Pt and Ru X-ray absorption spectroscopy of PtRu anode catalysts in operating direct methanol fuel cells.

Science.gov (United States)

Stoupin, Stanislav; Chung, Eun-Hyuk; Chattopadhyay, Soma; Segre, Carlo U; Smotkin, Eugene S

2006-05-25

In situ X-ray absorption spectroscopy, ex situ X-ray fluorescence, and X-ray powder diffraction enabled detailed core analysis of phase segregated nanostructured PtRu anode catalysts in an operating direct methanol fuel cell (DMFC). No change in the core structures of the phase segregated catalyst was observed as the potential traversed the current onset potential of the DMFC. The methodology was exemplified using a Johnson Matthey unsupported PtRu (1:1) anode catalyst incorporated into a DMFC membrane electrode assembly. During DMFC operation the catalyst is essentially metallic with half of the Ru incorporated into a face-centered cubic (FCC) Pt alloy lattice and the remaining half in an amorphous phase. The extended X-ray absorption fine structure (EXAFS) analysis suggests that the FCC lattice is not fully disordered. The EXAFS indicates that the Ru-O bond lengths were significantly shorter than those reported for Ru-O of ruthenium oxides, suggesting that the phases in which the Ru resides in the catalysts are not similar to oxides.

Preparation and characterization of Pt/C and Pt sbnd Ru/C electrocatalysts for direct ethanol fuel cells

Science.gov (United States)

Liu, Zhaolin; Ling, Xing Yi; Su, Xiaodi; Lee, Jim Yang; Gan, Leong Ming

Nano-sized Pt and Pt sbnd Ru colloids are prepared by a microwave-assisted polyol process, and transferred to a toluene solution of decanthiol. Vulcan XC-72 is then added to the toluene solution to adsorb the thiolated Pt and Pt sbnd Ru colloids. Transmission electron microscopy examinations show nearly spherical particles and narrow size distributions for both supported and unsupported metals. The carbon-supported Pt and Pt sbnd Ru nanoparticles are activated by thermal treatment to remove the thiol stabilizing shell. All Pt and Pt sbnd Ru catalysts (except Pt 23sbnd Ru 77) give the X-ray diffraction pattern of a face-centered cubic (fcc) crystal structure, whereas the Pt 23sbnd Ru 77 alloy is more typical of the hexagonal close packed (hcp) structure. The electro-oxidation of liquid ethanol on these catalysts is investigated at room temperature by cyclic voltammetry. The results demonstrate that the alloy catalyst is catalytically more active than pure platinum. Preliminary tests on a single cell of a direct ethanol fuel cell (DEFC) indicate that a Pt 52sbnd Ru 48/C anode catalyst gives the best electrocatalytic performance among all the carbon-supported Pt and Pt sbnd Ru catalysts.

Methanol oxidation catalysis and substructure of PtRu bimetallic nanoparticles

Energy Technology Data Exchange (ETDEWEB)

Nitani, Hiroaki; Nakagawa, Takashi; Ono, Takahiro; Honda, Yusuke; Koizumi, Akiko; Seino, Satoshi; Yamamoto, Takao A. [Graduate School of Engineering, Osaka University, 2-1 Yamada-oka, Suita, Osaka 565-0871 (Japan); Daimon, Hideo; Kurobe, Yukiko [Development and Technology Division, Hitachi Maxell Ltd., 6-20-1 Kinunodai, Tsukubamirai, Ibaraki 300-2496 (Japan)

2007-07-15

Catalytic material of PtRu nanoparticles supported on carbon (PtRu/C) for direct methanol fuel cells was synthesized by a polyol reduction method. Addition of phosphorus was effective for downsizing PtRu particles and improving their catalytic activity. The activity obtained was six times of that of a commercial catalysis. The samples were analyzed by techniques of X-ray absorption fine structure (XAFS) at Pt L{sub III}-edge and Ru K-edge, transmission electron microscope (TEM), X-ray diffraction (XRD) and X-ray fluorescence (XRF). These results indicated a core-shell structure consisting of a Pt-rich core and Ru-rich shell. By examining coordination numbers determined by XAFS analysis, we found a clear correlation between the catalytic activity and the Pt-Ru atomic pair frequency occurring on the particle surface, which supports the 'bi-functional mechanism'. (author)

Activity of carbon supported Pt3Ru2 nanocatalyst in CO oxidation

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KSENIJA DJ. POPOVIĆ

2009-08-01

Full Text Available The electrocatalytic activity of Pt3Ru2/C nanocatalyst toward the electro-oxidation of bulk CO was examined in acid and alkaline solution at ambient temperature using the thin-film, rotating disk electrode (RDE method. The catalyst was characterized by XRD analysis. The XRD pattern revealed that the Pt3Ru2/C catalyst consisted of two structures, i.e., Pt–Ru-fcc and Ru-hcp (a solid solution of Ru in Pt and a small amount of Ru or a solid solution of Pt in Ru. Electrocatalytic activities were measured by applying potentiodynamic and steady state techniques. The oxidation of CO on the Pt3Ru2/C catalyst was influenced by pH and anions from the supporting electrolytes. The Pt3Ru2/C was more active in alkaline than in acid solution, as well as in perchloric than in sulfuric acid. Comparison of CO oxidation on Pt3Ru2/C and Pt/C revealed that the Pt3Ru2/C was more active than Pt/C in acid solution, while both catalysts had a similar activity in alkaline solution.

Preparation of supported PtRu/C electrocatalyst for direct methanol fuel cells

International Nuclear Information System (INIS)

Jiang Luhua; Sun Gongquan; Zhao Xinsheng; Zhou Zhenhua; Yan Shiyou; Tang Shuihua; Wang Guoxiong; Zhou Bing; Xin Qin

2005-01-01

In this work, high-surface supported PtRu/C were prepared with Ru(NO)(NO 3 ) 3 and [Pt(H 2 NCH 2 CH 2 NH 2 ) 2 ]Cl 2 as the precursors and hydrogen as a reducing agent. XRD and TEM analyses showed that the PtRu/C catalysts with different loadings possessed small and homogeneous metal particles. Even at high metal loading (40 wt.% Pt, 20 wt.% Ru) the mean metal particle size is less than 4 nm. Meanwhile, the calculated Pt crystalline lattice parameter and Pt (2 2 0) peak position indicated that the geometric structure of Pt was modified by Ru atoms. Among the prepared catalysts, the lattice parameter of 40-20 wt.% PtRu/C contract most. Cyclic voltammetry (CV), chronoamperometry (CA), CO stripping and single direct methanol fuel cell tests jointly suggested that the 40-20 wt.% PtRu/C catalyst has the highest electrochemical activity for methanol oxidation

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

Science.gov (United States)

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

2009-07-07

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

Pt and PtRu catalyst bilayers increase efficiencies for ethanol oxidation in proton exchange membrane electrolysis and fuel cells

Science.gov (United States)

Altarawneh, Rakan M.; Pickup, Peter G.

2017-10-01

Polarization curves, product distributions, and reaction stoichiometries have been measured for the oxidation of ethanol at anodes consisting of Pt and PtRu bilayers and a homogeneous mixture of the two catalysts. These anode structures all show synergies between the two catalysts that can be attributed to the oxidation of acetaldehyde produced at the PtRu catalyst by the Pt catalyst. The use of a PtRu layer over a Pt layer produces the strongest effect, with higher currents than a Pt on PtRu bilayer, mixed layer, or either catalyst alone, except for Pt at high potentials. Reaction stoichiometries (average number of electrons transferred per ethanol molecule) were closer to the values for Pt alone for both of the bilayer configurations but much lower for PtRu and mixed anodes. Although Pt alone would provide the highest overall fuel cell efficiency at low power densities, the PtRu on Pt bilayer would provide higher power densities without a significant loss of efficiency. The origin of the synergy between the Pt and PtRu catalysts was elucidated by separation of the total current into the individual components for generation of carbon dioxide and the acetaldehyde and acetic acid byproducts.

The electrocatalytic properties of carbon supported PtRu/C nanoalloys in oxidation of small organic molecules: Comparison with Pt/C catalyst

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Lović Jelena D.

2012-01-01

Full Text Available The electrocatalytic activity of carbon supported PtRu/C catalysts, with different composition, toward the electrooxidation of methanol, CO and formic acid were examined in acid and alkaline solution at ambient temperature using thin-film rotating disk electrode (RDE method and compared with activity of Pt/C. The catalysts were characterized by XRD, AFM and STM techniques. XRD pattern revealed that PtRu-1/C catalyst is consisted of two structures e.g. Pt-Ru-fcc and Ru-hcp (the solid solution of Ru in Pt and the small amount of Ru or solid solution of Pt in Ru, as opposed to PtRu-2/C catalyst which is consisted of one structure mostly, Pt-Ru-fcc. According to STM images, PtRu as well as Pt, particles size were between 2 and 6 nm, which is in a good agreement with the mean particles size determined by XRD. To establish the activity and stability of the catalysts potentiodynamic and quasi steady-state measurements were performed. It was found that the activity of Pt and PtRu for CO and methanol oxidation is a strong function of pH of solution. The kinetics are much higher in alkaline than in acid solution and the difference between Pt/C and PtRu/C is much less pronounced in alkaline media. Results presented in this work indicate that activity of PtRu catalysts depends on catalyst composition, e.g. on Pt/Ru atomic ratio, as well as on alloying degree of catalysts. Comparison of CO, methanol and formic acid oxidation on PtRu-2/C, PtRu-1/C and Pt/C catalysts revealed that PtRu-2/C is the most active one. It was shown that the PtRu-2/C catalyst, due to fact that it is consisted of only one phase, with high alloying degree, through the bifunctional mechanism improved by electronic effect, achieve the activity two times higher related to PtRu-1/C in the oxidation of all organic molecules investigated, and about three times higher compared to Pt/C in the oxidation of methanol and CO, and five times higher in formic acid oxidation.

Comparison of different promotion effect of PtRu/C and PtSn/C electrocatalysts for ethanol electro-oxidation

Energy Technology Data Exchange (ETDEWEB)

Li, Huanqiao; Cao, Lei [Direct Alcohol Fuel Cell Laboratory, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023 (China); Graduate School of the Chinese Academy Sciences, Beijing 100039 (China); Sun, Gongquan; Jiang, Luhua [Direct Alcohol Fuel Cell Laboratory, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023 (China); Xin, Qin [Direct Alcohol Fuel Cell Laboratory, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023 (China); State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023 (China)

2007-08-01

Well dispersed PtSn/C, PtRu/C and Pt/C electrocatalysts were synthesized by a modified polyol process and characterized by X-ray diffraction (XRD), transmission electron microscope (TEM) and inductively coupled plasma-atomic emission spectrometry techniques. XRD patterns show that Ru induces the contraction of Pt lattice parameter while Sn makes the Pt crystal lattice extended. Ethanol oxidation activities on the catalysts were studied via cyclic voltammetry (CV) and chronoamperometry (CA) methods at room temperature. It is found that the electrode potential plays an important role in the electrochemical behavior of ethanol oxidation on PtRu/C and PtSn/C catalysts. In the lower potential region, PtSn/C possesses higher performance for ethanol oxidation, while in the higher potential region PtRu/C is more active. The different promotion effects of PtSn/C and PtRu/C to ethanol oxidation can be explained by the structural effect and modified bi-functional mechanism in different potential region. Single cell test of a direct ethanol fuel cell (DEFC) was also carried out to elucidate the promotion effect of PtRu/C and PtSn/C catalysts on the ethanol oxidation at 90 C. (author)

Comparison of different promotion effect of PtRu/C and PtSn/C electrocatalysts for ethanol electro-oxidation

International Nuclear Information System (INIS)

Li, Huanqiao; Sun, Gongquan; Cao, Lei; Jiang, Luhua; Xin, Qin

2007-01-01

Well dispersed PtSn/C, PtRu/C and Pt/C electrocatalysts were synthesized by a modified polyol process and characterized by X-ray diffraction (XRD), transmission electron microscope (TEM) and inductively coupled plasma-atomic emission spectrometry techniques. XRD patterns show that Ru induces the contraction of Pt lattice parameter while Sn makes the Pt crystal lattice extended. Ethanol oxidation activities on the catalysts were studied via cyclic voltammetry (CV) and chronoamperometry (CA) methods at room temperature. It is found that the electrode potential plays an important role in the electrochemical behavior of ethanol oxidation on PtRu/C and PtSn/C catalysts. In the lower potential region, PtSn/C possesses higher performance for ethanol oxidation, while in the higher potential region PtRu/C is more active. The different promotion effects of PtSn/C and PtRu/C to ethanol oxidation can be explained by the structural effect and modified bi-functional mechanism in different potential region. Single cell test of a direct ethanol fuel cell (DEFC) was also carried out to elucidate the promotion effect of PtRu/C and PtSn/C catalysts on the ethanol oxidation at 90 o C

Spontaneous deposition of Ru on Pt (100: morphological and electrochemical studies. Preliminary results of ethanol oxidation at Pt(100/Ru

Directory of Open Access Journals (Sweden)

Colle Vinicius D.

2003-01-01

Full Text Available In the present work ruthenium was deposited in submonolayer amounts on Pt(100 by spontaneous deposition at several deposition times. The Pt (100/Ru surfaces were analyzed using ex-situ STM to image the deposits characteristic of ruthenium on Pt (100. It was observed the formation of ruthenium islands with diameters between 1.0 and 4.5 nm with bi-atomic thickness in the center of the islands. A homogeneous distribution of the ruthenium islands on the platinum terraces was found, with no preferential deposition on steps or surface defect sites. The ruthenium coverage degree had been calculated by the decrease of charge of the hydrogen adsorption-desorption peaks in the cyclic voltammograms of the Pt(100/Ru electrodes. The Pt(100/Ru electrodes with a ruthenium coverage degree of ca. 0.3 showed a high activity for the ethanol electrooxidation. The electrochemical experimental results support strongly the bifunctional mechanism for the enhanced ethanol oxidation.

Effect of the structural characteristics of binary Pt-Ru and ternary Pt-Ru-M fuel cell catalysts on the activity of ethanol electrooxidation in acid medium.

Science.gov (United States)

Antolini, Ermete

2013-06-01

In view of their possible use as anode materials in acid direct ethanol fuel cells, the electrocatalytic activity of Pt-Ru and Pt-Ru-M catalysts for ethanol oxidation has been investigated. This minireview examines the effects of the structural characteristics of Pt-Ru, such as the degree of alloying and Ru oxidation state, on the electrocatalytic activity for ethanol oxidation. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Study the Polyol Process of Preparing the ru Doped FePt Nanoparticles

Science.gov (United States)

Lee, Chih-Hao; Hsu, Jen-Ho; Su, Hui-Chia; Huang, Tzu Wen

The structure of Ru doped FePt nanoparticles using polyol process was studied. The particle size grown is around 5 nm, and a shell structure might be formed. By selecting the time and temperature of adding the Ru precursors into solution, three different processes to synthesize the FePtRu particles were studied resulting in different growing mechanics. The possible models during the reaction process are also discussed. The phase transition temperature for the as-grown FCC FePt nanoparticle to transform into L10 FePt nanoparticle is about 823 K which is about the same as the one without doping Ru atoms. From the XAS study of each element, the possible scenario is that: although Ru atoms with the size close to the Pt, they do not totally replace the Pt sites in the FePt alloy. Instead, most of Ru formed a shell outside the FePt nanoparticles and Fe atoms are replaced.

Core-level binding energy shifts in Pt Ru nanoparticles: A puzzle resolved

Science.gov (United States)

Lewera, Adam; Zhou, Wei Ping; Hunger, Ralf; Jaegermann, Wolfram; Wieckowski, Andrzej; Yockel, Scott; Bagus, Paul S.

2007-10-01

Synchrotron measurements of Pt and Ru core-level binding energies, BE's, in Pt-Ru nanoparticles, as a function of Pt content, quantify earlier indications that the Pt 4f BE shift is much larger than the Ru 3d BE shift. A complementary theoretical analysis relates the BE shifts to changes in the metal-metal distances as the composition of the nanoparticle changes. We establish that the large Pt and small Ru BE shifts arise from the different response of these metals to changes in the bond distances, an unexpected result. Our results give evidence that the magnitudes of the BE shifts depend on whether the d band is open, as for Ru, or essentially filled, as for Pt.

Pt and PtRu nanoparticles supported on N-doped carbons as electrocatalysts for methanol electro oxidation

Energy Technology Data Exchange (ETDEWEB)

Pereira, Viviane Santos; Silva, Julio Cesar Martins; Oliveira Neto, Almir; Spinace, Estevam Vitorio, E-mail: viviane_sp_saopaulo@yahoo.com.br [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil)

2016-07-01

Full text: Methanol is a liquid transportation fuel that can be produced from fossil or renewable resources. Fuel cells employing methanol directly as fuel (Direct Methanol Fuel Cell - DMFC) are very attractive as power source for portable, mobile and stationary applications [1]. PtRu/C electrocatalyst has been considered the best electrocatalyst for methanol electro-oxidation, however, its performance is strongly dependent on the method of preparation and on the characteristics of the carbon support. N-doped carbons with different N contents (1, 2 and 5 wt%) were prepared by thermal treatment of carbon with urea at 800 deg C. Pt and PtRu nanoparticles were supported on N-doped carbons by coreduction of Pt(IV) and Ru(III) ions using an alcohol-reduction process [2]. The obtained materials were characterized by Energy Dispersive X-ray spectroscopy, X-ray diffraction, Transmission electron microscopy and Cyclic Voltammetry. Pt and PtRu nanoparticles supported on N-doped carbons showed superior performance for methanol electro-oxidation when compared to the materials supported on non-modified carbon and to Pt/C and PtRu/C commercial electrocatalysts. Pt/C and PtRu/C prepared with the carbon modified with 2.5 wt% of N content showed the best activities. (author) [1] Y. Zhou, K. Neyerlin, T.S. Olson, S. Pylypenko, J. Bult, H.N. Dinh, T. Gennett, Z. Shao and R. O'Hayre, Energy Environ. Sci. 3, 1437 (2010); [2] E.V. Spinace, A.Oliveira Neto, T.R.R. Vasconcellos, M. Linardi, J. Power Sources 137, 17 (2004)

Electro-oxidation of ethanol and ethylene glycol on carbon-supported nano-Pt and -PtRu catalyst in acid solution

International Nuclear Information System (INIS)

Chatterjee, Moitrayee; Chatterjee, Abhik; Ghosh, Susanta; Basumallick, I.

2009-01-01

Present paper reports kinetics of electro-oxidation of ethanol (EtOH) and ethylene glycol (EG) onto Pt and PtRu nanocatalysts of different compositions in the temperature range of 298-318 K. These catalysts have been characterized by SEM, EDX, XRD, CV and amperometry. It has been observed that apparent activation energies for oxidation of EtOH and EG pass through a minimum at about 15-20 at.% of Ru in the PtRu alloy catalysts. Anodic peak current vs. composition curve also shows a maximum around this composition. The results have been explained by a geometric model, which proposes requirement of an ensemble of three Pt atoms with an adjacent Ru atom onto PtRu surface for an efficient electro-oxidation of EtOH or EG. This is further supported from statistical data analysis of probability of occurrence of such ensembles onto PtRu alloy surface. Present results also suggest that electro-oxidation of EG onto nano-PtRu catalyst surfaces follows a different path from that of EtOH at alloy composition less than 15 at.% of Ru.

Electro-oxidation of ethanol and ethylene glycol on carbon-supported nano-Pt and -PtRu catalyst in acid solution

Energy Technology Data Exchange (ETDEWEB)

Chatterjee, Moitrayee; Chatterjee, Abhik; Ghosh, Susanta [Electrochemical Laboratory, Department of Chemistry, Visva-Bharati University, Santiniketan 731235 (India); Basumallick, I., E-mail: ibasumallick@yahoo.co.u [Electrochemical Laboratory, Department of Chemistry, Visva-Bharati University, Santiniketan 731235 (India)

2009-12-01

Present paper reports kinetics of electro-oxidation of ethanol (EtOH) and ethylene glycol (EG) onto Pt and PtRu nanocatalysts of different compositions in the temperature range of 298-318 K. These catalysts have been characterized by SEM, EDX, XRD, CV and amperometry. It has been observed that apparent activation energies for oxidation of EtOH and EG pass through a minimum at about 15-20 at.% of Ru in the PtRu alloy catalysts. Anodic peak current vs. composition curve also shows a maximum around this composition. The results have been explained by a geometric model, which proposes requirement of an ensemble of three Pt atoms with an adjacent Ru atom onto PtRu surface for an efficient electro-oxidation of EtOH or EG. This is further supported from statistical data analysis of probability of occurrence of such ensembles onto PtRu alloy surface. Present results also suggest that electro-oxidation of EG onto nano-PtRu catalyst surfaces follows a different path from that of EtOH at alloy composition less than 15 at.% of Ru.

Nanoscale decomposition of Nb-Ru-O

Science.gov (United States)

Music, Denis; Geyer, Richard W.; Chen, Yen-Ting

2016-11-01

A correlative theoretical and experimental methodology has been employed to explore the decomposition of amorphous Nb-Ru-O at elevated temperatures. Density functional theory based molecular dynamics simulations reveal that amorphous Nb-Ru-O is structurally modified within 10 ps at 800 K giving rise to an increase in the planar metal - oxygen and metal - metal population and hence formation of large clusters, which signifies atomic segregation. The driving force for this atomic segregation process is 0.5 eV/atom. This is validated by diffraction experiments and transmission electron microscopy of sputter-synthesized Nb-Ru-O thin films. Room temperature samples are amorphous, while at 800 K nanoscale rutile RuO2 grains, self-organized in an amorphous Nb-O matrix, are observed, which is consistent with our theoretical predictions. This amorphous/crystalline interplay may be of importance for next generation of thermoelectric devices.

Radiolytic synthesis of carbon-supported PtRu nanoparticles using high-energy electron beam: effect of pH control on the PtRu mixing state and the methanol oxidation activity

International Nuclear Information System (INIS)

Ohkubo, Yuji; Kageyama, Satoru; Seino, Satoshi; Nakagawa, Takashi; Kugai, Junichiro; Nitani, Hiroaki; Ueno, Koji; Yamamoto, Takao A.

2013-01-01

Electrode catalysts composed of carbon-supported PtRu nanoparticles (PtRu/C) for use as a direct methanol fuel cell anode were synthesized by the reduction of precursor ions in an aqueous solution via irradiation with a high-energy electron beam. The effect of pH control in the precursor solution on the PtRu mixing state and the methanol oxidation activity was studied in order to enhance the catalytic activity for methanol oxidation. The PtRu/C structures were characterized by transmission electron microscopy, inductively coupled plasma atomic emission spectrometry, X-ray fluorescence spectrometry, and X-ray diffraction and X-ray absorption fine structure techniques. The methanol oxidation activity was evaluated by linear sweep voltammetry. The initial pH of the precursor solution has little influence on the average grain size for the metal particles (approximately 3.5 nm) on the carbon particle supports, but the dispersibility of the metal particles, PtRu mixing state, and methanol oxidation activity differed. The maintenance of a low pH in the precursor solution gave the best dispersibility of the PtRu nanoparticles supported on the surface of the carbon particles, whereas, a high pH gave the best PtRu mixing state and the highest oxidation current although a low dispersibility of the PtRu nanoparticles supported on the surface of the carbon particles was obtained. The PtRu mixing state strongly correlated with the methanol oxidation current. In addition, a high pH was more effective for PtRu mixing when using an electron beam irradiation reduction method, because the complexation reaction of the chelating agents was improved, which resulted in an enhancement of the catalytic activity for methanol oxidation.

Radiolytic synthesis of carbon-supported PtRu nanoparticles using high-energy electron beam: effect of pH control on the PtRu mixing state and the methanol oxidation activity

Energy Technology Data Exchange (ETDEWEB)

Ohkubo, Yuji, E-mail: okubo@mit.eng.osaka-u.ac.jp; Kageyama, Satoru; Seino, Satoshi; Nakagawa, Takashi; Kugai, Junichiro [Osaka University, Graduate School of Engineering (Japan); Nitani, Hiroaki [High Energy Accelerator Research Organization (KEK), Institute of Materials Structure Science (Japan); Ueno, Koji [Japan Electron Beam Irradiation Service Ltd (Japan); Yamamoto, Takao A. [Osaka University, Graduate School of Engineering (Japan)

2013-05-15

Electrode catalysts composed of carbon-supported PtRu nanoparticles (PtRu/C) for use as a direct methanol fuel cell anode were synthesized by the reduction of precursor ions in an aqueous solution via irradiation with a high-energy electron beam. The effect of pH control in the precursor solution on the PtRu mixing state and the methanol oxidation activity was studied in order to enhance the catalytic activity for methanol oxidation. The PtRu/C structures were characterized by transmission electron microscopy, inductively coupled plasma atomic emission spectrometry, X-ray fluorescence spectrometry, and X-ray diffraction and X-ray absorption fine structure techniques. The methanol oxidation activity was evaluated by linear sweep voltammetry. The initial pH of the precursor solution has little influence on the average grain size for the metal particles (approximately 3.5 nm) on the carbon particle supports, but the dispersibility of the metal particles, PtRu mixing state, and methanol oxidation activity differed. The maintenance of a low pH in the precursor solution gave the best dispersibility of the PtRu nanoparticles supported on the surface of the carbon particles, whereas, a high pH gave the best PtRu mixing state and the highest oxidation current although a low dispersibility of the PtRu nanoparticles supported on the surface of the carbon particles was obtained. The PtRu mixing state strongly correlated with the methanol oxidation current. In addition, a high pH was more effective for PtRu mixing when using an electron beam irradiation reduction method, because the complexation reaction of the chelating agents was improved, which resulted in an enhancement of the catalytic activity for methanol oxidation.

Preparation of PtRu/C and PtSn/C electrocatalysts using electron beam irradiation for direct and ethanol fuel cell

International Nuclear Information System (INIS)

Silva, Dionisio Furtunato da

2009-01-01

PtRu/C and PtSn/C electrocatalysts were prepared using electron beam irradiation. The metal ions were dissolved in water/2-propanol and water/ethylene glycol solutions and the carbon support was added. The resulting mixtures were irradiated under stirring. The effect of water/ethylene glycol and water/2-propanol (v/v) ratio, Pt:Ru and Pt:Sn atomic ratios, the irradiation time and dose rate were studied. The obtained materials were characterized by Energy dispersive analysis of X-rays (EDX), X-ray diffraction (XRD), cyclic voltammetry (CV) and Moessbauer spectroscopy. The electro-oxidation of methanol and ethanol were studied by cyclic voltammetry and chronoamperometry using the thin porous coating technique. The electrocatalysts were also tested on the Direct Methanol and Ethanol Fuel Cells. PtRu/C electrocatalysts prepared in water/ethylene glycol showed Pt:Ru atomic ratios different from the nominal ones. The results suggested that part of the Ru(III) ions were not reduced. The obtained materials showed the face-centered cubic (fcc) structure of Pt and Pt alloys with crystallite sizes of 2-3 nm. PtRu/C electrocatalysts prepared in water/2-propanol showed Pt:Ru atomic ratios similar to the nominal ones. The obtained materials also showed the fcc structure of platinum and platinum alloys with crystallite sizes of 3-4 nm. PtSn/C electrocatalysts prepared in water/ethylene glycol and water/2-propanol showed Pt:Sn atomic ratios similar to the nominal ones. The obtained materials showed the platinum (fcc) phase with crystallite sizes in the range of 2 - 4 nm and a SnO 2 (cassiterite) phase. The obtained PtRu/C and PtSn/C electrocatalysts showed similar or superior performance for methanol and ethanol electro-oxidation compared to commercial PtRu/C (E-TEK) and PtSn/C (BASF) electrocatalysts. (author)

PtRu nanoparticles dispersed on nitrogen-doped carbon nanohorns as an efficient electrocatalyst for methanol oxidation reaction

International Nuclear Information System (INIS)

Zhang, Linwei; Gao, Ang; Liu, Yan; Wang, Yuan; Ma, Jiantai

2014-01-01

Highlights: • A novel anode catalyst is synthesized using N-doped carbon nanohorns as support. • PtRu/NCNHs exhibits an excellent activity for MOR relative to PtRu/C catalysts. • The enhancement is due to the electronic interaction between NCNHs and PtRu NPs. - Abstract: A novel anode catalyst (PtRu/NCNHs) assembled with nitrogen-doped carbon nanohorns (NCNHs) and PtRu nanoparticles (1.9 nm) exhibits an obvious enhancement in the tolerance to carbonaceous intermediates and the electocatalytic activity for methanol oxidation reaction (MOR) in comparison to a commercial PtRu/C-JM catalyst and a home-made PtRu/Vulcan catalyst. The MOR mass activity of PtRu/NCNHs (850 mA mg −1 PtRu ) is 2.5 times as high as that of PtRu/C-JM (341 mA mg −1 PtRu ). The MOR specific activity of PtRu/NCNHs is 1.8 times as high as that of PtRu/Vulcan having similar Pt/Ru atomic ratios, specific electrochemical surface areas and particle sizes of PtRu NPs. The electronic interaction between PtRu NPs and NCNHs is responsible for the enhancement in the MOR activity of PtRu/NCNHs

Preparation and characterization of multi-walled carbon nanotube (MWCNTs)-supported Pt-Ru catalyst for methanol electrooxidation

Energy Technology Data Exchange (ETDEWEB)

Yang Chunwei [Department of Applied Chemistry, Harbin Institute of Technology, Harbin 150001 (China)], E-mail: cw.yang@hit.edu.cn; Wang Dianlong; Hu Xinguo; Dai Changsong [Department of Applied Chemistry, Harbin Institute of Technology, Harbin 150001 (China); Zhang Liang [School of Materials Science and Engineering, Beijing Institute of Technology, Beijing 100081 (China)

2008-01-10

Multi-walled carbon nanotubes (MWCNTs) as a support of PtRu catalyst nanocomposites were prepared by colloid method in this work. Transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) all indicate that ultrasonic treatment can effectively functionalize MWCNTs, endowing them with groups that can act as nucleation sites which can favor well-dispersed deposition of PtRu clusters on their surface. The PtRu/MWCNTs catalysts have a high and homogeneous dispersion of spherical PtRu metal particles with a narrow particle-size distribution. From XPS tests, in PtRu/MWCNTs catalysts Ru can weaken the out-shell electrons of Pt because a part of Ru form alloy with Pt. The remnant Ru exists in oxidation and provides abundant oxygen to nearby Pt, as accelerated desorption and oxidation of intermediate products of methanol oxidation at surface of Pt. By a series of electrochemistry measurements, the PtRu/MWCNTs catalysts display significantly higher performance than the PtRu/XC-72 catalysts. Finally, schematic procedures for the oxidation of MWCNTs and synthesis of PtRu/MWCNTs catalysts were given.

Preparation and characterization of multi-walled carbon nanotube (MWCNTs)-supported Pt-Ru catalyst for methanol electrooxidation

International Nuclear Information System (INIS)

Yang Chunwei; Wang Dianlong; Hu Xinguo; Dai Changsong; Zhang Liang

2008-01-01

Multi-walled carbon nanotubes (MWCNTs) as a support of PtRu catalyst nanocomposites were prepared by colloid method in this work. Transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) all indicate that ultrasonic treatment can effectively functionalize MWCNTs, endowing them with groups that can act as nucleation sites which can favor well-dispersed deposition of PtRu clusters on their surface. The PtRu/MWCNTs catalysts have a high and homogeneous dispersion of spherical PtRu metal particles with a narrow particle-size distribution. From XPS tests, in PtRu/MWCNTs catalysts Ru can weaken the out-shell electrons of Pt because a part of Ru form alloy with Pt. The remnant Ru exists in oxidation and provides abundant oxygen to nearby Pt, as accelerated desorption and oxidation of intermediate products of methanol oxidation at surface of Pt. By a series of electrochemistry measurements, the PtRu/MWCNTs catalysts display significantly higher performance than the PtRu/XC-72 catalysts. Finally, schematic procedures for the oxidation of MWCNTs and synthesis of PtRu/MWCNTs catalysts were given

Effects of composition on structure and activity of PtRu/C catalysts.

Science.gov (United States)

Wiltshire, Richard J K; King, Colin R; Rose, Abigail; Wells, Peter P; Davies, Hazel; Hogarth, Martin P; Thompsett, David; Theobald, Brian; Mosselmans, Fredrick W; Roberts, Mark; Russell, Andrea E

2009-04-07

A series of carbon supported PtRu bimetallic catalysts with varying Pt:Ru ratio were prepared and characterised using ex situ and in situ XRD, in situ EXAFS at 0 V vs. RHE, ex situ XPS and monolayer CO stripping voltammetry. Although the catalysts were found to be well mixed/alloyed, with no evidence of unalloyed Ru (oxides) present, the surfaces of the electrocatalyst nanoparticles were found to be enriched with Pt compared to the nominal bulk composition. The methanol oxidation activities of the catalysts were determined in 1.0 mol dm(-3) H2SO4. In agreement with published studies of polycrystalline bulk PtRu alloys the catalyst with a 0.6 surface fraction of Pt was found to give the best methanol oxidation activity at 30 degrees C. However, at 80 degrees C a greater surface fraction of Ru could be tolerated, with some activity at low current densities found for a Pt surface fraction as low as 0.2. The results support the conclusion that a limited amount of methanol dehydrogenation occurs at Ru sites or Ru dominated surface ensembles at 80 degrees C.

O2-enhanced methanol oxidation reaction at novel Pt-Ru-C co-sputtered electrodes

International Nuclear Information System (INIS)

Umeda, Minoru; Matsumoto, Yosuke; Inoue, Mitsuhiro; Shironita, Sayoko

2013-01-01

Highlights: ► Novel Pt-Ru-C electrodes were prepared by a co-sputtering technique. ► Co-sputtered electrodes with C result in highly efficient O 2 -enhanced methanol oxidation. ► Pt–Ru-alloy-based co-sputtered electrode induces a negative onset potential of methanol oxidation. ► The Pt-Ru-C electrodes allow a negative onset potential of O 2 -enhanced methanol oxidation. ► The optimum atomic ratios of Pt-Ru-C are Pt: 0.24–0.80, Ru: 0.14–0.61, C: 0.06–0.37. -- Abstract: A Pt-Ru-C electrode has been developed using a co-sputtering technique for use as the anode catalyst of a mixed-reactant fuel cell. The physical and electrochemical characteristics of the electrodes demonstrate that co-sputtered Pt and Ru form a Pt–Ru alloy. The crystallite sizes of the catalysts investigated in this study are reduced by the addition of C to the Pt–Ru alloy. Cu stripping voltammograms suggest that the sputtering of C and the formation of the Pt–Ru alloy synergically increase the electrochemical surface area of the electrodes. The methanol oxidation performances of the prepared electrodes were evaluated in N 2 and O 2 atmospheres; the Pt-Ru-C electrodes achieve an O 2 -induced negative shift in the onset potential of the methanol oxidation (E onset ) and enhance the methanol oxidation current density in the O 2 atmosphere. The mechanism of O 2 -enhanced methanol oxidation with a negative E onset at the Pt-Ru-C electrodes is attributed to a change in the electronic structure of Pt due to the formation of Pt–Ru alloy and the generation of O-based adsorption species by the reduction of O 2 . Finally, the composition of the Pt-Ru-C electrode for the O 2 -enhanced methanol oxidation with a negative E onset was found to be optimal at an atomic ratio of Pt: 0.24–0.80, Ru: 0.14–0.61, and C: 0.06–0.37

Particle size dependence of CO tolerance of anode PtRu catalysts for polymer electrolyte fuel cells

Science.gov (United States)

Yamanaka, Toshiro; Takeguchi, Tatsuya; Wang, Guoxiong; Muhamad, Ernee Noryana; Ueda, Wataru

An anode catalyst for a polymer electrolyte fuel cell must be CO-tolerant, that is, it must have the function of hydrogen oxidation in the presence of CO, because hydrogen fuel gas generated by the steam reforming process of natural gas contains a small amount of CO. In the present study, PtRu/C catalysts were prepared with control of the degree of Pt-Ru alloying and the size of PtRu particles. This control has become possible by a new method of heat treatment at the final step in the preparation of catalysts. The CO tolerances of PtRu/C catalysts with the same degree of Pt-Ru alloying and with different average sizes of PtRu particles were thus compared. Polarization curves were obtained with pure H 2 and CO/H 2 (CO concentrations of 500-2040 ppm). It was found that the CO tolerance of highly dispersed PtRu/C (high dispersion (HD)) with small PtRu particles was much higher than that of poorly dispersed PtRu/C (low dispersion (LD)) with large metal particles. The CO tolerance of PtRu/C (HD) was higher than that of any commercial PtRu/C. The high CO tolerance of PtRu/C (HD) is thought to be due to efficient concerted functions of Pt, Ru, and their alloy.

Ternary Pt-Ru-Ni catalytic layers for methanol electrooxidation prepared by electrodeposition and galvanic replacement

Directory of Open Access Journals (Sweden)

Athanasios ePapaderakis

2014-06-01

Full Text Available Ternary Pt-Ru-Ni deposits on glassy carbon substrates, Pt-Ru(Ni/GC, have been formed by initial electrodeposition of Ni layers onto glassy carbon electrodes, followed by their partial exchange for Pt and Ru, upon their immersion into equimolar solutions containing complex ions of the precious metals. The overall morphology and composition of the deposits has been studied by SEM microscopy and EDS spectroscopy. Continuous but nodular films have been confirmed, with a Pt÷Ru÷Ni % bulk atomic composition ratio of 37÷12÷51 (and for binary Pt-Ni control systems of 47÷53. Fine topographical details as well as film thickness have been directly recorded using AFM microscopy. The composition of the outer layers as well as the interactions of the three metals present have been studied by XPS spectroscopy and a Pt÷Ru÷Ni % surface atomic composition ratio of 61÷12÷27 (and for binary Pt-Ni control systems of 85÷15 has been found, indicating the enrichment of the outer layers in Pt; a shift of the Pt binding energy peaks to higher values was only observed in the presence of Ru and points to an electronic effect of Ru on Pt. The surface electrochemistry of the thus prepared Pt-Ru(Ni/GC and Pt(Ni/GC electrodes in deaerated acid solutions (studied by cyclic voltammetry proves the existence of a shell consisting exclusively of Pt-Ru or Pt. The activity of the Pt-Ru(Ni deposits towards methanol oxidation (studied by slow potential sweep voltammetry is higher from that of the Pt(Ni deposit and of pure Pt; this enhancement is attributed both to the well-known Ru synergistic effect due to the presence of its oxides but also (based on the XPS findings to a modification effect of Pt electronic properties.

H2-splitting on Pt/Ru alloys supported on sputtered HOPG

DEFF Research Database (Denmark)

Fiordaliso, Elisabetta Maria; Dahl, Søren; Chorkendorff, Ib

2011-01-01

to strain and ligand effects, caused by the compression of the surface due to the presence of the larger Pt atoms in the neighboring Ru atoms. The apparent energy of desorption at equilibrium, Eapp, for the three Pt-Ru systems is found to decrease with an increasing amount of Ru in the alloys...

PtRu colloid nanoparticles for CO oxidation in microfabricated reactors

DEFF Research Database (Denmark)

Klerke, Asbjørn; Saadi, Souheil; Toftegaard, Maja Bøg

2006-01-01

The catalytic activity of PtRu colloid nanoparticles for CO oxidation is investigated in microfabricated reactors. The measured catalytic performance describes a volcano curve as a function of the Pt/Ru ratio. The apparent activation energies for the different alloy catalysts are between 21 and 1...

Preparation and characterization of PtRu/C, PtBi/C, PtRuBi/C electrocatalysts for direct electro-oxidation of ethanol in PEM fuels cells using the method of reduction by sodium borohydride

International Nuclear Information System (INIS)

Brandalise, Michele

2010-01-01

Pt/C, PtBi/C, PtRu/C and PtRuBi/C electrocatalysts were prepared by a borohydride reduction methodology and tested for ethanol oxidation. This methodology consists in mix a solution with sodium hydroxide and sodium borohydride to a mixture containing water/isopropyl alcohol, metallic precursors and the Vulcan XC 72 carbon support. It was studied the addition method of borohydride (drop by drop addition or rapid addition). The obtained electrocatalysts were characterized by energy dispersive X ray spectroscopy (EDX), thermogravimetric analysis (TGA), X ray diffraction (XRD), transmission electron microscope (TEM) and cyclic voltammetry. The ethanol electro-oxidation was studied by cyclic voltammetry and chronoamperometry using the thin porous coating technique. The electrocatalysts were tested in real conditions of operation by unit cell tests. The stability of PtRuBi/C electrocatalysts was evaluated by cyclic voltammetry, chronoamperometry using the ultra-thin porous coating technique and ring-disk electrode. The PtRuBi/C electro catalyst apparently presented a good performance for ethanol electro-oxidation but experimental evidences showed accentuated bismuth dissolution. (author)

PtRu nanoparticles embedded in nitrogen doped carbon with highly stable CO tolerance and durability

Science.gov (United States)

Ling, Ying; Yang, Zehui; Yang, Jun; Zhang, Yunfeng; Zhang, Quan; Yu, Xinxin; Cai, Weiwei

2018-02-01

As is well known, the lower durability and sluggish methanol oxidation reaction (MOR) of PtRu alloy electrocatalyst blocks the commercialization of direct methanol fuel cells (DMFCs). Here, we design a new PtRu electrocatalyst, with highly stable CO tolerance and durability, in which the PtRu nanoparticles are embedded in nitrogen doped carbon layers derived from carbonization of poly(vinyl pyrrolidone). The newly fabricated electrocatalyst exhibits no loss in electrochemical surface area (ECSA) and MOR activity after potential cycling from 0.6-1.0 V versus reversible hydrogen electrode, while commercial CB/PtRu retains only 50% of its initial ECSA. Meanwhile, due to the same protective layers, the Ru dissolution is decelerated, resulting in stable CO tolerance. Methanol oxidation reaction (MOR) testing indicates that the activity of newly fabricated electrocatalyst is two times higher than that of commercial CB/PtRu, and the fuel cell performance of the embedded PtRu electrocatalyst was comparable to that of commercial CB/PtRu. The embedded PtRu electrocatalyst is applicable in real DMFC operation. This study offers important and useful information for the design and fabrication of durable and CO tolerant electrocatalysts.

Effect of TiO_2 Loading on Pt-Ru Catalysts During Alcohol Electrooxidation

International Nuclear Information System (INIS)

Hasa, Bjorn; Kalamaras, Evangelos; Papaioannou, Evangelos I.; Vakros, John; Sygellou, Labrini; Katsaounis, Alexandros

2015-01-01

Highlights: • TiO_2 can be used to modify Pt-Ru based electrodes for alcohol oxidation. • TiO_2 modified electrodes with lower amount of metals had higher active surface area than pure Pt-Ru electrodes. • TiO_2 modified electrodes showed comparable performance with pure Pt-Ru electrode both in a single cell and in a PEM fuel cell under alcohol fuelling. - Abstract: In this study, Pt-Ru based electrodes modified by TiO_2 were prepared by means of thermal decomposition of chloride and isopropoxide precursors on Ti substrates, characterised by X-ray Diffraction (XRD), Scanning Electron Microscopy (SEM), X-ray Photoelectron Spectroscopy (XPS), electrochemical techniques and CO stripping and used as anodes for alcohol oxidation. The minimization of the metal loading without electrocatalytic activity losses was also explored. TiO_2 was chosen due to its chemical stability, low cost and excellent properties as substrate for metal dispersion. It was found that TiO_2 loading up to 50% results in a 3-fold increase of the Electrochemically Active Surface (EAS). This conclusion has been confirmed by CO stripping experiments. All samples have been evaluated during the electrochemical oxidation of methanol, ethanol and glycerol. In all cases, the Pt_2_5-Ru_2_5-(TiO_2)_5_0 electrode had better electrocatalytic activity than the pure Pt_5_0-Ru_5_0 anode. The best modified electrode, (Pt_2_5-Ru_2_5-(TiO_2)_5_0), was also evaluated as anode in a PEM fuel cell under methanol fuelling conditions. The observed higher performance of the TiO_2 modified electrodes was attributed to the enhanced Pt-Ru dispersion as well as the formation of smaller Pt and Ru particles.

Engineering Ru@Pt Core-Shell Catalysts for Enhanced Electrochemical Oxygen Reduction Mass Activity and Stability.

Science.gov (United States)

Jackson, Ariel; Strickler, Alaina; Higgins, Drew; Jaramillo, Thomas Francisco

2018-01-12

Improving the performance of oxygen reduction reaction (ORR) electrocatalysts is essential for the commercial efficacy of many renewable energy technologies, including low temperature polymer electrolyte fuel cells (PEFCs). Herein, we report highly active and stable carbon-supported Ru@Pt core-shell nanoparticles (Ru@Pt/C) prepared by a wet chemical synthesis technique. Through rotating disc electrode testing, the Ru@Pt/C achieves an ORR Pt mass-based activity of 0.50 A mg Pt -1 at 0.9 V versus the reversible hydrogen electrode (RHE), which exceeds the activity of the state-of-the-art commercial Pt/C catalyst as well as the Department of Energy 2020 PEFC electrocatalyst activity targets for transportation applications. The impact of various synthetic parameters, including Pt to Ru ratios and catalyst pretreatments (i.e., annealing) are thoroughly explored. Pt-based mass activity of all prepared Ru@Pt/C catalysts was found to exceed 0.4 mg Pt -1 across the range of compositions investigated, with the maximum activity catalyst having a Ru:Pt ratio of 1:1. This optimized composition of Ru@Pt/C catalyst demonstrated remarkable stability after 30,000 accelerated durability cycles (0.6 to 1.0 V vs. RHE at 125 mV s -1 ), maintaining 85% of its initial mass activity. Scanning transmission electron microscopy energy dispersive spectroscopy (STEM-EDS) analysis at various stages of electrochemical testing demonstrated that the Pt shell can provide sufficient protection against the dissolution of the otherwise unstable Ru core.

Effect of W on activity of Pt-Ru/C catalyst for methanol electrooxidation in acidic medium

International Nuclear Information System (INIS)

Wang Zhenbo; Zuo Pengjian; Yin Geping

2009-01-01

The effect of W on the activity of Pt-Ru/C catalyst was investigated. The Pt-Ru-W/C and Pt-Ru/C-TR catalysts were prepared by thermal reduction method. Comparison was made to a homemade Pt-Ru/C-CR catalyst prepared by chemical reduction. Their performances were tested by using a glassy carbon thin film electrode through cyclic voltammetric and chronoamperometric curves. The particle size, structure, composition, and surface state of homemade catalyst were determined by means of X-ray diffraction (XRD), energy dispersive analysis of X-ray (EDAX), transmission electron microscopy (TEM), and X-ray photoelectron spectrometry (XPS). The result of XRD analysis shows that the homemade ternary catalyst exhibits face-centered cubic structure and has smaller lattice parameter than Pt-alone and homemade Pt-Ru/C catalysts. The particle size of Pt-Ru-W/C catalyst is relatively large of 6.5 nm. Its electrochemically active specific area is 20 m 2 g -1 less than that of Pt-Ru/C-CR, and much twice as big as that of Pt-Ru/C-TR. But, XPS analysis shows that the addition of W changes the surface state of Pt components in the alloy and can clean Pt surface active sites which are adsorbed by hydrogen. The electrocatalytic activity and tolerance performance to CO ads of Pt-Ru-W/C catalyst for methanol electrooxidation is the best due to the promoting function of W in comparison with homemade Pt-Ru/C ones.

Incorporation of Pt, Ru and Pt-Ru nanoparticles into ordered mesoporous carbons for efficient oxygen reduction reaction in alkaline media

International Nuclear Information System (INIS)

Stojmenović, Marija; Momčilović, Milan; Gavrilov, Nemanja; Pašti, Igor A.; Mentus, Slavko; Jokić, Bojan; Babić, Biljana

2015-01-01

Ordered mesoporous carbon, volume-doped up to 3 w.% with Pt, Ru and Pt-Ru nanoparticles was synthesized by evaporation-induced self-assembly method, under acidic conditions. The content of incorporated metal was determined by EDX analysis. The X-ray diffractometry confirmed the existence of highly dispersed metallic phases in doped samples. Specific surface area was determined by N 2 -physisorption measurements to range between 452 and 545 m 2 g −1 . Raman spectroscopy of investigated materials indicated highly disordered carbon structure with crystallite sizes around 1.4 nm. In a form of thin-layer electrode on glassy carbon support, in 0.1 M KOH solution, the prepared materials displayed high activity toward oxygen reduction reaction (ORR) in alkaline media, with onset potentials more positive than −0.10 V vs. SCE. The kinetics of O 2 reduction was found to be affected by both the specific surface area and the concentration of metal dopants. The ethanol tolerance of (Pt, Ru)-doped OMCs was found to be higher than that of common Pt/C ORR catalysts. Presented study provides a new route for the synthesis of active and selective ORR catalysts in alkaline media, being competitive with, or superior to, the existing ones in terms of performance and price

Pt-Ru nanoparticles supported on functionalized carbon as electrocatalysts for the methanol oxidation

International Nuclear Information System (INIS)

Salgado, J.R.C.; Fernandes, J.C.S.; Botelho do Rego, A.M.; Ferraria, A.M.; Duarte, R.G.; Ferreira, M.G.S.

2011-01-01

Highlights: → The functionalized carbon using acid solutions contains surface oxygenated groups. → Uniform dispersion of PtRu nanoparticles on the carbon surface was achieved. → Physical analysis showed the formation of PtRu alloy catalysts on functionalized carbon. → PtRu alloy catalysts on functionalized carbon enhanced the methanol oxidation rate. - Abstract: Platinum-ruthenium alloy electrocatalysts, for methanol oxidation reaction, were prepared on carbons thermally treated in helium atmosphere or chemically functionalized in H 2 O 2 , or in HNO 3 + H 2 SO 4 or in HNO 3 solutions. The functionalized carbon that is produced using acid solutions contains more surface oxygenated functional groups than carbon treated with H 2 O 2 solution or HeTT. The XRD/HR-TEM analysis have showed the existence of a higher alloying degree for Pt-Ru electrocatalysts supported on functionalized carbon, which present superior electrocatalytic performance, assessed by cyclic voltammetry, chronoamperometry and electrochemical impedance spectroscopy, as compared to electrocatalysts on unfunctionalized carbon. It also was found that Pt-Ru alloy electrocatalysts on functionalized carbon improve the reaction rate compared to Pt-Ru on carbons treated with H 2 O 2 solution and thermally. A mechanism is discussed, where oxygenated groups generated from acid functionalization of carbon and adsorbed on Pt-Ru electrocatalysts are considered to enhance the electrocatalytic activity of the methanol oxidation reaction.

Electrocatalytic activity of atomic layer deposited Pt-Ru catalysts onto N-doped carbon nanotubes

NARCIS (Netherlands)

Johansson, A.-C.; Larsen, J.V.; Verheijen, M.A.; Haugshøj, K.B.; Clausen, H.; Kessels, W.M.M.; Christensen, L.H.; Thomsen, E.V.

2014-01-01

Pt-Ru catalysts of various compositions, between 0 and 100 at.% of Ru, were deposited onto N-doped multi-walled carbon nanotubes (N-CNTs) by atomic layer deposition (ALD) at 250 C. The Pt and Ru precursors were trimethyl(methylcyclopentadienyl)platinum (MeCpPtMe3) and

Electrochemical, spectroscopic, and photophysical properties of structurally diverse polyazine-bridged Ru(II),Pt(II) and Os(II),Ru(II),Pt(II) supramolecular motifs.

Science.gov (United States)

Knoll, Jessica D; Arachchige, Shamindri M; Wang, Guangbin; Rangan, Krishnan; Miao, Ran; Higgins, Samantha L H; Okyere, Benjamin; Zhao, Meihua; Croasdale, Paul; Magruder, Katherine; Sinclair, Brian; Wall, Candace; Brewer, Karen J

2011-09-19

Five new tetrametallic supramolecules of the motif [{(TL)(2)M(dpp)}(2)Ru(BL)PtCl(2)](6+) and three new trimetallic light absorbers [{(TL)(2)M(dpp)}(2)Ru(BL)](6+) (TL = bpy = 2,2'-bipyridine or phen = 1,10-phenanthroline; M = Ru(II) or Os(II); BL = dpp = 2,3-bis(2-pyridyl)pyrazine, dpq = 2,3-bis(2-pyridyl)quinoxaline, or bpm = 2,2'-bipyrimidine) were synthesized and their redox, spectroscopic, and photophysical properties investigated. The tetrametallic complexes couple a Pt(II)-based reactive metal center to Ru and/or Os light absorbers through two different polyazine BL to provide structural diversity and interesting resultant properties. The redox potential of the M(II/III) couple is modulated by M variation, with the terminal Ru(II/III) occurring at 1.58-1.61 V and terminal Os(II/III) couples at 1.07-1.18 V versus Ag/AgCl. [{(TL)(2)M(dpp)}(2)Ru(BL)](PF(6))(6) display terminal M(dπ)-based highest occupied molecular orbitals (HOMOs) with the dpp(π*)-based lowest unoccupied molecular orbital (LUMO) energy relatively unaffected by the nature of BL. The coupling of Pt to the BL results in orbital inversion with localization of the LUMO on the remote BL in the tetrametallic complexes, providing a lowest energy charge separated (CS) state with an oxidized terminal Ru or Os and spatially separated reduced BL. The complexes [{(TL)(2)M(dpp)}(2)Ru(BL)](6+) and [{(TL)(2)M(dpp)}(2)Ru(BL)PtCl(2)](6+) efficiently absorb light throughout the UV and visible regions with intense metal-to-ligand charge transfer (MLCT) transitions in the visible at about 540 nm (M = Ru) and 560 nm (M = Os) (ε ≈ 33,000-42,000 M(-1) cm(-1)) and direct excitation to the spin-forbidden (3)MLCT excited state in the Os complexes about 720 nm. All the trimetallic and tetrametallic Ru-based supramolecular systems emit from the terminal Ru(dπ)→dpp(π*) (3)MLCT state, λ(max)(em) ≈ 750 nm. The tetrametallic systems display complex excited state dynamics with quenching of the (3)MLCT emission at

Pt-Ru/CeO2/carbon nanotube nanocomposites: an efficient electrocatalyst for direct methanol fuel cells.

Science.gov (United States)

Sun, Zhenyu; Wang, Xiang; Liu, Zhimin; Zhang, Hongye; Yu, Ping; Mao, Lanqun

2010-07-20

Pt-Ru/CeO(2)/multiwalled carbon nanotube (MWNT) electrocatalysts were prepared using a rapid sonication-facilitated deposition method and were characterized by X-ray diffraction (XRD), X-ray photoemission spectroscopy (XPS), transmission electron microscopy (TEM), energy-dispersive spectroscopy (EDS), and voltammetry. Morphological characterization by TEM revealed that CeO(2) nanoparticles (NPs) were in intimate contact with Pt-Ru NPs, and both were highly dispersed on the exteriors of nanotubes with a small size and a very narrow size distribution. Compared with the Pt-Ru/MWNT and Pt/MWNT electrocatalysts, the as-prepared Pt-Ru/CeO(2)/MWNT exhibited a significantly improved electrochemically active surface area (ECSA) and a remarkably enhanced activity toward methanol oxidation. The effects of the Pt-Ru loading and the Pt-to-Ru molar ratio on the electrocatalytic activity of Pt-Ru/CeO(2)/MWNT for methanol oxidation were investigated. We found that a maximum activity toward methanol oxidation reached at the 10 wt % of Pt-Ru loading and 1:1 of Pt-to-Ru ratio. Moreover, the role of CeO(2) in the catalysts for the enhancement of methanol oxidation was discussed in terms of both bifunctional mechanism and electronic effects.

Ethylene glycol oxidation on Pt and Pt-Ru nanoparticle decorated polythiophene/multiwalled carbon nanotube composites for fuel cell applications

International Nuclear Information System (INIS)

Selvaraj, Vaithilingam; Alagar, Muthukaruppan

2008-01-01

A novel supporting material containing polythiophene (PTh) and multiwalled carbon nanotubes (MWCNTs) (PTh-CNTs) is prepared by in situ polymerization of thiophene on carbon nanotubes using FeCl 3 as oxidizing agent under sonication. The prepared polythiophene/CNT composites are further decorated with Pt and Pt-Ru nanoparticles by chemical reduction of the corresponding metal salts using HCHO as reducing agent at pH = 11 (Pt/PTh-CNT and Pt-Ru/PTh-CNT). The fabricated composite films decorated with nanoparticles were investigated towards the electrochemical oxidation of ethylene glycol (EG). The presence of carbon nanotubes in conjugation with a conducting polymer produces a good catalytic effect, which might be due to the higher electrochemically accessible surface areas, electronic conductivity and easier charge-transfer at polymer/electrolyte interfaces, which allows higher dispersion of Pt and Pt-Ru nanoparticles. Such nanoparticle modified PTh-CNT electrodes exhibit better catalytic behavior towards ethylene glycol oxidation. Results show that Pt/PTh-CNT and Pt-Ru/PTh-CNT modified electrodes show enhanced electrocatalytic activity and stability towards the electro-oxidation of ethylene glycol than the Pt/PTh electrodes, which shows that the composite film is more promising for applications in fuel cells

CO tolerance of PdPt/C and PdPtRu/C anodes for PEMFC

International Nuclear Information System (INIS)

Garcia, Amanda C.; Paganin, Valdecir A.; Ticianelli, Edson A.

2008-01-01

The performance of H 2 /O 2 proton exchange membrane fuel cells (PEMFCs) fed with CO-contaminated hydrogen was investigated for anodes with PdPt/C and PdPtRu/C electrocatalysts. The physicochemical properties of the catalysts were characterized by energy dispersive X-ray (EDX) analyses, X-ray diffraction (XRD) and 'in situ' X-ray absorption near edge structure (XANES). Experiments were conducted in electrochemical half and single cells by cyclic voltammetry (CV) and I-V polarization measurements, while DEMS was employed to verify the formation of CO 2 at the PEMFC anode outlet. A quite high performance was achieved for the PEMFC fed with H 2 + 100 ppm CO with the PdPt/C and PdPtRu/C anodes containing 0.4 mg metal cm -2 , with the cell presenting potential losses below 200 mV at 1 A cm -2 , with respect to the system fed with pure H 2 . For the PdPt/C catalysts no CO 2 formation was seen at the PEMFC anode outlet, indicating that the CO tolerance is improved due to the existence of more free surface sites for H 2 electrooxidation, probably due to a lower Pd-CO interaction compared to pure Pd or Pt. For PdPtRu/C the CO tolerance may also have a contribution from the bifunctional mechanism, as shown by the presence of CO 2 in the PEMFC anode outlet

Kinetic study of methanol oxidation on carbon-supported PtRu electrocatalyst

International Nuclear Information System (INIS)

Gojkovic, S.Lj.; Vidakovic, T.R.; Durovic, D.R.

2003-01-01

Methanol electrooxidation was investigated on the carbon-supported PtRu electrocatalyst (1:1 atomic ratio) in acid media. X-ray diffraction measurement indicated alloying of Pt and Ru. Cyclic voltammetry of the sample reflects the amount of Ru in the catalyst and its ability to adsorb OH radicals. Tafel plots for the oxidation of 0.02-3 M methanol in the solutions containing 0.05-1 M HClO 4 and in the temperature range 27-40 deg. C showed reasonably well-defined linear region with the slope of about 115 mV dec -1 at the low currents, irrespective of the experimental conditions employed. Reaction order with respect to methanol was found to be 0.5. A correlation between methanol oxidation rate and pseudocapacitive current of OH adsorption on Ru sites was established. It was proposed that bifunctional mechanism is operative with the reaction between methanol residues adsorbed on Pt sites and OH radicals adsorbed on Ru sites as the rate-determining step

Preparation of Pt Ru/C + rare earths by the method of reduction by alcohol for the electro-oxidation of ethanol; Preparacao de eletrocatalisadores PtRu/C + terras raras pelo metodo da reducao por alcool para a eletro-oxidacao do etanol

Energy Technology Data Exchange (ETDEWEB)

Tusi, M M; Rodrigues, R M.S.; Spinace, E V; Oliveira Neto, A., E-mail: aolivei@ipen.b, E-mail: espinace@ipen.b [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil)

2010-07-01

PtRu/C electrocatalyst was prepared in a single step, while that PtRu/85%C-15%Ce, PtRu/85%C-15%La, PtRu/85%C-15%Nd and PtRu/85%C-15%Er electrocatalyst were prepared in a two step. In the first step a Carbon Vulcan XC72 + rare earth supports were prepared. In the second step PtRu electrocatalyst were prepared by an alcohol-reduction process using ethylene glycol as solvent and reducing agent and supported on Vulcan XC72 + earth rare. The obtained electrocatalysts were characterized by EDAX, XRD and chronoamperometry. The electro-oxidation of ethanol was studied by chronoamperometry at room temperature. PtRu/85%C- 15%Ce electrocatalyst showed a significant increase of performance for ethanol oxidation compared to PtRu/C electrocatalyst. (author)

Engineering Ru@Pt Core-Shell Catalysts for Enhanced Electrochemical Oxygen Reduction Mass Activity and Stability

Directory of Open Access Journals (Sweden)

Ariel Jackson

2018-01-01

Full Text Available Improving the performance of oxygen reduction reaction (ORR electrocatalysts is essential for the commercial efficacy of many renewable energy technologies, including low temperature polymer electrolyte fuel cells (PEFCs. Herein, we report highly active and stable carbon-supported Ru@Pt core-shell nanoparticles (Ru@Pt/C prepared by a wet chemical synthesis technique. Through rotating disc electrode testing, the Ru@Pt/C achieves an ORR Pt mass-based activity of 0.50 A mgPt−1 at 0.9 V versus the reversible hydrogen electrode (RHE, which exceeds the activity of the state-of-the-art commercial Pt/C catalyst as well as the Department of Energy 2020 PEFC electrocatalyst activity targets for transportation applications. The impact of various synthetic parameters, including Pt to Ru ratios and catalyst pretreatments (i.e., annealing are thoroughly explored. Pt-based mass activity of all prepared Ru@Pt/C catalysts was found to exceed 0.4 mgPt−1 across the range of compositions investigated, with the maximum activity catalyst having a Ru:Pt ratio of 1:1. This optimized composition of Ru@Pt/C catalyst demonstrated remarkable stability after 30,000 accelerated durability cycles (0.6 to 1.0 V vs. RHE at 125 mV s−1, maintaining 85% of its initial mass activity. Scanning transmission electron microscopy energy dispersive spectroscopy (STEM-EDS analysis at various stages of electrochemical testing demonstrated that the Pt shell can provide sufficient protection against the dissolution of the otherwise unstable Ru core.

Methanol electro-oxidation and direct methanol fuel cell using Pt/Rh and Pt/Ru/Rh alloy catalysts

International Nuclear Information System (INIS)

Choi, Jong-Ho; Park, Kyung-Won; Park, In-Su; Nam, Woo-Hyun; Sung, Yung-Eun

2004-01-01

Pt-based binary or ternary catalysts containing Rh for use as anodes in direct methanol fuel cells (DMFC) were synthesized by borohydride reduction method combined with freeze-drying. The resulting catalysts had a specific surface area of approximately 65-75 m 2 /g. X-ray diffraction (XRD) patterns indicated that the catalysts were well alloyed and the average size of alloy catalysts was confirmed by transmission electron microscopy (TEM). The Pt/Rh (2:1) and Pt/Ru/Rh (5:4:1) alloy catalysts showed better catalytic activities for methanol electro-oxidation than Pt or Pt/Ru (1:1), respectively

Effect of the structure of Pt-Ru/C particles on COad monolayer vibrational properties and electrooxidation kinetics

International Nuclear Information System (INIS)

Maillard, Frederic; Bonnefont, Antoine; Chatenet, Marian; Guetaz, Laure; Doisneau-Cottignies, Beatrice; Roussel, Herve; Stimming, Ulrich

2007-01-01

In this paper, we combined FTIR spectroscopy and CO ad stripping voltammetry to investigate CO ad adsorption and electrooxidation on Pt-Ru/C nanoparticles. The Pt:Ru elemental composition and the metal loading were determined by ICP-AES. The X-ray diffraction patterns of the Pt-Ru/C indicated formation of a Pt-Ru (fcc) alloy. HREM images revealed an increase in the fraction of agglomerated Pt-Ru/C particles with increasing the metal loading and showed that agglomerated Pt-Ru/C nanoparticles present structural defects such as twins or grain boundaries. In addition, isolated Pt-Ru/C nanoparticles have similar mean particle size (ca. 2.5 nm) and particle size distributions whatever the metal loading. Therefore, we could determine precisely the effect of particle agglomeration on the CO ad vibrational properties and electrooxidation kinetics. FTIR measurements revealed a main CO ad stretching band at ca. ν-bar CO L =2030cm -1 , which we ascribed to a-top CO ad on Pt domains electronically modified by the presence of Ru. As the metal loading increased, the position of this band was blue shifted by ca. 5 cm -1 and a shoulder around 2005 cm -1 developed, which was ascribed to a-top CO ad on Ru domains. The reason for this was suggested to be the increasing size of Ru domains on agglomerated Pt-Ru/C particles, which lifts dipole-dipole coupling and allows two vibrational features to be observed (CO ad /Ru, CO ad /Pt). This is evidence that FTIR spectroscopy can be used to probe small chemical fluctuations of the Pt-Ru/C surface. Finally, we comment on the CO ad electrooxidation kinetics. We observed that CO ad was converted more easily into CO 2 as the metal loading, i.e. the fraction of agglomerated Pt-Ru/C nanoparticles, increased

Kinetic study of methanol oxidation on Pt2Ru3/C catalyst in the alkaline media

Directory of Open Access Journals (Sweden)

A. V. TRIPKOVIC

2007-11-01

Full Text Available The interaction of acridine orange (AO with double-stranded (ds The electrochemical oxidation of methanol in NaOH solution was examined on a thin film Pt2Ru3/C electrode. The XRD pattern revealed that the Pt2Ru3 alloy consisted of a solid solution of Ru in Pt and a small amount of Ru or a solid solution of Pt in Ru. It was shown that in alkaline solution, the difference in activity between Pt/C and Pt2Ru3/C is significantly smaller than in acid solution. It is proposed that the reaction follows a quasi bifunctional mechanism. The kinetic parameters indicated that the chemical reaction between adsorbed COad and OHad species could be the rate limiting step.

Combinatorial investigation of Pt-Ru-Sn alloys as an anode electrocatalysts for direct alcohol fuel cells

Energy Technology Data Exchange (ETDEWEB)

Chu, Young Hwan [Department of New Energy.Resource Engineering, College of Science and Engineering, Sangji University, 124, Sangjidae-gil, Wonju-si, Gangwon-Do 220-702 (Korea); Shul, Yong Gun [Department of Chemical and Biomolecular Engineering, Yonsei University, 134, Shinchon-Dong, Seodaemun-Gu, Seoul 120-749 (Korea)

2010-10-15

Low-temperature direct alcohol fuel cells fed with different kinds of alcohol (methanol, ethanol and 2-propanol) have been investigated by employing ternary electrocatalysts (Pt-Ru-Sn) as anode catalysts. Combinatorial chemistry has been applied to screen the 66-PtRuSn-anode arrays at the same time to reduce cost, time, and effort when we select the optimum composition of electrocatalysts for DAFCs (Direct Alcohol Fuel Cells). PtRuSn (80:20:0) showed the lowest onset potential for methanol electro-oxidation, PtRuSn (50:0:50) for ethanol, and PtRuSn (20:70:10) for 2-propanol in CV results respectively, and single cell performance test indicated that Ru is more suitable for direct methanol fuel cell system, Sn for direct ethanol fuel cell system, and 2-propanol could be applied as fuel with low platinum composition anode electrocatalyst. The single cell performance results and electrochemical results (CV) were well matched with the combinatorial electrochemical results. As a result, we could verify the availability of combinatorial chemistry by comparing the results of each extreme electrocatalysts compositions as follows: PtRuSn (80:20:0) for methanol, PtRuSn (50:0:50) for ethanol and PtRuSn (20:70:10) for 2-propanol. (author)

Challenges in bimetallic multilayer structure formation: Pt growth on Cu monolayers on Ru(0001)

DEFF Research Database (Denmark)

Mancera, Luis A.; Engstfeld, Albert Kilian; Bensch, Andreas

2017-01-01

In a joint experimental and theoretical study, we investigated the formation and morphology of PtCu/Ru(0001) bimetallic surfaces grown at room and higher temperatures under UHV conditions. We obtained the PtCu/Ru(0001) surfaces by deposition of Pt atoms on a previously created Cu/Ru(0001) structure...... which includes only one Cu monolayer. Bimetallic surfaces prepared at different Pt coverages are investigated using STM imaging, revealing the existence of reconstruction lines and Cu islands. Although primarily created Cu islands continue growing in size by increasing Pt coverage, a continuous...

Sol-Gel Process for Making Pt-Ru Fuel-Cell Catalysts

Science.gov (United States)

Narayanan, Sekharipuram; Valdez, Thomas; Kumta, Prashant; Kim, Y.

2005-01-01

A sol-gel process has been developed as a superior alternative to a prior process for making platinum-ruthenium alloy catalysts for electro-oxidation of methanol in fuel cells. The starting materials in the prior process are chloride salts of platinum and ruthenium. The process involves multiple steps, is time-consuming, and yields a Pt-Ru product that has relatively low specific surface area and contains some chloride residue. Low specific surface area translates to incomplete utilization of the catalytic activity that might otherwise be available, while chloride residue further reduces catalytic activity ("poisons" the catalyst). In contrast, the sol-gel process involves fewer steps and less time, does not leave chloride residue, and yields a product of greater specific area and, hence, greater catalytic activity. In this sol-gel process (see figure), the starting materials are platinum(II) acetylacetonate [Pt(C5H7O2)2, also denoted Pt-acac] and ruthenium(III) acetylacetonate [Ru(C5H7O2)3, also denoted Ru-acac]. First, Pt-acac and Ru-acac are dissolved in acetone at the desired concentrations (typically, 0.00338 moles of each salt per 100 mL of acetone) at a temperature of 50 C. A solution of 25 percent tetramethylammonium hydroxide [(CH3)4NOH, also denoted TMAH] in methanol is added to the Pt-acac/Ruacac/ acetone solution to act as a high-molecular-weight hydrolyzing agent. The addition of the TMAH counteracts the undesired tendency of Pt-acac and Ru-acac to precipitate as separate phases during the subsequent evaporation of the solvent, thereby helping to yield a desired homogeneous amorphous gel. The solution is stirred for 10 minutes, then the solvent is evaporated until the solution becomes viscous, eventually transforming into a gel. The viscous gel is dried in air at a temperature of 170 C for about 10 hours. The dried gel is crushed to make a powder that is the immediate precursor of the final catalytic product. The precursor powder is converted to the

Evaluation of Pt-Ru-Ni and Pt-Sn-Ni catalysts as anodes in direct ethanol fuel cells

Energy Technology Data Exchange (ETDEWEB)

Ribadeneira, Esteban; Hoyos, Bibian A. [Escuela de Procesos y Energia, Facultad de Minas, Universidad Nacional de Colombia, Medellin (Colombia)

2008-05-15

In this study, the electrooxidation of ethanol on carbon supported Pt-Ru-Ni and Pt-Sn-Ni catalysts is electrochemically studied through cyclic voltammetry at 50 C in direct ethanol fuel cells. All electrocatalysts are prepared using the ethylene glycol-reduction process and are chemically characterized by energy-dispersive X-ray analysis (EDX). For fuel cell evaluation, electrodes are prepared by the transfer-decal method. Nickel addition to the anode improves DEFC performance. When Pt{sub 75}Ru{sub 15}Ni{sub 10}/C is used as an anode catalyst, the current density obtained in the fuel cell is greater than that of all other investigated catalysts. Tri-metallic catalytic mixtures have a higher performance relative to bi-metallic catalysts. These results are in agreement with CV results that display greater activity for PtRuNi at higher potentials. (author)

Soft landing of bare PtRu nanoparticles for electrochemical reduction of oxygen.

Science.gov (United States)

Johnson, Grant E; Colby, Robert; Engelhard, Mark; Moon, Daewon; Laskin, Julia

2015-08-07

Magnetron sputtering of two independent Pt and Ru targets coupled with inert gas aggregation in a modified commercial source has been combined with soft landing of mass-selected ions to prepare bare 4.5 nm diameter PtRu nanoparticles on glassy carbon electrodes with controlled size and morphology for electrochemical reduction of oxygen in solution. Employing atomic force microscopy (AFM) it is shown that the nanoparticles bind randomly to the glassy carbon electrode at a relatively low coverage of 7 × 10(4) ions μm(-2) and that their average height is centered at 4.5 nm. Scanning transmission electron microscopy images obtained in the high-angle annular dark field mode (HAADF-STEM) further confirm that the soft-landed PtRu nanoparticles are uniform in size. Wide-area scans of the electrodes using X-ray photoelectron spectroscopy (XPS) reveal the presence of both Pt and Ru in atomic concentrations of ∼9% and ∼33%, respectively. Deconvolution of the high energy resolution XPS spectra in the Pt 4f and Ru 3d regions indicates the presence of both oxidized Pt and Ru. The substantially higher loading of Ru compared to Pt and enrichment of Pt at the surface of the nanoparticles is confirmed by wide-area analysis of the electrodes using time-of-flight medium energy ion scattering (TOF-MEIS) employing both 80 keV He(+) and O(+) ions. The activity of electrodes containing 7 × 10(4) ions μm(-2) of bare 4.5 nm PtRu nanoparticles toward the electrochemical reduction of oxygen was evaluated employing cyclic voltammetry (CV) in 0.1 M HClO4 and 0.5 M H2SO4 solutions. In both electrolytes a pronounced reduction peak was observed during O2 purging of the solution that was not evident during purging with Ar. Repeated electrochemical cycling of the electrodes revealed little evolution in the shape or position of the voltammograms indicating high stability of the nanoparticles supported on glassy carbon. The reproducibility of the nanoparticle synthesis and deposition was

Electrocatalytic properties of carbon-supported Pt-Ru catalysts with the high alloying degree for formic acid electrooxidation

Energy Technology Data Exchange (ETDEWEB)

Chen, Yu.; Zhou, Yiming; Tang, Yawen; Lu, Tianhong [College of Chemistry and Environmental Science, Nanjing Normal University, Nanjing 210097 (China)

2010-07-01

A series of carbon-supported bimetallic Pt-Ru catalysts with high alloying degree and different Pt/Ru atomic ratio have been prepared by a chemical reduction method in the H{sub 2}O/ethanol/tetrahydrofuran (THF) mixture solvent. The structural and electronic properties of catalysts are characterized using X-ray reflection (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM). The electrooxidation of formic acid on these Pt-Ru nanoparticles are investigated by using cyclic voltammetry, chronoamperometry and CO-stripping measurements. The results of electrochemical measurements illustrate that the alloying degree and Pt/Ru atomic ratio of Pt-Ru catalyst play an important role in the electrocatalytic activity of the Pt-Ru/C catalyst for formic acid electrooxidation due to the bifunctional mechanism and the electronic effect. Since formic acid is an intermediate in the methanol electrooxidation on Pt electrode in acidic electrolyte, the observation provides an additional fundamental understanding of the structure-activity relationship of Pt-Ru catalyst for methanol electrooxidation. (author)

Co-catalytic effect of nickel in Pt-Ru/C and Pt-Sn/C electrocatalysts for ethanol electrooxidation

OpenAIRE

Ribadeneira, R. E.; Hoyos, B. A.

2010-01-01

In the present study, we examined the effect of adding nickel to Pt-Ru and Pt-Sn catalysts for ethanol electrooxidation. The alcohol-reduction process with ethylene glycol was used to prepare ten electrocatalysts. These were microchemically and physically characterized by EDX and XRD analysis. The electrocatalysts were evaluated at mini-electrodes with cyclic voltammetry at 25 and 50 °C in sulfuric acid and ethanol solutions, and as anodes in fuel cell tests. Nickel addition to Pt-Ru mixtures...

Synthesis and Electrocatalytic Performance of Multi-Component Nanoporous PtRuCuW Alloy for Direct Methanol Fuel Cells

Directory of Open Access Journals (Sweden)

Xiaoting Chen

2015-06-01

Full Text Available We have prepared a multi-component nanoporous PtRuCuW (np-PtRuCuW electrocatalyst via a combined chemical dealloying and mechanical alloying process. The X-ray diffraction (XRD, transmission electron microscopy (TEM and electrochemical measurements have been applied to characterize the microstructure and electrocatalytic activities of the np-PtRuCuW. The np-PtRuCuW catalyst has a unique three-dimensional bi-continuous ligament structure and the length scale is 2.0 ± 0.3 nm. The np-PtRuCuW catalyst shows a relatively high level of activity normalized to mass (467.1 mA mgPt−1 and electrochemically active surface area (1.8 mA cm−2 compared to the state-of-the-art commercial PtC and PtRu catalyst at anode. Although the CO stripping peak of np-PtRuCuW 0.47 V (vs. saturated calomel electrode, SCE is more positive than PtRu, there is a 200 mV negative shift compared to PtC (0.67 V vs. SCE. In addition, the half-wave potential and specific activity towards oxygen reduction of np-PtRuCuW are 0.877 V (vs. reversible hydrogen electrode, RHE and 0.26 mA cm−2, indicating a great enhancement towards oxygen reduction than the commercial PtC.

High-temperature electrochemical characterization of Ru core Pt shell fuel cell catalyst

Energy Technology Data Exchange (ETDEWEB)

Bokach, D.; Fuente, J.L.G. de la; Tsypkin, M.; Ochal, P.; Tunold, R.; Sunde, S.; Seland, F. [Department of Materials Science and Engineering, Norwegian University of Science and Technology (NTNU), Sem Saelands veg 12, N-7491 Trondheim (Norway); Endsjoe, I.C. [Washington Mills AS, NO-7300 Orkanger (Norway)

2011-12-15

The electrooxidation of methanol was studied at elevated temperature and pressure by cyclic voltammetry and constant potential experiments at real fuel cell electrocatalysts. Ruthenium core and platinum shell nanoparticles were synthesized by a sequential polyol route, and characterized electrochemically by CO stripping at room temperature to quickly confirm the structure of the synthesized core-shell structure as compared to pure commercial Pt/C and Pt-Ru/C alloy catalysts. A significant promotional effect of Pt decorated Ru cores in the methanol oxidation was found at elevated temperatures and rather high-electrode potentials. A negative potential shift of the methanol oxidation peak is observed for the Ru rate at Pt/C core-shell catalyst at moderate temperatures, while a significant shift to positive potentials of the methanol oxidation peak occurs for Pt/C catalysts. The onset potential for methanol oxidation is lowered some 200 mV from room temperature and up to 120 C for all electrocatalysts, indicating that it is the thermal activity of water adsorption that dictates the onset potential. Direct methanol fuel cell experiments showed only small performance differences between Ru rate at Pt/C and Pt/C anode electrocatalysts, suggesting the necessity of render possible the formation of surface oxygen species at lower electrode potentials. (Copyright copyright 2011 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Synthesis and characterization of PtRuMo/C nanoparticle electrocatalyst for direct ethanol fuel cell

Energy Technology Data Exchange (ETDEWEB)

Wang, Zhen-Bo; Yin, Ge-Ping [Department of Applied Chemistry, Harbin Institute of Technology, Harbin 150001 (China); Lin, Yong-Ge [Department of Chemistry, University of Puerto Rico, Rio Piedras Campus, San Juan, PR 00931 (United States)

2007-07-10

This research aims at enhancement of the performance of anodic catalysts for the direct ethanol fuel cell (DEFC). Two distinct DEFC nanoparticle electrocatalysts, PtRuMo/C and PtRu/C, were prepared and characterized, and one glassy carbon working electrode for each was employed to evaluate the catalytic performance. The cyclic-voltammetric, chronoamperometric, and amperometric current-time measurements were done in the solution 0.5 mol L{sup -1} CH{sub 3}CH{sub 2}OH and 0.5 mol L{sup -1} H{sub 2}SO{sub 4}. The composition, particle sizes, lattice parameters, morphology, and the oxidation states of the metals on nanoparticle catalyst surfaces were determined by energy dispersive analysis of X-ray (EDAX), X-ray diffraction (XRD), transmission electron micrographs (TEM) and X-ray photoelectron spectrometer (XPS), respectively. The results of XRD analysis showed that both PtRuMo/C and PtRu/C had a face-centered cubic (fcc) structure with smaller lattice parameters than that of pure platinum. The typical particle sizes were only about 2.5 nm. Both electrodes showed essentially the same onset potential as shown in the CV for ethanol electrooxidation. Despite their comparable active specific areas, PtRuMo/C was superior to PtRu/C in respect of the catalytic activity, durability and CO-tolerance. The effect of Mo in the PtRuMo/C nanoparticle catalyst was illustrated with a bifunctional mechanism, hydrogen-spillover effect and the modification on the Pt electronic states. (author)

Measurement of the Ru surface content of electrodeposited PtRu electrodes with the electrochemical quartz crystal microbalance: implications for methanol and CO electrooxidation

NARCIS (Netherlands)

Frelink, T.; Visscher, W.; Veen, van J.A.R.

1996-01-01

To obtain the surface content of Ru in rough electrocodeposited PtRu electrodes, the mass change of a Pt electrode during Ru deposition was measured with the electrochemical quartz crystal microbalance (EQCMB). It is shown that there is a correlation between the potential of the surface oxide

Electrocatalytic oxidation of methanol on (Pb) lead modified by Pt, Pt-Ru and Pt-Sn microparticles dispersed into poly(o-phenylenediamine) film

Energy Technology Data Exchange (ETDEWEB)

Golikand, Ahmad Nozad; Maragheh, Mohammad Ghannadi; Irannejad, Leila [Jaber Ibn Hayan Research Lab., Atomic Energy Organization of Iran (AEOI), Tehran (Iran); Golabi, Seyed Mehdi [Electroanalytical Chemistry Lab., Faculty of Chemistry, University of Tabriz, Tabriz (Iran)

2005-08-18

The electrocatalytic oxidation of methanol at a (Pb) lead electrode modified by Pt, Pt-Ru and Pt-Sn microparticles dispersed into poly(o-phenylenediamine) (PoPD) film has been investigated using cyclic voltammetry as analytical technique and 0.5M sulfuric acid as supporting electrolyte. It has been shown that the presence of PoPD film increases considerably the efficiency of deposited Pt and Pt alloys microparticles toward the electrocatalytic oxidation of methanol. The catalytic activity of Pt particles is further enhanced when Ru and especially Sn, is co-deposited in the polymer film. The effects of various parameters such as concentration of methanol, medium temperature as well as the long term stability of modified electrodes have also been investigated. (author)

Diethyl Ether Production during Catalytic Dehydration of Ethanol over Ru- and Pt- modified H-beta Zeolite Catalysts.

Science.gov (United States)

Kamsuwan, Tanutporn; Praserthdam, Piyasan; Jongsomjit, Bunjerd

2017-01-01

In the present study, the catalytic dehydration of ethanol over H-beta zeolite (HBZ) catalyst with ruthenium (Ru-HBZ) and platinum (Pt-HBZ) modification was investigated. Upon the reaction temperature between 200 and 400°C, it revealed that ethanol conversion and ethylene selectivity increased with increasing temperature for both Ru and Pt modification. At lower temperature (200 to 250°C), diethyl ether (DEE) was the major product. It was found that Ru and Pt modification on HBZ catalyst can result in increased DEE yield at low reaction temperature due to increased ethanol conversion without a significant change in DEE selectivity. By comparing the DEE yield of all catalysts in this study, the Ru-HBZ catalyst apparently exhibited the highest DEE yield (ca. 47%) at 250°C. However, at temperature from 350 to 400°C, the effect of Ru and Pt was less pronounced on ethylene yield. With various characterization techniques, the effects of Ru and Pt modification on HBZ catalyst were elucidated. It revealed that Ru and Pt were present in the highly dispersed forms and well distributed in the catalyst granules. It appeared that the weak acid sites measured by NH 3 temperature-programmed desorption technique also decreased with Ru and Pt promotion. Thus, the increased DEE yields with the Ru and Pt modification can be attributed to the presence of optimal weak acid sites leading to increased intrinsic activity of the catalysts. It can be concluded that the modification of Ru and Pt on HBZ catalyst can improve the DEE yields by ca. 10%.

Improvement on electrochemical performance by partial replacement of Ru@Pt core-shell nanocatalyst by temperature modification

International Nuclear Information System (INIS)

Chang, Chih-Juei; Lin, Liang-You; Tseng, Fan-Gang

2014-01-01

In this paper, the homemade open-loop reduction system (OLRS), and redox transmetalation method were utilized to produce the core-shell Ru (ruthenium)/Pt (platinum) catalysts on the carbon cloth (CC) for direct methanol fuel cell (DMFC) application. By adjusting pH value and heating to proper temperature of the ionized reduction environment, Pt 4+ can be first converted into Pt 2+ to allow partial Ru replacement with Pt by redox transmetalation and produce Ru@Pt core-shell nanostructures[1]. And we change the reduction temperature to see how it affects the efficiency of the DMFC. The scanning electron microscopic (SEM) top-view micrographs showing that the apparent Ru@Pt nanoparticles successfully deposited on both the inner and outer surfaces of the hydrophilically-treated CC. At high SEM magnification, the small size and high-density distribution of the Ru@Pt nanoparticles were clearly observed on the hydrophilically-treated CC, and much more Pt@Ru catalyst deposit on the CC surface with the sample of 80 °C. The electrosorption charges of hydrogen ion (Q H ) and the peak current density (I P ) of the samples in the cyclic voltammetry (CV) curves. The magnitude of peak current density is positive correlation to the temperature. However, the CO tolerance, indicated that the better CO tolerance contributed to the less Pt replace on Ru cluster, which allow the Ru oxidizing CO to CO 2 efficiently, is negative correlation-- to the temperature. The sample of 50 °C shows the better combination catalyst efficiency between the CO tolerance and the electrochemical performance

PtRu catalysts supported on heteropolyacid and chitosan functionalized carbon nanotubes for methanol oxidation reaction of fuel cells.

Science.gov (United States)

Cui, Zhiming; Li, Chang Ming; Jiang, San Ping

2011-09-28

A simple self-assembly approach has been developed to functionalize carbon nanotubes (CNTs) with chitosan (CS) and heteropolyacids (HPAs) of phosphomolybdic acid (H(3)PMo(12)O(40), HPMo) and phosphotungstic acid (H(3)PW(12)O(40), HPW). The non-covalent functionalization method, which introduces homogenous surface functional groups with no detrimental effect on graphene structures of CNTs, can be carried out at room temperature without the use of corrosive acids. The PtRu nanoparticles supported on HPAs-CS-CNTs have a uniform distribution and much smaller size as compared to those of the PtRu nanoparticles supported on conventional acid treated CNTs (PtRu/AO-CNTs). The onset and peak potentials for CO(ad) oxidation on PtRu/HPAs-CS-CNTs catalysts are more negative than those on PtRu/AO-CNTs, indicating that HPAs facilitate the electro-oxidation of CO. The PtRu/HPMo-CS-CNTs catalyst has a higher electrocatalytic activity for methanol oxidation and higher tolerance toward CO poisoning than PtRu/HPW-CS-CNTs. The better electrocatalytic enhancement of HPMo on the PtRu/HPAs-CS-CNTs catalyst is most likely related to the fact that molybdenum-containing HPAs such as HPMo have more labile terminal oxygen to provide additional active oxygen sites while accelerating the CO and methanol oxidation in a similar way to that of Ru in the PtRu binary alloy system.

Investigation of ethanol electrooxidation on a Pt-Ru-Ni/C catalyst for a direct ethanol fuel cell

Energy Technology Data Exchange (ETDEWEB)

Wang, Zhen-Bo; Yin, Ge-Ping; Zhang, Jian; Sun, Ying-Chao; Shi, Peng-Fei [Department of Applied Chemistry, Harbin Institute of Technology, Harbin (China 150001)

2006-09-29

This research is aimed to improve the utilization and activity of anodic alloy catalysts and thus to lower the contents of noble metals and the catalyst loading on anodes for ethanol electrooxidation. The DEFC anodic catalysts, Pt-Ru-Ni/C and Pt-Ru/C, were prepared by a chemical reduction method. Their performances were tested by using a glassy carbon working electrode and cyclic voltammetric curves, chronoamperometric curves and half cell measurement in a solution of 0.5molL{sup -1} CH{sub 3}CH{sub 2}OH and 0.5molL{sup -1} H{sub 2}SO{sub 4}. The composition of the Pt-Ru-Ni and Pt-Ru surface particles were determined by EDAX analysis. The particle size and lattice parameter of the catalysts were determined by means of X-ray diffraction (XRD). XRD analysis showed that both of the catalysts exhibited face centered cubic structures and had smaller lattice parameters than a Pt-alone catalyst. Their particle sizes were small, about 4.5nm. No significant differences in the ethanol electrooxidation on both electrodes were found using cyclic voltammetry, especially regarding the onset potential for ethanol electrooxidation. The electrochemically active specific areas of the Pt-Ru-Ni/C and Pt-Ru/C catalysts were almost the same. But, the catalytic activity of the Pt-Ru-Ni/C catalyst was higher for ethanol electrooxidation than that of the Pt-Ru/C catalyst. Their tolerance to CO formed as one of the intermediates of ethanol electrooxidation, was better than that of the Pt-Ru/C catalyst. (author)

Synthesis and characterization of PtRu/C catalysts obtained by colloidal and deposition methods for fuel cell applications

Directory of Open Access Journals (Sweden)

Egberto Gomes Franco

2005-06-01

Full Text Available The purpose of this investigation was to compare catalysts produced by the Bönnemann - colloidal method (PtRu (B1 and PtRu (B2, and those produced by the spontaneous deposition method (PtRu (SD. The catalysts produced by both methods had good electrochemical behavior for methanol oxidation for proton exchange membrane fuel cell applications. The structure of the catalyst was examined by transmission electron microscopy (TEM. Energy dispersive spectroscopic analysis (EDS was used to determine the semi-quantitative composition of the catalysts, and the electrochemical behavior was determined by cyclic voltammetry (CV. The diffractograms of the binary catalysts revealed platinum and ruthenium as the only crystalline phases, as per ICDD data base. The PtRu (B1 catalyst, treated in a reducing atmosphere, has the same structure as PtRu (B2, treated in an oxidising/reducing atmosphere, except that the crystallite size was around 1.7 nm for PtRu (B1 instead of 9.9 nm for PtRu (B2. The catalysts PtRu (B2 and PtRu (SD showed similar cyclic voltammetric behavior, which was better than that of PtRu (B1. Both methods are suitable for the production of electrocatalysts for fuel cell applications. The colloidal method is more expensive than the deposition method, but the former permits the production of ternary and quaternary catalyst systems with enhanced CO tolerance.

Preparation of Pt Ru/C + rare earths by the method of reduction by alcohol for the electro-oxidation of ethanol

International Nuclear Information System (INIS)

Tusi, M.M.; Rodrigues, R.M.S.; Spinace, E.V.; Oliveira Neto, A.

2010-01-01

PtRu/C electrocatalyst was prepared in a single step, while that PtRu/85%C-15%Ce, PtRu/85%C-15%La, PtRu/85%C-15%Nd and PtRu/85%C-15%Er electrocatalyst were prepared in a two step. In the first step a Carbon Vulcan XC72 + rare earth supports were prepared. In the second step PtRu electrocatalyst were prepared by an alcohol-reduction process using ethylene glycol as solvent and reducing agent and supported on Vulcan XC72 + earth rare. The obtained electrocatalysts were characterized by EDAX, XRD and chronoamperometry. The electro-oxidation of ethanol was studied by chronoamperometry at room temperature. PtRu/85%C- 15%Ce electrocatalyst showed a significant increase of performance for ethanol oxidation compared to PtRu/C electrocatalyst. (author)

Mixed phase Pt-Ru catalyst for direct methanol fuel cell anode by flame aerosol synthesis

DEFF Research Database (Denmark)

Chakraborty, Debasish; Bischoff, H.; Chorkendorff, Ib

2005-01-01

A spray-flame aerosol catalyzation technique was studied for producing Pt-Ru anode electrodes for the direct methanol fuel cell. Catalysts were produced as aerosol nanoparticles in a spray-flame reactor and deposited directly as a thin layer on the gas diffusion layer. The as-prepared catalyst wa......Ru1/Vulcan carbon. The kinetics of methanol oxidation on the mixed phase catalyst was also explored by electrochemical impedance spectroscopy. (c) 2005 The Electrochemical Society.......A spray-flame aerosol catalyzation technique was studied for producing Pt-Ru anode electrodes for the direct methanol fuel cell. Catalysts were produced as aerosol nanoparticles in a spray-flame reactor and deposited directly as a thin layer on the gas diffusion layer. The as-prepared catalyst...... was found to be a mixture of nanocrystalline, mostly unalloyed Pt and an amorphous phase mostly of Ru and to a lesser extent of Pt oxides on top of the crystalline phase. The flame-produced Pt1Ru1 demonstrated similar onset potential but similar to 60% higher activity compared to commercially available Pt1...

Highly effective and CO-tolerant PtRu electrocatalysts supported on poly(ethyleneimine) functionalized carbon nanotubes for direct methanol fuel cells

International Nuclear Information System (INIS)

Cheng, Yi; Jiang, San Ping

2013-01-01

A highly efficient and CO tolerant PtRu electrocatalysts supported on amino-rich, cationic poly(ethyleneimine) polyelectrolyte functionalized multi-walled carbon nanotubes (PtRu/PEI-MWCNTs) has been developed. The catalysts were characterized by thermogravimetric analysis, Raman spectroscopy, cyclic voltammograms, CO stripping, chronoamperometry, transmission electron microscopy (TEM) and X-ray diffraction (XRD). The PtRu particles with average size ∼2.5 nm are well dispersed on PEI-MWCNTs. The peak current for the methanol oxidation reaction on 40% PtRu/PEI-MWCNTs is 636mAmg Pt −1 , 5.7 times higher than 112mA mg Pt −1 measured on the 40% PtRu supported on acid treated MWCNTs (PtRu/AO-MWCNTs) under identical conditions. PtRu/PEI-MWCNTs catalysts exhibit a superior electrocatalytic activity and stability for the methanol oxidation reaction due to its high tolerance toward CO poisoning as compared with PtRu/AO-MWCNTs for direct methanol fuel cells

Characterization and evaluation of Pt-Ru catalyst supported on multi-walled carbon nanotubes by electrochemical impedance

Energy Technology Data Exchange (ETDEWEB)

Ocampo, A.L.; Miranda-Hernandez, M.; Sebastian, P.J. [Centro de Investigacion en Energia-UNAM, Temixco, 62580 Morelos (Mexico); Morgado, J.; Montoya, J.A. [IMP, Eje Central Lazaro Cardenas 152, 07730 D.F. Mexico (Mexico)

2006-10-06

In this work the authors present the results of a systematic characterization and evaluation of the carbon nanotube supported Pt-Ru (Pt-Ru/CNT) for its use as methanol oxidation catalyst. Its activity was compared with that of Pt and Pt-Ru catalysts supported on Vulcan and synthesized from carbonyl precursors, and another commercial Pt-Ru catalyst. The cyclic voltammetry, CO stripping and electrochemical impedance techniques were employed to determine the electrocatalytic activity of the catalysts. The electrochemical studies were performed in 0.5M H{sub 2}SO{sub 4} containing different concentrations of methanol (0.05-1M). The results showed a noticeable influence of the catalyst support (CNT) on the performance of the catalyst for CO oxidation. The electrochemical impedance studies allowed us to separate the different steps in the methanol oxidation reaction and to control these steps or reactions by varying the applied potential and the methanol concentration. At low methanol concentration and potentials the de-hydrogenation of methanol predominated. But, at high potential and methanol concentrations, the CO oxidation predominated. These results allowed us to clearly describe at what potential and concentration ranges the bi-functional effect of Ru becomes evident. Our results indicated that the CO oxidation occurs both on Pt and Ru. Compared to other catalysts, Pt-Ru supported on carbon nanotubes showed superior catalytic activity for CO and methanol oxidation. (author)

Derivation of the liquidus surface projection for the Al-Pt-Ru system from as-cast samples

CSIR Research Space (South Africa)

Prins, SN

2005-11-10

Full Text Available -rich corner. Two new ternary phases similar to Ru12Pt15Al73 and similar to Ru18Pt28Al64 were observed near the Al-corner. The similarity to Ru12Pt15Al73 phase has a primitive cubic structure, lattice parameter of similar to 0.7721 nm, and is stable to room...

Electrooxidation of ethanol on Pt and PtRu surfaces investigated by ATR surface-enhanced infrared absorption spectroscopy

Energy Technology Data Exchange (ETDEWEB)

Silva, Marcio F.; Camara, Giuseppe A., E-mail: giuseppe.silva@ufms.br [Departamento de Quimica, Universidade Federal do Mato Grosso do Sul, Campo Grande-MS (Brazil); Batista, Bruno C.; Boscheto, Emerson [Instituto de Quimica de Sao Carlos, Universidade de Sao Paulo, Sao Carlos-SP, (Brazil); Varela, Hamilton, E-mail: varela@iqsc.usp.br [Ertl Center for Electrochemistry and Catalysis, Gwangju Institute of Science and Technology (GIST), Gwangju (Korea, Republic of)

2012-05-15

Herein, it was investigated for the first time the electro-oxidation of ethanol on Pt and PtRu electrodeposits in acidic media by using in situ surface enhanced infrared absorption spectroscopy with attenuated total reflection (ATR-SEIRAS). The experimental setup circumvents the weak absorbance signals related to adsorbed species, usually observed for rough, electrodeposited surfaces, and allows a full description of the CO coverage with the potential for both catalysts. The dynamics of adsorption-oxidation of CO was accessed by ATR-SEIRAS experiments (involving four ethanol concentrations) and correlated with expressions derived from a simple kinetic model. Kinetic analysis suggests that the growing of the CO adsorbed layer is nor influenced by the presence of Ru neither by the concentration of ethanol. The results suggest that the C-C scission is not related to the presence of Ru and probably happens at Pt sites. (author)

Electrooxidations of ethanol, acetaldehyde and acetic acid using PtRuSn/C catalysts prepared by modified alcohol-reduction process

Energy Technology Data Exchange (ETDEWEB)

Wu, Gang [Department of Chemical Engineering, University of South Carolina, Columbia, SC 29208 (United States); Swaidan, Raja [Department of Chemical Engineering, Cooper Union, New York, NY 10003 (United States); Cui, Guofeng [School of Chemistry and Chemical Engineering, Sun-Yat Sen University, Guangzhou 510275 (China)

2007-10-11

Well-dispersed ternary PtRuSn catalysts of various atomic ratios (60:30:10, 60:20:20 and 60:10:30) were deposited onto carbon using modified alcohol-reduction process for electrochemical oxidation of ethanol. The alloy phase structure and surface morphology for each variation of the PtRuSn/C catalysts were determined by XRD and HRTEM. In order to evaluate the contributions of Ru and Sn in the different stages of ethanol oxidation, electrochemical oxidations of adsorbed CO, ethanol, acetaldehyde and acetic acid were performed on each PtRuSn/C catalyst. The results indicated that the Ru-rich PtRuSn/C catalyst (60:30:10) exhibited the lowest onset potential for the electrooxidations of adsorbed CO, ethanol and acetaldehyde, revealing that the removal through oxidation of the intermediate C{sub 1} and C{sub 2} species from Pt sites is primarily attributed to the Ru and Pt{sub 3}Sn alloy structures. However, for the overall oxidation of ethanol, the Sn-rich PtRuSn/C catalyst (60:10:30) containing PtSn phase and SnO{sub 2} structure is favorable for the activation of C-C bond breaking, thereby generating higher current density (mass activity) at higher potentials. Moreover, in the electrooxidation of acetic acid, a remarkable improvement for oxidizing acetic acid to C{sub 1} species was observed in the Sn-rich PtRuSn/C catalyst (60:10:30), while the Ru-rich PtRuSn/C catalyst (60:30:10) was almost incapable of breaking the C-C bond to further oxidize acetic acid. The possible reasons for the different reactivities on the studied PtRuSn/C catalysts were discussed based on the removal of intermediates and activation of the C-C bonds on the different surfaces. (author)

Low Pt content Pt-Ru-Ir-Sn quaternary catalysts for anodic methanol oxidation in DMFC

Energy Technology Data Exchange (ETDEWEB)

Neburchilov, Vladimir; Wang, Haijiang; Zhang, Jiujun [Institute for Fuel Cell Innovation, National Research Council (Canada)

2007-07-15

In this communication we report our research work on low Pt content Pt-Ru-Ir-Sn quaternary catalysts for use in DMFC anodes. The carbon-supported quaternary metal alloy catalyst was synthesized according to the solution reduction method and was deposited onto a carbon fiber paper or a carbon aerogel nanofoam to form the anode for direct methanol fuel cells. The Pt loading of the electrode is 0.1 mg/cm{sup 2}. The testing results from a three-electrode electrochemical cell show that the simultaneous use of higher Ir (25-35 wt.%) and Sn (10 wt.%) content gives satisfactory stability and higher activity for methanol oxidation than the commercially available E-TEK anode (80%[0.5Pt 0.5Ru]/C on carbon cloth). Energy dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), scanning electron microscope (SEM), and Bruner-Emmett-Teller method (BET) measurements were carried out to characterize the composition, structure, morphology, and surface area of the developed catalysts. (author)

Carbon-Supported PtRuMo Electrocatalysts for Direct Alcohol Fuel Cells

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José L.G. Fierro

2013-10-01

Full Text Available The review article discusses the current status and recent findings of our investigations on the synthesis and characterization of carbon-supported PtRuMo electrocatalysts for direct alcohol fuel cells. In particular, the effect of the carbon support and the composition on the structure, stability and the activity of the PtRuMo nanoparticles for the electrooxidation of CO, methanol and ethanol have been studied. Different physicochemical techniques have been employed for the analysis of the catalysts structures: X-ray analytical methods (XRD, XPS, TXRF, thermogravimetry (TGA and transmission electron microscopy (TEM, as well as a number of electrochemical techniques like CO adsorption studies, current-time curves and cyclic voltammetry measurements. Furthermore, spectroscopic methods adapted to the electrochemical systems for in situ studies, such as Fourier transform infrared spectroscopy (FTIRS and differential electrochemical mass spectrometry (DEMS, have been used to evaluate the oxidation process of CO, methanol and ethanol over the carbon-supported PtRuMo electrocatalysts.

Effects of the Electrodeposition Time in the Synthesis of Carbon-Supported Pt(Cu and Pt-Ru(Cu Core-Shell Electrocatalysts for Polymer Electrolye Fuel Cells

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Griselda Caballero-Manrique

2016-08-01

Full Text Available Pt(Cu/C and Pt-Ru(Cu/C electrocatalysts with core-shell structure supported on Vulcan Carbon XC72R have been synthesized by potentiostatic deposition of Cu nanoparticles on the support, galvanic exchange with Pt and spontaneous deposition of Ru species. The duration of the electrodeposition time of the different species has been modified and the obtained electrocatalysts have been characterized using electrochemical and structural techniques. The High Resolution Transmission Electron Microscopy (HRTEM, Fast Fourier Transform (FFT and Energy Dispersive X-ray (EDX microanalyses allowed the determining of the effects of the electrodeposition time on the nanoparticle size and composition. The best conditions identified from Cyclic Voltammetry (CV corresponded to onset potentials for CO and methanol oxidation on Pt-Ru(Cu/C of 0.41 and 0.32 V vs. the Reversible Hydrogen Electrode (RHE, respectively, which were smaller by about 0.05 V than those determined for Ru-decorated commercial Pt/C. The CO oxidation peak potentials were about 0.1 V smaller when compared to commercial Pt/C and Pt-Ru/C. The positive effect of Cu was related to its electronic effect on the Pt shells and also to the generation of new active sites for CO oxidation. The synthesis conditions to obtain the best performance for CO and methanol oxidation on the core-shell Pt-Ru(Cu/C electrocatalysts were identified. When compared to previous results in literature for methanol, ethanol and formic acid oxidation on Pt(Cu/C catalysts, the present results suggest an additional positive effect of the deposited Ru species due to the introduction of the bifunctional mechanism for CO oxidation.

Ni2P Makes Application of the PtRu Catalyst Much Stronger in Direct Methanol Fuel Cells.

Science.gov (United States)

Chang, Jinfa; Feng, Ligang; Liu, Changpeng; Xing, Wei

2015-10-12

PtRu is regarded as the best catalyst for direct methanol fuel cells, but the performance decay resulting from the loss of Ru seriously hinders commercial applications. Herein, we demonstrated that the presence of Ni2 P largely reduces Ru loss, which thus makes the application of PtRu much stronger in direct methanol fuel cells. Outstanding catalytic activity and stability were observed by cyclic voltammetry. Upon integrating the catalyst material into a practical direct methanol fuel cell, the highest maximum power density was achieved on the PtRu-Ni2P/C catalyst among the reference catalysts at different temperatures. A maximum power density of 69.9 mW cm(-2) at 30 °C was obtained on PtRu-Ni2P/C, which is even higher than the power density of the state-of-the-art commercial PtRu catalyst at 70 °C (63.1 mW cm(-2)). Moreover, decay in the performance resulting from Ru loss was greatly reduced owing to the presence of Ni2 P, which is indicative of very promising applications. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fabrication and performance of the Pt-Ru/Ni-P/FTO counter electrode for dye-sensitized solar cells

International Nuclear Information System (INIS)

Ma, Huanmei; Tian, Jianhua; Bai, Shuming; Liu, Xiaodong; Shan, Zhongqiang

2014-01-01

Highlights: • Pt-Ru alloy acts as the catalyst of counter electrodes in dye-sensitized solar cell. • Ni-P/FTO (fluorine-doped SnO 2 ) substrate is prepared by electroless plating method. • Pt-Ru/Ni-P/FTO counter electrode is fabricated by electrodeposition method. • The Ni-P sublayer improves the conductivity and light reflectance of FTO substrate. • The cell with Pt-Ru/Ni-P/FTO counter electrode exhibits an improved efficiency. - Abstract: In this paper, Pt-Ru/Ni-P/FTO has been designed and fabricated as the counter electrode for dye-sensitized solar cells. The Pt-Ru catalytic layer and Ni-P alloy sublayer are prepared by traditional electrodeposition method and a simple electroless plating method, respectively, and the preparation conditions have been optimized. The scanning electron microscopy (SEM) images show that the Pt-Ru particles are evenly distributed on FTO and Ni-P/FTO substrate. By X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS), it is confirmed that the Ni-P amorphous alloy has been formed, and no other compounds involved Ni and P have been formed. The electrochemical measurement results reveal that the Pt-Ru electrode has higher catalytic activity and stability towards tri-iodine reduction reaction than Pt electrode in the organic medium. The Ni-P sublayer deposited on FTO glasses increases the conductivity and light-reflection ability of the counter electrode, and this contributes to lowering the inner resistance of the cell and improving the light utilization efficiency. Through the photovoltaic test, it is confirmed that the energy conversion efficiency of a single DSSC with the optimized Pt-Ru/Ni-P/FTO counter electrode is increased by 29% compared with that of the cell based on the Pt/FTO counter electrode under the same conditions

In situ Ru K-edge EXAFS of CO adsorption on a Ru modified Pt/C fuel cell catalyst

International Nuclear Information System (INIS)

Rose, Abigail; Bilsborrow, Robert; King, Colin R.; Ravikumar, M.K.; Qian Yangdong; Wiltshire, Richard J.K.; Crabb, Eleanor M.; Russell, Andrea E.

2009-01-01

The Ru-CO bond of CO adsorbed on a Ru modified Pt/C fuel cell catalyst has been directly probed by in situ EXAFS at the Ru K-edge, providing evidence of a CO:metal surface atom ratio greater than 1:1 and that CO is adsorbed at bridging sites associated with Ru atoms at the surface of the catalyst nanoparticles. This result illustrates the limitations of single crystal models as representations of the bonding of adsorbed species at nanoparticle surfaces.

Radiolytic Synthesis of Pt-Ru Catalysts Based on Functional Polymer-Grafted MWNT and Their Catalytic Efficiency for CO and MeOH

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Dae-Soo Yang

2011-01-01

Full Text Available Pt-Ru catalysts based on functional polymer-grafted MWNT (Pt-Ru@FP-MWNT were prepared by radiolytic deposition of Pt-Ru nanoparticles on functional polymer-grafted multiwalled carbon nanotube (FP-MWNT. Three different types of functional polymers, poly(acrylic acid (PAAc, poly(methacrylic acid (PMAc, and poly(vinylphenyl boronic acid (PVPBAc, were grafted on the MWNT surface by radiation-induced graft polymerization (RIGP. Then, Pt-Ru nanoparticles were deposited onto the FP-MWNT supports by the reduction of metal ions using γ-irradiation to obtain Pt-Ru@FP-MWNT catalysts. The Pt-Ru@FP-MWNT catalysts were then characterized by XRD, XPS, TEM ,and elemental analysis. The catalytic efficiency of Pt-Ru@FP-MWNT catalyst was examined for CO stripping and MeOH oxidation for use in a direct methanol fuel cell (DMFC. The Pt-Ru@PVPBAc-MWNT catalyst shows enhanced activity for electro-oxidation of CO and MeOH oxidation over that of the commercial E-TEK catalyst.

Novel Pt-Ru nanoparticles formed by vapour deposition as efficient electrocatalyst for methanol oxidation

International Nuclear Information System (INIS)

Sivakumar, Pasupathi; Tricoli, Vincenzo

2006-01-01

The methods developed and described in paper-part I are employed to prepare nanometer size Pt-Ru particles on a Vulcan[reg] XC72R substrate with controlled metal loading. Transmission Electron Microscopy (TEM) confirmed uniform particles size (average diameter 2 nm) and homogeneous dispersion of the particles over the substrate. Energy Dispersive X-ray absorption (EDX) analysis confirmed the compositional homogeneity. The catalytic activity of these supported nanoparticles with regard to methanol electrooxidation is investigated using cyclic voltammetry (CV), chronoamperometry (CA) and CO-stripping voltammetry techniques at temperatures between 25 and 60 deg. C. Such investigation concerns supported catalysts prepared with ca. 10 and 18 wt.% overall metal loading (Pt + Ru) onto the Vulca[reg] XC72R substrate. Comparative testing of our catalysts and a commercial Pt-Ru/Vulcan reveals markedly superior activity for our catalysts. In fact, we observe for the latter a five-fold increase of the oxidation current as compared to a commercial Pt-Ru/Vulcan with equal metal loading. One of the reasons for the greater activity is found to be the very high dispersion of the metals over the substrate, i.e. the large surface area of the active phase. Other reasons are plausibly ascribable to the varied Pt/Ru composition and/or reduced presence of contaminants at the catalyst surface

Electrocatalytic Activity for CO, MeOH, and EtOH Oxidation on the Surface of Pt-Ru Nanoparticles Supported by Metal Oxide

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Kwang-Sik Sim

2011-01-01

Full Text Available This paper describes the electrocatalytic activity for CO, MeOH, and EtOH oxidation on the surface of Pt-Ru nanoparticles supported by metal oxide (Nb-TiO2-H prepared for use in a fuel cell. To prepare Nb-TiO2-supported Pt-Ru nanoparticles, first, the Nb-TiO2 supports were prepared by sol-gel reaction of titanium tetraisopropoxide with a small amount of the niobium ethoxide in polystyrene (PS colloids. Second, Pt-Ru nanoparticles were then deposited by chemical reduction of the Pt4+ and Ru3+ ions onto Nb-TiO2 supports (Pt-Ru@Nb-TiO2-CS. Nb element was used to reduce electrical resistance to facilitate electron transport during the electrochemical reactions on a fuel cell electrode. Finally, the Pt-Ru@Nb-TiO2-H catalysts were formed by the removal of core-polystyrene ball from Pt-Ru@TiO2-CS at 500∘C. The successfully prepared Pt-Ru electrocatalysts were confirmed via TEM, XPS, and ICP analysis. The electrocatalytic efficiency of Pt-Ru nanoparticles was evaluated via CO, MeOH, and EtOH oxidation for use in a direct methanol fuel cell (DMFC. As a result, the Pt-Ru@Nb-TiO2-H electrodes showed high electrocatalytic activity for the electrooxidation of CO, MeOH, and EtOH.

SiO2 decoration dramatically enhanced the stability of PtRu electrocatalysts with undetectable deterioration in fuel cell performance

Science.gov (United States)

Yu, Xinxin; Xu, Zejun; Yang, Zehui; Xu, Sen; Zhang, Quan; Ling, Ying; Zhang, Yunfeng; Cai, Weiwei

2018-06-01

Prevention of Ru dissolution is essential for steady CO tolerance of anodic electrocatalysts in direct methanol fuel cells. Here, we demonstrate a facile way to stabilize Ru atoms by decorating commercial CB/PtRu with SiO2, which shows a six-fold higher stability and similar activity toward a methanol oxidation reaction leading to no discernible degradation in fuel cell performance compared to commercial CB/PtRu electrocatalysts. The higher stability and stable CO tolerance of SiO2-decorated electrocatalysts originate from the SiO2 coating, since Ru atoms are partially ionized during SiO2 decorating, resulting in difficulties in dissolution; while, in the case of commercial CB/PtRu, the dissolved Ru offers active sites for Pt coalescences and CO species resulting in the rapid decay of the electrochemical surface area and fuel cell performance. To the best of our knowledge, this is the first study about the stabilization of Ru atoms by SiO2. The highest stability is obtained for a PtRu electrocatalyst with negligible effect on the electrochemical properties.

The Effect of PtRuIr Nanoparticle Crystallinity in Electrocatalytic Methanol Oxidation

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Vladimir Linkov

2013-04-01

Full Text Available Two structural forms of a ternary alloy PtRuIr/C catalyst, one amorphous and one highly crystalline, were synthesized and compared to determine the effect of their respective structures on their activity and stability as anodic catalysts in methanol oxidation. Characterization techniques included TEM, XRD, and EDX. Electrochemical analysis using a glassy carbon disk electrode for cyclic voltammogram and chronoamperometry were tested in a solution of 0.5 mol L−1 CH3OH and 0.5 mol L−1 H2SO4. Amorphous PtRuIr/C catalyst was found to have a larger electrochemical surface area, while the crystalline PtRuIr/C catalyst had both a higher activity in methanol oxidation and increased CO poisoning rate. Crystallinity of the active alloy nanoparticles has a big impact on both methanol oxidation activity and in the CO poisoning rate.

Preparation of PtRu/C anode electrocatalysts using gamma radiation for methanol electro-oxidation; Preparacao de eletrocatalisadores PtRu/C utilizando radiacao gama para aplicacao como anodo na oxidacao direta de metanol

Energy Technology Data Exchange (ETDEWEB)

Silva, Dionisio Fortunato da

2006-07-01

Pt Ru/C (carbon-supported Pt Ru nanoparticles) anode electrocatalysts were prepared using radiolytic process (gamma radiation) and tested for methanol electro-oxidation. In this process, water/2-propanol and water/ethylene glycol solutions containing the metallic ions and the carbon support were submitted to gamma radiation under stirring. The water/alcohol ratio (v/v) and the total dose (kGy) were studied. A nominal Pt Ru atomic ratio of 50:50 were used in all experiments. The electrocatalysts were characterized by energy dispersive X-ray analysis (EDX), X-ray diffraction (XRD), transmission electron microscopy (TEM) and cyclic voltammetry (CV). The electro-oxidation of methanol was studied by cyclic voltammetry using the thin porous coating technique. The electrocatalysts prepared in water/2-propanol showed crystallite size in the range of 3-5 nm and Pt Ru atomic ratio of 50:50. The electrocatalysts prepared in water/ethylene glycol showed crystallite size (2-3 nm) smaller than the ones obtained in water/2-propanol, however, the Pt Ru atomic ratios obtained were approximately 80:20, showing that only part of ruthenium ions were reduced. For methanol oxidation the electrocatalytic activity depends on the water/2-propanol and water/ethylene glycol ratio used in the reaction medium. The electrocatalysts prepared in water/2-propanol showed inferior performance to the ones prepared in water/ethylene glycol, which showed similar or superior performances (amperes per gram of platinum) to the commercial electrocatalyst from E-TEK. (author)

Effect of heat treatment on stability of gold particle modified carbon supported Pt-Ru anode catalysts for a direct methanol fuel cell

International Nuclear Information System (INIS)

Li Xiaowei; Liu Juanying; Huang Qinghong; Vogel, Walter; Akins, Daniel L.; Yang Hui

2010-01-01

Carbon supported Au-PtRu (Au-PtRu/C) catalysts were prepared as the anodic catalysts for the direct methanol fuel cell (DMFC). The procedure involved simple deposition of Au particles on a commercial Pt-Ru/C catalyst, followed by heat treatment of the resultant composite catalyst at 125, 175 and 200 o C in a N 2 atmosphere. High-resolution transmission electron microscopy (HR-TEM) measurements indicated that the Au nanoparticles were attached to the surface of the Pt-Ru nanoparticles. We found that the electrocatalytic activity and stability of the Au-PtRu/C catalysts for methanol oxidation is better than that of the PtRu/C catalyst. An enhanced stability of the electrocatalyst is observed and attributable to the promotion of CO oxidation by the Au nanoparticles adsorbed onto the Pt-Ru particles, by weakening the adsorption of CO, which can strongly adsorb to and poison Pt catalyst. XPS results show that Au-PtRu/C catalysts with heat treatment lead to surface segregation of Pt metal and an increase in the oxidation state of Ru, which militates against the dissolution of Ru. We additionally find that Au-PtRu/C catalysts heat-treated at 175 o C exhibit the highest electrocatalytic stability among the catalysts prepared by heat treatment: this observation is explained as due to the attainment of the highest relative concentration of gold and the highest oxidation state of Ru oxides for the catalyst pretreated at this temperature.

Ethanol electrooxidation using Ti/(RuO2)(x) Pt(1-x) electrodes prepared by the polymeric precursor method

Energy Technology Data Exchange (ETDEWEB)

Freitas, R.G.; Marchesi, L.F.Q.P.; Forim, M.R.; Pereira, E.C. [Departamento de Quimica, Universidade Federal de Sao Carlos, Sao Carlos, SP (Brazil); Bulhoes, L.O.S [CENIP, Centro Universitario Central Paulista, Sao Carlos, SP (Brazil); Santos, M.C. [LEMN, Centro de Ciencias Naturais e Humanas, Universidade Federal do ABC, Santo Andre, SP (Brazil); Oliveira, R.T.S., E-mail: robson@icbn.uftm.edu.br [Instituto de Ciencias Biologicas e Naturais, Universidade Federal do Triangulo Mineiro, Uberaba, MG (Brazil)

2011-09-15

This work describes a detailed study of the ethanol electrooxidation on Ti/(RuO{sub 2}){sub (x)}Pt{sub (1-x)} electrodes using several compositions prepared by the polymeric precursor method. The results obtained using cyclic voltammetry and chronoamperometry showed that the best composition of Ti/(RuO{sub 2}){sub (x)}Pt{sub (1-x)} electrodes for CO and ethanol oxidation processes is Ti/(RuO{sub 2}){sub 0.50}Pt{sub 0.50}. On this electrode composition the onset of CO and the ethanol oxidation occurred at 380 mV and 220 mV more negative than on Ti/Pt, respectively. Besides, there was an increase of 2.5-fold in the current density for ethanol electrooxidation under constant potential polarization. The Ti/(RuO{sub 2}){sub 0.50}Pt{sub 0.50}. electrodes produced lower amount of acetic acid compared to Ti/Pt and polycrystalline Pt electrodes using in situ HPLC spectrometric analysis. Also, a non common product from ethanol oxidation could be observed on higher RuO{sub 2} loads: ethyl acetate. Finally, the impedance data showed that Ti/(RuO{sub 2}){sub 0.50}Pt{sub 0.50}. electrode composition had the smallest charge transfer resistance for ethanol oxidation among those compositions investigated. (author)

STUDY OF THE Pt/Ru(0001) INTERFACE

DEFF Research Database (Denmark)

Godowski, P.J.; Li, Zheshen; Bork, J.

2007-01-01

to the different stages of the deposition were analyzed. Up to ca. two adsorbate monolayers, the intensity changes of the peaks indicated layer-by-layer growth mode. The surface core level shifts of Ru and Pt levels were evaluated as -0.33 and -0.476 eV, respectively. The valence band spectra show a rather weak...

Promotion of Pt-Ru/C catalysts driven by heat treated induced surface segregation for methanol oxidation reaction

International Nuclear Information System (INIS)

Wei Yuchen; Liu Chenwei; Chang Weijung; Wang Kuanwen

2011-01-01

Research highlights: → Thermal treatments on the Pt-Ru/C induce different extents of surface segregation. → O 2 treatment results in obvious Ru segregation and formation of RuO 2 . → Catalysts treated in H 2 have the excellent CO de-poisoning ability. → N 2 treatment suppresses the surface Pt depletion and hence promotes the MOR. - Abstract: Carbon supported Pt-Ru/C (1:1) alloy catalysts supplied by E-TEK are widely used for fuel cell research. Heat treatments in various atmospheres are conducted for the promotion of the methanol oxidation reaction (MOR) and the investigation of the structure-activity relationship (SAR) of the catalysts. The alloy structures, surface compositions, surface species, and electro-catalytic activities of the alloy catalysts are characterized by X-ray diffraction (XRD), temperature-programmed reduction (TPR), X-ray photoelectron spectroscopy (XPS), and cyclic voltammetry (CV), respectively. The as-received Pt-Ru/C catalysts have a Ru rich in the inner core and Pt rich on the outer shell structure. Thermal treatments on the catalysts induce Ru surface segregation in different extents and thereby lead to their alteration of the alloying degrees. O 2 treatment results in obvious Ru segregation and formation of RuO 2 . Catalysts treated in H 2 have the highest I f /I b value in the CV scans among all samples, indicating the catalysts have the excellent CO de-poisoning ability as evidenced by anodic CO stripping experiments. N 2 treatment may serve as an adjustment process for the surface composition and structure of the catalysts, which can suppress the surface Pt depletion (∼60% Pt on the surface), make the components stable and hence promote the MOR significantly.

Promotion of Pt-Ru/C catalysts driven by heat treated induced surface segregation for methanol oxidation reaction

Energy Technology Data Exchange (ETDEWEB)

Wei Yuchen; Liu Chenwei; Chang Weijung [Institute of Materials Science and Engineering, National Central University, Taoyuan 32001, Taiwan (China); Wang Kuanwen, E-mail: kuanwen.wang@gmail.com [Institute of Materials Science and Engineering, National Central University, Taoyuan 32001, Taiwan (China)

2011-01-12

Research highlights: > Thermal treatments on the Pt-Ru/C induce different extents of surface segregation. > O{sub 2} treatment results in obvious Ru segregation and formation of RuO{sub 2}. > Catalysts treated in H{sub 2} have the excellent CO de-poisoning ability. > N{sub 2} treatment suppresses the surface Pt depletion and hence promotes the MOR. - Abstract: Carbon supported Pt-Ru/C (1:1) alloy catalysts supplied by E-TEK are widely used for fuel cell research. Heat treatments in various atmospheres are conducted for the promotion of the methanol oxidation reaction (MOR) and the investigation of the structure-activity relationship (SAR) of the catalysts. The alloy structures, surface compositions, surface species, and electro-catalytic activities of the alloy catalysts are characterized by X-ray diffraction (XRD), temperature-programmed reduction (TPR), X-ray photoelectron spectroscopy (XPS), and cyclic voltammetry (CV), respectively. The as-received Pt-Ru/C catalysts have a Ru rich in the inner core and Pt rich on the outer shell structure. Thermal treatments on the catalysts induce Ru surface segregation in different extents and thereby lead to their alteration of the alloying degrees. O{sub 2} treatment results in obvious Ru segregation and formation of RuO{sub 2}. Catalysts treated in H{sub 2} have the highest I{sub f}/I{sub b} value in the CV scans among all samples, indicating the catalysts have the excellent CO de-poisoning ability as evidenced by anodic CO stripping experiments. N{sub 2} treatment may serve as an adjustment process for the surface composition and structure of the catalysts, which can suppress the surface Pt depletion ({approx}60% Pt on the surface), make the components stable and hence promote the MOR significantly.

Synthesis of Pt-Ru PSB-Py catalysis by {gamma}-irradiation and their electrocatalytic efficiency for methanol oxidation

Energy Technology Data Exchange (ETDEWEB)

Yoon, Jung Ah; Sim, Kwang Sik; Choi, Seong Ho [Hannam University, Daejeon (Korea, Republic of); Jung, Sung Hee [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of)

2009-09-15

We report here that deposition of Pt-Ru catalysis on the surface of core-shell conductive balls by radiation-chemical reduction of Pt and Ru ions, in order to use as catalysis in a fuel cell. The poly(styrene-co-4-vinylphenylboronic acid)-pyrrole (PSB-Py) with core-shell structure was obtained by in situ polymerization of pyrrole in the presence of the poly(styrene-co-4-vinylphenylboronic acid) (PSB). Subsequently, Pt-Ru catalysis were deposited onto PSB-Py ball by {gamma}-irradiation, in the presence/absence of poly(vinypyrolidone) (PVP) to prepare electrocatalysis for a fuel cell. The catalytic efficiency of Pt-Ru PSB-Py catalyst was examined for carbon monoxide (CO) stripping and methanol oxidation.

Synthesis of Pt-Ru PSB-Py catalysis by γ-irradiation and their electrocatalytic efficiency for methanol oxidation

International Nuclear Information System (INIS)

Yoon, Jung Ah; Sim, Kwang Sik; Choi, Seong Ho; Jung, Sung Hee

2009-01-01

We report here that deposition of Pt-Ru catalysis on the surface of core-shell conductive balls by radiation-chemical reduction of Pt and Ru ions, in order to use as catalysis in a fuel cell. The poly(styrene-co-4-vinylphenylboronic acid)-pyrrole (PSB-Py) with core-shell structure was obtained by in situ polymerization of pyrrole in the presence of the poly(styrene-co-4-vinylphenylboronic acid) (PSB). Subsequently, Pt-Ru catalysis were deposited onto PSB-Py ball by γ-irradiation, in the presence/absence of poly(vinypyrolidone) (PVP) to prepare electrocatalysis for a fuel cell. The catalytic efficiency of Pt-Ru PSB-Py catalyst was examined for carbon monoxide (CO) stripping and methanol oxidation

Co-catalytic effect of Ni in the methanol electro-oxidation on Pt-Ru/C catalyst for direct methanol fuel cell

International Nuclear Information System (INIS)

Wang, Z.B.; Yin, G.P.; Zhang, J.; Sun, Y.C.; Shi, P.F.

2006-01-01

This research is aimed to improve the utilization and activity of anodic catalysts, thus to lower the contents of noble metals loading in anodes for methanol electro-oxidation. The direct methanol fuel cell anodic catalysts, Pt-Ru-Ni/C and Pt-Ru/C, were prepared by chemical reduction method. Their performances were tested by using a glassy carbon working electrode through cyclic voltammetric curves, chronoamperometric curves and half-cell measurement in a solution of 0.5 mol/L CH 3 OH and 0.5 mol/L H 2 SO 4 . The composition of the Pt-Ru-Ni and Pt-Ru surface particles were determined by EDAX analysis. The particle size and lattice parameter of the catalysts were determined by means of X-ray diffraction (XRD). XRD analysis showed that both of the catalysts exhibited face-centered cubic structures and had smaller lattice parameters than Pt-alone catalyst. Their sizes are small, about 4.5 nm. No significant differences in the methanol electro-oxidation on both electrodes were found by using cyclic voltammetry, especially regarding the onset potential for methanol electro-oxidation. The electrochemically active-specific areas of the Pt-Ru-Ni/C and Pt-Ru/C catalysts are almost the same. But, the catalytic activity of the Pt-Ru-Ni/C catalyst is higher for methanol electro-oxidation than that of the Pt-Ru/C catalyst. Its tolerance performance to CO formed as one of the intermediates of methanol electro-oxidation is better than that of the Pt-Ru/C catalyst

Preparation of PtRu/C anode electrocatalysts using gamma radiation for methanol electro-oxidation

International Nuclear Information System (INIS)

Silva, Dionisio Fortunato da

2006-01-01

Pt Ru/C (carbon-supported Pt Ru nanoparticles) anode electrocatalysts were prepared using radiolytic process (gamma radiation) and tested for methanol electro-oxidation. In this process, water/2-propanol and water/ethylene glycol solutions containing the metallic ions and the carbon support were submitted to gamma radiation under stirring. The water/alcohol ratio (v/v) and the total dose (kGy) were studied. A nominal Pt Ru atomic ratio of 50:50 were used in all experiments. The electrocatalysts were characterized by energy dispersive X-ray analysis (EDX), X-ray diffraction (XRD), transmission electron microscopy (TEM) and cyclic voltammetry (CV). The electro-oxidation of methanol was studied by cyclic voltammetry using the thin porous coating technique. The electrocatalysts prepared in water/2-propanol showed crystallite size in the range of 3-5 nm and Pt Ru atomic ratio of 50:50. The electrocatalysts prepared in water/ethylene glycol showed crystallite size (2-3 nm) smaller than the ones obtained in water/2-propanol, however, the Pt Ru atomic ratios obtained were approximately 80:20, showing that only part of ruthenium ions were reduced. For methanol oxidation the electrocatalytic activity depends on the water/2-propanol and water/ethylene glycol ratio used in the reaction medium. The electrocatalysts prepared in water/2-propanol showed inferior performance to the ones prepared in water/ethylene glycol, which showed similar or superior performances (amperes per gram of platinum) to the commercial electrocatalyst from E-TEK. (author)

Electrooxidation of C{sub 1} to C{sub 3} alcohols with Pt and Pt-Ru sputter deposited interdigitated array electrodes

Energy Technology Data Exchange (ETDEWEB)

Lee, Choong-Gon [Department of Chemical Engineering, Faculty of Engineering, Hanbat National University, San 16-1, Dukmyeong-dong, Yuseong-gu, Daejeon 305-719 (Korea, Republic of)], E-mail: leecg@hanbat.ac.kr; Ojima, Hiroyuki [Department of Applied Chemistry, Graduate School of Engineering, Tohoku University, Aramaki-Aoba 07, Aoba-ku, Sendai 980-8579 (Japan); Umeda, Minoru [Department of Materials Science and Technology, Faculty of Engineering, Nagaoka University of Technology, Kamitomioka 1603-1, Nagaoka, Niigata 940-2188 (Japan)], E-mail: mumeda@vos.nagaokaut.ac.jp

2008-02-25

The electrooxidation of methanol, ethanol, and 2-propanol was investigated with interdigitated array electrodes (IDAEs). The IDAE oxidizes alcohol at the generator and reduces the reaction intermediates produced by the oxidation process at the collector. Thus, the reaction intermediates can be estimated with the IDAE. The IDAE in the present work was made of sputter deposited Pt and Pt-Ru. The use of Ru free and added electrodes provides information on the effect of Ru addition on the alcohol oxidation. Cyclic voltammetric analyses revealed that Ru addition enhances the oxidation currents and reduces the E{sub onset} of the alcohols. The detectable reaction intermediate at the methanol and ethanol oxidation was proton, while the intermediate species was acetone in 2-propnaol oxidation.

A durable PtRu/C catalyst with a thin protective layer for direct methanol fuel cells.

Science.gov (United States)

Shimazaki, Yuzuru; Hayasaka, Sho; Koyama, Tsubasa; Nagao, Daisuke; Kobayashi, Yoshio; Konno, Mikio

2010-11-15

A methanol oxidation catalyst with improved durability in acidic environments is reported. The catalyst consists of PtRu alloy nanoparticles on a carbon support that were stabilized with a silane-coupling agent. The catalyst was prepared by reducing ions of Pt and Ru in the presence of a carbon support and the silane-coupling agent. The careful choice of preparatory conditions such as the concentration of the silane-coupling agent and solution pH resulted in the preparation of catalyst in which the PtRu nanoparticles were dispersively adsorbed onto the carbon support. The catalytic activity was similar to that of a commercial catalyst and was unchanged after immersion in sulfuric acid solution for 1000 h, suggesting the high durability of the PtRu catalyst for the anode of direct methanol fuel cells. Copyright © 2010 Elsevier Inc. All rights reserved.

Functional separation of oxidation–reduction reactions and electron transport in PtRu/ND and conductive additive hybrid electrocatalysts during methanol oxidation

Energy Technology Data Exchange (ETDEWEB)

Zhang, Yan; Wang, Yanhui [State Key Laboratory of Metastable Materials Science and Technology, College of Materials Science and Engineering, Yanshan University, Qinhuangdao 066004 (China); Bian, Linyan [College of Physics and Chemistry, Henan Polytechnic University, Jiaozuo, Henan 454000 (China); Lu, Rui [State Key Laboratory of Metastable Materials Science and Technology, College of Materials Science and Engineering, Yanshan University, Qinhuangdao 066004 (China); Zang, Jianbing, E-mail: jbzang@ysu.edu.cn [State Key Laboratory of Metastable Materials Science and Technology, College of Materials Science and Engineering, Yanshan University, Qinhuangdao 066004 (China)

2016-02-28

Graphical abstract: - Highlights: • Functional separation of reactions and electron transport in PtRu/ND + AB (or CNT). • A conductive network was formed after the addition of AB or CNT. • PtRu/ND + AB (or CNT) exhibited enhanced activity and stability than PtRu/ND. - Abstract: Undoped nanodiamond (ND) supported PtRu (PtRu/ND) electrocatalyst for methanol oxidation reactions (MOR) in direct methanol fuel cells was prepared by a microwave-assisted polyol reduction method. Sp{sup 3}-bonded ND possesses high electrochemical stability but low conductivity, while sp{sup 2}-bonded carbon nanomaterials with high conductivity are prone to oxidation. Therefore, the functions of the supporting material were separated in this study. ND (sp{sup 3}), as a support, and AB or CNTs (sp{sup 2}), as a conductive additive, were combined to form the hybrid electrocatalysts PtRu/ND + AB and PtRu/ND + CNT for MOR. The morphology of the electrocatalysts was characterized by scanning electron microscopy and electrochemical measurements were performed using an electrochemical workstation. The results indicated that the electrocatalytic activity of PtRu/ND for MOR was improved with the addition of AB or CNTs as a conductive additive. Moreover, adding CNTs to PtRu/ND as a conductive additive showed better electrocatalytic activities than adding AB, which can be ascribed to the better electron-transfer ability of CNTs.

Nitrogen Doped Ordered Mesoporous Carbon as Support of PtRu Nanoparticles for Methanol Electro-Oxidation

Directory of Open Access Journals (Sweden)

David Sebastián

2018-04-01

Full Text Available The low oxidation kinetics of alcohols and the need for expensive platinum group metals are still some of the main drawbacks for the commercialization of energy efficient direct alcohol fuel cells. In this work, we investigate the influence of nitrogen doping of ordered mesoporous carbon (CMK as support on the electrochemical activity of PtRu nanoparticles. Nitrogen doping procedures involve the utilization of pyrrole as both nitrogen and carbon precursor by means of a templating method using mesoporous silica. This method allows obtaining carbon supports with up to 14 wt. % nitrogen, with an effective introduction of pyridinic, pyrrolic and quaternary nitrogen. PtRu nanoparticles were deposited by sodium formate reduction method. The presence of nitrogen mainly influences the Pt:Ru atomic ratio at the near surface, passing from 50:50 on the bare (un-doped CMK to 70:30 for the N-doped CMK catalyst. The electroactivity towards the methanol oxidation reaction (MOR was evaluated in acid and alkaline electrolytes. The presence of nitrogen in the support favors a faster oxidation of methanol due to the enrichment of Pt at the near surface together with an increase of the intrinsic activity of PtRu nanoparticles.

A comprehensive study on the effect of Ru addition to Pt electrodes ...

Indian Academy of Sciences (India)

Administrator

The electro-oxidation of ethanol was studied over nanosized Pt and different compositions of ... The onset potential of ethanol electro-oxidation is lowered on bimetallic PtRu ..... Hogarth M P and Ralph T R 2002 Platinum Metals Review 46.

Improvements of electrocatalytic activity of PtRu nanoparticles on multi-walled carbon nanotubes by a H2 plasma treatment in methanol and formic acid oxidation

International Nuclear Information System (INIS)

Jiang Zhongqing; Jiang Zhongjie

2011-01-01

Graphical abstract: A H 2 plasma, that aims at reducing the fraction of the oxidized species at the outermost perimeter of metal particles, has been used to treat the PtRu nanoparticles supported on the plasma functionalized multi-walled carbon nanotubes (PtRu/PS-MWCNTs). The plasma treated PtRu/PS-MWCNTs exhibit increased electrochemically active surface area, reduced charge transfer resistance, improved electrocatalytic activity and long term stability toward methanol and formic acid oxidation, and enhanced tolerance to carbonaceous species relative to the sample untreated with the H 2 plasma. Highlights: → A H 2 plasma technique is used to treat the PtRu nanoparticles. → The H 2 plasma treated PtRu/PS-MWCNTs exhibit improved electrocatalytic activity. → The H 2 plasma treated PtRu/PS-MWCNTs have significantly reduced charge transfer resistance. → The H 2 plasma treated PtRu/PS-MWCNTs show the increased stability. → The Pt:Ru atomic ratio of PtRu nanoparticles has a significant effect on the electrochemical activity. - Abstract: A H 2 plasma has been used to treat the PtRu nanoparticles supported on the plasma functionalized multi-walled carbon nanotubes (PtRu/PS-MWCNTs). The plasma treatment does not change the size and crystalline structure of PtRu nanoparticles, but reduces the fraction of the oxidized species at the outermost perimeter of particles. The electrochemical results show that these plasma treated PtRu/PS-MWCNTs exhibit increased electrochemically active surface area, improved electrocatalytic activity and long term stability toward methanol and formic acid oxidation, and enhanced tolerance to carbonaceous species relative to the sample untreated with the H 2 plasma. The electrocatalytic activities of the plasma treated PtRu/PS-MWCNTs are found to be dependent upon the Pt:Ru atomic ratios of PtRu nanoparticles. The catalysts with a Pt:Ru atomic ratio close to 1:1 show superior properties in the electrooxidation of methanol and formic acid

High activity PtRu/C catalysts synthesized by a modified impregnation method for methanol electro-oxidation

International Nuclear Information System (INIS)

Ma Liang; Liu Changpeng; Liao Jianhui; Lu Tianhong; Xing Wei; Zhang Jiujun

2009-01-01

A modified impregnation method was used to prepare highly dispersive carbon-supported PtRu catalyst (PtRu/C). Two modifications to the conventional impregnation method were performed: one was to precipitate the precursors ((NH 4 ) 2 PtCl 6 and Ru(OH) 3 ) on the carbon support before metal reduction; the other was to add a buffer into the synthetic solution to stabilize the pH. The prepared catalyst showed a much higher activity for methanol electro-oxidation than a catalyst prepared by the conventional impregnation method, even higher than that of current commercially available, state-of-the-art catalysts. The morphology of the prepared catalyst was characterized using TEM and XRD measurements to determine particle sizes, alloying degree, and lattice parameters. Electrochemical methods were also used to ascertain the electrochemical active surface area and the specific activity of the catalyst. Based on XPS measurements, the high activity of this catalyst was found to originate from both metallic Ru (Ru 0 ) and hydrous ruthenium oxides (RuO x H y ) species on the catalyst surface. However, RuO x H y was found to be more active than metallic Ru. In addition, the anhydrous ruthenium oxide (RuO 2 ) species on the catalyst surface was found to be less active.

Assessment for the role of rare earth oxide in the R2O3 - RuO2 - Pt composite electrode

International Nuclear Information System (INIS)

Do Ngoc Lien; Nguyen Van Sinh

2004-01-01

Our work has showed several results related to assessment for the role of rare earth oxide in the R 2 O 3 - RuO 2 - Pt composite electrode. The precursor method was used for preparing composite electrode in the following forms: a- RuO 2 - Pt electrode b- La 2 O 3 (55%) - RuO 2 (45%) - Pt electrode c- CeO 2 (60%) - RuO 2 (40%) - Pt electrode By measurements of anodic polarization and cyclic potential for the types of a, b, c electrodes we can see that the La 2 O 3 (55%) - 45% RuO 2 - Pt electrode will be the best anodic electrode. It means that the partial replacement of ruthenium oxide by lanthanum oxide in composite oxide electrode will be an effective one. (author)

Ultrasonically treated multi-walled carbon nanotubes (MWCNTs) as PtRu catalyst supports for methanol electrooxidation

Energy Technology Data Exchange (ETDEWEB)

Yang, Chunwei; Hu, Xinguo; Wang, Dianlong; Dai, Changsong [Department of Applied Chemistry, Harbin Institute of Technology, Harbin 150001 (China); Zhang, Liang; Jin, Haibo [School of Materials Science and Engineering, Beijing Institute of Technology, Beijing 100081 (China); Agathopoulos, Simeon [Department of Materials Science and Engineering, University of Ioannina, GR-451 10 Ioannina (Greece)

2006-09-29

In the quest of fabricating supported catalysts, experimental results of transmission electron microscopy, Raman and infrared spectroscopy indicate that ultrasonic treatment effectively functionalizes multi-walled carbon nanotubes (MWCNTs), endowing them with groups that can act as nucleation sites which can favor well-dispersed depositions of PtRu clusters on their surface. Ultrasonic treatment seems to be superior than functionalization via regular refluxing. This is confirmed by the determination of the electrochemistry active surface area (ECA) and the CO-tolerance performance of the PtRu catalysts, measured by adsorbed CO-stripping voltammetry in 0.5M sulfuric acid solution, and the real surface area of the PtRu catalysts, evaluated by Brunauer-Emmett-Teller (BET) measurements. Finally, the effectiveness for methanol oxidation is assessed by cyclic voltammetry (CV) in a sulfuric acid and methanol electrolyte. (author)

Enhancement of ethanol oxidation at Pt and PtRu nanoparticles dispersed over hybrid zirconia-rhodium supports

Science.gov (United States)

Rutkowska, Iwona A.; Koster, Margaretta D.; Blanchard, Gary J.; Kulesza, Pawel J.

2014-12-01

A catalytic material for electrooxidation of ethanol that utilizes PtRu nanoparticles dispersed over thin films of rhodium-free and rhodium-containing zirconia (ZrO2) supports is described here. The enhancement of electrocatalytic activity (particularly in the potential range as low as 0.25-0.5 V vs. RHE), that has been achieved by dispersing PtRu nanoparticles (loading, 100 μg cm-2) over the hybrid Rh-ZrO2 support composed of nanostructured zirconia and metallic rhodium particles, is clearly evident from comparison of the respective voltammetric and chronoamperometric current densities recorded at room temperature (22 °C) in 0.5 mol dm-3 H2SO4 containing 0.5 mol dm-3 ethanol. Porous ZrO2 nanostructures, that provide a large population of hydroxyl groups in acidic medium in the vicinity of PtRu sites, are expected to facilitate the ruthenium-induced removal of passivating CO adsorbates from platinum, as is apparent from the diagnostic experiments with a small organic molecule such as methanol. Although Rh itself does not show directly any activity toward ethanol oxidation, the metal is expected to facilitate C-C bond splitting in C2H5OH. It has also been found during parallel voltammetric and chronoamperometric measurements that the hybrid Rh-ZrO2 support increases activity of the platinum component itself toward ethanol oxidation in the low potential range.

Methanol oxidation reaction on Ti/RuO{sub 2(x)}Pt{sub (1-x)} electrodes prepared by the polymeric precursor method

Energy Technology Data Exchange (ETDEWEB)

Freitas, R.G.; Marchesi, L.F.; Mattos-Costa, F.I.; Pereira, E.C. [Laboratorio Interdisciplinar de Eletroquimica e Ceramica, Centro Multidisciplinar para o Desenvolvimento de Materiais Ceramicos, Departamento de Quimica, Universidade Federal de Sao Carlos, Caixa Postal 676, 13560-905 Sao Carlos, SP (Brazil); Oliveira, R.T.S. [Laboratorio Interdisciplinar de Eletroquimica e Ceramica, Centro Multidisciplinar para o Desenvolvimento de Materiais Ceramicos, Departamento de Quimica, Universidade Federal de Sao Carlos, Caixa Postal 676, 13560-905 Sao Carlos, SP (Brazil); Grupo de Materiais Eletroquimicos e Metodos Eletroanaliticos, Instituto de Quimica de Sao Carlos, Universidade de Sao Paulo, Caixa Postal 780, 13566-590 Sao Carlos, SP (Brazil); LEMN, Laboratorio de Eletroquimica e Materiais Nanoestruturados, CCNH-Centro de Ciencias Naturais e Humanas, UFABC-Universidade Federal do ABC, CEP 09.210-170, Rua Santa Adelia 166, Bairro Bangu, Santo Andre, SP (Brazil); Bulhoes, L.O.S. [Laboratorio Interdisciplinar de Eletroquimica e Ceramica, Centro Multidisciplinar para o Desenvolvimento de Materiais Ceramicos, Departamento de Quimica, Universidade Federal de Sao Carlos, Caixa Postal 676, 13560-905 Sao Carlos, SP (Brazil); CENIP, Centro Universitario Central Paulista, UNICEP, Rua Miguel Petroni, 5111, CEP 13563-470, Sao Carlos, SP (Brazil); Santos, M.C. [Laboratorio Interdisciplinar de Eletroquimica e Ceramica, Centro Multidisciplinar para o Desenvolvimento de Materiais Ceramicos, Departamento de Quimica, Universidade Federal de Sao Carlos, Caixa Postal 676, 13560-905 Sao Carlos, SP (Brazil); LEMN, Laboratorio de Eletroquimica e Materiais Nanoestruturados, CCNH-Centro de Ciencias Naturais e Humanas, UFABC-Universidade Federal do ABC, CEP 09.210-170, Rua Santa Adelia 166, Bairro Bangu, Santo Andre, SP (Brazil)

2007-09-27

In this work, ruthenium oxide films containing platinum nanoparticles were prepared using the polymeric precursor method on Ti substrates with several molar ratios. This paper aims at presenting the characterization of the Pt content effect in the methanol electrochemical oxidation reaction. The films were physically characterized using X-ray diffraction and both Pt and RuO{sub 2} (rutile) phases were observed. The mean crystallite sizes were 6 nm for Pt and 25 nm for RuO{sub 2}. The X-ray photoelectronic results indicated that on the electrodes surfaces, depending on the substrate, there was RuO{sub 2}, Ru metal and Pt metal. Besides, it was not observed the formation of PtRu alloys. The atomic force microscopy images of the films showed highly rough surfaces. A decrease in the roughness mean square values is observed as the Pt content increases. These last results are similar to electroactive surface area values calculated by redox-couple (K{sub 4}FeCN{sub 6}/K{sub 3}FeCN{sub 6}). There was an increase in the globular size observed on the electrode surface and lower particle dispersion as the Pt content is increased from 12.5 to 75 mol%. Regarding the eletrode electrocatalytical behavior for methanol oxidation, it was observed that the onset oxidation overpotential is displaced towards more negative values as Pt content is decreased. Besides, an increase has been shown in the current density for methanol oxidation of 600% using a Ti/RuO{sub 2}-Pt (87.5:12.5) electrode compared to polycrystalline Pt. (author)

Influence of alcohol additives in the preparation of electrodeposited Pt-Ru catalysts on oxidized graphite cloths

International Nuclear Information System (INIS)

Sieben, Juan Manuel; Duarte, Marta M.E.; Mayer, Carlos E.

2011-01-01

Research highlights: → Pt-Ru catalysts were prepared by potential pulse electrodeposition from solutions containing EtOH or EG at pH 2 and 5. → The catalyst particle size, loading and dispersion were influenced by solution pH and alcohol addition. → The deposits prepared at pH 2 exhibited large irregular agglomerates while those prepared at pH 5 presented smaller globular particles. → Pt-Ru system prepared using EG at pH 5 exhibited the best performance for CH 3 OH oxidation. - Abstract: Carbon supported Pt-Ru catalysts were prepared by multiple cycles of potentiostatic pulses from aqueous diluted chloroplatinic acid and ruthenium chloride solutions in the presence of ethanol or ethylene glycol at pH 2 and 5. SEM images showed that the metallic deposit prepared at pH 2 consisted of large irregular agglomerates, whereas smaller globular particles were obtained at pH 5. In addition, the average particle size was considerably decreased in the presence of the stabilizers. The supported Pt-Ru alloys were tested as catalysts for methanol electro-oxidation in acid media. Electrocatalytic activity measurements indicated that the most active electrode was obtained with ethylene glycol as additive at pH 5.

Surface and electrochemical characterization of electrodeposited PtRu alloys

Science.gov (United States)

Richarz, Frank; Wohlmann, Bernd; Vogel, Ulrich; Hoffschulz, Henning; Wandelt, Klaus

1995-07-01

PtRu alloys of different compositions were electrodeposited on Au. Twelve alloys between 0% and 100% Pt were characterized with surface sensitive spectroscopies (XPS, LEIS) after transfer from an electrochemical cell to an ultra high vaccum chamber without contact to air. The composition of the thus prepared alloys showed a linear dependence on the concentrations of the deposition solution, but was Pt-enriched both in the bulk and (even more so) at the surface. During the electrochemical reduction of the metal cations, sulfur from the supporting electrolyte 1N H 2SO 4 was found to be incorporated into the electrodes. Cyclic voltammetry was used for the determination of the electrocatalytic activity of the electrodes for the oxidation of carbon monoxide. The highest activity for this oxidation as measured by the (peak) potential of the CO oxidation cyclovoltammograms was found for a surface concentration of ˜ 50%Pt. The asymmetry of this "activity curve" (oxidation potential versus Pt surface concentration) is tentatively explained in terms of a surface structural phase separation.

Quaternary Pt{sub 2}Ru{sub 1}Fe{sub 1}M{sub 1}/C (M=Ni, Mo, or W) catalysts for methanol electro-oxidation reaction

Energy Technology Data Exchange (ETDEWEB)

Jeon, Min Ku; Lee, Ki Rak; Kang, Kweon Ho; Park, Geun Il [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of); Jeon, Hyung Joon [Kyoto University, Kyoto (Japan); McGinn, Paul J. [University of Notre Dame, Indiana (United States)

2015-02-15

Quaternary Pt{sub 2}Ru{sub 1}Fe{sub 1}M{sub 1}/C (M=Ni, Mo, or W) catalysts were investigated for the methanol electro-oxidation reaction (MOR). Electrocatalytic activities of the quaternary catalysts for CO electro-oxidation were studied via CO stripping experiments, and the Pt{sub 2}Ru{sub 1}Fe{sub 1}Ni{sub 1}/C and Pt{sub 2}Ru{sub 1}Fe{sub 1}W{sub 1}/C catalysts exhibited lowered on-set potential compared to that of a commercial PtRu/C catalyst. MOR activities of the quaternary catalysts were determined by linear sweep voltammetry (LSV) experiments, and the Pt{sub 2}Ru{sub 1}Fe{sub 1}W{sub 1}/C catalyst outperformed the commercial PtRu/C catalyst by 170 and 150% for the mass and specific activities, respectively. X-ray photoelectron spectroscopy (XPS) was employed to analyze surface oxidation states of constituent atoms, and it was identified that the structure of the synthesized catalysts are close to a nano-composite of Pt and constituent metal hydroxides and oxides. In addition, the XPS results suggested that the bi-functional mechanism accounts for the improved performance of the Pt{sub 2}Ru{sub 1}Fe{sub 1}Ni{sub 1}/C and Pt{sub 2}Ru{sub 1} Fe{sub 1}W{sub 1}/C catalysts.

Electrical enhancement of direct methanol fuel cells by metal-plasma ion implantation Pt-Ru/C multilayer catalysts.

Science.gov (United States)

Weng, Ko-Wei; Chen, Yung-Lin; Chen, Ya-Chi; Lin, Tai-Nan

2009-02-01

Direct methanol fuel cells (DMFC) have been widely studied owing to their simple cell configuration, high volume energy density, short start-up time, high operational reliability and other favorable characteristics. However, major limitations include high production cost, poisoning of the catalyst and methanol crossover. This study adopts a simple technique for preparing Pt-Ru/C multilayer catalysts, including magnetron sputtering (MS) and metal-plasma ion implantation (MPII). The Pt catalysts were sputtered onto the gas diffusion layer (GDL), followed by the implantation of Ru catalysts using MPII (at an accelerating voltage of 20 kV and an implantation dose of 1 x 10(16) ions/cm2). Pt-Ru is repeatedly processed to prepare Pt-Ru/C multilayer catalysts. The catalyst film structure and microstructure were analyzed by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and scanning electronic microscopy (SEM), respectively. The cell performance was tested using a potential stat/galvano-stat. The results reveal that the membrane electrode assembly (MEA) of four multilayer structures enhances the cell performance of DMFC. The measured power density is 2.2 mW/cm2 at a methanol concentration of 2 M, with an OCV of 0.493 V.

In Situ Synthesis and Characterization of Polyethyleneimine-Modified Carbon Nanotubes Supported PtRu Electrocatalyst for Methanol Oxidation

Directory of Open Access Journals (Sweden)

Xi Geng

2015-01-01

Full Text Available PtRu bimetallic nanoparticles were successfully synthesized on polyethyleneimine- (PEI- functionalized multiwalled carbon nanotubes (MWCNTs via an effective and facile polyol reduction approach. Noncovalent surface modification of MWCNTs with PEI was confirmed by FTIR and zeta potential measurements. The morphology, crystalline structure, and composition of the hybrid material were characterized by transmission electron microscopy (TEM, scanning electron microscopy (SEM, X-ray powder diffraction (XRD, and energy dispersive X-ray spectroscopy (EDX, respectively. According to SEM and TEM observations, PtRu nanoparticles with narrow size distribution were homogeneously deposited on PEI-MWCNTs. Cyclic voltammetry tests demonstrated that the as-prepared PtRu/PEI-MWCNTs nanocomposite had a large electrochemical surface area and exhibited enhanced electrocatalytic activity towards methanol oxidation in comparison with oxidized MWCNTs as catalyst support. PEI-functionalized CNTs, as useful building blocks for the assembly of Pt-based electrocatalyst, may have great potential for applications such as direct methanol fuel cell (DMFC.

Analysis of the kinetics of methanol oxidation in a porous Pt-Ru anode

Energy Technology Data Exchange (ETDEWEB)

Sun, Yan-Ping; Xing, Lei [Chemical Engineering Department, Taiyuan University of Technology, Shanxi 030024 (China); Scott, Keith [School of Chemical Engineering and Advanced Materials, Merz Court, University of Newcastle, Newcastle upon Tyne NE1 7RU (United Kingdom)

2010-01-01

A kinetic model of a porous Pt-Ru anode for methanol oxidation is presented. It was based on the dual-site mechanism for methanol oxidation and used to predict anode performance and the influence of species adsorption on the overall oxidation (macro-) kinetics. The performance of the porous Pt-Ru anode depended on the parameters of the intrinsic chemical kinetics of methanol oxidation and physical parameters such as electrode thickness, surface area, effective diffusion and charge transfer coefficients and concentration of methanol and temperature. The model was solved by using the finite difference method with a subroutine for solving a set of nonlinear algebraic equations in each step. Surface coverage ratio distributions of adsorbed species, effectiveness of the porous electrode and macro-polarisation curves were obtained. The simulated polarisation curves were compared to experimental polarisation data for methanol oxidation on Pt-Ru porous anodes at different temperatures and methanol concentrations. The intrinsic kinetic parameters were regressed from the corresponding experimental data. The predicted polarisation curves calculated by the model, were consistent with experimental polarisation data at lower current densities. The departure of experimental data from the predicted polarisation curves at high concentration and high apparent current densities was believed to be due to two-phase flow in the electrode. (author)

The kinetics and mechanism of methanol oxidation on Pt and PtRu catalysts in alkaline and acid media

Directory of Open Access Journals (Sweden)

JELENA LOVIC

2007-07-01

Full Text Available The kinetic of methanol electrochemical oxidation for a series of platinum and platinum–ruthenium catalysts was investigated. A correlation between the beginning of OHad adsorption and methanol oxidation was demonstarated on Pt single crystals and Pt nanocatalyst. The activity of the nano-structured Pt catalyst was compared with single crystal platinum electrodes assuming the Kinoshita model of nanoparticles. The ruthenium-containing catalysts shifted the onset of methanol oxidation to more negative potentials. The effect was more pronounced in acid than in alkaline media. Based on the established diagnostic criteria, the reaction between COad and OHad species according to the Langmuir–Hinshelwood mechanism was proposed as the rate determining step in alkaline and acid media on Pt and PtRu catalysts.

Novel Pt-Ru nanoparticles formed by vapour deposition as efficient electrocatalyst for methanol oxidation

International Nuclear Information System (INIS)

Sivakumar, Pasupathi; Ishak, Randa; Tricoli, Vincenzo

2005-01-01

Bimetallic Pt-Ru nanoparticles supported on carbon substrates have been prepared reproducibly by a simple method that utilizes commercially available metal-organic precursors at low temperature in vacuum. Particles morphology, composition and structure have been investigated using HRTEM, EDX, selected area electron diffraction (SAED) and powder XRD analysis. TEM shows that the obtained nanoparticles are homogeneously dispersed on the substrate surface and exhibit narrow size distribution, the average diameter being ca. 2 nm. Point resolved EDX analysis demonstrates co-presence of both Pt and Ru in each particle, thereby indicating that truly bimetallic nanoparticles have been obtained. Moreover, EDX performed on several areas of the sample evidences uniform particles composition. The latter can be controlled very easily and effectively by regulating the operation temperature during particles preparation. HRTEM imaging shows that the particles possess crystalline structure. Both SAED and XRD analyses indicate presence of nanoparticles exhibiting structure consistent with that of an f.c.c. Pt-Ru alloy. Besides the f.c.c. alloy, an additional crystalline phase might also be present as noticed by SAED. These nanoparticles display electrocatalytic activity with regard to methanol oxidation as evidenced by cyclic voltammetry (CV)

Barrier characteristics of Pt/Ru Schottky contacts on n-type GaN ...

Indian Academy of Sciences (India)

Pt/Ru Schottky rectifiers; n-type GaN; temperature–dependent electrical properties; inhomogeneous barrier heights .... a 2 μm thick Si-doped GaN films which were grown by .... ted values of ap using (9) for two Gaussian distributions of bar-.

Pt-Ni and Pt-M-Ni (M = Ru, Sn Anode Catalysts for Low-Temperature Acidic Direct Alcohol Fuel Cells: A Review

Directory of Open Access Journals (Sweden)

Ermete Antolini

2017-01-01

Full Text Available In view of a possible use as anode materials in acidic direct alcohol fuel cells, the electro-catalytic activity of Pt-Ni and Pt-M-Ni (M = Ru, Sn catalysts for methanol and ethanol oxidation has been widely investigated. An overview of literature data regarding the effect of the addition of Ni to Pt and Pt-M on the methanol and ethanol oxidation activity in acid environment of the resulting binary and ternary Ni-containing Pt-based catalysts is presented, highlighting the effect of alloyed and non-alloyed nickel on the catalytic activity of these materials.

Ru-decorated Pt nanoparticles on N-doped multi-walled carbon nanotubes by atomic layer deposition for direct methanol fuel cells

DEFF Research Database (Denmark)

Johansson, Anne-Charlotte Elisabeth Birgitta; Yang, R.B.; Haugshøj, K.B.

2013-01-01

We present atomic layer deposition (ALD) as a new method for the preparation of highly dispersed Ru-decorated Pt nanoparticles for use as catalyst in direct methanol fuel cells (DMFCs). The nanoparticles were deposited onto N-doped multi-walled carbon nanotubes (MWCNTs) at 250 °C using trimethyl......(methylcyclopentadienyl)platinum MeCpPtMe3, bis(ethylcyclopentadienyl)ruthenium Ru(EtCp)2 and O2 as the precursors. Catalysts with 5, 10 and 20 ALD Ru cycles grown onto the CNT-supported ALD Pt nanoparticles (150 cycles) were prepared and tested towards the electro-oxidation of CO and methanol, using cyclic voltammetry...... and chronoamperometry in a three-electrode electrochemical set-up. The catalyst decorated with 5 ALD Ru cycles was of highest activity in both reactions, followed by the ones with 10 and 20 ALD Ru cycles. It is demonstrated that ALD is a promising technique in the field of catalysis as highly dispersed nanoparticles...

Preparation and characterization of Pt Sn / C-rare earth and PtRu / C-rare earth using an alcohol reduction process for ethanol electron-oxidation

International Nuclear Information System (INIS)

Rodrigues, Rita Maria de Sousa

2011-01-01

The electro catalyst PtRu / C-rare earth and PtSn/C-rare earth (20 wt%) were prepared by alcohol reduction method using H 2 PtCl 6 .6H 2 O Ru Cl xH 2 O, SnCl 2 .2H 2 O as a source of metals 85 % Vulcan - 15 % rare earth as a support and, finally, ethylene glycol as reducing agent. The electrocatalysts were characterized physically by X-ray diffraction (XRD), energy dispersive X-ray (EDX), and transmission electron microscopy (TEM). Analyses by EDX showed that the atomic ratios of different electrocatalysts, prepared by alcohol reduction method are similar to the nominal starting compositions indicating that this methodology is promising for the preparation of electrocatalysts. In all the XRD patterns for the prepared electrocatalysts there is a broad peak at about 2θ = 25 o , which is associated with the carbon support and four additional diffraction peaks at approximately 2θ = 40 o , 47 o , 67 o e 82 o , which in turn are associated with the plans (111), (200), (220) e (311), respectively, of face-centered cubic structure (FCC) platinum. The results of X-ray diffraction also showed average crystallite sizes between 2.0 and 4.0 nm for PtSn e 2,0 a 3,0 para PtRu. The studies for the electrochemical oxidation of ethanol in acid medium were carried out using the technique of chronoamperometry in a solution 0,5 mol.L-1 H 2 SO 4 , + 1,0 mol.L-1 de C 2 H 5 OH. The polarization curves obtained in the fuel cell unit, powered directly by ethanol, are in agreement with the results of voltammetry and chronoamperometry noting the beneficial effect of rare earths in the preparation of electrocatalysts and attesting that the electrocatalysts PtSn/C are more effective than PtRu/C for the oxidation of ethanol.

Electrochemical promotion of catalytic reactions with Pt/C (or Pt/Ru/C)//PBI catalysts

DEFF Research Database (Denmark)

Petrushina, Irina; Bjerrum, Niels; Bandur, Viktor

2007-01-01

The paper is an overview of the results of the investigation on electrochemical promotion of three catalytic reactions: methane oxidation with oxygen, NO reduction with hydrogen at 135 degrees C and Fischer-Tropsch synthesis (FTS) at 170 degrees C in the [CH4/O-2(or NO/H-2 or CO/H-2)/Ar//Pt(or Pt....../Ru)//PBI(H3PO4)/H-2, Ar] fuel cell. It has been shown that the partial methane oxidation to C2H2 and the C-2 selectivity were electrochemically promoted by the negative catalyst polarization. This was also the case in NO reduction with hydrogen for low NO and H-2 partial pressures. In both cases the catalytic...... reactions have been promoted by the electrochemically produced hydrogen. It has been found that the NO reduction with hydrogen on the Pt/PBI strongly depends on NO and hydrogen partial pressures in the working gas mixture. At higher NO and H-2 partial pressures the catalysis is promoted...

Structural and magnetic properties of UCo1/3T2/3Al solid solutions (T = Ru, Pt, Rh)

International Nuclear Information System (INIS)

Andreev, A. V.; Bordallo, H. N.; Chang, S.; Nakotte, H.; Schultz, A. J.; Sechovsky, V.; Torikachvili, M. S.

1999-01-01

We report on neutron diffraction studies of UCo 1/3 T 2/3 Al (T = Ru, Pt, Rh). All three solid solutions form in the hexagonal ZrNiAl structure. The Ru-containing compound is found to be chemically ordered, while the Pt-containing compound is nearly disordered and the Rh-containing compound is purely disordered. All three compounds exhibit long-range magnetic order with rather small U moments

Ionic Liquid Gating Control of RKKY Interaction in FeCoB/Ru/FeCoB and (Pt/Co)₂/Ru/(Co/Pt)₂ Multilayers.

Energy Technology Data Exchange (ETDEWEB)

Yang, Qu; Wang, Lei; Zhou, Ziyao; Wang, Liqian; Zhang, Yijun; Zhao, Shishun; Dong, Guohua; Cheng, Yuxin; Min, Tai; Hu, Zhongqiang; Chen, Wei; Xia, Ke; Liu, Ming

2018-03-07

To overcome the fundamental challenge of the weak natural response of antiferromagnetic materials under a magnetic field, voltage manipulation of antiferromagnetic interaction is developed to realize ultrafast, high-density, and power efficient antiferromagnetic spintronics. Here, we report a low voltage modulation of Ruderman–Kittel–Kasuya–Yosida (RKKY) interaction via ionic liquid gating in synthetic antiferromagnetic multilayers of FeCoB/Ru/FeCoB and (Pt/Co)₂/Ru/(Co/Pt)₂. At room temperature, the distinct voltage control of transition between antiferromagnetic and ferromagnetic ordering is realized and up to 80% of perpendicular magnetic moments manage to switch with a small-applied voltage bias of 2.5 V. We related this ionic liquid gating-induced RKKY interaction modification to the disturbance of itinerant electrons inside synthetic antiferromagnetic heterostructure and the corresponding change of its Fermi level. Voltage tuning of RKKY interaction may enable the next generation of switchable spintronics between antiferromagnetic and ferromagnetic modes with both fundamental and practical perspectives.

Pulse electrodeposition of Pt and Pt–Ru methanol-oxidation nanocatalysts onto carbon nanotubes in citric acid aqueous solutions

Energy Technology Data Exchange (ETDEWEB)

Chou, Huei-Yu [Department of Engineering and System Science, National Tsing Hua University, Hsinchu 30013, Taiwan, ROC (China); Hsieh, Chien-Kuo [Department of Materials Engineering, Ming Chi University of Technology, New Taipei City 24301, Taiwan, ROC (China); Tsai, Ming-Chi; Wei, Yu-Hsuan; Yeh, Tsung-Kuang [Department of Engineering and System Science, National Tsing Hua University, Hsinchu 30013, Taiwan, ROC (China); Tsai, Chuen-Horng, E-mail: tsai@aec.gov.tw [Department of Engineering and System Science, National Tsing Hua University, Hsinchu 30013, Taiwan, ROC (China)

2015-06-01

In this study, platinum nanoparticle/carbon nanotube (Pt NP/CNT) and platinum–ruthenium nanoparticle (Pt–Ru NP/CNT) hybrid nanocatalysts were prepared by the pulse-electrodeposition method in different aqueous solutions containing citric acid (CA) or sulfuric acid (SA). The electrocatalytic properties of the Pt NP/CNT and Pt–Ru NP/CNT electrodes prepared using different aqueous solutions were investigated for methanol oxidation. The results show that the electrochemical mass activities of these hybrid nanocatalysts prepared in the CA aqueous solution were increased by factors of 1.46 and 2.77 for Pt NPs and Pt–Ru NPs, respectively, compared with those prepared in SA aqueous solutions using the same procedure. These increased mass activities are attributed to the CA playing dual roles as both a stabilizing agent and a particle size reducing agent in the aqueous solutions. The approach developed in this work enables further reductions in the particle sizes of noble-metal nanocatalysts. - Highlights: • Pulse-electrodeposition of Pt or Pt–Ru nanoparticles on carbon nanotubes • Carbon nanotubes used as a catalyst-supporting material • Citric acid used as reducing agent in the aqueous electrodeposition solutions • Electrochemical activity for methanol oxidation improved by a factor of 1.46 to 2.77.

Improved reaction kinetics and selectivity by the TiO2-embedded carbon nanofiber support for electro-oxidation of ethanol on PtRu nanoparticles

Science.gov (United States)

Nakagawa, Nobuyoshi; Ito, Yudai; Tsujiguchi, Takuya; Ishitobi, Hirokazu

2014-02-01

The electro-oxidation of ethanol by the catalyst of PtRu nanoparticles supported on a TiO2-embedded carbon nanofiber (PtRu/TECNF), which has recently been proposed by the authors as a highly active catalyst for methanol oxidation, is investigated by cyclic voltammetry using a glassy carbon electrode and by operating a direct ethanol fuel cell (DEFC) with the catalyst. The mass activity obtained from the cyclic voltammogram for the ethanol oxidation is compared to that for the methanol oxidation reported in our recent paper. The mass activity for the ethanol oxidation is comparable or slightly higher than that for the methanol oxidation, and the relationship between the TECNF composition, i.e., the Ti/C mass ratio, and the activity are also similar to that for the methanol oxidation. A DEFC fabricated with the PtRu/TECNF shows a higher power output compared to that with the commercial PtRu/C catalyst. An analysis of the reaction products by a simple two-step reaction model reveals that the PtRu/TECNF increases the rate constant for the reaction steps from ethanol to acetaldehyde and subsequently to CO2, but decreases that from acetaldehyde to acetic acid. This means that the PtRu/TECNF improves not only the kinetics, but also the selectivity to acetaldehyde.

Electrodeposition of mesoscopic Pt-Ru on reticulated vitreous carbon from reverse emulsions and microemulsions: Application to methanol electro-oxidation

International Nuclear Information System (INIS)

Cheng, Tommy T.; Gyenge, Elod L.

2006-01-01

High surface area Pt-Ru (between 120 and 400 cm 2 mg -1 ) meso-sized particles and mesoporous coatings were electrodeposited on reticulated vitreous carbon (RVC) three-dimensional electrodes using reverse emulsions and microemulsions. The organic phase of the colloidal media was composed of cyclohexane, Triton X-100 non-ionic surfactant and tetrabutylammonium perchlorate (for ionic conductivity) while the aqueous phase contained H 2 PtCl 6 and RuCl 3 (or (NH 4 ) 2 RuCl 6 ). For microemulsification to occur isopropanol was also added as co-surfactant. The catalytic activity for the electro-oxidation of methanol was assessed by cyclic voltammetry and chronopotentiometry in conjunction with surface area measurement by Cu underpotential deposition. The composition and morphology of the Pt-Ru deposit was analyzed by inductively coupled plasma atomic emission spectroscopy and scanning electron microscopy, respectively. The effects on the catalytic activity of the deposition current density, temperature, RVC pretreatment and plating bath composition are presented. It was found that the electrodeposition of Pt-Ru in reverse microemulsion yielded the highest specific surface area (400 cm 2 mg -1 ) and catalytic activity toward CH 3 OH electro-oxidation as shown, for example, by a 50-200 mV more negative anode potential determined by chronopotentiometry compared to a catalyst obtained by pure aqueous and emulsion electroplating

Electrodeposition of mesoscopic Pt-Ru on reticulated vitreous carbon from reverse emulsions and microemulsions: Application to methanol electro-oxidation

Energy Technology Data Exchange (ETDEWEB)

Cheng, Tommy T. [2360 East Mall, Department of Chemical and Biological Engineering, University of British Columbia, Vancouver, BC, V6T 1Z3 (Canada); Gyenge, Elod L. [2360 East Mall, Department of Chemical and Biological Engineering, University of British Columbia, Vancouver, BC, V6T 1Z3 (Canada)]. E-mail: egyenge@chml.ubc.ca

2006-05-20

High surface area Pt-Ru (between 120 and 400 cm{sup 2} mg{sup -1}) meso-sized particles and mesoporous coatings were electrodeposited on reticulated vitreous carbon (RVC) three-dimensional electrodes using reverse emulsions and microemulsions. The organic phase of the colloidal media was composed of cyclohexane, Triton X-100 non-ionic surfactant and tetrabutylammonium perchlorate (for ionic conductivity) while the aqueous phase contained H{sub 2}PtCl{sub 6} and RuCl{sub 3} (or (NH{sub 4}){sub 2}RuCl{sub 6}). For microemulsification to occur isopropanol was also added as co-surfactant. The catalytic activity for the electro-oxidation of methanol was assessed by cyclic voltammetry and chronopotentiometry in conjunction with surface area measurement by Cu underpotential deposition. The composition and morphology of the Pt-Ru deposit was analyzed by inductively coupled plasma atomic emission spectroscopy and scanning electron microscopy, respectively. The effects on the catalytic activity of the deposition current density, temperature, RVC pretreatment and plating bath composition are presented. It was found that the electrodeposition of Pt-Ru in reverse microemulsion yielded the highest specific surface area (400 cm{sup 2} mg{sup -1}) and catalytic activity toward CH{sub 3}OH electro-oxidation as shown, for example, by a 50-200 mV more negative anode potential determined by chronopotentiometry compared to a catalyst obtained by pure aqueous and emulsion electroplating.

Revisiting anomalous B(E2;41+→21+)/B(E2;21+→01+) values in 98Ru and 180Pt

International Nuclear Information System (INIS)

Williams, E.; Plettner, C.; McCutchan, E. A.; Levine, H.; Casten, R. F.; Ai, H.; Heinz, A.; Qian, J.; Meyer, D. A.; Werner, V.; Zamfir, N. V.; Cakirli, R. B.; Beausang, C. W.; Guerdal, G.; Pietralla, N.

2006-01-01

Recently, a set of nine nonmagic nuclei with anomalous values of the B(E2) ratio B 4/2 ≡B(E2;4 1 + →2 1 + )/B(E2;2 1 + →0 1 + ) 1 + →2 1 + ) values for two of these nuclei, 98 Ru and 180 Pt, were re-measured to determine if the current literature values for these nuclei are correct. 98 Ru was studied in a 27 Al( 98 Ru, 98 Ru*) Coulomb excitation experiment in inverse kinematics, while the lifetime of the 4 1 + state in 180 Pt was measured in a 122 Sn( 62 Ni, 4n) 180 Pt recoil distance method (RDM) experiment. For both nuclei, the remeasured B 4/2 values are well above 1, removing the deviations from collective models

Synergistic effects for the TiO2/RuO2/Pt photodissociation of water

Energy Technology Data Exchange (ETDEWEB)

Blondel, G; Harriman, A; Williams, D

1983-07-01

Compressed discs of naked TiO2 or TiO2 coated with a thin film of a noble metal (e.g. Pt) do not photodissociate water upon illumination with UV light, but small amounts of H2 are generated if the TiO2 has been reduced in a stream of H2 at 600 C. Discs prepared from mixtures of TiO2/RuO2 facilitate the UV photodissociation of water into H2 and O2 although the yields are very low. When a thin (about 9 nm) film of Pt is applied to the TiO2/RuO2 discs, the yields of H2 and O2 observed upon irradiation with UV light are improved drastically. 25 references.

Tetrapropylammonium ion influence on the synthesis of Pt Ru/carbon hybrids by hydrothermal carbonization

International Nuclear Information System (INIS)

Tusi, M.M.; Polanco, N.S.O.; Brandalise, M.; Correa, O.V.; Silva, A.C.; Oliveira Neto, A.; Linardi, M.; Spinace, E.V.

2010-01-01

PtRu/Carbon hybrid materials were prepared by hydrothermal carbonization using starch as carbon source and reducing agent and H 2 PtCl 6 .6H 2 O e RuCl 3 .xH 2 O as metals source and catalyst of the carbonization process. The materials were prepared in the following conditions: without pH adjustment, in the absence and in the presence of tetrapropylammonium chloride (TPACl), and adjusting the pH using potassium hydroxide (KOH) or tetrapropylammonium hydroxide (TPAOH). The obtained materials were treated under argon atmosphere at 900 deg C and characterized by SEM/EDX, BET isotherm, XRD and TEM. The electro-oxidation of methanol was studied by chronoamperometry. The material prepared using TPAOH showed the best performance for methanol electro-oxidation. (author)

Incorporation of metals (Pt-Ni-Ru) in the zeolite ZSM-5 through ion exchange competitive: synthesis and characterization

International Nuclear Information System (INIS)

Barbosa, A.S.; Rodrigues, M.G.F.

2012-01-01

Zeolites are very important materials due to their high specific surface area. Moreover, they are suitable for use as catalyst support. Noble metals supported on zeolites have been widely used as catalysts in the petrochemical industry. This paper was prepared and characterized, a powder aiming its use in heterogeneous catalysis. Support was used as ZSM-5 and the method of incorporation of the metals (Ru-PtNi) was competitive ion exchange. The materials (ZSM-5 and Pt-Ni-Ru/ZSM-5) were characterized by spectrophotometry Energy Dispersive X-ray (EDX), X-Ray Diffraction (XRD) and nitrogen physisorption (BET method). Based on the results of X-ray diffraction, it is possible to demonstrate the preservation of the structure of zeolite ZSM-5 after the competitive ion Exchange with metals (Ru-Pt-Ni) and calcination. The dispersion of metals on ZSM-5 did not change the textural characteristics of the zeolite. (author)

Chemometric study of the effects of PtRu:BH4-molar ratio and solvent used in the preparation of PtRu/C electrocatalysts for for direct methanol fuel cell anodes

Energy Technology Data Exchange (ETDEWEB)

Polanco, N.S.O.; Neto, A.O.; Spinace, E.V. [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil); Tusi, M.M. [Universidade Regional Integrada do Alto Uruguai e das Missoes (URI), Santiago, RS (Brazil); Brandalise, M. [Instituto Federal Fluminense (IFF), Campos dos Goyracazes, RJ (Brazil)

2014-07-01

PtRu/C electrocatalysts were prepared by borohydride reduction method and a chemometric study was performed to evaluate the influence of the solvent (water and isopropyl alcohol) and amount of reducing agent (PtRu:BH4- molar ratios of 5 and 15) in maximum power density. In borohydride reduction method, a solution containing sodium hydroxide and sodium borohydride (NaBH4) is added to a mixture containing water, isopropyl alcohol, metallic precursors and the carbon support Vulcan XC72. The obtained materials were characterized by energy-dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD) and transmission electron microscopy (TEM). Membrane Electrode Assemblies (MEA's) were produced and tests in single direct methanol fuel cells were performed. The amount of sodium borohydride used in the reduction showed more influence on the maximum power density than the change of solvent of the reaction. (author)

Influence of method of preparation of Pt Ru/C electrocatalysts on the catalytic activity for the ethanol oxidation reaction in acidic medium; Influencia do metodo de preparacao de eletrocatalisadores PtRu/C sobre a atividade catalitica frente a reacao de oxidacao de etanol em meio acido

Energy Technology Data Exchange (ETDEWEB)

Gomes, Walber dos Santos; Silva, Uriel Lean Valente; Souza, Jose Pio Iudice de, E-mail: jpio@ufpa.br [Universidade Federal do Para, (UFPA), Belem, PA (Brazil). Instituto de Ciencias Exatas e Naturais. Faculdade de Quimica

2013-09-01

In this work the influence of variations in the borohydrate reduction method on the properties of Pt Ru/C electrocatalysts was investigated. The electrocatalysts were prepared using 1:1 ; 2:1; 5:1; 50:1 and 250:1 molar ratios of NaBH{sub 4} to metals. The reduction was also performed by dripping or by fast addition of the solution. The results showed that Pt Ru nanoparticles obtained by fast addition had the smallest crystallite sizes. It was also noted that the catalytic activity increased as the borohydrate:metal molar ratio increased. The Pt Ru/C electrocatalysts (50:1) obtained by fast addition presented the best catalytic activity for ethanol electro-oxidation. (author)

Electrodeposition of Pt-Ru nanoparticles on fibrous carbon substrates in the presence of nonionic surfactant: Application for methanol oxidation

International Nuclear Information System (INIS)

Bauer, Alex; Gyenge, Elod L.; Oloman, Colin W.

2006-01-01

Liquid crystalline and micellar aqueous solutions of the nonionic surfactant Triton X-100 were used to direct the electrodeposition of Pt-Ru nanoparticles onto graphite felts, which were investigated as novel anodes for the direct methanol fuel cell. The effects of surfactant concentration, current density and deposition time in the preparation of these three-dimensional electrodes were studied in a factorial experiment and the electrodes were characterized by SEM and ICP-AES. Cyclic voltammetry, chronoamperometry and chronopotentiometry were carried out to assess the activity of the catalyzed felts for methanol oxidation. The presence of Triton X-100 (40-60 wt.%) coupled with an acidic plating solution were essential for the efficient co-electrodeposition of Ru in the presence of Pt to yield approximately a 1:1 Pt:Ru atomic ratio in the deposit. The highest mass specific activity, 24 A g -1 at 298 K (determined by chronoamperometry after 180 s at 0 V versus Hg/Hg 2 SO 4 , K 2 SO 4std ), was obtained for the Pt-Ru electrodeposited in the presence of 40 wt.% Triton X-100 at 60 A m -2 , 298 K for 90 min. Surfactant mediated electrodeposition is a promising method for meso-scale (ca. 10-60 nm diameter) catalyst particle preparation on three-dimensional electrodes

Cyclic voltammetric analysis of C 1-C 4 alcohol electrooxidations with Pt/C and Pt-Ru/C microporous electrodes

Science.gov (United States)

Lee, Choong-Gon; Umeda, Minoru; Uchida, Isamu

The effect of temperature on methanol, ethanol, 2-propanol, and 2-butanol electrooxidation is investigated with Pt/C and Pt-Ru/C microporous electrodes. Cyclic voltammetry is employed in temperatures ranging from 25 to 80 °C to provide quantitative and qualitative information on the kinetics of alcohol oxidation. Methanol displays the greatest activity atom alcohols. The addition of ruthenium reduces the poisoning effect, although it is ineffective with secondary alcohols. Secondary alcohols undergo a different oxidation mechanism at higher temperatures. Microporous electrodes provide detailed information on alcohol oxidation.

Structure and magnetic properties of L10-FePt thin films on TiN/RuAl underlayers

International Nuclear Information System (INIS)

Yang En; Ratanaphan, Sutatch; Zhu Jiangang; Laughlin, David E.

2011-01-01

Highly ordered L1 0 FePt-oxide thin films with small grains were prepared by using a RuAl layer as a grain size defining seed layer along with a TiN barrier layer. Different HAMR (Heat Assisted Magnetic Recording) favorable underlayers were studied to encourage perpendicular texture and preferred microstructure. It was found that the epitaxial and small grain growth from the RuAl/TiN underlayer results in small and uniform grains in the FePt layer with perpendicular texture. By introducing the grain size defining underlayers, the FePt grain size can be reduced from 30 to 6 nm with the same volume fraction (9%) of SiO 2 in the film, excellent perpendicular texture, and very high order parameter at 520 deg. C.

Electrodeposition of Pt-Ru nanoparticles on fibrous carbon substrates in the presence of nonionic surfactant: Application for methanol oxidation

Energy Technology Data Exchange (ETDEWEB)

Bauer, Alex; Gyenge, Elod L.; Oloman, Colin W. [Department of Chemical and Biological Engineering, University of British Columbia, 2360 East Mall, Vancouver, BC (Canada)

2006-07-28

Liquid crystalline and micellar aqueous solutions of the nonionic surfactant Triton X-100 were used to direct the electrodeposition of Pt-Ru nanoparticles onto graphite felts, which were investigated as novel anodes for the direct methanol fuel cell. The effects of surfactant concentration, current density and deposition time in the preparation of these three-dimensional electrodes were studied in a factorial experiment and the electrodes were characterized by SEM and ICP-AES. Cyclic voltammetry, chronoamperometry and chronopotentiometry were carried out to assess the activity of the catalyzed felts for methanol oxidation. The presence of Triton X-100 (40-60wt.%) coupled with an acidic plating solution were essential for the efficient co-electrodeposition of Ru in the presence of Pt to yield approximately a 1:1 Pt:Ru atomic ratio in the deposit. The highest mass specific activity, 24Ag{sup -1} at 298K (determined by chronoamperometry after 180s at 0V versus Hg/Hg{sub 2}SO{sub 4}, K{sub 2}SO{sub 4std}), was obtained for the Pt-Ru electrodeposited in the presence of 40wt.% Triton X-100 at 60Am{sup -2}, 298K for 90min. Surfactant mediated electrodeposition is a promising method for meso-scale (ca. 10-60nm diameter) catalyst particle preparation on three-dimensional electrodes. (author)

Preparation of Pt Ru/C electrocatalysts using gamma radiation for application as anode in direct methanol fuel cell

International Nuclear Information System (INIS)

Spinace, Estevam V.; Silva, Dionisio F. da; Cruz, Victor A. da; Oliveira Neto, Almir; Machado, Luci D.B.; Pino, Eddy S.; Linardi, Marcelo

2005-01-01

PtRu nanoparticles supported on carbon (PtRu/C electrocatalysts) were prepared submitting a water/2-propanol mixture containing the metal ions and the carbon support to gamma radiation. The water/2-propanol (v/v) and the total dose (kGy) were studied. The electrocatalysts were characterized by EDX, XRD and cyclic voltammetry. The methanol electro-oxidation was studied by cyclic voltammetry using the thin porous coating. In the studied conditions, the electrocatalytic activity of the prepared electrocatalysts depend on the water/2-propanol ratio used in the reaction medium. (author)

H2 splitting on Pt, Ru and Rh nanoparticles supported on sputtered HOPG

DEFF Research Database (Denmark)

Fiordaliso, Elisabetta Maria; Murphy, Shane; Nielsen, R.M.

2012-01-01

The equilibrium hydrogen exchange rate between adsorbed and gas phase hydrogen at 1bar is measured for Pt, Ru and Rh nanoparticles supported on a sputtered HOPG substrate. The particles are prepared by Electron Beam Physical Vapor Deposition and the diameter of the particles varies between 2 and ...

Influence of polymolybdate adsorbates on electrooxidation of ethanol at PtRu nanoparticles: Combined electrochemical, mass spectrometric and X-ray photoelectron spectroscopic studies

Science.gov (United States)

Gralec, Barbara; Lewera, Adam; Kulesza, Pawel J.

2016-05-01

The role Keggin-type phosphomolybdate (PMo12O403-) ions (adsorbed on carbon-supported PtRu, PtRu/C) on electrooxidation of ethanol is addressed here. The combined results obtained using Differential Electrochemical Mass Spectrometry, X-ray Photoelectron Spectroscopy and Cyclic Voltammetry are consistent with the view that presence of the Keggin-type polyoxometallate, phosphomolybdate, ions (adsorbates) leads to enlargement of the current densities associated with electrooxidation of ethanol at potentials greater than 700 mV vs. RHE. This increase of the anodic currents is correlated with the higher acetaldehyde yield which is likely to reflect changes in the reaction kinetics (e.g. more dynamic dehydrogenation of ethanol leading to acetaldehyde) or in the reaction mechanism defined by the preferential surface modification resulting not only in faster kinetics but also in higher selectivity with respect to acetaldehyde production. It is apparent from the spectroscopic data that modification of PtRu/C nanoparticles with phosphomolybdate ions leads to suppression of the formation of Ru surface oxides.

Development of a database for the prediction of phases in Pt-Al-Cr-Ru alloys for high-temperature and corrosive environments: Al-Cr-Ru

International Nuclear Information System (INIS)

Suess, R.; Watson, A.; Cornish, L.A.; Compton, D.N.

2009-01-01

Platinum-based alloys for high-temperature corrosive environments are being developed which have microstructures that are analogous to the γ/γ' microstructure of the nickel-based superalloys. The need for a predictive thermodynamic database for these alloys was identified. Because experimental studies suggested that such a database should be based on Pt-Al-Cr-Ru, the Al-Cr-Ru system is of importance in this research programme. Using the CALPHAD method and Thermo-Calc software, existing binary data were used to optimise a ternary database for Al-Cr-Ru against available experimental ternary data. The database gives good predictions with regards to phase equilibria in the system as well as the nature of the primary solidification phases.

Cyclic voltammetric analysis of C{sub 1}-C{sub 4} alcohol electrooxidations with Pt/C and Pt-Ru/C microporous electrodes

Energy Technology Data Exchange (ETDEWEB)

Lee, Choong-Gon [Department of Chemical Engineering, Hanbat National University, San 16-1 Dukmyung-dong, Yusong-gu, Daejon (Korea); Umeda, Minoru [Department of Chemistry, Nagaoka University of Technology, Kamitomioka, Nagaoka (Japan); Uchida, Isamu [Department of Applied Chemistry, Tohoku University, Aramaki-aoba, Aoba-ku, Sendai (Japan)

2006-09-29

The effect of temperature on methanol, ethanol, 2-propanol, and 2-butanol electrooxidation is investigated with Pt/C and Pt-Ru/C microporous electrodes. Cyclic voltammetry is employed in temperatures ranging from 25 to 80{sup o}C to provide quantitative and qualitative information on the kinetics of alcohol oxidation. Methanol displays the greatest activity atom alcohols. The addition of ruthenium reduces the poisoning effect, although it is ineffective with secondary alcohols. Secondary alcohols undergo a different oxidation mechanism at higher temperatures. Microporous electrodes provide detailed information on alcohol oxidation. (author)

Bifunctional electrodes with ir and Ru oxide mixtures and pt for unified regenerative cells; Electrodos bifuncionales basados en mezclas de oxidos de Ir y Ru con Pt para celdas regenerativas unificadas

Energy Technology Data Exchange (ETDEWEB)

Duron-Torres, S.M.; Escalante-Garcia, I.L. [Universidad Autonoma de Zacatecas, Zacatecas (Mexico); Cruz, J. C.; Arriaga-Hurtado; L.G. [Centro de Investigacion y Desarrollo Tecnologico en Electroquimica, Pedro Escobedo, Queretaro (Mexico)]. E-mail: duronsm@prodigy.net.mx

2009-09-15

Unified regenerative fuel cells (URFC) represent an attractive option to obtain hydrogen and generate energy using a compact device. Nevertheless, the fusion of a fuel cell (PEMFC) and a water electrolyzer continue to be a challenge because of the wide range of conditions to which this type of device is subject. Because of its kinetic characteristics, oxygen reduction reaction (ORR) in PEMFC and oxygen evolution reaction (OER) in PEMWE are the limiting stages of the URFC depending on the mode of operation. The primary focus of research related to URFC is the obtainment of bifunctional electrocatalysts that satisfactorily perform in both oxygen reactions and support the different working conditions found in a fuel cell and an electrolyzer. The present work contributes to the research on bifunctional electrocatalysts and shows some preliminary results from the electrochemical study of different Pt gcc, IrO{sub 2} and RuO{sub 2} mixtures supported in Ebonex® as oxygen electrodes. The electrochemical characterization with cyclic voltamperometry (CV), linear voltamperometry (LV) and electrochemical impedance spectroscopy (EIS) in H{sub 2}SO{sub 4} 0.5 M, in the absence and present of oxygen shows that Ebonex®-supported bifunctional electrodes IrO{sub 2}-Pt and RuO{sub 2}-Pt present reasonable electrocatalytic properties for oxygen evolution and reduction reactions and present the possibility of their use in an URFC. The Ir- based oxide electrodes show greater stability than ruthenium-oxide electrodes. [Spanish] Las celdas de combustible regenerativas unificadas (URFC) representan una atractiva opcion para la obtencion de hidrogeno y generacion de energia en un dispositivo compacto. Sin embargo, la fusion de una celda de combustible (PEMFC) y un electrolizador de agua (PEMWE) sigue siendo un reto por la amplia gama de condiciones a que se sujeta un dispositivo de este tipo. Por sus caracteristicas cineticas, la reaccion de reduccion de oxigeno (ORR) en la PEMFC y la

Electrocatalytical activity of Pt, SnO2 and RuO2 mixed electrodes for the electrooxidation of formic acid and formaldehyde

International Nuclear Information System (INIS)

Profeti, L.P.R.; Profeti, D.; Olivi, P.

2005-01-01

The electrocatalytical activity of binary electrodes of Pt and SnO 2 and ternary electrodes of Pt and SnO 2 and RuO 2 for the electrooxidation of formic acid and formaldehyde was investigated by cyclic voltammetry and chronoamperometry techniques. The electrode materials were prepared by the thermal decomposition of polymeric precursors at 400 deg C. The cyclic voltammetry results showed that the methanol electrooxidation process presents peak potentials for those electrodes approximately 100 mV lower than the values obtained for metallic platinum electrodes. The Pt 0.6 Ru 0.2 Sn 0.2 O y electrodes presented the highest current density values for potentials lower than the peak potential values. The chronoamperometric experiments also showed that the addition of SnO 2 and RuO 2 contributed for the enhancement of the electrode activity in low potential values. The preparation method was found to be useful to obtain high active materials. (author)

Unraveling micro- and nanoscale degradation processes during operation of high-temperature polymer-electrolyte-membrane fuel cells

Science.gov (United States)

Hengge, K.; Heinzl, C.; Perchthaler, M.; Varley, D.; Lochner, T.; Scheu, C.

2017-10-01

The work in hand presents an electron microscopy based in-depth study of micro- and nanoscale degradation processes that take place during the operation of high-temperature polymer-electrolyte-membrane fuel cells (HT-PEMFCs). Carbon supported Pt particles were used as cathodic catalyst material and the bimetallic, carbon supported Pt/Ru system was applied as anode. As membrane, cross-linked polybenzimidazole was used. Scanning electron microscopy analysis of cross-sections of as-prepared and long-term operated membrane-electrode-assemblies revealed insight into micrometer scale degradation processes: operation-caused catalyst redistribution and thinning of the membrane and electrodes. Transmission electron microscopy investigations were performed to unravel the nanometer scale phenomena: a band of Pt and Pt/Ru nanoparticles was detected in the membrane adjacent to the cathode catalyst layer. Quantification of the elemental composition of several individual nanoparticles and the overall band area revealed that they stem from both anode and cathode catalyst layers. The results presented do not demonstrate any catastrophic failure but rather intermediate states during fuel cell operation and indications to proceed with targeted HT-PEMFC optimization.

Metamorphosis of the mixed phase PtRu anode catalyst for direct methanol fuel cells after exposure of methanol: In situ and ex situ characterizations

Energy Technology Data Exchange (ETDEWEB)

Chakraborty, Debasish [Center for Individual Nanoparticle Functionality (CINF), Technical University of Denmark, DK-2800 Kgs. Lyngby (Denmark); Aerosol Laboratory, Nano.DTU, Department of Chemical Engineering, Technical University of Denmark, DK-2800 Kgs. Lyngby (Denmark); Chorkendorff, Ib [Center for Individual Nanoparticle Functionality (CINF), Technical University of Denmark, DK-2800 Kgs. Lyngby (Denmark); Department of Physics, Technical University of Denmark, DK-2800 Kgs. Lyngby (Denmark); Johannessen, Tue [Aerosol Laboratory, Nano.DTU, Department of Chemical Engineering, Technical University of Denmark, DK-2800 Kgs. Lyngby (Denmark)

2007-11-08

The change in the mixed phase heavily oxidized PtRu anode with the exposure of methanol in a direct methanol fuel cell (DMFC) has been investigated by electrochemical impedance spectroscopy (EIS) and X-ray diffraction (XRD). The investigation had two major objectives: (i) to explore the original state of the active catalyst and (ii) to understand if alloying of Pt and Ru is a requirement for higher methanol oxidation activity. It was found that the methanol oxidation activity gradually improved for {proportional_to}2 h of exposure. The impedance spectra were taken at different times within this time of improvement of activity. The impedance spectra were deconvoluted in different contributions like membrane resistance (R{sub m}), charge transfer resistance (R{sub Ct}), adsorption resistance (R{sub ad}), and oxidation resistance (R{sub ox}). The improvement of the activity was explained in terms of the effect of the pretreatment on different contributions. XRD was done on the virgin and methanol exposed sample as a possible mean to identify the difference. It was postulated that the reduction of the as prepared PtRu after exposure was responsible for the activity improvement. Also, it was shown that bulk alloy formation is not a necessary condition for higher methanol activity of PtRu catalysts. (author)

PENGARUH KUALITAS KEHIDUPAN KERJA DAN KEPUASAN KERJA TERHADAP KINERJA KARYAWAN PT PERTAMINA PERSERO RU IV CILACAP

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Astrianditya Januar Ristanti

2017-04-01

These results indicate that the quality of work life has significant influence but not the performance, job satisfaction has a significant impact on performance, while the quality of work life and job satisfaction has a significant impact on employee performance remains part of PT Pertamina Persero shift RU Cilacap.

Mixed valent noble metal perovskites Ba/sub 3/B/sup 3 +/Pt/sub x/Ru/sub 2-x//sup 4. 5+/O/sub 9/

Energy Technology Data Exchange (ETDEWEB)

Moessner, B; Kemmler-Sack, S; Ehmann, A [Tuebingen Univ. (Germany, F.R.). Lehrstuhl fuer Anorganische Chemie 2

1982-04-01

In perovskites of type Ba/sub 3/B/sup 3 +/Pt/sub x/Ru/sub 2-x//sup 4.5+/O/sub 9/ the ruthenium can be substituted by platinum up to x = 1. The compounds crystallize in a 1:2 ordered hexagonal BaTiO/sub 3/ structure (sequence (hcc)/sub 2/) with face connected Pt/sub x/Ru/sub 2-x/O/sub 9/ double octahedra. Intensity calculations on powder data of Ba/sub 3/YPt/sub 1/2/Ru/sub 3/2/O/sub 9/ (space group P6/sub 3//mmc) gave a refined, intensity related R' value of 8.6%. The vibrational spectroscopic and catalytic properties are reported.

Effect of Ni and noble metals (Ru, Pd and Pt) on performance of bifunctional MoP/SiO2 for hydroconversion of methyl laurate

Science.gov (United States)

Nie, Ziyang; Zhang, Zhena; Chen, Jixiang

2017-10-01

SiO2 supported bifunctional MoP catalysts modified with different metal promoters (Ni, Ru, Pd, Pt), where Mo/Ni and Mo/M(M = Ru, Pd and Pt) atomic ratios was respectively 10 and 40, were prepared by TPR method from the phosphate precursors. It was found that the introduction of metal promoters facilitated the reduction of phosphate precursor and enhanced the dispersion of MoP. However, the MoP catalyst acidity was scarcely influenced by the small amount of metal promoters. In the hydroconversion of methyl laurate, the promoters enhanced the MoP catalyst activity for conversion of methyl laurate and hydrogenation of alkenes (intermediate), but reduced isomerization ability. Among the promoters, Ru was an optimum to decrease selectivity to alkenes while maintain high selectivity to iso-alkanes, and Mo40RuP showed better stability than MoP. At 380 °C and 3.0 MPa, the conversion of methyl laurate, the total selectivity to C11 and C12 hydrocarbons and the selectivity to iso-alkanes maintained at 100%, ∼94% and ∼30% on Mo40RuP during 102 h, respectively. The good stability of Mo40RuP is ascribed to that the presence of Ru prevented the sintering of MoP particles and suppressed carbon deposition.

Investigation of the behavior of Pt-Ru mixtures with nafion in the oxygen reduction reaction; Investigacion del comportamiento de mezclas de Pt-Ru con nafion en la reaccion de reduccion de oxigeno

Energy Technology Data Exchange (ETDEWEB)

Enriquez M, O

2005-07-01

In this work the electrochemical study for the reduction reaction of oxygen (RRO) of ruthenium, platinum and two mixtures of Pt-Ru (10:90) and Pt-Ru (50:50); to this last its were determined the kinetic and electrochemical parameters. The platinum used was analytical platinum and the ruthenium it was obtained of the decarboxylation of 200 mg of ruthenium dode carbonyl with 200 ml of 1-2 dichlorobenzene under a reflux system by 20 hours with agitation. Decanted and centrifuged by 30 minutes, the obtained ruthenium was washed with ether and it was evaporated for it later use. The material was characterized by means of X-ray diffraction, elementary analysis, scanning electron microscopy and infrared spectroscopy. To determine the optimum quantity of nafion to be deposited on the catalytic material, they were carried out tests with different quantities deposited on the electrodes with 1, 2, 4 and 8 {mu}L, giving better result 2 {mu}L for that it was opted for to work with this proportion in the mixtures. The electrochemical performance of 2 ruthenium relationships and platinum 0.05 mg - 0.45 mg and 0.25 mg - 0.25 mg respectively were studied with a potentiostat galvanostat EG and G Princeton Applied Research model 273a; it was found that the electrode with the mixture of 0.25 mg of platinum with 0.25 mg of ruthenium has a bigger response of current intensity after to deposit the nafion in the surface. The electro active area was determined carrying out recurrent voltametry to different scanning velocities (5, 10, 20, 30, 40, 50, 60, 70 and 80 mV/s) in the non faraday region with a value of 0.2082 cm{sup 2}. The mixture Pt-Ru (50:50) it presents a first order kinetics for the RRO and it is carried out via 4 electrons; the study of current density in function of the temperature presents values of 0.47 {+-} 0.3 for the charge transfer coefficient, of 118 mV/decade for the Tafel slope and it has an activation energy of 0.39 eV. (Author)

Diamond nanoparticles as a support for Pt and PtRu catalysts for direct methanol fuel cells.

Science.gov (United States)

La-Torre-Riveros, Lyda; Guzman-Blas, Rolando; Méndez-Torres, Adrián E; Prelas, Mark; Tryk, Donald A; Cabrera, Carlos R

2012-02-01

Diamond in nanoparticle form is a promising material that can be used as a robust and chemically stable catalyst support in fuel cells. It has been studied and characterized physically and electrochemically, in its thin film and powder forms, as reported in the literature. In the present work, the electrochemical properties of undoped and boron-doped diamond nanoparticle electrodes, fabricated using the ink-paste method, were investigated. Methanol oxidation experiments were carried out in both half-cell and full fuel cell modes. Platinum and ruthenium nanoparticles were chemically deposited on undoped and boron doped diamond nanoparticles through the use of NaBH(4) as reducing agent and sodium dodecyl benzene sulfonate (SDBS) as a surfactant. Before and after the reduction process, samples were characterized by electron microscopy and spectroscopic techniques. The ink-paste method was also used to prepare the membrane electrode assembly with Pt and Pt-Ru modified undoped and boron-doped diamond nanoparticle catalytic systems, to perform the electrochemical experiments in a direct methanol fuel cell system. The results obtained demonstrate that diamond supported catalyst nanomaterials are promising for methanol fuel cells.

Mixed-valent perovskites of the type Ba/sub 3/Bsup(III)PtRuO/sub 9/

Energy Technology Data Exchange (ETDEWEB)

Kemmler-Sack, S; Ehmann, A; Herrmann, M [Tuebingen Univ. (Germany, F.R.). Lehrstuhl fuer Anorganische Chemie 2

1981-08-01

Compounds of type Ba/sub 3/Bsup(III)PtRuO/sub 9/ - with a mean oxydation state of the noble metals of +4.5 - crystallize with Bsup(III) = Gd-Lu, Y in a variant of hexagonal BaTiO/sub 3/ type with ordered cationic distribution. Intensity calculations on powder data of Ba/sub 3/YPtRuO/sub 9/ (a = 5.88/sub 8/; c = 14.7/sub 0/ A) gave in the space group P6/sub 3//mmc (sequence (hcc)/sub 2/) a refined, intensity related R' value of 5.9%. With Bsup(III) = Eu the lattice is monoclinic and for Bsup(III) = Sm, Nd, La triclinic distorted.

Dynamics of electrocatalytic oxidation of ethylene glycol, methanol and formic acid at MWCNT platform electrochemically modified with Pt/Ru nanoparticles

CSIR Research Space (South Africa)

Maxakato, NW

2010-03-01

Full Text Available Comparative electrocatalytic behavior of functionalized multiwalled carbon nanotubes (fMWCNTs) electrodecorated with Pt/Ru nanoparticles towards the oxidation of methanol (MeOH), ethylene glycol (EG) and formic acid (FA) has been investigated...

Nano-composite of PtRu alloy electrocatalyst and electronically conducting polymer for use as the anode in a direct methanol fuel cell

Energy Technology Data Exchange (ETDEWEB)

Jongho Choi; Kyungwon Park; Hyekyung Lee; Youngmin Kim; Jaesuk Lee; Yungeun Sung [Kwangju Inst. of Science and Technology, Dept. of Materials Science and Engineering, Gwangju (Korea)

2003-08-15

Nano-composites comprised of PtRu alloy nanoparticles and an electronically conducting polymer for the anode electrode in direct methanol fuel cell (DMFC) were prepared. Two conducting polymers of poly(N-vinyl carbazole) and poly(9-(4-vinyl-phenyl)carbazole) were used for the nano-composite electrodes. Structural analyses were carried out using Fourier transform nuclear magnetic resonance spectroscopy, AC impedance spectroscopy, X-ray diffraction (XRD), and transmission electron microscopy (TEM). Electrocatalytic activities were investigated by voltammetry and chronoamperometry in a 2 M CH{sub 3}OH/{sub 0.5} M H{sub 2}SO{sub 4} solution and the data compared with a carbon-supported PtRu electrode. XRD patterns indicated good alloy formation and nano-composite formation was confirmed by TEM. Electrochemical measurements and DMFC unit-cell tests indicate that the nano-composites could be useful in a DMFC, but its performance would be slightly lower than that of a carbon-supported electrode. The interfacial property between the PtRu-polymer nano-composite anode and the polymer electrolyte was good, as evidenced by scanning electron microscopy. For better performance in a DMFC, a higher electric conductivity of the polymer and a lower catalyst loss are needed in nano-composite electrodes. (Author)

Inelastic scattering on 100Ru

International Nuclear Information System (INIS)

Sirota, S.

1987-01-01

Aspects of the nuclear structure of 100 Ru whe investigated by means of the scattering of 100 Ru (p,p') 100 Ru* with 16 MeV protons, where 21 states were investigated. The emergent protons were analysed by a magnetic spectrograph, of the enge type with a typical resolution of ≅ 9 KeV. (A.C.A.S.) [pt

Conductivity study of thermally stabilized RuO2/polythiophene nanocomposites

Science.gov (United States)

Hebbar, Vidyashree; Bhajantri, R. F.

2018-04-01

The polymer nanocomposites of Ruthenium oxide (RuO2) filled polythiophene (PT) were synthesized by polymerization using chemical method. The purity of the synthesized polymer composite is verified using X-Ray diffraction (XRD). The structural discrepancies of the RuO2 filled PT composites are studied by Fourier transform infrared (FT-IR) spectroscopy. The phase transition and thermal stability of the prepared composite is revised by thermal characterization such as differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The DC conductivity of RuO2 filled PT composite in the form of pellets is calculated using current-voltage (I-V) characterization by two-probe method. The enhancement in conductivity with increased RuO2 content in PT matrix is examined, which is the required property for electrical and electronic applications in supercapacitors.

Amplified amperometric aptasensor for selective detection of protein using catalase-functional DNA-PtNPs dendrimer as a synergetic signal amplification label.

Science.gov (United States)

Zhang, Juan; Yuan, Yali; biXie, Shun; Chai, Yaqin; Yuan, Ruo

2014-10-15

In this work, we present a new strategy to construct an electrochemical aptasensor for sensitive detection of platelet-derived growth factor BB (PDGF-BB) based on the synergetic amplification of a three-dimensional (3D) nanoscale catalase (CAT) enzyme-functional DNA-platinum nanoparticles (PtNPs) dendrimer through autonomous layer-by-layer assembly. Firstly, polyamidoaminedendrimer (PAMAM) with a hyper-branched and three-dimensional structure was served as nanocarriers to coimmobilize a large number of PDGF-BB binding aptamer (PBA II) and ssDNA 1 (S1) to form PBA II-PAMAM-S1 bioconjugate. In the presence of PDGF-BB, the bioconjugate was self-assembled on the electrode by sandwich assay. Following that, the carried S1 propagated a chain reaction of hybridization events between CAT-PtNPs-S1 and CAT-PtNPs-ssDNA 2 (S2) to form a 3D nanoscale CAT-functional PtNPs-DNA dendrimer, which successfully immobilized substantial CAT enzyme and PtNPs with superior catalysis activity. In this process, the formed negatively charged double-helix DNA could cause the intercalation of hexaammineruthenium(III) chloride (RuHex) into the groove via electrostatic interactions. Thus, numerous RuHex redox probes and CAT were decorated inside/outside of the dendrimer. In the presence of H2O2 in electrolytic cell, the synergistic reaction of CAT and PtNPs towards electrocatalysis could further amplify electrochemical signal. Under optimal condition, the CAT-PtNPs-DNA dendrimer-based sensing system presented a linear dependence between the reduction peak currents and logarithm of PDGF-BB concentrations in the range of 0.00005-35 nM with a relatively low detection limit of 0.02 pM. Copyright © 2014 Elsevier B.V. All rights reserved.

Fabrication of Nonenzymatic Glucose Sensors Based on Multiwalled Carbon Nanotubes with Bimetallic Pt-M (M = Ru and Sn Catalysts by Radiolytic Deposition

Directory of Open Access Journals (Sweden)

Sun-Young Kwon

2012-01-01

Full Text Available Nonenzymatic glucose sensors employing multiwalled carbon nanotubes (MWNTs with highly dispersed Pt-M (M = Ru and Sn nanoparticles (Pt-M@PVP-MWNTs were fabricated by radiolytic deposition. The Pt-M nanoparticles on the MWNTs were characterized by transmittance electron microscopy, elemental analysis, and X-ray diffraction. They were found to be well dispersed and to exhibit alloy properties on the MWNT support. Electrochemical testing showed that these nonenzymatic sensors had larger currents (mA than that of a bare glassy carbon (GC electrode and one modified with MWNTs. The sensitivity (A mM−1, linear range (mM, and detection limit (mM (S/N = 3 of the glucose sensor with the Pt-Ru catalyst in NaOH electrolyte were determined as 18.0, 1.0–2.5, 0.7, respectively. The corresponding data of the sensor with Pt-Sn catalyst were 889.0, 1.00–3.00, and 0.3, respectively. In addition, these non-enzymatic sensors can effectively avoid interference arising from the oxidation of the common interfering species ascorbic acid and uric acid in NaOH electrolyte. The experimental results show that such sensors can be applied in the detection of glucose in commercial red wine samples.

Investigation of nano Pt and Pt-based alloys electrocatalysts for direct methanol fuel cells and their properties

Directory of Open Access Journals (Sweden)

Chunguang Suo

2014-03-01

Full Text Available The electrocatalysts used in micro direct methanol fuel cell (μDMFC, such as Pt/C and Pt alloy/C, prepared by liquid-phase NaBH4 reduction method have been investigated. XC-72 (Cobalt corp. Company, U.S.A is chosen as the activated carrier for the electrocatalysts to keep the catalysts powder in the range of several nanometers. The XRD, SEM, EDX analyses indicated that the catalysts had small particle size in several nanometers, in excellent dispersed phase and the molar ratio of the precious metals was found to be optimal. The performances of the DMFCs using cathodic catalyst with Pt percentage of 30wt% and different anodic catalysts (Pt-Ru, Pt-Ru-Mo were tested. The polarization curves and power density curves of the cells were measured to determine the optimal alloy composition and condition for the electrocatalysts. The results showed that the micro direct methanol fuel cell with 30wt% Pt/C as the cathodic catalyst and n(Pt:n(Ru:n(Mo = 3:2:2 PtRuMo/C as the anodic catalyst at room temperature using 2.0mol/L methanol solution has the best performances.

Nanoscale insight of high piezoelectricity in high-TC PMN-PH-PT ceramics

Science.gov (United States)

Zhu, Rongfeng; Zhang, Qihui; Fang, Bijun; Zhang, Shuai; Zhao, Xiangyong; Ding, Jianning

2018-03-01

The piezoelectric properties of the high-Curie temperature (high-TC) 0.15Pb(Mg1/3Nb2/3)O3-0.38PbHfO3-0.47PbTiO3 (0.15PMN-0.38PH-0.47PT) ceramics prepared by three different methods were compared. The 0.15PMN-0.38PH-0.47PT ceramics synthesized by the partial oxalate route exhibit the optimum properties, in which d33* = 845.3 pm/V, d33 = 456.2 pC/N, Kp = 67.2%, and TC = 291 °C. The nanoscale origin of the high piezoelectric response of the 0.15PMN-0.38PH-0.47PT ceramics was investigated by piezoresponse force microscopy (PFM) using the ceramics synthesized by the partial oxalate route. Large quantities of fine stripe submicron ferroelectric domains are observed, which form large island domains. In order to give further insights into the piezoelectric properties of the 0.15PMN-0.38PH-0.47PT ceramics from a microscopic point of view, the local poling experiments and local switching spectroscopy piezoresponse force microscopy (SS-PFM) were investigated, from which the local converse piezoelectric coefficient d33*(l) is calculated as 220 pm/V.

Electrochemical oxidation of methanol on Pt/(RuxSn1-xO2 nanocatalyst

Directory of Open Access Journals (Sweden)

Krstajić Mila N.

2013-01-01

Full Text Available The Ru-doped SnO2 powder, (RuxSn1-xO2, with the Sn:Ru atomic ratio of 9:1 was synthesized and used as a support for Pt nanoparticles (30 mass% loading. The (RuxSn1-xO2 support and Pt/(RuxSn1-xO2 catalyst were characterized by X-ray diffraction, energy dispersive X-ray spectroscopy and transmission electron microscopy (TEM. (RuxSn1-xO2 was found to be two-phase material consisting of probably solid solution of RuO2 in SnO2 and pure RuO2. The average Pt particle size determined by TEM was 5.3 nm. Cyclic voltammetry of Pt/(RuxSn1-xO2 indicated good conductivity of the sup-port and displayed usual features of Pt. The results of the electrochemical oxidation of COads and methanol on Pt/(RuxSn1-xO2 were compared with those on commercial Pt/C and PtRu/C catalysts. Oxidation of COads on Pt/(RuxSn1-xO2 starts at less positive potentials than on PtRu/C and Pt/C. Potentiodynamic polarization curves and chronoamperometric curves of methanol oxidation indicated higher initial activity of Pt/(RuxSn1-xO2 catalyst compared to PtRu/C, but also a greater loss in the current density over time. Potentiodynamic stability test of the catalysts revealed that deactivation of the Pt/(RuxSn1-xO2 and Pt/C was primarily caused by the poisoning of Pt surface by the methanol oxidation residues, which mostly occurred during the first potential cycle. In the case of PtRu/C the poisoning of the surface was minor and deactivation was caused by the PtRu surface area loss. [Projekat Ministarstva nauke Republike Srbije, br. ON-172054

Electrochemical properties of mixed WC and Pt-black powders

Directory of Open Access Journals (Sweden)

MAJA D. OBRADOVIC

2008-12-01

Full Text Available The electrochemical characteristics of a mixture of Pt-black and WC powders and its catalytic activity for methanol and formic acid oxidation were investigated in acid solution. XRD and AFM measurements revealed that the WC powder employed for the investigation was a single-phase material consisting of crystallites/spherical particles of average size of about 50 nm, which were agglomerated into much larger particles. Cyclic voltammetry showed that the WC underwent electrochemical oxidation, producing tungstate species. In the case of the mixed Pt + WC powders, the tungstate species were deposited on the Pt as a thin film of hydrous tungsten oxide. Enhanced hydrogen intercalation in the hydrous tungsten oxide was observed and it was proposed to be promoted in mixed powders by the presence of hydrogen adatoms on bare Pt sites. The determination of Pt surface area in the Pt + WC layer by stripping of underpotentially deposited Cu revealed that the entire Pt surface was accessible for underpotential deposition of Cu. Investigation of the electrochemical oxidation of methanol and formic acid on Pt + WC and pure Pt layers did not indicate electrocatalytic promotion due to the presence of WC.

Room temperature magnetism of few-nanometers-thick Fe{sub 3}O{sub 4}(111) films on Pt(111) and Ru(0001) studied in ambient conditions

Energy Technology Data Exchange (ETDEWEB)

Lewandowski, M., E-mail: lewandowski@amu.edu.pl [NanoBioMedical Centre, Adam Mickiewicz University, Umultowska 85, 61-614 Poznań (Poland); Institute of Molecular Physics, Polish Academy of Sciences, M. Smoluchowskiego 17, 60-179 Poznań (Poland); Miłosz, Z.; Michalak, N.; Ranecki, R. [Institute of Molecular Physics, Polish Academy of Sciences, M. Smoluchowskiego 17, 60-179 Poznań (Poland); Sveklo, I.; Kurant, Z.; Maziewski, A. [Faculty of Physics, University of Białystok, Lipowa 41, 15-424 Białystok (Poland); Mielcarek, S. [Faculty of Physics, Adam Mickiewicz University, Umultowska 85, 61-614 Poznań (Poland); Luciński, T. [Institute of Molecular Physics, Polish Academy of Sciences, M. Smoluchowskiego 17, 60-179 Poznań (Poland); Jurga, S. [NanoBioMedical Centre, Adam Mickiewicz University, Umultowska 85, 61-614 Poznań (Poland)

2015-09-30

Few-nanometers-thick Fe{sub 3}O{sub 4}(111) films were epitaxially grown on Pt(111) and Ru(0001) single crystal supports by sequential iron deposition and oxidation in an ultra-high vacuum chamber. The growth of well-ordered magnetite films was confirmed by low energy electron diffraction. The films were covered with a protective Au layer and subjected to magnetic and structural studies in ambient conditions. Magnetic hysteresis loops, recorded using magneto-optical Kerr effect apparatus, confirmed magnetic ordering in both films at room temperature. The Kerr measurements indicated in-plane orientation of magnetization, which was supported by the lack of magnetic contrast in magnetic force microscopy images. Atomic force microscopy revealed significant differences in morphology of the films, tentatively attributed to different lattice mismatch with Pt(111) and Ru(0001) single crystal supports. - Highlights: • Few-nanometers-thick Fe{sub 3}O{sub 4}(111) films were grown on Pt(111) and Ru(0001). • Magnetic properties were studied using MOKE and AFM/MFM in ambient conditions. • The films exhibited in-plane magnetic ordering at room temperature. • Differences in magnetic properties were tentatively assigned to structural differences.

Preparation of Pb(Zr0.52Ti0.48)O3 thin films on Pt/RuO2 double electrode by a new sol-gel route

International Nuclear Information System (INIS)

Kim, S.; Choi, Y.; Kim, C.; Oh, Y.

1997-01-01

Pb(Zr 0.52 Ti 0.48 )O 3 (PZT) thin film on Pt/RuO 2 double electrode was successfully prepared by using new alkoxide endash alkanolamine, sol-gel method. It was observed that the use of Pt/RuO 2 double electrode reduced leakage current, resulting in a marked improvement in the leakage characteristics and more reliable capacitors. Typical P-E hysteresis behavior was observed even at low applied voltage of 5 V, manifesting greatly improved remanance and coercivity. Fatigue and breakdown characteristic, measured at 5 V, showed stable behavior and no degradation in polarization was observed up to 10 11 cycles.copyright 1997 Materials Research Society

Oxidation study of Cr-Ru hard coatings

Energy Technology Data Exchange (ETDEWEB)

Chen, Yung-I, E-mail: yichen@mail.ntou.edu.tw; Kuo, Yu-Chu; Chen, Sin-Min

2012-01-01

Cr-Ru alloy coatings with Cr content ranging from 47 to 83 at.% were deposited at 400 Degree-Sign C by direct current magnetron co-sputtering with a Ti interlayer on silicon substrates. With a total input power of 300 W, the Cr content in the Cr-Ru coatings increased linearly with the increasing input power of Cr. The intermetallic compound phase Cr{sub 2}Ru with columnar structure was identified for the as-deposited Cr{sub 56}Ru{sub 44} and Cr{sub 65}Ru{sub 35} coatings, resulting in an increase of hardness up to 15-16 GPa. To evaluate the performance of Cr-Ru coatings as a protective coating on glass molding dies, the annealing treatment was conducted at 600 Degree-Sign C in a 50 ppm O{sub 2}-N{sub 2} atmosphere. The outward diffusion and preferential oxidization of Cr in the Cr-Ru coatings resulted in the variations of the crystalline structure, chemical composition distribution, and surface hardness after annealing. X-ray diffraction and transmission electron microscopy (TEM) proved that an oxide scale consisting of Cr{sub 2}O{sub 3} formed on the free surface. Scanning electron microscopy and TEM observed the surface morphology and structural variation. The chemical composition depth profiles were analyzed by Auger electron microscopy, verifying the presence of a Cr-depleted zone beneath the oxide scale. The hardness of Cr{sub 56}Ru{sub 44} and Cr{sub 65}Ru{sub 35} coatings decreased to 11-12 GPa after annealing, accompanied by the replacement of the Cr{sub 2}Ru phase by the Ru phase. - Highlights: Black-Right-Pointing-Pointer We prepared crystalline Cr-Ru alloy coatings by direct current magnetron sputtering. Black-Right-Pointing-Pointer Cr-Ru coatings were annealed at 600 Degree-Sign C for 2 h in a 50 ppm O{sub 2}-N{sub 2} atmosphere. Black-Right-Pointing-Pointer Cr diffused outwardly and oxidized to form a stable and protective oxide scale. Black-Right-Pointing-Pointer The original columnar grains recrystallized to polycrystalline grains.

Pt{sub X}Ru{sub Y}Ir{sub Z} as a bifunctional electrocatalyst for oxygen reduction reaction in a PEM fuel cell; Pt{sub X}Ru{sub Y}Ir{sub Z} como electrocatalizador bifuncional para la reaccion redox del oxigeno en una celda tipo PEM

Energy Technology Data Exchange (ETDEWEB)

Morales, L.; Fernandez, A.M. [Centro de Investigacion en Energia, Universidad Nacional Autonoma de Mexico, Temixco, Morelos (Mexico)]. E-mail: limos@cie.unam.mx; Cano, U. [Instituto de Investigaciones Electricas, Cuernavaca, Morelos (Mexico)

2009-09-15

This work presents the synthesis and characterization of the ternary material Pt{sub X}Ru{sub Y}Ir{sub Z}, obtained by chemical reduction with NaBH{sub 4}. Two different atomic compositions were developed (sample A and B) in order to observe the kinetic effect, as suggested by the combinatorial libraries. The main objective of this synthesis is to study the oxygen reduction reaction (ORR and OER) and its potential use in the construction of a bifunctional catalyst. In addition, each of the metals are synthesized separately using the same technique in order to make the corresponding comparison. The compounds obtained were characterized by sweep electron microscopy, x-ray diffraction and composition using fluorescence and energy-dispersive x-ray spectroscopy. The results showed a displacement of the x-ray diffraction peaks for Ir and Pt in sample A, and displacement in sample B for Ru and Ir peaks. These changes suggest the possible formation of a solid solution substitution. Separate cyclic and linear voltamperometry studies were performed for the oxygen reduction and release reactions. The electrochemical analysis showed improved kinetic behavior when combining the three metals according to the composition of sample B. [Spanish] En este trabajo se presenta la sintesis y caracterizacion del material ternario Pt{sub X}Ru{sub Y}Ir{sub Z}, elaborado por la tecnica de Reduccion Quimica utilizando al NaBH{sub 4}. Se elaboraron dos composiciones atomicas diferentes (Muestra A y B) con el fin de observar el efecto cinetico, como lo sugieren las librerias combinatorias. El objetivo principal de esta sintesis es para el estudio de la Reaccion Redox del Oxigeno (RRO y REO) y su potencial uso para la construccion de un catalizador bifuncional. Asi mismo, se realiza la sintesis de cada uno de los metales por separado empleando la misma tecnica, con el proposito de realizar la comparacion correspondiente. Los compuestos obtenidos se caracterizaron por Microscopia Electronica de

Effect of the solvent in the catalyst ink preparation on the properties and performance of unsupported PtRu catalyst layers in direct methanol fuel cells

International Nuclear Information System (INIS)

Alcaide, Francisco; Álvarez, Garbiñe; Cabot, Pere L.; Genova-Koleva, Radostina; Grande, Hans-Jürgen; Miguel, Oscar

2017-01-01

The effect of the organic solvent polarity on the properties of unsupported PtRu catalyst inks and on the performance of the catalyst layers prepared with them for the methanol electrooxidation, has been studied. The light scattering results indicate that the PtRu-Nafion ® aggregates in the inks prepared with n-butyl acetate (NBA) are larger than those prepared with 2-propanol (IPA). The lower polarity of the former favours the aggregation of Nafion ® and nanoparticles. The electron microscopy images and porosimetry measurements of the catalyst layers show that the secondary pore volume between the agglomerates is larger for NBA. The linear sweep voltammetry and eis results for the methanol electrooxidation in the three-electrode cell denote the higher active surface area for NBA and comparable specific oxidation rates of the intermediates in both catalysts layers. The current densities for PtRu anode catalyst layers in single DMFC are higher when the solvent is NBA, the mass transport limitations being much more apparent with IPA. The adapted transmission line equivalent circuit to interpret the impedance results in single DMFC indicates that the proton resistance for NBA is significantly lower than for IPA, thus suggesting that the greater number of accessible active sites for methanol oxidation in the former are well connected to the Nafion ® ionomers and easier transported to the membrane.

[Zn(NH3)4][PtCl6] and [Cd(NH3)4][PtCl6] as precursors for intermetallic compounds PtZn and PtCd

International Nuclear Information System (INIS)

Zadesenets, A.V.; Venediktov, A.B.; Shubin, Yu.V.; Korenev, S.V.

2007-01-01

Double complex salts (tetraamminezinc and tetraamminecadmium hexachloroplatinates) have been synthesized. Their thermal properties have been studied, as well as the products of their degradation in hydrogen and helium atmospheres. Optimal thermolysis schedules have been determined. Thermolysis under hydrogen yields intermetallic compounds PtZn and PtCd [ru

Low-Temperature Preparation of (111)-oriented Pb(Zr,Ti)O3 Films Using Lattice-Matched (111)SrRuO3/Pt Bottom Electrode by Metal-Organic Chemical Vapor Deposition

Science.gov (United States)

Kuwabara, Hiroki; Sumi, Akihiro; Okamoto, Shoji; Hoko, Hiromasa; Cross, Jeffrey S.; Funakubo, Hiroshi

2009-04-01

Pb(Zr0.35Ti0.65)O3 (PZT) films 170 nm thick were prepared at 415 °C by pulsed metal-organic chemical vapor deposition. The (111)-oriented PZT films with local epitaxial growth were obtained on (111)SrRuO3/(111)Pt/TiO2/SiO2/Si substrates and their ferroelectricities were ascertained. Ferroelectricity was improved by postannealing under O2 gas flow up to 550 °C. Larger remanent polarization and better fatigue endurance were obtained using a SrRuO3 top electrode compared to a Pt top electrode for PZT films after annealing at 500 °C.

Temperature-Dependent Physical and Memory Characteristics of Atomic-Layer-Deposited RuOx Metal Nanocrystal Capacitors

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S. Maikap

2011-01-01

Full Text Available Physical and memory characteristics of the atomic-layer-deposited RuOx metal nanocrystal capacitors in an n-Si/SiO2/HfO2/RuOx/Al2O3/Pt structure with different postdeposition annealing temperatures from 850–1000°C have been investigated. The RuOx metal nanocrystals with an average diameter of 7 nm and a highdensity of 0.7 × 1012/cm2 are observed by high-resolution transmission electron microscopy after a postdeposition annealing temperature at 1000°C. The density of RuOx nanocrystal is decreased (slightly by increasing the annealing temperatures, due to agglomeration of multiple nanocrystals. The RuO3 nanocrystals and Hf-silicate layer at the SiO2/HfO2 interface are confirmed by X-ray photoelectron spectroscopy. For post-deposition annealing temperature of 1000°C, the memory capacitors with a small equivalent oxide thickness of ~9 nm possess a large hysteresis memory window of >5 V at a small sweeping gate voltage of ±5 V. A promising memory window under a small sweeping gate voltage of ~3 V is also observed due to charge trapping in the RuOx metal nanocrystals. The program/erase mechanism is modified Fowler-Nordheim (F-N tunneling of the electrons and holes from Si substrate. The electrons and holes are trapped in the RuOx nanocrystals. Excellent program/erase endurance of 106 cycles and a large memory window of 4.3 V with a small charge loss of ~23% at 85°C are observed after 10 years of data retention time, due to the deep-level traps in the RuOx nanocrystals. The memory structure is very promising for future nanoscale nonvolatile memory applications.

The influence of methanol on the chemical state of PtRu anodes in a high-temperature direct methanol fuel cell studied in situ by synchrotron-based near-ambient pressure x-ray photoelectron spectroscopy

International Nuclear Information System (INIS)

Saveleva, Viktoriia A; Savinova, Elena R; Daletou, Maria K

2017-01-01

Synchrotron radiation-based near-ambient pressure x-ray photoelectron spectroscopy (NAP-XPS) has recently become a powerful tool for the investigation of interfacial phenomena in electrochemical power sources such as batteries and fuel cells. Here we present an in situ NAP-XPS study of the anode of a high-temperature direct methanol fuel cell with a phosphoric acid-doped hydrocarbon membrane, which reveals an enhanced flooding of the Pt 3 Ru anode with phosphoric acid in the presence of methanol. An analysis of the electrode surface composition depending on the cell voltage and on the presence of methanol reveals the strong influence of the latter on the extent of Pt oxidation and on the transformation of Ru into Ru (IV) hydroxide. (paper)

The influence of methanol on the chemical state of PtRu anodes in a high-temperature direct methanol fuel cell studied in situ by synchrotron-based near-ambient pressure x-ray photoelectron spectroscopy

Science.gov (United States)

Saveleva, Viktoriia A.; Daletou, Maria K.; Savinova, Elena R.

2017-01-01

Synchrotron radiation-based near-ambient pressure x-ray photoelectron spectroscopy (NAP-XPS) has recently become a powerful tool for the investigation of interfacial phenomena in electrochemical power sources such as batteries and fuel cells. Here we present an in situ NAP-XPS study of the anode of a high-temperature direct methanol fuel cell with a phosphoric acid-doped hydrocarbon membrane, which reveals an enhanced flooding of the Pt3Ru anode with phosphoric acid in the presence of methanol. An analysis of the electrode surface composition depending on the cell voltage and on the presence of methanol reveals the strong influence of the latter on the extent of Pt oxidation and on the transformation of Ru into Ru (IV) hydroxide.

Platinum assisted by carbon quantum dots for methanol electro-oxidation

Science.gov (United States)

Pan, Dan; Li, Xingwei; Zhang, Aofeng

2018-01-01

Various types of fuel cells as clean and portable power sources show a great attraction, especially direct methanol fuel cell (DMFC) having high energy density, low operating temperature and convenient fuel storage. However, the preparation of low-cost Pt-based catalysts with satisfactory catalytic performance still faces many challenges for its commercialization on large scale. Here, Pt catalysts assisted by carbon quantum dots (CQDs) are reported. The synergistic effect of carbon quantum dots and Pt metals is similar to a bi-component catalyst, such as PtRu. First, carbon quantum dots derived from Vulcan XC-72 carbon black are synthesized by mixed acid etching. Then, carbon black (Vulcan XC-72) is soaked in carbon quantum dots solution for several days to obtain carbon black modified by carbon quantum dots (XC-72-CQDs). Finally, Pt catalysts are supported on XC-72-CQDs (Pt/XC-72-CQDs) through a simple chemical reduction method. For methanol electro-oxidation reaction, the catalytic performance of Pt/XC-72-CQDs is compared with commercial PtRu/C (30% Pt + 15% Ru). Results show that a typical product (Pt/XC-72-CQDs5) exhibits a better catalytic activity than PtRu/C. In cyclic voltammetry test, the specific activity of Pt/XC-72-CQDs5 is 1.06 mA cm-2 Pt and 477.6 mA mg-1 Pt, while that of PtRu/C is 0.77 mA cm-2 Pt and 280.6 mA mg-1 Pt.

Use of Dendrimers during the Synthesis of Pt-Ru Electrocatalysts for PEM Fuel Cells: Effects on the Physical and Electrochemical Properties

Directory of Open Access Journals (Sweden)

J. C. Calderón

2011-01-01

Full Text Available In this work, Pt-Ru catalysts were synthesized by a novel methodology which includes the use as encapsulating molecules of dendrimers of different generation: zero (DN-0, one (DN-1, two (DN-2, and three (DN-3. Synthesized catalysts were heat-treated at 350°C, and the effects of this treatment was established from the physical (X-ray dispersive energy (XDE and X-ray diffraction (XRD and electrochemical characterization (cyclic voltammetry and chronoamperometry. Results showed that the heat-treatment benefits the catalytic properties of synthesized materials in terms of CO and methanol electrochemical oxidation. The curves for CO stripping were more defined for heat-treated catalysts, and methanol oxidation current densities were higher for these materials. These changes are principally explained from the removal of organic residues remaining on the surface of the Pt-Ru nanoparticles after the synthesis procedure. After the activation of the catalysts by heating at 350°C, the real importance of the use of these encapsulating molecules and the effect of the generation of the dendrimer become visible. From these results, it can be concluded that synthesized catalysts are good catalytic anodes for direct methanol fuel cells (DMFCs.

Surface noble metal modified PdM/C (M = Ru, Pt, Au) as anode catalysts for direct ethanol fuel cells

International Nuclear Information System (INIS)

Mao, Han; Huang, Tao; Yu, Aishui

2016-01-01

In this article, we studied the surface noble metal modification on Pd nanoparticles, other than the homogeneous or core-shell structure. The surface modification will lead to the uneven constitution within the nanoparticles and thus more obvious optimization effect toward the catalyst brought by the lattice deformation. The surface of the as-prepared Pd nanoparticles was modified with Ru, Pt or Au by a moderate and green approach, respectively. XPS results confirm the interactive electron effects between Pd and the modified noble metal. Electrochemical measurements show that the surface noble metal modified catalysts not only show higher catalytic activity, but also better stability and durability. The PdM/C catalysts all exhibit good dispersion and very little agglomeration after long-term potential cycles toward ethanol oxidation. With only 10% metallic atomic ratio of Au, PdAu/C catalyst shows extraordinary catalytic activity and stability, the peak current reaches 1700 mA mg"−"1 Pd, about 2.5 times that of Pd/C. Moreover, the PdAu/C maintains 40% of the catalytic activity after 4500 potential cycles. - Highlights: • Pd-based catalysts with complicated exposed facets. • Much enhanced electrocatalytic activity and stability with about 10% noble metal M (M = Ru, Pt, Au) on Pd nanoparticles. • The outstanding electrocatalytic performance of PdAu/C towards ethanol oxidation after the Au modification.

Surface noble metal modified PdM/C (M = Ru, Pt, Au) as anode catalysts for direct ethanol fuel cells

Energy Technology Data Exchange (ETDEWEB)

Mao, Han; Huang, Tao, E-mail: huangt@fudan.edu.cn; Yu, Aishui, E-mail: asyu@fudan.edu.cn

2016-08-15

In this article, we studied the surface noble metal modification on Pd nanoparticles, other than the homogeneous or core-shell structure. The surface modification will lead to the uneven constitution within the nanoparticles and thus more obvious optimization effect toward the catalyst brought by the lattice deformation. The surface of the as-prepared Pd nanoparticles was modified with Ru, Pt or Au by a moderate and green approach, respectively. XPS results confirm the interactive electron effects between Pd and the modified noble metal. Electrochemical measurements show that the surface noble metal modified catalysts not only show higher catalytic activity, but also better stability and durability. The PdM/C catalysts all exhibit good dispersion and very little agglomeration after long-term potential cycles toward ethanol oxidation. With only 10% metallic atomic ratio of Au, PdAu/C catalyst shows extraordinary catalytic activity and stability, the peak current reaches 1700 mA mg{sup −1} Pd, about 2.5 times that of Pd/C. Moreover, the PdAu/C maintains 40% of the catalytic activity after 4500 potential cycles. - Highlights: • Pd-based catalysts with complicated exposed facets. • Much enhanced electrocatalytic activity and stability with about 10% noble metal M (M = Ru, Pt, Au) on Pd nanoparticles. • The outstanding electrocatalytic performance of PdAu/C towards ethanol oxidation after the Au modification.

Laminated structure in internally oxidized Ru-Ta coatings

Energy Technology Data Exchange (ETDEWEB)

Chen, Yung-I, E-mail: yichen@mail.ntou.edu.tw

2012-12-01

During the development of refractory alloy coatings for protective purposes at high temperature under oxygen-containing atmospheres, previous studies noted and examined the internal oxidation phenomenon for Mo-Ru and Ru-Ta coatings. The internally oxidized zone shows a laminated structure, consisting of alternating oxygen-rich and deficient layers stacked with a general orientation. Previous studies proposed a forming mechanism. To investigate in detail, Ru-Ta coatings were prepared with various rotating speeds of a substrate-holder. The coatings were annealed at 600 Degree-Sign C in an atmosphere continuously purged with 1% O{sub 2}-99% Ar mixed gas for 30 min. Transmission electron microscopy was used to examine the laminated-layer periods. Auger electron spectroscopy depth profiles certified the periodical variation of the related constituents. X-ray photoelectron spectroscopy proved the valence variation of Ta in the near surface, accompanied by the introduction of oxygen ions. The inward diffusion of oxygen was dominated by lattice diffusion. - Highlights: Black-Right-Pointing-Pointer Laminated Ru-Ta coatings consisted of a cyclical gradient concentration. Black-Right-Pointing-Pointer The as-deposited coatings showed a laminated structure with a period of 4-34 nm. Black-Right-Pointing-Pointer Internal oxidation of Ru-Ta coatings executed after annealing in 1% O{sub 2}-Ar atmosphere. Black-Right-Pointing-Pointer Oxygen inward diffusion was dominated by lattice diffusion.

Chalcogenide oxygen reduction reaction catalysis: X-ray photoelectron spectroscopy with Ru, Ru/Se and Ru/S samples emersed from aqueous media

Energy Technology Data Exchange (ETDEWEB)

Lewera, A. [Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, IL 61801 (United States); Department of Chemistry, Warsaw University, Pasteura 1, 02-093 Warsaw (Poland); Inukai, J. [Clean Energy Research Center, University of Yamanashi, 7-32 Miyamae-cho, Kofu 400-0006 (Japan); Zhou, W.P. [Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, IL 61801 (United States); Cao, D. [Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, IL 61801 (United States); College of Material Science and Chemical Engineering, Harbin Engineering University, Harbin 150001 (China); Duong, H.T. [Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, IL 61801 (United States); Alonso-Vante, N. [Laboratory of Electrocatalysis, UMR-CNRS 6503, University of Poitiers, F-86022 Poitiers (France)]. E-mail: Nicolas.Alonso.Vante@univ-poitiers.fr; Wieckowski, A. [Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, IL 61801 (United States)]. E-mail: andrzej@scs.uiuc.edu

2007-05-10

Oxygen reduction Ru/Se and Ru/S fuel cell surface chalcogenide catalysts were prepared via chemical reaction of reduced Ru nanoparticles with selenium and sulfur in xylenes [D. Cao, A. Wieckowski, J. Inukai, N. Alonso-Vante, J. Electrochem. Soc. 153 (2006) A869]. The chalcogenide samples - as well as the starting chalcogens-free Ru nanoparticle material - were immobilized on a gold disk for X-ray Photoelectron Spectroscopy (XPS) characterization. While we found oxygen in most of the samples, predominantly from Ru oxides, we conclude that the oxygen on Ru/S may be located in subsurface sites: the subsurface oxygen. We also found that the transformation of the oxidized Ru black to metallic Ru required intensive electrochemical treatment, including hydrogen evolution. In contrast, five cyclic voltammetric scans in the potential range from 0.00 and 0.75 V versus RHE were sufficient to remove the oxygen forms from Ru/Se and, to a large extent, from Ru/S. We therefore conclude that Ru metal is protected against oxidation to Ru oxides by the chalcogens additives. The voltammetric treatment in the 0.00 and 0.75 V range also removed the SeO{sub 2} or SO {sub x} forms leaving anionic/elemental Se or S on the surface. Upon larger amplitude voltammetric cycling, from 0.00 to 1.20 V versus RHE, both Se and S were dissolved and the dissolution process was coincidental with the oxygen growth in/on the Ru samples.

Chalcogenide oxygen reduction reaction catalysis: X-ray photoelectron spectroscopy with Ru, Ru/Se and Ru/S samples emersed from aqueous media

International Nuclear Information System (INIS)

Lewera, A.; Inukai, J.; Zhou, W.P.; Cao, D.; Duong, H.T.; Alonso-Vante, N.; Wieckowski, A.

2007-01-01

Oxygen reduction Ru/Se and Ru/S fuel cell surface chalcogenide catalysts were prepared via chemical reaction of reduced Ru nanoparticles with selenium and sulfur in xylenes [D. Cao, A. Wieckowski, J. Inukai, N. Alonso-Vante, J. Electrochem. Soc. 153 (2006) A869]. The chalcogenide samples - as well as the starting chalcogens-free Ru nanoparticle material - were immobilized on a gold disk for X-ray Photoelectron Spectroscopy (XPS) characterization. While we found oxygen in most of the samples, predominantly from Ru oxides, we conclude that the oxygen on Ru/S may be located in subsurface sites: the subsurface oxygen. We also found that the transformation of the oxidized Ru black to metallic Ru required intensive electrochemical treatment, including hydrogen evolution. In contrast, five cyclic voltammetric scans in the potential range from 0.00 and 0.75 V versus RHE were sufficient to remove the oxygen forms from Ru/Se and, to a large extent, from Ru/S. We therefore conclude that Ru metal is protected against oxidation to Ru oxides by the chalcogens additives. The voltammetric treatment in the 0.00 and 0.75 V range also removed the SeO 2 or SO x forms leaving anionic/elemental Se or S on the surface. Upon larger amplitude voltammetric cycling, from 0.00 to 1.20 V versus RHE, both Se and S were dissolved and the dissolution process was coincidental with the oxygen growth in/on the Ru samples

Improvement of energy conversion efficiency and power generation in direct borohydride-hydrogen peroxide fuel cell: The effect of Ni-M core-shell nanoparticles (M = Pt, Pd, Ru)/Multiwalled Carbon Nanotubes on the cell performance

Science.gov (United States)

Hosseini, M. G.; Mahmoodi, R.

2017-12-01

In this study, core@shell nanoparticles with Ni as a core material and Pt, Pd and Ru as shell materials are synthesized on multiwalled carbon nanotube (MWCNT) as catalyst support using the sequence reduction method. The influence of Ni@Pt, Ni@Pd and Ni@Ru core@shell nanoparticles on MWCNT toward borohydride oxidation in alkaline solution is investigated by various three-electrode electrochemical techniques. Also, the impact of these anodic electrocatalysts on the performance of direct borohydride-hydrogen peroxide fuel cell (DBHPFC) is evaluated. The structural and morphological properties of electrocatalysts are studied by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), energy-dispersive X-ray spectroscopy (EDX), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HR-TEM) and X-ray photoelectron spectroscopy (XPS). The results of three electrode investigations show that Ni@Pd/MWCNT has excellent catalytic activity since borohydride oxidation current density on Ni@Pd/MWCNT (34773.27 A g-1) is 1.37 and 9.19 times higher than those of Ni@Pt/MWCNT (25347.27 A g-1) and Ni@Ru/MWCNT (3782.83 A g-1), respectively. Also, the energy conversion efficiency and power density of DBHPFC with Ni@Pd/MWCNT (246.82 mW cm-2) increase to 34.27% and 51.53% respect to Ni@Pt/MWCNT (162.24 mW cm-2) and Ni@Ru/MWCNT (119.62 mW cm-2), respectively. This study reveals that Ni@Pd/MWCNT has highest activity toward borohydride oxidation and stability in fuel cell.

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.

Science.gov (United States)

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.

Pt20RuxSny nanoparticles dispersed on mesoporous carbon CMK-3 and their application in the oxidation of 2-carbon alcohols and fermentation effluent

International Nuclear Information System (INIS)

Lo, An-Ya; Chung, Yi-Chen; Hung, Wei-Hsuan; Hsu, Yun-Chi; Tseng, Chuan-Ming; Zhang, Wei-Lun; Wang, Fu-Kai; Lin, Chiu-Yue

2017-01-01

Highlights: • Pt 20 Ru x Sn y @C catalysts are formed by dispersing Pt-Sn and Pt-Ru-Sn NPs on CMK-3. • They are tested in fuel cells using ethanol, ethylene glycol, and CFHPE as fuels. • Higher Sn contents improve catalytic efficiency of Pt 20 Ru x Sn y when x = 0 or x = 10. • Role of Sn in C−C bond cleavage and improving poisoning tolerance is explained. • Pt 20 Ru 10 Sn 15 @C is used to show feasibility of using bioalcohol from CFHPE as fuel. - Abstract: We report the synthesis of Pt-Sn binary and Pt-Ru-Sn ternary alloy nanoparticles (NPs) dispersed on mesoporous carbon CMK-3 for bioalcohol fuel cell applications where ethanol, ethylene glycol, and fermentative hydrogen production effluent were used as the fuels. The proposed alloy electrocatalysts, denoted as Pt 20 Ru x Sn y @C (where 20, x, and y represent the weight fractions of Pt, Ru, and Sn, respectively), were examined using scanning electron microscopy, energy-dispersive X-ray spectroscopy mapping, transmission electron microscopy, Brunauer-Emmett-Teller measurements, X-ray diffraction analysis, and electrochemical measurements, in order to determine their morphologies, microstructures, compositions, phase structures, and electrochemical characteristics. The effects of the Sn content on the following factors were examined: 1) average particle size of the alloy NPs, 2) mesoporosity, 3) electrochemically active surfaces of Pt 20 Ru x Sn y @C, and 4) ethanol oxidation reaction and ethylene glycol oxidation reaction activities. Higher Sn contents improved the catalytic efficiency of Pt 20 Ru x Sn y when x = 0 or x = 10, with the optimized compositions being Pt 20 Sn 30 and Pt 20 Ru 10 Sn 15 for the binary and ternary alloys, respectively. Based on the ethanol and ethylene glycol oxidation reactions, we explain the role of Sn in promoting C−C bond cleavage and in improving catalyst tolerance against poisoning. Overall, for both the ethanol system and the ethylene glycol system, the catalytic

Novel synthesis of core-shell Au-Pt dendritic nanoparticles supported on carbon black for enhanced methanol electro-oxidation

Science.gov (United States)

Cao, Ribing; Xia, Tiantian; Zhu, Ruizhi; Liu, Zhihua; Guo, Jinming; Chang, Gang; Zhang, Zaoli; Liu, Xiong; He, Yunbin

2018-03-01

Core-shell Au-Pt dendritic nanoparticles (Au-Pt NPs) has been synthesized via a facile seed-mediated growth method, in which dendritic Pt nanoparticles as shell grow on the surface of gold nanocores by using ascorbic acid (AA) as "green" reducing reagents. The morphologies and compositions of the as-prepared nanocomposites with core-shell structure are characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS). Electrochemical experiments, including cyclic voltammetry (CV) and chronoamperometry (CA) are performed to investigate the electrocatalytic properties of the Au-Pt NPs loaded carbon black composites (Au-Pt NPs/V) towards methanol oxidation in an alkaline solution. It is found that the reduction time of AA could regulate the thickness and amount of Pt on the Au nanocores, which significantly affect catalytic activity of the Au-Pt NPs/V toward methanol oxidation. Au-Pt NPs/V with optimum reduction time 4 h exhibit 2.3-times higher electrocatalytic activity than that of a commercial catalyst (Pt/carbon black) and an excellent CO tolerance toward methanol oxidation. This behavior is attributed to large active electrochemical area of the bimetallic nanocomposites and the change in the electronic structure of Pt when Au surface modified with fewer Pt nanoparticles.

Structural, optical and magnetic characterization of Ru doped ZnO nanorods

International Nuclear Information System (INIS)

Kumar, Sanjeev; Kaur, Palvinder; Chen, C.L.; Thangavel, R.; Dong, C.L.; Ho, Y.K.; Lee, J.F.; Chan, T.S.; Chen, T.K.; Mok, B.H.; Rao, S.M.; Wu, M.K.

2014-01-01

Graphical abstract: Ruthenium (Ru = 0%, 1% and 2%) doped nano-crystalline zinc oxide (ZnO) nanorods were synthesized by using well-known sol–gel technique. X-ray diffraction (XRD) results show that Ru (0%, 1% and 2%) doped ZnO nanorods crystallized in the wurtzite structure having space group C 3v (P6 3 mc). Williamson and Hall plot reveal that in the nanoscale dimensions, incorporation of Ru induced the tensile strain in ZnO host matrix. Photoluminescence (PL) and Raman studies of Ru doped ZnO nanorods show the formation of singly ionized oxygen vacancies which may account for the observed room temperature ferromagnetism (RTFM) in 2% Ru doped ZnO. X-ray absorption spectroscopy (XAS) reveals that Ru replace the Zn atoms in the host lattice and maintain the crystal symmetry with slightly lattice distortion. Highlights: • Ru doped ZnO nanorods crystallized in the wurtzite structure having space group C 3v (P6 3 mc). • PL and Raman studies show the formation of singly ionized oxygen vacancies in 2% Ru doped ZnO. • XAS reveals that Ru replace the Zn atoms in the host lattice with slightly lattice distortion. • Doping of Ru in ZnO nanostructures gives rise to RTFM ordering. -- Abstract: Ruthenium (Ru = 0%, 1% and 2%) doped nano-crystalline zinc oxide (ZnO) nanorods were synthesized by using well-known sol–gel technique. X-ray diffraction (XRD) results show that Ru (0%, 1% and 2%) doped ZnO nanorods crystallized in the wurtzite structure having space group C 3v (P6 3 mc). Williamson and Hall plot reveal that in the nanoscale dimensions, incorporation of Ru induced the tensile strain in ZnO host matrix. Photoluminescence (PL) and Raman studies of Ru doped ZnO nanorods show the formation of singly ionized oxygen vacancies which may account for the observed room temperature ferromagnetism (RTFM) in 2% Ru doped ZnO. X-ray absorption spectroscopy (XAS) reveals that Ru replace the Zn atoms in the host lattice and maintain the crystal symmetry with slightly lattice

Nanoscale compositional changes and modification of the surface reactivity of Pt3Co/C nanoparticles during proton-exchange membrane fuel cell operation

International Nuclear Information System (INIS)

Dubau, L.; Maillard, F.; Chatenet, M.; Andre, J.; Rossinot, E.

2010-01-01

This study bridges the structure/composition of Pt-Co/C nanoparticles with their surface reactivity and their electrocatalytic activity. We show that Pt 3 Co/C nanoparticles are not stable during PEMFC operation (H 2 /air; j = 0.6 A cm -2 , T = 70 o C) but suffer compositional changes at the nanoscale. In the first hours of operation, the dissolution of Co atoms at their surface yields to the formation of a Pt-enriched shell covering a Pt-Co alloy core ('Pt-skeleton') and increases the affinity of the surface to oxygenated and hydrogenated species. This structure does not ensure stability in PEMFC conditions but is rather a first step towards the formation of 'Pt-shell/Pt-Co alloy core' structures with depleted Co content. In these operating conditions, the Pt-Co/C specific activity for the ORR varies linearly with the fraction of Co alloyed to Pt present in the core and is severely depreciated (ca. -50%) after 1124 h of operation. This is attributed to: (i) the decrease of both the strain and the ligand effect of Co atoms contained in the core (ii) the changes in the surface structure of the electrocatalyst (formation of a multilayer-thick Pt shell) and (iii) the relaxation of the Pt surface atoms.

Applications Ni59Nb40Pt(1-x) Xx (X= Sn,Sby and Ru) amorphous alloy as anodes for direct methanol (DMFC) fuel cells

International Nuclear Information System (INIS)

Rodriguez Pierna, A

2005-01-01

The search of new anode materials of amorphous nature for methanol fuel cells is one of the aims of this work.The main problem that fuel cells present is related to the catalytic material and its distribution in a suitable matrix.Amorphous alloys are particularly attractive materials as catalyst supports because of their high conductivity, high corrosion resistance in sulphuric acid, as well as the possibility of a good distribution of the electrocatalytic particles, mainly platinum and platinum-tin, on a conducting matrix.The electrooxidation of methanol, in percloric acid medium, has been used as probe to evaluate the performance of metallic amorphous electrodes, with compositions Ni 5 9Nb 4 0Pt 1 , Ni 5 9Nb 4 0Pt 0 .6Sn0.4, Ni 5 9Nb 4 0Pt 0 .6Sb 0 .4 and Ni 5 9Nb 4 0Pt 0 .6Ru 0 .4.The electrocatalytic activity of the alloyed ribbons of compositions (x = 0.6, 1% at. in platinum) is improved considerably, so much for the change in their composition, as for the roughness degree that the catalytic surfaces present. The increase of the tolerance to adsorbed species, and better resistance to the poisoning of their catalytic centers, can be observed by means of voltammetric experiments at different activation times with HF 48%. The electrooxidation of methanol in the amorphous alloy of composition Ni 5 9Nb 4 0Pt 1 , is influenced by the nature of the used electrolyte, presenting smaller values of current density in solutions 1M H 2 SO 4 than in 1M of HClO 4 .This behavior is not observed in the alloy Ni 5 9Nb 4 0Pt 0 .6Sn 0 .4, Ni 5 9Nb 4 0Pt 0 .6Sb 0 .4 and Ni 5 9Nb 4 0Pt 0 .6Ru 0 .4which does not present a poisoning of the catalytic centers depending on the used electrolyte.Adding tin to the alloys showed the existence of a synergetic effect in the methanol electrooxidation process, attaining to a descent of 20 mV vs Ag/AgCl in the onset potential, and about 200 mV in the maximun peak potential

Electrochemical oxidation of ammonia-containing wastewater using Ti/RuO2-Pt electrode

Directory of Open Access Journals (Sweden)

Wei-wu Hu

2009-12-01

Full Text Available The electrochemical oxidation degradation processes for artificial and actual wastewater containing ammonia were carried out with a Ti/RuO2-Pt anode and a Ti plate cathode. We studied the effects of different current densities, space sizes between the two electrodes, and amounts of added NaCl on ammonia-containing wastewater treatment. It was shown that, after a 30-min treatment under the optimal conditions, which were a current density of 20 mA/cm2, a space size between the two electrodes of 1 cm, and an added amount of 0.5 g/L of NaCl, the COD concentration in municipal wastewater was 40 mg/L, a removal rate of 90%; and the NH3-N concentration was 7 mg/L, a removal rate of 88.3%. The effluent of municipal wastewater qualified for Class A of the Discharge Standard of Pollutants for Municipal Wastewater Treatment Plant (GB18918-2002.

Analisis Bahaya Fisik: Hubungan Tingkat Pencahayaan dan Keluhan Mata Pekerja pada Area Perkantoran Health, Safety, and Environmental (HSE PT. Pertamina RU VI Balongan

Directory of Open Access Journals (Sweden)

Dina Rahmayanti

2016-04-01

Full Text Available The eyes are part of the body that must be protected workers safety and health. Sufficient light is one of the most important aspects that determine the health of the eye, excellent lighting intensity affects the eyes. This study was performed at PT Pertamina RU VI Balongan, based on observation in the work area, it is necessary to evaluate the intensity of light and eye strain workers in a unit of PT. Pertamina Refinery Unit VI Balongan.Be collected from primary and secondary data and processing in the form of statistical testing using Microsoft Excel and SPSS Software 2.0. Tests conducted on four types of questionnaires and data variables intensity lighting in the office area of HSE unit RU VI Balongan.There are 12 rooms which have the following illumination standard (under 300 lux. Based on a statistical test between the variable quality of the lighting of the eye complaints get results there are two variables that have a relationship. In addition, all respondents had complaints of eye fatigue that varies with the highest percentage of 80% with complaints of eye feel sleepy and 63% of workers feel pain in the neck or shoulder.

The use of nanoscale visible light-responsive photocatalyst TiO2-Pt for the elimination of soil-borne pathogens.

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Ya-Lei Chen

Full Text Available Exposure to the soil-borne pathogens Burkholderia pseudomallei and Burkholderia cenocepacia can lead to severe infections and even mortality. These pathogens exhibit a high resistance to antibiotic treatments. In addition, no licensed vaccine is currently available. A nanoscale platinum-containing titania photocatalyst (TiO(2-Pt has been shown to have a superior visible light-responsive photocatalytic ability to degrade chemical contaminants like nitrogen oxides. The antibacterial activity of the catalyst and its potential use in soil pathogen control were evaluated. Using the plating method, we found that TiO(2-Pt exerts superior antibacterial performance against Escherichia coli compared to other commercially available and laboratory prepared ultraviolet/visible light-responsive titania photocatalysts. TiO(2-Pt-mediated photocatalysis also affectively eliminates the soil-borne bacteria B. pseudomallei and B. cenocepacia. An air pouch infection mouse model further revealed that TiO(2-Pt-mediated photocatalysis could reduce the pathogenicity of both strains of bacteria. Unexpectedly, water containing up to 10% w/v dissolved soil particles did not reduce the antibacterial potency of TiO(2-Pt, suggesting that the TiO(2-Pt photocatalyst is suitable for use in soil-contaminated environments. The TiO(2-Pt photocatalyst exerted superior antibacterial activity against a broad spectrum of human pathogens, including B. pseudomallei and B. cenocepacia. Soil particles (<10% w/v did not significantly reduce the antibacterial activity of TiO(2-Pt in water. These findings suggest that the TiO(2-Pt photocatalyst may have potential applications in the development of bactericides for soil-borne pathogens.

Low Pt content direct methanol fuel cell anode catalyst: nanophase PtRuNiZr

Science.gov (United States)

Narayanan, Sekharipuram R. (Inventor); Whitacre, Jay F. (Inventor)

2010-01-01

A method for the preparation of a metallic material having catalytic activity that includes synthesizing a material composition comprising a metal content with a lower Pt content than a binary alloy containing Pt but that displays at least a comparable catalytic activity on a per mole Pt basis as the binary alloy containing Pt; and evaluating a representative sample of the material composition to ensure that the material composition displays a property of at least a comparable catalytic activity on a per mole Pt basis as a representative binary alloy containing Pt. Furthermore, metallic compositions are disclosed that possess substantial resistance to corrosive acids.

Pt based anode catalysts for direct ethanol fuel cells

Energy Technology Data Exchange (ETDEWEB)

Zhou, Weijiang; Zhou, Zhenhua; Song, Shuqin; Li, Wenzhen; Sun, Gongquan; Xin, Qin [Direct Alcohol Fuel Cell Laboratory, Dalian Institute of Chemical Physics, CAS, P.O. Box 110, Dalian 116023 (China); Tsiakaras, Panagiotis [Department of Mechanical and Industrial Engineering, University of Thessalia, Pedion Areos, GR 38334 Volos (Greece) 7

2003-11-10

In the present work several Pt-based anode catalysts supported on carbon XC-72R were prepared with a novel method and characterized by means of XRD, TEM and XPS analysis. It was found that all these catalysts are consisted of uniform nanosized particles with sharp distribution and Pt lattice parameter decreases with the addition of Ru or Pd and increases with the addition of Sn or W. Cyclic voltammetry (CV) measurements and single direct ethanol fuel cell (DEFC) tests jointly showed that the presence of Sn, Ru and W enhances the activity of Pt towards ethanol electro-oxidation in the following order: Pt{sub 1}Sn{sub 1}/C>Pt{sub 1}Ru{sub 1}/C>Pt{sub 1}W{sub 1}/C>Pt{sub 1}Pd{sub 1}/C>Pt/C. Moreover, Pt{sub 1}Ru{sub 1}/C further modified by W and Mo showed improved ethanol electro-oxidation activity, but its DEFC performance was found to be inferior to that measured for Pt{sub 1}Sn{sub 1}/C. Under this respect, several PtSn/C catalysts with different Pt/Sn atomic ratio were also identically prepared and characterized and their direct ethanol fuel cell performances were evaluated. It was found that the single direct ethanol fuel cell having Pt{sub 1}Sn{sub 1}/C or Pt{sub 3}Sn{sub 2}/C or Pt{sub 2}Sn{sub 1}/C as anode catalyst showed better performances than those with Pt{sub 3}Sn{sub 1}/C or Pt{sub 4}Sn{sub 1}/C. It was also found that the latter two cells exhibited higher performances than the single cell using Pt{sub 1}Ru{sub 1}/C, which is exclusively used in PEMFC as anode catalyst for both methanol electro-oxidation and CO-tolerance. This distinct difference in DEFC performance between the catalysts examined here would be attributed to the so-called bifunctional mechanism and to the electronic interaction between Pt and additives. It is thought that an amount of -OH{sub ads}, an amount of surface Pt active sites and the conductivity effect of PtSn/C catalysts would determine the activity of PtSn/C with different Pt/Sn ratios. At lower temperature values or at low

Low-Pt-Content Anode Catalyst for Direct Methanol Fuel Cells

Science.gov (United States)

Narayanan, Sekharipuram; Whitacre, Jay

2008-01-01

Combinatorial experiments have led to the discovery that a nanophase alloy of Pt, Ru, Ni, and Zr is effective as an anode catalyst material for direct methanol fuel cells. This discovery has practical significance in that the electronic current densities achievable by use of this alloy are comparable or larger than those obtained by use of prior Pt/Ru catalyst alloys containing greater amounts of Pt. Heretofore, the high cost of Pt has impeded the commercialization of direct methanol fuel cells. By making it possible to obtain a given level of performance at reduced Pt content (and, hence, lower cost), the discovery may lead to reduction of the economic impediment to commercialization.

The influence of alizarin and fluorescein on the photoactivity of Ni, Pt and Ru-doped TiO2 layers

International Nuclear Information System (INIS)

Rosu, Marcela-Corina; Suciu, Ramona-Crina; Lazar, Mihaela D.; Bratu, I.

2013-01-01

Highlights: ► The Ni, Pt, Ru-doped TiO 2 materials and sensitized with alizarin and fluorescein dyes were prepared by wet chemical route. ► The samples were characterized by: UV–vis spectroscopy, spectrofluorimetry, FT/IR spectroscopy and microscopy, X-ray diffraction and N 2 physisorption measurements. ► A combined influence of the dopants and dyes was observed, leading to a beneficial effect to TiO 2 photoactivity. -- Abstract: The doping with different metal ions and sensitization with organic compounds are two well known methods used to improve the photoactivity of TiO 2 . In this respect, the metallic ions-doped TiO 2 samples were prepared by embedding Ni, Pt and Ru ions into TiO 2 crystalline network and then, each sample was sensitized with alizarin and fluorescein dyes. The qualitative evaluation of prepared TiO 2 -based materials was made by: UV–vis spectroscopy, spectrofluorimetry, FT/IR spectroscopy and microscopy, X-ray diffraction and N 2 physisorption measurements. The optoelectronic properties investigated by UV–vis spectroscopy show that the optical response of Ni-doped TiO 2 layer shifts to visible. The X-ray spectra do not show peaks of nickel, platinum and ruthenium oxide crystals or pure metals. The FT/IR spectra proved the presence of dye molecules adsorbed on titania nanoparticles surface. These results demonstrated that the studied dopants and dyes have potential to promote modified TiO 2 -based materials as good candidates to be used in photolectrocatalytic processes

Mixed valent perovskites Ba/sub 3/B/sup 3 +/Ru/sub 2/sup(4. 5+)O/sub 9/. Catalytic activity of perovskite oxides with noble metals

Energy Technology Data Exchange (ETDEWEB)

Treiber, U; Kemmler-Sack, S; Ehmann, A; Schaller, H U; Duerrschmidt, E; Thumm, I; Bader, H [Tuebingen Univ. (Germany, F.R.). Lehrstuhl fuer Anorganische Chemie 2

1981-10-01

The black compounds Ba/sub 3/B/sup 3 +/Ru/sub 2/O/sub 9/ crystallize with B/sup 3 +/ = La, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb, and Y in a hexagonal BaTiO/sub 3/ structure (6L, sequence (hcc)/sub 2/) with an ordered distribution (1:2 order) of B/sup 3 +/ and ruthenium (BO/sub 6/ single octahedra; Ru/sub 2/O/sub 9/ double groups). The mean oxidation state of ruthenium is about +4.5. The properties are compared with those of other isotypic stacking polytypes Ba/sub 3/B/sup 3 +/M/sub 2/sup(4.5)O/sub 9/ (M/sub 2/ = IrRu, Ir/sub 2/, PtRu) and Ba/sub 3/B/sup 2 +/M/sub 2//sup 5 +/O/sub 9/ (M = Ru, Ir). The results of activity tests concerning the efficiency of perovskite oxides with noble metals in respect of the oxidation of CO or CHsub(x) and the reduction of NOsub(x) are reported.

Reforming of Ethanol to Produce Hydrogen over PtRuMg/ZrO2 Catalyst

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Josh Y. Z. Chiou

2012-01-01

Full Text Available A modified PtRu/ZrO2 catalyst with Mg is evaluated for the oxidative steam reforming of ethanol (OSRE and the steam reforming of ethanol (SRE. In order to understand the variation in the reaction mechanism on OSRE and SRE, further analysis of both fresh and used catalyst is concentrated on for TEM, TG, Raman, and TPR characterization. The results show that the OSRE reaction requires a higher temperature (∼390°C to achieve 100% ethanol conversion than the SRE reaction (∼2500°C. The distribution of CO is minor for both reactions (< 5% for OSRE, < 1% for SRE. This demonstrates that the water gas shift (WGS reaction is an important side-reaction in the reforming of ethanol to produce H2 and CO2. A comparison of the temperature of WGS (WGS shows it is lower for the SRE reaction (WGS∼250°C for SRE, ~340°C for OSRE.

Theoretical insights into the interaction between RunPt13-n (n=4, 7 and 9) clusters and [BMIM]+ based ionic liquids: Effect of anion.

Science.gov (United States)

Cheng, Ping; Yang, Yongpeng; Huang, Shiping

2017-06-01

Density functional theory has been performed to systematically study the interactions between Ru n Pt 13-n (n=4, 7 and 9) clusters and [BMIM] + based ionic liquids. Ionic liquids [BMIM][Br], [BMIM][BF 4 ], [BMIM][PF 6 ], [BMIM][CF 3 SO 3 ], and [BMIM][NTf 2 ] have different effects on the stability of Ru 7 Pt 6 . Ionic liquids with median size anions of PF 6 - and CF 3 SO 3 - can better improve the stability of Ru 7 Pt 6 than those with the small anions of Br - and BF 4 - and large anion of NTf 2 - . Based on negative relaxation energies, the stabilities of Ru 4 Pt 9 , Ru 7 Pt 6 , and Ru 9 Pt 4 are all enhanced after interacting with [BMIM][CF 3 SO 3 ]. The stability enhanced degree is in agreement with the interaction strength. For Ru 7 Pt 6 -n{[BMIM][CF 3 SO 3 ]} (n=1, 2, 3, 4), the interaction between ionic liquid and cluster plays the primary role in stabilizing the cluster in Ru 7 Pt 6 -[BMIM][CF 3 SO 3 ]. With the increase of the number of [BMIM][CF 3 SO 3 ], the role of the interaction in stabilizing the cluster is getting weaker, while the role of steric protection is getting more important. Copyright © 2017 Elsevier Inc. All rights reserved.

Fuel cycle integration issues associated with P/T technology

International Nuclear Information System (INIS)

Michaels, G.E.; Ludwig, S.B.

1992-01-01

The three primary interfaces between a generic partitioning and transmutation (P/T) technology and the existing United States fuel cycle are the light-water reactor (LWR) spent fuel inventory, the reprocessed uranium (RU) stream, and the high-level waste stream. The features and implications of these three interfaces are reviewed and their implications for P/T system design and for waste management are assessed. The variability of transuranic nuclide composition in the LWR spent fuel is calculated and its potential implications for transmutation system core design are discussed. The radiological characteristics of the RU stream are presented, and options for disposition of the stream are reviewed. Most P/T scenarios assume that RU will be recycled to LWRs. This study demonstrates, however, that LWR recycle cannot totally consume the reprocessed stream, and disposal of a waste uranium steam with high levels of radiologically-significant isotopes will still be necessary. The radioactivity of the tails stream for enrichment plants resulting from a dedicated RU campaign is calculated. The tendency of gaseous diffusion plant enrichment technology to deplete the tails stream of minor uranium isotopes is seen as a benefit and an advantage over Atomic Vapor Laser Isotope Separation-type technology. Finally, the implications of P/T on LWR-origin wastes reporting to the repository is discussed, and several significant differences between LWR-origin waste originating from transmutation systems are assessed

The influence of alizarin and fluorescein on the photoactivity of Ni, Pt and Ru-doped TiO{sub 2} layers

Energy Technology Data Exchange (ETDEWEB)

Rosu, Marcela-Corina, E-mail: marcela.rosu@itim-cj.ro [National Institute for Research and Development of Isotopic and Molecular Technologies, 65-103 Donath Street, 400293, Cluj-Napoca (Romania); Suciu, Ramona-Crina; Lazar, Mihaela D.; Bratu, I. [National Institute for Research and Development of Isotopic and Molecular Technologies, 65-103 Donath Street, 400293, Cluj-Napoca (Romania)

2013-04-20

Highlights: ► The Ni, Pt, Ru-doped TiO{sub 2} materials and sensitized with alizarin and fluorescein dyes were prepared by wet chemical route. ► The samples were characterized by: UV–vis spectroscopy, spectrofluorimetry, FT/IR spectroscopy and microscopy, X-ray diffraction and N{sub 2} physisorption measurements. ► A combined influence of the dopants and dyes was observed, leading to a beneficial effect to TiO{sub 2} photoactivity. -- Abstract: The doping with different metal ions and sensitization with organic compounds are two well known methods used to improve the photoactivity of TiO{sub 2}. In this respect, the metallic ions-doped TiO{sub 2} samples were prepared by embedding Ni, Pt and Ru ions into TiO{sub 2} crystalline network and then, each sample was sensitized with alizarin and fluorescein dyes. The qualitative evaluation of prepared TiO{sub 2}-based materials was made by: UV–vis spectroscopy, spectrofluorimetry, FT/IR spectroscopy and microscopy, X-ray diffraction and N{sub 2} physisorption measurements. The optoelectronic properties investigated by UV–vis spectroscopy show that the optical response of Ni-doped TiO{sub 2} layer shifts to visible. The X-ray spectra do not show peaks of nickel, platinum and ruthenium oxide crystals or pure metals. The FT/IR spectra proved the presence of dye molecules adsorbed on titania nanoparticles surface. These results demonstrated that the studied dopants and dyes have potential to promote modified TiO{sub 2}-based materials as good candidates to be used in photolectrocatalytic processes.

Influence of plasma treatment of carbon blacks on electrochemical activity of Pt/carbon blacks catalysts for DMFCs

Science.gov (United States)

Kim, Seok; Cho, Mi-Hwa; Lee, Jae-Rock; Park, Soo-Jin

In this work, in order to improve the dispersion of platinum catalysts deposited on carbon materials, the effects of surface plasma treatment of carbon blacks (CBs) were investigated. The surface characteristics of the CBs were determined by fourier transformed-infrared (FT-IR), X-ray photoelectron spectroscopy (XPS), and Boehm's titration method. The electrochemical properties of the plasma-treated CBs-supported Pt (Pt/CBs) catalysts were analyzed by linear sweep voltammetry (LSV) experiments. From the results of FT-IR and acid-base values, N 2-plasma treatment of the CBs at 300 W intensity led to a formation of a free radical on the CBs. The peak intensity increased with increase of the treatment time, due to the formation of new basic functional groups (such as C-N, C dbnd N, -NH 3 +, -NH, and dbnd NH) by the free radical on the CBs. Accordingly, the basic values were enhanced by the basic functional groups. However, after a specific reaction time, N 2-plasma treatment could hardly influence on change of the surface functional groups of CBs, due to the disappearance of free radical. Consequently, it was found that optimal treatment time was 30 s for the best electro activity of Pt/CBs catalysts and the N 2-plasma treated Pt/CBs possessed the better electrochemical properties than the pristine Pt/CBs.

Activity and Stability of Dispersed Multi Metallic Pt-based Catalysts for CO Tolerance in Proton Exchange Membrane Fuel Cell Anodes.

Science.gov (United States)

Hassan, Ayaz; Ticianelli, Edson A

2018-01-01

Studies aiming at improving the activity and stability of dispersed W and Mo containing Pt catalysts for the CO tolerance in proton exchange membrane fuel cell (PEMFC) anodes are revised for the following catalyst systems: (1) a carbon supported PtMo electrocatalyst submitted to heat treatments; (2) Pt and PtMo nanoparticles deposited on carbon-supported molybdenum carbides (Mo2C/C); (3) ternary and quaternary materials formed by PtMoFe/C, PtMoRu/C and PtMoRuFe/C and; (4) Pt nanoparticles supported on tungsten carbide/carbon catalysts and its parallel evaluation with carbon supported PtW catalyst. The heat-treated (600 oC) Pt-Mo/C catalyst showed higher hydrogen oxidation activity in the absence and in the presence of CO and better stability, compared to all other Mo-containing catalysts. PtMoRuFe, PtMoFe, PtMoRu supported on carbon and Pt supported on Mo2C/C exhibited similar CO tolerances but better stability, as compared to as-prepared PtMo supported on carbon. Among the tungsten-based catalysts, tungsten carbide supported Pt catalyst showed reasonable performance and reliable stability in comparison to simple carbon supported PtW catalyst, though an uneven level of catalytic activity towards H2 oxidation in presence of CO is observed for the former as compared to Mo containing catalyst. However, a small dissolution of Mo, Ru, Fe and W from the anodes and their migration toward cathodes during the cell operation is observed. These results indicate that the fuel cell performance and stability has been improved but not yet totally resolved.

Activity and Stability of Dispersed Multi Metallic Pt-based Catalysts for CO Tolerance in Proton Exchange Membrane Fuel Cell Anodes

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AYAZ HASSAN

2018-04-01

Full Text Available ABSTRACT Studies aiming at improving the activity and stability of dispersed W and Mo containing Pt catalysts for the CO tolerance in proton exchange membrane fuel cell (PEMFC anodes are revised for the following catalyst systems: (1 a carbon supported PtMo electrocatalyst submitted to heat treatments; (2 Pt and PtMo nanoparticles deposited on carbon-supported molybdenum carbides (Mo2C/C; (3 ternary and quaternary materials formed by PtMoFe/C, PtMoRu/C and PtMoRuFe/C and; (4 Pt nanoparticles supported on tungsten carbide/carbon catalysts and its parallel evaluation with carbon supported PtW catalyst. The heat-treated (600 oC Pt-Mo/C catalyst showed higher hydrogen oxidation activity in the absence and in the presence of CO and better stability, compared to all other Mo-containing catalysts. PtMoRuFe, PtMoFe, PtMoRu supported on carbon and Pt supported on Mo2C/C exhibited similar CO tolerances but better stability, as compared to as-prepared PtMo supported on carbon. Among the tungsten-based catalysts, tungsten carbide supported Pt catalyst showed reasonable performance and reliable stability in comparison to simple carbon supported PtW catalyst, though an uneven level of catalytic activity towards H2 oxidation in presence of CO is observed for the former as compared to Mo containing catalyst. However, a small dissolution of Mo, Ru, Fe and W from the anodes and their migration toward cathodes during the cell operation is observed. These results indicate that the fuel cell performance and stability has been improved but not yet totally resolved.

Carbon monoxide oxidation on bimetallic Ru/Au(111 surfaces

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ROLF-JÜRGEN BEHM

2001-02-01

Full Text Available The electrochemical deposition of Ru on Au(111 was performed in 0.5 M H2SO4+10-4 M RuCl3 . The obtained bimetallic Ru/Au(111 surfaces were character-ised by cyclic voltammetry and in situ STM in 0.5 MH2SO4. The Ru deposit consists of nanoscale islands, which merge with increasing coverage. Two different types of bimetallic Ru/Au(111 surfaces with respect to the distribution of Ru islands over the Au(111 substrate surface were obtained. When the deposition was performed at potentials more positive than the range of Au(111 reconstruction, homogeneous nucleation occured resulting in a random distribution of Ru islands. When the deposition was performed on reconstructed Au(111 at low overpotentials, selective nucleation occured resulting in the replication of the Au(111 reconstruction. Only at higher deposition overpotentials, can multilayer deposits be formed, which exhibit a very rough surface morphology. The electrocatalytic activity of such structurally well defined Ru/Au(111 bimetallic surfaces was studied towards CO oxidation with the Ru coverage ranging from submonolayer to several monolayer. COstripping commences at about 0.2 Vand occurs over a broad potential range. The observed influence of the Ru structure on the CO stripping voltammetry is explained by local variations in the COadsorption energy, caused by differences in the local Ru structure and by effects induced by the Au(111 substrate.

Synthesis and electrochemical study of Pt-based nanoporous materials

International Nuclear Information System (INIS)

Wang Jingpeng; Holt-Hindle, Peter; MacDonald, Duncan; Thomas, Dan F.; Chen Aicheng

2008-01-01

In the present work, a variety of Pt-based bimetallic nanostructured materials including nanoporous Pt, Pt-Ru, Pt-Ir, Pt-Pd and Pt-Pb networks have been directly grown on titanium substrates via a facile hydrothermal method. The as-fabricated electrodes were characterized by scanning electron microscopy, energy dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, X-ray diffraction and electrochemical methods. The active surface areas of these nanoporous Pt-based alloy catalysts are increased by over 68 (Pt-Pd), 69 (Pt-Ru) and 113 (Pt-Ir) fold compared to a polycrystalline Pt electrode. All these synthesized nanoporous electrodes exhibit superb electrocatalytic performance towards electrochemical oxidation of methanol and formic acid. Among the five nanoporous Pt-based electrodes, the Pt-Ir shows the highest peak current density at +0.50 V, with 68 times of enhancement compared to the polycrystalline Pt for methanol oxidation, and with 86 times of enhancement in formic acid oxidation; whereas the catalytic activity of the nanoporous Pt-Pb electrode outperforms the other materials in formic acid oxidation at the low potential regions, delivering an enhanced current density by 280-fold compared to the polycrystalline Pt at +0.15 V. The new approach described in this study is suitable for synthesizing a wide range of bi-metallic and tri-metallic nanoporous materials, desirable for electrochemical sensor design and potential application in fuel cells

Synthesis and electrochemical study of Pt-based nanoporous materials

Energy Technology Data Exchange (ETDEWEB)

Wang Jingpeng [Department of Chemistry, Lakehead University, Thunder Bay, Ontario P7B 5E1 (Canada); Department of Chemistry, University of Guelph, Guelph, Ontario N1G 2W1 (Canada); Holt-Hindle, Peter; MacDonald, Duncan [Department of Chemistry, Lakehead University, Thunder Bay, Ontario P7B 5E1 (Canada); Thomas, Dan F. [Department of Chemistry, University of Guelph, Guelph, Ontario N1G 2W1 (Canada); Chen Aicheng [Department of Chemistry, Lakehead University, Thunder Bay, Ontario P7B 5E1 (Canada)], E-mail: aicheng.chen@lakeheadu.ca

2008-10-01

In the present work, a variety of Pt-based bimetallic nanostructured materials including nanoporous Pt, Pt-Ru, Pt-Ir, Pt-Pd and Pt-Pb networks have been directly grown on titanium substrates via a facile hydrothermal method. The as-fabricated electrodes were characterized by scanning electron microscopy, energy dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, X-ray diffraction and electrochemical methods. The active surface areas of these nanoporous Pt-based alloy catalysts are increased by over 68 (Pt-Pd), 69 (Pt-Ru) and 113 (Pt-Ir) fold compared to a polycrystalline Pt electrode. All these synthesized nanoporous electrodes exhibit superb electrocatalytic performance towards electrochemical oxidation of methanol and formic acid. Among the five nanoporous Pt-based electrodes, the Pt-Ir shows the highest peak current density at +0.50 V, with 68 times of enhancement compared to the polycrystalline Pt for methanol oxidation, and with 86 times of enhancement in formic acid oxidation; whereas the catalytic activity of the nanoporous Pt-Pb electrode outperforms the other materials in formic acid oxidation at the low potential regions, delivering an enhanced current density by 280-fold compared to the polycrystalline Pt at +0.15 V. The new approach described in this study is suitable for synthesizing a wide range of bi-metallic and tri-metallic nanoporous materials, desirable for electrochemical sensor design and potential application in fuel cells.0.

Synthesis and electrochemical study of Pt-based nanoporous materials

Energy Technology Data Exchange (ETDEWEB)

Wang, Jingpeng [Department of Chemistry, Lakehead University, Thunder Bay, Ontario P7B 5E1 (Canada); Department of Chemistry, University of Guelph, Guelph, Ontario N1G 2W1 (Canada); Holt-Hindle, Peter; MacDonald, Duncan; Chen, Aicheng [Department of Chemistry, Lakehead University, Thunder Bay, Ontario P7B 5E1 (Canada); Thomas, Dan F. [Department of Chemistry, University of Guelph, Guelph, Ontario N1G 2W1 (Canada)

2008-10-01

In the present work, a variety of Pt-based bimetallic nanostructured materials including nanoporous Pt, Pt-Ru, Pt-Ir, Pt-Pd and Pt-Pb networks have been directly grown on titanium substrates via a facile hydrothermal method. The as-fabricated electrodes were characterized by scanning electron microscopy, energy dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, X-ray diffraction and electrochemical methods. The active surface areas of these nanoporous Pt-based alloy catalysts are increased by over 68 (Pt-Pd), 69 (Pt-Ru) and 113 (Pt-Ir) fold compared to a polycrystalline Pt electrode. All these synthesized nanoporous electrodes exhibit superb electrocatalytic performance towards electrochemical oxidation of methanol and formic acid. Among the five nanoporous Pt-based electrodes, the Pt-Ir shows the highest peak current density at +0.50 V, with 68 times of enhancement compared to the polycrystalline Pt for methanol oxidation, and with 86 times of enhancement in formic acid oxidation; whereas the catalytic activity of the nanoporous Pt-Pb electrode outperforms the other materials in formic acid oxidation at the low potential regions, delivering an enhanced current density by 280-fold compared to the polycrystalline Pt at +0.15 V. The new approach described in this study is suitable for synthesizing a wide range of bi-metallic and tri-metallic nanoporous materials, desirable for electrochemical sensor design and potential application in fuel cells. (author)

Functional properties of electrospun NiO/RuO{sub 2} composite carbon nanofibers

Energy Technology Data Exchange (ETDEWEB)

Wu Yongzhi [Healthcare and Energy Materials Laboratory, Nanoscience and Nanotechnology Initiative, National University of Singapore, Singapore 117576 (Singapore); Physics Department, National University of Singapore, Singapore 117542 (Singapore); NUS Graduate School for Integrated Science and Engineering, 10 Kent Ridge Crescent, National University of Singapore, Singapore 119260 (Singapore); Balakrishna, Rajiv [Healthcare and Energy Materials Laboratory, Nanoscience and Nanotechnology Initiative, National University of Singapore, Singapore 117576 (Singapore); Physics Department, National University of Singapore, Singapore 117542 (Singapore); Reddy, M.V., E-mail: phymvv@nus.edu.sg [Physics Department, National University of Singapore, Singapore 117542 (Singapore); Nair, A. Sreekumaran, E-mail: nniansn@nus.edu.sg [Healthcare and Energy Materials Laboratory, Nanoscience and Nanotechnology Initiative, National University of Singapore, Singapore 117576 (Singapore); Chowdari, B.V.R. [Physics Department, National University of Singapore, Singapore 117542 (Singapore); Ramakrishna, S. [Healthcare and Energy Materials Laboratory, Nanoscience and Nanotechnology Initiative, National University of Singapore, Singapore 117576 (Singapore); Kind Saud University, Riyadh 11451 (Saudi Arabia)

2012-03-15

Highlights: Black-Right-Pointing-Pointer Fabrication of carbon nanofibers with nickel-ruthenium composites by electrospinning. Black-Right-Pointing-Pointer An interesting observation of increase in capacitance with increase in the number of cycles for supercapacitor applications. Black-Right-Pointing-Pointer Li ion battery testing showed a stable capacity ranging from 350 mAh g{sup -1} to 400 mAh g{sup -1}. Black-Right-Pointing-Pointer Lower impedance with the incorporation of 15 wt% Ru precursor than those without Ru. - Abstract: One-dimensional (1D) nickel oxide/ruthenium oxide (NiO/RuO{sub 2})-carbon composite nanofibers (NiRu-C-NFs) were fabricated via electrospinning of a homogenous mixture of polyacrylonitrile (PAN) and Ni/Ru salt precursors at different ratios followed by heat treatments. The 1D nanostructures of the composite material were characterized by field-emission scanning electron microscopy (FE-SEM), powder X-ray diffraction (XRD), Rietveld refinement and Brunauer-Emmett-Teller (BET) surface area measurements. Li-cycling properties were evaluated using cyclic voltammetry and galvanostatic properties. The asymmetric hybrid supercapacitor studies were carried out with activated carbon as a cathode and NiRu-C-NFs composites as anodes in the cycling range, 0.005-3.0 V using 1 M LiPF{sub 6} (EC;DMC) electrolyte. NiRu-C-NFs fabricated from 5 wt% nickel (II) and 15 wt% ruthenium (III) precursors showed a capacitance up to {approx}60 F g{sup -1} after 30 cycles. Anodic Li-cycling studies of NiRu-C-NF-0 and NiRu-C-NF-2 composite samples showed a reversible capacity of 230 and 350 m Ahg{sup -1} at current rate of 72 mA g{sup -1} at the end of 40th cycle in the voltage range of 0.005-3.0 V. Electrochemical impedance studies (EIS) on NiRu-C-NFs showed lower impedance value for 15 wt% Ru than the bare sample.

Effects of microstructure and composition of anode Pt based electrocatalysts on performance of direct alcohol fuel cells

Energy Technology Data Exchange (ETDEWEB)

Jiang, L.; Li, H.; Yan, S.; Sun, G. [Dalian Inst. of Chemical Physics, Dalian (China). Direct Alcohol Fuel Cell Lab; Xin, Q. [Dalian Inst. of Chemical Physics, Dalian (China). Direct Alcohol Fuel Cell Lab; Dalian Inst. of Chemical Physics, Dalian (China). State Key Laboratory of Catalysis

2008-07-01

This paper reported on a study in which platinum (Pt)-based electrocatalysts were synthesized and characterized by XRD, TEM and EDS. The focus of the study was on the relationship between the microstructure and components of PtRu and PtSn catalysts and the performance of direct alcohol fuel cells (DAFCs). All of the Pt-based electrocatalysts were prepared by a modified polyol method. XRD patterns of the 2 catalysts showed that both catalysts have an fcc pattern of Pt. This was also confirmed by the shift of diffraction peaks of Pt in both catalysts. Electrochemical measurements were carried out using an EG and G model 273A potentiostat/galvanostat and a three-electrode test cell at room temperature. Membrane electrode assemblies (MEAs) were fabricated with a pair of stainless steel plates with parallel flow-fields. The MEAs were activated by 1 M methanol/ethanol at 75 degrees C for 3 hours before all the data were collected. The study showed that PtRu is active to methanol electrooxidation while PtSn is active to ethanol electrooxidation. Based on the above experimental analysis, it was determined that the dilatation of Pt lattice parameter is favourable for ethanol adsorption, while the suitable contract of Pt lattice parameter is favorable for methanol electrooxidation. Since Pt is more electronegative than Sn, the partial electrons of Sn atom could be transferred to Pt atom leading to filling of Pt d band. Although Ru is as electronegative as Pt, the electric effect of Pt and Ru may not be as pronounced. 4 refs., 4 figs.

Sonoelectrochemical one-pot synthesis of Pt - Carbon black nanocomposite PEMFC electrocatalyst.

Science.gov (United States)

Karousos, Dionysios S; Desdenakis, Kostantinos I; Sakkas, Petros M; Sourkouni, Georgia; Pollet, Bruno G; Argirusis, Christos

2017-03-01

Simultaneous electrocatalytic Pt-nanoparticle synthesis and decoration of Vulcan XC-72 carbon black substrate was achieved in a novel one-step-process, combining galvanostatic pulsed electrodeposition and pulsed ultrasonication with high power, low-frequency (20kHz) ultrasound. Aqueous chloroplatinic acid precursor baths, as well as carbon black suspensions in the former, were examined and decoration was proven by a combination of characterization methods, namely: dynamic light scattering, transmission electron microscopy, scanning electron microscopy with EDX-analysis and cyclic voltammetry. In particular, PVP was shown to have a beneficial stabilizing effect against free nanoparticle aggregation, ensuring narrow size distributions of the nanoparticles synthesized, but is also postulated to prevent the establishment of a strong metal-substrate interaction. Current pulse amplitude was identified as the most critical nanoparticle size-determining parameters, while only small size particles, under 10nm, appeared to be attached to carbon black. Copyright © 2016 Elsevier B.V. All rights reserved.

Ternary Pt9RhFex Nanoscale Alloys as Highly Efficient Catalysts with Enhanced Activity and Excellent CO-Poisoning Tolerance for Ethanol Oxidation.

Science.gov (United States)

Wang, Peng; Yin, Shibin; Wen, Ying; Tian, Zhiqun; Wang, Ningzhang; Key, Julian; Wang, Shuangbao; Shen, Pei Kang

2017-03-22

To address the problems of high cost and poor stability of anode catalysts in direct ethanol fuel cells (DEFCs), ternary nanoparticles Pt 9 RhFe x (x = 1, 3, 5, 7, and 9) supported on carbon powders (XC-72R) have been synthesized via a facile method involving reduction by sodium borohydride followed by thermal annealing in N 2 at ambient pressure. The catalysts are physically characterized by X-ray diffraction, scanning transmission electron microscopy, and X-ray photoelectron spectroscopy, and their catalytic performance for the ethanol oxidation reaction (EOR) is evaluated by cyclic and linear scan voltammetry, CO-stripping voltammograms, and chronopotentiometry. All the Pt 9 RhFe x /C catalysts of different atomic ratios produce high EOR catalytic activity. The catalyst of atomic ratio composition 9:1:3 (Pt/Rh/Fe) has the highest activity and excellent CO-poisoning tolerance. Moreover, the enhanced EOR catalytic activity on Pt 9 RhFe 3 /C when compared to Pt 9 Rh/C, Pt 3 Fe/C, and Pt/C clearly demonstrates the presence of Fe improves catalytic performance. Notably, the onset potential for CO oxidation on Pt 9 RhFe 3 /C (0.271 V) is ∼55, 75, and 191 mV more negative than on Pt 9 Rh/C (0.326 V), Pt 3 Fe/C (0.346 V), and Pt/C (0.462 V), respectively, which implies the presence of Fe atoms dramatically improves CO-poisoning tolerance. Meanwhile, compared to the commercial PtRu/C catalyst, the peak potential on Pt 9 RhFe 3 /C for CO oxidation was just slightly changed after several thousand cycles, which shows high stability against the potential cycling. The possible mechanism by which Fe and Rh atoms facilitate the observed enhanced performance is also considered herein, and we conclude Pt 9 RhFe 3 /C offers a promising anode catalyst for direct ethanol fuel cells.

Ni@Ru and NiCo@Ru Core-Shell Hexagonal Nanosandwiches with a Compositionally Tunable Core and a Regioselectively Grown Shell.

Science.gov (United States)

Hwang, Hyeyoun; Kwon, Taehyun; Kim, Ho Young; Park, Jongsik; Oh, Aram; Kim, Byeongyoon; Baik, Hionsuck; Joo, Sang Hoon; Lee, Kwangyeol

2018-01-01

The development of highly active electrocatalysts is crucial for the advancement of renewable energy conversion devices. The design of core-shell nanoparticle catalysts represents a promising approach to boost catalytic activity as well as save the use of expensive precious metals. Here, a simple, one-step synthetic route is reported to prepare hexagonal nanosandwich-shaped Ni@Ru core-shell nanoparticles (Ni@Ru HNS), in which Ru shell layers are overgrown in a regioselective manner on the top and bottom, and around the center section of a hexagonal Ni nanoplate core. Notably, the synthesis can be extended to NiCo@Ru core-shell nanoparticles with tunable core compositions (Ni 3 Co x @Ru HNS). Core-shell HNS structures show superior electrocatalytic activity for the oxygen evolution reaction (OER) to a commercial RuO 2 black catalyst, with their OER activity being dependent on their core compositions. The observed trend in OER activity is correlated to the population of Ru oxide (Ru 4+ ) species, which can be modulated by the core compositions. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effects of nanoscale coatings on reliability of MEMS ohmic contact switches

Science.gov (United States)

Tremper, Amber Leigh

This thesis examines how the electrical and mechanical behavior of Au thin films is altered by the presence of ultra-thin metallic coatings. To examine the mechanical behavior, nanoindentation, nano-scratch, and atomic force microscopy (AFM) testing was performed. The electrical behavior was evaluated through Kelvin probe contact resistance measurements. This thesis shows that ultra-thin, hard, ductile coatings on a softer, ductile underlying layer (such as Ru or Pt on Au) had a significant effect on mechanical behavior of the system, and can be tailored to control the deformation resistance of the thin film system. Despite Ru and Pt having a higher hardness and plane strain modulus than Au, the Ru and Pt coatings decreased both the hardness and plane strain modulus of the layered system when the indentation depth was on the order of the coating thickness. Alternately, when the indentation depth was several times the coating thickness, the ductile, plastically hard, elastically stiff layer significantly hardened the contact response. These results correlate well with membrane stress theoretical predictions, and demonstrate that membrane theory can be applied even when the ratio of indentation depth, h, to coating thickness, t, is very large ( h/telectrical behavior of the Ru-coated Au films was examined, it was found that all the measured resistances of the Au-only film and Ru-coated systems were several orders of magnitude larger than those predicted by Holm's law, but were still in good agreement with previously reported values in the literature. Previous studies attributed the high contact resistances to a variety of causes, including the buildup of an insulating contamination layer. This thesis determined the cause of the deviations to be large sheet resistance contributions to the total measured resistance. Further, studies on aged samples (with thicker contamination layers) conclusively showed that, while contamination increases the contact resistance, it

Characterization and methanol electrooxidation studies of Pt(111)/Os surfaces prepared by spontaneous deposition.

Science.gov (United States)

Johnston, Christina M; Strbac, Svetlana; Lewera, Adam; Sibert, Eric; Wieckowski, Andrzej

2006-09-12

Catalytic activity of the Pt(111)/Os surface toward methanol electrooxidation was optimized by exploring a wide range of Os coverage. Various methods of surface analyses were used, including electroanalytical, STM, and XPS methods. The Pt(111) surface was decorated with nanosized Os islands by spontaneous deposition, and the Os coverage was controlled by changing the exposure time to the Os-containing electrolyte. The structure of Os deposits on Pt(111) was characterized and quantified by in situ STM and stripping voltammetry. We found that the optimal Os surface coverage of Pt(111) for methanol electrooxidation was 0.7 +/- 0.1 ML, close to 1.0 +/- 0.1 Os packing density. Apparently, the high osmium coverage Pt(111)/Os surface provides more of the necessary oxygen-containing species (e.g., Os-OH) for effective methanol electrooxidation than the Pt(111)/Os surfaces with lower Os coverage (vs e.g., Ru-OH). Supporting evidence for this conjecture comes from the CO electrooxidation data, which show that the onset potential for CO stripping is lowered from 0.53 to 0.45 V when the Os coverage is increased from 0.2 to 0.7 ML. However, the activity of Pt(111)/Os for methanol electrooxidation decreases when the Os coverage is higher than 0.7 +/- 0.1 ML, indicating that Pt sites uncovered by Os are necessary for sustaining significant methanol oxidation rates. Furthermore, osmium is inactive for methanol electrooxidation when the platinum substrate is absent: Os deposits on Au(111), a bulk Os ingot, and thick films of electrodeposited Os on Pt(111), all compare poorly to Pt(111)/Os. We conclude that a bifunctional mechanism applies to the methanol electrooxidation similarly to Pt(111)/Ru, although with fewer available Pt sites. Finally, the potential window for methanol electrooxidation on Pt(111)/Os was observed to shift positively versus Pt(111)/Ru. Because of the difference in the Os and Ru oxophilicity under electrochemical conditions, the Os deposit provides fewer

Enhanced interfacial Dzyaloshinskii-Moriya interaction and isolated skyrmions in the inversion-symmetry-broken Ru/Co/W/Ru films

Science.gov (United States)

Samardak, Alexander; Kolesnikov, Alexander; Stebliy, Maksim; Chebotkevich, Ludmila; Sadovnikov, Alexandr; Nikitov, Sergei; Talapatra, Abhishek; Mohanty, Jyoti; Ognev, Alexey

2018-05-01

An enhancement of the spin-orbit effects arising on an interface between a ferromagnet (FM) and a heavy metal (HM) is possible through the strong breaking of the structural inversion symmetry in the layered films. Here, we show that an introduction of an ultrathin W interlayer between Co and Ru in Ru/Co/Ru films enables to preserve perpendicular magnetic anisotropy (PMA) and simultaneously induce a large interfacial Dzyaloshinskii-Moriya interaction (iDMI). The study of the spin-wave propagation in the Damon-Eshbach geometry by Brillouin light scattering spectroscopy reveals the drastic increase in the iDMI value with the increase in W thickness (tW). The maximum iDMI of -3.1 erg/cm2 is observed for tW = 0.24 nm, which is 10 times larger than for the quasi-symmetrical Ru/Co/Ru films. We demonstrate the evidence of the spontaneous field-driven nucleation of isolated skyrmions supported by micromagnetic simulations. Magnetic force microscopy measurements reveal the existence of sub-100-nm skyrmions in the zero magnetic field. The ability to simultaneously control the strength of PMA and iDMI in quasi-symmetrical HM/FM/HM trilayer systems through the interface engineered inversion asymmetry at the nanoscale excites new fundamental and practical interest in ultrathin ferromagnets, which are a potential host for stable magnetic skyrmions.

In situ TEM study of the coarsening of carbon black supported Pt nanoparticles in hydrogen

DEFF Research Database (Denmark)

Simonsen, Søren Bredmose; Wang, Yan; Jensen, Jens Oluf

2017-01-01

The control of sizes and shapes of nanostructures is of tremendous importance for the catalytic activity in electrochemistry and in catalysis more generally. However, due to relatively large surface free energies, nanostructures often sinter to form coarser and more stable structures that may...... not have the intended physicochemical properties. Pt is known to be a very active catalyst in several chemical reactions and for example as carbon supported nanoparticles in fuel cells. The presentation focusses on coarsening mechanisms of Pt nanoparticles supported on carbon black during exposure...... to hydrogen. By means of in situ transmission electron microscopy (TEM), Pt nanoparticle coarsening was monitored in 6 mbar 20 % H2/Ar while ramping up the temperature to ca. 900 °C. Time-resolved TEM images directly reveal that separated ca. 3 nm sized Pt nanoparticles in the pure hydrogen environment...

Electrochemical evaluation of Pt-Based binary catalysts on various supports for the direct methanol fuel cell

CSIR Research Space (South Africa)

Khotseng, L

2016-01-01

Full Text Available Ru/MoO(sub2) > PtSn/TiO(sub2) > PtRu/TiO(sub2). It was also observed that catalysts supported on MWCNTs were more active than those supported on metal oxides. Furthermore, catalysts supported on MWCNTs proved to be more stable than all the other supported...

Electrocatalytic activity of atomic layer deposited Pt–Ru catalysts onto N-doped carbon nanotubes

DEFF Research Database (Denmark)

Johansson, Anne-Charlotte Elisabeth Birgitta; Larsen, Jackie Vincent; Verheijen, Marcel A.

2014-01-01

(ethylcyclopentadienyl)ruthenium (Ru(EtCp)2), respectively. O2 was used as the reactant in both processes. The composition of the catalysts was easily tuned by varying the Pt-to-Ru ALD cycle ratio. The catalysts were tested toward the CO oxidation and methanol oxidation reaction (MOR) in a three-electrode electrochemical set...

Novel RuCoSe as non-platinum catalysts for oxygen reduction reaction in microbial fuel cells

Science.gov (United States)

Rozenfeld, Shmuel; Schechter, Michal; Teller, Hanan; Cahan, Rivka; Schechter, Alex

2017-09-01

Microbial electrochemical cells (MECs) are explored for the conversion of acetate directly to electrical energy. This device utilizes a Geobacter sulfurreducens anode and a novel RuCoSe air cathode. RuCoSe synthesized in selected compositions by a borohydride reduction method produces amorphous structures of powdered agglomerates. Oxygen reduction reaction (ORR) was measured in a phosphate buffer solution pH 7 using a rotating disc electrode (RDE), from which the kinetic current (ik) was measured as a function of potential and composition. The results show that ik of RuxCoySe catalysts increases in the range of XRu = 0.25 > x > 0.7 and y < 0.15 for all tested potentials. A poisoning study of RuCoSe and Pt catalysts in a high concentration acetate solution shows improved tolerance of RuCoSe to this fuel at acetate concentration ≥500 mM. MEC discharge plots under physiological conditions show that ∼ RuCo2Se (sample S3) has a peak power density of 750 mW cm-2 which is comparable with Pt 900 mW cm-2.

A novel binary Pt 3Te x/C nanocatalyst for ethanol electro-oxidation

Science.gov (United States)

Huang, Meihua; Wang, Fei; Li, Lirong; Guo, Yonglang

The Pt 3Te x/C nanocatalyst was prepared and its catalytic performance for ethanol oxidation was investigated for the first time. The Pt 3Te/C nanoparticles were characterized by an X-ray diffractometer (XRD), transmission electron microscope (TEM) and energy dispersive X-ray spectroscopy equipped with TEM (TEM-EDX). The Pt 3Te/C catalyst has a typical fcc structure of platinum alloys with the presence of Te. Its particle size is about 2.8 nm. Among the synthesized catalysts with different atomic ratios, the Pt 3Te/C catalyst has the highest anodic peak current density. The cyclic voltammograms (CV) show that the anodic peak current density for the Pt 3Te/C, commercial PtRu/C and Pt/C catalysts reaches 1002, 832 and 533 A g -1, respectively. On the current-time curve, the anodic current on the Pt 3Te/C catalyst was higher than those for the catalysts reported. So, these findings show that the Pt 3Te/C catalyst has uniform nanoparticles and the best activity among the synthesized catalysts, and it is better than commercial PtRu/C and Pt/C catalysts for ethanol oxidation at room temperature.

Nanoscale monoclinic domains in epitaxial SrRuO3 thin films deposited by pulsed laser deposition

Science.gov (United States)

Ghica, C.; Negrea, R. F.; Nistor, L. C.; Chirila, C. F.; Pintilie, L.

2014-07-01

In this paper, we analyze the structural distortions observed by transmission electron microscopy in thin epitaxial SrRuO3 layers used as bottom electrodes in multiferroic coatings onto SrTiO3 substrates for future multiferroic devices. Regardless of the nature and architecture of the multilayer oxides deposited on the top of the SrRuO3 thin films, selected area electron diffraction patterns systematically revealed the presence of faint diffraction spots appearing in forbidden positions for the SrRuO3 orthorhombic structure. High-resolution transmission electron microscopy (HRTEM) combined with Geometric Phase Analysis (GPA) evidenced the origin of these forbidden diffraction spots in the presence of structurally disordered nanometric domains in the SrRuO3 bottom layers, resulting from a strain-driven phase transformation. The local high compressive strain (-4% ÷ -5%) measured by GPA in the HRTEM images induces a local orthorhombic to monoclinic phase transition by a cooperative rotation of the RuO6 octahedra. A further confirmation of the origin of the forbidden diffraction spots comes from the simulated diffraction patterns obtained from a monoclinic disordered SrRuO3 structure.

Platinum-group elements fractionation by selective complexing, the Os, Ir, Ru, Rh-arsenide-sulfide systems above 1020 °C

Science.gov (United States)

Helmy, Hassan M.; Bragagni, Alessandro

2017-11-01

The platinum-group element (PGE) contents in magmatic ores and rocks are normally in the low μg/g (even in the ng/g) level, yet they form discrete platinum-group mineral (PGM) phases. IPGE (Os, Ir, Ru) + Rh form alloys, sulfides, and sulfarsenides while Pt and Pd form arsenides, tellurides, bismuthoids and antimonides. We experimentally investigate the behavior of Os, Ru, Ir and Rh in As-bearing sulfide system between 1300 and 1020 °C and show that the prominent mineralogical difference between IPGE (+Rh) and Pt and Pd reflects different chemical preference in the sulfide melt. At temperatures above 1200 °C, Os shows a tendency to form alloys. Ruthenium forms a sulfide (laurite RuS2) while Ir and Rh form sulfarsenides (irarsite IrAsS and hollingworthite RhAsS, respectively). The chemical preference of PGE is selective: IPGE + Rh form metal-metal, metal-S and metal-AsS complexes while Pt and Pd form semimetal complexes. Selective complexing followed by mechanical separation of IPGE (and Rh)-ligand from Pt- and Pd-ligand associations lead to PGE fractionation.

A DFT study of Ru, Rh, Pd, Os, Ir, and Pt clusters as catalysts for methane dissociation in a direct methane fuel cell (DMHFC)

Energy Technology Data Exchange (ETDEWEB)

Psofogiannakisa, G. [Ottawa Univ., Ottawa, ON (Canada). Dept. of Chemical Engineering; Ottawa, Univ., Ottawa, ON (Canada). Centre for Catalysis Research and Innovation; St-Amant, A. [Ottawa Univ., Ottawa, ON (Canada). Dept. of Chemistry; Ternan, M. [Ottawa Univ., Ottawa, ON (Canada). Centre for Catalysis Research and Innovation; EnPross Inc., Ottawa, ON (Canada)

2008-07-01

The rate limiting step in a direct methane hydrocarbon fuel cell (DMHFC) is the dissociative chemisorption of methane. Quantum mechanical computations were used to examine the terrace, kink, and step sites on 6 different clusters of group 8 transition metals, notably Ru, Rh, Pd, Os, Ir, and Pt. The computations involved the anodic reaction of a DMHFC with a polymer electrolyte that operates at atmospheric pressure and temperatures higher than 120 degrees C. The interaction between molecular fragments and a surface (Pt) were described and density functional theory (DFT) calculations were performed using Guassian software. The geometries of 5 different platinum clusters were examined along with their electronic energy barriers. The biggest contribution to the stabilization energy came from the overlap between the sigma bond in methane and unoccupied sd hybrid orbitals in the Pt bonding atom. The study showed that when relaxation was allowed, the displacement of the bonding metal atom was 0.36 to 0.52 A. The electronic energy barrier often increased as d-orbital occupancy increased. For the kink surface sites, the energy barriers were considerably smaller for the 5d transition metals than for the 4d transition metals. 5 refs., 1 tab.

PAMAM templated N,Pt co-doped TiO2 for visible light photodegradation of brilliant black.

Science.gov (United States)

Nzaba, Sarre Kadia Myra; Ntsendwana, Bulelwa; Mamba, Bhekie Brilliance; Kuvarega, Alex Tawanda

2018-05-01

This study examined the photocatalytic degradation of an azo dye brilliant black (BB) using non-metal/metal co-doped TiO 2 . N,Pt co-doped TiO 2 photocatalysts were prepared by a modified sol-gel method using amine-terminated polyamidoamine dendrimer generation 0 (PG0) as a template and source of nitrogen. Structural, morphological, and textural properties were evaluated using scanning electron microscopy coupled to energy-dispersive X-ray spectroscopy (SEM/EDX), high-resolution transmission electron microscopy (HRTEM), X-ray diffraction spectroscopy (XRD), X-ray photoelectron spectroscopy (XPS), thermal gravimetric analysis (TGA), Fourier transform infrared (FTIR), Raman spectroscopy (RS), photoluminescence (PL) and ultra-violet/visible spectroscopy (UV-Vis). The synthesized photocatalysts exhibited lower band gap energies as compared to the Degussa P-25, revealing a red shift in band gap towards the visible light absorption region. Photocatalytic activity of N,Pt co-doped TiO 2 was measured by the reaction of photocatalytic degradation of BB dye. Enhanced photodegradation efficiency of BB was achieved after 180-min reaction time with an initial concentration of 50 ppm. This was attributed to the rod-like shape of the materials, larger surface area, and enhanced absorption of visible light induced by N,Pt co-doping. The N,Pt co-doped TiO 2 also exhibited pseudo-first-order kinetic behavior with half-life and rate constant of 0.37 and 0.01984 min -1 , respectively. The mechanism of the photodegradation of BB under the visible light irradiation was proposed. The obtained results prove that co-doping of TiO 2 with N and Pt contributed to the enhanced photocatalytic performances of TiO 2 for visible light-induced photodegradation of organic contaminants for environmental remediation. Therefore, this work provides a new approach to the synthesis of PAMAM templated N,Pt co-doped TiO 2 for visible light photodegradation of brilliant black.

Engineering Platinum Alloy Electrocatalysts in Nanoscale for PEMFC Application

Energy Technology Data Exchange (ETDEWEB)

He, Ting [Idaho National Laboratory

2016-03-01

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.

Atomic layer deposition of Ru thin film using N{sub 2}/H{sub 2} plasma as a reactant

Energy Technology Data Exchange (ETDEWEB)

Hong, Tae Eun [Busan Center, Korea Basic Science Institute, 1275 Jisadong, Gangseogu, Busan, 618-230 (Korea, Republic of); Mun, Ki-Yeung; Choi, Sang-Kyung; Park, Ji-Yoon [School of Materials Science and Engineering Yeungnam University 214-1, Dae-dong, Gyeongsan-si, Gyeongsangbuk-do, 712-749 (Korea, Republic of); Kim, Soo-Hyun, E-mail: soohyun@ynu.ac.kr [School of Materials Science and Engineering Yeungnam University 214-1, Dae-dong, Gyeongsan-si, Gyeongsangbuk-do, 712-749 (Korea, Republic of); Cheon, Taehoon [Center for Core Research Facilities, Daegu Gyeongbuk Institute of Science and Technology, Sang-ri, Hyeonpung-myeon, Dalseong-gun, Daegu (Korea, Republic of); Kim, Woo Kyoung [School of Chemical Engineering, Yeungnam University, 214-1, Dae-dong, Gyeongsan-si, Gyeongsangbuk-do, 712-749 (Korea, Republic of); Lim, Byoung-Yong; Kim, Sunjung [School of Materials Science and Engineering, University of Ulsan, Mugeo-dong, Nam-go, Ulsan, 680-749 (Korea, Republic of)

2012-07-31

Ruthenium (Ru) thin films were grown by atomic layer deposition using IMBCHRu [({eta}6-1-Isopropyl-4-MethylBenzene)({eta}4-CycloHexa-1,3-diene)Ruthenium(0)] as a precursor and a nitrogen-hydrogen mixture (N{sub 2}/H{sub 2}) plasma as a reactant, at the substrate temperature of 270 Degree-Sign C. In the wide range of the ratios of N{sub 2} and total gas flow rates (fN{sub 2}/N{sub 2} + H{sub 2}) from 0.12 to 0.70, pure Ru films with negligible nitrogen incorporation of 0.5 at.% were obtained, with resistivities ranging from {approx} 20 to {approx} 30 {mu} Ohm-Sign cm. A growth rate of 0.057 nm/cycle and negligible incubation cycle for the growth on SiO{sub 2} was observed, indicating the fast nucleation of Ru. The Ru films formed polycrystalline and columnar grain structures with a hexagonal-close-packed phase. Its resistivity was dependent on the crystallinity, which could be controlled by varying the deposition parameters such as plasma power and pulsing time. Cu was electroplated on a 10-nm-thick Ru film. Interestingly, it was found that the nitrogen could be incorporated into Ru at a higher reactant gas ratio of 0.86. The N-incorporated Ru film ({approx} 20 at.% of N) formed a nanocrystalline and non-columnar grain structure with the resistivity of {approx} 340 {mu} Ohm-Sign cm. - Highlights: Black-Right-Pointing-Pointer Atomic layer deposition (ALD) of Ru and N-incorporated Ru film using N{sub 2}/H{sub 2} plasma. Black-Right-Pointing-Pointer The growth rate of 0.057 nm/cycle and negligible incubation cycle. Black-Right-Pointing-Pointer A low resistivity of Ru ({approx} 16.5 {mu} Ohm-Sign cm) at the deposition temperature of 270 Degree-Sign C. Black-Right-Pointing-Pointer Electroplating of Cu on a 10-nm-thick ALD-Ru film.

Annealing-temperature-dependent voltage-sign reversal in all-oxide spin Seebeck devices using RuO2

Science.gov (United States)

Kirihara, Akihiro; Ishida, Masahiko; Yuge, Ryota; Ihara, Kazuki; Iwasaki, Yuma; Sawada, Ryohto; Someya, Hiroko; Iguchi, Ryo; Uchida, Ken-ichi; Saitoh, Eiji; Yorozu, Shinichi

2018-04-01

Thermoelectric converters based on the spin Seebeck effect (SSE) have attracted great attention due to their potential to offer novel applications such as energy harvesting and heat-flow sensing. For converting a SSE-induced spin current into an electric current, a transition metal film such as Pt, which exhibits large inverse spin-Hall effect (ISHE), has been typically used. In this work, we show an all-oxide SSE device using ruthenium oxide (RuO2) as a conductive film. We found that both the sign and magnitude of the SSE-induced ISHE voltage V appearing in the RuO2 film changes depending on the post annealing temperature, and that the magnitude can become larger than that of a standard SSE device using Pt. The similar sign change was also observed in Hall-resistance measurements of the RuO2 films. X-ray absorption fine structure (XAFS) spectra of as-deposited and annealed RuO2 revealed that the annealing process substantially improved the long-range crystalline order in RuO2. This suggests that change in the crystalline order may modify the dominant ISHE mechanism or electronic states in RuO2, leading to the sign reversal of V as well as the Hall coefficient. Our result demonstrates that RuO2 is an interesting material not only as a practical ISHE film but also as a testbed to study physics of spin-to-charge converters that depend on their crystalline order.

Hydrothermal synthesis of highly crystalline RuS2 nanoparticles as cathodic catalysts in the methanol fuel cell and hydrochloric acid electrolysis

International Nuclear Information System (INIS)

Li, Yanjuan; Li, Nan; Yanagisawa, Kazumichi; Li, Xiaotian; Yan, Xiao

2015-01-01

Highlights: • Highly crystalline RuS 2 nanoparticles have been first synthesized by a “one-step” hydrothermal method. • The product presents a pure cubic phase of stoichiometric ratio RuS 2 with average particle size of 14.8 nm. • RuS 2 nanoparticles were used as cathodic catalysts in methanol fuel cell and hydrochloric acid electrolysis. • The catalyst outperforms commercial Pt/C in methanol tolerance and stability towards Cl − . - Abstract: Highly crystalline ruthenium sulfide (RuS 2 ) nanoparticles have been first synthesized by a “one-step” hydrothermal method at 400 °C, using ruthenium chloride and thiourea as reactants. The products were characterized by powder X-ray diffraction (XRD), scanning electron microscopy/energy disperse spectroscopy (SEM/EDS), thermo gravimetric-differential thermal analyze (TG-DTA), transmission electron microscopy equipped with selected area electron diffraction (TEM/SAED). Fourier transform infrared spectra (IR), and X-ray photoelectron spectroscopy (XPS). XRD result illustrates that the highly crystalline product presents a pure cubic phase of stoichiometric ratio RuS 2 and the average particle size is 14.8 nm. SEM and TEM images display the products have irregular shape of 6–25 nm. XPS analyst indicates that the sulfur exists in the form of S 2 2− . Cyclic voltammetry (CV), rotating disk electrode (RDE), chronoamperometry (CA) and electrochemical impedance spectroscopy (EIS) measurements are conducted to evaluate the electrocatalytic activity and stability of the highly crystalline RuS 2 nanoparticles in oxygen reduction reaction (ORR) for methanol fuel cell and hydrochloric acid electrolysis. The results illustrate that RuS 2 is active towards oxygen reduction reaction. Although the activity of RuS 2 is lower than that of Pt/C, the RuS 2 catalyst outperforms commercial Pt/C in methanol tolerance and stability towards Cl −

Estudo do efeito de tratamentos térmicos em catalisadores de PtRu/C frente à reação de oxidação de hidrogênio na presença de CO Study of the effect of thermal treatments of PtRu/C catalysts on the hydrogen oxidation reaction in the presence of CO

Directory of Open Access Journals (Sweden)

Pietro Papa Lopes

2007-10-01

Full Text Available In this work the effects of time and temperature of thermal treatments under reducing atmosphere (H2 on PtRu/C catalysts for the hydrogen oxidation reaction (HOR in the presence of CO on a proton exchange membrane fuel cell (PEMFC single cells have been studied. It can be seen that the increase of the treatment temperature leads to an increasing sintering of the catalyst particles with reduction of the active area, although the catalyst treated at 550 ºC presents more CO tolerance for the HOR.

Inhibition of ammonia poisoning by addition of platinum to Ru/α-Al2 O3 for preferential CO oxidation in fuel cells.

Science.gov (United States)

Sato, Katsutoshi; Yagi, Sho; Zaitsu, Shuhei; Kitayama, Godai; Kayada, Yuto; Teramura, Kentaro; Takita, Yusaku; Nagaoka, Katsutoshi

2014-12-01

In polymer electrolyte fuel cell (PEFC) systems, small amounts of ammonia (NH3 ) present in the reformate gas deactivate the supported ruthenium catalysts used for preferential oxidation (PROX) of carbon monoxide (CO). In this study, we investigated how the addition of a small amount of platinum to a Ru/α-Al2 O3 catalyst (Pt/Ru=1:9 w/w) affected the catalyst's PROX activity in both the absence and the presence of NH3 (130 ppm) under conditions mimicking the reformate conditions during steam reforming of natural gas. The activity of undoped Ru/α-Al2 O3 decreased sharply upon addition of NH3 , whereas Pt/Ru/α-Al2 O3 exhibited excellent PROX activity even in the presence of NH3 . Ruthenium K-edge X-ray absorption near-edge structure (XANES) spectra indicated that in the presence of NH3 , some of the ruthenium in the undoped catalyst was oxidized in the presence of NH3 , whereas ruthenium oxidation was not observed with Pt/Ru/α-Al2 O3 . These results suggest that ruthenium oxidation is retarded by the platinum, so that the catalyst shows high activity even in the presence of NH3 . © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Characterization of highly (110)- and (111)-oriented Pb(Zr,Ti)O3 films on BaPbO3 electrode using Ru conducting barrier

International Nuclear Information System (INIS)

Liang, C.-S.; Wu, J.-M.

2005-01-01

Highly non-(001)-oriented Pb(Zr,Ti)O 3 (PZT) films have been fabricated by rf-magnetron sputtering. The preferential (110)-oriented BaPbO 3 (BPO) deposited on Ru buffer layer induces the growth of (110)-oriented PZT film. With the aid of self-organized growth of PZT, the orientation of the film deposited on random-oriented BPO/Pt(111)/Ru(002) is (111)-preferred. The insertion of Pt layer between BPO and Ru changes the orientation of PZT from (110) to (111) and prevents the oxygen diffusion. These non-(001)-oriented PZT films possess more superior ferroelectric, fatigue, and retention properties than those of (001)-oriented PZT films

A novel binary Pt{sub 3}Te{sub x}/C nanocatalyst for ethanol electro-oxidation

Energy Technology Data Exchange (ETDEWEB)

Huang, Meihua; Wang, Fei; Li, Lirong; Guo, Yonglang [College of Chemistry and Chemical Engineering, Fuzhou University, Fuzhou 350002 (China)

2008-03-15

The Pt{sub 3}Te{sub x}/C nanocatalyst was prepared and its catalytic performance for ethanol oxidation was investigated for the first time. The Pt{sub 3}Te/C nanoparticles were characterized by an X-ray diffractometer (XRD), transmission electron microscope (TEM) and energy dispersive X-ray spectroscopy equipped with TEM (TEM-EDX). The Pt{sub 3}Te/C catalyst has a typical fcc structure of platinum alloys with the presence of Te. Its particle size is about 2.8 nm. Among the synthesized catalysts with different atomic ratios, the Pt{sub 3}Te/C catalyst has the highest anodic peak current density. The cyclic voltammograms (CV) show that the anodic peak current density for the Pt{sub 3}Te/C, commercial PtRu/C and Pt/C catalysts reaches 1002, 832 and 533 A g{sup -1}, respectively. On the current-time curve, the anodic current on the Pt{sub 3}Te/C catalyst was higher than those for the catalysts reported. So, these findings show that the Pt{sub 3}Te/C catalyst has uniform nanoparticles and the best activity among the synthesized catalysts, and it is better than commercial PtRu/C and Pt/C catalysts for ethanol oxidation at room temperature. (author)

Exchange-coupled nanoscale SmCo/NdFeB hybrid magnets

Energy Technology Data Exchange (ETDEWEB)

Wang Dapeng; Poudyal, Narayan; Rong, Chuanbing [Department of Physics, University of Texas at Arlington, Arlington, TX 76019 (United States); Zhang Ying [Department of Physics, University of Texas at Arlington, Arlington, TX 76019 (United States); Materials Science and Engineering, Ames Laboratory, USDOE, Iowa State University, Ames, IA 50011 (United States); Kramer, M.J. [Materials Science and Engineering, Ames Laboratory, USDOE, Iowa State University, Ames, IA 50011 (United States); Liu, J. Ping, E-mail: pliu@uta.edu [Department of Physics, University of Texas at Arlington, Arlington, TX 76019 (United States)

2012-09-15

Nanoscale hybrid magnets containing SmCo{sub 5} and Nd{sub 2}Fe{sub 14}B hard magnetic phases have been produced via a novel 'in-one-pot' processing route. The grain size of the processed bulk composite materials is controlled below 20 nm. The refinement of the nanoscale morphology leads to effective inter-phase exchange coupling that results in single-phase like magnetic properties. Energy product of 14 MGOe was obtained in the isotropic nanocomposite magnets at room temperature. At elevated temperatures, the hybrid magnets have greatly improved thermal stability compared to the Nd{sub 2}Fe{sub 14}B single-phase counterpart and have substantially increased magnetization and energy products compared to the single-phase SmCo{sub 5} counterpart. - Highlights: Black-Right-Pointing-Pointer We realize interphase exchange coupling in nanoscale SmCo{sub 5}/Nd{sub 2}Fe{sub 14}B magnets. Black-Right-Pointing-Pointer We observe homogenously distributed two-phase grains with size smaller than 20 nm. Black-Right-Pointing-Pointer We observe a common Curie temperature in the hybrid magnet. Black-Right-Pointing-Pointer High-temperature magnetic properties of the hybrid magnets greatly improved. Black-Right-Pointing-Pointer Plastic deformation of composite materials leads to self-nanoscaling of grains.

Phosphate-Doped Carbon Black as Pt Catalyst Support: Co-catalytic Functionality for Dimethyl Ether and Methanol Electro-oxidation

DEFF Research Database (Denmark)

Yin, Min; Huang, Yunjie; Li, Qingfeng

2014-01-01

). The supported Pt catalysts show significant improvement in catalytic activity towards the direct oxidation of methanol and DME, attributable to the enhanced adsorption and dehydrogenation of methanol and DME, as well as the presence of activated OH species in the catalysts. The latter is demonstrated......Niobium-phosphate-doped (NbP-doped) carbon blacks were prepared as the composite catalyst support for Pt nanoparticles. Functionalities of the composite include intrinsic proton conductivity, surface acidity, and interfacial synergistic interactions with methanol and dimethyl ether (DME...... to facilitate the removal of CO intermediates formed during the oxidation reactions....

Characterization of RuO sub 2 electrodes for ferroelectric thin films prepared by metal-organic chemical-vapor deposition using Ru(C sub 1 sub 1 H sub 1 sub 9 O sub 2) sub 3

CERN Document Server

Lee, J M; Shin, J C; Hwang, C S; Kim, H J; Suk, C G

1999-01-01

Pure and conducting RuO sub 2 thin films were deposited on Si substrates at 250 approx 450 .deg. C using Ru(C sub 1 sub 1 H sub 1 sub 9 O sub 2) sub 3 as a precursor by low-pressure metal-organic chemical-vapor deposition (LP-MOCVD). At a lower deposition temperature,smoother and denser RuO sub 2 thin films were deposited. The RuO sub 2 thin films, which were crack free, adhered well onto the substrates and showed very low resistivities around 45 approx 60 mu OMEGA cm. RuO sub 2 thin films on (Ba, Sr)/TiO sub 3 /Pt/SiO sub 2 /Si showed good properties, indicating that MOCVD RuO sub 2 thin films from Ru(C sub 1 sub 1 H sub 1 sub 9 O sub 2) sub 3 can be applied as electrodes of high-dielectric thin films for capacitors in ultra-large-scale DRAMs.

Study of reactivities of electro-catalytic oxidation of organic substrates with Ru(IV) complex

International Nuclear Information System (INIS)

Madurro, J.M.; Oliveira, S.M. de; Campos, J.L.

1988-01-01

An electrocatalytic procedure for the oxidation of olefines, ketones, heterocycles and ethers using the Ru IV oxidant RuO (bpy) (trpy) 2+ (bpy is 2,2 - bipyridine; trpy is 2,2', 2''' - terpyridine), is described. The relative reactivities of the substrates are determined by analysis of the exponential i x t curves, using simple linear and exponential least-square programme. Mechanistics considerations based on the observed relative reactivities are discussed. (M.J.C.) [pt

Structural and physical properties of new uranium and transition element ternary stannides (Fe, Co, Ni, Ru, Rh, Pd, Ir, Pt); Proprietes structurales et physiques de nouveaux stannures ternaires a base d'uranium et d'element de transition (Fe, Co, Ni, Rh, Pd, Ir, Pt)

Energy Technology Data Exchange (ETDEWEB)

Mirambet, F

1993-12-15

This work is dedicated to the study of ternary stannides based on uranium. The author reviews the structural, magnetic and electric properties of different families of stannides. The study of the U{sub 2}M{sub 2}Sn family where M stands for Fe, Co, Ni, Ru, Rh, Pd, Ir and Pt shows that the magnetic behaviour of uranium in these compounds is strongly influenced by the transition element M, which is explained by the hybridization force 5f(U) - nd(M) that depends on the number of electrons on the d shell of the M element. For instance, for the elements whose d shell is low filled (Fe, Ru), the U{sub 2}M{sub 2}Sn stannides show no magnetic order. On the other hand, when the number of d-electrons increases, a magnetic order appears progressively.

Measurement of benzenethiol adsorption to nanostructured Pt, Pd, and PtPd films using Raman spectroelectrochemistry.

Science.gov (United States)

Pomfret, Michael B; Pietron, Jeremy J; Owrutsky, Jeffrey C

2010-05-04

Raman spectroscopy and electrochemical methods were used to study the behavior of the model adsorbate benzenethiol (BT) on nanostructured Pt, Pd, and PtPd electrodes as a function of applied potential. Benzenethiol adsorbs out of ethanolic solutions as the corresponding thiolate, and voltammetric stripping data reveal that BT is oxidatively removed from all of the nanostructured metals upon repeated oxidative and reductive cycling. Oxidative stripping potentials for BT increase in the order Pt oxidizing potentials via cleavage of the Pt-S bond. In contrast, on nanoscale Pd and PtPd, BT is irreversibly lost due to cleavage of BT C-S bonds at oxidizing potentials, which leaves adsorbed sulfur oxides on Pd and PtPd films and effects the desulfurization of BT. While Pd and PtPd films are less sulfur-resistant than Pt films, palladium oxides, which form at higher potentials than Pt oxides, oxidatively desulfurize BT. In situ spectroelectrochemical Raman spectroscopy provides real-time, chemically specific information that complements the cyclic voltammetric data. The combination of these techniques affords a powerful and convenient method for guiding the development of sulfur-tolerant PEMFC catalysts.

Preparação e caracterização de eletrocatalisadores PtRu/C e PtSn/C via redução química por ácido cítrico para oxidação direta de alcoóis em células a combustível tipo PEM

OpenAIRE

Roberto Willyan Ramon Verjulio-Silva

2008-01-01

Neste trabalho, os sistemas de eletrocatalisadores platina-rutênio (PtRu/C) e platina-estanho (PtSn/C) suportados em carbono de alta área superficial XC72R (Cabot) foram preparados pela redução química de precursores metálicos em solução usando o ácido cítrico como agente redutor. Os eletrocatalisadores foram preparados em diferentes valores de pH, com o objetivo de obter as condições de sínteses mais otimizadas para cada um dos sistemas preparados. O método otimizado mostrou-se eficiente na ...

Strong Metal Support Interaction of Pt and Ru Nanoparticles Deposited on HOPG Probed by the H-D Exchange Reaction

DEFF Research Database (Denmark)

Fiordaliso, Elisabetta M.; Dahl, Søren; Chorkendorff, Ib

2012-01-01

The interaction between metals and support is investigated in the case of 50 Å Pt and 50 Å Ru films deposited on a HOPG substrate. The films are prepared by electron beam physical vapor deposition and annealed in UHV to temperatures up to 700 °C. The equilibrium hydrogen exchange rate between...... adsorbed and gas phase at 1 bar is measured before and after annealing. The rate is measured in the temperature range of 40–200 °C at 1 bar, by utilization of the H-D exchange reaction. Experiments are performed on fresh cleaved and sputtered HOPG, which give similar results. We find that annealing...... the films from 150 up to 700 °C increases the amount of carbon present in the films up to 95%, as derived by surface analysis, indicating the formation of a carbon layer on top of the metal films. The exchange rate decreases dramatically with increasing carbon content on the films for both metals, pointing...

Fabrication of ultra-thin cerium oxide layers on Ru(0001) single crystal surfaces. Scanning tunneling microscopic and photoelectron spectroscopic studies on growth, structure and properties; Herstellung ultraduenner Ceroxidschichten auf Ru(0001)-Einkristallflaechen. Rastertunnelmikroskopische und photoelektronenspektroskopische Untersuchungen zu Wachstum, Struktur und Eigenschaften

Energy Technology Data Exchange (ETDEWEB)

Bouchtaoui, Mustapha

2016-12-07

The thesis at hand aims at a study of structure and properties of well-defined ultrathin CeO{sub 2} films supported on Ru(0001). Such systems may serve as model systems in heterogenous catalysis. The epitaxial growth of ceria films on Ru(0001) surface has been achieved by electron beam evaporation of metal Cer at low background oxygen pressure of 10{sup -6} mbar under ultrahigh-vacuum conditions at room temperature. Cerium oxide qualifies for proper oxygen-storage in oxidation reactions, and hence it widely used in heterogenous catalysis. The oxidation begins with the adsorption of CO on the CeO{sub 2}(111) surface, and it ends with participation of lattice oxygen leading to vacancy formation and CO{sub 2} desorption. We investigate the geometric structure by means of scanning tunneling microscopy and low energy electron diffraction. The coverage of 2.5 monolayers (ML) was sufficient to cover the substrate almost completely. We further analysed the interaction of CO with the CeO{sub 2}/Ru(0001) and the Pt/CeO{sub 2}/Ru(0001) systems. During the interaction process the ratio of Ce{sup 4+} and Ce{sup 3+} changes significantly. This ratio change as well as the effect of Pt evaporated onto the surface with respect to the reducibility of CeO{sub 2}/Ru(0001) in CO environment has been studied by X-ray photoemission spectroscopy and it has been confirmed with thermal desorption spectroscopy. It is revealed that the Pt-Nanoparticles with a height from 7.15 Aa to 9.73 Aa clearly enhances the reducibility of CeO{sub 2}.

Hydrothermal synthesis of highly crystalline RuS{sub 2} nanoparticles as cathodic catalysts in the methanol fuel cell and hydrochloric acid electrolysis

Energy Technology Data Exchange (ETDEWEB)

Li, Yanjuan [Key Laboratory of Marine Chemistry Theory and Technology, Minisry of Education Ocean University of China, Qingdao, 266100 (China); College of Material Science and Engineering, Key Laboratory of Automobile Materials of Ministry of Education, Jilin University, 2699 Qianjin Street, Changchun 130012 (China); Li, Nan, E-mail: lin@jlu.edu.cn [College of Material Science and Engineering, Key Laboratory of Automobile Materials of Ministry of Education, Jilin University, 2699 Qianjin Street, Changchun 130012 (China); Yanagisawa, Kazumichi [Research Laboratory of Hydrothermal Chemistry, Kochi University, Kochi 780-8520 (Japan); Li, Xiaotian [College of Material Science and Engineering, Key Laboratory of Automobile Materials of Ministry of Education, Jilin University, 2699 Qianjin Street, Changchun 130012 (China); Yan, Xiao [Key Laboratory of Physics and Technology for Advanced Batteries (Ministry of Education), College of Physics, Jilin University, Changchun 130012 (China)

2015-05-15

Highlights: • Highly crystalline RuS{sub 2} nanoparticles have been first synthesized by a “one-step” hydrothermal method. • The product presents a pure cubic phase of stoichiometric ratio RuS{sub 2} with average particle size of 14.8 nm. • RuS{sub 2} nanoparticles were used as cathodic catalysts in methanol fuel cell and hydrochloric acid electrolysis. • The catalyst outperforms commercial Pt/C in methanol tolerance and stability towards Cl{sup −}. - Abstract: Highly crystalline ruthenium sulfide (RuS{sub 2}) nanoparticles have been first synthesized by a “one-step” hydrothermal method at 400 °C, using ruthenium chloride and thiourea as reactants. The products were characterized by powder X-ray diffraction (XRD), scanning electron microscopy/energy disperse spectroscopy (SEM/EDS), thermo gravimetric-differential thermal analyze (TG-DTA), transmission electron microscopy equipped with selected area electron diffraction (TEM/SAED). Fourier transform infrared spectra (IR), and X-ray photoelectron spectroscopy (XPS). XRD result illustrates that the highly crystalline product presents a pure cubic phase of stoichiometric ratio RuS{sub 2} and the average particle size is 14.8 nm. SEM and TEM images display the products have irregular shape of 6–25 nm. XPS analyst indicates that the sulfur exists in the form of S{sub 2}{sup 2−}. Cyclic voltammetry (CV), rotating disk electrode (RDE), chronoamperometry (CA) and electrochemical impedance spectroscopy (EIS) measurements are conducted to evaluate the electrocatalytic activity and stability of the highly crystalline RuS{sub 2} nanoparticles in oxygen reduction reaction (ORR) for methanol fuel cell and hydrochloric acid electrolysis. The results illustrate that RuS{sub 2} is active towards oxygen reduction reaction. Although the activity of RuS{sub 2} is lower than that of Pt/C, the RuS{sub 2} catalyst outperforms commercial Pt/C in methanol tolerance and stability towards Cl{sup −}.

Structure and composition of single Pt–Ru electrocatalyst nanoparticles supported on multiwall carbon nanotubes

International Nuclear Information System (INIS)

Paraguay-Delgado, Francisco; Malac, Marek; Alonso-Nuñez, Gabriel

2014-01-01

Individual Pt-Ru nanoparticles (NPs) supported on multiwall carbon nanotubes (MWCNTs) synthesized by microemulsion method were characterized by nano beam diffraction (NBD) and high resolution imaging in transmission electron microscopy (TEM). Comparing the TEM images and NBD to simulations provided insight into particle composition, structure and morphology in three dimensions. In particular, the NBD allowed us to detect various components of the individual NPs that would be difficult to observe otherwise. We find that the NPs contain four different components: Pt–RuO 2 , Pt–Ru, RuO 2 and metallic Pt. Often an individual NP is composed of more than one component. The most frequently encountered external morphology is close to a spherical shape and ∼3.7 nm in diameter. The collective properties of NPs’ assemblies were studied by thermogravimetry, differential thermal analysis and x-ray diffraction. The results allowed us to gain some insight into the relation of the NPs’ structure and composition with their catalytic performance, and revealed the presence of components not detectable by bulk methods. The electrocatalytic properties were evaluated by CO stripping, methanol oxidation and oxygen reduction. Bulk characterization methods miss many properties and structures present in the sample due to low volume fraction and due to overlap of reflections. Single NPs should be analyzed to obtain reliable indication of sample composition. (paper)

Pt/AlPO{sub 4} nanocomposite thin-film electrodes for ethanol electrooxidation

Energy Technology Data Exchange (ETDEWEB)

Oh, Yuhong; Kang, Joonhyeon; Nam, Seunghoon; Byun, Sujin [WCU Hybrid Materials Program, Department of Materials Science and Engineering, Research Institute of Advanced Materials, Seoul National University, Seoul 151-744 (Korea, Republic of); Park, Byungwoo, E-mail: byungwoo@snu.ac.kr [WCU Hybrid Materials Program, Department of Materials Science and Engineering, Research Institute of Advanced Materials, Seoul National University, Seoul 151-744 (Korea, Republic of)

2012-07-16

The enhanced catalytic properties toward ethanol electrooxidation on Pt/AlPO{sub 4} nanocomposite thin-film electrodes were investigated. The Pt/AlPO{sub 4} nanocomposites with various Al/Pt ratios (0.27, 0.57, and 0.96) were fabricated by a co-sputtering method. All of the Pt/AlPO{sub 4} nanocomposites showed a negative shift in the onset potential and a higher current density than those of pure Pt electrode for the electrooxidation of ethanol. Among the various Pt/AlPO{sub 4} nanocomposite thin-film electrodes, the electrode with an atomic ratio of Al to Pt of 0.57 showed the highest electrocatalytic activity for ethanol electrooxidation. The activation enthalpy for the optimum Pt/AlPO{sub 4} nanocomposite was approximately 0.05 eV lower than that of pure Pt. It is believed that the enhancement in catalytic activity is due to the electron-rich Pt resulting from the Fermi-energy difference between Pt and AlPO{sub 4}. - Highlights: Black-Right-Pointing-Pointer The enhanced ethanol electrooxidation on Pt/AlPO{sub 4} nanocomposites is investigated. Black-Right-Pointing-Pointer The Pt/AlPO{sub 4} exhibits higher current density and lower onset potential than pure Pt. Black-Right-Pointing-Pointer The activation enthalpy for optimum Pt/AlPO{sub 4} electrode is {approx}0.05 eV lower than pure Pt. Black-Right-Pointing-Pointer XPS shows electron-rich Pt due to Fermi-energy difference between Pt and AlPO{sub 4}.

Synthesis process and structural characterization of the Sr{sub 2}EuRuO{sub 6} complex perovskite

Energy Technology Data Exchange (ETDEWEB)

Triana, C.A.; Landinez Tellez, D.A. [Grupo de Fisica de Nuevos Materiales (GFNM), Departamento de Fisica, Universidad Nacional de Colombia, Bogota D.C. A.A. 5997 (Colombia); Roa-Rojas, J., E-mail: jroar@unal.edu.co [Grupo de Fisica de Nuevos Materiales (GFNM), Departamento de Fisica, Universidad Nacional de Colombia, Bogota D.C. A.A. 5997 (Colombia)

2012-03-05

Highlights: Black-Right-Pointing-Pointer Crystal structure, surface morphology and composition of Sr{sub 2}EuRuO{sub 6} have been studied. Black-Right-Pointing-Pointer Sr{sub 2}EuRuO{sub 6} crystallize in a monoclinic perovskite-type structure in P2{sub 1}/n space group. Black-Right-Pointing-Pointer Ru{sup 5+} and Eu{sup 3+} ions are on the six coordinate M sites, Sr{sup 2+} is located in the A-site. Black-Right-Pointing-Pointer Scanning electron microscopy and Scherrer formula shows a particle size of D = 34.2 nm. Black-Right-Pointing-Pointer Activation energy Q through the Arrhenius plot for Sr{sub 2}EuRuO{sub 6} is close to 39.6 kJ/mol. - Abstract: The Sr{sub 2}EuRuO{sub 6} complex perovskite has been synthesized by the solid-state reaction method and the crystal structure, surface morphology and composition have been investigated. Results of powder X-ray diffraction measurements and Rietveld analysis show that this compound crystallizes in a monoclinic distorted perovskite-type structure, which belongs to the monoclinic P2{sub 1}/n (no. 14) space group, that corresponds to the (a{sup +}b{sup -}b{sup -}) tilt system on the Glazer notation. The structure presents an alternating distribution of the Ru{sup 5+} and Eu{sup 3+} ions on the six coordinate M sites, while the Sr{sup 2+} is located in the A-site of the Sr{sub 2}EuRuO{sub 6} complex perovskite, with lattice parameters a = 5.7996(5) Angstrom-Sign , b = 5.8960(7) Angstrom-Sign , c = 8.3234(6) Angstrom-Sign , angle {beta} = 90.234(7) Degree-Sign and V = 284.61(4) Angstrom-Sign {sup 3}. Morphological analysis of this material, performed by scanning electron microscopy (SEM), allows to establish the granular feature of compound with agglomerates from amongst Almost-Equal-To 1 to 3 {mu}m size, and by means of the Scherrer formula was calculated a particle size of D = 34.2 nm. Result suggests that crystal structure of the Sr{sub 2}EuRuO{sub 6} suffers grain size-induced polarization rotation, which produces a

Study on oxidization of Ru and its application as electrode of PZT capacitor for FeRAM

International Nuclear Information System (INIS)

Jia Ze; Ren Tianling; Liu Tianzhi; Hu Hong; Zhang Zhigang; Xie Dan; Liu Litian

2007-01-01

Oxidization for Ru through anneal with plenteous oxygen atmosphere and its application as the top electrode of sol-gel PZT capacitor are investigated in this study. PZT capacitor with RuO 2 or oxygen-doped Ru as top electrode can be obtained from Ru/PZT/Pt capacitor through slow-rate anneal at 650 deg. C for 20 min in cannulation furnace. It has larger remanent polarization, better rectangle shape, better fatigue properties and lower leakage current than the other capacitors with PZT film prepared by the same process and different top electrodes in this study. Plenteous oxygen atmosphere and 650 deg. C in cannulation furnace are important conditions for the oxidation of Ru and renewed crystallization of PZT in this capacitor. Plenteous oxygen at interface can compensate the oxygen vacancies at PZT/electrode interface, which results in the above good characteristics

Novel anode catalyst for direct methanol fuel cells.

Science.gov (United States)

Basri, S; Kamarudin, S K; Daud, W R W; Yaakob, Z; Kadhum, A A H

2014-01-01

PtRu catalyst is a promising anodic catalyst for direct methanol fuel cells (DMFCs) but the slow reaction kinetics reduce the performance of DMFCs. Therefore, this study attempts to improve the performance of PtRu catalysts by adding nickel (Ni) and iron (Fe). Multiwalled carbon nanotubes (MWCNTs) are used to increase the active area of the catalyst and to improve the catalyst performance. Electrochemical analysis techniques, such as energy dispersive X-ray spectrometry (EDX), X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), and X-ray photoelectron spectroscopy (XPS), are used to characterize the kinetic parameters of the hybrid catalyst. Cyclic voltammetry (CV) is used to investigate the effects of adding Fe and Ni to the catalyst on the reaction kinetics. Additionally, chronoamperometry (CA) tests were conducted to study the long-term performance of the catalyst for catalyzing the methanol oxidation reaction (MOR). The binding energies of the reactants and products are compared to determine the kinetics and potential surface energy for methanol oxidation. The FESEM analysis results indicate that well-dispersed nanoscale (2-5 nm) PtRu particles are formed on the MWCNTs. Finally, PtRuFeNi/MWCNT improves the reaction kinetics of anode catalysts for DMFCs and obtains a mass current of 31 A g(-1) catalyst.

On new ternary equiatomic scandium transition metal aluminum compounds ScTAl with T = Cr, Ru, Ag, Re, Pt, and Au

Energy Technology Data Exchange (ETDEWEB)

Radzieowski, Mathis; Janka, Oliver [Muenster Univ. (Germany). Inst. fuer Anorganische und Analytische Chemie; Benndorf, Christopher [Muenster Univ. (Germany). Inst. fuer Anorganische und Analytische Chemie; Muenster Univ. (Germany). Inst. fuer Physikalische Chemie; Haverkamp, Sandra [Muenster Univ. (Germany). Inst. fuer Physikalische Chemie; Eckert, Hellmut [Muenster Univ. (Germany). Inst. fuer Physikalische Chemie; University of Sao Paulo, Sao Carlos, SP (Brazil). Inst. of Physics

2016-08-01

The new equiatomic scandium transition metal aluminides ScTAl for T = Cr, Ru, Ag, Re, Pt, and Au were obtained by arc-melting of the elements followed by subsequent annealing for crystal growth. The samples were studied by powder and single crystal X-ray diffraction. The structures of three compounds were refined from single crystal X-ray diffractometer data: ScCrAl, MgZn{sub 2} type, P6{sub 3}/mmc, a = 525.77(3), c = 858.68(5) pm, R{sub 1} = 0.0188, wR{sub 2} = 0.0485, 204 F{sup 2} values, 13 variables, ScPtAl, TiNiSi type, Pnma, a = 642.83(4), b = 428.96(2), c = 754.54(5) pm, R{sub 1} = 0.0326, wR{sub 2} = 0.0458, 448 F{sup 2} values, 20 variables and ScAuAl, HfRhSn type, P anti 62c, a = 722.88(4), c = 724.15(4) pm, R{sub 1} = 0.0316, wR{sub 2} = 0.0653, 512 F{sup 2} values, 18 variables. Phase pure samples of all compounds were furthermore investigated by magnetic susceptibility measurements, and Pauli-paramagnetism but no superconductivity was observed down to 2.1 K for all of them. The local structural features and disordering phenomena have been characterized by {sup 27}Al and {sup 45}Sc magic angle spinning (MAS) and static NMR spectroscopic investigations.

Activity and Stability of Nanoscale Oxygen Reduction Catalysts

Energy Technology Data Exchange (ETDEWEB)

Shao-Horn, Yang

2015-07-28

Design of highly active and stable nanoscale catalysts for electro-oxidation of small organic molecules is of great importance to the development of efficient fuel cells. The amount and instability of Pt-based catalysts in the cathode limits the cost, efficiency and lifetime of proton exchange membrane fuel cells. We developed a microscopic understanding of the factors governing activity and stability in Pt and PtM alloys. Experimental efforts were focused on probing the size and shape dependence of ORR activity of Pt-based nanoparticles supported on carbon nanotubes. A microscopic understanding of the activity was achieved by correlating voltammetry and rotating ring disk electrodes to surface atomic and electronic structures, which were elucidated predominantly by high-resolution transmission electron microscopy (HRTEM), Scanning transmission electron microscopy energy dispersive X-ray Spectroscopy (STEM-EDS) and synchrotron X-ray absorption spectroscopy (XAS).

One-Pot and Facile Fabrication of Hierarchical Branched Pt-Cu Nanoparticles as Excellent Electrocatalysts for Direct Methanol Fuel Cells.

Science.gov (United States)

Cao, Yanqin; Yang, Yong; Shan, Yufeng; Huang, Zhengren

2016-03-09

Hierarchical branched nanoparticles are one promising nanostructure with three-dimensional open porous structure composed of integrated branches for superior catalysis. We have successfully synthesized Pt-Cu hierarchical branched nanoparticles (HBNDs) with small size of about 30 nm and composed of integrated ultrathin branches by using a modified polyol process with introduction of poly(vinylpyrrolidone) and HCl. This strategy is expected to be a general strategy to prepare various metallic nanostructures for catalysis. Because of the special open porous structure, the as-prepared Pt-Cu HBNDs exhibit greatly enhanced specific activity toward the methanol oxidation reaction as much as 2.5 and 1.7 times compared with that of the commercial Pt-Ru and Pt-Ru/C catalysts, respectively. Therefore, they are potentially applicable as electrocatalysts for direct methanol fuel cells.

Preparation and electrocatalytic properties of Pt-SiO2 nanocatalysts for ethanol electrooxidation.

Science.gov (United States)

Liu, B; Chen, J H; Zhong, X X; Cui, K Z; Zhou, H H; Kuang, Y F

2007-03-01

Due to their high stability in general acidic solutions, SiO(2) nanoparticles were selected as the second catalyst for ethanol oxidation in sulfuric acid aqueous solution. Pt-SiO(2) nanocatalysts were prepared in this paper. The micrography and elemental composition of Pt-SiO(2) nanoparticles were characterized by scanning electron microscopy and energy dispersive X-ray spectroscopy, respectively. The electrocatalytic properties of Pt-SiO(2) nanocatalysts for ethanol oxidation were investigated by cyclic voltammetry. Under the same Pt loading mass and experimental conditions for ethanol oxidation, Pt-SiO(2) nanocatalysts show higher activity than PtRu/C (E-Tek), Pt/C (E-Tek), and Pt catalysts. Additionally, Pt-SiO(2) nanocatalysts possess good anti-poisoning ability. The results indicate that Pt-SiO(2) nanocatalysts may have good potential applications in direct ethanol fuel cells.

Black hole physics from two-dimensional dilaton gravity based on the SL(2,R)/U(1) coset model

International Nuclear Information System (INIS)

Nojiri, S.; Oda, I.

1994-01-01

We analyze the quantum two-dimensional dilaton gravity model, which is described by the SL(2,R)/U(1) gauged Wess-Zumino-Witten model deformed by a (1,1) operator. We show that the curvature singularity does not appear when the central charge c matter of the matter fields is given by 22 matter matter matter ∝δ(x + -x 0 + ), create a kind of wormholes, i.e., causally disconnected regions. Most of the quantum information in past null infinity is lost in future null infinity but the lost information would be carried by the wormholes. We also discuss the problem of defining the mass of quantum black holes. On the basis of the argument by Regge and Teitelboim, we show that the ADM mass measured by the observer who lives in one of the asymptotically flat regions is finite and does not vanish in general. On the other hand, the Bondi mass is ill defined in this model. Instead of the Bondi mass, we consider the mass measured by observers who live in an asymptotically flat region at first. A class of observers finds the mass of the black hole created by a shock wave changes as the observers' proper time goes by, i.e., they observe Hawking radiation. The measured mass vanishes after the infinite proper time and the black hole evaporates completely. Therefore the total Hawking radiation is positive even when N<24

PdRu/C catalysts for ethanol oxidation in anion-exchange membrane direct ethanol fuel cells

Science.gov (United States)

Ma, Liang; He, Hui; Hsu, Andrew; Chen, Rongrong

2013-11-01

Carbon supported PdRu catalysts with various Pd:Ru atomic ratios were synthesized by impregnation method, and characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), electrochemical half-cell tests, and the anion-exchange membrane direct ethanol fuel cell (AEM-DEFC) tests. XRD results suggest that the PdRu metal exists on carbon support in an alloy form. TEM study shows that the bimetallic PdRu/C catalysts have slightly smaller average particle size than the single metal Pd/C catalyst. Lower onset potential and peak potential and much higher steady state current for ethanol oxidation in alkaline media were observed on the bimetallic catalysts (PdxRuy/C) than on the Pd/C, while the activity for ethanol oxidation on the pure Ru/C was not noticeable. By using Pd/C anode catalysts and MnO2 cathode catalysts, AEM-DEFCs free from the expensive Pt catalyst were assembled. The AEM DEFC using the bimetallic Pd3Ru/C anode catalyst showed a peak power density as high as 176 mW cm-2 at 80 °C, about 1.8 times higher than that using the single metal Pd/C catalyst. The role of Ru for enhancing the EOR activity of Pd/C catalysts is discussed.

Novel Anode Catalyst for Direct Methanol Fuel Cells

Directory of Open Access Journals (Sweden)

S. Basri

2014-01-01

Full Text Available PtRu catalyst is a promising anodic catalyst for direct methanol fuel cells (DMFCs but the slow reaction kinetics reduce the performance of DMFCs. Therefore, this study attempts to improve the performance of PtRu catalysts by adding nickel (Ni and iron (Fe. Multiwalled carbon nanotubes (MWCNTs are used to increase the active area of the catalyst and to improve the catalyst performance. Electrochemical analysis techniques, such as energy dispersive X-ray spectrometry (EDX, X-ray diffraction (XRD, field emission scanning electron microscopy (FESEM, and X-ray photoelectron spectroscopy (XPS, are used to characterize the kinetic parameters of the hybrid catalyst. Cyclic voltammetry (CV is used to investigate the effects of adding Fe and Ni to the catalyst on the reaction kinetics. Additionally, chronoamperometry (CA tests were conducted to study the long-term performance of the catalyst for catalyzing the methanol oxidation reaction (MOR. The binding energies of the reactants and products are compared to determine the kinetics and potential surface energy for methanol oxidation. The FESEM analysis results indicate that well-dispersed nanoscale (2–5 nm PtRu particles are formed on the MWCNTs. Finally, PtRuFeNi/MWCNT improves the reaction kinetics of anode catalysts for DMFCs and obtains a mass current of 31 A g−1 catalyst.

High temperature-induced phase transitions in Sr{sub 2}GdRuO{sub 6} complex perovskite

Energy Technology Data Exchange (ETDEWEB)

Triana, C.A.; Corredor, L.T.; Landinez Tellez, D.A. [Grupo de Fisica de Nuevos Materiales, Departamento de Fisica, Universidad Nacional de Colombia, Bogota D.C. A.A. 14490 (Colombia); Roa-Rojas, J., E-mail: jroar@unal.edu.co [Grupo de Fisica de Nuevos Materiales, Departamento de Fisica, Universidad Nacional de Colombia, Bogota D.C. A.A. 14490 (Colombia)

2011-12-15

Highlights: Black-Right-Pointing-Pointer Crystal structure, thermal expansion and phase transitions at high-temperature of Sr{sub 2}GdRuO{sub 6} perovskite has been investigated. Black-Right-Pointing-Pointer X-ray diffraction pattern at 298 K of Sr{sub 2}GdRuO{sub 6} corresponds to monoclinic perovskite-type structure with P2{sub 1}/n space group. Black-Right-Pointing-Pointer Evolution of X-ray diffraction patterns at high-temperature shows that the Sr{sub 2}GdRuO{sub 6} perovskite suffers two-phase transitions. Black-Right-Pointing-Pointer At 573 K the X-ray diffraction pattern of Sr{sub 2}GdRuO{sub 6} corresponds to monoclinic perovskite-type structure with I2/m space group. Black-Right-Pointing-Pointer At 1273 K the Sr{sub 2}GdRuO{sub 6} perovskite suffers a complete phase-transition from monoclinic I2/m (no. 12) to tetragonal I4/m (no. 87). -- Abstract: The crystal structure behavior of the Sr{sub 2}GdRuO{sub 6} complex perovskite at high-temperature has been investigated over a wide temperature range between 298 K {<=} T {<=} 1273 K. Measurements of X-ray diffraction at room-temperature and Rietveld analysis of the experimental patterns show that this compound crystallizes in a monoclinic perovskite-like structure, which belongs to the P2{sub 1}/n (no. 14) space group and 1:1 ordered arrangement of Ru{sup 5+} and Gd{sup 3+} cations over the six-coordinate M sites. Experimental lattice parameters were obtained to be a =5.8103(5) Angstrom-Sign , b =5.8234(1) Angstrom-Sign , c =8.2193(9) Angstrom-Sign , V = 278.11(2) Angstrom-Sign {sup 3} and angle {beta} = 90.310(5) Degree-Sign . The high-temperature analysis shows the occurrence of two-phase transitions on this material. First, at 573 K it adopts a monoclinic perovskite-type structure with I2/m (no. 12) space group with lattice parameters a = 5.8275(6) Angstrom-Sign , b = 5.8326(3) Angstrom-Sign , c = 8.2449(2) Angstrom-Sign , V = 280.31(3) Angstrom-Sign {sup 3} and angle {beta} = 90.251(3) Degree-Sign . Close

Structural control of ultra-fine CoPt nanodot arrays via electrodeposition process

Energy Technology Data Exchange (ETDEWEB)

Wodarz, Siggi [Department of Applied Chemistry, Waseda University, Shinjuku, Tokyo 169-8555 (Japan); Hasegawa, Takashi; Ishio, Shunji [Department of Materials Science, Akita University, Akita City 010-8502 (Japan); Homma, Takayuki, E-mail: t.homma@waseda.jp [Department of Applied Chemistry, Waseda University, Shinjuku, Tokyo 169-8555 (Japan)

2017-05-15

CoPt nanodot arrays were fabricated by combining electrodeposition and electron beam lithography (EBL) for the use of bit-patterned media (BPM). To achieve precise control of deposition uniformity and coercivity of the CoPt nanodot arrays, their crystal structure and magnetic properties were controlled by controlling the diffusion state of metal ions from the initial deposition stage with the application of bath agitation. Following bath agitation, the composition gradient of the CoPt alloy with thickness was mitigated to have a near-ideal alloy composition of Co:Pt =80:20, which induces epitaxial-like growth from Ru substrate, thus resulting in the improvement of the crystal orientation of the hcp (002) structure from its initial deposition stages. Furthermore, the cross-sectional transmission electron microscope (TEM) analysis of the nanodots deposited with bath agitation showed CoPt growth along its c-axis oriented in the perpendicular direction, having uniform lattice fringes on the hcp (002) plane from the Ru underlayer interface, which is a significant factor to induce perpendicular magnetic anisotropy. Magnetic characterization of the CoPt nanodot arrays showed increase in the perpendicular coercivity and squareness of the hysteresis loops from 2.0 kOe and 0.64 (without agitation) to 4.0 kOe and 0.87 with bath agitation. Based on the detailed characterization of nanodot arrays, the precise crystal structure control of the nanodot arrays with ultra-high recording density by electrochemical process was successfully demonstrated. - Highlights: • Ultra-fine CoPt nanodot arrays were fabricated by electrodeposition. • Crystallinity of hcp (002) was improved with uniform composition formation. • Uniform formation of hcp lattices leads to an increase in the coercivity.

Ethanol electrooxidation on Pt/C and Pd/C catalysts promoted with oxide

Energy Technology Data Exchange (ETDEWEB)

Xu, Changwei [Department of Chemistry and Institute of Nanochemistry, Jinan University, Guangzhou 510632 (China); State Key Laboratory of Optoelectronic Materials and Technologies, School of Physics and Engineering, Sun Yat-Sen University, Guangzhou 510275 (China); Shen, Pei kang [State Key Laboratory of Optoelectronic Materials and Technologies, School of Physics and Engineering, Sun Yat-Sen University, Guangzhou 510275 (China); Liu, Yingliang [Department of Chemistry and Institute of Nanochemistry, Jinan University, Guangzhou 510632 (China)

2007-02-10

This research aims to investigate Pd-based catalysts as a replacement for Pt-based catalysts for ethanol electrooxidation in alkaline media. The results show that Pd/C has a higher catalytic activity and better steady-state behaviour for ethanol oxidation than that of Pt/C. The effect of the addition of CeO{sub 2} and NiO to the Pt/C and Pd/C electrocatalysts on ethanol oxidation is also studied in alkaline media. The electrocatalysts with a weight ratio of noble metal (Pt, Pd) to CeO{sub 2} of 2:1 and a noble metal to NiO ration 6:1 show the highest catalytic activity for ethanol oxidation. The oxide promoted Pt/C and Pd/C electrocatalysts show a higher activity than the commercial E-TEK PtRu/C electrocatalyst for ethanol oxidation in alkaline media. (author)

Nano-scale islands of ruthenium oxide as an electrochemical sensor for iodate and periodate determination

International Nuclear Information System (INIS)

Chatraei, Fatemeh; Zare, Hamid R.

2013-01-01

In this study, a promising electrochemical sensor was fabricated by the electrodeposition of nano-scale islands of ruthenium oxide (ruthenium oxide nanoparticles, RuON) on a glassy carbon electrode (RuON–GCE). Then, the electrocatalytic oxidation of iodate and periodate was investigated on it, using cyclic voltammetry, chronoamperometry and amperometry as diagnostic techniques. The charge transfer coefficient, α, and the charge transfer rate constant, k s , for electron transfer between RuON and GCE were calculated as 0.5 ± 0.03 and 9.0 ± 0.7 s −1 respectively. A comparison of the data obtained from the electrocatalytic reduction of iodate and periodate at a bare GCE (BGCE) and RuON–GCE clearly shows that the unique electronic properties of nanoparticles definitely improve the characteristics of iodate and periodate electrocatalytic reduction. The kinetic parameters such as the electron transfer coefficient, α, and the heterogeneous electron transfer rate constant, k′, for the reduction of iodate and periodate at RuON–GCE surface were determined using cyclic voltammetry. Amperometry revealed a good linear relationship between the peak current and the concentration of iodate and periodate. The detection limits of 0.9 and 0.2 μM were calculated for iodate and periodate respectively. Highlights: ► Ruthenium oxide nanoparticles, RuON, were used for electrocatalytic reduction iodate and periodate. ► Formal potential, E 0 ′, of the surface redox couple of RuON is pH-dependent. ► The heterogeneous electron transfer rate constant values between both analytes and RuON were calculated.

Methanol oxidation at carbon paste electrodes modified with (Pt–Ru)/carbon aerogels nanocomposites

Energy Technology Data Exchange (ETDEWEB)

Fort, Carmen I., E-mail: iladiu@chem.ubbcluj.ro [Laboratory of Electrochemical Research and Nonconventional Materials, Babes-Bolyai University, Arany Janos 11, RO-400028, Cluj-Napoca (Romania); Cotet, Liviu C. [Laboratory of Electrochemical Research and Nonconventional Materials, Babes-Bolyai University, Arany Janos 11, RO-400028, Cluj-Napoca (Romania); Vasiliu, Florin [The National Institute of Materials Physics, Atomistilor str. 105 bis, PO Box MG. 7, Magurele, RO 077125, Bucharest (Romania); Marginean, Petre [National Institute for Research and Development of Isotopic and Molecular Technologies, RO 400293, Cluj-Napoca (Romania); Danciu, Virginia; Popescu, Ionel C. [Laboratory of Electrochemical Research and Nonconventional Materials, Babes-Bolyai University, Arany Janos 11, RO-400028, Cluj-Napoca (Romania)

2016-04-01

Mesoporous carbon aerogels (CAs) impregnated with (Pt–Ru) nanoparticles were prepared, incorporated into carbon paste electrodes (CPEs) and investigated as electrocatalysts for CH{sub 3}OH electro-oxidation. The sol–gel method, followed by supercritical drying with liquid CO{sub 2} and thermal pyrolysis in an inert atmosphere, was used to obtain high mesoporous CAs. (Pt–Ru)/CAs nanocomposites with various (Pt–Ru) loading were prepared by using Ru(AcAc){sub 3} and H{sub 2}PtCl{sub 6} as metal precursors and the impregnation method. The morpho-structural peculiarities of the so prepared (Pt–Ru)/CAs electrocatalysts were examined by using elemental analysis, N{sub 2} adsorption-desorption isotherms, transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM), energy dispersive X-ray (EDX) and selected area electron diffraction (SAED). Cyclic voltammetry measurements, carried out at (Pt–Ru)/CA-CPEs incorporating nanocomposites with various Pt–Ru loading and different specific surface areas, showed that CA with the highest specific surface area (843 m{sup 2}/g) and impregnated with 6% (w/w) (Pt–Ru) nanoparticles exhibit the best CH{sub 3}OH electro-oxidation efficiency. The Michaelis–Menten formalism was used to describe the dependence of the oxidation peak current on the CH{sub 3}OH concentration, allowing the estimation of the modified electrodes sensitivities. Thus, for (Pt–Ru, 10%)/CA{sub 535}-CPE was observed the highest sensitivity (12.5 ± 0.8 mA/M) and, at the same time, the highest maximum current density ever reported (153.1 mA/cm{sup 2} for 2 M CH{sub 3}OH and an applied potential of 600 mV vs. SHE). - Highlights: • (Pt–Ru) nanoparticles were deposited on high mesoporous carbon aerogels (CAs). • (Pt–Ru)/CAs were characterized by TEM, EDX, SAED and N{sub 2} adsorption-desorption. • Carbon paste electrodes modified with (Pt–Ru)/CA were used for CH{sub 3}OH oxidation. • (Pt–Ru, 10

Several novel Ru(II) and Ru(III) complexes formed by reduction of (RuO4bipy) and (RuO3phen)2O with hydroquinone and methanol

International Nuclear Information System (INIS)

Ishiyama, Toshio

1975-01-01

The geometrical isomers, cis-dichloro-trans-(methanol)(hydroquinone)(2,2'-bipyridine)ruthenium(II) and cis-dichloro-cis-(methanol)(hydroquinone)(2,2'-bipyridine)ruthenium(II), [RuCl 2 (MeOH)(QH 2 )bipy] (complex I and II), were synthesized by reduction and substitution reactions of [RuO 4 bipy] and [RuO 2 (OH) 2 bipy] with hydroquinone in hydrochloric acid solution, and methanol. cis-Chloro(hydroquinonato)bis(2,2'-bipyridine)ruthenium(II), cis-[RuCl(QH)(bipy) 2 ], was obtained from the substitution reaction of complex I or II with 2,2'-bipyridine in methanol, and cis-chloro(hydroquinone)bis(2,2'-bipyridine)ruthenium(II) chloride, cis-[RuCl(QH 2 )(bipy) 2 ]Cl, was also obtained from the substitution of cis-trans-[RuCl 2 (MeOH)(QH 2 )bipy] in methanol containing hydrochloric acid. cis-Dihydroxobis(2,2'-bipyridine)ruthenium(II), cis-[Ru(OH) 2 (bipy) 2 ], was obtained by heating an aqueous solution of cis-[RuCl(QH)(bipy) 2 ]. Trihydroxoaquo(1,10-phenanthroline)ruthenium(III), [Ru(OH) 3 (H 2 O)phen] was also synthesized from [RuO 3 phen] 2 O and [Ru(OH) 3 phen] 2 O by reduction reactions similar to those used for [RuCl 2 (MeOH)(QH 2 )bipy]. These complexes were characterized by the infrared, visible and ultraviolet absorption spectra, and also by polarographic and magnetic measurements. The structures are discussed. (auth.)

Novel Electronic Structures of Ru-pnictides RuPn (Pn = P, As, Sb)

Science.gov (United States)

Goto, H.; Toriyama, T.; Konishi, T.; Ohta, Y.

Density-functional-theory-based electronic structure calculations are made to consider the novel electronic states of Ru-pnictides RuP and RuAs where the intriguing phase transitions and superconductivity under doping of Rh have been reported. We find that there appear nearly degenerate flat bands just at the Fermi level in the high-temperature metallic phase of RuP and RuAs; the flat-band states come mainly from the 4dxy orbitals of Ru ions and the Rh doping shifts the Fermi level just above the flat bands. The splitting of the flat bands caused by their electronic instability may then be responsible for the observed phase transition to the nonmagnetic insulating phase at low temperatures. We also find that the band structure calculated for RuSb resembles that of the doped RuP and RuAs, which is consistent with experiment where superconductivity occurs in RuSb without Rh doping.

Nanoscale electrochemical metallization memories based on amorphous (La, Sr)MnO3 using ultrathin porous alumina masks

International Nuclear Information System (INIS)

Liu, Dongqing; Zhang, Chaoyang; Wang, Nannan; Cheng, Haifeng; Wang, Guang; Shao, Zhengzheng; Zhu, Xuan

2014-01-01

Nanoscale electrochemical metallization (ECM) memories based on amorphous La 1−x Sr x MnO 3 (a-LSMO) were fabricated using ultrathin porous alumina masks. The ultrathin alumina masks, with thicknesses of about 200 nm and pore diameters of about 80 nm, were fabricated through a typical two-step anodization electrochemical procedure and transferred onto conductive Pt/Ti/SiO 2 /Si substrates. Resistive switching (RS) properties of the individual Ag/a-LSMO/Pt ECM cell were directly measured using a conductive atomic force microscope. The cells exhibited typical RS characteristics and the OFF/ON resistance ratio is as high as 10 2 . Reproducible RS behaviours on the same ECM cell and the I–V cycles obtained from different ECM cells ensured that the RS properties in nanoscale Ag/a-LSMO/Pt cells are reproducible and reliable. This work provides an effective approach for the preparation of nanostructured large-scale ordered ECM memories or memristors. (paper)

P-T data from central Bhutan imply distributed extensional shear at the Black Mountain "klippe"

Science.gov (United States)

Corrie, S. L.; Kohn, M. J.; Long, S. P.; McQuarrie, N.; Tobgay, T.

2011-12-01

The Southern Tibetan Detachment system (STDS) occurs along the entire length of the Himalayan orogen, and extensionally emplaces low-grade to unmetamorphosed Tethyan Himalayan (TH) rocks over highly metamorphosed Greater Himalayan sequence (GH) rocks. The base of TH remnants preserved in northern Bhutan all have top-to-the-north shear sense indicators (C'-type shear bands, asymmetric folds, and boudinaged leucogranite dikes) that are interpreted to reflect a discrete shear zone. In contrast, the GH-TH contact in the southernmost TH remnant (the Black Mountain region, central Bhutan) has been interpreted as depositional. A depositional contact limits the magnitude of displacement along the early STDS to 10's of km. If the GH-TH contact in the Black Mountain region is instead a discrete shear zone, as observed farther north, displacement on the STDS could be as high as 100's of km. To discriminate between these two interpretations, we determined peak metamorphic P-T conditions through the GH and TH sections, reasoning that a discrete shear zone would produce a distinct jump in metamorphic temperature, pressure or both. Thin section-scale kinematic indicators reveal pervasive top-to-the-north shear from 2-3 km structurally above the Main Central thrust (MCT) through the rest of the 11 km thick GH and TH sections. P-T conditions were determined from immediately above the MCT to 4 km above the GH-TH contact, with 19 samples from the GH, 6 from the overlying Chekha Fm (TH), and 9 from the overlying Maneting Fm (TH). We applied standard Fe-Mg exchange thermometers and Ca net-transfer barometers involving garnet. P-T conditions range from 700 °C and 11 kbar in migmatitic GHS to 600 °C and 8 kbar at the GH-Chekha contact, and 500 °C and 5 kbar at the top of the Maneting. We found no jumps in either temperature or pressure at any level, but a steeper than lithostatic pressure gradient, which we interpret to result from distributed extensional shear. The average thermal

Nanostructured electrocatalyst for fuel cells : silica templated synthesis of Pt/C composites.

Energy Technology Data Exchange (ETDEWEB)

Stechel, Ellen Beth; Switzer, Elise E.; Fujimoto, Cy H.; Atanassov, Plamen Borissov; Cornelius, Christopher James; Hibbs, Michael R.

2007-09-01

Platinum-based electrocatalysts are currently required for state-of-the-art fuel cells and represent a significant portion of the overall fuel cell cost. If fuel cell technology is to become competitive with other energy conversion technologies, improve the utilization of precious metal catalysts is essential. A primary focus of this work is on creating enhanced nanostructured materials which improve precious-metal utilization. The goal is to engineer superior electrocatalytic materials through the synthesis, development and investigation of novel templated open frame structures synthesized in an aerosol-based approach. Bulk templating methods for both Pt/C and Pt-Ru composites are evaluated in this study and are found to be limited due to the fact that the nanostructure is not maintained throughout the entire sample. Therefore, an accurate examination of structural effects was previously impossible. An aerosol-based templating method of synthesizing nanostructured Pt-Ru electrocatalysts has been developed wherein the effects of structure can be related to electrocatalytic performance. The aerosol-based templating method developed in this work is extremely versatile as it can be conveniently modified to synthesize alternative materials for other systems. The synthesis method was able to be extended to nanostructured Pt-Sn for ethanol oxidation in alkaline media. Nanostructured Pt-Sn electrocatalysts were evaluated in a unique approach tailored to electrocatalytic studies in alkaline media. At low temperatures, nanostructured Pt-Sn electrocatalysts were found to have significantly higher ethanol oxidation activity than a comparable nanostructured Pt catalyst. At higher temperatures, the oxygen-containing species contribution likely provided by Sn is insignificant due to a more oxidized Pt surface. The importance of the surface coverage of oxygen-containing species in the reaction mechanism is established in these studies. The investigations in this work present

Conducting filaments in Pt/ZrCuO{sub y}/Pt resistive switching memory cells

Energy Technology Data Exchange (ETDEWEB)

Tulu, Berhanu [Department of Materials Science and Engineering, National Taiwan University of Science and Technology, Taipei 10607, Taiwan (China); Chu, Jinn P., E-mail: jpchu@mail.ntust.edu.tw [Department of Materials Science and Engineering, National Taiwan University of Science and Technology, Taipei 10607, Taiwan (China); Wang, Sea-Fue [Department of Materials and Minerals Resources Engineering, National Taipei University of Technology, Taipei 10608, Taiwan (China)

2015-11-15

Forming-free unipolar resistive switching with good retention time, low voltage (<1.9 V) and thin thickness (∼11 nm) is obtained in oxygen deficient Pt/ZrCuO{sub y}/Pt devices. Annealing at 150 °C is beneficial to improve the endurance from 286 to >6 × 10{sup 3} and the resistance ratio from ∼13 to ∼25. Nanoscale current path images observed using a conductive atomic force microscope reveal a current density of ∼3.0 × 10{sup 2} nA/μm{sup 2} in the ON state, almost four orders of magnitude higher than ∼3.3 × 10{sup −2} nA/μm{sup 2} in the OFF state. The resistive switching is thought to be dominated by the oxygen vacancies, which serves as the filamentary conduction in the film. - Highlights: • Oxygen deficient Pt/ZrCuOy/Pt device after annealing at 150 °C is studied. • Forming-free resistive switching with good retention time, low voltage is obtained. • Annealing is shown to improve the endurance from 286 to >6 × 10{sup 3}. • The resistive switching is thought to be dominated by the oxygen vacancies.

RuP{sub 2}-based catalysts with platinum-like activity and higher durability for the hydrogen evolution reaction at all pH values

Energy Technology Data Exchange (ETDEWEB)

Pu, Zonghua; Amiinu, Ibrahim Saana; Kou, Zongkui; Li, Wenqiang; Mu, Shichun [State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology (China)

2017-09-11

Highly active, stable, and cheap Pt-free catalysts for the hydrogen evolution reaction (HER) are under increasing demand for future energy conversion systems. However, developing HER electrocatalysts with Pt-like activity that can function at all pH values still remains as a great challenge. Herein, based on our theoretical predictions, we design and synthesize a novel N,P dual-doped carbon-encapsulated ruthenium diphosphide (RuP{sub 2} rate at NPC) nanoparticle electrocatalyst for HER. Electrochemical tests reveal that, compared with the Pt/C catalyst, RuP{sub 2} rate at NPC not only has Pt-like HER activity with small overpotentials at 10 mA cm{sup -2} (38 mV in 0.5 m H{sub 2}SO{sub 4}, 57 mV in 1.0 m PBS and 52 mV in 1.0 m KOH), but demonstrates superior stability at all pH values, as well as 100 % Faradaic yields. Therefore, this work adds to the growing family of transition-metal phosphides/heteroatom-doped carbon heterostructures with advanced performance in HER. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

Ethanol tolerant Pt-alloy cathodes for DEFC applications

Energy Technology Data Exchange (ETDEWEB)

Rodriguez Valera, F.J. [CINVESTAV Unidad Saltillo, Coahuila (Mexico). Grupo de Recursos Minerales y Energeticos; Savadogo, O. [Ecole Polytechnique de Montreal, Montreal, PQ (Canada). Laboratoire de nouveaux materiaux pour l' energie et l' electrochimie

2008-07-01

Direct ethanol fuel cells (DEFCs) based on Ru/C cathodes have interesting current density versus cell voltage behaviour. In particular, the selectivity towards the oxygen reduction reaction (ORR) in acid medium in the presence of ethanol was improved when this cathode material was used. This study quantified the degree of tolerance to ethanol and the electrocatalytic activity for the ORR. It compared the specific activity towards the ORR for Pt1Co1/C and Pt3Cr1/C. The study showed that these cathodes have a high tolerance to this alcohol and demonstrated the good performance of this type of Pt-alloy in a DEFC as oxygen reduction cathodes. The performance of the Pt1Co1/C alloy was shown to be better than the Pt3Cr1/C, even when the former had a lower Pt content. The enhanced catalytic behaviour of the PtCo/C alloy can be attributed to the higher degree of allying or a smaller mean particle size and a larger surface area. Polarization measurements with relatively high ethanol concentrations confirmed the good catalytic behaviour of the PtCo/C alloy as cathode in a DEFC operating at 90 degrees C. Current work is focusing on the variation of Co content in the alloy structure and the analysis of this change in terms of ORR activity, tolerance to ethanol and electrochemical behaviour in a DEFC. 10 refs., 5 figs.

Preparation of Pt Nanocatalyst on Carbon Materials via a Reduction Reaction of a Pt Precursor in a Drying Process.

Science.gov (United States)

Lee, Jae-Young; Lee, Woo-Kum; Rim, Hyung-Ryul; Joung, Gyu-Bum; Weidner, John W; Lee, Hong-Ki

2016-06-01

Platinum (Pt) nanocatalyst for a proton-exchange membrane fuel cell (PEMFC) was prepared on a carbon black particle or a graphite particle coated with a nafion polymer via a reduction of platinum(II) bis(acetylacetonate) denoted as Pt(acac)2 as a Pt precursor in a drying process. Sublimed Pt(acac)2 adsorbed on the nafion-coated carbon materials was reduced to Pt nanoparticles in a glass reactor at 180 degrees C of N2 atmosphere. The morphology of Pt nanoparticles on carbon materials was observed by scanning electron microscopy (SEM) and the distribution of Pt nanoparticles was done by transmission electron microscopy (TEM). The particle size was estimated by analyzing the TEM image using an image analyzer. It was found that nano-sized Pt particles were deposited on the surface of carbon materials, and the number density and the average particle size increased with increasing reduction time.

Multi-color imaging of magnetic Co/Pt heterostructures

Directory of Open Access Journals (Sweden)

Felix Willems

2017-01-01

Full Text Available We present an element specific and spatially resolved view of magnetic domains in Co/Pt heterostructures in the extreme ultraviolet spectral range. Resonant small-angle scattering and coherent imaging with Fourier-transform holography reveal nanoscale magnetic domain networks via magnetic dichroism of Co at the M2,3 edges as well as via strong dichroic signals at the O2,3 and N6,7 edges of Pt. We demonstrate for the first time simultaneous, two-color coherent imaging at a free-electron laser facility paving the way for a direct real space access to ultrafast magnetization dynamics in complex multicomponent material systems.

The emergence of nonbulk properties in supported metal clusters: negative thermal expansion and atomic disorder in Pt nanoclusters supported on gamma-Al2O3.

Science.gov (United States)

Sanchez, Sergio I; Menard, Laurent D; Bram, Ariella; Kang, Joo H; Small, Matthew W; Nuzzo, Ralph G; Frenkel, Anatoly I

2009-05-27

The structural dynamics-cluster size and adsorbate-dependent thermal behaviors of the metal-metal (M-M) bond distances and interatomic order-of Pt nanoclusters supported on a gamma-Al(2)O(3) are described. Data from scanning transmission electron microscopy (STEM) and X-ray absorption spectroscopy (XAS) studies reveal that these materials possess a dramatically nonbulklike nature. Under an inert atmosphere small, subnanometer Pt/gamma-Al(2)O(3) clusters exhibit marked relaxations of the M-M bond distances, negative thermal expansion (NTE) with an average linear thermal expansion coefficient alpha = (-2.4 +/- 0.4) x 10(-5) K(-1), large static disorder and dynamical bond (interatomic) disorder that is poorly modeled within the constraints of classical theory. The data further demonstrate a significant temperature-dependence to the electronic structure of the Pt clusters, thereby suggesting the necessity of an active model to describe the cluster/support interactions mediating the cluster's dynamical structure. The quantitative dependences of these nonbulklike behaviors on cluster size (0.9 to 2.9 nm), ambient atmosphere (He, 4% H(2) in He or 20% O(2) in He) and support identity (gamma-Al(2)O(3) or carbon black) are systematically investigated. We show that the nonbulk structural, electronic and dynamical perturbations are most dramatically evidenced for the smallest clusters. The adsorption of hydrogen on the clusters leads to an increase of the Pt-Pt bondlengths (due to a lifting of the surface relaxation) and significant attenuation of the disorder present in the system. Oxidation of these same clusters has the opposite effect, leading to an increase in Pt-Pt bond strain and subsequent enhancement in nonbulklike thermal properties. The structural and electronic properties of Pt nanoclusters supported on carbon black contrast markedly with those of the Pt/gamma-Al(2)O(3) samples in that neither NTE nor comparable levels of atomic disorder are observed. The Pt

101Ru NQR study in superconducting CeRu2

International Nuclear Information System (INIS)

Matsuda, Kazuyuki; Kohori, Yoh; Kohara, Takao

1995-01-01

We present measurements of the NQR spectrum and the nuclear spin lattice relaxation rate, 1/T 1 , of 101 Ru in superconducting CeRu 2 from 1.9 K to 10 K. From the NQR spectrum, the electric quadrupole interaction parameters were determined to be ν Q =13.2 MHz and η=0.1/T 1 varies in proportion to temperature in the normal state, and has the Hebel-Slichter coherence peak just below the superconducting transition temperature, T C , of 6.2 K, and decreases exponentially at low temperatures with the energy gap of 2Δ=4.0k B T C . 101 Ru NQR study indicates that CeRu 2 is an s-wave and strong-coupling superconductor. (author)

Investigation of as-cast alloys in the Pt-Al-Cr system

International Nuclear Information System (INIS)

Suess, R.; Cornish, L.A.; Witcomb, M.J.

2010-01-01

Platinum-based alloys are being developed which have microstructures that are analogous to the γ/γ' microstructure of the nickel-based superalloys. These Pt-based alloys have the potential to be used for high-temperature applications. The ternary Pt-Al-Cr system was investigated as part of the continued development of a thermodynamic database for the Pt-Al-Cr-Ru system. Scanning electron microscopy (SEM) with energy dispersive X-ray spectroscopy (EDX) and X-ray diffraction (XRD) analyses were used to obtain phase equilibria data. The alloys were studied in the as-cast condition. A solidification projection was constructed and a liquidus surface derived. It was concluded that all phase regions were identified correctly since the results were self-consistent. Three ternary phases and 21 ternary invariant reactions were identified.

Is carbon-supported Pt-WOx composite a CO-tolerant material?

International Nuclear Information System (INIS)

Maillard, F.; Peyrelade, E.; Soldo-Olivier, Y.; Chatenet, M.; Chainet, E.; Faure, R.

2007-01-01

Pt-WO x /C composite materials elaborated via a two-step impregnation/electrochemical reduction method have been characterized and tested for the electrooxidation of CO/H 2 mixtures. TEM and EDS measurements revealed that WO x covered imperfectly the C particles. Nanometer-sized or agglomerated Pt particles were found on the WO x /C surface. XRD measurements revealed the absence of diffraction peaks characteristic of crystalline WO x and could indicate that this material is amorphous. No evidence of alloying between the Pt and W was observed. A significant improvement toward the electrooxidation of a CO ads monolayer was observed for the composite material compared to pure Pt/C electrocatalyst, which is evidenced by a new electrooxidation peak at 0.55V versus RHE (v=0.02Vs -1 ). As the electrical charge below this electrooxidation peak is sweep rate dependant, it is probably associated to the electrooxidation of CO ads on Pt sites at the interface with the WO x /C support. The performance of the Pt-WO x /C material for the electrooxidation of CO/H 2 mixtures was tested by polarization curves under steady-state conditions (0.001Vs -1 ) or potentiostatic measurements under fuel cell relevant conditions and compared with that of commercial 20wt% Pt/C and Pt-Ru/C materials

Synthesis and magnetic properties of carbon-coated FeRu, CoRu, and NiRu nanoalloys

Energy Technology Data Exchange (ETDEWEB)

El-Gendy, A.A.; Khavrus, V.O.; Hampel, S.; Leonhardt, A.; Klingeler, R.; Buechner, B. [Leibniz Institute for Solid State and Materials Research (IFW) Dresden (Germany)

2010-07-01

Carbon coated FeRu, CoRu and NiRu nanoalloys have been synthesised by high pressure chemical vapour deposition (HPCVD). The formation of the core-shell nanoalloys with a mean diameter around 8 nm has been confirmed by means of high resolution transmission electron microscopy imaging (HRTEM), energy dispersive X-ray (EDX) analysis, and X-ray diffraction (XRD). We show the effect of the synthesis parameters on the actual composition of the nanoalloys and on their magnetic properties and we discuss their feasibility for applications in medical hyperthermia.

Fuel cell testing of Pt–Ru catalysts supported on differently prepared and pretreated carbon nanotubes

International Nuclear Information System (INIS)

Tokarz, Wojciech; Lota, Grzegorz; Frackowiak, Elzbieta; Czerwiński, Andrzej; Piela, Piotr

2013-01-01

Proton-exchange membrane fuel cell (PEMFC) testing of Pt–Ru catalysts supported on differently prepared multiwall carbon nanotube (MCNT) supports was performed to elucidate the influence of the different supports on the operating characteristics of the catalysts under real direct methanol fuel cell (DMFC) anode and H 2 -PEMFC anode conditions. The MCNTs were either thin, entangled or thick, disentangled. Pretreatment of the MCNTs was also done and it was either high-temperature KOH etching or annealing (graphitization). The performance of the catalysts was compared against the performance of a commercial Pt–Ru catalyst supported on a high-surface-area carbon black. Among the different MCNT supports, the graphitized, entangled support offered the best performance in all tests, which was equal to the performance of the commercial catalyst, despite the MCNT catalyst layer was ca. 2.2 times thicker than the carbon black catalyst layer. Even for an MCNT catalyst layer, which was almost 7 times thicker than the carbon black catalyst layer, the transport limitations were not prohibitive. This confirmed the expected potential of nanotube supports for providing superior reactant transport properties of the PEMFC catalyst layers

Activity of PtSnRh/C nanoparticles for the electrooxidation of C1 and C2 alcohols

Energy Technology Data Exchange (ETDEWEB)

Teran, Freddy E. [Universite de Poitiers, IC2MP UMR CNRS 7285, ' Equipe E-lyse' , 4 rue Michel Brunet-B27, BP 633, 86022 Poitiers cedex (France); Santos, Deise M. [Departamento de Quimica, CCE-UFES, Av. Fernando Ferrari, 514, Goiabeiras-Vitoria, ES (Brazil); Ribeiro, Josimar, E-mail: josimar.ribeiro@ufes.br [Universite de Poitiers, IC2MP UMR CNRS 7285, ' Equipe E-lyse' , 4 rue Michel Brunet-B27, BP 633, 86022 Poitiers cedex (France); Departamento de Quimica, CCE-UFES, Av. Fernando Ferrari, 514, Goiabeiras-Vitoria, ES (Brazil); Kokoh, Kouakou B. [Universite de Poitiers, IC2MP UMR CNRS 7285, ' Equipe E-lyse' , 4 rue Michel Brunet-B27, BP 633, 86022 Poitiers cedex (France)

2012-07-01

A systematic investigation of alcohol adsorption and oxidation on binary and ternary electrocatalysts in acid medium was performed. Binary (PtRh) and ternary (PtRhSn) were prepared by the Pechini modified method on carbon Vulcan XC-72, and different nominal compositions were characterized by energy dispersive X-ray and X-ray diffraction (XRD) techniques. The XRD results showed that the Pt{sub 80}Rh{sub 20}/C and Pt{sub 70}Sn{sub 10}Rh{sub 20}/C electrocatalysts consisted of the Pt displaced phase, suggesting the formation of a solid solution between the metals Pt/Rh and Pt/Sn. Electrochemical investigations on these different electrode materials were carried out as a function of the electrocatalyst composition, in acid medium (0.5 mol dm{sup -3} H{sub 2}SO{sub 4}), and in the absence and presence of different alcohols (methanol, ethanol and ethylene glycol). The electrochemical results obtained at room temperature have shown that the Pt{sub 70}Sn{sub 10}Rh{sub 20}/C catalyst display better catalytic activity for alcohol oxidation compared with the binary catalyst. In situ reflectance infrared spectroscopy measurements have shown that the oxidation of alcohols mentioned produced CO{sub 2} at low potentials indicating that the materials synthesized could be used as efficient anodes in the fuel cell applications. - Highlights: Black-Right-Pointing-Pointer Pt-based catalysts were synthesized by thermal decomposition polymeric precursors. Black-Right-Pointing-Pointer Pt{sub 70}Sn{sub 10}Rh{sub 20}/C displays better catalytic activity for the oxidation of alcohols. Black-Right-Pointing-Pointer The co-catalysts tin and rhodium promote the removal of CO to CO{sub 2} at low potentials. Black-Right-Pointing-Pointer Ethylene glycol is oxidizing strongly to CO{sub 2} at low potentials. Black-Right-Pointing-Pointer Pt{sub 70}Sn{sub 10}Rh{sub 20}/C catalyst is an efficient anode material for a direct alcohol fuel cell.

Sol-gel processed thin-layer ruthenium oxide/carbon black supercapacitors: A revelation of the energy storage issues

Energy Technology Data Exchange (ETDEWEB)

Panic, V.V.; Dekanski, A.B.; Stevanovic, R.M. [Institute of Chemistry, Technology and Metallurgy, Department of Electrochemistry, University of Belgrade, Njegoseva 12, Belgrade 125213 (RS)

2010-07-01

Hydrous ruthenium oxide/carbon black nanocomposites were prepared by impregnation of the carbon blacks by differently aged inorganic RuO{sub 2} sols, i.e. of different particle size. Commercial Black Pearls 2000 {sup registered} (BP) and Vulcan {sup registered} XC-72 R (XC) carbon blacks were used. Capacitive properties of BP/RuO{sub 2} and XC/RuO{sub 2} composites were investigated by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) in H{sub 2}SO{sub 4} solution. Capacitance values and capacitance distribution through the composite porous layer were found different if high- (BP) and low- (XC) surface-area carbons are used as supports. The aging time (particle size) of Ru oxide sol as well as the concentration of the oxide solid phase in the impregnating medium influenced the capacitive performance of prepared composites. While the capacitance of BP-supported oxide decreases with the aging time, the capacitive ability of XC-supported oxide is promoted with increasing oxide particle size. The increase in concentration of the oxide solid phase in the impregnating medium caused an improvement of charging/discharging characteristics due to pronounced pseudocapacitance contribution of the increasing amount of inserted oxide. The effects of these variables in the impregnation process on the energy storage capabilities of prepared nanocomposites are envisaged as a result of intrinsic way of population of the pores of carbon material by hydrous Ru oxide particle. (author)

Micro Galvanic Cell To Generate PtO and Extend the Triple-Phase Boundary during Self-Assembly of Pt/C and Nafion for Catalyst Layers of PEMFC.

Science.gov (United States)

Long, Zhi; Gao, Liqin; Li, Yankai; Kang, Baotao; Lee, Jin Yong; Ge, Junjie; Liu, Changpeng; Ma, Shuhua; Jin, Zhao; Ai, Hongqi

2017-11-08

The self-assembly powder (SAP) with varying Nafion content was synthesized and characterized by XRD, XPS, HRTEM, and mapping. It is observed that the oxygen from oxygen functional groups transfers to the surface of Pt and generate PtO during the process of self-assembly with the mechanism of micro galvanic cell, where Pt, carbon black, and Nafion act as the anode, cathode and electrolyte, respectively. The appearance of PtO on the surface of Pt leads to a turnover of Nafion structure, and therefore more hydrophilic sulfonic groups directly contact with Pt, and thus the triple-phase boundary (TPB) has been expanded.

Interactions of RuO4(g) with different surfaces in nuclear reactor containments

International Nuclear Information System (INIS)

Holm, J.; Glaenneskog, H.; Ekberg, C.

2008-07-01

During a severe nuclear reactor accident with air ingress, ruthenium in the form of RuO4 can be released from the nuclear fuel. Hence, it is important to investigate how the reactor containment is able to reduce the source term of ruthenium. This work has investigated the distribution of RuO4 between an aqueous and gaseous phase in the temperature interval of 20-50 deg. C by on-line measurements with an experimental set-up made of glass. The experiments showed that RuO4 is almost immediately distributed in the aqueous phase after its introduction in the set-up in the entire temperature interval. However, the deposition of ruthenium on the glass surfaces in the system was significant. The speciation of the ruthenium on the glass surfaces was studied by SEM-EDX and ESCA and was determined to be the expected RuO2. Experiments of interactions between gaseous ruthenium tetroxide and the metals aluminium, copper and zinc have been investigated. The metals were treated by RuO4 (g) at room temperature and analyzed with ESCA, SEM and XRD. The analyses show that the black ruthenium deposits on the metal surfaces were RuO2, i.e. the RuO4 (g) has been transformed on the metal surfaces to RuO2(s). The analyses showed also that there was a significant deposition of ruthenium tetroxide especially on the copper and zinc samples. Aluminium has a lower ability to deposit gaseous ruthenium tetroxide than the other metals. The conclusion that can be made from the results is that surfaces in nuclear reactor containments will likely reduce the source term in the case of a severe accident in a nuclear power plant. (au)

Metalloradical Reactivity of RuI and Ru0 Stabilized by an Indole-Based Tripodal Tetraphosphine Ligand

NARCIS (Netherlands)

van de Watering, F.F.; van der Vlugt, J.I.; Dzik, W.I.; de Bruin, B.; Reek, J.N.H.

2017-01-01

The tripodal, tetradentate tris(1-(diphenylphosphanyl)-3-methyl-1H-indol-2-yl)phosphane PP3-ligand 1 stabilizes Ru in the RuII, RuI, and Ru0 oxidation states. The octahedral [(PP3)RuII(Cl)2] ( 2 ), distorted trigonal bipyramidal [(PP3)RuI(Cl)] ( 3 ), and trigonal bipyramidal [(PP3)Ru0(N2)] ( 4 )

Measuring size dependent electrical properties from nanoneedle structures: Pt/ZnO Schottky diodes

International Nuclear Information System (INIS)

Mao, Shimin; Anderson, Daniel D.; Shang, Tao; Park, Byoungnam; Dillon, Shen J.

2014-01-01

This work reports the fabrication and testing of nanoneedle devices with well-defined interfaces that are amenable to a variety of structural and electrical characterization, including transmission electron microscopy. Single Pt/ZnO nanoneedle Schottky diodes were fabricated by a top down method using a combination of electro-polishing, sputtering, and focused ion beam milling. The resulting structures contained nanoscale planar heterojunctions with low ideality factors, the dimensions of which were tuned to study size-dependent electrical properties. The diameter dependence of the Pt/ZnO diode barrier height is explained by a joule heating effect and/or electronic inhomogeneity in the Pt/ZnO contact area

Magnetic properties of Heusler alloy Mn2RuGe and Mn2RuGa ribbons

International Nuclear Information System (INIS)

Yang, Ling; Liu, Bohua; Meng, Fanbin; Liu, Heyan; Luo, Hongzhi; Liu, Enke; Wang, Wenhong; Wu, Guangheng

2015-01-01

Heusler alloys Mn 2 RuGe and Mn 2 RuGa have been prepared by melt-spinning method successfully. Theoretical and experimental studies reveal a ferrimagnetic ground state in the two alloys. The Curie temperatures are 303 K for Mn 2 RuGe and 272 K for Mn 2 RuGa. The calculated total spin moments of Mn 2 RuGe and Mn 2 RuGa are integral values of 2.00 μ B and 1.03 μ B , respectively. And the theoretical spin polarization ratio is also quite high. However, due to the atomic disorder in the ribbons, the saturation moments of them measured at 5 K are smaller than the calculated values, especially that of Mn 2 RuGa. This coincides with the disappearance of the superlattice reflection (111) and (200) peaks in the XRD pattern of Mn 2 RuGa. Annealing Mn 2 RuGa ribbon at 773 K can enhance the atomic ordering. Both saturation magnetic moment and Curie temperature increase obviously after the heat treatment. - Highlights: • Mn 2 RuGe and Mn 2 RuGa have been prepared by melt-spinning successfully. • Ferrimagnetic ground state has been confirmed in Mn 2 RuGe and Mn 2 RuGa. • High spin polarization has been predicted in Mn 2 RuGe. • Melt-spinning can be a possible way to adjust the atomic order of Heusler alloys

Relationship between the catalytic activity of Pt/alumina and the relaxation process of the photoexcited electrons

Energy Technology Data Exchange (ETDEWEB)

Ito, Junji, E-mail: j-itou@mail.nissan.co.jp [Advanced Materials Laboratory, Nissan Research Center, NISSAN MOTOR CO., LTD., 1 Natsushima-cho, Yokosuka-shi, Kanagawa 237-8523 (Japan); Department of Applied Physics and Chemistry, The University of Electro-Communications, 1-5-1 Chofugaoka, Chofu, Tokyo 182-8585 (Japan); Hanaki, Yasunari [Advanced Materials Laboratory, Nissan Research Center, NISSAN MOTOR CO., LTD., 1 Natsushima-cho, Yokosuka-shi, Kanagawa 237-8523 (Japan); Shen, Qing [Department of Applied Physics and Chemistry, The University of Electro-Communications, 1-5-1 Chofugaoka, Chofu, Tokyo 182-8585 (Japan); Department of Engineering Science, The University of Electro-Communications, 1-5-1 Chofugaoka, Chofu, Tokyo 182-8585 (Japan); PRESTO, Japan Science and Technology Agency (JST), 4-1-8 Honcho, Kawaguchi, Saitama 332-0012 (Japan); Toyoda, Taro [Department of Applied Physics and Chemistry, The University of Electro-Communications, 1-5-1 Chofugaoka, Chofu, Tokyo 182-8585 (Japan); Department of Engineering Science, The University of Electro-Communications, 1-5-1 Chofugaoka, Chofu, Tokyo 182-8585 (Japan)

2012-12-15

Highlights: Black-Right-Pointing-Pointer We determined the decay time of photoexcited electrons of Pt/Al{sub 2}O{sub 3}. Black-Right-Pointing-Pointer Faster decay of excited electrons in Pt/Al{sub 2}O{sub 3} leads to its faster oxidation rate. Black-Right-Pointing-Pointer Decreasing excited electron lifetime in Pt/Al{sub 2}O{sub 3} may decrease Pt consumption in catalytic convertors. - Abstract: In order to decrease the consumption of precious metals used in the catalytic converters used in automobiles, we studied the relationship between the catalytic activity of Pt/alumina (Pt/Al{sub 2}O{sub 3}) and the relaxation process of photoexcited electrons. Firstly, we studied the relationship between the size of the Pt particles in Pt/Al{sub 2}O{sub 3} and catalytic performance. Secondly, the relationship between the size of the Pt particles in Pt/Al{sub 2}O{sub 3} and the decay time of the excited electrons was studied using an improved transient grating (TG) technique. The results showed that faster decay of the excited electrons leads to greater oxidation rates. The decay time obtained with the improved TG technique gives an indication of the time that the exited electrons take to return to the ground state. According to studies utilizing FT-IR, one of the processes necessary for quickly generating CO{sub 2} with Pt is that the electron in the Pt-O bond moves to the Pt side and that the Pt{sup +} becomes Pt metal. Thus, the decay time obtained with the improved TG technique corresponds to the process whereby Pt{sup +} returns to Pt metal. Thus, we found that the consumption of precious metals can be reduced by increasing the speed of the decay of the excited electrons.

Structure, microstructure and magnetic properties of electrodeposited Co and Co-Pt in different nanoscale geometries

Energy Technology Data Exchange (ETDEWEB)

Khatri, Manvendra Singh

2010-07-09

Thin films and nanowires of Co-Pt have been prepared by means of electrodeposition. Composition, structure, microstructure and magnetic properties have been intensively studied using X-ray diffraction, scanning electron microscopy and vibrating sample magnetometry and correlated to the deposition parameters such as electrolyte composition, deposition current and/or potential. Co rich Co-Pt films have been deposited at various current densities. A nearly constant composition of Co{sub 70}Pt{sub 30} was achieved for current densities between 18 and 32 mA/cm{sup 2}. Detailed texture measurements confirmed an increasing fraction of the hexagonal phase with its c-axis aligned perpendicular to the film plane with increasing current density. Accordingly, magnetic properties are strongly affected by the magnetocrystalline anisotropy of the hexagonal phase that competes with the shape anisotropy of the thin film geometry. Co-Pt nanowires have been prepared within alumina templates at different deposition potentials between -0.6 and -0.9 V{sub SCE} changing the composition from nearly pure Pt to Co. The composition Co{sub 80}Pt{sub 20} was observed at a deposition potential of -0.7 V{sub SCE}. Co-Pt nanowires are nanocrystalline in the as-deposited state. Magnetic measurements reveal changing fcc and hcp phase fractions within the wires as the effective anisotropy significantly differs from the expected shape anisotropy for nanowires with high aspect ratio. This change in effective anisotropy is attributed to the preferential alignment of the c-axis of hcp Co-Pt phase perpendicular to the nanowires axis. A promising alternative with much smaller feature sizes is the diblock copolymer template. Electrodeposition of Co and Co-Pt into these templates has been carried out. Inhomogeneities in the template thickness as well as a certain substrate roughness have been identified to be the reasons for inhomogeneous template filling. Thus magnetic properties are dominated by large

Synthesis, crystal structure investigation and magnetism of the complex metal-rich boride series Cr{sub x}(Rh{sub 1-y}Ru{sub y}){sub 7-x}B{sub 3} (x=0.88-1; y=0-1) with Th{sub 7}Fe{sub 3}-type structure

Energy Technology Data Exchange (ETDEWEB)

Misse, Patrick R.N.; Mbarki, Mohammed [Institute of Inorganic Chemistry, RWTH Aachen University, 52066 Aachen (Germany); Fokwa, Boniface P.T., E-mail: boniface.fokwa@ac.rwth-aachen.de [Institute of Inorganic Chemistry, RWTH Aachen University, 52066 Aachen (Germany)

2012-08-15

Powder samples and single crystals of the new complex boride series Cr{sub x}(Rh{sub 1-y}Ru{sub y}){sub 7-x}B{sub 3} (x=0.88-1; y=0-1) have been synthesized by arc-melting the elements under purified argon atmosphere on a water-cooled copper crucible. The products, which have metallic luster, were structurally characterized by single-crystal and powder X-ray diffraction as well as EDX measurements. Within the whole solid solution range the hexagonal Th{sub 7}Fe{sub 3} structure type (space group P6{sub 3}mc, no. 186, Z=2) was identified. Single-crystal structure refinement results indicate the presence of chromium at two sites (6c and 2b) of the available three metal Wyckoff sites, with a pronounced preference for the 6c site. An unexpected Rh/Ru site preference was found in the Ru-rich region only, leading to two different magnetic behaviors in the solid solution: The Rh-rich region shows a temperature-independent (Pauli) paramagnetism whereas an additional temperature-dependent paramagnetic component is found in the Ru-rich region. - Graphical abstract: The new complex boride series Cr{sub x}(Rh{sub 1-y}Ru{sub y}){sub 7-x}B{sub 3} (x=0.88-1; y=0-1) has been synthesized by arc melting the elements under purified argon atmosphere. Beside the 3d/4d site preference within the whole solid solution, an unexpected Rh/Ru site preference was found in the Ru-rich region only, leading to two different magnetic behaviors: The Rh-rich region shows a temperature-independent (Pauli) paramagnetism whereas an additional temperature-dependent paramagnetic component is found in the Ru-rich region. Highlights: Black-Right-Pointing-Pointer Synthesis of a new boride series fulfilling Vegard Acute-Accent s rule. Black-Right-Pointing-Pointer 3d/4d site preference. Black-Right-Pointing-Pointer Unexpected Ru/Rh site preference. Black-Right-Pointing-Pointer Rh-rich region is Pauli paramagnetic. Black-Right-Pointing-Pointer Ru-rich region is Pauli and temperature-dependent paramagnetic.

Low content of Pt supported on Ni-MoCx/carbon black as a highly durable and active electrocatalyst for methanol oxidation, oxygen reduction and hydrogen evolution reactions in acidic condition

Science.gov (United States)

Zhang, Yan; Zang, Jianbing; Jia, Shaopei; Tian, Pengfei; Han, Chan; Wang, Yanhui

2017-08-01

Nickel and molybdenum carbide modified carbon black (Ni-MoCx/C) was synthesized by a two-step microwave-assisted deposition/carbonthermal reduction method and characterized by X-ray diffraction, transmission electron microscopy, energy dispersive spectroscopy and X-ray photoelectron spectroscopy. The as-prepared Ni-MoCx/C supported Pt (10 wt%) electrocatalyst (10Pt/Ni-MoCx/C) was synthesized through a microwave-assisted reduction method and 10Pt/Ni-MoCx/C exhibited high electrocatalytic activity for methanol oxidation, oxygen reduction and hydrogen evolution reactions. Results showed that 10Pt/Ni-MoCx/C electrocatalyst had better electrocatalytic activity and stability performance than 20 wt% Pt/C (20Pt/C) electrocatalyst. Among them, the electrochemical surface area of 10Pt/Ni-MoCx/C reached 68.4 m2 g-1, which was higher than that of 20Pt/C (63.2 m2 g-1). The enhanced stability and activity of 10Pt/Ni-MoCx/C electrocatalyst were attributed to: (1) an anchoring effect of Ni and MoCx formed during carbonthermal reduction process; (2) a synergistic effect among Pt, Ni, MoOx and MoCx. These findings indicated that 10Pt/Ni-MoCx/C was a promising electrocatalyst for direct methanol fuel cells.

Nanoconstruction by welding individual metallic nanowires together using nanoscale solder

International Nuclear Information System (INIS)

Peng, Y; Inkson, B J; Cullis, A G

2010-01-01

This work presents a new bottom-up nanowelding technique enabling building blocks to be assembled and welded together into complex 3D nanostructures using nanovolumes of metal solder. The building blocks of gold nanowires, (Co 72 Pt 28 /Pt) n multilayer nanowires, and nanosolder Sn 99 Au 1 alloy nanowires were successfully fabricated by a template technique. Individual metallic nanowires were picked up and assembled together. Conductive nanocircuits were then welded together using similar or dissimilar nanosolder material. At the weld sites, nanoscale volumes of a chosen metal are deposited using nanosolder of a sacrificial nanowire, which ensures that the nanoobjects to be bonded retain their structural integrity. The whole nanowelding process is clean, controllable and reliable, and ensures both mechanically strong and electrically conductive contacts.

Effect of ordered mesoporous carbon contact layer on the sensing performance of sputtered RuO2 thin film pH sensor.

Science.gov (United States)

Lonsdale, W; Maurya, D K; Wajrak, M; Alameh, K

2017-03-01

The effect of contact layer on the pH sensing performance of a sputtered RuO 2 thin film pH sensor is investigated. The response of pH sensors employing RuO 2 thin film electrodes on screen-printed Pt, carbon and ordered mesoporous carbon (OMC) contact layers are measured over a pH range from 4 to 10. Working electrodes with OMC contact layer are found to have Nernstian pH sensitivity (-58.4mV/pH), low short-term drift rate (5.0mV/h), low hysteresis values (1.13mV) and fast reaction times (30s), after only 1h of conditioning. A pH sensor constructed with OMC carbon contact layer displays improved sensing performance compared to Pt and carbon-based counterparts, making this electrode more attractive for applications requiring highly-accurate pH sensing with reduced conditioning time. Copyright © 2016 Elsevier B.V. All rights reserved.

Syntheses, structures, and physicochemical properties of diruthenium compounds of tetrachlorocatecholate with metal-metal bonded Ru(3+)(mu-OR)(2)Ru(3+) and Ru(3.5+)(mu-OR)(2)Ru(3.5+) cores (R = CH(3) and C(2)H(5)).

Science.gov (United States)

Miyasaka, H; Chang, H C; Mochizuki, K; Kitagawa, S

2001-07-02

Metal-metal bonded Ru(3+)(mu-OR)(2)Ru(3+) and Ru(3.5+)(mu-OR)(2)Ru(3.5+) (R = CH(3) and CH(3)CH(2)) compounds with tetrachlorocatecholate (Cl(4)Cat) have been synthesized in the corresponding alcohol, MeOH and EtOH, from a nonbridged Ru(2+)-Ru(3+) compound, Na(3)[Ru(2)(Cl(4)Cat)(4)(THF)].3H(2)O.7THF (1). In alcohol solvents, compound 1 is continuously oxidized by oxygen to form Ru(3+)(mu-OR)(2)Ru(3+) and Ru(3.5+)(mu-OR)(2)Ru(3.5+) species. The presence of a characteristic countercation leads to selective isolation of either Ru(3+)(mu-OR)(2)Ru(3+) or Ru(3.5+)(mu-OR)(2)Ru(3.5+) as a stable adduct species. In methanol, Ph(4)PCl and dibenzo-18-crown-6-ether afford Ru(3+)(mu-OMe)(2)Ru(3+) species, [A](2)[Ru(2)(Cl(4)Cat)(4)(mu-OMe)(2)Na(2)(MeOH)(6)] ([A](+) = Ph(4)P(+) (2), [Na(dibenzo-18-crown-6)(H(2)O)(MeOH)](+) (3)), while benzo-15-crown-5-ether provides a Ru(3.5+)(mu-OMe)(2)Ru(3.5+) species, [Na(benzo-15-crown-5)(2)][Ru(2)(Cl(4)Cat)(4)(mu-OMe)(2)Na(2)(MeOH)(6)] (4). The air oxidation of 1 in a MeOH/EtOH mixed solvent (1:1 v/v) containing benzo-15-crown-5-ether provides a Ru(3.5+)(mu-OMe)(2)Ru(3.5+) species, [Na(benzo-15-crown-5)(H(2)O)][Ru(2)(Cl(4)Cat)(2)(mu-OMe)(2)Na(2)(EtOH)(2)(H(2)O)(2)(MeOH)(2)].(benzo-15-crown-5) (5). Similarly, the oxidation of 1 in ethanol with Ph(4)PCl provides a Ru(3.5+)(mu-OEt)(2)Ru(3.5+) species, (Ph(4)P)[Ru(2)(Cl(4)Cat)(4)(mu-OEt)(2)Na(2)(EtOH)(6)] (7). A selective formation of a Ru(3+)(mu-OEt)(2)Ru(3+) species, (Ph(4)P)(2)[Ru(2)(Cl(4)Cat)(4)(mu-OEt)(2)Na(2)(EtOH)(2)(H(2)O)(2)] (6), is found in the presence of pyrazine or 2,5-dimethylpyrazine. The crystal structures of these compounds, except 2 and 7, have been determined by X-ray crystallography, and all compounds have been characterized by several spectroscopic and magnetic investigations. The longer Ru-Ru bonds are found in the Ru(3+)(mu-OR)(2)Ru(3+) species (2.606(1) and 2.628(2) A for 3 and 6, respectively) compared with those of Ru(3.5+)(mu-OMe)(2)Ru(3.5+) species (2.5260(6) A and 2

Effects of Nanoscale Carbon Black Modified by HNO3 on Immobilization and Phytoavailability of Ni in Contaminated Soil

Directory of Open Access Journals (Sweden)

Jiemin Cheng

2015-01-01

Full Text Available A surface-modified nanoscale carbon black (MCB as Ni adsorbent in contaminated soil was prepared by oxidizing the carbon black with 65% HNO3. The surface properties of the adsorbent were characterized by zeta potential analysis, scanning electron microscopy (SEM, and Fourier transform infrared spectroscopy (FTIRs. Batch experiments were conducted to evaluate the improvement of Ni2+ adsorption by MCB. Greenhouse cultivation experiments were conducted to examine the effect of MCB on the DTPA-extractable Ni2+ in soil, Ni2+ uptake of ryegrass shoot, and growth of ryegrass. Results indicated that MCB had much lower negative zeta potential, more functional groups for exchange and complexation of cation, and more heterogeneous pores and cavities for the adsorption of cation than the unmodified parent one (CB. MCB showed enhanced sorption capacity for Ni (qmax, 49.02 mg·g−1 compared with CB (qmax, 39.22 mg·g−1. Greenhouse cultivation experiment results showed that the biomass of ryegrass shoot and the Ni uptake of the ryegrass shoot were significantly increased and the concentrations of DTPA-extractable Ni in soil were significantly decreased with the increasing of MCB amount. It is clear from this work that the MCB had good adsorption properties for the Ni and could be applied in the in situ immobilization and remediation of heavy metal contaminated saline-alkali soils.

Performance of direct alcohol fuel cells fed with mixed methanol/ethanol solutions

Energy Technology Data Exchange (ETDEWEB)

Wongyao, N. [The Joint Graduate School of Energy and Environment, King Mongkut' s University of Technology Thonburi, 126 Pracha-Uthit Rd., Bang Mod, Thung Khru, Bangkok 10140 (Thailand); Therdthianwong, A., E-mail: apichai.the@kmutt.ac.t [Fuel Cell and Hydrogen Research and Engineering Center, Clean Energy System Group, PDTI, King Mongkut' s University of Technology Thonburi, 126 Pracha-Uthit Rd., Bang Mod, Thung Khru, Bangkok 10140 (Thailand); Therdthianwong, S. [Department of Chemical Engineering, Faculty of Engineering, King Mongkut' s University of Technology Thonburi, 126 Pracha-Uthit Rd., Bang Mod, Thung Khru, Bangkok 10140 (Thailand)

2011-07-15

Research highlights: {yields} We examined the performance of direct alcohol fuel cells fed with mixed alcohol. {yields} PtRu-PtSn/C and PtRu/C as catalysts for mixed alcohol electrooxidation reaction. {yields} Misplace adsorption of ethanol on PtRu/C caused the cell performance drop. {yields} PtRu/C showed higher performance than PtRu-PtSn/C for mixed alcohol fuel. -- Abstract: In combining the advantages of both methanol and ethanol, direct alcohol fuel cells fed with mixed alcohol solutions (1 M methanol and 1 M ethanol in varying volume ratios) were tested for performance. Employing a PtRu-PtSn/C catalyst as anode, cell performance was found to diminish rapidly even at 2.5% by volume ethanol mixture. Further increase of ethanol exceeded 10%, the cell performance gradually decreased and finally approached that of direct ethanol fuel cells. The causes of the decrease in the cell performance were the slow electro-oxidation of ethanol and the misplaced adsorption of ethanol on PtRu/C. By comparing the PtRu-PtSn/C cell with the PtRu/C cell operated with mixed alcohol solutions, the cell using PtRu/C as an anode catalyst provided higher power density since more PtRu/C surface was available for methanol oxidation reaction and less ohmic resistance of PtRu/C than that of PtRu-PtSn/C. In order to reach optimization of DAFC performance fed with mixed alcohol, the electrocatalyst used for the anode must selectively adsorb an alcohol, especially ethanol.

Performance of direct alcohol fuel cells fed with mixed methanol/ethanol solutions

International Nuclear Information System (INIS)

Wongyao, N.; Therdthianwong, A.; Therdthianwong, S.

2011-01-01

Research highlights: → We examined the performance of direct alcohol fuel cells fed with mixed alcohol. → PtRu-PtSn/C and PtRu/C as catalysts for mixed alcohol electrooxidation reaction. → Misplace adsorption of ethanol on PtRu/C caused the cell performance drop. → PtRu/C showed higher performance than PtRu-PtSn/C for mixed alcohol fuel. -- Abstract: In combining the advantages of both methanol and ethanol, direct alcohol fuel cells fed with mixed alcohol solutions (1 M methanol and 1 M ethanol in varying volume ratios) were tested for performance. Employing a PtRu-PtSn/C catalyst as anode, cell performance was found to diminish rapidly even at 2.5% by volume ethanol mixture. Further increase of ethanol exceeded 10%, the cell performance gradually decreased and finally approached that of direct ethanol fuel cells. The causes of the decrease in the cell performance were the slow electro-oxidation of ethanol and the misplaced adsorption of ethanol on PtRu/C. By comparing the PtRu-PtSn/C cell with the PtRu/C cell operated with mixed alcohol solutions, the cell using PtRu/C as an anode catalyst provided higher power density since more PtRu/C surface was available for methanol oxidation reaction and less ohmic resistance of PtRu/C than that of PtRu-PtSn/C. In order to reach optimization of DAFC performance fed with mixed alcohol, the electrocatalyst used for the anode must selectively adsorb an alcohol, especially ethanol.

103Ru for tumor scanning, 2

International Nuclear Information System (INIS)

Mizukawa, Kiichiro

1979-01-01

The mechanism of 103 Ru-uptake in tumors was investigated through the incubation of rat ascites hepatoma cells (AH-130) in vitro with various concentrations of Ru-chloride containing 103 Ru-chloride as a tracer. Quantitative analysis of Ru binding to the cells indicated that ascites hepatoma cells contained high- and low-affinity binding sites for Ru. When ascites hepatoma cells were incubated with Ru after incubation with a low concentration of papain, most of the Ru was not bound to the cells but was found in the medium containing solubilized glycoproteins. However Ru bound mainly to washed cells after the incubation with papain. About 65% of the Ru bound to ascites hepatoma cells was liberated by the papain treatment, and about 45% of the liberated Ru was precipitated by cetyltrimethylammonium bromide, indicating that Ru bound tightly to glycopeptides. These results suggest that the tumor affinity of 103 Ru is related to specific binding to glycopeptides on the tumor cell surface. (author)

Oxygen perovskites of type Ba/sub 3/Bsup(III)RuIrO/sub 9/

Energy Technology Data Exchange (ETDEWEB)

Duerrschmidt, E; Kemmler-Sack, S [Tuebingen Univ. (Germany, F.R.). Lehrstuhl fuer Anorganische Chemie 2

1980-11-01

The black perovskites Ba/sub 3/Bsup(III)RuIrO/sub 9/ with Bsup(III) = La, Nd, Sm, Gd, Dy, Er, Yb, In, Sc are isotypic. They crystallize in a hexagonal BaTiO/sub 3/ structure (sequence (hcc)/sub 2/). The mean oxydation state of the noble metal ions is +4.5.

Electronic structure of nanoscale Cu/Pt alloys: A combined X-ray diffraction and X-ray absorption investigations

International Nuclear Information System (INIS)

Chen Xing; Chu Wangsheng; Cai Quan; Xia Dingguo; Wu Zhonghua; Wu Ziyu

2006-01-01

PVP-protected Cu/Pt clusters were prepared by glycol/water reduction method and characterized with transmission electron microscopy (TEM), X-ray diffraction (XRD) and absorption spectra. TEM and XRD analysis show that the Cu/Pt clusters with different molar ratio have fcc structure with particle size of about 4 nm, while the lattice parameters in these clusters reduce with increasing Cu concentration. From the X-ray absorption near edge structure (XANES) at Cu-K edge and Pt-L 2,3 edge, we demonstrate that the d-electronic states of Cu and Pt are affected by the local environment as a function of Cu/Pt molar ratio. With increasing Cu concentration, Pt loses a fraction of 5d electrons and the hybridization between p- and d-states at Cu sites is enhanced

Electronic structure of nanoscale Cu/Pt alloys: A combined X-ray diffraction and X-ray absorption investigations

Energy Technology Data Exchange (ETDEWEB)

Chen Xing [Beijing Synchrotron Radiation Facility, Institute of High Energy Physics, CAS, Beijing (China); Graduate School of the Chinese Academy of Sciences, 100864 Beijing (China); Chu Wangsheng [Beijing Synchrotron Radiation Facility, Institute of High Energy Physics, CAS, Beijing (China); University of Science and Technology of China, Hefei, 230036 (China); Cai Quan [Beijing Synchrotron Radiation Facility, Institute of High Energy Physics, CAS, Beijing (China); Graduate School of the Chinese Academy of Sciences, 100864 Beijing (China); Xia Dingguo [College of Environmental and Energy Engineering, Beijing University of Technology, 100022 Beijing (China); Wu Zhonghua [Beijing Synchrotron Radiation Facility, Institute of High Energy Physics, CAS, Beijing (China); Wu Ziyu [Beijing Synchrotron Radiation Facility, Institute of High Energy Physics, CAS, Beijing (China) and National Center for Nanoscience and Technology (China)]. E-mail: wuzy@ihep.ac.cn

2006-11-15

PVP-protected Cu/Pt clusters were prepared by glycol/water reduction method and characterized with transmission electron microscopy (TEM), X-ray diffraction (XRD) and absorption spectra. TEM and XRD analysis show that the Cu/Pt clusters with different molar ratio have fcc structure with particle size of about 4 nm, while the lattice parameters in these clusters reduce with increasing Cu concentration. From the X-ray absorption near edge structure (XANES) at Cu-K edge and Pt-L{sub 2,3} edge, we demonstrate that the d-electronic states of Cu and Pt are affected by the local environment as a function of Cu/Pt molar ratio. With increasing Cu concentration, Pt loses a fraction of 5d electrons and the hybridization between p- and d-states at Cu sites is enhanced.

Pt coating on flame-generated carbon particles

International Nuclear Information System (INIS)

Choi, In Dae; Lee, Dong Geun

2008-01-01

Carbon black, activated carbon and carbon nanotube have been used as supporting materials for precious metal catalysts used in fuel cell electrodes. One-step flame synthesis method is used to coat 2-5nm Pt dots on flame-generated carbon particles. By adjusting flame temperature, gas flow rates and resident time of particles in flame, we can obtain Pt/C nano catalyst-support composite particles. Additional injection of hydrogen gas facilitates pyrolysis of Pt precursor in flame. The size of as-incepted Pt dots increases along the flame due to longer resident time and sintering in high temperature flame. Surface coverage and dispersion of the Pt dots is varied at different sampling heights and confirmed by Transmission Electron Microscopy (TEM), Energy Dispersive Spectra (EDS) and X-Ray Diffraction (XRD). Crystallinity and surface bonding groups of carbon are investigated through X-ray Photoelectron Spectroscoy (XPS) and Raman spectroscopy

Design of ultrathin Pt-Mo-Ni nanowire catalysts for ethanol electrooxidation.

Science.gov (United States)

Mao, Junjie; Chen, Wenxing; He, Dongsheng; Wan, Jiawei; Pei, Jiajing; Dong, Juncai; Wang, Yu; An, Pengfei; Jin, Zhao; Xing, Wei; Tang, Haolin; Zhuang, Zhongbin; Liang, Xin; Huang, Yu; Zhou, Gang; Wang, Leyu; Wang, Dingsheng; Li, Yadong

2017-08-01

Developing cost-effective, active, and durable electrocatalysts is one of the most important issues for the commercialization of fuel cells. Ultrathin Pt-Mo-Ni nanowires (NWs) with a diameter of ~2.5 nm and lengths of up to several micrometers were synthesized via a H 2 -assisted solution route (HASR). This catalyst was designed on the basis of the following three points: (i) ultrathin NWs with high numbers of surface atoms can increase the atomic efficiency of Pt and thus decrease the catalyst cost; (ii) the incorporation of Ni can isolate Pt atoms on the surface and produce surface defects, leading to high catalytic activity (the unique structure and superior activity were confirmed by spherical aberration-corrected electron microscopy measurements and ethanol oxidation tests, respectively); and (iii) the incorporation of Mo can stabilize both Ni and Pt atoms, leading to high catalytic stability, which was confirmed by experiments and density functional theory calculations. Furthermore, the developed HASR strategy can be extended to synthesize a series of Pt-Mo-M (M = Fe, Co, Mn, Ru, etc.) NWs. These multimetallic NWs would open up new opportunities for practical fuel cell applications.

Density of states in Mo-Ru amorphous alloys

International Nuclear Information System (INIS)

Miyakawa, W.

1985-01-01

The density of states is calculated for several compositions of amorphous Mo 1-x Ru x . In order to simulate amorphous clusters, the structures (atomic positions) utilized in the calculations were built from a small dense randomly packed unit of hard spheres with periodic boundary conditions. The density of states is calculated from a tight-binding Hamiltonian with hopping integrals parametrized in terms of the ddσ, ddΠ and ddδ molecular integrals. The results for pure Mo and pure Ru, compared in the canonical band aproximation, agree well with the literature. For binary alloys, the comparison of the calculated density of states with the rigid band aproximation results indicates that a more complex approach than the rigid band model must be used, even when the two atoms have similar bands, with band centers at nearly the same energy. The results also indicate that there is no relation between the peak in the superconducting critical temperature as a function of the number of valence eletrons per atom (e/a) in the region near Mo(e/a=6) and the peak of the density of states at the Fermi level in the same region, as has been sugested by some authors. (Author) [pt

Electrocatalytic reduction of H{sub 2}O{sub 2} by Pt nanoparticles covalently bonded to thiolated carbon nanostructures

Energy Technology Data Exchange (ETDEWEB)

You, Jung-Min; Kim, Daekun [Department of Chemistry and Institute of Basic Science, Chonnam National University, Gwangju 500-757 (Korea, Republic of); Jeon, Seungwon [Department of Chemistry and Institute of Basic Science, Chonnam National University, Gwangju 500-757 (Korea, Republic of)

2012-03-30

Highlights: Black-Right-Pointing-Pointer Novel thiolated carbon nanostructures - platinum nanoparticles [t-GO-C(O)-pt and t-MWCNT-C(O)-S-pt] have been synthesized, and [t-GO-C(O)-pt and t-MWCNT-C(O)-S-pt] denotes as t-GO-pt and t-MWCNT-Pt in manuscript, respectively. Black-Right-Pointing-Pointer The modified electrode denoted as PDDA/t-GO-pt/GCE was used for the electrochemical determination of H{sub 2}O{sub 2} for the first time. Black-Right-Pointing-Pointer The results show that PDDA/t-GO-pt nanoparticles have the promising potential as the basic unit of the electrochemical biosensors for the detection of H{sub 2}O{sub 2}. Black-Right-Pointing-Pointer The proposed H{sub 2}O{sub 2} biosensors exhibited wide linear ranges and low detection limits, giving fast responses within 10 s. - Abstract: Glassy carbon electrodes were coated with thiolated carbon nanostructures - multi-walled carbon nanotubes and graphene oxide. The subsequent covalent addition of platinum nanoparticles and coating with poly(diallydimethylammonium chloride) resulted in biosensors that detected hydrogen peroxide through its electrocatalytic reduction. The sensors were easily and quickly prepared and showed improved sensitivity to the electrocatalytic reduction of H{sub 2}O{sub 2}. The Pt nanoparticles covalently bonded to the thiolated carbon nanostructures were characterized by transmission electron microscopy, X-ray photoelectron spectroscopy, and energy dispersive X-ray spectroscopy. Cyclic voltammetry and amperometry were used to characterize the biosensors' performances. The sensors exhibited wide linear ranges and low detection limits, giving fast responses within 10 s, thus demonstrating their potential for use in H{sub 2}O{sub 2} analysis.

Substituent-directed structural and physicochemical controls of diruthenium catecholate complexes with ligand-unsupported Ru-Ru bonds.

Science.gov (United States)

Chang, Ho-Chol; Mochizuki, Katsunori; Kitagawa, Susumu

2005-05-30

A family of diruthenium complexes with ligand-unsupported Ru-Ru bonds has been systematically synthesized, and their crystal structures and physical properties have been examined. A simple, useful reaction between Ru2(OAc)4Cl (OAc- = acetate) and catechol derivatives in the presence of bases afforded a variety of diruthenium complexes, generally formulated as [Na(n){Ru2(R4Cat)4}] (n = 2 or 3; R4 = -F4, -Cl4, -Br4, -H4, -3,5-di-t-Bu, and -3,6-di-t-Bu; Cat(2-) = catecholate). The most characteristic feature of the complexes is the formation of short ligand-unsupported Ru-Ru bonds (2.140-2.273 A). These comprehensive studies were carried out to evaluate the effects of the oxidation states and the substituents governing the molecular structures and physicochemical properties. The Ru-Ru bond distances, rotational conformations, and bending structures of the complexes were successfully varied. The results presented in this manuscript clearly demonstrate that the complexes with ligand-unsupported Ru-Ru bonds can sensitively respond to redox reactions and ligand substituents on the basis of the greater degree of freedom in their molecular structures.

Synthesis and characterization of FePt nanoparticles by high energy ball milling with and without surfactant

Energy Technology Data Exchange (ETDEWEB)

Velasco, V., E-mail: vvjimeno@fis.ucm.es [Instituto de Magnetismo Aplicado, UCM-ADIF-CSIC, 28230 Las Rozas (Spain); Martinez, A.; Recio, J. [Instituto de Magnetismo Aplicado, UCM-ADIF-CSIC, 28230 Las Rozas (Spain); Hernando, A.; Crespo, P. [Instituto de Magnetismo Aplicado, UCM-ADIF-CSIC, 28230 Las Rozas (Spain); Dpto. de Fisica de Materiales, UCM, 28040 Madrid (Spain)

2012-09-25

Highlights: Black-Right-Pointing-Pointer Fe and Pt powders in the presence of surfactants don't alloyed by HEBM technique. Black-Right-Pointing-Pointer FePt alloys obtained by dry milling exhibit particle sizes of around 10 {mu}m. Black-Right-Pointing-Pointer FePt alloys obtained by dry milling exhibit soft magnetic behavior. Black-Right-Pointing-Pointer A thermal treatment induces a phase transformation from FCC to FCT. - Abstract: FePt nanoparticles were prepared by high energy ball milling (HEBM) in two different ways. In the first one, elemental powders were mixed and milled whereas in the second one the milling was performed in the presence of oleyl amine and oleic acid as surfactants and hexane as a solvent. X-ray diffraction shows that when the milling is performed in dry conditions, Fe and Pt are alloyed after 5 h, whereas in the wet milling procedure alloying does not take place. In the first case, the diffraction pattern corresponds to the disordered FCC phase. This behavior is also corroborated by the evolution of the magnetic characteristics. In the case of the alloy obtained in dry conditions, the powder was heat treated in order to induce the transformation to the ordered phase. Coercivities of 2.5 kOe are obtained after 650 Degree-Sign C for 2 h.

Electrocatalytic activity of Pt nanoparticles on bamboo shaped carbon nanotubes for ethanol oxidation

International Nuclear Information System (INIS)

Zhu Zanzan; Wang Jianlong; Munir, Ahsan; Zhou, H. Susan

2010-01-01

Recently, bamboo shaped carbon nanotubes (BCNTs) have received increased attention for its bamboo shaped structure associated properties and its application in direct methanol/ethanol fuel cell. In this work, the potential to use BCNTs as the support material of high loaded Pt nanoparticles for improving the efficiency of ethanol/methanol fuel cell is explored. The structure and nature of the resulting Pt-BCNTS composite were characterized by transmission electron microscopy (TEM) and energy dispersive spectroscopy (EDS) spectrum, it was found that Pt nanoparticles were homogeneously dispersed on the BCNTs surfaces with 23.5% by weight. Cyclic voltammogram (CV) indicated that the Pt-BCNTs catalyst displayed excellent electrocatalytic activity and long-term stability toward ethanol oxidation. The excellent performance may be attributed to the high dispersion of nanoscale Pt catalysts and the unique nature of BCNTs. The results imply that doping N atom introduces some defective sites and active sites onto the surface of CNTs. In general, this paper demonstrates that BCNTs are promising support material for Pt-nanoparticles catalyst and can be used to enhance the efficiency of fuel cell.

Design criteria for stable Pt/C fuel cell catalysts

Directory of Open Access Journals (Sweden)

Josef C. Meier

2014-01-01

Full Text Available Platinum and Pt alloy nanoparticles supported on carbon are the state of the art electrocatalysts in proton exchange membrane fuel cells. To develop a better understanding on how material design can influence the degradation processes on the nanoscale, three specific Pt/C catalysts with different structural characteristics were investigated in depth: a conventional Pt/Vulcan catalyst with a particle size of 3–4 nm and two Pt@HGS catalysts with different particle size, 1–2 nm and 3–4 nm. Specifically, Pt@HGS corresponds to platinum nanoparticles incorporated and confined within the pore structure of the nanostructured carbon support, i.e., hollow graphitic spheres (HGS. All three materials are characterized by the same platinum loading, so that the differences in their performance can be correlated to the structural characteristics of each material. The comparison of the activity and stability behavior of the three catalysts, as obtained from thin film rotating disk electrode measurements and identical location electron microscopy, is also extended to commercial materials and used as a basis for a discussion of general fuel cell catalyst design principles. Namely, the effects of particle size, inter-particle distance, certain support characteristics and thermal treatment on the catalyst performance and in particular the catalyst stability are evaluated. Based on our results, a set of design criteria for more stable and active Pt/C and Pt-alloy/C materials is suggested.

Inner-shell photodetachment from Ru-

International Nuclear Information System (INIS)

Dumitriu, I.; Gorczyca, T. W.; Berrah, N.; Bilodeau, R. C.; Pesic, Z. D.; Rolles, D.; Walter, C. W.; Gibson, N. D.

2010-01-01

Inner-shell photodetachment from Ru - was studied near and above the 4p excitation region, 29-to-91-eV photon energy range, using a merged ion-photon-beam technique. The absolute photodetachment cross sections of Ru - ([Kr]4d 7 5s 2 ) leading to Ru + , Ru 2+ , and Ru 3+ ion production were measured. In the near-threshold region, a Wigner s-wave law, including estimated postcollision interaction effects, locates the 4p 3/2 detachment threshold between 40.10 and 40.27 eV. Additionally, the Ru 2+ product spectrum provides evidence for simultaneous two-electron photodetachment (likely to the Ru + 4p 5 4d 6 5s 2 state) located near 49 eV. Resonance effects are observed due to interference between transitions of the 4p electrons to the quasibound 4p 5 4d 8 5s 2 states and the 4d→εf continuum. Despite the large number of possible terms resulting from the Ru - 4d open shell, the cross section obtained from a 51-state LS-coupled R-matrix calculation agrees qualitatively well with the experimental data.

DNA-templated synthesis of Pt nanoparticles on single-walled carbon nanotubes.

Science.gov (United States)

Dong, Lifeng

2009-11-18

A series of electron microscopy characterizations demonstrate that single-stranded deoxyribonucleic acid (ssDNA) can bind to nanotube surfaces and disperse bundled single-walled carbon nanotubes (SWCNTs) into individual tubes. The ssDNA molecules on the nanotube surfaces demonstrate various morphologies, such as aggregated clusters and spiral wrapping around a nanotube with different pitches and spaces, indicating that the morphology of the SWCNT/DNA hybrids is not related solely to the base sequence of the ssDNA or the chirality or the diameter of the nanotubes. In addition to serving as a non-covalent dispersion agent, the ssDNA molecules bonded to the nanotube surface can provide addresses for localizing Pt(II) complexes along the nanotubes. The Pt nanoparticles obtained by a reduction of the Pt2+-DNA adducts are crystals with a size of direct ethanol/methanol fuel cells and nanoscale electronics.

Pt-Ni and Pt-Co Catalyst Synthesis Route for Fuel Cell Applications

Science.gov (United States)

Firdosy, Samad A.; Ravi, Vilupanur A.; Valdez, Thomas I.; Kisor, Adam; Narayan, Sri R.

2013-01-01

Oxygen reduction reactions (ORRs) at the cathode are the rate-limiting step in fuel cell performance. The ORR is 100 times slower than the corresponding hydrogen oxidation at the anode. Speeding up the reaction at the cathode will improve fuel cell efficiency. The cathode material is generally Pt powder painted onto a substrate (e.g., graphite paper). Recent efforts in the fuel cell area have focused on replacing Pt with Pt-X alloys (where X = Co, Ni, Zr, etc.) in order to (a) reduce cost, and (b) increase ORR rates. One of these strategies is to increase ORR rates by reducing the powder size, which would result in an increase in the surface area, thereby facilitating faster reaction rates. In this work, a process has been developed that creates Pt-Ni or Pt-Co alloys that are finely divided (on the nano scale) and provide equivalent performance at lower Pt loadings. Lower Pt loadings will translate to lower cost. Precursor salts of the metals are dissolved in water and mixed. Next, the salt mixtures are dried on a hot plate. Finally, the dried salt mixture is heattreated in a furnace under flowing reducing gas. The catalyst powder is then used to fabricate a membrane electrode assembly (MEA) for electrochemical performance testing. The Pt- Co catalyst-based MEA showed comparable performance to an MEA fabri cated using a standard Pt black fuel cell catalyst. The main objective of this program has been to increase the overall efficiencies of fuel cell systems to support power for manned lunar bases. This work may also have an impact on terrestrial programs, possibly to support the effort to develop a carbon-free energy source. This catalyst can be used to fabricate high-efficiency fuel cell units that can be used in space as regenerative fuel cell systems, and terrestrially as primary fuel cells. Terrestrially, this technology will become increasingly important when transition to a hydrogen economy occurs.

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

Science.gov (United States)

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

2014-06-01

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

Co-catalytic effect of Rh and Ru for the ethanol electro-oxidation in amorphous microparticulated alloys

Energy Technology Data Exchange (ETDEWEB)

Blanco, Tamara C.; Pierna, Angel R.; Barroso, Javier [Dpto. de Ingenieria Quimica y del Medio Ambiente, Universidad del Pais Vasco, San Sebastian (Spain)

2011-11-15

The ethanol electro-oxidation on platinum catalyst in acid media leads to the formation of acetaldehyde and acetic acid as main products. Another problem is the poisoning of the electro-catalyst surface with CO formed during the fuel oxidation reaction. To increase the performance of Direct Ethanol Fuel Cells (DEFCs) it is necessary to develop new electrode materials or modification of the existing Pt catalysts. This work presents the electrochemical response to ethanol and CO oxidation of different compositional amorphous alloys obtained by ball milling technique, used as electrodes. Alloys with Ni{sub 59}Nb{sub 40}Pt{sub 0.6}Rh{sub 0.4} and Ni{sub 59}Nb{sub 40}Pt{sub 0.6}Rh{sub 0.2}Ru{sub 0.2} composi-tions were studied. The current density towards ethanol oxidation decreases with the presence of ruthenium; however, this electrode shows the best tolerance to CO, with lower surface coverage (copyright 2011 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

Co-catalytic effect of Rh and Ru for the ethanol electro-oxidation in amorphous microparticulated alloys

International Nuclear Information System (INIS)

Blanco, Tamara C.; Pierna, Angel R.; Barroso, Javier

2011-01-01

The ethanol electro-oxidation on platinum catalyst in acid media leads to the formation of acetaldehyde and acetic acid as main products. Another problem is the poisoning of the electro-catalyst surface with CO formed during the fuel oxidation reaction. To increase the performance of Direct Ethanol Fuel Cells (DEFCs) it is necessary to develop new electrode materials or modification of the existing Pt catalysts. This work presents the electrochemical response to ethanol and CO oxidation of different compositional amorphous alloys obtained by ball milling technique, used as electrodes. Alloys with Ni 59 Nb 40 Pt 0.6 Rh 0.4 and Ni 59 Nb 40 Pt 0.6 Rh 0.2 Ru 0.2 composi-tions were studied. The current density towards ethanol oxidation decreases with the presence of ruthenium; however, this electrode shows the best tolerance to CO, with lower surface coverage (copyright 2011 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

Synthesis and characterization of ruthenium-decorated nanoporous platinum materials

International Nuclear Information System (INIS)

Peng Xinsheng; Koczkur, Kallum; Chen, Aicheng

2007-01-01

We report on the synthesis of novel three-dimensional nanoporous Pt-Ru bimetallic networks by decorating nanoporous Pt networks with Ru using a hydrothermally assisted precipitating process. Scanning electron microscopy (SEM) and energy dispersive x-ray spectroscopy (EDS) were used to characterize the morphology and the composition of the nanoporous Pt-Ru networks formed. X-ray diffraction analysis confirmed that, after protected annealing treatment, Pt-Ru bimetallic material was formed. The electrocatalytic activity of the synthesized nanoporous Pt-Ru networks was characterized using electrochemical oxidation of methanol as a probe. The electrocatalytic activity of the nanoporous Pt networks significantly increases with the increments of decorated Ru and reaches the highest value with 41% of Ru. The peak current of methanol oxidation on the nanoporous Pt-Ru(41%) bimetallic networks is over 180% higher than that on the nanoporous Pt networks without Ru decoration. This is very desirable for fuel cell development and electrochemical sensor design

Ru-assisted synthesis of Pd/Ru nanodendrites with high activity for ethanol electrooxidation

Science.gov (United States)

Zhang, Ke; Bin, Duan; Yang, Beibei; Wang, Caiqin; Ren, Fangfang; Du, Yukou

2015-07-01

Due to the specific physical and chemical properties of a highly branched noble metal, the controllable synthesis has attracted much attention. This article reports the synthesis of Pd/Ru nanodendrites by a facile method using an oil bath in the presence of polyvinyl pyrrolidone, potassium bromide and ascorbic acid. The morphology, structure, and composition of the as-prepared catalysts were characterized by means of X-ray diffraction, X-ray photoelectron spectroscopy and transmission electron microscopy. In the electrochemical measurement, the as-prepared Pd7/Ru1 bimetallic nanodendrites provide a large electrochemically active surface area and exhibit high peak current density in the forward scan toward ethanol electrooxidation, which is nearly four times higher than those of a pure Pd catalyst. The as-prepared Pd7/Ru1 catalysts also exhibit significantly enhanced cycling stability toward ethanol oxidation in alkaline medium, which are mainly ascribed to the synergetic effect between Pd and Ru. This indicates that the Pd7/Ru1 catalysts should have great potential applications in direct ethanol fuel cells.Due to the specific physical and chemical properties of a highly branched noble metal, the controllable synthesis has attracted much attention. This article reports the synthesis of Pd/Ru nanodendrites by a facile method using an oil bath in the presence of polyvinyl pyrrolidone, potassium bromide and ascorbic acid. The morphology, structure, and composition of the as-prepared catalysts were characterized by means of X-ray diffraction, X-ray photoelectron spectroscopy and transmission electron microscopy. In the electrochemical measurement, the as-prepared Pd7/Ru1 bimetallic nanodendrites provide a large electrochemically active surface area and exhibit high peak current density in the forward scan toward ethanol electrooxidation, which is nearly four times higher than those of a pure Pd catalyst. The as-prepared Pd7/Ru1 catalysts also exhibit significantly

Comparison of hydration reactions for "piano-stool" RAPTA-B and [Ru(η6- arene)(en)Cl]+ complexes: Density functional theory computational study

Science.gov (United States)

Chval, Zdeněk; Futera, Zdeněk; Burda, Jaroslav V.

2011-01-01

The hydration process for two Ru(II) representative half-sandwich complexes: Ru(arene)(pta)Cl2 (from the RAPTA family) and [Ru(arene)(en)Cl]+ (further labeled as Ru_en) were compared with analogous reaction of cisplatin. In the study, quantum chemical methods were employed. All the complexes were optimized at the B3LYP/6-31G(d) level using Conductor Polarizable Continuum Model (CPCM) solvent continuum model and single-point (SP) energy calculations and determination of electronic properties were performed at the B3LYP/6-311++G(2df,2pd)/CPCM level. It was found that the hydration model works fairly well for the replacement of the first chloride by water where an acceptable agreement for both Gibbs free energies and rate constants was obtained. However, in the second hydration step worse agreement of the experimental and calculated values was achieved. In agreement with experimental values, the rate constants for the first step can be ordered as RAPTA-B > Ru_en > cisplatin. The rate constants correlate well with binding energies (BEs) of the Pt/Ru-Cl bond in the reactant complexes. Substitution reactions on Ru_en and cisplatin complexes proceed only via pseudoassociative (associative interchange) mechanism. On the other hand in the case of RAPTA there is also possible a competitive dissociation mechanism with metastable pentacoordinated intermediate. The first hydration step is slightly endothermic for all three complexes by 3-5 kcal/mol. Estimated BEs confirm that the benzene ligand is relatively weakly bonded assuming the fact that it occupies three coordination positions of the Ru(II) cation.

Electrochemically shape-controlled synthesis in deep eutectic solvents of Pt nanoflowers with enhanced activity for ethanol oxidation

International Nuclear Information System (INIS)

Wei Lu; Fan Youjun; Wang Honghui; Tian Na; Zhou Zhiyou; Sun Shigang

2012-01-01

Highlights: ► The electrochemically shape-controlled synthesis in deep eutectic solvents (DESs) has been applied to produce the uniform Pt nanoflowers with sharp single crystal petals and high density of atomic steps. ► The as-prepared Pt nanoflowers exhibit higher electrocatalytic activity and stability than commercial Pt black catalyst toward ethanol electrooxidation. ► The growth of Pt nanoflowers in DESs by the simple electrochemical route is straightforward and controllable in terms of nanoflowers’ shape and size. - Abstract: The electrochemically shape-controlled synthesis in deep eutectic solvents (DESs) has been applied to produce the electrocatalyst of Pt nanoflowers. The uniform Pt nanoflowers with sharp single crystal petals and high density of atomic steps were characterized by SEM, TEM, XRD, XPS and electrochemical tests. The results illustrated that the as-prepared Pt nanoflowers exhibit higher electrocatalytic activity and stability than commercial Pt black catalyst toward ethanol electrooxidation. The growth of Pt nanoflowers in DESs by the simple electrochemical route is straightforward and controllable in terms of nanoflowers’ shape and size, which can be applied in shape-controlled synthesis of other noble metal nanoparticles with high catalytic activity.

Reduction of RuVI≡N to RuIII-NH3 by Cysteine in Aqueous Solution.

Science.gov (United States)

Wang, Qian; Man, Wai-Lun; Lam, William W Y; Yiu, Shek-Man; Tse, Man-Kit; Lau, Tai-Chu

2018-05-21

The reduction of metal nitride to ammonia is a key step in biological and chemical nitrogen fixation. We report herein the facile reduction of a ruthenium(VI) nitrido complex [(L)Ru VI (N)(OH 2 )] + (1, L = N, N'-bis(salicylidene)- o-cyclohexyldiamine dianion) to [(L)Ru III (NH 3 )(OH 2 )] + by l-cysteine (Cys), an ubiquitous biological reductant, in aqueous solution. At pH 1.0-5.3, the reaction has the following stoichiometry: [(L)Ru VI (N)(OH 2 )] + + 3HSCH 2 CH(NH 3 )CO 2 → [(L)Ru III (NH 3 )(OH 2 )] + + 1.5(SCH 2 CH(NH 3 )CO 2 ) 2 . Kinetic studies show that at pH 1 the reaction consists of two phases, while at pH 5 there are three distinct phases. For all phases the rate law is rate = k 2 [1][Cys]. Studies on the effects of acidity indicate that both HSCH 2 CH(NH 3 + )CO 2 - and - SCH 2 CH(NH 3 + )CO 2 - are kinetically active species. At pH 1, the reaction is proposed to go through [(L)Ru IV (NHSCH 2 CHNH 3 CO 2 H)(OH 2 )] 2+ (2a), [(L)Ru III (NH 2 SCH 2 CHNH 3 CO 2 H)(OH 2 )] 2+ (3), and [(L)Ru IV (NH 2 )(OH 2 )] + (4) intermediates. On the other hand, at pH around 5, the proposed intermediates are [(L)Ru IV (NHSCH 2 CHNH 3 CO 2 )(OH 2 )] + (2b) and [(L)Ru IV (NH 2 )(OH 2 )] + (4). The intermediate ruthenium(IV) sulfilamido species, [(L)Ru IV (NHSCH 2 CHNH 3 CO 2 H)(OH 2 )] 2+ (2a) and the final ruthenium(III) ammine species, [(L)Ru III (NH 3 )(MeOH)] + (5) (where H 2 O was replaced by MeOH) have been isolated and characterized by various spectroscopic methods.

Microstructural and magnetic properties of L10 FePt-C (0 0 1) textured nanocomposite films grown on different intermediate layers

International Nuclear Information System (INIS)

Chen, J S; Chow, G M; Lim, B C; Hu, J F; Ding, Y F; Ju, G

2008-01-01

The FePt : C films with different volume fractions of carbon and different thicknesses were epitaxially grown on a CrRu(2 0 0) underlayer with Pt and MgO intermediate layers. The magnetic properties and microstructure of these FePt : C films were investigated. The FePt : C films grown on the Pt intermediate layer consisted of a continuous layer of FePt, with overlying granular FePt grains, while the FePt : C films grown on the MgO intermediate layer consisted of granular FePt : C layers with overlying granular grains. The formation of the overlying granular FePt grains was attributed to carbon diffusion to the surface which resulted in the second nucleation of FePt. The different interface energies and surface energies of FePt on Pt and MgO intermediate layers caused the formation of an initial continuous FePt layer on the Pt intermediate layer and initial granular FePt layers on the MgO intermediate layer. The coupling between the continuous FePt layer or the granular FePt layer and the overlying granular FePt grains resulted in simultaneous magnetization reversal and thus strong exchange coupling in FePt : C films.

General aspects of surface alloy formation

Energy Technology Data Exchange (ETDEWEB)

Bergbreiter, Andreas; Engstfeld, Albert K.; Roetter, Ralf T.; Hoster, Harry E.; Behm, R. Juergen [Institute of Surface Chemistry and Catalysis, Ulm University, D-89069 Ulm (Germany); Berko, Andras

2010-07-01

Surface confined alloys are excellent model systems for studies of structure-property relationships of bimetallic surfaces. They are formed by deposition of a guest metal B onto a substrate A, followed by annealing to a temperature, where place exchange between adatoms and atoms from the underlying surface layer becomes possible and diffusion into the bulk is sufficiently slow. We exemplarily confirmed by scanning tunneling microscopy and Auger electron spectroscopy for PtRu/Ru(0001), PdRu/Ru(0001), AuPt/Pt(111), AgPt/Pt(111), and AgPd/Pd(111), surface alloys are obtained for systems where metal B has a negative surface segregation energy within metal A. By exchanging A and B, however, AB surface alloys are most likely overgrown by metal B, which we demonstrate for RuPt/Pt(111) in comparison to PtRu/Ru(0001).

Mobility of gamma-emitting fission products in typical black and laterite soils

International Nuclear Information System (INIS)

D'Souza, T.J.; Mistry, K.B.

1981-01-01

Studies on the movement of the gamma-emitting fission products 106 Ru, 125 Sb, 137 Cs and 144 Ce, surface deposited on columns of the black and laterite soils revealed that the mobility of these nuclides in the two soils depended mainly on the ionic form of the nuclide, soil reaction and predominant clay mineral type in the soil. Results showed a rapid breakthrough of 106 Ru in the black soil and considerable migration to the lower layers in the laterite soil on leaching with rain water, or moderately high calcium or sodium irrigation waters. While near complete fixation of 144 Ce and 137 Cs in the top contaminated layer of both soils was observed, a slight movement of 125 Sb only in the black soil was noticed. Incorporation of organic matter had no effects on the movement of fission products in both soil types, whereas ethylenediaminetraacetic acid (EDTA) induced variable movement of the different radionuclides in the two soil types. (author)

Pt-doped In{sub 2}O{sub 3} nanoparticles prepared by flame spray pyrolysis for NO{sub 2} sensing

Energy Technology Data Exchange (ETDEWEB)

Inyawilert, K. [Chiang Mai University, Department of Physics and Materials Science, Faculty of Science (Thailand); Channei, D. [Naresuan University, Department of Chemistry, Faculty of Science (Thailand); Tamaekong, N. [Maejo University, Program in Materials Science, Faculty of Science (Thailand); Liewhiran, C. [Chiang Mai University, Department of Physics and Materials Science, Faculty of Science (Thailand); Wisitsoraat, A.; Tuantranont, A. [National Electronics and Computer Technology Center (NECTEC), Nanoelectronics and MEMS Laboratory (Thailand); Phanichphant, S., E-mail: sphanichphant@gmail.com [Chiang Mai University, Faculty of Science, Materials Science Research Center (Thailand)

2016-02-15

Undoped In{sub 2}O{sub 3} and 0.25–1.00 wt% M (M=Pt, Nb, and Ru)-doped/loaded In{sub 2}O{sub 3} nanoparticles were successfully synthesized in a single-step flame spray pyrolysis technique using indium nitrate, platinum (II) acetylacetonate, niobium ethoxide, and ruthenium (III) acetylacetonate precursors. The undoped In{sub 2}O{sub 3} and M-doped In{sub 2}O{sub 3} nanoparticles were characterized by Brunauer–Emmett–Teller (BET) analysis, X-ray diffraction (XRD), and scanning and transmission electron microscopy (SEM & TEM). The BET average diameter of spherical nanoparticles was found to be in the range of 10.2–15.2 nm under 5/5 (precursor/oxygen) flame conditions. All XRD peaks were confirmed to correspond to the cubic structure of In{sub 2}O{sub 3}. TEM images showed that there is no Pt nanoparticle loaded on In{sub 2}O{sub 3} surface, suggesting that Pt should form solid solution with the In{sub 2}O{sub 3} lattice. Gas sensing studies showed that 0.5 wt% Pt doping in In{sub 2}O{sub 3} nanoparticles gave a significant enhancement of NO{sub 2} sensing performances in terms of sensor response and selectivity. 0.5 wt% Pt/In{sub 2}O{sub 3} exhibited a high NO{sub 2} response of ∼1904 to 5 ppm NO{sub 2} at 250 °C and good NO{sub 2} selectivity against NO, H{sub 2}S, H{sub 2}, and C{sub 2}H{sub 5}OH. In contrast, Nb and Ru loading resulted in deteriorated NO{sub 2} response. Therefore, Pt is demonstrated to be an effective additive to enhance NO{sub 2} sensing performances of In{sub 2}O{sub 3}-based sensors.

Preparation of PtSnCu/C and PtSn/C electrocatalysts and activation by dealloying processes for ethanol electrooxidation

International Nuclear Information System (INIS)

Crisafulli, Rudy

2013-01-01

PtSnCu/C (with different Pt:Sn:Cu atomic ratios) and PtSn/C (50:50) electrocatalysts were prepared by borohydride (BR) and alcohol-reduction (AR) processes using H 2 PtCl 6 .6H 2 O, SnCl 2 .2H 2 O and CuCl 2 .2H 2 O as metal sources, NaBH 4 and ethylene glycol as reducing agents, 2-propanol and ethylene glycol/water as solvents and carbon black as support. In a further step, these electrocatalysts were activated by chemical (CD) and electrochemical (ED) dealloying processes through acid treatment and thin porous coating technique, respectively. These materials were characterized by energy dispersive X-ray, Xray diffraction, transmission electron microscopy, line scan energy dispersive Xray and cyclic voltammetry. Electrochemical studies for ethanol electro-oxidation were performed by cyclic voltammetry, chronoamperometry and in single Direct Ethanol Fuel Cell using Membrane Electrode Assembly (MEA). The anodic effluents were analysed by gas chromatography. The X-ray diffractograms of the as-synthesized electrocatalysts showed the typical face-centered cubic structure (FCC) of platinum and its alloys. After dealloying, the X-ray diffractograms showed that the Pt FCC structure was preserved. The crystallite sizes of the assynthesized electrocatalysts were in the range of PtSnCu/C (50:40:10) AR/ED > PtSnCu/C (50:10:40) BR/CD. PtSn/C (50:50) BR/CD, PtSnCu/C (50:10:40) BR/CD, PtSnCu/C (50:40:10) AR/CD electrocatalysts and Pt/C BASF, PtSn/C (75:25) BASF commercial electrocatalysts were tested in single Direct Ethanol Fuel Cell. The results showed the following performance for ethanol electro-oxidation: PtSn/C (50:50) BR/CD > PtSnCu/C (50:40:10) AR/CD > PtSnCu/C > PtSn/C (75:25) BASF > PtSnCu/C (50:10:40) BR/CD > Pt/C BASF. (author)

Electrogenerated chemiluminescence quenching of Ru(bpy){sub 3} {sup 2+} (bpy=2,2 Prime -bipyridine) in the presence of acetaminophen, salicylic acid and their metabolites

Energy Technology Data Exchange (ETDEWEB)

Haslag, Catherine S. [Department of Chemistry, Missouri State University, Springfield, Missouri 65897 (United States); Richter, Mark M., E-mail: MarkRichter@missouristate.edu [Department of Chemistry, Missouri State University, Springfield, Missouri 65897 (United States)

2012-03-15

Quenching of Ru(bpy) {sub 3}{sup 2+} (bpy=2,2 Prime -bipyridine) coreactant electrogenerated chemiluminescence (ECL) has been observed in the presence of acetaminophen, salicylic acid and related complexes. However, no quenching is observed with the acetylsalicylic acid. In most instances, quenching is observed with 100-fold excess of quencher (compared to ECL luminophore) with complete quenching observed between 10,000 and 100,000 fold excess. Fluorescence and UV-vis experiments coupled with bulk electrolysis support the formation of benzoquinone products upon electrochemical oxidation. The mechanism of quenching may involve the interaction of the electrochemically generated benzoquinone species with (i) the {sup Low-Asterisk }Ru(bpy){sub 3}{sup 2+} excited state or (ii) highly energetic coreactant radicals. - Highlights: Black-Right-Pointing-Triangle Efficient quenching of the electrogenerated chemiluminescence is observed. Black-Right-Pointing-Triangle Acetaminophen, salicylic acid and related compounds can be detected. Black-Right-Pointing-Triangle The mechanism of quenching involves benzoquinones formed upon electrolysis.

Unravelling the dependence of hydrogen oxidation kinetics on the size of Pt nanoparticles by in operando nanoplasmonic temperature sensing

DEFF Research Database (Denmark)

Wettergren, Kristina; Hellman, Anders; Cavalca, Filippo Carlo

2015-01-01

We use a noninvasive nanoscale optical-temperature measurement method based on localized surface plasmon resonance to investigate the particle size-dependence of the hydrogen oxidation reaction kinetics on model supported Pt nanocatalysts at atmospheric pressure in operando. With decreasing average...

Metabolism and dosimetry of 106Ru inhaled as 106RuO4 by beagle dogs

International Nuclear Information System (INIS)

Snipes, M.B.

1981-01-01

This report provides metabolism and dosimetry data for inhaled ruthenium developed from studies in Beagle dogs that were exposed by inhalation to 106 RuO 4 . Twenty-six dogs were exposed nose-only to 106 RuO 4 and sacrificed at times from 2 hr to 512 days after inhalation exposure. Ninety-nine percent of the initial body burden was retained with an effective half-time of 1.2 days, 0.7% with a half-time of 14 days and 0.3% with a half-time of 170 days. Initial deposition was primarily in the nasopharyngeal and tracheobronchial regions. Results for deposition and retention of 106 Ru inhaled as 106 RuO 4 in dogs were similar to what has been observed for humans. The data for dogs were used to develop a model to predict potential radiation exposure patterns for humans after inhalation exposure to 106 RuO 4 . The model indicates that for humans the nasopharyngeal region, lower large intestine, and tracheobronchial epithelium would receive approx. 36, 13 and 10 times, respectively, the dose to 500 days after inhalation exposure to 106 RuO 4 that the lung would receive. The nasopharyngeal region should be considered the critical region for inhalation exposures to 106 RuO 4 . (author)

Adherent diamond film deposited on Cu substrate by carbon transport from nanodiamond buried under Pt interlayer

Energy Technology Data Exchange (ETDEWEB)

Liu Xuezhang [School of Materials Science and Engineering, Central South University, Changsha, 410083 (China); Wei Qiuping, E-mail: qiupwei@csu.edu.cn [School of Materials Science and Engineering, Central South University, Changsha, 410083 (China); State Key Laboratory of Powder Metallurgy, Central South University, Changsha, 410083 (China); Yu Zhiming, E-mail: zhiming@csu.edu.cn [School of Materials Science and Engineering, Central South University, Changsha, 410083 (China); State Key Laboratory of Powder Metallurgy, Central South University, Changsha, 410083 (China); Yang Taiming; Zhai Hao [School of Materials Science and Engineering, Central South University, Changsha, 410083 (China)

2013-01-15

Highlights: Black-Right-Pointing-Pointer Adherent polycrystalline diamond films were grown on copper substrate by carbon transport. Black-Right-Pointing-Pointer The nucleation density was increased to 10{sup 11} cm{sup -2}. Black-Right-Pointing-Pointer Diamond films were a composite structure of nano-crystalline diamond layer and micro-crystalline diamond layer. Black-Right-Pointing-Pointer Diamond nucleation was based by carbon dissolving from UDDs to Pt interlayer and formation of sp{sup 3}-bonded diamond clusters at the Pt surface. - Abstract: Diamond film deposited on Cu suffered from poor adhesion mainly due to the large mismatch of thermal expansion coefficients and the lack of affinity between carbon and Cu. Enhancing diamond nucleation by carbon transport from buried nanodiamond through a Pt ultrathin interlayer, adherent diamond film was then deposited on Cu substrate without distinctly metallic interlayer. This novel nucleation mechanism increased diamond nucleation density to 10{sup 11} cm{sup -2}, and developed diamond film with a composite structure of nano-crystalline diamond (NCD) layer and micro-crystalline diamond layer. Diamond film was characterized by the scanning electron microscope (SEM) and Raman spectroscope, respectively. The composition of diamond film/Cu substrate interface was examined by electron probe microanalysis (EPMA). The adhesion of diamond film was evaluated by indentation test. Those results show that a Pt ultrathin interlayer provides stronger chemically bonded interfaces and improve film adhesion.

Destructive impact of molecular noise on nanoscale electrochemical oscillators

Science.gov (United States)

Cosi, Filippo G.; Krischer, Katharina

2017-06-01

We study the loss of coherence of electrochemical oscillations on meso- and nanosized electrodes with numeric simulations of the electrochemical master equation for a prototypical electrochemical oscillator, the hydrogen peroxide reduction on Pt electrodes in the presence of halides. On nanoelectrodes, the electrode potential changes whenever a stochastic electron-transfer event takes place. Electrochemical reaction rate coefficients depend exponentially on the electrode potential and become thus fluctuating quantities as well. Therefore, also the transition rates between system states become time-dependent which constitutes a fundamental difference to purely chemical nanoscale oscillators. Three implications are demonstrated: (a) oscillations and steady states shift in phase space with decreasing system size, thereby also decreasing considerably the oscillating parameter regions; (b) the minimal number of molecules necessary to support correlated oscillations is more than 10 times as large as for nanoscale chemical oscillators; (c) the relation between correlation time and variance of the period of the oscillations predicted for chemical oscillators in the weak noise limit is only fulfilled in a very restricted parameter range for the electrochemical nano-oscillator.

Synthesis of kaolin supported nanoscale zero-valent iron and its degradation mechanism of Direct Fast Black G in aqueous solution

Energy Technology Data Exchange (ETDEWEB)

Jin, Xiaoying; Chen, Zhengxian [Fujian Key Laboratory of Pollution Control and Resource Reuse, School of Environmental Science and Engineering, Fujian Normal University, Fuzhou 350007, Fujian Province (China); Zhou, Rongbing [Institute of Environ Sci and Engineering, Hangzhou Dianzi University, Hangzhou, Zhejiang 310018 (China); Chen, Zuliang, E-mail: Zuliang.chen@unisa.edu.au [Fujian Key Laboratory of Pollution Control and Resource Reuse, School of Environmental Science and Engineering, Fujian Normal University, Fuzhou 350007, Fujian Province (China); Centre for Environmental Risk Assessment and Remediation, University of South Australia, Mawson Lakes, SA 5095 (Australia)

2015-01-15

Graphical abstract: UV–visible spectra of DFBG solution using K-nZVI (1:1) nanoparticles. (a) Before reaction; (b) during reaction; (c) after reaction. - Highlights: • Kaolin-supported Fe{sup 0} nanoparticle (K-nZVI) was synthesized. • Degradation of Direct Fast Black by K-nZVI was studied. • K-nZVI was characterized by SEM, XRD, UV and FIIR. • Degradation mechanism of Direct Fast Black was proposed. - Abstract: Calcinated kaolin supported nanoscale zero-valent iron (K-nZVI) was synthesized and used for the removal of tetrad azo-group dye-Direct Fast Black G (DFBG) from aqueous solution. The results demonstrated that after reacting for 10 min with an initial concentration of DFBG 100 mg L{sup −1} (pH 9.49), 78.60% of DFBG was removed using K-nZVI, while only 41.39% and 12.56% of DFBG were removed using nZVI and kaolin, respectively. K-nZVI with a mass ratio of nZVI nanoparticles versus kaolin at 1:1 was found to have a high degree of reactivity. Furthermore, scanning electron microscopy (SEM) confirmed that nZVI was better dispersed when kaolin was present. XRD patterns indicated that iron oxides were formed after reaction. Fourier transforms infrared spectra (FTIR) and UV–visible demonstrated that the peak in the visible light region of DFBG was degraded and new bands were observed. Kinetics studies showed that the degradation of DFBG fitted well to the pseudo first-order model. The degradation of DFBG by K-nZVI was based on its adsorption onto kaolin and iron oxides, and subsequently reduction using nZVI was proposed. A significant outcome emerged in that 99.84% of DFBG in wastewater was removed using K-nZVI after reacting for 60 min.

Synthesis of kaolin supported nanoscale zero-valent iron and its degradation mechanism of Direct Fast Black G in aqueous solution

International Nuclear Information System (INIS)

Jin, Xiaoying; Chen, Zhengxian; Zhou, Rongbing; Chen, Zuliang

2015-01-01

Graphical abstract: UV–visible spectra of DFBG solution using K-nZVI (1:1) nanoparticles. (a) Before reaction; (b) during reaction; (c) after reaction. - Highlights: • Kaolin-supported Fe 0 nanoparticle (K-nZVI) was synthesized. • Degradation of Direct Fast Black by K-nZVI was studied. • K-nZVI was characterized by SEM, XRD, UV and FIIR. • Degradation mechanism of Direct Fast Black was proposed. - Abstract: Calcinated kaolin supported nanoscale zero-valent iron (K-nZVI) was synthesized and used for the removal of tetrad azo-group dye-Direct Fast Black G (DFBG) from aqueous solution. The results demonstrated that after reacting for 10 min with an initial concentration of DFBG 100 mg L −1 (pH 9.49), 78.60% of DFBG was removed using K-nZVI, while only 41.39% and 12.56% of DFBG were removed using nZVI and kaolin, respectively. K-nZVI with a mass ratio of nZVI nanoparticles versus kaolin at 1:1 was found to have a high degree of reactivity. Furthermore, scanning electron microscopy (SEM) confirmed that nZVI was better dispersed when kaolin was present. XRD patterns indicated that iron oxides were formed after reaction. Fourier transforms infrared spectra (FTIR) and UV–visible demonstrated that the peak in the visible light region of DFBG was degraded and new bands were observed. Kinetics studies showed that the degradation of DFBG fitted well to the pseudo first-order model. The degradation of DFBG by K-nZVI was based on its adsorption onto kaolin and iron oxides, and subsequently reduction using nZVI was proposed. A significant outcome emerged in that 99.84% of DFBG in wastewater was removed using K-nZVI after reacting for 60 min

Adsorption and diffusion of Ru adatoms on Ru(0001)-supported graphene: Large-scale first-principles calculations

Energy Technology Data Exchange (ETDEWEB)

Han, Yong; Evans, James W. [Department of Physics and Astronomy, Iowa State University, Ames, Iowa 50011, USA and Ames Laboratory—U.S. Department of Energy, Iowa State University, Ames, Iowa 50011 (United States)

2015-10-28

Large-scale first-principles density functional theory calculations are performed to investigate the adsorption and diffusion of Ru adatoms on monolayer graphene (G) supported on Ru(0001). The G sheet exhibits a periodic moiré-cell superstructure due to lattice mismatch. Within a moiré cell, there are three distinct regions: fcc, hcp, and mound, in which the C{sub 6}-ring center is above a fcc site, a hcp site, and a surface Ru atom of Ru(0001), respectively. The adsorption energy of a Ru adatom is evaluated at specific sites in these distinct regions. We find the strongest binding at an adsorption site above a C atom in the fcc region, next strongest in the hcp region, then the fcc-hcp boundary (ridge) between these regions, and the weakest binding in the mound region. Behavior is similar to that observed from small-unit-cell calculations of Habenicht et al. [Top. Catal. 57, 69 (2014)], which differ from previous large-scale calculations. We determine the minimum-energy path for local diffusion near the center of the fcc region and obtain a local diffusion barrier of ∼0.48 eV. We also estimate a significantly lower local diffusion barrier in the ridge region. These barriers and information on the adsorption energy variation facilitate development of a realistic model for the global potential energy surface for Ru adatoms. This in turn enables simulation studies elucidating diffusion-mediated directed-assembly of Ru nanoclusters during deposition of Ru on G/Ru(0001)

Understanding Pt-ZnO:In Schottky nanocontacts by conductive atomic force microscopy

Science.gov (United States)

Chirakkara, Saraswathi; Choudhury, Palash Roy; Nanda, K. K.; Krupanidhi, S. B.

2016-04-01

Undoped and In doped ZnO (IZO) thin films are grown on Pt coated silicon substrates Pt/Si by pulsed laser deposition to fabricate Pt/ZnO:In Schottky diodes. The Schottky diodes were investigated by conventional two-probe current-voltage (I-V) measurements and by the I-V spectroscopy tool of conductive atomic force microscopy (C-AFM). The large deviation of the ideality factor from unity and the temperature dependent Schottky barrier heights (SBHs) obtained from the conventional method imply the presence of inhomogeneous interfaces. The inhomogeneity of SBHs is confirmed by C-AFM. Interestingly, the I-V curves at different points are found to be different, and the SBHs deduced from the point diodes reveal inhomogeneity at the nanoscale at the metal-semiconductor interface. A reduction in SBH and turn-on voltage along with enhancement in forward current are observed with increasing indium concentration.

Compositional changes of human hair melanin resulting from bleach treatment investigated by nanoscale secondary ion mass spectrometry.

Science.gov (United States)

Kojima, Toru; Yamada, Hiromi; Isobe, Mitsuru; Yamamoto, Toshihiko; Takeuchi, Miyuki; Aoki, Dan; Matsushita, Yasuyuki; Fukushima, Kazuhiko

2014-11-01

It is important to understand the influence of bleach treatment on human hair because it is one of the most important chemical treatments in hair cosmetic processes. A comparison of the elemental composition of melanin between virgin hair and bleached hair would provide important information about the structural changes of melanin. To investigate the elemental composition of melanin granules in virgin black hair and bleached hair, these hair cross-sections are analyzed by using a nanoscale secondary ion mass spectrometry (NanoSIMS). The virgin black hair and bleached hair samples were embedded in resin and smooth hair cross-sections were obtained using an ultramicrotome. NanoSIMS measurements were performed using a Cs(+) primary ion beam to detect negative secondary ions. More intensive (16) O(-) ions were detected from the melanin granules of bleached hair than from those of virgin black hair in NanoSIMS (16) O(-) ion image. In addition, it was indicated that (16) O(-) ion intensity and (16) O(-) /(12) C(14) N(-) ion intensity ratio of melanin granules in bleached hair were higher than those in virgin black hair. Nanoscale secondary ion mass spectrometry analysis of the cross-sections of virgin black hair and bleached hair indicated that the oxygen content in melanin granules was increased by bleach treatment. © 2014 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

Nanoscale Tapered Pt Bottom Electrode Fabricated by FIB for Low Power and Highly Stable Operations of Phase Change Memory

International Nuclear Information System (INIS)

Shi-Long, Lv; Zhi-Tang, Song; Yan, Liu; Song-Lin, Feng

2010-01-01

Phase change random access memory (PC-RAM) based on Si 2 Sb 2 Te 5 with a Pt tapered heating electrode (Pt-THE), which is fabricated using a focus ion beam (FIB), is investigated. Compared with the tungsten electrode, the Pt-THE facilitates the temperature rise in phase change material, which causes the decrease of reset voltage from 3.6 to 2.7 V. The programming region of the cell with the Pt-THE is smaller than that of the cell with a cylindrical tungsten heating electrode. The improved performance of the PC-RAM with a Pt-THE is attributed to the higher resistivity and lower thermal conductivity of the Pt electrode, and the reduction of the programming region, which is also verified by thermal simulation. (cross-disciplinary physics and related areas of science and technology)

Wall-to-liquid mass transfer in fluidized beds and vertical transport of inert particles

Directory of Open Access Journals (Sweden)

NEVENKA BOSKOVIC–VRAGOLOVIC

2007-11-01

Full Text Available The electrochemical oxidation of methanol in NaOH solution was examined on a thin film Pt2Ru3/C electrode. The XRD pattern revealed that the Pt2Ru3 alloy consisted of a solid solution of Ru in Pt and a small amount of Ru or a solid solution of Pt in Ru. It was shown that in alkaline solution, the difference in activity between Pt/C and Pt2Ru3/C is significantly smaller than in acid solution. It is proposed that the reaction follows a quasi bifunctional mechanism. The kinetic parameters indicated that the chemical reaction between adsorbed COad and OHad species could be the rate limiting step.

Facile synthesis of a platinum-lead oxide nanocomposite catalyst with high activity and durability for ethanol electrooxidation.

Science.gov (United States)

Yang, Wei-Hua; Wang, Hong-Hui; Chen, De-Hao; Zhou, Zhi-You; Sun, Shi-Gang

2012-12-21

Aimed at searching for highly active and stable nano-scale Pt-based catalysts that can improve significantly the energy conversion efficiency of direct ethanol fuel cells (DEFCs), a novel Pt-PbO(x) nanocomposite (Pt-PbO(x) NC) catalyst with a mean size of 3.23 nm was synthesized through a simple wet chemistry method without using a surfactant, organometallic precursors and high temperature. Electrocatalytic tests demonstrated that the as-prepared Pt-PbO(x) NC catalyst possesses a much higher catalytic activity and a longer durability than Pt nanoparticles (nm-Pt) and commercial Pt black catalysts for ethanol electrooxidation. For instance, Pt-PbO(x) NC showed an onset potential that was 30 mV and 44 mV less positive, together with a peak current density 1.7 and 2.6 times higher than those observed for nm-Pt and Pt black catalysts in the cyclic voltammogram tests. The ratio of current densities per unit Pt mass on Pt-PbO(x) NC, nm-Pt and Pt black catalysts is 27.3 : 3.4 : 1 for the long-term (2 hours) chronoamperometric experiments measured at -0.4 V (vs. SCE). In situ FTIR spectroscopic studies revealed that the activity of breaking C-C bonds of ethanol of the Pt-PbO(x) NC is as high as 5.17 times that of the nm-Pt, which illustrates a high efficiency of ethanol oxidation to CO(2) on the as-prepared Pt-PbO(x) NC catalyst.

Laser Spectroscopy of Ruthenium Containing Diatomic Molecules: RuH/D and RuP.

Science.gov (United States)

Adam, Allan G.; Konder, Ricarda M.; Nickerson, Nicole M.; Linton, Colan; Tokaryk, D. W.

2015-06-01

In the last few years, the Cheung group in Hong Kong and the Steimle group in Arizona have successfully studied several ruthenium containing diatomic molecules, RuX (X =C, O, N, B, using the laser-ablation molecular jet technique. Based on this success, the UNB spectroscopy group decided to try and find the optical signatures of other RuX molecules. Using CH_3OH and PH_3 as reactant gases, the RuH and RuP diatomic molecules have been detected in surveys of the 420 - 675 nm spectral region. RuD has also been made using fully deuterated methanol as a reactant. Dispersed fluorescence experiments have been performed to determine ground state vibrational frequencies and the presence of any low-lying electronic states. Rotationally resolved spectra for these molecules have also been taken and the analysis is proceeding. The most recent results will be presented. F. Wang et al., Journal of Chemical Physics 139, 174318 (2013). N. Wang et al., Journal of Physical Chemistry A 117, 13279 (2013). T. Steimle et al., Journal of Chemical Physics 119, 12965 (2003). N. Wang et al., Chemical Physics Letters 547, 21 (2012).

Crystal structures, stability, electronic and elastic properties of 4d and 5d transition metal monoborides: First-principles calculations

Energy Technology Data Exchange (ETDEWEB)

Wang, Y.; Chen, W. [International Center for New-Structured Materials (ICNSM), Zhejiang University, and Laboratory of New-Structured Materials, State Key Laboratory of Silicon Materials, Department of Materials Science and Engineering, Zhejiang University, Hangzhou 310027 (China); Chen, X.; Liu, H.Y. [State Key Laboratory of Superhard Materials, Jilin University, Changchun 130012 (China); Ding, Z.H.; Ma, Y.M. [State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University, Changchun 130012 (China); Wang, X.D.; Cao, Q.P. [International Center for New-Structured Materials (ICNSM), Zhejiang University, and Laboratory of New-Structured Materials, State Key Laboratory of Silicon Materials, Department of Materials Science and Engineering, Zhejiang University, Hangzhou 310027 (China); Jiang, J.Z., E-mail: jiangjz@zju.edu.cn [International Center for New-Structured Materials (ICNSM), Zhejiang University, and Laboratory of New-Structured Materials, State Key Laboratory of Silicon Materials, Department of Materials Science and Engineering, Zhejiang University, Hangzhou 310027 (China)

2012-10-15

Highlights: Black-Right-Pointing-Pointer Changes from NaCl-, WC- to anti-NiAs-type structures are for 4d and 5d metal monoborides. Black-Right-Pointing-Pointer Vickers hardnesses of monoborides are relatively low. Black-Right-Pointing-Pointer B-vacancies cause the difference in lattice parameters for IrB and PtB. Black-Right-Pointing-Pointer Nonstoichiometric IrB and PtB phases synthesized. - Abstract: The crystal structures, stability, electronic and elastic properties of 4d and 5d transition metal monoborides have been studied by first principles calculations. It is found that NaCl-type ZrB, NbB, MoB, HfB, TaB and WB, WC-type TcB, RuB, ReB, OsB and IrB, and anti-NiAs-type RhB and PdB are thermodynamically stable at zero pressure. They all are metallic. The Vickers hardnesses of these monoborides are relatively low as compared with monocarbides and mononitrides. It is clarified that the presence of B-vacancies is the origin for the difference of lattice parameters between theoretical and experimental results for WC-type IrB and anti-NiAs-type PtB while IrB and PtB with stoichiometry from calculations are revealed to be mechanically unstable and dynamically unstable, respectively.

Thermodynamic assessment of the Al-Ru system

CSIR Research Space (South Africa)

Prins, SN

2003-03-01

Full Text Available describes the order disorder transformation with one Gibbs energy function. The RuAl6 phase was described as a stoichiometric phase and the remaining intermetallic phases (Ru4Al13, RuAl2 and Ru2Al3) were modelled with the sublattice model. The solubility...

Ruthenium and osmium carbonyl nitrosyl complexes: Matrix infrared spectra and density functional calculations for M(CO){sub 2}(NO){sub 2} and M(CO)(NO) (M = Ru, Os)

Energy Technology Data Exchange (ETDEWEB)

Song, Zhenjun [Department of Chemistry, Tongji University, Shanghai 200092 (China); Wang, Xuefeng, E-mail: xfwang@tongji.edu.cn [Department of Chemistry, Tongji University, Shanghai 200092 (China); Key Laboratory of Yangtze River Water Environment, Ministry of Education, Tongji University (China)

2012-10-15

Highlights: Black-Right-Pointing-Pointer Laser-ablated ruthenium or osmium atom reactions with CO and NO mixtures in solid argon. Black-Right-Pointing-Pointer Metal carbonyl nitrosyls including M(CO)(NO) and 18-electron configuration M(CO){sub 2}(NO){sub 2} molecules (M = Ru, Os). Black-Right-Pointing-Pointer The observed absorption bands of reaction products are identified by isotopic substitution and DFT calculations. Black-Right-Pointing-Pointer The bonding and reaction mechanism are discussed in detail. -- Abstract: Laser-ablated ruthenium or osmium atom reactions with CO and NO mixtures in solid argon produce unsaturated metal carbonyl nitrosyls including M(CO)(NO) and 18-electron configuration M(CO){sub 2}(NO){sub 2} molecules (M = Ru, Os). The observed absorption bands of reaction products are identified by isotopic substitution, isotopic ratios and isotopic distributions ({sup 13}CO, {sup 15}NO, and mixtures). DFT (B3LYP and BP86) vibrational fundamental calculations reproduce observed frequencies and isotopic shifts very well. The bonding and reaction mechanism are discussed.

Determination of itopride hydrochloride by high-performance liquid chromatography with Ru(bpy)3(2+) electrogenerated chemiluminescence detection.

Science.gov (United States)

Sun, Yonghua; Zhang, Zhujun; Xi, Zhijun; Shi, Zuolong; Tian, Wei

2009-08-26

In this work, a stable electrogenerated chemiluminescence (ECL) detector was developed. The detector was prepared by packing cation-exchanged resin particles in a glass tube, followed by inserting Pt wires (working electrode) in this tube and sealing. The leakage of Ru(bpy)(3)(2+) can be compensated by adding a small amount of Ru(bpy)(3)(2+) into solution phase. Coupled with high-performance liquid chromatography separation, the detector has been used for determination of itopride hydrochloride in human serum. Under the optimal conditions, the ECL intensity has a linear relationship with the concentration of itopride hydrochloride in the range of 1.0 x 10(-8) g mL(-1) to 1.0 x 10(-6) g mL(-1) and the detection limit was 3 x 10(-9) g mL(-1) (S/N=3). The as-prepared ECL detector displayed good sensitivity and stability.

Synthesis of bimetallic Pt-Pd core-shell nanocrystals and their high electrocatalytic activity modulated by Pd shell thickness

Science.gov (United States)

Li, Yujing; Wang, Zhi Wei; Chiu, Chin-Yi; Ruan, Lingyan; Yang, Wenbing; Yang, Yang; Palmer, Richard E.; Huang, Yu

2012-01-01

Bimetallic Pt-Pd core-shell nanocrystals (NCs) are synthesized through a two-step process with controlled Pd thickness from sub-monolayer to multiple atomic layers. The oxygen reduction reaction (ORR) catalytic activity and methanol oxidation reactivity of the core-shell NCs for fuel cell applications in alkaline solution are systematically studied and compared based on different Pd thickness. It is found that the Pd shell helps to reduce the over-potential of ORR by up to 50mV when compared to commercial Pd black, while generating up to 3-fold higher kinetic current density. The carbon monoxide poisoning test shows that the bimetallic NCs are more resistant to the CO poisoning than Pt NCs and Pt black. It is also demonstrated that the bimetallic Pt-Pd core-shell NCs can enhance the current density of the methanol oxidation reaction, lowering the over-potential by 35 mV with respect to the Pt core NCs. Further investigation reveals that the Pd/Pt ratio of 1/3, which corresponds to nearly monolayer Pd deposition on Pt core NCs, gives the highest oxidation current density and lowest over-potential. This study shows for the first time the systematic investigation of effects of Pd atomic shells on Pt-Pd bimetallic nanocatalysts, providing valuable guidelines for designing high-performance catalysts for fuel cell applications.Bimetallic Pt-Pd core-shell nanocrystals (NCs) are synthesized through a two-step process with controlled Pd thickness from sub-monolayer to multiple atomic layers. The oxygen reduction reaction (ORR) catalytic activity and methanol oxidation reactivity of the core-shell NCs for fuel cell applications in alkaline solution are systematically studied and compared based on different Pd thickness. It is found that the Pd shell helps to reduce the over-potential of ORR by up to 50mV when compared to commercial Pd black, while generating up to 3-fold higher kinetic current density. The carbon monoxide poisoning test shows that the bimetallic NCs are more

Preparation and evaluation of a multi-component catalyst by using a co-sputtering system for anodic oxidation of ethanol

Energy Technology Data Exchange (ETDEWEB)

Tanaka, S.; Usui, Y.; Kimura, O. [Environmental Technology R and D Center, Ricoh Company, Ltd., 16-1 Shinei-cho, Tsuzuki-ku, Yokohama 224-0035 (Japan); Umeda, M. [Department of Chemistry, Faculty of Engineering, Nagaoka University of Technology, Kamitomioka 1603-1, Nagaoka, Niigata 940-2188 (Japan); Ojima, H.; Uchida, I. [Department of Applied Chemistry, Graduate School of Engineering, Tohoku University, Aramaki-Aoba 07, Aoba-ku, Sendai 980-8579 (Japan)

2005-12-01

In this study, a remarkable promotion of ethanol electrooxidation by a Pt--Ru-W alloy is reported for an improvement of the anodic reaction of a direct ethanol fuel cell (DEFC). Pt-based binary and ternary electrocatalysts including Pt-Ru-W deposited onto a Au substrate were prepared by co-sputtering process. By using this process, several metals can be arranged simultaneously and uniformly. The catalysts deposited onto Au were evaluated for anodic electrode in 1moldm{sup -3} ethanol+0.5 moldm{sup -3} sulfuric acid by electrochemical measurements. The performance of Pt-Ru-W was desirable in comparison to that of binary alloys, such as Pt-W, Pt-Sn and Pt-Ru, which exhibit higher catalytic activity than single Pt metal layer electrode. Ethanol electrooxidation on Pt-Ru-W alloy showed a cathodic shift in the onset potential and a higher current density than the binary alloy electrodes. It was found that Pt-Ru-W ternary catalyst effects to not only methanol oxidation reaction but also ethanol oxidation reaction and that the current density of ethanol oxidation with Pt-Ru-W is about 2/3 to that of methanol at 0.5V versus Ag/AgCl. The onset potentials for the ethanol oxidation reaction matched well the anodic peak potentials of the background volutammograms, i.e., 0.15V versus Ag/AgCl for Pt-Ru-W and 0.35V versus Ag/AgCl for Pt-W and Pt-Ru electrodes. That is, it was postulated that the background peak current indicates the generation of oxide species like metal-OH necessary to complete the ethanol oxidation to CO{sub 2}. (author)

Significance of β-dehydrogenation in ethanol electro-oxidation on platinum doped with Ru, Rh, Pd, Os and Ir.

Science.gov (United States)

Sheng, Tian; Lin, Wen-Feng; Hardacre, Christopher; Hu, P

2014-07-14

In the exploration of highly efficient direct ethanol fuel cells (DEFCs), how to promote the CO2 selectivity is a key issue which remains to be solved. Some advances have been made, for example, using bimetallic electrocatalysts, Rh has been found to be an efficient additive to platinum to obtain high CO2 selectivity experimentally. In this work, the mechanism of ethanol electrooxidation is investigated using the first principles method. It is found that CH3CHOH* is the key intermediate during ethanol electrooxidation and the activity of β-dehydrogenation is the rate determining factor that affects the completeness of ethanol oxidation. In addition, a series of transition metals (Ru, Rh, Pd, Os and Ir) are alloyed on the top layer of Pt(111) in order to analyze their effects. The elementary steps, α-, β-C-H bond and C-C bond dissociations, are calculated on these bimetallic M/Pt(111) surfaces and the formation potential of OH* from water dissociation is also calculated. We find that the active metals increase the activity of β-dehydrogenation but lower the OH* formation potential resulting in the active site being blocked. By considering both β-dehydrogenation and OH* formation, Ru, Os and Ir are identified to be unsuitable for the promotion of CO2 selectivity and only Rh is able to increase the selectivity of CO2 in DEFCs.

One-pot synthesis of Pd-Pt@Pd core-shell nanocrystals with enhanced electrocatalytic activity for formic acid oxidation

KAUST Repository

Yuan, Qiang

2014-01-01

Well-defined Pd-Pt@Pd core-shell nanocrystals with a Pd-Pt alloy core and a conformal Pd shell of ~2-3 nm were directly synthesized through a one-pot, aqueous solution approach without any preformed Pd or Pt seeds. These Pd-Pt@Pd core-shell nanocrystals show an enhanced electrocatalytic activity for formic acid oxidation compared with commercial Pd black. This journal is © 2014 The Royal Society of Chemistry.

Effectiveness of matured Morus nigra L. (black mulberry) fruit extract ...

African Journals Online (AJOL)

ajl yemi

2011-11-14

Nov 14, 2011 ... Morin, a form of flavonoid that is highly found in black mulberry, has been ... determined by the method of Shimoi et al. (1994) with the .... quantified by DAD following HPLC separation at 280 nm for CA and. NA, 254 nm for RU, ...

Electronic structure of Pt-Co cathode catalysts in membrane electrolyte assembly observed by X-ray absorption fine structure spectroscopy with different probing depth

International Nuclear Information System (INIS)

Kobayashi, M.; Hidai, S.; Niwa, H.; Harada, Y.; Oshima, M.; Ofuchi, H.; Nakamori, Y.; Aoki, T.

2010-01-01

Electronic structures of Pt-Co cathode and Pt-Ru anode catalysts in membrane electrolyte assemblies (MEAs) for polymer electrolyte fuel cell have been investigated using X-ray absorption near edge structure (XANES) spectroscopy, and the changes of electronic structures accompanied with degradation have been observed by comparison between spectra obtained by fluorescence-yield (FY) and conversion-electron-yield (CEY) methods, probing depths of which are several hundreds μm and ∼100 nm, respectively. The Co K XANES spectra of the as-fabricated MEA show that the Co atoms in the cathode are metallic and oxidized Co ions exist at the interface between the cathode and electrolyte. The spectra of the long-time operated MEA suggest that the oxidation of Co makes progress with degradation of the cathode catalysts. In contrast to the Co K XANES spectra, the line shape of the Ru K XANES spectra is unchanged even after the long-time operation.

Low content of Pt supported on Ni-MoC{sub x}/carbon black as a highly durable and active electrocatalyst for methanol oxidation, oxygen reduction and hydrogen evolution reactions in acidic condition

Energy Technology Data Exchange (ETDEWEB)

Zhang, Yan; Zang, Jianbing; Jia, Shaopei; Tian, Pengfei; Han, Chan; Wang, Yanhui, E-mail: diamond_wangyanhui@163.com

2017-08-01

Highlights: • Ni-MoC{sub x}/C catalyst support was synthesized by a two-step method. • 10Pt/Ni-MoC{sub x}/C was an active and durable low Pt catalyst for MOR, ORR and HER. • The high stability of 10Pt/Ni-MoC{sub x}/C was ascribed to the anchoring effect of MoC{sub x}. • High activity of 10Pt/Ni-MoC{sub x}/C was due to a synergistic of Pt, Ni, MoO{sub x} and MoC{sub x}. - Abstract: Nickel and molybdenum carbide modified carbon black (Ni-MoC{sub x}/C) was synthesized by a two-step microwave-assisted deposition/carbonthermal reduction method and characterized by X-ray diffraction, transmission electron microscopy, energy dispersive spectroscopy and X-ray photoelectron spectroscopy. The as-prepared Ni-MoC{sub x}/C supported Pt (10 wt%) electrocatalyst (10Pt/Ni-MoC{sub x}/C) was synthesized through a microwave-assisted reduction method and 10Pt/Ni-MoC{sub x}/C exhibited high electrocatalytic activity for methanol oxidation, oxygen reduction and hydrogen evolution reactions. Results showed that 10Pt/Ni-MoC{sub x}/C electrocatalyst had better electrocatalytic activity and stability performance than 20 wt% Pt/C (20Pt/C) electrocatalyst. Among them, the electrochemical surface area of 10Pt/Ni-MoC{sub x}/C reached 68.4 m{sup 2} g{sup −1}, which was higher than that of 20Pt/C (63.2 m{sup 2} g{sup −1}). The enhanced stability and activity of 10Pt/Ni-MoC{sub x}/C electrocatalyst were attributed to: (1) an anchoring effect of Ni and MoC{sub x} formed during carbonthermal reduction process; (2) a synergistic effect among Pt, Ni, MoO{sub x} and MoC{sub x}. These findings indicated that 10Pt/Ni-MoC{sub x}/C was a promising electrocatalyst for direct methanol fuel cells.

Identification of nanoscale structure and morphology reconstruction in oxidized a-SiC:H thin films

Energy Technology Data Exchange (ETDEWEB)

Vasin, A.V.; Rusavsky, A.V.; Nazarov, A.N.; Lysenko, V.S.; Lytvyn, P.M.; Strelchuk, V.V. [Lashkaryov Institute of Semiconductor Physics, 41 Nauki Pr., Kiev 03028 (Ukraine); Kholostov, K.I.; Bondarenko, V.P. [Belarusian State University of Informatics and Radioelectronics, 6P. Brovki Str., Minsk 220013 (Belarus); Starik, S.P. [Bakul Institute of Superhard Materials, 2 Avtzavodskaya Str., Kiev 04074 (Ukraine)

2012-11-01

Highlights: Black-Right-Pointing-Pointer Increase of magnetron discharge power results in densification of a-SiC:H thin films. Black-Right-Pointing-Pointer The denser a-SiC:H material the better resistance to oxidation by oxygen. Black-Right-Pointing-Pointer Oxidation of soft a-SiC:H films can result in increase of electric conductivity. Black-Right-Pointing-Pointer Formation of graphitic clusters was found in a-SiC:H after annealing in oxygen. - Abstract: Oxidation behavior of a-SiC:H layers deposited by radio-frequency magnetron sputtering technique was examined by Kelvin probe force microscopy (KPFM) in combination with scanning electron microscopy, Fourier-transform infra-red spectroscopy and submicron selected area Raman scattering spectroscopy. Partially oxidized a-SiC:H samples (oxidation at 600 Degree-Sign C in oxygen) were examined to clarify mechanism of the oxidation process. Nanoscale and microscale morphological defects (pits) with dimension of about 50 nm and several microns respectively have appeared after thermal treatment. KPFM measurements exhibited the surface potential of the material in micro pits is significantly smaller in comparison with surrounding material. Submicron RS measurements indicates formation of graphite-like nano-inclusions in the pit defects. We conclude that initial stage of oxidation process in a-SiC:H films takes place not homogeneously throughout the layer but it is initiated in local nanoscale regions followed by spreading over all layer.

Effect of carbon additive on microstructure evolution and magnetic properties of epitaxial FePt (001) thin films

International Nuclear Information System (INIS)

Ding, Y.F.; Chen, J.S.; Liu, E.; Lim, B.C.; Hu, J.F.; Liu, B.

2009-01-01

FePt:C thin films were deposited on CrRu underlayers by DC magnetron co-sputtering. The effects of C content, FePt:C film thickness and substrate temperature on the microstructural and magnetic properties of the epitaxial FePt (001) films were studied. Experimental results showed that even with 30 vol.% C doping, the FePt films could keep a (001) preferred orientation at 350 deg. C . When a FePt:C film was very thin (< 5 nm), the film had a continuous microstructure instead of a granual structure with C diffused onto the film surface. With further increased film thickness, the film started to nucleate and formed a column microstructure over continuous FePt films. A strong exchange coupling in the FePt:C films was believed to be due to the presence of a thin continuous FePt layer attributed to the carbon diffusion during the initial stage of the FePt:C film growth. Despite the presence of a strong exchange coupling in the FePt:C (20 vol.% C) film, the SNR ratio of the FePt:C media was about 10 dB better than that of the pure FePt media. The epitaxial growth of the FePt:C films on the Pt layers was observed from high resolution TEM cross sectional images even for the films grown at about 200 deg. C . The TEM images did not show an obvious change in the morphology of the FePt:C films deposited at different temperatures (from 200 deg. C to 350 deg. C ), though the ordering degree and coercivity of the films increased with increased substrate temperature

RuPd, RuCo, PdCo and RuPdCo materials as candidates for cathode catalyzers in PEM fuel cells; Materiales RuPd, RuCo, PdCo y RuPdCo como candidatos a catalizadores catodicos en celdas de combustible tipo PEM

Energy Technology Data Exchange (ETDEWEB)

Leyva Noyola, Fatima; Solorza Feria, Omar [Centro de Investigacion y Estudios Superiores del IPN, Mexico, D.F. (Mexico)]. E-mail: fleyva@cinvestav.mx

2009-09-15

This work reports on the catalytic activity of RuPd, RuCo, PdCo and RuPdCo material for oxygen reduction reaction (ORR). These materials were synthesized using chemical reduction with NaBH{sub 4} as a reducing agent in THF, in ambient temperature and pressure conditions. The evaluation of the catalytic activity was done using cyclic voltamperometry (CV) and rotary disc electrode (RDE) in H{sub 2}SO{sub 4} 0.5 M. The kinetic results showed that the electrochemical reaction involves 4 electrons and the transfer of the first electron is the determinant stage. The values of {alpha}, i0 and the Tafel slope were very similar for the four materials studied, around 0.4, 5x10{sup -6} mA cm{sup -2} and 60 mV dec-1, respectively. Although these values are less than those reported for nanostructured platinum, they are better than those reported for other materials such as pure Pd, which enables them to be considered as cathode catalysts for a proton exchange membrane fuel cell. [Spanish] En este trabajo se reporta la actividad catalitica de los materiales RuPd, RuCo, PdCo y RuPdCo para la reaccion de reduccion de oxigeno (RRO). Estos materiales fueron sintetizados por el metodo de reduccion quimica, usando NaBH{sub 4} como agente reductor en THF, en condiciones de temperatura y presion ambiental. La evaluacion de la actividad catalitica fue realizada usando Voltamperometria Ciclica (VC) y Electrodo Disco Rotatorio (EDR) en H{sub 2}SO{sub 4} 0.5 M. Los resultados cineticos mostraron que la reaccion electroquimica procede por la via de 4 electrones y la etapa determinante es la transferencia del primer electron. Los valores de {alpha}, i0 y pendiente de Tafel fueron muy similares para los 4 materiales estudiados, siendo estos de alrededor de 0.4, 5x10{sup -6} mA cm{sup -2} y 60 mV dec{sup -1}, respectivamente. Sin embargo, aun cuando estos valores son menores que los reportados para platino nanoestructurado, son mejores que los reportados para otros materiales como el Pd puro

Dynamics of test black holes

International Nuclear Information System (INIS)

Epikhin, E.N.

1981-01-01

A concept of a test object is introduced. This definition includes also small black holes. Reduced approximation of testing permits to unambiguously introduce a concept of background space-time. Dynamic values for test objects are introduced by means of the Noether theorem which gave the possibility to covariantly generalize pseudotensor of the Papapetru energy-momentum for the case of curved background space-time. Additional use of radiation approximation and the accountancy of the zero and first momenta of dynamic values lead to the conclusion that motion of the test object (including small black holes) is subordinated to the Matthiessen-Papapetru equations. The above results are testified to the accountancy of a proper gravitational field of the test object in integrated dynamic values [ru

Atomic layer deposition of ruthenium surface-coating on porous platinum catalysts for high-performance direct ethanol solid oxide fuel cells

Science.gov (United States)

Jeong, Heon Jae; Kim, Jun Woo; Jang, Dong Young; Shim, Joon Hyung

2015-09-01

Pt-Ru bi-metallic catalysts are synthesized by atomic layer deposition (ALD) of Ru surface-coating on sputtered Pt mesh. The catalysts are evaluated in direct ethanol solid oxide fuel cells (DESOFCs) in the temperature range of 300-500 °C. Island-growth of the ALD Ru coating is confirmed by transmission electron microscopy and X-ray photoelectron spectroscopy (XPS) analyses. The performance of the DESOFCs is evaluated based on the current-voltage output and electrochemical impedance spectroscopy. Genuine reduction of the polarization impedance, and enhanced power output with improved surface kinetics are achieved with the optimized ALD Ru surface-coating compared to bare Pt. The chemical composition of the Pt/ALD Ru electrode surface after fuel cell operation is analyzed via XPS. Enhanced cell performance is clearly achieved, attributed to the effective Pt/ALD Ru bi-metallic catalysis, including oxidation of Cdbnd O by Ru, and de-protonation of ethanol and cleavage of C-C bonds by Pt, as supported by surface morphology analysis which confirms formation of a large amount of carbon on bare Pt after the ethanol-fuel-cell test.

Integrated high-efficiency Pt/carbon nanotube arrays for PEM fuel cells

Energy Technology Data Exchange (ETDEWEB)

Zhang, Weimin; Minett, Andrew I.; Zhao, Jie; Razal, Joselito M.; Wallace, Gordon G.; Romeo, Tony; Chen, Jun [Intelligent Polymer Research Institute, AIIM Facility, Innovation Campus, University of Wollongong, NSW 2522 (Australia); Gao, Mei [Division of Materials Science and Engineering, CSIRO, Bayview Ave, Clayton, VIC 3168 (Australia)

2011-07-15

A facile strategy to deposit Pt nanoparticles with various metal-loading densities on vertically aligned carbon nanotube (ACNT) arrays as electrocatalysts for proton exchange membrane (PEM) fuel cells is described. The deposition is achieved by electrostatic adsorption of the Pt precursor on the positively charged polyelectrolyte functionalized ACNT arrays and subsequent reduction by L-ascorbic acid. The application of the aligned electrocatalysts in fuel cells is realized by transferring from a quartz substrate to nafion membrane using a hot-press procedure to fabricate the membrane electrode assembly (MEA). It is shown that the MEA with vertically aligned structured electrocatalysts provides better Pt utilization than that with Pt on conventional carbon nanotubes or carbon black, resulting in higher fuel cell performance. (Copyright copyright 2011 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Small-sized and contacting Pt-WC nanostructures on graphene as highly efficient anode catalysts for direct methanol fuel cells.

Science.gov (United States)

Wang, Ruihong; Xie, Ying; Shi, Keying; Wang, Jianqiang; Tian, Chungui; Shen, Peikang; Fu, Honggang

2012-06-11

The synergistic effect between Pt and WC is beneficial for methanol electro-oxidation, and makes Pt-WC catalyst a promising anode candidate for the direct methanol fuel cell. This paper reports on the design and synthesis of small-sized and contacting Pt-WC nanostructures on graphene that bring the synergistic effect into full play. Firstly, DFT calculations show the existence of a strong covalent interaction between WC and graphene, which suggests great potential for anchoring WC on graphene with formation of small-sized, well-dispersed WC particles. The calculations also reveal that, when Pt attaches to the pre-existing WC/graphene hybrid, Pt particles preferentially grow on WC rather than graphene. Our experiments confirmed that highly disperse WC nanoparticles (ca. 5 nm) can indeed be anchored on graphene. Also, Pt particles 2-3 nm in size are well dispersed on WC/graphene hybrid and preferentially grow on WC grains, forming contacting Pt-WC nanostructures. These results are consistent with the theoretical findings. X-ray absorption fine structure spectroscopy further confirms the intimate contact between Pt and WC, and demonstrates that the presence of WC can facilitate the crystallinity of Pt particles. This new Pt-WC/graphene catalyst exhibits a high catalytic efficiency toward methanol oxidation, with a mass activity 1.98 and 4.52 times those of commercial PtRu/C and Pt/C catalysts, respectively. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Tailoring Ruthenium Exposure to Enhance the Performance of fcc Platinum@Ruthenium Core-Shell Electrocatalysts in the Oxygen Evolution Reaction

KAUST Repository

AlYami, Noktan

2016-05-17

The catalytic properties of noble metal nanocrystals are a function of their size, structure, and surface composition. In particular, achieving high activity without sacrificing stability is essential for designing commercially viable catalysts. A major challenge in designing state-of-the-art Ru-based catalysts for the oxygen evolution reaction (OER), which is a key step in water splitting, is the poor stability and surface tailorability of these catalysts. In this study, we designed rapidly synthesizable size-controlled, morphology-selective, and surface-tailored platinum-ruthenium core-shell (Pt@Ru) and alloy (PtRu) nanocatalysts in a scalable continuous-flow reactor. These core-shell nanoparticles with atomically precise shells were produced in a single synthetic step with carbon monoxide as the reducing agent. By varying the metal precursor concentration, a dendritic or layer-by-layer ruthenium shell can be grown. The catalytic activities of the synthesized Pt@Ru and PtRu nanoparticles exhibit noticeably higher electrocatalytic activity in the OER compared to that of pure Pt and Ru nanoparticles. Promisingly, Pt@Ru nanocrystals with a ~2-3 atomic layer Ru cuboctahedral shell surpass conventional Ru nanoparticles in terms of both durability and activity.

Tailoring Ruthenium Exposure to Enhance the Performance of fcc Platinum@Ruthenium Core-Shell Electrocatalysts in the Oxygen Evolution Reaction

KAUST Repository

AlYami, Noktan; LaGrow, Alec P.; Joya, khurram; Hwang, Jinyeon; Katsiev, Khabiboulakh; Anjum, Dalaver H.; Losovyj, Yaroslav; Sinatra, Lutfan; Kim, Jin Young; Bakr, Osman

2016-01-01

The catalytic properties of noble metal nanocrystals are a function of their size, structure, and surface composition. In particular, achieving high activity without sacrificing stability is essential for designing commercially viable catalysts. A major challenge in designing state-of-the-art Ru-based catalysts for the oxygen evolution reaction (OER), which is a key step in water splitting, is the poor stability and surface tailorability of these catalysts. In this study, we designed rapidly synthesizable size-controlled, morphology-selective, and surface-tailored platinum-ruthenium core-shell (Pt@Ru) and alloy (PtRu) nanocatalysts in a scalable continuous-flow reactor. These core-shell nanoparticles with atomically precise shells were produced in a single synthetic step with carbon monoxide as the reducing agent. By varying the metal precursor concentration, a dendritic or layer-by-layer ruthenium shell can be grown. The catalytic activities of the synthesized Pt@Ru and PtRu nanoparticles exhibit noticeably higher electrocatalytic activity in the OER compared to that of pure Pt and Ru nanoparticles. Promisingly, Pt@Ru nanocrystals with a ~2-3 atomic layer Ru cuboctahedral shell surpass conventional Ru nanoparticles in terms of both durability and activity.

Synthesis of three-dimensionally ordered macro-/mesoporous Pt with high electrocatalytic activity by a dual-templating approach

Science.gov (United States)

Zhang, Chengwei; Yang, Hui; Sun, Tingting; Shan, Nannan; Chen, Jianfeng; Xu, Lianbin; Yan, Yushan

2014-01-01

Three dimensionally ordered macro-/mesoporous (3DOM/m) Pt catalysts are fabricated by chemical reduction employing a dual-templating synthesis approach combining both colloidal crystal (opal) templating (hard-templating) and lyotropic liquid crystal templating (soft-templating) techniques. The macropore walls of the prepared 3DOM/m Pt exhibit a uniform mesoporous structure composed of polycrystalline Pt nanoparticles. Both the size of the mesopores and Pt nanocrystallites are in the range of 3-5 nm. The 3DOM/m Pt catalyst shows a larger electrochemically active surface area (ECSA), and higher catalytic activity as well as better poisoning tolerance for methanol oxidation reaction (MOR) than the commercial Pt black catalyst.

Pseudogap behavior of RuP probed by photoemission spectroscopy

OpenAIRE

Sato, K.; Ootsuki, D.; Wakisaka, Y.; Saini, N. L.; Mizokawa, T.; Arita, M.; Anzai, H.; Namatame, H.; Taniguchi, M.; Hirai, D.; Takagi, H.

2012-01-01

We have studied the electronic structure of RuP and related Ru pnictides using photoemission spectroscopy. Ru 3d core-level and valence-band spectra of RuP show that the Ru valence is +3 with t_{2g}^5 configuration. The photoemisson spectral weight near the Fermi level is moderately suppressed in the pseudogap phase of RuP, consistent with the pseudogap opening of 2\\Delta/k_BT_c ~ 3 (gap size \\Delta ~ 50 meV and transition temperature T_c ~ 330 K). The Ru 3d peak remains sharp in the pseudoga...

Catalytic wet oxidation of ammonia solution: Activity of the nanoscale platinum-palladium-rhodium composite oxide catalyst

International Nuclear Information System (INIS)

Hung, C.-M.

2009-01-01

Aqueous solutions of 400-1000 mg/L of ammonia were oxidized in a trickle-bed reactor (TBR) in this study of nanoscale platinum-palladium-rhodium composite oxide catalysts, which were prepared by the co-precipitation of H 2 PtCl 6 , Pd(NO 3 ) 3 and Rh(NO 3 ) 3 . Hardly any of the dissolved ammonia was removed by wet oxidation in the absence of any catalyst, whereas about 99% of the ammonia was reduced during wet oxidation over nanoscale platinum-palladium-rhodium composite oxide catalysts at 503 K in an oxygen partial pressure of 2.0 MPa. A synergistic effect exists in the nanoscale platinum-palladium-rhodium composite structure, which is the material with the highest ammonia reduction activity. The nanometer-sized particles were characterized by TEM, XRD and FTIR. The effect of the initial concentration and reaction temperature on the removal of ammonia from the effluent streams was also studied at a liquid hourly space velocity of under 9 h -1 in the wet catalytic processes

Catalytic wet oxidation of ammonia solution: Activity of the nanoscale platinum-palladium-rhodium composite oxide catalyst

Energy Technology Data Exchange (ETDEWEB)

Hung, C.-M. [Department of Industry Engineering and Management, Yung-Ta Institute of Technology and Commerce, 316 Chung-shan Road, Linlo, Pingtung 909, Taiwan (China)], E-mail: hungcm1031@gmail.com

2009-04-15

Aqueous solutions of 400-1000 mg/L of ammonia were oxidized in a trickle-bed reactor (TBR) in this study of nanoscale platinum-palladium-rhodium composite oxide catalysts, which were prepared by the co-precipitation of H{sub 2}PtCl{sub 6}, Pd(NO{sub 3}){sub 3} and Rh(NO{sub 3}){sub 3}. Hardly any of the dissolved ammonia was removed by wet oxidation in the absence of any catalyst, whereas about 99% of the ammonia was reduced during wet oxidation over nanoscale platinum-palladium-rhodium composite oxide catalysts at 503 K in an oxygen partial pressure of 2.0 MPa. A synergistic effect exists in the nanoscale platinum-palladium-rhodium composite structure, which is the material with the highest ammonia reduction activity. The nanometer-sized particles were characterized by TEM, XRD and FTIR. The effect of the initial concentration and reaction temperature on the removal of ammonia from the effluent streams was also studied at a liquid hourly space velocity of under 9 h{sup -1} in the wet catalytic processes.

Catalytic wet oxidation of ammonia solution: activity of the nanoscale platinum-palladium-rhodium composite oxide catalyst.

Science.gov (United States)

Hung, Chang-Mao

2009-04-15

Aqueous solutions of 400-1000 mg/L of ammonia were oxidized in a trickle-bed reactor (TBR) in this study of nanoscale platinum-palladium-rhodium composite oxide catalysts, which were prepared by the co-precipitation of H(2)PtCl(6), Pd(NO(3))(3) and Rh(NO(3))(3). Hardly any of the dissolved ammonia was removed by wet oxidation in the absence of any catalyst, whereas about 99% of the ammonia was reduced during wet oxidation over nanoscale platinum-palladium-rhodium composite oxide catalysts at 503 K in an oxygen partial pressure of 2.0 MPa. A synergistic effect exists in the nanoscale platinum-palladium-rhodium composite structure, which is the material with the highest ammonia reduction activity. The nanometer-sized particles were characterized by TEM, XRD and FTIR. The effect of the initial concentration and reaction temperature on the removal of ammonia from the effluent streams was also studied at a liquid hourly space velocity of under 9 h(-1) in the wet catalytic processes.

Peierls-distorted Ru-chains and boron dumbbells in Nb{sub 2}RuB{sub 2} and Ta{sub 2}RuB{sub 2} from first-principles calculations and experiments

Energy Technology Data Exchange (ETDEWEB)

Touzani, Rachid S.; Mbarki, Mohammed; Chen, Ximeng [Institute of Inorganic Chemistry, RWTH Aachen University (Germany); Fokwa, Boniface P.T. [Institute of Inorganic Chemistry, RWTH Aachen University (Germany); Department of Chemistry, University of California Riverside (UCR), Riverside, CA (United States)

2016-09-15

Nb{sub 2}RuB{sub 2} and Ta{sub 2}RuB{sub 2} phases were recently predicted by GGA-VASP structure optimization to crystallize in the Nb{sub 2}OsB{sub 2}-type structure. Although the Fe-based (Mo{sub 2}FeB{sub 2} type) and Os-based (Nb{sub 2}OsB{sub 2} type, superstructure variant of Mo{sub 2}FeB{sub 2} type) analogues have been synthesized and characterized successfully, the Ru-based phases remained unknown. Crystal structure prediction of Nb{sub 2}RuB{sub 2} and Ta{sub 2}RuB{sub 2} phases, using an evolutionary algorithm, led to the AlMn{sub 2}B{sub 2}-type structure in contrast to the aforementioned optimization; however, phonon calculations showed that the Nb{sub 2}OsB{sub 2}-type phases are dynamically more stable than the AlMn{sub 2}B{sub 2}-type phases. A slightly modified synthetic strategy finally led to the successful preparation of the predicted phases. The extremely quick arc-melting procedure, under argon atmosphere, not only led to a quantitative amount of the phases but also to single crystals suitable for structure determination. Powder and single-crystal X-ray diffraction as well as EDX analysis of the metal ratio have confirmed the GGA-VASP structure optimization: Nb{sub 2}RuB{sub 2} and Ta{sub 2}RuB{sub 2} compounds indeed crystallize isotypically with Nb{sub 2}OsB{sub 2} structure, a superstructure variant of Mo{sub 2}FeB{sub 2} type, in which B-dumbbells and Peierls-distorted Ru-chains are found. Susceptibility measurements on a Ta{sub 2}RuB{sub 2} single crystal reveal no superconducting transition down to 2 K, even though some features in the band structures of both phases, similar to those reported in superconducting NbRuB, hinted at possible superconductivity. (copyright 2016 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Controlled Synthesis of Pt Nanowires with Ordered Large Mesopores for Methanol Oxidation Reaction

Science.gov (United States)

Zhang, Chengwei; Xu, Lianbin; Yan, Yushan; Chen, Jianfeng

2016-08-01

Catalysts for methanol oxidation reaction (MOR) are at the heart of key green-energy fuel cell technology. Nanostructured Pt materials are the most popular and effective catalysts for MOR. Controlling the morphology and structure of Pt nanomaterials can provide opportunities to greatly increase their activity and stability. Ordered nanoporous Pt nanowires with controlled large mesopores (15, 30 and 45 nm) are facilely fabricated by chemical reduction deposition from dual templates using porous anodic aluminum oxide (AAO) membranes with silica nanospheres self-assembled in the channels. The prepared mesoporous Pt nanowires are highly active and stable electrocatalysts for MOR. The mesoporous Pt nanowires with 15 nm mesopores exhibit a large electrochemically active surface area (ECSA, 40.5 m2 g-1), a high mass activity (398 mA mg-1) and specific activity (0.98 mA cm-2), and a good If/Ib ratio (1.15), better than the other mesoporous Pt nanowires and the commercial Pt black catalyst.

Surface studies by low energy ion beams: Cu/Ru(0001) and Cu/O/Ru(0001)

Energy Technology Data Exchange (ETDEWEB)

Shen, Y.G.; O`Connor, D.J.; MacDonald, R.J. [Newcastle Univ., NSW (Australia). Dept. of Physics; Wandelt, H. [Institut fur Physikalische und Theoretische Chemie der Universitat Bonn, Bonn (Germany).; Zee, H. van [Eindhoven University of Technology, Eindhoven (Netherlands) Dept. of Physics

1993-12-31

The surface structure of Cu on Ru(OOO1) has been studied by low energy Li{sup +} ion scattering. It was found that Cu forms pseudomorphic islands for two layers. The effects of Cu on an O-precovered RU(OOO1) surface has also been investigated using keV He{sup +} ions. The results show that during the deposition of Cu, O is displaced from the Ru surface and migrated onto the top of the surface of the growing overlayer. The floated out O has been tested, showing a disordered overlayer. 5 refs., 3 figs.

Surface studies by low energy ion beams: Cu/Ru(0001) and Cu/O/Ru(0001)

Energy Technology Data Exchange (ETDEWEB)

Shen, Y G; O` Connor, D J; MacDonald, R J [Newcastle Univ., NSW (Australia). Dept. of Physics; Wandelt, H [Institut fur Physikalische und Theoretische Chemie der Universitat Bonn, Bonn (Germany).; Zee, H van [Eindhoven University of Technology, Eindhoven (Netherlands) Dept. of Physics

1994-12-31

The surface structure of Cu on Ru(OOO1) has been studied by low energy Li{sup +} ion scattering. It was found that Cu forms pseudomorphic islands for two layers. The effects of Cu on an O-precovered RU(OOO1) surface has also been investigated using keV He{sup +} ions. The results show that during the deposition of Cu, O is displaced from the Ru surface and migrated onto the top of the surface of the growing overlayer. The floated out O has been tested, showing a disordered overlayer. 5 refs., 3 figs.

Formation of graphene on Ru(0001) surface

Institute of Scientific and Technical Information of China (English)

Pan Yi; Shi Dong-Xia; Gao Hong-Jun

2007-01-01

We report on the formation of a graphene monolayer on a Ru(0001) surface by annealing the Ru(0001) crystal.The samples are characterized by scanning tunnelling microscopy (STM) and Auger electron spectroscopy (AES). STM images show that the Moiré pattern is caused by the graphene layer mismatched with the underlying Ru(0001) surface and has an N × N superlattice. It is further found that the graphene monolayer on a Ru(0001) surface is very stable at high temperatures. Our results provide a simple and convenient method to produce a graphene monolayer on the Ru(0001) surface, which is used as a template for fabricating functional nanostructures needed in future nano devices and catalysis.

Nanoscale Topography on Black Titanium Imparts Multi-biofunctional Properties for Orthopedic Applications

Science.gov (United States)

Hasan, Jafar; Jain, Shubham; Chatterjee, Kaushik

2017-01-01

We have developed a chlorine based reactive ion etching process to yield randomly oriented anisotropic nanostructures that render the titanium metal surface ‘black’ similar to that of black silicon. The surface appears black due to the nanostructures in contrast to the conventional shiny surface of titanium. The nanostructures were found to kill bacteria on contact by mechanically rupturing the cells as has been observed previously on wings of certain insects. The etching was optimized to yield nanostructures of ≈1 μm height for maximal bactericidal efficiency without compromising cytocompatibility. Within 4 hours of contact with the black titanium surface, 95% ± 5% of E. coli, 98% ± 2% of P. aeruginosa, 92% ± 5% of M. smegmatis and 22% ± 8% of S. aureus cells that had attached were killed. The killing efficiency for the S. aureus increased to 76% ± 4% when the cells were allowed to adhere up to 24 hours. The black titanium supported the attachment and proliferation of human mesenchymal stem cells and augmented osteogenic lineage commitment in vitro. Thus, the bioinspired nanostructures on black titanium impart multi-biofunctional properties toward engineering the next-generation biomaterials for orthopedic implants.

Ru nanostructure fabrication using an anodic aluminum oxide nanotemplate and highly conformal Ru atomic layer deposition

Energy Technology Data Exchange (ETDEWEB)

Kim, Woo-Hee; Park, Sang-Joon; Son, Jong-Yeog; Kim, Hyungjun [Department of Material Science and Engineering, POSTECH Pohang University of Science and Technology, San 31, Hyoja-Dong, Nam-Gu, Pohang 790-784 (Korea, Republic of)

2008-01-30

We fabricated metallic nanostructures directly on Si substrates through a hybrid nanoprocess combining atomic layer deposition (ALD) and a self-assembled anodic aluminum oxide (AAO) nanotemplate. ALD Ru films with Ru(DMPD)(EtCp) as a precursor and O{sub 2} as a reactant exhibited high purity and low resistivity with negligible nucleation delay and low roughness. These good growth characteristics resulted in the excellent conformality for nanometer-scale vias and trenches. Additionally, AAO nanotemplates were fabricated directly on Si and Ti/Si substrates through a multiple anodization process. AAO nanotemplates with various hole sizes (30-100 nm) and aspect ratios (2:1-20:1) were fabricated by controlling the anodizing process parameters. The barrier layers between AAO nanotemplates and Si substrates were completely removed by reactive ion etching (RIE) using BCl{sub 3} plasma. By combining the ALD Ru and the AAO nanotemplate, Ru nanostructures with controllable sizes and shapes were prepared on Si and Ti/Si substrates. The Ru nanowire array devices as a platform for sensor devices exhibited befitting properties of good ohmic contact and high surface/volume ratio.

Reactions of ethanol on Ru

NARCIS (Netherlands)

Sturm, Jacobus Marinus; Liu, Feng; Lee, Christopher James; Bijkerk, Frederik

2012-01-01

The adsorption and reactions of ethanol on Ru(0001) were studied with temperatureprogrammed desorption (TPD) and reflection-absorption infrared spectroscopy (RAIRS). Ethanol was found to adsorb intact onto Ru(0001) below 100 K. Heating to 250 K resulted in formation of ethoxy groups, which undergo

X-ray absorption spectroscopy for characterisation of catalysts for PEM fuel cells; Roentgenabsorptionsspektroskopie zur Charakterisierung von Katalysatoren fuer die PEM-Brennstoffzelle

Energy Technology Data Exchange (ETDEWEB)

Koehl, G.

2001-10-01

The investigation of bimetallic nanoparticles is of great interest for the development of powerful anode catalysts in PEM fuel cells. The determination of their electronic and geometric structure is crucial for the optimization of the activity and selectivity in the fuel cell. Especially carbon supported PtRu particles have shown superior activity as anode catalysts due to their high CO tolerance. To state the reason on an atomic level, X-ray absorption spectroscopy (XAS) with synchrotron radiation has been used to examine several Pt and PtRu nanoparticle systems. They were either prepared on the basis of preformed PtRu alloy colloids stabilized by different surfactants or by chemical reduction of precursors, Na{sub 6}Pt(SO{sub 3}){sub 4} and Na{sub 6}Ru(SO{sub 3}){sub 4}. Although a PtRu interaction was observed in all systems, a nonstatistical distribution of Pt and Ru atoms in the nanoparticles could be verified. In additional investigations the reaction mechanism during the synthesis of an organometallic stabilized Pt colloid was examined. In-situ measurements revealed the formation of an hitherto unknown Pt complex as intermediate state prior to the nucleation of the particles. (orig)

Synthesis and Biological Evaluation of Ru(II) and Pt(II) Complexes Bearing Carboxyl Groups as Potential Anticancer Targeted Drugs.

Science.gov (United States)

Martínez, Ma Ángeles; Carranza, M Pilar; Massaguer, Anna; Santos, Lucia; Organero, Juan A; Aliende, Cristina; de Llorens, Rafael; Ng-Choi, Iteng; Feliu, Lidia; Planas, Marta; Rodríguez, Ana M; Manzano, Blanca R; Espino, Gustavo; Jalón, Félix A

2017-11-20

The synthesis and characterization of Pt(II) (1 and 2) and Ru(II) arene (3 and 4) or polypyridine (5 and 6) complexes is described. With the aim of having a functional group to form bioconjugates, one uncoordinated carboxyl group has been introduced in all complexes. Some of the complexes were selected for their potential in photodynamic therapy (PDT). The molecular structures of complexes 2 and 5, as well as that of the sodium salt of the 4'-(4-carboxyphenyl)-2,2':6',2″-terpyridine ligand (cptpy), were determined by X-ray diffraction. Different techniques were used to evaluate the binding capacity to model DNA molecules, and MTT cytotoxicity assays were performed against four cell lines. Compounds 3, 4, and 5 showed little tendency to bind to DNA and exhibited poor biological activity. Compound 2 behaves as bonded to DNA probably through a covalent interaction, although its cytotoxicity was very low. Compound 1 and possibly 6, both of which contain a cptpy ligand, were able to intercalate with DNA, but toxicity was not observed for 6. However, compound 1 was active in all cell lines tested. Clonogenic assays and apoptosis induction studies were also performed on the PC-3 line for 1. The photodynamic behavior for complexes 1, 5, and 6 indicated that their nuclease activity was enhanced after irradiation at λ = 447 nm. The cell viability was significantly reduced only in the case of 5. The different behavior in the absence or presence of light makes complex 5 a potential prodrug of interest in PDT. Molecular docking studies followed by molecular dynamics simulations for 1 and the counterpart without the carboxyl group confirmed the experimental data that pointed to an intercalation mechanism. The cytotoxicity of 1 and the potential of 5 in PDT make them good candidates for subsequent conjugation, through the carboxyl group, to "selected peptides" which could facilitate the selective vectorization of the complex toward receptors that are overexpressed in

A Renewable and Ultrasensitive Electrochemiluminescence Immunosenor Based on Magnetic RuL@SiO2-Au~RuL-Ab2 Sandwich-Type Nano-Immunocomplexes

Directory of Open Access Journals (Sweden)

Ning Gan

2011-08-01