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Sample records for surface pt oxide

  1. First principles mechanistic study of borohydride oxidation over the Pt(1 1 1) surface

    International Nuclear Information System (INIS)

    Rostamikia, Gholamreza; Janik, Michael J.

    2010-01-01

    The mechanism of borohydride oxidation and the competing hydrolysis reaction are examined over Pt(1 1 1) using density functional theory (DFT) methods. Adsorption of BH 4 - over Au(1 1 1) and Pt(1 1 1) is examined. Adsorption over Pt(1 1 1) is dissociative and extremely exothermic at potentials of interest, leading to a high surface coverage of H * for which gaseous hydrogen evolution is competitive with oxidation. Elementary surface reactions oxidizing B-containing intermediates are favorable over Pt(1 1 1) at -0.85 V (SHE), consistent with experimental voltammetry results in the literature. The energetics of the initial adsorption step dictate the activity limitation of gold anodes and the selectivity limitation of platinum electrodes. This adsorption energy can be rapidly calculated with DFT methods, enabling screening of pure metals, alloys, poisons, and promoters to optimize borohydride oxidation catalyst design.

  2. Surface enrichment of Pt in stable Pt-Ir nano-alloy particles on MgAl 2 O 4 spinel in oxidizing atmosphere

    Energy Technology Data Exchange (ETDEWEB)

    Li, Weizhen; Nie, Lei; Chen, Ying; Kovarik, Libor; Liu, Jun; Wang, Yong

    2017-04-01

    With the capability of MgAl2O4 spinel {111} nano-facets in stabilizing small Rh, Ir and Pt particles, bimetallic Ir-Pt catalysts on the same support were investigated, aiming at further lowering the catalyst cost by substituting expensive Pt with cheaper Ir in the bulk. Small Pt-Ir nano-alloy particles (< 2nm) were successfully stabilized on the spinel {111} nano-facets as expected. Interestingly, methanol oxidative dehydrogenation (ODH) rate on the surface Pt atoms increases with oxidizing aging but decreases upon reducing treatment, where Ir is almost inactive under the same reaction conditions. Up to three times enhancement in Pt exposure was achieved when the sample was oxidized at 800 °C in air for 1 week and subsequently reduced by H2 for 2 h, demonstrating successful surface enrichment of Pt on Pt-Ir nano-alloy particles. A dynamic stabilization mechanism involving wetting\

  3. Pt-Si Bifunctional Surfaces for CO and Methanol Electro-Oxidation

    DEFF Research Database (Denmark)

    Permyakova, Anastasia A.; Han, Binghong; Jensen, Jens Oluf

    2015-01-01

    Bimetallic surfaces offer activity benefits derived from synergistic effects among active sites with uniquely different functions, which is particularly important for the development of highly effective heterogeneous catalysts for specific technological applications, such as energy conversion...... and storage. Here we report on Pt-Si bulk samples prepared by arc-melting, for the first time, with high activities toward the electro-oxidation of CO and methanol. Increasing the Si concentration on the surface was correlated with the shifts of onset oxidation potentials to lower values and higher activities...... for CO and methanol electro-oxidation. It is proposed that the reaction on the Pt-Si catalyst could follow a Langmuir-Hinshelwood type of mechanism, where substantially enhanced catalytic activity is attributed to the fine-tuning of the surface Pt-Si atomic structure....

  4. Carbon monoxide oxidation on Pt-Ru electrocatalysts supported on high surface area carbon

    Directory of Open Access Journals (Sweden)

    Colmati Jr. Flavio

    2002-01-01

    Full Text Available This work describes the preparation and characterization of Pt-Ru alloys dispersed on high surface area carbon, which were evaluated for CO oxidation on thin porous coating rotating disk electrodes and for hydrogen oxidation on polymer electrolyte fuel cells fed with hydrogen containing 100 ppm CO. A thermal treatment (H2, 300 ºC applied to the catalysts improves the tolerance to small quantities of CO and, in some cases, reduces the potential necessary to promote the CO oxidation during a linear potential scan. Under operational conditions in a fuel cell in the presence of CO it was observed that the best results were obtained when the Pt-Ru/C alloy was prepared by simultaneous reduction of the ions Pt (IV and Ru (III, as opposed to a sequential reduction.

  5. Kinetically induced irreversibility in electro-oxidation and reduction of Pt surface

    Science.gov (United States)

    Jinnouchi, Ryosuke; Kodama, Kensaku; Suzuki, Takahisa; Morimoto, Yu

    2015-05-01

    A mean field kinetic model was developed for electrochemical oxidations and reductions of Pt(111) on the basis of density functional theory calculations, and the reaction mechanisms were analyzed. The model reasonably describes asymmetric shapes of cyclic voltammograms and small Tafel slopes of relevant redox reactions observed in experiments without assuming any unphysical forms of rate equations. Simulations using the model indicate that the oxidation of Pt(111) proceeds via an electrochemical oxidation from Pt to PtOH and a disproportionation reaction from PtOH to PtO and Pt, while its reduction proceeds via two electrochemical reductions from PtO to PtOH and from PtOH to Pt.

  6. Surface properties and catalytic performance of Pt/LaSrCoO4 catalysts in the oxidation of hexane

    Directory of Open Access Journals (Sweden)

    Hua Zhong

    2007-08-01

    Full Text Available Perovskite-type La2 –xSrxCoO4 mixed oxides have been prepared by calcination at various temperatures of precipitates obtained from aqueous solutions in the presence of citric or ethylenediamintetraacetic (EDTA acids, and have been studied by X-ray diffraction (XRD, surface area (BET measurements, temperature programmed desorption (TPD, temperature programmed reduction (TPR and X-ray photoelectron spectroscopy (XPS. These oxides are catalysts for hexane oxidation, with the greatest activity for LaSrCoO4 calcined at 750 C. This has extensive oxygen vacancies and large internal surface area. Pt-modified LaSrCoO4 catalysts are significantly more active than the Pt-free system. Both surface and bulk phases of the preovskitetype oxides contribute to hexane oxidation.

  7. 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.

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

    Science.gov (United States)

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

    2018-03-01

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

  9. Surface chemistry on bimetallic alloy surfaces: adsorption of anions and oxidation of CO on Pt3Sn(111).

    Science.gov (United States)

    Stamenković, Vojislav R; Arenz, Matthias; Lucas, Christopher A; Gallagher, Mark E; Ross, Philip N; Marković, Nenad M

    2003-03-05

    The microscopic structure of the Pt(3)Sn(111) surface in an electrochemical environment has been studied by a combination of ex situ low-energy electron diffraction (LEED), Auger electron spectroscopy (AES), and low-energy ion scattering (LEIS) and in situ surface X-ray scattering (SXS) and Fourier transform infrared (FTIR) spectroscopy. In ultrahigh vacuum (UHV) the clean-annealed surface produces a p(2 x 2) LEED pattern consistent with the surface composition, determined by LEIS, of 25 at. % Sn. SXS results show that the p(2 x 2) structure can be "transferred" from UHV into 0.5 M H(2)SO(4) and that the surface structure remains stable from 0.05 to 0.8 V. At 0.05 V the expansion of Pt surface atoms, ca. +2% from the bulk lattice spacing, is induced by adsorption of underpotential-deposited (UPD) hydrogen. At 0.5 V, where Pt atoms are covered by (bi)sulfate anions, the topmost layer is contracted relative to 0.05 V, although Sn atoms expand significantly, ca. 8.5%. The p(2 x 2) structure is stable even in solutions containing CO. In contrast to the Pt(111)-CO system, no ordered structures of CO are formed on the Pt(3)Sn(111) surface and the topmost layer expands relatively little (ca. 1.5%) from the bulk lattice spacing upon the adsorption of CO. The binding site geometry of CO on Pt(3)Sn(111) is determined by FTIR. In contrast to the near invariant band shape of a-top CO on Pt(111), changes in band morphology (splitting of the band) and vibrational properties (increase in the frequency mode) are clearly visible on the Pt(3)Sn(111) surface. To explain the line shape of the CO bands, we suggest that in addition to alloying effects other factors, such as intermolecular repulsion between coadsorbed CO and OH species, are controlling segregation of CO into cluster domains where the local CO coverage is different from the coverage expected for the CO-CO interaction on an unmodified Pt(111) surface.

  10. Time Resolved Operando X-ray Techniques in Catalysis, a Case Study: CO Oxidation by O2 over Pt Surfaces and Alumina Supported Pt Catalysts

    Directory of Open Access Journals (Sweden)

    Mark A. Newton

    2017-02-01

    Full Text Available The catalytic oxidation of CO by O2 to form CO2 over Pt surfaces and supported catalysts is one of the most studied catalytic reactions from both fundamental and applied points of view. This review aims to show how the application of a range of time resolved, X-ray based techniques, such as X-ray diffraction (XRD, Surface X-ray diffraction (SXRD, total X-ray scattering/pair distribution function (PDF, X-ray absorption (XAFS, X-ray emission (XES, and X-ray photoelectron spectroscopies (XPS, applied under operando conditions and often coupled to adjunct techniques (for instance mass spectrometry (MS and infrared spectroscopy (IR have shed new light on the structures and mechanisms at work in this most studied of systems. The aim of this review is therefore to demonstrate how a fusion of the operando philosophy with the ever augmenting capacities of modern synchrotron sources can lead to new insight and catalytic possibilities, even in the case of a process that has been intensely studied for almost 100 years.

  11. Investigation of oxygen reduction and methanol oxidation reaction activity of PtAu nano-alloy on surface modified porous hybrid nanocarbon supports

    Science.gov (United States)

    Parambath Vinayan, Bhaghavathi; Nagar, Rupali; Ramaprabhu, Sundara

    2016-09-01

    We investigate the electrocatalytic activity of PtAu alloy nanoparticles supported on various chemically modified carbon morphologies towards oxygen reduction reaction (ORR) and methanol oxidation reaction (MOR). The surface-modification of graphene nanosheets (f-G), multi-walled carbon nanotubes (f-MWNTs) and (graphene nanosheets-carbon nanotubes) hybrid support (f-G-MWNTs) were carried out by soft functionalization method using a cationic polyelectrolyte poly-(diallyldimethyl ammonium chloride). The Pt and PtAu alloy nanoparticles were dispersed over chemically modified carbon supports by sodium-borohydride assisted modified polyol reduction method. The electrochemical performance of all electrocatalysts were studied by half- and full-cell proton exchange membrane fuel cell (PEMFC) measurements and PtAu/f-G-MWNTs catalyst comparatively yielded the best catalytic performance. PEMFC full cell measurements of PtAu/f-G-MWNTs cathode electrocatalyst yield a maximum power density of 319 mW cm-2 at 60 °C without any back pressure,which is 2.1 times higher than that of cathode electrocatalyst Pt on graphene support. The high ORR and MOR activity of PtAu/f-G-MWNTs electrocatalyst is due to the alloying effect and inherent beneficial properties of porous hybrid nanocarbon support.

  12. Mesoporous Pt and Pt/Ru alloy electrocatalysts for methanol oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Franceschini, Esteban A. [Grupo de Celdas de Combustible, Departamento de Fisica de la Materia Condensada, Centro Atomico Constituyentes, CNEA. Av. General Paz 1499 (1650), San Martin, Buenos Aires (Argentina); Planes, Gabriel A. [Departamento de Quimica, Facultad de Ciencias Exactas, Fisicoquimicas y Naturales, Universidad Nacional de Rio Cuarto, Agencia Postal No 3, 5800, Rio Cuarto (Argentina); Williams, Federico J. [Departamento de Quimica Inorganica, Analitica y Quimica-Fisica, INQUIMAE CONICET, Facultad Ciencias Exactas y Naturales, Pabellon 2, Ciudad Universitaria, Buenos Aires (Argentina); Soler-Illia, Galo J.A.A. [Gerencia de Quimica, Centro Atomico Constituyentes, CNEA. Av. General Paz 1499 (1650), San Martin, Buenos Aires (Argentina); Corti, Horacio R. [Grupo de Celdas de Combustible, Departamento de Fisica de la Materia Condensada, Centro Atomico Constituyentes, CNEA. Av. General Paz 1499 (1650), San Martin, Buenos Aires (Argentina); Departamento de Quimica Inorganica, Analitica y Quimica-Fisica, INQUIMAE CONICET, Facultad Ciencias Exactas y Naturales, Pabellon 2, Ciudad Universitaria, Buenos Aires (Argentina)

    2011-02-15

    Mesoporous Pt and Pt/Ru catalysts with 2D-hexagonal mesostructure were synthesized using a triblock poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) copolymer (Pluronic F127 {sup registered}) template, on a gold support. Large electrochemical surface areas were observed for the catalysts prepared at high overpotentials. Compared to the Pt catalyst, the Pt/Ru alloy containing 3 at% of Ru exhibited lower onset potential and more than three times the limit mass activity for methanol oxidation. This behavior is assigned to the larger pore size of the mesoporous Pt and Pt/Ru catalysts obtained with this template that seems to improve the methanol accessibility to the active sites compared to those obtained using lyotropic liquid crystals. (author)

  13. Comparative Analysis of Cobalt Oxide Nanoisland Stability and Edge Structures on Three Related Noble Metal Surfaces: Au (111), Pt (111) and Ag (111)

    DEFF Research Database (Denmark)

    Fester, Jakob; Bajdich, Michal; Walton, Alexander

    2017-01-01

    Metal oxide nanostructures and thin films grown on metallic substrates have attracted strong attention as model catalysts and as interesting inverse catalyst systems in their own right. In this study, we investigate the role of metal support in the growth and stabilization of cobalt oxide...... nanostructures on the three related (111) surfaces of Au, Pt and Ag, as investigated by means of high-resolution scanning tunneling microscopy and DFT calculations. All three substrates promote the growth of crystalline CoOx (x = 1−2) islands under oxidative conditions, but we find several noteworthy differences...

  14. A cast-mold approach to iron oxide and Pt/iron oxide nanocontainers and nanoparticles with a reactive concave surface.

    Science.gov (United States)

    George, Chandramohan; Dorfs, Dirk; Bertoni, Giovanni; Falqui, Andrea; Genovese, Alessandro; Pellegrino, Teresa; Roig, Anna; Quarta, Alessandra; Comparelli, Roberto; Curri, M Lucia; Cingolani, Roberto; Manna, Liberato

    2011-02-23

    We report the synthesis of various iron oxide nanocontainers and Pt-iron oxide nanoparticles based on a cast-mold approach, starting from nanoparticles having a metal core (either Au or AuPt) and an iron oxide shell. Upon annealing, the particles evolve to asymmetric core-shells and then to heterodimers. If iodine is used to leach Au out of these structures, asymmetric core-shells evolve into "nanocontainers", that is, iron oxide nanoparticles enclosing a cavity accessible through nanometer-sized pores, while heterodimers evolve into particles with a concave region. When starting from a metal domain made of AuPt, selective leaching of the Au atoms yields the same iron oxide nanoparticle morphologies but now encasing Pt domains (in their concave region or in their cavity). We found that the concave nanoparticles are capable of destabilizing Au nanocrystals of sizes matching that of the concave region. In addition, for the nanocontainers, we propose two different applications: (i) we demonstrate loading of the cavity region of the nanocontainers with the antitumoral drug cis-platin; and (ii) we show that nanocontainers encasing Pt domains can act as recoverable photocatalysts for the reduction of a model dye.

  15. Activation of surface lattice oxygen in single-atom Pt/CeO 2 for low-temperature CO oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Nie, Lei; Mei, Donghai; Xiong, Haifeng; Peng, Bo; Ren, Zhibo; Pereira Hernandez, Xavier I.; DelaRiva, Andrew; Wang, Meng; Engelhard, Mark H.; Kovarik, Libor; Datye, Abhaya K.; Wang, Yong

    2017-12-14

    While single-atom catalysts can provide high catalytic activity and selectivity, application in industrial catalysts demands long term performance and the ability to regenerate the catalysts. We have investigated the factors that lead to improved catalytic activity of a Pt/CeO2 catalyst for low temperature CO oxidation. Single-atom Pt/CeO2 becomes active for CO oxidation under lean condition only at elevated temperatures, because CO is strongly bound to ionic Pt sites. Reducing the catalyst, even under mild conditions, leads to onset of CO oxidation activity even at room temperature. This high activity state involves the transformation of mononuclear Pt species to sub-nanometer sized Pt particles. Under oxidizing conditions, the Pt can be restored to its stable, single-atom state. The key to facile regeneration is the ability to create mobile Pt species and suitable trapping sites on the support, making this a prototypical catalyst system for industrial application of single-atom catalysis.

  16. Dynamics of Surface Exchange Reactions Between Au and Pt for HER and HOR

    DEFF Research Database (Denmark)

    Abrams, Billie; Vesborg, Peter Christian Kjærgaard; Bonde, Jacob Lindner

    2009-01-01

    Cyclic voltammetric analysis of the Pt-on-Au system for hydrogen evolution and oxidation reactions (HER/HOR) indicates that dynamic surface exchange reactions occur between Pt and Au. HER/HOR activities depend on the dominant surface species present, which is controllable by the potential applied...... to the system. Bulk Au is not very active for HER/HOR; however, when Pt is deposited onto the Au surface, the system becomes active. The Pt-on-Au system can subsequently be deactivated by cycling to potentials cathodic of the OH-adsorption and Pt-dissolution potentials (~+1.18 V vs normal hydrogen electrode...... reaction is attributed to the lower surface energy of Au relative to Pt causing Au to migrate to the surface. When the system is deactivated, Au is present at the surface. However, Pt migrates back to the surface at higher positive potentials, where PtOx/PtOHx is formed, leading to adsorbate...

  17. Enhanced activity of rare earth doped PtRu/C catalysts for methanol electro-oxidation

    International Nuclear Information System (INIS)

    An Xiaosha; Fan Youjun; Chen Dejun; Wang Qiang; Zhou Zhiyou; Sun Shigang

    2011-01-01

    Highlights: → The electrocatalytic activity of PtRuRE/C catalysts is higher than that of the JM PtRu/C for methanol oxidation (except for PtRuGd/C), generating a decreasing order of PtRuEu/C > PtRuEr/C > PtRuY/C > PtRuSm/C > PtRuLa/C > JM PtRu/C > PtRuGd/C. → The CO-tolerance performance of PtRuRE/C catalysts is better than JM PtRu/C. → The electronic effect of rare earth plays an important role in the catalytic performance of PtRuRE/C for methanol electrooxidation. - Abstract: PtRuRE/C catalysts were prepared through doping the commercial JM PtRu/C catalyst with rare earth (RE = La, Eu, Gd, Y, Sm and Er). The doping was conducted by chemical reduction and sintering treatment methods. The catalysts were characterized by transmission electron microscopy (TEM), energy dispersive X-ray (EDX) spectroscopy, X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The results demonstrated that the rare earth doping did not significantly change the average size of the JM PtRu/C particles, and modified the PtRu surface with two element states of the metal and oxide. Studies of cyclic voltammetry and chronoamperometry indicated that the electrocatalytic activity of PtRuRE/C catalysts was higher than that of the JM PtRu/C for methanol oxidation (except for PtRuGd/C), generating a decreasing order of PtRuEu/C > PtRuEr/C > PtRuY/C > PtRuSm/C > PtRuLa/C > JM PtRu/C > PtRuGd/C. It has revealed that among the PtRuRE/C catalysts the PtRuEu/C exhibited the best performance. In addition, the reaction process of methanol electrocatalytic oxidation on several catalysts was investigated by in situ FTIR spectroscopy at molecule level. The results demonstrated that the adsorbates derived from methanol dissociative adsorption on the catalysts were the linear-bonded CO (CO L ), and the CO-tolerance performance of PtRuRE/C catalysts was better than JM PtRu/C. It has revealed also that the electronic effect of rare earth plays an important role in the catalytic performance

  18. Nanocomposite for methanol oxidation: synthesis and characterization of cubic Pt nanoparticles on graphene sheets

    Directory of Open Access Journals (Sweden)

    Tung-Yuan Yung, Jer-Yeu Lee and Ling-Kang Liu

    2013-01-01

    Full Text Available We present our recent results on Pt nanoparticles on graphene sheets (Pt-NPs/G, a nanocomposite prepared with microwave assistance in ionic liquid 2-hydroxyethanaminiumformate. Preparation of Pt-NPs/G was achieved without the addition of extra reductant such as hydrazine or ethylene glycol. The Pt nanoparticles on graphene have a cubic-like shape (about 60 wt% Pt loading, Pt-NPs/G and the particle size is 6 ± 3 nm from transmission electron microscopy results. Electrochemical cyclic voltammetry studies in 0.5 M aqueous H2SO4 were performed using Pt-NPs/G and separately, for comparison, using a commercially available electrocatalyst (60 wt% Pt loading, Pt/C. The electrochemical surface ratio of Pt-NPs/G to Pt/C is 0.745. The results of a methanol oxidation reaction (MOR in 0.5 M aqueous H2SO4 + 1.0 M methanol for the two samples are presented. The MOR results show that the ratios of the current density of oxidation (If to the current density of reduction (Ib are 3.49 (Pt-NPs/G and 1.37 (Pt/C, respectively, with a preference by 2.55 times favoring Pt-NPs/G. That is, the tolerance CO poisoning of Pt-NPs/G is better than that of commercial Pt/C.

  19. Nanocomposite for methanol oxidation: synthesis and characterization of cubic Pt nanoparticles on graphene sheets

    Science.gov (United States)

    Yung, Tung-Yuan; Lee, Jer-Yeu; Liu, Ling-Kang

    2013-06-01

    We present our recent results on Pt nanoparticles on graphene sheets (Pt-NPs/G), a nanocomposite prepared with microwave assistance in ionic liquid 2-hydroxyethanaminiumformate. Preparation of Pt-NPs/G was achieved without the addition of extra reductant such as hydrazine or ethylene glycol. The Pt nanoparticles on graphene have a cubic-like shape (about 60 wt% Pt loading, Pt-NPs/G) and the particle size is 6 ± 3 nm from transmission electron microscopy results. Electrochemical cyclic voltammetry studies in 0.5 M aqueous H2SO4 were performed using Pt-NPs/G and separately, for comparison, using a commercially available electrocatalyst (60 wt% Pt loading, Pt/C). The electrochemical surface ratio of Pt-NPs/G to Pt/C is 0.745. The results of a methanol oxidation reaction (MOR) in 0.5 M aqueous H2SO4 + 1.0 M methanol for the two samples are presented. The MOR results show that the ratios of the current density of oxidation (If) to the current density of reduction (Ib) are 3.49 (Pt-NPs/G) and 1.37 (Pt/C), respectively, with a preference by 2.55 times favoring Pt-NPs/G. That is, the tolerance CO poisoning of Pt-NPs/G is better than that of commercial Pt/C.

  20. Efficient Aerobic Oxidation of Cyclohexane to KA Oil Catalyzed by Pt ...

    Indian Academy of Sciences (India)

    Pt-Sn supported on MWCNTs were synthesized and characterized by SEM, EDX, XRD, XRF and surface area and pore size analyzer. The catalyst was used for the partial oxidation of cyclohexane in a Parr type reactor. It was found that Pt-Sn supported on MWCNTs can act as an efficient catalyst for the partial oxidation of ...

  1. Another 2-dimensional oxide quasicrystal: Strontium titanate on Pt(111)

    Energy Technology Data Exchange (ETDEWEB)

    Schenk, Sebastian; Hammer, Rene; Schumann, Florian; Foerster, Stefan; Meinel, Klaus [Institute of Physics, Martin-Luther-Universitaet Halle-Wittenberg, Halle (Germany); Widdra, Wolf [Institute of Physics, Martin-Luther-Universitaet Halle-Wittenberg, Halle (Germany); Max-Planck-Institut fuer Mikrostrukturphysik, Halle (Germany)

    2016-07-01

    Recently the formation of a BaTiO{sub 3}-derived 2-dimensional oxide quasicrystal (OQC) with 12-fold diffraction symmetry has been discovered on Pt(111) substrates [1]. Following an analogous preparation procedure, we show that SrTiO{sub 3} on Pt(111) develops an OQC as well. First, a closed SrTiO{sub 3} film on Pt(111) has been prepared using MBE. The stoichiometry and structure of the film has been analyzed by means of AES and SPA-LEED. Annealing the film in an O{sub 2} atmosphere yields the formation of 3-dimensional SrTiO{sub 3} islands with bare Pt(111) in between. Annealing in UHV causes a rewetting on the Pt(111) via surface diffusion of SrTiO{sub 3} from the islands. SPA-LEED and STM reveal that at temperatures around 700 C an OQC is formed in the rewetting layer. The SrTiO{sub 3} derived OQC is composed by quadratic, triangular, and rhombic elements of equal side length of about 0.6 nm. They form an aperiodic structure, which displays a well-ordered 12-fold diffraction pattern. Our results suggest that OQC formation is a general process of oxide perovskites on suitable substrates.

  2. CO surface electrochemistry on Pt-nanoparticles: A selective review

    Energy Technology Data Exchange (ETDEWEB)

    Mayrhofer, K.J.J. [Materials Science Division, Lawrence Berkeley National Laboratory, University of California, Berkeley, CA 94720 (United States); Arenz, M. [Materials Science Division, Lawrence Berkeley National Laboratory, University of California, Berkeley, CA 94720 (United States); Blizanac, B.B. [Materials Science Division, Lawrence Berkeley National Laboratory, University of California, Berkeley, CA 94720 (United States); Stamenkovic, V. [Materials Science Division, Lawrence Berkeley National Laboratory, University of California, Berkeley, CA 94720 (United States); Ross, P.N. [Materials Science Division, Lawrence Berkeley National Laboratory, University of California, Berkeley, CA 94720 (United States); Markovic, N.M. [Materials Science Division, Lawrence Berkeley National Laboratory, University of California, Berkeley, CA 94720 (United States)]. E-mail: nmmarkovic@lbl.gov

    2005-09-05

    Oxidation of CO on platinum nanoparticles ranging in size from 1 to 30 nm has been studied in acid electrolytes. We found that Pt nanoparticles, characterized by transmission electron microscopy, are not perfect cubo-octahedrons and that large particles have 'rougher' surfaces than small particles. The importance of 'defect' sites for the catalytic properties of nanoparticles was probed by using infrared reflection absorption spectroscopy (IRAS) and rotating disk electrode. From IRAS experiments, by monitoring how the vibrational frequency of a-top CO ({nu} {sub CO}) as well as the concomitant development of dissolved CO{sub 2} are affected by the number of defects on Pt nanoparticles, we suggested that defects play a significant role in CO 'clustering' on nanoparticles, causing CO to decrease/increase in local coverage, which results in anomalous redshift/blueshift {nu} {sub CO} frequency deviations from the normal Stark-tuning behavior. The observed {nu} {sub CO} deviations are accompanied by CO{sub 2} production, which increases by increasing the number of defects on the nanoparticles, i.e., 1 {<=} 2 < 5 << 30 nm. We suggest that the catalytic activity for CO adlayer oxidation (CO stripping) is predominantly influenced by the ability of the surface to dissociate water and to form OH{sub ad} on defect sites. We demonstrate that the catalytic activity of Pt nanoparticles for CO oxidation under the condition of continuous CO supply to the surface depends on the pre-history of the electrode. If the surface is precovered by CO, the particle size has a negligible effect on CO oxidation. However, on an oxide-precovered surface CO bulk oxidation increases with decreasing particle size, i.e., with increasing oxophilicity of the particles. We found, if specific sites on the surface are active for OH adsorption, then the electrocatalytic activity for CO oxidation changes as the concentration of these sites changes with particle size.

  3. CO oxidation on PtSn nanoparticle catalysts occurs at the interface of Pt and Sn oxide domains formed under reaction conditions

    KAUST Repository

    Michalak, William D.

    2014-04-01

    The barrier to CO oxidation on Pt catalysts is the strongly bound adsorbed CO, which inhibits O2 adsorption and hinders CO2 formation. Using reaction studies and in situ X-ray spectroscopy with colloidally prepared, monodisperse ∼2 nm Pt and PtSn nanoparticle catalysts, we show that the addition of Sn to Pt provides distinctly different reaction sites and a more efficient reaction mechanism for CO oxidation compared to pure Pt catalysts. To probe the influence of Sn, we intentionally poisoned the Pt component of the nanoparticle catalysts using a CO-rich atmosphere. With a reaction environment comprised of 100 Torr CO and 40 Torr O2 and a temperature range between 200 and 300 C, Pt and PtSn catalysts exhibited activation barriers for CO2 formation of 133 kJ/mol and 35 kJ/mol, respectively. While pure Sn is readily oxidized and is not active for CO oxidation, the addition of Sn to Pt provides an active site for O2 adsorption that is important when Pt is covered with CO. Sn oxide was identified as the active Sn species under reaction conditions by in situ ambient pressure X-ray photoelectron spectroscopy measurements. While chemical signatures of Pt and Sn indicated intermixed metallic components under reducing conditions, Pt and Sn were found to reversibly separate into isolated domains of Pt and oxidic Sn on the nanoparticle surface under reaction conditions of 100 mTorr CO and 40 mTorr O2 between temperatures of 200-275 C. Under these conditions, PtSn catalysts exhibited apparent reaction orders in O2 for CO 2 production that were 0.5 and lower with increasing partial pressures. These reaction orders contrast the first-order dependence in O 2 known for pure Pt. The differences in activation barriers, non-first-order dependence in O2, and the presence of a partially oxidized Sn indicate that the enhanced activity is due to a reaction mechanism that occurs at a Pt/Sn oxide interface present at the nanoparticle surface. © 2014 Published by Elsevier Inc.

  4. Ab-initio study of the coadsorption of Li and H on Pt(001), Pt(110) and Pt(111) surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Saad, Farida [Laboratoire de Physique et Chimie Quantique, Faculte des Sciences, Universite Mouloud Mammeri, 15000 Tizi-Ouzou (Algeria); Zemirli, Mourad, E-mail: zemirlimourad@mail.ummto.dz [Laboratoire de Physique et Chimie Quantique, Faculte des Sciences, Universite Mouloud Mammeri, 15000 Tizi-Ouzou (Algeria); Benakki, Mouloud; Bouarab, Said [Laboratoire de Physique et Chimie Quantique, Faculte des Sciences, Universite Mouloud Mammeri, 15000 Tizi-Ouzou (Algeria)

    2012-02-15

    The coadsorption of Li and H atoms on Pt(001), Pt(110) and Pt(111) surfaces is studied using density functional theory with generalised gradient approximation. In all calculations Li, H and the two topmost layers of the metal were allowed to relax. At coverage of 0.25 mono-layer in a p(2 Multiplication-Sign 2) unit cell, lithium adsorption at the hollow site for the three surfaces is favoured over top and bridge sites. The most favoured adsorption sites for H atom on the Pt(001) and Pt(110) surfaces are the top and bridge sites, while on Pt(111) surface the fcc site appears to be slightly favoured over the hcp site. The coadsorption of Li and atomic hydrogen shows that the interaction between the two adsorbates is stabilising when they are far from each other. The analysis of Li, H and Pt local density of states shows that Li strongly interacts with the Pt surfaces.

  5. Pt-Pd nanoelectrocatalyst of ultralow Pt content for the oxidation of ...

    Indian Academy of Sciences (India)

    Significant negative shift (∼350 mV) in the oxidation peak potential and remarkable enhancement in the current density (2.6 times) are observed for Pt4Pd96 nanoparticles with respect to Pt47Pd53. The absence of three adjacent Pt and Pd atoms could be the reason for the suppression of CO pathway. The electrochemical ...

  6. Electrocatalytic performance of Pt nanoparticles sputter-deposited on indium tin oxide toward methanol oxidation reaction: The particle size effect

    Science.gov (United States)

    Ting, Chao-Cheng; Chao, Chih-Hsuan; Tsai, Cheng Yu; Cheng, I.-Kai; Pan, Fu-Ming

    2017-09-01

    We sputter-deposited Pt nanoparticles with an average size ranging from 2.0 nm to 8.5 nm on the indium-tin oxide (ITO) glass substrate, and studied the effect of the size of Pt nanoparticles on electrocatalytic activity of the Pt/ITO electrode toward methanol oxidation reaction (MOR) in acidic solution. X-ray photoelectron spectroscopy (XPS) reveals an interfacial oxidized Pt layer present between Pt nanoparticles and the ITO substrate, which may modify the surface electronic structure of Pt nanoparticles and thus influences the electrocatalytic properties of the Pt catalyst toward MOR. According to electrochemical analyses, smaller Pt nanoparticles exhibit slower kinetics for CO electrooxidation and MOR. However, a smaller particle size enables better CO tolerance because the bifunctional mechanism is more effective on smaller Pt nanoparticles. The electrocatalytic activity decays rapidly for Pt nanoparticles with a size smaller than 3 nm and larger than 8 nm. The rapid activity decay is attributed to Pt dissolution for smaller nanoparticles and to CO poisoning for larger ones. Pt nanoparticles of 5-6 nm in size loaded on ITO demonstrate a greatly improved electrocatalytic activity and stability compared with those deposited on different substrates in our previous studies.

  7. Enhanced methanol electro-oxidation activity of Pt/MWCNTs electro-catalyst using manganese oxide deposited on MWCNTs

    International Nuclear Information System (INIS)

    Nouralishahi, Amideddin; Khodadadi, Abbas Ali; Mortazavi, Yadollah; Rashidi, Alimorad; Choolaei, Mohammadmehdi

    2014-01-01

    Highlights: • Promoting effects of manganese oxide (MnO x ) on methanol electro-oxidation over Pt/MWCNTs are studied. • 3.3 times higher activity and improved stability are observed on Pt/MnO x -MWCNTs in MOR. • Both hydrogen spill over and bi-functional mechanism are facilitated in presence of MnO x . • MnO x significantly enhances electrochemical active surface area and dispersion of Pt nanoparticles. • Proton conductivity of electrocatalyst layer is improved upon MnO x incorporation. - Abstract: Electro-oxidation of methanol on platinum nanoparticles supported on a nanocomposite of manganese oxide (MnO x ) and multi-wall carbon nanotubes (MWCNTs) is investigated. The morphology, structure, and chemical composition of the electro-catalysts are characterized by TEM, XRD, EDS, TGA, and H 2 -TPR. The electro-catalytic properties of electrodes are examined by cyclic voltammetry, CO-stripping, electrochemical impedance spectroscopy (EIS), and linear sweep voltammetry (LSV). Compared to Pt/MWCNTs, the Pt/MnO x -MWCNTs electro-catalyst exhibits about 3.3 times higher forward peak current density, during cyclic voltammetry, and 4.6 times higher exchange current density in methanol electro-oxidation reaction. In addition, deposition of manganese oxide onto MWCNTs dramatically increases the electrochemical active surface area from 29.7 for Pt/MWCNTs to 89.4 m 2 g −1 Pt for Pt/MnO x -MWCNTs. The results of long-term cyclic voltammetry show superior stability of Pt nanoparticles upon addition of manganese oxide to the support. Furthermore, the kinetics of formation of the chemisorbed OH groups improves upon manganese oxide incorporation. This leads to a lower onset potential of CO ads oxidation on Pt/MnO x -MWCNTs than on Pt/MWCNTs

  8. Effect of flattened surface morphology of anodized aluminum oxide templates on the magnetic properties of nanoporous Co/Pt and Co/Pd thin multilayered films

    Science.gov (United States)

    Nguyen, T. N. Anh; Fedotova, J.; Kasiuk, J.; Bayev, V.; Kupreeva, O.; Lazarouk, S.; Manh, D. H.; Vu, D. L.; Chung, S.; Åkerman, J.; Altynov, V.; Maximenko, A.

    2018-01-01

    For the first time, nanoporous Al2O3 templates with smoothed surface relief characterized by flattened interpore areas were used in the fabrication of Co/Pd and Co/Pt multilayers (MLs) with strong perpendicular magnetic anisotropy (PMA). Alternating gradient magnetometry (AGM) revealed perfectly conserved PMA in the Co/Pd and Co/Pt porous MLs (antidot arrays) with a ratio of remanent magnetization (Mr) to saturation magnetization (MS) of about 0.99, anisotropy fields (Ha) of up to 2.6 kOe, and a small deviation angle of 8° between the easy magnetization axis and the normal to the film surface. The sufficient magnetic hardening of the porous MLs with enhanced coercive field HC of up to ∼1.9 kOe for Co/Pd and ∼1.5 kOe for Co/Pt MLs, as compared to the continuous reference samples (∼1.5-2 times), is associated with the pinning of the magnetic moments on the nanopore edges. Application of the Stoner-Wohlfarth model for fitting the experimental M/MS(H) curves yielded clear evidence of the predominantly coherent rotation mechanism of magnetization reversal in the porous films.

  9. Investigation on CO catalytic oxidation reaction kinetics of faceted perovskite nanostructures loaded with Pt

    KAUST Repository

    Yin, S. M.

    2017-01-18

    Perovskite lead titanate nanostructures with specific {111}, {100} and {001} facets exposed, have been employed as supports to investigate the crystal facet effect on the growth and CO catalytic activity of Pt nanoparticles. The size, distribution and surface chemical states of Pt on the perovskite supports have been significantly modified, leading to a tailored conversion temperature and catalytic kinetics towards CO catalytic oxidation.

  10. Pt supported on nanosized oxides for electrocatalyst used in polymer electrolyte fuel cells

    DEFF Research Database (Denmark)

    Banu, N.; Serban, E. C.; Marinescu, A.

    2011-01-01

    Even though Pt is a standard catalyst for fuel cells, new advanced materials with low activation energy and high specific surface area are required. Researches proved that conducting oxides are the emerging candidates as support for Pt catalysts targeting replacement of nanocarbons. This paper...

  11. Pt supported on nanosized oxides for electrocatalyst used in polymer electrolyte fuel cells

    DEFF Research Database (Denmark)

    Banu, N.; Serban, E. C.; Marinescu, A.

    2011-01-01

    Even though Pt is a standard catalyst for fuel cells, new advanced materials with low activation energy and high specific surface area are required. Researches proved that conducting oxides are the emerging candidates as support for Pt catalysts targeting replacement of nanocarbons. This paper pr...

  12. Synthesis, characterization and catalytic activity toward methanol oxidation of electrocatalyst Pt4+-NH2-MCM-41

    International Nuclear Information System (INIS)

    Zheng Huajun; Chen Zuo; Wang Limin; Ma Chun’an

    2012-01-01

    Highlights: ► It was first confirmed that the Pt 4+ exhibited a good electro-catalytic property for methanol oxidation. ► The Pt 4+ perfectly distributed on a mesoporous molecular sieve matrix synthesis by a facile method. ► The good performance of catalyst resistance to poisoning because of a homogeneous distribution of Pt 4+ and large specific surface area. - Abstract: Mesoporous material with functional group (Pt 4+ -NH 2 -MCM-41) was prepared by grafting aminopropyl group and adsorbing platinum ions on the surface of the commercial molecular sieve (MCM-41). The characterization carried out by X-ray photoelectron spectroscopy, X-ray diffraction, and N 2 adsorption–desorption measurement pointed out that Pt was adsorbed on the NH 2 -MCM-41 surface as the oxidation state (Pt 4+ ) and the surface area of Pt 4+ -NH 2 -MCM-41 was up to 564 m 2 /g. Transmission electron microscopy and elemental mapping indicated a homogeneous distribution of Pt 4+ throughout all surface of the mesoporous materials. Electro-catalytic properties of methanol oxidation on the Pt 4+ -NH 2 -MCM-41 electrode were investigated with electrochemical methods. The results showed that the Pt 4+ -NH 2 -MCM-41 electrode exhibited catalytic activity in the methanol electro-oxidation with the apparent activation energy being 49.29 kJ/mol, and the control step of methanol electro-oxidation was the mass transfer process. It is first proved that platinum ions had good electro-catalytic property for methanol oxidation and provided a new idea for developing electrode materials in future.

  13. CO oxidation on Pt(111) at near ambient pressures

    Science.gov (United States)

    Krick Calderón, S.; Grabau, M.; Ã`vári, L.; Kress, B.; Steinrück, H.-P.; Papp, C.

    2016-01-01

    The oxidation of CO on Pt(111) was investigated simultaneously by near ambient pressure X-ray photoelectron spectroscopy and online gas analysis. Different CO:O2 reaction mixtures at total pressures of up to 1 mbar were used in continuous flow mode to obtain an understanding of the surface chemistry. By temperature-programmed and by isothermal measurements, the onset temperature of the reaction was determined for the different reactant mixtures. Highest turnover frequencies were found for the stoichiometric mixture. At elevated temperatures, the reaction becomes diffusion-limited in both temperature-programmed and isothermal measurements. In the highly active regime, no adsorbates were detected on the surface; it is therefore concluded that the catalyst surface is in a metallic state, within the detection limits of the experiment, under the applied conditions. Minor bulk impurities such as silicon were observed to influence the reaction up to total inhibition by formation of non-platinum oxides.

  14. CO oxidation on Pt(111) at near ambient pressures

    International Nuclear Information System (INIS)

    Krick Calderón, S.; Grabau, M.; Kress, B.; Papp, C.; Óvári, L.; Steinrück, H.-P.

    2016-01-01

    The oxidation of CO on Pt(111) was investigated simultaneously by near ambient pressure X-ray photoelectron spectroscopy and online gas analysis. Different CO:O 2 reaction mixtures at total pressures of up to 1 mbar were used in continuous flow mode to obtain an understanding of the surface chemistry. By temperature-programmed and by isothermal measurements, the onset temperature of the reaction was determined for the different reactant mixtures. Highest turnover frequencies were found for the stoichiometric mixture. At elevated temperatures, the reaction becomes diffusion-limited in both temperature-programmed and isothermal measurements. In the highly active regime, no adsorbates were detected on the surface; it is therefore concluded that the catalyst surface is in a metallic state, within the detection limits of the experiment, under the applied conditions. Minor bulk impurities such as silicon were observed to influence the reaction up to total inhibition by formation of non-platinum oxides

  15. Surface electrochemistry of CO on Pt(110)-(1 × 2) and Pt(110)-(1 × 1) surfaces

    Science.gov (United States)

    Marković, N. M.; Grgur, B. N.; Lucas, C. A.; Ross, P. N.

    1997-07-01

    A new type of flame-annealing method has been developed for the preparation of surfaces having either fcc(110)-(1 × 1) or fcc(110)-(1 × 2) symmetry. In situ X-ray scattering studies show that both the Pt(110)-(1 × 2) and Pt(110)-(1 × 1) surfaces are stable in the potential region between 0 and 1.0 V. Adsorption of CO on the (1 × 2) surface in solution does not induce the (1 × 2)→(1 × 1) transition that is observed in UHV upon adsorption of CO. Nominally identical saturation coverages of hydrogen (H upd) and CO ad are observed on the two surfaces, implying that two H upd atoms or two CO ad molecules are adsorbed per unit cell of the reconstructed (1 × 2) surface. A significant increase in the interatomic spacing between the first and second layer of the reconstructed (1 × 2) surface occurs upon hydrogen adsorption to full coverage. Occupation of subsurface sites for H upd are inferred from this result. The (1 × 2) surface is found to have a much higher catalytic activity for the electro-oxidation of CO; the anodic oxidation of either CO ad or dissolved CO gas occurs at ≈ 0.3 V lower potential on the (1 × 2) than the (1 × 1) surface.

  16. 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

  17. Promotion effect of manganese oxide on the electrocatalytic activity of Pt/C for methanol oxidation in acid medium

    Science.gov (United States)

    Abdel Hameed, R. M.; Fetohi, Amani E.; Amin, R. S.; El-Khatib, K. M.

    2015-12-01

    The modification of Pt/C by incorporating metal oxides for electrocatalytic oxidation of methanol has gained major attention because of the efficiency loss during the course of long-time operation. This work describes the preparation of Pt-MnO2/C electrocatalysts through a chemical route using ethylene glycol or a mixture of ethylene glycol and sodium borohydride as a reducing agent. The crystallite structure and particle size of synthesized electrocatalysts are determined using X-ray diffraction (XRD) and transmission electron microscopy (TEM). The addition of MnO2 improves the dispersion of Pt nanoparticles. The electrocatalytic activity of Pt-MnO2/C towards methanol oxidation in H2SO4 solution is investigated using cyclic voltammetry and electrochemical impedance spectroscopy. The onset potential value of methanol oxidation peak is negatively shifted by 169 mV when MnO2 is introduced to Pt/C. Moreover, the charge transfer resistance value at Pt-MnO2/C is about 10 times as low as that at Pt/C. Chronoamperometry and chronopotentiometry show that CO tolerance is greatly improved at Pt-MnO2/C. The increased electrocatalytic activity and enhanced ability to clean platinum surface elect manganese oxide as a suitable promoter for the anode performance in direct methanol fuel cells (DMFCs).

  18. Simulating Linear Sweep Voltammetry from First-Principles: Application to Electrochemical Oxidation of Water on Pt(111) and Pt3Ni(111)

    DEFF Research Database (Denmark)

    Viswanathan, Venkatasubramanian; Hansen, Heine Anton; Rossmeisl, Jan

    2012-01-01

    Cyclic voltammetry is a fundamental experimental method for characterizing adsorbates on electrochemical surfaces. We present a model for the electrochemical solid–liquid interface, and we simulate the linear sweep voltammogram of the electrochemical oxidation of H2O on Pt(111) and Pt3Ni(111...

  19. Pt3Zr(0001): A substrate for growing well-ordered ultrathin zirconia films by oxidation

    Science.gov (United States)

    Antlanger, Moritz; Mayr-Schmölzer, Wernfried; Pavelec, Jiří; Mittendorfer, Florian; Redinger, Josef; Varga, Peter; Diebold, Ulrike; Schmid, Michael

    2012-07-01

    We have studied the surface of pure and oxidized Pt3Zr(0001) by scanning tunneling microscopy (STM), Auger electron microscopy, and density functional theory (DFT). The well-annealed alloy surface shows perfect long-range chemical order. Occasional domain boundaries are probably caused by nonstoichiometry. Pt3Zr exhibits ABAC stacking along [0001]; only the A-terminated surfaces are seen by STM, in agreement with DFT results showing a lower surface energy for the A termination. DFT further predicts a stronger inward relaxation of the surface Zr than for Pt, in spite of the larger atomic size of Zr. A closed ZrO2 film is obtained by oxidation in 10-7 mbar O2 at 400 ∘C and post-annealing at ≈800∘C. The oxide consists of an O-Zr-O trilayer, equivalent to a (111) trilayer of the fluorite structure of cubic ZrO2, but contracted laterally. The oxide forms a (19×19)R23∘ superstructure. The first monolayer of the substrate consists of Pt and contracts, similar to the metastable reconstruction of pure Pt(111). DFT calculations show that the oxide trilayer binds rather weakly to the substrate. In spite of the O-terminated oxide, bonding to the substrate mainly occurs via the Zr atoms in the oxide, which strongly buckle down toward the Pt substrate atoms if near a Pt position. According to DFT, the oxide has a band gap; STM indicates that the conduction band minimum lies ≈2.3 eV above EF.

  20. Synthesis, shape control, and methanol electro-oxidation properties of Pt-Zn alloy and Pt3Zn intermetallic nanocrystals.

    Science.gov (United States)

    Kang, Yijin; Pyo, Jun Beom; Ye, Xingchen; Gordon, Thomas R; Murray, Christopher B

    2012-06-26

    We report the first synthesis of highly monodisperse Pt(3)Zn nanocrystals (NCs). Shape-controlled synthesis generates cubic and spherical Pt-Zn NCs. Reaction temperature is the key to incorporate Zn into Pt, even in the absence of a strong reducing agent. The Pt-Zn NCs are active toward methanol oxidation, with the spherical NCs exhibiting higher activity than the cubic NCs. The Pt-Zn alloy phase can be transformed into the Pt(3)Zn intermetallic phase, upon annealing. The intermetallic Pt(3)Zn shows better performance than the alloy phase Pt-Zn. Besides the activity toward methanol oxidation, Pt-Zn NCs show excellent poisoning tolerance. With activities comparable to the commercial Pt catalyst, enhanced poisoning tolerance and lower cost, Pt-Zn and Pt(3)Zn NCs are a promising new family of catalysts for direct methanol fuel cells.

  1. Modeling the electro-oxidation of CO and H2/CO on Pt, Ru, PtRu and Pt3Sn

    DEFF Research Database (Denmark)

    Liu, Ping; Logadottir, Ashildur; Nørskov, Jens Kehlet

    2003-01-01

    is developed to describe the electro-oxidation of CO and H-2 at conditions relevant to the anode of a PEM fuel cell. The model is very simple and allows us to express the kinetics of a promoted anode surface relative to the activity of pure Pt directly from the calculated adsorption energy differences...... poorer than Pt. Within the model we can analyze the origin of the promoting effect of alloying. We find that for the CO oxidation reaction the lower overpotentials for Ru, PtRu and Pt3Sn are due to the fact that Ru and Sn are much better than Pt at dissociating H2O. The promoting effect of Ru and Sn on H...... geometry is the same. This ligand effect is ascribed to changes in the electronic structure of the surface atoms due to interactions with the surroundings, and the physical origin of the effect is discussed. The calculated adsorption energetics is used as input into a simple kinetic model, which...

  2. Ag/Au/Pt trimetallic nanoparticles with defects: preparation, characterization, and electrocatalytic activity in methanol oxidation

    Science.gov (United States)

    Thongthai, Kontee; Pakawanit, Phakkhananan; Chanlek, Narong; Kim, Jun-Hyun; Ananta, Supon; Srisombat, Laongnuan

    2017-09-01

    Two series of Ag x /Au/Pt y trimetallic nanoparticles (Ag x Au1Pt2 with x ranging from 1-5 and Ag4Au1Pt y with y ranging from 1-3) were prepared by a sequential chemical reduction method that involved the deposition of Pt on preformed Ag/Au core-shell particles by systematically controlling the amount of Ag, Au, and Pt metal precursor solutions. The structural changes (the diameters and increased surface roughness from the defective features) and absorption patterns (the significant reduction of the peak intensities) of the nanoparticles examined with TEM and UV-vis spectroscopy indicated the selective incorporation of Pt on the Ag/Au nanoparticles regardless of their compositions. In addition, a combination of WDX, XRD, and XPS analyses quantitatively and qualitatively confirmed the successful formation of the Ag x Au1Pt2 and Ag4Au1Pt y trimetallic nanoparticles. Subsequently, these series of nanoparticles were deposited on multi-wall carbon nanotubes (MWCNTs) to evaluate their electrocatalytic property in the methanol oxidation reaction (MOR) as a function of their metal compositions. The results showed that the electrocatalytic activities of all Ag4/Au1/Pt y systems were higher than those of typical Pt on the MWCNTs. In particular, the Ag4Au1Pt2 nanoparticles exhibited the highest electrocatalytic property for the MOR, suggesting the importance of the proper combination of metal constituents and structures to regulate the activity in electrocatalytic systems.

  3. Characterization of a surface modified carbon cryogel and a carbon supported Pt catalyst

    Directory of Open Access Journals (Sweden)

    BILJANA M. BABIĆ

    2007-08-01

    Full Text Available A carbon cryogel, synthesized by carbonization of a resorcinol/formaldehyde cryogel and oxidized in nitric acid, was used as catalyst support for Pt nano-particles. The Pt/C catalyst was prepared by a modified polyol synthesis method in an ethylene glycol (EG solution. Characterization by nitrogen adsorption showed that the carbon cryogel support and the Pt/C catalyst were mesoporous materials with high specific surface areas (SBET > 400 m2 g-1 and large mesoporous volumes. X-Ray diffraction of the catalyst demonstrated the successful reduction of the Pt precursor to metallic form. TEM Images of the Pt/C catalyst and Pt particle size distribution showed that the mean Pt particle size was about 3.3 nm. Cyclic voltammetry (CV experiments at various scan rates (from 2 to 200 mV s-1 were performed in 0.5 mol dm-3 HClO4 solution. The large capacitance of the oxidized carbon cryogel electrode, which arises from a combination of the double-layer capacitance and pseudocapacitance, associated with the participation of surface redox-type reactions was demonstrated. For the oxidized carbon cryogel, the total specific capacitance determined by 1/C vs. ν0.5 extrapolation method was found to be 386 F g-1. The hydrogen oxidation reaction at the investigated Pt/C catalyst proceeded as an electrochemically reversible, two-electron direct discharge reaction.

  4. Oxidation of Ni(Pt)Si by molecular vs. atomic oxygen

    International Nuclear Information System (INIS)

    Manandhar, Sudha; Copp, Brian; Kelber, J.A.

    2008-01-01

    X-ray photoelectron spectroscopy (XPS) has been used to characterize the oxidation of a clean Ni(Pt)Si surface under two distinct conditions: exposure to a mixed flux of atomic and molecular oxygen (O + O 2 ; P O+O 2 = 5 x 10 -6 Torr) and pure molecular oxygen (O 2 ; P O 2 = 10 -5 Torr) at ambient temperatures. Formation of the clean, stoichiometric (nickel monosilicide) phase under vacuum conditions results in the formation of a surface layer enriched in PtSi. Oxidation of this surface in the presence of atomic oxygen initially results in formation of a silicon oxide overlayer. At higher exposures, kinetically limited oxidation of Pt results in Pt silicate formation. No passivation of oxygen uptake of the sample is observed for total O + O 2 exposure 4 L, at which point the average oxide/silicate overlayer thickness is 23 (3) A (uncertainty in the last digit in parentheses). In contrast, exposure of the clean Ni(Pt)Si surface to molecular oxygen only (maximum exposure: 5 x 10 5 L) results in slow growth of a silicon oxide overlayer, without silicate formation, and eventual passivation at a total average oxide thickness of 8(1) A, compared to a oxide average thickness of 17(2) A (no silicate formation) for the as-received sample (i.e., exposed to ambient.) The aggressive silicon oxidation by atomic oxygen, results in Ni-rich silicide formation in the substrate and the kinetically limited oxidation of the Pt

  5. Electrochemical fabrication of clean dendritic Au supported Pt clusters for electrocatalytic oxidation of formic acid

    International Nuclear Information System (INIS)

    Xia Yue; Liu Jun; Huang Wei; Li Zelin

    2012-01-01

    Highlights: ► A smooth Au surface was rebuilt into clean dendrite via square wave potential pulses. ► It was performed in blank H 2 SO 4 solution without Au(III) species and other additives. ► Dendritic Au provided certain advantage for dispersing Pt due to its unique structure. ► Pt-decorated dendritic Au demonstrated high activity for the HCOOH electrooxidation. - Abstract: We report here the fabrication of clean dendritic gold (DG) directly on a smooth Au electrode via square wave potential pulses (SWPPs) in a blank H 2 SO 4 solution containing no Au(III) species and additives. The effects of potential range, frequency and duration time of SWPPs and H 2 SO 4 concentration on the construction of DG were systematically investigated. A possible mechanism was proposed to explain the growth of DG. The whole process was templateless and surfactantless, and therefore effectively avoided possible contaminations that occurred in other synthetic routes. Further, the prepared DG electrode functioned as a scaffold to support electrodeposited Pt clusters, producing Pt-decorated DG (Pt-DG) electrodes. The electrocatalytic properties of Pt-DG electrodes with various Pt loadings were examined for the oxidation of formic acid. The low Pt loading Pt-DG demonstrated different electrochemical behavior from that on Pt-decorated smooth gold (Pt-SG) and on Pt-decorated gold nanoparticles because there were more defect sites like steps and edges on the DG surface. Ensemble effect, as well as electronic effect, accounts for the improved electrocatalytic activity of low Pt loading Pt-DG.

  6. Graphene-oxide-supported Pt nanoparticles with high activity and stability for hydrazine electro-oxidation in a strong acidic solution

    Science.gov (United States)

    Kim, Ji Dang; Choi, Myong Yong; Choi, Hyun Chul

    2017-10-01

    Graphene-oxide-supported Pt (GO-Pt) nanoparticles were prepared by performing diimide-activated amidation and used in an electrocatalyst for hydrazine electro-oxidation in 0.5 M H2SO4 solution. The physico-chemical properties of the GO-Pt nanoparticles were characterized with various techniques, which revealed that highly dispersed Pt nanoparticles with an average size of 2.6 nm were densely deposited on the amidated GO due to their strong adhesion. Cyclic voltammograms were obtained and demonstrate that the GO-Pt catalyst exhibits significantly improved catalytic activity and long-term stability in hydrazine electro-oxidation in a strong acidic solution when compared to commercial Pt/C and Pt metal electrodes. These enhanced electrochemical properties are attributed to the large electrochemically active surface area that results from the smaller size and excellent dispersion of the Pt nanoparticles on amidated GO.

  7. Bimetallic Ag-Pt Sub-nanometer Supported Clusters as Highly Efficient and Robust Oxidation Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Negreiros, Fabio R. [CNR-ICCOM & IPCF, Consiglio Nazionale delle Ricerche, Pisa Italy; Halder, Avik [Materials Science Division, Argonne National Laboratory, Lemont IL USA; Yin, Chunrong [Materials Science Division, Argonne National Laboratory, Lemont IL USA; Singh, Akansha [Harish-Chandra Research Institute, HBNI, Chhatnag Road Jhunsi Allahabad 211019 India; Barcaro, Giovanni [CNR-ICCOM & IPCF, Consiglio Nazionale delle Ricerche, Pisa Italy; Sementa, Luca [CNR-ICCOM & IPCF, Consiglio Nazionale delle Ricerche, Pisa Italy; Tyo, Eric C. [Materials Science Division, Argonne National Laboratory, Lemont IL USA; Pellin, Michael J. [Materials Science Division, Argonne National Laboratory, Lemont IL USA; Bartling, Stephan [Institut für Physik, Universität Rostock, Rostock Germany; Meiwes-Broer, Karl-Heinz [Institut für Physik, Universität Rostock, Rostock Germany; Seifert, Sönke [X-ray Science Division, Argonne National Laboratory, Lemont IL USA; Sen, Prasenjit [Harish-Chandra Research Institute, HBNI, Chhatnag Road Jhunsi Allahabad 211019 India; Nigam, Sandeep [Chemistry Division, Bhabha Atomic Research Centre, Trombay Mumbai- 400 085 India; Majumder, Chiranjib [Chemistry Division, Bhabha Atomic Research Centre, Trombay Mumbai- 400 085 India; Fukui, Nobuyuki [East Tokyo Laboratory, Genesis Research Institute, Inc., Ichikawa Chiba 272-0001 Japan; Yasumatsu, Hisato [Cluster Research Laboratory, Toyota Technological Institute: in, East Tokyo Laboratory, Genesis Research Institute, Inc. Ichikawa, Chiba 272-0001 Japan; Vajda, Stefan [Materials Science Division, Argonne National Laboratory, Lemont IL USA; Nanoscience and Technology Division, Argonne National Laboratory, Lemont IL USA; Institute for Molecular Engineering, University of Chicago, Chicago IL USA; Fortunelli, Alessandro [CNR-ICCOM & IPCF, Consiglio Nazionale delle Ricerche, Pisa Italy; Materials and Process Simulation Center, California Institute of Technology, Pasadena CA USA

    2017-12-29

    A combined experimental and theoretical investigation of Ag-Pt sub-nanometer clusters as heterogeneous catalysts in the CO -> CO2 reaction (COox) is presented. Ag9Pt2 and Ag9Pt3 clusters are size-selected in the gas phase, deposited on an ultrathin amorphous alumina support, and tested as catalysts experimentally under realistic conditions and by first-principles simulations at realistic coverage. Insitu GISAXS/TPRx demonstrates that the clusters do not sinter or deactivate even after prolonged exposure to reactants at high temperature, and present comparable, extremely high COox catalytic efficiency. Such high activity and stability are ascribed to a synergic role of Ag and Pt in ultranano-aggregates, in which Pt anchors the clusters to the support and binds and activates two CO molecules, while Ag binds and activates O-2, and Ag/Pt surface proximity disfavors poisoning by CO or oxidized species.

  8. Microwave sinthesys and characterization of Pt and Pt-Rh-Sn electrocatalysts for ethanol oxidation

    Directory of Open Access Journals (Sweden)

    Jovanović Vladislava M.

    2011-01-01

    Full Text Available Carbon supported Pt and Pt-Rh-Sn catalysts were synthesized by microwave-polyol method in ethylene glycol solution and investigated for the ethanol electro-oxidation reaction. The catalysts were characterized in terms of structure, morphology and composition by employing XRD, STM and EDX techniques. STM analysis indicated rather uniform particles and particle size of below 2 nm for both catalysts. XRD analysis of the Pt/C catalyst revealed two phases, one with the main characteristic peaks of face centered cubic crystal structure (fcc of platinum and another related to graphite like structure of carbon support Vulcan XC-72R. However, in XRD pattern of the Pt-Rh-Sn/C catalyst diffraction peaks for Pt, Rh or Sn cannot be resolved, indicating an extremely low crystallinity. The small particle sizes and homogeneous size distributions of both catalysts should be attributed to the advantages of microwave assisted modified polyol process in ethylene glycol solution. Pt-Rh- Sn/C catalyst is highly active for the ethanol oxidation with the onset potential shifted for more than 150 mV to negative values and with currents nearly 5 times higher in comparison to Pt/C catalyst. The stability tests of the catalysts, as studied by the chronoamperometric experiments, reveal that the Pt-Rh-Sn/C catalyst is evidently less poisoned then Pt/C catalyst. The increased activity of Pt-Rh-Sn/C in comparison to Pt/C catalyst is most probably promoted by bifunctional mechanism and the electronic effect of alloyed metals.

  9. Pt surface segregation in bimetallic Pt 3M alloys: A density functional theory study

    Science.gov (United States)

    Ma, Yuguang; Balbuena, Perla B.

    A simplified 5-layer slab model is used to study Pt segregation at Pt 3M(1 1 1) surfaces (M = Ag, Au, Co, Cr, Cu, Fe, Ir, Mn, Mo, Ni, Pd, Re, Rh, Ru, Ti, V). The calculated segregation energies are generally in good agreement with the experimental results. However, for Pt 3Ti(1 1 1) and Pt 3Mn(1 1 1), the model is unable to give the correct prediction because the experimental subsurface compositions are very different from those of the model. Pt segregation is found to be correlated with the subsurface atomic structure, the size of metal atoms and the surface energy. Interestingly, the calculations show that the displacement of M atoms at the topmost Pt 3M layer can be used to predict the surface segregation trend. The local geometries for the segregation and non-segregation structures are carefully compared and the surface geometric effect on the oxygen reduction reaction (ORR) activity is discussed. In particular, it is determined that the enhanced ORR activity for the Pt-skin surfaces of Pt 3Ni(1 1 1) and Pt 3Co(1 1 1) alloys are not caused by geometric effects.

  10. SURFACE PROPERTIES AND CATALYTIC PERFORMANCE OF Pt ...

    African Journals Online (AJOL)

    Perovskite-type La2 –xSrxCoO4 mixed oxides have been prepared by calcination at various temperatures of precipitates obtained from aqueous solutions in the presence of citric or ethylenediamintetraacetic (EDTA) acids, and have been studied by X-ray diffraction (XRD), surface area (BET) measurements, temperature ...

  11. 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

  12. Iron oxide surfaces

    Science.gov (United States)

    Parkinson, Gareth S.

    2016-03-01

    was recently challenged and a new structure based on a thin film of Fe3O4(111) on α-Fe2O3(0001) was proposed. The merits of the competing models are discussed. The α-Fe2O3(1 1 bar02) "R-cut" surface is recommended as an excellent prospect for future study given its apparent ease of preparation and its prevalence in nanomaterial. In the latter sections the literature regarding adsorption on iron oxides is reviewed. First, the adsorption of molecules (H2, H2O, CO, CO2, O2, HCOOH, CH3OH, CCl4, CH3I, C6H6, SO2, H2S, ethylbenzene, styrene, and Alq3) is discussed, and an attempt is made to relate this information to the reactions in which iron oxides are utilized as a catalyst (water-gas shift, Fischer-Tropsch, dehydrogenation of ethylbenzene to styrene) or catalyst supports (CO oxidation). The known interactions of iron oxide surfaces with metals are described, and it is shown that the behaviour is determined by whether the metal forms a stable ternary phase with the iron oxide. Those that do not, (e.g. Au, Pt, Ag, Pd) prefer to form three-dimensional particles, while the remainder (Ni, Co, Mn, Cr, V, Cu, Ti, Zr, Sn, Li, K, Na, Ca, Rb, Cs, Mg, Ca) incorporate within the oxide lattice. The incorporation temperature scales with the heat of formation of the most stable metal oxide. A particular effort is made to underline the mechanisms responsible for the extraordinary thermal stability of isolated metal adatoms on Fe3O4 surfaces, and the potential application of this model system to understand single atom catalysis and sub-nano cluster catalysis is discussed. The review ends with a brief summary, and a perspective is offered including exciting lines of future research.

  13. Efficient C-C bond splitting on Pt monolayer and sub-monolayer catalysts during ethanol electro-oxidation: Pt layer strain and morphology effects.

    Science.gov (United States)

    Loukrakpam, Rameshwori; Yuan, Qiuyi; Petkov, Valeri; Gan, Lin; Rudi, Stefan; Yang, Ruizhi; Huang, Yunhui; Brankovic, Stanko R; Strasser, Peter

    2014-09-21

    Efficient catalytic C-C bond splitting coupled with complete 12-electron oxidation of the ethanol molecule to CO2 is reported on nanoscale electrocatalysts comprised of a Pt monolayer (ML) and sub-monolayer (sML) deposited on Au nanoparticles (Au@Pt ML/sML). The Au@Pt electrocatalysts were synthesized using surface limited redox replacement (SLRR) of an underpotentially deposited (UPD) Cu monolayer in an electrochemical cell reactor. Au@Pt ML showed improved catalytic activity for ethanol oxidation reaction (EOR) and, unlike their Pt bulk and Pt sML counterparts, was able to generate CO2 at very low electrode potentials owing to efficient C-C bond splitting. To explain this, we explore the hypothesis that competing strain effects due to the Pt layer coverage/morphology (compressive) and the Pt-Au lattice mismatch (tensile) control surface chemisorption and overall activity. Control experiments on well-defined model Pt monolayer systems are carried out involving a wide array of methods such as high-energy X-ray diffraction, pair-distribution function (PDF) analysis, in situ electrochemical FTIR spectroscopy, and in situ scanning tunneling microscopy. The vibrational fingerprints of adsorbed CO provide compelling evidence on the relation between surface bond strength, layer strain and morphology, and catalytic activity.

  14. Critical assessment of Pt surface energy - An atomistic study

    Science.gov (United States)

    Kim, Jin-Soo; Seol, Donghyuk; Lee, Byeong-Joo

    2018-04-01

    Despite the fact that surface energy is a fundamental quantity in understanding surface structure of nanoparticle, the results of experimental measurements and theoretical calculations for the surface energy of pure Pt show a wide range of scattering. It is necessary to further ensure the surface energy of Pt to find the equilibrium shape and atomic configuration in Pt bimetallic nanoparticles accurately. In this article, we critically assess and optimize the Pt surface energy using a semi-empirical atomistic approach based on the second nearest-neighbor modified embedded-atom method interatomic potential. That is, the interatomic potential of pure Pt was adjusted in a way that the surface segregation tendency in a wide range of Pt binary alloys is reproduced in accordance with experimental information. The final optimized Pt surface energy (mJ/m2) is 2036 for (100) surface, 2106 for (110) surface, and 1502 for (111) surface. The potential can be utilized to find the equilibrium shape and atomic configuration of Pt bimetallic nanoparticles more accurately.

  15. Synthesis of PtNi Alloy Nanoparticles on Graphene-Based Polymer Nanohybrids for Electrocatalytic Oxidation of Methanol

    Directory of Open Access Journals (Sweden)

    Tung-Yuan Yung

    2016-12-01

    Full Text Available We have successfully produced bimetallic PtNi alloy nanoparticles on poly(diallyldimethylammonium chloride (PDDA-modified graphene nanosheets (PtNi/PDDA-G by the “one-pot” hydrothermal method. The size of PtNi alloy nanoparticles is approximately 2–5 nm. The PDDA-modified graphene nanosheets (PDDA-G provides an anchored site for metal precursors; hence, the PtNi nanoparticles could be easily bond on the PDDA-G substrate. PtNi alloy nanoparticles (2–5 nm display a homogenous alloy phase embedded on the PDDA-G substrate, evaluated by Raman, X-ray diffractometer (XRD, thermal gravity analysis (TGA, electron surface chemical analysis (ESCA, and electron energy loss spectroscopy (EELS. The Pt/Ni ratio of PtNi alloy nanoparticles is ~1.7, examined by the energy dispersive spectroscopy (EDS spectra of transmitting electron microscopy (EDS/TEM spectra and mapping technique. The methanol electro-oxidation of PtNi/PDDA-G was evaluated by cyclic voltammetry (CV in 0.5 M of H2SO4 and 0.5 M of CH3OH. Compared to Pt on carbon nanoparticles (Pt/C and Pt on Graphene (Pt/G, the PtNi/PDDA-G exhibits the optimal electrochemical surface area (ECSA, methanol oxidation reaction (MOR activity, and durability by chrono amperometry (CA test, which can be a candidate for MOR in the electro-catalysis of direct methanol fuel cells (DMFC.

  16. First principles Tafel kinetics of methanol oxidation on Pt(111)

    Science.gov (United States)

    Fang, Ya-Hui; Liu, Zhi-Pan

    2015-01-01

    Electrocatalytic methanol oxidation is of fundamental importance in electrochemistry and also a key reaction in direct methanol fuel cell. To resolve the kinetics at the atomic level, this work investigates the potential-dependent reaction kinetics of methanol oxidation on Pt(111) using the first principles periodic continuum solvation model based on modified-Poisson-Boltzmann equation (CM-MPB), focusing on the initial dehydrogenation elementary steps. A theoretical model to predict Tafel kinetics (current vs potential) is established by considering that the rate-determining step of methanol oxidation (to CO) is the first Csbnd H bond breaking (CH3OH(aq) → CH2OH* + H*) according to the computed free energy profile. The first Csbnd H bond breaking reaction needs to overcome a large entropy loss during methanol approaching to the surface and replacing the adsorbed water molecules. While no apparent charge transfer is involved in this elementary step, the charge transfer coefficient of the reaction is calculated to be 0.36, an unconventional value for charge transfer reactions, and the Tafel slope is deduced to be 166 mV. The results show that the metal/adsorbate interaction and the solvation environment play important roles on influencing the Tafel kinetics. The knowledge learned from the potential-dependent kinetics of methanol oxidation can be applied in general for understanding the electrocatalytic reactions of organic molecules at the solid-liquid interface.

  17. 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.

  18. Active Pt3Ni (111) Surface of Pt3Ni Icosahedron for Oxygen Reduction.

    Science.gov (United States)

    Zhu, Jianbing; Xiao, Meiling; Li, Kui; Liu, Changpeng; Zhao, Xiao; Xing, Wei

    2016-11-09

    Highly active, durable oxygen reduction reaction (ORR) electrocatalysts are extremely important for fuel cell applications. Herein, we provide an efficient way to synthesis of activity Pt 3 M icosahedra by the one-pot hydrothermal method in the presence of glucosamine which can well adjust the reduction rate of Pt 4+ and efficiently control the morphology of final catalysts. Compared to Pt/C, the Pt 3 Ni icosahedra show 32-fold and 12-fold enhancement in specific and mass activity, respectively. Furthermore, robust durability was also observed in the accelerated durability test. Thus, this Pt 3 Ni icosahedron is found among the best Pt-based ORR catalysts, moreover, the findings also demonstrate how to mimic active extended surfaces in nanoscale.

  19. 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.

  20. Dispersion of Pt Nanoparticle-Doped Reduced Graphene Oxide Using Aniline as a Stabilizer

    Directory of Open Access Journals (Sweden)

    Hyoung-Joon Jin

    2012-12-01

    Full Text Available In this study, a simple one-step method was developed to load small-sized Pt nanoparticles (3.1 ± 0.3 nm in large quantities (50 wt % on aniline-functionalized and reduced graphene oxide (r-fGO. In the process, an ethylene glycol solution and aniline-functionalized moiety play the roles of reducing agent and stabilizer for the Pt nanoparticles, respectively, without damaging the graphite structures of the r-fGO. The Pt nanoparticles loading on the surface of r-fGO with uniform dispersion have a great effect on the electrical conductivity.

  1. Metal Phosphate-Supported Pt Catalysts for CO Oxidation

    Science.gov (United States)

    Qian, Xiaoshuang; Qin, Hongmei; Meng, Tao; Lin, Yi; Ma, Zhen

    2014-01-01

    Oxides (such as SiO2, TiO2, ZrO2, Al2O3, Fe2O3, CeO2) have often been used to prepare supported Pt catalysts for CO oxidation and other reactions, whereas metal phosphate-supported Pt catalysts for CO oxidation were rarely reported. Metal phosphates are a family of metal salts with high thermal stability and acid-base properties. Hydroxyapatite (Ca10(PO4)6(OH)2, denoted as Ca-P-O here) also has rich hydroxyls. Here we report a series of metal phosphate-supported Pt (Pt/M-P-O, M = Mg, Al, Ca, Fe, Co, Zn, La) catalysts for CO oxidation. Pt/Ca-P-O shows the highest activity. Relevant characterization was conducted using N2 adsorption-desorption, inductively coupled plasma (ICP) atomic emission spectroscopy, X-ray diffraction (XRD), transmission electron microscopy (TEM), CO2 temperature-programmed desorption (CO2-TPD), X-ray photoelectron spectroscopy (XPS), and H2 temperature-programmed reduction (H2-TPR). This work furnishes a new catalyst system for CO oxidation and other possible reactions. PMID:28788293

  2. Metal Phosphate-Supported Pt Catalysts for CO Oxidation

    Directory of Open Access Journals (Sweden)

    Xiaoshuang Qian

    2014-12-01

    Full Text Available Oxides (such as SiO2, TiO2, ZrO2, Al2O3, Fe2O3, CeO2 have often been used to prepare supported Pt catalysts for CO oxidation and other reactions, whereas metal phosphate-supported Pt catalysts for CO oxidation were rarely reported. Metal phosphates are a family of metal salts with high thermal stability and acid-base properties. Hydroxyapatite (Ca10(PO46(OH2, denoted as Ca-P-O here also has rich hydroxyls. Here we report a series of metal phosphate-supported Pt (Pt/M-P-O, M = Mg, Al, Ca, Fe, Co, Zn, La catalysts for CO oxidation. Pt/Ca-P-O shows the highest activity. Relevant characterization was conducted using N2 adsorption-desorption, inductively coupled plasma (ICP atomic emission spectroscopy, X-ray diffraction (XRD, transmission electron microscopy (TEM, CO2 temperature-programmed desorption (CO2-TPD, X-ray photoelectron spectroscopy (XPS, and H2 temperature-programmed reduction (H2-TPR. This work furnishes a new catalyst system for CO oxidation and other possible reactions.

  3. Pt nanoparticle-reduced graphene oxide nanohybrid for proton exchange membrane fuel cells.

    Science.gov (United States)

    Park, Dae-Hwan; Jeon, Yukwon; Ok, Jinhee; Park, Jooil; Yoon, Seong-Ho; Choy, Jin-Ho; Shul, Yong-Gun

    2012-07-01

    A platinum nanoparticle-reduced graphene oxide (Pt-RGO) nanohybrid for proton exchange membrane fuel cell (PEMFC) application was successfully prepared. The Pt nanoparticles (Pt NPs) were deposited onto chemically converted graphene nanosheets via ethylene glycol (EG) reduction. According to the powder X-ray diffraction (XRD) pattern and transmission electron microscopy (TEM) analysis, the face-centered cubic Pt NPs (3-5 nm in diameter) were homogeneously dispersed on the RGO nanosheets. The electrochemically active surface area and PEMFC power density of the Pt-RGO nanohybrid were determined to be 33.26 m2/g and 480 mW/cm2 (maximum values), respectively, at 75 degrees C and at a relative humidity (RH) of 100% in a single-cell test experiment.

  4. Efficient C–C bond splitting on Pt monolayer and sub-monolayer catalysts during ethanol electro-oxidation: Pt layer strain and morphology effects

    Energy Technology Data Exchange (ETDEWEB)

    Loukrakpam, Rameshwori; Yuan, Qiuyi; Petkov, Valeri; Gan, Lin; Rudi, Stefan; Yang, Ruizhi; Huang, Yunhui; Brankovic, Stanko R.; Strasser, Peter (TU Berlin); (Soochow); (CMU); (Huazhong); (Houston)

    2014-07-23

    Efficient catalytic C–C bond splitting coupled with complete 12-electron oxidation of the ethanol molecule to CO2 is reported on nanoscale electrocatalysts comprised of a Pt monolayer (ML) and sub-monolayer (sML) deposited on Au nanoparticles (Au@Pt ML/sML). The Au@Pt electrocatalysts were synthesized using surface limited redox replacement (SLRR) of an underpotentially deposited (UPD) Cu monolayer in an electrochemical cell reactor. Au@Pt ML showed improved catalytic activity for ethanol oxidation reaction (EOR) and, unlike their Pt bulk and Pt sML counterparts, was able to generate CO2 at very low electrode potentials owing to efficient C–C bond splitting. To explain this, we explore the hypothesis that competing strain effects due to the Pt layer coverage/morphology (compressive) and the Pt–Au lattice mismatch (tensile) control surface chemisorption and overall activity. Control experiments on well-defined model Pt monolayer systems are carried out involving a wide array of methods such as high-energy X-ray diffraction, pair-distribution function (PDF) analysis, in situ electrochemical FTIR spectroscopy, and in situ scanning tunneling microscopy. The vibrational fingerprints of adsorbed CO provide compelling evidence on the relation between surface bond strength, layer strain and morphology, and catalytic activity.

  5. Evaluation of the Scaffolding Effect of Pt Nanowires Supported on Reduced Graphene Oxide in PEMFC Electrodes

    Directory of Open Access Journals (Sweden)

    Peter Mardle

    2018-01-01

    Full Text Available The stacking and overlapping effect of two-dimensional (2D graphene nanosheets in the catalyst coating layer is a big challenge for their practical application in proton exchange membrane fuel cells (PEMFCs. These effects hinder the effective transfer of reactant gases to reach the active catalytic sites on catalysts supported on the graphene surface and the removal of the produced water, finally leading to large mass transfer resistances in practical electrodes and poor power performance. In this work, we evaluate the catalytic power performance of aligned Pt nanowires grown on reduced graphene oxide (rGO (PtNW/rGO as cathodes in 16-cm2 single PEMFCs. The results are compared to Pt nanoparticles deposited on rGO (Pt/rGO and commercial Pt/C nanoparticle catalysts. It is found that the scaffolding effect from the aligned Pt nanowire structure reduces the mass transfer resistance in rGO-based catalyst electrodes, and a nearly double power performance is achieved as compared with the Pt/rGO electrodes. However, although a higher mass activity was observed for PtNW/rGO in membrane electrode assembly (MEA measurement, the power performance obtained at a large current density region is still lower than the Pt/C in PEMFCs because of the stacking effect of rGO.

  6. Temperature-dependence of hydrogen oxidation reaction rates and CO-tolerance at carbon-supported Pt, Pt-Co, and Pt-Ru catalysts.

    Science.gov (United States)

    Uchida, Hiroyuki; Izumi, Kenji; Aoki, Koichi; Watanabe, Masahiro

    2009-03-21

    The temperature-dependence of the hydrogen oxidation reaction (HOR) rate was examined at commercial Pt, Pt3Co, PtRu, and PtRu(1.5) nano-sized catalysts (diameter, d = ca. 3 nm) supported on carbon black in 0.1 M HClO4 solution in the presence and absence of carbon monoxide by use of a channel flow electrode at temperatures from 30 to 90 degrees C. It was found that the values of the apparent rate constant k(app) (per real Pt active surface area) for the HOR at these supported catalysts agreed beautifully with those of the corresponding bulk electrodes in the whole temperature range. The dependence of the kinetically controlled current density (jk) on CO coverage at each supported catalyst was also identical to that of the bulk. Hence, no particle size effect was observed on the HOR activity and the CO tolerance, at least, was brought down to d = 3 nm.

  7. Suppression of oxidation in nickel germanosilicides by Pt incorporation

    International Nuclear Information System (INIS)

    Rahman, Md. Anisur; Osipowicz, Thomas; Pey, K.L.; Jin, L.J.; Choi, W.K.; Chi, D.Z.; Antoniadis, D.A.; Fitzgerald, E.A.; Isaacson, D.M.

    2005-01-01

    The effect of oxidation of 10 nm Ni/Si 0.75 Ge 0.25 and 10 nm Ni(10 at. %Pt)/Si 0.75 Ge 0.25 thin films at annealing temperatures ranging from 400 to 800 deg. C has been studied in detail by Rutherford backscattering spectrometry analysis, cross-sectional transmission electron microscopy, energy dispersive x-ray, and sheet resistance measurements. It is observed that for the films without Pt incorporation, almost two-thirds of the germanosilicide is oxidized. The incorporation of a Pt(10 at. %) into Ni not only dramatically reduces the oxidation of the germanosilicides, but also improves the interfacial roughness and morphology. The integral amount of oxygen found in the germanosilicide in the Ni(10 at. %Pt)Si 0.75 Si 0.25 films [(1.1±0.17)x10 17 at./cm 2 ] is approximately four times less than that of NiSi 0.75 Si 0.25 [(4.0±0.28)x10 17 at./cm 2 ]. This result is explained in terms of the roles of the higher melting point and bond energy of PtSi in NiSi and NiGe, and much lower free energy of the formation of platinum oxide

  8. 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.

  9. The Effect of PtRuIr Nanoparticle Crystallinity in Electrocatalytic Methanol Oxidation

    Directory of Open Access Journals (Sweden)

    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.

  10. The Effect of PtRuIr Nanoparticle Crystallinity in Electrocatalytic Methanol Oxidation

    Science.gov (United States)

    Ma, Yanjiao; Wang, Rongfang; Wang, Hui; Liao, Shijun; Key, Julian; Linkov, Vladimir; Ji, Shan

    2013-01-01

    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. PMID:28809233

  11. Pt nanocrystals electrodeposited on reduced graphene oxide/carbon fiber paper with efficient electrocatalytic properties

    Directory of Open Access Journals (Sweden)

    Zhiling Chen

    2017-08-01

    Full Text Available Carbon fiber paper (CFP wrapped with reduced graphene oxide (rGO film as the composite support (rGO/CFP of Pt catalysts was studied. It was found that rGO could affect the size and morphology of Pt nanocrystals (NCs. Concave nanocubes (CNC Pt NCs ~ 20 nm were uniformly electrodeposited on high reduced HrGO/CFP while irregular Pt NCs ~ 62 nm were loaded on low reduced LrGO. Compared with Pt-LrGO/CFP and Pt-MrGO/CFP, the CNC Pt-HrGO/CFP exhibited a higher electrochemically active surface area (121.7 m2 g−1, as well as enhanced electrooxidation activity of methanol (499 mA mg−1 and formic acid (950 mA mg−1. The results further demonstrated that the CNC Pt-HrGO/CFP could serve as the gas diffusion electrode in fuel cells and yielded a satisfactory performance (1855 mW mg−1. The work can provide an attractive perspective on the convenient preparation of the novel gas diffusion electrode for proton exchange membrane fuel cells.

  12. Initial stages of Pt(111) electrooxidation: dynamic and structural studies by surface X-ray diffraction

    International Nuclear Information System (INIS)

    Drnec, Jakub; Ruge, Martin; Reikowski, Finn; Rahn, Björn; Carlà, Francesco; Felici, Roberto; Stettner, Jochim; Magnussen, Olaf M.; Harrington, David A.

    2017-01-01

    In-situ surface X-ray diffraction is used to characterize the surface oxides on a Pt(111) surface in 0.1 M HClO 4 . Detailed analysis at two potentials confirms that the surface restructuring in the initial oxidation stages is consistent with a place exchange process between Pt and O atoms, and the exchanged Pt atoms are located above their original positions in the Pt(111) lattice. The (1,1,1.5) reflection is used to dynamically study the surface during cyclic voltammetry. The restructuring associated with the place exchange initiates with the CV peak at 1.05 V, even though multiple cycles to 1.17 V lead to no changes in the CV. The restructuring is reversible below a critical coverage of place exchanged Pt atoms, which we estimate to be between 0.07 and 0.15 ML. Extensive cycling to potentials higher or equal to 1.17 V leads to progressive disordering of the surface.

  13. Bulk ordering and surface segregation in Ni50Pt50

    DEFF Research Database (Denmark)

    Pourovskii, L.P.; Ruban, Andrei; Abrikosov, I.A.

    2001-01-01

    in the bulk compare well with experimental data. The surface-alloy compositions for the (111) and (110) facets above the ordering transition temperature are also found to be in a good agreement with experiments. It is demonstrated that the segregation profile at the (110) surface of NiPt is mainly caused...... by the unusually strong segregation of Pt into the second layer and the interlayer ordering due to large chemical nearest-neighbor interactions....

  14. Insight into the Effect of Sn on CO and Formic Acid Oxidation at PtSn Catalysts

    DEFF Research Database (Denmark)

    Stevanović, S.; Tripković, D.; Tripkovic, Vladimir

    2014-01-01

    adsorbed tin, Snirr. The presence of Sn in any form (oxide, alloyed, or Snirr) on the surface shifts the onset potential for the CO oxidation negatively by more than 0.4 V in comparison to equivalently treated Pt/C catalysts. For the CO-annealed PtSn/C catalyst, a so-called skeleton structure, Sn...... is present only in the subsurface layers. The subsurface Sn has a mild effect on the CO activity, and hence the onset potential is only marginally shifted to cathodic potentials by ∼50 mV compared to that on Pt/C. The formic acid oxidation is enhanced at any of the PtSn/C surfaces with Sn in the surface...... layer. The activity enhancement is explained by a reduced CO poisoning of the surface Pt sites. As a consequence, the current is not entering plateau as on the Pt/C catalysts. Furthermore, the skeleton PtSn/C is ∼2 times more active than similarly treated Pt/C. The results have been substantiated...

  15. Effect of water vapor on evolution of a thick Pt-layer modified oxide on the NiCoCrAl alloy at high temperature

    Science.gov (United States)

    Song, Peng; He, Xuan; Xiong, Xiping; Ma, Hongqing; Song, Qunling; Lü, Jianguo; Lu, Jiansheng

    2018-03-01

    To investigate the effect of water vapor on the novel Pt-containing oxide growth behavior, Pt-addition within the oxide layer on the surface of NiCoCrAl coating and furnace cycle tests were carried out at 1050 °C in air and air plus water vapor. The thick Pt-containing oxide layer on NiCoCrAl exhibits a different oxidation growth behavior compared to the conventional Pt-diffusion metallic coatings. The Pt-containing oxide after oxidation in air plus water vapor showed a much thicker oxide layer compare to the ones without Pt addition, and also presented a much better coating adhesion. During the oxidation process in air, Pt promotes the spinel (NiCr2O4) formation. However, the Cr2O3 formed in air with water vapor and fixed Pt within the complex oxide layer. The water vapor promoted the Ni and Co outer-diffusion, and combined with Pt to form CoPt compounds on the surface of the NiCoCrAl coating system.

  16. 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.

  17. Hydrothermal synthesis of size-dependent Pt in Pt/MWCNTs nanocomposites for methanol electro-oxidation

    International Nuclear Information System (INIS)

    Chen Liang; Lu Gongxuan

    2008-01-01

    A hydrothermal method has been developed to prepare size-controlled Pt nanoparticles dispersed highly on multiwalled carbon nanotubes (Pt/MWCNTs). It was found that the size of Pt nanoparticles was strongly dependent on the solution pH in synthesis. The Pt nanoparticles with mean size of 3.0, 4.2 and 9.1 nm were obtained at pHs 13, 12 and 10 separately. After Pt/MWCNTs composites were fabricated, the different properties of cyclic voltammetry and chronoamperometry in electro-oxidation of methanol were found. The results showed that the smaller diameter Pt deposited Pt/MWCNTs nanocomposites exhibited higher electrocatalytic activity for methanol oxidation. By characterization of X-ray diffraction (XRD), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS), size-dependent activities were identified

  18. Pt/MOx/SiO2, Pt/MOx/TiO2, and Pt/MOx/Al2O3 Catalysts for CO Oxidation

    Directory of Open Access Journals (Sweden)

    Hongmei Qin

    2015-04-01

    Full Text Available Conventional supported Pt catalysts have often been prepared by loading Pt onto commercial supports, such as SiO2, TiO2, Al2O3, and carbon. These catalysts usually have simple metal-support (i.e., Pt-SiO2 interfaces. To tune the catalytic performance of supported Pt catalysts, it is desirable to modify the metal-support interfaces by incorporating an oxide additive into the catalyst formula. Here we prepared three series of metal oxide-modified Pt catalysts (i.e., Pt/MOx/SiO2, Pt/MOx/TiO2, and Pt/MOx/Al2O3, where M = Al, Fe, Co, Cu, Zn, Ba, La for CO oxidation. Among them, Pt/CoOx/SiO2, Pt/CoOx/TiO2, and Pt/CoOx/Al2O3 showed the highest catalytic activities. Relevant samples were characterized by N2 adsorption-desorption, X-ray diffraction (XRD, transmission electron microscopy (TEM, H2 temperature-programmed reduction (H2-TPR, X-ray photoelectron spectroscopy (XPS, CO temperature-programmed desorption (CO-TPD, O2 temperature-programmed desorption (O2-TPD, and CO2 temperature-programmed desorption (CO2-TPD.

  19. Detecting decompositions of sulfur hexafluoride using reduced graphene oxide decorated with Pt nanoparticles

    Science.gov (United States)

    Chen, Dachang; Tang, Ju; Zhang, Xiaoxing; Fang, Jiani; Li, Yi; Zhuo, Ran

    2018-05-01

    The resistance-typed gas sensing material of Pt nanoparticles (PtNPs) decorated reduced graphene oxide (RGO) synthesized by one-step chemical reduction for the detection of four types of SF6 decompositions was explored. The PtNPs disperse uniformly on RGO with particle size near 2–4 nm and a small number of particles are larger than 10 nm. Gas sensing tests suggest that the introduction of PtNPs increases the response to SO2, SOF2 and H2S compared to pure RGO and PtNPs-RGO experiences resistance reducing in SO2 and SOF2 while presenting the opposite case in H2S. Elevating the temperature enhances the recovery properties to SO2 and H2S but lowers the sensitivity. The sensing mechanism for Pt-RGO in low oxygen and water environment depends mainly on the charge transfer between gas and adsorbent and the solvent on material surface. The work provides experimental investigation of Pt-RGO to detect SF6 decompositions.

  20. Surface Modification and Heat Generation of FePt Nanoparticles

    Directory of Open Access Journals (Sweden)

    Da-Hua Wei

    2017-02-01

    Full Text Available The chemical reduction of ferric acetylacetonate (Fe(acac3 and platinum acetylacetonate (Pt(acac2 using the polyol solvent of phenyl ether as an agent as well as an effective surfactant has successfully yielded monodispersive FePt nanoparticles (NPs with a hydrophobic ligand and a size of approximately 3.8 nm. The present FePt NPs synthesized using oleic acid and oleylamine as the stabilizers under identical conditions were achieved with a simple method. The surface modification of FePt NPs by using mercaptoacetic acid (thiol as a phase transfer reagent through ligand exchange turned the NPs hydrophilic, and the FePt NPs were water-dispersible. The hydrophilic NPs indicated slight agglomeration which was observed by transmission electron microscopy images. The thiol functional group bond to the FePt atoms of the surface was confirmed by Fourier transform infrared spectroscopy (FTIR spectra. The water-dispersible FePt NPs employed as a heating agent could reach the requirement of biocompatibility and produce a sufficient heat response of 45 °C for magnetically induced hyperthermia in tumor treatment fields.

  1. Catalytically favorable surface patterns in Pt-Au nanoclusters

    KAUST Repository

    Mokkath, Junais Habeeb

    2013-01-01

    Motivated by recent experimental demonstrations of novel PtAu nanoparticles with highly enhanced catalytic properties, we present a systematic theoretical study that explores principal catalytic indicators as a function of the particle size and composition. We find that Pt electronic states in the vicinity of the Fermi level combined with a modified electron distribution in the nanoparticle due to Pt-to-Au charge transfer are the origin of the outstanding catalytic properties. From our model we deduce the catalytically favorable surface patterns that induce ensemble and ligand effects. © The Royal Society of Chemistry 2013.

  2. N, P-codoped Mesoporous Carbon Supported PtCox Nanoparticles and Their Superior Electrochemical toward Methanol Oxidation

    Science.gov (United States)

    Cui, Hangjun; Li, Yueming; Liu, Shimin

    2018-03-01

    In this report, a novel strategy by using the N, P co-doped mesoporous carbon structure as catalyst support to enhance the electrochemical catalytic activity of Pt-based catalysts is proposed. The as-synthesized PtCox@N, P-doped mesoporous carbon nanocomposties have been studied as an anode catalyst toward methanol oxidation, exhibiting greatly improved electrochemical activity and stability compared with Pt@mesoporous carbon. The synergistic effects of N, P dual-doping and porous carbon structure help to achieve better electron transport at the electrode surface, which eventually leads to greatly enhanced catalytic activity compared to the pristine Pt/mesoporous carbon.…

  3. Modeling Electrocatalysis -- Electro-oxidation of Pt(111)

    Science.gov (United States)

    Jacob, Timo; Scheffler, Matthias

    2006-03-01

    Electrochemical reactions (such as in fuel cells) usually occur under conditions of finite temperature, pressure, and electrode potential, implying a very involved situation, possibly leading to novel surface materials. Especially the presence of an electrode potential, which results in the formation of an electric double-layer, affects the composition and structure of the electrode/electrolyte-interface. Towards a more realistic treatment of electrocatalysis we developed an appropriate theory in which the electrode of the interface is assumed to be in contact with a bulk-electrode reservoir (at chemical potential μel) while the electrolyte is in contact with a bulk-electrolyte reservoir. Although we are in the process of simulating the entire electric-double layer self-consistently, the present approach already allows us to estimate the limites of the expected effects. As a first application we studied the electro-oxidation of Pt(111) by calculating the p/T/φ-phase diagram. The obtained behavior, that positive electrode potentials stabilize higher oxygen coverages, is in qualitative agreement with cyclic-voltammetry experiments.

  4. The Pt-enriched PtNi alloy surface and its excellent catalytic performance in hydrolytic hydrogenation of cellulose.

    Science.gov (United States)

    Liang, Guanfeng; He, Limin; Arai, Masahiko; Zhao, Fengyu

    2014-05-01

    Ni-based catalysts are currently a subject of intense research in the hydrolytic hydrogenation of cellulose. We previously reported that Ni/ZSM-5 catalyst gave high yield of hexitols. However, Ni-based catalysts suffered fast deactivation in hot-compressed water. In this follow-up study we designed highly active Ni-based bimetallic catalysts with excellent hydrothermal stability for the hydrolytic hydrogenation of microcrystalline cellulose. PtNi/ZSM-5 shows a 76.9 % yield of hexitols, which is the best obtained so far in the hydrolytic hydrogenation of microcrystalline cellulose over Ni-based catalysts. Furthermore, the yield of hexitols remained greater than 55 % after the catalyst was reused for 4 times. The results showed that PtNi nanoparticles were formed with a Pt-enriched alloy surface as confirmed by XRD, H2-TPR (temperature-programmed H2 reduction), XPS (X-ray photoelectron spectroscopy), and H2-TPD (temperature-programmed H2 desorption). The surface features of these nano-particles were characterized by CO-TPD (temperature-programmed CO desorption), CO-FTIR (CO adsorption FTIR spectroscopy), HRTEM (high resolution TEM), and O2-TPO (temperature programmed oxidation) and this special surface structure may be responsible for the high activity, selectivity, and stability in the hydrolytic hydrogenation of cellulose in hot-compressed water. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Plasma-induced synthesis of Pt nanoparticles supported on TiO2 nanotubes for enhanced methanol electro-oxidation

    Science.gov (United States)

    Su, Nan; Hu, Xiulan; Zhang, Jianbo; Huang, Huihong; Cheng, Jiexu; Yu, Jinchen; Ge, Chao

    2017-03-01

    A Pt/C/TiO2 nanotube composite catalyst was successfully prepared for enhanced methanol electro-oxidation. Pt nanoparticles with a particle size of 2 nm were synthesized by plasma sputtering in water, and anatase TiO2 nanotubes with an inner diameter of approximately 100 nm were prepared by a simple two-step anodization method and annealing process. Field-emission scanning electron microscopy images indicated that the different morphologies of TiO2 synthesized on the surface of Ti foils were dependent on the different anodization parameters. The electrochemical performance of Pt/C/TiO2 catalysts for methanol oxidation showed that TiO2 nanotubes were more suitable for use as Pt nanoparticle support materials than irregular TiO2 short nanorods due to their tubular morphology and better electronic conductivity. X-ray photoelectron spectroscopy characterization showed that the binding energies of the Pt 4f of the Pt/C/TiO2 nanotubes exhibited a slightly positive shift caused by the relatively strong interaction between Pt and the TiO2 nanotubes, which could mitigate the poisoning of the Pt catalyst by COads, and further enhance the electrocatalytic performance. Thus, the as-obtained Pt/C/TiO2 nanotubes composites may become a promising catalyst for methanol electro-oxidation.

  6. A volcano curve: optimizing methanol electro-oxidation on Pt-decorated Ru nanoparticles.

    Science.gov (United States)

    Du, Bingchen; Rabb, Savelas A; Zangmeister, Christopher; Tong, YuYe

    2009-10-01

    Controlled Pt adlayers were deposited on commercial Ru nanoparticles (NPs) using an industrially scalable one-pot ethylene glycol (EG) reduction based method and were characterized by X-ray diffraction (XRD), electrochemical (EC) CO stripping voltammetry, inductively-coupled plasma optical emission spectrometry (ICP-OES), X-ray photoemission spectroscopy (XPS), and transmission electron microscopy (TEM). Compared with the previously used "spontaneous deposition", the wet chemistry-based EG method is less technically demanding, i.e. no need to handle high-temperature hydrogen reduction, offers a better control of the Pt packing density (PD), enables the formation of stable, segregated Pt surface adlayers for optimal tuning and use of Pt, and effectively prevents NPs sintering. Two batches of a total of 11 (8 vs. 3) samples with different values of Pt PD ranging from 0.05 to 0.93 were prepared, with a time interval of more than 18 months between the sytheses of the two batches of samples, and an excellent reproducibility of results was observed. All samples were investigated in terms of methanol (MeOH) electro-oxidation (EO) by cyclic voltammetry (CV) and chronoamperometry (CA). Although the peak current of CV increased as the Pt content increased, the long-term steady-state MeOH electro-oxidation current density of the Pt-decorated Ru NPs measured by CA showed a volcano curve as a function of the Pt PD, with the maximum appearing at the PD of 0.31. The optimal peak activity was approximately 150% higher than that of the industrial benchmark PtRu (1 : 1) alloy NPs and could deliver the same performance at half the electrode material cost. Fundamentally, such a volcano curve in the reaction current is the result of two competing processes of the EO of MeOH: the triple dehydrogenation of MeOH that prefers more Pt ensemble sites, and the elimination of poisonous CO that is enhanced by more adjacent Ru/Pt sites via the so-called bifunctional mechanism and also by

  7. Highly Selective TiN-Supported Highly Dispersed Pt Catalyst: Ultra Active toward Hydrogen Oxidation and Inactive toward Oxygen Reduction.

    Science.gov (United States)

    Luo, Junming; Tang, Haibo; Tian, Xinlong; Hou, Sanying; Li, Xiuhua; Du, Li; Liao, Shijun

    2018-01-31

    The severe dissolution of the cathode catalyst, caused by an undesired oxygen reduction reaction at the anode during startup and shutdown, is a fatal challenge to practical applications of polymer electrolyte membrane fuel cells. To address this important issue, according to the distinct structure-sensitivity between the σ-type bond in H 2 and the π-type bond in O 2 , we design a HD-Pt/TiN material by highly dispersing Pt on the TiN surface to inhibit the unwanted oxygen reduction reaction. The highly dispersed Pt/TiN catalyst exhibits excellent selectivity toward hydrogen oxidation and oxygen reduction reactions. With a Pt loading of 0.88 wt %, our catalyst shows excellent hydrogen oxidation reaction activity, close to that of commercial 20 wt % Pt/C catalyst, and much lower oxygen reduction reaction activity than the commercial 20 wt % Pt/C catalyst. The lack of well-ordered Pt facets is responsible for the excellent selectivity of the HD-Pt/TiN materials toward hydrogen oxidation and oxygen reduction reactions. Our work provides a new and cost-effective solution to design selective catalysts toward hydrogen oxidation and oxygen reduction reactions, making the strategy of using oxygen-tolerant anode catalyst to improve the stability of polymer electrolyte membrane fuel cells during startup and shutdown more affordable and practical.

  8. Characterization of Pt-Pd/C Electrocatalyst for Methanol Oxidation in Alkaline Medium

    Directory of Open Access Journals (Sweden)

    S. S. Mahapatra

    2011-01-01

    Full Text Available The Pt-Pd/C electrocatalyst was synthesized on graphite substrate by the electrochemical codeposition technique. The physicochemical characterization of the catalyst was done by SEM, XRD, and EDX. The electrochemical characterization of the Pt-Pd/C catalyst for methanol electro-oxidation was studied over a range of NaOH and methanol concentrations using cyclic voltammetry, quasisteady-state polarization, chronoamperometry, and electrochemical impedance spectroscopy. The activity of methanol oxidation increased with pH due to better OH species coverage on the electrode surface. At methanol concentration (>1.0 M, there is no change in the oxidation peak current density because of excess methanol at the electrode surface and/or depletion of OH− at the electrode surface. The Pt-Pd/C catalyst shows good stability and the low value of Tafel slope and charge transfer resistance. The enhanced electrocatalytic activity of the electrodes is ascribed to the synergistic effect of higher electrochemical surface area, preferred OH− adsorption, and ad-atom contribution on the alloyed surface.

  9. Exotic high activity surface patterns in PtAu nanoclusters

    KAUST Repository

    Mokkath, Junais Habeeb

    2013-05-09

    The structure and chemical ordering of PtAu nanoclusters of 79, 135, and 201 atoms are studied via a combination of a basin hopping atom-exchange technique (to locate the lowest energy homotops at fixed composition), a symmetry orbit technique (to find the high symmetry isomers), and density functional theory local reoptimization (for determining the most stable homotop). The interatomic interactions between Pt and Au are derived from the empirical Gupta potential. The lowest energy structures show a marked tendency toward PtcoreAushell chemical ordering by enrichment of the more cohesive Pt in the core region and of Au in the shell region. We observe a preferential segregation of Pt atoms to (111) facets and Au atoms to (100) facets of the truncated octahedron cluster motif. Exotic surface patterns are obtained particularly for Pt-rich compositions, where Pt atoms are being surrounded by Au atoms. These surface arrangements boost the catalytic activity by creating a large number of active sites. © 2013 American Chemical Society.

  10. Vanadium oxide decorated carbon nanotubes as a promising support of Pt nanoparticles for methanol electro-oxidation reaction.

    Science.gov (United States)

    Nouralishahi, Amideddin; Khodadadi, Abbas Ali; Rashidi, Ali Morad; Mortazavi, Yadollah

    2013-03-01

    VO(x)-MWCNTs nanocomposite was prepared via deposition-precipitation method followed by microwave treatment. Platinum nanoparticles were dispersed via polyol process over the nanocomposite support, and thus, prepared electro-catalyst was employed in methanol electro-oxidation reaction. The electro-catalysts were characterized by means of TGA, XRD, EDS, FESEM, TEM, and H(2)-TPR analysis. The electro-catalytic activity and stability of the electrodes toward methanol oxidation reaction in acidic medium were studied by using cyclic voltammetry (CV), CO-stripping, and electrochemical impedance spectroscopy (EIS) techniques. Compared to the Pt/MWCNTs, the Pt/VO(x)-MWCNTs electro-catalyst not only exhibits high electro-catalytic activity, but also shows very good stability during methanol electro-oxidation reaction. In addition, the presence of VO(x) in the composite support dramatically increases the electrochemical active surface area of platinum nanoparticles. The results of electrochemical impedance spectroscopy reveal that formation kinetics of adsorbed hydroxyl group on surface of the electro-catalysts is improved upon vanadium oxide addition to the support. This phenomenon is very helpful to facilitate oxidative removal of adsorbed CO group through bifunctional mechanism on Pt/VO(x)-MWCNTs. Copyright © 2012 Elsevier Inc. All rights reserved.

  11. Electrochemical characterization of Pt-Ru-Pd catalysts for methanol oxidation reaction in direct methanol fuel cells.

    Science.gov (United States)

    Choi, M; Han, C; Kim, I T; An, J C; Lee, J J; Lee, H K; Shim, J

    2011-01-01

    PtRuPd nanoparticles on carbon black were prepared and characterized as electrocatalysts for methanol oxidation reaction in direct methanol fuel cells. Nano-sized Pd (2-4 nm) particles were deposited on Pt/C and PtRu/C (commercial products) by a simple chemical reduction process. The structural and physical information of the PtRuPd/C were confirmed by TEM and XRD, and their electrocatalytic activities were measured by cyclic voltammetry and linear sweep voltammetry. The catalysts containing Pd showed higher electrocatalytic activity for methanol oxidation reaction than the other catalysts. This might be attributed to an increase in the electrochemical surface area of Pt, which is caused by the addition of Pd; this results in increased catalyst utilization.

  12. Promotion effect of manganese oxide on the electrocatalytic activity of Pt/C for methanol oxidation in acid medium

    Energy Technology Data Exchange (ETDEWEB)

    Abdel Hameed, R.M., E-mail: randa311eg@yahoo.com [Chemistry Department, Faculty of Science, Cairo University, Giza (Egypt); Fetohi, Amani E.; Amin, R.S.; El-Khatib, K.M. [Chemical Engineering Department, National Research Center, Dokki, Giza (Egypt)

    2015-12-30

    Graphical abstract: Physical and electrochemical properties of Pt/C, Pt–MnO{sub 2}/C-1 and Pt–MnO{sub 2}/C-2 electrocatalysts. - Highlights: • Adding MnO{sub 2} to Pt/C improved the dispersion of Pt nanoparticles. • The existence of MnO{sub 2} improved the kinetics of methanol oxidation reaction. • R{sub ct} value of Pt–MnO{sub 2}/C was about 10 times as low as that at Pt/C. • The removal of CO{sub ads} poisoning species was facilitated at Pt–MnO{sub 2}/C. - Abstract: The modification of Pt/C by incorporating metal oxides for electrocatalytic oxidation of methanol has gained major attention because of the efficiency loss during the course of long-time operation. This work describes the preparation of Pt–MnO{sub 2}/C electrocatalysts through a chemical route using ethylene glycol or a mixture of ethylene glycol and sodium borohydride as a reducing agent. The crystallite structure and particle size of synthesized electrocatalysts are determined using X-ray diffraction (XRD) and transmission electron microscopy (TEM). The addition of MnO{sub 2} improves the dispersion of Pt nanoparticles. The electrocatalytic activity of Pt–MnO{sub 2}/C towards methanol oxidation in H{sub 2}SO{sub 4} solution is investigated using cyclic voltammetry and electrochemical impedance spectroscopy. The onset potential value of methanol oxidation peak is negatively shifted by 169 mV when MnO{sub 2} is introduced to Pt/C. Moreover, the charge transfer resistance value at Pt–MnO{sub 2}/C is about 10 times as low as that at Pt/C. Chronoamperometry and chronopotentiometry show that CO tolerance is greatly improved at Pt–MnO{sub 2}/C. The increased electrocatalytic activity and enhanced ability to clean platinum surface elect manganese oxide as a suitable promoter for the anode performance in direct methanol fuel cells (DMFCs).

  13. Feasible synthesis of protein-templated zinc phosphate-supported Pt nanoparticle with enhanced electrocatalysis for methanol oxidation

    Science.gov (United States)

    Song, Yingpan; Ji, Hongfei; Wang, Minghua; He, Linghao; Song, Ruirui; Zhang, Zhihong

    2017-11-01

    Bovine serum albumin (BSA)-templated zinc phosphate (Zn3(PO4)2@BSA) was synthesized by a feasible self-assembly method and applied as support for platinum nanoparticles (Pt NPs). The possible formation mechanism of Zn3(PO4)2@BSA nanocomposite was investigated using time-dependent experiments. We found that Zn3(PO4)2@BSA nanocomposite was transformed from its nanoplate counterpart. Furthermore, the amount of the precursor H2PtCl6 used in the formation of PtNP@Zn3(PO4)2@BSA plays an important role in the electrocatalytic activity of the developed PtNP@Zn3(PO4)2@BSA electrocatalyst. Results showed that the deposition of Pt onto the surface of Zn3(PO4)2@BSA nanocomposite with 150 μL of H2PtCl6 produced the most uniformly distributed Pt NPs, with an average size of approximately 2 nm. The as-prepared novel PtNP@Zn3(PO4)2@BSA electrocatalyst exhibits considerably enhanced electrocatalytic activity and stability for methanol oxidation compared with multi-walled carbon nanotube-supported Pt NP electrocatalyst. The introduction of Zn3(PO4)2@BSA nanocomposite as new support material demonstrated a new strategy that can potentially accelerate electrode reactions toward methanol oxidation.

  14. Efficiency of bimetallic PtPd on polydopamine modified on various carbon supports for alcohol oxidations

    Science.gov (United States)

    Pinithchaisakula, A.; Ounnunkad, K.; Themsirimongkon, S.; Promsawan, N.; Waenkaew, P.; Saipanya, S.

    2017-02-01

    In this work, the preparation, characterization, and electrocatalytic analysis of the catalysts on various carbon substrates for direct alcohol fuel cells were studied. Selected carbons were modified with/without polydopamine (labelled as PDA-C and C) and further metal electrodeposited incorporated onto the glassy carbon (labelled as 5Pt1Pd/PDA-C and 5Pt1Pd/C). Four various carbon materials were used e.g. graphite (G), carbon nanotube (CNT), graphene (GP) and graphene oxide (GO) and the carbons were modified with PDA denoted as PDA-G, PDA-CNT, PDA-GP and PDA-GO, respectively. The transmission electron microscopy (TEM) and scanning electron microscopy (SEM) experimental observation showed narrow size distribution of metal anchored on the PDA-C and C materials. Chemical compositions and oxidation states of the catalysts were determined by X-ray photoelectron spectroscopy (XPS) and energy-dispersive X-ray spectroscopy (EDX). The catalytic performances for small organic electro-oxidation (e.g. methanol and ethanol) were measured by cyclic voltammetry (CV). Among different PDA-C and C catalysts, monometallic Pt showed less activity than the bimetallic catalysts. Among catalysts with PDA, the 5Pt1Pd/PDA-GO catalyst facilitated methanol and ethanol oxidations with high oxidation currents and If/Ib value and stability with low potentials while among catalysts without PDA, the 5Pt1Pd/CNT provides highest activity and stability. It was found that the catalysts with PDA provided high activity and stability than the catalysts without PDA. The improved catalytic performance of the prepared catalysts could be related to the higher active surface area from polymer modification and bimetallic catalyst system in the catalyst composites.

  15. Automated galaxy surface photometry: Pt. 5

    International Nuclear Information System (INIS)

    Irwin, M.J.; Davies, J.I.; Disney, M.J.; Phillipps, S.

    1990-01-01

    We show that APM measurement of a standard deep UKSTU plate is equally as successful as photographic amplification in the detection of very low surface brightness galaxies. This method has the advantage of allowing us to detect and quantitatively measure images at the same time (i.e. without recourse to further observations). Suitable median filtering techniques allow us to detect galaxies with scale sizes of a few arcseconds and central surface brightnesses as low as 26.5 B mag arcsec -2 . (author)

  16. Methanol electrocatalytic oxidation on Pt nanoparticles on nitrogen doped graphene prepared by the hydrothermal reaction of graphene oxide with urea

    International Nuclear Information System (INIS)

    Xu, Xiao; Zhou, Yingke; Yuan, Tao; Li, Yawei

    2013-01-01

    A facile hydrothermal reaction of graphene oxide with urea was used to produce nitrogen doped graphene, and Pt nanoparticles were deposited on the obtained nitrogen doped graphene by the NaBH 4 reduction route. The morphology and microstructure of the synthesized catalysts were characterized by transmission electron microscopy, X-ray powder diffraction and X-ray photoelectron spectroscopy, while the functional groups on the surface of the catalysts were investigated by the Fourier transform infrared spectroscopy and ultraviolet-visible absorption spectra. Cyclic voltammetry, chronoamperometry and electrochemical impedance techniques were carried out to evaluate the methanol electrocatalytic oxidation activity and durability of Pt catalysts supported on the nitrogen doped graphene. The results showed that nitrogen doping and reduction of GO were achieved simultaneously by the facile hydrothermal reaction, which had beneficial effects for the deposition process and electrocatalytic activity of Pt nanoparticles. The Pt catalysts supported on the nitrogen doped graphene substrate presented excellent activity and durability of methanol oxidation reaction, which might be promising for application in direct methanol fuel cells

  17. Defects at oxide surfaces

    CERN Document Server

    Thornton, Geoff

    2015-01-01

    This book presents the basics and characterization of defects at oxide surfaces. It provides a state-of-the-art review of the field, containing information to the various types of surface defects, describes analytical methods to study defects, their chemical activity and the catalytic reactivity of oxides. Numerical simulations of defective structures complete the picture developed. Defects on planar surfaces form the focus of much of the book, although the investigation of powder samples also form an important part. The experimental study of planar surfaces opens the possibility of applying the large armoury of techniques that have been developed over the last half-century to study surfaces in ultra-high vacuum. This enables the acquisition of atomic level data under well-controlled conditions, providing a stringent test of theoretical methods. The latter can then be more reliably applied to systems such as nanoparticles for which accurate methods of characterization of structure and electronic properties ha...

  18. Shape-dependent surface magnetism of Co-Pt and Fe-Pt nanoparticles from first principles

    Science.gov (United States)

    Liu, Zhenyu; Wang, Guofeng

    2017-12-01

    In this paper, we have performed the first-principles density functional theory calculations to predict the magnetic properties of the CoPt and FePt nanoparticles in cuboctahedral, decahedral, and icosahedral shapes. The modeled alloy nanoparticles have a diameter of 1.1 nm and consist of 31 5 d Pt atoms and 24 3 d Co (or Fe) atoms. For both CoPt and FePt, we found that the decahedral nanoparticles had appreciably lower surface magnetic moments than the cuboctahedral and icosahedral nanoparticles. Our analysis indicated that this reduction in the surface magnetism was related to a large contraction of atomic spacing and high local Co (or Fe) concentration in the surface of the decahedral nanoparticles. More interestingly, we predicted that the CoPt and FePt cuboctahedral nanoparticles exhibited dramatically different surface spin structures when noncollinear magnetism was taken into account. Our calculation results revealed that surface anisotropy energy decided the fashion of surface spin canting in the CoPt and FePt nanoparticles, confirming previous predictions from atomistic Monte Carlo simulations.

  19. Enhanced Electrocatalytic Activity of Pt Particles Supported on Reduced Graphene Oxide/Poly(3,4-ethylenedioxythiophene RGO/PEDOT Composite towards Ethanol Oxidation

    Directory of Open Access Journals (Sweden)

    Juanito Raphael F. Foronda

    2013-01-01

    Full Text Available Catalysts in fuel cells are normally platinum based because platinum exhibits high electrocatalytic activity towards ethanol oxidation in acidic medium. However, bulk Pt is expensive and rare in nature. To reduce the consumption of Pt, a support material or matrix is needed to disperse Pt on its surface as micro- or nanoparticles with potential application as anode material in direct ethanol fuel cells (DEFCs. In this study, a composite material consisting of platinum particles dispersed on reduced graphene oxide/poly(3,4-ethylenedioxythiophene (RGO/PEDOT support was electrochemically prepared for ethanol oxidation in sulfuric acid electrolyte. PEDOT, a conductive polymer, was potentiodynamically polymerized from the corresponding monomer, 0.10 M EDOT in 0.10 M HClO4 electrolyte. The PEDOT-modified electrode was used as a substrate for exfoliated graphene oxide (EGO which was prepared by electrochemical exfoliation of graphite from carbon rod of spent batteries and subsequently reduced to form RGO. The Pt/RGO/PEDOT composite gave the highest electrocatalytic activity with an anodic current density of 2688.7 mA·cm−2 at E = 0.70 V (versus Ag/AgCl towards ethanol oxidation compared to bare Pt electrode and other composites. Scanning electron microscopy (SEM revealed the surface morphology of the hybrid composites while energy dispersive X-ray (EDX confirmed the presence of all the elements for the Pt/RGO/PEDOT composite.

  20. Oxidation of Propylene on catalytic Pt-Cu/y alumina. (Part I) Characterization of catalysts of Pt-Cu/y alumina for chemisorption of H2

    International Nuclear Information System (INIS)

    Carballo, Luis M; Zea, Hugo R

    1999-01-01

    In this work the effect of the composition of catalysts of Pt-Cu/y-alumina is analyzed on the superficial area it reactivates corresponding to the total oxidation of propylene. The experimental essays were also made in a differential reactor that was used so much for the characterization of the catalyst in situ by means of the measurement of the selective chemisorption of H 2 , the effects and the bimetallic interactions are discussed that frequently happen in the supported catalysts. Starting from the studies of chemical adsorption of H 2 on the supported catalysts of Pt-Cu was, by means of the application of the theory of the regular solution to the surface of the glasses and keeping in mind that the H 2 it adsorbs chemically only on the superficial atoms of Pt (it was observed that the hydrogen not it chemi-absorb on the Cu) that the Cu atoms are segregated to the surface of the bimetallic crystals

  1. Surface Relaxation and Electronic States of Pt(111) Surface with Varying Slab Thickness

    International Nuclear Information System (INIS)

    Kaushal, Ashok K.; Mullick, Shanta; Ahluwalia, P. K.

    2011-01-01

    Surface relaxation and electronic DOS's of Pt(111) surface have been studied with varying slab thickness using ab-initio SIESTA method. We found the expansion in the top layer and contraction in the subsurface layers of Pt(111) surface. Our results match with the experimental results. Also observing electronic density of states we found that as we increase the thickness of slab, the PDOS of Pt(111) surface goes towards the bulk density of states and Fermi energy shifts towards the bulk fermi energy.

  2. Unusual attempt to direct the growth of bimetallic Ag@Pt nanorods on electrochemically reduced graphene oxide nanosheets by electroless exchange of Cu by Pt for an efficient alcohol oxidation

    International Nuclear Information System (INIS)

    Jeena, S. E.; Gnanaprakasam, P.; Selvaraju, T.

    2017-01-01

    A simple and an efficient tool for the direct growth of bimetallic Ag@Pt nanorods (NRDs) on electrochemically reduced graphene oxide (ERGO) nanosheets was developed at glassy carbon electrode (GCE). Initially, Cu shell was grown on Ag core as Ag@Cu NRD by the seed-mediated growth method. Accordingly, Cu shell has been successfully replaced by Pt using the electroless galvanic replacement method with ease by effective functionalization of L-tryptophan on ERGO surface (L-ERGO), which eventually plays an important role in the direct growth of one-dimensional bimetallic NRDs. As a result, the synthesized Ag@Pt NRD-supported L-ERGO nanosheets (Ag@Pt NRDs/L-ERGO/GCE) were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), energy-dispersive X-ray analysis (EDAX) and Raman spectroscopy. Anodic stripping voltammetry was used to explore its electrochemical properties. Finally, the developed bimetallic Ag@Pt NRDs/L-ERGO/GCEs were studied as a better electrocatalyst compared to the commercial catalysts such as Pt 40 /C or Pt 20 /C-loaded electrode for the oxidation of ethanol or methanol with a high tolerance level and an enhanced current density. In addition, the long-term stability was studied using chronoamperometry for 1000 s at the bimetallic NRD electrode for alcohol oxidation which impedes the fouling properties. The unfavourable and favourable electrooxidation of ethanol at Ag@Cu NRDs/L-ERGO/GCE (a) and Ag@Pt NRDs/L-ERGO/GCE (b) is discussed. The synergistic effect of Ag core and catalytic properties of Pt shell at Ag@Pt NRDs/L-ERGO/GCE tend to strongly minimize the CO poisoning effect and enhanced ethanol electrooxidation.

  3. Unusual attempt to direct the growth of bimetallic Ag@Pt nanorods on electrochemically reduced graphene oxide nanosheets by electroless exchange of Cu by Pt for an efficient alcohol oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Jeena, S. E.; Gnanaprakasam, P. [Karunya University, Department of Chemistry (India); Selvaraju, T., E-mail: veluselvaraju@gmail.com [Bharathiar University, Department of Chemistry (India)

    2017-01-15

    A simple and an efficient tool for the direct growth of bimetallic Ag@Pt nanorods (NRDs) on electrochemically reduced graphene oxide (ERGO) nanosheets was developed at glassy carbon electrode (GCE). Initially, Cu shell was grown on Ag core as Ag@Cu NRD by the seed-mediated growth method. Accordingly, Cu shell has been successfully replaced by Pt using the electroless galvanic replacement method with ease by effective functionalization of L-tryptophan on ERGO surface (L-ERGO), which eventually plays an important role in the direct growth of one-dimensional bimetallic NRDs. As a result, the synthesized Ag@Pt NRD-supported L-ERGO nanosheets (Ag@Pt NRDs/L-ERGO/GCE) were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), energy-dispersive X-ray analysis (EDAX) and Raman spectroscopy. Anodic stripping voltammetry was used to explore its electrochemical properties. Finally, the developed bimetallic Ag@Pt NRDs/L-ERGO/GCEs were studied as a better electrocatalyst compared to the commercial catalysts such as Pt{sub 40}/C or Pt{sub 20}/C-loaded electrode for the oxidation of ethanol or methanol with a high tolerance level and an enhanced current density. In addition, the long-term stability was studied using chronoamperometry for 1000 s at the bimetallic NRD electrode for alcohol oxidation which impedes the fouling properties. The unfavourable and favourable electrooxidation of ethanol at Ag@Cu NRDs/L-ERGO/GCE (a) and Ag@Pt NRDs/L-ERGO/GCE (b) is discussed. The synergistic effect of Ag core and catalytic properties of Pt shell at Ag@Pt NRDs/L-ERGO/GCE tend to strongly minimize the CO poisoning effect and enhanced ethanol electrooxidation.

  4. Unusual attempt to direct the growth of bimetallic Ag@Pt nanorods on electrochemically reduced graphene oxide nanosheets by electroless exchange of Cu by Pt for an efficient alcohol oxidation

    Science.gov (United States)

    Jeena, S. E.; Gnanaprakasam, P.; Selvaraju, T.

    2017-01-01

    A simple and an efficient tool for the direct growth of bimetallic Ag@Pt nanorods (NRDs) on electrochemically reduced graphene oxide (ERGO) nanosheets was developed at glassy carbon electrode (GCE). Initially, Cu shell was grown on Ag core as Ag@Cu NRD by the seed-mediated growth method. Accordingly, Cu shell has been successfully replaced by Pt using the electroless galvanic replacement method with ease by effective functionalization of L-tryptophan on ERGO surface (L-ERGO), which eventually plays an important role in the direct growth of one-dimensional bimetallic NRDs. As a result, the synthesized Ag@Pt NRD-supported L-ERGO nanosheets (Ag@Pt NRDs/L-ERGO/GCE) were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), energy-dispersive X-ray analysis (EDAX) and Raman spectroscopy. Anodic stripping voltammetry was used to explore its electrochemical properties. Finally, the developed bimetallic Ag@Pt NRDs/L-ERGO/GCEs were studied as a better electrocatalyst compared to the commercial catalysts such as Pt40/C or Pt20/C-loaded electrode for the oxidation of ethanol or methanol with a high tolerance level and an enhanced current density. In addition, the long-term stability was studied using chronoamperometry for 1000 s at the bimetallic NRD electrode for alcohol oxidation which impedes the fouling properties. The unfavourable and favourable electrooxidation of ethanol at Ag@Cu NRDs/L-ERGO/GCE (a) and Ag@Pt NRDs/L-ERGO/GCE (b) is discussed. The synergistic effect of Ag core and catalytic properties of Pt shell at Ag@Pt NRDs/L-ERGO/GCE tend to strongly minimize the CO poisoning effect and enhanced ethanol electrooxidation.

  5. Electrochemical Synthesis of Mesoporous CoPt Nanowires for Methanol Oxidation.

    Science.gov (United States)

    Serrà, Albert; Montiel, Manuel; Gómez, Elvira; Vallés, Elisa

    2014-03-28

    A new electrochemical method to synthesize mesoporous nanowires of alloys has been developed. Electrochemical deposition in ionic liquid-in-water (IL/W) microemulsion has been successful to grow mesoporous CoPt nanowires in the interior of polycarbonate membranes. The viscosity of the medium was high, but it did not avoid the entrance of the microemulsion in the interior of the membrane's channels. The structure of the IL/W microemulsions, with droplets of ionic liquid (4 nm average diameter) dispersed in CoPt aqueous solution, defined the structure of the nanowires, with pores of a few nanometers, because CoPt alloy deposited only from the aqueous component of the microemulsion. The electrodeposition in IL/W microemulsion allows obtaining mesoporous structures in which the small pores must correspond to the size of the droplets of the electrolytic aqueous component of the microemulsion. The IL main phase is like a template for the confined electrodeposition. The comparison of the electrocatalytic behaviours towards methanol oxidation of mesoporous and compact CoPt nanowires of the same composition, demonstrated the porosity of the material. For the same material mass, the CoPt mesoporous nanowires present a surface area 16 times greater than compact ones, and comparable to that observed for commercial carbon-supported platinum nanoparticles.

  6. Electrochemical Synthesis of Mesoporous CoPt Nanowires for Methanol Oxidation

    Directory of Open Access Journals (Sweden)

    Albert Serrà

    2014-03-01

    Full Text Available A new electrochemical method to synthesize mesoporous nanowires of alloys has been developed. Electrochemical deposition in ionic liquid-in-water (IL/W microemulsion has been successful to grow mesoporous CoPt nanowires in the interior of polycarbonate membranes. The viscosity of the medium was high, but it did not avoid the entrance of the microemulsion in the interior of the membrane’s channels. The structure of the IL/W microemulsions, with droplets of ionic liquid (4 nm average diameter dispersed in CoPt aqueous solution, defined the structure of the nanowires, with pores of a few nanometers, because CoPt alloy deposited only from the aqueous component of the microemulsion. The electrodeposition in IL/W microemulsion allows obtaining mesoporous structures in which the small pores must correspond to the size of the droplets of the electrolytic aqueous component of the microemulsion. The IL main phase is like a template for the confined electrodeposition. The comparison of the electrocatalytic behaviours towards methanol oxidation of mesoporous and compact CoPt nanowires of the same composition, demonstrated the porosity of the material. For the same material mass, the CoPt mesoporous nanowires present a surface area 16 times greater than compact ones, and comparable to that observed for commercial carbon-supported platinum nanoparticles.

  7. Hydrothermal synthesis of PtRu on CNT/SnO2 composite as anode catalyst for methanol oxidation fuel cell

    International Nuclear Information System (INIS)

    Kakati, Nitul; Maiti, Jatindranath; Jee, Seung Hyun; Lee, Seok Hee; Yoon, Young Soo

    2011-01-01

    Graphical abstract: Display Omitted Highlights: → CNTs are homogeneously covered by the porous SnO 2 layer which enhanced the electronic property of the catalyst support as well as the catalyst and fuel interaction. → PtRu/SnO 2 /CNT catalyst shows an electrochemically active surface area of 81.84 m 2 g Pt -1 and a mass activity of 890mAmg Pt -1 . → Hydrothermal synthesis offers small particle size as well as well dispersion of the catalyst nanoparticles. → Addition of SnO 2 with PtRu provides an additional route for OH ads formation and hence accelerates methanol oxidation. - Abstract: An electrocatalyst support comprising of carbon nanotube and tin oxide (CNT/SnO 2 ) was prepared by an ethylene glycol mediated synthesis procedure and proposed as an improved catalyst support for direct methanol fuel cell. CNTs are covered by the porous SnO 2 layer which is homogeneously distributed over CNT surface. PtRu alloy nanoparticles were deposited over this composite material by a hydrothermal synthesis method. The CNT/SnO 2 composite and its supported PtRu catalyst (PtRu/SnO 2 /CNT) were characterized by X-ray diffraction, field emission scanning electron microscopy and transmission electron microscopy. The electrocatalytic activity of PtRu/SnO 2 /CNT catalyst for methanol oxidation has been studied by cyclic voltammetry, impedance spectroscopy and chronoamperometry. The results were compared with Pt/SnO 2 /CNT and PtRu/CNT catalysts synthesized by the same procedure. PtRu/SnO 2 /CNT catalyst shows an electrochemically active surface area of 81.84 m 2 g Pt -1 and a mass activity of 890mAmg Pt -1 . The presence of SnO 2 layer over CNT can further improve the electrocatalytic activity of PtRu alloy nanoparticles for methanol oxidation.

  8. 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.

  9. Hydrogen peroxide treatment on ZnO substrates to investigate the characteristics of Pt and Pt oxide Schottky contacts

    International Nuclear Information System (INIS)

    Tsai, Chia-Hung; Hung, Chen-I; Yang, Cheng-Fu; Houng, Mau-Phon

    2010-01-01

    We utilize hydrogen peroxide (H 2 O 2 ) treatment on (0 0 0 1) ZnO substrates to investigate the characteristics of Pt and Pt oxide Schottky contacts (SCs). X-ray rocking curves show the mosaicity structure becomes larger after H 2 O 2 treatment. Photoluminescence (PL) spectra show the yellow-orange emission peaking at ∼576-580 nm with respect to deep level of oxygen interstitials introduced by H 2 O 2 treatment. The threshold formation of ZnO 2 resistive layer on H 2 O 2 -treated ZnO for 45 min is observed from grazing-incidence X-ray diffraction. The better electrical characteristic is performed by Pt oxide SC with the larger barrier height (1.09 eV) and the lower leakage current (9.52 x 10 -11 A/cm 2 at -2 V) than Pt SC on the H 2 O 2 -treated ZnO for 60 min. X-ray photoelectron spectroscopy (XPS) and secondary ion mass spectrometer (SIMS) examinations indicate the promoted interface oxide bonding and Zn outdiffusion for Pt oxide contact, different from Pt contact. Based on current-voltage, capacitance-voltage, X-ray diffraction, PL spectra, XPS, and SIMS results, the possible mechanism for effective rectifying characteristic and enhanced Schottky fbehavior is given.

  10. Ethanol electro-oxidation on carbon-supported Pt, PtRu and Pt{sub 3}Sn catalysts: A quantitative DEMS study

    Energy Technology Data Exchange (ETDEWEB)

    Wang, H.; Jusys, Z.; Behm, R.J. [Department Surface Chemistry and Catalysis, University of Ulm, D-89069 Ulm (Germany)

    2006-03-21

    The electrocatalytic activity of commercial carbon supported PtRu/Vulcan and Pt{sub 3}Sn/Vulcan bimetallic catalysts (E-TEK, Inc.) for ethanol oxidation under well defined electrolyte transport conditions and their selectivity for complete oxidation were evaluated using cyclic voltammetry combined with on-line differential electrochemistry mass spectrometry (DEMS) measurements and compared to the activity/selectivity of standard Pt/Vulcan catalysts. The main reaction products CO{sub 2}, acetaldehyde and acetic acid were determined quantitatively, by appropriate calibration procedures, current efficiencies and product yields were calculated. Addition of Ru or Sn in binary Pt catalysts lowers the onset potential for ethanol electro-oxidation and leads to a subtle increase of the total activity of the Pt{sub 3}Sn/Vulcan catalyst. It does not improve, however, the selectivity for complete oxidation to CO{sub 2}, which is about 1% for all three catalysts under present reaction conditions-incomplete ethanol oxidation to acetaldehyde and acetic acid prevails on all three catalysts. The results demonstrate that the performance of the respective catalysts is limited by their ability for C-C bond breaking rather than by their activity for the oxidation of poisoning adsorbed intermediates such as CO{sub ad} or CH{sub x,ad} species. (author)

  11. Ethanol electro-oxidation on carbon-supported Pt, PtRu and Pt 3Sn catalysts: A quantitative DEMS study

    Science.gov (United States)

    Wang, H.; Jusys, Z.; Behm, R. J.

    The electrocatalytic activity of commercial carbon supported PtRu/Vulcan and Pt 3Sn/Vulcan bimetallic catalysts (E-TEK, Inc.) for ethanol oxidation under well defined electrolyte transport conditions and their selectivity for complete oxidation were evaluated using cyclic voltammetry combined with on-line differential electrochemistry mass spectrometry (DEMS) measurements and compared to the activity/selectivity of standard Pt/Vulcan catalysts. The main reaction products CO 2, acetaldehyde and acetic acid were determined quantitatively, by appropriate calibration procedures, current efficiencies and product yields were calculated. Addition of Ru or Sn in binary Pt catalysts lowers the onset potential for ethanol electro-oxidation and leads to a subtle increase of the total activity of the Pt 3Sn/Vulcan catalyst. It does not improve, however, the selectivity for complete oxidation to CO 2, which is about 1% for all three catalysts under present reaction conditions-incomplete ethanol oxidation to acetaldehyde and acetic acid prevails on all three catalysts. The results demonstrate that the performance of the respective catalysts is limited by their ability for C-C bond breaking rather than by their activity for the oxidation of poisoning adsorbed intermediates such as CO ad or CH x,ad species.

  12. Porous Ni@Pt core-shell nanotube array electrocatalyst with high activity and stability for methanol oxidation.

    Science.gov (United States)

    Ding, Liang-Xin; Li, Gao-Ren; Wang, Zi-Long; Liu, Zhao-Qing; Liu, Hong; Tong, Ye-Xiang

    2012-07-02

    Bimetallic core-shell nanostructures are emerging as more important materials than monometallic nanostructures, and have much more interesting potential applications in various fields, including catalysis and electronics. In this work, we demonstrate the facile synthesis of core-shell nanotube array catalysts consisting of Pt thin layers as the shells and Ni nanotubes as the cores. The porous Ni@Pt core-shell nanotube arrays were fabricated by ZnO nanorod-array template-assisted electrodeposition, and they represent a new class of nanostructures with a high electrochemically active surface area of 50.08 m(2)  (g Pt)(-1), which is close to the value of 59.44 m(2)  (g Pt)(-1) for commercial Pt/C catalysts. The porous Ni@Pt core-shell nanotube arrays also show markedly enhanced electrocatalytic activity and stability for methanol oxidation compared with the commercial Pt/C catalysts. The attractive performances exhibited by these prepared porous Ni@Pt core-shell nanotube arrays make them promising candidates as future high-performance catalysts for methanol electrooxidation. The facile method described herein is suitable for large-scale, low-cost production, and significantly lowers the Pt loading, and thus, the cost of the catalysts. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Oxide Scales Formed on NiTi and NiPtTi Shape Memory Alloys

    Science.gov (United States)

    Smialek, James L.; Garg, Anita; Rogers, Richard B.; Noebe, Ronald D.

    2011-01-01

    Ni-49Ti and Ni-30Pt-50Ti (at.%) shape memory alloys were oxidized isothermally in air over the temperature range of 500 to 900 C. The microstructure, composition, and phase content of the scales were studied by SEM, EDS, XRD, and metallography. Extensive plan view SEM/EDS identified various features of intact or spalled scale surfaces. The outer surface of the scale was a relatively pure TiO2 rutile structure, typified by a distinct highly striated and faceted crystal morphology. Crystal size increased significantly with temperature. Spalled regions exhibited some porosity and less distinct features. More detailed information was obtained by correlation of SEM/EDS studies of 700 C/100 hr cross-sections with XRD analyses of serial or taper-polishing of plan surfaces. Overall, multiple layers exhibited graded mixtures of NiO, TiO2, NiTiO3, Ni(Ti) or Pt(Ni,Ti) metal dispersoids, Ni3Ti or Pt3Ti depletion zones, and substrate, in that order. The NiTi alloy contained a 3 at.% Fe impurity that appeared in embedded localized Fe-Ti-rich oxides, while the NiPtTi alloy contained a 2 v/o dispersion of TiC that appeared in lower layers. The oxidation kinetics of both alloys (in a previous report) indicated parabolic growth and an activation energy (250 kJ/mole) near those reported in other Ti and NiTi studies. This is generally consistent with TiO2 existing as the primary scale constituent, as described here.

  14. Ru-decorated Pt surfaces as model fuel cell electrocatalysts for CO electrooxidation.

    Science.gov (United States)

    Maillard, F; Lu, G-Q; Wieckowski, A; Stimming, U

    2005-09-01

    This feature article concerns Pt surfaces modified (decorated) by ruthenium as model fuel cell electrocatalysts for electrooxidation processes. This work reveals the role of ruthenium promoters in enhancing electrocatalytic activity toward organic fuels for fuel cells, and it particularly concerns the methanol decomposition product, surface CO. A special focus is on surface mobility of the CO as it is catalytically oxidized to CO(2). Different methods used to prepare Ru-decorated Pt single crystal surfaces as well as Ru-decorated Pt nanoparticles are reviewed, and the methods of characterization and testing of their activity are discussed. The focus is on the origin of peak splitting involved in the voltammetric electrooxidation of CO on Ru-decorated Pt surfaces, and on the interpretative consequences of the splitting for single crystal and nanoparticle Pt/Ru bimetallic surfaces. Apparently, screening through the literature allows formulating several models of the CO stripping reaction, and the validity of these models is discussed. Major efforts are made in this article to compare the results reported by the Urbana-Champaign group and the Munich group, but also by other groups. As electrocatalysis is progressively more and more driven by theory, our review of the experimental findings may serve to summarize the state of the art and clarify the roads ahead. Future studies will deal with highly dispersed and reactive nanoscale surfaces and other more advanced catalytic materials for fuel cell catalysis and related energy applications. It is expected that the metal/metal and metal/substrate interactions will be increasingly investigated on atomic and electronic levels, with likewise increasing participation of theory, and the structure and reactivity of various monolayer catalytic systems involving more than two metals (that is ternary and quaternary systems) will be interrogated.

  15. Localized Pd Overgrowth on Cubic Pt Nanocrystals for Enhanced Electrocatalytic Oxidation of Formic Acid

    Energy Technology Data Exchange (ETDEWEB)

    Lee, H.; Habas, S.E.; Somorjai, G.A.; Yang, P.

    2008-03-20

    Binary Pt/Pd nanoparticles were synthesized by localized overgrowth of Pd on cubic Pt seeds for the investigation of electrocatalytic formic acid oxidation. The binary particles exhibited much less self-poisoning and a lower activation energy relative to Pt nanocubes, consistent with the single crystal study.

  16. Preparation of PtSn/C, PtRu/C, PtRh/C, PtRuRh/C and PtSnRh/C electrocatalysts using an alcohol-reduction process for methanol and ethanol oxidation; Preparacao e caracterizacao de eletrocatalisadores PtRu, PtSn, PtRh, PtRuRh e PtSnRh para oxidacao direta de alcoois em celulas a combustivel tipo PEM utilizando a metodologia da reducao por alcool

    Energy Technology Data Exchange (ETDEWEB)

    Dias, Ricardo Rodrigues

    2009-07-01

    In this work, Pt/C, PtRh (90:10), PtRh/C (50:50), PtSn/C (50:50), PtRu (50:50)/C, PtRuRh/C (50:40:10) and PtSnRh/C (50:40:10) were prepared by an alcohol-reduction process with metal loading of 20 wt.% using H{sub 2}PtCl{sub 6}.6H{sub 2}O (Aldrich), SnCl{sub 2}.2H{sub 2}O (Aldrich),and RhCl{sub 2}.XH{sub 2}O (Aldrich) as metals sources and Vulcan XC72 as support. The electrocatalysts were characterized by EDX, XRD and cyclic voltammetry (CV). The electro-oxidation of ethanol was studied by CV, chronoamperomety at room temperature in acid medium and tests at 100 deg C on a single cell of a direct methanol or ethanol fuel cell. The EDX analysis showed that the metal atomic ratios of the obtained electrocatalysts were similar to the nominal atomic ratios used in the preparation. The diffractograms of electrocatalysts prepared showed four peaks at approximately 2{theta} =40 deg, 47 deg, 67 deg and 82 deg, which are associated with the (111), (200), (220) and (311) planes, respectively, of a face cubic-centered (fcc) structure characteristic of platinum and platinum alloys. The average crystallite sizes using the Scherrer equation and the calculated values were in the range of 2-3 nm. For Pt Sn/C and PtSnRh/C two additional peaks were observed at 2 = 34 deg and 52 deg that were identified as a SnO{sub 2} phase. Pt Sn/C (50:50) and PtSnRh/C (50:40:10) electro catalyst showed the best performance for ethanol oxidation at room temperature. For methanol oxidation at room temperature Pt Ru/C, Pt Sn/C and PtRuRh/C electrocatalysts showed the best performance. Tests at 100 deg C on a single cell of a direct ethanol fuel cell PtSnRh/C showed the best performance, for methanol oxidation PtRuRh/C showed the best performance. (author)

  17. From Au to Pt via surface limited redox replacement of Pb UPD in one-cell configuration.

    Science.gov (United States)

    Fayette, M; Liu, Y; Bertrand, D; Nutariya, J; Vasiljevic, N; Dimitrov, N

    2011-05-03

    This work is aimed at developing a protocol based on surface limited redox replacement (SLRR) of underpotentially deposited (UPD) Pb layers for the growth of epitaxial and continuous Pt thin films on polycrystalline and single crystalline Au surfaces. Different from previously reported papers using SLRR in multiple immersion or flow cell setups, this work explores the one-cell configuration setup as an alternative to improve the efficiency and quality of the growth. Open circuit chronopotentiometry and quartz-crystal microbalance experiments demonstrate steady displacement kinetics and a yield that is higher than the stoichiometric Pt(II)-Pb exchange ratio (1:1). This high yield is attributed to oxidative adsorption of OH(ad) taking place on Pt along with the displacement process. Also, ex situ scanning tunneling microscopy surface characterization reveals after the first replacement event the formation of a dense Pt cluster network that homogenously covers the Au surface. The Pt films grow homogenously with no significant changes in the cluster distribution and surface roughness observed up to 10 successive replacement events. X-ray diffraction analysis shows distinct (111) crystallographic orientation of thicker Pt films deposited on (111) textured Au thin films. Coarse energy dispersive spectroscopy measurements and finer X-ray photoelectron spectroscopy suggest at least 4 atom % Pb incorporating into the Pt layer compared to 13 atom % alloyed Cu when the growth is carried out by SLRR of Cu UPD.

  18. Desorption of Furfural from Bimetallic Pt-Fe Oxides/Alumina Catalysts

    Directory of Open Access Journals (Sweden)

    Gloria Lourdes Dimas-Rivera

    2014-01-01

    Full Text Available In this work, the desorption of furfural, which is a competitive intermediate during the production of biofuel and valuable aromatic compounds, was studied using pure alumina, as well as alumina impregnated with iron and platinum oxides both individually and in combination, using thermogravimetric analysis (TGA. The bimetallic sample exhibited the lowest desorption percentage for furfural. High-resolution transmission electron microscopy (HRTEM imaging revealed the intimate connection between the iron and platinum oxide species on the alumina support. The mechanism of furfural desorption from the Pt-Fe/Al2O3 0.5%-0.5% sample was determined using physisorbed furfural instead of chemisorbed furfural; this mechanism involved the oxidation of the C=O group on furfural by the catalyst. The oxide nanoparticles on γ-Al2O3 support helped to stabilize the furfural molecule on the surface.

  19. Probing adsorption phenomena on a single crystal Pt-alloy surface under oxygen reduction reaction conditions

    DEFF Research Database (Denmark)

    Bondarenko, Alexander S.; Stephens, Ifan E.L.; Bech, Lone

    2012-01-01

    The adsorption dynamics of *OH and *O species at Pt(111) and Cu/Pt(111) near-surface alloy (NSA) surfaces in oxygen-free and O2-saturated 0.1M HClO4 was investigated. Subsurface Cu modifies the electronic structure at the Pt(111) surface resulting in weaker bonding to adsorbates like *OH, *H or *...

  20. 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...

  1. Sensitive electrochemical detection of nitric oxide based on AuPt and reduced graphene oxide nanocomposites.

    Science.gov (United States)

    Liu, Zhonggang; Forsyth, Heidi; Khaper, Neelam; Chen, Aicheng

    2016-06-20

    Since nitric oxide (NO) plays a critical role in many biological processes, its precise detection is essential toward an understanding of its specific functions. Here we report on a facile and environmentally compatible strategy for the construction of an electrochemical sensor based on reduced graphene oxide (rGO) and AuPt bimetallic nanoparticles. The prepared nanocomposites were further employed for the electroanalysis of NO using differential pulse voltammetry (DPV) and amperometric methods. The dependence of AuPt molar ratios on the electrochemical performance was investigated. Through the combination of the advantages of the high conductivity from rGO and highly electrocatalytic activity from AuPt bimetallic nanoparticles, the AuPt-rGO based NO sensor exhibited a high sensitivity of 7.35 μA μM(-1) and a low detection limit of 2.88 nM. Additionally, negligible interference from common ions or organic molecules was observed, and the AuPt-rGO modified electrode demonstrated excellent stability. Moreover, this optimized electrochemical sensor was practicable for efficiently monitoring the NO released from rat cardiac cells, which were stimulated by l-arginine (l-arg), showing that stressed cells generated over 10 times more NO than normal cells. The novel sensor developed in this study may have significant medical diagnostic applications for the prevention and monitoring of disease.

  2. Bimetallic Pt-Au nanocatalysts electrochemically deposited on graphene and their electrocatalytic characteristics towards oxygen reduction and methanol oxidation.

    Science.gov (United States)

    Hu, Yaojuan; Zhang, Hua; Wu, Ping; Zhang, Hui; Zhou, Bo; Cai, Chenxin

    2011-03-07

    The burgeoning demand for clean and energy-efficient fuel cell system requires electrocatalysts to deliver greater activity and selectivity. Bimetallic catalysts have proven superior to single metal catalysts in this respect. This work reports the preparation, characterization, and electrocatalytic characteristics of a new bimetallic nanocatalyst. The catalyst, Pt-Au-graphene, was synthesized by electrodeposition of Pt-Au nanostructures on the surface of graphene sheets, and characterized by scanning electron microscopy (SEM), energy-dispersive spectroscopy (EDS), X-ray powder diffraction (XRD), and voltammetry. The morphology and composition of the nanocatalyst can be easily controlled by adjusting the molar ratio between Pt and Au precursors. The electrocatalytic characteristics of the nanocatalysts for the oxygen reduction reaction (ORR) and the methanol oxidation reaction (MOR) were systematically investigated by cyclic voltammetry. The Pt-Au-graphene catalysts exhibits higher catalytic activity than Au-graphene and Pt-graphene catalysts for both the ORR and the MOR, and the highest activity is obtained at a Pt/Au molar ratio of 2:1. Moreover, graphene can significantly enhance the long-term stability of the nanocatalyst toward the MOR by effectively removing the accumulated carbonaceous species formed in the oxidation of methanol from the surface of the catalyst. Therefore, this work has demonstrated that a higher performance of ORR and the MOR could be realized at the Pt-Au-graphene electrocatalyst while Pt utilization also could be greatly diminished. This method may open a general approach for the morphology-controlled synthesis of bimetallic Pt-M nanocatalysts, which can be expected to have promising applications in fuel cells.

  3. Methanol Oxidation on Pt3Sn(111) for Direct Methanol Fuel Cells: Methanol Decomposition.

    Science.gov (United States)

    Lu, Xiaoqing; Deng, Zhigang; Guo, Chen; Wang, Weili; Wei, Shuxian; Ng, Siu-Pang; Chen, Xiangfeng; Ding, Ning; Guo, Wenyue; Wu, Chi-Man Lawrence

    2016-05-18

    PtSn alloy, which is a potential material for use in direct methanol fuel cells, can efficiently promote methanol oxidation and alleviate the CO poisoning problem. Herein, methanol decomposition on Pt3Sn(111) was systematically investigated using periodic density functional theory and microkinetic modeling. The geometries and energies of all of the involved species were analyzed, and the decomposition network was mapped out to elaborate the reaction mechanisms. Our results indicated that methanol and formaldehyde were weakly adsorbed, and the other derivatives (CHxOHy, x = 1-3, y = 0-1) were strongly adsorbed and preferred decomposition rather than desorption on Pt3Sn(111). The competitive methanol decomposition started with the initial O-H bond scission followed by successive C-H bond scissions, (i.e., CH3OH → CH3O → CH2O → CHO → CO). The Brønsted-Evans-Polanyi relations and energy barrier decomposition analyses identified the C-H and O-H bond scissions as being more competitive than the C-O bond scission. Microkinetic modeling confirmed that the vast majority of the intermediates and products from methanol decomposition would escape from the Pt3Sn(111) surface at a relatively low temperature, and the coverage of the CO residue decreased with an increase in the temperature and decrease in partial methanol pressure.

  4. How Pt nanoparticles affect TiO2-induced gas-phase photocatalytic oxidation reactions

    NARCIS (Netherlands)

    Fraters, B.D.; Amrollahi Buky, Rezvaneh; Mul, Guido

    2015-01-01

    The effect of Pt nanoparticles on the gas-phase photocatalytic oxidation activity of TiO2 is shown to be largely dependent on the molecular functionality of the substrate. We demonstrate that Pt nanoparticles decrease rates in photocatalytic oxidation of propane, whereas a strong beneficial effect

  5. Bifunctional Pt-Si Alloys for Small Organic Molecule Electro-oxidation

    DEFF Research Database (Denmark)

    Permyakova, Anastasia Aleksandrovna; Suntivich, Jin; Han, Binghong

    Designing highly active catalysts for electro-oxidation of small organic molecules can help to reduce the anodic overpotential for more efficient utilization of hydrocarbon fuels. The challenge in developing more active electrocatalysts for electro-oxidation reactions is to satisfy the stringent...... adsorption site. We will discuss the enhanced activity of Pt-Si alloys for small organic molecule oxidation, which can be attributed to the improved CO electro-oxidation kinetics on Pt-Si....

  6. Study of the oxidation effects on isothermal solidification based high temperature stable Pt/In/Au and Pt/In/Ag thick film interconnections on LTCC substrate

    Science.gov (United States)

    Kumar, Duguta Suresh; Suri, Nikhil; Khanna, P. K.; Sharma, R. P.

    2016-03-01

    The objective of the presented paper is to determine the oxidized phase compositions of indium lead-free solders during solidification at 190 ° C under room environment with the help of X-ray diffraction (XRD) and Energy dispersive spectroscopy (EDX). Many lead-free solders alloys available oxidizes and have poor wetting properties. The oxidation of pure indium solder foil, Au, Pt, and Ag alloys were identified and investigated, in the process of isothermal solidification based solder joints construction at room environment and humidity. Both EDX and XRD characterization techniques were performed to trace out the amount of oxide levels and variety of oxide formations at solder interface respectively. The paper also aims to report the isothermal solidification technique to provide interconnections to pads on Low temperature co-fired ceramic (LTCC) substrate. It also elaborates advantages of isothermal solidification over the other methods of interconnection. Scanning electron microscope (SEM) used to identify the oxidized spots on the surface of Pt, Ag substrates and In solder. The identified oxides were reported.

  7. Study of the oxidation effects on isothermal solidification based high temperature stable Pt/In/Au and Pt/In/Ag thick film interconnections on LTCC substrate

    Energy Technology Data Exchange (ETDEWEB)

    Kumar, Duguta Suresh, E-mail: sureshduguta@gmail.com; Khanna, P. K., E-mail: pkk@ceeri.ernet.in [CSIR – Central Electronics Engineering Research Institute, Pilani (India); Academy of Scientific and Innovative Research, New Delhi (India); Suri, Nikhil, E-mail: surinikhil@rediffmail.com [CSIR – Central Electronics Engineering Research Institute, Pilani (India); Sharma, R. P., E-mail: rpsbtti@yahoo.com [BK Birla Institute of Engineering & Technology, Pilani (India)

    2016-03-09

    The objective of the presented paper is to determine the oxidized phase compositions of indium lead-free solders during solidification at 190 ° C under room environment with the help of X-ray diffraction (XRD) and Energy dispersive spectroscopy (EDX). Many lead-free solders alloys available oxidizes and have poor wetting properties. The oxidation of pure indium solder foil, Au, Pt, and Ag alloys were identified and investigated, in the process of isothermal solidification based solder joints construction at room environment and humidity. Both EDX and XRD characterization techniques were performed to trace out the amount of oxide levels and variety of oxide formations at solder interface respectively. The paper also aims to report the isothermal solidification technique to provide interconnections to pads on Low temperature co-fired ceramic (LTCC) substrate. It also elaborates advantages of isothermal solidification over the other methods of interconnection. Scanning electron microscope (SEM) used to identify the oxidized spots on the surface of Pt, Ag substrates and In solder. The identified oxides were reported.

  8. Ethanol Electrooxidation on Pt with Lanthanum Oxide as Cocatalyst in a DAFC

    Directory of Open Access Journals (Sweden)

    T. A. B. Santoro

    2012-01-01

    Full Text Available Electrocatalytic activity toward ethanol electrooxidation of Pt particles in PtLa/C catalysts with different Pt : La ratios has been studied with different electrochemical and spectroscopic techniques, and the results were compared to those of Pt/C catalyst. Significant enhancement in the electrocatalytic activity has been achieved by depositing the Pt particles with lanthanum oxides/hydroxides using an alcohol reduction method. Compared to Pt/C catalyst, PtLa/C materials exhibit a lower onset potential and a higher electron-transfer rate constant for the investigated reaction. These studies illustrate the possibility of utilizing Pt/C with La oxides/hidroxides as electrocatalyst for direct alcohol fuel cells (DAFCs.

  9. 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.

  10. Availability of surface boron species in improved oxygen reduction activity of Pt catalysts: A first-principles study

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Libo; Zhou, Gang, E-mail: gzhou@mail.buct.edu.cn [State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029 (China)

    2016-04-14

    The oxidation process of boron (B) species on the Pt(111) surface and the beneficial effects of boron oxides on the oxygen reduction activity are investigated by first-principles calculations. The single-atom B anchored on the Pt surface has a great attraction for the oxygen species in the immediate environment. With the dissociation of molecular oxygen, a series of boron oxides is formed in succession, both indicating exothermic oxidation reactions. After BO{sub 2} is formed, the subsequent O atom immediately participates in the oxygen reduction reaction. The calculated O adsorption energy is appreciably decreased as compared to Pt catalysts, and more approximate to the optimal value of the volcano plot, from which is clear that O hydrogenation kinetics is improved. The modulation mechanism is mainly based on the electron-deficient nature of stable boron oxides, which normally reduces available electronic states of surface Pt atoms that bind the O by facilitating more electron transfer. This modification strategy from the exterior opens the new way, different from the alloying, to efficient electrocatalyst design for PEMFCs.

  11. Bifunctional Pt-Si Alloys for Small Organic Molecule Electro-oxidation

    DEFF Research Database (Denmark)

    Permyakova, Anastasia Aleksandrovna; Suntivich, Jin; Han, Binghong

    Designing highly active catalysts for electro-oxidation of small organic molecules can help to reduce the anodic overpotential for more efficient utilization of hydrocarbon fuels. The challenge in developing more active electrocatalysts for electro-oxidation reactions is to satisfy the stringent...... bifunctional requirement, which demands both adsorption and water oxidation sites. In this contribution, we explore the possibility of using Pt-Si alloys to fulfill this bifunctional requirement. Silicon, a highly oxophillic element, is alloyed into Pt as a site for water oxidation, while Pt serves as a CO...

  12. Effects of Nanowire Length and Surface Roughness on the Electrochemical Sensor Properties of Nafion-Free, Vertically Aligned Pt Nanowire Array Electrodes

    Directory of Open Access Journals (Sweden)

    Zhiyang Li

    2015-09-01

    Full Text Available In this paper, vertically aligned Pt nanowire arrays (PtNWA with different lengths and surface roughnesses were fabricated and their electrochemical performance toward hydrogen peroxide (H2O2 detection was studied. The nanowire arrays were synthesized by electroplating Pt in nanopores of anodic aluminum oxide (AAO template. Different parameters, such as current density and deposition time, were precisely controlled to synthesize nanowires with different surface roughnesses and various lengths from 3 μm to 12 μm. The PtNWA electrodes showed better performance than the conventional electrodes modified by Pt nanowires randomly dispersed on the electrode surface. The results indicate that both the length and surface roughness can affect the sensing performance of vertically aligned Pt nanowire array electrodes. Generally, longer nanowires with rougher surfaces showed better electrochemical sensing performance. The 12 μm rough surface PtNWA presented the largest sensitivity (654 μA·mM−1·cm−2 among all the nanowires studied, and showed a limit of detection of 2.4 μM. The 12 μm rough surface PtNWA electrode also showed good anti-interference property from chemicals that are typically present in the biological samples such as ascorbic, uric acid, citric acid, and glucose. The sensing performance in real samples (river water was tested and good recovery was observed. These Nafion-free, vertically aligned Pt nanowires with surface roughness control show great promise as versatile electrochemical sensors and biosensors.

  13. Unusual Activity Trend for CO Oxidation on Pd(x)Au(140-x)@Pt Core@Shell Nanoparticle Electrocatalysts.

    Science.gov (United States)

    Luo, Long; Zhang, Liang; Henkelman, Graeme; Crooks, Richard M

    2015-07-02

    A theoretical and experimental study of the electrocatalytic oxidation of CO on PdxAu140-x@Pt dendrimer-encapsulated nanoparticle (DEN) catalysts is presented. These nanoparticles are comprised of a core having an average of 140 atoms and a Pt monolayer shell. The CO oxidation activity trend exhibits an unusual koppa shape as the number of Pd atoms in the core is varied from 0 to 140. Calculations based on density functional theory suggest that the koppa-shaped trend is driven primarily by structural changes that affect the CO binding energy on the surface. Specifically, a pure Au core leads to deformation of the Pt shell and a compression of the Pt lattice. In contrast, Pd, from the pure Pd cores, tends to segregate on the DEN surface, forming an inverted configuration having Pt within the core and Pd in the shell. With a small addition of Au, however, the alloy PdAu cores stabilize the core@shell structures by preventing Au and Pd from escaping to the particle surface.

  14. On the design of Pt based catalysts. Combining porous architecture with surface modification by Sn for electrocatalytic activity enhancement

    Science.gov (United States)

    Flórez-Montaño, Jonathan; García, Gonzalo; Rodríguez, José L.; Pastor, Elena; Cappellari, Paula; Planes, Gabriel A.

    2015-05-01

    Metallic mesoporous (MP) catalysts with large surface area can be obtained in-situ, in a single step, by electrochemical reduction. In this work, the electrochemical behavior of MPPt and Sn modified mesoporous Pt (MPPt/Sn) was studied and compared with commercial carbon supported PtSn alloy (3:1). The electrochemical activity toward carbon monoxide and methanol oxidation reactions were evaluated by cyclic voltammetry and chronoamperometry, whereas X-ray photoelectron spectroscopy was used to determine the surface composition and oxidation state of the atoms in the top layers of the catalysts. The analysis of methanol conversion to CO2 was performed with aid of differential electrochemical mass spectrometry (DEMS). Results reveal a better performance of the MPPt/Sn, which shows higher current density and energy conversion efficiency of fuel to CO2 than conventional carbon supported PtSn alloy (3:1).

  15. The origin of SO{sub 2} promotion of propane oxidation over Pt/Al{sub 2}O{sub 3} catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Lee, A.F.; Wilson, K.; Lambert, R.M. [Univ. of Cambridge (United Kingdom). Dept. of Chemistry; Hubbard, C.P.; Hurley, R.G.; McCabe, R.W.; Gandhi, H.S. [Ford Motor Co., Dearborn, MI (United States). Research Lab.

    1999-06-10

    XAFS, XRD, and TEM measurements on dispersed Pt/Al{sub 2}O{sub 3} catalysts have elucidated the promotional effect of SO{sub 2} in propane oxidation over these systems. At low loadings (0.05 wt%), Pt/Al{sub 2}O{sub 3} catalysts initially contain small (<20 {angstrom}) stoichiometric {beta}-PtO{sub 2} particles. Catalyst sulfation is accompanied by reduction and concomitant sintering of these oxidic particles, resulting in metallic Pt clusters exhibiting similar structural and reactive properties to their counterparts formed at higher loading (9 wt%). The formation of stable SO{sub 4} species on both alumina support and on the Pt surface facilitates the dissociative chemisorption of propane onto both support and metal. Evidence is presented for the role of interfacial sulfate in the activation and subsequent oxidation of propane via a bifunctional mechanism.

  16. Surface-effect enhanced magneto-electric coupling in FePt/PMN-PT multiferroic heterostructures

    Science.gov (United States)

    Yang, Y. T.; Li, J.; Peng, X. L.; Hong, B.; Wang, X. Q.; Ge, H. L.; Wang, D. H.; Du, Y. W.

    2017-05-01

    A series of FePt films with different film thickness are deposited on Pb(Mg1/3Nb2/3)O3-PbTiO3 (PMN-PT) substrates. A standard symmetric `Butterfly' shaped Δ M /M -Ed c loops is obtained in 8 nm FePt/PMN-PT heterostrucuture via strain mediated magnetoelectric coupling. For the 3 nm FePt/PMN-PT heterostructure, the loop-like in-plane magnetization (M) -E curve shares a similar shape with the electric polarization of PMN-PT as a function of electric field. The value of MS shows a dramatic change of 30.9% with Edc changing from 0 to 8 kV/cm, this giant magnetoelectric effect in 3 nm FePt/PMN-PT heterostructure results from the remnant polarization induced charge on FePt/PMN-PT interface via the screening charge effect. The enhanced magnetoelectric coupling in thin magnetic/ferroelectric heterostructures opens a promising avenue for the design of ultralow power magnetoelectric devices and information storage devices.

  17. Methanol Electro-Oxidation on Pt-Ru Alloy Nanoparticles Supported on Carbon Nanotubes

    Directory of Open Access Journals (Sweden)

    Yangchuan Xing

    2009-09-01

    Full Text Available Carbon nanotubes (CNTs have been investigated in recent years as a catalyst support for proton exchange membrane fuel cells. Improved catalyst activities were observed and attributed to metal-support interactions. We report a study on the kinetics of methanol electro-oxidation on CNT supported Pt-Ru alloy nanoparticles. Alloy catalysts with different compositions, Pt53Ru47/CNT, Pt69Ru31/CNT and Pt77Ru23/CNT, were prepared and investigated in detail. Experiments were conducted at various temperatures, electrode potentials, and methanol concentrations. It was found that the reaction order of methanol electro-oxidation on the PtRu/CNT catalysts was consistent with what has been reported for PtRu alloys with a value of 0.5 in methanol concentrations. However, the electro-oxidation reaction on the PtRu/CNT catalysts displayed much lower activation energies than that on the Pt-Ru alloy catalysts unsupported or supported on carbon black (PtRu/CB. This study provides an overall kinetic evaluation of the PtRu/CNT catalysts and further demonstrates the beneficial role of CNTs.

  18. Mechanistic studies of formic acid oxidation at polycarbazole supported Pt nanoparticles

    International Nuclear Information System (INIS)

    Moghaddam, Reza B.; Pickup, Peter G.

    2013-01-01

    Highlights: •A polycarbazole support decreases the accumulation of adsorbed intermediates on Pt during formic acid oxidation. •Polycarbazole causes a bilayer of Cu to form on Pt nanoparticles during Cu underpotential deposition. •XPS suggests that both of these effects are due to electron donation from the metal (Pt or Cu) into the polymer π-system. -- Abstract: Mechanistic aspects of the promotion of formic acid oxidation at Pt nanoparticles supported on a thin layer of polycarbazole (PCZ) have been investigated by voltammetry and X-ray photoelectron spectroscopy (XPS). The Pt nanoparticles were drop coated onto a glassy carbon (GC) electrode coated with a ca. 9 nm layer of electrochemically deposited polycarbazole. After 500 s of formic acid oxidation at 0 V vs. SCE, the current at a GC/PCZ/Pt electrode was 25 times higher than at a GC/Pt electrode. Voltammetry in formic acid free H 2 SO 4 following potentiostatic oxidation of formic acid revealed that there was less accumulation of adsorbed intermediates for the polycarbazole supported Pt nanoparticles than for those deposited directly onto the glassy carbon with, 50% more Pt sites remaining available for the GC/PCZ/Pt electrode relative to the GC/Pt electrode. Independent CO stripping experiments revealed only slight differences, while Cu underpotential deposition surprisingly resulted in the deposition of a ca. two-fold excess of Cu on the polycarbazole supported particles. This observation was supported by XPS which also revealed a second Cu signal at a higher binding energy, suggesting electron donation into the conjugated π system of the polymer. Such an interaction of Pt with the polycarbazole may be responsible for its higher activity for formic acid oxidation

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

    Directory of Open Access Journals (Sweden)

    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.

  20. Template preparation of Pt-Ru and Pt nanowire array electrodes on a Ti/Si substrate for methanol electro-oxidation

    Science.gov (United States)

    Zhao, Guang-Yu; Xu, Cai-Ling; Guo, Dao-Jun; Li, Hua; Li, Hu-Lin

    Pt and Pt-Ru nanowire array electrodes were obtained by dc (direct current) electrodeposition of Pt and Ru into the pores of an anodic aluminum oxide (AAO) template on a Ti/Si substrate. Transmission electron microscope (TEM) examination showed all the nanowires had a uniform diameter of about 30 nm. The brush shaped Pt and Pt-Ru nanowire array electrodes could be seen clearly by scanning electron microscope. Pt and Pt-Ru nanowire array electrodes gave the X-ray diffraction pattern of a face-centered cubic (fcc) crystal structure. The electro-oxidation of methanol on these electrodes was investigated at room temperature using cyclic voltammetry. The results demonstrated that the alloy nanowire array electrode was catalytically more active than a pure platinum nanowire array electrode and the Pt-Ru nanowire array electrode may have good potential for applications in portable fuel cell power sources.

  1. FePt and CoPt nanoparticles prepared by micellar method. Effects of A1{yields}L1{sub 0} transition on oxidation resistance and magnetic properties

    Energy Technology Data Exchange (ETDEWEB)

    Han, Luyang

    2011-02-15

    In this thesis FePt and CoPt alloy nanoparticles are prepared with reverse micelles. The metallic nanoparticles with diameters of 2-12 nm and interparticle distances of 20-140 nm are obtained on Si substrates. The magnetic properties of FePt and CoPt nanoparticles as well as oxidation behavior of FePt nanoparticles are investigated. X-ray magnetic circular dichroism (XMCD) measurements on 5.8 nm FePt nanoparticles after hydrogen plasma reduction at 300 C reveals that the magnetic moment per Fe atom and magnetic anisotropy energy match chemically disordered FePt in A1 phase. Annealing at 650 C transform portion of FePt particles to chemically ordered L1{sub 0} phase. The presense of nanoparticles in L1{sub 0} phase is identified by high-resolution transmission electronmicroscopy (HRTEM) investigation, where it is also observed that large fraction of the particles contain defects such as twin boundaries and stacking faults. By increasing the annealing temperature or prolonging annealing time, ratio of transformed particles increases. The average magnetic anisotropy energy of the transformed particles is below 30% of the value of bulk FePt in L1{sub 0} phase. Annealing at above 750 C, however, decreases the average magnetic anisotropy in the sample. Similar A1 {yields} L1{sub 0} transition is observed in FePt nanoparticles with different diameters as well as in CoPt nanoparticles. The spin moment of Fe in FePt nanoparticles decreases with smaller particle diameter, while the orbital moment stays almost constant. Magnetic moments at room temperature are significantly reduced compared to those at low temperature, suggesting the Curie temperatures in FePt and CoPt nanoparticles are significantly lower than in the bulk. The annealing also induces Pt segregation towards the surface in FePt nanoparticles, which is identified by the decreased apparent Fe content measured by X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy (XAS). The segregation of Pt

  2. Stability issues in Pd-based catalysts: the role of surface Pt in improving the stability and oxygen reduction reaction (ORR) activity.

    Science.gov (United States)

    Singh, R K; Rahul, R; Neergat, M

    2013-08-21

    Carbon-supported Pd and Pd3Co catalysts have been electrochemically characterized in 0.1 M HClO4 solution and we found that both catalysts were unstable. On repeated potential cycling, the electrochemical surface area of the catalysts decreases and the oxygen reduction reaction (ORR) activity suffers. To stabilize surface Pd atoms of both Pd and Pd3Co catalysts, we deposited Pt using adsorbed hydrogen on the catalytically active Pd sites. The Pt : Pd ratio of Pt-coated Pd and Pt-coated Pd3Co catalysts suggests half-a-monolayer coverage of Pt (two hydrogen atoms required for reducing a Pt(2+) ion). The Pt : Pd ratio of Pt-coated Pd3Co catalyst obtained from the simple geometrical hard sphere model, energy-dispersive X-ray spectroscopy (EDS) line scan and bulk EDS agrees very well with that calculated from the hydrogen desorption (H(des)) charge of Pd3Co. At the same time, the Pt : Pd ratio of Pt-coated Pd calculated from the H(des) charge of Pd catalyst is significantly lower than the ratio obtained from the other methods. Thus, the Pt : Pd ratio of the Pt-coated Pd catalyst estimated from the H(des) region of Pd is an underestimation of the composition. This suggests that Pd forms an electrochemically inactive species from the H(upd) region itself and Co in Pd3Co seems to stabilize Pd against oxidation by delaying the formation of electrochemically inactive species to higher potentials above the H(upd) region. The voltammograms along with the peroxide formation characteristics of the catalysts support the above observations. The deposited Pt on the surface of the Pd and Pd3Co catalysts masks active Pd sites from the electrochemical environment and even partial coverage with Pt improves the stability and ORR activity of the catalysts when compared to that of the respective Pt-free counterparts.

  3. Plasma-induced synthesis of Pt nanoparticles supported on TiO{sub 2} nanotubes for enhanced methanol electro-oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Su, Nan [College of Materials Science and Engineering, Nanjing Tech University, Xin-Mo-Fan Road No. 5, 210009, Nanjing, Jiangsu (China); The Synergetic Innovation Center for Advanced Materials, Xin-Mo-Fan Road No. 5, 210009, Nanjing, Jiangsu (China); Jiangsu National Synergetic Innovation Center for Advanced Materials (SICAM), Xin-Mo-Fan Road No. 5, 210009, Nanjing, Jiangsu (China); Hu, Xiulan, E-mail: whoxiulan@163.com [College of Materials Science and Engineering, Nanjing Tech University, Xin-Mo-Fan Road No. 5, 210009, Nanjing, Jiangsu (China); The Synergetic Innovation Center for Advanced Materials, Xin-Mo-Fan Road No. 5, 210009, Nanjing, Jiangsu (China); Jiangsu National Synergetic Innovation Center for Advanced Materials (SICAM), Xin-Mo-Fan Road No. 5, 210009, Nanjing, Jiangsu (China); Zhang, Jianbo; Huang, Huihong; Cheng, Jiexu; Yu, Jinchen; Ge, Chao [College of Materials Science and Engineering, Nanjing Tech University, Xin-Mo-Fan Road No. 5, 210009, Nanjing, Jiangsu (China)

    2017-03-31

    Highlights: • Pt nanoparticles are synthesized by plasma sputtering in water. • Pt/C/TiO{sub 2} nanotubes shows better mass activity and CO-poisoning tolerance than Pt/C. • TiO{sub 2} nanotubes are more suitable for support materials than TiO{sub 2} small particles. • The metal-support interactions between Pt and TiO{sub 2} nanotubes are detected by XPS. - Abstract: A Pt/C/TiO{sub 2} nanotube composite catalyst was successfully prepared for enhanced methanol electro-oxidation. Pt nanoparticles with a particle size of 2 nm were synthesized by plasma sputtering in water, and anatase TiO{sub 2} nanotubes with an inner diameter of approximately 100 nm were prepared by a simple two-step anodization method and annealing process. Field-emission scanning electron microscopy images indicated that the different morphologies of TiO{sub 2} synthesized on the surface of Ti foils were dependent on the different anodization parameters. The electrochemical performance of Pt/C/TiO{sub 2} catalysts for methanol oxidation showed that TiO{sub 2} nanotubes were more suitable for use as Pt nanoparticle support materials than irregular TiO{sub 2} short nanorods due to their tubular morphology and better electronic conductivity. X-ray photoelectron spectroscopy characterization showed that the binding energies of the Pt 4f of the Pt/C/TiO{sub 2} nanotubes exhibited a slightly positive shift caused by the relatively strong interaction between Pt and the TiO{sub 2} nanotubes, which could mitigate the poisoning of the Pt catalyst by CO{sub ads}, and further enhance the electrocatalytic performance. Thus, the as-obtained Pt/C/TiO{sub 2} nanotubes composites may become a promising catalyst for methanol electro-oxidation.

  4. 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

  5. The tunable plasma synthesis of Pt-reduced graphene oxide nanocomposites

    Directory of Open Access Journals (Sweden)

    Yulong Ma

    2017-06-01

    Full Text Available Herein, we have developed Pt-plasma reduced graphene oxide (Pt/P-rGO catalysts displaying high overpotentials for methanol oxidation reaction (MOR through facile and tunable plasma treatments. We provide insight into the improved performance of these catalysts by combining electrochemical measurements with microscopic and spectroscopic characterization techniques. The analysis results showed that the Pt nanoparticles (NPs were successfully deposited on P-rGO. The deposition and uniformity of Pt NPs were influenced by tuning the discharge power of the plasma. The catalytic performance towards the methanol oxidation reaction is investigated. The Pt/P-rGO NPs composites under 100 W show the best electrocatalytic activity. These results were vital to the further application of graphene-based metal nanocomposites synthesized by plasma technology.

  6. CO oxidation mechanism on the γ-Al{sub 2}O{sub 3} supported single Pt atom: First principle study

    Energy Technology Data Exchange (ETDEWEB)

    Gao, Hongwei, E-mail: gaohongw369@ms.xjb.ac.cn

    2016-08-30

    Highlights: • DFT studied on CO oxidation mechanism on Pt/γ-Al{sub 2}O{sub 3} catalyst. • DFT studied on the adsorption properties of single Pt on Pt/γ-Al{sub 2}O{sub 3} catalyst. • Pt adsorptions on the Al-terminated surface are more favorable than the ones on the O-terminated surface. • The reactive O*−O−C*=O intermediate mechanism is the dominant reaction pathway for CO oxidation on Pt/γ-Al{sub 2}O{sub 3}. - Abstract: Understanding the role of metal-support interaction for the supported single-atom catalysts is very important in heterogeneous catalysis. Here, Three different CO oxidation mechanisms on Pt/γ-Al{sub 2}O{sub 3} catalyst were probed by periodic density functional theory (DFT) calculations in detail, namely the reactive O*−O−C*=O intermediate mechanism, the reactive CO{sub 3} intermediate mechanism and the Pt-Al{sup 3+} double sites mechanism. According to the calculated results analysis, we concluded that the dominant reaction pathway at the low temperatures is the reactive O*−O−C*=O intermediate mechanism. Our results are in very good agreement with the experimental evidence for O*−O−C*=O coverage on Pt/γ-Al{sub 2}O{sub 3} at room temperature by an in situ diffuse reflectance infrared detector.

  7. Electrochemical Oxidation of the Carbon Support to Synthesize Pt(Cu and Pt-Ru(Cu Core-Shell Electrocatalysts for Low-Temperature Fuel Cells

    Directory of Open Access Journals (Sweden)

    Griselda Caballero-Manrique

    2015-04-01

    Full Text Available The synthesis of core-shell Pt(Cu and Pt-Ru(Cu electrocatalysts allows for a reduction in the amount of precious metal and, as was previously shown, a better CO oxidation performance can be achieved when compared to the nanoparticulated Pt and Pt-Ru ones. In this paper, the carbon black used as the support was previously submitted to electrochemical oxidation and characterized by XPS. The new catalysts thus prepared were characterized by HRTEM, FFT, EDX, and electrochemical techniques. Cu nanoparticles were generated by electrodeposition and were further transformed into Pt(Cu and Pt-Ru(Cu core-shell nanoparticles by successive galvanic exchange with Pt and spontaneous deposition of Ru species, the smallest ones being 3.3 nm in mean size. The onset potential for CO oxidation was as good as that obtained for the untreated carbon, with CO stripping peak potentials about 0.1 and 0.2 V more negative than those corresponding to Pt/C and Ru-decorated Pt/C, respectively. Carbon oxidation yielded an additional improvement in the catalyst performance, because the ECSA values for hydrogen adsorption/desorption were much higher than those obtained for the non-oxidized carbon. This suggested a higher accessibility of the Pt sites in spite of having the same nanoparticle structure and mean size.

  8. Seed-mediated synthesis of cross-linked Pt-NiO nanochains for methanol oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Gu, Zhulan; Bin, Duan; Feng, Yue; Zhang, Ke; Wang, Jin; Yan, Bo; Li, Shumin; Xiong, Zhiping; Wang, Caiqin; Shiraishi, Yukihide; Du, Yukou, E-mail: duyk@suda.edu.cn

    2017-07-31

    Highlights: • Cross-linked Pt-NiO nanochains using seed-mediated growth method are synthesized. • The as-prepared catalysts exhibit higher electrocatalytic activity than Pt/C for MOR. • The Pt-NiO(1:1 by molar) catalyst shows the best electrocatalytic property towards MOR. - Abstract: A simple method was reported for employing NiO nanoparticles act as seeds and then different amounts of Pt{sup 2+} were reduced on the NiO nanoparticles, forming a cross-linked Pt-NiO nanocatalysts. These as-prepared catalysts were characterized using different physical-chemical techniques, including X-ray diffraction (XRD), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The results indicate that the morphology of the cross-linked Pt-NiO nanochain was successfully produced regardless of the molar ratio of Pt{sup 2+} to NiO precursors. The electrochemical characteristics of Pt-NiO nanochain catalysts were evaluated for the oxidation of methanol as a model reaction, which verify that the Pt-NiO catalysts show enhanced activity and high stability in comparison with the commercial Pt/C catalyst. The optimized ratio of Pt to NiO is 1:1, then tuned by simple adjusting the feed ratio of the precursors as well. The synthesized nanocatalysts will be found the great potential applications as electrocatalysts for fuel cells owe to their enhanced catalytic performance and long-term stability.

  9. Seed-mediated synthesis of cross-linked Pt-NiO nanochains for methanol oxidation

    International Nuclear Information System (INIS)

    Gu, Zhulan; Bin, Duan; Feng, Yue; Zhang, Ke; Wang, Jin; Yan, Bo; Li, Shumin; Xiong, Zhiping; Wang, Caiqin; Shiraishi, Yukihide; Du, Yukou

    2017-01-01

    Highlights: • Cross-linked Pt-NiO nanochains using seed-mediated growth method are synthesized. • The as-prepared catalysts exhibit higher electrocatalytic activity than Pt/C for MOR. • The Pt-NiO(1:1 by molar) catalyst shows the best electrocatalytic property towards MOR. - Abstract: A simple method was reported for employing NiO nanoparticles act as seeds and then different amounts of Pt 2+ were reduced on the NiO nanoparticles, forming a cross-linked Pt-NiO nanocatalysts. These as-prepared catalysts were characterized using different physical-chemical techniques, including X-ray diffraction (XRD), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The results indicate that the morphology of the cross-linked Pt-NiO nanochain was successfully produced regardless of the molar ratio of Pt 2+ to NiO precursors. The electrochemical characteristics of Pt-NiO nanochain catalysts were evaluated for the oxidation of methanol as a model reaction, which verify that the Pt-NiO catalysts show enhanced activity and high stability in comparison with the commercial Pt/C catalyst. The optimized ratio of Pt to NiO is 1:1, then tuned by simple adjusting the feed ratio of the precursors as well. The synthesized nanocatalysts will be found the great potential applications as electrocatalysts for fuel cells owe to their enhanced catalytic performance and long-term stability.

  10. Robust non-carbon titanium nitride nanotubes supported Pt catalyst with enhanced catalytic activity and durability for methanol oxidation reaction

    International Nuclear Information System (INIS)

    Xiao, Yonghao; Zhan, Guohe; Fu, Zhenggao; Pan, Zhanchang; Xiao, Chumin; Wu, Shoukun; Chen, Chun; Hu, Guanghui; Wei, Zhigang

    2014-01-01

    By the combination of solvothermal alcoholysis and post-nitriding method, titanium nitride nanotubes (TiN NTs), with high surface area, hollow and interior porous structure are prepared successfully and used at a support for Pt nanoparticles. The TiN NTs supported Pt (Pt/TiN NTs) catalyst displays enhanced activity and durability towards methanol oxidation reaction (MOR) compared with the commercial Pt/C (E-TEK) catalyst. X ray diffraction (XRD), nitrogen adsorption/desorption, transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) measurements are performed to investigate the physicochemical properties of the synthesized catalyst. SEM and TEM images reveal that the wall of the TiN NTs is porous and Pt nanoparticles supported on the dendritic TiN nanocrystals exhibit small size and good dispersion. Effects of inherent corrosion-resistant, tubular and porous nanostructures and electron transfer due to the strong metal–support interactions of TiN NTs contribute to the enhanced catalytic activity and stability of Pt/TiN NTs towards the MOR

  11. One‐Electron Oxidation of [M(PtBu3)2] (M=Pd, Pt): Isolation of Monomeric [Pd(PtBu3)2]+ and Redox‐Promoted C−H Bond Cyclometalation

    Science.gov (United States)

    Troadec, Thibault; Tan, Sze‐yin; Wedge, Christopher J.; Rourke, Jonathan P.; Unwin, Patrick R.

    2016-01-01

    Abstract Oxidation of zero‐valent phosphine complexes [M(PtBu3)2] (M=Pd, Pt) has been investigated in 1,2‐difluorobenzene solution using cyclic voltammetry and subsequently using the ferrocenium cation as a chemical redox agent. In the case of palladium, a mononuclear paramagnetic PdI derivative was readily isolated from solution and fully characterized (EPR, X‐ray crystallography). While in situ electrochemical measurements are consistent with initial one‐electron oxidation, the heavier congener undergoes C−H bond cyclometalation and ultimately affords the 14 valence‐electron PtII complex [Pt(κ 2 PC‐PtBu2CMe2CH2)(PtBu3)]+ with concomitant formation of [Pt(PtBu3)2H]+. PMID:26879233

  12. Hydrogen poisoning of the CO oxidation reaction on Pt and Pd under ultrahigh vacuum conditions

    International Nuclear Information System (INIS)

    Strozier, J.A.

    1977-01-01

    The poisoning by hydrogen of the catalyzed oxidation of CO on Pt and Pd under ultrahigh vacuum conditions was investigated. ac pulsing techniques are used in which the pressure of the reactant CO in the reaction chamber is modulated periodically by means of a fast piezoelectric ultrahigh vacuum valve, and the ac component of the product CO 2 is recorded mass spectroscopically by phase-sensitive techniques. The ac CO 2 production rate is measured as a function of hydrogen pressure (1 - 10 x 10 -9 toor) at constant CO and O 2 pressures (approximately equal to 5 x 10 -8 torr), and constant temperature (approximately equal to 700 K). Exact theoretical calculations of CO 2 production rates were carried out employing several models, i.e., oxygen burn-off by hydrogen, incorporating both the Eley-Rideal and Langmuir-Hinshelwood mechanisms. From a comparison with the experimental results, the probable reaction is of the Langmuir-Hinshelwood type and the relevant rate constant is also determined. These results are compared with other results in the literature on hydrogen oxidation on the surface of Pt

  13. Synthesis of Pt-Ni/graphene via in situ reduction and its enhanced catalyst activity for methanol oxidation.

    Science.gov (United States)

    Li, Lihong; Wu, Yuen; Lu, Jun; Nan, Caiyun; Li, Yadong

    2013-09-04

    A simple in situ reduction approach was used to obtain Pt3Ni/reduced graphene oxide (rGO) with dominant {111} facets. The catalytic activity of Pt-Ni/rGO toward methanol electro-oxidation was studied by performing cyclic voltammetry. The Pt3Ni/rGO nanocatalysts exhibited improved catalytic activity and durability.

  14. CeO2/rGO/Pt sandwich nanostructure: rGO-enhanced electron transmission between metal oxide and metal nanoparticles for anodic methanol oxidation of direct methanol fuel cells.

    Science.gov (United States)

    Yu, Xue; Kuai, Long; Geng, Baoyou

    2012-09-21

    Pt-based nanocomposites have been of great research interest. In this paper, we design an efficient MO/rGO/Pt sandwich nanostructure as an anodic electrocatalyst for DMFCs with combination of the merits of rigid structure of metallic oxides (MOs) and excellent electronic conductivity of reduced oxidized graphene (rGO) as well as overcoming their shortcomings. In this case, the CeO(2)/rGO/Pt sandwich nanostructure is successfully fabricated through a facile hydrothermal approach in the presence of graphene oxide and CeO(2) nanoparticles. This structure has a unique building architecture where rGO wraps up the CeO(2) nanoparticles and Pt nanoparticles are homogeneously dispersed on the surface of rGO. This novel structure endows this material with great electrocatalytic performance in methanol oxidation: it reduces the overpotential of methanol oxidation significantly and its electrocatalytic activity and stability are much enhanced compared with Pt/rGO, CeO(2)/Pt and Pt/C catalysts. This work supplies a unique MO/rGO/Pt sandwich nanostructure as an efficient way to improve the electrocatalytic performance, which will surely shed some light on the exploration of some novel structures of electrocatalyst for DMFCs.

  15. CASSCF/CI calculations of electronic states and potential energy surfaces of PtH2

    International Nuclear Information System (INIS)

    Balasubramanian, K.

    1987-01-01

    Complete active space MCSCF followed by MRSDCI (multireference singles and doubles configuration interaction) calculations are carried out on the electronic states of PtH 2 . Spin--orbit interaction is introduced using a relativistic configuration interaction scheme on PtH + whose d orbital Mulliken population is close to that of the d population of PtH 2 and thus enables calculation of spin--orbit splittings for the electronic states of PtH 2 . The bending potential energy surfaces of the 1 A 1 and 3 A 1 states are obtained. The 1 A 1 surface has a bent minimum and dissociates almost without a barrier into Pt( 1 S 0 ) and H 2 , while the 3 A 1 state has a large (--55 kcal/mol) barrier to dissociation into Pt( 3 D 3 )+H 2 . The ground state of PtH 2 is a bent 1 A 1 state (θ = 85 0 )

  16. Green synthesis of Pt-on-Pd bimetallic nanodendrites on graphene via in situ reduction, and their enhanced electrocatalytic activity for methanol oxidation

    International Nuclear Information System (INIS)

    Cai, Zhi-xiong; Liu, Cong-cong; Wu, Geng-huang; Chen, Xiao-mei; Chen, Xi

    2014-01-01

    Graphical abstract: - Highlights: • Porous 3D dendrite-like structure of Pt-on-Pd bimetallic nanostructures supported on graphene were prepared. • The surface of nanostructures was very “clean” because of the surfactant-free formation process and the use of green reagent. • The hetero-nanostructures showed excellent electrocatalytic performance in methanol oxidation. - Abstract: A green synthesis of Pt-on-Pd bimetallic nanodendrites supported on graphene (GPtPdNDs) with a Pd interior and a dendrite-like Pt exterior was achieved using a two-step preparation, mixing graphene and PdCl 4 2− first, then adding PtCl 4 2− and ethanol without any other solvent. The morphology, structure and composition of the thus-prepared GPtPdNDs were characterized by transmission electron microscopy (TEM), high resolution TEM, energy-dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy. Because no halide ions (refer in particular to Br - , I − ) or surfactant was involved in the synthesis, the prepared GPtPdNDs were directly modified onto a glassy carbon electrode and showed excellent electrocatalytic performance in methanol oxidation without any pretreatments. Moreover, with the special structure of PtPdNDs and the synergetic effects of Pt and Pd and the enhanced electron transfer by graphene, the GPtPdNDs composites exhibited higher electrocatalytic activity and better tolerance to Pt nanoparticles supported on graphene (GPtNPs) and Pt/C for methanol oxidation

  17. CO oxidation catalyzed by Pt-embedded graphene: A first-principles investigation

    KAUST Repository

    Liu, Xin

    2014-01-01

    We addressed the potential catalytic role of Pt-embedded graphene in CO oxidation by first-principles-based calculations. We showed that the combination of highly reactive Pt atoms and defects over graphene makes the Pt-embedded graphene a superior mono-dispersed atomic catalyst for CO oxidation. The binding energy of a single Pt atom onto monovacancy defects is up to -7.10 eV, which not only ensures the high stability of the embedded Pt atom, but also vigorously excludes the possibility of diffusion and aggregation of embedded Pt atoms. This strong interfacial interaction also tunes the energy level of Pt-d states for the activation of O2, and promotes the formation and dissociation of the peroxide-like intermediate. The catalytic cycle of CO oxidation is initiated through the Langmuir-Hinshelwood mechanism, with the formation of a peroxide-like intermediate by the coadsorbed CO and O2, by the dissociation of which the CO2 molecule and an adsorbed O atom are formed. Then, another gaseous CO will react with the remnant O atom and make the embedded Pt atom available for the subsequent reaction. The calculated energy barriers for the formation and dissociation of the peroxide-like intermediate are as low as 0.33 and 0.15 eV, respectively, while that for the regeneration of the embedded Pt atom is 0.46 eV, indicating the potential high catalytic performance of Pt-embedded graphene for low temperature CO oxidation.

  18. Facile synthesis of hydrangea-like core-shell Pd@Pt/graphene composite as an efficient electrocatalyst for methanol oxidation

    Science.gov (United States)

    Xu, Shuhong; Li, Zhongshui; Lei, Fengling; Wang, Yanli; Xie, Yixin; Lin, Shen

    2017-12-01

    Core-shell palladium@platinum/graphene composite (denoted as Pd@Pt/GNs (PDDA)) was synthesized by successive reduction with formic acid as a reducing agent and poly(diallyldimethylammonium chloride) solution (PDDA) as a structure-directing agent at ambient temperature. The as-synthesized Pd@Pt/GNs (PDDA) was characterized by transmission electron microscopy (TEM), high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). The results indicate that hydrangea-like PtPd bimetallic nanoclusters on graphene (GNs) are formed with the aid of morphology control of PDDA. Especially, they are in a typical core-shell structure with Pd as core and Pt as shell, which are uniformly dispersed on the surface of GNs. Electrocatalytic tests show that Pd@Pt/GNs (PDDA) exhibits superior electrocatalytic activity for methanol oxidation (with the mass activities of 870.8 mA mg-1 Pt) in comparison with the commercial Pt/C and alloyed Pd-Pt/GNs (PDDA) catalysts owing to its unique Pd core Pt shell hydrangea-like structure and the synergistic effects between Pd@Pt and GNs.

  19. TiO2 and Al2O3 promoted Pt/C nanocomposites as low temperature fuel cell catalysts for electro oxidation of methanol in acidic media

    International Nuclear Information System (INIS)

    Naeem, Rabia; Ahmed, Riaz; Ansari, Muhammad Shahid

    2014-01-01

    Carbon corrosion and platinum dissolution are the two major catalyst layer degradation problems in polymer electrolyte membrane fuel cells (PEMFC). Ceramic addition can reduce the corrosion of carbon and increase the stability of catalysts. Pt/TiO 2 , Pt/TiO 2 -C, Pt/Al 2 O 3 and Pt/Al 2 O 3 -C catalysts were synthesized and characterized. Electrochemical surface area of Pt/TiO 2 -C and Pt/Al 2 O 3 -C nanocomposite catalysts was much higher than the Pt/TiO 2 and Pt/Al 2 O 3 catalysts. Peak current, specific activity and mass activity of the catalysts was also determined by cyclic voltammetry and were much higher for the carbon nanocomposites. Exchange current densities were determined from Tafel plots. Heterogeneous rates of reaction of electro oxidation of methanol were determined for all the catalysts and were substantially higher for titania catalysts as compared to alumina added catalysts. Mass activity of Pt/TiO 2 -C was much higher than mass activity of Pt/Al 2 O 3 -C. Stability studies showed that addition of ceramics have increased the catalytic activity and durability of the catalysts considerably

  20. 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.

  1. Synthesis of honeycomb-like mesoporous nitrogen-doped carbon nanospheres as Pt catalyst supports for methanol oxidation in alkaline media

    Science.gov (United States)

    Zhang, Yunmao; Liu, Yong; Liu, Weihua; Li, Xiying; Mao, Liqun

    2017-06-01

    This paper reports the convenient synthesis of honeycomb-like mesoporous nitrogen-doped carbon spheres (MNCS) using a self-assembly strategy that employs dopamine (DA) as a carbon and nitrogen precursor and a polystyrene-b-poly(ethylene oxide) (PS173-b-PEO170) diblock copolymer as a soft template. The MNCS have large BET surface areas of up to 554 m2 g-1 and high nitrogen contents of up to 6.9 wt%. The obtained MNCS are used as a support for Pt catalysts, which promote methanol oxidation in alkaline media. The MNCS-supported Pt (Pt/MNCS) catalyst has a larger electrochemically active surface area (ESA) (89.2 m2 g-1) than does a commercially available Vulcan XC-72R supported Pt/C catalyst. Compared to the Pt/C catalyst, Pt/MNCS displays a higher peak current density (1007 mA mg-1) and is more stable during methanol oxidation. These improvements are attributed to the honeycomb-like porous structure of the MNCS and the introduction of nitrogen to the carbon support. The MNCS effectively stabilize Pt nanoparticles and assuage the agglomeration of the nanoparticles, suggesting that MNCS are potential and promising application as electrocatalyst supports in alkaline direct methanol fuel cells.

  2. 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.

  3. Kinetically controlled synthesis of Pt-Cu alloy concave nanocubes with high-index facets for methanol electro-oxidation.

    Science.gov (United States)

    Qi, Yue; Bian, Ting; Choi, Sang-Il; Jiang, Yingying; Jin, Chuanhong; Fu, Maoshen; Zhang, Hui; Yang, Deren

    2014-01-18

    Pt-Cu alloy concave nanocubes enclosed by high-index {511} facets were synthesized in high yields and exhibited substantially enhanced electrocatalytic properties for methanol oxidation relative to commercial Pt/C.

  4. Theoretical study of CCl(4) adsorption and hydrogenation on a Pt (111) surface.

    Science.gov (United States)

    Lu, Guiwu; Lan, Jianhui; Li, Chunxi; Wang, Wenchuan; Wang, Chunlei

    2006-12-07

    The adsorption and hydrogenation of carbon tetrachloride (CCl(4)) on a Pt (111) surface have been investigated using density functional theory (DFT). We have performed calculations on the adsorption energies and structures of CCl(4) on four different adsorption sites of a Pt (111) surface using the full adsorbate geometry optimization method. The results show that the adsorption energy of all of the potential sites is less than -17 kcal/mol, which indicates that CCl(4) is physiosorbed on a Pt (111) surface through van der Waals interactions. The dissociation and hydrogenation pathways were investigated by a transition state search. For the Pt(15), Pt(19), and Pt(25) cluster surfaces, the activation energies of dissociation obtained in this work are 15.69, 16.94, and 16.77 kcal/mol, respectively. The hydrogenation of CCl(3). was studied at the on-top site of the Pt(15) cluster, and the calculated activation energy is 5.06 kcal/mol. The small activation energies indicate that the Pt (111) surface has high catalytic activity for the CCl(4) hydrogenation reaction. In addition, the Hirshfeld population analysis reveals that the charge transfer from the Pt (111) surface to the adsorbates occurs in both the dissociation and hydrogenation pathways.

  5. Supported 3-D Pt nanostructures: the straightforward synthesis and enhanced electrochemical performance for methanol oxidation in an acidic medium

    International Nuclear Information System (INIS)

    Li, Zesheng; Ji, Shan; Pollet, Bruno G.; Shen, Pei Kang

    2013-01-01

    Noble metal nanostructures with branched morphologies [i.e., 3-D Pt nanoflowers (NFs)] by tri-dimensionally integrating onto conductive carbon materials are proved to be an efficient and durable electrocatalysts for methanol oxidation. The well-supported 3-D Pt NFs are readily achieved by an efficient cobalt-induced/carbon-mediated galvanic reaction approach. Due to the favorable nanostructures (3-D Pt configuration allowing a facile mass transfer) and supporting effects (including framework stabilization, spatially separate feature, and improved charge transport effects), these 3-D Pt NFs manifest much higher electrocatalytic activity and stability toward methanol oxidation than that of the commercial Pt/C and Pt-based electrocatalysts

  6. Morphology-dependent activity of Pt nanocatalysts for ethanol oxidation in acidic media: Nanowires versus nanoparticles

    International Nuclear Information System (INIS)

    Zhou Weiping; Li Meng; Koenigsmann, Christopher; Ma Chao; Wong, Stanislaus S.; Adzic, Radoslav R.

    2011-01-01

    Highlights: → We demonstrate the morphology effect of Pt catalysts in electrooxidation of ethanol and CO in an acidic solution. → Pt nanowires and nanoparticles were used as catalysts. → Pt nanowires display a higher catalytic activity by a factor of at least two relative to those nanoparticles for ethanol oxidation. → The rate for CO monolayer oxidation exhibits similar morphology-dependent behavior with a markedly enhanced rate on the Pt nanowires. - Abstract: The morphology of nanostructured Pt catalysts is known to affect significantly the kinetics of various reactions. Herein, we report on a pronounced morphology effect in the electrooxidation of ethanol and carbon monoxide (CO) on Pt nanowires and nanoparticles in an acidic solution. The high resolution transmission electron microscopy analysis showed the inherent morphology difference between these two nanostructured catalysts. Voltammetric and chronoamperometric studies of the ethanol electrooxidation revealed that these nanowires had a higher catalytic activity by a factor of two relative to these nanoparticles. The rate for CO monolayer oxidation exhibits similar morphology-dependent behavior with a markedly enhanced rate on the Pt nanowires. In situ infrared reflection-absorption spectroscopy measurements revealed a different trend for chemisorbed CO formation and CO 2 -to-acetic acid reaction product ratios on these two nanostructures. The morphology-induced change in catalytic activity and selectivity in ethanol electrocatalysis is discussed in detail.

  7. Effects of Alloyed Metal on the Catalysis Activity of Pt for Ethanol Partial Oxidation: Adsorption and Dehydrogenation on Pt(3)M (M=Pt, Ru, Sn, Re, Rh, and Pd).

    Science.gov (United States)

    Xu, Zhen-Feng; Wang, Yixuan

    2011-10-27

    The adsorption and dehydrogenation reactions of ethanol over bimetallic clusters, Pt(3)M (M = Pt, Ru, Sn, Re, Rh, and Pd), have been extensively investigated with density functional theory. Both the α-hydrogen and hydroxyl adsorptions on Pt as well as on the alloyed transition metal M sites of PtM were considered as initial reaction steps. The adsorptions of ethanol on Pt and M sites of some PtM via the α-hydrogen were well established. Although the α-hydrogen adsorption on Pt site is weaker than the hydroxyl, the potential energy profiles show that the dehydrogenation via the α-hydrogen path has much lower energy barrier than that via the hydroxyl path. Generally for the α-hydrogen path the adsorption is a rate-determining-step because of rather low dehydrogenation barrier for the α-hydrogen adsorption complex (thermodynamic control), while the hydroxyl path is determined by its dehydrogenation step (kinetic control). The effects of alloyed metal on the catalysis activity of Pt for ethanol partial oxidation, including adsorption energy, energy barrier, electronic structure, and eventually rate constant were discussed. Among all of the alloyed metals only Sn enhances the rate constant of the dehydrogenation via the α-hydrogen path on the Pt site of Pt(3)Sn as compared with Pt alone, which interprets why the PtSn is the most active to the oxidation of ethanol.

  8. Characterizing electrocatalytic surfaces: Electrochemical and NMR studies of methanol and carbon monoxide on Pt/C

    Energy Technology Data Exchange (ETDEWEB)

    McGrath, Patrick; Fojas, Aurora Marie; Rush, Benjamin; Reimer, Jeffrey A.; Cairns, Elton J. [Lawrence Berkeley National Laboratory and University of California, Berkeley, CA 94720 (United States)

    2007-12-20

    We use cyclic voltammetry (CV) on fuel cell electrodes to elucidate the important differences between adsorbates resulting from carbon monoxide adsorption and methanol adsorption onto commercial Pt/C electrocatalysts in a sulfuric acid electrolyte. Under open circuit conditions, methanol was found to adsorb preferentially onto the Pt sites associated with 'strongly bound' hydrogen. The sites associated with 'weakly bound' hydrogen adsorbed methanol more slowly. In the case of CO adsorption, which requires no adsorbate dehydrogenation, all adsorption sites showed similar affinity towards the adsorbate. Electrochemical oxidation of the adsorbates derived from both methanol and CO exposure exhibit slower oxidation when the adsorbate is associated with cubic-packed-like sites than from close-packed-steps and other sites. NMR of a {sup 13}CO-adlayer prepared by electrochemical adsorption from low concentration {sup 13}CH{sub 3}OH shows a lower NMR shift and smaller linewidth than the previously reported values for electrochemically adsorbed {sup 13}CO gas. These results are interpreted in terms of adsorbate motion on the electrocatalyst surface. (author)

  9. Microstructure and oxidation performance of a γ–γ ′ Pt-aluminide ...

    Indian Academy of Sciences (India)

    Administrator

    base superalloy has been examined and its cyclic oxidation performance at 1100 °C in air is comparatively evaluated with that of a conventional β-(Ni, Pt)Al bond coat. The γ–γ ′ bond coat was effective in imparting oxidation resistance to the.

  10. Impact of support oxide acidity in Pt-catalyzed HMF hydrogenation in alcoholic medium

    DEFF Research Database (Denmark)

    Al-Shamery, Katharina; Ly, Nhu; Chan-Thaw, Carine E.

    2017-01-01

    Abstract: Silica and three mixed silica oxides (silica–alumina, silica–niobia, and silica–zirconia) with nominally 5 wt% of the added element (Al, Nb and Zr) were prepared and used as supports for dispersing monometallic Pt-nanoparticles. The presence of the second oxide component on the silica s...

  11. Improving the Ethanol Oxidation Activity of Pt-Mn Alloys through the Use of Additives during Deposition

    Directory of Open Access Journals (Sweden)

    Mohammadreza Zamanzad Ghavidel

    2015-06-01

    Full Text Available In this work, sodium citrate (SC was used as an additive to control the particle size and dispersion of Pt-Mn alloy nanoparticles deposited on a carbon support. SC was chosen, since it was the only additive tested that did not prevent Mn from co-depositing with Pt. The influence of solution pH during deposition and post-deposition heat treatment on the physical and electrochemical properties of the Pt-Mn alloy was examined. It was determined that careful control over pH is required, since above a pH of four, metal deposition was suppressed. Below pH 4, the presence of sodium citrate reduced the particle size and improved the particle dispersion. This also resulted in larger electrochemically-active surface areas and greater activity towards the ethanol oxidation reaction (EOR. Heat treatment of catalysts prepared using the SC additive led to a significant enhancement in EOR activity, eclipsing the highest activity of our best Pt-Mn/C prepared in the absence of SC. XRD studies verified the formation of the Pt-Mn intermetallic phase upon heat treatment. Furthermore, transmission electron microscopy studies revealed that catalysts prepared using the SC additive were more resistant to particle size growth during heat treatment.

  12. Thermally stable single atom Pt/m-Al2O3 for selective hydrogenation and CO oxidation

    KAUST Repository

    Zhang, Zailei

    2017-07-27

    Single-atom metal catalysts offer a promising way to utilize precious noble metal elements more effectively, provided that they are catalytically active and sufficiently stable. Herein, we report a synthetic strategy for Pt single-atom catalysts with outstanding stability in several reactions under demanding conditions. The Pt atoms are firmly anchored in the internal surface of mesoporous Al2O3, likely stabilized by coordinatively unsaturated pentahedral Al3+ centres. The catalyst keeps its structural integrity and excellent performance for the selective hydrogenation of 1,3-butadiene after exposure to a reductive atmosphere at 200 °C for 24 h. Compared to commercial Pt nanoparticle catalyst on Al2O3 and control samples, this system exhibits significantly enhanced stability and performance for n-hexane hydro-reforming at 550 °C for 48 h, although agglomeration of Pt single-atoms into clusters is observed after reaction. In CO oxidation, the Pt single-atom identity was fully maintained after 60 cycles between 100 and 400 °C over a one-month period.

  13. Steam reforming, partial oxidation, and oxidative steam reforming of ethanol over Pt/CeZrO2 catalyst

    OpenAIRE

    Noronha, Fábio Bellot

    2008-01-01

    The catalytic performance of a Pt/CeZrO2 catalyst was tested for ethanol decomposition, steam reforming, partial oxidation, and oxidative steam reforming. At low temperature, the catalyst underwent significant deactivation during ethanol decomposition and steam reforming reactions. Co-feeding oxygen decreased the deactivation rate of the catalyst but adversely affected the selectivity to hydrogen.

  14. Promoting effect of vanadium on catalytic activity of Pt/Ce-Zr-O diesel oxidation catalysts.

    Science.gov (United States)

    Huang, Haifeng; Jiang, Bo; Gu, Lei; Qi, Zhonghua; Lu, Hanfeng

    2015-07-01

    A series of Pt-V/Ce-Zr-O diesel oxidation catalysts was prepared using the impregnation method. The catalytic activity and sulfur resistance of Pt-V/Ce-Zr-O were investigated in the presence of simulated diesel exhaust. The effect of vanadium on the structure and redox properties of the catalysts was also investigated using the Brunauer-Emmett-Teller method, X-ray diffraction, H2 temperature-programmed reduction, CO temperature-programmed desorption, X-ray photoelectron spectroscopy, and Energy Dispersive Spectroscopy. Results showed that the Pt particles were well dispersed on the Ce-Zr-O carrier through the vanadium isolation effect, which significantly improved the oxidation activity toward CO and hydrocarbons. An electron-withdrawing phenomenon occurred from V to Pt, resulting in an increase in the metallic nature of platinum, which was beneficial to hydrocarbon molecular activation. Copyright © 2015. Published by Elsevier B.V.

  15. Ultra-long Pt nanolawns supported on TiO2-coated carbon fibers as 3D hybrid catalyst for methanol oxidation.

    Science.gov (United States)

    Shen, Yu-Lin; Chen, Shih-Yun; Song, Jenn-Ming; Chen, In-Gann

    2012-06-26

    In this study, TiO2 thin film photocatalyst on carbon fibers was used to synthesize ultra-long single crystalline Pt nanowires via a simple photoreduction route (thermally activated photoreduction). It also acted as a co-catalytic material with Pt. Taking advantage of the high-aspect ratio of the Pt nanostructure as well as the excellent catalytic activity of TiO2, this hybrid structure has the great potential as the active anode in direct methanol fuel cells. The electrochemical results indicate that TiO2 is capable of transforming CO-like poisoning species on the Pt surface during methanol oxidation and contributes to a high CO tolerance of this Pt nanowire/TiO2 hybrid structure.

  16. Kinetics of ammonia oxidation over Pt foil studied in a micro-structured quartz-reactor

    OpenAIRE

    Kraehnert, Ralf; Baerns, Manfred

    2008-01-01

    The kinetics of Pt-catalyzed ammonia oxidation on polycrystalline Pt were investigated at partial pressures of ammonia and oxygen up to 6 kPa and temperatures between 286 and 385 °C, applying a micro-structured reactor that ascertained temperature control of the exothermic reaction. Using literature-based mechanistic models, a micro-kinetic model was derived based on parameter optimization and a model discrimination procedure. The model described the rates of formation of all nitrogen-contain...

  17. The use of graphite oxide to produce mesoporous carbon supporting Pt, Ru, or Pd nanoparticles

    OpenAIRE

    Gotoh, Kazuma; Kawabata, Koji; Fujii, Eiji; Morishige, Kunimitsu; Kinumoto, Taro; Miyazaki, Yuki; Ishida, Hiroyuki

    2009-01-01

    Mesoporous carbon having platinum, ruthenium or palladium nanoparticles on exfoliated graphene sheets were produced from graphite oxide (GO) and metal complexes. The Pt included carbon was made by heating of the intercalation compound including tetraammineplatinum (II) chloride monohydrate. Samples having Ru or Pd are producible by heating in nitrogen gas atmosphere using hexaammineruthenium (III) chloride or tetraamminepalladium (II) chloride monohydrate instead of Pt complex. The particle s...

  18. Magnetic properties of thermally reduced graphene oxide decorated with PtNi nanoparticles

    International Nuclear Information System (INIS)

    Huízar-Félix, A.M.; Cruz-Silva, R.; Barandiarán, J.M.; García-Gutiérrez, D.I.; Orue, I.

    2016-01-01

    Nanocomposites of reduced graphene oxide (RGO) with PtNi nanoparticles were obtained by in situ thermal reduction of a physical mixture of GO and metallic precursors. RGO and PtNiRGO nanocomposites were studied by differential thermal analysis and thermogravimetry, Fourier transform infrared spectroscopy (FTIR), powder X-ray diffraction (XRD), as well as scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The method presented here is a one-step thermal reduction procedure that allows the deposition of bimetallic PtNi nanoparticles with tetragonal crystalline structure and particle size ranging from 3 nm to 30 nm on RGO. The magnetic properties of the RGO and PtNiRGO nanocomposites were measured by vibrating sample magnetometry, which revealed that the RGO exhibited diamagnetism at room temperature and paramagnetism at temperatures below 10 K. PtNiRGO nanocomposites show hysteresis and ferromagnetic ordering at room temperature with a Curie temperature of 658 K. In addition, its magnetic properties at low temperature were strongly influenced by the paramagnetic contribution of RGO and the morphology of the bimetallic nanoparticles. - Highlights: • Simultaneous synthesis method for growth of PtNi nanoparticles on RGO. • Microstructural features of PtNiRGO nanocomposite were studied with extensive characterization. • Diamagnetic behavior of RGO and ferromagnetic ordering for PtNiRGO nanocomposite.

  19. Seed-mediated synthesis of cross-linked Pt-NiO nanochains for methanol oxidation

    Science.gov (United States)

    Gu, Zhulan; Bin, Duan; Feng, Yue; Zhang, Ke; Wang, Jin; Yan, Bo; Li, Shumin; Xiong, Zhiping; Wang, Caiqin; Shiraishi, Yukihide; Du, Yukou

    2017-07-01

    A simple method was reported for employing NiO nanoparticles act as seeds and then different amounts of Pt2+ were reduced on the NiO nanoparticles, forming a cross-linked Pt-NiO nanocatalysts. These as-prepared catalysts were characterized using different physical-chemical techniques, including X-ray diffraction (XRD), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The results indicate that the morphology of the cross-linked Pt-NiO nanochain was successfully produced regardless of the molar ratio of Pt2+ to NiO precursors. The electrochemical characteristics of Pt-NiO nanochain catalysts were evaluated for the oxidation of methanol as a model reaction, which verify that the Pt-NiO catalysts show enhanced activity and high stability in comparison with the commercial Pt/C catalyst. The optimized ratio of Pt to NiO is 1:1, then tuned by simple adjusting the feed ratio of the precursors as well. The synthesized nanocatalysts will be found the great potential applications as electrocatalysts for fuel cells owe to their enhanced catalytic performance and long-term stability.

  20. Pt nanocatalysts supported on reduced graphene oxide for selective conversion of cellulose or cellobiose to sorbitol.

    Science.gov (United States)

    Wang, Ding; Niu, Wenqi; Tan, Minghui; Wu, Mingbo; Zheng, Xuejun; Li, Yanpeng; Tsubaki, Noritatsu

    2014-05-01

    Pt nanocatalysts loaded on reduced graphene oxide (Pt/RGO) were prepared by means of a convenient microwave-assisted reduction approach with ethylene glycol as reductant. The conversion of cellulose or cellobiose into sorbitol was used as an application reaction to investigate their catalytic performance. Various metal nanocatalysts loaded on RGO were compared and RGO-supported Pt exhibited the highest catalytic activity with 91.5 % of sorbitol yield from cellobiose. The catalytic performances of Pt nanocatalysts supported on different carbon materials or on silica support were also compared. The results showed that RGO was the best catalyst support, and the yield of sorbitol was as high as 91.5 % from cellobiose and 58.9 % from cellulose, respectively. The improvement of catalytic activity was attributed to the appropriate Pt particle size and hydrogen spillover effect of Pt/RGO catalyst. Interestingly, the size and dispersion of supported Pt particles could be easily regulated by convenient adjustment of the microwave heating temperature. The catalytic performance was found to initially increase and then decrease with increasing particle size. The optimum Pt particle size was 3.6 nm. These findings may offer useful guidelines for designing novel catalysts with beneficial catalytic performance for biomass conversion. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Magnetic properties of thermally reduced graphene oxide decorated with PtNi nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Huízar-Félix, A.M. [Universidad Autónoma de Nuevo León, UANL, Facultad de Ingeniería Mecánica y Eléctrica, FIME, Ave. Pedro de Alba s/n, Ciudad Universitaria, C.P.66455 San Nicolás de los Garza, N.L. (Mexico); Departamento de Electricidad y Electrónica, Universidad del País Vasco (UPV/EHU), 48940 Leioa (Spain); BC Materials, Basque Centre for Materials, Applications and Nanostructures, 48160 Derio (Spain); Cruz-Silva, R. [Research Center for Exotic NanoCarbon, Shinshu University, 4-17-1 Wakasato, Nagano 380-8553 (Japan); Barandiarán, J.M. [Departamento de Electricidad y Electrónica, Universidad del País Vasco (UPV/EHU), 48940 Leioa (Spain); BC Materials, Basque Centre for Materials, Applications and Nanostructures, 48160 Derio (Spain); García-Gutiérrez, D.I. [Universidad Autónoma de Nuevo León, UANL, Facultad de Ingeniería Mecánica y Eléctrica, FIME, Ave. Pedro de Alba s/n, Ciudad Universitaria, C.P.66455 San Nicolás de los Garza, N.L. (Mexico); Orue, I. [SGIKER Medidas Magnéticas, Facultad de Ciencia y Tecnología, Universidad del País Vasco (UPV/EHU), 48940 Leioa (Spain); and others

    2016-09-05

    Nanocomposites of reduced graphene oxide (RGO) with PtNi nanoparticles were obtained by in situ thermal reduction of a physical mixture of GO and metallic precursors. RGO and PtNiRGO nanocomposites were studied by differential thermal analysis and thermogravimetry, Fourier transform infrared spectroscopy (FTIR), powder X-ray diffraction (XRD), as well as scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The method presented here is a one-step thermal reduction procedure that allows the deposition of bimetallic PtNi nanoparticles with tetragonal crystalline structure and particle size ranging from 3 nm to 30 nm on RGO. The magnetic properties of the RGO and PtNiRGO nanocomposites were measured by vibrating sample magnetometry, which revealed that the RGO exhibited diamagnetism at room temperature and paramagnetism at temperatures below 10 K. PtNiRGO nanocomposites show hysteresis and ferromagnetic ordering at room temperature with a Curie temperature of 658 K. In addition, its magnetic properties at low temperature were strongly influenced by the paramagnetic contribution of RGO and the morphology of the bimetallic nanoparticles. - Highlights: • Simultaneous synthesis method for growth of PtNi nanoparticles on RGO. • Microstructural features of PtNiRGO nanocomposite were studied with extensive characterization. • Diamagnetic behavior of RGO and ferromagnetic ordering for PtNiRGO nanocomposite.

  2. Potential Energy Surface of NO on Pt(997: Adsorbed States and Surface Diffusion

    Directory of Open Access Journals (Sweden)

    N. Tsukahara

    2012-01-01

    Full Text Available The potential energy surface (PES of NO on Pt(997 has been elucidated: the adsorption states and diffusion processes of NO on Pt(997 at low coverage were investigated by using infrared reflection absorption spectroscopy (IRAS and scanning tunneling microscopy (STM. When NO molecules adsorb on a surface at a low temperature (11 K, each molecule transiently migrates on the surface from the first impact point to a possible adsorption site. We found that there are four stable adsorption sites for NO on Pt(997: a bridge site of the upper step, an fcc- (or hcp- hollow site of the terrace, an on-top site of the terrace, and an fcc-hollow site of the lower step. At higher temperatures above 45 K, NO molecules start to migrate thermally to more stable adsorption sites on a terrace, and they are finally trapped at the bridge sites of the step, which are the most stable among the four sites.

  3. The Effects of Conducting Polymers on Formic Acid Oxidation at Pt Nanoparticles

    International Nuclear Information System (INIS)

    Moghaddam, Reza B.; Ali, Osama Y.; Javashi, Mohammad; Warburton, Peter L.; Pickup, Peter G.

    2015-01-01

    Highlights: • The activity of Pt nanoparticles for formic acid oxidation varies with the chemical structure of the polymer support. • Polycarbazole is strongly activating while a polypyrrole support inhibits formic acid oxidation. • There is a correlation between activity and the energy of the lowest unoccupied orbital of the repeat unit of the polymer. • An electronic effect involving electron donation from Pt to the polymer may be responsible for the differences in activity. - Abstract: The effects of polyaniline, polypyrrole, polyindole and polycarbazole on formic acid oxidation at Pt nanoparticles are compared. The observed trend in activity (polypyrrole < polyaniline ∼ polyindole < polycarbazole) correlates with the decreasing LUMO energies of the monomers (pyrrole > aniline > indole > carbazole), supporting previous evidence of electron donation from Pt nanoparticles into the π-system of a polycarbazole support layer. Density functional theory calculations on CO and carbazole binding to Pt 4 clusters show that the electronic effect of carbazole in a carbazole-Pt 4 -CO ensemble considerably weakens the binding of CO. The magnitude of this effect is comparable to the effects of graphite and graphene supports reported by other researchers, and stronger than the effect calculated here for indole

  4. Electrochemical evaluation of adsorption and oxidation of the carbon monoxide towards ordered intermetallic phases Pt-M (M=Mn, Pb, Sb e Sn); Avaliacao eletroquimica da adsorcao e oxidacao do monoxido de carbono sobre fases intermetalicas ordenadas Pt-M (M=Mn, Pb, Sb e Sn)

    Energy Technology Data Exchange (ETDEWEB)

    Nicolai, A.L.; Miguel-Junior, E.; Silva, R.I.V. da; Angelo, A.C.D. [UNESP, Bauru, SP (Brazil). Depto. de Quimica. Lab. de Eletrocatalise

    2004-07-01

    This paper presents the experimental results obtained from the electrochemical evaluation of Pt ordered intermetallic phases (PtMn, PtPb, PtSb, PtSn) as electrode materials towards the CO oxidation reaction. The intermetallics showed a higher performance than pure Pt in the same experimental conditions. PtSn has presented the highest performance among the evaluated materials. There was not observed a clear relationship between the electrocatalytic activity of the materials and their ability in producing oxygen species at lower anodic potentials, suggesting that surface electronic density and structural characteristics of the electrode surfaces must be the properties to be investigated in order to explain the obtained results. (author)

  5. Facial synthesis of porous hematite supported Pt catalyst and its photo enhanced electrocatalytic ethanol oxidation performance

    International Nuclear Information System (INIS)

    Kang, Shuai; Shen, Pei Kang

    2015-01-01

    Graphical Abstract: A porous α-Fe 2 O 3 supported Pt catalyst has been synthesized by a facial thermal treatment assisted precipitation method and the materials show a illumination enhanced performance for ethanol oxidation. Display Omitted -- Highlights: •A porous α-Fe 2 O 3 supported Pt catalyst has been synthesized for the first time. •With the addition of α-Fe 2 O 3 , the current density of Pt/C grows about 51% under illumination and 32% in the dark compared with unsupported catalyst. •The current increases under illuminationin chronoamperometric experiments at a given potential of 0.7 V due to the photons from light provide energy for CO stripping. •This work demostrates an optical strategy to accelerate electrode reactions towards ethanol oxidation reaction. -- Abstract: The porous α-Fe 2 O 3 supported Pt catalyst is synthesized by a facial thermal treatment assisted precipitation method. The particle size of Pt is less than 3 nm. The pore diameters of α-Fe 2 O 3 particles are concentrated to 2.46 nm in a mesooporous scale. Its electrochemical performance is tested. The ethanol oxidation current of the Pt/Fe 2 O 3 catalsyt obviously improves under illumination, compared with that in the dark, during the optical switching operation. Moreover, with the addition of α-Fe 2 O 3 , the ethanol oxidation current of Pt/C grows about 51% under illumination and 32% in the dark; the onset potential shifts negtively for about 20 mV. This work demostrates an optical strategy which can be a potential alternative to accelerate electrode reactions towards ethanol oxidation reaction

  6. Antisite-defect-induced surface segregation in ordered NiPt alloy

    DEFF Research Database (Denmark)

    Pourovskii, L.V.; Ruban, Andrei; Abrikosov, I.A.

    2003-01-01

    alloys corresponds to the (111) truncation of the bulk L1(0) ordered structure. However, the (111) surface of the nickel deficient Ni49Pt51 alloy is strongly enriched by Pt and should exhibit the pattern of the 2x2 structure. Such a drastic change in the segregation behavior is due to the presence...

  7. Stripping and bulk CO electro-oxidation at the Pt-electrode interface: Dynamic Monte Carlo simulations

    Science.gov (United States)

    Saravanan, Chandra; Markovic, N. M.; Head-Gordon, M.; Ross, P. N.

    2001-04-01

    We perform dynamic Monte Carlo simulations to understand the kinetics of CO oxidation on Pt surface. Our simulations are performed on a model for CO electro-oxidation, where oxygen-containing species (adsorbed OH) formed on the Pt surface reacts with adsorbed CO by a Langmuir-Hinshelwood mechanism to form CO2. A systematic study of the model parameters shows that we obtain better electrocatalytic activity by increasing the surface diffusion coefficient of CO (kD) or the rate of reaction between adsorbed CO and adsorbed OH. We also show that if the initial state of adsorbed CO is a closely packed structure, increasing the surface coverage can result in negative voltammetry peak shifts because of the formation of weakly adsorbed states of CO. We have also modeled bulk CO voltammetry by introducing a CO adsorption rate, k4. We show that near-zero currents are obtained for the potentials (E) where the rate of OH adsorption, k1(E), is much smaller than k4. We also note that kD plays no significant role in CO oxidation when kD≪k4. Our results also show that bulk CO voltammetry peaks shift to more positive potentials compared to the stripping, as observed in experiments. Our potential step simulations show no difference in bulk and stripping current transients in the potential regions where k1(E)≫k4, whereas they vary significantly when k4≅k1(E).

  8. Use of PtAu/C electrocatalysts toward formate oxidation: electrochemical and fuel cell considerations

    Directory of Open Access Journals (Sweden)

    Sirlane G. da Silva

    2016-09-01

    Full Text Available Abstract This study reports the use of PtAu/C electrocatalysts with different atomic ratios (90:10, 70:30 and 50:50 supported on Vulcan XC 72 carbon and prepared by the sodium borohydride method toward formate electro-oxidation in alkaline media. The materials were characterized by X-ray diffraction, showing peaks characteristics of Pt and Au face-centered-cubic structures, and also by transmission electron micrographs that show the nanoparticles well dispersed on carbon and a mean particle size between 4 and 5 nm for all electrocatalysts. Electrochemical experiments show PtAu/C as promising catalysts toward formate oxidation, while single cell experiments reveal PtAu/C 90:10 as the best material since it provides a power density higher than Pt/C. The incorporation of Au could increase formate oxidation for more than one reason: (i a facilitated rupture of C–H bond; (ii the Au/oxide interface or (iii by regenerating active sites.

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

    Science.gov (United States)

    Merati, Zohreh; Basiri Parsa, Jalal

    2018-03-01

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

  10. Direct ethanol fuel cell, CO and ethanol oxidation on core-shell C/Ni-Au-[Pt and (Pt- Ir)] catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Rodrigues, C.A.D.; Tremiliosi-Filho, G. [Universidade de Sao Paulo (IQSC/USP), Sao Carlos, SP (Brazil). Inst. de Quimica], Email: cesaraug@sc.usp.br; Kokoh, K.B.; Coutanceau, C.; Baranton, S. [Universite de Poitiers (France). Lab. de Catalyse en Chimie Organique (LACCO). Equipe Electrocatalyse

    2010-07-01

    In this paper presents to study of the Pt and Pt-Ir monolayer that were deposited on core-shell Ni-Au nanoparticles supported on carbon. Catalysts with the following molar ratios were prepared: Pt and Pt{sub 65}Ir{sub 35}, Pt{sub 75}Ir{sub 2}5, Pt{sub 80}Ir{sub 20} and Pt{sub 85}Ir{sub 15}. The means particle sizes were in the range of 2 - 6 nm for all catalysts. The electrochemical properties examined in the ethanol and CO oxidation by cyclic voltammetry, and In situ IR spectroscopy measurements (SPAIRS) enabled to determine intermediates and reaction products as a function of the metallic compositions of catalysts. All of the catalysts were tested as anodes of a single direct ethanol fuel cell (DEFC) tests in 1.0 M ethanol solution. As a result, higher power densities were obtained with the core-shell particles in comparison to those issued from the commercial catalyst (Pt-ETEK). Thus, the maximum power densities at 90 deg C for the different systems are: (i) commercial C/Pt catalyst (E-TEK): ca. 0.010 W cm{sup -2}, C/Ni-Au-(Pt{sub 85}Ir{sub 15}): ca. 0.013 W cm{sup -2} and C/Ni-Au-Pt: ca. 0.018 W cm{sup -2} (all core-shell systems were normalization by Pt load). As a result, the performance of the core-shell nanoparticles is much better than that produced for the commercial catalyst and the C/Ni-Au-Pt system showed the best performance. (author)

  11. Pt-Pd nanoelectrocatalyst of ultralow Pt content for the oxidation of ...

    Indian Academy of Sciences (India)

    Synthesis of highly efficient functional electrocatalyst that favours the electrochemical oxidation of formic acid via CO-free dehydrogenation pathway is required for direct formic acid fuel cells. Traditional catalysts favour the dehydration pathway involving the generation of poisonous CO. Herein we demonstrate the superior ...

  12. Nonradical oxidation from electrochemical activation of peroxydisulfate at Ti/Pt anode: Efficiency, mechanism and influencing factors.

    Science.gov (United States)

    Song, Haoran; Yan, Linxia; Ma, Jun; Jiang, Jin; Cai, Guangqiang; Zhang, Wenjuan; Zhang, Zhongxiang; Zhang, Jiaming; Yang, Tao

    2017-06-01

    Electrochemical activation of peroxydisulfate (PDS) at Ti/Pt anode was systematically investigated for the first time in this work. The synergistic effect produced from the combination of electrolysis and the addition of PDS demonstrates that PDS can be activated at Ti/Pt anode. The selective oxidation towards carbamazepine (CBZ), sulfamethoxazole (SMX), propranolol (PPL), benzoic acid (BA) rather than atrazine (ATZ) and nitrobenzene (NB) was observed in electrochemical activation of PDS process. Moreover, addition of excess methanol or tert-butanol had negligible impact on CBZ (model compound) degradation, demonstrating that neither sulfate radical (SO 4 - ) nor hydroxyl radical (HO) was produced in electrochemical activation of PDS process. Direct oxidation (PDS oxidation alone and electrolysis) and nonradical oxidation were responsible for the degradation of contaminants. The results of linear sweep voltammetry (LSV) and chronoamperometry suggest that electric discharge may integrate PDS molecule with anode surface into a unique transition state structure, which is responsible for the nonradical oxidation in electrochemical activation of PDS process. Adjustment of the solution pH from 1.0 to 7.0 had negligible effect on CBZ degradation. Increase of either PDS concentration or current density facilitated the degradation of CBZ. The presence of chloride ion (Cl - ) significantly enhanced CBZ degradation, while addition of bicarbonate (HCO 3 - ), phosphate (PO 4 3- ) and humic acid (HA) all inhibited CBZ degradation with the order of HA > HCO 3 -  > PO 4 3- . The degradation products of CBZ and chlorinated products were also identified. Electrochemical activation of PDS at Ti/Pt anode may serve as a novel technology for selective oxidation of organic contaminants in water and soil. Copyright © 2017. Published by Elsevier Ltd.

  13. Freeze drying-assisted synthesis of Pt@reduced graphene oxide nanocomposites as excellent hydrogen sensor

    Science.gov (United States)

    Lu, Xiaojing; Song, Xinjie; Gu, Cuiping; Ren, Haibo; Sun, Yufeng; Huang, Jiarui

    2018-05-01

    Quick and efficient detection of low concentrations of hydrogen remains a challenge because of the stability of hydrogen. A sensor based on reduced oxide graphene functionalized with Pt nanoparticles is successfully fabricated using a freeze-drying method followed by heat treatment. The structure and morphology of the Pt@rGO nanocomposites are well analyzed by X-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy, Raman spectroscopy, and X-ray photoelectron spectroscopy. The as-prepared Pt@rGO nanocomposites show excellent hydrogen gas sensing properties at a low working temperature of 50 °C. The sensitivity toward 0.5% hydrogen is 8%. The response and recovery times of the sensor exposed to 0.5% hydrogen are 63 and 104 s, respectively. The gas-sensing mechanism of Pt@rGO sensor is also discussed.

  14. Enhancement in electro-oxidation of methanol over PtRu black catalyst through strong interaction with iron oxide nanocluster.

    Science.gov (United States)

    Jeon, Min Ku; Lee, Ki Rak; Woo, Seong Ihl

    2010-11-02

    One of the major issues in direct methanol fuel cell research is to develop a new catalyst for methanol electro-oxidation reaction (MOR) with high activity and low cost. In this study, a new, simple, and economic way was introduced to improve the catalytic activity of commercial PtRu black catalyst for the MOR. A nanocomposite electrode was fabricated by mixing the PtRu catalyst with Fe(2)O(3) nanoclusters. When 10 wt % of the PtRu catalyst was replaced by the Fe(2)O(3) nanoclusters, mass activity (A/g(Pt)) increased by 80% compared to that of the pure PtRu catalyst. Specific activity of the mixed catalyst was 100% higher than that of the pure PtRu catalyst. The nanocomposite catalysts were also applied to single cells. Although the amount of the PtRu catalyst was reduced by 10 wt %, 10% higher potential was observed in the nanocomposite catalysts at a current density of 100 mA/cm(2).

  15. Towards a highly-efficient fuel-cell catalyst: optimization of Pt particle size, supports and surface-oxygen group concentration.

    Science.gov (United States)

    Muthuswamy, Navaneethan; de la Fuente, Jose Luis Gomez; Ochal, Piotr; Giri, Rajiv; Raaen, Steinar; Sunde, Svein; Rønning, Magnus; Chen, De

    2013-03-21

    In the present work, methanol oxidation reaction was investigated on Pt particles of various diameters on carbon-nanofibers and carbon-black supports with different surface-oxygen concentrations, aiming for a better understanding of the relationship between the catalyst properties and the electrochemical performance. The pre-synthesized Pt nanoparticles in ethylene glycol, prepared by the polyol method without using any capping agents, were deposited on different carbon supports. Removal of oxygen-groups from the carbon supports had profound positive effects on not only the Pt dispersion but also the specific activity. The edge structures on the stacked graphene sheets in the platelet carbon-nanofibers provided a strong interaction with the Pt particles, significantly reconstructing them in the process. Such reconstruction resulted in the formation of more plated Pt particles on the CNF than on the carbon-black and exposure of more Pt atoms with relatively high co-ordination numbers, and thereby higher specific activity. Owing to the combined advantages of optimum Pt particle diameter, an oxygen-free surface and the unique properties of CNFs, Pt supported on heat-treated CNFs exhibited a higher mass activity twice of that of its commercial counterpart.

  16. Catalyst Architecture for Stable Single Atom Dispersion Enables Site-Specific Spectroscopic and Reactivity Measurements of CO Adsorbed to Pt Atoms, Oxidized Pt Clusters, and Metallic Pt Clusters on TiO2.

    Science.gov (United States)

    DeRita, Leo; Dai, Sheng; Lopez-Zepeda, Kimberly; Pham, Nicholas; Graham, George W; Pan, Xiaoqing; Christopher, Phillip

    2017-10-11

    Oxide-supported precious metal nanoparticles are widely used industrial catalysts. Due to expense and rarity, developing synthetic protocols that reduce precious metal nanoparticle size and stabilize dispersed species is essential. Supported atomically dispersed, single precious metal atoms represent the most efficient metal utilization geometry, although debate regarding the catalytic activity of supported single precious atom species has arisen from difficulty in synthesizing homogeneous and stable single atom dispersions, and a lack of site-specific characterization approaches. We propose a catalyst architecture and characterization approach to overcome these limitations, by depositing ∼1 precious metal atom per support particle and characterizing structures by correlating scanning transmission electron microscopy imaging and CO probe molecule infrared spectroscopy. This is demonstrated for Pt supported on anatase TiO 2 . In these structures, isolated Pt atoms, Pt iso , remain stable through various conditions, and spectroscopic evidence suggests Pt iso species exist in homogeneous local environments. Comparing Pt iso to ∼1 nm preoxidized (Pt ox ) and prereduced (Pt metal ) Pt clusters on TiO 2 , we identify unique spectroscopic signatures of CO bound to each site and find CO adsorption energy is ordered: Pt iso ≪ Pt metal atoms bonded to TiO 2 and that Pt iso exhibits optimal reactivity because every atom is exposed for catalysis and forms an interfacial site with TiO 2 . This approach should be generally useful for studying the behavior of supported precious metal atoms.

  17. Single-step synthesis of PtRu/N-doped graphene for methanol electrocatalytic oxidation

    International Nuclear Information System (INIS)

    Xu, Xiao; Zhou, Yingke; Lu, Jiming; Tian, Xiaohui; Zhu, Hongxi; Liu, Jiangbo

    2014-01-01

    In this work, a single-step route was applied to achieve the reduction of graphene oxide, functional doping of graphene with nitrogen, and deposition of well-dispersed PtRu alloy nanoparticles on the doped graphene simultaneously in the solvent mixture of ethylene glycol and N-methyl-2-pyrrolidone. Transmission electron microscopy, X-ray powder diffraction, Raman spectroscopy and X-ray photoelectron spectroscopy were used to characterize the morphology and microstructure, while cyclic voltammetry, chronoamperometry and electrochemical impedance techniques were carried out to evaluate the electrocatalytic methanol oxidation activity and durability of the obtained PtRu/nitrogen-doped graphene catalysts. Compared to undoped PtRu/graphene, the nitrogen-doped PtRu/graphene catalyst presented better particle size distribution and improved activity and durability of methanol electrocatalytic oxidation, which could be further improved by optimization of the reaction time, temperature, as well as the composition of the reaction medium. The convenient single-step synthesis process for the PtRu/nitrogen-doped graphene catalysts is promising for the potential application of direct methanol fuel cells

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

    Science.gov (United States)

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

    2018-03-01

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

  19. A theoretical analysis of small Pt particles on rutile TiO$_2$(110) surfaces

    OpenAIRE

    Celik, Veysel; Unal, Hatice; Mete, Ersen; Ellialtioglu, Sinasi

    2010-01-01

    The adsorption profiles and electronic structures of Pt$_n$ (n = 1--4) clusters on stoichiometric, reduced and reconstructed rutile TiO$_2$(110) surfaces were systematically studied using on site d-d Coulomb interaction corrected hybrid density functional theory calculations. The atomic structure of small Pt cluster adsorbates mainly depend on the stoichiometry of the corresponding titania support. The cluster shapes on the bulk terminated ideal surface look like their gas phase low energy st...

  20. Surface science approach to Pt/carbon model catalysts: XPS, STM and microreactor studies

    Science.gov (United States)

    Motin, Abdul Md.; Haunold, Thomas; Bukhtiyarov, Andrey V.; Bera, Abhijit; Rameshan, Christoph; Rupprechter, Günther

    2018-05-01

    Pt nanoparticles supported on carbon are an important technological catalyst. A corresponding model catalyst was prepared by physical vapor deposition (PVD) of Pt on sputtered HOPG (highly oriented pyrolytic graphite). The carbon substrate before and after sputtering as well as the Pt/HOPG system before and after Pt deposition and annealing were examined by XPS and STM. This yielded information on the surface density of defects, which serve as nucleation centres for Pt, and on the size distribution (mean size/height) of the Pt nanoparticles. Two different model catalysts were prepared with mean sizes of 2.0 and 3.6 nm, both turned out to be stable upon UHV-annealing to 300 °C. After transfer into a UHV-compatible flow microreactor and subsequent cleaning in UHV and under mbar pressure, the catalytic activity of the Pt/HOPG model system for ethylene hydrogenation was examined under atmospheric pressure flow conditions. This enabled to determine temperature-dependent conversion rates, turnover frequencies (TOFs) and activation energies. The catalytic results obtained are in line with the characteristics of technological Pt/C, demonstrating the validity of the current surface science based model catalyst approach.

  1. Electrochemical oxidation of hydrolyzed poly oxymethylene-dimethyl ether by PtRu catalysts on Nb-doped SnO(2-δ) supports for direct oxidation fuel cells.

    Science.gov (United States)

    Kakinuma, Katsuyoshi; Kim, In-Tae; Senoo, Yuichi; Yano, Hiroshi; Watanabe, Masahiro; Uchida, Makoto

    2014-12-24

    We synthesized Pt and PtRu catalysts supported on Nb-doped SnO(2-δ) (Pt/Sn0.99Nb0.01O(2-δ), PtRu/Sn0.99Nb0.01O(2-δ)) for direct oxidation fuel cells (DOFCs) using poly oxymethylene-dimethyl ether (POMMn, n = 2, 3) as a fuel. The onset potential for the oxidation of simulated fuels of POMMn (methanol-formaldehyde mixtures; n = 2, 3) for Pt/Sn0.99Nb0.01O(2-δ) and PtRu/Sn0.99Nb0.01O(2-δ) was less than 0.3 V vs RHE, which was much lower than those of two commercial catalysts (PtRu black and Pt2Ru3/carbon black). In particular, the onset potential of the oxidation reaction of simulated fuels of POMMn (n = 2, 3) for PtRu/Sn0.99Nb0.01O(2-δ) sintered at 800 °C in nitrogen atmosphere was less than 0.1 V vs RHE and is thus considered to be a promising anode catalyst for DOFCs. The mass activity (MA) of PtRu/Sn0.99Nb0.01O(2-δ) sintered at 800 °C was more than five times larger than those of the commercial catalysts in the measurement temperature range from 25 to 80 °C. Even though the MA for the methanol oxidation reaction was of the same order as those of the commercial catalysts, the MA for the formaldehyde oxidation reaction was more than five times larger than those of the commercial catalysts. Sn from the Sn0.99Nb0.01O(2-δ) support was found to have diffused into the Pt catalyst during the sintering process. The Sn on the top surface of the Pt catalyst accelerated the oxidation of carbon monoxide by a bifunctional mechanism, similar to that for Pt-Ru catalysts.

  2. Active Pt-Pb Ox/C anodes to promote the formic acid oxidation in presence of sulfuric acid

    Energy Technology Data Exchange (ETDEWEB)

    Buzzo, Guilherme S.; Niquirilo, Rafael V.; Suffredini, Hugo B. [Universidade Federal do ABC (UFABC), Santo Andre, SP (Brazil). Centro de Ciencias Naturais e Humanas

    2010-07-01

    The performance of Pt-Pb Ox-based catalysts to promote the formic acid oxidation is described here. All materials were synthesized by a modified sol-gel method. Voltammetric studies showed that the Pt-Pb Ox/C anode starts the oxidation process at extremely low potentials. Quasi-stationary polarization experiments and current vs. time measurements confirmed this affirmation. (author)

  3. A comparative study of the adsorption and hydrogenation of acrolein on Pt(1 1 1), Ni(1 1 1) film and Pt Ni Pt(1 1 1) bimetallic surfaces

    Science.gov (United States)

    Murillo, Luis E.; Chen, Jingguang G.

    In this study we have investigated the reaction pathways for the decomposition and hydrogenation of acrolein (CH 2dbnd CH-CH dbnd O) on Ni/Pt(1 1 1) surfaces under ultra-high vacuum (UHV) conditions using temperature programmed desorption (TPD) and high-resolution electron energy loss spectroscopy (HREELS). While gas-phase hydrogenation products are not observed from clean Pt(1 1 1), the subsurface Pt-Ni-Pt(1 1 1), with Ni residing below the first layer of Pt, is active for the self-hydrogenation of the C dbnd O bond to produce unsaturated alcohol (2-propenol) and the C dbnd C bond to produce saturated aldehyde (propanal), with the latter being the main hydrogenation product without the consecutive hydrogenation to saturated alcohol. For a thick Ni(1 1 1) film prepared on Pt(1 1 1), the self-hydrogenation yields for both products are lower than that from the Pt-Ni-Pt(1 1 1) surface. The presence of pre-adsorbed hydrogen further enhances the selectivity toward C dbnd O bond hydrogenation on the Pt-Ni-Pt(1 1 1) surface. In addition, HREELS studies of the adsorption of the two hydrogenation products, 2-propenol and propanal, are performed on the Pt-Ni-Pt(1 1 1) surface to identify the possible surface intermediates during the reaction of acrolein. The results presented here indicate that the hydrogenation activity and selectivity of acrolein on Pt(1 1 1) can be significantly modified by the formation of the bimetallic surfaces.

  4. Microstructure and oxidation performance of a γ–γ ′ Pt-aluminide ...

    Indian Academy of Sciences (India)

    Administrator

    of γ–γ ′ bond coats to reduce rumpling, their oxidation resistance needs to improve significantly for them to be considered as an alternative to conventional β-(Ni, Pt)Al bond coats for use in TBCs. Acknowledgements. The authors acknowledge the assistance provided by the. ETC, MEG, SFAG and EMG groups of DMRL.

  5. Efficient Aerobic Oxidation of Cyclohexane to KA Oil Catalyzed by Pt ...

    Indian Academy of Sciences (India)

    Efficient Aerobic Oxidation of Cyclohexane to KA Oil Catalyzed by. Pt-Sn supported on MWCNTs. MOHAMMAD SADIQa,∗, MUHAMMAD ALIa, RASHID IQBALa, KHALID SAEEDa,. AIMAL KHANa, MUHAMMAD NAVEED UMARa and HAROON UR RASHIDb. aDepartment of Chemistry, University of Malakand, Chakdara, Dir ...

  6. Monolayer-directed Assembly and Magnetic Properties of FePt Nanoparticles on Patterned Aluminum Oxide

    NARCIS (Netherlands)

    Yildirim, O.; Gang, T.; Kinge, S.S.; Reinhoudt, David; Blank, David H.A.; van der Wiel, Wilfred Gerard; Rijnders, Augustinus J.H.M.; Huskens, Jurriaan

    2010-01-01

    FePt nanoparticles (NPs) were assembled on aluminum oxide substrates, and their ferromagnetic properties were studied before and after thermal annealing. For the first time, phosph(on)ates were used as an adsorbate to form self-assembled monolayers (SAMs) on alumina to direct the assembly of NPs

  7. Enhanced electrocatalytic activity of pulse deposited Pt particles dispersed on PEDOT-modified Au electrode towards ethanol oxidation

    International Nuclear Information System (INIS)

    Mendoza, Maria Krisandra L.; Tongol, Bernard John V.

    2013-01-01

    Poly(3,4-ethylenedioxythiophene) (PEDOT)-modified Au electrodes were electrochemically prepared via potentiodynamic polymerization using 0.01 M EDOT and 0.10 M HClO 4 on a Au substrate at a potential range from 0.0 to 1.10 V (vs. Ag/AgCl). The PEDOT-modified AU electrode was electrochemically characterized in a monomer-free 0.10M HClO 4 electrolyte. Meanwhile, the surface morphology was probed using Scanning Electron Microscopy (SEM). Platinum particles dispersed on PEDOT-modified Au electrodes were prepared in two steps: (i) aqueous electropolymerization of EDOT and (ii) pulse deposition of platinum. Pulse deposition of Pt nanoparticles was carried out using the following optimized parameters: -30 mA/cm”2 of pulse current with 0.2 s on-time and 0.4 s off-time at 700 pulses. Electrocatalytic activity of the prepared Pt/PEDOT/Au electrode was evaluated towards ethanol oxidation using 1.0 M ethanol in 0.10 M H 2 SO 4 electrolyte solution from E = 0.0 V to E = 0.90 V (vs. Ag/AgCl) at a scan rate of 100 mV s”-“1. The CV profile of the prepared nanocomposite shows an anodic peak at E = +0.700V which is an indication of the presence of the platinum. Examination of the surface morphology of the Pt nanoparticles (Pt NPs)/PEDOT/Au-modified electrode revealed well-dispersed platinum particles on the polymer matrix with a diameter of less than 100 nm. Enhancement of the electrocatalytic activity towards ethanol oxidation was observed in pulse-deposited platinum particles compared to potentiodynamically-deposited platinum particles on PEDOT-modified Au electrode. (author)

  8. Boosting fuel cell performance with a semiconductor photocatalyst: TiO2/Pt-Ru hybrid catalyst for methanol oxidation.

    Science.gov (United States)

    Drew, Kristine; Girishkumar, G; Vinodgopal, K; Kamat, Prashant V

    2005-06-23

    A hybrid carbon fiber electrode (CFE) consisting of TiO2 semiconductor photocatalyst and Pt-Ru catalyst has been developed to boost the performance of direct methanol fuel cells (DMFC). These two catalyst nanoparticles are deposited on opposite sides of the carbon fiber paper such that methanol oxidation is carried out catalytically on Pt-Ru and photocatalytically on TiO2 under UV-light irradiation. Since both catalysts carry out methanol oxidation independently, we observe an additive effect in the current generation. The carbon support fibers provide a large network to collect the electrons from both of these catalytic processes and thus assist in efficient current generation. In addition, TiO2 improves the performance of the Pt-Ru catalyst in dark, indicating possible surface area improvement or diminished poisoning effects. The concept of incorporating a photocatalyst provides new ways to minimize precious metal content and enhance the performance of DMFCs. At low catalyst loadings (0.15 mg/cm2) at 295 K, a 25% enhancement in the peak power density is observed upon illumination with light.

  9. Theoretical study of the surface resistivity of (111) surfaces of NixPt1-x(111) alloys

    International Nuclear Information System (INIS)

    Rous, P. J.

    2001-01-01

    A layer-Korringa - Kohn - Rostoker calculation is used to study the compositional dependence of the surface resistivity of the (111) surface of Ni x Pt 1-x (111) alloys. The compositional disorder in the bulk and at the surface is described by the coherent potential approximation. If it is assumed that the atomic planes near the (111) surface Ni x Pt 1-x have the same composition as the bulk layers, then a weak Nordheim effect is observed in the compositional dependence of the surface resistivity. However, we show that surface segregation in Ni x Pt 1-x (111) causes an inverse Nordheim dependence in the actual surface resistivity as the bulk composition is varied. [copyright] 2001 American Institute of Physics

  10. The synthesis of PdPt/carbon paper via surface limited redox replacement reactions for oxygen reduction reaction

    CSIR Research Space (South Africa)

    Motsoeneng, RG

    2015-09-01

    Full Text Available Surface-limited redox replacement reactions using the electrochemical atomic layer deposition (EC-ALD) technique were used to synthesize PdPt bimetallic electrocatalysts on carbon paper substrate. Electrocatalysts having different Pd:Pt ratio were...

  11. Preparation and characterization of Pt-Sn/C and Pt-Ir/C catalysts for the electrochemical oxidation of ethanol in polymer electrolyte membrane fuel cell

    CSIR Research Space (South Africa)

    Masombuka, T

    2007-11-01

    Full Text Available Low temperature fuel cells with methanol or ethanol as the fuel represent an environmentally friendly technology and are attracting considerable interest as a means of producing electricity. High surface area carbon supported Pt is recognised...

  12. Modification of titanium oxide membranes by Pt electrodeposition

    International Nuclear Information System (INIS)

    Avalle, L.; Santos, E.; Leiva, E.P.M.; Macagno, V.A.

    1990-01-01

    Electrochemistry techniques mainly voltamperometry and measures of impedance with titanium oxides changed by platinum atoms incorporation, were studied. This changes production some alteration in the physical chemical and electrocatalytic properties, as an example the improvement of corrosion resistance and the uses in nuclear industry. (author)

  13. Effect of reduction conditions on electrocatalytic activity of a ternary PtNiCr/C catalyst for methanol electro-oxidation

    International Nuclear Information System (INIS)

    Jeon, Min Ku; Zhang Yuan; McGinn, Paul J.

    2009-01-01

    The effect of reduction conditions on a Pt 28 Ni 36 Cr 36 /C catalyst was investigated by using two different reduction methods: hydrogen reduction and NaBH 4 reduction. In hydrogen reduced catalysts, dissolution of metallic Ni and Cr was observed during cyclic voltammetry (CV) tests, and a larger amount of Ni and Cr was dissolved when reduced at higher temperatures. For methanol electro-oxidation, the highest specific current density of 1.70 A m -2 at 600 s of the chronoamperometry tests was observed in the catalyst reduced at 300 deg. C, which was ∼24 times that of a Pt/C catalyst (0.0685 A m -2 ). In NaBH 4 reduced catalysts, formation of an amorphous phase and a more Pt-rich surface was observed in X-ray diffraction and CV results, respectively, with increasing amounts of NaBH 4 . When reduced by 50 times of the stoichiometric amount of NaBH 4 , the PtNiCr/C catalyst (PtNiCr-50t) showed a current density of 34.1 A g noblemetal -1 , which was 81% higher than the 18.8 A g noblemetal -1 value of a PtRu/C catalyst at 600 s of the chronoamperometry tests. After 13 h of chronoamperometry testing, the activity of the PtNiCr-50t (15.0 A g noblemetal -1 ) was 110% higher than the PtRu/C catalyst (7.15 A g noblemetal -1 ). The PtNiCr/C catalyst shows promise as a Ru-free methanol oxidation catalyst

  14. 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 117...... kJ/mol, which agree well with literature. The size distribution of the colloid nanoparticles is determined from STM and TEM, from which an average size of the colloid nanoparticles of 2.2 +/- 0.5 nm is determined....

  15. Preparation Effects on the Performance of Silica-Doped Hydrous Titanium Oxide (HTO:Si)-Supported Pt Catalysts for Lean-Burn NOx Reduction by Hydrocarbons; TOPICAL

    International Nuclear Information System (INIS)

    GARDNER, TIMOTHY J.; MCLAUGHLIN, LINDA I.; MOWERY, DEBORAH L.; SANDOVAL, RONALD S.

    2002-01-01

    This report describes the development of bulk hydrous titanium oxide (HTO)- and silica-doped hydrous titanium oxide (HTO:Si)-supported Pt catalysts for lean-burn NOx catalyst applications. The effects of various preparation methods, including both anion and cation exchange, and specifically the effect of Na content on the performance of Pt/HTO:Si catalysts, were evaluated. Pt/HTO:Si catalysts with low Na content ( and lt; 0.5 wt.%) were found to be very active for NOx reduction in simulated lean-burn exhaust environments utilizing propylene as the major reductant species. The activity and performance of these low Na Pt/HTO:Si catalysts were comparable to supported Pt catalysts prepared using conventional oxide or zeolite supports. In ramp down temperature profile test conditions, Pt/HTO:Si catalysts with Na contents in the range of 3-5 wt.% showed a wide temperature window of appreciable NOx conversion relative to low Na Pt/HTO:Si catalysts. Full reactant species analysis using both ramp up and isothermal test conditions with the high Na Pt/HTO:Si catalysts, as well as diffuse reflectance FTIR studies, showed that this phenomenon was related to transient NOx storage effects associated with NaNO(sub 2)/NaNO(sub 3) formation. These nitrite/nitrate species were found to decompose and release NOx at temperatures above 300 C in the reaction environment (ramp up profile). A separate NOx uptake experiment at 275 C in NO/N(sub 2)/O(sub 2) showed that the Na phase was inefficiently utilized for NOx storage. Steady state tests showed that the effect of increased Na content was to delay NOx light-off and to decrease the maximum NOx conversion. Similar results were observed for high K Pt/HTO:Si catalysts, and the effects of high alkali content were found to be independent of the sample preparation technique. Catalyst characterization (BET surface area, H(sub 2) chemisorption, and transmission electron microscopy) was performed to elucidate differences between the HTO- and HTO

  16. Effect of calcination temperature on formaldehyde oxidation performance of Pt/TiO2 nanofiber composite at room temperature

    Science.gov (United States)

    Xu, Feiyan; Le, Yao; Cheng, Bei; Jiang, Chuanjia

    2017-12-01

    Catalytic oxidation at room temperature over well-designed catalysts is an environmentally friendly method for the abatement of indoor formaldehyde (HCHO) pollution. Herein, nanocomposites of platinum (Pt) and titanium dioxide (TiO2) nanofibers with various phase compositions were prepared by calcining the electrospun TiO2 precursors at different temperatures and subsequently depositing Pt nanoparticles (NPs) on the TiO2 through a NaBH4-reduction process. The phase compositions and structures of Pt/TiO2 can be easily controlled by varying the calcination temperature. The Pt/TiO2 nanocomposites showed a phase-dependent activity towards the catalytic HCHO oxidation. Pt/TiO2 containing pure rutile phase showed enhanced activity with a turnover frequency (TOF) of 16.6 min-1 (for a calcination temperature of 800 °C) as compared to those containing the anatase phase or mixed phases. Density functional theory calculation shows that TiO2 nanofibers with pure rutile phase have stronger adsorption ability to Pt atoms than anatase phase, which favors the reduction of Pt over rutile phase TiO2, leading to higher contents of metallic Pt in the nanocomposite. In addition, the Pt/TiO2 with rutile phase possesses more abundant oxygen vacancies, which is conducive to the activation of adsorbed oxygen. Consequently, the Pt/rutile-TiO2 nanocomposite exhibited better catalytic activity towards HCHO oxidation at room temperature.

  17. Folic acid bio-inspired route for facile synthesis of AuPt nanodendrites as enhanced electrocatalysts for methanol and ethanol oxidation reactions

    Science.gov (United States)

    Wang, Ai-Jun; Ju, Ke-Jian; Zhang, Qian-Li; Song, Pei; Wei, Jie; Feng, Jiu-Ju

    2016-09-01

    Folic acid (FA), as an important biomolecule in cell division and growth, is firstly employed as the structure director and stabilizing agent for controlled synthesis of uniform Au65Pt35 nanodendrites (NDs) by a one-pot wet-chemical bio-inspired route at room temperature. No pre-seed, template, organic solvent, polymer, surfactant or complex instrument is involved. The products are mainly characterized by transmission electron microscopy (TEM), high angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), X-ray diffraction (XRD), and X-Ray photoelectron spectroscopy (XPS). The architectures have enlarged electrochemically active surface area (60.6 m2 gPt-1), enhanced catalytic activity and durability for methanol and ethanol oxidation in contrast with commercial Pt black and the other AuPt alloys by tuning the molar ratios of Au to Pt (e.g., Au31Pt69 and Au82Pt18 nanoparticles). This strategy would be applied to fabricate other bimetallic nanocatalysts in fuel cells.

  18. Surface Pourbaix diagrams and oxygen reduction activity of Pt, Ag and Ni(111) surfaces studied by DFT

    DEFF Research Database (Denmark)

    Hansen, Heine Anton; Rossmeisl, Jan; Nørskov, Jens Kehlet

    2008-01-01

    The electrochemical most stable surface structures is investigated as function of pH and potential for Pt, Ag and Ni based on DFT calculations and constructed surface Pourbaix diagrams. It is also explained why metals such as Ag and Ni may be used successfully in alkaline fuel cells but not in ac......The electrochemical most stable surface structures is investigated as function of pH and potential for Pt, Ag and Ni based on DFT calculations and constructed surface Pourbaix diagrams. It is also explained why metals such as Ag and Ni may be used successfully in alkaline fuel cells...

  19. Facile Synthesis of Pt-/Pd-MODIFIED NiTi Electrode with Superior Electro-Catalytic Activities Toward Methanol, Ethanol and Ethylene Glycol Oxidation

    Science.gov (United States)

    He, Yongwei; Wang, Mei; Ma, Zizai; Li, Ruixue; Kundu, Manab; Ma, Guanshui; Lin, Naiming; Tang, Bin; Wang, Xiaoguang

    2016-11-01

    Surface functional modification of NiTi electrode with noble Pt and Pd metal has been successfully carried out by simple and cost effective electro-spark deposition technique (ESD). Thin-film X-ray diffraction (TF-XRD), scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX) and cyclic voltammetry (CV) have been carried out in order to investigate the structure, morphology, chemical composition and electrochemical behavior of the modified electrode surface. The modified Pt/NiTi and Pd/NiTi electrode surface exhibit a circular splash pattern with a tiny amount of Pt (˜5.30 at.% Pt) and Pd (˜5.71 at.% Pd) existence. The electrochemical results demonstrate that the Pt/NiTi and Pd/NiTi electrode possess an improved electro-catalytic activities toward methanol (MeOH), ethanol (EtOH) and ethylene glycol (EG) oxidation in alkaline media in comparison with the bare NiTi electrode. In acidic environments, the Pt/NiTi electrode exhibits even much better catalytic activities than the pure Pt sheet electrode due to the bi-functional mechanism. In the same way, the electro-catalytic activity of the modified Pd/NiTi electrode is also slightly larger than that of the pure Pd sheet electrode in alkaline environment. The electro-spark surface modification approach is rapid and environmentally-benign, being attractive to widen the application of traditional surface modification technique in the field of material surface/interface design and functionalization.

  20. Theoretical analysis of small Pt particles on rutile TiO2(110) surfaces

    Science.gov (United States)

    Çelik, Veysel; Ünal, Hatice; Mete, Ersen; Ellialtıoǧlu, Şinasi

    2010-11-01

    The adsorption profiles and electronic structures of Ptn(n=1-4) clusters on stoichiometric, reduced and reconstructed rutile TiO2(110) surfaces were systematically studied using on site d-d Coulomb interaction corrected hybrid density-functional-theory (DFT) calculations. The atomic structure of small Pt cluster adsorbates mainly depends on the stoichiometry of the corresponding titania support. The cluster shapes on the bulk terminated ideal surface look like their gas phase low-energy structures. However, for instance, they get significantly distorted on the reduced surfaces with increasing oxygen vacancies. On nonstoichiometric surfaces, Pt-Ti coordination becomes dominant in the determination of the adsorption geometries. The electronic structure of Ptn/TiO2(110) systems cannot be correctly described by pure DFT methods, particularly for nonstoichiometric cases due to the inappropriate treatment of the correlation for d electrons. We performed DFT+U calculations to give a reasonable description of the reconstructed rutile (110) surface. Pt clusters induce local surface relaxations that influence band edges of titania support and bring a number of band-gap states depending on the cluster size. Significant band gap narrowing occurs upon Ptn -surface interaction due to adsorbate driven states on the bulk terminated and reduced surfaces. On the other hand, they give rise to a band-gap widening associated to partial reoxidation of the reconstructed surface. No metallization arises even for Pt4 on rutile.

  1. Pt-Fe catalyst nanoparticles supported on single-wall carbon nanotubes: Direct synthesis and electrochemical performance for methanol oxidation

    Science.gov (United States)

    Ma, Xiaohui; Luo, Liqiang; Zhu, Limei; Yu, Liming; Sheng, Leimei; An, Kang; Ando, Yoshinori; Zhao, Xinluo

    2013-11-01

    Single-wall carbon nanotubes (SWCNTs) supported Pt-Fe nanoparticles have been prepared by one-step hydrogen arc discharge evaporation of carbon electrode containing both Pt and Fe metal elements. The formation of SWCNTs and Pt-Fe nanoparticles occur simultaneously during the evaporation process. High-temperature hydrogen treatment and hydrochloric acid soaking have been carried out to purify and activate those materials in order to obtain a new type of Pt-Fe/SWCNTs catalyst for methanol oxidation. The Pt-Fe/SWCNTs catalyst performs much higher electrocatalytic activity for methanol oxidation, better stability and better durability than a commercial Pt/C catalyst according to the electrochemical measurements, indicating that it has a great potential for applications in direct methanol fuel cells.

  2. Oxygen reduction and methanol oxidation behaviour of SiC based Pt nanocatalysts for proton exchange membrane fuel cells

    DEFF Research Database (Denmark)

    Dhiman, Rajnish; Stamatin, Serban Nicolae; Andersen, Shuang Ma

    2013-01-01

    with the present carbon based substrates. We have recently examined suitably sized silicon carbide (SiC) particles as catalyst supports for fuel cells based on the stable chemical and mechanical properties of this material. In the present study, we have continued our work with studies of the oxygen reduction...... and methanol oxidation reactions of SiC supported catalysts and measured them against commercially available carbon based catalysts. The deconvolution of the hydrogen desorption signals in CV cycles shows a higher contribution of Pt (110) & Pt (111) peaks compared to Pt (100) for SiC based supports than...... for carbon based commercial catalyst, when HClO4 is used as electrolyte. The Pt (110) & Pt (111) facets are shown to have higher electrochemical activities than Pt (100) facets. To the best of our knowledge, methanol oxidation studies and the comparison of peak deconvolutions of the H desorption region in CV...

  3. The surface brightness of spiral galaxies: Pt. 4

    International Nuclear Information System (INIS)

    Phillipps, S.; Disney, M.; Ohio State Univ., Columbus

    1988-01-01

    Using measurements from IRAS correlations are found between optical surface brightness and both infrared-to-optical flux ratio and infrared colour temperature, in the sense that galaxies with high surface brightness have higher FIR emission and higher temperatures. (author)

  4. Pulse plating of Pt on n-GaAs (1 0 0) wafer surfaces: Synchrotron induced photoelectron spectroscopy and XPS of wet fabrication processes

    International Nuclear Information System (INIS)

    Ensling, D.; Hunger, R.; Kraft, D.; Mayer, Th.; Jaegermann, W.; Rodriguez-Girones, M.; Ichizli, V.; Hartnagel, H.L.

    2003-01-01

    Preparation steps of Pt/n-GaAs Schottky contacts as applied in the fabrication process of varactor diode arrays for THz applications are analysed by photoelectron spectroscopy. Pulsed cathodic deposition of Pt onto GaAs (1 0 0) wafer surfaces from acidic solution has been studied by core level photoelectron spectroscopy using different excitation energies. A laboratory AlKα source as well as synchrotron radiation of hν=130 and 645 eV at BESSY was used. Chemical analyses and semiquantitative estimates of layer thickness are given for the natural oxide of an untreated wafer surface, a surface conditioning NH 3 etching step, and stepwise pulse plating of Pt. The structural arrangement of the detected species and interface potentials are considered

  5. Influence of surface treatment on the oxidation behavior of zirconium and zircaloy-4

    International Nuclear Information System (INIS)

    Costa, I.; Ramanathan, L.V.

    1986-01-01

    The influence of fluoride concentration in surface treatment solutions on the oxidation behavior of Zr and Zircaloy-4 in the temperature range 350-760 0 C have been studied by means of thermogravimetric analysis. Two solutions containing different concentrations of hydrofluoric acid have been used for surface treatments, following which surface roughness measurements were also carried out. The influence of fluoride ion concentration on oxidation behavior has been found to be significant at higher temperatures. (Author) [pt

  6. 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

    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). The sup......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......). 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...

  7. Fabrication of reduced graphene oxide/macrocyclic cobalt complex nanocomposites as counter electrodes for Pt-free dye-sensitized solar cells

    Science.gov (United States)

    Tsai, Chih-Hung; Shih, Chun-Jyun; Wang, Wun-Shiuan; Chi, Wen-Feng; Huang, Wei-Chih; Hu, Yu-Chung; Yu, Yuan-Hsiang

    2018-03-01

    In this study, macrocyclic Co complexes were successfully grafted onto graphene oxide (GO) to produce GO/Co nanocomposites with a large surface area, high electrical conductivity, and excellent catalytic properties. The novel GO/Co nanocomposites were applied as counter electrodes for Pt-free dye-sensitized solar cells (DSSCs). Various ratios of macrocyclic Co complexes were used as the reductant to react with the GO, with which the surface functional groups of the GO were reduced and the macrocyclic ligand of the Co complexes underwent oxidative dehydrogenation, after which the conjugated macrocyclic Co systems were grafted onto the surface of the reduced GO to form GO/Co nanocomposites. The surface morphology, material structure, and composition of the GO/Co composites and their influences on the power-conversion efficiency of DSSC devices were comprehensively investigated. The results showed that the GO/Co (1:10) counter electrode (CE) exhibited an optimal power conversion efficiency of 7.48%, which was higher than that of the Pt CE. The GO/Co (1:10) CE exhibited superior electric conductivity, catalytic capacity, and redox capacity. Because GO/Co (1:10) CEs are more efficient and cheaper than Pt CEs, they could potentially be used as a replacement for Pt electrodes.

  8. Effect of Ni Core Structure on the Electrocatalytic Activity of Pt-Ni/C in Methanol Oxidation

    Science.gov (United States)

    Kang, Jian; Wang, Rongfang; Wang, Hui; Liao, Shijun; Key, Julian; Linkov, Vladimir; Ji, Shan

    2013-01-01

    Methanol oxidation catalysts comprising an outer Pt-shell with an inner Ni-core supported on carbon, (Pt-Ni/C), were prepared with either crystalline or amorphous Ni core structures. Structural comparisons of the two forms of catalyst were made using transmission electron microscopy (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS), and methanol oxidation activity compared using CV and chronoamperometry (CA). While both the amorphous Ni core and crystalline Ni core structures were covered by similar Pt shell thickness and structure, the Pt-Ni(amorphous)/C catalyst had higher methanol oxidation activity. The amorphous Ni core thus offers improved Pt usage efficiency in direct methanol fuel cells. PMID:28811402

  9. Effect of Ni Core Structure on the Electrocatalytic Activity of Pt-Ni/C in Methanol Oxidation

    Directory of Open Access Journals (Sweden)

    Vladimir Linkov

    2013-07-01

    Full Text Available Methanol oxidation catalysts comprising an outer Pt-shell with an inner Ni-core supported on carbon, (Pt-Ni/C, were prepared with either crystalline or amorphous Ni core structures. Structural comparisons of the two forms of catalyst were made using transmission electron microscopy (TEM, X-ray diffraction (XRD and X-ray photoelectron spectroscopy (XPS, and methanol oxidation activity compared using CV and chronoamperometry (CA. While both the amorphous Ni core and crystalline Ni core structures were covered by similar Pt shell thickness and structure, the Pt-Ni(amorphous/C catalyst had higher methanol oxidation activity. The amorphous Ni core thus offers improved Pt usage efficiency in direct methanol fuel cells.

  10. Monodisperse Pt atoms anchored on N-doped graphene as efficient catalysts for CO oxidation: A first-principles investigation

    KAUST Repository

    Liu, Xin

    2015-01-01

    We performed first-principles based calculations to investigate the electronic structure and the potential catalytic performance of Pt atoms monodispersed on N-doped graphene in CO oxidation. We showed that N-doping can introduce localized defect states in the vicinity of the Fermi level of graphene which will effectively stabilize the deposited Pt atoms. The binding energy of a single Pt atom onto a stable cluster of 3 pyridinic N (PtN3) is up to -4.47 eV, making the diffusion and aggregation of anchored Pt atoms difficult. Both the reaction thermodynamics and kinetics suggest that CO oxidation over PtN3 would proceed through the Langmuir-Hinshelwood mechanism. The reaction barriers for the formation and dissociation of the peroxide-like intermediate are determined to be as low as 0.01 and 0.08 eV, respectively, while that for the regeneration is only 0.15 eV, proving the potential high catalytic performance of PtN3 in CO oxidation, especially at low temperatures. The Pt-d states that are up-shifted by the Pt-N interaction account for the enhanced activation of O2 and the efficient formation and dissociation of the peroxide-like intermediate.

  11. Microstructure and oxidation performance of a γ–γ′ Pt-aluminide ...

    Indian Academy of Sciences (India)

    247LC alloy for about 100 h, whereas the coating imparted oxidation resistance for significantly longer duration of about 1000 h. The nature of surface damage that occurred to the -' coating during oxidation has been compared with that ...

  12. Facile synthesis of PtAu nanoparticles supported on polydopamine reduced and modified graphene oxide as a highly active catalyst for methanol oxidation

    International Nuclear Information System (INIS)

    Ren, Fangfang; Zhai, Chunyang; Zhu, Mingshan; Wang, Caiqin; Wang, Huiwen; Bin, Duan; Guo, Jun; Yang, Ping; Du, Yukou

    2015-01-01

    Graphical abstract: A facile and clean method for the synthesis of PtAu nanoparticles with different Pt/Au ratios supported on polydopamine reduced and modified graphene oxide (PtAu/PDA-RGO) is reported, which exhibit higher electro-catalytic performance and stability towards methanol oxidation in alkaline medium. - Highlights: • GO could be reduced and modified simultaneously by PDA without using reducing agents. • PDA plays an important role in enhancing the dispersion and stability of the catalyst. • The bimetallic PtAu/PDA-RGO catalysts exhibits higher catalytic activity than the monometallic Pt/PDA-RGO toward MOR. • The PtAu(3:1)/PDA-RGO catalyst also shows better catalytic activity for MOR than PtAu(3:1)/RGO and PtAu(3:1)/C catalysts. - Abstract: In this paper, a facile strategy for the synthesis of PtAu nanoparticles (NPs) with different Pt/Au ratios supported on polydopamine reduced and modified graphene oxide (PtAu/PDA-RGO) is reported. The as-prepared PtAu/PDA-RGO composites were extensively analyzed by transmission electron microscopy (TEM), high-resolution TEM (HRTEM), Raman spectroscopy, energy dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and electrochemical measurements. It is found that PDA plays an important role in enhancing the dispersion and stability of the catalyst. Moreover, the bimetallic PtAu/PDA-RGO catalysts exhibits higher catalytic activity than the monometallic Pt/PDA-RGO toward methanol oxidation reaction (MOR), with the best performance found for the Pt/Au molar ratio of 3/1. The PtAu(3:1)/PDA-RGO catalyst also shows better catalytic activity for MOR than PtAu(3:1)/RGO and PtAu(3:1)/C catalysts, suggesting that PDA-RGO can be a promising catalyst support for fuel cells. These findings also indicate that the molar ratios of Pt/Au and the catalyst support are the two critical factors to affect the overall performance of the catalyst

  13. 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)

  14. Laser spectroscopy and photochemistry on metal surfaces, pt.2

    CERN Document Server

    Dai, HL

    1995-01-01

    Using lasers to induce and probe surface processes has the advantages of quantum state specificity, species selectivity, surface sensitivity, fast time-resolution, high frequency resolution, and accessibility to full pressure ranges. These advantages make it highly desirable to use light to induce, control, or monitor surface chemical and physical processes. Recent applications of laser based techniques in studying surface processes have stimulated new developments and enabled the understanding of fundamental problems in energy transfer and reactions. This volume will include discussions on sp

  15. Laser spectroscopy and photochemistry on metal surfaces, pt.1

    CERN Document Server

    Dai, HL

    1995-01-01

    Using lasers to induce and probe surface processes has the advantages of quantum state specificity, species selectivity, surface sensitivity, fast time-resolution, high frequency resolution, and accessibility to full pressure ranges. These advantages make it highly desirable to use light to induce, control, or monitor surface chemical and physical processes. Recent applications of laser based techniques in studying surface processes have stimulated new developments and enabled the understanding of fundamental problems in energy transfer and reactions. This volume will include discussions on sp

  16. Characterization of Pt catalysts supported in mixed oxides; Caracterizacion de catalizadores de Pt soportado en oxidos mixtos

    Energy Technology Data Exchange (ETDEWEB)

    Perez H, R.; Garcia C, M.A.; Gomez C, A.; Diaz, G. [Instituto Nacional de Investigaciones Nucleares, A.P. 18-1027, 11801 Mexico D.F. (Mexico)

    2000-07-01

    The catalytic supports TiO{sub 2}, ZrO{sub 2} and TiO{sub 2}-ZrO{sub 2} were prepared by the sol-gel technique. The incorporation of Pt to the supports was by the classical impregnation method. The catalytic materials were characterized (Pt/TiO{sub 2}, Pt/ZrO{sub 2} and Pt/TiO{sub 2}-ZrO{sub 2}) by diverse techniques to determine: the texture (BET), evolution of the catalytic materials synthesised after drying and calcination (Infrared spectroscopy) and by Thermogravimetric analysis. (Author)

  17. Dipole moments associated with edge atoms; a comparative study on stepped Pt, Au and W surfaces

    International Nuclear Information System (INIS)

    Besocke, K.; Krahl-Urban, B.; Wagner, H.

    1977-01-01

    Work function measurements have been performed on stepped Pt and Au surfaces with (111) terraces and on W surfaces with (110) terraces. In each case the work function decreases linearly with increasing step density and depends on the step orientation. The work function changes are attributed to dipole moments associated with the step edges. The dipole moments per unit step length are larger for open edge structures than for densely packed ones. The dipole moments for Pt are about twice as large as for Au and W. (Auth.)

  18. Effects of different additives on bimetallic Au-Pt nanoparticles electrodeposited onto indium tin oxide electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Ballarin, Barbara, E-mail: ballarin@ms.fci.unibo.i [Dipartimento di Chimica Fisica ed Inorganica, Universita di Bologna, V.le Risorgimento, 4, 40136-Bologna (Italy)] [INSTM, UdR Bologna (Italy); Gazzano, Massimo [ISOF-CNR, V. Selmi, 40126-Bologna (Italy); Tonelli, Domenica [Dipartimento di Chimica Fisica ed Inorganica, Universita di Bologna, V.le Risorgimento, 4, 40136-Bologna (Italy)] [INSTM, UdR Bologna (Italy)

    2010-09-01

    Bimetallic Au-Pt nanoparticles (Au-Pt{sub NPs}) have been synthesized using an electrochemical reduction approach. The effects of the addition of different additives in the electrodeposition bath namely KI, 1-nonanesulfonic acid sodium salt and Triton X-100 have been investigated. The structural characterization of the bimetallic nanoparticles has been carried out using scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), UV-vis spectroscopy, X-ray diffraction (XRD) and cyclic voltammetry (CV). The Au-Pt{sub NPs} prepared in the presence of KI and Triton X-100 characterized by a relatively narrow size distribution as well as a higher particle density and surface coverage whereas no changes in the morphology were observed. These results suggest a dependence of the size and distribution of the bimetallic nanoparticles from the type and concentration of the additives employed.

  19. Synthesis and electrocatalytic effect of Ag@Pt core-shell nanoparticles supported on reduced graphene oxide for sensitive and simple label-free electrochemical aptasensor.

    Science.gov (United States)

    Mazloum-Ardakani, Mohammad; Hosseinzadeh, Laleh; Taleat, Zahra

    2015-12-15

    Bimetallic Ag@Pt core-shell nanoparticles supported on reduced graphene oxide nanosheets (Ag@Pt-GRs) was synthesized and used as novel desirable sensor platform and electrocatalyst for catechol as probe in aptasensor. Gold screen-printed electrodes modified with Ag@Pt-GRs and applied to advance enzyme-free and label-free electrochemical aptasensor for detection of protein biomarker tumor necrosis factor-alpha (TNF-α). The morphology of the Ag@Pt-GRs could be characterized by transmission electron microscopy, X-ray diffraction and UV-vis spectra. The results showed that these nanocomposite exhibited attractive electrocatalytic activity and also yielded large surface area, which improve the amount of immobilized TNF-α aptamer. Due to the excellent electrocatalytic activity of Ag@Pt-GRs towards the oxidation of catechol, determination of TNF-α antigen was based on its obstruction to the electrocatalytic oxidation of catechol by Ag@Pt-GRs after binding to the surface of electrode through interaction with the aptamer. The calibration curve was obtained by differential pulse voltammetry and square wave voltammetry. Under optimum conditions, the results demonstrated that this electrochemical aptasensor possessed a dynamic range from 0.0 pg/mL to 60 pg/mL with a low detection limit of 2.07 pg/mL for TNF-α. The analytical usefulness of the aptasensor was finally demonstrated analyzing serum samples. The simple fabrication method, high sensitivity, specificity, good reproducibility and stability as well as acceptable accuracy for TNF-α detection in human serum samples are the main advantages of this aptasensor, which might have broad applications in protein diagnostics and bioassay. Copyright © 2015 Elsevier B.V. All rights reserved.

  20. Highly open bowl-like PtAuAg nanocages as robust electrocatalysts towards ethylene glycol oxidation

    Science.gov (United States)

    Xu, Hui; Yan, Bo; Li, Shumin; Wang, Jin; Song, Pingping; Wang, Caiqin; Guo, Jun; Du, Yukou

    2018-04-01

    A novel combined seed mediated and galvanic replacement method has been demonstrated to synthesize a new class of trimetallic PtAuAg nanocatalysts with highly open bowl-like nanocage structure. The newly-generated PtAuAg nanocages catalysts exhibit superior electrocatalytic performances towards ethylene glycol oxidation with the mass activity of 6357.1 mA mg-1, 5.5 times higher than that of commercial Pt/C (1151.1 mA mg-1). This work demonstrates the first example of designing shape-controlled architectures of trimetallic bowl-like PtAuAg nanocages for liquid fuel electrooxidation.

  1. Ternary Pt/Rh/SnO2 electrocatalysts for oxidizing ethanol to CO2

    Science.gov (United States)

    Kowal, A.; Li, M.; Shao, M.; Sasaki, K.; Vukmirovic, M. B.; Zhang, J.; Marinkovic, N. S.; Liu, P.; Frenkel, A. I.; Adzic, R. R.

    2009-04-01

    Ethanol, with its high energy density, likely production from renewable sources and ease of storage and transportation, is almost the ideal combustible for fuel cells wherein its chemical energy can be converted directly into electrical energy. However, commercialization of direct ethanol fuel cells has been impeded by ethanol's slow, inefficient oxidation even at the best electrocatalysts. We synthesized a ternary PtRhSnO2/C electrocatalyst by depositing platinum and rhodium atoms on carbon-supported tin dioxide nanoparticles that is capable of oxidizing ethanol with high efficiency and holds great promise for resolving the impediments to developing practical direct ethanol fuel cells. This electrocatalyst effectively splits the C-C bond in ethanol at room temperature in acid solutions, facilitating its oxidation at low potentials to CO2, which has not been achieved with existing catalysts. Our experiments and density functional theory calculations indicate that the electrocatalyst's activity is due to the specific property of each of its constituents, induced by their interactions. These findings help explain the high activity of Pt-Ru for methanol oxidation and the lack of it for ethanol oxidation, and point to the way to accomplishing the C-C bond splitting in other catalytic processes.

  2. Double stripe reconstruction of the Pt(111) surface

    Indian Academy of Sciences (India)

    Unknown

    surface density and alternating hcp and fcc domains, arranged to form a honeycomb pattern with a very large repeat distance of 100–300 Å. In this ... 1992, it was found in X-ray scattering experiments. (Sandy et al 1992; Grübel et al 1993) ... second, third or fourth layers, the surface atoms are said to be occupying the 'top', ...

  3. 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.

  4. Excellent performance of Pt-C/TiO2 for methanol oxidation: Contribution of mesopores and partially coated carbon

    Science.gov (United States)

    Wu, Xinbing; Zhuang, Wei; Lu, Linghong; Li, Licheng; Zhu, Jiahua; Mu, Liwen; Li, Wei; Zhu, Yudan; Lu, Xiaohua

    2017-12-01

    Partial deposition of carbon onto mesoporous TiO2 (C/TiO2) were prepared as supporting substrate for Pt catalyst development. Carbon deposition is achieved by in-situ carbonization of furfuryl alcohol. The hybrid catalysts were characterized by XRD, Raman, SEM and TEM and exhibited outstanding catalytic activity and stability in methanol oxidation reaction. The heterogeneous carbon coated on mesoporous TiO2 fibers provided excellent electrical conductivity and strong interfacial interaction between TiO2 support and Pt metal nanoparticles. Methanol oxidation reaction results showed that the activity of Pt-C/TiO2 is 3.0 and 1.5 times higher than that of Pt-TiO2 and Pt-C, respectively. In addition, the Pt-C/TiO2 exhibited a 6.7 times enhanced stability compared with Pt-C after 2000 cycles. The synergistic effect of C/TiO2 is responsible for the enhanced activity of Pt-C/TiO2, and its excellent durability could be ascribed to the strong interfacial interaction between Pt nanoparticles and C/TiO2 support.

  5. First principles investigation of the activity of thin film Pt, Pd and Au surface alloys for oxygen reduction

    DEFF Research Database (Denmark)

    Tripkovic, Vladimir; Hansen, Heine Anton; Rossmeisl, Jan

    2015-01-01

    active binary thin films are near-surface alloys of Pt with subsurface Pd and certain PdAu and PtAu thin films with surface and/or subsurface Au. The most active ternary thin films are with pure metal Pt or Pd skins with some degree of Au in the surface and/or subsurface layer and the near-surface alloys...... driving force for surface segregation, diffusion to defects or surface self-assembling. On the basis of stability and activity analysis we conclude that the near surface alloy of Pd in Pt and some PdAu binary and PtPdAu ternary thin films with a controlled amount of Au are the best catalysts for oxygen...

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

    Science.gov (United States)

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

    2018-03-23

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

  7. Template preparation of Pt nanowire array electrode on Ti/Si substrate for methanol electro-oxidation

    Science.gov (United States)

    Zhao, Guang-Yu; Xu, Cai-Ling; Guo, Dao-Jun; Li, Hua; Li, Hu-Lin

    2007-01-01

    Platinum (Pt) nanowire array electrode is obtained by dc electrodeposition of Pt into the pores of anodic aluminum oxide (AAO) template on Ti/Si substrate. Transmission electron microscope (TEM) examination shows all the nanowires have uniform diameter of about 30 nm. The brush shapes Pt nanowire array electrode can be seen clearly by field emission scanning electron microscope (FESEM). Pt nanowire array electrode gives the X-ray diffraction (XRD) pattern of face-centered cubic (fcc) crystal structure. The electro-oxidation of methanol on this electrode is investigated at room temperature by cyclic voltammetry. The results demonstrated that the Pt nanowire array electrode will have good potential applications in portable power sources.

  8. Structure–activity relationships of Pt/Al2O3 catalysts for CO and NO oxidation at diesel exhaust conditions

    DEFF Research Database (Denmark)

    Boubnov, Alexey; Dahl, Søren; Johnson, Erik

    2012-01-01

    Structure–performance relationships for Pt/Al2O3 catalysts with mean Pt particle sizes of 1, 2, 3, 5 and 10nm are investigated for the catalytic oxidation of CO and NO under lean-burning diesel exhaust conditions. The most active catalysts for CO oxidation exhibit Pt particles of 2–3nm, having a ...

  9. Fabrication and Surface Properties of Composite Films of SAM/Pt/ZnO/SiO 2

    KAUST Repository

    Yao, Ke Xin

    2008-12-16

    Through synthetic architecture and functionalization with self-assembled monolayers (SAMs), complex nanocomposite films of SAM/Pt/ZnO/SiO2 have been facilely prepared in this work. The nanostructured films are highly uniform and porous, showing a wide range of tunable wettabilities from superhydrophilicity to superhydrophobicity (water contact angles: 0° to 170°). Our approach offers synthetic flexibility in controlling film architecture, surface topography, coating texture, crystallite size, and chemical composition of modifiers (e.g., SAMs derived from alkanethiols). For example, wettability properties of the nanocomposite films can be finely tuned with both inorganic phase (i.e., ZnO/SiO2 and Pt/ZnO/SiO2) and organic phase (i.e., SAMs on Pt/ZnO/SiO2). Due to the presence of catalytic components Pt/ZnO within the nanocomposites, surface reactions of the organic modifiers can further take place at room temperature and elevated temperatures, which provides a means for SAM formation and elimination. Because the Pt/ZnO forms an excellent pair of metal-semiconductors for photocatalysis, the anchored SAMs can also be modified or depleted by UV irradiation (i.e., the films possess self-cleaning ability). Potential applications of these nanocomposite films have been addressed. Our durability tests also confirm that the films are thermally stable and structurally robust in modification- regeneration cycles. © 2008 American Chemical Society.

  10. Microwave-assisted rapid synthesis of Pt/graphene nanosheet composites and their application for methanol oxidation

    Science.gov (United States)

    Liu, Sen; Wang, Lei; Tian, Jingqi; Lu, Wenbo; Zhang, Yingwei; Wang, Xiaodan; Sun, Xuping

    2011-10-01

    Polymer-free Pt/graphene nanosheet (GN) composites have been rapidly prepared by a one-step microwave-assisted reduction method, carried out by ethylene glycol reduction of H2PtCl6 in a graphene oxide suspension. Several analytic techniques including UV-vis spectroscopy, Raman spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and transmission electron microscopy have been used to characterize the resulting Pt/GN composites. It suggests that such composites exhibit good catalytic activity toward methanol oxidation.

  11. Exploring the Effect of Au/Pt Ratio on Glycerol Oxidation in Presence and Absence of a Base

    Directory of Open Access Journals (Sweden)

    Alberto Villa

    2018-01-01

    Full Text Available Bimetallic AuPt nanoparticles with different Au:Pt ratios (molar ratio: 9-1, 8-2, 6-4, 2-8, 1-9 and the corresponding Au and Pt monometallic ones were prepared by sol immobilization and immobilized on commercial TiO2 (P25. The catalytic activity was evaluated in the liquid phase glycerol oxidation in presence and absence of a base (NaOH. It was found that the Au:Pt molar ratio and reaction conditions strongly influence the catalytic performance. In the presence of NaOH, Au-rich catalysts were more active than Pt-rich ones, with the highest activity observed for Au9Pt1/TiO2 (6575 h−1. In absence of a base, a higher content of Pt is needed to produce the most active catalyst (Au6Pt4/TiO2, 301 h−1. In terms of selectivity, in presence of NaOH, Au-rich catalysts showed a high selectivity to C3 products (63–72% whereas Pt-rich catalysts promote the formation of formic and glycolic acids. The opposite trend was observed in absence of a base with Pt-rich catalysts showing higher selectivity to C3 products (83–88%.

  12. Study of the Isothermal Oxidation Process and Phase Transformations in B2-(Ni,PtAl/RENE-N5 System

    Directory of Open Access Journals (Sweden)

    Luis Alberto Cáceres-Díaz

    2016-09-01

    Full Text Available Changes in composition, crystal structure and phase transformations of B2-(Ni,PtAl coatings upon isothermal oxidation experiments (natural and scale free oxidation at 1100 °C, as a function of time beyond their martensitic transformation, are reported. Specifically, the analysis of lattice parameter and composition are performed to identify changes in the B2-(Ni,PtAl phase upon the chemically-driven L10-(Ni,PtAl and L12-(Ni,Pt3Al transformations. The B2-(Ni,PtAl phase was found to disorder and transform the martensite during the heat treatments for both oxidation experiments at approximately 36.3 and 40.9 at. % of Al, 47.7 and 42.9 at. % of Ni, 6.2 and 8.5 at. % of Pt, 4.2 and 2.9 at. % of Cr and 4.4 and 3.8 at. % of Co. The lattice constant and the long-range order parameter of the B2-(Ni,PtAl phase decreased linearly as a function of the elemental content irrespective of the nature of the oxidation experiments.

  13. Synthesis and physicochemical characterizations of nanostructured Pt/Al{sub 2}O{sub 3}-CeO{sub 2} catalysts for total oxidation of VOCs

    Energy Technology Data Exchange (ETDEWEB)

    Abbasi, Zahra [Chemical Engineering Department, Sahand University of Technology, P.O. Box 51335-1996, Sahand New Town, Tabriz (Iran, Islamic Republic of); Reactor and Catalysis Research Center (RCRC), Sahand University of Technology, P.O. Box 51335-1996, Sahand New Town, Tabriz (Iran, Islamic Republic of); Haghighi, Mohammad, E-mail: haghighi@sut.ac.ir [Chemical Engineering Department, Sahand University of Technology, P.O. Box 51335-1996, Sahand New Town, Tabriz (Iran, Islamic Republic of); Reactor and Catalysis Research Center (RCRC), Sahand University of Technology, P.O. Box 51335-1996, Sahand New Town, Tabriz (Iran, Islamic Republic of); Environmental Engineering Research Center (EERC), Sahand University of Technology, P.O. Box 51335-1996, Sahand New Town, Tabriz (Iran, Islamic Republic of); Fatehifar, Esmaeil [Chemical Engineering Department, Sahand University of Technology, P.O. Box 51335-1996, Sahand New Town, Tabriz (Iran, Islamic Republic of); Reactor and Catalysis Research Center (RCRC), Sahand University of Technology, P.O. Box 51335-1996, Sahand New Town, Tabriz (Iran, Islamic Republic of); Environmental Engineering Research Center (EERC), Sahand University of Technology, P.O. Box 51335-1996, Sahand New Town, Tabriz (Iran, Islamic Republic of); Saedy, Saeed [Chemical Engineering Department, Sahand University of Technology, P.O. Box 51335-1996, Sahand New Town, Tabriz (Iran, Islamic Republic of); Reactor and Catalysis Research Center (RCRC), Sahand University of Technology, P.O. Box 51335-1996, Sahand New Town, Tabriz (Iran, Islamic Republic of)

    2011-02-28

    Pt/Al{sub 2}O{sub 3}-CeO{sub 2} nanocatalysts with Pt loading of 1% and ceria loading of 10, 20 and 30% were successfully prepared via wet impregnation method to be utilized in catalytic oxidation of BTX. The nanocatalysts were characterized using XRD, FESEM, TEM, N{sub 2} adsorption, FTIR and TPR-H{sub 2} techniques. The XRD patterns confirmed the formation of cerium oxide as the crystalline phase on alumina with the average crystallite size of 8.1-8.7 nm, derived by Scherrer equation. FESEM images confirmed that these nanocatalysts had ceria particles in nano-ranges. TEM analysis showed that platinum particles were fairly well dispersed on Al{sub 2}O{sub 3}-CeO{sub 2} with an average size of 5-20 nm. BET surface area presented large surface area for nanocatalysts. TPR patterns showed that by adding 1% platinum to support, the reducibility is highly increased. These patterns also revealed the promoting effect of ceria on reducibility of Pt and Al{sub 2}O{sub 3}. The results of toluene oxidation indicated that the synthesized nanocatalysts were highly active and able to remove nearly 100% of toluene and xylene and about 85% of benzene as representative VOCs. The presence of nanoparticles along with good characteristics of the synthesized nanocatalysts presented them as highly efficient materials for catalytic oxidation of VOCs.

  14. Synthesis and physicochemical characterizations of nanostructured Pt/Al2O3-CeO2 catalysts for total oxidation of VOCs.

    Science.gov (United States)

    Abbasi, Zahra; Haghighi, Mohammad; Fatehifar, Esmaeil; Saedy, Saeed

    2011-02-28

    Pt/Al(2)O(3)-CeO(2) nanocatalysts with Pt loading of 1% and ceria loading of 10, 20 and 30% were successfully prepared via wet impregnation method to be utilized in catalytic oxidation of BTX. The nanocatalysts were characterized using XRD, FESEM, TEM, N(2) adsorption, FTIR and TPR-H(2) techniques. The XRD patterns confirmed the formation of cerium oxide as the crystalline phase on alumina with the average crystallite size of 8.1-8.7 nm, derived by Scherrer equation. FESEM images confirmed that these nanocatalysts had ceria particles in nano-ranges. TEM analysis showed that platinum particles were fairly well dispersed on Al(2)O(3)-CeO(2) with an average size of 5-20 nm. BET surface area presented large surface area for nanocatalysts. TPR patterns showed that by adding 1% platinum to support, the reducibility is highly increased. These patterns also revealed the promoting effect of ceria on reducibility of Pt and Al(2)O(3). The results of toluene oxidation indicated that the synthesized nanocatalysts were highly active and able to remove nearly 100% of toluene and xylene and about 85% of benzene as representative VOCs. The presence of nanoparticles along with good characteristics of the synthesized nanocatalysts presented them as highly efficient materials for catalytic oxidation of VOCs. Copyright © 2010 Elsevier B.V. All rights reserved.

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

    Science.gov (United States)

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

    2011-01-07

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

  16. In Situ X-Ray Probing Reveals Fingerprints of Surface Platinum Oxide

    Energy Technology Data Exchange (ETDEWEB)

    Friebel, Daniel

    2011-08-24

    In situ x-ray absorption spectroscopy (XAS) at the Pt L{sub 3} edge is a useful probe for Pt-O interactions at polymer electrolyte membrane fuel cell (PEMFC) cathodes. We show that XAS using the high energy resolution fluorescence detection (HERFD) mode, applied to a well-defined monolayer Pt/Rh(111) sample where the bulk penetrating hard x-rays probe only surface Pt atoms, provides a unique sensitivity to structure and chemical bonding at the Pt-electrolyte interface. Ab initio multiple-scattering calculations using the FEFF8 code and complementary extended x-ray absorption fine structure (EXAFS) results indicate that the commonly observed large increase of the white-line at high electrochemical potentials on PEMFC cathodes originates from platinum oxide formation, whereas previously proposed chemisorbed oxygen-containing species merely give rise to subtle spectral changes.

  17. TiO2 Nanotube-Carbon (TNT-C) as Support for Pt-based Catalyst for High Methanol Oxidation Reaction in Direct Methanol Fuel Cell

    Science.gov (United States)

    Abdullah, M.; Kamarudin, S. K.; Shyuan, L. K.

    2016-12-01

    In this study, TiO2 nanotubes (TNTs) were synthesized via a hydrothermal method using highly concentrated NaOH solutions varying from 6 to 12 M at 180 °C for 48 h. The effects of the NaOH concentration and the TNT crystal structure on the performance for methanol oxidation were investigated to determine the best catalyst support for Pt-based catalysts. The results showed that TNTs produced with 10 M NaOH exhibited a length and a diameter of 550 and 70 nm, respectively; these TNTs showed the best nanotube structure and were further used as catalyst supports for a Pt-based catalyst in a direct methanol fuel cell. The synthesized TNT and Pt-based catalysts were analysed by FESEM, TEM, BET, EDX, XRD and FTIR. The electrochemical performance of the catalysts was investigated using cyclic voltammetry (CV) and chronoamperometric (CA) analysis to further understand the methanol oxidation in the direct methanol fuel cell (DMFC). Finally, the result proves that Pt-Ru/TNT-C catalyst shows high performance in methanol oxidation as the highest current density achieved at 3.3 mA/cm2 (normalised by electrochemically active surface area) and high catalyst tolerance towards poisoning species was established.

  18. TiO2Nanotube-Carbon (TNT-C) as Support for Pt-based Catalyst for High Methanol Oxidation Reaction in Direct Methanol Fuel Cell.

    Science.gov (United States)

    Abdullah, M; Kamarudin, S K; Shyuan, L K

    2016-12-01

    In this study, TiO 2 nanotubes (TNTs) were synthesized via a hydrothermal method using highly concentrated NaOH solutions varying from 6 to 12 M at 180 °C for 48 h. The effects of the NaOH concentration and the TNT crystal structure on the performance for methanol oxidation were investigated to determine the best catalyst support for Pt-based catalysts. The results showed that TNTs produced with 10 M NaOH exhibited a length and a diameter of 550 and 70 nm, respectively; these TNTs showed the best nanotube structure and were further used as catalyst supports for a Pt-based catalyst in a direct methanol fuel cell. The synthesized TNT and Pt-based catalysts were analysed by FESEM, TEM, BET, EDX, XRD and FTIR. The electrochemical performance of the catalysts was investigated using cyclic voltammetry (CV) and chronoamperometric (CA) analysis to further understand the methanol oxidation in the direct methanol fuel cell (DMFC). Finally, the result proves that Pt-Ru/TNT-C catalyst shows high performance in methanol oxidation as the highest current density achieved at 3.3 mA/cm 2 (normalised by electrochemically active surface area) and high catalyst tolerance towards poisoning species was established.

  19. Energetics of methanol and formic acid oxidation on Pt(111): Mechanistic insights from adsorption calorimetry

    Science.gov (United States)

    Silbaugh, Trent L.; Karp, Eric M.; Campbell, Charles T.

    2016-08-01

    The catalytic and electrocatalytic oxidation and reforming of methanol and formic acid have received intense interest due to potential use in direct fuel cells and as prototype models for understanding electrocatalysis. Consequently, the reaction energy diagram (energies of all the adsorbed intermediates and activation energies of all the elementary steps) have been estimated for these reactions on Pt(111) by density functional theory (DFT) in several studies. However, no experimental measurement of these energy diagrams have been reported, nor is there a consensus on the mechanisms. Here, we use energies of key intermediates on Pt(111) from single crystal adsorption calorimetry (SCAC) and temperature programmed desorption (TPD) to build a combined energy diagram for these reactions. It suggests a new pathway involving monodentate formate as a key intermediate, with bidentate formate only being a spectator species that slows the rate. This helps reconcile conflicting proposed mechanisms.

  20. Surface composition of magnetron sputtered Pt-Co thin film catalyst for proton exchange membrane fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Vorokhta, Mykhailo, E-mail: vorohtam@gmail.com [Charles University in Prague, Faculty of Mathematics and Physics, Department of Surface and Plasma Science, V Holešovičkách 2, 18000 Prague (Czech Republic); Khalakhan, Ivan; Václavů, Michal [Charles University in Prague, Faculty of Mathematics and Physics, Department of Surface and Plasma Science, V Holešovičkách 2, 18000 Prague (Czech Republic); Kovács, Gábor; Kozlov, Sergey M. [Departament de Química Física and Institut de Química Teòrica i Computacional (IQTCUB), Universitat de Barcelona, c/ Martí i Franquès 1, 08028 Barcelona (Spain); Kúš, Peter; Skála, Tomáš; Tsud, Natalia; Lavková, Jaroslava [Charles University in Prague, Faculty of Mathematics and Physics, Department of Surface and Plasma Science, V Holešovičkách 2, 18000 Prague (Czech Republic); Potin, Valerie [Laboratoire Interdisciplinaire Carnot de Bourgogne, UMR 6303 CNRS-Université Bourgogne, 9 Av. A. Savary, BP 47870, F-21078 Dijon Cedex (France); and others

    2016-03-01

    Graphical abstract: - Highlights: • Nanostructured Pt-Co thin catalyst films were grown on carbon by magnetron sputtering. • The surface composition of the nanostructured Pt-Co films was investigated by surface analysis techniques. • We carried out modeling of Pt-Co nanoalloys by computational methods. • Both experiment and modeling based on density functional theory showed that the surface of Pt-Co nanoparticles is almost exclusively composed of Pt atoms. - Abstract: Recently we have tested a magnetron sputtered Pt-Co catalyst in a hydrogen-fed proton exchange membrane fuel cell and showed its high catalytic activity for the oxygen reduction reaction. Here we present further investigation of the magnetron sputtered Pt-Co thin film catalyst by both experimental and theoretical methods. Scanning electron microscopy and transmission electron microscopy experiments confirmed the nanostructured character of the catalyst. The surface composition of as-deposited and annealed at 773 K Pt-Co films was investigated by surface analysis techniques, such as synchrotron radiation photoelectron spectroscopy and X-ray photoelectron spectroscopy. Modeling based on density functional theory showed that the surface of 6 nm large 1:1 Pt-Co nanoparticles is almost exclusively composed of Pt atoms (>90%) at typical operation conditions and the Co content does not exceed 20% at 773 K, in agreement with the experimental characterization of such films annealed in vacuum. According to experiment, the density of valence states of surface atoms in Pt-Co nanostructures is shifted by 0.3 eV to higher energies, which can be associated with their higher activity in the oxygen reduction reaction. The changes in electronic structure caused by alloying are also reflected in the measured Pt 4f, Co 3p and Co 2p photoelectron peak binding energies.

  1. Statistical analysis of the electrocatalytic activity of Pt nanoparticles supported on novel functionalized reduced graphene oxide-chitosan for methanol electrooxidation

    Science.gov (United States)

    Ekrami-Kakhki, Mehri-Saddat; Abbasi, Sedigheh; Farzaneh, Nahid

    2018-01-01

    The purpose of this study is to statistically analyze the anodic current density and peak potential of methanol oxidation at Pt nanoparticles supported on functionalized reduced graphene oxide (RGO), using design of experiments methodology. RGO is functionalized with methyl viologen (MV) and chitosan (CH). The novel Pt/MV-RGO-CH catalyst is successfully prepared and characterized with transmission electron microscopy (TEM) image. The electrocatalytic activity of Pt/MV-RGOCH catalyst is experimentally evaluated for methanol oxidation. The effects of methanol concentration and scan rate factors are also investigated experimentally and statistically. The effects of these two main factors and their interactions are investigated, using analysis of variance test, Duncan's multiple range test and response surface method. The results of the analysis of variance show that all the main factors and their interactions have a significant effect on anodic current density and peak potential of methanol oxidation at α = 0.05. The suggested models which encompass significant factors can predict the variation of the anodic current density and peak potential of methanol oxidation. The results of Duncan's multiple range test confirmed that there is a significant difference between the studied levels of the main factors. [Figure not available: see fulltext.

  2. Localized Pd Overgrowth on Cubic Pt Nanocrystals for Enhanced Electrocatalytic Oxidation of Formic Acid

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Hyunjoo; Habas, Susan; Somorjai, Gabor; Yang, Peidong

    2007-12-14

    Single crystalline surface such as (100), (111), (110) has been studied as an idealized platform for electrocatalytic reactions since the atomic arrangement affects a catalytic property. The secondary metal deposition on these surfaces also alters the catalytic property often showing improvement such as poisoning decrease. On the other hand, electrocatalysts used for practical purpose usually have a size on the order of nanometers. Therefore, linking the knowledge from single crystalline studies to nanoparticle catalysts is of enormous importance. Recently, the Pt nanoparticles which surface structure was preferentially oriented was synthesized and used as electrocatalysts. Here, we demonstrate a rational design of a binary metallic nanocatalyst based on the single crystalline study.

  3. Recent Advances on Electro-Oxidation of Ethanol on Pt- and Pd-Based Catalysts: From Reaction Mechanisms to Catalytic Materials

    Directory of Open Access Journals (Sweden)

    Ye Wang

    2015-09-01

    Full Text Available The ethanol oxidation reaction (EOR has drawn increasing interest in electrocatalysis and fuel cells by considering that ethanol as a biomass fuel has advantages of low toxicity, renewability, and a high theoretical energy density compared to methanol. Since EOR is a complex multiple-electron process involving various intermediates and products, the mechanistic investigation as well as the rational design of electrocatalysts are challenging yet essential for the desired complete oxidation to CO2. This mini review is aimed at presenting an overview of the advances in the study of reaction mechanisms and electrocatalytic materials for EOR over the past two decades with a focus on Pt- and Pd-based catalysts. We start with discussion on the mechanistic understanding of EOR on Pt and Pd surfaces using selected publications as examples. Consensuses from the mechanistic studies are that sufficient active surface sites to facilitate the cleavage of the C–C bond and the adsorption of water or its residue are critical for obtaining a higher electro-oxidation activity. We then show how this understanding has been applied to achieve improved performance on various Pt- and Pd-based catalysts through optimizing electronic and bifunctional effects, as well as by tuning their surface composition and structure. Finally we point out the remaining key problems in the development of anode electrocatalysts for EOR.

  4. Fabrication and enhanced photocatalytic properties of Pt@SiO2@TiO2 composites by surface plasma resonance from Pt nanoparticles

    Science.gov (United States)

    Zhang, Fangfang; Liu, Wei; Liu, Yousong; Wang, Junyi; Ji, Guangbin

    2015-02-01

    Pt@SiO2@TiO2 composites with an average diameter of about 120 nm were synthesized by an aqueous method. Morphology, microstructure, and light absorption performance of as-prepared samples were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and UV-Vis diffuse reflectance spectroscopy. The results indicate that 5-nm-thick SiO2 interlayer coated on the Pt nanoparticles were used to separate the Pt from the TiO2. The covering SiO2 layer between Pt nanoparticles and TiO2 layer present a wide spectral response. The enhanced photocatalytic efficiency under both the full spectrum and visible light can be attributed to the existence of Pt nanoparticles and interlayer SiO2. The coupling processes between TiO2 and plasmon were presented and the mechanism was discussed. The localized surface plasmon resonance effect of Pt nanoparticles is the main reason for the enhanced photocatalytic activity of the composite Pt@SiO2@TiO2.

  5. 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

  6. 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.

  7. 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)

  8. Combined quantum chemistry and Monte Carlo simulation of competitive adsorption of O{sub 2} and OH on Pt surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Li, Rui, E-mail: ruililcu@gmail.com [Department of Chemistry, Liaocheng University, Liaocheng 252059 (China); Li, Haibo; Xu, Shuling [Department of Chemistry, Liaocheng University, Liaocheng 252059 (China); Liu, Jifeng, E-mail: liujifeng111@gmail.com [Key Laboratory of Food Nutrition and Safety, Ministry of Education of China, Tianjin University of Science and Technology, Tianjin 300457 (China)

    2017-07-15

    Highlights: • Competitive adsorption of O{sub 2} and OH on different Pt surfaces was theoretically studied. • The adsorption energies of O{sub 2} and OH depend on the Pt surfaces and the adsorption sites. • The order of O{sub 2} adsorption efficiency was characterized. - Abstract: To obtain a microscopic explanation on the difference of oxygen reduction reaction activity on different Pt low index surfaces, we simulated competitive adsorptions of O{sub 2} and OH on four Pt low index surfaces. Firstly, all possible chemical adsorption configurations of the O{sub 2} and OH molecules on the three surfaces were acquired through density functional theory. The distribution of these configurations on the different surfaces was collected from Monte Carlo simulations. Our results demonstrated that the adsorption energy order of O{sub 2} on different surfaces was (110)(1 × 2) > (110) > (100) > (111) and that the adsorption energy order of the OH molecules on Pt surfaces was the same. Considering the competitive adsorption of O{sub 2} and OH on Pt surfaces, the final O{sub 2} adsorption efficiencies order of three surfaces was (111) > (110) > (100) > (110)(1 × 2), which was consistent with the experimental activities of oxygen reduction. Our study provided theoretical references for previous experimental studies and had important significance for the understanding of oxygen adsorption on Pt surfaces.

  9. Self-Stable WP/C Support with Excellent Cocatalytic Functionality for Pt: Enhanced Catalytic Activity and Durability for Methanol Electro-Oxidation.

    Science.gov (United States)

    Duan, Yaqiang; Sun, Ye; Pan, Siyu; Dai, Ying; Hao, Liang; Zou, Jinlong

    2016-12-14

    To endow catalyst support with excellent stability and cocatalytic activity toward methanol, oxidation reaction (MOR) is an effective way to strengthen the electrocatalytic activity of Pt-based catalysts. Tungsten phosphide/3D-corrugated porous carbon (WP/C) composite as Pt-support and cocatalyst for MOR is prepared via a synchronous synthesis method. Porous 3D-tufted structure and high surface area of WP/C with abundant oxygen-containing groups (such as C-O-C, C-O-H, or C-OH) can significantly improve the exposure of active sites, which enlarge the contact area with electrolyte and facilitate the mass transfer and absorption of methanol for promoting the MOR activity in acidic electrolyte. Pt-WP/C exhibits a considerably higher mass activity (1559.3 mA mg Pt -1 ) for MOR than that of Pt/C (488.2 mA mg Pt -1 ), owing to the special activity of W δ+ and P δ- sites for the decomposition reaction of water. With the introduction of W species, more available P species (passivated or not) are activated for further enhancing the cocatalytic activity of WP for MOR. Furthermore, the CO tolerance and durability of Pt-WP/C are also remarkable, which should benefit from the fast surface transport of adsorbed CO on different crystalline faces of WP and the extremely stable WP-C structure originating from the existence of P-P chains between the adjacent WP particles, respectively. The design of the porous structure and cocatalytic effect of this catalyst support (WP/C) provides a promising method to drastically enhance MOR activity.

  10. Adsorption and Oxidation Investigations over Pt/Al2O3 Catalyst: A Microcalorimetric Study

    Directory of Open Access Journals (Sweden)

    Oana Mihai

    2016-05-01

    Full Text Available The differential adsorption heats of oxygen and NO, as well as catalytic oxidation behavior during NO oxidation and NO2 dissociation reactions over supported Pt-catalysts, were investigated by microcalorimetric measurements. The average heat of adsorption (∆H of oxygen ranged from 310 kJ/mol at 200 °C to 289 kJ/mol at 400 °C. Over this temperature range formation of platinum oxides and coverage dependence caused variations in the apparent heat of adsorption. NO heat of adsorption from 50 to 150 °C was near constant with an average value of 202 kJ/mol over the temperature range.

  11. Sn surface-enriched Pt-Sn bimetallic nanoparticles as a selective and stable catalyst for propane dehydrogenation

    KAUST Repository

    Zhu, Haibo

    2014-12-01

    A new one pot, surfactant-free, synthetic route based on the surface organometallic chemistry (SOMC) concept has been developed for the synthesis of Sn surface-enriched Pt-Sn nanoparticles. Bu3SnH selectively reacts with [Pt]-H formed in situ at the surface of Pt nanoparticles, Pt NPs, obtained by reduction of K2PtCl4 by LiB(C2H5)3H. Chemical analysis, 1H MAS and 13C CP/MAS solid-state NMR as well as two-dimensional double-quantum (DQ) and triple-quantum (TQ) experiments show that organo-tin moieties Sn(n-C4H9) are chemically linked to the surface of Pt NPs to produce, in fine, after removal of most of the n-butyl fragment, bimetallic Pt-Sn nanoparticles. The Sn(n-CH2CH2CH2CH3) groups remaining at the surface are believed to stabilize the as-synthesized Pt-Sn NPs, enabling the bimetallic NPs to be well dispersed in THF. Additionally, the Pt-Sn nanoparticles can be supported on MgAl2O4 during the synthesis of the nanoparticles. Some of the Pt-Sn/MgAl2O4 catalyst thus prepared exhibits high activity in PROX of CO and an extremely high selectivity and stability in propane dehydrogenation to propylene. The enhanced activity in propane dehydrogenation is associated with the high concentration of inactive Sn at the surface of Pt nanoparticles which ”isolates” the active Pt atoms. This conclusion is confirmed by XRD, NMR, TEM, and XPS analysis.

  12. Structure vs chemistry: friction and wear of Pt-based metallic surfaces.

    Science.gov (United States)

    Caron, A; Louzguine-Luzguin, D V; Bennewitz, R

    2013-11-13

    In comparison of a Pt57.5Cu14.7Ni5.3P22.5 metallic glass with a Pt(111) single crystal we find that wearless friction is determined by chemistry through bond formation alloying, while wear is determined by structure through plasticity mechanisms. In the wearless regime, friction is affected by the chemical composition of the counter body and involves the formation of a liquid-like neck and interfacial alloying. The wear behavior of Pt-based metallic surfaces is determined by their structural properties and corresponding mechanisms for plastic deformation. In the case of Pt(111) wear occurs by dislocation-mediated homogeneous plastic deformation. In contrast the wear of Pt57.5Cu14.7Ni5.3P22.5 metallic glass occurs through localized plastic deformation in shear bands that merge together in a single shear zone above a critical load and corresponds to the shear softening of metallic glasses. These results open a new route in the control of friction and wear of metals and are relevant for the development of self-lubricated and wear-resistant mechanical devices.

  13. Cu-capped surface alloys of Pt/Cu left brace 100 right brace

    CERN Document Server

    Alshamaileh, E; Wander, A

    2003-01-01

    The room-temperature deposition of 0.5 monolayer (ML) Pt on Cu left brace 100 right brace followed by annealing to 525 K results in a sharp c(2 x 2) low-energy electron diffraction (LEED) pattern. The structure of this surface alloy is investigated by means of symmetrized automated tensor low-energy electron diffraction (SATLEED) analysis and ab initio plane wave density functional calculations. The results are then compared with those for the similar system 0.5 ML Pd/Cu left brace 100 right brace. SATLEED results for the Pt/Cu left brace 100 right brace show that it consists of an ordered c(2 x 2) Cu-Pt second layer alloy capped with a pure Cu first layer. The first and second interlayer spacings are found to be expanded by +5.1 +- 1.7 and +3.5 +- 1.7% respectively (relative to the bulk Cu interlayer spacing of 1.807 A) due to the insertion of the 8% larger Pt atoms into the second layer. The ordered mixed layer is found to be rippled by 0.08 +- 0.06 A with Pt atoms rippled outwards towards the solid-vacuum ...

  14. Interfacial-Bonding-Regulated CO Oxidation over Pt Atoms Immobilized on Gas-Exfoliated Hexagonal Boron Nitride

    KAUST Repository

    Liu, Xin

    2017-10-12

    We compared the electronic structure and CO oxidation mechanisms over Pt atoms immobilized by both B-vacancies and N-vacancies on gas-exfoliated hexagonal boron nitride. We showed that chemical bonds are formed between the B atoms associated with dangling bonds around the vacancies and Pt atoms. These bonds not only alter the thermodynamics and kinetics for the aggregation and effectively immobilize Pt atoms, but also significantly change the composition and energetic distribution of the electronic states of the composites to circumvent CO poisoning and to favour coadsorption of CO and O2, which further regulates the reactions to proceed through a Langmuir-Hinshelwood mechanism. The CO oxidation over Pt atoms immobilized at N-vacancies involves formation of an intermediate with –C(O)-O−O- bonded to Pt, the generation of CO2 by peroxo O−O bond scission and the reduction of the remnant oxygen, and the calculated energy barriers are 0.49, 0.23 and 0.18 eV, respectively. Such small energy barriers are comparable to those over Pt atoms trapped at B-vacancies, showing the effectiveness of Pt/hexagonal boron nitride atomic composites as catalysts for CO oxidation. These findings also suggest the feasibility of regulating the reaction pathways over single atom catalysts via interfacial engineering.

  15. Electrocatalytic oxidation of salicylic acid by a cobalt hydrotalcite-like compound modified Pt electrode.

    Science.gov (United States)

    Gualandi, Isacco; Scavetta, Erika; Zappoli, Sergio; Tonelli, Domenica

    2011-03-15

    In this paper a study of the electrocatalytic oxidation of salicylic acid (SA) at a Pt electrode coated with a Co/Al hydrotalcite-like compound (Co/Al HTLC coated-Pt) film is presented. The voltammetric behaviour of the modified electrode in 0.1M NaOH shows two different redox couples: Co(II)/Co(III) and Co(III)/Co(IV). The electrocatalysis occurs at the same potential of the latter couple, showing that Co(IV) centers act as the oxidant. The CV investigation demonstrates that the process is controlled both by mass and charge transfer and that the Co(IV) centers involved in the oxidation are two for each SA molecule. The estimated value of the catalytic constant is 4×10(4) M(-1) s(-1). The determination of salicylic acid was performed both by DPV and chronoamperometry. The linearity ranges and the LOD values resulted 1×10(-5) to 5×10(-4), 5×10(-7) to 1×10(-4), 6×10(-6) and 2×10(-7) M, respectively. The Co/Al HTLC electrode has been used for SA determination in BAYER Aspirina® and the obtained results are consistent with an independent HPLC analysis. Copyright © 2011 Elsevier B.V. All rights reserved.

  16. Confined Catalysis in the g-C3N4/Pt(111) Interface: Feasible Molecule Intercalation, Tunable Molecule-Metal Interaction, and Enhanced Reaction Activity of CO Oxidation.

    Science.gov (United States)

    Wang, Shujiao; Feng, Yingxin; Yu, Ming'an; Wan, Qiang; Lin, Sen

    2017-09-27

    The deposition of a two-dimensional (2D) atomic nanosheet on a metal surface has been considered as a new route for tuning the molecule-metal interaction and surface reactivity in terms of the confinement effect. In this work, we use first-principles calculations to systematically explore a novel nanospace constructed by placing a 2D graphitic carbon nitride (g-C 3 N 4 ) nanosheet over a Pt(111) surface. The confined catalytic activity in this nanospace is investigated using CO oxidation as a model reaction. With the inherent triangular pores in the g-C 3 N 4 overlayer being taken advantage of, molecules such as CO and O 2 can diffuse to adsorb on the Pt(111) surface underneath the g-C 3 N 4 overlayer. Moreover, the mechanism of intercalation is also elucidated, and the results reveal that the energy barrier depends mainly on the properties of the molecule and the channel. Importantly, the molecule-catalyst interaction can be tuned by the g-C 3 N 4 overlayer, considerably reducing the adsorption energy of CO on Pt(111) and leading to enhanced reactivity in CO oxidation. This work will provide important insight for constructing a promising nanoreactor in which the following is observed: The molecule intercalation is facile; the molecule-metal interaction is efficiently tuned; the metal-catalyzed reaction is promoted.

  17. Pt atoms stabilized on hexagonal boron nitride as efficient single-atom catalysts for CO oxidation: A first-principles investigation

    KAUST Repository

    Liu, Xin

    2015-01-01

    Taking CO oxidation as a probe, we investigated the electronic structure and reactivity of Pt atoms stabilized by vacancy defects on hexagonal boron nitride (h-BN) by first-principles-based calculations. As a joint effect of the high reactivity of both a single Pt atom and a boron vacancy defect (PtBV), the Pt-N interaction is -4.40 eV and is already strong enough to prohibit the diffusion and aggregation of the stabilized Pt atom. Facilitated by the upshifted Pt-d states originated from the Pt-N interaction, the barriers for CO oxidation through the Langmuir-Hinshelwood mechanism for formation and dissociation of peroxide-like intermediate and the regeneration are as low as 0.38, 0.10 and 0.04 eV, respectively, suggesting the superiority of PtBV as a catalyst for low temperature CO oxidation.

  18. Electrochemical immunosensor for detecting typical bladder cancer biomarker based on reduced graphene oxide-tetraethylene pentamine and trimetallic AuPdPt nanoparticles.

    Science.gov (United States)

    Ma, Hongmin; Zhang, Xiaoyue; Li, Xiaojian; Li, Rongxia; Du, Bin; Wei, Qin

    2015-10-01

    A highly sensitive electrochemical immunosensor for detection of typical bladder cancer biomarker-nuclear matrix protein 22 (NMP22) was developed by using reduced graphene oxide-tetraethylene pentamine (rGO-TEPA) and trimetallic AuPdPt nanoparticles (NPs). rGO-TEPA was used as the ideal material for signal amplification and AuPdPt NPs immobilization due to its excellent conductivity and large surface area. An effective platform was constructed for antibodies anchoring by using AuPdPt NPs, which kept the antibodies' high stability and bioactivity. Moreover, AuPdPt NPs could accelerate the electron transfer and enhance the signal response, which assisted by the synergistic effect of the three different metals (Au, Pd and Pt). The proposed immunosensor showed satisfied performance such as simple fabrication, low detection limits (0.01 U/mL), wide linear range (from 0.040 to 20 U/mL), short analysis time (2 min), high stability and selectivity in the detection of NMP22. Furthermore, the proposed immunosensor was employed to test real urine samples with satisfactory results. Copyright © 2015 Elsevier B.V. All rights reserved.

  19. Two dimensional visible-light-active Pt-BiOI photoelectrocatalyst for efficient ethanol oxidation reaction in alkaline media

    Science.gov (United States)

    Zhai, Chunyang; Hu, Jiayue; Sun, Mingjuan; Zhu, Mingshan

    2018-02-01

    Two dimensional (2D) BiOI nanoplates were synthesized and used as support for the deposition of Pt nanoparticles. Owing to broad visible light absorption (up to 660 nm), the as-obtained Pt-BiOI electrode was used as effective photoelectrocatalyst in the application of catalytic ethanol oxidation in alkaline media under visible light irradiation. Compared to dark condition, the Pt-BiOI modified electrode displayed 3 times improved catalytic activity towards ethanol oxidation under visible light irradiation. The synergistic effect of electrocatalytic and photocatalytic, and the unique of 2D structures contribute to the improvement of catalytic activity. The mechanism of enhanced photoelectrocatalytic process is proposed. The present results suggest that 2D visible-light-activated BiOI can be served as promising support for the decoration of Pt and applied in the fields of photoelectrochemical and photo-assisted fuel cell applications

  20. Investigating the addition of silicon oxide to carbon: Effects of amount and heat treatment on anti-aggregation and electrochemical performance of Pt catalysts

    Science.gov (United States)

    Wu, Yan-Ni; Liao, Shi-Jun; Zeng, Jian-Huang

    Small nanoparticles offer high surface areas and are certainly desirable for electrocatalytic reactions and fuel cells. However, the drawback of using small nanoparticles is their tendency towards particle aggregation. This paper aims to inhibit platinum agglomeration by adding silicon oxide to a carbon support for enhanced catalytic activity in low-temperature fuel cells. The catalysts are characterized by X-ray diffraction and transmission electron microscopy. Physical characterization and cyclic voltammetry techniques at room temperature are used to assess the effects of silicon oxide amount, post-heating temperature, and holding time on particle size and dispersion of active components, and the catalysts' activity towards the methanol oxidation and oxygen reduction reactions. It is found that using a support of carbon powder with 3 wt.% silicon oxide can enhance the electrochemically active surface area of Pt catalysts and their activity towards the anodic oxidation of methanol and reduction of oxygen. The active components are also more resistant than Pt/C to agglomeration upon heating.

  1. Pt nanoparticles modified by rare earth oxides: Electronic effect and influence to catalytic hydrogenation of 3-phenoxybenzaldehyde

    International Nuclear Information System (INIS)

    Mou, Zhigang; Han, Ming; Li, Gang; Du, Yukou; Yang, Ping; Zhang, Hailu; Deng, Zongwu

    2013-01-01

    Graphical abstract: - Highlights: • The rare earths modified Pt/Al 2 O 3 were prepared by colloidal deposition method. • Modification of Pt by the rare earth enhanced catalytic hydrogenation activity. • The activity improvement is due to electron interaction between Pt and rare earth. • The hydrogenation mechanism of rare earth modified Pt catalyst was proposed. - Abstract: The rare earth elements (La, Ce, Nd, Sm, Pr, and Gd) modified Pt/Al 2 O 3 catalysts were prepared by the colloidal deposition and chemical reduction methods, respectively. Pt nanoparticles with average size 3 ± 0.5 nm were uniformly dispersed on the surface of Al 2 O 3 for the samples prepared by the colloidal deposition method, which exhibited higher activities in the hydrogenation of 3-phenoxybenzadehyde than the corresponding samples prepared by chemical reduction method. Moreover, except Gd, the catalysts modified by rare earth elements showed better catalytic performance than unmodified Pt/Al 2 O 3 . For Pt–Ce/Al 2 O 3 catalyst, when the weight percent of Pt and Ce was 0.5 and 0.25, respectively, the hydrogenation conversion of 3-phenoxybenzaldehyde was 97.3% after 6 h reaction. This activity improvement is due to the electronic interaction between Pt and rare earth elements, which was investigated by X-ray photoelectron spectroscopy

  2. Pt nanoparticles modified by rare earth oxides: Electronic effect and influence to catalytic hydrogenation of 3-phenoxybenzaldehyde

    Energy Technology Data Exchange (ETDEWEB)

    Mou, Zhigang; Han, Ming; Li, Gang; Du, Yukou [College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123 (China); Yang, Ping, E-mail: pyang@suda.edu.cn [College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123 (China); Zhang, Hailu [Suzhou Institute of Nano-tech and Nano-bionics, Chinese Academy of Sciences, Suzhou 215123 (China); Deng, Zongwu, E-mail: zwdeng2007@sinano.ac.cn [Suzhou Institute of Nano-tech and Nano-bionics, Chinese Academy of Sciences, Suzhou 215123 (China)

    2013-11-15

    Graphical abstract: - Highlights: • The rare earths modified Pt/Al{sub 2}O{sub 3} were prepared by colloidal deposition method. • Modification of Pt by the rare earth enhanced catalytic hydrogenation activity. • The activity improvement is due to electron interaction between Pt and rare earth. • The hydrogenation mechanism of rare earth modified Pt catalyst was proposed. - Abstract: The rare earth elements (La, Ce, Nd, Sm, Pr, and Gd) modified Pt/Al{sub 2}O{sub 3} catalysts were prepared by the colloidal deposition and chemical reduction methods, respectively. Pt nanoparticles with average size 3 ± 0.5 nm were uniformly dispersed on the surface of Al{sub 2}O{sub 3} for the samples prepared by the colloidal deposition method, which exhibited higher activities in the hydrogenation of 3-phenoxybenzadehyde than the corresponding samples prepared by chemical reduction method. Moreover, except Gd, the catalysts modified by rare earth elements showed better catalytic performance than unmodified Pt/Al{sub 2}O{sub 3}. For Pt–Ce/Al{sub 2}O{sub 3} catalyst, when the weight percent of Pt and Ce was 0.5 and 0.25, respectively, the hydrogenation conversion of 3-phenoxybenzaldehyde was 97.3% after 6 h reaction. This activity improvement is due to the electronic interaction between Pt and rare earth elements, which was investigated by X-ray photoelectron spectroscopy.

  3. Adsorption and reaction of propanal, 2-propenol and 1-propanol on Ni/Pt(111) bimetallic surfaces

    Science.gov (United States)

    Murillo, Luis E.; Chen, Jingguang G.

    2008-07-01

    The hydrogenation of acrolein (CH 2dbnd CH sbnd CH dbnd O) can lead to the formation of three hydrogenation products, 2-propenol (CH 2dbnd CH sbnd CH 2sbnd OH), propanal (CH 3sbnd CH 2sbnd CH dbnd O), and 1-propanol (CH 3sbnd CH 2sbnd CH 2sbnd OH). In the current study the adsorption and reaction of these three molecules were investigated on Ni/Pt(111) surfaces to understand the different hydrogenation pathways of acrolein, using temperature programmed desorption (TPD) and high resolution electron energy loss spectroscopy (HREELS). TPD experiments showed that 2-propenol underwent isomerization toward propanal on Pt(111) and the Pt sbnd Ni sbnd Pt(111) bimetallic surface, with a dominant decarbonylation pathway on the Pt(111) surface. A self-hydrogenation (disproportionation) pathway toward 1-propanol was observed on the Ni(111) film, however, the decarbonylation pathway was found to be the most dominant on this surface. Unlike 2-propenol, propanal did not undergo isomerization or self-hydrogenation pathways on any of the surfaces, with the dominant pathway being primarily the decarbonylation on Pt(111) and Ni(111). In contrast, 1-propanol underwent mainly molecular desorption from all three surfaces. These results provided additional understanding of previous studies of hydrogenation pathways of acrolein on the Ni/Pt(111) surfaces.

  4. Synthesis of PtSn nanostructured catalysts supported over TiO{sub 2} and Ce-doped TiO{sub 2} particles for the electro-oxidation of ethanol

    Energy Technology Data Exchange (ETDEWEB)

    Alvarez, A.E. [Instituto de Ingeniería Electroquímica y Corrosión (INIEC), CONICET, Universidad Nacional del Sur. Av. Alem 1253, Bahía Blanca B8000CPB (Argentina); Gravina, A.N. [Departamento de Química, INQUISUR, CONICET, Universidad Nacional del Sur, Av. Alem 1253, Bahía Blanca B8000CPB (Argentina); Sieben, J.M., E-mail: jmsieben@uns.edu.ar [Instituto de Ingeniería Electroquímica y Corrosión (INIEC), CONICET, Universidad Nacional del Sur. Av. Alem 1253, Bahía Blanca B8000CPB (Argentina); Messina, P.V. [Departamento de Química, INQUISUR, CONICET, Universidad Nacional del Sur, Av. Alem 1253, Bahía Blanca B8000CPB (Argentina); Duarte, M.M.E. [Instituto de Ingeniería Electroquímica y Corrosión (INIEC), CONICET, Universidad Nacional del Sur. Av. Alem 1253, Bahía Blanca B8000CPB (Argentina)

    2016-09-15

    Highlights: • PtSn particles supported on TiO2 and Ce-doped TiO2 were evaluated as catalysts for EOR. • PtSn/TiO2 showed better mass current and higher TON than PtSn/Ce–TiO2 materials. • The activity for EOR decreased markedly with increasing Ce content in the TiO2. - Abstract: PtSn/TiO2 and PtSn/Ce-doped TiO2 catalysts were synthesized and evaluated for ethanol electro-oxidation in acid media. Titanium dioxide and Ce-doped TiO2 nanoparticles were prepared by hydrothermal method followed by calcination at 923 K. Bimetallic PtSn catalysts supported on the oxide materials were synthesized by microwave assisted reduction in ethylene glycol (EG). The structural properties of the resulting materials were evaluated via TEM and XRD, and the compositions were assessed by EDX and ICP-AES analysis. PtSn nanoparticles of about 3–4 nm were deposited on TiO2 and Ce–TiO2 particles. It was found that the catalyst composition is scarcely influenced by the cerium content in the mixed oxides while the electrochemical surface area per unit mass decreases upon the incorporation of Ce in the anatase lattice. The electrochemical tests pointed out that the electrocatalytic activity for ethanol oxidation decreases markedly as the Ce content increases. The results indicate that the presence of cerium in the titanium dioxide crystalline network induces local structural and electronic modifications, thereby leading to a reduction of the crystallinity, surface conductivity and the amount of OH species adsorbed on the surface of the oxide support.

  5. Methanol electro-oxidation on Pt-Ru-P/C and Pt-Ru-P/MWCNT in acidic medium

    CSIR Research Space (South Africa)

    Modibedi, M

    2009-06-01

    Full Text Available Pt-Ru-P was prepared by the chemical reduction method using sodium hypophoshite as a reducing agent on Vulcan XC 72 and multi-walled carbon nano-tubes (MWCNTs). Sodium citrate was added as the stabilizer during electro-catalyst preparation...

  6. The Effect of Pt Particle Size on the Oxidation of CO, C3H6, and NO Over Pt/Al2O3 for Diesel Exhaust Aftertreatment

    DEFF Research Database (Denmark)

    Hansen, Thomas Klint; Høj, Martin; Hansen, Brian Brun

    2017-01-01

    . Activity measurements for CO, C3H6, and NO oxidation showed an optimal Pt particle size with respect to the mass based activity between 2 and 4 nm for all three reactions. From measured turnover frequencies and site statistics of Pt particles, the reactions appear to be mainly catalyzed by terrace atoms...... for CO, hydrocarbon, and NO oxidation was studied. 1 wt% Pt/Al2O3 catalysts were prepared by wet impregnation, drying, and different calcination and thermal treatments, yielding Pt particles with diameters between 1.3 and 18.7 nm, as determined by CO pulse titration and transmission electron microscopy...

  7. Adsorption and activation of methane and methanol on Pt(100) surface: a density functional study

    International Nuclear Information System (INIS)

    Moussounda, P.S.

    2006-11-01

    The activation of methane (CH 4 ) and methanol (CH 3 OH) on Pt(100) surface has been investigated using density functional theory calculations based on plane-wave basis and pseudo-potential. We optimised CH 4 /Pt(100) system. The calculated adsorption energies over the top, bridge and hollow sites are small, weakly dependent on the molecular orientation. The nature of the CH 4 -Pt interaction was examined through the electronic structure changes. The adsorption of methyl (CH 3 ) and hydrogen (H) and the co-adsorption of CH 3 +H were also calculated. From these results, we examined the dissociation of CH 4 to CH 3 +H, and the activation energies found are in good agreement with the experimental and theoretical values. The activation of CH 3 OH/Pt(100) has been studied. All the sites have almost the same adsorption energy. The adsorption of oxygen (O) and the co-adsorption of CH 4 and O were also examined. In addition, the formation of CH 3 OH assuming a one-step mechanism step via the co-adsorption of CH 4 +O has been studied and the barrier height was found to be high. (authors)

  8. Preservation of the Pt(100) surface reconstruction after growth of a continuous layer of graphene

    DEFF Research Database (Denmark)

    Nilsson, Louis; Andersen, Mie; Bjerre, Jacob

    2012-01-01

    Scanning tunneling microscopy shows that a layer of graphene can be grown on the hex-reconstructed Pt(100) surface and that the reconstruction is preserved after growth. A continuous sheet of graphene can be grown across domain boundaries and step edges without loss of periodicity or change in di...... to accommodation of edge dislocations. The defect formation energy and the induced buckling of the graphene have been characterized by DFT calculations.......Scanning tunneling microscopy shows that a layer of graphene can be grown on the hex-reconstructed Pt(100) surface and that the reconstruction is preserved after growth. A continuous sheet of graphene can be grown across domain boundaries and step edges without loss of periodicity or change...... in direction. Density functional theory calculations on a simple model system support the observation that the graphene can have different rotation angles relative to the hex-reconstructed Pt surface. The graphene sheet direction can be changed by incorporating pentagon-heptagon defects giving rise...

  9. Oxide driven strength evolution of silicon surfaces

    Science.gov (United States)

    Grutzik, Scott J.; Milosevic, Erik; Boyce, Brad L.; Zehnder, Alan T.

    2015-11-01

    Previous experiments have shown a link between oxidation and strength changes in single crystal silicon nanostructures but provided no clues as to the mechanisms leading to this relationship. Using atomic force microscope-based fracture strength experiments, molecular dynamics modeling, and measurement of oxide development with angle resolved x-ray spectroscopy we study the evolution of strength of silicon (111) surfaces as they oxidize and with fully developed oxide layers. We find that strength drops with partial oxidation but recovers when a fully developed oxide is formed and that surfaces intentionally oxidized from the start maintain their high initial strengths. MD simulations show that strength decreases with the height of atomic layer steps on the surface. These results are corroborated by a completely separate line of testing using micro-scale, polysilicon devices, and the slack chain method in which strength recovers over a long period of exposure to the atmosphere. Combining our results with insights from prior experiments we conclude that previously described strength decrease is a result of oxidation induced roughening of an initially flat silicon (1 1 1) surface and that this effect is transient, a result consistent with the observation that surfaces flatten upon full oxidation.

  10. First-principles study on surface reconstruction and magnetic phase stability of an FePt3 film on a Pt(110) substrate

    Science.gov (United States)

    Kim, Hanchul; Kim, Miyoung

    2016-01-01

    The FePt3 alloy is one of the most investigated materials for high density storage applications due to its rich variety of magnetic structures which transform sensitively depending on change in its local structure. Here, we present the ab-initio total energy and electronic structure calculations within the framework of density functional theory for an FePt3 film of 0.5 nm in thickness on a Pt (110) surface. The results show that a missing-row surface reconstruction along the [1overline 1 0] direction is energetically more stable over the unreconstructed clean surface, which is attributed to the energy gain by the spill out of p-electron charge to the large facet area from Pt atoms at the second and third atomic layers. The missing-row reconstruction is found to enhance the stability of the ferromagnetic phase over the antiferromagnetic bulk ground-state phase and to induce possible concurrence of a meta-stable atomic structure with an in-plane anti-phase boundary along the orientation of missing-row in addition to the conventional L12 surface, implying the observation of various magnetic phases.

  11. Localized-Surface-Plasmon Enhanced the 357 nm Forward Emission from ZnMgO Films Capped by Pt Nanoparticles

    Directory of Open Access Journals (Sweden)

    Song XM

    2009-01-01

    Full Text Available Abstract The Pt nanoparticles (NPs, which posses the wider tunable localized-surface-plasmon (LSP energy varying from deep ultraviolet to visible region depending on their morphology, were prepared by annealing Pt thin films with different initial mass-thicknesses. A sixfold enhancement of the 357 nm forward emission of ZnMgO was observed after capping with Pt NPs, which is due to the resonance coupling between the LSP of Pt NPs and the band-gap emission of ZnMgO. The other factors affecting the ultraviolet emission of ZnMgO, such as emission from Pt itself and light multi-scattering at the interface, were also discussed. These results indicate that Pt NPs can be used to enhance the ultraviolet emission through the LSP coupling for various wide band-gap semiconductors.

  12. Electrocatalytic oxidation behavior of NADH at Pt/Fe{sub 3}O{sub 4}/reduced-graphene oxide nanohybrids modified glassy carbon electrode and its determination

    Energy Technology Data Exchange (ETDEWEB)

    Roushani, Mahmoud, E-mail: mahmoudroushani@yahoo.com [Department of Chemistry, Faculty of Sciences, Ilam University, Ilam, 69315516 (Iran, Islamic Republic of); Hoseini, S. Jafar [Department of Chemistry, Faculty of Sciences, Yasouj University, Yasouj, 7591874831 (Iran, Islamic Republic of); Azadpour, Mitra [Department of Chemistry, Faculty of Sciences, Ilam University, Ilam, 69315516 (Iran, Islamic Republic of); Heidari, Vahid; Bahrami, Mehrangiz; Maddahfar, Mahnaz [Department of Chemistry, Faculty of Sciences, Yasouj University, Yasouj, 7591874831 (Iran, Islamic Republic of)

    2016-10-01

    We have developed Pt/Fe{sub 3}O{sub 4}/reduced-graphene oxide nanohybrids modified glassy carbon (Pt/Fe{sub 3}O{sub 4}/RGO/GC) electrode as a novel system for the preparation of electrochemical sensing platform. Characterization of as-made composite was determined using Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), transmission electron microscopy (TEM), atomic force microscopy (AFM) and energy-dispersive analysis of X-ray (EDAX) where the Pt, Fe, Si, O and C elements were observed. The Pt/Fe{sub 3}O{sub 4}/RGO/GC electrode was characterized by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). Due to the synergistic effect between Pt, Fe{sub 3}O{sub 4} and RGO, the nanohybrid exhibited excellent performance toward dihydronicotinamide adenine dinucleotide (NADH) oxidation in 0.1 M phosphate buffer solution, pH 7.0, with a low detection limit of 5 nM. - Highlights: • Preparation of a novel electrochemical sensing platform system • Excellent performance of Pt/Fe{sub 3}O{sub 4}/reduced-graphene oxide nanohybrids • Dihydronicotinamide adenine dinucleotide oxidation with a low detection limit of 5 nM.

  13. Uniform dispersion of 1 : 1 PtRu nanoparticles in ordered mesoporous carbon for improved methanol oxidation.

    Science.gov (United States)

    Li, Fujun; Chan, Kwong-Yu; Yung, Hoi; Yang, Chunzhen; Ting, Siu Wa

    2013-08-28

    PtRu nanoparticles dispersed in CMK3 mesoporous carbons have been prepared via a CPDM (carbonization over poly-furfuryl alcohol-protected dispersed mixed metals) method. The as-synthesized CMK3 supported PtRu nanoparticles are characterized using tomography and cross-sectional TEM analysis and are compared against those synthesized by the conventional ethylene glycol (EG) method. The atomic ratio of Pt : Ru, which has an essential role on methanol oxidation, is found to be consistent at the nanometer scale. The good dispersion and uniform composition of PtRu nanoparticles result in improved methanol oxidation performance including higher methanol oxidation current and long-term stability.

  14. Electrocatalysis of fuel cells reaction on Pt and Pt-bimetallic anode catalysts: A selective review

    Directory of Open Access Journals (Sweden)

    Stamenković Vojislav

    2002-01-01

    Full Text Available In this review we selectively summarize recent progress, primarily from our laboratory, in the development of interrelationships between the kinetics of the fuel cells reactions and the structure/composition of anode catalysts. The focus is placed on two types of metallic surfaces: platinum single crystals and bimetallic surfaces based on Pt. In the first part it was illustrated that the hydcogen reaction is structure sensitive process, with Pt(110 being an order of magnitude more active than either of the atomically "flatter" (100 and (111 surfaces. The hydrogen reaction on Pt(hkl modified by pseudomorphic Pd (submonolayers shows the "volcano-like" behavior, having the maximum rate on Pt(111 modified by 1 ML of Pd. The Pt(111-Pd system is used to demonstrate how the energetics of intermediates formed in the hydrogen reaction is affected by interfacial bonding and energetic constraints produced between pseudomorphic Pd films and the Pt(111 substrate. In the second part it was shown that the oxidation of Ha in the presence of CO occurs concurrently with CO oxidation on Pt and Pt bimetallic surfaces. The Pt-Ru system is used to demonstrate that both the bifunctional effect and the ligand effect contribute to the influence of Ru on the CO oxidation rate and for Hz oxidation process in the presence of CO. The knowledge is then used to create the real-life catalyst with the catalytic activities which are, to the greatest extend possible similar to the tailor-made surface.

  15. High Temperature Oxidation Behavior of gamma-Ni+gamma'-Ni3Al Alloys and Coatings Modified with Pt and Reactive Elements

    Energy Technology Data Exchange (ETDEWEB)

    Mu, Nan [Iowa State Univ., Ames, IA (United States)

    2007-12-01

    Materials for high-pressure turbine blades must be able to operate in the high-temperature gases (above 1000 C) emerging from the combustion chamber. Accordingly, the development of nickel-based superalloys has been constantly motivated by the need to have improved engine efficiency, reliability and service lifetime under the harsh conditions imposed by the turbine environment. However, the melting point of nickel (1455 C) provides a natural ceiling for the temperature capability of nickel-based superalloys. Thus, surface-engineered turbine components with modified diffusion coatings and overlay coatings are used. Theses coatings are capable of forming a compact and adherent oxide scale, which greatly impedes the further transport of reactants between the high-temperature gases and the underlying metal and thus reducing attack by the atmosphere. Typically, these coatings contain β-NiAl as a principal constituent phase in order to have sufficient aluminum content to form an Al2O3 scale at elevated temperatures. The drawbacks to the currently-used {beta}-based coatings, such as phase instabilities, associated stresses induced by such phase instabilities, and extensive coating/substrate interdiffusion, are major motivations in this study to seek next-generation coatings. The high-temperature oxidation resistance of novel Pt + Hf-modified γ-Ni + γ-Ni3Al-based alloys and coatings were investigated in this study. Both early-stage and 4-days isothermal oxidation behavior of single-phase γ-Ni and γ'-Ni3Al alloys were assessed by examining the weight changes, oxide-scale structures, and elemental concentration profiles through the scales and subsurface alloy regions. It was found that Pt promotes Al2O3 formation by suppressing the NiO growth on both γ-Ni and γ'Ni3Al single-phase alloys. This effect increases with increasing Pt content. Moreover, Pt exhibits this effect even at

  16. Chemisorption of (CHx and C2Hy) hydrocarbons on Pt(111) clusters and surfaces from DFT studies.

    Science.gov (United States)

    Jacob, Timo; Goddard, William A

    2005-01-13

    We used the B3LYP flavor of density functional theory (DFT) to study the chemisorption of all CH(x) and C(2)H(y) intermediates on the Pt(111) surface. The surface was modeled with the 35 atom Pt(14.13.8) cluster, which was found to be reliable for describing all adsorption sites. We find that these hydrocarbons all bind covalently (sigma-bonds) to the surface, in agreement with the studies by Kua and Goddard on small Pt clusters. In nearly every case the structure of the adsorbed hydrocarbon achieves a saturated configuration in which each C is almost tetrahedral with the missing H atoms replaced by covalent bonds to the surface Pt atoms. Thus, (Pt(3))CH prefers a mu(3) hollow site (fcc), (Pt(2))CH(2) prefers a mu(2) bridge site, and PtCH(3) prefers mu(1) on-top sites. Vinyl leads to (Pt(2))CH-CH(2)(Pt), which prefers a mu(3) hollow site (fcc). The only exceptions to this model are ethynyl (CCH), which binds as (Pt(2))C=CH(Pt), retaining a CC pi-bond while binding at a mu(3) hollow site (fcc), and HCCH, which binds as (Pt)HC=CH(Pt), retaining a pi bond that coordinates to a third atom of a mu(3) hollow site (fcc) to form an off center structure. These structures are in good agreement with available experimental data. For all species we calculated heats of formation (DeltaH(f)) to be used for considering various reaction pathways on Pt(111). For conditions of low coverage, the most strongly bound CH(x) species is methylidyne (CH, BE = 146.61 kcal/mol), and ethylidyne (CCH(3), BE = 134.83 kcal/mol) among the C(2)H(y) molecules. We find that the net bond energy is nearly proportional to the number of C-Pt bonds (48.80 kcal/mol per bond) with the average bond energy decreasing slightly with the number of C ligands.

  17. Effect of local metal microstructure on adsorption on bimetallic surfaces: Atomic nitrogen on Ni/Pt(111)

    Science.gov (United States)

    Guo, Wei; Vlachos, Dionisios G.

    2013-05-01

    The adsorption of atomic nitrogen on Ni/Pt(111) surface bimetallics has been investigated as a function of the local microstructure of Ni and Pt atoms via density functional theory (DFT) calculations. Microstructures include surface and subsurface Ni atoms on Pt(111) as limiting cases, and also small clusters of Ni in the first and/or second layer of Pt. It is shown that the binding energy of N can be approximated as a perturbation from that on the host metal (Pt) with a linear short-ranged correction from the guest metal (Ni) that accounts for the coordination environment of nitrogen up to the 3rd nearest Ni neighbor. This model is rationalized with the d-band center theory. Coverage effects are also included. The model can be parameterized with a limited number of DFT calculations and applied to other bimetallic catalysts to estimate the coverage dependent binding energy on complex metal microstructures.

  18. 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.

  19. First principles investigation of the activity of thin film Pt, Pd and Au surface alloys for oxygen reduction

    DEFF Research Database (Denmark)

    Tripkovic, Vladimir; Hansen, Heine Anton; Rossmeisl, Jan

    2015-01-01

    driving force for surface segregation, diffusion to defects or surface self-assembling. On the basis of stability and activity analysis we conclude that the near surface alloy of Pd in Pt and some PdAu binary and PtPdAu ternary thin films with a controlled amount of Au are the best catalysts for oxygen......Further advances in fuel cell technologies are hampered by kinetic limitations associated with the sluggish cathodic oxygen reduction reaction. We have investigated a range of different formulations of binary and ternary Pt, Pd and Au thin films as electrocatalysts for oxygen reduction. The most...... active binary thin films are near-surface alloys of Pt with subsurface Pd and certain PdAu and PtAu thin films with surface and/or subsurface Au. The most active ternary thin films are with pure metal Pt or Pd skins with some degree of Au in the surface and/or subsurface layer and the near-surface alloys...

  20. CO oxidation on PdO surfaces

    DEFF Research Database (Denmark)

    Hirvi, Janne T.; Kinnunen, Toni-Jani J.; Suvanto, Mika

    2010-01-01

    Density functional calculations were performed in order to investigate CO oxidation on two of the most stable bulk PdO surfaces. The most stable PdO(100) surface, with oxygen excess, is inert against CO adsorption, whereas strong adsorption on the stoichiometric PdO(101) surface leads to favorable...... oxidation via the Langmuir–Hinshelwood mechanism. The reaction with a surface oxygen atom has an activation energy of 0.66 eV, which is comparable to the lowest activation energies observed on metallic surfaces. However, the reaction rate may be limited by the coverage of molecular oxygen. Actually...... adsorption, following the Eley–Rideal mechanism and taking advantage of the reaction tunnel provided by the adjacent palladium atom, has an activation energy of only 0.24 eV. The reaction mechanism and activation energy for the palladium activated CO oxidation on the most stable PdO(100)–O surface...

  1. A study on H{sub 2}-TPR of Pt/Ce{sub 0.27}Zr{sub 0.73}O{sub 2} and Pt/Ce{sub 0.27}Zr{sub 0.70}La{sub 0.03}O{sub x} for soot oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Hailong [College of Chemical Engineering, Sichuan University, Chengdu 610064 (China); Wang, Jianli; Zhang, Yanhua [College of Chemistry, Sichuan University, Chengdu 610064 (China); Jiao, Yi [Xi’an Modern Chemistry Research Institute, Xi’an 710065 (China); Ren, Chengjun; Gong, Maochu [College of Chemistry, Sichuan University, Chengdu 610064 (China); Chen, Yaoqiang, E-mail: nic7501@scu.edu.cn [College of Chemical Engineering, Sichuan University, Chengdu 610064 (China); College of Chemistry, Sichuan University, Chengdu 610064 (China); Sichuan Provincial Vehicular Exhaust Gases Abatement Engineering Technology Center, Chengdu 610064 (China); Sichuan Provincial Environmental Catalytic Material Engineering Technology Center, Chengdu 610064 (China)

    2016-07-30

    Highlights: • The H{sub 2} consumption of the catalyst increases after aging. • The availability of surface lattice oxygen could be improved after aging. • Sintering and encapsulation of Pt weaken H{sub 2} spillover mechanism. • Soot oxidation activity is closely related to reduction temperature. - Abstract: Pt/Ce{sub 0.27}Zr{sub 0.73}O{sub 2} and Pt/Ce{sub 0.27}Zr{sub 0.70}La{sub 0.03}O{sub x} catalysts, prepared by co-precipitation and impregnation methods, were thermally treated at different temperatures for 10 h and then characterized by X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET), X-ray photoelectron spectroscopy (XPS), H{sub 2} temperature-programmed reduction (H{sub 2}-TPR), thermogravimetric analysis (TGA) and soot temperature-programmed oxidation (soot-TPO). Due to thermal effect on the structural and textural properties, the aged catalysts show increased reduction temperatures. But, interestingly, more H{sub 2} consumption is detected, which would be ascribed to the increased mobility of bulk oxygen and surface lattice oxygen. The promoting and synergistic roles of Pt in H{sub 2}-TPR are discussed and it reveals that the sintering and encapsulation of Pt would weaken the H{sub 2} spillover mechanism and the addition of La is beneficial to stabilize the synergistic effect between Pt and Ce. On the other hand, a humble role of Pt on promoting soot oxidation activity is found in this study. Not all oxygen species available in H{sub 2}-TPR can be used for soot oxidation. The deactivation of the aged catalysts is closely related to the reduction temperature.

  2. Metal nanostructures with complex surface morphology: The case of supported lumpy Pd and Pt nanoparticles produced by laser processing of metal films

    Science.gov (United States)

    Ruffino, F.; Maugeri, P.; Cacciato, G.; Zimbone, M.; Grimaldi, M. G.

    2016-09-01

    In this work we report on the formation of lumpy Pd and Pt nanoparticles on fluorine-doped tin oxide/glass (FTO/glass) substrate by a laser-based approach. In general, complex-surface morphology metal nanoparticles can be used in several technological applications exploiting the peculiarities of their physical properties as modulated by nanoscale morphology. For example plasmonic metal nanoparticles presenting a lumpy morphology (i.e. larger particles coated on the surface by smaller particles) can be used in plasmonic solar cell devices providing broadband scattering enhancement over the smooth nanoparticles leading, so, to the increase of the device efficiency. However, the use of plasmonic lumpy nanoparticles remains largely unexplored due to the lack of simply, versatile, low-cost and high-throughput methods for the controllable production of such nanostructures. Starting from these considerations, we report on the observation that nanoscale-thick Pd and Pt films (17.6 and 27.9 nm, 12.1 and 19.5 nm, respectively) deposited on FTO/glass surface irradiated by nanosecond pulsed laser at fluences E in the 0.5-1.5 J/cm2 range, produce Pd and Pt lumpy nanoparticles on the FTO surface. In addition, using scanning electron microscopy analyses, we report on the observation that starting from each metal film of fixed thickness h, the fraction F of lumpy nanoparticles increases with the laser fluence E and saturates at the higher fluences. For each fixed fluence, F was found higher starting from the Pt films (at each starting film thickness h) with respect to the Pd films. For each fixed metal and fluence, F was found to be higher decreasing the starting thickness of the deposited film. To explain the formation of the lumpy Pd and Pt nanoparticles and the behavior of F as a function of E and h both for Pd and Pt, the thermodynamic behavior of the Pd and Pt films and nanoparticles due to the interaction with the nanosecond laser is discussed. In particular, the

  3. Oxygen surface exchange and oxidative dehydrogenation on oxide ion conductors

    NARCIS (Netherlands)

    Song, C.

    2012-01-01

    The research described in this thesis mainly aims at investigation of the rate of oxygen exchange at the surface of oxide ion conductors. The introduction is given in Chapter 1. A fast and simple method, referred to as pulse 18O-16O isotopic exchange (PIE), for measurement of the rate of surface

  4. Characterization of azo dyes on Pt and Pt/polyaniline/dispersed Pt electrodes

    International Nuclear Information System (INIS)

    Molina, J.; Fernández, J.; Río, A.I. del; Bonastre, J.; Cases, F.

    2012-01-01

    The electrochemical characterization of two organic dyes (amaranth and procion orange MX-2R) has been performed on Pt electrodes and Pt electrodes coated with polyaniline and dispersed Pt. Electrodes with different Pt loads have been synthesized and characterized obtaining that a load of 300 μg cm -2 was the optimum one. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) was employed to observe the distribution and morphology of the Pt nanoparticles. The electroactivity of the electrodes has also been characterized by means of scanning electrochemical microscopy (SECM). The chemical characterization of Pt dispersed Pani coated Pt electrodes (Pt-Pani-Pt) was performed by means of X-ray photoelectron spectroscopy (XPS). The electrochemical characterization of the dyes has been performed by means of cyclic voltammetry. Voltammograms have shown that the presence of the dyes diminishes characteristic Pt oxidation and reduction peaks. However, redox processes due to the dyes, appeared in the voltammograms. The different species responsible of these redox processes were generated in the vicinity of the electrode and were not adsorbed on the electrode surface since after stirring, the different redox processes disappeared. Characterization with different scan rates showed that redox processes of both dyes were controlled by diffusion.

  5. Oxidation Kinetics of a NiPtTi High Temperature Shape Memory Alloy

    Science.gov (United States)

    Smialek, James L.; Humphrey, Donald L.; Noebe, Ronald D.

    2007-01-01

    A high temperature shape memory alloy (HTSMA), Ni30Pt50Ti, with an M(sub s) near 600 C, was isothermally oxidized in air for 100 hr over the temperature range of 500 to 900 C. Parabolic kinetics were confirmed by log-log and parabolic plots and showed no indication of fast transient oxidation. The overall behavior could be best described by the Arrhenius relationship: k(sub p) = 1.64 x 10(exp 12)[(-250 kJ/mole)/RT] mg(sup 2)/cm(sup 4)hr. This is about a factor of 4 reduction compared to values measured here for a binary Ni47Ti commercial SMA. The activation energy agreed with most literature values for TiO2 scale growth measured for elemental Ti and other NiTi alloys. Assuming uniform alloy depletion of a 20 mil (0.5 mm) dia. HTSMA wire, approx. 1 percent Ti reduction is predicted after 20,000 hr oxidation at 500 C, but becomes much more serious at higher temperatures.

  6. Reduced and oxidized forms of the Pt-organometallic version of polyaniline.

    Science.gov (United States)

    Kenny, Tommy; Lamare, Simon; Aly, Shawkat M; Fortin, Daniel; Brisard, Gessie; Harvey, Pierre D

    2012-12-17

    )H(4)-N═C(6)X(4)═N-C(6)H(4)C≡C-PtL(2))(n) polymers, the completely oxidized form for X = H was isolated (pernigraniline), but for X = F and Cl, only the largely reduced mixed-valence form (i.e., emaraldine) was obtained via chemical routes. In acidic solutions, the chemically accessible polymer for X = H, (C≡CC(6)H(4)-N═C(6)H(4)═N-C(6)H(4)C≡C-PtL(2))(n), exhibits two chemically reversible waves indicating that the reduced form (C≡CC(6)H(4)NH-C(6)H(4)-NHC(6)H(4)C≡C-PtL(2))(n) can be generated. The absorption spectra of the highly colored diimine-containing species exhibit a broad charge transfer band (assigned based on DFT calculations (B3LYP); C(6)H(4)C≡C-PtL(2)-C≡CC(6)H(4) → N═C(6)X(4)═N) in the 450-800 nm window red shifting according X = H → Cl → F, consistent with their relative inductive effect. The largest absorptivity is measured for X = H because this polymer is fully oxidized whereas for the cases where X = F and Cl, these polymers exists in the mixed valence form. The ns transient absorption spectra of two polymers (X = F; reduced and mixed-valence polymers) were measured. The triplet excited state in the mixed-valence polymer is dominated by the reduced diamine residue and the T(1)-T(n) absorption of the diimine is entirely quenched.

  7. Surface self-diffusion of adatom on Pt cluster with truncated octahedron structure

    Energy Technology Data Exchange (ETDEWEB)

    Yang Jianyu, E-mail: wuliyangjianyu@yahoo.com.c [Department of Maths and Physics, Hunan Institute of Engineering, Xiangtan 411104 (China); Hu Wangyu, E-mail: wangyuhu2001@yahoo.com.c [Department of Applied Physics, Hunan University, Changsha 410082 (China); Chen Shuguang [Department of Applied Physics, Hunan University, Changsha 410082 (China)

    2010-05-03

    Surface diffusion of single Pt adatom on Pt cluster with truncated octahedron structure is investigated through a combination of molecular dynamics and nudged elastic band method. Using an embedded atom method to describe the atomic interactions, the minimum energy paths are determined and the energy barriers for adatom diffusion across and along step are evaluated. The diffusion of adatom crossing step edge between {l_brace}111{r_brace} and {l_brace}100{r_brace} facets has a surprisingly low barrier of 0.03 eV, which is 0.12 eV lower than the barrier for adatom diffusion from {l_brace}111{r_brace} to neighboring {l_brace}111{r_brace} facet. Owing to the small barrier of adatom diffusion across the step edge between {l_brace}111{r_brace} and {l_brace}100{r_brace} facets, the diffusion of adatom along the step edge cannot occur. The molecular dynamics simulations at low temperatures also support these results. Our results show that mass transport will prefer step with {l_brace}100{r_brace} microfacet and the Pt clusters can have only {l_brace}111{r_brace} facets in epitaxial growth.

  8. 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.

  9. Surface structure of MgO underlayer with Ti diffusion for (002) oriented L10 FePt-based heat assisted magnetic recording media

    Science.gov (United States)

    Hinata, Sintaro; Jo, Shin; Saito, Shin

    2018-05-01

    Surface morphology of the MgO layer and magnetic properties of FePt-C layer deposited on the MgO were investigated for the FePt-based heat assisted magnetic recording media. Stacking structure of the underlayer for the FePt-C layer was MgO (0-5 nm)/Cr80Mn20 (0-30 nm)/Cr50Ti50 (0-50 nm)/glass sub.. Surface observation result for the MgO film by using an atomic force microscope revealed the existence of nodules with a height of about 2 nm and a network-like convex structure with a height difference of about sub nm (boundary wall, BW) on the MgO crystal grain boundary. Density of the nodules largely depends on the surface roughness of the CrTi layer, RaCrTi and it is suppressed from 10 to 2/0.5 μm2 by reducing RaCrTi from 420 to 260 pm. Height of the BW depends on thickness of the MgO layer, tMgO and it can be suppressed by reducing tMgO to less than 4 nm. From the cross-sectional energy dispersive x-ray mapping, it is clarified that the BW is formed by atomic diffusion of Ti atoms from CrTi layer due to the substrate heating process, and a compound consists of Mg, Ti and O atoms. This BW can be used as a template to magnetically isolate the FePt column in the FePt-based granular film, such as FePt-SiO2, if the size of the BW is reduced to less than 10 nm. M-H loop of the FePt-C granular film deposited on the underlayer showed that the nodule and BW induce oxidation of the FePt grains, and reduction of intergranular exchange coupling.

  10. One-step flame synthesis of an active Pt/TiO2 catalyst for SO2 oxidation

    DEFF Research Database (Denmark)

    Johannessen, Tue; Koutsopoulos, Sotiris

    2002-01-01

    Flame synthesis as a route for production of composite metal oxides has been employed for the one-step synthesis of a supported noble metal catalyst, i.e. a Pt/TiO2 catalyst, by simultaneous combustion of Ti-isopropoxide and platinum acetylacetonate in a quench-cooled flame reactor. The average...

  11. Electrochemical oxidation of carbon monoxide: from platinum single crystals to low temperature fuel catalysts. Part II: Electrooxidation of H2, CO and H2/CO mixtures on well characterized PtMo alloy

    Directory of Open Access Journals (Sweden)

    PHILIP N. ROSS JR.

    2003-03-01

    Full Text Available The oxidation of hydrogen and hydrogen–carbon monoxide mixture has been investigated on well-characterized metallurgically prepared platinum–molybdenum (PtMo alloys. It was concluded that the optimum surface concentration of molybdenum is near 23 mol.%. Based on experimentally determined parameters and simulations, the mechanism of the oxidation of CO/H2 mixtures is discussed.

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

    Directory of Open Access Journals (Sweden)

    Md Faruk Hossain

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

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

    Science.gov (United States)

    Hossain, Md Faruk; Park, Jae Y

    2017-01-01

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

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

    Science.gov (United States)

    Zhang, Yan; Wang, Yanhui; Bian, Linyan; Lu, Rui; Zang, Jianbing

    2016-02-01

    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. Sp3-bonded ND possesses high electrochemical stability but low conductivity, while sp2-bonded carbon nanomaterials with high conductivity are prone to oxidation. Therefore, the functions of the supporting material were separated in this study. ND (sp3), as a support, and AB or CNTs (sp2), 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.

  15. Influence of deuterium on kinetics of methane isotope exchange with surface deuteroxy groups of Pt/SiO2 catalysts

    International Nuclear Information System (INIS)

    Musoyan, L.M.; Aliev, R.K.

    1990-01-01

    Reaction of isotope methane exchange with surface deuteroxy groups of 2 % Pt/SiO 2 catalyst was studied. It is shown that preliminarily chemisorbed deuterium does not decelerate the exchange reaction, but changes its mechanism. Activation energy of exchange on clean surface is equal to 25 kJ/mol; it grows in the presence of deuterium on the surface

  16. A solvent approach to the size-controllable synthesis of ultrafine Pt catalysts for methanol oxidation in direct methanol fuel cells

    International Nuclear Information System (INIS)

    Ye, Feng; Liu, Hui; Feng, Yan; Li, Jianling; Wang, Xindong; Yang, Jun

    2014-01-01

    Graphical abstract: - Highlights: • An ethylene glycol-based approach for the synthesis of Pt/C catalysts with uniform Pt nanoparticles. • Superior catalytic activity of Pt/C catalysts synthesized at EG/water volume ratio of 1/1 for methanol oxidation reaction. • High performance of MEA for DMFC using Pt/C catalysts synthesized at EG/water volume ratio of 1/1 at anode. - Abstract: An ethylene glycol (EG)-based approach has been developed for the synthesis of Pt/C catalysts with uniform Pt nanoparticles. A number of characterization techniques, including scanning electron microscopy (SEM), transmission electron microscopy (TEM), and electrochemical measurements are used to characterize the as-prepared Pt catalysts. The well-dispersed Pt nanoparticles with average size of approximate 2 nm could be obtained in the EG/water mixture with volume ratio of 1/1, which display higher activity for methanol oxidation than that of the Pt/C products prepared at other EG/water volume ratios (0:1, 2:1, and 1:0). In particular, the performance of the Pt nanoparticles prepared at EG/water volume ratio of 1/1 in the membrane electrode assembly for direct methanol fuel cells has also been evaluated and benchmarked by commercial Pt/C catalysts. This study offers a vivid example to synthesize Pt nanoparticles with fine size and good catalytic activity by simply tuning the solvent ratio in colloidal chemistry methods

  17. Fabrication of superhydrophobic Pt3Fe/Fe surface for its application

    Science.gov (United States)

    Cui, Shuo; Lu, Shixiang; Xu, Wenguo; Wu, Bei

    2017-10-01

    Well-defined Pt3Fe/Fe superhydrophobic materials on iron sheet with special properties, such as corrosion resistance, superhydrophobicity and superoleophilicity, was fabricated. The fabrication process involved etching in hydrochloric acid aqueous solution and simple replacement deposition process without using any seed and organic solvent, and then annealing. The electrochemical measurements show that the resultant surface in 3.5% sodium chloride solution displays good corrosion resistance. Also, it is proved that the obtained surface has better mechanical abrasion resistance via scratch test. The superoleophilicity and low water adhesion force of the obtained surface endow it high oil/water separation capacity. The as-prepared nanocomposites display enhanced catalytic activity and kinetics toward degradation of methyl orange. In particular, it possesses the most efficient degradation capacity (95%) towards methyl orange at a high concentration (17.5 mg/L) in 80 min. The improved stability and excellent catalytic activity of the Pt3Fe/Fe nanocomposites promise new opportunities for the development of waste water treatment.

  18. Sputter deposition on gas diffusion electrodes of Pt-Au nanoclusters for methanol oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Giorgi, L.; Giorgi, R.; Gagliardi, S.; Serra, E. [ENEA Casaccia Research Center, Rome (Italy). Physics Technologies and New Materials; Alvisi, M.; Signore, M.A. [ENEA Brindisi Research Center, Brindisi (Italy). Physics Technologies and New Materials

    2008-07-01

    Polymer electrolyte fuel cells (PEFCs) are suited for use in commercial electrical vehicle and electric power applications. The gas diffusion electrodes of PEFCs are catalyzed by the deposition of platinum (Pt) nanoparticles on carbon powder. The particles must be localized on the electrode surface in order to achieve high electrocatalyst utilization. This study discussed a method of preparing PEFC electrodes using sputter deposition of a Pt-gold (Au) alloy nanoparticles on carbon powders. The method was designed to improve electrode performance and catalyst utilization. The nano-sized alloy clusters were deposited on a gas diffusion electrode at room temperature. The deposits were then characterized using field emission scanning electron microscopy (FE-SEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) in order to examine the effect of the deposition technique on the nano-morphology and electrocatalytic performance of the electrode. Results of the study showed that the technique can be used in the large-scale manufacture of fuel cell electrodes. 3 refs., 1 fig.

  19. Azo dyes degradation using TiO2-Pt/graphene oxide and TiO2-Pt/reduced graphene oxide photocatalysts under UV and natural sunlight irradiation

    Science.gov (United States)

    Rosu, Marcela-Corina; Coros, Maria; Pogacean, Florina; Magerusan, Lidia; Socaci, Crina; Turza, Alexandru; Pruneanu, Stela

    2017-08-01

    The photocatalytic degradation of azo dyes with different structures (amaranth, sunset yellow and tartrazine) using TiO2-Pt nanoparticles (TPt), TiO2-Pt/graphene oxide (TPt-GO) and TiO2-Pt/reduced graphene oxide (TPt-rGO) composites were investigated in the presence of UV and natural sunlight irradiation. The composites were prepared by a combined chemical-thermal method and characterized by Transmission Electron Microscopy (TEM), X-ray powder diffraction (XRD), Infrared (FTIR) and UV-Vis spectroscopy. The modification of TiO2-Pt with graphene oxide shifted its optical absorption edge towards the visible region and increased its photocatalytic activity under UV and natural sunlight irradiation. The efficiency of catalysts on azo dyes degradation (in similar conditions) reached high values (above 99%) under sunlight conditions, proving the remarkable photocatalytic activities of obtained composites. TPt-GO nanocomposite exhibited higher photoactivity than TPt or TPt-rGO, demonstrating degradation efficiencies of 99.56% for amaranth, 99.15% for sunset yellow and 96.23% for tartrazine. The dye photodegradation process follows a pseudo-first-order kinetic with respect to the Langmuir-Hinshelwood reaction mechanism. A direct dependence between azo dyes degradation rate and chemical structure of dyes has been observed.

  20. Preparation and Catalytic Activity for Aerobic Glucose Oxidation of Crown Jewel Structured Pt/Au Bimetallic Nanoclusters

    Science.gov (United States)

    Zhang, Haijun; Wang, Liqiong; Lu, Lilin; Toshima, Naoki

    2016-08-01

    Understanding of the “structure-activity” relations for catalysts at an atomic level has been regarded as one of the most important objectives in catalysis studies. Bimetallic nanoclusters (NCs) in its many types, such as core/shell, random alloy, cluster-in-cluster, bi-hemisphere, and crown jewel (one kind of atom locating at the top position of another kind of NC), attract significant attention owing to their excellent optical, electronic, and catalytic properties. PVP-protected crown jewel-structured Pt/Au (CJ-Pt/Au) bimetallic nanoclusters (BNCs) with Au atoms located at active top sites were synthesized via a replacement reaction using 1.4-nm Pt NCs as mother clusters even considering the fact that the replacement reaction between Pt and Au3+ ions is difficult to be occurred. The prepared CJ-Pt/Au colloidal catalysts characterized by UV-Vis, TEM, HR-TEM and HAADF-STEM-EELS showed a high catalytic activity for aerobic glucose oxidation, and the top Au atoms decorating the Pt NCs were about 15 times more active than the Au atoms of Au NCs with similar particle size.

  1. Photocatalytic Ethanol Oxidative Dehydrogenation over Pt/TiO2: Effect of the Addition of Blue Phosphors

    Directory of Open Access Journals (Sweden)

    J. J. Murcia

    2012-01-01

    Full Text Available Ethanol oxidative dehydrogenation over Pt/TiO2 photocatalyst, in the presence and absence of blue phosphors, was performed. The catalyst was prepared by photodeposition of Pt on sulphated TiO2. This material was tested in a gas-solid photocatalytic fluidized bed reactor at high illumination efficiency. The effect of the addition of blue phosphors into the fluidized bed has been evaluated. The synthesized catalysts were extensively characterized by different techniques. Pt/TiO2 with a loading of 0.5 wt% of Pt appeared to be an active photocatalyst in the selective partial oxidation of ethanol to acetaldehyde improving its activity and selectivity compared to pure TiO2. In the same way, a notable enhancement of ethanol conversion in the presence of the blue phosphors has been obtained. The blue phosphors produced an increase in the level of ethanol conversion over the Pt/TiO2 catalyst, keeping at the same time the high selectivity to acetaldehyde.

  2. Platinum-coated gold nanoporous film surface: electrodeposition and enhanced electrocatalytic activity for methanol oxidation.

    Science.gov (United States)

    Jia, Jianbo; Cao, Linyuan; Wang, Zhenhui

    2008-06-03

    This report describes the preparation of Pt-nanoparticle-coated gold-nanoporous film (PGNF) on a gold substrate via a simple "green" approach. The gold electrode that has been anodized under a high potential of 5 V is reduced by freshly prepared ascorbic acid (AA) solution to obtain gold nanoporous film electrode. Then the Pt nanoparticle is grown on the electrode by cyclic voltammetry (CV). The resulting PGNF electrode has highly ordered arrangement and large surface area, as verified by scanning electron microscopy (SEM) and CV, suggesting that the nanoporous gold film electrode provides a good matrix for obtaining PGNF with high surface area. Furthermore, the as-prepared PGNF electrode exhibited high electrocatalytic activity toward methanol oxidation in a 0.5 M H 2SO 4 solution containing 1.5 M methanol. The present novel strategy is expected to reduce the cost of the Pt catalyst remarkably.

  3. Preparation of PtSnSb/C electrocatalizers for the electro-oxidation of the ethanol; Preparacao de eletrocatalizadores PtSnSb/C para a eletrooxidacao do etanol

    Energy Technology Data Exchange (ETDEWEB)

    Tusi, M.M.; Ayoub, J.M.S.; Costa, T.C.; Spinace, E.V.; Neto, A.O., 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

    PtSn/C (Pt:Sn atomic ratio of 50:50) and PtSnSb/C (Pt:Sn:Sb atomic ratio of 50:45:05, 50:40:10 and 50:10:40) electrocatalysts were prepared (20 wt% metal loading) by an alcohol-reduction process using ethylene glycol as reducing agent, H{sub 2}PtCl{sub 6}.6H{sub 2}O, SnCl{sub 2}.H{sub 2}O and Sb(OOCCH{sub 3}){sub 3} and carbon Vulcan XC72 as support. The obtained materials were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and chronoamperometry. The PtSnSb/C (50:45:05) prepared by an alcohol-reduction process showed the best performance for ethanol electro-oxidation compared to the others catalysts. (author)

  4. Hollow Au@Pd and Au@Pt core-shell nanoparticles as electrocatalysts for ethanol oxidation reactions

    KAUST Repository

    Song, Hyon Min

    2012-09-27

    Hybrid alloys among gold, palladium and platinum become a new category of catalysts primarily due to their enhanced catalytic effects. Enhancement means not only their effectiveness, but also their uniqueness as catalysts for the reactions that individual metals may not catalyze. Here, preparation of hollow Au@Pd and Au@Pt core-shell nanoparticles (NPs) and their use as electrocatalysts are reported. Galvanic displacement with Ag NPs is used to obtain hollow NPs, and higher reduction potential of Au compared to Ag, Pd, and Pt helps to produce hollow Au cores first, followed by Pd or Pt shell growth. Continuous and highly crystalline shell growth was observed in Au@Pd core-shell NPs, but the sporadic and porous-like structure was observed in Au@Pt core-shell NPs. Along with hollow core-shell NPs, hollow porous Pt and hollow Au NPs are also prepared from Ag seed NPs. Twin boundaries which are typically observed in large size (>20 nm) Au NPs were not observed in hollow Au NPs. This absence is believed to be due to the role of the hollows, which significantly reduce the strain energy of edges where the two lattice planes meet. In ethanol oxidation reactions in alkaline medium, hollow Au@Pd core-shell NPs show highest current density in forward scan. Hollow Au@Pt core-shell NPs maintain better catalytic activities than metallic Pt, which is thought to be due to the better crystallinity of Pt shells as well as the alloy effect of Au cores. © 2012 The Royal Society of Chemistry.

  5. Ionic-liquid-assisted synthesis of core-shell RuNi@Pt nanoparticles on multiwall carbon nanotubes for methanol oxidation

    Science.gov (United States)

    Kakati, Nitul; Yoon, Young Soo

    2016-01-01

    Core-shell RuNi@Pt nanoparticles were synthesized on multiwall carbon nanotubes by using an ionic-liquid-assisted polyol synthesis method. The catalysts were characterized by using transmission electron microscopy. The synthesized catalysts were very active towards electrocatalytic oxidation of methanol. The catalytic activities were found to increase with decreasing Pt content on the shells of the nanoparticles. The electrocatalytic activities of the RuNi@Pt/MWCNTs were higher than those of PtRuNi/MWCNTs with higher amounts of Pt.

  6. Analysis of oxide formed on Ti during exposure in bentonite clay. Pt. 2

    International Nuclear Information System (INIS)

    Mattsson, H.; Li Changhai; Olefjord, I.

    1990-01-01

    Titanium owes its excellent corrosion properties due to a passive oxide layer on its surface. In a long term perspective a change of the oxide structure may influence these properties. This is an important question when titanium is used as an overpack material for storage of spent nuclear fuel. The structure of the oxide formed on titanium during exposure in ground-water saturated bentonite clay at 95deg C up to six years is reported. The initially formed oxide is amorphous. Exposures for 3 to 6 years causes crystallization of the oxide. The microcrystals (rutile) are about 50-100 A and coexist with the amorphous phase. The crystallinity increases with exposure time. The reason for crystallization is a driving force toward the thermodynamically most stable state. A consequence of the crystallization is an increasing oxidation rate where the grain-boundaries provide a short diffusion path for the ions. A dedicated investigation of the influence of the sample preparation technique and the electron beam irradiation was performed since it was feared that these could create structural artifacts. These experiments showed that it was possible to analyze the true structure of titanium oxides if certain precautions were taken. (orig.) [de

  7. Negative resistance for methanol electro-oxidation on platinum/carbon (Pt/C) catalyst investigated by an electrochemical impedance spectroscopy

    Science.gov (United States)

    Cai, Guang-Xu; Guo, Jian-Wei; Wang, Jia; Li, Song

    2015-02-01

    The poisoning of Pt-based catalyst occurs generally during methanol electro-oxidation. Though traditional electrochemical techniques have probed these issues intensively, it is amazing to find that the negative resistance presents in the intermediate potential zone during an electrochemical impedance spectroscopy (EIS) measurement. Based on the chemical reaction analysis, we establish an EIS model and make some numerical analyses, thus determining the specific EIS shapes and equivalent circuits relating to various potential zones. These results not only compensate the drawback for traditional electrochemical approaches, but also reveal the dynamic adsorption of CO and OH species on Pt surfaces, providing a chance for understanding bifunctional mechanism towards quantitative manners. Significantly, we clarify that the negative resistance begins from the maximum catalysis of methanol electro-catalysis and ends in the initial passive state on Pt surfaces, offering a tool for further improvement. Interestingly, our discovery for negative resistance is consistent with that in general electrochemical system, facilitating its extension and direction in future.

  8. Possible origin of linear magnetoresistance: Observation of Dirac surface states in layered PtBi2

    Science.gov (United States)

    Thirupathaiah, S.; Kushnirenko, Y.; Haubold, E.; Fedorov, A. V.; Rienks, E. D. L.; Kim, T. K.; Yaresko, A. N.; Blum, C. G. F.; Aswartham, S.; Büchner, B.; Borisenko, S. V.

    2018-01-01

    The nonmagnetic compounds showing extremely large magnetoresistance are attracting a great deal of research interest due to their potential applications in the field of spintronics. PtBi2 is one of such interesting compounds showing large linear magnetoresistance (MR) in both the hexagonal and pyrite crystal structure. We use angle-resolved photoelectron spectroscopy and density functional theory calculations to understand the mechanism of liner MR observed in the layered PtBi2. Our results uncover linear dispersive surface Dirac states at the Γ ¯ point, crossing the Fermi level with a node at a binding energy of ≈900 meV, in addition to the previously reported Dirac states at the M ¯ point in the same compound. We further notice from our dichroic measurements that these surface states show an asymmetric spectral intensity when measured with left and right circularly polarized light, hinting at a substantial spin polarization of the bands. Following these observations, we suggest that the linear dispersive Dirac states at the Γ ¯ and M ¯ points are likely to play a crucial role for the linear field dependent magnetoresistance recorded in this compound.

  9. The operating performance and products distribution of the catalytic oxidation of methyl-isobutyl-ketone over a Pt/gamma-Al2O3 catalyst.

    Science.gov (United States)

    Tseng, Ting-Ke; Chu, Hsin; Ko, Tzu-Hsing; Chung, Lung-Kai

    2005-06-30

    Catalytic oxidation is one of the cost-effective technologies to solve the troublesome volatile organic compounds. This study treated methyl-isobutyl-ketone (MIBK) by a commercial catalyst, Pt/gamma-Al(2)O(3), in a fixed-bed reactor. The effects of operating factors, such as operating temperature, MIBK concentration, space velocity, and O(2) concentration, on the performance of the catalyst were investigated. The products and reactants distributions from the oxidation of MIBK over Pt/gamma-Al(2)O(3) were observed. The results show that the products containing carbon atoms are CO, CO(2), and C(3)H(6)O. Two catalyst life-tests were also carried out to characterize the deactivation effect of MIBK. The result shows that the deactivation effect may be due to the coke on the catalyst surface at 423 K. From the statistical analysis, the operating temperature is the most effective factor on the conversion of MIBK. The catalysts were also characterized by surface area analysis and elemental analysis before and after the test. The results show that the catalytic deactivation may be due to carbon coating. At low temperature (423 K), the phenomenon of carbon coating was more obvious than that at high temperature (573 K). The product distributions from the oxidation of MIBK over Pt/gamma-Al(2)O(3) were analyzed by GC. The results indicate that the C(3)H(6)O is formed from the beginning, presenting a peak at 423 K, 6.54 ppm. The CO concentration also peaked at the same temperature, 6.84 ppm.

  10. Synthesis of Supported NiPt Bimetallic Nanoparticles, Methods for Controlling the Surface Coverage of Ni Nanoparticles With Pt, Methods Of Making NiPt Multilayer Core-Shell Structures and Application of the Supported Catalysts for CO2 Reforming

    KAUST Repository

    Li, Lidong

    2015-06-25

    Embodiments of the present disclosure provide for supported Ni/Pt bimetallic nanoparticles, compositions including supported NiPt nanoparticles, methods of making supported NiPt nanoparticles, methods of using supported NiPt nanoparticles, and the like.

  11. 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)

  12. Biobutanol as Fuel for Direct Alcohol Fuel Cells-Investigation of Sn-Modified Pt Catalyst for Butanol Electro-oxidation.

    Science.gov (United States)

    Puthiyapura, Vinod Kumar; Brett, Dan J L; Russell, Andrea E; Lin, Wen-Feng; Hardacre, Christopher

    2016-05-25

    Direct alcohol fuel cells (DAFCs) mostly use low molecular weight alcohols such as methanol and ethanol as fuels. However, short-chain alcohol molecules have a relative high membrane crossover rate in DAFCs and a low energy density. Long chain alcohols such as butanol have a higher energy density, as well as a lower membrane crossover rate compared to methanol and ethanol. Although a significant number of studies have been dedicated to low molecular weight alcohols in DAFCs, very few studies are available for longer chain alcohols such as butanol. A significant development in the production of biobutanol and its proposed application as an alternative fuel to gasoline in the past decade makes butanol an interesting candidate fuel for fuel cells. Different butanol isomers were compared in this study on various Pt and PtSn bimetallic catalysts for their electro-oxidation activities in acidic media. Clear distinctive behaviors were observed for each of the different butanol isomers using cyclic voltammetry (CV), indicating a difference in activity and the mechanism of oxidation. The voltammograms of both n-butanol and iso-butanol showed similar characteristic features, indicating a similar reaction mechanism, whereas 2-butanol showed completely different features; for example, it did not show any indication of poisoning. Ter-butanol was found to be inactive for oxidation on Pt. In situ FTIR and CV analysis showed that OHads was essential for the oxidation of primary butanol isomers which only forms at high potentials on Pt. In order to enhance the water oxidation and produce OHads at lower potentials, Pt was modified by the oxophilic metal Sn and the bimetallic PtSn was studied for the oxidation of butanol isomers. A significant enhancement in the oxidation of the 1° butanol isomers was observed on addition of Sn to the Pt, resulting in an oxidation peak at a potential ∼520 mV lower than that found on pure Pt. The higher activity of PtSn was attributed to the

  13. 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.

  14. Synthesis and characterization of supported Pt and Pt alloys nanoparticles used for the catalytic oxidation of sulfur dioxide

    DEFF Research Database (Denmark)

    Koutsopoulos, Sotiris; Eriksen, Kim Michael; Fehrmann, Rasmus

    2006-01-01

    Controlled pore glass silica (CPG) was used as support to prepare platinum-based catalysts using the wet impregnation method and DMSO or CHCl3 as solvent. In all cases, the catalyst loading with the active phase was 2 wt%. The catalysts were tested for the SO2 oxidation reaction at atmospheric pr...

  15. Electrocatalytic properties of Pt/carbon composite nanofibers

    International Nuclear Information System (INIS)

    Lin Zhan; Ji Liwen; Zhang Xiangwu

    2009-01-01

    Pt/carbon composite nanofibers were prepared by electrodepositing Pt nanoparticles directly onto electrospun carbon nanofibers. The morphology and size of Pt nanoparticles were controlled by the electrodeposition time. The resulting Pt/carbon composite nanofibers were characterized by running cyclic voltammograms in 0.20 M H 2 SO 4 and 5.0 mM K 4 [Fe(CN) 6 ] + 0.10 M KCl solutions. The electrocatalytic activities of Pt/carbon composite nanofibers were measured by the oxidation of methanol. Results show that Pt/carbon composite nanofibers possess the properties of high active surface area and fast electron transfer rate, which lead to a good performance towards the electrocatalytic oxidation of methanol. It is also found that the Pt/carbon nanofiber electrode with a Pt loading of 0.170 mg cm -2 has the highest activity.

  16. Sintering of oxide-supported Pt and Pd nanoparticles in air studied by in situ TEM

    DEFF Research Database (Denmark)

    Simonsen, Søren Bredmose

    of the sintering mechanisms of nanoparticles is important for making improvements to their long term catalytic activity. Diesel oxidation catalysts are usually composed of noble metal nanoparticles on a complex three-dimensional high surface area oxide. The complex support structure makes it difficult to directly...... observe dynamical processes such as particle sintering with the present state of the art microscope techniques, and consequently it is difficult to relate experimental observations and theoretical sintering models. To reduce the complexity, the present study uses planar model catalysts. These are composed...

  17. Preparation and Characterization of Zirconia-Coated Nanodiamonds as a Pt Catalyst Support for Methanol Electro-Oxidation

    Directory of Open Access Journals (Sweden)

    Jing Lu

    2016-12-01

    Full Text Available Zirconia-coated nanodiamond (ZrO2/ND electrode material was successfully prepared by one-step isothermal hydrolyzing from ND-dispersed ZrOCl2·8H2O aqueous solution. High-resolution transmission electron microscopy reveals that a highly conformal and uniform ZrO2 shell was deposited on NDs by this simple method. The coating obtained at 90 °C without further calcination was mainly composed of monoclinic nanocrystalline ZrO2 rather than common amorphous Zr(OH4 clusters. The ZrO2/NDs and pristine ND powder were decorated with platinum (Pt nanoparticles by electrodeposition from 5 mM chloroplatinic acid solution. The electrochemical studies indicate that Pt/ZrO2/ND catalysts have higher electrocatalytic activity and better stability for methanol oxidation than Pt/ND catalysts in acid.

  18. Modification of polycarbonate surface in oxidizing plasma

    Science.gov (United States)

    Ovtsyn, A. A.; Smirnov, S. A.; Shikova, T. G.; Kholodkov, I. V.

    2017-11-01

    The properties of the surface of the film polycarbonate Lexan 8010 were experimentally studied after treatment in a DC discharge plasma in oxygen and air at pressures of 50-300 Pa and a discharge current of 80 mA. The contact angles of wetting and surface energies are measured. The topography of the surface was investigated by atomic force microscopy. The chemical composition of the surface was determined from the FT-IR spectroscopy data in the variant of total internal reflection, as well as X-ray photoelectron spectroscopy. Treatment in the oxidizing plasma leads to a change in morphology (average roughness increases), an increase in the surface energy, and the concentration of oxygen-containing groups (hydroxyl groups, carbonyl groups in ketones or aldehydes and in oxyketones) on the surface of the polymer. Possible reasons for the difference in surface properties of polymer under the action of oxygen and air plasma on it are discussed.

  19. Direct synthesis of bimetallic PtCo mesoporous nanospheres as efficient bifunctional electrocatalysts for both oxygen reduction reaction and methanol oxidation reaction

    Science.gov (United States)

    Wang, Hongjing; Yu, Hongjie; Li, Yinghao; Yin, Shuli; Xue, Hairong; Li, Xiaonian; Xu, You; Wang, Liang

    2018-04-01

    The engineering of electrocatalysts with high performance for cathodic and/or anodic catalytic reactions is of great urgency for the development of direct methanol fuel cells. Pt-based bimetallic alloys have recently received considerable attention in the field of fuel cells because of their superior catalytic performance towards both fuel molecule electro-oxidation and oxygen reduction. In this work, bimetallic PtCo mesoporous nanospheres (PtCo MNs) with uniform size and morphology have been prepared by a one-step method with a high yield. The as-made PtCo MNs show superior catalytic activities for both oxygen reduction reaction and methanol oxidation reaction relative to Pt MNs and commercial Pt/C catalyst, attributed to their mesoporous structure and bimetallic composition.

  20. Atomically flat single terminated oxide substrate surfaces

    Science.gov (United States)

    Biswas, Abhijit; Yang, Chan-Ho; Ramesh, Ramamoorthy; Jeong, Yoon H.

    2017-05-01

    Scientific interest in atomically controlled layer-by-layer fabrication of transition metal oxide thin films and heterostructures has increased intensely in recent decades for basic physics reasons as well as for technological applications. This trend has to do, in part, with the coming post-Moore era, and functional oxide electronics could be regarded as a viable alternative for the current semiconductor electronics. Furthermore, the interface of transition metal oxides is exposing many new emergent phenomena and is increasingly becoming a playground for testing new ideas in condensed matter physics. To achieve high quality epitaxial thin films and heterostructures of transition metal oxides with atomically controlled interfaces, one critical requirement is the use of atomically flat single terminated oxide substrates since the atomic arrangements and the reaction chemistry of the topmost surface layer of substrates determine the growth and consequent properties of the overlying films. Achieving the atomically flat and chemically single terminated surface state of commercially available substrates, however, requires judicious efforts because the surface of as-received substrates is of chemically mixed nature and also often polar. In this review, we summarize the surface treatment procedures to accomplish atomically flat surfaces with single terminating layer for various metal oxide substrates. We particularly focus on the substrates with lattice constant ranging from 4.00 Å to 3.70 Å, as the lattice constant of most perovskite materials falls into this range. For materials outside the range, one can utilize the substrates to induce compressive or tensile strain on the films and explore new states not available in bulk. The substrates covered in this review, which have been chosen with commercial availability and, most importantly, experimental practicality as a criterion, are KTaO3, REScO3 (RE = Rare-earth elements), SrTiO3, La0.18Sr0.82Al0.59Ta0.41O3 (LSAT), Nd

  1. PtNi supported on binary metal oxides: Potential bifunctional electrocatalysts for low-temperature fuel cells?

    Science.gov (United States)

    Martins, M.; Šljukić, B.; Sequeira, C. A. C.; Soylu, G. S. P.; Yurtcan, A. B.; Bozkurt, G.; Sener, T.; Santos, D. M. F.

    2018-01-01

    PtNi nanoparticles (NPs) were synthesised by microwave irradiation technique and supported onto Mn2O3 and two binary metal oxides, Mn2O3-TiO2 and Mn2O3-NiO, prepared by solid-state dispersion method. TEM analysis revealed formation of PtNi NPs of 2-3 nm diameter on the metal oxides. Their activity for oxygen reduction reaction (ORR) and borohydride oxidation reaction (BOR) in alkaline media was studied using voltammetric, amperometric and electrochemical impedance spectroscopy techniques. The effect of electrolyte composition and operation temperature on the catalysts performance was also examined. ORR and BOR kinetic parameters, namely Tafel slope, kinetic current density, order of reaction and activation energy were evaluated, enabling direct comparison of the three electrocatalysts performance. The results show that PtNi NPs anchored on binary metal oxide supports possess superior activity for BOR in alkaline media, suggesting their potential application as anodes in low-temperature fuel cells.

  2. Improving electromechanical output of IPMC by high surface area Pd-Pt electrodes and tailored ionomer membrane thickness

    Directory of Open Access Journals (Sweden)

    Viljar Palmre

    2014-04-01

    Full Text Available In this study, we attempt to improve the electromechanical performance of ionic polymer–metal composites (IPMCs by developing high surface area Pd-Pt electrodes and tailoring the ionomer membrane thickness. With proper electroless plating techniques, a high dispersion of palladium particles is achieved deep in the ionomer membrane, thereby increasing notably the interfacial surface area of electrodes. The membrane thickness is increased using 0.5 and 1 mm thick ionomer films. For comparison, IPMCs with the same ionomer membranes, but conventional Pt electrodes, are also prepared and studied. The electromechanical, mechanoelectrical, electrochemical and mechanical properties of different IPMCs are characterized and discussed. Scanning electron microscopy-energy dispersive X-ray (SEM-EDS is used to investigate the distribution of deposited electrode metals in the cross section of Pd-Pt IPMCs. Our experiments demonstrate that IPMCs assembled with millimeter thick ionomer membranes and newly developed Pd-Pt electrodes are superior in mechanoelectrical transduction, and show significantly higher blocking force compared to conventional type of IPMCs. The blocking forces of more than 0.3 N were measured at 4V DC input, exceeding the force output of typical Nafion® 117-based Pt IPMCs more than two orders of magnitude. The newly designed Pd-Pt IPMCs can be useful in more demanding applications, e.g., in biomimetic underwater robotics, where high stress and drag forces are encountered.

  3. A microelectrode array electrodeposited with reduced graphene oxide and Pt nanoparticles for norepinephrine and electrophysiological recordings

    Science.gov (United States)

    Wang, Li; Song, Yilin; Zhang, Yu; Xu, Shengwei; Xu, Huiren; Wang, Mixia; Wang, Yang; Cai, Xinxia

    2017-11-01

    Norepinephrine (NE), a common neurotransmitter released by locus coeruleus neurons, plays an essential role in the communication mechanism of the mammalian nervous system. In this work, a microelectrode array (MEA) was fabricated by micro-electromechanical system (MEMS) technology to provide a rapid, sensitive and reliable method for the direct determination in NE dynamic secretion. To improve the electrical performance, the MEA was electrodeposited with the reduced graphene oxide and Pt nanoparticles (rGOPNps). rGOPNps-MEA was investigated using scanning electron microscopy, atomic force microscopy and electrochemical impedance spectroscopy, differential pulse voltammetry exhibited remarkably electrocatalytic properties towards NE. Calibration results showed a sensitivity of 1.03 nA µM-1 to NE with a detection limit of 0.08 µM. In Particular, the MEA was successfully used for measuring dynamic extracellular NE secretion from the locus coeruleus brain slice, as well as monitoring spike firing from the hippocampal brain slice. This fabricated device has potential in studies of spatially resolved delivery of trace neurochemicals and electrophysiological activities of a variety of biological tissues in vitro.

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

    Science.gov (United States)

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

    2017-05-01

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

  5. Titania Supported Pt and Pt/Pd Nano-particle Catalysts for the Oxidation of Sulfur Dioxide

    DEFF Research Database (Denmark)

    Koutsopoulos, Sotiris; Johannessen, Tue; Eriksen, Kim Michael

    2006-01-01

    Several types of titania (anatase) were used as supports for pure platinum and Pt–Pd bimetallic alloy catalysts. The preparation methods, normal wet impregnation technique and flame aerosol synthesis, obtained metal loadings of 2% by weight. The prepared catalysts were tested for SO2 oxidation...... activity at atmospheric pressure in the temperature range 250–600 °C. The SO2 to SO3 conversion efficiency of the Pt–Pd alloy was significantly higher than that of the individual metals. The effects of the preparation method and the titania type used on the properties and activity of the resulting catalyst...

  6. The surface brightness of 1550 galaxies in Fornax: automated galaxy surface photometry: Pt. 2

    International Nuclear Information System (INIS)

    Phillipps, S.; Disney, M.J.; Kibblewhite, E.J.; Cawson, M.G.M.

    1987-01-01

    A survey of a complete sample of galaxies in the region of the Fornax cluster is presented. Measurements with the Automatic Plate Measuring machine are used to derive the observed distribution of galaxy surface brightness for 1550 objects. Corrections for surface brightness dependent selection effects are then made in order to estimate the true distribution. It is found that the sample (with 16.6 ≤ Msub(APM) ≤ 19.1) is divided into two distinct populations. The 'normal' galaxies with extrapolated central surface brightness Ssub(x) ≤ 22.5 Bμ form a uniformly distributed background of field galaxies. Low surface brightness galaxies (Ssub(x) ≥ 22.5 Bμ), on the other hand, are strongly clumped about the cluster centre. There appear to be few low surface brightness field galaxies. (author)

  7. 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.

  8. Adsorption of Ni, Pd, Pt, Cu, Ag and Au on the Fe3O4(111) surface

    Science.gov (United States)

    Yu, Xiaohu; Tian, Xinxin; Wang, Shengguang

    2014-10-01

    The interaction of Group 10 and 11 transition metals with the magnetite (111) surface has been investigated using the GGA + U density functional theory and periodic slab surface models. It was found that these transition metals adsorb stronger on an oxygen-terminated magnetite (111) surface than on an iron-terminated surface. On an oxygen-terminated surface, the adsorption strength is in the order of Ni > Pt Cu > Pd > Ag Au. In contrast, the order on an iron-terminated surface is Ni > Pt Cu > Au > Pd Ag. The adsorption strength was found to correlate well with the average lengths of metal-oxygen bonds. The magnetite (111) surfaces largely modify the electronic structures of the transition metals. Compared to their density of states in bulk structures, the atomically adsorbed transition metals have narrower d bands, and their d-band centers are closer to the Fermi levels. This implies the higher activities of the atomically adsorbed transition metals.

  9. Electrochemical promotion of propane oxidation on Pt deposited on a dense β"-Al2O3 ceramic Ag+ conductor

    Directory of Open Access Journals (Sweden)

    Michail eTsampas

    2013-08-01

    Full Text Available A new kind of electrochemical catalyst based on a Pt porous catalyst film deposited on a β"-Al2O3 ceramic Ag+ conductor was developed and evaluated during propane oxidation. It was observed that upon anodic polarization, the rate of propane combustion was significantly electropromoted up to 400%. Moreover, for the first time, exponential increase of the catalytic rate was evidenced during galvanostatic transient experiment in excellent agreement with EPOC equation.

  10. Electrochemical promotion of propane oxidation on Pt deposited on a dense β"-Al2O3 ceramic Ag+ conductor

    Science.gov (United States)

    Tsampas, Michail; Kambolis, Anastasios; Obeid, Emil; Lizarraga, Leonardo; Sapountzi, Foteini; Vernoux, Philippe

    2013-08-01

    A new kind of electrochemical catalyst based on a Pt porous catalyst film deposited on a β"-Al2O3 ceramic Ag+ conductor was developed and evaluated during propane oxidation. It was observed that upon anodic polarization, the rate of propane combustion was significantly electropromoted up to 400%. Moreover, for the first time, exponential increase of the catalytic rate was evidenced during galvanostatic transient experiment in excellent agreement with EPOC equation.

  11. The interplay between surface-water and hydrogen bonding in a water adlayer on Pt(111) and Ag(111)

    Energy Technology Data Exchange (ETDEWEB)

    Delle Site, Luigi [Max-Planck-Institut fuer Polymerforschung, Ackermannweg 10, D-55128 Mainz (Germany); Ghiringhelli, Luca M [Max-Planck-Institut fuer Polymerforschung, Ackermannweg 10, D-55128 Mainz (Germany); Andreussi, Oliviero [Scuola Normale Superiore, Piazza dei Cavalieri 7, 56100 Pisa (Italy); Donadio, Davide [Computational Science, Department of Chemistry and Applied Biosciences, ETH Zurich, USI-Campus, via Giuseppe Buffi 13, CH-6900 Lugano (Switzerland); Parrinello, Michele [Scuola Normale Superiore, Piazza dei Cavalieri 7, 56100 Pisa (Italy)

    2007-06-20

    The structure of a water adlayer on a Pt(111) surface is investigated by means of extensive first-principles calculations. Allowing for proton disorder, the ground state energy for the {radical}3 x {radical}3R30{sup o} structure can be found. This results from an interplay between water/metal chemical bonding and the hydrogen bonding of the water network. This picture is supported by substituting Pt(111) with Ag(111): the almost inert surface allows for the reconstruction of the hydrogen network. (fast track communication)

  12. The interplay between surface-water and hydrogen bonding in a water adlayer on Pt(111) and Ag(111)

    International Nuclear Information System (INIS)

    Delle Site, Luigi; Ghiringhelli, Luca M; Andreussi, Oliviero; Donadio, Davide; Parrinello, Michele

    2007-01-01

    The structure of a water adlayer on a Pt(111) surface is investigated by means of extensive first-principles calculations. Allowing for proton disorder, the ground state energy for the √3 x √3R30 o structure can be found. This results from an interplay between water/metal chemical bonding and the hydrogen bonding of the water network. This picture is supported by substituting Pt(111) with Ag(111): the almost inert surface allows for the reconstruction of the hydrogen network. (fast track communication)

  13. Adsorption and revaporisation studies on iodine oxide aerosols deposited on containment surface materials in LWR

    Energy Technology Data Exchange (ETDEWEB)

    Tietze, S.; Foreman, M.R.StJ.; Ekberg, C. [Chalmers Univ. of Technology, Goeteborg (Sweden); Kaerkelae, T.; Auvinen, A.; Tapper, U.; Lamminmaeki, S.; Jokiniemi, J. [VTT Technical Research Centre of Finland, Espoo (Finland)

    2012-12-15

    During a hypothetical severe nuclear accident, the radiation field will be very high in the nuclear reactor containment building. As a result gaseous radiolysis products will be formed. Elemental iodine can react in the gaseous phase with ozone to form solid iodine oxide aerosol particles (iodine oxide). Within the AIAS (Adsorption of Iodine oxide Aerosols on Surfaces) project the interactions of iodine oxide (IOx) aerosols with common containment surface materials were investigated. Common surface materials in Swedish and Finnish LWRs are Teknopox Aqua V A paint films and metal surfaces such as Cu, Zn, Al and SS, as well as Pt and Pd surfaces from hydrogen recombiners. Non-radioactive and {sup 131}I labelled iodine oxide aerosols were produced with the EXSI CONT facility from elemental iodine and ozone at VTT Technical Research Centre of Finland. The iodine oxide deposits were analysed with microscopic and spectroscopic measurement techniques to identify the kind of iodine oxide formed and if a chemical conversion on the different surface materials occurs. The revaporisation behaviour of the deposited iodine oxide aerosol particles from the different surface materials was studied under the influence of heat, humidity and gamma irradiation at Chalmers University of Technology, Sweden. Studies on the effects of humidity were performed using the FOMICAG facility, while heat and irradiation experiments were performed in a thermostated heating block and with a gammacell 22 having a dose rate of 14 kGy/h. The revaporisation losses were measured using a HPGe detector. The revaporisated {sup 131}I species from the surfaces were chemically tested for elemental iodine formation. The parameter dominating the degradation of the produced iodine oxide aerosols was humidity. Cu and Zn surfaces were found to react with iodine from the iodine oxide aerosols to form iodides, while no metal iodides were detected for Al and SS samples. Most of the iodine oxide aerosols are assumed to

  14. Correlação entre a estrutura atômica superficial e o processo de adsorção-dessorção reversível de hidrogênio em eletrodos monocristalinos Pt(111, Pt(100 e Pt(110 The correlation between the atomic surface structure and the reversible adsorption-desorption of hydrogen on single crystal Pt (111, Pt (100 and Pt (110 electrodes

    Directory of Open Access Journals (Sweden)

    Valderi Pacheco dos Santos

    2001-12-01

    Full Text Available Platinum is widely used as electrode in electrocatalytic processes, however the use of polycrystalline electrodes introduces a series of variables in the electrochemical system due to the aleatory contribution of all the crystallographic orientations with different surface packing of atoms. Single crystal platinum electrodes of low Miller index present surface structure of high regularity and serve as model to establish a correlation among the macroscopic and microscopic properties of the electrochemical interface. Therefore, the main aim of this work is the study of the voltammetric profiles of the reversible adsorption-desorption of hydrogen on Pt(100, Pt(110 and Pt(111, in order to correlate the electrochemical properties of each different orientation with the surface atomic structure.

  15. The Electronic Band Structure of Platinum Oxide (PtO) | Omehe ...

    African Journals Online (AJOL)

    We have performed the electronic band structure of the bulk and monolayer of PtO using the full potential linear muffin-tin orbital and the projector augmented wave method with the density functional theory. We applied the LDA and LDA+U scheme to both methods. It was found out that the LDA calculation of bulk PtO ...

  16. The Electronic Band Structure of Platinum Oxide (PtO) | Omehe ...

    African Journals Online (AJOL)

    It was found out that the LDA calculation of bulk PtO predicted a metallic nature in agreement with previous LDA and GGA calculations but in disagreement with the semiconductor nature favored by experiment. Our LDA+U calculation for both methods predicted PtO to be a semiconductor with a band gap value of 1.4 eV ...

  17. Controllable pt nanoparticle deposition on carbon nanotubes as an anode catalyst for direct methanol fuel cells.

    Science.gov (United States)

    Mu, Yongyan; Liang, Hanpu; Hu, Jinsong; Jiang, Li; Wan, Lijun

    2005-12-01

    We report a novel process to prepare well-dispersed Pt nanoparticles on CNTs. Pt nanoparticles, which were modified by the organic molecule triphenylphosphine, were deposited on multiwalled carbon nanotubes by the organic molecule, which acts as a cross linker. By manipulating the relative ratio of Pt nanoparticles and multiwalled carbon nanotubes in solution, Pt/CNT composites with different Pt content were achieved. The so-prepared Pt/CNT composite materials show higher electrocatalytic activity and better tolerance to poisoning species in methanol oxidation than the commercial E-TEK catalyst, which can be ascribed to the high dispersion of Pt nanoparticles on the multiwalled carbon nanotube surface.

  18. 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.

  19. Analysis of oxide formed on Ti during exposure in bentonite clay. Pt. 1

    International Nuclear Information System (INIS)

    Mattsson, H.; Olefjord, I.

    1990-01-01

    Titanium is a candidate as a canister material for the encapsulation of spent nuclear fuel due to its excellent corrosion properties. The aim of this paper is to determine the corrosion rate of titanium in ground-water saturated bentonite clay at 95deg C. The exposure times were ranging from 4 months to 6 years. The analysis tool was ESCA. The results show that the oxide consists mainly of TiO 2 and is 65-90 A thick. A few monolayers of TiO and Ti 2 O 3 exist close to the metal interface. It is found, that the oxide follows the same logarithmic growth law as in aqueous solutions: y = 71.7 + 3.65 ln t (y in A and t in years). This law applies irrespective of salt or oxygen content or if bentonite is present on the surface. No influence of the alloying element Pd was found. Deviations from the logarithmic growth law was also found, which indicates that a change of growth can occur in a long term perspective. It is suggested that the increased growth rate is caused by crystallization of the oxide. The influence of bentonite is that the majority component montmorillonite is adsorbed in a 10-40 A thick layer on the surface. (orig.) [de

  20. Surface-modified low-temperature solid oxide fuel cell

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Young Beom; Holme, Timothy P. [Department of Mechanical Engineering, Stanford University, Stanford, CA 94305 (United States); Guer, Turgut M. [Department of Materials Science and Engineering, Stanford University, Stanford, CA 94305 (United States); Prinz, Fritz B. [Department of Mechanical Engineering, Stanford University, Stanford, CA 94305 (United States); Department of Materials Science and Engineering, Stanford University, Stanford, CA 94305 (United States)

    2011-12-20

    This paper reports both experimental and theoretical results of the role of surface modification on the oxygen reduction reaction in low-temperature solid oxide fuel cells (LT-SOFC). Epitaxial ultrathin films of yttria-doped ceria (YDC) cathode interlayers (<10-130 nm) are grown by pulsed laser deposition (PLD) on single-crystalline YSZ(100). Fuel cell current-voltage measurements and electrochemical impedance spectroscopy are performed in the temperature range of 350 C {approx} 450 C. Quantum mechanical simulations of oxygen incorporation energetics support the experimental results and indicate a low activation energy of only 0.07 eV for YDC, while the incorporation reaction on YSZ is activated by a significantly higher energy barrier of 0.38 eV. Due to enhanced oxygen incorporation at the modified Pt/YDC interface, the cathodic interface resistance is reduced by two-fold, while fuel cell performance shows more than a two-fold enhancement with the addition of an ultrathin YDC interlayer at the cathode side of an SOFC element. The results of this study open up opportunities for improving cell performance, particularly of LT-SOFCs by adopting surface modification of YSZ surface with catalytically superior, ultrathin cathodic interlayers. (Copyright copyright 2011 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  1. A novel structural design of a Pt/C-CeO{sub 2} catalyst with improved performance for methanol electro-oxidation by {beta}-cyclodextrin carbonization

    Energy Technology Data Exchange (ETDEWEB)

    Chu, Yuan-Yuan; Jiang, Zheng-Zhi [School of Chemical Engineering and Technology, Harbin Institute of Technology, No.92 West-Da Zhi Street, Harbin (China); School of Science, Harbin Institute of Technology, Harbin (China); Wang, Zhen-Bo; Yin, Ge-Ping [School of Chemical Engineering and Technology, Harbin Institute of Technology, No.92 West-Da Zhi Street, Harbin (China); Gu, Da-Ming [School of Science, Harbin Institute of Technology, Harbin (China)

    2011-07-19

    A novel structural Pt/C-CeO{sub 2} catalyst synthesized using MP-CeO{sub 2} coated with carbon by in situ {beta}-cyclodextrin carbonization and then depositing Pt nanoparticles using a fast and facile microwave-assisted polyol process. The increased electron conductivity and the more oxygen-containing species of carbon available for the Pt site contribute to the improved activity and stability for methanol oxidation compared to Pt/CeO{sub 2}. (Copyright copyright 2011 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  2. Characterization of the inside and outside oxide surfaces of irradiated pressure tubes of Embalse nuclear power plant

    International Nuclear Information System (INIS)

    Bordoni, Roberto A.; Olmedo, Ana M.

    2004-01-01

    The inside and outside surfaces of two pressure tubes (PT) removed from Embalse nuclear power plant (CNE) after 10 of effective full power years (EFPY) were characterized. The oxide thickness of both faces, in different zones, was also measured. The inside surfaces of both PTs, B-102 (A-14) and B-298 (L-12), were covered with a black oxide that replicates the original PT surface. A network of microcracks perpendicular to the inside surface in contact with the coolant was found. In some cases, near the outlet of the PT, some spalling of the oxide was also found. These small microcracks and spalling do not affect the protective character of the oxide since a thickness about 5 or 6 μm of an undamaged oxide is found at the metal/oxide interface side. The oxide thickness changes between approximately 6 to 12 μm for B-102 tube and around 7 to 15 μm for B-298 tube. The average corrosion rate is 1.16 μm/10 4 HH for B-102 tube and 1.35 μm/10 4 HH for B-298 tube at 5.8 m position for both PTs. These corrosion rates show good corrosion behaviour of CNE PTs. The average corrosion rate of the inside surface of the PTs depends on the coolant temperature but not on fast neutron flux. The outside oxide film is black, shiny, compact and protective, replicating also the original surface. The oxide thickness changes between 2 to 6.5 μm in B-102 tube and between 1.8 to 3.7 μm B-298 tube. These oxide thicknesses are within the values reported for PTs in CANDU Stations. (author) [es

  3. Patterning pentacene surfaces by local oxidation nanolithography

    International Nuclear Information System (INIS)

    Losilla, N.S.; Martinez, J.; Bystrenova, E.; Greco, P.; Biscarini, F.; Garcia, R.

    2010-01-01

    Sequential and parallel local oxidation nanolithographies have been applied to pattern pentacene samples by creating a variety of nanostructures. The sequential local oxidation process is performed with an atomic force microscope and requires the application of a sequence of voltage pulses of 36 V for 1 ms. The parallel local oxidation process is performed by using a conductive and patterned stamp. Then, a voltage pulse is applied between the stamp and the pentacene surface. Patterns formed by arrays of parallel lines covering 1 mm 2 regions and with a periodicity of less than 1 μm have been generated in a few seconds. We also show that the patterns can be used as templates for the deposition of antibodies.

  4. Patterning pentacene surfaces by local oxidation nanolithography

    Energy Technology Data Exchange (ETDEWEB)

    Losilla, N.S., E-mail: nuria@imm.cnm.csic.es [Instituto de Microelectronica de Madrid: CSIC, Isaac Newton 8, 28760 Tres Cantos, Madrid (Spain); Martinez, J. [Instituto de Microelectronica de Madrid: CSIC, Isaac Newton 8, 28760 Tres Cantos, Madrid (Spain); Bystrenova, E.; Greco, P.; Biscarini, F. [Institute for Nanostructured Materials: CNR (ISMN-CNR), Via Gobetti 101, 40129 Bologna (Italy); Garcia, R., E-mail: rgarcia@imm.cnm.csic.es [Instituto de Microelectronica de Madrid: CSIC, Isaac Newton 8, 28760 Tres Cantos, Madrid (Spain)

    2010-05-15

    Sequential and parallel local oxidation nanolithographies have been applied to pattern pentacene samples by creating a variety of nanostructures. The sequential local oxidation process is performed with an atomic force microscope and requires the application of a sequence of voltage pulses of 36 V for 1 ms. The parallel local oxidation process is performed by using a conductive and patterned stamp. Then, a voltage pulse is applied between the stamp and the pentacene surface. Patterns formed by arrays of parallel lines covering 1 mm{sup 2} regions and with a periodicity of less than 1 {mu}m have been generated in a few seconds. We also show that the patterns can be used as templates for the deposition of antibodies.

  5. Methanol oxidation reaction activity of microwave irradiated and heat-treated Pt/Co and Pt/Ni nano-electrocatalysts

    CSIR Research Space (South Africa)

    Mathe, NR

    2014-11-01

    Full Text Available Bimetallic Pt nanoparticles were prepared by alloying Pt with the non-noble transition metals, Co and Ni, using a conventional heat-treatment (HT) method and microwaveirradiation (MW). The resulting samples were PteCo-Ht, PteNi-HT, PteCo, MW and Pt...

  6. 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.

  7. Nucleation and growth of C60 overlayers on the Ag/Pt(111) dislocation network surface

    International Nuclear Information System (INIS)

    Ait-Mansour, K; Ruffieux, P; Xiao, W; Fasel, R; Groening, P; Groening, O

    2007-01-01

    We have investigated the room temperature growth of C 60 overlayers on the strainrelief dislocation network formed by two monolayers of Ag on Pt(111) by means of scanning tunneling microscopy. Extended domains of highly ordered dislocation networks with a typical superlattice parameter of 6.8 nm have been prepared, serving as templates for subsequent C 60 depositions. For low C 60 coverages, the molecules decorate the step-edges, where also the first islands nucleate. This indicates that at room temperature the C 60 molecules are sufficiently mobile to cross the dislocation lines and to diffuse to the step-edges. For C 60 coverages of 0.4 monolayer, besides the islands nucleated at the step-edges, C 60 islands also grow in the middle of terraces. The C 60 islands typically extend over several unit cells of the dislocation network and show an unusual orientation of the hexagonally close-packed C 60 lattice as compared to that found on the bare Ag(111) surface. Whereas C 60 grows preferentially in a (2 √3 x 2 √3) R30 0 structure on Ag(111), on the Ag/Pt(111) dislocation network the C 60 lattice adopts an orientation rotated by 30 0 , with the close-packed C 60 rows aligned along the dislocations which themselves are aligned along the Ag(1-10) directions. For higher coverages in the range of 1-2 monolayers, the growth of C 60 continues in a layer-by-layer fashion

  8. Temperature effect on surface oxidation of titanium

    International Nuclear Information System (INIS)

    Vaquilla, I.; Barco, J.L. del; Ferron, J.

    1990-01-01

    The effect of temperature on the first stages of the superficial oxidation of polycrystalline titanium was studied using both Auger electron spectroscopy (AES) and emission shreshold (AEAPS). The number of compounds present on the surface was determined by application of the factor analysis technique. Reaction evolution was followed through the relative variation of Auger LMM and LMV transitions which are characteristic of titanium. Also the evolution of the chemical shift was determined by AEAPS. The amount of oxygen on the surface was quantified using transition KLL of oxygen. It was found that superficial oxidation depends on temperature. As much as three different compounds were determined according to substrate temperature and our exposure ranges. (Author). 7 refs., 5 figs

  9. Effects of Alloyed Metal on the Catalysis Activity of Pt for Ethanol Partial Oxidation: Adsorption and Dehydrogenation on Pt3M (M=Pt, Ru, Sn, Re, Rh, and Pd)

    OpenAIRE

    Xu, Zhen-Feng; Wang, Yixuan

    2011-01-01

    The adsorption and dehydrogenation reactions of ethanol over bimetallic clusters, Pt3M (M = Pt, Ru, Sn, Re, Rh, and Pd), have been extensively investigated with density functional theory. Both the α-hydrogen and hydroxyl adsorptions on Pt as well as on the alloyed transition metal M sites of PtM were considered as initial reaction steps. The adsorptions of ethanol on Pt and M sites of some PtM via the α-hydrogen were well established. Although the α-hydrogen adsorption on Pt site is weaker th...

  10. Fundamental Mechanistic Understanding of Electrocatalysis of Oxygen Reduction on Pt and Non-Pt Surfaces: Acid versus Alkaline Media

    Directory of Open Access Journals (Sweden)

    Nagappan Ramaswamy

    2012-01-01

    Full Text Available Complex electrochemical reactions such as Oxygen Reduction Reaction (ORR involving multi-electron transfer is an electrocatalytic inner-sphere electron transfer process that exhibit strong dependence on the nature of the electrode surface. This criterion (along with required stability in acidic electrolytes has largely limited ORR catalysts to the platinum-based surfaces. New evidence in alkaline media, discussed here, throws light on the involvement of surface-independent outer-sphere electron transfer component in the overall electrocatalytic process. This surface non-specificity gives rise to the possibility of using a wide-range of non-noble metal surfaces as electrode materials for ORR in alkaline media. However, this outer-sphere process predominantly leads only to peroxide intermediate as the final product. The importance of promoting the electrocatalytic inner-sphere electron transfer by facilitation of direct adsorption of molecular oxygen on the active site is emphasized by using pyrolyzed metal porphyrins as electrocatalysts. A comparison of ORR reaction mechanisms between acidic and alkaline conditions is elucidated here. The primary advantage of performing ORR in alkaline media is found to be the enhanced activation of the peroxide intermediate on the active site that enables the complete four-electron transfer. ORR reaction schemes involving both outer- and inner-sphere electron transfer mechanisms are proposed.

  11. Supersaturation-controlled surface structure evolution of Pd@Pt core-shell nanocrystals: enhancement of the ORR activity at a sub-10 nm scale

    Science.gov (United States)

    Qi, Kun; Zheng, Weitao; Cui, Xiaoqiang

    2016-01-01

    Here, we designed and implemented a facile strategy for controlling the surface evolution of Pd@Pt core-shell nanostructures by simply adjusting the volume of OH- to control the reducing ability of ascorbic acid and finally manipulating the supersaturation in the reaction system. The surface structure of the obtained Pd@Pt bimetallic nanocrystals transformed from a Pt {111} facet-exposed island shell to a conformal Pt {100} facet-exposed shell by increasing the pH value. The as-prepared well aligned Pd@Pt core-island shell nanocubes present both significantly enhanced electrocatalytic activity and favorable long-term stability toward the oxygen reduction reaction in alkaline media.Here, we designed and implemented a facile strategy for controlling the surface evolution of Pd@Pt core-shell nanostructures by simply adjusting the volume of OH- to control the reducing ability of ascorbic acid and finally manipulating the supersaturation in the reaction system. The surface structure of the obtained Pd@Pt bimetallic nanocrystals transformed from a Pt {111} facet-exposed island shell to a conformal Pt {100} facet-exposed shell by increasing the pH value. The as-prepared well aligned Pd@Pt core-island shell nanocubes present both significantly enhanced electrocatalytic activity and favorable long-term stability toward the oxygen reduction reaction in alkaline media. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr07940c

  12. Nitric oxide-induced eosinophil apoptosis is dependent on mitochondrial permeability transition (mPT, JNK and oxidative stress: apoptosis is preceded but not mediated by early mPT-dependent JNK activation

    Directory of Open Access Journals (Sweden)

    Ilmarinen-Salo Pinja

    2012-08-01

    Full Text Available Abstract Background Eosinophils are critically involved in the pathogenesis of asthma. Nitric oxide (NO is produced in high amounts in asthmatic lungs and has an important role as a regulator of lung inflammation. NO was previously shown to induce eosinophil apoptosis mediated via c-jun N-terminal kinase (JNK and caspases. Our aim was to clarify the cascade of events leading to NO-induced apoptosis in granulocyte macrophage-colony stimulating factor (GM-CSF-treated human eosinophils concentrating on the role of mitochondria, reactive oxygen species (ROS and JNK. Methods Apoptosis was determined by flow cytometric analysis of relative DNA content, by Annexin-V labelling and/or morphological analysis. Immunoblotting was used to study phospho-JNK (pJNK expression. Mitochondrial membrane potential was assessed by JC-1-staining and mitochondrial permeability transition (mPT by loading cells with calcein acetoxymethyl ester (AM and CoCl2 after which flow cytometric analysis was conducted. Statistical significance was calculated by repeated measures analysis of variance (ANOVA or paired t-test. Results NO-donor S-nitroso-N-acetyl-D,L-penicillamine (SNAP induced late apoptosis in GM-CSF-treated eosinophils. SNAP-induced apoptosis was suppressed by inhibitor of mPT bongkrekic acid (BA, inhibitor of JNK SP600125 and superoxide dismutase-mimetic AEOL 10150. Treatment with SNAP led to late loss of mitochondrial membrane potential. Additionally, we found that SNAP induces early partial mPT (1 h that was followed by a strong increase in pJNK levels (2 h. Both events were prevented by BA. However, these events were not related to apoptosis because SNAP-induced apoptosis was prevented as efficiently when BA was added 16 h after SNAP. In addition to the early and strong rise, pJNK levels were less prominently increased at 20–30 h. Conclusions Here we demonstrated that NO-induced eosinophil apoptosis is mediated via ROS, JNK and late mPT. Additionally

  13. Influence of Pt nanoparticles modified by La and Ce oxides on catalytic dehydrocyclization of n-alkanes

    Directory of Open Access Journals (Sweden)

    A.H. Samia

    2015-06-01

    Full Text Available Catalytic reforming accounts for a large share of the world’s gasoline production, it is the most important source of aromatics for the petrochemical industry. In addition, reforming of hydrocarbon on the dual-function catalysts has been found to form fundamentally different products in hydrogen diluents. Typical catalysts employed for this reforming process are Pt/Al2O3 and Pt-M/Al2O3, M being the promoter. These solids are characterized by both acid and metal functions which catalyze dehydrocyclization, dehydrogenation, isomerization and cracking processes. In this regard, information about cerium and lanthanum, as promoters, is hardly revealed. The present work aims to study the performance of Pt/Al2O3 catalysts modified by lanthanum or cerium during the conversion of cyclohexane, n-hexane and n-heptane. Catalytic activities of the prepared catalysts were tested using a micro catalytic pulse technique. Physicochemical characterization of the solid catalysts such as, surface area (SBET, Fourier transform infrared (FTIR, differential scanning calorimetry (DSC, thermogravimetric analysis (TGA, hydrogen-temperature programed reduction (H2-TPR, hydrogen-temperature-programed desorption (H2-TPD, CO2-TPD, NH3-TPD, high resolution transmission electron microscopy (HRTEM and X-ray diffraction (XRD were depicted. Results indicated clearly that Pt/Al2O3 catalyst is selective toward dehydrogenation to benzene which could be explained as due to the decrease in the active acid sites and the comparative segregation of the alumina support especially at 3% load of CeO. The presence of La2O3 in the Pt/Al2O3 catalyst promotes aromatization of n-hexane and n-heptane, also the dehydrocyclization of n-hexane is more difficult than that of n-heptane. Thus, modification of the Pt/Al2O3 catalyst by La, resulted in a more active and selective reforming catalyst.

  14. Photovoltaic effect in an indium-tin-oxide/ZnO/BiFeO3/Pt heterostructure

    International Nuclear Information System (INIS)

    Fan, Zhen; Yao, Kui; Wang, John

    2014-01-01

    We have studied the photovoltaic effect in a metal/semiconductor/ferroelectric/metal heterostructure of In 2 O 3 -SnO 2 /ZnO/BiFeO 3 /Pt (ITO/ZnO/BFO/Pt) multilayer thin films. The heterolayered structure shows a short-circuit current density (J sc ) of 340 μA/cm 2 and an energy conversion efficiency of up to 0.33% under blue monochromatic illumination. The photovoltaic mechanism, specifically in terms of the major generation site of photo-excited electron-hole (e-h) pairs and the driving forces for the separation of e-h pairs, is clarified. The significant increase in photocurrent of the ITO/ZnO/BFO/Pt compared to that of ITO/BFO/Pt is attributed to the abundant e-h pairs generated from ZnO. Ultraviolet photoelectron spectroscopy reveals the energy band alignment of ITO/ZnO/BFO/Pt, where a Schottky barrier and an n + -n junction are formed at the BFO/Pt and ZnO/BFO interfaces, respectively. Therefore, two built-in fields developed at the two interfaces are constructively responsible for the separation and transport of photo-excited e-h pairs.

  15. Surface Chemistry and Spectroscopy of Chromium in Inorganic Oxides

    NARCIS (Netherlands)

    Weckhuysen, B.M.; Wachs, I.E.; Schoonheydt, R.A.

    1996-01-01

    Focuses on the surface chemistry and spectroscopy of chromium in inorganic oxides. Characterization of the molecular structures of chromium; Mechanics of hydrogenation-dehydrogenation reactions; Mobility and reactivity on oxidic surfaces.

  16. The role of water in the initial steps of methanol oxidation on Pt(211)

    International Nuclear Information System (INIS)

    Hartnig, C.; Grimminger, J.; Spohr, E.

    2007-01-01

    We report results of quantum-chemical calculations within the framework of density functional theory for the oxidation of methanol on the (211) face of a platinum single crystal. Similar to the reaction pathway on the low indexed (111) crystal face water plays an important role as found from energy minimization calculations: the adsorption of methanol on charged and uncharged surfaces is strongly enhanced by the formation of a hydrogen bond to a coadsorbed water molecule. The methanol is adsorbed via a methyl hydrogen atom preceding scission of one of the CH-bonds as the first reaction step. In the presence of additional water, e.g., from a liquid phase, the onset of the oxidation reaction is favored by a coadsorbed neighboring water molecule which forms a hydrogen bond with the methanol OH-group. At a minimum number of adjacent water molecules (n>=2) the CH-bond as well as the OH-bond are cleaved on charged surfaces. The protonic charge stemming from the dissociation of the methanol hydroxyl group is delocalized inside the aqueous cluster and formaldehyde is formed as an intermediate product

  17. High-temperature catalytic reforming of n-hexane over supported and core-shell Pt nanoparticle catalysts: role of oxide-metal interface and thermal stability.

    Science.gov (United States)

    An, Kwangjin; Zhang, Qiao; Alayoglu, Selim; Musselwhite, Nathan; Shin, Jae-Youn; Somorjai, Gabor A

    2014-08-13

    Designing catalysts with high thermal stability and resistance to deactivation while simultaneously maintaining their catalytic activity and selectivity is of key importance in high-temperature reforming reactions. We prepared Pt nanoparticle catalysts supported on either mesoporous SiO2 or TiO2. Sandwich-type Pt core@shell catalysts (SiO2@Pt@SiO2 and SiO2@Pt@TiO2) were also synthesized from Pt nanoparticles deposited on SiO2 spheres, which were encapsulated by either mesoporous SiO2 or TiO2 shells. n-Hexane reforming was carried out over these four catalysts at 240-500 °C with a hexane/H2 ratio of 1:5 to investigate thermal stability and the role of the support. For the production of high-octane gasoline, branched C6 isomers are more highly desired than other cyclic, aromatic, and cracking products. Over Pt/TiO2 catalyst, production of 2-methylpentane and 3-methylpentane via isomerization was increased selectively up to 420 °C by charge transfer at Pt-TiO2 interfaces, as compared to Pt/SiO2. When thermal stability was compared between supported catalysts and sandwich-type core@shell catalysts, the Pt/SiO2 catalyst suffered sintering above 400 °C, whereas the SiO2@Pt@SiO2 catalyst preserved the Pt nanoparticle size and shape up to 500 °C. The SiO2@Pt@TiO2 catalyst led to Pt nanoparticle sintering due to incomplete protection of the TiO2 shells during the reaction at 500 °C. Interestingly, over the Pt/TiO2 catalyst, the average size of Pt nanoparticles was maintained even after 500 °C without sintering. In situ ambient pressure X-ray photoelectron spectroscopy demonstrated that the Pt/TiO2 catalyst did not exhibit TiO2 overgrowth on the Pt surface or deactivation by Pt sintering up to 600 °C. The extraordinarily high stability of the Pt/TiO2 catalyst promoted high reaction rates (2.0 μmol · g(-1) · s(-1)), which was 8 times greater than other catalysts and high isomer selectivity (53.0% of C6 isomers at 440 °C). By the strong metal-support interaction

  18. Mathematical Modeling of Ammonia Electro-Oxidation on Polycrystalline Pt Deposited Electrodes

    Science.gov (United States)

    Diaz Aldana, Luis A.

    The ammonia electrolysis process has been proposed as a feasible way for electrochemical generation of fuel grade hydrogen (H2). Ammonia is identified as one of the most suitable energy carriers due to its high hydrogen density, and its safe and efficient distribution chain. Moreover, the fact that this process can be applied even at low ammonia concentration feedstock opens its application to wastewater treatment along with H 2 co-generation. In the ammonia electrolysis process, ammonia is electro-oxidized in the anode side to produce N2 while H2 is evolved from water reduction in the cathode. A thermodynamic energy requirement of just five percent of the energy used in hydrogen production from water electrolysis is expected from ammonia electrolysis. However, the absence of a complete understanding of the reaction mechanism and kinetics involved in the ammonia electro-oxidation has not yet allowed the full commercialization of this process. For that reason, a kinetic model that can be trusted in the design and scale up of the ammonia electrolyzer needs to be developed. This research focused on the elucidation of the reaction mechanism and kinetic parameters for the ammonia electro-oxidation. The definition of the most relevant elementary reactions steps was obtained through the parallel analysis of experimental data and the development of a mathematical model of the ammonia electro-oxidation in a well defined hydrodynamic system, such as the rotating disk electrode (RDE). Ammonia electro-oxidation to N 2 as final product was concluded to be a slow surface confined process where parallel reactions leading to the deactivation of the catalyst are present. Through the development of this work it was possible to define a reaction mechanism and values for the kinetic parameters for ammonia electro-oxidation that allow an accurate representation of the experimental observations on a RDE system. Additionally, the validity of the reaction mechanism and kinetic parameters

  19. Investigation of the oxygen exchange mechanism on Pt|yttria stabilized zirconia at intermediate temperatures: Surface path versus bulk path

    International Nuclear Information System (INIS)

    Opitz, Alexander K.; Lutz, Alexander; Kubicek, Markus; Kubel, Frank; Hutter, Herbert; Fleig, Juergen

    2011-01-01

    Highlights: → Oxygen exchange kinetics of Pt on YSZ investigated by means of Pt model electrodes. → Two different geometry dependencies of the polarization resistance identified. → At higher temperatures the oxygen exchange reaction proceeds via a Pt surface path. → At lower temperatures a bulk path through the Pt thin film electrode is discussed. - Abstract: The oxygen exchange kinetics of platinum on yttria-stabilized zirconia (YSZ) was investigated by means of geometrically well-defined Pt microelectrodes. By variation of electrode size and temperature it was possible to separate two temperature regimes with different geometry dependencies of the polarization resistance. At higher temperatures (550-700 deg. C) an elementary step located close to the three phase boundary (TPB) with an activation energy of ∼1.6 eV was identified as rate limiting. At lower temperatures (300-400 deg. C) the rate limiting elementary step is related to the electrode area and exhibited a very low activation energy in the order of 0.2 eV. From these observations two parallel pathways for electrochemical oxygen exchange are concluded. The nature of these two elementary steps is discussed in terms of equivalent circuits. Two combinations of parallel rate limiting reaction steps are found to explain the observed geometry dependencies: (i) Diffusion through an impurity phase at the TPB in parallel to diffusion of oxygen through platinum - most likely along Pt grain boundaries - as area-related process. (ii) Co-limitation of oxygen diffusion along the Pt|YSZ interface and charge transfer at the interface with a short decay length of the corresponding transmission line (as TPB-related process) in parallel to oxygen diffusion through platinum.

  20. Oxides Surfaces and Novel Electronic Properties

    Science.gov (United States)

    Koirala, Pratik

    The scope of this thesis extends to the study of surface structures and electronic properties in a number of complex oxides. The c(6x2) surface reconstruction on SrTiO3 (001) was solved using a combination of plan view transmission electron microscopy imaging, atomic resolution secondary electron imaging, and density functional theory calculations. This work provided fundamental insights on the effects of dielectric screening in secondary electron generation. A thorough analysis on the limitation and functionality of transmission plan view imaging showed that the kinematical approximations used in the separation of top and bottom surfaces is only valid in thin samples (˜5 nm or less for SrTiO3). The presence of an inversion center in the surface structure also made separation of the top and bottom surfaces more robust. Surface studies of two other oxides, KTaO3 and NdGaO3, provided understanding on the mechanism of surface heterogeneity and segregation. In the case of KTaO3, selective ion sputtering and the loss of K resulted in large stoichiometric variations at the surface. Annealing of such samples led to the formation of a potassium deficient tetragonal phase (K 6Ta10.8O30) on the surface. A similar phenomenon was also observed in NdGaO3. Exploratory surface studies of the rare earth scandates (ReScO3 , Re = Gd, Tb, Dy) led to the observation of large flexoelectric bending inside an electron microscope. Thin rods of these scandates bent by up to 90 degree under a focused electron beam; the bending was fully reversible. Ex-situ measurements of flexoelectric coe cient performed by an- other graduate student, Christopher Mizzi, confirmed that the scandates have a large flexocoupling voltage (˜42 V). Electronic structure of the lanthanide scandates was studied using temperature depen- dent X-ray photoelectron spectroscopy and hybrid density functional theory calculations. The amount of charging under X-ray illumination was greatly reduced with increasing

  1. Reaction of Br2 with adsorbed CO on Pt, studied by the surface interrogation mode of scanning electrochemical microscopy.

    Science.gov (United States)

    Wang, Qian; Rodríguez-López, Joaquín; Bard, Allen J

    2009-12-02

    Scanning electrochemical microscopy surface interrogation (SI-SECM) in the cyclic voltammetry mode was successfully used to detect and quantify adsorbed CO on a Pt electrode by reaction with electrogenerated Br(2). The two-electrode setup used in this new technique allowed the production of Br(2) on an interrogator tip, which reported a transient positive feedback above a Pt substrate at open circuit as an indication of the reactivity of this halogen with CO((ads)). Br(-) and CO(2) are shown to be the main products of the reaction (in the absence of O(2)), which may involve the formation of bromophosgene as a hydrolyzable intermediate. Under saturation conditions, CO((ads)) was reproducibly quantified at the polycrystalline Pt surface with theta(CO) approximately = 0.5. The reaction is shown to be blocked by the action of pre-adsorbed cyanide, which demonstrates the surface character of the process. The formation of CO(2) as an end product was further tested in a bulk experiment: addition of Pt black to a mixture of Br(2) in 0.5 M H(2)SO(4) through which CO was bubbled gave a precipitate of BaCO(3) in a saturated solution of Ba(OH)(2). The use of SI-SECM allowed access to a reaction that would otherwise be difficult to prove through conventional electrochemistry on a single electrode.

  2. Self-assembled monolayers of 1-alkenes on oxidized platinum surfaces as platforms for immobilized enzymes for biosensing

    Energy Technology Data Exchange (ETDEWEB)

    Alonso, Jose Maria; Bielen, Abraham A.M. [Laboratory of Organic Chemistry, Wageningen University, Dreijenplein 8, 6703 HB, Wageningen (Netherlands); Olthuis, Wouter [BIOS Lab on a Chip Group, MESA+ and MIRA Institutes, University of Twente, P.O. Box 217, 7500 AE Enschede (Netherlands); Kengen, Servé W.M. [Laboratory of Microbiology, Wageningen University, 6703HB Wageningen (Netherlands); Zuilhof, Han, E-mail: han.zuilhof@wur.nl [Laboratory of Organic Chemistry, Wageningen University, Dreijenplein 8, 6703 HB, Wageningen (Netherlands); Department of Chemical and Materials Engineering, King Abdulaziz University, Jeddah 22254 (Saudi Arabia); Franssen, Maurice C.R., E-mail: maurice.franssen@wur.nl [Laboratory of Organic Chemistry, Wageningen University, Dreijenplein 8, 6703 HB, Wageningen (Netherlands)

    2016-10-15

    Highlights: • Three different oxidases are covalently attached to alkene based SAMs on PtOx. • Attached enzymes remain active and their activity is assessed by chronoamperometry. • Functionalized PtOx allows electron mediator free chronoamperometry measurements. • The thus formed enzyme electrodes are useful as biosensors for glucose and lactate. • Immobilization of human HAOX foresees in vivo lactate monitoring in humans. - Abstract: Alkene-based self-assembled monolayers grafted on oxidized Pt surfaces were used as a scaffold to covalently immobilize oxidase enzymes, with the aim to develop an amperometric biosensor platform. NH{sub 2}-terminated organic layers were functionalized with either aldehyde (CHO) or N-hydroxysuccinimide (NHS) ester-derived groups, to provide anchoring points for enzyme immobilization. The functionalized Pt surfaces were characterized by X-ray photoelectron spectroscopy (XPS), static water contact angle (CA), infrared reflection absorption spectroscopy (IRRAS) and atomic force microscopy (AFM). Glucose oxidase (GOX) was covalently attached to the functionalized Pt electrodes, either with or without additional glutaraldehyde crosslinking. The responses of the acquired sensors to glucose concentrations ranging from 0.5 to 100 mM were monitored by chronoamperometry. Furthermore, lactate oxidase (LOX) and human hydroxyacid oxidase (HAOX) were successfully immobilized onto the PtOx surface platform. The performance of the resulting lactate sensors was investigated for lactate concentrations ranging from 0.05 to 20 mM. The successful attachment of active enzymes (GOX, LOX and HAOX) on Pt electrodes demonstrates that covalently functionalized PtOx surfaces provide a universal platform for the development of oxidase enzyme-based sensors.

  3. Preparation of Pt Ag alloy nanoisland/graphene hybrid composites and its high stability and catalytic activity in methanol electro-oxidation

    Directory of Open Access Journals (Sweden)

    Feng Lili

    2011-01-01

    Full Text Available Abstract In this article, PtAg alloy nanoislands/graphene hybrid composites were prepared based on the self-organization of Au@PtAg nanorods on graphene sheets. Graphite oxides (GO were prepared and separated to individual sheets using Hummer's method. Graphene nano-sheets were prepared by chemical reduction with hydrazine. The prepared PtAg alloy nanomaterial and the hybrid composites with graphene were characterized by SEM, TEM, and zeta potential measurements. It is confirmed that the prepared Au@PtAg alloy nanorods/graphene hybrid composites own good catalytic function for methanol electro-oxidation by cyclic voltammograms measurements, and exhibited higher catalytic activity and more stability than pure Au@Pt nanorods and Au@AgPt alloy nanorods. In conclusion, the prepared PtAg alloy nanoislands/graphene hybrid composites own high stability and catalytic activity in methanol electro-oxidation, so that it is one kind of high-performance catalyst, and has great potential in applications such as methanol fuel cells in near future.

  4. AFM studies and electrochemical characterization of boron-doped diamond surfaces modified with metal oxides by the Sol-Gel method

    Directory of Open Access Journals (Sweden)

    Suffredini Hugo B.

    2006-01-01

    Full Text Available Continuing previous investigations, direct surface modifications of boron-doped diamond (BDD electrodes with metal oxides (PtOx, RuO2, IrO2 and PbO2 and with some mixed composites were carried out by the Sol-Gel technique. The materials were studied by atomic force microscopy (AFM to determine their surface topologies and by electrochemical techniques to establish the catalytic activity towards the oxygen evolution reaction (OER and also, for the PtOx and PtOx-RuO2 composites, the ethanol oxidation reactions in acid media. The stability of PtOx coating covered by a Nafion® film was also tested by long-term operation. The AFM results indicated sites of heterogeneous deposition and the electrochemical studies demonstrated that the active surface area changed considerably with the proposed method of modification. The IrO2/BDD electrode showed the best performance to the OER with the onset of the oxidation current at ~1.4 V, a value 200 mV lower than for the PtOx/BDD electrode. The enhanced stability of PtOx/BDD electrodes achieved by the application of a Nafion® film and already reported in acid media was further proved using the ethanol oxidation reaction. Only a small loss of activity (6% was observed after 4-hours electrolysis while one-thousand voltammetric cycles left the surface practically unchanged. In addition, preliminary studies for the same reaction on PtOx/BDD and PtOx-RuO2/BDD electrodes demonstrated the excellent activity of these mixed Sol-Gel coatings on the BDD surface and the possibility of further investigations for practical applications.

  5. Surface characterization and dehydrocyclization activity of Pt/KL catalysts prepared by different methods

    International Nuclear Information System (INIS)

    Arcoya, Adolfo; Seoane, Xose Lois; Grau, Javier Mario

    2002-01-01

    Three Pt/KL-zeolite catalysts containing 1 wt.% of metal were prepared by different procedures: CI-1 and CI-2 by wetness impregnation of the zeolite with aqueous solutions of Pt(NH 3 ) 4 (OH) 2 and Pt(NH 3 ) 4 (NO 3 ) 2 , respectively, and CE-3 by ion exchange with a Pt(NH 3 ) 4 (OH) 2 solution. These samples were successively calcined at 573 K and reduced at 773 K. An additional sample, CE-3-n, was obtained from CE-3 by ion-exchange with KNO 3 . The catalysts were characterized by H 2 -O 2 titration, TPD of NH 3 , XRD, CO-FTIR and XPS and tested in the dehydrocyclization of n-heptane to toluene at 723 K, 100 kPa, WHSV=3.4 h -1 and H 2 /nC 7 =7.3 mol mol -1 in a fixed bed tubular reactor. Characterization results show that Pt dispersion for the ion exchanged samples is higher than for the impregnated ones and CE-3 is the more acidic catalyst. FTIR measurements indicate that the highest population of electron reach platinum species (Pt δ- ) is found in CE-3-n, while CE-3 exhibits the highest concentration of electron deficient platinum species (Pt δ+ ). The order of dehydrocyclization activity, CE-3-n>CI-2>CI-1>CE-3, roughly correlates with that of the intensity of the FTIR bands attributed to Pt δ- . The low selectivity toward toluene of CE-3 is attributed to the protons generated during the reduction of Pt 2+ exchanged

  6. Sputtering ultra-small Pt on nanographitic flakes deposited by electrophoresis for ethanol electro oxidation

    Science.gov (United States)

    Daryakenari, Ahmad Ahmadi; Daryakenari, Mohammad Ahmadi; Omidvar, Hamid

    2018-01-01

    To acquire highly efficient and cost-effective fuel cells, numerous research works have been carried out to the development low cost and excellent performance of electrocatalysts. In this paper, a solution-based electrophoretic deposition (EPD) technique for fabrication of Pt-based catalyst layers is studied. Nanographitic flake coatings used as catalyst support for sputtered platinium (Pt) were fabricated via the electrophoretic deposition (EPD) of dispersed nanographitic flakes in isopropyl alcohol. Magnesium nitrate hexahydrate (MNH) was used as an additive binder in the EPD process. Subsequently, the platinium particles were deposited by a direct sputtering on the fabricated nanographitic flake coatings.

  7. Influence of the concentration of borohydride towards hydrogen production and escape for borohydride oxidation reaction on Pt and Au electrodes - experimental and modelling insights

    Science.gov (United States)

    Olu, Pierre-Yves; Bonnefont, Antoine; Braesch, Guillaume; Martin, Vincent; Savinova, Elena R.; Chatenet, Marian

    2018-01-01

    The Borohydride Oxidation Reaction (BOR), the anode reaction in a Direct borohydride fuel cell (DBFC), is complex and still poorly understood, which impedes the development and deployment of the DBFC technology. In particular, no practical electrocatalyst is capable to prevent gaseous hydrogen generation and escape from its anode upon operation, which lowers the fuel-efficiency of the DBFC and raises safety issues in operation. The nature of the anode electrocatalysts strongly influences the hydrogen escape characteristics of the DBFC, which demonstrates how important it is to isolate the BOR mechanism in conditions relevant to DBFC operation. In this paper, from a selected literature review and BOR experiments performed in differential electrochemical mass spectrometry (DEMS) in a wide range of NaBH4 concentration (5-500 mM), a microkinetic model of the BOR for both Pt and Au surfaces is proposed; this model takes into account the hydrogen generation and escape.

  8. One-pot ionic liquid-assisted synthesis of highly dispersed PtPd nanoparticles/reduced graphene oxide composites for nonenzymatic glucose detection.

    Science.gov (United States)

    Li, Mian; Bo, Xiangjie; Zhang, Yufan; Han, Ce; Guo, Liping

    2014-06-15

    A series of highly dispersed bimetallic PtPd alloy nanoparticles (NPs) anchored on reduced graphene oxide (RGO) have been synthesized with the assistance of ionic liquid (IL: [VEIM]BF4). Different ratios of (PtCl6)(2-) and (PdCl4)(2-) ions were firstly attached to IL functionalized graphene oxide (GO) sheets in ethylene glycol (EG), and then the encased metal ions and graphene oxide sheets were reduced simultaneously by EG with the assistance of microwave. The characterization results of scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and X-ray diffraction (XRD) demonstrate that PtPd alloy NPs with small particle sizes are uniformly dispersed on RGO. Electrochemical measurements reveal that PtPd-IL-RGO modified electrode can directly catalyze glucose oxidation and display enhanced current response compared with PtPd-RGO (such as: a response time within 3s, a linear range from 0.1 to 22 mM at 0 V, good reproducibility, considerable stability, and excellent anti-interference to electroactive molecules and Cl(-)). The superior catalytic activity and selectivity make PtPd-IL-RGO nanomaterials very promising for applications in direct detection of glucose. Copyright © 2014 Elsevier B.V. All rights reserved.

  9. The effect of Rhδ+ dopant in SrTiO3 on the active oxidation state of co-catalytic Pt nanoparticles in overall water splitting

    NARCIS (Netherlands)

    Zoontjes, M.G.C.; Han, Kai; Han, K.; Huijben, Mark; van der Wiel, Wilfred Gerard; Mul, Guido

    2016-01-01

    We report on the oxidation state of Pt nanoparticles when deposited on SrTiO3 or Rh-doped SrTiO3 under realistic solar water-splitting conditions. The oxidation state was investigated using state-of-the-art analysis of the reaction in a continuously stirred tank reactor (CSTR) connected to a micro

  10. The structure and reactivity of adsorbates on stepped Rh and Pt surfaces investigated by LEED, HREELS, TPD, XPS and STM

    Energy Technology Data Exchange (ETDEWEB)

    Batteas, J.D. [Univ. of California, Berkeley, CA (United States). Dept. of Chemistry]|[Lawrence Berkeley Lab., CA (United States). Materials Science Div.

    1995-06-01

    Defects on surfaces such as steps play an important role in surface chemistry. In order to obtain an understanding of the influence of steps in surface chemical reactions, the structure and reactivity of small molecules (O{sub 2}, CO, H{sub 2}S, and C{sub 2}H{sub 4}) on atomically stepped surfaces of RH and Pt have been investigated. The detailed structures of CO and oxygen bonded to the Rh(110) surface were determined. The CO molecules bond near the short bridge sites with the CO molecular axis tilted approximately 24{degree} from the surface normal. Oxygen atoms are bound asymmetrically in the 3-fold fcc hollow-sites to the (111) facets of the steps. The interactions of CO and oxygen on the Rh(311) surface were examined. The reaction of CO with the ordered phases of O shows two distinct reaction channels, a low temperature reaction limited channel (200 K) and a high temperature diffusion limited channel (350 K). Models of the reaction geometry and dynamics are proposed. The thermal decomposition of ethylene was examined on the Rh(311) surface. The stable decomposition species (C{sub 2}H, CH and C{sub 2}) are formed near 300 K, approximately 100 K lower on the stepped Rh(311) than on the flatter Rh(111) surface. The formation of these species at lower temperatures is attributed to the stepped nature of the surface. Finally, in situ STM was used to examine surface structural changes of a stepped Pt(111) crystal under coadsorption of sulfur and CO. This is the first direct evidence for a new mechanism by which a surface covered with an unreactive, strongly chemisorbed overlayer can form new sites, for bonding and reactions to occur, by massive surface restructuring at the step edges. This new surface phenomenon answers some of the puzzles of metal surface catalysis and its implications are described. 278 refs.

  11. Preparation of catalysts PtSb2O5.SnO2 supported on carbon and ATO using the alcohol reduction method for electrochemical oxidation of ethanol

    International Nuclear Information System (INIS)

    Ayoub, Jamil Mahmoud Said

    2013-01-01

    Pt Sn/C-ATO electrocatalysts with different Pt:Sn atomic ratios (90:10, 70:30 and 50:50) were prepared in a single step by an alcohol-reduction process using H 2 PtCl 6 .6H 2 O and SnCl 2 .2H 2 O as metal sources and ethylene glycol as solvent and reducing agent and a physical mixture of carbon Vulcan XC72 (85 wt%) and Sb 2 O 5 .SnO 2 (15 wt%) as support (C-ATO). The obtained materials were characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The catalytic activity for ethanol electro-oxidation in acid medium was investigated by cyclic voltammetry and chronoamperometry and in single direct ethanol fuel cell (DEFC). XRD analyses showed that Pt(FCC), SnO 2 , carbon and ATO phases coexist in the obtained materials. The electrochemical studies showed that PtSn/C-ATO electrocatalysts were more active for ethanol electro-oxidation than PtSn/C electrocatalyst. The experiments at 100 deg C on a single DEFC showed that the power density of the cell using Pt Sn/C-ATO (90:10) was nearly 100% higher than the one obtained using Pt Sn/C (50:50). FTIR measurements showed that the addition of ATO to Pt Sn/C favors the formation of acetic acid as a product while for PtSn/C acetaldehyde was the principal product formed. (author)

  12. Photocatalysis of Modified Transition Metal Oxide Surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Batzill, Matthias

    2018-02-28

    The goal of this project has been to establish a cause-effect relationship for photocatalytic activity variations of different structures of the same material; and furthermore gain fundamental understanding on modification of photocatalysts by compositional or surface modifications. The reasoning is that gaining atomic scale understanding of how surface and bulk modifications alter the photo reactivity will lead to design principles for next generation photocatalysts. As a prototypical photocatalyst the research focused on TiO2 synthesized in well-defined single crystalline form to enable fundamental characterizations.We have obtained results in the following areas: (a) Preparation of epitaxial anataseTiO2 samples by pulsed laser deposition. (b) Comparison of hydrogen diffusion on different crystallographic surface. (c) Determining the stability of the TiO2(011)-2x1 reconstruction upon interactions with adsorbates. (d) Characterization of adsorption and (thermal and photo) reaction of molecules with nitro-endgroups, (e) Exploring the possibility of modifying planar model photocatalyst surfaces with graphene to enable fundamental studies on reported enhanced photocatalytic activities of graphene modified transition metal oxides, (f) gained fundamental understanding on the role of crystallographic polymorphs of the same material for their photocatalytic activities.

  13. Performance of PtPd electrocatalysts in direct methanol fuel cell.

    Science.gov (United States)

    Kim, In-Tae; Choi, Mahnsoo; An, Jung-Chul; Lee, Hong-Ki; Shim, Joongpyo

    2010-05-01

    PtPd nanoparticles on carbon black were prepared to investigate the role of Pd in the anode and cathode of a direct methanol fuel cell (DMFC). The PtPd catalysts in the anode showed a significantly lower performance than the PtRu catalyst. However, the cell performances of these catalysts in the cathode were comparable to that of the Pt catalyst. From cyclic voltammetry, it was observed that the Pd with the Pt catalyst lowered the peak potential and increased the coulombic charge for oxide reduction on the surface of the catalyst. Also, the Pd catalyst without Pt showed relatively high activity for oxygen reduction reaction.

  14. On the stability of the CO adsorption-induced and self-organized CuPt surface alloy

    DEFF Research Database (Denmark)

    Andersson, Klas Jerker; Chorkendorff, Ib

    2010-01-01

    The stability of the recently discovered CO-induced and self-organized CuPt surface alloy was explored at near ambient pressures of O-2 (200 mbar) at room temperature, in a CO + H-2 mix (P-tot = 220 mbar, 4% CO) from room temperature to 573 K, as well as in a CO + H2O mix (P-tot = 17 mbar, 50% CO...

  15. 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)

  16. Effect of P on the electrochemical activity of carbon supported Pt-Ru alloy catalyst for methanol oxidation.

    CSIR Research Space (South Africa)

    Mohlala, M

    2007-11-01

    Full Text Available In polymer electrolyte membrane fuel cell (PEMFC), platinum is recognized to be the most active metal for methanol oxidation, however there is a strong CO adsorption tendency, which blocks the surface for further methanol adsorption and leads...

  17. Stable structures and potential energy surface of the metallic clusters: Ni, Cu, Ag, Au, Pd, and Pt

    Science.gov (United States)

    Wu, Xia; Sun, Yan

    2017-06-01

    Metallic clusters have been widely studied due to their special electrical, optical, and catalytic properties. The many-body Gupta potential is applied to describe the interatomic interaction of Ni, Cu, Ag, Au, Pd, and Pt clusters, and their global minimal structures within 100 atoms are optimized using dynamic lattice searching (DLS) method. The configurational distribution of global minima is analyzed, and the geometrical difference among these clusters is demonstrated. Results show that the dominant motif of Ni and Cu clusters is the icosahedron, and in Ag and Au clusters the number of decahedra is slightly larger than that of the icosahedra. However, more face-centered cubic (fcc), stacking fault fcc, and amorphous structures are formed in Au clusters than in Ag clusters. Furthermore, the main motif of Pd and Pt clusters is the decahedron. In particular, Ni98 adopts a Leary tetrahedral motif, and Pt54 is a central vacant icosahedron. The difference related to the potential parameters of these metallic clusters is further investigated by energy analysis. Moreover, the potential energy surfaces (PES) of 38-atom metallic clusters is characterized in terms of conformational analysis. It was found that the sequence of the number of local minima on the PES from large to low is Ni, Cu, Ag, Pt, Pd, and Au.

  18. Electrocatalysis of the Ethylene glycol oxidation reaction and in situ Fourier-transform infared study on PtMo/C electrocatalysts in alkaline and acid media

    Science.gov (United States)

    Pech-Rodríguez, W. J.; Calles-Arriaga, C.; González-Quijano, D.; Vargas-Gutiérrez, G.; Morais, C.; Napporn, T. W.; Rodríguez-Varela, F. J.

    2018-01-01

    PtMo/C (Pt:Mo atomic ratios of 1:1, 2:1 and 3:1) and Pt/C electrocatalysts synthesized by the formic acid method are investigated for the ethylene glycol oxidation reaction (EGOR) in alkaline and acid media. From XRD measurements, the crystallite sizes are between 2.5 and 4.3 nm. Electrochemical characterization of the EGOR on the electrocatalysts shows that the PtMo/C series exhibit higher electrocatalytic activity. When comparing the two electrolytes, the mass current densities obtained in alkaline media are significantly higher than in the acid counterpart. Among the bimetallic anodes, Pt1Mo1/C delivered a high performance in both media. In situ FTIR spectroscopy analysis has been performed to study the pathway of the EGOR. In alkaline media, the PtMo/C electrocatalysts have a higher selectivity for the C2 pathway resulting in the formation of species such as glycolate, glyoxal and glyoxylate. On the other hand, in acid electrolyte, the PtMo/C anodes show a preferential C1 pathway at high potentials and the main intermediate is identified as glycolic acid. The results indicate that the higher catalytic activity of PtMo/C electrocatalysts towards the EGOR may be attributed to the bifunctional mechanism and also to an electronic effect because of the incorporation of Mo atoms into the catalysts structure.

  19. Towards the elucidation of the high oxygen electroreduction activity of PtxY: surface science and electrochemical studies of Y/Pt(111)

    DEFF Research Database (Denmark)

    Johansson, Tobias Peter; Ulrikkeholm, Elisabeth Therese; Hernandez-Fernandez, Patricia

    2014-01-01

    programmed desorption of CO. When depositing a large amount of yttrium at 1173 K, a (1.88 × 1.88)R30° structure relative to Pt(111) was observed by low energy electron diffraction. Such an electron diffraction pattern could correspond to a (2 × 2)R30° structure under 6% compressive strain. This structure...... is in agreement with the structure of the vacancies in a Pt Kagomé layer in Pt5Y rotated 30° with respect to the bulk of the Pt(111). The Pt overlayer is relatively stable in air; however, after performing oxygen reduction activity measurements in an electrochemical cell, a thick Pt overlayer was measured...

  20. Freestanding graphene paper decorated with 2D-assembly of Au@Pt nanoparticles as flexible biosensors to monitor live cell secretion of nitric oxide.

    Science.gov (United States)

    Zan, Xiaoli; Fang, Zheng; Wu, Jin; Xiao, Fei; Huo, Fengwei; Duan, Hongwei

    2013-11-15

    We report the development of a new type of flexible electrochemical biosensors based on graphene paper loaded with closely-packed Au@Pt core-shell nanoparticles as a freestanding cell culture substrate for real-time monitoring cell secretion of nitric oxide. The hybrid electrode was fabricated through a modular approach in which 2D-assembly of nanoparticles formed at the oil-water interface was transferred onto graphene paper by dip-coating. We have shown that the independently optimized metal nanostructures and graphene paper were integrated into functional electrodes with high electrocatalytic activity. When used for the detection of nitric oxide, the flexible electrodes have demonstrated high sensitivity, a wide linear range, and a low detection limit, which, in combination with its biocompatibility, offer unique opportunities for the real-time monitoring of nitric oxide secretion by human endothelial vein cells grown on the electrode. These interesting findings collectively demonstrate the potential of our modular approach for designing high-performance flexible electrodes with tailored surface properties. Copyright © 2013 Elsevier B.V. All rights reserved.

  1. Pt nanoparticle modified single walled carbon nanotube network electrodes for electrocatalysis: control of the specific surface area over three orders of magnitude

    NARCIS (Netherlands)

    Miller, T.S.; Sansuk, S.; Lai, Stanley; Macpherson, J.V.; Unwin, P.R.

    2015-01-01

    The electrodeposition of Pt nanoparticles (NPs) on two-dimensional single walled carbon nanotube (SWNT) network electrodes is investigated as a means of tailoring electrode surfaces with a well-defined amount of electrocatalytic material. Both Pt NP deposition and electrocatalytic studies are

  2. Preparation and Thermoelectric Characteristics of ITO/PtRh:PtRh Thin Film Thermocouple

    Science.gov (United States)

    Zhao, Xiaohui; Wang, Hongmin; Zhao, Zixiang; Zhang, Wanli; Jiang, Hongchuan

    2017-12-01

    Thin film thermocouples (TFTCs) can provide more precise in situ temperature measurement for aerospace propulsion systems without disturbance of gas flow and surface temperature distribution of the hot components. ITO /PtRh:PtRh TFTC with multilayer structure was deposited on alumina ceramic substrate by magnetron sputtering. After annealing, the TFTC was statically calibrated for multiple cycles with temperature up to 1000 °C. The TFTC with excellent stability and repeatability was realized for the negligible variation of EMF in different calibration cycles. It is believed that owing to oxygen diffusion barriers by the oxidation of top PtRh layer and Schottky barriers formed at the grain boundaries of ITO, the variation of the carrier concentration of ITO film is minimized. Meanwhile, the life time of TFTC is more than 30 h in harsh environment. This makes ITO/PtRh:PtRh TFTC a promising candidate for precise surface temperature measurement of hot components of aeroengines.

  3. Clarification of the mechanism of sulfur trioxide electrolysis. Evaluation of SO3 and O atom adsorbed on Pt surface

    International Nuclear Information System (INIS)

    Suzuki, Chikashi; Nakagiri, Toshio

    2008-01-01

    We developed a hybrid thermo-chemical process, which included a SO 3 electrolysis process utilizing the heat supplied by a fast breeder reactor (FBR), as a new hydrogen production process. To clarify the mechanism of SO 3 electrolysis, we evaluated the electronic states of SO 3 and O atom adsorbed on the Pt (111) surface using first-principles calculations with a slab model. Moreover, we evaluated the chemical bonding states of SO 3 and adsorbed O using molecular orbital calculation on the basis of the calculations using a slab model. We found that there were two stable adsorbed SO 3 configurations on the Pt surface. From the molecular orbital calculation, it was found that the S-O bond became weak by SO 3 absorption, and it was conjectured that SO 3 dissociation proceeded through the intermediate state of adsorbed SO 2 and adsorbed O on the Pt surface. Moreover, we derived the O coverage considering the adsorbed SO 2 and evaluated the influence of SO 3 adsorption energy on the O coverage. (author)

  4. Pt promotion and spill-over processes during deposition and desorption of upd-H(ad) and OH(ad) on Pt(x)Ru(1-x)/Ru(0001) surface alloys.

    Science.gov (United States)

    Hoster, Harry E; Janik, Michael J; Neurock, Matthew; Behm, R Jürgen

    2010-09-21

    The electrochemical adsorption of underpotential deposited hydrogen (upd-H(ad)) and OH(ad) on structurally well-defined Pt(x)Ru(1-x)/Ru(0001) surface alloys was investigated by cyclic voltammetry and density functional theory (DFT) calculations. The adsorption energies of both upd-H(ad) and OH(ad) decrease with increasing Pt content in the adsorption ensemble, shifting the onset of upd-H(ad) and OH(ad) formation to increasingly cathodic and anodic potentials, respectively. For bare Ru(0001) and for Ru(3) sites in the surface alloy, the stability regions of these two species overlap or almost overlap, respectively. Similar to previous findings for upd-H(ad) adsorption/desorption on partly Pt monolayer island covered Ru(0001) surfaces (J. Phys. Chem. B 2004, 108, 14780), we find a sharp peak at approximately 100 mV vs. RHE in each scan direction, which is attributed to a Pt catalyzed OH(ad) upd-H(ad) replacement on Ru(3) sites, via adsorption on Pt rich sites and spill-over to Ru(3) sites. The decrease of the integrated charge in these peaks with the third power of the Ru surface concentration, which for a random distribution of surface atoms reflects the availability of Ru(3) sites, supports the above assignment.

  5. Highly Effective Pt-Based Water-Gas Shift Catalysts by Surface Modification with Alkali Hydroxide Salts.

    Science.gov (United States)

    Kusche, Matthias; Bustillo, Karen; Agel, Friederike; Wasserscheid, Peter

    2015-03-01

    Herein, we describe an economical and convenient method to improve the performance of Pt/alumina catalysts for the water-gas shift reaction through surface modification of the catalysts with alkali hydroxides according to the solid catalyst with ionic liquid layer approach. The results are in agreement with our findings reported earlier for methanol steam reforming. This report indicates that alkali doping of the catalyst plays an important role in the observed catalyst activation. In addition, the basic and hygroscopic nature of the salt coating contributes to a significant improvement in the performance of the catalyst. During the reaction, a partly liquid film of alkali hydroxide forms on the alumina surface, which increases the availability of H 2 O at the catalytically active sites. Kinetic studies reveal a negligible effect of the KOH coating on the rate dependence of CO and H 2 O partial pressures. TEM studies indicate an agglomeration of the active Pt clusters during catalyst preparation; restructuring of Pt nanoparticles occurs under reaction conditions, which leads to a highly active and stable system over 240 h time on stream. Excessive pore fillings with KOH introduce a mass transfer barrier as indicated in a volcano-shaped curve of activity versus salt loading. The optimum KOH loading was found to be 7.5 wt %.

  6. Small-Sized Tungsten Nitride Particles Strongly Anchored on Carbon Nanotubes and their Use as Supports for Pt for Methanol Electro-oxidation.

    Science.gov (United States)

    Liu, Yuan; Yan, Haijing; Zhou, Xiaoguang; Li, Mingxia; Fu, Honggang

    2015-12-07

    The anchoring of small-sized WN (tungsten nitride) nanoparticles (NPs) with good dispersion on carbon nanotubes (CNTs) offers an effective means of obtaining promising materials for use in electrocatalysis. Herein, an effective method based on grinding treatment followed by a nitridation process is proposed to realize this goal. In the synthesis, a solution containing H4 [SiO4 (W3 O9 )4 ] (SiW12 ) and CNTs modified with polyethylenimine (PEI-CNTs) was ground to dryness. Small-sized WN NPs were anchored onto the CNTs with good dispersion after calcination under NH3 . Under hydrothermal assembly conditions (absence of grinding), WN particles of larger size and with inferior dispersion were obtained, demonstrating the important role of the grinding process. The benefit of the small-sized WN has been demonstrated by using WN/CNTs as a support for Pt to catalyze the methanol electro-oxidation reaction. The mass activity of Pt-WN/CNTs-G-70 (where G denotes the grinding treatment, and 70 is the loading amount (%) of WN in the WN/CNTs) was evaluated as about 817 mA mg(-1) Pt , better that those of commercial Pt/C (340 mA mg(-1) Pt ) and Pt/CNTs (162 mA mg(-1) Pt ). The Pt-WN/CNTs-G also displayed good CO tolerance. In contrast, Pt-WN/CNTs prepared without the grinding process displayed an activity of 344 mA mg(-1) Pt , verifying the key role of grinding treatment in the preparation of WN/CNTs with good co-catalytic effect. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. 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)

  8. Electrochemical synthesis of mesoporous CoPt nanowires for methanol oxidation

    OpenAIRE

    Serrà, Albert; Montiel Argaiz, Manuel; Gómez, Elvira; Vallés Giménez, Elisa

    2014-01-01

    A new electrochemical method to synthesize mesoporous nanowires of alloys has been developed. Electrochemical deposition in ionic liquid-in-water (IL/W) microemulsion has been successful to grow mesoporous CoPt nanowires in the interior of polycarbonate membranes. The viscosity of the medium was high, but it did not avoid the entrance of the microemulsion in the interior of the membrane’s channels. The structure of the IL/W microemulsions, with droplets of ionic liquid (4 nm average diameter)...

  9. Study on single step solid state synthesis of WC@C nanocomposite and electrochemical stability of synthesized WC@C & Pt/WC@C for alcohol oxidation (methanol/ethanol)

    Energy Technology Data Exchange (ETDEWEB)

    Singla, Gourav, E-mail: gsinghla@gmail.com; Singh, K., E-mail: kusingh@thapar.edu; Pandey, O.P., E-mail: oppandey@thapar.edu

    2016-04-25

    WC@C nano composite was prepared by a single step solid–state reaction through in situ reduction and carburization of WO{sub 3} in the presence of Mg and activated charcoal. The XRD results and thermodynamics analysis showed that the optimization of reaction temperature facilitates the reduction as well as carburization of tungsten oxide(s) at different reaction temperature. Thermogravimetric analysis of the product was done to assess the thermal stability in air. The Raman spectroscopy was used to find out the nature (amorphous/graphitic) of carbon in the obtained phase. The N{sub 2} adsorption–desorption measurement showed a narrow pore size distribution from 3 to 4 nm with BET surface area of up to 522.5 m{sup 2}/g. TEM/HRTEM images confirmed formation of the WC nano particles with spherical morphology. Electrochemical stability of pure and platinized carbide sample (Pt/WC) has been investigated using cyclic voltammetry in acidic media for alcohol (methanol and ethanol) oxidation. - Highlights: • Tungsten carbide nano powder was synthesized using charcoal as carbon source. • Formation of WC occurs through the formation of lower tungsten oxide. • CO{sub 2}/CO ratio effect the formation of WC. • Mesoporous tungsten carbide with surface areas 522.5 m{sup 2}/g obtained by using charcoal. • Pt modified WC powder showed higher electrochemical stability.

  10. Control of Surface and Edge Oxidation on Phosphorene.

    Science.gov (United States)

    Kuntz, Kaci L; Wells, Rebekah A; Hu, Jun; Yang, Teng; Dong, Baojuan; Guo, Huaihong; Woomer, Adam H; Druffel, Daniel L; Alabanza, Anginelle; Tománek, David; Warren, Scott C

    2017-03-15

    Phosphorene is emerging as an important two-dimensional semiconductor, but controlling the surface chemistry of phosphorene remains a significant challenge. Here, we show that controlled oxidation of phosphorene determines the composition and spatial distribution of the resulting oxide. We used X-ray photoemission spectroscopy to measure the binding energy shifts that accompany oxidation. We interpreted these spectra by calculating the binding energy shift for 24 likely bonding configurations, including phosphorus oxides and hydroxides located on the basal surface or edges of flakes. After brief exposure to high-purity oxygen or high-purity water vapor at room temperature, we observed phosphorus in the +1 and +2 oxidation states; longer exposures led to a large population of phosphorus in the +3 oxidation state. To provide insight into the spatial distribution of the oxide, transmission electron microscopy was performed at several stages during the oxidation. We found crucial differences between oxygen and water oxidants: while pure oxygen produced an oxide layer on the van der Waals surface, water oxidized the material at pre-existing defects such as edges or steps. We propose a mechanism based on the thermodynamics of electron transfer to interpret these observations. This work opens a route to functionalize the basal surface or edges of two-dimensional (2D) black phosphorus through site-selective chemical reactions and presents the opportunity to explore the synthesis of 2D phosphorene oxide by oxidation.

  11. Dicationic ionic liquid mediated fabrication of Au@Pt nanoparticles supported on reduced graphene oxide with highly catalytic activity for oxygen reduction and hydrogen evolution

    Science.gov (United States)

    Shi, Ya-Cheng; Chen, Sai-Sai; Feng, Jiu-Ju; Lin, Xiao-Xiao; Wang, Weiping; Wang, Ai-Jun

    2018-05-01

    Ionic liquids as templates or directing agents have attracted great attention for shaping-modulated synthesis of advanced nanomaterials. In this work, reduced graphene oxide supported uniform core-shell Au@Pt nanoparticles (Au@Pt NPs/rGO) were fabricated by a simple one-pot aqueous approach, using N-methylimidazolium-based dicationic ionic liquid (1,1-bis(3-methylimadazoilum-1-yl)butylene bromide, [C4(Mim)2]2Br) as the shape-directing agent. The morphology evolution, structural information and formation mechanism of Au@Pt NPs anchored on rGO were investigated by a series of characterization techniques. The obtained nanocomposites displayed superior electrocatalytic features toward hydrogen evolution reaction (HER) and oxygen reduction reaction (ORR) compared with commercial Pt/C catalyst. This approach provides a novel route for facile synthesis of nanocatalysts in fuel cells.

  12. Investigation of the electrochemical behaviour of thermally prepared Pt-IrO2 electrodes

    Directory of Open Access Journals (Sweden)

    Konan Honoré Kondro

    2008-04-01

    Full Text Available Different IrO2 electrodes in which the molar percentage of platinum (Pt varies from 0 %mol Pt to 100 %mol Pt were prepared on titanium (Ti substrate by thermal decomposition techniques. The electrodes were characterized physically (SEM, XPS and electrochemically and then applied to methanol oxidation. The SEM micrographs indicated that the electrodes present different morphologies depending on the amount of platinum in the deposit and the cracks observed on the 0 %mol Pt electrode diminish in size tending to a compact and rough surface for 70 %mol Pt electrode. XPS results indicate good quality of the coating layer deposited on the titanium substrate. The voltammetric investigations in the supporting electrolyte indicate that the electrodes with low amount of platinum (less than 10 %mol Pt behave as pure IrO2. But in the case of electrodes containing more than 40 %mol Pt, the voltammograms are like that of platinum. Electrocatalytic activity towards methanol oxidation was observed with the electrodes containing high amount of platinum. Its oxidation begins at a potential of about 210 mV lower on such electrodes than the pure platinum electrode (100 %mol Pt. But for electrode containing low quantity of Pt, the surface of the coating is essentially composed of IrO2 and methanol oxidation occurs in the domain of water decomposition solely. The increase of the electrocatalytic behaviour of the electrodes containing high amount of Pt towards methanol oxidation is due to the bifunctional behaviour of the electrodes.

  13. Deep catalytic oxidation of heavy hydrocarbons on Pt/Al{sub 2}O{sub 3} catalysts; Oxydation catalytique totale des hydrocarbures lourds sur Pt/Al{sub 2}O{sub 3}

    Energy Technology Data Exchange (ETDEWEB)

    Diehl, F.

    1998-12-09

    Deep oxidation by air on Pt supported on alumina of a large number of heavy hydrocarbons representative of those found in a real Diesel car exhaust has been studied. Light-off temperatures between 140 and 320 deg. C on 1%Pt/alumina (80% metal dispersion) have been found. Results show that not only the physical state around the conversion area but also the chemical nature of the hydrocarbon plays an important role. Heavy hydrocarbons deep oxidation behaviour has been classified as a function of their chemical category (alkane, alkene, aromatics etc..). Oxidation of binary mixtures of hydrocarbons has shown strong inhibition effects on n-alkane or CO oxidation by polycyclic compounds like 1-methyl-naphthalene. In some cases, by-product compounds in the gas effluent (other than CO{sub 2} and H{sub 2}O) have been identified by mass-spectrometry leading to oxidation mechanism proposals for different hydrocarbons. Catalyst nature (metal dispersion, content) influence has also been studied. It is shown that turn-over activity is favoured by the increase of the metal bulk size. Acidity influence of the carrier has shown only very little influence on n-alkane or di-aromatic compound oxidation. (author)

  14. Effect of CO on surface oxidation of uranium metal

    International Nuclear Information System (INIS)

    Wang, X.; Fu, Y.; Xie, R.

    1997-01-01

    The surface reactions of uranium metal with carbon monoxide at 25 and 200 deg C have been studied by X-ray photoelectron spectroscopy (XPS);respectively. Adsorption of carbon monoxide on the surface layer of uranium metal leads to partial reduction of surface oxide and results in U4f photoelectron peak shifting to the lower binding energy. The content of oxygen in the surface oxide is decreased and O1s/O4f ratio decreases with increasing the exposure of carbon monoxide. The investigation indicates the surface layer of uranium metal has resistance to further oxidation in the atmosphere of carbon monoxide. (author)

  15. Surface acoustic load sensing using a face-shear PIN-PMN-PT single-crystal resonator.

    Science.gov (United States)

    Kim, Kyungrim; Zhang, Shujun; Jiang, Xiaoning

    2012-11-01

    Pb(In(0.5)Nb(0.5))O(3)-Pb(Mg(1/3)Nb(2/3))O(3)-PbTiO(3) (PIN-PMN-PT) resonators for surface acoustic load sensing are presented in this paper. Different acoustic loads are applied to thickness mode, thickness-shear mode, and face-shear mode resonators, and the electrical impedances at resonance and anti-resonance frequencies are recorded. More than one order of magnitude higher sensitivity (ratio of electrical impedance change to surface acoustic impedance change) at the resonance is achieved for the face-shear-mode resonator compared with other resonators with the same dimensions. The Krimholtz, Leedom, and Matthaei (KLM) model is used to verify the surface acoustic loading effect on the electrical impedance spectrum of face-shear PIN-PMN-PT single-crystal resonators. The demonstrated high sensitivity of face-shear mode resonators to surface loads is promising for a broad range of applications, including artificial skin, biological and chemical sensors, touch screens, and other touch-based sensors.

  16. 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.

  17. Diffusion and adsorption of dimers on reconstructed Pt(1 1 0) surfaces: First principle and EAM studies

    Science.gov (United States)

    Matrane, I.; Mazroui, M.; Sbiaai, K.

    2018-03-01

    We present a density functional theory (DFT) and embedded atom method (EAM) studies of Pt2 , Au2 and AuPt dimers adsorption and diffusion on the clean Pt (1 1 0) (1 × 1) surface and (1 × 2) (1 × 3) and (1 × 4) missing row reconstructed geometries. As a first step, adsorption energies are calculated for all considered dimers, and their stability is checked by computing the binding energies. Furthermore, the energy barriers for the elementary diffusion mechanisms (concerted jump, dissociation-reassociation and leapfrog) are calculated for dimers diffusion on all considered geometries. The potential energy profile for the leapfrog mechanism is provided for dimers diffusion on the (1 × 2) (1 × 3) and (1 × 4) missing row reconstructed geometries. Our results show that each of the three dimers exhibits a qualitatively different behaviours. In addition, the obtained results provide interesting atomistic information about dimers stability and mobility, which is required for understanding the macroscopic kinetics of crystal growth.

  18. The influence of surface oxide on the growth of metal/semiconductor nanowires.

    Science.gov (United States)

    Lu, Kuo-Chang; Wu, Wen-Wei; Ouyang, Hao; Lin, Yung-Chen; Huang, Yu; Wang, Chun-Wen; Wu, Zheng-Wei; Huang, Chun-Wei; Chen, Lih J; Tu, K N

    2011-07-13

    We report the critical effects of oxide on the growth of nanostructures through silicide formation. Under an in situ ultrahigh vacuum transmission electron microscope, it is observed from the conversion of Si nanowires into the metallic PtSi grains epitaxially through controlled reactions between lithographically defined Pt pads and Si nanowires. With oxide, instead of contact area, single crystal PtSi grains start forming either near the center between two adjacent pads or from the ends of Si nanowires, resulting in the heterostructure formation of Si/PtSi/Si. Without oxide, transformation from Si into PtSi begins at the contact area between them, resulting in the heterostructure formation of PtSi/Si/PtSi. The nanowire heterostructures have an atomically sharp interface with epitaxial relationships of Si(20-2)//PtSi(10-1) and Si[111]//PtSi[111]. Additionally, it has been observed that the existence of oxide significantly affects not only the growth position but also the growth behavior and the growth rate by two orders of magnitude. Molecular dynamics simulations have been performed to support our experimental results and the proposed growth mechanisms. In addition to fundamental science, the significance of the study matters for future processing techniques in nanotechnology and related applications as well.

  19. Ambient-temperature diffusion and gettering of Pt atoms in GaN with surface defect region under 60Co gamma or MeV electron irradiation

    Science.gov (United States)

    Hou, Ruixiang; Li, Lei; Fang, Xin; Xie, Ziang; Li, Shuti; Song, Weidong; Huang, Rong; Zhang, Jicai; Huang, Zengli; Li, Qiangjie; Xu, Wanjing; Fu, Engang; Qin, G. G.

    2018-01-01

    Generally, the diffusion and gettering of impurities in GaN needs high temperature. Calculated with the ambient-temperature extrapolation value of the high temperature diffusivity of Pt atoms in GaN reported in literature, the time required for Pt atoms diffusing 1 nm in GaN at ambient temperature is about 19 years. Therefore, the ambient-temperature diffusion and gettering of Pt atoms in GaN can hardly be observed. In this work, the ambient-temperature diffusion and gettering of Pt atoms in GaN is reported for the first time. It is demonstrated by use of secondary ion mass spectroscopy that in the condition of introducing a defect region on the GaN film surface by plasma, and subsequently, irradiated by 60Co gamma-ray or 3 MeV electrons, the ambient-temperature diffusion and gettering of Pt atoms in GaN can be detected. It is more obvious with larger irradiation dose and higher plasma power. With a similar surface defect region, the ambient-temperature diffusion and gettering of Pt atoms in GaN stimulated by 3 MeV electron irradiation is more marked than that stimulated by gamma irradiation. The physical mechanism of ambient-temperature diffusion and gettering of Pt atoms in a GaN film with a surface defect region stimulated by gamma or MeV electron irradiation is discussed.

  20. Shape-selected nanocrystals for in situ spectro-electrochemistry studies on structurally well defined surfaces under controlled electrolyte transport: A combined in situ ATR-FTIR/online DEMS investigation of CO electrooxidation on Pt

    Science.gov (United States)

    Jusys, Zenonas; Behm, R Jürgen

    2014-01-01

    Summary The suitability and potential of shape selected nanocrystals for in situ spectro-electrochemical and in particular spectro-electrocatalytic studies on structurally well defined electrodes under enforced and controlled electrolyte mass transport will be demonstrated, using Pt nanocrystals prepared by colloidal synthesis procedures and a flow cell set-up allowing simultaneous measurements of the Faradaic current, FTIR spectroscopy of adsorbed reaction intermediates and side products in an attenuated total reflection configuration (ATR-FTIRS) and differential electrochemical mass spectrometry (DEMS) measurements of volatile reaction products. Batches of shape-selected Pt nanocrystals with different shapes and hence different surface structures were prepared and structurally characterized by transmission electron microscopy (TEM) and electrochemical methods. The potential for in situ spectro-electrocatalytic studies is illustrated for COad oxidation on Pt nanocrystal surfaces, where we could separate contributions from two processes occurring simultaneously, oxidative COad removal and re-adsorption of (bi)sulfate anions, and reveal a distinct structure sensitivity in these processes and also in the structural implications of (bi)sulfate re-adsorption on the CO adlayer. PMID:24991511

  1. Radiolytic Preparation of Electrocatalysts with Pt-Co and Pt-Sn Nanoparticles for a Proton Exchange Membrane Fuel Cell

    Directory of Open Access Journals (Sweden)

    Sang Kyum Kim

    2014-01-01

    Full Text Available Nanosized Pt-Sn/VC and Pt-Co/VC electrocatalysts were prepared by a one-step radiation-induced reduction (30 kGy process using distilled water as the solvent and Vulcan XC72 as the supporting material. While the Pt-Co/VC electrodes were compared with Pt/VC (40 wt%, HiSpec 4000, in terms of their electrocatalytic activity towards the oxidation of H2, the Pt-Co/VC electrodes were evaluated in terms of their activity towards the hydrogen oxidation reaction (HOR and compared with Pt/VC (40 wt%, HiSpec 4000, Pt-Co/VC, and Pt-Sn/VC in a single cell. Additionally, the prepared electrocatalyst samples (Pt-Co/VC and Pt-Sn/VC were characterized by transmission electron microscopy (TEM, scanning electron microscope (SEM, thermogravimetric analysis (TGA, X-ray diffraction (XRD, X-ray photoelectron spectroscopy (XPS, electrochemical surface area (ECSA, and fuel cell polarization performance.

  2. Temperature effects on surface activity and application in oxidation ...

    Indian Academy of Sciences (India)

    Keywords. Surface activity; cetyl trimethylammonium bromide; sodium dodecyl sulfate; temperature; oxidation. ... Catalytic effect on oxidation of toluene derivatives with potassium permanganate follows the order CTAB-SDS > SDS > CTAB. This is not caused by the dissociative effect of CTAB-SDS with low surface activity at ...

  3. Surface oxidation of cobalt nanoparticles studied by Mossbauer spectroscopy

    DEFF Research Database (Denmark)

    Bødker, Franz; Mørup, Steen; Charles, S.W.

    1999-01-01

    The surface oxide formed on cobalt nanoparticles has been studied by Mossbauer emission spectroscopy. Exposure of the cobalt particles to oxygen at room temperature was found to result in the formation of a relatively well-ordered surface oxide with Mossbauer parameters similar to those of CoO....

  4. 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 temperature. The similarity to Ru18Pt28Al64 phase is a high-temperature phase, and decomposes to form similar to Ru12Pt15Al73 and similar to PtAl2. There is a ternary eutectic near 23 at.% Al, 55at.% Pt and 22at.% Ru, whereas most of the other reactions were...

  5. Site-specific Pt deposition and etching on electrically and thermally isolated SiO2 micro-disk surfaces

    International Nuclear Information System (INIS)

    Saraf, Laxmikant V

    2010-01-01

    Electrically and thermally isolated surfaces are crucial for improving the detection sensitivity of microelectronic sensors. The site-specific in situ growth of Pt nano-rods on thermally and electrically isolated SiO 2 micro-disks using wet chemical etching and a focused ion/electron dual beam (FIB-SEM) is demonstrated. Fabrication of an array of micro-cavities on top of a micro-disk is also demonstrated. The FIB source is utilized to fabricate through-holes in the micro-disks. Due to the amorphous nature of SiO 2 micro-disks, the Ga implantation possibly modifies through-hole sidewall surface chemistry rather than affecting its transport properties. Some sensor design concepts based on micro-fabrication of SiO 2 micro-disks utilizing thermally and electrically isolated surfaces are discussed from the viewpoint of applications in photonics and bio-sensing.

  6. LEED crystallography studies of the structure of clean and adsorbate-covered Ir, Pt and Rh crystal surfaces

    International Nuclear Information System (INIS)

    Koestner, R.J.

    1982-08-01

    There have only been a few Low Energy Electron Diffraction (LEED) intensity analyses carried out to determine the structure of molecules adsorbed on metal surfaces; most surface crystallography studies concentrated on the structure of clean unreconstructed or atomic adsorbate-covered transition metal faces. The few molecular adsorption systems already investigated by dynamical LEED are CO on Ni(100), Cu(100) and Pd(100) as well as C 2 H 2 and C 2 H 4 adsorbed on Pt(111). The emphasis of this thesis research has been to extend the applicability of LEED crystallography to the more complicated unit cells found in molecular overlayers on transition metals or in there constructed surfaces of clean transition metals

  7. LEED crystallography studies of the structure of clean and adsorbate-covered Ir, Pt and Rh crystal surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Koestner, R.J.

    1982-08-01

    There have only been a few Low Energy Electron Diffraction (LEED) intensity analyses carried out to determine the structure of molecules adsorbed on metal surfaces; most surface crystallography studies concentrated on the structure of clean unreconstructed or atomic adsorbate-covered transition metal faces. The few molecular adsorption systems already investigated by dynamical LEED are CO on Ni(100), Cu(100) and Pd(100) as well as C/sub 2/H/sub 2/ and C/sub 2/H/sub 4/ adsorbed on Pt(111). The emphasis of this thesis research has been to extend the applicability of LEED crystallography to the more complicated unit cells found in molecular overlayers on transition metals or in there constructed surfaces of clean transition metals.

  8. Mechanism and Thermochemistry of Coal Char Oxidation and Desorption of Surface Oxides

    DEFF Research Database (Denmark)

    Levi, Gianluca; Causà, Mauro; Lacovig, Paolo

    2017-01-01

    The present study investigates the coal char combustion by a combination of thermochemical and X-ray photoemission spectroscopy (XPS) analyses. Thermoanalytical methods (differential thermogravimetry, differential scanning calorimetry, and temperature-programmed desorption) are used to identify...... the key reactive steps that occur upon oxidation and heating of coal char (chemisorption, structural rearrangement and switchover of surface oxides, and desorption) and their energetics. XPS is used to reveal the chemical nature of the surface oxides that populate the char surface and to monitor...

  9. New methods of controlled monolayer-to-multilayer deposition of Pt for designing electrocatalysts at an atomic level

    Directory of Open Access Journals (Sweden)

    J. X. WANG

    2001-12-01

    Full Text Available Two new methods for monolayer-to-multileyer Pt deposition are presented. One involves Pt deposition by the replacement of an UPD metal monolayer on an electrode surface and the other the spontaneous deposition of Pt on Ru. The first method, exemplified by the replacement of a Cu monolayer on a Au(111 surface, occurs as a spontaneous irreversible redox reaction in which the Cu monolayer is oxidized by Pt cations, which are reduced and simultaneously deposited. The second method is illustrated by the deposition of Pt on a Ru(0001 surface and on carbon-supported Ru nanoparticles. This deposition takes place upon immersion of a UHV-prepared Ru(0001 crystal or Ru nanoparticles, reduced in H2, in a solution containing PtCl62- ions. The oxidation of Ru to RuOH by a local cell mechanism appears to be coupled with Pt deposition. This method facilitates the design of active Pt-Ru catalysts with ultimately low Pt loadings. Only a quarter of a monolayer of Pt on Ru nanoparticles yields an electrocatalyst with higher activity and CO tolerance for H2/CO oxidation than commercial Pt-Ru alloy electrocatalysts with considerably higher Pt loadings.

  10. Production of renewable hydrogen from aqueous-phase reforming of glycerol over Pt catalysts supported on different oxides

    Energy Technology Data Exchange (ETDEWEB)

    Menezes, Andre O. [Instituto Nacional de Tecnologia/MCT, Laboratorio de Catalise, Av. Venezuela 82/507, Rio de Janeiro/RJ 22081-312 (Brazil); Instituto Militar de Engenharia, Praca General Tiburcio, 80 Praia Vermelha, Rio de Janeiro/RJ 22290-270 (Brazil); Rodrigues, Michelly T.; Zimmaro, Adriana; Fraga, Marco A. [Instituto Nacional de Tecnologia/MCT, Laboratorio de Catalise, Av. Venezuela 82/507, Rio de Janeiro/RJ 22081-312 (Brazil); Borges, Luiz E.P. [Instituto Militar de Engenharia, Praca General Tiburcio, 80 Praia Vermelha, Rio de Janeiro/RJ 22290-270 (Brazil)

    2011-02-15

    Aqueous-phase reforming of oxygenated hydrocarbons for hydrogen production presents several advantages as feed molecules can be easily found in a wide range of biomass, there is no need for its vaporization and the process allows thorough exploitation of the environmental benefits of using hydrogen as an energy carrier. The use of glycerol in particular is motivated due to its availability as a consequence of increasing biodiesel production worldwide. In this contribution, the performance of Pt-based catalysts supported on different oxides (Al{sub 2}O{sub 3}, ZrO{sub 2}, MgO and CeO{sub 2}) is studied on glycerol reforming. All catalysts led to a hydrogen-rich gas phase. However, a good potential activity with high production of hydrogen and low concentration of undesired hydrocarbons was accomplished over the catalysts supported on MgO and ZrO{sub 2}. The high electron donating character of such oxides indicates the influence of the nature of the support in catalytic performance for glycerol reforming. (author)

  11. Efficient Aerobic Oxidation of Cyclohexane to KA Oil Catalyzed by Pt ...

    Indian Academy of Sciences (India)

    raw material for the manufacture of nylon 6 and nylon. 6, 6.1 Conventionally, the oxidation of cyclohexanol to ... reported to produce KA oil with 92% selectivity at a 25% cyclohexane conversion ratio, while Fe-MIL- ..... A remarkable advantage of the catalyst is that it can be used several times without any loss of activity.

  12. Hydrogen peroxide modified Mg-Al-O oxides supported Pt-Sn catalysts for paraffin dehydrogenation

    NARCIS (Netherlands)

    Lai, Y.; He, Songbo; Luo, S.; Bi, W.; Li, XianRu; Sun, Chenglin; Seshan, Kulathuiyer

    2015-01-01

    In this work, a new method to prepare Mg–Al–O oxide by co-precipitation method with addition of H2O2 was developed. The application of Mg–Al–O as a support of Pt–Sn catalysts for paraffin dehydrogenation was investigated. Characterization results indicated that modification of H2O2 (i) enlarged the

  13. Base case short-term Pu-oxide store. 2. Pt

    International Nuclear Information System (INIS)

    1978-08-01

    This paper describes the interim storage of plutonium oxide after its conversion from plutonium nitrate and before fabrication into fuel elements. The capacity of the store is 3 tons Pu. A description of the major handling, criticality, maintenance and physical protection philosophy is given, together with comments on the safety of the store and its impact on the environment

  14. Electronic state of europium atoms on surface of oxidized tungsten

    CERN Document Server

    Davydov, S Y

    2001-01-01

    The energy scheme of the europium atoms adsorption system on the tungsten surface, coated with the oxygen monolayer, is considered. The evaluations of the europium adatoms charged state on the oxidized tungsten surface are performed. It is established, that europium, adsorbed at the oxidized tungsten surface, is a positive ion with the charge close to the unit. The zonal scheme of the Eu-O/W adsorption system for the europium low and high concentrations is proposed

  15. Volcano Relations for Oxidation of Hydrogen Halides over Rutile Oxide Surfaces

    DEFF Research Database (Denmark)

    Toftelund, Anja; Man, Isabela C.; Hansen, Heine A.

    2012-01-01

    We investigate the heterogeneously catalysed oxidation of HX (X=Cl, Br and I) on the RuO2 (110) surface with DFT. We also solve a micro-kinetic model of HX oxidation and compare oxidation activity at different coverages. We further establish linear energy relations for the reaction intermediates ...

  16. Surface Structure of Aerobically Oxidized Diamond Nanocrystals

    Science.gov (United States)

    2014-10-27

    cleavage during ball-milling and aerobic oxidation.28−30 Removal of graphitic carbon impurities after oxidation at temperatures from 475 to 575 °C is...spectroscopic investigations. Samples were fixed on a machined Al sample bar with Cu tape. NEXAFS and XPS measurements were performed at beamline 10-1... Graphene . Phys. Rep.: Rev. Sect. Phys. Lett. 2009, 473, 51−87. (34) Ferrari, A. C.; Meyer, J. C.; Scardaci, V.; Casiraghi, C.; Lazzeri, M.; Mauri, F

  17. High catalytic performance and stability of Pt/C using acetic acid functionalized carbon

    Energy Technology Data Exchange (ETDEWEB)

    Ye, Jilei; Zhou, Yi; Gu, Jun; Yu, Tao [Eco-materials and Renewable Energy Research Center, Department of Physics and National Laboratory of Solid State Microstructures, Nanjing University, Nanjing 210093 (China); Liu, Jianguo; Zou, Zhigang [Eco-materials and Renewable Energy Research Center, Department of Physics and National Laboratory of Solid State Microstructures, Nanjing University, Nanjing 210093 (China); Department of Materials Science and Engineering, Nanjing University, Nanjing 210093 (China)

    2009-12-01

    Carbon (Vulcan XC-72, Cobat Corp.) is pretreated using acetic acid (HAC) before the Pt deposition by microwave assisted glycol method. TEM and XRD results indicate that 3 nm Pt nano-particles are uniformly dispersed on the surface of modified XC-72. In order to examine the interaction between Pt nano-particles and carbon, Pt/C-HAC and commercial Pt/C (Johnson Matthey Corp.) are calcined at 500 C for 2 h under nitrogen atmosphere. The average Pt particle size of Pt/C-HAC after calcination is only 10-12 nm in diameter while commercial Pt particles grow up to 25-35 nm with a broad size distribution. Meanwhile, electrochemical studies of Pt/C-HAC reveal higher activity and stability for both methanol oxidation and oxygen reduction than that of Pt/C-JM. The pore structure and surface composition are investigated by BET and XPS, which implies that much microporous structure and carbonyl functional groups on carbon surface are obtained after HAC treatment. The high catalytic performance and stability might mainly be due to the strong interaction between Pt nano-particles and carbon by carbonyl functional groups. Therefore, HAC treatment is proved to be a facile and effective method for carbon as the support for Pt as fuel cell catalyst. (author)

  18. Interaction of oxygen and carbon monoxide with Pt(111) at intermediate pressure and temperature : revisiting the fruit fly of surface science

    NARCIS (Netherlands)

    Bashlakov, Dmytro

    2014-01-01

    This thesis uses the surface science approach to address questions regarding the interaction of oxygen with platinum and its subsequent reaction with carbon monoxide. A Pt(111) single crystal surface is used as a model for the catalyst. Chapter 1 provides an overview of the literature on the

  19. Graphitized nanodiamond supporting PtNi alloy as stable anodic and cathodic electrocatalysts for direct methanol fuel cell

    International Nuclear Information System (INIS)

    Wang, Yongjiao; Zang, Jianbing; Dong, Liang; Pan, Hong; Yuan, Yungang; Wang, Yanhui

    2013-01-01

    Highlights: • The graphitized nanodiamond (GND) showed a higher oxidation-resistance than XC-72. • The PtNi/GND electrocatalytic exhibited greater stability than PtNi/XC-72. • The PtNi/GND had a better catalytic activity for MOR and ORR than Pt/GND. -- Abstract: Surface graphitized nanodiamond (GND) with a diamond core covered by a graphitic carbon shell was prepared by annealing ND at the temperature of 1300 °C in a vacuum of 10 −3 Pa. PtNi electrocatalysts were prepared by a microwave heating polyol method using the prepared GND as a support. The composition and morphology of the PtNi electrocatalysts supported on GND (PtNi/GND) were characterized by X-ray diffraction, transmission electron microscopy and energy dispersion spectra. The results showed that nano-scaled PtNi alloy particles with an atomic ratio of approximately 1:1 were uniformly deposited on the GND through co-reduction process. The electrocatalytic activities of the PtNi/GND electrocatalysts for methanol oxidation reaction (MOR) and oxygen reduction reaction (ORR) were investigated by cyclic voltammetry, chronoamperometry and linear sweep voltammetry. The PtNi/GND exhibited better electrocatalytic activities than the Pt/GND either for MOR and ORR. In comparison with traditional carbon support Vulcan XC-72, GND showed higher oxidation-resistance, and consequently led to greater stability for the PtNi/GND than PtNi/XC-72

  20. A genetically optimized kinetic model for ethanol electro-oxidation on Pt-based binary catalysts used in direct ethanol fuel cells

    Science.gov (United States)

    Sánchez-Monreal, Juan; García-Salaberri, Pablo A.; Vera, Marcos

    2017-09-01

    A one-dimensional model is proposed for the anode of a liquid-feed direct ethanol fuel cell. The complex kinetics of the ethanol electro-oxidation reaction is described using a multi-step reaction mechanism that considers free and adsorbed intermediate species on Pt-based binary catalysts. The adsorbed species are modeled using coverage factors to account for the blockage of the active reaction sites on the catalyst surface. The reaction rates are described by Butler-Volmer equations that are coupled to a one-dimensional mass transport model, which incorporates the effect of ethanol and acetaldehyde crossover. The proposed kinetic model circumvents the acetaldehyde bottleneck effect observed in previous studies by incorporating CH3CHOHads among the adsorbed intermediates. A multi-objetive genetic algorithm is used to determine the reaction constants using anode polarization and product selectivity data obtained from the literature. By adjusting the reaction constants using the methodology developed here, different catalyst layers could be modeled and their selectivities could be successfully reproduced.

  1. Thermal instability of GaSb surface oxide

    Science.gov (United States)

    Tsunoda, K.; Matsukura, Y.; Suzuki, R.; Aoki, M.

    2016-05-01

    In the development of InAs/GaSb Type-II superlattice (T2SL) infrared photodetectors, the surface leakage current at the mesa sidewall must be suppressed. To achieve this requirement, both the surface treatment and the passivation layer are key technologies. As a starting point to design these processes, we investigated the GaSb oxide in terms of its growth and thermal stability. We found that the formation of GaSb oxide was very different from those of GaAs. Both Ga and Sb are oxidized at the surface of GaSb. In contrast, only Ga is oxidized and As is barely oxidized in the case of GaAs. Interestingly, the GaSb oxide can be formed even in DI water, which results in a very thick oxide film over 40 nm after 120 minutes. To examine the thermal stability, the GaSb native oxide was annealed in a vacuum and analyzed by XPS and Raman spectroscopy. These analyses suggest that SbOx in the GaSb native oxide will be reduced to metallic Sb above 300°C. To directly evaluate the effect of oxide instability on the device performance, a T2SL p-i-n photodetector was fabricated that has a cutoff wavelength of about 4 μm at 80 K. As a result, the surface leakage component was increased by the post annealing at 325°C. On the basis of these results, it is possible to speculate that a part of GaSb oxide on the sidewall surface will be reduced to metallic Sb, which acts as an origin of additional leakage current path.

  2. Integrability of Liouville system on high genus Riemann surface: Pt. 1

    International Nuclear Information System (INIS)

    Chen Yixin; Gao Hongbo

    1992-01-01

    By using the theory of uniformization of Riemann-surfaces, we study properties of the Liouville equation and its general solution on a Riemann surface of genus g>1. After obtaining Hamiltonian formalism in terms of free fields and calculating classical exchange matrices, we prove the classical integrability of Liouville system on high genus Riemann surface

  3. One-Pot Polyol Synthesis of Pt/CeO2 and Au/CeO2 Nanopowders as Catalysts for CO Oxidation.

    Science.gov (United States)

    Pilger, Frank; Testino, Andrea; Lucchini, Mattia Alberto; Kambolis, Anastasios; Tarik, Mohammed; El Kazzi, Mario; Arroyo, Yadira; Rossell, Marta D; Ludwig, Christian

    2015-05-01

    The facile one-pot synthesis of CeO2-based catalysts has been developed to prepare a relatively large amount of nanopowders with relevant catalytic activity towards CO oxidation. The method consists of a two-steps process carried out in ethylene glycol: in the first step, 5 nm well-crystallized pure CeO2 is prepared. In a subsequent second step, a salt of a noble metal is added to the CeO2 suspension and the deposition of the noble metal on the nanocrystalline CeO2 is induced by heating. Two catalysts were prepared: Pt/CeO2 and Au/CeO2. The as-prepared catalysts, the thermally treated catalysts, as well as the pure CeO2, are characterized by XRD, TGA, XPS, FTIR, HR-TEM, STEM, particle size distribution, and N2-physisorption. In spite of the identical preparation protocol, Au and Pt behave in a completely different way: Au forms rather large particles, most of them with triangular shape, easily identifiable and dispersed in the CeO2 matrix. In contrast, Pt was not identified as isolated particles. The high resolution X-ray diffraction carried out on the Pt/CeO2 thermally treated sample (500 degrees C for 1 h) shows a significant CeO2 lattice shrinkage, which can be interpreted as an at least partial incorporation of Pt into the CeO2 crystal lattice. Moreover, only Pt2+ and Pt4+ species were identified by XPS. In literature, the incorporation of Pt into the CeO2 lattice is supported by first-principle calculations and experimentally demonstrated only by combustion synthesis methods. To the best of our knowledge this is the first report where ionically dispersed Pt into the CeO2 lattice is obtained via a liquid synthesis method. The thermally treated Pt/CeO2 sample revealed good activity with 50% CO conversion at almost room temperature.

  4. Surface Embedded Metal Oxide Sensors (SEMOS)

    DEFF Research Database (Denmark)

    Jespersen, Jesper Lebæk; Talat Ali, Syed; Pleth Nielsen, Lars

    is the second and main part of the project. The main challenges in developing metal oxide sensors are proper choice of the material, sensor location and fabrication technique due to lifetime and cross sensitivity issues in harsh environment where the problems like de-bonding or some kind of diffusion......SEMOS is a joint project between Aalborg University, Danish Technological Institute and Danish Technical University in which micro temperature sensors and metal oxide-based gas sensors are developed and tested in a simulated fuel cell environment as well as in actual working fuel cells. Initially...... complex and sensors are not easily implemented in the construction. Hence sensor interface and sensor position must therefore be chosen carefully in order to make the sensors as non-intrusive as possible. Metal Oxide Sensors (MOX) for measuring H2, O2 and CO concentration in a fuel cell environment...

  5. Improve oxidation resistance at high temperature by nanocrystalline surface layer

    OpenAIRE

    Xia, Z. X.; Zhang, C.; Huang, X. F.; Liu, W. B.; Yang, Z. G.

    2015-01-01

    An interesting change of scale sequence occurred during oxidation of nanocrystalline surface layer by means of a surface mechanical attrition treatment. The three-layer oxide structure from the surface towards the matrix is Fe3O4, spinel FeCr2O4 and corundum (Fe,Cr)2O3, which is different from the typical two-layer scale consisted of an Fe3O4 outer layer and an FeCr2O4 inner layer in conventional P91 steel. The diffusivity of Cr, Fe and O is enhanced concurrently in the nanocrystalline surfac...

  6. Surface-Controlled Metal Oxide Resistive Memory

    KAUST Repository

    Ke, Jr-Jian

    2015-10-28

    To explore the surface effect on resistive random-access memory (ReRAM), the impact of surface roughness on the characteristics of ZnO ReRAM were studied. The thickness-independent resistance and the higher switching probability of ZnO ReRAM with rough surfaces indicate the importance of surface oxygen chemisorption on the switching process. Furthermore, the improvements in switching probability, switching voltage and resistance distribution observed for ReRAM with rough surfaces can be attributed to the stable oxygen adatoms under various ambience conditions. The findings validate the surface-controlled stability and uniformity of ReRAM and can serve as the guideline for developing practical device applications.

  7. Methanol Oxidation on Model Elemental and Bimetallic Transition Metal Surfaces

    DEFF Research Database (Denmark)

    Tritsaris, G. A.; Rossmeisl, J.

    2012-01-01

    Direct methanol fuel cells are a key enabling technology for clean energy conversion. Using density functional theory calculations, we study the methanol oxidation reaction on model electrodes. We discuss trends in reactivity for a set of monometallic and bimetallic transition metal surfaces, flat...... sites on the surface and to screen for novel bimetallic surfaces of enhanced activity. We suggest platinum copper surfaces as promising anode catalysts for direct methanol fuel cells....

  8. 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.

  9. The nature of transition-metal-oxide surfaces

    Science.gov (United States)

    Henrich, V. E.

    The surfaces of the 3d-transition-metal oxides form a rich and important system in which to study the effects of atomic geometry, ligand coordination and d-orbital population on surface electronic structure and chemisorption. This article considers the properties of those surfaces in terms of the types of surface structures that can exist, including steps and point defects, and their relation to the experimental data that is available for well characterized, single-crystal surfaces. The electronic structure of nearly perfect surfaces is very similar to that of the bulk for many of the oxides that have been studied; atoms at step sites also appear to have properties similar to those of atoms on terraces. Point defects are often associated with surfaces 0 vacancies and attendant transfer of electrons to adjacent metal cations. Those cations are poorly screened from each other, and the excess charge is presumably shared between two or more cations having reduced ligand coordination. Point defects are generally more active for chemisorption than are perfect surfaces, however for Ti 2O 3 and V 2O 3, whose cations have 3d 1 and 3d 2 electronic configurations respectively, the cleaved (047) surface is more active than are surfaces having a high density of defects. The chemisorption behavior of both nearly perfect and defect surfaces of 3d-transition-metal oxides varies widely from one material to another, and it is suggestive to correlate this with cation d-orbital population. However, too few oxides have yet been studied to draw any firm conclusions. Additional theoretical work on perfect surfaces, defects and chemisorption is also necessary in order to gain a more complete understanding of transition-metal-oxide surfaces.

  10. Bright galaxies in the Fornax cluster. Automated galaxy surface photometry: Pt. 7

    International Nuclear Information System (INIS)

    Disney, M.J.; Phillipps, S.; Davies, J.L.; Cawson, M.G.M.; Kibblewhite, E.J.

    1990-01-01

    We have determined surface-brightness profiles for all galaxies down to magnitude B = 16 in the central region of the Fornax cluster. Using existing redshift data, we have determined the distributions of surface brightness for both the whole sample and for cluster disc galaxies only. Although both distributions peak at extrapolated central surface brightness ∼ 21.7B mag/arcsec 2 (the canonical result), it is shown that they are, in fact, consistent with very broad distributions of disc central surface brightness once selection effects and the effects of bulge contamination of the profile are taken into account. (author)

  11. Hydrogen adsorption and hydrogen evolution reaction on a polycrystalline Pt electrode studied by surface-enhanced infrared absorption spectroscopy

    International Nuclear Information System (INIS)

    Kunimatsu, Keiji; Senzaki, Takahiro; Samjeske, Gabor; Tsushima, Minoru; Osawa, Masatoshi

    2007-01-01

    Hydrogen evolution reaction (HER) on a polycrystalline Pt electrode has been investigated in Ar-purged acids by surface-enhanced infrared absorption spectroscopy and electrochemical kinetic analysis (Tafel plot). A vibrational mode characteristic to H atom adsorbed at atop sites (terminal H) was observed at 2080-2095 cm -1 . This band appears at 0.1 V (RHE) and grows at more negative potentials in parallel to the increase in hydrogen evolution current. Good signal-to-noise ratio of the spectra enabled us to establish the quantitative relation between the band intensity (equivalently, coverage) of terminal H and the kinetics of HER, from which we conclude that terminal H atom is the reaction intermediate in HER and the recombination of two terminal H atoms is the rate-determining step. The quantitative analysis of the infrared data also revealed that the adsorption of terminal H follows the Frumkin isotherm with repulsive interaction

  12. Electrochemistry of Phosphorous and Hypophosphorous Acid on a Pt electrode

    International Nuclear Information System (INIS)

    Prokop, M.; Bystron, T.; Bouzek, K.

    2015-01-01

    Highlights: • H 3 PO 3 and H 3 PO 2 oxidation on Pt electrode proceed at high overpotential. • H 3 PO 2 oxidation proceeds via H 3 PO 3 as intermediate. • H 3 PO 3 and H 3 PO 2 adsorb on Pt electrode, adsorption isotherms determined. • Adsorption is more pronounced at elevated temperature. • Tautomeric equilibria plays an important role in the acids behaviour. - Abstract: H 3 PO 4 is commonly used as a proton-conducting phase in high temperature proton exchange membrane fuel cell membranes. However, its reduction with hydrogen at elevated temperatures yields compounds like H 3 PO 3 and phosphorus. The aim of this work was to describe the basic electrochemical behaviour of H 3 PO 3 and H 3 PO 2 on a Pt electrode in diluted aqueous H 2 SO 4 solutions. The results show that adsorption of both phosphorus acids studied becomes important at an oxoacid bulk concentration around and below 10 mol dm −3 . Adsorption isotherms at 25 and 70 °C were determined for both acids. Unusually, the extent of adsorption increases with rising temperature. H 3 PO 3 is anodically oxidised on a bare Pt as well as on a PtO surface. H 3 PO 2 oxidation proceeds mainly on a PtO surface, with the intermediate product being H 3 PO 3 . High overvoltage around 1 V is characteristic of all anodic oxidation reactions occurring in the temperature range studied

  13. An amplified electrochemical immunosensor based on in situ-produced 1-naphthol as electroactive substance and graphene oxide and Pt nanoparticles functionalized CeO2 nanocomposites as signal enhancer.

    Science.gov (United States)

    Yang, Zhe-Han; Zhuo, Ying; Yuan, Ruo; Chai, Ya-Qin

    2015-07-15

    In this work, an amplified electrochemical immunosensor based on 1-naphthol as electroactive substance and Pt/CeO2/GO composites as catalytic amplifier was constructed for sensitive detection influenza. Through "sandwich" reaction, the Pt/CeO2/GO functionalized bioconjugates were captured on electrode surface and the electrochemical signal directly originated from 1-naphthol, which was in situ produced with high local concentration though the hydrolysis of 1-naphthyl phosphate catalyzed by ALP. Then, 1-naphthol as new reactant was oxidized by Pt/CeO2/GO composites with outstanding catalytic performance, resulting in detection signal amplification. In addition, as compared to label electroactive substance to antibodies, a simplified preparative step of immunosensor could be achieved because the signal probe get rid of introducation other electroactive substances. The proposed immunosensor achieved a linear range of 1.0×10(-3)-1.0ngmL(-1) and 5.0 to 1.0×10(2)ngmL(-1) with a detection limit of 0.43pgmL(-1) (defined as S/N=3). Copyright © 2015. Published by Elsevier B.V.

  14. Carbon monoxide oxidation on Pt single crystal electrodes: understanding the catalysis for low temperature fuel cells.

    Science.gov (United States)

    García, Gonzalo; Koper, Marc T M

    2011-08-01

    Herein the general concepts of fuel cells are discussed, with special attention to low temperature fuel cells working in alkaline media. Alkaline low temperature fuel cells could well be one of the energy sources in the next future. This technology has the potential to provide power to portable devices, transportation and stationary sectors. With the aim to solve the principal catalytic problems at the anode of low temperature fuel cells, a fundamental study of the mechanism and kinetics of carbon monoxide as well as water dissociation on stepped platinum surfaces in alkaline medium is discussed and compared with those in acidic media. Furthermore, cations involved as promoters for catalytic surface reactions are also considered. Therefore, the aim of the present work is not only to provide the new fundamental advances in the electrocatalysis field, but also to understand the reactions occurring at fuel cell catalysts, which may help to improve the fabrication of novel electrodes in order to enhance the performance and to decrease the cost of low temperature fuel cells. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Facile synthesis of PbTiO3 truncated octahedra via solid-state reaction and their application in low-temperature CO oxidation by loading Pt nanoparticles

    KAUST Repository

    Yin, Simin

    2014-01-01

    Perovskite PbTiO3 (PTO) nanocrystals with a truncated octahedral morphology have been prepared by a facile solid-state reaction. Pt nanoparticles preferentially nucleated on the {111} facet of PTO nanocrystals exhibit a remarkable low-temperature catalytic activity towards CO oxidation from a temperature as low as 30 °C and achieve 100% conversion at ∼50 °C. © 2014 the Partner Organisations.

  16. Electrochemical promotion of propane oxidation on Pt deposited on a dense β″-Al2O3 ceramic Ag+ conductor

    Science.gov (United States)

    Tsampas, Mihalis N.; Kambolis, Anastasios; Obeid, Emil; Lizarraga, Leonardo; Sapountzi, Foteini M.; Vernoux, Philippe

    2013-01-01

    A new kind of electrochemical catalyst based on a Pt porous catalyst film deposited on a β″-Al2O3 ceramic Ag+ conductor was developed and evaluated during propane oxidation. It was observed that, upon anodic polarization, the rate of propane combustion was significantly electropromoted up to 400%. Moreover, for the first time, exponential increase of the catalytic rate was evidenced during galvanostatic transient experiment in excellent agreement with EPOC equation. PMID:24790942

  17. Dynamics of oxide growth on Pt nanoparticles electrodes in the presence of competing halides by operando energy dispersive X-Ray absorption spectroscopy

    KAUST Repository

    Minguzzi, Alessandro

    2018-03-17

    In this work we studied the kinetics of oxide formation and reduction on Pt nanoparticles in HClO4 in the absence and in the presence of Br− and Cl− ions. The study combines potential step methods (i.e. chronoamperometry and choronocoulometry) with energy dispersive X-ray absorption spectroscopy (ED-XAS), which in principle allows to record a complete XAS spectrum in the timescale of milliseconds. Here, the information on the charge state and on the atomic surrounding of the considered element provided by XAS was exploited to monitor the degree of occupancy of 5d states of Pt in the course of oxide formation and growth, and to elucidate the competing halide adsorption/desorption phenomena. Electrochemical methods and XAS agree on the validity of a log(t) depending growth of Pt oxide, that is significantly delayed in the presence of Cl− and Br− anions. In the proximity of formation of one monolayer, the growth is further slowed down.

  18. Properties of Pt-supported iron oxide ultra-thin films: similarity of Hubbard-corrected and hybrid density functional theory description.

    Science.gov (United States)

    Prada, Stefano; Giordano, Livia; Pacchioni, Gianfranco; Noguera, Claudine; Goniakowski, Jacek

    2014-10-14

    We report a first principles study on the properties of Pt(111)-supported FeO(111) monolayer. We confront results issued from PBE+U and HSE06 approximations, and analyze the impact of the more accurate hybrid description of the electronic structure of the metal/oxide interface on a large variety of calculated characteristics of this system. In particular, we analyze the behavior of its work function and its consequences on the spontaneous charging of adsorbed Au adatoms. We also consider the FeO2 nano-oxide phase and its peculiar oxygen storage characteristics, responsible for the unusual catalytic properties of FeO(x)/Pt system. We show that while the hybrid approximation does indeed substantially improve the electronic characteristics of iron oxide, of individual Au adatoms, or oxygen molecules, its overall impact on the calculated properties of the composed FeO/Pt system is very small. We assign this to the relatively small effect of the hybrid approximation on the band structure alignment. This shows that the less computationally demanding DFT+U approximation remains a fully adequate tool in theoretical studies on this kind of systems. This is particularly important for calculations on realistic systems, with large-size reconstructions induced by the lattice mismatch at the interface between the two materials.

  19. Fractional surface termination of diamond by electrochemical oxidation.

    Science.gov (United States)

    Hoffmann, René; Obloh, Harald; Tokuda, Norio; Yang, Nianjun; Nebel, Christoph E

    2012-01-10

    The crystalline form of sp(3)-hybridized carbon, diamond, offers various electrolyte-stable surface terminations. The H-termination-selective attachment of nitrophenyl diazonium, imaged by AFM, shows that electrochemical oxidation can control the fractional hydrogen/oxygen surface termination of diamond on the nanometer scale. This is of particular interest for all applications relying on interfacial electrochemistry, especially for biointerfaces.

  20. Measuring Forces between Oxide Surfaces Using the Atomic Force Microscope

    DEFF Research Database (Denmark)

    Pedersen, Henrik Guldberg; Høj, Jakob Weiland

    1996-01-01

    The interactions between colloidal particles play a major role in processing of ceramics, especially in casting processes. With the Atomic Force Microscope (AFM) it is possible to measure the inter-action force between a small oxide particle (a few micron) and a surface as function of surface...

  1. Self-assembling behaviour of Pt nanoparticles onto surface of TiO2 ...

    Indian Academy of Sciences (India)

    platinum) onto the surface of host support (titanium dioxide) during photodeposition process as a function of solution pH has been explored in detail by means of transmission electron microscope (TEM). The photocatalytic activity of the ...

  2. Surface and Core Electronic Structure of Oxidized Silicon Nanocrystals

    Directory of Open Access Journals (Sweden)

    Noor A. Nama

    2010-01-01

    Full Text Available Ab initio restricted Hartree-Fock method within the framework of large unit cell formalism is used to simulate silicon nanocrystals between 216 and 1000 atoms (1.6–2.65 nm in diameter that include Bravais and primitive cell multiples. The investigated properties include core and oxidized surface properties. Results revealed that electronic properties converge to some limit as the size of the nanocrystal increases. Increasing the size of the core of a nanocrystal resulted in an increase of the energy gap, valence band width, and cohesive energy. The lattice constant of the core and oxidized surface parts shows a decreasing trend as the nanocrystal increases in a size that converges to 5.28 Ǻ in a good agreement with the experiment. Surface and core convergence to the same lattice constant reflects good adherence of oxide layer at the surface. The core density of states shows highly degenerate states that split at the oxygenated (001-(1×1 surface due to symmetry breaking. The nanocrystal surface shows smaller gap and higher valence and conduction bands when compared to the core part, due to oxygen surface atoms and reduced structural symmetry. The smaller surface energy gap shows that energy gap of the nanocrystal is controlled by the surface part. Unlike the core part, the surface part shows a descending energy gap that proves its obedience to quantum confinement effects. Nanocrystal geometry proved to have some influence on all electronic properties including the energy gap.

  3. Vertically aligned carbon nanotubes/carbon fiber paper composite to support Pt nanoparticles for direct methanol fuel cell application

    Science.gov (United States)

    Zhang, Jing; Yi, Xi-bin; Liu, Shuo; Fan, Hui-Li; Ju, Wei; Wang, Qi-Chun; Ma, Jie

    2017-03-01

    Vertically aligned carbon nanotubes (VACNTs) grown on carbon fiber paper (CFP) by plasma enhanced chemical vapor deposition is introduced as a catalyst support material for direct methanol fuel cells (DMFCs). Well dispersed Pt nanoparticles on VACNTs surface are prepared by impregnation-reduction method. The VACNTs on CFP possess well-maintained alignment, large surface area and good electrical conductivity, which leading to the formation of Pt particles with a smaller size and enhance the Pt utilization rate. The structure and nature of resulting Pt/VACNTs/CFP catalysts for methanol oxidation are investigated by transmission electron microscopy (TEM), X-ray diffraction (XRD) and scanning electron microscope (SEM). With the aid of VACNTs, well-dispersed Pt catalysts enable the reversibly rapid redox kinetic since electron transport efficiently passes through a one-dimensional pathway, which leads to enhance the catalytic activity and Pt utilization rate. Compared with the Pt/XC-72/CFP electrode, the electrochemical measurements results display that the Pt/VACNTs/CFP catalyst shows much higher electrocatalytic activity and better stability for methanol oxidation. In addition, the oxidation current from 200 to 1200 s decayed more slowly for the Pt/VACNTs/CFP than that of the Pt/XC-72/CFP catalysts, indicating less accumulation of adsorbed CO species. All those results imply that the Pt/VACNTs/CFP has a great potential for applications in DMFCs.

  4. Some positive effects of introducing Pt4+ and Fe3+ to the MnMo-oxide anode deposited on IrO2/Ti substrate for best oxygen evolution efficiency during electrolysis in 0.5 M NaCl solution

    Directory of Open Access Journals (Sweden)

    R.M. Abou Shahba

    2013-06-01

    Full Text Available NaCl solution (0.5 M of pH 2 was electrolyzed at 1000 Am−2 at room temperature. Addition of Pt4+ and Fe3+ to the prepared MnMo-oxide anode deposited on IrO2/Ti substrate, significantly improves the performance of anode for the oxygen evolution reaction (OER during NaCl electrolysis. After 2000 h of electrolysis, the oxygen evolution efficiency (OEE is in the order of MnMoPt-oxide > MnMoFe-oxide > MnMo-oxide anodes with 100%, 99%, and 93.2% OEE, respectively. The loss in weight of MnMo-oxide is reduced from about 13% to 3.2% and 0.0% by addition of iron and platinum cations, to the deposition electrolyte. The mean average grain size of MnO2, MnMo-, MnMoFe- and MnMoPt-oxide deposits prepared in electrolytes of pH 0.0 are in the range of 25.5, 16.22, 13.5 ∼ 16.5 and 13 ∼ 17.5 nm, respectively. The physicochemical properties of the deposits were characterized using X-ray diffraction spectroscopy (XRD, energy dispersive X-ray spectroscopy (EDX, scanning electron microscopy (SEM and electrochemical techniques. EDX analysis illustrates that IrO2/Ti is stable during the deposition process and behaves only as conductive substrate. SEM illustrates that, all elements constituting MnMoPt- and MnMoFe-oxide deposits are homogeneously distributed in the oxide surface.

  5. Self-assembling behaviour of Pt nanoparticles onto surface of TiO2 ...

    Indian Academy of Sciences (India)

    In the present study, self-assembling behaviour of guest nanoparticles (platinum) onto the surface of host support (titanium dioxide) during photodeposition process as a function of solution pH has been explored in detail by means of transmission electron microscope (TEM). The photocatalytic activity of the resulting ...

  6. Surface enhanced vibrational spectroscopy and first-principles study of L-cysteine adsorption on noble trimetallic Au/Pt@Rh clusters.

    Science.gov (United States)

    Loganathan, B; Chandraboss, V L; Senthilvelan, S; Karthikeyan, B

    2015-09-07

    The Rh shell of the Au/Pt/Rh trimetallic nanoparticles induces a wide variety of interesting surface reactions by allowing the adsorption of amino acids like L-cysteine (L-Cys). We present a snapshot of theoretical and experimental investigation of L-Cys adsorption on the surface of noble trimetallic Au/Pt@Rh colloidal nanocomposites. Density functional theoretical (DFT) investigations of L-Cys interaction with the Rhodium (Rh) shell of a trimetallic Au/Pt@Rh cluster in terms of geometry, binding energy (E(B)), binding site, energy gap (E(g)), electronic and spectral properties have been performed. L-Cys establishes a strong interaction with the Rh shell. It binds to Rh by the S1-site, which makes a stable L-Cys-Rh surface complex. DFT can be taken as a valuable tool to assign the vibrational spectra of the adsorption of L-Cys on trimetallic Au/Pt@Rh colloidal nanocomposites and mono-metallic Rh nanoparticles. Surface-enhanced infrared spectroscopy (SEIRS) with L-Cys on a Rh6 cluster surface has been simulated for the first time. Experimental information on the L-Cys-Rh surface complex is included to examine the interaction. The experimental spectral observations are in good agreement with the simulated DFT results. Characterization of the synthesized trimetallic Au/Pt@Rh colloidal nanocomposites has been done by high-resolution transmission electron microscopy (HR-TEM) with selected area electron diffraction (SAED) pattern, energy dispersive X-ray (EDX) spectroscopy, dynamic light scattering (DLS) measurements, zeta potential, zeta deviation analysis and UV-visible (UV-Vis) spectroscopic studies.

  7. Reporting central tendencies of chamber measured surface emission and oxidation.

    Science.gov (United States)

    Abichou, Tarek; Clark, Jeremy; Chanton, Jeffery

    2011-05-01

    Methane emissions, concentrations, and oxidation were measured on eleven MSW landfills in eleven states spanning from California to Pennsylvania during the three year study. The flux measurements were performed using a static chamber technique. Initial concentration samples were collected immediately after placement of the flux chamber. Oxidation of the emitted methane was evaluated using stable isotope techniques. When reporting overall surface emissions and percent oxidation for a landfill cover, central tendencies are typically used to report "averages" of the collected data. The objective of this study was to determine the best way to determine and report central tendencies. Results showed that 89% of the data sets of collected surface flux have lognormal distributions, 83% of the surface concentration data sets are also lognormal. Sixty seven percent (67%) of the isotope measured percent oxidation data sets are normally distributed. The distribution of data for all eleven landfills provides insight of the central tendencies of emissions, concentrations, and percent oxidation. When reporting the "average" measurement for both flux and concentration data collected at the surface of a landfill, statistical analyses provided insight supporting the use of the geometric mean. But the arithmetic mean can accurately represent the percent oxidation, as measured with the stable isotope technique. We examined correlations between surface CH(4) emissions and surface air CH(4) concentrations. Correlation of the concentration and flux values using the geometric mean proved to be a good fit (R(2)=0.86), indicating that surface scans are a good way of identifying locations of high emissions. Copyright © 2010 Elsevier Ltd. All rights reserved.

  8. Universality in Oxygen Evolution Electrocatalysis on Oxide Surfaces

    DEFF Research Database (Denmark)

    Man, Isabela Costinela; Su, Hai-Yan; Vallejo, Federico Calle

    2011-01-01

    Trends in electrocatalytic activity of the oxygen evolution reaction (OER) are investigated on the basis of a large database of HO* and HOO* adsorption energies on oxide surfaces. The theoretical overpotential was calculated by applying standard density functional theory in combination with the c......Trends in electrocatalytic activity of the oxygen evolution reaction (OER) are investigated on the basis of a large database of HO* and HOO* adsorption energies on oxide surfaces. The theoretical overpotential was calculated by applying standard density functional theory in combination...... that was the same for a wide variety of oxide catalyst materials and a universal descriptor for the oxygen evolution activity, which suggests a fundamental limitation on the maximum oxygen evolution activity of planar oxide catalysts....

  9. Rate law analysis of water oxidation on a hematite surface.

    Science.gov (United States)

    Le Formal, Florian; Pastor, Ernest; Tilley, S David; Mesa, Camilo A; Pendlebury, Stephanie R; Grätzel, Michael; Durrant, James R

    2015-05-27

    Water oxidation is a key chemical reaction, central to both biological photosynthesis and artificial solar fuel synthesis strategies. Despite recent progress on the structure of the natural catalytic site, and on inorganic catalyst function, determining the mechanistic details of this multiredox reaction remains a significant challenge. We report herein a rate law analysis of the order of water oxidation as a function of surface hole density on a hematite photoanode employing photoinduced absorption spectroscopy. Our study reveals a transition from a slow, first order reaction at low accumulated hole density to a faster, third order mechanism once the surface hole density is sufficient to enable the oxidation of nearest neighbor metal atoms. This study thus provides direct evidence for the multihole catalysis of water oxidation by hematite, and demonstrates the hole accumulation level required to achieve this, leading to key insights both for reaction mechanism and strategies to enhance function.

  10. First-principles calculations on Fe-Pt nanoclusters of various morphologies.

    Science.gov (United States)

    Platonenko, Alexander; Piskunov, Sergei; Bocharov, Dmitry; Zhukovskii, Yuri F; Evarestov, Robert A; Bellucci, Stefano

    2017-09-05

    Bimetallic FePt nanoparticles with L1 0 structure are attracting a lot of attention due to their high magnetocrystalline anisotropy and high coercivity what makes them potential material for storage of ultra-high density magnetic data. FePt nanoclusters are considered also as nanocatalysts for growth of carbon nanotubes of different chiralities. Using the DFT-LCAO CRYSTAL14 code, we have performed large-scale spin-polarized calculations on 19 different polyhedral structures of FePt nanoparticles in order to estimate which icosahedral or hcp-structured morphology is the energetically more preferable. Surface energy calculations of all aforementioned nanoparticles indicate that the global minimum corresponds to the nanocluster possessing the icosahedron "onion-like" structure and Fe 43 Pt 104 morphology where the outer layer consists of Pt atoms. The presence of the Pt-enriched layer around FePt core explains high oxidation resistance and environmental stability, both observed experimentally.

  11. PtRu/Ti anodes with varying Pt ratio: Ru ratio prepared by electrodeposition for the direct methanol fuel cell.

    Science.gov (United States)

    Shao, Zhi-Gang; Zhu, Fuyun; Lin, Wen-Feng; Christensen, Paul A; Zhang, Huamin

    2006-06-21

    PtRu/Ti anodes with varying Pt ratio Ru ratio were prepared by electrodeposition of a thin PtRu catalyst layer onto Ti mesh for a direct methanol fuel cell (DMFC). The morphology and structure of the catalyst layers were analyzed by SEM, EDX and XRD. The catalyst coating layer shows an alloy character. The relative activities of the PtRu/Ti electrodes were assessed and compared in half cell and single DMFC experiments. The results show that these electrodes are very active for the methanol oxidation and that the optimum Ru surface coverage was ca. 9 at.% for DMFC operating at 20 degrees C and 11 at.% at 60 degrees C. The PtRu/Ti anode shows a performance comparable to that of the conventional carbon-based anode in a DMFC operating with 0.25 M or 0.5 M methanol solution and atmosphere oxygen gas at 90 degrees C.

  12. Surface Properties of Photo-Oxidized Bituminous Coals: Final report

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1998-09-01

    Natural weathering has a detrimental effect on the hydrophobic nature of coal, which in turn can influence clean-coal recovery during flotation. Few techniques are available that can establish the quality of coal surfaces and that have a short analysis time to provide input for process control. Luminescence emissions which can be quantified with an optical microscope and photometer system, are measurably influenced by degree of weathering as well as by mild storage deterioration. In addition, it has been shown that when vitrinite is irradiated with a relatively high intensity flux of violet- or ultraviolet- light in the presence of air, photo-oxidation of the surface occurs. The combination of measuring the change in luminescence emission intensity with degree of surface oxidation provided the impetus for the current investigation. The principal aim of this research was to determine whether clear correlations could be established among surface oxygen functionality, hydrophobicity induced by photo-oxidation, and measurements of luminescence intensity and alteration. If successful, the project would result in quantitative luminescence techniques based on optical microscopy that would provide a measure of the changes in surface properties as a function of oxidation and relate them to coal cleanability. Two analytical techniques were designed to achieve these goals. Polished surfaces of vitrain bands or a narrow size fraction of powdered vitrain concentrates were photo-oxidized using violet or ultraviolet light fluxes and then changes in surface properties and chemistry were measured using a variety of near-surface analytical techniques. Results from this investigation demonstrate that quantitative luminescence intensity measurements can be performed on fracture surfaces of bituminous rank coals (vitrains) and that the data obtained do reveal significant variations depending upon the level of surface oxidation. Photo-oxidation induced by violet or ultraviolet light

  13. Surface characterization of low-temperature grown yttrium oxide

    Science.gov (United States)

    Krawczyk, Mirosław; Lisowski, Wojciech; Pisarek, Marcin; Nikiforow, Kostiantyn; Jablonski, Aleksander

    2018-04-01

    The step-by-step growth of yttrium oxide layer was controlled in situ using X-ray photoelectron spectroscopy (XPS). The O/Y atomic concentration (AC) ratio in the surface layer of finally oxidized Y substrate was found to be equal to 1.48. The as-grown yttrium oxide layers were then analyzed ex situ using combination of Auger electron spectroscopy (AES), elastic-peak electron spectroscopy (EPES) and scanning electron microscopy (SEM) in order to characterize their surface chemical composition, electron transport phenomena and surface morphology. Prior to EPES measurements, the Y oxide surface was pre-sputtered by 3 kV argon ions, and the resulting AES-derived composition was found to be Y0.383O0.465C0.152 (O/Y AC ratio of 1.21). The SEM images revealed different surface morphology of sample before and after Ar sputtering. The oxide precipitates were observed on the top of un-sputtered Y oxide layer, whereas the oxide growth at the Ar ion-sputtered surface proceeded along defects lines normal to the layer plane. The inelastic mean free path (IMFP) characterizing electron transport was evaluated as a function of energy in the range of 0.5-2 keV from the EPES method. Two reference materials (Ni and Au) were used in these measurements. Experimental IMFPs determined for the Y0.383O0.465C0.152 and Y2O3 surface compositions, λ, were uncorrected for surface excitations and approximated by the simple function λ = kEp at electron energies E between 500 eV and 2000 eV, where k and p were fitted parameters. These values were also compared with IMFPs resulting from the TPP-2 M predictive equation for both oxide compositions. The fitted functions were found to be reasonably consistent with the measured and predicted IMFPs. In both cases, the average value of the mean percentage deviation from the fits varied between 5% and 37%. The IMFPs measured for Y0.383O0.465C0.152 surface composition were found to be similar to the IMFPs for Y2O3.

  14. Surface Passivation of CIGS Solar Cells Using Gallium Oxide

    KAUST Repository

    Garud, Siddhartha

    2018-02-27

    This work proposes gallium oxide grown by plasma-enhanced atomic layer deposition, as a surface passivation material at the CdS buffer interface of Cu(In,Ga)Se2 (CIGS) solar cells. In preliminary experiments, a metal-insulator-semiconductor (MIS) structure is used to compare aluminium oxide, gallium oxide, and hafnium oxide as passivation layers at the CIGS-CdS interface. The findings suggest that gallium oxide on CIGS may show a density of positive charges and qualitatively, the least interface trap density. Subsequent solar cell results with an estimated 0.5 nm passivation layer show an substantial absolute improvement of 56 mV in open-circuit voltage (VOC), 1 mA cm−2 in short-circuit current density (JSC), and 2.6% in overall efficiency as compared to a reference (with the reference showing 8.5% under AM 1.5G).

  15. The Electrochemical Development of Pt(111 Stepped Surfaces and Its Influence on Methanol Electrooxidation

    Directory of Open Access Journals (Sweden)

    E. Teliz

    2011-01-01

    Full Text Available The progress in the preparation of new electrode surfaces by electrochemical treatments exhibiting high faradaic efficiencies towards industrial electrocatalytic processes has gained more attention in today's scientific community. Most of the papers report new catalysts dispersed on different substrates, but some fundamental studies required for electrochemical and physical characterizations are sometimes forgotten. In this paper, we make a full staging of two electrochemical treatments that can be conducted to enhance the electrocatalytic activity of platinum surfaces, such as, electrofacetting through square wave potential programs and constant cathodic polarizations in the net hydrogen evolution region. The cathodic treatment applied at −2 V clearly develops (111 stepped planes similarly to the electrofacetting performed after applying the square wave program between 1.40 V and 0.70 V at 2.5 kHz. The X-ray diffraction patterns of both surfaces as well as on other electrofacetted platinum electrodes are obtained for comparison purposes. Moreover, the electrocatalytic activity towards methanol electrooxidation also exhibits equivalent coulombic efficiencies and 200% higher than on polycrystalline platinum as demonstrated by linear sweep voltammetry and potentiostatic current decays.

  16. Growth of Ag, Au, Cu, and Pt nanostructures on surfaces by micropatterned laser-image formations

    Science.gov (United States)

    Pacheco-Londono, Leonardo C.; Aparicio-Bolaño, Joaquín.; Primera-Pedrozo, Oliva M.; Hernandez-Rivera, Samuel P.

    2011-07-01

    Silver, gold, copper and platinum nanoparticles (NPs) were grown on surfaces in the form of patterns by the exposure of laser radiation onto droplets of metal ion solutions and the aid of a reducing agent. The generation of patterns from metallic NPs was achieved by combining induced growth of NPs and nanostructures by laser incidence directly on surfaces and optical image formation techniques for transferring the patterns. Near-UV (363.8nm) and visible (532nm) laser wavelengths were used for the laser-induced growth of NPs into microstructures on glass, quartz, stainless steel, silicon, and gold-on-silicon substrates. The sizes of the patterns formed were on the micrometer scale and the sizes of the transferred patterns were on the millimeter scale. The patterns formed were generated by optical transference of image and interference of laser beams. Ag and Au substrates were highly active in surface enhanced Raman spectroscopy (SERS). The enhanced Raman activity was measured for SERS probe molecules: 9H-purin-6-amine (adenine) and 1,2-bis (4-pyridyl)-ethane analytes on Ag and Au substrates, respectively. The enhancement factors obtained were 1.8×105 and 6.2×106, respectively.

  17. Surface chemistry of rare-earth oxide surfaces at ambient conditions: reactions with water and hydrocarbons.

    Science.gov (United States)

    Külah, Elçin; Marot, Laurent; Steiner, Roland; Romanyuk, Andriy; Jung, Thomas A; Wäckerlin, Aneliia; Meyer, Ernst

    2017-03-22

    Rare-earth (RE) oxide surfaces are of significant importance for catalysis and were recently reported to possess intrinsic hydrophobicity. The surface chemistry of these oxides in the low temperature regime, however, remains to a large extent unexplored. The reactions occurring at RE surfaces at room temperature (RT) in real air environment, in particular, in presence of polycyclic aromatic hydrocarbons (PAHs), were not addressed until now. Discovering these reactions would shed light onto intermediate steps occurring in automotive exhaust catalysts before reaching the final high operational temperature and full conversion of organics. Here we first address physical properties of the RE oxide, nitride and fluoride surfaces modified by exposure to ambient air and then we report a room temperature reaction between PAH and RE oxide surfaces, exemplified by tetracene (C 18 H 12 ) on a Gd 2 O 3 . Our study evidences a novel effect - oxidation of higher hydrocarbons at significantly lower temperatures (~300 K) than previously reported (>500 K). The evolution of the surface chemical composition of RE compounds in ambient air is investigated and correlated with the surface wetting. Our surprising results reveal the complex behavior of RE surfaces and motivate follow-up studies of reactions between PAH and catalytic surfaces at the single molecule level.

  18. Adsorption/oxidation of CO on highly dispersed Pt catalyst studied by combined electrochemical and ATR-FTIRAS methods

    Energy Technology Data Exchange (ETDEWEB)

    Sato, T.; Kunimatsu, K. [Clean Energy Research Center, University of Yamanashi, 4 Takeda, Kofu 400-8510 (Japan); Uchida, H. [Interdisciplinary Graduate School of Medicine and Engineering, University of Yamanashi, 4 Takeda, Kofu 400-8510 (Japan); Watanabe, M. [Clean Energy Research Center, University of Yamanashi, 4 Takeda, Kofu 400-8510 (Japan)], E-mail: m-watanabe@yamanashi.ac.jp

    2007-12-20

    Elecrochemical ATR-FTIRAS measurements were conducted for the first time to investigate nature of CO adsorbed under potential control on a highly dispersed Pt catalyst with average particle size of 2.6 nm supported on carbon black (Pt/C) and carbon un-supported Pt black catalyst (Pt-B). Each catalyst was uniformly dispersed by 10 {mu}g Pt/cm{sup 2} and fixed by Nafion film of 0.05 {mu}m thick on a gold film chemically deposited on a Si ATR prism window. Adsorption of CO was conducted at 0.05 V on the catalysts in 1 and 100% CO atmospheres, for which CO coverage, {theta}{sub CO}, was 0.69 and 1, respectively. Two well-defined {nu}(CO) bands free from band anomalies assigned to atop CO (CO(L)) and symmetrically bridge bonded CO (CO(B){sub sym.}) were observed. It was newly found that the CO(L) band was spitted into two well-defined peaks, particularly in 1% CO, from very early stage of adsorption, which was interpreted in terms of simultaneous occupation of terrace and step-edge sites, denoted as CO(L){sub terrace} and CO(L){sub edge}, respectively. This simultaneous occupation was commonly observed in our work both on Pt/C and Pt-B. A new band was also observed around 1950 cm{sup -1} in addition to the bands of CO(L) and CO(B){sub sym.}, which was assigned to asymmetric bridge CO, CO(B){sub asym.}, adsorbed on (1 0 0) terraces, based on our previous ECSTM observation of CO adsorption structures on (1 0 0) facet. The CO(B){sub asym.} on the Pt/C, particularly in 100% CO atmosphere, results in growth of a sharp band at 3650 cm{sup -1} accompanied by a concomitant development of a band around 3500 cm{sup -1}. The former and the latter are assigned to {nu}(OH) vibrations of non-hydrogen bonded and hydrogen bonded water molecules adsorbed on Pt, respectively, interpreted in term of results from a bond scission of the existing hydrogen bonded networks by CO(L)s and from a promotion of new hydrogen bonding among water molecules presumably by CO(B){sub asym.}. It was found

  19. Electrochemical oxidation of ethanol using PtRh/C electrocatalysts in alkaline medium and synthesized by sodium borohydride and alcohol reduction

    International Nuclear Information System (INIS)

    Fontes, Eric Hossein

    2017-01-01

    PtRh/C were prepared by the following atomic proportions: (100,0), (0,100), (90,10), (70,30) and (50,50). The methods employed in the synthesis of these materials were reduction by sodium borohydride and reduction by alcohol. The metal salts used were H 2 PtCl 6 3•6H 2 0 and (RhNO 3 ) 3 , the support used was Carbon black XC72 and the bulk metal composition was 20% and 80% of support. The electrocatalysts were characterized by Energy Dispersive X-ray spectroscopy, X-ray diffraction and Transmission electron microscopy. The ethanol electrochemical oxidation mechanism was investigated by in situ Fourier Transform Infrared Spectroscopy couple to an Attenuated Total Reflection technique. The electrocatalytic activity were evaluated by Cyclic Voltammetry, Linear Sweep Voltammetry and Chronoamperometry techniques. The Fuel Cells tests were made in a single direct alcohol fuel cell with alkaline membrane. The working electrodes were prepared by a thin porous coating technique. X-ray diffraction allowed to verify metallic alloys, segregate phases and to calculate the percentage of metallic alloys. It was else possible to identify crystallographic phases. Infrared Spectroscopy allowed to verify that the electrochemical oxidation of ethanol was carried out by an incomplete mechanism. PtRh(70:30)/C prepared by sodium borohydride produced large amounts of carbon dioxide and acetaldehyde. Rh/C showed electrocatalytic activity when compared with other materials studied.

  20. Pt-decorated zinc oxide nanorod arrays with graphitic carbon nitride nanosheets for highly efficient dual-functional gas sensing.

    Science.gov (United States)

    Tian, Hailin; Fan, Huiqing; Ma, Jiangwei; Liu, Zhiyong; Ma, Longtao; Lei, Shenhui; Fang, Jiawen; Long, Changbai

    2018-01-05

    In this work, well-aligned ZnO nanorods were grown on the substrate of exfoliated g-C 3 N 4 nanosheets via a microwave-assisted hydrothermal synthesis, and then Pt/ZnO/g-C 3 N 4 nanostructures were obtained after the deposition of Pt nanoparticles. The growth of vertically ordered ZnO nanorods was occurred on g-C 3 N 4 nanosheets through the bonding interaction between Zn and N atoms, which was confirmed by XPS, FT-IR data and molecular orbital theory. The Pt/ZnO/g-C 3 N 4 nanostructures sensor exhibited the remarkable sensitivity, selectivity, and fast response/recovery time for air pollutants of ethanol and NO 2 . The application of Pt/ZnO/g-C 3 N 4 nanostructures could be used as a dual-functional gas sensor through the controlled working temperature. Besides, the Pt/ZnO/g-C 3 N 4 nanostructures sensor could be applied to the repeating detection of ethanol and NO 2 in the natural environment. The synergistic effect and improved the separation of electron-hole pairs in Pt/ZnO/g-C 3 N 4 nanostructures had been verified for the gas sensing mechanism. Additionally, Pt/ZnO/g-C 3 N 4 nanostructures revealed the excellent charge carriers transport properties in electrochemical impedance spectroscopy (EIS), such as the longer electron lifetime (τ n ), higher electron diffusion coefficient (D n ) and bigger effective diffusion length (L n ), which also played an important role for Pt/ZnO/g-C 3 N 4 nanostructures with striking gas sensing activities. Copyright © 2017 Elsevier B.V. All rights reserved.

  1. Probing Hot Electron Flow Generated on Pt Nanoparticles with Au/TiO2 Schottky Diodes during Catalytic CO Oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Park, Jeong Y.; Lee, Hyunjoo; Renzas, J. Russell; Zhang, Yawen; Somorjai, G.A.

    2008-05-01

    Hot electron flow generated on colloid platinum nanoparticles during exothermic catalytic carbon monoxide oxidation was directly detected with Au/TiO{sub 2} diodes. Although Au/TiO{sub 2} diodes are not catalytically active, platinum nanoparticles on Au/TiO{sub 2} exhibit both chemicurrent and catalytic turnover rate. Hot electrons are generated on the surface of the metal nanoparticles and go over the Schottky energy barrier between Au and TiO{sub 2}. The continuous Au layer ensures that the metal nanoparticles are electrically connected to the device. The overall thickness of the metal assembly (nanoparticles and Au thin film) is comparable to the mean free path of hot electrons, resulting in ballistic transport through the metal. The chemicurrent and chemical reactivity of nanoparticles with citrate, hexadecylamine, hexadecylthiol, and TTAB (Tetradecyltrimethylammonium Bromide) capping agents were measured during catalytic CO oxidation at pressures of 100 Torr O{sub 2} and 40 Torr CO at 373-513 K. We found that chemicurrent yield varies with each capping agent, but always decreases with increasing temperature. We suggest that this inverse temperature dependence is associated with the influence of charging effects due to the organic capping layer during hot electron transport through the metal-oxide interface.

  2. Surface oxide formation during corona discharge treatment of AA 1050 aluminium surfaces

    DEFF Research Database (Denmark)

    Minzari, Daniel; Møller, Per; Kingshott, Peter

    2008-01-01

    process modifies aluminium AA 1050 surface, the oxide growth and resulting corrosion properties. The corona treatment is carried out in atmospheric air. Treated surfaces are characterized using XPS, SEM/EDS, and FIB-FESEM and results suggest that an oxide layer is grown, consisting of mixture of oxide...... and hydroxide. The thickness of the oxide layer extends to 150–300 nm after prolonged treatment. Potentiodynamic polarization experiments show that the corona treatment reduces anodic reactivity of the surface significantly and a moderate reduction of the cathodic reactivity.......Atmospheric plasmas have traditionally been used as a non-chemical etching process for polymers, but the characteristics of these plasmas could very well be exploited for metals for purposes more than surface cleaning that is presently employed. This paper focuses on how the corona discharge...

  3. 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

  4. Investigation of the Si(111) surface in uhv: oxidation and the effect of surface phosphorus

    International Nuclear Information System (INIS)

    Tom, H.W.K.; Zhu, X.D.; Shen, Y.R.; Somorjai, G.A.

    1984-06-01

    We have studied the initial stages of oxidation, the segregation of phosphorus, and the effect of phosphorus on oxidation of the Si(111) 7 x 7 surface using optical second-harmonic generation. We have also observed a (√3 x √3)R30 0 LEED pattern for P on Si

  5. Probing the oxidation state of iron in the deep mantle using high P,T Mössbauer spectroscopy

    Science.gov (United States)

    McCammon, C. A.; Kupenko, I.; Sinmyo, R.; Cerantola, V.; Potapkin, V.; Chumakov, A. I.; Kantor, A.; Rüffer, R.; Dubrovinsky, L. S.

    2014-12-01

    The bulk of the Earth's interior is not directly accessible, yet redox processes occurring deep within drive many of the events observed at its surface. Laboratory studies of the relevant minerals at the appropriate pressure and temperature conditions have been pivotal in advancing our understanding of the Earth's interior. Iron plays an important role because it is the only major element with multiple electronic configurations (oxidation and spin state); however most of our knowledge regarding the oxidation state of iron in deep mantle phases is based on measurements of samples quenched from high temperature and sometimes also from high pressure. Mössbauer spectroscopy has been a key player in such studies and results on quenched samples have shown that the oxidation state of iron varies considerably through the mantle, from predominantly ferrous iron in upper mantle and transition zone phases to roughly 50% ferric iron in silicate perovskite (bridgmanite) due to the strong affinity of ferric iron for that phase in the presence of trivalent aluminium. Mössbauer measurements at pressures and temperatures along the geotherm are impractical using conventional radioactive sources due to their low brightness and the extremely limited possibilities for focusing in a laboratory setting. To address these limitations, we have developed an energy domain Synchrotron Mössbauer Source (SMS) on beamline ID18 at the European Synchrotron Radiation Facility that enables rapid collection of high quality energy domain Mössbauer spectra, and coupled with a portable double-sided laser heating system, SMS spectra can be collected on iron-containing mantle phases at pressures and temperatures up to those near the Earth's core in only a few hours (or less). Th