nitrogen atoms in N-RGO. The good electrochemical performance of N-RGO is attributed to its high surface area, high electrical conductivity, and low oxygen content.« less

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

PubMed

Cai, Nan; Larese-Casanova, Philip

2014-07-15

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

Synthesis of antimony-doped tin oxide (ATO) nanoparticles by the nitrate-citrate combustion method

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

Zhang Jianrong; Gao Lian

2004-12-02

Antimony-doped tin oxide (ATO) nanoparticles having rutile structure have been synthesized by the combustion method using citric acid (CA) as fuel and nitrate as an oxidant, the metal sources were granulated tin and Sb{sub 2}O{sub 3}. The influence of citric acid (fuel) to metal ratio on the average crystallite size, specific surface area and morphology of the nanoparticles has been investigated. X-ray diffraction showed the tin ions were reduced to elemental tin during combustion reaction. The average ATO crystallite size increased with the increase of citric acid (fuel). Powder morphology and the comparison of crystallite size and grain size showsmore » that the degree of agglomeration of the powder decreased with an increase of the ratio. The highest specific surface area was 37.5 m{sup 2}/g when the citric acid to tin ratio was about 6.« less

Study on the NO removal efficiency of the lignite pyrolysis coke catalyst by selective catalytic oxidation method

PubMed Central

Wen, Xin; Ma, Zhenhua; Zhang, Lei; Sha, Xiangling; He, Huibin; Zeng, Tianyou; Wang, Yusu; Chen, Jihao

2017-01-01

Selective catalytic oxidation (SCO) method is commonly used in wet denitration technology; NO after the catalytic oxidation can be removed with SO2 together by wet method. Among the SCO denitration catalysts, pyrolysis coke is favored by the advantages of low cost and high catalytic activity. In this paper, SCO method combined with pyrolysis coke catalyst was used to remove NO from flue gas. The effects of different SCO operating conditions and different pyrolysis coke catalyst made under different process conditions were studied. Besides, the specific surface area of the catalyst and functional groups were analyzed with surface area analyzer and Beohm titration. The results are: (1) The optimum operating conditions of SCO is as follows: the reaction temperature is 150°C and the oxygen content is 6%. (2) The optimum pyrolysis coke catalyst preparation processes are as follows: the pyrolysis final temperature is 750°C, and the heating rate is 44°C / min. (3) The characterization analysis can be obtained: In the denitration reaction, the basic functional groups and the phenolic hydroxyl groups of the catalyst play a major role while the specific surface area not. PMID:28793346

Reduced graphene oxide wrapped Ag nanostructures for enhanced SERS activity

NASA Astrophysics Data System (ADS)

Nair, Anju K.; Kala, M. S.; Thomas, Sabu; Kalarikkal, Nandakumar

2018-04-01

Graphene - metal nanoparticle hybrids have received great attention due to their unique electronic properties, large specific surface area, very high conductivity and more charge transfer. Thus, it is extremely advantages to develop a simple and efficient process to disperse metal nanostructures over the surface of graphene sheets. Herein, we report a hydrothermal assisted strategy for developing reduced graphene oxide /Ag nanomorphotypes (cube, wire) for surface enhanced Raman scattering (SERS) applications, considering the advantages of synergistic effect of graphene and plasmonic properties of Ag nanomorphotypes.

Electrical resistance behavior of oxyfluorinated graphene under oxidizing and reducing gas exposure.

PubMed

Im, Ji Sun; Bae, Tae-Sung; Shin, Eunjeong; Lee, Young-Seak

2014-03-01

The electrical resistance behavior of graphene was studied under oxidizing and reducing gas exposure. The graphene surface was modified via oxyfluorination to obtain a specific surface area and oxygen functional groups. Fluorine radicals provided improved pore structure and introduction of an oxygen functional group. A high-performance gas sensor was obtained based on enlarged target gas adsorption sites and an enhanced electron charge transfer between the target gas and carbon surface via improved pore structure and the introduction of oxygen functional groups, respectively.

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

Wang, Hongfen, E-mail: wanghongfen11@163.com; Wang, Zhiqi; Chen, Shougang

Molybdenum carbides with surfactants as carbon sources were prepared using the carbothermal reduction of the appropriate precursors (molybdenum oxides deposited on surfactant micelles) at 1023 K under hydrogen gas. The carburized products were characterized using scanning electron microscopy (SEM), X-ray diffraction and BET surface area measurements. From the SEM images, hollow microspherical and rod-like molybdenum carbides were observed. X-ray diffraction patterns showed that the annealing time of carburization had a large effect on the conversion of molybdenum oxides to molybdenum carbides. And BET surface area measurements indicated that the difference of carbon sources brought a big difference in specific surfacemore » areas of molybdenum carbides. - Graphical abstract: Molybdenum carbides having hollow microspherical and hollow rod-like morphologies that are different from the conventional monodipersed platelet-like morphologies. Highlights: Black-Right-Pointing-Pointer Molybdenum carbides were prepared using surfactants as carbon sources. Black-Right-Pointing-Pointer The kinds of surfactants affected the morphologies of molybdenum carbides. Black-Right-Pointing-Pointer The time of heat preservation at 1023 K affected the carburization process. Black-Right-Pointing-Pointer Molybdenum carbides with hollow structures had larger specific surface areas.« less

Surface segregation of additives on SnO 2 based powders and their relationship with macroscopic properties

NASA Astrophysics Data System (ADS)

Pereira, Gilberto J.; Castro, Ricardo H. R.; Hidalgo, Pilar; Gouvêa, Douglas

2002-07-01

Surface properties of ceramic powders frequently play an important role in producing high-quality, high-performance, and reliable ceramic products. These properties are related to the surface bond types and interactions with the surroundings. Oxide surfaces generally contain adsorbed hydroxyl groups and modifications in the chemical composition of the surface may be studied by infrared spectroscopy. In this work, we prepared SnO 2 containing Fe or Mg ions by organic chemical route derived from Pechini's method. The prepared powders were characterized by infrared spectroscopy (FT-IR), X-ray diffraction (XRD), dynamic electrophoretic mobility and surface area determination. Results demonstrated that the studied additives segregate onto the oxide surface and modify the hydroxyl IR bands of the adsorbed hydroxyl groups. These surface modifications change some macroscopic properties of the powder such as the isoelectric point (IEP) in aqueous suspensions and the final specific surface area. The increase of the surface area with additive concentration is supposedly due to the reduction of surface energy of the powders when additives segregate on the powder surface.

High-Surface-Area Nitrogen-Doped Reduced Graphene Oxide for Electric Double-Layer Capacitors.

PubMed

Youn, Hee-Chang; Bak, Seong-Min; Kim, Myeong-Seong; Jaye, Cherno; Fischer, Daniel A; Lee, Chang-Wook; Yang, Xiao-Qing; Roh, Kwang Chul; Kim, Kwang-Bum

2015-06-08

A two-step method consisting of solid-state microwave irradiation and heat treatment under NH3 gas was used to prepare nitrogen-doped reduced graphene oxide (N-RGO) with a high specific surface area (1007 m(2)  g(-1) ), high electrical conductivity (1532 S m(-1) ), and low oxygen content (1.5 wt %) for electrical double-layer capacitor applications. The specific capacitance of N-RGO was 291 F g(-1) at a current density of 1 A g(-1) , and a capacitance of 261 F g(-1) was retained at 50 A g(-1) , which indicated a very good rate capability. N-RGO also showed excellent cycling stability and preserved 96 % of the initial specific capacitance after 100 000 cycles. Near-edge X-ray absorption fine-structure spectroscopy results provided evidenced for the recovery of π conjugation in the carbon networks with the removal of oxygenated groups and revealed chemical bonding of the nitrogen atoms in N-RGO. The good electrochemical performance of N-RGO is attributed to its high surface area, high electrical conductivity, and low oxygen content. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Structure, morphology and reducibility of ceria-doped zirconia

NASA Astrophysics Data System (ADS)

Aribi, Koubra; Soltani, Zohra; Ghelamallah, Madani; Granger, Pascal

2018-03-01

Zr1-xCexOx has been prepared by hydrolysis, in neutral medium, starting from rough ZrO2 and CeO2 materials as simple and cheaper synthesis method compared to sol-gel routes. The oxy-hydroxide precursors thus obtained were calcined under air at 450 °C, 900 °C and 1200 °C. The impact of those thermal treatments on the structure, texture and related redox properties has been investigated. Higher specific surface area than those observed on ceria were observed after calcination at low temperature, i.e., 450 °C. Above that temperature thermal sintering occurs having a detrimental effect on the specific surface area related to crystal growth more accentuated on CeO2. The formation of several Zrsbnd Ce mixed oxide phases formed by incorporation and substitution of Zr in the structure of ceria was characterized. A complete loss of specific surface area is noticeable after calcination at 1200 °C. XRD and SEM analysis revealed the formation of two mixed oxides structure, i.e. Ce2Zr2O7.04 and Ce2Zr2O7 corresponding to different redox behavior evidenced from H2-TPR experiments.

Synthesis and characterization of binary titania-silica mixed oxides

NASA Astrophysics Data System (ADS)

Budhi, Sridhar

A series of binary titania-silica mixed oxides were synthesized by the sol-gel method at room temperature. The mixed oxides were prepared that involved the hydrolysis of titanium isopropoxide and tetraethylorthosilicate (TEOS) by co-solvent induced gelation usually in acidic media. The resulting gels were dried, calcined and then characterized by powder X-ray diffractometric studies, nitrogen sorption studies (at 77K), diffuse reflectance spectroscopy, Raman microscopy and transmission electron microscopic studies. The nitrogen sorption studies indicate that the specific surface areas, pore volume, pore diameter and pore size distribution of the mixed oxides were substantially enhanced when non-polar solvents such as toluene, p-xylene or mesitylene were added as co-solvents to the synthesis gel. Transmission electron microscopic (TEM) studies confirm the results obtained from the nitrogen sorption studies. Our results indicate that we can obtain binary metal oxides possessing high surface area and large pore volumes with tunable pore size distribution at room temperature. Photocatalytic evaluation of the mixed oxides is currently in progress.

Chemical degradation of trimethyl phosphate as surrogate for organo-phosporus pesticides on nanostructured metal oxides

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

Štengl, Václav, E-mail: stengl@iic.cas.cz; Henych, Jiří; Grygar, Tomáš

Nanostructured TiO{sub 2} and mixed oxides of Ti and Fe, Hf, In, Mn or Zr -were prepared by homogeneous hydrolysis of aqueous solution of metal sulphates with urea. The oxides were characterised by X-ray powder diffraction (XRD), scanning electron microscopy, particle size distribution, surface area and porosity. The oxide materials consists of a few nanometre primary crystals (mainly anatase) arranged in a few micrometre regular spherical agglomerates with specific surface area 133–511 m{sup 2} g{sup −1}. The FTIR diffuse spectroscopy was used for monitoring chemical degradation of trimethylphosphate (TMP) as a surrogate for organo-phosphorus pesticides under ambient and higher temperatures.more » Undoped TiO{sub 2} and Ti,Mn-mixed oxide were most active in cleavage (hydrolysis) of CH{sub 3}O from TMP at room temperature and 100 °C. Cleavage of CH{sub 3}O in the other studied mixed oxides was not complete until temperature exceeds the boiling point of TMP.« less

Microwave exfoliated graphene oxide/TiO{sub 2} nanowire hybrid for high performance lithium ion battery

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

Ishtiaque Shuvo, Mohammad Arif; Rodriguez, Gerardo; Karim, Hasanul

Lithium ion battery (LIB) is a key solution to the demand of ever-improving, high energy density, clean-alternative energy systems. In LIB, graphite is the most commonly used anode material; however, lithium-ion intercalation in graphite is limited, hindering the battery charge rate and capacity. To date, one of the approaches in LIB performance improvement is by using porous carbon (PC) to replace graphite as anode material. PC's pore structure facilitates ion transport and has been proven to be an excellent anode material candidate in high power density LIBs. In addition, to overcome the limited lithium-ion intercalation obstacle, nanostructured anode assembly hasmore » been extensively studied to increase the lithium-ion diffusion rate. Among these approaches, high specific surface area metal oxide nanowires connecting nanostructured carbon materials accumulation have shown promising results for enhanced lithium-ion intercalation. Herein, we demonstrate a hydrothermal approach of growing TiO{sub 2} nanowires (TON) on microwave exfoliated graphene oxide (MEGO) to further improve LIB performance over PC. This MEGO-TON hybrid not only uses the high surface area of MEGO but also increases the specific surface area for electrode–electrolyte interaction. Therefore, this new nanowire/MEGO hybrid anode material enhances both the specific capacity and charge–discharge rate. Scanning electron microscopy and X-ray diffraction were used for materials characterization. Battery analyzer was used for measuring the electrical performance of the battery. The testing results have shown that MEGO-TON hybrid provides up to 80% increment of specific capacity compared to PC anode.« less

Quantitative Detection of Prostatic-Specific Antigens by Using Scanning Electron Microscopy for the Analysis of Protein Chips.

PubMed

Lee, Jisu; Jung, Moon Youn; Park, Hyung Ju

2017-04-01

We reported that quantitative detection of prostatic-specific antigen (PSA), which is the biomarker of prostate cancer, could be carried out by calculating the number density and the area ratio of gold nanoparticle probes on the surface of silicon oxide chips. When chips selectively activated with PSA were immersed in the gold nanoparticles conjugated with prostatic specific antigens-poly clonal antibodies (PSA-pAb), it was possible to observe changes in the number density and the area ratio of gold nanoparticles on the surface of the chips according to the concentration of PSA with scanning electron microscopy (SEM) images. As PSA concentration increased, the number density and the area ratio of gold nanoparticle probes on the surfaces of the chips increased accordingly. Conversely, with lower concentration, the number density and the area ratio of gold nanoparticle probes on the surfaces decreased at a certain ratio. We observed the correlations between PSA concentration and number density, area ratio of gold nanoparticle probes through the analysis of SEM images. In addition, it was confirmed that the sizes of the gold nanoparticles affected the detection limit of the number density and the area ratio of gold nanoparticle probes on the surface.

A Semi-Empirical Two Step Carbon Corrosion Reaction Model in PEM Fuel Cells

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

Young, Alan; Colbow, Vesna; Harvey, David

2013-01-01

The cathode CL of a polymer electrolyte membrane fuel cell (PEMFC) was exposed to high potentials, 1.0 to 1.4 V versus a reversible hydrogen electrode (RHE), that are typically encountered during start up/shut down operation. While both platinum dissolution and carbon corrosion occurred, the carbon corrosion effects were isolated and modeled. The presented model separates the carbon corrosion process into two reaction steps; (1) oxidation of the carbon surface to carbon-oxygen groups, and (2) further corrosion of the oxidized surface to carbon dioxide/monoxide. To oxidize and corrode the cathode catalyst carbon support, the CL was subjected to an accelerated stressmore » test cycled the potential from 0.6 VRHE to an upper potential limit (UPL) ranging from 0.9 to 1.4 VRHE at varying dwell times. The reaction rate constants and specific capacitances of carbon and platinum were fitted by evaluating the double layer capacitance (Cdl) trends. Carbon surface oxidation increased the Cdl due to increased specific capacitance for carbon surfaces with carbon-oxygen groups, while the second corrosion reaction decreased the Cdl due to loss of the overall carbon surface area. The first oxidation step differed between carbon types, while both reaction rate constants were found to have a dependency on UPL, temperature, and gas relative humidity.« less

Sulfur-Doping Templated Synthesis of Nanoporous Graphitic Nanocages and Its Supported Catalysts for Efficient Methanol Oxidation.

PubMed

Sheng, Zhao Min; Hong, Cheng Yang; Dai, Xian You; Chang, Cheng Kang; Chen, Jian Bin; Liu, Yan

2015-04-01

We demonstrate a new sulfur (S)-doping templated approach to fabricate highly nanoporous graphitic nanocages (GNCs) by air-oxidizing the templates in the graphitic shells to create nanopores. Sulfur can be introduced, when Fe@C core-shell nanoparticles are prepared and then S-doped GNCs can be obtained by removing their ferrous cores. Due to removing S-template, both the specific surface area (from 540 to 850 m2 g(-1)) and the mesopore volume (from 0.44 to 0.9 cm3 g(-1)) of the graphitic nanocages have sharply risen. Its high specific surface area improves catalyst loading to provide more reaction electro-active sites while its high mesopore volume pro- motes molecule diffusion across the nanocages, making it an excellent material to support Pt/Ru catalysts for direct methanol fuel cells.

Agarose template for the fabrication of macroporous metal oxide structures.

PubMed

Zhou, Jingfang; Zhou, Meifang; Caruso, Rachel A

2006-03-28

Agarose gels have been applied as templates for the formation of macroporous metal oxide structures. The preparation of the agarose template is extremely simple, and with variation of the agarose content, control over morphology is demonstrated: The average pore size decreases from 180 to 55 nm and the surface area increases from 238 to 271 m2 g(-1) with increasing agarose content in the gel. The gelling temperature was also found to influence the final template morphology. Conducting sol-gel chemistry within the template structure followed by removal of the template by heating to 450 degrees C gives porous inorganic oxides. The technique has been demonstrated for the oxides of titanium, zirconium, niobium, and tin. The final morphology of the metal oxide is homogeneous and results from a coating of the agarose structure. The pore diameter decreased and the specific surface area of the titanium dioxide materials increased from 28 to 66 m2 g(-1) as the agarose content in the template is increased from 0.5 to 5.0 wt%. The overall pore size and surface area are lower than the original gel due to shrinkage occurring with the sol-gel process, as well as crystallization and a loss of microporosity in the final material.

Final report of CCQM-K136 measurement of porosity properties (specific adsorption, BET specific surface area, specific pore volume and pore diameter) of nanoporous Al2O3

NASA Astrophysics Data System (ADS)

Sobina, E.; Zimathis, A.; Prinz, C.; Emmerling, F.; Unger, W.; de Santis Neves, R.; Galhardo, C. E.; De Robertis, E.; Wang, H.; Mizuno, K.; Kurokawa, A.

2016-01-01

CCQM key comparison K-136 Measurement of porosity properties (specific adsorption, BET specific surface area, specific pore volume and pore diameter) of nanoporous Al2O3 has been performed by the Surface Analysis Working Group (SAWG) of the Consultative Committee for Amount of Substance (CCQM). The objective of this key comparison is to compare the equivalency of the National Metrology Institutes (NMIs) and Designated Institutes (DIs) for the measurement of specific adsorption, BET specific surface area, specific pore volume and pore diameter) of nanoporous substances (sorbents, catalytic agents, cross-linkers, zeolites, etc) used in advanced technology. In this key comparison, a commercial sorbent (aluminum oxide) was supplied as a sample. Five NMIs participated in this key comparison. All participants used a gas adsorption method, here nitrogen adsorption at 77.3 K, for analysis according to the international standards ISO 15901-2 and 9277. In this key comparison, the degrees of equivalence uncertainties for specific adsorption, BET specific surface area, specific pore volume and pore diameter was established. Main text To reach the main text of this paper, click on Final Report. Note that this text is that which appears in Appendix B of the BIPM key comparison database kcdb.bipm.org/. The final report has been peer-reviewed and approved for publication by the CCQM, according to the provisions of the CIPM Mutual Recognition Arrangement (CIPM MRA).

Porous Aluminum Oxide and Magnesium Oxide Films Using Organic Hydrogels as Structure Matrices

PubMed Central

Chen, Zimei

2018-01-01

We describe the synthesis of mesoporous Al2O3 and MgO layers on silicon wafer substrates by using poly(dimethylacrylamide) hydrogels as porogenic matrices. Hydrogel films are prepared by spreading the polymer through spin-coating, followed by photo-cross-linking and anchoring to the substrate surface. The metal oxides are obtained by swelling the hydrogels in the respective metal nitrate solutions and subsequent thermal conversion. Combustion of the hydrogel results in mesoporous metal oxide layers with thicknesses in the μm range and high specific surface areas up to 558 m2∙g−1. Materials are characterized by SEM, FIB ablation, EDX, and Kr physisorption porosimetry. PMID:29565802

Area-Selective Atomic Layer Deposition of Metal Oxides on Noble Metals through Catalytic Oxygen Activation

PubMed Central

2017-01-01

Area-selective atomic layer deposition (ALD) is envisioned to play a key role in next-generation semiconductor processing and can also provide new opportunities in the field of catalysis. In this work, we developed an approach for the area-selective deposition of metal oxides on noble metals. Using O2 gas as co-reactant, area-selective ALD has been achieved by relying on the catalytic dissociation of the oxygen molecules on the noble metal surface, while no deposition takes place on inert surfaces that do not dissociate oxygen (i.e., SiO2, Al2O3, Au). The process is demonstrated for selective deposition of iron oxide and nickel oxide on platinum and iridium substrates. Characterization by in situ spectroscopic ellipsometry, transmission electron microscopy, scanning Auger electron spectroscopy, and X-ray photoelectron spectroscopy confirms a very high degree of selectivity, with a constant ALD growth rate on the catalytic metal substrates and no deposition on inert substrates, even after 300 ALD cycles. We demonstrate the area-selective ALD approach on planar and patterned substrates and use it to prepare Pt/Fe2O3 core/shell nanoparticles. Finally, the approach is proposed to be extendable beyond the materials presented here, specifically to other metal oxide ALD processes for which the precursor requires a strong oxidizing agent for growth. PMID:29503508

Micro/nanostructured porous Fe-Ni binary oxide and its enhanced arsenic adsorption performances.

PubMed

Liu, Shengwen; Kang, Shenghong; Wang, Guozhong; Zhao, Huijun; Cai, Weiping

2015-11-15

A simple method is presented to synthesize micro/nano-structured Fe-Ni binary oxides based on co-precipitation and subsequent calcination. It has been found that the Fe-Ni binary oxides are composed of the porous microsized aggregates built with nanoparticles. When the atomic ratio of Fe to Ni is 2 to 1 the binary oxide is the micro-scaled aggregates consisting of the ultrafine NiFe2O4 nanoparticles with 3-6nm in size, and shows porous structure with pore diameter of 3nm and a specific surface area of 245m(2)g(-1). Such material is of abundant surface functional groups and has exhibited high adsorption performance to As(III) and As(V). The kinetic adsorption can be described by pseudo-second order model and the isothermal adsorption is subject to Langmuir model. The maximum adsorption capacity on such Fe-Ni porous binary oxide is up to 168.6mgg(-1) and 90.1mgg(-1) for As(III) and As(V), respectively, which are much higher than the arsenic adsorption capacity for most commercial adsorbents. Such enhanced adsorption ability for this material is mainly attributed to its porous structure and high specific surface area as well as the abundant surface functional groups. Further experiments have revealed that the influence of the anions such as sulfate, carbonate, and phosphate, which commonly co-exist in water, on the arsenic adsorption is insignificant, exhibiting strong adsorption selectivity to arsenic. This micro/nano-structured porous Fe-Ni binary oxide is hence of good practicability to be used as a highly efficient adsorbent for arsenic removal from the real arsenic-contaminated waters. Copyright © 2015 Elsevier Inc. All rights reserved.

On the formation of nanocrystalline active zinc oxide from zinc hydroxide carbonate

NASA Astrophysics Data System (ADS)

Moezzi, Amir; Cortie, Michael; Dowd, Annette; McDonagh, Andrew

2014-04-01

The decomposition of zinc hydroxide carbonate, Zn5(CO3)2(OH)6 (ZHC), into the high surface area form of ZnO known as "active zinc oxide" is examined. In particular, the nucleation and evolution of the ZnO nanocrystals is of interest as the size of these particles controls the activity of the product. The decomposition process was studied using X-ray diffraction, thermogravimetric analysis, scanning electron microscopy, transmission electron microscopy and BET surface area measurements. At about 240 °C ZHC decomposes to porous ZnO in a single step. The product material has a specific surface area in the range of 47-65 m2 g-1 and initially has a crystallite size that is of the order of 10 nm. A further increase in temperature, however, causes the particles to coarsen to over 25 nm in diameter. In principle, the coarsening phenomenon may be interrupted to control the particle size.

Removal of sulfur and nitrogen containing pollutants from discharge gases

DOEpatents

Joubert, James I.

1986-01-01

Oxides of sulfur and of nitrogen are removed from waste gases by reaction with an unsupported copper oxide powder to form copper sulfate. The resulting copper sulfate is dissolved in water to effect separation from insoluble mineral ash and dried to form solid copper sulfate pentahydrate. This solid sulfate is thermally decomposed to finely divided copper oxide powder with high specific surface area. The copper oxide powder is recycled into contact with the waste gases requiring cleanup. A reducing gas can be introduced to convert the oxide of nitrogen pollutants to nitrogen.

Nanoparticles in natural systems I: The effective reactive surface area of the natural oxide fraction in field samples

NASA Astrophysics Data System (ADS)

Hiemstra, Tjisse; Antelo, Juan; Rahnemaie, Rasoul; van Riemsdijk, Willem H.

2010-01-01

Information on the particle size and reactive surface area of natural samples is essential for the application of surface complexation models (SCM) to predict bioavailability, toxicity, and transport of elements in the natural environment. In addition, this information will be of great help to enlighten views on the formation, stability, and structure of nanoparticle associations of natural organic matter (NOM) and natural oxide particles. Phosphate is proposed as a natively present probe ion to derive the effective reactive surface area of natural samples. In the suggested method, natural samples are equilibrated (⩾10 days) with 0.5 M NaHCO 3 (pH = 8.5) at various solid-solution ratios. This matrix fixes the pH and ionic strength, suppresses the influence of Ca 2+ and Mg 2+ ions by precipitation these in solid carbonates, and removes NOM due to the addition of activated carbon in excess, collectively leading to the dominance of the PO 4-CO 3 interaction in the system. The data have been interpreted with the charge distribution (CD) model, calibrated for goethite, and the analysis results in an effective reactive surface area (SA) and a reversibly bound phosphate loading Γ for a series of top soils. The oxidic SA varies between about 3-30 m 2/g sample for a large series of representative agricultural top soils. Scaling of our data to the total iron and aluminum oxide content (dithionite-citrate-bicarbonate extractable), results in the specific surface area between about 200-1200 m 2/g oxide for most soils, i.e. the oxide particles are nano-sized with an equivalent diameter in the order of ˜1-10 nm if considered as non-porous spheres. For the top soils, the effective surface area and the soil organic carbon fraction are strongly correlated. The oxide particles are embedded in a matrix of organic carbon (OC), equivalent to ˜1.4 ± 0.2 mg OC/m 2 oxide for many soils of the collection, forming a NOM-mineral nanoparticle association with an average NOM volume fraction of ˜80%. The average mass density of such a NOM-mineral association is ˜1700 ± 100 kg/m 3 (i.e. high-density NOM). The amount of reversibly bound phosphate is rather close to the amount of phosphate that is extractable with oxalate. The phosphate loading varies remarkably ( Γ ≈ 1-3 μmol/m 2 oxide) in the samples. As discussed in part II of this paper series ( Hiemstra et al., 2010), the phosphate loading ( Γ) of field samples is suppressed by surface complexation of NOM, where hydrophilic, fulvic, and humic acids act as a competitor for (an)ions via site competition and electrostatic interaction.

Heat Treatment of Tantalum and Niobium Powders Prepared by Magnesium-Thermic Reduction

NASA Astrophysics Data System (ADS)

Orlov, V. M.; Prokhorova, T. Yu.

2017-11-01

Changes in the specific surface area and porous structure of tantalum and niobium powders, which were prepared by magnesium-thermic reduction of Ta2O5, Mg4Ta2O9, and Mg4Nb2O9 oxide compounds and subjected to heat treatments at temperatures of 600-1500°C, have been studied. It is noted that, owing to the mesoporous structure of the magnesium-thermic powders, the decrease in the surface area during heat treatment, first of all, is related to a decrease in the amount of pores less than 10 nm in size. The heat treatment of a reacting mass is shown to allow us to correct the specific surface area of the powder without any increase in the oxygen content in it. Data on the effect of heat treatment conditions on the specific charge of capacitor anodes are reported.

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

Nonlinear electronic transport and enhanced catalytic behavior caused by native oxides on Cu nanowires

NASA Astrophysics Data System (ADS)

Hajimammadov, Rashad; Csendes, Zita; Ojakoski, Juha-Matti; Lorite, Gabriela Simone; Mohl, Melinda; Kordas, Krisztian

2017-09-01

Electrical transport properties of individual nanowires (both in axial and transversal directions) and their random networks suggest rapid oxidation when Cu is exposed to ambient conditions. The oxidation process is elucidated by thorough XRD, XPS and Raman analyzes conducted for a period of 30 days. Based on the obtained experimental data, we may conclude that first, cuprous oxide and copper hydroxide form that finally transform to cupric oxide. In electrical applications, oxidation of copper is not a true problem as long as thin films or bulk metal is concerned. However, as highlighted in our work, this is not the case for nanowires, since the oxidized surface plays quite important role in the contact formation and also in the conduction of percolated nanowire networks. On the other hand, by taking advantage of the mixed surface oxide states present on the nanowires along with their large specific surface area, we tested and found excellent catalytic activity of the oxidized nanowires in phenol oxidation, which suggests further applications of these materials in catalysis.

Supercapacitors based on nitrogen-doped reduced graphene oxide and borocarbonitrides

NASA Astrophysics Data System (ADS)

Gopalakrishnan, K.; Moses, Kota; Govindaraj, A.; Rao, C. N. R.

2013-12-01

Nitrogen-doped reduced graphene oxide (RGO) samples with different nitrogen content, prepared by two different methods, as well as nitrogen-doped few-layer graphene have been investigated as supercapacitor electrodes. Two electrode measurements have been carried out both in aqueous (6M KOH) and in ionic liquid media. Nitrogen-doped reduced graphene oxides exhibit satisfactory specific capacitance, the values reaching 126F/g at a scan rate of 10mV/s in aqueous medium. Besides providing supercapacitor characteristics, the study has shown the nitrogen content and surface area to be important factors. High surface-area borocarbonitrides, BxCyNz, prepared by the urea route appear to be excellent supercapacitor electrode materials. Thus, BC4.5N exhibits a specific capacitance of 169F/g at a scan rate of 10mV/s in aqueous medium. In an ionic liquid medium, nitrogen-doped RGO and BC4.5N exhibit specific capacitance values of 258F/g and 240F/g at a scan rate of 5mV/s. The ionic liquid enables a larger operating voltage range of 0.0-2.5V compared to 0.0-1V in aqueous medium.

Tungsten carbide/porous carbon composite as superior support for platinum catalyst toward methanol electro-oxidation

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

Jiang, Liming; Fu, Honggang, E-mail: fuhg@vip.sina.com; Key Laboratory of Functional Inorganic Material Chemistry, Heilongjiang University, Harbin 150080

2014-01-01

Graphical abstract: The WC nanoparticles are well dispersed in the carbon matrix. The size of WC nanoparticles is about 30 nm. It can be concluded that tungsten carbide and carbon composite was successfully prepared by the present synthesis conditions. - Highlights: • The WC/PC composite with high specific surface area was prepared by a simple way. • The Pt/WC/PC catalyst has superior performance toward methanol electro-oxidation. • The current density for methanol electro-oxidation is as high as 595.93 A g{sup −1} Pt. • The Pt/WC/PC catalyst shows better durability and stronger CO electro-oxidation. • The performance of Pt/WC/PC is superiormore » to the commercial Pt/C (JM) catalyst. - Abstract: Tungsten carbide/porous carbon (WC/PC) composites have been successfully synthesized through a surfactant assisted evaporation-induced-assembly method, followed by a thermal treatment process. In particular, WC/PC-35-1000 composite with tungsten content of 35% synthesized at the carbonized temperature of 1000 °C, exhibited a specific surface area (S{sub BET}) of 457.92 m{sup 2} g{sup −1}. After loading Pt nanoparticles (NPs), the obtained Pt/WC/PC-35-1000 catalyst exhibits the highest unit mass electroactivity (595.93 A g{sup −1} Pt) toward methanol electro-oxidation, which is about 2.6 times as that of the commercial Pt/C (JM) catalyst. Furthermore, the Pt/WC/PC-35-1000 catalyst displays much stronger resistance to CO poisoning and better durability toward methanol electrooxidation compared with the commercial Pt/C (JM) catalyst. The high electrocatalytic activity, strong poison-resistivity and good stability of Pt/WC/PC-35-1000 catalyst are attributed to the porous structures and high specific surface area of WC/PC support could facilitate the rapid mass transportation. Moreover, synergistic effect between WC and Pt NPs is favorable to the higher catalytic performance.« less

Fabrication of hollow boron-doped diamond nanostructure via electrochemical corrosion of a tungsten oxide template.

PubMed

Lim, Young-Kyun; Lee, Eung-Seok; Lee, Choong-Hyun; Lim, Dae-Soon

2018-08-10

In the study, a hollow boron-doped diamond (BDD) nanostructure electrode is fabricated to increase the reactive surface area for electrochemical applications. Tungsten oxide nanorods are deposited on the silicon substrate as a template by the hot filament chemical vapor deposition (HFCVD) method. The template is coated with a 100 nm BDD layer deposited by HFCVD to form a core-shell nanostructure. The WO x core is finally electrochemically dissolved to form hollow BDD nanostructure. The fabricated hollow BDD nanostructure electrode is investigated via scanning electron microscopy, transmission electron microscopy, and Raman spectroscopy. The specific surface areas of the electrodes were analyzed and compared by using Brunauer-Emmett-Teller method. Furthermore, cyclic voltammetry and chronocoulometry are used to investigate the electrochemical characteristics and the reactive surface area of the as-prepared hollow BDD nanostructure electrode. A hollow BDD nanostructure electrode exhibits a reactive area that is 15 times that of a planar BDD thin electrode.

The effects of cetyltrimethylammonium bromide surfactant on alumina modified zinc oxides

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

Gac, Wojciech, E-mail: wojciech.gac@umcs.lublin.pl; Zawadzki, Witold; Słowik, Grzegorz

Highlights: • Synthesis of novel ZnO−Al{sub 2}O{sub 3} oxides in the presence of CTAB surfactant. • Determination of the structural, surface and optical properties. • Nanocrystalline, high-surface area ZnO−Al{sub 2}O{sub 3} oxides. • ZnO-Al{sub 2}O{sub 3} materials of different gap energy. - Abstract: Novel alumina modified zinc oxide materials were prepared by co-precipitation method in the presence of different amounts of cetyltrimethylammonium bromide (CTAB) surfactant. X-ray diffraction, {sup 27}Al magic-angle spinning Nuclear Magnetic Resonance Spectroscopy, and transmission electron microscopy studies evidenced formation of 10–15 nm zinc oxide nanoparticles in the presence of the small amounts of surfactant. Amorphous alumina andmore » zinc aluminate phases of different coordination environment of Al sites were identified. An increase of surfactant concentration led to the elongation of nanoparticles and changes of the nature of hydroxyl groups. Precipitation in the high CTAB concentration conditions facilitated formation of mesoporous materials of high specific surface area. The materials were composed of very small (2–3 nm) zinc aluminate spinel nanoparticles. High concentration of CTAB induced widening of band gap energy.« less

Microanalytical X-ray imaging of depleted uranium speciation in environmentally aged munitions residues.

PubMed

Crean, Daniel E; Livens, Francis R; Stennett, Martin C; Grolimund, Daniel; Borca, Camelia N; Hyatt, Neil C

2014-01-01

Use of depleted uranium (DU) munitions has resulted in contamination of the near-surface environment with penetrator residues. Uncertainty in the long-term environmental fate of particles produced by impact of DU penetrators with hard targets is a specific concern. In this study DU particles produced in this way and exposed to the surface terrestrial environment for longer than 30 years at a U.K. firing range were characterized using synchrotron X-ray chemical imaging. Two sites were sampled: a surface soil and a disposal area for DU-contaminated wood, and the U speciation was different between the two areas. Surface soil particles showed little extent of alteration, with U speciated as oxides U3O7 and U3O8. Uranium oxidation state and crystalline phase mapping revealed these oxides occur as separate particles, reflecting heterogeneous formation conditions. Particles recovered from the disposal area were substantially weathered, and U(VI) phosphate phases such as meta-ankoleite (K(UO2)(PO4) · 3H2O) were dominant. Chemical imaging revealed domains of contrasting U oxidation state linked to the presence of both U3O7 and meta-ankoleite, indicating growth of a particle alteration layer. This study demonstrates that substantial alteration of DU residues can occur, which directly influences the health and environmental hazards posed by this contamination.

Two orders of magnitude enhancement in oxygen evolution reactivity on amorphous Ba0.5Sr0.5Co0.8Fe0.2O3−δ nanofilms with tunable oxidation state

PubMed Central

Chen, Gao; Zhou, Wei; Guan, Daqin; Sunarso, Jaka; Zhu, Yanping; Hu, Xuefeng; Zhang, Wei; Shao, Zongping

2017-01-01

Perovskite oxides exhibit potential for use as electrocatalysts in the oxygen evolution reaction (OER). However, their low specific surface area is the main obstacle to realizing a high mass-specific activity that is required to be competitive against the state-of-the-art precious metal–based catalysts. We report the enhanced performance of Ba0.5Sr0.5Co0.8Fe0.2O3−δ (BSCF) for the OER with intrinsic activity that is significantly higher than that of the benchmark IrO2, and this result was achieved via fabrication of an amorphous BSCF nanofilm on a surface-oxidized nickel substrate by magnetron sputtering. The surface nickel oxide layer of the Ni substrate and the thickness of the BSCF film were further used to tune the intrinsic OER activity and stability of the BSCF catalyst by optimizing the electronic configuration of the transition metal cations in BSCF via the interaction between the nanofilm and the surface nickel oxide, which enables up to 315-fold enhanced mass-specific activity compared to the crystalline BSCF bulk phase. Moreover, the amorphous BSCF–Ni foam anode coupled with the Pt–Ni foam cathode demonstrated an attractive small overpotential of 0.34 V at 10 mA cm−2 for water electrolysis, with a BSCF loading as low as 154.8 μg cm−2. PMID:28691090

Electrochemical properties of reduced graphene oxide derived through camphor assisted combustion of graphite oxide.

PubMed

Ramesh, A; Jeyavelan, M; Leo Hudson, M Sterlin

2018-04-17

A facile method was demonstrated for the one-step synthesis of reduced graphene oxide (rGO) from graphite oxide (GO) using a camphor assisted combustion (CAC) process. Analysis of samples was carried out using FT-IR, XRD, TGA, Raman, BET, SEM and TEM techniques. The electrochemical properties of the rGO samples derived through the CAC process were determined using cyclic voltammetry, galvanostatic charge/discharge and impedance spectroscopy. It has been observed that the specific surface area and porosity of the rGO samples decrease with the increasing concentration of camphor during the CAC synthesis process. Thus, different mass ratios of GO and camphor such as 1 : 12, 1 : 16, and 1 : 20 in the CAC process yield rGO samples having surface areas (SBET) of 313.3, 297.5 and 177.4 m2 g-1. The pore volumes of the respective samples are 0.44, 0.45 and 0.23 cm3 g-1, respectively. The rGO derived using the 1 : 12 mass ratio of GO and camphor (rGO-12C) exhibits a high specific capacitance of 241 F g-1, which is significantly higher than that observed for chemically reduced graphene oxide (rGO-CR), which exhibits a specific capacitance value of only 153 F g-1. The capacitance retention of rGO-12C was found to be 98% even after 1000 galvanostatic charge-discharge (GCD) cycles, suggesting its potential applications in electrochemical energy storage.

Electrochemical studies on nanometal oxide-activated carbon composite electrodes for aqueous supercapacitors

NASA Astrophysics Data System (ADS)

Ho, Mui Yen; Khiew, Poi Sim; Isa, Dino; Chiu, Wee Siong

2014-11-01

In present study, the electrochemical performance of eco-friendly and cost-effective titanium oxide (TiO2)-based and zinc oxide-based nanocomposite electrodes were studied in neutral aqueous Na2SO3 electrolyte, respectively. The electrochemical properties of these composite electrodes were studied using cyclic voltammetry (CV), galvanostatic charge-discharge (CD) and electrochemical impedance spectroscopy (EIS). The experimental results reveal that these two nanocomposite electrodes achieve the highest specific capacitance at fairly low oxide loading onto activated carbon (AC) electrodes, respectively. Considerable enhancement of the electrochemical properties of TiO2/AC and ZnO/AC nanocomposite electrodes is achieved via synergistic effects contributed from the nanostructured metal oxides and the high surface area mesoporous AC. Cations and anions from metal oxides and aqueous electrolyte such as Ti4+, Zn2+, Na+ and SO32- can occupy some pores within the high-surface-area AC electrodes, forming the electric double layer at the electrode-electrolyte interface. Additionally, both TiO2 and ZnO nanoparticles can provide favourable surface adsorption sites for SO32- anions which subsequently facilitate the faradaic processes for pseudocapacitive effect. These two systems provide the low cost material electrodes and the low environmental impact electrolyte which offer the increased charge storage without compromising charge storage kinetics.

The nanophase iron mineral(s) in Mars soil

NASA Technical Reports Server (NTRS)

Banin, A.; Ben-Shlomo, T.; Margulies, L.; Blake, D. F.; Mancinelli, R. L.; Gehring, A. U.

1993-01-01

A series of surface-modified clays containing nanophase (np) iron oxide/oxyhydroxides of extremely small particle sizes, with total iron contents as high as found in Mars soil, were prepared by iron deposition on the clay surface from ferrous chloride solution. Comprehensive studies of the iron mineralogy in these "Mars-soil analogs" were conducted using chemical extractions, solubility analyses, pH and redox, x ray and electron diffractometry, electron microscopic imaging, specific surface area and particle size determinations, differential thermal analyses, magnetic properties characterization, spectral reflectance, and Viking biology simulation experiments. The clay matrix and the procedure used for synthesis produced nanophase iron oxides containing a certain proportion of divalent iron, which slowly converts to more stable, fully oxidized iron minerals. The clay acted as an effective matrix, both chemically and sterically, preventing the major part of the synthesized iron oxides from ripening, i.e., growing and developing larger crystals. The precipitated iron oxides appear as isodiametric or slightly elongated particles in the size range 1-10 nm, having large specific surface area. The noncrystalline nature of the iron compounds precipitated on the surface of the clay was verified by their complete extractability in oxalate. Lepidocrocite (gamma-FeOOH) was detected by selected area electron diffraction. It is formed from a double iron Fe(II)/Fe(III) hydroxy mineral such as "green rust," or ferrosic hydroxide. Magnetic measurements suggested that lepidocrocite converted to the more stable maghemite (gamma-Fe2O3) by mild heat treatment and then to nanophase hematite (alpha-Fe2O3) by extensive heat treatment. After mild heating, the iron-enriched clay became slightly magnetic, to the extent that it adheres to a hand-held magnet, as was observed with Mars soil. The chemical reactivity of the iron-enriched clays strongly resembles, and offers a plausible mechanism for, the somewhat puzzling observations of the Viking biology experiments. Their unique chemical reactivities are attributed to the combined catalytic effects of the iron oxide/oxyhydroxides and silicate phase surfaces. The reflectance spectrum of the clay-iron preparations in the visible range is generally similar to the reflectance curves of bright regions on Mars. This strengthens the evidence for the predominance of nanophase iron oxides/oxyhydroxides in Mars soil. The mode of formation of these nanophase iron oxides on Mars is still unknown. It is puzzling that despite the long period of time since aqueous weathering took place on Mars, they have not developed from their transitory stage to well-crystallized end-members. The possibility is suggested that these phases represent a continuously on-going, extremely slow weathering process.

Correlation between the microstructures of graphite oxides and their catalytic behaviors in air oxidation of benzyl alcohol.

PubMed

Geng, Longlong; Wu, Shujie; Zou, Yongcun; Jia, Mingjun; Zhang, Wenxiang; Yan, Wenfu; Liu, Gang

2014-05-01

A series of graphite oxide (GO) materials were obtained by thermal treatment of oxidized natural graphite powder at different temperatures (from 100 to 200 °C). The microstructure evolution (i.e., layer structure and surface functional groups) of the graphite oxide during the heating process is studied by various characterization means, including XRD, N2 adsorption, TG-DTA, in situ DRIFT, XPS, Raman, TEM and Boehm titration. The characterization results show that the structures of GO materials change gradually from multilayer sheets to a transparent ultrathin 2D structure of the carbon sheets. The concentration of surface COH and HOCO groups decrease significantly upon treating temperature increasing. Benzyl alcohol oxidation with air as oxidant source was carried out to detect the catalytic behaviors of different GO materials. The activities of GO materials decrease with the increase of treating temperatures. It shows that the structure properties, including ultrathin sheets and high specific surface area, are not crucial factors affecting the catalytic activity. The type and amount of surface oxygen-containing functional groups of GO materials tightly correlates with the catalytic performance. Carboxylic groups on the surface of GO should act as oxidative sites for benzyl alcohol and the reduced form could be reoxidized by molecular oxygen. Copyright © 2014 Elsevier Inc. All rights reserved.

Size-Dependent Specific Surface Area of Nanoporous Film Assembled by Core-Shell Iron Nanoclusters

DOE PAGES

Antony, Jiji; Nutting, Joseph; Baer, Donald R.; ...

2006-01-01

Nmore » anoporous films of core-shell iron nanoclusters have improved possibilities for remediation, chemical reactivity rate, and environmentally favorable reaction pathways. Conventional methods often have difficulties to yield stable monodispersed core-shell nanoparticles. We produced core-shell nanoclusters by a cluster source that utilizes combination of Fe target sputtering along with gas aggregations in an inert atmosphere at 7 ∘ C . Sizes of core-shell iron-iron oxide nanoclusters are observed with transmission electron microscopy (TEM). The specific surface areas of the porous films obtained from Brunauer-Emmett-Teller (BET) process are size-dependent and compared with the calculated data.« less

Synthesis and characterization of MOF-aminated graphite oxide composites for CO2 capture

NASA Astrophysics Data System (ADS)

Zhao, Yunxia; Ding, Huiling; Zhong, Qin

2013-11-01

A kind of metal-organic frameworks (MOF-5) and aminated graphite oxide (AGO) composites were prepared for CO2 capture to mitigate global warming. MOF-5, MOF-5/GO (composite of MOF-5 and graphite oxide) and MOF-5/AGO samples were characterized by X-ray powder diffraction (XRD), infrared spectroscopy (IR), scanning electron microscope (SEM), nitrogen adsorption as well as thermogravimetric analysis to figure out their chemistry and structure information. Three types of samples with suitable specific surface area and pore diameter were chosen to test CO2 adsorption performance and stability under humidity conditions. The results indicate that high surface area and pore volume, pore similar in size to the size of gas adsorbate, and extra reactive sites modified in the composites contributes to the high CO2 capacity. Besides, the composites involved by GO or AGO show better anti-moisture performance than the parent MOF.

Investigation of the degradation mechanism of catalytic wires during oxidation of ammonia process

NASA Astrophysics Data System (ADS)

Pura, Jarosław; Wieciński, Piotr; Kwaśniak, Piotr; Zwolińska, Marta; Garbacz, Halina; Zdunek, Joanna; Laskowski, Zbigniew; Gierej, Maciej

2016-12-01

The most common catalysts for the ammonia oxidation process are 80 μm diameter platinum-rhodium wires knitted or woven into the form of a gauze. In an aggressive environment and under extreme conditions (temperature 800-900 °C, intensive gas flow, high pressure) precious elements are drained from the surface of the wires. Part of this separated material quickly decomposes on the surface in the form of characteristic "cauliflower-shape protrusions". The rest of the platinum is captured by palladium-nickel catalytic-capture gauzes located beneath. In our investigation we focused on the effects of the degradation of gauzes from one industrial catalytic system. The aim of the study was to compare the degree and the mechanism of degradation of gauzes from a different part of the reactor. The study covered PtRh7 catalytic and PdNi5 catalytic-capture gauzes. X-ray computer microtomography investigation revealed that despite strong differences in morphology, each Pt-Rh wire has a similar specific surface area. This indicates that the oxidation process and morphological changes of the wires occur in a self-regulating balance, resulting in the value of the specific surface area of the catalyst. Microtomography analysis of Pd-Ni wires revealed strong redevelopment of the wires' surface, which is related to the platinum capture phenomenon. Scanning electron microscope observations also revealed the nanostructure in the cauliflower-shape protrusions and large grains in the wires' preserved cores. The high temperature in the reactor and the long-term nature of the process do not favor the occurrence of the nanostructure in this type of material. Further and detailed analysis of this phenomena will provide a better understanding of the precious metals etching and deposition processes during oxidation.

Nanostructured porous Si optical biosensors: effect of thermal oxidation on their performance and properties.

PubMed

Shtenberg, Giorgi; Massad-Ivanir, Naama; Fruk, Ljiljana; Segal, Ester

2014-09-24

The influence of thermal oxidation conditions on the performance of porous Si optical biosensors used for label-free and real-time monitoring of enzymatic activity is studied. We compare three oxidation temperatures (400, 600, and 800 °C) and their effect on the enzyme immobilization efficiency and the intrinsic stability of the resulting oxidized porous Si (PSiO2), Fabry-Pérot thin films. Importantly, we show that the thermal oxidation profoundly affects the biosensing performance in terms of greater optical sensitivity, by monitoring the catalytic activity of horseradish peroxidase and trypsin-immobilized PSiO2. Despite the significant decrease in porous volume and specific surface area (confirmed by nitrogen gas adsorption-desorption studies) with elevating the oxidation temperature, higher content and surface coverage of the immobilized enzymes is attained. This in turn leads to greater optical stability and sensitivity of PSiO2 nanostructures. Specifically, films produced at 800 °C exhibit stable optical readout in aqueous buffers combined with superior biosensing performance. Thus, by proper control of the oxide layer formation, we can eliminate the aging effect, thus achieving efficient immobilization of different biomolecules, optical signal stability, and sensitivity.

Low-surface-area hard carbon anode for Na-ion batteries via graphene oxide as a dehydration agent

DOE PAGES

Luo, Wei; Bommier, Clement; Jian, Zelang; ...

2015-02-04

Na-ion batteries are emerging as one of the most promising energy storage technologies, particularly for grid-level applications. Among anode candidate materials, hard carbon is very attractive due to its high capacity and low cost. However, hard carbon anodes often suffer a low first-cycle Coulombic efficiency and fast capacity fading. In this study, we discover that doping graphene oxide into sucrose, the precursor for hard carbon, can effectively reduce the specific surface area of hard carbon to as low as 5.4 m²/g. We further reveal that such doping can effectively prevent foaming during caramelization of sucrose and extend the pyrolysis burn-offmore » of sucrose caramel over a wider temperature range. Thus, the obtained low-surface-area hard carbon greatly improves the first-cycle Coulombic efficiency from 74% to 83% and delivers a very stable cyclic life with 95% of capacity retention after 200 cycles.« less

Low-Surface-Area Hard Carbon Anode for Na-Ion Batteries via Graphene Oxide as a Dehydration Agent

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

Luo, W; Bommier, C; Jian, ZL

2015-02-04

Na-ion batteries are emerging as one of the most promising energy storage technologies, particularly for grid-level applications. Among anode candidate materials, hard carbon is very attractive due to its high capacity and low cost. However, hard carbon anodes often suffer a low first-cycle Coulombic efficiency and fast capacity fading. In this study, we discover that doping graphene oxide into sucrose, the precursor for hard carbon, can effectively reduce the specific surface area of hard carbon to as low as 5.4 m(2)/g. We further reveal that such doping can effectively prevent foaming during caramelization of sucrose and extend the pyrolysis burnoffmore » of sucrose caramel over a wider temperature range. The obtained low-surface-area hard carbon greatly improves the first-cycle Coulombic efficiency from 74% to 83% and delivers a very stable cyclic life with 95% of capacity retention after 200 cycles.« less

Advanced cathode materials for polymer electrolyte fuel cells based on pt/ metal oxides: from model electrodes to catalyst systems.

PubMed

Fabbri, Emiliana; Pătru, Alexandra; Rabis, Annett; Kötz, Rüdiger; Schmidt, Thomas J

2014-01-01

The development of stable catalyst systems for application at the cathode side of polymer electrolyte fuel cells (PEFCs) requires the substitution of the state-of-the-art carbon supports with materials showing high corrosion resistance in a strongly oxidizing environment. Metal oxides in their highest oxidation state can represent viable support materials for the next generation PEFC cathodes. In the present work a multilevel approach has been adopted to investigate the kinetics and the activity of Pt nanoparticles supported on SnO2-based metal oxides. Particularly, model electrodes made of SnO2 thin films supporting Pt nanoparticles, and porous catalyst systems made of Pt nanoparticles supported on Sb-doped SnO2 high surface area powders have been investigated. The present results indicate that SnO2-based supports do not modify the oxygen reduction reaction mechanism on the Pt nanoparticle surface, but rather lead to catalysts with enhanced specific activity compared to Pt/carbon systems. Different reasons for the enhancement in the specific activity are considered and discussed.

Synthesis and Electrochemical Analyses of Manganese Oxides for Super-Capacitors.

PubMed

Kim, Taewoo; Hwang, Hyein; Jang, Jaeyong; Park, Inyeong; Shim, Sang Eun; Baeck, Sung-Hyeon

2015-11-01

δ-Phase and α-phase manganese oxides were prepared using a hydrothermal method and their electrochemical properties were characterized. The influence of calcination temperature on the properties of manganese oxides was studied. Crystallinities were studied by X-ray diffraction, and scanning and transmission electron microscopy were utilized to examine morphologies. Average pore sizes and specific surface areas of samples were analyzed using the Barret-Joyner-Halenda and Brunauer-Emmett-Teller methods, respectively. After calcination in the range 300 degrees C to 600 degrees C, changes in morphology and crystallinity were observed. The flower-like shape of as synthesized samples became nanorod-like and the δ-phase changed to the α-phase. These changes may have been due to the removal of water during calcination. Furthermore, a transition stage in which the two phases coexisted was observed. Synthesized manganese oxides were mixed with carbon by sonification, to increase electric conductivity and to induce a synergistic effect between pseudo-capacitor and electric double layer capacitor (EDLC). Specific capacitances and rate durability of each composite were investigated by cyclic voltammetry in 1 M Na2SO4 electrolyte at different scan rates. MnO2 calcined at 400 degrees C exhibited the highest capacitance, probably due to its high surface area and more porous structure.

Production of Biogenic Mn Oxides by Leptothrix discophora SS-1 in a Chemically Defined Growth Medium and Evaluation of Their Pb Adsorption Characteristics

PubMed Central

Nelson, Yarrow M.; Lion, Leonard W.; Ghiorse, William C.; Shuler, Michael L.

1999-01-01

Biogenic Mn oxides were produced by the bacterium Leptothrix discophora SS-1 (= ATCC 3182) in a chemically defined mineral salts medium, and the Pb binding and specific surface area of these oxides were characterized. Growth of SS-1 in the defined medium with pyruvate as a carbon and energy source required the addition of vitamin B12. Complete oxidation of Mn(II) within 60 h required the addition of ≥0.1 μM FeSO4. Pb adsorption isotherms were determined for the biogenic Mn oxides (and associated cells with their extracellular polymer) and compared to the Pb adsorption isotherms of cells and exopolymer alone, as well as to abiotic Mn oxides. The Pb adsorption to cells and exopolymer with biogenic Mn oxides (0.8 mmol of Mn per g) at pH 6.0 and 25°C was 2 orders of magnitude greater than the Pb adsorption to cells and exopolymer alone (on a dry weight basis). The Pb adsorption to the biogenic Mn oxide was two to five times greater than the Pb adsorption to a chemically precipitated abiotic Mn oxide and several orders of magnitude greater than the Pb adsorption to two commercially available crystalline MnO2 minerals. The N2 Brunauer-Emmet-Teller specific surface areas of the biogenic Mn oxide and fresh Mn oxide precipitate (224 and 58 m2/g, respectively) were significantly greater than those of the commercial Mn oxide minerals (0.048 and 4.7 m2/g). The Pb adsorption capacity of the biogenic Mn oxide also exceeded that of a chemically precipitated colloidal hydrous Fe oxide under similar solution conditions. These results show that amorphous biogenic Mn oxides similar to those produced by SS-1 may play a significant role in the control of trace metal phase distribution in aquatic systems. PMID:9872777

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.

Heat transfer from an oxidized large copper surface to liquid helium: Dependence on surface orientation and treatment

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

Iwamoto, A.; Mito, T.; Takahata, K.

Heat transfer of large copper plates (18 x 76 mm) in liquid helium has been measured as a function of orientation and treatment of the heat transfer surface. The results relate to applications of large scale superconductors. In order to clarify the influence of the area where the surface treatment peels off, the authors studied five types of heat transfer surface areas including: (a) 100% polished copper sample, (b) and (c) two 50% oxidized copper samples having different patterns of oxidation, (d) 75% oxidized copper sample, (e) 90% oxidized copper sample, and (f) 100% oxidized copper sample. They observed thatmore » the critical heat flux depends on the heat transfer surface orientation. The critical heat flux is a maximum at angles of 0{degrees} - 30{degrees} and decreases monotonically with increasing angles above 30{degrees}, where the angle is taken in reference to the horizontal axis. On the other hand, the minimum heat flux is less dependent on the surface orientation. More than 75% oxidation on the surface makes the critical heat flux increase. The minimum heat fluxes of the 50 and 90% oxidized Cu samples approximately agree with that of the 100% oxidized Cu sample. Experiments and calculations show that the critical and the minimum heat fluxes are a bilinear function of the fraction of oxidized surface area.« less

Regeneration of Waste Edible Oil by the Use of Virgin and Calcined Magnesium Hydroxide as Adsorbents.

PubMed

Ogata, Fumihiko; Kawasaki, Naohito

2016-01-01

In this study, we prepared virgin (S, L) and calcined (S-380, S-1000, L-380, L-1000) magnesium hydroxide for regeneration of waste edible oil. Deterioration of soybean oil, rapeseed oil, and olive oil was achieved by heat and aeration treatment. The properties of the different adsorbents were investigated using specific surface area measurements, scanning electron microscopy, X-ray diffraction analysis, thermogravimetric-differential thermal analysis, and surface pH measurement. Moreover, the relationship between the changes in acid value (AV) and carbonyl value (CV) and the adsorbent properties were evaluated. The specific surface areas of S-380 and L-380 were greater than that of other adsorbents. In addition, the XRD results show that S-380 and L-380 contain both magnesium hydroxide and magnesium oxide structures. The decreases in AV and CV using S-380 and L-380 were greater than achieved using other adsorbents. The correlation coefficients between the decrease in AV and CV and specific surface area were 0.947 for soybean oil, 0.649 for rapeseed oil, and 0.773 for olive oil, respectively. The results obtained in this study suggest that a physical property of the adsorbent, namely specific surface area, was primarily responsible for the observed decreases in AV and CV. Overall, the results suggest that S-380 and L-380 are useful for the regeneration of waste edible oil.

Mesoporous Transition Metal Oxides for Supercapacitors.

PubMed

Wang, Yan; Guo, Jin; Wang, Tingfeng; Shao, Junfeng; Wang, Dong; Yang, Ying-Wei

2015-10-14

Recently, transition metal oxides, such as ruthenium oxide (RuO₂), manganese dioxide (MnO₂), nickel oxides (NiO) and cobalt oxide (Co₃O₄), have been widely investigated as electrode materials for pseudo-capacitors. In particular, these metal oxides with mesoporous structures have become very hot nanomaterials in the field of supercapacitors owing to their large specific surface areas and suitable pore size distributions. The high specific capacities of these mesoporous metal oxides are resulted from the effective contacts between electrode materials and electrolytes as well as fast transportation of ions and electrons in the bulk of electrode and at the interface of electrode and electrolyte. During the past decade, many achievements on mesoporous transition metal oxides have been made. In this mini-review, we select several typical nanomaterials, such as RuO₂, MnO₂, NiO, Co₃O₄ and nickel cobaltite (NiCo₂O₄), and briefly summarize the recent research progress of these mesoporous transition metal oxides-based electrodes in the field of supercapacitors.

Mesoporous Transition Metal Oxides for Supercapacitors

PubMed Central

Wang, Yan; Guo, Jin; Wang, Tingfeng; Shao, Junfeng; Wang, Dong; Yang, Ying-Wei

2015-01-01

Recently, transition metal oxides, such as ruthenium oxide (RuO2), manganese dioxide (MnO2), nickel oxides (NiO) and cobalt oxide (Co3O4), have been widely investigated as electrode materials for pseudo-capacitors. In particular, these metal oxides with mesoporous structures have become very hot nanomaterials in the field of supercapacitors owing to their large specific surface areas and suitable pore size distributions. The high specific capacities of these mesoporous metal oxides are resulted from the effective contacts between electrode materials and electrolytes as well as fast transportation of ions and electrons in the bulk of electrode and at the interface of electrode and electrolyte. During the past decade, many achievements on mesoporous transition metal oxides have been made. In this mini-review, we select several typical nanomaterials, such as RuO2, MnO2, NiO, Co3O4 and nickel cobaltite (NiCo2O4), and briefly summarize the recent research progress of these mesoporous transition metal oxides-based electrodes in the field of supercapacitors. PMID:28347088

Preparation of surface modified TiO2/rGO microspheres and application in the photocatalytic decomposition of oleic acid

NASA Astrophysics Data System (ADS)

Wu, Xin; Zeng, Min; Tong, Xiaoling; Li, Fuyun; Xu, Youyou

2018-05-01

The comprehensive utilization of waste cooking oil is an important research topic in food science. In this study, the surface modified mesoporous anatase TiO2/reduced graphene oxide (rGO) microspheres with a high specific surface area have been successfully synthesized, through hydrothermal routes and hydrazine reduced graphene oxide. The photocatalytic decomposition of waste rapeseed oil has also been studied using TiO2/rGO microspheres as photocatalyst. The result shows that the reduced graphene oxide in these nanocomposites can act as adsorbent and photocatalyst, and the temperature and the oxygen amount also are the most important factors affecting the oleic acid decomposition products. There interesting results not only helpful for the study of the mechanism of photocatalytic, but also useful for the rational use of waste cooking oil.

Determination of the surface area of smectite in water by ethylene oxide chain adsorption.

PubMed

Yuang, Paul-Cheng; Shen, Yun-Hwei

2005-05-15

This study investigates the feasibility of using ethylene oxide (EO) chain adsorption to determine the surface area of smectite in water. Experimental results indicate that high-molecular-weight poly(ethylene oxide) (PEO) should be used to provide reasonable estimations for monolayer capacity of PEO on smectite. The surface areas of smectites in water are calculated from the monolayer capacity of PEO adsorbed on smectite by taking the area per EO unit as 8.05 A(2). The method measures the actual surface area of smectite exposed when dispersed in water, which is important to applications of smectite under aqueous conditions.

Electrocatalytic oxidation of small organic molecules in acid medium: enhancement of activity of noble metal nanoparticles and their alloys by supporting or modifying them with metal oxides.

PubMed

Kulesza, Pawel J; Pieta, Izabela S; Rutkowska, Iwona A; Wadas, Anna; Marks, Diana; Klak, Karolina; Stobinski, Leszek; Cox, James A

2013-11-01

Different approaches to enhancement of electrocatalytic activity of noble metal nanoparticles during oxidation of small organic molecules (namely potential fuels for low-temperature fuel cells such as methanol, ethanol and formic acid) are described. A physical approach to the increase of activity of catalytic nanoparticles (e.g. platinum or palladium) involves nanostructuring to obtain highly dispersed systems of high surface area. Recently, the feasibility of enhancing activity of noble metal systems through the formation of bimetallic (e.g. PtRu, PtSn, and PdAu) or even more complex (e.g. PtRuW, PtRuSn) alloys has been demonstrated. In addition to possible changes in the electronic properties of alloys, specific interactions between metals as well as chemical reactivity of the added components have been postulated. We address and emphasize here the possibility of utilization of noble metal and alloyed nanoparticles supported on robust but reactive high surface area metal oxides (e.g. WO 3 , MoO 3 , TiO 2 , ZrO 2 , V 2 O 5 , and CeO 2 ) in oxidative electrocatalysis. This paper concerns the way in which certain inorganic oxides and oxo species can act effectively as supports for noble metal nanoparticles or their alloys during electrocatalytic oxidation of hydrogen and representative organic fuels. Among important issues are possible changes in the morphology and dispersion, as well as specific interactions leading to the improved chemisorptive and catalytic properties in addition to the feasibility of long time operation of the discussed systems.

Electrocatalytic oxidation of small organic molecules in acid medium: enhancement of activity of noble metal nanoparticles and their alloys by supporting or modifying them with metal oxides

PubMed Central

Kulesza, Pawel J.; Pieta, Izabela S.; Rutkowska, Iwona A.; Wadas, Anna; Marks, Diana; Klak, Karolina; Stobinski, Leszek; Cox, James A.

2013-01-01

Different approaches to enhancement of electrocatalytic activity of noble metal nanoparticles during oxidation of small organic molecules (namely potential fuels for low-temperature fuel cells such as methanol, ethanol and formic acid) are described. A physical approach to the increase of activity of catalytic nanoparticles (e.g. platinum or palladium) involves nanostructuring to obtain highly dispersed systems of high surface area. Recently, the feasibility of enhancing activity of noble metal systems through the formation of bimetallic (e.g. PtRu, PtSn, and PdAu) or even more complex (e.g. PtRuW, PtRuSn) alloys has been demonstrated. In addition to possible changes in the electronic properties of alloys, specific interactions between metals as well as chemical reactivity of the added components have been postulated. We address and emphasize here the possibility of utilization of noble metal and alloyed nanoparticles supported on robust but reactive high surface area metal oxides (e.g. WO3, MoO3, TiO2, ZrO2, V2O5, and CeO2) in oxidative electrocatalysis. This paper concerns the way in which certain inorganic oxides and oxo species can act effectively as supports for noble metal nanoparticles or their alloys during electrocatalytic oxidation of hydrogen and representative organic fuels. Among important issues are possible changes in the morphology and dispersion, as well as specific interactions leading to the improved chemisorptive and catalytic properties in addition to the feasibility of long time operation of the discussed systems. PMID:24443590

Oxidation of platinum nickel nanowires to improve durability of oxygen-reducing electrocatalysts

DOE PAGES

Alia, Shaun M.; Pylypenko, Svitlana; Dameron, Arrelaine; ...

2016-01-12

In this study, the impact of heat treating platinum-coated nickel (Pt-Ni) nanowires in oxygen is examined to determine the effect on oxygen reduction (ORR) activity and durability. Pt-Ni nanowires exhibit promising ORR mass activities (3 times greater than Pt nanoparticles, 1.5 times greater than U.S. Department of Energy target) both before and after potential cycling for all but the highest annealing temperatures explored. The annealing of Pt-Ni nanowires in oxygen with increasing temperature is found to reduce surface area and ORR activity in comparison to the untreated material, but also reduces activity losses following durability testing. Following potential cycling, unannealedmore » Pt-Ni nanowires show significant losses in surface area (23%) and specific activity (18%) while Pt-Ni nanowires annealed at 200°C show modest increases in surface area (2%) and specific activity (6%) after potential cycling. Increasing annealing temperatures also show a clear trend of decreasing Ni dissolution rates. While oxygen annealing has shown the ability to improve durability of Pt-Ni nanowires, significant Ni dissolution was observed in all samples and suggests oxide passivation while showing promise for improved durability, when employed by itself is insufficient to prevent all contamination concerns involving Ni dissolution.« less

A facile one-pot self-assembly approach to incorporate SnOx nanoparticles in ordered mesoporous carbon with soft templating for fuel cells.

PubMed

Huang, Yingqiang; Zhai, Zhicheng; Luo, Zhigang; Liu, Yingju; Liang, Zhurong; Fang, Yueping

2014-04-04

Unique SnO(x) (x = 1,2)/ordered mesoporous carbon nanocomposites (denoted as SnO(x)/OMC) are firstly synthesized through a 'one-pot' synthesis together with the soft template self-assembly approach. The obtained SnO(x)/OMC nanocomposites with various SnO(x) contents exhibit uniform pore sizes between 3.9 and 4.2 nm, high specific surface areas between 497 and 595 m(2) g(-1), and high pore volumes between 0.39 and 0.48 cm(3) g(-1). With loading of Pt, Pt-SnO(x)/OMC with relatively low SnO(x) content exhibits superior electrocatalytic performance, long-term durability, and resistance to CO poisoning for methanol oxidation, as compared to Pt/OMC, PtRu/C and Pt-SnO(x)/C, which may be attributed not only to the synergetic effect of embedded SnO(x), but also to the highly ordered mesostructure with high specific surface areas and large pore volumes affording plenty of surface area for support of Pt nanoparticles. This work supplies an efficient way to synthesize novel ordered mesoporous carbon self-supported metallic oxide as catalyst support and its further potential application to reduce the cost of catalysts in direct methanol fuel cells.

A facile one-pot self-assembly approach to incorporate SnOx nanoparticles in ordered mesoporous carbon with soft templating for fuel cells

NASA Astrophysics Data System (ADS)

Huang, Yingqiang; Zhai, Zhicheng; Luo, Zhigang; Liu, Yingju; Liang, Zhurong; Fang, Yueping

2014-04-01

Unique SnOx (x = 1,2)/ordered mesoporous carbon nanocomposites (denoted as SnOx/OMC) are firstly synthesized through a ‘one-pot’ synthesis together with the soft template self-assembly approach. The obtained SnOx/OMC nanocomposites with various SnOx contents exhibit uniform pore sizes between 3.9 and 4.2 nm, high specific surface areas between 497 and 595 m2 g-1, and high pore volumes between 0.39 and 0.48 cm3 g-1. With loading of Pt, Pt-SnOx/OMC with relatively low SnOx content exhibits superior electrocatalytic performance, long-term durability, and resistance to CO poisoning for methanol oxidation, as compared to Pt/OMC, PtRu/C and Pt-SnOx/C, which may be attributed not only to the synergetic effect of embedded SnOx, but also to the highly ordered mesostructure with high specific surface areas and large pore volumes affording plenty of surface area for support of Pt nanoparticles. This work supplies an efficient way to synthesize novel ordered mesoporous carbon self-supported metallic oxide as catalyst support and its further potential application to reduce the cost of catalysts in direct methanol fuel cells.

Kinetics of sorption and abiotic oxidation of arsenic(III) by aquifer materials

USGS Publications Warehouse

Amirbahman, A.; Kent, D.B.; Curtis, G.P.; Davis, J.A.

2006-01-01

The fate of arsenic in groundwater depends largely on its interaction with mineral surfaces. We investigated the kinetics of As(III) oxidation by aquifer materials collected from the USGS research site at Cape Cod, MA, USA, by conducting laboratory experiments. Five different solid samples with similar specific surface areas (0.6-0.9 m2 g-1) and reductively extractable iron contents (18-26 ??mol m-2), but with varying total manganese contents (0.5-3.5 ??mol m-2) were used. Both dissolved and adsorbed As(III) and As(V) concentrations were measured with time up to 250 h. The As(III) removal rate from solution increased with increasing solid manganese content, suggesting that manganese oxide is responsible for the oxidation of As(III). Under all conditions, dissolved As(V) concentrations were very low. A quantitative model was developed to simulate the extent and kinetics of arsenic transformation by aquifer materials. The model included: (1) reversible rate-limited adsorption of As(III) onto both oxidative and non-oxidative (adsorptive) sites, (2) irreversible rate-limited oxidation of As(III), and (3) equilibrium adsorption of As(V) onto adsorptive sites. Rate constants for these processes, as well as the total oxidative site densities were used as the fitting parameters. The total adsorptive site densities were estimated based on the measured specific surface area of each material. The best fit was provided by considering one fast and one slow site for each adsorptive and oxidative site. The fitting parameters were obtained using the kinetic data for the most reactive aquifer material at different initial As(III) concentrations. Using the same parameters to simulate As(III) and As(V) surface reactions, the model predictions were compared to observations for aquifer materials with different manganese contents. The model simulated the experimental data very well for all materials at all initial As(III) concentrations. The As(V) production rate was related to the concentrations of the free oxidative surface sites and dissolved As(III), as r As(V) = k???ox [Mn(IV) OH3][AsO3] with apparent second-order rate constants of koxf??? = 6.28 ?? 10-1 and koxs??? = 1.25 ?? 10-2 M-1 s-1 for the fast and the slow oxidative sites, respectively. The As(III) removal rate decreased approximately by half for a pH increase from 4 to 7. The pH dependence was explained using the acid-base behavior of the surface oxidative sites by considering a surface pKa = 6.2 (I = 0). In the presence of excess surface adsorptive and oxidative sites, phosphate diminished the rate of As(III) removal and As(V) production only slightly due to its interaction with the oxidative sites. The observed As(III) oxidation rate here is consistent with previous observations of As(III) oxidation over short transport distances during field-scale transport experiments. The model developed here may be incorporated into groundwater transport models to predict arsenic speciation and transport in chemically heterogeneous systems. ?? 2005 Elsevier Inc. All rights reserved.

Removal of sulfa drugs by sewage treatment in aqueous solution systems: activated carbon treatment and ozone oxidation.

PubMed

Ogata, Fumihiko; Tominaga, Hisato; Kangawa, Moe; Inoue, Kenji; Kawasaki, Naohito

2012-01-01

This study investigates the activated carbon (AC) treatment and ozone oxidation of the sulfa drugs--sulfamethoxazole (SMX), sulfamonomethoxine (SMM), sulfadimidine (SDD), and sulfadimethoxine (SDM)--in aqueous solution systems. Three AC samples were prepared from Shirasagi (AC1 and AC2) and coal (AC3), and the surface functional groups, solution pH, specific surface areas, pore volumes, and morphologies of the three samples were evaluated. The specific surface areas were in the following order: AC1 (1391 m²/g) > AC2 (1053 m²/g) > AC3 (807 m²/g). The pore volume and mean pore diameter of AC3 were greater than those of AC1 and AC2. The concentration of sulfa drugs adsorbed onto the AC samples reached equilibrium within 150 h. Experimental data of the adsorption rate were fitted to a pseudo-second-order model. The amount of sulfa drugs adsorbed onto the AC samples was in the order of SDM < SMM < SDD < SMX; the mechanism of adsorption of the sulfa drugs onto the AC samples depended on the hydrophobicity of the AC surface. The adsorption isotherm data were fitted to Freundlich and Langmuir models. Ozone was generated from oxygen gas using an A-27 ozone generator, and the complete degradation of the sulfa drugs by ozone treatment at 60 mL/min was achieved within 50 min. Ozone treatment caused the structure of the sulfa drugs to decompose via ozone oxidation.

Nanostructure and burning mode of light-duty diesel particulate with conventional diesel, biodiesel, and intermediate blends

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

Strzelec, Andrea; Vander Wal, Randy L.; Lewis, Samuel A.

The nanostructure of diesel particulates has been shown to impact its oxidation rate and burnout trajectory. Additionally, this nanostructure can evolve during the oxidation process, furthering its influence on the burnout process. For this paper, exhaust particulates were generated on a light-duty diesel engine with conventional diesel fuel, biodiesel, and intermediate blends of the two at a single load-speed point. Despite the singular engine platform and operating point, the different fuels created particulates with varied nanostructure, thereby greatly expanding the window for observing nanostructure evolution and oxidation. The physical and chemical properties of the particulates in the nascent state andmore » at partial oxidation states were measured in a laboratory reactor and by high-resolution transmission electron microscopy as a function of the degree of oxidation in O 2. X-ray photoacoustic spectroscopy analysis, thermal desorption, and solvent extraction of the nascent particulate samples reveal a significant organic content in the biodiesel-derived particulates, likely accounting for differences in the nanostructure. This study reports the nanoscale structural changes in the particulate with biofuel blend level and during O 2 oxidation as observed by high-resolution transmission electron microscopy and quantitated by fringe analysis and Brunnauer–Emmet–Teller total surface area measurements. It was observed that initial fuel-related differences in the lamella lengths, spacing, and curvature disappear when the particulate reaches approximately 50% burnout. Specifically, the initial ordered, fullerenic, and amorphous nanostructures converge during the oxidation process and the surface areas of these particulates appear to grow through these complex changes in internal particle structure. The specific surface area, measured at several points along the burnout trajectory, did not match the shrinking core projection and in contrast suggested that internal porosity was increasing. Thus, the appropriate burnout model for these particulates is significantly different from the standard shrinking core assumption, which does not account for any internal structure. Finally, an alternative burnout model is supported by high-resolution transmission electron microscopy image analysis.« less

Nanostructure and burning mode of light-duty diesel particulate with conventional diesel, biodiesel, and intermediate blends

DOE PAGES

Strzelec, Andrea; Vander Wal, Randy L.; Lewis, Samuel A.; ...

2017-01-18

The nanostructure of diesel particulates has been shown to impact its oxidation rate and burnout trajectory. Additionally, this nanostructure can evolve during the oxidation process, furthering its influence on the burnout process. For this paper, exhaust particulates were generated on a light-duty diesel engine with conventional diesel fuel, biodiesel, and intermediate blends of the two at a single load-speed point. Despite the singular engine platform and operating point, the different fuels created particulates with varied nanostructure, thereby greatly expanding the window for observing nanostructure evolution and oxidation. The physical and chemical properties of the particulates in the nascent state andmore » at partial oxidation states were measured in a laboratory reactor and by high-resolution transmission electron microscopy as a function of the degree of oxidation in O 2. X-ray photoacoustic spectroscopy analysis, thermal desorption, and solvent extraction of the nascent particulate samples reveal a significant organic content in the biodiesel-derived particulates, likely accounting for differences in the nanostructure. This study reports the nanoscale structural changes in the particulate with biofuel blend level and during O 2 oxidation as observed by high-resolution transmission electron microscopy and quantitated by fringe analysis and Brunnauer–Emmet–Teller total surface area measurements. It was observed that initial fuel-related differences in the lamella lengths, spacing, and curvature disappear when the particulate reaches approximately 50% burnout. Specifically, the initial ordered, fullerenic, and amorphous nanostructures converge during the oxidation process and the surface areas of these particulates appear to grow through these complex changes in internal particle structure. The specific surface area, measured at several points along the burnout trajectory, did not match the shrinking core projection and in contrast suggested that internal porosity was increasing. Thus, the appropriate burnout model for these particulates is significantly different from the standard shrinking core assumption, which does not account for any internal structure. Finally, an alternative burnout model is supported by high-resolution transmission electron microscopy image analysis.« less

Improved Electrochromic Characteristics of a Honeycomb-Structured Film Composed of NiO.

PubMed

Yang, Hyeeun; Lee, Yulhee; Kim, Dong In; Seo, Hyeon Jin; Yu, Jung-Hoon; Nam, Sang-Hun; Boo, Jin-Hyo

2018-09-01

Color changes controlled by electronic energies have been studied for many years in order to fabricate energy-efficient smart windows. Reduction and oxidization of nickel oxide under the appropriate voltage can change the color of a window. For a superior nickel oxide (NiO) electrochromic device (ECD), it is important to control the chemical and physical characteristics of the surface. In this study, we applied polystyrene bead templates to nickel oxide films to fabricate a honeycomb-structured electrochromic (EC) layer. We synthesized uniform polystyrene beads using the chemical wet method and placed them on substrates to create honeycomb-structured NiO films. Then, the EC characteristics of the nickel oxide films with a honeycomb structure were evaluated with UV-Visible and cyclic voltammetry. FE-SEM and AFM were used to measure the morphologies of the nanostructures and the efficiencies of the redox reactions related to the specific surface area.

Facile Synthesis of Self-Assembled Flower-Like Mesoporous Zinc Oxide Nanoflakes for Energy Applications

NASA Astrophysics Data System (ADS)

Saranya, P. E.; Selladurai, S.

Flower-shaped self-assembled zinc oxide (ZnO) nanoflakes were successfully synthesized via a temperature-controlled hydrothermal method. The crystallinity and phase formation of the compound were determined from powder X-ray diffraction (PXRD) result. Surface morphology investigations reveal the self-assembled ZnO nanoflakes to form a spherical flower-like structure. In addition, the particle size was determined from high-resolution transmission electron microscope measurement as 18nm which is in accord with XRD and UV results. X-ray photo electron spectroscopy studies reveal the chemical composition and oxidation state of the ZnO nanoparticle. The specific surface area was calculated, and mesoporous nature was confirmed using Brunauer-Emmett-Teller analysis. Results support the superior interaction between the electrode and electrolyte ions through surface pores. Capacitive performance of the ZnO electrode material was determined using cyclic voltammetry and galvanostatic charge/discharge studies, and a maximum specific capacitance of 322F/g was obtained at 5mV/sec. Electrochemical impedance spectrum reveals the materials fast charge transfer kinetics.

Meso and micro-scale response of post carbon removal nitrifying MBBR biofilm across carrier type and loading.

PubMed

Young, Bradley; Banihashemi, Bahman; Forrest, Daina; Kennedy, Kevin; Stintzi, Alain; Delatolla, Robert

2016-03-15

This study investigates the effects of three specific moving bed biofilm reactor (MBBR) carrier types and two surface area loading rates on biofilm thickness, morphology and bacterial community structure of post carbon removal nitrifying MBBR systems along with the effects of carrier type and loading on ammonia removal rates and effluent solids settleability. The meso and micro analyses show that the AOB kinetics vary based on loading condition, but irrespective of carrier type. The meso-scale response to increases in loading was shown to be an increase in biofilm thickness with higher surface area carriers being more inclined to develop and maintain thicker biofilms. The pore spaces of these higher surface area to volume carriers also demonstrated the potential to become clogged at higher loading conditions. Although the biofilm thickness increased during higher loading conditions, the relative percentages of both the embedded viable and non-viable cells at high and conventional loading conditions remained stable; indicating that the reduced ammonia removal kinetics observed during carrier clogging events is likely due to the observed reduction in the surface area of the attached biofilm. Microbial community analyses demonstrated that the dominant ammonia oxidizing bacteria for all carriers is Nitrosomonas while the dominant nitrite oxidizing bacteria is Nitrospira. The research showed that filamentous species were abundant under high loading conditions, which likely resulted in the observed reduction in effluent solids settleability at high loading conditions as opposed to conventional loading conditions. Although the settleability of the effluent solids was correlated to increases in abundances of filamentous organisms in the biofilm, analyzed using next generation sequencing, the ammonia removal rate was not shown to be directly correlated to specific meso or micro-scale characteristics. Instead post carbon removal MBBR ammonia removal kinetics were shown to be related to the viable AOB cell coverage of the carriers; which was calculated by normalizing the surface area removal rate by the biofilm thickness, the bacterial percent abundance of ammonia oxidizing bacteria and the percentage of viable cells. Copyright © 2016 Elsevier Ltd. All rights reserved.

Clay mineralogy in different geomorphic surfaces in sugarcane areas

NASA Astrophysics Data System (ADS)

Camargo, L.; Marques, J., Jr.

2012-04-01

The crystallization of the oxides and hydroxides of iron and aluminum and kaolinite of clay fraction is the result of pedogenetic processes controlled by the relief. These minerals have influence on the physical and chemical attributes of soil and exhibit spatial dependence. The pattern of spatial distribution is influenced by forms of relief as the geomorphic surfaces. In this sense, the studies aimed at understanding the relationship between relief and the distribution pattern of the clay fraction attributes contribute to the delineation of specific areas of management in the field. The objective of this study was to evaluate the spatial distribution of oxides and hydroxides of iron and aluminum and kaolinite of clay fraction and its relationship with the physical and chemical attributes in different geomorphic surfaces. Soil samples were collected in a transect each 25 m (100 samples) and in the sides of the same (200 samples) as well as an area of 500 ha (1 sample each six hectare). Geomorphic surfaces (GS) in the transect were mapped in detail to support mapping the entire area. The soil samples were taken to the laboratory for chemical, physical, and mineralogical analysis, and the pattern of spatial distribution of soil attributes was obtained by statistics and geostatistics. The GS I is considered the oldest surface of the study area, with depositional character, and a slope ranging from 0 to 4%. GS II and III are considered to be eroded, and the surface II plan a gentle slope that extends from the edge of the surface until the beginning of I and III. The crystallographic characteristics of the oxides and hydroxides of iron and aluminum and kaolinite showed spatial dependence and the distribution pattern corresponding to the limits present of the GS in the field. Surfaces I and II showed the best environments to the degree of crystallinity of hematite and the surface III to the greatest degree of crystallinity of goethite agreeing to the pedoenvironment conditions of each surface. The rate goethite/(goethite+hematite) decreases the surface I to III this result is the variation of the source material that has an increase of clay which is characteristic of sandstone rock (Adamantine Formation) in the surface III. The rate kaolinite/(kaolinite+gibbsite) also shows a decrease of the surface I to the surface III. The spatial distribution pattern of mineralogy influenced the pattern of physical and chemical properties. On the surface III (with higher iron and gibbsite) had the best physical condition (lower density, higher porosity and aggregates) and greater phosphorus sorption. In this sense, the identification and mapping of the GSs, allowed a better understanding of cause and effect of the distribution of soils in the area, and the recognition of areas of controlled variability of soil attributes. These areas can be considered specific areas of management, useful for planning and management practices in the culture of sugarcane. Besides, suggesting criteria for the recognition of map units that would be equivalent to the future series of soils of the Brazilian System of Soil Classification.

Fabrication and characterization of akaganeite/graphene oxide nanocomposite for arsenic removal from water

NASA Astrophysics Data System (ADS)

Trang, Nguyen Thi Thuy; Thy, Lu Thi Mong; Cuong, Pham Mai; Tu, Tran Hoang; Hieu, Nguyen Huu

2018-04-01

In this study, akageneite/graphene oxide (β-FeOOH/GO) nanocomposite was fabricated by in situ forced hydrolysis of iron (III) chloride. The structure and morphology of β-FeOOH/GO were characterized by Fourier Transform Infrared Spectroscopy (FTIR), X-ray diffraction (XRD), transmission electron microscopy (TEM), and Brunauer-Emmett- Teller (BET) specific surface area. XRD, FTIR, and TEM results indicated that β-FeOOH nanoparticles were successfully decorated on the surface of GO nanosheets. The BET specific surface area of β-FeOOH/GO was observed of 97.94 m2/g. The nanocomposite was used as an adsorbent for removal of arsenic (As5+) from water. Adsorption experiments were carried out to investigate contact time, pH values, and As5+ initial concentrations. The adsorption equilibrium time was reached within 180 minutes. The adsorption was well-fitted by a pseudo-second-order kinetic and Langmuir isotherm model. The maximum adsorption capacity of β-FeOOH/GO for As5+ ions of 94.34 mg/g that was calculated from the Langmuir model at pH 3. Accordingly, the nanocomposite β-FeOOH/GO could be considered as a highly efficient adsorbent for removing arsenic from water.

The nanosphere iron mineral(s) in Mars soil

NASA Technical Reports Server (NTRS)

Banin, A.; Ben-Shlomo, T.; Margulies, L.; Blake, D. F.; Mancinelli, R. L.; Gehring, A. U.

1993-01-01

A series of surface-modified clays containing nanophase (np) iron/oxyhydroxides of extremely small particle sizes, with total iron contents as high as found in Mars soil, were prepared by iron deposition on the clay surface from ferrous chloride solution. Comprehensive studies of the iron mineralogy in these 'Mars-soil analogs' were conducted using chemical extractions, solubility analyses, pH and redox, x ray and electron diffractometry, electron microscopic imaging specific surface area and particle size determinations, differential thermal analyses, magnetic properties characterization, spectral reflectance, and Viking biology simulation experiments. The clay matrix and the procedure used for synthesis produced nanophase iron oxides containing a certain proportion of divalent iron, which slowly converts to more stable, fully oxidized iron minerals. The noncrystalline nature of the iron compounds precipitated on the surface of the clay was verified by their complete extractability in oxalate. Lepidocrocite (gamma-FeOOH) was detected by selected area electron diffraction. It is formed from a double iron Fe(II)/Fe(III) hydroxyl mineral such as 'green rust', or ferrosic hydroxide. Magnetic measurements suggested that lepidocrocite converted to the more stable meaghemite (gamma-Fe203) by mild heat treatment and then to nanophase hematite (aplha-Fe203) by extensive heat treatment. Their chemical reactivity offers a plausible mechanism for the somewhat puzzling observations of the Viking biology experiments. Their unique chemical reactivities are attributed to the combined catalytic effects of the iron oxide/oxyhydroxide and silicate phase surfaces. The mode of formation of these (nanophase) iron oxides on Mars is still unknown.

Preparation and characterization of vanadia-titania mixed oxide for immobilization of Serratia rubidaea CCT 5732 and Klebsiella marcescens bacteria

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

Saragiotto Colpini, Leda Maria; Correia Goncalves, Regina A.; Goncalves, Jose Eduardo

2008-08-04

Vanadia-titania mixed oxide was synthesized by sol-gel method and characterized by several techniques. Texturally, it is formed by mesopores and presents high-specific surface area and controlled porosity. Scanning electron microscopy revealed that vanadium is homogeneously distributed in the material. Structurally, it was possible to identify characteristic V=O stretching bands by IR. The analysis of X-ray diffraction showed that the material, particularly vanadium, is highly dispersed. Application experiments were carried out through the immobilization of Serratia rubidae CCT 5732 and Klebsiella marcescens bacteria by adsorption on the surface of mixed oxide. The micrographies revealed that the bacteria were adsorbed on themore » entire support, with average surface densities of 8.55 x 10{sup 11} cells/m{sup 2} (Serratia rubidae CCT 5732) and 3.40 x 10{sup 11} cells/m{sup 2} (K. marcescens)« less

Inorganic nanostructured materials for high performance electrochemical supercapacitors

NASA Astrophysics Data System (ADS)

Liu, Sheng; Sun, Shouheng; You, Xiao-Zeng

2014-01-01

Electrochemical supercapacitors (ES) are a well-known energy storage system that has high power density, long life-cycle and fast charge-discharge kinetics. Nanostructured materials are a new generation of electrode materials with large surface area and short transport/diffusion path for ions and electrons to achieve high specific capacitance in ES. This mini review highlights recent developments of inorganic nanostructure materials, including carbon nanomaterials, metal oxide nanoparticles, and metal oxide nanowires/nanotubes, for high performance ES applications.

Inorganic nanostructured materials for high performance electrochemical supercapacitors.

PubMed

Liu, Sheng; Sun, Shouheng; You, Xiao-Zeng

2014-02-21

Electrochemical supercapacitors (ES) are a well-known energy storage system that has high power density, long life-cycle and fast charge-discharge kinetics. Nanostructured materials are a new generation of electrode materials with large surface area and short transport/diffusion path for ions and electrons to achieve high specific capacitance in ES. This mini review highlights recent developments of inorganic nanostructure materials, including carbon nanomaterials, metal oxide nanoparticles, and metal oxide nanowires/nanotubes, for high performance ES applications.

Porous polymeric materials for hydrogen storage

DOEpatents

Yu, Luping [Hoffman Estates, IL; Liu, Di-Jia [Naperville, IL; Yuan, Shengwen [Chicago, IL; Yang, Junbing [Westmont, IL

2011-12-13

Porous polymers, tribenzohexazatriphenylene, poly-9,9'-spirobifluorene, poly-tetraphenyl methane and their derivatives for storage of H.sub.2 prepared through a chemical synthesis method. The porous polymers have high specific surface area and narrow pore size distribution. Hydrogen uptake measurements conducted for these polymers determined a higher hydrogen storage capacity at the ambient temperature over that of the benchmark materials. The method of preparing such polymers, includes oxidatively activating solids by CO.sub.2/steam oxidation and supercritical water treatment.

Porous polymeric materials for hydrogen storage

DOEpatents

Yu, Luping; Liu, Di-Jia; Yuan, Shengwen; Yang, Junbing

2013-04-02

A porous polymer, poly-9,9'-spirobifluorene and its derivatives for storage of H.sub.2 are prepared through a chemical synthesis method. The porous polymers have high specific surface area and narrow pore size distribution. Hydrogen uptake measurements conducted for these polymers determined a higher hydrogen storage capacity at the ambient temperature over that of the benchmark materials. The method of preparing such polymers, includes oxidatively activating solids by CO.sub.2/steam oxidation and supercritical water treatment.

Calculations and measurements of contact resistance of semi-transparent Ni/Pd contacts to p-GaN.

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

Crofton, John; Bogart, Katherine Huderle Andersen

2005-06-01

Calculations of specific contact resistance as a function of doping and barrier height were performed for p-type GaN. These calculations took into account two valence bands, each with different effective masses, and show that at low doping, the heavy hole band accounts for most of the conduction, whereas at heavier doping, the light hole band dominates conduction. These calculations also indicate the barrier height for typical contacts to p-GaN is between 0.75 eV and 1 eV. Specific contact resistance measurements were made for oxidized Ni/Au, Pd, and oxidized Ni/Pd ohmic contact metal schemes to p-GaN. The Ni/Pd contact had themore » lowest specific contact resistance, 6 x 10{sup -4} {Omega} cm{sup 2}. Auger sputter depth profile analysis showed some Ni diffused away from the GaN surface to the contact surface with the bulk of the Pd located in between two areas of Ni. Both Ni and Pd interdiffused with the GaN at the semiconductor surface. The majority of the oxygen observed was with the Ni as NiO. Angle-resolved-x-ray photoelectron spectroscopy (AR-XPS) analyses showed the formation of predominantly NiO and PdO species, with higher Ni and Pd oxides at the contact surface.« less

Porous carbon nanotube/graphene composites for high-performance supercapacitors

NASA Astrophysics Data System (ADS)

Li, Jing; Tang, Jie; Yuan, Jinshi; Zhang, Kun; Yu, Xiaoliang; Sun, Yige; Zhang, Han; Qin, Lu-Chang

2018-02-01

Carbon nanotubes (CNTs) are an effective spacer to prevent the re-stacking of graphene layers. However, the aggregation of CNTs always reduces the specific surface area of resulting CNT/graphene composites. Meanwhile, different pores always have different contributions to the specific capacitance. In this study, CNT/graphene composites with different porous structures are synthesized by co-reduction of oxidized CNTs and graphene oxide with different mixing ratios. With an optimized CNT content of 20%, the CNT/graphene composite shows 206 F g-1 in 1-ethyl-3-methylimidazolium tetrafluoroborate electrolyte. It is found that pores larger than twice the size of electrolyte ions can make greater contributions to the specific capacitance.

Nanoporous graphene obtained by hydrothermal process in H2O2 and its application for supercapacitors

NASA Astrophysics Data System (ADS)

Lv, Jinlong; Liang, Tongxiang

2016-08-01

Nanohole graphene oxide (NHGO) was obtained in a homogeneous aqueous mixture of graphene oxide (GO) and H2O2 at 120 °C. Supercapacitors were fabricated as the electrode material by using NHGO. A specific capacitance of 240.1 F g-1 was obtained at a current density of 1 A g-1 in 6 m KOH electrolyte and specific capacitance remained 193.6 F g-1 at the current density of 20 A g-1. This was attributed to reducing the inner space between the double-layers, enhanced ion diffusion and large specific surface area. Supercapacitor prepared with NHGO electrodes also exhibited an excellent cycle stability.

Facile Synthesis of Wormhole-Like Mesoporous Tin Oxide via Evaporation-Induced Self-Assembly and the Enhanced Gas-Sensing Properties

NASA Astrophysics Data System (ADS)

Li, Xiaoyu; Peng, Kang; Dou, Yewei; Chen, Jiasheng; Zhang, Yue; An, Gai

2018-01-01

Wormhole-like mesoporous tin oxide was synthesized via a facile evaporation-induced self-assembly (EISA) method, and the gas-sensing properties were evaluated for different target gases. The effect of calcination temperature on gas-sensing properties of mesoporous tin oxide was investigated. The results demonstrate that the mesoporous tin oxide sensor calcined at 400 °C exhibits remarkable selectivity to ethanol vapors comparison with other target gases and has a good performance in the operating temperature and response/recovery time. This might be attributed to their high specific surface area and porous structure, which can provide more active sites and generate more chemisorbed oxygen spices to promote the diffusion and adsorption of gas molecules on the surface of the gas-sensing material. A possible formation mechanism of the mesoporous tin oxide and the enhanced gas-sensing mechanism are proposed. The mesoporous tin oxide shows prospective detecting application in the gas sensor fields.

Effect of CO on the field emission properties of tetrapod zinc oxide cathode.

PubMed

Wang, Jinchan; Zhang, Xiaobing; Lei, Wei; Mao, Fuming; Cui, Yunkang; Xiao, Mei

2012-08-01

Tetrapod zinc oxide (T-ZnO), being a kind of nano-material, has large specific surface area and surface binding energy, which will make it sensitive to the ambient gas condition. So the field emission properties will be influenced by the gas adsorption when being applied as the cathode materials of field emission devices. Carbon monoxide is the main residual gas in T-ZnO field emission devices. In this paper, carbon monoxide was introduced into a field emission device with T-ZnO emitters. The field emission currents of tetrapod ZnO were compared before and after exposure to CO.

Enlargement of halloysite clay nanotube lumen by selective etching of aluminum oxide.

PubMed

Abdullayev, Elshad; Joshi, Anupam; Wei, Wenbo; Zhao, Yafei; Lvov, Yuri

2012-08-28

Halloysite clay tubes have 50 nm diameter and chemically different inner and outer walls (inner surface of aluminum oxide and outer surface of silica). Due to this different chemistry, the selective etching of alumina from inside the tube was realized, while preserving their external diameter (lumen diameter changed from 15 to 25 nm). This increases 2-3 times the tube lumen capacity for loading and further sustained release of active chemical agents such as metals, corrosion inhibitors, and drugs. In particular, halloysite loading efficiency for the benzotriazole increased 4 times by selective etching of 60% alumina within the tubes' lumens. Specific surface area of the tubes increased over 6 times, from 40 to 250 m(2)/g, upon acid treatment.

A novel high specific surface area conducting paper material composed of polypyrrole and Cladophora cellulose.

PubMed

Mihranyan, Albert; Nyholm, Leif; Bennett, Alfonso E Garcia; Strømme, Maria

2008-10-02

We present a novel conducting polypyrrole-based composite material, obtained by polymerization of pyrrole in the presence of iron(III) chloride on a cellulose substrate derived from the environmentally polluting Cladophora sp. algae. The material, which was doped with chloride ions, was molded into paper sheets and characterized using scanning and transmission electron microscopy, N 2 gas adsorption analysis, cyclic voltammetry, chronoamperometry and conductivity measurements at varying relative humidities. The specific surface area of the composite was found to be 57 m (2)/g and the fibrous structure of the Cladophora cellulose remained intact even after a 50 nm thick layer of polypyrrole had been coated on the cellulose fibers. The composite could be repeatedly used for electrochemically controlled extraction and desorption of chloride and an ion exchanging capacity of 370 C per g of composite was obtained as a result of the high surface area of the cellulose substrate. The influence of the oxidation and reduction potentials on the chloride ion exchange capacity and the nucleation of delocalized positive charges, forming conductive paths in the polypyrrole film, was also investigated. The creation of conductive paths during oxidation followed an effective medium rather than a percolative behavior, indicating that some conduction paths survive the polymer reduction steps. The present high surface area material should be well-suited for use in, e.g., electrochemically controlled ion exchange or separation devices, as well as sensors based on the fact that the material is compact, light, mechanically stable, and moldable into paper sheets.

Synthesis and properties of ternary mixture of nickel/cobalt/tin oxides for supercapacitors

NASA Astrophysics Data System (ADS)

Ferreira, C. S.; Passos, R. R.; Pocrifka, L. A.

2014-12-01

The present study reports the synthesis and morphological, structural and electrochemical characterization of ternary oxides mixture containing nickel, cobalt and tin. The ternary oxide is synthesized by Pechini method with subsequent deposition onto a titanium substrate in a thin-film form. XRD and EDS analysis confirm the formation of ternary film with amorphous nature. SEM analysis show that cracks on the film favor the gain of the surface area that is an interesting feature for electrochemical capacitors. The ternary film is investigated in KOH electrolyte solution using cyclic voltammetry and charge-discharge study with a specific capacitance of 328 F g-1, and a capacitance retention of 86% over 600 cycles. The values of specific power and specific energy was 345.7 W kg-1 and 18.92 Wh kg-1, respectively.

Characterization and electrochemical application of carbon materials based on poly(phenylene oxide)

NASA Astrophysics Data System (ADS)

Gray, Hunter

Carbon materials possess excellent electrical and surface properties for the next generation of energy storage devices. Polymers provide a carbon rich and tailorable precursor for the production of carbon materials. Therefore, activated carbons were prepared from poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) via a three step process: thermal oxidation, carbonization, and activation with KOH. The activated carbons are predominately microporous with BET specific surface areas up to 2638 m2/g. Impedance spectroscopy revealed these carbons possess electrical conductivities comparable to commercial carbon blacks and consequently were employed in thin-film composite electrodes in electrochemical double-layer capacitors. Cyclic voltammetry confirmed maximum specific capacitances of 13.23 F/g and 2.848 F/g for aqueous and organic electrolyte systems, respectively. Additionally, carbon nanotubes were synthesized from PPO and other polymers with a nickel catalyst via chemical vapor deposition as revealed by transmission electron microscopy. This is the first report of carbon nanotubes produced from PPO.

Formula of an ideal carbon nanomaterial supercapacitor

NASA Astrophysics Data System (ADS)

Samuilova, Larissa; Frenkel, Alexander; Samuilov, Vladimir

2014-03-01

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

Thermodynamics of manganese oxides: Sodium, potassium, and calcium birnessite and cryptomelane

PubMed Central

Birkner, Nancy; Navrotsky, Alexandra

2017-01-01

Manganese oxides with layer and tunnel structures occur widely in nature and inspire technological applications. Having variable compositions, these structures often are found as small particles (nanophases). This study explores, using experimental thermochemistry, the role of composition, oxidation state, structure, and surface energy in the their thermodynamic stability. The measured surface energies of cryptomelane, sodium birnessite, potassium birnessite and calcium birnessite are all significantly lower than those of binary manganese oxides (Mn3O4, Mn2O3, and MnO2), consistent with added stabilization of the layer and tunnel structures at the nanoscale. Surface energies generally decrease with decreasing average manganese oxidation state. A stabilizing enthalpy contribution arises from increasing counter-cation content. The formation of cryptomelane from birnessite in contact with aqueous solution is favored by the removal of ions from the layered phase. At large surface area, surface-energy differences make cryptomelane formation thermodynamically less favorable than birnessite formation. In contrast, at small to moderate surface areas, bulk thermodynamics and the energetics of the aqueous phase drive cryptomelane formation from birnessite, perhaps aided by oxidation-state differences. Transformation among birnessite phases of increasing surface area favors compositions with lower surface energy. These quantitative thermodynamic findings explain and support qualitative observations of phase-transformation patterns gathered from natural and synthetic manganese oxides. PMID:28130549

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

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

Supported versus colloidal zinc oxide for advanced oxidation processes

NASA Astrophysics Data System (ADS)

Laxman, Karthik; Al Rashdi, Manal; Al Sabahi, Jamal; Al Abri, Mohammed; Dutta, Joydeep

2017-07-01

Photocatalysis is a green technology which typically utilizes either supported or colloidal catalysts for the mineralization of aqueous organic contaminants. Catalyst surface area and surface energy are the primary factors determining its efficiency, but correlation between the two is still unclear. This work explores their relation and hierarchy in a photocatalytic process involving both supported and colloidal catalysts. In order to do this the active surface areas of supported zinc oxide nanorods (ZnO NR's) and colloidal zinc oxide nanoparticles (having different surface energies) were equalized and their phenol oxidation mechanism and capacity was analyzed. It was observed that while surface energy had subtle effects on the oxidation rate of the catalysts, the degradation efficiency was primarily a function of the surface area; which makes it a better parameter for comparison when studying different catalyst forms of the same material. Thus we build a case for the use of supported catalysts, wherein their catalytic efficiency was tested to be unaltered over several days under both natural and artificial light, suggesting their viability for practical applications.

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

NASA Astrophysics Data System (ADS)

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

2006-10-01

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

Synthesis and characterization of Co3O4 prepared from atmospheric pressure acid leach liquors of nickel laterite ores

NASA Astrophysics Data System (ADS)

Meng, Long; Guo, Zhan-cheng; Qu, Jing-kui; Qi, Tao; Guo, Qiang; Hou, Gui-hua; Dong, Peng-yu; Xi, Xin-guo

2018-01-01

A chemical precipitation-thermal decomposition method was developed to synthesize Co3O4 nanoparticles using cobalt liquor obtained from the atmospheric pressure acid leaching process of nickel laterite ores. The effects of the precursor reaction temperature, the concentration of Co2+, and the calcination temperature on the specific surface area, morphology, and the electrochemical behavior of the obtained Co3O4 particles were investigated. The precursor basic cobaltous carbonate and cobaltosic oxide products were characterized and analyzed by Fourier transform infrared spectroscopy, thermogravimetric differential thermal analysis, X-ray diffraction, field-emission scanning electron microscopy, specific surface area analysis, and electrochemical analysis. The results indicate that the specific surface area of the Co3O4 particles with a diameter of 30 nm, which were obtained under the optimum conditions of a precursor reaction temperature of 30°C, 0.25 mol/L Co2+, and a calcination temperature of 350°C, was 48.89 m2/g. Electrodes fabricated using Co3O4 nanoparticles exhibited good electrochemical properties, with a specific capacitance of 216.3 F/g at a scan rate of 100 mV/s.

Surface functionalization of magnetic nanoparticles formed by self-associating hydrophobized oxidized dextrans

NASA Astrophysics Data System (ADS)

Farber, Shimon; Ickowicz, Diana E.; Melnik, Kristie; Yudovin-Farber, Ira; Recko, Daniel; Rampersaud, Arfaan; Domb, Abraham J.

2014-06-01

Magnetic iron oxide nanoparticles surface covered with oleic acid layer followed by a second layer of hydrophobized oxidized dextran aldehyde were prepared and tested for physico-chemical properties and ligand- and cell-specific binding. It was demonstrated that oleic acid-iron oxide nanoparticles coated with an additional layer of hydrophobized oxidized dextran were dispersible in buffer solutions and possess surface aldehyde active groups available for further binding of ligands or markers via imine or amine bond formation. Hydrophobized dextrans were synthesized by periodate oxidation and conjugation of various alkanamines to oxidized dextran by imination. Physico-chemical properties, as separation using magnetic field, magnetite concentration, and particle diameter, of the prepared magnetic samples are reported. The biotin-binding protein, neutravidin, was coupled to the particle surface by a simple reductive amination procedure. The particles were used for specific cell separation with high specificity.

Design and synthesis of inorganic/organic hybrid electrochemical materials

NASA Astrophysics Data System (ADS)

Harreld, John H.

An ambient pressure method for drying sol-gel materials is developed to synthesize high porosity (80--90%), high surface area vanadium oxide and silica aerogel materials (150--300 and 1000 m2/g for vanadium pentoxide and silica, respectively). The synthesis approach uses liquid exchange to replace the pore fluid with a low surface tension, nonpolar solvent which reduces the capillary pressures developed during drying. The Good-Girifalco interaction parameter is used to calculate pore stresses resulting from drying silica gels from various liquids. Vanadium oxide/polypyrrole hybrid aerogels are prepared using three strategies. These approaches focus on either sequential or consecutive polymerization of the inorganic and organic networks. Microcomposite aerogels are synthesized by encapsulating a dispersion of preformed polypyrrole in a vanadium pentoxide gel. In the second approach, pyrrole is polymerized and doped within the pore volume of preformed vanadium pentoxide gel. When the inorganic and organic precursors are polymerized simultaneously, the resulting gels exhibited a nanometer scaled microstructure with homogeneous distributions of either phases. Through this route, a suitable microstructure and composition for a lithium secondary battery cathode is obtained. Lithiated aerogels of hydrated nickel, cobalt, and mixed nickel-cobalt oxides are synthesized from lithium hydroxide and transition metal acetate precursors. The XRD analyses indicate that the nickel containing gels exhibit a lithium deficiency (less than 1 Li/transition metal. By increasing the concentration of the lithium precursor the lithium content in nickel oxides is increased, and additional base solution is no longer required to catalyze gelation. A non-hydrolytic sol-gel approach is utilized to create tin oxide and tin-aluminum binary oxide aerogels with high porosity (90%) and high surface area (300 m2/g). XRD data from single phase tin oxide aerogel indicates the growth of SnO2 crystallites between 150--400°C in air, accompanied by a reduction in surface area (30 m2/g). Heated tin oxide aerogel exhibits comparable reversible specific capacity (390 mAh/g) as that of commercial SnO2 (420 mAh/g). Amorphous tin oxide aerogel is stabilized to higher temperatures when aluminum oxide is incorporated into the structure. The tin oxide phase remains electrochemically active towards lithium insertion and exhibits excellent reversibility during cycling.

Oxidation Resistance of Materials Based on Ti3AlC2 Nanolaminate at 600 °C in Air

NASA Astrophysics Data System (ADS)

Ivasyshyn, Andrij; Ostash, Orest; Prikhna, Tatiana; Podhurska, Viktoriya; Basyuk, Tatiana

2016-08-01

The oxidation behavior of Ti3AlC2-based materials had been investigated at 600 °C in static air for 1000 h. It was shown that the intense increase of weight gain per unit surface area for sintered material with porosity of 22 % attributed to oxidation of the outer surface of the specimen and surfaces of pores in the bulk material. The oxidation kinetics of the hot-pressed Ti3AlC2-based material with 1 % porosity remarkably increased for the first 15 h and then slowly decreased. The weight gain per unit surface area for this material was 1.0 mg/cm2 after exposition for 1000 h. The intense initial oxidation of Ti3AlC2-based materials can be eliminated by pre-oxidation treatment at 1200 °C in air for 2 h. As a result, the weight gain per unit surface area for the pre-oxidized material did not exceed 0.11 mg/cm2 after 1000 h of exposition at 600 °C in air. It was demonstrated that the oxidation resistance of Ti3AlC2-based materials can be significantly improved by niobium addition.

Using reduced graphene oxide-Ca:CdSe nanocomposite to enhance photoelectrochemical activity of gold nanoparticles functionalized tungsten oxide for highly sensitive prostate specific antigen detection.

PubMed

Wang, Xueping; Xu, Rui; Sun, Xu; Wang, Yaoguang; Ren, Xiang; Du, Bin; Wu, Dan; Wei, Qin

2017-10-15

An ultrasensitive sandwich-type photoelectrochemical (PEC) immunosensor was constructed for the detection of prostate specific antigen (PSA). In this work, Au-nanoparticle-loaded tungsten oxide (WO 3 -Au) hybrid composites was applied as PEC sensing platform, while Ca ions doped CdSe equipped on the conducting framework of reduced graphene oxide (rGO-Ca:CdSe) nanocomposites were employed as the signal amplification probe. As for WO 3 -Au, massive Au nanoparticles were formed on the surface of WO 3 without any additional reducing agent, providing a novel nanocarriers for anchoring plenty of the primary antibodies due to the large specific surface area and good biocompatibility by chemical bonding between Au nanoparticles and -NH 2 of antibodies. Besides, the incorporation of the rGO and the doping of Ca ions could improve the conductivity and hinder the recombination of electron-hole pairs of CdSe nanoparticles effectively, thereby enhancing the photocurrent conversion efficiency. Based on the sandwich immunoreaction, the primary antibody was immobilized onto WO 3 -Au substrate, after the formed rGO-Ca:CdSe labels were captured onto the electrode surface via the specific antibody-antigen interaction, the photocurrent intensity could be further enhanced due to the sensitization effect. Under the optimal conditions, the proposed PEC immunosensor shows a linear relationship between photocurrent variation and the logarithm of PSA concentration in the wide range of 5pgmL -1 to 50ngmL -1 with a low detection limit of 2.6pgmL -1 (S/N=3). Moreover, it also presented good stability and acceptable specificity, indicating the potential applications in clinical diagnostics. Copyright © 2017 Elsevier B.V. All rights reserved.

Graphene oxide-based benzimidazole-crosslinked networks for high-performance supercapacitors.

PubMed

Cui, Yi; Cheng, Qian-Yi; Wu, Haiping; Wei, Zhixiang; Han, Bao-Hang

2013-09-21

The synthesis of graphene oxide (GO)-based benzimidazole-crosslinked network (GOBIN) materials is presented. These materials are prepared by the covalent crosslinking of GO sheets using a condensation reaction between the carboxylic acid moieties on the GO surface and the o-aminophenyl end groups of 3,3'-diaminobenzidine (or 1,2,4,5-benzenetetraamine tetrahydrochloride). An efficient one-pot catalyst- and template-free synthesis was performed. The obtained porous GO-based materials possess a Brunauer-Emmett-Teller specific surface area ranging from 260 to 920 m(2) g(-1). Electrochemical testing indicates that the GOBIN materials display a specific capacitance up to 370 F g(-1) at a current density of 0.1 A g(-1) and about 90% of the original capacitance is retained after 5000 cycles at a current density of 3 A g(-1). Therefore, GOBIN materials can be employed as promising electrode materials for high-performance supercapacitors with outstanding cycling stability. Furthermore, owing to their significantly high specific surface area, these materials also show hydrogen uptake (up to 1.24 wt%, at 77 K and 1.0 bar) and carbon dioxide capture (up to 14.2 wt%, at 273 K and 1.0 bar) properties. As a result, these GO-based porous materials improve both the supercapacitor performance and gas sorption property, which demonstrate an excellent performance in the practical application of energy storage.

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

PubMed

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

2018-04-19

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

Adsorption and chemical reaction of gaseous mixtures of hydrogen chloride and water on aluminum oxide and application to solid-propellant rocket exhaust clouds

NASA Technical Reports Server (NTRS)

Cofer, W. R., III; Pellett, G. L.

1978-01-01

Hydrogen chloride (HCl) and aluminum oxide (Al2O3) are major exhaust products of solid rocket motors (SRM). Samples of calcination-produced alumina were exposed to continuously flowing mixtures of gaseous HCl/H2O in nitrogen. Transient sorption rates, as well as maximum sorptive capacities, were found to be largely controlled by specific surface area for samples of alpha, theta, and gamma alumina. Sorption rates for small samples were characterized linearly with an empirical relationship that accounted for specific area and logarithmic time. Chemisorption occurred on all aluminas studied and appeared to form from the sorption of about a 2/5 HCl-to-H2O mole ratio. The chemisorbed phase was predominantly water soluble, yielding chloride/aluminum III ion mole ratios of about 3.3/1 suggestive of dissolved surface chlorides and/or oxychlorides. Isopiestic experiments in hydrochloric acid indicated that dissolution of alumina led to an increase in water-vapor pressure. Dissolution in aqueous SRM acid aerosol droplets, therefore, might be expected to promote evaporation.

Evaluation of current techniques for isolation of chars as natural adsorbents

USGS Publications Warehouse

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

2004-01-01

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

Sol-gel synthesis and adsorption properties of mesoporous manganese oxide

NASA Astrophysics Data System (ADS)

Ivanets, A. I.; Kuznetsova, T. F.; Prozorovich, V. G.

2015-03-01

Sol-gel synthesis of mesoporous xerogels of manganese oxide with different phase compositions has been performed. The manganese oxide sols were obtained by redox reactions of potassium permanganate with hydrogen peroxide or manganese(II) chloride in aqueous solutions. The isotherms of the low-temperature adsorption-desorption of nitrogen with manganese oxide xerogels treated at 80, 200, 400, and 600°C were measured. The samples were studied by electron microscopy and thermal and XRD analysis. The phase transformation and the changes in the adsorption and capillary-condensation properties of manganese oxide were shown to depend on the sol synthesis conditions and the temperature of the thermal treatment of the gel. The X-ray amorphous samples heated at 80°C were shown to have low values of the specific surface; at higher temperatures, the xerogel crystallized into mixed phases with various compositions and its surface area increased at 200-400°C and decreased at 600°C.

Advanced oxidation of biorefractory organics in aqueous solution together with bioelectricity generation by microbial fuel cells with composite FO/GPEs

NASA Astrophysics Data System (ADS)

Fu, Bao-rong; Shen, Chao; Ren, Jing; Chen, Jia-yi; Zhao, Lin

2018-03-01

In this study, ferric oxide loading graphite particle electrodes (FO/GPEs) were prepared as cathode of a three-dimensional electrode MFC-Fenton system. The properties of the composite cathode were examined with higher surface area and more mesopores. FO/GPEs could work as both cathode and Fenton iron reagents, contributing to high oxidation activity and better performance of electricity generation. The application of FO/GPEs MFC-Fenton system on degrading p-nitrophenol presented high catalytic efficiency in a wide range of pH value. The removal of p-nitrophenol and TOC attained to about 85 % within 8 and 64 h at neutral pH, respectively. A neutral FO/GPEs MFC-Fenton oxidation mechanism was also proposed. Specifically, both the surface iron sites and dissolved iron ions catalyzed the decomposition of H2O2. As results, the generated hydroxyl radicals were used for p-nitrophenol degradation and the iron oxide was recycled.

Schwertmannite Synthesis through Ferrous Ion Chemical Oxidation under Different H2O2 Supply Rates and Its Removal Efficiency for Arsenic from Contaminated Groundwater.

PubMed

Liu, Fenwu; Zhou, Jun; Zhang, Shasha; Liu, Lanlan; Zhou, Lixiang; Fan, Wenhua

2015-01-01

Schwertmannite-mediated removal of arsenic from contaminated water has attracted increasing attention. However, schwertmannite chemical synthesis behavior under different H2O2 supply rates for ferrous ions oxidation is unclear. This study investigated pH, ferrous ions oxidation efficiency, and total iron precipitation efficiency during schwertmannite synthesis by adding H2O2 into FeSO4 · 7H2O solution at different supply rates. Specific surface area and arsenic (III) removal capacity of schwertmannite have also been studied. Results showed that pH decreased from ~3.48 to ~1.96, ~2.06, ~2.12, ~2.14, or ~2.17 after 60 h reaction when the ferrous ions solution received the following corresponding amounts of H2O2: 1.80 mL at 2 h (treatment 1); 0.90 mL at 2 h and 14 h (treatment 2); 0.60 mL at 2, 14, and 26 h (treatment 3); 0.45 mL at 2, 14, 26, and 38 h (treatment 4), or 0.36 mL at 2, 14, 26, 38, and 50 h (treatment 5). Slow H2O2 supply significantly inhibited the total iron precipitation efficiency but improved the specific surface area or arsenic (III) removal capacity of schwertmannite. For the initial 50.0 μg/L arsenic (III)-contaminated water under pH ~7.0 and using 0.25 g/L schwertmannite as an adsorbent, the total iron precipitation efficiency, specific surface area of the harvested schwertmannite, and schwertmannite arsenic(III) removal efficiency were 29.3%, 2.06 m2/g, and 81.1%, respectively, in treatment 1. However, the above parameters correspondingly changed to 17.3%, 16.30 m2/g, and 96.5%, respectively, in treatment 5.

Cu-modified carbon spheres/reduced graphene oxide as a high sensitivity of gas sensor for NO2 detection at room temperature

NASA Astrophysics Data System (ADS)

Su, Zhibin; Tan, Li; Yang, Ruiqiang; Zhang, Yu; Tao, Jin; Zhang, Nan; Wen, Fusheng

2018-03-01

Nitrogen dioxide (NO2) as one of the most serious air pollution is harmful to people's health, therefore high-performance gas sensors is critically needed. Here, Cu-modified carbon spheres/reduced graphene oxide (Cu@CS/RGO) composite have been prepared as NO2 gas sensor material. Carbon sphere in the interlayer of RGO can increase the specific surface area of RGO. Copper nanoparticles decorated on the surface of CS can effectively enhance the adsorption activity of RGO as supplier of free electrons. The experimental results showed that its particular structure improved the gas sensitivity of RGO at different NO2 concentrations at room temperature.

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

Enhanced glucose biosensor properties of gold nanoparticle-decorated ZnO nanorods

NASA Astrophysics Data System (ADS)

Wang, Zi-Hao; Yang, Chih-Chiang; Su, Yan-Kuin; Ruand, Jian-Long

2017-04-01

As new materials have been reported and more knowledge on detailed mechanism of glucose oxidation has been unveiled, the non-enzymatic glucose sensor keeps coming closer to practical applications. Nanostructures with higher surface specific area has great potential applications in sensing devices ZnO nanoords were synthesized in a hydrothermal method using simply available laboratory chemicals. Results showed that as-synthesized Gold Nanoparticle-decorated ZnO Nanorods possessing higher specific surface area, significantly increased the non-enzyme efficiency which in turn improved the sensing performances. The electrode also demonstrated excellent performance in sensing glucose concentration with remarkable sensitivity (46.6 μA/mM-cm2) and good repeatability. This work is expected to open a new avenue to fabricate non-enzymatic electrochemical sensors of glucose involving co-mediating.

Influence of peracetic acid modification on the physicochemical properties of activated carbon and its performance in the ozone-catalytic oxidation of gaseous benzene

NASA Astrophysics Data System (ADS)

Fang, Ruimei; Huang, Haibao; Huang, Wenjun; Ji, Jian; Feng, Qiuyu; Shu, Yajie; Zhan, Yujie; Liu, Gaoyuan; Xie, Ruijie

2017-10-01

Coal based activated carbon (AC) was pretreated by peracetic acid solution and used for supporting Mn catalyst towards oxidation of gaseous benzene by catalytic ozonation. The as-obtained activated carbon was characterized by XPS, BET, SEM, and TG technologies. It indicates that peracetic acid solution modification not only raised the quantity of chemisorbed oxygen or water, and hydroxyl group on activated carbon material surface, but also increased the specific surface area and benzene adsorption capacity of activated carbon. Benzene could be completely removed in 300 min and CO2 selectivity reached to 61.9% over Mn/AC-modified catalyst. A possible catalytic ozonation mechanism of activated carbon which was treated by peracetic acid solution supported Mn catalyst for oxidation of benzene was proposed.

Pd/Cu-Oxide Nanoconjugate at Zeolite-Y Crystallite Crafting the Mesoporous Channels for Selective Oxidation of Benzyl-Alcohols.

PubMed

Sharma, Mukesh; Das, Biraj; Sharma, Mitu; Deka, Biplab K; Park, Young-Bin; Bhargava, Suresh K; Bania, Kusum K

2017-10-11

Solid-state grinding of palladium and copper salts allowed the growth of palladium/copper oxide interface at the zeolite-Y surface. The hybrid nanostructured material was used as reusable heterogeneous catalyst for selective oxidation of various benzyl alcohols. The large surface area provided by the zeolite-Y matrix highly influenced the catalytic activity, as well as the recyclability of the synthesized catalyst. Impregnation of PdO-CuO nanoparticles on zeolite crystallite leads to the generation of mesoporous channel that probably prevented the leaching of the metal-oxide nanoparticles and endorsed high mass transfer. Formation of mesoporous channel at the external surface of zeolite-Y was evident from transmission electron microscopy and surface area analysis. PdO-CuO nanoparticles were found to be within the range of 2-5 nm. The surface area of PdO-CuO-Y catalyst was found to be much lower than parent zeolite-Y. The decrease in surface area as well as the presence of hysteresis loop in the N 2 -adsoprtion isotherm further suggested successful encapsulation of PdO-CuO nanoparticles via the mesoporous channel formation. The high positive shifting in binding energy in both Pd and Cu was attributed to the influence of zeolite-Y framework on lattice contraction of metal oxides via confinement effect. PdO-CuO-Y catalyst was found to oxidize benzyl alcohol with 99% selectivity. On subjecting to microwave irradiation the same oxidation reaction was found to occur at ambient condition giving same conversion and selectivity.

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

NASA Astrophysics Data System (ADS)

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

2018-03-01

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

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

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.

Cellulose Surface Degradation by a Lytic Polysaccharide Monooxygenase and Its Effect on Cellulase Hydrolytic Efficiency*

PubMed Central

Eibinger, Manuel; Ganner, Thomas; Bubner, Patricia; Rošker, Stephanie; Kracher, Daniel; Haltrich, Dietmar; Ludwig, Roland; Plank, Harald; Nidetzky, Bernd

2014-01-01

Lytic polysaccharide monooxygenase (LPMO) represents a unique principle of oxidative degradation of recalcitrant insoluble polysaccharides. Used in combination with hydrolytic enzymes, LPMO appears to constitute a significant factor of the efficiency of enzymatic biomass depolymerization. LPMO activity on different cellulose substrates has been shown from the slow release of oxidized oligosaccharides into solution, but an immediate and direct demonstration of the enzyme action on the cellulose surface is lacking. Specificity of LPMO for degrading ordered crystalline and unordered amorphous cellulose material of the substrate surface is also unknown. We show by fluorescence dye adsorption analyzed with confocal laser scanning microscopy that a LPMO (from Neurospora crassa) introduces carboxyl groups primarily in surface-exposed crystalline areas of the cellulosic substrate. Using time-resolved in situ atomic force microscopy we further demonstrate that cellulose nano-fibrils exposed on the surface are degraded into shorter and thinner insoluble fragments. Also using atomic force microscopy, we show that prior action of LPMO enables cellulases to attack otherwise highly resistant crystalline substrate areas and that it promotes an overall faster and more complete surface degradation. Overall, this study reveals key characteristics of LPMO action on the cellulose surface and suggests the effects of substrate morphology on the synergy between LPMO and hydrolytic enzymes in cellulose depolymerization. PMID:25361767

Oxidation Resistance of Materials Based on Ti3AlC2 Nanolaminate at 600 °C in Air.

PubMed

Ivasyshyn, Andrij; Ostash, Orest; Prikhna, Tatiana; Podhurska, Viktoriya; Basyuk, Tatiana

2016-12-01

The oxidation behavior of Ti3AlC2-based materials had been investigated at 600 °C in static air for 1000 h. It was shown that the intense increase of weight gain per unit surface area for sintered material with porosity of 22 % attributed to oxidation of the outer surface of the specimen and surfaces of pores in the bulk material. The oxidation kinetics of the hot-pressed Ti3AlC2-based material with 1 % porosity remarkably increased for the first 15 h and then slowly decreased. The weight gain per unit surface area for this material was 1.0 mg/cm(2) after exposition for 1000 h. The intense initial oxidation of Ti3AlC2-based materials can be eliminated by pre-oxidation treatment at 1200 °C in air for 2 h. As a result, the weight gain per unit surface area for the pre-oxidized material did not exceed 0.11 mg/cm(2) after 1000 h of exposition at 600 °C in air. It was demonstrated that the oxidation resistance of Ti3AlC2-based materials can be significantly improved by niobium addition.

Flame oxidation of stainless steel felt enhances anodic biofilm formation and current output in bioelectrochemical systems.

PubMed

Guo, Kun; Donose, Bogdan C; Soeriyadi, Alexander H; Prévoteau, Antonin; Patil, Sunil A; Freguia, Stefano; Gooding, J Justin; Rabaey, Korneel

2014-06-17

Stainless steel (SS) can be an attractive material to create large electrodes for microbial bioelectrochemical systems (BESs), due to its low cost and high conductivity. However, poor biocompatibility limits its successful application today. Here we report a simple and effective method to make SS electrodes biocompatible by means of flame oxidation. Physicochemical characterization of electrode surface indicated that iron oxide nanoparticles (IONPs) were generated in situ on an SS felt surface by flame oxidation. IONPs-coating dramatically enhanced the biocompatibility of SS felt and consequently resulted in a robust electroactive biofilm formation at its surface in BESs. The maximum current densities reached at IONPs-coated SS felt electrodes were 16.5 times and 4.8 times higher than the untreated SS felts and carbon felts, respectively. Furthermore, the maximum current density achieved with the IONPs-coated SS felt (1.92 mA/cm(2), 27.42 mA/cm(3)) is one of the highest current densities reported thus far. These results demonstrate for the first time that flame oxidized SS felts could be a good alternative to carbon-based electrodes for achieving high current densities in BESs. Most importantly, high conductivity, excellent mechanical strength, strong chemical stability, large specific surface area, and comparatively low cost of flame oxidized SS felts offer exciting opportunities for scaling-up of the anodes for BESs.

Growth of porous anodized alumina on the sputtered aluminum films with 2D-3D morphology for high specific surface area

NASA Astrophysics Data System (ADS)

Liao, M. W.; Chung, C. K.

2014-08-01

The porous anodic aluminum oxide (AAO) with high-aspect-ratio pore channels is widely used as a template for fabricating nanowires or other one-dimensional (1D) nanostructures. The high specific surface area of AAO can also be applied to the super capacitor and the supporting substrate for catalysis. The rough surface could be helpful to enhance specific surface area but it generally results in electrical field concentration even to ruin AAO. In this article, the aluminum (Al) films with the varied 2D-3D morphology on Si substrates were prepared using magnetron sputtering at a power of 50 W-185 W for 1 h at a working pressure of 2.5 × 10-1 Pa. Then, AAO was fabricated from the different Al films by means of one-step hybrid pulse anodizing (HPA) between the positive 40 V and the negative -2 V (1 s:1 s) for 3 min in 0.3 M oxalic acid at a room temperature. The microstructure and morphology of Al films were characterized by X-ray diffraction, scanning electron microscope and atomic force microscope, respectively. Some hillocks formed at the high target power could be attributed to the grain texture growth in the normal orientation of Al(1 1 1). The 3D porous AAO structure which is different from the conventional 2D planar one has been successfully demonstrated using HPA on the film with greatly rough hillock-surface formed at the highest power of 185 W. It offers a potential application of the new 3D AAO to high specific surface area devices.

MOF-templated synthesis of porous Co(3)O(4) concave nanocubes with high specific surface area and their gas sensing properties.

PubMed

Lü, Yinyun; Zhan, Wenwen; He, Yue; Wang, Yiting; Kong, Xiangjian; Kuang, Qin; Xie, Zhaoxiong; Zheng, Lansun

2014-03-26

Porous metal oxides nanomaterials with controlled morphology have received great attention because of their promising applications in catalysis, energy storage and conversion, gas sensing, etc. In this paper, porous Co3O4 concave nanocubes with extremely high specific surface area (120.9 m(2)·g(-1)) were synthesized simply by calcining Co-based metal-organic framework (Co-MOF, ZIF-67) templates at the optimized temperature (300 °C), and the formation mechanism of such highly porous structures as well as the influence of the calcination temperature are well explained by taking into account thermal behavior and intrinsic structural features of the Co-MOF precursors. The gas-sensing properties of the as-synthesized porous Co3O4 concave nanocubes were systematically tested towards volatile organic compounds including ethanol, acetone, toluene, and benzene. Experimental results reveal that the porous Co3O4 concave nanocubes present the highest sensitivity to ethanol with fast response/recovery time (< 10 s) and a low detection limit (at least 10 ppm). Such outstanding gas sensing performance of the porous Co3O4 concave nanocubes benefits from their high porosity, large specific surface area, and remarkable capabilities of surface-adsorbed oxygen.

Mass or total surface area with aerosol size distribution as exposure metrics for inflammatory, cytotoxic and oxidative lung responses in rats exposed to titanium dioxide nanoparticles.

PubMed

Noël, A; Truchon, G; Cloutier, Y; Charbonneau, M; Maghni, K; Tardif, R

2017-04-01

There is currently no consensus on the best exposure metric(s) for expressing nanoparticle (NP) dose. Although surface area has been extensively studied for inflammatory responses, it has not been as thoroughly validated for cytotoxicity or oxidative stress effects. Since inhaled NPs deposit and interact with lung cells based on agglomerate size, we hypothesize that mass concentration combined with aerosol size distribution is suitable for NP risk assessment. The objective of this study was to evaluate different exposure metrics for inhaled 5 nm titanium dioxide aerosols composed of small (SA < 100 nm) or large (LA > 100 nm) agglomerates at 2, 7, and 20 mg/m 3 on rat lung inflammatory, cytotoxicity, and oxidative stress responses. We found a significant positive correlation ( r = 0.98, p < 0.01) with the inflammatory reaction, measured by the number of neutrophils and the mass concentration when considering all six (SA + LA) aerosols. This correlation was similar ( r = 0.87) for total surface area. Regarding cytotoxicity and oxidative stress responses, measured by lactate dehydrogenase and 8-isoprostane, respectively, and mass or total surface area as an exposure metric, we observed significant positive correlations only with SA aerosols for both the mass concentration and size distribution ( r > 0.91, p < 0.01), as well as for the total surface area ( r > 0.97, p < 0.01). These data show that mass or total surface area concentrations alone are insufficient to adequately predict oxidant and cytotoxic pulmonary effects. Overall, our study indicates that considering NP size distribution along with mass or total surface area concentrations contributes to a more mechanistic discrimination of pulmonary responses to NP exposure.

SnO2 Nanostructures: Effect of Processing Parameters on Their Structural and Functional Properties

NASA Astrophysics Data System (ADS)

Dontsova, Tetiana A.; Nagirnyak, Svitlana V.; Zhorov, Vladyslav V.; Yasiievych, Yuriy V.

2017-05-01

Zero- and 1D (one-dimensional) tin (IV) oxide nanostructures have been synthesized by thermal evaporation method, and a comparison of their morphology, crystal structure, sorption properties, specific surface area, as well as electrical characteristics has been performed. Synthesized SnO2 nanomaterials were studied by X-ray diffraction, scanning and transmission electron microscopy (SEM and TEM), N2 sorption/desorption technique, IR spectroscopy and, in addition, their current-voltage characteristics have also been measured. The single crystalline structures were obtained both in case of 0D (zero-dimensional) SnO2 powders and in case of 0D nanofibers, as confirmed by electron diffraction of TEM. It was found that SnO2 synthesis parameters significantly affect materials' properties by contributing to the difference in morphology, texture formation, changes in IR spectra of 1D structure as compared to 0D powders, increases in the specific surface area of nanofibers, and the alteration of current-voltage characteristics 0D and 1D SnO2 nanostructures. It was established that gas sensors utilizing of 1D nanofibers significantly outperform those based on 0D powders by providing higher specific surface area and ohmic I-V characteristics.

Synthesizing new types of ultrathin 2D metal oxide nanosheets via half-successive ion layer adsorption and reaction

NASA Astrophysics Data System (ADS)

Gao, Linjie; Li, Yaguang; Xiao, Mu; Wang, Shufang; Fu, Guangsheng; Wang, Lianzhou

2017-06-01

Two-dimensional (2D) metal oxide nanosheets have demonstrated their great potential in a broad range of applications. The existing synthesis strategies are mainly preparing 2D nanosheets from layered and specific transition metal oxides. How to prepare the other types of metal oxides as ultrathin 2D nanosheets remains unsolved, especially for metal oxides containing alkali, alkaline earth metal, and multiple metal elements. Herein, we developed a half-successive ion layer adsorption and reaction (SILAR) method, which could synthesize those types of metal oxides as ultrathin 2D nanosheets. The synthesized 2D metal oxides nanosheets are within 1 nm level thickness and 500 m2 · g-1 level surface area. This method allows us to develop many new types of ultrathin 2D metal oxides nanosheets that have never been prepared before.

Ambient temperature NO oxidation over Cr-based amorphous mixed oxide catalysts: effects from the second oxide components

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

Wang, Aiyong; Lin, Bo; Zhang, Hanlei

2017-01-01

Three series of Cr-based mixed oxides (Cr-Co, Cr-Fe, and Cr-Ni oxides) with high specific surface areas and amorphous textures were synthesized using a novel sol-gel method. These mixed oxides, in comparison to their pure metal oxide (CrOx, Co3O4, FeOx and NiO) counterparts, display enhanced performance for catalytic oxidation of low-concentration NO at room temperature. The best performing catalysts achieve 100% NO conversion for ~30 h of operation at a high space velocity of 45,000 ml g-1 h-1. The amorphous structure was found to be critical for these catalysts to maintain high activity and durability. Control of Cr/M (M=Co, Fe andmore » Ni) molar ratio, nitrate precursor decomposition temperature and catalyst calcination temperature was key to the synthesis of these highly active catalysts.« less

Tribological performance of titanium samples oxidized by fs-laser radiation, thermal heating, or electrochemical anodization

NASA Astrophysics Data System (ADS)

Kirner, S. V.; Slachciak, N.; Elert, A. M.; Griepentrog, M.; Fischer, D.; Hertwig, A.; Sahre, M.; Dörfel, I.; Sturm, H.; Pentzien, S.; Koter, R.; Spaltmann, D.; Krüger, J.; Bonse, J.

2018-04-01

Commercial grade-1 titanium samples (Ti, 99.6%) were treated using three alternative methods, (i) femtosecond laser processing, (ii) thermal heat treatment, and (iii) electrochemical anodization, respectively, resulting in the formation of differently conditioned superficial titanium oxide layers. The laser processing (i) was carried out by a Ti:sapphire laser (pulse duration 30 fs, central wavelength 790 nm, pulse repetition rate 1 kHz) in a regime of generating laser-induced periodic surface structures (LIPSS). The experimental conditions (laser fluence, spatial spot overlap) were optimized in a sample-scanning setup for the processing of several square-millimeters large surface areas covered homogeneously by these nanostructures. The differently oxidized titanium surfaces were characterized by optical microscopy, micro Raman spectroscopy, variable angle spectroscopic ellipsometry, and instrumented indentation testing. The tribological performance was characterized in the regime of mixed friction by reciprocating sliding tests against a sphere of hardened steel in fully formulated engine oil as lubricant. The specific tribological performance of the differently treated surfaces is discussed with respect to possible physical and chemical mechanisms.

Electrochemically driven host-guest interactions on patterned donor/acceptor self-assembled monolayers.

PubMed

Maglione, Maria Serena; Casado-Montenegro, Javier; Fritz, Eva-Corinna; Crivillers, Núria; Ravoo, Bart Jan; Rovira, Concepció; Mas-Torrent, Marta

2018-03-25

Here, on ITO//Au patterned substrates SAMs of ferrocene (Fc) on the Au regions and of anthraquinone (AQ) on the ITO areas are prepared, exhibiting three stable redox states. Furthermore, by selectively oxidizing or reducing the Fc or AQ units, respectively, the surface properties are locally modified. As a proof-of-concept, such a confinement of the properties is exploited to locally form host-guest complexes with β-cyclodextrin on specific surface regions depending on the applied voltage.

On the validity of specific rate constants (kSA) in Fe0/H2O systems.

PubMed

Noubactep, C

2009-05-30

The validity of the specific reaction rate constants (k(SA)) in modelling contaminant removal in Fe(0)/H(2)O systems is questioned. It is shown that the current k(SA)-model does not consider the large reactive surface area provided by the in-situ formed oxide film, and thus the adsorptive interactions between contaminants and film materials. Furthermore, neither the dynamic nature of film formation nor the fact that the Fe(0) surface is shielded by the film is considered. Suggestions are made how the k(SA)-model could be further developed to meet its original goal.

Lanthanum-promoted copper-based hydrotalcites derived mixed oxides for NO{sub x} adsorption, soot combustion and simultaneous NO{sub x}-soot removal

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

Wang, Zhongpeng; Inorganic Chemistry Laboratory, University of Oxford, South Parks Road, Oxford OX1 3QR; Yan, Xiaotong

Graphical abstract: - Highlights: • The addition of La in Cu-based oxides increased the types of active oxygen. • NO{sub x} adsorption, soot oxidation and simultaneous NO{sub x}-soot removal were enhanced. • The possible catalytic mechanism was studied via in situ FTIR analysis. • Soot oxidation was promoted by the NO{sub 2} intermediate. - Abstract: La-promoted Cu-based hydrotalcites derived mixed oxides were prepared and their catalytic activities for NO{sub x} adsorption, soot oxidation, and simultaneous NO{sub x}-soot removal were investigated. The catalysts were characterized by XRD, DTG, BET, FTIR, H2-TPR, TPD and TPO techniques. The oxides catalysts exhibited mesoporous propertiesmore » with specific surface area of 45–160 m{sup 2}/g. The incorporation of La and Cu decreased the amount of basic sites due to the large decrease in surface areas. Under O{sub 2} atmosphere, La incorporation is dominant for soot oxidation activity, while Cu favors high selectivity to CO{sub 2} formation. A synergetic effect between La and Cu for catalyzed soot oxidation lies in the improved redox property and suitable basicity. The presence of NO in O{sub 2} significantly promoted soot oxidation on the catalysts with the ignition temperature decreased to about 300 °C. In O{sub 2}/NO atmosphere, NO{sub 2} acts as an intermediate which oxidizes soot to CO{sub 2} at a lower temperature with itself reduced to NO or N{sub 2}, contributing to the high catalytic performance in simultaneous removal of NO{sub x} and soot.« less

Computer Simulation Study of Graphene Oxide Supercapacitors: Charge Screening Mechanism.

PubMed

Park, Sang-Won; DeYoung, Andrew D; Dhumal, Nilesh R; Shim, Youngseon; Kim, Hyung J; Jung, YounJoon

2016-04-07

Graphene oxide supercapacitors in the parallel plate configuration are studied via molecular dynamics (MD) simulations. The full range of electrode oxidation from 0 to 100% is examined by oxidizing the graphene surface with hydroxyl groups. Two different electrolytes, 1-ethyl-3-methylimidazolium tetrafluoroborate (EMI(+)BF4(-)) as an ionic liquid and its 1.3 M solution in acetonitrile as an organic electrolyte, are considered. While the area-specific capacitance tends to decrease with increasing electrode oxidation for both electrolytes, its details show interesting differences between the organic electrolyte and ionic liquid, including the extent of decrease. For detailed insight into these differences, the screening mechanisms of electrode charges by electrolytes and their variations with electrode oxidation are analyzed with special attention paid to the aspects shared by and the contrasts between the organic electrolyte and ionic liquid.

Environmental and Biomedical Applications of Iron Oxide/Mesoporous Silica Core-Shell Nanocomposites

NASA Astrophysics Data System (ADS)

Egodawatte, Shani Nirasha

Mesoporous silica has shown great potential as an adsorbent for environmental contaminants and as a host for imaging and therapeutic agents. Mesoporous silica materials have a high surface area, tunable pore sizes and well defined surface properties which are governed by the surface hydroxyl groups. Surface modification of the mesoporous silica can tailor the adsorption properties for a specific metal ion or a small drug molecule by providing better sites for chelation or electrostatic interactions. Iron oxide / mesoporous silica core shell materials couple the favorable properties of both the iron oxide and mesoporous silica materials. The core-shell materials have higher adsorption properties compared to the parent material. With magnetic iron oxide nanoparticle cores, an additional magnetic property is introduced that can be used as magnetic recovery or separation. Heavy metals such as Chromium (Cr) and Arsenic (As) discharged from residential and environmental sources pose a serious threat to human health as well as groundwater pollution. In this thesis, iron oxide nanoparticles and nanofibers were coated with mesoporous silica and functionalized with (3-aminopropyl)triethoxysilane (APTES) using the post synthesis grafting method. The parent and the functionalized magnetic silica samples were characterized using powder X-ray diffraction (pXRD), thermal gravimetric analysis (TGA), Fourier Transform Infrared (FTIR) spectroscopy and nitrogen adsorption desorption isotherms for surface area and pore volumes. These materials were evaluated for Cr(III) and As(III)/As(V) adsorption from aqueous solutions in the optimum pH range for the specific metal. The aminopropyl functionalized magnetic mesoporous silica displayed the highest adsorption capacity for Cr(III) and Cu(II) of all the materials evaluated in this study. The high heavy metal adsorption capacity was attributed to a synergistic effect of iron oxide nanoparticles and amine functionalization on mesoporous silica as well as a judicious choice of pH. Modified magnetic mesoporous silica material was also found to have high adsorption capacity for high and low pH aqueous solutions of Uranium (VI). Tuning the loading and release of a small drug molecule (5-FU) onto these iron oxide/ mesoporous silica core-shell materials was also investigated. The polarity of the solvent used to load 5-FU onto the host had an impact not only on the loading but also on the release percentage of 5-FU. The synthesis of a novel core-shell material with a hematite nanofiber core and a SBA type mesoporous silica shell was also explored.

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.

Synthesis and Microstructural Characterization of Manganese Oxide Electrodes for Application as Electrochemical Supercapacitors

NASA Astrophysics Data System (ADS)

Babakhani, Banafsheh

The aim of this thesis work was to synthesize Mn-based oxide electrodes with high surface area structures by anodic electrodeposition for application as electrochemical capacitors. Rod-like structures provide large surface areas leading to high specific capacitances. Since templated electrosynthesis of rods is not easy to use in practical applications, it is more desirable to form rod-like structures without using any templates. In this work, Mn oxide electrodes with rod-like structures (˜1.5 µm in diameter) were synthesized from a solution of 0.01 M Mn acetate under galvanostatic control without any templates, on Au coated Si substrates. The electrochemical properties of the synthesized nanocrystalline electrodes were investigated to determine the effect of morphology, chemistry and crystal structure on the corresponding electrochemical behavior of Mn oxide electrodes. Mn oxides prepared at different current densities showed a defective antifluoritetype crystal structure. The rod-like Mn oxide electrodes synthesized at low current densities (5 mAcm.2) exhibited a high specific capacitance due to their large surface areas. Also, specific capacity retention after 250 cycles in an aqueous solution of 0.5 M Na2SO4 at 100 mVs -1 was about 78% of the initial capacity (203 Fg-1 ). To improve the electrochemical capacitive behavior of Mn oxide electrodes, a sequential approach and a one-step method were adopted to synthesize Mn oxide/PEDOT electrodes through anodic deposition on Au coated Si substrates from aqueous solutions. In the former case, free standing Mn oxide rods (about 10 µm long and less than 1.5 µm in diameter) were first synthesized, then coated by electro-polymerization of a conducting polymer (PEDOT) giving coaxial rods. The one-step, co-electrodeposition method produced agglomerated Mn oxide/PEDOT particles. The electrochemical behavior of the deposits depended on the morphology and crystal structure of the fabricated electrodes, which were affected by the composition and pH of the electrolyte, temperature, current density and polymer deposition time. Mn oxide/PEDOT coaxial core/shell rods consisted of MnO2 with an antifluorite-type structure coated with amorphous PEDOT. The Mn oxide/PEDOT coaxial core/shell electrodes prepared by the sequential method showed significantly better specific capacity and redox performance properties relative to both uncoated Mn oxide rods and co- electrodeposited Mn oxide/PEDOT electrodes. The best specific capacitance for Mn oxide/PEDOT rods produced sequentially was ˜295 F g-1 with ˜92% retention after 250 cycles in 0.5 M Na2SO4 at 100 mV s-1. To further improve the electrochemical capacitive behavior of Mn oxide electrodes, Co-doped and Fe-doped Mn oxide electrodes with a rod-like morphology and antifluorite-type crystal structure were synthesized by anodic electrodeposition, on Au coated Si substrates, from dilute solutions of Mn acetate and Co sulphate and Mn acetate and Fe chloride. Also, Mn-Co oxide/PEDOT coaxial core/shell rods were synthesized by applying a shell of PEDOT on Mn-Co oxide electrodes. Mn-Co oxide/PEDOT electrodes consisted of MnO2, with partial Co 2+ and Co3+ ion substitution for Mn4+, and amorphous PEDOT. Mn-Fe oxide electrodes consisted of MnO2, with partial Fe2+ and Fe3+ ion substitution for Mn4+. Electrochemical analysis showed that the capacitance values for all deposits increased with increasing scan rate to 100 mVs -1, and then decreased after 100 mVs-1. The Mn-Co oxide/PEDOT electrodes showed improved specific capacity and electrochemical cyclability relative to uncoated Mn-Co oxides and Mn-Fe oxides. Mn-Co oxide/PEDOT electrodes with rod-like structures had high capacitances (up to 310 Fg -1) at a scan rate of 100 mVs-1 and maintained their capacitance after 500 cycles in 0.5 M Na2SO4 (91% retention). Capacitance reduction for the deposits was mainly due to the loss of Mn ions by dissolution in the electrolyte solution. To better understand the nucleation and growth mechanisms of Mn oxide electrodes, the effects of supersaturation ratio on the morphology and crystal structure of electrodeposited Mn oxide were studied. By changing deposition parameters, including deposition current density, electrolyte composition, pH and temperature, a series of nanocrystalline Mn oxide electrodes with various morphologies (continuous coatings, rod-like structures, aggregated rods and thin sheets) and an antifluorite-type crystal structure was obtained. Mn oxide thin sheets showed instantaneous nucleation and single crystalline growth; rods had a mix of instantaneous/progressive nucleation and polycrystalline growth and continuous coatings formed by progressive nucleation and polycrystalline growth. Electrochemical analysis revealed the best capacitance behaviour obtained for Mn oxide thin sheets followed by Mn oxide rods, with dimensions on the microscale, and then continuous coatings. The highest specific capacitance (˜230 Fg-1) and capacitance retention rates (˜88%) were obtained for Mn oxide thin sheets after 250 cycles in 0.5 M Na2 SO4 at 20 mVs-1.

Accumulation of iron and arsenic in the Chandina alluvium of the lower delta plain, Southeastern Bangladesh

USGS Publications Warehouse

Zahid, A.; Hassan, M.Q.; Breit, G.N.; Balke, K.-D.; Flegr, M.

2009-01-01

Accumulations of iron, manganese, and arsenic occur in the Chandina alluvium of southeastern Bangladesh within 2.5 m of the ground surface. These distinctive orange-brown horizons are subhorizontal and consistently occur within 1 m of the contact of the aerated (yellow-brown) and water-saturated (gray) sediment. Ferric oxyhydroxide precipitates that define the horizons form by oxidation of reduced iron in pore waters near the top of the saturated zone when exposed to air in the unsaturated sediment. Hydrous Fe-oxide has a high specific surface area and thus a high adsorption capacity that absorbs the bulk of arsenic also present in the reduced pore water, resulting in accumulations containing as much as 280 ppm arsenic. The steep redox gradient that characterizes the transition of saturated and unsaturated sediment also favors accumulation of manganese oxides in the oxidized sediment. Anomalous concentrations of phosphate and molybdenum also detected in the ferric oxyhydroxide-enriched sediment are attributed to sorption processes. ?? Springer Science+Business Media B.V. 2008.

Synthesis of porous graphene powder through improved Hummers' method

NASA Astrophysics Data System (ADS)

Gupta, Siddhant; Bonageri, Shrilakshmi; Achar, Siddarth Krishnaraja; Menon, Atul; Basavaraja R., J.

2018-05-01

Graphene due to its high specific surface area is considered to be a potential adsorbent for air and water purification systems. In this study, graphene was synthesized using the recently developed Improved Hummers' method to achieve a high oxidation rate and thermal treatment of the synthesized graphene was done to increase its pore size and make it more capable for applications in purification systems. Graphite flakes were oxidized to obtain graphene oxide which was then reduced to obtain graphene. The synthesized graphene was then thermally treated at 200 °C for two hours in a muffle furnace to improve its surface properties. The characterization results of graphene oxide and graphene show the presence of many impurities which is inferred to be the result of contaminated water used in the experimentation. The analysis of the characterization results also shows that the thermally treated graphene has more spacing and voids when compared to graphene which makes it a better suit for adsorption of gases such as carbon dioxide.

Graphene oxide-based benzimidazole-crosslinked networks for high-performance supercapacitors

NASA Astrophysics Data System (ADS)

Cui, Yi; Cheng, Qian-Yi; Wu, Haiping; Wei, Zhixiang; Han, Bao-Hang

2013-08-01

The synthesis of graphene oxide (GO)-based benzimidazole-crosslinked network (GOBIN) materials is presented. These materials are prepared by the covalent crosslinking of GO sheets using a condensation reaction between the carboxylic acid moieties on the GO surface and the o-aminophenyl end groups of 3,3'-diaminobenzidine (or 1,2,4,5-benzenetetraamine tetrahydrochloride). An efficient one-pot catalyst- and template-free synthesis was performed. The obtained porous GO-based materials possess a Brunauer-Emmett-Teller specific surface area ranging from 260 to 920 m2 g-1. Electrochemical testing indicates that the GOBIN materials display a specific capacitance up to 370 F g-1 at a current density of 0.1 A g-1 and about 90% of the original capacitance is retained after 5000 cycles at a current density of 3 A g-1. Therefore, GOBIN materials can be employed as promising electrode materials for high-performance supercapacitors with outstanding cycling stability. Furthermore, owing to their significantly high specific surface area, these materials also show hydrogen uptake (up to 1.24 wt%, at 77 K and 1.0 bar) and carbon dioxide capture (up to 14.2 wt%, at 273 K and 1.0 bar) properties. As a result, these GO-based porous materials improve both the supercapacitor performance and gas sorption property, which demonstrate an excellent performance in the practical application of energy storage.The synthesis of graphene oxide (GO)-based benzimidazole-crosslinked network (GOBIN) materials is presented. These materials are prepared by the covalent crosslinking of GO sheets using a condensation reaction between the carboxylic acid moieties on the GO surface and the o-aminophenyl end groups of 3,3'-diaminobenzidine (or 1,2,4,5-benzenetetraamine tetrahydrochloride). An efficient one-pot catalyst- and template-free synthesis was performed. The obtained porous GO-based materials possess a Brunauer-Emmett-Teller specific surface area ranging from 260 to 920 m2 g-1. Electrochemical testing indicates that the GOBIN materials display a specific capacitance up to 370 F g-1 at a current density of 0.1 A g-1 and about 90% of the original capacitance is retained after 5000 cycles at a current density of 3 A g-1. Therefore, GOBIN materials can be employed as promising electrode materials for high-performance supercapacitors with outstanding cycling stability. Furthermore, owing to their significantly high specific surface area, these materials also show hydrogen uptake (up to 1.24 wt%, at 77 K and 1.0 bar) and carbon dioxide capture (up to 14.2 wt%, at 273 K and 1.0 bar) properties. As a result, these GO-based porous materials improve both the supercapacitor performance and gas sorption property, which demonstrate an excellent performance in the practical application of energy storage. Electronic supplementary information (ESI) available: Detailed methods of preparation of GOBINPPA, SEM images, IR spectra, TGA, nitrogen adsorption-desorption isotherms, pore size distribution, gravimetric hydrogen adsorption, carbon dioxide adsorption isotherms, and virial analysis of the adsorption data for GOBIN materials. See DOI: 10.1039/c3nr01480k

Stabilizing nanostructured solid oxide fuel cell cathode with atomic layer deposition.

PubMed

Gong, Yunhui; Palacio, Diego; Song, Xueyan; Patel, Rajankumar L; Liang, Xinhua; Zhao, Xuan; Goodenough, John B; Huang, Kevin

2013-09-11

We demonstrate that the highly active but unstable nanostructured intermediate-temperature solid oxide fuel cell cathode, La0.6Sr0.4CoO3-δ (LSCo), can retain its high oxygen reduction reaction (ORR) activity with exceptional stability for 4000 h at 700 °C by overcoating its surfaces with a conformal layer of nanoscale ZrO2 films through atomic layer deposition (ALD). The benefits from the presence of the nanoscale ALD-ZrO2 overcoats are remarkable: a factor of 19 and 18 reduction in polarization area-specific resistance and degradation rate over the pristine sample, respectively. The unique multifunctionality of the ALD-derived nanoscaled ZrO2 overcoats, that is, possessing porosity for O2 access to LSCo, conducting both electrons and oxide-ions, confining thermal growth of LSCo nanoparticles, and suppressing surface Sr-segregation is deemed the key enabler for the observed stable and active nanostructured cathode.

Synthesis and characterization of MnS2/reduced graphene oxide nanohybrids for with photocatalytic and antibacterial activity.

PubMed

Fakhri, Ali; Kahi, Delaram Salehpour

2017-01-01

A facile one-step hydrothermal route was developed here to prepare MnS 2 /reduced graphene oxide nanohybrids. The crystal morphologies could be controlled by adjusting the solvent, surfactant, and pH of the precursor solution. X-ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), UV-Vis absorption spectra, and photoluminescence spectra (PL), were used to characterize the structures of the samples were used to characterize the structures of the samples, and the specific surface area was determined using the Brunauer-Emmett-Teller (BET) method. The thickness of the MnS 2 nanoparticles and MnS 2 /reduced graphene oxide nanohybrids were measured to be about 20 and 5nm, respectively. The total pore volume and specific surface area were 0.540 and 1.173cm 3 g -1 and 45.91 and 98.23m 2 g -1 for pure MnS 2 and MnS 2 /r-GO hybrids, respectively. Carbophenothion as an insecticide photodegradation was used to estimate the photocatalytic activity of the MnS 2 /reduced graphene oxide nanohybrids morphologies under UV light. The Carbophenothion hardly decomposed during photolysis over a period of 45min. The rate constant, k value, for the photocatalysis of Carbophenothion by MnS 2 /reduced graphene oxide nanohybrids under UV light radiation is 0.134min -1 . The antibacterial properties of the nanohybrids were evaluated by determining their minimum inhibitory and bactericidal concentrations (MIC and MBC), using a broth microdilution assay for Escherichia coli (E. coli) bacteria. The MIC and MBC values are 4.0 and 32.0μg/mL. Copyright © 2016 Elsevier B.V. All rights reserved.

Adsorption as a method of doping 3-mol%-yttria-stabilized zirconia powder with copper oxides

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

Seidensticker, J.R.; Mayo, M.J.; Osseo-Asare, K.

The adsorption behavior of Cu[sup 2+] on 3-mol%-yttria-stabilized tetragonal zirconia polycrystalline (3Y-TZP) powder was studied. There is a window of pH values (10 < pH < 11) where adsorption may be used as a method of doping 3Y-TZP with Cu[sup 2+]. The maximum mole percent of the CuO additions is determined by the specific surface area of the 3Y-TZP powder; a powder with a specific surface area of 16.1 m[sup 2]/g is limited to about 1 mol% CuO. Compacts made from powders doped with CuO using this method exhibited an enhancement in superplasticity comparable to that observed in other studiesmore » using samples doped with CuO by attrition milling.« less

Investigation of hydrogen evolution activity for the nickel, nickel-molybdenum nickel-graphite composite and nickel-reduced graphene oxide composite coatings

NASA Astrophysics Data System (ADS)

Jinlong, Lv; Tongxiang, Liang; Chen, Wang

2016-03-01

The nickel, nickel-molybdenum alloy, nickel-graphite and nickel-reduced graphene oxide composite coatings were obtained by the electrodeposition technique from a nickel sulfate bath. Nanocrystalline molybdenum, graphite and reduced graphene oxide in nickel coatings promoted hydrogen evolution reaction in 0.5 M H2SO4 solution at room temperature. However, the nickel-reduced graphene oxide composite coating exhibited the highest electrocatalytic activity for the hydrogen evolution reaction in 0.5 M H2SO4 solution at room temperature. A large number of gaps between 'cauliflower' like grains could decrease effective area for hydrogen evolution reaction in slight amorphous nickel-molybdenum alloy. The synergistic effect between nickel and reduced graphene oxide promoted hydrogen evolution, moreover, refined grain in nickel-reduced graphene oxide composite coating and large specific surface of reduced graphene oxide also facilitated hydrogen evolution reaction.

Oxide modified air electrode surface for high temperature electrochemical cells

DOEpatents

Singh, Prabhakar; Ruka, Roswell J.

1992-01-01

An electrochemical cell is made having a porous cermet electrode (16) and a porous lanthanum manganite electrode (14), with solid oxide electrolyte (15) between them, where the lanthanum manganite surface next to the electrolyte contains a thin discontinuous layer of high surface area cerium oxide and/or praseodymium oxide, preferably as discrete particles (30) in contact with the air electrode and electrolyte.

Morphology effect on photocatalytic activity in Bi3Fe0.5Nb1.5O9.

PubMed

Yin, Xiaofeng; Li, Xiaoning; Gu, Wen; Zou, Wei; Liu, Huan; Zhu, Liuyang; Fu, Zhengping; Lu, Yalin

2018-06-29

In this work, the Aurivillius-phase ferroelectric Bi 3 Fe 0.5 Nb 1.5 O 9 were synthesized by hydrothermal (BFNO-H) and solid state methods (BFNO-S), respectively. The BFNO-H shows a hierarchical morphology, which is stacked by intersecting single-crystal nanosheets with {001} and {110} exposed facets, while the BFNO-S shows disorganized micron-scale morphology. BFNO-H shows a much stronger photodegradation activity (10.4 times and 9.8 times) than BFNO-S in the visible-light photodegradation of rhodamine B (RhB) and salicylic acid. The higher photodegradation activity of BFNO-H was firstly ascribed to the hierarchical structure and the larger specific surface area (16.586 m 2 g -1 ) because a large specific surface area can increase reactive sites and shorten photogenerated carrier migration distance. However, after being normalized by the specific surface area, BFNO-H still performs better than BFNO-S, implying that the specific surface area is not the only factor that determines the photocatalytic activity. Considering that the built-in electric field originating from spontaneous polarization in Bi 3 Fe 0.5 Nb 1.5 O 9 has existed in both ab plane and c direction, it matches well with the {001} and {110} exposed facets of BFNO-H nanosheets. This appropriate matching in BFNO-H nanosheets may improve the separation and transmission of photogenerated electron-hole pairs and further enhance its photocatalytic activity. Moreover, the trapping experiments reveals that holes (h + ) are the main active species and hole-derived oxidation is the main redox reaction during photodegradation of organic pollutions.

Morphology effect on photocatalytic activity in Bi3Fe0.5Nb1.5O9

NASA Astrophysics Data System (ADS)

Yin, Xiaofeng; Li, Xiaoning; Gu, Wen; Zou, Wei; Liu, Huan; Zhu, Liuyang; Fu, Zhengping; Lu, Yalin

2018-06-01

In this work, the Aurivillius-phase ferroelectric Bi3Fe0.5Nb1.5O9 were synthesized by hydrothermal (BFNO-H) and solid state methods (BFNO-S), respectively. The BFNO-H shows a hierarchical morphology, which is stacked by intersecting single-crystal nanosheets with {001} and {110} exposed facets, while the BFNO-S shows disorganized micron-scale morphology. BFNO-H shows a much stronger photodegradation activity (10.4 times and 9.8 times) than BFNO-S in the visible-light photodegradation of rhodamine B (RhB) and salicylic acid. The higher photodegradation activity of BFNO-H was firstly ascribed to the hierarchical structure and the larger specific surface area (16.586 m2 g‑1) because a large specific surface area can increase reactive sites and shorten photogenerated carrier migration distance. However, after being normalized by the specific surface area, BFNO-H still performs better than BFNO-S, implying that the specific surface area is not the only factor that determines the photocatalytic activity. Considering that the built-in electric field originating from spontaneous polarization in Bi3Fe0.5Nb1.5O9 has existed in both ab plane and c direction, it matches well with the {001} and {110} exposed facets of BFNO-H nanosheets. This appropriate matching in BFNO-H nanosheets may improve the separation and transmission of photogenerated electron–hole pairs and further enhance its photocatalytic activity. Moreover, the trapping experiments reveals that holes (h +) are the main active species and hole-derived oxidation is the main redox reaction during photodegradation of organic pollutions.

Carbon-Nanotubes-Supported Pd Nanoparticles for Alcohol Oxidations in Fuel Cells: Effect of Number of Nanotube Walls on Activity.

PubMed

Zhang, Jin; Lu, Shanfu; Xiang, Yan; Shen, Pei Kang; Liu, Jian; Jiang, San Ping

2015-09-07

Carbon nanotubes (CNTs) are well known electrocatalyst supports due to their high electrical conductivity, structural stability, and high surface area. Here, we demonstrate that the number of inner tubes or walls of CNTs also have a significant promotion effect on the activity of supported Pd nanoparticles (NPs) for alcohol oxidation reactions of direct alcohol fuel cells (DAFCs). Pd NPs with similar particle size (2.1-2.8 nm) were uniformly assembled on CNTs with different number of walls. The results indicate that Pd NPs supported on triple-walled CNTs (TWNTs) have the highest mass activity and stability for methanol, ethanol, and ethylene glycol oxidation reactions, as compared to Pd NPs supported on single-walled and multi-walled CNTs. Such a specific promotion effect of TWNTs on the electrocatalytic activity of Pd NPs is not related to the contribution of metal impurities in CNTs, oxygen-functional groups of CNTs or surface area of CNTs and Pd NPs. A facile charge transfer mechanism via electron tunneling between the outer wall and inner tubes of CNTs under electrochemical driving force is proposed for the significant promotion effect of TWNTs for the alcohol oxidation reactions in alkaline solutions. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Analysis of Wear Behavior of Graphene OXIDE — Polyamide Gears for Engineering Applications

NASA Astrophysics Data System (ADS)

Rajamani, Geetha; Paulraj, Jawahar; Krishnan, Kanny

Recent advances in polymer nanocomposites open a wide range of applications in various industrial sectors. Due to their high potential properties, these materials are replacing the usage of metals for many heavier components in automobile industries. In this experimental work, the tribological performance of Graphene oxide (GO) — Polyamide is investigated against pristine polyamide by fabricating gears for the usage in engineering applications. A gear test rig was developed in-house for analysis to study the specific wear rate and temperature gradient at different conditions of load and speeds. The wear resistance of the polyamide gears with the addition of 0.03wt.% of graphene oxide is better than the pristine polyamide gears and the specific wear rate is reduced significantly. The reduced specific wear rate of these polymer nanocomposite gears is attributed to the superior properties of graphene oxide such as High specific surface area, good adhesion properties and enhanced glass transition temperatures. The GO nanocomposite gear seems to be a potential alternative against conventional gears for engineering applications. Finally, the wear mechanisms and the potential of GO-based polyamide nanocomposite gears were proposed tentatively in the development of transmission gears for engineering applications.

Fabrication and characterization of crushed titanium-beryllium intermetallic compounds

NASA Astrophysics Data System (ADS)

Kim, Jae-Hwan; Nakamichi, Masaru

2018-01-01

To develop a technique for the mass production of beryllide pebbles, a crushing method for the granulation of beryllides was used in this study. Two types of crushed Be12Ti pebbles were prepared using mortar-ground (MG) and planetary-ball-milled (PM) powders. A granulation yield of approximately 50 wt.% with sizes in the range of 0.85-1.18 mm was achieved. Scanning electron microscopy (SEM) images revealed that the MG pebbles exhibited larger porosity because the larger size of the powder resulted in lower density with higher porosity. However, the considerably larger fraction of fine pores in the PM pebbles resulted in an increased Brunauer-Emmett-Teller (BET) specific surface area, as clearly demonstrated by high-magnification SEM images. To evaluate the reactivity with water vapor, the weight gain and H2 generation rate were also investigated. The results suggested that the PM pebbles exhibited notably lower reactivity, weight gain, and H2 generation rate, which may be due to the dramatically decreased BET specific surface. The fine pores were filled with stable oxides followed by a significant decrease of the surface area during oxidation. Optimization was performed to improve the circularity of the crushed pebbles. Grinding tests using planetary milling without balls for different times clearly demonstrated that the circularity improved (with an estimated value of 0.8) by cutting and polishing the sharp edges; however, long-duration milling for 99 h resulted in attachment of the polished powders to the pebble surface, leading to surface color variation of the crushed pebbles.

Effects of Post-Pyrolysis Air Oxidation of Biomass Chars on Adsorption of Neutral and Ionizable Compounds.

PubMed

Xiao, Feng; Pignatello, Joseph J

2016-06-21

This study was conducted to understand the effects of thermal air oxidation of biomass chars experienced during formation or production on their adsorptive properties toward various compounds, including five neutral nonpolar and polar compounds and seven weak acids and bases (pKa = 3-5.2) selected from among industrial chemicals and the triazine and phenoxyacetic acid herbicide classes. Post-pyrolysis air oxidation (PPAO) at 400 °C of anoxically prepared wood and pecan shell chars for up to 40 min enhanced the mass-normalized adsorption at pH ∼ 7.4 of all test compounds, especially the weak acids and bases, by up to 100-fold. Both general and specific effects were identified. The general effect results from "reaming" of pores by the oxidative removal of pore wall matter and/or tarry deposits generated during the pyrolysis step. Reaming creates new surface area and enlarges nanopores, which helps relieve steric hindrance to adsorption. The specific effect results from creation of new acidic functionality that provides sites for the formation of very strong, charge-assisted hydrogen bonds (CAHB) with solutes having comparable pKa. The CAHB hypothesis was supported by competition experiments and the finding that weak acid anion adsorption increased with surface carboxyl content, despite electrostatic repulsion from the growing negative charge. The results provide insight into the effects of air oxidation on pollutant retention.

Degradation of nonmodified and rhodium modified aluminide coating deposited on CMSX 4 superalloy.

PubMed

Zagula-Yavorska, Maryana; Wierzbińska, Małgorzata; Gancarczyk, Kamil; Sieniawski, Jan

2016-07-01

The Ni-base superalloy CMSX 4 used in the turbine blades of aircraft engines was coated with rhodium layer (0.5-μm thick). Next coated CMSX 4 superalloy was aluminized by the CVD method. The rhodium modified aluminide coating and nonmodified aluminide coating were oxidized at 1100°C at the air atmosphere. The rhodium modified aluminide coating showed about twice better oxidation resistance than the nonmodified one. The spallation equal 62% of the total area was observed on the surface of the nonmodified coating whereas only 36% spallation area was observed on the surface of the rhodium modified aluminide coating after the oxidation test. The oxide layer formed on the surface of the nonmodified coating was composed of nonprotective (Ni,Cr)Al2 O4 and (Ni,Cr)O phases. Aluminium in the coating reacts with oxygen, forming a protective α-Al2 O3 oxide on the surface of the rhodium modified aluminide coating. When the oxide cracks and spalls due to oxidation, additional aluminium from the coating diffuses to the surface to form the oxide. The presence of protective Al2 O3 oxide on the surface of the rhodium modified aluminide coating slows coating degradation. Therefore, rhodium modified aluminide coating has better oxidation resistance than the nonmodified one. © 2016 The Authors Journal of Microscopy © 2016 Royal Microscopical Society.

Iron Oxide Silica Derived from Sol-Gel Synthesis

PubMed Central

Darmawan, Adi; Smart, Simon; Julbe, Anne; Diniz da Costa, João Carlos

2011-01-01

In this work we investigate the effect of iron oxide embedded in silica matrices as a function of Fe/Si molar ratio and sol pH. To achieve homogeneous dispersion of iron oxide particles, iron nitrate nonahydrate was dissolved in hydrogen peroxide and was mixed with tetraethyl orthosilicate and ethanol in a sol-gel synthesis method. Increasing the calcination temperature led to a reduction in surface area, although the average pore radius remained almost constant at about 10 Å, independent of the Fe/Si molar ratio or sol pH. Hence, the densification of the matrix was accompanied by similar reduction in pore volume. However, calcination at 700 °C resulted in samples with similar surface area though the iron oxide content increased from 5% to 50% Fe/Si molar ratio. As metal oxide particles have lower surface area than polymeric silica structures, these results strongly suggest that the iron oxides opposed the silica structure collapse. The effect of sol pH was found to be less significant than the Fe/Si molar ratio in the formation of molecular sieve structures derived from iron oxide silica. PMID:28879999

Magnetic Photocatalyst BiVO₄/Mn-Zn ferrite/Reduced Graphene Oxide: Synthesis Strategy and Its Highly Photocatalytic Activity.

PubMed

Xie, Taiping; Li, Hui; Liu, Chenglun; Yang, Jun; Xiao, Tiancun; Xu, Longjun

2018-05-29

Magnetic photocatalyst BiVO₄/Mn-Zn ferrite (Mn 1- x Zn x Fe₂O₄)/reduced graphene oxide (RGO) was synthesized by a simple calcination and reduction method. The magnetic photocatalyst held high visible light-absorption ability with low band gap energy and wide absorption wavelength range. Electrochemical impedance spectroscopies illustrated good electrical conductivity which indicated low charge-transfer resistance due to incorporation of Mn 1- x Zn x Fe₂O₄ and RGO. The test of photocatalytic activity showed that the degradation ratio of rhodamine B (RhB) reached 96.0% under visible light irradiation after only 1.5 h reaction. The photocatalytic mechanism for the prepared photocatalyst was explained in detail. Here, the incorporation of RGO enhanced the specific surface area compared with BiVO4/Mn 1- x Zn x Fe₂O₄.The larger specific surface area provided more active surface sites, more free space to improve the mobility of photo-induced electrons, and further facilitated the effective migration of charge carriers, leading to the remarkable improvement of photocatalytic performance. Meanwhile, RGO was the effective acceptor as well as transporter of photo-generated electron hole pairs. •O₂ - was the most active species in the photocatalytic reaction. BiVO₄/Mn 1- x Zn x Fe₂O₄/RGO had quite a wide application in organic contaminants removal or environmental pollution control.

Significant Improvement of Thermal Stability for CeZrPrNd Oxides Simply by Supercritical CO2 Drying

PubMed Central

Fan, Yunzhao; Wang, Zizi; Xin, Ying; Li, Qian; Zhang, Zhaoliang; Wang, Yingxia

2014-01-01

Pr and Nd co-doped Ce-Zr oxide solid solutions (CZPN) were prepared using co-precipitation and microemulsion methods. It is found that only using supercritical CO2 drying can result in a significant improvement of specific surface area and oxygen storage capacity at lower temperatures for CZPN after aging at 1000°C for 12 h in comparison with those using conventional air drying and even supercritical ethanol drying. Furthermore, the cubic structure was obtained in spite of the fact that the atomic ratio of Ce/(Ce+Zr+Pr+Nd) is as low as 29%. The high thermal stability can be attributed to the loosely aggregated morphology and the resultant Ce enrichment on the nanoparticle surface, which are caused by supercritical CO2 drying due to the elimination of surface tension effects on the gas-liquid interface. PMID:24516618

Soft-Template Synthesis of Mesoporous Anatase TiO₂ Nanospheres and Its Enhanced Photoactivity.

PubMed

Li, Xiaojia; Zou, Mingming; Wang, Yang

2017-11-10

Highly crystalline mesoporous anatase TiO₂ nanospheres with high surface area (higher than P25 and anatase TiO₂) are prepared by a soft-template method. Despite the high specific surface area, these samples have three times lower equilibrium adsorption (<2%) than Degussa P25. The rate constant of the mesoporous anatase TiO₂ (0.024 min -1 ) reported here is 364% higher than that of P25 (0.0066 min -1 ), for the same catalytic loading. The results of oxidation-extraction photometry using several reactive oxygen species (ROS) scavengers indicated that mesoporous anatase TiO₂ generates more ROS than P25 under UV-light irradiation. This significant improvement in the photocatalytic performance of mesoporous spherical TiO₂ arises from the following synergistic effects in the reported sample: (i) high surface area; (ii) improved crystallinity; (iii) narrow pore wall thicknesses (ensuring the rapid migration of photogenerated carriers to the surface of the material); and (iv) greater ROS generation under UV-light.

Three dimensional graphene foam supported platinum-ruthenium bimetallic nanocatalysts for direct methanol and direct ethanol fuel cell applications

NASA Astrophysics Data System (ADS)

Kung, Chih-Chien; Lin, Po-Yuan; Xue, Yuhua; Akolkar, Rohan; Dai, Liming; Yu, Xiong; Liu, Chung-Chiun

2014-06-01

A novel composite material of hierarchically structured platinum-ruthenium (PtRu) nanoparticles grown on large surface area three dimensional graphene foam (3D GF) is reported. 3D GF was incorporated with PtRu bimetallic nanoparticles as an electrochemical nanocatalyst for methanol and ethanol oxidation. PtRu/3D GF nanocatalyst showed a higher tolerance to poisoning by CO and exhibited improved catalytic activity for both methanol oxidation reaction (MOR) and ethanol oxidation reaction (EOR). Cyclic voltammetry (CV) results and long-term cycling stability tests demonstrated that GF provided a promising platform for the development of electrochemical nanocatalysts. Specifically, PtRu/3D GF nanocatalyst showed excellent catalytic activity toward MOR and EOR compared with PtRu/Graphene (Commercial graphene), PtRu/C (Vulcan XC-72R carbon), and PtRu alone. The crystal size of PtRu on 3D GF was reduced to 3.5 nm and its active surface area was enhanced to 186.2 m2 g-1. Consequently, the MOR and EOR rates were nearly doubled on PtRu/3D GF compared to those on PtRu/Graphene.

Electrospun N-Doped Porous Carbon Nanofibers Incorporated with NiO Nanoparticles as Free-Standing Film Electrodes for High-Performance Supercapacitors and CO2 Capture.

PubMed

Li, Qi; Guo, Jiangna; Xu, Dan; Guo, Jianqiang; Ou, Xu; Hu, Yin; Qi, Haojun; Yan, Feng

2018-04-01

Carbon nanofibers (CNF) with a 1D porous structure offer promising support to encapsulate transition-metal oxides in energy storage/conversion relying on their high specific surface area and pore volume. Here, the preparation of NiO nanoparticle-dispersed electrospun N-doped porous CNF (NiO/PCNF) and as free-standing film electrode for high-performance electrochemical supercapacitors is reported. Polyacrylonitrile and nickel acetylacetone are selected as precursors of CNF and Ni sources, respectively. Dicyandiamide not only improves the specific surface area and pore volume, but also increases the N-doping level of PCNF. Benefiting from the synergistic effect between NiO nanoparticles (NPs) and PCNF, the prepared free-standing NiO/PCNF electrodes show a high specific capacitance of 850 F g -1 at a current density of 1 A g -1 in 6 m KOH aqueous solution, good rate capability, as well as excellent long-term cycling stability. Moreover, NiO NPs dispersed in PCNF and large specific surface area provide many electroactive sites, leading to high CO 2 uptake, and high-efficiency CO 2 electroreduction. The synthesis strategy in this study provides a new insight into the design and fabrication of promising multifunctional materials for high-performance supercapacitors and CO 2 electroreduction. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrochemically Active Polyaniline (PANi) Coated Carbon Nanopipes and PANi Nanofibers Containing Composite.

PubMed

Ramana, G Venkata; Kumar, P Sampath; Srikanth, Vadali V S S; Padya, Balaji; Jain, P K

2015-02-01

A composite constituted by carbon nanopipes (CNPs) and polyaniline nanofibers (PANi NFs) is synthesized using in-situ chemical oxidative polymerization. Owing to its electrochemical activity the composite is found to be suitable as a working electrode material in hybrid type supercapacitors. Microstructural and phase analyses of the composite showed that (i) CNP surfaces are coated with PANi and (ii) PANi coated CNPs are distributed among PANi NFs. The composite shows an excellent electrochemical activity and a high specific capacitance of ~224.39 F/g. The electro-chemical activity of the composite is explicated in correlation with crystallinity, intrinsic oxidation state, and doping degree of PANi in the composite. The electro-chemical activity of the composite is also explicated in correlation with BET surface area and ordered meso-porosity pertaining to the composite. Charge/discharge curves indicate that the specific capacitance of the composite is a result of electric double-layer capacitance offered by CNPs and Faradaic pseudo capacitance offered by PANi NFs.

Thermal treatment effects on charge storage performance of graphene-based materials for supercapacitors.

PubMed

Zhang, Hongxin; Bhat, Vinay V; Gallego, Nidia C; Contescu, Cristian I

2012-06-27

Graphene materials were synthesized by reduction of exfoliated graphite oxide and then thermally treated in nitrogen to improve the surface area and their electrochemical performance as electrical double-layer capacitor electrodes. The structural and surface properties of the prepared reduced graphite oxide (RGO) were investigated using atomic force microscopy, scanning electron microscopy, Raman spectra, X-ray diffraction pattern analysis, and nitrogen adsorption/desorption studies. RGO forms a continuous network of crumpled sheets, which consist of large amounts of few-layer and single-layer graphenes. Electrochemical studies were conducted by cyclic voltammetry, impedance spectroscopy, and galvanostatic charge-discharge measurements. The modified RGO materials showed enhanced electrochemical performance, with maximum specific capacitance of 96 F/g, energy density of 12.8 Wh/kg, and power density of 160 kW/kg. These results demonstrate that thermal treatment of RGO at selected conditions is a convenient and efficient method for improving its specific capacitance, energy, and power density.

Biological effects of carbon black nanoparticles are changed by surface coating with polycyclic aromatic hydrocarbons.

PubMed

Lindner, Karina; Ströbele, Michael; Schlick, Sandra; Webering, Sina; Jenckel, André; Kopf, Johannes; Danov, Olga; Sewald, Katherina; Buj, Christian; Creutzenberg, Otto; Tillmann, Thomas; Pohlmann, Gerhard; Ernst, Heinrich; Ziemann, Christina; Hüttmann, Gereon; Heine, Holger; Bockhorn, Henning; Hansen, Tanja; König, Peter; Fehrenbach, Heinz

2017-03-21

Carbon black nanoparticles (CBNP) are mainly composed of carbon, with a small amount of other elements (including hydrogen and oxygen). The toxicity of CBNP has been attributed to their large surface area, and through adsorbing intrinsically toxic substances, such as polycyclic aromatic hydrocarbons (PAH). It is not clear whether a PAH surface coating changes the toxicological properties of CBNP by influencing their physicochemical properties, through the specific toxicity of the surface-bound PAH, or by a combination of both. Printex ® 90 (P90) was used as CBNP; the comparators were P90 coated with either benzo[a]pyrene (BaP) or 9-nitroanthracene (9NA), and soot from acetylene combustion that bears various PAHs on the surface (AS-PAH). Oxidative stress and IL-8/KC mRNA expression were determined in A549 and bronchial epithelial cells (16HBE14o-, Calu-3), mouse intrapulmonary airways and tracheal epithelial cells. Overall toxicity was tested in a rat inhalation study according to Organization for Economic Co-operation and Development (OECD) criteria. Effects on cytochrome monooxygenase (Cyp) mRNA expression, cell viability and mucociliary clearance were determined in acute exposure models using explanted murine trachea. All particles had similar primary particle size, shape, hydrodynamic diameter and ζ-potential. All PAH-containing particles had a comparable specific surface area that was approximately one third that of P90. AS-PAH contained a mixture of PAH with expected higher toxicity than BaP or 9NA. PAH-coating reduced some effects of P90 such as IL-8 mRNA expression and oxidative stress in A549 cells, granulocyte influx in the in vivo OECD experiment, and agglomeration of P90 and mucus release in the murine trachea ex vivo. Furthermore, P90-BaP decreased particle transport speed compared to P90 at 10 μg/ml. In contrast, PAH-coating induced IL-8 mRNA expression in bronchial epithelial cell lines, and Cyp mRNA expression and apoptosis in tracheal epithelial cells. In line with the higher toxicity compared to P90-BaP and P90-9NA, AS-PAH had the strongest biological effects both ex vivo and in vivo. Our results demonstrate that the biological effect of CBNP is determined by a combination of specific surface area and surface-bound PAH, and varies in different target cells.

Effects of specific surface area of metallic nickel particles on carbon deposition kinetics

NASA Astrophysics Data System (ADS)

Chen, Zhi-yuan; Bian, Liu-zhen; Yu, Zi-you; Wang, Li-jun; Li, Fu-shen; Chou, Kuo-Chih

2018-02-01

Carbon deposition on nickel powders in methane involves three stages in different reaction temperature ranges. Temperature programing oxidation test and Raman spectrum results indicated the formation of complex and ordered carbon structures at high deposition temperatures. The values of I(D)/ I(G) of the deposited carbon reached 1.86, 1.30, and 1.22 in the first, second, and third stages, respectively. The structure of carbon in the second stage was similar to that in the third stage. Carbon deposited in the first stage rarely contained homogeneous pyrolytic deposit layers. A kinetic model was developed to analyze the carbon deposition behavior in the first stage. The rate-determining step of the first stage is supposed to be interfacial reaction. Based on the investigation of carbon deposition kinetics on nickel powders from different resources, carbon deposition rate is suggested to have a linear relation with the square of specific surface area of nickel particles.

Variation with thermal cycling in microstructure and area specific resistance of a ferritic stainless steel having rough surfaces

NASA Astrophysics Data System (ADS)

Song, Myoung Youp; Mumm, Daniel R.; Song, Jiunn

2013-03-01

Crofer22 APU specimens were prepared by grinding with grit 120 and 400 SiC grinding papers, and were then thermally cycled. The variation in oxidation behavior with thermal cycling was then investigated. Observation of microstructures, measurement of area-specific resistance (ASR), analysis of the atomic percentages of the elements by EDX, and XRD analysis were performed. XRD patterns showed that the (Cr, Mn)3O4 spinel phase grew on the surface of the Crofer22 APU samples ground using grit 120. For the samples ground with grit 400, ASR increased as the number of thermal cycles ( n) increased. Plots of ln (ASR/T) vs. 1/ T for the samples ground with grit 400 after n = 4, 20, and 40 exhibited good linearity, and the apparent activation energies were between 73.4 kJ/mole and 82.5 kJ/mole.

Comparative study of the biodegradability of porous silicon films in simulated body fluid.

PubMed

Peckham, J; Andrews, G T

2015-01-01

The biodegradability of oxidized microporous, mesoporous and macroporous silicon films in a simulated body fluid with ion concentrations similar to those found in human blood plasma were studied using gravimetry. Film dissolution rates were determined by periodically weighing the samples after removal from the fluid. The dissolution rates for microporous silicon were found to be higher than those for mesoporous silicon of comparable porosity. The dissolution rate of macroporous silicon was much lower than that for either microporous or mesoporous silicon. This is attributed to the fact that its specific surface area is much lower than that of microporous and mesoporous silicon. Using an equation adapted from [Surf. Sci. Lett. 306 (1994), L550-L554], the dissolution rate of porous silicon in simulated body fluid can be estimated if the film thickness and specific surface area are known.

Lack of enhanced photocatalytic formation of iodine on particulate semiconductor mixtures.

PubMed

Karunakaran, C; Anilkumar, P; Vinayagamoorthy, P

2012-12-01

Under UV-A light illumination, formation of iodine from iodide ion on the surfaces of anatase TiO(2), ZnO, Fe(2)O(3), CeO(2), MoO(3), Bi(2)O(3), and Nb(2)O(5) increases with the concentration of iodide ion, airflow rate and light intensity and conform to the Langmuir-Hinshelwood kinetic model. Measurement of the particle size of the semiconductor oxides by light scattering method and deduction of the same from the determined specific surface area show that the oxide particles agglomerate in suspension. However, mixtures of any two listed particulate semiconductors do not show enhanced photocatalytic formation of iodine indicating absence of interparticle charge transfer. The results are rationalized. Copyright © 2012 Elsevier B.V. All rights reserved.

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

DTIC Science & Technology

1983-05-20

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

Variability in goethite surface site density: evidence from proton and carbonate sorption.

PubMed

Villalobos, Mario; Trotz, Maya A; Leckie, James O

2003-12-15

Goethite is a representative iron oxide in natural environments due to its abundance and thermodynamic stability and may be responsible for many surface-mediated processes, including ion retention and mobility in aqueous settings. A large variability in morphologies and specific surface areas of goethite crystals exists but little work has been done to compare surface reactivity between them. The present work offers experimental evidence for the existence of an inverse relationship between sorption capacity for protons and carbonate ions and specific surface area of goethite for three synthetic goethite preparations spanning surface area differences by a factor of 2. An explanation for this was found by assuming a variable reactive site density between preparations in direct relationship to their sorption capacity based on congruency of carbonate sorption computed on a per-site basis. Previous evidence of maximum sorption capacities supports this explanation, and site density ratios between the goethites studied here were obtained. Triple layer surface complexation modeling was successful in describing adsorption data for all goethite preparations using equal stoichiometries. A new formulation of standard state for activities of surface species based on a 1.0 mole fraction of sites on the solid allowed transformation of the conventional molar concentration-based affinity constants to values based on site occupancy. In this fashion, by applying the appropriate site density ratios, a single set of affinity constant values was found that described accurately the adsorption data for all preparations.

Preparation and tribological properties of MoS2/graphene oxide composites

NASA Astrophysics Data System (ADS)

Song, Haojie; Wang, Biao; Zhou, Qiang; Xiao, Jiaxuan; Jia, Xiaohua

2017-10-01

A hydrothermal route is developed for the synthesis of MoS2/graphene oxide (GO) composites based on the hydrothermal reduction of Na2MoO4 and GO sheets with L-cysteine. The MoS2/GO composites in improving friction and wear of the sunshine oil on sliding steel surfaces under low or high applied load were demonstrated. In tests with sliding steel surfaces, the sunshine oil that contains small amounts of MoS2/GO composites exhibited the lowest specific friction coefficient and wear rate under all of the sliding conditions. Scanning electron microscopy and energy dispersive spectrometer performed to analyze the wear scar surfaces after friction confirmed that the outstanding lubrication performance of MoS2/GO composites could be attributed to their good dispersion stability and extremely thin laminated structure, which allow the MoS2/GO composites to easily enter the contact area, thereby preventing the rough surfaces from coming into direct contact.

Separation medium containing thermally exfoliated graphite oxide

NASA Technical Reports Server (NTRS)

Prud'homme, Robert K. (Inventor); Aksay, Ilhan A. (Inventor); Herrera-Alonso, Margarita (Inventor)

2012-01-01

A separation medium, such as a chromatography filling or packing, containing a modified graphite oxide material, which is a thermally exfoliated graphite oxide with a surface area of from about 300 m.sup.2/g to 2600 m.sup.2/g, wherein the thermally exfoliated graphite oxide has a surface that has been at least partially functionalized.

Surface-catalyzed air oxidation of hydrazines: Environmental chamber studies

NASA Technical Reports Server (NTRS)

Kilduff, Jan E.; Davis, Dennis D.; Koontz, Steven L.

1988-01-01

The surface-catalyzed air oxidation reactions of fuel hydrazines were studied in a 6500-liter fluorocarbon-film chamber at 80 to 100 ppm concentrations. First-order rate constants for the reactions catalyzed by aluminum, water-damaged aluminum (Al/Al2O3), stainless steel 304L, galvanized steel and titanium plates with surface areas of 2 to 24 sq m were determined. With 23.8 sq m of Al/Al2O3 the surface-catalyzed air oxidation of hydrazine had a half-life of 2 hours, diimide (N2H2) was observed as an intermediate and traces of ammonia were present in the final product mixture. The Al/Al2O3 catalyzed oxidation of monomethylhydrazine yielded methyldiazine (HN = NCH3) as an intermediate and traces of methanol. Unsymmetrical dimethylhydrazine gave no detectable products. The relative reactivities of hydrazine, MMH and UDMH were 130 : 7.3 : 1.0, respectively. The rate constants for Al/Al2O3-catalyzed oxidation of hydrazine and MMH were proportional to the square of the surface area of the plates. Mechanisms for the surface-catalyzed oxidation of hydrazine and diimide and the formation of ammonia are proposed.

Two 3D structured Co-Ni bimetallic oxides as cathode catalysts for high-performance alkaline direct methanol fuel cells

NASA Astrophysics Data System (ADS)

Liu, Yan; Shu, Chengyong; Fang, Yuan; Chen, Yuanzhen; Liu, Yongning

2017-09-01

Two NiCo2O4 bimetallic oxides were synthesized via a facile hydrothermal method. SEM and TEM observations show that these materials have three-dimensional (3D) dandelion-like (DL) and flower-like (FL) morphologies. Their large specific surface areas (90.68 and 19.8 m2·g-1) and porous structures provide many active sites and effective transport pathways for the oxygen reduction reaction (ORR). Electrochemical measurements with a rotating ring-disc electrode (RRDE) indicate that the electron transfer numbers of the NiCo2O4-DL and NiCo2O4-FL catalysts for ORR in an alkaline solution are 3.97 and 3.91, respectively. Fuel cells were assembled with the bimetallic oxides, PtRu/C and a polymer fiber membrane (PFM) as cathode catalysts, anode catalyst and electrolyte film, respectively. For NiCo2O4-DL, the peak power density reaches up to 73.5 mW·cm-2 at 26 °C, which is the highest room-temperature value reported to date. The high catalytic activity of NiCo2O4 is mainly attributed to the presence of many Co3+ cations that directly donate electrons to O2 to reduce it via a more efficient and effective route. Furthermore, the catalytic performance of NiCo2O4-DL is superior to that of NiCo2O4-FL because it has a higher specific surface area and is less crystalline.

Removal of urea from dilute streams using RVC/nano-NiO x -modified electrode.

PubMed

Tammam, Reham H; Touny, Ahmed H; Saleh, Mahmoud M

2018-05-08

Reticulated vitreous carbon (RVC), a high surface area electrode (40 cm 2 /cm 3 ), has been modified with nickel oxide nanoparticles (nano-NiO x ) and used for electrochemical oxidation of urea from alkaline solution. For the cyclic voltammetry measurements, the used dimensions are 0.8 cm × 0.8 cm × 0.3 cm. The purpose was to offer high specific surface area using a porous open network structure to accelerate the electrochemical conversion. NiO x nanoparticles have been synthesized via an electrochemical route at some experimental conditions. The morphological, structural, and electrochemical properties of the RVC/nano-NiO x are characterized by using scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), cyclic voltammetry (CV), and potentiostatic measurements. The fabricated electrode, RVC/nano-NiO x , demonstrates high electrocatalytic activity towards urea oxidation in an alkaline electrolyte. The onset potential of the RVC/nano-NiO x compared to that of the planar GC/NiO x is shifted to more negative value with higher specific activity. The different loadings of the NiO x have a substantial influence on the conversion of urea which has been evaluated from concentration-time curves. The urea concentration decreases with time to a limit dependent on the loading extent. Maximum conversion is obtained at 0.86 mg of NiO x per cm 3 of the RVC matrix.

High temperature regenerative H.sub.2 S sorbents

NASA Technical Reports Server (NTRS)

Flytani-Stephanopoulos, Maria (Inventor); Gavalas, George R. (Inventor); Tamhankar, Satish S. (Inventor)

1988-01-01

Efficient, regenerable sorbents for removal of H.sub.2 S from high temperature gas streams comprise porous, high surface area particles. A first class of sorbents comprise a thin film of binary oxides that form a eutectic at the temperature of the gas stream coated onto a porous, high surface area refractory support. The binary oxides are a mixture of a Group VB or VIB metal oxide with a Group IB, IIB or VIII metal oxide such as a film of V-Zn-O, V-Cu-O, Cu-Mo-O, Zn-Mo-O or Fe-Mo-O coated on an alumina support. A second class of sorbents consist of particles of unsupported mixed oxides in the form of highly dispersed solid solutions of solid compounds characterized by small crystallite size, high porosity and relatively high surface area. The mixed oxide sorbents contain one Group IB, IIB or VIIB metal oxide such as copper, zinc or manganese and one or more oxides of Groups IIIA, VIB or VII such as aluminum, iron or molybdenum. The presence of iron or aluminum maintains the Group IB, IIB or VIIB metal in its oxidized state. Presence of molybdenum results in eutectic formation at sulfidation temperature and improves the efficiency of the sorbent.

Kinetic Model Development for the Combustion of Particulate Matter from Conventional and Soy Methyl Ester Diesel Fuels

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

Strzelec, Andrea

2009-12-01

The primary objective of this research has been to investigate how the oxidation characteristics of diesel particulate matter (PM) are affected by blending soy-based biodiesel fuel with conventional ultra low sulfur diesel (ULSD) fuel. PM produced in a light duty engine from different biodiesel-conventional fuel blends was subjected to a range of physical and chemical measurements in order to better understand the mechanisms by which fuel-related changes to oxidation reactivity are brought about. These observations were then incorporated into a kinetic model to predict PM oxidation. Nanostructure of the fixed carbon was investigated by HR-TEM and showed that particulates frommore » biodiesel had a more open structure than particulates generated from conventional diesel fuel, which was confirmed by BET surface area measurements. Surface area evolution with extent of oxidation reaction was measured for PM from ULSD and biodiesel. Biodiesel particulate has a significantly larger surface area for the first 40% of conversion, at which point the samples become quite similar. Oxidation characteristics of nascent PM and the fixed carbon portion were measured by temperature programmed oxidation (TPO) and it was noted that increased biodiesel blending lowered the light-off temperature as well as the temperature where the peak rate of oxidation occurred. A shift in the oxidation profiles of all fuels was seen when the mobile carbon fraction was removed, leaving only the fixed carbon, however the trend in temperature advantage of the biofuel blending remained. The mobile carbon fraction was measured by temperature programmed desorption found to generally increase with increasing biodiesel blend level. The relative change in the light-off temperatures for the nascent and fixed carbon samples was found to be related to the fraction of mobile carbon. Effective Arrhenius parameters for fixed carbon oxidation were directly measured with isothermal, differential oxidation experiments. Normalizing the reaction rate to the total carbon surface area available for reaction allowed for the definition of a single reaction rate with constant activation energy (112.5 {+-} 5.8 kJ/mol) for the oxidation of PM, independent of its fuel source. A kinetic model incorporating the surface area dependence of fixed carbon oxidation rate and the impact of the mobile carbon fraction was constructed and validated against experimental data.« less

Thermodynamic Versus Surface Area Control of Microbial Fe(III) Oxide Reduction Kinetics

NASA Astrophysics Data System (ADS)

Roden, E. E.

2003-12-01

Recent experimental studies of synthetic and natural Fe(III) oxide reduction permit development of conceptual and quantitative models of enzymatic Fe(III) oxide reduction at circumneutral pH that can be compared to and contrasted with established models of abiotic mineral dissolution. The findings collectively support a model for controls on enzymatic reduction that differs fundamentally from those applied to abiotic reductive dissolution as a result of two basic phenomena: (1) the relatively minor influence of oxide mineralogical and thermodynamic properties on surface area-normalized rates of enzymatic reduction compared to abiotic reductive dissolution; and (2) the major limitation which sorption and/or surface precipitation of biogenic Fe(II) on residual oxide and Fe(III)-reducing bacterial cell surfaces poses to enzymatic electron transfer in the presence of excess electron donor. Parallel studies with two major Fe(III)-reducing bacteria genera (Shewanella and Geobacter) lead to common conclusions regarding the importance of these phenomena in regulating the rate and long-term extent of Fe(III) oxide reduction. Although the extent to which these phenomena can be traced to underlying kinetic vs. thermodynamic effects cannot be resolved with current information, models in which rates of enzymatic reduction are limited kinetically by the abundance of "available" oxide surface sites (as controlled by oxide surface area and the abundance of surface-bound Fe(II)) provide an adequate macroscopic description of controls on the initial rate and long-term extent of oxide reduction. In some instances, thermodynamic limitation posed by the accumulation of aqueous reaction end-products (i.e. Fe(II) and alkalinity) must also be invoked to explain observed long-term patterns of reduction. In addition, the abundance of Fe(III)-reducing microorganisms plays an important role in governing rates of reduction and needs to be considered in models of Fe(III) reduction in nonsteady-state systems, e.g. subsurface environments in which Fe(III) reduction is stimulated by contamination with organics or for the purposes of metal/radionuclide bioremediation.

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.

Synthesis and Characterization of Mixed Iron-Manganese Oxide Nanoparticles and Their Application for Efficient Nickel Ion Removal from Aqueous Samples

PubMed Central

Serra, Antonio; Monteduro, Anna Grazia; Padmanabhan, Sanosh Kunjalukkal; Licciulli, Antonio; Bonfrate, Valentina; Salvatore, Luca; Calcagnile, Lucio

2017-01-01

Mixed iron-manganese oxide nanoparticles, synthesized by a simple procedure, were used to remove nickel ion from aqueous solutions. Nanostructures, prepared by using different weight percents of manganese, were characterized by transmission electron microscopy, selected area diffraction, X-ray diffraction, Raman spectroscopy, and vibrating sample magnetometry. Adsorption/desorption isotherm curves demonstrated that manganese inclusions enhance the specific surface area three times and the pores volume ten times. This feature was crucial to decontaminate both aqueous samples and food extracts from nickel ion. Efficient removal of Ni2+ was highlighted by the well-known dimethylglyoxime test and by ICP-MS analysis and the possibility of regenerating the nanostructure was obtained by a washing treatment in disodium ethylenediaminetetraacetate solution. PMID:28804670

Synthesis and capacitance properties of N-doped porous carbon/NiO nanosheet composites using coal-based polyaniline as carbon and nitrogen source

NASA Astrophysics Data System (ADS)

Wang, Xiaoqin; Li, Qiaoqin; Zhang, Yong; Yang, Yufei; Cao, Zhi; Xiong, Shanxin

2018-06-01

A novel synthesis approach of N-doped porous carbon (NPC)/NiO composites possessing some honeycomb-shaped nanoporous carbon and plentiful NiO nanosheets is exploited. First NPC/Ni composites are achieved with NPC yield of 52.9% through a catalytic pyrolysis method, using coal-based polyaniline particles prepared by an in-situ polymerization method as a carbon and nitrogen source, and nickel particles as a catalyst, respectively. Next NPC/NiO composites are achieved unexpectedly with plentiful NiO nanosheets and N content of 1.00 wt% after a liquid oxidation process. In NPC/NiO composites, porous carbon mainly presents in the amorphous state, while the incorporated nitrogen mainly presents in the form of pyrrolic N (92.9 at.%) and oxidized N (7.1 at.%). Plentiful NiO nanosheets are embedded in the pores or on the NPC surface. 33.3 at.% Ni2O3 components exist in the surface of NiO nanosheets. NPC/NiO composites possess not only rich micropores, but also significant mesopores and nanoscale macropores. The BET specific surface area, BET average pore width and BJH adsorption average pore diameter are 627.5 m2/g, 2.0 nm and 5.1 nm, respectively. NPC/NiO composites demonstrate a high specific capacitance of 404.1 F/g at 1 A/g, and a good cycling stability maintaining high specific capacitance of 212.4 F/g (84.3% of the initial capacitance) at 5 A/g after 5000 cycles of charge and discharge, attributed to some honeycomb-shaped nanopores of carbon and large specific surface area of NiO nanosheets, and the synergistic effects between electric double-layer capacitance of NPC and pseudocapacitance of NiO. This study may provide a novel approach for the value-added applications of low-rank coal.

Unzipping of multi-wall carbon nanotubes with different diameter distributions: Effect on few-layer graphene oxide obtention

NASA Astrophysics Data System (ADS)

Torres, D.; Pinilla, J. L.; Suelves, I.

2017-12-01

Few-layer graphene oxide (FLGO) was obtained by chemical unzipping of multi-wall carbon nanotubes (MWCNT) of different diameter distributions. MWCNT were synthesized by catalytic decomposition of methane using Fe-Mo/MgO catalysts. The variation in the Fe/Mo ratio (1, 2 and 5) was very influential in MWCNT diameter distribution and type of MWCNT obtained, including textural, chemical, structural and morphological characteristics. MWCNT diameter distribution and surface defects content had a profound impact on the characteristics of the resulting FLGO. Thus, MWCNT obtained with the catalyst with a Fe/Mo: 5 and presenting a narrow diameter distribution centered at 8.6 ± 3.3 nm led to FLGO maintaining non-oxidized graphite stacking (according to XRD analysis), lower specific surface area and higher thermostability as compared to FLGO obtained from MWCNT showing wider diameter distributions. The presence of more oxygen-containing functionalities and structural defects in large diameter nanotubes promotes the intercalation of species towards the inner layers of the nanotube, resulting in an enhanced MWCNT oxidation and opening into FLGO, what improves both micro- and mesoporosity.

Silver decorated polymer supported semiconductor thin films by UV aided metalized laser printing

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

Halbur, Jonathan C.; Padbury, Richard P.; Jur, Jesse S., E-mail: jsjur@ncsu.edu

2016-05-15

A facile ultraviolet assisted metalized laser printing technique is demonstrated through the ability to control selective photodeposition of silver on flexible substrates after atomic layer deposition pretreatment with zinc oxide and titania. The photodeposition of noble metals such as silver onto high surface area, polymer supported semiconductor metal oxides exhibits a new route for nanoparticle surface modification of photoactive enhanced substrates. Photodeposited silver is subsequently characterized using low voltage secondary electron microscopy, x-ray diffraction, and time of flight secondary ion mass spectroscopy. At the nanoscale, the formation of specific morphologies, flake and particle, is highlighted after silver is photodeposited onmore » zinc oxide and titania coated substrates, respectively. The results indicate that the morphology and composition of the silver after photodeposition has a strong dependency on the morphology, crystallinity, and impurity content of the underlying semiconductor oxide. At the macroscale, this work demonstrates how the nanoscale features rapidly coalesce into a printed pattern through the use of masks or an X-Y gantry stage with virtually unlimited design control.« less

Graphene oxide/MnO2 nanocomposite as destructive adsorbent of nerve-agent simulants in aqueous media

NASA Astrophysics Data System (ADS)

Šťastný, Martin; Tolasz, Jakub; Štengl, Václav; Henych, Jiří; Žižka, David

2017-08-01

Graphene oxide/MnO2 nanocomposite was prepared by thermal hydrolysis of potassium permanganate (KMnO4) and 2-chloroacetamide aqueous solutions with graphene oxide (GO) suspension. The synthesized samples were characterized by specific surface area (BET) and porosity determination (BJH), X-ray Diffraction (XRD) and high-resolution electron microscopes (HRSEM, HRTEM). These nanocomposites were used in an experimental evaluation of their adsorption activity with nerve agent simulants dimethyl methyl phosphonate (DMMP) and triethyl phosphate (TEP) in aqueous media. The nanocomposites exhibited enhanced adsorptive degradation ability compared to pure manganese oxide (MnO2) and GO. The GO amount in the nanocomposites affected their degradation activity substantially. The best adsorption efficiency was observed for samples with moderate GO amount. Three methods were used to observe the mechanism of the nerve-agent simulants deactivation: Gas chromatography with mass spectrometry (GC-MS), High-Performance Liquid Chromatography (HPLC) and in situ Infrared spectroscopy (FTIR). It was shown that the hydrolysis on the surface of prepared nanocomposites yields volatile primary alcohols (methanol and ethanol) as the main hydrolysis products.

Fabrication of CuO-doped catalytic material containing zeolite synthesized from red mud and rice husk ash for CO oxidation

NASA Astrophysics Data System (ADS)

Hieu Do Thi, Minh; Thinh Tran, Quoc; Nguyen, Tri; Van Nguyen Thi, Thuy; Huynh, Ky Phuong Ha

2018-06-01

In this study a series of the CuO-doped materials containing zeolite with varying CuO contents were synthesized from red mud (RM) and rice husk ash (RHA). The rice husk ash/red mud with the molar ratio of , and being 1.8, 2.5 and 60, respectively, were maintained during the synthetic process of materials. The characteristic structure samples were analyzed by x-ray diffraction (XRD), Fourier transformed infrared spectroscopy (FTIR), scanning electron microscopy (SEM), transmission electron microscope (TEM), Brunauer–Emmett–Teller (BET) surface area and H2 temperature program reduction (H2-TPR). The catalytic activity of samples was evaluated in CO oxidation reaction in a microflow reactor at temperature range 200 °C–350 °C. The obtained results showed that all synthetic samples there exist the A-type zeolites with the average crystal size of 15–20 nm, the specific surface area of , and pore volume of . The material synthesized from RM and RHA with the zeolite structure (ZRM, undoped CuO) could also oxidize CO completely at 350 °C, and its activity was increase significantly when doped with CuO. CuO-doped materials with the zeolite structure exhibited excellent catalytic activity in CO oxidation. The ZRM sample loading 5 wt% CuO with particle nanosize about 10–30 nm was the best one for CO oxidation with complete conversion temperature at 275 °C.

Pulsed photonic fabrication of nanostructured metal oxide thin films

NASA Astrophysics Data System (ADS)

Bourgeois, Briley B.; Luo, Sijun; Riggs, Brian C.; Adireddy, Shiva; Chrisey, Douglas B.

2017-09-01

Nanostructured metal oxide thin films with a large specific surface area are preferable for practical device applications in energy conversion and storage. Herein, we report instantaneous (milliseconds) photonic synthesis of three-dimensional (3-D) nanostructured metal oxide thin films through the pulsed photoinitiated pyrolysis of organometallic precursor films made by chemical solution deposition. High wall-plug efficiency-pulsed photonic irradiation (xenon flash lamp, pulse width of 1.93 ms, fluence of 7.7 J/cm2 and frequency of 1.2 Hz) is used for scalable photonic processing. The photothermal effect of subsequent pulses rapidly improves the crystalline quality of nanocrystalline metal oxide thin films in minutes. The following paper highlights pulsed photonic fabrication of 3-D nanostructured TiO2, Co3O4, and Fe2O3 thin films, exemplifying a promising new method for the low-cost and high-throughput manufacturing of nanostructured metal oxide thin films for energy applications.

The role of CO 2 as a soft oxidant for dehydrogenation of ethylbenzene to styrene over a high-surface-area ceria catalyst

DOE PAGES

Zhang, Li; Wu, Zili; Nelson, Nicholas; ...

2015-09-22

Catalytic performance and the nature of surface adsorbates were investigated for high-surface-area ceria during ethylbenzene oxidative dehydrogenation (ODH) reaction using CO2 as a soft oxidant. A template assisted method was used to synthesize the high-surface-area ceria. The interactions between ethylbenzene, styrene and CO2 on the surface of ceria and the role of CO2 for the ethylbenzene ODH reaction have been investigated in detail by using activity test, in situ Diffuse Reflectance Infrared and Raman spectroscopy. Not only did CO2 as an oxidant favor the higher yield of styrene, but it also inhibited the deposition of coke during the ethylbenzene ODHmore » reaction. Ethylbenzene ODH reaction over ceria followed a two-step pathway: Ethylbenzene is first dehydrogenated to styrene with H2 formed simultaneously, and then CO2 reacts with H2 via the reverse water gas shift. The styrene produced can easily polymerize to form polystyrene, a key intermediate for coke formation. In the absence of CO2, the polystyrene transforms into graphite-like coke at temperatures above 500 °C, which leads to catalyst deactivation. While in the presence of CO2, the coke deposition can be effectively removed via oxidation with CO2.« less

Weaving a two-dimensional fishing net from titanoniobate nanosheets embedded with Fe3O4 nanocrystals for highly efficient capture and isotope labeling of phosphopeptides

NASA Astrophysics Data System (ADS)

Chen, Xueqin; Li, Siyuan; Zhang, Xiaoxia; Min, Qianhao; Zhu, Jun-Jie

2015-03-01

Qualitative and quantitative characterization of phosphopeptides by means of mass spectrometry (MS) is the main goal of MS-based phosphoproteomics, but suffers from their low abundance in the large haystack of various biological molecules. Herein, we introduce two-dimensional (2D) metal oxides to tackle this biological separation issue. A nanocomposite composed of titanoniobate nanosheets embedded with Fe3O4 nanocrystals (Fe3O4-TiNbNS) is constructed via a facile cation-exchange approach, and adopted for the capture and isotope labeling of phosphopeptides. In this nanoarchitecture, the 2D titanoniobate nanosheets offer enlarged surface area and a spacious microenvironment for capturing phosphopeptides, while the Fe3O4 nanocrystals not only incorporate a magnetic response into the composite but, more importantly, also disrupt the restacking process between the titanoniobate nanosheets and thus preserve a greater specific surface for binding phosphopeptides. Owing to the extended active surface, abundant Lewis acid sites and excellent magnetic controllability, Fe3O4-TiNbNS demonstrates superior sensitivity, selectivity and capacity over homogeneous bulk metal oxides, layered oxides, and even restacked nanosheets in phosphopeptide enrichment, and further allows in situ isotope labeling to quantify aberrantly-regulated phosphopeptides from sera of leukemia patients. This composite nanosheet greatly contributes to the MS analysis of phosphopeptides and gives inspiration in the pursuit of 2D structured materials for separation of other biological molecules of interests.Qualitative and quantitative characterization of phosphopeptides by means of mass spectrometry (MS) is the main goal of MS-based phosphoproteomics, but suffers from their low abundance in the large haystack of various biological molecules. Herein, we introduce two-dimensional (2D) metal oxides to tackle this biological separation issue. A nanocomposite composed of titanoniobate nanosheets embedded with Fe3O4 nanocrystals (Fe3O4-TiNbNS) is constructed via a facile cation-exchange approach, and adopted for the capture and isotope labeling of phosphopeptides. In this nanoarchitecture, the 2D titanoniobate nanosheets offer enlarged surface area and a spacious microenvironment for capturing phosphopeptides, while the Fe3O4 nanocrystals not only incorporate a magnetic response into the composite but, more importantly, also disrupt the restacking process between the titanoniobate nanosheets and thus preserve a greater specific surface for binding phosphopeptides. Owing to the extended active surface, abundant Lewis acid sites and excellent magnetic controllability, Fe3O4-TiNbNS demonstrates superior sensitivity, selectivity and capacity over homogeneous bulk metal oxides, layered oxides, and even restacked nanosheets in phosphopeptide enrichment, and further allows in situ isotope labeling to quantify aberrantly-regulated phosphopeptides from sera of leukemia patients. This composite nanosheet greatly contributes to the MS analysis of phosphopeptides and gives inspiration in the pursuit of 2D structured materials for separation of other biological molecules of interests. Electronic supplementary information (ESI) available: Sequence of phosphopeptides from the digests of α- and β-casein percentages of the 4 methylated products from peptide β1 at different labeling reaction times; sequence of serum phosphopeptides; XPS spectra of Nb 3d and Ti 2p in layered oxides and H+-stacked nanosheets; phosphopeptide enrichment sensitivity of bulk oxides, layered oxides and H+-stacked nanosheets; AFM image of TiNbNS; saturated adsorption isotherm for pNPP adsorbed on bulk oxides, layered oxides and H+-stacked nanosheets; XPS spectra of Fe3O4-TiNbNS nitrogen adsorption-desorption isotherms and pore size distribution curves for the Fe3O4 nanocrystals; phosphopeptide enrichment sensitivity, capacity and selectivity of the Fe3O4-TiNbNS composites; MS/MS spectra of phosphopeptides enriched from serum; linear relationship between the logarithms of peak area ratio and loading volume ratio. See DOI: 10.1039/c4nr07041k

Screening for oxidative damage by engineered nanomaterials: a comparative evaluation of FRAS and DCFH

NASA Astrophysics Data System (ADS)

Pal, Anoop K.; Hsieh, Shu-Feng; Khatri, Madhu; Isaacs, Jacqueline A.; Demokritou, Philip; Gaines, Peter; Schmidt, Daniel F.; Rogers, Eugene J.; Bello, Dhimiter

2014-02-01

Several acellular assays are routinely used to measure oxidative stress elicited by engineered nanomaterials (ENMs), yet little comparative evaluations of such methods exist. This study compares for the first time the performance of the dichlorofluorescein (DCFH) assay which measures reactive oxygen species (ROS) generation, to that of the ferric-reducing ability of serum (FRAS) assay, which measures biological oxidant damage in serum. A diverse set of 28 commercially important and extensively characterized ENMs were tested on both the assays. Intracellular oxidative stress was also assessed on a representative subset of seven ENMs in THP-1 (phorbol 12-myristate 13-acetate matured human monocytes) cells. Associations between assay responses and ENM physicochemical properties were assessed via correlation and regression analysis. DCFH correlated strongly with FRAS after dose normalization for mass ( R 2 = 0.78) and surface area ( R 2 = 0.68). Only 10/28 ENMs were positive in DCFH versus 21/28 in FRAS. Both assays were strongly associated with specific surface area and transition metal content. Qualitatively, a similar response ranking was observed for acellular FRAS and intracellular reduced:oxidized glutathione ratio (GSH:GSSG) in cells. Quantitatively, weak correlation was found between intracellular GSSG and FRAS or DCFH ( R 2 < 0.25) even after calculating effective dose to cells. The FRAS assay was more sensitive than DCFH, especially for ENMs with low to moderate oxidative damage potential, and may serve as a more biologically relevant substitute for acellular ROS measurements of ENMs. Further in vitro and in vivo validations of FRAS against other toxicological endpoints with larger datasets are recommended.

Porous nickel hydroxide-manganese dioxide-reduced graphene oxide ternary hybrid spheres as excellent supercapacitor electrode materials.

PubMed

Chen, Hao; Zhou, Shuxue; Wu, Limin

2014-06-11

This paper reports the first nickel hydroxide-manganese dioxide-reduced graphene oxide (Ni(OH)2-MnO2-RGO) ternary hybrid sphere powders as supercapacitor electrode materials. Due to the abundant porous nanostructure, relatively high specific surface area, well-defined spherical morphology, and the synergetic effect of Ni(OH)2, MnO2, and RGO, the electrodes with the as-obtained Ni(OH)2-MnO2-RGO ternary hybrid spheres as active materials exhibited significantly enhanced specific capacitance (1985 F·g(-1)) and energy density (54.0 Wh·kg(-1)), based on the total mass of active materials. In addition, the Ni(OH)2-MnO2-RGO hybrid spheres-based asymmetric supercapacitor also showed satisfying energy density and electrochemical cycling stability.

Ultralight boron nitride aerogels via template-assisted chemical vapor deposition

PubMed Central

Song, Yangxi; Li, Bin; Yang, Siwei; Ding, Guqiao; Zhang, Changrui; Xie, Xiaoming

2015-01-01

Boron nitride (BN) aerogels are porous materials with a continuous three-dimensional network structure. They are attracting increasing attention for a wide range of applications. Here, we report the template-assisted synthesis of BN aerogels by catalyst-free, low-pressure chemical vapor deposition on graphene-carbon nanotube composite aerogels using borazine as the B and N sources with a relatively low temperature of 900 °C. The three-dimensional structure of the BN aerogels was achieved through the structural design of carbon aerogel templates. The BN aerogels have an ultrahigh specific surface area, ultralow density, excellent oil absorbing ability, and high temperature oxidation resistance. The specific surface area of BN aerogels can reach up to 1051 m2 g−1, 2-3 times larger than the reported BN aerogels. The mass density can be as low as 0.6 mg cm−3, much lower than that of air. The BN aerogels exhibit high hydrophobic properties and can absorb up to 160 times their weight in oil. This is much higher than porous BN nanosheets reported previously. The BN aerogels can be restored for reuse after oil absorption simply by burning them in air. This is because of their high temperature oxidation resistance and suggests broad utility as water treatment tools. PMID:25976019

Ultralight boron nitride aerogels via template-assisted chemical vapor deposition.

PubMed

Song, Yangxi; Li, Bin; Yang, Siwei; Ding, Guqiao; Zhang, Changrui; Xie, Xiaoming

2015-05-15

Boron nitride (BN) aerogels are porous materials with a continuous three-dimensional network structure. They are attracting increasing attention for a wide range of applications. Here, we report the template-assisted synthesis of BN aerogels by catalyst-free, low-pressure chemical vapor deposition on graphene-carbon nanotube composite aerogels using borazine as the B and N sources with a relatively low temperature of 900 (°)C. The three-dimensional structure of the BN aerogels was achieved through the structural design of carbon aerogel templates. The BN aerogels have an ultrahigh specific surface area, ultralow density, excellent oil absorbing ability, and high temperature oxidation resistance. The specific surface area of BN aerogels can reach up to 1051 m(2) g(-1), 2-3 times larger than the reported BN aerogels. The mass density can be as low as 0.6 mg cm(-3), much lower than that of air. The BN aerogels exhibit high hydrophobic properties and can absorb up to 160 times their weight in oil. This is much higher than porous BN nanosheets reported previously. The BN aerogels can be restored for reuse after oil absorption simply by burning them in air. This is because of their high temperature oxidation resistance and suggests broad utility as water treatment tools.

Hollow spiny shell of porous Ni-Mn oxides: A facile synthesis route and their application as electrode in supercapacitors

NASA Astrophysics Data System (ADS)

Wan, Houzhao; Lv, Lin; Peng, Lu; Ruan, Yunjun; Liu, Jia; Ji, Xiao; Miao, Ling; Jiang, Jianjun

2015-07-01

Hollow spiny shell Ni-Mn precursors composed of one-dimensional nanoneedles were synthesized via a simple hydrothermal method without any template. The hollow Spiny shell Ni-Mn oxides are obtained under thermal treatment at different temperatures. The BET surface areas of Ni-Mn oxides reach up to 112 and 133 m2 g-1 when calcination temperatures occur at 300 and 400 °C, respectively. The electrochemical performances of as-synthesized hollow spiny shell Ni-Mn oxides gradually die down with annealing temperatures increasing. The porous hollow spiny shell Ni-Mn oxide obtained at 300 °C delivers a maximum capacitance of 1140 F g-1 at a high current density of 1 A g-1 after 1000th cycles and the specific capacitance of Ni-Mn oxide will increase with cycling times increasing. So, porous hollow spiny shell Ni-Mn oxide obtained at low annealing temperature can form a competitive electrode material for supercapacitors.

Gas sensing in 2D materials

NASA Astrophysics Data System (ADS)

Yang, Shengxue; Jiang, Chengbao; Wei, Su-huai

2017-06-01

Two-dimensional (2D) layered inorganic nanomaterials have attracted huge attention due to their unique electronic structures, as well as extraordinary physical and chemical properties for use in electronics, optoelectronics, spintronics, catalysts, energy generation and storage, and chemical sensors. Graphene and related layered inorganic analogues have shown great potential for gas-sensing applications because of their large specific surface areas and strong surface activities. This review aims to discuss the latest advancements in the 2D layered inorganic materials for gas sensors. We first elaborate the gas-sensing mechanisms and introduce various types of gas-sensing devices. Then, we describe the basic parameters and influence factors of the gas sensors to further enhance their performance. Moreover, we systematically present the current gas-sensing applications based on graphene, graphene oxide (GO), reduced graphene oxide (rGO), functionalized GO or rGO, transition metal dichalcogenides, layered III-VI semiconductors, layered metal oxides, phosphorene, hexagonal boron nitride, etc. Finally, we conclude the future prospects of these layered inorganic materials in gas-sensing applications.

Destructive behavior of iron oxide in projectile impact

NASA Astrophysics Data System (ADS)

Shang, Wang; Xiaochen, Wang; Quan, Yang; Zhongde, Shan

2017-12-01

The damage strain values of Q235-A surface oxide scale were obtained by scanning electron microscopy (SEM/EDS) and universal tensile testing machine. The finite element simulation was carried out to study the destruction effects of oxidation at different impact rates. The results show that the damage value of the oxide strain is 0.08%. With the increase of the projectile velocity, the damage area of the oxide scale is increased, and the damage area is composed of the direct destruction area and the indirect failure area. The indirect damage area is caused by the stress/strain to the surrounding expansion after the impact of the steel body.

Ultrathin Nickel Hydroxide and Oxide Nanosheets: Synthesis, Characterizations and Excellent Supercapacitor Performances

PubMed Central

Zhu, Youqi; Cao, Chuanbao; Tao, Shi; Chu, Wangsheng; Wu, Ziyu; Li, Yadong

2014-01-01

High-quality ultrathin two-dimensional nanosheets of α-Ni(OH)2 are synthesized at large scale via microwave-assisted liquid-phase growth under low-temperature atmospheric conditions. After heat treatment, non-layered NiO nanosheets are obtained while maintaining their original frame structure. The well-defined and freestanding nanosheets exhibit a micron-sized planar area and ultrathin thickness (<2 nm), suggesting an ultrahigh surface atom ratio with unique surface and electronic structure. The ultrathin 2D nanostructure can make most atoms exposed outside with high activity thus facilitate the surface-dependent electrochemical reaction processes. The ultrathin α-Ni(OH)2 and NiO nanosheets exhibit enhanced supercapacitor performances. Particularly, the α-Ni(OH)2 nanosheets exhibit a maximum specific capacitance of 4172.5 F g−1 at a current density of 1 A g−1. Even at higher rate of 16 A g−1, the specific capacitance is still maintained at 2680 F g−1 with 98.5% retention after 2000 cycles. Even more important, we develop a facile and scalable method to produce high-quality ultrathin transition metal hydroxide and oxide nanosheets and make a possibility in commercial applications. PMID:25168127

The preparation of large surface area lanthanum based perovskite supports for AuPt nanoparticles: tuning the glycerol oxidation reaction pathway by switching the perovskite B site

PubMed Central

Evans, Christopher D.; Smith, Paul J.; Manning, Troy D.; Miedziak, Peter J.; Brett, Gemma L.; Armstrong, Robert D.; Bartley, Jonathan K.; Taylor, Stuart H.; Rosseinsky, Matthew J.; Hutchings, Graham J.

2016-01-01

Gold and gold alloys, in the form of supported nanoparticles, have been shown over the last three decades to be highly effective oxidation catalysts. Mixed metal oxide perovskites, with their high structural tolerance, are ideal for investigating how changes in the chemical composition of supports affect the catalysts' properties, while retaining similar surface areas, morphologies and metal co-ordinations. However, a significant disadvantage of using perovskites as supports is their high crystallinity and small surface area. We report the use of a supercritical carbon dioxide anti-solvent precipitation methodology to prepare large surface area lanthanum based perovskites, making the deposition of 1 wt% AuPt nanoparticles feasible. These catalysts were used for the selective oxidation of glycerol. By changing the elemental composition of the perovskite B site, we dramatically altered the reaction pathway between a sequential oxidation route to glyceric or tartronic acid and a dehydration reaction pathway to lactic acid. Selectivity profiles were correlated to reported oxygen adsorption capacities of the perovskite supports and also to changes in the AuPt nanoparticle morphologies. Extended time on line analysis using the best oxidation catalyst (AuPt/LaMnO3) produced an exceptionally high tartronic acid yield. LaMnO3 produced from alternative preparation methods was found to have lower activities, but gave comparable selectivity profiles to that produced using the supercritical carbon dioxide anti-solvent precipitation methodology. PMID:27074316

The preparation of large surface area lanthanum based perovskite supports for AuPt nanoparticles: tuning the glycerol oxidation reaction pathway by switching the perovskite B site.

PubMed

Evans, Christopher D; Kondrat, Simon A; Smith, Paul J; Manning, Troy D; Miedziak, Peter J; Brett, Gemma L; Armstrong, Robert D; Bartley, Jonathan K; Taylor, Stuart H; Rosseinsky, Matthew J; Hutchings, Graham J

2016-07-04

Gold and gold alloys, in the form of supported nanoparticles, have been shown over the last three decades to be highly effective oxidation catalysts. Mixed metal oxide perovskites, with their high structural tolerance, are ideal for investigating how changes in the chemical composition of supports affect the catalysts' properties, while retaining similar surface areas, morphologies and metal co-ordinations. However, a significant disadvantage of using perovskites as supports is their high crystallinity and small surface area. We report the use of a supercritical carbon dioxide anti-solvent precipitation methodology to prepare large surface area lanthanum based perovskites, making the deposition of 1 wt% AuPt nanoparticles feasible. These catalysts were used for the selective oxidation of glycerol. By changing the elemental composition of the perovskite B site, we dramatically altered the reaction pathway between a sequential oxidation route to glyceric or tartronic acid and a dehydration reaction pathway to lactic acid. Selectivity profiles were correlated to reported oxygen adsorption capacities of the perovskite supports and also to changes in the AuPt nanoparticle morphologies. Extended time on line analysis using the best oxidation catalyst (AuPt/LaMnO3) produced an exceptionally high tartronic acid yield. LaMnO3 produced from alternative preparation methods was found to have lower activities, but gave comparable selectivity profiles to that produced using the supercritical carbon dioxide anti-solvent precipitation methodology.

Penetration of carbon-fabric-reinforced composites by edge cracks during thermal aging

NASA Technical Reports Server (NTRS)

Bowles, Kenneth J.; Kamvouris, John E.

1994-01-01

Thermo-oxidative stability (TOS) test results are significantly influenced by the formation and growth or presence of interlaminar and interlaminar cracks in the cut edges of all carbon-fiber-crosslinked high-temperature polymer matrix composites(exp 1-5) (i.e., unidirectional, crossplied, angle-plied, and fabric composites). The thermo-oxidative degradation of these composites is heavily dependent on the surface area that is exposed to the harmful environment and on the surface-to-volume ratio of the structure under study. Since the growth of cracks and voids on the composite surfaces significantly increases the exposed surface areas, it is imperative that the interaction between the aging process and the formation of new surface area as the aging time progresses be understood.

Surface characterization studies of walnut-shell biochar catalysts for simultaneously removing of organic sulfur from yellow phosphorus tail gas

NASA Astrophysics Data System (ADS)

Song, Xin; Li, Kai; Ning, Ping; Wang, Chi; Sun, Xin; Tang, Lihong; Ruan, Haotian; Han, Shuang

2017-12-01

The influences of different preparation conditions for surface characteristics on removing organic sulfur were studied. From BET, XRD, FTIR, DRIFTS, TG/DTA, CO2-TPD results, it can be seen that these preparation conditions had great influences on the pore structure, specific surface area, crystal structure and surface functional groups. The micropore volume, amorphous structure and alkalinity site strength played major roles in desulfurization process. H2S was oxidized by oxygen containing functional groups, such as sbnd COO, sbnd Cdbnd O. H2O molecule could be converted into some groups, such as sbnd CH and Csbnd OH groups, and promoted the hydrolysis reaction. The strong alkalinity site was the key factor for chemical adsorption and hydrolysis. H2O molecule, sbnd CH, Csbnd OH groups promoted the hydrolysis reaction and sbnd COO, sbnd Cdbnd O groups promoted the oxidation of H2S on the surface of WSB. Meanwhile, the main desulfurization process over WSB after carbonization was adsorption and it changed to hydrolysis reaction after activation on the surface of WSB. Furthermore, the reaction mechanism was investigated by DRIFTS measurement according to the change of surface functional groups.

Novel carbon nanostructures as catalyst support for polymer electrolyte membrane fuel cells

NASA Astrophysics Data System (ADS)

Natarajan, Sadesh Kumar

Polymer electrolyte membrane fuel cell (PEMFC) technology has advanced rapidly in recent years, with one of active area focused on improving the long-term performance of carbon supported catalysts, which has been recognized as one of the most important issues to be addressed for the commercialization of PEMFCs. The central part of a PEMFC is the membrane electrode assembly (MEA) which consists of two electrodes (anode and cathode) and a cation exchange membrane. These electrodes are commonly made of carbon black (most often, Vulcan XC-72) supported on carbon paper or carbon cloth backings. It is the primary objective of this thesis to prepare and investigate carbon nanostructures (CNS, licensed to Hydrogen Research Institute -- IRH, Quebec, Canada), the carbon material with more graphite component like carbon nanotubes (CNTs) for use as catalyst support in PEMFCs. High energy ball-milling of activated carbon along with transition metal catalysts under hydrogen atmosphere, followed by heat-treatment leads to nanocrystalline structures of carbon called CNS. However, CNS formed in the quartz tube after heat-treatment is inevitably accompanied by many impurities such as metal particles, amorphous carbon and other carbon nanoparticules. Such impurities are a serious impediment to detailed characterization of the properties of nanostructures. In addition, since the surface of CNS is itself rather inert, it is difficult to control the homogeneity and size distribution of Pt nanoparticules. In this thesis work, we demonstrated a novel mean to purify and functionalize CNS via acid-oxidation under reflux conditions. To investigate and quantify these nanostructures X-ray diffraction, electrical conductivity measurements, specific surface area measurements, thermogravimetric analysis, X-ray photoelectron spectroscopy and transmission electron microscopy studies were used. Cyclic voltammetry studies were performed on different samples to derive estimates for the relationship between the composition of the acid mixture and their influence in producing high density of surface functional groups. Such surface functionalization on CNS enhances the reactivity, improves the specificity and provides an avenue for Pt deposition. It was also shown that a 1:1 mixture of 7.5 M sulphuric acid and 15 M nitric acid have generated higher composition of non-acidic functional groups over other acid compositions discussed in this thesis. In this thesis, we also demonstrated a novel method to deposit and disperse platinum clusters on carbon nanotubes via a chemically specific nucleation mechanism. To investigate and quantify these platinized CNS X-ray diffraction, thermogravimetric analysis, atomic adsorption spectroscopy and high resolution transmission electron microscopy were used. An average Pt cluster size of 4 nm was dispersed homogeneously on CNS that was functionalized with the method described above. The corrosive nature of carbon support material is a crucial issue for the commercialization of PEMFC systems. Therefore, electrochemical oxidations of Pt/CNS compared with Pt/C were studied in this thesis with the aim to understand their durability as catalyst support in PEMFCs. The surface oxidation of the catalyst materials has been compared following potentiostatic treatments up to 200 h under condition simulating the PEMFC cathode environment (80°C, nitrogen purged 0.5 M sulphuric acid, and a constant potential of 1.2 V). The degradation of Pt catalysts and the carbon support was also evaluated by measuring the cell voltage at constant load after different oxidation intervals at 1.2 V. The agglomeration of Pt catalyst particles and the changes in surface functional groups of the carbon material at different intervals of electrochemical oxidation was evaluated using X-ray diffraction and thermogravimetric studies. The subsequent electrochemical characterization at different treatment time intervals by both the above methods suggests that CNS is electrochemically more stable than Vulcan XC-72 with less surface oxide formation and Pt surface area loss without sacrificing catalytic activity. (Abstract shortened by UMI.)

Adsorption of bovine serum albumin on nano and bulk oxide particles in deionized water.

PubMed

Song, Lei; Yang, Kun; Jiang, Wei; Du, Peng; Xing, Baoshan

2012-06-01

In this work, the influence of particle size and surface functional groups on the adsorption behavior of bovine serum albumin (BSA) by three types of oxide nanoparticles (NPs), TiO(2) (50±5 nm), SiO(2) (30±5 nm), and Al(2)O(3) (150±5 nm for α type and 60±5 nm for γ type) was investigated in deionized water, in order to explore their interaction mechanisms without competitive influence of other ions. Bulkparticles (BPs) were also used for comparison with NPs. BSA adsorption maxima on oxide particles were controlled by the surface area and hydrogen content, while adsorption process was primarily induced by electrostatic interaction, hydrophobic interaction and ligand exchange between BSA and oxide surfaces. With the increase of hydrogen content, the BSA adsorption mechanism switched from mainly hydrophobic interaction to hydrogen bonding and ligand exchange. Calculations, based on surface area and BSA size, suggested that a multilayer of BSA covered on α-Al(2)O(3), and single layer on the other oxide particle surfaces. BPs led to greater conformational change of BSA molecules after the adsorption on the surfaces of oxide particles though NPs adsorbed more BSA than BPs. Copyright © 2012 Elsevier B.V. All rights reserved.

Effect of calcination temperatures on microstructures and photocatalytic activity of tungsten trioxide hollow microspheres.

PubMed

Yu, Jiaguo; Qi, Lifang; Cheng, Bei; Zhao, Xiufeng

2008-12-30

Tungsten trioxide hollow microspheres were prepared by immersing SrWO4 microspheres in a concentrated HNO3 solution, and then calcined at different temperatures. The prepared tungsten oxide samples were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, Fourier transform infrared spectra, differential thermal analysis-thermogravimetry, UV-visible spectrophotometry, scanning electron microscopy, N2 adsorption/desorption measurements. The photocatalytic activity of the samples was evaluated by photocatalytic decolorization of rhodamine B aqueous solution under visible-light irradiation. It was found that with increasing calcination temperatures, the average crystallite size and average pore size increased, on the contrary, Brunauer-Emmett-Teller-specific surface areas decreased. However, pore volume and porosity increased firstly, and then decreased. Increasing calcination temperatures resulted in the changes of surface morphology of hollow microspheres. The un-calcined and 300 degrees C-calcined samples showed higher photocatalytic activity than other samples. At 400 degrees C, the photocatalytic activity decreased greatly due to the decrease of specific surface areas. At 500 degrees C, the photocatalytic activity of the samples increased again due to the junction effect of two phases.

C-IOP/NiO/Ni7S6 composite with the inverse opal lattice as an electrode for supercapacitors

NASA Astrophysics Data System (ADS)

Sukhinina, Nadezhda S.; Masalov, Vladimir M.; Zhokhov, Andrey A.; Zverkova, Irina I.; Emelchenko, Gennadi A.

2015-06-01

In this work, we demonstrate the results of studies on the synthesis, the structure and properties of carbon inverted opal (C-IOP) nanostructures, the surface of which is modified by oxide and sulfide of nickel. It is shown that the modification of the matrix C-IOP by nickel compounds led to a decreasing the specific surface area more than three times and was 250 m2/g. The specific capacitance of the capacitor with the C-IOP/NiO/Ni7S6 composite as electrode has increased more than 4 times, from 130 F/g to 600 F/g, as compared with the sample C-IOP without the modification by nickel compounds. The significant contribution of the faradaic reactions in specific capacitance of the capacitor electrodes of the composites is marked.

Finely Tuned SnO2 Nanoparticles for Efficient Detection of Reducing and Oxidizing Gases: The Influence of Alkali Metal Cation on Gas-Sensing Properties.

PubMed

Lee, Szu-Hsuan; Galstyan, Vardan; Ponzoni, Andrea; Gonzalo-Juan, Isabel; Riedel, Ralf; Dourges, Marie-Anne; Nicolas, Yohann; Toupance, Thierry

2018-03-28

Tin dioxide (SnO 2 ) nanoparticles were straightforwardly synthesized using an easily scaled-up liquid route that involves the hydrothermal treatment, either under acidic or basic conditions, of a commercial tin dioxide particle suspension including potassium counterions. After further thermal post-treatment, the nanomaterials have been thoroughly characterized by Fourier transform infrared and Raman spectroscopy, powder X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, and nitrogen sorption porosimetry. Varying pH conditions and temperature of the thermal treatment provided cassiterite SnO 2 nanoparticles with crystallite sizes ranging from 7.3 to 9.7 nm and Brunauer-Emmett-Teller surface areas ranging from 61 to 106 m 2 ·g -1 , acidic conditions favoring potassium cation removal. Upon exposure to a reducing gas (H 2 , CO, and volatile organic compounds such as ethanol and acetone) or oxidizing gas (NO 2 ), layers of these SnO 2 nanoparticles led to highly sensitive, reversible, and reproducible responses. The sensing results were discussed in regard to the crystallite size, specific area, valence band energy, Debye length, and chemical composition. Results highlight the impact of the counterion residuals, which affect the gas-sensing performance to an extent much higher than that of size and surface area effects. Tin dioxide nanoparticles prepared under acidic conditions and calcined in air showed the best sensing performances because of lower amount of potassium cations and higher crystallinity, despite the lower surface area.

Sorption of N2 and EGME vapors on some soils, clays, and mineral oxides and determination of sample surface areas by use of sorption data

USGS Publications Warehouse

Chiou, C.T.; Rutherford, D.W.; Manes, M.

1993-01-01

Vapor sorption isotherms of ethylene glycol monoethyl ether (EGME) at room temperature and isotherms of N2 gas at liquid nitrogen temperature were determined for various soils and minerals. The N2 monolayer capacities [Qm (N2)] were calculated from the BET equation and used to determine the surface areas. To examine whether EGME is an appropriate adsorbate for determination of surface areas, the apparent EGME monolayer capacities [Qm (EGME)ap] were also obtained by use of the BET equation. For sand, aluminum oxide, kaolinite, hematite, and synthetic hydrous iron oxide, which are relatively free of organic impurity and expanding/solvating minerals, the Qm (EGME)ap values are in good conformity with the corresponding Qm (N2) values and would give surface areas consistent with BET (N2) values. For other samples (Woodburn soil, a natural hydrous iron oxide, illite, and montmorillonite), the Qm (EGME)ap values overestimate the Qm (N2) values from a moderate to a large extent, depending on the sample. A high-organic-content peat shows a very small BET (N2) surface area; the EGME/ peat isotherm is linear and does not yield a calculation of the surface area. Large discrepancies between results of the two methods for some samples are attributed to the high solubility of polar EGME in soil organic matter and/ or to the cation solvation of EGME with solvating clays. The agreement for other samples is illustrative of the consistency of the BET method when different adsorbates are used, so long as they do not exhibit bulk penetration and/or cation solvation. ?? 1993 American Chemical Society.

Manganese-cerium oxide catalysts prepared by non-thermal plasma for NO oxidation: Effect of O2 in discharge atmosphere

NASA Astrophysics Data System (ADS)

Liu, Lu; Zheng, Chenghang; Wu, Shenghao; Gao, Xiang; Ni, Mingjiang; Cen, Kefa

2017-09-01

Non-thermal plasma with different O2 concentration in discharge atmosphere was applied to synthesize manganese and cerium mixed-oxides catalysts, which were compared in NO oxidation activity. Discharge atmosphere displayed a crucial influence on the performance of the catalysts prepared by plasma. Relatively low O2 concentration in discharge atmosphere allows synthesizing manganese-cerium oxides catalysts in a moderate environment and therefore is favorable for better physicochemical properties which lead to superior catalytic behavior. The best catalyst was obtained by treatment with 10% O2/N2 plasma and presented over 80% NO conversion in the temperature range of 275-325 °C, whereas catalyst prepared in pure O2 discharge atmosphere had the same activity with a catalyst prepared by calcinations. A correlation between the surface properties of the plasma prepared catalysts and its catalytic activity in NO oxidation is proposed. The amount of the surface adsorbed oxygen has an obvious linear correlation with the amount of Ce3+, the H2 consumption at low temperatures and the catalytic performance. The superior catalytic performance is mainly attributed to the stronger interaction between manganese oxides and ceria, and the formation of poorly crystallized Mn-O-Ce phase in the catalyst which resulted from the slow decomposition of nitrates and organics during plasma treatment. Catalysts prepared in relatively low O2 concentration have large specific surface area and is abundant in Ce3+ species and active oxygen species. The study suggests that plasma treatment with proper discharge gas components is a promising method to prepare effective manganese- cerium oxides catalyst for NO oxidation.

Mesoporous composite nickel cobalt oxide/graphene oxide synthesized via a template-assistant co-precipitation route as electrode material for supercapacitors

NASA Astrophysics Data System (ADS)

Xu, Yanjie; Wang, Lincai; Cao, Peiqi; Cai, Chuanlin; Fu, Yanbao; Ma, Xiaohua

2016-02-01

A simple co-precipitation method utilizing SDS (sodium dodecyl sulfate) as template and ammonia as precipitant is successfully employed to synthesize nickel cobalt oxide/graphene oxide (NiCo2O4/GO) composite. The as-prepared composite (NCG-10) exhibits a high capacitance of 1211.25 F g-1, 687 F g-1 at the current density of 1 A g-1, 10 A g-1 and good cycling ability which renders NCG-10 as promising electrode material for supercapacitors. An asymmetric supercapacitor (ASC) (full button cell) has been constructed with NCG-10 as positive electrode and lab-made reduced graphene oxide (rGO) as negative electrode. The fabricated NCG-10//rGO with an extended stable operational voltage of 1.6 V can deliver a high specific capacitance of 144.45 F g-1 at a current density of 1 A g-1. The as-prepared NCG-10//rGO demonstrates remarkable energy density (51.36 W h kg-1 at 1 A g-1), high power density (50 kW kg-1 at 20 A g-1). The retention of capacitance is 88.6% at the current density of 8 A g-1 after 2000 cycles. The enhanced capacitive performance can be attributed to the improved specific surface area and 3D open area of NCG-10 generated by the pores and channels with the substantial function of SDS.

In-situ upgrading of biomass pyrolysis vapors: catalyst screening on a fixed bed reactor.

PubMed

Stefanidis, S D; Kalogiannis, K G; Iliopoulou, E F; Lappas, A A; Pilavachi, P A

2011-09-01

In-situ catalytic upgrading of biomass fast pyrolysis vapors was performed in a fixed bed bench-scale reactor at 500°C, for catalyst screening purposes. The catalytic materials tested include a commercial equilibrium FCC catalyst (E-cat), various commercial ZSM-5 formulations, magnesium oxide and alumina materials with varying specific surface areas, nickel monoxide, zirconia/titania, tetragonal zirconia, titania and silica alumina. The bio-oil was characterized measuring its water content, the carbon-hydrogen-oxygen (by difference) content and the chemical composition of its organic fraction. Each catalytic material displayed different catalytic effects. High surface area alumina catalysts displayed the highest selectivity towards hydrocarbons, yielding however low organic liquid products. Zirconia/titania exhibited good selectivity towards desired compounds, yielding higher organic liquid product than the alumina catalysts. The ZSM-5 formulation with the highest surface area displayed the most balanced performance having a moderate selectivity towards hydrocarbons, reducing undesirable compounds and producing organic liquid products at acceptable yields. Copyright © 2011 Elsevier Ltd. All rights reserved.

Pyrolytic synthesis and characterization of N-doped carbon nanoflakes for electrochemical applications

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

Savilov, S.V., E-mail: savilov@chem.msu.ru; N.S. Kurnakov Institute of General and Inorganic Chemistry Of Russian Academy of Sciences, Leninsky avenue, 31, Moscow 119991; Arkhipova, E.A.

2015-09-15

Highlights: • Carbon nanoflakes doped with nitrogen were produced by a pyrolytic technique. • Quarternary, pyrrolic and pyridinic types of nitrogen are confirmed by XPS. • Nitrogen content depends on precursor used and temperature processed. • Specific surface area values decrease with increasing of synthesis duration. • N-doped carbon nanoflakes may be suitable for electrochemical applications. - Abstract: Nitrogen doped carbon nanoflakes, which are very important for many electrochemical applications, were synthesized by pyrolysis of nitrogen containing organic compounds over metal oxide template. Acetonitrile, pyridine and butylamine, which are of different volatility were tested as N-containing precursors. Morphology, structure andmore » chemical composition of the as-synthesized materials were investigated by scanning electron microscopy (SEM), high resolution transmission electron microscopy (TEM), Raman spectroscopy and X-ray photoelectron spectroscopy (XPS). It was found that materials are highly defective and consist of a few malformed graphene layers. X-ray photoelectron spectra reflect the dominant graphitic and pyridinic N-bonding configuration. It was also noted that specific surface area depends on the duration and temperature of the reaction. Increase in duration and temperature led to decrease of the specific surface area from 1000 to 160 m{sup 2}/g, 1170 to 210 m{sup 2}/g and 1180 to 480 m{sup 2}/g for acetonitrile, butylamine and pyridine precursors, respectively.« less

Ab initio study of perovskite type oxide materials for solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Lee, Yueh-Lin

2011-12-01

Perovskite type oxides form a family of materials of significant interest for cathodes and electrolytes of solid oxide fuel cells (SOFCs). These perovskites not only are active catalysts for surface oxygen reduction (OR) reactions but also allow incorporating the spilt oxygen monomers into their bulk, an unusual and poorly understood catalytic mechanism that couples surface and bulk properties. The OR mechanisms can be influenced strongly by defects in perovskite oxides, composition, and surface defect structures. This thesis work initiates a first step in developing a general strategy based on first-principles calculations for detailed control of oxygen vacancy content, transport rates of surface and bulk oxygen species, and surface/interfacial reaction kinetics. Ab initio density functional theory methods are used to model properties relevant for the OR reactions on SOFC cathodes. Three main research thrusts, which focus on bulk defect chemistry, surface defect structures and surface energetics, and surface catalytic properties, are carried to investigate different level of material chemistry for improved understanding of key physics/factors that govern SOFC cathode OR activity. In the study of bulk defect chemistry, an ab initio based defect model is developed for modeling defect chemistry of LaMnO 3 under SOFC conditions. The model suggests an important role for defect interactions, which are typically excluded in previous defect models. In the study of surface defect structures and surface energetics, it is shown that defect energies change dramatically (1˜2 eV lower) from bulk values near surfaces. Based on the existing bulk defect model with the calculated ab initio surface defect energetics, we predict the (001) MnO 2 surface oxygen vacancy concentration of (La0.9Sr0.1 )MnO3 is about 5˜6 order magnitude higher than that of the bulk under typical SOFC conditions. Finally, for surface catalytic properties, we show that area specific resistance, oxygen exchange rates, and key OR energetics of the SOFC cathode perovskites, can be described by a single descriptor, either the bulk O p-band or the bulk oxygen vacancy formation energy. These simple descriptors will further enable first-principles optimization/design of new SOFC cathodes.

Enhanced adsorption and catalytic oxidation of ciprofloxacin by an Ag/AgCl@N-doped activated carbon composite

NASA Astrophysics Data System (ADS)

Nekouei, Farzin; Nekouei, Shahram; Noorizadeh, Hossein

2018-03-01

In this study, we synthesized a new nanocomposite catalyst comprising Ag/AgCl@N-doped activated carbon (Ag/AgCl@N-AC) and demonstrated its high efficiency during the enhanced adsorptive removal and catalytic oxidation of ciprofloxacin (CIP) with peroxymonosulfate (PMS) and persulfate (PS) as oxidants in aqueous solution. The efficiency of the new nanocomposite was compared with those of both pristine AC and N-AC under the same conditions. Furthermore, the effects of oxidants on the catalytic oxidation of CIP were assessed using PMS and PS. We found that the degradation efficiency of CIP with Ag/AgCl@N-AC was higher when using PS as an oxidant, whereas the use of PMS obtained relatively better results with both AC and N-AC. The adsorption processes for AC, N-AC, and Ag/AgCl@N-AC were dominated not only by electrostatic attraction but also by π-π interactions, which had higher impacts on the adsorption processes than the specific surface area.

Change of properties after oxidation of IG-11 graphite by air and CO 2 gas

NASA Astrophysics Data System (ADS)

Lim, Yun-Soo; Chi, Se-Hwan; Cho, Kwang-Yun

2008-02-01

Artificial graphite is typically manufactured by carbonization of a shaped body of a kneaded mixture using granular cokes as a filler and pitch as a binder. It undergoes a pitch impregnation process if necessary and finally applying graphitization heat treatment. The effect of thermal oxidation in air or a CO 2 atmosphere on IG-11 graphite samples is investigated in this study. The results show a localized oxidation process that progressively reveals the large coke particles with increasing level of overall weight loss in air. The surface of the graphite was peeled off and no change was found in the specific gravity after air oxidation. However, the specific gravity of graphite was continuously decreased by CO 2 oxidation. The decrease in the specific gravity by CO 2 oxidation was due to CO 2 gas that progressed from the surface to the interior. The pore shape after CO 2 oxidation differed from that under air oxidation.

Stripe distribution on graphene-coated Cu surface and its effect on oxidation and corrosion resistance of graphene

NASA Astrophysics Data System (ADS)

Zhang, Yanhui; Zhang, Haoran; Chen, Zhiying; Ge, Xiaoming; Liang, Yijian; Hu, Shike; Deng, Rongxuan; Sui, Yan-ping; Yu, Guang-hui

2017-06-01

The morphology and distribution of the stripes caused by Cu surface reconstruction were measured, and the effects of stripes on graphene stability were studied by oxidation and corrosion. The results reveal that the stripes are determined by the crystal orientation of both the Cu surface and graphene, which can both change the stripe distribution, and the stripes can also be influenced by the graphene thickness. The stripes would not induce cracks or destruction to the graphene. The oxidation resistance of graphene can be improved by Cu surface reconstruction. The local nonuniform distortion of the stripe area may induce a bigger strain in the graphene which, in turn, may induce structure instability and result in local stability degeneration in the stripe area.

Multimetallic nanosheets: synthesis and applications in fuel cells.

PubMed

Zeb Gul Sial, Muhammad Aurang; Ud Din, Muhammad Aizaz; Wang, Xun

2018-04-03

Two-dimensional nanomaterials, particularly multimetallic nanosheets with single or few atoms thickness, are attracting extensive research attention because they display remarkable advantages over their bulk counterparts, including high electron mobility, unsaturated surface coordination, a high aspect ratio, and distinctive physical, chemical, and electronic properties. In particular, their ultrathin thickness endows them with ultrahigh specific surface areas and a relatively high surface energy, making them highly favorable for surface active applications; for example, they have great potential for a broad range of fuel cell applications. First, the state-of-the-art research on the synthesis of nanosheets with a controlled size, thickness, shape, and composition is described and special emphasis is placed on the rational design of multimetallic nanosheets. Then, a correlation is performed with the performance of multimetallic nanosheets with modified and improved electrochemical properties and high stability, including for the oxygen reduction reaction (ORR), hydrogen evolution reaction (HER), formic acid oxidation (FAO), methanol oxidation reaction (MOR), ethanol oxidation reaction (EOR), and methanol tolerance are outlined. Finally, some perspectives and advantages offered by this class of materials are highlighted for the development of highly efficient fuel cell electrocatalysts, featuring low cost, enhanced performance, and high stability, which are the key factors for accelerating the commercialization of future promising fuel cells.

Thermochemical CO2 splitting via redox cycling of ceria reticulated foam structures with dual-scale porosities.

PubMed

Furler, Philipp; Scheffe, Jonathan; Marxer, Daniel; Gorbar, Michal; Bonk, Alexander; Vogt, Ulrich; Steinfeld, Aldo

2014-06-14

Efficient heat transfer of concentrated solar energy and rapid chemical kinetics are desired characteristics of solar thermochemical redox cycles for splitting CO2. We have fabricated reticulated porous ceramic (foam-type) structures made of ceria with dual-scale porosity in the millimeter and micrometer ranges. The larger void size range, with dmean = 2.5 mm and porosity = 0.76-0.82, enables volumetric absorption of concentrated solar radiation for efficient heat transfer to the reaction site during endothermic reduction, while the smaller void size range within the struts, with dmean = 10 μm and strut porosity = 0-0.44, increases the specific surface area for enhanced reaction kinetics during exothermic oxidation with CO2. Characterization is performed via mercury intrusion porosimetry, scanning electron microscopy, and thermogravimetric analysis (TGA). Samples are thermally reduced at 1773 K and subsequently oxidized with CO2 at temperatures in the range 873-1273 K. On average, CO production rates are ten times higher for samples with 0.44 strut porosity than for samples with non-porous struts. The oxidation rate scales with specific surface area and the apparent activation energy ranges from 90 to 135.7 kJ mol(-1). Twenty consecutive redox cycles exhibited stable CO production yield per cycle. Testing of the dual-scale RPC in a solar cavity-receiver exposed to high-flux thermal radiation (3.8 kW radiative power at 3015 suns) corroborated the superior performance observed in the TGA, yielding a shorter cycle time and a mean solar-to-fuel energy conversion efficiency of 1.72%.

Structured mesoporous Mn, Fe, and Co oxides: Synthesis, physicochemical, and catalytic properties

NASA Astrophysics Data System (ADS)

Maerle, A. A.; Karakulina, A. A.; Rodionova, L. I.; Moskovskaya, I. F.; Dobryakova, I. V.; Egorov, A. V.; Romanovskii, B. V.

2014-02-01

Structured mesoporous Mn, Fe, and Co oxides are synthesized using "soft" and "hard" templates; the resulting materials are characterized by XRD, SEM, TEM, BET, and TG. It is shown that in the first case, the oxides have high surface areas of up to 450 m2/g that are preserved after calcination of the material up to 300°C. Even though, the surface area of the oxides prepared by the "hard-template" method does not exceed 100 m2/g; it is, however, thermally stable up to 500°C. Catalytic activity of mesoporous oxides in methanol conversion was found to depend on both the nature of the transition metal and the type of template used in synthesis.

Asymmetric Supercapacitors Using 3D Nanoporous Carbon and Cobalt Oxide Electrodes Synthesized from a Single Metal-Organic Framework.

PubMed

Salunkhe, Rahul R; Tang, Jing; Kamachi, Yuichiro; Nakato, Teruyuki; Kim, Jung Ho; Yamauchi, Yusuke

2015-06-23

Nanoporous carbon and nanoporous cobalt oxide (Co3O4) materials have been selectively prepared from a single metal-organic framework (MOF) (zeolitic imidazolate framework, ZIF-67) by optimizing the annealing conditions. The resulting ZIF-derived carbon possesses highly graphitic walls and a high specific surface area of 350 m(2)·g(-1), while the resulting ZIF-derived nanoporous Co3O4 possesses a high specific surface area of 148 m(2)·g(-1) with much less carbon content (1.7 at%). When nanoporous carbon and nanoporous Co3O4 were tested as electrode materials for supercapacitor application, they showed high capacitance values (272 and 504 F·g(-1), respectively, at a scan rate of 5 mV·s(-1)). To further demonstrate the advantages of our ZIF-derived nanoporous materials, symmetric (SSCs) and asymmetric supercapacitors (ASCs) were also fabricated using nanoporous carbon and nanoporous Co3O4 electrodes. Improved capacitance performance was successfully realized for the ASC (Co3O4//carbon), better than those of the SSCs based on nanoporous carbon and nanoporous Co3O4 materials (i.e., carbon//carbon and Co3O4//Co3O4). The developed ASC with an optimal mass loading can be operated within a wide potential window of 0.0-1.6 V, which leads to a high specific energy of 36 W·h·kg(-1). More interestingly, this ASC also exhibits excellent rate capability (with the highest specific power of 8000 W·kg(-1) at a specific energy of 15 W·h·kg(-1)) combined with long-term stability up to 2000 cycles.

Selected Topics on the Synthesis, Properties and Applications of Multiwalled Carbon Nanotubes

PubMed Central

Stoner, B.R.; Brown, B.; Glass, J.T.

2014-01-01

Summary In summary, MWCNTs have been examined for a variety of electronic applications due to their unique structure and chemistry. Electrodes for field emission, energy and sensor applications hold particular interest. MWCNTs provide a very high surface area, relatively easy methods of surface modification, controllable and high concentration of reactive surface sites, and high specific capacitance. Combining MWCNTs with graphene structures, oxide and metal nanoparticles and certain polymers extends their performance and functionality. Such hybrid structures have been produced in situ during CNT growth and in two-step processes. Excellent progress on understanding the mechanisms of CNT growth has enabled numerous growth methods to all yield MWCNT structures in a variety of morphologies. PMID:24910503

Role of Exposed Surfaces on Zinc Oxide Nanostructures in the Catalytic Ethanol Transformation.

PubMed

Morales, María V; Asedegbega-Nieto, Esther; Iglesias-Juez, Ana; Rodríguez-Ramos, Inmaculada; Guerrero-Ruiz, Antonio

2015-07-08

For a series of nanometric ZnO materials, the relationship between their morphological and surface functionalities and their catalytic properties in the selective decomposition of ethanol to yield acetaldehyde was explored. Six ZnO solids were prepared by a microemulsion-precipitation method and the thermal decomposition of different precursors and compared with a commercial sample. All these materials were characterized intensively by XRD and SEM to obtain their morphological specificities. Additionally, surface area determinations and IR spectroscopy were used to detect differences in the surface properties. The density of acid surface sites was determined quantitatively using an isopropanol dehydration test. Based on these characterization studies and on the results of the catalytic tests, it has been established that ZnO basal surfaces seem to be responsible for the production of ethylene as a minor product as well as for secondary reactions that yield acetyl acetate. Furthermore, one specific type of exposed hydroxyl groups appears to govern the surface catalytic properties. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Iron oxide inside SBA-15 modified with amino groups as reusable adsorbent for highly efficient removal of glyphosate from water

NASA Astrophysics Data System (ADS)

Fiorilli, Sonia; Rivoira, Luca; Calì, Giada; Appendini, Marta; Bruzzoniti, Maria Concetta; Coïsson, Marco; Onida, Barbara

2017-07-01

Iron oxide clusters were incorporated into amino-functionalized SBA-15 in order to obtain a magnetically recoverable adsorbent. The physical-chemical properties of the material were characterized by FE-SEM, STEM, XRD, TGA, XPS, FT-IR and acid-base titration analysis. Iron oxide nanoparticles were uniformly dispersed into the pore of mesoporous silica and that the adsorbent is characterized high specific surface area (177 m2/g) and accessible porosity. The sorbent was successfully tested for the removal of glyphosate in real water matrices. Despite the significant content of inorganic ions, a quantitative removal of the contaminant was found. The complete regeneration of the sorbent after the adsorption process through diluted NaOH solution was also proved.

Core-shell rhodium sulfide catalyst for hydrogen evolution reaction / hydrogen oxidation reaction in hydrogen-bromine reversible fuel cell

NASA Astrophysics Data System (ADS)

Li, Yuanchao; Nguyen, Trung Van

2018-04-01

Synthesis and characterization of high electrochemical active surface area (ECSA) core-shell RhxSy catalysts for hydrogen evolution oxidation (HER)/hydrogen oxidation reaction (HOR) in H2-Br2 fuel cell are discussed. Catalysts with RhxSy as shell and different percentages (5%, 10%, and 20%) of platinum on carbon as core materials are synthesized. Cyclic voltammetry is used to evaluate the Pt-equivalent mass specific ECSA and durability of these catalysts. Transmission electron microscopy (TEM), X-ray Photoelectron spectroscopy (XPS) and Energy-dispersive X-ray spectroscopy (EDX) techniques are utilized to characterize the bulk and surface compositions and to confirm the core-shell structure of the catalysts, respectively. Cycling test and polarization curve measurements in the H2-Br2 fuel cell are used to assess the catalyst stability and performance in a fuel cell. The results show that the catalysts with core-shell structure have higher mass specific ECSA (50 m2 gm-Rh-1) compared to a commercial catalyst (RhxSy/C catalyst from BASF, 6.9 m2 gm-Rh-1). It also shows better HOR/HER performance in the fuel cell. Compared to the platinum catalyst, the core-shell catalysts show more stable performance in the fuel cell cycling test.

Synthesis of boron, nitrogen co-doped porous carbon from asphaltene for high-performance supercapacitors

NASA Astrophysics Data System (ADS)

Zhou, Ying; Wang, Dao-Long; Wang, Chun-Lei; Jin, Xin-Xin; Qiu, Jie-Shan

2014-08-01

Oxidized asphaltene (OA), a thermosetting material with plenty of functional groups, is synthesized from asphaltene (A) using HNO3/H2SO4 as the oxidizing agent. Boron, nitrogen co-doped porous carbon (BNC—OA) is prepared by carbonization of the mixture of boric acid and OA at 1173 K in an argon atmosphere. X-ray photoelectron spectroscopy (XPS) characterization reveals that the BNC—OA has a nitrogen content of 3.26 at.% and a boron content of 1.31 at.%, while its oxidation-free counterpart (BNC—SA) has a nitrogen content of 1.61 at.% and a boron content of 3.02 at.%. The specific surface area and total pore volume of BNC—OA are 1103 m2·g-1 and 0.921 cm3·g-1, respectively. At a current density of 0.1 A·g-1, the specific capacitance of BNC-OA is 335 F·g-1 and the capacitance retention can still reach 83% at 1 A·g-1. The analysis shows that the superior electrochemical performance of the BNC—OA is attributed to the pseudocapacitance behavior of surface heteroatom functional groups and an abundant pore-structure. Boron, nitrogen co-doped porous carbon is a promising electrode material for supercapacitors.

Ceruloplasmin and cardiovascular disease

NASA Technical Reports Server (NTRS)

Fox, P. L.; Mazumder, B.; Ehrenwald, E.; Mukhopadhyay, C. K.

2000-01-01

Transition metal ion-mediated oxidation is a commonly used model system for studies of the chemical, structural, and functional modifications of low-density lipoprotein (LDL). The physiological relevance of studies using free metal ions is unclear and has led to an exploration of free metal ion-independent mechanisms of oxidation. We and others have investigated the role of human ceruloplasmin (Cp) in oxidative processes because it the principal copper-containing protein in serum. There is an abundance of epidemiological data that suggests that serum Cp may be an important risk factor predicting myocardial infarction and cardiovascular disease. Biochemical studies have shown that Cp is a potent catalyst of LDL oxidation in vitro. The pro-oxidant activity of Cp requires an intact structure, and a single copper atom at the surface of the protein, near His(426), is required for LDL oxidation. Under conditions where inhibitory protein (such as albumin) is present, LDL oxidation by Cp is optimal in the presence of superoxide, which reduces the surface copper atom of Cp. Cultured vascular endothelial and smooth muscle cells also oxidize LDL in the presence of Cp. Superoxide release by these cells is a critical factor regulating the rate of oxidation. Cultured monocytic cells, when activated by zymosan, can oxidize LDL, but these cells are unique in their secretion of Cp. Inhibitor studies using Cp-specific antibodies and antisense oligonucleotides show that Cp is a major contributor to LDL oxidation by these cells. The role of Cp in lipoprotein oxidation and atherosclerotic lesion progression in vivo has not been directly assessed and is an important area for future studies.

A novel solution for hydroxylated PAHs removal by oxidative coupling reaction using Mn oxide.

PubMed

Kang, Ki-Hoon; Lim, Dong-Min; Shin, Hyun-Sang

2008-01-01

In this study, removals of 1-naphthol by oxidative-coupling reaction using birnessite, one of the natural Mn oxides present in soil, was investigated in various experimental conditions (reaction time, Mn oxide loadings, pH). The removal efficiency of 1-naphthol by birnessite was high in all the experimental conditions, and UV-visible and mass spectrometric analyses on the supernatant after reaction confirmed that the reaction products were oligomers formed by oxidative-coupling reaction. Pseudo-first order rate constants, k, for the oxidative transformation of 1-naphthol by birnessite was derived from the kinetic experiments under various amounts of birnessite loadings, and using the observed pseudo-first order rate constants with respect to birnessite loadings, the surface area normalised specific rate constant, k(surf), was also determined to be 9.3 x 10(-4) (L/m(2).min) for 1-naphthol. In addition, the oxidative transformation of 1-naphthol was found to be dependent on solution pH, and the pseudo-first order rate constants were increased from 0.129 at pH 10 to 0.187 at pH 4. (c) IWA Publishing 2008.

Biological consequences from interaction of nanosized titanium(iv) oxides with defined human blood components

NASA Astrophysics Data System (ADS)

Stella, Aaron

The utility of engineered nanomaterials is growing, particularly the titanium(iv) oxide (titanium dioxide, TiO2) nanoparticles. TiO 2 is very useful for brightening paints, and coloring foods. Nano-sized TiO2 is also useful for sunscreens, cosmetics, and can be utilized as a photocatalyst. However, the nanometer size of the TiO2 nanoparticle is a characteristic that may contribute oxidative stress to red blood cells (RBCs) in humans. This study utilized screening methods to evaluate different forms of TiO2 nanoparticles which differ by primary particle size, specific surface area, crystalline phase, and surface polarity. RBCs are rich in the intracellular antioxidant glutathione (GSH). HPLC analysis revealed that some TiO2 nanoparticles caused oxidation of GSH to glutathione disulfide (GSSG). Vitamin E is a major membrane-bound antioxidant. Vitamin E levels were then determined by HPLC in the RBC membrane after exposure to TiO2 nanoparticles. The HPLC results showed that each nanoparticle oxidized RBC glutathione and membrane vitamin E at different rates. When hemoglobin was mixed with each TiO2 nanoparticle, hemoglobin was adsorbed at varying rates to the surface of the nanoparticles. Similarly, the aminothiol homocysteine was also adsorbed at different rates by the TiO2 nanoparticles. Using light microscopy, some TiO2 nanoparticles caused the formation of RBC aggregates which significantly changed the RBC morphology. The aggregation data was quantified using a hemacytometer. The TiO2 nanoparticles also caused hemolysis of RBCs. Hemolysis is considered to be a toxic endpoint for RBCs. Changes in the nucleated lymphocyte gene expression of certain oxidative stress genes were also observed using real-time polymerase chain reaction (qPCR). The data indicates that RBCs can ultimately be hemolyzed by biological oxidative damage resulting from a combination of oxidative mechanisms. Additionally, the TiO2 nanoparticles demonstrated the ability to adsorb biomolecules to their surface which could be useful for nanomedicine purposes or biosensing applications. The changes in lymphocyte gene expression at different doses indicate that these TiO2 nanoparticles are capable of disrupting nuclear activity. The use of multiple screening methods provided an effective approach to evaluate nano-bio interactions. The use of a biologically-relevant matrix combined with specific detection methods yielded results which accurately predict biological adversity.

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.

Catalytic oxidation of 1,2-DCBz over V2O5/TiO2-CNTs: effect of CNT diameter and surface functional groups.

PubMed

Du, Cuicui; Wang, Qiulin; Peng, Yaqi; Lu, Shengyong; Ji, Longjie; Ni, Mingjiang

2017-02-01

A series of V 2 O 5 /TiO 2 -carbon nanotube (CNT) catalysts were prepared and tested to decompose gaseous 1,2-dichlorobenzene (1,2-DCBz). Several physicochemical methods, including nitrogen adsorption, scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and H 2 temperature-programmed reduction (TPR) were employed to characterise their physicochemical properties. To better understand the effect of CNT properties on the reactivity of V 2 O 5 /TiO 2 -CNT catalysts, the 1,2-DCBz residue remaining in the off-gas and on the catalyst surface were both collected and analysed. The results indicate that the outer diameter and the surface functional groups (hydroxide radical and carboxyl) of CNTs significantly influence upon the catalytic activity of CNT-containing V 2 O 5 /TiO 2 catalysts: the CNT outer diameter mainly affects the aggregation of CNTs and the π-π interaction between the benzene ring and CNTs, while the introduction of -OH and -COOH groups by acid treatment can further enlarge specific surface area (SSA) and contribute to a higher average oxidation state of vanadium (V aos ) and supplemental surface chemisorbed oxygen (O ads ). In addition, the enhanced mobility of lattice oxygen (O latt) also improves the oxidation ability of the catalysts.

Specific surface area of a crushed welded tuff before and after aqueous dissolution

USGS Publications Warehouse

Reddy, M.M.; Claassen, H.C.

1994-01-01

Specific surface areas were measured for several reference minerals (anorthoclase, labradorite and augite), welded tuff and stream sediments from Snowshoe Mountain, near Creede, Colorado. Crushed and sieved tuff had an unexpectedly small variation in specific surface area over a range of size fractions. Replicate surface area measurements of the largest and smallest tuff particle size fractions examined (1-0.3 mm and <0.212 mm) were 2.3 ?? 0.2 m2/g for each size fraction. Reference minerals prepared in the same way as the tuff had smaller specific surface areas than that of the tuff of the same size fraction. Higher than expected tuff specific surface areas appear to be due to porous matrix. Tuff, reacted in solutions with pH values from 2 to 6, had little change in specific surface area in comparison with unreacted tuff. Tuff, reacted with solutions having high acid concentrations (0.1 M hydrochloric acid or sulfuric-hydrofluoric acid), exhibited a marked increase in specific surface area compared to unreacted tuff. ?? 1994.

Facile synthesis of reduced graphene oxide/peroxomolybdate(VI)-citrate composite and its potential energy storage application

NASA Astrophysics Data System (ADS)

Ciszewski, Mateusz; Benke, Grzegorz; Leszczyńska-Sejda, Katarzyna; Kopyto, Dorota

2017-11-01

A new energy storage material based on molybdate active species has been presented. Molybdenum seems to be a perspective material in supercapacitors because of numerous possible metal oxidation states, electrolyte storage by means of various chemical reactions and availability in comparison to other refractory metals. Material synthesized within this research was composed of reduced graphene oxide matrix and peroxomolybdate(VI)-citrate active dimers. It was showed that peroxomolybdate(VI)-citrate structure enhanced electrochemical activity of symmetric supercapacitor. Simple methodology was used to synthesize a composite with pH adjustment as the key step. The specific capacity calculated from galvanostatic charge/discharge curves was as high as 250 F/g. Material was distinguished by good cyclability with 5% capacity loss after 1000 cycles. The increase in charge transfer resistance, induced by metal-oxygen compound within the carbon matrix was relatively low, compared to parent reduced graphene oxide. Amorphous structure of peroxomolybdate(VI)-modified material was observed with slight increase in the interlayer distance in comparison to parent reduced graphene oxide. The height and lateral size of crystallites were also determined. Significant decrease in the specific surface area of peroxomolybdate(VI)-modified composite was observed, in comparison to the parent reduced graphene oxide.

Microstructure and thermal conductivity of surfactant-free NiO nanostructures

NASA Astrophysics Data System (ADS)

Sahoo, Pranati; Misra, Dinesh K.; Salvador, Jim; Makongo, Julien P. A.; Chaubey, Girija S.; Takas, Nathan J.; Wiley, John B.; Poudeu, Pierre F. P.

2012-06-01

High purity, nanometer sized surfactant-free nickel oxide (NiO) particles were produced in gram scale using a solution combustion method and characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), gas pycnometry and gas adsorption analysis (BET). The average particle size of the as-synthesized NiO increases significantly with the preheating temperature of the furnace, while the specific surface area decreases. A BET specific surface area of ∼100 m2/g was obtained for NiO nanoparticles with size as small as 3 nm synthesized at 300 °C. The thermal conductivity (κ) of pressed pellets of the synthesized NiO nanoparticles obtained using spark plasma sintering (SPS) and uniaxial hot pressing is drastically decreased (∼60%) compared to that of NiO single crystal. This strong reduction in κ with particle size suggests the suitability of the synthesized surfactant-free NiO nanoparticles for use as nanoinclusions when designing high performance materials for waste heat recovery.

Mesoporous silica obtained with methyltriethoxysilane as co-precursor in alkaline medium

NASA Astrophysics Data System (ADS)

Putz, Ana-Maria; Wang, Kunzhou; Len, Adél; Plocek, Jiri; Bezdicka, Petr; Kopitsa, Gennady P.; Khamova, Tamara V.; Ianăşi, Cătălin; Săcărescu, Liviu; Mitróová, Zuzana; Savii, Cecilia; Yan, Minhao; Almásy, László

2017-12-01

Mesoporous silica particles have been synthesized by sol-gel method from tetraethoxysilane (tetraethylorthosilicate, TEOS) and methyltriethoxysilane (MTES), in ethanol and water mixture, at different ratios of the of the silica precursors. Ammonia was used as catalyst at room temperature and hexadecyltrimethylammonium bromide (cetyltrimethylammonium bromide, CTAB) as the structure directing agent. Nitrogen sorption, X-ray diffraction and small-angle neutron scattering gave information on the evolution of the gel structure and pore morphologies in the function of MTES/TEOS molar ratio. Thermogravimetric and differential thermal analysis showed that with addition of MTES the exothermic peak indicating the oxidation of the low molecular weight organic fragments shift to higher temperature. A room-temperature, one-pot synthesis of MCM-41 type materials is presented, in which the variation of the MTES concentration allows to change the hydrophobicity, preserving the specific properties materials, like the ordered pore structure, large specific surface area and high porosity. Specifically, the obtained materials had cylindrical pores, specific surface areas up to 1101 m2/g and total pore volumes up to 0.473 cm3/g. The obtained mesoporous materials are susceptible for further functionalization to improve their selective uptake of guest species in drug delivery applications.

Investigating the oxidation mechanism of tantalum nanoparticles at high heating rates

NASA Astrophysics Data System (ADS)

DeLisio, Jeffery B.; Wang, Xizheng; Wu, Tao; Egan, Garth C.; Jacob, Rohit J.; Zachariah, Michael R.

2017-12-01

Reduced diffusion length scales and increased specific surface areas of nanosized metal fuels have recently demonstrated increased reaction rates for these systems, increasing their relevance in a wide variety of applications. The most commonly employed metal fuel, aluminum, tends to oxidize rapidly near its melting point (660 °C) in addition to undergoing a phase change of the nascent oxide shell. To further expand on the understanding of nanosized metal fuel oxidation, tantalum nanoparticles were studied due to their high melting point (3017 °C) in comparison to aluminum. Both traditional slow heating rate and in-situ high heating rate techniques were used to probe the oxidation of tantalum nanoparticles in oxygen containing environments in addition to nanothermite mixtures. When oxidized by gas phase oxygen, the oxide shell of the tantalum nanoparticles rapidly crystallized creating cracks that may attribute to enhanced oxygen diffusion into the particle. In the case of tantalum based nanothermites, oxide shell crystallization was shown to induce reactive sintering with the metal oxide resulting in a narrow range of ignition temperatures independent of the metal oxide used. The oxidation mechanism was modeled using the Deal-Grove model to extract rate parameters, and theoretical burn times for tantalum based nanocomposites were calculated.

Fabrication and Performance Study on Individual Zno Nanowires Based Bioelectrode

NASA Astrophysics Data System (ADS)

Zhao, Yanguang; Yan, Xiaoqin; Kang, Zhuo; Lin, Pei

2012-08-01

One-dimensional zinc oxide nanowires (ZnO NWs) have unique advantages for use in biosensors as follows: oxide stable surface, excellent biosafety, high specific surface area, high isoelectric point (IEP = 9.5). In this work, we have prepared a kind of electrochemical bioelectrode based on individual ZnO NWs. Here, ZnO NWs with high quality were successfully synthesized by CVD method, which were characterized by scanning electron microscopy, X-ray diffraction and photoluminescence. Then the Raman spectra and electrical characterization demonstrated the adsorption of uricase on ZnO wires. At last, a series of electrochemical measurements were carried out by using an electrochemical workstation with a conventional three-electrode system to obtain the cyclic voltammetry characteristics of the bioelectrodes. The excellent performance of the fabricated bioelectrode implies the potential application for single ZnO nanowire to construct electrochemical biosensor for the detection of uric acid.

Dye-sensitized solar cell employing zinc oxide aggregates grown in the presence of lithium

DOEpatents

Zhang, Qifeng; Cao, Guozhong

2013-10-15

Provided are a novel ZnO dye-sensitized solar cell and method of fabricating the same. In one embodiment, deliberately added lithium ions are used to mediate the growth of ZnO aggregates. The use of lithium provides ZnO aggregates that have advantageous microstructure, morphology, crystallinity, and operational characteristics. Employing lithium during aggregate synthesis results in a polydisperse collection of ZnO aggregates favorable for porosity and light scattering. The resulting nanocrystallites forming the aggregates have improved crystallinity and more favorable facets for dye molecule absorption. The lithium synthesis improves the surface stability of ZnO in acidic dyes. The procedures developed and disclosed herein also help ensure the formation of an aggregate film that has a high homogeneity of thickness, a high packing density, a high specific surface area, and good electrical contact between the film and the fluorine-doped tin oxide electrode and among the aggregate particles.

Water-gas-shift over metal-free nanocrystalline ceria: An experimental and theoretical study

DOE PAGES

Guild, Curtis J.; Vovchok, Dimitriy; Kriz, David A.; ...

2017-01-23

A tandem experimental and theoretical investigation of a mesoporous ceria catalyst reveals the properties of the metal oxide are conducive for activity typically ascribed to metals, suggesting reduced Ce 3+ and oxygen vacancies are responsible for the inherent bi-functionality of CO oxidation and dissociation of water required for facilitating the production of H 2. The degree of reduction of the ceria, specifically the (1 0 0) face, is found to significantly influence the binding of reagents, suggesting reduced surfaces harbor the necessary reactive sites. The metal-free catalysis of the reaction is significant for catalyst design considerations, and the suite ofmore » in situ analyses provides a comprehensive study of the dynamic nature of the high surface area catalyst system. Finally, this study postulates feasible improvements in catalytic activity may redirect the purpose of the water-gas shift reaction from CO purification to primary hydrogen production.« less

Water-gas-shift over metal-free nanocrystalline ceria: An experimental and theoretical study

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

Guild, Curtis J.; Vovchok, Dimitriy; Kriz, David A.

A tandem experimental and theoretical investigation of a mesoporous ceria catalyst reveals the properties of the metal oxide are conducive for activity typically ascribed to metals, suggesting reduced Ce 3+ and oxygen vacancies are responsible for the inherent bi-functionality of CO oxidation and dissociation of water required for facilitating the production of H 2. The degree of reduction of the ceria, specifically the (1 0 0) face, is found to significantly influence the binding of reagents, suggesting reduced surfaces harbor the necessary reactive sites. The metal-free catalysis of the reaction is significant for catalyst design considerations, and the suite ofmore » in situ analyses provides a comprehensive study of the dynamic nature of the high surface area catalyst system. Finally, this study postulates feasible improvements in catalytic activity may redirect the purpose of the water-gas shift reaction from CO purification to primary hydrogen production.« less

Thermally exfoliated graphite oxide

NASA Technical Reports Server (NTRS)

Prud'Homme, Robert K. (Inventor); Aksay, Ilhan A. (Inventor); Abdala, Ahmed (Inventor)

2011-01-01

A modified graphite oxide material contains a thermally exfoliated graphite oxide with a surface area of from about 300 sq m/g to 2600 sq m/g, wherein the thermally exfoliated graphite oxide displays no signature of the original graphite and/or graphite oxide, as determined by X-ray diffraction.

Interfacial Interaction in Anodic Aluminum Oxide Templates Modifies Morphology, Surface Area, and Crystallization of Polyamide-6 Nanofibers.

PubMed

Xue, Junhui; Xu, Yizhuang; Jin, Zhaoxia

2016-03-08

Here, we demonstrated that, when the precipitation process of polyamide-6 (PA6) solution happens in cylindrical channels of an anodized aluminum oxide membrane (AAO), interface interactions between a solid surface, solvent, non-solvent, and PA6 will influence the obtained polymer nanostructures, resulting in complex morphologies, increased surface area, and crystallization changes. With the enhancing interaction of PA6 and the AAO surface, the morphology of PA6 nanostructures changes from solid nanofibers, mesoporous, to bamboo-like, while at the same time, metastable γ-phase domains increase in these PA6 nanostructures. Brunauer-Emmett-Teller (BET) surface areas of solid, bamboo-like, and mesoporous PA6 nanofibers rise from 16, 20.9, to 25 m(2)/g. This study shows that interfacial interaction in AAO template fabrication can be used in manipulating the morphology and crystallization of one-dimensional polymer nanostructures. It also provides us a simple and novel method to create porous PA6 nanofibers with a large surface area.

A new approach to the immobilisation of poly(ethylene oxide) for the reduction of non-specific protein adsorption on conductive substrates

NASA Astrophysics Data System (ADS)

Cole, Martin A.; Thissen, Helmut; Losic, Dusan; Voelcker, Nicolas H.

2007-04-01

Biomedical and biotechnological devices often require surface modifications to improve their performance. In most cases, uniform coatings are desired which provide a specific property or lead to a specific biological response. In the present work, we have generated pinhole-free coatings providing amine functional groups achieved by electropolymerisation of tyramine on highly doped silicon substrates. Furthermore, amine groups were used for the subsequent grafting of poly(ethylene oxide) aldehyde via reductive amination. All surface modification steps were characterized by X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). The results indicate that the stability and the density of amine functional groups introduced at the surface via electropolymerisation compare favourably with alternative coatings frequently used in biomedical and biotechnological devices such as plasma polymer films. Furthermore, protein adsorption on amine and poly(ethylene oxide) coatings was studied by XPS and a colorimetric assay to test enzymatic activity. The grafting of poly(ethylene oxide) under cloud point conditions on electropolymerised tyramine layers resulted in surfaces with extremely low protein fouling character.

Characteristics of nano-sized yttria powder synthesized by a polyvinyl alcohol solution route at low temperature.

PubMed

Lee, Sang-Jin; Jung, Choong-Hwan

2012-01-01

Nano-sized yttria (Y2O3) powders were successfully synthesized at a low temperature of 400 degrees C by a simple polymer solution route. PVA polymer, as an organic carrier, contributed to an atom-scale homogeneous precursor gel and it resulted in fully crystallized, nano-sized yttria powder with high specific surface area through the low temperature calcination. In this process, the content of PVA, calcination temperature and heating time affected the microstructure and crystallization behavior of the powders. The development of crystalline phase and the final particle size were strongly dependant on the oxidation reaction from the polymer burn-out step and the PVA content. In this paper, the PVA solution technique for the fabrication of nano-sized yttria powders is introduced. The effects of PVA content and holding time on the powder morphology and powder specific surface area are also studied. The characterization of the synthesized powders is examined by using XRD, DTA/TG, SEM, TEM and nitrogen gas adsorption. The yttria powder synthesized from the PVA content of 3:1 ratio and calcined at 400 degrees C had a crystallite size of about 20 nm or less with a high surface areas of 93.95-120.76 m2 g(-1).

Gaseous Oxidized Mercury Dry Deposition Measurements in the FourCorners Area and Eastern Oklahoma, U.S.A.

EPA Science Inventory

Gaseous oxidized mercury (GOM) dry deposition measurements using surrogate surface passive samplers were collected in the Four Corners area and eastern Oklahoma from August, 2009–August, 2011. Using data from a six site area network, a characterization of the magnitude and spatia...

Oxidation Resistant, Cr Retaining, Electrically Conductive Coatings on Metallic Alloys for SOFC Interconnects

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

Vladimir Gorokhovsky

2008-03-31

This report describes significant results from an on-going, collaborative effort to enable the use of inexpensive metallic alloys as interconnects in planar solid oxide fuel cells (SOFCs) through the use of advanced coating technologies. Arcomac Surface Engineering, LLC, under the leadership of Dr. Vladimir Gorokhovsky, is investigating filtered-arc and filtered-arc plasma-assisted hybrid coating deposition technologies to promote oxidation resistance, eliminate Cr volatility, and stabilize the electrical conductivity of both standard and specialty steel alloys of interest for SOFC metallic interconnect (IC) applications. Arcomac has successfully developed technologies and processes to deposit coatings with excellent adhesion, which have demonstrated a substantialmore » increase in high temperature oxidation resistance, stabilization of low Area Specific Resistance values and significantly decrease Cr volatility. An extensive matrix of deposition processes, coating compositions and architectures was evaluated. Technical performance of coated and uncoated sample coupons during exposures to SOFC interconnect-relevant conditions is discussed, and promising future directions are considered. Cost analyses have been prepared based on assessment of plasma processing parameters, which demonstrate the feasibility of the proposed surface engineering process for SOFC metallic IC applications.« less

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

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

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

2016-05-09

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

Bioactivity of self-organized TiO2 nanotubes used as surface treatment on Ti biomaterials

NASA Astrophysics Data System (ADS)

Souza, M. R.; Reyes, K. M.; Oliveira, N. T. C.; Kuromoto, N. K.; Marino, C. E. B.

2016-03-01

Titanium and its alloys are widely used as implants due to their excellent mechanical properties, corrosion resistance and biocompatibility. TiO2 nanotubes have been studied as surface treatment to increase the specific area and to improve osseointegration. However, the thermodynamic stability and bioactivity of these nanostructures must be evaluated. The objective of this research was to obtain nanotubes oxides on Ti6Al4V alloy and to analyze the electrochemical stability in physiological solution at 37 °C and the bioactive response of the biomaterial. The nanotubes were obtained by potentiostatic anodization. The morphology of the oxides was evaluated by scanning electron microscopy. The chemical characterization was analyzed by energy dispersive spectroscopy and x-ray photoelectron spectroscopy techniques. The electrochemical stability was analyzed by open circuit potential (OCP) and the bioactivity by biomimetic test in a simulated body fluid (SBF) solution. The OCP of the nanotubes oxides was shown to be more noble and stable than the compacted oxides. The biomaterial covered with theses oxides showed sealing by Ca and P after 30 d immersion in artificial blood. And after 15 d of immersion in SBF, the hydroxyapatite could be seen on the non-sealed nanotubes. TiO2 nanotube layers could improve the superficial chemical stability and also the osseointegration process.

[Synergetic effects of silicon carbide and molecular sieve loaded catalyst on microwave assisted catalytic oxidation of toluene].

PubMed

Wang, Xiao-Hui; Bo, Long-Li; Liu, Hai-Nan; Zhang, Hao; Sun, Jian-Yu; Yang, Li; Cai, Li-Dong

2013-06-01

Molecular sieve loaded catalyst was prepared by impregnation method, microwave-absorbing material silicon carbide and the catalyst were investigated for catalytic oxidation of toluene by microwave irradiation. Research work examined effects of silicon carbide and molecular sieve loading Cu-V catalyst's mixture ratio as well as mixed approach changes on degradation of toluene, and characteristics of catalyst were measured through scanning electron microscope, specific surface area test and X-ray diffraction analysis. The result showed that the fixed bed reactor had advantages of both thermal storage property and low-temperature catalytic oxidation when 20% silicon carbide was filled at the bottom of the reactor, and this could effectively improve the utilization of microwave energy as well as catalytic oxidation efficiency of toluene. Under microwave power of 75 W and 47 W, complete-combustion temperatures of molecular sieve loaded Cu-V catalyst and Cu-V-Ce catalyst to toluene were 325 degrees C and 160 degrees C, respectively. Characteristics of the catalysts showed that mixture of rare-earth element Ce increased the dispersion of active components in the surface of catalyst, micropore structure of catalyst effectively guaranteed high adsorption capacity for toluene, while amorphous phase of Cu and V oxides increased the activity of catalyst greatly.

Adsorption of Cd(II) from aqueous solutions by rape straw biochar derived from different modification processes.

PubMed

Li, Bing; Yang, Lan; Wang, Chang-Quan; Zhang, Qing-Pei; Liu, Qing-Cheng; Li, Yi-Ding; Xiao, Rui

2017-05-01

In order to deal with cadmium (Cd(II)) pollution, three modified biochar materials: alkaline treatment of biochar (BC-NaOH), KMnO 4 impregnation of biochar (BC-MnO x ) and FeCl 3 magnetic treatment of biochar (BC-FeO x ), were investigated. Nitrogen adsorption-desorption isotherms, Fourier transform infrared spectroscopy (FTIR), Boehm titration, and scanning electron microscopy (SEM) were used to determine the characteristics of adsorbents and explore the main adsorption mechanism. The results show that manganese oxide particles are carried successfully within the biochar, contributing to micropore creation, boosting specific surface area and forming innersphere complexes with oxygen-containing groups, while also increasing the number of oxygen-containing groups. The adsorption sites created by the loaded manganese oxide, rather than specific surface areas, play the most important roles in cadmium adsorption. Batch adsorption experiments demonstrate a Langmuir model fit for Cd(II), and BC-MnO x provided the highest sorption capacity (81.10 mg g -1 ). The sorption kinetics of Cd(II) on adsorbents follows pseudo-second-order kinetics and the adsorption rate of the BC-MnO x material was the highest (14.46 g (mg·h) -1 ). Therefore, biochar modification methods involving KMnO 4 impregnation may provide effective ways of enhancing Cd(II) removal from aqueous solutions. Copyright © 2017 Elsevier Ltd. All rights reserved.

Mixed titanium, silicon, and aluminum oxide nanostructures as novel adsorbent for removal of rhodamine 6G and methylene blue as cationic dyes from aqueous solution.

PubMed

Pal, Umapada; Sandoval, Alberto; Madrid, Sergio Isaac Uribe; Corro, Grisel; Sharma, Vivek; Mohanty, Paritosh

2016-11-01

Mixed oxide nanoparticles containing Ti, Si, and Al of 8-15 nm size range were synthesized using a combined sol-gel - hydrothermal method. Effects of composition on the structure, morphology, and optical properties of the nanoparticles were studied using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), microRaman spectroscopy, and diffuse reflectance spectroscopy (DRS). Dye removal abilities of the nanoparticles from aqueous solutions were tested for different cationic dyes. While all the mixed oxide nanoparticles revealed high and fast adsorption of cationic dyes, the particles containing Ti and Si turned out to be the best. The adsorption kinetics and equilibrium adsorption behavior of the adsorbate - adsorbent systems could be well described by pseudo-second-order kinetics and Langmuir isotherm model, respectively. Estimated thermodynamic parameters revealed the adsorption process is spontaneous, driven mainly by the electrostatic force between the cationic dye molecules and negative charge at nanoparticle surface. Highest dye adsorption capacity (162.96 mg MB/g) of the mixed oxide nanostructures containing Ti and Si is associated to their high specific surface area, and the presence of surface Si-O(δ-) groups, in addition to the hydroxyl groups of amorphous titania. Mixed oxide nanoparticles containing 75% Ti and 25% Si seen to be the most efficient adsorbents for removing cationic dye molecules from wastewater. Copyright © 2016 Elsevier Ltd. All rights reserved.

Evolution of Active Sites in Pt-Based Nanoalloy Catalysts for the Oxidation of Carbonaceous Species by Combined in Situ Infrared Spectroscopy and Total X-ray Scattering.

PubMed

Petkov, Valeri; Maswadeh, Yazan; Lu, Aolin; Shan, Shiyao; Kareem, Haval; Zhao, Yinguang; Luo, Jin; Zhong, Chuan-Jian; Beyer, Kevin; Chapman, Karena

2018-04-04

We present results from combined in situ infrared spectroscopy and total X-ray scattering studies on the evolution of catalytically active sites in exemplary binary and ternary Pt-based nanoalloys during a sequence of CO oxidation-reactivation-CO oxidation reactions. We find that when within a particular compositional range, the fresh nanoalloys may exhibit high catalytic activity for low-temperature CO oxidation. Using surface-specific atomic pair distribution functions (PDFs) extracted from the in situ total X-ray scattering data, we find that, regardless of their chemical composition and initial catalytic activity, the fresh nanoalloys suffer a significant surface structural disorder during CO oxidation. Upon reactivation in oxygen atmosphere, the surface of used nanoalloy catalysts both partially oxidizes and orders. Remarkably, it largely retains its structural state when the nanoalloys are reused as CO oxidation catalysts. The seemingly inverse structural changes of studied nanoalloy catalysts occurring under CO oxidation and reactivation conditions affect the active sites on their surface significantly. In particular, through different mechanisms, both appear to reduce the CO binding strength to the nanoalloy's surface and thus increase the catalytic stability of the nanoalloys. The findings provide clues for further optimization of nanoalloy catalysts for the oxidation of carbonaceous species through optimizing their composition, activation, and reactivation. Besides, the findings demonstrate the usefulness of combined in situ infrared spectroscopy and total X-ray scattering coupled to surface-specific atomic PDF analysis to the ongoing effort to produce advanced catalysts for environmentally and technologically important applications.

"Sizing" Heterogeneous Chemistry in the Conversion of Gaseous Dimethyl Sulfide to Atmospheric Particles.

PubMed

Enami, Shinichi; Sakamoto, Yosuke; Hara, Keiichiro; Osada, Kazuo; Hoffmann, Michael R; Colussi, Agustín J

2016-02-16

The oxidation of biogenic dimethyl sulfide (DMS) emissions is a global source of cloud condensation nuclei. The amounts of the nucleating H2SO4(g) species produced in such process, however, remain uncertain. Hydrophobic DMS is mostly oxidized in the gas phase into H2SO4(g) + DMSO(g) (dimethyl sulfoxide), whereas water-soluble DMSO is oxidized into H2SO4(g) in the gas phase and into SO4(2-) + MeSO3(-) (methanesulfonate) on water surfaces. R = MeSO3(-)/(non-sea-salt SO4(2-)) ratios would therefore gauge both the strength of DMS sources and the extent of DMSO heterogeneous oxidation if Rhet = MeSO3(-)/SO4(2-) for DMSO(aq) + ·OH(g) were known. Here, we report that Rhet = 2.7, a value obtained from online electrospray mass spectra of DMSO(aq) + ·OH(g) reaction products that quantifies the MeSO3(-) produced in DMSO heterogeneous oxidation on aqueous aerosols for the first time. On this basis, the inverse R dependence on particle radius in size-segregated aerosol collected over Syowa station and Southern oceans is shown to be consistent with the competition between DMSO gas-phase oxidation and its mass accommodation followed by oxidation on aqueous droplets. Geographical R variations are thus associated with variable contributions of the heterogeneous pathway to DMSO atmospheric oxidation, which increase with the specific surface area of local aerosols.

High energy density asymmetric supercapacitors with a nickel oxide nanoflake cathode and a 3D reduced graphene oxide anode

NASA Astrophysics Data System (ADS)

Luan, Feng; Wang, Gongming; Ling, Yichuan; Lu, Xihong; Wang, Hanyu; Tong, Yexiang; Liu, Xiao-Xia; Li, Yat

2013-08-01

Here we demonstrate a high energy density asymmetric supercapacitor with nickel oxide nanoflake arrays as the cathode and reduced graphene oxide as the anode. Nickel oxide nanoflake arrays were synthesized on a flexible carbon cloth substrate using a seed-mediated hydrothermal method. The reduced graphene oxide sheets were deposited on three-dimensional (3D) nickel foam by hydrothermal treatment of nickel foam in graphene oxide solution. The nanostructured electrodes provide a large effective surface area. The asymmetric supercapacitor device operates with a voltage of 1.7 V and achieved a remarkable areal capacitance of 248 mF cm-2 (specific capacitance of 50 F g-1) at a charge/discharge current density of 1 mA cm-2 and a maximum energy density of 39.9 W h kg-1 (based on the total mass of active materials of 5.0 mg). Furthermore, the device showed an excellent charge/discharge cycling performance in 1.0 M KOH electrolyte at a current density of 5 mA cm-2, with a capacitance retention of 95% after 3000 cycles.

Nano Copper Oxide-Modified Carbon Cloth as Cathode for a Two-Chamber Microbial Fuel Cell

PubMed Central

Dong, Feng; Zhang, Peng; Li, Kexun; Liu, Xianhua; Zhang, Pingping

2016-01-01

In this work, Cu2O nanoparticles were deposited on a carbon cloth cathode using a facile electrochemical method. The morphology of the modified cathode, which was characterized by scanning electron microscopy (SEM) and Brunauer-Emmett-Teller (BET) tests, showed that the porosity and specific surface area of the cathode improved with longer deposition times. X-ray photoelectron spectroscopy (XPS) and cyclic voltammetry (CV) results showed that cupric oxide and cuprous oxide coexisted on the carbon cloth, which improved the electrochemical activity of cathode. The cathode with a deposition time of 100 s showed the best performance, with a power density twice that of bare carbon cloth. Linear sweep voltammetry (LSV) and electrochemical impedance spectroscopy (EIS) results revealed that moderate deposition of nano copper oxide on carbon cloth could dramatically reduce the charge transfer resistance, which contributed to the enhanced electrochemical performance. The mediation mechanism of copper oxide nanocatalyst was illustrated by the fact that the recycled conversion between cupric oxide and cuprous oxide accelerated the electron transfer efficiency on the cathode. PMID:28335366

High energy density asymmetric supercapacitors with a nickel oxide nanoflake cathode and a 3D reduced graphene oxide anode.

PubMed

Luan, Feng; Wang, Gongming; Ling, Yichuan; Lu, Xihong; Wang, Hanyu; Tong, Yexiang; Liu, Xiao-Xia; Li, Yat

2013-09-07

Here we demonstrate a high energy density asymmetric supercapacitor with nickel oxide nanoflake arrays as the cathode and reduced graphene oxide as the anode. Nickel oxide nanoflake arrays were synthesized on a flexible carbon cloth substrate using a seed-mediated hydrothermal method. The reduced graphene oxide sheets were deposited on three-dimensional (3D) nickel foam by hydrothermal treatment of nickel foam in graphene oxide solution. The nanostructured electrodes provide a large effective surface area. The asymmetric supercapacitor device operates with a voltage of 1.7 V and achieved a remarkable areal capacitance of 248 mF cm(-2) (specific capacitance of 50 F g(-1)) at a charge/discharge current density of 1 mA cm(-2) and a maximum energy density of 39.9 W h kg(-1) (based on the total mass of active materials of 5.0 mg). Furthermore, the device showed an excellent charge/discharge cycling performance in 1.0 M KOH electrolyte at a current density of 5 mA cm(-2), with a capacitance retention of 95% after 3000 cycles.

Nano Copper Oxide-Modified Carbon Cloth as Cathode for a Two-Chamber Microbial Fuel Cell.

PubMed

Dong, Feng; Zhang, Peng; Li, Kexun; Liu, Xianhua; Zhang, Pingping

2016-12-09

In this work, Cu₂O nanoparticles were deposited on a carbon cloth cathode using a facile electrochemical method. The morphology of the modified cathode, which was characterized by scanning electron microscopy (SEM) and Brunauer-Emmett-Teller (BET) tests, showed that the porosity and specific surface area of the cathode improved with longer deposition times. X-ray photoelectron spectroscopy (XPS) and cyclic voltammetry (CV) results showed that cupric oxide and cuprous oxide coexisted on the carbon cloth, which improved the electrochemical activity of cathode. The cathode with a deposition time of 100 s showed the best performance, with a power density twice that of bare carbon cloth. Linear sweep voltammetry (LSV) and electrochemical impedance spectroscopy (EIS) results revealed that moderate deposition of nano copper oxide on carbon cloth could dramatically reduce the charge transfer resistance, which contributed to the enhanced electrochemical performance. The mediation mechanism of copper oxide nanocatalyst was illustrated by the fact that the recycled conversion between cupric oxide and cuprous oxide accelerated the electron transfer efficiency on the cathode.

Synthetic coprecipitates of exopolysaccharides and ferrihydrite. Part I: Characterization

NASA Astrophysics Data System (ADS)

Mikutta, Christian; Mikutta, Robert; Bonneville, Steeve; Wagner, Friedrich; Voegelin, Andreas; Christl, Iso; Kretzschmar, Ruben

2008-02-01

Iron(III) (hydr)oxides formed at extracellular biosurfaces or in the presence of exopolymeric substances of microbes and plants may significantly differ in their structural and physical properties from their inorganic counterparts. We synthesized ferrihydrite (Fh) in solutions containing acid polysaccharides [polygalacturonic acid (PGA), alginate, xanthan] and compared its properties with that of an abiotic reference by means of X-ray diffraction, transmission electron microscopy, gas adsorption (N 2, CO 2), X-ray absorption spectroscopy, 57Fe Mössbauer spectroscopy, and electrophoretic mobility measurements. The coprecipitates formed contained up to 37 wt% polymer. Two-line Fh was the dominant mineral phase in all precipitates. The efficacy of polymers to precipitate Fh at neutral pH was higher for polymers with more carboxyl C (PGA ˜ alginate > xanthan). Pure Fh had a specific surface area of 300 m 2/g; coprecipitation of Fh with polymers reduced the detectable mineral surface area by up to 87%. Likewise, mineral micro- (<2 nm) and mesoporosity (2-10 nm) decreased by up to 85% with respect to pure Fh, indicative of a strong aggregation of Fh particles by polymers in freeze-dried state. C-1s STXM images showed the embedding of Fh particles in polymer matrices on the micrometer scale. Iron EXAFS spectroscopy revealed no significant changes in the local coordination of Fe(III) between pure Fh and Fh contained in PGA coprecipitates. 57Fe Mössbauer spectra of coprecipitates confirmed Fh as dominant mineral phase with a slightly reduced particle size and crystallinity of coprecipitate-Fh compared to pure Fh and/or a limited magnetic super-exchange between Fh particles in the coprecipitates due to magnetic dilution by the polysaccharides. The pH iep of pure Fh in 0.01 M NaClO 4 was 7.1. In contrast, coprecipitates of PGA and alginate had a pH iep < 2. Considering the differences in specific surface area, porosity, and net charge between the coprecipitates and pure Fh, composites of exopolysaccharides and Fe(III) (hydr)oxides are expected to differ in their geochemical reactivity from pure Fe(III) (hydr)oxides, even if the minerals have a similar crystallinity.

A Dual Role of Graphene Oxide Sheet Deposition on Titanate Nanowire Scaffolds for Osteo-implantation: Mechanical Hardener and Surface Activity Regulator

NASA Astrophysics Data System (ADS)

Dong, Wenjun; Hou, Lijuan; Li, Tingting; Gong, Ziqiang; Huang, Huandi; Wang, Ge; Chen, Xiaobo; Li, Xiaoyun

2015-12-01

Scaffold biomaterials with open pores and channels are favourable for cell growth and tissue regeneration, however the inherent poor mechanical strength and low surface activity limit their applications as load-bearing bone grafts with satisfactory osseointegration. In this study, macro-porous graphene oxide (GO) modified titanate nanowire scaffolds with desirable surface chemistry and tunable mechanical properties were prepared through a simple hydrothermal process followed by electrochemical deposition of GO nanosheets. The interconnected and porous structure of the GO/titanate nanowire scaffolds provides a large surface area for cellular attachment and migration and displays a high compressive strength of approximately 81.1 MPa and a tunable Young’s modulus over the range of 12.4-41.0 GPa, which satisfies site-specific requirements for implantation. Surface chemistry of the scaffolds was modulated by the introduction of GO, which endows the scaffolds flexibility in attaching and patterning bioactive groups (such as -OH, -COOH and -NH2). In vitro cell culture tests suggest that the GO/titanate nanowire scaffolds act as a promising biomaterial candidate, in particular the one terminated with -OH groups, which demonstrates improved cell viability, and proliferation, differentiation and osteogenic activities.

A Dual Role of Graphene Oxide Sheet Deposition on Titanate Nanowire Scaffolds for Osteo-implantation: Mechanical Hardener and Surface Activity Regulator.

PubMed

Dong, Wenjun; Hou, Lijuan; Li, Tingting; Gong, Ziqiang; Huang, Huandi; Wang, Ge; Chen, Xiaobo; Li, Xiaoyun

2015-12-21

Scaffold biomaterials with open pores and channels are favourable for cell growth and tissue regeneration, however the inherent poor mechanical strength and low surface activity limit their applications as load-bearing bone grafts with satisfactory osseointegration. In this study, macro-porous graphene oxide (GO) modified titanate nanowire scaffolds with desirable surface chemistry and tunable mechanical properties were prepared through a simple hydrothermal process followed by electrochemical deposition of GO nanosheets. The interconnected and porous structure of the GO/titanate nanowire scaffolds provides a large surface area for cellular attachment and migration and displays a high compressive strength of approximately 81.1 MPa and a tunable Young's modulus over the range of 12.4-41.0 GPa, which satisfies site-specific requirements for implantation. Surface chemistry of the scaffolds was modulated by the introduction of GO, which endows the scaffolds flexibility in attaching and patterning bioactive groups (such as -OH, -COOH and -NH2). In vitro cell culture tests suggest that the GO/titanate nanowire scaffolds act as a promising biomaterial candidate, in particular the one terminated with -OH groups, which demonstrates improved cell viability, and proliferation, differentiation and osteogenic activities.

Design Strategies for CeO2-MoO3 Catalysts for DeNOx and Hg(0) Oxidation in the Presence of HCl: The Significance of the Surface Acid-Base Properties.

PubMed

Chang, Huazhen; Wu, Qingru; Zhang, Tao; Li, Mingguan; Sun, Xiaoxu; Li, Junhua; Duan, Lei; Hao, Jiming

2015-10-20

A series of CeMoOx catalysts with different surface Ce/Mo ratios was synthesized by a coprecipitation method via changing precipitation pH value. The surface basicity on selective catalytic reduction (SCR) catalysts (CeMoOx and VMo/Ti) was characterized and correlated to the durability and activity of catalyst for simultaneous elimination of NOx and Hg(0). The pH value in the preparation process affected the surface concentrations of Ce and Mo, the Brunauer-Emmett-Teller (BET) specific surface area, and the acid-base properties over the CeMoOx catalysts. The O 1s X-ray photoelectron spectroscopy (XPS) spectra and CO2-temperature programmed desorption (TPD) suggested that the surface basicity increased as the pH value increased. The existence of strong basic sites contributed to the deactivation effect of HCl over the VMo/Ti and CeMoOx catalysts prepared at pH = 12. For the CeMoOx catalysts prepared at pH = 9 and 6, the appearance of surface molybdena species replaced the surface -OH, and the existence of appropriate medium-strength basic sites contributed to their resistance to HCl poisoning in the SCR reaction. Moreover, these sites facilitated the adsorption and activation of HCl and enhanced Hg(0) oxidation. On the other hand, the inhibitory effect of NH3 on Hg(0) oxidation was correlated with the competitive adsorption of NH3 and Hg(0) on acidic surface sites. Therefore, acidic surface sites may play an important role in Hg(0) adsorption. The characterization and balance of basicity and acidity of an SCR catalyst is believed to be helpful in preventing deactivation by acid gas in the SCR reaction and simultaneous Hg(0) oxidation.

All-solid-state flexible supercapacitors based on highly dispersed polypyrrole nanowire and reduced graphene oxide composites.

PubMed

Yu, Chenfei; Ma, Peipei; Zhou, Xi; Wang, Anqi; Qian, Tao; Wu, Shishan; Chen, Qiang

2014-10-22

Highly dispersed polypyrrole nanowires are decorated on reduced graphene oxide sheets using a facile in situ synthesis route. The prepared composites exhibit high dispersibility, large effective surface area, and high electric conductivity. All-solid-state flexible supercapacitors are assembled based on the prepared composites, which show excellent electrochemical performances with a specific capacitance of 434.7 F g(-1) at a current density of 1 A g(-1). The as-fabricated supercapacitor also exhibits excellent cycling stability (88.1% capacitance retention after 5000 cycles) and exceptional mechanical flexibility. In addition, outstanding power and energy densities were obtained, demonstrating the significant potential of prepared material for flexible and portable energy storage devices.

Performance of magnetic zirconium-iron oxide nanoparticle in the removal of phosphate from aqueous solution

NASA Astrophysics Data System (ADS)

Zhang, Chang; Li, Yongqiu; Wang, Fenghua; Yu, Zhigang; Wei, Jingjing; Yang, Zhongzhu; Ma, Chi; Li, Zihao; Xu, ZiYi; Zeng, Guangming

2017-02-01

In this study, magnetic zirconium-iron oxide nanoparticles (MZION) of different Fe/Zr molar ratios were successfully prepared using the co-precipitation method, and their performance for phosphate removal was systematically evaluated. The as-obtained adsorbents were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Zeta potential analyzer, Fourier transform infrared spectroscopy (FT-IR) and Brunauer Emmett Teller (BET) specific surface area analysis. The effects of pH, ionic strength, and co-existing ions (including Cl-, SO42-, NO3- and HCO3-) were measured to evaluate the adsorption performance in batch experiments. The results showed that decreasing the Fe/Zr molar ratios increased the specific surface area that was propitious to adsorption process, but the adsorption capacity enhanced with the decrease of Fe/Zr molar ratios. Phosphate adsorption on MZION could be well described by the Freundlich equilibrium model and pseudo-second-order kinetics. The adsorption of phosphate was highly pH dependent and decreased with increasing pH from 1.5 to 10.0. The adsorption was slightly affected by ionic strength. With the exception of HCO3-, co-existing anions showed minimum or no effect on their adsorption performance. After adsorption, phosphate on these MZION could be easily desorbed by 0.1 M NaOH solution. The phosphate adsorption mechanism of MZION followed the inner-sphere complexing mechanism, and the surface sbnd OH groups played a significant role in the phosphate adsorption. Additionally, the main advantages of MZION consisted in its separation convenience and highly adsorption capacity compared to other adsorbents.

Appearance of the minority dz2 surface state and disappearance of the image-potential state: Criteria for clean Fe(001)

NASA Astrophysics Data System (ADS)

Eibl, Christian; Schmidt, Anke B.; Donath, Markus

2012-10-01

The unoccupied surface electronic structure of clean and oxidized Fe(001) was studied with spin-resolved inverse photoemission and target current spectroscopy. For the clean surface, we detected a dz2 surface state with minority spin character just above the Fermi level, while the image-potential surface state disappears. The opposite is observed for the ordered p(1×1)O/Fe(001) surface: the dz2-type surface state is quenched, while the image-potential state shows up as a pronounced feature. This behavior indicates enhanced surface reflectivity at the oxidized surface. The appearance and disappearance of specific unoccupied surface states prove to be decisive criteria for a clean Fe(001) surface. In addition, enhanced spin asymmetry in the unoccupied states is observed for the oxidized surface. Our results have implications for the use of clean and oxidized Fe(001) films as spin-polarization detectors.

Surface-Casting Synthesis of Mesoporous Zirconia with a CMK-5-Like Structure and High Surface Area.

PubMed

Gu, Dong; Schmidt, Wolfgang; Pichler, Christian M; Bongard, Hans-Josef; Spliethoff, Bernd; Asahina, Shunsuke; Cao, Zhengwen; Terasaki, Osamu; Schüth, Ferdi

2017-09-04

About 15 years ago, the Ryoo group described the synthesis of CMK-5, a material consisting of a hexagonal arrangement of carbon nanotubes. Extension of the surface casting synthesis to oxide compositions, however, was not possible so far, in spite of many attempts. Here it is demonstrated, that crystalline mesoporous hollow zirconia materials with very high surface areas up to 400 m 2  g -1 , and in selected cases in the form of CMK-5-like, are indeed accessible via such a surface casting process. The key for the successful synthesis is an increased interaction between the silica hard template surface and the zirconia precursor species by using silanol group-rich mesoporous silica as a hard template. The surface areas of the obtained zirconias exceed those of conventionally hard-templated ones by a factor of two to three. The surface casting process seems to be applicable also to other oxide materials. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Enhanced Catalytic Activities of NiPt Truncated Octahedral Nanoparticles toward Ethylene Glycol Oxidation and Oxygen Reduction in Alkaline Electrolyte.

PubMed

Xia, Tianyu; Liu, Jialong; Wang, Shouguo; Wang, Chao; Sun, Young; Gu, Lin; Wang, Rongming

2016-05-04

The high cost and poor durability of Pt nanoparticles (NPs) are great limits for the proton exchange membrane fuel cells (PEMFCs) from being scaled-up for commercial applications. Pt-based bimetallic NPs together with a uniform distribution can effectively reduce the usage of expensive Pt while increasing poison resistance of intermediates. In this work, a simple one-pot method was used to successfully synthesize ultrafine (about 7.5 nm) uniform NiPt truncated octahedral nanoparticles (TONPs) in dimethylformamid (DMF) without any seeds or templates. The as-prepared NiPt TONPs with Pt-rich surfaces exhibit greatly improved catalytic activities together with good tolerance and better stability for ethylene glycol oxidation reaction (EGOR) and oxygen reduction reaction (ORR) in comparison with NiPt NPs and commercial Pt/C catalysts in alkaline electrolyte. For example, the value of mass and specific activities for EGOR are 23.2 and 17.6 times higher comparing with those of commercial Pt/C, respectively. Our results demonstrate that the dramatic enhancement is mainly attributed to Pt-rich surface, larger specific surface area, together with coupling between Ni and Pt atoms. This developed method provides a promising pathway for simple preparation of highly efficient electrocatalysts for PEMFCs in the near future.

Process for Making a Noble Metal on Tin Oxide Catalyst

NASA Technical Reports Server (NTRS)

Davis, Patricia; Miller, Irvin; Upchurch, Billy

2010-01-01

To produce a noble metal-on-metal oxide catalyst on an inert, high-surface-area support material (that functions as a catalyst at approximately room temperature using chloride-free reagents), for use in a carbon dioxide laser, requires two steps: First, a commercially available, inert, high-surface-area support material (silica spheres) is coated with a thin layer of metal oxide, a monolayer equivalent. Very beneficial results have been obtained using nitric acid as an oxidizing agent because it leaves no residue. It is also helpful if the spheres are first deaerated by boiling in water to allow the entire surface to be coated. A metal, such as tin, is then dissolved in the oxidizing agent/support material mixture to yield, in the case of tin, metastannic acid. Although tin has proven especially beneficial for use in a closed-cycle CO2 laser, in general any metal with two valence states, such as most transition metals and antimony, may be used. The metastannic acid will be adsorbed onto the high-surface-area spheres, coating them. Any excess oxidizing agent is then evaporated, and the resulting metastannic acid-coated spheres are dried and calcined, whereby the metastannic acid becomes tin(IV) oxide. The second step is accomplished by preparing an aqueous mixture of the tin(IV) oxide-coated spheres, and a soluble, chloride-free salt of at least one catalyst metal. The catalyst metal may be selected from the group consisting of platinum, palladium, ruthenium, gold, and rhodium, or other platinum group metals. Extremely beneficial results have been obtained using chloride-free salts of platinum, palladium, or a combination thereof, such as tetraammineplatinum (II) hydroxide ([Pt(NH3)4] (OH)2), or tetraammine palladium nitrate ([Pd(NH3)4](NO3)2).

Wall-like hierarchical metal oxide nanosheet arrays grown on carbon cloth for excellent supercapacitor electrodes

NASA Astrophysics Data System (ADS)

Huang, Zongyu; Zhang, Zhen; Qi, Xiang; Ren, Xiaohui; Xu, Guanghua; Wan, Pengbo; Sun, Xiaoming; Zhang, Han

2016-07-01

Recently, considerable efforts have been made to satisfy the future requirements of electrochemical energy storage using novel functional electrode materials. Binary transition metal oxides (BTMOs) possess multiple oxidation states that enable multiple redox reactions, showing higher supercapacitive properties than single component metal oxides. In this work, a facile hydrothermal method is provided for the synthesis of wall-like hierarchical metal oxide MMoO4 (M = Ni, Co) nanosheet arrays, which are directly grown on flexible carbon cloth for use as advanced binder-free electrodes for supercapacitors. By virtue of their intriguing structure, the resulted active material nanosheets with a high specific surface area can provide a large electroactive region, which could facilitate easy accession of electrolyte ions and fast charge transport, resulting in an enhanced electrochemical performance. Separately, the as-synthesized MMoO4 (M = Ni, Co) samples have exhibited superior specific capacitances (1483 F g-1 of NiMoO4 and 452 F g-1 of CoMoO4 at a current density of 2 A g-1), as well as excellent cycling stability (93.1% capacitance retention of NiMoO4 and 95.9% capacitance retention of CoMoO4 after 2000 cycles). The results show that the binder-free electrodes constructed by deposition of MMoO4 (M = Ni, Co) nanosheets on carbon cloth are promising candidates for the application of supercapacitors.Recently, considerable efforts have been made to satisfy the future requirements of electrochemical energy storage using novel functional electrode materials. Binary transition metal oxides (BTMOs) possess multiple oxidation states that enable multiple redox reactions, showing higher supercapacitive properties than single component metal oxides. In this work, a facile hydrothermal method is provided for the synthesis of wall-like hierarchical metal oxide MMoO4 (M = Ni, Co) nanosheet arrays, which are directly grown on flexible carbon cloth for use as advanced binder-free electrodes for supercapacitors. By virtue of their intriguing structure, the resulted active material nanosheets with a high specific surface area can provide a large electroactive region, which could facilitate easy accession of electrolyte ions and fast charge transport, resulting in an enhanced electrochemical performance. Separately, the as-synthesized MMoO4 (M = Ni, Co) samples have exhibited superior specific capacitances (1483 F g-1 of NiMoO4 and 452 F g-1 of CoMoO4 at a current density of 2 A g-1), as well as excellent cycling stability (93.1% capacitance retention of NiMoO4 and 95.9% capacitance retention of CoMoO4 after 2000 cycles). The results show that the binder-free electrodes constructed by deposition of MMoO4 (M = Ni, Co) nanosheets on carbon cloth are promising candidates for the application of supercapacitors. Electronic supplementary information (ESI) available: XRD pattern and charge-discharge plots. See DOI: 10.1039/c6nr04020a

Effect of synthesized ZnO nanoparticles on thermal conductivity and mechanical properties of natural rubber

NASA Astrophysics Data System (ADS)

Suntako, R.

2018-01-01

Zinc oxide (ZnO) is widely used in rubber industry as a cure activator for rubber vulcanization. In this work, comparison of cure characteristic, mechanical properties, thermal conductivity and volume swell testing in oil no.1 and oil no.3 between natural rubber (NR) filled synthesized ZnO nanoparticles (sZnO) by precipitation method and NR filled conventional ZnO (cZnO). The particle size of sZnO is 41.50 nm and specific area of 27.92 m2/g, the particle size of cZnO is 312.92 nm and specific surface area of 1.35 m2/g. It has been found that NR filled sZnO not only improves rubber mechanical properties, volume swell testing but also improves thermal conductivity and better than NR filled cZnO. Thermal conductivity of NR filled sZnO increases by 10.34%, 12.90% and 20.00%, respectively when compared with NR filled cZnO in same loading content (various concentrations of ZnO at 5, 8 and 10 parts per hundred parts of rubber). This is due to small particle size and large specific surface area of sZnO which lead to an increase in crosslinking in rubber chain and enhance heat transfer performance.

Enhanced hydrophilicity of chlorided aluminum oxide particulates

NASA Technical Reports Server (NTRS)

Cofer, W. R., III

1978-01-01

An enhancement of hydrophilicity for chlorided aluminas was demonstrated by the results obtained from gaseous H2O sorptions at 70-, 80-, and 86-percent relative humidity on alpha and gamma aluminum oxide particulates and on alpha and gamma aluminum oxide particulates with a chemisorbed surface chloride phase (produced by reactions of gaseous HCl + H2O on alumina). Continuous sorption histories for H2O on chlorided aluminas having specific surface areas that range from 7 to 227 sq m/g before chloriding indicated that initial sorption rates were directly linked to the extent of chemisorbed chlorided coverage and implied the same relationship for sorption capacities. The initial sorption rate on chlorided aluminas was found to be slower for the first exposure to H2O than for subsequent exposures (which reached equilibrated H2O coverages much faster), suggesting that slow chemical reactions between H2O and chlorided alumina may have been operative during initial exposures. Chlorided alumina particles were found to remain very hydrophilic (relative to nonchlorided analogs) for several H2O sorption/desorption cycles.

Influence of oxygenation on chromium redox reactions with manganese sulfide (MnS(s)).

PubMed

Wadhawan, Amar R; Livi, Kenneth J; Stone, Alan T; Bouwer, Edward J

2015-03-17

Manganese sulfide (MnS(s)) minerals exist in sulfidic environments and can have unique reactive abilities because of sulfide, which is a known reductant, and Mn, the oxyhydroxides of which are known oxidants. This study elucidated the role of MnS(s) in controlling Cr speciation with implications on its fate and toxicity in the natural environment, specifically sulfidic sediments that undergo biogeochemical changes due to sediment resuspension during dredging, bioturbation, and flood events. In continuously mixed batch reaction experiments, aqueous CrVI reduction under anaerobic conditions occurred primarily on the surface of MnS(s) displaying a biphasic behavior- the initial rapid removal of CrVI from solution was followed by a slow decline due to surface passivation by reaction products, mainly sorbed or precipitated CrIII. The reaction progress increased with MnS(s) surface area loading but decreased on increasing CrVI concentration and pH, suggesting that surface site regeneration through product desorption was the rate-controlling mechanism. Below circum-neutral pH, higher solubility of MnS(s) resulted in additional CrVI reduction by reduced sulfur species in solution, whereas increased CrIII solubility lowered surface passivation allowing for more reactive sites to participate in the reaction. Aeration of MnS(s) at pH≥7 caused the formation of a heterogeneous MnIII(hydr)oxide that was composed of hausmanite and manganite. CrVI reoccurrence was observed on aeration of CrVI-spiked MnS(s) from the oxidation of product CrIII. The reoccurrence at pH≥7 was attributed to the oxidation of product CrIII by MnIII(hydr)oxide, whereas the reoccurrence at pH<7 was hypothesized from the oxidation of product CrIII by intermediate aqueous MnIII and/or sulfur species. Just as with Cr, MnS(s) may play an important role in speciation, fate, and transport of other environmental contaminants.

Thermal and sonochemical synthesis of porous (Ce,Zr)O2 mixed oxides from metal β-diketonate precursors and their catalytic activity in wet air oxidation process of formic acid.

PubMed

Cau, Camille; Guari, Yannick; Chave, Tony; Larionova, Joulia; Nikitenko, Sergey I

2014-07-01

Porous (Ce0.5Zr0.5)O2 solid solutions were prepared by thermolysis (T=285 °C) or sonolysis (20 kHz, I=32 W cm(-2), Pac=0.46 W mL(-1), T=200 °C) of Ce(III) and Zr(IV) acetylacetonates in oleylamine or hexadecylamine under argon followed by heat treatment of the precipitates obtained in air at 450 °C. Transmission Electron Microscopy images of the samples show nanoparticles of ca. 4-6 nm for the two synthetic approaches. The powder X-ray diffraction, scanning electron microscopy, energy dispersive X-ray and μ-Raman spectroscopy of solids obtained after heat treatment indicate the formation of (Ce0.5Zr0.5)O2 solid solutions with a metastable tetragonal crystal structure for the two synthetic routes. The specific surface area of the samples varies between 78 and 149 m(2) g(-1) depending on synthesis conditions. The use of Barrett-Joyner-Halenda and t-plot methods reveal the formation of mixed oxides with a hybrid morphology that combines mesoporosity and microporosity regardless of the method of preparation. Platinum nanoparticles were deposited on the surface of the mixed oxides by sonochemical reduction of Pt(IV). It was found that the materials prepared by sonochemistry exhibit better resistance to dissolution during the deposition process of platinum. X-ray photoelectron spectroscopy analysis shows the presence of Pt(0) and Pt(II) on the surface of mixed oxides. Porous (Ce0.5Zr0.5)O2 mixed oxides loaded with 1.5%wt. platinum exhibit high activity in catalytic wet air oxidation of formic acid at 40 °C. Copyright © 2014 Elsevier B.V. All rights reserved.

Preparation of extrusions of bulk mixed oxide compounds with high macroporosity and mechanical strength

DOEpatents

Flytzani-Stephanopoulos, Maria; Jothimurugesan, Kandaswami

1990-01-01

A simple and effective method for producing bulk single and mixed oxide absorbents and catalysts is disclosed. The method yields bulk single oxide and mixed oxide absorbent and catalyst materials which combine a high macroporosity with relatively high surface area and good mechanical strength. The materials are prepared in a pellet form using as starting compounds, calcined powders of the desired composition and physical properties these powders are crushed to broad particle size distribution, and, optionally may be combined with an inorganic clay binder. The necessary amount of water is added to form a paste which is extruded, dried and heat treated to yield and desired extrudate strength. The physical properties of the extruded materials (density, macroporosity and surface area) are substantially the same as the constituent powder is the temperature of the heat treatment of the extrudates is approximately the same as the calcination temperature of the powder. If the former is substantially higher than the latter, the surface area decreases, but the macroporosity of the extrusions remains essentially constant.

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.

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

PubMed

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

2014-01-01

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

Measuring the specific surface area of natural and manmade glasses: effects of formation process, morphology, and particle size

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

Papelis, Charalambos; Um, Wooyong; Russel, Charles E.

2003-03-28

The specific surface area of natural and manmade solid materials is a key parameter controlling important interfacial processes in natural environments and engineered systems, including dissolution reactions and sorption processes at solid-fluid interfaces. To improve our ability to quantify the release of trace elements trapped in natural glasses, the release of hazardous compounds trapped in manmade glasses, or the release of radionuclides from nuclear melt glass, we measured the specific surface area of natural and manmade glasses as a function of particle size, morphology, and composition. Volcanic ash, volcanic tuff, tektites, obsidian glass, and in situ vitrified rock were analyzed.more » Specific surface area estimates were obtained using krypton as gas adsorbent and the BET model. The range of surface areas measured exceeded three orders of magnitude. A tektite sample had the highest surface area (1.65 m2/g), while one of the samples of in situ vitrified rock had the lowest surf ace area (0.0016 m2/g). The specific surface area of the samples was a function of particle size, decreasing with increasing particle size. Different types of materials, however, showed variable dependence on particle size, and could be assigned to one of three distinct groups: (1) samples with low surface area dependence on particle size and surface areas approximately two orders of magnitude higher than the surface area of smooth spheres of equivalent size. The specific surface area of these materials was attributed mostly to internal porosity and surface roughness. (2) samples that showed a trend of decreasing surface area dependence on particle size as the particle size increased. The minimum specific surface area of these materials was between 0.1 and 0.01 m2/g and was also attributed to internal porosity and surface roughness. (3) samples whose surface area showed a monotonic decrease with increasing particle size, never reaching an ultimate surface area limit within the particle size range examined. The surface area results were consistent with particle morphology, examined by scanning electron microscopy, and have significant implications for the release of radionuclides and toxic metals in the environment.« less

E-beam and UV induced fabrication of CeO2, Eu2O3 and their mixed oxides with UO2

NASA Astrophysics Data System (ADS)

Pavelková, Tereza; Vaněček, Vojtěch; Jakubec, Ivo; Čuba, Václav

2016-07-01

CeO2, Eu2O3 and mixed oxides of CeO2-UO2, Eu2O3-UO2 were fabricated. The preparative method was based on the irradiation of aqueous solutions containing cerium/europium (and uranyl) nitrates and ammonium formate. In the course of irradiation, the solid phase (precursor) was precipitated. The composition of irradiated solutions significantly affected the properties of precursor formed in the course of the irradiation. However, subsequent heat treatment of (amorphous) precursors at temperatures ≤650 °C invariably resulted in the formation of powder oxides with well-developed nanocrystals with linear crystallite size 13-27 nm and specific surface area 10-46 m2 g-1. The applicability of both ionizing (e-beam) and non-ionizing (UV) radiation was studied.

Basic Research of Intrinsic Tamper Indication Markings Defined by Pulsed Laser Irradiation (Quad Chart).

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

Moody, Neville R.

Objective: We will research how short (ns) and ultrashort (fs) laser pulses interact with the surfaces of various materials to create complex color layers and morphological patterns. Method: We are investigating the site-specific, formation of microcolor features. Also, research includes a fundamental study of the physics underlying periodic ripple formation during femtosecond laser irradiation. Status of effort: Laser induced color markings were demonstrated on an increased number of materials (including metal thin films) and investigated for optical properties and microstructure. Technology that allows for marking curved surfaces (and large areas) has been implemented. We have used electro-magnetic solvers to modelmore » light-solid interactions leading to periodic surface ripple patterns. This includes identifying the roles of surface plasmon polaritons. Goals/Milestones: Research corrosion resistance of oxide color markings (salt spray, fog, polarization tests); Through modeling, investigate effects of multi-source scattering and interference on ripple patterns; Investigate microspectrophotometry for mapping color; and Investigate new methods for laser color marking curved surfaces and large areas.« less

Method of physical vapor deposition of metal oxides on semiconductors

DOEpatents

Norton, David P.

2001-01-01

A process for growing a metal oxide thin film upon a semiconductor surface with a physical vapor deposition technique in a high-vacuum environment and a structure formed with the process involves the steps of heating the semiconductor surface and introducing hydrogen gas into the high-vacuum environment to develop conditions at the semiconductor surface which are favorable for growing the desired metal oxide upon the semiconductor surface yet is unfavorable for the formation of any native oxides upon the semiconductor. More specifically, the temperature of the semiconductor surface and the ratio of hydrogen partial pressure to water pressure within the vacuum environment are high enough to render the formation of native oxides on the semiconductor surface thermodynamically unstable yet are not so high that the formation of the desired metal oxide on the semiconductor surface is thermodynamically unstable. Having established these conditions, constituent atoms of the metal oxide to be deposited upon the semiconductor surface are directed toward the surface of the semiconductor by a physical vapor deposition technique so that the atoms come to rest upon the semiconductor surface as a thin film of metal oxide with no native oxide at the semiconductor surface/thin film interface. An example of a structure formed by this method includes an epitaxial thin film of (001)-oriented CeO.sub.2 overlying a substrate of (001) Ge.

Controlling the physics and chemistry of binary and ternary praseodymium and cerium oxide systems.

PubMed

Niu, Gang; Zoellner, Marvin Hartwig; Schroeder, Thomas; Schaefer, Andreas; Jhang, Jin-Hao; Zielasek, Volkmar; Bäumer, Marcus; Wilkens, Henrik; Wollschläger, Joachim; Olbrich, Reinhard; Lammers, Christian; Reichling, Michael

2015-10-14

Rare earth praseodymium and cerium oxides have attracted intense research interest in the last few decades, due to their intriguing chemical and physical characteristics. An understanding of the correlation between structure and properties, in particular the surface chemistry, is urgently required for their application in microelectronics, catalysis, optics and other fields. Such an understanding is, however, hampered by the complexity of rare earth oxide materials and experimental methods for their characterisation. Here, we report recent progress in studying high-quality, single crystalline, praseodymium and cerium oxide films as well as ternary alloys grown on Si(111) substrates. Using these well-defined systems and based on a systematic multi-technique surface science approach, the corresponding physical and chemical properties, such as the surface structure, the surface morphology, the bulk-surface interaction and the oxygen storage/release capability, are explored in detail. We show that specifically the crystalline structure and the oxygen stoichiometry of the oxide thin films can be well controlled by the film preparation method. This work leads to a comprehensive understanding of the properties of rare earth oxides and highlights the applications of these versatile materials. Furthermore, methanol adsorption studies are performed on binary and ternary rare earth oxide thin films, demonstrating the feasibility of employing such systems for model catalytic studies. Specifically for ceria systems, we find considerable stability against normal environmental conditions so that they can be considered as a "materials bridge" between surface science models and real catalysts.

Energetic basis of catalytic activity of layered nanophase calcium manganese oxides for water oxidation

PubMed Central

Birkner, Nancy; Nayeri, Sara; Pashaei, Babak; Najafpour, Mohammad Mahdi; Casey, William H.; Navrotsky, Alexandra

2013-01-01

Previous measurements show that calcium manganese oxide nanoparticles are better water oxidation catalysts than binary manganese oxides (Mn3O4, Mn2O3, and MnO2). The probable reasons for such enhancement involve a combination of factors: The calcium manganese oxide materials have a layered structure with considerable thermodynamic stability and a high surface area, their low surface energy suggests relatively loose binding of H2O on the internal and external surfaces, and they possess mixed-valent manganese with internal oxidation enthalpy independent of the Mn3+/Mn4+ ratio and much smaller in magnitude than the Mn2O3-MnO2 couple. These factors enhance catalytic ability by providing easy access for solutes and water to active sites and facile electron transfer between manganese in different oxidation states. PMID:23667149

Energetic basis of catalytic activity of layered nanophase calcium manganese oxides for water oxidation.

PubMed

Birkner, Nancy; Nayeri, Sara; Pashaei, Babak; Najafpour, Mohammad Mahdi; Casey, William H; Navrotsky, Alexandra

2013-05-28

Previous measurements show that calcium manganese oxide nanoparticles are better water oxidation catalysts than binary manganese oxides (Mn3O4, Mn2O3, and MnO2). The probable reasons for such enhancement involve a combination of factors: The calcium manganese oxide materials have a layered structure with considerable thermodynamic stability and a high surface area, their low surface energy suggests relatively loose binding of H2O on the internal and external surfaces, and they possess mixed-valent manganese with internal oxidation enthalpy independent of the Mn(3+)/Mn(4+) ratio and much smaller in magnitude than the Mn2O3-MnO2 couple. These factors enhance catalytic ability by providing easy access for solutes and water to active sites and facile electron transfer between manganese in different oxidation states.

La and Al co-doped CaMnO3 perovskite oxides: From interplay of surface properties to anion exchange membrane fuel cell performance

NASA Astrophysics Data System (ADS)

Dzara, Michael J.; Christ, Jason M.; Joghee, Prabhuram; Ngo, Chilan; Cadigan, Christopher A.; Bender, Guido; Richards, Ryan M.; O'Hayre, Ryan; Pylypenko, Svitlana

2018-01-01

This work reports the first account of perovskite oxide and carbon composite oxygen reduction reaction (ORR) catalysts integrated into anion exchange membrane fuel cells (AEMFCs). Perovskite oxides with a theoretical stoichiometry of Ca0.9La0.1Al0.1Mn0.9O3-δ are synthesized by an aerogel method and calcined at various temperatures, resulting in a set of materials with varied surface chemistry and surface area. Material composition is evaluated by X-ray diffraction, energy dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy. The perovskite oxide calcined at 800 °C shows the importance of balance between surface area, purity of the perovskite phase, and surface composition, resulting in the highest ORR mass activity when evaluated in rotating disk electrodes. Integration of this catalyst into AEMFCs reveals that the best AEMFC performance is obtained when using composites with 30:70 perovskite oxide:carbon composition. Doubling the loading leads to an increase in the power density from 30 to 76 mW cm-2. The AEMFC prepared with a composite based on perovskite oxide and N-carbon achieves a power density of 44 mW cm-2, demonstrating an ∼50% increase when compared to the highest performing composite with undoped carbon at the same loading.

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.

Surface characteristics and bioactivity of oxide film on titanium metal formed by thermal oxidation.

PubMed

Park, Yeong-Joon; Song, Ho-Jun; Kim, In; Yang, Hong-So

2007-04-01

In this study, we characterized the surface of oxide film formed on titanium metal through the use of thermal treatment and investigated the effect of surface characteristics on the bioactivity of titanium. The as-received sample group was prepared by polishing and cleaning CP-Ti as a control group, and thermally oxidized sample groups were prepared by heat treating at 530, 600, 700, 800, 900, and 1000 degrees C respectively. Micro-morphology, crystalline structure, chemical composition, and binding state were evaluated using FE-SEM, XRD, and XPS. The bioactivity of sample groups was investigated by observing the degree of calcium phosphate formation from immersion testing in MEM. The surface characterization tests showed that hydroxyl group content in titanium oxide film was increased, as the density of titanium atoms was high and the surface area was large. In MEM immersion test, initial calcium phosphate formation was dependent upon the thickness of titanium oxide, and resultant calcium phosphate formation depended on the content of the hydroxyl group of the titanium oxide film surface.

Low temperature ozone oxidation of solid waste surrogates

NASA Astrophysics Data System (ADS)

Nabity, James A.; Lee, Jeffrey M.

2015-09-01

Solid waste management presents a significant challenge to human spaceflight and especially, long-term missions beyond Earth orbit. A six-month mission will generate over 300 kg of solid wastes per crewmember that must be dealt with to eliminate the need for storage and prevent it from becoming a biological hazard to the crew. There are several methods for the treatment of wastes that include oxidation via ozone, incineration, microbial oxidation or pyrolysis and physical methods such as microwave drying and compaction. In recent years, a low temperature oxidation process using ozonated water has been developed for the chemical conversion of organic wastes to CO2 and H2O. Experiments were conducted to evaluate the rate and effectiveness with which ozone oxidized several different waste materials. Increasing the surface area by chopping or shredding the solids into small pieces more than doubled the rate of oxidation. A greater flow of ozone and agitation of the ozonated water system also increased processing rates. Of the materials investigated, plastics have proven the most difficult to oxidize. The processing of plastics above the glass transition temperatures caused the plastics to clump together which reduced the exposed surface area, while processing at lower temperatures reduced surface reaction kinetics.

Adsorption of cadmium by activated carbon cloth: influence of surface oxidation and solution pH.

PubMed

Rangel-Mendez, J R; Streat, M

2002-03-01

The surface of activated carbon cloth (ACC), based on polyacrylonitrile fibre as a precursor, was oxidised using nitric acid, ozone and electrochemical oxidation to enhance cadmium ion exchange capacity. Modified adsorbents were physically and chemically characterised by pH titration, direct titration, X-ray photoelectron spectroscopy, elemental analysis, surface area and porosimetry, and scanning electron microscopy. BET surface area decreased after oxidation, however, the total ion exchange capacity increased by a factor of approximately 3.5 compared to the commercial as-received ACC. A very significant increase in cadmium uptake, by a factor of 13, was observed for the electrochemically oxidised ACC. Equilibrium sorption isotherms were determined at pH 4, 5 and 6 and these showed that cadmium uptake increased with increasing pH. There was clear evidence of physical damage to ozone-oxidised fibre, however, acid and electrochemically oxidised samples were completely stable.

Recent Progress in Self-Supported Metal Oxide Nanoarray Electrodes for Advanced Lithium-Ion Batteries.

PubMed

Zhang, Feng; Qi, Limin

2016-09-01

The rational design and fabrication of electrode materials with desirable architectures and optimized properties has been demonstrated to be an effective approach towards high-performance lithium-ion batteries (LIBs). Although nanostructured metal oxide electrodes with high specific capacity have been regarded as the most promising alternatives for replacing commercial electrodes in LIBs, their further developments are still faced with several challenges such as poor cycling stability and unsatisfying rate performance. As a new class of binder-free electrodes for LIBs, self-supported metal oxide nanoarray electrodes have many advantageous features in terms of high specific surface area, fast electron transport, improved charge transfer efficiency, and free space for alleviating volume expansion and preventing severe aggregation, holding great potential to solve the mentioned problems. This review highlights the recent progress in the utilization of self-supported metal oxide nanoarrays grown on 2D planar and 3D porous substrates, such as 1D and 2D nanostructure arrays, hierarchical nanostructure arrays, and heterostructured nanoarrays, as anodes and cathodes for advanced LIBs. Furthermore, the potential applications of these binder-free nanoarray electrodes for practical LIBs in full-cell configuration are outlined. Finally, the future prospects of these self-supported nanoarray electrodes are discussed.

Characterization And Dissolution Properties Of Ruthenium Oxides

EPA Science Inventory

Ruthenium oxides (RuO₂•1.10H₂O and RuO₂) have been synthesized by forced hydrolysis and oxidation of ruthenium chloride. The resulting materials were extensively characterized to determine the crystallinity, surface area, and ruthenium oxidation ...

Laser-induced reduction of graphene oxide powders by high pulsed ultraviolet laser irradiations

NASA Astrophysics Data System (ADS)

Yang, Chii-Rong; Tseng, Shih-Feng; Chen, Yu-Ting

2018-06-01

This study aims to develop a laser-induced reduction approach for graphene oxide (GO) powders fabricated by using high pulsed ultraviolet laser irradiations. Before and after the laser irradiation with different fluences, the physical and electrical properties of homemade GO powders and reduced graphene oxide (rGO) powders were measured and analyzed using Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), surface area analyzer, and four-point probe instrument. The laser irradiation parameters included the pulse repetition frequency of 100 kHz, the scanning speed of galvanometers of 50 mm/s, the number of laser irradiated cycles of 10, and the laser fluences of ranging from 0.153 mJ/cm2 to 0.525 mJ/cm2. The laser reduction experiments of GO powders demonstrated that the largest relative intensity of the 2D peak and specific surface area were found at the laser fluence of 0.438 mJ/cm2. Moreover, the electrical resistance sharply decreased from 280 MΩ in the initial GO powders to 0.267 MΩ in rGO powders at a laser irradiation fluence of 0.438. The C/O ratio was increased from 0.232 in the initial GO powders to 1.86 in the rGO powders at a laser irradiation fluence of 0.525 mJ/cm2; furthermore, the C/O ratios increased with increasing the laser fluences.

Tailoring the structure of metal oxide nanostructures towards enhanced sensing properties for environmental applications.

PubMed

Yang, Mingqing; He, Junhui

2012-02-15

The present article reviews recent works in our laboratory about the sensing properties to toxic gases using nanostructured WO(3), TiO(2), FTiO(2), and CuO functionalized quartz crystal microbalance (QCM) sensors. WO(3) and TiO(2) functionalized QCM sensors have much shorter response time than those functionalized by conventional hydrogen-bond acidic branched copolymers for detection of dimethyl methylphosphonate (DMMP). FTiO(2) functionalized QCM sensors can improve the gas sensing characteristics by shortening the response time but at the price of partial irreversibility. The sensing mechanism was examined by diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). Varied CuO nanostructures were synthesized by simple modulation of reaction conditions. All the as-prepared CuO was applied on QCM resonators and explored for HCN sensing. Surprisingly, responses of all the sensors to HCN were found to be in an opposite direction as compared with other common volatile substances, offering excellent selectivity for HCN detection. The sensitivity was very high, and the response and recovery were very fast. Comparison of the specific surface areas of CuO nanostructures showed that CuO of higher surface area is more sensitive than that of lower surface area, indicating that the specific surface area of these CuO nanostructures plays an important role in the sensitivity of related sensors. Based on experimental results, a sensing mechanism was proposed in which a surface redox reaction occurs between CuO and Cu(2)O on the CuO nanostructures reversibly upon contact with HCN and air, respectively. The CuO functionalized QCM sensors are considered to be a promising candidate for trace HCN gas detection in practical applications. Copyright © 2011 Elsevier Inc. All rights reserved.

Solution combustion synthesis of metal oxide nanomaterials for energy storage and conversion.

PubMed

Li, Fa-tang; Ran, Jingrun; Jaroniec, Mietek; Qiao, Shi Zhang

2015-11-14

The design and synthesis of metal oxide nanomaterials is one of the key steps for achieving highly efficient energy conversion and storage on an industrial scale. Solution combustion synthesis (SCS) is a time- and energy-saving method as compared with other routes, especially for the preparation of complex oxides which can be easily adapted for scale-up applications. This review summarizes the synthesis of various metal oxide nanomaterials and their applications for energy conversion and storage, including lithium-ion batteries, supercapacitors, hydrogen and methane production, fuel cells and solar cells. In particular, some novel concepts such as reverse support combustion, self-combustion of ionic liquids, and creation of oxygen vacancies are presented. SCS has some unique advantages such as its capability for in situ doping of oxides and construction of heterojunctions. The well-developed porosity and large specific surface area caused by gas evolution during the combustion process endow the resulting materials with exceptional properties. The relationship between the structural properties of the metal oxides studied and their performance is discussed. Finally, the conclusions and perspectives are briefly presented.

Solution combustion synthesis of metal oxide nanomaterials for energy storage and conversion

NASA Astrophysics Data System (ADS)

Li, Fa-Tang; Ran, Jingrun; Jaroniec, Mietek; Qiao, Shi Zhang

2015-10-01

The design and synthesis of metal oxide nanomaterials is one of the key steps for achieving highly efficient energy conversion and storage on an industrial scale. Solution combustion synthesis (SCS) is a time- and energy-saving method as compared with other routes, especially for the preparation of complex oxides which can be easily adapted for scale-up applications. This review summarizes the synthesis of various metal oxide nanomaterials and their applications for energy conversion and storage, including lithium-ion batteries, supercapacitors, hydrogen and methane production, fuel cells and solar cells. In particular, some novel concepts such as reverse support combustion, self-combustion of ionic liquids, and creation of oxygen vacancies are presented. SCS has some unique advantages such as its capability for in situ doping of oxides and construction of heterojunctions. The well-developed porosity and large specific surface area caused by gas evolution during the combustion process endow the resulting materials with exceptional properties. The relationship between the structural properties of the metal oxides studied and their performance is discussed. Finally, the conclusions and perspectives are briefly presented.

Porous Ni-Co-Mn oxides prisms for high performance electrochemical energy storage

NASA Astrophysics Data System (ADS)

Zhao, Jianbo; Li, Man; Li, Junru; Wei, Chengzhen; He, Yuyue; Huang, Yixuan; Li, Qiaoling

2017-12-01

Porous Ni-Co-Mn oxides prisms have been successfully synthesized via a facile route. The process involves the preparation of nickel-cobalt-manganese acetate hydroxide by a simple co-precipitation method and subsequently the thermal treatment. The as-synthesized Ni-Co-Mn oxides prisms had a large surface area (96.53 m2 g-1) and porous structure. As electrode materials for supercapacitors, porous Ni-Co-Mn oxides prisms showed a high specific capacitance of 1623.5 F g-1 at 1.0 A g-1. Moreover, the porous Ni-Co-Mn oxides prisms were also employed as positive electrode materials to assemble flexible solid-state asymmetric supercapacitors. The resulting flexible device had a maximum volumetric energy density (0.885 mW h cm-3) and power density (48.9 mW cm-3). Encouragingly, the flexible device exhibited good cycling stability with only about 2.2% loss after 5000 charge-discharge cycles and excellent mechanical stability. These results indicate that porous Ni-Co-Mn oxides prisms have the promising application in high performance electrochemical energy storage.

Preparation of lignin-based carbon aerogels as biomaterials for nano-supercapacitor

NASA Astrophysics Data System (ADS)

Yang, Bong Suk; Kang, Kyu-Young; Jeong, Myung-Joon

2017-10-01

Kraft and organosolv lignins, generally produced in chemical pulping and bio-refinery processes of lignocellulosic biomass, were used to prepare lignin-based carbon aerogels for supercapacitors as raw materials. The difference between lignins and lignin-based aerogels were compared by analyzing physical and chemical properties, including molecular weight, polydispersity, and reactivity with formaldehyde. Also, density, shrinkage, Brunauer-Emmett-Teller (BET) surface area and scanning electron microscope (SEM) images of the lignin-based aerogel were investigated. Kraft lignin consisting of coniferyl alcohol (G) and p-coumaryl alcohol (H) increased the reactivity of formaldehyde, formed a hydrogel well (porosity > 0.45), and specific surface area higher than organosolv lignin. In the case of kraft lignin, there were irregular changes such as oxidation and condensation in the pulping process. However, reaction sites with aromatic rings in lignin impacted the production of aerogel and required a long gelation period. The molecular weight of lignin influences the gelation time in producing lignin-based aerogel, and lignin composition affects the BET surface area and pore structures of the lignin-based carbon aerogels.

Effect of bead milling on chemical and physical characteristics of activated carbons pulverized to superfine sizes.

PubMed

Partlan, Erin; Davis, Kathleen; Ren, Yiran; Apul, Onur Guven; Mefford, O Thompson; Karanfil, Tanju; Ladner, David A

2016-02-01

Superfine powdered activated carbon (S-PAC) is an adsorbent material with particle size between roughly 0.1-1 μm. This is about an order of magnitude smaller than conventional powdered activated carbon (PAC), typically 10-50 μm. S-PAC has been shown to outperform PAC for adsorption of various drinking water contaminants. However, variation in S-PAC production methods and limited material characterization in prior studies lead to questions of how S-PAC characteristics deviate from that of its parent PAC. In this study, a wet mill filled with 0.3-0.5 mm yttrium-stabilized zirconium oxide grinding beads was used to produce S-PAC from seven commercially available activated carbons of various source materials, including two coal types, coconut shell, and wood. Particle sizes were varied by changing the milling time, keeping mill power, batch volume, and recirculation rate constant. As expected, mean particle size decreased with longer milling. A lignite coal-based carbon had the smallest mean particle diameter at 169 nm, while the wood-based carbon had the largest at 440 nm. The wood and coconut-shell based carbons had the highest resistance to milling. Specific surface area and pore volume distributions were generally unchanged with increased milling time. Changes in the point of zero charge (pH(PZC)) and oxygen content of the milled carbons were found to correlate with an increasing specific external surface area. However, the isoelectric point (pH(IEP)), which measures only external surfaces, was unchanged with milling and also much lower in value than pH(PZC). It is likely that the outer surface is easily oxidized while internal surfaces remain largely unchanged, which results in a lower average pH as measured by pH(PZC). Copyright © 2015 Elsevier Ltd. All rights reserved.

Pore size dependent molecular adsorption of cationic dye in biomass derived hierarchically porous carbon.

PubMed

Chen, Long; Ji, Tuo; Mu, Liwen; Shi, Yijun; Wang, Huaiyuan; Zhu, Jiahua

2017-07-01

Hierarchically porous carbon adsorbents were successfully fabricated from different biomass resources (softwood, hardwood, bamboo and cotton) by a facile two-step process, i.e. carbonization in nitrogen and thermal oxidation in air. Without involving any toxic/corrosive chemicals, large surface area of up to 890 m 2 /g was achieved, which is comparable to commercial activated carbon. The porous carbons with various surface area and pore size were used as adsorbents to investigate the pore size dependent adsorption phenomenon. Based on the density functional theory, effective (E-SSA) and ineffective surface area (InE-SSA) was calculated considering the geometry of used probing adsorbate. It was demonstrated that the adsorption capacity strongly depends on E-SSA instead of total surface area. Moreover, a regression model was developed to quantify the adsorption capacities contributed from E-SSA and InE-SSA, respectively. The applicability of this model has been verified by satisfactory prediction results on porous carbons prepared in this work as well as commercial activated carbon. Revealing the pore size dependent adsorption behavior in these biomass derived porous carbon adsorbents will help to design more effective materials (either from biomass or other carbon resources) targeting to specific adsorption applications. Copyright © 2017 Elsevier Ltd. All rights reserved.

Robust, self-assembled, biocompatible films

DOEpatents

Swanson, Basil I; Anderson, Aaron S.; Dattelbaum, Andrew M.; Schmidt, Jurgen G.

2014-06-24

The present invention provides a composite material including a substrate having an oxide surface, and, a continuous monolayer on the oxide surface, the monolayer including a silicon atom from a trifunctional alkyl/alkenyl/alkynyl silane group that attaches to the oxide surface, an alkyl/alkenyl/alkynyl portion of at least three carbon atoms, a polyalkylene glycol spacer group, and either a reactive site (e.g., a recognition ligand) or a site resistant to non-specific binding (e.g., a methoxy or the like) at the terminus of each modified SAM. The present invention further provides a sensor element, a sensor array and a method of sensing, each employing the composite material. Patterning is also provided together with backfilling to minimize non-specific binding.

Influence of specific surface area on coal dust explosibility using the 20-L chamber.

PubMed

Zlochower, Isaac A; Sapko, Michael J; Perera, Inoka E; Brown, Connor B; Harris, Marcia L; Rayyan, Naseem S

2018-07-01

The relationship between the explosion inerting effectiveness of rock dusts on coal dusts, as a function of the specific surface area (cm 2 /g) of each component is examined through the use of 20-L explosion chamber testing. More specifically, a linear relationship is demonstrated for the rock dust to coal dust (or incombustible to combustible) content of such inerted mixtures with the specific surface area of the coal and the inverse of that area of the rock dust. Hence, the inerting effectiveness, defined as above, is more generally linearly dependent on the ratio of the two surface areas. The focus on specific surface areas, particularly of the rock dust, provide supporting data for minimum surface area requirements in addition to the 70% less than 200 mesh requirement specified in 30 CFR 75.2.

Prediction of Surface and pH-Specific Binding of Peptides to Metal and Oxide Nanoparticles

NASA Astrophysics Data System (ADS)

Heinz, Hendrik; Lin, Tzu-Jen; Emami, Fateme Sadat; Ramezani-Dakhel, Hadi; Naik, Rajesh; Knecht, Marc; Perry, Carole C.; Huang, Yu

2015-03-01

The mechanism of specific peptide adsorption onto metallic and oxidic nanostructures has been elucidated in atomic resolution using novel force fields and surface models in comparison to measurements. As an example, variations in peptide adsorption on Pd and Pt nanoparticles depending on shape, size, and location of peptides on specific bounding facets are explained. Accurate computational predictions of reaction rates in C-C coupling reactions using particle models derived from HE-XRD and PDF data illustrate the utility of computational methods for the rational design of new catalysts. On oxidic nanoparticles such as silica and apatites, it is revealed how changes in pH lead to similarity scores of attracted peptides lower than 20%, supported by appropriate model surfaces and data from adsorption isotherms. The results demonstrate how new computational methods can support the design of nanoparticle carriers for drug release and the understanding of calcification mechanisms in the human body.

Mesoporous transition metal oxides quasi-nanospheres with enhanced electrochemical properties for supercapacitor applications.

PubMed

Wang, Lu; Duan, Guorong; Zhu, Junwu; Chen, Shen-Ming; Liu, Xiao-Heng; Palanisamy, Selvakumar

2016-12-01

In this report, we obtain mesoporous transition metal oxides quasi-nanospheres (includes MnO2, NiO, and Co3O4) by utilizing mesoporous silica nanospheres as a template for high-performance supercapacitor electrodes. All samples have a large specific surface area of approximately 254-325m(2)g(-1) and a relatively narrow pore size distribution in the region of 7nm. Utilization of a nanosized template resulted in a product with a relative uniform morphology and a small particle diameter in the region of 50-100nm. As supercapacitor electrodes, MnO2, NiO, and Co3O4 exhibit an outstanding capacity as high as 838-1185Fg(-1) at 0.5Ag(-1) and a superior long-term stability with minimal loss of 3-7% after 6000 cycles at 1Ag(-1). Their excellent electrochemical performances are attributed to favorable morphologies with a large surface area and a uniform architecture with abundant pores. The associated enhancement of electrolyte ion circulation within the electrode facilitates a significant increase in availability of Faradic reaction electroactive sites. Copyright © 2016 Elsevier Inc. All rights reserved.

Distinctive toxicity of TiO2 rutile/anatase mixed phase nanoparticles on Caco-2 cells.

PubMed

Gerloff, Kirsten; Fenoglio, Ivana; Carella, Emanuele; Kolling, Julia; Albrecht, Catrin; Boots, Agnes W; Förster, Irmgard; Schins, Roel P F

2012-03-19

Titanium dioxide has a long-standing use as a food additive. Micrometric powders are, e.g., applied as whiteners in confectionary or dairy products. Possible hazards of ingested nanometric TiO(2) particles for humans and the potential influence of varying specific surface area (SSA) are currently under discussion. Five TiO(2)-samples were analyzed for purity, crystallinity, primary particle size, SSA, ζ potential, and aggregation/agglomeration. Their potential to induce cytotoxicity, oxidative stress, and DNA damage was evaluated in human intestinal Caco-2 cells. Only anatase-rutile containing samples, in contrast to the pure anatase samples, induced significant LDH leakage or mild DNA damage (Fpg-comet assay). Evaluation of the metabolic competence of the cells (WST-1 assay) revealed a highly significant correlation between the SSA of the anatase samples and cytotoxicity. The anatase/rutile samples showed higher toxicity per unit surface area than the pure anatase powders. However, none of the samples affected cellular markers of oxidative stress. Our findings suggest that both SSA and crystallinity are critical determinants of TiO(2)-toxicity toward intestinal cells. © 2012 American Chemical Society

Liquefied petroleum gas sensor based on manganese (III) oxide and zinc manganese (III) oxide nanoparticles

NASA Astrophysics Data System (ADS)

Sharma, Shiva; Chauhan, Pratima; Husain, Shahid

2018-01-01

In this paper, {{{Mn}}}2{{{O}}}3 and {{{ZnMn}}}2{{{O}}}4 nanoparticles (NPs) are successfully synthesized using chemical co-precipitation method at room temperature and further annealed at 450 °C. The structure, crystallite size, morphology, specific surface area (SSA) and band gap energy have been determined by x-ray diffraction, transmission electron microscopy, Brunauer-Emmett-Teller surface area analysis, scanning electron microscopy (SEM-EDS) and UV-visible spectrophotometer. The sensor films of the {{{Mn}}}2{{{O}}}3 NPs and {{{ZnMn}}}2{{{O}}}4 NPs have been fabricated onto glass substrate using spin coater system separately. These sensor films are investigated for different concentrations (200-1200 ppm) of liquefied petroleum gas (LPG) at different operating temperatures ranging from 100 °C to 400 °C. A comparative study of gas sensing properties shows that spinel {{{ZnMn}}}2{{{O}}}4 sensor film exhibit excellent response (≈ 80 % ) towards 1000 ppm LPG at 300 °C in comparison to {{{Mn}}}2{{{O}}}3 sensor films. The enhancement in the gas sensing characteristics of {{{ZnMn}}}2{{{O}}}4 sensor film is attributed to the reduced crystallite size, greater SSA, and modification in structure as well as morphology.

Characterization of un-hydrated and hydrated BioAggregate™ and MTA Angelus™.

PubMed

Camilleri, J; Sorrentino, F; Damidot, D

2015-04-01

BioAggregate™ is a novel material introduced for use as a root-end filling material. It is tricalcium silicate-based, free of aluminium and uses tantalum oxide as radiopacifier. BioAggregate contains additives to enhance the material performance. The purpose of this research was to characterize the un-hydrated and hydrated forms of BioAggregate using a combination of techniques, verify whether the additives if present affect the properties of the set material and compare these properties to those of MTA Angelus™. Un-hydrated and hydrated BioAggregate and MTA Angelus were assessed. Un-hydrated cement was tested for chemical composition, specific surface area, mineralogy and kinetics of hydration. The set material was investigated for mineralogy, microstructure and bioactivity. Scanning electron microscopy, X-ray energy dispersive spectroscopic analysis, X-ray fluorescence spectroscopy, X-ray diffraction and isothermal calorimetry were employed. The specific surface area was investigated using a gas adsorption method with nitrogen as the probe. BioAggregate was composed of tricalcium silicate, tantalum oxide, calcium phosphate and silicon dioxide and was free of aluminium. On hydration, the tricalcium silicate produced calcium silicate hydrate and calcium hydroxide. The former was deposited around the cement grains, while the latter reacted with the silicon dioxide to form additional calcium silicate hydrate. This resulted in reduction of calcium hydroxide in the aged cement. MTA Angelus reacted in a similar fashion; however, since it contained no additives, the calcium hydroxide was still present in the aged cement. Bioactivity was demonstrated by deposition of hydroxyapatite. BioAggregate exhibited a high specific surface area. Nevertheless, the reactivity determined by isothermal calorimetry appeared to be slow compared to MTA Angelus. The tantalum oxide as opposed to bismuth oxide was inert, and tantalum was not leached in solution. BioAggregate exhibited high calcium ion release early, which was maintained over the 28-day period as opposed to MTA Angelus, which demonstrated low early calcium ion release which increased as the material aged. The mineralogical composition of BioAggregate was different to MTA Angelus. As opposed to MTA Angelus, BioAggregate did not contain aluminium and contained additives such as calcium phosphate and silicon dioxide. As a consequence, BioAggregate reacted more slowly and formation of calcium hydroxide and leaching of calcium ions in solution were not evident as the material aged. The additives in BioAggregate modify the kinetics and the end products of hydration. Although newer generation tricalcium silicate-based materials contain similar constituents to MTA, they do not undergo the same setting reactions, and thus, their clinical performance will not be comparable to that of MTA.

Packaging material and flexible medical tubing containing thermally exfoliated graphite oxide

NASA Technical Reports Server (NTRS)

Prud'homme, Robert K. (Inventor); Aksay, Ilhan A. (Inventor)

2011-01-01

A packaging material or flexible medical tubing containing a modified graphite oxide material, which is a thermally exfoliated graphite oxide with a surface area of from about 300 m.sup.2/g to 2600 m.sup.2/g.

Manganese oxide nanowires wrapped with nitrogen doped carbon layers for high performance supercapacitors.

PubMed

Li, Ying; Mei, Yuan; Zhang, Lin-Qun; Wang, Jian-Hai; Liu, An-Ran; Zhang, Yuan-Jian; Liu, Song-Qin

2015-10-01

In this study, manganese oxide nanowires wrapped by nitrogen-doped carbon layers (MnO(x)@NCs) were prepared by carbonization of poly(o-phenylenediamine) layer coated onto MnO2 nanowires for high performance supercapacitors. The component and structure of the MnO(x)@NCs were controlled through carbonization procedure under different temperatures. Results demonstrated that this composite combined the high conductivity and high specific surface area of nitrogen-doped carbon layers with the high pseudo-capacitance of manganese oxide nanowires. The as-prepared MnO(x)@NCs exhibited superior capacitive properties in 1 M Na2SO4 aqueous solution, such as high conductivity (4.167×10(-3) S cm(-1)), high specific capacitance (269 F g(-1) at 10 mV s(-1)) and long cycle life (134 F g(-1) after 1200 cycles at a scan rate of 50 mV s(-1)). It is reckoned that the present novel hybrid nanowires can serve as a promising electrode material for supercapacitors and other electrochemical devices. Copyright © 2015 Elsevier Inc. All rights reserved.

Reduced graphite oxide in supercapacitor electrodes.

PubMed

Lobato, Belén; Vretenár, Viliam; Kotrusz, Peter; Hulman, Martin; Centeno, Teresa A

2015-05-15

The current energy needs have put the focus on highly efficient energy storage systems such as supercapacitors. At present, much attention focuses on graphene-like materials as promising supercapacitor electrodes. Here we show that reduced graphite oxide offers a very interesting potential. Materials obtained by oxidation of natural graphite and subsequent sonication and reduction by hydrazine achieve specific capacitances as high as 170 F/g in H2SO4 and 84F/g in (C2H5)4NBF4/acetonitrile. Although the particle size of the raw graphite has no significant effect on the physico-chemical characteristics of the reduced materials, that exfoliated from smaller particles (<75 μm) result more advantageous for the release of the stored electrical energy. This effect is particularly evident in the aqueous electrolyte. Graphene-like materials may suffer from a drop in their specific surface area upon fabrication of electrodes with features of the existing commercial devices. This should be taken into account for a reliable interpretation of their performance in supercapacitors. Copyright © 2015 Elsevier Inc. All rights reserved.

Impact of Exposure to Pressure of 50 MPa on the Specific Surface Area of Clay

NASA Astrophysics Data System (ADS)

Koszela-Marek, Ewa

2017-12-01

The paper presents results of laboratory tests conducted to determine the impact of pressure of 50 MPa on specific surface area of clay. These tests were carried out in an original, high-pressure test stand. The specific surface area of clay extracted directly from an open pit mine was compared with the specific surface area of the same clay subjected to the pressure of 50 MPa in a high-pressure chamber. The study found that the specific surface area of the clay subjected to the pressure of 50 MPa increased distinctly by over 35 %. The increase in specific surface can be a result of changes in the microstructure of clay particles and microstructural alteration in the soil skeleton, caused by the pressure.

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.

Carbon Materials Research

DTIC Science & Technology

2005-08-01

is an angular surface. This phenomena has important applications in areas as diverse as heat exchange and catalysis. JOURNAL PAPERS W.P...densify these composites. In addressing the oxidation protection of carbon-carbon composites, the entirely new field of microtube technology was born...nozzle; exit cone; missile nosetip; hypersonic vehicle; oxidation resistance; cost; densification; MEMs; surface tension; microtube 16. SECURITY

Control of the Pore Texture in Nanoporous Silicon via Chemical Dissolution.

PubMed

Secret, Emilie; Wu, Chia-Chen; Chaix, Arnaud; Galarneau, Anne; Gonzalez, Philippe; Cot, Didier; Sailor, Michael J; Jestin, Jacques; Zanotti, Jean-Marc; Cunin, Frédérique; Coasne, Benoit

2015-07-28

The surface and textural properties of porous silicon (pSi) control many of its physical properties essential to its performance in key applications such as optoelectronics, energy storage, luminescence, sensing, and drug delivery. Here, we combine experimental and theoretical tools to demonstrate that the surface roughness at the nanometer scale of pSi can be tuned in a controlled fashion using partial thermal oxidation followed by removal of the resulting silicon oxide layer with hydrofluoric acid (HF) solution. Such a process is shown to smooth the pSi surface by means of nitrogen adsorption, electron microscopy, and small-angle X-ray and neutron scattering. Statistical mechanics Monte Carlo simulations, which are consistent with the experimental data, support the interpretation that the pore surface is initially rough and that the oxidation/oxide removal procedure diminishes the surface roughness while increasing the pore diameter. As a specific example considered in this work, the initial roughness ξ ∼ 3.2 nm of pSi pores having a diameter of 7.6 nm can be decreased to 1.0 nm following the simple procedure above. This study allows envisioning the design of pSi samples with optimal surface properties toward a specific process.

Platinum and Palladium Overlayers Dramatically Enhance the Activity of Ruthenium Nanotubes for Alkaline Hydrogen Oxidation

DOE PAGES

St. John, Samuel; Atkinson, Robert W.; Unocic, Kinga A.; ...

2015-10-18

Templated vapor synthesis and thermal annealing were used to synthesize unsupported metallic Ru nanotubes with Pt or Pd overlayers. By controlling the elemental composition and thickness of these overlayers, we obtain nanostructures with very high alkaline hydrogen oxidation activity. For nanotubes with a nominal atomic composition of Ru 0.90Pt 0.10 display a surface-specific activity (2.4 mA/cm 2) that is 35 times greater than that of pure Ru nanotubes at a 50 mV overpotential and 2.5 times greater than that of pure Pt nanotubes (0.98 mA/cm 2). The surface-segregated structure also confers dramatically increased Pt utilization efficiency. We find a platinum-mass-specificmore » activity of 1240 A/gPt for the optimized nanotube versus 280 A/gPt for carbon-supported Pt nanoparticles and 109 A/gPt for monometallic Pt nanotubes. Here, we attribute the enhancement of both area- and platinum-mass-specific activity to the atomic-scale homeomorphism of the nanotube form factor with adlayer-modified polycrystals. Subsurface ligand and bifunctional effects previously observed on segregated, adlayer-modified polycrystals are translated to nanoscale catalysts.« less

Influence of surface oxides on the adsorption of naphthalene onto multiwalled carbon nanotubes.

PubMed

Cho, Hyun-Hee; Smith, Billy A; Wnuk, Joshua D; Fairbrother, D Howard; Ball, William P

2008-04-15

As greater quantities of carbon nanotubes (CNTs) enter the environment, they will have an increasingly important effect on the availability and transport of aqueous contaminants. As a consequence of purification, deliberate surface functionalization, and/or exposure to oxidizing agents after release to the environment, CNTs often contain surface oxides (i.e., oxygen containing functional groups). To probe the influence that surface oxides exert on CNT sorption properties, multiwalled CNTs (MWCNTs) with varying oxygen concentrations were studied with respect to their sorption properties toward naphthalene. For pristine (as-received) MWCNTs, the sorption capacity was intermediate between that of a natural char and a granular activated carbon. Sorption data also reveal that a linear relationship exists between the oxygen content of MWCNTs and their maximum adsorption capacity for naphthalene, with 10% surface oxygen concentration resulting in a roughly 70% decrease in maximum adsorption capacity. The relative distribution of sorption energies, as characterized by Freundlich isotherm exponents was, however, unaffected by oxidation. Thus, the data are consistent with the idea that incorporated surface oxides create polar regions that reduce the surface area available for naphthalene sorption. These results highlight the important role of surface chemistry in controlling the environmental properties of CNTs.

Pseudocapacitive performance of electrodeposited porous Co3O4 film on electrophoretically modified graphite electrodes with carbon nanotubes

NASA Astrophysics Data System (ADS)

Kazazi, Mahdi; Sedighi, Ali Reza; Mokhtari, Mohammad Amin

2018-05-01

A facile and efficient two-step procedure was developed for the fabrication of a high-performance and binder-free cobalt oxide-carbon nanotubes (CO/CNT) pseudocapacitive electrode. First, CNTs were deposited on the surface of a chemically activated graphite sheet by cathodic electrophoretic deposition technique from their ethanolic suspension. In the next step, a thin film of cobalt oxide was electrodeposited on the CNTs coated graphite substrate by a galvanostatic method, followed by a thermal treatment in air. The structure and morphology of the prepared cobaltite electrode with and without CNT interlayer were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM) and nitrogen adsorption-desorption measurement. The results indicated that Co3O4 nanoparticles were uniformly attached on the surface of CNTs, to form a porous-structured CO/CNT composite electrode with a high specific surface area of 144.9 m2 g-1. Owing to the superior electrical conductivity of CNTs, high surface area and open porous structure, and improved integrity of the electrode structure, the composite electrode delivered a high areal capacitance of 4.96F cm-2 at a current density of 2 mA cm-2, a superior rate performance (64.7% capacitance retention from 2 mA cm-2 to 50 mA cm-2), as well as excellent cycling stability (91.8% capacitance retention after 2000 cycles), which are higher than those of the pure cobaltite electrode.

Size- and shape-controlled synthesis and catalytic performance of iron-aluminum mixed oxide nanoparticles for NOX and SO₂ removal with hydrogen peroxide.

PubMed

Ding, Jie; Zhong, Qin; Zhang, Shule; Cai, Wei

2015-01-01

A novel, simple, reproducible and low-cost strategy is introduced for the size- and shape-controlled synthesis of iron-aluminum mixed oxide nanoparticles (NIAO(x/y)). The as-synthesized NIAO(x/y) catalyze decomposition of H2O2 yielding highly reactive hydroxyl radicals (OH) for NOX and SO2 removal. 100% SO2 removal is achieved. NIAO(x/y) with Fe/Al molar ratio of 7/3 (NIAO(7/3)) shows the highest NOX removal of nearly 80% at >170°C, whereas much lower NOX removal (<63%) is obtained for NIAO(3/7). The melting of aluminum oxides in NIAO(7/3) promotes the formation of lamellar products, thus improving the specific surface areas and mesoporous distribution, benefiting the production of OH radicals. Furthermore, the NIAO(7/3) leads to the minor increase of points of zero charges (PZC), apparent enhancement of FeOH content and high oxidizing ability of Fe(III), further improving the production of OH radicals. However, the NIAO(3/7) results in the formation of aluminum surface-enriched spherical particles, thus decreasing the surface atomic ratio of iron oxides, decreasing OH radical production. More importantly, the generation of FeOAl causes the decline of active sites. Finally, the catalytic decomposition of H2O2 on NIAO(x/y) is proposed. And the well catalytic stability of NIAO(7/3) is obtained for evaluation of 30 h. Copyright © 2014 Elsevier B.V. All rights reserved.

Corrosion Experiments Using Spherical Uranium Powders

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

Powell, G. L.; Siekhaus, W. J.; Teslich, N. E.

2017-02-01

Corrosion experiments using spherical U powders are continuing with scanning electron microscopy (SEM) showing that the particles are highly textured, 5 m to 25 m diameters with 4% larger particles that are fused smaller particles. This U has a high specific surface area with no corners or back-sides, is well annealed with no machining work, and coated with a coherent oxide film, 30 nm to 300 nm thick. Exposure of this powder to low vapor pressure H 2O in the absence of O 2, i.e., a vacuum desiccator, resulted in a coherent oxide film growth of ~1 m/y, ~ 10Xmore » the growth rate in ambient air, displaying fracture along the growth plane at ~300 nm.« less

Spinel lithium manganese oxide nanoparticles: unique molten salt synthesis strategy and excellent electrochemical performances.

PubMed

Wang, Xiong; Zhu, Juanjuan; Liu, Yingjie

2009-11-01

As a promising candidate cathode material, spinel lithium manganese oxide nanoparticles were successfully synthesized through a novel molten salt synthesis route at relatively low temperature, using manganese dioxide nanowires as precursor. A variety of techniques were applied to characterize the spinel nanomaterial, including X-ray diffraction, transmission electron microscopy, field-emission scanning electron microscopy, and X-ray photoelectron spectroscopy. The average particle size of the resulting spinel nanoparticles was about 80 nm with narrow distribution. As cathode material for rechargeable lithium ion battery, the electrochemical properties were investigated. All the results show that the electrochemical performances of the homogeneous spinel nanoparticles were improved, which might be ascribed to large specific surface area, fairly narrow size distribution, and the unique synthesis strategy.

Influence of surface defects on the tensile strength of carbon fibers

NASA Astrophysics Data System (ADS)

Vautard, F.; Dentzer, J.; Nardin, M.; Schultz, J.; Defoort, B.

2014-12-01

The mechanical properties of carbon fibers, especially their tensile properties, are affected by internal and surface defects. In order to asses in what extent the generation of surface defects can result in a loss of the mechanical properties, non-surface treated carbon fibers were oxidized with three different surface treatment processes: electro-chemical oxidation, oxidation in nitric acid, and oxidation in oxygen plasma. Different surface topographies and surface chemistries were obtained, as well as different types and densities of surface defects. The density of surface defects was measured with both a physical approach (Raman spectroscopy) and a chemical approach (Active Surface Area). The tensile properties were evaluated by determining the Weibull modulus and the scale parameter of each reference, after measuring the tensile strength for four different gauge lengths. A relationship between the tensile properties and the nature and density of surface defects was noticed, as large defects largely control the value of the tensile strength. When optimized, some oxidation surface treatment processes can generate surface functional groups as well as an increase of the mechanical properties of the fibers, because of the removal of the contamination layer of pyrolytic carbon generated during the carbonization of the polyacrylonitrile precursor. Oxidation in oxygen plasma revealed to be a promising technology for alternative surface treatment processes, as high levels of functionalization were achieved and a slight improvement of the mechanical properties was obtained too.

The effect of grain size and surface area on organic matter, lignin and carbohydrate concentration, and molecular compositions in Peru Margin sediments

USGS Publications Warehouse

Bergamaschi, B.A.; Tsamakis, E.; Keil, R.G.; Eglinton, T.I.; Montlucon, D.B.; Hedges, J.I.

1997-01-01

A C-rich sediment sample from the Peru Margin was sorted into nine hydrodynamically-determined grain size fractions to explore the effect of grain size distribution and sediment surface area on organic matter content and composition. The neutral monomeric carbohydrate composition, lignin oxidation product yields, total organic carbon, and total nitrogen contents were determined independently for each size fraction, in addition to sediment surface area and abundance of biogenic opal. The percent organic carbon and percent total nitrogen were strongly related to surface area in these sediments. In turn, the distribution of surface area closely followed mass distribution among the textural size classes, suggesting hydrodynamic controls on grain size also control organic carbon content. Nevertheless, organic compositional distinctions were observed between textural size classes. Total neutral carbohydrate yields in the Peru Margin sediments were found to closely parallel trends in total organic carbon, increasing in abundance among grain size fractions in proportion to sediment surface area. Coincident with the increases in absolute abundance, rhamnose and mannose increased as a fraction of the total carbohydrate yield in concert with surface area, indicating these monomers were preferentially represented in carbohydrates associated with surfaces. Lignin oxidation product yields varied with surface area when normalized to organic carbon, suggesting that the terrestrially-derived component may be diluted by sorption of marine derived material. Lignin-based parameters suggest a separate source for terrestrially derived material associated with sand-size material as opposed to that associated with silts and clays. Copyright ?? 1997 Elsevier Science Ltd.

The effect of grain size and surface area on organic matter, lignin and carbohydrate concentration, and molecular compositions in Peru Margin sediments

NASA Astrophysics Data System (ADS)

Bergamaschi, Brian A.; Tsamakis, Elizabeth; Keil, Richard G.; Eglinton, Timothy I.; Montluçon, Daniel B.; Hedges, John I.

1997-03-01

A C-rich sediment sample from the Peru Margin was sorted into nine hydrodynamically-determined grain size fractions to explore the effect of grain size distribution and sediment surface area on organic matter content and composition. The neutral monomeric carbohydrate composition, lignin oxidation product yields, total organic carbon, and total nitrogen contents were determined independently for each size fraction, in addition to sediment surface area and abundance of biogenic opal. The percent organic carbon and percent total nitrogen were strongly related to surface area in these sediments. In turn, the distribution of surface area closely followed mass distribution among the textural size classes, suggesting hydrodynamic controls on grain size also control organic carbon content. Nevertheless, organic compositional distinctions were observed between textural size classes. Total neutral carbohydrate yields in the Peru Margin sediments were found to closely parallel trends in total organic carbon, increasing in abundance among grain size fractions in proportion to sediment surface area. Coincident with the increases in absolute abundance, rhamnose and mannose increased as a fraction of the total carbohydrate yield in concert with surface area, indicating these monomers were preferentially represented in carbohydrates associated with surfaces. Lignin oxidation product yields varied with surface area when normalized to organic carbon, suggesting that the terrestrially-derived component may be diluted by sorption of marine derived material. Lignin-based parameters suggest a separate source for terrestrially derived material associated with sand-size material as opposed to that associated with silts and clays.

Ethanedithiol-treated manganese oxide nanoparticles for rapidly responsive and transparent supercapacitors

NASA Astrophysics Data System (ADS)

Ryu, Ilhwan; Kim, Green; Park, Dasom; Yim, Sanggyu

2015-11-01

Metal oxide nanoparticles (NPs) provide a large surface area and short diffusion pathways for ions in supercapacitor electrode materials. However, binders and conductive additives used for tight connections with current collectors and improved conductivity hamper these benefits. In this work, we successfully fix manganese oxide (Mn3O4) NPs onto ITO current collectors by a simple 1,2-ethanedithiol (EDT) treatment without using any binders or conductive additives. As compared to the electrode fabricated using binder-mixed Mn3O4 NPs, the EDT-treated electrode shows significantly improved specific capacitance of 403 F g-1 at a scan rate of 10 mV s-1. The EDT-treatment is more effective at higher scan rates. The specific capacitances, 278 F g-1 at 100 mV s-1 and 202 F g-1 at 200 mV s-1, are larger than those reported so far at scan rates ≥100 mV s-1. The deconvolution of capacitive elements indicates that these improved capacitive properties are attributed to large insertion elements of the binder-free NP electrodes. Furthermore, this additive-free electrode is highly transparent and can be easily fabricated by simple spray-coating on various substrates including polymer films, implying that this new method is promising for the fabrication of large-area, transparent and flexible electrodes for next-generation supercapacitors.

Synthesis and visible light photocatalytic properties of iron oxide–silver orthophosphate composites

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

Febiyanto,; Eliani, Irma Vania; Riapanitra, Anung

2016-04-19

The iron oxide-silver orthophosphate composites were successfully synthesized by co-precipitation method using Fe(NO{sub 3}){sub 3}.9H{sub 2}O, AgNO{sub 3}, and Na{sub 2}HPO{sub 4}.12 H{sub 2}O, followed by calcination at 500°C for 5 hours. The Fe/Ag mole ratios of iron oxide-silver orthophosphate composites were designed at 0, 0.1, 0.2, 0.3 and 0.4. The samples were characterized using X-ray Diffraction, Diffuse Reflectance Spectroscopy, Scanning Electron Microscopy and Specific Surface Area. The photocatalytic activities were evaluated using Rhodamine B degradation under visible light irradiation. The iron oxide-silver orthophosphate composite with the Fe/Ag mole ratio of 0.2 exhibited higher photocatalytic activity compared to the puremore » Ag{sub 3}PO{sub 4} under visible light irradiation. The enhanced photocatalytic activity could be attributed to the effective separation of hole (+) and electron pairs in the iron oxide-silver orthophosphate composite.« less

A Sinter-Resistant Catalytic System Based on Platinum Nanoparticles Supported on TiO2 Nanofibers and Covered by Porous Silica

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

Dai, Yunqian; Lim, Byungkwon; Yang, Yong

2010-10-25

Platinum is a key catalyst that is invaluable in many important industrial processes such as CO oxidation in catalytic converters, oxidation and reduction reactions in fuel cells, nitric acid production, and petroleum cracking.[1] Many of these applications utilize Pt nanoparticles supported on oxides or porous carbon.[2] However, in practical applications that involve high temperatures (typically higher than 3008C), the Pt nanoparticles tend to lose their specific surface area and thus catalytic activity during operation because of sintering. Recent studies have shown that a porous oxide shell can act as a physical barrier to prevent sintering of unsupported metal nanoparticles and,more » at the same time, provide channels for chemical species to reach the surface of the nanoparticles, thus allowing the catalytic reaction to occur. This concept has been demonstrated in several systems, including Pt@SiO2,[3] Pt@CoO,[4] Pt/CeO2@SiO2,[5] Pd@SiO2,[6] Au@SiO2,[7] Au@SnO2 [8] and Au@ZrO2 [9] core– shell nanostructures. Despite these results, a sinter-resistant system has not been realized in supported Pt nanoparticle catalysts.« less

Synthesis of low-size flower-like AlOOH structures

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

Bakina, Olga V., E-mail: ovbakina@ispms.tsc.ru, E-mail: eagl@ispms.tsc.ru; Glazkova, Elena A., E-mail: ovbakina@ispms.tsc.ru, E-mail: eagl@ispms.tsc.ru; Lozhkomoev, Aleksandr S., E-mail: asl@ispms.tsc.ru

Al/Cu, Al/Zn, and Al/Fe bimetallic nanoparticles have been obtained using the method of simultaneous electrical explosion of metal pairs in an argon atmosphere. The nanoparticles are chemically active and interact with water at 60°C forming flower-like hierarchical porous structures with a high specific surface area. As the Al/Cu nanopowder is oxidized with water, flower-like pseudoboehmite composite structures are formed with the size of under 1.0 μm; structurally heterogeneous electron-dense spherical inclusions of unreacted metal copper and intermetallides are identified inside them. Al/Fe product transformations are presented by the flower-like pseudoboehmite surrounded by lamellar structures enriched with ferric oxides. Al/Zn nanoparticlesmore » react with water, forming the flower-like pseudoboehmite and mainly hexagonal zinc oxide laminae. The composite particles obtained can be used as antibacterial agents in manufacturing medical supplies.« less

Structural and surface properties of CuO-ZnO-Cr{sub 2}O{sub 3} catalysts and their relationship with selectivity to higher alcohol synthesis

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

Campos-Martin, J.M.; Fierro, J.L.G.; Guerrero-Ruiz, A.

1995-10-01

A series of copper-zinc-chromium catalysts of different compositions and calcination temperatures has been prepared, characterized by several techniques (BET specific surface area, XRD, gravimetric TPR, TPD-CO, and XPS), and tested under high alcohol synthesis (HAS) conditions. CO hydrogenation was carried out at reaction temperatures of 523-598 K and 50 bar total pressure. The influence of catalyst composition, calcination temperature, and surface characteristics on the HAS selectivity was studied. The optimum HAS yields were found in the low Cr content region, but chromium was needed. Although chromium oxide does not seem to be involved in the catalytic site, its presence inmore » the catalyst composition is essential, owing to the larger specific surfaces and catalyst stability obtained at the highest reaction temperatures. For low Cr content composition, the temperature-programmed reduction (TPR) profiles were shifted to higher temperatures and simultaneously larger CO{sub 2} amounts were found in the temperature-programmed desorption profiles of adsorbed CO (TPD-CO). Photoelectron spectra (XPS) revealed that the oxidation state of copper is Cu{sup 2+} in the calcined catalysts and Cu{sup O} in the reduced ones; Cu{sup +} was only stabilized in a CuCr{sub 2}O{sub 4} spinel in the Cr-rich catalysts. These features derived from catalyst characterization are discussed in the framework of the catalytic behaviour for HAS synthesis. 53 refs., 7 figs., 4 tabs.« less

Controllable in situ synthesis of epsilon manganese dioxide hollow structure/RGO nanocomposites for high-performance supercapacitors

NASA Astrophysics Data System (ADS)

Lin, Mei; Chen, Bolei; Wu, Xiao; Qian, Jiasheng; Fei, Linfeng; Lu, Wei; Chan, Lai Wa Helen; Yuan, Jikang

2016-01-01

Well-organized epsilon-MnO2 hollow spheres/reduced graphene oxide (MnO2HS/RGO) composites have been successfully constructed via a facile and one-pot synthetic route. The ε-MnO2 hollow spheres with the diameter of ~500 nm were grown in situ with homogeneous distribution on both sides of graphene oxide (GO) sheets in aqueous suspensions. The formation mechanism of the MnO2HS/RGO composites has been systematically investigated, and a high specific capacitance and good cycling capability were achieved on using the composites as supercapacitors. The galvanostatic charge/discharge curves show a specific capacitance of 471.5 F g-1 at 0.8 A g-1. The hollow structures of ε-MnO2 and the crumpled RGO sheets can enhance the electroactive surface area and improve the electrical conductivity, thus further facilitating the charge transport. The MnO2HS/RGO composite exhibits a high capacitance of 272 F g-1 at 3 A g-1 (92% retention) even after 1000 cycles. The prominent electrochemical performance might be attributed to the combination of the pseudo-capacitance of the MnO2 nanospheres with a hollow structure and to the good electrical conductivity of the RGO sheets. This work explores a new concept in designing metal oxides/RGO composites as electrode materials.Well-organized epsilon-MnO2 hollow spheres/reduced graphene oxide (MnO2HS/RGO) composites have been successfully constructed via a facile and one-pot synthetic route. The ε-MnO2 hollow spheres with the diameter of ~500 nm were grown in situ with homogeneous distribution on both sides of graphene oxide (GO) sheets in aqueous suspensions. The formation mechanism of the MnO2HS/RGO composites has been systematically investigated, and a high specific capacitance and good cycling capability were achieved on using the composites as supercapacitors. The galvanostatic charge/discharge curves show a specific capacitance of 471.5 F g-1 at 0.8 A g-1. The hollow structures of ε-MnO2 and the crumpled RGO sheets can enhance the electroactive surface area and improve the electrical conductivity, thus further facilitating the charge transport. The MnO2HS/RGO composite exhibits a high capacitance of 272 F g-1 at 3 A g-1 (92% retention) even after 1000 cycles. The prominent electrochemical performance might be attributed to the combination of the pseudo-capacitance of the MnO2 nanospheres with a hollow structure and to the good electrical conductivity of the RGO sheets. This work explores a new concept in designing metal oxides/RGO composites as electrode materials. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr07900d

Self-Assembly Template Driven 3D Inverse Opal Microspheres Functionalized with Catalyst Nanoparticles Enabling a Highly Efficient Chemical Sensing Platform.

PubMed

Wang, Tianshuang; Can, Inci; Zhang, Sufang; He, Junming; Sun, Peng; Liu, Fangmeng; Lu, Geyu

2018-02-14

The design of semiconductor metal oxides (SMOs) with well-ordered porous structure has attracted tremendous attention owing to their larger specific surface area. Herein, three-dimensional inverse opal In 2 O 3 microspheres (3D-IO In 2 O 3 MSs) were fabricated through one-step ultrasonic spray pyrolysis (USP) which employed self-assembly sulfonated polystyrene (S-PS) spheres as a sacrificial template. The spherical pores observed in the 3D-IO In 2 O 3 MSs had diameters of about 4 and 80 nm. Subsequently, the catalytic palladium oxide nanoparticles (PdO NPs) were loaded on 3D-IO In 2 O 3 MSs via a simple impregnation method, and their gas sensing properties were investigated. In a comparison with pristine 3D-IO In 2 O 3 MSs, the 3D-IO PdO@In 2 O 3 MSs exhibited a 3.9 times higher response (R air /R gas = 50.9) to 100 ppm acetone at 250 °C and a good acetone selectivity. The detection limit for acetone could extend down to ppb level. Furthermore, the 3D-IO PdO@In 2 O 3 MSs-based sensor also possess good long-term stability. The extraordinary sensing performance can be attributed to the novel 3D periodic porous structure, highly three-dimensional interconnection, larger specific surface area, size-tunable (meso- and macroscale) bimodal pores, and PdO NP catalysts.

Co@Carbon and Co 3 O4@Carbon nanocomposites derived from a single MOF for supercapacitors.

PubMed

Dai, Engao; Xu, Jiao; Qiu, Junjie; Liu, Shucheng; Chen, Ping; Liu, Yi

2017-10-03

Developing a composite electrode containing both carbon and transition metal/metal oxide as the supercapacitor electrode can combine the merits and mitigate the shortcomings of both the components. Herein, we report a simple strategy to prepare the hybrid nanostructure of Co@Carbon and Co 3 O 4 @Carbon by pyrolysis a single MOFs precursor. Co-based MOFs (Co-BDC) nanosheets with morphology of regular parallelogram slice have been prepared by a bottom-up synthesis strategy. One-step pyrolysis of Co-BDC, produces a porous carbon layer incorporating well-dispersed Co and Co 3 O 4 nanoparticles. The as-prepared cobalt-carbon composites exhibit the thin layer morphology and large specific surface area with hierarchical porosity. These features significantly improve the ion-accessible surface area for charge storage and shorten the ion transport length in thin dimension, thus contributing to a high specific capacitance. Improved capacitance performance was successfully realized for the asymmetric supercapacitors (ASCs) (Co@Carbon//Co 3 O 4 @Carbon), better than those of the symmetric supercapacitors (SSCs) based on Co@Carbon and Co 3 O 4 @Carbon materials (i.e., Co@Carbon//Co@Carbon and Co 3 O 4 @Carbon//Co 3 O 4 @Carbon). The working voltage of the ASCs can be extended to 1.5 V and show a remarkable high power capability in aqueous electrolyte. This work provides a controllable strategy for nanostructured carbon-metal and carbon-metal oxide composite electrodes from a single precursor.

Modification of implant material surface properties by means of oxide nano-structured coatings deposition

NASA Astrophysics Data System (ADS)

Safonov, Vladimir; Zykova, Anna; Smolik, Jerzy; Rogowska, Renata; Lukyanchenko, Vladimir; Kolesnikov, Dmitrii

2014-08-01

The deposition of functional coatings on the metal surface of artificial joints is an effective way of enhancing joint tribological characteristics. It is well-known that nanostructured oxide coatings have specific properties advantageous for future implant applications. In the present study, we measured the high hardness parameters, the adhesion strength and the low friction coefficient of the oxide magnetron sputtered coatings. The corrosion test results show that the oxide coating deposition had improved the corrosion resistance by a factor of ten for both stainless steel and titanium alloy substrates. Moreover, the hydrophilic nature of coated surfaces in comparison with the metal ones was investigated in the tensiometric tests. The surfaces with nanostructured oxide coatings demonstrated improved biocompatibility for in vitro and in vivo tests, attributed to the high dielectric constants and the high values of the surface free energy parameters.

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

NASA Astrophysics Data System (ADS)

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

2017-04-01

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

Ethylene oxide-block-butylene oxide copolymer uptake by silicone hydrogel contact lens materials

NASA Astrophysics Data System (ADS)

Huo, Yuchen; Ketelson, Howard; Perry, Scott S.

2013-05-01

Four major types of silicone hydrogel contact lens material have been investigated following treatments in aqueous solutions containing poly(ethylene oxide) and poly(butylenes oxide) block copolymer (EO-BO). The extent of lens surface modification by EO-BO and the degree of bulk uptake were studied using X-ray photoelectron spectroscopy (XPS) and ultra-performance liquid chromatography (UPLC), respectively. The experimental results suggest that different interaction models exist for the lenses, highlighting the influence of both surface and bulk composition, which greatly differs between the lenses examined. Specifically, lenses with hydrophilic surface treatments, i.e., PureVision® (balafilcon A) and O2OPTIX (lotrafilcon B), demonstrated strong evidence of preferential surface adsorption within the near-surface region. In comparison, surface adsorption on ACUVUE® Oasys® (senofilcon A) and Biofinity® (comfilcon A) was limited. As for bulk absorption, the amount of EO-BO uptake was the greatest for balafilcon A and comfilcon A, and least for lotrafilcon B. These findings confirm the presence of molecular concentration gradients within the silicone hydrogel lenses following exposure to EO-BO solutions, with the nature of such concentration gradients found to be lens-specific. Together, the results suggest opportunities for compositional modifications of lenses for improved performance via solution treatments containing surface-active agents.

Automotive body panel containing thermally exfoliated graphite oxide

NASA Technical Reports Server (NTRS)

Aksay, Ilhan A. (Inventor); Abdala, Ahmed (Inventor); Prud'Homme, Robert K. (Inventor); Adamson, Douglas (Inventor)

2011-01-01

An automotive body panel containing a polymer composite formed of at least one polymer and a modified graphite oxide material, which is a thermally exfoliated graphite oxide with a surface area of from about 300 m.sup.2/g to 2600 m.sup.2/g.

Non-activated high surface area expanded graphite oxide for supercapacitors

NASA Astrophysics Data System (ADS)

Vermisoglou, E. C.; Giannakopoulou, T.; Romanos, G. E.; Boukos, N.; Giannouri, M.; Lei, C.; Lekakou, C.; Trapalis, C.

2015-12-01

Microwave irradiation of graphite oxide constitutes a facile route toward production of reduced graphene oxide, since during this treatment both exfoliation and reduction of graphite oxide occurs. In this work, the effect of pristine graphite (type, size of flakes), pretreatment and oxidation cycles on the finally produced expanded material was examined. All the types of graphite that were tested afforded materials with high BET surface areas ranging from 940 m2/g to 2490 m2/g, without intervening an activation stage at elevated temperature. SEM and TEM images displayed exfoliated structures, where the flakes were significantly detached and curved. The quality of the reduced graphene oxide sheets was evidenced both by X-ray photoelectron spectroscopy and Raman spectroscopy. The electrode material capacitance was determined via electrochemical impedance spectroscopy and cyclic voltammetry. The materials with PEDOT binder had better performance (∼97 F/g) at low operation rates while those with PVDF binder performed better (∼20 F/g) at higher rates, opening up perspectives for their application in supercapacitors.

Microbiologically Influenced Corrosion

DTIC Science & Technology

2009-01-01

related directly to the biomineralized deposits on the surface. Ennoble- ment in marine waters has been attributed to depolarization of the oxygen... abiotic ally oxi- dized metal precipitates, and still others that derive energy by oxidizing metals. Manganese. Manganese oxidation is coupled to cell...circumstances, pitting involves the conventional features of differential aeration, a large cathode: anode surface area, and the development of

La and Al co-doped CaMnO 3 perovskite oxides: From interplay of surface properties to anion exchange membrane fuel cell performance

DOE PAGES

Dzara, Michael J.; Christ, Jason M.; Joghee, Prabhuram; ...

2017-09-01

This work reports the first account of perovskite oxide and carbon composite oxygen reduction reaction (ORR) catalysts integrated into anion exchange membrane fuel cells (AEMFCs). Perovskite oxides with a theoretical stoichiometry of Ca 0.9La 0.1Al 0.1Mn 0.9O 3-δ are synthesized by an aerogel method and calcined at various temperatures, resulting in a set of materials with varied surface chemistry and surface area. Material composition is evaluated by X-ray diffraction, energy dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy. The perovskite oxide calcined at 800 degrees C shows the importance of balance between surface area, purity of the perovskite phase, and surfacemore » composition, resulting in the highest ORR mass activity when evaluated in rotating disk electrodes. Integration of this catalyst into AEMFCs reveals that the best AEMFC performance is obtained when using composites with 30:70 perovskite oxide:carbon composition. Doubling the loading leads to an increase in the power density from 30 to 76 mW cm -2. The AEMFC prepared with a composite based on perovskite oxide and N-carbon achieves a power density of 44 mW cm -2, demonstrating an ~50% increase when compared to the highest performing composite with undoped carbon at the same loading.« less

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

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

Preliminary investigation of phosphorus adsorption onto two types of iron oxide-organic matter complexes.

PubMed

Yan, Jinlong; Jiang, Tao; Yao, Ying; Lu, Song; Wang, Qilei; Wei, Shiqiang

2016-04-01

Iron oxide (FeO) coated by natural organic matter (NOM) is ubiquitous. The associations of minerals with organic matter (OM) significantly changes their surface properties and reactivity, and thus affect the environmental fate of pollutants, including nutrients (e.g., phosphorus (P)). In this study, ferrihydrite/goethite-humic acid (FH/GE-HA) complexes were prepared and their adsorption characteristics on P at various pH and ionic strength were investigated. The results indicated that the FeO-OM complexes showed a decreased P adsorption capacity in comparison with bare FeO. The maximum adsorption capacity (Qmax) decreased in the order of FH (22.17 mg/g)>FH-HA (5.43 mg/g)>GE (4.67 mg/g)>GE-HA (3.27 mg/g). After coating with HA, the amorphous FH-HA complex still showed higher P adsorption than the crystalline GE-HA complex. The decreased P adsorption observed might be attributed to changes of the FeO surface charges caused by OM association. The dependence of P adsorption on the specific surface area of adsorbents suggests that the FeO component in the complexes is still the main contributor for the adsorption surfaces. The P adsorptions on FeO-HA complexes decreased with increasing initial pH or decreasing initial ionic strength. A strong dependence of P adsorption on ionic strength and pH may demonstrate that outer-sphere complexes between the OM component on the surface and P possibly coexist with inner-sphere surface complexes between the FeO component and P. Therefore, previous over-emphasis on the contributions of original minerals to P immobilization possibly over-estimates the P loading capacity of soils, especially in humic-rich areas. Copyright © 2015. Published by Elsevier B.V.

Efficient adsorption of Au(CN)2- from gold cyanidation with graphene oxide-polyethylenimine hydrogel as adsorbent

NASA Astrophysics Data System (ADS)

Yang, Lang; Jia, Feifei; Yang, Bingqiao; Song, Shaoxian

The adsorption of gold cyanide complex ion (Au(CN)2-) on graphene oxide-polyethylenimine hydrogel (GO/PEI hydrogel) from gold cyanidation has been studied to explore the possibility of the application of GO/PEI hydrogel in gold cyanidation process for extracting gold from ores. The adsorption was carried out in artificial Au(CN)2- aqueous solution with GO/PEI hydrogel as adsorbent. The experimental results, as well as IR, XPS and SEM-EDS, have shown that GO/PEI hydrogel exhibited a high adsorption capacity and a fast adsorption rate of Au(CN)2-, suggesting that GO/PEI hydrogel might be a good adsorbent for the recovery of Au(CN)2-. The adsorption of Au(CN)2- on GO/PEI hydrogel obeyed the Langmuir isotherm model and fitted well with the pseudo second order model. The good recovery of Au(CN)2- was largely related to the porous structure, large specific surface area, as well as the oxygenous functional groups on the surface of GO/PEI hydrogel.

Controllably annealed CuO-nanoparticle modified ITO electrodes: Characterisation and electrochemical studies

NASA Astrophysics Data System (ADS)

Wang, Tong; Su, Wen; Fu, Yingyi; Hu, Jingbo

2016-12-01

In this paper, we report a facile and controllable two-step approach to produce indium tin oxide electrodes modified by copper(II) oxide nanoparticles (CuO/ITO) through ion implantation and annealing methods. After annealing treatment, the surface morphology of the CuO/ITO substrate changed remarkably and exhibited highly electroactive sites and a high specific surface area. The effects of annealing treatment on the synthesis of CuO/ITO were discussed based on various instruments' characterisations, and the possible mechanism by which CuO nanoparticles were generated was also proposed in this work. Cyclic voltammetric results indicated that CuO/ITO electrodes exhibited effective catalytic responses toward glucose in alkaline solution. Under optimal experimental conditions, the proposed CuO/ITO electrode showed sensitivity of 450.2 μA cm-2 mM-1 with a linear range of up to ∼4.4 mM and a detection limit of 0.7 μM (S/N = 3). Moreover, CuO/ITO exhibited good poison resistance, reproducibility, and stability properties.

Heterogeneous Catalysts for VOC Oxidation from Red Mud and Bagasse Ash Carbon

NASA Astrophysics Data System (ADS)

Pande, Gaurav

A range of VOC oxidation catalysts have been prepared in this study from agricultural and industrial waste as the starting point. The aim is to prepare catalysts with non-noble metal oxides as the active catalytic component (iron in red mud). The same active component was also supported on activated carbon obtained from unburned carbon in bagasse ash. Red mud which is an aluminum industry waste and rich in different phases of iron as oxide and hydroxide is used as the source for the catalytically active species. It is our aim to enhance the catalytic performance of red mud which though high in iron concentration has a low surface area and may not have the properties of an ideal catalyst by itself. In one of the attempts to enhance the catalytic performance, we have tried to leach red mud for which we have explored a range of leaching acids for effecting the leaching most efficiently and then precipitated the iron from the leachate as its hydroxide by precipitating with alkali solution followed by drying and calcination to give high surface area metal oxide material. Extensive surface characterization and VOC oxidation catalytic testing were performed for these solids. In a step to further enhance the catalytic activity towards oxidation, copper was introduced by taking another industrial waste from the copper tubing industry viz. the pickling acid. Copper has a more favourable redox potential making it catalytically more effective than iron. To make the mixed metal oxide, red mud leachate was mixed with the pickling acid in a pre-decided ratio before precipitating with alkali solution followed by drying and calcination as was done with the red mud leachate. The results from these experiments are encouraging. The temperature programmed reduction (TPR) of the solids show that the precipitate of red mud leachates show hydrogen uptake peak at a lower temperature than for just the calcined red mud. This could be due to the greatly enhanced surface area of the prepared solids. The highest surface area of 311 m2/g was for the sample prepared from oxalic acid and l-ascorbic acid as the leaching acid; as received red mud has a surface area of 11.5 m2/g. This sample showed better catalytic performance than the ones made from hydrochloric acid as the leaching acid in spite of a similar increase in surface area. High temperature XRD shows the reason for this difference in catalytic properties could be due to both the solids reducing in a different way to give different phases though they are both derived from red mud as the starting material. Also, the sample prepared with oxalic acid leachate had higher surface iron concentration. For the best catalyst (oxalic acid derived) the light off temperature is about 300 °C for toluene oxidation. For solids prepared from red mud leachate for iron source and pickling acid for copper source, it was seen that the TPR gave hydrogen absorption at temperatures even lower than that for red mud leachate precipitates. In another set of experiments, iron oxide impregnated on activated carbon supports were prepared. Activated carbon is known for its adsorption properties which could give a better access of the impregnated metal oxide catalyst to perform the catalytic oxidation on the adsorbed substrate. Unburned carbon in bagasse ash which is a sugar industry agricultural waste was used to get the activated carbon. This material was separated from the ash and further modified to enhance the activity and increase the porosity. To this effect steam activation was performed. To impart thermal stability for oxidation reaction, the carbon was impregnated by phosphoric acid at activated at high temperatures in inert atmosphere. These carbons were thermally stable due to the surface C--O--P groups. Toluene adsorption studies were also performed for both the steam activated as well as phosphoric acid activated carbon and it was found that the steam activated carbons with less surface oxygen had reasonable adsorption attributes. For iron impregnation onto the prepared bagasse ash carbons, two different methods of impregnation viz. incipient wetness method as well as impregnation by precipitation of the red mud leachate by adding alkali to a slurry of carbon and leachate (Pratt method) was used. It was found that impregnation by precipitation led to better butanol oxidation performing catalyst than the one prepared by impregnating by incipient wetness method. The best performing catalyst amongst the iron impregnated on carbon types was found to give 100% butanol conversion at 200 °C. It was also observed that red mud leachate precipitated catalyst performed well for toluene oxidation and not for butanol oxidation while carbon supported iron oxide catalysts worked better for butanol oxidation than for toluene oxidation.

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.

Local oxidative stress in interdigital tinea pedis.

PubMed

Ozturk, Perihan; Arican, Ozer; Kurutas, Ergul B; Karakas, Tugba; Gungor, Meltem

2013-02-01

Several skin diseases are believed to be associated with oxidative stress. Tinea pedis is an infection of the feet caused by fungi. The infectious diseases caused by dermatophytes are mainly related to the enzymes produced by these fungi. The cutaneous oxidative stress status of tinea pedis has not been demonstrated in the published work up to now. The aim of the present study was to evaluate the role of oxidative stress in affected skin areas in a group of patients with interdigital tinea pedis. Thirty-one consecutive patients with a diagnosis of unilateral interdigital tinea pedis were enrolled. The samples were obtained by scraping the skin surface. Oxidative stress biomarkers such as superoxide dismutase, catalase and malondialdehyde levels were measured spectrophotometrically. The activities of superoxide dismutase and catalase and the levels of malondialdehyde were significantly higher on the lesional area than the non-lesional area (P < 0.001). According to sex and fungal subtypes, there was no significant difference in the levels of oxidative stress biomarkers in patients with tinea pedis (P > 0.05). Our results suggested that antioxidant defense of lesional skin surface was higher compared to non-lesional skin. This is possibly due to a compensatory response to various fungal infections and thereby protects the cells against oxidative damage. © 2012 Japanese Dermatological Association.

Laser induced single spot oxidation of titanium

NASA Astrophysics Data System (ADS)

Jwad, Tahseen; Deng, Sunan; Butt, Haider; Dimov, S.

2016-11-01

Titanium oxides have a wide range of applications in industry, and they can be formed on pure titanium using different methods. Laser-induced oxidation is one of the most reliable methods due to its controllability and selectivity. Colour marking is one of the main applications of the oxidation process. However, the colourizing process based on laser scanning strategies is limited by the relative large processing area in comparison to the beam size. Single spot oxidation of titanium substrates is proposed in this research in order to increase the resolution of the processed area and also to address the requirements of potential new applications. The method is applied to produce oxide films with different thicknesses and hence colours on titanium substrates. High resolution colour image is imprinted on a sheet of pure titanium by converting its pixels' colours into laser parameter settings. Optical and morphological periodic surface structures are also produced by an array of oxide spots and then analysed. Two colours have been coded into one field and the dependencies of the reflected colours on incident and azimuthal angles of the light are discussed. The findings are of interest to a range of application areas, as they can be used to imprint optical devices such as diffusers and Fresnel lenses on metallic surfaces as well as for colour marking.

ZIF-67-derived hollow nanocages with layered double oxides shell as high-Efficiency catalysts for CO oxidation

NASA Astrophysics Data System (ADS)

Kong, Wenpeng; Li, Jing; Chen, Yao; Ren, Yuqing; Guo, Yonghua; Niu, Shengli; Yang, Yanzhao

2018-04-01

Constructing non-precious hybrid metal oxides with specific morphology as cost-effective and highly efficient catalysts is a promising way for the automotive exhaust purification. In this work, we report a facile strategy for the fabrication of a unique hollow Co-Ni layered double oxides (HLDO) nanocages by using zeolitic imidazole frameworks (ZIFs) as template. The synthesis of intermediate core-shell and hollow Co-Ni layered double hydroxides (HLDH) nanoflakes as well as the corresponding Co-Ni oxides products were successfully controlled, and the formation process was also explained. Among ZIF-67-derived oxides, HLDO exhibits excellent catalytic activities (complete conversion of CO into CO2 at 118 °C) and long-term stability for CO oxidation. The remarkable catalytic activities of HLDO can be attributed to high surface area (258 m2 g-1) inherited from the HLDH, which could provide more active sites for CO oxidation. In addition, active oxygen species indicated by the O 1 s XPS spectrum and improved synergistic effect between NiO and Co3O4 reflected by H2-TPR, further explain the enhanced performance of the HLDO catalysts. The presented strategy for controlled design and synthesis of hollow multicomponent metal oxides will provide prospects in developing highly effective catalysts.

CoxFe1-x oxide coatings on metallic interconnects for solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Shen, Fengyu; Lu, Kathy

2016-10-01

In order to improve the performance of Cr-containing steel as an interconnect material for solid oxide fuel cells, CoFe alloy coatings with Co:Fe ratios of 9:1, 8:2, 7:3, 6:4, and 5:5 are deposited by electrodeposition and then oxidized to CoxFe1-x oxide coatings with a thickness of ∼6 μm as protective layers on the interconnect. The area specific resistance of the coated interconnect increases with the Fe content. Higher Co content oxide coatings are more effective in limiting the growth of the chromia scale while all coatings are effective in inhibiting Cr diffusion and evaporation. With the Co0.8Fe0.2 oxide coated interconnect, the electrochemical performance of the Sm0.5Sr0.5Co0.2Fe0.8O3 cathode is improved. Only 1.54 atomic percentage of Cr is detected on the surface of the Sm0.5Sr0.5Co0.2Fe0.8O3 cathode while no Cr is detected 0.66 μm or more into the cathode. CoxFe1-x oxide coatings are promising candidates for solid oxide fuel cell interconnects with the advantage of using existing cathode species for compatibility and performance enhancement.

Surface properties of calcium and magnesium oxide nanopowders grafted with unsaturated carboxylic acids studied with inverse gas chromatography.

PubMed

Maciejewska, Magdalena; Krzywania-Kaliszewska, Alicja; Zaborski, Marian

2012-09-28

Inverse gas chromatography (IGC) was applied at infinite dilution to evaluate the surface properties of calcium and magnesium oxide nanoparticles and the effect of surface grafted unsaturated carboxylic acid on the nanopowder donor-acceptor characteristics. The dispersive components (γ(s)(D)) of the free energy of the nanopowders were determined by Gray's method, whereas their tendency to undergo specific interactions was estimated based on the electron donor-acceptor approach presented by Papirer. The calcium and magnesium oxide nanoparticles exhibited high surface energies (79 mJ/m² and 74 mJ/m², respectively). Modification of nanopowders with unsaturated carboxylic acids decreased their specific adsorption energy. The lowest value of γ(s)(D) was determined for nanopowders grafted with undecylenic acid, approximately 55 mJ/m². The specific interactions were characterised by the molar free energy (ΔG(A)(SP)) and molar enthalpy (ΔH(A)(SP)) of adsorption as well as the donor and acceptor interaction parameters (K(A), K(D)). Copyright © 2012 Elsevier B.V. All rights reserved.

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.

Electrical, thermal and electrochemical properties of disordered carbon prepared from palygorskite and cane molasses

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

Alvarez, Edelio Danguillecourt, E-mail: edelioalvarez42@gmail.com; Laffita, Yodalgis Mosqueda, E-mail: yodalgis@imre.uh.cu; Montoro, Luciano Andrey, E-mail: landrey.montoro@gmail.com

We have synthesized and electrochemically tested a carbon sample that was suitable as anode for lithium secondary battery. The synthesis was based on the use of the palygorskite clay as template and sugar cane molasses as carbon source. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, Brunauer–Emmett–Teller (BET) measurements and High Resolution Transmission Electron Microscope (HRTEM) analysis showed that the nanometric carbon material has a highly disordered graphene-like wrinkled structure and large specific surface area (467 m{sup 2} g{sup −1}). The compositional characterization revealed a 14% of heteroatoms-containing groups (O, H, N, S) doping the as-prepared carbon. Thermophysicalmore » measurements revealed the good thermal stability and an acceptable thermal diffusivity (9·10{sup −7} m{sup 2} s{sup −1}) and conductivity (1.1 W m{sup −1} K{sup −1}) of this carbon. The electrical properties showed an electronic conductivity of hole-like carriers of approximately one S/cm in a 173–293 K range. The testing of this material as anodes in a secondary lithium battery displayed a high specific capacity and excellent performance in terms of number of cycles. A high reversible capacity of 356 mA h g{sup −1} was reached. - Graphical abstract: TEM image and electrochemistry behavior of a new graphene oxide-like carbon. - Highlights: • A high disordered graphene oxide-like conducting carbon is reported. • The synthesis was based on palygorskite and sugar cane molasses as precursors. • The disordered conducting carbon is composed of doped- graphene heterogeneous domains. • This material combines a large specific surface area and high electric conductivity. • The thermophysical and electrochemical properties of this material reveal adequate behavior.« less

The Influence of Fe Substitution in Lanthanum Calcium Cobalt Oxide on the Oxygen Evolution Reaction in Alkaline Media

DOE PAGES

Abreu-Sepulveda, Maria A.; Dhital, Chetan; Huq, Ashfia; ...

2016-07-30

The effect due to systematic substitution of cobalt by iron in La 0.6Ca 0.4Co 1-xFe xO 3 towards the oxygen evolution reaction(OER) in alkaline media has been investigated. We synthesized these compounds by a facile glycine-nitrate synthesis and the phase formation was confirmed by X-ray diffraction and Neutron Diffraction elemental analysis. The apparent OER activity was evaluated by quasi steady state current measurements in alkaline media using a traditional three-electrode cell. X-ray photoelectron spectroscopy shows iron substitution causes an increase in the surface concentration of various cobalt oxidation states. Tafel slope in the vicinity of 60 mV/decade and electrochemical reactionmore » order towards OH- near unity were achieved for the unsubstituted La 0.6Ca 0.4CoO 3. Moreover, a decrease in the Tafel slope to 49 mV/decade was observed when iron is substituted in high amounts in the perovskite structure. The area specific current density showed dependence on the Fe fraction, however the relationship of specific current density with Fe fraction is not linear. High Fe substitutions, La 0.6Ca 0.4Co 0.2Fe 0.8O 3 and La 0.6Ca 0.4Co 0.1Fe 0.9O 3 showed higher area specific activity towards OER than La 0.6Ca 0.4CoO 3 or La 0.6Ca 0.4FeO 3. Finally, we believe iron inclusion in the cobalt sites of the perovskite helps decrease the electron transfer barrier and facilitates the formation of cobalt-hydroxide at the surface. Possible OER mechanisms based on the observed kinetic parameters will be discussed.« less

Layered manganese oxides-decorated and nickel foam-supported carbon nanotubes as advanced binder-free supercapacitor electrodes

NASA Astrophysics Data System (ADS)

Huang, Ming; Mi, Rui; Liu, Hao; Li, Fei; Zhao, Xiao Li; Zhang, Wei; He, Shi Xuan; Zhang, Yu Xin

2014-12-01

Three-dimensional carbon nanotubes@MnO2 core-shell nanostructures grown on Ni foam for binder-free capacitor electrodes have been fabricated by a floating catalyst chemical vapor deposition process and a facile hydrothermal approach. Ultrathin layered MnO2 nanosheets are uniformly coated on the surface of the carbon nanotubes (CNTs), directly grown on Ni foam. This unique well-designed binder-free electrode exhibits a high specific capacitance (325.5 F g-1 at a current density of 0.3 A g-1), good rate capability (70.7% retention), and excellent cycling stability (90.5% capacitance retention after 5000 cycles), due to the high conductivity of the close contact between CNTs and Ni foam, as well as the moderate specific surface area of the CNTs@MnO2 core-shell nanostructures. The developed synthetic strategy may provide design guidelines for constructing advanced binder-free supercapacitors electrode.

A hybrid monolithic column based on boronate-functionalized graphene oxide nanosheets for online specific enrichment of glycoproteins.

PubMed

Zhou, Chanyuan; Chen, Xiaoman; Du, Zhuo; Li, Gongke; Xiao, Xiaohua; Cai, Zongwei

2017-05-19

A hybrid monolithic column based on aminophenylboronic acid (APBA)-functionalized graphene oxide (GO) has been developed and used for selective enrichment of glycoproteins. The APBA/GO composites were homogeneously incorporated into a polymer monolithic column with the help of oligomer matrix and followed by in situ polymerization. The effect of dispersion of APBA/GO composites in the polymerization mixture on the performance of the monolithic column was explored in detail. The presence of graphene oxide not only enlarged the BET surface area from 6.3m 2 /g to 169.4m 2 /g, but also provided abundant boronic acid moieties for glycoprotein extraction, which improved the enrichment selectivity and efficiency for glycoproteins. The APBA/GO hybrid monolithic column was incorporated into a sequential injection system, which facilitated online extraction of proteins. Combining the superior properties of extraordinary surface area of GO and the affinity interaction of APBA to glycoproteins, the APBA/GO hybrid monolithic column showed higher enrichment factors for glycoproteins than other proteins without cis-diol-containing groups. Also, under comparable or even shorter processing time and without the addition of any organic solvent, it showed higher binding capacity toward glycoproteins compared with the conventional boronate affinity monolithic column. The practical applicability of this system was demonstrated by processing of egg white samples for extraction of ovalbumin and ovotransferrin, and satisfactory results were obtained by assay with SDS-PAGE. Copyright © 2017 Elsevier B.V. All rights reserved.

Hierarchically porous LaFeO3 perovskite prepared from the pomelo peel bio-template for catalytic oxidation of NO

NASA Astrophysics Data System (ADS)

Zhao, Shaojun; Wang, Li; Wang, Ying; Li, Xing

2018-05-01

In this paper, pomelo peel was used as biological template to obtain hierarchically porous LaFeO3 perovskite for the catalytic oxidation of NO to NO2. In addition, X-ray diffraction (XRD), scanning electron microscopy (SEM), N2 adsorption-desorption analyses, X-ray photoelectron spectra (XPS), NO temperature-programmed desorption (NO-TPD), oxygen temperature-programmed desorption (O2-TPD) and hydrogen temperature-programmed reduction (H2-TPR) were used to investigate the micro-structure and the redox properties of the hierarchically porous LaFeO3 perovskite prepared from pomelo peel biological template and the LaFeO3 perovskite without the biological template. The results indicated that the hierarchically porous LaFeO3 perovskite successfully replicated the porous structure of pomelo peel with high specific surface area. Compared to the LaFeO3 perovskite prepared without the pomelo peel template, the hierarchically porous LaFeO3 perovskite showed better catalytic oxidization of NO to NO2 under the same conditions. The maximum NO conversions for LaFeO3 prepared with and without template were 90% at 305 °C and 76% at 313 °C, respectively. This is mainly attributed to the higher ratio of Fe4+/Fe3+, the hierarchically porous structure with more adsorbed oxygen species and higher surface area for the hierarchically porous LaFeO3 perovskite compared with the sample prepared without the pomelo peel template.

Mechanisms of Pb(II) sorption on a biogenic manganese oxide.

PubMed

Villalobos, Mario; Bargar, John; Sposito, Garrison

2005-01-15

Macroscopic Pb(II) uptake experiments and Pb L3-edge extended X-ray absorption fine structure (EXAFS) spectroscopy were combined to examine the mechanisms of Pb(II) sequestration by a biogenic manganese oxide and its synthetic analogues, all of which are layer-type manganese oxides (phyllomanganates). Relatively fast Pb(II) sorption was observed, as well as extremely high sorption capacities, suggesting Pb incorporation into the structure of the oxides. EXAFS analysis revealed similar uptake mechanisms regardless of the specific nature of the phyllomanganate, electrolyte background, total Pb(II) loading, or equilibration time. One Pb-O and two Pb-Mn shells at distances of 2.30, 3.53, and 3.74 A, respectively, were found, as well as a linear relationship between Brunauer-Emmett-Teller (BET; i.e., external) specific surface area and maximum Pb(II) sorption that also encompassed data from previous work. Both observations support the existence of two bonding mechanisms in Pb(II) sorption: a triple-corner-sharing complex in the interlayers above/ below cationic sheet vacancies (N theoretical = 6), and a double-corner-sharing complex on particle edges at exposed singly coordinated -O(H) bonds (N theoretical = 2). General prevalence of external over internal sorption is predicted, but the two simultaneous sorption mechanisms can account for the widely noted high affinity of manganese oxides for Pb(ll) in natural environments.

Measured and modeled dry deposition velocities over the ESCOMPTE area

NASA Astrophysics Data System (ADS)

Michou, M.; Laville, P.; Serça, D.; Fotiadi, A.; Bouchou, P.; Peuch, V.-H.

2005-03-01

Measurements of the dry deposition velocity of ozone have been made by the eddy correlation method during ESCOMPTE (Etude sur Site pour COntraindre les Modèles de Pollution atmosphérique et de Transport d'Emissions). The strong local variability of natural ecosystems was sampled over several weeks in May, June and July 2001 for four sites with varying surface characteristics. The sites included a maize field, a Mediterranean forest, a Mediterranean shrub-land, and an almost bare soil. Measurements of nitrogen oxide deposition fluxes by the relaxed eddy correlation method have also been carried out at the same bare soil site. An evaluation of the deposition velocities computed by the surface module of the multi-scale Chemistry and Transport Model MOCAGE is presented. This module relies on a resistance approach, with a detailed treatment of the stomatal contribution to the surface resistance. Simulations at the finest model horizontal resolution (around 10 km) are compared to observations. If the seasonal variations are in agreement with the literature, comparisons between raw model outputs and observations, at the different measurement sites and for the specific observing periods, are contrasted. As the simulated meteorology at the scale of 10 km nicely captures the observed situations, the default set of surface characteristics (averaged at the resolution of a grid cell) appears to be one of the main reasons for the discrepancies found with observations. For each case, sensitivity studies have been performed in order to see the impact of adjusting the surface characteristics to the observed ones, when available. Generally, a correct agreement with the observations of deposition velocities is obtained. This advocates for a sub-grid scale representation of surface characteristics for the simulation of dry deposition velocities over such a complex area. Two other aspects appear in the discussion. Firstly, the strong influence of the soil water content to the plant response, specifically in conditions of stress, is confirmed. Second, we point out the difficulty in interpreting measurements of nitrogen oxide deposition velocities: a synergetic approach combining measurements and modeling is practical.

A theranostic prodrug delivery system based on Pt(IV) conjugated nano-graphene oxide with synergistic effect to enhance the therapeutic efficacy of Pt drug.

PubMed

Li, Jingwen; Lyv, Zhonglin; Li, Yanli; Liu, Huan; Wang, Jinkui; Zhan, Wenjun; Chen, Hong; Chen, Huabing; Li, Xinming

2015-05-01

Due to their high NIR-optical absorption and high specific surface area, graphene oxide and graphene oxide-based nanocomposites have great potential in both drug delivery and photothermal therapy. In the work reported herein we successfully integrate a Pt(IV) complex (c,c,t-[Pt(NH3)2Cl2(OH)2]), PEGylated nano-graphene oxide (PEG-NGO), and a cell apoptosis sensor into a single platform to generate a multifunctional nanocomposite (PEG-NGO-Pt) which shows potential for targeted drug delivery and combined photothermal-chemotherapy under near infrared laser irradiation (NIR), and real-time monitoring of its therapeutic efficacy. Non-invasive imaging using a fluorescent probe immobilized on the GO shows an enhanced therapeutic effect of PEG-NGO-Pt in cancer treatment via apoptosis and cell death. Due to the enhanced cytotoxicity of cisplatin and the highly specific tumor targeting of PEG-NGO-Pt at elevated temperatures, this nanocomposite displays a synergistic effect in improving the therapeutic efficacy of the Pt drug with complete destruction of tumors, no tumor recurrence and minimal systemic toxicity in comparison with chemotherapy or photothermal treatment alone, highlighting the advantageous effects of integrating Pt(IV) with GO for anticancer treatment. Copyright © 2015 Elsevier Ltd. All rights reserved.

Recent Progress in Self‐Supported Metal Oxide Nanoarray Electrodes for Advanced Lithium‐Ion Batteries

PubMed Central

Zhang, Feng

2016-01-01

The rational design and fabrication of electrode materials with desirable architectures and optimized properties has been demonstrated to be an effective approach towards high‐performance lithium‐ion batteries (LIBs). Although nanostructured metal oxide electrodes with high specific capacity have been regarded as the most promising alternatives for replacing commercial electrodes in LIBs, their further developments are still faced with several challenges such as poor cycling stability and unsatisfying rate performance. As a new class of binder‐free electrodes for LIBs, self‐supported metal oxide nanoarray electrodes have many advantageous features in terms of high specific surface area, fast electron transport, improved charge transfer efficiency, and free space for alleviating volume expansion and preventing severe aggregation, holding great potential to solve the mentioned problems. This review highlights the recent progress in the utilization of self‐supported metal oxide nanoarrays grown on 2D planar and 3D porous substrates, such as 1D and 2D nanostructure arrays, hierarchical nanostructure arrays, and heterostructured nanoarrays, as anodes and cathodes for advanced LIBs. Furthermore, the potential applications of these binder‐free nanoarray electrodes for practical LIBs in full‐cell configuration are outlined. Finally, the future prospects of these self‐supported nanoarray electrodes are discussed. PMID:27711259

Pyrite Stability Under Venus Surface Conditions

NASA Astrophysics Data System (ADS)

Kohler, E.; Craig, P.; Port, S.; Chevrier, V.; Johnson, N.

2015-12-01

Radar mapping of the surface of Venus shows areas of high reflectivity in the Venusian highlands, increasing to 0.35 ± 0.04 to 0.43 ± 0.05 in the highlands from the planetary average of 0.14 ± 0.03. Iron sulfides, specifically pyrite (FeS2), can explain the observed high reflectivity. However, several studies suggest that pyrite is not stable under Venusian conditions and is destroyed on geologic timescales. To test the stability of pyrite on the Venusian surface, pyrite was heated in the Venus simulation chamber at NASA Goddard Space Flight Center to average Venusian surface conditions, and separately to highland conditions under an atmosphere of pure CO2 and separately under an atmosphere of 96.5% CO2, 3.5% N2 and 150 ppm SO2. After each run, the samples were weighed and analyzed using X-Ray Diffraction (XRD) to identify possible phase changes and determine the stability of pyrite under Venusian surface conditions. Under a pure CO2 atmosphere, the Fe in pyrite oxidizes to form hematite which is more stable at higher temperatures corresponding to the Venusian lowlands. Magnetite is the primary iron oxide that forms at lower temperatures corresponding to the radar-bright highlands. Our experiments also showed that the presence of atmospheric SO2 inhibits the oxidation of pyrite, increasing its stability under Venusian conditions, especially those corresponding to the highlands. This indicates that the relatively high level of SO2 in the Venusian atmosphere is key to the stability of pyrite, making it a possible candidate for the bright radar signal in the Venusian highlands.

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

Zhang, Li; Wu, Zili; Nelson, Nicholas

Catalytic performance and the nature of surface adsorbates were investigated for high-surface-area ceria during ethylbenzene oxidative dehydrogenation (ODH) reaction using CO2 as a soft oxidant. A template assisted method was used to synthesize the high-surface-area ceria. The interactions between ethylbenzene, styrene and CO2 on the surface of ceria and the role of CO2 for the ethylbenzene ODH reaction have been investigated in detail by using activity test, in situ Diffuse Reflectance Infrared and Raman spectroscopy. Not only did CO2 as an oxidant favor the higher yield of styrene, but it also inhibited the deposition of coke during the ethylbenzene ODHmore » reaction. Ethylbenzene ODH reaction over ceria followed a two-step pathway: Ethylbenzene is first dehydrogenated to styrene with H2 formed simultaneously, and then CO2 reacts with H2 via the reverse water gas shift. The styrene produced can easily polymerize to form polystyrene, a key intermediate for coke formation. In the absence of CO2, the polystyrene transforms into graphite-like coke at temperatures above 500 °C, which leads to catalyst deactivation. While in the presence of CO2, the coke deposition can be effectively removed via oxidation with CO2.« less

Tire containing thermally exfoliated graphite oxide

NASA Technical Reports Server (NTRS)

Prud'homme, Robert K. (Inventor); Aksay, Ilhan A. (Inventor)

2011-01-01

A tire, tire lining or inner tube, containing a polymer composite, made of at least one rubber and/or at least one elastomer and a modified graphite oxide material, which is a thermally exfoliated graphite oxide with a surface area of from about 300 sq m/g to 2600 sq m/g.

Analysis of the sorption properties of different soils using water vapour adsorption and potentiometric titration methods

NASA Astrophysics Data System (ADS)

Skic, Kamil; Boguta, Patrycja; Sokołowska, Zofia

2016-07-01

Parameters of specific surface area as well as surface charge were used to determine and compare sorption properties of soils with different physicochemical characteristics. The gravimetric method was used to obtain water vapour isotherms and then specific surface areas, whereas surface charge was estimated from potentiometric titration curves. The specific surface area varied from 12.55 to 132.69 m2 g-1 for Haplic Cambisol and Mollic Gleysol soil, respectively, and generally decreased with pH (R=0.835; α = 0.05) and when bulk density (R=-0.736; α = 0.05) as well as ash content (R=-0.751; α = 0.05) increased. In the case of surface charge, the values ranged from 63.00 to 844.67 μmol g-1 Haplic Fluvisol and Mollic Gleysol, respecively. Organic matter gave significant contributions to the specific surface area and cation exchange capacity due to the large surface area and numerous surface functional groups, containing adsorption sites for water vapour molecules and for ions. The values of cation exchange capacity and specific surface area correlated linearly at the level of R=0.985; α = 0.05.

In vitro effects of cisplatin-functionalized silica nanoparticles on chondrocytes

NASA Astrophysics Data System (ADS)

Bhowmick, Tridib Kumar; Yoon, Diana; Patel, Minal; Fisher, John; Ehrman, Sheryl

2010-10-01

In this study, we evaluated the combined effect of a known toxic molecule, cisplatin, in combination with relatively nontoxic nanoparticles, amorphous fumed silica, on chondrocyte cells. Cisplatin was attached to silica nanoparticles using aminopropyltriethoxy silane as a linker molecule, and characterized in terms of size, shape, specific surface area, as well as the dissolution of cisplatin from the silica surface. The primary particle diameter of the as-received silica nanoparticles ranged from 7.1 to 61 nm, estimated from measurements of specific surface area, and the primary particles were aggregated. The effects of cisplatin-functionalized silica particles with different specific surface areas (41, 85, 202, 237, and 297 m2/g) were compared in vitro on chondrocytes, the parenchymal cell of hyaline cartilage. The results show that adverse effects on cell function, as evidenced by reduced metabolic activity measured by the MTT assay and increased membrane permeability observed using the Live/Dead stain, can be correlated with specific surface area of the silica. Cisplatin-functionalized silica nanoparticles with the highest specific surface area incited the greatest response, which was almost equivalent to that induced by free cisplatin. This result suggests the importance of particle specific surface area in interactions between cells and surface-functionalized nanomaterials.

Stabilizing platinum in phosphoric acid fuel cells

NASA Technical Reports Server (NTRS)

Remick, R. J.

1981-01-01

The cathode of the phosphoric acid fuel cell uses a high surface area platinum catalyst supported on a carbon substrate. During operation, the small platinum crystallites sinter, causing loss in cell performance. A support was developed that stabilizes platinum in the high surface area condition by retarding or preventing the sintering process. The approach is to form etch pits in the carbon by oxidizing the carbon in the presence of a metal oxide catalyst, remove the metal oxide by an acid wash, and then deposit platinum in these pits. Results confirm the formation of etch pits in each of the three supports chosen for investigation: Vulcan XC-72R, Vulcan XC-72 that was graphized at 2500 C, and Shawinigan Acetylene Black.

Catalyst for hydrotreating carbonaceous liquids

DOEpatents

Berg, Lloyd; McCandless, Frank P.; Ramer, Ronald J.

1982-01-01

A catalyst for denitrogenating and desulfurating carbonaceous liquid such as solvent refined coal includes catalytic metal oxides impregnated within a porous base of mostly alumina with relatively large pore diameters, surface area and pore volume. The base material includes pore volumes of 0.7-0.85 ml/g, surface areas of 200-350 m.sup.2 /g and pore diameters of 85-200 Angstroms. The catalytic metals impregnated into these base materials include the oxides of Group VI metals, molybdenum and tungsten, and the oxides of Group VIII metals, nickel and cobalt, in various combinations. These catalysts and bases in combination have effectively promoted the removal of chemically combined sulfur and nitrogen within a continuous flowing mixture of carbonaceous liquid and hydrogen gas.

Adsorption of water vapour and the specific surface area of arctic zone soils (Spitsbergen)

NASA Astrophysics Data System (ADS)

Cieśla, Jolanta; Sokołowska, Zofia; Witkowska-Walczak, Barbara; Skic, Kamil

2018-01-01

Water vapour/nitrogen adsorption were investigated and calculated the specific surface areas of arctic-zone soil samples (Turbic Cryosols) originating from different micro-relief forms (mud boils, cell forms and sorted circles) and from different depths. For the characterisation of the isotherms obtained for arctic soils, the Brunauer-Emmet-Teller model was then compared with the two other models (Aranovich-Donohue and Guggenheim-Anderson-de Boer) which were developed from Brunauer-Emmet-Teller. Specific surface area was calculated using the Brunauer-Emmet-Teller model at p p0-1 range of 0.05-0.35 for the water vapour desorption and nitrogen adsorption isotherms. The values of total specific surface area were the highest in Cryosols on mud boils, lower on cell forms, and the lowest on sorted circles. Such tendency was observed for the results obtained by both the water vapour and nitrogen adsorption. The differences in the values of specific surface area at two investigated layers were small. High determination coefficients were obtained for relationships between the specific surface areas and contents of clay and silt fraction in Cryosols. No statistically significant correlation between the total carbon amount and the values of specific surface area in Cryosols has been found.

Oxide surfaces and metal/oxide interfaces studied by grazing incidence X-ray scattering

NASA Astrophysics Data System (ADS)

Renaud, Gilles

Experimental determinations of the atomic structure of insulating oxide surfaces and metal/oxide interfaces are scarce, because surface science techniques are often limited by the insulating character of the substrate. Grazing incidence X-ray scattering (GIXS), which is not subject to charge effects, can provide very precise information on the atomic structure of oxide surfaces: roughness, relaxation and reconstruction. It is also well adapted to analyze the atomic structure, the registry, the misfit relaxation, elastic or plastic, the growth mode and the morphology of metal/oxide interfaces during their growth, performed in situ. GIXS also allows the analysis of thin films and buried interfaces, in a non-destructive way, yielding the epitaxial relationships, and, by variation of the grazing incidence angle, the lattice parameter relaxation along the growth direction. On semi-coherent interfaces, the existence of an ordered network of interfacial misfit dislocations can be demonstrated, its Burger's vector determined, its ordering during in situ annealing cycles followed, and sometimes even its atomic structure can be addressed. Careful analysis during growth allows the modeling of the dislocation nucleation process. This review emphasizes the new information that GIXS can bring to oxide surfaces and metal/oxide interfaces by comparison with other surface science techniques. The principles of X-ray diffraction by surfaces and interfaces are recalled, together with the advantages and properties of grazing angles. The specific experimental requirements are discussed. Recent results are presented on the determination of the atomic structure of relaxed or reconstructed oxide surfaces. A description of results obtained during the in situ growth of metal on oxide surfaces is also given, as well as investigations of thick metal films on oxide surfaces, with lattice parameter misfit relaxed by an array of dislocations. Recent work performed on oxide thin films having important physical properties such as superconductivity or magnetism is also briefly reviewed. The strengths and limitations of the technique, such as the need for single crystals and surfaces of high crystalline quality are discussed. Finally, an outlook of future prospects in the field is given, such as the study of more complex oxide surfaces, vicinal surfaces, reactive metal/oxide interfaces, metal oxidation processes, the use of surfactants to promote wetting of a metal deposited on an oxide surface or the study of oxide/liquid interfaces in a non-UHV environment.

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

PubMed

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

2015-12-01

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

A simplified biomolecule attachment strategy for biosensing using a porous Si oxide interferometer

PubMed Central

Perelman, Loren A.; Schwartz, Michael P.; Wohlrab, Aaron M.; VanNieuwenhze, Michael S.; Sailor, Michael J.

2008-01-01

A simple strategy for linking biomolecules to porous Si surfaces and detecting peptide/drug binding is described. Porous Si is prepared using an electrochemical etch and then thermally oxidized by heating in ambient atmosphere. Bovine serum albumin (BSA) is then non-covalently adsorbed to the inner pore walls of the porous Si oxide (PSiO2) matrix. The BSA layer is used as a linker for covalent attachment of the peptide Ac-L-Lysine-D-Alanine-D-Alanine (KAA) using published bioconjugation chemistry. BSA-coated surfaces functionalized with KAA display specificity for the glycopeptide vancomycin while resisting adsorption of non-specific reagents. While the biomolecule attachment strategy reported here is used to bind peptides, the scheme can be generalized to the linking of any primary amine-containing molecule to PSiO2 surfaces. PMID:18458749

Differential proteomics analysis of the surface heterogeneity of dextran iron oxide nanoparticles and the implications for their in vivo clearance

PubMed Central

Simberg, Dmitri; Park, Ji-Ho; Karmali, Priya P.; Zhang, Wan-Ming; Merkulov, Sergei; McCrae, Keith; Bhatia, Sangeeta; Sailor, Michael; Ruoslahti, Erkki

2009-01-01

In order to understand the role of plasma proteins in the rapid liver clearance of dextran-coated superparamagnetic iron oxide (SPIO) in vivo, we analyzed the full repertoire of SPIO-binding blood proteins using novel two-dimensional differential mass spectrometry approach. The identified proteins showed specificity for surface domains of the nanoparticles: mannan-binding lectins bound to the dextran coating, histidine-rich glycoprotein and kininogen bound to the iron oxide part, and the complement lectin and contact clotting factors were secondary binders. Nanoparticle clearance studies in knockout mice suggested that these proteins, as well as several previously identified opsonins, do not play a significant role in the SPIO clearance. However, both the dextran coat and the iron oxide core remained accessible to specific probes after incubation of SPIO in plasma, suggesting that the nanoparticle surface could be available for recognition by macrophages, regardless of protein coating. These data provide guidance to rational design of bioinert, long-circulating nanoparticles. PMID:19394687

Differential proteomics analysis of the surface heterogeneity of dextran iron oxide nanoparticles and the implications for their in vivo clearance.

PubMed

Simberg, Dmitri; Park, Ji-Ho; Karmali, Priya P; Zhang, Wan-Ming; Merkulov, Sergei; McCrae, Keith; Bhatia, Sangeeta N; Sailor, Michael; Ruoslahti, Erkki

2009-08-01

In order to understand the role of plasma proteins in the rapid liver clearance of dextran-coated superparamagnetic iron oxide (SPIO) in vivo, we analyzed the full repertoire of SPIO-binding blood proteins using novel two-dimensional differential mass spectrometry approach. The identified proteins showed specificity for surface domains of the nanoparticles: mannan-binding lectins bound to the dextran coating, histidine-rich glycoprotein and kininogen bound to the iron oxide part, and the complement lectin and contact clotting factors were secondary binders. Nanoparticle clearance studies in knockout mice suggested that these proteins, as well as several previously identified opsonins, do not play a significant role in the SPIO clearance. However, both the dextran coat and the iron oxide core remained accessible to specific probes after incubation of SPIO in plasma, suggesting that the nanoparticle surface could be available for recognition by macrophages, regardless of protein coating. These data provide guidance to rational design of bioinert, long-circulating nanoparticles.

Ferrate (IV) as a Possible Oxidant on the Martian Surface

NASA Astrophysics Data System (ADS)

Tsapin, Alexandre; Goldfeld, M. G.; McDonald, G. D.; Nealson, K. H.; Mohnke, J.; Moskovitz, B.; Solheid, P.; Kemner, K. H.; Orlandini, K.

Viking experiments showed that Martian soil has a very strong oxidant, which could be responsible for the results of experiments performed on Viking landers. These experiments were designed specifically to detect life on Mars. The nature of that oxidant was not determined during Viking mission. Later several groups tried to reconstruct Viking experiments and find out the nature of Martian oxidant. None of these attempts were completely successful. The general perception was that there are several chemically different oxidants on Martian surface. In this study we suggested that potassium ferrate K_2FeO_4 can be Martian oxidant responsible at least partially for the results of experiments on Viking landers. We characterized liquid and powder preparation of Fe (VI) with EPR, optical spectroscopy, Mossbauer spectroscopy, and by Fe-XANES. All properties of our preparations of (FeVI) are consistent with the proposal role of that compound as a strong oxidant on Martian surface.

Low-damage direct patterning of silicon oxide mask by mechanical processing

PubMed Central

2014-01-01

To realize the nanofabrication of silicon surfaces using atomic force microscopy (AFM), we investigated the etching of mechanically processed oxide masks using potassium hydroxide (KOH) solution. The dependence of the KOH solution etching rate on the load and scanning density of the mechanical pre-processing was evaluated. Particular load ranges were found to increase the etching rate, and the silicon etching rate also increased with removal of the natural oxide layer by diamond tip sliding. In contrast, the local oxide pattern formed (due to mechanochemical reaction of the silicon) by tip sliding at higher load was found to have higher etching resistance than that of unprocessed areas. The profile changes caused by the etching of the mechanically pre-processed areas with the KOH solution were also investigated. First, protuberances were processed by diamond tip sliding at lower and higher stresses than that of the shearing strength. Mechanical processing at low load and scanning density to remove the natural oxide layer was then performed. The KOH solution selectively etched the low load and scanning density processed area first and then etched the unprocessed silicon area. In contrast, the protuberances pre-processed at higher load were hardly etched. The etching resistance of plastic deformed layers was decreased, and their etching rate was increased because of surface damage induced by the pre-processing. These results show that etching depth can be controlled by controlling the etching time through natural oxide layer removal and mechanochemical oxide layer formation. These oxide layer removal and formation processes can be exploited to realize low-damage mask patterns. PMID:24948891

Surface premelting/recrystallization governing the collapse of open-cell nanoporous Cu via thermal annealing.

PubMed

Wang, L; Zhang, X M; Deng, L; Tang, J F; Xiao, S F; Deng, H Q; Hu, W Y

2018-06-04

We systematically investigate the collapse of a set of open-cell nanoporous Cu (np-Cu) materials with the same porosity and shape but different specific surface areas, during thermal annealing, by performing large-scale molecular dynamics simulations. Two mechanisms govern the collapse of np-Cu. One is direct surface premelting, facilitating the collapse of np-Cu, when the specific surface area is less than a critical value (∼2.38 nm-1). The other is recrystallization followed by surface premelting, accelerating the sloughing of ligaments and the annihilation of voids, when the critical specific surface area is exceeded. Surface premelting results from surface reconstruction by prompting localized "disordering" and "chaos" on the surface, and the melting temperature reduces linearly with the increase of the specific surface area. Recrystallization is followed by surface premelting as the melting temperature is below the supercooling point, where a liquid is unstable and instantaneously recrystallizes.

Easy-to-Fabricate and High-Sensitivity LSPR Type Specific Protein Detection Sensor Using AAO Nano-Pore Size Control

PubMed Central

Kim, Sae-Wan; Lee, Jae-Sung; Lee, Sang-Won; Kang, Byoung-Ho; Kwon, Jin-Beom; Kim, Ok-Sik; Kim, Ju-Seong; Kim, Eung-Soo; Kwon, Dae-Hyuk; Kang, Shin-Won

2017-01-01

In this study, we developed a pore size/pore area-controlled optical biosensor-based anodic aluminum oxide (AAO) nanostructure. As the pore size of AAO increases, the unit cell of AAO increases, which also increases the non-pore area to which the antibody binds. The increase in the number of antibodies immobilized on the surface of the AAO enables effective detection of trace amounts of antigen, because increased antigen-antibody bonding results in a larger surface refractive index change. High sensitivity was thus achieved through amplification of the interference wave of two vertically-incident reflected waves through the localized surface plasmon resonance phenomenon. The sensitivity of the fabricated sensor was evaluated by measuring the change in wavelength with the change in the refractive index of the device surface, and sensitivity was increased with increasing pore-size and non-pore area. The sensitivity of the fabricated sensor was improved and up to 11.8 ag/mL serum amyloid A1 antigen was detected. In addition, the selectivity of the fabricated sensor was confirmed through a reaction with a heterogeneous substance, C-reactive protein antigen. By using hard anodization during fabrication of the AAO, the fabrication time of the device was reduced and the AAO chip was fabricated quickly and easily. PMID:28406469

Nanoparticle-induced oxidation of corona proteins initiates an oxidative stress response in cells†

PubMed Central

Jayaram, Dhanya T.; Runa, Sabiha; Kemp, Melissa L.

2017-01-01

Titanium dioxide nanoparticles (TiO2 NPs), used as pigments and photocatalysts, are ubiquitous in our daily lives. Previous work has observed cellular oxidative stress in response to the UV-excitation of photocatalytic TiO2 NPs. In comparison, most human exposure to TiO2 NPs takes place in the dark, in the lung following inhalation or in the gut following consumption of TiO2 NP food pigment. Our spectroscopic characterization shows that both photocatalytic and food grade TiO2 NPs, in the dark, generate low levels of reactive oxygen species (ROS), specifically hydroxyl radicals and superoxides. These ROS oxidize serum proteins that form a corona of proteins on the NP surface. This protein layer is the interface between the NP and the cell. An oxidized protein corona triggers an oxidative stress response, detected with PCR and western blotting. Surface modification of TiO2 NPs to increase or decrease surface defects correlates with ROS generation and oxidative stress, suggesting that NP surface defects, likely oxygen vacancies, are the underlying cause of TiO2 NP-induced oxidative stress. PMID:28537609

Properties that influence the specific surface areas of carbon nanotubes and nanofibers.

PubMed

Birch, M Eileen; Ruda-Eberenz, Toni A; Chai, Ming; Andrews, Ronnee; Hatfield, Randal L

2013-11-01

Commercially available carbon nanotubes and nanofibers were analyzed to examine possible relationships between their Brunauer-Emmett-Teller specific surface areas (SSAs) and their physical and chemical properties. Properties found to influence surface area were number of walls/diameter, impurities, and surface functionalization with hydroxyl and carboxyl groups. Characterization by electron microscopy, energy-dispersive X-ray spectrometry, thermogravimetric analysis, and elemental analysis indicates that SSA can provide insight on carbon nanomaterials properties, which can differ vastly depending on synthesis parameters and post-production treatments. In this study, how different properties may influence surface area is discussed. The materials examined have a wide range of surface areas. The measured surface areas differed from product specifications, to varying degrees, and between similar products. Findings emphasize the multiple factors that influence surface area and mark its utility in carbon nanomaterial characterization, a prerequisite to understanding their potential applications and toxicities. Implications for occupational monitoring are discussed.

Method and apparatus for detecting the presence and thickness of carbon and oxide layers on EUV reflective surfaces

DOEpatents

Malinowski, Michael E.

2005-01-25

The characteristics of radiation that is reflected from carbon deposits and oxidation formations on highly reflective surfaces such as Mo/Si mirrors can be quantified and employed to detect and measure the presence of such impurities on optics. Specifically, it has been shown that carbon deposits on a Mo/Si multilayer mirror decreases the intensity of reflected HeNe laser (632.8 nm) light. In contrast, oxide layers formed on the mirror should cause an increase in HeNe power reflection. Both static measurements and real-time monitoring of carbon and oxide surface impurities on optical elements in lithography tools should be achievable.

Effect of Reacting Surface Density on the Overall Graphite Oxidation Rate

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

Chang H. Oh; Eung Kim; Jong Lim

2009-05-01

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

Assessing the Increase in Specific Surface Area for Electrospun Fibrous Network due to Pore Induction.

PubMed

Katsogiannis, Konstantinos Alexandros G; Vladisavljević, Goran T; Georgiadou, Stella; Rahmani, Ramin

2016-10-26

The effect of pore induction on increasing electrospun fibrous network specific surface area was investigated in this study. Theoretical models based on the available surface area of the fibrous network and exclusion of the surface area lost due to fiber-to-fiber contacts were developed. The models for calculation of the excluded area are based on Hertzian, Derjaguin-Muller-Toporov (DMT), and Johnson-Kendall-Roberts (JKR) contact models. Overall, the theoretical models correlated the network specific surface area to the material properties including density, surface tension, Young's modulus, Poisson's ratio, as well as network physical properties, such as density and geometrical characteristics including fiber radius, fiber aspect ratio and network thickness. Pore induction proved to increase the network specific surface area up to 52%, compared to the maximum surface area that could be achieved by nonporous fiber network with the same physical properties and geometrical characteristics. The model based on Johnson-Kendall-Roberts contact model describes accurately the fiber-to-fiber contact area under the experimental conditions used for pore generation. The experimental results and the theoretical model based on Johnson-Kendall-Roberts contact model show that the increase in network surface area due to pore induction can reach to up to 58%.

Linking interfacial chemistry of CO2 to surface structures of hydrated metal oxide nanoparticles: hematite.

PubMed

Chernyshova, Irina V; Ponnurangam, Sathish; Somasundaran, Ponisseril

2013-05-14

A better understanding of interaction with dissolved CO2 is required to rationally design and model the (photo)catalytic and sorption processes on metal (hydr)oxide nanoparticles (NPs) in aqueous media. Using in situ FTIR spectroscopy, we address this problem for rhombohedral 38 nm hematite (α-Fe2O3) nanoparticles as a model. We not only resolve the structures of the adsorbed carbonate species, but also specify their adsorption sites and their location on the nanoparticle surface. The spectral relationships obtained present a basis for a new method of characterizing the microscopic structural and acid-base properties (related to individual adsorption sites) of hydrated metal (hydr)oxide NPs using atmospherically derived CO2 as a probe. Specifically, we distinguish two carbonate species suggesting two principally different adsorption mechanisms. One species, which is more weakly adsorbed, has an inner-sphere mononuclear monodentate structure which is formed by a conventional ligand-exchange mechanism. At natural levels of dissolved carbonate and pH from 3 to 11, this species is attached to the most acidic/reactive surface cations (surface states) associated with ferrihydrite-like surface defects. The second species, which is more strongly adsorbed, presents a mixed C and O coordination of bent CO2. This species uniquely recognizes the stoichiometric rhombohedral {104} facets in the NP texture. Like in gas phase, it is formed through the surface coordination of molecular CO2. We address how the adsorption sites hosting these two carbonate species are affected by the annealing and acid etching of the NPs. These results support the nanosize-induced phase transformation of hematite towards ferrihydrite under hydrous conditions, and additionally show that the process starts from the roughened areas of the facet intersections.

Application of sludge-based carbonaceous materials in a hybrid water treatment process based on adsorption and catalytic wet air oxidation.

PubMed

Julcour Lebigue, Carine; Andriantsiferana, Caroline; N'Guessan Krou; Ayral, Catherine; Mohamed, Elham; Wilhelm, Anne-Marie; Delmas, Henri; Le Coq, Laurence; Gerente, Claire; Smith, Karl M; Pullket, Suangusa; Fowler, Geoffrey D; Graham, Nigel J D

2010-12-01

This paper describes a preliminary evaluation of the performance of carbonaceous materials prepared from sewage sludges (SBCMs) in a hybrid water treatment process based on adsorption and catalytic wet air oxidation; phenol was used as the model pollutant. Three different sewage sludges were treated by either carbonisation or steam activation, and the physico-chemical properties of the resultant carbonaceous materials (e.g. hardness, BET surface area, ash and elemental content, surface chemistry) were evaluated and compared with a commercial reference activated carbon (PICA F22). The adsorption capacity for phenol of the SBCMs was greater than suggested by their BET surface area, but less than F22; a steam activated, dewatered raw sludge (SA_DRAW) had the greatest adsorption capacity of the SBCMs in the investigated range of concentrations (<0.05 mol L(-1)). In batch oxidation tests, the SBCMs demonstrated catalytic behaviour arising from their substrate adsorptivity and metal content. Recycling of SA_DRAW in successive oxidations led to significant structural attrition and a hardened SA_DRAW was evaluated, but found to be unsatisfactory during the oxidation step. In a combined adsorption-oxidation sequence, both the PICA carbon and a selected SBCM showed deterioration in phenol adsorption after oxidative regeneration, but a steady state performance was reached after 2 or 3 cycles. Copyright © 2010 Elsevier Ltd. All rights reserved.

Variable Lysozyme Transport Dynamics on Oxidatively Functionalized Polystyrene Films.

PubMed

Moringo, Nicholas A; Shen, Hao; Tauzin, Lawrence J; Wang, Wenxiao; Bishop, Logan D C; Landes, Christy F

2017-10-17

Tuning protein adsorption dynamics at polymeric interfaces is of great interest to many biomedical and material applications. Functionalization of polymer surfaces is a common method to introduce application-specific surface chemistries to a polymer interface. In this work, single-molecule fluorescence microscopy is utilized to determine the adsorption dynamics of lysozyme, a well-studied antibacterial protein, at the interface of polystyrene oxidized via UV exposure and oxygen plasma and functionalized by ligand grafting to produce varying degrees of surface hydrophilicity, surface roughness, and induced oxygen content. Single-molecule tracking indicates lysozyme loading capacities, and surface mobility at the polymer interface is hindered as a result of all functionalization techniques. Adsorption dynamics of lysozyme depend on the extent and the specificity of the oxygen functionalities introduced to the polystyrene surface. Hindered adsorption and mobility are dominated by hydrophobic effects attributed to water hydration layer formation at the functionalized polystyrene surfaces.

Prediction of Isoelectric Point of Manganese and Cobalt Lamellar Oxides: Application to Controlled Synthesis of Mixed Oxides.

PubMed

Tang, Céline; Giaume, Domitille; Guerlou-Demourgues, Liliane; Lefèvre, Grégory; Barboux, Philippe

2018-05-30

To design novel layered materials, bottom-up strategy is very promising. It consists of (1) synthesizing various layered oxides, (2) exfoliating them, then (3) restacking them in a controlled way. The last step is based on electrostatic interactions between different layered oxides and is difficult to control. The aim of this study is to facilitate this step by predicting the isoelectric point (IEP) of exfoliated materials. The Multisite Complexation model (MUSIC) was used for this objective and was shown to be able to predict IEP from the mean oxidation state of the metal in the (hydr)oxides, as the main parameter. Moreover, the effect of exfoliation on IEP has also been calculated. Starting from platelets with a high basal surface area over total surface area, we show that the exfoliation process has no impact on calculated IEP value, as verified with experiments. Moreover, the restacked materials containing different monometallic (hydr)oxide layers also have an IEP consistent with values calculated with the model. This study proves that MUSIC model is a useful tool to predict IEP of various complex metal oxides and hydroxides.

Rapid assessment of oxidation via middle-down LCMS correlates with methionine side-chain solvent-accessible surface area for 121 clinical stage monoclonal antibodies.

PubMed

Yang, Rong; Jain, Tushar; Lynaugh, Heather; Nobrega, R Paul; Lu, Xiaojun; Boland, Todd; Burnina, Irina; Sun, Tingwan; Caffry, Isabelle; Brown, Michael; Zhi, Xiaoyong; Lilov, Asparouh; Xu, Yingda

Susceptibility of methionine to oxidation is an important concern for chemical stability during the development of a monoclonal antibody (mAb) therapeutic. To minimize downstream risks, leading candidates are usually screened under forced oxidation conditions to identify oxidation-labile molecules. Here we report results of forced oxidation on a large set of in-house expressed and purified mAbs with variable region sequences corresponding to 121 clinical stage mAbs. These mAb samples were treated with 0.1% H 2 O 2 for 24 hours before enzymatic cleavage below the hinge, followed by reduction of inter-chain disulfide bonds for the detection of the light chain, Fab portion of heavy chain (Fd) and Fc by liquid chromatography-mass spectrometry. This high-throughput, middle-down approach allows detection of oxidation site(s) at the resolution of 3 distinct segments. The experimental oxidation data correlates well with theoretical predictions based on the solvent-accessible surface area of the methionine side-chains within these segments. These results validate the use of upstream computational modeling to predict mAb oxidation susceptibility at the sequence level.

Surface functionalized magnetic nanoparticles for cancer therapy applications

NASA Astrophysics Data System (ADS)

Wydra, Robert John

Despite recent advances, cancer remains the second leading cause of deaths in the United States. Magnetic nanoparticles have found various applications in cancer research as drug delivery platforms, enhanced contrast agents for improved diagnostic imaging, and the delivery of thermal energy as standalone therapy. Iron oxide nanoparticles absorb the energy from an alternating magnetic field and convert it into heat through Brownian and Neel relaxations. To better utilize magnetic nanoparticles for cancer therapy, surface functionalization is essential for such factors as decreasing cytotoxicity of healthy tissue, extending circulation time, specific targeting of cancer cells, and manage the controlled delivery of therapeutics. In the first study, iron oxide nanoparticles were coated with a poly(ethylene glycol) (PEG) based polymer shell. The PEG coating was selected to prevent protein adsorption and thus improve circulation time and minimize host response to the nanoparticles. Thermal therapy application feasibility was demonstrated in vitro with a thermoablation study on lung carcinoma cells. Building on the thermal therapy demonstration with iron oxide nanoparticles, the second area of work focused on intracellular delivery. Nanoparticles can be appropriately tailored to enter the cell and deliver energy on the nanoscale eliminating individual cancer cells. The underlying mechanism of action is still under study, and we were interested in determining the role of reactive oxygen species (ROS) catalytically generated from the surface of iron oxide nanoparticles in this measured cytotoxicity. When exposed to an AMF, the nanoscale heating effects are capable of enhancing the Fenton-like generation of ROS determined through a methylene blue degradation assay. To deliver this enhanced ROS effect to cells, monosaccharide coated nanoparticles were developed and successfully internalized by colon cancer cell lines. Upon AMF exposure, there was a measured increase in cellular ROS and apoptosis that was attributed to lysosomal disruption since the surface functionalization selected inhibited the Fenton-like surface chemistry. To overcome this surface inhibition, a biodegradable poly(beta-amino ester) (PBAE) polymer coating was synthesized to deliver bare iron oxide to intracellular components. Delivering enhanced ROS to cancer cells is a promising new route of therapy that deserves future studies.

A noncovalent compatibilization approach to improve the filler dispersion and properties of polyethylene/graphene composites.

PubMed

Vasileiou, Alexandros A; Kontopoulou, Marianna; Docoslis, Aristides

2014-02-12

Graphene was prepared by low temperature vacuum-assisted thermal exfoliation of graphite oxide. The resulting thermally reduced graphene oxide (TRGO) had a specific surface area of 586 m(2)/g and consisted of a mixture of single-layered and multilayered graphene. The TRGO was added to maleated linear low-density polyethylene LLDPE and to its derivatives with pyridine aromatic groups by melt compounding. The LLDPE/TRGO composites exhibited very low electrical percolation thresholds, between 0.5 and 0.9 vol %, depending on the matrix viscosity and the type of functional groups. The dispersion of the TRGO in the compatibilized composites was improved significantly, due to enhanced noncovalent interactions between the aromatic moieties grafted onto the polymer matrix and the filler. Better dispersion resulted in a slight increase in the rheological and electrical percolation thresholds, and to significant improvements in mechanical properties and thermal conductivity, compared to the noncompatibilized composites. The presence of high surface area nanoplatelets within the polymer also resulted in a substantially improved thermal stability. Compared to their counterparts containing multiwalled carbon nanotubes, LLDPE/TRGO composites had lower percolation thresholds. Therefore, lower amounts of TRGO were sufficient to impart electrical conductivity and modulus improvements, without compromising the ductility of the composites.

Photocatalytic activity enhancement of anatase-graphene nanocomposite for methylene removal: Degradation and kinetics

NASA Astrophysics Data System (ADS)

Rezaei, Mostafa; Salem, Shiva

2016-10-01

In the present research, the TiO2-graphene nanocomposite was synthesized by an eco-friendly method. The blackberry juice was introduced to graphene oxide (GO) as a reducing agent to produce the graphene nano-sheets. The nanocomposite of anatase-graphene was developed as a photocatalyst for the degradation of methylene blue, owing to the larger specific surface area and synergistic effect of reduced graphene oxide (RGO). The UV spectroscopy measurements showed that the prepared nanocomposite exhibited an excellent photocatalytic activity toward the methylene blue degradation. The rate of electron transfer of redox sheets is much higher than that observed on GO, indicating the applicability of proposed method for the production of anatase-RGO nanocomposite for treatment of water contaminated by cationic dye. The prepared materials were characterized with Fourier transform infrared spectroscopy, X-ray diffraction, Brunauer-Emmett-Teller surface area measurement, scanning electron microscopy and transmission electron microscopy. A facile and rapid route was applied for the uniform deposition of anatase nanoparticles on the sheets. The resulting nanocomposite contained nanoparticles with a mean diameter of 10 nm. A mechanism for the photocatalytic activity of nanocomposite was suggested and the degradation reaction obeyed the second-order kinetics. It was concluded that the degradation kinetics is changed due to the reduction of GO in the presence of blackberry juice.

Boosting the Supercapacitance of Nitrogen-Doped Carbon by Tuning Surface Functionalities.

PubMed

Biemolt, Jasper; Denekamp, Ilse M; Slot, Thierry K; Rothenberg, Gadi; Eisenberg, David

2017-10-23

The specific capacitance of a highly porous, nitrogen-doped carbon is nearly tripled by orthogonal optimization of the microstructure and surface chemistry. First, the carbons' hierarchical pore structure and specific surface area were tweaked by controlling the temperature and sequence of the thermal treatments. The best process (pyrolysis at 900 °C, washing, and subsequent annealing at 1000 °C) yielded a carbon with a specific capacitance of 117 F g -1 -nearly double that of a carbon made by a typical single-step synthesis at 700 °C. Following the structural optimization, the surface chemistry of the carbons was enriched by applying an oxidation routine based on a mixture of nitric and sulfuric acid in a 1:4 ratio at two different treatment temperatures (0 and 20 °C) and different treatment times. The optimal treatment times were 4 h at 0 °C and only 1 h at 20 °C. Overall, the specific capacitance nearly tripled relative to the original carbon, reaching 168 F g -1 . The inherent nitrogen doping of the carbon comes into interplay with the acid-induced surface functionalization, creating a mixture of oxygen- and nitrogen-oxygen functionalities. The evolution of the surface chemistry was carefully followed by X-ray photoelectron spectroscopy and by N 2 sorption porosimetry, revealing stepwise surface functionalization and simultaneous carbon etching. Overall, these processes are responsible for the peak-shaped capacitance trends in the carbons. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Zirconium doped nano-dispersed oxides of Fe, Al and Zn for destruction of warfare agents

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

Stengl, Vaclav, E-mail: stengl@uach.cz; Houskova, Vendula; Bakardjieva, Snejana

2010-11-15

Zirconium doped nano dispersive oxides of Fe, Al and Zn were prepared by a homogeneous hydrolysis of the respective sulfate salts with urea in aqueous solutions. Synthesized metal oxide hydroxides were characterized using Brunauer-Emmett-Teller (BET) surface area and Barrett-Joiner-Halenda porosity (BJH), X-ray diffraction (XRD), infrared spectroscopy (IR), scanning electron microscopy (SEM) and energy-dispersive X-ray microanalysis (EDX). These oxides were taken for an experimental evaluation of their reactivity with sulfur mustard (HD or bis(2-chloroethyl)sulfide), soman (GD or (3,3'-Dimethylbutan-2-yl)-methylphosphonofluoridate) and VX agent (S-[2-(diisopropylamino)ethyl]-O-ethyl-methylphosphonothionate). The presence of Zr{sup 4+} dopant can increase both the surface area and the surface hydroxylation of the resultingmore » doped oxides, decreases their crystallites' sizes thereby it may contribute in enabling the substrate adsorption at the oxide surface thus it can accelerate the rate of degradation of warfare agents. Addition of Zr{sup 4+} converts the product of the reaction of ferric sulphate with urea from ferrihydrite to goethite. We found out that doped oxo-hydroxides Zr-FeO(OH) - being prepared by a homogeneous hydrolysis of ferric and zirconium oxo-sulfates mixture in aqueous solutions - exhibit a comparatively higher degradation activity towards chemical warfare agents (CWAs). Degradation of soman or VX agent on Zr-doped FeO(OH) containing ca. 8.3 wt.% of zirconium proceeded to completion within 30 min.« less

Solid oxide fuel cell electrolytes produced via very low pressure suspension plasma spray and electrophoretic deposition

NASA Astrophysics Data System (ADS)

Fleetwood, James D.

Solid oxide fuel cells (SOFCs) are a promising element of comprehensive energy policies due to their direct mechanism for converting the oxidization of fuel, such as hydrogen, into electrical energy. Both very low pressure plasma spray and electrophoretic deposition allow working with high melting temperature SOFC suspension based feedstock on complex surfaces, such as in non-planar SOFC designs. Dense, thin electrolytes of ideal composition for SOFCs can be fabricated with each of these processes, while compositional control is achieved with dissolved dopant compounds that are incorporated into the coating during deposition. In the work reported, sub-micron 8 mole % Y2O3-ZrO2 (YSZ) and gadolinia-doped ceria (GDC), powders, including those in suspension with scandium-nitrate dopants, were deposited on NiO-YSZ anodes, via very low pressure suspension plasma spray (VLPSPS) at Sandia National Laboratories' Thermal Spray Research Laboratory and electrophoretic deposition (EPD) at Purdue University. Plasma spray was carried out in a chamber held at 320 - 1300 Pa, with the plasma composed of argon, hydrogen, and helium. EPD was characterized utilizing constant current deposition at 10 mm electrode separation, with deposits sintered from 1300 -- 1500 °C for 2 hours. The role of suspension constituents in EPD was analyzed based on a parametric study of powder loading, powder specific surface area, polyvinyl butyral (PVB) content, polyethyleneimine (PEI) content, and acetic acid content. Increasing PVB content and reduction of particle specific surface area were found to eliminate the formation of cracks when drying. PEI and acetic acid content were used to control suspension stability and the adhesion of deposits. Additionally, EPD was used to fabricate YSZ/GDC bilayer electrolyte systems. The resultant YSZ electrolytes were 2-27 microns thick and up to 97% dense. Electrolyte performance as part of a SOFC system with screen printed LSCF cathodes was evaluated with peak power densities as high as 520 mW/cm2 at 800 °C for YSZ and 350 mW/cm 2 at 800 °C for YSZ/GDC bilayer electrolytes.

Highly Self-Healable 3D Microsupercapacitor with MXene-Graphene Composite Aerogel.

PubMed

Yue, Yang; Liu, Nishuang; Ma, Yanan; Wang, Siliang; Liu, Weijie; Luo, Cheng; Zhang, Hang; Cheng, Feng; Rao, Jiangyu; Hu, Xiaokang; Su, Jun; Gao, Yihua

2018-05-22

High-performance microsupercapacitors (MSCs) with three-dimensional (3D) structure provide an effective approach to improve the ability of energy storage. Because the electrodes with 3D structure are generally easily destroyed under mechanical deformation in practical applications, we fabricated a self-healable 3D MSC consisting of MXene (Ti 3 C 2 T x )-graphene (reduced graphene oxide, rGO) composite aerogel electrode by wrapping it with a self-healing polyurethane as an outer shell. The MXene-rGO composite aerogel combining large specific surface area of rGO and high conductivity of the MXene can not only prevent the self-restacking of the lamella structure but also resist the poor oxidization of MXene to a degree. The MSC based on a 3D MXene-rGO aerogel delivers a large area specific capacitance of 34.6 mF cm -2 at a scan rate of 1 mV s -1 and an outstanding cycling performance with a capacitance retention up to 91% over 15 000 cycles. The 3D MSC presents an excellent self-healing ability with specific capacitance retention of 81.7% after the fifth healing. The preparation of this self-healable 3D MSC can provide a method for designing and manufacturing next-generation long-life multifunctional electronic devices further to meet the requirements of sustainable development.

Development and Testing of High Surface Area Iridium Anodes for Molten Oxide Electrolysis

NASA Technical Reports Server (NTRS)

Shchetkovskiy, Anatoliy; McKechnie, Timothy; Sadoway, Donald R.; Paramore, James; Melendez, Orlando; Curreri, Peter A.

2010-01-01

Processing of lunar regolith into oxygen for habitat and propulsion is needed to support future space missions. Direct electrochemical reduction of molten regolith is an attractive method of processing, because no additional chemical reagents are needed. The electrochemical processing of molten oxides requires high surface area, inert anodes. Such electrodes need to be structurally robust at elevated temperatures (1400-1600?C), be resistant to thermal shock, have good electrical conductivity, be resistant to attack by molten oxide (silicate), be electrochemically stable and support high current density. Iridium with its high melting point, good oxidation resistance, superior high temperature strength and ductility is the most promising candidate for anodes in high temperature electrochemical processes. Several innovative concepts for manufacturing such anodes by electrodeposition of iridium from molten salt electrolyte (EL-Form? process) were evaluated. Iridium electrodeposition to form of complex shape components and coating was investigated. Iridium coated graphite, porous iridium structure and solid iridium anodes were fabricated. Testing of electroformed iridium anodes shows no visible degradation. The result of development, manufacturing and testing of high surface, inert iridium anodes will be presented.

Development and Testing of High Surface Area Iridium Anodes for Molten Oxide Electrolysis

NASA Technical Reports Server (NTRS)

Shchetkovskiy, Anatoliy; McKechnie, Timothy; Sadoway, Donald R.; Paramore, James; Melendez, Orlando; Curreri, Peter A.

2010-01-01

Processing of lunar regolith into oxygen for habitat and propulsion is needed to support future space missions. Direct electrochemical reduction of molten regolith is an attractive method of processing, because no additional chemical reagents are needed. The electrochemical processing of molten oxides requires high surface area, inert anodes. Such electrodes need to be structurally robust at elevated temperatures (1400-1600 C), be resistant to thermal shock, have good electrical conductivity, be resistant to attack by molten oxide (silicate), be electrochemically stable and support high current density. Iridium with its high melting point, good oxidation resistance, superior high temperature strength and ductility is the most promising candidate for anodes in high temperature electrochemical processes. Several innovative concepts for manufacturing such anodes by electrodeposition of iridium from molten salt electrolyte (EL-Form process) were evaluated. Iridium electrodeposition to form of complex shape components and coating was investigated. Iridium coated graphite, porous iridium structure and solid iridium anodes were fabricated. Testing of electroformed iridium anodes shows no visible degradation. The result of development, manufacturing and testing of high surface, inert iridium anodes will be presented.

Modeling sorption of divalent metal cations on hydrous manganese oxide using the diffuse double layer model

USGS Publications Warehouse

Tonkin, J.W.; Balistrieri, L.S.; Murray, J.W.

2004-01-01

Manganese oxides are important scavengers of trace metals and other contaminants in the environment. The inclusion of Mn oxides in predictive models, however, has been difficult due to the lack of a comprehensive set of sorption reactions consistent with a given surface complexation model (SCM), and the discrepancies between published sorption data and predictions using the available models. The authors have compiled a set of surface complexation reactions for synthetic hydrous Mn oxide (HMO) using a two surface site model and the diffuse double layer SCM which complements databases developed for hydrous Fe (III) oxide, goethite and crystalline Al oxide. This compilation encompasses a range of data observed in the literature for the complex HMO surface and provides an error envelope for predictions not well defined by fitting parameters for single or limited data sets. Data describing surface characteristics and cation sorption were compiled from the literature for the synthetic HMO phases birnessite, vernadite and ??-MnO2. A specific surface area of 746 m2g-1 and a surface site density of 2.1 mmol g-1 were determined from crystallographic data and considered fixed parameters in the model. Potentiometric titration data sets were adjusted to a pH1EP value of 2.2. Two site types (???XOH and ???YOH) were used. The fraction of total sites attributed to ???XOH (??) and pKa2 were optimized for each of 7 published potentiometric titration data sets using the computer program FITEQL3.2. pKa2 values of 2.35??0.077 (???XOH) and 6.06??0.040 (???YOH) were determined at the 95% confidence level. The calculated average ?? value was 0.64, with high and low values ranging from 1.0 to 0.24, respectively. pKa2 and ?? values and published cation sorption data were used subsequently to determine equilibrium surface complexation constants for Ba2+, Ca2+, Cd 2+, Co2+, Cu2+, Mg2+, Mn 2+, Ni2+, Pb2+, Sr2+ and Zn 2+. In addition, average model parameters were used to predict additional sorption data for which complementary titration data were not available. The two-site model accounts for variability in the titration data and most metal sorption data are fit well using the pKa2 and ?? values reported above. A linear free energy relationship (LFER) appears to exist for some of the metals; however, redox and cation exchange reactions may limit the prediction of surface complexation constants for additional metals using the LFER. ?? 2003 Elsevier Ltd. All rights reserved.

Thiolated polyethylene oxide as a non-fouling element for nano-patterned bio-devices

NASA Astrophysics Data System (ADS)

Lisboa, Patrícia; Valsesia, Andrea; Colpo, Pascal; Gilliland, Douglas; Ceccone, Giacomo; Papadopoulou-Bouraoui, Andri; Rauscher, Hubert; Reniero, Fabiano; Guillou, Claude; Rossi, François

2007-03-01

This work describes the synthesis of a thiolated polyethylene oxide that self-assembles on gold to create a non-fouling surface. Thiolated polyethylene oxide was synthesised by reacting 16-mercaptohexadecanoic acid with polyethylene glycol mono methyl ether. The coverage of the thiolated polyethylene oxide on gold was studied by cyclic voltammetry, and the modified surfaces were characterised by X-ray photoelectron spectroscopy and ellipsometry. Protein resistance was assessed using quartz crystal microbalance. Results showed a non-fouling character produced by the thiolated polyethylene oxide. The synthesised product was used as the passivation layer on nano-patterned surfaces consisting of arrayed nano-spots, fabricated by plasma based colloidal lithography. The specific adsorption of anti-bovine serum albumin in the mercaptohexadecanoic acid spots was verified by atomic force microscopy.

Surface speciation and interactions between adsorbed chloride and water on cerium dioxide

NASA Astrophysics Data System (ADS)

Sutherland-Harper, Sophie; Taylor, Robin; Hobbs, Jeff; Pimblott, Simon; Pattrick, Richard; Sarsfield, Mark; Denecke, Melissa; Livens, Francis; Kaltsoyannis, Nikolas; Arey, Bruce; Kovarik, Libor; Engelhard, Mark; Waters, John; Pearce, Carolyn

2018-06-01

Ceria particles with different specific surface areas (SSA) were contaminated with chloride and water, then heat treated at 500 and 900 °C to investigate sorption behaviour of these species on metal oxides. Results from x-ray photoelectron spectroscopy and infrared spectroscopy showed chloride and water adsorption onto particles increased with surface area and that these species were mostly removed on heat treatment (from 6.3 to 0.8 at% Cl- on high SSA and from 1.4 to 0.4 at% on low SSA particles). X-ray diffraction revealed that chloride was not incorporated into the bulk ceria structure, but crystal size increased upon contamination. Ce LIII-edge x-ray absorption spectroscopy confirmed that chloride was not present in the first co-ordination sphere around Ce(IV) ions, so was not bonded to Ce as chloride in the bulk structure. Sintering of contaminated high SSA particles occurred with heat treatment at 900 °C, and they resembled low SSA particles synthesised at this temperature. Physical chloride-particle interactions were investigated using electron microscopy and energy dispersive x-ray analysis, showing that chloride was homogeneously distributed on ceria and that reduction of porosity did not trap surface-sorbed chloride inside the particles as surface area was reduced during sintering. This has implications for stabilisation of chloride-contaminated PuO2 for long term storage.

Characterization of hematite nanoparticles synthesized via two different pathways

NASA Astrophysics Data System (ADS)

Das, Soumya; Hendry, M. Jim

2014-08-01

Hematite is one of the most common and thermodynamically stable iron oxides found in both natural and anthropogenic systems. Owing to its ubiquity, stability, moderate specific surface area, and ability to sequester metals and metalloids from aquatic systems, it has been the subject of a large number of adsorption studies published during the past few decades. Although preparation techniques are known to affect the surface morphology of hematite nanoparticles, the effects of aging under environmentally relevant conditions have yet to be tested with respect to surface morphology, surface area, and adsorptive capacity. We prepared hematite via two different pathways and aged it under highly alkaline conditions encountered in many mill tailings settings. Crystal habits and morphologies of the hematite nanoparticles were analyzed via scanning electron microscopy and transmission electron microscopy. X-ray diffraction, Raman spectroscopy, and Brunauer-Emmett-Teller surface area analyses were also conducted on the hematite nanoparticles before and after aging. The hematite synthesized via an Fe(III) salt solution (average particle size 37 nm) was morphologically and structurally different from the hematite synthesized via ferrihydrite aging (average particle size 144 nm). Overall, our data demonstrate that the crystallinity of hematite produced via ferrihydrite transformation is susceptible to morphological alterations/modifications. In contrast, the hematite formed via hydrolysis of an Fe(III) salt solution remains very stable in terms of structure, size, and morphology even under extreme experimental conditions.

Influence of the sulfur species reactivity on biofilm conformation during pyrite colonization by Acidithiobacillus thiooxidans.

PubMed

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

2012-08-01

Massive pyrite (FeS₂) electrodes were potentiostatically modified by means of variable oxidation pulse to induce formation of diverse surface sulfur species (S(n)²⁻, S⁰). The evolution of reactivity of the resulting surfaces considers transition from passive (e.g., Fe(1-x )S₂) to active sulfur species (e.g., Fe(1-x )S(2-y ), S⁰). Selected modified pyrite surfaces were incubated with cells of sulfur-oxidizing Acidithiobacillus thiooxidans for 24 h in a specific culture medium (pH 2). Abiotic control experiments were also performed to compare chemical and biological oxidation. After incubation, the attached cells density and their exopolysaccharides were analyzed by confocal laser scanning microscopy (CLMS) and atomic force microscopy (AFM) on bio-oxidized surfaces; additionally, S(n)²⁻/S⁰ speciation was carried out on bio-oxidized and abiotic pyrite surfaces using Raman spectroscopy. Our results indicate an important correlation between the evolution of S(n)²⁻/S⁰ surface species ratio and biofilm formation. Hence, pyrite surfaces with mainly passive-sulfur species were less colonized by A. thiooxidans as compared to surfaces with active sulfur species. These results provide knowledge that may contribute to establishing interfacial conditions that enhance or delay metal sulfide (MS) dissolution, as a function of the biofilm formed by sulfur-oxidizing bacteria.

High Performance of N-Doped Graphene with Bubble-like Textures for Supercapacitors.

PubMed

Zhang, Shuo; Sui, Lina; Kang, Hongquan; Dong, Hongzhou; Dong, Lifeng; Yu, Liyan

2018-02-01

Nitrogen-doped graphene (NG) with wrinkled and bubble-like texture is fabricated by a thermal treatment. Especially, a novel sonication-assisted pretreatment with nitric acid is used to further oxidize graphene oxide and its binding with melamine molecules. There are many bubble-like nanoflakes with a dimension of about 10 nm appeared on the undulated graphene nanosheets. The bubble-like texture provides more active sites for effective ion transport and reversible capacitive behavior. The specific surface area of NG (5.03 at% N) can reach up to 438.7 m 2 g -1 , and the NG electrode demonstrates high specific capacitance (481 F g -1 at 1 A g -1 , four times higher than reduced graphene oxide electrode (127.5 F g -1 )), superior cycle stability (the capacitance retention of 98.9% in 2 m KOH and 99.2% in 1 m H 2 SO 4 after 8000 cycles), and excellent energy density (42.8 Wh kg -1 at power density of 500 W kg -1 in 2 m KOH aqueous electrolyte). The results indicate the potential use of NG as graphene-based electrode material for energy storage devices. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

PubMed Central

Johnson, Ian; Liu, Huinan

2013-01-01

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

Method of forming macro-structured high surface area transparent conductive oxide electrodes

DOEpatents

Forman, Arnold J.; Chen, Zhebo; Jaramillo, Thomas F.

2016-01-05

A method of forming a high surface area transparent conducting electrode is provided that includes depositing a transparent conducting thin film on a conductive substrate, where the transparent conducting thin film includes transparent conductive particles and a solution-based transparent conducting adhesive layer which serves to coat and bind together the transparent conducting particles, and heat treating the transparent conducting adhesion layer on the conductive substrate, where an increased surface area transparent conducting electrode is formed.

Polymerization method for formation of thermally exfoliated graphite oxide containing polymer

NASA Technical Reports Server (NTRS)

Prud'Homme, Robert K. (Inventor); Aksay, Ilhan A. (Inventor); Adamson, Douglas (Inventor)

2010-01-01

A process for polymerization of at least one monomer including polymerizing the at least one monomer in the presence of a modified graphite oxide material, which is a thermally exfoliated graphite oxide with a surface area of from about 300 m(esp 2)/g to 2600 m(esp 2/g.

Facile self-assembly and stabilization of metal oxide nanoparticles.

PubMed

Charbonneau, Cecile; Holliman, Peter J; Davies, Matthew L; Watson, Trystan M; Worsley, David A

2015-03-15

This paper describes a facile method of self-assembling different metal oxide nanoparticles into nanostructured materials via di-carboxylate linkers (oxalic acid) using TiO2 as an example. In this method, the di-carboxylate linkers react with surface hydroxyls on metal oxide nanoparticles forming covalent, ester-like bonds, which enable the binding of two metal oxide particles, one at either end of the linker and facilitates efficient self-assembly of one group of metal oxide nanoparticles homogeneously distributed onto the surface of another group. The oxalate linkers can then be removed by thermal decomposition. This approach is shown to be effective using differently-sized TiO2 nanoparticles, namely in-house synthesized 3-5nm anatase nanocrystals and Degussa P25 titania particles (mean 21nm particle size). Our data show that the application of a high temperature heat treatment (450°C for 30min), conventionally applied to achieve a stable porous structure by thermal decomposition of the linker molecules and by inducing inter-particle necking, damages the surface area of the nanostructured material. However, here we show that sintering at 300°C for 30min or by flash near infrared radiation sintering for 12s efficiently decomposes the oxalate linkers and stabilizes the nanostructure of the material whilst maintaining its high surface area. Copyright © 2013 Elsevier Inc. All rights reserved.

Studies of reaction geometry in oxidation and reduction of the alkaline silver electrode

NASA Technical Reports Server (NTRS)

Butler, E. A.; Blackham, A. U.

1971-01-01

Two methods of surface area estimations of sintered silver electrodes have given roughness factors of 58 and 81. One method is based on constant current oxidation, the other is based on potentiostatic oxidation. Examination of both wire and sintered silver electrodes via scanning electron microscopy at various stages of oxidation have shown that important structural features are mounds of oxide. In potentiostatic oxidations these appear to form on sites instantaneously nucleated while in constant current oxidations progressive nucleation is indicated.

N-doped structures and surface functional groups of reduced graphene oxide and their effect on the electrochemical performance of supercapacitor with organic electrolyte

NASA Astrophysics Data System (ADS)

Li, Shin-Ming; Yang, Shin-Yi; Wang, Yu-Sheng; Tsai, Hsiu-Ping; Tien, Hsi-Wen; Hsiao, Sheng-Tsung; Liao, Wei-Hao; Chang, Chien-Liang; Ma, Chen-Chi M.; Hu, Chi-Chang

2015-03-01

Nitrogen-doped reduced graphene oxide (N-rGO) has been synthesized using a simple, efficient method combining instant thermal exfoliation and covalent bond transformation from a melamine-graphene oxide mixture. The capacitive performance of N-rGO has been tested in both aqueous (0.5 M H2SO4) and organic (1 M tetraethyl-ammonium tetrafluoroborate (TEABF4) in propylene carbonate (PC)) electrolytes, which are compared with those obtained from thermal-reduced graphene oxide (T-rGO) and chemical-reduced graphene oxide (C-rGO). The contributions of scan-rate-independent (double-layer-like) and scan-rate-dependent (pseudo-capacitance-like) capacitance of all reduced graphene oxides in both aqueous and organic electrolytes were evaluated and compared. The results show that relatively rich oxygen-containing functional groups on C-rGO form significant ion-diffusion barrier, resulting in worse electrochemical responses in organic electrolyte. By contrast, the N-doped structures, large surface area, and lower density of oxygen-containing groups make N-rGO become a promising electrode material for organic electric double-layer capacitors (EDLCs). The capacitance rate-retention of N-rGO reaches 71.1% in 1 M TEABF4/PC electrolyte when the scan rate is elevated to 200 mVs-1, demonstrating that N-rGO improves the relatively low-power drawback of EDLCs in organic electrolytes. The specific energy and power of a symmetric N-rGO cell in the organic electrolyte reach 25 Wh kg-1 and 10 kW kg-1, respectively.

Three-Dimensionally Hierarchical Graphene Based Aerogel Encapsulated Sulfur as Cathode for Lithium/Sulfur Batteries

PubMed Central

Li, Haipeng; Sun, Liancheng; Wang, Zhuo; Zhang, Yongguang; Tan, Taizhe; Wang, Gongkai

2018-01-01

A simple and effective method was developed to obtain the electrode for lithium/sulfur (Li/S) batteries with high specific capacity and cycling durability via adopting an interconnected sulfur/activated carbon/graphene (reduced graphene oxide) aerogel (S/AC/GA) cathode architecture. The AC/GA composite with a well-defined interconnected conductive network was prepared by a reduction-induced self-assembly process, which allows for obtaining compact and porous structures. During this process, reduced graphene oxide (RGO) was formed, and due to the presence of oxygen-containing functional groups on its surface, it not only improves the electronic conductivity of the cathode but also effectively inhibits the polysulfides dissolution and shuttle. The introduced activated carbon allowed for lateral and vertical connection between individual graphene sheets, completing the formation of a stable three-dimensionally (3D) interconnected graphene framework. Moreover, a high specific surface area and 3D interconnected porous structure efficiently hosts a higher amount of active sulfur material, about 65 wt %. The designed S/AC/GA composite electrodes deliver an initial capacity of 1159 mAh g−1 at 0.1 C and can retain a capacity of 765 mAh g−1 after 100 cycles in potential range from 1 V to 3 V. PMID:29373525

Sorption of uranium (VI) on homoionic sodium smectite experimental study and surface complexation modeling.

PubMed

Korichi, Smain; Bensmaili, Aicha

2009-09-30

This paper is an extension of a previous paper where the natural and purified clay in the homoionic Na form were physico-chemically characterized (doi:10.1016/j.clay.2008.04.014). In this study, the adsorption behavior of U (VI) on a purified Na-smectite suspension is studied using batch adsorption experiments and surface complexation modeling (double layer model). The sorption of uranium was investigated as a function of pH, uranium concentration, solid to liquid ratio, effect of natural organic matter (NOM) and NaNO(3) background electrolyte concentration. Using the MINTEQA2 program, the speciation of uranium was calculated as a function of pH and uranium concentration. Model predicted U (VI) aqueous speciation suggests that important aqueous species in the [U (VI)]=1mg/L and pH range 3-7 including UO(2)(2+), UO(2)OH(+), and (UO(2))(3)(OH)(5)(+). The concentration of UO(2)(2+) decreased and that of (UO(2))(3)(OH)(5)(+) increased with increasing pH. The potentiometric titration values and uptake of uranium in the sodium smectite suspension were simulated by FITEQL 4.0 program using a two sites model, which is composed of silicate and aluminum reaction sites. We compare the acidity constants values obtained by potentiometric titration from the purified sodium smectite with those obtained from single oxides (quartz and alpha-alumina), taking into account the surface heterogeneity and the complex nature of natural colloids. We investigate the uranium sorption onto purified Na-smectite assuming low, intermediate and high edge site surfaces which are estimated from specific surface area percentage. The sorption data is interpreted and modeled as a function of edge site surfaces. A relationship between uranium sorption and total site concentration was confirmed and explained through variation in estimated edge site surface value. The modeling study shows that, the convergence during DLM modeling is related to the best estimation of the edge site surface from the N(2)-BET specific surface area, SSA(BET) (thus, total edge site concentrations). The specific surface area should be at least 80-100m(2)/g for smectite clays in order to reach convergence during the modeling. The range of 10-20% SSA(BET) was used to estimate the values of edge site surfaces that led to the convergence during modeling. An agreement between the experimental data and model predictions is found reasonable when 15% SSA(BET) was used as edge site surface. However, the predicted U (VI) adsorption underestimated and overestimated the experimental observations at the 10 and 20% of the measured SSA(BET), respectively. The dependence of uranium sorption modeling results on specific surface area and edge site surface is useful to describe and predict U (VI) retardation as a function of chemical conditions in the field-scale reactive transport simulations. Therefore this approach can be used in the environmental quality assessment.

Thermal oxidation synthesis hollow MoO{sub 3} microspheres and their applications in lithium storage and gas-sensing

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

Zhao, Xinyu; School of Petrochemical Engineering, Shenyang University of Technology, Liaoyang 111003; Cao, Minhua, E-mail: caomh@bit.edu.cn

2013-06-01

Graphical abstract: MoO{sub 3} hollow microspheres were synthesized via a facile and template-free solvothermal route and subsequent heat treatment in air. The MoO{sub 3} hollow microspheres exhibit an improved lithium storage and gas-sensing performance. Highlights: ► Hollow MoO{sub 3} microspheres were synthesized by thermal oxidation of hollow MoO{sub 2}. ► The MoO{sub 3} hollow microspheres have a relatively high specific surface area. ► The MoO{sub 3} hollow microspheres exhibit improved lithium storage performance. ► The MoO{sub 3} hollow microspheres show good responses to ammonia gas. - Abstract: In this paper, MoO{sub 3} hollow microspheres were synthesized via a facile andmore » template-free solvothermal route and subsequent heat treatment in air. The MoO{sub 3} hollow microspheres have a relatively high specific surface area, and with such a feature, the as-synthesized MoO{sub 3} hollow microspheres have potential applications in Li-ion battery and gas-sensor. When tested as a Li-storage anode material, the MoO{sub 3} hollow microspheres show a higher discharge capacity of 1377.1 mA h g{sup −1} in the first discharge and a high reversible capacity of 780 mA h g{sup −1} after 100 cycles at a rate of 1 C. Furthermore, as a gas sensing material, the MoO{sub 3} hollow microspheres exhibit an improved sensitivity and short response/recovery time to trace levels of ammonia gas.« less

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

PubMed

Stepniowski, Wojciech J; Misiolek, Wojciech Z

2018-05-29

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

Defects and Small Polarons on Oxide Surfaces

NASA Astrophysics Data System (ADS)

Janotti, Anderson

The presence and behavior of defects on the surface of oxides are central in many research areas, including catalysis, photochemistry, solar cells, and surface science in general. Experimental characterization of individual defects and their activities are challenging and often requires special preparations of the surface. First-principles calculations based on density functional theory are a powerful tool to study surfaces and defects, often providing information on properties that are difficult to access experimentally. Here we discuss the behavior of defects on oxide surfaces from the perspective on first-principles calculations. We use the oxygen vacancy on TiO2 surface as example, a system that has been extensively reported in the literature. Using DFT with a hybrid function, we discuss surface states induced by the defect and localization of the excess charge in the form of small polarons. We then discuss the effects of hydrogen and compare the behavior of these defects on the surface with that in the bulk. We also compare our recent results with previous theoretical studies and experiments. Finally, we generalize the findings on TiO2 to the surfaces of other oxides. This work was supported by the NSF.

Catalytic Properties of Fe-containing Layered Aluminosilicates in Photo-oxidation of Dye “Methyl Green”

NASA Astrophysics Data System (ADS)

Shadrina, O. A.; Dashinamzhilova, E. Ts; Khankhasaeva, S. Ts

2017-11-01

The iron-containing materials with an iron content of 40 mg/g and 52.5 mg/g, a specific surface area of 107 m2/g and 96 m2/g are developed on the basis of natural layered aluminosilicate (montmorillonite) and polyhydroxo complexes of iron. It is shown that the materials exhibit high catalytic activity in the photo-oxidation of dye “Methyl Green”. The influence of physicochemical parameters (loading of the catalyst, a ratio of initial concentrations [H2O2]/[MG] on the efficiency of the dye photo-oxidation was established. The optimum conditions, which made it possible to achieve high mineralization and 100 % the dye oxidation efficiency were determined: the catalyst loading equal to 1.0 g/l and the ratio of [H2O2] and [MG] equal to stoichiometric ratio (55 mol/mol). The decrease of the total organic carbon content after photo-oxidation reaction was 56.5%. The average value of the quantum yield of the dye photo-oxidation was to 0.30 mol/Einstein. The results of the conducted research show that the developed iron-containing materials are the promising catalysts for photo-Fenton processes of oxidative degradation of organic compounds. The materials are of interest for use in wastewater treatment processes from toxic organic pollutants.

Tin oxide nanosheet assembly for hydrophobic/hydrophilic coating and cancer sensing.

PubMed

Masuda, Yoshitake; Ohji, Tatsuki; Kato, Kazumi

2012-03-01

Tin oxide nanosheets were crystallized on transparent conductive oxide substrates of fluorine-doped tin oxide in aqueous solutions. The nanosheets had chemical ratio of Sn:O:F = 1:1.85:0.076, suggesting fluorine doping into SnO(2). They were hydrophobic surfaces with contact angle of 140°. They were converted to hydrophilic surfaces with contact angle of below 1° by light irradiation. The simple water process will be applied to surface coating of polymers, metals, biomaterials, papers, etc. Furthermore, the tin oxide nanosheets were modified with dye-labeled monoclonal antibody. Monoclonal antibody reacts with human alpha-fetoprotein in blood serum of hepatocellular cancer patient. Photoluminescence and photocurrent were obtained from the nanosheets under excitation light. Photoelectric conversion was an essence in the sensing system. The tin oxide nanosheets with dye-labeled prostate specific antigen will be used for electrodes of prostate cancer sensors. © 2012 American Chemical Society

Natural oxidation of a temperature series of biochars: opposite effect on the sorption of aromatic cationic herbicides.

PubMed

Shi, Kaishun; Xie, Ya; Qiu, Yuping

2015-04-01

The natural oxidation of biochar in the environment has been widely observed. However, its influence on the sorption of organic contaminants remains poorly understood. In the present study, a series of wood-based biochars prepared between 300 and 600°C (referred to as BC300-BC600) was abiotically incubated for one year to examine the aging effect of the temperature series of biochars on their sorption of aromatic cationic herbicides (ACHs, paraquat and diquat) as well as a nonpolar reference adsorbate (naphthalene). One year of oxidation showed no obvious effect on the surface area, but distinct increases in the O/C elemental ratio, density of the surface groups and cation exchange capacity (CEC) were observed. Therefore, these properties were significantly affected by the charring temperature. After incubation, high-temperature biochars (BC500 and BC600) displayed a 14.1-36.3% decrease in the sorption (qm) of ACHs. The alteration of their sorption tendency was similar to the reduced sorption of naphthalene on oxidized biochars, in which the increased surface groups lowered the surface area accessible to adsorbates because of blockage by adsorbed water molecule clusters. Conversely, a pronounced increase of ACHs sorption by 121.7-201.1% on the low-temperature biochar (BC300) was observed, presumably due to the increase of CEC values after oxidation. This result was further demonstrated by a significant linear relationship between the paraquat sorption (qm) and CEC values (R(2)=0.9895) of oxidized biochars. Interestingly, one year of oxidation simultaneously resulted in an enhanced sorption of paraquat and a reduced sorption of diquat on BC400, which indicated that the oxidation-induced sorption change of ACHs is a complex function of changes in the surface properties of the biochars as well as the molecular structure of the solute. Copyright © 2015 Elsevier Inc. All rights reserved.

Magnetic field controlled graphene oxide-based origami with enhanced surface area and mechanical properties.

PubMed

Park, Ok-Kyung; Tiwary, Chandra Sekhar; Yang, Yang; Bhowmick, Sanjit; Vinod, Soumya; Zhang, Qingbo; Colvin, Vicki L; Asif, S A Syed; Vajtai, Robert; Penev, Evgeni S; Yakobson, Boris I; Ajayan, Pulickel M

2017-06-01

One can utilize the folding of paper to build fascinating 3D origami architectures with extraordinary mechanical properties and surface area. Inspired by the same, the morphology of 2D graphene can be tuned by addition of magnetite (Fe 3 O 4 ) nanoparticles in the presence of a magnetic field. The innovative 3D architecture with enhanced mechanical properties also shows a high surface area (∼2500 m 2 g -1 ) which is utilized for oil absorption. Detailed microscopy and spectroscopy reveal rolling of graphene oxide (GO) sheets due to the magnetic field driven action of magnetite particles, which is further supported by molecular dynamics (MD) simulations. The macroscopic and local deformation resulting from in situ mechanical loading inside a scanning electron microscope reveals a change in the mechanical response due to a change internal morphology, which is further supported by MD simulation.

Impedance spectroscopy study on graphene wrapped nanocrystalline V{sub 2}O{sub 5}

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

Bhaskaram, D. Surya, E-mail: dsurya.b@gmail.com; Govindaraj, G.; Cheruku, Rajesh

2016-05-23

Nanocrystalline V{sub 2}O{sub 5} was synthesized by solvothermal technique, which has potential application as electrode material in supercapacitors. The graphene oxide (GO) was prepared by modified Hummer’s method. The V{sub 2}O{sub 5}/ reduced graphene oxide (RGO) composite was synthesized using surfactant free hydrothermal technique to enhance the functionality in terms of conductivity and surface area of V{sub 2}O{sub 5}. The structural characterization was accomplished through X-ray diffraction and Raman spectroscopy. Morphology was identified by SEM and surface area of VRGO was enhanced by 8 times in comparison with V{sub 2}O{sub 5} nano particles, as confirmed through BET surface area analysis.more » Electrical characterization was done through impedance spectroscopy and the results showed decrease in sample resistance after wrapping V{sub 2}O{sub 5} with RGO.« less

Effects of Nano-CeO₂ with Different Nanocrystal Morphologies on Cytotoxicity in HepG2 Cells.

PubMed

Wang, Lili; Ai, Wenchao; Zhai, Yanwu; Li, Haishan; Zhou, Kebin; Chen, Huiming

2015-09-02

Cerium oxide nanoparticles (nano-CeO₂) have been reported to cause damage and apoptosis in human primary hepatocytes. Here, we compared the toxicity of three types of nano-CeO₂ with different nanocrystal morphologies (cube-, octahedron-, and rod-like crystals) in human hepatocellular carcinoma cells (HepG2). The cells were treated with the nano-CeO₂ at various concentrations (6.25, 12.5, 25, 50, 100 μg/mL). The crystal structure, size and morphology of nano-CeO₂ were investigated by X-ray diffractometry and transmission electron microscopy. The specific surface area was detected using the Brunauer, Emmet and Teller method. The cellular morphological and internal structure were observed by microscopy; apoptotic alterations were measured using flow cytometry; nuclear DNA, mitochondrial membrane potential (MMP), reactive oxygen species (ROS) and glutathione (GSH) in HepG2 cells were measured using high content screening technology. The scavenging ability of hydroxyl free radicals and the redox properties of the nano-CeO₂ were measured by square-wave voltammetry and temperature-programmed-reduction methods. All three types of nano-CeO₂ entered the HepG2 cells, localized in the lysosome and cytoplasm, altered cellular shape, and caused cytotoxicity. The nano-CeO₂ with smaller specific surface areas induced more apoptosis, caused an increase in MMP, ROS and GSH, and lowered the cell's ability to scavenge hydroxyl free radicals and antioxidants. In this work, our data demonstrated that compared with cube-like and octahedron-like nano-CeO₂, the rod-like nano-CeO₂ has lowest toxicity to HepG2 cells owing to its larger specific surface areas.

Rapid in situ generation of two patterned chemoselective surface chemistries from a single hydroxy-terminated surface using controlled microfluidic oxidation.

PubMed

Pulsipher, Abigail; Westcott, Nathan P; Luo, Wei; Yousaf, Muhammad N

2009-06-10

In this work, we develop a new, rapid and inexpensive method to generate spatially controlled aldehyde and carboxylic acid surface groups by microfluidic oxidation of 11-hydroxyundecylphosphonic acid self-assembled monolayers (SAMs) on indium tin oxide (ITO) surfaces. SAMs are activated and patterned using a reversibly sealable, elastomeric polydimethylsiloxane cassette, fabricated with preformed micropatterns by soft lithography. By flowing the mild oxidant pyridinium chlorochromate through the microchannels, only selected areas of the SAM are chemically altered. This microfluidic oxidation strategy allows for ligand immobilization by two chemistries originating from a single SAM composition. ITO is robust, conductive, and transparent, making it an ideal platform for studying interfacial interactions. We display spatial control over the immobilization of a variety of ligands on ITO and characterize the resulting oxime and amide linkages by electrochemistry, X-ray photoelectron spectroscopy, contact angle, fluorescence microscopy, and atomic force microscopy. This general method may be used with many other materials to rapidly generate patterned and tailored surfaces for studies ranging from molecular electronics to biospecific cell-based assays and biomolecular microarrays.

Mesoporous ZnS–NiS Nanocomposites for Nonenzymatic Electrochemical Glucose Sensors

PubMed Central

Wei, Chengzhen; Cheng, Cheng; Zhao, Junhong; Wang, Zhangtao; Wu, Haipeng; Gu, Kaiyue; Du, Weimin; Pang, Huan

2015-01-01

Mesoporous ZnS–NiS composites are prepared via ion- exchange reactions using ZnS as the precursor. The prepared mesoporous ZnS–NiS composite materials have large surface areas (137.9 m2 g−1) compared with the ZnS precursor. More importantly, the application of these mesoporous ZnS–NiS composites as nonenzymatic glucose sensors was successfully explored. Electrochemical sensors based on mesoporous ZnS–NiS composites exhibit a high selectivity and a low detection limit (0.125 μm) toward the oxidation of glucose, which can mainly be attributed to the morphological characteristics of the mesoporous structure with high specific surface area and a rational composition of the two constituents. In addition, the mesoporous ZnS–NiS composites coated on the surface of electrodes can be used to modify the mass transport regime, and this alteration can, in favorable circumstances, facilitate the amperometric discrimination between species. These results suggest that such mesoporous ZnS–NiS composites are promising materials for nonenzymatic glucose sensors. PMID:25861568

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

PubMed

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

2009-02-01

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

Thin film passivation of laser generated 3D micro patterns in lithium manganese oxide cathodes

NASA Astrophysics Data System (ADS)

Pröll, J.; Kohler, R.; Bruns, M.; Oberst, V.; Weidler, P. G.; Heißler, S.; Kübel, C.; Scherer, T.; Prang, R.; Seifert, H. J.; Pfleging, W.

2013-03-01

The increasing need for long-life lithium-ion batteries requires the further development of electrode materials. Especially on the cathode side new materials or material composites are needed to increase the cycle lifetime. On the one hand, spinel-type lithium manganese oxide is a promising candidate to be used as cathode material due to its non-toxicity, low cost and good thermal stability. On the other hand, the spinel structure suffers from change in the oxidation state of manganese during cycling which is also accompanied by loss of active material into the liquid electrolyte. The general trend is to enhance the active surface area of the cathode in order to increase lithium-ion mobility through the electrode/electrolyte interface, while an enhanced surface area will also promote chemical degradation. In this work, laser microstructuring of lithium manganese oxide thin films was applied in a first step to increase the active surface area. This was done by using 248 nm excimer laser radiation and chromium/quartz mask imaging techniques. In a second step, high power diode laser-annealing operating at a wavelength of 940 nm was used for forming a cubic spinel-like battery phase. This was verified by means of Raman spectroscopy and cyclic voltammetric measurements. In a last step, the laser patterned thin films were coated with indium tin oxide (ITO) layers with a thickness of 10 nm to 50 nm. The influence of the 3D surface topography as well as the ITO thickness on the electrochemical performance was studied by cyclic voltammetry. Post-mortem studies were carried out by using scanning electron microscopy and focused ion beam analysis.

Quantitative control of poly(ethylene oxide) surface antifouling and biodetection through azimuthally enhanced grating coupled-surface plasmon resonance sensing

NASA Astrophysics Data System (ADS)

Sonato, Agnese; Silvestri, Davide; Ruffato, Gianluca; Zacco, Gabriele; Romanato, Filippo; Morpurgo, Margherita

2013-12-01

Grating Coupled-Surface Plasmon reflectivity measurements carried out under azimuth and polarization control (GC-SPR φ ≠ 0°) were used to optimize the process of gold surface dressing with poly(ethylene oxide) (PEO) derivatives of different molecular weight, with the final goal to maximize the discrimination between specific and non-specific binding events occurring at the surface. The kinetics of surface deposition of thiol-ending PEOs (0.3, 2 and 5 kDa), introduced as antifouling layers, was monitored. Non-specific binding events upon immersion of the surfaces into buffers containing either 0.1% bovine serum albumin or 1% Goat Serum, were evaluated as a function of polymer size and density. A biorecognition event between avidin and biotin was then monitored in both buffers at selected low and high polymer surface densities and the contribution of analyte and fouling elements to the signal was precisely quantified. The 0.3 kDa PEO film was unable to protect the surface from non-specific interactions at any tested density. On the other hand, the 2 and 5 kDa polymers at their highest surface densities guaranteed full protection from non-specific interactions from both buffers. These densities were reached upon a long deposition time (24-30 h). The results pave the way toward the application of this platform for the detection of low concentration and small dimension analytes, for which both non-fouling and high instrumental sensitivity are fundamental requirements.

PREPARATION OF REFRACTORY OXIDE CRYSTALS

DOEpatents

Grimes, W.R.; Shaffer, J.H.; Watson, G.M.

1962-11-13

A method is given for preparing uranium dioxide, thorium oxide, and beryllium oxide in the form of enlarged individual crystals. The surface of a fused alkali metal halide melt containing dissolved uranium, thorium, or beryllium values is contacted with a water-vapor-bearing inert gas stream at a rate of 5 to 10 cubic centimeters per minute per square centimeter of melt surface area. Growth of individual crystals is obtained by prolonged contact. Beryllium oxide-coated uranium dioxide crystals are prepared by disposing uranium dioxide crystals 5 to 20 microns in diameter in a beryllium-containing melt and contacting the melt with a water-vapor-bearing inert gas stream in the same manner. (AEC)

Effect of mass density on surface morphology of electrodeposited manganese oxide films

NASA Astrophysics Data System (ADS)

Singh, Avtar; Kumar, Davinder; Thakur, Anup; Kaur, Raminder

2018-05-01

This work focus on high surface area morphology of manganese oxide films which are currently required for electrochemical capacitor electrode to enhance their performance. Electrodeposition of manganese oxide films was carried out using Chronoamperometry for different deposition time ranging from 30 to 120 sec. Cronoamperomertic I-T integrated data have been used to analyze active mass of all electrodeposited films. Morphological study of the deposited films with different mass was carried out through scanning electron microscopy. Film deposited for 30 sec time show highest porous morphology than others. Manganese oxide films with high porosity are suitable for electrochemical capacitor electrode.

High reduction of interfacial charge recombination in colloidal quantum dot solar cells by metal oxide surface passivation.

PubMed

Chang, Jin; Kuga, Yuki; Mora-Seró, Iván; Toyoda, Taro; Ogomi, Yuhei; Hayase, Shuzi; Bisquert, Juan; Shen, Qing

2015-03-12

Bulk heterojunction (BHJ) solar cells based on colloidal QDs and metal oxide nanowires (NWs) possess unique and outstanding advantages in enhancing light harvesting and charge collection in comparison to planar architectures. However, the high surface area of the NW structure often brings about a large amount of recombination (especially interfacial recombination) and limits the open-circuit voltage in BHJ solar cells. This problem is solved here by passivating the surface of the metal oxide component in PbS colloidal quantum dot solar cells (CQDSCs). By coating thin TiO2 layers onto ZnO-NW surfaces, the open-circuit voltage and power conversion efficiency have been improved by over 40% in PbS CQDSCs. Characterization by transient photovoltage decay and impedance spectroscopy indicated that the interfacial recombination was significantly reduced by the surface passivation strategy. An efficiency as high as 6.13% was achieved through the passivation approach and optimization for the length of the ZnO-NW arrays (device active area: 16 mm2). All solar cells were tested in air, and exhibited excellent air storage stability (without any performance decline over more than 130 days). This work highlights the significance of metal oxide passivation in achieving high performance BHJ solar cells. The charge recombination mechanism uncovered in this work could shed light on the further improvement of PbS CQDSCs and/or other types of solar cells.

Startup of reactors for anoxic ammonium oxidation: experiences from the first full-scale anammox reactor in Rotterdam.

PubMed

van der Star, Wouter R L; Abma, Wiebe R; Blommers, Dennis; Mulder, Jan-Willem; Tokutomi, Takaaki; Strous, Marc; Picioreanu, Cristian; van Loosdrecht, Mark C M

2007-10-01

The first full-scale anammox reactor in the world was started in Rotterdam (NL). The reactor was scaled-up directly from laboratory-scale to full-scale and treats up to 750 kg-N/d. In the initial phase of the startup, anammox conversions could not be identified by traditional methods, but quantitative PCR proved to be a reliable indicator for growth of the anammox population, indicating an anammox doubling time of 10-12 days. The experience gained during this first startup in combination with the availability of seed sludge from this reactor, will lead to a faster startup of anammox reactors in the future. The anammox reactor type employed in Rotterdam was compared to other reactor types for the anammox process. Reactors with a high specific surface area like the granular sludge reactor employed in Rotterdam provide the highest volumetric loading rates. Mass transfer of nitrite into the biofilm is limiting the conversion of those reactor types that have a lower specific surface area. Now the first full-scale commercial anammox reactor is in operation, a consistent and descriptive nomenclature is suggested for reactors in which the anammox process is employed.

Aerosol-spray diverse mesoporous metal oxides from metal nitrates.

PubMed

Kuai, Long; Wang, Junxin; Ming, Tian; Fang, Caihong; Sun, Zhenhua; Geng, Baoyou; Wang, Jianfang

2015-04-21

Transition metal oxides are widely used in solar cells, batteries, transistors, memories, transparent conductive electrodes, photocatalysts, gas sensors, supercapacitors, and smart windows. In many of these applications, large surface areas and pore volumes can enhance molecular adsorption, facilitate ion transfer, and increase interfacial areas; the formation of complex oxides (mixed, doped, multimetallic oxides and oxide-based hybrids) can alter electronic band structures, modify/enhance charge carrier concentrations/separation, and introduce desired functionalities. A general synthetic approach to diverse mesoporous metal oxides is therefore very attractive. Here we describe a powerful aerosol-spray method for synthesizing various mesoporous metal oxides from low-cost nitrate salts. During spray, thermal heating of precursor droplets drives solvent evaporation and induces surfactant-directed formation of mesostructures, nitrate decomposition and oxide cross-linking. Thirteen types of monometallic oxides and four groups of complex ones are successfully produced, with mesoporous iron oxide microspheres demonstrated for photocatalytic oxygen evolution and gas sensing with superior performances.

Laser surface treatment of porous ceramic substrate for application in solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Mahmod, D. S. A.; Khan, A. A.; Munot, M. A.; Glandut, N.; Labbe, J. C.

2016-08-01

Laser has offered a large number of benefits for surface treatment of ceramics due to possibility of localized heating, very high heating/cooling rates and possibility of growth of structural configurations only produced under non-equilibrium high temperature conditions. The present work investigates oxidation of porous ZrB2-SiC sintered ceramic substrates through treatment by a 1072 ± 10 nm ytterbium fiber laser. A multi-layer structure is hence produced showing successively oxygen rich distinct layers. The porous bulk beneath these layers remained unaffected as this laser-formed oxide scale and protected the substrate from oxidation. A glassy SiO2 structure thus obtained on the surface of the substrate becomes subject of interest for further research, specifically for its utilization as solid protonic conductor in Solid Oxide Fuel Cells (SOFCs).

Pseudo-Capacitors: SPPS Deposition and Electrochemical Analysis of α-MoO3 and Mo2N Coatings

NASA Astrophysics Data System (ADS)

Golozar, Mehdi; Chien, Ken; Lian, Keryn; Coyle, Thomas W.

2013-06-01

Solution precursor plasma spraying (SPPS) is a novel thermal spray process in which a solution precursor is injected into the high-temperature zone of a DC-arc plasma jet to allow solvent evaporation from the precursor droplets, solute precipitation, and precipitate pyrolysis prior to substrate impact. This investigation explored the potential of SPPS to fabricate α-MoO3 coatings with fine grain sizes, high porosity levels, and high surface area: characteristics needed for application as pseudo-capacitor electrodes. Since molybdenum nitride has shown a larger electrochemical stability window and higher specific area capacitance, the α-MoO3 deposits were subsequently converted into molybdenum nitride. A multistep heat-treatment procedure resulted in a topotactic phase-transformation mechanism, which retained the high surface area lath-shaped features of the original α-MoO3. The electrochemical behaviors of molybdenum oxide and molybdenum nitride deposits formed under different deposition conditions were studied using cyclic voltammetry to assess the influence of the resulting microstructure on the charge storage behavior and potential for use in pseudo-capacitors.

Liquid-Phase Exfoliation into Monolayered BiOBr Nanosheets for Photocatalytic Oxidation and Reduction

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

Yu, Hongjian; Huang, Hongwei; Xu, Kang

2017-09-26

Monolayered photocatalytic materials have attracted huge research interests in terms of their large specific surface area and ample active sites. Sillén-structured layered BiOX (X = Cl, Br, I) casts great prospects owing to their strong photo-oxidation ability and high stability. Fabrication of monolayered BiOX by a facile, low-cost, and scalable approach is highly challenging and anticipated. Herein, we describe the large-scale preparation of monolayered BiOBr nanosheets with a thickness of ~0.85 nm via a readily achievable liquid-phase exfoliation strategy with assistance of formamide at ambient conditions. The as-obtained monolayered BiOBr nanosheets are allowed diverse superiorities, such as enhanced specific surfacemore » area, promoted band structure, and strengthened charge separation. Profiting from these benefits, the advanced BiOBr monolayers not only show excellent adsorption and photodegradation performance for treating contaminants, but also demonstrate a greatly promoted photocatalytic activity for CO2 reduction into CO and CH4. Additionally, monolayered BiOI nanosheets have also been obtained by the same synthetic approach. Our work offers a mild and general approach for preparation of monolayered BiOX, and may have huge potential to be extended to the synthesis of other single-layer two-dimensional materials.« less

Conductive Circuit Containing a Polymer Composition Containing Thermally Exfoliated Graphite Oxide and Method of Making the Same

NASA Technical Reports Server (NTRS)

Aksay, Ilhan A. (Inventor); Prud'Homme, Robert K. (Inventor)

2017-01-01

A conductive circuit containing a polymer composite, which contains at least one polymer and a modified graphite oxide material, containing thermally exfoliated graphite oxide having a surface area of from about 300 sq m/g to 2600 sq m/g, and a method of making the same.

Conductive Circuit Containing a Polymer Composition Containing Thermally Exfoliated Graphite Oxide and Method of Making the Same

NASA Technical Reports Server (NTRS)

Prud'Homme, Robert K. (Inventor); Aksay, Ilhan A. (Inventor)

2014-01-01

A conductive circuit containing a polymer composite, which contains at least one polymer and a modified graphite oxide material, containing thermally exfoliated graphite oxide having a surface area of from about 300 m(sup.2)/g to 2600 m(sup.2)/g, and a method of making the same.

Electrospray painted article containing thermally exfoliated graphite oxide and method for their manufacture

NASA Technical Reports Server (NTRS)

Prud'Homme, Robert K. (Inventor); Aksay, Ilhan A. (Inventor); Korkut, Sibel (Inventor)

2011-01-01

A painted polymer part containing a conductive polymer composition containing at least one polymer and a modified graphite oxide material, which is a thermally exfoliated graphite oxide with a surface area of from about 300 sq m/g to 2600 sq m/g, wherein the painted polymer part has been electrospray painted.

Metal oxide nanosensors using polymeric membranes, enzymes and antibody receptors as ion and molecular recognition elements.

PubMed

Willander, Magnus; Khun, Kimleang; Ibupoto, Zafar Hussain

2014-05-16

The concept of recognition and biofunctionality has attracted increasing interest in the fields of chemistry and material sciences. Advances in the field of nanotechnology for the synthesis of desired metal oxide nanostructures have provided a solid platform for the integration of nanoelectronic devices. These nanoelectronics-based devices have the ability to recognize molecular species of living organisms, and they have created the possibility for advanced chemical sensing functionalities with low limits of detection in the nanomolar range. In this review, various metal oxides, such as ZnO-, CuO-, and NiO-based nanosensors, are described using different methods (receptors) of functionalization for molecular and ion recognition. These functionalized metal oxide surfaces with a specific receptor involve either a complex formation between the receptor and the analyte or an electrostatic interaction during the chemical sensing of analytes. Metal oxide nanostructures are considered revolutionary nanomaterials that have a specific surface for the immobilization of biomolecules with much needed orientation, good conformation and enhanced biological activity which further improve the sensing properties of nanosensors. Metal oxide nanostructures are associated with certain unique optical, electrical and molecular characteristics in addition to unique functionalities and surface charge features which shows attractive platforms for interfacing biorecognition elements with effective transducing properties for signal amplification. There is a great opportunity in the near future for metal oxide nanostructure-based miniaturization and the development of engineering sensor devices.

Estimation of the specific surface area for a porous carrier.

PubMed

Levstek, Meta; Plazl, Igor; Rouse, Joseph D

2010-03-01

In biofilm systems, treatment performance is primarily dependent upon the available biofilm growth surface area in the reactor. Specific surface area is thus a parameter that allows for making comparisons between different carrier technologies used for wastewater treatment. In this study, we estimated the effective surface area for a spherical, porous polyvinyl alcohol (PVA) gel carrier (Kuraray) that has previously demonstrated effectiveness for retention of autotrophic and heterotrophic biomass. This was accomplished by applying the GPS-X modeling tool (Hydromantis) to a comparative analysis of two moving-bed biofilm reactor (MBBR) systems. One system consisted of a lab-scale reactor that was fed synthetic wastewater under autotrophic conditions where only the nitrification process was studied. The other was a pre-denitrification pilot-scale plant that was fed real, primary-settled wastewater. Calibration of an MBBR process model for both systems indicated an effective specific surface area for PVA gel of 2500 m2/m3, versus a specific surface area of 1000 m2/m3 when only the outer surface of the gel beads is considered. In addition, the maximum specific growth rates for autotrophs and heterotrophs were estimated to be 1.2/day and 6.0/day, respectively.

Photocatalytic and electrochemical performance of three-Dimensional reduced graphene Oxide/WS2/Mg-doped ZnO composites

NASA Astrophysics Data System (ADS)

Yu, Weiwei; Chen, Xi'an; Mei, Wei; Chen, Chuansheng; Tsang, Yuenhong

2017-04-01

To improve the dispersion of reduced graphene oxide and enhance the photocatalytic property of reduced graphene oxide/Mg-doped ZnO composites (rGMZ), the reduced graphene oxide/WS2/Mg-doped ZnO composites (rGWMZ) were prepared by electrostatic self-assembly and coprecipitation methods. The effects of mass ratio of WS2 nanosheets to reduced graphene oxide (WS2/rGO wt.%) and calcination temperature on the photocatalytic and electrochemical property of rGWMZ composites were investigated. Experimental results showed that the photocatalytic efficiency of rGWMZ composites is three-fold compared with that of rGMZ composites when the WS2/rGO wt.% is 20.8% and calcination temperature is 500 °C, in which the degradation ratio Rhodamin B (RhB) can reach 95% within 15 min under the UV light and 90% within 90 min under simulated solar light. In addition, the rGWMZ show larger capacitance and smaller resistance than rGMZ. The enhancement for photocatalytic activity and electrochemical performance of rGWMZ is ascribed to improving the specific surface area, electrical conductivity and electronic storage capability because of the synergistic effect of rGO and WS2 nanosheets.

LaCrO3/CuFe2O4 Composite-Coated Crofer 22 APU Stainless Steel Interconnect of Solid Oxide Fuel Cells

NASA Astrophysics Data System (ADS)

Hosseini, Seyedeh Narjes; Enayati, Mohammad Hossein; Karimzadeh, Fathallah; Dayaghi, Amir Masoud

2017-07-01

Rapidly rising contact resistance and cathode Cr poisoning are the major problems associated with unavoidable chromia scale growth on ferritic stainless steel (FSS) interconnects of solid oxide fuel cells. This work investigates the performance of the novel screen-printed composite coatings consisting of dispersed conductive LaCrO3 particles in a CuFe2O4 spinel matrix for Crofer 22 APU FSS, with emphasis on the oxidation behavior and electrical conductivity of these coatings. The results show that the presence of protective spinel coating, accompanied by the effective role of LaCrO3 particle incorporation, prevents the Cr2O3 subscale growth as well as chromium migration into the coating surface at the end of 400 hours of oxidation at 1073 K (800 °C) in air. In addition, the composite coatings decreased the area specific resistance (ASR) from 51.7 and 13.8 mΩ cm2 for uncoated and spinel-coated samples, respectively, to a maximum of 7.7 mΩ cm2 for composite-coated samples after 400 hours of oxidation.

Arsenic removal in aqueous solution by a novel Fe-Mn modified biochar composite: Characterization and mechanism.

PubMed

Lin, Lina; Qiu, Weiwen; Wang, Di; Huang, Qing; Song, Zhengguo; Chau, Henry Wai

2017-10-01

The aim of this study was to develop a cost-effective method for As removal from aqueous systems. To this end, pristine biochar (BC) was impregnated with Fe-Mn oxides and a comparative analysis was conducted on the adsorption capacities of BC, Fe-Mn binary oxide (FMO), and Fe/Mn modified biochar (FMBC). The ferromanganese oxides increased the specific surface areas of BC. FMBC presented greater adsorption of As (Q max = 8.25mgg -1 ) than FMO and BC. Energy dispersive spectrometer analysis and electron microscope scanning revealed numerous pores of FMBC with the existence of Fe-Mn oxide using. Distinguished binding energy shifting of the As3d, Fe2p, O1s, and Mn2p3/2 regions after As sorption were found, indicating that Mn(III) oxidation and interaction of oxygen-containing function groups in the FMBC promoted the conversion of As(III) to As(V). Furthermore, chemisorption was found to be the main mechanism for As sorption on FMBC. Thus, the results suggest that FMBC could be used as an inexpensive and highly efficient adsorbent for As removal from water environment. Copyright © 2017 Elsevier Inc. All rights reserved.

Low-Temperature Fluorination of Soft-Templated Mesoporous Carbons for a High-Power Lithium/Carbon Fluoride Battery

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

Fulvio, Pasquale F; Dai, Sheng; Guo, Bingkun

Soft-templated mesoporous carbons and activated mesoporous carbons were fluorinated using elemental fluorine between room temperature and 235 C. The mesoporous carbons were prepared via self-assembly synthesis of phloroglucinol formaldehyde as a carbon precursor in the presence of triblock ethylene oxide propylene oxide ethylene oxide copolymer BASF Pluronic F127 as the template. The F/C ratios ranged from 0.15 to 0.75 according to gravimetric, energy dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy analysis. Materials have mesopore diameters up to 11 nm and specific surface areas as high as 850 m2 g 1 after fluorination as calculated from nitrogen adsorption isotherms at 196more » C. Furthermore, the materials exhibit higher discharge potentials and energy and power densities as well as faster reaction kinetics under high current densities than commercial carbon fluorides with similar fluorine contents when tested as cathodes for Li/CFx batteries.« less

Controlled Synthesis of Pt Nanowires with Ordered Large Mesopores for Methanol Oxidation Reaction

NASA Astrophysics Data System (ADS)

Zhang, Chengwei; Xu, Lianbin; Yan, Yushan; Chen, Jianfeng

2016-08-01

Catalysts for methanol oxidation reaction (MOR) are at the heart of key green-energy fuel cell technology. Nanostructured Pt materials are the most popular and effective catalysts for MOR. Controlling the morphology and structure of Pt nanomaterials can provide opportunities to greatly increase their activity and stability. Ordered nanoporous Pt nanowires with controlled large mesopores (15, 30 and 45 nm) are facilely fabricated by chemical reduction deposition from dual templates using porous anodic aluminum oxide (AAO) membranes with silica nanospheres self-assembled in the channels. The prepared mesoporous Pt nanowires are highly active and stable electrocatalysts for MOR. The mesoporous Pt nanowires with 15 nm mesopores exhibit a large electrochemically active surface area (ECSA, 40.5 m2 g-1), a high mass activity (398 mA mg-1) and specific activity (0.98 mA cm-2), and a good If/Ib ratio (1.15), better than the other mesoporous Pt nanowires and the commercial Pt black catalyst.

Mesoporous metal oxide microsphere electrode compositions and their methods of making

DOEpatents

Paranthaman, Mariappan Parans; Liu, Hansan; Brown, Gilbert M.; Sun, Xiao-Guang; Bi, Zhonghe

2016-12-06

Compositions and methods of making are provided for mesoporous metal oxide microspheres electrodes. The mesoporous metal oxide microsphere compositions comprise (a) microspheres with an average diameter between 200 nanometers (nm) and 10 micrometers (.mu.m); (b) mesopores on the surface and interior of the microspheres, wherein the mesopores have an average diameter between 1 nm and 50 nm and the microspheres have a surface area between 50 m.sup.2/g and 500 m.sup.2/g. The methods of making comprise forming composite powders. The methods may also comprise refluxing the composite powders in a basic solution to form an etched powder, washing the etched powder with an acid to form a hydrated metal oxide, and heat-treating the hydrated metal oxide to form mesoporous metal oxide microspheres.

Fabrication and characterization of iron oxide dextran composite layers

NASA Astrophysics Data System (ADS)

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

2018-02-01

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

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

PubMed

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

2018-03-15

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

Iron oxide and gold nanoparticles in cancer therapy

NASA Astrophysics Data System (ADS)

Gotman, Irena; Psakhie, Sergey G.; Lozhkomoev, Aleksandr S.; Gutmanas, Elazar Y.

2016-08-01

Continuous research activities in the field of nanomedicine in the past decade have, to a great extent, been focused on nanoparticle technologies for cancer therapy. Gold and iron oxide nanoparticles (NP) are two of the most studied inorganic nanomaterials due to their unique optical and magnetic properties. Both types of NPs are emerging as promising systems for anti-tumor drug delivery and for nanoparticle-mediated thermal therapy of cancer. In thermal therapy, localized heating inside tumors or in proximity of tumor cells can be induced, for example, with Au NPs by radiofrequency ablation heating or conversion of photon energy (photothermal therapy) and in iron oxide magnetic NPs by heat generation through relaxation in an alternating magnetic field (magnetic hyperthermia). Furthermore, the superparamagnetic properties of iron oxide nanoparticles have led to their use as potent MRI (magnetic resonance imaging) contrast agents. Surface modification/coating can produce NPs with tailored and desired properties, such as enhanced blood circulation time, stability, biocompatibility and water solubility. To target nanoparticles to specific tumor cells, NPs should be conjugated with targeting moieties on the surface which bind to receptors or other molecular structures on the cell surface. The article presents several approaches to enhancing the specificity of Au and iron oxide nanoparticles for tumor tissue by appropriate surface modification/functionalization, as well as the effect of these treatments on the saturation magnetization value of iron oxide NPs. The use of other nanoparticles and nanostructures in cancer treatment is also briefly reviewed.

Preparation and performance of manganese-oxide-coated zeolite for the removal of manganese-contamination in groundwater.

PubMed

Lyu, Cong; Yang, Xuejiao; Zhang, Shengyu; Zhang, Qihui; Su, Xiaosi

2017-12-29

A promising and easily prepared catalytic filler media, manganese-oxide-coated zeolite (MOCZ), for the removal of Mn (II) contamination in groundwater was studied. The optimal condition for MOCZ preparation was given as follows: acid activation of zeolite with 5% HCl mass percent for 12 h, then soaking of acid-activated zeolite with 7% KMnO 4 mass percent for 8 h, and finally calcination at 300°C for 5 h. Acid activation significantly enlarged the specific surface area of the zeolite (>79 m 2  g -1 ), subsequently enhancing the coating of manganese oxides onto the surface of the zeolite. This was further supported by the manganese-to-zeolite ratio (γ Mn ) and Energy dispersive analysis-mapping. The γ Mn was over 12.26 mg Mn g -1 zeolite, representing more active sites for the adsorption and catalytic-oxidation of Mn (II). As such, great performance of Mn (II) removal by MOCZ was obtained in the filter experiment. An estimated 98-100% removal efficiency of Mn (II) was achieved in a greatly short startup time (only 2 h). During the filtration process, newborn flocculent manganese oxides with a mixed-valence of manganese (Mn (II) and Mn (IV)) were generated on the MOCZ surface, further facilitating the adsorption and catalytic-oxidation of Mn (II). The filter with MOCZ as adsorbent had a great performance on the Mn (II) removal in a wide range of hydraulic retention time (HRT) (4-40 min), particularly in a short HRT. Besides, the filter prolonged the filtration period (60 days), which would significantly reduce the frequency of backwash. Thus, it could be concluded that MOCZ prepared in this study showed a good performance in terms of Mn (II) removal in waterworks, especially small waterworks in the villages/towns.

Multifunctional Hybrid Multilayer Gate Dielectrics with Tunable Surface Energy for Ultralow-Power Organic and Amorphous Oxide Thin-Film Transistors.

PubMed

Byun, Hye-Ran; You, Eun-Ah; Ha, Young-Geun

2017-03-01

For large-area, printable, and flexible electronic applications using advanced semiconductors, novel dielectric materials with excellent capacitance, insulating property, thermal stability, and mechanical flexibility need to be developed to achieve high-performance, ultralow-voltage operation of thin-film transistors (TFTs). In this work, we first report on the facile fabrication of multifunctional hybrid multilayer gate dielectrics with tunable surface energy via a low-temperature solution-process to produce ultralow-voltage organic and amorphous oxide TFTs. The hybrid multilayer dielectric materials are constructed by iteratively stacking bifunctional phosphonic acid-based self-assembled monolayers combined with ultrathin high-k oxide layers. The nanoscopic thickness-controllable hybrid dielectrics exhibit the superior capacitance (up to 970 nF/cm 2 ), insulating property (leakage current densities <10 -7 A/cm 2 ), and thermal stability (up to 300 °C) as well as smooth surfaces (root-mean-square roughness <0.35 nm). In addition, the surface energy of the hybrid multilayer dielectrics are easily changed by switching between mono- and bifunctional phosphonic acid-based self-assembled monolayers for compatible fabrication with both organic and amorphous oxide semiconductors. Consequently, the hybrid multilayer dielectrics integrated into TFTs reveal their excellent dielectric functions to achieve high-performance, ultralow-voltage operation (< ± 2 V) for both organic and amorphous oxide TFTs. Because of the easily tunable surface energy, the multifunctional hybrid multilayer dielectrics can also be adapted for various organic and inorganic semiconductors, and metal gates in other device configurations, thus allowing diverse advanced electronic applications including ultralow-power and large-area electronic devices.

Nanostructured Metal Oxides for Stoichiometric Degradation of Chemical Warfare Agents.

PubMed

Štengl, Václav; Henych, Jiří; Janoš, Pavel; Skoumal, Miroslav

2016-01-01

Metal oxides have very important applications in many areas of chemistry, physics and materials science; their properties are dependent on the method of preparation, the morphology and texture. Nanostructured metal oxides can exhibit unique characteristics unlike those of the bulk form depending on their morphology, with a high density of edges, corners and defect surfaces. In recent years, methods have been developed for the preparation of metal oxide powders with tunable control of the primary particle size as well as of a secondary particle size: the size of agglomerates of crystallites. One of the many ways to take advantage of unique properties of nanostructured oxide materials is stoichiometric degradation of chemical warfare agents (CWAs) and volatile organic compounds (VOC) pollutants on their surfaces.

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

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

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

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

α-Fe2O3 nanotubes-reduced graphene oxide composites as synergistic electrochemical capacitor materials.

PubMed

Lee, K K; Deng, S; Fan, H M; Mhaisalkar, S; Tan, H R; Tok, E S; Loh, K P; Chin, W S; Sow, C H

2012-04-28

We present a facile approach for the fabrication of a nanocomposite comprising α-Fe(2)O(3) nanotubes (NTs) anchored on reduced graphene oxide (rGO) for electrochemical capacitors (ECs). The hollow tubular structure of the α-Fe(2)O(3) NTs presents a high surface area for reaction, while the incorporation of rGO provides an efficient two-dimensional conductive pathway to allow fast, reversible redox reaction. As a result, the nanocomposite materials exhibit a specific capacitance which is remarkably higher (~7 times) than α-Fe(2)O(3) NTs alone. In addition, the nanocomposites show excellent cycling life and large negative potential window. These findings suggest that such nanocomposites are a promising candidate as negative electrodes in asymmetrical capacitors with neutral electrolytes. This journal is © The Royal Society of Chemistry 2012

In situ synthesis of ultra-fine, porous, tin oxide-carbon nanocomposites via a molten salt method for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Liu, Bin; Guo, Zai Ping; Du, Guodong; Nuli, Yanna; Hassan, Mohd Faiz; Jia, Dianzeng

Ultra-fine, porous, tin oxide-carbon (SnO 2/C) nanocomposites are fabricated by a molten salt method at 300 °C, and malic acid is decomposed as the carbon source. In situ synthesis is favourable for the combination of carbon and SnO 2. The structure and morphology are confirmed by X-ray diffraction analysis, specific surface-area measurements, and transmission electron microscopy (TEM). Examination of TEM images reveals that the SnO 2 nanoparticles are embedded in the carbon matrix, with sizes between 2 and 5 nm. The electrochemical measurements show that the nanocomposite delivers a high capacity with good capacity retention as an anode material for lithium-ion batteries, due to the combination of the ultra-fine porous structure and the carbon component.

Destructive adsorption of Diazinon pesticide by activated carbon nanofibers containing Al2O3 and MgO nanoparticles.

PubMed

Behnam, Roghaye; Morshed, Mohammad; Tavanai, Hossein; Ghiaci, Mehran

2013-10-01

We report the destructive adsorption of Diazinon pesticide by porous webs of activated carbon nanofibers containing Al2O3 and MgO nanoparticles. The results show that, the presence of Al2O3 and MgO nanoparticles in the activated carbon nanofibers increases the amount of destructively adsorbed Diazinon pesticide by activated carbon nanofibers. Moreover, type, amount, and specific surface area of metal oxide nanoparticles affect the adsorption rate as well as the total destructively adsorbed Diazinon. Liquid chromatography proved the degradation of Diazinon by chemical reaction with Al2O3 and MgO nanoparticles. Liquid chromatography-mass spectrometry showed that the main product of reaction between Diazinon and the metal oxides is 2-isopropyl-6-methyl-4-pyrimidinol with less toxicity than Diazinon.

Transformation of zinc hydroxide chloride monohydrate to crystalline zinc oxide.

PubMed

Moezzi, Amir; Cortie, Michael; McDonagh, Andrew

2016-04-25

Thermal decomposition of layered zinc hydroxide double salts provides an interesting alternative synthesis for particles of zinc oxide. Here, we examine the sequence of changes occurring as zinc hydroxide chloride monohydrate (Zn5(OH)8Cl2·H2O) is converted to crystalline ZnO by thermal decomposition. The specific surface area of the resultant ZnO measured by BET was 1.3 m(2) g(-1). A complicating and important factor in this process is that the thermal decomposition of zinc hydroxide chloride is also accompanied by the formation of volatile zinc-containing species under certain conditions. We show that this volatile compound is anhydrous ZnCl2 and its formation is moisture dependent. Therefore, control of atmospheric moisture is an important consideration that affects the overall efficiency of ZnO production by this process.

Deposition of conductive TiN shells on SiO2 nanoparticles with a fluidized bed ALD reactor

NASA Astrophysics Data System (ADS)

Didden, Arjen; Hillebrand, Philipp; Wollgarten, Markus; Dam, Bernard; van de Krol, Roel

2016-02-01

Conductive TiN shells have been deposited on SiO2 nanoparticles (10-20 nm primary particle size) with fluidized bed atomic layer deposition using TDMAT and NH3 as precursors. Analysis of the powders confirms that shell growth saturates at approximately 0.4 nm/cycle at TDMAT doses of >1.2 mmol/g of powder. TEM and XPS analysis showed that all particles were coated with homogeneous shells containing titanium. Due to the large specific surface area of the nanoparticles, the TiN shells rapidly oxidize upon exposure to air. Electrical measurements show that the partially oxidized shells are conducting, with apparent resistivity of approximately 11 kΩ cm. The resistivity of the powders is strongly influenced by the NH3 dose, with a smaller dose giving an order-of-magnitude higher resistivity.

Mesoporous silica wrapped with graphene oxide-conducting PANI nanowires as a novel hybrid electrode for supercapacitor

NASA Astrophysics Data System (ADS)

Javed, Mohsin; Abbas, Syed Mustansar; Siddiq, Mohammad; Han, Dongxue; Niu, Li

2018-02-01

A high charge-carrier transport is an important aim in the synthesis of nanostructures for an effective supercapacitor. This article describes a methodology to prepare mesoporous silica nanoparticles (MSNs) wrapped with graphene oxide (GO) together with conducting polyaniline (PANI) wires. The morphology and chemical structure of the prepared samples have been tested by transmission electron microscopy (TEM), high-resolution TEM (HRTEM), and X-ray diffraction (XRD), whereas the stability and electrostatic interaction of the structures have been verified by thermogravimetric analysis (TGA) and Fourier-transform infrared (FT-IR) spectroscopy, respectively. The supercapacitive behaviour of these nanocomposites has been analysed by cyclic voltammetry (CV), charge-discharge tests, and electrochemical impedance spectroscopy (EIS). Compared with pristine MSNs and PANI, the 20%-GO@MSNs/PANI nanocomposite had the highest specific capacitance, reaching 412 F g-1. The nanocomposite structure maximizes the synergy between mesoporous metal oxide, conducting PANI, and GO, yielding a significantly enhanced specific capacitance, rapid charge-discharge rates, and good cycling stability of the resulting device. The wrapping with GO prevents the structural breakdown and acts as a highly conductive pathway by bridging the individual particles, whereas the MSNs nanoparticles greatly enlarge the specific surface area to facilitate ion transport and charge transfer throughout the cycling performance of supercapacitor. The approach adopted in this article can be applied for preparing similar novel functional materials in future for electrochemical applications.

The role of reduced graphene oxide on the electrochemical activity of MFe2O4 (M = Fe, Co, Ni and Zn) nanohybrids

NASA Astrophysics Data System (ADS)

Suresh, Shravan; Prakash, Anand; Bahadur, D.

2018-02-01

In this work, a comparative study of electrochemical performance of reduced graphene oxide-ferrites (RGO-MFe2O4, M = Fe, Co, Ni, and Zn) nanohybrids synthesized by hydrothermal method was done. The structural morphology and investigation of other physical properties of nanohybrids confirm the cubic spinel phase of the MFe2O4, reduction of graphene oxide and the distribution of ferrite nanoparticles (NPs) on RGO nanosheets. The role of RGO on the electrochemical behavior of nanohybrids was understood by quantifying the charge storage capacitance and charging-discharging behavior in a 0.1 M Na2SO4 electrolyte. The specific capacitance values of pristine Fe3O4, CoFe2O4, NiFe2O4, and ZnFe2O4 are 128, 117, 15.2 and 9.1 F g-1 respectively whereas specific capacitance of RGO-Fe3O4, RGO-CoFe2O4, RGO-NiFe2O4 and RGO-ZnFe2O4 are 233, 200, 25 and 66.8 F g-1 respectively. Our investigation suggests that apart from specific surface area of nanohybrids other factors such as structural morphology determine interaction between nanohybrids and electrolyte ions which play critical role in elevating the performance of electrodes.

Solvent free tin oxide nanoparticle for gas sensing application

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

Ranjan, Pranay, E-mail: pranjan@iitp.ac.in; Thakur, Ajay D.; Centre for Energy and Environment, Indian Institute of Technology Patna, Patliputra, Patna 800013 India

2016-05-06

A new modified technique of synthesizing tin oxide nanoparticles with crystallite size of 2 nm to 6 nm has been developed. Surface area of the nanoparticle has been increased as we approached towards the Debye length. Such a techniques for approaching the Debye length is expected to bring remarkable changes in the properties of resistive based gas sensors. The technique used here is less toxic, economical and has high yield. Phase purity, size, shape and composition has been investigated using x-ray diffraction, micro Raman, scanning electron microscopy and energy dispersive x ray spectroscopy. While surface area has been calculated through Brunaur-Emmett-Teller (BET).

Thin coatings for protecting titanium aluminides in high-temperature oxidizing environments

NASA Technical Reports Server (NTRS)

Wiedemann, K. E.; Taylor, P. J.; Clark, R. K.; Wallace, T. A.

1991-01-01

Titanium aluminides have high specific strengths at high temperatures but are susceptible to environmental attack. Their use in many aerospace applications would require that they be protected with coatings that, for structural efficiency, must be thin. It is conceivable that acceptable coatings might be found in several oxide systems, and consequently, oxide coatings of many compositions were prepared from sol-gels for study. Response-surface methodology was used to refine coating compositions and factorial experiments were used to develop coating strategies. Oxygen permeability diagrams of two-layer coatings for several oxide systems, an analysis of multiple-layer coatings on rough and polished surfaces, and modeling of the oxidation weight gain are presented.

An electrochemical impedance spectroscopy study of polymer electrolyte membrane fuel cells electrocatalyst single wall carbon nanohorns-supported.

PubMed

Brandão, Lúcia; Boaventura, Marta; Passeira, Carolina; Gattia, Daniele Mirabile; Marazzi, Renzo; Antisari, Marco Vittori; Mendes, Adélio

2011-10-01

Electrochemical impedance spectroscopy (EIS) was used to study the polymer electrolyte membrane fuel cells (PEMFC) performance when using single wall carbon nanohorns (SWNH) to support Pt nanoparticles. Additionally, as-prepared and oxidized SWNH Pt-supports were compared with conventional carbon black. Two different oxidizing treatments were considered: oxygen flow at 500 degrees C and reflux in an acid solution at 85 degrees C. Both oxidizing treatments increased SWNH surface area; oxygen treatment increased surface area 4 times while acid treatment increased 2.6 times. The increase in surface area should be related to the opening access to the inner tube of SWNH. Acid treatment of SWNH increased chemical fragility and decreased electrocatalyst load in comparison with as-prepared SWNH. On the other hand, the oxygen treated SWNH sample allowed to obtain the highest electrocatalyst load. The use of as-prepared and oxygen treated SWNH showed in both cases catalytic activities 60% higher than using conventional carbon black as electrocatalyst support in PEMFC. Moreover, EIS analysis indicated that the major improvement in performance is related to the cathode kinetics in the as-prepared SWNH sample, while concerning the oxidized SWNH sample, the improvements are related to the electrokinetics in both anode and cathode electrodes. These improvements should be related with differences in the hydrophobic character between SWNH and carbon black.

Core-shell monodisperse spherical mSiO2/Gd2O3:Eu3+@mSiO2 particles as potential multifunctional theranostic agents

NASA Astrophysics Data System (ADS)

Eurov, Daniil A.; Kurdyukov, Dmitry A.; Kirilenko, Demid A.; Kukushkina, Julia A.; Nashchekin, Alexei V.; Smirnov, Alexander N.; Golubev, Valery G.

2015-02-01

Core-shell nanoparticles with diameters in the range 100-500 nm have been synthesized as monodisperse spherical mesoporous (pore diameter 3 nm) silica particles with size deviation of less than 4 %, filled with gadolinium and europium oxides and coated with a mesoporous silica shell. It is shown that the melt technique developed for filling with gadolinium and europium oxides provides a nearly maximum filling of mesopores in a single-run impregnation, with gadolinium and europium uniformly distributed within the particles and forming no bulk oxides on their surface. The coating with a shell does not impair the monodispersity and causes no coagulation. The coating technique enables controlled variation of the shell thickness within the range 5-100 % relative to the core diameter. The thus produced nanoparticles are easily dispersed in water, have large specific surface area (300 m2 g-1) and pore volume (0.3 cm3 g-1), and are bright solid phosphor with superior stability in aqueous media. The core-shell structured particles can be potentially used for cancer treatment as a therapeutic agent (gadolinium neutron-capture therapy and drug delivery system) and, simultaneously, as a multimodal diagnostic tool (fluorescence and magnetic resonance imaging), thereby serving as a multifunctional theranostic agent.

Ternary carbon composite films for supercapacitor applications

NASA Astrophysics Data System (ADS)

Tran, Minh-Hai; Jeong, Hae Kyung

2017-09-01

A simple, binder-free, method of making supercapacitor electrodes is introduced, based on modification of activated carbon with graphite oxide and carbon nanotubes. The three carbon precursors of different morphologies support each other to provide outstanding electrochemical performance, such as high capacitance and high energy density. The ternary carbon composite shows six times higher specific capacitance compared to that of activated carbon itself with high retention. The excellent electrochemical properties of the ternary composite attribute to the high surface area of 1933 m2 g-1 and low equivalent series resistance of 2 Ω, demonstrating that it improve the electrochemical performance for supercapacitor applications.

Tissue Repair and Regeneration Following Orthopedic and Craniofacial Trauma

DTIC Science & Technology

2012-07-01

than amines to aldehydes and ketones , and reaction of hydrazines with aldehydes results in the formation of a stable hydrazone bond. In that regard...their N-terminus that was oxidized with periodate to obtain a single aldehyde group at the same location, which can be used for the site-specific...specific immobiliza- tion on the HA surface. Specifically, both proteins were oxidized selectively to obtain an N-terminal aldehyde and immobilized on the

The effect of Co-doping on the humidity sensing properties of ordered mesoporous TiO2

NASA Astrophysics Data System (ADS)

Li, Zhong; Haidry, Azhar Ali; Gao, Bin; Wang, Tao; Yao, ZhengJun

2017-08-01

Monitoring of humidity is of utmost importance as it is essential part of almost every process in our life. Many commercial humidity sensors based on metal oxide semiconductors are available in the market, but there is still need to synthesize low-cost, fast and highly sensitive humidity sensors with no interference from background environment. The aim of this work was to fabricate the ordered mesoporous un-doped and Co-doped TiO2 (0.1-5 mol% Co) and to analyze its humidity sensing properties at room temperatures. The ordered mesoporous powders with high specific surface area (SSA) were prepared by multicomponent self-assembly procedure and then spray-coated onto the sensor substrates with interdigitated gold electrodes. The sensors exhibited excellent stability and reproducible resistance change under various relative humidity percentages (9-90% RH) with negligible effect of background environment. For instance, the response to 90% RH at room temperature was about five orders of magnitude (∼1.39 × 105) and the response time (Tres) was ∼24 s. The reaction/recovery times of the sensors were compared with commercial humidity sensor to show that the reaction times in this work are not given by the surface reaction of water vapor on the sensor surfaces, rather these are mainly influenced by the experimental setup. The sensor response increased up to 3 mol% Co-contents and then decreased for 5 mol% Co-contents. Based on the experimental results, the surface reaction of humidity is discussed related to specific surface area, average grain size and cobalt contents to understand the humidity sensing mechanism.

Room Temperature Electrochemical Sintering of Zn Microparticles and Its Use in Printable Conducting Inks for Bioresorbable Electronics.

PubMed

Lee, Yoon Kyeung; Kim, Jeonghyun; Kim, Yerim; Kwak, Jean Won; Yoon, Younghee; Rogers, John A

2017-10-01

This study describes a conductive ink formulation that exploits electrochemical sintering of Zn microparticles in aqueous solutions at room temperature. This material system has relevance to emerging classes of biologically and environmentally degradable electronic devices. The sintering process involves dissolution of a surface passivation layer of zinc oxide in CH 3 COOH/H 2 O and subsequent self-exchange of Zn and Zn 2+ at the Zn/H 2 O interface. The chemical specificity associated with the Zn metal and the CH 3 COOH/H 2 O solution is critically important, as revealed by studies of other material combinations. The resulting electrochemistry establishes the basis for a remarkably simple procedure for printing highly conductive (3 × 10 5 S m -1 ) features in degradable materials at ambient conditions over large areas, with key advantages over strategies based on liquid phase (fusion) sintering that requires both oxide-free metal surfaces and high temperature conditions. Demonstrations include printed magnetic loop antennas for near-field communication devices. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Influence of non-migratory metal-chelating active packaging film on food quality: impact on physical and chemical stability of emulsions.

PubMed

Tian, Fang; Decker, Eric A; McClements, D Julian; Goddard, Julie M

2014-05-15

Previously, we developed a novel metal-chelating packaging film (PP-g-PAA) by grafting acrylic acid (AA) monomer from polypropylene (PP) film surface, and demonstrated its potential in controlling iron-promoted lipid oxidation. Herein, we further established the industrial practicality of this active film. Specifically, the influence of film surface area-to-product volume ratio (SA/V) and product pH on the application of the film was investigated using an oil-in-water emulsion system. The films equally inhibited lipid oxidation throughout the range of SA/V ratios tested (2-8 cm(2)/ml). PP-g-PAA films were most effective at pH 7.0, and the activity decreased with decreasing pH. The particle size examination of emulsions indicated no adverse influence from the active film on the stability of this emulsion system. FTIR analysis suggested a non-migratory nature of PP-g-PAA films. These results provide fundamental knowledge that will facilitate the application of this effective and economical active packaging film in the food industry. Copyright © 2013 Elsevier Ltd. All rights reserved.

Effect of Morphology and Manganese Valence on the Voltage Fade and Capacity Retention of Li[Li 2/12Ni 3/12Mn 7/12]O 2

DOE PAGES

Verde, Michael G.; Liu, Haodong; Carroll, Kyler J.; ...

2014-10-02

We have determined the electrochemical characteristics of the high voltage, high capacity Li-ion battery cathode material Li[Li 2/12Ni 3/12Mn 7/12]O 2 prepared using three different synthesis routes: sol-gel, hydroxide co-precipitation, and carbonate co-precipitation. Each route leads to distinct morphologies and surface areas while maintaining the same crystal structures. X-ray photoelectron spectroscopy (XPS) measurements reveal differences in their surface chemistries upon cycling, which correlate with voltage fading. As expected, we observed the valence state of Mn on the surface to decrease upon lithiation, and this reduction is specifically correlated to discharging below 3.6V. Furthermore, the data shows a correlation of themore » formation of Li 2CO 3 with Mn oxidation state from the« less

Functionalization of Ti99.2 substrates surface by hybrid treatment investigated with spectroscopic methods

NASA Astrophysics Data System (ADS)

Jasinski, Jaroslaw Jan; Lubas, Malgorzata; Kurpaska, Lukasz; Napadlek, Wojciech; Sitarz, Maciej

2018-07-01

The article presents spectroscopic investigation of Ti 99.2 based functional substrates formed by hybrid oxidation process. Surface treatments were performed by combining methods of fluidized bed atmospheric diffusion treatment (FADT) with physical vapor deposition (PVD) - magnetron sputtering and laser surface texturing (LST) treatments. The processes were implemented to form a titanium diffusive layer saturated with oxygen in the substrate and a tight homogeneous oxide coating on Ti surface deposited with magnetron sputtering or laser texturing technique. The hybrid treatment was realized in Al2O3 fluidized bed reactor with air atmosphere, at 640 °C for 8 h and 12 h. At the same time, magnetron sputtering with the use of TiO2 target at a pressure of 3 × 102 mbar and laser surface texturing treatment with Nd:YAG λ = 1064 nm was performed. In order to investigate the effects of hybrid oxidation, microscopic (AFM, CLSM, SEM/SEM-EDX), spectroscopic (RS) and X-ray investigations (GID-XRD) were performed. Applied hybrid technique made possible to combine the effects of the generated layers and to reduce the stresses in the area of the PVD coating/oxidized Ti substrate interface. Furthermore, Raman spectroscopy results obtained at oxide layers manufactured with different variants of oxidation allowed detailed analysis of the created oxides. The coatings have shown structure with a Tiα(O) diffusion zone, a TiO2 rutile and anatase oxide zone deposited and textured on the substrate. Phase composition and morphology of these oxides is essential for the osseointegration process i.e. intensity of hydroxyapatite growing on the implant surface. Performed processes influenced the surface roughness parameter and cause the increase of substrate functional properties, which are important for biomedical applications.

Nonfouling Characteristics of Dextran-Containing Surfaces

PubMed Central

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

2008-01-01

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

Surface Selective Oxidation of Sn-Added CMnSi TRIP Steel

NASA Astrophysics Data System (ADS)

Cho, Lawrence; Seo, Eun Jung; Jung, Geun Su; Suh, Dong Woo; De Cooman, Bruno C.

2016-04-01

The influence of the addition of Sn on the selective oxidation and the reactive wetting of CMnSi transformation-induced plasticity (TRIP) steels was studied by means of galvanizing simulator tests. A reference TRIP steel and TRIP steels containing Sn in the range of 0.05 to 1 wt pct were intercritically annealed at 1093 K (820 °C) in an N2+ 5 pct H2 gas atmosphere with a dew point of -60 °C. The thin-film oxides formed on the surface of the Sn-added CMnSi TRIP steel were investigated using transmission electron microscopy and 3-dimensional atom probe tomography. The addition of Sn (≥0.05 wt pct) changed the morphology of the xMnO·SiO2 surface oxides from a continuous film morphology to a lens-shaped island morphology. It also suppressed the formation of the Mn-rich oxides of MnO and 2MnO·SiO2. The changes in the morphology and chemistry of the surface oxides were clearly related to the surface segregation of Sn, which appeared to result in a decrease of the oxygen permeability at the surface. The formation of lens-shaped oxides improved the wettability of the CMnSi TRIP steel surface by the molten Zn. The improved wetting effect was attributed to an increased area fraction of the surface where the oxide layer was thinner. This enabled a direct, unhindered reaction between Fe and the Al in the liquid Zn and the formation of the inhibition layer in the initial stages of the hot dipping. The addition of a small amount of Sn was also found to decrease significantly the density of Zn-coating defects on CMnSi TRIP steel.

Mesoporous metal oxide graphene nanocomposite materials

DOEpatents

Liu, Jun; Aksay, Ilhan A.; Kou, Rong; Wang, Donghai

2016-05-24

A nanocomposite material formed of graphene and a mesoporous metal oxide having a demonstrated specific capacity of more than 200 F/g with particular utility when employed in supercapacitor applications. A method for making these nanocomposite materials by first forming a mixture of graphene, a surfactant, and a metal oxide precursor, precipitating the metal oxide precursor with the surfactant from the mixture to form a mesoporous metal oxide. The mesoporous metal oxide is then deposited onto a surface of the graphene.

Optimized spherical manganese oxide-ferroferric oxide-tin oxide ternary composites as advanced electrode materials for supercapacitors.

PubMed

Zhu, Jian; Tang, Shaochun; Vongehr, Sascha; Xie, Hao; Meng, Xiangkang

2015-09-18

Inexpensive MnO2 is a promising material for supercapacitors (SCs), but its application is limited by poor electrical conductivity and low specific surface area. We design and fabricate hierarchical MnO2-based ternary composite nanostructures showing superior electrochemical performance via doping with electrochemically active Fe3O4 in the interior and electrically conductive SnO2 nanoparticles in the surface layer. Optimization composition results in a MnO2-Fe3O4-SnO2 composite electrode material with 5.9 wt.% Fe3O4 and 5.3 wt.% SnO2, leading to a high specific areal capacitance of 1.12 F cm(-2) at a scan rate of 5 mV s(-1). This is two to three times the values for MnO2-based binary nanostructures at the same scan rate. The low amount of SnO2 almost doubles the capacitance of porous MnO2-Fe3O4 (before SnO2 addition), which is attributed to an improved conductivity and remaining porosity. In addition, the optimal ternary composite has a good rate capability and an excellent cycling performance with stable capacitance retention of ~90% after 5000 charge/discharge cycles at 7.5 mA cm(-2). All-solid-state SCs are assembled with such electrodes using polyvinyl alcohol/Na2SO4 electrolyte. An integrated device made by connecting two identical SCs in series can power a light-emitting diode indicator for more than 10 min.

Optimized spherical manganese oxide-ferroferric oxide-tin oxide ternary composites as advanced electrode materials for supercapacitors

NASA Astrophysics Data System (ADS)

Zhu, Jian; Tang, Shaochun; Vongehr, Sascha; Xie, Hao; Meng, Xiangkang

2015-09-01

Inexpensive MnO2 is a promising material for supercapacitors (SCs), but its application is limited by poor electrical conductivity and low specific surface area. We design and fabricate hierarchical MnO2-based ternary composite nanostructures showing superior electrochemical performance via doping with electrochemically active Fe3O4 in the interior and electrically conductive SnO2 nanoparticles in the surface layer. Optimization composition results in a MnO2-Fe3O4-SnO2 composite electrode material with 5.9 wt.% Fe3O4 and 5.3 wt.% SnO2, leading to a high specific areal capacitance of 1.12 F cm-2 at a scan rate of 5 mV s-1. This is two to three times the values for MnO2-based binary nanostructures at the same scan rate. The low amount of SnO2 almost doubles the capacitance of porous MnO2-Fe3O4 (before SnO2 addition), which is attributed to an improved conductivity and remaining porosity. In addition, the optimal ternary composite has a good rate capability and an excellent cycling performance with stable capacitance retention of ˜90% after 5000 charge/discharge cycles at 7.5 mA cm-2. All-solid-state SCs are assembled with such electrodes using polyvinyl alcohol/Na2SO4 electrolyte. An integrated device made by connecting two identical SCs in series can power a light-emitting diode indicator for more than 10 min.

The kinetics of influenza-virus adsorption on iron oxide in the process of viral purification and concentration

PubMed Central

Larin, N. M.; Gallimore, P. H.

1971-01-01

This paper reports a study carried out to clarify the mechanisms involved in adsorption of influenza A and B viruses on iron oxide. Accordingly, the amounts of virus that are adsorbed from virus suspensions of varying concentrations per unit surface area of magnetic or non-magnetic oxide at fixed temperature and time have been determined. The principles involved are clearly the same as those involved in multiple equilibria during the interaction of particles with a large number of combining sites with different intrinsic affinity. Consequently, the amount of virus that is adsorbed per unit mass of iron oxide depends on the size of the adsorbent area, not on its magnetic property. Owing to a significant difference between the affinities of influenza A and B particles for the binding sites on iron oxide, unit surface area of the adsorbent is invariably capable of adsorbing significantly greater amounts of influenza A than B particles. The practical implications of these findings are that a better understanding of the mechanisms involved in virus adsorption on iron oxide will permit a more efficient separation of virus particles from impurities. The simplicity and the rapidity of the technique and the cheapness of the equipment required suggest that the iron oxide method is of great value for both small- or large-scale viral purification, whether it is used as a single step procedure or as a primary step followed by zonal separation. PMID:5291749

Significantly enhanced dye removal performance of hollow tin oxide nanoparticles via carbon coating in dark environment and study of its mechanism

NASA Astrophysics Data System (ADS)

Yang, Shuanglei; Wu, Zhaohui; Huang, LanPing; Zhou, Banghong; Lei, Mei; Sun, Lingling; Tian, Qingyong; Pan, Jun; Wu, Wei; Zhang, Hongbo

2014-08-01

Understanding the correlation between physicochemical properties and morphology of nanostructures is a prerequisite for widespread applications of nanomaterials in environmental application areas. Herein, we illustrated that the uniform-sized SnO2@C hollow nanoparticles were large-scale synthesized by a facile hydrothermal method. The size of the core-shell hollow nanoparticles was about 56 nm, and the shell was composed of a solid carbon layer with a thickness of 2 ~ 3 nm. The resulting products were characterized in terms of morphology, composition, and surface property by various analytical techniques. Moreover, the SnO2@C hollow nanoparticles are shown to be effective adsorbents for removing four different dyes from aqueous solutions, which is superior to the pure hollow SnO2 nanoparticles and commercial SnO2. The enhanced mechanism has also been discussed, which can be attributed to the high specific surface areas after carbon coating.

The influence of Ce doping of titania on the photodegradation of phenol.

PubMed

Martin, Marcela V; Villabrille, Paula I; Rosso, Janina A

2015-09-01

Pure and cerium-doped [0.05, 0.1, 0.3, 0.5, and 1.0 Ce nominal atomic % (at.%)] TiO2 was synthesized by the sol-gel method. The obtained catalysts were characterized by X-ray diffraction (XRD), UV-visible diffused reflectance spectroscopy (DRS), Raman, and BET surface area measurement. The photocatalytic activity of synthesized samples for the oxidative degradation of phenol in aqueous suspension was investigated. The content of Ce in the catalysts increases both the transition temperature for anatase to rutile phase transformation and the specific surface area, and decreases the crystallite size of anatase phase, the crystallinity, and the band gap energy value. The material with higher efficiency corresponds to 0.1 Ce nominal at.%. Under irradiation with 350 nm lamps, the degradation of phenol could be described as an exponential trend, with an apparent rate constant of (9.1 ± 0.6) 10(-3) s(-1) (r(2) = 0.98). Hydroquinone was identified as the main intermediate.

Graphene-Based Materials for Lithium-Ion Hybrid Supercapacitors.

PubMed

Ma, Yanfeng; Chang, Huicong; Zhang, Miao; Chen, Yongsheng

2015-09-23

Lithium-ion hybrid supercapacitors (LIHSs), also called Li-ion capacitors, have attracted much attention due to the combination of the rapid charge-discharge and long cycle life of supercapacitors and the high energy-storage capacity of lithium-ion batteries. Thus, LIHSs are expected to become the ultimate power source for hybrid and all-electric vehicles in the near future. As an electrode material, graphene has many advantages, including high surface area and porous structure, high electric conductivity, and high chemical and thermal stability, etc. Compared with other electrode materials, such as activated carbon, graphite, and metal oxides, graphene-based materials with 3D open frameworks show higher effective specific surface area, better control of channels, and higher conductivity, which make them better candidates for LIHS applications. Here, the latest advances in electrode materials for LIHSs are briefly summarized, with an emphasis on graphene-based electrode materials (including 3D graphene networks) for LIHS applications. An outlook is also presented to highlight some future directions. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Pulmonary toxicity of manufactured nanoparticles

NASA Astrophysics Data System (ADS)

Peebles, Brian Christopher

Manufactured nanomaterials have become ubiquitous in science, industry, and medicine. Although electron microscopy and surface probe techniques have improved understanding of the physicochemical properties of nanomaterials, much less is known about what makes nanomaterials toxic. Particulate matter less than 2.5 mum in effective aerodynamic diameter is easily inhaled and taken deep into the lungs. The toxicity of inhaled particulate matter is related to its size and surface chemistry; for instance, the smaller the size of particles, the greater their specific surface area. The chemistry and toxicity of insoluble particles depends on their surface area, since chemical reactions may happen with the environment on the surface. Oxidation and reduction may occur on the surfaces of particles after they are produced. For instance, it is known that carbonaceous particles from vehicle exhaust and industrial emission may interact with reactive species like ozone in their ambient environment, altering the surface chemistry of the particles. Reaction with species in the environment may cause changes in the chemical functionality of the surface and change the toxic properties of the particles when they are inhaled. Furthermore, metals on the surface of inhalable particles can contribute to their toxicity. Much attention has been given to the presence of iron on the surfaces of inhalable particles in the environment. After particle inhalation, particles are endocytosed by alveolar macrophages in the immune response to foreign matter. They are exposed to hydrogen peroxide in the oxidative burst, which can cause the iron-mediated production of hydroxyl free radicals via the Fenton reaction, causing oxidative stress that leads to inflammation and cell death. The toxicity of particles that contain metals depends on the redox activity and bioavailability of the metals, the causes of thich have not yet been adequately explored. In this thesis, electron paramagnetic spectroscopy showed that carbon blacks contain free radical and other surface functionality as manufactured, and that exposure to ozone further functionalizes the surface. Samples of carbon black that have been exposed to ozone react with their ambient environment so that acid anhydride and cyclic ether functionality hydrolyze to form carboxylic acid functionality, observable by transmission Fourier transform infrared spectroscopy. Persistent free radical content, but not free radical content from ozone exposure, may mediate the toxic response of cells to carbon blacks in vitro. Results showed that macrophages exposed to carbon blacks that had been exposed to ozone were not less viable in vitro than macrophages exposed to carbon blacks as manufactured because the free radical content that resulted from ozone exposure was not persistent in an aqueous medium. Furthermore, concurrent exposure to ozonated carbon blacks and ozone was less lethal to macrophages than carbon black exposure alone, possibly because the ozone oxidatively preconditioned the macrophages to resist oxidative stress. The nature of redox-active iron species on the surface of iron-loaded synthetic carbon particles was explored. The particles had been shown in previous studies to provoke an inflammatory response involving the release of tumor necrosis factor (TNF)-alpha, which was correlated with their production of hydroxyl free radicals via the Fenton reaction in the presence of hydrogen peroxide. It was found that the source of bioavailable Fenton-active iron on the surfaces of the particles was fluoride species that were byproducts of a step in the synthetic process. Fluoride ligated the iron already on the surface, forming a complex that resisted precipitation in the biological medium and thus made the iron more bioavailable. The results of this thesis aim to clarify whether the size and surface chemistry of nanoparticles should be considered more closely as criteria with which to develop better environmental controls for occupational health. Permissible exposure limits to micrometer-size particulate matter in the workplace are in place, but current limits do not specifically address the role of surface chemistry and the potentially higher toxicity of nanomaterials. The size, agglomeration characteristics, and surface chemistry of carbon nanoparticles are being studied and manipulated to explore the causes of their toxicity. Inflammatory response and cytotoxicity following exposure of human and murine macrophages to nanoparticles are being employed as indicators of the ability of particles to cause respiratory harm. The results are expected to lead to more effective standards for nanomaterial exposure in the workplace and pathways to toxicity mitigation.

Assessment of geometrical characteristics of dental endodontic micro-instruments utilizing X-ray micro computed tomography

PubMed Central

Al JABBARI, Youssef S.; TSAKIRIDIS, Peter; ELIADES, George; AL-HADLAQ, Solaiman M.; ZINELIS, Spiros

2012-01-01

Objective The aim of this study was to quantify the surface area, volume and specific surface area of endodontic files employing quantitative X-ray micro computed tomography (mXCT). Material and Methods Three sets (six files each) of the Flex-Master Ni-Ti system (Nº 20, 25 and 30, taper .04) were utilized in this study. The files were scanned by mXCT. The surface area and volume of all files were determined from the cutting tip up to 16 mm. The data from the surface area, volume and specific area were statistically evaluated using the one-way ANOVA and SNK multiple comparison tests at α=0.05, employing the file size as a discriminating variable. The correlation between the surface area and volume with nominal ISO sizes were tested employing linear regression analysis. Results The surface area and volume of Nº 30 files showed the highest value followed by Nº 25 and Nº 20 and the differences were statistically significant. The Nº 20 files showed a significantly higher specific surface area compared to Nº 25 and Nº 30. The increase in surface and volume towards higher file sizes follows a linear relationship with the nominal ISO sizes (r2=0.930 for surface area and r2=0.974 for volume respectively). Results indicated that the surface area and volume demonstrated an almost linear increase while the specific surface area exhibited an abrupt decrease towards higher sizes. Conclusions This study demonstrates that mXCT can be effectively applied to discriminate very small differences in the geometrical features of endodontic micro-instruments, while providing quantitative information for their geometrical properties. PMID:23329248

Bonding between oxide ceramics and adhesive cement systems: a systematic review.

PubMed

Papia, Evaggelia; Larsson, Christel; du Toit, Madeleine; Vult von Steyern, Per

2014-02-01

The following aims were set for this systematic literature review: (a) to make an inventory of existing methods to achieve bondable surfaces on oxide ceramics and (b) to evaluate which methods might provide sufficient bond strength. Current literature of in vitro studies regarding bond strength achieved using different surface treatments on oxide ceramics in combination with adhesive cement systems was selected from PubMed and systematically analyzed and completed with reference tracking. The total number of publications included for aim a was 127 studies, 23 of which were used for aim b. The surface treatments are divided into seven main groups: as-produced, grinding/polishing, airborne particle abrasion, surface coating, laser treatment, acid treatment, and primer treatment. There are large variations, making comparison of the studies difficult. An as-produced surface of oxide ceramic needs to be surface treated to achieve durable bond strength. Abrasive surface treatment and/or silica-coating treatment with the use of primer treatment can provide sufficient bond strength for bonding oxide ceramics. This conclusion, however, needs to be confirmed by clinical studies. There is no universal surface treatment. Consideration should be given to the specific materials to be cemented and to the adhesive cement system to be used. Copyright © 2013 Wiley Periodicals, Inc.

Dual-Templated Cobalt Oxide for Photochemical Water Oxidation.

PubMed

Deng, Xiaohui; Bongard, Hans-Josef; Chan, Candace K; Tüysüz, Harun

2016-02-19

Mesoporous Co3 O4 was prepared using a dual templating approach whereby mesopores inside SiO2 nanospheres, as well as the void spaces between the nanospheres, were used as templates. The effect of calcination temperature on the crystallinity, morphology, and textural parameters of the Co3 O4 replica was investigated. The catalytic activity of Co3 O4 for photochemical water oxidation in a [Ru(bpy)3 ](2+) [S2 O8 ](2-) system was evaluated. The Co3 O4 replica calcined at the lowest temperature (150 °C) exhibited the best performance as a result of the unique nanostructure and high surface area arising from the dual templating. The performance of Co3 O4 with highest surface area was further examined in electrochemical water oxidation. Superior activity over high temperature counterpart and decent stability was observed. Furthermore, CoO with identical morphology was prepared from Co3 O4 using an ethanol reduction method and a higher turnover-frequency number for photochemical water oxidation was obtained. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fabrication of long-term stable superoleophobic surface based on copper oxide/cobalt oxide with micro-nanoscale hierarchical roughness

NASA Astrophysics Data System (ADS)

Barthwal, Sumit; Lim, Si-Hyung

2015-02-01

We have demonstrated a simple and cost-effective technique for the large-area fabrication of a superoleophobic surface using copper as a substrate. The whole process included three simple steps: First, the copper substrate was oxidized under hot alkaline conditions to fabricate flower-like copper oxide microspheres by heating at a particular temperature for an interval of time. Second, the copper-oxide-covered copper substrate was further heated in a solution of cobalt nitrate and ammonium nitrate in the presence of an ammonia solution to fabricate cobalt oxide nanostructures. We applied this second step to increase the surface roughness because it is an important criterion for improved superoleophobicity. Finally, to reduce the surface energy of the fabricated structures, the surfaces were chemically modified with perfluorooctyltrichlorosilane. Contact-angle measurements indicate that the micro-nano binary (MNB) hierarchical structures fabricated on the copper substrate became super-repellent toward a broad range of liquids with surface tension in the range of 21.5-72 mN/m. In an attempt to significantly improve the superoleophobic property of the surface, we also examined and compared the role of nanostructures in MNB hierarchical structures with only micro-fabricated surfaces. The fabricated MNB hierarchical structures also displays thermal stability and excellent long-term stability after exposure in air for more than 9 months. Our method might provide a general route toward the preparation of novel hierarchical films on metal substrates for various industrial applications.

Hydrothermal synthesis of zinc oxide nanoparticles using rice as soft biotemplate.

PubMed

Ramimoghadam, Donya; Bin Hussein, Mohd Zobir; Taufiq-Yap, Yun Hin

2013-01-01

Rice as a renewable, abundant bio-resource with unique characteristics can be used as a bio-template to synthesize various functional nanomaterials. Therefore, the effect of uncooked rice flour as bio-template on physico-chemical properties, especially the morphology of zinc oxide nanostructures was investigated in this study. The ZnO particles were synthesized through hydrothermal-biotemplate method using zinc acetate-sodium hydroxide and uncooked rice flour at various ratios as precursors at 120°C for 18 hours. The results indicate that rice as a bio-template can be used to modify the shape and size of zinc oxide particles. Different morphologies, namely flake-, flower-, rose-, star- and rod-like structures were obtained with particle size at micro- and nanometer range. Pore size and texture of the resulting zinc oxide particles were found to be template-dependent and the resulting specific surface area enhanced compared to the zinc oxide synthesized without rice under the same conditions. However, optical property particularly the band gap energy is generally quite similar. Pure zinc oxide crystals were successfully synthesized using rice flour as biotemplate at various ratios of zinc salt to rice. The size- and shape-controlled capability of rice to assemble the ZnO particles can be employed for further useful practical applications.

Self-Assembled Three-Dimensional Graphene Macrostructures: Synthesis and Applications in Supercapacitors.

PubMed

Xu, Yuxi; Shi, Gaoquan; Duan, Xiangfeng

2015-06-16

Graphene and its derivatives are versatile building blocks for bottom-up assembly of advanced functional materials. In particular, with exceptionally large specific surface area, excellent electrical conductivity, and superior chemical/electrochemical stability, graphene represents the ideal material for various electrochemical energy storage devices including supercapacitors. However, due to the strong π-π interaction between graphene sheets, the graphene flakes tend to restack to form graphite-like powders when they are processed into practical electrode materials, which can greatly reduce the specific surface area and lead to inefficient utilization of the graphene layers for electrochemical energy storage. The self-assembly of two-dimensional graphene sheets into three-dimensional (3D) framework structures can largely retain the unique properties of individual graphene sheets and has recently garnered intense interest for fundamental investigations and potential applications in diverse technologies. In this Account, we review the recent advances in preparing 3D graphene macrostructures and exploring them as a unique platform for supercapacitor applications. We first describe the synthetic strategies, in which reduction of a graphene oxide dispersion above a certain critical concentration can induce the reduced graphene oxide sheets to cross-link with each other via partial π-π stacking interactions to form a 3D interconnected porous macrostructure. Multiple reduction strategies, including hydrothermal/solvothermal reduction, chemical reduction, and electrochemical reduction, have been developed for the preparation of 3D graphene macrostructures. The versatile synthetic strategies allow for easy incorporation of heteroatoms, carbon nanomaterials, functional polymers, and inorganic nanostructures into the macrostructures to yield diverse composites with tailored structures and properties. We then summarize the applications of the 3D graphene macrostructures for high-performance supercapacitors. With a unique framework structure in which the graphene sheets are interlocked in 3D space to prevent their restacking, the graphene macrostructures feature very high specific surface areas, rapid electron and ion transport, and superior mechanical strength. They can thus be directly used as supercapacitor electrodes with excellent specific capacitances, rate capabilities, and cycling stabilities. We finally discuss the current challenges and future opportunities in this research field. By regarding the graphene as both a single-atom-thick carbon sheet and a conjugated macromolecule, our work opens a new avenue to bottom-up self-assembly of graphene macromolecule sheets into functional 3D graphene macrostructures with remarkable electrochemical performances. We hope that this Account will promote further efforts toward fundamental investigation of graphene self-assembly and the development of advanced 3D graphene materials for their real-world applications in electrochemical energy storage devices and beyond.

Chemisorption studies of Pt/SnO2 catalysts

NASA Technical Reports Server (NTRS)

Brown, Kenneth G.; Ohorodnik, Susan K.; Vannorman, John D.; Schryer, Jacqueline; Upchurch, Billy T.; Schryer, David R.

1990-01-01

The low temperature CO oxidation catalysts that are being developed and tested at NASA-Langley are fairly unique in their ability to efficiently oxidize CO at low temperatures (approx. 303 K). The bulk of the reaction data that has been collected in the laboratory has been determined using plug flow reactors with a low mass of Pt/SnO2/SiO2 catalyst (approx. 0.1 g) and a modest flow rate (5 to 10 sc sm). The researchers have previously characterized the surface solely in terms of N2 BET surface areas. These surface areas have not been that indicative of reaction rate. Indeed, some of the formulations with high BET surface area have yielded lower reaction rates than those with lower BET surface areas. As a result researchers began a program of determining the chemisorption of the various species involved in the reaction; CO, O2 and CO2. Such a determination of will lead to a better understanding of the mechanism and overall kinetics of the reaction. The pulsed-reactor technique, initially described by Freel, is used to determine the amount of a particular molecule that is adsorbed on the catalyst. Since there is some reaction of CO with the surface to produce CO2, the pulsed reactor had to be coupled with a gas chromatograph in order to distinguish between the loss of CO that is due to adsorption by the surface and the loss that is due to reaction with the surface.

Polymer adsorption on silica and wettability of graphene oxide surfaces, experiments and simulations

NASA Astrophysics Data System (ADS)

Mortazavian, Hamid

Among the various classifications of polymer composites, studying polymers adsorbed to a surface such as silica is important due to their numerous applications. Adsorbed polymers usually show different properties than their bulk counterparts due to their interactions with the surface. In this study, we observed tightly- and loosely-bound polymer and mobile components in poly(vinyl acetate) (PVAc) on silica both with temperature-modulated differential scanning calorimetry (TMDSC) experiments and computer simulations. The more-mobile component which correlated to the region of low density at the air interface is reported for the first time using TMDSC thermograms. Pore size distribution and pore volume development of adsorbed PMMA samples showed different behavior below and above the tightly-bound amount of the polymer. The amount of tightly-bound polymer was obtained by a linear regression analysis of the ratio of the area under the two glass transitions. The values obtained vary from 0.52 to 0.86 mg PVAc/m2 silica depending upon the molecular mass for the amounts of PVAc and the specific surface area of fumed silica. Direct comparisons of the thermal properties and intermolecular interactions were performed between PVAc and poly(methyl methacrylate) (PMMA) with similar molecular masses and adsorbed amounts on silica. A larger amount of tightly-bound polymer and a greater change in glass transition were observed for adsorbed PMMA compared to adsorbed PVAc. These observations suggested that the interactions between PMMA and silica were stronger than those between PVAc and silica. Molecular modeling of these surface polymers showed that PMMA associates more strongly with silica than does PVAc through additional hydrogen-bonding interactions. Graphene oxide (GO) material surface characteristics make it easy to functionalize, making it a water repellant surface. To test the effect of chemical makeup and size of attached groups on the surface wettability of GO, we performed experimental water contact angle measurements and molecular modeling investigations on functionalized GO surfaces. Experimental and molecular simulation water contact angle measurements showed quantitative agreement for functionalizing groups with the same chain length at a variety of surface coverages.

Effects of pyrolysis temperature, time and leaf litter and powder coal ash addition on sludge-derived adsorbents for nitrogen oxide.

PubMed

Ren, Xiaoli; Liang, Baohong; Liu, Min; Xu, Xiaoyuan; Cui, Meihua

2012-12-01

The objective of this research was to seek a cost effective solution to prepare adsorbents for nitrogen oxide from surplus sludge. Leaf litter and powder coal ash were used as cheap and easily available additives. An adsorbent for nitrogen oxide was prepared by pyrolysis of dried sludge mixed with zinc chloride. Under optimum pyrolysis conditions of 375°C for 90 min and a zinc chloride content of 30%, the surface area of the adsorbent with leaf litter was 514.41 m(2)/g, the surface area of the adsorbent with powder coal ash was 432.34 m(2)/g, respectively, corresponding to an increase of 90.70% and 60.27% when compared to the adsorbent without the additives. The saturated adsorption quantity of the adsorbent with leaf litter reached 271 mg/g at 20°C. The results indicated that the sludge-derived adsorbent was quite promising for nitrogen oxide removal. Copyright © 2012 Elsevier Ltd. All rights reserved.

Electrophoretically deposited multiwalled carbon nanotube based amperometric genosensor for E.coli detection

NASA Astrophysics Data System (ADS)

Bhardwaj, Hema; Solanki, Shipra; Sumana, Gajjala

2016-04-01

This work reports on a sensitive and selective genosensor fabrication method for Escherichia coli (E.coli) detection. The functionalized multiwalled carbon nanotubes (MWCNT) synthesized via chemical vapour deposition have been deposited electrophoretically onto indium tin oxide coated glass surface and have been utilized as matrices for the covalent immobilization of E.coli specific probe oligonucleotide that was identified from the 16s rRNA coding region of the E.coli genome. This fabricated functionalized MWCNT based platform sought to provide improved fundamental characteristics to electrode interface in terms of electro-active surface area and diffusion coefficient. Electrochemical cyclic voltammetry revealed that this genosensor exhibits a linear response to complementary DNA in the concentration range of 10-7 to 10-12 M with a detection limit of 1×10-12 M.

Room temperature synthesis and enhanced photocatalytic property of CeO2/ZnO heterostructures

NASA Astrophysics Data System (ADS)

Wang, Chao; Fan, Huiqing; Ren, Xiaohu; Fang, Jiawen

2018-02-01

To achieve better photocatalytic performance, we proposed a facile solid-state reaction method to produce CeO2/ZnO heterostructures. Ceria and zinc oxide were synthesized simultaneously by thoroughly grinding the mixture of zinc acetate dihydrate, cerium nitrate hexahydrate and sodium hydroxide. The morphology of the as-prepared heterostructures varies dramatically as different amount of ceria was introduced in the composition. The photocatalytic performance of CeO2/ZnO heterojunctions was 4.6 times higher than that of pure ZnO. The enhanced photocatalytic activity could be ascribed to that more electrons and holes could transport to the surface of catalysts and react with the pollution due to the extended light-responsive range, accelerated migration, increased specific surface area and suppressed recombination of photogenerated carriers.

Improved electrochemical performance of polyindole/carbon nanotubes composite as electrode material for supercapacitors

NASA Astrophysics Data System (ADS)

Cai, Zhi-Jiang; Zhang, Qin; Song, Xian-You

2016-09-01

Polyindole/carbon nanotubes (PIN/CNTs) composite was prepared by an in-situ chemical oxidative polymerization of indole monomer with CNTs using ammonium persulfate as oxidant. The obtained composite material was characterized by SEM, TEM, FT-IR, Raman spectroscopy, XPS, XRD and BET surface areas measurements. It was found that the CNTs were incorporated into the PIN matrix and nanoporous structure was formed. Spectroscopy results showed that interfacial interaction bonds might be formed between the polyindole chains and CNTs during the in-situ polymerization. PIN/CNTs composite was evaluated by electrochemical impedance spectroscopy, cyclic voltammetry and charge/discharge tests to determine electrode performances in relation to supercapacitors properties in both aqueous and non-aqueous system. A maximum specific capacitance and specific volumetric capacitance of 555.6 F/g and 222.2 F/cm3 can be achieved at 0.5 A/g in non-aqueous system. It also displayed good rate performance and cycling stability. The specific capacitance retention is over 60% at 10 A/g and 91.3% after 5000 cycles at 2 A/g, respectively. These characteristics point to its promising applications in the electrode material for supercapacitors.

The electrochemical oxide growth behaviour on titanium in acid and alkaline electrolytes.

PubMed

Sul, Y T; Johansson, C B; Jeong, Y; Albrektsson, T

2001-06-01

Titanium implants have a thin oxide surface layer. The properties of this oxide layer may explain the good biocompatibility of titanium implants. Anodic oxidation results in a thickening of the oxide film, with possible improved biocompatability of anodized implants. The aim of the present study was twofold: (1) firstly, to characterize the growth behaviour of galvanostatically prepared anodic oxide films on commercially pure (c.p.) titanium and (2) secondly, to establish a better understanding of the electroche0mical growth behaviour of anodic oxide on commercially pure titanium (ASTM grade 1) after changes of the electrochemical parameters in acetic acid, phosphoric acid, calcium hydroxide, and sodium hydroxide under galvanostatic anodizing mode. The oxide thickness was measured by Ar sputter etching in Auger Electron spectroscopy (AES) and the colours were estimated by an L*a*b* system (lightness, hue and saturation) using a spectrophotometer. In the first part of our study, it was demonstrated that the interference colours were useful to identify the thickness of titanium oxide. It was also found that the anodic forming voltages with slope (dV/dt) in acid electrolytes were higher than in alkaline electrolytes. Each of the used electrolytes demonstrates an intrinsically specific growth constant (nm/V) in the range of 1.4--2.78 nm/V. In the second part of our study we found, as a general trend, that an increase of electrolyte concentration and electrolyte temperature respectively decreases the anodic forming voltage, the anodic forming rate (nm/s) and the current efficiency (nm.cm(2)/C), while an increase of the current density and the surface area ratio of the anode to cathode increase the anodic forming voltage, the anodic forming rate and the current efficiency. The effects of electrolyte concentration, electrolyte temperature, and agitation speed were explained on the basis of the model of the electrical double layer.