Electrodeposition of platinum and silver into chemically modified microporous silicon electrodes

PubMed Central

2012-01-01

Electrodeposition of platinum and silver into hydrophobic and hydrophilic microporous silicon layers was investigated using chemically modified microporous silicon electrodes. Hydrophobic microporous silicon enhanced the electrodeposition of platinum in the porous layer. Meanwhile, hydrophilic one showed that platinum was hardly deposited within the porous layer, and a film of platinum on the top of the porous layer was observed. On the other hand, the electrodeposition of silver showed similar deposition behavior between these two chemically modified electrodes. It was also found that the electrodeposition of silver started at the pore opening and grew toward the pore bottom, while a uniform deposition from the pore bottom was observed in platinum electrodeposition. These electrodeposition behaviors are explained on the basis of the both effects, the difference in overpotential for metal deposition on silicon and on the deposited metal, and displacement deposition rate of metal. PMID:22720690

Platinum nanowire microelectrode arrays for neurostimulation applications: Fabrication, characterization, and in-vitro retinal cell stimulation

NASA Astrophysics Data System (ADS)

Whalen, John J., III

Implantable electrical neurostimulating devices are being developed for a number of applications, including artificial vision through retinal stimulation. The epiretinal prosthesis will use a two-dimensional array microelectrodes to address individual cells of the retina. MEMS fabrication processes can produce arrays of microelectrodes with these dimensions, but there are two critical issues that they cannot satisfy. One, the stimulating electrodes are the only part of the implanted electrical device that penetrate through the water impermeable package, and must do so without sacrificing hermeticity. Two, As electrode size decreases, the current density (A cm-2 ) increases, due to increased electrochemical impedance. This reduces the amount of charge that can be safely injected into the tissue. To date, MEMS processing method, cannot produce electrode arrays with good, prolonged hermetic properties. Similarly, MEMS approaches do not account for the increased impedance caused by decreased surface area. For these reasons there is a strong motivation for the development of a water-impermeable, substrate-penetrating electrode array with low electrochemical impedance. This thesis presents a stimulating electrode array fabricated from platinum nanowires using a modified electrochemical template synthesis approach. Nanowires are electrochemically deposited from ammonium hexachloroplatinate solution into lithographically patterned nanoporous anodic alumina templates to produce microarrays of platinum nanowires. The platinum nanowires penetrating through the ceramic aluminum oxide template serve as parallel electrical conduits through the water impermeable, electrically insulating substrate. Electrode impedance can be adjusted by either controlling the nanowire hydrous platinum oxide content or by partially etching the alumina template to expose additional surface area. A stepwise approach to this project was taken. First, the electrochemistry of ammonium hexachloroplatinate solution was characterized, and physical properties of electrodeposited thin films were correlated to deposition conditions used. Second, platinum nanowires were fabricated and their properties characterized, using similar deposition conditions. Third, the feasibility of fabricating platinum nanowire stimulating electrode arrays with a variety of surface structures was demonstrated. Fourth, the enhanced charge transfer characteristics of these structures were demonstrated using electrochemical techniques. Finally, retinal cell stimulation was demonstrated using electrodes from platinum nanowire arrays.

Plain to point network reduced graphene oxide - activated carbon composites decorated with platinum nanoparticles for urine glucose detection

NASA Astrophysics Data System (ADS)

Hossain, Mohammad Faruk; Park, Jae Y.

2016-02-01

In this study, a hydrothermal technique was applied to synthesize glucose-treated reduced graphene oxide-activated carbon (GRGO/AC) composites. Platinum nanoparticles (PtNP) were electrochemically deposited on the modified GRGO/AC surface, and chitosan-glucose oxidase (Chit-GOx) composites and nafion were integrated onto the modified surface of the working electrode to prepare a highly sensitive glucose sensor. The fabricated biosensor exhibited a good amperometric response to glucose in the detection range from 0.002 mM to 10 mM, with a sensitivity of 61.06 μA/mMcm2, a short response time (4 s) and a low detection limit of 2 μM (signal to noise ratio is 3). The glucose sensor exhibited a negligible response to interference and good stability. In addition, the glucose levels in human urine were tested in order to conduct a practical assessment of the proposed sensor, and the results indicate that the sensor had superior urine glucose recognition. These results thus demonstrate that the noble nano-structured electrode with a high surface area and electrocatalytic activity offers great promise for use in urine glucose sensing applications.

Plain to point network reduced graphene oxide - activated carbon composites decorated with platinum nanoparticles for urine glucose detection

PubMed Central

Hossain, Mohammad Faruk; Park, Jae Y.

2016-01-01

In this study, a hydrothermal technique was applied to synthesize glucose-treated reduced graphene oxide-activated carbon (GRGO/AC) composites. Platinum nanoparticles (PtNP) were electrochemically deposited on the modified GRGO/AC surface, and chitosan-glucose oxidase (Chit-GOx) composites and nafion were integrated onto the modified surface of the working electrode to prepare a highly sensitive glucose sensor. The fabricated biosensor exhibited a good amperometric response to glucose in the detection range from 0.002 mM to 10 mM, with a sensitivity of 61.06 μA/mMcm2, a short response time (4 s) and a low detection limit of 2 μM (signal to noise ratio is 3). The glucose sensor exhibited a negligible response to interference and good stability. In addition, the glucose levels in human urine were tested in order to conduct a practical assessment of the proposed sensor, and the results indicate that the sensor had superior urine glucose recognition. These results thus demonstrate that the noble nano-structured electrode with a high surface area and electrocatalytic activity offers great promise for use in urine glucose sensing applications. PMID:26876368

Photoinduced DNA damage and cytotoxicity by a triphenylamine-modified platinum-diimine complex.

PubMed

Zhang, Zhigang; Dai, Ruihui; Ma, Jiajia; Wang, Shuying; Wei, Xuehong; Wang, Hongfei

2015-02-01

Many planar photosensitizers tend to self-aggregate via van der Waals interactions between π-conjugated systems. The self-aggregation of the photosensitizer may reduce the efficiency of the photosensitizer to generate singlet oxygen, thereby diminishing its photodynamic activity. Efforts have been made to improve the photodynamic activity of bis-(o-diiminobenzosemiquinonato)platinum(II) which has planar geometry by the introduction of the sterically hindered triphenylamine moiety into the ligand. Herein we report the photoinduced DNA damage and cytotoxicity by a triphenylamine-modified platinum-diimine complex in red light studied by fluorescence spectra, agarose gel assay and cell viability assay. The results suggest that the triphenylamine-modified platinum-diimine complex has better capability to generate singlet oxygen than bis-(o-diiminobenzosemiquinonato)platinum(II), and it can induce DNA damage in red light, causing high photocytotoxicity in HepG-2 cells in vitro. Copyright © 2014 Elsevier Inc. All rights reserved.

The effect of nanoparticles size on photocatalytic and antimicrobial properties of Ag-Pt/TiO2 photocatalysts

NASA Astrophysics Data System (ADS)

Zielińska-Jurek, Anna; Wei, Zhishun; Wysocka, Izabela; Szweda, Piotr; Kowalska, Ewa

2015-10-01

Ag-Pt-modified TiO2 nanocomposites were synthesized using the sol-gel method. Bimetallic modified TiO2 nanoparticles exhibited improved photocatalytic activity under visible-light irradiation, better than monometallic Ag/TiO2 and Pt/TiO2 nanoparticles (NPs). All modified powders showed localized surface plasmon resonance (LSPR) in visible region. The photocatalysts' characteristics by X-ray diffractometry (XRD), scanning transmission electron microscopy (STEM), diffuse reflectance spectroscopy (DRS), X-ray photoelectron spectroscopy (XPS), nitrogen adsorption (BET method for specific surface area) showed that sample with the highest photocatalytic activity had anatase structure, about 93 m2/g specific surface area, maximum plasmon absorption at ca. 420 nm and contained small NPs of silver of 6 nm and very fine platinum NPs of 3 nm. The photocatalytic activity was estimated by measuring the decomposition rate of phenol in 0.2 mM aqueous solution under Vis and UV/vis light irradiation. It was found that size of platinum was decisive for the photocatalytic activity under visible light irradiation, i.e., the smaller Pt NPs were, the higher was photocatalytic activity. While, antimicrobial activities, estimated for bacteria Escherichia coli and Staphylococcus aureus, and pathogenic fungi belonging to Candida family, were only observed for photocatalysts containing silver, i.e., Ag/TiO2 and Ag-Pt/TiO2 nanocomposites.

Electroanalytical method for determination of lead(II) in orange and apple using kaolin modified platinum electrode.

PubMed

El Mhammedi, M A; Achak, M; Bakasse, M; Chtaini, A

2009-08-01

This paper reports on the use of platinum electrode modified with kaolin (K/Pt) and square wave voltammetry for analytical detection of trace lead(II) in pure water, orange and apple samples. The electroanalytical procedure for determination of the Pb(II) comprises two steps: the chemical accumulation of the analyte under open-circuit conditions followed by the electrochemical detection of the preconcentrated species using square wave voltammetry. The analytical performances of the extraction method has been explored by studying the incubating time, and effect of interferences due to other ions. During the preconcentration step, Pb(II) was accumulated on the surface of the kaolin. The observed detection and quantification limits in pure water were 3.6x10(-9)molL(-1) and 1.2x10(-8)molL(-1), respectively. The precision of the method was also determined; the results was 2.35% (n=5).

Enhanced anti-cancer efficacy to cancer cells by doxorubicin loaded water-soluble amino acid-modified β-cyclodextrin platinum complexes.

PubMed

Zhao, Mei-Xia; Zhao, Meng; Zeng, Er-Zao; Li, Yang; Li, Jin-Ming; Cao, Qian; Tan, Cai-Ping; Ji, Liang-Nian; Mao, Zong-Wan

2014-08-01

The effective targeted delivery of insoluble anticancer drugs to increase the intracellular drug concentration has become a focus in cancer therapy. In this system, two water-soluble amino acid-modified β-cyclodextrin (β-CD) platinum complexes were reported. They showed preferable binding ability to DNA and effective inhibition to cancer cells, and they could bind and unwind pBR322 DNA in a manner which was similar to cisplatin. Besides, our platinum complexes could effectively deliver the anticancer drug doxorubicin (Dox) into cells and had higher cell inhibition ratio, but less toxicity on the normal cells, compared with cancer cells. In this combination system, Dox was encapsulated into the hydrophobic cavities of β-CD at the optimum molar ratio of 1:1, which were validated by UV-visible (UV-vis) absorption spectroscopy, fluorescence spectroscopy and MTT experiments. Moreover, the combination system had higher cell inhibition ratio than free Dox and amino acid-modified β-CD platinum complexes, and the results of high content screening (HCS) showed that Dox-loaded amino acid-modified β-CD platinum complexes could permeate the cell membrane and enter cells, suggesting the efficient transport of Dox across the membranes with the aid of the β-CD. We expect that the amino acid-modified β-CD platinum complexes will deliver the antitumor drug Dox to enhance intracellular drug accumulation and such combination system showed great potential as an antitumor drug. Copyright © 2014 Elsevier Inc. All rights reserved.

Laser patterning of platinum electrodes for safe neurostimulation

NASA Astrophysics Data System (ADS)

Green, R. A.; Matteucci, P. B.; Dodds, C. W. D.; Palmer, J.; Dueck, W. F.; Hassarati, R. T.; Byrnes-Preston, P. J.; Lovell, N. H.; Suaning, G. J.

2014-10-01

Objective. Laser surface modification of platinum (Pt) electrodes was investigated for use in neuroprosthetics. Surface modification was applied to increase the surface area of the electrode and improve its ability to transfer charge within safe electrochemical stimulation limits. Approach. Electrode arrays were laser micromachined to produce Pt electrodes with smooth surfaces, which were then modified with four laser patterning techniques to produce surface structures which were nanosecond patterned, square profile, triangular profile and roughened on the micron scale through structured laser interference patterning (SLIP). Improvements in charge transfer were shown through electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV) and biphasic stimulation at clinically relevant levels. A new method was investigated and validated which enabled the assessment of in vivo electrochemically safe charge injection limits. Main results. All of the modified surfaces provided electrical advantage over the smooth Pt. The SLIP surface provided the greatest benefit both in vitro and in vivo, and this surface was the only type which had injection limits above the threshold for neural stimulation, at a level shown to produce a response in the feline visual cortex when using an electrode array implanted in the suprachoroidal space of the eye. This surface was found to be stable when stimulated with more than 150 million clinically relevant pulses in physiological saline. Significance. Critical to the assessment of implant devices is accurate determination of safe usage limits in an in vivo environment. Laser patterning, in particular SLIP, is a superior technique for improving the performance of implant electrodes without altering the interfacial electrode chemistry through coating. Future work will require chronic in vivo assessment of these electrode patterns.

Low-temperature direct heterogeneous bonding of polyether ether ketone and platinum.

PubMed

Fu, Weixin; Shigetou, Akitsu; Shoji, Shuichi; Mizuno, Jun

2017-10-01

Direct heterogeneous bonding between polyether ether ketone (PEEK) and Pt was realized at the temperatures lower than 150°C. In order to create sufficient bondability to diverse materials, the surface was modified by vacuum ultraviolet (VUV) irradiation, which formed hydrate bridges. For comparison, direct bonding between surfaces atomically cleaned via Ar fast atom bombardment (FAB) was conducted in a vacuum. The VUV irradiation was found to be effective for creating an ultrathin hydrate bridge layer from the residual water molecules in the chamber. Tight bonds were formed through dehydration of the hydrate bridges by heating at 150°C, which also contributed to enhancing interdiffusion across the interface. The VUV-modified surfaces showed bondability as good as that of the FAB-treated surfaces, and the VUV-modified samples had shear strengths at the same level as those of FAB-treated surfaces. This technology will be of practical use in the packaging of lightweight, flexible biomedical devices. Copyright © 2017 Elsevier B.V. All rights reserved.

Determination of platinum surface contamination in veterinary and human oncology centres using inductively coupled plasma mass spectrometry.

PubMed

Janssens, T; Brouwers, E E M; de Vos, J P; de Vries, N; Schellens, J H M; Beijnen, J H

2015-09-01

The objective of this study was to determine the surface contamination with platinum-containing antineoplastic drugs in veterinary and human oncology centres. Inductively coupled plasma mass spectrometry was used to measure platinum levels in surface samples. In veterinary and human oncology centres, 46.3 and 68.9% of the sampled surfaces demonstrated platinum contamination, respectively. Highest platinum levels were found in the preparation rooms (44.6 pg cm(-2)) in veterinary centres, while maximal levels in human centres were found in oncology patient-only toilets (725 pg cm(-2)). Transference of platinum by workers outside areas where antineoplastic drugs were handled was observed in veterinary and human oncology centres. In conclusion, only low levels of platinum contamination attributable to carboplatin were found in the sampled veterinary oncology centres. However, dispersion of platinum outside areas where antineoplastic drugs were handled was detected in veterinary and human oncology centres. Consequently, not only personnel, but also others may be exposed to platinum. © 2013 Blackwell Publishing Ltd.

Preparation of platinum modified titanium dioxide nanoparticles with the use of laser ablation in water.

PubMed

Siuzdak, K; Sawczak, M; Klein, M; Nowaczyk, G; Jurga, S; Cenian, A

2014-08-07

We report on the preparation method of nanocrystalline titanium dioxide modified with platinum by using nanosecond laser ablation in liquid (LAL). Titania in the form of anatase crystals has been prepared in a two-stage process. Initially, irradiation by laser beam of a titanium metal plate fixed in a glass container filled with deionized water was conducted. After that, the ablation process was continued, with the use of a platinum target placed in a freshly obtained titania colloid. In this work, characterization of the obtained nanoparticles, based on spectroscopic techniques--Raman, X-ray photoelectron and UV-vis reflectance spectroscopy--is given. High resolution transmission electron microscopy was used to describe particle morphology. On the basis of photocatalytic studies we observed the rate of degradation process of methylene blue (MB) (a model organic pollution) in the presence of Pt modified titania in comparison to pure TiO2--as a reference case. Physical and chemical mechanisms of the formation of platinum modified titania are also discussed here. Stable colloidal suspensions containing Pt modified titanium dioxide crystalline anatase particles show an almost perfect spherical shape with diameters ranging from 5 to 30 nm. The TiO2 nanoparticles decorated with platinum exhibit much higher (up to 30%) photocatalytic activity towards the degradation of MB under UV illumination than pure titania.

Microwave-assisted synthesis of gold, silver, platinum and palladium nanostructures and their use in electrocatalytic applications.

PubMed

Safavi, Afsaneh; Tohidi, Maryam

2014-09-01

Microwave-assisted ionic liquid method was used for synthesis of various noble metals, such as gold, silver, platinum and palladium nanomaterials. This route does not employ any template agent, surface capping agents or reducing agents. The process is fast, simple and of high yield. Different metal precursors in various ionic liquids media (1-butyl-3-methylimidazolium tetrafluoroborate, octyl pyridinium hexaflurophosphate and 1-octyl-3-methylimidazolium hexaflurophosphate) were applied to produce metal nanomaterials. Silver, platinium and palladium nanoparticles exhibit spherical morphology while nanosheets with high aspect ratio were obtained for gold. These metal nanostructures were incorporated into a carbon ionic liquid electrode to investigate their electrocatalytic properties. It was found that synthesis in different ionic liquids result in different activity. Excellent electrocatalytic effects toward adenine, hydrazine, formaldehyde and ethanol were observed for the modified electrodes with different nanoparticles synthesized in 1-butyl-3-methylimidazolium tetrafluoroborate. The high conductivity, large surface-to-volume ratio and active sites of nanosized metal particles are responsible for their electrocatalytic activity. In contrast, the carbon ionic liquid electrode modified with synthesized metal nanoparticles in octyl pyridinium hexaflurophosphate and 1-octyl-3-methylimidazolium hexaflurophosphate showed negligible activity for detection of these probes.

Platinum Monolayer Shell on Non-Noble Metal Core Electrocatalysts for the Hydrogen Oxidation Reaction

NASA Astrophysics Data System (ADS)

Teeluck, Krishani Malini

According to the United States Environmental Protection Agency, as of 2015, transportation accounted for 32% of the carbon dioxide emissions in the United States (and all carbon dioxide emissions in the U.S. accounted for 82.2% of all greenhouse gases from human activity). A hydrogen fuel cell is a device that efficiently produces electrical energy directly from a chemical reaction, with zero carbon emissions, and therefore holds great promise in alleviating our dependence on harmful use of energy sources. Due to their clean emissions and high efficiencies, there has been focus on the hydrogen fuel cell for vehicle applications using proton exchange membrane and alkaline fuel cells. Although the proton exchange membrane fuel cell is currently being used in vehicles, their high cost limits their feasibility in the market. This has inspired the development of the alkaline fuel cell whose efficiency and simplicity suggest the possibility of manufacturing high power fuel cell vehicles at a low cost, since the electrocatalysts in the alkaline fuel cell can be made from non-noble metals. Although the hydrogen oxidation reaction is one of the fastest electrochemical reactions in acidic media, it is two orders of magnitude slower in alkaline media, which hinders the overall efficiency of the alkaline fuel cell. Pure platinum is currently the best catalyst for the hydrogen oxidation reaction, but platinum’s high cost and rarity yields economic issues, rendering the technology futile if it cannot be commercialized. Furthermore, platinum’s hydrogen binding energy is slightly stronger than the optimal hydrogen binding energy. As the hydrogen oxidation reaction happens only on the surface of the catalyst, there is no need for platinum content beyond the exterior. Since tungsten and nickel are cheap, as well as abundant, they are ideal elements to replace the core of the catalyst with, while leaving a platinum shell surrounding this core. The activity of the hydrogen oxidation reaction when using a platinum monolayer shell on a nickel tungsten core electrocatalyst is explored, and it was found that the novel catalyst created here exhibits kinetics that rival pure platinum, but at less than half the platinum content, suggesting that nickel and tungsten modify the electronic properties of platinum in a way that enhances its activity for the hydrogen oxidation reaction. Furthermore, the hydrogen binding energy of this novel electrocatalyst was found to be weaker than the optimal binding energy (rather than stronger, as seen in pure platinum), indicating the possibility of modifying the electronic properties of platinum for a more optimal hydrogen binding energy.

Enhancement of the catalytic activity of Pt nanoparticles toward methanol electro-oxidation using doped-SnO2 supporting materials

NASA Astrophysics Data System (ADS)

Merati, Zohreh; Basiri Parsa, Jalal

2018-03-01

Catalyst supports play important role in governing overall catalyst activity and durability. In this study metal oxides (SnO2, Sb and Nb doped SnO2) were electrochemically deposited on titanium substrate (Ti) as a new support material for Pt catalyst in order to electro-oxidation of methanol. Afterward platinum nanoparticles were deposited on metal oxide film via electro reduction of platinum salt in an acidic solution. The surface morphology of modified electrodes were evaluated by field-emission scanning electron microscopy (FESEM) and energy dispersive X-ray analysis (EDX) techniques. The electro-catalytic activities of prepared electrodes for methanol oxidation reaction (MOR) and oxidation of carbon monoxide (CO) absorbed on Pt was considered with cyclic voltammetry. The results showed high catalytic activity for Pt/Nb-SnO2/Ti electrode. The electrochemical surface area (ECSA) of a platinum electro-catalyst was determined by hydrogen adsorption. Pt/Nb-SnO2/Ti electrode has highest ECSA compared to other electrode resulting in high activity toward methanol electro-oxidation and CO stripping experiments. The doping of SnO2 with Sb and Nb improved ECSA and MOR activity, which act as electronic donors to increase electronic conductivity.

Electrochemical oxygen reduction behavior of selectively deposited platinum atoms on gold nanoparticles.

PubMed

Sarkar, A; Kerr, J B; Cairns, E J

2013-07-22

Carbon-supported Pt@Au "core-shell" nanoparticles with varying surface concentration of platinum atoms have been synthesized using a novel redox-mediated synthesis approach. The synthesis technique allows for a selective deposition of platinum atoms on the surface of prefabricated gold nanoparticles. Energy dispersive spectroscopic analyses in a scanning electron microscope reveal that the platinum to gold atomic ratios are close to the nominal values, validating the synthesis scheme. X-ray diffraction data indicate an un-alloyed structure. The platinum to gold surface atomic ratio determined from cyclic voltammetry and copper under-potential deposition experiments reveal good agreement with the calculated values at low platinum concentration. However, there is an increase in non-uniformity in the deposition process upon increasing the platinum concentration. Koutecky-Levich analysis of the samples indicates a transition of the total number of electrons transferred (n) in the electrochemical oxygen reduction reaction from two to four electrons upon increasing the surface concentration of platinum atoms. Furthermore, the data indicate that isolated platinum atoms can reduce molecular oxygen but via a two-electron route. Moreover, successful four-electron reduction of molecular oxygen requires clusters of platinum atoms. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fabrication and surface-modification of implantable microprobes for neuroscience studies

NASA Astrophysics Data System (ADS)

Cao, H.; Nguyen, C. M.; Chiao, J. C.

2012-06-01

In this work implantable micro-probes for central nervous system (CNS) studies were developed on silicon and polyimide substrates. The probes which contained micro-electrode arrays with different surface modifications were designed for implantation in the CNS. The electrode surfaces were modified with nano-scale structures that could greatly increase the active surface area in order to enhance the electrochemical current outputs while maintaining micro-scale dimensions of the electrodes and probes. The electrodes were made of gold or platinum, and designed with different sizes. The silicon probes were modified by silicon nanowires fabricated with the vapor-liquid-solid mechanism at high temperatures. With polyimide substrates, the nanostructure modification was carried out by applying concentrated gold or silver colloid solutions onto the micro-electrodes at room temperature. The surfaces of electrodes before and after modification were observed by scanning electron microscopy. The silicon nanowire-modified surface was characterized by cyclic voltammetry. Experiments were carried out to investigate the improvement in sensing performance. The modified electrodes were tested with H2O2, electrochemical L-glutamate and dopamine. Comparisons between electrodes with and without nanostructure modification were conducted showing that the modifications have enhanced the signal outputs of the electrochemical neurotransmitter sensors.

Bimetallic alloy electrocatalysts with multilayered platinum-skin surfaces

DOEpatents

Stamenkovic, Vojislav R.; Wang, Chao; Markovic, Nenad M.

2016-01-26

Compositions and methods of preparing a bimetallic alloy having enhanced electrocatalytic properties are provided. The composition comprises a PtNi substrate having a surface layer, a near-surface layer, and an inner layer, where the surface layer comprises a nickel-depleted composition, such that the surface layer comprises a platinum skin having at least one atomic layer of platinum.

Monitoring of platinum surface contamination in seven Dutch hospital pharmacies using inductively coupled plasma mass spectrometry

PubMed Central

Huitema, A. D. R.; Bakker, E. N.; Douma, J. W.; Schimmel, K. J. M.; van Weringh, G.; de Wolf, P. J.; Schellens, J. H. M.; Beijnen, J. H.

2007-01-01

Objective: To develop, validate, and apply a method for the determination of platinum contamination, originating from cisplatinum, oxaliplatinum, and carboplatinum. Methods: Inductively coupled plasma mass spectrometry (ICP-MS) was used to determine platinum in wipe samples. The sampling procedure and the analytical conditions were optimised and the assay was validated. The method was applied to measure surface contamination in seven Dutch hospital pharmacies. Results: The developed method allowed reproducible quantification of 0.50 ng l−1 platinum (5 pg/wipe sample). Recoveries for stainless steel and linoleum surfaces ranged between 50.4 and 81.4% for the different platinum compounds tested. Platinum contamination was reported in 88% of the wipe samples. Although a substantial variation in surface contamination of the pharmacies was noticed, in most pharmacies, the laminar-airflow (LAF) hoods, the floor in front of the LAF hoods, door handles, and handles of service hatches showed positive results. This demonstrates that contamination is spread throughout the preparation rooms. Conclusion: We developed and validated an ultra sensitive and reliable ICP-MS method for the determination of platinum in surface samples. Surface contamination with platinum was observed in all hospital pharmacies sampled. The interpretation of these results is, however, complicated. PMID:17377802

Synthesis and properties of platinum on multiwall carbon nanotube modified by chitosan

NASA Astrophysics Data System (ADS)

Fikriyyah, A. K.; Chaldun, E. R.; Indriyati

2018-03-01

Platinum nanoparticles on multiwall carbon nanotubes (Pt/MWCNT) play an important role in fuel cell to convert the chemical energy from a fuel into electricity. In this study, Pt/MWCNT electrocatalysts were prepared by chemical reduction of the metal salts in chitosan as the support. Firstly, commercial MWCNTs were functionalized by oxidative process using a mixture of nitric acid and sulfuric acid. Then, functionalized MWCNTs were mixed with chitosan-acetic acid solution to conduct grafting reaction with NH2 groups in chitosan by solution polymerization method. Platinum nanoparticles were loaded onto the surface of the MWCNTs after hexachloroplatinic acid was reduced by sodium hydroxide solution. The result showed that Pt was attached on MWCNT based on analysis from EDS, XRD, and UV Vis Spectroscopy. UV Vis analysis indicates the plasmon absorbance band of Pt nanoparticles in Pt/MWCNT, while XRD analysis confirmed the size of Pt particle in nanometer. This elucidates the potential procedure to synthesize Pt/MWCNT using chitosan.

Methanol Steam Reforming Promoted by Molten Salt-Modified Platinum on Alumina Catalysts

PubMed Central

Kusche, Matthias; Agel, Friederike; Ní Bhriain, Nollaig; Kaftan, Andre; Laurin, Mathias; Libuda, Jörg; Wasserscheid, Peter

2014-01-01

We herein describe a straight forward procedure to increase the performance of platinum-on-alumina catalysts in methanol steam reforming by applying an alkali hydroxide coating according to the “solid catalyst with ionic liquid layer” (SCILL) approach. We demonstrate by diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and temperature-programmed desorption (TPD) studies that potassium doping plays an important role in the catalyst activation. Moreover, the hygroscopic nature and the basicity of the salt modification contribute to the considerable enhancement in catalytic performance. During reaction, a partly liquid film of alkali hydroxides/carbonates forms on the catalyst/alumina surface, thus significantly enhancing the availability of water at the catalytically active sites. Too high catalyst pore fillings with salt introduce a considerable mass transfer barrier into the system as indicated by kinetic studies. Thus, the optimum interplay between beneficial catalyst modification and detrimental mass transfer effects had to be identified and was found on the applied platinum-on-alumina catalyst at KOH loadings around 7.5 mass %. PMID:25124120

Sorption and recovery of platinum from simulated spent catalyst solution and refinery wastewater using chemically modified biomass as a novel sorbent.

PubMed

Garole, Dipak J; Choudhary, Bharat C; Paul, Debajyoti; Borse, Amulrao U

2018-04-01

In this study, Lagerstroemia speciosa biomass modified by polyethylenimine (PEI-LS) was developed as a potential biosorbent for sorption and recovery of platinum(II) from platinum bearing waste solutions. Batch experiments were conducted to study the effect of various parameters on the sorption and recovery of platinum(II) using PEI-LS. The equilibrium time for platinum(II) sorption process was found to be 6 h. Both the sorption kinetics and sorption isotherm data fits pseudo second-order kinetic model and Langmuir isotherm, respectively. The maximum sorption capacity of platinum(II) onto PEI-LS at pH 2 for the studied temperature range (25-45 °C) is in the range of 122-154 mg/g. Evaluation of thermodynamic parameters suggests that the platinum(II) sorption is spontaneous and endothermic in nature. The regeneration of PEI-LS can be achieved using acidic thiourea as an eluent for recovery of platinum from the biosorbent. Fourier transform infrared (FT-IR) analysis suggests many functional groups were involved in platinum(II) sorption onto PEI-LS. Both the scanning electron microscope/energy dispersive spectroscopy (SEM/EDS) and X-ray photoelectron spectroscopy (XPS) analysis suggest a successful modification of raw biomass with PEI. The XPS analysis further concludes that platinum(II) sorption is governed by ion-exchange and co-ordination reaction. Finally, the PEI-LS was shown to recover ≥ 90% of platinum from two simulated solutions: the acid-leached spent catalyst solution and refinery wastewater. The biosorbent developed in this study is a low-cost and eco-friendly media that can be effectively used for platinum recovery from industrial wastewater.

Amorphous nickel boride membrane on a platinum-nickel alloy surface for enhanced oxygen reduction reaction.

PubMed

He, Daping; Zhang, Libo; He, Dongsheng; Zhou, Gang; Lin, Yue; Deng, Zhaoxiang; Hong, Xun; Wu, Yuen; Chen, Chen; Li, Yadong

2016-08-09

The low activity of the oxygen reduction reaction in polymer electrolyte membrane fuel cells is a major barrier for electrocatalysis, and hence needs to be optimized. Tuning the surface electronic structure of platinum-based bimetallic alloys, a promising oxygen reduction reaction catalyst, plays a key role in controlling its interaction with reactants, and thus affects the efficiency. Here we report that a dealloying process can be utilized to experimentally fabricate the interface between dealloyed platinum-nickel alloy and amorphous nickel boride membrane. The coating membrane works as an electron acceptor to tune the surface electronic structure of the platinum-nickel catalyst, and this composite catalyst composed of crystalline platinum-nickel covered by amorphous nickel boride achieves a 27-times enhancement in mass activity relative to commercial platinum/carbon at 0.9 V for the oxygen reduction reaction performance. Moreover, this interactional effect between a crystalline surface and amorphous membrane can be readily generalized to facilitate the 3-times higher catalytic activity of commercial platinum/carbon.

Shaped platinum nanoparticles directly synthesized inside mesoporous silica supports

NASA Astrophysics Data System (ADS)

Kim, Jiwhan; Bae, Youn-Sang; Lee, Hyunjoo

2014-10-01

It is difficult to deposit shape-controlled nanoparticles into a mesoporous framework while preserving the shape. For shaped platinum nanoparticles, which are typically 5-10 nm in size, capillary inclusion by sonication or the formation of a mesoporous framework around the shaped platinum nanoparticles has been attempted, but the nanoparticles aggregated or their shapes were degraded easily. In this work, we directly nucleated platinum on the surface inside a mesoporous silica support and controlled the overgrowth step, producing cubic shaped nanoparticles. Mercaptopropyltrimethoxysilane was used as an anchoring agent causing nucleation at the silica surface, and it also helped to shape the nanoparticles. Platinum nanocubes, which were synthesized with polymeric capping agents separately, were deposited inside the mesoporous silica by sonication, but most of the nanoparticles were clogged at the entrance to the pores, and the surface of the platinum had very few sites that were catalytically active, as evidenced by the small H2 uptake. Unshaped platinum nanoparticles, which were prepared by conventional wet impregnation, showed a similar amount of H2 uptake as the in situ shaped platinum cubes, but the selectivity for pyrrole hydrogenation was poorer towards the production of pyrrolidine. The mesoporosity and the residual thiol groups on the surface of the in situ shaped Pt nanocubes might cause a high selectivity for pyrrolidine.It is difficult to deposit shape-controlled nanoparticles into a mesoporous framework while preserving the shape. For shaped platinum nanoparticles, which are typically 5-10 nm in size, capillary inclusion by sonication or the formation of a mesoporous framework around the shaped platinum nanoparticles has been attempted, but the nanoparticles aggregated or their shapes were degraded easily. In this work, we directly nucleated platinum on the surface inside a mesoporous silica support and controlled the overgrowth step, producing cubic shaped nanoparticles. Mercaptopropyltrimethoxysilane was used as an anchoring agent causing nucleation at the silica surface, and it also helped to shape the nanoparticles. Platinum nanocubes, which were synthesized with polymeric capping agents separately, were deposited inside the mesoporous silica by sonication, but most of the nanoparticles were clogged at the entrance to the pores, and the surface of the platinum had very few sites that were catalytically active, as evidenced by the small H2 uptake. Unshaped platinum nanoparticles, which were prepared by conventional wet impregnation, showed a similar amount of H2 uptake as the in situ shaped platinum cubes, but the selectivity for pyrrole hydrogenation was poorer towards the production of pyrrolidine. The mesoporosity and the residual thiol groups on the surface of the in situ shaped Pt nanocubes might cause a high selectivity for pyrrolidine. Electronic supplementary information (ESI) available: Fig. S1-S9. See DOI: 10.1039/c4nr03951c

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

PubMed Central

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

2016-01-01

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

To alloy or not to alloy? Cr modified Pt/C cathode catalysts for PEM fuel cells.

PubMed

Wells, Peter P; Qian, Yangdong; King, Colin R; Wiltshire, Richard J K; Crabb, Eleanor M; Smart, Lesley E; Thompsett, David; Russell, Andrea E

2008-01-01

The cathode electrocatalysts for proton exchange membrane (PEM) fuel cells are commonly platinum and platinum based alloy nanoparticles dispersed on a carbon support. Control over the particle size and composition has, historically, been attained empirically, making systematic studies of the effects of various structural parameters difficult. The controlled surface modification methodology used in this work has enabled the controlled modification of carbon supported Pt nanoparticles by Cr so as to yield nanoalloy particles with defined compositions. Subsequent heat treatment in 5% H2 in N2 resulted in the formation of a distinct Pt3Cr alloy phase which was either restricted to the surface of the particles or present throughout the bulk of the particle structure. Measurement of the oxygen reduction activity of the catalysts was accomplished using the rotating thin film electrode method and the activities obtained were related to the structure of the nanoalloy catalyst particles, largely determined using Cr K edge and Pt L3 edge XAS.

Deposition of platinum nanoparticles on carbon nanotubes by supercritical fluid method.

PubMed

Yen, Clive H; Cui, Xiaoli; Pan, Horng-Bin; Wang, Shaofen; Lin, Yuehe; Wai, Chien M

2005-11-01

Carbon nanotube-supported platinum nanoparticles with a 5-15 nm diameter size range can be synthesized by hydrogen reduction of platinum(ll) acetylacetonate in methanol modified supercritical carbon dioxide. X-ray photoelectron spectroscopy and X-ray diffraction spectra indicate that the carbon nanotubes contain zero-valent platinum metal and high-resolution transmission electron microscopy images show that the visible lattice fringes of platinum nanoparticles are crystallites. Carbon nanotubes synthesized with 25% by weight of platinum nanoparticles exhibit a higher activity for hydrogenation of benzene compared with a commercial carbon black platinum catalyst. The carbon nanotube-supported platinum nanocatalyst can be reused at least six times for the hydrogenation reaction without losing activity. The carbon nanotube-supported platinum nanoparticles are also highly active for electrochemical oxidation of methanol and for reduction of oxygen suggesting their potential use as a new electrocatalyst for proton exchange membrane fuel cell applications.

Photo-stimulated low electron temperature high current diamond film field emission cathode

DOEpatents

Shurter,; Roger Philips, Devlin [Los Alamos, NM; David James, Moody [Santa Fe, NM; Nathan Andrew, Taccetti [Los Alamos, NM; Jose Martin, Russell [Santa Fe, NM; John, Steven [Los Alamos, NM

2012-07-24

An electron source includes a back contact surface having a means for attaching a power source to the back contact surface. The electron source also includes a layer comprising platinum in direct contact with the back contact surface, a composite layer of single-walled carbon nanotubes embedded in platinum in direct contact with the layer comprising platinum. The electron source also includes a nanocrystalline diamond layer in direct contact with the composite layer. The nanocrystalline diamond layer is doped with boron. A portion of the back contact surface is removed to reveal the underlying platinum. The electron source is contained in an evacuable container.

Use of microelectrodes for electrochemical measurement of nitric oxide in natural seawater

NASA Astrophysics Data System (ADS)

Zhang, Zhengbin; Xing, Lei; Cai, Weijun; Ren, Chunyan; Jiang, Liqing

2004-12-01

In this paper, the application of a homemade Nafion and Co(Salen) modified platinum microelectrode and an ISO-NOPMC microsensor (World Precision Instruments, USA) to measure nitric oxide in natural seawater is reported. These two microelectrodes are suitable for the measurement. In natural seawater, the sensitivity and stability of the ISO-NOPMC microsensor are higher than that of the homemade Nafion and Co(Salen) modified platinum microelectrode.

Amperometric Biosensor Based on Diamine Oxidase/Platinum Nanoparticles/Graphene/Chitosan Modified Screen-Printed Carbon Electrode for Histamine Detection.

PubMed

Apetrei, Irina Mirela; Apetrei, Constantin

2016-03-24

This work describes the development and optimization studies of a novel biosensor employed in the detection and quantification of histamine in freshwater fish samples. The proposed biosensor is based on a modified carbon screen-printed electrode with diamineoxidase, graphene and platinum nanoparticles, which detects the hydrogen peroxide formed by the chemical process biocatalysed by the enzyme diamine oxidase and immobilized onto the nanostructurated surface of the receptor element. The amperometric measurements with the biosensor have been implemented in buffer solution of pH 7.4, applying an optimal low potential of +0.4 V. The novel biosensor shows high sensitivity (0.0631 μA·μM), low detection limit (2.54 × 10(-8) M) and a broad linear domain from 0.1 to 300 μM. The applicability in natural complex samples and the analytical parameters of this enzyme sensor have been performed in the quantification of histamine in freshwater fish. An excellent correlation among results achieved with the developed biosensor and results found with the standard method for all freshwater fish samples has been achieved.

Amperometric Biosensor Based on Diamine Oxidase/Platinum Nanoparticles/Graphene/Chitosan Modified Screen-Printed Carbon Electrode for Histamine Detection

PubMed Central

Apetrei, Irina Mirela; Apetrei, Constantin

2016-01-01

This work describes the development and optimization studies of a novel biosensor employed in the detection and quantification of histamine in freshwater fish samples. The proposed biosensor is based on a modified carbon screen-printed electrode with diamineoxidase, graphene and platinum nanoparticles, which detects the hydrogen peroxide formed by the chemical process biocatalysed by the enzyme diamine oxidase and immobilized onto the nanostructurated surface of the receptor element. The amperometric measurements with the biosensor have been implemented in buffer solution of pH 7.4, applying an optimal low potential of +0.4 V. The novel biosensor shows high sensitivity (0.0631 μA·μM), low detection limit (2.54 × 10−8 M) and a broad linear domain from 0.1 to 300 μM. The applicability in natural complex samples and the analytical parameters of this enzyme sensor have been performed in the quantification of histamine in freshwater fish. An excellent correlation among results achieved with the developed biosensor and results found with the standard method for all freshwater fish samples has been achieved. PMID:27023541

Electron microscopic visualization of complementary labeled DNA with platinum-containing guanine derivative.

PubMed

Loukanov, Alexandre; Filipov, Chavdar; Mladenova, Polina; Toshev, Svetlin; Emin, Saim

2016-04-01

The object of the present report is to provide a method for a visualization of DNA in TEM by complementary labeling of cytosine with guanine derivative, which contains platinum as contrast-enhanced heavy element. The stretched single-chain DNA was obtained by modifying double-stranded DNA. The labeling method comprises the following steps: (i) stretching and adsorption of DNA on the support film of an electron microscope grid (the hydrophobic carbon film holding negative charged DNA); (ii) complementary labeling of the cytosine bases from the stretched single-stranded DNA pieces on the support film with platinum containing guanine derivative to form base-specific hydrogen bond; and (iii) producing a magnified image of the base-specific labeled DNA. Stretched single-stranded DNA on a support film is obtained by a rapid elongation of DNA pieces on the surface between air and aqueous buffer solution. The attached platinum-containing guanine derivative serves as a high-dense marker and it can be discriminated from the surrounding background of support carbon film and visualized by use of conventional TEM observation at 100 kV accelerated voltage. This method allows examination of specific nucleic macromolecules through atom-by-atom analysis and it is promising way toward future DNA-sequencing or molecular diagnostics of nucleic acids by electron microscopic observation. © 2016 Wiley Periodicals, Inc.

Methanol steam reforming promoted by molten salt-modified platinum on alumina catalysts.

PubMed

Kusche, Matthias; Agel, Friederike; Ní Bhriain, Nollaig; Kaftan, Andre; Laurin, Mathias; Libuda, Jörg; Wasserscheid, Peter

2014-09-01

We herein describe a straight forward procedure to increase the performance of platinum-on-alumina catalysts in methanol steam reforming by applying an alkali hydroxide coating according to the "solid catalyst with ionic liquid layer" (SCILL) approach. We demonstrate by diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and temperature-programmed desorption (TPD) studies that potassium doping plays an important role in the catalyst activation. Moreover, the hygroscopic nature and the basicity of the salt modification contribute to the considerable enhancement in catalytic performance. During reaction, a partly liquid film of alkali hydroxides/carbonates forms on the catalyst/alumina surface, thus significantly enhancing the availability of water at the catalytically active sites. Too high catalyst pore fillings with salt introduce a considerable mass transfer barrier into the system as indicated by kinetic studies. Thus, the optimum interplay between beneficial catalyst modification and detrimental mass transfer effects had to be identified and was found on the applied platinum-on-alumina catalyst at KOH loadings around 7.5 mass%. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Growth mechanism of surface roughed platinum nanowires through electrodeposition current control and their electrochemical applications

NASA Astrophysics Data System (ADS)

Ruan, Dajiang

The aim of this work is to investigate the effect of current density on the grain size and surface morphology of electrodeposited platinum nanowires and their applications. Platinum (Pt) nanowires were fabricated by a galvanostatic electrodeposition method in a porous anodic alumina oxide (AAO) template with different current densities. Both direct current and pulse current electrodeposition were used to synthesize the Pt nanowires. The grain size and surface morphology of the Pt nanowires were studied by field emission scanning electron microscopy (FE-SEM), transmission electron microcopy (TEM) and X-ray diffraction (XRD). The experimental results showed that the current density was the key factor to control the surface roughness. The surface of the Pt nanowires became rougher and the grain sizes were increased by increasing the current densities. From the experimental results, a growth mechanism of Pt nanowires based on progressive nucleation and crystallization was proposed in order to find out the relationship between the surface morphology and current density. The electrochemical properties and catalytic activities of these surface roughed Pt nanowires were investigated in the detection of H20 2 and for the methanol oxidation. Cyclic voltammograms of Pt nanowire modified electrodes were obtained using a potentiostat, which showed that rougher Pt nanowires have higher response and better activity than that of smooth nanowires. For H202 detection, the effect of scan rate and H202 concentration were studied and it was found that the peak current for hydrogen peroxide reduction became larger with the increasing of either scan rate or H202 concentration. It can be inferred that the process of electrocatalytic hydrogen peroxide reduction may be controlled by diffusion of hydrogen peroxide and the Pt nanowire modified glassy carbon electrode (GCE) is well suited for the detection of H202. From the relationship between the peak current and square root of scan rates for methanol oxidation, it can be inferred that the process of electrocatalytic methanol oxidation was controlled by diffusion of methanol. To understand the effect of the morphological feature on the electrocatalytic activity of the Pt nanowire catalysts, the electrochemically active surface area (ECSA) as a function of deposited current density was investigated, which suggests that Pt nanowire catalysts deposited at highest current density had the most ECSA surface morphology of the Pt nanowires. The chronoamperometric curves and electrochemical impedance spectroscopy (EIS) results confirmed that the Pt nanowire catalyst synthesized at higher current density possessed longer durability and gave more efficient electrochemical performance.

Biosensors Based on Urease Adsorbed on Nickel, Platinum, and Gold Conductometric Transducers Modified with Silicalite and Nanozeolites

NASA Astrophysics Data System (ADS)

Kucherenko, Ivan S.; Soldatkin, Oleksandr O.; Kasap, Berna Ozansoy; Kurç, Burcu Akata; Melnyk, Volodymir G.; Semenycheva, Lyudmila M.; Dzyadevych, Sergei V.; Soldatkin, Alexei P.

This work describes urease-based conductometric biosensors that were created using nontypical method of urease immobilization via adsorption on micro- and nanoporous particles: silicalite and nanocrystalline zeolites Beta (BEA) and L. Conductometric transducers with nickel, gold, and platinum interdigitated electrodes were used. Active regions of the nickel transducers were modified with microparticles using two procedures—spin coating and drop coating. Gold and platinum transducers were modified with silicalite using drop coating since it was more effective. Scanning electron microscopy was used to evaluate effectiveness of these procedures. The procedure of spin coating produced more uniform layers of particles (and biosensors had good reproducibility of preparation), but it was more complicated, drop coating was easier and led to formation of a bulk of particles; thus, biosensors had bigger sensitivity but worse reproducibility of preparation. Urease was immobilized onto transducers modified with particles by physical adsorption. Analytical characteristics of the obtained biosensors for determination of urea (calibration curves, sensitivity, limit of detection, linear concentration range, noise of responses, reproducibility of signal during a day, and operational stability during 3 days) were compared. Biosensors with all three particles deposited by spin coating showed similar characteristics; however, silicalite was a bit more effective. Biosensors based on nickel transducers modified by drop coating had better characteristics in comparison with modification by spin coating (except reproducibility of preparation). Transducers with gold electrodes showed best characteristics while creating biosensors, platinum electrodes were slightly inferior to them, and nickel electrodes were the worst.

Photoelectrochemical electrodes

NASA Technical Reports Server (NTRS)

Williams, R. M.; Rembaum, A. (Inventor)

1983-01-01

The surface of a moderate band gap semiconductor such as p-type molybdenum sulfide is modified to contain an adherent film of charge mediating ionene polymer containing an electroactive unit such as bipyridimium. Electron transport between the electrode and the mediator film is favorable and photocorrosion and recombination processes are suppressed. Incorporation of particles of catalyst such as platinum within the film provides a reduction in overvoltage. The polymer film is readily deposited on the electrode surface and can be rendered stable by ionic or addition crosslinking. Catalyst can be predispersed in the polymer film or a salt can be impregnated into the film and reduced therein.

Electron-Transfer Kinetics of Redox Centers Anchored to Metal Surfaces: Weak- versus Strong-Overlap Reaction Pathways.

DTIC Science & Technology

1983-11-01

constants ket are presented for the one-electron electroreduction of various Co1]:I(NH3)5X complexes bound to mercury, platinum, and gold surfaces...electroreduction of various Co^^(NH𔃽)𔃿X complexes bound to mercury, platinum, and gold surfaces via either small inorganic or extended organic ligands X. t...platinum, gold , and copper, to enable values of ke* to be obtained for the one-electron reduction of the surface-Douna_redox center.2.3 These

The adsorption and dissociation of O2 on Pd and Pt modified TaC (1 0 0) surface: A first principles study

NASA Astrophysics Data System (ADS)

Meng, Yanan; Zhang, Xilin; Mao, Jianjun; Xu, Xiaopei; Yang, Zongxian

2018-05-01

The adsorption and dissociation of O2 on the palladium and platinum modified TaC (1 0 0) surfaces were investigated based on the density functional theory calculations. It is found that the adsorption sites of O2 are the Ta-Ta bridge sites on both the partially covered TaC (1 0 0) surfaces by Pd and Pt, M4/TaC (1 0 0) (M = Pd and Pt), while the 4-fold metal hollow sites and the metal-metal bridge sites are preferred on the fully covered TaC (1 0 0) surfaces by Pd and Pt monolayer, MML/TaC (1 0 0), respectively. The deposition of Pd or Pt can enhance the oxidation resistance of TaC (1 0 0). Meanwhile, the TaC (1 0 0) decorated by monolayer Pd still exhibited outstanding catalytic activity for O2 dissociation. Our study might be useful to designing efficient catalysts for the oxygen reduction reaction.

Chemistry and biological activity of platinum amidine complexes.

PubMed

Michelin, Rino A; Sgarbossa, Paolo; Sbovata, Silvia Mazzega; Gandin, Valentina; Marzano, Cristina; Bertani, Roberta

2011-07-04

Platinum amidine complexes represent a new class of potential antitumor drugs that contain the imino moiety HN=C(sp(2)) bonded to the platinum center. They can be related to the iminoether derivatives, which were recently shown to be the first Pt(II) compounds with a trans configuration endowed with anticancer activity. The chemical and biological properties of platinum amidine complexes, and more generally of platinum imino derivatives, can be rationally modified through suitable synthetic procedures with the aim of improving their cytotoxicity and antitumor activity. The addition of protic nucleophiles to nitriles coordinated to platinum in various oxidation states can offer a wide variety of complexes with chemical, structural, and physical properties specifically tuned for a more efficacious biological response. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fuel cell electrodes

DOEpatents

Strmcnik, Dusan; Cuesta, Angel; Stamenkovic, Vojislav; Markovic, Nenad

2015-06-23

A process includes patterning a surface of a platinum group metal-based electrode by contacting the electrode with an adsorbate to form a patterned platinum group metal-based electrode including platinum group metal sites blocked with adsorbate molecules and platinum group metal sites which are not blocked.

Biological role in the transformation of platinum-group mineral grains

NASA Astrophysics Data System (ADS)

Reith, Frank; Zammit, Carla M.; Shar, Sahar S.; Etschmann, Barbara; Bottrill, Ralph; Southam, Gordon; Ta, Christine; Kilburn, Matthew; Oberthür, Thomas; Ball, Andrew S.; Brugger, Joël

2016-04-01

Platinum-group elements are strategically important metals. Finding new deposits is becoming increasingly difficult owing to our limited understanding of the processes that affect their mobility in surface environments. Microorganisms have been shown to promote the mobility of metals around ore deposits. Here we show that microorganisms influence the mobility of platinum-group elements in mineral grains collected from Brazil, Australia and Colombia. Scanning electron microscopy showed biofilms covering the platinum-group mineral grains. The biofilms contained abundant platinum-group element nanoparticles and microcrystalline aggregates, and were dominated by Proteobacteria, many of which were closely related to known metal-resistant species. Some platinum-group mineral grains contained carbon, nitrogen, sulfur, selenium and iodine, suggesting the grains may be biogenic in origin. Molecular analyses show that Brazilian platinum-palladium grains hosted specific bacterial communities, which were different in composition from communities associated with gold grains, or communities in surrounding soils and sediments. Nano-phase metallic platinum accumulated when a metallophillic bacterium was incubated with a percolating platinum-containing medium, suggesting that biofilms can cause the precipitation of mobile platinum complexes. We conclude that biofilms are capable of forming or transforming platinum-group mineral grains, and may play an important role for platinum-group element dispersion and re-concentration in surface environments.

Remarkable NO oxidation on single supported platinum atoms

DOE PAGES

Narula, Chaitanya K.; Allard, Lawrence F.; Stocks, G. M.; ...

2014-11-28

Our first-principles density functional theoretical modeling suggests that NO oxidation is feasible on fully oxidized single θ-alumina-supported platinum atoms via a modified Langmuir-Hinshelwood pathway. This is in contrast to the known decrease in NO oxidation activity of supported platinum with decreasing Pt particle size believed to be due to increased platinum oxidation. In order to validate our theoretical study, we evaluated single θ-Al 2O 3-supported platinum atoms and found them to exhibit remarkable NO oxidation activity. A comparison of turnover frequencies (TOF) of single supported Pt atoms with those of platinum particles for NO oxidation shows that single supported Ptmore » atoms are as active as fully formed platinum particles. The overall picture of NO oxidation on supported Pt is that NO oxidation activity decreases with decreasing Pt particle size but accelerates when Pt is present only as single atoms.« less

Synthesis of platinum nanowire networks using a soft template.

PubMed

Song, Yujiang; Garcia, Robert M; Dorin, Rachel M; Wang, Haorong; Qiu, Yan; Coker, Eric N; Steen, William A; Miller, James E; Shelnutt, John A

2007-12-01

Platinum nanowire networks have been synthesized by chemical reduction of a platinum complex using sodium borohydride in the presence of a soft template formed by cetyltrimethylammonium bromide in a two-phase water-chloroform system. The interconnected polycrystalline nanowires possess the highest surface area (53 +/- 1 m2/g) and electroactive surface area (32.4 +/- 3.6 m2/g) reported for unsupported platinum nanomaterials; the high surface area results from the small average diameter of the nanowires (2.2 nm) and the 2-10 nm pores determined by nitrogen adsorption measurements. Synthetic control over the network was achieved simply by varying the stirring rate and reagent concentrations, in some cases leading to other types of nanostructures including wormlike platinum nanoparticles. Similarly, substitution of a palladium complex for platinum gives palladium nanowire networks. A mechanism of formation of the metal nanowire networks is proposed based on confined metal growth within a soft template consisting of a network of swollen inverse wormlike micelles.

Stabilizing platinum in phosphoric acid fuel cells

NASA Technical Reports Server (NTRS)

Remick, R. J.

1982-01-01

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

An Investigation of the Oxide Adhesion and Growth Characteristics on Platinum Modified Aluminide Coatings.

DTIC Science & Technology

1986-09-01

OfI STANDARITD N0 A S In 0 Lfl NAVAL POSTGRADUATE SCHOOL Monterey, California THESIS 49 o AN INVESTIGATION OF THE OXIDE ADHESION AND GROWTH...CHARACTERISTICS ON PLATINUM MODIFIED ALUMIINIDE COATINGS by Margaret Shannon Farrell September 1986 Thesis Advisor: P. H. Boone Approved for public release...COVERED 14 DATE OF REPORT (Year, Month. Day) 15 PAGE COLNT Mlaster’s Thesis FROM TO__ 1986 September 61 𔄀 5i-PALEV ENTARY NOTATION - COSATI CODES 18

Formation, Characteristics and Electrocatalytic Properties of Nanoporous Metals Formed by Dealloying of Ternary-Noble Alloys

NASA Astrophysics Data System (ADS)

Vega Zuniga, Adrian A.

Nanoporous metals formed by electrochemical dealloying of silver from Ag-Au-Pt alloys, with 77 at.% silver and platinum contents of 1, 2 and 3 at.%, have been studied. The presence of platinum, which is immobile relative to gold, refine the ligament size and stabilized the nanostructure against coarsening, even under experimental conditions that would be expected to promote coarsening (e.g., exposure to high temperature, longer dealloying times). By adding only 1 at.% Pt to the alloy precursor, the ligament/pore size was reduced by 50% with respect to that in nanoporous gold (NPG), which was formed on a Ag-Au alloy with the same silver content as ternary alloys. A further decrease in the ligament size was observed by increasing the platinum content of the precursor; however, most of the improvement occurred with 1 at.% Pt. The adsorbate-induced surface segregation of platinum was also investigated for these nanoporous metals. By exposing freshly-dealloyed nanostructures to moderate temperatures in the presence of air, platinum segregated to the ligament surface; in contrast, in an inert atmosphere (Ar-H 2), platinum mostly reverted to the bulk of the ligaments. This thermally activated process was thermodynamically driven by the interaction between platinum and oxygen; however, at the desorption temperature of oxygen, platinum de-segregated from the surface. Moreover, the co-segregation of platinum and oxygen hindered the thermal coarsening of the ligaments. Finally, the electrocatalytic abilities of these nanostructures were studied towards methanol and ethanol electro-oxidation, in alkaline and acidic media, showing significantly improved response in comparison to that observed in NPG. The synergistic effect between gold and platinum atoms and the smaller feature size of the nanostructures were directly associated with this behaviour. In alkaline electrolyte, the nanostructure formed on the alloy with 1 at.% Pt showed higher catalytic response than the other two ternary nanostructures, which could be associated with the platinum/gold ratio on the surface of the structure. In acidic electrolyte, the nanostructure with the highest platinum content displayed the highest electrocatalytic response. Furthermore, the presence of platinum changed the selectivity of both reactions: the concentrations of carbonate produced increased by increasing the platinum content in the alloy precursor.

Enhancement of catalytic activity of platinum-based nanoparticles towards electrooxidation of ethanol through interfacial modification with heteropolymolybdates

NASA Astrophysics Data System (ADS)

Barczuk, Piotr J.; Lewera, Adam; Miecznikowski, Krzysztof; Zurowski, Artur; Kulesza, Pawel J.

As evidenced from the increase of electrocatalytic currents measured under voltammetric and chronoamperometric conditions, the activity of bimetallic Pt-Ru and Pt-Sn nanoparticles towards oxidation of ethanol is increased by modification of their surfaces with ultra-thin films of phosphododecamolybdic acid (H 3PMo 12O 40). The enhancement effect has been most pronounced in a case of heteropolymolybdate-modified carbon-supported Pt-Sn catalysts. Independent high-resolution XPS measurements indicate the ability of heteropolymolybdates to stabilize tin (in bimetallic Pt-Sn particles) at higher oxidation states (presumably as tin oxo species). The overall activation effect may also be ascribed to changes in the morphology of catalytic films following modification with heteropolymolybdates. Presence of the polyoxometallate is also likely to increase of the interfacial population of reactive oxo groups in the vicinity of platinum centers.

Exploring the Efficacy of Platinum and Palladium Nanostructures for Organic Molecule Detection via Raman Spectroscopy

PubMed Central

Tran, Minh; Whale, Alison

2018-01-01

Noble transition metals, like palladium (Pd) and platinum (Pt), have been well-known for their excellent catalytic and electrochemical properties. However, they have been considered non-active for surface enhanced Raman spectroscopy (SERS). In this work, we explore the scattering contributions of Pd and Pt for the detection of organic molecules. The Pd and Pt nanostructures were synthesized on silicon substrate using a modified galvanic displacement method. The results show Pt nanoparticles and dendritic Pd nanostructures with controlled density and size. The influence of surfactants, including sodium dodecyl sulfate and cetyltrimethylammonium bromide, on the size and morphology of the nanostructures was investigated. The Pd and Pt nanostructures with a combination of large size and high density were then used to explore their applicability for the detection of 10−5 M Rhodamine 6G and 10−2 M paraoxon. PMID:29316659

Pt(110)(1×1) surfaces prepared by low temperature platinum deposition: surface characterization and stability

NASA Astrophysics Data System (ADS)

Alnot, M.; Ehrhardt, J. J.

1993-05-01

Adsorption of platinum atoms on Pt(110)(1×2) at low temperature has been studied by LEED, photoemission of adsorbed xenon (PAX) and Δφ measurements. Deposition of half a monolayer of platinum at 150 K produces a sharp (1×1) LEED pattern. A possible structural disorder of the as-grown surface is discussed. The (1×1) → (1×2) reconstruction is observed after annealing at a temperature slightly higher than 300 K.

Fuel blends: Enhanced electro-oxidation of formic acid in its blend with methanol at platinum nanoparticles modified glassy carbon electrodes

NASA Astrophysics Data System (ADS)

El-Deab, Mohamed S.; El-Nagar, Gumaa A.; Mohammad, Ahmad M.; El-Anadouli, Bahgat E.

2015-07-01

The current study addresses, for the first time, the enhanced direct electro-oxidation of formic acid (FA) at platinum-nanoparticles modified glassy carbon (nano-Pt/GC) electrode in the presence of methanol (MeOH) as a blending fuel. This enhancement is probed by: (i) the increase of the direct oxidation current of FA to CO2 (Ipd, dehydrogenation pathway), (ii) suppressing the dehydration pathway (Ipind, producing the poisoning intermediate CO) and (iii) a favorable negative shift of the onset potential of Ipd with increasing the mole fraction of MeOH in the blend. Furthermore, the charge of the direct FA oxidation in 0.3 M FA + 0.3 M MeOH blend is by 14 and 21times higher than that observed for 0.3 M FA and 0.3 M MeOH, respectively. MeOH is believed to adsorb at the Pt surface sites and thus disfavor the "non-faradaic" dissociation of FA (which produces the poisoning CO intermediate), i.e., MeOH induces a high CO tolerance of the Pt catalyst. The enhanced oxidation activity indicates that FA/MeOH blend is a promising fuel system.

Polyamidoamine dendrimers-assisted electrodeposition of gold-platinum bimetallic nanoflowers.

PubMed

Qian, Lei; Yang, Xiurong

2006-08-24

Novel Au-Pt bimetallic flower nanostructures fabricated on a polyamidoamine dendrimers-modified surface by electrodeposition are reported. These polyamidoamine dendrimers were stable, and they assisted the formation of Au-Pt bimetallic nanoflowers during the electrodeposition process. These nanoflowers were characterized by field-emitted scanning electron microscopy (FE-SEM), energy-dispersive spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), X-ray diffraction, and electrochemical methods. FE-SEM images showed that the bimetallic nanoflower included two parts: the "light" and the "pale" part. The two parts consisted of many small bimetallic nanoparticles, which was attributed to the progressive nucleation process. Moreover, the "light" part contained more bimetallic nanoparticles. The morphologies of bimetallic nanoflowers depended on the electrodeposition time and potential and the layer number of assembled dendrimers. The average size of nanoflowers increased with the increase in electrodeposition time. The layer number of assembled dendrimers obviously affected the size and morphologies of the "pale" parts of deposited nanoflowers. EDS and XPS indicated that the content of Au element was higher than that of Pt element in the nanoflowers. The bimetallic nanoflowers-modified electrode had electrochemical properties similar to those of bare gold and platinum electrodes. It also exhibited significant electrocatalytic activities toward oxygen reduction.

Study of the capacitance technique for measuring high-temperature blade tip clearance on ceramic rotors

NASA Technical Reports Server (NTRS)

Barranger, John P.

1993-01-01

Higher operating temperatures required for increased engine efficiency can be achieved by using ceramic materials for engine components. Ceramic turbine rotors are subject to the same limitations with regard to gas path efficiency as their superalloy predecessors. In this study, a modified frequency-modulation system is proposed for the measurement of blade tip clearance on ceramic rotors. It is expected to operate up to 1370 C (2500 F), the working temperature of present engines with ceramic turbine rotors. The design of the system addresses two special problems associated with nonmetallic blades: the capacitance is less than that of a metal blade and the effects of temperature may introduce uncertainty with regard to the blade tip material composition. To increase capacitance and stabilize the measurement, a small portion of the rotor is modified by the application of 5-micron-thick platinum films. The platinum surfaces on the probe electrodes and rotor that are exposed to the high-velocity gas stream are coated with an additional 10-micron-thick protective ceramic topcoat. A finite-element method is applied to calculate the capacitance as a function of clearance.

Preparation of low-sulfur platinum and platinum aluminide layers in thermal barrier coatings

NASA Technical Reports Server (NTRS)

Spitsberg, Irene T. (Inventor); Walston, William S. (Inventor); Schaeffer, Jon C. (Inventor)

2003-01-01

A method for preparing a coated nickel-base superalloy article reduces the sulfur content of the surface region of the metallic coating layers to low levels, thereby improving the adhesion of the coating layers to the article. The method includes depositing a first layer of platinum overlying the surface of a substrate, depositing a second layer of aluminum over the platinum, and final desulfurizing the article by heating the article to elevated temperature, preferably in hydrogen, and removing a small amount of material from the surface that was exposed during the step of heating. A ceramic layer may be deposited over the desulfurized article. The article may also be similarly desulfurized at other points in the fabrication procedure.

Evaluation of cellular influences of platinum nanoparticles by stable medium dispersion.

PubMed

Horie, Masanori; Kato, Haruhisa; Endoh, Shigehisa; Fujita, Katsuhide; Nishio, Keiko; Komaba, Lilian Kaede; Fukui, Hiroko; Nakamura, Ayako; Miyauchi, Arisa; Nakazato, Tetsuya; Kinugasa, Shinichi; Yoshida, Yasukazu; Hagihara, Yoshihisa; Morimoto, Yasuo; Iwahashi, Hitoshi

2011-11-01

Platinum nanoparticles have industrial application, for example in catalysis, and are used in consumer products such as cosmetics and supplements. Therefore, among the many nanoparticles, platinum is one of the more accessible nanoparticles for consumers. Most platinum nanoparticles that are used in cosmetics and supplements which have an anti-oxidant activity are modified particles. However, the cellular influences of pristine platinum nanoparticles are still unclear, although it has been reported that platinum nanoparticles induce oxidative stress. In this study, we investigated the cellular influences induced by pure pristine platinum nanoparticles. Platinum nanoparticles of 100% purity were dispersed in a cell culture medium and stable medium dispersion was obtained. The platinum nanoparticle medium dispersion was applied to two kinds of cultured cells, A549 and HaCaT cells, and the cellular influences were examined. Cell viability (MTT assay), cell proliferation (clonogenic assay), apoptosis induction (caspase-3 activity), intracellular ROS level (DCFH assay), and lipid peroxidation level (DPPP assay) were measured as markers of cellular influences. Transmission electron microscope observation showed cellular uptake of platinum nanoparticles. However, the platinum nanoparticles did not drive any markers. It is known that some metal oxide nanoparticles such as NiO and CuO show severe cytotoxicity via metal ion release. Compared with these toxic nanoparticles, the platinum nanoparticles used in this study did not release platinum ions into the culture media. These results suggest that the physically and chemically inactive cellular influences of platinum nanoparticles are small.

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.

Electrochemical Reconstitution of Biomolecules for Applications as Electrocatalysts for the Bionanofuel Cell

NASA Technical Reports Server (NTRS)

Kim, Jae-Woo; Choi, Sang H.; Lillehei, Peter T.; King, Glen C.; Watt, Gerald D.; Chu, Sang-Hyon; Park, Yeonjoon; Thibeault, Sheila

2004-01-01

Platinum-cored ferritins were synthesized as electrocatalysts by electrochemical biomineralization of immobilized apoferritin with platinum. The platinum cored ferritin was fabricated by exposing the immobilized apoferritin to platinum ions at a reduction potential. On the platinum-cored ferritin, oxygen is reduced to water with four protons and four electrons generated from the anode. The ferritin acts as a nano-scale template, a biocompatible cage, and a separator between the nanoparticles. This results in a smaller catalyst loading of the electrodes for fuel cells or other electrochemical devices. In addition, the catalytic activity of the ferritin-stabilized platinum nanoparticles is enhanced by the large surface area and particle size phenomena. The work presented herein details the immobilization of ferritin with various surface modifications, the electrochemical biomineralization of ferritin with different inorganic cores, and the fabrication of self-assembled 2-D arrays with thiolated ferritin.

A Novel Method for Depositing Precious Metal Films on Difficult Surfaces

NASA Technical Reports Server (NTRS)

Veitch, L. C.; Phillip, W. H.

1994-01-01

A guanidine-based vehicle was developed to deposit precious metal coatings on surfaces known to be difficult to coat. To demonstrate this method, a platinum coating was deposited on alumina fibers using a guanidine-platinum solution. X-ray diffraction confirmed that the only species present in the coating was platinum and that all of the carbon species had been removed upon heat treatment. SEM results showed that some porosity was present but that the coatings uniformly covered the fiber surface and adhered well to the finer.

Photoresponsive peptide azobenzene conjugates that specifically interact with platinum surfaces

NASA Astrophysics Data System (ADS)

Dinçer, S.; Tamerler, C.; Sarıkaya, M.; Pişkin, E.

2008-05-01

The aim of this study is to prepare photoresponsive peptide-azobenzene compounds which interacts with platinum surfaces specifically, in order to create smart surfaces for further novel applications in design of smart biosensors and array platforms. Here, a water-soluble azobenzene molecule, 4-hydroxyazo benzene,4-sulfonic acid was synthesized by diazo coupling reaction. A platinum-specific peptide, originally selected by a phage display technique was chemically synthesized/purchased, and conjugated with the azobenzene compound activated with carbonyldiimidazole. Both azobenzene and its conjugate were characterized (including photoresponsive properties) by FTIR, NMR, and UV-spectrophotometer. The yield of conjugation reaction estimated by ninhydrin assay was about 65%. Peptide incorporation did not restrict the light-sensitivity of azobenzene. Adsorption of both the peptide and its azobenzene conjugate was followed by Quartz Crystal Microbalance (QCM) system. The kinetic evaluations exhibited that both molecules interact platinum surfaces, quite rapidly and strongly.

Natural diatomite modified as novel hydrogen storage material

NASA Astrophysics Data System (ADS)

Jin, Jiao; Zheng, Chenghui; Yang, Huaming

2014-03-01

Natural diatomite, subjected to different modifications, is investigated for hydrogen adsorption capacities at room temperature. An effective metal-modified strategy is developed to disperse platinum (Pt) and palladium (Pd) nanoparticles on the surface of diatomite. Hydrogen adsorption capacity of pristine diatomite (diatomite) is 0.463 wt.% at 2.63 MPa and 298 K, among the highest of the known sorbents, while that of acid-thermally activated diatomite (A-diatomite) could reach up to 0.833 wt.% due to the appropriate pore properties by activation. By incorporation with a small amount of Pt and Pd ( 0.5 wt.%), hydrogen adsorption capacities are enhanced to 0.696 wt.% and 0.980 wt.%, respectively, indicating that activated diatomite shows interesting application in the field of hydrogen storage at room temperature.

Surface modification of platinum by laser-produced X-rays

NASA Astrophysics Data System (ADS)

Latif, Hamid; Shahid Rafique, M.; Khaleeq-ur-Rahaman, M.; Sattar, Abdul; Anjum, S.; Usman, A.; Zaheer, S.; Rawat, R. S.

2014-11-01

Laser-induced plasma is used as an X-ray source for the growth of hillocks like nanostructures on platinum surface. To generate X-rays, plasma is produced by Nd:YAG laser, which is operated at second harmonics (λ = 532 nm, E = 400 mJ). Analytical grade 5 N pure Al, Cu and W are used as laser targets for X-rays production. X-rays produced from Al, Cu and W plasmas are used to irradiate three analytical grade (5 N pure) platinum substrates, respectively, under the vacuum ∼10-4 torr. XRD analysis shows considerable structural changes in the exposed platinum. The decrement in reflection intensities, increment in dislocation line density, change in d-spacing and disturbance in the periodicity of planes evidently prove these structural changes. Atomic force microscope AFM topographic analysis of the platinum exposed to X-rays emitted from Al, Cu and W targets showed that nanometer-size hillocks are produced on the platinum surface irrespective of the source. It has also been observed that due to these hillocks, the roughness of the surface has increased. Conductivity of hillocks produced from X-rays produced by Al, Cu and W targets is compared and it is shown that the hillocks produced by Al target X-rays have better conductivity compared to the hillocks produced by X-rays from Cu and W targets.

Morphology controlled synthesis of platinum nanoparticles performed on the surface of graphene oxide using a gas-liquid interfacial reaction and its application for high-performance electrochemical sensing.

PubMed

Bai, Wushuang; Sheng, Qinglin; Zheng, Jianbin

2016-07-21

In this paper, we report a novel morphology-controlled synthetic method. Platinum (Pt) nanoparticles with three kinds of morphology (aggregation-like, cube-like and globular) were grown on the surface of graphene oxide (GO) using a simple gas-liquid interfacial reaction and Pt/GO nanocomposites were obtained successfully. According to the experimental results, the morphology of the Pt nanoparticles can be controlled by adjusting the reaction temperature with the protection of chitosan. The obtained Pt/GO nanocomposites were characterized using transmission electron microscopy (TEM), X-ray diffraction (XRD) and fourier transform infrared spectroscopy (FTIR). Then the Pt/GO nanocomposites with the three kinds of morphology were all used to fabricate electrochemical sensors. The electrochemical experimental results indicated that compared with various reported electrochemical sensors, the Pt/GO modified sensors in this work exhibit a low detection limit, high sensitivity and an extra wide linear range for the detection of nitrite. In addition, the synthesis of Pt particles based on a gas-liquid interfacial reaction provides a new platform for the controllable synthesis of nanomaterials.

Hydrogen peroxide sensing using ultrathin platinum-coated gold nanoparticles with core@shell structure.

PubMed

Li, Yongxin; Lu, Qiufang; Wu, Shengnan; Wang, Lun; Shi, Xianming

2013-03-15

Ultrathin platinum-coated gold (Pt@Au) nanoparticles with core@shell structure have been developed by under-potential deposition (UPD) redox replacement technique. A single UPD Cu replacement with Pt(2+) produced a uniform Pt monolayer on the surface of gold nanoparticles, which are immobilized on glassy carbon electrode (GCE) surface based on electrostatic interaction. The ultrathin Pt@Au nanoparticles were confirmed by cyclic voltammetry and X-ray photoelectron spectroscopy (XPS). Voltammetry and amperometric methodologies were used to evaluate the electrocatalytic activity of the Pt@Au nanoparticles modified electrode towards the reduction of hydrogen peroxide under the physiological condition. The present results show that ultrathin Pt coating greatly enhances the electrocatalytic activity towards the reduction of hydrogen peroxide, which can be utilized to fabricate the hydrogen peroxide sensor. Chronoamperometric experiments showed that at an applied potential of 0.08 V (vs. Ag/AgCl), the current reduction of hydrogen peroxide was linear to its concentration in the range of 1-450 μΜ, and the detection limit was found to be 0.18 μM (signal-to-noise ratio, S/N=3). Copyright © 2012 Elsevier B.V. All rights reserved.

SEM method for direct visual tracking of nanoscale morphological changes of platinum based electrocatalysts on fixed locations upon electrochemical or thermal treatments.

PubMed

Zorko, Milena; Jozinović, Barbara; Bele, Marjan; Hodnik, Nejc; Gaberšček, Miran

2014-05-01

A general method for tracking morphological surface changes on a nanometer scale with scanning electron microscopy (SEM) is introduced. We exemplify the usefulness of the method by showing consecutive SEM images of an identical location before and after the electrochemical and thermal treatments of platinum-based nanoparticles deposited on a high surface area carbon. Observations reveal an insight into platinum based catalyst degradation occurring during potential cycling treatment. The presence of chloride clearly increases the rate of degradation. At these conditions the dominant degradation mechanism seems to be the platinum dissolution with some subsequent redeposition on the top of the catalyst film. By contrast, at the temperature of 60°C, under potentiostatic conditions some carbon corrosion and particle aggregation was observed. Temperature treatment simulating the annealing step of the synthesis reveals sintering of small platinum based composite aggregates into uniform spherical particles. The method provides a direct proof of induced surface phenomena occurring on a chosen location without the usual statistical uncertainty in usual, random SEM observations across relatively large surface areas. Copyright © 2014 Elsevier B.V. All rights reserved.

Novel ferrocene-anchored ZnO nanoparticle/carbon nanotube assembly for glucose oxidase wiring: application to a glucose/air fuel cell.

PubMed

Haddad, Raoudha; Mattei, Jean-Gabriel; Thery, Jessica; Auger, Aurélien

2015-06-28

Glucose oxidase (GOx) is immobilized on ZnO nanoparticle-modified electrodes. The immobilized glucose oxidase shows efficient mediated electron transfer with ZnO nanoparticles to which the ferrocenyl moiety is π-stacked into a supramolecular architecture. The constructed ZnO-Fc/CNT modified electrode exhibits high ferrocene surface coverage, preventing any leakage of the π-stacked ferrocene from the newly described ZnO hybrid nanoparticles. The use of the new architecture of ZnO supported electron mediators to shuttle electrons from the redox centre of the enzyme to the surface of the working electrode can effectively bring about successful glucose oxidation. These modified electrodes evaluated as a highly efficient architecture provide a catalytic current for glucose oxidation and are integrated in a specially designed glucose/air fuel cell prototype using a conventional platinum-carbon (Pt/C) cathode at physiological pH (7.0). The obtained architecture leads to a peak power density of 53 μW cm(-2) at 300 mV for the Nafion® based biofuel cell under "air breathing" conditions at room temperature.

Encapsulation, controlled release, and antitumor efficacy of cisplatin delivered in liposomes composed of sterol-modified phospholipids

DOE PAGES

Kieler-Ferguson, Heidi M.; Chan, Darren; Sockolosky, Jonathan; ...

2017-03-03

Here, we employed a recently introduced class of sterol-modified lipids (SML) to produce m-PEG-DSPE containing liposome compositions with a range of cis-platinum content release rates. SML have a cholesterol succinate attached to the phosphatidylglycerol head group and a fatty acid at the 2 position. These compositions were compared to the well-studied liposome phospholipid compositions: mPEG-DSPE/Hydrogenated Soy PC/cholesterol or mPEG-DSPE/POPC/cholesterol to determine the effect of the cis-platinum release extent on C26 tumor proliferation in the BALB/c colon carcinoma mouse model. The release rates of cis-platinum from liposomes composed of SML are a function of the acyl chain length. SML-liposomes with shortermore » acyl chain lengths C-8 provided more rapid cisplatin release, lower in vitro IC50, and were easier to formulate compared to liposomes using traditional phospholipid compositions. Similar to other liposome cis-platinum formulations, the half-life of m-PEG-DSPE SML liposome cisplatin is substantially longer than the free drug. This resulted in a higher tumor cisplatin concentration at 48 h post-dosing compared to the free drug and higher Pt-DNA adducts in the tumor. Moreover, the maximum tolerated dose of the liposome formulations where up to four fold greater than the free drug. Using X-ray fluorescence spectroscopy on tumor sections, we compared the location of platinum, to the location of a fluorescence lipid incorporated in the liposomes. The liposome platinum co-localized with the fluorescent lipid and both were non-uniformly distributed in the tumor. Non-encapsulated Cis-platinum, albeit at a low concentration, was more uniformly distributed thorough the tumor. Three liposome formulations, including the well studied hydrogenated HSPC composition, had better antitumor activity in the murine colon 26 carcinoma model as compared to the free drug at the same dose but the SML liposome platinum formulations did not perform better than the HSPC formulation.« less

Encapsulation, controlled release, and antitumor efficacy of cisplatin delivered in liposomes composed of sterol-modified phospholipids

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

Kieler-Ferguson, Heidi M.; Chan, Darren; Sockolosky, Jonathan

Here, we employed a recently introduced class of sterol-modified lipids (SML) to produce m-PEG-DSPE containing liposome compositions with a range of cis-platinum content release rates. SML have a cholesterol succinate attached to the phosphatidylglycerol head group and a fatty acid at the 2 position. These compositions were compared to the well-studied liposome phospholipid compositions: mPEG-DSPE/Hydrogenated Soy PC/cholesterol or mPEG-DSPE/POPC/cholesterol to determine the effect of the cis-platinum release extent on C26 tumor proliferation in the BALB/c colon carcinoma mouse model. The release rates of cis-platinum from liposomes composed of SML are a function of the acyl chain length. SML-liposomes with shortermore » acyl chain lengths C-8 provided more rapid cisplatin release, lower in vitro IC50, and were easier to formulate compared to liposomes using traditional phospholipid compositions. Similar to other liposome cis-platinum formulations, the half-life of m-PEG-DSPE SML liposome cisplatin is substantially longer than the free drug. This resulted in a higher tumor cisplatin concentration at 48 h post-dosing compared to the free drug and higher Pt-DNA adducts in the tumor. Moreover, the maximum tolerated dose of the liposome formulations where up to four fold greater than the free drug. Using X-ray fluorescence spectroscopy on tumor sections, we compared the location of platinum, to the location of a fluorescence lipid incorporated in the liposomes. The liposome platinum co-localized with the fluorescent lipid and both were non-uniformly distributed in the tumor. Non-encapsulated Cis-platinum, albeit at a low concentration, was more uniformly distributed thorough the tumor. Three liposome formulations, including the well studied hydrogenated HSPC composition, had better antitumor activity in the murine colon 26 carcinoma model as compared to the free drug at the same dose but the SML liposome platinum formulations did not perform better than the HSPC formulation.« less

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

PubMed

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

2015-10-14

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

Electrochemical sensor based on molecularly imprinted membranes at platinum nanoparticles-modified electrode for determination of 17β-estradiol.

PubMed

Yuan, Lihua; Zhang, Jun; Zhou, Ping; Chen, Jiaxing; Wang, Ruoyu; Wen, Tingting; Li, Yun; Zhou, Xuemin; Jiang, Huijun

2011-11-15

In this paper, an electrochemical sensor for 17β-estradiol (E2) based on the molecular imprinting polymer (MIP) membranes had been constructed. 6-mercaptonicotinic acid (MNA) and E2 were first assembled on the surface of platinum nanoparticles-modified glassy carbon electrode (PtNPs/GCE) by the formation of Pt-S bonds and hydrogen-bonding interactions, and subsequently the polymer membranes were formed by electropolymerization. Finally, a novel molecularly imprinted sensor (MIS) was obtained after removal of E2. Experimental parameters such as deposition time, scan cycles, pH value and accumulation condition were optimized. Under optimal conditions, the MIS exhibited a large adsorption capacity and high selectivity. A good linearity was obtained in the range of 3.0×10(-8)-5.0×10(-5)molL(-1) (r=0.996) with an estimated detection limit of 1.6×10(-8)molL(-1). MIS had been successfully used to analyze E2 in water samples without complex pretreatment. Meanwhile, the average recoveries were higher than 93.9% with RSD<3.7%. All results above reveal that MIS is an effective electrochemical technique to determine E2 real-time in complicated matrix. Copyright © 2011 Elsevier B.V. All rights reserved.

Atomic layer deposition-based functionalization of materials for medical and environmental health applications

PubMed Central

Narayan, Roger J.; Adiga, Shashishekar P.; Pellin, Michael J.; Curtiss, Larry A.; Hryn, Alexander J.; Stafslien, Shane; Chisholm, Bret; Shih, Chun-Che; Shih, Chun-Ming; Lin, Shing-Jong; Su, Yea-Yang; Jin, Chunming; Zhang, Junping; Monteiro-Riviere, Nancy A.; Elam, Jeffrey W.

2010-01-01

Nanoporous alumina membranes exhibit high pore densities, well-controlled and uniform pore sizes, as well as straight pores. Owing to these unusual properties, nanoporous alumina membranes are currently being considered for use in implantable sensor membranes and water purification membranes. Atomic layer deposition is a thin-film growth process that may be used to modify the pore size in a nanoporous alumina membrane while retaining a narrow pore distribution. In addition, films deposited by means of atomic layer deposition may impart improved biological functionality to nanoporous alumina membranes. In this study, zinc oxide coatings and platinum coatings were deposited on nanoporous alumina membranes by means of atomic layer deposition. PEGylated nanoporous alumina membranes were prepared by self-assembly of 1-mercaptoundec-11-yl hexa(ethylene glycol) on platinum-coated nanoporous alumina membranes. The pores of the PEGylated nanoporous alumina membranes remained free of fouling after exposure to human platelet-rich plasma; protein adsorption, fibrin networks and platelet aggregation were not observed on the coated membrane surface. Zinc oxide-coated nanoporous alumina membranes demonstrated activity against two waterborne pathogens, Escherichia coli and Staphylococcus aureus. The results of this work indicate that nanoporous alumina membranes may be modified using atomic layer deposition for use in a variety of medical and environmental health applications. PMID:20308114

Characterization and bacterial anti-adherent effect on modified PMMA denture acrylic resin containing platinum nanoparticles

PubMed Central

2014-01-01

PURPOSE This study characterized the synthesis of a modified PMMA (Polymethyl methacrylate) denture acrylic loading platinum nanoparticles (PtN) and assessed its bacterial inhibitory efficacy to produce novel antimicrobial denture base material. MATERIALS AND METHODS Polymerized PMMA denture acrylic disc (20 mm × 2 mm) specimens containing 0 (control), 10, 50, 100 and 200 mg/L of PtN were fabricated respectively. The obtained platinum-PMMA nanocomposite (PtNC) was characterized by TEM (transmission electron microscopy), SEM/EDX (scanning electron microscope/energy dispersive X-ray spectroscopy), thermogravimetric and atomic absorption spectrophotometer analysis. In antimicrobial assay, specimens were placed on the cell culture plate, and 100 µL of microbial suspensions of S. mutans (Streptococcus mutans) and S. sobrinus (Streptococcus sobrinus) were inoculated then incubated at 37℃ for 24 hours. The bacterial attachment was tested by FACS (fluorescence-activated cell sorting) analysis after staining with fluorescent probe. RESULTS PtN were successfully loaded and uniformly immobilized into PMMA denture acrylic with a proper thermal stability and similar surface morphology as compared to control. PtNC expressed significant bacterial anti-adherent effect rather than bactericidal effect above 50 mg/L PtN loaded when compared to pristine PMMA (P=.01) with no or extremely small amounts of Pt ion eluted. CONCLUSION This is the first report on the synthesis and its antibacterial activity of Pt-PMMA nanocomposite. PMMA denture acrylic loading PtN could be a possible intrinsic antimicrobial denture material with proper mechanical characteristics, meeting those specified for denture bases. For clinical application, future studies including biocompatibility, color stability and warranting the long-term effect were still required. PMID:25006385

Highly sensitive and rapid detection of acetylcholine using an ITO plate modified with platinum-graphene nanoparticles.

PubMed

Chauhan, Nidhi; Narang, Jagriti; Jain, Utkarsh

2015-03-21

Determining the concentrations of acetylcholine (ACh) and choline (Ch) is clinically important. ACh is a neurotransmitter that acts as a key link in the communication between neurons in the spinal cord and in nerve skeletal junctions in vertebrates, and plays an important role in transmitting signals in the brain. A bienzymatic sensor for the detection of ACh was prepared by co-immobilizing choline oxidase (ChO) and acetylcholinesterase (AChE) on graphene matrix/platinum nanoparticles, and then electrodepositing them on an ITO-coated glass plate. Graphene nanoparticles were decorated with platinum nanoparticles and were electrodeposited on a modified ITO-coated glass plate to form a modified electrode. The modified electrode was characterized by scanning electron microscopy (SEM), cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) studies. The optimum response of the enzyme electrode was obtained at pH 7.0 and 35 °C. The response time of this ACh-sensing system was shown to be 4 s. The linear range of responses to ACh was 0.005-700 μM. This biosensor exhibits excellent anti-interferential abilities and good stability, retaining 50% of its original current even after 4 months. It has been applied for the detection of ACh levels in human serum samples.

Thin film temperature sensor

NASA Technical Reports Server (NTRS)

Grant, H. P.; Przybyszewski, J. S.

1980-01-01

Thin film surface temperature sensors were developed. The sensors were made of platinum-platinum/10 percent rhodium thermocouples with associated thin film-to-lead wire connections and sputtered on aluminum oxide coated simulated turbine blades for testing. Tests included exposure to vibration, low velocity hydrocarbon hot gas flow to 1250 K, and furnace calibrations. Thermal electromotive force was typically two percent below standard type S thermocouples. Mean time to failure was 42 hours at a hot gas flow temperature of 1250 K and an average of 15 cycles to room temperature. Failures were mainly due to separation of the platinum thin film from the aluminum oxide surface. Several techniques to improve the adhesion of the platinum are discussed.

Mesoporous Aluminosilicate Catalysts for the Selective Isomerization of n-Hexane: The Roles of Surface Acidity and Platinum Metal.

PubMed

Musselwhite, Nathan; Na, Kyungsu; Sabyrov, Kairat; Alayoglu, Selim; Somorjai, Gabor A

2015-08-19

Several types of mesoporous aluminosilicates were synthesized and evaluated in the catalytic isomerization of n-hexane, both with and without Pt nanoparticles loaded into the mesopores. The materials investigated included mesoporous MFI and BEA type zeolites, MCF-17 mesoporous silica, and an aluminum modified MCF-17. The acidity of the materials was investigated through pyridine adsorption and Fourier Transform-Infrared Spectroscopy (FT-IR). It was found that the strong Brönsted acid sites in the micropores of the zeolite catalysts facilitated the cracking of hexane. However, the medium strength acid sites on the Al modified MCF-17 mesoporous silica greatly enhanced the isomerization reaction. Through the loading of different amounts of Pt into the mesopores of the Al modified MCF-17, the relationship between the metal nanoparticles and acidic sites on the support was revealed.

Intermediate stages of electrochemical oxidation of single-crystalline platinum revealed by in situ Raman spectroscopy

PubMed Central

Huang, Yi-Fan; Kooyman, Patricia J.; Koper, Marc T. M.

2016-01-01

Understanding the atomistic details of how platinum surfaces are oxidized under electrochemical conditions is of importance for many electrochemical devices such as fuel cells and electrolysers. Here we use in situ shell-isolated nanoparticle-enhanced Raman spectroscopy to identify the intermediate stages of the electrochemical oxidation of Pt(111) and Pt(100) single crystals in perchloric acid. Density functional theory calculations were carried out to assist in assigning the experimental Raman bands by simulating the vibrational frequencies of possible intermediates and products. The perchlorate anion is suggested to interact with hydroxyl phase formed on the surface. Peroxo-like and superoxo-like two-dimensional (2D) surface oxides and amorphous 3D α-PtO2 are sequentially formed during the anodic polarization. Our measurements elucidate the process of the electrochemical oxidation of platinum single crystals by providing evidence for the structure-sensitive formation of a 2D platinum-(su)peroxide phase. These results may contribute towards a fundamental understanding of the mechanism of degradation of platinum electrocatalysts. PMID:27514695

Platinum and rhenium extraction from a spent refinery catalyst using Bacillus megaterium as a cyanogenic bacterium: statistical modeling and process optimization.

PubMed

Motaghed, M; Mousavi, S M; Rastegar, S O; Shojaosadati, S A

2014-11-01

The present study evaluated the potential of Bacillus megaterium as a cyanogenic bacterium to produce cyanide for solubilization of platinum and rhenium from a spent refinery catalyst. Response surface methodology was applied to study the effects and interaction between two main effective parameters including initial glycine concentration and pulp density. Maximum Pt and Re recovery was obtained 15.7% and 98%, respectively, under optimum conditions of 12.8 g/l initial glycine concentration and 4% (w/v) pulp density after 7 days. Increasing the free cyanide concentration to 3.6 mg/l, varying the pH from 6.7 to 9, and increasing the dissolved oxygen from 2 to 5mg/l demonstrated the growth characteristics of B. megaterium during bioleaching process. The modified shrinking core model was used to determine the rate limiting step of the process. It was found that diffusion through the product layer is the rate controlling step. Copyright © 2014 Elsevier Ltd. All rights reserved.

Environmental and biological monitoring of platinum-containing drugs in two hospital pharmacies using positive air pressure isolators.

PubMed

Kopp, Bettina; Crauste-Manciet, Sylvie; Guibert, Agnès; Mourier, Wilhelmine; Guerrault-Moro, Marie-Noelle; Ferrari, Sylvie; Jomier, Jean-Yves; Brossard, Denis; Schierl, Rudolf

2013-04-01

Environmental and biological monitoring of platinum containing drugs was implemented in two French hospital pharmacies using positive air pressure isolators and having similar working procedures when preparing antineoplastic drugs. Wipe sampling of surfaces, gloves, and vials was performed in the preparation room and in storage areas. All employees involved in the preparation of antineoplastic drugs were tested for urinary platinum on Monday before work and Friday after shift. Only traces of platinum were detected on surfaces in the preparation room outside the isolators (less than 1.61 pg cm(-2)). However, in one center, significant contamination was found in the storage area of the drug vials, which can most likely be linked to the rupture of a platinum vial and due to inefficient cleaning procedures. Surfaces inside the isolators were found to be contaminated (maximum: 198.4 pg cm(-2)). A higher level of contamination was detected in one pharmacy and could be explained by the lack of overgloving with regular changes during the preparation process. Nitrile gloves used during drug handling outside the isolator showed the highest platinum concentration (maximum: 5.86 ng per pair). With regards to platinum urine concentration, no significant difference was found between exposed and unexposed pharmacy personnel. Isolator technology combined with individual protective measures seems to be efficient to protect workers from occupational exposure to antineoplastic drugs, whereas specific individual protective procedures implemented were focussing on the risk of handling vials outside the isolator (e.g. high frequency of glove changing). Moreover, overgloving inside the isolator would contribute to substantially decrease inner surface contamination and should be recommended in order to limit the transfer of chemical contamination to the end products.

Improved Electrochemical Detection of Zinc Ions Using Electrode Modified with Electrochemically Reduced Graphene Oxide

PubMed Central

Kudr, Jiri; Richtera, Lukas; Nejdl, Lukas; Xhaxhiu, Kledi; Vitek, Petr; Rutkay-Nedecky, Branislav; Hynek, David; Kopel, Pavel; Adam, Vojtech; Kizek, Rene

2016-01-01

Increasing urbanization and industrialization lead to the release of metals into the biosphere, which has become a serious issue for public health. In this paper, the direct electrochemical reduction of zinc ions is studied using electrochemically reduced graphene oxide (ERGO) modified glassy carbon electrode (GCE). The graphene oxide (GO) was fabricated using modified Hummers method and was electrochemically reduced on the surface of GCE by performing cyclic voltammograms from 0 to −1.5 V. The modification was optimized and properties of electrodes were determined using electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). The determination of Zn(II) was performed using differential pulse voltammetry technique, platinum wire as a counter electrode, and Ag/AgCl/3 M KCl reference electrode. Compared to the bare GCE the modified GCE/ERGO shows three times better electrocatalytic activity towards zinc ions, with an increase of reduction current along with a negative shift of reduction potential. Using GCE/ERGO detection limit 5 ng·mL−1 was obtained. PMID:28787832

Silver Nanoparticle Modified Electrode Covered by Graphene Oxide for the Enhanced Electrochemical Detection of Dopamine

PubMed Central

Shin, Jae-Wook; Kim, Kyeong-Jun; Yoon, Jinho; Jo, Jinhee; El-Said, Waleed Ahmed; Choi, Jeong-Woo

2017-01-01

Several neurological disorders such as Alzheimer’s disease and Parkinson’s disease have become a serious impediment to aging people nowadays. One of the efficient methods used to monitor these neurological disorders is the detection of neurotransmitters such as dopamine. Metal materials, such as gold and platinum, are widely used in this electrochemical detection method; however, low sensitivity and linearity at low dopamine concentrations limit the use of these materials. To overcome these limitations, a silver nanoparticle (SNP) modified electrode covered by graphene oxide for the detection of dopamine was newly developed in this study. For the first time, the surface of an indium tin oxide (ITO) electrode was modified using SNPs and graphene oxide sequentially through the electrochemical deposition method. The developed biosensor provided electrochemical signal enhancement at low dopamine concentrations in comparison with previous biosensors. Therefore, our newly developed SNP modified electrode covered by graphene oxide can be used to monitor neurological diseases through electrochemical signal enhancement at low dopamine concentrations. PMID:29186040

Silver Nanoparticle Modified Electrode Covered by Graphene Oxide for the Enhanced Electrochemical Detection of Dopamine.

PubMed

Shin, Jae-Wook; Kim, Kyeong-Jun; Yoon, Jinho; Jo, Jinhee; El-Said, Waleed Ahmed; Choi, Jeong-Woo

2017-11-29

Several neurological disorders such as Alzheimer's disease and Parkinson's disease have become a serious impediment to aging people nowadays. One of the efficient methods used to monitor these neurological disorders is the detection of neurotransmitters such as dopamine. Metal materials, such as gold and platinum, are widely used in this electrochemical detection method; however, low sensitivity and linearity at low dopamine concentrations limit the use of these materials. To overcome these limitations, a silver nanoparticle (SNP) modified electrode covered by graphene oxide for the detection of dopamine was newly developed in this study. For the first time, the surface of an indium tin oxide (ITO) electrode was modified using SNPs and graphene oxide sequentially through the electrochemical deposition method. The developed biosensor provided electrochemical signal enhancement at low dopamine concentrations in comparison with previous biosensors. Therefore, our newly developed SNP modified electrode covered by graphene oxide can be used to monitor neurological diseases through electrochemical signal enhancement at low dopamine concentrations.

Friction behavior of members of the platinum metals group with gold

NASA Technical Reports Server (NTRS)

Buckley, D. H.

1975-01-01

The adhesion and friction behavior of the platinum metals group was examined with clean surfaces and surfaces selectively contaminated with oxygen, vinyl chloride (C2H3Cl), and methyl mercaptan (CH3SH). A pin or disk specimen configuration was used with the pin being a single crystal of gold of the (111) orientation and with the platinum metal disks also being single crystals of the (111) or (0001) orientation. Loads applied ranged from 1 to 10 g and a sliding velocity of 0.7 mm/min was employed. Results indicate adhesion and transfer of gold to all of the platinum metals. Despite this observation friction differences existed among the metals in the group. These differences are related to surface chemical activity. Adsorption of various friction reducing species was selective. With some adsorbates present strong adhesive forces between metals were still observed.

Alkali metal-refractory metal biphase electrode for AMTEC

NASA Technical Reports Server (NTRS)

Williams, Roger M. (Inventor); Bankston, Clyde P. (Inventor); Cole, Terry (Inventor); Khanna, Satish K. (Inventor); Jeffries-Nakamura, Barbara (Inventor); Wheeler, Bob L. (Inventor)

1989-01-01

An electrode having increased output with slower degradation is formed of a film applied to a beta-alumina solid electrolyte (BASE). The film comprises a refractory first metal M.sup.1 such as a platinum group metal, suitably platinum or rhodium, capable of forming a liquid or a strong surface adsorption phase with sodium at the operating temperature of an alkali metal thermoelectric converter (AMTEC) and a second refractory metal insoluble in sodium or the NaM.sup.1 liquid phase such as a Group IVB, VB or VIB metal, suitably tungsten, molybdenum, tantalum or niobium. The liquid phase or surface film provides fast transport through the electrode while the insoluble refractory metal provides a structural matrix for the electrode during operation. A trilayer structure that is stable and not subject to deadhesion comprises a first, thin layer of tungsten, an intermediate co-deposited layer of tungsten-platinum and a thin surface layer of platinum.

Green synthesis of platinum nanoparticles that induce cell death and G2/M-phase cell cycle arrest in human cervical cancer cells.

PubMed

Alshatwi, Ali A; Athinarayanan, Jegan; Vaiyapuri Subbarayan, Periasamy

2015-01-01

Platinum-based chemotherapeutic drugs, including cisplatin, carboplatin, and oxaliplatin, have been used to manage cancer in spite of dose-dependent side effects, including nephrotoxicity, neurotoxicity and ototoxicity. These disadvantages have prompted the development of new strategies for cancer therapy that utilize functionalized nanoparticles as nanomedicines. In the present investigation, we have synthesized platinum nanoparticles using tea polyphenol (TPP) as both a reducing and surface modifying agent. The crystalline nature and morphology of the prepared TPP-functionalized platinum nanoparticles (TPP@Pt) were analyzed using X-ray diffraction (XRD) and transmission electron microscopy (TEM). The XRD results revealed that the TPP@Pt had a crystalline nature with a face-centered cubic structure. TEM imaging suggested that the TTP@Pt are flower shaped with a well-dispersed 30-60 nm-sized TPP@Pt formation. Cervical cancer cells (SiHa) were then treated with different concentrations of TPP@Pt. The effects of TPP@Pt on cell viability, nuclear morphology and cell cycle distribution were investigated. A cell viability assay revealed that the proliferation of SiHa cells was inhibited by TPP@Pt. Propidium iodide nuclear staining indicated that TPP@Pt induced nuclear fragmentation and chromatin condensation. Treatment with TPP@Pt significantly increased the percentage of cells in the G2/M phase, which indicates induced cell cycle arrest in the G2/M phase and an increased number of cells in the subG0 cell death phase. These findings highlight a potential use of TPP@Pt in cervical cancer treatment.

Effect of the Platinum Electroplated Layer Thickness on the Coatings' Microstructure

NASA Astrophysics Data System (ADS)

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

2017-03-01

CMSX 4 and Inconel 625 superalloys were coated by platinum layers (3 and 7 μm thick) in the electroplating process. The heat treatment of platinum layers (at 1,050 ˚C for 2 h) was performed to increase platinum adherence to the superalloys substrate. The diffusion zone obtained on CMSX 4 superalloy (3 and 7 μm platinum thick before heat treatment) consisted of two phases: γ-Ni(Al, Cr) and (Al0.25Pt0.75)Ni3. The diffusion zone obtained on Inconel 625 superalloy (3 μm platinum thick before heat treatment) consisted of the α-Pt(Ni, Cr, Al) phase. Moreover, γ-Ni(Cr, Al) phase was identified. The X-ray diffraction (XRD) results revealed the presence of platinum in the diffusion zone of the heat-treated coating (7 μm platinum thick) on Inconel 625 superalloy. The surface roughness parameter Ra of heat-treated coatings increased with the increase of platinum layers thickness. This was due to the unequal mass flow of platinum and nickel.

Phosphorus adlayers on Platinum (110)

NASA Astrophysics Data System (ADS)

Heikkinen, Olli; Riihimäki, Ari; Sainio, Jani; Lahtinen, Jouko

2017-10-01

Platinum is a metal utilized in many applications. Its catalytic activity can be decreased due to chemical poisoning caused e.g. by phosphorus. To gain more understanding of its poisoning, we present a study of phosphorus adsorption on a platinum (110) single crystal surface. Using X-ray photoelectron spectroscopy, we have found that the adsorbate coverage saturates at around 3 monolayers. Annealing the phosphorus-covered platinum surface at 750 °C gives rise to three different ordered adlayer structures, with symmetries of 2 × 3, 11 × 4 and √{ 2} × 1 , from the lowest to the highest coverage, detected with low-energy electron diffraction. We have studied the sample topography with scanning tunnelling microscopy. We also present a tentative model for the observed structures and their evolution.

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

NASA Astrophysics Data System (ADS)

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

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

Role of bonding mechanisms during transfer hydrogenation reaction on heterogeneous catalysts of platinum nanoparticles supported on zinc oxide nanorods

NASA Astrophysics Data System (ADS)

Al-Alawi, Reem A.; Laxman, Karthik; Dastgir, Sarim; Dutta, Joydeep

2016-07-01

For supported heterogeneous catalysis, the interface between a metal nanoparticle and the support plays an important role. In this work the dependency of the catalytic efficiency on the bonding chemistry of platinum nanoparticles supported on zinc oxide (ZnO) nanorods is studied. Platinum nanoparticles were deposited on ZnO nanorods (ZnO NR) using thermal and photochemical processes and the effects on the size, distribution, density and chemical state of the metal nanoparticles upon the catalytic activities are presented. The obtained results indicate that the bonding at Pt-ZnO interface depends on the deposition scheme which can be utilized to modulate the surface chemistry and thus the activity of the supported catalysts. Additionally, uniform distribution of metal on the catalyst support was observed to be more important than the loading density. It is also found that oxidized platinum Pt(IV) (platinum hydroxide) provided a more suitable surface for enhancing the transfer hydrogenation reaction of cyclohexanone with isopropanol compared to zero valent platinum. Photochemically synthesized ZnO supported nanocatalysts were efficient and potentially viable for upscaling to industrial applications.

Surface Plasmon Resonance Evaluation of Colloidal Metal Aerogel Filters

NASA Technical Reports Server (NTRS)

Smith, David D.; Sibille, Laurent; Cronise, Raymond J.; Noever, David A.

1997-01-01

We have fabricated aerogels containing gold, silver, and platinum nanoparticles for gas catalysis applications. By applying the concept of an average or effective dielectric constant to the heterogeneous interlayer surrounding each particle, we extend the technique of immersion spectroscopy to porous or heterogeneous media. Specifically, we apply the predominant effective medium theories for the determination of the average fractional composition of each component in this inhomogeneous layer. Hence, the surface area of metal available for catalytic gas reaction is determined. The technique is satisfactory for statistically random metal particle distributions but needs further modification for aggregated or surfactant modified systems. Additionally, the kinetics suggest that collective particle interactions in coagulated clusters are perturbed during silica gelation resulting in a change in the aggregate geometry.

X-ray photoemission analysis of clean and carbon monoxide-chemisorbed platinum(111) stepped surfaces using a curved crystal

DOE PAGES

Walter, Andrew L.; Schiller, Frederik; Corso, Martina; ...

2015-11-12

Surface chemistry and catalysis studies could significantly gain from the systematic variation of surface active sites, tested under the very same conditions. Curved crystals are excellent platforms to perform such systematics, which may in turn allow to better resolve fundamental properties and reveal new phenomena. This is demonstrated here for the carbon monoxide/platinum system. We curve a platinum crystal around the high-symmetry (111) direction and carry out photoemission scans on top. This renders the spatial core-level imaging of carbon monoxide adsorbed on a 'tunable' vicinal surface, allowing a straightforward visualization of the rich chemisorption phenomenology at steps and terraces. Throughmore » such photoemission images we probe a characteristic elastic strain variation at stepped surfaces, and unveil subtle stress-release effects on clean and covered vicinal surfaces. Lastly, these results offer the prospect of applying the curved surface approach to rationally investigate the chemical activity of surfaces under real pressure conditions.« less

X-ray photoemission analysis of clean and carbon monoxide-chemisorbed platinum(111) stepped surfaces using a curved crystal

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

Walter, Andrew L.; Schiller, Frederik; Corso, Martina

Surface chemistry and catalysis studies could significantly gain from the systematic variation of surface active sites, tested under the very same conditions. Curved crystals are excellent platforms to perform such systematics, which may in turn allow to better resolve fundamental properties and reveal new phenomena. This is demonstrated here for the carbon monoxide/platinum system. We curve a platinum crystal around the high-symmetry (111) direction and carry out photoemission scans on top. This renders the spatial core-level imaging of carbon monoxide adsorbed on a 'tunable' vicinal surface, allowing a straightforward visualization of the rich chemisorption phenomenology at steps and terraces. Throughmore » such photoemission images we probe a characteristic elastic strain variation at stepped surfaces, and unveil subtle stress-release effects on clean and covered vicinal surfaces. Lastly, these results offer the prospect of applying the curved surface approach to rationally investigate the chemical activity of surfaces under real pressure conditions.« less

Theoretical Study of the Structure, Stability and Oxygen Reduction Activity of Ultrathin Platinum Nanowires

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

Matanovic, Ivana; Kent, Paul; Garzon, Fernando

2012-10-10

We use density functional theory to study the difference in the structure, stability and catalytic reactivity between ultrathin, 0.5- 1.0 nm diameter, platinum nanotubes and nanowires. Model nanowires were formed by inserting an inner chain of platinum atoms in small diameter nanotubes. In this way more stable, nonhollow structures were formed. The difference in the electronic structure of platinum nanotubes and nanowires was examined by inspecting the density of surface states and band structure. Furthermore, reactivity towards the oxygen reduction reaction of platinum nanowires was addressed by studying the change in the chemisorption energies of oxygen and hydroxyl groups, inducedmore » by inserting the inner chain of platinum atoms into the hollow nanotubes. Both ultrathin platinum nanotubes and nanowires show distinct properties compared to bulk platinum. Nanotubes with diameters larger than 1 nm show promise for use as oxygen reduction catalysts.« less

Density Functional Study of the Structure, Stability and Oxygen Reduction Activity of Ultrathin Platinum Nanowires

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

Matanovic, Ivana; Kent, Paul; Garzon, Fernando

2013-03-14

We used density functional theory to study the difference in the structure, stability and catalytic reactivity between ultrathin, 0.5–1.0 nm diameter, platinum nanotubes and nanowires. Model nanowires were formed by inserting an inner chain of platinum atoms in small diameter nanotubes. In this way more stable, non-hollow structures were formed. The difference in the electronic structure of platinum nanotubes and nanowires was examined by inspecting the density of surface states and band structure. Furthermore, reactivity toward the oxygen reduction reaction of platinum nanowires was assessed by studying the change in the chemisorption energies of oxygen, hydroxyl, and hydroperoxyl groups, inducedmore » by converting the nanotube models to nanowires. Both ultrathin platinum nanotubes and nanowires show distinct properties compared to bulk platinum. Single-wall nanotubes and platinum nanowires with diameters larger than 1 nm show promise for use as oxygen reduction catalysts.« less

Facile Preparation of a Platinum Silicide Nanoparticle-Modified Tip Apex for Scanning Kelvin Probe Microscopy.

PubMed

Lin, Chun-Ting; Chen, Yu-Wei; Su, James; Wu, Chien-Ting; Hsiao, Chien-Nan; Shiao, Ming-Hua; Chang, Mao-Nan

2015-12-01

In this study, we propose an ultra-facile approach to prepare a platinum silicide nanoparticle-modified tip apex (PSM tip) used for scanning Kelvin probe microscopy (SKPM). We combined a localized fluoride-assisted galvanic replacement reaction (LFAGRR) and atmospheric microwave annealing (AMA) to deposit a single platinum silicide nanoparticle with a diameter of 32 nm on the apex of a bare silicon tip of atomic force microscopy (AFM). The total process was completed in an ambient environment in less than 3 min. The improved potential resolution in the SKPM measurement was verified. Moreover, the resolution of the topography is comparable to that of a bare silicon tip. In addition, the negative charges found on the PSM tips suggest the possibility of exploring the use of current PSM tips to sense electric fields more precisely. The ultra-fast and cost-effective preparation of the PSM tips provides a new direction for the preparation of functional tips for scanning probe microscopy.

Investigation of interaction between the Pt(II) ions and aminosilane-modified silica surface in heterogeneous system

NASA Astrophysics Data System (ADS)

Nowicki, Waldemar; Gąsowska, Anna; Kirszensztejn, Piotr

2016-05-01

UV-vis spectroscopy measurements confirmed the reaction in heterogeneous system between Pt(II) ions and ethylenediamine type ligand, n-(2-aminoethyl)-3-aminopropyl-trimethoxysilane, immobilized at the silica surface. The formation of complexes is a consequence of interaction between the amine groups from the ligand grafted onto SiO2 and ions of platinum. A potentiometric titration technique was to determine the stability constants of complexes of Pt(II) with immobilized insoluble ligand (SG-L), on the silica gel. The results show the formation of three surface complexes of the same type (PtHSG-L, Pt(HSG-L)2, PtSG-L) with SG-L ligand, in a wide range of pH for different Debye length. The concentration distribution of the complexes in a heterogeneous system is evaluated.

Construction of an electrochemical sensor based on the electrodeposition of Au-Pt nanoparticles mixtures on multi-walled carbon nanotubes film for voltammetric determination of cefotaxime.

PubMed

Shahrokhian, Saeed; Rastgar, Shokoufeh

2012-06-07

Mixtures of gold-platinum nanoparticles (Au-PtNPs) are fabricated consecutively on a multi-walled carbon nanotubes (MWNT) coated glassy carbon electrode (GCE) by the electrodeposition method. The surface morphology and nature of the hybrid film (Au-PtNPs/MWCNT) deposited on glassy carbon electrodes is characterized by scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD), electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) techniques. The modified electrode is used as a new and sensitive electrochemical sensor for the voltammetric determination of cefotaxime (CFX). The electrochemical behavior of CFX is investigated on the surface of the modified electrode using linear sweep voltammetry (LSV). The results of voltammetric studies exhibited a considerable improvement in the oxidation peak current of CFX compared to glassy carbon electrodes individually coated with MWCNT or Au-PtNPs. Under the optimized conditions, the modified electrode showed a wide linear dynamic range of 0.004-10.0 μM with a detection limit of 1.0 nM for the voltammetric determination of CFX. The modified electrode was successfully applied for the accurate determination of trace amounts of CFX in pharmaceutical and clinical preparations.

Thermally stable single-atom platinum-on-ceria catalysts via atom trapping

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

Jones, John; Xiong, Haifeng; DelaRiva, Andrew

2016-07-08

Catalysts based on single atoms of scarce precious metals can lead to more efficient use through enhanced reactivity and selectivity. However, single atoms on catalyst supports can be mobile and aggregate into nanoparticles when heated at elevated temperatures. High temperatures are detrimental to catalyst performance unless these mobile atoms can be trapped. We used ceria powders having similar surface areas but different exposed surface facets. When mixed with a platinum/ aluminum oxide catalyst and aged in air at 800°C, the platinum transferred to the ceria and was trapped. Polyhedral ceria and nanorods were more effective than ceria cubes at anchoringmore » the platinum. Performing synthesis at high temperatures ensures that only the most stable binding sites are occupied, yielding a sinter-resistant, atomically dispersed catalyst.« less

Identification of the formation of metal-vinylidene interfacial bonds of alkyne-capped platinum nanoparticles by isotopic labeling.

PubMed

Hu, Peiguang; Chen, Limei; Deming, Christopher P; Bonny, Lewis W; Lee, Hsiau-Wei; Chen, Shaowei

2016-10-07

Stable platinum nanoparticles were prepared by the self-assembly of 1-dodecyne and dodec-1-deuteroyne onto bare platinum colloid surfaces. The nanoparticles exhibited consistent core size and optical properties. FTIR and NMR measurements confirmed the formation of Pt-vinylidene (Pt[double bond, length as m-dash]C[double bond, length as m-dash]CH-) interfacial linkages rather than Pt-acetylide (Pt-C[triple bond, length as m-dash]C-) and platinum-hydride (Pt-H) bonds.

Effect of Surface Preparation and Gas Flow on Nitrogen Atom Surface Recombination

NASA Technical Reports Server (NTRS)

Prok, George M.

1961-01-01

The effects of surface preparation and gas flow on the recombination of nitrogen atoms at copper and platinum surfaces were determined. Atoms were generated by an electrodeless 2450-megacycle-per-second discharge, and their concentration was measured by gas-phase titration with nitric oxide. Test surfaces were either vacuum-evaporated films or spheres machined from bulk metal and cemented around small glass-bead thermistors. Heat released by recombination was measured as the difference in electrical energy required to maintain a given thermistor temperature with and without a catalytic surface exposed. Recombination coefficients measured at flow velocities of 1120, 1790, 2250, and 3460 centimeters per second and at pressures of 0.42 and 0.59 millimeter of mercury showed that flow conditions had no effect. The results were also independent of atom concentration. A rough indication of the temperature dependence was obtained; it was greater for copper than for platinum. Platinum films deposited on platinum or on glass had the same activity - about 3 percent of the atoms impinging recombined. With copper, however, the glass substrate greatly reduced the percent of atoms recombining over that of a bulk copper substrate where 4 percent of the impinging atoms recombined. This effect could be overcome by depositing a second film on top of the first. Bulk metal samples were subjected to various surface treatments including polishing, degreasing with a chlorinated hydrocarbon, washing with nitric acid, and rinsing with water. Polished, degreased platinum had low activity compared to an evaporated film, but nitric acid treatment made it equivalent. Polished, degreased copper was only slightly less active than a copper film; nitric acid etching decreased the activity still further, probably by preferentially exposing facets of low catalytic efficiency.

Determination of the amount of physical adsorption of water vapour on platinum-iridium surfaces

NASA Astrophysics Data System (ADS)

Mizushima, S.; Ueda, K.; Ooiwa, A.; Fujii, K.

2015-08-01

This paper presents the measurement of the physical adsorption of water vapour on platinum-iridium surfaces using a vacuum mass comparator. This value is of importance for redefining the kilogram, which will be realized under vacuum in the near future. Mirror-polished artefacts, consisting of a reference artefact and a test artefact, were manufactured for this experiment. The surface area difference between the reference and test artefacts was 226.2 cm2. This surface area difference was approximately 3.2 times the geometric surface area of the prototype of the kilogram made of platinum-iridium (71.7 cm2). The measurement results indicate that the amount of physical adsorption at a relative humidity of 50% is 0.0129 μg cm{{-}2} , with a standard uncertainty of 0.0016 μg cm{{-}2} . This value is 0.03 to 0.16 times that observed in other studies.

Analyzing the electrooxidation of ethylene glycol and glucose over platinum-modified gold electrocatalysts in alkaline electrolyte using in-situ infrared spectroscopy

NASA Astrophysics Data System (ADS)

Mahoney, Elizabeth G.; Sheng, Wenchao; Cheng, Mei; Lee, Kevin X.; Yan, Yushan; Chen, Jingguang G.

2016-02-01

Platinum modified gold (Pt/Au) catalysts are evaluated for the electrooxidation of ethylene glycol (EG) and glucose (Glc). The Pt/Au catalysts are synthesized on an Au disk and supported Au/C particles through the galvanic displacement of a copper monolayer with Pt. The Pt/Au catalysts are compared to monometallic Pt and Au catalysts for the oxidation of EG and Glc in alkaline electrolyte. The Pt/Au disk has an onset potential for these reactions that is similar to Pt and is lower than Au. The supported catalysts are less active toward the electrooxidation of EG and Glc than the corresponding disk electrodes, but the Pt/Au/C also has an onset potential similar to Pt/C. In-situ FTIR is used to analyze the C-C bond scission in both reactions on the surfaces of Pt, Au, and Pt/Au disks. While the Pt/Au disk is found to have a low onset potential for the oxidation of EG, it does not produce as much CO2 as bulk Pt. On the other hand, the FTIR results show that CO2 is produced for the oxidation of Glc on the Pt/Au disk. These results show promise for the possibility of decreasing the amount of Pt needed for the electrooxidation of polyol molecules.

Electrodeposition of flower-like platinum on electrophoretically grown nitrogen-doped graphene as a highly sensitive electrochemical non-enzymatic biosensor for hydrogen peroxide detection

NASA Astrophysics Data System (ADS)

Tajabadi, M. T.; Sookhakian, M.; Zalnezhad, E.; Yoon, G. H.; Hamouda, A. M. S.; Azarang, Majid; Basirun, W. J.; Alias, Y.

2016-11-01

An efficient non-enzymatic biosensor electrode consisting of nitrogen-doped graphene (N-graphene) and platinum nanoflower (Pt NF) with different N-graphene loadings were fabricated on indium tin oxide (ITO) glass using a simple layer-by-layer electrophoretic and electrochemical sequential deposition approach. N-graphene was synthesized by annealing graphene oxide with urea at 900 °C. The structure and morphology of the as-fabricated non-enzymatic biosensor electrodes were determined using X-ray diffraction, field emission electron microscopy, transmission electron microscopy, Raman and X-ray photoelectron spectra. The as-fabricated Pt NF-N-graphene-modified ITO electrodes with different N-graphene loadings were utilized as a non-enzymatic biosensor electrode for the detection of hydrogen peroxide (H2O2). The behaviors of the hybrid electrodes towards H2O2 reduction were assessed using chronoamperometry, cyclic voltammetry and electrochemical impedance spectroscopy analysis. The Pt NF-N-graphene-modified ITO electrode with a 0.05 mg ml-1 N-graphene loading exhibited the lowest detection limit, fastest amperometric sensing, a wide linear response range, excellent stability and reproducibility for the non-enzymatic H2O2 detection, due to the synergistic effect between the electrocatalytic activity of the Pt NF and the high conductivity and large surface area of N-graphene.

Elucidating the alkaline oxygen evolution reaction mechanism on platinum

DOE PAGES

Favaro, M.; Valero-Vidal, C.; Eichhorn, J.; ...

2017-03-07

Understanding the interplay between surface chemistry, electronic structure, and reaction mechanism of the catalyst at the electrified solid/liquid interface will enable the design of more efficient materials systems for sustainable energy production. The substantial progress in operando characterization, particularly using synchrotron based X-ray spectroscopies, provides the unprecedented opportunity to uncover surface chemical and structural transformations under various (electro)chemical reaction environments. In this work, we study a polycrystalline platinum surface under oxygen evolution conditions in an alkaline electrolyte by means of ambient pressure X-ray photoelectron spectroscopy performed at the electrified solid/liquid interface. We elucidate previously inaccessible aspects of the surface chemistrymore » and structure as a function of the applied potential, allowing us to propose a reaction mechanism for oxygen evolution on a platinum electrode in alkaline solutions.« less

Infrared absorption spectroscopy characterization of liquid-solid interfaces: The case of chiral modification of catalysts

NASA Astrophysics Data System (ADS)

Zaera, Francisco

2018-03-01

An overview is provided here of our work on the characterization of chiral modifiers for the bestowing of enantioselectivity to metal-based hydrogenation catalysts, with specific reference to the so-called Orito reaction. We start with a brief discussion of the use of infrared absorption spectroscopy (IR) for the characterization of chemical species at liquid-solid interfaces, describing the options available as well as the information that can be extracted from such experiments and the advantages and disadvantages associated with the technique. We then summarize the main results that we have reported to date from our IR study of the adsorption of cinchona alkaloids and related compounds from solutions onto platinum surfaces. Several observations are highlighted and placed in context in terms of the existing knowledge and their relevance to catalysis. Key conclusions include the uniqueness of the nature of the adsorbed species when in the presence of the solvent (versus when the uptake is done under vacuum, or versus the pure or dissolved molecules), the fact that each modifier adopts unique and distinct adsorption geometries on the surface and that those change with the concentration of the solution in ways that correlate well with the performance of the catalyst, the potential tendency of at least some of these chiral modifiers to bind to the surface primarily via the nitrogen atom of the amine group, not the aromatic ring as it is often assumed, and the observation that the ability of one modifier to dominate the catalytic chemistry in solutions containing mixtures of two or more of those is linked to their capacity for displacing each other from the surface, which in turn is determined by a balance between the strength of their binding to the surface and their solubility in the liquid solvent.

Electron Field Emission Properties of Textured Platinum Surfaces

NASA Technical Reports Server (NTRS)

Sovey, James S.

2002-01-01

During ground tests of electric microthrusters and space tests of electrodynamic tethers the electron emitters must successfully operate at environmental pressures possibly as high as 1x10(exp -4) Pa. High partial pressures of oxygen, nitrogen, and water vapor are expected in such environments. A textured platinum surface was used in this work for field emission cathode assessments because platinum does not form oxide films at low temperatures. Although a reproducible cathode conditioning process did not evolve from this work, some short term tests for periods of 1 to 4 hours showed no degradation of emission current at an electric field of 8 V/mm and background pressures of about 1x10(exp -6) Pa. Increases of background pressure by air flow to about 3x10(exp -4) Pa yield a hostile environment for the textured platinum field emission cathode.

Platinum single-atom and cluster catalysis of the hydrogen evolution reaction

NASA Astrophysics Data System (ADS)

Cheng, Niancai; Stambula, Samantha; Wang, Da; Banis, Mohammad Norouzi; Liu, Jian; Riese, Adam; Xiao, Biwei; Li, Ruying; Sham, Tsun-Kong; Liu, Li-Min; Botton, Gianluigi A.; Sun, Xueliang

2016-11-01

Platinum-based catalysts have been considered the most effective electrocatalysts for the hydrogen evolution reaction in water splitting. However, platinum utilization in these electrocatalysts is extremely low, as the active sites are only located on the surface of the catalyst particles. Downsizing catalyst nanoparticles to single atoms is highly desirable to maximize their efficiency by utilizing nearly all platinum atoms. Here we report on a practical synthesis method to produce isolated single platinum atoms and clusters using the atomic layer deposition technique. The single platinum atom catalysts are investigated for the hydrogen evolution reaction, where they exhibit significantly enhanced catalytic activity (up to 37 times) and high stability in comparison with the state-of-the-art commercial platinum/carbon catalysts. The X-ray absorption fine structure and density functional theory analyses indicate that the partially unoccupied density of states of the platinum atoms' 5d orbitals on the nitrogen-doped graphene are responsible for the excellent performance.

Platinum single-atom and cluster catalysis of the hydrogen evolution reaction

PubMed Central

Cheng, Niancai; Stambula, Samantha; Wang, Da; Banis, Mohammad Norouzi; Liu, Jian; Riese, Adam; Xiao, Biwei; Li, Ruying; Sham, Tsun-Kong; Liu, Li-Min; Botton, Gianluigi A.; Sun, Xueliang

2016-01-01

Platinum-based catalysts have been considered the most effective electrocatalysts for the hydrogen evolution reaction in water splitting. However, platinum utilization in these electrocatalysts is extremely low, as the active sites are only located on the surface of the catalyst particles. Downsizing catalyst nanoparticles to single atoms is highly desirable to maximize their efficiency by utilizing nearly all platinum atoms. Here we report on a practical synthesis method to produce isolated single platinum atoms and clusters using the atomic layer deposition technique. The single platinum atom catalysts are investigated for the hydrogen evolution reaction, where they exhibit significantly enhanced catalytic activity (up to 37 times) and high stability in comparison with the state-of-the-art commercial platinum/carbon catalysts. The X-ray absorption fine structure and density functional theory analyses indicate that the partially unoccupied density of states of the platinum atoms' 5d orbitals on the nitrogen-doped graphene are responsible for the excellent performance. PMID:27901129

Hierarchical Nanoporous Gold-Platinum with Heterogeneous Interfaces for Methanol Electrooxidation

PubMed Central

Xiao, Shuang; Xiao, Fei; Hu, Yuan; Yuan, Songliu; Wang, Shuai; Qian, Lihua; Liu, Yunqi

2014-01-01

The electrocatalysts utilized as the prospective electrodes in fuel cells and high efficient energy conversion devices require both the interconnected channels for efficient electrolyte transportation and the superior catalytic activity with long service life. In this work, nanoporous gold with the rigid skeletons in three dimensions is partially decorated by porous platinum shell containing nanoscale interstitials, aiming to create the heterogeneous gold-platinum interfaces and facilitate the electrolyte transportation as well. In comparison with no catalytic activity of bare nanoporous gold, the catalytic activity of hierarchical nanoporous gold-platinum towards electrochemical oxidation of methanol increases with the loading level of platinum shells, resulting in the highest electrochemical area of 70.4 m2·g−1 after the normalization by the mass of platinum. Heterogeneous gold-platinum interfaces affect the tolerance of the absorbed intermediate species because of the oxidization by the oxygenated species absorbed on the gold surface and the enhanced ion transportation within the porous platinum shell. PMID:24621809

Research on rechargeable oxygen electrodes

NASA Technical Reports Server (NTRS)

Giner, J.; Malachesky, P. A.; Holleck, G.

1971-01-01

Studies were carried out on a number of factors which may influence the behavior of the platinum electrocatalyst of oxygen electrodes for use in rechargeable metal-oxygen batteries or hydrogen-oxygen fuel cells. The effects of pretreatments for various potentials and added ionic species, which could be present in such systems, were studied with reguard to: (1) the state of surface oxidation, (2) platinum dissolution, (3) the kinetics of oxygen evolution and reduction (including the role of hydrogen peroxide), and (4) changes in porous electrode structure. These studies were carried out on smooth platinum, platinized platinum, and Teflon-bonded platinum black electrodes in carefully purified electrolyte solutions. The main factors which appear to affect rechargeable oxygen electrode performance and life are: (1) the buildup of a refractory anodic layer on extended cycling, and (2) the dissolution of platinum.

Facile one-pot synthesis of platinum nanoparticles decorated nitrogen-graphene with high electrocatalytic performance for oxygen reduction and anodic fuels oxidation

NASA Astrophysics Data System (ADS)

Navaee, Aso; Salimi, Abdollah; Soltanian, Saeid; Servati, Peyman

2015-03-01

Due to exceptional electronic properties of graphene (Gr) and nitrogen doped graphene (N-Gr), they are considered as superior supporting platforms for novel metal nanoparticle decorations. Here, we report, a novel one-step electrochemical method for synthesis of Nitrogen-doped graphene sheets uniformly decorated with platinum nanoparticles (Pt/N-Gr). A graphite rod and platinum wire are respectively used for graphene and platinum nanoparticles production. The potential is cycled from -3V to +3V in acetonitrile solution as a nitrogen dopant source. By increasing the number of cycles the nitrogen-doped graphene/platinum nanoparticles composite is generated. After heat-treating the composite is characterized with various techniques such as FTIR, Raman, XPS, SEM and TEM. The electrocatalytic activity of the prepared composite toward the reduction of O2 and the oxidation of usual anodic fuels such as methanol, ethanol, hydrazine and formic acid is investigated using cyclic voltammetry technique. In comparison to commercial platinum/carbon, the onset potentials and the current densities for both O2 reduction and fuels oxidation are remarkably improved. Furthermore, the modified electrode by this composite shows good long-term stability and poisoning tolerance.

Ganoderma-Like MoS2 /NiS2 with Single Platinum Atoms Doping as an Efficient and Stable Hydrogen Evolution Reaction Catalyst.

PubMed

Guan, Yongxin; Feng, Yangyang; Wan, Jing; Yang, Xiaohui; Fang, Ling; Gu, Xiao; Liu, Ruirui; Huang, Zhengyong; Li, Jian; Luo, Jun; Li, Changming; Wang, Yu

2018-05-27

Herein, a unique ganoderma-like MoS 2 /NiS 2 hetero-nanostructure with isolated Pt atoms anchored is reported. This novel ganoderma-like heterostructure can not only efficiently disperse and confine the few-layer MoS 2 nanosheets to fully expose the edge sites of MoS 2 , and provide more opportunity to capture the Pt atoms, but also tune the electronic structure to modify the catalytic activity. Because of the favorable dispersibility and exposed large specific surface area, single Pt atoms can be easily anchored on MoS 2 nanosheets with ultrahigh loading of 1.8 at% (the highest is 1.3 at% to date). Owing to the ganoderma-like structure and platinum atoms doping, this catalyst shows Pt-like catalytic activity for the hydrogen evolution reaction with an ultralow overpotential of 34 mV and excellent durability of only 2% increase in overpotential for 72 h under the constant current density of 10 mA cm -2 . © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ultrasensitive electrochemical immunosensors for multiplexed determination using mesoporous platinum nanoparticles as nonenzymatic labels.

PubMed

Cui, Zhentao; Wu, Dan; Zhang, Yong; Ma, Hongmin; Li, He; Du, Bin; Wei, Qin; Ju, Huangxian

2014-01-07

An ultrasensitive multiplexed immunoassay method was developed at a disposable immunosensor array using mesoporous platinum nanoparticles (M-Pt NPs) as nonenzymatic labels. M-Pt NPs were prepared by ultrasonic method and employed to label the secondary antibody (Ab2) for signal amplification. The immunosensor array was constructed by covalently immobilizing capture antibody (Ab1) on graphene modified screen printed carbon electrodes (SPECs). After the sandwich-type immunoreactions, the M-Pt-Ab2 was bound to immunosensor surface to catalyze the electro-reduction of H2O2 reaction, which produced detectable signals for readout of analytes. Using breast cancer related panel of tumor markers (CA125, CA153 and CEA) as model analytes, this method showed wide linear ranges of over 4 orders of magnitude with the detection limits of 0.002 U mL(-1), 0.001 U mL(-1) and 7.0 pg mL(-1) for CA125, CA153 and CEA, respectively. The disposable immunosensor array possessed excellent clinical value in cancer screening as well as convenient point of care diagnostics. Copyright © 2013 Elsevier B.V. All rights reserved.

Fabrication of rippled surfaces for diffraction gratings by plastic deformation of platinum foils and metallic glasses

NASA Astrophysics Data System (ADS)

Korsukov, V. E.; Malygin, G. A.; Korsukova, M. M.; Nyapshaev, I. A.; Obidov, B. A.

2015-12-01

Thin platinum foils and metallic glass ribbons with a fractal surface consisting of different-scale unidirectionally oriented ripples have been fabricated using special thermoplastic processing. The general fractal dimension of the rippled surface and dimensions along and across the ripples have been measured. The optical spectra of a PRK-4 lamp using rippled Pt(111) foils as reflective diffraction gratings have been determined. A model describing the mechanism of the formation of surface unidirectional fractal structures during deformation has been proposed.

Antibacterial activity of microstructured sacrificial anode thin films by combination of silver with platinum group elements (platinum, palladium, iridium).

PubMed

Köller, Manfred; Bellova, Petri; Javid, Siyamak Memar; Motemani, Yahya; Khare, Chinmay; Sengstock, Christina; Tschulik, Kristina; Schildhauer, Thomas A; Ludwig, Alfred

2017-05-01

Five different Ag dots arrays (16 to 400dots/mm 2 ) were fabricated on a continuous platinum, palladium, or iridium thin film and for comparison also on titanium film by sputter deposition and photolithographic patterning. To analyze the antibacterial activity of these microstructured films Staphylococcus aureus (S. aureus) were placed onto the array surfaces and cultivated overnight. To analyze the viability of planktonic as well as surface adherent bacteria, the applied bacterial fluid was subsequently aspirated, plated on blood agar plates and adherent bacteria were detected by fluorescence microscopy. A particular antibacterial effect towards S. aureus was induced by Ag dot arrays on each of the platinum group thin film (sacrificial anode system for Ag) in contrast to Ag dot arrays fabricated on the Ti thin films (non-sacrificial anode system for Ag). Among platinum group elements the Ir-Ag system exerted the highest antibacterial activity which was accompanied by most advanced dissolution of the Ag dots and Ag ion release compared to Ag dots on Pt or Pd. Copyright © 2016 Elsevier B.V. All rights reserved.

Nanoparticles based fiber optic SPR sensor

NASA Astrophysics Data System (ADS)

Shah, Kruti; Sharma, Navneet K.

2018-05-01

Localized surface plasmon resonance based fiber optic sensor using platinum nanoparticles is proposed and theoretically analyzed. Increase in thickness of nanoparticles layer increases the sensitivity of sensor. 50 nm thick platinum nanoparticles layer based sensor reveals highest sensitivity.

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

NASA Astrophysics Data System (ADS)

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

2018-01-01

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

Molecular Engineering of Platinum(II) Terpyridine Complexes with Tetraphenylethylene-Modified Alkynyl Ligands: Supramolecular Assembly via Pt···Pt and/or π-π Stacking Interactions and the Formation of Various Superstructures.

PubMed

Cheng, Heung-Kiu; Yeung, Margaret Ching-Lam; Yam, Vivian Wing-Wah

2017-10-18

A series of platinum(II) terpyridine complexes with tetraphenylethylene-modified alkynyl ligands has been designed and synthesized. The introduction of the tetraphenylethylene motif has led to aggregation-induced emission (AIE) properties, which upon self-assembly led to the formation of metal-metal-to-ligand charge transfer (MMLCT) behavior stabilized by Pt···Pt and/or π-π interactions. Tuning the steric bulk or hydrophilicity through molecular engineering of the platinum(II) complexes has been found to alter their spectroscopic properties and result in interesting superstructures (including nanorods, nanospheres, nanowires, and nanoleaves) in the self-assembly process. The eye-catching color and emission changes upon varying the solvent compositions may have potential applications in chemosensing materials for the detection of microenvironment changes. Furthermore, the importance of the directional Pt···Pt and/or π-π interactions on the construction of distinctive superstructures has also been examined by UV-vis absorption and emission spectroscopy and transmission electron microscopy. This work represents the interplay of both inter- and intramolecular interactions as well as the energies of the two different chromophoric/luminophoric systems that may open up a new route for the development of platinum(II)-AIE hybrids as functional materials.

Adsorption of xenon on vicinal copper and platinum surfaces

NASA Astrophysics Data System (ADS)

Baker, Layton

The adsorption of xenon was studied on Cu(111), Cu(221), Cu(643) and on Pt(111), Pt(221), and Pt(531) using low energy electron diffraction (LEED), temperature programmed desorption (TPD) of xenon, and ultraviolet photoemission of adsorbed xenon (PAX). These experiments were performed to study the atomic and electronic structure of stepped and step-kinked, chiral metal surfaces. Xenon TPD and PAX were performed on each surface in an attempt to titrate terrace, step edge, and kink adsorption sites by adsorption energetics (TPD) and local work function differences (PAX). Due to the complex behavior of xenon on the vicinal copper and platinum metal surfaces, adsorption sites on these surfaces could not be adequately titrated by xenon TPD. On Cu(221) and Cu(643), xenon desorption from step adsorption sites was not apparent leading to the conclusion that the energy difference between terrace and step adsorption is minuscule. On Pt(221) and Pt(531), xenon TPD indicated that xenon prefers to bond at step edges and that the xenon-xenon interaction at step edges in repulsive but no further indication of step-kink adsorption was observed. The Pt(221) and Pt(531) TPD spectra indicated that the xenon overlayer undergoes strong compression near monolayer coverage on these surfaces due to repulsion between step-edge adsorbed xenon and other encroaching xenon atoms. The PAX experiments on the copper and platinum surfaces demonstrated that the step adsorption sites have lower local work functions than terrace adsorption sites and that higher step density leads to a larger separation in the local work function of terrace and step adsorption sites. The PAX spectra also indicated that, for all surfaces studied at 50--70 K, step adsorption is favored at low coverage but the step sites are not saturated until monolayer coverage is reached; this observation is due to the large entropy difference between terrace and step adsorption states and to repulsive interactions between xenon atoms adsorbed at step edges (on the platinum surfaces). The results herein provide several novel observations regarding the adsorptive behavior of xenon on vicinal copper and platinum surfaces.

Correlation between the Knight shift of chemisorbed CO and the Fermi level local density of states at clean platinum catalyst surfaces

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

Tong, Y.Y.; Rice, C.; Godbout, N.

1999-04-07

Due to its fundamental importance in heterogeneous catalysis, as well as in electrocatalysis, the chemisorption and reaction of CO on transition metal surfaces has been an important focus of modern surface science. Here, the NMR spectroscopy of {sup 13}CO adsorbed onto transition metal surfaces has been shown to be a very powerful probe of molecular structure and dynamics of CO itself, as well as a probe of the electronic properties of the transition metal surfaces onto which it is adsorbed. The authors have investigated the {sup 195}Pt and {sup 13}C nuclear magnetic resonance (NMR) spectroscopy of clean-surface platinum catalysts andmore » of CO chemisorbed onto Pt catalysts surfaces. They use Knight shift, relaxation, and J-coupling data to deduce information about the Fermi level local density of states (E{sub f}-LDOS) at catalyst surfaces. There is a linear correlation between the Knight shifts of chemisorbed CO and the clean surface E{sub f}-LDOS of platinum onto which the CO is bound, as determined by {sup 13}C and {sup 195}Pt NMR. The correlation amounts to {approximately} 12 ppm/Ry{sup {minus}1} {center_dot} atom{sup {minus}1}, the same as that which can be deduced for CO on palladium, as well as from the electrode potential dependence of {sup 13}C Knight shifts and infrared vibrational frequencies, {nu}{sub CO}, and the relationship between {nu}{sub CO} and the E{sub f}-LDOS at clean platinum surfaces. The ability to now directly relate meal and adsorbate electronic properties opens up new avenues for investigating metal-ligand interactions in heterogeneous catalysis and electrocatalysis.« less

Bioinspired hierarchical nanotubular titania immobilized with platinum nanoparticles for photocatalytic hydrogen production.

PubMed

Liu, Xiaoyan; Li, Jiao; Zhang, Yiming; Huang, Jianguo

2015-05-11

A bioinspired nanocomposite composed of platinum nanoparticles and nanotubular titania was fabricated in which the titania matter was templated by natural cellulose substance. The composite possesses three- dimensional hierarchical structures, and ultrafine metallic platinum particles with sizes of ca. 2 nm were immobilized uniformly on the surfaces of the titania nanotubes. Such a nanocomposite with 1.06 wt % of platinum content shows the optimal photocatalytic hydrogen production activity from water splitting of 16.44 mmol h(-1)  g(-1) , and excessive loading of platinum results in poorer photocatalytic performance. The structural integrity of the nanocomposite upon cyclic water-splitting processes results in its sufficient photocatalytic stability. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Etching nano-holes in silicon carbide using catalytic platinum nano-particles

NASA Astrophysics Data System (ADS)

Moyen, E.; Wulfhekel, W.; Lee, W.; Leycuras, A.; Nielsch, K.; Gösele, U.; Hanbücken, M.

2006-09-01

The catalytic reaction of platinum during a hydrogen etching process has been used to perform controlled vertical nanopatterning of silicon carbide substrates. A first set of experiments was performed with platinum powder randomly distributed on the SiC surface. Subsequent hydrogen etching in a hot wall reactor caused local atomic hydrogen production at the catalyst resulting in local SiC etching and hole formation. Secondly, a highly regular and monosized distribution of Pt was obtained by sputter deposition of Pt through an Au membrane serving as a contact mask. After the lift-off of the mask, the hydrogen etching revealed the onset of well-controlled vertical patterned holes on the SiC surface.

Modeling the migration of platinum nanoparticles on surfaces using a kinetic Monte Carlo approach

DOE PAGES

Li, Lin; Plessow, Philipp N.; Rieger, Michael; ...

2017-02-15

We propose a kinetic Monte Carlo (kMC) model for simulating the movement of platinum particles on supports, based on atom-by-atom diffusion on the surface of the particle. The proposed model was able to reproduce equilibrium cluster shapes predicted using Wulff-construction. The diffusivity of platinum particles was simulated both purely based on random motion and assisted using an external field that causes a drift velocity. The overall particle diffusivity increases with temperature; however, the extracted activation barrier appears to be temperature independent. Additionally, this barrier was found to increase with particle size, as well as, with the adhesion between the particlemore » and the support.« less

Efficient water reduction with gallium phosphide nanowires

PubMed Central

Standing, Anthony; Assali, Simone; Gao, Lu; Verheijen, Marcel A.; van Dam, Dick; Cui, Yingchao; Notten, Peter H. L.; Haverkort, Jos E. M.; Bakkers, Erik P. A. M.

2015-01-01

Photoelectrochemical hydrogen production from solar energy and water offers a clean and sustainable fuel option for the future. Planar III/V material systems have shown the highest efficiencies, but are expensive. By moving to the nanowire regime the demand on material quantity is reduced, and new materials can be uncovered, such as wurtzite gallium phosphide, featuring a direct bandgap. This is one of the few materials combining large solar light absorption and (close to) ideal band-edge positions for full water splitting. Here we report the photoelectrochemical reduction of water, on a p-type wurtzite gallium phosphide nanowire photocathode. By modifying geometry to reduce electrical resistance and enhance optical absorption, and modifying the surface with a multistep platinum deposition, high current densities and open circuit potentials were achieved. Our results demonstrate the capabilities of this material, even when used in such low quantities, as in nanowires. PMID:26183949

Correlation of Electrode Kinetics with Surface Structure.

DTIC Science & Technology

1980-09-01

platinum and gold electrodes is sufficiently strong so that monolayers are formed upon contact even with small (millimolar) bulk iodide concentrations...transition-metal reactants, we have monitored the effects of altering the electrode material from mercury to silver, platinum, and gold upon the...strikingly different behavior for the reduction of Co III(NH3)5X and Co II(en)2X2 at platinum and gold electrodes. 1 0 For halide bridging ligands (X

Platinum particle size and support effects in NO(x) mediated carbon oxidation over platinum catalysts.

PubMed

Villani, Kenneth; Vermandel, Walter; Smets, Koen; Liang, Duoduo; van Tendeloo, Gustaaf; Martens, Johan A

2006-04-15

Platinum metal was dispersed on microporous, mesoporous, and nonporous support materials including the zeolites Na-Y, Ba-Y, Ferrierite, ZSM-22, ETS-10, and AIPO-11, alumina, and titania. The oxidation of carbon black loosely mixed with catalyst powder was monitored gravimetrically in a gas stream containing nitric oxide, oxygen, and water. The carbon oxidation activity of the catalysts was found to be uniquely related to the Pt dispersion and little influenced by support type. The optimum dispersion is around 3-4% corresponding to relatively large Pt particle sizes of 20-40 nm. The carbon oxidation activity reflects the NO oxidation activity of the platinum catalyst, which reaches an optimum in the 20-40 nm Pt particle size range. The lowest carbon oxidation temperatures were achieved with platinum loaded ZSM-22 and AIPO-11 zeolite crystallites bearing platinum of optimum dispersion on their external surfaces.

Electrochemical growth of CoNi and Pt-CoNi soft magnetic composites on an alkanethiol monolayer-modified ITO substrate.

PubMed

Escalera-López, D; Gómez, E; Vallés, E

2015-07-07

CoNi and Pt-CoNi magnetic layers on indium-tin oxide (ITO) substrates modified by an alkanethiol self-assembled monolayer (SAM) have been electrochemically obtained as an initial stage to prepare semiconducting layer-SAM-magnetic layer hybrid structures. The best conditions to obtain the maximum compactness of adsorbed layers of dodecanethiol (C12-SH) on ITO substrate have been studied using contact angle, AFM, XPS and electrochemical tests. The electrochemical characterization (electrochemical probe or voltammetric response in blank solutions) is fundamental to ensure the maximum blocking of the substrate. Although the electrodeposition process on the SAM-modified ITO substrate is very slow if the blocking of the surface is significant, non-cracked metallic layers of CoNi, with or without a previously electrodeposited seed-layer of platinum, have been obtained by optimizing the deposition potentials. Initial nucleation is expected to take place at the pinhole defects of the C12-SH SAM, followed by a mushroom-like growth regime through the SAM interface that allows the formation of a continuous metallic layer electrically connected to the ITO surface. Due to the potential of the methodology, the preparation of patterned metallic deposits on ITO substrate using SAMs with different coverage as templates is feasible.

Platinum stable isotopes in ferromanganese crust and nodules

NASA Astrophysics Data System (ADS)

Corcoran, Loretta; Seward, Terry; Handler, Monica R.

2015-04-01

Hydrogenetic ferromanganese (Fe-Mn) crust and nodules are slow-growing chemical sediments that form by direct precipitation from seawater, resulting in a record of changing seawater chemistry. These sediments are the primary sink for platinum in the modern oxic marine environment, hosting well-documented enrichments over other platinum-group elements (PGEs): the Pt anomaly [1]. Platinum is a non-bio-essential, highly siderophile, transition metal with six stable isotopes (190Pt, 192Pt, 194Pt, 195Pt, 196Pt, and 198Pt) with several oxidation states (Pt0, Pt2+ and Pt4+). Platinum is generally considered to exist in the hydrosphere as Pt2+ although its behaviour in the marine environment is poorly constrained, and Pt4+may also be present. Variations in ocean redox state, together with changes in source fluxes to the oceans, may therefore lead to small variations (< ±1) in the stable isotopic composition of marine platinum, raising the potential of adding platinum to the growing arsenal of paleoceanographic tracers. A method has been developed to measure the platinum isotopic composition using double spike MC-ICPMS analysis [2]and applied to a global suite of modern Fe-Mn crust and nodules. Combining synchrotron XAFS analyses of platinum adsorbed onto Fe-Mn oxide and oxyhydroxide surfaces to determine oxidation state and bonding environment, with platinum stable isotopic measurements allowing us to evaluate both platinum incorporation onto these sediments and the associated degree of platinum isotopic fractionation. Leaching experiments conducted on platinum rich terrestrial materials underwent platinum stable isotopic measurement as an analogue for the Pt isotopic fractionation associated with continental weathering. [1] Hodge, V.F. et al. (1985) Earth and Planetary Science Letters, 72, 158-162. [2] Creech, J. et al. (2013) Journal of Analytical Atomic Spectrometry, 28. 853-865.

Modeling the interface of platinum and α-quartz(001): Implications for sintering

DOE PAGES

Plessow, Philipp N.; Sánchez-Carrera, Roel S.; Li, Lin; ...

2016-05-04

We present a first-principles study which aims to understand the metal–support interaction of platinum nanoparticles on α-quartz(001) and, more generally, silica. The thermodynamic stability of the α-quartz(001) surface and its interface with Pt(111) are investigated as a function of temperature and partial pressure of H 2O and O 2. Potential defects in the α-quartz(001) surface as well as the adsorption energies of the Pt atom are also studied. This allows us to draw conclusions concerning nanoparticle shape and the resistance toward particle migration based on the interface free energies. We find that, as for the clean α-quartz(001) surface, a dry,more » reconstructed interface is expected at temperatures that are high but within experimentally relevant ranges. On an ideal, dry, reconstructed surface, particle migration is predicted to be a fast sintering mechanism. On real surfaces, defects may locally prevent reconstruction and act as anchoring points. Finally, the energetics of the adsorption of platinum atoms on α-quartz(001) do not support surface-mediated single-atom migration as a viable path for sintering on the investigated surfaces.« less

Platinum nanoparticles decorated dendrite-like gold nanostructure on glassy carbon electrodes for enhancing electrocatalysis performance to glucose oxidation

NASA Astrophysics Data System (ADS)

Jia, Hongmei; Chang, Gang; Lei, Ming; He, Hanping; Liu, Xiong; Shu, Honghui; Xia, Tiantian; Su, Jie; He, Yunbin

2016-10-01

Platinum nanoparticles decorated dendrite-like gold nanostructure, bimetal composite materials on glassy carbon electrode (Pt/DGNs/GC) for enhancing electrocatalysis to glucose oxidation was designed and successfully fabricated by a facile two-step deposition method without any templates, surfactants, or stabilizers. Dendrite-like gold nanostructure was firstly deposited on the GC electrode via the potentiostatic method, and then platinum nanoparticles were decorated on the surface of gold substrate through chemical reduction deposition. X-ray diffraction (XRD), field-emission scanning electron microscope (FE-SEM), energy-dispersive X-ray spectroscopy (EDS) were applied to characterize the evolution of morphology and structure of the as-prepared Pt/DGNs/GC. Based on electrochemical measurements such as cyclic voltammetry, linear voltammetry and chronoamperometry, Pt/DGNs/GC exhibited significantly enhanced electrocatalytic performance to glucose oxidation compared those of pure dendrite-like Au nanoparticles in our previous report. Controlling chemical reduction deposition time, the amount of platinum nanoparticles on Au surface could be regulated, which further tuned electrocatalytic properties toward glucose oxidation. The dendrite-like gold surface partially covered by platinum nanoparticles dramatically enhanced the electrocatalytic performance for the oxidation of glucose because of excellent synergetic effects between gold and platinum species and the increased electrochemical active area from Pt nanoparticles loading. The non-enzymatic glucose biosensor based on Pt/DGNs/GC showed a rapid respond time (within 2 s), wide linear range (from 0.1 mM to 14 mM), low detection limit (0.01 mM), supernal sensitivity (275.44 μA cm-2 mM-1, R = 0.993), satisfactory reproducibility and good stability for glucose sensing. It was demonstrated that Pt/DGNs/GC could work as promising candidate for factual non-enzymatic glucose detection.

Effects of para-substituents of styrene derivatives on their chemical reactivity on platinum nanoparticle surfaces.

PubMed

Hu, Peiguang; Chen, Limei; Deming, Christopher P; Lu, Jia-En; Bonny, Lewis W; Chen, Shaowei

2016-06-09

Stable platinum nanoparticles were successfully prepared by the self-assembly of para-substituted styrene derivatives onto the platinum surfaces as a result of platinum-catalyzed dehydrogenation and transformation of the vinyl groups to the acetylene ones, forming platinum-vinylidene/-acetylide interfacial bonds. Transmission electron microscopic measurements showed that the nanoparticles were well dispersed without apparent aggregation, suggesting sufficient protection of the nanoparticles by the organic capping ligands, and the average core diameter was estimated to be 2.0 ± 0.3 nm, 1.3 ± 0.2 nm, and 1.1 ± 0.2 nm for the nanoparticles capped with 4-tert-butylstyrene, 4-methoxystyrene, and 4-(trifluoromethyl)styrene, respectively, as a result of the decreasing rate of dehydrogenation with the increasing Taft (polar) constant of the para-substituents. Importantly, the resulting nanoparticles exhibited unique photoluminescence, where an increase of the Hammett constant of the para-substituents corresponded to a blue-shift of the photoluminescence emission, suggesting an enlargement of the HOMO-LUMO band gap of the nanoparticle-bound acetylene moieties. Furthermore, the resulting nanoparticles exhibited apparent electrocatalytic activity towards oxygen reduction in acidic media, with the best performance among the series of samples observed with the 4-tert-butylstyrene-capped nanoparticles due to an optimal combination of the nanoparticle core size and ligand effects on the bonding interactions between platinum and oxygen species.

A Chemical Approach to Understanding Oxide Surface Structure and Reactivity

NASA Astrophysics Data System (ADS)

Enterkin, James Andrew

Transmission electron microscopy and diffraction are powerful tools for solving complex structural problems. They complement other analytical techniques, such as x-ray diffraction, elucidating problems which cannot be solved by other techniques. One area where they are of particularly great value is in the determination of surface structures. The research presented herein uses electron microscopy and diffraction as the primary experimental techniques in the development of a chemistry of surface structures. High-resolution electron microscopy revealed that the La4Cu 3MoO12 structure has turbostratic disorder and a lower symmetry space group (Pm) than was previously found. The refinement of the x-ray data was significantly improved by using a disordered model and the Pm space group. A bond valence analysis confirmed that the disordered structure is the superior model. Strontium titanate, SrTiO3, single crystal surfaces were examined principally via transmission electron diffraction. A homologous series with intergrowths was discovered on the (110) surface of strontium titanate, marking the first time that these important concepts of solid state chemistry have been found at the surface. Atmospheric adsorbates, such as H2O and CO2, were found to help to stabilize undercoordinated surface structures on the (100) surface. It was shown that chemical bonding, bond valence, atomic coordination, and stoichiometry greatly influence the development of surface structures. Additionally, such chemistry based analysis was demonstrated to be able to predict surface structure stability and reactivity. Application of a modified Wulff construction to the observed shape of strontium titanate nanocuboids revealed that the surface structure and particle stoichiometry are interlinked, with control over one allowing equally precise control over the other. Platinum nanoparticles on the strontium titanate nanocuboids were shown via high resolution electron microscopy to have cube-on-cube epitaxy, with the shape of the platinum nanoparticles governed by the Winterbottom construction. Precise modification of the support surface will therefore allow engineering of supported metal particles with precise control over which facets are exposed. These results suggest that control over the support surface chemistry can be used to engineer thermodynamically stable, face selective catalysts.

Graphene-supported platinum catalyst prepared with ionomer as surfactant for anion exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Zeng, L.; Zhao, T. S.; An, L.; Zhao, G.; Yan, X. H.; Jung, C. Y.

2015-02-01

In this work, we have synthesized an ionomer-coated graphene-supported platinum catalyst for anion exchange membrane fuel cells. Unlike the common surfactant stabilized colloidal method, we employ a home-made anion exchange ionomer (AEI), namely quaternary ammonia poly (2, 6-dimethyl-1, 4-phenylene oxide) (QAPPO), as the surfactant. The AEI coated on reduced graphene oxide (rGO) surfaces serves as a stabilizer to anchor the platinum precursor on rGO surfaces due to electrostatic interactions. As a result, platinum nanoparticles (Pt NPs) can be easily deposited onto rGO surfaces with a uniform distribution. The remarkable feature of the present synthesis method is that the surfactant, the coated AEI, does not need to be removed from the catalyst, but serves as hydroxide-conductive paths in the catalyst layer, leading to enhanced triple phase boundaries. It is demonstrated that the use of the catalyst obtained with the present method enables a H2/O2 AEMFC to yield a peak power density of 264.8 mW cm-2 at 60 °C, which is 30% higher than that produced from the same fuel cell but with the use of the catalyst synthesized by the conventional synthesis method.

The molecular shape and the field similarities as criteria to interpret SAR studies for fragment-based design of platinum(IV) anticancer agents. Correlation of physicochemical properties with cytotoxicity.

PubMed

Lorenzo, Julia; Montaña, Ángel M

2016-09-01

Molecular shape similarity and field similarity have been used to interpret, in a qualitative way, the structure-activity relationships in a selected series of platinum(IV) complexes with anticancer activity. MM and QM calculations have been used to estimate the electron density, electrostatic potential maps, partial charges, dipolar moments and other parameters to correlate the stereo-electronic properties with the differential biological activity of complexes. Extended Electron Distribution (XED) field similarity has been also evaluated for the free 1,4-diamino carrier ligands, in a fragment-based drug design approach, comparing Connolly solvent excluded surface, hydrophobicity field surface, Van der Waals field surface, nucleophilicity field surface, electrophilicity field surface and the extended electron-distribution maxima field points. A consistency has been found when comparing the stereo-electronic properties of the studied series of platinum(IV) complexes and/or the free ligands evaluated and their in vitro anticancer activity. Copyright © 2016 Elsevier Inc. All rights reserved.

Platinum redispersion on metal oxides in low temperature fuel cells.

PubMed

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

2013-03-07

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

Platinum-TM (TM = Fe, Co) alloy nanoparticles dispersed nitrogen doped (reduced graphene oxide-multiwalled carbon nanotube) hybrid structure cathode electrocatalysts for high performance PEMFC applications.

PubMed

Vinayan, B P; Ramaprabhu, S

2013-06-07

The efforts to push proton exchange membrane fuel cells (PEMFC) for commercial applications are being undertaken globally. In PEMFC, the sluggish kinetics of oxygen reduction reactions (ORR) at the cathode can be improved by the alloying of platinum with 3d-transition metals (TM = Fe, Co, etc.) and with nitrogen doping, and in the present work we have combined both of these aspects. We describe a facile method for the synthesis of a nitrogen doped (reduced graphene oxide (rGO)-multiwalled carbon nanotubes (MWNTs)) hybrid structure (N-(G-MWNTs)) by the uniform coating of a nitrogen containing polymer over the surface of the hybrid structure (positively surface charged rGO-negatively surface charged MWNTs) followed by the pyrolysis of these (rGO-MWNTs) hybrid structure-polymer composites. The N-(G-MWNTs) hybrid structure is used as a catalyst support for the dispersion of platinum (Pt), platinum-iron (Pt3Fe) and platinum-cobalt (Pt3Co) alloy nanoparticles. The PEMFC performances of Pt-TM alloy nanoparticle dispersed N-(G-MWNTs) hybrid structure electrocatalysts are 5.0 times higher than that of commercial Pt-C electrocatalysts along with very good stability under acidic environment conditions. This work demonstrates a considerable improvement in performance compared to existing cathode electrocatalysts being used in PEMFC and can be extended to the synthesis of metal, metal oxides or metal alloy nanoparticle decorated nitrogen doped carbon nanostructures for various electrochemical energy applications.

Platinum clusters supported in zeolite LTL: Influence of catalyst morphology on performance in n-hexane reforming

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

Jentoft, R.E.; Gates, B.C.; Tsapatsis, M.

KLTL zeolite-supported platinum catalysts were synthesized from aqueous tetraammineplatinum(II) nitrate solutions and nonacidic KLTL zeolite crystallites, including some with dimensions as little as 300 x 500 {angstrom}. The zeolite crystallites had various morphologies, some being predominantly disk-shaped particles and some predominantly mosaics of rod-like domains with a range of c-dimension lengths. The activity and selectivity of each catalyst were evaluated for dehydrocyclization of n-hexane in the presence of H{sub 2} to form predominantly benzene at conversions of typically 45--90%. The data presented here provide a detailed characterization of the deactivation of such catalysts in the absence of sulfur. EXAFS datamore » show that the platinum in each catalyst was present in clusters of about 20 atoms each, on average. Electron micrographs show that the platinum clusters were nearly evenly dispersed on the surfaces of the zeolite crystallites, including the intracrystalline and extracrystalline surfaces. The catalytic performance was virtually independent of the zeolite channel length, but activity, selectivity, and resistance to deactivation were found to be correlated with the ratio of the surface area external to the crystallite domains to that within the intracrystalline pores. The catalyst performance is dependent on this ratio (which is related to the zeolite morphology) as follows: in comparison with the others, the catalysts with the relatively low fractions of platinum outside the intracrystalline pores are more active, more selective for benzene formation, and more resistant to deactivation.« less

Surface engineering of hierarchical platinum-cobalt nanowires for efficient electrocatalysis

DOE PAGES

Bu, Lingzheng; Guo, Shaojun; Zhang, Xu; ...

2016-06-29

Despite intense research in past decades, the lack of high-performance catalysts for fuel cell reactions remains a challenge in realizing fuel cell technologies for transportation applications. Here we report a facile strategy for synthesizing hierarchical platinum-cobalt nanowires with high-index, platinum-rich facets and ordered intermetallic structure. These structural features enable unprecedented performance for the oxygen reduction and alcohol oxidation reactions. The specific/mass activities of the platinum-cobalt nanowires for oxygen reduction reaction are 39.6/33.7 times higher than commercial Pt/C catalyst, respectively. Density functional theory simulations reveal that the active threefold hollow sites on the platinum-rich high-index facets provide an additional factor inmore » enhancing oxygen reduction reaction activities. The nanowires are stable in the electrochemical conditions and also thermally stable. Furthermore, this work may represent a key step towards scalable production of high performance platinum-based nanowires for applications in catalysis and energy conversion.« less

Palladium–platinum core-shell icosahedra with substantially enhanced activity and durability towards oxygen reduction

DOE PAGES

Wang, Xue; Choi, Sang-Il; Roling, Luke T.; ...

2015-07-02

Conformal deposition of platinum as ultrathin shells on facet-controlled palladium nanocrystals offers a great opportunity to enhance the catalytic performance while reducing its loading. Here we report such a system based on palladium icosahedra. Owing to lateral confinement imposed by twin boundaries and thus vertical relaxation only, the platinum overlayers evolve into a corrugated structure under compressive strain. For the core-shell nanocrystals with an average of 2.7 platinum overlayers, their specific and platinum mass activities towards oxygen reduction are enhanced by eight- and sevenfold, respectively, relative to a commercial catalyst. Density functional theory calculations indicate that the enhancement can bemore » attributed to the weakened binding of hydroxyl to the compressed platinum surface supported on palladium. After 10,000 testing cycles, the mass activity of the core-shell nanocrystals is still four times higher than the commercial catalyst. Ultimately, these results demonstrate an effective approach to the development of electrocatalysts with greatly enhanced activity and durability.« less

Nonenzymatic glucose detection by using a three-dimensionally ordered, macroporous platinum template.

PubMed

Song, Yan-Yan; Zhang, Dai; Gao, Wei; Xia, Xing-Hua

2005-03-18

A three-dimensionally ordered, macroporous, inverse-opal platinum film was synthesized electrochemically by the inverted colloidal-crystal template technique. The inverse-opal film that contains platinum nanoparticles showed improved electrocatalytic activity toward glucose oxidation with respect to the directly deposited platinum; this improvement is due to the interconnected porous structure and the greatly enhanced effective surface area. In addition, the inverse-opal Pt-film electrode responds more sensitively to glucose than to common interfering species of ascorbic acid, uric acid, and p-acetamidophenol due to their different electrochemical reaction mechanisms. Results showed that the ordered macroporous materials with enhanced selectivity and sensitivity are promising for fabrication of nonenzymatic glucose biosensors.

The use of precious-metal-modified nickel-based superalloys for thin gage applications

NASA Astrophysics Data System (ADS)

Ballard, Donna L.; Pilchak, Adam L.

2010-10-01

Precious-metal-modified nickel-based superalloys are being investigated for use in thin gage applications, such as thermal protection systems or heat exchangers, due to their strength and inherent oxidation resistance at temperatures in excess of 1,050°C. This overview paper summarizes the Air Force Research Laboratory (AFRL) interest in experimental two-phase γ-Ni + γ'-Ni3Al superalloys. The AFRL is interested in alloys with a based composition of Ni-15Al-5Cr (at. %) with carbon, boron, and zirconium additions for grain-boundary refinement and strengthening. The alloys currently being evaluated also contain 4-5 at.% of platinum-group metals, in this case platinum and iridium. The feasibility of hot rolling these alloys to a final thickness of 0.12-0.25 mm and obtaining a nearly fully recrystallized microstructure was demonstrated.

Coating Carbon Fibers With Platinum

NASA Technical Reports Server (NTRS)

Effinger, Michael R.; Duncan, Peter; Coupland, Duncan; Rigali, Mark J.

2007-01-01

A process for coating carbon fibers with platinum has been developed. The process may also be adaptable to coating carbon fibers with other noble and refractory metals, including rhenium and iridium. The coated carbon fibers would be used as ingredients of matrix/fiber composite materials that would resist oxidation at high temperatures. The metal coats would contribute to oxidation resistance by keeping atmospheric oxygen away from fibers when cracks form in the matrices. Other processes that have been used to coat carbon fibers with metals have significant disadvantages: Metal-vapor deposition processes yield coats that are nonuniform along both the lengths and the circumferences of the fibers. The electrical resistivities of carbon fibers are too high to be compatible with electrolytic processes. Metal/organic vapor deposition entails the use of expensive starting materials, it may be necessary to use a furnace, and the starting materials and/or materials generated in the process may be hazardous. The present process does not have these disadvantages. It yields uniform, nonporous coats and is relatively inexpensive. The process can be summarized as one of pretreatment followed by electroless deposition. The process consists of the following steps: The surfaces of the fiber are activated by deposition of palladium crystallites from a solution. The surface-activated fibers are immersed in a solution that contains platinum. A reducing agent is used to supply electrons to effect a chemical reduction in situ. The chemical reduction displaces the platinum from the solution. The displaced platinum becomes deposited on the fibers. Each platinum atom that has been deposited acts as a catalytic site for the deposition of another platinum atom. Hence, the deposition process can also be characterized as autocatalytic. The thickness of the deposited metal can be tailored via the duration of immersion and the chemical activity of the solution.

Enhanced vapour sensing using silicon nanowire devices coated with Pt nanoparticle functionalized porous organic frameworks.

PubMed

Cao, Anping; Shan, Meixia; Paltrinieri, Laura; Evers, Wiel H; Chu, Liangyong; Poltorak, Lukasz; Klootwijk, Johan H; Seoane, Beatriz; Gascon, Jorge; Sudhölter, Ernst J R; de Smet, Louis C P M

2018-04-19

Recently various porous organic frameworks (POFs, crystalline or amorphous materials) have been discovered, and used for a wide range of applications, including molecular separations and catalysis. Silicon nanowires (SiNWs) have been extensively studied for diverse applications, including as transistors, solar cells, lithium ion batteries and sensors. Here we demonstrate the functionalization of SiNW surfaces with POFs and explore its effect on the electrical sensing properties of SiNW-based devices. The surface modification by POFs was easily achieved by polycondensation on amine-modified SiNWs. Platinum nanoparticles were formed in these POFs by impregnation with chloroplatinic acid followed by chemical reduction. The final hybrid system showed highly enhanced sensitivity for methanol vapour detection. We envisage that the integration of SiNWs with POF selector layers, loaded with different metal nanoparticles will open up new avenues, not only in chemical and biosensing, but also in separations and catalysis.

Effects of para-substituents of styrene derivatives on their chemical reactivity on platinum nanoparticle surfaces

NASA Astrophysics Data System (ADS)

Hu, Peiguang; Chen, Limei; Deming, Christopher P.; Lu, Jia-En; Bonny, Lewis W.; Chen, Shaowei

2016-06-01

Stable platinum nanoparticles were successfully prepared by the self-assembly of para-substituted styrene derivatives onto the platinum surfaces as a result of platinum-catalyzed dehydrogenation and transformation of the vinyl groups to the acetylene ones, forming platinum-vinylidene/-acetylide interfacial bonds. Transmission electron microscopic measurements showed that the nanoparticles were well dispersed without apparent aggregation, suggesting sufficient protection of the nanoparticles by the organic capping ligands, and the average core diameter was estimated to be 2.0 +/- 0.3 nm, 1.3 +/- 0.2 nm, and 1.1 +/- 0.2 nm for the nanoparticles capped with 4-tert-butylstyrene, 4-methoxystyrene, and 4-(trifluoromethyl)styrene, respectively, as a result of the decreasing rate of dehydrogenation with the increasing Taft (polar) constant of the para-substituents. Importantly, the resulting nanoparticles exhibited unique photoluminescence, where an increase of the Hammett constant of the para-substituents corresponded to a blue-shift of the photoluminescence emission, suggesting an enlargement of the HOMO-LUMO band gap of the nanoparticle-bound acetylene moieties. Furthermore, the resulting nanoparticles exhibited apparent electrocatalytic activity towards oxygen reduction in acidic media, with the best performance among the series of samples observed with the 4-tert-butylstyrene-capped nanoparticles due to an optimal combination of the nanoparticle core size and ligand effects on the bonding interactions between platinum and oxygen species.Stable platinum nanoparticles were successfully prepared by the self-assembly of para-substituted styrene derivatives onto the platinum surfaces as a result of platinum-catalyzed dehydrogenation and transformation of the vinyl groups to the acetylene ones, forming platinum-vinylidene/-acetylide interfacial bonds. Transmission electron microscopic measurements showed that the nanoparticles were well dispersed without apparent aggregation, suggesting sufficient protection of the nanoparticles by the organic capping ligands, and the average core diameter was estimated to be 2.0 +/- 0.3 nm, 1.3 +/- 0.2 nm, and 1.1 +/- 0.2 nm for the nanoparticles capped with 4-tert-butylstyrene, 4-methoxystyrene, and 4-(trifluoromethyl)styrene, respectively, as a result of the decreasing rate of dehydrogenation with the increasing Taft (polar) constant of the para-substituents. Importantly, the resulting nanoparticles exhibited unique photoluminescence, where an increase of the Hammett constant of the para-substituents corresponded to a blue-shift of the photoluminescence emission, suggesting an enlargement of the HOMO-LUMO band gap of the nanoparticle-bound acetylene moieties. Furthermore, the resulting nanoparticles exhibited apparent electrocatalytic activity towards oxygen reduction in acidic media, with the best performance among the series of samples observed with the 4-tert-butylstyrene-capped nanoparticles due to an optimal combination of the nanoparticle core size and ligand effects on the bonding interactions between platinum and oxygen species. Electronic supplementary information (ESI) available: TGA curves and additional voltammograms. See DOI: 10.1039/c6nr02296k

Platinum nanocatalysts prepared with different surfactants for C1-C3 alcohol oxidations and their surface morphologies by AFM

NASA Astrophysics Data System (ADS)

Ertan, Salih; Şen, Fatih; Şen, Selda; Gökağaç, Gülsün

2012-06-01

In this study, platinum nanoparticle catalysts have been prepared using PtCl4 as a starting material and 1-octanethiol, 1-decanethiol, 1-dodecanethiol, and 1-hexadecanethiol as surfactants for methanol, ethanol, and 2-propanol oxidation reactions. The structure, particle sizes, and surface morphologies of the catalysts were characterized by X-ray diffraction (XRD), atomic force microscopy and transmission electron microscopy (TEM). XRD and TEM results indicate that all prepared catalysts have a face-centered cubic structure and are homogeneously dispersed on the carbon support with a narrow size distribution (2.0-1.3 nm). X-ray photoelectron spectra of the catalysts were examined and it is found that platinum has two different oxidation states, Pt (0) and Pt(IV), oxygen and sulfur compounds are H2Oads and OHads, bound and unbound thiols. The electrochemical and electrocatalytic properties of these catalysts were investigated with respect to C1-C3 alcohol oxidations by cyclic voltammetry and chronoamperometry. The highest electrocatalytic activity was obtained from catalyst I which was prepared with 1-octanethiol. This may be attributed to a decrease in the ratio of bound to unbound thiol species increase in Pt (0)/Pt(IV), H2Oads/OHads ratios, electrochemical surface area, CO tolerance and percent platinum utility.

Propitious Dendritic Cu2O-Pt Nanostructured Anodes for Direct Formic Acid Fuel Cells.

PubMed

El-Nagar, Gumaa A; Mohammad, Ahmad M; El-Deab, Mohamed S; El-Anadouli, Bahgat E

2017-06-14

This study introduces a novel competent dendritic copper oxide-platinum nanocatalyst (nano-Cu 2 O-Pt) immobilized onto a glassy carbon (GC) substrate for formic acid (FA) electro-oxidation (FAO); the prime reaction in the anodic compartment of direct formic acid fuel cells (DFAFCs). Interestingly, the proposed catalyst exhibited an outstanding improvement for FAO compared to the traditional platinum nanoparticles (nano-Pt) modified GC (nano-Pt/GC) catalyst. This was evaluated from steering the reaction mechanism toward the desired direct route producing carbon dioxide (CO 2 ); consistently with mitigating the other undesired indirect pathway producing carbon monoxide (CO); the potential poison deteriorating the catalytic activity of typical Pt-based catalysts. Moreover, the developed catalyst showed a reasonable long-term catalytic stability along with a significant lowering in onset potential of direct FAO that ultimately reduces the polarization and amplifies the fuel cell's voltage. The observed catalytic enhancement was believed to originate bifunctionally; while nano-Pt represented the base for the FA adsorption, nanostructured copper oxide (nano-Cu 2 O) behaved as a catalytic mediator facilitating the charge transfer during FAO and providing the oxygen atmosphere inspiring the poison's (CO) oxidation at relatively lower potential. Surprisingly, moreover, nano-Cu 2 O induced a surface retrieval of nano-Pt active sites by capturing the poisoning CO via "a spillover mechanism" to renovate the Pt surface for the direct FAO. Finally, the catalytic tolerance of the developed catalyst toward halides' poisoning was discussed.

Design of ultrasensitive bisphenol A-aptamer based on platinum nanoparticles loading to polyethyleneimine-functionalized carbon nanotubes.

PubMed

Derikvandi, Zeinab; Abbasi, Amir Reza; Roushani, Mahmoud; Derikvand, Zohreh; Azadbakht, Azadeh

2016-11-01

Here, a highly sensitive electrochemical aptasensor based on a novel signal amplification strategy for the determination of bisphenol A (BPA) was developed. Construction of the aptasensor began with the deposition of highly dispersed platinum nanoparticles (PtNPs)/acid-oxidized carbon nanotubes (CNTs-COOH) functionalized with polyethyleneimine (PEI) at the surface of glassy carbon (PtNPs/PEI/CNTs-COOH/GC) electrode. After immobilizing the amine-capped capture probe (ssDNA1) through the covalent amide bonds formed by the carboxyl groups on the nanotubes and the amino groups on the oligonucleotides, we employed a designed complementary BPA-aptamer (ssDNA2) as a detection probe to hybridize with the ssDNA1. By adding BPA as a target, the aptamer specifically bound to BPA and its end folded into a BPA-binding junction. Because of steric/conformational restrictions caused by aptamer-BPA complex formation at the surface of modified electrode, the interfacial electron transfer of [Fe(CN)6](3-/4-) as a probe was blocked. Sensitive quantitative detection of BPA was carried out by monitoring the decrease of differential pulse voltammetric responses of [Fe(CN)6](3-/4-) peak current with increasing BPA concentrations. The newly developed aptasensor embraced a number of attractive features such as ease of fabrication, low detection limit, excellent selectivity, good stability and a wide linear range with respect to BPA. Copyright © 2016 Elsevier Inc. All rights reserved.

Electrocatalysts having platium monolayers on palladium, palladium alloy, and gold alloy core-shell nanoparticles, and uses thereof

DOEpatents

Adzic, Radoslav; Mo, Yibo; Vukmirovic, Miomir; Zhang, Junliang

2010-12-21

The invention relates to platinum-coated particles useful as fuel cell electrocatalysts. The particles are composed of a noble metal or metal alloy core at least partially encapsulated by an atomically thin surface layer of platinum atoms. The invention particularly relates to such particles having a palladium, palladium alloy, gold alloy, or rhenium alloy core encapsulated by an atomic monolayer of platinum. In other embodiments, the invention relates to fuel cells containing these electrocatalysts and methods for generating electrical energy therefrom.

Methods of producing porous platinum-based catalysts for oxygen reduction

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

Erlebacher, Jonah D.; Snyder, Joshua D.

A porous metal that comprises platinum and has a specific surface area that is greater than 5 m 2/g and less than 75 m 2/g. A fuel cell includes a first electrode, a second electrode spaced apart from the first electrode, and an electrolyte arranged between the first and the second electrodes. At least one of the first and second electrodes is coated with a porous metal catalyst for oxygen reduction, and the porous metal catalyst comprises platinum and has a specific surface area that is greater than 5 m 2/g and less than 75 m 2/g. A method ofmore » producing a porous metal according to an embodiment of the current invention includes producing an alloy consisting essentially of platinum and nickel according to the formula Pt xNi 1-x, where x is at least 0.01 and less than 0.3; and dealloying the alloy in a substantially pH neutral solution to reduce an amount of nickel in the alloy to produce the porous metal.« less

Porous platinum-based catalysts for oxygen reduction

DOEpatents

Erlebacher, Jonah D; Snyder, Joshua D

2014-11-25

A porous metal that comprises platinum and has a specific surface area that is greater than 5 m.sup.2/g and less than 75 m.sup.2/g. A fuel cell includes a first electrode, a second electrode spaced apart from the first electrode, and an electrolyte arranged between the first and the second electrodes. At least one of the first and second electrodes is coated with a porous metal catalyst for oxygen reduction, and the porous metal catalyst comprises platinum and has a specific surface area that is greater than 5 m.sup.2/g and less than 75 m.sup.2/g. A method of producing a porous metal according to an embodiment of the current invention includes producing an alloy consisting essentially of platinum and nickel according to the formula Pt.sub.xNi.sub.1-x, where x is at least 0.01 and less than 0.3; and dealloying the alloy in a substantially pH neutral solution to reduce an amount of nickel in the alloy to produce the porous metal.

High frequency reference electrode

DOEpatents

Kronberg, J.W.

1994-05-31

A high frequency reference electrode for electrochemical experiments comprises a mercury-calomel or silver-silver chloride reference electrode with a layer of platinum around it and a layer of a chemically and electrically resistant material such as TEFLON around the platinum covering all but a small ring or halo' at the tip of the reference electrode, adjacent to the active portion of the reference electrode. The voltage output of the platinum layer, which serves as a redox electrode, and that of the reference electrode are coupled by a capacitor or a set of capacitors and the coupled output transmitted to a standard laboratory potentiostat. The platinum may be applied by thermal decomposition to the surface of the reference electrode. The electrode provides superior high-frequency response over conventional electrodes. 4 figs.

High frequency reference electrode

DOEpatents

Kronberg, James W.

1994-01-01

A high frequency reference electrode for electrochemical experiments comprises a mercury-calomel or silver-silver chloride reference electrode with a layer of platinum around it and a layer of a chemically and electrically resistant material such as TEFLON around the platinum covering all but a small ring or "halo" at the tip of the reference electrode, adjacent to the active portion of the reference electrode. The voltage output of the platinum layer, which serves as a redox electrode, and that of the reference electrode are coupled by a capacitor or a set of capacitors and the coupled output transmitted to a standard laboratory potentiostat. The platinum may be applied by thermal decomposition to the surface of the reference electrode. The electrode provides superior high-frequency response over conventional electrodes.

Nanostructured gold and platinum electrodes on silicon structures for biosensing

NASA Astrophysics Data System (ADS)

Ogurtsov, V. I.; Sheehan, M. M.

2005-01-01

Gold and platinum metal electrodes on Si/SiO2 having undergone anisotropic potassium hydroxide (KOH) etch treatment are considered. This treatment etches at different rates and directions in the material resulting in creation of numerous pyramid shaped holes in the silicon substrate. This surface is used to make metal electrodes with increased electrode efficiency. The electrodes can serve as the sensors or as the sensor substrates (for surface polymer modification) and because both gold and platinum are inert they have applications for food safety biosensing. Wine, an economically significant food product, was chosen as a matrix, and impedance spectroscopy (EIS) was selected as a method of investigation of electrode behaviour. Based on results of EIS, different complexity equivalent circuits were determined by applying fitting mean square root optimisation of sensor complex impedance measurements.

Targeting RNA polymerase I transcription machinery in cancer cells by a novel monofunctional platinum-based agent.

PubMed

Zhang, Zhen-Lei; Zhao, Chun-Lai; Chen, Qian; Xu, Kai; Qiao, Xin; Xu, Jing-Yuan

2018-06-01

Aberrant ribosome biogenesis and enlarged nucleoli have long been used by pathologists as a marker of aggressive tumors. Suppression of RNA polymerase I (Pol I) transcription machinery within the nucleolus could be a direct way to trigger the nucleolar stress and to inhibit the rapid proliferation of cancer cells. Here we modified cisplatin with an analogue of the selective inhibitor of RNA polymerase I-mediated transcription BMH-21 to develop a novel platinum-based Pol I selective inhibitor. We show that this novel monofunctional platinum-based agent, P1-B1, had enhanced antitumor activity of up to 17-fold greater than the clinical drug cisplatin in cisplatin-resistant non-small cell lung cancer cells. P1-B1 also had significantly lower cytotoxicity compared to cisplatin as well as the Pol I selective inhibitor BMH-21 in MRC-5 normal lung fibroblast cells, and the selectivity index (SI) greatly increases. Mechanistic investigations revealed that P1-B1 displayed significant nucleolar accumulation, selectively inhibited Pol I transcription, and induced nucleolar stress, leading to S-phase arrest and apoptosis. Our results suggest that the effects of P1-B1 are mechanistically distinct from those of conventional platinum agents and the recently described non-classical platinum compounds and that functionalizing platinum-based agents with directly Pol I transcription inhibition properties may represent an improved modality for cancer treatment. Copyright © 2018 Elsevier Masson SAS. All rights reserved.

Citric acid functionalized carbon materials for fuel cell applications

NASA Astrophysics Data System (ADS)

Poh, Chee Kok; Lim, San Hua; Pan, Hui; Lin, Jianyi; Lee, Jim Yang

Carbon materials can be easily functionalized using citric acid (CA) treatment. The CA modification of carbon materials is both simple and effective. It requires no prolonged heating, filtration and washing, and produces more functional groups such as carboxyl and hydroxide on CA-modified carbon nanotubes and XC72 carbon blacks than on HNO 3-H 2SO 4 oxidized carbon nanotubes and as-purchased XC72. Platinum nanoparticles are deposited on these functionalized carbon materials by means of a microwave-assisted polyol process. The investigations using TEM, XRD, FTIR and TGA indicate that CA modification creates more functional groups and thus deposits more Pt nanoparticles with smaller average particle size on the surface of carbon materials. Electrochemical studies of the Pt/C samples for methanol oxidation reveal higher activity for Pt on CA-modified carbon materials. It is therefore considered that this method can find important applications in reducing the cost and improving performance of proton-exchange membrane fuel cells.

Structures of 38-atom gold-platinum nanoalloy clusters

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

Ong, Yee Pin; Yoon, Tiem Leong; Lim, Thong Leng

2015-04-24

Bimetallic nanoclusters, such as gold-platinum nanoclusters, are nanomaterials promising wide range of applications. We perform a numerical study of 38-atom gold-platinum nanoalloy clusters, Au{sub n}Pt{sub 38−n} (0 ≤ n ≤ 38), to elucidate the geometrical structures of these clusters. The lowest-energy structures of these bimetallic nanoclusters at the semi-empirical level are obtained via a global-minimum search algorithm known as parallel tempering multi-canonical basin hopping plus genetic algorithm (PTMBHGA), in which empirical Gupta many-body potential is used to describe the inter-atomic interactions among the constituent atoms. The structures of gold-platinum nanoalloy clusters are predicted to be core-shell segregated nanoclusters. Gold atomsmore » are observed to preferentially occupy the surface of the clusters, while platinum atoms tend to occupy the core due to the slightly smaller atomic radius of platinum as compared to gold’s. The evolution of the geometrical structure of 38-atom Au-Pt clusters displays striking similarity with that of 38-atom Au-Cu nanoalloy clusters as reported in the literature.« less

Characterization of Platinum and Iridium Oxyhydrate Surface Layers from Platinum and Iridium Foils.

PubMed

Johnson, Benjamin; Ranjan, Chinmoy; Greiner, Mark; Arrigo, Rosa; Schuster, Manfred Erwin; Höpfner, Britta; Gorgoi, Mihaela; Lauermann, Iver; Willinger, Marc; Knop-Gericke, Axel; Schlögl, Robert

2016-07-07

Platinum and iridium polycrystalline foils were oxidized electrochemically through anodization to create thin platinum and iridium hydrous oxide layers, which were analyzed through laboratory photoelectron spectroscopy during heating and time series (temperature-programmed spectroscopy). The films contain oxygen in the form of bound oxides, water, and hydroxides and were investigated by depth profiling with high-energy photoelectron spectroscopy. The Pt films are unstable and begin to degrade immediately after removal from the electrolyte to form core-shell structures with a metallic inner core and a hydrous oxide outer shell almost devoid of Pt. However, evidence was found for metastable intermediate states of degradation; therefore, it may be possible to manufacture PtOx phases with increased stability. Heating the film to even 100 °C causes accelerated degradation, which shows that stoichiometric oxides such as PtO2 or PtO are not the active species in the electrolyte. The Ir films exhibit increased stability and higher surface Ir content, and gentle heating at low temperatures leads to a decrease in defect density. Although both layers are based on noble metals, their surface structures are markedly different. The complexity of such hydrous oxide systems is discussed in detail with the goal of identifying the film composition more precisely. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

SERS and DFT study of water on metal cathodes of silver, gold and platinum nanoparticles.

PubMed

Li, Jian-Feng; Huang, Yi-Fan; Duan, Sai; Pang, Ran; Wu, De-Yin; Ren, Bin; Xu, Xin; Tian, Zhong-Qun

2010-03-14

The observed surface-enhanced Raman scattering (SERS) spectra of water adsorbed on metal film electrodes of silver, gold, and platinum nanoparticles were used to infer interfacial water structures on the basis of the change of the electrochemical vibrational Stark tuning rates and the relative Raman intensity of the stretching and bending modes. To explain the increase of the relative Raman intensity ratio of the bending and stretching vibrations at the very negative potential region, density functional theory calculations provide the conceptual model. The specific enhancement effect for the bending mode was closely associated with the water adsorption structure in a hydrogen bonded configuration through its H-end binding to surface sites with large polarizability due to strong cathodic polarization. The present results allow us to propose that interfacial water molecules exist on these metal cathodes with different hydrogen bonding interactions, i.e., the HO-HH-Pt dihydrogen bond for platinum and the HO-HAg(Au) for silver and gold. This dihydrogen bonding configuration on platinum is further supported from observation of the Pt-H stretching band. Furthermore, the influences of the pH effect on SERS intensity and vibrational Stark effect on the gold electrode indicate that the O-H stretching SERS signals are enhanced in the alkaline solutions because of the hydrated hydroxide surface species adsorbed on the gold cathode.

Carbon monoxide tolerant electrocatalyst with low platinum loading and a process for its preparation

DOEpatents

Adzic, Radoslav; Brankovic, Stanko; Wang, Jia

2003-12-30

An electrocatalyst is provided for use in a fuel cell that has low platinum loading and a high tolerance to carbon monoxide poisoning. The fuel cell anode includes an electrocatalyst that has a conductive support material, ruthenium nanoparticles reduced in H.sub.2 and a Group VIII noble metal in an amount of between about 0.1 and 25 wt % of the ruthenium nanoparticles, preferably between about 0.5 and 15 wt %. The preferred Group VIII noble metal is platinum. In one embodiment, the anode can also have a perfluorinated polymer membrane on its surface.

Addition of platinum and silver nanoparticles to toughen dental porcelain.

PubMed

Fujieda, Tokushi; Uno, Mitsunori; Ishigami, Hajime; Kurachi, Masakazu; Wakamatsu, Nobukazu; Doi, Yutaka

2012-01-01

Several studies have investigated toughening porcelain that is layered over a frame or a core. The introduction of residual compressive stress to the surface of porcelain has been shown to be effective to strengthen it. In the present study, nanoparticles of precious metals of silver and platinum (rather than non-precious metals) were used to evaluate if they could increase the fracture resistance of porcelain. The addition of silver and platinum nanoparticles was found to improve the mechanical properties of porcelain since it increased both the Young's modulus and the fracture toughness of commercial porcelain.

Fabrication of sensitive enzymatic biosensor based on multi-layered reduced graphene oxide added PtAu nanoparticles-modified hybrid electrode

PubMed Central

Hossain, Md Faruk; Park, Jae Y.

2017-01-01

A highly sensitive amperometric glucose sensor was developed by immobilization of glucose oxidase (GOx) onto multi-layer reduced graphene oxide (MRGO) sheets decorated with platinum and gold flower-like nanoparticles (PtAuNPs) modified Au substrate electrode. The fabricated MRGO/PtAuNPs modified hybrid electrode demonstrated high electrocatalytic activities toward oxidation of H2O2, to which it had a wide linear response that ranged from 0.5 to 8 mM (R2 = 0.997), and high sensitivity of 506.25 μA/mMcm2. Furthermore, glucose oxidase-chitosan composite and cationic polydiallyldimethylammonium chloride (PDDA) were assembled by a casting method on the surface of MRGO/PtAuNPs modified electrode. This as-fabricated hybrid biosensor electrode exhibited high electrocatalytic activity for the detection of glucose in PBS. It demonstrated good analytical properties in terms of a low detection limit of 1 μM (signal-to-noise ratio of 3), short response time (3 s), high sensitivity (17.85 μA/mMcm2), and a wide linear range (0.01–8 mM) for glucose sensing. These results reveal that the newly developed sensing electrode offers great promise for new type enzymatic biosensor applications. PMID:28333943

New electrocatalysts for unitized regenerative fuel cell: Pt-Ir alloy deposited on the proton exchange membrane surface by impregnation-reduction method.

PubMed

Wan, Chieh-Hao; Wu, Chun-Lin; Lin, Meng-Tsun; Shih, Chihhsiong

2010-07-01

In this paper, a modified technique to prepare Pt-Ir catalyst layer on the proton exchange membrane (PEM) surface using the impregnation-reduction (IR) method is proposed to improve the electrocatalytic activity as well as the life cycle of the bifunctional oxygen electrode (BOE). The resulted electrocatalysts were characterized by the Scanning Electron Microscopy (SEM), X-ray Diffraction (XRD), Electron Probe Micro-Analysis (EPMA), and Transmission Electron Microscope (TEM). The electrocatalytic properties of the Pt-Ir layer on PEM surface for the oxygen reduction and water oxidation reactions as well as the life cycle of MEA were investigated. Experimental results showed that the Ir particles were dispersed densely in the platinum layer through the modified IR technique. The atomic ratio of Pt over Ir elements was 9:1, and the resulted thickness of the obtained Pt-Ir catalyst layer was about 1.0 microm. The Pt-Ir catalyst layer was composed of Pt layer doped with Ir nano-particles comprising nano Pt-Ir alloy phase. The large surface area of Ir core with Pt shell particles and the presence of nano Pt-Ir alloy phase led to a higher electrocatalytic activity of BOE. Due to the good binding between the Nafion membrane and the Pt-Ir alloy catalyst, as well as the composite structure of the resulted Pt-Ir, the life cycle of Unitized Regenerative Fuel Cell (URFC) is improved through this novel BOE.

Multi-walled carbon nanotubes decorated by platinum catalyst nanoparticles--examination and microanalysis using scanning and transmission electron microscopies.

PubMed

Guinel, M J-F; Brodusch, N; Verde-Gómez, Y; Escobar-Morales, B; Gauvin, R

2013-10-01

Carbon nanotubes (CNTs) decorated with platinum (Pt) nanoparticles (NPs) have been characterized using a cold field-emission scanning electron microscope (SEM) and a high resolution field-emission transmission electron microscope (TEM). With this particular composite material, the complementary nature of the two instruments was demonstrated. Although the long CNTs were found to be mostly bent and defective in some parts, the nucleation of Pt occurred randomly and uniformly covered the CNTs. The NPs displayed a large variation in size, were sometimes defective with twins and stacking faults, and were found to be faceted with the presence of surface steps. The shape and size of the NPs and the presence of defects may have significant consequences on the activity of the Pt catalyst material. Also, thin layers of platinum oxide were identified on the surface of some NPs. © 2013 The Authors Journal of Microscopy © 2013 Royal Microscopical Society.

Nanofiber-deposited porous platinum enables glucose fuel cell anodes with high current density in body fluids

NASA Astrophysics Data System (ADS)

Frei, Maxi; Erben, Johannes; Martin, Julian; Zengerle, Roland; Kerzenmacher, Sven

2017-09-01

The poisoning of platinum anodes by body-fluid constituents such as amino acids is currently the main hurdle preventing the application of abiotic glucose fuel cells as battery-independent power supply for medical implants. We present a novel anode material that enables continuous operation of glucose oxidation anodes in horse serum for at least 30 days at a current density of (7.2 ± 1.9) μA cm-2. The fabrication process is based on the electro-deposition of highly porous platinum onto a 3-dimensional carbon nanofiber support, leading to approximately 2-fold increased electrode roughness factors (up to 16500 ± 2300). The material's superior performance is not only related to its high specific surface area, but also to an improved catalytic activity and/or poisoning resistance. Presumably, this results from the micro- and nanostructure of the platinum deposits. This represents a major step forward in the development of implantable glucose fuel cells based on long-term stable platinum electrodes.

Rapid epitaxy-free graphene synthesis on silicidated polycrystalline platinum

PubMed Central

Babenko, Vitaliy; Murdock, Adrian T.; Koós, Antal A.; Britton, Jude; Crossley, Alison; Holdway, Philip; Moffat, Jonathan; Huang, Jian; Alexander-Webber, Jack A.; Nicholas, Robin J.; Grobert, Nicole

2015-01-01

Large-area synthesis of high-quality graphene by chemical vapour deposition on metallic substrates requires polishing or substrate grain enlargement followed by a lengthy growth period. Here we demonstrate a novel substrate processing method for facile synthesis of mm-sized, single-crystal graphene by coating polycrystalline platinum foils with a silicon-containing film. The film reacts with platinum on heating, resulting in the formation of a liquid platinum silicide layer that screens the platinum lattice and fills topographic defects. This reduces the dependence on the surface properties of the catalytic substrate, improving the crystallinity, uniformity and size of graphene domains. At elevated temperatures growth rates of more than an order of magnitude higher (120 μm min−1) than typically reported are achieved, allowing savings in costs for consumable materials, energy and time. This generic technique paves the way for using a whole new range of eutectic substrates for the large-area synthesis of 2D materials. PMID:26175062

Controlled surface segregation leads to efficient coke-resistant nickel/platinum bimetallic catalysts for the dry reforming of methane

DOE PAGES

Li, Lidong; Zhou, Lu; Ould-Chikh, Samy; ...

2015-02-03

Surface composition and structure are of vital importance for heterogeneous catalysts, especially for bimetallic catalysts, which often vary as a function of reaction conditions (known as surface segregation). The preparation of bimetallic catalysts with controlled metal surface composition and structure is very challenging. In this study, we synthesize a series of Ni/Pt bimetallic catalysts with controlled metal surface composition and structure using a method derived from surface organometallic chemistry. The evolution of the surface composition and structure of the obtained bimetallic catalysts under simulated reaction conditions is investigated by various techniques, which include CO-probe IR spectroscopy, high-angle annular dark-field scanningmore » transmission electron microscopy, energy-dispersive X-ray spectroscopy, extended X-ray absorption fine structure analysis, X-ray absorption near-edge structure analysis, XRD, and X-ray photoelectron spectroscopy. It is demonstrated that the structure of the bimetallic catalyst is evolved from Pt monolayer island-modified Ni nanoparticles to core–shell bimetallic nanoparticles composed of a Ni-rich core and a Ni/Pt alloy shell upon thermal treatment. As a result, these catalysts are active for the dry reforming of methane, and their catalytic activities, stabilities, and carbon formation vary with their surface composition and structure.« less

Colorimetric assay of heparin in plasma based on the inhibition of oxidase-like activity of citrate-capped platinum nanoparticles.

PubMed

You, Jyun-Guo; Liu, Yao-Wen; Lu, Chi-Yu; Tseng, Wei-Lung; Yu, Cheng-Ju

2017-06-15

We report citrate-capped platinum nanoparticles (Pt NPs) as oxidase mimetics for effectively catalyzing the oxidation of 3,3',5,5'-tetramethylbenzidine (TMB), 2,2'-azino-bis (3-ethylbenzthiazoline-6-sulfonic acid), dopamine, and methylene blue in the presence of O 2 . To confirm oxidase-like activity of citrate-capped Pt NPs, their activity toward oxygen reduction reaction was studied using cyclic voltammetry and rotating ring-disk electrode method. The results obtained showed that Pt NP NPs can catalyze the oxidation of organic substrates to the colored product and the reduction of oxygen to water through a four-electron exchange process. Because the aggregation of Pt NPs can inhibit their oxidase-like activity and protamine can recognize heparin, we prepared the protamine-modified Pt NPs through direct adsorption on the surface of citrate-capped Pt NPs. The electrostatic attraction between heparin and protamine-stabilized Pt NPs induced nanoparticle aggregation, inhibiting their catalytic activity. Therefore, the lowest detectable heparin concentrations through UV-vis absorption and by the naked eye were estimated to be 0.3 and 60nM, respectively. Moreover, the proposed system enabled the determination of the therapeutic heparin concentration in a single drop of blood. Copyright © 2016 Elsevier B.V. All rights reserved.

Electron transfer processes occurring on platinum neural stimulating electrodes: pulsing experiments for cathodic-first, charge-balanced, biphasic pulses for 0.566  ⩽  k  ⩽  2.3 in rat subcutaneous tissues

NASA Astrophysics Data System (ADS)

Kumsa, Doe W.; Bhadra, Narendra; Hudak, Eric M.; Mortimer, J. Thomas

2017-10-01

Objective. Our mission is twofold: (1) find a way to safely inject more charge through platinum electrodes than the Shannon limit (k  =  1.75) permits and (2) nurture an interest in the neural stimulation community to understand the electron transfer process occurring on neural stimulating electrodes. Approach. We report here on measurements of the electrode potential, performed on platinum neural stimulating electrodes in the subcutaneous space of an anesthetized rat under neural stimulation conditions. Main results. The results for six platinum electrodes with areas ranging from 0.2 mm2 to 12.7 mm2 were similar to prior results in sulfuric acid, except that the measured potentials were shifted negative 0.36 V because of the pH difference between the two media. The anodic ‘end’ potential, measured at t  =  20 ms after the onset of the biphasic current pulse, was the primary focus of the data collected because previous results had shown that as charge injection crosses the Shannon limit (k  =  1.75), this potential moves into a range where platinum surface oxidation and dissolution is likely to occur. The behavior of V e(t  =  20 ms) over a range of electrode surface areas studied was consistent with our sulfuric acid study. Implicit, but little noticed, in Shannon’s formulation is that small and large platinum electrodes behave the same in terms of k value; our data supports this idea. Significance. We hypothesize that the k  =  1.75 Shannon limit for safe stimulation designates a charge-injection boundary above which platinum toxicity becomes a relevant consideration for living cells around an electrode, a possibility that can be directly tested, and is a vital step forward in mission (1).

Electron transfer processes occurring on platinum neural stimulating electrodes: pulsing experiments for cathodic-first, charge-balanced, biphasic pulses for 0.566  ⩽  k  ⩽  2.3 in rat subcutaneous tissues.

PubMed

Kumsa, Doe W; Bhadra, Narendra; Hudak, Eric M; Mortimer, J Thomas

2017-10-01

Our mission is twofold: (1) find a way to safely inject more charge through platinum electrodes than the Shannon limit (k  =  1.75) permits and (2) nurture an interest in the neural stimulation community to understand the electron transfer process occurring on neural stimulating electrodes. We report here on measurements of the electrode potential, performed on platinum neural stimulating electrodes in the subcutaneous space of an anesthetized rat under neural stimulation conditions. The results for six platinum electrodes with areas ranging from 0.2 mm 2 to 12.7 mm 2 were similar to prior results in sulfuric acid, except that the measured potentials were shifted negative 0.36 V because of the pH difference between the two media. The anodic 'end' potential, measured at t  =  20 ms after the onset of the biphasic current pulse, was the primary focus of the data collected because previous results had shown that as charge injection crosses the Shannon limit (k  =  1.75), this potential moves into a range where platinum surface oxidation and dissolution is likely to occur. The behavior of V e (t  =  20 ms) over a range of electrode surface areas studied was consistent with our sulfuric acid study. Implicit, but little noticed, in Shannon's formulation is that small and large platinum electrodes behave the same in terms of k value; our data supports this idea. We hypothesize that the k  =  1.75 Shannon limit for safe stimulation designates a charge-injection boundary above which platinum toxicity becomes a relevant consideration for living cells around an electrode, a possibility that can be directly tested, and is a vital step forward in mission (1).

Evaluation of industrial platinum resistance thermometers

NASA Technical Reports Server (NTRS)

Daryabeigi, Kamran; Dillontownes, Lawrence A.; Alderfer, David W.

1987-01-01

The calibration and stability of four surface temperature measuring industrial platinum resistance thermometers for use in the temperature range -120 C to 160 C was investigated. It was found that the calibration formulation of the International Practical Temperature Scale of 1968 provided the most accurate calibration. It was also found that all the resistance thermometers suffered from varying degrees of instability and hysteresis.

21 CFR 177.1010 - Acrylic and modified acrylic plastics, semirigid and rigid.

Code of Federal Regulations, 2013 CFR

2013-04-01

...) Selection of extractability conditions. These are to be chosen as provided in § 176.170(c) of this chapter..., weighed platinum dish, evaporated to 2-5 milliliters on a nonsparking, low-temperature hot plate and dried...

21 CFR 177.1010 - Acrylic and modified acrylic plastics, semirigid and rigid.

Code of Federal Regulations, 2011 CFR

2011-04-01

...) Selection of extractability conditions. These are to be chosen as provided in § 176.170(c) of this chapter..., weighed platinum dish, evaporated to 2-5 milliliters on a nonsparking, low-temperature hot plate and dried...

21 CFR 177.1010 - Acrylic and modified acrylic plastics, semirigid and rigid.

Code of Federal Regulations, 2012 CFR

2012-04-01

...) Selection of extractability conditions. These are to be chosen as provided in § 176.170(c) of this chapter..., weighed platinum dish, evaporated to 2-5 milliliters on a nonsparking, low-temperature hot plate and dried...

Hydroisomerization of n-hexadecane: remarkable selectivity of mesoporous silica post-synthetically modified with aluminum

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

Sabyrov, Kairat; Musselwhite, Nathan; Melaet, Gérôme

As the impact of acids on catalytically driven chemical transformations is tremendous, fundamental understanding of catalytically relevant factors is essential for the design of more efficient solid acid catalysts. In this work, we employed a post-synthetic doping method to synthesize a highly selective hydroisomerization catalyst and to demonstrate the effect of acid strength and density, catalyst microstructure, and platinum nanoparticle size on the reaction rate and selectivity. Aluminum doped mesoporous silica catalyzed gas-phase n-hexadecane isomerization with remarkably high selectivity to monobranched isomers (~95%), producing a substantially higher amount of isomers than traditional zeolite catalysts. Mildly acidic sites generated by post-syntheticmore » aluminum grafting were found to be the main reason for its high selectivity. The flexibility of the post-synthetic doping method enabled us to systematically explore the effect of the acid site density on the reaction rate and selectivity, which has been extremely difficult to achieve with zeolite catalysts. We found that a higher density of Brønsted acid sites leads to higher cracking of n-hexadecane presumably due to an increased surface residence time. Furthermore, regardless of pore size and microstructure, hydroisomerization turnover frequency linearly increased as a function of Brønsted acid site density. In addition to strength and density of acid sites, platinum nanoparticle size affected catalytic activity and selectivity. The smallest platinum nanoparticles produced the most effective bifunctional catalyst presumably because of higher percolation into aluminum doped mesoporous silica, generating more 'intimate' metallic and acidic sites. Finally, the aluminum doped silica catalyst was shown to retain its remarkable selectivity towards isomers even at increased reaction conversions.« less

Hydroisomerization of n-hexadecane: remarkable selectivity of mesoporous silica post-synthetically modified with aluminum

DOE PAGES

Sabyrov, Kairat; Musselwhite, Nathan; Melaet, Gérôme; ...

2017-01-01

As the impact of acids on catalytically driven chemical transformations is tremendous, fundamental understanding of catalytically relevant factors is essential for the design of more efficient solid acid catalysts. In this work, we employed a post-synthetic doping method to synthesize a highly selective hydroisomerization catalyst and to demonstrate the effect of acid strength and density, catalyst microstructure, and platinum nanoparticle size on the reaction rate and selectivity. Aluminum doped mesoporous silica catalyzed gas-phase n-hexadecane isomerization with remarkably high selectivity to monobranched isomers (~95%), producing a substantially higher amount of isomers than traditional zeolite catalysts. Mildly acidic sites generated by post-syntheticmore » aluminum grafting were found to be the main reason for its high selectivity. The flexibility of the post-synthetic doping method enabled us to systematically explore the effect of the acid site density on the reaction rate and selectivity, which has been extremely difficult to achieve with zeolite catalysts. We found that a higher density of Brønsted acid sites leads to higher cracking of n-hexadecane presumably due to an increased surface residence time. Furthermore, regardless of pore size and microstructure, hydroisomerization turnover frequency linearly increased as a function of Brønsted acid site density. In addition to strength and density of acid sites, platinum nanoparticle size affected catalytic activity and selectivity. The smallest platinum nanoparticles produced the most effective bifunctional catalyst presumably because of higher percolation into aluminum doped mesoporous silica, generating more 'intimate' metallic and acidic sites. Finally, the aluminum doped silica catalyst was shown to retain its remarkable selectivity towards isomers even at increased reaction conversions.« less

Selecting the swimming mechanisms of colloidal particles: bubble propulsion versus self-diffusiophoresis.

PubMed

Wang, Sijia; Wu, Ning

2014-04-01

Bubble propulsion and self-diffusiophoresis are two common mechanisms that can drive autonomous motion of microparticles in hydrogen peroxide. Although microtubular particles, when coated with platinum in their interior concave surfaces, can propel due to the formation and release of bubbles from one end, the convex Janus particles usually do not generate any visible bubble. They move primarily due to the self-diffusiophoresis. Coincidentally, the platinum films on those particles were typically coated by physical evaporation. In this paper, we use a simple chemical deposition method to make platinum-polystyrene Janus dimers. Surprisingly, those particles are propelled by periodic growth and collapse of bubbles on the platinum-coated lobes. We find that both high catalytic activity and rough surface are necessary to change the propulsion mode from self-diffusiophoresis to bubble propulsion. Our Janus dimers, with combined geometric and interfacial anisotropy, also exhibit distinctive motions at the respective stages of bubble growth and collapse, which differ by 5-6 orders of magnitude in time. Our study not only provides insight into the link between self-diffusiophoresis and bubble propulsion but also reveals the intriguing impacts of the combined geometric and interfacial anisotropy on self-propulsion of particles.

Formic acid electrooxidation on thallium-decorated shape-controlled platinum nanoparticles: an improvement in electrocatalytic activity.

PubMed

Busó-Rogero, Carlos; Perales-Rondón, Juan V; Farias, Manuel J S; Vidal-Iglesias, Francisco J; Solla-Gullon, Jose; Herrero, Enrique; Feliu, Juan M

2014-07-21

Thallium modified shape-controlled Pt nanoparticles were prepared and their electrocatalytic activity towards formic acid electrooxidation was evaluated in 0.5 M sulfuric acid. The electrochemical and in situ FTIR spectroscopic results show a remarkable improvement in the electrocatalytic activity, especially in the low potential region (around 0.1-0.2 V vs. RHE). Cubic Pt nanoparticles modified with Tl were found to be more active than the octahedral Pt ones in the entire range of Tl coverages and potential windows. In situ FTIR spectra indicate that the promotional effect produced by Tl results in the inhibition of the poisoning step leading to COads, thus improving the onset potential for the complete formic acid oxidation to CO2. Chronoamperometric experiments were also performed at 0.2 V to evaluate the stability of the electrocatalysts at constant potential. Finally, experiments with different concentrations of formic acid (0.05-1 M) were also carried out. In all cases, Tl-modified cubic Pt nanoparticles result to be the most active. All these facts reinforce the importance of controlling the surface structure of the electrocatalysts to optimize their electrocatalytic properties.

Catalytic ozonation of paracetamol using commercial and Pt-supported nanocomposites of Al2O3: The impact of ultrasound.

PubMed

Ziylan-Yavaş, Asu; Ince, Nilsun H

2018-01-01

The study is the assessment of commercial γ-Al 2 O 3 and its sonolytically modified nanocomposite in catalytic ozonation of paracetamol (PCT), which is an emerging water contaminant and a highly reactive compound with ozone. The results showed that commercial alumina was ineffective regardless of the solution pH, due to the low affinity of the catalyst surface for PCT and the high reactivity of the solute with molecular ozone. The modified catalyst, which was synthesized by decoration of the original surface with nanoparticles of platinum provided considerable improvement in the performance of the catalyst, particularly in mineralization of the target compound. The presence of OH scavenging agents in solution markedly retarded the rate of PCT oxidation and organic carbon decay, to signal the importance of radical-mediated reaction mechanisms on the degradation of the compound. Finally, the attempt to accelerate the reactions by running them in the presence of ultrasound was found inadequate for the early oxidation, but highly adequate for the longer mineralization process. The failure was attributed to the diffusion of a large fraction of ozone into the gaseous cavity bubbles (reduced probability of direct reactions) and the extreme conditions of cavitation collapse that partially damaged the catalyst surface. The success (in mineralization) was explained by the shift of the reaction site from the bulk solution (poor adsorption on catalyst surfaces) to the solid surface and the gaseous cavity bubbles (via enhanced hydrophobicity), both being considerably more active reaction media. Copyright © 2017 Elsevier B.V. All rights reserved.

Fast batch injection analysis of H(2)O(2) using an array of Pt-modified gold microelectrodes obtained from split electronic chips.

PubMed

Pacheco, Bruno D; Valério, Jaqueline; Angnes, Lúcio; Pedrotti, Jairo J

2011-06-24

A fast and robust analytical method for amperometric determination of hydrogen peroxide (H(2)O(2)) based on batch injection analysis (BIA) on an array of gold microelectrodes modified with platinum is proposed. The gold microelectrode array (n=14) was obtained from electronic chips developed for surface mounted device technology (SMD), whose size offers advantages to adapt them in batch cells. The effect of the dispensing rate, volume injected, distance between the platinum microelectrodes and the pipette tip, as well as the volume of solution in the cell on the analytical response were evaluated. The method allows the H(2)O(2) amperometric determination in the concentration range from 0.8 μmolL(-1) to 100 μmolL(-1). The analytical frequency can attain 300 determinations per hour and the detection limit was estimated in 0.34 μmolL(-1) (3σ). The anodic current peaks obtained after a series of 23 successive injections of 50 μL of 25 μmolL(-1) H(2)O(2) showed an RSD<0.9%. To ensure the good selectivity to detect H(2)O(2), its determination was performed in a differential mode, with selective destruction of the H(2)O(2) with catalase in 10 mmolL(-1) phosphate buffer solution. Practical application of the analytical procedure involved H(2)O(2) determination in rainwater of São Paulo City. A comparison of the results obtained by the proposed amperometric method with another one which combines flow injection analysis (FIA) with spectrophotometric detection showed good agreement. Copyright © 2011 Elsevier B.V. All rights reserved.

In vitro biocompatibility and electrical stability of thick-film platinum/gold alloy electrodes printed on alumina

NASA Astrophysics Data System (ADS)

Carnicer-Lombarte, Alejandro; Lancashire, Henry T.; Vanhoestenberghe, Anne

2017-06-01

Objective. High-density electrode arrays are a powerful tool in both clinical neuroscience and basic research. However, current manufacturing techniques require the use of specialised techniques and equipment, which are available to few labs. We have developed a high-density electrode array with customisable design, manufactured using simple printing techniques and with commercially available materials. Approach. Electrode arrays were manufactured by thick-film printing a platinum-gold alloy (Pt/Au) and an insulating dielectric on 96% alumina ceramic plates. Arrays were conditioned in serum and serum-free conditions, with and without 1 kHz, 200 µA, charge balanced stimulation for up to 21 d. Array biocompatibility was assessed using an extract assay and a PC-12 cell contact assay. Electrode impedance, charge storage capacity and charge injection capacity were before and after array conditioning. Main results. The manufactured Pt/Au electrodes have a highly porous surface and exhibit electrical properties comparable to arrays manufactured using alternative techniques. Materials used in array manufacture were found to be non-toxic to L929 fibroblasts by extract assay, and neuronal-like PC-12 cells adhered and extended neurites on the array surfaces. Arrays remained functional after long-term delivery of electrical pulses while exposed to protein-rich environments. Charge storage capacities and charge injection capacities increased following stimulation accounted for by an increase in surface index (real surface area) observed by vertical scanning interferometry. Further, we observed accumulation of proteins at the electrode sites following conditioning in the presence of serum. Significance. This study demonstrates the in vitro biocompatibility of commercially available thick-film printing materials. The printing technique is both simple and versatile, with layouts readily modified to produce customized electrode arrays. Thick-film electrode arrays are an attractive tool that may be implemented for general tissue engineering and neuroscience research.

Site-Dependent Vibrational Coupling of CO Adsorbates on Well-Defined Step and Terrace Sites of Monocrystalline Platinum: Mixed-Isotope Studies at Pt(335) and Pt(111) in the Aqueous Electrochemical Environment

DTIC Science & Technology

1994-09-15

and Terrace Sites of Monocrystalline Platinum: Mixed-Isotope Studies at Pt(335) and Pt(1 11) in the Aqueous Electrochemical Environment by Chung S. Kim... monocrystalline metals. These materials have structurally well-defined step and kink structures, which serve as models for the surface defect sites found on...and molecular interactions at stepped monocrystalline electrode surfaces [3,4]. A notable property of Pt(335)/CO is that the CO occupancy at step and

Rare isotope studies involving catalytic oxidation of CO over platinum-tin oxide

NASA Technical Reports Server (NTRS)

Upchurch, Billy T.; Wood, George M., Jr.; Hess, Robert V.; Hoyt, Ronald F.

1987-01-01

Results of studies utilizing normal and rare oxygen isotopes in the catalytic oxidation of carbon monoxide over a platinum-tin oxide catalyst substrate are presented. Chemisorption of labeled carbon monoxide on the catalyst followed by thermal desorption yielded a carbon dioxide product with an oxygen-18 composition consistent with the formation of a carbonate-like intermediate in the chemisorption process. The efficacy of a method developed for the oxygen-18 labeling of the platinum-tin oxide catalyst surface for use in closed cycle pulsed care isotope carbon dioxide lasers is demonstrated for the equivalent of 10 to the 6th power pulses at 10 pulses per second.

Architecting Graphene Oxide Rolled-Up Micromotors: A Simple Paper-Based Manufacturing Technology.

PubMed

Baptista-Pires, Luis; Orozco, Jahir; Guardia, Pablo; Merkoçi, Arben

2018-01-01

A graphene oxide rolled-up tube production process is reported using wax-printed membranes for the fabrication of on-demand engineered micromotors at different levels of oxidation, thickness, and lateral dimensions. The resultant graphene oxide rolled-up tubes can show magnetic and catalytic movement within the addition of magnetic nanoparticles or sputtered platinum in the surface of graphene-oxide-modified wax-printed membranes prior to the scrolling process. As a proof of concept, the as-prepared catalytic graphene oxide rolled-up micromotors are successfully exploited for oil removal from water. This micromotor production technology relies on an easy, operator-friendly, fast, and cost-efficient wax-printed paper-based method and may offer a myriad of hybrid devices and applications. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Article having an improved platinum-aluminum-hafnium protective coating

NASA Technical Reports Server (NTRS)

Nagaraj, Bangalore Aswatha (Inventor); Williams, Jeffrey Lawrence (Inventor)

2005-01-01

An article protected by a protective coating has a substrate and a protective coating having an outer layer deposited upon the substrate surface and a diffusion zone formed by interdiffusion of the outer layer and the substrate. The protective coating includes platinum, aluminum, no more than about 2 weight percent hafnium, and substantially no silicon. The outer layer is substantially a single phase.

Compatibility of grain-stabilized platinum with candidate propellants for resistojets

NASA Technical Reports Server (NTRS)

Whalen, M. V.; Grisnik, S. P.

1985-01-01

Resistojets are candidates for space station auxiliary propulsion, and should be characterized by both long life and multipropellant operations, requirements limited by available materials. Grain stabilized platinum is examined for use as a resistojet thruster material. Use of platinum in other applications indicates it can be used at moderately high temperatures for extended periods of time. Past results indicate that grain-stabilized platinum should be sufficiently inert in candidate propellant environments. Therefore, compatibility of platinum-yttria (P/Y2O3) and platinum-zirconia (Pt/ZrO2) with carbon dioxide, methane, hydrogen and ammonia is examined. A series of 1000 hr tests in CO2, H2, and NH3 is conducted at 1400 C and a series of 1000 hr tests in CH4 is conducted at about 500 C. Scanning electron microscopy, Auger electron spectroscopy and depth profiling analysis are then used to determine the effects of propellants on the material surface, to evaluate possible material contamination and to evaluate grain growth. The results indicate that there is carbon deposition on the surface of the Pt/Y2O3 and Pt/ZrO2 in both the CO2 and CH4 environments. In the H2 environment, the Pt/Y2O3 and Pt/ZrO2 specimen surfaces are roughened. After exposure to the NH3 environment, the Pt/Y2O3 and Pt/ZrO2 are roughened and pitted over the entire heated area with some pitted areas along the grain boundaries. SEM photos show grain growth in cross-sectional views of all the Pt/Y2O3 samples and the Pt/ZrO2 samples, except that tested in methane. Mass loss measurements indicate that Pt/Y2O3 and Pt/ZrO2 would last in excess of 200,000 hr in each propellant environment. However, in NH3 both Pt/Y2O3 and Pt/ZrO2 are severely pitted, with voids up to 50 percent into the material. Pt/Y2O3 and Pt/ZrO2 are not recommended for high temperature service in NH3.

A Study of Iron-Nitrogen-Carbon Fuel Cell Catalysts: Chemistry - Nanostructure - Performance

NASA Astrophysics Data System (ADS)

Workman, Michael J., Jr.

Fuel cells have the potential to be a pollution-free, low-cost, and energy efficient alternative to the internal combustion engine for transportation and small-scale stationary power applications. The current state of fuel cell technology has already achieved two of these three lofty goals. The remaining barrier to wide-scale deployment is the high cost, which is primarily caused by dependence on large amounts of platinum to catalyze the energy conversion reactions. To overcome this barrier and facilitate the integration of fuel cells into mainstream applications, research into a new class of catalyst materials that do not require platinum is needed. There has been a significant amount of research effort directed toward the development of platinum-group metal free (PGM-free) catalysts, yet there is a lack of consensus on both the engineering parameters necessary to improve the technology and the fundamental science that would facilitate rational design. I have engaged in research on PGM-free catalysts based on inexpensive and abundant reagents, specifically: nicarbazin and iron. Catalysts made from these precursors have previously proven to be among the best PGM-free catalysts, but their continued advancement suffered from the same lack of understanding that besets all catalysts in this class. The work I have performed address both engineering concerns and fundamental underlying principles. I present results demonstrating correlations between physical structure, chemical speciation, and synthesis parameters, as well as addressing active site chemistry and likely locations. My research presented herein introduces new morphology analysis techniques and elucidates several key structure-to-property characteristics of catalysts derived from iron and nicarbazin. I discuss the development and application of a new length-scale specific surface analysis technique that allows for analysis of well-defined size ranges from a few nm to several microns. The existing technique of focused ion beam tomography is modified and optimized for platinum-group metal free catalyst layers, facilitating direct observation of catalyst integration into catalyst layers. I present evidence supporting the hypothesis that atomically dispersed iron coordinated with nitrogen are the dominant active sites in these catalysts. Further, that the concentration of surface oxides in the carbon structure, which can be directly influenced by synthesis parameters, correlates with both the concentration of active sites in the material and with fuel cell performance. Catalyst performance is hindered by the addition of carbon nanotubes and by the presence of metallic iron. Evidence consistent with the catalytic active sites residing in the graphitic plane is also presented.

Platinum nanoparticles: a non-toxic, effective and thermally stable alternative plasmonic material for cancer therapy and bioengineering.

PubMed

Samadi, Akbar; Klingberg, Henrik; Jauffred, Liselotte; Kjær, Andreas; Bendix, Poul Martin; Oddershede, Lene B

2018-05-17

Absorption of near infrared (NIR) light by metallic nanoparticles can cause extreme heating and is of interest for instance in cancer treatment since NIR light has a relatively large penetration depth into biological tissue. Here, we quantify the extraordinary thermoplasmonic properties of platinum nanoparticles and demonstrate their efficiency in photothermal cancer therapy. Although platinum nanoparticles are extensively used for catalysis, they are much overlooked in a biological context. Via direct measurements based on a biological matrix we show that individual irradiated platinum nanoparticles with diameters of 50-70 nm can easily reach surface temperatures up to 900 K. In contrast to gold nanoshells, which are often used for photothermal purposes, we demonstrate that the platinum particles remain stable at these extreme temperatures. The experiments are paralleled by finite element modeling confirming the experimental results and establishing a theoretical understanding of the particles' thermoplasmonic properties. At extreme temperatures it is likely that a vapor layer will form around the plasmonic particle, and we show this scenario to be consistent with direct measurements and simulations. Viability studies demonstrate that platinum nanoparticles themselves are non-toxic at therapeutically relevant concentrations, however, upon laser irradiation we show that they efficiently kill human cancer cells. Therefore, platinum nanoparticles are highly promising candidates for thermoplasmonic applications in the life sciences, in nano-medicine, and for bio-medical engineering.

Exposure of the German general population to platinum and rhodium - Urinary levels and determining factors.

PubMed

Munker, Sven; Kilo, Sonja; Röß, Christoph; Jeitner, Peter; Schierl, Rudolf; Göen, Thomas; Drexler, Hans

2016-11-01

In this study the exposure of the general population in Germany to platinum and rhodium and its determinants was investigated in 259 participants (subdivided in three groups) by urine analyses and assessment of the dental status. Complementary, an interview including questions characterising possible exposure to traffic exhaust was conducted. The median excretion was 2.42ng platinum/g creatinine and 7.27ng rhodium/g creatinine. The detailed analysis of the collected data showed significant higher platinum excretion values with increasing number of surfaces covered with restorations containing precious metals (R=0.389; p<0.001), but also higher values for habitants of urban areas (median=3.43ng/g creatinine; 95th percentile=25.2ng/g) compared with those of rural areas (median=2.06ng/g creatinine; 95th percentile=20.0ng/g). Also, participants working in urban areas showed higher platinum excretion values (median=3.27ng/g; 95th percentile=19.6ng/g). Male participants living and working next to highly frequented roads showed higher rhodium excretion values (median=7.27ng/g; 95th percentile=13.5 ng/g). In summary, the study showed that exhaust emissions have an influence on platinum and rhodium excretion, but for platinum this influence is rather low compared to the influence of precious metals containing restorations. Copyright © 2016 Elsevier GmbH. All rights reserved.

Inhibition of nuclear factor kappaB proteins-platinated DNA interactions correlates with cytotoxic effectiveness of the platinum complexes

PubMed Central

Brabec, Viktor; Kasparkova, Jana; Kostrhunova, Hana; Farrell, Nicholas P.

2016-01-01

Nuclear DNA is the target responsible for anticancer activity of platinum anticancer drugs. Their activity is mediated by altered signals related to programmed cell death and the activation of various signaling pathways. An example is activation of nuclear factor kappaB (NF-κB). Binding of NF-κB proteins to their consensus sequences in DNA (κB sites) is the key biochemical activity responsible for the biological functions of NF-κB. Using gel-mobility-shift assays and surface plasmon resonance spectroscopy we examined the interactions of NF-κB proteins with oligodeoxyribonucleotide duplexes containing κB site damaged by DNA adducts of three platinum complexes. These complexes markedly differed in their toxic effects in tumor cells and comprised highly cytotoxic trinuclear platinum(II) complex BBR3464, less cytotoxic conventional cisplatin and ineffective transplatin. The results indicate that structurally different DNA adducts of these platinum complexes exhibit a different efficiency to affect the affinity of the platinated DNA (κB sites) to NF-κB proteins. Our results support the hypothesis that structural perturbations induced in DNA by platinum(II) complexes correlate with their higher efficiency to inhibit binding of NF-κB proteins to their κB sites and cytotoxicity as well. However, the full generalization of this hypothesis will require to evaluate a larger series of platinum(II) complexes. PMID:27574114

Inhibition of nuclear factor kappaB proteins-platinated DNA interactions correlates with cytotoxic effectiveness of the platinum complexes.

PubMed

Brabec, Viktor; Kasparkova, Jana; Kostrhunova, Hana; Farrell, Nicholas P

2016-08-30

Nuclear DNA is the target responsible for anticancer activity of platinum anticancer drugs. Their activity is mediated by altered signals related to programmed cell death and the activation of various signaling pathways. An example is activation of nuclear factor kappaB (NF-κB). Binding of NF-κB proteins to their consensus sequences in DNA (κB sites) is the key biochemical activity responsible for the biological functions of NF-κB. Using gel-mobility-shift assays and surface plasmon resonance spectroscopy we examined the interactions of NF-κB proteins with oligodeoxyribonucleotide duplexes containing κB site damaged by DNA adducts of three platinum complexes. These complexes markedly differed in their toxic effects in tumor cells and comprised highly cytotoxic trinuclear platinum(II) complex BBR3464, less cytotoxic conventional cisplatin and ineffective transplatin. The results indicate that structurally different DNA adducts of these platinum complexes exhibit a different efficiency to affect the affinity of the platinated DNA (κB sites) to NF-κB proteins. Our results support the hypothesis that structural perturbations induced in DNA by platinum(II) complexes correlate with their higher efficiency to inhibit binding of NF-κB proteins to their κB sites and cytotoxicity as well. However, the full generalization of this hypothesis will require to evaluate a larger series of platinum(II) complexes.

Selection of a platinum-binding sequence in a loop of a four-helix bundle protein.

PubMed

Yagi, Sota; Akanuma, Satoshi; Kaji, Asumi; Niiro, Hiroya; Akiyama, Hayato; Uchida, Tatsuya; Yamagishi, Akihiko

2018-02-01

Protein-metal hybrids are functional materials with various industrial applications. For example, a redox enzyme immobilized on a platinum electrode is a key component of some biofuel cells and biosensors. To create these hybrid materials, protein molecules are bound to metal surfaces. Here, we report the selection of a novel platinum-binding sequence in a loop of a four-helix bundle protein, the Lac repressor four-helix protein (LARFH), an artificial protein in which four identical α-helices are connected via three identical loops. We created a genetic library in which the Ser-Gly-Gln-Gly-Gly-Ser sequence within the first inter-helical loop of LARFH was semi-randomly mutated. The library was then subjected to selection for platinum-binding affinity by using the T7 phage display method. The majority of the selected variants contained the Tyr-Lys-Arg-Gly-Tyr-Lys (YKRGYK) sequence in their randomized segment. We characterized the platinum-binding properties of mutant LARFH by using quartz crystal microbalance analysis. Mutant LARFH seemed to interact with platinum through its loop containing the YKRGYK sequence, as judged by the estimated exclusive area occupied by a single molecule. Furthermore, a 10-residue peptide containing the YKRGYK sequence bound to platinum with reasonably high affinity and basic side chains in the peptide were crucial in mediating this interaction. In conclusion, we have identified an amino acid sequence, YKRGYK, in the loop of a helix-loop-helix motif that shows high platinum-binding affinity. This sequence could be grafted into loops of other polypeptides as an approach to immobilize proteins on platinum electrodes for use as biosensors among other applications. Copyright © 2017 The Society for Biotechnology, Japan. Published by Elsevier B.V. All rights reserved.

Modification of molybdenum disulfide in methanol solvent for hydrogen evolution reaction

NASA Astrophysics Data System (ADS)

Niyitanga, Theophile; Jeong, Hae Kyung

2018-05-01

Molybdenum disulfide is a promising catalyst to replace the expensive platinum as an electrocatalyst but needs to be modified to present excellent electrocatalytic properties. Herein, we successfully modify molybdenum disulfide in methanol solvent for hydrogen evolution reaction by using a simple hydrothermal method. Overpotential reduced to -0.6 V from -1.5 V, and energy band gap decreased from 1.73 eV to 1.58 eV after the modification. The modified molybdenum disulfide also demonstrated lower resistance (42 Ω) at high frequency (1000 kHz) compared with that (240 Ω) of the precursor, showing that conductivity of the modified molybdenum disulfide has improved.

Scaling behavior of the surface roughness of platinum films grown by oblique angle deposition

NASA Astrophysics Data System (ADS)

Dolatshahi-Pirouz, A.; Hovgaard, M. B.; Rechendorff, K.; Chevallier, J.; Foss, M.; Besenbacher, F.

2008-03-01

Thin platinum films with well-controlled rough surface morphologies are grown by e-gun evaporation at an oblique angle of incidence between the deposition flux and the substrate normal. Atomic force microscopy is used to determine the root-mean-square value w of the surface roughness on the respective surfaces. From the scaling behavior of w , we find that while the roughness exponent α remains nearly unchanged at about 0.90, the growth exponent β changes from 0.49±0.04 to 0.26±0.01 as the deposition angle approaches grazing incidence. The values of the growth exponent β indicate that the film growth is influenced by both surface diffusion and shadowing effects, while the observed change from 0.49 to 0.26 can be attributed to differences in the relative importance of diffusion and shadowing with the deposition angle.

The possibility of using platinum foils with a rippled surface as diffraction gratings

NASA Astrophysics Data System (ADS)

Korsukov, V. E.; Ankudinov, A. V.; Butenko, P. N.; Knyazev, S. A.; Korsukova, M. M.; Obidov, B. A.; Shcherbakov, I. P.

2014-09-01

The atomic structure and surface relief of thin cold-rolled platinum foils upon recrystallization annealing and loading under ultrahigh vacuum conditions have been studied by low energy electron diffraction (LEED), atomic force microscopy (AFM), and scanning tunneling microscopy (STM). The surface of samples upon high-temperature annealing and subsequent uniaxial extension of recrystallized Pt foils represents a fractal structure of unidirectional ripples on various spatial scales. The total fractal dimension of this surface is D GW = 2.3, while the fractal dimensions along and across ripples are D ‖ ≈ 1 and D ⊥ ≈ 1.3, respectively. The optical spectra of a halogen lamp and a PRK-2 mercury lamp were recorded using these rippled Pt foils as reflection diffraction gratings. It is shown that Pt foils with this surface relief can be used as reflection diffraction gratings for electromagnetic radiation in a broad spectral range.

Nanodroplet impact onto solid platinum surface: Spreading and bouncing

NASA Astrophysics Data System (ADS)

Lussier, Daniel; Ventikos, Yiannis

2009-11-01

The impact of droplets onto solid surfaces is found in a huge variety of natural and technological applications, from rain drops splashing on the pavement, to material manufacturing by molten droplet deposition. Taking inspiration from existing microfluidic technologies (i.e. lab-on-chip), there is increasing interest in the use of nanodroplets (D < 100 nm) for a number of applications such as drug delivery and semiconductor device manufacturing. However, as the size of the droplet is reduced into the nanoscale, the direct use of previously obtained macroscopic results is not guaranteed. At the nanoscale, important effects due to the molecular nature of the fluid, thermal fluctuations and reduced dimensionality can play a critical role in determining system dynamics. In this paper we present the results of large-scale, fully atomistic, three-dimensional molecular dynamics (MD) simulation of an argon nanodroplet (D = 18 nm, 54 000 atoms) impact onto a solid platinum surface, using the LAMMPS software package. The fluid argon is modeled using the well-known Lennard-Jones (LJ) potential, while the embedded-atom model (EAM) potential is used for the solid platinum. By varying both the impact velocities (10-1000 m/s) and the wettability of the solid surface a wide range of impact behaviors is observed, from smooth spreading, to bouncing recoil, pointing towards a wide array of potential applications.

Statistical Simulation of the Performance and Degradation of a PEMFC Membrane Electrode Assembly

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

Harvey, David; Bellemare-Davis, Alexander; Karan, Kunal

2012-07-01

A 1-D MEA Performance model was developed that considered transport of liquid water, agglomerate catalyst structure, and the statistical variation of the MEA characteristic parameters. The model was validated against a low surface area carbon supported catalyst across various platinum loadings and operational conditions. The statistical variation was found to play a significant role in creating noise in the validation data and that there was a coupling effect between movement in material properties with liquid water transport. Further, in studying the low platinum loaded catalyst layers it was found that liquid water played a significant role in the increasing themore » overall transport losses. The model was then further applied to study platinum dissolution via potential cycling accelerated stress tests, in which the platinum was found to dissolve nearest the membrane effectively resulting in reaction distribution shifts within the layer.« less

Carbon Nanotubes as Support in the Platinum-Catalyzed Hydrolytic Dehydrogenation of Ammonia Borane.

PubMed

Chen, Wenyao; Duan, Xuezhi; Qian, Gang; Chen, De; Zhou, Xinggui

2015-09-07

We report remarkable support effects for carbon nanotubes (CNTs) in the Pt/CNT-catalyzed hydrolytic dehydrogenation of ammonia borane. The origin of the support-dependent activity and durability is elucidated by combining the catalytic and durability testing with characterization by a range of spectroscopy and high-angle annular dark-field scanning transmission electron microscopy techniques and ICP analysis. The effects mainly arise from different electronic properties and different abilities for the adsorption of boron-containing species on platinum surfaces and changes in size and shape of the platinum particles during the reaction. Defect-rich CNTs in particular are a promising support material, as it not only enhances the platinum binding energy, leading to the highest hydrogen generation rate, but also inhibits the adsorption of boron-containing species and stabilizes the platinum nanoparticles to resist the agglomeration during the reaction, leading to the highest durability. The insights revealed herein may pave the way for the rational design of highly active and durable metal/carbon catalysts for the hydrolytic dehydrogenation of ammonia borane. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Oxygen reduction reaction on stepped platinum surfaces in alkaline media.

PubMed

Rizo, Ruben; Herrero, Enrique; Feliu, Juan M

2013-10-07

The oxygen reduction reaction (ORR) in 0.1 M NaOH on platinum single crystal electrodes has been studied using hanging meniscus rotating disk electrode configuration. Basal planes and stepped surfaces with (111) and (100) terraces have been employed. The results indicate that the Pt(111) electrode has the highest electrocatalytic activity among all the studied surfaces. The addition of steps on this electrode surface significantly diminishes the reactivity of the surface towards the ORR. In fact, the reactivity of the steps on the surfaces with wide terraces can be considered negligible with respect to that measured for the terrace. On the other hand, Pt(100) and Pt(110) electrodes have much lower activity than the Pt(111) electrode. These results have been compared with those obtained in acid media to understand the effect of the pH and the adsorbed OH on the mechanism. It is proposed that the surface covered by adsorbed OH is active for the reduction of the oxygen molecules.

Glutathione modified CdTe quantum dots as a label for studying DNA interactions with platinum based cytostatics.

PubMed

Ryvolova, Marketa; Smerkova, Kristyna; Chomoucka, Jana; Hubalek, Jaromir; Adam, Vojtech; Kizek, Rene

2013-03-01

Cisplatin, carboplatin, and oxaliplatin represent three generations of platinum based drugs applied successfully for cancer treatment. As a consequence of the employment of platinum based cytostatics in the cancer treatment, it became necessary to study the mechanism of their action. Current accepted opinion is the formation of Pt-DNA adducts, but the mechanism of their formation is still unclear. Nanomaterials, as a progressively developing branch, can offer a tool for studying the interactions of these drugs with DNA. In this study, fluorescent CdTe quantum dots (QDs, λem = 525 nm) were employed to investigate the interactions of platinum cytostatics (cisplatin, carboplatin, and oxaliplatin) with DNA fragment (500 bp, c = 25 μg/mL). Primarily, the fluorescent behavior of QDs in the presence of platinum cytostatics was monitored and major differences in the interaction of QDs with tested drugs were observed. It was found that the presence of carboplatin (c = 0.25 mg/mL) had no significant influence on QDs fluorescence; however cisplatin and oxaliplatin quenched the fluorescence significantly (average decrease of 20%) at the same concentration. Subsequently, the amount of platinum incorporated in DNA was determined by QDs fluorescence quenching. Best results were reached using oxaliplatin (9.4% quenching). Linear trend (R(2) = 0.9811) was observed for DNA platinated by three different concentrations of oxaliplatin (0.250, 0.125, and 0.063 mg/mL). Correlation with differential pulse voltammetric measurements provided linear trend (R(2) = 0.9511). As a conclusion, especially in the case of oxaliplatin-DNA adducts, the quenching was the most significant compared to cisplatin and nonquenching carboplatin. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Platinum(II)-dendrimer conjugates: synthesis and investigations on cytotoxicity, cellular distribution, platinum release, DNA, and protein binding.

PubMed

Kapp, Timo; Dullin, Anja; Gust, Ronald

2010-02-17

A set of polyamidoamine dendrimers were modified in such a way that they are able to act as carrier and drug delivery systems for cytostatics. The terminal binding of the non-proteinogenic D,L-2,3-diaminopropionic acid allowed the attachment of the cytotoxic PtX(2) moiety (X = Cl, I: A(PtI(2))(2), A(PtCl(2))(2), B(PtI(2))(2), B(PtCl(2))(2)), while the 2-carboxypentanedioic acid acted as leaving group for [meso-1,2-bis(4-fluorophenyl)ethylenediamine]platinum(II) ((m-4F-Pt)(3)C, (m-4F-Pt)(3)D). Poly(ethylene glycol) chains at C(PtI(2))(3) and C(PtCl(2))(3) as well as (m-4F-Pt)(3)C and (m-4F-Pt)(3)D mediated sufficient water solubility. Additional dansyl residues (B(PtI(2))(2) and (m-4F-Pt)(3)D) made a simultaneous determination of platinum (graphite furnace atomic absorption spectroscopy (GF-AAS)) and dendrimer (fluorimetry) possible. The ethylenediamine-terminated dendrimers were typically accumulated into MCF-7 cells in clathrin-dependent pathways and targeted the platinum moieties to the nuclear compartment. The highest intracellular platinum concentration and DNA binding caused the dendrimers A(PtX(2))(2) and B(PtX(2))(2). A coordinative DNA binding, however, is very unlikely because of low cytotoxic effects. (m-4F-Pt)(3)C and (m-4F-Pt)(3)D are labile conjugates and liberated the m-4F-Pt moiety in biological systems. The effects of these dendrimers were similar to that of the reference compounds m-4F-PtCl(2) and m-4F-Pt(H(2)O)(2).

MHD generator electrode development. Summary report, July 1, 1981-September 30, 1982

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

Rossing, B.R.; Buckman, R.W. Jr.; Pouchot, W.D.

Emphasis on this program was the development of and understanding wastage mechanism(s) of metallic electrodes which may be suitable alternatives to platinum anode material for use in long-term open cycle, coal-fired MHD generator operations. The laboratory tests simulate both modes of material wastage observed in MHD electrode operation; i.e., arc erosion (melting/vaporization) and electrochemical corrosion. Based on experimental results from the electrochemical tests at 1473/sup 0/K, the rank order listing of the materials tested for anode applications were platinum, E-Brite 26-1 modified with a five percent addition of platinum, chromium, IN 601, E-Brite 26-1, and 330 stainless steel ranked inmore » decreasing order. The rank order listing based on the arc erosion test was platinum, chromium, E-Brite 26-1, 330 stainless steel, and IN 601. The relative arc erosion resistance of materials based on the AVCO Mark VII generator test results gave a rank order of platinum, 330 stainless steel, IN 601, and E-Brite 26-1. Engineering tests under simulated open-cycle coal-fired MHD operating conditions were performed in the 500 kW Westinghouse Electrode System Test Facility (WESTF). Tests were conducted on candidate metallic anode materials (cold wall) and ceramic anode (hot wall) materials. A ten-hour duration cold wall slagging test was conducted on platinum, E-Brite 26-1, 330 stainless steel and IN 601 and the results were similar to those obtained for those materials in the AVCO Mark VII generator tests. Non-slagging, super hot (>1700/sup 0/C) wall hafnia-rare earth oxide electrodes were tested in a sulfurous, western coal-fired MHD environment. All four ceramic electrode pairs were destroyed. 20 references.« less

Insights into PEMFC Performance Degradation from HCl in Air

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

O Baturina; A Epshteyn; P Northrup

2011-12-31

The performance degradation of a proton exchange membrane fuel cell (PEMFC) is studied in the presence of HCl in the air stream. The cathode employing carbon-supported platinum nanoparticles (Pt/C) was exposed to 4 ppm HCl in air while the cell voltage was held at 0.6 V. The HCl poisoning results in generation of chloride and chloroplatinate ions on the surface of Pt/C catalyst as determined by a combination of electrochemical tests and ex-situ chlorine K-edge X-Ray absorption near-edge structure (XANES) spectroscopy. The chloride ions inhibit the oxygen reduction reaction (ORR) and likely affect the wetting properties of diffusion media/catalyst layer,more » while the chloroplatinate ions are responsible for enhanced platinum particle growth most likely due to platinum dissolution-redeposition. The chloride ions can cause corrosion of the Pt nanoparticles in the presence of aqueous HCl in air even if no potential is applied. Although the majority of chloride ions are desorbed from the Pt surface by hydrogen treatment of the cathode, they partially remain in the system and re-adsorb on platinum at cell voltages of 0.5-0.9 V. Chloride ions are removed from the system and fuel cell performance at 0.5-0.7 V is restored by multiple exposures to low potentials.« less

Effects of histidin-2-ylidene vs. imidazol-2-ylidene ligands on the anticancer and antivascular activity of complexes of ruthenium, iridium, platinum, and gold.

PubMed

Schmitt, Florian; Donnelly, Kate; Muenzner, Julienne K; Rehm, Tobias; Novohradsky, Vojtech; Brabec, Viktor; Kasparkova, Jana; Albrecht, Martin; Schobert, Rainer; Mueller, Thomas

2016-10-01

Couples of N-heterocyclic carbene complexes of ruthenium, iridium, platinum, and gold, each differing only in the carbene ligand being either 1,3-dimethylimidazol-2-ylidene (IM) or 1,3-dimethyl-N-boc-O-methylhistidin-2-ylidene (HIS), were assessed for their antiproliferative effect on seven cancer cell lines, their interaction with DNA, their cell cycle interference, and their vascular disrupting properties. In MTT [3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide] assays only the platinum complexes were cytotoxic at single-digit micromolar IC 50 concentrations with the (HIS)Pt complex being on average twice as active as the (IM)Pt complex. The former was highly efficacious against cisplatin-resistant HT-29 colon carcinoma cells where the latter had no effect. Both Pt complexes were accumulated by cancer cells and bound to double-helical DNA equally well. Only the (HIS)Pt complex modified the electrophoretic mobility of circular DNA in vitro due to the HIS ligand causing greater morphological changes to the DNA. Both platinum complexes induced accumulation of 518A2 melanoma cells in G2/M and S phase of the cell cycle. A disruption of blood vessels in the chorioallantoic membrane of fertilized chicken eggs was observed for both platinum complexes and the (IM)gold complex. The (HIS)platinum complex was as active as cisplatin in tumor xenografted mice while being tolerated better. We found that the HIS ligand may augment the cytotoxicity of certain antitumoral metal fragments in two ways: by acting as a transmembrane carrier increasing the cellular accumulation of the complex, and by initiating a pronounced distortion and unwinding of DNA. We identified a new (HIS)platinum complex which was highly cytotoxic against cancer cells including cisplatin-resistant ones. Copyright © 2016 Elsevier Inc. All rights reserved.

Nanoscale investigation of platinum nanoparticles on strontium titanium oxide grown via physical vapor deposition and atomic layer deposition

NASA Astrophysics Data System (ADS)

Christensen, Steven Thomas

This dissertation examines growth of platinum nanoparticles from vapor deposition on SrTiO3 using a characterization approach that combines imaging techniques and X-ray methods. The primary suite of characterization probes includes atomic force microscopy (AFM), grazing-incidence small-angle X-ray scattering (GISAXS), X-ray fluorescence (XRF), scanning electron microscopy (SEM), and X-ray absorption spectroscopy (XAS). The vapor deposition techniques include physical vapor deposition (PVD) by evaporation and atomic layer deposition (ALD). For the PVD platinum study, AFM/XRF showed ˜10 nm nanoparticles separated by an average of 100 nm. The combination of AFM, GISAXS, and XRF indicated that the nanoparticles observed with AFM were actually comprised of closely spaced, smaller nanoparticles. These conclusions were supported by high-resolution SEM. The unusual behavior of platinum nanoparticles to aggregate without coalescence or sintering was observed previously by other researchers using transmissision electron microscopy (TEM). Platinum nanoparticle growth was also investigated on SrTiO3 (001) single crystals using ALD to nucleate nanoparticles that subsequently grew and coalesced into granular films as the ALD progresses. The expected growth rate for the early stages of ALD showed a two-fold increase which was attributed to the platinum deposition occurring faster on the bare substrate. Once the nanoparticles had coalesced into a film, steady state ALD growth proceeded. The formation of nanoparticles was attributed to the atomic diffusion of platinum atoms on the surface in addition to direct growth from the ALD precursor gases. The platinum ALD nanoparticles were also studied on SrTiO3 nanocube powders. The SrTiO3 nanocubes average 60 nm on a side and the cube faces have a {001} orientation. The ALD proceeded in a similar fashion as on the single crystal substrates where the deposition rate was twice as fast as the steady state growth rate. The Pt nanoparticle size increased linearly starting at ˜0.7 nm for 1 ALD cycle to ˜3 nm for 5 ALD cycles. The platinum chemical state was also investigated using X-ray absorption spectroscopy. Platinum nanoparticles ˜1 nm or smaller tended to be oxidized. For larger nanoparticles, the platinum state systematically approached that of bulk platinum metal as the size (number of ALD cycles) increased. The platinum loading was exceptionally low, ˜10 -3 mg cm-2.

Effect of Nitrogen Post-Doping on a Commercial Platinum-Ruthenium/Carbon Anode Catalyst

DTIC Science & Technology

2014-02-15

polymer electrolyte membrane fuel cells ( PEMFCs ) closer to commercial viability. However, further improvements in fuel cell durability, particularly...have recently led to significant improvements [3e5]. The genesis of interest in modified carbon support materials for PEMFCs and DMFCs originated in

DcR3 binds to ovarian cancer via heparan sulfate proteoglycans and modulates tumor cells response to platinum with corresponding alteration in the expression of BRCA1

PubMed Central

2012-01-01

Background Overcoming platinum resistance is a major obstacle in the treatment of Epithelial Ovarian Cancer (EOC). In our previous work Decoy Receptor 3 (DcR3) was found to be related to platinum resistance. The major objective of this work was to define the cellular interaction of DcR3 with EOC and to explore its effects on platinum responsiveness. Methods We studied cell lines and primary cultures for the expression of and the cells ability to bind DcR3. Cells were cultured with DcR3 and then exposed to platinum. Cell viability was determined by MTT assay. Finally, the cells molecular response to DcR3 was studied using real time RT-PCR based differential expression arrays, standard RT-PCR, and Western blot. Results High DcR3 in the peritoneal cavity of women with EOC is associated with significantly shorter time to first recurrence after platinum based therapy (p = 0.02). None-malignant cells contribute DcR3 in the peritoneal cavity. The cell lines studied do not secrete DcR3; however they all bind exogenous DcR3 to their surface implying that they can be effected by DcR3 from other sources. DcR3s protein binding partners are minimally expressed or negative, however, all cells expressed the DcR3 binding Heparan Sulfate Proteoglycans (HSPGs) Syndecans-2, and CD44v3. DcR3 binding was inhibited by heparin and heparinase. After DcR3 exposure both SKOV-3 and OVCAR-3 became more resistant to platinum with 15% more cells surviving at high doses. On the contrary CaOV3 became more sensitive to platinum with 20–25% more cell death. PCR array analysis showed increase expression of BRCA1 mRNA in SKOV-3 and OVCAR-3 and decreased BRCA1 expression in CaOV-3 after exposure to DcR3. This was confirmed by gene specific real time PCR and Western blot analysis. Conclusions Non-malignant cells contribute to the high levels of DcR3 in ovarian cancer. DcR3 binds readily to EOC cells via HSPGs and alter their responsiveness to platinum chemotherapy. The paradoxical responses seen were related to the expression pattern of HSPGs available on the cells surface to interact with. Although the mechanism behind this is not completely known alterations in DNA repair pathways including the expression of BRCA1 appear to be involved. PMID:22583667

Theoretical studies of Pt-Ti nanoparticles for potential use as PEMFC electrocatalysts.

PubMed

Jennings, Paul C; Pollet, Bruno G; Johnston, Roy L

2012-03-07

A theoretical investigation is presented of alloying platinum with titanium to form binary Pt-Ti nanoalloys as an alternative to the expensive pure platinum catalysts commonly used for Proton Exchange Membrane Fuel Cell cathode electrocatalysts. Density Functional Theory calculations are performed to investigate compositional effects on structural properties as well as Oxygen Reduction Reaction kinetics and poisoning effects. High symmetry A(32)-B(6) clusters are studied to investigate structural properties. From these structures binding energies of hydroxyl and carbon monoxide are studied on a range of sites on the surface of the clusters. Promising results are obtained suggesting that the bimetallic Pt-Ti nanoalloys may exhibit enhanced properties compared to pure platinum catalysts.

Fabrication of SrTiO3 Layer on Pt Electrode for Label-Free Capacitive Biosensors

PubMed Central

Carapella, Giovanni; Pilloton, Roberto; Di Matteo, Marisa

2018-01-01

Due to their interesting ferroelectric, conductive and dielectric properties, in recent years, perovskite-structured materials have begun to attract increasing interest in the biosensing field. In this study, a strontium titanate perovskite layer (SrTiO3) has been synthesized on a platinum electrode and exploited for the development of an impedimetric label-free immunosensor for Escherichia coli O157:H7 detection. The electrochemical characterization of the perovskite-modified electrode during the construction of the immunosensor, as well as after the interaction with different E. coli O157:H7 concentrations, showed a reproducible decrease of the total capacitance of the system that was used for the analytical characterization of the immunosensor. Under optimized conditions, the capacitive immunosensor showed a linear relationship from to 1 to 7 log cfu/mL with a low detection limit of 1 log cfu/mL. Moreover, the atomic force microscopy (AFM) technique underlined the increase in roughness of the SrTiO3-modified electrode surface after antibody immobilization, as well as the effective presence of cells with the typical size of E. coli. PMID:29547521

Synthesis of a new π-conjugated redox oligomer: Electrochemical and optical investigation

NASA Astrophysics Data System (ADS)

Blili, Saber; Zaâboub, Zouhour; Maaref, Hassen; Haj Said, Ayoub

2017-01-01

A new π-conjugated redox oligomer was prepared according a two-Step Synthesis. Firstly, an oligophenylene (OMPA) was obtained from the anodic oxidation of the (4-methoxyphenyl)acetonitrile. Then, the resulting material was chemically modified by the Knoevenagel condensation with the ferrocenecarboxaldehyde. This reaction led to a redox-conjugated oligomer the Fc-OMPA. The synthesized material was characterized using different spectroscopic techniques: NMR, FTIR, UV-vis and photoluminescence (PL) spectroscopy. The Fc-OMPA was used to modify a platinum electrode surface and the electrochemical response of the ferrocene redox-center was investigated by cyclic voltammetry. Moreover, the room temperature PL spectra of Fc-OMPA revealed that the ferrocene moiety, which acts as an electron donor, can effectively quench the oligomer luminescence. However, when ferrocene was oxidized to ferrocenium ion, the intramolecular charge transfer process was prevented which consequently enhanced the light emission. Thus, the oligomer light-emission can be, chemically or electrochemically tuned. The obtained results showed that the prepared material is a good candidate for the elaboration of electrochemical sensors and for the development of luminescent Redox-switchable devices.

Hemispherical platinum : silver core : shell nanoparticles for miRNA detection.

PubMed

Spain, Elaine; Adamson, Kellie; Elshahawy, Mohammad; Bray, Isabella; Keyes, Tia E; Stallings, Raymond L; Forster, Robert J

2017-02-27

Defects within a self-assembled monolayer (SAM) of dodecanethiol on gold have been used as nucleation sites for the electrodeposition of mushroom shaped platinum nanoparticles (PtNPs). The top surfaces of these PtNPs were then decorated with a layer of silver creating a hemispherical - platinum : silver core : shell nanoparticle (Pt-AgNP). Thiolated probe strand miRNA was then immobilised onto the upper silver surface. These regioselectively modified particles were desorbed by applying a current jump to yield nanoparticles capable of hybridising to a complementary miRNA target with electrocatalysis occurring on the non-functionalized lower surface. A second electrode was functionalized with single stranded capture miRNA that has a sequence that is complementary to an miRNA, miR-132, associated with the childhood cancer, Neuroblastoma but leaves a section of the target available to bind the nucleic acid sequence on the core : shell Pt-AgNPs. Following hybridization of the target and capture strands the surface was exposed to the miRNA labelled electrocatalytic Pt-AgNPs. The concentration of the target was then determined by monitoring the current associated with the reduction of hydrogen peroxide in a solution of H 2 SO 4 . Calibration plots of the log[miRNA] vs. faradaic current were linear from 1 aM to 1 μM and aM concentrations could be detected without the need for chemical amplification of the target, e.g., using PCR or NASBA. The regioselectively modified particles were also immobilised within the interior of gold microcavity arrays via miRNA hybridisation and their Raman properties investigated.

From well-defined Pt(II) surface species to the controlled growth of silica supported Pt nanoparticles.

PubMed

Laurent, Pierre; Veyre, Laurent; Thieuleux, Chloé; Donet, Sébastien; Copéret, Christophe

2013-01-07

Silica-supported Pt nanoparticles were prepared from well-defined surface platinum(II) surface species, obtained by grafting of well-defined Pt(II) molecular precursors with specific ligands (Cl, Me, N(SiMe(3))(2), OSi(OtBu)(3)) onto silica partially dehydroxylated at 200 and 700 °C yielding well-defined platinum(II) surface species. This approach allowed for testing the effect of Pt density and ligands on nanoparticle size. Higher grafting densities are achieved on silica partially dehydroxylated at 200 °C due to its initially higher surface silanol density. Surface species have been synthesized from symmetrical and dissymmetrical complexes, namely (COD)Pt(Me)(2), (COD)Pt(OSi(OtBu)(3))(2), (COD)Pt(Me)(OSi(OtBu)(3)), (COD)Pt(Me)(N(SiMe(3))(2)), (COD)Pt(Cl)(N(SiMe(3))(2)) and (COD)Pt(N(SiMe(3))(2))(OSi(OtBu)(3)) yielding mono-grafted complexes of general formula (COD)Pt(R)(OSi≡) according to elemental analyses, diffuse reflectance infrared fourier transform (DRIFT) and carbon-13 solid-state nuclear magnetic resonance (NMR) spectroscopies. While the dimethyl-complex shows low reactivity towards grafting, bis-siloxy and dissymmetric complexes demonstrate better reactivity yielding platinum loadings up to 7.4 wt%. Upon grafting amido complexes, the surface passivation yielding Me(3)SiOSi≡ surface species is demonstrated. Nanoparticles have been synthesized from these well-defined surface species by reduction under H(2) at 300 °C, under static or flow conditions. This process yields nanoparticles with sizes ranging from 2 to 3.3 nm and narrow size dispersion from 0.5 to 1.2 nm. Interestingly, the chloride complex yields large nanoparticles from 5 to 40 nm demonstrating the strong influence of chloride over the nanoparticles growth.

Catalysis of a 1,3-dipolar reaction by distorted DNA incorporating a heterobimetallic platinum(ii) and copper(ii) complex.

PubMed

Rivilla, Iván; de Cózar, Abel; Schäfer, Thomas; Hernandez, Frank J; Bittner, Alexander M; Eleta-Lopez, Aitziber; Aboudzadeh, Ali; Santos, José I; Miranda, José I; Cossío, Fernando P

2017-10-01

A novel catalytic system based on covalently modified DNA is described. This catalyst promotes 1,3-dipolar reactions between azomethine ylides and maleimides. The catalytic system is based on the distortion of the double helix of DNA by means of the formation of Pt(ii) adducts with guanine units. This distortion, similar to that generated in the interaction of DNA with platinum chemotherapeutic drugs, generates active sites that can accommodate N -metallated azomethine ylides. The proposed reaction mechanism, based on QM(DFT)/MM calculations, is compatible with thermally allowed concerted (but asynchronous) [π4s + π2s] mechanisms leading to the exclusive formation of racemic endo -cycloadducts.

Formation of Platinum Catalyst on Carbon Black Using an In-Liquid Plasma Method for Fuel Cells.

PubMed

Show, Yoshiyuki; Ueno, Yutaro

2017-01-31

Platinum (Pt) catalyst was formed on the surface of carbon black using an in-liquid plasma method. The formed Pt catalyst showed the average particle size of 4.1 nm. This Pt catalyst was applied to a polymer electrolyte membrane fuel cell (PEMFC). The PEMFC showed an open voltage of 0.85 V and a maximum output power density of 216 mW/cm2.

Formation of Platinum Catalyst on Carbon Black Using an In-Liquid Plasma Method for Fuel Cells

PubMed Central

Show, Yoshiyuki; Ueno, Yutaro

2017-01-01

Platinum (Pt) catalyst was formed on the surface of carbon black using an in-liquid plasma method. The formed Pt catalyst showed the average particle size of 4.1 nm. This Pt catalyst was applied to a polymer electrolyte membrane fuel cell (PEMFC). The PEMFC showed an open voltage of 0.85 V and a maximum output power density of 216 mW/cm2. PMID:28336864

Heat-Flux Sensor For Hot Engine Cylinders

NASA Technical Reports Server (NTRS)

Kim, Walter S.; Barrows, Richard F.; Smith, Floyd A.; Koch, John

1989-01-01

Heat-flux sensor includes buried wire thermocouple and thin-film surface thermocouple, made of platinum and platinum with 13 percent rhodium. Sensor intended for use in ceramic-insulated, low-heat-rejection diesel engine at temperatures of about 1,000 K. Thermocouple junction resists environment in cylinder of advanced high-temperature diesel engine created by depositing overlapping films of Pt and 0.87 Pt/0.13 Rh on iron plug. Plug also contains internal thermocouple.

Gold-based thin multilayers for ohmic contacts in RF-MEMS switches

NASA Astrophysics Data System (ADS)

Mulloni, V.; Iannacci, J.; Bartali, R.; Micheli, V.; Colpo, S.; Laidani, N.; Margesin, B.

2011-06-01

In RF-MEMS switches many reliability issues are related to the metal contacts in the switching area. The characteristics of this contact influence not only contact resistance and insertion loss, but also the most relevant switch failure mechanisms that are wear of ohmic contact, adhesion and stiction. Gold is widely used for this purpose because of its good conductivity and chemical inertness, but is a soft metal, and the development of hard contact materials with low resistivity is of great interest for RF-MEMS switch reliability. It is possible to increase the contact hardness preserving the convenient gold properties alternating gold layers with thin layers of different metals. The material becomes harder not only by simple alloying but also by the presence of interfaces which act as barriers for mechanical dislocation migration. A detailed study of mechanical, electrical and morphological properties of gold-chromium, gold-platinum and gold-palladium multilayers is presented and discussed. It is found that the annealing treatments are important for tuning hardness values, and a careful choice of the alloying metal is essential when the material is inserted in a real switch fabrication cycle, because hardness improvements can vanish during oxygen plasma treatments usually involved in RF-switches fabrication. Platinum is the only metal tested that is unaffected by oxidation, and also modifies the chromium adhesion layer diffusion on the contact surface.

Electropolymerization of Uniform Polyaniline Nanorod Arrays on Conducting Oxides as Counter Electrodes in Dye-Sensitized Solar Cells.

PubMed

He, Ziming; Liu, Jing; Khoo, Si Yun; Tan, Timothy Thatt Yang

2016-01-01

Conventional techniques for the synthesis of oriented polyaniline (PANI) nanostructures are often complex or time consuming. Through an innovative reduced graphene oxide (rGO) modified FTO and a low-potential electropolymerization strategy, the rapid and template-free growth of a highly ordered PANI nanorod array on the FTO substrate is realized. The highly ordered nanostructure of the PANI array leads to a high electrocatalytic activity and chemical stability. The importance of the polymerization potential and rGO surface modification to achieve this nanostructure is revealed. Compared to platinum, the PANI nanorod array exhibits an enhanced performance and stability as counter electrodes in dye-sensitized solar cells, with a 17.6 % enhancement in power conversion efficiency. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Catalytic hydrogen sensing using microheated platinum nanoparticle-loaded graphene aerogel

DOE PAGES

Harley-Trochimczyk, Anna; Chang, Jiyoung; Zhou, Qin; ...

2014-10-02

We present that low power catalytic hydrogen sensors are fabricated by functionalizing low power polysilicon microheaters with platinum nanoparticle catalyst loaded in a high surface area graphene aerogel support. Fabrication and characterization of the polysilicon microheaters are described. The platinum nanoparticle-loaded graphene aerogel is characterized by transmission electron microscopy, scanning electron microscopy, and energy dispersive X-ray spectroscopy. Finally, the catalytic hydrogen sensors consume as little as 2.2 mW of power, have sensitivity of 1.6%/10,000 ppm hydrogen, a t90 response and recovery time of 0.97 s and 0.72 s, respectively, a lower detection limit of approximately 65 ppm, and negligible crossmore » sensitivity to methane, n-pentane, and diethylether.« less

Orientational behavior of thin films of poly(3-methylthiophene) on platinium: A FTIR and near edge x-ray absorption fine structure (NEXAFS) study

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

Yang, X.Q.; Chen, J.; Hale, P.D.

1988-01-01

Near edge x-ray absorption fine structure (NEXAFS) and infrared reflection-absorption spectroscopy (IRRAS) have been used to study the orientational behavior of thin films of poly(3-methylthiophene) electrochemically polymerized on a platinum surface. Clear orientational effects, with the thiophene rings predominantly oriented parallel to the platinum surface, were observed when the thickness of the polymer films were within a few hundred /angstrom/A. It was found that more highly ordered films were produced at lower polymerization potential (1.4V vs SCE) than at higher potential (1.8V vs SCE). 5 refs., 4 figs., 2 tabs.

Preparation and characterization of Fe3O4-Pt nanoparticles

NASA Astrophysics Data System (ADS)

Andrade, Ângela Leão; Cavalcante, Luis Carlos Duarte; Fabris, José Domingos; Pereira, Márcio César; Ardisson, José Domingos; Domingues, Rosana Zacarias

2017-11-01

Pt and Pt-based nanomaterials are active anticancer drugs for their ability to inhibit the division of living cells. Nanoparticles of magnetite containing variable proportions of platinum were prepared in the laboratory. The magnetite nanoparticles with platinum (Pt-Fe3O4) were obtained by reducing the Fe3+ of the maghemite ( γ Fe2O3) mixed with platinum (II) acetylacetonate and sucrose in two inversely coupled ceramic crucibles and heated in a furnace at 400 °C for 20 min. The formed carbon during this preparation acts to chemically reduce the ferric iron in maghemite. Moreover, its residual layer on the particle surface prevents the forming magnetite from oxidizing in air and helps retain the platinum in the solid mixture. The produced Pt-magnetite samples were characterized by 57Fe-Mössbauer spectroscopy, powder X-ray diffraction, scanning electron microscopy, and magnetization measurements. Measurements of AC magnetic-field-induced heating properties of the obtained nanocomposites, in aqueous solution, showed that they are suitable as a hyperthermia agent for biological applications.

Tracking the shape-dependent sintering of platinum-rhodium model catalysts under operando conditions

NASA Astrophysics Data System (ADS)

Hejral, Uta; Müller, Patrick; Balmes, Olivier; Pontoni, Diego; Stierle, Andreas

2016-03-01

Nanoparticle sintering during catalytic reactions is a major cause for catalyst deactivation. Understanding its atomic-scale processes and finding strategies to reduce it is of paramount scientific and economic interest. Here, we report on the composition-dependent three-dimensional restructuring of epitaxial platinum-rhodium alloy nanoparticles on alumina during carbon monoxide oxidation at 550 K and near-atmospheric pressures employing in situ high-energy grazing incidence x-ray diffraction, online mass spectrometry and a combinatorial sample design. For platinum-rich particles our results disclose a dramatic reaction-induced height increase, accompanied by a corresponding reduction of the total particle surface coverage. We find this restructuring to be progressively reduced for particles with increasing rhodium composition. We explain our observations by a carbon monoxide oxidation promoted non-classical Ostwald ripening process during which smaller particles are destabilized by the heat of reaction. Its driving force lies in the initial particle shape which features for platinum-rich particles a kinetically stabilized, low aspect ratio.

Surface kinetics for catalytic combustion of hydrogen-air mixtures on platinum at atmospheric pressure in stagnation flows

NASA Astrophysics Data System (ADS)

Ikeda, H.; Sato, J.; Williams, F. A.

1995-03-01

Experimental studies of the combustion of premixed hydrogen-air mixtures impinging on the surface of a heated platinum plate at normal atmospheric pressure were performed and employed to draw inferences concerning surface reaction mechanisms and rate parameters applicable under practical conditions of catalytic combustion. Plate and gas temperatures were measured by thermocouples, and concentration profiles of major stable species in the gas were measured by gas-chromatographic analyses of samples withdrawn by quartz probes. In addition, ignition and extinction phenomena were recorded and interpreted with the aid of a heat balance at the surface and a previous flow-field analysis of the stagnation-point boundary layer. From the experimental and theoretical results, conclusions were drawn concerning the surface chemical-kinetic mechanisms and values of the elementary rate parameters that are consistent with the observations. In particular, the activation energy for the surface oxidation step H + OH → H 2O is found to be appreciably less at these high surface coverages than in the low-coverage limit.

Size-dependent phase diagrams of metallic alloys: A Monte Carlo simulation study on order–disorder transitions in Pt–Rh nanoparticles

PubMed Central

Stahl, Christian; Albe, Karsten

2012-01-01

Summary Nanoparticles of Pt–Rh were studied by means of lattice-based Monte Carlo simulations with respect to the stability of ordered D022- and 40-phases as a function of particle size and composition. By thermodynamic integration in the semi-grand canonical ensemble, phase diagrams for particles with a diameter of 7.8 nm, 4.3 nm and 3.1 nm were obtained. Size-dependent trends such as the lowering of the critical ordering temperature, the broadening of the compositional stability range of the ordered phases, and the narrowing of the two-phase regions were observed and discussed in the context of complete size-dependent nanoparticle phase diagrams. In addition, an ordered surface phase emerges at low temperatures and low platinum concentration. A decrease of platinum surface segregation with increasing global platinum concentration was observed, when a second, ordered phase is formed inside the core of the particle. The order–disorder transitions were analyzed in terms of the Warren–Cowley short-range order parameters. Concentration-averaged short-range order parameters were used to remove the surface segregation bias of the conventional short-range order parameters. Using this procedure, it was shown that the short-range order in the particles at high temperatures is bulk-like. PMID:22428091

Bacterial adhesion affinities of various implant abutment materials.

PubMed

Yamane, Koichi; Ayukawa, Yasunori; Takeshita, Toru; Furuhashi, Akihiro; Yamashita, Yoshihisa; Koyano, Kiyoshi

2013-12-01

To investigate bacterial adhesion to various abutment materials. Thirty volunteers participated in this study. Resin splints were fabricated, and five types of disks were fabricated from pure titanium, gold-platinum alloy, zirconia, alumina, and hydroxyapatite with uniform surface roughness and attached to the buccal surface of each splint. After 4 days of use by the subjects, the plaque accumulated on the disk surfaces was analyzed. The bacterial community structure was evaluated using 16S rRNA gene profiling with terminal restriction fragment length polymorphism analysis. The total bacterial count on each disk was estimated using quantitative polymerase chain reaction. Terminal restriction fragment length polymorphism profiles were more similar between tested materials than between subjects, suggesting that the bacterial community structures on the abutment material were influenced more by the individuals than by the type of material. However, the total number of bacteria attached to a disk was significantly different among five materials (P < 0.001, Brunner-Langer test for longitudinal data). Fewer bacteria were attached to the gold-platinum alloy than to the other materials. Gold-platinum alloy appears to be useful material for abutments when considering the accumulation of plaque. However, alternative properties of the abutment material, such as effects on soft tissue healing, should also be taken into consideration when choosing an abutment material. © 2012 John Wiley & Sons A/S.

A novel electroless method to prepare a platinum electrocatalyst on diamond for fuel cell applications

NASA Astrophysics Data System (ADS)

Lyu, Xiao; Hu, Jingping; Foord, John S.; Wang, Qiang

2013-11-01

A novel electroless deposition method was demonstrated to prepare a platinum electrocatalyst on boron doped diamond (BDD) substrates without the need for pre-activation. This green method addresses the uniformity and particle size issues associated with electrodeposition and circumvents the pre-activation procedure which is necessary for conventional electroless deposition. The inert BDD substrate formed a galvanic couple with an iron wire, to overcome the activation barrier associated with conventional electroless deposition on diamond, leading to the formation of Pt nanoparticles on the electrode surface in a galvanic process coupled to a chemical process. When sodium hypophosphite was employed as the reducing agent to drive the electroless reaction Pt deposits which were contaminated with iron and phosphorus resulted. In contrast, the reducing agent ascorbic acid gave rise to high purity Pt nanoparticles. Optimal deposition conditions with respect to bath temperature, pH value and stabilizing additives are identified. Using this approach, high purity and uniformly distributed platinum nanoparticles are obtained on the diamond electrode surface, which demonstrate a high electrochemical activity towards methanol oxidation.

In vitro corrosion behaviour and microhardness of high-copper amalgams with platinum and indium.

PubMed

Ilikli, B G; Aydin, A; Işimer, A; Alpaslan, G

1999-02-01

Samples prepared from Luxalloy, GS-80, Permite-C and Logic and polished after 24 h by traditional methods were stored in polypropylene tubes containing phosphate-buffered saline solutions (pH 3.5 and 6.5) and distilled water. The amounts of mercury, silver, tin, copper, zinc, platinum and indium in the test solutions were determined at the first, second, eighth, 52nd and 78th week by atomic absorption spectrometry. At the end of the eighth week the amalgam samples were removed from solutions and evaluated by Rockwell Super Scial Microhardness tester. Statistically significant low amounts of metal ions were measured for Permite-C containing indium and Logic containing platinum. The microhardness test results showed that there were statistically significant increases in the microhardness of Permite-C and Logic. As a result it was shown that the amalgam samples were affected from corrosion conditions to different degrees. Sample of the Logic group that was stored in distilled water, showed smoother surface properties than other amalgam samples containing high copper. However, it was observed that samples of Permite-C group had the smoothest surface properties.

On the behavior of reduced graphene oxide based electrodes coated with dispersed platinum by alternate current methods in the electrochemical degradation of reactive dyes.

PubMed

Del Río, A I; García, C; Molina, J; Fernández, J; Bonastre, J; Cases, F

2017-09-01

The electrochemical behavior of different carbon-based electrodes with and without nanoparticles of platinum electrochemically dispersed on their surface has been studied. Among others, reduced graphene oxide based electrodes was used to determine the best conditions for the decolorization/degradation of the reactive dye C.I. Reactive Orange 4 in sulfuric medium. Firstly, the electrochemical behavior was evaluated by cyclic voltammetry. Secondly, different electrolyses were performed using two cell configurations: cell with anodic and cathodic compartments separated (divided configuration) and without any separation (undivided configuration). The best results were obtained when reduced graphene oxide based anodes were used. The degree of decolorization was monitored by spectroscopic methods and high performance liquid chromatography. It was found that all of them followed pseudo-first order kinetics. When reduced graphene oxide-based electrodes coated with dispersed platinum by alternate current methods electrodes were used, the lowest energy consumption and the higher decolorization kinetics rate were obtained. Scanning Electronic Microscopy was used to observe the morphological surface differences. Copyright © 2017 Elsevier Ltd. All rights reserved.

Anthropogenic disturbance of element cycles at the Earth's surface.

PubMed

Sen, Indra S; Peucker-Ehrenbrink, Bernhard

2012-08-21

The extent to which humans are modifying Earth's surface chemistry can be quantified by comparing total anthropogenic element fluxes with their natural counterparts (Klee and Graedel, 2004). We quantify anthropogenic mass transfer of 77 elements from mining, fossil fuel burning, biomass burning, construction activities, and human apportionment of terrestrial net primary productivity, and compare it to natural mass transfer from terrestrial and marine net primary productivity, riverine dissolved and suspended matter fluxes to the ocean, soil erosion, eolian dust, sea-salt spray, cosmic dust, volcanic emissions, and for helium, hydrodynamic escape from the Earth's atmosphere. We introduce an approach to correct for losses during industrial processing of elements belonging to geochemically coherent groups, and explicitly incorporate uncertainties of element mass fluxes through Monte Carlo simulations. We find that at the Earth's surface anthropogenic fluxes of iridium, osmium, helium, gold, ruthenium, antimony, platinum, palladium, rhenium, rhodium and chromium currently exceed natural fluxes. For these elements mining is the major factor of anthropogenic influence, whereas petroleum burning strongly influences the surficial cycle of rhenium. Our assessment indicates that if anthropogenic contributions to soil erosion and eolian dust are considered, anthropogenic fluxes of up to 62 elements surpass their corresponding natural fluxes.

Characterization of sputtered iridium oxide thin films on planar and laser micro-structured platinum thin film surfaces for neural stimulation applications

NASA Astrophysics Data System (ADS)

Thanawala, Sachin

Electrical stimulation of neurons provides promising results for treatment of a number of diseases and for restoration of lost function. Clinical examples include retinal stimulation for treatment of blindness and cochlear implants for deafness and deep brain stimulation for treatment of Parkinsons disease. A wide variety of materials have been tested for fabrication of electrodes for neural stimulation applications, some of which are platinum and its alloys, titanium nitride, and iridium oxide. In this study iridium oxide thin films were sputtered onto laser micro-structured platinum thin films by pulsed-DC reactive sputtering of iridium metal in oxygen-containing atmosphere, to obtain high charge capacity coatings for neural stimulation applications. The micro-structuring of platinum films was achieved by a pulsed-laser-based technique (KrF excimer laser emitting at lambda=248nm). The surface morphology of the micro-structured films was studied using different surface characterization techniques. In-vitro biocompatibility of these laser micro-structured films coated with iridium oxide thin films was evaluated using cortical neurons isolated from rat embryo brain. Characterization of these laser micro-structured films coated with iridium oxide, by cyclic voltammetry and impedance spectroscopy has revealed a considerable decrease in impedance and increase in charge capacity. A comparison between amorphous and crystalline iridium oxide thin films as electrode materials indicated that amorphous iridium oxide has significantly higher charge capacity and lower impedance making it preferable material for neural stimulation application. Our biocompatibility studies show that neural cells can grow and differentiate successfully on our laser micro-structured films coated with iridium oxide. This indicates that reactively sputtered iridium oxide (SIROF) is biocompatible.

Oxygen Reduction Reaction Activity of Platinum Thin Films with Different Densities

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

Ergul, Busra; Begum, Mahbuba; Kariuki, Nancy

Platinum thin films with different densities were grown on glassy carbon electrodes by high pressure sputtering deposition and evaluated as oxygen reduction reaction catalysts for polymer electrolyte fuel cells using cyclic voltammetry and rotating disk electrode techniques in aqueous perchloric acid electrolyte. The electrochemically active surface area, ORR mass activity (MA) and specific activity (SA) of the thin film electrodes were obtained. MA and SA were found to be higher for low-density films than for high-density film.

Advanced hydrogen electrode for hydrogen-bromide battery

NASA Technical Reports Server (NTRS)

Kosek, Jack A.; Laconti, Anthony B.

1987-01-01

Binary platinum alloys are being developed as hydrogen electrocatalysts for use in a hydrogen bromide battery system. These alloys were varied in terms of alloy component mole ratio and heat treatment temperature. Electrocatalyst evaluation, performed in the absence and presence of bromide ion, includes floating half cell polarization studies, electrochemical surface area measurements, X ray diffraction analysis, scanning electron microscopy analysis and corrosion measurements. Results obtained to date indicate a platinum rich alloy has the best tolerance to bromide ion poisoning.

Novel multifunctional graphene sheets with encased Au/Ag nanoparticles for advanced electrochemical analysis of organic compounds.

PubMed

Pruneanu, Stela; Biris, Alexandru R; Pogacean, Florina; Lazar, Diana Mihaela; Ardelean, Stefania; Watanabe, Fumyia; Dervishi, Enkeleda; Biris, Alexandru S

2012-11-12

This work is the first presentation of the synthesis of few-layer graphene decorated with gold and silver nanoparticles (Gr-Au-Ag) by chemical vapor deposition over a catalytic system formed of bimetallic Au-Ag nanoclusters supported on MgO and with methane used as the source of carbon. The sheetlike morphology of the graphene nanostructures, with mean sizes in the range of hundreds of nanometers, was observed by high-resolution electron microscopy. The distinctive feature found in all the samples was the regular rectangular or square shapes. This multi-component organic-inorganic nanomaterial was used to modify a platinum substrate and subsequently employed for the detection of carbamazepine, an anti-convulsion drug. UV/Vis spectroscopy revealed that a strong hypochromism occurred over time, after mixing solutions of graphene-Au-Ag with carbamazepine. This can be attributed to π-π stacking between the aromatic groups of the two compounds. Linear sweep voltammetry (LCV) provided evidence that the modified platinum substrate presented a significant electrocatalytic reaction toward the oxidation of carbamazepine. The intensity of the current was found to increase by up to 2.5 times, and the oxidation potential shifted from +1.5 to +1.35 V(Ag/AgCl) in comparison with the unmodified electrode. Electrochemical impedance spectroscopy (EIS) was further used to thoroughly assess the activity of the platinum electrode that was modified by the deposition of the Gr-Au-Ag composites in the presence of various concentrations of carbamazepine. The experimental EIS records were used for the generation of an equivalent electrical circuit, based on the charge-transfer resistance (R(ct)), Warburg impedance (Z(D)), solution resistance (R(s)), and a constant phase element (CPE) that characterizes the non-ideal interface capacitive responses. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Investigating the cellular fate of a DNA-targeted platinum-based anticancer agent by orthogonal double-click chemistry

PubMed Central

Qiao, Xin; Ding, Song; Liu, Fang; Kucera, Gregory L.

2014-01-01

Confocal fluorescence microscopy was used to study a platinum-based anticancer agent in intact NCI-H460 lung cancer cells. Orthogonal copper-catalyzed azide–alkyne cycloaddition (click) reactions were used to simultaneously determine the cell-cycle-specific localization of the azide-functionalized platinum–acridine agent 1 and monitor its effects on nucleic acid metabolism. Copper-catalyzed postlabeling showed advantages over copper-free click chemistry using a dibenzocyclooctyne (DIBO)-modified reporter dye, which produced high background levels in microscopic images and failed to efficiently label platinum adducts in chromatin. Compound 1 was successfully labeled with the fluorophore DIBO to yield 1* (characterized by in-line high-performance liquid chromatography/electrospray mass spectrometry). 1 and 1* show a high degree of colocalization in the confocal images, but the ability of 1* to target the (compacted) chromatin was markedly reduced, most likely owing to the steric bulk introduced by the DIBO tag. Nuclear platinum levels correlated inversely with the ability of the cells to synthesize DNA and cause cell cycle arrest, as confirmed by bivariate flow cytometry analysis. In addition, a decrease in the level of cellular transcription, shrinkage of the nucleolar regions, and redistribution of RNA into the cytosol were observed. Postlabeling in conjunction with colocalization experiments is a useful tool for studying the cell killing mechanism of this type of DNA-targeted agent. PMID:24407462

Diffusion and Surface Reaction in Heterogeneous Catalysis

ERIC Educational Resources Information Center

Baiker, A.; Richarz, W.

1978-01-01

Ethylene hydrogenation on a platinum catalyst, electrolytically applied to a tube wall, is a good system for the study of the interactions between diffusion and surface reaction in heterogeneous catalysis. Theoretical background, apparatus, procedure, and student performance of this experiment are discussed. (BB)

Ultrathin platinum nanowires grown on single-layered nickel hydroxide with high hydrogen evolution activity.

PubMed

Yin, Huajie; Zhao, Shenlong; Zhao, Kun; Muqsit, Abdul; Tang, Hongjie; Chang, Lin; Zhao, Huijun; Gao, Yan; Tang, Zhiyong

2015-03-02

Design and synthesis of effective electrocatalysts for hydrogen evolution reaction in alkaline environments is critical to reduce energy losses in alkaline water electrolysis. Here we report a hybrid nanomaterial comprising of one-dimensional ultrathin platinum nanowires grown on two-dimensional single-layered nickel hydroxide. Judicious surface chemistry to generate the fully exfoliated nickel hydroxide single layers is explored to be the key for controllable growth of ultrathin platinum nanowires with diameters of about 1.8 nm. Impressively, this hybrid nanomaterial exhibits superior electrocatalytic activity for hydrogen evolution reaction in alkaline solution, which outperforms currently reported catalysts, and the obviously improved catalytic stability. We believe that this work may lead towards the development of single-layered metal hydroxide-based hybrid materials for applications in catalysis and energy conversion.

Fractal growth of platinum electrodeposits revealed by in situ electron microscopy.

PubMed

Wang, Lifen; Wen, Jianguo; Sheng, Huaping; Miller, Dean J

2016-10-06

Fractals are commonly observed in nature and elucidating the mechanisms of fractal-related growth is a compelling issue for both fundamental science and technology. Here we report an in situ electron microscopy study of dynamic fractal growth of platinum during electrodeposition in a miniaturized electrochemical cell at varying growth conditions. Highly dendritic growth - either dense branching or ramified islands - are formed at the solid-electrolyte interface. We show how the diffusion length of ions in the electrolyte influences morphology selection and how instability induced by initial surface roughness, combined with local enhancement of electric field, gives rise to non-uniform branched deposition as a result of nucleation/growth at preferred locations. Comparing the growth behavior under these different conditions provides new insight into the fundamental mechanisms of platinum nucleation.

Nanoporous gold membranes: From morphological control to fuel cell catalysis

NASA Astrophysics Data System (ADS)

Ding, Yi

Porous noble metals are particularly attractive for scientific research and industrial applications such as catalysis, sensing, and filtration. In this thesis, I will discuss the fabrication, characterization, and application of a new class of porous metals, called nanoporous metals (NPM). NPM is made during selective dissolution (also called dealloying) of reactive components (e.g., silver) from multi-component alloys (e.g., Ag/Au alloy). Commercially available white gold leaf (Ag65Au35) can, for example, be etched into nanoporous gold (NPG) membrane by simply floating the leaf on concentrated nitric acid for periods of a few minutes. NPG leaf adopts a single crystal porous structure within individual grains. The microstructure of NPG, such as the pore size, is tunable between a few nanometers to sub-micron length scale by either thermal annealing or post-treatment in nitric acid for extended period of time. A new gas-liquid-solid interface electroless plating technique is developed to uniformly cover the NPG surface with other metals, such as silver and platinum. This technique allows new opportunities of making functionalized nanostructures. We show that a combination of silver plating and dealloying can be used to make multimodal porous metals, which are expected to have application in sensing field. Electroless platinum plating onto NPG shows very usual growth mode. TEM observation indicates that the platinum layer on NPG surface takes a novel form of layer-islanding growth (Stranski-Krastanov growth). Annealing the Pt/NPG composite smoothens the Pt islands and forms a 1 nm coherent Pt layer on the NPG backbone, possibly with dislocation formation at the Pt/Au interface. Furthermore, it was found that we could dissolve the gold away in aqueous gold etchant, leaving behind the 1 nm-thick Pt shell, a structure we call nanotubular mesoporous platinum (NMP). Pt plated NPG has a series of unique structural properties, such as high active surface area, thermally stable, low Pt usage, and better tolerance to CO poisoning. We incorporated it as a membrane electrode into a working proton exchange membrane fuel cells (PEMFC). Preliminary results show that Pt/NPG has very good fuel cell performance at a very low platinum loading.

Modification and uptake of a cisplatin carbonato complex by Jurkat cells.

PubMed

Centerwall, Corey R; Tacka, Kirk A; Kerwood, Deborah J; Goodisman, Jerry; Toms, Bonnie B; Dubowy, Ronald L; Dabrowiak, James C

2006-07-01

The interactions of Jurkat cells with cisplatin, cis-[Pt(15NH3)2Cl2]1, are studied using 1H-15N heteronuclear single quantum coherence (HSQC) NMR and inductively coupled plasma mass spectrometry. We show that Jurkat cells in culture rapidly modify the monocarbonato complex cis-[Pt(15NH3)2(CO3)Cl]- (4), a cisplatin species that forms in culture media and probably also in blood. Analysis of the HSQC NMR peak intensity for 4 in the presence of different numbers of Jurkat cells reveals that each cell is capable of modifying 0.0028 pmol of 4 within approximately 0.6 h. The amounts of platinum taken up by the cell, weakly bound to the cell surface, remaining in the culture medium, and bound to genomic DNA were measured as functions of time of exposure to different concentrations of drug. The results show that most of the 4 that has been modified by the cells remains in the culture medium as a substance of molecular mass <3 kDa, which is HSQC NMR silent, and is not taken up by the cell. These results are consistent with a hitherto undocumented extracellular detoxification mechanism in which the cells rapidly modify 4, which is present in the culture medium, so it cannot bind to the cell. Because there is only a slow decrease in the amount of unmodified 4 remaining in the culture medium after 1 h, -1.1 +/- 0.4 microM h(-1), the cells subsequently lose their ability to modify 4. These observations have important implications for the mechanism of action of cisplatin.

Novel electrochemical biosensor based on cationic peptide modified hemin/G-quadruples enhanced peroxidase-like activity.

PubMed

Yu, Qian; Wu, Yongmei; Liu, Zi; Lei, Sheng; Li, Gaiping; Ye, Baoxian

2018-06-01

This work designed an artificial substrate peptide to synthesize peptide-hemin/G-quadruplex (peptide-DNAzyme) conjugates. In addition to enhancing catalytic activity of hemin/G-quadruplex, the peptide could also be induced and cleaved by prostate specific antigen (PSA). It was the first report on peptide-DNAzyme conjugates in application of the peptide biosensor. The polyethyleneimine-reduced graphene oxide@hollow platinum nanotubes (PEI-rGO@PtNTs) nanocomposites were cast on the glassy carbon electrode in order to form the interface of biocompatibility and huge surface area for bioprobes immobilization. In absence of PSA, the peptide-DNAzyme conjugates retained intact on the surface of the electrode to produce a strong response signal. But in presence of PSA, the peptide-DNAzyme conjugates were destroyed to release electron mediators, resulting in dramatical decrease of the electrochemicl signal. Therefore, the method had high sensitivity and super selectivity with the limit of detection calculated as 2.0 fg/mL. Furthermore, the strategy would be promising to apply for other proteases by transforming the synthetic peptide module of target. Copyright © 2018 Elsevier B.V. All rights reserved.

Synthesis of silver-platinum nanoferns substrates used in surface-enhanced Raman spectroscopy sensors to detect creatinine

NASA Astrophysics Data System (ADS)

Adliha Abdullah, Nur; Abu Bakar, Norhayati; Shapter, Joseph G.; Mat Salleh, Muhamad; Umar, Akrajas Ali

2017-06-01

Creatinine is one of the most commonly used bio markers of renal function. This paper reports a study on detection of creatinine using silver-platinum (AgPt) nanoferns substrates to fabricate a surface-enhanced Raman spectroscopy (SERS) sensor. The AgPt nanoferns were synthesized by liquid phase deposition (LPD) where the morphology structures and thickness of the AgPt nanoferns were controlled by varying the concentration of formic acid which was acting as the reducing agent. We have obtained four different nanoferns structures and thicknesses. This study showed that the AgPt nanoferns structure synthesized with 40 mM formic acid give the highest Raman peak intensity for a 0.05 M creatinine sample.

Ordered macroporous platinum electrode and enhanced mass transfer in fuel cells using inverse opal structure.

PubMed

Kim, Ok-Hee; Cho, Yong-Hun; Kang, Soon Hyung; Park, Hee-Young; Kim, Minhyoung; Lim, Ju Wan; Chung, Dong Young; Lee, Myeong Jae; Choe, Heeman; Sung, Yung-Eun

2013-01-01

Three-dimensional, ordered macroporous materials such as inverse opal structures are attractive materials for various applications in electrochemical devices because of the benefits derived from their periodic structures: relatively large surface areas, large voidage, low tortuosity and interconnected macropores. However, a direct application of an inverse opal structure in membrane electrode assemblies has been considered impractical because of the limitations in fabrication routes including an unsuitable substrate. Here we report the demonstration of a single cell that maintains an inverse opal structure entirely within a membrane electrode assembly. Compared with the conventional catalyst slurry, an ink-based assembly, this modified assembly has a robust and integrated configuration of catalyst layers; therefore, the loss of catalyst particles can be minimized. Furthermore, the inverse-opal-structure electrode maintains an effective porosity, an enhanced performance, as well as an improved mass transfer and more effective water management, owing to its morphological advantages.

Creating a bio-hybrid signal transduction pathway: opening a new channel of communication between cells and machines.

PubMed

Yarkoni, Orr; Donlon, Lynn; Frankel, Daniel

2012-12-01

Manipulation of signal transduction pathways presents a viable mechanism to interface cells with electronics. In this work, we present a two-step signal transduction pathway involving cellular and electronic transduction elements. In order to circumvent many of the conventional difficulties encountered when harnessing chemical signalling for the purpose of electronics communication, gaseous nitric oxide (NO) was selected as the signalling molecule. By genetic engineering of the nitric oxide synthase protein eNOS and insertion of light-oxygen-voltage (LOV) domains, we have created a photoactive version of the protein. The novel chimeric eNOS was found to be capable of producing NO in response to excitation by visible light. By coupling these mutant cells to a surface modified platinum electrode, it was possible to convert an optical signal into a chemical one, followed by subsequent conversion of the chemical signal into an electrical output.

Label-free DNA biosensor based on resistance change of platinum nanoparticles assemblies.

PubMed

Skotadis, Evangelos; Voutyras, Konstantinos; Chatzipetrou, Marianneza; Tsekenis, Georgios; Patsiouras, Lampros; Madianos, Leonidas; Chatzandroulis, Stavros; Zergioti, Ioanna; Tsoukalas, Dimitris

2016-07-15

A novel nanoparticle based biosensor for the fast and simple detection of DNA hybridization events is presented. The sensor utilizes hybridized DNA's charge transport properties, combining them with metallic nanoparticle networks that act as nano-gapped electrodes. The DNA hybridization events can be detected by a significant reduction in the sensor's resistance due to the conductive bridging offered by hybridized DNA. By modifying the nanoparticle surface coverage, which can be controlled experimentally being a function of deposition time, and the structural properties of the electrodes, an optimized biosensor for the in situ detection of DNA hybridization events is ultimately fabricated. The fabricated biosensor exhibits a wide response range, covering four orders of magnitude, a limit of detection of 1nM and can detect a single base pair mismatch between probe and complementary DNA. Copyright © 2016 Elsevier B.V. All rights reserved.

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

PubMed

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

2015-06-25

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

Measuring the thermal boundary resistance of van der Waals contacts using an individual carbon nanotube.

PubMed

Hirotani, Jun; Ikuta, Tatsuya; Nishiyama, Takashi; Takahashi, Koji

2013-01-16

Interfacial thermal transport via van der Waals interaction is quantitatively evaluated using an individual multi-walled carbon nanotube bonded on a platinum hot-film sensor. The thermal boundary resistance per unit contact area was obtained at the interface between the closed end or sidewall of the nanotube and platinum, gold, or a silicon dioxide surface. When taking into consideration the surface roughness, the thermal boundary resistance at the sidewall is found to coincide with that at the closed end. A new finding is that the thermal boundary resistance between a carbon nanotube and a solid surface is independent of the materials within the experimental errors, which is inconsistent with a traditional phonon mismatch model, which shows a clear material dependence of the thermal boundary resistance. Our data indicate the inapplicability of existing phonon models when weak van der Waals forces are dominant at the interfaces.

Observation and measurement of negative differential resistance on PtSi Schottky junctions on porous silicon.

PubMed

Banihashemian, Seyedeh Maryam; Hajghassem, Hassan; Erfanian, Alireza; Aliahmadi, Majidreza; Mohtashamifar, Mansor; Mosakazemi, Seyed Mohamadhosein

2010-01-01

Nanosize porous Si is made by two step controlled etching of Si. The first etching step is carried on the Si surface and the second is performed after deposition of 75 Å of platinum on the formed surface. A platinum silicide structure with a size of less than 25 nm is formed on the porous Si surface, as measured with an Atomic Forced Microscope (AFM). Differential resistance curve as a function of voltage in 77 K and 100 K shows a negative differential resistance and indicates the effect of quantum tunneling. In general form, the ratio of maximum to minimum tunneling current (PVR) and the number of peaks in I-V curves reduces by increasing the temperature. However, due to accumulation of carriers behind the potential barrier and superposition of several peaks, it is observed that the PVR increases at 100 K and the maximum PVR at 100 K is 189.6.

Efficient Synthesis of a Maghemite/Gold Hybrid Nanoparticle System as a Magnetic Carrier for the Transport of Platinum-Based Metallotherapeutics

PubMed Central

Štarha, Pavel; Smola, David; Tuček, Jiří; Trávníček, Zdeněk

2015-01-01

The preparation and thorough characterization of a hybrid magnetic carrier system for the possible transport of activated platinum-based anticancer drugs, as demonstrated for cisplatin (cis-[Pt(NH3)2Cl2], CDDP), are described. The final functionalized mag/Au–LA–CDDP* system consists of maghemite/gold nanoparticles (mag/Au) coated by lipoic acid (HLA; LA stands for deprotonated form of lipoic acid) and functionalized by activated cisplatin in the form of cis-[Pt(NH3)2(H2O)2]2+ (CDDP*). The relevant techniques (XPS, EDS, ICP-MS) proved the incorporation of the platinum-containing species on the surface of the studied hybrid system. HRTEM, TEM and SEM images showed the nanoparticles as spherical with an average size of 12 nm, while their superparamagnetic feature was proven by 57Fe Mössbauer spectroscopy. In the case of mag/Au, mag/Au–HLA and mag/Au–LA–CDDP*, weaker magnetic interactions among the Fe3+ centers of maghemite, as compared to maghemite nanoparticles (mag), were detected, which can be associated with the non-covalent coating of the maghemite surface by gold. The pH and time-dependent stability of the mag/Au–LA–CDDP* system in different media, represented by acetate (pH 5.0), phosphate (pH 7.0) and carbonate (pH 9.0) buffers and connected with the release of the platinum-containing species, showed the ability of CDDP* to be released from the functionalized nanosystem. PMID:25603182

Design and fabrication of nanoelectrodes for applications with scanning electrochemical microscopy

NASA Astrophysics Data System (ADS)

Thakar, Rahul

Scanning electrochemical microscope (SECM) was introduced two decades ago and has since emerged as a powerful research tool to investigate localized electrochemical reactions at the surface of material and biological samples. The ability to obtain chemical information at a surface differentiates SECM from competing scanning probe microscopy (SPM) techniques. Although, chemical specificity is a unique advantage offered by SECM, inherent limitations due to a slow feedback response, and challenges associated with production of smaller electrodes have remained major drawbacks. Initially in this research, SECM was utilized as a characterization and investigative tool. Later, advances in SECM imaging were achieved with design and production of multifunctional nanoelectrodes. At first, platinum based nanoelectrodes were fabricated for use as electrochemical probes to investigate local electron transfer at chemically-modified surfaces. Further, micron and sub-micron platinum electrodes with chemically modified shrouds were prepared and characterized with voltammetric measurements. Studies reveal experimental evidence for the presence of edge-effects that are typically associated with submicron electrodes. Interestingly, we observed selectivity of these electrodes based on hydrophobic/ hydrophilic character. Through vapor deposition of parylene over microstructured material, single-pore membranes and porous membrane arrays were produced. Pore size characterization within porous membranes was performed with templated growth of micro/nanostructures. Characterization of transport properties of ions and redox-active molecules through hydrophobic parylene membranes was investigated with ion conductance microscopy and SECM, individually. Parylene is an insulative material that is chemically resistant, deposits conformally over high-aspect ratio objects and also converts into conductive carbon at high-temperature pyrolysis. Motivated by these results we identified a unique strategy to fabricate parylene based carbon electrodes Here, we have developed a unique strategy to obtain carbon based nanoelectrodes from vapor deposition of parylene over pulled glass nanopipettes. With this approach, multiple electrode geometries were constructed and the application of individual geomtery with SECM is demonstrated. In particular, enhanced spatial resolution and electrochemical information were obtained with the use of carbon ring/nanopore electrodes. Practical implications of edge-effects observed with carbon ring/nanopore electrodes is discussed with substrate generation tip collection (SG/TC) SECM Carbon ring/nanopore electrodes have also enabled the use of SECM in conjunction with ion conductance microscopy to alleviate the issue of poor feedback response. This has further helped in deconvolution of electrochemcial and topographical signals. Although, use of carbon nanoelectrodes is discussed with specific applications to electrochemcial microscopy, these probes have wide utility in electroanalytical applications. Initial proof-of-concept experiments along with future directions for this work are presented.

Tuning selectivity in catalysis by controlling particle shape

NASA Astrophysics Data System (ADS)

Lee, Ilkeun; Delbecq, Françoise; Morales, Ricardo; Albiter, Manuel A.; Zaera, Francisco

2009-02-01

A catalytic process for the selective formation of cis olefins would help minimize the production of unhealthy trans fats during the partial hydrogenation of edible oils. Here we report on the design of such a process on the basis of studies with model systems. Temperature programmed desorption data on single crystals showed that the isomerization of trans olefins to their cis counterparts is promoted by (111) facets of platinum, and that such selectivity is reversed on more open surfaces. Quantum mechanics calculations suggested that the extra stability of cis olefins seen on hydrogen-saturated Pt(111) surfaces may be due to a lesser degree of surface reconstruction, a factor found to be significant in the adsorption on close-packed platinum surfaces. Kinetic data using catalysts made out of dispersed tetrahedral Pt nanoparticles corroborated the selective promotion of the trans-to-cis isomerization on the (111) facets of the metal. Our work provides an example for how catalytic selectivity may be controlled by controlling the shape of the catalytic particles.

Miniaturized flow system based on enzyme modified PMMA microreactor for amperometric determination of glucose.

PubMed

Cerdeira Ferreira, Luís Marcos; da Costa, Eric Tavares; do Lago, Claudimir Lucio; Angnes, Lúcio

2013-09-15

This paper describes the development of a microfluidic system having as main component an enzymatic reactor constituted by a microchannel assembled in poly(methyl methacrylate) (PMMA) substrate connected to an amperometric detector. A CO2 laser engraving machine was used to make the channels, which in sequence were thermally sealed. The internal surfaces of the microchannels were chemically modified with polyethyleneimine (PEI), which showed good effectiveness for the immobilization of the glucose oxidase enzyme using glutaraldehyde as crosslinking agent, producing a very effective microreactor for the detection of glucose. The hydrogen peroxide generated by the enzymatic reaction was detected in an electrochemical flow cell localized outside of the reactor using a platinum disk as the working electrode. The proposed system was applied to the differential amperometric determination of glucose content in soft drinks showing good repeatability (DPR=1.72%, n=50), low detection limit (1.40×10(-6)molL(-1)), high sampling frequency (calculated as 345 samples h(-1)), and relatively good stability for long-term use. The results were in close agreement with those obtained by the classical spectrophotometric method utilized to quantify glucose in biological fluids. Copyright © 2013 Elsevier B.V. All rights reserved.

Electrochemical sensor based on gold nanoparticles fabricated molecularly imprinted polymer film at chitosan-platinum nanoparticles/graphene-gold nanoparticles double nanocomposites modified electrode for detection of erythromycin.

PubMed

Lian, Wenjing; Liu, Su; Yu, Jinghua; Xing, Xianrong; Li, Jie; Cui, Min; Huang, Jiadong

2012-01-01

A molecularly imprinted electrochemical sensor was fabricated based on gold electrode decorated by chitosan-platinum nanoparticles (CS-PtNPs) and graphene-gold nanoparticles (GR-AuNPs) nanocomposites for convenient and sensitive determination of erythromycin. The synergistic effects of CS-PtNPs and GR-AuNPs nanocomposites improved the electrochemical response and the sensitivity of the sensor. The molecularly imprinted polymers (MIPs) were prepared by HAuCl(4), 2-mercaptonicotinic acid (MNA) and erythromycin. Erythromycin and MNA were used as template molecule and functional monomer, respectively. They were first assembled on the surface of GR-AuNPs/CS-PtNPs/gold electrode by the formation of Au-S bonds and hydrogen-bonding interactions. Then the MIPs were formed by electropolymerization of HAuCl(4), MNA and erythromycin. The sensor was characterized by cyclic voltammetry (CV), scanning electron microscope (SEM), UV-visible (UV-vis) absorption speactra and amperometry. The linear range of the sensor was from 7.0 × 10(-8)mol/L-9.0 × 10(-5)mol/L, with the limit of detection (LOD) of 2.3 × 10(-8)mol/L (S/N=3). The sensor showed high selectivity, excellent stability and good reproducibility for the determination of erythromycin, and it was successfully applied to the detection of erythromycin in real spiked samples. Copyright © 2012 Elsevier B.V. All rights reserved.

Gelatin-encapsulated iron oxide nanoparticles for platinum (IV) prodrug delivery, enzyme-stimulated release and MRI.

PubMed

Cheng, Ziyong; Dai, Yunlu; Kang, Xiaojiao; Li, Chunxia; Huang, Shanshan; Lian, Hongzhou; Hou, Zhiyao; Ma, Pingan; Lin, Jun

2014-08-01

A facile method for transferring hydrophobic iron oxide nanoparticles (IONPs) from chloroform to aqueous solution via encapsulation of FITC-modified gelatin based on the hydrophobic-hydrophobic interaction is described in this report. Due to the existence of large amount of active groups such as amine groups in gelatin, the fluorescent labeling molecules of fluorescein isothiocyanate (FITC) and platinum (IV) prodrug functionalized with carboxylic groups can be conveniently conjugated on the IONPs. The nanoparticles carrying Pt(IV) prodrug exhibit good anticancer activities when the Pt(IV) complexes are reduced to Pt(II) in the intracellular environment, while the pure Pt(IV) prodrug only presents lower cytotoxicity on cancer cells. Meanwhile, fluorescence of FITC on the surface of nanoparticles was completely quenched due to the possible Förster Resonance Energy Transfer (FRET) mechanism and showed a fluorescence recovery after gelatin release and detachment from IONPs. Therefore FITC as a fluorescence probe can be used for identification, tracking and monitoring the drug release. In addition, adding pancreatic enzyme can effectively promote the gelatin release from IONPs owing to the degradation of gelatin. Noticeable darkening in magnetic resonance image (MRI) was observed at the tumor site after in situ injection of nanoparticles, indicating the IONPs-enhanced T2-weighted imaging. Our results suggest that the gelatin encapsulated Fe3O4 nanoparticles have potential applications in multi-functional drug delivery system for disease therapy, MR imaging and fluorescence sensor. Copyright © 2014 Elsevier Ltd. All rights reserved.

Electrodeposition of gold-platinum alloy nanoparticles on ionic liquid-chitosan composite film and its application in fabricating an amperometric cholesterol biosensor.

PubMed

Safavi, Afsaneh; Farjami, Fatemeh

2011-01-15

An electrodeposition method was applied to form gold-platinum (AuPt) alloy nanoparticles on the glassy carbon electrode (GCE) modified with a mixture of an ionic liquid (IL) and chitosan (Ch) (AuPt-Ch-IL/GCE). AuPt nanoparticles were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and electrochemical methods. AuPt-Ch-IL/GCE electrocatalyzed the reduction of H(2)O(2) and thus was suitable for the preparation of biosensors. Cholesterol oxidase (ChOx) was then, immobilized on the surface of the electrode by cross-linking ChOx and chitosan through addition of glutaraldehyde (ChOx/AuPt-Ch-IL/GCE). The fabricated biosensor exhibited two wide linear ranges of responses to cholesterol in the concentration ranges of 0.05-6.2 mM and 6.2-11.2 mM. The sensitivity of the biosensor was 90.7 μA mM(-1) cm(-2) and the limit of detection was 10 μM of cholesterol. The response time was less than 7 s. The Michaelis-Menten constant (K(m)) was found as 0.24 mM. The effect of the addition of 1 mM ascorbic acid and glucose was tested on the amperometric response of 0.5 mM cholesterol and no change in response current of cholesterol was observed. Copyright © 2010 Elsevier B.V. All rights reserved.

Ultra-fine Pt nanoparticles on graphene aerogel as a porous electrode with high stability for microfluidic methanol fuel cell

NASA Astrophysics Data System (ADS)

Kwok, Y. H.; Tsang, Alpha C. H.; Wang, Yifei; Leung, Dennis Y. C.

2017-05-01

Platinum-decorated graphene aerogel as a porous electrode for flow-through direct methanol microfluidic fuel cell is introduced. Ultra-fine platinum nanoparticles with size ranged from diameter 1.5 nm-3 nm are evenly anchored on the graphene nanosheets without agglomeration. The electrode is characterized by scanning electron microscopy, transmission electron microscopy and energy-dispersive X-ray spectroscopy. Catalytic activity is confirmed by cyclic voltammetry. The electroactive surface area and catalytic activity of platinum on graphene oxide (Pt/GO) are much larger than commercial platinum on carbon black (Pt/C). A counterflow microfluidic fuel cell is designed for contrasting the cell performance between flow-over type and flow-through type electrodes using Pt/C on carbon paper and Pt/GO, respectively. The Pt/GO electrode shows 358% increment in specific power compared with Pt/C anode. Apart from catalytic activity, the effect of porous electrode conductivity to cell performance is also studied. The conductivity of the porous electrode should be further enhanced to achieve higher cell performance.

Favorable effect of in-situ generated platinum in the membrane on fuel cell membrane durability

NASA Astrophysics Data System (ADS)

Macauley, Natalia; Wong, Ka Hung; Watson, Mark; Kjeang, Erik

2015-12-01

The overall lifetime of polymer electrolyte fuel cells is often determined by the membrane durability. Platinum, which may dissolve from the catalyst layers during fuel cell operation and deposit in the membrane, has been shown to have both positive and negative effects on membrane stability. In the present work, we analyze what specific conditions are required in order to reach a favorable, membrane stabilizing effect with the controlled use of platinum in the membrane. Using accelerated membrane durability testing, field operated membrane samples, and electron microscopy, we demonstrate that a high platinum concentration with specific particle shapes and sizes is essential for enhanced membrane stability. Specifically, star shaped and dendritic particles with high particle density and high surface area are shown to be preferable. These particles contain high levels of Pt(111) and are expected to have high catalytic activity toward peroxide quenching and crossover gas consumption, thereby mitigating chemical membrane degradation. On the other hand, small, dispersed cubic particles are found to have no effect or the opposite, negative effect on membrane stability.

Platinum Nanoparticle Loading of Boron Nitride Aerogel and Its Use as a Novel Material for Low-Power Catalytic Gas Sensing

DOE PAGES

Harley-Trochimczyk, Anna; Pham, Thang; Chang, Jiyoung; ...

2015-12-09

We report that a high-surface-area, highly crystalline boron nitride aerogel synthesized with nonhazardous reactants has been loaded with crystalline platinum nanoparticles to form a novel nanomaterial that exhibits many advantages for use in a catalytic gas sensing application. The platinum nanoparticle-loaded boron nitride aerogel integrated onto a microheater platform allows for calorimetric propane detection. The boron nitride aerogel exhibits thermal stability up to 900 °C and supports disperse platinum nanoparticles, with no sintering observed after 24 h of high-temperature testing. The high thermal conductivity and low density of the boron nitride aerogel result in an order of magnitude faster responsemore » and recovery times (<2 s) than reported on alumina support and allow for 10% duty cycling of the microheater with no loss in sensitivity. Lastly, the resulting 1.5 mW sensor power consumption is two orders of magnitude less than commercially available catalytic gas sensors and unlocks the potential for wireless, battery-powered catalytic gas sensing.« less

Electroreduction of Er 3+ in nonaqueous solvents

DOE PAGES

Small, Leo J.; Sears, Jeremiah M.; Lambert, Timothy N.; ...

2016-09-15

Here, the electroreduction of Er 3+ in propylene carbonate, N,N-dimethylformamide, or a variety of quaternary ammonium ionic liquids (ILs) was investigated using [Er(OTf) 3] and [Er(NTf 2) 3]. Systematic variation of the ILs' cation and anion, Er 3+ salt, and electrode material revealed a disparity in electrochemical interactions not previously seen. For most ILs at a platinum electrode, cyclic voltammetry exhibits irreversible interactions between Er 3+ salts and the electrode at potentials significantly less than the theoretical reduction potential for Er 3+. Throughout all solvent–salt systems tested, a deposit could be formed on the electrode, though obtaining a high purity,more » crystalline Er 0 deposit is challenging due to the extreme reactivity of the deposit and resulting chemical interactions, often resulting in the formation of a complex, amorphous solid–electrolyte interface that slowed deposition rates. Comparison of platinum, gold, nickel, and glassy carbon (GC) working electrodes revealed oxidation processes unique to the platinum surface. While no appreciable reduction current was observed on GC at the potentials investigated, deposits were seen on platinum, gold, and nickel electrodes.« less

Outdoor surface temperature measurement: ground truth or lie?

NASA Astrophysics Data System (ADS)

Skauli, Torbjorn

2004-08-01

Contact surface temperature measurement in the field is essential in trials of thermal imaging systems and camouflage, as well as for scene modeling studies. The accuracy of such measurements is challenged by environmental factors such as sun and wind, which induce temperature gradients around a surface sensor and lead to incorrect temperature readings. In this work, a simple method is used to test temperature sensors under conditions representative of a surface whose temperature is determined by heat exchange with the environment. The tested sensors are different types of thermocouples and platinum thermistors typically used in field trials, as well as digital temperature sensors. The results illustrate that the actual measurement errors can be much larger than the specified accuracy of the sensors. The measurement error typically scales with the difference between surface temperature and ambient air temperature. Unless proper care is taken, systematic errors can easily reach 10% of this temperature difference, which is often unacceptable. Reasonably accurate readings are obtained using a miniature platinum thermistor. Thermocouples can perform well on bare metal surfaces if the connection to the surface is highly conductive. It is pointed out that digital temperature sensors have many advantages for field trials use.

Determination of caffeic acid in wine using PEDOT film modified electrode.

PubMed

Bianchini, C; Curulli, A; Pasquali, M; Zane, D

2014-08-01

A novel method using PEDOT (poly(3,4-ethylenedioxy) thiophene) modified electrode was developed for the determination of caffeic acid (CA) in wine. Cyclic voltammetry (CV) with the additions standard method was used to quantify the analyte at PEDOT modified electrodes. PEDOT films were electrodeposited on Platinum electrode (Pt) in aqueous medium by galvanostatic method using sodium poly(styrene-4-sulfonate) (PSS) as electrolyte and surfactant. CV allows detecting the analyte over a wide concentration range (10.0nmoll(-1)-6.5mmoll(-1)). The electrochemical method proposed showed good statistical and analytical parameters as linearity range, LOD, LOQ and sensitivity. Copyright © 2014 Elsevier Ltd. All rights reserved.

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

PubMed

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

2014-01-22

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

Direct Imaging Mass Spectrometry of Plant Leaves Using Surface-assisted Laser Desorption/Ionization with Sputter-deposited Platinum Film.

PubMed

Ozawa, Tomoyuki; Osaka, Issey; Hamada, Satoshi; Murakami, Tatsuya; Miyazato, Akio; Kawasaki, Hideya; Arakawa, Ryuichi

2016-01-01

Plant leaves administered with systemic insecticides as agricultural chemicals were analyzed using imaging mass spectrometry (IMS). Matrix-assisted laser desorption/ionization (MALDI) is inadequate for the detection of insecticides on leaves because of the charge-up effect that occurs on the non-conductive surface of the leaves. In this study, surface-assisted laser desorption/ionization with a sputter-deposited platinum film (Pt-SALDI) was used for direct analysis of chemicals in plant leaves. Sputter-deposited platinum (Pt) films were prepared on leaves administered with the insecticides. A sputter-deposited Pt film with porous structure was used as the matrix for Pt-SALDI. Acephate and acetamiprid contained in the insecticides on the leaves could be detected using Pt-SALDI-MS, but these chemical components could not be adequately detected using MALDI-MS because of the charge-up effect. Enhancement of ion yields for the insecticides was achieved using Pt-SALDI, accompanied by prevention of the charge-up effect by the conductive Pt film. The movement of systemic insecticides in plants could be observed clearly using Pt-SALDI-IMS. The distribution and movement of components of systemic insecticides on leaves could be analyzed directly using Pt-SALDI-IMS. Additionally, changes in the properties of the chemicals with time, as an indicator of the permeability of the insecticides, could be evaluated.

M13 bacteriophage displaying DOPA on surfaces: fabrication of various nanostructured inorganic materials without time-consuming screening processes.

PubMed

Park, Joseph P; Do, Minjae; Jin, Hyo-Eon; Lee, Seung-Wuk; Lee, Haeshin

2014-01-01

M13 bacteriophage (phage) was engineered for the use as a versatile template for preparing various nanostructured materials via genetic engineering coupled to enzymatic chemical conversions. First, we engineered the M13 phage to display TyrGluGluGlu (YEEE) on the pVIII coat protein and then enzymatically converted the Tyr residue to 3,4-dihydroxyl-l-phenylalanine (DOPA). The DOPA-displayed M13 phage could perform two functions: assembly and nucleation. The engineered phage assembles various noble metals, metal oxides, and semiconducting nanoparticles into one-dimensional arrays. Furthermore, the DOPA-displayed phage triggered the nucleation and growth of gold, silver, platinum, bimetallic cobalt-platinum, and bimetallic iron-platinum nanowires. This versatile phage template enables rapid preparation of phage-based prototype devices by eliminating the screening process, thus reducing effort and time.

Platinum/Tin Oxide/Silica Gel Catalyst Oxidizes CO

NASA Technical Reports Server (NTRS)

Upchurch, Billy T.; Davis, Patricia P.; Schryer, David R.; Miller, Irvin M.; Brown, David; Van Norman, John D.; Brown, Kenneth G.

1991-01-01

Heterogeneous catalyst of platinum, tin oxide, and silica gel combines small concentrations of laser dissociation products, CO and O2, to form CO22 during long times at ambient temperature. Developed as means to prevent accumulation of these products in sealed CO2 lasers. Effective at ambient operating temperatures and installs directly in laser envelope. Formulated to have very high surface area and to chemisorb controlled quantities of moisture: chemisorbed water contained within and upon its structure, makes it highly active and very longlived so only small quantity needed for long times.

Electrifying model catalysts for understanding electrocatalytic reactions in liquid electrolytes.

PubMed

Faisal, Firas; Stumm, Corinna; Bertram, Manon; Waidhas, Fabian; Lykhach, Yaroslava; Cherevko, Serhiy; Xiang, Feifei; Ammon, Maximilian; Vorokhta, Mykhailo; Šmíd, Břetislav; Skála, Tomáš; Tsud, Nataliya; Neitzel, Armin; Beranová, Klára; Prince, Kevin C; Geiger, Simon; Kasian, Olga; Wähler, Tobias; Schuster, Ralf; Schneider, M Alexander; Matolín, Vladimír; Mayrhofer, Karl J J; Brummel, Olaf; Libuda, Jörg

2018-07-01

Electrocatalysis is at the heart of our future transition to a renewable energy system. Most energy storage and conversion technologies for renewables rely on electrocatalytic processes and, with increasing availability of cheap electrical energy from renewables, chemical production will witness electrification in the near future 1-3 . However, our fundamental understanding of electrocatalysis lags behind the field of classical heterogeneous catalysis that has been the dominating chemical technology for a long time. Here, we describe a new strategy to advance fundamental studies on electrocatalytic materials. We propose to 'electrify' complex oxide-based model catalysts made by surface science methods to explore electrocatalytic reactions in liquid electrolytes. We demonstrate the feasibility of this concept by transferring an atomically defined platinum/cobalt oxide model catalyst into the electrochemical environment while preserving its atomic surface structure. Using this approach, we explore particle size effects and identify hitherto unknown metal-support interactions that stabilize oxidized platinum at the nanoparticle interface. The metal-support interactions open a new synergistic reaction pathway that involves both metallic and oxidized platinum. Our results illustrate the potential of the concept, which makes available a systematic approach to build atomically defined model electrodes for fundamental electrocatalytic studies.

Enhancement of oxidative electrocatalytic properties of platinum nanoparticles by supporting onto mixed WO3/ZrO2 matrix

NASA Astrophysics Data System (ADS)

Rutkowska, Iwona A.; Wadas, Anna; Kulesza, Pawel J.

2016-12-01

Nanostructured mixed metal (W, Zr) oxide matrices (in a form of layered intercalated films of WO3 and ZrO2) are considered here for supporting and activating catalytic platinum nanoparticles toward electrooxidation of ethanol. Remarkable increases of electrocatalytic (voltammetric, chronoamperometric) currents measured in 0.5 mol dm-3 H2SO4 (containing 0.5 mol dm-3 ethanol) have been observed. Comparison has been made to the behavior of methanol and acetaldehyde under analogous conditions. The enhancement effects are interpreted in terms of specific interactions between platinum nanoparticles and the metal oxide species, high acidity of the mixed oxide sites, as well as high population of surface hydroxyl groups and high mobility of protons existing in close vicinity of Pt catalytic sites. The metal oxide nanostructures are expected to interact competitively (via the surface hydroxyl groups) with adsorbates of the undesirable reaction intermediates, including CO, facilitating their desorption ("third body effect"), or even oxidative removal (e.g., of CO to CO2). The fact that the partially reduced tungsten oxide (HxWO3) component is characterized by fast electron transfers coupled to proton displacements tends to improve the overall charge propagation at the electrocatalytic interface.

Platinum-gold nanoclusters as catalyst for direct methanol fuel cells.

PubMed

Giorgi, L; Giorgi, R; Gagliardi, S; Serra, E; Alvisi, M; Signore, M A; Piscopiello, E

2011-10-01

Nanosized platinum-gold alloys clusters have been deposited on gas diffusion electrode by sputter deposition. The deposits were characterized by FE-SEM, TEM and XPS in order to verify the formation of alloy nanoparticles and to study the influence of deposition technique on the nanomorphology. The deposition by sputtering process allowed a uniform distribution of metal particles on porous surface of carbon supports. Typical island growth mode was observed with the formation of a dispersed metal nanoclusters (mean size about 5 nm). Cyclic voltammetry was used to determine the electrochemical active surface and the electrocatalytic performance of the PtAu electrocatalysts for methanol oxidation reaction. The data were re-calculated in the form of mass specific activity (MSA). The sputter-catalyzed electrodes showed higher performance and stability compared to commercial catalysts.

Heat flux microsensor measurements and calibrations

NASA Technical Reports Server (NTRS)

Terrell, James P.; Hager, Jon M.; Onishi, Shinzo; Diller, Thomas E.

1992-01-01

A new thin-film heat flux gage has been fabricated specifically for severe high temperature operation using platinum and platinum-10 percent rhodium for the thermocouple elements. Radiation calibrations of this gage were performed at the AEDC facility over the available heat flux range (approx. 1.0 - 1,000 W/cu cm). The gage output was linear with heat flux with a slight increase in sensitivity with increasing surface temperature. Survivability of gages was demonstrated in quench tests from 500 C into liquid nitrogen. Successful operation of gages to surface temperatures of 750 C has been achieved. No additional cooling of the gages is required because the gages are always at the same temperature as the substrate material. A video of oxyacetylene flame tests with real-time heat flux and temperature output is available.

Testing superalloys at 2000 (1367) and 2200 F (1478 K) in a Mach 4.6 airstream

NASA Technical Reports Server (NTRS)

Land, D. W.; Williams, R. R.; Rinehart, W. A.

1972-01-01

Seven superalloy models were tested in a plasma arc tunnel facility. The test models were 3 in. (7.62cm) square flat surfaces (nominally 0.01 to 0.02 in. (0.0254 to 0.0508 cm) thick) held in a water-cooled wedge holder at a 60 deg (1.05 rad) angle of attack. The models were cycled 25 times (two were cycled 50 times) for 10 min each cycle in a Mach 4.6 test stream with the model leading edge temperature maintained at 2200 F (1478 K) (one at 2000 F (1367 K)). Backface temperatures were measured with four platinum-platinum 10% rhodium thermocouples and the front surface temperatures with an optical pyrometer. Four different nickel base alloy materials and one cobalt material were evaluated.

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.

Highly-sensitive cholesterol biosensor based on platinum-gold hybrid functionalized ZnO nanorods.

PubMed

Wang, Chengyan; Tan, Xingrong; Chen, Shihong; Yuan, Ruo; Hu, Fangxin; Yuan, Dehua; Xiang, Yun

2012-05-30

A novel scheme for the fabrication of gold/platinum hybrid functionalized ZnO nanorods (Pt-Au@ZnONRs) and multiwalled carbon nanotubes (MWCNTs) modified electrode is presented and its application for cholesterol biosensor is investigated. Firstly, Pt-Au@ZnONRs was prepared by the method of chemical synthesis. Then, the Pt-Au@ZnONRs suspension was dropped on the MWCNTs modified glass carbon electrode, and followed with cholesterol oxidase (ChOx) immobilization by the adsorbing interaction between the nano-material and ChOx as well as the electrostatic interaction between ZnONRs and ChOx molecules. The combination of MWCNTs and Pt-Au@ZnONRs provided a favorable environment for ChOx and resulted in the enhanced analytical response of the biosensor. The resulted biosensor exhibited a linear response to cholesterol in the wide range of 0.1-759.3 μM with a low detection limit of 0.03 μM and a high sensitivity of 26.8 μA mM(-1). The calculated apparent Michaelis constant K(M)(app) was 1.84 mM, indicating a high affinity between ChOx and cholesterol. Copyright © 2012 Elsevier B.V. All rights reserved.

Microgravity Effects on Chronoamperometric Ammonia Oxidation Reaction at Platinum Nanoparticles on Modified Mesoporous Carbon Supports

NASA Astrophysics Data System (ADS)

Poventud-Estrada, Carlos M.; Acevedo, Raúl; Morales, Camila; Betancourt, Luis; Diaz, Diana C.; Rodriguez, Manuel A.; Larios, Eduardo; José-Yacaman, Miguel; Nicolau, Eduardo; Flynn, Michael; Cabrera, Carlos R.

2017-10-01

The effect of microgravity on the electrochemical oxidation of ammonia at platinum nanoparticles supported on modified mesoporous carbons (MPC) with three different pore diameters (64, 100, and 137 Å) was studied via the chronoamperometric technique in a half-cell. The catalysts were prepared by a H2 reductive process of PtCl6^{4-} in presence of the mesoporous carbon support materials. A microgravity environment was obtained with an average gravity of less than 0.02 g created aboard an airplane performing parabolic maneuvers. Results show the chronoamperommetry of the ammonia oxidation reaction in 1.0 M NH4OH at 0.60 V vs. RHE under microgravity conditions. The current density, in all three catalysts, decreased while in microgravity conditions when compared to ground based experiments. Under microgravity, all three catalysts yielded a decrease in ammonia oxidation reaction current density between 25 to 63% versus terrestrial experimental results, in time scales between 1 and 15 s. The Pt catalyst prepared with mesoporous carbon of 137 Å porous showed the smallest changes, between 25 to 48%. Nanostructuring catalyst materials have an effect on the level of current density decrease under microgravity conditions.

Novel 3-hydroxypropyl bonded phase by direct hydrosilylation of allyl alcohol on amorphous hydride silica

PubMed Central

Gómez, Jorge E.; Navarro, Fabián H.; Sandoval, Junior E.

2015-01-01

A novel 3-hydroxypropyl (propanol) bonded silica phase has been prepared by hydrosilylation of allyl alcohol on a hydride silica intermediate, in the presence of platinum (0)-divinyltetramethyldisiloxane (Karstedt's catalyst). The regio-selectivity of this synthetic approach had been correctly predicted by previous reports involving octakis(dimethylsiloxy)octasilsesquioxane (Q8M8H) and hydrogen silsesquioxane (T8H8), as molecular analogs of hydride amorphous silica. Thus, C-silylation predominated (~ 94%) over O-silylation, and high surface coverages of propanol groups (5±1 µmol/m2) were typically obtained in this work. The propanol-bonded phase was characterized by spectroscopic (IR and solid state NMR on silica microparticles), contact angle (on fused-silica wafers) and CE (on fused-silica tubes) techniques. CE studies of the migration behavior of pyridine, caffeine, tris(2,2’-bipyridine)Ru(II) chloride and lysozyme on propanol-modified capillaries were carried out. The adsorption properties of these select silanol-sensitive solutes were compared to those on the unmodified and hydride-modified tubes. It was found that hydrolysis of the SiH species underlying the immobilized propanol moieties leads mainly to strong ion-exchange based interactions with the basic solutes at pH 4, particularly with lysozyme. Interestingly, and in agreement with water contact angle and electroosmotic mobility figures, the silanol-probe interactions on the buffer-exposed (hydrolyzed) hydride surface are quite different from those of the original unmodified tube. PMID:24934906

Vertically grown zinc oxide nanorods functionalized with ferric oxide for in vivo and non-enzymatic glucose detection

NASA Astrophysics Data System (ADS)

Marie, Mohammed; Manoharan, Anishkumar; Kuchuk, Andrian; Ang, Simon; Manasreh, M. O.

2018-03-01

An enzyme-free glucose sensor based on vertically grown zinc oxide nanorods (NRs) functionalized with ferric oxide (Fe2O3) is investigated. The well-aligned and high density ZnO NRs were synthesized on an FTO/glass substrate by a sol-gel and hydrothermal growth method. A dip-coating technique was utilized to modify the surface of the as-grown ZnO NRs with Fe2O3. The immobilized surface was coated with a layer of nafion membrane. The fabricated glucose sensor was characterized amperometrically at room temperature using three electrodes stationed in the phosphate buffer solution, where ZnO NRs/Fe2O3/nafion membrane was the sensing or working electrode, and platinum plate and silver/silver chloride were used as the counter and reference electrodes, respectively. The proposed non-enzymatic and modified glucose sensor exhibited a high sensitivity in the order of 0.052 μA cm-2 (mg/dL)-1, a lower detection limit of around 0.95 mmol L-1, a sharp and fast response time of ˜1 s, and a linear response to changes in glucose concentrations from 100-400 mg dL-1. The linear amperometric response of the sensor covers the physiological and clinical interest of glucose levels for diabetic patients. The device continues to function accurately after multiple measurements with a good reproducibility. The proposed glucose sensor is expected to be used clinically for in vivo monitoring of glucose.

Low-level (PPB) determination of cisplatin in cleaning validation (rinse water) samples. II. A high-performance liquid chromatographic method.

PubMed

Raghavan, R; Burchett, M; Loffredo, D; Mulligan, J A

2000-04-01

A high-performance liquid chromatographic (HPLC) method is described for the determination of residual levels of cisplatin from extracts of surfaces with very low surface area; from extracts of surfaces of coupons made of Teflon (polytetrafluoroethylene, PTFE), stainless steel, and glass; and in aqueous solution collected after rinsing equipment and parts. Initially, the method was developed to determine cisplatin at concentrations ranging from 20 to 200 ng/ml by direct injection. Retaining the same method conditions, the scope of the method was expanded by the addition of a sample preconcentration step, allowing analyses at levels ranging from 0.5 ng to 20 ng/ml. Preconcentration is necessary for the determination of cisplatin in rinse waters at a quantifiable concentration of about 2 PPB. Under these conditions, the detection limit is about 0.2 to 0.3 ng/ml. Residual cisplatin on different types of surfaces, including surfaces with very low surface area, can be determined by swabbing each test surface with a derivatizing solution. The cisplatin recovered in the swabbing solution can be analyzed by HPLC using direct injection or preconcentration, depending on the expected level of cisplatin in the sample. Initial methods were developed to quantitate at a cisplatin concentration of about 100 PPB or higher in solution extracted from surfaces. However, when surface areas are limited because of the size of the parts, solution concentration becomes very low as a result of the minimum volume required for extraction. To support the application of swabbing techniques to surface analysis, stainless steel, Teflon, and glass surfaces were spiked with cisplatin at 2.5 to 20 ng/cm2. Satisfactory overall recoveries of 90% +/- 10% were obtained from all surfaces. Cisplatin has no ultraviolet/visible (UV/Vis) spectral-active functional group that can be used to detect low levels of cisplatin. Hence, diethyldithiocarbamate (DDTC) was used as a derivatizing agent to increase sensitivity to UV absorption at 340 nm. Diethyldithiocarbamate forms complexes with the platinum in cisplatin to yield a platinum-DDTC (Pt-DDTC) complex with a high molar-extinction coefficient. The Pt(DDTC)2 complex thus formed was chromatographically separated and the quantitated by comparison of its detector response to that of a similarly derivatized standard preparation. DDTC also has application as a cleaning agent for cisplatin (e.g., for production equipment cleaning, spill cleanup). Destruction of cisplatin can be affected by the reaction of cisplatin with this cleaning agent. Derivatization of cisplatin will convert active cisplatin to platinum-DDTC on surfaces or in solution. Final cleaning can be accomplished using a water-for-injection rinse. After such a cleaning process, the rinse water, when collected and analyzed, showed levels of free cisplatin less than the detection concentration of 0.2 PPB and a total platinum concentration less than 10 PPB as Pt-DDTC complex.

A novel material screening platform for nanoporous gold-based neural electrodes

NASA Astrophysics Data System (ADS)

Chapman, Christopher Abbott Reece

Neural-electrical interfaces have emerged in the past decades as a promising modality to facilitate the understanding of the electropathophysiology of neurological disorders as well as the normal functioning of the central nervous system, and enable the treatment of neurological defects through electrical stimulation or electrically-controlled drug delivery. However, chronically implanted electrodes face a myriad of design challenges, including their coupling to neural tissue (biocompatibility), small form factor requirement, and their electrical properties (maintaining a low electrical impedance). Planar electrode materials such as planar platinum and gold experience a large increase in electrical impedance when electrode dimensions are reduced to increase spatial resolution of neural recordings. A decrease in electrode surface area reduces the total capacitance of the electrode double layer resulting in an increase in electrode impedance. This high impedance can reduce the signal amplitude and increase the thermal noise, resulting in degradation of signal-to-noise ratio. Conventionally, this increase in electrical impedance at small electrode dimensions has been mitigated by coatings with rough morphologies such as platinum black, conducting polymers, and titanium nitride. Porous surfaces have high effective surface area enabling low impedance at small electrode dimensions. However, achieving long-term stability of cellular coupling to the electrode surface has remained difficult. Designing electrodes that can physically couple with neurons successfully and maintain low impedance at small electrode dimensions necessitates consideration of novel electrode coatings, such as carbon nanotubes and gold nanopillars. Another promising material, and focus of this proposal, is thin film nanoporous gold (np-Au). Nanoporous gold is a promising material for addressing these limitations because of its inherently large effective surface area allows for lower impedances at small form factors, and its modifiable surface morphology can be used to control cell-electrode coupling. Additionally, thin film nanoporous gold is fabricated by traditional microfabrication methods, and thus can be directly adopted by the current state-of-the-art neural electrode fabrication processes. All these properties make thin film nanoporous gold a promising candidate for use in neural electrode surfaces. This dissertation seeks to characterize both the morphological and the electrical response of neural cells to thin film nanoporous gold morphologies using an in vitro electrode morphology screening platform. The specific aims for this proposal are to: (i) develop a electrode morphology library that displays varying topographies to study structure-property relationships of thin film nanoporous gold and cellular response, (ii) characterize neural cell response to identified nanoporous gold topographies that reduce adverse tissue response in vitro, and (iii) develop an electrophysiology platform to characterize neural coupling to each identified nanoporous gold topography.

Adsorption of benzene on low index surfaces of platinum in the presence of van der Waals interactions

NASA Astrophysics Data System (ADS)

K, Ayishabi P.; Chatanathodi, Raghu

2017-10-01

We have studied the adsorption of benzene on three low index surfaces of platinum using plane-wave Density Functional Theory (DFT) calculations, taking into consideration van der Waals (vdW) interaction. Experimentally, it is known that benzene adsorbs at the bridge site on the (111) surface, but in case of (110) and (100), this is not known yet. Our calculations show that benzene preferably adsorbs on bridge position on Pt(111) surface, whereas on Pt(110) and Pt(100) surfaces, the hollow position is energetically more favoured. The structural and electronic modifications of molecule and the surfaces are also examined. In all cases, adsorption-induced distortions of adsorbate-substrate complex are found to be modest in character, but relatively maximum in case of the (110) facet. The molecule is bound most strongly to the (110) surface. Importantly, we find that adsorption at bridge and atop positions are energetically feasible on the (110) surface, with the canting of benzene ring at a small angle from the metal plane. We study changes in electronic structure and the net charge transfer upon adsorption of benzene on all three low index planes. Inclusion of vdW interactions is important for obtaining realistic adsorption strengths for benzene on various Pt facets.

Release of low molecular weight silicones and platinum from silicone breast implants.

PubMed

Lykissa, E D; Kala, S V; Hurley, J B; Lebovitz, R M

1997-12-01

We have conducted a series of studies addressing the chemical composition of silicone gels from breast implants as well as the diffusion of low molecular weight silicones (LM-silicones) and heavy metals from intact implants into various surrounding media, namely, lipid-rich medium (soy oil), aqueous tissue culture medium (modified Dulbecco's medium, DMEM), or an emulsion consisting of DMEM plus 10% soy oil. LM-silicones in both implants and surrounding media were detected and quantitated using gas chromatography (GC) coupled with atomic emission (GC-AED) as well as mass spectrometric (GC/MS) detectors, which can detect silicones in the nanogram range. Platinum, a catalyst used in the preparation of silicone gels, was detected and quantitated using inductive argon-coupled plasma/mass spectrometry (ICP-MS), which can detect platinum in the parts per trillion range. Our results indicate that GC-detectable low molecular weight silicones contribute approximately 1-2% to the total gel mass and consist predominantly of cyclic and linear poly-(dimethylsiloxanes) ranging from 3 to 20 siloxane [(CH3)2-Si-O] units (molecular weight 200-1500). Platinum can be detected in implant gels at levels of approximately 700 micrograms/kg by ICP-MS. The major component of implant gels appears to be high molecular weight silicone polymers (HM-silicones) too large to be detected by GC. However, these HM-silicones can be converted almost quantitatively (80% by mass) to LM-silicones by heating implant gels at 150-180 degrees C for several hours. We also studied the rates at which LM-silicones and platinum leak through the intact implant outer shell into the surrounding media under a variety of conditions. Leakage of silicones was greatest when the surrounding medium was lipid-rich, and up to 10 mg/day LM-silicones was observed to diffuse into a lipid-rich medium per 250 g of implant at 37 degrees C. This rate of leakage was maintained over a 7-day experimental period. Similarly, platinum was also observed to leak through intact implants into lipid-containing media at rates of approximately 20-25 micrograms/day/250 g of implant at 37 degrees C. The rates at which both LM-silicones and platinum have been observed to leak from intact implants could lead to significant accumulation within lipid-rich tissues and should be investigated more fully in vivo.

Influence of crystal phases on electro-optic properties of epitaxially grown lanthanum-modified lead zirconate titanate films

NASA Astrophysics Data System (ADS)

Masuda, Shin; Seki, Atsushi; Masuda, Yoichiro

2010-02-01

We describe here how we have improved the crystal qualities and controlled the crystal phase of the lanthanum-modified lead zirconate titanate (PLZT) film without changing the composition ratio using an oxygen-pressure crystallization process. A PLZT film deposited on a SrTiO3 substrate with the largest electro-optic (EO) coefficient of 498 pm/V has been achieved by controlling the crystal phase of the film. Additionally, a fatigue-free lead zirconate titanate (PZT) capacitor with platinum electrodes has been realized by reducing the oxygen vacancies in the films.

Controlling the Growth and Catalytic Activity of Platinum Nanoparticles Using Peptide and Polymer Ligands

NASA Astrophysics Data System (ADS)

Forbes, Lauren Marie

Heterogeneous catalysts have widespread industrial applications. Platinum nanomaterials in particular, due to their particularly high electrocatalytic activity and durability, are used to catalyze a wide variety of reactions, including oxygen reduction, which is frequently used as the cathode reaction in fuel cells. As platinum is a very expensive material, a high priority in fuel cell research is the exploration of less expensive, more efficient catalysts for the oxygen reduction reaction (ORR). We demonstrate here the use of phage display to identify peptides that bind to Pt (100) which were then used to synthesize platinum cubes in solution. However, while the peptides were able to control particle growth, the bio-synthesized Pt particles showed extremely poor activity when tested for ORR. This could be attributed to peptide coverage on the surface or strong interactions between particular amino acids and the metal that are detrimental for catalysis. To investigate this further, we decided to investigate the role of individual amino acids on Pt nanocrystal synthesis and catalysis. For this, we conjugated the R-groups of single amino acids to polyethylene glycol (PEG) chains. Through this work we have determined that the identity of the amino acid R-group is important in both the synthesis and the catalytic activity of the particles. For Pt nanoparticle synthesis, we found that the hydrophobicity of the functional groups affected their ability to interact well with the particles during nucleation and growth, and thus only the hydrophilic functional groups were capable of mediating the synthesis to produce well-defined faceted particles. With respect to ORR, we found distinct trends that showed that the inclusion of certain amino acids could significantly enhance catalysis---even at high polymer loadings. This work presents evidence that counters the common conception that organic capping ligands decrease catalytic activity; in fact activity may actually be improved over bare metal through judicious choice and design of ligands that inhibit Pt oxidation and control chain packing at the Pt surface. Therefore, it may be possible to have ligands on a nanoparticle surface that allow the particles to be well-dispersed on an electrode surface, while simultaneously enhancing catalysis.

Rough Gold Electrodes for Decreasing Impedance at the Electrolyte/Electrode Interface

PubMed Central

Koklu, Anil; Sabuncu, Ahmet C.; Beskok, Ali

2016-01-01

Electrode polarization at the electrolyte/electrode interface is often undesirable for bio-sensing applications, where charge accumulated over an electrode at constant potential causes large potential drop at the interface and low measurement sensitivity. In this study, novel rough electrodes were developed for decreasing electrical impedance at the interface. The electrodes were fabricated using electrochemical deposition of gold and sintering of gold nanoparticles. The performances of the gold electrodes were compared with platinum black electrodes. A constant phase element model was used to describe the interfacial impedance. Hundred folds of decrease in interfacial impedance were observed for fractal gold electrodes and platinum black. Biotoxicity, contact angle, and surface morphology of the electrodes were investigated. Relatively low toxicity and hydrophilic nature of the fractal and granulated gold electrodes make them suitable for bioimpedance and cell electromanipulation studies compared to platinum black electrodes which are both hydrophobic and toxic. PMID:27695132

Gold-promoted structurally ordered intermetallic palladium cobalt nanoparticles for the oxygen reduction reaction.

PubMed

Kuttiyiel, Kurian A; Sasaki, Kotaro; Su, Dong; Wu, Lijun; Zhu, Yimei; Adzic, Radoslav R

2014-11-06

Considerable efforts to make palladium and palladium alloys active catalysts and a possible replacement for platinum have had a marginal success. Here we report on a structurally ordered Au10Pd₄₀Co₅₀ catalyst that exhibits comparable activity to conventional platinum catalysts in both acid and alkaline media. Electron microscopic techniques demonstrate that, at elevated temperatures, palladium cobalt nanoparticles undergo an atomic structural transition from core-shell to a rare intermetallic ordered structure with twin boundaries forming stable {111}, {110} and {100} facets via addition of gold atoms. The superior stability of this catalyst compared with platinum after 10,000 potential cycles in alkaline media is attributed to the atomic structural order of PdCo nanoparticles along with protective effect of clusters of gold atoms on the surface. This strategy of making ordered palladium intermetallic alloy nanoparticles can be used in diverse heterogeneous catalysis where particle size and structural stability matter.

Estimation of the alpha decay of Platinum isotopes using different versions of theoretical formula

NASA Astrophysics Data System (ADS)

Hosseini, S. S.; Hassanabadi, H.; Sobhani, H.

The alpha decay half-lives of even-even and even-odd Platinum (Pt) nuclei have been studied within the Coulomb and proximity potential model (CPPM). The present study is restricted to even-even nuclei with A = 166-198. The results are compared with other calculations such as the Semi-empirical formula (SemFIS) from Poenaru et al. based on fission theory of alpha decay, the Viola-Seaborg (VS), Royer (R) and Brown formulae. Also, the alpha decay half-lives have been calculated using the Scaling law of Brown (SLB), the Universal Decay Law (UDL) of Qi et al., the Scaling Law of Horoi et al. (SLH), and Akrawy-Dorin formula (ADF) of Akrawy and Poenaru, which are the Royer modified formula for alpha decay half-live by adding asymmetry term.

Characteristics of Hydrogen Sensors Based on Thin Tin Dioxide Films Modified with Gold

NASA Astrophysics Data System (ADS)

Almaev, A. V.; Gaman, V. I.

2017-11-01

Effect of hydrogen in the concentration range from 10 to 2000 ppm on the characteristics of sensors based on thin films of tin dioxide modified with gold (Au/SnO2:Sb, Au) is studied in the thermo-cyclic mode at temperatures from 623 to 773 K and absolute humidity from 2.5 to 20 g/m3. Experimental data are discussed using expressions obtained within the framework of a model that takes into account the presence of three types of adsorbed particles (O¯, OH, and OH¯) on the surface of SnO2 nanocrystals. The characteristics of the sensors based on thin Pt/Pd/SnO2:Sb films (the first series) are compared with those of Au/SnO2:Sb, Au films (the second series). It is found that the degree of dissociation of molecular hydrogen into atoms during adsorption on the sensor under interaction with Au particles on the SnO2 surface is 4 times greater than that under interaction with Pt/Pd particles. The degree of dissociation of H2O molecules into hydrogen atoms and hydroxyl groups in pure moist air on the surface of the sensors of the second series is 1.6 times greater than that for the sensors of the first series. Thus, gold is a more effective stimulator of the dissociation of H2 and H2O molecules than platinum and palladium. A formula is obtained that describes more accurately the dependence of the response of the sensors of both series to the effect of hydrogen on the concentration of this gas and on the temperature of the measuring devices.

Hollow microspheres with a tungsten carbide kernel for PEMFC application.

PubMed

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

2011-07-28

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

Thermal stability of Pt-Ti bilayer films annealing in vacuum and ambient atmosphere

NASA Astrophysics Data System (ADS)

Weng, Sizhe; Qiao, Li; Wang, Peng

2018-06-01

The thermal stability of platinum/titanium bilayer film dominates the performance when the film electrodes operate under extreme conditions, such as high temperature. In this study, a platinum/titanium bilayer film deposited by magnetron sputtering was used as a model system to study the influence of annealing in vacuum and ambient atmosphere on structural and electrical resistivity changes. The results show that in both cases blow 773 K annealing the metal platinum is the dominant phase, the alloying and the diffusion happen only at the interface of Pt and Ti. Two different structural evolutions set in when the temperature above 873 K, in vacuum an alloying process promotes with increasing of annealing temperature and metal Pt phase transforms to TiPt8 and finally to TiPt3 compounds, which leads to the increase of electrical resistivity. In ambient atmosphere annealing, when titanium diffused out to the surface of film, the oxidation reaction between titanium and oxygen suppresses the alloying process between platinum and titanium, in this case the metal Pt phase remains in the film and starts to agglomerate, defects such as grain boundary and voids in film reduced due to the recrystallization, results in the reduction of electrical resistivity.

Highly Crystalline Multimetallic Nanoframes with Three-Dimensional Electrocatalytic Surfaces

DOE PAGES

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

2014-02-27

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

Cathode catalyst for primary phosphoric fuel cells

NASA Technical Reports Server (NTRS)

Walsh, F.

1980-01-01

Alkylation of Vulcan XC-72 provided the most stable bond type for linking CoTAA to the surface of the carbon; this result is based on data obtained by cyclic voltammetry, pulse voltammetry and by release of 14C from bonded CoTAA. Half-cell tests at 100 C in 85% phosphoric acid showed that CoTAA bonded to the surface of carbon (Vulcan XC-72) via an alkylation procedure is a more active catalyst than is platinum based on a factor of two improvement in Tafel slope; dimeric CoTAA has catalytic activity equal to platinum. Half-cell tests also showed that bonded CoTAA catalysts do not suffer a loss in potential when air is used as a fuel rather than oxygen. Commercially available PTFE was shown to be stable for four months in 200 C 85% phosphoric acid based on lack of change in surface wetting properties, IR and physical characteristics. When stressed electrochemically in 150 C 85% phosphoric acid, PTFE also showed no changes after one month.

Quantitative determination of Escherichia coli based on the electrochemical measurement of bacterial catalase activity using H2O2-selective organic/inorganic-hybrid sol-gel film-modified Pt electrode.

PubMed

Hasebe, Yasushi; Fukuzawa, Michiru; Matsuhisa, Hironori

2009-01-01

Quantitative determination of Escherichia coli (E. coli) concentration was achieved by measuring the intrinsic catalase activity of E. coli using novel H2O2-selective organic/inorganic-hybrid sol-gel film-modified platinum (Pt) wire electrode. This hybrid sol-gel film is composed of three kinds of organosilanes and two biopolymers (i.e., chitosan and bovine serum albumin), and exhibited an excellent permselectivity toward H2O2 based on a size-exclusive mechanism. The steady-state anodic current for 100 [xmol/L H2O2 at +0.6 V (vs. Ag/AgCl) in 0.1 mol/L phosphate buffer (pH 6.5) solution was apparently diminished by the addition of E. coli samples, due to the decomposition of H2O2 by intrinsic catalase activity of E. coli. The time-dependent decrease in current (-AI/At) was significantly dependent on the E. coli concentration. The -AI/At was enhanced by the permeabilization pretreatment of E. coli samples with the mixed solution of polymyxin B and lysozyme. This H2O2-selective organic/inorganic-hybrid sol-gel film-modified platinum (Pt) wire electrode allowed quantitative determination of E. coli concentration ranging from 10(6) to 10(9) CFU/mL within 30 min. This method required no label and complicated procedure, and allowed rapid, simple and cost-effective quantitative electrochemical determination of catalase-positive bacteria.

In situ X-ray probing reveals fingerprints of surface platinum oxide.

PubMed

Friebel, Daniel; Miller, Daniel J; O'Grady, Christopher P; Anniyev, Toyli; Bargar, John; Bergmann, Uwe; Ogasawara, Hirohito; Wikfeldt, Kjartan Thor; Pettersson, Lars G M; Nilsson, Anders

2011-01-07

In situ X-ray absorption spectroscopy (XAS) at the Pt L(3) edge is a useful probe for Pt-O interactions at polymer electrolyte membrane fuel cell (PEMFC) cathodes. We show that XAS using the high energy resolution fluorescence detection (HERFD) mode, applied to a well-defined monolayer Pt/Rh(111) sample where the bulk penetrating hard X-rays probe only surface Pt atoms, provides a unique sensitivity to structure and chemical bonding at the Pt-electrolyte interface. Ab initio multiple-scattering calculations using the FEFF code and complementary extended X-ray absorption fine structure (EXAFS) results indicate that the commonly observed large increase of the white-line at high electrochemical potentials on PEMFC cathodes originates from platinum oxide formation, whereas previously proposed chemisorbed oxygen-containing species merely give rise to subtle spectral changes.

Photomicrographic Investigation of Spontaneous Freezing Temperatures of Supercooled Water Droplets

NASA Technical Reports Server (NTRS)

Dorsch, R. G.; Hacker, P. T.

1950-01-01

A photomicrographic technique for investigating eupercooled. water droplets has been devised and. used. to determine the spontaneous freezing temperatures of eupercooled. water droplets of the size ordinarily found. in the atmosphere. The freezing temperatures of 4527 droplets ranging from 8.75 to 1000 microns in diameter supported on a platinum surface and 571 droplets supported on copper were obtained. The average spontaneous freezing temperature decreased with decrease in the size of the droplets. The effect of size on the spontaneous freezing temperature was particularly marked below 60 microns. Frequency-distribution curves of the spontaneous freezing temperatures observed for droplets of a given size were obtained. Although no droplet froze at a temperature above 20 0 F, all droplets melted at 32 F. Results obtained with a copper support did not differ essentially from those obtained with a platinum surface.

SFG experiment and ab initio study of the chemisorption of CN - on low-index platinum surfaces

NASA Astrophysics Data System (ADS)

Tadjeddine, M.; Flament, J.-P.; Le Rille, A.; Tadjeddine, A.

2006-05-01

A dual analysis is proposed in order to have a better understanding of the adsorption of the cyanide ions on a platinum electrode. The SFG (Sum Frequency Generation) spectroscopy allows the in situ vibrational study and the SFG spectra of the CN - species adsorbed on single crystal Pt electrode allow a systematic study of the low-index platinum surfaces. This experimental work is supported by ab initio calculations using density functional theory and cluster models. For each surface orientation and each geometry, a cluster model of 20-30 Pt atoms has been built in order to interpret the chemisorption of the CN - ions through four kinds of adsorption geometry: on-top or bridge site, bonding via C or N atoms. Geometries have been optimized and adsorption energies, electronic properties and vibrational frequencies have been computed. From the electronic properties, we can propose an analysis of the bonding mechanism for each studied kind of adsorption. The SFG spectra of the CN -/Pt(1 1 1) system present an unique resonance owing to the top C adsorption. It is mainly the same for the CN -/Pt(1 0 0) system. It is also the case for the SFG spectra of the CN -/Pt(1 1 0) system recorded at negative electrochemical voltage; at more positive voltage, a second resonance appears at a lower frequency, owing to the top N adsorption. Experimental and theoretical values of the C-N stretching frequencies are in excellent agreement.

77 FR 75239 - Self-Regulatory Organizations; NYSE Arca, Inc.; Order Approving a Proposed Rule Change, as...

Federal Register 2010, 2011, 2012, 2013, 2014

2012-12-19

... SECURITIES AND EXCHANGE COMMISSION [Release No. 34-68430; File No. SR-NYSEArca-2012-111] Self-Regulatory Organizations; NYSE Arca, Inc.; Order Approving a Proposed Rule Change, as Modified by Amendment No. 1, To List and Trade Units of the Sprott Physical Platinum and Palladium Trust Pursuant to NYSE Arca Equities Rule 8.201 December 13, 2012. I...

Pt/Ceria-based Catalysts for Small Alcohol Electrooxidation

NASA Astrophysics Data System (ADS)

Menendez-Mora, Christian L.

High emissions of fossil-based energy sources have led to scientists around the world to develop new alternatives for the future. In this sense, fuel cells are a remarkable and promising energy option with less environmental impact. The most used fuels for this technology are hydrogen and small chain alcohols, which can be oxidized to transform their chemical energy into electrical power. To do this, fuel cells need catalysts that will act as an active surface where the oxidation can take place. The problem with platinum catalysts is its possible CO poisoning with intermediates that are produced before the complete oxidation of alcohol to CO2. Different approaches have been taken to try to resolve this issue. In this case, cerium oxide (ceria) was selected as a co-catalyst to mitigate the effect of CO poisoning of platinum. Ceria is a compound that has the ability to work as an "oxygen tank" and can donate oxygen to carbon monoxide that is strongly adsorbed at platinum surface to produce CO2 (carbon dioxide), regenerating the Pt surface for further alcohol oxidation. Therefore, enhancing the current density as well as the power output of a fuel cell. First, an occlusion deposition technique was used to prepare platinum/ceria composite electrodes and tested them towards small chain alcohol oxidation such as methanol oxidation reaction in acidic and alkaline media. The preliminary results demonstrated that the Pt/ceria electrodes were more efficient towards methanol electrooxidation when compared to Pt electrodes. This enhancement was attributed to the presence of ceria. A second preparation method was selected for the synthesis of ceria/Pt catalysts. In this case, a hydrothermal method was used and the catalysis were studied for the effect of MeOH, EtOH and n-BuOH oxidation. The observed effect was that electrodes made of Pt/Pt:CeO2-x showed better catalytic effect than Pt/ceria and platinum electrodes. Moreover, a comparison between ceria nanorods versus nanoparticles as substrates was done. The general result was that ceria nanoparticles showed better electrocatalytic behavior towards the oxidation of methanol in alkaline medium. Finally, as an outreach activity, an educational module to reinforce the electrochemical concepts in the General Chemistry Laboratory course at UPR-RP was developed. The module was based on Volta's Experiment and an improvement on students learning was detected when comparing this activity with the normal Daniel's cell experience that is used in most Universities at the undergraduate level. In summary, the findings of this thesis conclude that ceria is a compound that may enhance platinum catalytic activity by CO oxidation, promoting the oxidation of alcohols in acidic and alkaline medium. Moreover, catalysis depends on the morphology of the ceria that is used as the catalysts support.

Recent Advances in Catalyst Accelerated Stress Tests for Polymer Electrolyte Membrane Fuel Cells

DOE PAGES

Stariha, Sarah; Macauley, Natalia; Sneed, Brian T.; ...

2018-03-15

The U.S. Department of Energy (DOE) set the 2020 durability target for polymer electrolyte membrane fuel cell transportation applications at 5000 hours. Since it is impractical to test every fuel cell for this length of time, there is ever increasing interest in developing accelerated stress tests (ASTs) that can accurately simulate the material component degradation in the membrane electrode assembly (MEA) observed under automotive operating conditions, but over a much shorter time frame. In this study, a square-wave catalyst AST was examined that shows a 5X time acceleration factor over the triangle-wave catalyst AST and a 25X time acceleration factormore » over the modified wet drive-cycle catalyst durability protocol, significantly decreasing the testing time. These acceleration factors were correlated to the platinum (Pt) particle size increase and associated decrease in electrochemical surface area (ECSA). This square-wave AST has been adopted by the DOE as a standard protocol to evaluate catalyst durability. We also compare three catalyst-durability protocols using state-of-the-art platinum-cobalt catalysts supported on high surface area carbon (SOA Pt-Co/HSAC) in the cathode catalyst layer. The results for each of the three tests showed both catalyst particle size increase and transition metal leaching. Moreover the acceleration factors for the alloy catalysts were smaller due to Co leaching being the predominant mechanism of voltage decay in ~5 nm PtCo/C catalysts. Finally, an extremely harsh carbon corrosion AST was run using the same SOA Pt-Co/HSAC catalyst. This showed minimal change in particle size and a low percentage Co loss from the cathode catalyst particles, despite a significant loss in catalyst layer thickness and cell performance. The carbon corrosion rates during these various ASTs were directly measured by monitoring the CO 2 emission from the cathode, further confirming the ability of the square-wave AST to evaluate the electro-catalyst independently of the support.« less

Recent Advances in Catalyst Accelerated Stress Tests for Polymer Electrolyte Membrane Fuel Cells

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

Stariha, Sarah; Macauley, Natalia; Sneed, Brian T.

The U.S. Department of Energy (DOE) set the 2020 durability target for polymer electrolyte membrane fuel cell transportation applications at 5000 hours. Since it is impractical to test every fuel cell for this length of time, there is ever increasing interest in developing accelerated stress tests (ASTs) that can accurately simulate the material component degradation in the membrane electrode assembly (MEA) observed under automotive operating conditions, but over a much shorter time frame. In this study, a square-wave catalyst AST was examined that shows a 5X time acceleration factor over the triangle-wave catalyst AST and a 25X time acceleration factormore » over the modified wet drive-cycle catalyst durability protocol, significantly decreasing the testing time. These acceleration factors were correlated to the platinum (Pt) particle size increase and associated decrease in electrochemical surface area (ECSA). This square-wave AST has been adopted by the DOE as a standard protocol to evaluate catalyst durability. We also compare three catalyst-durability protocols using state-of-the-art platinum-cobalt catalysts supported on high surface area carbon (SOA Pt-Co/HSAC) in the cathode catalyst layer. The results for each of the three tests showed both catalyst particle size increase and transition metal leaching. Moreover the acceleration factors for the alloy catalysts were smaller due to Co leaching being the predominant mechanism of voltage decay in ~5 nm PtCo/C catalysts. Finally, an extremely harsh carbon corrosion AST was run using the same SOA Pt-Co/HSAC catalyst. This showed minimal change in particle size and a low percentage Co loss from the cathode catalyst particles, despite a significant loss in catalyst layer thickness and cell performance. The carbon corrosion rates during these various ASTs were directly measured by monitoring the CO 2 emission from the cathode, further confirming the ability of the square-wave AST to evaluate the electro-catalyst independently of the support.« less

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

Stariha, Sarah; Macauley, Natalia; Sneed, Brian T.

The U.S. Department of Energy (DOE) set the 2020 durability target for polymer electrolyte membrane fuel cell transportation applications at 5000 hours. Since it is impractical to test every fuel cell for this length of time, there is ever increasing interest in developing accelerated stress tests (ASTs) that can accurately simulate the material component degradation in the membrane electrode assembly (MEA) observed under automotive operating conditions, but over a much shorter time frame. In this study, a square-wave catalyst AST was examined that shows a 5X time acceleration factor over the triangle-wave catalyst AST and a 25X time acceleration factormore » over the modified wet drive-cycle catalyst durability protocol, significantly decreasing the testing time. These acceleration factors were correlated to the platinum (Pt) particle size increase and associated decrease in electrochemical surface area (ECSA). This square-wave AST has been adopted by the DOE as a standard protocol to evaluate catalyst durability. We also compare three catalyst-durability protocols using state-of-the-art platinum-cobalt catalysts supported on high surface area carbon (SOA Pt-Co/HSAC) in the cathode catalyst layer. The results for each of the three tests showed both catalyst particle size increase and transition metal leaching. Moreover the acceleration factors for the alloy catalysts were smaller due to Co leaching being the predominant mechanism of voltage decay in ~5 nm PtCo/C catalysts. Finally, an extremely harsh carbon corrosion AST was run using the same SOA Pt-Co/HSAC catalyst. This showed minimal change in particle size and a low percentage Co loss from the cathode catalyst particles, despite a significant loss in catalyst layer thickness and cell performance. The carbon corrosion rates during these various ASTs were directly measured by monitoring the CO 2 emission from the cathode, further confirming the ability of the square-wave AST to evaluate the electro-catalyst independently of the support.« less

Neuropilin-1-targeted gold nanoparticles enhance therapeutic efficacy of platinum(IV) drug for prostate cancer treatment.

PubMed

Kumar, Anil; Huo, Shuaidong; Zhang, Xu; Liu, Juan; Tan, Aaron; Li, Shengliang; Jin, Shubin; Xue, Xiangdong; Zhao, YuanYuan; Ji, Tianjiao; Han, Lu; Liu, Hong; Zhang, XiaoNing; Zhang, Jinchao; Zou, Guozhang; Wang, Tianyou; Tang, Suoqin; Liang, Xing-Jie

2014-05-27

Platinum-based anticancer drugs such as cisplatin, oxaliplatin, and carboplatin are some of the most potent chemotherapeutic agents but have limited applications due to severe dose-limiting side effects and a tendency for cancer cells to rapidly develop resistance. The therapeutic index can be improved through use of nanocarrier systems to target cancer cells efficiently. We developed a unique strategy to deliver a platinum(IV) drug to prostate cancer cells by constructing glutathione-stabilized (Au@GSH) gold nanoparticles. Glutathione (GSH) has well-known antioxidant properties, which lead to cancer regression. Here, we exploit the advantages of both the antioxidant properties and high surface-area-to-volume ratio of Au@GSH NPs to demonstrate their potential for delivery of a platinum(IV) drug by targeting the neuropilin-1 receptor (Nrp-1). A lethal dose of a platinum(IV) drug functionalized with the Nrp-1-targeting peptide (CRGDK) was delivered specifically to prostate cancer cells in vitro. Targeted peptide ensures specific binding to the Nrp-1 receptor, leading to enhanced cellular uptake level and cell toxicity. The nanocarriers were themselves nontoxic, but exhibited high cytotoxicity and increased efficacy when functionalized with the targeting peptide and drug. The uptake of drug-loaded nanocarriers is dependent on the interaction with Nrp-1 in cell lines expressing high (PC-3) and low (DU-145) levels of Nrp-1, as confirmed through inductively coupled plasma mass spectrometry and confocal microscopy. The nanocarriers have effective anticancer activity, through upregulation of nuclear factor kappa-B (NF-κB) protein (p50 and p65) expression and activation of NF-κB-DNA-binding activity. Our preliminary investigations with platinum(IV)-functionalized gold nanoparticles along with a targeting peptide hold significant promise for future cancer treatment.

Molecular dynamics study of solid-liquid heat transfer and passive liquid flow

NASA Astrophysics Data System (ADS)

Yesudasan Daisy, Sumith

High heat flux removal is a challenging problem in boilers, electronics cooling, concentrated photovoltaic and other power conversion devices. Heat transfer by phase change is one of the most efficient mechanisms for removing heat from a solid surface. Futuristic electronic devices are expected to generate more than 1000 W/cm2 of heat. Despite the advancements in microscale and nanoscale manufacturing, the maximum passive heat flux removal has been 300 W/cm2 in pool boiling. Such limitations can be overcome by developing nanoscale thin-film evaporation based devices, which however require a better understanding of surface interactions and liquid vapor phase change process. Evaporation based passive flow is an inspiration from the transpiration process that happens in trees. If we can mimic this process and develop heat removal devices, then we can develop efficient cooling devices. The existing passive flow based cooling devices still needs improvement to meet the future demands. To improve the efficiency and capacity of these devices, we need to explore and quantify the passive flow happening at nanoscales. Experimental techniques have not advanced enough to study these fundamental phenomena at the nanoscale, an alternative method is to perform theoretical study at nanoscales. Molecular dynamics (MD) simulation is a widely accepted powerful tool for studying a range of fundamental and engineering problems. MD simulations can be utilized to study the passive flow mechanism and heat transfer due to it. To study passive flow using MD, apart from the conventional methods available in MD, we need to have methods to simulate the heat transfer between solid and liquid, local pressure, surface tension, density, temperature calculation methods, realistic boundary conditions, etc. Heat transfer between solid and fluids has been a challenging area in MD simulations, and has only been minimally explored (especially for a practical fluid like water). Conventionally, an equilibrium canonical ensemble (NVT) is simulated using thermostat algorithms. For research in heat transfer involving solid liquid interaction, we need to perform non equilibrium MD (NEMD) simulations. In such NEMD simulations, the methods used for simulating heating from a surface is very important and must capture proper physics and thermodynamic properties. Development of MD simulation techniques to simulate solid-liquid heating and the study of fundamental mechanism of passive flow is the main focus of this thesis. An accurate surface-heating algorithm was developed for water which can now allow the study of a whole new set of fundamental heat transfer problems at the nanoscale like surface heating/cooling of droplets, thin-films, etc. The developed algorithm is implemented in the in-house developed C++ MD code. A direct two dimensional local pressure estimation algorithm is also formulated and implemented in the code. With this algorithm, local pressure of argon and platinum interaction is studied. Also, the surface tension of platinum-argon (solid-liquid) was estimated directly from the MD simulations for the first time. Contact angle estimation studies of water on platinum, and argon on platinum were also performed. A thin film of argon is kept above platinum plate and heated in the middle region, leading to the evaporation and pressure reduction thus creating a strong passive flow in the near surface region. This observed passive liquid flow is characterized by estimating the pressure, density, velocity and surface tension using Eulerian mapping method. Using these simulation, we have demonstrated the fundamental nature and origin of surface-driven passive flow. Heat flux removed from the surface is also estimated from the results, which shows a significant improvement can be achieved in thermal management of electronic devices by taking advantage of surface-driven strong passive liquid flow. Further, the local pressure of water on silicon di-oxide surface is estimated using the LAMMPS atomic to continuum (ATC) package towards the goal of simulating the passive flow in water.

Engineering Platinum Alloy Electrocatalysts in Nanoscale for PEMFC Application

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

He, Ting

2016-03-01

Fuel cells are expected to be a key next-generation energy source used for vehicles and homes, offering high energy conversion efficiency and minimal pollutant emissions. However, due to large overpotentials on anode and cathode, the efficiency is still much lower than theoretically predicted. During the past decades, considerable efforts have been made to investigate synergy effect of platinum alloyed with base metals. But, engineering the alloy particles in nanoscale has been a challenge. Most important challenges in developing nanostructured materials are the abilities to control size, monodispersity, microcomposition, and even morphology or self-assembly capability, so called Nanomaterials-by-Design, which requires interdisciplinarymore » collaborations among computational modeling, chemical synthesis, nanoscale characterization as well as manufacturing processing. Electrocatalysts, particularly fuel cell catalysts, are dramatically different from heterogeneous catalysts because the surface area in micropores cannot be electrochemically controlled on the same time scale as more transport accessible surfaces. Therefore, electrocatalytic architectures need minimal microporous surface area while maximizing surfaces accessible through mesopores or macropores, and to "pin" the most active, highest performance physicochemical state of the materials even when exposed to thermodynamic forces, which would otherwise drive restructuring, crystallization, or densification of the nanoscale materials. In this presentation, results of engineering nanoscale platinum alloy particles down to 2 ~ 4 nm will be discussed. Based on nature of alloyed base metals, various synthesis technologies have been studied and developed to achieve capabilities of controlling particle size and particle microcomposition, namely, core-shell synthesis, microemulsion technique, thermal decomposition process, surface organometallic chemical method, etc. The results show that by careful engineering the particle size and microcomposition in nanoscale, it is able to achieve superior electrocatalytic activities comparing with traditional preparative methods. Examples to be discussed are high surface area carbon supported Pt, PtM binary, and PtMN ternary alloys, their synthesis processes, characterizations and electrocatalytic activities towards molecular oxygen reduction.« less

Wetting and evaporation of salt-water nanodroplets: A molecular dynamics investigation.

PubMed

Zhang, Jun; Borg, Matthew K; Sefiane, Khellil; Reese, Jason M

2015-11-01

We employ molecular dynamics simulations to study the wetting and evaporation of salt-water nanodroplets on platinum surfaces. Our results show that the contact angle of the droplets increases with the salt concentration. To verify this, a second simulation system of a thin salt-water film on a platinum surface is used to calculate the various surface tensions. We find that both the solid-liquid and liquid-vapor surface tensions increase with salt concentration and as a result these cause an increase in the contact angle. However, the evaporation rate of salt-water droplets decreases as the salt concentration increases, due to the hydration of salt ions. When the water molecules have all evaporated from the droplet, two forms of salt crystals are deposited, clump and ringlike, depending on the solid-liquid interaction strength and the evaporation rate. To form salt crystals in a ring, it is crucial that there is a pinned stage in the evaporation process, during which salt ions can move from the center to the rim of the droplets. With a stronger solid-liquid interaction strength, a slower evaporation rate, and a higher salt concentration, a complete salt crystal ring can be deposited on the surface.

A new route for degradation of volatile organic compounds under visible light: using the bifunctional photocatalyst Pt/TiO2-xNx in H2-O2 atmosphere.

PubMed

Li, Danzhen; Chen, Zhixin; Chen, Yilin; Li, Wenjuan; Huang, Hanjie; He, Yunhui; Fu, Xianzhi

2008-03-15

The bifunctional photocatalyst Pt/TiO2-xNx has been successfully prepared by wet impregnation. The properties of Pt/ TiO2-xNx have been investigated by diffuse reflectance spectra, X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, a photoluminescence technique with terephthalic acid, and electric field induced surface photovoltage spectra. The photocatalytic activity of the sample was evaluated by the decomposition of volatile organic pollutants (VOCs) in a H2-O2 atmosphere under visible light irradiation. The results demonstrated that nitrogen-doped and platinum-modified TiO2 in a H2-O2 atmosphere could enormously increase the quantum efficiency of the photocatalytic system with excellent photocatalytic activity and high catalytic stability. The increased quantum efficiency can be explained by enhanced separation efficiency of photogenerated electron-hole pairs, higher interface electron transfer rate, and an increased number of surface hydroxyl radicals in the photocatalytic process. A mechanism was proposed to elucidate the degradation of VOCs over PtTiO(2-x)Nx in a H2-O2 atmosphere under visible light irradiation.

Refinement of Promising Coating Compositions for Directionally Cast Eutectics

NASA Technical Reports Server (NTRS)

Strangman, T. E.; Felten, E. J.; Benden, R. S.

1976-01-01

The successful application of high creep strength, directionally solidified gamma/gamma prime-delta (Ni-19.7Cb-6Cr-2.5Al) eutectic superalloy turbine blades requires the development of suitable coatings for airfoil, root and internal blade surfaces. In order to improve coatings for the gamma/gamma prime-delta alloy, the current investigation had the goals of (1) refining promising coating compositions for directionally solidified eutectics, (2) evaluating the effects of coating/ substrate interactions on the mechanical properties of the alloy, and (3) evaluating diffusion aluminide coatings for internal surfaces. Burner rig cyclic oxidation, furnace cyclic hot corrosion, ductility, and thermal fatigue tests indicated that NiCrAlY+Pt(63 to 127 micron Ni-18Cr-12Al-0.3Y + 6 micron Pt) and NiCrAlY(63 to 127 micron Ni-18Cr-12Al-0.3Y) coatings are capable of protecting high temperature gas path surfaces of eutectic alloy airfoils. Burner rig (Mach 0.37) testing indicated that the useful coating life of the 127 micron thick coatings exceeded 1000 hours at 1366 K (2000 deg F). Isothermal fatigue and furnance hot corrosion tests indicated that 63 micron NiCrAlY, NiCrAlY + Pt and platinum modified diffusion aluminide (Pt + Al) coating systems are capable of protecting the relatively cooler surfaces of the blade root. Finally, a gas phase coating process was evaluated for diffusion aluminizing internal surfaces and cooling holes of air-cooled gamma/gamma prime-delta turbine blades.

Energy recovery during advanced wastewater treatment: simultaneous estrogenic activity removal and hydrogen production through solar photocatalysis.

PubMed

Zhang, Wenlong; Li, Yi; Wang, Chao; Wang, Peifang; Wang, Qing

2013-03-01

Simultaneous estrogenic activity removal and hydrogen production from secondary effluent were successfully achieved using TiO(2) microspheres modified with both platinum nanoparticles and phosphates (P-TiO(2)/Pt) for the first time. The coexistence of platinum and phosphate on the surface of TiO(2) microspheres was confirmed by transmission electron microscope, energy-dispersive X-ray and X-ray photoelectron spectroscopy analyses. P-TiO(2)/Pt microspheres showed a significantly higher photocatalytic activity than TiO(2) microspheres and TiO(2) powders (P25) for the removal of estrogenic activity from secondary effluent with the removal ratio of 100%, 58.2% and 48.5% in 200 min, respectively. Moreover, the marked production of hydrogen (photonic efficiency: 3.23 × 10(-3)) was accompanied by the removal of estrogenic activity only with P-TiO(2)/Pt as photocatalysts. The hydrogen production rate was increasing with decreased DO concentration in secondary effluent. Results of reactive oxygen species (ROS) evaluation during P-TiO(2)/Pt photocatalytic process showed that O(2)(-)and OH were dominant ROS in aerobic phase, while OH was the most abundant ROS in anoxic phase. Changes of effluent organic matter (EfOM) during photocatalysis revealed that aromatic, hydrophobic, and high molecular weight fractions of EfOM were preferentially transformed into non-humic, hydrophilic, and low MW fractions (e.g. aldehydes and carboxylic acids), which were continuously utilized as electron donors in hydrogen production process. Copyright © 2012 Elsevier Ltd. All rights reserved.

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).

Water-soluble platinum nanoparticles stabilized by sulfonated N-heterocyclic carbenes: influence of the synthetic approach.

PubMed

Baquero, Edwin A; Tricard, Simon; Coppel, Yannick; Flores, Juan C; Chaudret, Bruno; de Jesús, Ernesto

2018-03-28

The synthesis of metal nanoparticles (NPs) under controlled conditions in water remains a challenge in nanochemistry. Two different approaches to obtain platinum NPs, which involve the treatment of aqueous solutions of preformed sulfonated (NHC)Pt(ii) dimethyl complexes with carbon monoxide, and of (NHC)Pt(0) diolefin complexes with dihydrogen (NHC = N-heterocyclic carbene), are disclosed here. The resulting NPs were found to be highly stable in water under air for an indefinite time period. Coordination of the NHC ligands to the platinum surface via the carbenic carbon was monitored by solid-state NMR spectroscopy, and the presence of a platinum-carbon bond was unambiguously evidenced by the determination of a 13 C- 195 Pt coupling constant (1106 and 1050 Hz for NPs containing 13 C labeled-NHC ligands and prepared under CO and H 2 , respectively). The coordination of CO to the (NHC)Pt(ii) precursors prior to formation of the NPs was confirmed by NMR spectroscopy. When using a disulfonated NHC ligand, a second coordination sphere containing bis(NHC)Pt(ii) complexes is described. Under CO, the formation of NPs was found to be slower than in a previously reported thermal method (Angew. Chem., Int. Ed., 2014, 53, 13220-13224), but led to NPs of similar sizes, whereas under H 2 , the synthesis of platinum NPs progressed even more slowly and produced larger NPs. In addition to the influence of the synthetic approach, the present study highlights the importance of ligand design for NP stabilization.

Atomic layer deposition of Al{sub 2}O{sub 3} for single electron transistors utilizing Pt oxidation and reduction

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

McConnell, Michael S., E-mail: mmcconn5@nd.edu; Schneider, Louisa C.; Karbasian, Golnaz

This work describes the fabrication of single electron transistors using electron beam lithography and atomic layer deposition to form nanoscale tunnel transparent junctions of alumina (Al{sub 2}O{sub 3}) on platinum nanowires using either water or ozone as the oxygen precursor and trimethylaluminum as the aluminum precursor. Using room temperature, low frequency conductance measurements between the source and drain, it was found that devices fabricated using water had higher conductance than devices fabricated with ozone. Subsequent annealing caused both water- and ozone-based devices to increase in conductance by more than 2 orders of magnitude. Furthermore, comparison of devices at low temperaturesmore » (∼4 K) showed that annealed devices displayed much closer to the ideal behavior (i.e., constant differential conductance) outside of the Coulomb blockade region and that untreated devices showed nonlinear behavior outside of the Coulomb blockade region (i.e., an increase in differential conductance with source-drain voltage bias). Transmission electron microscopy cross-sectional images showed that annealing did not significantly change device geometry, but energy dispersive x-ray spectroscopy showed an unusually large amount of oxygen in the bottom platinum layer. This suggests that the atomic layer deposition process results in the formation of a thin platinum surface oxide, which either decomposes or is reduced during the anneal step, resulting in a tunnel barrier without the in-series native oxide contribution. Furthermore, the difference between ozone- and water-based devices suggests that ozone promotes atomic layer deposition nucleation by oxidizing the surface but that water relies on physisorption of the precursors. To test this theory, devices were exposed to forming gas at room temperature, which also reduces platinum oxide, and a decrease in resistance was observed, as expected.« less

Electron-driven and thermal chemistry during water-assisted purification of platinum nanomaterials generated by electron beam induced deposition

PubMed Central

Warneke, Jonas; Kopyra, Janina

2018-01-01

Focused electron beam induced deposition (FEBID) is a versatile tool for the direct-write fabrication of nanostructures on surfaces. However, FEBID nanostructures are usually highly contaminated by carbon originating from the precursor used in the process. Recently, it was shown that platinum nanostructures produced by FEBID can be efficiently purified by electron irradiation in the presence of water. If such processes can be transferred to FEBID deposits produced from other carbon-containing precursors, a new general approach to the generation of pure metallic nanostructures could be implemented. Therefore this study aims to understand the chemical reactions that are fundamental to the water-assisted purification of platinum FEBID deposits generated from trimethyl(methylcyclopentadienyl)platinum(IV) (MeCpPtMe3). The experiments performed under ultrahigh vacuum conditions apply a combination of different desorption experiments coupled with mass spectrometry to analyse reaction products. Electron-stimulated desorption monitors species that leave the surface during electron exposure while post-irradiation thermal desorption spectrometry reveals products that evolve during subsequent thermal treatment. In addition, desorption of volatile products was also observed when a deposit produced by electron exposure was subsequently brought into contact with water. The results distinguish between contributions of thermal chemistry, direct chemistry between water and the deposit, and electron-induced reactions that all contribute to the purification process. We discuss reaction kinetics for the main volatile products CO and CH4 to obtain mechanistic information. The results provide novel insights into the chemistry that occurs during purification of FEBID nanostructures with implications also for the stability of the carbonaceous matrix of nanogranular FEBID materials under humid conditions. PMID:29441253

Low-energy-electron interactions with DNA: approaching cellular conditions with atmospheric experiments

NASA Astrophysics Data System (ADS)

Alizadeh, Elahe; Sanche, Léon

2014-04-01

A novel technique has been developed to investigate low energy electron (LEE)-DNA interactions in the presence of small biomolecules (e.g., N2, O2, H2O) found near DNA in the cell nucleus, in order to simulate cellular conditions. In this technique, LEEs are emitted from a metallic surface exposed by soft X-rays and interact with DNA thin films at standard ambient temperature and pressure (SATP). Whereas atmospheric N2 had little effect on the yields of LEE-induced single and double strand breaks, both O2 and H2O considerably modified and increased such damage. The highest yields were obtained when DNA is embedded in a combined O2 and H2O atmosphere. In this case, the amount of additional double strand breaks was supper-additive. The effect of modifying the chemical and physical stability of DNA by platinum-based chemotherapeutic agents (Pt-drugs) including cisplatin, carboplatin and oxaliplatin was also investigated with this technique. The results obtained provide information on the role played by subexcitation-energy electrons and dissociative electron attachment in the radiosensitization of DNA by Pt-drugs, which is an important step to unravel the mechanisms of radiosensitisation of these agents in chemoradiation cancer therapy.

Advances in UV-Plasmonics: A Detailed Analysis of Metallic Materials as Candidates for New Applications in Nanothecnology

DTIC Science & Technology

2014-08-26

Indium, Rhodium, Ruthenium, Tungsten, Titanium, Chromium, Palladium, Copper, Platinum and Magnesium . These have been chosen because all of them...performance. vii. Considering that the observed behaviors occur precisely where UV surface-enhanced Raman spectra indicated strong local field...research objective was centered on the UV plasmonic properties of Rh NPs by means of surface-enhanced Raman spectroscopy, surface-enhanced

n-hydrocarbons conversions over metal-modified solid acid catalysts

NASA Astrophysics Data System (ADS)

Zarubica, A.; Ranđelović, M.; Momčilović, M.; Radulović, N.; Putanov, P.

2013-12-01

The quality of a straight-run fuel oil can be improved if saturated n-hydrocarbons of low octane number are converted to their branched counterparts. Poor reactivity of traditional catalysts in isomerization reactions imposed the need for the development of new catalysts among which noble metal promoted acid catalysts, liquid and/or solid acid catalysts take a prominent place. Sulfated zirconia and metal promoted sulfated zirconia exhibit high activity for the isomerization of light alkanes at low temperatures. The present paper highlights the original results which indicate that the modification of sulfated zirconia by incorporation of metals (platinum and rhenium) significantly affects catalytic performances in n-hydrocarbon conversion reactions. Favourable activity/selectivity of the promoted sulfated zirconia depends on the crystal phase composition, critical crystallites sizes, platinum dispersion, total acidity and type of acidity. Attention is also paid to the recently developed solid acid catalysts used in other conversion reactions of hydrocarbons.

Sensitive determination of citrinin based on molecular imprinted electrochemical sensor

NASA Astrophysics Data System (ADS)

Atar, Necip; Yola, Mehmet Lütfi; Eren, Tanju

2016-01-01

In this report, a novel molecular imprinted voltammetric sensor based on glassy carbon electrode (GCE) modified with platinum nanoparticles (PtNPs) involved in a polyoxometalate (H3PW12O40, POM) functionalized reduced graphene oxide (rGO) was prepared for the determination of citrinin (CIT). The developed surfaces were characterized by using scanning electron microscope (SEM), transmission electron microscope (TEM), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) method. CIT imprinted GCE was prepared via electropolymerization process of 80.0 mM pyrrole as monomer in the presence of phosphate buffer solution (pH 6.0) containing 20.0 mM CIT. The linearity range and the detection limit of the developed method were calculated as 1.0 × 10-12-1.0 × 10-10 M and 2.0 × 10-13 M, respectively. In addition, the voltammetric sensor was applied to rye samples. The stability and selectivity of the voltammetric sensor were also reported.

Infrared absorptivities of transition metals at room and liquid-helium temperatures.

NASA Technical Reports Server (NTRS)

Jones, M. C.; Palmer, D. C.; Tien, C. L.

1972-01-01

Evaluation of experimental data concerning the normal spectral absorptivities of the transition metals, nickel, iron, platinum, and chromium, at both room and liquid-helium temperatures in the wavelength range from 2.5 to 50 microns. The absorptivities were derived from reflectivity measurements made relative to a room-temperature vapor-deposited gold reference mirror. The absorptivity of the gold reference mirror was measured calorimetrically, by use of infrared laser sources. Investigation of various methods of sample-surface preparation resulted in the choice of a vacuum-annealing process as the final stage. The experimental results are discussed on the basis of the anomalous-skin-effect theory modified for multiple conduction bands. As predicted, the results approach a single-band model toward the longer wavelengths. Agreement between theory and experiment is considerably improved by taking into account the modification of the relaxation time due to the photon-electron-phonon interaction proposed by Holstein (1954) and Gurzhi (1958); but, particularly at helium temperatures, the calculated curve is consistently below the experimental results.

Composite catalysts supported on modified carbon substrates and methods of making the same

DOEpatents

Popov, Branko N [Columbia, SC; Subramanian, Nalini [Kennesaw, GA; Colon-Mercado, Hector R [Columbia, SC

2009-11-17

A method of producing a composite carbon catalyst is generally disclosed. The method includes oxidizing a carbon precursor (e.g., carbon black). Optionally, nitrogen functional groups can be added to the oxidized carbon precursor. Then, the oxidized carbon precursor is refluxed with a non-platinum transitional metal precursor in a solution. Finally, the solution is pyrolyzed at a temperature of at least about 500.degree. C.

Modification of Glucose Oxidase biofuel cell by multi-walled carbon nanotubes

NASA Astrophysics Data System (ADS)

Lotfi, Ladan; Farahbakhsh, Afshin; Aghili, Sina

2018-01-01

Biofuel cells are a subset of fuel cells that employ biocatalysts. Enzyme-based biofuel cells (EBFCs) generate electrical energy from biofuels such as glucose and ethanol, which are renewable and sustainable energy sources. Glucose biofuel cells (GBFCs) are particularly interesting nowadays due to continuous harvesting of oxygen and glucose from bioavailable substrates, activity inside the human body, and environmental benign, which generate electricity through oxidation of glucose on the anode and reduction of oxygen on the cathode. Promoting the electron transfer of redox enzymes at modified electrode utilizing Nano size materials, such as carbon nanotubes (CNT), to achieve the direct electrochemistry of enzymes has been reported. The polypyrrole-MWCNTs-glucose oxidase (PY-CNT-GOx) electrode has been investigated in the present work. Cyclic voltammetry tests were performed in a three-electrode electrochemical set-up with modified electrode (Pt/PPy/MWCNTs/GOx) was used as working electrode. Platinum flat and Ag/AgCl (saturated KCl) were used as counter electrode and the reference electrode, respectively. The biofuel cells probe was prepared by immobilizing MWCNTs at the tip of a platinum (Pt) electrode (0.5 cm2) with PPy as the support matrix We have demonstrated a well-dispersed nanomaterial PPy/MWNT, which is able to immobilize GOx firmly under the condition of the absence of any other cross-linking agent.

Direct alcohol fuel cells: Increasing platinum performance by modification with sp-group metals

NASA Astrophysics Data System (ADS)

Figueiredo, Marta C.; Sorsa, Olli; Doan, Nguyet; Pohjalainen, Elina; Hildebrand, Helga; Schmuki, Patrik; Wilson, Benjamin P.; Kallio, Tanja

2015-02-01

By using sp group metals as modifiers, the catalytic properties of Pt can be improved toward alcohols oxidation. In this work we report the performance increase of direct alcohol fuel cells (DAFC) fuelled with ethanol or 2-propanol with platinum based anode electrodes modified with Bi and Sb adatoms. For example, by simply adding Sb to the Pt/C based anode ink during membrane electrode assembly fabrication of a direct ethanol fuel cell (DEFC) its performance is improved three-fold, with more than 100 mV increase in the open circuit potential. For the fuel cell fuelled with 2-propanol high power densities are obtained at very high potentials with these catalyst materials suggesting a great improvement for practical applications. Particularly in the case of Pt/C-Bi, the improvement is such that within 0.6 V (from 0.7 to 0.1 V) the power densities are between 7 and 9 mW/cm2. The results obtained with these catalysts are in the same range as those obtained with other bimetallic catalysts comprising of PtRu and PtSn, which are currently considered to be the best for these type of fuel cells and that are obtained by more complicated (and consequently more expensive) methods.

21 CFR 892.5730 - Radionuclide brachytherapy source.

Code of Federal Regulations, 2014 CFR

2014-04-01

... radionuclide which may be enclosed in a sealed container made of gold, titanium, stainless steel, or platinum and intended for medical purposes to be placed onto a body surface or into a body cavity or tissue as...

21 CFR 892.5730 - Radionuclide brachytherapy source.

Code of Federal Regulations, 2013 CFR

2013-04-01

... radionuclide which may be enclosed in a sealed container made of gold, titanium, stainless steel, or platinum and intended for medical purposes to be placed onto a body surface or into a body cavity or tissue as...

21 CFR 892.5730 - Radionuclide brachytherapy source.

Code of Federal Regulations, 2012 CFR

2012-04-01

... radionuclide which may be enclosed in a sealed container made of gold, titanium, stainless steel, or platinum and intended for medical purposes to be placed onto a body surface or into a body cavity or tissue as...

21 CFR 892.5730 - Radionuclide brachytherapy source.

Code of Federal Regulations, 2011 CFR

2011-04-01

... radionuclide which may be enclosed in a sealed container made of gold, titanium, stainless steel, or platinum and intended for medical purposes to be placed onto a body surface or into a body cavity or tissue as...

High aspect ratio AFM Probe processing by helium-ion-beam induced deposition.

PubMed

Onishi, Keiko; Guo, Hongxuan; Nagano, Syoko; Fujita, Daisuke

2014-11-01

A Scanning Helium Ion Microscope (SHIM) is a high resolution surface observation instrument similar to a Scanning Electron Microscope (SEM) since both instruments employ finely focused particle beams of ions or electrons [1]. The apparent difference is that SHIMs can be used not only for a sub-nanometer scale resolution microscopic research, but also for the applications of very fine fabrication and direct lithography of surfaces at the nanoscale dimensions. On the other hand, atomic force microscope (AFM) is another type of high resolution microscopy which can measure a three-dimensional surface morphology by tracing a fine probe with a sharp tip apex on a specimen's surface.In order to measure highly uneven and concavo-convex surfaces by AFM, the probe of a high aspect ratio with a sharp tip is much more necessary than the probe of a general quadrangular pyramid shape. In this paper we report the manufacture of the probe tip of the high aspect ratio by ion-beam induced gas deposition using a nanoscale helium ion beam of SHIM.Gas of platinum organic compound was injected into the sample surface neighborhood in the vacuum chamber of SHIM. The decomposition of the gas and the precipitation of the involved metal brought up a platinum nano-object in a pillar shape on the normal commercial AFM probe tip. A SHIM system (Carl Zeiss, Orion Plus) equipped with the gas injection system (OmniProbe, OmniGIS) was used for the research. While the vacuum being kept to work, we injected platinum organic compound ((CH3)3(CH3C5H4)Pt) into the sample neighborhood and irradiated the helium ion beam with the shape of a point on the apex of the AFM probe tip. It is found that we can control the length of the Pt nano-pillar by irradiation time of the helium ion beam. The AFM probe which brought up a Pt nano-pillar is shown in Figure 1. It is revealed that a high-aspect-ratio Pt nano-pillar of ∼40nm diameter and up to ∼2000 nm length can be grown. In addition, for possible heating by the helium ion beam, it was observed that an original probe shape was transformed. AFM measurement of a reference sample (pitch 100-500 nm, depth 100 nm) of the lines and spaces was performed using the above probes. The conventional probes which did not bring up platinum was not able to get into the ditch enough. Therefore it was found that a salient was big and a reentrant was shallow. On the other hand, the probe which brought up platinum was able to enter enough to the depths of the ditch.jmicro;63/suppl_1/i30-a/DFU075F1F1DFU075F1Fig.1.SHIM image of the AFM probe with the Pt nano-pillar fabricated by ion-beam induced deposition. © The Author 2014. Published by Oxford University Press on behalf of The Japanese Society of Microscopy. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

Prototype thin-film thermocouple/heat-flux sensor for a ceramic-insulated diesel engine

NASA Technical Reports Server (NTRS)

Kim, Walter S.; Barrows, Richard F.

1988-01-01

A platinum versus platinum-13 percent rhodium thin-film thermocouple/heat-flux sensor was devised and tested in the harsh, high-temperature environment of a ceramic-insulated, low-heat-rejection diesel engine. The sensor probe assembly was developed to provide experimental validation of heat transfer and thermal analysis methodologies applicable to the insulated diesel engine concept. The thin-film thermocouple configuration was chosen to approximate an uninterrupted chamber surface and provide a 1-D heat-flux path through the probe body. The engine test was conducted by Purdue University for Integral Technologies, Inc., under a DOE-funded contract managed by NASA Lewis Research Center. The thin-film sensor performed reliably during 6 to 10 hr of repeated engine runs at indicated mean surface temperatures up to 950 K. However, the sensor suffered partial loss of adhesion in the thin-film thermocouple junction area following maximum cyclic temperature excursions to greater than 1150 K.

Enantioselective recognition at mesoporous chiral metal surfaces.

PubMed

Wattanakit, Chularat; Côme, Yémima Bon Saint; Lapeyre, Veronique; Bopp, Philippe A; Heim, Matthias; Yadnum, Sudarat; Nokbin, Somkiat; Warakulwit, Chompunuch; Limtrakul, Jumras; Kuhn, Alexander

2014-01-01

Chirality is widespread in natural systems, and artificial reproduction of chiral recognition is a major scientific challenge, especially owing to various potential applications ranging from catalysis to sensing and separation science. In this context, molecular imprinting is a well-known approach for generating materials with enantioselective properties, and it has been successfully employed using polymers. However, it is particularly difficult to synthesize chiral metal matrices by this method. Here we report the fabrication of a chirally imprinted mesoporous metal, obtained by the electrochemical reduction of platinum salts in the presence of a liquid crystal phase and chiral template molecules. The porous platinum retains a chiral character after removal of the template molecules. A matrix obtained in this way exhibits a large active surface area due to its mesoporosity, and also shows a significant discrimination between two enantiomers, when they are probed using such materials as electrodes.

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

PubMed

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

2017-09-13

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

Carbon nanotube modified probes for stable and high sensitivity conductive atomic force microscopy

NASA Astrophysics Data System (ADS)

Slattery, Ashley D.; Shearer, Cameron J.; Gibson, Christopher T.; Shapter, Joseph G.; Lewis, David A.; Stapleton, Andrew J.

2016-11-01

Conductive atomic force microscopy (C-AFM) is used to characterise the nanoscale electrical properties of many conducting and semiconducting materials. We investigate the effect of single walled carbon nanotube (SWCNT) modification of commercial Pt/Ir cantilevers on the sensitivity and image stability during C-AFM imaging. Pt/Ir cantilevers were modified with small bundles of SWCNTs via a manual attachment procedure and secured with a conductive platinum pad. AFM images of topography and current were collected from heterogeneous polymer and nanomaterial samples using both standard and SWCNT modified cantilevers. Typically, achieving a good current image comes at the cost of reduced feedback stability. In part, this is due to electrostatic interaction and increased tip wear upon applying a bias between the tip and the sample. The SWCNT modified tips displayed superior current sensitivity and feedback stability which, combined with superior wear resistance of SWCNTs, is a significant advancement for C-AFM.

Surface restructuring behavior of various types of poly(dimethylsiloxane) in water detected by SFG.

PubMed

Chen, Chunyan; Wang, Jie; Chen, Zhan

2004-11-09

Surface structures of several different poly(dimethylsiloxane) (PDMS) materials, tetraethoxysilane-cured hydroxy-terminated PDMS (TEOS-PDMS), platinum-cured vinyl-terminated PDMS (Pt-PDMS), platinum-cured vinyl-terminated poly(diphenylsiloxane)-co-poly(dimethylsiloxane) (PDPS-co-PDMS), and PDMS-co-polystyrene (PDMS-co-PS) copolymer in air and water have been investigated by sum frequency generation (SFG) vibrational spectroscopy. The SFG spectra collected from all PDMS surfaces in both air and water are dominated by methyl group stretches, indicating that all the surfaces are mainly covered by methyl groups. Other than surface-dominating methyl groups, some -Si-CH2-CH2- moieties on the Pt-PDMS surface have also been detected in air, which are present at cross-linking points. Information about the average orientation angle and angle distribution of the methyl groups on the PDMS surface has been evaluated. Surface restructuring of the methyl groups has been observed for all PDMS surfaces in water. Upon contacting water, the methyl groups on all PDMS surfaces tilt more toward the surface. The detailed restructuring behaviors of several PDMS surfaces in water and the effects of molecular weight on restructuring behaviors have been investigated. For comparison, in addition to air and water, surface structures of PDMS materials mentioned above in a nonpolar solvent, FC-75, have also been studied. By comparing the different response of phenyl groups to water on both PDPS-co-PDMS and PS-co-PDMS surfaces, we have demonstrated how the restructuring behaviors of surface phenyl groups are affected by the structural flexibility of the molecular chains where they are attached.

Redox competition mode of scanning electrochemical microscopy (RC-SECM) for visualisation of local catalytic activity.

PubMed

Eckhard, Kathrin; Chen, Xingxing; Turcu, Florin; Schuhmann, Wolfgang

2006-12-07

In order to locally analyse catalytic activity on modified surfaces a transient redox competition mode of scanning electrochemical microscopy (SECM) has been developed. In a bi-potentiostatic experiment the SECM tip competes with the sample for the very same analyte. This leads to a current decrease at the SECM tip, if it is positioned in close proximity to an active catalyst site on the surface. Specifically, local catalytic activity of a Pt-catalyst modified sample with respect to the catalytic reduction of molecular oxygen was investigated. At higher local catalytic activity the local 02 partial pressure within the gap between accurately positioned SECM tip and sample is depleted, leading to a noticeable tip current decrease over active sites. A flexible software module has been implemented into the SECM to adapt the competition conditions by proper definition of tip and sample potentials. A potential pulse profile enables the localised electrochemically induced generation of molecular oxygen prior to the competition detection. The current decay curves are recorded over the entire duration of the applied reduction pulse. Hence, a time resolved processing of the acquired current values provides movies of the local oxygen concentration against x,y-position. The SECM redox competition mode was verified with a macroscopic Pt-disk electrode as a test sample to demonstrate the feasibility of the approach. Moreover, highly dispersed electro-deposited spots of gold and platinum on glassy carbon were visualised using the redox competition mode of SECM. Catalyst spots of different nature as well as activity inhomogeneities within one spot caused by local variations in Pt-loading were visualised successfully.

Method for high temperature mercury capture from gas streams

DOEpatents

Granite, Evan J [Wexford, PA; Pennline, Henry W [Bethel Park, PA

2006-04-25

A process to facilitate mercury extraction from high temperature flue/fuel gas via the use of metal sorbents which capture mercury at ambient and high temperatures. The spent sorbents can be regenerated after exposure to mercury. The metal sorbents can be used as pure metals (or combinations of metals) or dispersed on an inert support to increase surface area per gram of metal sorbent. Iridium and ruthenium are effective for mercury removal from flue and smelter gases. Palladium and platinum are effective for mercury removal from fuel gas (syngas). An iridium-platinum alloy is suitable for metal capture in many industrial effluent gas streams including highly corrosive gas streams.

A phototactic micromotor based on platinum nanoparticle decorated carbon nitride.

PubMed

Ye, Zhenrong; Sun, Yunyu; Zhang, Hui; Song, Bo; Dong, Bin

2017-11-30

In this paper, we report a unique phototactic (both positive and negative) micromotor based on platinum nanoparticle decorated carbon nitride. The phototaxis relies on the self-diffusiophoretic mechanism and different surface modifications. The micromotor reported in the current study does not require the addition of any external fuels and shows versatile motion behaviour, i.e. start, stop, directional and programmable motion, which is controlled by light. In addition, since the actuation of the precipitated micromotors at the bottom of a solution using light results in the opacity changes from transparent to translucent, we anticipate that the current micromotor may have potential application in the field of smart windows.

Design and fabrication of miniaturized PEM fuel cell combined microreactor with self-regulated hydrogen mechanism

NASA Astrophysics Data System (ADS)

Balakrishnan, A.; Frei, M.; Kerzenmacher, S.; Reinecke, H.; Mueller, C.

2015-12-01

In this work we present the design and fabrication of the miniaturized PEM fuel cell combined microreactor system with hydrogen regulation mechanism and testing of prototype microreactor. The system consists of two components (i) fuel cell component and (ii) microreactor component. The fuel cell component represents the miniaturized PEM fuel cell system (combination of screen printed fuel cell assembly and an on-board hydrogen storage medium). Hydrogen production based on catalytic hydrolysis of chemical hydride takes place in the microreactor component. The self-regulated hydrogen mechanism based on the gaseous hydrogen produced from the catalytic hydrolysis of sodium borohydride (NaBH4) gets accumulated as bubbles at the vicinity of the hydrophobic coated hydrogen exhaust holes. When the built up hydrogen bubbles pressure exceeds the burst pressure at the hydrogen exhaust holes the bubble collapses. This collapse causes a surge of fresh NaBH4 solution onto the catalyst surface leading to the removal of the reaction by-products formed at the active sites of the catalyst. The catalyst used in the system is platinum deposited on a base substrate. Nickel foam, carbon porous medium (CPM) and ceramic plate were selected as candidates for base substrate for developing a robust catalyst surface. For the first time the platinum layer fabricated by pulsed electrodeposition and dealloying (EPDD) technique is used for hydrolysis of NaBH4. The major advantages of such platinum catalyst layers are its high surface area and their mechanical stability. Prototype microreactor system with self-regulated hydrogen mechanism is demonstrated.

Compatability of dispersion-strengthened platinum with resistojet propellants

NASA Technical Reports Server (NTRS)

Whalen, Margaret V.; Nathal, Michael V.

1987-01-01

Resistojets for the Space Station require long life and multipropellant capability. The choice of available materials to meet these requirements is limited. Dispersion-strengthened platinum was selected. Past results indicated that it should be suffieiently inert in candidate propellant environments and should be capable of operating at moderate temperatures for extended periods. A series of propellant compatibility tests was done with platinum strengthened with either yttria or zirconia. Data presented included the results of 1000-hr tests in CO2, H2, ammonia (NH3), N2, steam, hydrazine (N2H4), and methane (CH4); and 2000-hr tests in H2 and NH3. The platinum samples were tested at 1400 C in CO2, H2, NH3, N2, steam, and N2H4; at 500 C in CH4; and at 800 C in N2H4. The mass-loss results indicated material life, exptrapolated from experimental mass-loss data, in excess of 100 000 hr in all environments except steam and N2H4, where it was greater than or =45000 hr. Generally, on the basis of mass loss, there were no compatibility concerns in any of the environments considered. Optical and scanning electron microscopy were used to determine the effect of propellants on the material surface and to evaluate material stability.

Facile detection of Troponin I using dendritic platinum nanoparticles and capillary tube indicators.

PubMed

Lee, Sanghee; Kwon, Donghoon; Yim, Changyong; Jeon, Sangmin

2015-01-01

A facile method was developed for the detection of Troponin I (TnI) using dendritic platinum nanoparticles and capillary tube indicators. Dendritic platinum nanoparticles were functionalized with TnI antibodies, which were used to capture TnI in human serum. The captured TnI was conjugated to the inner surface of a glass vial, to which a hydrogen peroxide (H2O2) solution was added. After the glass vial was sealed with a screw cap containing a silicon septum, a capillary tube containing a drop of ink was inserted through the septum. The catalytic dissociation of H2O2 to water and oxygen increased the pressure inside the glass vial and raised the ink level in the capillary tube. The ink level increased with the platinum nanoparticle concentration, which is proportional to the TnI concentration. The sensitivity of this assay for TnI in human serum after a 5 min dissociation reaction, detected with the naked eye, was 0.1 ng/mL, which was better than the sensitivity of the conventional colorimetric method using the TMB oxidation reaction under the same experimental conditions. A control experiment using alpha-fetoprotein, interleukin-5, and C-reactive protein revealed that the developed method was highly selective for the detection of TnI.

Tailoring molecular specificity toward a crystal facet: a lesson from biorecognition toward Pt{111}.

PubMed

Ruan, Lingyan; Ramezani-Dakhel, Hadi; Chiu, Chin-Yi; Zhu, Enbo; Li, Yujing; Heinz, Hendrik; Huang, Yu

2013-02-13

Surfactants with preferential adsorption to certain crystal facets have been widely employed to manipulate morphologies of colloidal nanocrystals, while mechanisms regarding the origin of facet selectivity remain an enigma. Similar questions exist in biomimetic syntheses concerning biomolecular recognition to materials and crystal surfaces. Here we present mechanistic studies on the molecular origin of the recognition toward platinum {111} facet. By manipulating the conformations and chemical compositions of a platinum {111} facet specific peptide, phenylalanine is identified as the dominant motif to differentiate {111} from other facets. The discovered recognition motif is extended to convert nonspecific peptides into {111} specific peptides. Further extension of this mechanism allows the rational design of small organic molecules that demonstrate preferential adsorption to the {111} facets of both platinum and rhodium nanocrystals. This work represents an advance in understanding the organic-inorganic interfacial interactions in colloidal systems and paves the way to rational and predictable nanostructure modulations for many applications.

Gold–promoted structurally ordered intermetallic palladium cobalt nanoparticles for the oxygen reduction reaction

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

Kuttiyiel, Kurian A.; Sasaki, Kotaro; Su, Dong

2014-11-06

Considerable efforts to make palladium and palladium alloys active catalysts and a possible replacement for platinum have had a marginal success. Here, we report on a structurally ordered Au₁₀Pd₄₀Co₅₀ catalyst that exhibits comparable activity to conventional platinum catalysts in both acid and alkaline media. Electron microscopic techniques demonstrate that via addition of gold atoms PdCo nanoparticles undergo at elevated temperatures an atomic structural transition from core-shell to a rare intermetallic ordered structure with twin boundaries forming stable {111}, {110} and {100} facets. The superior stability of this catalyst compared to platinum after 10,000 potential cycles in alkaline media is attributedmore » to the atomic structural order of PdCo nanoparticles along with protective effect of clusters of gold atoms on the surface. This strategy of making ordered palladium intermetallic alloy nanoparticles can be used in diverse heterogeneous catalysis where particle size and structural stability matters.« less

Synergistic effect of Brønsted acid and platinum on purification of automobile exhaust gases

PubMed Central

Fu, Wei; Li, Xin-Hao; Bao, Hong-Liang; Wang, Kai-Xue; Wei, Xiao; Cai, Yi-Yu; Chen, Jie-Sheng

2013-01-01

The catalytic purification of automobile exhaust gases (CO, NOx and hydrocarbons) is one of the most practiced conversion processes used to lower the emissions and to reduce the air pollution. Nevertheless, the good performance of exhaust gas purification catalysts often requires the high consumption of noble metals such as platinum. Here we report that the Brønsted acid sites on the external surface of a microporous silicoaluminophosphate (SAPO) act as a promoter for exhaust gas purification, effectively cutting the loading amount of platinum in the catalyst without sacrifice of performance. It is revealed that in the Pt-loaded SAPO-CHA catalyst, there exists a remarkable synergistic effect between the Brønsted acid sites and the Pt nanoparticles, the former helping to adsorb and activate the hydrocarbon molecules for NO reduction during the catalytic process. The thermal stability of SAPO-CHA also makes the composite catalyst stable and reusable without activity decay. PMID:23907148

Synergistic effect of Brønsted acid and platinum on purification of automobile exhaust gases.

PubMed

Fu, Wei; Li, Xin-Hao; Bao, Hong-Liang; Wang, Kai-Xue; Wei, Xiao; Cai, Yi-Yu; Chen, Jie-Sheng

2013-01-01

The catalytic purification of automobile exhaust gases (CO, NOx and hydrocarbons) is one of the most practiced conversion processes used to lower the emissions and to reduce the air pollution. Nevertheless, the good performance of exhaust gas purification catalysts often requires the high consumption of noble metals such as platinum. Here we report that the Brønsted acid sites on the external surface of a microporous silicoaluminophosphate (SAPO) act as a promoter for exhaust gas purification, effectively cutting the loading amount of platinum in the catalyst without sacrifice of performance. It is revealed that in the Pt-loaded SAPO-CHA catalyst, there exists a remarkable synergistic effect between the Brønsted acid sites and the Pt nanoparticles, the former helping to adsorb and activate the hydrocarbon molecules for NO reduction during the catalytic process. The thermal stability of SAPO-CHA also makes the composite catalyst stable and reusable without activity decay.

Platinum Monolayer Electrocatalysts for Anodic Oxidation of Alcohols.

PubMed

Li, Meng; Liu, Ping; Adzic, Radoslav R

2012-12-06

The slow, incomplete oxidation of methanol and ethanol on platinum-based anodes as well as the high price and limited reserves of Pt has hampered the practical application of direct alcohol fuel cells. We describe the electrocatalysts consisting of one Pt monolayer (one atom thick layer) placed on extended or nanoparticle surfaces having the activity and selectivity for the oxidation of alcohol molecules that can be controlled with platinum-support interaction. The suitably expanded Pt monolayer (i.e., Pt/Au(111)) exhibits a factor of 7 activity increase in catalyzing methanol electrooxidation relative to Pt(111). Sizable enhancement is also observed for ethanol electrooxidation. Furthermore, a correlation between substrate-induced lateral strain in a Pt monolayer and its activity/selectivity is established and rationalized by experimental and theoretical studies. The knowledge we gained with single-crystal model catalysts was successfully applied in designing real nanocatalysts. These findings for alcohols are likely to be applicable for the oxidation of other classes of organic molecules.

Biocompatibility of platinum-metallized silicone rubber: in vivo and in vitro evaluation.

PubMed

Vince, V; Thil, M A; Veraart, C; Colin, I M; Delbeke, J

2004-01-01

Silicone rubber is commonly used for biomedical applications, including implanted cuff electrodes for both recording and stimulation of peripheral nerves. This study was undertaken to evaluate the consequences of a new platinum metallization method on the biocompatibility of silicone rubber cuff electrodes. This method was introduced in order to allow the manufacture of spiral nerve cuff electrodes with a large number of contacts. The metallization process, implying silicone coating with poly(methyl methacrylate) (PMMA), its activation by an excimer laser and subsequent electroless metal deposition, led to a new surface microtexture. The neutral red cytotoxicity assay procedure was first applied in vitro on BALB/c 3T3 fibroblasts in order to analyze the cellular response elicited by the studied material. An in vivo assay was then performed to investigate the tissue reaction after chronic subcutaneous implantation of the metallized material. Results demonstrate that silicone rubber biocompatibility is not altered by the new platinum metallization method.

In Situ Structural Studies of the Underpotential Deposition of Copper onto an Iodine Covered Platinum Surface Using X-Ray Standing Waves

DTIC Science & Technology

1991-01-01

electrocrystallization, catalysis, and surface chemistry. In this process, submonolayer to monolayer(s) amounts of a metal can be electrodeposited on a foreign...mechanisms involving nucleation and growth processes. Although electrochemical methods are invaluable in controlling and measuring thermodynamic...obtain direct atomic structural information about metal deposits on an iodine covered Pt(IIl) surface . They found that electrodeposition occurred in a

Nanoparticle mediated micromotor motion

NASA Astrophysics Data System (ADS)

Liu, Mei; Liu, Limei; Gao, Wenlong; Su, Miaoda; Ge, Ya; Shi, Lili; Zhang, Hui; Dong, Bin; Li, Christopher Y.

2015-03-01

In this paper, we report the utilization of nanoparticles to mediate the motion of a polymer single crystal catalytic micromotor. Micromotors have been fabricated by directly self-assembling functional nanoparticles (platinum and iron oxide nanoparticles) onto one or both sides of two-dimensional polymer single crystals. We show that the moving velocity of these micromotors in fluids can be readily tuned by controlling the nanoparticles' surface wettability and catalytic activity. A 3 times velocity increase has been achieved for a hydrophobic micromotor as opposed to the hydrophilic ones. Furthermore, we demonstrate that the catalytic activity of platinum nanoparticles inside the micromotor can be enhanced by their synergetic interactions with iron oxide nanoparticles and an electric field. Both strategies lead to dramatically increased moving velocities, with the highest value reaching ~200 μm s-1. By decreasing the nanoparticles' surface wettability and increasing their catalytic activity, a maximum of a ~10-fold increase in the moving speed of the nanoparticle based micromotor can be achieved. Our results demonstrate the advantages of using nanoparticles in micromotor systems.In this paper, we report the utilization of nanoparticles to mediate the motion of a polymer single crystal catalytic micromotor. Micromotors have been fabricated by directly self-assembling functional nanoparticles (platinum and iron oxide nanoparticles) onto one or both sides of two-dimensional polymer single crystals. We show that the moving velocity of these micromotors in fluids can be readily tuned by controlling the nanoparticles' surface wettability and catalytic activity. A 3 times velocity increase has been achieved for a hydrophobic micromotor as opposed to the hydrophilic ones. Furthermore, we demonstrate that the catalytic activity of platinum nanoparticles inside the micromotor can be enhanced by their synergetic interactions with iron oxide nanoparticles and an electric field. Both strategies lead to dramatically increased moving velocities, with the highest value reaching ~200 μm s-1. By decreasing the nanoparticles' surface wettability and increasing their catalytic activity, a maximum of a ~10-fold increase in the moving speed of the nanoparticle based micromotor can be achieved. Our results demonstrate the advantages of using nanoparticles in micromotor systems. Electronic supplementary information (ESI) available: Fig. S1-S5 and Video S1-S3. See DOI: 10.1039/c4nr07558g

Applications of Thin Film Thermocouples for Surface Temperature Measurement

NASA Technical Reports Server (NTRS)

Martin, Lisa C.; Holanda, Raymond

1994-01-01

Thin film thermocouples provide a minimally intrusive means of measuring surface temperature in hostile, high temperature environments. Unlike wire thermocouples, thin films do not necessitate any machining of the surface, therefore leaving intact its structural integrity. Thin films are many orders of magnitude thinner than wire, resulting in less disruption to the gas flow and thermal patterns that exist in the operating environment. Thin film thermocouples have been developed for surface temperature measurement on a variety of engine materials. The sensors are fabricated in the NASA Lewis Research Center's Thin Film Sensor Lab, which is a class 1000 clean room. The thermocouples are platinum-13 percent rhodium versus platinum and are fabricated by the sputtering process. Thin film-to-leadwire connections are made using the parallel-gap welding process. Thermocouples have been developed for use on superalloys, ceramics and ceramic composites, and intermetallics. Some applications of thin film thermocouples are: temperature measurement of space shuttle main engine turbine blade materials, temperature measurement in gas turbine engine testing of advanced materials, and temperature and heat flux measurements in a diesel engine. Fabrication of thin film thermocouples is described. Sensor durability, drift rate, and maximum temperature capabilities are addressed.

Comparative electron microscopic study of the surface structure of gold, Teflon, and titanium stapes prostheses.

PubMed

Kwok, P; Fisch, U; Strutz, J; Jacob, P

2001-09-01

The goal of this study was to compare stapes prostheses of different materials with respect to their surface structures and to discuss their suitability for their use in stapes surgery. The surface condition of a stapes prosthesis plays an important role in relation to the type of membrane that forms between the stapes piston and the bony edge of the stapedotomy opening. The quality of this membrane in thickness and mobility is one of the determinants for postoperative hearing improvement. The surface conditions of gold, Teflon/steel, Teflon/platinum, and titanium stapes prostheses were examined with a scanning electron microscope. The loop, shaft, and end of each prosthesis were studied. The gold piston was the smoothest of the four pistons examined. When it was cut with a scalpel, a very smooth surface was achieved at the end area. The Teflon piston had the roughest surface. However, when it was cut, a smooth surface with a parallel arrangement of fibers resulted. Its steel loop was the smoothest, followed by gold and platinum. The titanium shaft had a scaly surface, which remained when the end of the shaft was shortened. Because a certain roughness of the piston surface is necessary for the development of a stable membrane between the piston and the edge of the stapedotomy opening, the titanium prosthesis is considered to be the most suitable for stapes surgery of the three pistons examined.

Methane steam reforming rates over Pt, Rh and Ni(111) accounting for H tunneling and for metal lattice vibrations

NASA Astrophysics Data System (ADS)

German, Ernst D.; Sheintuch, Moshe

2017-02-01

Microkinetic models of methane steam reforming (MSR) over bare platinum and rhodium (111) surfaces are analyzed in present work using calculated rate constants. The individual rate constants are classified into three different sets: (i) rate constants of adsorption and desorption steps of CH4, H2O, CO and of H2; (ii) rate constants of dissociation and formation of A-H bonds (A = C, O, and H), and (iii) rate constants of dissociation and formation of C-O bond. The rate constants of sets (i) and (iii) are calculated using transition state theory and published thermochemical data. The rate constants of H-dissociation reactions (set (ii)) are calculated in terms of a previously-developed approach that accounts for thermal metal lattice vibrations and for H tunneling through a potential barrier of height which depends on distance of AH from a surface. Pre-exponential factors of several group (ii) steps were calculated to be usually lower than the traditional kBT/h due to tunneling effect. Surface composition and overall MSR rates over platinum and rhodium surfaces are compared with those over nickel surface showing that operating conditions strongly affect on the activity order of the catalysts.

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

Interactions of small platinum clusters with the TiC(001) surface

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

Mao, Jianjun; Li, Shasha; Chu, Xingli

2015-11-14

Density functional theory calculations are used to elucidate the interactions of small platinum clusters (Pt{sub n}, n = 1–5) with the TiC(001) surface. The results are analyzed in terms of geometric, energetic, and electronic properties. It is found that a single Pt atom prefers to be adsorbed at the C-top site, while a Pt{sub 2} cluster prefers dimerization and a Pt{sub 3} cluster forms a linear structure on the TiC(001). As for the Pt{sub 4} cluster, the three-dimensional distorted tetrahedral structure and the two-dimensional square structure almost have equal stability. In contrast with the two-dimensional isolated Pt{sub 5} cluster, the adsorbed Pt{submore » 5} cluster prefers a three-dimensional structure on TiC(001). Substantial charge transfer takes place from TiC(001) surface to the adsorbed Pt{sub n} clusters, resulting in the negatively charged Pt{sub n} clusters. At last, the d-band centers of the absorbed Pt atoms and their implications in the catalytic activity are discussed.« less

Synthesis of Platinum-nickel Nanowires and Optimization for Oxygen Reduction Performance.

PubMed

Alia, Shaun M; Pivovar, Bryan S

2018-04-27

Platinum-nickel (Pt-Ni) nanowires were developed as fuel cell electrocatalysts, and were optimized for the performance and durability in the oxygen reduction reaction. Spontaneous galvanic displacement was used to deposit Pt layers onto Ni nanowire substrates. The synthesis approach produced catalysts with high specific activities and high Pt surface areas. Hydrogen annealing improved Pt and Ni mixing and specific activity. Acid leaching was used to preferentially remove Ni near the nanowire surface, and oxygen annealing was used to stabilize near-surface Ni, improving durability and minimizing Ni dissolution. These protocols detail the optimization of each post-synthesis processing step, including hydrogen annealing to 250 °C, exposure to 0.1 M nitric acid, and oxygen annealing to 175 °C. Through these steps, Pt-Ni nanowires produced increased activities more than an order of magnitude than Pt nanoparticles, while offering significant durability improvements. The presented protocols are based on Pt-Ni systems in the development of fuel cell catalysts. These techniques have also been used for a variety of metal combinations, and can be applied to develop catalysts for a number of electrochemical processes.

Conical Tungsten Tips as Substrates for the Preparation of Ultramicroelectrodes

PubMed Central

Hermans, Andre; Wightman, R. Mark

2008-01-01

Here we describe a simple method to prepare voltammetric microelectrodes using tungsten wires as a substrate. Tungsten wires have high tensile modulus and enable the fabrication of electrodes that have small dimensions overall while retaining rigidity. In this work, 125 μm tungsten wires with a conical tip were employed. For the preparation of gold or platinum ultramicroelectrodes, commercial tungsten microelectrodes, completely insulated except at the tip, were used as substrates. Following removal of oxides from the exposed tungsten, platinum or gold was electroplated yielding surfaces with an electroactive area of between 1×10−6 cm2 to 2×10−6 cm2. Carbon surfaces on the etched tip of tungsten microwires were prepared by coating with photoresist followed by pyrolysis. The entire electrode was then insulated with Epoxylite except the tip yielding an exposed carbon surface with an area of around 4×10−6 cm2 to 6×10−6 cm2. All three types of ultramicroelectrodes fabricated on the tungsten wire had similar electrochemical behavior to electrodes fabricated from wires or fibers insulated with glass tubes. PMID:17129002

Advances in Thin Film Sensor Technologies for Engine Applications

NASA Technical Reports Server (NTRS)

Lei, Jih-Fen; Martin, Lisa C.; Will, Herbert A.

1997-01-01

Advanced thin film sensor techniques that can provide accurate surface strain and temperature measurements are being developed at NASA Lewis Research Center. These sensors are needed to provide minimally intrusive characterization of advanced materials (such as ceramics and composites) and structures (such as components for Space Shuttle Main Engine, High Speed Civil Transport, Advanced Subsonic Transports and General Aviation Aircraft) in hostile, high-temperature environments and for validation of design codes. This paper presents two advanced thin film sensor technologies: strain gauges and thermocouples. These sensors are sputter deposited directly onto the test articles and are only a few micrometers thick; the surface of the test article is not structurally altered and there is minimal disturbance of the gas flow over the surface. The strain gauges are palladium-13% chromium based and the thermocouples are platinum-13% rhodium vs. platinum. The fabrication techniques of these thin film sensors in a class 1000 cleanroom at the NASA Lewis Research Center are described. Their demonstration on a variety of engine materials, including superalloys, ceramics and advanced ceramic matrix composites, in several hostile, high-temperature test environments are discussed.

Detection of platinum species in plant material.

PubMed

Messerschmidt, J; Alt, F; Tölg, G

1995-05-01

Model experiments for the detection of platinum species in extracts from native and platinum-treated grass cultivations are described. The procedural steps are cultivation of the grass samples, extraction and concentration of the platinum species by ultrafiltration and freeze-drying, preparative separation of the species by gel chromatography followed by isotachophoresis, and sequential analytical detection of the separated platinum species by adsorptive voltammetry. After isotachophoresis, sharp peaks of platinum species could be detected. In the native grass extract only one platinum species (160-200 kDa) was found. In the platinum-treated grass extracts several platinum species were observed in the molecular mass range from 1 to > 1000 kDa. By an extremely sensitive platinum determination method (adsorptive voltammetry; detection limit, 2 pg Pt abs.) it was possible to detect platinum even in stained protein bands from horizontal gel electrophoresis of platinum containing fractions obtained after isotachophoresis.

Structural Property Effects for Platinum Modified Aluminide Coatings.

DTIC Science & Technology

1986-09-01

change from a low energy fracture to a high energy one occurs is called the DBTT. Transition temperatures are exhibited by body centered cubic and...tdapcrature as a result of residual ~:n~~.’ estresses unless the sample had been plastically deformed. Use ofpl~stic ..... .:,.as jilwed exam-ination of a...34 Fracture Properties of Superalloys," Superalloys Source Book, American Society for Metals, 1984. 11. American Society for Metals, Metals Handbook, Desk

Selective electrocatalytic oxidation of sorbitol to fructose and sorbose.

PubMed

Kwon, Youngkook; de Jong, Ed; van der Waal, Jan Kees; Koper, Marc T M

2015-03-01

A new electrocatalytic method for the selective electrochemical oxidation of sorbitol to fructose and sorbose is demonstrated by using a platinum electrode promoted by p-block metal atoms. By the studying a range of C4, C5 and C6 polyols, it is found that the promoter interferes with the stereochemistry of the polyol and thereby modifies its reactivity. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Schwarz, Kathleen; Xu, Bingjun; Yan, Yushan

The design of better heterogeneous catalysts for applications such as fuel cells and electrolyzers requires a mechanistic understanding of electrocatalytic reactions and the dependence of their activity on operating conditions such as pH. A satisfactory explanation for the unexpected pH dependence of electrochemical properties of platinum surfaces has so far remained elusive, with previous explanations resorting to complex co-adsorption of multiple species and resulting in limited predictive power. This knowledge gap suggests that the fundamental properties of these catalysts are not yet understood, limiting systematic improvement. In this paper, we analyze the change in charge and free energies upon adsorptionmore » using density-functional theory (DFT) to establish that water adsorbs on platinum step edges across a wide voltage range, including the double-layer region, with a loss of approximately 0.2 electrons upon adsorption. We show how this as-yet unreported change in net surface charge due to this water explains the anomalous pH variations of the hydrogen underpotential deposition (H upd) and the potentials of zero total charge (PZTC) observed in published experimental data. This partial oxidation of water is not limited to platinum metal step edges, and we report the charge of the water on metal step edges of commonly used catalytic metals, including copper, silver, iridium, and palladium, illustrating that this partial oxidation of water broadly influences the reactivity of metal electrodes.« less

Dimethyl ether electro-oxidation on platinum surfaces

DOE PAGES

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

2016-02-27

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

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

PubMed

Somorjai, Gabor A; Marsh, Anderson L

2005-04-15

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

Platinum porous nanoparticles hybrid with metal ions as probes for simultaneous detection of multiplex cancer biomarkers.

PubMed

Wang, Zifeng; Liu, Na; Ma, Zhanfang

2014-03-15

In this work, platinum porous nanoparticles (PtPNPs) absorbed metal ions as electrochemical signals were fabricated. Clean-surface PtPNPs were prepared by a surfactant-free method and decorated with amino groups via 2-aminoethanethiol. Amino capped PtPNPs complexation with Cd(2+) and Cu(2+) to form PtPNPs-Cd(2+) and PtPNPs-Cu(2+) hybrids, respectively. Anti-CEA and Anti-AFP separately labeled with PtPNPs-Cd(2+) and PtPNPs-Cu(2+) were used as distinguishable signal tags for capturing antigens. The metal ions were detected in a single run through differential pulse voltammetry (DPV) without acid dissolution, electric potentials and peak heights of which reflected the identity and concentrations of the corresponding antigen. Ionic liquid reduced graphene oxide (IL-rGO) modified glassy carbon electrode (GCE) was used as a substrate, which was rich in amino groups to immobilize antibodies by glutaraldehyde through cross-link between aldehyde groups and amino groups. Using the proposed probes and platform, a novel sandwich-type electrochemical immunosensor for simultaneous detecting carcinoembryonic antigen (CEA) and alpha-fetoprotein (AFP) was successfully developed. This immunoassay possessed good linearity from 0.05 ng mL(-1) to 200 ng mL(-1) for both CEA and AFP. The detection limit of CEA was 0.002 ng mL(-1) and that of AFP was 0.05 ng mL(-1) (S/N=3). Furthermore, analysis of clinical serum samples using this immunosensor was well consistent with the data determined by the enzyme-linked immunosorbent assay (ELISA). It suggested that the proposed electrochemical immunoassay provided a potential application of clinical screening for early-stage cancers. © 2013 Published by Elsevier B.V.

X-ray Crystal Truncation Rod Studies of Surface Oxidation and Reduction on Pt(111)

DOE PAGES

Liu, Yihua; Barbour, Andi; Komanicky, Vladimir; ...

2016-02-26

Here, we present X-ray crystal truncation rods measurements of Pt(111) surface under electrochemical conditions. Analyses of crystal truncation rods reveal that surface oxide formation buckles the top surface layer of platinum to two different heights at the potential (0.95 V vs RHE) below the so-called place-exchange potential. While the anti-Bragg intensity, sensitive to the top surface layer, drops in response to the anodic charge transfers, its responses to the cathodic charge transfers are significantly delayed. Implications to the surface oxidation and reduction behaviors are discussed.

Gas sensitive materials for gas detection and method of making

DOEpatents

Trakhtenberg, Leonid Israilevich; Gerasimov, Genrikh Nikolaevich; Gromov, Vladimir Fedorovich; Rozenberg, Valeriya Isaakovna

2012-12-25

A gas sensitive material comprising SnO2 nanocrystals doped with In2O3 and an oxide of a platinum group metal, and a method of making the same. The platinum group metal is preferably Pd, but also may include Pt, Ru, Ir, and combinations thereof. The SnO2 nanocrystals have a specific surface of 7 or greater, preferably about 20 m2/g, and a mean particle size of between about 10 nm and about 100 nm, preferably about 40 nm. A gas detection device made from the gas sensitive material deposited on a substrate, the gas sensitive material configured as a part of a current measuring circuit in communication with a heat source.

Non-contact Thermophysical Property Measurements of Liquid and Supercooled Platinum

NASA Astrophysics Data System (ADS)

Ishikawa, Takehiko; Paradis, Paul‑François; Koike, Noriyuki

2006-03-01

Thermophysical properties of equilibrium and supercooled liquid platinum were measured using non-contact diagnostic techniques with an electrostatic levitator. Over the 1691 to 2216 K temperature range, the density can be expressed as ρ(T)=19.2 × 103-0.96(T-Tm) (kg \\cdot m-3) with Tm=2041 K, yielding a volume expansion coefficient of 5.0 × 10-5 K-1. In addition, the surface tension can be expressed as γ(T)=1.80 × 103-0.14(T-Tm) (10-3 N \\cdot m-1) and the viscosity as η(T)=0.25 \\exp[4.99 × 104/(RT)] (10-3 Pa \\cdot s) over the 1743 to 2313 K temperature range.

Method for in-situ restoration of platinum resistance thermometer calibration

DOEpatents

Carroll, R.M.

1987-10-23

A method is provided for in-situ restoration of platinum resistance thermometers (PRT's) that have undergone surface oxide contamination and/or stain-related damage causing decalibration. The method, which may be automated using a programmed computer control arrangement, consists of applying a dc heating current to the resistive sensing element of the PRT of sufficient magnitude to heat the element to an annealing temperature and maintaining the temperature for a specified period to restore the element to a stress-free calibration condition. The process anneals the sensing element of the PRT without subjecting the entire PRT assembly to the annealing temperature and may be used in the periodic maintenance of installed PRT's. 1 fig.

A genosensor for detection of consensus DNA sequence of Dengue virus using ZnO/Pt-Pd nanocomposites.

PubMed

Singhal, Chaitali; Pundir, C S; Narang, Jagriti

2017-11-15

An electrochemical genosensor based on Zinc oxide/platinum-palladium (ZnO/Pt-Pd) modified fluorine doped tin oxide (FTO) glass plate was fabricated for detection of consensus DNA sequence of Dengue virus (DENV) using methylene blue (MB) as an intercalating agent. To achieve it, probe DNA (PDNA) was immobilized on the surface of ZnO/Pt-Pd nanocomposites modified FTO electrode. The synthesized nano-composites were characterized by high resolution transmission electron microscopy (HRTEM), energy dispersive X-ray analysis (EDX), atomic force microscopy (AFM), scanning electron microscopy (SEM), UV-Vis spectroscopy, X-ray diffraction (XRD) analysis and Fourier transform infra-red (FTIR) spectroscopy. This PDNA modified electrode (PDNA/ZnO/Pt-Pd/FTO) served as a signal amplification platform for the detection of the target hybridized DNA (TDNA). The hybridization between PDNA and TDNA was detected by reduction in current, generated by interaction of anionic mediator, i.e., methylene blue (MB) with free guanine (3'G) of ssDNA. The sensor showed a dynamic linear range of 1 × 10 -6 M to 100 × 10 -6 M with LOD as 4.3 × 10 -5 M and LOQ as 9.5 × 10 -5 M. Till date, majorly serotype specific biosensors for dengue detection have been developed. The genosensor reported here eliminates the possibility of false result as in case of serotype specific DNA sensor. This is the report where conserved sequences present in all the serotypes of Dengue virus has been employed for fabrication of a genosensor. Copyright © 2017 Elsevier B.V. All rights reserved.

A comparative study of carbon-platinum hybrid nanostructure architecture for amperometric biosensing.

PubMed

Vanegas, Diana C; Taguchi, Masashige; Chaturvedi, Prachee; Burrs, Stephanie; Tan, Michael; Yamaguchi, Hitomi; McLamore, Eric S

2014-02-07

Carbon and noble metal nanomaterials exhibit unique properties that have been explored over the last few decades for developing electrochemical sensors and biosensors. Hybridization of nanometals to carbon nanomaterials such as graphene or carbon nanotubes produces a synergistic effect on the electrocatalytic activity when compared to either material alone. However, to date there are no comparative studies that directly investigate the effects of nanocarbon concentration and nanocomposite arrangement on electron transport. This comparative study investigated the efficacy of various platinum-carbon hybrid nanostructures for amperometric biosensing. Electroactive surface area, sensitivity towards hydrogen peroxide, response time, limit of detection, and surface roughness were measured for various hybrid nanomaterial arrangements. Both design factors (nanocarbon concentration and network arrangement) influenced the performance of the reduced graphene oxide-based platforms; whereas only nanomaterial arrangement affected the performance of the carbon nanotube-composites. The highest sensitivity towards hydrogen peroxide for reduced graphene oxide nanocomposites (45 ± 3.2 μA mM(-1)) was measured for a graphene concentration of 2 mg mL(-1) in a "sandwich" structure; nanoplatinum layers enveloping the reduced graphene oxide. Likewise, the best carbon nanotube performance toward H2O2 (49 ± 1.4 μA mM(-1)) was measured for a sandwich-type structure with nanoplatinum. The enhanced electrocatalytic activity of this "sandwich" structure was due to a combined effect of electrical junctions formed amongst nanocarbon, and nanocomposite soldering to the electrode surface. The top-down carbon-platinum hybrid nanocomposites in this paper represent a simple, low-cost, approach for formation of high fidelity amperometric sensors with remarkable performance characteristics that are similar to bottom-up fabrication approaches.

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.

Elucidating Complex Surface Reconstructions with Atomic-Resolution Scanning Tunneling Microscopy: Au(100)-Aqueous Electrochemical Interface

DTIC Science & Technology

1992-05-01

that unusually high-quality STM data of this type 5-7can be obtained at ordered gold -aqueous interfaces. Reconstruction is seen 2 to be triggered on...all three low-index gold surfaces by altering the potential to values corresponding to small (10-15 pC cm-2 ) negative surface electronic 5-7 charges...connections. The former was platinum and the latter was a freshly electrooxidized gold wire. All electrode potentials quoted here, however, are

Schiff Base modified on CPE electrode and PCB gold electrode for selective determination of silver ion

NASA Astrophysics Data System (ADS)

Leepheng, Piyawan; Suramitr, Songwut; Phromyothin, Darinee

2017-09-01

The schiff base was synthesized by 2,5-thiophenedicarboxaldehyde and 1,2,4-thiadiazole-3,5-diamine with condensation method. There was modified on carbon paste electrode (CPE) and Printed circuit board (PCB) gold electrode for determination silver ion. The schiff base modified electrodes was characterized by atomic force microscopy (AFM) and scanning electron microscopy (SEM), respectively. The electrochemical study was reported by cyclic voltammetry method and impedance spectroscopy using modified electrode as working electrode, platinum wire and Ag/AgCl as counter electrode and reference electrode, respectively. The modified electrodes have suitable detection for Ag+. The determination of silver ions using the modified electrodes depended linearly on Ag+ concentration in the range 1×10-10 M to 1×10-7 M, with cyclic voltammetry sensitivity were 2.51×108 μAM-1 and 1.88×108 μAM-1 for PCB gold electrode and CPE electrode, respectively, limits of detection were 5.33×10-9 M and 1.99×10-8 M for PCB gold electrode and CPE electrode, respectively. The modified electrodes have high accuracy, inexpensive and can applied to detection Ag+ in real samples.

Nanostructured Platinum Alloys for Use as Catalyst Materials

NASA Technical Reports Server (NTRS)

Narayan, Sri R. (Inventor); Hays, Charles C. (Inventor)

2015-01-01

A series of binary and ternary Pt-alloys, that promote the important reactions for catalysis at an alloy surface; oxygen reduction, hydrogen oxidation, and hydrogen and oxygen evolution. The first two of these reactions are essential when applying the alloy for use in a PEMFC.

Nanostructured Platinum Alloys for Use as Catalyst Materials

NASA Technical Reports Server (NTRS)

Hays, Charles C. (Inventor); Narayan, Sri R. (Inventor)

2013-01-01

A series of binary and ternary Pt-alloys, that promote the important reactions for catalysis at an alloy surface; oxygen reduction, hydrogen oxidation, and hydrogen and oxygen evolution. The first two of these reactions are essential when applying the alloy for use in a PEMFC.

Topotecan, pegylated liposomal doxorubicin hydrochloride, paclitaxel, trabectedin and gemcitabine for advanced recurrent or refractory ovarian cancer: a systematic review and economic evaluation.

PubMed

Edwards, Steven J; Barton, Samantha; Thurgar, Elizabeth; Trevor, Nicola

2015-01-01

Ovarian cancer is the fifth most common cancer in the UK, and the fourth most common cause of cancer death. Of those people successfully treated with first-line chemotherapy, 55-75% will relapse within 2 years. At this time, it is uncertain which chemotherapy regimen is more clinically effective and cost-effective for the treatment of recurrent, advanced ovarian cancer. To determine the comparative clinical effectiveness and cost-effectiveness of topotecan (Hycamtin(®), GlaxoSmithKline), pegylated liposomal doxorubicin hydrochloride (PLDH; Caelyx(®), Schering-Plough), paclitaxel (Taxol(®), Bristol-Myers Squibb), trabectedin (Yondelis(®), PharmaMar) and gemcitabine (Gemzar(®), Eli Lilly and Company) for the treatment of advanced, recurrent ovarian cancer. Electronic databases (MEDLINE(®), EMBASE, Cochrane Central Register of Controlled Trials, Health Technology Assessment database, NHS Economic Evaluations Database) and trial registries were searched, and company submissions were reviewed. Databases were searched from inception to May 2013. A systematic review of the clinical and economic literature was carried out following standard methodological principles. Double-blind, randomised, placebo-controlled trials, evaluating topotecan, PLDH, paclitaxel, trabectedin and gemcitabine, and economic evaluations were included. A network meta-analysis (NMA) was carried out. A de novo economic model was developed. For most outcomes measuring clinical response, two networks were constructed: one evaluating platinum-based regimens and one evaluating non-platinum-based regimens. In people with platinum-sensitive disease, NMA found statistically significant benefits for PLDH plus platinum, and paclitaxel plus platinum for overall survival (OS) compared with platinum monotherapy. PLDH plus platinum significantly prolonged progression-free survival (PFS) compared with paclitaxel plus platinum. Of the non-platinum-based treatments, PLDH monotherapy and trabectedin plus PLDH were found to significantly increase OS, but not PFS, compared with topotecan monotherapy. In people with platinum-resistant/-refractory (PRR) disease, NMA found no statistically significant differences for any treatment compared with alternative regimens in OS and PFS. Economic modelling indicated that, for people with platinum-sensitive disease and receiving platinum-based therapy, the estimated probabilistic incremental cost-effectiveness ratio [ICER; incremental cost per additional quality-adjusted life-year (QALY)] for paclitaxel plus platinum compared with platinum was £24,539. Gemcitabine plus carboplatin was extendedly dominated, and PLDH plus platinum was strictly dominated. For people with platinum-sensitive disease and receiving non-platinum-based therapy, the probabilistic ICERs associated with PLDH compared with paclitaxel, and trabectedin plus PLDH compared with PLDH, were estimated to be £25,931 and £81,353, respectively. Topotecan was strictly dominated. For people with PRR disease, the probabilistic ICER associated with topotecan compared with PLDH was estimated to be £324,188. Paclitaxel was strictly dominated. As platinum- and non-platinum-based treatments were evaluated separately, the comparative clinical effectiveness and cost-effectiveness of these regimens is uncertain in patients with platinum-sensitive disease. For platinum-sensitive disease, it was not possible to compare the clinical effectiveness and cost-effectiveness of platinum-based therapies with non-platinum-based therapies. For people with platinum-sensitive disease and treated with platinum-based therapies, paclitaxel plus platinum could be considered cost-effective compared with platinum at a threshold of £30,000 per additional QALY. For people with platinum-sensitive disease and treated with non-platinum-based therapies, it is unclear whether PLDH would be considered cost-effective compared with paclitaxel at a threshold of £30,000 per additional QALY; trabectedin plus PLDH is unlikely to be considered cost-effective compared with PLDH. For patients with PRR disease, it is unlikely that topotecan would be considered cost-effective compared with PLDH. Randomised controlled trials comparing platinum with non-platinum-based treatments might help to verify the comparative effectiveness of these regimens. This study is registered as PROSPERO CRD42013003555. The National Institute for Health Research Health Technology Assessment programme.

Spontaneous incorporation of gold in palladium-based ternary nanoparticles makes durable electrocatalysts for oxygen reduction reaction

PubMed Central

Wang, Deli; Liu, Sufen; Wang, Jie; Lin, Ruoqian; Kawasaki, Masahiro; Rus, Eric; Silberstein, Katharine E.; Lowe, Michael A.; Lin, Feng; Nordlund, Dennis; Liu, Hongfang; Muller, David A.; Xin, Huolin L.; Abruña, Héctor D.

2016-01-01

Replacing platinum by a less precious metal such as palladium, is highly desirable for lowering the cost of fuel-cell electrocatalysts. However, the instability of palladium in the harsh environment of fuel-cell cathodes renders its commercial future bleak. Here we show that by incorporating trace amounts of gold in palladium-based ternary (Pd6CoCu) nanocatalysts, the durability of the catalysts improves markedly. Using aberration-corrected analytical transmission electron microscopy in conjunction with synchrotron X-ray absorption spectroscopy, we show that gold not only galvanically replaces cobalt and copper on the surface, but also penetrates through the Pd–Co–Cu lattice and distributes uniformly within the particles. The uniform incorporation of Au provides a stability boost to the entire host particle, from the surface to the interior. The spontaneous replacement method we have developed is scalable and commercially viable. This work may provide new insight for the large-scale production of non-platinum electrocatalysts for fuel-cell applications. PMID:27336795

Application of green chemistry techniques to prepare electrocatalysts for direct methanol fuel cells.

PubMed

Shimizu, Kenichi; Wang, Joanna S; Wai, Chien M

2010-03-25

A series of green techniques for synthesizing carbon nanotube-supported platinum nanoparticles and their high electrocatalytic activity toward methanol fuel cell applications are reported. The techniques utilize either the supercritical fluid carbon dioxide or water as a medium for depositing platinum nanoparticles on surfaces of multiwalled or single-walled carbon nanotubes. The catalytic properties of the carbon nanotubes-supported Pt nanoparticle catalysts prepared by four different techniques are compared for anodic oxidation of methanol and cathodic reduction of oxygen using cyclic voltammetry. One technique using galvanic exchange of Pt(2+) in water with zerovalent iron present on the surfaces of as-grown single-walled carbon nanotubes produces a Pt catalyst that shows an unusually high catalytic activity for reduction of oxygen but a negligible activity for oxidation of methanol. This fuel-selective catalyst may have a unique application as a cathode catalyst in methanol fuel cells to alleviate the problems caused by crossover of methanol through the polymer electrolyte membrane.

Nanoparticle mediated micromotor motion.

PubMed

Liu, Mei; Liu, Limei; Gao, Wenlong; Su, Miaoda; Ge, Ya; Shi, Lili; Zhang, Hui; Dong, Bin; Li, Christopher Y

2015-03-21

In this paper, we report the utilization of nanoparticles to mediate the motion of a polymer single crystal catalytic micromotor. Micromotors have been fabricated by directly self-assembling functional nanoparticles (platinum and iron oxide nanoparticles) onto one or both sides of two-dimensional polymer single crystals. We show that the moving velocity of these micromotors in fluids can be readily tuned by controlling the nanoparticles' surface wettability and catalytic activity. A 3 times velocity increase has been achieved for a hydrophobic micromotor as opposed to the hydrophilic ones. Furthermore, we demonstrate that the catalytic activity of platinum nanoparticles inside the micromotor can be enhanced by their synergetic interactions with iron oxide nanoparticles and an electric field. Both strategies lead to dramatically increased moving velocities, with the highest value reaching ∼200 μm s(-1). By decreasing the nanoparticles' surface wettability and increasing their catalytic activity, a maximum of a ∼10-fold increase in the moving speed of the nanoparticle based micromotor can be achieved. Our results demonstrate the advantages of using nanoparticles in micromotor systems.

A Generic Wet Impregnation Method for Preparing Substrate-Supported Platinum Group Metal and Alloy Nanoparticles with Controlled Particle Morphology.

PubMed

Zhang, Changlin; Oliaee, Shirin Norooz; Hwang, Sang Youp; Kong, Xiangkai; Peng, Zhenmeng

2016-01-13

Mass production of shape-controlled platinum group metal (PGM) and alloy nanoparticles is of high importance for their many fascinating properties in catalysis, electronics, and photonics. Despite of successful demonstrations at milligram scale using wet chemistry syntheses in many fundamental studies, there is still a big gap between the current methods and their real applications due to the complex synthetic procedures, scale-up difficulty, and surface contamination problem of the made particles. Here we report a generic wet impregnation method for facile, surfactant-free, and scalable preparation of nanoparticles of PGMs and their alloys on different substrate materials with controlled particle morphology and clean surface, which bridges the outstanding properties of these nanoparticles to practical important applications. The underlying particle growth and shape formation mechanisms were investigated using a combination of ex situ and in situ characterizations and were attributed to their different interactions with the applied gas molecules.

Investigating the effects of proton exchange membrane fuel cell conditions on carbon supported platinum electrocatalyst composition and performance

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

Patel, Anant; Artyushkova, Kateryna; Atanassov, Plamen

2011-12-01

Changes that carbon-supported platinum electrocatalysts undergo in a proton exchange membrane fuel cell environment were simulated by ex situ heat treatment of catalyst powder samples at 150 C and 100% relative humidity. In order to study modifications that are introduced to chemistry, morphology, and performance of electrocatalysts, XPS, HREELS and three-electrode rotating disk electrode experiments were performed. Before heat treatment, graphitic content varied by 20% among samples with different types of carbon supports, with distinct differences between bulk and surface compositions within each sample. Following the aging protocol, the bulk and surface chemistry of the samples were similar, with graphitemore » content increasing or remaining constant and Pt-carbide decreasing for all samples. From the correlation of changes in chemical composition and losses in performance of the electrocatalysts, we conclude that relative distribution of Pt particles on graphitic and amorphous carbon is as important for electrocatalytic activity as the absolute amount of graphitic carbon present« less

Spontaneous incorporation of gold in palladium-based ternary nanoparticles makes durable electrocatalysts for oxygen reduction reaction

DOE PAGES

Wang, Deli; Liu, Sufen; Wang, Jie; ...

2016-06-23

Replacing platinum by a less precious metal such as palladium, is highly desirable for lowering the cost of fuel-cell electrocatalysts. However, the instability of palladium in the harsh environment of fuel-cell cathodes renders its commercial future bleak. Here we show that by incorporating trace amounts of gold in palladium-based ternary (Pd6CoCu) nanocatalysts, the durability of the catalysts improves markedly. Using aberration-corrected analytical transmission electron microscopy in conjunction with synchrotron X-ray absorption spectroscopy, we show that gold not only galvanically replaces cobalt and copper on the surface, but also penetrates through the Pd–Co–Cu lattice and distributes uniformly within the particles. Themore » uniform incorporation of Au provides a stability boost to the entire host particle, from the surface to the interior. The spontaneous replacement method we have developed is scalable and commercially viable. This work may provide new insight for the large-scale production of non-platinum electrocatalysts for fuel-cell applications.« less

Mesoporous Colloidal Superparticles of Platinum-Group Nanocrystals with Surfactant-Free Surfaces and Enhanced Heterogeneous Catalysis

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

Hu, Yongxing; Liu, Yuzi; Sun, Yugang

2015-01-23

Synthesis of colloidal superparticles (CSPs) of nanocrystals, a class of assembled nanocrystals in the form of colloidal particles, has been emerging as a new frontier in the field of nanotechnology because of their potential novel properties originated from coupling of individual nanocrystals in CSPs. Here, a facile approach is reported for the controlled synthesis of mesoporous CSPs made of various platinum-group nanocrystals that exhibit high colloidal stability and ligand-free surfaces to significantly benefit their applications in solution-phase heterogeneous catalysis. The synthesis relies on self-limiting growth of composite particles through coprecipitation of both Pt-group nanocrystals (or their precursor compounds) and silvermore » halides on sacrificial substrates of colloidal silver particles. The intermediate silver halides in the composite particles play the critical role in limiting the continuous growth (and/or coalescence) of individual Pt-group nanocrystals and they can be selectively dissolved to create nanoscale pores in the resulting CSPs.« less

Anisotropic etching of platinum electrodes at the onset of cathodic corrosion

PubMed Central

Hersbach, Thomas J. P.; Yanson, Alexei I.; Koper, Marc T. M.

2016-01-01

Cathodic corrosion is a process that etches metal electrodes under cathodic polarization. This process is presumed to occur through anionic metallic reaction intermediates, but the exact nature of these intermediates and the onset potential of their formation is unknown. Here we determine the onset potential of cathodic corrosion on platinum electrodes. Electrodes are characterized electrochemically before and after cathodic polarization in 10 M sodium hydroxide, revealing that changes in the electrode surface start at an electrode potential of −1.3 V versus the normal hydrogen electrode. The value of this onset potential rules out previous hypotheses regarding the nature of cathodic corrosion. Scanning electron microscopy shows the formation of well-defined etch pits with a specific orientation, which match the voltammetric data and indicate a remarkable anisotropy in the cathodic etching process, favouring the creation of (100) sites. Such anisotropy is hypothesized to be due to surface charge-induced adsorption of electrolyte cations. PMID:27554398

Low platinum loading cathode modified with Cs3H2PMo10V2O40 for polymer electrolyte membrane fuel cells

NASA Astrophysics Data System (ADS)

Renzi, M.; D'Angelo, G.; Marassi, R.; Nobili, F.

2016-09-01

The catalytic activity of commercial Pt nanoparticles mixed with mesoporous polyoxometalate Cs3H2PMo10V2O40 towards oxygen reduction reaction is evaluated. The polyoxometalate co-catalyst is prepared by titration of an aqueous solution of phosphovanadomolibdic acid. SEM micrography shows reduction particle size to less than 300 nm, while XRD confirms that the resulting salt maintains the Kegging structure. The composite catalyst is prepared by mixing the POM salt with Pt/C by sonication. RRDE studies show better kinetics for ORR with low Pt loading at the electrode surface. A MEA is assembled by using a Pt/POM-based cathode, in order to assess performance in a working fuel cell. Current vs. potential curves reveals comparable or better performances at 100%, 62% and 17% relative humidity for the POM-modified MEA with respect to a commercial MEA with higher Pt loading at the cathode. Electrochemical impedance spectroscopy (EIS) confirms better kinetics at low relative humidity. Finally, an accelerated stress test (AST) with square wave (SW) between 0.4 V and 0.8 V is performed to evaluate MEA stability for at least 100 h and make predictions about lifetime, showing that after initial losses the catalytic system can retain stable performance and good morphological stability.

Hydrogen Sorption Kinetics on Bare and Platinum-Modified Palladium Nanofilms, Grown by Electrochemical Atomic Layer Deposition (E-ALD)

DOE PAGES

Jagannathan, Kaushik; Benson, David M.; Robinson, David B.; ...

2016-01-01

Nanofilms of Pd were grown using an electrochemical form of atomic layer deposition (E-ALD) on 100 nm evaporated Au films on glass. Multiple cycles of surface-limited redox replacement (SLRR) were used to grow deposits. Each SLRR involved the underpotential deposition (UPD) of a Cu atomic layer, followed by open circuit replacement via redox exchange with tetrachloropalladate, forming a Pd atomic layer: one E-ALD deposition cycle. That cycle was repeated in order to grow deposits of a desired thickness. 5 cycles of Pd deposition were performed on the Au on glass substrates, resulting in the formation of 2.5 monolayers of Pd.more » Those Pd films were then modified with varying coverages of Pt, also formed using SLRR. The amount of Pt was controlled by changing the potential for Cu UPD, and by increasing the number of Pt deposition cycles. Hydrogen absorption was studied using coulometry and cyclic voltammetry in 0.1 M H 2SO 4 as a function of Pt coverage. The presence of even a small fraction of a Pt monolayer dramatically increased the rate of hydrogen desorption. However, this did not reduce the films’ hydrogen storage capacity. The increase in desorption rate in the presence of Pt was over an order of magnitude.« less

Eribulin mesylate (halichondrin B Analog E7389) in platinum-resistant and platinum-sensitive ovarian cancer: a two-cohort, phase II study

PubMed Central

Hensley, Martee L.; Kravetz, Sara; Jia, Xiaoyu; Iasonos, Alexia; Tew, William; Pereira, Lauren; Sabbatini, Paul; Whalen, Christin; Aghajanian, Carol A.; Zarwan, Corinne; Berlin, Suzanne

2011-01-01

Background Eribulin mesylate is a tubulin inhibitor with activity superior to paclitaxel in NIH:OVCAR-3 human epithelial ovarian cancer xenograft models. We sought to assess the efficacy of eribulin in platinum-resistant and platinum-sensitive recurrent ovarian cancer. Methods Patients with recurrent measurable epithelial ovarian cancer, ≤2 prior cytotoxic regimens, and adequate organ function were enrolled into two separate cohorts: 1) Platinum resistant (progression-free interval from last platinum-based therapy <6 months); and 2) Platinum sensitive (progression-free interval from last platinum-based therapy ≥6 months). Treatment: Eribulin 1.4 mg/m2 over 15 minutes by vein on days 1 and 8, every 21 days. Efficacy was determined by objective response by computed tomography. Results Platinum-resistant cohort: Thirty-seven patients enrolled. Thirty-six patients were evaluable for response and toxicity. Two patients achieved partial response (PR, 5.5%). Sixteen (44%) had a best response of stable disease. Median progression-free survival was 1.8 months (95% confidence interval, 1.4–2.8 months). Platinum-sensitive cohort: Thirty-seven patients enrolled, and all were evaluable for response. Seven patients achieved partial response (PR, 19%). Median progression-free survival was 4.1 months (95% confidence interval, 2.8–5.8 months). The major toxicity was grade 3 or 4 neutropenia (42% in platinum-resistant patients; 54% in platinum-sensitive patients). Conclusions Eribulin achieved objective response in 5.5% of women with platinum-resistant recurrent ovarian cancer and in 19% of women with platinum-sensitive disease. Median progression-free survival was 1.8 months in the platinum-resistant group and 4.1 months in the platinum-sensitive group. PMID:21935916

Catalysis of a 1,3-dipolar reaction by distorted DNA incorporating a heterobimetallic platinum(ii) and copper(ii) complex† †Electronic supplementary information (ESI) available: Experimental details, characterization of cycloadducts and intermediates, computational data. CCDC 1411372 and 1411373. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c7sc02311a

PubMed Central

Rivilla, Iván; de Cózar, Abel; Schäfer, Thomas; Hernandez, Frank J.; Bittner, Alexander M.; Eleta-Lopez, Aitziber; Aboudzadeh, Ali; Santos, José I.; Miranda, José I.

2017-01-01

A novel catalytic system based on covalently modified DNA is described. This catalyst promotes 1,3-dipolar reactions between azomethine ylides and maleimides. The catalytic system is based on the distortion of the double helix of DNA by means of the formation of Pt(ii) adducts with guanine units. This distortion, similar to that generated in the interaction of DNA with platinum chemotherapeutic drugs, generates active sites that can accommodate N-metallated azomethine ylides. The proposed reaction mechanism, based on QM(DFT)/MM calculations, is compatible with thermally allowed concerted (but asynchronous) [π4s + π2s] mechanisms leading to the exclusive formation of racemic endo-cycloadducts. PMID:29147531

A Thin Film Multifunction Sensor for Harsh Environments

NASA Technical Reports Server (NTRS)

Wrbanek, John D.; Fralick, Gustave C.; Martin, Lisa C.; Blaha, Charles A.

2001-01-01

The status of work at NASA Glenn Research Center to develop a minimally intrusive integrated sensor to provide realtime measurement of strain, heat flux and flow in high temperature environments is presented in this paper. The sensor can be beneficial as a single package to characterize multiple stress and strain modes simultaneously on materials and components during engine development and validation. A major technical challenge is to take existing individual gauge designs and modify them into one integrated thin film sensor. Ultimately, the goal is to develop the ability to deposit the sensors directly onto internal engine parts or on a small thin substrate that can be attached to engine components. Several prototype sensors constructed of platinum, platinum-rhodium alloy, and alumina on constant-strain alumina beams have been built and bench-tested. The technical challenges of the design. construction, and testing are discussed. Data from the preliminary testing of the sensor array is presented. The future direction for the sensor development is discussed as well.

Development of advanced fuel cell system, phase 3

NASA Technical Reports Server (NTRS)

Handley, L. M.; Meyer, A. P.; Bell, W. F.

1975-01-01

A multiple task research and development program was performed to improve the weight, life, and performance characteristics of hydrogen-oxygen alkaline fuel cells for advanced power systems. Gradual wetting of the anode structure and subsequent long-term performance loss was determined to be caused by deposition of a silicon-containing material on the anode. This deposit was attributed to degradation of the asbestos matrix, and attention was therefore placed on development of a substitute matrix of potassium titanate. An 80 percent gold 20 percent platinum catalyst cathode was developed which has the same performance and stability as the standard 90 percent gold - 10 percent platinum cathode but at half the loading. A hybrid polysulfone/epoxy-glass fiber frame was developed which combines the resistance to the cell environment of pure polysulfone with the fabricating ease of epoxy-glass fiber laminate. These cell components were evaluated in various configurations of full-size cells. The ways in which the baseline engineering model system would be modified to accommodate the requirements of the space tug application are identified.

Tissue Platinum Concentration and Tumor Response in Non–Small-Cell Lung Cancer

PubMed Central

Kim, Eric S.; Lee, J. Jack; He, Guangan; Chow, Chi-Wan; Fujimoto, Junya; Kalhor, Neda; Swisher, Stephen G.; Wistuba, Ignacio I.; Stewart, David J.; Siddik, Zahid H.

2012-01-01

Purpose Platinum resistance is a major limitation in the treatment of advanced non–small-cell lung cancer (NSCLC). Reduced intracellular drug accumulation is one of the most consistently identified features of platinum-resistant cell lines, but clinical data are limited. We assessed the effects of tissue platinum concentrations on response and survival in NSCLC. Patients and Methods We measured total platinum concentrations by flameless atomic absorption spectrophotometry in 44 archived fresh-frozen NSCLC specimens from patients who underwent surgical resection after neoadjuvant platinum-based chemotherapy. Tissue platinum concentration was correlated with percent reduction in tumor size on post- versus prechemotherapy computed tomography scans. The relationship between tissue platinum concentration and survival was assessed by univariate and multicovariate Cox proportional hazards regression model analysis and Kaplan-Meier analysis. Results Tissue platinum concentration correlated significantly with percent reduction in tumor size (P < .001). The same correlations were seen with cisplatin, carboplatin, and all histology subgroups. Furthermore, there was no significant impact of potential variables such as number of cycles and time lapse from last chemotherapy on platinum concentration. Patients with higher platinum concentration had longer time to recurrence (P = .034), progression-free survival (P = .018), and overall survival (P = .005) in the multicovariate Cox model analysis after adjusting for number of cycles. Conclusion This clinical study established a relationship between tissue platinum concentration and response in NSCLC. It suggests that reduced platinum accumulation might be an important mechanism of platinum resistance in the clinical setting. Further studies investigating factors that modulate intracellular platinum concentration are warranted. PMID:22891266

KOH-activated multi-walled carbon nanotubes as platinum supports for oxygen reduction reaction

NASA Astrophysics Data System (ADS)

He, Chaoxiong; Song, Shuqin; Liu, Jinchao; Maragou, Vasiliki; Tsiakaras, Panagiotis

In the present investigation, multi-walled carbon nanotubes (MWCNTs) thermally treated by KOH were adopted as the platinum supporting material for the oxygen reduction reaction electrocatalysts. FTIR and Raman spectra were used to investigate the surface state of MWCNTs treated by KOH at different temperatures (700, 800, and 900 °C) and showed MWCNTs can be successfully functionalized. The structural properties of KOH-activated MWCNTs supported Pt were determined by X-ray diffraction (XRD) and transmission electron microscopy (TEM), and their electrochemical performance was evaluated by the aid of cyclic voltammetry (CV) and rotating disk electrode (RDE) voltammetry. According to the experimental findings of the present work, the surrface of MWCNTs can be successfully functionalized with oxygen-containing groups after activation by KOH, favoring the good dispersion of Pt nanoparticles with narrow size distribution. The as-prepared Pt catalysts supported on KOH treated MWCNTs at higher temperature, possess higher electrochemical surface area and exhibit desirable activity towards oxygen reduction reaction (ORR). More precisely, it has been found that the electrochemical active area of Pt/MWCNTs-900 is approximately two times higher than that of Pt/MWCNTs. It can be concluded that KOH activation is an effective way to decorate MWCNTs' surface with oxygen-containing groups and bigger surface area, which makes them more suitable as electrocatalyst support materials.

Effect of Organic Cations on Hydrogen Oxidation Reaction of Carbon Supported Platinum

DOE PAGES

Chung, Hoon Taek; Choe, Yong-Kee; Martinez, Ulises; ...

2016-11-02

Effect of organic cations on hydrogen oxidation reaction (HOR) of carbon supported platinum (Pt/C) is investigated using three 0.1 M alkaline electrolytes, tetramethylammonium hydroxide (TMAOH), tetrabutylammonium hydroxide (TBAOH) and tetrabutylphosphonium hydroxide (TBPOH). Rotating disk electrode experiments indicate that the HOR of Pt/C is adversely impacted by time-dependent and potential-driven chemisorption of organic cations. In-situ infrared reflection adsorption spectroscopy experiments indicated that the specific chemisorption of organic cations drives the hydroxide co-adsorption on Pt surface. The co-adsorption of TMA + and hydroxide at 0.1 V vs. reversible hydrogen electrode is the strongest; consequently, complete removal of the co-adsorbed layer from Ptmore » surface is difficult even after exposure the Pt surface to 1.2 V. Conversely, the chemisorption of TBP+ is the weakest, yet notable decrease of HOR current density is still observed. The adsorption energies, ΔE, for TMA +, TBA +, and TBP + on Pt (111) surface from density functional theory are computed to be -2.79, -2.42 and -2.00 eV, respectively. The relatively low adsorption energy of TBP + is explained by the steric hindrance and electronic effect. This study emphasizes the importance of cationic group on HOR activity of alkaline anion exchange membrane fuel cells.« less

Reacting Flow in the Entrance to a Channel with Surface and Gas-Phase Kinetics

NASA Astrophysics Data System (ADS)

Mikolaitis, David; Griffen, Patrick

2006-11-01

In many catalytic reactors the conversion process is most intense at the very beginning of the channel where the flow is not yet fully developed; hence there will be important interactions between the developing flow field and reaction. To study this problem we have written an object-oriented code for the analysis of reacting flow in the entrance of a channel where both surface reaction and gas-phase reaction are modeled with detailed kinetics. Fluid mechanical momentum and energy equations are modeled by parabolic ``boundary layer''-type equations where streamwise gradient terms are small and the pressure is constant in the transverse direction. Transport properties are modeled with mixture-averaging and the chemical kinetic sources terms are evaluated using Cantera. Numerical integration is done with Matlab using the function pdepe. Calculations were completed using mixtures of methane and air flowing through a channel with platinum walls held at a fixed temperature. GRI-Mech 3.0 was used to describe the gas-phase chemistry and Deutchmann's methane-air-platinum model was used for the surface chemistry. Ignition in the gas phase is predicted for high enough wall temperatures. A hot spot forms away from the walls just before ignition that is fed by radicals produced at the surface.

Microscopic modeling of gas-surface scattering: II. Application to argon atom adsorption on a platinum (111) surface

NASA Astrophysics Data System (ADS)

Filinov, A.; Bonitz, M.; Loffhagen, D.

2018-06-01

A new combination of first principle molecular dynamics (MD) simulations with a rate equation model presented in the preceding paper (paper I) is applied to analyze in detail the scattering of argon atoms from a platinum (111) surface. The combined model is based on a classification of all atom trajectories according to their energies into trapped, quasi-trapped and scattering states. The number of particles in each of the three classes obeys coupled rate equations. The coefficients in the rate equations are the transition probabilities between these states which are obtained from MD simulations. While these rates are generally time-dependent, after a characteristic time scale t E of several tens of picoseconds they become stationary allowing for a rather simple analysis. Here, we investigate this time scale by analyzing in detail the temporal evolution of the energy distribution functions of the adsorbate atoms. We separately study the energy loss distribution function of the atoms and the distribution function of in-plane and perpendicular energy components. Further, we compute the sticking probability of argon atoms as a function of incident energy, angle and lattice temperature. Our model is important for plasma-surface modeling as it allows to extend accurate simulations to longer time scales.

Structure and Dynamics of Individual Diastereomeric Complexes on Platinum: Surface Studies Related to Heterogeneous Enantioselective Catalysis.

PubMed

Dong, Yi; Goubert, Guillaume; Groves, Michael N; Lemay, Jean-Christian; Hammer, Bjørk; McBreen, Peter H

2017-05-16

The modification of heterogeneous catalysts through the chemisorption of chiral molecules is a method to create catalytic sites for enantioselective surface reactions. The chiral molecule is called a chiral modifier by analogy to the terms chiral auxiliary or chiral ligand used in homogeneous asymmetric catalysis. While there has been progress in understanding how chirality transfer occurs, the intrinsic difficulties in determining enantioselective reaction mechanisms are compounded by the multisite nature of heterogeneous catalysts and by the challenges facing stereospecific surface analysis. However, molecular descriptions have now emerged that are sufficiently detailed to herald rapid advances in the area. The driving force for the development of heterogeneous enantioselective catalysts stems, at the minimum, from the practical advantages they might offer over their homogeneous counterparts in terms of process scalability and catalyst reusability. The broader rewards from their study lie in the insights gained on factors controlling selectivity in heterogeneous catalysis. Reactions on surfaces to produce a desired enantiomer in high excess are particularly challenging since at room temperature, barrier differences as low as ∼2 kcal/mol between pathways to R and S products are sufficient to yield an enantiomeric ratio (er) of 90:10. Such small energy differences are comparable to weak interadsorbate interaction energies and are much smaller than chemisorption or even most physisorption energies. In this Account, we describe combined experimental and theoretical surface studies of individual diastereomeric complexes formed between chiral modifiers and prochiral reactants on the Pt(111) surface. Our work is inspired by the catalysis literature on the enantioselective hydrogenation of activated ketones on cinchona-modified Pt catalysts. Using scanning tunneling microscopy (STM) measurements and density functional theory (DFT) calculations, we probe the structures and relative abundances of non-covalently bonded complexes formed between three representative prochiral molecules and (R)-(+)-1-(1-naphthyl)ethylamine ((R)-NEA). All three prochiral molecules, 2,2,2-trifluoroacetophenone (TFAP), ketopantolactone (KPL), and methyl 3,3,3-trifluoropyruvate (MTFP), are found to form multiple complexation configurations around the ethylamine group of chemisorbed (R)-NEA. The principal intermolecular interaction is NH···O H-bonding. In each case, submolecularly resolved STM images permit the determination of the prochiral ratio (pr), pro-R to pro-S, proper to specific locations around the ethylamine group. The overall pr observed in experiments on large ensembles of KPL-(R)-NEA complexes is close to the er reported in the literature for the hydrogenation of KPL to pantolactone on (R)-NEA-modified Pt catalysts at 1 bar H 2 . The results of independent DFT and STM studies are merged to determine the geometries of the most abundant complexation configurations. The structures reveal the hierarchy of chemisorption and sometimes multiple H-bonding interactions operating in complexes. In particular, privileged complexes formed by KPL and MTFP reveal the participation of secondary CH···O interactions in stereocontrol. State-specific STM measurements on individual TFAP-(R)-NEA complexes show that complexation states interconvert through processes including prochiral inversion. The state-specific information on structure, prochirality, dynamics, and energy barriers delivered by the combination of DFT and STM provides insight on how to design better chiral modifiers.

Platinum-bearing chromite layers are caused by pressure reduction during magma ascent.

PubMed

Latypov, Rais; Costin, Gelu; Chistyakova, Sofya; Hunt, Emma J; Mukherjee, Ria; Naldrett, Tony

2018-01-31

Platinum-bearing chromitites in mafic-ultramafic intrusions such as the Bushveld Complex are key repositories of strategically important metals for human society. Basaltic melts saturated in chromite alone are crucial to their generation, but the origin of such melts is controversial. One concept holds that they are produced by processes operating within the magma chamber, whereas another argues that melts entering the chamber were already saturated in chromite. Here we address the problem by examining the pressure-related changes in the topology of a Mg 2 SiO 4 -CaAl 2 Si 2 O 8 -SiO 2 -MgCr 2 O 4 quaternary system and by thermodynamic modelling of crystallisation sequences of basaltic melts at 1-10 kbar pressures. We show that basaltic melts located adjacent to a so-called chromite topological trough in deep-seated reservoirs become saturated in chromite alone upon their ascent towards the Earth's surface and subsequent cooling in shallow-level chambers. Large volumes of these chromite-only-saturated melts replenishing these chambers are responsible for monomineralic layers of massive chromitites with associated platinum-group elements.

Single-wall carbon nanotube-based proton exchange membrane assembly for hydrogen fuel cells.

PubMed

Girishkumar, G; Rettker, Matthew; Underhile, Robert; Binz, David; Vinodgopal, K; McGinn, Paul; Kamat, Prashant

2005-08-30

A membrane electrode assembly (MEA) for hydrogen fuel cells has been fabricated using single-walled carbon nanotubes (SWCNTs) support and platinum catalyst. Films of SWCNTs and commercial platinum (Pt) black were sequentially cast on a carbon fiber electrode (CFE) using a simple electrophoretic deposition procedure. Scanning electron microscopy and Raman spectroscopy showed that the nanotubes and the platinum retained their nanostructure morphology on the carbon fiber surface. Electrochemical impedance spectroscopy (EIS) revealed that the carbon nanotube-based electrodes exhibited an order of magnitude lower charge-transfer reaction resistance (R(ct)) for the hydrogen evolution reaction (HER) than did the commercial carbon black (CB)-based electrodes. The proton exchange membrane (PEM) assembly fabricated using the CFE/SWCNT/Pt electrodes was evaluated using a fuel cell testing unit operating with H(2) and O(2) as input fuels at 25 and 60 degrees C. The maximum power density obtained using CFE/SWCNT/Pt electrodes as both the anode and the cathode was approximately 20% better than that using the CFE/CB/Pt electrodes.

Effect of pressure on the sorption correction to stainless steel, platinum/iridium and silicon mass artefacts

NASA Astrophysics Data System (ADS)

Berry, James; Davidson, Stuart

2014-04-01

This paper reports work undertaken to evaluate the change in mass of platinum/iridium, stainless steel and silicon artefacts measured at atmospheric pressure and in vacuum at a range of pressures typical of those used in vacuum mass comparators and watt balances and for x-ray crystal density (XRCD) measurements. The sets of platinum/iridium, stainless steel and silicon artefacts used in this work have different surface areas and the effect of transferring them between atmospheric pressure and different levels of vacuum was evaluated by measuring the relative changes in mass between them. Reversible variations in the mass differences between the artefacts were found over the pressure range from 0.1 Pa to 100 000 Pa (atmospheric pressure). At lower pressures (0.001 Pa to 0.1 Pa) the mass differences between all the artefacts were stable and no evidence for hysteresis over this range was found when going down in pressure compared with increasing pressure. Therefore consistent results between watt balance, XRCD measurements and vacuum mass measurements can be realized providing the measurements are performed within this pressure range.

75 FR 77572 - Proposed Revision of Class E Airspace; Platinum AK

Federal Register 2010, 2011, 2012, 2013, 2014

2010-12-13

... proposes to revise Class E airspace at Platinum AK. The creation of a new Standard Instrument Approach... Platinum Airport, in Platinum, AK, to accommodate the creation of a new SIAP at the Platinum Airport. This...

Partial oxidation of step-bound water leads to anomalous pH effects on metal electrode step-edges

DOE PAGES

Schwarz, Kathleen; Xu, Bingjun; Yan, Yushan; ...

2016-05-26

The design of better heterogeneous catalysts for applications such as fuel cells and electrolyzers requires a mechanistic understanding of electrocatalytic reactions and the dependence of their activity on operating conditions such as pH. A satisfactory explanation for the unexpected pH dependence of electrochemical properties of platinum surfaces has so far remained elusive, with previous explanations resorting to complex co-adsorption of multiple species and resulting in limited predictive power. This knowledge gap suggests that the fundamental properties of these catalysts are not yet understood, limiting systematic improvement. In this paper, we analyze the change in charge and free energies upon adsorptionmore » using density-functional theory (DFT) to establish that water adsorbs on platinum step edges across a wide voltage range, including the double-layer region, with a loss of approximately 0.2 electrons upon adsorption. We show how this as-yet unreported change in net surface charge due to this water explains the anomalous pH variations of the hydrogen underpotential deposition (H upd) and the potentials of zero total charge (PZTC) observed in published experimental data. This partial oxidation of water is not limited to platinum metal step edges, and we report the charge of the water on metal step edges of commonly used catalytic metals, including copper, silver, iridium, and palladium, illustrating that this partial oxidation of water broadly influences the reactivity of metal electrodes.« less

Durability of De-Alloyed Platinum-Nickel Cathode Catalyst in Low Platinum Loading Membrane-Electrode Assemblies Subjected to Accelerated Stress Tests

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

Ahluwalia, R. K.; Wang, X.; Peng, J. -K.

Here, the durability of de-alloyed platinum-nickel catalysts supported on high-surface area carbon (d-PtNi/C) in optimized electrodes and membrane electrode assemblies (MEAs) under an accelerated stress test (AST) protocol is investigated with the objective of developing a quantitative understanding of the degradation mechanisms and their relationship to the electrode structure, pre-conditioning, and operating conditions. It is found that the cell degradation can be mitigated by controlling the voltage cycle, acid washing the MEA to remove Ni contaminants that enter the electrode and membrane during fabrication, and monitoring the operating conditions. For example, the electrochemical surface area (ECSA) loss is <25% aftermore » 30,000 triangle cycles with 0.925 V upper potential limit if the MEA is acid washed and extensive diagnostics are avoided. The parameters that exacerbate the cell degradation also accelerate the rate at which Ni leaches out from the catalyst. A mechanistic model is presented for the degradation in performance of d-PtNi/C electrodes. The model correlates a) the degradation in ORR mass and specific activities with ECSA and Ni losses, b) the decrease in limiting current density ( iL), which is inversely proportional to the O 2 mass transport resistance, with the degradation in catalyst roughness factor, and c) the increase in mass transfer overpotentials with the reduced current density, i/iL .« less

Highly active carbon supported Pd cathode catalysts for direct formic acid fuel cells

NASA Astrophysics Data System (ADS)

Mikolajczuk-Zychora, A.; Borodzinski, A.; Kedzierzawski, P.; Mierzwa, B.; Mazurkiewicz-Pawlicka, M.; Stobinski, L.; Ciecierska, E.; Zimoch, A.; Opałło, M.

2016-12-01

One of the drawbacks of low-temperature fuel cells is high price of platinum-based catalysts used for the electroreduction of oxygen at the cathode of the fuel cell. The aim of this work is to develop the palladium catalyst that will replace commonly used platinum cathode catalysts. A series of palladium catalysts for oxygen reduction reaction (ORR) were prepared and tested on the cathode of Direct Formic Acid Fuel Cell (DFAFC). Palladium nanoparticles were deposited on the carbon black (Vulcan) and on multiwall carbon nanotubes (MWCNTs) surface by reduction of palladium(II) acetate dissolved in ethanol. Hydrazine was used as a reducing agent. The effect of functionalization of the carbon supports on the catalysts physicochemical properties and the ORR catalytic activity on the cathode of DFAFC was studied. The supports were functionalized by treatment in nitric acid for 4 h at 80 °C. The structure of the prepared catalysts has been characterized by thermogravimetric analysis (TGA), X-ray diffraction (XRD), transmission electron microscope (TEM) and cyclic voltammetry (CV). Hydrophilicity of the catalytic layers was determined by measuring contact angles of water droplets. The performance of the prepared catalysts has been compared with that of the commercial 20 wt.% Pt/C (Premetek) catalyst. The maximum power density obtained for the best palladium catalyst, deposited on the surface of functionalized carbon black, is the same as that for the commercial Pt/C (Premetek). Palladium is cheaper than platinum, therefore the developed cathode catalyst is promising for future applications.

Durability of De-Alloyed Platinum-Nickel Cathode Catalyst in Low Platinum Loading Membrane-Electrode Assemblies Subjected to Accelerated Stress Tests

DOE PAGES

Ahluwalia, R. K.; Wang, X.; Peng, J. -K.; ...

2018-04-25

Here, the durability of de-alloyed platinum-nickel catalysts supported on high-surface area carbon (d-PtNi/C) in optimized electrodes and membrane electrode assemblies (MEAs) under an accelerated stress test (AST) protocol is investigated with the objective of developing a quantitative understanding of the degradation mechanisms and their relationship to the electrode structure, pre-conditioning, and operating conditions. It is found that the cell degradation can be mitigated by controlling the voltage cycle, acid washing the MEA to remove Ni contaminants that enter the electrode and membrane during fabrication, and monitoring the operating conditions. For example, the electrochemical surface area (ECSA) loss is <25% aftermore » 30,000 triangle cycles with 0.925 V upper potential limit if the MEA is acid washed and extensive diagnostics are avoided. The parameters that exacerbate the cell degradation also accelerate the rate at which Ni leaches out from the catalyst. A mechanistic model is presented for the degradation in performance of d-PtNi/C electrodes. The model correlates a) the degradation in ORR mass and specific activities with ECSA and Ni losses, b) the decrease in limiting current density ( iL), which is inversely proportional to the O 2 mass transport resistance, with the degradation in catalyst roughness factor, and c) the increase in mass transfer overpotentials with the reduced current density, i/iL .« less

Electron tomography and 3D molecular simulations of platinum nanocrystals

NASA Astrophysics Data System (ADS)

Florea, Ileana; Demortière, Arnaud; Petit, Christophe; Bulou, Hervé; Hirlimann, Charles; Ersen, Ovidiu

2012-07-01

This work reports on the morphology of individual platinum nanocrystals with sizes of about 5 nm. By using the electron tomography technique that gives 3D spatial selectivity, access to quantitative information in the real space was obtained. The morphology of individual nanoparticles was characterized using HAADF-STEM tomography and it was shown to be close to a truncated octahedron. Using molecular dynamics simulations, this geometrical shape was found to be the one minimizing the nanocrystal energy. Starting from the tomographic reconstruction, 3D crystallographic representations of the studied Pt nanocrystals were obtained at the nanometer scale, allowing the quantification of the relative amount of the crystallographic facets present on the particle surface.This work reports on the morphology of individual platinum nanocrystals with sizes of about 5 nm. By using the electron tomography technique that gives 3D spatial selectivity, access to quantitative information in the real space was obtained. The morphology of individual nanoparticles was characterized using HAADF-STEM tomography and it was shown to be close to a truncated octahedron. Using molecular dynamics simulations, this geometrical shape was found to be the one minimizing the nanocrystal energy. Starting from the tomographic reconstruction, 3D crystallographic representations of the studied Pt nanocrystals were obtained at the nanometer scale, allowing the quantification of the relative amount of the crystallographic facets present on the particle surface. Electronic supplementary information (ESI) available. See DOI: 10.1039/c2nr30990d

Photoelectrocatalytic reduction of CO2 into chemicals using Pt-modified reduced graphene oxide combined with Pt-modified TiO2 nanotubes.

PubMed

Cheng, Jun; Zhang, Meng; Wu, Gai; Wang, Xin; Zhou, Junhu; Cen, Kefa

2014-06-17

The photoelectrocatalytic (PEC) reduction of CO2 into high-value chemicals is beneficial in alleviating global warming and advancing a low-carbon economy. In this work, Pt-modified reduced graphene oxide (Pt-RGO) and Pt-modified TiO2 nanotubes (Pt-TNT) were combined as cathode and photoanode catalysts, respectively, to form a PEC reactor for converting CO2 into valuable chemicals. XRD, XPS, TEM, AFM, and SEM were employed to characterize the microstructures of the Pt-RGO and Pt-TNT catalysts. Reduction products, such as C2H5OH and CH3COOH, were obtained from CO2 under band gap illumination and biased voltage. A combined liquid product generation rate (CH3OH, C2H5OH, HCOOH, and CH3COOH) of approximately 600 nmol/(h·cm(2)) was observed. Carbon atom conversion rate reached 1,130 nmol/(h·cm(2)), which were much higher than those achieved using Pt-modified carbon nanotubes and platinum carbon as cathode catalysts.

Osimertinib or Platinum-Pemetrexed in EGFR T790M-Positive Lung Cancer.

PubMed

Mok, Tony S; Wu, Yi-Long; Ahn, Myung-Ju; Garassino, Marina C; Kim, Hye R; Ramalingam, Suresh S; Shepherd, Frances A; He, Yong; Akamatsu, Hiroaki; Theelen, Willemijn S M E; Lee, Chee K; Sebastian, Martin; Templeton, Alison; Mann, Helen; Marotti, Marcelo; Ghiorghiu, Serban; Papadimitrakopoulou, Vassiliki A

2017-02-16

Osimertinib is an epidermal growth factor receptor tyrosine kinase inhibitor (EGFR-TKI) that is selective for both EGFR-TKI sensitizing and T790M resistance mutations in patients with non-small-cell lung cancer. The efficacy of osimertinib as compared with platinum-based therapy plus pemetrexed in such patients is unknown. In this randomized, international, open-label, phase 3 trial, we assigned 419 patients with T790M-positive advanced non-small-cell lung cancer, who had disease progression after first-line EGFR-TKI therapy, in a 2:1 ratio to receive either oral osimertinib (at a dose of 80 mg once daily) or intravenous pemetrexed (500 mg per square meter of body-surface area) plus either carboplatin (target area under the curve, 5 [AUC5]) or cisplatin (75 mg per square meter) every 3 weeks for up to six cycles; maintenance pemetrexed was allowed. In all the patients, disease had progressed during receipt of first-line EGFR-TKI therapy. The primary end point was investigator-assessed progression-free survival. The median duration of progression-free survival was significantly longer with osimertinib than with platinum therapy plus pemetrexed (10.1 months vs. 4.4 months; hazard ratio; 0.30; 95% confidence interval [CI], 0.23 to 0.41; P<0.001). The objective response rate was significantly better with osimertinib (71%; 95% CI, 65 to 76) than with platinum therapy plus pemetrexed (31%; 95% CI, 24 to 40) (odds ratio for objective response, 5.39; 95% CI, 3.47 to 8.48; P<0.001). Among 144 patients with metastases to the central nervous system (CNS), the median duration of progression-free survival was longer among patients receiving osimertinib than among those receiving platinum therapy plus pemetrexed (8.5 months vs. 4.2 months; hazard ratio, 0.32; 95% CI, 0.21 to 0.49). The proportion of patients with adverse events of grade 3 or higher was lower with osimertinib (23%) than with platinum therapy plus pemetrexed (47%). Osimertinib had significantly greater efficacy than platinum therapy plus pemetrexed in patients with T790M-positive advanced non-small-cell lung cancer (including those with CNS metastases) in whom disease had progressed during first-line EGFR-TKI therapy. (Funded by AstraZeneca; AURA3 ClinicalTrials.gov number, NCT02151981 .).

A Single-Site Platinum CO Oxidation Catalyst in Zeolite KLTL: Microscopic and Spectroscopic Determination of the Locations of the Platinum Atoms

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

Kistler, Joseph D.; Chotigkrai, Nutchapon; Xu, Pinghong

2014-07-01

A stable site-isolated mononuclear platinum catalyst with a well-defined structure is presented. Platinum complexes supported in zeolite KLTL were synthesized from [Pt(NH 3) 4](NO 3) 2, oxidized at 633 K, and used to catalyze CO oxidation. Finally, IR and X-ray absorption spectra and electron micrographs determine the structures and locations of the platinum complexes in the zeolite pores, demonstrate the platinum-support bonding, and show that the platinum remained site isolated after oxidation and catalysis.

Synthesis of Platinum-nickel Nanowires and Optimization for Oxygen Reduction Performance

DOE PAGES

Alia, Shaun M.; Pivovar, Bryan S.

2018-01-01

Platinum-nickel (Pt-Ni) nanowires were developed as fuel cell electrocatalysts, and were optimized for the performance and durability in the oxygen reduction reaction. Spontaneous galvanic displacement was used to deposit Pt layers onto Ni nanowire substrates. The synthesis approach produced catalysts with high specific activities and high Pt surface areas. Hydrogen annealing improved Pt and Ni mixing and specific activity. Acid leaching was used to preferentially remove Ni near the nanowire surface, and oxygen annealing was used to stabilize near-surface Ni, improving durability and minimizing Ni dissolution. These protocols detail the optimization of each post-synthesis processing step, including hydrogen annealing tomore » 250 degrees C, exposure to 0.1 M nitric acid, and oxygen annealing to 175 degrees C. Through these steps, Pt-Ni nanowires produced increased activities more than an order of magnitude than Pt nanoparticles, while offering significant durability improvements. The presented protocols are based on Pt-Ni systems in the development of fuel cell catalysts. Furthermore, these techniques have also been used for a variety of metal combinations, and can be applied to develop catalysts for a number of electrochemical processes.« less

Platinum group metal-free electrocatalysts: Effects of synthesis on structure and performance in proton-exchange membrane fuel cell cathodes

NASA Astrophysics Data System (ADS)

Workman, Michael J.; Dzara, Michael; Ngo, Chilan; Pylypenko, Svitlana; Serov, Alexey; McKinney, Sam; Gordon, Jonathan; Atanassov, Plamen; Artyushkova, Kateryna

2017-04-01

Development of platinum group metal free catalysts for the oxygen reduction reaction (ORR) in proton exchange membrane fuel cells (PEMFCs) requires understanding of the interactions between surface chemistry and performance, both of which are strongly dependent on synthesis conditions. To elucidate these complex relationships, a set of Fe-N-C catalysts derived from the same set of precursor materials is fabricated by varying several key synthetic parameters under controlled conditions. The results of physicochemical characterization are presented and compared with the results of rotating disk electrode (RDE) analysis and fuel cell testing. We find that electrochemical performance is strongly correlated with three key properties related to catalyst composition: concentrations of 1) atomically dispersed Fe species, 2) species in which N is bound to Fe, and 3) surface oxides. Not only are these factors related to performance, these types of chemical species are shown to correlate with each other. This study provides evidence supporting the role of iron coordinated with nitrogen as an active species for the ORR, and offers synthetic pathways to increase the density of atomically dispersed iron species and surface oxides for optimum performance.

Synthesis of Platinum-nickel Nanowires and Optimization for Oxygen Reduction Performance

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

Alia, Shaun M.; Pivovar, Bryan S.

Platinum-nickel (Pt-Ni) nanowires were developed as fuel cell electrocatalysts, and were optimized for the performance and durability in the oxygen reduction reaction. Spontaneous galvanic displacement was used to deposit Pt layers onto Ni nanowire substrates. The synthesis approach produced catalysts with high specific activities and high Pt surface areas. Hydrogen annealing improved Pt and Ni mixing and specific activity. Acid leaching was used to preferentially remove Ni near the nanowire surface, and oxygen annealing was used to stabilize near-surface Ni, improving durability and minimizing Ni dissolution. These protocols detail the optimization of each post-synthesis processing step, including hydrogen annealing tomore » 250 degrees C, exposure to 0.1 M nitric acid, and oxygen annealing to 175 degrees C. Through these steps, Pt-Ni nanowires produced increased activities more than an order of magnitude than Pt nanoparticles, while offering significant durability improvements. The presented protocols are based on Pt-Ni systems in the development of fuel cell catalysts. Furthermore, these techniques have also been used for a variety of metal combinations, and can be applied to develop catalysts for a number of electrochemical processes.« less

Application of liposomal technologies for delivery of platinum analogs in oncology

PubMed Central

Liu, Demin; He, Chunbai; Wang, Andrew Z; Lin, Wenbin

2013-01-01

Platinum-based chemotherapy, such as cisplatin, oxaliplatin, and carboplatin, is one of the most widely utilized classes of cancer therapeutics. While highly effective, the clinical applications of platinum-based drugs are limited by their toxicity profiles as well as suboptimal pharmacokinetic properties. Therefore, one of the key research areas in oncology has been to develop novel platinum analog drugs and engineer new platinum drug formulations to improve the therapeutic ratio further. Such efforts have led to the development of platinum analogs including nedaplatin, heptaplatin, and lobaplatin. Moreover, reformulating platinum drugs using liposomes has resulted in the development of L-NDPP (Aroplatin™), SPI-77, Lipoplatin™, Lipoxal™, and LiPlaCis®. Liposomes possess several attractive biological activities, including biocompatibility, high drug loading, and improved pharmacokinetics, that are well suited for platinum drug delivery. In this review, we discuss the various platinum drugs and their delivery using liposome-based drug delivery vehicles. We compare and contrast the different liposome platforms as well as speculate on the future of platinum drug delivery research. PMID:24023517

Phosphoric acid fuel cell platinum use study

NASA Technical Reports Server (NTRS)

Lundblad, H. L.

1983-01-01

The U.S. Department of Energy is promoting the private development of phosphoric acid fuel cell (PAFC) power plants for terrestrial applications. Current PAFC technology utilizes platinum as catalysts in the power electrodes. The possible repercussions that the platinum demand of PAFC power plant commercialization will have on the worldwide supply and price of platinum from the outset of commercialization to the year 2000 are investigated. The platinum demand of PAFC commercialization is estimated by developing forecasts of platinum use per unit of generating capacity and penetration of PAFC power plants into the electric generation market. The ability of the platinum supply market to meet future demands is gauged by assessing the size of platinum reserves and the capability of platinum producers to extract, refine and market sufficient quantities of these reserves. The size and timing of platinum price shifts induced by the added demand of PAFC commercialization are investigated by several analytical methods. Estimates of these price shifts are then used to calculate the subsequent effects on PAFC power plant capital costs.

Phosphoric acid fuel cell platinum use study

NASA Astrophysics Data System (ADS)

Lundblad, H. L.

1983-05-01

The U.S. Department of Energy is promoting the private development of phosphoric acid fuel cell (PAFC) power plants for terrestrial applications. Current PAFC technology utilizes platinum as catalysts in the power electrodes. The possible repercussions that the platinum demand of PAFC power plant commercialization will have on the worldwide supply and price of platinum from the outset of commercialization to the year 2000 are investigated. The platinum demand of PAFC commercialization is estimated by developing forecasts of platinum use per unit of generating capacity and penetration of PAFC power plants into the electric generation market. The ability of the platinum supply market to meet future demands is gauged by assessing the size of platinum reserves and the capability of platinum producers to extract, refine and market sufficient quantities of these reserves. The size and timing of platinum price shifts induced by the added demand of PAFC commercialization are investigated by several analytical methods. Estimates of these price shifts are then used to calculate the subsequent effects on PAFC power plant capital costs.

Uptake and metabolism of cisplatin by rat kidney.

PubMed

Safirstein, R; Miller, P; Guttenplan, J B

1984-05-01

Cisplatin, an effective antineoplastic agent, is toxic to the kidney. Since the kidney's vulnerability to cisplatin may originate in its ability to accumulate and retain platinum to a greater degree than other organs, we studied the characteristics of the renal accumulation of platinum and investigated the nature of intracellular platinum. Cisplatin and ethylenediamminedichloroplatinum, nephrotoxic and antineoplastic liganded platinum compounds, were concentrated in rat renal cortical slices fivefold above medium concentration. Platinum uptake was energy- and temperature-dependent and could be inhibited by drugs which inhibit base transport. The organic anions para-aminohippurate and pyrazinoate did not reduce renal slice platinum uptake. Unbound platinum in the blood and urine was predominantly cisplatin but unbound platinum in kidney cytosol was not. This latter compound, in contrast to cisplatin, was not active as a mutagen. These studies suggest that the kidney accumulates platinum in part by transport or specific binding to the base transport system in the kidney and biotransforms it intracellularly. Unbound platinum in the cell is not cisplatin and may no longer be toxic.

Evaluation of platinum resistance thermometers

NASA Technical Reports Server (NTRS)

Daryabeigi, Kamran; Dillon-Townes, Lawrence A.

1988-01-01

An evaluation procedure for the characterization of industrial platinum resistance thermometers (PRTs) for use in the temperature range -120 to 160 C was investigated. This evaluation procedure consisted of calibration, thermal stability and hysteresis testing of four surface measuring PRTs. Five different calibration schemes were investigated for these sensors. The IPTS-68 formulation produced the most accurate result, yielding average sensor systematic error of 0.02 C and random error of 0.1 C. The sensors were checked for thermal stability by successive and thermal cycling between room temperature, 160 C, and boiling point of nitrogen. All the PRTs suffered from instability and hysteresis. The applicability of the self-heating technique as an in situ method for checking the calibration of PRTs located inside wind tunnels was investigated.

Defect Detection in Fuel Cell Gas Diffusion Electrodes Using Infrared Thermography

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

Ulsh, Michael; Porter, Jason M.; Bittinat, Daniel C.

2016-04-01

Polymer electrolyte membrane fuel cells are energy conversion devices that offer high power densities and high efficiencies for mobile and other applications. Successful introduction into the marketplace requires addressing cost barriers such as production volumes and platinum loading. For cost reduction, it is vital to minimize waste and maximize quality during the manufacturing of platinum-containing electrodes, including gas diffusion electrodes (GDEs). In this work, we report on developing a quality control diagnostic for GDEs, involving creating an ex situ exothermic reaction on the electrode surface and using infrared thermography to measure the resulting temperature profile. Experiments with a moving GDEmore » containing created defects were conducted to demonstrate the applicability of the diagnostic for real-time web-line inspection.« less

Gas sensitive materials for gas detection and methods of making

DOEpatents

Trakhtenberg, Leonid Israilevich; Gerasimov, Genrikh Nikolaevich; Gromov, Vladimir Fedorovich; Rozenberg, Valeriya Isaakovna

2014-07-15

A gas sensitive material comprising SnO.sub.2 nanocrystals doped with In.sub.2O.sub.3 and an oxide of a platinum group metal, and a method of making the same. The platinum group metal is preferably Pd, but also may include Pt, Ru, Ir, and combinations thereof. The SnO.sub.2 nanocrystals have a specific surface of 7 or greater, preferably about 20 m2/g, and a mean particle size of between about 10 nm and about 100 nm, preferably about 40 nm. A gas detection device made from the gas sensitive material deposited on a substrate, the gas sensitive material configured as a part of a current measuring circuit in communication with a heat source.

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

Simoes, A.Z.; Riccardi, C.S.; Cavalcante, L.S.

The film thickness dependence on the ferroelectric properties of lanthanum modified bismuth titanate Bi{sub 3.25}La{sub 0.75}Ti{sub 3}O{sub 12} was investigated. Films with thicknesses ranging from 230 to 404 nm were grown on platinum-coated silicon substrates by the polymeric precursor method. The internal strain is strongly influenced by the film thickness. The morphology of the film changes as the number of layers increases indicating a thickness dependent grain size. The leakage current, remanent polarization and drive voltage were also affected by the film thickness.

Quantitative skin prick and bronchial provocation tests with platinum salt.

PubMed Central

Merget, R; Schultze-Werninghaus, G; Bode, F; Bergmann, E M; Zachgo, W; Meier-Sydow, J

1991-01-01

Occupational asthma due to platinum salts is a frequent disease in platinum refineries. The diagnosis is based upon a history of work related symptoms and a positive skin prick test with platinum salts. Bronchial provocation tests have not been performed in epidemiological studies because the skin test is believed to be highly specific and sensitive. As no reliable data about this issue currently exist, this study assesses the use of skin prick and bronchial provocation tests with methacholine and platinum salt in platinum refinery workers. Twenty seven of 35 workers, who were referred to our clinic with work related symptoms and nine control subjects with bronchial hyperreactivity underwent a skin prick test and bronchial provocation with methacholine and platinum salt. For skin prick and bronchial provocation tests with platinum salt a 10(-2)-10(-8) mol/l hexachloroplatinic acid solution, in 10-fold dilutions was used. Four of the 27 subjects and all controls showed neither a bronchial reaction nor a skin reaction. Twenty three subjects were considered allergic to platinum salt; 22 of these showed a fall of 50% or more in specific airway conductance after inhalation of the platinum salt solution. Four workers experienced a positive bronchial reaction despite a negative skin prick test. No correlation of responsiveness to methacholine with responsiveness to platinum salt was found, but the skin prick test correlated with the bronchial reaction to platinum salt (rs = 0.50, p less than 0.023, n = 22). One dual reaction was seen in bronchial provocation tests. Side effects of both skin tests and bronchial provocation tests with platinum salt were rare and were not encountered in workers without a skin reaction to platinum salt. It is concluded that bronchial provocation tests with platinum salts should be performed on workers with work related symptoms but negative skin tests with platinum salts. PMID:1772797

Request for Correction 11001 Toxicological Review of Halogenated Platinum Salts and Platinum Compounds

EPA Pesticide Factsheets

Request for Correction by the International Platinum Group Metals Association seeking the correction of information disseminated in the draft EPA document Toxicological Review of Halogenated Platinum Salts and Platinum Compounds: In Support of Summary Information on the Integrated Risk Information System (IRIS).

Mass spectra of neutral particles released during electrical breakdown of thin polymer films

NASA Technical Reports Server (NTRS)

Kendall, B. R. F.

1985-01-01

A special type of time-of-flight mass spectrometer triggered from the breakdown event was developed to study the composition of the neutral particle flux released during the electrical breakdown of polymer films problem. Charge is fed onto a metal-backed polymer surface by a movable smooth platinum contact. A slowly increasing potential from a high-impedance source is applied to the contact until breakdown occurs. The breakdown characteristics is made similar to those produced by an electron beam charging system operating at similar potentials. The apparatus showed that intense instantaneous fluxes of neutral particles are released from the sites of breakdown events. For Teflon FEP films of 50 and 75 microns thickness the material released consists almost entirely of fluorocarbon fragments, some of them having masses greater than 350 atomic mass units amu, while the material released from a 50 micron Kapton film consists mainly of light hydrocarbons with masses at or below 44 amu, with additional carbon monoxide and carbon dioxide. The apparatus is modified to allow electron beam charging of the samples.

Ionic liquids as electrolytes for the development of a robust amperometric oxygen sensor.

PubMed

Wang, Zhe; Lin, Peiling; Baker, Gary A; Stetter, Joseph; Zeng, Xiangqun

2011-09-15

A simple Clark-type online electrochemical cell design, consisting of a platinum gauze working electrode and incorporating ionic liquids (IL) as electrolytes, has been successfully applied for the amperometric sensing of oxygen. Studying ILs comprising the bis(trifluoromethylsulfonyl)imide anion, the obtained analytical parameters were found to be strongly dependent on the choice of cation. Compared with a conventional Clark cell design based on an aqueous supporting electrolyte, the modified oxygen sensor achieves substantial improvements in performance and stability. A limit of detection for oxygen as low as 0.05 vol %, linearity over an oxygen partial pressure between 0% and 20%, and a steady-state response time of 2 min was demonstrated, with a stable analytical response shown over the examined period of 90 days with no obvious fouling of the electrode surface. Based on the attractive physical attributes of ionic liquids (e.g., thermal stability beyond 150 °C), one can envision intriguing utility in nonstandard conditions and long-term online applications, as well as extension to the determination of other gases, such as methane and nitric oxide.

Highly efficient temperature-induced visible light photocatalytic hydrogen production

NASA Astrophysics Data System (ADS)

Han, Bing

Photocatalysis is the acceleration of photoreaction in presence of a photocatalyst. Semiconductor photocatalysis has obtained much attention as a potential solution to the worldwide energy storage due to its promising ability to directly convert solar energy into chemical fuels. This dissertation research mainly employ three approaches to enhance photocatalytic activities, which includes (I) Modifying semiconductor nanomaterials for visible and near-IR light absorption; (II) Synthesis of light-diffuse-reflection-surface of SiO2 substrate to utilize scattered light; and (III) design of a hybrid system that combines light and heat to enhance visible light photocatalytic activity. Those approaches were applied to two systems: (1) hydrogen production from water; (2) carbon dioxide reforming of methane. The activity of noble metals such as platinum were investigated as co-catalysts and cheap earth abundant catalysts as alternatives to reduce cost were also developed. Stability, selectivity, mechanism were investigated. Great enhancement of visible light activity over a series of semiconductors/heterostructures were observed. Such extraordinary performance of artificial photosynthetic hydrogen production system would provide a novel approach for the utilization of solar energy for chemical fuel production.

40 CFR 440.110 - Applicability; description of the platinum ore subcategory.

Code of Federal Regulations, 2013 CFR

2013-07-01

... platinum ore subcategory. 440.110 Section 440.110 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Platinum Ores Subcategory § 440.110 Applicability; description of the platinum ore subcategory. The provisions of this subpart K are applicable to discharges from (a) mines that produce platinum ore and (b...

40 CFR 440.110 - Applicability; description of the platinum ore subcategory.

Code of Federal Regulations, 2014 CFR

2014-07-01

... platinum ore subcategory. 440.110 Section 440.110 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Platinum Ores Subcategory § 440.110 Applicability; description of the platinum ore subcategory. The provisions of this subpart K are applicable to discharges from (a) mines that produce platinum ore and (b...

40 CFR 440.110 - Applicability; description of the platinum ore subcategory.

Code of Federal Regulations, 2012 CFR

2012-07-01

... platinum ore subcategory. 440.110 Section 440.110 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Platinum Ores Subcategory § 440.110 Applicability; description of the platinum ore subcategory. The provisions of this subpart K are applicable to discharges from (a) mines that produce platinum ore and (b...

Novel platinum black electroplating technique improving mechanical stability.

PubMed

Kim, Raeyoung; Nam, Yoonkey

2013-01-01

Platinum black microelectrodes are widely used as an effective neural signal recording sensor. The simple fabrication process, high quality signal recording and proper biocompatibility are the main advantages of platinum black microelectrodes. When microelectrodes are exposed to actual biological system, various physical stimuli are applied. However, the porous structure of platinum black is vulnerable to external stimuli and destroyed easily. The impedance level of the microelectrode increases when the microelectrodes are damaged resulting in decreased recording performance. In this study, we developed mechanically stable platinum black microelectrodes by adding polydopamine. The polydopamine layer was added between the platinum black structures by electrodeposition method. The initial impedance level of platinum black only microelectrodes and polydopamine added microelectrodes were similar but after applying ultrasonication the impedance value dramatically increased for platinum black only microelectrodes, whereas polydopamine added microelectrodes showed little increase which were nearly retained initial values. Polydopamine added platinum black microelectrodes are expected to extend the availability as neural sensors.

Oxidation-induced structural changes in sub-nanometer platinum supported on alumina

DOE PAGES

DeBusk, Melanie Moses; Allard, Jr, Lawrence Frederick; Blom, Douglas Allen; ...

2015-06-26

Platinum supported on alumina is an essential component of emission treatment catalysts used in transportation. Theoretical, experimental, and mechanistic aspects of platinum particles supported on a variety of supports have been extensively studied; however, available experimental information on the behavior of single vs. sub-nanometer platinum is extremely limited. To bridge the knowledge gap between single supported platinum and well-formed supported platinum nanoparticles, we have carried out synthesis, characterization, and CO and NO oxidation studies of sub-nanometer platinum supported on α, θ, and γ-Al 2O 3 and monitored changes in structure upon exposure to CO and NO oxidation conditions. Furthermore, wemore » find that sub-nanometer Pt is highly effective for CO oxidation due to high platinum dispersion but is not very efficient as NO oxidation catalyst. Lastly, sub-nanometer platinum agglomerates rapidly under CO or NO oxidation conditions to form nanoparticles.« less

Rapid biological synthesis of platinum nanoparticles using Ocimum sanctum for water electrolysis applications.

PubMed

Soundarrajan, C; Sankari, A; Dhandapani, P; Maruthamuthu, S; Ravichandran, S; Sozhan, G; Palaniswamy, N

2012-06-01

The leaf extract of Ocimum sanctum was used as a reducing agent for the synthesis of platinum nanoparticles from an aqueous chloroplatinic acid (H(2)PtCl(6)·6H(2)O). A greater conversion of platinum ions to nanoparticles was achieved by employing a tulsi leaf broth with a reaction temperature of 100 °C. Energy-dispersive absorption X-ray spectroscopy confirmed the platinum particles as major constituent in the reduction process. It is evident from scanning electron microscopy that the reduced platinum particles were found as aggregates with irregular shape. Fourier-transform infrared spectroscopy revealed that the compounds such as ascorbic acid, gallic acid, terpenoids, certain proteins and amino acids act as reducing agents for platinum ions reduction. X-ray diffraction spectroscopy suggested the associated forms of platinum with other molecules and the average particle size of platinum nanoparticle was 23 nm, calculated using Scherer equation. The reduced platinum showed similar hydrogen evolution potential and catalytic activity like pure platinum using linear scan voltammetry. This environmentally friendly method of biological platinum nanoparticles production increases the rates of synthesis faster which can potentially be used in water electrolysis applications.

Exploration of the Ionizable Metal Cluster-Electrode Surface Analogy: Infrared Spectroelectrochemistry of (Pt24(CO)30)n, (Pt26(CO)32)n, and (Pt38(CO) 44)n (n=0 to -10), and Comparisons with Potential-Dependent Spectra of CO adlayers on Platinum Surfaces

DTIC Science & Technology

1992-05-01

100"C under vacuum for 24 hours. The corresponding tetraethylammonium hexafluorophosphate (TEAH) was prepared similarly by using ammonium...the four electrolytes examined in acetonitrile (Table III). Nevertheless, use of lithium perchlorate in acetonitrile restricted the range of cluster

Revealing the Atomic Restructuring of Pt–Co Nanoparticles

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

Xin, Huolin L.; Alayoglu, Selim; Tao, Runzhe

2014-06-11

We studied Pt-Co bimetallic nanoparticles during oxidation in O2 and reduction in H2 atmospheres using an aberration corrected environmental transmission electron microscope. During oxidation Co migrates to the nanoparticle surface forming a strained epitaxial CoO film. It subsequently forms islands via strain relaxation. The atomic restructuring is captured as a function of time. During reduction cobalt migrates back to the bulk, leaving a monolayer of platinum on the surface.

The Next Generation of Platinum Drugs: Targeted Pt(II) Agents, Nanoparticle Delivery, and Pt(IV) Prodrugs

PubMed Central

Johnstone, Timothy C.; Suntharalingam, Kogularamanan; Lippard, Stephen J.

2016-01-01

The platinum drugs, cisplatin, carboplatin, and oxaliplatin, prevail in the treatment of cancer,, but new platinum agents have been very slow to enter the clinic. Recently, however, there has been a surge of activity, based on a great deal of mechanistic information, aimed at developing non-classical platinum complexes that operate via mechanisms of action distinct from those of the approved drugs. The use of nanodelivery devices has also grown and many different strategies have been explored to incorporate platinum warheads into nanomedicine constructs. In this review, we discuss these efforts to create the next generation of platinum anticancer drugs. The introduction provides the reader with a brief overview of the use, development, and mechanism of action of the approved platinum drugs to provide the context in which more recent research has flourished. We then describe approaches that explore non-classical platinum(II) complexes with trans geometry and with a monofunctional coordination mode, polynuclear platinum(II) compounds, platinum(IV) prodrugs, dual-treat agents, and photoactivatable platinum(IV) complexes. Nanodelivery particles designed to deliver platinum(IV) complexes will also be discussed, including carbon nanotubes, carbon nanoparticles, gold nanoparticles, quantum dots, upconversion nanoparticles, and polymeric micelles. Additional nanoformulations including supramolecular self-assembled structures, proteins, peptides, metal-organic frameworks, and coordination polymers will then be described. Finally, the significant clinical progress made by nanoparticle formulations of platinum(II) agents will be reviewed. We anticipate that such a synthesis of disparate research efforts will not only help to generate new drug development ideas and strategies, but also reflect our optimism that the next generation of platinum cancer drugs is about to arrive. PMID:26865551

Phase II randomized study of PM01183 versus topotecan in patients with platinum-resistant/refractory advanced ovarian cancer

PubMed Central

Poveda, A.; del Campo, J. M.; Ray-Coquard, I.; Alexandre, J.; Provansal, M.; Guerra Alía, E. M.; Casado, A.; Gonzalez-Martin, A.; Fernández, C.; Rodriguez, I.; Soto, A.; Kahatt, C.; Fernández Teruel, C.; Galmarini, C. M.; Pérez de la Haza, A.; Bohan, P.; Berton-Rigaud, D.

2017-01-01

Background PM01183 is a new compound that blocks active transcription, produces DNA breaks and apoptosis, and affects the inflammatory microenvironment. PM01183 showed strong antitumor activity in preclinical models of cisplatin-resistant epithelial ovarian cancer. Patients and methods Patients with platinum-resistant/refractory ovarian cancer were included in a two-stage, controlled, randomized (in a second stage), multicenter, phase II study. Primary endpoint was overall response rate (ORR) by RECIST and/or GCIG criteria. The exploratory first stage (n = 22) confirmed the activity of PM01183 as a single agent at 7.0 mg flat dose every 3 weeks (q3wk). The second stage (n = 59) was randomized and controlled with topotecan on days 1–5 q3wk or weekly (every 4 weeks, q4wk). Results ORR was 23% (95% CI, 13%–37%) for 52 PM01183-treated patients. Median duration of response was 4.6 months (95% CI, 2.5–6.9 months), and 23% (95% CI, 0%–51%) of responses lasted 6 months or more. Ten of the 12 confirmed responses were reported for 33 patients with platinum-resistant disease [ORR = 30% (95% CI, 16%–49%)]; for the 29 patients treated with topotecan in the second stage, no responses were found. Median PFS for all PM01183-treated patients was 4.0 months (95% CI, 2.7–5.6 months), and 5.0 months (95% CI, 2.7–6.9 months) for patients with platinum-resistant disease. Grade 3/4 neutropenia in 85% of patients; febrile neutropenia in 21% and fatigue (grade 3 in 35%) were the principal safety findings for PM01183. Conclusion PM01183 is an active drug in platinum-resistant/refractory ovarian cancer and warrants further development. The highest activity was observed in platinum-resistant disease. Its safety profile indicates the dose should be adjusted to body surface area (mg/m2). Trial code EudraCT 2011-002172-16. PMID:28368437

Phase II randomized study of PM01183 versus topotecan in patients with platinum-resistant/refractory advanced ovarian cancer.

PubMed

Poveda, A; Del Campo, J M; Ray-Coquard, I; Alexandre, J; Provansal, M; Guerra Alía, E M; Casado, A; Gonzalez-Martin, A; Fernández, C; Rodriguez, I; Soto, A; Kahatt, C; Fernández Teruel, C; Galmarini, C M; Pérez de la Haza, A; Bohan, P; Berton-Rigaud, D

2017-06-01

PM01183 is a new compound that blocks active transcription, produces DNA breaks and apoptosis, and affects the inflammatory microenvironment. PM01183 showed strong antitumor activity in preclinical models of cisplatin-resistant epithelial ovarian cancer. Patients with platinum-resistant/refractory ovarian cancer were included in a two-stage, controlled, randomized (in a second stage), multicenter, phase II study. Primary endpoint was overall response rate (ORR) by RECIST and/or GCIG criteria. The exploratory first stage (n = 22) confirmed the activity of PM01183 as a single agent at 7.0 mg flat dose every 3 weeks (q3wk). The second stage (n = 59) was randomized and controlled with topotecan on days 1-5 q3wk or weekly (every 4 weeks, q4wk). ORR was 23% (95% CI, 13%-37%) for 52 PM01183-treated patients. Median duration of response was 4.6 months (95% CI, 2.5-6.9 months), and 23% (95% CI, 0%-51%) of responses lasted 6 months or more. Ten of the 12 confirmed responses were reported for 33 patients with platinum-resistant disease [ORR = 30% (95% CI, 16%-49%)]; for the 29 patients treated with topotecan in the second stage, no responses were found. Median PFS for all PM01183-treated patients was 4.0 months (95% CI, 2.7-5.6 months), and 5.0 months (95% CI, 2.7-6.9 months) for patients with platinum-resistant disease. Grade 3/4 neutropenia in 85% of patients; febrile neutropenia in 21% and fatigue (grade 3 in 35%) were the principal safety findings for PM01183. PM01183 is an active drug in platinum-resistant/refractory ovarian cancer and warrants further development. The highest activity was observed in platinum-resistant disease. Its safety profile indicates the dose should be adjusted to body surface area (mg/m2). EudraCT 2011-002172-16. © The Author 2017. Published by Oxford University Press on behalf of the European Society for Medical Oncology.

Investigations of the Binding of [Pt2(DTBPA)Cl2](II) and [Pt2(TPXA)Cl2](II) to DNA via Various Cross-Linking Modes

PubMed Central

Yue, Hongwei; Yang, Bo; Wang, Yan; Chen, Guangju

2013-01-01

We have constructed models for a series of platinum-DNA adducts that represent the binding of two agents, [Pt2(DTBPA)Cl2](II) and [Pt2(TPXA)Cl2](II), to DNA via inter- and intra-strand cross-linking, and carried out molecular dynamics simulations and DNA conformational dynamics calculations. The effects of trans- and cis-configurations of the centers of these di-nuclear platinum agents, and of different bridging linkers, have been investigated on the conformational distortions of platinum-DNA adducts formed via inter- and intra-strand cross-links. The results demonstrate that the DNA conformational distortions for the various platinum-DNA adducts with differing cross-linking modes are greatly influenced by the difference between the platinum-platinum distance for the platinum agent and the platinum-bound N7–N7 distance for the DNA molecule, and by the flexibility of the bridging linkers in the platinum agent. However, the effects of trans/cis-configurations of the platinum-centers on the DNA conformational distortions in the platinum-DNA adducts depend on the inter- and intra-strand cross-linking modes. In addition, we discuss the relevance of DNA base motions, including opening, shift and roll, to the changes in the parameters of the DNA major and minor grooves caused by binding of the platinum agent. PMID:24077126

Antitumor effects of nano-bubble hydrogen-dissolved water are enhanced by coexistent platinum colloid and the combined hyperthermia with apoptosis-like cell death.

PubMed

Asada, Ryoko; Kageyama, Katsuhiro; Tanaka, Hiroshi; Matsui, Hisakazu; Kimura, Masatsugu; Saitoh, Yasukazu; Miwa, Nobuhiko

2010-12-01

In order to erase reactive oxygen species (ROS) related with the proliferation of tumor cells by reducing activity of hydrogen, we developed functional water containing nano-bubbles (diameters: <900 nm for 71%/population) hydrogen of 1.1-1.5 ppm (the theoretical maximum: 1.6 ppm) with a reducing ability (an oxidation-reduction potential -650 mV, normal water: +100-200 mV) using a microporous-filter hydrogen-jetting device. We showed that hydrogen water erased ROS indispensable for tumor cell growth by ESR/spin trap, the redox indicator CDCFH-DA assay, and was cytotoxic to Ehrlich ascites tumor cells as assessed by WST-8 assay, crystal violet dye stain and scanning electron microscopy, after 24-h or 48-h incubation sequent to warming at 37°C or 42°C. Hydrogen water supplemented with platinum colloid (0.3 ppm Pt in 4% polyvinylpyrrolidone) had more antitumor activity than hydrogen water alone, mineral water alone (15.6%), hydrogen water plus mineral water, or platinum colloid alone as observed by decreased cell numbers, cell shrinkage and pycnosis (nuclear condensation)/karyorrhexis (nuclear fragmentation) indicative of apoptosis, together with cell deformation and disappearance of microvilli on the membrane surface. These antitumor effects were promoted by combination with hyperthermia at 42°C. Thus, the nano-bubble hydrogen water with platinum colloid is potent as an anti-tumor agent.

Motion-Based pH Sensing Based on the Cartridge-Case-like Micromotor.

PubMed

Su, Yajun; Ge, Ya; Liu, Limei; Zhang, Lina; Liu, Mei; Sun, Yunyu; Zhang, Hui; Dong, Bin

2016-02-17

In this paper, we report a novel cartridge-case-like micromotor. The micromotor, which is fabricated by the template synthesis method, consists of a gelatin shell with platinum nanoparticles decorating its inner surface. Intriguingly, the resulting cartridge-case-like structure exhibits a pH-dependent "open and close" feature, which originates from the pH responsiveness of the gelatin material. On the basis of the catalytic activity of the platinum nanoparticle inside the gelatin shell, the resulting cartridge-case-like structure is capable of moving autonomously in the aqueous solution containing the hydrogen peroxide fuel. More interestingly, we find out that the micromotor can be utilized as a motion-based pH sensor over the whole pH range. The moving velocity of the micromotor increases monotonically with the increase of pH of the analyte solution. Three different factors are considered to be responsible for the proportional relation between the motion speed and pH of the analyte solution: the peroxidase-like and oxidase-like catalytic behavior of the platinum nanoparticle at low and high pH, the volumetric decomposition of the hydrogen peroxide under the basic condition and the pH-dependent catalytic activity of the platinum nanoparticle caused by the swelling/deswelling behavior of the gelatin material. The current work highlights the impact of the material properties on the motion behavior of a micromotor, thus paving the way toward its application in the motion-based sensing field.

Permeation of platinum and rhodium nanoparticles through intact and damaged human skin

NASA Astrophysics Data System (ADS)

Mauro, Marcella; Crosera, Matteo; Bianco, Carlotta; Adami, Gianpiero; Montini, Tiziano; Fornasiero, Paolo; Jaganjac, Morana; Bovenzi, Massimo; Filon, Francesca Larese

2015-06-01

The aim of the study was to evaluate percutaneous penetration of platinum and rhodium nanoparticles (PtNPs: 5.8 ± 0.9 nm, RhNPs: 5.3 ± 1.9 nm) through human skin. Salts compounds of these metals are sensitizers and some also carcinogenic agents. In vitro permeation experiments were performed using Franz diffusion cells with intact and damaged skin. PtNPs and RhNPs, stabilized with polyvinylpyrrolidone, were synthesized by reduction of Na2PtCl6 and RhCl3·3H2O respectively. Suspensions with a concentration of 2.0 g/L of PtNPs and RhNPs were dispersed separately in synthetic sweat at pH 4.5 and applied as donor phases to the outer surface of the skin for 24 h. Measurements of the content of the metals in the receiving solution and in the skin were performed subsequently. Rhodium skin permeation was demonstrated through damaged skin, with a permeation flux of 0.04 ± 0.04 μg cm-2 h-1 and a lag time of 7.9 ± 1.1 h, while no traces of platinum were found in receiving solutions. Platinum and rhodium skin-analysis showed significantly higher concentrations of the metals in damaged skin. Rh and Pt applied as NPs can penetrate the skin barrier and Rh can be found in receiving solutions. These experiments pointed out the need for skin contamination prevention, since even a minor injury to the skin barrier can significantly increase penetration.

Isotope dilution inductively coupled plasma quadrupole mass spectrometry in connection with a chromatographic separation for ultra trace determinations of platinum group elements (Pt, Pd, Ru, Ir) in environmental samples.

PubMed

Müller, M; Heumann, K G

2000-09-01

An isotope dilution inductively coupled plasma quadrupole mass spectrometric (ID-ICP-QMS) method was developed for the simultaneous determination of the platinum group elements Pt, Pd, Ru, and Ir in environmental samples. Spike solutions, enriched with the isotopes 194Pt, 108Pd, 99Ru, and 191Ir, were used for the isotope dilution step. Interfering elements were eliminated by chromatographic separation using an anion-exchange resin. Samples were dissolved with aqua regia in a high pressure asher. Additional dissolution of possible silicate portions by hydrofluoric acid was usually not necessary. Detection limits of 0.15 ng x g(-1), 0.075 ng x g(-1), and 0.015 ng x g(-1) were achieved for Pt, Pd, Ru, and Ir, respectively, using sample weights of only 0.2 g. The reliability of the ID-ICP-QMS method was demonstrated by analyzing a Canadian geological reference material and by participating in an interlaboratory study for the determination of platinum and palladium in a homogenized road dust sample. Surface soil, sampled at different distances from a highway, showed concentrations in the range of 0.1-87 ng x g(-1). An exponential decrease of the platinum and palladium concentration with increasing distance and a small anthropogenic contribution to the natural background concentration of ruthenium and iridium was found in these samples.

A nanohybrid of platinum nanoparticles-porous ZnO-hemin with electrocatalytic activity to construct an amplified immunosensor for detection of influenza.

PubMed

Yang, Zhe-Han; Zhuo, Ying; Yuan, Ruo; Chai, Ya-Qin

2016-04-15

In this work, a nanohybrid of platinum nanoparticles-porous ZnO spheres-hemin (Pt-pZnO-hemin) was synthesized for construction of alkaline phosphatase-based immunosensor for detection of influenza. Briefly, porous ZnO spheres (pZnO) were prepared using soluble starches as the capping agent, followed by surface functionalization of platinum nanoparticles via a hydrothermal method (Pt-pZnO). Then, hemin with carboxylic functionality was spontaneously adsorbed onto Pt-pZnO by ester-like binding between carboxylic group of hemin and ZnO. Compared with platinum nanoparticles and hemin, the resulting Pt-pZnO-hemin nanohybrid showed more excellent electrocatalysis activity toward 1-naphthol (1-NP). Taking advantage of the Pt-pZnO-hemin, we have developed an amplified electrochemical immunosensor based on in situ generation of redox probe by alkaline phosphatase (ALP) and Pt-pZnO-hemin as signal enhancer. Herein, electrochemically active 1-NP was generated by enzymatic hydrolysis of inactive 1-naphthyl phosphate by ALP, then Pt-pZnO-hemin was used as catalyst to catalytically oxidize 1-NP, resulting in electrochemical signal amplification. Furthermore, in comparison with other nanomaterials including Au-pZnO, Pt-pZnO and Au-pZnO-hemin, the excellent catalytical property of Pt-pZnO-hemin make it a promising nanohybrid material for ALP-based immunosensor for signal amplification. Copyright © 2015. Published by Elsevier B.V.

Impact of Prior Platinum-Based Therapy on Patients Receiving Salvage Systemic Treatment for Advanced Urothelial Carcinoma.

PubMed

Sonpavde, G; Pond, G R; Di Lorenzo, G; Buonerba, C; Rozzi, A; Lanzetta, G; Necchi, A; Giannatempo, P; Raggi, D; Matsumoto, K; Choueiri, T K; Mullane, S; Niegisch, G; Albers, P; Lee, J L; Kitamura, H; Kume, H; Bellmunt, J

2016-12-01

Trials of salvage therapy for advanced urothelial carcinoma have required prior platinum-based therapy. This practice requires scrutiny because non-platinum-based first-line therapy may be offered to cisplatin-ineligible patients. Data of patients receiving salvage systemic chemotherapy were collected. Data on prior first-line platinum exposure were required in addition to treatment-free interval, hemoglobin, Eastern Cooperative Oncology Group performance status, albumin, and liver metastasis status. Cox proportional hazard regression was used to evaluate their association with overall survival (OS) after accounting for salvage single-agent or combination chemotherapy. Data were obtained from 455 patients previously exposed to platinum-based therapy and 37 not exposed to platinum. In the group exposed to prior platinum therapy, salvage therapy consisted of a single-agent taxane (n = 184) or a taxane-containing combination chemotherapy (n = 271). In the group not exposed to prior platinum therapy, salvage therapy consisted of taxane or vinflunine (n = 20), 5-fluorouracil (n = 1), taxane-containing combination chemotherapy (n = 12), carboplatin-based combinations (n = 2), and cisplatin-based combinations (n = 2). The median OS for the prior platinum therapy group was 7.8 months (95% confidence interval, 7.0, 8.1), and for the group that had not received prior platinum therapy was 9.0 months (95% confidence interval, 6.0, 11.0; P = .50). In the multivariable analysis, prior platinum therapy versus no prior platinum exposure did not confer an independent impact on OS (hazard ratio, 1.10; 95% confidence interval, 0.75, 1.64; P = .62). Prior platinum- versus non-platinum-based chemotherapy did not have a prognostic impact on OS after accounting for major prognostic factors in patients receiving salvage systemic chemotherapy for advanced urothelial carcinoma. Lack of prior platinum therapy should not disqualify patients from inclusion onto trials of salvage therapy. Copyright © 2016 Elsevier Inc. All rights reserved.

Epirubicin, Cisplatin, and Capecitabine for Primary Platinum-Resistant or Platinum-Refractory Epithelial Ovarian Cancer

PubMed Central

Sayal, Karen; Gounaris, Ioannis; Basu, Bristi; Freeman, Sue; Moyle, Penny; Hosking, Karen; Iddawela, Mahesh; Jimenez-Linan, Mercedes; Abraham, Jean; Brenton, James; Hatcher, Helen; Earl, Helena; Parkinson, Christine

2015-01-01

Objective Primary platinum-resistant epithelial ovarian cancer (EOC) is an area of unmet medical need. There is limited evidence from small studies that platinum-based combinations can overcome “resistance” in a proportion of patients. We investigated the efficacy and toxicity of platinum-based combination chemotherapy in the platinum-resistant and platinum-refractory setting. Methods Epirubicin, cisplatin, and capecitabine (ECX) combination chemotherapy was used at our institution for the treatment of relapsed EOC. From the institutional database, we identified all patients with primary platinum-refractory or platinum-resistant relapse treated with ECX as second-line therapy between 2001 and 2012. We extracted demographic, clinical, treatment, and toxicity data and outcomes. We used logistic and Cox regression models to identify predictors of response and survival respectively. Results Thirty-four 34 patients (8 refractory, 26 resistant) were treated with ECX. Response Evaluation Criteria In Solid Tumors (RECIST) response rate was 45%, median progression-free survival (PFS) was 6.4 months, and overall survival (OS) was 10.6 months. Platinum-resistant patients had better outcomes than did platinum-refractory patients (response rate, 54% vs 0%, P = 0.047; PFS 7.2 vs 1.8 months, P < 0.0001; OS 14.4 vs 3 months, P < 0.001). In regression models, time to progression after first-line treatment and platinum-refractory status were the strongest predictors of response and PFS or OS, respectively. Patients with time to progression after first-line treatment longer than 3 months showed PFS and OS of 7.9 and 14.7 months, respectively. Toxicity was manageable, with only 13% of cycles administered at reduced doses. Conclusions Epirubicin, cisplatin, and capecitabine seems to be active in platinum-resistant relapsed EOC with manageable toxicity. Further prospective investigation of platinum-anthracycline combinations is warranted in patients who relapse 3 to 6 months after first-line platinum-taxane treatment. PMID:25962114

Platinum coat color in red fox (Vulpes vulpes) is caused by a mutation in an autosomal copy of KIT.

PubMed

Johnson, J L; Kozysa, A; Kharlamova, A V; Gulevich, R G; Perelman, P L; Fong, H W F; Vladimirova, A V; Oskina, I N; Trut, L N; Kukekova, A V

2015-04-01

The red fox (Vulpes vulpes) demonstrates a variety of coat colors including platinum, a common phenotype maintained in farm-bred fox populations. Foxes heterozygous for the platinum allele have a light silver coat and extensive white spotting, whereas homozygosity is embryonic lethal. Two KIT transcripts were identified in skin cDNA from platinum foxes. The long transcript was identical to the KIT transcript of silver foxes, whereas the short transcript, which lacks exon 17, was specific to platinum. The KIT gene has several copies in the fox genome: an autosomal copy on chromosome 2 and additional copies on the B chromosomes. To identify the platinum-specific KIT sequence, the genomes of one platinum and one silver fox were sequenced. A single nucleotide polymorphism (SNP) was identified at the first nucleotide of KIT intron 17 in the platinum fox. In platinum foxes, the A allele of the SNP disrupts the donor splice site and causes exon 17, which is part of a segment that encodes a conserved tyrosine kinase domain, to be skipped. Complete cosegregation of the A allele with the platinum phenotype was confirmed by linkage mapping (LOD 25.59). All genotyped farm-bred platinum foxes from Russia and the US were heterozygous for the SNP (A/G), whereas foxes with different coat colors were homozygous for the G allele. Identification of the platinum mutation suggests that other fox white-spotting phenotypes, which are allelic to platinum, would also be caused by mutations in the KIT gene. © 2015 Stichting International Foundation for Animal Genetics.

Atomistic modelling of evaporation and explosive boiling of thin film liquid argon over internally recessed nanostructured surface

NASA Astrophysics Data System (ADS)

Hasan, Mohammad Nasim; Shavik, Sheikh Mohammad; Rabbi, Kazi Fazle; Haque, Mominul

2016-07-01

Molecular dynamics (MD) simulations have been carried out to investigate evaporation and explosive boiling phenomena of thin film liquid argon on nanostructured solid surface with emphasis on the effect of solid-liquid interfacial wettability. The nanostructured surface considered herein consists of trapezoidal internal recesses of the solid platinum wall. The wetting conditions of the solid surface were assumed such that it covers both the hydrophilic and hydrophobic conditions and hence effect of interfacial wettability on resulting evaporation and boiling phenomena was the main focus of this study. The initial configuration of the simulation domain comprised of a three phase system (solid platinum, liquid argon and vapor argon) on which equilibrium molecular dynamics (EMD) was performed to reach equilibrium state at 90 K. After equilibrium of the three-phase system was established, the wall was set to different temperatures (130 K and 250 K for the case of evaporation and explosive boiling respectively) to perform non-equilibrium molecular dynamics (NEMD). The variation of temperature and density as well as the variation of system pressure with respect to time were closely monitored for each case. The heat flux normal to the solid surface was also calculated to illustrate the effectiveness of heat transfer for hydrophilic and hydrophobic surfaces in cases of both nanostructured surface and flat surface. The results obtained show that both the wetting condition of the surface and the presence of internal recesses have significant effect on normal evaporation and explosive boiling of the thin liquid film. The heat transfer from solid to liquid in cases of surface with recesses are higher compared to flat surface without recesses. Also the surface with higher wettability (hydrophilic) provides more favorable conditions for boiling than the low-wetting surface (hydrophobic) and therefore, liquid argon responds quickly and shifts from liquid to vapor phase faster in case of hydrophilic surface. The heat transfer rate is also much higher in case of hydrophilic surface.

Atomistic modelling of evaporation and explosive boiling of thin film liquid argon over internally recessed nanostructured surface

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

Hasan, Mohammad Nasim, E-mail: nasim@me.buet.ac.bd.com; Shavik, Sheikh Mohammad, E-mail: shavik@me.buet.ac.bd.com; Rabbi, Kazi Fazle, E-mail: rabbi35.me10@gmail.com

2016-07-12

Molecular dynamics (MD) simulations have been carried out to investigate evaporation and explosive boiling phenomena of thin film liquid argon on nanostructured solid surface with emphasis on the effect of solid-liquid interfacial wettability. The nanostructured surface considered herein consists of trapezoidal internal recesses of the solid platinum wall. The wetting conditions of the solid surface were assumed such that it covers both the hydrophilic and hydrophobic conditions and hence effect of interfacial wettability on resulting evaporation and boiling phenomena was the main focus of this study. The initial configuration of the simulation domain comprised of a three phase system (solidmore » platinum, liquid argon and vapor argon) on which equilibrium molecular dynamics (EMD) was performed to reach equilibrium state at 90 K. After equilibrium of the three-phase system was established, the wall was set to different temperatures (130 K and 250 K for the case of evaporation and explosive boiling respectively) to perform non-equilibrium molecular dynamics (NEMD). The variation of temperature and density as well as the variation of system pressure with respect to time were closely monitored for each case. The heat flux normal to the solid surface was also calculated to illustrate the effectiveness of heat transfer for hydrophilic and hydrophobic surfaces in cases of both nanostructured surface and flat surface. The results obtained show that both the wetting condition of the surface and the presence of internal recesses have significant effect on normal evaporation and explosive boiling of the thin liquid film. The heat transfer from solid to liquid in cases of surface with recesses are higher compared to flat surface without recesses. Also the surface with higher wettability (hydrophilic) provides more favorable conditions for boiling than the low-wetting surface (hydrophobic) and therefore, liquid argon responds quickly and shifts from liquid to vapor phase faster in case of hydrophilic surface. The heat transfer rate is also much higher in case of hydrophilic surface.« less

Expression of domains for protein-protein interaction of nucleotide excision repair proteins modifies cancer cell sensitivity to platinum derivatives and genomic stability.

PubMed

Jordheim, Lars Petter; Cros-Perrial, Emeline; Matera, Eva-Laure; Bouledrak, Karima; Dumontet, Charles

2014-10-01

Nucleotide excision repair (NER) is involved in the repair of DNA damage caused by platinum derivatives and has been shown to decrease the cytotoxic activity of these drugs. Because protein-protein interactions are essential for NER activity, we transfected human cancer cell lines (A549 and HCT116) with plasmids coding the amino acid sequences corresponding to the interacting domains between excision repair cross-complementation group 1 (ERCC1) and xeroderma pigmentosum, complementation group A (XPA), as well as ERCC1 and xeroderma pigmentosum, complementation group F (XPF), all NER proteins. Using the 3-(4,5-dimethyl-2 thiazoyl)-2,5-diphenyl-2H-tetrazolium bromide (MTT) assay and annexin V staining, we showed that transfected A549 cells were sensitized 1.2-2.2-fold to carboplatin and that transfected HCT116 cells were sensitized 1.4-5.4-fold to oxaliplatin in vitro. In addition, transfected cells exhibited modified in vivo sensitivity to the same drugs. Finally, in particular cell models of the interaction between ERCC1 and XPF, DNA repair was decreased, as evidenced by increased phosphorylation of the histone 2AX after exposure to mitomycin C, and genomic instability was increased, as determined by comparative genomic hybridization studies. The results indicate that the interacting peptides act as dominant negatives and decrease NER activity through inhibition of protein-protein interactions. © 2014 Wiley Publishing Asia Pty Ltd.

Method for forming porous platinum films

DOEpatents

Maya, Leon

2000-01-01

A method for forming a platinum film includes providing a substrate, sputtering a crystalline platinum oxide layer over at least a portion of the substrate, and reducing the crystalline platinum oxide layer to form the platinum film. A device includes a non-conductive substrate and a platinum layer having a density of between about 2 and 5 g/cm.sup.3 formed over at least a portion of the non-conductive substrate. The platinum films produced in accordance with the present invention provide porous films suitable for use as electrodes, yet require few processing steps. Thus, such films are less costly. Such films may be formed on both conductive and non-conductive substrates. While the invention has been illustrated with platinum, other metals, such as noble metals, that form a low density oxide when reactively sputtered may also be used.

An Evaluation of Plaque and Gingivitis Reduction Following Home Use of Sonicare FlexCare Platinum with Premium Plaque Control Brush Head and a Manual Toothbrush.

PubMed

Jenkins, Wendy; Souza, Sonia; Ward, Marilyn; Defenbaugh, Jodi; Milleman, Kimberly R; Milleman, Jeffery L

2017-03-01

To assess the effect of the Philips Sonicare FlexCare Platinum with Premium plaque control brush head on gingival inflammation, bleeding, and supragingival plaque reduction following a six-week period of home use compared to a manual toothbrush. This was a randomized, single-blind, parallel-design clinical trial. Subjects included in the study were routine manual toothbrush users who were generally healthy non-smokers, aged 18-65 years, with mild to moderate gingivitis. Subjects with advanced periodontal disease, excessive gingival recession, and heavy deposits of calculus or rampant decay were excluded from the study. Eligible participants were dispensed either Philips Sonicare FlexCare Platinum with Premium plaque control brush head (PC), or an ADA Reference manual toothbrush (MTB) for twice-daily home oral hygiene procedures for six weeks. Efficacy measures included the Lobene and Soparker Modification of Quigley and Hein Plaque Index (MPI), the Modified Gingival Index (MGI), and Gingival Bleeding Index (GBI). Safety was evaluated by oral examination and subject report. Efficacy and safety were assessed at Baseline, and at two and six weeks following product home use. Of 154 subjects randomized, 143 subjects completed the study. For the primary endpoint, MGI at Week 2, statistically significantly larger reductions in MGI were observed for PC versus MTB, p < 0.0001. The adjusted mean reduction and standard error estimates (SE) for MGI, expressed as percent reduction versus Baseline to Week 2, were 41.73% (2.00%) for PC and 7.38% (2.02%) for MTB. Statistically significant differences were also observed for MPI and GBI at Week 2, and for all metrics at Week 6. Philips Sonicare FlexCare Platinum with Premium plaque control brush head statistically significantly reduces gingival inflammation, gingival bleeding, and plaque following two and six weeks of home use, compared to manual tooth brushing alone.

Determination of human body burden baseline date of platinum through autopsy tissue analysis.

PubMed Central

Vandiver, F; Duffield, F V; Yoakum, A; Bumgarner, J; Moran, J

1976-01-01

Results of analysis for platinum in 97 autopsy sets are presented. Analysis was performed by a specially developed emission spectrochemical method. Almost half of the individuals studied were found to have detectable platinum in one or more tissue samples. Platinum was found to be deposited in 13 of 21 tissue types investigated. Surprisingly high values were observed in subcutaneous fat, previously not considered to be a target site for platinum deposition. These data will serve as a human tissue platinum burden baseline in EPA's Catalyst Research Program. PMID:1001291

Effect of Graphitic Content on Carbon Supported Catalyst Performance

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

Patel, Anant; Artyushkova, Kateryna; Atanassov, Plamen

2011-07-01

The effect of graphitic content on carbon supported platinum catalysts was investigated in order to investigate its influence on catalyst performance. Four catalysts of varying surface areas and graphitic content were analyzed using XPS, HREELS, and tested using RDE experiments. The catalysts were also heat treated at 150oC and 100%RH as means to uniformly age them. The heat treated samples were analyzed using the same methods to determine what changes had occurred due to this aging process. When compared to the BOL catalysts, heat treated catalysts displayed increased graphitic carbon and platinum metalic content, however they also showed depressed catalyticmore » activity. The primary cause is still under investigation, though it is believed to be related to loss of amorphous carbon content.« less

Preparation and evaluation of advanced electrocatalysts for phosphoric acid fuel cells

NASA Technical Reports Server (NTRS)

Stonehart, P.; Baris, J.; Hochmuth, J.; Pagliaro, P.

1981-01-01

The highest performance fuel cell cathode electrocatalyst combination ever observed gives 755 mV vs hydrogen at 100 ASF on air at 180 C and shows a potential improvement to 775 mV vs hydrogen for better electrode structures. A pressurized fuel cell (UTC at 5 atm) would then give 805 mV at 320 ASF and 180 C. Another activity diagnostic is the performance of this electrocatalyst on oxygen at 900 mV vs hydrogen. The value for electrocatalyst is 44 mA per milligram of platinum and is projected to reach 60 mA per milligram of platinum with improved electrode structures. Since the electrocatalyst surface area and the electrode structure are not yet optimized there is considerable room for performance enhancement beyond these values, especially at higher temperatures.

Manufacturing and actuation characterization of ionic polymer metal composites with silver as electrodes

NASA Astrophysics Data System (ADS)

Pandita, Surya D.; Lim, Hyoung Tae; Yoo, Youngtai; Park, Hoon Cheol

2006-03-01

Manufacturing and characterization of ionic polymer metal composites (IPMCs) with silver as electrodes have been investigated. Tollen's reagent that contains ion Ag(NH 3) II + was used as a raw material for silver deposition on the surfaces of the polymer membrane Nafion"R". Two types of inner solvents, namely common water based electrolyte solution (LiOH 1N) and ionic liquid were used and investigated. Compared to IPMCs with platinum electrodes, silver-plated IPMCs with water electrolyte showed higher conductivity. The actuation response of silver-plated IPMCs with the water based electrolyte was faster than that of platinum IPMCs. However, the silver electrode was too brittle and severely damaged during the solvent exchange process from water to ionic liquid, resulted in high resistance and hence very low actuation behavior.

Platinum-Based Nanocages with Subnanometer-Thick Walls and Well-Defined Facets

DOE PAGES

Zhang, Lei; Wang, Xue; Chi, Miaofang; ...

2015-07-24

A cost-effective catalyst should have a high dispersion of the active atoms, together with a controllable surface structure for the optimization of activity, selectivity, or both. We fabricated nanocages by depositing a few atomic layers of platinum (Pt) as conformal shells on palladium (Pd) nanocrystals with well-defined facets and then etching away the Pd templates. Density functional theory calculations suggest that the etching is initiated via a mechanism that involves the formation of vacancies through the removal of Pd atoms incorporated into the outermost layer during the deposition of Pt. With the use of Pd nanoscale cubes and octahedra asmore » templates, we obtained Pt cubic and octahedral nanocages enclosed by {100} and {111} facets, respectively, which exhibited distinctive catalytic activities toward oxygen reduction.« less

p-type doping by platinum diffusion in low phosphorus doped silicon

NASA Astrophysics Data System (ADS)

Ventura, L.; Pichaud, B.; Vervisch, W.; Lanois, F.

2003-07-01

In this work we show that the cooling rate following a platinum diffusion strongly influences the electrical conductivity in weakly phosphorus doped silicon. Diffusions were performed at the temperature of 910 °C in the range of 8 32 hours in 0.6, 30, and 60 Ωrm cm phosphorus doped silicon samples. Spreading resistance profile analyses clearly show an n-type to p-type conversion under the surface when samples are cooled slowly. On the other hand, a compensation of the phosphorus donors can only be observed when samples are quenched. One Pt related acceptor deep level at 0.43 eV from the valence band is assumed to be at the origin of the type conversion mechanism. Its concentration increases by lowering the applied cooling rate. A complex formation with fast species such as interstitial Pt atoms or intrinsic point defects is expected. In 0.6 Ωrm cm phosphorus doped silicon, no acceptor deep level in the lower band gap is detected by DLTS measurement. This removes the opportunity of a pairing between phosphorus and platinum and suggests the possibility of a Fermi level controlled complex formation.

Palladium-platinum core-shell electrocatalysts for oxygen reduction reaction prepared with the assistance of citric acid

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

Zhang, Lulu; Su, Dong; Zhu, Shangqian

Core–shell structure is a promising alternative to solid platinum (Pt) nanoparticles as electrocatalyst for oxygen reduction reaction (ORR) in proton exchange membrane fuel cells (PEMFCs). A simple method of preparing palladium (Pd)–platinum (Pt) core–shell catalysts (Pd@Pt/C) in a gram-batch was developed with the assistance of citric acid. The Pt shell deposition involves three different pathways: galvanic displacement reaction between Pd atoms and Pt cations, chemical reduction by citric acid, and reduction by negative charges on Pd surfaces. The uniform ultrathin (~0.4 nm) Pt shell was characterized by in situ X-ray diffraction (XRD) and high-angle annular dark-field scanning transmission electron microscopymore » (HAADF-STEM) images combined with electron energy loss spectroscopy (EELS). Compared with state-of-the-art Pt/C, the Pd@Pt/C core–shell catalyst showed 4 times higher Pt mass activity and much better durability upon potential cycling. As a result, both the mass activity and durability were comparable to that of Pd@Pt/C synthesized by a Cu-mediated-Pt-displacement method, which is more complicated and difficult for mass production.« less

Inert gas enhanced laser-assisted purification of platinum electron-beam-induced deposits

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

Stanford, Michael G.; Lewis, Brett B.; Noh, Joo Hyon

Electron-beam-induced deposition patterns, with composition of PtC 5, were purified using a pulsed laser-induced purification reaction to erode the amorphous carbon matrix and form pure platinum deposits. Enhanced mobility of residual H 2O molecules via a localized injection of inert Ar–H 2 (4%) is attributed to be the reactive gas species for purification of the deposits. Surface purification of deposits was realized at laser exposure times as low as 0.1 s. The ex situ purification reaction in the deposit interior was shown to be rate-limited by reactive gas diffusion into the deposit, and deposit contraction associated with the purification processmore » caused some loss of shape retention. To circumvent the intrinsic flaws of the ex situ anneal process, in situ deposition and purification techniques were explored that resemble a direct write atomic layer deposition (ALD) process. First, we explored a laser-assisted electron-beam-induced deposition (LAEBID) process augmented with reactive gas that resulted in a 75% carbon reduction compared to standard EBID. Lastly, a sequential deposition plus purification process was also developed and resulted in deposition of pure platinum deposits with high fidelity and shape retention.« less

Palladium-platinum core-shell electrocatalysts for oxygen reduction reaction prepared with the assistance of citric acid

DOE PAGES

Zhang, Lulu; Su, Dong; Zhu, Shangqian; ...

2016-04-26

Core–shell structure is a promising alternative to solid platinum (Pt) nanoparticles as electrocatalyst for oxygen reduction reaction (ORR) in proton exchange membrane fuel cells (PEMFCs). A simple method of preparing palladium (Pd)–platinum (Pt) core–shell catalysts (Pd@Pt/C) in a gram-batch was developed with the assistance of citric acid. The Pt shell deposition involves three different pathways: galvanic displacement reaction between Pd atoms and Pt cations, chemical reduction by citric acid, and reduction by negative charges on Pd surfaces. The uniform ultrathin (~0.4 nm) Pt shell was characterized by in situ X-ray diffraction (XRD) and high-angle annular dark-field scanning transmission electron microscopymore » (HAADF-STEM) images combined with electron energy loss spectroscopy (EELS). Compared with state-of-the-art Pt/C, the Pd@Pt/C core–shell catalyst showed 4 times higher Pt mass activity and much better durability upon potential cycling. As a result, both the mass activity and durability were comparable to that of Pd@Pt/C synthesized by a Cu-mediated-Pt-displacement method, which is more complicated and difficult for mass production.« less

Inert gas enhanced laser-assisted purification of platinum electron-beam-induced deposits

DOE PAGES

Stanford, Michael G.; Lewis, Brett B.; Noh, Joo Hyon; ...

2015-06-30

Electron-beam-induced deposition patterns, with composition of PtC 5, were purified using a pulsed laser-induced purification reaction to erode the amorphous carbon matrix and form pure platinum deposits. Enhanced mobility of residual H 2O molecules via a localized injection of inert Ar–H 2 (4%) is attributed to be the reactive gas species for purification of the deposits. Surface purification of deposits was realized at laser exposure times as low as 0.1 s. The ex situ purification reaction in the deposit interior was shown to be rate-limited by reactive gas diffusion into the deposit, and deposit contraction associated with the purification processmore » caused some loss of shape retention. To circumvent the intrinsic flaws of the ex situ anneal process, in situ deposition and purification techniques were explored that resemble a direct write atomic layer deposition (ALD) process. First, we explored a laser-assisted electron-beam-induced deposition (LAEBID) process augmented with reactive gas that resulted in a 75% carbon reduction compared to standard EBID. Lastly, a sequential deposition plus purification process was also developed and resulted in deposition of pure platinum deposits with high fidelity and shape retention.« less

Single-Atom Catalyst of Platinum Supported on Titanium Nitride for Selective Electrochemical Reactions.

PubMed

Yang, Sungeun; Kim, Jiwhan; Tak, Young Joo; Soon, Aloysius; Lee, Hyunjoo

2016-02-05

As a catalyst, single-atom platinum may provide an ideal structure for platinum minimization. Herein, a single-atom catalyst of platinum supported on titanium nitride nanoparticles were successfully prepared with the aid of chlorine ligands. Unlike platinum nanoparticles, the single-atom active sites predominantly produced hydrogen peroxide in the electrochemical oxygen reduction with the highest mass activity reported so far. The electrocatalytic oxidation of small organic molecules, such as formic acid and methanol, also exhibited unique selectivity on the single-atom platinum catalyst. A lack of platinum ensemble sites changed the reaction pathway for the oxygen-reduction reaction toward a two-electron pathway and formic acid oxidation toward direct dehydrogenation, and also induced no activity for the methanol oxidation. This work demonstrates that single-atom platinum can be an efficient electrocatalyst with high mass activity and unique selectivity. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nanocarriers for delivery of platinum anticancer drugs☆

PubMed Central

Oberoi, Hardeep S.; Nukolova, Natalia V.; Kabanov, Alexander V.; Bronich, Tatiana K.

2014-01-01

Platinum based anticancer drugs have revolutionized cancer chemotherapy, and continue to be in widespread clinical use especially for management of tumors of the ovary, testes, and the head and neck. However, several dose limiting toxicities associated with platinum drug use, partial anti-tumor response in most patients, development of drug resistance, tumor relapse, and many other challenges have severely limited the patient quality of life. These limitations have motivated an extensive research effort towards development of new strategies for improving platinum therapy. Nanocarrier-based delivery of platinum compounds is one such area of intense research effort beginning to provide encouraging preclinical and clinical results and may allow the development of the next generation of platinum chemotherapy. This review highlights current understanding on the pharmacology and limitations of platinum compounds in clinical use, and provides a comprehensive analysis of various platinum–polymer complexes, micelles, dendrimers, liposomes and other nanoparticles currently under investigation for delivery of platinum drugs. PMID:24113520

Compression Ratio and Catalyst Aging Effects on Aqueous Ethanol Ignition (Year 2) : Part 2 Catalyst Aging and Effects of Water on Ignition

DOT National Transportation Integrated Search

2009-09-01

A tubular plug-flow reactor under low Reynolds Numbers Re flow regimes, along with a 127 um diameter coiled platinum (Pt) wire, were used to study catalytic surface reactions of nonflammable, fuel-lean mixtures of propane, oxygen, and water vapor dil...

METHOD FOR ELECTRODEPOSITING POLONIUM

DOEpatents

Wehrmann, R.F.

1960-08-30

The deposition of a thick uniform layer of polonium metal from aqueous solutions can be carried out by electrolyzing an aqueous solution of 1 N hydrofluoric acid containing about 0.13 curie of polonium per cubic centimeter of solution with platinum electrodes and a current density of about 1.2 ma/cm/sup 2/ of cathode surface.

Unsupported platinum nanoparticles as effective sensors of neurotransmitters and possible drug curriers

NASA Astrophysics Data System (ADS)

Tąta, Agnieszka; Gralec, Barbara; Proniewicz, Edyta

2018-03-01

Herein, surface-enhanced Raman scattering (SERS) activity of positively charged unsupported platinum nanoparticles (PtNPs) with ∼12 nm size and narrow size distribution, in an aqueous solution, towards neurotransmitters was monitored at 785 nm excitation wavelength. The pure PtNPs were synthetized by polyol method. Their morphology and structure were checked by scanning electron microscopy (SEM) and X-ray diffraction spectroscopy (XRD) measurements. As a neurotransmitter bombesin (BN), which exhibits autocrine effect on the growth of normal and tumour tissues, and its fragments from the C-terminal end: BN13-14, BN12-14, BN11-14, BN10-14, BN9-14, and BN8-14 (X-14 fragments of the BN amino acid sequence) were chosen. The collected spectra were interpreted and discussed. This is to determine the adsorption mode of bombesin onto the PtNPs surface and changes in this mode as a result of the bombesin backbone shortening from the N-terminal end. This is important from the point of using PtNPs as potential BN carrier into the cancerous tissue and antitumor drug.

Attachment of Single-wall Carbon Nanotubes (SWNTs) on Platinum Surfaces by Self-Assembling Techniques

NASA Technical Reports Server (NTRS)

Rosario-Castro, Belinda I.; Cabrera, Carlos R.; Perez-Davis, Maria; Lebron, Marisabel; Meador, Michael

2003-01-01

Single-wall carbon nanotubes (SWNTs) are very interesting materials because of their morphology, electronic and mechanical properties. Its morphology (high length-to-diameter ratio) and electronic properties suggest potential application of SWNTs as anode material for lithium ion secondary batteries. The introduction of SWNTs on these types of sources systems will improve their performance, efficiency, and capacity to store energy. A purification method has been applied for the removal of iron and amorphous carbon from the nanotubes. Unpurified and purified SWNTs were characterized by transmission electron microscopy (TEM), and thermogravimetric analysis (TGA). In order to attach carbon nanotubes on platinum electrode surfaces, a self-assembled monolayer (SAM) of 4-aminothiophenol (4-ATP) was deposited over the electrodes. The amino-terminated SAM obtained was characterized by cyclic voltammetry, X-ray photoelectron spectroscopy (XPS), and Fourier-transforms infrared (FTIR) spectroscopy. Carbon nanotubes were deposited over the amino-terminated SAM by an amide bond formed between SAM amino groups and carboxylic acid groups at the open ends of the carbon nanotubes.This deposition was characterized using Raman spectroscopy and Scanning Electron microscopy (SEM).

Anthropogenic osmium in rain and snow reveals global-scale atmospheric contamination.

PubMed

Chen, Cynthia; Sedwick, Peter N; Sharma, Mukul

2009-05-12

Osmium is one of the rarer elements in seawater, with typical concentration of approximately 10 x 10(-15) g g(-1) (5.3 x 10(-14) mol kg(-1)). The osmium isotope composition ((187)Os/(188)Os ratio) of deep oceans is 1.05, reflecting a balance between inputs from continental crust (approximately 1.3) and mantle/cosmic dust (approximately 0.13). Here, we show that the (187)Os/(188)Os ratios measured in rain and snow collected around the world range from 0.16 to 0.48, much lower than expected (>1), but similar to the isotope composition of ores (approximately 0.2) that are processed to extract platinum and other metals to be used primarily in automobile catalytic converters. Present-day surface seawater has a lower (187)Os/(188)Os ratio (approximately 0.95) than deep waters, suggesting that human activities have altered the isotope composition of the world's oceans and impacted the global geochemical cycle of osmium. The contamination of the surface ocean is particularly remarkable given that osmium has few industrial uses. The pollution may increase with growing demand for platinum-based catalysts.

Fundamental technical elements of freeze-fracture/freeze-etch in biological electron microscopy.

PubMed

Carson, Johnny L

2014-09-11

Freeze-fracture/freeze-etch describes a process whereby specimens, typically biological or nanomaterial in nature, are frozen, fractured, and replicated to generate a carbon/platinum "cast" intended for examination by transmission electron microscopy. Specimens are subjected to ultrarapid freezing rates, often in the presence of cryoprotective agents to limit ice crystal formation, with subsequent fracturing of the specimen at liquid nitrogen cooled temperatures under high vacuum. The resultant fractured surface is replicated and stabilized by evaporation of carbon and platinum from an angle that confers surface three-dimensional detail to the cast. This technique has proved particularly enlightening for the investigation of cell membranes and their specializations and has contributed considerably to the understanding of cellular form to related cell function. In this report, we survey the instrument requirements and technical protocol for performing freeze-fracture, the associated nomenclature and characteristics of fracture planes, variations on the conventional procedure, and criteria for interpretation of freeze-fracture images. This technique has been widely used for ultrastructural investigation in many areas of cell biology and holds promise as an emerging imaging technique for molecular, nanotechnology, and materials science studies.

A comparative study of different bleaching agents on the morphology of human enamel: an in vitro SEM study.

PubMed

Uthappa, Roshan; Suprith, M L; Bhandary, Shreetha; Dash, Sumit

2012-11-01

The purpose of the study was to compare two different commercial bleaching agents, Opalescence with Colgate Platinum, and 30% phosphoric acid used as aggressive agent on the morphology of human enamel. Ten freshly extracted, noncarious, human maxillary central incisors extracted for periodontal reasons were used in this study. The labial surface of the disinfected teeth were polished using a polishing paste with the help of rubber cup and a slow speed handpiece. Each tooth was sectioned at cement-enamel junction and the crown was separated into four specimens, all taken from labial surface. Group 1 was treated with Colgate Platinum for 7 hours, group 2 with Opalescence for 7 hours, group 3 was treated with 30% phosphoric acid for 30 seconds and group 4 was untreated and used as control. After the treatment period, the specimens were washed with normal saline and stored in sterile bottle and sealed. Photomicrographs obtained from the scanning electron microscopy (SEM) after surface treatments were examined for no alteration, slight alteration, moderate alteration and severe alterations. The specimens treated with commercial bleaching agents revealed no enamel surface morphologic alterations compared to control group. The specimen treated with phosphoric acid showed severe alterations. Ten percent carbamide peroxide evaluated in this study does not etch tooth enamel or alter enamel surface morphology as do conventional etching techniques. Carbamine peroxide is a safe and effective tooth whitening agent even when used for extended period of time. The enamel surface remains smooth which reduces caries due to plaque collection.

PLATINUM AND FUEL CELLS

EPA Science Inventory

Platinum requirements for fuel cell vehicles (FCVS) have been identified as a concern and possible problem with FCV market penetration. Platinum is a necessary component of the electrodes of fuel cell engines that power the vehicles. The platinum is deposited on porous electrodes...

Platinum-decorated reduced graphene oxide/polyaniline:poly(4-styrenesulfonate) hybrid paste for flexible dipole tag-antenna applications

NASA Astrophysics Data System (ADS)

Lee, Jun Seop; Kim, Minkyu; Lee, Choonghyeon; Cho, Sunghun; Oh, Jungkyun; Jang, Jyongsik

2015-02-01

With recent developments in technology, tremendous effort has been devoted to producing materials for flexible device systems. As a promising approach, solution-processed conducting polymers (CPs) have been extensively studied owing to their facile synthesis, high electrical conductivity, and various morphologies with diverse substrates. Here, we report the demonstration of platinum decorated reduced graphene oxide intercalated polyanililne:poly(4-styrenesulfonate) (Pt_rGO/PANI:PSS) hybrid paste for flexible electric devices. First, platinum decorated reduced graphene oxide (Pt_rGO) was fabricated through the chemical reduction of platinum cations and subsequent heat reduction of GO sheets. Then, the Pt_rGO was mixed with PANI:PSS solution dispersed in diethylene glycol (DEG) using sonication to form a hybrid PANI-based paste (Pt_rGO/PANI:PSS). The Pt_rGO/PANI:PSS was printed as a micropattern and exhibited high electrical conductivity (245.3 S cm-1) with flexible stability. Moreover, it was used in a dipole tag antenna application, where it displayed 0.15 GHz bandwidth and high transmitted power efficiency (99.6%).With recent developments in technology, tremendous effort has been devoted to producing materials for flexible device systems. As a promising approach, solution-processed conducting polymers (CPs) have been extensively studied owing to their facile synthesis, high electrical conductivity, and various morphologies with diverse substrates. Here, we report the demonstration of platinum decorated reduced graphene oxide intercalated polyanililne:poly(4-styrenesulfonate) (Pt_rGO/PANI:PSS) hybrid paste for flexible electric devices. First, platinum decorated reduced graphene oxide (Pt_rGO) was fabricated through the chemical reduction of platinum cations and subsequent heat reduction of GO sheets. Then, the Pt_rGO was mixed with PANI:PSS solution dispersed in diethylene glycol (DEG) using sonication to form a hybrid PANI-based paste (Pt_rGO/PANI:PSS). The Pt_rGO/PANI:PSS was printed as a micropattern and exhibited high electrical conductivity (245.3 S cm-1) with flexible stability. Moreover, it was used in a dipole tag antenna application, where it displayed 0.15 GHz bandwidth and high transmitted power efficiency (99.6%). Electronic supplementary information (ESI) available: TEM images of Pr_rGOs, XRD spectra of various PANI-based hybrid materials, electrical conductivity of Pt_rGO/PANI:PSS with different Pt amounts, surface resistance changes of micropatterns, return loss of the antenna with bending deformation, and transmitted power efficiency of the antenna with bending cycles. See DOI: 10.1039/c4nr06189f

Leaching under Oxygen Pressure with Carbonate Solution Reduction by Hydrogen; LIXIVIATION OXYDANTE DES PECHBLENDES ET PRECIPITATION DE L'URANIUM PAR L'HYDROGENE. APPLICATION AUX MINERAIS PAUVRES FRANCAIS

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

Balaceanu, J.C.; Coussemant, F.; Mouret, P.

1959-10-31

A study was made of the basic characteristics of the leaching with carbonate solution under oxygen pressure and of the catalytic hydrogen reduction of low-grade French ores. Pure U/sub 3/O/sub 8/ was used in the investigations on leaching. The effects of oxygen pressure, temperature, initial surface of the oxide, surfuce during the course of the reaction, and concentration of the carbonate solution were determined. It was shown that the heterogeneous reactions involve a constant surface and two steps. A pilot plant experiment was made on a number of low-grade French ores. With ores the leaching is not sensitive to oxygenmore » pressure. Dilute solutions of sodium uranyl carbonate are obtained from the leaching. The uranium can be precipitated as an oxide of a lower valent state by catalytic reduction with hydrogen. The study of this step was made on pure solutions of sodium uranyl carbonate in the presence of nickel and platinum catalysts. The reaction is strongly modified by the presence of even low concentrations of sodium bicarbonate. The reaction velocity increases with hydrogen pressure up to 5 atm, but then becomes independent of the pressure. The precipitation is accelerated by an increase in temperature. (J.S.R.)« less

Ultrasensitive electroanalytical tool for detecting, sizing, and evaluating the catalytic activity of platinum nanoparticles.

PubMed

Dasari, Radhika; Robinson, Donald A; Stevenson, Keith J

2013-01-16

Here we describe a very simple, reliable, low-cost electrochemical approach to detect single nanoparticles (NPs) and evaluate NP size distributions and catalytic activity in a fast and reproducible manner. Single NPs are detected through an increase in current caused by electrocatalytic oxidation of N(2)H(4) at the surface of the NP when it contacts a Hg-modified Pt ultramicroelectrode (Hg/Pt UME). Once the NP contacts the Hg/Pt UME, Hg poisons the Pt NP, deactivating the N(2)H(4) oxidation reaction. Hence, the current response is a "spike" that decays to the background current level rather than a stepwise "staircase" response as previously described for a Au UME. The use of Hg as an electrode material has several quantitative advantages including suppression of the background current by 2 orders of magnitude over a Au UME, increased signal-to-noise ratio for detection of individual collisions, precise integration of current transients to determine charge passed and NP size, reduction of surface-induced NP aggregation and electrode fouling processes, and reproducible and renewable electrodes for routine detection of catalytic NPs. The NP collision frequency was found to scale linearly with the NP concentration (0.016 to 0.024 pM(-1)s(-1)). NP size distributions of 4-24 nm as determined from the current-time transients correlated well with theory and TEM-derived size distributions.

An ultrasensitive luminol cathodic electrochemiluminescence immunosensor based on glucose oxidase and nanocomposites: graphene-carbon nanotubes and gold-platinum alloy.

PubMed

Jiang, Xinya; Chai, Yaqin; Yuan, Ruo; Cao, Yaling; Chen, Yingfeng; Wang, Haijun; Gan, Xianxue

2013-06-14

In the present study, a novel and ultrasensitive electrochemiluminescence (ECL) immunosensor based on luminol cathodic ECL was fabricated by using Au nanoparticles and Pt nanoparticles (nano-AuPt) electrodeposited on graphene-carbon nanotubes nanocomposite as platform for the detection of carcinoembryonic antigen (CEA). For this introduced immunosensor, graphene (GR) and single wall carbon nanotubes (CNTs) dispersed in chitosan (Chi-GR-CNTs) were firstly decorated on the bare gold electrode (GE) surface. Then nano-AuPt were electrodeposited (DpAu-Pt) on the Chi-GR-CNTs modified electrode. Subsequently, glucose oxidase (GOD) was employed to block the non-specific sites of electrode surface. When glucose was present in the working buffer solution, GOD immediately catalyzed the oxidation of glucose to in situ generate hydrogen peroxide (H2O2), which could subsequently promote the oxidation of luminol with an amplified cathodic ECL signal. The proposed immunosensor was performed at low potential (-0.1 to 0.4V) and low concentration of luminol. The CEA was determined in the range of 0.1 pg mL(-1) to 40 ng mL(-1) with a limit of detection down to 0.03 pg mL(-1) (SN(-1)=3). Moreover, with excellent sensitivity, selectivity, stability and simplicity, the as-proposed luminol-based ECL immunosensor provided great potential in clinical applications. Copyright © 2013 Elsevier B.V. All rights reserved.

Synthesis and comparative photocatalytic activity of Pt/WO 3 and Au/WO 3 nanocomposites under sunlight-type excitation

NASA Astrophysics Data System (ADS)

Qamar, M.; Yamani, Z. H.; Gondal, M. A.; Alhooshani, K.

2011-09-01

The article deals with the synthesis of highly active visible-light-driven nanocomposite for the decontamination of water hazards under sunlight-type excitation. The surface of visible-light-active nanostructured photocatalyst tungsten oxide (WO 3) was modified with noble metals, such as platinum (Pt) and gold (Au) nanoparticles, and the resulting photocatalytic activity of the nanocomposites was investigated by studying the removal of Methyl Orange and 2,4-Dichlorophenoxyacetic acid (2,4-D) under sunlight-type excitation. The study revealed that the deposited noble metals are not always favorable for the enhancement of photocatalytic response of catalysts; the activity of WO 3 was enhanced manyfold (˜8 times) by depositing an optimum amount of Pt nanoparticles after certain photodeposition time whereas the presence of Au nanoparticles onto the WO 3 surface, under identical experimental conditions, affected the removal process negatively. The variation in the photocatalytic activity of nanocomposites was attributed to the size of the deposited metals; Pt nanoparticles were uniformly dispersed with narrow size distribution (2-4 nm) while the size distribution of Au nanoparticles was found to be 10-15 nm for similar preparation conditions. The effects of critical parameters, such as metal deposition time and metal contents, on the photocatalytic activity of WO 3 were investigated. Furthermore, Pt/WO 3 nanocomposites showed good stability and recyclability under the conditions studied.

Atomic layer deposition of nanoporous biomaterials.

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

Narayan, R. J.; Adiga, S. P.; Pellin, M. J.

2010-03-01

Due to its chemical stability, uniform pore size, and high pore density, nanoporous alumina is being investigated for use in biosensing, drug delivery, hemodialysis, and other medical applications. In recent work, we have examined the use of atomic layer deposition for coating the surfaces of nanoporous alumina membranes. Zinc oxide coatings were deposited on nanoporous alumina membranes using atomic layer deposition. The zinc oxide-coated nanoporous alumina membranes demonstrated antimicrobial activity against Escherichia coli and Staphylococcus aureus bacteria. These results suggest that atomic layer deposition is an attractive technique for modifying the surfaces of nanoporous alumina membranes and other nanostructured biomaterials.more » Nanoporous alumina, also known as anodic aluminum oxide (AAO), is a nanomaterial that exhibits several unusual properties, including high pore densities, straight pores, small pore sizes, and uniform pore sizes. In 1953, Keller et al. showed that anodizing aluminum in acid electrolytes results in a thick layer of nearly cylindrical pores, which are arranged in a close-packed hexagonal cell structure. More recently, Matsuda & Fukuda demonstrated preparation of highly ordered platinum and gold nanohole arrays using a replication process. In this study, a negative structure of nanoporous alumina was initially fabricated and a positive structure of a nanoporous metal was subsequently fabricated. Over the past fifteen years, nanoporous alumina membranes have been used as templates for growth of a variety of nanostructured materials, including nanotubes, nanowires, nanorods, and nanoporous membranes.« less

Platinum recycling in the United States in 1998

USGS Publications Warehouse

Hilliard, Henry E.

2001-01-01

In the United States, catalytic converters are the major source of secondary platinum for recycling. Other sources of platinum scrap include reforming and chemical process catalysts. The glass industry is a small but significant source of platinum scrap. In North America, it has been estimated that in 1998 more than 20,000 kilograms per year of platinum-group metals from automobile catalysts were available for recycling. In 1998, an estimated 7,690 kilograms of platinum were recycled in the United States. U.S. recycling efficiency was calculated to have been 76 percent in 1998; the recycling rate was estimated at 16 percent.

Characterization of Platinum Nanoparticles Deposited on Functionalized Graphene Sheets

PubMed Central

Chiang, Yu-Chun; Liang, Chia-Chun; Chung, Chun-Ping

2015-01-01

Due to its special electronic and ballistic transport properties, graphene has attracted much interest from researchers. In this study, platinum (Pt) nanoparticles were deposited on oxidized graphene sheets (cG). The graphene sheets were applied to overcome the corrosion problems of carbon black at operating conditions of proton exchange membrane fuel cells. To enhance the interfacial interactions between the graphene sheets and the Pt nanoparticles, the oxygen-containing functional groups were introduced onto the surface of graphene sheets. The results showed the Pt nanoparticles were uniformly dispersed on the surface of graphene sheets with a mean Pt particle size of 2.08 nm. The Pt nanoparticles deposited on graphene sheets exhibited better crystallinity and higher oxygen resistance. The metal Pt was the predominant Pt chemical state on Pt/cG (60.4%). The results from the cyclic voltammetry analysis showed the value of the electrochemical surface area (ECSA) was 88 m2/g (Pt/cG), much higher than that of Pt/C (46 m2/g). The long-term test illustrated the degradation in ECSA exhibited the order of Pt/C (33%) > Pt/cG (7%). The values of the utilization efficiency were calculated to be 64% for Pt/cG and 32% for Pt/C. PMID:28793577

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

Chlorobenzene Poisoning and Recovery of Platinum-Based Cathodes in Proton Exchange Membrane Fuel Cells

PubMed Central

Zhai, Yunfeng; Baturina, Olga; Ramaker, David; Farquhar, Erik; St-Pierre, Jean; Swider-Lyons, Karen

2015-01-01

The platinum electrocatalysts found in proton exchange membrane fuel cells are poisoned both reversibly and irreversibly by air pollutants and residual manufacturing contaminants. In this work, the poisoning of a Pt/C PEMFC cathode was probed by a trace of chlorobenzene in the air feed. Chlorobenzene inhibits the oxygen reduction reaction and causes significant cell performance loss. The performance loss is largely restored by neat air operation and potential cycling between 0.08 V and 1.2 V under H2/N2 (anode/cathode). The analysis of emissions, in situ X-ray absorption spectroscopy and electrochemical impedance spectra show the chlorobenzene adsorption/reaction and molecular orientation on Pt surface depend on the electrode potential. At low potentials, chlorobenzene deposits either on top of adsorbed H atoms or on the Pt surface via the benzene ring and is converted to benzene (ca. 0.1 V) or cyclohexane (ca. 0 V) upon Cl removal. At potentials higher than 0.2 V, chlorobenzene binds to Pt via the Cl atom and can be converted to benzene (less than 0.3 V) or desorbed. Cl− is created and remains in the membrane electrode assembly. Cl− binds to the Pt surface much stronger than chlorobenzene, but can slowly be flushed out by liquid water. PMID:26388963

Effect of γ-irradiation on the temperature coefficient of surface resistivity of two-dimensional island platinum films

NASA Astrophysics Data System (ADS)

Bishay, A. G.; El-Gamal, S.

2011-05-01

Three sets (A, B and C) of two-dimensional island platinum films (2D-I(Pt)Fs) were prepared via the thermal evaporation technique, where the substrates are corning 7059 glass slides. The mass thickness ( d m) of the films of different sets is 5, 10 and 20 Å, respectively. The Pt films were exposed to γ-rays from 137Cs (0.662 MeV) radiation source of dose rate 0.5 Gy/min. and the different doses are 100, 200, 300, 500 and 700 Gy. The dependence of the surface resistivity ( ρ) on temperature over the range of 100-300 K was undertaken at different d m and doses then the temperature coefficient of surface resistivity ( α) was deduced. It was found that; (i) for particular d m and T, the absolute value of α decreases as the dose increases (ii) for particular dose and T, the absolute value of α decreases as d m increases (iii) for particular dose and d m, the absolute value of α decreases as T increases. Qualitative interpretation for the results was offered on the ground that the electrons transfer among islands takes place by the activated tunneling mechanism and the γ-irradiation has changed the shape of islands from spherical to prolate spheroid.

Cathode catalysts for primary phosphoric acid fuel cells

NASA Technical Reports Server (NTRS)

1981-01-01

Alkylation or carbon Vulcan XC-72, the support carbon, was shown to provide the most stable bond type for linking cobalt dehydrodibenzo tetraazannulene (CoTAA) to the surface of the carbon; this result is based on data obtained by cyclic voltammetry, pulse voltammetry and by release of 14C from bonded CoTAA. Half-cell tests at 100 C in 85% phosphoric acid showed that CoTAA bonded to the surface of carbon (Vulcan XC-72) via an alkylation procedure is a more active catalyst than is platinum based on a factor of two improvement in Tafel slope; dimeric CoTAA had catalytic activity equal to platinum. Half-cell tests also showed that bonded CoTAA catalysts do not suffer a loss in potential when air is used as a fuel rather than oxygen. Commercially available polytetrafluroethylene (PTFE) was shown to be unstable in the fuel cell environment with degradation occurring in 2000 hours or less. The PTFE was stressed at 200 C in concentrated phosphoric acid as well as electrochemically stressed in 150 C concentrated phosphoric acid; the surface chemistry of PTFE was observed to change significantly. Radiolabeled PTFE was prepared and used to verify that such chemical changes also occur in the primary fuel cell environment.

Reactivity and biological properties of a series of cytotoxic PtI2(amine)2 complexes, either cis or trans configured.

PubMed

Messori, Luigi; Cubo, Leticia; Gabbiani, Chiara; Álvarez-Valdés, Amparo; Michelucci, Elena; Pieraccini, Giuseppe; Ríos-Luci, Carla; León, Leticia G; Padrón, José M; Navarro-Ranninger, Carmen; Casini, Angela; Quiroga, Adoración G

2012-02-06

Six diiodido-diamine platinum(II) complexes, either cis or trans configured, were prepared, differing only in the nature of the amine ligand (isopropylamine, dimethylamine, or methylamine), and their antiproliferative properties were evaluated against a panel of human tumor cell lines. Both series of complexes manifested pronounced cytotoxic effects, with the trans isomers being, generally, more effective than their cis counterparts. Cell cycle analysis revealed different modes of action for these new Pt(II) complexes with respect to cisplatin. The reactivity of these platinum compounds with a number of biomolecules, including cytochrome c, two sulfur containing modified amino acids, 9-ethylguanine, and a single strand oligonucleotide, was analyzed in depth by mass spectrometry and NMR spectroscopy. Interestingly, significant differences in the reactivity of the investigated compounds toward the various model biomolecules were observed: in particular we observed that trans complexes preferentially release their iodide ligands upon biomolecule binding, while the cis isomers may release the amine ligands with retention of iodides. Such differences in reactivity may have important mechanistic implications and a relevant impact on the respective pharmacological profiles.

Stability of reference masses: VII. Cleaning methods in air and vacuum applied to a platinum mass standard similar to the international and national kilogram prototypes

NASA Astrophysics Data System (ADS)

Cumpson, Peter J.; Sano, Naoko; Barlow, Anders J.; Portoles, Jose F.

2013-10-01

Mercury contamination and the build-up of carbonaceous contamination are two contributing factors to the instability observed in kilogram prototype masses. The kilogram prototypes that lie at the core of the dissemination of the SI base unit were manufactured in the late 19th century, and have polished surfaces. In papers IV and V of this series we developed a method for cleaning noble metal mass standards in air to remove carbonaceous contamination. At the core of this ‘UVOPS’ protocol is the application of UV light and ozone gas generated in situ in air. The precise nature of the carbonaceous contamination that builds up on such surfaces is difficult to mimic demonstrably or quickly on new test surfaces, yet data from such tests are needed to provide the final confidence to allow UVOPS to be applied to a real 19th century kilogram prototype. Therefore, in the present work we have applied the UVOPS method to clean a platinum avoirdupois pound mass standard, ‘RS2’, manufactured in the mid-19th century. This is thought to have been polished in a similar manner to the kilogram prototypes. To our knowledge this platinum surface has not previously been cleaned by any method. We used x-ray photoelectron spectroscopy to identify organic contamination, and weighing to quantify the mass lost at each application of the UVOPS procedure. The UVOPS procedure is shown to be very effective. It is likely that the redefinition of the kilogram will require mass comparisons in vacuum in the years to come. Therefore, in addition to UVOPS a cleaning method for use in vacuum will also be needed. We introduce and evaluate gas cluster ion-beam (GCIB) treatment as a potential method for cleaning reference masses in vacuum. Again, application of this GCIB cleaning to a real artefact, RS2, allows us to make a realistic evaluation of its performance. While it has some attractive features, we cannot recommend it for cleaning mass standards in its present form.

Synthesis of Cluster-Derived PtFe/SiO(2) Catalysts for the Oxidation of CO

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

Siani, A.; Alexeev, O.S.; Captain, B.

2009-05-27

Infrared (FTIR) and extended X-ray absorption fine structure (EXAFS) spectroscopy measurements were used to characterize the species formed after impregnation of Pt{sub 5}Fe{sub 2}(COD){sub 2}(CO){sub 12} onto silica, before and after removal of the organic ligands. The results indicate that the Pt{sub 5}Fe{sub 2}(COD){sub 2}(CO){sub 12} cluster adsorbs weakly on the SiO{sub 2} surface. Nevertheless, partial disintegration of the cluster was observed during aging even under He and at room temperature, related to the loss of CO ligands due to their interactions with silanol groups of the support. The organic ligands can be removed from a freshly impregnated cluster bymore » thermal treatment in either He or H{sub 2}, but the surface species formed in each case have different structures. Treatment in He at 350 {sup o}C leads to a complete disintegration of the Pt-Fe bimetallic core and results in the formation of highly dispersed Pt clusters with a nuclearity of six, along with surface Fe oxide-like species. In contrast, bimetallic PtFe nanoparticles with an average size of approximately 1 nm were formed when a similar H{sub 2} treatment was used. In this case, a greater degree of metal dispersion and a larger fraction of Pt-Fe interactions were observed compared to the PtFe/SiO{sub 2} samples prepared by co-impregnation of monometallic salt precursors. Electronic interactions between Pt and Fe atoms in such cluster-derived samples led to an increased electron density on platinum, as indicated by a red shift of the frequencies of FTIR bands for adsorbed NO and CO. These electronic interactions affect the strength of the CO adsorption on platinum. All bimetallic samples were found to be more active than Pt/SiO{sub 2} for the oxidation of CO in air; however, the activity depends strongly on the structure of the surface species, the fraction of Pt-Fe bimetallic contributions, the degree of electronic interactions between Pt and Fe, and the strength of the CO adsorption on platinum.« less

Particle size and support effects in electrocatalysis.

PubMed

Hayden, Brian E

2013-08-20

Researchers increasingly recognize that, as with standard supported heterogeneous catalysts, the activity and selectivity of supported metal electrocatalysts are influenced by particle size, particle structure, and catalyst support. Studies using model supported heterogeneous catalysts have provided information about these effects. Similarly, model electrochemical studies on supported metal electrocatalysts can provide insight into the factors determining catalytic activity. High-throughput methods for catalyst synthesis and screening can determine systematic trends in activity as a function of support and particle size with excellent statistical certainty. In this Account, we describe several such studies investigating methods for dispersing precious metals on both carbon and oxide supports, with particular emphasis on the prospects for the development of low-temperature fuel-cell electrocatalysts. One key finding is a decrease in catalytic activity with decreasing particle size independent of the support for both oxygen reduction and CO oxidation on supported gold and platinum. For these reactions, there appears to be an intrinsic particle size effect that results in a loss of activity at particle sizes below 2-3 nm. A titania support, however, also increases activity of gold particles in the electrooxidation of CO and in the reduction of oxygen, with an optimum at 3 nm particle size. This optimum may represent the superposition of competing effects: a titania-induced enhanced activity versus deactivation at small particle sizes. The titania support shows catalytic activity at potentials where carbon-supported and bulk-gold surfaces are normally oxidized and CO electrooxidation is poisoned. On the other hand, platinum on amorphous titania shows a different effect: the oxidation reduction reaction is strongly poisoned in the same particle size range. We correlated the influence of the titania support with titania-induced changes in the surface redox behavior of the platinum particles. For both supported gold and platinum particles in electrocatalysis, we observe parallels to the effects of particle size and support in the equivalent heterogeneous catalysts. Studies of model supported-metal electrocatalysts, performs efficiently using high throughput synthetic and screening methodologies, will lead to a better understanding of the mechanisms responsible for support and particle size effects in electrocatalysis, and will drive the development of more effective and robust catalysts in the future.

Oxygen-induced excitability of the belousov-zhabotinskii oscillatory system

NASA Astrophysics Data System (ADS)

Treindl, Ľudovit; Mrákavová, Marta

1985-12-01

The modified Belousov-Zhabotinskii ferroin-catalyzed oscillatory system with the ethyl ester of 3-oxobutanoic acid is described. After an induction period of about 120 s its oscillatory state consisting of four or five oscillations of absorbancy at a wavenumber of 22×10 3 cm -1 can be revived three or four times, if the solution is shaken for 25 s after the oscillatory state has finished. This apparently "mechanical" excitability, which can be observed spectrophotometrically and also polarographically using a rotating platinum disc electrode, proved to be oxygen-induced.

Large Meteorite Impacts and Planetary Evolution

NASA Technical Reports Server (NTRS)

1997-01-01

Topics considered include: Petrography, geochemistry and geochronology; impact-induced hydrothermal base metal mineralization; nickel-and platinum group element -enriched quartz norite in the latest jurassic morokweng impact structure, south Africa; extraterrestrial helium trapped in fullerenes in the sudbury; synthetic aperture radar characteristics of a glacially modified meltsheet; the chicxulub seismic experiment; chemical compositions of chicxulub impact breccias; experimental investigation of the chemistry of vaporization of targets in relation to the chicxulub impact; artificial ozone hole generation following a large meteoroid impact into an oceanic site; three dimensional modeling of impactite bodies of popigai impact crater, Russia.

Incipient triple point for adsorbed xenon monolayers: Pt(111) versus graphite substrates

NASA Astrophysics Data System (ADS)

Novaco, Anthony D.; Bruch, L. W.; Bavaresco, Jessica

2015-04-01

Simulation evidence of an incipient triple point is reported for xenon submonolayers adsorbed on the (111) surface of platinum. This is in stark contrast to the "normal" triple point found in simulations and experiments for xenon on the basal plane surface of graphite. The motions of the atoms in the surface plane are treated with standard 2D "NVE" molecular dynamics simulations using modern interactions. The simulation evidence strongly suggests an incipient triple point in the 120 -150 K range for adsorption on the Pt (111) surface while the adsorption on graphite shows a normal triple point at about 100 K.

Elution of platinum from carboplatin-impregnated calcium sulfate hemihydrate beads in vitro.

PubMed

Tulipan, Rachel J; Phillips, Heidi; Garrett, Laura D; Dirikolu, Levent; Mitchell, Mark A

2016-11-01

OBJECTIVE To characterize the elution of platinum from carboplatin-impregnated calcium sulfate hemihydrate (CSH) beads in vitro. SAMPLE 60 carboplatin-impregnated CSH beads and 9 CSH beads without added carboplatin (controls). PROCEDURES Carboplatin-impregnated CSH beads (each containing 4.6 mg of carboplatin [2.4 mg of platinum]) were placed into separate 10-mL plastic tubes containing 5 mL of PBSS in groups of 1, 3, 6, or 10; 3 control beads were placed into a single tube of PBSS at the same volume. Experiments were conducted in triplicate at 37°C and a pH of 7.4 with constant agitation. Eluent samples were collected at 1, 2, 3, 6, 12, 24, and 72 hours. Samples were analyzed for platinum content by inductively coupled plasma-mass spectrometry. RESULTS The mean concentration of platinum released per carboplatin-impregnated bead over 72 hours was 445.3 mg/L. Cumulative concentrations of platinum eluted increased as the number of beads per tube increased. There was a significant difference in platinum concentrations over time, with values increasing over the first 12 hours and then declining for all tubes. There was also a significant difference in percentage of total incorporated platinum released into tubes with different numbers of beads: the percentage of eluted platinum was higher in tubes containing 1 or 3 beads than in those containing 6 or 10 beads. CONCLUSIONS AND CLINICAL RELEVANCE Carboplatin-impregnated CSH beads eluted platinum over 72 hours. Further studies are needed to determine whether implantation of carboplatin-impregnated CSH beads results in detectable levels of platinum systemically and whether the platinum concentrations eluted locally are toxic to tumor cells.

Stepped Single Crystals as Improved Model for Supported Catalysts: Ethylene, Methanol and Assorted Molecules on PLATINUM(511) and PLATINUM(331)

NASA Astrophysics Data System (ADS)

Spaendonk, Vincent Van

Past research has shown unusual activity of the (1 x 1)Pt(110) surface to break carbon-carbon and carbon -oxygen bonds. Methane formation from ethylene or ethane has been reported for supported platinum catalysts. A model for the methane formation on (1 x 1)Pt(110), was proposed by Yagasaki. In this study, the mechanism of methane formation has been further investigated, and Yagasaki's model tested, by studying the decomposition of ethylene and methanol on the stepped surfaces Pt(511) and Pt(331) with Temperature Programmed Desorption. The experiments have been carried out in a Ultra High Vacuum system, equipped with a mass spectrometer, LEED and AES. Hydrogen and carbon monoxide desorption show that on Pt(511) different adsorption sites are available than on Pt(331). Ethylene decomposition on Pt(511) leads to small amounts of methane formation compared to (1 x 1)Pt(110). The metastable (1 x 1) phase of Pt(511) is 2-3 times more active than the stable (hex) phase. When ^{13}C_2H _4 is used, ^{13 }CH_4 is not detected. Methane formation is not seen on the Pt(331) surface. Arguments are given why Pt(511) is a superior model for supported catalysts compared to (1 x 1)Pt(110). The carbon-oxygen bond of methanol is not broken on either Pt(511) or Pt(331), whether the surface is clean or covered with oxygen. Hydrogen saturating the surface, prevents the chemisorption of ethylene and the formation of methane. Postadsorption of hydrogen does not lead to an increase in methane formation. Coadsorption of ethylene with carbon monoxide shows a maximum methane formation at 0.3 L carbon monoxide exposure. Poison experiments with 'oxide' and carbon indicate that the active site for methane formation is located at the step. The amount of carbon deposited during ethylene decomposition, increases in the order (1 x 1)Pt(511) to (hex)Pt(511) to Pt(331). This is also the order for decreasing methane activity. In a new model, it is proposed that in order to be active for methane formation, a surface has to prevent the polymerization of single carbon species to inactive graphite. The model predicts that surfaces with large enough (111) terraces have higher diffusion rates and allow the single carbon species to convert to graphite before the species can be hydrogenated.

Molecular-Orbital Models for the Catayltic Activity and Selectivity of Coordinatively Unsaturated Platinum Surfaces and Complexes.

DTIC Science & Technology

1980-12-31

surfaces. Reactions involving the Pt(O)- triphenylphosphine complexes Pt(PPh 3)n, where n = 2, 3, 4, have been shown to have precise analogues on Pt...12], the triphenylphosphine (PPh 3 ) group is modeled by the simpler but chemically similar phosphine (PH3) group. The appropriate Pt-P bond distances...typically refractory oxides ) are of sufficient magnitude as to suggest significant chemical and electronic modifications of the metal at the metal-support

Thermal sensing of cryogenic wind tunnel model surfaces Evaluation of silicon diodes

NASA Technical Reports Server (NTRS)

Daryabeigi, K.; Ash, R. L.; Dillon-Townes, L. A.

1986-01-01

Different sensors and installation techniques for surface temperature measurement of cryogenic wind tunnel models were investigated. Silicon diodes were selected for further consideration because of their good inherent accuracy. Their average absolute temperature deviation in comparison tests with standard platinum resistance thermometers was found to be 0.2 K in the range from 125 to 273 K. Subsurface temperature measurement was selected as the installation technique in order to minimize aerodynamic interference. Temperature distortion caused by an embedded silicon diode was studied numerically.

Thermal sensing of cryogenic wind tunnel model surfaces - Evaluation of silicon diodes

NASA Technical Reports Server (NTRS)

Daryabeigi, Kamran; Ash, Robert L.; Dillon-Townes, Lawrence A.

1986-01-01

Different sensors and installation techniques for surface temperature measurement of cryogenic wind tunnel models were investigated. Silicon diodes were selected for further consideration because of their good inherent accuracy. Their average absolute temperature deviation in comparison tests with standard platinum resistance thermometers was found to be 0.2 K in the range from 125 to 273 K. Subsurface temperature measurement was selected as the installation technique in order to minimize aerodynamic interference. Temperature distortion caused by an embedded silicon diode was studied numerically.