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Sample records for active pt surface

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

    PubMed

    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 Pt3M 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 Pt3Ni 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 Pt3Ni icosahedron is found among the best Pt-based ORR catalysts, moreover, the findings also demonstrate how to mimic active extended surfaces in nanoscale.

  2. Surface Activation of Pt Nanoparticles Synthesised by “Hot Injection” in the Presence of Oleylamine

    PubMed Central

    Humphrey, Jo J L; Sadasivan, Sajanikumari; Plana, Daniela; Celorrio, Verónica; Tooze, Robert A; Fermín, David J

    2015-01-01

    Oleylamine (OA) based “hot injection” colloidal synthesis offers a versatile approach to the synthesis of highly monodisperse metallic and multi-metallic alloyed nanostructures in the absence of potentially toxic and unstable phosphine compounds. For application in heterogeneous catalysis and electrocatalysis, the adsorbed OA species at the metal surfaces should be effectively removed without compromising the structure and composition of the nanostructures. Herein, we investigate the removal of OA from colloidal Pt nanoparticles through 1) “chemical methods” such as washing in acetic acid or ethanol, and ligand exchange with pyridine; and 2) thermal pre-treatment between 185 and 400 °C in air, H2 or Ar atmospheres. The electrochemical reactivity of Pt nanoparticles is acutely affected by the presence of surface organic impurities, making this material ideal for monitoring the effectiveness of OA removal. The results showed that thermal treatment in Ar at temperatures above 400 °C provides highly active particles, with reactivity comparable to the benchmark commercial catalyst, Pt/ETEK. The mechanism involved in thermal desorption of OA was also investigated by thermogravimetric analysis coupled to mass spectrometry (TGA-MS). Oxidation of HCOOH and adsorbed CO in acidic solution were used as test reactions to assess the Pt electrocatalytic activity. PMID:26201954

  3. Surface-Limited Synthesis of Pt Nanocluster Decorated Pd Hierarchical Structures with Enhanced Electrocatalytic Activity toward Oxygen Reduction Reaction.

    PubMed

    Yang, Tao; Cao, Guojian; Huang, Qingli; Ma, Yanxia; Wan, Sheng; Zhao, Hong; Li, Na; Sun, Xia; Yin, Fujun

    2015-08-12

    Exploring superior catalysts with high catalytic activity and durability is of significant for the development of an electrochemical device involving the oxygen reduction reaction. This work describes the synthesis of Pt-on-Pd bimetallic heterogeneous nanostructures, and their high electrocatalytic activity toward the oxygen reduction reaction (ORR). Pt nanoclusters with a size of 1-2 nm were generated on Pd nanorods (NRs) through a modified Cu underpotential deposition (UPD) process free of potential control and a subsequent surface-limited redox reaction. The Pt nanocluster decorated Pd nanostructure with a ultralow Pt content of 1.5 wt % exhibited a mass activity of 105.3 mA mg(-1) (Pt-Pd) toward ORR, comparable to that of the commercial Pt/C catalyst but 4 times higher than that of carbon supported Pd NRs. More importantly, the carbon supported Pt-on-Pd catalyst displays relatively small losses of 16% in electrochemical surface area (ECSA) and 32% in mass activity after 10 000 potential sweeps, in contrast to respective losses of 46 and 64% for the commercial Pt/C catalyst counterpart. The results demonstrated that Pt decoration might be an efficient way to improve the electrocatalytic activity of Pd and in turn allow Pd to be a promising substitution for commercial Pt catalyst.

  4. Surface and interface engineering of FePt/C nanocatalysts for electro-catalytic methanol oxidation: enhanced activity and durability.

    PubMed

    Wang, Junmei; Wang, Zhenlei; Li, Shuai; Wang, Rongming; Song, Yujun

    2017-03-23

    A methodology by coupling a microfluidic-batch process with in situ carbon-black mixing, successive annealing and de-alloying post-treatment was developed for engineering surface and interface microstructures of FePt/C nanocomposites. Ultra-small angular FePt nanocrystals rich in vertexes/terraces/steps and with Pt contents gradually increasing from the inner to the outer part can be synthesized at certain Fe/Pt atomic ratios (2/1 or 1.1/1), which can directly grow on carbon-black for enhanced nanocrystal-carbon interface interaction by introducing the in situ carbon-black mixing process. Composition and structure characterization suggests that FePt@(Fe1-xPtx)Oy(OH)z/C nanocomposites with FePt alloy cores and surface Pt-doping hydroxyl iron oxide shells are formed after annealing. After controlled de-alloying of Fe in annealed nanocrystals with a Fe/Pt ratio of 2/1, the finally formed nanocatalysts exhibited excellent electrochemical catalytic performance using the methanol oxidation reaction as a model, preserving an activity of 1610 mA mg(-1) Pt(-1) (12 times the commercial Pt/C catalysts, higher than the best result (7.9 times the commercial Pt/C catalysts) just published in Science (Science, 2016, 354, 1410-1414), enhanced durability and high tolerance to CO poisoning.

  5. Aniline hydrogenolysis on the Pt(111) single crystal surface: Mechanisms for C-N bond activation

    SciTech Connect

    Huang, S.X.; Gland, J.L.; Fischer, D.A. |

    1993-12-31

    Hydrogenolysis of C-N bond on transition metals is a crucial step in hydrodenitrogenation (HDN) reactions. Despite the overall complexity of HDN processes, the details of important surface reactions can be characterized using model reactions of organonitrogen compounds on single crystal model catalysts. The structure and reactivity of well characterized aniline monolayers on the Pt(111) surface both in vacuum and in the presence of hydrogen is discussed here. Adsorption and reactions of aniline were studied by Gland and Somorjai on the Pt(111) and Pt(100) surfaces, and more recently by Benziger`s group on the Ni(111) and Ni(100) surfaces. On both Pt and Ni surfaces, aniline {pi} bonds through the aromatic ring with its ring parallel to the substrate surface.

  6. Hydrogen induced C-C, C-N, and C-S bond activation on Pt and Ni surfaces

    SciTech Connect

    Gland, J.L.

    1992-12-01

    The work has focussed on hydrogen induced bond activation in adsorbed organic molecules and intermediates containin C-S and C-N and C-C bonds on Ni(100), Ni(111), and Pt(111) surfaces. Fluorescence Yield Near Edge Spectroscopy (FYNES) above the carbon K edge was used for adsorbed organic reactants and in-situ kinetic studies of bond activation. Results indicate that the activation is enhanced on Ni relative to Pt. Methylthiolate and methylamine adsorbed on Pt(111) were studied.

  7. Hydrogen induced C-C, C-N, and C-S bond activation on Pt and Ni surfaces

    SciTech Connect

    Gland, J.L.

    1992-01-01

    The work has focussed on hydrogen induced bond activation in adsorbed organic molecules and intermediates containin C-S and C-N and C-C bonds on Ni(100), Ni(111), and Pt(111) surfaces. Fluorescence Yield Near Edge Spectroscopy (FYNES) above the carbon K edge was used for adsorbed organic reactants and in-situ kinetic studies of bond activation. Results indicate that the activation is enhanced on Ni relative to Pt. Methylthiolate and methylamine adsorbed on Pt(111) were studied.

  8. Effect of gold subsurface layer on the surface activity and segregation in Pt/Au/Pt{sub 3}M (where M = 3d transition metals) alloy catalyst from first-principles

    SciTech Connect

    Kim, Chang-Eun; Lim, Dong-Hee; Jang, Jong Hyun; Kim, Hyoung Juhn; Yoon, Sung Pil; Han, Jonghee; Nam, Suk Woo; Hong, Seong-Ahn; Soon, Aloysius E-mail: hchahm@kist.re.kr; Ham, Hyung Chul E-mail: hchahm@kist.re.kr

    2015-01-21

    The effect of a subsurface hetero layer (thin gold) on the activity and stability of Pt skin surface in Pt{sub 3}M system (M = 3d transition metals) is investigated using the spin-polarized density functional theory calculation. First, we find that the heterometallic interaction between the Pt skin surface and the gold subsurface in Pt/Au/Pt{sub 3}M system can significantly modify the electronic structure of the Pt skin surface. In particular, the local density of states projected onto the d states of Pt skin surface near the Fermi level is drastically decreased compared to the Pt/Pt/Pt{sub 3}M case, leading to the reduction of the oxygen binding strength of the Pt skin surface. This modification is related to the increase of surface charge polarization of outmost Pt skin atoms by the electron transfer from the gold subsurface atoms. Furthermore, a subsurface gold layer is found to cast the energetic barrier to the segregation loss of metal atoms from the bulk (inside) region, which can enhance the durability of Pt{sub 3}M based catalytic system in oxygen reduction condition at fuel cell devices. This study highlights that a gold subsurface hetero layer can provide an additional mean to tune the surface activity toward oxygen species and in turn the oxygen reduction reaction, where the utilization of geometric strain already reaches its practical limit.

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

    PubMed

    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.

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

    NASA Astrophysics Data System (ADS)

    Zhang, Libo; Zhou, Gang

    2016-04-01

    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 BO2 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. Identical Location Transmission Electron Microscopy Imaging of Site-Selective Pt Nanocatalysts: Electrochemical Activation and Surface Disordering.

    PubMed

    Arán-Ais, Rosa M; Yu, Yingchao; Hovden, Robert; Solla-Gullón, Jose; Herrero, Enrique; Feliu, Juan M; Abruña, Héctor D

    2015-12-02

    We have employed identical location transmission electron microscopy (IL-TEM) to study changes in the shape and morphology of faceted Pt nanoparticles as a result of electrochemical cycling; a procedure typically employed for activating platinum surfaces. We find that the shape and morphology of the as-prepared hexagonal nanoparticles are rapidly degraded as a result of potential cycling up to +1.3 V. As few as 25 potential cycles are sufficient to cause significant degradation, and after about 500-1000 cycles the particles are dramatically degraded. We also see clear evidence of particle migration during potential cycling. These finding suggest that great care must be exercised in the use and study of shaped Pt nanoparticles (and related systems) as electrocatlysts, especially for the oxygen reduction reaction where high positive potentials are typically employed.

  12. Surface structure and chemistry of Pt/Cu/Pt(1 1 1) near surface alloy model catalyst in CO

    NASA Astrophysics Data System (ADS)

    Zeng, Shibi; Nguyen, Luan; Cheng, Fang; Liu, Lacheng; Yu, Ying; Tao, Franklin (Feng)

    2014-11-01

    Near surface alloy (NSA) model catalyst Pt/Cu/Pt(1 1 1) was prepared on Pt(1 1 1) through a controlled vapor deposition of Cu atoms. Different coordination environments of Pt atoms of the topmost Pt layer with the underneath Cu atoms in the subsurface result in different local electronic structures of surface Pt atoms. Surface structure and chemistry of the NAS model catalyst in Torr pressure of CO were studied with high pressure scanning tunneling microscopy (HP-STM) and ambient pressure X-ray photoelectron spectroscopy (AP-XPS). In Torr pressure of CO, the topmost Pt layer of Pt/Cu/Pt(1 1 1) is restructured to thin nanoclusters with size of about 1 nm. Photoemission feature of O 1s of CO on Pt/Cu/Pt(1 1 1) suggests CO adsorbed on both edge and surface of these formed nanoclusters. This surface is active for CO oxidation. Atomic layers of carbon are formed on Pt/Cu/Pt(1 1 1) at 573 K in 2 Torr of CO.

  13. Surface segregation effects in electrocatalysis: Kinetics ofoxygen reduction reaction on polycrystalline Pt3Ni alloy surfaces

    SciTech Connect

    Stamenkovic, V.; Schmidt, T.J.; Ross, P.N.; Markovic, N.M.

    2002-11-01

    Effects of surface segregation on the oxygen reduction reaction (ORR) have been studied on a polycrystalline Pt3Ni alloy in acid electrolyte using ultra high vacuum (UHV) surface sensitive probes and the rotating ring disk electrode (RRDE) method. Preparation, modification and characterization of alloy surfaces were done in ultra high vacuum (UHV). Depending on the preparation method, two different surface compositions of the Pt3Ni alloy are produced: a sputtered surface with 75 % Pt and an annealed surface (950 K ) with 100 % Pt. The latter surface is designated as the 'Pt-skin' structure, and is a consequence of surface segregation, i.e., replacement of Ni with Pt atoms in the first few atomic layers. Definitive surface compositions were established by low energy ion scattering spectroscopy (LEISS). The cyclic voltammetry of the 'Pt-skin' surface as well as the pseudocapacitance in the hydrogen adsorption/desorption potential region is similar to a polycrystalline Pt electrode. Activities of ORR on Pt3Ni alloy surfaces were compared to polycrystalline Pt in 0.1M HClO4 electrolyte for the observed temperature range of 293 < T < 333 K. The order of activities at 333 K was: 'Pt-skin' > Pt3Ni (75% Pt) > Pt with the maximum catalytic enhancement obtained for the 'Pt-skin' being 4 times that for pure Pt. Catalytic improvement of the ORR on Pt3Ni and 'Pt-skin' surfaces was assigned to the inhibition of Pt-OHad formation (on Pt sites) versus polycrystalline Pt. Production of H2O2 on both surfaces were similar compared to the pure Pt. Kinetic analyses of RRDE data confirmed that kinetic parameters for the ORR on the Pt3Ni and 'Pt-skin' surfaces are the same as on pure Pt: reaction order, m=1, two identical Tafel slopes, activation energy, {approx} 21-25 kJ/mol. Therefore the reaction mechanism on both Pt3Ni and 'Pt-skin' surfaces is the same as one proposed for pure Pt i.e. 4e{sup -} reduction pathway.

  14. Superior long-term activity for a Pt-Re alloy compared to Pt in methanol oxidation reactions

    NASA Astrophysics Data System (ADS)

    Duke, Audrey S.; Xie, Kangmin; Monnier, John R.; Chen, Donna A.

    2017-03-01

    Pt-Re bimetallic catalysts have shown enhanced activity compared to pure Pt for reactions involving oxidation, but the origins of this improved activity are not fully understood. Methanol oxidation on a Pt-Re alloy surface and pure Pt foil was studied in a microreactor coupled to an ultrahigh vacuum chamber. For reaction at 60 °C, the Pt-Re alloy surface exhibits superior long-term activity over a 24 h reaction period compared to pure Pt. The initial activity of Pt is 10-15% higher than on Pt-Re; however, the Pt surface gradually loses activity after 10 h online, whereas the activity of Pt-Re does not diminish. Post-reaction XPS shows that more carbon accumulates on the Pt than on Pt-Re, and the improved long-term activity is attributed to a greater ability of Pt-Re to oxidize the carbonaceous intermediates that eventually poison active sites. Both Pt and Pt-Re surfaces have almost no activity for methanol oxidation until a minimum coverage of oxygen is achieved from O2 dissociation. A comparison with methanol oxidation studies on Pt and Pt-Re in a pressure regime that is 150 times lower than in this work demonstrates that more carbon and less oxygen accumulate on the surfaces during reaction at the lower pressures.

  15. Intrinsic activity and poisoning rate for HCOOH oxidation at Pt(100) and vicinal surfaces containing monoatomic (111) steps.

    PubMed

    Grozovski, Vitali; Climent, Víctor; Herrero, Enrique; Feliu, Juan M

    2009-08-03

    Pulsed voltammetry is used to study formic acid oxidation on Pt(2n-1,1,1) surfaces and determine the effects of the size of the (100) terrace and the (111) step density on the reaction mechanism. The intrinsic activity of the electrode through the active intermediate reaction path (j(theta=) (0)), as well as the rate constant for the CO formation (k(ads)), are calculated from the current transients obtained at different potentials. For surfaces with wide terraces, j(theta=) (0) and k(ads) are almost insensitive to the step density, which suggests that step and terrace sites have a similar activity for this reaction. For narrow terraces (n<6), the intrinsic activity diminishes. The dependence of the reaction rates on the electrode potential is also elucidated. The CO formation only takes place in a narrow potential window, very close to the potential of zero total charge, while the direct oxidation takes place even when the surface is covered by anions. The different behavior for both reactions suggests that the adsorption mode of formic acid is different for each path.

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

    NASA Astrophysics Data System (ADS)

    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.

  17. Pt +-mediated activation of methane: theory and experiment

    NASA Astrophysics Data System (ADS)

    Heinemann, Christoph; Wesendrup, Ralf; Schwarz, Helmut

    1995-06-01

    A combined theoretical and experimental study on the Pt +-mediated activation of methane is presented. Dehydrogenation of CH 4 by thermalized Pt + cations (Pt + + CH 4 ← PtCH 2+ + H 2) proceeds along a doublet ground state potential energy surface and is found to be reversible under the conditions of Fourier transform ion-cyclotron resonance mass spectrometry. The recently reported oxidation of the cationic platinum carbene PtCH 2+ by O 2 produces electronically excited Pt + cations, which are detected in the 4F9/2 state by means of charge-transfer bracketing experiments.

  18. Surface chemistry of aromatic reactants on Pt- and Mo-modified Pt catalysts

    SciTech Connect

    Robinson, Allison M.; Mark, Lesli; Rasmussen, Mathew J.; Hensley, Jesse E.; Medlin, J. Will

    2016-11-01

    Supported catalysts containing an oxophilic metal such as Mo and a noble metal such as Pt have shown promising activity and selectivity for deoxygenation of biomass-derived compounds. Here, we report that PtMo catalysts also promote hydrogenolysis of the model compound benzyl alcohol, while decarbonylation is most prevalent over unmodified Pt. A combination of single crystal surface science studies, density functional theory (DFT) calculations, and vapor phase upgrading experiments using supported catalysts was carried out to better understand the mechanism by which Mo promotes deoxygenation. Molybdenum was deposited in submonolayer quantities on a Pt(111) surface and reduced at high temperature. Temperature-programmed desorption (TPD) experiments using benzyl alcohol as a reactant showed greatly enhanced yields of the deoxygenation product toluene at moderate Mo coverages. To understand how the interaction of the aromatic group with the surface influenced this reactivity, we investigated the adsorption of toluene as a probe molecule. We found that the addition of Mo to Pt(111) resulted in a significant decrease in toluene decomposition. DFT calculations indicated that this decrease was consistent with decreased aromatic adsorption strengths that accompany incorporation of Mo into the Pt subsurface. The weaker aromatic-surface interaction on Pt/Mo surfaces led to a tilted adsorption geometry for benzyl alcohol, which presumably promotes hydrogenolysis to produce toluene instead of decarbonylation to produce benzene and CO. Alumina-supported Pt and PtMo catalysts were also tested for benzyl alcohol deoxygenation. PtMo catalysts had a higher rate of toluene production and lower rates of benzene and benzaldehyde production. Additionally, when benzaldehyde was used as the reactant to measure decarbonylation activity the mass-normalized rate of benzene production was 2.5 times higher on Pt than PtMo. Altogether, the results of TPD, DFT, and supported catalyst

  19. Surface chemistry of aromatic reactants on Pt- and Mo-modified Pt catalysts

    DOE PAGES

    Robinson, Allison M.; Mark, Lesli; Rasmussen, Mathew J.; ...

    2016-11-01

    Supported catalysts containing an oxophilic metal such as Mo and a noble metal such as Pt have shown promising activity and selectivity for deoxygenation of biomass-derived compounds. Here, we report that PtMo catalysts also promote hydrogenolysis of the model compound benzyl alcohol, while decarbonylation is most prevalent over unmodified Pt. A combination of single crystal surface science studies, density functional theory (DFT) calculations, and vapor phase upgrading experiments using supported catalysts was carried out to better understand the mechanism by which Mo promotes deoxygenation. Molybdenum was deposited in submonolayer quantities on a Pt(111) surface and reduced at high temperature. Temperature-programmedmore » desorption (TPD) experiments using benzyl alcohol as a reactant showed greatly enhanced yields of the deoxygenation product toluene at moderate Mo coverages. To understand how the interaction of the aromatic group with the surface influenced this reactivity, we investigated the adsorption of toluene as a probe molecule. We found that the addition of Mo to Pt(111) resulted in a significant decrease in toluene decomposition. DFT calculations indicated that this decrease was consistent with decreased aromatic adsorption strengths that accompany incorporation of Mo into the Pt subsurface. The weaker aromatic-surface interaction on Pt/Mo surfaces led to a tilted adsorption geometry for benzyl alcohol, which presumably promotes hydrogenolysis to produce toluene instead of decarbonylation to produce benzene and CO. Alumina-supported Pt and PtMo catalysts were also tested for benzyl alcohol deoxygenation. PtMo catalysts had a higher rate of toluene production and lower rates of benzene and benzaldehyde production. Additionally, when benzaldehyde was used as the reactant to measure decarbonylation activity the mass-normalized rate of benzene production was 2.5 times higher on Pt than PtMo. Altogether, the results of TPD, DFT, and supported catalyst

  20. Adsorption of hydrogen on Pt(111) and Pt(100) surfaces and its role in the HOR.

    SciTech Connect

    Strmcnik, D.; Tripkovic, D.; van der Vliet, D.; Stamenkovic, V.; Markovic, N. M.; Materials Science Division

    2008-10-01

    Hydrogen adsorption isotherms, evaluated by combination of cyclic voltammetry and chronoamperometry, are reported on Pt(1 1 1) and Pt(1 0 0) surfaces in 0.1 M HClO{sub 4}. We found that at E > 0.05 V Pt(1 1 1) and Pt(1 0 0) are only partially covered by the adsorbed hydrogen (H{sub ad}). On both surfaces, a full monolayer of the adsorbed hydrogen is completed at -0.1 V, i.e. the adsorption of atomic hydrogen is observed in the hydrogen evolution potential region. We also found, that the activity of the hydrogen oxidation reaction is mirrored by the shape of the hydrogen adsorption isotherms, implying that H{sub ad} is in fact a spectator in the HOR.

  1. Surface termination of CePt5/Pt (111 ): The key to chemical inertness

    NASA Astrophysics Data System (ADS)

    Praetorius, C.; Zinner, M.; Held, G.; Fauth, K.

    2015-11-01

    The surface termination of CePt5/Pt (111 ) is determined experimentally by LEED-IV. In accordance with recent theoretical predictions, a dense Pt terminated surface is being found. Whereas the CePt5 volume lattice comprises Pt kagome layers, additional Pt atoms occupy the associated hole positions at the surface. This finding provides a natural explanation for the remarkable inertness of the CePt5 intermetallic. Implications of the structural relaxations determined by LEED-IV analysis are discussed with regard to observations by scanning tunneling microscopy and electron spectroscopies.

  2. Reducing Pt use in the catalysts for formic acid electrooxidation via nanoengineered surface structure

    NASA Astrophysics Data System (ADS)

    Liao, Mengyin; Wang, Yulu; Chen, Guoqin; Zhou, Hua; Li, Yunhua; Zhong, Chuan-Jian; Chen, Bing H.

    2014-07-01

    The design of active and durable catalysts for formic acid (FA) electrooxidation requires controlling the amount of three neighboring platinum atoms in the surface of Pt-based catalysts. Such requirement is studied by preparing Pt decorated Pd/C (donated as Pt-Pd/C) with various Pt:Pd molar ratios via galvanic displacement making the amount of three neighboring Pt atoms in the surface of Pt-Pd/C tunable. The decorated nanostructures are confirmed by XPS, HS-LEIS, cyclic voltammetry and chronoamperometric measurements, demonstrating that Pt-Pd/C (the optimal molar ratio, Pt:Pd = 1:250) exhibits superior activity and durability than Pd/C and commercial Pt/C (J-M, 20%) catalysts for FA electrooxidation. The mass activity of Pt-Pd/C (Pt:Pd = 1:250) (3.91 A mg-1) is about 98 and 6 times higher than that of commercial Pt/C (0.04 A mg-1) and Pd/C (0.63 A mg-1) at a given potential of 0.1 V vs SCE, respectively. The controlled synthesis of Pt-Pd/C lead to the formation of largely discontinuous Pd and Pt sites and inhibition of CO formation, exhibiting unprecedented electrocatalytic performance toward FA electrooxidation while the cost of the catalyst almost the same as Pd/C. These findings have profound implications to the design and nanoengineering of decorated surfaces of catalysts for FA electrooxidation.

  3. CO adsorption on (111) and (100) surfaces of the Pt sub 3 Ti alloy. Evidence for parallel binding and strong activation of CO

    NASA Technical Reports Server (NTRS)

    Mehandru, S. P.; Anderson, A. B.; Ross, P. N.

    1985-01-01

    The CO adsorption on a 40 atom cluster model of the (111) surface and a 36 atom cluster model of the (100) surface of the Pt3Ti alloy was studied. Parallel binding to high coordinate sites associated with Ti and low CO bond scission barriers are predicted for both surfaces. The binding of CO to Pt sites occurs in an upright orientation. These orientations are a consequence of the nature of the CO pi donation interactions with the surface. On the Ti sites the orbitals donate to the nearly empty Ti 3d band and the antibonding counterpart orbitals are empty. On the Pt sites, however, they are in the filled Pt 5d region of the alloy band, which causes CO to bond in a vertical orientation by 5 delta donation from the carbon end.

  4. Surface diffusion of xenon on Pt(111)

    NASA Astrophysics Data System (ADS)

    Meixner, D. Laurence; George, Steven M.

    1993-06-01

    The surface diffusion of xenon on the Pt(111) surface was investigated using laser induced thermal desorption (LITD) and temperature programmed desorption (TPD) techniques. The surface diffusion coefficient at 80 K decreased dramatically from D=8×10-7 cm2/s at θ=0.05θs to approximately D=2×10-8 cm2/s at θ=θs, where θs denotes the saturation coverage at 85 K, corresponding to a commensurate monolayer coverage of 5.0×1014 xenon atoms/cm2. This coverage dependence was consistent with attractive interactions between the adsorbed xenon atoms and the existence of two-dimensional condensed phases of xenon on Pt(111). The kinetic parameters for surface diffusion at θ=θs were Edif=1.3±0.1 kcal/mol and D0=1.1×10-4±0.2 cm2/s. The magnitude of Edif at θ=θs represented the combined effect of the intrinsic corrugation of the adsorbate-surface potential and attractive interactions between the adsorbed xenon atoms. LITD experiments at θ=0.25 θs revealed diffusion kinetic parameters of Edif=1.2±0.2 kcal/mol and D0=3.4×10-4±0.5 cm2/s. The constant Edif at low and high coverage was attributed to the ``breakaway'' of xenon atoms from the edges of condensed phase xenon islands. The coverage dependence of the surface diffusion coefficient for Xe/Pt(111) was explained by a multiple site diffusion mechanism, where collisions with xenon islands limit diffusional motion. Thermal desorption kinetics for xenon on Pt(111) were determined using TPD experiments. Using the variation of heating rates method, the desorption parameters were Edes=6.6±0.2 kcal/mol and νdes=1.3×1013±0.4 s-1, in good agreement with previous studies. The xenon TPD peak shifted to higher temperature versus initial coverage at a fixed heating rate, providing further evidence for attractive interactions between the adsorbed xenon atoms.

  5. Understanding the Effects of Surface Chemistry and Microstructure on the Activity and Stability of Pt Electrocatalysts on Non-Carbon Supports

    SciTech Connect

    Mustain, William

    2015-02-12

    The objective of this project is to elucidate the effects of the chemical composition and microstructure of the electrocatalyst support on the activity, stability and utilization of supported Pt clusters.

  6. Silicide induced surface defects in FePt nanoparticle fcc-to-fct thermally activated phase transition

    NASA Astrophysics Data System (ADS)

    Chen, Shu; Lee, Stephen L.; André, Pascal

    2016-11-01

    Magnetic nanoparticles (MnPs) are relevant to a wide range of applications including high density information storage and magnetic resonance imaging to name but a few. Among the materials available to prepare MnPs, FePt is attracting growing attention. However, to harvest the strongest magnetic properties of FePt MnPs, a thermal annealing is often required to convert face-centered cubic as synthesized nPs into its tetragonal phase. Rarely addressed are the potential side effects of such treatments on the magnetic properties. In this study, we focus on the impact of silica shells often used in strategies aiming at overcoming MnP coalescence during the thermal annealing. While we show that this shell does prevent sintering, and that fcc-to-fct conversion does occur, we also reveal the formation of silicide, which can prevent the stronger magnetic properties of fct-FePt MnPs from being fully realised. This report therefore sheds lights on poorly investigated and understood interfacial phenomena occurring during the thermal annealing of MnPs and, by doing so, also highlights the benefits of developing new strategies to avoid silicide formation.

  7. Interface Architecture Determined Electrocatalytic Activity of Pt on Vertically Oriented TiO2 Nanotubes

    SciTech Connect

    R Rettew; N Allam; F Alamgir

    2011-12-31

    The surface atomic structure and chemical state of Pt is consequential in a variety of surface-intensive devices. Herein we present the direct interrelationship between the growth scheme of Pt films, the resulting atomic and electronic structure of Pt species, and the consequent activity for methanol electro-oxidation in Pt/TiO{sub 2} nanotube hybrid electrodes. X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy (XAS) measurements were performed to relate the observed electrocatalytic activity to the oxidation state and the atomic structure of the deposited Pt species. The atomic structure as well as the oxidation state of the deposited Pt was found to depend on the pretreatment of the TiO{sub 2} nanotube surfaces with electrodeposited Cu. Pt growth through Cu replacement increases Pt dispersion, and a separation of surface Pt atoms beyond a threshold distance from the TiO{sub 2} substrate renders them metallic, rather than cationic. The increased dispersion and the metallic character of Pt results in strongly enhanced electrocatalytic activity toward methanol oxidation. This study points to a general phenomenon whereby the growth scheme and the substrate-to-surface-Pt distance dictates the chemical state of the surface Pt atoms, and thereby, the performance of Pt-based surface-intensive devices.

  8. Surface reconstruction of Pt(001) quantitatively revisited

    NASA Astrophysics Data System (ADS)

    Hammer, R.; Meinel, K.; Krahn, O.; Widdra, W.

    2016-11-01

    The complex hexagonal reconstructions of the (001) surfaces of platinum and gold have been under debate for decades. Here, the structural details of the Pt(001) reconstruction have been quantitatively reinvestigated by combining the high resolving power of scanning tunneling microscopy (STM) and spot profile analysis low energy electron diffraction (SPA-LEED). In addition, LEED simulations based on a Moiré approach have been applied. Annealing temperatures around 850 °C yield a superstructure that approaches a commensurable c (26.6 ×118 ) substrate registry. It evolves from a Moiré-like buckling of a compressed hexagonal top layer (hex) where atomic rows of the hex run parallel to atomic rows of the square substrate. Annealing at 920 °C stimulates a continuous rotation of the hex where all angles between ±0.7° are simultaneously realized. At temperatures around 1080 °C, the nonrotated hex coexists with a hex that is rotated by about 0.75°. Annealing at temperatures around 1120 °C yield a locking of the hex in fixed rotation angles of 0.77°, 0.88°, and 0.94°. At temperatures around 1170 °C, the Pt(001)-hex-R 0.94° prevails as the energetically most favored form of the rotated hex.

  9. The effect of the surface composition of Ru-Pt bimetallic catalysts for methanol oxidation

    DOE PAGES

    Garrick, Taylor R.; Diao, Weijian; Tengco, John M.; ...

    2016-02-23

    Here, a series of Ru-Pt bimetallic catalysts prepared by the electroless deposition of controlled and variable amounts of Ru on the Pt surface of a commercially-available 20 wt% Pt/C catalyst has been characterized and evaluated for the oxidation of methanol. The activity of each Ru-Pt catalyst was determined as a function of surface composition via cyclic voltammetry. For the Ru-Pt bimetallic catalysts, activity passed through a maximum at approximately 50% monodisperse Ru surface coverage. However, due to the monolayer coverage of Ru on Pt, the amount of metal in the catalyst is minimized compared to a bulk 1:1 atomic ratiomore » of Ru:Pt seen in commercial bimetallic catalysts. Chemisorption and temperature programmed reduction experiments confirmed that the surface had characteristics of a true bimetallic catalyst. On a mass of Pt basis, the activity of this composition for methanol oxidation was 7 times higher than pure Pt and 3.5 times higher than a commercial catalyst with a 1:1 Pt:Ru bulk atomic ratio.« less

  10. The effect of the surface composition of Ru-Pt bimetallic catalysts for methanol oxidation

    SciTech Connect

    Garrick, Taylor R.; Diao, Weijian; Tengco, John M.; Stach, Eric A.; Senanayake, Sanjaya D.; Chen, Donna A.; Monnier, John R.; Weidner, John W.

    2016-02-23

    Here, a series of Ru-Pt bimetallic catalysts prepared by the electroless deposition of controlled and variable amounts of Ru on the Pt surface of a commercially-available 20 wt% Pt/C catalyst has been characterized and evaluated for the oxidation of methanol. The activity of each Ru-Pt catalyst was determined as a function of surface composition via cyclic voltammetry. For the Ru-Pt bimetallic catalysts, activity passed through a maximum at approximately 50% monodisperse Ru surface coverage. However, due to the monolayer coverage of Ru on Pt, the amount of metal in the catalyst is minimized compared to a bulk 1:1 atomic ratio of Ru:Pt seen in commercial bimetallic catalysts. Chemisorption and temperature programmed reduction experiments confirmed that the surface had characteristics of a true bimetallic catalyst. On a mass of Pt basis, the activity of this composition for methanol oxidation was 7 times higher than pure Pt and 3.5 times higher than a commercial catalyst with a 1:1 Pt:Ru bulk atomic ratio.

  11. Pd-Pt Bimetallic Nanodendrites with High Activity for Oxygen Reduction

    SciTech Connect

    Lim, B.; Tao, J.; Jiang, M.; Camargo, P.H.C.; Cho, E.C.; Lu, X.; Zhu, Y.; Xia, Y.

    2009-06-05

    Controlling the morphology of Pt nanostructures can provide a great opportunity to improve their catalytic properties and increase their activity on a mass basis. We synthesized Pd-Pt bimetallic nanodendrites consisting of a dense array of Pt branches on a Pd core by reducing K{sub 2}PtCl{sub 4} with L-ascorbic acid in the presence of uniform Pd nanocrystal seeds in an aqueous solution. The Pt branches supported on faceted Pd nanocrystals exhibited relatively large surface areas and particularly active facets toward the oxygen reduction reaction (ORR), the rate-determining step in a proton-exchange membrane fuel cell. The Pd-Pt nanodendrites were two and a half times more active on the basis of equivalent Pt mass for the ORR than the state-of-the-art Pt/C catalyst and five times more active than the first-generation supportless Pt-black catalyst.

  12. Synthesis and characterization of polyhedral and quasi-sphere non-polyhedral Pt nanoparticles: effects of their various surface morphologies and sizes on electrocatalytic activity for fuel cell applications

    NASA Astrophysics Data System (ADS)

    Long, Nguyen Viet; Ohtaki, Michitaka; Hien, Tong Duy; Jalem, Randy; Nogami, Masayuki

    2011-10-01

    In this article, polyhedral and non-polyhedral Pt nanoparticles were prepared by modified polyol method using AgNO3 as a good structure-modifying agent. Their TEM and HRTEM images showed the particle size in the range of 8-16 nm for both the above cases. The structures and properties of the surfaces of Pt nanoparticles were investigated through cyclic voltammetry in dilute perchloric acid (HClO4) electrolyte solution. A comparison of the electrocatalytic property in methanol electrooxidation was made. Here, the effects of polyhedral and non-polyhedral morphologies on their catalytic properties were studied. The results revealed that the special catalytic activity of quasi-sphere non-polyhedral Pt nanoparticles is higher than that of polyhedral Pt nanoparticles. In addition, Pt nanoparticles of un-sharp and quasi-sphere morphologies exhibit the tolerance to poisoning species better than that of Pt nanoparticles of sharp and polyhedral morphologies due to the various morphologies of the catalyst surfaces in the chronoamperometric plots. Therefore, these experimental evidences showed the morphology-dependent catalytic property according to the various morphologies and complexity of their catalyst surfaces.

  13. Adsorption and coupling of 4-aminophenol on Pt(111) surfaces

    NASA Astrophysics Data System (ADS)

    Otero-Irurueta, G.; Martínez, J. I.; Bueno, R. A.; Palomares, F. J.; Salavagione, H. J.; Singh, M. K.; Méndez, J.; Ellis, G. J.; López, M. F.; Martín-Gago, J. A.

    2016-04-01

    We have deposited 4-aminophenol on Pt(111) surfaces in ultra-high vacuum and studied the strength of its adsorption through a combination of STM, LEED, XPS and ab initio calculations. Although an ordered (2√3 × 2√3)R30° phase appears, we have observed that molecule-substrate interaction dominates the adsorption geometry and properties of the system. At RT the high catalytic activity of Pt induces aminophenol to lose the H atom from the hydroxyl group, and a proportion of the molecules lose the complete hydroxyl group. After annealing above 420 K, all deposited aminophenol molecules have lost the OH moiety and some hydrogen atoms from the amino groups. At this temperature, short single-molecule oligomer chains can be observed. These chains are the product of a new reaction that proceeds via the coupling of radical species that is favored by surface diffusion.

  14. Adsorption and Coupling of 4-aminophenol on Pt(111) surfaces.

    PubMed

    Otero-Irurueta, G; Martínez, J I; Bueno, R A; Palomares, F J; Salavagione, H J; Singh, M K; Méndez, J; Ellis, G J; López, M F; Martín-Gago, J A

    2015-09-06

    We have deposited 4-aminophenol on Pt(111) surfaces in ultra-high vacuum and studied the strength of its adsorption through a combination of STM, LEED, XPS and ab initio calculations. Although an ordered (2√3×2√3)R30° phase appears, we have observed that molecule-substrate interaction dominates the adsorption geometry and properties of the system. At RT the high catalytic activity of Pt induces aminophenol to lose the H atom from the hydroxyl group, and a proportion of the molecules lose the complete hydroxyl group. After annealing above 420K, all deposited aminophenol molecules have lost the OH moiety and some hydrogen atoms from the amino groups. At this temperature, short single-molecule oligomer chains can be observed. These chains are the product of a new reaction that proceeds via the coupling of radical species that is favoured by surface diffusion.

  15. Adsorption and Coupling of 4-aminophenol on Pt(111) surfaces

    PubMed Central

    Otero-Irurueta, G.; Martínez, J. I.; Bueno, R.A.; Palomares, F. J.; Salavagione, H. J.; Singh, M. K.; Méndez, J.; Ellis, G. J.; López, M. F.; Martín-Gago, J. A.

    2016-01-01

    We have deposited 4-aminophenol on Pt(111) surfaces in ultra-high vacuum and studied the strength of its adsorption through a combination of STM, LEED, XPS and ab initio calculations. Although an ordered (2√3×2√3)R30° phase appears, we have observed that molecule-substrate interaction dominates the adsorption geometry and properties of the system. At RT the high catalytic activity of Pt induces aminophenol to lose the H atom from the hydroxyl group, and a proportion of the molecules lose the complete hydroxyl group. After annealing above 420K, all deposited aminophenol molecules have lost the OH moiety and some hydrogen atoms from the amino groups. At this temperature, short single-molecule oligomer chains can be observed. These chains are the product of a new reaction that proceeds via the coupling of radical species that is favoured by surface diffusion. PMID:27279673

  16. Beneficial compressive strain for oxygen reduction reaction on Pt (111) surface

    SciTech Connect

    Kattel, Shyam; Wang, Guofeng

    2014-09-28

    We investigated the influence of compressive surface strain on the progression of oxygen reduction reaction (ORR) on Pt(111) surface using the density functional theory (DFT) calculation method. Specifically, we calculated the binding energies of all the chemical species possibly involved in ORR and the reaction energies (heat of reaction and activation energy) of all the possible ORR elementary reactions on the Pt(111) surfaces with −2% and −3% strain. Our DFT results indicate that all the ORR species bind more weakly on the compressively strained surfaces than on an unstrained surface owing to strain-induced d-electron band broadening. Our DFT calculations further predict that both OOH dissociation and HOOH dissociation pathways could be active for ORR on the Pt(111) surface with compressive strain between −2% and −3%. Moreover, the activation energies of the ORR rate-determining steps on the compressively strained Pt(111) surfaces were found to be lower than that on the unstrained Pt(111) surface. It was thus inferred that a −2% to −3% surface strain could lead to enhanced ORR activity on the Pt(111) catalysts. Consequently, our study suggests that tuning surface strain is an effective way to improve the performance of Pt-based electrocatalysts for ORR.

  17. A first-principle calculation of sulfur oxidation on metallic Ni(111) and Pt(111), and bimetallic Ni@Pt(111) and Pt@Ni(111) surfaces.

    PubMed

    Yeh, Chen-Hao; Ho, Jia-Jen

    2012-09-17

    Sulfur, a pollutant known to poison fuel-cell electrodes, generally comes from S-containing species such as hydrogen sulfide (H(2)S). The S-containing species become adsorbed on a metal electrode and leave atomic S strongly bound to the metal surface. This surface sulfur is completely removed typically by oxidation with O(2) into gaseous SO(2). According to our DFT calculations, the oxidation of sulfur at 0.25 ML surface sulfur coverage on pure Pt(111) and Ni(111) metal surfaces is exothermic. The barriers to the formation of SO(2) are 0.41 and 1.07 eV, respectively. Various metals combined to form bimetallic surfaces are reported to tune the catalytic capabilities toward some reactions. Our results show that it is more difficult to remove surface sulfur from a Ni@Pt(111) surface with reaction barrier 1.86 eV for SO(2) formation than from a Pt@Ni(111) surface (0.13 eV). This result is in good agreement with the statement that bimetallic surfaces could demonstrate more or less activity than to pure metal surfaces by comparing electronic and structural effects. Furthermore, by calculating the reaction free energies we found that the sulfur oxidation reaction on the Pt@Ni(111) surface exhibits the best spontaneity of SO(2) desorption at either room temperature or high temperatures.

  18. Designed nanostructured pt film for electrocatalytic activities by underpotential deposition combined chemical replacement techniques.

    PubMed

    Huang, Minghua; Jin, Yongdong; Jiang, Heqing; Sun, Xuping; Chen, Hongjun; Liu, Baifeng; Wang, Erkang; Dong, Shaojun

    2005-08-18

    Multiple-deposited Pt overlayer modified Pt nanoparticle (MD-Pt overlayer/PtNPs) films were deliberately constructed on glassy carbon electrodes through alternately multiple underpotential deposition (UPD) of Ag followed redox replacement reaction by Pt (II) cations. The linear and regular growth of the films characterized by cyclic voltammetry was observed. Atomic force spectroscopy (AFM) provides the surface morphology of the nanostructured Pt films. Rotating disk electrode (RDE) voltammetry and rotating ring-disk electrode (RRDE) voltammetry demonstrate that the MD-Pt overlayer/PtNPs films can catalyze an almost four-electron reduction of O(2) to H(2)O in air-saturated 0.1 M H(2)SO(4). Thus-prepared Pt films behave as novel nanostructured electrocatalysts for dioxygen reduction and hydrogen evolution reaction (HER) with enhanced electrocatalytic activities, in terms of both reduction peak potential and peak current, when compared to that of the bulk polycrystalline Pt electrode. Additionally, it is noted that after multiple replacement cycles, the electrocatalytic activities improved remarkably, although the increased amount of Pt is very low in comparison to that of pre-modified PtNPs due to the intrinsic feature of the UPD-redox replacement technique. In other words, the electrocatalytic activities could be improved markedly without using very much Pt by the technique of tailoring the catalytic surface. These features may provide an interesting way to produce Pt catalysts with a reliable catalytic performance as well as a reduction in cost.

  19. Design and synthesis of bimetallic electrocatalyst with multilayered Pt-skin surfaces.

    SciTech Connect

    Wang, C.; Chi, M.; Li, D.; Strmcnik, D.; van der Vliet, D.; Wang, G.; Komanicky, V.; Chang, K.-C.; Paulikas, A. P.; Tripkovic, D.; Pearson, J.; More, K. L.; Markovic, N. M.; Stamenkovic, V. R.

    2011-01-01

    Advancement in heterogeneous catalysis relies on the capability of altering material structures at the nanoscale, and that is particularly important for the development of highly active electrocatalysts with uncompromised durability. Here, we report the design and synthesis of a Pt-bimetallic catalyst with multilayered Pt-skin surface, which shows superior electrocatalytic performance for the oxygen reduction reaction (ORR). This novel structure was first established on thin film extended surfaces with tailored composition profiles and then implemented in nanocatalysts by organic solution synthesis. Electrochemical studies for the ORR demonstrated that after prolonged exposure to reaction conditions, the Pt-bimetallic catalyst with multilayered Pt-skin surface exhibited an improvement factor of more than 1 order of magnitude in activity versus conventional Pt catalysts. The substantially enhanced catalytic activity and durability indicate great potential for improving the material properties by fine-tuning of the nanoscale architecture.

  20. Design and Synthesis of Bimetallic Electrocatalyst with Multilayered Pt-Skin Surfaces

    SciTech Connect

    Wang, Chao; Chi, Miaofang; Li, Dongguo; Strmcnik, Dusan; Van der Vliet, Dennis; Wang, Guofeng; Komanicky, Vladimir; Chang, Kee-Chul; Paulikas, Arvydas; Tripkovic, Dusan; Pearson, John; More, Karren Leslie; Markovic, Nenad; Stamenkovic, Vojislav

    2011-01-01

    Advancement in heterogeneous catalysis relies on the capability of altering material structures at the nanoscale, and that is particularly important for the development of highly active electrocatalysts with uncompromised durability. Here, we report the design and synthesis of a Pt-bimetallic catalyst with multilayered Pt-skin surface, which shows superior electrocatalytic performance for the oxygen reduction reaction (ORR). This novel structure was first established on thin film extended surfaces with tailored composition profiles and then implemented in nanocatalysts by organic solution synthesis. Electrochemical studies for the ORR demonstrated that after prolonged exposure to reaction conditions, the Pt-bimetallic catalyst with multilayered Pt-skin surface exhibited an improvement factor of more than 1 order of magnitude in activity versus conventional Pt catalysts. The substantially enhanced catalytic activity and durability indicate great potential for improving the material properties by fine-tuning of the nanoscale architecture.

  1. Site preference of NH3-adsorption on Co, Pt and CoPt surfaces: the role of charge transfer, magnetism and strain.

    PubMed

    Bhattacharjee, S; Gupta, K; Jung, N; Yoo, S J; Waghmare, U V; Lee, S C

    2015-04-14

    Oxidation of Co at the surface poses a major problem in the cyclable use of CoPt, a cost-effective catalyst for proton exchange membrane fuel cells. This can be alleviated by attaching a ligand selectively to Co-sites to stop its oxidation without compromising the catalytic activity. Here, we present a comparative analysis of adsorption of NH3 on the (0001) surface of Co in the HCP structure and (111) surfaces of Pt and CoPt alloy in the FCC structure, using first-principles density functional theoretical calculations. While NH3 binds more strongly with the Pt surface than with the Co surface, we find that its binding with the Co atom is stronger than that with the Pt atom on the surface of the CoPt alloy. Our analysis of the charge density and electronic structure shows how this originates from (a) the electron transfer from the minority spin d-band of Co to Pt, and (b) shift in the energy of d-bands and the magnetic moments of Co atoms on the surface of the CoPt alloy relative to those on the (0001) surface of Co. Hybridization of the d-states of Co in CoPt with pz states of N in NH3 used to stop Co oxidation also results in improving the charge transfer from Co to Pt that is relevant to the catalytic activity of CoPt. We finally present the analysis of how the interaction of NH3 with the CoPt surface can be tuned with strain.

  2. PT AND PT/NI "NEEDLE" ELETROCATALYSTS ON CARBON NANOTUBES WITH HIGH ACTIVITY FOR THE ORR

    SciTech Connect

    Colon-Mercado, H.

    2011-11-10

    Platinum and platinum/nickel alloy electrocatalysts supported on graphitized (gCNT) or nitrogen doped carbon nanotubes (nCNT) are prepared and characterized. Pt deposition onto carbon nanotubes results in Pt 'needle' formations that are 3.5 nm in diameter and {approx}100 nm in length. Subsequent Ni deposition and heat treatment results in PtNi 'needles' with an increased diameter. All Pt and Pt/Ni materials were tested as electrocatalysts for the oxygen reduction reaction (ORR). The Pt and Pt/Ni catalysts showed excellent performance for the ORR, with the heat treated PtNi/gCNT (1.06 mA/cm{sup 2}) and PtNi/nCNT (0.664 mA/cm{sup 2}) showing the highest activity.

  3. Anomalous surface phase formation on Pt sub 3 Sn <110>

    SciTech Connect

    Haner, A.N.; Ross, P.N. ); Bardi, U. . Dipt. di Chimica)

    1990-06-01

    LEED analysis of the clean annealed surface of a {l angle}110{r angle} oriented Pt{sub 3}Sn single crystal surface indicates the formation of a multilayer surface phase which does not have the L1{sub 2} bulk structure. LEISS analysis indicates a surface stoichiometry of ca. 1:1 with Sn atoms displaced ca. 1.4 above the plane of Pt atoms. The surface phase is hypothesized to be a rhombic distortion of the {l angle}0001{r angle} plant of PtSn, which has a B8{sub 1} (NiAs-type) bulk structure. It is not clear whether the phase forms by precipitation of PtSn due to a slight (0.5%) stoichiometric excess of Sn in the bulk, or due to multilayer reconstruction driven by surface segregation. 20 refs., 3 figs.

  4. Tuning the surface electronic structure of a Pt3Ti(111) electro catalyst

    NASA Astrophysics Data System (ADS)

    Paßens, M.; Caciuc, V.; Atodiresei, N.; Moors, M.; Blügel, S.; Waser, R.; Karthäuser, S.

    2016-07-01

    Increasing the efficiency and stability of bimetallic electro catalysts is particularly important for future clean energy technologies. However, the relationship between the surface termination of these alloys and their catalytic activity is poorly understood. Therefore, we report on fundamental UHV-SPM, LEED, and DFT calculations of the Pt3Ti(111) single crystal surface. Using voltage dependent imaging the surface termination of Pt3Ti(111) was studied with atomic resolution. Combining these images with simulated STM maps based on ab initio DFT calculations allowed us to identify the three upper layers of the Pt3Ti(111) single crystal and their influence upon the surface electronic structure. Our results show that small changes in the composition of the second and third atomic layer are of significant influence upon the surface electronic structure of the Pt3Ti electro catalyst. Furthermore, we provide relevant insights into the dependence of the surface termination on the preparation conditions.Increasing the efficiency and stability of bimetallic electro catalysts is particularly important for future clean energy technologies. However, the relationship between the surface termination of these alloys and their catalytic activity is poorly understood. Therefore, we report on fundamental UHV-SPM, LEED, and DFT calculations of the Pt3Ti(111) single crystal surface. Using voltage dependent imaging the surface termination of Pt3Ti(111) was studied with atomic resolution. Combining these images with simulated STM maps based on ab initio DFT calculations allowed us to identify the three upper layers of the Pt3Ti(111) single crystal and their influence upon the surface electronic structure. Our results show that small changes in the composition of the second and third atomic layer are of significant influence upon the surface electronic structure of the Pt3Ti electro catalyst. Furthermore, we provide relevant insights into the dependence of the surface termination on the

  5. Surface morphology after low coverage Pt deposition on Cu(110)

    NASA Astrophysics Data System (ADS)

    Hugenschmidt, Markus B.; de Beauvais, Christophe

    1994-04-01

    The morphology of a Cu(110) surface after low coverage Pt atom deposition from the vapour phase is studied with thermal energy atom scattering (TEAS) in the temperature range of 200-800 K. Both cross section measurements and diffraction analysis reveal different structures. At low temperatures, isolated defects containing a metal adatom are observed. Between 350 and 650 K, experimental results suggest that these aggregates are dissociated, leaving behind them an almost flat surface patch with an incorporated Pt atom. Above 650 K, bulk dissolution of Pt occurs.

  6. Enhanced Activity and Stability of Pt catalysts on Functionalized Graphene Sheets for Electrocatalytic Oxygen Reduction

    SciTech Connect

    Kou, Rong; Shao, Yuyan; Wang, Donghai; Engelhard, Mark H.; Kwak, Ja Hun; Wang, Jun; Viswanathan, Vilayanur V.; Wang, Chong M.; Lin, Yuehe; Wang, Yong; Aksay, Ilhan A.; Liu, Jun

    2009-04-30

    Electrocatalysis of oxygen reduction using Pt nanoparticles supported on functionalized graphene sheets (FGSs) was studied. FGSs were prepared by thermal expansion of graphite oxide. Pt nanoparticles with average diameter of 2 nm were uniformly loaded on FGSs by impregnation methods. Pt-FGS showed a higher electrochemical surface area and oxygen reduction activity with improved stability as compared with commercial catalyst. Transmission electron microscopy, X-ray photoelectron spectroscopy, and electrochemical characterization suggest that the improved performance of Pt-FGS can be attributed to smaller particle size and less aggregation of Pt nanoparticles on the functionalized graphene sheets.

  7. Enhancing oxygen reduction reaction activity of Pt-shelled catalysts via subsurface alloying.

    PubMed

    Cheng, Daojian; Qiu, Xiangguo; Yu, Haiyan

    2014-10-14

    Despite remarkable efforts have been put into the field of Pt-shelled catalysts containing an atomically thin Pt surface layer for the oxygen reduction reaction (ORR) in the last decade, further development of new Pt-shelled catalysts is still necessary. Here, a new set of Pt-shelled catalysts by subsurface alloying with early transition metals such as Mn and Fe is predicted to be a good candidate for the ORR by using density functional theory (DFT) calculations. Trends in oxygen reduction activity of Pt-alloy catalysts are determined with calculations of oxygen binding by using the slab and cluster models. It is found that the subsurface alloys by the incorporation of submonolayer M (M = Mn and Fe) into Pt(111) in the slab model result in the enhancement of ORR activity, compared with the well-known Pt(111)-skin-M, pure Pt, and Pt3M alloy catalysts. For the cluster model, the Pt12Mn and Pt12Fe clusters are also found to be the optimal catalysts for the ORR. It is expected that this work can open up new opportunities for enhancing the ORR activity of Pt-alloy catalysts by subsurface alloying.

  8. SISGR: Theoretically relating the surface composition of Pt alloys to their performance as the electrocatalysts of low-temperature fuel cells

    SciTech Connect

    Wang, Guofeng

    2010-12-31

    The main goal of this project is to gain fundamental knowledge about the relation between surface composition and catalytic performance of Pt alloy catalysts for oxygen reduction reaction (ORR). Specific objectives are: to develop and improve a first-principles based multiscale computation approach to simulating surface segregation phenomena in Pt alloy surfaces; to evaluate the surface electronic structure and catalytic activity of Pt alloy catalysts and; to relate the surface composition to the catalytic performance of Pt alloy catalysts.

  9. Pd surface and Pt subsurface segregation in Pt1-c Pd c nanoalloys

    NASA Astrophysics Data System (ADS)

    De Clercq, A.; Giorgio, S.; Mottet, C.

    2016-02-01

    The structure and chemical arrangement of Pt1-c Pd c nanoalloys with the icosahedral and face centered cubic symmetry are studied using Monte Carlo simulations with a tight binding interatomic potential fitted to density-functional theory calculations. Pd surface segregation from the lowest to the highest coordinated sites is predicted by the theory together with a Pt enrichment at the subsurface, whatever the structure and the size of the nanoparticles, and which subsists when increasing the temperature. The onion-shell chemical configuration is found for both symmetries and is initiated from the Pd surface segregation. It is amplified in the icosahedral symmetry and small sizes but when considering larger sizes, the oscillating segregation profile occurs near the surface on about three to four shells whatever the structure. Pd segregation results from the significant lower cohesive energy of Pd as compared to Pt and the weak ordering tendency leads to the Pt subsurface segregation. The very weak size mismatch does not prevent the bigger atoms (Pt) from occupying subsurface sites which are in compression whereas the smaller ones (Pd) occupy the central site of the icosahedra where the compression is an order of magnitude higher.

  10. Real-time investigations of Pt(111) surface transformations in sulfuric acid solutions.

    PubMed

    Braunschweig, Björn; Mukherjee, Prabuddha; Dlott, Dana D; Wieckowski, Andrzej

    2010-10-13

    We present the first broadband sum-frequency generation (SFG) spectra of adlayers from sulfuric acid solutions on Pt(111) surfaces and reveal surface transformations of (bi)sulfate anions in unprecedented detail. SFG amplitudes, bandwidth, and electrochemical Stark tuning of (bi)sulfate vibrational bands centered at 1250-1290 cm(-1) strongly depend on the applied potential and are correlated with prominent voltammetric features. (Bi)sulfate adlayers on Pt(111) are important model systems for weak, specific adsorption of anions on catalytically active surfaces. Although the existence of surface transformations on Pt(111) in dilute H(2)SO(4) solutions has been established by previous studies, so far they have not been observed with surface vibrational spectroscopy. Our results confirm previous reports of a surface transformation at 0.21 V and provide new information on a second transformation at 0.5 V due to surface hydroxyl formation and rearrangement of the electric double layer.

  11. A Cu/Pt Near-Surface Alloy for Water-Gas Shift Catalysis.

    SciTech Connect

    Knudsen, Jan; Nilekar, Anand U.; Vang, Ronnie T.; Schnadt, Joachim; Kunkes, Edward L.; Dumesic, James A.; Mavrikakis, Manos; Besenbacher, Fleming

    2007-05-01

    The research described in this product was performed in part in the Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory. The primary route to hydrogen production from fossil fuels involves the water-gas shift (WGS) reaction, and an improvement in the efficiency of WGS catalysts could therefore lead to a major leap forward in the realization of hydrogen economy. On the basis of a combination of high-resolution scanning tunneling microscopy, X-ray photoelectron spectroscopy, and density functional theory (DFT) calculations, we suggest the existence of a new thermodynamically stable Cu/Pt near-surface alloy (NSA). Temperature-programmed desorption and DFT reveal that this Cu/Pt NSA binds CO significantly more weakly than does Pt alone, thereby implying a considerable reduction in the potential for CO poisoning of the Cu/Pt NSA surface as compared to that of pure Pt. In addition, DFT calculations show that this Cu/Pt NSA is able to activate H2O easily, which is the rate-determining step for the WGS on several metal surfaces, and, at the same time, to bind the products of that reaction and formate intermediates rather weakly, thus avoiding possible poisoning of the catalyst surface. The Cu/Pt NSA is thus a promising candidate for an improved WGS catalyst.

  12. Stellated Ag-Pt bimetallic nanoparticles: An effective platform for catalytic activity tuning

    PubMed Central

    Liu, Hui; Ye, Feng; Yao, Qiaofeng; Cao, Hongbin; Xie, Jianping; Lee, Jim Yang; Yang, Jun

    2014-01-01

    The usefulness of Pt-based nanomaterials for catalysis can be greatly enhanced by coupling morphology engineering to the strategic presence of a second or even third metal. Here we demonstrate the design and preparation of stellated Ag-Pt bimetallic nanoparticles where significant activity difference between the methanol oxidation reaction (MOR) and the oxygen reduction reaction (ORR) may be realized by relegating Ag to the core or by hollowing out the core. In particular the stellated Pt surface, with an abundance of steps, edges, corner atoms, and {111} facets, is highly effective for the ORR but is ineffective for MOR. MOR activity is only observed in the presence of a Ag core through electronic coupling to the stellated Pt shell. The bimetallic Ag-Pt stellates therefore demonstrate the feasibility of tuning a Pt surface for two very different structure sensitive catalytic reactions. Stellated bimetallics may therefore be an effective platform for highly tunable catalyst designs. PMID:24495979

  13. In situ electro-deposition of Pt micro-nano clusters on the surface of {[PMo12O40]3-/PAMAM}n multilayer composite films and their electrocatalytic activities regarding methanol oxidation.

    PubMed

    Li, Zhong-Shui; Lin, Shen; Chen, Zu-liang; Shi, Yuan-De; Huang, Xiao-Mei

    2012-02-15

    The {[PMo(12)O(40)](3-)/PAMAM}(n) multilayer films are prepared by LBL electrostatic assembly technique, and their uniform and homogeneous traits have been verified by cyclic voltammetry. The {[PMo(12)O(40)](3-)/PAMAM}(n) multilayer films with PAMAM as the outmost layer, having an open structure and exhibiting good penetrability for the solvent molecules at low pH, are used as matrices for electro-deposition of Pt micro-nano clusters in situ. X-ray photoelectron spectroscopy (XPS) analysis and field emission scanning electron microscope (FE-SEM) characterization show that the unique Pt micro-nano clusters with flower-like structure have been immobilized on the surface of {[PMo(12)O(40)](3-)/PAMAM}(n) multilayer films. The morphologies of Pt micro-nano clusters are influenced by electro-deposition conditions such as deposition potential, deposition time, and the number of layers of {[PMo(12)O(40)](3-)/PAMAM}(n) multilayer films. Pt(-clusters)-{PMo(12)/PAMAM}(3) composite films demonstrate good electrocatalytic activities regarding methanol oxidation and improved tolerance of CO.

  14. Heterogeneous Au-Pt nanostructures with enhanced catalytic activity toward oxygen reduction.

    PubMed

    Ye, Feng; Liu, Hui; Hu, Weiwei; Zhong, Junyu; Chen, Yingying; Cao, Hongbin; Yang, Jun

    2012-03-14

    Heterogeneous Au-Pt nanostructures have been synthesized using a sacrificial template-based approach. Typically, monodispersed Au nanoparticles are prepared first, followed by Ag coating to form core-shell Au-Ag nanoparticles. Next, the galvanic replacement reaction between Ag shells and an aqueous H(2)PtCl(6) solution, whose chemical reaction can be described as 4Ag + PtCl(6)(2-)→ Pt + 4AgCl + 2Cl(-), is carried out at room temperature. Pure Ag shell is transformed into a shell made of Ag/Pt alloy by galvanic replacement. The AgCl formed simultaneously roughens the surface of alloy Ag-Pt shells, which can be manipulated to create a porous Pt surface for oxygen reduction reaction. Finally, Ag and AgCl are removed from core-shell Au-Ag/Pt nanoparticles using bis(p-sulfonatophenyl)phenylphosphane dihydrate dipotassium salt to produce heterogeneous Au-Pt nanostructures. The heterogeneous Au-Pt nanostructures have displayed superior catalytic activity towards oxygen reduction in direct methanol fuel cells because of the electronic coupling effect between the inner-placed Au core and the Pt shell.

  15. Surface enrichment of Pt in Ga2O3 films grown on liquid Pt/Ga alloys

    NASA Astrophysics Data System (ADS)

    Grabau, Mathias; Krick Calderón, Sandra; Rietzler, Florian; Niedermaier, Inga; Taccardi, Nicola; Wasserscheid, Peter; Maier, Florian; Steinrück, Hans-Peter; Papp, Christian

    2016-09-01

    The formation of surface Ga2O3 films on liquid samples of Ga, and Pt-Ga alloys with 0.7 and 1.8 at.% Pt was examined using near-ambient pressure (NAP) X-ray photoelectron spectroscopy (XPS). Thickness, composition and growth of the oxide films were deduced as a function of temperature and Pt content of the alloys, in ultra-high vacuum and at oxygen pressures of 3 × 10- 7, 3 × 10- 3 and 1 mbar. We examined oxide layers up to a thickness of 37 Å. Different growth modes were found for oxidation at low and high pressures. The formed Ga2O3 oxide films showed an increased Pt content, while the pristine GaPt alloy showed a surface depletion of Pt at the examined temperatures. Upon growth of Ga2O3 on Pt/Ga alloys a linear increase of Pt content was observed, due to the incorporation of 3.6 at.% Pt in the Ga2O3. The Pt content in Ga2O3, at the examined temperatures and bulk Pt concentrations is found to be independent of pressure, temperature and the nominal Pt content of the metallic alloy.

  16. Mesoporous graphene-like nanobowls as Pt electrocatalyst support for highly active and stable methanol oxidation

    NASA Astrophysics Data System (ADS)

    Yan, Zaoxue; He, Guoqiang; Jiang, Zhifeng; Wei, Wei; Gao, Lina; Xie, Jimin

    2015-06-01

    Mesoporous graphene-like nanobowls (GLBs) with high surface area of 1091 m2 g-1, high pore volume of 2.7 cm3 g-1 and average pore diameter of 9.8 nm are synthesized through template method. The GLBs with inherent excellent electrical conductivity and chemical inertia show the properties of well mass transfer, poison resistance and stable loading of smaller Pt particles. Therefore, the Pt/GLB catalyst shows much higher activity and stability than that of commercial Pt/C (TKK) for methanol oxidation reaction (MOR). Therein, the peak current density on Pt/GLB (2075 mA mgPt-1) for MOR is 2.87 times that of commercial Pt/C (723 mA mgPt-1); and the onset potential for the MOR on the former is negatively shifted about 160 mV compared with that on the latter. The catalytic performances of the Pt/GLB are also better than those of the Pt loading on mesoporous amorphous carbon nanobowls (Pt/BLC), indicating promotion effect of graphite on Pt catalytic performance.

  17. Improved electrocatalytic ethanol oxidation activity in acidic and alkaline electrolytes using size-controlled Pt-Sn nanoparticles.

    PubMed

    St John, Samuel; Boolchand, Punit; Angelopoulos, Anastasios P

    2013-12-31

    The promotion of the electrocatalytic ethanol oxidation reaction (EOR) on extended single-crystal Pt surfaces and dispersed Pt nanoparticles by Sn under acidic conditions is well known. However, the correlation of Sn coverage on Pt nanoparticle electrocatalysts to their size has proven difficult. The reason is that previous investigations have typically relied on commercially difficult to reproduce electrochemical treatments of prepared macroscopic electrodes to adsorb Sn onto exposed Pt surfaces. We demonstrate here how independent control over both Sn coverage and particle size can yield a significant enhancement in EOR activity in an acidic electrolyte relative to previously reported electrocatalysts. Our novel approach uses electroless nanoparticle synthesis where surface-adsorbed Sn is intrinsic to Pt particle formation. Sn serves as both a reducing agent and stabilizing ligand, producing particles with a narrow particle size distribution in a size range where the mass-specific electrocatalytic activity can be maximized (ca. 1-4 nm) as a result of the formation of a fully developed Sn shell. The extent of fractional Sn surface coverage on carbon-supported Pt nanoparticles can be systematically varied through wet-chemical treatment subsequent to nanoparticle formation but prior to incorporation into macroscopic electrodes. EOR activity for Pt nanoparticles is found to be optimum at a fractional Sn surface coverage of ca. 0.6. Furthermore, the EOR activity is shown to increase with Pt particle size and correlate with the active area of available Pt (110) surface sites for the corresponding Sn-free nanoparticles. The maximum area- and mass-specific EOR activities for the most active catalyst investigated were 17.9 μA/cm(2)Pt and 12.5 A/gPt, respectively, after 1 h of use at 0.42 V versus RHE in an acidic electrolyte. Such activity is a substantial improvement over that of commercially available Pt, Pt-Sn, and Pt-Ru alloy catalysts under either acidic or alkaline

  18. Effect of multiwalled carbon nanotubes with different specific surface areas on the stability of supported Pt catalysts

    NASA Astrophysics Data System (ADS)

    Zhao, Lei; Wang, Zhen-Bo; Sui, Xu-Lei; Yin, Ge-Ping

    2014-01-01

    Pt/MCNTs catalysts have been synthesized by the microwave-assisted polyol process (MAPP). Effect of multiwalled carbon nanotubes (MCNTs) with different specific surface areas on the stability of supported Pt catalysts has been investigated. The obtained Pt/MCNTs catalysts are characterized by X-ray diffraction (XRD), Energy dispersive analysis of X-ray (EDAX), transmission electron microscopy (TEM), cyclic voltammograms (CV), electrochemical impedance spectroscopy (EIS), and accelerated potential cycling tests (APCT) to present the stability of the catalysts. The experimental results indicate that the original electrochemically active specific surface areas (ESA) and the activity for methanol electrooxidation of the catalysts decrease with the decreasing of the specific surface areas of MCNTs, and the Pt/MCNTs-250 (MCNTs with pristine specific surface of 250 m2 g-1, below the same) catalysts show the best initial electrochemical activity. However, the activity of the Pt/MCNTs-250 is very close to that of the Pt/MCNTs-120 and the stability of the Pt/MCNTs-60 catalyst is the best after 1000 cycles APCT. Considering the factors of the activity and stability comprehensively, the optimized specific surface area of MCNTs in the Pt/MCNTs catalysts is 120 m2 g-1.

  19. Antiproliferative Pt(IV) complexes: synthesis, biological activity, and quantitative structure-activity relationship modeling.

    PubMed

    Gramatica, Paola; Papa, Ester; Luini, Mara; Monti, Elena; Gariboldi, Marzia B; Ravera, Mauro; Gabano, Elisabetta; Gaviglio, Luca; Osella, Domenico

    2010-09-01

    Several Pt(IV) complexes of the general formula [Pt(L)2(L')2(L'')2] [axial ligands L are Cl-, RCOO-, or OH-; equatorial ligands L' are two am(m)ine or one diamine; and equatorial ligands L'' are Cl- or glycolato] were rationally designed and synthesized in the attempt to develop a predictive quantitative structure-activity relationship (QSAR) model. Numerous theoretical molecular descriptors were used alongside physicochemical data (i.e., reduction peak potential, Ep, and partition coefficient, log Po/w) to obtain a validated QSAR between in vitro cytotoxicity (half maximal inhibitory concentrations, IC50, on A2780 ovarian and HCT116 colon carcinoma cell lines) and some features of Pt(IV) complexes. In the resulting best models, a lipophilic descriptor (log Po/w or the number of secondary sp3 carbon atoms) plus an electronic descriptor (Ep, the number of oxygen atoms, or the topological polar surface area expressed as the N,O polar contribution) is necessary for modeling, supporting the general finding that the biological behavior of Pt(IV) complexes can be rationalized on the basis of their cellular uptake, the Pt(IV)-->Pt(II) reduction, and the structure of the corresponding Pt(II) metabolites. Novel compounds were synthesized on the basis of their predicted cytotoxicity in the preliminary QSAR model, and were experimentally tested. A final QSAR model, based solely on theoretical molecular descriptors to ensure its general applicability, is proposed.

  20. Durable electrocatalytic-activity of Pt-Au/C cathode in PEMFCs.

    PubMed

    Selvaganesh, S Vinod; Selvarani, G; Sridhar, P; Pitchumani, S; Shukla, A K

    2011-07-21

    Longevity remains as one of the central issues in the successful commercialization of polymer electrolyte membrane fuel cells (PEMFCs) and primarily hinges on the durability of the cathode. Incorporation of gold (Au) to platinum (Pt) is known to ameliorate both the electrocatalytic activity and stability of cathode in relation to pristine Pt-cathodes that are currently being used in PEMFCs. In this study, an accelerated stress test (AST) is conducted to simulate prolonged fuel-cell operating conditions by potential cycling the carbon-supported Pt-Au (Pt-Au/C) cathode. The loss in performance of PEMFC with Pt-Au/C cathode is found to be ∼10% after 7000 accelerated potential-cycles as against ∼60% for Pt/C cathode under similar conditions. These data are in conformity with the electrochemical surface-area values. PEMFC with Pt-Au/C cathode can withstand >10,000 potential cycles with very little effect on its performance. X-ray diffraction and transmission electron microscopy studies on the catalyst before and after AST suggest that incorporating Au with Pt helps mitigate aggregation of Pt particles during prolonged fuel-cell operations while X-ray photoelectron spectroscopy reflects that the metallic nature of Pt is retained in the Pt-Au catalyst during AST in comparison to Pt/C that shows a major portion of Pt to be present as oxidic platinum. Field-emission scanning electron microscopy conducted on the membrane electrode assembly before and after AST suggests that incorporating Au with Pt helps mitigating deformations in the catalyst layer.

  1. Shape-dependent photocatalytic hydrogen evolution activity over a Pt nanoparticle coupled g-C3N4 photocatalyst.

    PubMed

    Cao, Shaowen; Jiang, Jing; Zhu, Bicheng; Yu, Jiaguo

    2016-07-28

    Cubic, octahedral and spherical platinum (Pt) nanoparticles (NPs) ex situ supported on a graphitic carbon nitride (g-C3N4) substrate are synthesized using a colloidal adsorption-deposition method for photocatalytic hydrogen evolution reactions. These Pt NPs of different shapes have similar sizes of around 10 nm but have different facets exposed. It is found that the visible-light-driven photocatalytic activities for the Pt/g-C3N4 hybrid photocatalysts follow the order as: cubic Pt/g-C3N4 < octahedral Pt/g-C3N4 < spherical Pt/g-C3N4, revealing the significant cocatalyst shape-sensitive photocatalytic activity in the Pt/g-C3N4 hybrids. This is mainly due to the different surface atomic structures of different exposed facets of Pt NPs, which lead to the disparity of active sites and adsorption energies in photocatalytic reactions.

  2. Electrodeposition and electrocatalytic activity of Pt and Pt-alloy nanoparticles and thin films on highly oriented pyrolytic graphite (HOPG)

    NASA Astrophysics Data System (ADS)

    Lu, Guojin

    Pt and Pt-based alloy catalysts were synthesized by electrodeposition on HOPG. The nucleation and growth, morphology, composition and crystal structure, and electrocatalytic activity (towards relevant reactions in the frame of PEMFCs and DMFCs) of these model electrodes were systematically investigated. The presence of chlorides inhibits the Pt reduction processes. There is a transition from progressive to instantaneous nucleation with increasing overpotential for the deposition from 1 mM H2PtCl6 electrolytes. The possibility of instantaneous nucleation at large overpotential by using electrolytes with large chloride concentration is advantageous for the growth of small, well dispersed nanoparticles. The electrochemical data were confirmed by AFM and SEM imaging studies. Relatively narrow size distributed nanoparticles can be obtained from the current system. While MOR activity decreases with decreasing particle size, the HER and HOR activity of deposited Pt particles increases with decreasing deposition period. The ORR activity first increases then decreases with increasing deposition time. Interactions between Pt and Ru, or Ni or Co are observed and they form solid solution as verified by XRD. Underpotential deposition occurs for Pt-Ni or Pt-Co co-electrodeposition. Pt-Ru deposition can be described as progressive nucleation at low overpotential and instantaneous nucleation at high overpotentials. Through direct morphological observations, the Pt-Ni or Pt-Co nucleation can be approximately described as progressive. Pt-Ru deposits are superior to Pt towards MOR. The optimum Ru content is about 50 at.%. Pt-Ni and Pt-Co deposits are more active than Pt for ORR. The optimum content is about 30 at.% Ni or 50 at.% Co. Dealloying of Pt-Ru and Pt-Ni or Pt-Co electrodeposit is observed after electrochemical characterization. The extent of dealloying increases with the content of the alloying element.

  3. Easy synthesis approach of Pt-nanoparticles on polyaniline surface: an efficient electro-catalyst for methanol oxidation reaction

    NASA Astrophysics Data System (ADS)

    Mondal, Sanjoy; Malik, Sudip

    2016-10-01

    A facile room temperature and surfactant free synthesis of platinum nanoparticles (Pt-NPs) on benzene tetra-carboxylic acid doped polyaniline (BDP) tube has been successfully demonstrated by solution dipping method. Preparation of Pt-NPs has been done through a red-ox reaction between BDP tubes and Pt-salt, as BDP itself acts as nontoxic reducing agent as well as template cum stabilizer for Pt-NPs. In BDP@Pt composites, ∼2.5 ± 0.5 nm spherical shaped Pt-NPs as observed from TEM studies are nicely decorated on the surface of BDP. The population or the loading density of Pt-NPs on BDP tube is greatly controlled by changing the w/w ratio of BDP to H2PtCl6. Synthesized BDP@Pt composites are subsequently employed as an efficient electro-catalyst for methanol oxidation reaction (MOR) in acidic medium. Furthermore, the observed catalytic activity is consequently ∼12 times higher than that of commercially available Pt/C catalyst. Depending on the loading density of Pt-NPs on BDP tubes, the efficiency and carbon monoxide (CO) tolerance ability of composites have been explored.

  4. Exceptional methanol electro-oxidation activity by bimetallic concave and dendritic Pt-Cu nanocrystals catalysts

    NASA Astrophysics Data System (ADS)

    Wang, Ying-Xia; Zhou, Hui-Jing; Sun, Ping-Chuan; Chen, Tie-Hong

    2014-01-01

    PtCux (x = 1, 2 and 3) bimetallic nanocrystals with concave surface and dendritic morphology were prepared and used as electrocatalysts in methanol oxidation reaction (MOR) for polymer electrolyte membrane fuel cells. The bimetallic nanocrystals were synthesized via one-pot co-reduction of H2PtCl6 and Cu(acac)2 by oleylamine and polyvinyl pyrrolidone (PVP) in an autoclave at 180 °C. The concave dendritic bimetallic nanostructure consisted of a core rich in Cu and nanodendrites rich in Pt, which was formed via galvanic replacement of Cu by Pt. It was found that PVP played an important role in initiating, facilitating, and directing the replacement reaction. The electrochemical properties of the PtCux were characterized by cyclic voltammetry (CV) and chronoamperometry (CA). The concave dendritic PtCu2/C nanocrystals exhibited exceptionally high activity and strong poisoning resistance in MOR. At 0.75 V (vs. reversible hydrogen electrode, RHE) the mass activity and specific activity of PtCu2/C were 3.3 and 4.1 times higher than those of the commercial Pt/C catalysts, respectively. The enhanced catalytic activity could be attributed to the unique concave dendritic morphology of the bimetallic nanocrystals.

  5. Synthesis and photocatalytic activity of Pt-ZnO hybrid nanocomposite by solution plasma technology.

    PubMed

    Hu, Xiulan; Xu, QiuCheng; Ge, Chao; Su, Nan; Zhang, Jianbo; Huang, Huihong; Zhu, Shoufeng; Xu, Yanqiu; Cheng, Jiexu

    2017-01-27

    In this paper, Pt-ZnO hybrid nanocomposites were prepared by solution plasma technology. X-ray diffraction (XRD) and energy dispersive x-ray analysis (EDX) were used to verify their chemical composition. The size and morphology of the Pt-ZnO hybrid nanocomposites were characterized by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). These results indicate that about 2-3 nm Pt nanoparticles (NPs) were synthesized and dispersed on the pyramid-like ZnO (20-60 nm) surface. Photodegradation of Rhodamine B (RhB) demonstrates that the Pt (5 wt%)-ZnO hybrid nanocomposite has better photocatalytic activity than commercial P25 because Pt NPs restrain the photogenerated electron/hole recombination and increase the catalyst activity.

  6. Synthesis and photocatalytic activity of Pt-ZnO hybrid nanocomposite by solution plasma technology

    NASA Astrophysics Data System (ADS)

    Hu, Xiulan; Xu, QiuCheng; Ge, Chao; Su, Nan; Zhang, Jianbo; Huang, Huihong; Zhu, Shoufeng; Xu, Yanqiu; Cheng, Jiexu

    2017-01-01

    In this paper, Pt-ZnO hybrid nanocomposites were prepared by solution plasma technology. X-ray diffraction (XRD) and energy dispersive x-ray analysis (EDX) were used to verify their chemical composition. The size and morphology of the Pt-ZnO hybrid nanocomposites were characterized by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). These results indicate that about 2-3 nm Pt nanoparticles (NPs) were synthesized and dispersed on the pyramid-like ZnO (20-60 nm) surface. Photodegradation of Rhodamine B (RhB) demonstrates that the Pt (5 wt%)-ZnO hybrid nanocomposite has better photocatalytic activity than commercial P25 because Pt NPs restrain the photogenerated electron/hole recombination and increase the catalyst activity.

  7. Suppression of oxygen reduction reaction activity on Pt-based electrocatalysts from ionomer incorporation

    SciTech Connect

    Shinozaki, Kazuma; Morimoto, Yu; Pivovar, Bryan S.; Kocha, Shyam S.

    2016-09-01

    The impact of Nafion on the oxygen reduction reaction (ORR) activity is studied for Pt/C and Pt-alloy/C catalysts using thin-film rotating disk electrode (TF-RDE) methods in 0.1 M HClO4. Ultrathin uniform catalyst layers and standardized activity measurement protocols are employed to obtain accurate and reproducible ORR activity. Nafion lowers the ORR activity which plateaus with increasing loading on Pt catalysts. Pt particle size is found not to have significant influence on the extent of the SA decrease upon Nafion incorporation. Catalysts using high surface area carbon (HSC) support exhibit attenuated activity loss resulting from lower ionomer coverage on catalyst particles located within the deep pores. The impact of metallic composition on the activity loss due to Nafion incorporation is also discussed.

  8. Temperature dependent surface electrochemistry on Pt singlecrystals in alkaline electrolyte: Part 3: The oxygen reductionreaction

    SciTech Connect

    tom.schmidt@psi.ch

    2002-08-01

    The kinetics of the oxygen reduction reaction (ORR) was studied in alkaline electrolyte at 293-333K on Pt(hkl) surfaces by means of the rotating ring-disk electrode technique with solution phase peroxide detected at the ring electrode. The ORR on Pt(hkl) was found to be highly structure sensitive with activities increasing in the sequence (111) > (100) > (110)(1x2). Very similar apparent activation energies (37-45 {+-} 5 kJmol-1, {eta} = 0.35 V) were found on all three surfaces. Furthermore, at elevated temperature, significantly smaller amounts of peroxide are formed in agreement with enhanced peroxide reduction rates by increasing temperature. We found that the Tafel slopes on all three single crystal surfaces decrease with increasing temperature, indicating that the logi-E relationship is not represented by a classical Butler-Volmer expression. Based on the kinetic analysis of the polarization curves and from simulations of logi-E curves, we propose that the rate of the ORR on Pt(hkl) in alkaline solution is mainly determined by the potential/temperature dependent surface coverage by OH{sub ad}. We propose two modes of action of the OH{sub ad}: (i) OH{sub ad} blocks the adsorption of O{sub 2} on active platinum sites; and (ii) OH{sub ad} alters the adsorption energy of intermediates which are formed during the ORR on Pt sites.

  9. Structural Evolution of Solid Pt Nanoparticles to a Hollow PtFe Alloy with a Pt-Skin Surface via Space-Confined Pyrolysis and the Nanoscale Kirkendall Effect.

    PubMed

    Wang, Qingmei; Chen, Siguo; Shi, Feng; Chen, Ke; Nie, Yao; Wang, Yao; Wu, Rui; Li, Jia; Zhang, Yun; Ding, Wei; Li, Yang; Li, Li; Wei, Zidong

    2016-12-01

    A space-confined interfacial conversion approach is developed to directly transform 3 nm solid Pt nanoparticles into a 5 nm hollow PtFe alloy featuring a Pt-skin surface. The approach presented for the structural evolution from solid Pt NPs to hollow PtFe alloy with controlled size, structure, and composition can be applied to other multimetallic electrocatalysts.

  10. Effects of a TiC substrate on the catalytic activity of Pt for NO reduction.

    PubMed

    Chu, Xingli; Fu, Zhaoming; Li, Shasha; Zhang, Xilin; Yang, Zongxian

    2016-05-11

    Density functional theory calculations are used to elucidate the catalytic properties of a Pt monolayer supported on a TiC(001) substrate (Pt/TiC) toward NO reduction. It is found that the compound system of Pt/TiC has a good stability due to the strong Pt-TiC interaction. The diverse dissociation paths (namely the direct dissociation mechanism and the dimeric mechanism) are investigated. The transition state searching calculations suggest that NO has strong diffusion ability and small activation energy for dissociation on the Pt/TiC. For NO reduction on the Pt/TiC surface, we have found that the direct dissociation mechanisms (NO + N + O → NO2 + N and NO + N + O → N2 + O + O) are easier with a smaller dissociation barrier than those on the Pt(111) surface; and the dimeric process (NO + NO → (NO)2 → N2O + O → N2 + O + O) is considered to be dominant or significant with even a lower energy barrier than that of the direct dissociation. The results show that Pt/TiC can serve as an efficient catalyst for NO reduction.

  11. Composition dependence of ternary Pt-Ni-Cr catalyst activity for the methanol electro-oxidation reaction

    NASA Astrophysics Data System (ADS)

    Jeon, Min Ku; McGinn, Paul J.

    Various compositions of binary and ternary Pt-Ni-Cr alloys were investigated as catalysts for the methanol electro-oxidation reaction (MOR). Among the binary (Pt 28Ni 72/C and Pt 28Cr 72/C) and ternary Pt-Ni-Cr catalysts (Pt 28Ni 36Cr 36/C, Pt 22Ni 39Cr 39/C, Pt 33Ni 31Cr 36/C, and Pt 33Ni 36Cr 31/C) examined, the Pt 28Ni 36Cr 36/C composition exhibited the highest MOR mass activity (4.42 A g cat. -1) in the as-prepared version, which was higher than the 3.58 A g cat. -1 value of the PtRu/C catalyst after 60 min of chronoamperometry testing. The order of mass activity for the MOR was Pt 28Ni 36Cr 36/C > Pt 33Ni 36Cr 31/C > Pt 22Ni 39Cr 39/C > Pt 33Ni 31Cr 36/C > Pt 28Cr 72/C > Pt 28Ni 72/C, which was slightly changed to Pt 28Ni 36Cr 36/C > Pt 22Ni 39Cr 39/C > Pt 33Ni 36Cr 31/C > Pt 33Ni 31Cr 36/C > Pt 28Cr 72/C > Pt 28Ni 72/C after a conditioning process. The effect of anodic conditioning was also studied. A combination of X-ray diffraction, cyclic voltammetry, and chronoamperometry experiments revealed that the conditioning process caused dissolution and an oxidation state change of metallic Ni and Cr 2O 3 in the binary catalysts. The higher MOR mass activities of the ternary catalysts compared to the binary ones is attributed to co-alloying of Ni and Cr, leading to exposure of more Pt on the catalyst surface without reducing specific activities of the catalysts. The results of this study also correlate well with a prior ranking of catalytic activity of the same compositions in the form of thin film catalysts that we processed and evaluated by a high-throughput combinatorial approach [J.S. Cooper, M.K. Jeon, P.J. McGinn, Electrochem. Commun. 10 (2008) 1545-1547].

  12. Surface morphology of atomic nitrogen on Pt(111)

    SciTech Connect

    Liang, Zhu; Trenary, Michael; Jin Yang, Hyun; Kim, Yousoo

    2014-03-21

    The surface morphology of chemisorbed N on the Pt(111) surface has been studied at the atomic level with low temperature scanning tunneling microscopy (STM). When N is coadsorbed with O on the surface, they form a mixed (2 × 2)-N+O structure. When the surface is covered with N atoms only, isolated atoms and incomplete (2 × 2) patches are observed at low coverages. In a dense N layer, two phases, (√3 × √3)R30°-N and p(2 × 2)-N, are found to coexist at temperatures between 360 and 400 K. The (√3 × √3)R30° phase converts to the (2 × 2) phase as temperature increases. For both phases, nitrogen occupies fcc-hollow sites. At temperatures above 420 K, nitrogen starts to desorb. The p(2 × 2)-N phase shows a honeycomb structure in STM images with three nitrogen and three platinum atoms forming a six-membered ring, which can be attributed to the strong nitrogen binding to the underlying Pt surface.

  13. Kinetic limitations in surface alloy formation: PtCu/Ru(0001)

    NASA Astrophysics Data System (ADS)

    Engstfeld, A. K.; Jung, C. K.; Behm, R. J.

    2016-01-01

    We have systematically investigated the structure and structure formation of two-dimensional PtCu monolayer surface alloys on Ru(0001) as model systems for bimetallic PtCu catalysts and surfaces by scanning tunneling microscopy (STM). The surface alloys were prepared by deposition of Pt and Cu on Ru(0001) and thermal intermixing; different procedures were developed and tested to produce bimetallic surfaces with homogeneous structure, including also a homogeneous distribution of the different surface species, while at the same time intermixing with the Ru(0001) substrate should be inhibited. STM imaging revealed that for Pt concentrations below 65% surface alloys with homogeneous distribution could be formed, while at higher concentrations in the mixed phase, up to 82%, pure Pt or Pt-rich surface areas were formed as well. At Pt contents of 0.20 < xPt < 0.65, the PtxCu1 -x/Ru(0001) surface alloys were pseudomorphic, while lower Pt contents resulted in triangular dislocation line patterns. Also at xPt > 0.65 line structures were observed, but of different nature. The distribution of surface atoms in the mixed phase was evaluated from STM images with chemical contrast, the related short-range order parameters were determined. The resulting structures and their energetics, the influence of different deposition and annealing procedures and the suitability of these surfaces as model systems for studies of the surface chemistry of bimetallic PtCu surfaces are discussed.

  14. Site-specific growth of a Pt shell on Au nanoplates: tailoring their surface plasmonic behavior

    NASA Astrophysics Data System (ADS)

    Jang, Hee-Jeong; Hong, Soonchang; Ham, Songyi; Shuford, Kevin L.; Park, Sungho

    2014-06-01

    In this report, we tune the surface plasmonic behavior of Au nanoplates depending on the morphology of the Pt shell in which Pt is considered as a less optically inactive element. We describe the synthesis of flat Au nanoplates coated with Pt via rim-preferential or uniform growth methods. Depending on the site-selective growth of Pt on core Au nanoplates, the aspect ratio of the resulting Au@Pt nanoplates was tunable and their corresponding surface plasmon resonance (SPR) bands were controlled accordingly. Although Pt is regarded as an optically weak component in visible and near infrared spectral windows, a Pt coating affects the SPR behavior of core Au nanoplates due to effective surface plasmon (SP) coupling between the Au core and the deposited Pt shell. We systematically investigated the optical properties of uniformly grown (Au@Pt(uni)) and rim-preferentially grown (Au@Pt(rim)) Au@Pt nanoplates by observing their SPR band shifts compared to SPR of Au nanoplates. Due to the structural rigidity conferred by the Pt coating, the Au@Pt nanoplates can be easily transferred to the investigated solvents.In this report, we tune the surface plasmonic behavior of Au nanoplates depending on the morphology of the Pt shell in which Pt is considered as a less optically inactive element. We describe the synthesis of flat Au nanoplates coated with Pt via rim-preferential or uniform growth methods. Depending on the site-selective growth of Pt on core Au nanoplates, the aspect ratio of the resulting Au@Pt nanoplates was tunable and their corresponding surface plasmon resonance (SPR) bands were controlled accordingly. Although Pt is regarded as an optically weak component in visible and near infrared spectral windows, a Pt coating affects the SPR behavior of core Au nanoplates due to effective surface plasmon (SP) coupling between the Au core and the deposited Pt shell. We systematically investigated the optical properties of uniformly grown (Au@Pt(uni)) and rim

  15. HYDROGEN CHEMISORPTION ON Pt SINGLE CRYSTAL SURFACES IN ACIDIC SOLUTIONS

    SciTech Connect

    Ross, Jr., Philip N.

    1980-04-01

    Hydrogen chemisorption from dilute acidic solution onto Pt single crystal surfaces was examined using an electrochemical cell directly coupled to LEED/Auger analytical system. No pre-anodization was used prior to observing hydrogen adsorption by cyclic voltammetry so that clean surfaces having the ordered structures indicated by LEED were studied. The problem of contributions from non-ordered parts of the electrode like support wires and edges was solved by using a gold evaporation masking technique. The specific contribution of atomic imperfections to the voltammetry curve was deduced from the ordered and countable imperfections occurring on high Miller index single crystal surfaces that have a stepped structure. The H-Pt bond energy Has found to be structure sensitive, and sensitive both to local site geometry and long range order in the surface. The bond strength was found to vary systematically: n(111)x(100) > (100) > n(111)x(111) > (110) > (111). Distinct states for hydrogen at steps versus hydrogen on terraces could be distinguished. The (110) surface is shown to be a (111) vicinal, probably the [3(111) x 2(111)] microfacetted surface. The zero coverage heat of adsorption on the well-ordered (111) surface (48 kJ/mol) in solutions is the same as the value reported by Ertl and co-workers for adsorption on a (111) surface in vacuum. Adsorption Isotherms for hydrogen on the (111) and (100) surfaces is adequately fit by the classical model for immobile adsorption at single sites with nearest neighbor repulsive interaction.

  16. Highly active dealloyed Cu@Pt core-shell electrocatalyst towards 2-propanol electrooxidation in acidic solution

    NASA Astrophysics Data System (ADS)

    Poochai, Chatwarin

    2017-02-01

    Dealloyed Cu@Pt core-shell electrocatalyst was fabricated by cyclic co-electrodeposition and selective Cu dealloying (CCEd-sCuD) on carbon paper (CP), namely Cu@Pt/CP. The Cu@Pt/CP exhibited a core-shell structure comprising with a Cu-rich core and a Pt-rich shell. The crystalline phases of Pt/CP and Cu@Pt/CP were a face-centered cubic (fcc). The compressive lattice strain approximately 0.85% was found in the Cu@Pt/CP owing to a lattice mismatch between a core and a shell region. In the core-region, Cu was formed Pt-Cu alloy as major and copper oxide and also metallic copper as minor. The morphology and grain size of the Cu@Pt/CP displayed a porous spherical shape with 100 nm in diameter, while those of Pt/CP seemed to be a cubic shape with smaller diameter of 40 nm. In electrochemical and catalytic activity, the surface of Cu@Pt/CP had a larger electrochemical active surface area (ECSA) than that of Pt/CP due to a porous formation caused by Cu dealloying. It is not surprising that the Cu@Pt/CP showed higher catalytic activity and greater stability towards 0.5 M 2-propanol electrooxidation in 0.5 M H2SO4 in terms of peak current density (jp), peak potential (Ep), onset potential (Eonset), diffusion coefficient (D), and charge transfer resistance (Rct) which were caused by electronic structure modification, higher compressive lattice strain, and larger ECSA, compared with Pt/CP.

  17. Catalytic Activity of Ultrathin Pt Films on Aligned Carbon Nanotube Arrays

    PubMed Central

    Su, Xin; Wu, Ji; Hinds, Bruce J.

    2013-01-01

    Uniform ultrathin Pt films were electrodeposited onto an aligned array of carbon nanotubes (CNTs) for high-area chemically stable methanol fuel cell anodes. Electrochemical treatment of the graphitic CNT surfaces by diazoniumbenzoic acid allowed for uniform Pt electroplating. The mass activity of the Pt thin film can reach 400 A/g at a scan rate of 20 mV/s and in a solution of 1 M CH3OH/0.5 M H2SO4. A programmed pulse potential at 0V was also seen to nearly eliminate the effects of carbon monoxide poisoning. The mass activity of Pt for methanol oxidation can be maintained at 300 A/g for more than 3000 s, which is 19 times of that under a constant potential of 0.7 V (vs Ag/AgCl). PMID:25132685

  18. Direct imaging of Pt single atoms adsorbed on TiO2 (110) surfaces.

    PubMed

    Chang, Teng-Yuan; Tanaka, Yusuke; Ishikawa, Ryo; Toyoura, Kazuaki; Matsunaga, Katsuyuki; Ikuhara, Yuichi; Shibata, Naoya

    2014-01-08

    Noble metal nanoparticles (e.g., gold and platinum) supported on TiO2 surfaces are utilized in many technological applications such as heterogeneous catalysts. To fully understand their enhanced catalytic activity, it is essential to unravel the interfacial interaction between the metal atoms and TiO2 surfaces at the level of atomic dimensions. However, it has been extremely difficult to directly characterize the atomic-scale structures that result when individual metal atoms are adsorbed on the TiO2 surfaces. Here, we show direct atomic-resolution images of individual Pt atoms adsorbed on TiO2 (110) surfaces using aberration-corrected scanning transmission electron microscopy. Subangstrom spatial resolution enables us to identify five different Pt atom adsorption sites on the TiO2 (110) surface. Combining this with systematic density functional theory calculations reveals that the most favorable Pt adsorption sites are on vacancy sites of basal oxygen atoms that are located in subsurface positions relative to the top surface bridging oxygen atoms.

  19. Active Site and Electronic Structure Elucidation of Pt Nanoparticles Supported on Phase-Pure Molybdenum Carbide Nanotubes.

    PubMed

    Tan, Shuai; Wang, Lucun; Saha, Shibely; Fushimi, Rebecca R; Li, Dongmei

    2017-03-22

    We recently showed that phase-pure molybdenum carbide nanotubes can be durable supports for platinum (Pt) nanoparticles in hydrogen evolution reaction (HER). In this paper we further characterize surface properties of the same Pt/β-Mo2C catalyst platform using carbon monoxide (CO)-Pt and CO-Mo2C bond strength of different Pt particle sizes in the <3 nm range. Results from diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and temporal analysis of products (TAP) revealed the existence of different active sites as Pt particle size increases. Correlation between the resultant catalyst activity and deposited Pt particle size was further investigated using water-gas-shift (WGS) as a probe reaction, suggesting that precise control of particle diameter and thickness is needed for optimized catalytic activity.

  20. Improving Electrocatalysts for O2 Reduction by Fine-Tuning the Pt-Support Interaction: Pt Monolayer on the Surfaces of a Pd3Fe(111) Single-Crystal Alloy

    SciTech Connect

    Zhou, W.P.; Yang, X.; Vukmirovic, M.B.; Koel, B.E.; Jiao, J.; Peng, G.; Mavrikakis, M.; Adzic, R.R.

    2009-09-09

    We improved the effectiveness of Pt monolayer electrocatalysts for the oxygen-reduction reaction (ORR) using a novel approach to fine-tuning the Pt monolayer interaction with its support, exemplified by an annealed Pd{sub 3}Fe(111) single-crystal alloy support having a segregated Pd layer. Low-energy ion scattering and low-energy electron diffraction studies revealed that a segregated Pd layer, with the same structure as Pd (111), is formed on the surface of high-temperature-annealed Pd{sub 3}Fe(111). This Pd layer is considerably more active than Pd(111); its ORR kinetics is comparable to that of a Pt(111) surface. The enhanced catalytic activity of the segregated Pd layer compared to that of bulk Pd apparently reflects the modification of Pd surface's electronic properties by underlying Fe. The Pd{sub 3}Fe(111) suffers a large loss in ORR activity when the subsurface Fe is depleted by potential cycling (i.e., repeated excursions to high potentials in acid solutions). The Pd{sub 3}Fe(111) surface is an excellent substrate for a Pt monolayer ORR catalyst, as verified by its enhanced ORR kinetics on PT{sub ML}/Pd/Pd{sub 3}Fe(111). Our density functional theory studies suggest that the observed enhancement of ORR activity originates mainly from the destabilization of OH binding and the decreased Pt-OH coverage on the Pt/Pd/Pd{sub 3}Fe(111) surface. The activity of Pt{sub ML}/Pd(111) and Pt(111) is limited by OH removal, whereas the activity of Pt{sub ML}/Pd/Pd{sub 3}Fe(111) is limited by the O-O bond scission, which places these two surfaces on the two sides of the volcano plot.

  1. Dual role of CO in the stability of subnano Pt clusters at the Fe3O4(001) surface

    PubMed Central

    Bliem, Roland; van der Hoeven, Jessi E. S.; Hulva, Jan; Pavelec, Jiri; Gamba, Oscar; de Jongh, Petra E.; Schmid, Michael; Blaha, Peter; Diebold, Ulrike; Parkinson, Gareth S.

    2016-01-01

    Interactions between catalytically active metal particles and reactant gases depend strongly on the particle size, particularly in the subnanometer regime where the addition of just one atom can induce substantial changes in stability, morphology, and reactivity. Here, time-lapse scanning tunneling microscopy (STM) and density functional theory (DFT)-based calculations are used to study how CO exposure affects the stability of Pt adatoms and subnano clusters at the Fe3O4(001) surface, a model CO oxidation catalyst. The results reveal that CO plays a dual role: first, it induces mobility among otherwise stable Pt adatoms through the formation of Pt carbonyls (Pt1–CO), leading to agglomeration into subnano clusters. Second, the presence of the CO stabilizes the smallest clusters against decay at room temperature, significantly modifying the growth kinetics. At elevated temperatures, CO desorption results in a partial redispersion and recovery of the Pt adatom phase. PMID:27457953

  2. Pt monolayer coating on complex network substrate with high catalytic activity for the hydrogen evolution reaction

    PubMed Central

    Li, Man; Ma, Qiang; Zi, Wei; Liu, Xiaojing; Zhu, Xuejie; Liu, Shengzhong (Frank)

    2015-01-01

    A deposition process has been developed to fabricate a complete-monolayer Pt coating on a large-surface-area three-dimensional (3D) Ni foam substrate using a buffer layer (Ag or Au) strategy. The quartz crystal microbalance, current density analysis, cyclic voltammetry integration, and X-ray photoelectron spectroscopy results show that the monolayer deposition process accomplishes full coverage on the substrate and the deposition can be controlled to a single atomic layer thickness. To our knowledge, this is the first report on a complete-monolayer Pt coating on a 3D bulk substrate with complex fine structures; all prior literature reported on submonolayer or incomplete-monolayer coating. A thin underlayer of Ag or Au is found to be necessary to cover a very reactive Ni substrate to ensure complete-monolayer Pt coverage; otherwise, only an incomplete monolayer is formed. Moreover, the Pt monolayer is found to work as well as a thick Pt film for catalytic reactions. This development may pave a way to fabricating a high-activity Pt catalyst with minimal Pt usage. PMID:26601247

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

    PubMed

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

    2010-07-01

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

  4. Surface Plasmon Enhanced Photocatalysis of Au/Pt-decorated TiO2 Nanopillar Arrays

    PubMed Central

    Shuang, Shuang; Lv, Ruitao; Xie, Zheng; Zhang, Zhengjun

    2016-01-01

    The low quantum yields and lack of visible light utilization hinder the practical application of TiO2 in high-performance photocatalysis. Herein, we present a design of TiO2 nanopillar arrays (NPAs) decorated with both Au and Pt nanoparticles (NPs) directly synthesized through successive ion layer adsorption and reaction (SILAR) at room temperature. Au/Pt NPs with sizes of ~4 nm are well-dispersed on the TiO2 NPAs as evidenced by electron microscopic analyses. The present design of Au/Pt co-decoration on the TiO2 NPAs shows much higher visible and ultraviolet (UV) light absorption response, which leads to remarkably enhanced photocatalytic activities on both the dye degradation and photoelectrochemical (PEC) performance. Its photocatalytic reaction efficiency is 21 and 13 times higher than that of pure TiO2 sample under UV-vis and visible light, respectively. This great enhancement can be attributed to the synergy of electron-sink function of Pt and surface plasmon resonance (SPR) of Au NPs, which significantly improves charge separation of photoexcited TiO2. Our studies demonstrate that through rational design of composite nanostructures one can harvest visible light through the SPR effect to enhance the photocatalytic activities initiated by UV-light, and thus realize more effectively utilization of the whole solar spectrum for energy conversion. PMID:27215703

  5. Synthesis of three-dimensionally ordered macro-/mesoporous Pt with high electrocatalytic activity by a dual-templating approach

    NASA Astrophysics Data System (ADS)

    Zhang, Chengwei; Yang, Hui; Sun, Tingting; Shan, Nannan; Chen, Jianfeng; Xu, Lianbin; Yan, Yushan

    2014-01-01

    Three dimensionally ordered macro-/mesoporous (3DOM/m) Pt catalysts are fabricated by chemical reduction employing a dual-templating synthesis approach combining both colloidal crystal (opal) templating (hard-templating) and lyotropic liquid crystal templating (soft-templating) techniques. The macropore walls of the prepared 3DOM/m Pt exhibit a uniform mesoporous structure composed of polycrystalline Pt nanoparticles. Both the size of the mesopores and Pt nanocrystallites are in the range of 3-5 nm. The 3DOM/m Pt catalyst shows a larger electrochemically active surface area (ECSA), and higher catalytic activity as well as better poisoning tolerance for methanol oxidation reaction (MOR) than the commercial Pt black catalyst.

  6. Functional link between surface low-coordination sites and the electrochemical durability of Pt nanoparticles

    NASA Astrophysics Data System (ADS)

    Chung, Dong Young; Shin, Heejong; Yoo, Ji Mun; Lee, Kug-Seung; Lee, Nam-Suk; Kang, Kisuk; Sung, Yung-Eun

    2016-12-01

    A promising strategy for achieving enhanced catalytic activity involves the use of nanoscale electrocatalysts; however, their low stability remains a major challenge. Among the various performance-degradation mechanisms, atomic dissolution is known to cause severe nanoparticle deactivation. To date, the factors influencing these catalysts' durability are not understood. Herein, we assess the role of low-coordination surface sites, focusing on the atomic dissolution of Pt nanoparticles. The density of low-coordination sites was finely controlled, and no significant size change occurred. Based on our findings, we suggest that the initial low-coordination sites trigger metal dissolution, which subsequently accelerates Pt dissolution. We believe that controlling the surface coordination number can open new routes for the design of highly durable nanoscale electrocatalysts.

  7. Coverage dependence and hydroperoxyl-mediated pathway of catalytic water formation on Pt (111) surface

    NASA Astrophysics Data System (ADS)

    Qi, Liang; Yu, Jianguo; Li, Ju

    2006-08-01

    Hydrogen oxidation on Pt (111) surface is modeled by density functional theory (DFT). Previous DFT calculations showed too large O2 dissociation barriers, but we find them highly coverage dependent: when the coverage is low, dissociation barriers close to experimental values (˜0.3eV) are obtained. For the whole reaction, a new pathway involving hydroperoxyl (OOH) intermediate is found, with the highest reaction barrier of only ˜0.4eV. This may explain the experimental observation of catalytic water formation on Pt (111) surface above the H2O desorption temperature of 170K, despite that the direct reaction between chemisorbed O and H atoms is a highly activated process with barrier ˜1eV as previous calculations showed.

  8. One pot aqueous synthesis of nanoporous Au85Pt15 material with surface bound Pt islands: an efficient methanol tolerant ORR catalyst

    NASA Astrophysics Data System (ADS)

    Anandha Ganesh, P.; Jeyakumar, D.

    2014-10-01

    For the first time, we are reporting the synthesis of Au100-xPtx nanoporous materials in the size range of 7-10 nm through the galvanic replacement of Ag by Pt from Au100-xAg2x spherical nano-alloys (x = 20, 15, 10 and 5) in an aqueous medium. The galvanic replacement reaction follows the `Volmer-Weber' growth mode, resulting in the formation of surface bound platinum islands on a nanoporous gold surface. The high angle annular dark field image and low angle X-ray diffraction studies confirm the presence of nanoporous Au100-xPtx NPs. The electrochemical studies using the Au85Pt15/C catalyst show excellent methanol tolerance behaviour and better performance towards oxygen reduction reaction (ORR) in terms of high mass activity, mass-specific activity and figure of merit (FOM) when compared to HiSPEC Pt/C commercial catalyst. Preliminary studies on a full cell using nanoporous Au85Pt15/C (loading 1.0 mg cm-2) as the cathode material and Pt-Ru/C (loading: 0.5 mg cm-2) as the anode material performed better (38 mW cm-2) than the HiSPEC Pt/C cathode material (16 mW cm-2).For the first time, we are reporting the synthesis of Au100-xPtx nanoporous materials in the size range of 7-10 nm through the galvanic replacement of Ag by Pt from Au100-xAg2x spherical nano-alloys (x = 20, 15, 10 and 5) in an aqueous medium. The galvanic replacement reaction follows the `Volmer-Weber' growth mode, resulting in the formation of surface bound platinum islands on a nanoporous gold surface. The high angle annular dark field image and low angle X-ray diffraction studies confirm the presence of nanoporous Au100-xPtx NPs. The electrochemical studies using the Au85Pt15/C catalyst show excellent methanol tolerance behaviour and better performance towards oxygen reduction reaction (ORR) in terms of high mass activity, mass-specific activity and figure of merit (FOM) when compared to HiSPEC Pt/C commercial catalyst. Preliminary studies on a full cell using nanoporous Au85Pt15/C (loading 1.0 mg

  9. Atomic Layer-by-Layer Deposition of Pt on Pd Nanocubes for Catalysts with Enhanced Activity and Durability toward Oxygen Reduction

    SciTech Connect

    Xie, Shuifen; Choi, Sang; Lu, Ning; Roling, Luke T.; Herron, Jeffrey A.; Zhang, Lei; Park, Jinho; Wang, Jinguo; Kim, Moon J.; Xie, Zhaoxiong; Mavrikakis, Manos; Xia, Younan

    2014-06-11

    An effective strategy for reducing the Pt content while retaining the activity of a Pt-based catalyst is to deposit the Pt atoms as ultrathin skins of only a few atomic layers thick on nanoscale substrates made of another metal. During deposition, however, the Pt atoms often take an island growth mode because of a strong bonding between Pt atoms. Here we report a versatile route to the conformal deposition of Pt as uniform, ultrathin shells on Pd nanocubes in a solution phase. The introduction of the Pt precursor at a relatively slow rate and high temperature allowed the deposited Pt atoms to spread across the entire surface of a Pd nanocube to generate a uniform shell. The thickness of the Pt shell could be controlled from one to six atomic layers by varying the amount of Pt precursor added into the system. Compared to a commercial Pt/C catalyst, the Pd@PnL (n = 1-6) core-shell nanocubes showed enhancements in specific activity and durability toward the oxygen reduction reaction (ORR). Density functional theory (DFT) calculations on model (100) surfaces suggest that the enhancement in specific activity can be attributed to the weakening of OH binding through ligand and strain effects, which, in turn, increases the rate of OH hydrogenation. A volcano-type relationship between the ORR specific activity and the number of Pt atomic layers was derived, in good agreement with the experimental results. Both theoretical and experimental studies indicate that the ORR specific activity was maximized for the catalysts based on Pd@Pt2-3L nanocubes. Because of the reduction in Pt content used and the enhancement in specific activity, the Pd@Pt1L nanocubes showed a Pt mass activity with almost three-fold enhancement relative to the Pt/C catalyst.

  10. Facile activation of dihydrogen by a phosphinito-bridged Pt(I)-Pt(I) complex.

    PubMed

    Mastrorilli, Piero; Latronico, Mario; Gallo, Vito; Polini, Flavia; Re, Nazzareno; Marrone, Alessandro; Gobetto, Roberto; Ellena, Silvano

    2010-04-07

    The phosphinito-bridged Pt(I) complex [(PHCy(2))Pt(mu-PCy(2)){kappa(2)P,O-mu-P(O)Cy(2)}Pt(PHCy(2))](Pt-Pt) (1) reversibly adds H(2) under ambient conditions, giving cis-[(H)(PHCy(2))Pt(1)(mu-PCy(2))(mu-H)Pt(2)(PHCy(2)){kappaP-P(O)Cy(2)}](Pt-Pt) (2). Complex 2 slowly isomerizes spontaneously into the corresponding more stable isomer trans-[(PHCy(2))(H)Pt(mu-PCy(2))(mu-H)Pt(PHCy(2)){kappaP-P(O)Cy(2)}](Pt-Pt) (3). DFT calculations indicate that the reaction of 1 with H(2) occurs through an initial heterolytic splitting of the H(2) molecule assisted by the phosphinito oxygen with breaking of the Pt-O bond and hydrogenation of the Pt and O atoms, leading to the formation of the intermediate [(PHCy(2))(H)Pt(mu-PCy(2))Pt(PHCy(2)){kappaP-P(OH)Cy(2)}](Pt-Pt) (D), where the two split hydrogen atoms interact within a six-membered Pt-H...H-O-P-Pt ring. Compound D is a labile intermediate which easily evolves into the final dihydride complex 2 through a facile (9-15 kcal mol(-1), depending on the solvent) hydrogen shift from the phosphinito oxygen to the Pt-Pt bond. Information obtained by addition of para-H(2) on 1 are in agreement with the presence of a heterolytic pathway in the 1 --> 2 transformation. NMR experiments and DFT calculations also gave evidence for the nonclassical dihydrogen complex [(PHCy(2))(eta(2)-H(2))Pt(mu-PCy(2))Pt(PHCy(2)){kappaP-P(O)Cy(2)}](Pt-Pt) (4), which is an intermediate in the dehydrogenation of 2 to 1 and is also involved in intramolecular and intermolecular exchange processes. Experimental and DFT studies showed that the isomerization 2 --> 3 occurs via an intramolecular mechanism essentially consisting of the opening of the Pt-Pt bond and of the hydrogen bridge followed by the rotation of the coordination plane of the Pt center with the terminal hydride ligand.

  11. [Fabrication and photocatalytic activity of Pt-inserted titania nanotubes].

    PubMed

    Li, Hai-Long; Luo, Wu-Lin; Tian, Wen-Yu; Chen, Tao; Li, Chun; Sun, Mao; Zhu, Di; Liu, Ran-Ran; Zhao, Yu-Liang; Liu, Chun-Li

    2009-06-01

    Titania nanotubes (TNTs) were synthesized by hydrothermal treatment of rutile-phase TiO2 nanoparticals in NaOH solution at 110 degrees C for 24 hours. After drying in aceton for 36 h, the TNTs were under vacuum drying for 24 h at room temperature. The Pt-inserted titania nanotubes (Pt/TNTs) were obtained by filling H2 PtCl6 ethanol solution into the TNTs after vacuum drying. The characterizations of the as-synthesized samples were confirmed by TEM, XRD, and UV-Vis. The photocatalytic activity of the Pt/TNTs was investigated by photo-induced decomposition of methyl orange(MO)under the main 365 nm UV-light. In order to comparison, the photocatalytic activity of both the rutile-phase TiO2 nanoparticles and pure TNTs were also investigated at the same time under the same experimental conditions. The TEM images show that the TNTs are hollow, a few hundred nanometers long, and the inner/outer diameter is about 6/10 nm. The crystal structure of TNTs is H2Ti2O5 x H2O with a little Na. Both the shape and the crystalline of the TNTs are not changed after the modification. The oval or round Pt0 nanoparticals, about 3 nm in diameter, are found only in the nanotubes. Pt/TNTs exhibit enhanced absorption at the visible range in the UV-Vis spectra and its start absorption band edge(lambda0 approximately 457 nm)is obviously redshifted compared to the rutile-phase TiO2 nanoparticals and pure TNTs. The Pt nanoparticles are found to significantly enhance the photocatalytic activity of TNTs. Pt/TNTs are demonstrated to be highly efficient for the UV-light induced photocatalytic decomposition of MO compared to both the rutile-phase TiO2 nanoparticals and pure TNTs. After irradiation for 60 min, the photocatalysis decomposition rate of MO in rutile-phase TiO2 nanoparticals, TNTs and Pt/TNTs are 46.8%, 57.2% and 84.6% respectively.

  12. Surface-Regulated Nano-SnO2/Pt3Co/C Cathode Catalysts for Polymer Electrolyte Fuel Cells Fabricated by a Selective Electrochemical Sn Deposition Method.

    PubMed

    Nagasawa, Kensaku; Takao, Shinobu; Nagamatsu, Shin-ichi; Samjeské, Gabor; Sekizawa, Oki; Kaneko, Takuma; Higashi, Kotaro; Yamamoto, Takashi; Uruga, Tomoya; Iwasawa, Yasuhiro

    2015-10-14

    We have achieved significant improvements for the oxygen reduction reaction activity and durability with new SnO2-nanoislands/Pt3Co/C catalysts in 0.1 M HClO4, which were regulated by a strategic fabrication using a new selective electrochemical Sn deposition method. The nano-SnO2/Pt3Co/C catalysts with Pt/Sn = 4/1, 9/1, 11/1, and 15/1 were characterized by STEM-EDS, XRD, XRF, XPS, in situ XAFS, and electrochemical measurements to have a Pt3Co core/Pt skeleton-skin structure decorated with SnO2 nanoislands at the compressive Pt surface with the defects and dislocations. The high performances of nano-SnO2/Pt3Co/C originate from efficient electronic modification of the Pt skin surface (site 1) by both the Co of the Pt3Co core and surface nano-SnO2 and more from the unique property of the periphery sites of the SnO2 nanoislands at the compressive Pt skeleton-skin surface (more active site 2), which were much more active than expected from the d-band center values. The white line peak intensity of the nano-SnO2/Pt3Co/C revealed no hysteresis in the potential up-down operations between 0.4 and 1.0 V versus RHE, unlike the cases of Pt/C and Pt3Co/C, resulting in the high ORR performance. Here we report development of a new class of cathode catalysts with two different active sites for next-generation polymer electrolyte fuel cells.

  13. Pt-content-controlled synthesis of Pd nanohollows/Pt nanorods core/shell composites with enhanced electrocatalytic activities for the methanol oxidation reaction

    NASA Astrophysics Data System (ADS)

    Lai, Shiqin; Fu, Chenglin; Chen, Yongxiang; Yu, Xiang; Lai, Xuandi; Ye, Cui; Hu, Jianqiang

    2015-01-01

    Pd nanohollows/Pt nanorods (PdNHs/PtNRs) core/shell composites have been synthesized by a multistep crystalline growth method, in which Pt NRs grow on the exterior surface of hollow Pd nanospheres in order. Moreover, the size and quantity of the Pt NRs in the PdNHs/PtNRs can be easily tailored and thus ameliorate Pt utilization efficiency through varying H2PtCl6 concentrations. By comparing with Pt NPs and commercial Pt/C (JM), the PdNHs/PtNRs prepared using 2.50 mL 0.02 M H2PtCl6 have larger surface area, better anti-CO poisoning ability and more excellent catalytic performance. Moreover, the catalytic properties of the PdNHs/PtNRs can be well tunable by modifying the Pt contents. Our studies indicate that the PdNHs/PtNRs prepared using 2.50 mL 0.02 M H2PtCl6, in which Pd NHs are nearly completely covered with Pt NRs, have the largest surface area, best antitoxic ability and most excellent catalytic performance, indicative of high Pt utilization efficiency of the PdNHs/PtNRs relative to Pt/C (JM), Pt NPs and other PdNHs/PtNRs prepared using other H2PtCl6 concentrations. Therefore, the strategy to the size and content control of the PdNHs/PtNRs nanocomposites can facilitate optimized design of Pt-based catalysts for direct methanol fuel cells.

  14. Controlled FCC/on-top binding of H/Pt(111) using surface stress

    NASA Astrophysics Data System (ADS)

    Shuttleworth, I. G.

    2016-08-01

    The preferred binding site of H/Pt(111) has been shown to be change from the on-top to FCC as the Pt(111) surface goes approximately from a state of compressive to tensile strain. A chemical analysis of the system has shown that for both FCC and on-top bound cases the H ssbnd Pt s and H ssbnd Pt d interactions have a similar importance in determining the preferred binding position. It has been seen that FCC-bound H forms a distinct state below the Pt d-band, whereas the on-top bound H does not.

  15. Carbon nanotubes decorated with Pt nanoparticles via electrostatic self-assembly: a highly active oxygen reduction electrocatalyst

    SciTech Connect

    Zhang, Sheng; Shao, Yuyan; Yin, Geping; Lin, Yuehe

    2010-03-20

    Carbon nanotubes (CNTs) are noncovalently functionalized with poly(allylamine hydrochloride) (PAH) and then employed as the support of Pt nanoparticles. X-Ray photoelectron spectroscopy confirms the successful functionalization of CNTs with PAH. The negatively charged Pt precursors are adsorbed on positively charged PAH-wrapping CNTs surface via electrostatic self-assembly and then in situ reduced in ethylene glycol. X-Ray diffraction and transmission electron microscope images reveal that Pt nanoparticles with an average size of 2.6 nm are uniformly dispersed on CNT surface. Pt/PAH-CNTs exhibit unexpectedly high activity towards oxygen reduction reaction, which can be attributed to the large electrochemical surface area of Pt nanoparticles. It also shows enhanced electrochemical stability due to the structural integrity of PAH-CNTs. This provides a facile approach to synthesize CNTs-based nanoelectrocatalysts.

  16. Improving Electrocatalysts for O2 Reduction by Fine-Tuning the Pt-Support Interaction: Pt Monolayer on the Surfaces of a Pd3Fe(111) Single-Crystal Alloy

    SciTech Connect

    Zhou, Wei-Ping; Yang, Xiaofang; Vukmirovic, Miomir B.; Koel, Bruce E.; Jiao, Jiao; Peng, Guowen; Mavrikakis, Manos; Adzic, Radoslav R.

    2009-09-09

    We improved the effectiveness of Pt monolayer electrocatalysts for the oxygen-reduction reaction (ORR) using a novel approach to fine-tuning the Pt monolayer interaction with its support, exemplified by an annealed Pd3Fe(111) single-crystal alloy support having a segregated Pd layer. Low-energy ion scattering and low-energy electron diffraction studies revealed that a segregated Pd layer, with the same structure as Pd (111), is formed on the surface of high-temperature-annealed Pd3Fe(111). This Pd layer is considerably more active than Pd(111); its ORR kinetics is comparable to that of a Pt(111) surface. The enhanced catalytic activity of the segregated Pd layer compared to that of bulk Pd apparently reflects the modification of Pd surface’s electronic properties by underlying Fe. The Pd3Fe(111) suffers a large loss in ORR activity when the subsurface Fe is depleted by potential cycling (i.e., repeated excursions to high potentials in acid solutions). The Pd3Fe(111) surface is an excellent substrate for a Pt monolayer ORR catalyst, as verified by its enhanced ORR kinetics on PTML/Pd/Pd3Fe(111). Our density functional theory studies suggest that the observed enhancement of ORR activity originates mainly from the destabilization of OH binding and the decreased Pt-OH coverage on the Pt/Pd/Pd3Fe(111) surface. The activity of PtML/Pd(111) and Pt(111) is limited by OH removal, whereas the activity of PtML/Pd/Pd3Fe(111) is limited by the O-O bond scission, which places these two surfaces on the two sides of the volcano plot.

  17. Enhanced electrocatalytic activity of the Au-electrodeposited Pt nanoparticles-coated conducting oxide for the quantum dot-sensitized solar cells

    NASA Astrophysics Data System (ADS)

    Yoon, Yeung-Pil; Kim, Jae-Hong; Kang, Soon-Hyung; Kim, Hyunsoo; Choi, Chel-Jong; Kim, Kyong-Kook; Ahn, Kwang-Soon

    2014-08-01

    Au was electrodeposited potentiostatically at 0.3 V for 5 min on nanoporous Pt nanoparticle-coated F-doped SnO2 (FTO/Pt) substrates. For comparison, Au-electrodeposited FTO (FTO/Au) and Au-uncoated FTO/Pt were prepared. FTO/Au showed large-sized Au clusters dispersed sparsely over FTO, which resulted in lower electrocatalytic activity than FTO/Pt. In contrast, FTO/Pt exhibited poor stability unlike FTO/Au due to poisoning by the adsorption of sulfur species. The Au-electrodeposited FTO/Pt (FTO/Pt/Au) consisted of small Au clusters deposited over the entire area of Pt due to the effective Au nucleation provided by nanoporous metallic Pt. FTO/Pt/Au exhibited enhanced electrocatalytic activity and excellent stability because the small Au particles well-dispersed over the nanoporous metallic Pt network provided numerous electrochemical reaction sites, and the Pt surface was not exposed to the electrolyte. When FTO/Pt/Au was used as the counter electrode (CE) of a quantum dot-sensitized solar cell, the significantly enhanced electrocatalytic activity of the FTO/Pt/Au CE facilitated the reduction reaction of Sn2- + 2e- (CE) → Sn-12- + S2- at the CE/electrolyte interface, resulting in a significantly hindered recombination reaction, Sn2- + 2e- (TiO2 in the photoanode) → Sn-12- + S2-, and significantly improved overall energy conversion efficiency.

  18. Influences of various Pt dopants over surface platinized TiO2 on the photocatalytic oxidation of nitric oxide.

    PubMed

    Wang, Haiqiang; Wu, Zhongbiao; Liu, Yue; Wang, Yuejun

    2009-02-01

    Various surface platinized TiO(2) were prepared by four different preparation methods and investigated with respect to their behaviors in UV photocatalytic oxidation of nitric oxide. The physicochemical properties of the Pt modified TiO(2) were investigated by X-ray diffraction analysis, X-ray photoelectron spectrum analysis, transmission electron microscopy, and photoluminescence spectra. From the experimental results, it was found that new electronic states were observed above the valence bands of PtOx-TiO(2) and PtClx-TiO(2). And the lifetime of electrons and holes was found prolonged in the PtOx-TiO(2) catalysts. The activity tests showed that the dopants existed as metallic Pt and platinum chloride had little contribution to the photocatalytic oxidation of NO in gas phase. However, the dopant which existed as PtOx could improve the NO photocatalytic oxidation efficiency and the reaction rate. The photocatalytic activity of the 0.05 at% PtOx-TiO(2) was nearly three times higher than that of the pure Degussa P25 with an inlet NO concentration of 200 ppm.

  19. Adsorption and ring-opening of lactide on the chiral metal surface Pt(321)S studied by density functional theory

    NASA Astrophysics Data System (ADS)

    Franke, J.-H.; Kosov, D. S.

    2015-01-01

    We study the adsorption and ring-opening of lactide on the naturally chiral metal surface Pt(321)S. Lactide is a precursor for polylactic acid ring-opening polymerization, and Pt is a well known catalyst surface. We study, here, the energetics of the ring-opening of lactide on a surface that has a high density of kink atoms. These sites are expected to be present on a realistic Pt surface and show enhanced catalytic activity. The use of a naturally chiral surface also enables us to study potential chiral selectivity effects of the reaction at the same time. Using density functional theory with a functional that includes the van der Waals forces in a first-principles manner, we find modest adsorption energies of around 1.4 eV for the pristine molecule and different ring-opened states. The energy barrier to be overcome in the ring-opening reaction is found to be very small at 0.32 eV and 0.30 eV for LL- and its chiral partner DD-lactide, respectively. These energies are much smaller than the activation energy for a dehydrogenation reaction of 0.78 eV. Our results thus indicate that (a) ring-opening reactions of lactide on Pt(321) can be expected already at very low temperatures, and Pt might be a very effective catalyst for this reaction; (b) the ring-opening reaction rate shows noticeable enantioselectivity.

  20. Kinetics and thermodynamics of H2O dissociation and CO oxidation on the Pt/WC (0001) surface: A density functional theory study

    NASA Astrophysics Data System (ADS)

    Liang, Yuanyuan; Chen, Litao; Ma, Chun'an

    2017-02-01

    Adsorptions of H2O and CO on the Pt/WC(0001) [pseudomorphic platinum monolayer on WC(0001)] surface have been studied with periodical slab model by PW91 approach of GGA within the framework of density functional theory (DFT). The reaction pathways and mechanisms of H2O dissociation and CO oxidation are also investigated. For a comparison, similar calculation scheme are performed on the Pt (111) surface as well. The adsorption energies of H2O and CO on both concerned surfaces suggest that H2O binds preferentially on the Pt/WC (0001) surface, while CO prefers the metal surface Pt (111), agreeing well with the experimental observation that the tungsten carbides based material is less susceptible to CO poisoning than platinum. The activation energies for the stepwise H2O dehydrogenation reaction show that the progress of H2O dissociation is similar on the two surfaces; and coincidentally the oxidation of CO by surface hydroxyl is much more likely to occur than that by surface oxygen which comes up with the H2O dissociation. Although the activation barrier of H2O dissociation on the Pt/WC (0001) is similar to that on Pt (111), the key oxidant OH specials which play a key role in turning over surface carbon monoxide to carbon dioxide prefer the Pt/WC(0001) surface, and the improved CO oxidation reaction progress confirms that the Pt/WC surface is more CO-tolerant than the pure Pt. According to the electronic structure analysis we find that the increased CO tolerance is ascribed to the downshift of Pt d-band center because of the charge transfer from WC support to the coating surface.

  1. Nanoparticles of Ag with a Pt and Pd rich surface supported on carbon as a new catalyst for the oxygen electroreduction reaction (ORR) in acid electrolytes: Part 2

    NASA Astrophysics Data System (ADS)

    Pech-Pech, I. E.; Gervasio, Dominic F.; Pérez-Robles, J. F.

    2015-02-01

    In the first part of this work, the feasibility of developing a catalyst with high activity for the oxygen electroreduction reaction (ORR) in acid media and with low Pt loading was demonstrated by over coating a silver (Ag) nanoparticle with a shell of platinum (Pt) and palladium (Pd) [7]. The results show that best activity is not directly related to a higher PtPd loading on the surface of the Ag. The best catalyst in a series of this type of catalyst is found with Ag@Pt0.3Pd0.3/C which gives a specific activity for oxygen reduction, jk (in units of mA cm-2 of real area), of 0.07 mA cm-2 at 0.85 V vs. NHE, as compared to 0.04 mA cm-2 when with a commercial Pt on carbon catalyst (Pt20/C) is used in an identical electrode except for the catalyst. The mass activity, jm (in units of mA μg-1 of Pt), for Ag@Pt0.3Pd0.3/C is 0.04 mA μg-1 of Pt at 0.85 V vs. NHE, whereas that for the Pt20/C gives 0.02 mA μg-1 of Pt, showing Ag@Pt0.3Pd0.3/C is a lower-cost catalyst, because using a Ag core and Pd with Pt in the shell gives the highest catalytic activity using less Pt.

  2. Adsorption of aromatics on the (111) surface of PtM and PtM 3 (M = Fe, Ni) alloys

    SciTech Connect

    Hensley, Alyssa J. R.; Schneider, Sebastian; Wang, Yong; McEwen, Jean-Sabin

    2015-01-01

    The adsorption of benzene and phenol was studied on PtM and PtM3 (111) surfaces, with M being either Ni or Fe. Under vacuum, the most favorable near surface structures showed an enrichment in Pt over the M species. An analysis of the electronic structure of the metal species in the clean surfaces with different near surface structures was done with the d-band model and showed that the Pt's d-states are significantly shifted away from the Fermi level due to the Pt-M interactions while the M species' d-states were less affected, with Ni's d-band shifting closer to the Fermi level and Fe's d-band shifting away from the Fermi level. The adsorption of aromatics, benzene and phenol, on several near surface structures for the PtM and PtM3 (111) surfaces showed that higher surface M concentrations resulted in a stronger adsorption due to the larger amount of charge transferred between the adsorbate and surface. However, compared to the adsorption of benzene and phenol on monometallic surfaces, the adsorption of these species on the PtM and PtM3 (111) surfaces was significantly weakened. Overall, our results show that the observed behavior of these Pt/Fe and Pt/Ni alloys is similar to that seen for the previously studied Pd/Fe surfaces. Furthermore, balancing the weakly adsorbing Pt surface species with the more strongly interacting Fe or Ni species can lead to the tailored adsorption of aromatics with applications in both hydrodeoxygenation and hydrogenation reactions by increasing the desorption rate of wanted aromatic products.

  3. Adsorption and decomposition of cyclohexanone (C6H10O) on Pt(111) and the (2 × 2) and (√3 × √3)r30°-Sn/Pt(111) surface alloys.

    PubMed

    Kim, Jooho; Welch, Lindsey A; Olivas, Amelia; Podkolzin, Simon G; Koel, Bruce E

    2010-11-02

    Adsorption and decomposition of cyclohexanone (C(6)H(10)O) on Pt(111) and on two ordered Pt-Sn surface alloys, (2 × 2)-Sn/Pt(111) and (√3 × √3)R30°-Sn/Pt(111), formed by vapor deposition of Sn on the Pt(111) single crystal surface were studied with TPD, HREELS, AES, LEED, and DFT calculations with vibrational analyses. Saturation coverage of C(6)H(10)O was found to be 0.25 ML, independent of the Sn surface concentration. The Pt(111) surface was reactive toward cyclohexanone, with the adsorption in the monolayer being about 70% irreversible. C(6)H(10)O decomposed to yield CO, H(2)O, H(2), and CH(4). Some C-O bond breaking occurred, yielding H(2)O and leaving some carbon on the surface after TPD. HREELS data showed that cyclohexanone decomposition in the monolayer began by 200 K. Intermediates from cyclohexanone decomposition were also relatively unstable on Pt(111), since coadsorbed CO and H were formed below 250 K. Surface Sn allowed for some cyclohexanone to adsorb reversibly. C(6)H(10)O dissociated on the (2 × 2) surface to form CO and H(2)O at low coverages, and methane and H(2) in smaller amounts than on Pt(111). Adsorption of cyclohexanone on (√3 × √3)R30°-Sn/Pt(111) at 90 K was mostly reversible. DFT calculations suggest that C(6)H(10)O adsorbs on Pt(111) in two configurations: by bonding weakly through oxygen to an atop Pt site and more strongly through simultaneously oxygen and carbon of the carbonyl to a bridged Pt-Pt site. In contrast, on alloy surfaces, C(6)H(10)O bonds preferentially to Sn. The presence of Sn, furthermore, is predicted to make the formation of the strongly bound C(6)H(10)O species bonding through O and C, which is a likely decomposition precursor, thermodynamically unfavorable. Alloying with Sn, thus, is shown to moderate adsorptive and reactive activity of Pt(111).

  4. Surface enhanced Raman scattering of 4-aminothiophenol sandwiched between Ag nanocubes and smooth Pt substrate: The effect of the thickness of Pt film

    NASA Astrophysics Data System (ADS)

    Zhu, Shuangmei; Fan, Chunzhen; Wang, Junqiao; He, Jinna; Liang, Erjun; Chao, Mingju

    2014-07-01

    Ag nanocubes (NCs)/4-aminothiophenol (p-ATP)/smooth platinum (Pt) film (Ag-NCs @ p-ATP/Pt) sandwich structure is created for surface enhanced Raman scattering (SERS). The proposed sandwich structure is shown to exhibit better performance than the Ag-NCs only as SERS substrate. The dependence of the Raman signal intensity on the thickness of the Pt films is examined. It is shown that the Raman signal increases with the thickness of the Pt films from 42 to 90 nm, suggesting the electromagnetic coupling of the localized surface plasmons of the Ag-NCs with the surface plasmon polaritons of the underneath Pt film, which is confirmed by our numerical simulations. The SERS enhancement factor in Ag-NCs @ p-ATP/Pt is estimated to be (4.1 ± 0.2) × 106 for a Pt film of 90 nm.

  5. Structural and electronic properties of bulk and low-index surfaces of zincblende PtC

    NASA Astrophysics Data System (ADS)

    Gokhan Sensoy, Mehmet; Toffoli, Daniele; Ustunel, Hande

    2017-03-01

    Transition metal carbides have been extensively used in diverse applications over the past decade. Their versatility is in part thanks to their unique bonding, which displays a mixture of ionic, metallic and covalent character. While the bulk structure of zincblende (ZB) PtC has been investigated several times, a detailed understanding of the electronic and structural properties of its low-index surfaces is lacking. In this work, we present an ab initio investigation of the properties of five crystallographic ZB PtC surfaces (Pt/C-terminated PtC(1 0 0), PtC(1 1 0) and Pt/C-terminated PtC(1 1 1)). Upon geometry optimization, both polar and nonpolar surfaces undergo a mild interlayer relaxation, without extensive reconstructions. Calculated vacancy formation energies indicate facile C removal on the (1 1 1) surface while Pt-vacancy formation is endothermic. Finally, atomic O adsorption energies on all surfaces reveal a high affinity of the C-terminated surfaces towards this species.

  6. How do random superficial defects influence the electro-oxidation of glycerol on Pt(111) surfaces?

    PubMed

    Fernández, Pablo S; Tereshchuk, Polina; Angelucci, Camilo A; Gomes, Janaina F; Garcia, Amanda C; Martins, Cauê A; Camara, Giuseppe A; Martins, María E; Da Silva, Juarez L F; Tremiliosi-Filho, Germano

    2016-09-14

    The glycerol electrooxidation reaction (GEOR) has attracted huge interest in the last decade due to the very low price and availability of this polyol. In this work, we studied the GEOR on Pt(111) electrodes by introducing different densities of random defects. Our results showed that the generation of defects on Pt(111) slightly modified the GEOR onset potential, however it generates changes in the voltammetric oxidation charges and also in the relative production of CO2 to carbonyl containing compounds, C[double bond, length as m-dash]O. The voltammetric profiles in the forward scan show two oxidation peaks. FTIR data show that the first one is connected with the GlOH dissociative adsorption to form CO (and others intermediates) while the second one, at higher potentials, matches the onsets of the CO oxidation to CO2 and the C[double bond, length as m-dash]O production. FTIR also confirms that the lower activity of defected electrodes at lower potentials is connected to a higher CO poisoning. DFT calculations show that the presence of CO molecules on a Pt defected surface keeps water and GlOH molecules far from the surface and linked by H bonds. This paper is the last of a series of three works where we explore the GEOR on an important number of different Pt surfaces. These works show that it is difficult to oxidize GlOH at potentials lower than 0.6 V (under our experimental conditions) without suffering an important electrode poisoning (mainly by CO). Since the structure of nanoparticles might be mimicked by defected single crystals, these sets of reports provide a considerable amount of information concerning the influence of such surfaces towards GlOH reaction in acidic media. Therefore, if the well-known "nano"-effect does not produce substantial changes in the activity of Pt materials, they are not useful to be applied in a Direct Glycerol Fuel Cell (DGFC). On the other hand, it is very interesting that the density of electrode defects permits us to tune the

  7. Low content Pt nanoparticles anchored on N-doped reduced graphene oxide with high and stable electrocatalytic activity for oxygen reduction reaction

    PubMed Central

    Li, Zeyu; Gao, Qiuming; Zhang, Hang; Tian, Weiqian; Tan, Yanli; Qian, Weiwei; Liu, Zhengping

    2017-01-01

    A novel kind of Pt/N-rGO hybrid possessing of low content 5.31 wt.% Pt anchored on the surface of nitrogen doped reduced graphene oxide (N-rGO) evenly was prepared. The Pt has uniformed 2.8 nm diameter and exposed (111) crystal planes; meanwhile, the N works as the bridge between Pt and rGO with the Pt-N and N-C chemical bonds in Pt/N-rGO. The Pt/N-rGO material has a very high electrocatalytic activity in oxygen reduction reaction with the mass catalytic activity more than 1.5 times of the commercial Pt/C due to the synergistic catalytic effect of both N-doped carbon matrix and Pt nanoparticles. Moreover, the Pt/N-rGO exhibits an excellent stability with hardly loss (only 0.4%) after accelerated durability tests of 5000 cycles based on the stable Pt-N-C chemical bonds in Pt/N-rGO, which can prevent the detachment, dissolution, migration and aggregation of Pt nanoparticles on the matrix during the long-term cycling. PMID:28233857

  8. Low content Pt nanoparticles anchored on N-doped reduced graphene oxide with high and stable electrocatalytic activity for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Li, Zeyu; Gao, Qiuming; Zhang, Hang; Tian, Weiqian; Tan, Yanli; Qian, Weiwei; Liu, Zhengping

    2017-02-01

    A novel kind of Pt/N-rGO hybrid possessing of low content 5.31 wt.% Pt anchored on the surface of nitrogen doped reduced graphene oxide (N-rGO) evenly was prepared. The Pt has uniformed 2.8 nm diameter and exposed (111) crystal planes; meanwhile, the N works as the bridge between Pt and rGO with the Pt-N and N-C chemical bonds in Pt/N-rGO. The Pt/N-rGO material has a very high electrocatalytic activity in oxygen reduction reaction with the mass catalytic activity more than 1.5 times of the commercial Pt/C due to the synergistic catalytic effect of both N-doped carbon matrix and Pt nanoparticles. Moreover, the Pt/N-rGO exhibits an excellent stability with hardly loss (only 0.4%) after accelerated durability tests of 5000 cycles based on the stable Pt-N-C chemical bonds in Pt/N-rGO, which can prevent the detachment, dissolution, migration and aggregation of Pt nanoparticles on the matrix during the long-term cycling.

  9. Ultralow content of Pt on Pd–Co–Cu/C ternary nanoparticles with excellent electrocatalytic activity and durability for the oxygen reduction reaction

    DOE PAGES

    Liu, Sufen; Xiao, Weiping; Wang, Jie; ...

    2016-08-01

    Optimizing the utilization of Pt to catalyze the sluggish kinetics of the oxygen reduction reaction (ORR) is of vital importance in proton exchange membrane fuel cells. One of the strategies is to spread Pt atoms over the surface of a substrate to increase the surface area. We report a facile method to synthesize Pd6CoCu@Pt/C core-shell nanoparticles with an ultralow amount of Pt. It was found that Pt-coated layer on Pd6CoCu cores plays a vital role in enhancing the ORR activity and the cycling stability. The half-wave potential of Pd6CoCu@Pt/C positively shifts about 50 mV and 17 mV relative to Pd6CoCu/Cmore » and Pt/C, respectively. The Pt mass activity on Pd6CoCu@Pt/C was calculated to be about 27 times higher than that on Pt/C catalysts at 0.9 V. Furthermore, the Pd6CoCu@Pt/C nanoparticles exhibit superior stability with almost no decay for the ORR polarization curves during 10,000 potential cycles and the core-shell structure remains with only a slight increase in the thickness of the Pt overlayer. Our findings provide a methodology for synthesizing highly efficient catalytic materials for the cathodic application in fuel cells.« less

  10. Ultralow content of Pt on Pd–Co–Cu/C ternary nanoparticles with excellent electrocatalytic activity and durability for the oxygen reduction reaction

    SciTech Connect

    Liu, Sufen; Xiao, Weiping; Wang, Jie; Zhu, Jing; Wu, Zexing; Xin, Huolin; Wang, Deli

    2016-08-01

    Optimizing the utilization of Pt to catalyze the sluggish kinetics of the oxygen reduction reaction (ORR) is of vital importance in proton exchange membrane fuel cells. One of the strategies is to spread Pt atoms over the surface of a substrate to increase the surface area. We report a facile method to synthesize Pd6CoCu@Pt/C core-shell nanoparticles with an ultralow amount of Pt. It was found that Pt-coated layer on Pd6CoCu cores plays a vital role in enhancing the ORR activity and the cycling stability. The half-wave potential of Pd6CoCu@Pt/C positively shifts about 50 mV and 17 mV relative to Pd6CoCu/C and Pt/C, respectively. The Pt mass activity on Pd6CoCu@Pt/C was calculated to be about 27 times higher than that on Pt/C catalysts at 0.9 V. Furthermore, the Pd6CoCu@Pt/C nanoparticles exhibit superior stability with almost no decay for the ORR polarization curves during 10,000 potential cycles and the core-shell structure remains with only a slight increase in the thickness of the Pt overlayer. Our findings provide a methodology for synthesizing highly efficient catalytic materials for the cathodic application in fuel cells.

  11. Ethanol oxidation on Pt single-crystal electrodes: surface-structure effects in alkaline medium.

    PubMed

    Busó-Rogero, Carlos; Herrero, Enrique; Feliu, Juan M

    2014-07-21

    Ethanol oxidation in 0.1 M NaOH on single-crystal electrodes has been studied using electrochemical and FTIR techniques. The results show that the activity order is the opposite of that found in acidic solutions. The Pt(111) electrode displays the highest currents and also the highest onset potential of all the electrodes. The onset potential for the oxidation of ethanol is linked to the adsorption of OH on the electrode surface. However, small (or even negligible) amounts of CO(ads) and carbonate are detected by FTIR, which implies that cleavage of the C-C bond is not favored in this medium. The activity of the electrodes diminishes quickly upon cycling. The diminution of the activity is proportional to the measured currents and is linked to the formation and polymerization of acetaldehyde, which adsorbs onto the electrode surface and prevents further oxidation.

  12. Enhancing the photovoltaic performance and stability of QDSSCs using surface reinforced Pt nanostructures with controllable morphology and superior electrocatalysis via cost-effective chemical bath deposition.

    PubMed

    Rao, S Srinivasa; Durga, Ikkurthi Kanaka; Kang, Tae-Su; Kim, Soo-Kyoung; Punnoose, Dinah; Gopi, Chandu V V M; Eswar Reddy, Araveeti; Krishna, T N V; Kim, Hee-Je

    2016-02-28

    To make quantum-dot sensitized solar cells (QDSSCs) competitive, photovoltaic parameters such as the power conversion efficiency (PCE) and fill factor (FF) must become comparable to those of other emerging solar cell technologies. In the present study, a novel strategy has been successfully developed for a highly efficient surface-modified platinum (Pt) counter electrode (CE) with high catalytic activity and long-term stability in a polysulfide redox electrolyte. The reinforcement of the Pt surface was performed using a thin passivating layer of CuS, NiS, or CoS by simple chemical bath deposition techniques. This method was a more efficient method for reducing the electron recombination in QDSSCs. The optimized Pt/CuS CE shows a very low charge transfer resistance of 37.01 Ω, which is an order of magnitude lower than those of bare Pt (86.32 Ω), Pt/NiS (53.83 Ω), and Pt/CoS (73.51 Ω) CEs. Therefore, the Pt/CuS CEs show much greater catalytic activity in the polysulfide redox electrolyte than Pt, Pt/NiS and Pt/CoS CEs. As a result, under one-sun illumination (AM 1.5G, 100 mW cm(-2)), the Pt/CuS CE exhibits a PCE of 4.32%, which is higher than the values of 1.77%, 2.95%, and 3.25% obtained with bare Pt, Pt/CoS, and Pt/NiS CEs, respectively. The performance of the Pt/CuS CE was enhanced by the improved current density, Cu vacancies with increased S composition, and surface morphology, which enable rapid electron transport and lower the electron recombination rate for the polysulfide electrolyte redox couple. Electrochemical impedance spectroscopy and Tafel polarization revealed that the hybrid CEs reduce interfacial recombination and exhibit better electrochemical and photovoltaic performance compared with a bare Pt CE. The Pt/CuS CE also shows superior stability in the polysulfide electrolyte in a working state for over 10 h, resulting in a long-term electrode stability than Pt CE.

  13. Facile Synthesis of Nanoporous Pt-Y alloy with Enhanced Electrocatalytic Activity and Durability.

    PubMed

    Cui, Rongjing; Mei, Ling; Han, Guangjie; Chen, Jiyun; Zhang, Genhua; Quan, Ying; Gu, Ning; Zhang, Lei; Fang, Yong; Qian, Bin; Jiang, Xuefan; Han, Zhida

    2017-02-02

    Recently, Pt-Y alloy has displayed an excellent electrocatalytic activity for oxygen reduction reaction (ORR), and is regarded as a promising cathode catalyst for fuel cells. However, the bulk production of nanoscaled Pt-Y alloy with outstanding catalytic performance remains a great challenge. Here, we address the challenge through a simple dealloying method to synthesize nanoporous Pt-Y alloy (NP-PtY) with a typical ligament size of ~5 nm. By combining the intrinsic superior electrocatalytic activity of Pt-Y alloy with the special nanoporous structure, the NP-PtY bimetallic catalyst presents higher activity for ORR and ethanol oxidation reaction, and better electrocatalytic stability than the commercial Pt/C catalyst and nanoporous Pt alloy. The as-made NP-PtY holds great application potential as a promising electrocatalyst in proton exchange membrane fuel cells due to the advantages of facile preparation and excellent catalytic performance.

  14. Facile synthesis of PtAu alloy nanoparticles with high activity for formic acid oxidation

    SciTech Connect

    Zhang, Sheng; Shao, Yuyan; Yin, Geping; Lin, Yuehe

    2010-02-15

    We report the facile synthesis of carbon supported PtAu alloy nanoparticles with high electrocatalytic activity as the anode catalyst for direct formic acid fuel cells (DFAFCs). PtAu alloy nanopaticles are synthesized by co-reducing HAuCl4 and H2PtCl6 with NaBH4 in the presence of sodium citrate and then the nanoparticles are deposited on Vulcan XC-72R carbon support (PtAu/C). The obtained catalysts are characterized with X-ray diffraction (XRD) and transmission electron microscope (TEM), which reveal PtAu alloy formation with an average diameter of 4.6 nm. PtAu/C exhibits 8 times higher catalytic activity toward formic acid oxidation than Pt/C. The enhanced activity of PtAu/C catalyst is attributed to noncontinuous Pt sites formed in the presence of the neighbored Au sites, which promotes direct oxidation of formic acid by avoiding poison CO.

  15. Facile Synthesis of Nanoporous Pt-Y alloy with Enhanced Electrocatalytic Activity and Durability

    NASA Astrophysics Data System (ADS)

    Cui, Rongjing; Mei, Ling; Han, Guangjie; Chen, Jiyun; Zhang, Genhua; Quan, Ying; Gu, Ning; Zhang, Lei; Fang, Yong; Qian, Bin; Jiang, Xuefan; Han, Zhida

    2017-02-01

    Recently, Pt-Y alloy has displayed an excellent electrocatalytic activity for oxygen reduction reaction (ORR), and is regarded as a promising cathode catalyst for fuel cells. However, the bulk production of nanoscaled Pt-Y alloy with outstanding catalytic performance remains a great challenge. Here, we address the challenge through a simple dealloying method to synthesize nanoporous Pt-Y alloy (NP-PtY) with a typical ligament size of ~5 nm. By combining the intrinsic superior electrocatalytic activity of Pt-Y alloy with the special nanoporous structure, the NP-PtY bimetallic catalyst presents higher activity for ORR and ethanol oxidation reaction, and better electrocatalytic stability than the commercial Pt/C catalyst and nanoporous Pt alloy. The as-made NP-PtY holds great application potential as a promising electrocatalyst in proton exchange membrane fuel cells due to the advantages of facile preparation and excellent catalytic performance.

  16. Facile Synthesis of Nanoporous Pt-Y alloy with Enhanced Electrocatalytic Activity and Durability

    PubMed Central

    Cui, Rongjing; Mei, Ling; Han, Guangjie; Chen, Jiyun; Zhang, Genhua; Quan, Ying; Gu, Ning; Zhang, Lei; Fang, Yong; Qian, Bin; Jiang, Xuefan; Han, Zhida

    2017-01-01

    Recently, Pt-Y alloy has displayed an excellent electrocatalytic activity for oxygen reduction reaction (ORR), and is regarded as a promising cathode catalyst for fuel cells. However, the bulk production of nanoscaled Pt-Y alloy with outstanding catalytic performance remains a great challenge. Here, we address the challenge through a simple dealloying method to synthesize nanoporous Pt-Y alloy (NP-PtY) with a typical ligament size of ~5 nm. By combining the intrinsic superior electrocatalytic activity of Pt-Y alloy with the special nanoporous structure, the NP-PtY bimetallic catalyst presents higher activity for ORR and ethanol oxidation reaction, and better electrocatalytic stability than the commercial Pt/C catalyst and nanoporous Pt alloy. The as-made NP-PtY holds great application potential as a promising electrocatalyst in proton exchange membrane fuel cells due to the advantages of facile preparation and excellent catalytic performance. PMID:28150732

  17. RKKY-like contributions to the magnetic anisotropy energy: 3 d adatoms on Pt(111) surface

    NASA Astrophysics Data System (ADS)

    Bouhassoune, Mohammmed; Dias, Manuel dos Santos; Zimmermann, Bernd; Dederichs, Peter H.; Lounis, Samir

    2016-09-01

    The magnetic anisotropy energy defines the energy barrier that stabilizes a magnetic moment. Utilizing density-functional-theory-based simulations and analytical formulations, we establish that this barrier is strongly modified by long-range contributions very similar to Friedel oscillations and Rudermann-Kittel-Kasuya-Yosida interactions. Thus, oscillations are expected and observed, with different decaying factors and highly anisotropic in realistic materials, which can switch nontrivially the sign of the magnetic anisotropy energy. This behavior is general, and for illustration we address the transition-metal adatoms, Cr, Mn, Fe, and Co deposited on a Pt(111) surface. We explain, in particular, the mechanisms leading to the strong site dependence of the magnetic anisotropy energy observed for Fe adatoms on a Pt(111) surface as revealed previously via first-principles-based simulations and inelastic scanning tunneling spectroscopy [A. A. Khajetoorians et al., Phys. Rev. Lett. 111, 157204 (2013), 10.1103/PhysRevLett.111.157204]. The same mechanisms are probably active for the site dependence of the magnetic anisotropy energy obtained for Fe adatoms on Pd or Rh(111) surfaces and for Co adatoms on a Rh(111) surface [P. Blonski et al., Phys. Rev. B 81, 104426 (2010), 10.1103/PhysRevB.81.104426].

  18. Effects of reduction temperature and metal-support interactions on the catalytic activity of Pt/gamma-Al2O3 and Pt/TiO2 for the oxidation of CO in the presence and absence of H2.

    PubMed

    Alexeev, Oleg S; Chin, Soo Yin; Engelhard, Mark H; Ortiz-Soto, Lorna; Amiridis, Michael D

    2005-12-15

    TiO2- and gamma-Al2O3-supported Pt catalysts were characterized by HRTEM, XPS, EXAFS, and in situ FTIR spectroscopy after activation at various conditions, and their catalytic properties were examined for the oxidation of CO in the absence and presence of H2 (PROX). When gamma-Al2O3 was used as the support, the catalytic, electronic, and structural properties of the Pt particles formed were not affected substantially by the pretreatment conditions. In contrast, the surface properties and catalytic activity of Pt/TiO2 were strongly influenced by the pretreatment conditions. In this case, an increase in the reduction temperature led to higher electron density on Pt, altering its chemisorptive properties, weakening the Pt-CO bonds, and increasing its activity for the oxidation of CO. The in situ FTIR data suggest that both the terminal and bridging CO species adsorbed on fully reduced Pt are active for this reaction. The high activity of Pt/TiO2 for the oxidation of CO can also be attributed to the ability of TiO2 to provide or stabilize highly reactive oxygen species at the metal-support interface. However, such species appear to be more reactive toward H2 than CO. Consequently, Pt/TiO2 shows substantially lower selectivities toward CO oxidation under PROX conditions than Pt/gamma-Al2O3.

  19. Synthesis and characterization of Pd@Pt-Ni core-shell octahedra with high activity toward oxygen reduction.

    PubMed

    Choi, Sang-Il; Shao, Minhua; Lu, Ning; Ruditskiy, Aleksey; Peng, Hsin-Chieh; Park, Jinho; Guerrero, Sandra; Wang, Jinguo; Kim, Moon J; Xia, Younan

    2014-10-28

    The oxygen reduction reaction (ORR) on the cathode of a polymer electrolyte fuel cell requires the use of a catalyst based on Pt, one of the most expensive metals on the earth. A number of strategies, including optimization of shape or facet, formation of alloys with other metals, and incorporation of a different metal into the core, have been investigated to enhance the activity of a Pt-based catalyst and thus reduce the loading of Pt. This article reports the synthesis and characterization of Pd@Pt-Ni core-shell octahedra with high activity toward ORR. The octahedra with an edge length of 8 nm were obtained by directly depositing thin, conformal shells of a Pt-Ni alloy on Pd octahedra of 6 nm in edge length. The key to the success of this synthesis is the use of an amphiphilic solvent to ensure good compatibility between the solvents typically used for the syntheses of Pd and Pt-Ni nanocrystals. The core-shell structure was confirmed by a number of techniques, including scanning transmission electron microscopy, energy-dispersive X-ray spectroscopy mapping, in situ X-ray diffraction under H2 and He, and electrochemical measurements. Relative to the state-of-the-art Pt/C catalyst, the Pd@Pt-Ni/C catalyst showed mass and specific ORR activities enhanced by 12.5- and 14-fold, respectively. The formation of a core-shell structure helped increase the electroactive surface area in terms of Pt and thus the mass activity. During an accelerated durability test, the mass activity of the Pd@Pt-Ni/C catalyst only dropped by 1.7% after 10,000 cycles.

  20. Immobilizing Highly Catalytically Active Pt Nanoparticles inside the Pores of Metal-Organic Framework: A Double Solvents Approach

    SciTech Connect

    Aijaz, Arshad; Karkamkar, Abhijeet J.; Choi, Young Joon; Tsumori, Nobuko; Ronnebro, Ewa; Autrey, Thomas; Shioyama, Hiroshi; Xu, Qiang

    2012-08-29

    Ultrafine Pt nanoparticles were successfully immobilized inside the pores of a metal-organic framework MIL-101 without deposition of Pt nanoparticles on the external surfaces of framework by using a 'double solvents' method. The resulting Pt@MIL-101 composites with different Pt loadings represent the first highly active MOF-immobilized metal nanocatalysts for catalytic reactions in all three phases: liquid-phase ammonia borane hydrolysis; solid-phase ammonia borane thermal dehy-drogenation and gas-phase CO oxidation. The observed excellent catalytic performances are at-tributed to the small Pt nanoparticles within the pores of MIL-101. 'We are thankful to AIST and METI for financial support. TA & AK are thankful for support from the US Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. PNNL is operated by Battelle.'

  1. Improving the electrical catalytic activity of Pt/TiO2 nanocomposites by a combination of electrospinning and microwave irradiation

    NASA Astrophysics Data System (ADS)

    Long, Qi; Cai, Mei; Li, Jinru; Rong, Huilin; Jiang, Long

    2011-04-01

    One of the greatest challenges in preparing TiO2-based oxygen electrodes for PEM fuel cells is increasing the electrical catalytic activity of Pt nanoparticle/TiO2 composites by improving the dispersion of Pt. This article describes a new way for improving the dispersion of Pt nanoparticles by depositing them on TiO2 fibers and using microwave irradiation. The Pt nanoparticles used in this experiment is about 5 nm in diameter and the diameter of TiO2 fibers could be controlled ranging from 30 to 60 nm and Pt nanoparticles still keep their size when the deposition amount is increased on the surface of TiO2 fibers. The Pt nanoparticles were highly dispersed without agglomeration even at a weight percentage of composites as high as 40%. The position of Pt nanoparticles located in the fiber and the composition of Pt/TiO2, which had great influence on the electric conductivity and electrical catalytic activity of the composite, could be easily controlled.

  2. Novel TiO2-Pt@SiO2 nanocomposites with high photocatalytic activity

    NASA Astrophysics Data System (ADS)

    Wu, Hao-Shuai; Sun, Ling-Dong; Zhou, Huan-Ping; Yan, Chun-Huan

    2012-05-01

    This article reports a facile and controllable two-step method to construct TiO2-Pt@SiO2 nanocomposites. TiO2 nanoparticles (NPs), with small size and high surface energy, were synthesized by a solvothermal reaction process. The TiO2-Pt@SiO2 nanocomposites were fabricated by a reverse micro-emulsion method. SiO2 shell coated NPs were adopted for further photocatalytic reaction. Because of their small size and high surface energy, TiO2@SiO2 and TiO2-Pt@SiO2 nanocomposites show higher photocatalytic activity than commercial Degussa P25. Compared with TiO2@SiO2, TiO2-Pt@SiO2nanocomposites have improved photocatalytic activity due to the Pt induced spatial separation of electrons and holes. The silica shells not only maintain the structure of the nanocomposites but also prevent their aggregation during the photocatalytic reactions, which is highly important for the good durability of the photocatalyst. This strategy is simple, albeit efficient, and can be extended to the synthesis of other composites of noble metals. It has opened a new window for the construction of hetero-nanocomposites with high activity and durability, which would serve as excellent models in catalytic systems of both theoretical and practical interest.This article reports a facile and controllable two-step method to construct TiO2-Pt@SiO2 nanocomposites. TiO2 nanoparticles (NPs), with small size and high surface energy, were synthesized by a solvothermal reaction process. The TiO2-Pt@SiO2 nanocomposites were fabricated by a reverse micro-emulsion method. SiO2 shell coated NPs were adopted for further photocatalytic reaction. Because of their small size and high surface energy, TiO2@SiO2 and TiO2-Pt@SiO2 nanocomposites show higher photocatalytic activity than commercial Degussa P25. Compared with TiO2@SiO2, TiO2-Pt@SiO2nanocomposites have improved photocatalytic activity due to the Pt induced spatial separation of electrons and holes. The silica shells not only maintain the structure of the

  3. Microcanonical unimolecular rate theory at surfaces. I. Dissociative chemisorption of methane on Pt(111)

    NASA Astrophysics Data System (ADS)

    Bukoski, A.; Blumling, D.; Harrison, I.

    2003-01-01

    A model of gas-surface reactivity is developed based on the ideas that (a) adsorbate chemistry is a local phenomenon, (b) the active system energy of an adsorbed molecule and a few immediately adjacent surface atoms suffices to fix microcanonical rate constants for surface kinetic processes such as desorption and dissociation, and (c) energy exchange between the local adsorbate-surface complexes and the surrounding substrate can be modeled via a Master equation to describe the system/heat reservoir coupling. The resulting microcanonical unimolecular rate theory (MURT) for analyzing and predicting both thermal equilibrium and nonequilibrium kinetics for surface reactions is applied to the dissociative chemisorption of methane on Pt(111). Energy exchange due to phonon-mediated energy transfer between the local adsorbate-surface complexes and the surface is explored and estimated to be insignificant for the reactive experimental conditions investigated here. Simulations of experimental molecular beam data indicate that the apparent threshold energy for CH4 dissociative chemisorption on Pt(111) is E0=0.61 eV (over a C-H stretch reaction coordinate), the local adsorbate-surface complex includes three surface oscillators, and the pooled energy from 16 active degrees of freedom is available to help surmount the dissociation barrier. For nonequilibrium molecular beam experiments, predictions are made for the initial methane dissociative sticking coefficient as a function of isotope, normal translational energy, molecular beam nozzle temperature, and surface temperature. MURT analysis of the thermal programmed desorption of CH4 physisorbed on Pt(111) finds the physisorption well depth is 0.16 eV. Thermal equilibrium dissociative sticking coefficients for methane on Pt(111) are predicted for the temperature range from 250-2000 K. Tolman relations for the activation energy under thermal equilibrium conditions and for a variety of "effective activation energies" under

  4. Origin of high oxygen reduction reaction activity of Pt12 and strategy to obtain better catalyst using sub-nanosized Pt-alloy clusters

    PubMed Central

    Miyazaki, Kasumi; Mori, Hirotoshi

    2017-01-01

    In the present study, methods to enhance the oxygen reduction reaction (ORR) activity of sub-nanosized Pt clusters were investigated in a theoretical manner. Using ab initio molecular dynamics and Monte Carlo simulations based on density functional theory, we have succeeded in determining the origin of the superior ORR activity of Pt12 compared to that of Pt13. That is, it was clarified that the electronic structure of Pt12 fluctuates to a greater extent compared to that of Pt13, which leads to stronger resistance against catalyst poisoning by O/OH. Based on this conclusion, a set of sub-nanosized Pt-alloy clusters was also explored to find catalysts with better ORR activities and lower financial costs. It was suggested that Ga4Pt8, Ge4Pt8, and Sn4Pt8 would be good candidates for ORR catalysts. PMID:28349985

  5. Pd@Pt core-shell concave decahedra: A class of catalysts for the oxygen reduction reaction with enhanced activity and durability

    SciTech Connect

    Wang, Xue; Vera, Madeline; Chi, Miaofang; Xia, Younan; Luo, Ming; Huang, Hongwen; Ruditskiy, Aleksey; Park, Jinho; Bao, Shixiong; Liu, Jingyue; Howe, Jane; Xie, Zhaoxiong

    2015-11-13

    Here, we report a facile synthesis of multiply twinned Pd@Pt core shell concave decahedra by controlling the deposition of Pt on preformed Pd decahedral seeds. The Pt atoms are initially deposited on the vertices of a decahedral seed, followed by surface diffusion to other regions along the edges/ridges and then across the faces. Different from the coating of a Pd icosahedral seed, the Pt atoms prefer to stay at the vertices and edges/ridges of a decahedral seed even when the deposition is conducted at 200 degrees C, naturally generating a core shell structure covered by concave facets. The nonuniformity in the Pt coating can be attributed to the presence of twin boundaries at the vertices, as well as the {100} facets and twin defects along the edges/ridges of a decahedron, effectively trapping the Pt adatoms at these high-energy sites. As compared to a commercial Pt/C catalyst, the Pd@Pt concave decahedra show substantial enhancement in both catalytic activity and durability toward the oxygen reduction reaction (ORR). For the concave decahedra with 29.6% Pt by weight, their specific (1.66 mA/cm2pt) and mass (1.60 A/mg/2pt) ORR activities are enhanced by 4.4 and 6.6 times relative to those of the Pt/C catalyst (0.36 mA/cm2pt and 0.32 A/mgpt, respectively). After 10 000 cycles of accelerated durability test, the concave decahedra still exhibit a mass activity of 0.69 A/mgpt, more than twice that of the pristine Pt/C catalyst.

  6. Sum-frequency generation of acetate adsorption on Au and Pt surfaces: Molecular structure effects

    NASA Astrophysics Data System (ADS)

    Braunschweig, Björn; Mukherjee, Prabuddha; Kutz, Robert B.; Wieckowski, Andrzej; Dlott, Dana D.

    2010-12-01

    The reversible adsorption of acetate on polycrystalline Au and Pt surfaces was investigated with broadband sum-frequency generation (SFG) and cyclic voltammetry. Specifically adsorbed acetate as well as coadsorbed sulfuric acid anions are observed for the first time with SFG and give rise to dramatically different SFG intensities on Au and Pt surfaces. While similar coverages of acetate adlayers on Au and Pt surfaces are well established by previous studies, an identification of the interfacial molecular structure has been elusive. However, we have applied the high sensitivity of SFG for interfacial polar ordering to identify different acetate structures at Au and Pt surfaces in contact with HClO4 and H2SO4 electrolytes. Acetate competes with the formation of surface oxides and shifts the oxidation threshold of both Au and Pt electrodes anodically. Effects of the supporting electrolyte on the formation of acetate adlayers are revealed by comparing SFG spectra in HClO4 and H2SO4 solutions: Sulfuric acid anions modify the potential-dependent acetate adsorption, compete with adsorbed acetate on Au and coadsorb with acetate on Pt surfaces.

  7. LEEM Investigation of the Faceting of the Pt Covered W (111) Surface

    SciTech Connect

    Hannon, J.B.; Kellogg, G.L.; Madey, T.E.; Pelhos, K.

    1999-01-20

    A low energy electron microscope (LEEM) has been used to investigate the faceting of W(111) as induced by Pt. The atomically rough W(111) surface, when fully covered with a monolayer film of Pt and annealed to temperatures higher than {approximately} 750 K, experiences a significant morphological restructuring: the initially planar surface undergoes a faceting transition and forms three-sided pyramids with {211} faces. The experiments demonstrate the capability of LEEM for imaging both the fully and partially faceted surface. In addition, we have observed the formation of the facets in real time, when Pt is dosed onto the heated surface. We find that the transition from planar surface, to partially faceted surface, and to fully faceted surface proceeds through the nucleation and growth of spatially separated faceted regions.

  8. Correlation of Pt-Re Surface Properties with Reaction Pathways for the Aqueous-Phase Reforming of Glycerol

    SciTech Connect

    Zhang, Liang; Karim, Ayman M.; Engelhard, Mark H.; Wei, Zhehao; King, D. L.; Wang, Yong

    2012-01-17

    The surface properties of Pt-Re catalytic nano-particles supported on carbon following exposure to a hydrogen reducing environment and subsequent hydrothermal conditions have been studied using in-situ X-ray photoelectron spectroscopy (XPS) and ammonia temperature programmed desorption (TPD). These properties have been correlated with the catalyst selectivity for the aqueous phase reforming of glycerol. We show that Pt in reduced Pt-Re/C becomes electron deficient, and a fraction of the Re becomes oxidized when the catalyst is subsequently exposed to hydrothermal reaction conditions. Oxidation of Pt-Re generates surface acidity, which drastically affects the reaction pathways. The acid site concentration, but not acid site strength, increases with Re loading. This acidity increase with Re addition favors C-O over C-C cleavage, which results in higher selectivity to liquid products and alkanes at the expense of hydrogen production. We propose a model for the Pt-Re active site and the origin of acidity enhanced by the addition of Re.

  9. A Nanostructured Bifunctional platform for Sensing of Glucose Biomarker in Artificial Saliva: Synergy in hybrid Pt/Au surfaces.

    PubMed

    Raymundo-Pereira, Paulo A; Shimizu, Flávio M; Coelho, Dyovani; Piazzeta, Maria H O; Gobbi, Angelo L; Machado, Sergio A S; Oliveira, Osvaldo N

    2016-12-15

    We report on a bimetallic, bifunctional electrode where a platinum (Pt) surface was patterned with nanostructured gold (Au) fingers with different film thicknesses, which was functionalized with glucose oxidase (GOx) to yield a highly sensitive glucose biosensor. This was achieved by using selective adsorption of a self-assembled monolayer (SAM) onto Au fingers, which allowed GOx immobilization only onto the Au-SAM surface. This modified electrode was termed bifunctional because it allowed to simultaneously immobilize the biomolecule (GOx) on gold to catalyze glucose, and detect hydrogen peroxide on Pt sites. Optimized electrocatalytic activity was reached for the architecture Pt/Au-SAM/GOx with 50nm thickness of Au, where synergy between Pt and Au allowed for detection of hydrogen peroxide (H2O2) at a low applied potential (0V vs. Ag/AgCl). Detection was performed for H2O2 in the range between 4.7 and 102.7 nmol L(-1), with detection limit of 3.4×10(-9) mol L(-1) (3.4 nmol L(-1)) and an apparent Michaelis-Menten rate constant of 3.2×10(-6)molL(-1), which is considerably smaller than similar devices with monometallic electrodes. The methodology was validated by measuring glucose in artificial saliva, including in the presence of interferents. The synergy between Pt and Au was confirmed in electrochemical impedance spectroscopy measurements with an increased electron transfer, compared to bare Pt and Au electrodes. The approach for fabricating the reproducible bimetallic Pt/Au electrodes is entirely generic and may be explored for other types of biosensors and biodevices where advantage can be taken of the combination of the two metals.

  10. Growth of epitaxial Pt1-xPbx alloys by surface limited redox replacement and study of their adsorption properties.

    PubMed

    Mercer, M P; Plana, D; Fermίn, D J; Morgan, D; Vasiljevic, N

    2015-10-06

    The surface limited redox replacement (SLRR) method has been used to design two-dimensional Pt-Pb nanoalloys with controlled thickness, composition, and structure. The electrochemical behavior of these alloys has been systematically studied as a function of alloy composition. A single-cell, two-step SLRR protocol based on the galvanic replacement of underpotentially deposited monolayers of Pb with Pt was used to grow epitaxial Pt1-xPbx (x < 0.1) alloys of up to 10 ML thickness on Au substrates. It is shown that by varying the terminating potential of the galvanic replacement step, the Pb atomic content can be controlled in the films. Electrochemical analysis of the alloys showed that the adsorption of both H and CO exhibits similar, and systematic, decreases with small increases in the Pb content. These measurements, commonly used in electrocatalysis for the determination of active surface areas of Pt, suggested area values much lower than those expected based on the net Pt composition in the alloy as measured by XPS. These results show that Pb has a strong screening effect on the adsorption of both H and CO. Moreover, changes in alloy composition result in a negative shift in the potential of the peaks of CO oxidation that scales with the increase of Pb content. The results suggest electronic and bifunctional effects of incorporated Pb on the electrochemical behavior of Pt. The study illustrates the potential of the SLRR methodology, which could be employed in the design of 2-dimensional bimetallic Pt nanoalloys for fundamental studies of electrocatalytic behavior in fuel cell reactions dependent on the nature of alloying metal and its composition.

  11. Molybdenum-Doped PdPt@Pt Core-Shell Octahedra Supported by Ionic Block Copolymer-Functionalized Graphene as a Highly Active and Durable Oxygen Reduction Electrocatalyst.

    PubMed

    Cho, Kie Yong; Yeom, Yong Sik; Seo, Heun Young; Kumar, Pradip; Lee, Albert S; Baek, Kyung-Youl; Yoon, Ho Gyu

    2017-01-18

    Development of highly active and durable electrocatalysts that can effectively electrocatalyze oxygen reduction reactions (ORR) still remains one important challenge for high-performance electrochemical conversion and storage applications such as fuel cells and metal-air batteries. Herein, we propose the combination of molybdenum-doped PdPt@Pt core-shell octahedra and the pyrene-functionalized poly(dimethylaminoethyl methacrylate)-b-poly[(ethylene glycol) methyl ether methacrylate] ionic block copolymer-functionalized reduced graphene oxide (Mo-PdPt@Pt/IG) to effectively augment the interfacial cohesion of both components using a tunable ex situ mixing strategy. The rationally designed Mo-PdPt@Pt core-shell octahedra have unique compositional benefits, including segregation of Mo atoms on the vertexes and edges of the octahedron and 2-3 shell layers of Pt atoms on a PdPt alloy core, which can provide highly active sites to the catalyst for ORR along with enhanced electrochemical stability. In addition, the ionic block copolymer functionalized graphene can facilitate intermolecular charge transfer and good stability of metal NPs, which arises from the ionic block copolymer interfacial layer. When the beneficial features of the Mo-PdPt@Pt and IG are combined, the Mo-PdPt@Pt/IG exhibits substantially enhanced activity and durability for ORR relative to those of commercial Pt/C. Notably, the Mo-PdPt@Pt/IG shows mass activity 31-fold higher than that of Pt/C and substantially maintains high activities after 10 000 cycles of intensive durability testing. The current study highlights the crucial strategies in designing the highly active and durable Pt-based octahedra and effective combination with functional graphene supports toward the synergetic effects on ORR.

  12. Calorimetry, activity, and micro-FTIR analysis of CO chemisorption, titration, and oxidation on supported Pt

    NASA Technical Reports Server (NTRS)

    Sermon, Paul A.; Self, Valerie A.; Vong, Mariana S. W.; Wurie, Alpha T.

    1990-01-01

    The value of in situ analysis on CO chemisorption, titration and oxidation over supported Pt catalysts using calorimetry, catalytic and micro-FTIR methods is illustrated using silica- and titania-supported samples. Isothermal CO-O and O2-CO titrations have not been widely used on metal surfaces and may be complicated if some oxide supports are reduced by CO titrant. However, they can illuminate the kinetics of CO oxidation on metal/oxide catalysts since during such titrations all O and CO coverages are scanned as a function of time. There are clear advantages in following the rates of the catalyzed CO oxidation via calorimetry and gc-ms simultaneously. At lower temperatures the evidence they provide is complementary. CO oxidation and its catalysis of CO oxidation have been extensively studied with hysteresis and oscillations apparent, and the present results suggest the benefits of a combined approach. Silica support porosity may be important in defining activity-temperature hysteresis. FTIR microspectroscopy reveals the chemical heterogeneity of the catalytic surfaces used; it is interesting that the evidence with regard to the dominant CO surface species and their reactivities with regard to surface oxygen for present oxide-supported Pt are different from those seen on graphite-supported Pt.

  13. Synthesis of Pt-Mo-N Thin Film and Catalytic Activity for Fuel Cells

    SciTech Connect

    Miura, Akira; Tague, Michele E.; Gregoire, John M.; Wen, Xiao-Dong; van Dover, R. Bruce; Abruña, Héctor D.; DiSalvo, Francis J.

    2010-05-13

    Pt-Mo-N composition gradient film was synthesized by combining thin-film deposition techniques and subsequent thermal nitridation. A ternary platinum-based nitride, Pt2Mo3N, showed catalytic activities for fuel cell applications and higher electrochemical stability when it was compared with a PtMo alloy with the same Pt:Mo ratio.

  14. Activation of Propane C-H and C-C Bonds by Gas-Phase Pt Atom: A Theoretical Study

    PubMed Central

    Li, Fang-Ming; Yang, Hua-Qing; Ju, Ting-Yong; Li, Xiang-Yuan; Hu, Chang-Wei

    2012-01-01

    The reaction mechanism of the gas-phase Pt atom with C3H8 has been systematically investigated on the singlet and triplet potential energy surfaces at CCSD(T)//BPW91/6-311++G(d, p), Lanl2dz level. Pt atom prefers the attack of primary over secondary C-H bonds in propane. For the Pt + C3H8 reaction, the major and minor reaction channels lead to PtC3H6 + H2 and PtCH2 + C2H6, respectively, whereas the possibility to form products PtC2H4 + CH4 is so small that it can be neglected. The minimal energy reaction pathway for the formation of PtC3H6 + H2, involving one spin inversion, prefers to start at the triplet state and afterward proceed along the singlet state. The optimal C-C bond cleavages are assigned to C-H bond activation as the first step, followed by cleavage of a C-C bond. The C-H insertion intermediates are kinetically favored over the C-C insertion intermediates. From C-C to C-H oxidative insertion, the lowering of activation barrier is mainly caused by the more stabilizing transition state interaction ΔE≠int, which is the actual interaction energy between the deformed reactants in the transition state. PMID:22942766

  15. Direct Visualization of Catalytically Active Sites at the FeO-Pt(111) Interface

    SciTech Connect

    Kudernatsch, Wilhelmine; Peng, Guowen; Zeuthen, Helene; Bai, Yunhai; Merte, L. R.; Lammich, Lutz; Besenbacher, Fleming; Mavrikakis, Manos; Wendt, Stefen

    2015-08-25

    Within the area of surface science, one of the “holy grails” is to directly visualize a chemical reaction at the atomic scale. Whereas this goal has been reached by high-resolution scanning tunneling microscopy (STM) in a number of cases for reactions occurring at flat surfaces, such a direct view is often inhibited for reaction occurring at steps and interfaces. Here we have studied the CO oxidation reaction at the interface between ultrathin FeO islands and a Pt(111) support by in situ STM and density functional theory (DFT) calculations. Time-lapsed STM imaging on this inverse model catalyst in O2 and CO environments revealed catalytic activity occurring at the FeO-Pt(111) interface and directly showed that the Fe-edges host the catalytically most active sites for the CO oxidation reaction. This is an important result since previous evidence for the catalytic activity of the FeO-Pt(111) interface is essentially based on averaging techniques in conjunction with DFT calculations. The presented STM results are in accord with DFTþU calculations, in which we compare possible CO oxidation pathways on oxidized Fe-edges and O-edges. We found that the CO oxidation reaction is more favorable on the oxidized Fe-edges, both thermodynamically and kinetically.

  16. On the adsorption and formation of Pt dimers on the CeO2(111) surface.

    PubMed

    Bruix, Albert; Nazari, Fariba; Neyman, Konstantin M; Illas, Francesc

    2011-12-28

    The direct adsorption of Pt(2) dimers on CeO(2)(111) and their formation from isolated adsorbed Pt atoms have been studied using periodic slab model calculations based on density functional theory and including the so-called on-site Hubbard parameter (GGA + U). In the most stable configuration Pt(2) is found to be almost parallel to the surface; the electronic ground state is closed shell and there is no evidence of charge transfer towards or from the surface. The formation of Pt(2) from two single adsorbed Pt atoms involves a rather small energy barrier of ~0.10 eV only. On the contrary, dissociation of adsorbed Pt(2) requires to overcome a considerable barrier of ~1.43 eV. This indicates that once Pt(2) is formed it will remain on the surface, thus likely triggering the growth of larger supported Pt particles.

  17. Nanoporous bimetallic Pt-Au alloy nanocomposites with superior catalytic activity towards electro-oxidation of methanol and formic acid

    NASA Astrophysics Data System (ADS)

    Zhang, Zhonghua; Wang, Yan; Wang, Xiaoguang

    2011-04-01

    We present a facile route to fabricate novel nanoporous bimetallic Pt-Au alloy nanocomposites by dealloying a rapidly solidified Al75Pt15Au10 precursor under free corrosion conditions. The microstructure of the precursor and the as-dealloyed sample was characterized using X-ray diffraction, scanning electron microscopy, transmission electron microscopy, high-resolution transmission electron microscopy, and energy dispersive X-ray (EDX) analysis. The Al75Pt15Au10 precursor is composed of a single-phase Al2(Au,Pt) intermetallic compound, and can be fully dealloyed in a 20 wt.% NaOH or 5 wt.% HCl aqueous solution. The dealloying leads to the formation of the nanoporous Pt60Au40 nanocomposites (np-Pt60Au40 NCs) with an fcc structure. The morphology, size and crystal orientation of grains in the precursor can be conserved in the resultant nanoporous alloy. The np-Pt60Au40 NCs consist of two zones with distinct ligament/channel sizes and compositions. The formation mechanism of these np-Pt60Au40 NCs can be rationalized based upon surface diffusion of more noble elements and spinodal decomposition during dealloying. Electrochemical measurements demonstrate that the np-Pt60Au40 NCs show superior catalytic activity towards the electro-oxidation of methanol and formic acid in the acid media compared to the commercial JM-Pt/C catalyst. This material can find potential applications in catalysis related areas, such as direct methanol or formic acidfuelcells. Our findings demonstrate that dealloying is an effective and simple strategy to realize the alloying of immiscible systems under mild conditions, and to fabricate novel nanostructures with superior performance.We present a facile route to fabricate novel nanoporous bimetallic Pt-Au alloy nanocomposites by dealloying a rapidly solidified Al75Pt15Au10 precursor under free corrosion conditions. The microstructure of the precursor and the as-dealloyed sample was characterized using X-ray diffraction, scanning electron

  18. The control of Pt and Ru nanoparticle size on high surface area supports.

    PubMed

    Liu, Qiuli; Joshi, Upendra A; Über, Kevin; Regalbuto, John R

    2014-12-28

    Supported Ru and Pt nanoparticles are synthesized by the method of strong electrostatic adsorption and subsequently treated under different steaming-reduction conditions to achieve a series of catalysts with controlled particle sizes, ranging from 1 to 8 nm. While in the case of oxidation-reduction conditions, only Pt yielded particles ranging from 2.5 to 8 nm in size and a loss of Ru was observed. Both Ru and Pt sinter faster in air than in hydrogen. This methodology allows the control of particle size using a "production-scalable" catalyst synthesis method which can be applied to high surface area supports with common metal precursors.

  19. Ab Initio Surface Phase Diagrams for Coadsorption of Aromatics and Hydrogen on the Pt(111) Surface

    DOE PAGES

    Ferguson, Glen Allen; Vorotnikov, Vassili; Wunder, Nicholas; ...

    2016-11-02

    Supported metal catalysts are commonly used for the hydrogenation and deoxygenation of biomass-derived aromatic compounds in catalytic fast pyrolysis. To date, the substrate-adsorbate interactions under reaction conditions crucial to these processes remain poorly understood, yet understanding this is critical to constructing detailed mechanistic models of the reactions important to catalytic fast pyrolysis. Density functional theory (DFT) has been used in identifying mechanistic details, but many of these works assume surface models that are not representative of realistic conditions, for example, under which the surface is covered with some concentration of hydrogen and aromatic compounds. In this study, we investigate hydrogen-guaiacolmore » coadsorption on Pt(111) using van der Waals-corrected DFT and ab initio thermodynamics over a range of temperatures and pressures relevant to bio-oil upgrading. We find that relative coverage of hydrogen and guaiacol is strongly dependent on the temperature and pressure of the system. Under conditions relevant to ex situ catalytic fast pyrolysis (CFP; 620-730 K, 1-10 bar), guaiacol and hydrogen chemisorb to the surface with a submonolayer hydrogen (~0.44 ML H), while under conditions relevant to hydrotreating (470-580 K, 10-200 bar), the surface exhibits a full-monolayer hydrogen coverage with guaiacol physisorbed to the surface. These results correlate with experimentally observed selectivities, which show ring saturation to methoxycyclohexanol at hydrotreating conditions and deoxygenation to phenol at CFP-relevant conditions. Additionally, the vibrational energy of the adsorbates on the surface significantly contributes to surface energy at higher coverage. Ignoring this contribution results in not only quantitatively, but also qualitatively incorrect interpretation of coadsorption, shifting the phase boundaries by more than 200 K and ~10-20 bar and predicting no guaiacol adsorption under CFP and hydrotreating conditions

  20. Ab Initio Surface Phase Diagrams for Coadsorption of Aromatics and Hydrogen on the Pt(111) Surface

    SciTech Connect

    Ferguson, Glen Allen; Vorotnikov, Vassili; Wunder, Nicholas; Clark, Jared; Gruchalla, Kenny; Bartholomew, Timothy; Robichaud, David J.; Beckham, Gregg T.

    2016-11-02

    Supported metal catalysts are commonly used for the hydrogenation and deoxygenation of biomass-derived aromatic compounds in catalytic fast pyrolysis. To date, the substrate-adsorbate interactions under reaction conditions crucial to these processes remain poorly understood, yet understanding this is critical to constructing detailed mechanistic models of the reactions important to catalytic fast pyrolysis. Density functional theory (DFT) has been used in identifying mechanistic details, but many of these works assume surface models that are not representative of realistic conditions, for example, under which the surface is covered with some concentration of hydrogen and aromatic compounds. In this study, we investigate hydrogen-guaiacol coadsorption on Pt(111) using van der Waals-corrected DFT and ab initio thermodynamics over a range of temperatures and pressures relevant to bio-oil upgrading. We find that relative coverage of hydrogen and guaiacol is strongly dependent on the temperature and pressure of the system. Under conditions relevant to ex situ catalytic fast pyrolysis (CFP; 620-730 K, 1-10 bar), guaiacol and hydrogen chemisorb to the surface with a submonolayer hydrogen (~0.44 ML H), while under conditions relevant to hydrotreating (470-580 K, 10-200 bar), the surface exhibits a full-monolayer hydrogen coverage with guaiacol physisorbed to the surface. These results correlate with experimentally observed selectivities, which show ring saturation to methoxycyclohexanol at hydrotreating conditions and deoxygenation to phenol at CFP-relevant conditions. Additionally, the vibrational energy of the adsorbates on the surface significantly contributes to surface energy at higher coverage. Ignoring this contribution results in not only quantitatively, but also qualitatively incorrect interpretation of coadsorption, shifting the phase boundaries by more than 200 K and ~10-20 bar and predicting no guaiacol adsorption under CFP and hydrotreating conditions. We

  1. A study on novel pulse preparation and electrocatalytic activities of Pt/C-Nafion electrodes for proton exchange membrane fuel cell

    NASA Astrophysics Data System (ADS)

    Li, Jingjing; Ye, Feng; Chen, Ling; Wang, Tongtao; Li, Jianling; Wang, Xindong

    To aim at reducing the platinum loading and increasing the utilization of platinum in PEMFC electrode, a new pulse electrodeposition technique for preparing proton exchange membrane fuel cell (PEMFC) electrodes has been developed in this paper. This method combines coating Pt seeds on the C-Nafion substrate and introducing polyethylene glycol (PEG) into the deposition solution. SEM images of the samples show that Pt seeds and PEG take an important role in the morphology of the Pt deposit. The surface area and average particle size of Pt were determined by charge integration under the hydrogen desorption peaks of cyclic voltammetry. The electrocatalytic activities of these electrodes towards oxygen reduction reaction (ORR) were investigated by using rotating disc electrode (RDE). The Pt catalyst which was prepared by Pt seeds and PEG, its active surface area and electrocatalytic activity towards ORR were improved remarkably. And the optimized electrode displayed higher catalytic activity than a conventional electrode made from commercial Pt/C catalyst. The possible reasons for the effects of Pt seeds and PEG on the higher catalytic activity of prepared Pt catalysts have been preliminarily discussed.

  2. Linking morphology with activity through the lifetime of pretreated PtNi nanostructured thin film catalysts

    SciTech Connect

    Cullen, David A.; Lopez-Haro, Miguel; Bayle-Guillemaud, Pascale; Debe, Mark; Steinbach, Andrew J.; Guetaz, L.

    2015-01-01

    In this study, the nanoscale morphology of highly active Pt3Ni7 nanostructured thin film fuel cell catalysts is linked with catalyst surface area and activity following catalyst pretreatments, conditioning and potential cycling. The significant role of fuel cell conditioning on the structure and composition of these extended surface catalysts is demonstrated by high resolution imaging, elemental mapping and tomography. The dissolution of Ni during fuel cell conditioning leads to highly complex, porous structures which were visualized in 3D by electron tomography. Quantification of the rendered surfaces following catalyst pretreatment, conditioning, and cycling shows the important role pore structure plays in surface area, activity, and durability.

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

    DOE PAGES

    Li, Wei-Zhen; Nie, Lei; Cheng, Yingwen; ...

    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 in this paper, aiming at further lowering the catalyst cost by substituting expensive Pt with cheaper Ir in the bulk. Small Pt-Ir nano-alloy particles (< 2 nm) 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 exposuremore » 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. Finally, a dynamic stabilization mechanism involving wetting/nucleation seems to be responsible for the evolution of surface compositions upon cyclic oxidizing and reducing thermal treatments.« less

  4. Surface enrichment of Pt in stable Pt-Ir nano-alloy particles on MgAl2O4 spinel in oxidizing atmosphere

    DOE PAGES

    Li, Wei -Zhen; Nie, Lei; Cheng, Yingwen; ...

    2017-01-13

    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 in this paper, aiming at further lowering the catalyst cost by substituting expensive Pt with cheaper Ir in the bulk. Small Pt-Ir nano-alloy particles (< 2 nm) 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 exposuremore » 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. Finally, a dynamic stabilization mechanism involving wetting/nucleation seems to be responsible for the evolution of surface compositions upon cyclic oxidizing and reducing thermal treatments.« less

  5. Nanoporous bimetallic Pt-Au alloy nanocomposites with superior catalytic activity towards electro-oxidation of methanol and formic acid.

    PubMed

    Zhang, Zhonghua; Wang, Yan; Wang, Xiaoguang

    2011-04-01

    We present a facile route to fabricate novel nanoporous bimetallic Pt-Au alloy nanocomposites by dealloying a rapidly solidified Al(75)Pt(15)Au(10) precursor under free corrosion conditions. The microstructure of the precursor and the as-dealloyed sample was characterized using X-ray diffraction, scanning electron microscopy, transmission electron microscopy, high-resolution transmission electron microscopy, and energy dispersive X-ray (EDX) analysis. The Al(75)Pt(15)Au(10) precursor is composed of a single-phase Al(2)(Au,Pt) intermetallic compound, and can be fully dealloyed in a 20 wt.% NaOH or 5 wt.% HCl aqueous solution. The dealloying leads to the formation of the nanoporous Pt(60)Au(40) nanocomposites (np-Pt(60)Au(40) NCs) with an fcc structure. The morphology, size and crystal orientation of grains in the precursor can be conserved in the resultant nanoporous alloy. The np-Pt(60)Au(40) NCs consist of two zones with distinct ligament/channel sizes and compositions. The formation mechanism of these np-Pt(60)Au(40) NCs can be rationalized based upon surface diffusion of more noble elements and spinodal decomposition during dealloying. Electrochemical measurements demonstrate that the np-Pt(60)Au(40) NCs show superior catalytic activity towards the electro-oxidation of methanol and formic acid in the acid media compared to the commercial JM-Pt/C catalyst. This material can find potential applications in catalysis related areas, such as direct methanol or formic acid fuel cells. Our findings demonstrate that dealloying is an effective and simple strategy to realize the alloying of immiscible systems under mild conditions, and to fabricate novel nanostructures with superior performance.

  6. Electrocatalytic activity of PtAu/C catalysts for glycerol oxidation.

    PubMed

    Jin, Changchun; Sun, Chao; Dong, Rulin; Chen, Zhidong

    2012-01-01

    The electrocatalytic oxidation of glycerol on PtAu/C catalysts has been investigated by cyclic voltammetry. PtAu bimetallic nanoparticles are prepared by chemical reduction. Carbon-supported PtAu catalysts are found to exhibit high electrocatalytic activity for the oxidation of glycerol in alkaline solution in terms of oxidation potential and current density as well as stability, and PtAu/C catalysts with different Pt:Au composition ratios show no much difference in catalytic activity. In acidic solution, PtAu/C catalysts exhibit similar to Pt/C catalysts in activity, but the advantage of the PtAu/C catalysts in terms of per unit mass of platinum is still obvious. The PtAu/C catalysts, in a wide Pt:Au ratio range, show a remarkable enhancement in the mass specific activity of platinum with decreasing platinum content in both alkaline and acidic solutions. This is of significance for reducing the usage of platinum and indicates that though platinum acts as main active sites, gold also plays an important role in the function of PtAu/C catalysts.

  7. Vibrational properties of the Pt(111)- p(2 × 2)-K surface superstructure

    NASA Astrophysics Data System (ADS)

    Rusina, G. G.; Eremeev, S. V.; Borisova, S. D.; Chulkov, E. V.

    2008-08-01

    The vibrational spectra of the Pt(111)- p(2 × 2)-K ordered surface superstructure formed on the platinum surface upon adsorption of 0.25 potassium monolayer are calculated using the interatomic interaction potentials obtained within the tight-binding approximation. The surface relaxation, the dispersion of surface phonons, the local density of surface vibrational states, and the polarization of vibrational modes of adatoms and substrate atoms are discussed. The theoretical results are in good agreement with the recently obtained experimental data.

  8. Nanoparticle cluster gas sensor: Pt activated SnO2 nanoparticles for NH3 detection with ultrahigh sensitivity.

    PubMed

    Liu, Xu; Chen, Nan; Han, Bingqian; Xiao, Xuechun; Chen, Gang; Djerdj, Igor; Wang, Yude

    2015-09-28

    Pt activated SnO2 nanoparticle clusters were synthesized by a simple solvothermal method. The structure, morphology, chemical state and specific surface area were analyzed by X-ray powder diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and N2-sorption studies, respectively. The SnO2 nanoparticle cluster matrix consists of tens of thousands of SnO2 nanoparticles with an ultra-small grain size estimated to be 3.0 nm. And there are abundant random-packed wormhole-like pores, caused by the inter-connection of the SnO2 nanoparticles, throughout each cluster. The platinum element is present in two forms including metal (Pt) and tetravalent metal oxide (PtO2) in the Pt activated SnO2 nanoparticle clusters. The as-synthesized pure and Pt activated SnO2 nanoparticle clusters were used to fabricate gas sensor devices. It was found that the gas response toward 500 ppm of ammonia was improved from 6.48 to 203.44 through the activation by Pt. And the results indicate that the sensor based on Pt activated SnO2 not only has ultrahigh sensitivity but also possesses good response-recovery properties, linear dependence, repeatability, selectivity and long-term stability, demonstrating the potential to use Pt activated SnO2 nanoparticle clusters as ammonia gas sensors. At the same time, the formation mechanisms of the unique nanoparticle clusters and highly enhanced sensitivity are also discussed.

  9. Pd@Pt core-shell concave decahedra: A class of catalysts for the oxygen reduction reaction with enhanced activity and durability

    DOE PAGES

    Wang, Xue; Vera, Madeline; Chi, Miaofang; ...

    2015-11-13

    Here, we report a facile synthesis of multiply twinned Pd@Pt core shell concave decahedra by controlling the deposition of Pt on preformed Pd decahedral seeds. The Pt atoms are initially deposited on the vertices of a decahedral seed, followed by surface diffusion to other regions along the edges/ridges and then across the faces. Different from the coating of a Pd icosahedral seed, the Pt atoms prefer to stay at the vertices and edges/ridges of a decahedral seed even when the deposition is conducted at 200 degrees C, naturally generating a core shell structure covered by concave facets. The nonuniformity inmore » the Pt coating can be attributed to the presence of twin boundaries at the vertices, as well as the {100} facets and twin defects along the edges/ridges of a decahedron, effectively trapping the Pt adatoms at these high-energy sites. As compared to a commercial Pt/C catalyst, the Pd@Pt concave decahedra show substantial enhancement in both catalytic activity and durability toward the oxygen reduction reaction (ORR). For the concave decahedra with 29.6% Pt by weight, their specific (1.66 mA/cm2pt) and mass (1.60 A/mg/2pt) ORR activities are enhanced by 4.4 and 6.6 times relative to those of the Pt/C catalyst (0.36 mA/cm2pt and 0.32 A/mgpt, respectively). After 10 000 cycles of accelerated durability test, the concave decahedra still exhibit a mass activity of 0.69 A/mgpt, more than twice that of the pristine Pt/C catalyst.« less

  10. Enhanced electrocatalytic activity of the Au-electrodeposited Pt nanoparticles-coated conducting oxide for the quantum dot-sensitized solar cells

    SciTech Connect

    Yoon, Yeung-Pil; Kim, Jae-Hong; Ahn, Kwang-Soon; Kang, Soon-Hyung; Kim, Hyunsoo; Choi, Chel-Jong; Kim, Kyong-Kook

    2014-08-25

    Au was electrodeposited potentiostatically at 0.3 V for 5 min on nanoporous Pt nanoparticle-coated F-doped SnO{sub 2} (FTO/Pt) substrates. For comparison, Au-electrodeposited FTO (FTO/Au) and Au-uncoated FTO/Pt were prepared. FTO/Au showed large-sized Au clusters dispersed sparsely over FTO, which resulted in lower electrocatalytic activity than FTO/Pt. In contrast, FTO/Pt exhibited poor stability unlike FTO/Au due to poisoning by the adsorption of sulfur species. The Au-electrodeposited FTO/Pt (FTO/Pt/Au) consisted of small Au clusters deposited over the entire area of Pt due to the effective Au nucleation provided by nanoporous metallic Pt. FTO/Pt/Au exhibited enhanced electrocatalytic activity and excellent stability because the small Au particles well-dispersed over the nanoporous metallic Pt network provided numerous electrochemical reaction sites, and the Pt surface was not exposed to the electrolyte. When FTO/Pt/Au was used as the counter electrode (CE) of a quantum dot-sensitized solar cell, the significantly enhanced electrocatalytic activity of the FTO/Pt/Au CE facilitated the reduction reaction of S{sub n}{sup 2− }+ 2e{sup −} (CE) → S{sub n−1}{sup 2−} + S{sup 2−} at the CE/electrolyte interface, resulting in a significantly hindered recombination reaction, S{sub n}{sup 2− }+ 2e{sup −} (TiO{sub 2} in the photoanode) → S{sub n-1}{sup 2−} + S{sup 2−}, and significantly improved overall energy conversion efficiency.

  11. Lifting of the Au(100) surface reconstruction by Pt, Cr, Fe, and Cu adsorption

    NASA Astrophysics Data System (ADS)

    Tempas, Christopher D.; Skomski, Daniel; Tait, Steven L.

    2016-12-01

    The adsorption and growth of metals on the surfaces of other metals is an important topic for studies of heterogeneous catalysis and bimetallic nanoparticles. The surface structure of these systems impacts nanoparticle growth, catalytic activity, and reaction selectivity. In these experiments, platinum, chromium, iron, or copper were vapor deposited on the reconstructed Au(100) surface. The initial growth of each metal was studied by scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS). Each of the four metals forms anisotropic rectangular islands oriented in the direction of the gold reconstruction rows. The gradual lifting of the surface reconstruction by increased metal coverage is observed, and the reconstruction is fully lifted after 0.5 ML of Pt, Cr, or Fe, or by 3.3 ML of Cu. After the reconstruction is lifted, the island shape changes from rectangular to square, illustrating the effect of surface structure on growth. Second layer islands begin to form before the completion of the first full layer.

  12. In situ measurements of change in work function of Pt, Pd and Au surfaces during desorption of oxygen by using photoemission yield spectrometer in air

    NASA Astrophysics Data System (ADS)

    Yamashita, Daisuke; Ishizaki, Atsushi

    2016-02-01

    We investigated the change in work function of Pt, Pd and Au surfaces during desorption of oxygen by using a photoemission yield spectrometer with an open counter. Oxygen coverage was formed by UV/ozone treatment, and then continuous change in work function with exposure to air was observed at various temperatures. Work function of Pt, Pd and Au surfaces decreased during desorption of oxygen, and finally returned to the initial value of untreated surfaces. Furthermore, temperature dependence on the change in work function was found. These characteristics were explained using chemical kinetics scheme. The exponential decay of work function was well reproduced by the first-order reaction rate equation, and it was confirmed that the order of rate constant, kr, is kr(Au) < kr(Pd) < kr(Pt). The activation energy was estimated to be 36, 38 and 28 kJ/mol for Pt, Pd, Au, respectively.

  13. Enhanced electrocatalytic activity and stability of Pd3V/C nanoparticles with a trace amount of Pt decoration for the oxygen reduction reaction

    DOE PAGES

    Liu, Sufen; Han, Lili; Zhu, Jing; ...

    2015-09-14

    In this study, carbon supported Pd3V bimetallic alloy nanoparticles (Pd3V/C) have been successfully synthesized via a simple impregnation–reduction method, followed by high temperature treatment under a H2 atmosphere. Electrochemical tests reveal that the half-wave potential of Pd3V/C-500 shifts positively 40 mV compared with Pd/C. However, the catalytic activity of Pd3V/C-500 suffers from serious degradation after 1k cycles. By a spontaneous displacement reaction or co-reduction method, a trace amount of Pt was decorated on the surface or inside of the Pd3V/C nanoparticles. The catalytic activity and stability of the Pd3V@Pt/C and Pt-Pd3V/C catalysts for the oxygen reduction reaction (ORR) are enhancedmore » significantly, and are comparable to commercial Pt/C. In addition, the Pt mass activity of Pd3V@Pt/C and Pt-Pd3V/C improves by factors of 10.9 and 6.5 at 0.80 V relative to Pt/C. Moreover, Pt-decorated Pd3V/C nanoparticles show almost no obvious morphology change after durability tests, because the Pt-rich shell plays an important role in preventing degradation.« less

  14. Ultrathin dendritic Pt3Cu triangular pyramid caps with enhanced electrocatalytic activity.

    PubMed

    Kuang, Yun; Cai, Zhao; Zhang, Ying; He, Dongsheng; Yan, Xiuling; Bi, Yongmin; Li, Yaping; Li, Ziyou; Sun, Xiaoming

    2014-10-22

    Here we report on the synthesis of novel dendritic Pt3Cu triangular pyramid caps via a solvothermal coreduction method. These caps had three-dimensional caved structures with ultrathin branches, as evidenced by high-resolution transmission electron microscopy (HRTEM) and HAADF-STEM characterization. Tuning the reduction kinetics of two metal precursors by an iodide ion was believed to be the key for the formation of an alloyed nanostructure. Electro-oxidation of methanol and formic acid showed dramatically improved electrocatalytic activities and poison-tolerance for these nanoalloys as compared to commercial Pt/C catalysts, which was attributed to their unique open porous structure with interconnected network, ultrahigh surface areas, as well as synergetic effect of the two metallic components.

  15. Highly Effective Pt-Based Water-Gas Shift Catalysts by Surface Modification with Alkali Hydroxide Salts

    SciTech Connect

    Kusche, Matthias; Bustillo, Karen; Agel, Friederike; Wasserscheid, Peter

    2015-01-29

    Here, 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 H2O at the catalytically active sites. Kinetic studies reveal a negligible effect of the KOH coating on the rate dependence of CO and H2O partial pressures. In conclusion, 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 240h 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 7.5wt%.

  16. Highly Effective Pt-Based Water-Gas Shift Catalysts by Surface Modification with Alkali Hydroxide Salts

    DOE PAGES

    Kusche, Matthias; Bustillo, Karen; Agel, Friederike; ...

    2015-01-29

    Here, 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 filmmore » of alkali hydroxide forms on the alumina surface, which increases the availability of H2O at the catalytically active sites. Kinetic studies reveal a negligible effect of the KOH coating on the rate dependence of CO and H2O partial pressures. In conclusion, 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 240h 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 7.5wt%.« less

  17. Controlling hydrogenation activity and selectivity of bimetallic surfaces and catalysts

    NASA Astrophysics Data System (ADS)

    Murillo, Luis E.

    Studies of bimetallic systems are of great interest in catalysis due to the novel properties that they often show in comparison with the parent metals. The goals of this dissertation are: (1) to expand the studies of self-hydrogenation and hydrogenation reactions on bimetallic surfaces under ultra high vacuum conditions (UHV) using different hydrocarbon as probe molecules; (2) to attempt to correlate the surface science findings with supported catalyst studies under more realistic conditions; and (3) to investigate the competitive hydrogenation of C=C versus C=O bonds on Pt(111) modified by different 3d transition metals. Hydrogenation studies using temperature programmed desorption (TPD) on Ni/Pt(111) bimetallic surfaces have demonstrated an enhancement in the low temperature hydrogenation activity relative to that of clean Pt(111). This novel hydrogenation pathway can be achieved under UHV conditions by controlling the structures of the bimetallic surfaces. A low temperature hydrogenation activity of 1-hexene and 1-butene has been observed on a Pt-Ni-Pt(111) subsurface structure, where Ni atoms are mainly present on the second layer of the Pt(111) single crystal. These results are in agreement with previous studies of self-hydrogenation and hydrogenation of cyclohexene. However, a much higher dehydrogenation activity is observed in the reaction of cyclohexene to produce benzene, demonstrating that the hydrocarbon structure has an effect on the reaction pathways. On the other hand, self-hydrogenation of 1-butene is not observed on the Pt-Ni-Pt(111) surface, indicating that the chain length (or molecular weight) has a significant effect on the selfhydrogenation activity. The gas phase reaction of cyclohexene on Ni/Pt supported on alumina catalysts has also shown a higher self-hydrogenation activity in comparison with the same reaction performed on supported monometallic catalysts. The effects of metal loading and impregnation sequence of the metal precursors are

  18. Linking morphology with activity through the lifetime of pretreated PtNi nanostructured thin film catalysts

    DOE PAGES

    Cullen, David A.; Lopez-Haro, Miguel; Bayle-Guillemaud, Pascale; ...

    2015-01-01

    In this study, the nanoscale morphology of highly active Pt3Ni7 nanostructured thin film fuel cell catalysts is linked with catalyst surface area and activity following catalyst pretreatments, conditioning and potential cycling. The significant role of fuel cell conditioning on the structure and composition of these extended surface catalysts is demonstrated by high resolution imaging, elemental mapping and tomography. The dissolution of Ni during fuel cell conditioning leads to highly complex, porous structures which were visualized in 3D by electron tomography. Quantification of the rendered surfaces following catalyst pretreatment, conditioning, and cycling shows the important role pore structure plays in surfacemore » area, activity, and durability.« less

  19. Break-up of Pt catalyst surfaces by high CO coverage

    SciTech Connect

    Tao, Feng; Dag, Sefa; Wang, Lin-Wang; Liu, Zhi; Butcher, Derek; Bluhm, Henrik; Salmeron, Miquel; Somorjai, Gabor

    2009-09-16

    Stepped Platinum surfaces were found to undergo extensive and reversible restructuring when exposed to CO at pressures above 0.1 Torr. This radically new and previously unknown restructuring phenomenon, has important implications for Pt based catalytic reactions. Novel Scanning Tunneling Microscopy and Photoelectron Spectroscopy techniques operating under gaseous environments near ambient pressure and temperature revealed that as the CO surface coverage approaches 100percent, the originally flat terraces of stepped Pt crystals break up into nanometer size clusters. At room temperature the crystal surface reverts to its initial flat morphology after pumping away the gas phase CO. Density Functional Theory energy calculations provide a rationale for the observations whereby the creation of increased concentrations of low coordination Pt sites at the edges of the formed nanoclusters relieves the strong CO-CO repulsion in the highly compressed adsorbate film.

  20. Molecular dynamics study of ethanol solvated by water on the Pt (1 1 1) surface

    NASA Astrophysics Data System (ADS)

    Kholmurodov, Kholmirzo; Dushanov, Ermuhammad; Yasuoka, Kenji; Khalil, Hagar; Galal, Ahmed; Ahmed, Sameh; Sweilam, Nasser; Moharram, Hatem

    2012-06-01

    An analysis of the molecular dynamics of ethanol solvated by water molecules in the absence and presence of the Pt (1 1 1) surface has been performed using DL_POLY version 2.19. The structure and diffusion properties of an ethanol-water system have been studied at various temperatures from 250 to 350 K. We have measured the self-diffusion coefficients of a 50:50% ethanol-water system; in the absence of a Pt surface our results have shown an excellent agreement with the experimental data (within an error of 7.4%). The enhancement of self-diffusion coefficients with the inclusion of the Pt (1 1 1) surface has been observed and estimated. Graphs of radial distribution functions (RDF) have been built; RDF correlations with the self-diffusion coefficients of both ethanol and water molecules are also illustrated.

  1. Enhanced activity and stability of Pt/TiO2/carbon fuel cell electrocatalyst prepared using a glucose modifier

    NASA Astrophysics Data System (ADS)

    Odetola, Christopher; Trevani, Liliana; Easton, E. Bradley

    2015-10-01

    Two TiO2-C composite materials were prepared through a conventional sol gel synthesis using Vulcan XC-72 carbon black. The carbon was initially functionalised to form acid treated Vulcan (ATV) prior to TiO2 deposition. In one composite, the ATV was further modified through glucose adsorption (G-ATV) in order to facilitate the growth of small and uniform TiO2 nanoparticles on the carbon surface. Platinum nanoparticles were deposited on TiO2/G-ATV and TiO2/ATV supports through reduction of H2PtCl6 with NaBH4 at 0 °C. The electrochemical properties of the two composite catalysts were compared with in house Pt/C catalyst. We observed a three-fold increase in TiO2 loading (14 wt%) on glucose doped carbon surface compared with just acid treated support (5 wt%). The beginning of life (BOL) electrochemical active surface area (ECSA) of Pt/14 wt%TiO2/G-ATV catalyst was 40.4 m2 g-1 compared to 37.1 m2 g-1 obtained for Pt on 5 wt% TiO2/ATV despite increased TiO2 loadings on the former. Furthermore these composite catalysts showed enhanced oxygen reduction activity and better durability during accelerated stress tests which was attributed to an electronic interaction between Pt and the TiO2 on the support.

  2. Correlation Between Surface Chemistry and Electrocatalytic Properties of Monodisperse Pt(x)Ni(1-x) Nanoparticles

    SciTech Connect

    Wang, Chao; Chi, Miaofang; Wang, Guofeng; Van der Vliet, Dennis; Li, Dongguo; More, Karren Leslie; Wang, Hsien-Hua; Schlueter, John; Markovic, Nenad; Stamenkovic, Vojislav

    2011-01-01

    Monodisperse and homogeneous Pt{sub x}Ni{sub 1-x} alloy nanoparticles of various compositions are synthesized via an organic solution approach in order to reveal the correlation between surface chemistry and their electrocatalytic properties. Atomic-level microscopic analysis of the compositional profile and modeling of nanoparticle structure are combined to follow the dependence of Ni dissolution on the initial alloy composition and formation of the Pt-skeleton nanostructures. The developed approach and acquired knowledge about surface structure-property correlation can be further generalized and applied towards the design of advanced functional nanomaterials.

  3. Photo-enhanced activity of Pt and Pt-Ru catalysts towards the electro-oxidation of methanol

    NASA Astrophysics Data System (ADS)

    Arulmani, Dheevesh V.; Eastcott, Jennie I.; Mavilla, Stephanie G.; Easton, E. Bradley

    2014-02-01

    Electrocatalyst materials, consisting of Pt or Pt-Ru supported on carbon with and without TiO2, are evaluated for their activity towards the methanol oxidation reaction (MOR) in 1.0 M H2SO4 at 25 °C in the presence and absence of visible light irradiation. Electrochemical studies showed that enhanced MOR activity is achieved upon irradiation with visible light for each catalyst, in both the presence and absence of TiO2. Irradiation leads to no improvement in activity towards the formic acid oxidation reaction (FAOR) indicating that irradiation aids in the removal of adsorbed intermediate species, such as CO, during MOR. While the presence of a TiO2 support does lead to an increase in activity upon irradiation, about 50% of the improvements arise solely from the irradiation of the metal-containing electrocatalysts themselves.

  4. Mechanism of oxygen reduction reaction on Pt(111) in alkaline solution: Importance of chemisorbed water on surface

    DOE PAGES

    Liu, Shizhong; White, Michael G.; Liu, Ping

    2016-06-30

    Here, we report a detailed mechanistic study of the oxygen reduction reaction (ORR) on Pt(111) in alkaline solution, combining density functional theory and kinetic Monte Carlo simulations. A complex reaction network including four possible pathways via either 2e– or 4e– transfer is established and is able to reproduce the experimental measured polarization curve at both low- and high-potential regions. Our results show that it is essential to account for solvation by water and the dynamic coverage of *OH to describe the reaction kinetics well. In addition, a chemisorbed water (*H2O)-mediated mechanism including 4e– transfers is identified, where the reduction stepsmore » via *H2O on the surface are potential-independent and only the final removal of *OH from the surface in the form of OH–(aq) contributes to the current. For the ORR in alkaline solutions, such a mechanism is more competitive than the associative and dissociative mechanisms typically used to describe the ORR in acid solution. Finally, *OH and **O2 intermediates are found to be critically important for tuning the ORR activity of Pt in alkaline solution. To enhance the activity, the binding of Pt should be tuned in such a way that *OH binding is weak enough to release more surface sites under working conditions, while **O2 binding is strong enough to enable the ORR via the 4e– transfer mechanism.« less

  5. Assessment of the ethanol oxidation activity and durability of Pt catalysts with or without a carbon support using Electrochemical Impedance Spectroscopy

    NASA Astrophysics Data System (ADS)

    Saleh, Farhana S.; Easton, E. Bradley

    2014-01-01

    We compared the stability and performance of 3 commercially available Johnson Matthey catalysts with various Pt loadings (20, 40 and 100%) using two different accelerated durability testing (ADT) protocols. The various Pt-loaded catalysts were tested by means of a series of intermittent life tests (1, 200, 400, 1000, 2000, 3000 and 4000 cycles). The electrochemical surface area (ECSA) loss of electrode was investigated by electrochemical technique (CV). The use of EIS as an accelerated-testing protocol distinctly elucidates the extent of degradation of Johnson Matthey catalysts with various Pt loading. Using EIS, it was possible to show that Pt-black catalyst layers suffer from increased electronic resistance over the course of ADT which is not observed when a corrosion stable carbon support is present. The effect of Pt loading was further elucidated by comparing the electrocatalytic activity of the catalyst layers towards ethanol oxidation reaction (EOR). The catalyst layer with the lowest Pt loading showed the enhanced EOR performance.

  6. Influence of the morphology on the platinum electrode surface activity

    NASA Astrophysics Data System (ADS)

    Reiner, Andreas; Steiger, Beat; Scherer, Günther G.; Wokaun, Alexander

    Polycrystalline Pt electrodes with different surface characteristics were investigated by cyclic voltammetry (CV) in 0.5 M H 2SO 4. Plane electrodes showed a decrease in electrochemically active surface area while cycling in the hydrogen underpotential region (H upd), in contrast, electrodes roughened by intensive pre-cycling exhibited a stable value for the electrochemically active surface.

  7. Antagonistic Activities of Novel Peptides from Bacillus amyloliquefaciens PT14 against Fusarium solani and Fusarium oxysporum.

    PubMed

    Kim, Young Gwon; Kang, Hee Kyoung; Kwon, Kee-Deok; Seo, Chang Ho; Lee, Hyang Burm; Park, Yoonkyung

    2015-12-09

    Bacillus species have recently drawn attention due to their potential use in the biological control of fungal diseases. This paper reports on the antifungal activity of novel peptides isolated from Bacillus amyloliquefaciens PT14. Reverse-phase high-performance liquid chromatography revealed that B. amyloliquefaciens PT14 produces five peptides (PT14-1, -2, -3, -4a, and -4b) that exhibit antifungal activity but are inactive against bacterial strains. In particular, PT14-3 and PT14-4a showed broad-spectrum antifungal activity against Fusarium solani and Fusarium oxysporum. The PT14-4a N-terminal amino acid sequence was identified through Edman degradation, and a BLAST homology analysis showed it not to be identical to any other protein or peptide. PT14-4a displayed strong fungicidal activity with minimal inhibitory concentrations of 3.12 mg/L (F. solani) and 6.25 mg/L (F. oxysporum), inducing severe morphological deformation in the conidia and hyphae. On the other hand, PT14-4a had no detectable hemolytic activity. This suggests PT14-4a has the potential to serve as an antifungal agent in clinical therapeutic and crop-protection applications.

  8. Activities and Stabilities of Au-Modified Stepped-Pt Single-Crystal Electrodes as Model Cathode Catalysts in Polymer Electrolyte Fuel Cells.

    PubMed

    Kodama, Kensaku; Jinnouchi, Ryosuke; Takahashi, Naoko; Murata, Hajime; Morimoto, Yu

    2016-03-30

    The purpose of this study is to test the concept of protecting vulnerable sites on cathode catalysts in polymer electrolyte fuel cells. Pt single-crystal surfaces were modified by depositing Au atoms selectively on (100) step sites and their electrocatalytic activities for oxygen reduction reaction (ORR) and stabilities against potential cycles were examined. The ORR activities were raised by 70% by the Au modifications, and this rise in the activity was ascribed to enhanced local ORR activities on Pt(111) terraces by the surface Au atoms. The Au modifications also stabilized the Pt surfaces against potential cycles by protecting the low-coordinated (100) step sites from surface reorganizations. Thus, the surface modification by selective Au depositions on vulnerable sites is a promising method to enhance both the ORR activity and durability of the catalysts.

  9. Sulfur deactivation mechanism of Pt/MnOx-CeO2 for soot oxidation: Surface property study

    NASA Astrophysics Data System (ADS)

    Zhang, Hailong; Hou, Zhongyan; Zhu, Yi; Wang, Jianli; Chen, Yaoqiang

    2017-02-01

    In this work, an advanced diffuse reflectance infrared fourier transform spectra (DRIFTS) technology is used to describe the formation of surface sulfates on Pt/MnOx-CeO2 and study the possible deactivation mechanism for soot oxidation reactions in NO + O2. IR spectra of CO adsorption and H2-TPR results reveal the surface coverage of Pt by sulfates and the loss of partial active oxygen species after the sulfation, respectively. More importantly, in situ DRIRT spectra show sulfur poisoning apparently inhibits the formation of surface intermediates such as monodentate/bidentate nitrates and nitro species, which directly limits the production of NO2. Furthermore, the O2-TPD results indicate that the sulfation weakens the desorption of surface active oxygen resulting from the decomposition of surface nitrates. The sulfate formation would affect the production of oxygen vacant sites and thereby the mobility of surface oxygen species in both NO + O2 and O2. These factors above would play an important role on the deactivation mechanism for soot oxidation.

  10. Kinetics of optically excited charge carriers at the GaN surface: Influence of catalytic Pt nanostructures

    SciTech Connect

    Winnerl, Andrea Pereira, Rui N.; Stutzmann, Martin

    2015-10-21

    In this work, we use GaN with different deposited Pt nanostructures as a controllable model system to investigate the kinetics of photo-generated charge carriers in hybrid photocatalysts. We combine conductance and contact potential difference measurements to investigate the influence of Pt on the processes involved in the capture and decay of photo-generated charge carriers at and close to the GaN surface. We found that in the presence of Pt nanostructures the photo-excitation processes are similar to those found in Pt free GaN. However, in GaN with Pt nanostructures, photo-generated holes are preferentially trapped in surface states of the GaN covered with Pt and/or in electronic states of the Pt and lead to an accumulation of positive charge there, whereas negative charge is accumulated in localized states in a shallow defect band of the GaN covered with Pt. This preferential accumulation of photo-generated electrons close to the surface is responsible for a dramatic acceleration of the turn-off charge transfer kinetics and a stronger dependence of the surface photovoltage on light intensity when compared to a Pt free GaN surface. Our study shows that in hybrid photocatalysts, the metal nanostructures induce a spatially inhomogeneous surface band bending of the semiconductor that promotes a lateral drift of photogenerated charges towards the catalytic nanostructures.

  11. The effect of low concentrations of tetrachloroethylene on H2 adsorption and activation on Pt in a fuel cell catalyst

    NASA Astrophysics Data System (ADS)

    Zhang, Jack Z.; Colón-Mercado, Héctor R.; Goodwin, James G.

    2011-10-01

    The poisoning effect of tetrachloroethylene (TTCE) on the activity of a Pt fuel cell catalyst for the adsorption and activation of H2 was investigated at 60 °C and 2 atm using hydrogen surface concentration measurements. The impurity was chosen as a model compound for chlorinated cleaning and degreasing agents that may be introduced into a fuel cell as a contaminant at a fueling station and/or during vehicle maintenance. In the presence of only H2, introduction of up to 540 ppm TTCE in H2 to Pt/C resulted in a reduction of available Pt surface atoms (measured by H2 uptake) by ca. 30%, which was not enough to shift the H2-D2 exchange reaction away from being equilibrium limited. Exposure of TTCE to Pt/C in a mixed redox environment (hydrogen + oxygen), similar to that at the cathode of a fuel cell, resulted in a much more significant loss of Pt surface atom availability, suggesting a role in TTCE decomposition and/or Cl poisoning. Regeneration of catalyst activity of poisoned Pt/C showed the highest level of recovery when regenerated in only H2, with much less recovery in H2 + O2 or O2. The results from this study are in good agreement with those found in a fuel cell study by Martínez-Rodríguez et al. [2] and confirm that the majority of the poisoning from TTCE on fuel cell performance is most likely at the cathode, rather than the anode.

  12. Quantum Dynamics Study on the Effects of Vibration, Translational Energy and Incident Angle on H2 Adsorption on a Defective Pt(111) Surface

    NASA Astrophysics Data System (ADS)

    Natividad, Michelle T.; Arboleda, Nelson B.; Kasai, Hideaki

    2014-12-01

    Quantum dynamics calculations via the local reflection matrix method are performed to investigate the effects of the vibration and initial translational energy on the dissociative adsorption of H2 approaching a defective Pt(111) surface at different incident angles and adsorption sites. The sticking probability plot for H2 incident on the top site at 15° shows that as the translational energy is increased, the probability rapidly rises to unity which suggests that H2 is easily adsorbed on the Pt surface. The plot also shows that even though the adsorption process is non-activated, there is a probability that H2 will not be adsorbed on the Pt surface at low translational energies due to quantum mechanical effects. For the rest of the configurations, an S-shaped region is observed in the plots suggesting an activated adsorption process. The plots show that when the initial translational energy (Et) is less that the barrier, H2 sticks to the Pt surface by tunneling through the barrier and when Et is greater than the barrier, H2 sticks on the Pt surface by using its available energy to overcome the barrier. The plots also show significant vibration assisted sticking (VAS) effect for all cases. VAS effect is most prominent for H2 approaching the vacant site at incident angles 15 and 30°.

  13. Adsorption and ring-opening of lactide on the chiral metal surface Pt(321){sup S} studied by density functional theory

    SciTech Connect

    Franke, J.-H.; Kosov, D. S.

    2015-01-28

    We study the adsorption and ring-opening of lactide on the naturally chiral metal surface Pt(321){sup S}. Lactide is a precursor for polylactic acid ring-opening polymerization, and Pt is a well known catalyst surface. We study, here, the energetics of the ring-opening of lactide on a surface that has a high density of kink atoms. These sites are expected to be present on a realistic Pt surface and show enhanced catalytic activity. The use of a naturally chiral surface also enables us to study potential chiral selectivity effects of the reaction at the same time. Using density functional theory with a functional that includes the van der Waals forces in a first-principles manner, we find modest adsorption energies of around 1.4 eV for the pristine molecule and different ring-opened states. The energy barrier to be overcome in the ring-opening reaction is found to be very small at 0.32 eV and 0.30 eV for LL- and its chiral partner DD-lactide, respectively. These energies are much smaller than the activation energy for a dehydrogenation reaction of 0.78 eV. Our results thus indicate that (a) ring-opening reactions of lactide on Pt(321) can be expected already at very low temperatures, and Pt might be a very effective catalyst for this reaction; (b) the ring-opening reaction rate shows noticeable enantioselectivity.

  14. CO Oxidation on supported single Pt atoms - Experimental and Ab Initio density functional studies of CO interaction with Pt atom on theta-alumina(010) surface

    SciTech Connect

    Narula, Chaitanya Kumar; Debusk, Melanie Moses; Yoon, Mina; Allard Jr, Lawrence Frederick; Mullins, David R; Wu, Zili; Yang, Xiaofan; Veith, Gabriel M; Stocks, George Malcolm

    2013-01-01

    Although there are only a few known examples of supported single atoms, they are unique because they bridge the gap between homogenous and heterogeneous catalysis. The metal center is single supported atoms can be isoelectronic with their homogenous catalyst counterpart and may allow mechanistic pathways normally seen in homogenous catalysts. Here, we report CO oxidation activity of mono-disperse single Pt atoms supported on an inert substrate, -alumina (Al2O3), in the presence of stoichiometric oxygen. Since CO oxidation on single Pt atoms cannot occur via a conventional Langmuir-Hinshelwood scheme (L-H scheme) which requires at least one Pt-Pt bond, we have carried out a first principles density functional theoretical study of a proposed pathway which is a variation on the conventional L-H scheme and is inspired by organometallic chemistry of platinum. We find that a single supported Pt atom prefers to bond to O2 over CO. The CO then bonds with the oxygenated Pt atom and forms a carbonate which dissociates to liberate CO2, leaving an oxygen atom on Pt. A subsequent reaction with another CO molecule regenerates the single atom catalyst. An in-situ diffuse reflectance infrared study of CO adsorption on the catalyst s supported single atoms has been carried out to infer information on CO absorption modes and compare the observed spectra with calculated ones for intermediates in the proposed CO oxidation pathway. Our results clearly show that supported Pt single atoms are catalytically active and that this catalytic activity can occur without involving the substrate. Characterization by electron microscopy and X-ray absorption studies of the mono-disperse Pt/ -Al2O3, synthesized by solution methods, are also presented.

  15. Surface and electronic structure of epitaxial PtLuSb (001) thin films

    SciTech Connect

    Patel, Sahil J.; Kawasaki, Jason K.; Logan, John; Schultz, Brian D.; Adell, J.; Thiagarajan, B.; Mikkelsen, A.; Palmstrøm, Chris J.

    2014-05-19

    The surface and electronic structure of single crystal thin films of PtLuSb (001) grown by molecular beam epitaxy were studied. Scanning tunneling spectroscopy (STS), photoemission spectroscopy, and temperature dependent Hall measurements of PtLuSb thin films are consistent with a zero-gap semiconductor or semi-metal. STS and photoemission measurements show a decrease in density of states approaching the Fermi level for both valence and conduction bands as well as a slight shift of the Fermi level position into the valence band. Temperature dependent Hall measurements also corroborate the Fermi level position by measurement of p-type carriers.

  16. Biopolymer-stabilized Pt nanoparticles colloid: a highly active and recyclable catalyst for biphasic catalysis

    NASA Astrophysics Data System (ADS)

    Wang, Yujia; Shen, Yueyue; Qiu, Yunfei; Zhang, Ting; Liao, Yang; Zhao, Shilin; Ma, Jun; Mao, Hui

    2016-10-01

    Noble metal nanoparticles are promising candidates to replace conventional bulk counterparts owing to their high activity and selectivity. To enable catalyst recovery, noble metal nanoparticles are often supported onto solid matrices to prepare heterogeneous catalyst. Although recycle of noble metal nanoparticles is realized by heterogenization, a loss of activity is usually encountered. In the present investigation, Pt nanoparticles with tunable particle size (1.85-2.80 nm) were facilely prepared by using polyphenols as amphiphilic stabilizers. The as-prepared Pt nanoparticles colloid solution could be used as highly active catalyst in aqueous-organic biphasic catalysis. The phenolic hydroxyls of polyphenols could constrain Pt nanoparticles in aqueous phase, and simultaneously, the aromatic scaffold of polyphenols ensured effective interactions between substrates and Pt nanoparticles. As a consequence, the obtained polyphenols-stabilized Pt nanoparticles exhibited high activity and cycling stability in biphasic hydrogenation of a series of unsaturated compounds. Compared with conventional heterogeneous Pt-C and Pt-Al2O3 catalysts, polyphenols-stabilized Pt nanoparticles showed obvious advantage both in activity and cycling stability.

  17. Finite electric field effects in the large perpendicular magnetic anisotropy surface Pt/Fe/Pt(001): a first-principles study.

    PubMed

    Tsujikawa, Masahito; Oda, Tatsuki

    2009-06-19

    We investigate crystalline magnetic anisotropy in the electric field (EF) for the FePt surface which has a large perpendicular anisotropy, by means of the first-principles approach. Anisotropy is reduced linearly with respect to the inward EF, associated with the induced spin density around the Fe layer. Although the magnetic anisotropy energy (MAE) density reveals large variation around the atoms, the intrinsic contribution to the MAE is found to mainly come from the Fe layer. The surface without the capping Pt layer also shows similar linear dependence.

  18. Understanding the electronic band structure of Pt-alloys for surface reactivity

    NASA Astrophysics Data System (ADS)

    Jung, Jongkeun; Kim, Beomyoung; Hong, Ji Sook; Jin, Tae Won; Shim, Ji Hoon; Nemsak, Slavomir; Denlinger, Jonathan D.; Masashi, Arita; Kenya, Shimada; Kim, Changyoung; Mun, Bongjin Simon

    In polymer exchange membrane fuel cell (PEMFC), the oxygen reduction reaction (ORR) at cathode side has been continuously investigated due to its critical importance in performance of fuel cell. So far, even with best industrial catalyst made with Pt, the performance of ORR is too far below from the commercial purpose. In 2007, Stamenkovic et al. showed that Pt alloys with 3- dtransition metal exhibited significantly improved ORR performance and pointed out the altered electronic structure of surface as the major contributing factor for enhanced ORR. Since 1990, with the advance of DFT calculation, the trend of surface chemical reactivity is explained with the analysis of d-band structures, known as d-band model. While d-band provides valid insight on surface chemical reactivity based on the valence band DOS, the relation between surface work function and DOS has not been well understood. The element-specific local electronic band structure of Pt alloys are identified by ARPES measurement, and the correlation between surface work function and local charge density is investigated.

  19. Oxidation mechanism of formic acid on the bismuth adatom-modified Pt(111) surface.

    PubMed

    Perales-Rondón, Juan Victor; Ferre-Vilaplana, Adolfo; Feliu, Juan M; Herrero, Enrique

    2014-09-24

    In order to improve catalytic processes, elucidation of reaction mechanisms is essential. Here, supported by a combination of experimental and computational results, the oxidation mechanism of formic acid on Pt(111) electrodes modified by the incorporation of bismuth adatoms is revealed. In the proposed model, formic acid is first physisorbed on bismuth and then deprotonated and chemisorbed in formate form, also on bismuth, from which configuration the C-H bond is cleaved, on a neighbor Pt site, yielding CO2. It was found computationally that the activation energy for the C-H bond cleavage step is negligible, which was also verified experimentally.

  20. Surface sensitivity of the spin Seebeck effect in the Pt/YIG system

    NASA Astrophysics Data System (ADS)

    Aqeel, Aisha; Vera-Marun, Ivan J.; van Wees, Bart J.; Palstra, Thomas T. M.

    2015-03-01

    It is well-known that the surface plays an important role in the spin Seebeck effect (SSE). However the effect of mechanical treatment on the SSE has not been systematically studied yet. Here, we have investigated the influence of the interface quality on the SSE in a bilayer system of platinum and yttrium iron garnet (Pt/YIG). The surfaces of the YIG crystals are modified by different types of mechanical polishing before Pt deposition for different samples. We observed that the magnitude and magnetic field dependence of the SSE is strongly influenced by mechanical treatment of the YIG surface. No definite relation has been found between the SSE response and the sample roughness. However, we observe a direct correlation between the saturation magnetic field (Hsat) of the SSE and the roughness of sample, as the former increases by moving from soft toward coarse particle polishing. The change in the magnitude of Hsat can be attributed to the presence of a perpendicular magnetic anisotropy due to the treatment induced surface strain or shape anisotropy in the Pt/YIG system.

  1. Enhancement of oxygen reduction reaction activities by Pt nanoclusters decorated on ordered mesoporous porphyrinic carbons

    SciTech Connect

    Sun-Mi Hwang; Choi, YongMan; Kim, Min Gyu; Sohn, Young-Jun; Cheon, Jae Yeong; Joo, Sang Hoon; Yim, Sung-Dae; Kuttiyiel, Kurian A.; Sasaki, Kotaro; Adzic, Radoslav R.; Park, Gu-Gon

    2016-03-08

    The high cost of Pt-based membrane electrode assemblies (MEAs) is a critical hurdle for the commercialization of polymer electrolyte fuel cells (PEFCs). Recently, non-precious metal-based catalysts (NPMCs) have demonstrated much enhanced activity but their oxygen reduction reaction (ORR) activity is still inferior to that of Pt-based catalysts resulting in a much thicker electrode in the MEA. For the reduction of mass transport and ohmic overpotential we adopted a new concept of catalyst that combines an ultra-low amount of Pt nanoclusters with metal–nitrogen (M–Nx) doped ordered mesoporous porphyrinic carbon (FeCo–OMPC(L)). The 5 wt% Pt/FeCo–OMPC(L) showed a 2-fold enhancement in activities compared to a higher loading of Pt. Our experimental results supported by first-principles calculations indicate that a trace amount of Pt nanoclusters on FeCo–OMPC(L) significantly enhances the ORR activity due to their electronic effect as well as geometric effect from the reduced active sites. Finally, in terms of fuel cell commercialization, this class of catalysts is a promising candidate due to the limited use of Pt in the MEA.

  2. Enhancement of oxygen reduction reaction activities by Pt nanoclusters decorated on ordered mesoporous porphyrinic carbons

    DOE PAGES

    Sun-Mi Hwang; Choi, YongMan; Kim, Min Gyu; ...

    2016-03-08

    The high cost of Pt-based membrane electrode assemblies (MEAs) is a critical hurdle for the commercialization of polymer electrolyte fuel cells (PEFCs). Recently, non-precious metal-based catalysts (NPMCs) have demonstrated much enhanced activity but their oxygen reduction reaction (ORR) activity is still inferior to that of Pt-based catalysts resulting in a much thicker electrode in the MEA. For the reduction of mass transport and ohmic overpotential we adopted a new concept of catalyst that combines an ultra-low amount of Pt nanoclusters with metal–nitrogen (M–Nx) doped ordered mesoporous porphyrinic carbon (FeCo–OMPC(L)). The 5 wt% Pt/FeCo–OMPC(L) showed a 2-fold enhancement in activities comparedmore » to a higher loading of Pt. Our experimental results supported by first-principles calculations indicate that a trace amount of Pt nanoclusters on FeCo–OMPC(L) significantly enhances the ORR activity due to their electronic effect as well as geometric effect from the reduced active sites. Finally, in terms of fuel cell commercialization, this class of catalysts is a promising candidate due to the limited use of Pt in the MEA.« less

  3. PtSerpin from the swimming crab Portunus trituberculatus, a putative regulator of prophenoloxidase activation with antibacterial activity.

    PubMed

    Liu, Yuan; Shi, Guohui; Cui, Zhaoxia; Luo, Danli; Song, Chengwen; Li, Xihong; Hui, Min; Li, Yingdong

    2014-08-01

    Serpin or serine protease inhibitor is the largest family of protease inhibitors involved in many innate immune pathways, particularly the prophenoloxidase (proPO) activating system in arthropod. Here, we report the molecular and functional characterization of PtSerpin identified from the swimming crab Portunus trituberculatus. The genomic sequence encoding mature peptide of PtSerpin gene contained two exons of 84 and 1098 bp separated by one intron of 111 bp. The recombinant PtSerpin (rPtSerpin) with a predicted size of 44 kDa was expressed in Escherichia coli system, purified and assayed for its activities. The rPtSerpin exhibited inhibitory activity against trypsin in a dose-dependent manner, but did not affect chymotrypsin, which could define a role for PtSerpin as a trypsin inhibitor. The rPtSerpin could inhibit the growth of Gram-negative bacterium Vibrio alginolyticus, but not the tested Gram-positive bacterium and fungus. Further phenoloxidase (PO) assay showed PO activity was dramatically increased in hemocyte lysate supernatant of P. trituberculatus upon bacterial challenge. The rPtSerpin could depress the crab proPO system activation in vitro, and it could lead to 100% inhibition of PO activity under the concentration of 8.62 μM. Moreover, the rPtSerpin was able to inhibit the PO activity induced by rPtcSP and rPtSPH1. These results together indicate that PtSerpin is a potential trypsin inhibitor and may participate in crab innate immunity by the inhibition of bacterial growth and the regulation of proPO system.

  4. Polarization effects on the surface chemistry of PbTiO3-supported Pt films.

    PubMed

    Kolpak, Alexie M; Grinberg, Ilya; Rappe, Andrew M

    2007-04-20

    To demonstrate a new paradigm of dynamical control of surface structure and reactivity, we perform density functional theory calculations of the adsorption of several molecules and atoms to the surface of ultrathin Pt(100) films supported on ferroelectric PbTiO3. We show that reorienting the polarization direction of the substrate can dramatically change the chemisorption energies of CO, O, C, and N and alter the reaction pathways for dissociation of CO, O2, N2, and NO. We discuss the structural and electronic effects of a polarized substrate on the metal surface, and we suggest potential applications in tunable catalysis.

  5. Mechanism of oxygen reduction reaction on Pt(111) in alkaline solution: Importance of chemisorbed water on surface

    SciTech Connect

    Liu, Shizhong; White, Michael G.; Liu, Ping

    2016-06-30

    Here, we report a detailed mechanistic study of the oxygen reduction reaction (ORR) on Pt(111) in alkaline solution, combining density functional theory and kinetic Monte Carlo simulations. A complex reaction network including four possible pathways via either 2e or 4e transfer is established and is able to reproduce the experimental measured polarization curve at both low- and high-potential regions. Our results show that it is essential to account for solvation by water and the dynamic coverage of *OH to describe the reaction kinetics well. In addition, a chemisorbed water (*H2O)-mediated mechanism including 4e transfers is identified, where the reduction steps via *H2O on the surface are potential-independent and only the final removal of *OH from the surface in the form of OH(aq) contributes to the current. For the ORR in alkaline solutions, such a mechanism is more competitive than the associative and dissociative mechanisms typically used to describe the ORR in acid solution. Finally, *OH and **O2 intermediates are found to be critically important for tuning the ORR activity of Pt in alkaline solution. To enhance the activity, the binding of Pt should be tuned in such a way that *OH binding is weak enough to release more surface sites under working conditions, while **O2 binding is strong enough to enable the ORR via the 4e transfer mechanism.

  6. The stability and catalytic activity of W13@Pt42 core-shell structure

    PubMed Central

    Huo, Jin-Rong; Wang, Xiao-Xu; Li, Lu; Cheng, Hai-Xia; Su, Yan-Jing; Qian, Ping

    2016-01-01

    This paper reports a study of the electronic properties, structural stability and catalytic activity of the W13@Pt42 core-shell structure using the First-principles calculations. The degree of corrosion of W13@Pt42 core-shell structure is simulated in acid solutions and through molecular absorption. The absorption energy of OH for this structure is lower than that for Pt55, which inhibits the poison effect of O containing intermediate. Furthermore we present the optimal path of oxygen reduction reaction catalyzed by W13@Pt42. Corresponding to the process of O molecular decomposition, the rate-limiting step of oxygen reduction reaction catalyzed by W13@Pt42 is 0.386 eV, which is lower than that for Pt55 of 0.5 eV. In addition by alloying with W, the core-shell structure reduces the consumption of Pt and enhances the catalytic efficiency, so W13@Pt42 has a promising perspective of industrial application. PMID:27759038

  7. The stability and catalytic activity of W13@Pt42 core-shell structure

    NASA Astrophysics Data System (ADS)

    Huo, Jin-Rong; Wang, Xiao-Xu; Li, Lu; Cheng, Hai-Xia; Su, Yan-Jing; Qian, Ping

    2016-10-01

    This paper reports a study of the electronic properties, structural stability and catalytic activity of the W13@Pt42 core-shell structure using the First-principles calculations. The degree of corrosion of W13@Pt42 core-shell structure is simulated in acid solutions and through molecular absorption. The absorption energy of OH for this structure is lower than that for Pt55, which inhibits the poison effect of O containing intermediate. Furthermore we present the optimal path of oxygen reduction reaction catalyzed by W13@Pt42. Corresponding to the process of O molecular decomposition, the rate-limiting step of oxygen reduction reaction catalyzed by W13@Pt42 is 0.386 eV, which is lower than that for Pt55 of 0.5 eV. In addition by alloying with W, the core-shell structure reduces the consumption of Pt and enhances the catalytic efficiency, so W13@Pt42 has a promising perspective of industrial application.

  8. The stability and catalytic activity of W13@Pt42 core-shell structure.

    PubMed

    Huo, Jin-Rong; Wang, Xiao-Xu; Li, Lu; Cheng, Hai-Xia; Su, Yan-Jing; Qian, Ping

    2016-10-19

    This paper reports a study of the electronic properties, structural stability and catalytic activity of the W13@Pt42 core-shell structure using the First-principles calculations. The degree of corrosion of W13@Pt42 core-shell structure is simulated in acid solutions and through molecular absorption. The absorption energy of OH for this structure is lower than that for Pt55, which inhibits the poison effect of O containing intermediate. Furthermore we present the optimal path of oxygen reduction reaction catalyzed by W13@Pt42. Corresponding to the process of O molecular decomposition, the rate-limiting step of oxygen reduction reaction catalyzed by W13@Pt42 is 0.386 eV, which is lower than that for Pt55 of 0.5 eV. In addition by alloying with W, the core-shell structure reduces the consumption of Pt and enhances the catalytic efficiency, so W13@Pt42 has a promising perspective of industrial application.

  9. Faraday efficiency and mechanism of electrochemical surface reactions: CO2 reduction and H2 formation on Pt(111).

    PubMed

    Hussain, Javed; Jónsson, Hannes; Skúlason, Egill

    2016-12-22

    An atomic scale model of the electrical double layer is used to calculate the mechanism and rate of electrochemical reduction of CO2 as well as H2 formation at a Pt(111) electrode. The water layer contains solvated protons and the electrode has excess electrons at the surface. Density functional theory within the generalized gradient approximation is used to describe the electronic structure while the mechanism and activation energy of the various elementary reactions is obtained by calculating minimum energy paths using the nudged elastic band method. The applied electrical potential is deduced from the calculated work function. The optimal reaction mechanism for CO2 reduction to either methane or methanol is found and the estimated rate compared with that of the competing reaction, H2 formation. When the free energy of only the intermediates and reactants is taken into account, not the activation energy, Pt(111) would seem to be a good electrocatalyst for CO2 reduction, significantly better than Cu(111). This, however, contradicts experimental findings. Detailed calculations reported here show that the activation energy for CO2 reduction is high for both Heyrovsky and Tafel mechanisms on Pt(111) in the relevant range of applied potential. The rate-limiting step of the Heyrovsky mechanism, *COOH + H(+) + e(-) → *CO + H2O, is estimated to have an activation energy of 0.95 eV at -0.9 V vs. standard hydrogen electrode. Under the same conditions, the activation energy for H2 formation is estimated to be only 0.5 eV. This explains why attempts to reduce CO2 using platinum electrodes have produced only H2. A comparison is made with analogous results for Cu(111) [J. Hussain et al., Procedia Comput. Sci., 2015, 51, 1865] where a reaction mechanism with low activation energy for CO2 electroreduction to methane was identified. The difference between the two electrocatalysts is discussed.

  10. Synthesis of Highly Active Sub-Nanometer Pt@Rh Core-Shell Nanocatalyst via a Photochemical Route: Porous Titania Nanoplates as a Superior Photoactive Support.

    PubMed

    Zhan, Wen-Wen; Zhu, Qi-Long; Dang, Song; Liu, Zheng; Kitta, Mitsunori; Suenaga, Kazutomo; Zheng, Lan-Sun; Xu, Qiang

    2017-02-02

    Sub-nanometer Pt@Rh nanoparticles highly dispersed on MIL-125-derived porous TiO2 nanoplates are successfully prepared for the first time by a photochemical route, where the porous TiO2 nanoplates with a relatively high specific surface area play a dual role as both effective photoreductant and catalyst support. The resulting Pt@Rh/p-TiO2 can be utilized as a highly active catalyst.

  11. Influences of surface coatings and components of FePt nanoparticles on the suppression of glioma cell proliferation.

    PubMed

    Sun, Haiming; Chen, Xiaohui; Chen, Dan; Dong, Mingyan; Fu, Xinning; Li, Qian; Liu, Xi; Wu, Qingzhi; Qiu, Tong; Wan, Tao; Li, Shipu

    2012-01-01

    Malignant gliomas are primary brain tumors with high rates of morbidity and mortality; they are the fourth most common cause of cancer death. Novel diagnostic and therapeutic techniques based on nanomaterials provide promising options in the treatment of malignant gliomas. In order to evaluate the potential of FePt nanoparticles (NPs) for malignant glioma therapy, FePt NPs with different surface coatings and components were tunably synthesized using oleic acid/oleylamine (OA/OA) and cysteines (Cys) as the capping agents, respectively. The samples were characterized using X-ray diffraction, transmission electron microscopy (TEM), X-ray photon spectroscopy, Fourier transform infrared spectroscopy, atomic absorption spectrum, and zeta potential. The influence of the surface coatings and components of the FePt NPs on the proliferation of glioma cells was assessed through MTT assay and TEM observation using three typical glioma cell lines (glioma U251 cells, astrocytoma U87 cells, and neuroglioma H4 cells) as in vitro models. The results showed that the proliferation of glioma cells was significantly suppressed by lipophilic FePt-OA/OA NPs in a time- and/or dose-dependent manner, while no or low cytotoxic effects were detected in the case of hydrophilic FePt-Cys NPs. The IC₅₀ value of FePt-OA/OA NPs on the three glioma cell lines was approximately 5-10 μg mL⁻¹ after 24 hours' incubation. Although the cellular uptake of FePt NPs was confirmed regardless of the surface coatings and components of the FePt NPs, the suppression of FePt NPs on glioma cell proliferation was dominantly determined by their surface coatings rather than their components. Therefore, these results demonstrate that, through engineering of the surface coating, FePt NPs can potentially be developed as novel therapeutic agents for malignant gliomas.

  12. PdCu@Pd Nanocube with Pt-like Activity for Hydrogen Evolution Reaction.

    PubMed

    Li, Jing; Li, Feng; Guo, Si-Xuan; Zhang, Jie; Ma, Jiantai

    2017-02-27

    The electronic properties of metal surfaces can be modulated to weaken the binding energy of adsorbed H-intermediates on the catalyst surface, thus enhancing catalytic activity for the hydrogen evolution reaction (HER). Here we first prepare PdCu alloy nanocubes (NCs) by coreduction of Cu(acac)2 (acac = acetylacetonate) and Na2PdCl4 in the presence of oleylamine (OAm) and trioctylphosphine (TOP). The PdCu NC coated glassy carbon electrode is then anodized at a constant potential of 0.51 V vs Ag/AgCl at room temperature in 0.5 M H2SO4 solution for 10 s, which converts PdCu NCs into core@shell PdCu@Pd NCs that show much enhanced Pt-like activity for the HER and much more robust durability. The improvements in surface property and HER activity are rationalized based on strain and ligand effects that enhance the activity of the edge-exposed Pd atoms on core@shell PdCu@Pd structure. This work opens up a new perspective for simultaneously reducing metal Pd cost and achieving excellent performance toward the HER.

  13. Effect of Sb Segregation on Conductance and Catalytic Activity at Pt/Sb-Doped SnO2 Interface: A Synergetic Computational and Experimental Study.

    PubMed

    Fu, Qiang; Colmenares Rausseo, Luis César; Martinez, Umberto; Dahl, Paul Inge; García Lastra, Juan Maria; Vullum, Per Erik; Svenum, Ingeborg-Helene; Vegge, Tejs

    2015-12-23

    Antimony-doped tin dioxide (ATO) is considered a promising support material for Pt-based fuel cell cathodes, displaying enhanced stability over carbon-based supports. In this work, the effect of Sb segregation on the conductance and catalytic activity at Pt/ATO interface was investigated through a combined computational and experimental study. It was found that Sb-dopant atoms prefer to segregate toward the ATO/Pt interface. The deposited Pt catalysts, interestingly, not only promote Sb segregation, but also suppress the occurrence of Sb(3+) species, a charge carrier neutralizer at the interface. The conductivity of ATO was found to increase, to a magnitude close to that of activated carbon, with an increment of Sb concentration before reaching a saturation point around 10%, and then decrease, indicating that Sb enrichment at the ATO surface may not always favor an increment of the electric current. In addition, the calculation results show that the presence of Sb dopants in ATO has little effect on the catalytic activity of deposited three-layer Pt toward the oxygen reduction reaction, although subsequent alloying of Pt and Sb could lower the corresponding catalytic activity. These findings help to support future applications of ATO/Pt-based materials as possible cathodes for proton exchange membrane fuel cell applications with enhanced durability under practical applications.

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

    NASA Astrophysics Data System (ADS)

    Nowicki, Waldemar; Gąsowska, Anna; Kirszensztejn, Piotr

    2016-05-01

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

  15. Chemiluminescence lateral flow immunoassay based on Pt nanoparticle with peroxidase activity.

    PubMed

    Park, Jong-Min; Jung, Ha-Wook; Chang, Young Wook; Kim, Hyung-Seok; Kang, Min-Jung; Pyun, Jae-Chul

    2015-01-01

    A lateral flow immunoassay (LF-immunoassay) with an enhanced sensitivity and thermostability was developed by using Pt nanoparticles with a peroxidase activity. The Pt nanoparticles were synthesized by citrate reduction method, and the peroxidase activity of Pt nanoparticles was optimized by adjusting reaction conditions. The peroxidase activity was estimated by using Michaelis-Menten kinetics model with TMB as a chromogenic substrate. The kinetics parameters of KM and Vmax were calculated and compared with horseradish peroxidase (HRP). The thermal stability of the Pt nanoparticles was compared with horseradish peroxidase (HRP) according to the storage temperature and long-term storage period. The feasibility of lateral flow immunoassay with a chemiluminescent signal band was demonstrated by the detection of human chorionic gonadotropin (hCG) as a model analyte, and the sensitivity was determined to be improved by as much as 1000-fold compared to the conventional rapid test based on colored gold-colloids.

  16. Tuning electrocatalytic activity of Pt monolayer shell by bimetallic Ir-M (M=Fe, Co, Ni or Cu) cores for the oxygen reduction reaction

    SciTech Connect

    Kuttiyiel, Kurian A.; Choi, YongMan; Sasaki, Kotaro; Su, Dong; Hwang, Sun -Mi; Yim, Sung -Dae; Yang, Tae -Hyun; Park, Gu -Gon; Adzic, Radoslav R.

    2016-05-18

    Here, platinum monolayer electrocatalyst are known to exhibit excellent oxygen reduction reaction (ORR) activity depending on the type of substrate used. Here we demonstrate a relationship between the ORR electrocatalytic activity and the surface electronic structure of Pt monolayer shell induced by various IrM bimetallic cores (M=Fe, Co, Ni or Cu). The relationship is rationalized by comparing density functional theory calculations and experimental results. For an efficient Pt monolayer electrocatalyst, the core should induce sufficient contraction to the Pt shell leading to a downshift of the d-band center with respect to the Fermi level. Depending on the structure of the IrM, relative to that of pure Ir, this interaction not only alters the electronic and geometric structure but also induces segregation effects. Combined these effects significantly enhance the ORR activities of the Pt monolayer shell on bimetallic Ir cores electrocatalysts.

  17. Tuning electrocatalytic activity of Pt monolayer shell by bimetallic Ir-M (M=Fe, Co, Ni or Cu) cores for the oxygen reduction reaction

    DOE PAGES

    Kuttiyiel, Kurian A.; Choi, YongMan; Sasaki, Kotaro; ...

    2016-05-18

    Here, platinum monolayer electrocatalyst are known to exhibit excellent oxygen reduction reaction (ORR) activity depending on the type of substrate used. Here we demonstrate a relationship between the ORR electrocatalytic activity and the surface electronic structure of Pt monolayer shell induced by various IrM bimetallic cores (M=Fe, Co, Ni or Cu). The relationship is rationalized by comparing density functional theory calculations and experimental results. For an efficient Pt monolayer electrocatalyst, the core should induce sufficient contraction to the Pt shell leading to a downshift of the d-band center with respect to the Fermi level. Depending on the structure of themore » IrM, relative to that of pure Ir, this interaction not only alters the electronic and geometric structure but also induces segregation effects. Combined these effects significantly enhance the ORR activities of the Pt monolayer shell on bimetallic Ir cores electrocatalysts.« less

  18. Enhanced electrocatalytic activity and stability of Pd3V/C nanoparticles with a trace amount of Pt decoration for the oxygen reduction reaction

    SciTech Connect

    Liu, Sufen; Han, Lili; Zhu, Jing; Xiao, Weiping; Wang, Jie; Liu, Hongfang; Xin, Huolin; Wang, Deli

    2015-09-14

    In this study, carbon supported Pd3V bimetallic alloy nanoparticles (Pd3V/C) have been successfully synthesized via a simple impregnation–reduction method, followed by high temperature treatment under a H2 atmosphere. Electrochemical tests reveal that the half-wave potential of Pd3V/C-500 shifts positively 40 mV compared with Pd/C. However, the catalytic activity of Pd3V/C-500 suffers from serious degradation after 1k cycles. By a spontaneous displacement reaction or co-reduction method, a trace amount of Pt was decorated on the surface or inside of the Pd3V/C nanoparticles. The catalytic activity and stability of the Pd3V@Pt/C and Pt-Pd3V/C catalysts for the oxygen reduction reaction (ORR) are enhanced significantly, and are comparable to commercial Pt/C. In addition, the Pt mass activity of Pd3V@Pt/C and Pt-Pd3V/C improves by factors of 10.9 and 6.5 at 0.80 V relative to Pt/C. Moreover, Pt-decorated Pd3V/C nanoparticles show almost no obvious morphology change after durability tests, because the Pt-rich shell plays an important role in preventing degradation.

  19. A Selective Blocking Method To Control the Overgrowth of Pt on Au Nanorods

    PubMed Central

    2013-01-01

    A method for the preparation of smooth deposits of Pt on Au nanorods is described, involving sequential deposition steps with selective blocking of surface sites that reduces Pt-on-Pt deposition. The Au–Pt nanorods prepared by this method have higher long-term stability than those prepared by standard Pt deposition. Electrochemical data show that the resulting structure has more extended regions of Pt surface and enhanced activity toward the carbon monoxide oxidation and oxygen reduction reactions. PMID:23594230

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

    NASA Astrophysics Data System (ADS)

    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.

  1. Investigation of the contrast inversion effect on hydrophilic surfaces using Pt/C whisker probes in a scanning force microscope

    NASA Astrophysics Data System (ADS)

    Zhukov, M. V.; Mukhin, I. S.; Levichev, V. V.; Golubok, A. O.

    2015-02-01

    We compare the spatial resolution and image contrast of an erythrocyte surface obtained by means of scanning force microscopy (SFM) with conventional hydrophobic Si probes and probes modified by hydrophilic Pt/C whisker probes. It is shown that probes with Pt/C nanowhiskers provide a higher spatial resolution and contrast when imaging relief on the surface of erythrocytes. The contrast inversion is revealed in some areas of the SFM images when replacing Si probes by probes with Pt/C nanowhiskers. The origin of this inversion in the tapping and contact modes is discussed.

  2. New Pt-NNSO core anticancer agents: Structural optimization and investigation of their anticancer activity.

    PubMed

    Chong, Shu Xian; Jin, Yinxue; Au-Yeung, Steve Chik Fun; To, Kenneth Kin Wah

    2017-02-12

    A series of new platinum Pt(II) compounds possessing a bidentate leaving ligand modified from oxaliplatin has been synthesized, with one of the oxygen ligating atom substituted for a sulphur atom (resulting in a Pt-NNSO coordination core structure). The general structures are R,R-diaminocyclohexane (DACH)-Pt-(methylthio)acetic acid (K4) and DACH-Pt-(thiophenylacetic acid) (K4 derivatives). Substitution of an electron donating or withdrawing group at the ortho or para position on the phenyl ring of K4 derivatives was found to affect the complexes' stability, reactivity with the biological molecules (5'-guanosine monophosphate (5'-GMP) and L-methionine (L-Met)) and anticancer activity. (1)H NMR experiments demonstrated that Pt-NNSO complexes formed a mixture of mono- and diadduct with 5'-GMP in various ratios, which are different from the classical Pt drugs (forming mainly diadduct). In addition, all of the K4 derivatives with improved lipophilicity are less deactivated by L-Met in comparison to cisplatin (CDDP) and oxaliplatin. Biological assessments showed that all Pt-NNSO complexes are less toxic than CDDP in normal porcine kidney cells and are minimally affected by drug resistance. Some of the new compounds also displayed comparable anticancer activity to CDDP or better than carboplatin in a few cancer cell lines. The lower reactivity of the Pt-NNSO compounds than CDDP towards thiol molecules, presumably leading to less efflux in resistant cancer cells, and the ability to inhibit autophagy were believed to allow the new compounds to be less affected by Pt resistance.

  3. Homogeneous Pt-bimetallic Electrocatalysts

    SciTech Connect

    Wang, Chao; Chi, Miaofang; More, Karren Leslie; Markovic, Nenad; Stamenkovic, Vojislav

    2011-01-01

    Alloying has shown enormous potential for tailoring the atomic and electronic structures, and improving the performance of catalytic materials. Systematic studies of alloy catalysts are, however, often compromised by inhomogeneous distribution of alloying components. Here we introduce a general approach for the synthesis of monodispersed and highly homogeneous Pt-bimetallic alloy nanocatalysts. Pt{sub 3}M (where M = Fe, Ni, or Co) nanoparticles were prepared by an organic solvothermal method and then supported on high surface area carbon. These catalysts attained a homogeneous distribution of elements, as demonstrated by atomic-scale elemental analysis using scanning transmission electron microscopy. They also exhibited high catalytic activities for the oxygen reduction reaction (ORR), with improvement factors of 2-3 versus conventional Pt/carbon catalysts. The measured ORR catalytic activities for Pt{sub 3}M nanocatalysts validated the volcano curve established on extended surfaces, with Pt{sub 3}Co being the most active alloy.

  4. Synthesis of surface roughed Pt nanowires and their application as electrochemical sensors for hydrogen peroxide detection.

    PubMed

    Gao, Fan; Li, Zhiyang; Ruan, Dajiang; Gu, Zhiyong

    2014-09-01

    In this paper, platinum nanowires with roughed surface textures were fabricated by a galvanostatic electrodeposition method for electrochemical sensors toward hydrogen peroxide detection. The electrochemical behavior of the glassy carbon electrode modified with these nanowires has been studied for oxidation of hydrogen peroxide by using cyclic voltammetry and amperometry in phosphate buffer solution. Surface roughness was found to enhance the sensitivity of the Pt nanowire based electrochemical sensor towards H2O2. The Pt nanowires with rough surfaces displayed higher electrocatalytic response compared to nanowires with smooth surfaces, with a sensitivity of 171 μA mM(-1) cm(-2), and linear dynamic range up to 35 mM. The nanowire concentration effect on the sensing behavior was investigated with the best sensitivity output found at a nanowire concentration of roughly 8.6 x 10(7) number of nanowires/cm2. The new sensor also showed good anti-interference property and exhibited high accuracy when a real water sample containing H2O2 was measured.

  5. Enhanced Activity of Supported Ni Catalysts Promoted by Pt for Rapid Reduction of Aromatic Nitro Compounds

    PubMed Central

    Shang, Huishan; Pan, Kecheng; Zhang, Lu; Zhang, Bing; Xiang, Xu

    2016-01-01

    To improve the activities of non-noble metal catalysts is highly desirable and valuable to the reduced use of noble metal resources. In this work, the supported nickel (Ni) and nickel-platinum (NiPt) nanocatalysts were derived from a layered double hydroxide/carbon composite precursor. The catalysts were characterized and the role of Pt was analysed using X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), energy dispersive X-ray spectroscopy (EDS) mapping, and X-ray photoelectron spectroscopy (XPS) techniques. The Ni2+ was reduced to metallic Ni0 via a self-reduction way utilizing the carbon as a reducing agent. The average sizes of the Ni particles in the NiPt catalysts were smaller than that in the supported Ni catalyst. The electronic structure of Ni was affected by the incorporation of Pt. The optimal NiPt catalysts exhibited remarkably improved activity toward the reduction of nitrophenol, which has an apparent rate constant (Ka) of 18.82 × 10−3 s−1, 6.2 times larger than that of Ni catalyst and also larger than most of the reported values of noble-metal and bimetallic catalysts. The enhanced activity could be ascribed to the modification to the electronic structure of Ni by Pt and the effect of exposed crystal planes. PMID:28335231

  6. Enhanced Activity of Supported Ni Catalysts Promoted by Pt for Rapid Reduction of Aromatic Nitro Compounds.

    PubMed

    Shang, Huishan; Pan, Kecheng; Zhang, Lu; Zhang, Bing; Xiang, Xu

    2016-06-04

    To improve the activities of non-noble metal catalysts is highly desirable and valuable to the reduced use of noble metal resources. In this work, the supported nickel (Ni) and nickel-platinum (NiPt) nanocatalysts were derived from a layered double hydroxide/carbon composite precursor. The catalysts were characterized and the role of Pt was analysed using X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), energy dispersive X-ray spectroscopy (EDS) mapping, and X-ray photoelectron spectroscopy (XPS) techniques. The Ni(2+) was reduced to metallic Ni⁰ via a self-reduction way utilizing the carbon as a reducing agent. The average sizes of the Ni particles in the NiPt catalysts were smaller than that in the supported Ni catalyst. The electronic structure of Ni was affected by the incorporation of Pt. The optimal NiPt catalysts exhibited remarkably improved activity toward the reduction of nitrophenol, which has an apparent rate constant (Ka) of 18.82 × 10(-3) s(-1), 6.2 times larger than that of Ni catalyst and also larger than most of the reported values of noble-metal and bimetallic catalysts. The enhanced activity could be ascribed to the modification to the electronic structure of Ni by Pt and the effect of exposed crystal planes.

  7. Lignin-derived oxygenate reforming on a bimetallic surface: The reaction of benzaldehyde on Zn/Pt(111)

    NASA Astrophysics Data System (ADS)

    Shi, Daming; Vohs, John M.

    2016-08-01

    Temperature programmed desorption (TPD) and high-resolution electron energy loss spectroscopy (HREELS) were used to characterize the adsorption and reaction of benzaldehyde (C6H5CHO) on hydrogen-covered Pt(111) and Zn-modified Pt(111) surfaces. Benzaldehyde was found to interact with Pt(111) via both the phenyl ring and carbonyl of the aldehyde group. This bonding configuration facilitates unselective decomposition of the benzaldehyde to produce CO, H2, and small hydrocarbon fragments at relatively low temperatures. On the other hand, benzaldehyde was found to bond to Zn-decorated Pt(111) surface exclusively via the carbonyl group in an η2(C, O) configuration, with the phenyl ring tilted away from the surface. This configuration weakens Csbnd O bond in the carbonyl facilitating its cleavage and helps prevent hydrogenation of the phenyl ring.

  8. Preparation and characterization of nano-sized Pt-Ru/C catalysts and their superior catalytic activities for methanol and ethanol oxidation.

    PubMed

    Şen, Selda; Şen, Fatih; Gökağaç, Gülsün

    2011-04-21

    Carbon-supported PtRu nanoparticles (Ru/Pt: 0.25) were prepared by three different methods; simultaneous reduction of PtCl(4) and RuCl(3) (catalyst I) and changing the reduction order of PtCl(4) and RuCl(3) (catalysts II and III) to enhance the performance of the anodic catalysts for methanol and ethanol oxidation. Structure, microstructure and surface characterizations of all the catalysts were carried out by X-ray diffraction (XRD), transmission electron microscopy (TEM) coupled with energy dispersive X-ray spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS). The results of the XRD analysis showed that all catalysts had a face-centered cubic (fcc) structure with different and smaller lattice parameters than that of pure platinum, showing that the Ru incorporates into the Pt fcc structure by different ratios in all the catalysts. The typical particle sizes of all catalysts were in the range of 2-3 nm. The most active and stable catalyst for methanol and ethanol oxidation is catalyst III, in which a large amount (more than 90%) of PtRu alloy formation was observed. It has been found that this catalyst is about 8.0 and 33.4 times more active at ∼0.60 V towards the methanol and ethanol oxidation reactions, respectively, compared to the commercial Pt catalyst.

  9. Synthesis and Catalytic Activity of Pt Monolayer on Pd Tetrahedral Nanocrystals with CO-adsorption-induced Removal of Surfactants

    SciTech Connect

    Gong K.; Vukmirovic M.B.; Ma C.; Zhu Y.; Adzic R.R.

    2011-11-01

    We synthesized the Pt monolayer shell-Pd tetrahedral core electrocatalysts that are notable for their high activity and stable performance. A small number of low-coordination sites and defects, and high content of the (1 1 1)-oriented facets on Pd tetrahedron makes them a suitable support for a Pt monolayer to obtain an active O{sub 2} reduction reaction (ORR) electrocatalyst. The surfactants, used to control size and shape of Pd tetrahedral nanoparticles, are difficult to remove and cause adverse effects on the ORR. We describe a simple and noninvasive method to synthesize high-purity tetrahedral Pd nanocrystals (TH Pd) by combining a hydrothermal route and CO adsorption-induced removal of surfactants. Poly(vinylpyrrolidone) (PVP), used as a protecting and reducing agent in hydrothermal reactions, is strongly bonded to the surface of the resulting nanocrystals. We demonstrate that PVP was displaced efficiently by adsorbed CO. A clean surface was achieved upon CO stripping at a high potential (1.0 V vs RHE). It played a decisive role in improving the activity of the Pt monolayer/TH Pd electrocatalyst for the ORR. Furthermore, the results demonstrate a versatile method for removal of surfactants from various nanoparticles that severely limited their applications.

  10. Light-controlled propulsion, aggregation and separation of water-fuelled TiO2/Pt Janus submicromotors and their ``on-the-fly'' photocatalytic activities

    NASA Astrophysics Data System (ADS)

    Mou, Fangzhi; Kong, Lei; Chen, Chuanrui; Chen, Zhihong; Xu, Leilei; Guan, Jianguo

    2016-02-01

    In this work, water-fuelled TiO2/Pt Janus submicromotors with light-controlled motions have been developed by utilizing the asymmetrical photocatalytic water redox reaction over TiO2/Pt Janus submicrospheres under UV irradiation. The motion state, speed, aggregation and separation behaviors of the TiO2/Pt Janus submicromotor can be reversibly, wirelessly and remotely controlled at will by regulating the ``on/off'' switch, intensity and pulsed/continuous irradiation mode of UV light. The motion of the water-fuelled TiO2/Pt Janus submicromotor is governed by light-induced self-electrophoresis under the local electrical field generated by the asymmetrical water oxidation and reduction reactions on its surface. The TiO2/Pt Janus submicromotors can interact with each other through the light-switchable electrostatic forces, and hence continuous and pulsed UV irradiation can make the TiO2/Pt Janus submicromotors aggregate and separate at will, respectively. Because of the enhanced mass exchange between the environment and active submicromotors, the separated TiO2/Pt Janus submicromotors powered by the pulsed UV irradiation show a much higher activity for the photocatalytic degradation of the organic dye than the aggregated TiO2/Pt submicromotors. The water-fuelled TiO2/Pt Janus submicromotors developed here have some outstanding advantages as ``swimming'' photocatalysts for organic pollutant remediation in the macro or microenvironment (microchannels and microwells in microchips) because of their small size, long-term stability, wirelessly controllable motion behaviors and long life span.In this work, water-fuelled TiO2/Pt Janus submicromotors with light-controlled motions have been developed by utilizing the asymmetrical photocatalytic water redox reaction over TiO2/Pt Janus submicrospheres under UV irradiation. The motion state, speed, aggregation and separation behaviors of the TiO2/Pt Janus submicromotor can be reversibly, wirelessly and remotely controlled at will by

  11. Controlled synthesis of Pt nanoparticles array through electroreduction of cisplatin bound at nucleobases terminated surface and application into H2O2 sensing.

    PubMed

    Ji, Shujun; Guo, Qingqing; Yue, Qiaoli; Wang, Lei; Wang, Huaisheng; Zhao, Jinsheng; Dong, Ruixin; Liu, Jifeng; Jia, Jianbo

    2011-01-15

    Fabrication of sub-monolayer array of Pt nanoparticles (PtNPs) assembled at nucleobases terminated layers and their application into H(2)O(2) and glucose sensing were reported. To prepare such a PtNPs assembly, 3-mercaptopropionic acid (MPA), Zr(4+), nucleotide-5'-monophosphate (NTMP including guanosine, adenosine, cytidine, uridine-5'-monophosphate, and abbreviations were GMP, AMP, CMP, UMP, respectively) were adsorbed onto Au substrate sequentially to form nucleobases terminated surface and Zr(4+) acted as binder to link carboxylic and phosphoric groups (NTMP/Zr(4+)/MPA/Au). Complexation of cisplatin, cis-Pt(NH(3))(2)Cl(2), with terminated nucleobases and following electrochemical reduction of surface-bound cisplatin gave PtNPs attached surface. Different PtNPs coverage or particle density was obtained depending on the NTMP used and decreased in the order: PtNPs/GMP/Zr(4+)/MPA/Au>PtNPs/AMP/Zr(4+)/MPA/Au>PtNPs/CMP/Zr(4+)/MPA/Au>PtNPs/UMP/Zr(4+)/MPA/Au. The surface loading of Pt was between 160 and 16 ng/cm(2). The as prepared PtNPs can be used as electrocatalysts for H(2)O(2) sensing (detection limit of H(2)O(2)<100 nM) and the sensitivity increased with decreasing PtNPs density. After adsorption of glucose oxidase, the modified electrode can be used as enzymatic electrode for glucose sensing and a detection limit of 38.5 μM was achieved. This study provided an example of fabricating PtNP arrays utilising surface complexation of cisplatin with nucleobases. The advantage of this method is that the NP density can be controlled through changing nucleobases or Pt complexes used to obtain suitable kinetics of the complexation reactions. Additionally, the PtNPs sub-monolayer as prepared has high sensitivity for H(2)O(2) sensing even at a very low loading of Pt.

  12. Density functional theory study of the adsorption of MeOH and EtOH on the surface of Pt-decorated graphene

    NASA Astrophysics Data System (ADS)

    Rad, Ali Shokuhi

    2016-09-01

    The adsorption energies and orientation of single alcohol molecule (methanol and ethanol) on the surface of Pt-decorated graphene (PtG) were determined from first-principles density functional (DFT) calculations. We found the same adsorption energies as well as connecting distances upon adsorption of MeOH and EtOH on PtG surface, in which at their relaxed structures, the O atom of alcohol is closed to the Pt of PtG surface. We found high adsorption energies, low connecting distances, and high orbital hybridizing upon adsorption of EtOH and MeOH molecules on PtG surface. There are significant shifts in the location of both the HOMO and LUMO, in addition to variation in the charge transfer when the MeOH and EtOH are adsorbed on PtG surface.

  13. Preparation of Pt/TiO2 hollow nanofibers with highly visible light photocatalytic activity

    NASA Astrophysics Data System (ADS)

    Yang, Ziling; Lu, Jing; Ye, Weichun; Yu, Chushu; Chang, Yanlong

    2017-01-01

    The Pt/TiO2 hollow nanofibers (HNFs) as a photocatalyst have been successfully prepared by a uniaxial electrospinning method combined with photo-deposition. The as-synthesized photocatalysts were characterized by TEM, XRD, SAED, EDX, XPS, N2 adsorption-desorption, and UV-vis DRS. The TiO2 HNFs were composed of an anatase-rutile mixed phase, with the ratio of ∼70:30. The band gap of TiO2 HNFs decreased from 3.09 down to 2.77 eV with 2 wt.% Pt loading, this led to an enhanced photocatalytic performance under visible light. By evaluating the degradation of azo dye Orange II, the pseudo-first-rate constant (k) of Pt/350-TiO2 HNFs system was 0.0069 min-1, which was 11.5 and 3.63 times higher than for TiO2 HNFs and Pt/P25, respectively. The main factors affecting the photocatalytic activity were further investigated, these included the loading amount of Pt, the calcination temperature of TiO2 HNFs, the pH of initial solution and the light source. The results of repeated use of the Pt/TiO2 HNFs demonstrated that the photocatalysts exhibited an excellent stability even after ten cycles. The possible degradation mechanism was also studied. It was shown that rad O2- radicals were the main reactive oxygen species for the degradation of Orange II.

  14. Preparation of preferentially exposed poison-resistant Pt(111) nanoplates with a nitrogen-doped graphene aerogel.

    PubMed

    Xie, Beibei; Zhang, Yong; Du, Na; Li, Haiping; Hou, Wanguo; Zhang, Renjie

    2016-12-11

    A poison-resistant and highly catalytically active Pt(111) lattice on ultrathin Pt nanoplates (Pt(111)NPTs) with a large ratio (28%) of surface active to sum Pt atoms is obtained with a dense small pore N-atom doped aerogel (NGA) featuring a large specific surface area and high N content in the graphene skeleton.

  15. Mild Synthesis of Pt/SnO2 /Graphene Nanocomposites with Remarkably Enhanced Ethanol Electro-oxidation Activity and Durability.

    PubMed

    Qu, Yunteng; Gao, Yunzhi; Wang, Long; Rao, Jiancun; Yin, Geping

    2016-01-04

    We have designed a new Pt/SnO2 /graphene nanomaterial by using L-arginine as a linker; this material shows the unique Pt-around-SnO2 structure. The Sn(2+) cations reduce graphene oxide (GO), leading to the in situ formation of SnO2 /graphene hybrids. L-Arginine is used as a linker and protector to induce the in situ growth of Pt nanoparticles (NPs) connected with SnO2 NPs and impede the agglomeration of Pt NPs. The obtained Pt/SnO2 /graphene composites exhibit superior electrocatalytic activity and stability for the ethanol oxidation reaction as compared with the commercial Pt/C catalyst owing to the close-connected structure between the Pt NPs and SnO2 NPs. This work should have a great impact on the rational design of future metal-metal oxide nanostructures with high catalytic activity and stability for fuel cell systems.

  16. Insight into the Role of Surface Wettability in Electrocatalytic Hydrogen Evolution Reactions Using Light-Sensitive Nanotubular TiO2 Supported Pt Electrodes

    PubMed Central

    Meng, Chenhui; Wang, Bing; Gao, Ziyue; Liu, Zhaoyue; Zhang, Qianqian; Zhai, Jin

    2017-01-01

    Surface wettability is of importance for electrochemical reactions. Herein, its role in electrochemical hydrogen evolution reactions is investigated using light-sensitive nanotubular TiO2 supported Pt as hydrogen evolution electrodes (HEEs). The HEEs are fabricated by photocatalytic deposition of Pt particles on TiO2 nanotubes followed by hydrophobization with vaporized octadecyltrimethoxysilane (OTS) molecules. The surface wettability of HEEs is subsequently regulated in situ from hydrophobicity to hydrophilicity by photocatalytic decomposition of OTS molecules using ultraviolet light. It is found that hydrophilic HEEs demonstrate a larger electrochemical active area of Pt and a lower adhesion force to a gas bubble when compared with hydrophobic ones. The former allows more protons to react on the electrode surface at small overpotential so that a larger current is produced. The latter leads to a quick release of hydrogen gas bubbles from the electrode surface at large overpotential, which ensures the contact between catalysts and electrolyte. These two characteristics make hydrophilic HEEs generate a much high current density for HERs. Our results imply that the optimization of surface wettability is of significance for improving the electrocatalytic activity of HEEs. PMID:28165487

  17. Insight into the Role of Surface Wettability in Electrocatalytic Hydrogen Evolution Reactions Using Light-Sensitive Nanotubular TiO2 Supported Pt Electrodes

    NASA Astrophysics Data System (ADS)

    Meng, Chenhui; Wang, Bing; Gao, Ziyue; Liu, Zhaoyue; Zhang, Qianqian; Zhai, Jin

    2017-02-01

    Surface wettability is of importance for electrochemical reactions. Herein, its role in electrochemical hydrogen evolution reactions is investigated using light-sensitive nanotubular TiO2 supported Pt as hydrogen evolution electrodes (HEEs). The HEEs are fabricated by photocatalytic deposition of Pt particles on TiO2 nanotubes followed by hydrophobization with vaporized octadecyltrimethoxysilane (OTS) molecules. The surface wettability of HEEs is subsequently regulated in situ from hydrophobicity to hydrophilicity by photocatalytic decomposition of OTS molecules using ultraviolet light. It is found that hydrophilic HEEs demonstrate a larger electrochemical active area of Pt and a lower adhesion force to a gas bubble when compared with hydrophobic ones. The former allows more protons to react on the electrode surface at small overpotential so that a larger current is produced. The latter leads to a quick release of hydrogen gas bubbles from the electrode surface at large overpotential, which ensures the contact between catalysts and electrolyte. These two characteristics make hydrophilic HEEs generate a much high current density for HERs. Our results imply that the optimization of surface wettability is of significance for improving the electrocatalytic activity of HEEs.

  18. Activated carbon fibers impregnated with Pd and Pt catalysts for toluene removal.

    PubMed

    Liu, Zhen-Shu; Chen, Jian-Yuan; Peng, Yu-Hui

    2013-07-15

    Few studies have investigated the use of activated carbon fibers (ACFs) impregnated with noble metals for the catalytic oxidation of volatile organic compounds (VOCs). This study determined the removal efficiency of toluene as a function of time over ACF-supported metal catalysts. Two catalysts (Pt and Pd), five reaction temperatures (120, 150, 200, 250, and 300°C), and three oxygen contents (6%, 10%, and 21%) were investigated to determine the removal of toluene. To study the effects of the characteristics of the catalysts on toluene removal, the composition and morphology of the ACFs were analyzed using the BET, XPS, ICP, and FE-SEM. The results showed that the 0.42%Pd/ACFs showed greater activity for toluene removal than did 2.68%Pt/ACFs at a reaction temperature of 200°C and an oxygen content of 10%. The main removal mechanism of toluene over the 2.68%Pt/ACFs at reaction temperatures less than 200°C was adsorption. The long-term catalytic activity of the 2.68%Pt/ACFs for toluene removal at a reaction temperature of 250°C and an oxygen content of 10% could be obtained. Furthermore, toluene removal over the 2.68%Pt/ACFs at 200°C could be enhanced with increasing oxygen content.

  19. Synthesis of Pt-Pd bimetallic nanoparticles anchored on graphene for highly active methanol electro-oxidation

    NASA Astrophysics Data System (ADS)

    Zhang, Yuting; Chang, Gang; Shu, Honghui; Oyama, Munetaka; Liu, Xiong; He, Yunbin

    2014-09-01

    A simple, one-step reduction route was employed to synthesize bimetallic Pt-Pd nanoparticles (Pt-PdNPs) supported on graphene (G) sheets, in which the reduction of graphite oxide and metal precursor was carried out simultaneously using ascorbic acid as a soft reductant. The morphology and structure of Pt-PdNPs/G composites were characterized using X-ray diffraction, Transmission Electron Microscopy, Field Emission Scanning Electron Microscopy and X-ray Photoelectron Spectroscopy analysis. The results show that Pt-Pd bimetallic nanoparticles were successfully synthesized and evenly anchored on the graphene sheets. Electrochemical experiments, including cyclic voltammetry and chronoamperometric measurements, were performed to investigate the electrochemical and electrocatalytic properties of the Pt-PdNPs/G composites. It was found that Pt-PdNPs/G composites show better electrocatalytic activity and stability towards the electro-oxidation of methanol than its counterparts such as composites composed of graphene-supported monometallic nanoparticles (PtNPs/G, PdNPs/G) and free-standing (Pt-PdNPs) and Vulcan-supported bimetallic Pt-Pd nanoparticles (Pt-PdNPs/V). The results could be attributed to the synergetic effects of the Pt-Pd nanoparticles and the enhanced electron transfer of graphene. The electrocatalytic activity of Pt-PdNPs/G changed with the Pd content in the Pt-Pd alloy, and the best performance was achieved with a Pt-Pd ratio of 1/3 in an alkaline environment. Our study indicates the potential use of Pt-PdNPs/G as new anode catalyst materials for direct methanol fuel cells.

  20. Growth and surface alloying of Fe on Pt(9 9 7)

    NASA Astrophysics Data System (ADS)

    Lee, Tae-Yon; Sarbach, Samuel; Kuhnke, Klaus; Kern, Klaus

    2006-08-01

    The growth of ultra-thin layers of Fe on the vicinal Pt(9 9 7) surface is studied by thermal energy He atom scattering (TEAS) and Auger Electron Spectroscopy (AES) in the temperature range between 175 K and 800 K. We find three distinct regimes of qualitatively different growth type. Below 450 K the formation of a smooth first monolayer, at and above 600 K the onset of bulk alloy formation, and at intermediate temperature 500-550 K the formation of a surface alloy. Monatomic Fe rows are observed to decorate the substrate steps between 175 K and 500 K. The importance of the high step density is discussed with respect to the promotion of smooth layer growth and with respect to the alloying process and its kinetics.

  1. [Hydrogen induced C-C, C-N, and C-S bond activities on Pi and Ni surfaces]: Summary

    SciTech Connect

    Gland, J.L.

    1994-12-31

    This document summarizes research applied to chemical bond activation studies. Topics summarized include: Carbon nitrogen bonds experimentation with aniline on Ni(111), Mi(100), and Pt(111) surfaces; carbon sulfur bonds experimentation with methanethiol, phenylthiol, and dimethyl disulfide on Pt(111) and Ni(111) surfaces; carbon-carbon bonds experimentation on Ni(100), Ni(111) and Pt(111) surfaces; and in-situ fluorescence yield near edge spectroscopy.

  2. Ground state of Ho atoms on Pt(111) metal surfaces: Implications for magnetism

    NASA Astrophysics Data System (ADS)

    Karbowiak, M.; Rudowicz, C.

    2016-05-01

    We investigated the ground state of Ho atoms adsorbed on the Pt(111) surface, for which conflicting results exist. The density functional theory (DFT) calculations yielded the Ho ground state as | Jz=±8 > . Interpretation of x-ray absorption spectroscopy and x-ray magnetic circular dichroism spectra and the magnetization curves indicated the ground state as | Jz=±6 > . Superposition model is employed to predict the crystal-field (CF) parameters based on the structural data for the system Ho/Pt(111) obtained from the DFT modeling. Simultaneous diagonalization of the free-ion (HFI) and the trigonal CF Hamiltonian (HCF) within the whole configuration 4 f10 of H o3 + ion was performed. The role of the trigonal CF terms, neglected in the pure uniaxial CF model used previously for interpretation of experimental spectra, is found significant, whereas the sixth-rank CF terms may be neglected in agreement with the DFT predictions. The results provide substantial support for the experimental designation of the | Jz=±6 > ground state, albeit with subtle difference due to admixture of other | Jz> states, but run against the DFT-based designation of the | Jz=±8 > ground state. A subtle splitting of the ground energy level with the state (predominantly), | Jz=±6 > is predicted. This paper provides better insight into the single-ion magnetic behavior of the Ho/Pt(111) system by helping to resolve the controversy concerning the Ho ground state. Experimental techniques with greater resolution powers are suggested for direct confirmation of this splitting and C3 v symmetry experienced by the Ho atom.

  3. Surface sites on Pt-CeO2 mixed oxide catalysts probed by CO adsorption: a synchrotron radiation photoelectron spectroscopy study.

    PubMed

    Neitzel, Armin; Lykhach, Yaroslava; Skála, Tomáš; Tsud, Nataliya; Vorokhta, Mykhailo; Mazur, Daniel; Prince, Kevin C; Matolín, Vladimír; Libuda, Jörg

    2014-12-07

    By means of synchrotron radiation photoemission spectroscopy, we have investigated Pt-CeO2 mixed oxide films prepared on CeO2(111)/Cu(111). Using CO molecules as a probe, we associate the corresponding surface species with specific surface sites. This allows us to identify the changes in the composition and morphology of Pt-CeO2 mixed oxide films caused by annealing in an ultrahigh vacuum. Specifically, two peaks in C 1s spectra at 289.4 and 291.2 eV, associated with tridentate and bidentate carbonate species, are formed on the nanostructured stoichiometric CeO2 film. The peak at 290.5-291.0 eV in the C 1s spectra indicates the onset of restructuring, i.e. coarsening, of the Pt-CeO2 film. This peak is associated with a carbonate species formed near an oxygen vacancy. The onset of cerium oxide reduction is indicated by the peak at 287.8-288.0 eV associated with carbonite species formed near Ce(3+) cations. The development of surface species on the Pt-CeO2 mixed oxides suggests that restructuring of the films occurs above 300 K irrespective of Pt loadings. We do not find any adsorbed CO species associated with Pt(4+) or Pt(2+). The onset of Pt(2+) reduction is indicated by the peak at 286.9 eV in the C 1s spectra due to CO adsorption on metallic Pt particles. The thermal stability of Pt(2+) in Pt-CeO2 mixed oxide depends on Pt loading. We find excellent stability of Pt(2+) for 12% Pt content in the CeO2 film, whereas at a Pt concentration of 25% in the CeO2 film, a large fraction of the Pt(2+) is converted into metallic Pt particles above 300 K.

  4. Synthesis and Antiproliferative Activity of Steroidal Thiosemicarbazone Platinum (Pt(II)) Complexes

    PubMed Central

    Huang, Yanmin; Kong, Erbin; Gan, Chunfang; Liu, Zhiping; Lin, Qifu; Cui, Jianguo

    2015-01-01

    Steroidal compounds exhibit particular physiological activities. In this paper, some steroidal thiosemicarbazones platinum (Pt(II)) complexes were synthesized by the condensation of steroidal ketones with thiosemicarbazide using estrone, chenodeoxycholic acid, and 7-deoxycholic acid as starting materials and complexation of steroidal thiosesemicarbazones with Pt(II). The complexes were characterized by IR, NMR, and MS, and their antiproliferative activities were evaluated. The results showed that some steroidal thiosemicarbazones platinum (Pt(II)) complexes displayed moderate cytotoxicity to HeLa and Bel-7404 cells. Thereinto, complex 6 showed an excellent inhibited selectivity to HeLa cells with an IC50 value of 9.2 μM and SI value of 21.7. At the same time, all compounds were almost inactive to HEK293T (normal kidney epithelial cells). The information obtained from the studies may be useful for the design of novel chemotherapeutic drugs. PMID:26635511

  5. Infrared-active quadruple contrast FePt nanoparticles for multiple scale molecular imaging.

    PubMed

    Chou, Shang-Wei; Liu, Chien-Liang; Liu, Tzu-Ming; Shen, Yu-Fang; Kuo, Lun-Chang; Wu, Cheng-Ham; Hsieh, Tsung-Yuan; Wu, Pei-Chun; Tsai, Ming-Rung; Yang, Che-Chang; Chang, Kai-Yao; Lu, Meng-Hua; Li, Pai-Chi; Chen, Shi-Ping; Wang, Yu-Hsin; Lu, Chen-Wen; Chen, Yi-An; Huang, Chih-Chia; Wang, Churng-Ren Chris; Hsiao, Jong-Kai; Li, Meng-Lin; Chou, Pi-Tai

    2016-04-01

    A single nanomaterial with multiple imaging contrasts and functions is highly desired for multiscale theragnosis. Herein, we demonstrate single 1-1.9 μm infrared-active FePt alloy nanoparticles (FePt NPs) offering unprecedented four-contrast-in-one molecular imaging - computed tomography (CT), magnetic resonance imaging (MRI), photoacoustic (PA) imaging, and high-order multiphoton luminescence (HOMPL) microscopy. The PA response of FePt NPs outperforms that of infrared-active gold nanorods by 3- to 5.6-fold under identical excitation fluence and particle concentrations. HOMPL (680 nm) of an isolated FePt NP renders spatial full-width-at-half-maximum values of 432 nm and 300 nm beyond the optical diffraction limit for 1230-nm and 920-nm excitation, respectively. The in vivo targeting function was successfully visualized using HOMPL, PA imaging, CT, and MRI, thereby validating FePt as a single nanomaterial system covering up to four types (Optical/PA/CT/MRI) of molecular imaging contrast, ranging from the microscopic level to whole-body scale investigation.

  6. Growth of Pt/Cu(100): An Atomistic Modeling Comparison with the Pd/Cu(100) Surface Alloy

    NASA Technical Reports Server (NTRS)

    Demarco, Gustavo; Garces, Jorge E.; Bozzolo, Guillermo

    2002-01-01

    The Bozzolo, Ferrante, and Smith (BFS) method for alloys is applied to the study of Pt deposition on Cu(100). The formation of a Cu-Pt surface alloy is discussed within the framework of previous results for Pd/Cu(100). In spite of the fact that both Pd and Pt share the same basic behavior when deposited on Cu, it is seen that subtle differences become responsible for the differences in growth observed at higher cover-ages. In agreement with experiment, all the main features of Pt/Cu(100) and Pd/Cu(100) are obtained by means of a simple modeling scheme, and explained in terms of a few basic ingredients that emerge from the BFS analysis.

  7. Synthesis and structure-activity relationship exploration of carbon-supported PtRuNi nanocomposite as a CO-tolerant electrocatalyst for proton exchange membrane fuel cells.

    PubMed

    Liang, Yongmin; Zhang, Huamin; Tian, Zhiqun; Zhu, Xiaobing; Wang, Xiaoli; Yi, Baolian

    2006-04-20

    A carbon-supported PtRuNi nanocomposite is synthesized via a microwave-irradiated polyol plus annealing synthesis strategy. The catalyst is characterized by transmission electron microscopy, powder X-ray diffraction, energy dispersive spectroscopy, and X-ray photoelectron spectroscopy. The data are discussed with respect to those for the carbon-supported PtRu nanocomposite prepared following the same way. The characterizations show that the inclusion of Ni in the PtRu system has only a small effect on the particle size, the structure, and the compositional homogeneity. CO-stripping voltammetry and measurements on the single proton exchange membrane fuel cells show that the PtRuNi/C catalyst has an improved activity for CO(ads) electro-oxidation. An accelerated durability test on the catalyst exhibits insignificant loss of activity in acidic media. On the basis of the exploration of the structure-activity relationship, a mechanism for the improved performance of the catalyst is proposed. It is suggested that the improved CO-tolerant performance of the PtRuNi/C nanocomposite should be related to the hydrogen spillover on the catalyst surface, the enhanced oxidation of CO(ads) by nickel hydroxides, and the high proton and electronic conductivity of the hydroxides. The nickel hydroxide passivated surface and/or anchoring of metallic nickel in the platinum lattice may contribute to the durability of the catalyst in acid solution.

  8. Flower like Bi structures on Pt surface facilitating effective cholesterol biosensing.

    PubMed

    V C, Soorya; Berchmans, Sheela

    2016-07-01

    This work demonstrates effective biosensing of cholesterol with the help of an efficient inorganic H2O2 transducer based on Pt-Bi combined with the organic enzyme platform. It could be shown that the Bi (bismuth) adatoms modified Pt (platinum) surface displays enhanced catalytic oxidation of H2O2 at neutral pH and the catalytic oxidation of H2O2 occurs at a lower potential of 0.25V vs NCE (normal calomel electrode). The sensing platform is highly sensitive and shows linear response towards [H2O2] in the absence of any redox mediator or enzyme. The H2O2 sensing platform, further modified with cholesterol oxidase led to cholesterol biosensing with a sensitivity of 3.41μAmM(-1)cm(-2). The apparent Michaelis-Menten constant (Km(app)) was calculated to be 0.43mM which indicates high binding affinity with the substrate. The cholesterol biosensor does not suffer from the interferences due to other common electroactive species and is highly stable.

  9. Electrospun Nb-doped TiO2 nanofiber support for Pt nanoparticles with high electrocatalytic activity and durability.

    PubMed

    Kim, MinJoong; Kwon, ChoRong; Eom, KwangSup; Kim, JiHyun; Cho, EunAe

    2017-03-14

    This study explores a facile method to prepare an efficient and durable support for Pt catalyst of polymer electrolyte membrane fuel cell (PEMFC). As a candidate, Nb-doped TiO2 (Nb-TiO2) nanofibers are simply fabricated using an electrospinning technique, followed by a heat treatment. Doping Nb into the TiO2 nanofibers leads to a drastic increase in electrical conductivity with doping level of up to 25 at. % (Nb0.25Ti0.75O2). Pt nanoparticles are synthesized on the prepared 25 at. % Nb-doped TiO2-nanofibers (Pt/Nb-TiO2) as well as on a commercial powdered carbon black (Pt/C). The Pt/Nb-TiO2 nanofiber catalyst exhibits similar oxygen reaction reduction (ORR) activity to that of the Pt/C catalyst. However, during an accelerated stress test (AST), the Pt/Nb-TiO2 nanofiber catalyst retained more than 60% of the initial ORR activity while the Pt/C catalyst lost 65% of the initial activity. The excellent durability of the Pt/Nb-TiO2 nanofiber catalyst can be attributed to high corrosion resistance of TiO2 and strong interaction between Pt and TiO2.

  10. Electrospun Nb-doped TiO2 nanofiber support for Pt nanoparticles with high electrocatalytic activity and durability

    PubMed Central

    Kim, MinJoong; Kwon, ChoRong; Eom, KwangSup; Kim, JiHyun; Cho, EunAe

    2017-01-01

    This study explores a facile method to prepare an efficient and durable support for Pt catalyst of polymer electrolyte membrane fuel cell (PEMFC). As a candidate, Nb-doped TiO2 (Nb-TiO2) nanofibers are simply fabricated using an electrospinning technique, followed by a heat treatment. Doping Nb into the TiO2 nanofibers leads to a drastic increase in electrical conductivity with doping level of up to 25 at. % (Nb0.25Ti0.75O2). Pt nanoparticles are synthesized on the prepared 25 at. % Nb-doped TiO2-nanofibers (Pt/Nb-TiO2) as well as on a commercial powdered carbon black (Pt/C). The Pt/Nb-TiO2 nanofiber catalyst exhibits similar oxygen reaction reduction (ORR) activity to that of the Pt/C catalyst. However, during an accelerated stress test (AST), the Pt/Nb-TiO2 nanofiber catalyst retained more than 60% of the initial ORR activity while the Pt/C catalyst lost 65% of the initial activity. The excellent durability of the Pt/Nb-TiO2 nanofiber catalyst can be attributed to high corrosion resistance of TiO2 and strong interaction between Pt and TiO2. PMID:28290503

  11. Electrospun Nb-doped TiO2 nanofiber support for Pt nanoparticles with high electrocatalytic activity and durability

    NASA Astrophysics Data System (ADS)

    Kim, Minjoong; Kwon, Chorong; Eom, Kwangsup; Kim, Jihyun; Cho, Eunae

    2017-03-01

    This study explores a facile method to prepare an efficient and durable support for Pt catalyst of polymer electrolyte membrane fuel cell (PEMFC). As a candidate, Nb-doped TiO2 (Nb-TiO2) nanofibers are simply fabricated using an electrospinning technique, followed by a heat treatment. Doping Nb into the TiO2 nanofibers leads to a drastic increase in electrical conductivity with doping level of up to 25 at. % (Nb0.25Ti0.75O2). Pt nanoparticles are synthesized on the prepared 25 at. % Nb-doped TiO2-nanofibers (Pt/Nb-TiO2) as well as on a commercial powdered carbon black (Pt/C). The Pt/Nb-TiO2 nanofiber catalyst exhibits similar oxygen reaction reduction (ORR) activity to that of the Pt/C catalyst. However, during an accelerated stress test (AST), the Pt/Nb-TiO2 nanofiber catalyst retained more than 60% of the initial ORR activity while the Pt/C catalyst lost 65% of the initial activity. The excellent durability of the Pt/Nb-TiO2 nanofiber catalyst can be attributed to high corrosion resistance of TiO2 and strong interaction between Pt and TiO2.

  12. Hydrothermal Synthesis of Ultrasmall Pt Nanoparticles as Highly Active Electrocatalysts for Methanol Oxidation

    PubMed Central

    Ji, Wenhai; Qi, Weihong; Tang, Shasha; Peng, Hongcheng; Li, Siqi

    2015-01-01

    Ultrasmall nanoparticles, with sizes in the 1–3 nm range, exhibit unique properties distinct from those of free molecules and larger-sized nanoparticles. Demonstrating that the hydrothermal method can serve as a facile method for the synthesis of platinum nanoparticles, we successfully synthesized ultrasmall Pt nanoparticles with an average size of 2.45 nm, with the aid of poly(vinyl pyrrolidone) (PVP) as reducing agents and capping agents. Because of the size effect, these ultrasmall Pt nanoparticles exhibit a high activity toward the methanol oxidation reaction.

  13. Anode activation polarization on Pt(h k l) electrodes in dilute sulphuric acid electrolyte

    NASA Astrophysics Data System (ADS)

    Mann, R. F.; Amphlett, J. C.; Peppley, B. A.; Thurgood, C. P.

    Proton exchange membrane (PEM) fuel cells have been under development for many years and appear to be the potential solution for many electricity supply applications. Modelling and computer simulation of PEM fuel cells have been equally active areas of work as a means of developing better understanding of cell and stack operation, facilitating design improvements and supporting system simulation studies. The prediction of activation polarization in our previous PEM modelling work, as in most PEM models, concentrated on the cathode losses. Anode losses are commonly much smaller and tend to be ignored compared to cathode losses. Further development of the anode activation polarization term is being undertaken in order to broaden the application and usefulness of PEM models in general. Previously published work on the kinetics of the hydrogen oxidation reaction using Pt(h k l) electrodes in dilute H 2SO 4 has been examined and further developed for eventual application to the modelling of PEM fuel cells. New correlations for the exchange current density are developed for Pt(1 0 0), Pt(1 1 0) and Pt(1 1 1) electrodes. Predictive equations for the anode activation polarization are also proposed. In addition, terminology has been modified to make the correlation approach and, eventually, the modelling method more easily understood and used by those without an extensive background in electrochemistry.

  14. Effect of Pt Nanoparticles on the Photocatalytic Activity of ZnO Nanofibers.

    PubMed

    Di Mauro, Alessandro; Zimbone, Massimo; Scuderi, Mario; Nicotra, Giuseppe; Fragalà, Maria Elena; Impellizzeri, Giuliana

    2015-12-01

    For this study, we originally realized ZnO nanofibers (∼50 nm in mean radius) mixed with Pt nanoparticles (∼30 nm in mean radius), prepared by pulsed laser ablation in liquid, and investigated their photocatalytic performance. The material was synthesized by the simple electrospinning method coupled with subsequent thermal treatments. Methylene blue was employed as a representative dye pollutant to evaluate the photocatalytic activity of the nanofibers. It was found that the Pt-ZnO fibers exhibit a photodegradation reaction rate that is ∼40 % higher than the one obtained for reference ZnO fibers. These encouraging results demonstrate that Pt-ZnO nanofibers can be fruitfully applied for environmental applications.

  15. Effect of Pt Nanoparticles on the Photocatalytic Activity of ZnO Nanofibers

    NASA Astrophysics Data System (ADS)

    Di Mauro, Alessandro; Zimbone, Massimo; Scuderi, Mario; Nicotra, Giuseppe; Fragalà, Maria Elena; Impellizzeri, Giuliana

    2015-12-01

    For this study, we originally realized ZnO nanofibers (˜50 nm in mean radius) mixed with Pt nanoparticles (˜30 nm in mean radius), prepared by pulsed laser ablation in liquid, and investigated their photocatalytic performance. The material was synthesized by the simple electrospinning method coupled with subsequent thermal treatments. Methylene blue was employed as a representative dye pollutant to evaluate the photocatalytic activity of the nanofibers. It was found that the Pt-ZnO fibers exhibit a photodegradation reaction rate that is ˜40 % higher than the one obtained for reference ZnO fibers. These encouraging results demonstrate that Pt-ZnO nanofibers can be fruitfully applied for environmental applications.

  16. Preparation of Pt-Ru-Ni ternary nanoparticles by microemulsion and electrocatalytic activity for methanol oxidation

    SciTech Connect

    Zhang Xin . E-mail: xzhang@stu.edu.cn; Zhang Feng; Guan Renfeng; Chan, K.-Y.

    2007-02-15

    Ternary platinum-ruthenium-nickel nanoparticles are prepared by water-in-oil reverse microemulsions of water/Triton X-100/propanol-2/cyclohexane. Nanoparticles formed in the microemulsions are characterized by transmission electron microscopy (TEM), electron diffraction (ED), X-ray diffractometry (XRD), energy dispersive X-ray analysis (EDX). These resulting materials showed a homogenous alloy structure, the mono-dispersion and an average diameter of 2.6 {+-} 0.3 nm with a narrow particle size distribution. The composition and particle size of ternary Pt-Ru-Ni nanoparticles can be controlled by adjusting the initial metal salt solution and preparation conditions. Pt-Ru-Ni ternary metallic nanoparticles showed an enhanced catalytic activity towards methanol oxidation compared to Pt-Ru bimetallic nanoparticles.

  17. Correlation between surface chemistry and electrocatalytic properties of monodisperse Pt{sub x}Ni{sub 1-x} nanoparticles.

    SciTech Connect

    Wang, C.; Chi, M.; Wang, G.; van der Vliet, D.; Li, D.; More, K.; Wang, H.-H.; Schlueter, J. A.; Markovic, N. M.; Stamenkovic, V. R.

    2011-01-07

    Monodisperse and homogeneous Pt{sub x}Ni{sub 1-x} alloy nanoparticles of various compositions are synthesized via an organic solution approach in order to reveal the correlation between surface chemistry and their electrocatalytic properties. Atomic-level microscopic analysis of the compositional profile and modeling of nanoparticle structure are combined to follow the dependence of Ni dissolution on the initial alloy composition and formation of the Pt-skeleton nanostructures. The developed approach and acquired knowledge about surface structure-property correlation can be further generalized and applied towards the design of advanced functional nanomaterials.

  18. Surface profile control of FeNiPt/Pt core/shell nanowires for oxygen reduction reaction

    SciTech Connect

    Zhu, Huiyuan; Zhang, Sen; Su, Dong; Jiang, Guangming; Sun, Shouheng

    2015-03-18

    The ever-increasing energy demand requires renewable energy schemes with low environmental impacts. Electrochemical energy conversion devices, such as fuel cells, combine fuel oxidization and oxygen reduction reactions and have been studied extensively for renewable energy applications. However, their energy conversion efficiency is often limited by kinetically sluggish chemical conversion reactions, especially oxygen reduction reaction (ORR). [1-5] To date, extensive efforts have been put into developing efficient ORR catalysts with controls on catalyst sizes, compositions, shapes and structures. [6-12] Recently, Pt-based catalysts with core/shell and one-dimensional nanowire (NW) morphologies were found to be promising to further enhance ORR catalysis. With the core/shell structure, the ORR catalysis of a nanoparticle (NP) catalyst can be tuned by both electronic and geometric effects at the core/shell interface. [10,13,14] With the NW structure, the catalyst interaction with the conductive support can be enhanced to facilitate electron transfer between the support and the NW catalyst and to promote ORR. [11,15,16]

  19. Surface profile control of FeNiPt/Pt core/shell nanowires for oxygen reduction reaction

    DOE PAGES

    Zhu, Huiyuan; Zhang, Sen; Su, Dong; ...

    2015-03-18

    The ever-increasing energy demand requires renewable energy schemes with low environmental impacts. Electrochemical energy conversion devices, such as fuel cells, combine fuel oxidization and oxygen reduction reactions and have been studied extensively for renewable energy applications. However, their energy conversion efficiency is often limited by kinetically sluggish chemical conversion reactions, especially oxygen reduction reaction (ORR). [1-5] To date, extensive efforts have been put into developing efficient ORR catalysts with controls on catalyst sizes, compositions, shapes and structures. [6-12] Recently, Pt-based catalysts with core/shell and one-dimensional nanowire (NW) morphologies were found to be promising to further enhance ORR catalysis. With themore » core/shell structure, the ORR catalysis of a nanoparticle (NP) catalyst can be tuned by both electronic and geometric effects at the core/shell interface. [10,13,14] With the NW structure, the catalyst interaction with the conductive support can be enhanced to facilitate electron transfer between the support and the NW catalyst and to promote ORR. [11,15,16]« less

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

    PubMed

    Li, Zhiyang; Leung, Calvin; Gao, Fan; Gu, Zhiyong

    2015-09-04

    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.

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

    PubMed Central

    Li, Zhiyang; Leung, Calvin; Gao, Fan; Gu, Zhiyong

    2015-01-01

    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. PMID:26404303

  2. AuPt Alloy Nanostructures with Tunable Composition and Enzyme-like Activities for Colorimetric Detection of Bisulfide

    NASA Astrophysics Data System (ADS)

    He, Weiwei; Han, Xiangna; Jia, Huimin; Cai, Junhui; Zhou, Yunlong; Zheng, Zhi

    2017-01-01

    Tuning the enzyme-like activity and studying the interaction between biologically relevant species and nano-enzymes may facilitate the applications of nanostructures in mimicking natural enzymes. In this work, AuPt alloy nanoparticles (NPs) with varying compositions were prepared through a facile method by co-reduction of Au3+ and Pt2+ in aqueous solutions. The composition could be tuned easily by adjusting the molar ratios of added Pt2+ to Au3+. It was found that both peroxidase-like and oxidase-like activity of AuPt alloy NPs were highly dependent on the alloy compositions, which thus suggesting an effective way to tailor their catalytic properties. By investigating the inhibitory effects of HS‑ on the enzyme-like activity of AuPt alloy NPs and natural enzyme, we have developed a method for colorimetric detection of HS‑ and evaluation of the inhibiting effects of inhibitors on natural and artificial enzymes. In addition, the responsive ability of this method was influenced largely by the composition: AuPt alloy NPs show much lower limit of detection for HS‑ than Pt NPs while Pt NPs show wider linear range than AuPt alloy NPs. This study suggests the facile way not only for synthesis of alloy nanostructures, but also for tuning their catalytic activities and for use in bioanalysis.

  3. AuPt Alloy Nanostructures with Tunable Composition and Enzyme-like Activities for Colorimetric Detection of Bisulfide

    PubMed Central

    He, Weiwei; Han, Xiangna; Jia, Huimin; Cai, Junhui; Zhou, Yunlong; Zheng, Zhi

    2017-01-01

    Tuning the enzyme-like activity and studying the interaction between biologically relevant species and nano-enzymes may facilitate the applications of nanostructures in mimicking natural enzymes. In this work, AuPt alloy nanoparticles (NPs) with varying compositions were prepared through a facile method by co-reduction of Au3+ and Pt2+ in aqueous solutions. The composition could be tuned easily by adjusting the molar ratios of added Pt2+ to Au3+. It was found that both peroxidase-like and oxidase-like activity of AuPt alloy NPs were highly dependent on the alloy compositions, which thus suggesting an effective way to tailor their catalytic properties. By investigating the inhibitory effects of HS− on the enzyme-like activity of AuPt alloy NPs and natural enzyme, we have developed a method for colorimetric detection of HS− and evaluation of the inhibiting effects of inhibitors on natural and artificial enzymes. In addition, the responsive ability of this method was influenced largely by the composition: AuPt alloy NPs show much lower limit of detection for HS− than Pt NPs while Pt NPs show wider linear range than AuPt alloy NPs. This study suggests the facile way not only for synthesis of alloy nanostructures, but also for tuning their catalytic activities and for use in bioanalysis. PMID:28051159

  4. High-activity PtRuPd/C catalyst for direct dimethyl ether fuel cells.

    PubMed

    Li, Qing; Wen, Xiaodong; Wu, Gang; Chung, Hoon T; Gao, Rui; Zelenay, Piotr

    2015-06-22

    Dimethyl ether (DME) has been considered as a promising alternative fuel for direct-feed fuel cells but lack of an efficient DME oxidation electrocatalyst has remained the challenge for the commercialization of the direct DME fuel cell. The commonly studied binary PtRu catalyst shows much lower activity in DME than methanol oxidation. In this work, guided by density functional theory (DFT) calculation, a ternary carbon-supported PtRuPd catalyst was designed and synthesized for DME electrooxidation. DFT calculations indicated that Pd in the ternary PtRuPd catalyst is capable of significantly decreasing the activation energy of the CO and CH bond scission during the oxidation process. As evidenced by both electrochemical measurements in an aqueous electrolyte and polymer-electrolyte fuel cell testing, the ternary catalyst shows much higher activity (two-fold enhancement at 0.5 V in fuel cells) than the state-of-the-art binary Pt50 Ru50 /C catalyst (HiSPEC 12100).

  5. Superior anti-CO poisoning capability: Au-decorated PtFe nanocatalysts for high-performance methanol oxidation.

    PubMed

    Cai, Zhao; Lu, Zhiyi; Bi, Yongmin; Li, Yaping; Kuang, Yun; Sun, Xiaoming

    2016-03-11

    Herein we demonstrate a surface engineering strategy, namely, decorating Au on the surface of bimetallic PtFe nanocatalysts, to effectively decrease the adsorption energy of CO on the Pt center, which promotes the electrocatalytic activity towards methanol oxidation, far better than those of PtFe and commercial Pt/C catalysts.

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

    PubMed

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

    2017-03-21

    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 (SO4(-)) 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 (HCO3(-)), phosphate (PO4(3-)) and humic acid (HA) all inhibited CBZ degradation with the order of HA > HCO3(-) > PO4(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.

  7. Mixed-phase Pd-Pt bimetallic alloy on graphene oxide with high activity for electrocatalytic applications

    NASA Astrophysics Data System (ADS)

    Khan, Majid; Yousaf, Ammar Bin; Chen, Mingming; Wei, Chengsha; Wu, Xibo; Huang, Ningdong; Qi, Zeming; Li, Liangbin

    2015-05-01

    Bimetallic PdPt alloy nanoparticles on graphene oxide (GO) have been prepared by a simple and facile chemical route, in which the reduction of metal precursors is carried out using CO as a reductant. Structural and morphological characterizations of GO/PdPt composites are performed using X-ray diffraction, X-ray photoelectron spectroscopy analysis and transmission electron microscopy. It is found that PdPt bimetallic nanoparticles are successfully synthesized and uniformly attached on the graphene sheets. The electrocatalytic and electrochemical properties of GO/PdPt composites including methanol oxidation reaction (MOR), oxygen reduction reaction (ORR) and methanol tolerant oxygen reduction reaction (MTORR) are studied in HClO4 aqueous solution. A significant improvement in the electrocatalytic activities is observed by increasing the atomic ratio of Pt in PdPt bimetallic alloys compared to the freestanding Pd nanoparticles on GO. The prepared GO/PdPt composites with an (Pd:Pt) atomic ratio of 40:60 exhibits higher methanol oxidation activity, higher specific ORR activity and better tolerance to CO poisoning. The results can be attributed to the collective effects of the PdPt nanoparticles and the enhanced electron transfer of graphene.

  8. Enhanced Activity and Durability of Nanosized Pt-SnO2/IrO2/CNTs Catalyst for Methanol Electrooxidation.

    PubMed

    Wang, Hongjuan; Wang, Xiaohui; Zheng, Jiadao; Peng, Feng; Yu, Hao

    2015-05-01

    Pt-SnO2/IrO2/CNTs anode catalyst for direct methanol fuel cell was designed and prepared with IrO2/CNTs as support for the subsequent immobilization of Pt and SnO2 at the same time. The structure of the catalysts and their catalytic performance in methanol electrooxidation were investigated and the roles of IrO2 and SnO2 in methanol electrooxidation were discussed as well. Results show that Pt-SnO2/IrO2/CNTs catalyst exhibits the best activity and durability for methanol electrooxidation when compared with Pt/CNTs, Pt/IrO2/CNTs and Pt-SnO2/CNTs. According to the results of electrochemical tests and physicochemical characterizations, the enhancements of Pt-SnO2/IrO2/CNTs were attributed to the special properties of IrO2 and SnO2, in which IrO2 mainly increases the methanol oxidation activity and SnO2 mainly improves the CO oxidation ability and durability. Therefore, Pt-SnO2/IrO2/CNTs exhibits excellent performance for methanol oxidation with higher electrocatalytic activity (I(f) of 1054 A g(Pt(-1)) and powerful anti-poisoning ability (the onset potential for CO oxidation of 0.3 V) and outstanding durability (the sustained time t in CP of 617 s), revealing a suitable anode catalyst for DMFCs.

  9. Abstraction of sulfur from Pt( 1 1 1 ) surfaces with thermal H atoms toward adsorbed and gaseous H 2S

    NASA Astrophysics Data System (ADS)

    Güttler, A.; Kolovos-Vellianitis, D.; Zecho, T.; Küppers, J.

    2002-09-01

    Sulphur layers on Pt(1 1 1) surfaces with coverages of 0.25 and 0.33 were prepared by H 2S adsorption at 85 K and subsequent annealing. H 2S adsorption on Pt, S/Pt and H/Pt surfaces and S adsorbate layers were characterized by Auger electron and thermal desorption spectroscopies. Admission of thermal H atoms to S covered Pt(1 1 1) at 85 K leads to formation of gaseous (80%) as well as adsorbed H 2S (20%). The yield of adsorbed H 2S decreases due to its isothermal desorption above 90 K. The interaction of H(g) with S(a) involves three reaction steps: 1. H(g)+S(a)→SH(a), 2. H(g)+SH(a)→H 2S(g,a), and 3. H(g)+SH(a)→H 2(g)+S(a) with apparent cross-sections σ1=0.3 Å 2, σ2=0.6 Å 2 and σ3=0.03 Å 2. Above 140 K the hydrogenation of SH toward H 2S(a,g) is blocked by thermal decomposition of H 2S. Impact of D on coadsorbed S, SH, and H 2S leads to desorption of H 2S.

  10. Electrospun TiC/C nano-felt surface-decorated with Pt nanoparticles as highly efficient and cost-effective counter electrode for dye-sensitized solar cells.

    PubMed

    Zhao, Yong; Thapa, Amit; Feng, Quan; Xi, Min; Qiao, Qiquan; Fong, Hao

    2013-12-07

    Electrospun nano-felt consisting of overlaid TiC/C composite nanofibers was surface-decorated with Pt nanoparticles (Pt NPs) for use as highly efficient and cost-effective counter electrode (CE) in dye-sensitized solar cells (DSSCs). In the nanofibers, the self-generated TiC crystallites (~70 wt%) with sizes of ~20 nm were randomly embedded in carbon (~30 wt%). Upon surface-decoration, most Pt NPs were distributed on TiC crystallites, leading to substantial enhancement in the electrocatalytic activity/efficiency of Pt due to the strong interaction between Pt and TiC as well as the resulting synergetic effect on electrocatalysis. Electrochemical measurements indicated that the TiC/C-Pt CE exhibited low charge transfer resistance (Rct), large capacitance (C), and fast reaction rate towards the reduction of I3(-) ions, and the prototype DSSC exhibited a performance comparable to that with conventional Pt CE in terms of short circuit current density (Jsc), open circuit voltage (Voc), fill factor (FF), and energy conversion efficiency (η).

  11. Reversible hydrogen activation by the Pt complex Pt(Sn(t)Bu3)2(CNtBu)2.

    PubMed

    Yempally, Veeranna; Zhu, Lei; Captain, Burjor

    2010-08-16

    The new platinum complex Pt(Sn(t)Bu(3))(2)(CN(t)Bu)(2)(H)(2), 1, was obtained in 32% yield from the reaction of Pt(COD)(2) with (t)Bu(3)SnH and CN(t)Bu at room temperature. Compound 1 is a mononuclear 18 electron platinum complex in an octahedral geometry which contains two Sn(t)Bu(3)'s, two CN(t)Bu's, and two hydride ligands. The two hydride ligands in 1 can be eliminated, both in solution and in the solid state, to yield the 16 electron complex Pt(Sn(t)Bu(3))(2)(CN(t)Bu)(2), 2. Compound 2 reacts with hydrogen at room temperature in solution and in the solid state to regenerate 1.

  12. Electrochemical Dealloying of PdCu3 Nanoparticles to Achieve Pt-like Activity for the Hydrogen Evolution Reaction.

    PubMed

    Jana, Rajkumar; Bhim, Anupam; Bothra, Pallavi; Pati, Swapan K; Peter, Sebastian C

    2016-10-20

    Manipulating the d-band center of the metal surface and hence optimizing the free energy of hydrogen adsorption (ΔGH ) close to the optimal adsorption energy (ΔGH =0) for hydrogen evolution reaction (HER), is an efficient strategy to enhance the activity for HER. Herein, we report a oleylamine-mediated (acting as the solvent, stabilizer, and reducing agent) strategy to synthesize intermetallic PdCu3 nanoparticles (NPs) without using any external reducing agent. Upon electrochemical cycling, PdCu3 transforms into Pd-rich PdCu (ΔGH =0.05 eV), exhibiting remarkably enhanced activity (with a current density of 25 mA cm(-2) at ∼69 mV overpotential) as an alternative to Pt for HER. The first-principle calculation suggests that formation of low coordination number Pd active sites alters the d-band center and hence optimal adsorption of hydrogen, leading to enhanced activity. This finding may provide guidelines towards the design and development of Pt-free highly active and robust electrocatalysts.

  13. Asymmetric Volcano Trend in Oxygen Reduction Activity of Pt and Non-Pt Catalysts: In Situ Identification of the Site-Blocking Effect.

    PubMed

    Li, Jingkun; Alsudairi, Amell; Ma, Zi-Feng; Mukerjee, Sanjeev; Jia, Qingying

    2017-02-01

    Proper understanding of the major limitations of current catalysts for oxygen reduction reaction (ORR) is essential for further advancement. Herein by studying representative Pt and non-Pt ORR catalysts with a wide range of redox potential (Eredox) via combined electrochemical, theoretical, and in situ spectroscopic methods, we demonstrate that the role of the site-blocking effect in limiting the ORR varies drastically depending on the Eredox of active sites; and the intrinsic activity of active sites with low Eredox have been markedly underestimated owing to the overlook of this effect. Accordingly, we establish a general asymmetric volcano trend in the ORR activity: the ORR of the catalysts on the overly high Eredox side of the volcano is limited by the intrinsic activity; whereas the ORR of the catalysts on the low Eredox side is limited by either the site-blocking effect and/or intrinsic activity depending on the Eredox.

  14. Structural and chemical characteristics of atomically smooth GaN surfaces prepared by abrasive-free polishing with Pt catalyst

    NASA Astrophysics Data System (ADS)

    Murata, Junji; Sadakuni, Shun; Okamoto, Takeshi; Hattori, Azusa N.; Yagi, Keita; Sano, Yasuhisa; Arima, Kenta; Yamauchi, Kazuto

    2012-06-01

    This paper reports the structural and chemical characteristics of atomically flat gallium nitride (GaN) surfaces prepared by abrasive-free polishing with platinum (Pt) catalyst. Atomic force microscopy revealed regularly alternating wide and narrow terraces with a step height equivalent to that of a single bilayer on the flattened GaN surfaces, which originate from the differences in etching rate of two neighboring terraces. The material removal characteristics of the method for GaN surfaces were investigated in detail. We confirmed that an atomically smooth GaN surface with an extremely small number of surface defects, including pits and scratches, can be achieved, regardless of the growth method, surface polarity, and doping concentration. X-ray photoelectron spectroscopy showed that the flattening method produces clean GaN surfaces with only trace impurities such as Ga oxide and metallic Ga. Contamination with the Pt catalyst was also evaluated using total-reflection X-ray fluorescence analysis. A wet cleaning method with aqua regia is proposed, which markedly eliminates this Pt contamination without affecting the surface morphology.

  15. Effect of impregnation protocol in the metallic sites of Pt-Ag/activated carbon catalysts for water denitration

    NASA Astrophysics Data System (ADS)

    Aristizábal, A.; Contreras, S.; Divins, N. J.; Llorca, J.; Medina, F.

    2014-04-01

    The influence of the Pt precursor and the impregnation protocol in the catalytic behavior of 3%Pt-1.5%Ag supported on activated carbon for water denitration in a continuous reactor was studied. Pt(NH3)4(NO3)2 and H2PtCl6 were selected as Pt precursors. Five protocols were investigated: sequential impregnations (both sequences), co-impregnation, physical mixture of monometallic catalysts, and physical mixture of a bimetallic catalyst with a Pt monometallic catalyst. The samples were characterized by XRD, XPS, TPR, HRTEM and physisorption. It was found that the catalytic activity strongly depends on the synthesis protocol and the Pt precursor, which modify the particle size. Higher nitrate rates are achieved using H2PtCl6 than Pt(NH3)4(NO3)2; this is mainly related to the smaller metal particle size of the former, evidenced by HRTEM. Nitrate consumption rate is directly related with the mean particle size. The physical mixture of monometallic catalysts resulted in the highest nitrogen rate.

  16. Pt/Mo2C/C-cp as a highly active and stable catalyst for ethanol electrooxidation

    NASA Astrophysics Data System (ADS)

    Lin, Lili; Sheng, Wenchao; Yao, Siyu; Ma, Ding; Chen, Jingguang G.

    2017-03-01

    A Pt/Mo2C/C-cp electrocatalyst with optimized Ptsbnd Mo2C chemical bonding is synthesized and evaluated for the ethanol oxidation reaction (EOR). The chemical bonding of Mo2C to Pt particles renders exceptional EOR activity at low potentials, which is 15 and 2.5 times higher than Pt/C and commercial 40% PtRu/C, respectively, at 0.6 V (vs. RHE). The stability of the Pt/Mo2C/C-cp electrocatalyst is comparable to the commercial 40% PtRu/C catalyst. CO stripping test demonstrates the existence of highly active sites for CO oxidation on the Pt/Mo2C/C-cp catalyst. In-situ infrared spectroscopic studies of EOR reveal that the excellent anti-poisoning ability of the Pt/Mo2C/C-cp catalyst is related to the relatively weak binding of carbonyl intermediates over the Pt/Mo2C/C-cp catalysts.

  17. Enhanced Catalytic Activity of Pt Supported on Nitrogen-Doped Reduced Graphene Oxide Electrodes for Fuel Cells.

    PubMed

    Sun, Qizhong; Park, Soo-Jin; Kim, Seok

    2015-11-01

    We report an efficient method for the synthesis of nitrogen-doped reduced graphene oxide supported Pt nanocatalysts (Pt/N-RGO). Nitrogen-doped reduced graphene oxide (N-RGO) was prepared by pyrolysis of graphene oxide with cyanamide as a nitrogen source. Then, the Pt nanoparticles were deposited over N-RGO by one-step chemical polyol reduction process. The morphology and structure of as-prepared catalysts were characterized by transmission electron microscopy (TEM), and X-ray diffraction (XRD). Subsequently, electrocatalytic activities of the catalysts were evaluated by cyclic voltammetry (CV). As a result, the Pt/N-RGO catalysts exhibit the superior electrochemical activity toward methanol oxidation in compared with that of Pt loaded on undoped reduced graphene oxide (Pt/RGO) and Pt/carbon blacks (Pt/C). This was mainly attributed to the better distribution of Pt nanoparticles as well as the synergistic electrochemical effects of the nitrogen doped supports. These results demonstrate that N-RGO could be a promising candidate as a high performance catalyst support for a fuel cell application.

  18. Colloidally prepared Pt nanowires versus impregnated Pt nanoparticles: comparison of adsorption and reaction properties.

    PubMed

    Haghofer, Andreas; Sonström, Patrick; Fenske, Daniela; Föttinger, Karin; Schwarz, Sabine; Bernardi, Johannes; Al-Shamery, Katharina; Bäumer, Marcus; Rupprechter, Günther

    2010-11-02

    Ligand-capped Pt nanowires, prepared by colloidal synthesis and deposited on a high surface area γ-Al(2)O(3) support, were subjected to surface characterization by electron microscopy and FTIR spectroscopy using CO as a probe molecule. The structural, adsorption, and catalytic reaction properties of the colloidal Pt nanowires were compared to those of conventional, impregnated Pt nanoparticles on the same Al(2)O(3) support. In situ FTIR spectroscopy indicated ligand effects on the CO resonance frequency, irreversible CO-induced surface roughening upon CO adsorption, and a higher resistance of colloidal catalysts toward oxidation (both in oxygen and during CO oxidation), suggesting that the organic ligands might protect the Pt surface. Elevated temperature induced a transformation of Pt nanowires to faceted Pt nanoparticles. The colloidal catalyst was active for hydrodechlorination of trichloroethylene (TCE), but no ligand effect on selectivity was obtained.

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

    PubMed Central

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

    2016-01-01

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

  20. Rotational effects in the dissociative adsorption of H2 on the Pt(211) stepped surface

    NASA Astrophysics Data System (ADS)

    Luppi, Marcello; McCormack, Drew A.; Olsen, Roar A.; Baerends, Evert Jan

    2005-10-01

    Rotational effects in the dissociative adsorption of H2 on the Pt(211) stepped surface have been studied using classical trajectory calculations on a six-dimensional, density-functional theory potential-energy surface. Reaction of rotating molecules via an indirect trapping mechanism exhibits an unexpected nonmonotonic dependence on the initial rotational quantum number J. Indirect reaction is first quenched with increasing J but is enhanced again for high J initial states. The quenching is attributed to rotational-to-translational energy transfer, which facilitates escape from the chemisorption wells responsible for molecular trapping. For high J, rotational and translational motions decouple, and the energy transfer is no longer possible, which leads again to trapping. Degeneracy-resolved calculations show that for high initial J, molecules rotating in a "cartwheel" fashion (mJ=0) are more likely to become trapped and react indirectly than "helicoptering" molecules (mJ=J). Experimental confirmation of this finding would lend strong support to the existence of the chemisorption wells that trap molecules prior to reaction.

  1. High-activity mesoporous Pt/Ru catalysts for methanol oxidation.

    PubMed

    Franceschini, Esteban A; Bruno, Mariano M; Williams, Federico J; Viva, Federico A; Corti, Horacio R

    2013-11-13

    High activity mesoporous Pt/Ru catalysts with 2D-hexagonal structure were synthesized using a triblock poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) copolymer (Pluronic F127) template. The normalized mass activities for the methanol oxidation reaction (MOR) of the Pt/Ru catalysts with a regular array of pores is higher than those reported for nanoparticulated Pt/Ru catalysts. Different kinetic parameters, as Tafel slope and activation energy, were obtained for the MOR on the mesoporous catalysts. Results indicated that catalysts performance depends on pore size. Mass activities and the CO2 conversion efficiency for large pore size mesoporous catalysts (10 nm) are greater than those reported for smaller pore size mesoporous catalysts with similar composition. The effect of pore size on catalysts performance is related to the greater accessibility of methanol to the active areas inside large pores. Consequently, the overall residence time of methanol increases as compared with mesoporous catalyst with small pores.

  2. One-Step Synthesis of Pt/Graphene Composites from Pt Acid Dissolved Ethanol via Microwave Plasma Spray Pyrolysis

    PubMed Central

    Jo, Eun Hee; Chang, Hankwon; Kim, Sun Kyung; Choi, Ji-Hyuk; Park, Su-Ryeon; Lee, Chong Min; Jang, Hee Dong

    2016-01-01

    Pt nanoparticles-laden graphene (Pt/GR) composites were synthesized in the gas phase from a mixture of ethanol and Pt precursor by microwave plasma spray pyrolysis. The morphology of Pt/GR composites has the shape of wrinkled sheets of paper, while Pt nanoparticles (Pt NPs) that are less than 2.6 nm in the mean diameter are uniformly well deposited on the surface of GR sheets stacked in only three layers. The Pt/GR composite prepared with 20 wt% of Pt had the highest specific surface area and electrochemical surface area of up to 402 m2 g−1 and 77 m2 g−1 (Pt), respectively. In addition, the composite showed superior electrocatalytic activity compared with commercial Pt-carbon black. The excellent electrocatalytic activity was attributed to the high specific surface area and electrochemical surface area of the Pt/GR composite directly produced by microwave plasma spray pyrolysis. Thus, it is clearly expected that the Pt/GR composite is a promising material for DMFC catalysts. PMID:27622908

  3. One-Step Synthesis of Pt/Graphene Composites from Pt Acid Dissolved Ethanol via Microwave Plasma Spray Pyrolysis.

    PubMed

    Jo, Eun Hee; Chang, Hankwon; Kim, Sun Kyung; Choi, Ji-Hyuk; Park, Su-Ryeon; Lee, Chong Min; Jang, Hee Dong

    2016-09-13

    Pt nanoparticles-laden graphene (Pt/GR) composites were synthesized in the gas phase from a mixture of ethanol and Pt precursor by microwave plasma spray pyrolysis. The morphology of Pt/GR composites has the shape of wrinkled sheets of paper, while Pt nanoparticles (Pt NPs) that are less than 2.6 nm in the mean diameter are uniformly well deposited on the surface of GR sheets stacked in only three layers. The Pt/GR composite prepared with 20 wt% of Pt had the highest specific surface area and electrochemical surface area of up to 402 m(2) g(-1) and 77 m(2) g(-1) (Pt), respectively. In addition, the composite showed superior electrocatalytic activity compared with commercial Pt-carbon black. The excellent electrocatalytic activity was attributed to the high specific surface area and electrochemical surface area of the Pt/GR composite directly produced by microwave plasma spray pyrolysis. Thus, it is clearly expected that the Pt/GR composite is a promising material for DMFC catalysts.

  4. One-Step Synthesis of Pt/Graphene Composites from Pt Acid Dissolved Ethanol via Microwave Plasma Spray Pyrolysis

    NASA Astrophysics Data System (ADS)

    Jo, Eun Hee; Chang, Hankwon; Kim, Sun Kyung; Choi, Ji-Hyuk; Park, Su-Ryeon; Lee, Chong Min; Jang, Hee Dong

    2016-09-01

    Pt nanoparticles-laden graphene (Pt/GR) composites were synthesized in the gas phase from a mixture of ethanol and Pt precursor by microwave plasma spray pyrolysis. The morphology of Pt/GR composites has the shape of wrinkled sheets of paper, while Pt nanoparticles (Pt NPs) that are less than 2.6 nm in the mean diameter are uniformly well deposited on the surface of GR sheets stacked in only three layers. The Pt/GR composite prepared with 20 wt% of Pt had the highest specific surface area and electrochemical surface area of up to 402 m2 g‑1 and 77 m2 g‑1 (Pt), respectively. In addition, the composite showed superior electrocatalytic activity compared with commercial Pt-carbon black. The excellent electrocatalytic activity was attributed to the high specific surface area and electrochemical surface area of the Pt/GR composite directly produced by microwave plasma spray pyrolysis. Thus, it is clearly expected that the Pt/GR composite is a promising material for DMFC catalysts.

  5. Role of electronic perturbation in stability and activity of Pt-based alloy nanocatalysts for oxygen reduction.

    PubMed

    Hwang, Seung Jun; Kim, Soo-Kil; Lee, June-Gunn; Lee, Seung-Cheol; Jang, Jong Hyun; Kim, Pil; Lim, Tae-Hoon; Sung, Yung-Eun; Yoo, Sung Jong

    2012-12-05

    The design of electrocatalysts for polymer electrolyte membrane fuel cells must satsify two equally important fundamental principles: optimization of electrocatalytic activity and long-term stability in acid media (pH <1) at high potential (0.8 V). We report here a solution-based approach to the preparation of Pt-based alloy with early transition metals and realistic parameters for the stability and activity of Pt(3)M (M = Y, Zr, Ti, Ni, and Co) nanocatalysts for oxygen reduction reaction (ORR). The enhanced stability and activity of Pt-based alloy nanocatalysts in ORR and the relationship between electronic structure modification and stability were studied by experiment and DFT calculations. Stability correlates with the d-band fillings and the heat of alloy formation of Pt(3)M alloys, which in turn depends on the degree of the electronic perturbation due to alloying. This concept provides realistic parameters for rational catalyst design in Pt-based alloy systems.

  6. A novel Pt-Co alloy hydrogen anode catalyst with superlative activity, CO-tolerance and robustness

    NASA Astrophysics Data System (ADS)

    Shi, G. Y.; Yano, H.; Tryk, D. A.; Watanabe, M.; Iiyama, A.; Uchida, H.

    2016-07-01

    PtCo nanoparticles, having two atomic layers of stabilized Pt skin, supported on carbon black (Pt2AL-PtCo/C), exhibited superlative mass activity for the CO-tolerant hydrogen oxidation reaction (HOR), together with high robustness with respect to air exposure, as a novel anode catalyst in reformate gas-based polymer electrolyte fuel cells. The high area-specific HOR activity and CO tolerance are consistent with DFT calculations.PtCo nanoparticles, having two atomic layers of stabilized Pt skin, supported on carbon black (Pt2AL-PtCo/C), exhibited superlative mass activity for the CO-tolerant hydrogen oxidation reaction (HOR), together with high robustness with respect to air exposure, as a novel anode catalyst in reformate gas-based polymer electrolyte fuel cells. The high area-specific HOR activity and CO tolerance are consistent with DFT calculations. Electronic supplementary information (ESI) available: Experimental details, TEM images and particle size distribution histograms of all catalysts, and details of the DFT calculations. See DOI: 10.1039/c6nr00778c

  7. Au-supported Pt-Au mixed atomic monolayer electrocatalyst with ultrahigh specific activity for oxidation of formic acid in acidic solution.

    PubMed

    Huang, Zhao; Liu, Yan; Xie, Fangyun; Fu, Yingchun; He, Yong; Ma, Ming; Xie, Qingji; Yao, Shouzhuo

    2012-12-25

    Au-supported Pt-Au mixed atomic monolayer electrocatalyst was prepared by underpotential deposition of Cu on Au and then redox replacement with noble metal atoms, which shows an ultrahigh Pt-mass (or Pt-area) normalized specific electrocatalytic activity of 102 mA μg(Pt)(-1) (124 mA cm(Pt)(-2)) for oxidation of formic acid in acidic aqueous solution.

  8. Surface Activation of Faceted Photocatalyst: When Metal Cocatalyst Determines the Nature of the Facets.

    PubMed

    Wang, Bin; Liu, Maochang; Zhou, Zhaohui; Guo, Liejin

    2015-11-01

    Pt nanoparticles with tunable size are prepared on the entire surface of facet-engineered Cu2WS4 decahedral photocatalyst via a kinetic-controlled chemical reduction process. The {101} facets of the photocatalyst which featured photo-oxidation, are successfully activated for photoreduction by Pt. The resulting photocatalyst shows an activity nine times higher compared to that of the only {001}-facets activated catalyst obtained by a conventional in situ photodeposition route.

  9. Generalized analysis of thermally activated domain-wall motion in Co/Pt multilayers

    NASA Astrophysics Data System (ADS)

    Emori, Satoru; Umachi, Chinedum K.; Bono, David C.; Beach, Geoffrey S. D.

    2015-03-01

    Thermally activated domain-wall (DW) motion driven by magnetic field and electric current is investigated experimentally in out-of-plane magnetized Pt(Co/Pt)3 multilayers. We directly extract the thermal activation energy barrier for DW motion and observe the dynamic regimes of creep, depinning, and viscous flow. Further analysis reveals that the activation energy must be corrected with a factor dependent on the Curie temperature, and we derive a generalized Arrhenius-like equation governing thermally activated motion. By using this generalized equation, we quantify the efficiency of current-induced spin torque in assisting DW motion. Current produces no effect aside from Joule heating in the multilayer with 7-Å thick Co layers, whereas it generates a finite spin torque on DWs in the multilayer with atomically thin 3-Å Co layers. These findings suggest that conventional spin-transfer torques from in-plane spin-polarized current do not drive DWs in ultrathin Co/Pt multilayers.

  10. Pt-Decorated PdCo@Pd/C Core-Shell Nanoparticles with Enhanced Stability and Electrocatalytic Activity for the Oxygen Reduction Reaction

    SciTech Connect

    Wang, Deli; Xin, Huolin L.; Yu, Yingchao; Wang, Hongsen; Rus, Eric; Muller, David A.; Abruña, Héctor D.

    2010-11-24

    A simple method for the preparation of PdCo@Pd core-shell nanoparticles supported on carbon based on an adsorbate-induced surface segregation effect has been developed. The stability of these PdCo@Pd nanoparticles and their electrocatalytic activity for the oxygen reduction reaction (ORR) were enhanced by decoration with a small amount of Pt deposited via a spontaneous displacement reaction. The facile method described herein is suitable for large-scale, lower-cost production and significantly lowers the Pt loading and thus the cost. The as-prepared PdCo@Pd and Pd-decorated PdCo@Pd nanocatalysts have a higher methanol tolerance than Pt/C in the ORR and are promising cathode catalysts for fuel cell applications.

  11. Correlating the chemical composition and size of various metal oxide substrates with the catalytic activity and stability of as-deposited Pt nanoparticles for the methanol oxidation reaction

    DOE PAGES

    Megan E. Scofield; Wong, Stanislaus S.; Koenigsmann, Christopher; ...

    2015-12-09

    The performance of electrode materials in conventional direct alcohol fuel cells (DAFC) is constrained by (i) the low activity of the catalyst materials relative to their overall cost, (ii) the poisoning of the active sites due to the presence of partially oxidized carbon species (such as but not limited to CO, formate, and acetate) produced during small molecule oxidation, and (iii) the lack of catalytic stability and durability on the underlying commercial carbon support. Therefore, as a viable alternative, we have synthesized various metal oxide and perovskite materials of different sizes and chemical compositions as supports for Pt nanoparticles (NPs).more » Our results including unique mechanistic studies demonstrate that the SrRuO3 substrate with immobilized Pt NPs at its surface evinces the best methanol oxidation performance as compared with all of the other substrate materials tested herein, including commercial carbon itself. In addition, data from electron energy loss spectroscopy (EELS) and X-ray photoelectron spectroscopy (XPS) confirmed the presence of electron transfer from bound Pt NPs to surface Ru species within the SrRuO3 substrate itself, thereby suggesting that favorable metal support interactions are responsible for the increased methanol oxidation reaction (MOR) activity of Pt species with respect to the underlying SrRuO3 composite catalyst material.« less

  12. Correlating the chemical composition and size of various metal oxide substrates with the catalytic activity and stability of as-deposited Pt nanoparticles for the methanol oxidation reaction

    SciTech Connect

    Megan E. Scofield; Wong, Stanislaus S.; Koenigsmann, Christopher; Bobb-Semple, Dara; Tao, Jing; Tong, Xiao; Wang, Lei; Lewis, Crystal S.; Vuklmirovic, Miomir; Zhu, Yimei; Adzic, Radoslav R.

    2015-12-09

    The performance of electrode materials in conventional direct alcohol fuel cells (DAFC) is constrained by (i) the low activity of the catalyst materials relative to their overall cost, (ii) the poisoning of the active sites due to the presence of partially oxidized carbon species (such as but not limited to CO, formate, and acetate) produced during small molecule oxidation, and (iii) the lack of catalytic stability and durability on the underlying commercial carbon support. Therefore, as a viable alternative, we have synthesized various metal oxide and perovskite materials of different sizes and chemical compositions as supports for Pt nanoparticles (NPs). Our results including unique mechanistic studies demonstrate that the SrRuO3 substrate with immobilized Pt NPs at its surface evinces the best methanol oxidation performance as compared with all of the other substrate materials tested herein, including commercial carbon itself. In addition, data from electron energy loss spectroscopy (EELS) and X-ray photoelectron spectroscopy (XPS) confirmed the presence of electron transfer from bound Pt NPs to surface Ru species within the SrRuO3 substrate itself, thereby suggesting that favorable metal support interactions are responsible for the increased methanol oxidation reaction (MOR) activity of Pt species with respect to the underlying SrRuO3 composite catalyst material.

  13. Chemical Strategies for Enhancing Activity and Charge Transfer in Ultrathin Pt Nanowires Immobilized onto Nanotube Supports for the Oxygen Reduction Reaction

    DOE PAGES

    Li, Luyao; Liu, Haiqing; Wang, Lei; ...

    2016-12-12

    Multiwalled carbon nanotubes (MWNTs) represent a promising support medium for electrocatalysts, especially Pt nanoparticles (NPs). The advantages of using MWNTs include their large surface area, high conductivity, as well as long-term stability. Surface functionalization of MWNTs with various terminal groups, such as -COOH, -SH, and -NH2, allows for rational electronic tuning of catalyst–support interactions. But, several issues still need to be addressed for such systems. Over the course of an electrochemical run, catalyst durability can decrease, due in part to metal NP dissolution, a process facilitated by the inherently high surface defect concentration within the support. Second, the covalent functionalizationmore » treatment of MWNTs adopted by most groups tends to lead to a loss of structural integrity of the nanotubes (NTs). In order to mitigate for all of these issues, we have utilized two different attachment approaches (i.e., covalent versus noncovalent) to functionalize the outer walls of pristine MWNTs and compared the catalytic performance of as-deposited ultrathin (<2 nm) 1D Pt nanowires with that of conventional Pt NPs toward the oxygen reduction reaction (ORR). Our results demonstrated that the electrochemical activity of Pt nanostructures immobilized onto functionalized carbon nanotube (CNT) supports could be dramatically improved by using ultrathin Pt nanowires (instead of NPs) with noncovalently (as opposed to covalently) functionalized CNT supports. Spectroscopic evidence corroborated the definitive presence of charge transfer between the metal catalysts and the underlying NT support, whose direction and magnitude are a direct function of (i) the terminal chemistry as well as (ii) the attachment methodology, both of which simultaneously impact upon the observed electrocatalytic performance. Specifically, the use of a noncovalent π–π stacking method coupled with a -COOH terminal moiety yielded the highest performance results, reported to

  14. Chemical Strategies for Enhancing Activity and Charge Transfer in Ultrathin Pt Nanowires Immobilized onto Nanotube Supports for the Oxygen Reduction Reaction

    SciTech Connect

    Li, Luyao; Liu, Haiqing; Wang, Lei; Yue, Shiyu; Tong, Xiao; Zaliznyak, Tatiana; Taylor, Gordon T.; Wong, Stanislaus S.

    2016-12-12

    Multiwalled carbon nanotubes (MWNTs) represent a promising support medium for electrocatalysts, especially Pt nanoparticles (NPs). The advantages of using MWNTs include their large surface area, high conductivity, as well as long-term stability. Surface functionalization of MWNTs with various terminal groups, such as -COOH, -SH, and -NH2, allows for rational electronic tuning of catalyst–support interactions. But, several issues still need to be addressed for such systems. Over the course of an electrochemical run, catalyst durability can decrease, due in part to metal NP dissolution, a process facilitated by the inherently high surface defect concentration within the support. Second, the covalent functionalization treatment of MWNTs adopted by most groups tends to lead to a loss of structural integrity of the nanotubes (NTs). In order to mitigate for all of these issues, we have utilized two different attachment approaches (i.e., covalent versus noncovalent) to functionalize the outer walls of pristine MWNTs and compared the catalytic performance of as-deposited ultrathin (<2 nm) 1D Pt nanowires with that of conventional Pt NPs toward the oxygen reduction reaction (ORR). Our results demonstrated that the electrochemical activity of Pt nanostructures immobilized onto functionalized carbon nanotube (CNT) supports could be dramatically improved by using ultrathin Pt nanowires (instead of NPs) with noncovalently (as opposed to covalently) functionalized CNT supports. Spectroscopic evidence corroborated the definitive presence of charge transfer between the metal catalysts and the underlying NT support, whose direction and magnitude are a direct function of (i) the terminal chemistry as well as (ii) the attachment methodology, both of which simultaneously impact upon the observed electrocatalytic performance. Specifically, the use of a noncovalent π–π stacking method coupled with a -COOH terminal moiety yielded the highest performance results, reported

  15. A rational computational study of surface defect-mediated stabilization of low-dimensional Pt nanostructures on TiN(100).

    PubMed

    Tak, Young Joo; Jang, Woosun; Richter, Norina A; Soon, Aloysius

    2015-04-21

    Platinum is known as a catalyst with exceptional reactivity for many important reactions, e.g. the oxygen reduction reaction. To reduce the high cost of pure platinum catalysts, platinum on a carbon support is widely used in industrial fuel cell applications. However, these Pt/C systems suffer from poor stability. As a cost-efficient and more durable alternative, Pt single-atom catalysts on a TiN support have recently been suggested, and it has been shown that the single-atom catalysts are stable when anchored at a nitrogen vacancy site on the TiN surface in a nitrogen-lean environment. To further explore the perspective of Pt/TiN catalytic systems, we provide insights into the stability and morphology of Pt nanostructures at the TiN(100) surface, using a density-functional theory approach in combination with ab initio atomistic thermodynamics. Our results show that the formation of two-dimensional Pt nano-layers is preferred over the formation of three-dimensional Pt nano-clusters on the TiN substrate. Similar to the single-atom catalysts, nano-layers of Pt can be stabilized on the TiN(100) surface by surface nitrogen vacancies under nitrogen-lean conditions. By analyzing the electronic metal-support interaction (EMSI) between the Pt nano-layer and the TiN surface with surface defects, we demonstrate that a strong EMSI between the surrounding Ti and Pt atoms is important for stabilizing the catalyst nano-layer at the TiN surface, and that N vacancies lead to stronger Pt-Ti interaction. This work provides a rational computational platform for the design of new generation high-performance Pt-based fuel cells.

  16. Tunable Surface Structuration of Silicon by Metal Assisted Chemical Etching with Pt Nanoparticles under Electrochemical Bias.

    PubMed

    Torralba, Encarnación; Le Gall, Sylvain; Lachaume, Raphaël; Magnin, Vincent; Harari, Joseph; Halbwax, Mathieu; Vilcot, Jean-Pierre; Cachet-Vivier, Christine; Bastide, Stéphane

    2016-11-16

    An in-depth study of metal assisted chemical etching (MACE) of p-type c-Si in HF/H2O2 aqueous solutions using Pt nanoparticles as catalysts is presented. Combination of cyclic voltammetry, open circuit measurements, chronoamperometry, impedance spectroscopy, and 2D band bending modeling of the metal/semiconductor/electrolyte interfaces at the nanoscale and under different etching conditions allows gaining physical insights into this system. Additionally, in an attempt to mimic the etching conditions, the modeling has been performed with a positively biased nanoparticle buried in the Si substrate. Following these findings, the application of an external polarization during etching is introduced as a novel efficient approach for achieving straightforward control of the pore morphology by acting upon the band bending at the Si/electrolyte junction. In this way, nanostructures ranging from straight mesopores to cone-shaped macropores are obtained as the Si sample is biased from negative to positive potentials. Remarkably, macroscopic cone-shaped pores in the 1-5 μm size range with a high aspect ratio (L/W ∼ 1.6) are obtained by this method. This morphology leads to a reduction of the surface reflectance below 5% over the entire VIS-NIR domain, which outperforms macrostructures made by state of the art texturization techniques for Si solar cells.

  17. Bulk and surface electronic structure of hexagonal structured PtBi2 studied by angle-resolved photoemission spectroscopy

    NASA Astrophysics Data System (ADS)

    Yao, Q.; Du, Y. P.; Yang, X. J.; Zheng, Y.; Xu, D. F.; Niu, X. H.; Shen, X. P.; Yang, H. F.; Dudin, P.; Kim, T. K.; Hoesch, M.; Vobornik, I.; Xu, Z.-A.; Wan, X. G.; Feng, D. L.; Shen, D. W.

    2016-12-01

    PtBi2 with a layered hexagonal crystal structure was recently reported to exhibit an unconventional large linear magnetoresistance, while the mechanism involved is still elusive. Using high-resolution angle-resolved photoemission spectroscopy, we present a systematic study on its bulk and surface electronic structure. Through careful comparison with first-principle calculations, our experiment distinguishes the low-lying bulk bands from entangled surface states, allowing the estimation of the real composition of samples. We find significant electron doping in PtBi2, implying a substantial Bi-deficiency-induced disorder therein. Intriguingly, we discover a Dirac-cone-like surface state on the boundary of the Brillouin zone, which is identified as an accidental Dirac band without topological protection. Our findings exclude linear band dispersion in the quantum limit as the cause of the unconventional large linear magnetoresistance but give support to the classical disorder model from the perspective of the electronic structure.

  18. The Effects of TI/PT Bottom Electrode on Crystallographic and Surface Characteristics of PZT Thick Films

    NASA Astrophysics Data System (ADS)

    Koochekzadeh, Ali; Keshavarz Alamdari, Eskandar; Barzegar, Abdolghafar

    The ceramic lead zirconate titanate (PZT) films near the morphotropic phase boundary are successfully integrated into MEMS devices, especially for applications in microsensors and actuators. The ferro/piezo electric properties of PZT thick films are widely dependent on its surface quality and crystallographic orientation growth. This paper indicates the influences of platinum bottom electrode on the surface and crystallographic properties of PZT. Ti (10nm) and Pt (100nm) thin films have been deposited on silicon substrate by thermal evaporation and electron beam respectively without vacuum breaking. After annealing treatment, the Pt film exhibited (111) preferred orientation. Finally one micron thick PZT (54/46) film was deposited by a RF magnetron sputtering at room temperature in pure Argon followed by a conventional post annealing treatment on silicon substrate. The XRD measurements have shown the provskite structure of PZT films with (100) preferred orientation at annealing temperatures above 600°C and (111) preferred orientation above 650°c. The SEM results demonstrate that whatever the annealing temperature is increased, recrystallization grains and black holes on Pt surface occurs and cause morphological change of PZT surface. The AFM test shows the strong RMS roughness of platinum surface after annealing temperature at 650°C.

  19. Spin Hall Magnetoresistance as a Probe for Surface Magnetization in Pt /Co Fe2O4 Bilayers

    NASA Astrophysics Data System (ADS)

    Isasa, Miren; Vélez, Saül; Sagasta, Edurne; Bedoya-Pinto, Amilcar; Dix, Nico; Sánchez, Florencio; Hueso, Luis E.; Fontcuberta, Josep; Casanova, Fèlix

    2016-09-01

    We study the spin Hall magnetoresistance (SMR) in Pt grown in situ on CoFe2O4 (CFO) ferrimagnetic insulating films. A careful analysis of the angle-dependent and field-dependent longitudinal magnetoresistance indicates that the SMR contains a contribution that does not follow the bulk magnetization of CFO, but it is a fingerprint of the complex magnetism at the surface of the CFO layer, thus signaling SMR as a tool for mapping surface magnetization. A systematic study of the SMR for different temperatures and CFO thicknesses gives us information impossible to obtain with any standard magnetometry technique. On one hand, the surface magnetization behaves independently of the CFO thickness and does not saturate up to high fields, evidencing that the surface has its own anisotropy. On the other hand, characteristic zero-field magnetization steps are not present at the surface while they are relevant in the bulk, strongly suggesting that antiphase boundaries are responsible for such intriguing features. In addition, a contribution from the ordinary magnetoresistance of Pt is identified, which is distinguishable only due to the low resistivity of the in situ grown Pt.

  20. CO oxidation on supported single Pt atoms: experimental and ab initio density functional studies of CO interaction with Pt atom on θ-Al2O3(010) surface.

    PubMed

    Moses-DeBusk, Melanie; Yoon, Mina; Allard, Lawrence F; Mullins, David R; Wu, Zili; Yang, Xiaofan; Veith, Gabriel; Stocks, G Malcolm; Narula, Chaitanya K

    2013-08-28

    Although there are only a few known examples of supported single-atom catalysts, they are unique because they bridge the gap between homogeneous and heterogeneous catalysis. Here, we report the CO oxidation activity of monodisperse single Pt atoms supported on an inert substrate, θ-alumina (Al2O3), in the presence of stoichiometric oxygen. Since CO oxidation on single Pt atoms cannot occur via a conventional Langmuir-Hinshelwood scheme (L-H scheme) which requires at least one Pt-Pt bond, we carried out a first-principles density functional theoretical study of a proposed pathway which is a variation on the conventional L-H scheme and inspired by the organometallic chemistry of platinum. We find that a single supported Pt atom prefers to bond to O2 over CO. CO then bonds with the oxygenated Pt atom and forms a carbonate which dissociates to liberate CO2, leaving an oxygen atom on Pt. Subsequent reaction with another CO molecule regenerates the single-atom catalyst. The energetics of the proposed mechanism suggests that the single Pt atoms will get covered with CO3 unless the temperature is raised to eliminate CO2. We find evidence for CO3 coverage at room temperature supporting the proposed mechanism in an in situ diffuse reflectance infrared study of CO adsorption on the catalyst's supported single atoms. Thus, our results clearly show that supported Pt single atoms are catalytically active and that this catalytic activity can occur without involving the substrate. Characterization by electron microscopy and X-ray absorption studies of the monodisperse Pt/θ-Al2O3 are also presented.

  1. The effect of H2O and pretreatment on the activity of a Pt/SnO2 catalyst

    NASA Technical Reports Server (NTRS)

    Vannorman, John D.; Brown, Kenneth G.; Schryer, Jacqueline; Schryer, David R.; Upchurch, Billy T.; Sidney, Barry D.

    1990-01-01

    CO oxidation catalysts with high activity at 25 C to 100 C are important for long-life, closed-cycle operation of pulsed CO2 lasers. A reductive pretreatment with either CO or H2 has been shown to significantly enhance the activity of a commercially available platinum on tin (IV) oxide (Pt/SnO2) catalyst relative to an oxidative or inert pretreatment or no pretreatment. Pretreatment at temperatures of 175 C and above causes an initial dip in the observed CO2 yield before the steady-state yield is attained. This dip has been found to be caused by dehydration of the catalyst during pretreatment and is readily eliminated by humidifying the catalyst or the reaction gas mixture. It is hypothesized that the effect of humidification is to increase the concentration of OH groups on the catalyst surface which play a role in the reaction mechanism.

  2. Structural and Electronic Transformations of Pt/C, Pd@Pt(1 ML)/C and Pd@Pt(2 ML)/C Cathode Catalysts in Polymer Electrolyte Fuel Cells during Potential-step Operating Processes Characterized by In-situ Time-resolved XAFS

    NASA Astrophysics Data System (ADS)

    Nagamatsu, Shin-ichi; Takao, Shinobu; Samjeské, Gabor; Nagasawa, Kensaku; Sekizawa, Oki; Kaneko, Takuma; Higashi, Kotaro; Uruga, Tomoya; Gayen, Sirshendu; Velaga, Srihari; Saniyal, Milan K.; Iwasawa, Yasuhiro

    2016-06-01

    The dynamic structural and electronic transformations of Pt/C, Pd@Pt(1 ML)/C, Pd@Pt(2 ML)/C cathode catalysts in polymer electrolyte fuel cells (PEFCs) during the potential-step operating processes between 0.4 and 1.4 VRHE (potential vs RHE) were characterized by in-situ (operando) time-resolved Pt LIII-edge quick-XAFS at 100 ms time-resolution. Potential-dependent surface structures and oxidation states of Pt, Pd@Pt(1 ML) and Pd@Pt(2 ML) nanoparticles on carbon at 0.4 and 1.4 VRHE were also analyzed by in-situ Pt LIII-edge and Pd K-edge quick-XAFS. The Pt, Pd@Pt(1 ML) and Pd@Pt(2 ML) nanoparticle surfaces were restructured and disordered at 1.4 VRHE, which were induced by strong Pt-O bonds as well as alloying effects. The rate constants for the changes of Pt valence, CN(Pt-Pt), CN(Pt-Pd) and CN(Pt-O) (CN: coordination number) in the potential-step operating processes were also determined and discussed in relation to the origin of oxygen reduction reaction (ORR) activities of the Pt/C, Pd@Pt(1 ML)/C and Pd@Pt(2 ML)/C cathode catalysts.

  3. Shape-controlled synthesis of porous AuPt nanoparticles and their superior electrocatalytic activity for oxygen reduction reaction

    PubMed Central

    Sun, Litai; Wang, Hongjing; Eid, Kamel; Wang, Liang

    2016-01-01

    Abstract Control of structure and morphology of Pt-based nanomaterials is of great importance for electrochemical energy conversions. In this work, we report an efficient one-step synthesis of bimetallic porous AuPt nanoparticles (PAuPt NPs) in an aqueous solution. The proposed synthesis is performed by a simple stirring treatment of an aqueous reactive mixture including K2PtCl4, HAuCl4, Pluronic F127 and ascorbic acid at a pH value of 1 without organic solvent or high temperature. Due to their porous structure and bimetallic composition, as-made PAuPt NPs exhibit excellent electrocatalytic activity for oxygen reduction reaction. PMID:27877858

  4. Antitumor activity of [Pt(O,O'-acac)(γ-acac)(DMS)] in mouse xenograft model of breast cancer

    PubMed Central

    Muscella, A; Vetrugno, C; Migoni, D; Biagioni, F; Fanizzi, F P; Fornai, F; De Pascali, S A; Marsigliante, S

    2014-01-01

    The higher and selective cytotoxicity of [Pt(O,O′-acac)(γ-acac)(DMS)] toward cancer cell in both immortalized cell lines and in breast cancer cells in primary cultures, stimulated a pre-clinical study so as to evaluate its therapeutic potential in vivo. The efficacy of [Pt(O,O′-acac)(γ-acac)(DMS)] was assessed using a xenograft model of breast cancer developed by injection of MCF-7 cells in the flank of BALB/c nude mice. Treatment of solid tumor-bearing mice with [Pt(O,O′-acac)(γ-acac)(DMS)] induced up to 50% reduction of tumor mass compared with an average 10% inhibition recorded in cisplatin-treated animals. Thus, chemotherapy with [Pt(O,O′-acac)(γ-acac)(DMS)] was much more effective than cisplatin. We also demonstrated enhanced in vivo pharmacokinetics, biodistribution and tolerability of [Pt(O,O′-acac)(γ-acac)(DMS)] when compared with cisplatin administered in Wistar rats. Pharmacokinetics studies with [Pt(O,O′-acac)(γ-acac)(DMS)] revealed prolonged Pt persistence in systemic blood circulation and decreased nefrotoxicity and hepatotoxicity, major target sites of cisplatin toxicity. Overall, [Pt(O,O′-acac)(γ-acac)(DMS)] turned out to be extremely promising in terms of greater in vivo anticancer activity, reduced nephrotoxicity and acute toxicity compared with cisplatin. PMID:24457958

  5. Self-Supported PtAuP Alloy Nanotube Arrays with Enhanced Activity and Stability for Methanol Electro-Oxidation.

    PubMed

    Zhang, Lili; Ding, Liang-Xin; Chen, Hongbin; Li, Dongdong; Wang, Suqing; Wang, Haihui

    2017-02-21

    Inhibiting CO formation can more directly address the problem of CO poisoning during methanol electro-oxidation. In this study, 1D self-supported porous PtAuP alloy nanotube arrays (ANTAs) are synthesized via a facile electro-codeposition approach and present enhanced activity and improved resistance to CO poisoning through inhibiting CO formation (non-CO pathway) during the methanol oxidation reaction in acidic medium. This well-controlled Pt-/transition metal-/nonmetal ternary nanostructure exhibits a specific electroactivity twice as great as that of PtAu alloy nanotube arrays and Pt/C. At the same time, PtAuP ANTAs show a higher ratio of forward peak current density (If ) to backward peak current density (Ib ) (2.34) than PtAu ANTAs (1.27) and Pt/C (0.78). The prominent If /Ib value of PtAuP ANTAs indicates that most of the intermediate species are electro-oxidized to carbon dioxide in the forward scan, which highlights the high electroactivity for methanol electro-oxidation.

  6. Effects of transition metal doping in Pt/M-TiO2 (M = V, Cr, and Nb) on oxygen reduction reaction activity

    NASA Astrophysics Data System (ADS)

    Kim, Jun-Hyuk; Kwon, Gihan; Lim, Hankwon; Zhu, Chenhui; You, Hoydoo; Kim, Yong-Tae

    2016-07-01

    High cost and low durability are unresolved issues that impede the commercialization of proton exchange membrane fuel cells (PEMFCs). To overcome these limitations, Pt/TiO2 is reported as an alternative electrocatalyst for enhancing the oxygen reduction reaction (ORR) activity and/or durability of the system. However, the low electrical conductivity of TiO2 is a drawback that may be addressed by doping. To date, most reports related to Pt/doped-TiO2 focus on changes in the catalyst activity caused by the Pt-TiO2 interaction (metal-support interaction), instead of the effect of doping itself; doping is merely considered to enhance the electrical conductivity of TiO2. In this study, we discuss the variation in the electronic fine structure of Pt caused by the dopant, and its correlation with the ORR activity. More extensive contraction of the Pt lattice in Pt/M-TiO2 (M = V, Cr, and Nb) relative to Pt/TiO2 and Pt/C leads to outstanding ORR specific activity of Pt/M-TiO2. Notably, a fourfold increase of the specific activity is achieved with Pt/V-TiO2 relative to Pt/C. Furthermore, an accelerated durability test (ADT) of Pt/V-TiO2 demonstrates that this system is three times more durable than conventional Pt/C due to the metal-support interaction.

  7. Electro-oxidation of ethanol on ternary non-alloyed Pt-Sn-Pr/C catalysts

    NASA Astrophysics Data System (ADS)

    Corradini, Patricia G.; Antolini, Ermete; Perez, Joelma

    2015-02-01

    Ternary Pt-Sn-Pr/C (70:10:20), (70:15:15) and (45:45:10) electro-catalysts were prepared by a modified formic acid method, and their activity for the ethanol oxidation reaction (EOR) was compared with that of Pt-Pr/C catalysts prepared by the same methods and that of commercial Pt-Sn/C (75:25) and Pt/C catalysts. Among all the catalysts, the Pt-Sn-Pr/C (45:45:10) catalyst presented both the highest mass activity and the highest specific activity. The steady state electrochemical stability of ternary Pt-Sn-Pr catalysts increased with the surface Sn/Pt atomic ratio. Following repetitive potential cycling (RPC), the activity for ethanol oxidation of Pt-Sn-Pr/C catalysts with high surface Sn/Pt atomic ratio was considerably higher than that of the corresponding as-prepared catalysts, and increased with increasing the Sn/Pt ratio. The increase of the EOR mass activity following RPC was ascribed to the increase of either the specific activity (for the Pt-Sn-Pr/C (70:15:15) catalyst) or the electrochemically active surface area (for the Pt-Sn-Pr/C (45:45:10) catalyst). Dissolution of Sn and Pr oxides from Pt-Sn-Pr/C catalyst surface was observed following RPC.

  8. The structure and reactivity of adsorbates on stepped Rh and Pt surfaces investigated by LEED, HREELS, TPD, XPS and STM

    SciTech Connect

    Batteas, J.D. |

    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.

  9. Steric Effect and Evolution of Surface Species in the Hydrodeoxygenation of Bio-Oil Model Compounds over Pt/HBEA

    DOE PAGES

    Foo, Guo Shiou; Rogers, Allyson K.; Yung, Matthew M.; ...

    2016-01-11

    The hydrodeoxygenation of various bio-oil model compounds (anisole, m-cresol and guaiacol) over Pt/HBEA and the evolution of surface species is investigated. Depending on the functional group, different surface species are formed when the compounds are adsorbed in the presence of Lewis acid sites. For anisole, the methoxy group is decomposed to form phenate species. The methyl and methoxy group remains intact on m-cresol and guaiacol to form cresolate and methoxy phenate species, respectively. The position of these functional groups have a strong influence in the degree of hydrodeoxygenation due to steric hindrance. Based on operando transmission FTIR spectroscopy, a timelinemore » for the formation of polynuclear aromatics and catalyst deactivation is constructed, which is also dependent on the substituents. The slow deactivation rate and low carbon content on Pt/HBEA is discussed.« less

  10. Steric Effect and Evolution of Surface Species in the Hydrodeoxygenation of Bio-Oil Model Compounds over Pt/HBEA

    SciTech Connect

    Foo, Guo Shiou; Rogers, Allyson K.; Yung, Matthew M.; Sievers, Carsten

    2016-01-11

    The hydrodeoxygenation of various bio-oil model compounds (anisole, m-cresol and guaiacol) over Pt/HBEA and the evolution of surface species is investigated. Depending on the functional group, different surface species are formed when the compounds are adsorbed in the presence of Lewis acid sites. For anisole, the methoxy group is decomposed to form phenate species. The methyl and methoxy group remains intact on m-cresol and guaiacol to form cresolate and methoxy phenate species, respectively. The position of these functional groups have a strong influence in the degree of hydrodeoxygenation due to steric hindrance. Based on operando transmission FTIR spectroscopy, a timeline for the formation of polynuclear aromatics and catalyst deactivation is constructed, which is also dependent on the substituents. The slow deactivation rate and low carbon content on Pt/HBEA is discussed.

  11. Reactivity of atomically dispersed Pt(2+) species towards H2: model Pt-CeO2 fuel cell catalyst.

    PubMed

    Lykhach, Yaroslava; Figueroba, Alberto; Camellone, Matteo Farnesi; Neitzel, Armin; Skála, Tomáš; Negreiros, Fabio R; Vorokhta, Mykhailo; Tsud, Nataliya; Prince, Kevin C; Fabris, Stefano; Neyman, Konstantin M; Matolín, Vladimír; Libuda, Jörg

    2016-03-21

    The reactivity of atomically dispersed Pt(2+) species on the surface of nanostructured CeO2 films and the mechanism of H2 activation on these sites have been investigated by means of synchrotron radiation photoelectron spectroscopy and resonant photoemission spectroscopy in combination with density functional calculations. Isolated Pt(2+) sites are found to be inactive towards H2 dissociation due to high activation energy required for H-H bond scission. Trace amounts of metallic Pt are necessary to initiate H2 dissociation on Pt-CeO2 films. H2 dissociation triggers the reduction of Ce(4+) cations which, in turn, is coupled with the reduction of Pt(2+) species. The mechanism of Pt(2+) reduction involves reverse oxygen spillover and formation of oxygen vacancies on Pt-CeO2 films. Our calculations suggest the existence of a threshold concentration of oxygen vacancies associated with the onset of Pt(2+) reduction.

  12. Ternary FexCo1-xP Nanowire Array as a Robust Hydrogen Evolution Reaction Electrocatalyst with Pt-like Activity: Experimental and Theoretical Insight.

    PubMed

    Tang, Chun; Gan, Linfeng; Zhang, Rong; Lu, Wenbo; Jiang, Xiue; Asiri, Abdullah M; Sun, Xuping; Wang, Jin; Chen, Liang

    2016-10-12

    Replacement of precious Pt with earth-abundant electrocatalysts for the hydrogen evolution reaction (HER) holds great promise for clean energy devices, but the development of low-cost and durable HER catalysts with Pt-like activity is still a huge challenge. In this communication, we report on the development of self-standing ternary FexCo1-xP nanowire array on carbon cloth (FexCo1-xP/CC) as a Pt-free HER catalyst with activities being strongly related to Fe substitution ratio. Electrochemical tests show that Fe0.5Co0.5P/CC not only possesses Pt-like activity with the need of overpotential of only 37 mV to drive 10 mA cm(-2), outperforming all non-noble-metal HER catalysts reported to date, but demonstrates superior long-term durability in 0.5 M H2SO4. Density functional theory calculations further reveal that Fe substitution of Co in CoP leads to more optimal free energy of hydrogen adsorption to the catalyst surface. This study offers us a promising flexible monolithic catalyst for practical applications.

  13. SOx Tolerant Pt/TiO2 Catalysts for CO Oxidation and the Effect of TiO2 Supports on Catalytic Activity.

    PubMed

    Taira, Kenji; Nakao, Kenji; Suzuki, Kimihito; Einaga, Hisahiro

    2016-09-06

    We developed a new technique for mitigating catalyst deactivation caused by SO2 in exhaust gases. A series of 0.1 wt %-Pt/TiO2 catalysts with different surface, crystal, and pore structures were prepared and tested for CO oxidation activity in the presence of SO2 and H2O. The order of the CO oxidation activity under the influence of SO2 was much different from that in the absence of SO2. Catalysts with a high ratio of larger pores exhibited higher catalytic activity under the influence of SO2 and H2O in the temperature range of 250-300 °C, whereas other parameters, such as BET surface area and crystal structure of the TiO2 support, had minor effects on the CO oxidation activity. The oxidation state of Pt differed significantly depending on the kind of TiO2 support. Some catalysts were less active without H2 reduction pretreatment due to the presence of oxidized Pt species.

  14. Catalytically Triggered Energy Release from Strained Organic Molecules: The Surface Chemistry of Quadricyclane and Norbornadiene on Pt(111).

    PubMed

    Bauer, Udo; Mohr, Susanne; Döpper, Tibor; Bachmann, Philipp; Späth, Florian; Düll, Fabian; Schwarz, Matthias; Brummel, Olaf; Fromm, Lukas; Pinkert, Ute; Görling, Andreas; Hirsch, Andreas; Bachmann, Julien; Steinrück, Hans-Peter; Libuda, Jörg; Papp, Christian

    2017-01-31

    We have investigated the surface chemistry of the polycyclic valence-isomer pair norbornadiene (NBD) and quadricyclane (QC) on Pt(111). The NBD/QC system is considered to be a prototype for energy storage in strained organic compounds. By using a multimethod approach, including UV photoelectron, high-resolution X-ray photoelectron, and IR reflection-absorption spectroscopic analysis and DFT calculations, we could unambiguously identify and differentiate between the two molecules in the multilayer phase, which implies that the energy-loaded QC molecule is stable in this state. Upon adsorption in the (sub)monolayer regime, the different spectroscopies yielded identical spectra for NBD and QC at 125 and 160 K, when multilayer desorption takes place. This behavior is explained by a rapid cycloreversion of QC to NBD upon contact with the Pt surface. The NBD adsorbs in a η(2) :η(1) geometry with an agostic Pt-H interaction of the bridgehead CH2 subunit and the surface. Strong spectral changes are observed between 190 and 220 K because the hydrogen atom that forms the agostic bond is broke. This reaction yields a norbornadienyl intermediate species that is stable up to approximately 380 K. At higher temperatures, the molecule dehydrogenates and decomposes into smaller carbonaceous fragments.

  15. 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.

    PubMed

    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.

  16. The SHORT-ROOT-like gene PtSHR2B is involved in Populus phellogen activity.

    PubMed

    Miguel, Andreia; Milhinhos, Ana; Novák, Ondřej; Jones, Brian; Miguel, Célia M

    2016-03-01

    SHORT-ROOT (SHR) is a GRAS transcription factor first characterized for its role in the specification of the stem cell niche and radial patterning in Arabidopsis thaliana (At) roots. Three SHR-like genes have been identified in Populus trichocarpa (Pt). PtSHR1 shares high similarity with AtSHR over the entire length of the coding sequence. The two other Populus SHR-like genes, PtSHR2A and PtSHR2B, are shorter in their 5' ends when compared with AtSHR. Unlike PtSHR1, that is expressed throughout the cambial zone of greenhouse-grown Populus trees, PtSHR2Bprom:uidA expression was detected in the phellogen. Additionally, PtSHR1 and PtSHR2B expression patterns markedly differ in the shoot apex and roots of in vitro plants. Transgenic hybrid aspen expressing PtSHR2B under the 35S constitutive promoter showed overall reduced tree growth while the proportion of bark increased relative to the wood. Reverse transcription-quantitative PCR (RT-qPCR) revealed increased transcript levels of cytokinin metabolism and response-related genes in the transgenic plants consistent with an increase of total cytokinin levels. This was confirmed by cytokinin quantification by LC-MS/MS. Our results indicate that PtSHR2B appears to function in the phellogen and therefore in the regulation of phellem and periderm formation, possibly acting through modulation of cytokinin homeostasis. Furthermore, this work points to a functional diversification of SHR after the divergence of the Populus and Arabidopsis lineages. This finding may contribute to selection and breeding strategies of cork oak in which, unlike Populus, the phellogen is active throughout the entire tree lifespan, being at the basis of a highly profitable cork industry.

  17. Effect of surface groups on the electrocatalytic behaviour of Pt-Fe-Co alloy-dispersed carbon electrodes in the phosphoric acid fuel cell

    NASA Astrophysics Data System (ADS)

    Pyun, Su-Il; Lee, Seung-Bok

    Effect of surface group on the electrocatalytic behaviour of 10 wt.% Pt-Fe-Co alloy-dispersed carbon (Pt-Fe-Co/C) electrode has been investigated as functions of applied potential and duration in 85% H 3PO 4 solution of 145°C, using Fourier transform infrared (FTIR) spectroscopy, combined with ac-impedance spectroscopy, potentiostatic current transient technique, and potentiodynamic polarization experiment. It was shown from FTIR spectra that surface group formed in this work mainly comprises carboxyl group and that the formation potential of carboxyl group lies between 600 and 700 mV RHE. From increase of charge transfer resistance ( Rct), and decrease of electrocatalytic activity for oxygen reduction with immersion time, it is suggested that above the formation potential of carboxyl group, further formation of carboxyl group on the carbon support around the catalyst particle reduces active surface area of the catalyst particle with immersion time. On the other hand, below the formation potential, dissolution of carboxyl group previously formed on the carbon support raises active surface area of the catalyst particle. In the present study, relationship between electrocatalytic aspect of the electrode, and the amount of carboxyl group formed on the carbon support around the catalyst particle was well discussed with a schematic illustration. The illustrative representation is underlain by formation on and dissolution from the catalyst particle of carboxyl group which cause the rise and fall in circumferential coverage of carboxyl group, respectively and hence the reduction and elevation in active surface area of the catalyst particle.

  18. A Strategy for Fabricating Porous PdNi@Pt Core-shell Nanostructures and Their Enhanced Activity and Durability for the Methanol Electrooxidation

    PubMed Central

    Liu, Xinyu; Xu, Guangrui; Chen, Yu; Lu, Tianhong; Tang, Yawen; Xing, Wei

    2015-01-01

    Three-dimensionally (3D) porous morphology of nanostructures can effectively improve their electrocatalytic activity and durability for various electrochemical reactions owing to big surface area and interconnected structure. Cyanogel, a jelly-like inorganic polymer, can be used to synthesize various three-dimensionally (3D) porous alloy nanomaterials owing to its double-metal property and particular 3D backbone. Here, 3D porous PdNi@Pt core-shell nanostructures (CSNSs) are facilely synthesized by first preparing the Pd-Ni alloy networks (Pd-Ni ANWs) core via cyanogel-reduction method followed by a galvanic displacement reaction to generate the Pt-rich shell. The as-synthesized PdNi@Pt CSNSs exhibit a much improved catalytic activity and durability for the methanol oxidation reaction (MOR) in the acidic media compared to the commercial used Pt black because of their specific structural characteristics. The facile and mild method described herein is highly attractive for the synthisis of 3D porous core-shell nanostructures. PMID:25557190

  19. State selective vibrational (2ν3) activation of the chemisorption of methane on Pt (111)

    NASA Astrophysics Data System (ADS)

    Higgins, J.; Conjusteau, A.; Scoles, G.; Bernasek, S. L.

    2001-03-01

    The state-selective dissociative sticking coefficient on Pt(111) surfaces for CH4 in the 2ν3 J=1,2 ro-vibrational levels has been measured using thermal energy atomic scattering. Continuous wave laser excitation of a molecular beam of CH4 seeded in He with a 1.5 μm color center laser, tunable around 6000 cm-1 and coupled to the beam by means of a resonant build-up cavity, allows pumping of up to 11% of the molecules to the excited ro-vibrational state. The laser/molecular beam combination allows precise control over the translational energy as well as the vibrational state of the methane that impinges on the clean Pt(111) surface. The intensity of the specular reflection of the incident helium beam is used to quantitatively monitor the coverage of chemisorbed methane on the platinum surface as a function of time (exposure). The sticking coefficient (S0) of CH4 with 5.4 kJ/mol normal translational energy is found to increase from 6.2×10-6 to 1.8×10-4 upon 2ν3 excitation (the overtone of the asymmetric stretch of methane). This represents a ˜30 fold enhancement in reactivity of the methane with the Pt(111) surface upon vibrational excitation. We also measured the changes of S0 obtained by varying the nozzle temperature and methane concentration over a tenfold range of energy. We find that 72 kJ/mol of vibrational energy in the excited CH4 is approximately equivalent to at least 30 kJ/mol of normal translational energy. This corresponds to a utilization efficiency of the 2ν3 vibrational energy of greater than 40%. In the only other measurement of this kind published in the literature, [L. B. F. Juurlink, P. R. McCabe, R. R. Smith, C. L. DiCologero, and A. L. Utz, Phys. Rev Lett. 83, 868 (1999)] for the fundamental (v=1) excitation of ν3 of CH4 on Ni(100) surfaces, a comparable value for the vibrational energy utilization efficiency was found (59%). Further work is necessary to determine if this result is general and if and how it may change by changing the

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

    PubMed

    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 Au(3+) 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. Halogen poisoning effect of Pt-TiO2 for formaldehyde catalytic oxidation performance at room temperature

    NASA Astrophysics Data System (ADS)

    Zhu, Xiaofeng; Cheng, Bei; Yu, Jiaguo; Ho, Wingkei

    2016-02-01

    Catalytic decomposition of formaldehyde (HCHO) at room temperature is an important method for HCHO removal. Pt-based catalysts are the optimal catalyst for HCHO decomposition at room temperature. However, the stability of this catalyst remains unexplored. In this study, Pt-TiO2 (Pt-P25) catalysts with and without adsorbed halogen ions (including F-, Cl-, Br-, and I-) were prepared through impregnation and ion modification. Pt-TiO2 samples with adsorbed halogen ions exhibited reduced catalytic activity for formaldehyde decomposition at room temperature compared with the Pt-TiO2 sample; the catalytic activity followed the order of F-Pt-P25, Cl-Pt-P25, Br-Pt-P25, and I-Pt-P25. Characterization results (including XRD, TEM, HRTEM, BET, XPS, and metal dispersion) showed that the adsorbed halogen ions can poison Pt nanoparticles (NPs), thereby reducing the HCHO oxidation activity of Pt-TiO2. The poison mechanism is due to the strong adsorption of halogen ions on the surface of Pt NPs. The adsorbed ions form coordination bonds with surface Pt atoms by transferring surplus electrons into the unoccupied 5d orbit of the Pt atom, thereby inhibiting oxygen adsorption and activation of the Pt NP surface. Moreover, deactivation rate increases with increasing diameter of halogen ions. This study provides new insights into the fabrication of high-performance Pt-based catalysts for indoor air purification.

  2. Biaxially strained PtPb/Pt core/shell nanoplate boosts oxygen reduction catalysis

    SciTech Connect

    Bu, Lingzheng; Zhang, Nan; Guo, Shaojun; Zhang, Xu; Li, Jing; Yao, Jianlin; Wu, Tao; Lu, Gang; Ma, Jing-Yuan; Su, Dong; Huang, Xiaoqing

    2016-12-16

    Compressive surface strains have been necessary to boost oxygen reduction reaction (ORR) activity in core/shell M/Pt catalysts (where M can be Ni, Co, Fe). We report a class of PtPb/Pt core/shell nanoplate catalysts that exhibit large biaxial tensile strains. The stable Pt (110) facets of the nanoplates have high ORR specific and mass activities that reach 7.8 milliampere per centimeter square and 4.3 ampere per milligram of platinum at 0.9 volts versus the reversible hydrogen electrode (RHE), respectively. Density functional theory calculations revealed that the edge-­Pt and top (bottom)-Pt (110) facets undergo large tensile strains that help optimize the Pt-­O bond strength. The intermetallic core and uniform 4 layers of Pt shell of the PtPb/Pt nanoplates appear to underlie the high endurance of these catalysts, which can undergo 50,000 voltage cycles with negligible activity decay and no apparent structure and composition changes.

  3. Biaxially strained PtPb/Pt core/shell nanoplate boosts oxygen reduction catalysis

    DOE PAGES

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

    2016-12-16

    Compressive surface strains have been necessary to boost oxygen reduction reaction (ORR) activity in core/shell M/Pt catalysts (where M can be Ni, Co, Fe). We report a class of PtPb/Pt core/shell nanoplate catalysts that exhibit large biaxial tensile strains. The stable Pt (110) facets of the nanoplates have high ORR specific and mass activities that reach 7.8 milliampere per centimeter square and 4.3 ampere per milligram of platinum at 0.9 volts versus the reversible hydrogen electrode (RHE), respectively. Density functional theory calculations revealed that the edge-­Pt and top (bottom)-Pt (110) facets undergo large tensile strains that help optimize the Pt-­Omore » bond strength. The intermetallic core and uniform 4 layers of Pt shell of the PtPb/Pt nanoplates appear to underlie the high endurance of these catalysts, which can undergo 50,000 voltage cycles with negligible activity decay and no apparent structure and composition changes.« less

  4. Activity, short-term stability (poisoning tolerance) and durability of carbon supported Pt-Pr catalysts for ethanol oxidation

    NASA Astrophysics Data System (ADS)

    Corradini, Patricia G.; Antolini, Ermete; Perez, Joelma

    2014-04-01

    Pt-Pr/C electrocatalysts were prepared by a modified formic acid method, and their activity for carbon monoxide and ethanol oxidation, their short term stability and durability were compared to that of commercial Pt/C and Pt-Sn/C (3:1) catalysts. By derivative voltammetry (DV) it was found that ethanol electro-oxidation takes place by two main pathways at different potentials. It was observed that, in the presence of Pr, ethanol electro-oxidation takes place mostly through the pathway at lower potential, which is the most interesting for fuel cell application. The Pt-Pr/C catalysts were less tolerant to poisoning by ethanol oxidation intermediate species than Pt/C. Durability test by a repetitive potential cycling under Ar atmosphere revealed a good structural stability of Pt-Pr/C catalysts. A repetitive potential cycling under CO atmosphere carried out on the Pt-Pr/C (1:1) catalyst, instead, indicated a structural change, likely by formation of a core-shell structure.

  5. Dendrimer Templated Synthesis of One Nanometer Rh and Pt Particles Supported on Mesoporous Silica: Catalytic Activity for Ethylene and Pyrrole Hydrogenation.

    SciTech Connect

    Huang, Wenyu; Kuhn, John N.; Tsung, Chia-Kuang; Zhang, Yawen; Habas, Susan E.; Yang, Peidong; Somorjai, Gabor A.

    2008-05-09

    Monodisperse rhodium (Rh) and platinum (Pt) nanoparticles as small as {approx}1 nm were synthesized within a fourth generation polyaminoamide (PAMAM) dendrimer, a hyperbranched polymer, in aqueous solution and immobilized by depositing onto a high-surface-area SBA-15 mesoporous support. X-ray photoelectron spectroscopy indicated that the as-synthesized Rh and Pt nanoparticles were mostly oxidized. Catalytic activity of the SBA-15 supported Rh and Pt nanoparticles was studied with ethylene hydrogenation at 273 and 293 K in 10 torr of ethylene and 100 torr of H{sub 2} after reduction (76 torr of H{sub 2} mixed with 690 torr of He) at different temperatures. Catalysts were active without removing the dendrimer capping but reached their highest activity after hydrogen reduction at a moderate temperature (423 K). When treated at a higher temperature (473, 573, and 673 K) in hydrogen, catalytic activity decreased. By using the same treatment that led to maximum ethylene hydrogenation activity, catalytic activity was also evaluated for pyrrole hydrogenation.

  6. Observation of unusual topological surface states in half-Heusler compounds LnPtBi (Ln=Lu, Y).

    PubMed

    Liu, Z K; Yang, L X; Wu, S-C; Shekhar, C; Jiang, J; Yang, H F; Zhang, Y; Mo, S-K; Hussain, Z; Yan, B; Felser, C; Chen, Y L

    2016-09-27

    Topological quantum materials represent a new class of matter with both exotic physical phenomena and novel application potentials. Many Heusler compounds, which exhibit rich emergent properties such as unusual magnetism, superconductivity and heavy fermion behaviour, have been predicted to host non-trivial topological electronic structures. The coexistence of topological order and other unusual properties makes Heusler materials ideal platform to search for new topological quantum phases (such as quantum anomalous Hall insulator and topological superconductor). By carrying out angle-resolved photoemission spectroscopy and ab initio calculations on rare-earth half-Heusler compounds LnPtBi (Ln=Lu, Y), we directly observe the unusual topological surface states on these materials, establishing them as first members with non-trivial topological electronic structure in this class of materials. Moreover, as LnPtBi compounds are non-centrosymmetric superconductors, our discovery further highlights them as promising candidates of topological superconductors.

  7. Role of the Pinning Points in epitaxial Graphene Moiré Superstructures on the Pt(111) Surface

    PubMed Central

    Martínez, José I.; Merino, Pablo; Pinardi, Anna L.; Gonzalo, Otero-Irurueta; López, María F.; Méndez, Javier; Martín-Gago, José A.

    2016-01-01

    The intrinsic atomic mechanisms responsible for electronic doping of epitaxial graphene Moirés on transition metal surfaces is still an open issue. To better understand this process we have carried out a first-principles full characterization of the most representative Moiré superstructures observed on the Gr/Pt(111) system and confronted the results with atomically resolved scanning tunneling microscopy experiments. We find that for all reported Moirés the system relaxes inducing a non-negligible atomic corrugation both, at the graphene and at the outermost platinum layer. Interestingly, a mirror “anti-Moiré” reconstruction appears at the substrate, giving rise to the appearance of pinning-points. We show that these points are responsible for the development of the superstructure, while charge from the Pt substrate is injected into the graphene, inducing a local n-doping, mostly localized at these specific pinning-point positions. PMID:26852920

  8. Role of the Pinning Points in epitaxial Graphene Moiré Superstructures on the Pt(111) Surface.

    PubMed

    Martínez, José I; Merino, Pablo; Pinardi, Anna L; Gonzalo, Otero-Irurueta; López, María F; Méndez, Javier; Martín-Gago, José A

    2016-02-08

    The intrinsic atomic mechanisms responsible for electronic doping of epitaxial graphene Moirés on transition metal surfaces is still an open issue. To better understand this process we have carried out a first-principles full characterization of the most representative Moiré superstructures observed on the Gr/Pt(111) system and confronted the results with atomically resolved scanning tunneling microscopy experiments. We find that for all reported Moirés the system relaxes inducing a non-negligible atomic corrugation both, at the graphene and at the outermost platinum layer. Interestingly, a mirror "anti-Moiré" reconstruction appears at the substrate, giving rise to the appearance of pinning-points. We show that these points are responsible for the development of the superstructure, while charge from the Pt substrate is injected into the graphene, inducing a local n-doping, mostly localized at these specific pinning-point positions.

  9. Observation of unusual topological surface states in half-Heusler compounds LnPtBi (Ln=Lu, Y)

    NASA Astrophysics Data System (ADS)

    Liu, Z. K.; Yang, L. X.; Wu, S.-C.; Shekhar, C.; Jiang, J.; Yang, H. F.; Zhang, Y.; Mo, S.-K.; Hussain, Z.; Yan, B.; Felser, C.; Chen, Y. L.

    2016-09-01

    Topological quantum materials represent a new class of matter with both exotic physical phenomena and novel application potentials. Many Heusler compounds, which exhibit rich emergent properties such as unusual magnetism, superconductivity and heavy fermion behaviour, have been predicted to host non-trivial topological electronic structures. The coexistence of topological order and other unusual properties makes Heusler materials ideal platform to search for new topological quantum phases (such as quantum anomalous Hall insulator and topological superconductor). By carrying out angle-resolved photoemission spectroscopy and ab initio calculations on rare-earth half-Heusler compounds LnPtBi (Ln=Lu, Y), we directly observe the unusual topological surface states on these materials, establishing them as first members with non-trivial topological electronic structure in this class of materials. Moreover, as LnPtBi compounds are non-centrosymmetric superconductors, our discovery further highlights them as promising candidates of topological superconductors.

  10. Observation of unusual topological surface states in half-Heusler compounds LnPtBi (Ln=Lu, Y)

    PubMed Central

    Liu, Z. K.; Yang, L. X.; Wu, S.-C.; Shekhar, C.; Jiang, J.; Yang, H. F.; Zhang, Y.; Mo, S.-K.; Hussain, Z.; Yan, B.; Felser, C.; Chen, Y. L.

    2016-01-01

    Topological quantum materials represent a new class of matter with both exotic physical phenomena and novel application potentials. Many Heusler compounds, which exhibit rich emergent properties such as unusual magnetism, superconductivity and heavy fermion behaviour, have been predicted to host non-trivial topological electronic structures. The coexistence of topological order and other unusual properties makes Heusler materials ideal platform to search for new topological quantum phases (such as quantum anomalous Hall insulator and topological superconductor). By carrying out angle-resolved photoemission spectroscopy and ab initio calculations on rare-earth half-Heusler compounds LnPtBi (Ln=Lu, Y), we directly observe the unusual topological surface states on these materials, establishing them as first members with non-trivial topological electronic structure in this class of materials. Moreover, as LnPtBi compounds are non-centrosymmetric superconductors, our discovery further highlights them as promising candidates of topological superconductors. PMID:27671444

  11. Reduction of surface roughness and Neel coupling in perpendicular magnetic tunnel junctions with L1{sub 0}-FePt electrodes by plasma treatments

    SciTech Connect

    Tsai, Wu-Chang; Lee, Jian-Wei; Chen, Chia-Hsiang; Lai, Chih-Huang; Yen, Cheng-Tyng; Wang, Yung-Hung

    2011-04-01

    The plasma treatment with O{sub 2}/Ar mixture was applied to reduce the surface roughness of the L1{sub 0}-FePt electrode in perpendicular magnetic tunnel junctions. The surface roughness (R{sub rms}) of the L1{sub 0}-FePt layer was decreased from 1.2 nm at the as-deposited state to 0.52 nm after the plasma treatment with the ratio of O{sub 2} to Ar equal to 0.5. The low surface roughness accompanying the formation of an oxide layer led to magnetic decoupling between free and reference layers after the plasma treatment on the surface of FePt layer. The existence of the oxide layer was confirmed by using transmission electron microscopy and x-ray photoelectron spectroscopy. The interfacial Pt-oxide layer plays a significant role in the magnetic decoupling.

  12. Pt interactions with annealed and chemically-etched Nb-doped SrTiO 3(0 0 1) surfaces: Metal/oxide surface chemical effects on band bending behavior

    NASA Astrophysics Data System (ADS)

    Vamala, Chiranjeevi; Manandhar, Sudha; Kelber, Jeff

    2009-01-01

    XPS and LEED have been used to characterize the interaction of sputter-deposited Pt (maximum coverage <5 ML) with Nb-doped SrTiO3(0 0 1) surfaces prepared either by annealing in O2 and then UHV, or by chemical-etching in aqua regia. The annealed surface exhibits an ordered (1 × 1) LEED pattern, with additional diffraction spots and streaks indicating the presence of oxygen vacancies. Increasing Pt coverage results in the decrease of the observed Pt(4f7/2) binding energy and the uniform shift of the Sr(3d), Ti(2p) and O(1s) levels to smaller binding energies, as expected for Pt cluster growth and surface-to-Pt charge donation on an n-type semiconductor. The etched surface is disordered, and exhibits a hydroxylated surface with a contaminant C film of ∼23 Ǻ average thickness. Pt deposition on the etched surface results in an immediate decrease in the intensity of the OH feature in the O(1s) spectrum, and a uniform shift of the Sr(3d), Ti(2p) and O(1s) levels to larger binding energies with increasing Pt coverage. The observed Pt(4f7/2) binding energy on the etched surface (∼72 eV) is independent of Pt coverage, and indicates substantial electronic charge donation from the Pt to surface hydroxyl species. The observation of band bending towards higher binding energies upon Pt deposition (behavior normally associated with p-type semiconductors) demonstrates that sub-monolayer quantities of adsorbates can alter metal/oxide interfacial charge transfer and reverse the direction of band bending, with important consequences for Schottky barrier heights and device applications.

  13. Evaluation of Pt Alloys as Electrocatalysts for Oxalic Acid Oxidation: A Combined Experimental and Computational Study

    DOE PAGES

    Perry, Albert; Babanova, Sofia; Matanovic, Ivana; ...

    2016-07-14

    Here in this study we combined experimental approaches and density functional theory to evaluate novel platinum-based materials as electrocatalysts for oxalic acid oxidation. Several Pt alloys, PtSn (1:1), PtSn (19:1), PtRu (1:4), PtRuSn (5:4:1), and PtRhSn (3:1:4), were synthetized using sacrificial support method and tested for oxidation of oxalic acid at pH 4. It was shown that PtSn (1:1) and PtRu (1:4) have higher mass activity relative to Pt. These two materials along with Pt and one of the least active alloys, PtSn (19:1), were further analyzed for the oxidation of oxalic acid at different pHs. The results show thatmore » all samples tested followed an identical trend of decreased onset potential with increased pH and increased catalytic activity with decreased pH. Density functional theory was further utilized to gain a fundamental knowledge about the mechanism of oxalic acid oxidation on Pt, PtSn (1:1), and PtRu (1:4). In conclusion, the results of the calculations along with the experimentally observed dependence of generated currents on the oxalic acid concentration indicate that the mechanism of oxalic acid oxidation on Pt proceeds without the participation of surface oxidizing species, while on Pt alloys it involves their participation.« less

  14. Evaluation of Pt Alloys as Electrocatalysts for Oxalic Acid Oxidation: A Combined Experimental and Computational Study

    SciTech Connect

    Perry, Albert; Babanova, Sofia; Matanovic, Ivana; Neumman, Anica; Serov, Alexey; Artyushkova, Kateryna; Atanassov, Plamen

    2016-07-14

    Here in this study we combined experimental approaches and density functional theory to evaluate novel platinum-based materials as electrocatalysts for oxalic acid oxidation. Several Pt alloys, PtSn (1:1), PtSn (19:1), PtRu (1:4), PtRuSn (5:4:1), and PtRhSn (3:1:4), were synthetized using sacrificial support method and tested for oxidation of oxalic acid at pH 4. It was shown that PtSn (1:1) and PtRu (1:4) have higher mass activity relative to Pt. These two materials along with Pt and one of the least active alloys, PtSn (19:1), were further analyzed for the oxidation of oxalic acid at different pHs. The results show that all samples tested followed an identical trend of decreased onset potential with increased pH and increased catalytic activity with decreased pH. Density functional theory was further utilized to gain a fundamental knowledge about the mechanism of oxalic acid oxidation on Pt, PtSn (1:1), and PtRu (1:4). In conclusion, the results of the calculations along with the experimentally observed dependence of generated currents on the oxalic acid concentration indicate that the mechanism of oxalic acid oxidation on Pt proceeds without the participation of surface oxidizing species, while on Pt alloys it involves their participation.

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

    PubMed Central

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

    2016-01-01

    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. PMID:27476577

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

    NASA Astrophysics Data System (ADS)

    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.

  17. Alkyl chain length-dependent surface reaction of dodecahydro-N-alkylcarbazoles on Pt model catalysts

    SciTech Connect

    Gleichweit, Christoph; Amende, Max; Bauer, Udo; Schernich, Stefan; Höfert, Oliver; Lorenz, Michael P. A.; Zhao, Wei; Bachmann, Philipp; Papp, Christian; Müller, Michael; Koch, Marcus; Wasserscheid, Peter; Libuda, Jörg; Steinrück, Hans-Peter

    2014-05-28

    The concept of liquid organic hydrogen carriers (LOHC) holds the potential for large scale chemical storage of hydrogen at ambient conditions. Herein, we compare the dehydrogenation and decomposition of three alkylated carbazole-based LOHCs, dodecahydro-N-ethylcarbazole (H{sub 12}-NEC), dodecahydro-N-propylcarbazole (H{sub 12}-NPC), and dodecahydro-N-butylcarbazole (H{sub 12}-NBC), on Pt(111) and on Al{sub 2}O{sub 3}-supported Pt nanoparticles. We follow the thermal evolution of these systems quantitatively by in situ high-resolution X-ray photoelectron spectroscopy. We show that on Pt(111) the relevant reaction steps are not affected by the different alkyl substituents: for all LOHCs, stepwise dehydrogenation to NEC, NPC, and NBC is followed by cleavage of the C–N bond of the alkyl chain starting at 380–390 K. On Pt/Al{sub 2}O{sub 3}, we discern dealkylation on defect sites already at 350 K, and on ordered, (111)-like facets at 390 K. The dealkylation process at the defects is most pronounced for NEC and least pronounced for NBC.

  18. Mitigation of CO Poisoning on Functionalized Pt/TiN(001) Surface: A Fundamental Study of the Next-Generation Fuel Cell Technologies

    DTIC Science & Technology

    2014-05-27

    Final 3. DATES COVERED (From - To) 25 Mar 2013 to 24 Mar 2014 4. TITLE AND SUBTITLE Mitigation of CO poisoning on functionalized Pt/ TiN (001) surface... TiN (100) surface (Pt/ TiN ) could be a promising catalyst for proton exchange membrane fuel cells (PEM FCs). The adsorption properties of molecules on Pt... TiN are an important step, when it is incorporated as the anode or cathode of PEM FCs. Utilizing the first principle calculations based on density

  19. Use of Hydrogen Chemisorption and Ethylene Hydrogenation as Predictors for Aqueous Phase Reforming of Lactose over Ni@Pt and Co@Pt Bimetallic Overlayer Catalysts

    SciTech Connect

    Lai, Qinghua; Skoglund, Michael D.; Zhang, Chen; Morris, Allen R.; Holles, Joseph H.

    2016-10-20

    Overlayer Pt on Ni (Ni@Pt) or Co (Co@Pt) were synthesized and tested for H2 generation from APR of lactose. H2 chemisorption descriptor showed that Ni@Pt and Co@Pt overlayer catalysts had reduced H2 adsorption strength compared to a Pt only catalyst, which agree with computational predictions. The overlayer catalysts also demonstrated lower activity for ethylene hydrogenation than the Pt only catalyst, which likely resulted from decreased H2 binding strength decreasing the surface coverage of H2. XAS results showed that overlayer catalysts exhibited higher white line intensity than the Pt catalyst, which indicates a negative d-band shift for the Pt overlayer, further providing evidence for overlayer formation. Lactose APR studies showed that lactose can be used as feedstock to produce H2 and CO under desirable reaction conditions. The Pt active sites of Ni@Pt and Co@Pt overlayer catalysts showed significantly enhanced H2 production selectivity and activity when compared with that of a Pt only catalyst. The single deposition overlayer with the largest d-band shift showed the highest H2 activity. The results suggest that overlayer formation using directed deposition technique could modify the behavior of the surface metal and ultimately modify the APR activity.

  20. Thermal inactivation of Salmonella enteritidis PT 30 in almond kernels as influenced by water activity.

    PubMed

    Villa-Rojas, Rossana; Tang, Juming; Wang, Shaojin; Gao, Mengxiang; Kang, Dong-Hyun; Mah, Jae-Hyung; Gray, Peter; Sosa-Morales, Maria Elena; López-Malo, Aurelio

    2013-01-01

    Salmonellosis outbreaks related to consumption of raw almonds have encouraged the scientific community to study the inactivation kinetics of pathogens in this dry commodity. However, the low moisture content of the product presents a challenge for thermal control, because the time required to achieve the desired thermal inactivation of microorganisms increases sharply with reduced moisture content and water activity. In this study, we explored and modeled the heat inactivation of Salmonella enterica serovar Enteritidis PT 30 in almond cultivar 'Nonpareil' kernel flour at four water activity (a(w)) values (0.601, 0.720, 0.888, and 0.946) using four temperatures for each a(w). The results showed that the inactivation was well fitted by both Weibull distribution (R(2) = 0.93 to 1.00) and first-order kinetics (R(2) = 0.82 to 0.96). At higher a(w) values, the rate of inactivation increased and less time was needed to achieve the required population reduction. These results suggest that, to avoid deterioration of product quality, shorter process times at lower temperatures may be used to achieve desired inactivation levels of Salmonella Enteritidis PT 30 by simply increasing the moisture content of almonds. These goals could be achieved with the use of existing procedures already practiced by the food industry, such as washing or prewetting scalding before heat inactivation.

  1. Surface acoustic load sensing using a face-shear PIN-PMN-PT single-crystal resonator.

    PubMed

    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.

  2. The role of the cationic Pt sites in the adsorption properties of water and ethanol on the Pt4/Pt(111) and Pt4/CeO2(111) substrates: A density functional theory investigation

    NASA Astrophysics Data System (ADS)

    Seminovski, Yohanna; Tereshchuk, Polina; Kiejna, Adam; Da Silva, Juarez L. F.

    2016-09-01

    Finite site platinum particles, Ptn, supported on reduced or unreduced cerium oxide surfaces, i.e., CeO2-x(111) ( 0 < x < /1 2 ), have been employed and studied as catalysts for a wide range of applications, which includes hydrogen production using the ethanol steam reforming processes. Our atomic-level understanding of the interaction of Pt with CeO2-x has been improved in the last years; however, the identification of the active sites on the Ptn/CeO2-x(111) substrates is still far from complete. In this work, we applied density functional theory based calculations with the addition of the on-site Coulomb interactions (DFT+U) for the investigation of the active sites and the role of the Pt oxidation state on the adsorption properties of water and ethanol (probe molecules) on four selected substrates, namely, Pt(111), Pt4/Pt(111), CeO2(111), and Pt4/CeO2(111). Our results show that water and ethanol preferentially bind in the cationic sites of the base of the tetrahedron Pt4 cluster instead of the anionic lower-coordinated Pt atoms located on the cluster-top or in the surface Ce (cationic) and O (anionic) sites. The presence of the Pt4 cluster contributes to increase the adsorption energy of both molecules on Pt(111) and CeO2(111) surfaces; however, its magnitude increases less for the case of Pt4/CeO2(111). Thus, the cationic Pt sites play a crucial role in the adsorption properties of water and ethanol. Both water and ethanol bind to on-top sites via the O atom and adopt parallel and perpendicular configurations on the Pt(111) and CeO2(111) substrates, respectively, while their orientation is changed once the Pt4 cluster is involved, favoring H binding with the surface sites.

  3. The role of the cationic Pt sites in the adsorption properties of water and ethanol on the Pt4/Pt(111) and Pt4/CeO2(111) substrates: A density functional theory investigation.

    PubMed

    Seminovski, Yohanna; Tereshchuk, Polina; Kiejna, Adam; Da Silva, Juarez L F

    2016-09-28

    Finite site platinum particles, Ptn, supported on reduced or unreduced cerium oxide surfaces, i.e., CeO2-x(111) (0Pt with CeO2-x has been improved in the last years; however, the identification of the active sites on the Ptn/CeO2-x(111) substrates is still far from complete. In this work, we applied density functional theory based calculations with the addition of the on-site Coulomb interactions (DFT+U) for the investigation of the active sites and the role of the Pt oxidation state on the adsorption properties of water and ethanol (probe molecules) on four selected substrates, namely, Pt(111), Pt4/Pt(111), CeO2(111), and Pt4/CeO2(111). Our results show that water and ethanol preferentially bind in the cationic sites of the base of the tetrahedron Pt4 cluster instead of the anionic lower-coordinated Pt atoms located on the cluster-top or in the surface Ce (cationic) and O (anionic) sites. The presence of the Pt4 cluster contributes to increase the adsorption energy of both molecules on Pt(111) and CeO2(111) surfaces; however, its magnitude increases less for the case of Pt4/CeO2(111). Thus, the cationic Pt sites play a crucial role in the adsorption properties of water and ethanol. Both water and ethanol bind to on-top sites via the O atom and adopt parallel and perpendicular configurations on the Pt(111) and CeO2(111) substrates, respectively, while their orientation is changed once the Pt4 cluster is involved, favoring H binding with the surface sites.

  4. Investigation of the oxygen exchange mechanism on Pt|yttria stabilized zirconia at intermediate temperatures: Surface path versus bulk path

    PubMed Central

    Opitz, Alexander K.; Lutz, Alexander; Kubicek, Markus; Kubel, Frank; Hutter, Herbert; Fleig, Jürgen

    2011-01-01

    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 °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 °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. PMID:22210951

  5. Investigation of the oxygen exchange mechanism on Pt|yttria stabilized zirconia at intermediate temperatures: Surface path versus bulk path.

    PubMed

    Opitz, Alexander K; Lutz, Alexander; Kubicek, Markus; Kubel, Frank; Hutter, Herbert; Fleig, Jürgen

    2011-11-30

    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 °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 °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.

  6. Improved Oxygen Reduction Activity and Durability of Dealloyed PtCo x Catalysts for Proton Exchange Membrane Fuel Cells: Strain, Ligand, and Particle Size Effects.

    PubMed

    Jia, Qingying; Caldwell, Keegan; Strickland, Kara; Ziegelbauer, Joseph M; Liu, Zhongyi; Yu, Zhiqiang; Ramaker, David E; Mukerjee, Sanjeev

    2015-01-02

    The development of active and durable catalysts with reduced platinum content is essential for fuel cell commercialization. Herein we report that the dealloyed PtCo/HSC and PtCo3/HSC nanoparticle (NP) catalysts exhibit the same levels of enhancement in oxygen reduction activity (~4-fold) and durability over pure Pt/C NPs. Surprisingly, ex situ high-angle annular dark field scanning transmission electron microscopy (HAADF STEM) shows that the bulk morphologies of the two catalysts are distinctly different: D-PtCo/HSC catalyst is dominated by NPs with solid Pt shells surrounding a single ordered PtCo core; however, the D-PtCo3/HSC catalyst is dominated by NPs with porous Pt shells surrounding multiple disordered PtCo cores with local concentration of Co. In situ X-ray absorption spectroscopy (XAS) reveals that these two catalysts possess similar Pt-Pt and Pt-Co bond distances and Pt coordination numbers (CNs), despite their dissimilar morphologies. The similar activity of the two catalysts is thus ascribed to their comparable strain, ligand, and particle size effects. Ex situ XAS performed on D-PtCo3/HSC under different voltage cycling stage shows that the continuous dissolution of Co leaves behind the NPs with a Pt-like structure after 30k cycles. The attenuated strain and/or ligand effects caused by Co dissolution are presumably counterbalanced by the particle size effects with particle growth, which likely accounts for the constant specific activity of the catalysts along with voltage cycling.

  7. Active particles on curved surfaces

    NASA Astrophysics Data System (ADS)

    Fily, Yaouen; Baskaran, Aparna; Hagan, Michael

    Active systems have proved to be very sensitive to the geometry of their environment. This is often achieved by spending significant time at the boundary, probing its shape by gliding along it. I will discuss coarse graining the microscopic dynamics of self-propelled particles on a general curved surface to predict the way the density profile on the surface depends on its geometry. Beyond confined active particles, this formalism is a natural starting point to study objects that cannot leave the boundary at all, such as cells crawling on a curved substrate, animals running on uneven ground, or active colloids trapped at an interface.

  8. Pillared honeycomb nanoarchitectures formed on solid surfaces by the self-assembly of lipid-packaged one-dimensional Pt complexes

    PubMed Central

    Chang-Soo, Lee; Kimizuka, Nobuo

    2002-01-01

    A highly lipophilic polyion complex [Pt(en)2][PtCl2(en)2](1)4 (en, 1,2-diaminoethane) is prepared from one-dimensional mixed valence PtII/PtIV complex and newly designed chiral amphiphile 1. The powdery sample showed purple color, which is a result of the mixed valence absorption of the linear chlorobridged complex (PtII-Cl-PtIV-Cl-)n. When the lipid complex is dispersed in dichloromethane, purple-colored dispersion is obtained at 0°C, whereas the color disappears after heating the solution to 21°C. The observed thermochromism is reversible with respect to the temperature changes and is ascribed to the reversible dissociation and reassembly of the self-assembling inorganic wires. Casting of the 0°C-purple dispersion on solid substrates affords honeycomb nanostructures in addition to the nanowires with the width of about 20 nm. The honeycomb patterns seem to be templated by the condensed water droplets that are formed and aligned on the rapidly evaporating dichloromethane solution. On the other hand, more regular honeycomb structures are exclusively obtained by casting the 21°C-colorless solution. These observations indicate that the ordered honeycomb structures are obtainable on solid surfaces by the self-assembly of molecularly dispersed components [Pt(en)2](1)2 and trans-[PtCl2(en)2](1)2. Very interestingly, formation of double-layered honeycomb nanostructure is observed by scanning electron microscopy. The unit hexagons and pillars of the honeycombs are made of nanowires that are hierarchically assembled from the lipid-packaged PtII/PtIV complexes. The surface self-organization of lipophilic inorganic complexes has a potential to fabricate novel nanoarchitectures with conjugated electronic structures. PMID:11929964

  9. Tuning oxygen reduction reaction activity via controllable dealloying: a model study of ordered Cu3Pt/C intermetallic nanocatalysts.

    PubMed

    Wang, Deli; Yu, Yingchao; Xin, Huolin L; Hovden, Robert; Ercius, Peter; Mundy, Julia A; Chen, Hao; Richard, Jonah H; Muller, David A; DiSalvo, Francis J; Abruña, Héctor D

    2012-10-10

    A promising electrocatalyst prototype of low Pt mole fraction, intermetallic nanoparticles of Cu(3)Pt, has been prepared using a simple impregnation-reduction method, followed by a post heat-treatment. Two dealloying methods (electrochemical and chemical) were implemented to control the atomic-level morphology and improve performance for the oxygen reduction reaction (ORR). The morphology and elemental composition of the dealloyed nanoparticles were characterized at angstrom resolution using an aberration-corrected scanning transmission electron microscope equipped with an electron energy loss spectrometer. We found that the electrochemical dealloying method led to the formation of a thin Pt skin of ca. 1 nm in thickness with an ordered Cu(3)Pt core structure, while chemical leaching gave rise to a "spongy" structure with no ordered structure being preserved. A three-dimensional tomographic reconstruction indicated that numerous voids were formed in the chemically dealloyed nanoparticles. Both dealloying methods yielded enhanced specific and mass activities toward the ORR and higher stability relative to Pt/C. The spongy nanoparticles exhibited better mass activity with a slightly lower specific activity than the electrochemically dealloyed nanoparticles after 50 potential cycles. In both cases, the mass activity was still enhanced after 5000 potential cycles.

  10. Atomically flat surface of (0 0 1) textured FePt thin films by residual stress control

    NASA Astrophysics Data System (ADS)

    Liu, S. H.; Hsiao, S. N.; Chou, C. L.; Chen, S. K.; Lee, H. Y.

    2015-11-01

    Single-layered Fe52Pt48 films with thickness of 10 nm were sputter-deposited on glass substrates. Rapid thermal annealing with different heating rates (10-110 K/s) was applied to transform as-deposited fcc phase into L10 phase and meanwhile to align [0 0 1]-axis of L10 crystal along plane normal direction. Based on X-ray diffractometry using synchrotron radiation source, the texture coefficient of (0 0 1)-plane increases with increasing heating rate from 10 to 40 K/s, which is correlated with perpendicular magnetic anisotropy and in-plane tensile stress analyzed by asymmetric sin2 ψ method. Furthermore, it was revealed by atomic force microscopy that the dewetting process occurred as heating rate was raised up to 80 K/s and higher. The change in the microstructure due to stress relaxation leads to the degradation of (0 0 1) orientation and magnetic properties. Surface roughness is closely related to the in-plane tensile stress. Enhanced perpendicular magnetic anisotropy and atomically flat surface were achieved for the samples annealed at 40 K/s, which may be suitable for further practical applications. This work also suggests a feasible way for surface engineering by controlling internal stress of the FePt without introducing cap layer.

  11. LEED crystallography studies of the structure of clean and adsorbate-covered Ir, Pt and Rh crystal surfaces

    SciTech Connect

    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.

  12. Observation of a topologically non-trivial surface state in half-Heusler PtLuSb (001) thin films

    NASA Astrophysics Data System (ADS)

    Logan, J. A.; Patel, S. J.; Harrington, S. D.; Polley, C. M.; Schultz, B. D.; Balasubramanian, T.; Janotti, A.; Mikkelsen, A.; Palmstrøm, C. J.

    2016-06-01

    The discovery of topological insulators, materials with bulk band gaps and protected cross-gap surface states in compounds such as Bi2Se3, has generated much interest in identifying topological surface states (TSSs) in other classes of materials. In particular, recent theoretical calculations suggest that TSSs may be found in half-Heusler ternary compounds. If experimentally realizable, this would provide a materials platform for entirely new heterostructure spintronic devices that make use of the structurally identical but electronically varied nature of Heusler compounds. Here we show the presence of a TSS in epitaxially grown thin films of the half-Heusler compound PtLuSb. Spin- and angle-resolved photoemission spectroscopy, complemented by theoretical calculations, reveals a surface state with linear dispersion and a helical tangential spin texture consistent with previous predictions. This experimental verification of topological behaviour is a significant step forward in establishing half-Heusler compounds as a viable material system for future spintronic devices.

  13. Observation of a topologically non-trivial surface state in half-Heusler PtLuSb (001) thin films.

    PubMed

    Logan, J A; Patel, S J; Harrington, S D; Polley, C M; Schultz, B D; Balasubramanian, T; Janotti, A; Mikkelsen, A; Palmstrøm, C J

    2016-06-27

    The discovery of topological insulators, materials with bulk band gaps and protected cross-gap surface states in compounds such as Bi2Se3, has generated much interest in identifying topological surface states (TSSs) in other classes of materials. In particular, recent theoretical calculations suggest that TSSs may be found in half-Heusler ternary compounds. If experimentally realizable, this would provide a materials platform for entirely new heterostructure spintronic devices that make use of the structurally identical but electronically varied nature of Heusler compounds. Here we show the presence of a TSS in epitaxially grown thin films of the half-Heusler compound PtLuSb. Spin- and angle-resolved photoemission spectroscopy, complemented by theoretical calculations, reveals a surface state with linear dispersion and a helical tangential spin texture consistent with previous predictions. This experimental verification of topological behaviour is a significant step forward in establishing half-Heusler compounds as a viable material system for future spintronic devices.

  14. Channeling effects observed in energy-loss spectra of nitrogen ions scattered off a Pt(110) surface

    NASA Astrophysics Data System (ADS)

    Robin, A.; Heiland, W.; Jensen, J.; Juaristi, J. I.; Arnau, A.

    2001-11-01

    We present measured energy-loss spectra of nitrogen ions, which are scattered off a (1×2) missing row reconstructed Pt(110) single-crystal surface. The primary energy is varied from below 1 keV up to above 1 MeV, i.e., 0.04v0surface channeling at all energies. Experimental results are compared with theoretical energy-loss values obtained from trajectory and stopping power calculations of charged particles scattered under grazing incidence conditions from metallic surfaces. The stopping power is calculated using the scattering theory formalism. Different trajectory classes are found by the calculations and assigned to different contributions in the energy-loss spectra. Regarding the simplicity of the presented model the agreement with the experiment is good.

  15. Active Free Surface Density Maps

    NASA Astrophysics Data System (ADS)

    Çelen, S.

    2016-10-01

    Percolation problems were occupied to many physical problems after their establishment in 1957 by Broadbent and Hammersley. They can be used to solve complex systems such as bone remodeling. Volume fraction method was adopted to set some algorithms in the literature. However, different rate of osteoporosis could be observed for different microstructures which have the same mass density, mechanical stimuli, hormonal stimuli and nutrition. Thus it was emphasized that the bone might have identical porosity with different specific surfaces. Active free surface density of bone refers the used total area for its effective free surface. The purpose of this manuscript is to consolidate a mathematical approach which can be called as “active free surface density maps” for different surface patterns and derive their formulations. Active free surface density ratios were calculated for different Archimedean lattice models according to Helmholtz free energy and they were compared with their site and bond percolation thresholds from the background studies to derive their potential probability for bone remodeling.

  16. Pt skin on AuCu intermetallic substrate: a strategy to maximize Pt utilization for fuel cells.

    PubMed

    Wang, Gongwei; Huang, Bing; Xiao, Li; Ren, Zhandong; Chen, Hao; Wang, Deli; Abruña, Héctor D; Lu, Juntao; Zhuang, Lin

    2014-07-09

    The dependence on Pt catalysts has been a major issue of proton-exchange membrane (PEM) fuel cells. Strategies to maximize the Pt utilization in catalysts include two main approaches: to put Pt atoms only at the catalyst surface and to further enhance the surface-specific catalytic activity (SA) of Pt. Thus far there has been no practical design that combines these two features into one single catalyst. Here we report a combined computational and experimental study on the design and implementation of Pt-skin catalysts with significantly improved SA toward the oxygen reduction reaction (ORR). Through screening, using density functional theory (DFT) calculations, a Pt-skin structure on AuCu(111) substrate, consisting of 1.5 monolayers of Pt, is found to have an appropriately weakened oxygen affinity, in comparison to that on Pt(111), which would be ideal for ORR catalysis. Such a structure is then realized by substituting the Cu atoms in three surface layers of AuCu intermetallic nanoparticles (AuCu iNPs) with Pt. The resulting Pt-skinned catalyst (denoted as Pt(S)AuCu iNPs) has been characterized in depth using synchrotron XRD, XPS, HRTEM, and HAADF-STEM/EDX, such that the Pt-skin structure is unambiguously identified. The thickness of the Pt skin was determined to be less than two atomic layers. Finally the catalytic activity of Pt(S)AuCu iNPs toward the ORR was measured via rotating disk electrode (RDE) voltammetry through which it was established that the SA was more than 2 times that of a commercial Pt/C catalyst. Taking into account the ultralow Pt loading in Pt(S)AuCu iNPs, the mass-specific catalytic activity (MA) was determined to be 0.56 A/mg(Pt)@0.9 V, a value that is well beyond the DOE 2017 target for ORR catalysts (0.44 A/mg(Pt)@0.9 V). These findings provide a strategic design and a realizable approach to high-performance and Pt-efficient catalysts for fuel cells.

  17. Electronic bands, Fermi surface, and elastic properties of new 4.2 K superconductor SrPtAs with a honeycomb structure from first principles calculations

    NASA Astrophysics Data System (ADS)

    Shein, I. R.; Ivanovskii, A. L.

    2011-10-01

    The hexagonal phase SrPtAs (s.g. P6/ mmm; #194) with a honeycomb lattice structure was recently declared as a new low-temperature ( T C ∼ 4.2 K) superconductor. Here, by means of first-principles calculations the optimized structural parameters, electronic bands, Fermi surface, total and partial densities of states, inter-atomic bonding picture, independent elastic constants, bulk and shear moduli for SrPtAs were obtained for the first time and analyzed in comparison with the related layered superconductor SrPt 2As 2.

  18. Potential energy barriers for interlayer mass transport in homoepitaxial growth on fcc(111) surfaces: Pt and Ag

    NASA Astrophysics Data System (ADS)

    Li, Yinggang; DePristo, Andrew E.

    1994-11-01

    The efficiency of interlayer mass transport determines the growth mode and film quality in molecular beam epitaxy. In this paper we report potential energy barriers (PEB) to interlayer diffusion for Pt and Ag homoepitaxial growth on fcc (111) surfaces, as calculated using the corrected effective medium theory. Various island structures were considered. The island sizes ranged from 3- to about 60-atom islands and to various steps ("infinite" large islands). We found that jumping directly over the island edge has a much higher PEB than does the so-called displacement-exchange mechanism. Exchange at edges with kink sites also had a higher or comparable PEB to those at the straight (perfect) edges, contrary to previous speculations [M. Henzler, T. Schmidt and E.Z. Luo, in: The Structure of Surfaces IV (World Scientific, Signapore, 1994)]. The PEB depended strongly on the local atomic arrangement but was insensitive to the global island size and shape as long as the island edges were at least five atoms long. For the displacement-exchange process, the PEB did not decrease monotonically with decreasing island size over the entire island size range. For very small islands of less than ten atoms the PEB increased abruptly by an order of magnitude. This qualitative behavior was exhibited by both Pt and Ag systems but the two differed quantitatively for island sizes above ten atoms. We discuss the relevance of these results to the experimental observations, i.e., the reentrant growth in Pt [R. Kunkel, B. Poelsema, L.K. Verheij and G. Comsa, Phys. Rev. Lett. 65 (1990) 733], layer-by-layer growth in Ag induced by surfactant [H.A. van der Vegt, H.M. van Pinxteren, M. Lohmerier and E. Vlieg, Phys. Rev. Lett. 68 (1992) 3335] or by high-density of islands [G. Rosenfeld, R. Servaty, C. Teichert, B. Poelsema and G. Comsa, Phys. Rev. Lett. 71 (1993) 895 ], as well as the different growth behaviors found in the two systems.

  19. Combining anti-cancer drugs with artificial sweeteners: synthesis and anti-cancer activity of saccharinate (sac) and thiosaccharinate (tsac) complexes cis-[Pt(sac)2(NH3)2] and cis-[Pt(tsac)2(NH3)2].

    PubMed

    Al-Jibori, Subhi A; Al-Jibori, Ghassan H; Al-Hayaly, Lamaan J; Wagner, Christoph; Schmidt, Harry; Timur, Suna; Baris Barlas, F; Subasi, Elif; Ghosh, Shishir; Hogarth, Graeme

    2014-12-01

    The new platinum(II) complexes cis-[Pt(sac)2(NH3)2] (sac=saccharinate) and cis-[Pt(tsac)2(NH3)2] (tsac=thiosaccharinate) have been prepared, the X-ray crystal structure of cis-[Pt(sac)2(NH3)2] x H2O reveals that both saccharinate anions are N-bound in a cis-arrangement being inequivalent in both the solid-state and in solution at room temperature. Preliminary anti-cancer activity has been assessed against A549 human alveolar type-II like cell lines with the thiosaccharinate complex showing good activity.

  20. Facile preparation of high-quality Pt/reduced graphene oxide nanoscrolls for methanol oxidation

    NASA Astrophysics Data System (ADS)

    Liu, Yu; Xia, Yunxue; Yang, Hongyu; Zhang, Yunsong; Zhao, Maojun; Pan, Guangtang

    2013-06-01

    A simple and novel approach for the preparation of a Pt/reduced graphene oxide nanoscroll (Pt/RGOS) nanocatalyst is reported for the first time. The Pt/reduced graphene oxide (Pt/RGO) was fabricated by the co-reduction of GO and Pt salt using ethylene glycol under microwave irradiation, then the Pt/RGOSs were obtained by oxygen implosion in situ rolling up of the Pt/RGO using catalytic decomposition of Pt towards H2O2 under ultrasonication. Transmission electron microscopy shows that the Pt nanoparticles are uniformly dispersed on the reduced graphene oxide nanoscrolls with tubular structure, open edges and ends, and tubular diameter ranging from 10 to 100 nm. X-ray diffraction indicates that the crystal structure and diffraction intensity of the platinum practically remains unchanged, and the RGO has not been oxidized before or after rolling. Raman spectroscopy reveals that the Pt/RGOSs have a higher D/G ratio (1.2) than Pt/RGO (1.1). BET (Brunauer, Emmett and Teller) results exhibit that the Pt/RGOSs possess higher specific surface area and broader pore size range (188 m2 g-1, 25-45 nm) than Pt/RGO (122 m2 g-1, 30-38 nm). Additionally, the electrocatalytic performance of the Pt/RGOSs for methanol oxidation was evaluated, and the results show that the Pt/RGOSs possess significantly higher electrocatalytic activity and stability than Pt/RGO.

  1. Surface area loss mechanisms of Pt3Co nanocatalysts in proton exchange membrane fuel cells

    NASA Astrophysics Data System (ADS)

    Rasouli, S.; Ortiz Godoy, R. A.; Yang, Z.; Gummalla, M.; Ball, S. C.; Myers, D.; Ferreira, P. J.

    2017-03-01

    Pt3Co catalyst nanoparticles of 4.9 nm size present on the cathode side of a PEMFC membrane-electrode assembly (MEA) were analyzed by transmission electron microscopy after 10 K voltage cycles under different operating conditions. The operating conditions include baseline (0.4-0.95 V, 80° C, 100% Relative Humidity (RH)), high potential (0.4-1.05 V, 80° C, 100% RH), high temperature (0.4-0.95 V, 90° C, 100% RH), and low humidity (0.4-0.95 V, 80° C, 30% RH). Particle growth and particle loss to the membrane is more severe in the high potential sample than in the high temperature and baseline MEAs, while no significant particle growth and particle precipitation in the membrane can be observed in the low humidity sample. Particles with different morphologies were seen in the cathode including: 1-Spherical individual particles resulting from modified electro-chemical Ostwald ripening and 2-aggregated and coalesced particles resulting from either necking of two or more particles or preferential deposition of Pt between particles with consequent bridging. The difference in the composition of these morphologies results in composition variations through the cathode from cathode/diffusion media (DM) to the cathode/membrane interface.

  2. Mode-selective chemistry on metal surfaces: The dissociative chemisorption of CH4 on Pt(111)

    DOE PAGES

    Guo, Han; Jackson, Bret

    2016-05-13

    A quantum approach based on an expansion in vibrationally adiabatic eigenstates is used to explore CH4 dissociation on Pt(111). Computed sticking probabilities for molecules in the ground, 1v3 and 2v3, states are in very good agreement with the available experimental data, reproducing the variation in reactivity with collision energy and vibrational state. As was found in similar studies on Ni(100) and Ni(111), exciting the 1v1 symmetric stretch of CH4 is more effective at promoting the dissociative chemisorption of CH4 than exciting the 1v3 antisymmetric stretch. This behavior is explained in terms of symmetry, mode-softening, and nonadiabatic transitions between vibrationally adiabaticmore » states. We find that the efficacies of the bending modes for promoting reaction are reasonably large, and similar to the 1v3 state. The vibrational efficacies for promoting reaction on Ni(111) are larger than for reaction on Pt(111), due to the larger nonadiabatic couplings. As a result, our computed sticking probabilities are in good agreement with results from recent ab initio molecular dynamics and reactive force field studies.« less

  3. Highly durable Pt/graphene oxide and Pt/C hybrid catalyst for polymer electrolyte membrane fuel cell

    NASA Astrophysics Data System (ADS)

    Jung, Ju Hae; Park, Hyang Jin; Kim, Junbom; Hur, Seung Hyun

    2014-02-01

    We report a highly durable hybrid catalyst composed of Pt/graphene oxide (GO) and Pt/C catalyst for polymer electrolyte membrane fuel cell (PEMFC). The accelerated durability tests in half-cell and full cell systems shows that the addition of small amount of Pt/GO catalyst significantly enhances the durability of commercial Pt/C catalyst without sacrificing initial electrochemical active surface area (ECSA). The XRD and TEM analysis reveal that the GO not only exhibits the high resistance to Pt agglomeration but also prevents the Pt agglomeration in Pt/C catalyst by providing the anchoring sites of eluted metal ions. We believe that this simple and effective approach can open a new way to fabricate highly durable electrocatalyst for the commercialization of fuel cell vehicles.

  4. Very low amount of TiO2 on N-doped carbon nanotubes significantly improves oxygen reduction activity and stability of supported Pt nanoparticles.

    PubMed

    Zhao, Anqi; Masa, Justus; Xia, Wei

    2015-04-28

    Electrochemical corrosion is a major problem for carbon materials used in electrocatalysis. Highly dispersed TiO2 was deposited on O-functionalized and N-doped carbon nanotubes by chemical vapour deposition to tackle the carbon corrosion problem. Very low Ti loadings of about 1 wt% were applied to minimize the negative influence of TiO2 as a semiconductor on the high conductivity of carbon materials. Both N doping and TiO2 coating facilitate strong metal-support interactions and favour the formation of small Pt particles. N doping improved the intrinsic catalytic activity of the carbon support and enhanced the conductivity due to the removal of surface oxygen groups, while the negative effect of TiO2 on conductivity is counterbalanced by its promoting effect on metal-support interactions leading to enhanced overall catalytic performance. Pt/TiO2/NCNTs showed the highest ORR activity, and significantly outperformed Pt/NCNTs in electrochemical stability tests.

  5. Dependence of Gas-Phase Crotonaldehyde Hydrogenation Selectivity and Activity on the Size of Pt Nanoparticles (1.7-7.1 nm) Supported on SBA-15

    SciTech Connect

    Grass, Michael; Rioux, Robert; Somorjai, Gabor A.

    2008-08-03

    The selectivity and activity for the hydrogenation of crotonaldehyde to crotyl alcohol and butyraldehyde was studied over a series of Pt nanoparticles (diameter of 1.7, 2.9, 3.6, and 7.1 nm). The nanoparticles were synthesized by the reduction of chloroplatinic acid by alcohol in the presence of poly(vinylpyrrolidone) (PVP), followed by encapsulation into mesoporous SBA-15 silica. The rate of crotonaldehyde hydrogenation and selectivity towards crotyl alcohol both increase with increasing particle size. The selectivity towards crotyl alcohol increased from 13.7 % to 33.9 % (8 Torr crotonaldehyde, 160 Torr H{sub 2} and 353 K), while the turnover frequency increases from 2.1 x 10{sup -2} s{sup -1} to 4.8 x 10{sup -2} s{sup -1} with an increase in the particle size from 1.7 nm to 7.1 nm. The decarbonylation pathway to form propene and CO is enhanced over the higher proportion of coordinatively unsaturated sites on the smaller nanoparticles. The apparent activation energy remains constant ({approx} 16 kcal mol{sup -1} for the formation of butyraldehyde and {approx} 8 kcal mol{sup -1} for the formation of crotyl alcohol) as a function of particle size. In the presence of 130-260 mTorr CO, the reaction rate decreases for all products with a CO reaction order of -0.9 for crotyl alcohol and butyraldehyde over 7.1 nm Pt particles; over 1.7 nm Pt particles, the order in CO is -1.4 and -0.9, respectively. Hydrogen reduction at 673 K after calcination in oxygen results in increased activity and selectivity relative to reduction at either higher or lower temperature; this is discussed with regards to the incomplete removal and/or change in morphology of the polymeric surface stabilizing agent, poly(vinylpyrrolidone) used for the synthesis of the Pt nanoparticles.

  6. A novel non-enzymatic glucose sensor based on Pt3Ru1 alloy nanoparticles with high density of surface defects.

    PubMed

    Yang, Jiangwei; Liang, Xinyi; Cui, Lan; Liu, Haiyan; Xie, Junbo; Liu, Weixing

    2016-06-15

    A novel non-enzymatic glucose sensor based on a glassy carbon electrode modified with Pt3Ru1 alloy nanoparticles (Pt3Ru1/GCE) was fabricated. Pt3Ru1 alloy nanoparticles were prepared by a reverse microemulsion method at room temperature. The X-ray diffraction (XRD) and energy dispersive X-ray spectroscopy (EDS) demonstrate that Pt3Ru1 nanoparticles are disordered alloy with face central cubic (fcc) structure and the atom ratio of Pt and Ru is 3:1. The high-resolution transmission electron microscopy (HRTEM) images show that Pt3Ru1 alloy nanoparticles were aggregated with a high density of surface defects. Furthermore, the sensor properties of Pt3Ru1/GCE were investigated by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and chronoamperometry (CA) in 0.01 M PBS (pH 7.4). The results indicate that the proposed sensor exhibits a wide linear range of 5 × 10(-7)M to 10(-2)M (R(2)=0.9988) with a low detection limit of 0.3 μM for glucose. Moreover, the sensor demonstrates good sensitivity, stability, reproducibility, and better anti-interference performance toward ascorbic acid (AA), uric acid (UA), and fructose (Fru).

  7. Simple one-pot synthesis of solid-core@porous-shell alloyed PtAg nanocrystals for the superior catalytic activity toward hydrogen evolution and glycerol oxidation.

    PubMed

    Weng, Xuexiang; Liu, Qing; Wang, Ai-Jun; Yuan, Junhua; Feng, Jiu-Ju

    2017-05-15

    In this work, solid-core@porous-shell alloyed PtAg nanocrystals (PtAg NCs) were fabricated via a simple one-pot co-reduction wet-chemical method on a large scale. Diprophylline (DPP) was employed as the stabilizing agent and shape-directing agent, without any surfactant, polymer, seed or template. The products were mainly analyzed by a series of characterization technique. The hierarchical architectures had enhanced stability and improved electrocatalytic activity for hydrogen evolution reaction (HER) and glycerol oxidation reaction (GOR) in contrast with commercial available Pt/C and Pt black catalysts. For the prepared PtAg NCs catalyst, the Tafel slope is 40mVdec(-1) toward HER in 0.5M H2SO4, coupled with the specific activity and mass activity of 77.91mAcm(-2) and 1303mAmg(-1)Pt toward GOR, respectively.

  8. Improved Oxygen Reduction Activity and Durability of Dealloyed PtCox Catalysts for Proton Exchange Membrane Fuel Cells: Strain, Ligand, and Particle Size Effects

    PubMed Central

    Jia, Qingying; Caldwell, Keegan; Strickland, Kara; Ziegelbauer, Joseph M.; Liu, Zhongyi; Yu, Zhiqiang; Ramaker, David E.; Mukerjee, Sanjeev

    2015-01-01

    The development of active and durable catalysts with reduced platinum content is essential for fuel cell commercialization. Herein we report that the dealloyed PtCo/HSC and PtCo3/HSC nanoparticle (NP) catalysts exhibit the same levels of enhancement in oxygen reduction activity (~4-fold) and durability over pure Pt/C NPs. Surprisingly, ex situ high-angle annular dark field scanning transmission electron microscopy (HAADF STEM) shows that the bulk morphologies of the two catalysts are distinctly different: D-PtCo/HSC catalyst is dominated by NPs with solid Pt shells surrounding a single ordered PtCo core; however, the D-PtCo3/HSC catalyst is dominated by NPs with porous Pt shells surrounding multiple disordered PtCo cores with local concentration of Co. In situ X-ray absorption spectroscopy (XAS) reveals that these two catalysts possess similar Pt–Pt and Pt–Co bond distances and Pt coordination numbers (CNs), despite their dissimilar morphologies. The similar activity of the two catalysts is thus ascribed to their comparable strain, ligand, and particle size effects. Ex situ XAS performed on D-PtCo3/HSC under different voltage cycling stage shows that the continuous dissolution of Co leaves behind the NPs with a Pt-like structure after 30k cycles. The attenuated strain and/or ligand effects caused by Co dissolution are presumably counterbalanced by the particle size effects with particle growth, which likely accounts for the constant specific activity of the catalysts along with voltage cycling. PMID:26413384

  9. Titanium oxynitride interlayer to influence oxygen reduction reaction activity and corrosion stability of Pt and Pt-Ni alloy.

    PubMed

    Tan, XueHai; Wang, Liya; Zahiri, Beniamin; Kohandehghan, Alireza; Karpuzov, Dimitre; Lotfabad, Elmira Memarzadeh; Li, Zhi; Eikerling, Michael H; Mitlin, David

    2015-01-01

    A key advancement target for oxygen reduction reaction catalysts is to simultaneously improve both the electrochemical activity and durability. To this end, the efficacy of a new highly conductive support that comprises of a 0.5 nm titanium oxynitride film coated by atomic layer deposition onto an array of carbon nanotubes has been investigated. Support effects for pure platinum and for a platinum (50 at %)/nickel alloy have been considered. Oxynitride induces a downshift in the d-band center for pure platinum and fundamentally changes the platinum particle size and spatial distribution. This results in major enhancements in activity and corrosion stability relative to an identically synthesized catalyst without the interlayer. Conversely, oxynitride has a minimal effect on the electronic structure and microstructure, and therefore, on the catalytic performance of platinum-nickel. Calculations based on density functional theory add insight with regard to compositional segregation that occurs at the alloy catalyst-support interface.

  10. In Vivo Neural Recording and Electrochemical Performance of Microelectrode Arrays Modified by Rough-Surfaced AuPt Alloy Nanoparticles with Nanoporosity

    PubMed Central

    Zhao, Zongya; Gong, Ruxue; Zheng, Liang; Wang, Jue

    2016-01-01

    In order to reduce the impedance and improve in vivo neural recording performance of our developed Michigan type silicon electrodes, rough-surfaced AuPt alloy nanoparticles with nanoporosity were deposited on gold microelectrode sites through electro-co-deposition of Au-Pt-Cu alloy nanoparticles, followed by chemical dealloying Cu. The AuPt alloy nanoparticles modified gold microelectrode sites were characterized by scanning electron microscopy (SEM), electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV) and in vivo neural recording experiment. The SEM images showed that the prepared AuPt alloy nanoparticles exhibited cauliflower-like shapes and possessed very rough surfaces with many different sizes of pores. Average impedance of rough-surfaced AuPt alloy nanoparticles modified sites was 0.23 MΩ at 1 kHz, which was only 4.7% of that of bare gold microelectrode sites (4.9 MΩ), and corresponding in vitro background noise in the range of 1 Hz to 7500 Hz decreased to 7.5 μVrms from 34.1 μVrms at bare gold microelectrode sites. Spontaneous spike signal recording was used to evaluate in vivo neural recording performance of modified microelectrode sites, and results showed that rough-surfaced AuPt alloy nanoparticles modified microelectrode sites exhibited higher average spike signal-to-noise ratio (SNR) of 4.8 in lateral globus pallidus (GPe) due to lower background noise compared to control microelectrodes. Electro-co-deposition of Au-Pt-Cu alloy nanoparticles combined with chemical dealloying Cu was a convenient way for increasing the effective surface area of microelectrode sites, which could reduce electrode impedance and improve the quality of in vivo spike signal recording. PMID:27827893

  11. Immobilization of superoxide dismutase on Pt-Pd/MWCNTs hybrid modified electrode surface for superoxide anion detection.

    PubMed

    Zhu, Xiang; Niu, Xiangheng; Zhao, Hongli; Tang, Jie; Lan, Minbo

    2015-05-15

    Monitoring of reactive oxygen species like superoxide anion (O2(∙-)) turns to be of increasing significance considering their potential damages to organism. In the present work, we fabricated a novel O2(∙-) electrochemical sensor through immobilizing superoxide dismutase (SOD) onto a Pt-Pd/MWCNTs hybrid modified electrode surface. The Pt-Pd/MWCNTs hybrid was synthesized via a facile one-step alcohol-reduction process, and well characterized by transmission electron microscopy, X-ray photoelectron spectroscopy and X-ray diffraction. The immobilization of SOD was accomplished using a simple drop-casting method, and the performance of the assembled enzyme-based sensor for O2(∙-) detection was systematically investigated by several electrochemcial techniques. Thanks to the specific biocatalysis of SOD towards O2(∙-) and the Pt-Pd/MWCNTs - promoted fast electron transfer at the fabricated interface, the developed biosensor exhibits a fast, selective and linear amperometric response upon O2(∙-) in the concentration scope of 40-1550 μM (R(2)=0.9941), with a sensitivity of 0.601 mA cm(-2) mM(-1) and a detection limit of 0.71 μM (S/N=3). In addition, the favorable biocompatibility of this electrode interface endows the prepared biosensor with excellent long-term stability (a sensitivity loss of only 3% over a period of 30 days). It is promising that the proposed sensor will be utilized as an effective tool to quantitatively monitor the dynamic changes of O2(∙-) in biological systems.

  12. Postassembly Transformation of a Catalytically Active Composite Material, Pt@ZIF-8, via Solvent-Assisted Linker Exchange.

    PubMed

    Stephenson, Casey J; Hupp, Joseph T; Farha, Omar K

    2016-02-15

    2-Methylimidazolate linkers of Pt@ZIF-8 are exchanged with imidazolate using solvent-assisted linker exchange (SALE) to expand the apertures of the parent material and create Pt@SALEM-2. Characterization of the material before and after SALE was performed. Both materials are active as catalysts for the hydrogenation of 1-octene, whereas the hydrogenation of cis-cyclohexene occurred only with Pt@SALEM-2, consistent with larger apertures for the daughter material. The largest substrate, β-pinene, proved to be unreactive with H2 when either material was employed as a candidate catalyst, supporting the contention that substrate molecules, for both composites, must traverse the metal-organic framework component in order to reach the catalytic nanoparticles.

  13. Effect of isotretinoin on prothrombin time (PT), international normalized ratio (INR), and activated partial thromboplastin time (aPTT).

    PubMed

    Kaptanoglu, Asli Feride; Uncu, Murat; Ozyurt, Selcuk; Hincal, Evren

    2013-08-01

    Patients with severe acne may need elective/urgent surgical interventions during treatment with isotretinoin and it is critical for the surgeon to consider the possible effects of this medication on coagulation systems. The aim of this study is to determine the changes in prothrombin time (PT), international normalized ratio (INR), and activated partial thromboplastin time (aPTT) during isotretinoin treatment. PT, aPTT, and INR values of 51 severe acne patients were evaluated during routine pre-treatment biochemical analysis. Only patients with normal values were included in the study. The results of before and after 1 month treatment were compared statistically. There were no statistically significant change in mean alanine aminotranferease (ALT), aspartate aminotransferase (AST), PT, and INR values after treatment. A significant increase in aPTT was detected. The INR values, which are more trusted and safe, showed no difference. Isotretinoin seems to have no effect on these coagulation parameters.

  14. Highly Active Supported Pt Nanocatalysts Synthesized by Alcohol Reduction towards Hydrogenation of Cinnamaldehyde: Synergy of Metal Valence and Hydroxyl Groups.

    PubMed

    Wang, Yanyan; He, Wanhong; Wang, Liren; Yang, Junjiao; Xiang, Xu; Zhang, Bing; Li, Feng

    2015-07-01

    The hydrogenation of α,β-unsaturated aldehydes to allylic alcohols or saturated aldehydes provides a typical example to study the catalytic effect on structure-sensitive reactions. In this work, supported platinum nanocatalysts over hydrotalcite were synthesized by an alcohol reduction method. The Pt catalyst prepared by the reduction with a polyol (ethylene glycol) outperforms those prepared with ethanol and methanol in the hydrogenation of cinnamaldehyde. The selectivity towards the C=O bond is the highest over the former, although its mean size of Pt particles is the smallest. The hydroxyl groups on hydrotalcite could act as an internally accessible promoter to enhance the selectivity towards the C=O bond. The optimal Pt catalyst showed a high activity with an initial turnover frequency (TOF) of 2.314 s(-1). This work unveils the synergic effect of metal valence and in situ promoter on the chemoselective hydrogenation, which could open up a new direction in designing hydrogenation catalysts.

  15. Active and responsive polymer surfaces.

    PubMed

    Zhang, Jilin; Han, Yanchun

    2010-02-01

    A central challenge in polymer science today is creating materials that dynamically alter their structures and properties on demand, or in response to changes in their environment. Surfaces represent an attractive area of focus, since they exert disproportionately large effects on properties such as wettability, adhesiveness, optical appearance, and bioactivity, enabling pronounced changes in properties to be accomplished through subtle changes in interfacial structure or chemistry. In this critical review, we review the recent research progress into active and responsive polymer surfaces. The chief purpose of this article is to summarize the advanced preparation techniques and applications in this field from the past decade. This review should be of interest both to new scientists in this field and the interdisciplinary researchers who are working on "intelligent" polymer surfaces (117 references).

  16. Long-range influence of steps on water adsorption on clean and D-covered Pt surfaces.

    PubMed

    den Dunnen, Angela; van der Niet, Maria J T C; Badan, Cansin; Koper, Marc T M; Juurlink, Ludo B F

    2015-04-07

    We have examined water desorption from Pt(111) terraces of varying width and its dependence on precoverage by deuterium (D) with temperature programmed desorption studies. We observe distinct water desorption from (100) steps and (111) terraces, with steps providing adsorption sites with a higher binding energy than terraces. Preadsorption of D at the steps causes annihilation of water stabilization at the steps, while it also causes an initial stabilization of water on the (111) terraces. When the (111) terraces also become precovered with D, this water stabilization trend reverses on all surfaces. Destabilization continues for stepped surfaces containing up to 8-atom wide (111) terraces with a (100) step type and these become hydrophobic, in contrast to surfaces with a (110) step type and with the infinite (111) terrace. Our results illustrate how surface defects and a delicate balance between intermolecular forces and the adsorption energy govern hydrophobic vs. hydrophilic behavior, and that the influence of steps on the adsorption of water on nano-structured platinum surfaces has a very long-ranged character.

  17. A first-principles study of Pt-Ni bimetallic cluster adsorption on the anatase TiO2 (1 0 1) surface: Probing electron effect of Ni in TiO2 (1 0 1)-bimetallic cluster (Pt-Ni) on the adsorption and dissociation of methanol

    NASA Astrophysics Data System (ADS)

    Liu, Feila; Xiao, Peng; Uchaker, Evan; He, Huichao; Zhou, Ming; Zhou, Xin; Zhang, Yunhuai

    2014-10-01

    A density functional theory (DFT) based method in conjunction with the projector augmented wave and pseudopotential methods have been applied to investigate the adsorption of Pt4 and Pt3Ni on the anatase TiO2 (1 0 1) surface. Two stable Pt3Ni adsorptions with considerable adsorption energies on the anatase TiO2 (1 0 1) surface were identified. Analysis of the partial density (PDOS) of states and Bader charge suggest that the electronic structure of Pt is modified by Ni due to the electron transfer from Ni to Pt atoms in the Pt3Ni clusters. The 2cO (3cO)-PtNi-5cTi conformation of the adsorbed Pt3Ni on the anatase TiO2 (1 0 1) surface provides a more feasible model for electron injection through the Pt3Ni/TiO2 interface. The reactivity of Pt3Ni/TiO2 is superior to Pt4/TiO2 and effectively manifests itself in the eased decomposition of Osbnd H bonds derived by methanol and alleviative CO adsorption.

  18. Exceptional activity of sub-nm Pt clusters on CdS for photocatalytic hydrogen production: A combined of experimental and first-principles study

    DOE PAGES

    Wu, Qiyuan; Su, Dong; Xiong, Shangmin; ...

    2014-12-24

    In this work we have explored a new concept of substantially increasing photocatalytic activity for H₂ production of conventional semiconductors by modifying them with sub-nm Pt particles. By combining both experimental and theoretical approaches, we have also developed new mechanistic insights into the 17 times increase in photocatalytic activity of Pt modified CdS catalysts.

  19. Quaternary PtMnCuX/C (X = Fe, Co, Ni, and Sn) and PtMnMoX/C (X = Fe, Co, Ni, Cu and Sn) alloys catalysts: Synthesis, characterization and activity towards ethanol electrooxidation

    NASA Astrophysics Data System (ADS)

    Ammam, Malika; Easton, E. Bradley

    2012-10-01

    In this account, two series of quaternary PtMnCuX/C (X = Fe, Co, Ni, and Sn) and PtMnMoX/C (X = Fe, Co, Ni, Cu and Sn) alloys catalysts have been synthesized and characterized by ICP, XRD, XPS, TEM and cyclic voltammetry. XRD spectra of each series illustrated that PtMnCuX/C (X = Fe, Co and Ni) and PtMnMoX/C (X = Fe, Co, Ni and Cu) alloys have been formed without significant free Mn, Cu, Mo or X co-catalysts. For PtMnCuSn/C and PtMnMoSn/C, in addition to alloy formation, significant free Sn-oxides are present in each catalyst. Cyclic voltammetry and chronoamperometry revealed that all quaternary showed superior electrocatalytic activity towards ethanol oxidation compared to the ternary precursor. Also, shift of the onset potential of ethanol oxidation towards less positive values were also recorded with the quaternary alloys, demonstrating a facilitated oxidation with the quaternary alloys compared to ternary alloy precursor. The magnitude of the gain in potential depend on the alloy composition and PtMnMoSn/C was found to be the best of all synthetized quaternary alloys with an onset potential of ethanol oxidation of only 0.059 V vs. Ag/AgCl.

  20. Deactivation mechanism of PtOx/TiO(2) photocatalyst towards the oxidation of NO in gas phase.

    PubMed

    Wu, Zhongbiao; Sheng, Zhongyi; Liu, Yue; Wang, Haiqiang; Mo, Jiansong

    2011-01-30

    This study has been undertaken to investigate the roles of PtO and PtO(2) deposits in photocatalytic oxidation of NO over Pt-modified TiO(2) catalysts. These photocatalysts were prepared by neutralization method and characterized by XRD, BET, XPS, TEM and FTIR. It was found that Pt dopant existed as PtO and PtO(2) particles in as-prepared photocatalysts. And these Pt dopants would change their oxidation states during the photocatalytic oxidation reaction. An in situ XPS study indicated that a portion of PtO(2) on the surface of Pt/TiO(2) was reduced to PtO under UV irradiation. The migration of electrons to PtO(2) particles could separate the electrons and holes, resulting in the improvement of photocatalytic activity. And the depletion of PtO(2) by electrons could lead to the deactivation of Pt/TiO(2) catalyst. Moreover, PtO particles could be corroded to form Pt(2+) ions by HNO(3), which was one of the products of photocatalytic oxidation of NO. NO would adsorb on Pt(2+) related sites to form Pt(n+)-NO nitrosyls, retarding photocatalytic oxidation of NO to NO(2).

  1. Oxide composite prepared from intermetallic and amorphous Zr67Fe30M3- (M=Au, Pt) alloys and their catalytic activity for CO oxidation

    NASA Astrophysics Data System (ADS)

    Huang, Yung-Han; Wang, Sea-Fue; Kameoka, Satoshi; Miyamoto, Kanji; Tsai, An-Pang

    2017-01-01

    In this study, Zr67Fe30M3 (M=Au, Pt) intermetallic compounds and amorphous alloys were prepared and used as precursors for the synthesis of oxides. Oxidation treatment of the intermetallic compounds at 500 °C followed by X-ray diffraction (XRD) analysis indicated that zirconium and iron were oxidized to ZrO2 and Fe2O3, respectively. In the case of Zr67Fe30M3 amorphous alloys, cubic Zr6Fe3O was observed on the surface of the ribbons after heat treatment at 500 °C in vacuum. Addition of 3% of gold or platinum to the alloy resulted in an increase in the lattice constants of the Zr6Fe3O phase. Grounding the treated ribbons into powders followed by an oxidation treatment at 500 °C in air produced Fe2O3 and ZrO2 supports, where Au and Pt are dissolved in the oxides as confirmed by X-ray photoelectron spectroscopy (XPS). No matter precursors are intermetallics or amorphous phases, the resultant oxides are the same. Although Pt and Au dissolved in the oxides, catalytic activities for CO oxidation were significant improved.

  2. Synthesis of yolk/shell Fe3O4-polydopamine-graphene-Pt nanocomposite with high electrocatalytic activity for fuel cells

    NASA Astrophysics Data System (ADS)

    Huang, Yingqiang; Liu, Yingju; Yang, Zhuohong; Jia, Jinliang; Li, Xin; Luo, Yan; Fang, Yueping

    2014-01-01

    A novel yolk/shell Fe3O4-polydopamine-graphene-Pt (Fe3O4@PDA/RGO/Pt) nanocomposite is synthesized using polydopamine as a moderate modifier for graphene as well as a coupling agent for the assembly of Pt nanoparticles. The morphology and structure of the as-prepared catalysts are characterized by transmission electron microscopy, X-ray photoelectron spectroscopy, X-ray diffraction and Fourier transform infrared spectroscopy. The detailed formation mechanism of such yolk/shell nanocomposite is discussed. Subsequently, its catalytic activity towards the methanol oxidation is evaluated by cyclic voltammetry, chronoamperometry, electrochemical impedance spectra and CO-stripping voltammetry. Results show that such york/shell Fe3O4@PDA/RGO/Pt exhibits higher electrochemical activity and stability to methanol oxidation than Pt/graphene, which is not only attributed to the synergetic cocatalytic effect at the heterojunction interfaces between the Pt nanoparticles and the support, but also due to the high immobilization of Pt nanoparticles by the functional groups of polydopamine. In addition, the separation ability of Pt nanoparticles from the nanocomposite by Fe3O4 can decrease the CO poison from free Pt nanoparticles. Therefore, this unique yolk/shell nanocomposite may be suitable for the production of catalysts with low-cost and high activity.

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

    NASA Astrophysics Data System (ADS)

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

    2015-11-01

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

  4. Platinum Monolayer Electrocatalysts for O2 Reduction: Pt Monolayer on Carbon-Supported PdIr Nanoparticles

    SciTech Connect

    Vukmirovic, M.B.; Knupp, S.L. Haldar, P.; Herron, J.A.: Mavrikakis, M.; Adzic, R.R.

    2010-11-01

    The kinetics of oxygen reduction was investigated in acid solutions on Pt monolayers deposited on modified carbon-supported PdIr nanoparticles using the rotating disk-electrode technique. Iridium is introduced into the Pd substrate in order to fine-tune the Pt-Pd interactions and to improve Pd stability under operating conditions of the fuel cell. The kinetics of the oxygen reduction reaction shows enhancement with the Pt monolayer on the PdIr nanoparticle surfaces in comparison with the reaction on Pt/C and Pt monolayer on Pd/C nanoparticles. The electrochemical measurements suggest that reduced oxidation of Pt monolayer on PdIr/C compared to Pt/C and Pt monolayer on Pd/C is the cause of enhanced activity. Besides a ligand effect induced to the Pt surface by the presence of PdIr in the second sublayer of the nanoparticle, as suggested by our density functional theory analysis, Ir also leads to a Pd skin contraction, so the Pt monolayer on PdIr/C is compressed more than on Pd/C. Both effects lead to further weakening of the Pt-OH interaction, thus increasing the ORR activity. The Pt-specific activity for Pt{sub ML}PdIr/C is three times and 25% higher than that of Pt/C and Pt{sub ML}Pd/C respectively; the Pt-mass activity of Pt{sub ML}PdIr/C is more than 20 times and 25% higher than that of Pt/C and Pt{sub ML}Pd/C, respectively.

  5. Observation of a topologically non-trivial surface state in half-Heusler PtLuSb (001) thin films

    PubMed Central

    Logan, J. A.; Patel, S. J.; Harrington, S. D.; Polley, C. M.; Schultz, B. D.; Balasubramanian, T.; Janotti, A.; Mikkelsen, A.; Palmstrøm, C. J.

    2016-01-01

    The discovery of topological insulators, materials with bulk band gaps and protected cross-gap surface states in compounds such as Bi2Se3, has generated much interest in identifying topological surface states (TSSs) in other classes of materials. In particular, recent theoretical calculations suggest that TSSs may be found in half-Heusler ternary compounds. If experimentally realizable, this would provide a materials platform for entirely new heterostructure spintronic devices that make use of the structurally identical but electronically varied nature of Heusler compounds. Here we show the presence of a TSS in epitaxially grown thin films of the half-Heusler compound PtLuSb. Spin- and angle-resolved photoemission spectroscopy, complemented by theoretical calculations, reveals a surface state with linear dispersion and a helical tangential spin texture consistent with previous predictions. This experimental verification of topological behaviour is a significant step forward in establishing half-Heusler compounds as a viable material system for future spintronic devices. PMID:27346655

  6. Observation of a topologically non-trivial surface state in half-Heusler PtLuSb (001) thin films

    DOE PAGES

    Logan, J. A.; Patel, S. J.; Harrington, S. D.; ...

    2016-06-27

    The discovery of topological insulators, materials with bulk band gaps and protected cross-gap surface states in compounds such as Bi2Se3, has generated much interest in identifying topological surface states (TSSs) in other classes of materials. In particular, recent theoretical calculations suggest that TSSs may be found in half-Heusler ternary compounds. If experimentally realizable, this would provide a materials platform for entirely new heterostructure spintronic devices that make use of the structurally identical but electronically varied nature of Heusler compounds. Here we show the presence of a TSS in epitaxially grown thin films of the half-Heusler compound PtLuSb. Spin- and angle-resolvedmore » photoemission spectroscopy, complemented by theoretical calculations, reveals a surface state with linear dispersion and a helical tangential spin texture consistent with previous predictions. As a result, this experimental verification of topological behavior is a significant step forward in establishing half-Heusler compounds as a viable material system for future spintronic devices.« less

  7. Observation of a topologically non-trivial surface state in half-Heusler PtLuSb (001) thin films

    SciTech Connect

    Logan, J. A.; Patel, S. J.; Harrington, S. D.; Polley, C. M.; Schultz, B. D.; Balasubramanian, T.; Janotti, A.; Mikkelsen, A.; Palmstrøm, C. J.

    2016-06-27

    The discovery of topological insulators, materials with bulk band gaps and protected cross-gap surface states in compounds such as Bi2Se3, has generated much interest in identifying topological surface states (TSSs) in other classes of materials. In particular, recent theoretical calculations suggest that TSSs may be found in half-Heusler ternary compounds. If experimentally realizable, this would provide a materials platform for entirely new heterostructure spintronic devices that make use of the structurally identical but electronically varied nature of Heusler compounds. Here we show the presence of a TSS in epitaxially grown thin films of the half-Heusler compound PtLuSb. Spin- and angle-resolved photoemission spectroscopy, complemented by theoretical calculations, reveals a surface state with linear dispersion and a helical tangential spin texture consistent with previous predictions. As a result, this experimental verification of topological behavior is a significant step forward in establishing half-Heusler compounds as a viable material system for future spintronic devices.

  8. Observation of a topologically non-trivial surface state in half-Heusler PtLuSb (001) thin films

    NASA Astrophysics Data System (ADS)

    Logan, John; Patel, Sahil; Harrington, Sean; Polley, Craig; Schultz, Brian; Balasubramanian, T.; Janotti, Anderson; Mikkelsen, Anders; Palmstrøm, Chris

    Topological insulators are a recently discovered new quantum state of matter that has a bulk band gap but also possesses cross-gap surface states which are protected by time-reversal symmetry. The experimental realization of topologically non-trivial surface states (TSSs) in materials such as Bi2Se3 has generated widespread interest in identifying other material systems that exhibit TSSs due to their many uses including spintronic devices. In particular, recent theory calculations suggest that TSSs may be found in certain half-Heusler ternary compounds. If experimentally realizable, this would provide an opportunity for the creation of entirely new heterostructure spintronic devices that make use of the structurally-identical but electronically-varied nature of Heusler compounds. Here, we show the presence of a TSS in the half-Heusler compound PtLuSb. Spin and angle-resolved photoemission spectroscopy reveals a surface state with linear dispersion and a helical tangential spin texture consistent with theoretical predictions and the expectation for a topological insulator.

  9. CO 2 Adsorption on Anatase TiO 2 (101) Surfaces in the Presence of Subnanometer Ag/Pt Clusters: Implications for CO 2 Photoreduction

    DOE PAGES

    Yang, Chi-Ta; Wood, Brandon C.; Bhethanabotla, Venkat R.; ...

    2014-10-20

    We show how CO2 adsorption on perfect and reduced anatase TiO2 (101) surfaces can be substantially modified by the presence of surface Ag and Pt octamer clusters, using density functional theory calculations. Furthermore, we found that adsorption was affected even at sites where the adsorbate was not in direct contact with the octamer, which we attributed to charge donation to CO2 from the Ag/Pt-modified surface, as well as an electrostatic competition between attractive (Ti–O) and repulsive (Ti–C) interactions. Additionally, TiO2-supported Pt octamers offer key advantages that could be leveraged for CO2 photoreduction, including providing additional stable adsorption sites for bentmore » CO2 species and facilitating charge transfer to aid in CO2– anion formation. Electronic structure analysis suggests these factors arise primarily from the hybridization of the bonding molecular orbitals of CO2 with d orbitals of the Pt atoms. Our results show that, for adsorption on TiO2-supported Pt octamers, the O–C–O bending and C–O asymmetric stretching frequencies can be used as reliable indicators of the presence of the CO2– anion intermediate as well as to distinguish unique adsorption geometries or sites. Finally, we suggest a possible pathway for subsequent CO2 dissociation to CO at the surface of a reduced anatase TiO2 (101)-supported Pt octamer, which has a computed energy barrier of 1.01 eV.« less

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

    PubMed Central

    Papaderakis, Athanasios; Pliatsikas, Nikolaos; Prochaska, Chara; Papazisi, Kalliopi M.; Balomenou, Stella P.; Tsiplakides, Dimitrios; Patsalas, Panagiotis; Sotiropoulos, Sotiris

    2014-01-01

    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 toward 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. PMID:24959530

  11. Performance and durability of Pt/C cathode catalysts with different kinds of carbons for polymer electrolyte fuel cells characterized by electrochemical and in situ XAFS techniques.

    PubMed

    Nagasawa, Kensaku; Takao, Shinobu; Higashi, Kotaro; Nagamatsu, Shin-ichi; Samjeské, Gabor; Imaizumi, Yoshiaki; Sekizawa, Oki; Yamamoto, Takashi; Uruga, Tomoya; Iwasawa, Yasuhiro

    2014-06-07

    The electrochemical activity and durability of Pt nanoparticles on different kinds of carbon supports in oxygen reduction reactions (ORR) were investigated using rotating disc electrodes (RDE) and the membrane electrode assemblies (MEA) of polymer electrolyte fuel cells (PEFC). The mass activity of Pt/C catalysts (ORR activity per 1 mg of Pt) at the RDE decreased, according to the type of carbon support, in the following order; Ketjenblack (KB) > acetylene black (AB) > graphene > multiwall carbon nanotube (MW-CNT) > carbon black (CB), whereas the average size of the Pt nanoparticles and the surface specific activity (ORR activity per electrochemical surface area) did not vary significantly between these carbon supports. These results indicate that the different mass activities of the Pt/C catalysts may originate from the differences in the fraction of Pt on the carbon supports which is available for utilization. The durability of the MEAs of the top two active catalysts Pt/KB and Pt/AB among the five catalysts was examined based on ORR performance, TEM and in situ XAFS. It was found that the performance of the Pt/KB cathode catalyst in PEFC MEA decreased significantly over 500 accelerated durability test (ADT) cycles, whereas the performance of the Pt/AB cathode catalyst in PEFC MEA did not decrease significantly during 500 ADT cycles, it was also found that the Pt/AB possesses 8 times higher durability compared with the Pt/KB. In situ Pt LIII-edge XAFS data in the ADT cycles and stepwise potential operations revealed the different oxidation-reduction behaviors of the Pt nanoparticles on the KB and AB supports. The Pt/KB was oxidized to form surface PtO layers more easily than the Pt/AB in the increasing potential operation from 0.4 VRHE to 1.4 VRHE, and the surface PtO layers of the Pt/AB were reduced to the metallic Pt state more readily than those of the Pt/KB in the decreasing potential operation from 1.4 VRHE to 0.4 VRHE. The XAFS analysis for the Pt valences

  12. Bifurcation analysis of the three-variable model for the NO+CO reaction on Pt surfaces

    NASA Astrophysics Data System (ADS)

    Imbihl, R.; Fink, Th.; Krischer, K.

    1992-04-01

    Under isothermal conditions at low pressure (10-6 mbar range), the NO+CO reaction exhibits oscillatory behavior on a Pt(100) surface. Based on the results of in situ low-energy electron diffraction (LEED) measurements which showed that the 1×1⇄hex phase transition is not essential for producing oscillations, a three-variable model of coupled differential equations was developed which instead relies solely on the autocatalysis provided by the stoichiometry of the individual reaction steps. This model has been analyzed with the help of bifurcation theory using realistic values for the constants in the equations. The results demonstrate that the model reproduces, quite well, the existence range for oscillations on Pt(100). Two oscillatory regions exist with a large one located above the stoichiometry ratio pNO: pCO=1 and a very small one which is found just below pNO: pCO=1. Only the former one has a counterpart in the experiment. At low temperature two isolated branches of the reaction exist which merge at higher T in a transcritical bifurcation thus creating a peculiar hysteresis loop in the shape of a mushroom. Bifurcation analysis has also been applied to investigate the role of the internal parameters, e.g., the role of the constants in the differential equations. The most critical constants were those which control the dissociation of NO and, therefore, are decisive whether ignition or extinction in the reaction takes place. The high degree of qualitative and quantitative agreement which could be achieved with the three-variable model demonstrates that the model provides a reasonable description of the experiments.

  13. Surface enhanced vibrational spectroscopy and first-principles study of L-cysteine adsorption on noble trimetallic Au/Pt@Rh clusters.

    PubMed

    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.

  14. (abstract) Optical Scattering and Surface Microroughness of Ion Beam Deposited Au and Pt Thin Films

    NASA Technical Reports Server (NTRS)

    Al-Jumaily, Ghanim A.; Raouf, Nasrat A.; Edlou, Samad M.; Simons, John C.

    1994-01-01

    Thin films of gold and platinum have been deposited onto superpolished fused silica substrates using thermal evaporation, ion assisted deposition (IAD), and ion assisted sputtering. The influence of ion beam flux, thin film material, and deposition rate on the films microroughness have been investigated. Short range surface microroughness of the films has been examined using scanning tunneling microscopy (STM) and atomic force microscopy (AFM). Long range surface microroughness has been characterized using an angle resolved optical scatterometer. Results indicate that ion beam deposited coatings have improved microstructure over thermally evaporated films.

  15. Fabrication of catalytically active Au/Pt/Pd trimetallic nanoparticles by rapid injection of NaBH{sub 4}

    SciTech Connect

    Zhang, Haijun; Lu, Lilin; Cao, Yingnan; Du, Shuang; Cheng, Zhong; Zhang, Shaowei

    2014-01-01

    Graphical abstract: The synthesis and characterization of 2.0 nm-diameter Au/Pt/Pd nanoparticles are reported. The catalytic activity for glucose oxidation of the nanoparticles is several times higher than that of Au nanoparticles with nearly same size. - Highlights: • PVP-protected Au/Pt/Pd trimetallic nanoparticles (TNPs) of 2.0 nm in diameter were prepared. • The catalytic activity of TNPs is several times higher than that of Au nanoparticles. • Negatively charged Au atoms in the TNPs were confirmed by DFT calculation. - Abstract: Au/Pt/Pd trimetallic nanoparticles (TNPs) with an alloyed structure and an average diameter of about 2.0 nm were prepared via reducing the corresponding ions with rapidly injected NaBH{sub 4}, and characterized by UV–vis, TEM and HR-TEM. The catalytic activity of as-prepared TNPs for the aerobic glucose oxidation is several times higher than that of Au monometallic nanoparticles with about the same average size, which could be attributed to the catalytically active sites provided by the negatively charged Au atoms as a result of the electron donation from the neighboring Pd atoms. This was well supported by the electron density calculations based on the density functional theory.

  16. Reexamination of CO formation during formic acid decomposition on the Pt(1 1 1) surface in the gas phase

    NASA Astrophysics Data System (ADS)

    Wang, Yingying; Zhang, Dongju; Liu, Peng; Liu, Chengbu

    2016-08-01

    Existing theoretical results for formic acid (HCOOH) decomposition on Pt(1 1 1) cannot rationalize the easy CO poisoning of the catalysts in the gas phase. The present work reexamined HCOOH decomposition on Pt(1 1 1) by considering the effect of the initial adsorption structure of the reactant on the reactivity. Our calculations present a new adsorption configuration of HCOOH on Pt(1 1 1), from which the formation of CO is found to be competing with the formation of CO2. The newly proposed mechanism improves our understanding for the mechanism of HCOOH decomposition catalyzed by Pt-based catalysts.

  17. A Compendium of Scale Surface Microstructures: Ni(pt)al Coatings Oxidized at 1150 C for 2000 1-h Cycles

    NASA Technical Reports Server (NTRS)

    Smialek, James L.; Garg, Anita

    2010-01-01

    The surface structure of scales formed on Ni(Pt)Al coatings was characterized by SEM/EDS/BSE in plan view. Two nominally identical {100} samples of aluminide coated CMSX4 single crystal were oxidized at 1150 C for 2000 1-h cycles and were found to produce somewhat disparate behavior. One sample, with less propensity for coating grain boundary ridge deformation, presented primarily alpha-Al2O3 scale structures, with minimal weight loss and spallation. The original scale structure, still retained over most of the sample, consisted of the classic theta-alpha transformation-induced ridge network structure, with approx. 25 nm crystallographic steps and terraces indicative of surface rearrangement to low energy alumina planes. The scale grain boundary ridges were often decorated with a fine, uniform distribution of (Hf,Ti)O2 particles. Another sample, producing steady state weight losses, exhibited much interfacial spallation and a complex assortment of different structures. Broad areas of interfacial spalling, crystallographically-faceted (Ni,Co)(Al,Cr)2O4 spinel, with an alpha-Al2O3 base scale, were the dominant features. Other regions exhibited nodular spinel grains, with fine or (Ta,Ti)-rich (rutile) particles decorating or interspersed with the spinel. While these features were consistent with a coating that presented more deformation at extruded grain boundaries, the root cause of the different behavior between the duplicate samples could not be conclusively identified.

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

    NASA Astrophysics Data System (ADS)

    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

  19. Light illuminated α-Fe2O3/Pt nanoparticles as water activation agent for photoelectrochemical water splitting.

    PubMed

    Li, Xiaodong; Wang, Zhi; Zhang, Zemin; Chen, Lulu; Cheng, Jianli; Ni, Wei; Wang, Bin; Xie, Erqing

    2015-03-16

    The photoelectrochemical (PEC) water splitting is hampered by strong bonds of H2O molecules and low ionic conductivity of pure water. The photocatalysts dispersed in pure water can serve as a water activation agent, which provides an alternative pathway to overcome such limitations. Here we report that the light illuminated α-Fe2O3/Pt nanoparticles may produce a reservoir of reactive intermediates including H2O2, ·OH, OH(-) and H(+) capable of promoting the pure water reduction/oxidation half-reactions at cathode and highly photocatalytic-active TiO2/In2S3/AgInS2 photoanode, respectively. Remarkable photocurrent enhancement has been obtained with α-Fe2O3/Pt as water activation agent. The use of α-Fe2O3/Pt to promote the reactivity of pure water represents a new paradigm for reproducible hydrogen fuel provision by PEC water splitting, allowing efficient splitting of pure water without adding of corrosive chemicals or sacrificial agent.

  20. Monodisperse core/shell Ni/FePt nanoparticles and their con-version to Ni/Pt to catalyze oxygen reduction

    DOE PAGES

    Zhang, Sen; Hao, Yizhou; Su, Dong; ...

    2014-10-28

    We report a size-controllable synthesis of monodisperse core/shell Ni/FePt nanoparticles (NPs) via a seed-mediated growth and their subsequent conversion to Ni/Pt NPs. Preventing surface oxidation of the Ni seeds is essential for the growth of uniform FePt shells. These Ni/FePt NPs have a thin (≈ 1 nm) FePt shell, and can be converted to Ni/Pt by acetic acid wash to yield active catalysts for oxygen reduction reaction (ORR). Tuning the core size allow for optimization of their electrocatalytic activity. The specific activity and mass activity of 4.2 nm/0.8 nm core/shell Ni/FePt reach 1.95 mA/cm² and 490 mA/mgPt at 0.9 Vmore » (vs. reversible hydrogen electrode, RHE), which are much higher than those of benchmark commercial Pt catalyst (0.34 mA/cm² and 92 mA/mgPt at 0.9 V). Our studies provide a robust approach to monodisperse core/shell NPs with non-precious metal core, making it possible to develop advanced NP catalysts with ultralow Pt content for ORR and many other heterogeneous reactions.« less

  1. Incorporation effect of nanosized perovskite LaFe₀.₇Co₀.₃O₃ on the electrochemical activity of Pt nanoparticles-multi walled carbon nanotube composite toward methanol oxidation

    SciTech Connect

    Noroozifar, Meissam; Khorasani-Motlagh, Mozhgan; Khaleghian-Moghadam, Roghayeh; Ekrami-Kakhki, Mehri-Saddat; Shahraki, Mohammad

    2013-05-01

    Nanosized perovskite LaFe₀.₇Co₀.₃O₃ (LFCO) is synthesized through conventional co-precipitation method and characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive X-ray (EDX) techniques. The incorporation effect of the mentioned perovskite to catalytic activity of the PtNPs-MWCNTs-nafion (or -chitosan) catalyst toward methanol oxidation has been studied by cyclic voltammetry. Based on the electrochemical studies, all MWCNTs-PtNPs-nafion (or chitosan) and MWCNTs-PtNPs-LFCO-nafion (or chitosan) catalysts show a considerable activity for methanol oxidation. However, a synergistic effect is observed when LFCO is added to the catalyst by decreasing the poisoning rate of the Pt catalyst. - Graphical abstract: Nanosized perovskite LaFe₀.₇Co₀.₃O₃ is synthesized and characterized. The incorporation effect of the mentioned perovskite to catalytic activity of the PtNPS-MWCNTs-nafion (or -chitosan) catalyst toward methanol oxidation is studied. Highlights: • Nanocrystalline LaFe₀.₇Co₀.₃O₃ (LFCO) is prepared by a new simple co-precipitation method. • Effect of LFCO to catalytic activity of PtNPS for methanol oxidation is studied. • A synergistic effect is observed when LFCO is added to the Pt catalyst. • Oxygen of LFCO could be considered as active oxygen to remove CO intermediates.

  2. Effect of water and ammonia on surface species formed during NO(x) storage-reduction cycles over Pt-K/Al2O3 and Pt-Ba/Al2O3 catalysts.

    PubMed

    Morandi, Sara; Prinetto, Federica; Castoldi, Lidia; Lietti, Luca; Forzatti, Pio; Ghiotti, Giovanna

    2013-08-28

    The effect of water, in the temperature range 25-350 °C, and ammonia at RT on two different surface species formed on Pt-K/Al2O3 and Pt-Ba/Al2O3 NSR catalysts during NO(x) storage-reduction cycles was investigated. The surface species involved are nitrates, formed during the NO(x) storage step, and isocyanates, which are found to be intermediates in N2 production during reduction by CO. FT-IR experiments demonstrate that the dissociative chemisorption of water and ammonia causes the transformation of the bidentate nitrates and linearly bonded NCO(-) species into more symmetric species that we call ionic species. In the case of water, the effect on nitrates is observable at all the temperatures studied; however, the extent of the transformation decreases upon increasing temperature, consistent with the decreased extent of dissociatively adsorbed water. It was possible to hypothesize that the dissociative chemisorption of water and ammonia takes place in a competitive way on surface sites able to give bidentate nitrates and linearly bonded NCO(-) that are dislocated, remaining on the surface as ionic species.

  3. Atomic Structure of Pt3Ni Nanoframe Electrocatalysts by in Situ X-ray Absorption Spectroscopy.

    PubMed

    Becknell, Nigel; Kang, Yijin; Chen, Chen; Resasco, Joaquin; Kornienko, Nikolay; Guo, Jinghua; Markovic, Nenad M; Somorjai, Gabor A; Stamenkovic, Vojislav R; Yang, Peidong

    2015-12-23

    Understanding the atomic structure of a catalyst is crucial to exposing the source of its performance characteristics. It is highly unlikely that a catalyst remains the same under reaction conditions when compared to as-synthesized. Hence, the ideal experiment to study the catalyst structure should be performed in situ. Here, we use X-ray absorption spectroscopy (XAS) as an in situ technique to study Pt3Ni nanoframe particles which have been proven to be an excellent electrocatalyst for the oxygen reduction reaction (ORR). The surface characteristics of the nanoframes were probed through electrochemical hydrogen underpotential deposition and carbon monoxide electrooxidation, which showed that nanoframe surfaces with different structure exhibit varying levels of binding strength to adsorbate molecules. It is well-known that Pt-skin formation on Pt-Ni catalysts will enhance ORR activity by weakening the binding energy between the surface and adsorbates. Ex situ and in situ XAS results reveal that nanoframes which bind adsorbates more strongly have a rougher Pt surface caused by insufficient segregation of Pt to the surface and consequent Ni dissolution. In contrast, nanoframes which exhibit extremely high ORR activity simultaneously demonstrate more significant segregation of Pt over Ni-rich subsurface layers, allowing better formation of the critical Pt-skin. This work demonstrates that the high ORR activity of the Pt3Ni hollow nanoframes depends on successful formation of the Pt-skin surface structure.

  4. Role of chemical composition in the enhanced catalytic activity of Pt-based alloyed ultrathin nanowires for the hydrogen oxidation reaction under alkaline conditions

    SciTech Connect

    Megan E. Scofield; Wong, Stanislaus S.; Zhou, Yuchen; Yue, Shiyu; Wang, Lei; Su, Dong; Tong, Xiao; Vukmirovic, Miomir B.; Adzic, Radoslav R.

    2016-05-11

    With the increased interest in the development of hydrogen fuel cells as a plausible alternative to internal combustion engines, recent work has focused on creating alkaline fuel cells (AFC), which employ an alkaline environment. Working in alkaline as opposed to acidic media yields a number of tangible benefits, including (i) the ability to use cheaper and plentiful precious-metal-free catalysts, due to their increased stability, (ii) a reduction in the amount of degradation and corrosion of Pt-based catalysts, and (iii) a longer operational lifetime for the overall fuel cell configuration. However, in the absence of Pt, no catalyst has achieved activities similar to those of Pt. Herein, we have synthesized a number of crystalline ultrathin PtM alloy nanowires (NWs) (M = Fe, Co, Ru, Cu, Au) in order to replace a portion of the costly Pt metal without compromising on activity while simultaneously adding in metals known to exhibit favorable synergistic ligand and strain effects with respect to the host lattice. In fact, our experiments confirm theoretical insights about a clear and correlative dependence between measured activity and chemical composition. We have conclusively demonstrated that our as-synthesized alloy NW catalysts yield improved hydrogen oxidation reaction (HOR) activities as compared with a commercial Pt standard as well as with our as-synthesized Pt NWs. The Pt7Ru3 NW system, in particular, quantitatively achieved an exchange current density of 0.493 mA/cm2, which is higher than the corresponding data for Pt NWs alone. In addition, the HOR activities follow the same expected trend as their calculated hydrogen binding energy (HBE) values, thereby confirming the critical importance and correlation of HBE with the observed activities.

  5. Plasmonic enhancements of photocatalytic activity of Pt/n-Si/Ag photodiodes using Au/Ag core/shell nanorods.

    PubMed

    Qu, Yongquan; Cheng, Rui; Su, Qiao; Duan, Xiangfeng

    2011-10-26

    We report the plasmonic enhancement of the photocatalytic properties of Pt/n-Si/Ag photodiode photocatalysts using Au/Ag core/shell nanorods. We show that Au/Ag core/shell nanorods can be synthesized with tunable plasmon resonance frequencies and then conjugated onto Pt/n-Si/Ag photodiodes using well-defined chemistry. Photocatalytic studies showed that the conjugation with Au/Ag core/shell nanorods can significantly enhance the photocatalytic activity by more than a factor of 3. Spectral dependence studies further revealed that the photocatalytic enhancement is strongly correlated with the plasmonic absorption spectra of the Au/Ag core/shell nanorods, unambiguously demonstrating the plasmonic enhancement effect.

  6. Effect of the state of distribution of supported Pt nanoparticles on effective Pt utilization in polymer electrolyte fuel cells.

    PubMed

    Uchida, Makoto; Park, Young-Chul; Kakinuma, Katsuyoshi; Yano, Hiroshi; Tryk, Donald A; Kamino, Takeo; Uchida, Hiroyuki; Watanabe, Masahiro

    2013-07-21

    In polymer electrolyte fuel cells, it is essential to minimize Pt loading, particularly at the cathode, without serious loss of performance. From this point of view, we will report an advanced concept for the design of high performance catalysts and membrane-electrode assemblies (MEAs): first, the evaluation of Pt particle distributions on both the interior and exterior walls of various types of carbon black (CB) particles used as supports with respect to the "effective surface (ES)"; second, control of both size and location of Pt particles by means of a new preparation method (nanocapsule method); and finally, a new evaluation method for the properties of MEAs based on the Pt utilization (UPt), mass activity (MA), and effectiveness of Pt (EfPt), based on the ES concept. The amounts of Pt catalyst particles located in the CB nanopores were directly evaluated using the transmission electron microscopy, scanning electron microscopy and corresponding three-dimensional images. By use of the nanocapsule method and optimization of the ionomer, increased MA and EfPt values for the MEA were achieved. The improvement in the cathode performance can be attributed to the sharp particle-size distribution for Pt and the highly uniform dispersion on the exterior surface of graphitized carbon black (GCB) supports.

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

    PubMed

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

    2017-03-13

    To address the problems of high cost and poor stability of anode catalysts in direct ethanol fuel cells (DEFCs), ternary nanoparticles Pt9RhFex (x = 1, 3, 5, 7, and 9) supported on carbon powders (XC-72R) have been synthesized via a facile method involving reduction by sodium borohydride followed by thermal annealing in N2 at ambient pressure. The catalysts are physically characterized by X-ray diffraction, scanning transmission electron microscopy, and X-ray photoelectron spectroscopy, and their catalytic performance for the ethanol oxidation reaction (EOR) is evaluated by cyclic and linear scan voltammetry, CO-stripping voltammograms, and chronopotentiometry. All the Pt9RhFex/C catalysts of different atomic ratios produce high EOR catalytic activity. The catalyst of atomic ratio composition 9:1:3 (Pt/Rh/Fe) has the highest activity and excellent CO-poisoning tolerance. Moreover, the enhanced EOR catalytic activity on Pt9RhFe3/C when compared to Pt9Rh/C, Pt3Fe/C, and Pt/C clearly demonstrates the presence of Fe improves catalytic performance. Notably, the onset potential for CO oxidation on Pt9RhFe3/C (0.271 V) is ∼55, 75, and 191 mV more negative than on Pt9Rh/C (0.326 V), Pt3Fe/C (0.346 V), and Pt/C (0.462 V), respectively, which implies the presence of Fe atoms dramatically improves CO-poisoning tolerance. Meanwhile, compared to the commercial PtRu/C catalyst, the peak potential on Pt9RhFe3/C for CO oxidation was just slightly changed after several thousand cycles, which shows high stability against the potential cycling. The possible mechanism by which Fe and Rh atoms facilitate the observed enhanced performance is also considered herein, and we conclude Pt9RhFe3/C offers a promising anode catalyst for direct ethanol fuel cells.

  8. 'Soft' Au, Pt and Cu contacts for molecular junctions through surface-diffusion-mediated deposition.

    PubMed

    Bonifas, Andrew P; McCreery, Richard L

    2010-08-01

    Virtually all types of molecular electronic devices depend on electronically addressing a molecule or molecular layer through the formation of a metallic contact. The introduction of molecular devices into integrated circuits will probably depend on the formation of contacts using a vapour deposition technique, but this approach frequently results in the metal atoms penetrating or damaging the molecular layer. Here, we report a method of forming 'soft' metallic contacts on molecular layers through surface-diffusion-mediated deposition, in which the metal atoms are deposited remotely and then diffuse onto the molecular layer, thus eliminating the problems of penetration and damage. Molecular junctions fabricated by this method exhibit excellent yield (typically >90%) and reproducibility, and allow examination of the effects of molecular-layer structure, thickness and contact work function.

  9. Vibrational states of the Pt(111)- $ ≤ft( {sqrt {3} × sqrt {3} } right) $ R30°-K surface structure

    NASA Astrophysics Data System (ADS)

    Rusina, G. G.; Borisov, S. D.; Eremeev, S. V.; Chulkov, E. V.

    2010-09-01

    Vibrational spectrum of the ordered Pt(111)- left( {sqrt {3} × sqrt {3} } right) R30°- K surface superstructure formed on the platinum surface with adsorption of 1/3 ML potassium is calculated with the use of the interatomic interaction potentials obtained in the strong bond approximation. Relaxation of the surface, dispersion of the surface phonons, local density of vibrational states, and polarization of phonon modes of adatoms and atoms of the substrate are discussed in the work. The theoretical results obtained agree well with the available experimental data.

  10. Role of chemical composition in the enhanced catalytic activity of Pt-based alloyed ultrathin nanowires for the hydrogen oxidation reaction under alkaline conditions

    DOE PAGES

    Megan E. Scofield; Wong, Stanislaus S.; Zhou, Yuchen; ...

    2016-05-11

    With the increased interest in the development of hydrogen fuel cells as a plausible alternative to internal combustion engines, recent work has focused on creating alkaline fuel cells (AFC), which employ an alkaline environment. Working in alkaline as opposed to acidic media yields a number of tangible benefits, including (i) the ability to use cheaper and plentiful precious-metal-free catalysts, due to their increased stability, (ii) a reduction in the amount of degradation and corrosion of Pt-based catalysts, and (iii) a longer operational lifetime for the overall fuel cell configuration. However, in the absence of Pt, no catalyst has achieved activitiesmore » similar to those of Pt. Herein, we have synthesized a number of crystalline ultrathin PtM alloy nanowires (NWs) (M = Fe, Co, Ru, Cu, Au) in order to replace a portion of the costly Pt metal without compromising on activity while simultaneously adding in metals known to exhibit favorable synergistic ligand and strain effects with respect to the host lattice. In fact, our experiments confirm theoretical insights about a clear and correlative dependence between measured activity and chemical composition. We have conclusively demonstrated that our as-synthesized alloy NW catalysts yield improved hydrogen oxidation reaction (HOR) activities as compared with a commercial Pt standard as well as with our as-synthesized Pt NWs. The Pt7Ru3 NW system, in particular, quantitatively achieved an exchange current density of 0.493 mA/cm2, which is higher than the corresponding data for Pt NWs alone. In addition, the HOR activities follow the same expected trend as their calculated hydrogen binding energy (HBE) values, thereby confirming the critical importance and correlation of HBE with the observed activities.« less

  11. Correction: Particle shape optimization by changing from an isotropic to an anisotropic nanostructure: preparation of highly active and stable supported Pt catalysts in microemulsions

    NASA Astrophysics Data System (ADS)

    Parapat, Riny Y.; Wijaya, Muliany; Schwarze, Michael; Selve, Sören; Willinger, Marc; Schomäcker, Reinhard

    2016-03-01

    Correction for `Particle shape optimization by changing from an isotropic to an anisotropic nanostructure: preparation of highly active and stable supported Pt catalysts in microemulsions' by Riny Y. Parapat et al., Nanoscale, 2013, 5, 796-805.

  12. Direct imaging of thermally-activated grain-boundary diffusion in Cu/Co/IrMn/Pt exchange-bias structures using atom-probe tomography

    NASA Astrophysics Data System (ADS)

    Letellier, F.; Lechevallier, L.; Lardé, R.; Le Breton, J.-M.; Akmaldinov, K.; Auffret, S.; Dieny, B.; Baltz, V.

    2014-11-01

    Magnetic devices are often subject to thermal processing steps, such as field cooling to set exchange bias and annealing to crystallize amorphous magnetic electrodes. These processing steps may result in interdiffusion and the subsequent deterioration of magnetic properties. In this study, we investigated thermally-activated diffusion in Cu/Co/IrMn/Pt exchange biased polycrystalline thin-film structures using atom probe tomography. Images taken after annealing at 400 °C for 60 min revealed Mn diffusion into Co grains at the Co/IrMn interface and along Pt grain boundaries for the IrMn/Pt stack, i.e., a Harrison type C regime. Annealing at 500 °C showed further Mn diffusion into Co grains. At the IrMn/Pt interface, annealing at 500 °C led to a type B behavior since Mn diffusion was detected both along Pt grain boundaries and also into Pt grains. The deterioration of the films' exchange bias properties upon annealing was correlated to the observed diffusion. In particular, the topmost Pt capping layer thickness turned out to be crucial since a faster deterioration of the exchange bias properties for thicker caps was observed. This is consistent with the idea that Pt acts as a getter for Mn, drawing Mn out of the IrMn layer.

  13. Direct imaging of thermally-activated grain-boundary diffusion in Cu/Co/IrMn/Pt exchange-bias structures using atom-probe tomography

    SciTech Connect

    Letellier, F.; Lardé, R.; Le Breton, J.-M.; Akmaldinov, K.; Auffret, S.; Dieny, B.; Baltz, V.

    2014-11-28

    Magnetic devices are often subject to thermal processing steps, such as field cooling to set exchange bias and annealing to crystallize amorphous magnetic electrodes. These processing steps may result in interdiffusion and the subsequent deterioration of magnetic properties. In this study, we investigated thermally-activated diffusion in Cu/Co/IrMn/Pt exchange biased polycrystalline thin-film structures using atom probe tomography. Images taken after annealing at 400 °C for 60 min revealed Mn diffusion into Co grains at the Co/IrMn interface and along Pt grain boundaries for the IrMn/Pt stack, i.e., a Harrison type C regime. Annealing at 500 °C showed further Mn diffusion into Co grains. At the IrMn/Pt interface, annealing at 500 °C led to a type B behavior since Mn diffusion was detected both along Pt grain boundaries and also into Pt grains. The deterioration of the films' exchange bias properties upon annealing was correlated to the observed diffusion. In particular, the topmost Pt capping layer thickness turned out to be crucial since a faster deterioration of the exchange bias properties for thicker caps was observed. This is consistent with the idea that Pt acts as a getter for Mn, drawing Mn out of the IrMn layer.

  14. Clean method for the synthesis of reduced graphene oxide-supported PtPd alloys with high electrocatalytic activity for ethanol oxidation in alkaline medium.

    PubMed

    Ren, Fangfang; Wang, Huiwen; Zhai, Chunyang; Zhu, Mingshan; Yue, Ruirui; Du, Yukou; Yang, Ping; Xu, Jingkun; Lu, Wensheng

    2014-03-12

    In this article, a clean method for the synthesis of PtPd/reduced graphene oxide (RGO) catalysts with different Pt/Pd ratios is reported in which no additional components such as external energy (e.g., high temperature or high pressure), surfactants, or stabilizing agents are required. The obtained catalysts were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), induced coupled plasma atomic emission spectroscopy (ICP-AES), and electrochemical measurements. The HRTEM measurements showed that all of the metallic nanoparticles (NPs) exhibited well-defined crystalline structures. The composition of these Pt-Pd/RGO catalysts can be easily controlled by adjusting the molar ratio of the Pt and Pd precursors. Both cyclic voltammetry (CV) and chronoamperometry (CA) results demonstrate that bimetallic PtPd catalysts have superior catalytic activity for the ethanol oxidation reaction compared to the monometallic Pt or Pd catalyst, with the best performance found with the PtPd (1:3)/RGO catalyst. The present study may open a new approach for the synthesis of PtPd alloy catalysts, which is expected to have promising applications in fuel cells.

  15. Microwave-assisted synthesis of Pt/CNT nanocomposite electrocatalysts for PEM fuel cells.

    PubMed

    Zhang, Weimin; Chen, Jun; Swiegers, Gerhard F; Ma, Zi-Feng; Wallace, Gordon G

    2010-02-01

    Microwave-assisted heating of functionalized, single-wall carbon nanotubes (FCNTs) in ethylene glycol solution containing H(2)PtCl(6), led to the reductive deposition of Pt nanoparticles (2.5-4 nm) over the FCNTs, yielding an active catalyst for proton-exchange membrane fuel cells (PEMFCs). In single-cell testing, the Pt/FCNT composites displayed a catalytic performance that was superior to Pt nanoparticles supported by raw (unfunctionalized) CNTs (RCNTs) or by carbon black (C), prepared under identical conditions. The supporting single-wall carbon nanotubes (SWNTs), functionalized with carboxyl groups, were studied by thermogravimetric analysis (TGA), cyclic voltammetry (CV), and Raman spectroscopy. The loading level, morphology, and crystallinity of the Pt/SWNT catalysts were determined using TGA, SEM, and XRD. The electrochemically active catalytic surface area of the Pt/FCNT catalysts was 72.9 m(2)/g-Pt.

  16. Ni-, Pd-, or Pt-catalyzed ethylene dimerization: a mechanistic description of the catalytic cycle and the active species.

    PubMed

    Roy, Dipankar; Sunoj, Raghavan B

    2010-03-07

    Two key mechanistic possibilities for group 10 transition metal [M(eta(3)-allyl)(PMe(3))](+) catalyzed (where M = Ni(II), Pd(II) and Pt(II)) ethylene dimerization are investigated using density functional theory methods. The nature of the potential active catalysts in these pathways is analyzed to gain improved insights into the mechanism of ethylene dimerization to butene. The catalytic cycle is identified as involving typical elementary steps in transition metal-catalyzed C-C bond formation reactions, such as oxidative insertion as well as beta-H elimination. The computed kinetic and thermodynamic features indicate that a commonly proposed metal hydride species (L(n)M-H) is less likely to act as the active species as compared to a metal-ethyl species (L(n)M-CH(2)CH(3)). Of the two key pathways considered, the active species is predicted to be a metal hydride in pathway-1, whereas a metal alkyl complex serves as the active catalyst in pathway-2. A metal-mediated hydride shift from a growing metal alkyl chain to the ethylene molecule, bound to the metal in an eta(2) fashion, is predicted to be the preferred route for the generation of the active species. Among the intermediates involved in the catalytic cycle, metal alkyls with a bound olefin are identified as thermodynamically stable for all three metal ions. In general, the Ni-catalyzed pathways are found to be energetically more favorable than those associated with Pd and Pt catalysts.

  17. Modeling bulk and surface Pt using the "Gaussian and plane wave" density functional theory formalism: validation and comparison to k-point plane wave calculations.

    PubMed

    Santarossa, Gianluca; Vargas, Angelo; Iannuzzi, Marcella; Pignedoli, Carlo A; Passerone, Daniele; Baiker, Alfons

    2008-12-21

    We present a study on structural and electronic properties of bulk platinum and the two surfaces (111) and (100) comparing the Gaussian and plane wave method to standard plane wave schemes, normally employed for density functional theory calculations on metallic systems. The aim of this investigation is the assessment of methods based on the expansion of the Kohn-Sham orbitals into localized basis sets and on the supercell approach, in the description of the metallicity of Pt. Electronic structure calculations performed at Gamma-point only on supercells of different sizes, from 108 up to 864 atoms, are compared to the results obtained for the unit cell of four Pt atoms where the k-point expansion of the wave function over Monkhorst-Pack grids up to (10x10x10) has been employed. The evaluation of the two approaches with respect to bulk properties is done through the calculation of the equilibrium lattice constant, the bulk modulus, and the total and the d-projected density of states. For the Pt(111) and Pt(100) surfaces, we consider the relaxation of the first layers, the surface energies, the work function, the total density of states, as well as the center and filling of the d bands. Our results confirm that the accuracy of two approaches in the description of electronic and structural properties of Pt is equivalent, providing that consistent supercells and k-point meshes are used. Moreover, we estimate the supercell size that can be safely adopted in the Gaussian and plane wave method in order to obtain the same reliability of previous theoretical studies based on well converged plane wave calculations available in literature. The latter studies, in turn, set the level of agreement with experimental data. In particular, we obtain excellent agreement in the evaluation of the density of states for either bulk and surface systems, and our data are also in good agreement with previous works on Pt reported in literature. We conclude that Gaussian and plane wave

  18. Preparation of PtRu nanoparticles on various carbon supports using surfactants and their catalytic activities for methanol electro-oxidation

    NASA Astrophysics Data System (ADS)

    Kim, Cham; Kwon, Heock-Hoi; Song, In Kyu; Sung, Yung-Eun; Chung, Won Seob; Lee, Ho-In

    In the anodes of direct methanol fuel cells (DMFCs), Pt poisoning by CO adsorption during methanol electro-oxidation has been a serious problem. Efforts to overcome or minimize this obstacle have largely involved investigations of PtRu bimetallic catalysts. In order to prepare fine PtRu alloyed hydrosols, we used non-ionic surfactants including L121, Pluronic P123, P65, Brij 35, and Tween 20 as stabilizers in this study. The sizes of the prepared metal particles change with the surfactant used. The finest metal hydrosol is obtained when Pluronic P123 and P65 are used. The resulting metal hydrosols with Pluronic P123, Brij 35 and Tween 20 are supported on Vulcan XC-72R. PtRu/XC-72R prepared with Pluronic P123 exhibits the best catalytic activity due to better dispersion of the alloyed metal. To improve further the activity of the PtRu catalyst, the commercial Vulcan XC-72R is replaced with carbon spherule (CS), a home-made carbon support. Electrochemical analyses such as cyclic voltammetry and galvanostatic-polarization tests are performed to evaluate the prepared catalyst. PtRu/CS has a superior performance to PtRu/XC-72R in methanol electro-oxidation when Pluronic P123 is employed as the stabilizer. The higher conductivity and larger inter-particle space of the CS appear to facilitate methanol electro-oxidation.

  19. Tri-iodide reduction activity of ultra-small size PtFe nanoparticles supported nitrogen-doped graphene as counter electrode for dye-sensitized solar cell.

    PubMed

    Nechiyil, Divya; Vinayan, B P; Ramaprabhu, S

    2017-02-15

    Efficient and cost effective counter electrode (CE) is pre-requisite for the commercialization of dye-sensitized solar cell (DSSC). Present work investigates ultra small size platinum-iron alloy nanoparticles dispersed over nitrogen-doped graphene (PtFe/NG) as an effective counter electrode for DSSC. Hereby we achieve low loading of Pt by alloying with Fe accompanied by superior electrocatalytic activity towards the iodide-triiodide (I(-)/I3(-)) mechanism. Enhancement in electrocatalytic performance of PtFe/NG has been shown by cyclic voltammetry, electrochemical impedance spectroscopy and Tafel polarization analysis. PtFe/NG counter electrode exhibits higher power conversion efficiency (∼6.12%) with lower charge transfer resistance, which helps in faster diffusion of I(-)/I3(-) ions as compared to NG and Pt/NG counter electrodes. The increased electrocatalytic activity of PtFe/NG is due to the collective effect of intrinsic electronic effects by alloying, uniform dispersion of small PtFe alloy nanoparticles over nitrogen doped graphene, and additional catalytic sites offered by nitrogen-doped graphene.

  20. Si microwire array photoelectrochemical cells: Stabilized and improved performances with surface modification of Pt nanoparticles and TiO2 ultrathin film

    NASA Astrophysics Data System (ADS)

    Yan, Jimu; Wu, Shaolong; Zhai, Xiongfei; Gao, Xiang; Li, Xiaofeng

    2017-02-01

    To achieve the semiconductor photoelectrochemical (PEC) cells targeting the industry applications with commercial competitiveness, high efficiency and good stability are requisite properties. To improve the PEC response, the vertically-aligned silicon microwire arrays (SiMWAs) modified with isolated Pt nanoparticles (PtNPs) and conformal TiO2 ultrathin film (TiO2/Pt@SiMWAs) are fabricated and examined in this study. The modified system shows the significantly enhanced responses and operation stability, that is, an enhancement of ∼30.0% in saturation photocurrent density (Jsat), a cathodic shift of ∼0.85 V (relative to the bare SiMWAs) in applied potential for Jsat, and an attenuation ratio of the photocurrent <1.5% during 1800-sec-continuous operation in an aqueous electrolyte. The underlying mechanisms are attributed to: (1) PtNPs concentrate the incident photons, promote the photo-carrier separation, and catalyze the chemical reaction at the photoelectrode-electrolyte interfaces; (2) conformal TiO2 ultrathin film protects the SiMWAs from photo-oxidation/corrosion as well as suppresses the surface recombination. Our results indicate a feasible route for the practical applications of oxidizable and corrodible semiconductor micro-/nanostructures in the fields of PEC solar cells, water splitting, photodegradation, and so on.

  1. Analysis of Pt/SnO(sub x) during catalysis of CO oxidation

    NASA Technical Reports Server (NTRS)

    Sermon, Paul A.; Self, Valerie A.; Barrett, E. P. S.

    1990-01-01

    Temperature-programmed reduction using 6kPaH2 suggests that a sample consisting of 3 percent Pt supported directly on SnO2 is, under conditions of catalysis of CO oxidation used here, best represented as 3 percent Pt/SnO sub x, since the support is likely to partially reduced, probably in the vicinity of the metal/oxide interface. Catalytic measurements at 421 to 424 K show that this 3 percent Pt/SnO sub x is significantly more active per unit area of Pt than 6 percent Pt/SiO2 in catalyzing the oxidation of CO. In situ micro-FTIR reveals that while the latter has predominantly linearly bound CO on the surface under reaction conditions, the Pt/SnO sub x also has a species absorbing at 2168 cm(exp -1) which may be CO upon Pt in a positive oxidation state or weakly chemisorbed CO on zero-valent Pt. This may be directly involved in the low temperature oxidation of CO on the Pt/SnO sub x, since being weakly held the activation energy for its surface diffusion to the metal/oxide interface will be low; such mobile species could allow the high rates of surface transport and an increase in the fraction of the surface over which the CO oxidation occurs. FTIR also reveals carbonate-type species on the P/SnO sub c surface.

  2. Surface Segregation of Fe in Pt-Fe Alloy Nanoparticles: Its Precedence and Effect on the Ordered-Phase Evolution during Thermal Annealing.

    PubMed

    Prabhudev, Sagar; Bugnet, Matthieu; Zhu, Guo-Zhen; Bock, Christina; Botton, Gianluigi A

    2015-11-01

    Coupling electron microscopy techniques with in situ heating ability allows us to study phase transformations on the single-nanoparticle level. We exploit this setup to study disorder-to-order transformation of Pt-Fe alloy nanoparticles, a material that is of great interest to fuel-cell electrocatalysis and ultrahigh density information storage. In contrast to earlier reports, we show that Fe (instead of Pt) segregates towards the particle surface during annealing and forms a Fe-rich FeO x outer shell over the alloy core. By combining both ex situ and in situ approaches to probe the interplay between ordering and surface-segregation phenomena, we illustrate that the surface segregation of Fe precedes the ordering process and affects the ordered phase evolution dramatically. We show that the ordering initiates preferably at the pre-existent Fe-rich shell than the particle core. While the material-specific findings from this study open interesting perspectives towards a controlled phase evolution of Pt-Fe nanoalloys, the characterization methodologies described are general and should prove useful to probing a wide-range of nanomaterials.

  3. A Novel Activated-Charcoal-Doped Multiwalled Carbon Nanotube Hybrid for Quasi-Solid-State Dye-Sensitized Solar Cell Outperforming Pt Electrode.

    PubMed

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

    2016-03-23

    Highly conductive mesoporous carbon structures based on multiwalled carbon nanotubes (MWCNTs) and activated charcoal (AC) were synthesized by an enzymatic dispersion method. The synthesized carbon configuration consists of synchronized structures of highly conductive MWCNT and porous activated charcoal morphology. The proposed carbon structure was used as counter electrode (CE) for quasi-solid-state dye-sensitized solar cells (DSSCs). The AC-doped MWCNT hybrid showed much enhanced electrocatalytic activity (ECA) toward polymer gel electrolyte and revealed a charge transfer resistance (RCT) of 0.60 Ω, demonstrating a fast electron transport mechanism. The exceptional electrocatalytic activity and high conductivity of the AC-doped MWCNT hybrid CE are associated with its synchronized features of high surface area and electronic conductivity, which produces higher interfacial reaction with the quasi-solid electrolyte. Morphological studies confirm the forms of amorphous and conductive 3D carbon structure with high density of CNT colloid. The excessive oxygen surface groups and defect-rich structure can entrap an excessive volume of quasi-solid electrolyte and locate multiple sites for iodide/triiodide catalytic reaction. The resultant D719 DSSC composed of this novel hybrid CE fabricated with polymer gel electrolyte demonstrated an efficiency of 10.05% with a high fill factor (83%), outperforming the Pt electrode. Such facile synthesis of CE together with low cost and sustainability supports the proposed DSSCs' structure to stand out as an efficient next-generation photovoltaic device.

  4. Measured Activities of Al and Ni in gamma-(Ni) and gamma'-(Ni)3Al in the Ni-Al-Pt System

    NASA Technical Reports Server (NTRS)

    Copland, Evan

    2007-01-01

    Adding Pt to Ni-Al coatings is critical to achieving the required oxidation protection of Ni-based superalloys, but the nature of the Pt effect remains unresolved. This research provides a fundamental part of the answer by measuring the influence of Pt on the activities of Al and Ni in gamma-(Ni), gamma prime-(Ni)3Al and liquid in the Ni-Al-Pt system. Measurements have been made at 25 compositions in the Ni-rich corner over the temperature range, T = 1400-1750 K, by the vapor pressure technique with a multiple effusion-cell mass spectrometer (multi-cell KEMS). These measurements clearly show adding Pt (for X(sub Pt) less than 0.25) decreases a(Al) while increasing a(Ni). This solution behavior supports the idea that Pt increases Al transport to an alloy / Al2O3 interface and also limits the interaction between the coating and substrate alloys in the gamma-(Ni) + gamma prime-(Ni)3Al region. This presentation will review the progress of this study.

  5. Carbon xerogels as Pt catalyst supports for polymer electrolyte membrane fuel-cell applications

    NASA Astrophysics Data System (ADS)

    Liu, Bing; Creager, Stephen

    Carbon xerogels prepared by the resorcinol-formaldehyde (RF) sol-gel method with ambient-pressure drying were explored as Pt catalyst supports for polymer electrolyte membrane (PEM) fuel cells. Carbon xerogel samples without Pt catalyst (CX) were characterized by the N 2 sorption method (BET, BJH, others), and carbon xerogel samples with supported Pt catalyst (Pt/CX) were characterized by thermogravimetry (TGA), powder X-ray diffraction (XRD), electron microscopy (SEM, TEM) and ex situ cyclic voltammetry for thin-film electrode samples supported on glassy carbon and studied in a sulfuric acid electrolyte. Experiments on Pt/CX were made in comparison with commercially obtained samples of Pt catalyst supported on a Vulcan XC-72R carbon black support (Pt/XC-72R). CX samples had high BET surface area with a relatively narrow pore size distribution with a peak pore size near 14 nm. Pt contents for both Pt/CX and Pt/XC-72R were near 20 wt % as determined by TGA. Pt catalyst particles on Pt/CX had a mean diameter near 3.3 nm, slightly larger than for Pt/XC-72R which was near 2.8 nm. Electrochemically active surface areas (ESA) for Pt as determined by ex situ CV measurements of H adsorption/desorption were similar for Pt/XC-72R and Pt/CX but those from CO stripping were slightly higher for Pt/XC-72R than for Pt/CX. Membrane-electrode assemblies (MEAs) were fabricated from both Pt/CX and Pt/XC-72R on Nafion 117 membranes using the decal transfer method, and MEA characteristics and single-cell performance were evaluated via in situ cyclic voltammetry, polarization curve, and current-interrupt and high-frequency impedance methods. In situ CV yielded ESA values for Pt/XC-72R MEAs that were similar to those obtained by ex situ CV in sulfuric acid, but those for Pt/CX MEAs were smaller (by 13-17%), suggesting that access of Nafion electrolyte to Pt particles in Pt/CX electrodes is diminished relative to that for Pt/XC-72R electrodes. Polarization curve analysis at low current

  6. Enhanced electrocatalytic performance of Pt monolayer on nanoporous PdCu alloy for oxygen reduction

    NASA Astrophysics Data System (ADS)

    Hou, Linxi; Qiu, Huajun

    2012-10-01

    By selectively dealloying Al from PdxCu20-xAl80 ternary alloys in 1.0 M NaOH solution, nanoporous PdCu (np-PdCu) alloys with different Pd:Cu ratios are obtained. By a mild electrochemical dealloying treatment, the np-PdCu alloys are facilely converted into np-PdCu near-surface alloys with a nearly pure-Pd surface and PdCu alloy core. The np-PdCu near-surface alloys are then used as substrates to fabricate core-shell catalysts with a Pt monolayer as shell and np-PdCu as core by a Cu-underpotential deposition-Pt displacement strategy. Electrochemical measurements demonstrate that the Pt monolayer on np-Pd1Cu1 (Pt/np-Pd1Cu1) exhibits the highest Pt surface-specific activity towards oxygen reduction, which is ˜5.8-fold that of state-of-the-art Pt/C catalyst. The Pt/np-Pd1Cu1 also shows much enhanced stability with ˜78% active surface retained after 10,000 cycles (0.6-1.2 V vs. RHE). Under the same condition, the active surface of Pt/C drops to ˜28%.

  7. Cluster adsorption on amorphous and crystalline surfaces - A molecular dynamics study of model Pt on Cu and model Pd on Pt

    NASA Technical Reports Server (NTRS)

    Garofalini, S. H.; Halicioglu, T.; Pound, G. M.

    1981-01-01

    Molecular dynamics was used to study the structure, dispersion and short-time behavior of ten-atom clusters adsorbed onto amorphous and crystalline substrates, in which the cluster atoms differed from the substrate atoms. Two adatom-substrate model systems were chosen; one, in which the interaction energy between adatom pairs was greater than that between substrate pairs, and the other, in which the reverse was true. At relatively low temperature ranges, increased dispersion of cluster atoms occurred: (a) on the amorphous substrate as compared to the FCC(100) surface, (b) with increasing reduced temperature, and (c) with adatom-substrate interaction energy stronger than adatom-adatom interaction. Two-dimensional clusters (rafts) on the FCC(100) surface displayed migration of edge atoms only, indicating a mechanism for the cluster rotation and shape changes found in experimental studies.

  8. Novel Pt/Mg(In)(Al)O catalysts for ethane and propane dehydrogenation

    SciTech Connect

    Sun, Pingping; Siddiqi, Georges; Vining, William C.; Chi, Miaofang; Bell, Alexis T.

    2011-10-28

    Catalysts for the dehydrogenation of light alkanes were prepared by dispersing Pt on the surface of a calcined hydrotalcite-like support containing indium, Mg(In)(Al)O. Upon reduction in H{sub 2} at temperatures above 673 K, bimetallic particles of PtIn are observed by TEM, which have an average diameter of 1 nm. Analysis of Pt LIII-edge extended X-ray absorption fine structure (EXAFS) data shows that the In content of the bimetallic particles increases with increasing bulk In/Pt ratio and reduction temperature. Pt LIII-edge X-ray absorption near edge structure (XANES) indicates that an increasing donation of electronic charge from In to Pt occurs with increasing In content in the PtIn particles. The activity and selectivity of the Pt/Mg(In)(Al)O catalysts for ethane and propane dehydrogenation reactions are strongly dependent on the bulk In/Pt ratio. For both reactants, maximum activity was achieved for a bulk In/Pt ratio of 0.48, and at this In/Pt ratio, the selectivity to alkene was nearly 100%. Coke deposition was observed after catalyst use for either ethane or propane dehydrogenation, and it was observed that the alloying of Pt with In greatly reduced the amount of coke deposited. Characterization of the deposit by Raman spectroscopy indicates that the coke is present as highly disordered graphite particles <30 nm in diameter. While the amount of coke deposited during ethane and propane dehydrogenation are comparable, the effects on activity are dependent on reactant composition. Coke deposition had no effect on ethane dehydrogenation activity, but caused a loss in propane dehydrogenation activity. This difference is attributed to the greater ease with which coke produced on the surface of PtIn nanoparticles migrates to the support during ethane dehydrogenation versus propane dehydrogenation.

  9. Single Pt nanowire electrode: preparation, electrochemistry, and electrocatalysis.

    PubMed

    Li, Yongxin; Wu, Qingqing; Jiao, Shoufeng; Xu, Chaodi; Wang, Lun

    2013-04-16

    A single Pt nanowire electrode (SPNE) was fabricated through HF etching process from Pt disk nanoelectrode and an underpotential deposition (UPD) redox replacement technique. The electrochemical experiments showed that SPNE had steady-state electrochemical responses at redox species solution and the mass transfer rates were affected by the lengths and radii of SPNEs. The prepared SPNEs were utilized to examine the oxygen-reduction reaction in a KOH solution to explore the feasibility of electrocatalytic activity of single Pt nanowire and the results showed that the electrocatalytic activity of SPNE was dependent on the surface position of single Pt nanowire: the tip end position is more active than the sidewall position. Meanwhile, the electrocatalytic activity of SPNE was related to the radius of nanowire. These observations are not only important to understand the structure-function relationship in single nanowire level but have significant implications for the synthesis and selection of novel catalysts with high efficiency used in electrochemistry, energy, bioanalysis, etc.

  10. Well-defined and high resolution Pt nanowire arrays for a high performance hydrogen sensor by a surface scattering phenomenon.

    PubMed

    Yoo, Hae-Wook; Cho, Soo-Yeon; Jeon, Hwan-Jin; Jung, Hee-Tae

    2015-02-03

    Developing hydrogen (H2) sensors with a high sensitivity, rapid response, long-term stability, and high throughput is one of the critical issues in energy and environmental technology [Hübert et al. Sens. Actuators, B 2011, 157, 329]. To date, H2 sensors have been mainly developed using palladium (Pd) as the channel material because of its high selectivity and strong affinity to the H2 molecule [(Xu et al. Appl. Phys. Lett. 2005, 86, 203104), (Offermans et al. Appl. Phys. Lett. 2009, 94, 223110), (Yang et al. Nano Lett. 2009, 9, 2177), (Yang et al. ACS Nano 2010, 4, 5233), and (Zou et al. Chem. Commun. 2012, 48, 1033)]. Despite significant progress in this area, Pd based H2 sensors suffer from fractures on their structure due to hydrogen adsorption induced volumetric swelling during the α → β phase transition, leading to poor long-term stability and reliability [(Favier et al. Science 2001, 293, 2227), (Walter et al. Microelectron. Eng. 2002, 61–62, 555), and (Walter et al. Anal. Chem. 2002, 74, 1546)]. In this study, we developed a platinum (Pt) nanostructure based H2 sensor that avoids the stability limitations of Pd based sensors. This sensor exhibited an excellent sensing performance, low limit of detection (LOD, 1 ppm), reproducibility, and good recovery behavior at room temperature. This Pt based H2 sensor relies on a highly periodic, small cross sectional dimension (10–40 nm) and a well-defined configuration of Pt nanowire arrays over a large area. The resistance of the Pt nanowire arrays significantly decreased upon exposure to H2 due to reduced electron scattering in the cross section of the hydrogen adsorbed Pt nanowires, as compared to the oxygen terminated original state. Therefore, these well-defined Pt nanowire arrays prepared using advanced lithographic techniques can facilitate the production of high performance H2 sensors.

  11. Electrochemical and surface characteristics of carbon-supported PtSn electrocatalysts for ethanol electro-oxidation: possible application for inkjet ink formulations

    NASA Astrophysics Data System (ADS)

    Hsu, H. Y.; Tongol, B. J.

    2013-03-01

    Pt and PtxSny catalysts with different atomic ratios (90:10, 80:20, 70:30, 60:40 and 50:50) supported on carbon support (Vulcan XC-72) were prepared using the modified polyol method. The composition, particle size and structure of these catalysts were characterized by energy dispersive x-ray spectroscopy (EDX) and x-ray diffraction (XRD). XRD data revealed that the estimated particle sizes of all synthesized catalysts were approximately 2.0-3.0 nm. Cyclic voltammetric data showed that Pt80Sn20 exhibited the highest catalytic activity toward ethanol oxidation compared to other ratios in terms of area-normalized current densities. Chronoamperometry (CA) data confirmed that Pt70Sn30 was the most stable among the prepared catalysts with long-term poisoning rate of 4.25 × 10-3 (% s-1), which was four times lower than Pt (1.70 × 10-2). The catalyst with the optimum performance was used as the ink pigment of the inkjet ink formulations.

  12. Intrinsic activity and poisoning rate for HCOOH oxidation on platinum stepped surfaces.

    PubMed

    Grozovski, Vitali; Climent, Víctor; Herrero, Enrique; Feliu, Juan M

    2010-08-21

    Pulsed voltammetry has been used to study formic acid oxidation on platinum stepped surfaces to determine the kinetics of the reaction and the role of the surface structure in the reactivity. From the current transients at different potentials, the intrinsic activity of the electrode through the active intermediate reaction path (j(theta = 0)), as well as the rate constant for the CO formation (k(ads)) have been calculated. The kinetics for formic acid oxidation through the active intermediate reaction path is strongly dependent on the surface structure of the electrode, with the highest activity found for the Pt(100) surface. The presence of steps, both on (100) and (111) terraces, does not increase the activity of these surfaces. CO formation only takes place in a narrow potential window very close to the local potential of zero total charge. The extrapolation of the results obtained with stepped surfaces with (111) terraces to zero step density indicates that CO formation should not occur on an ideal Pt(111) electrode. Additionally, the analysis of the Tafel slopes obtained for the different electrodes suggests that the oxidation of formic acid is strongly affected by the presence of adsorbed anions, hydrogen and water.

  13. Effects of interfacial charge and the particle size of titanate nanotube-supported Pt nanoparticles on the hydrogenation of cinnamaldehyde

    NASA Astrophysics Data System (ADS)

    Chiu, Tsai-Chin; Lee, Hsin-Yi; Li, Pei-Hua; Chao, Jiunn-Hsing; Lin, Chiu-Hsun

    2013-03-01

    The oxidation state and size of Pt nanoparticles attached to alkali metal titanate nanotubes (MTNTs=M2Ti3O7, M = Li+, Na+, K+, Cs+) via ion exchange (indicated by the added label ‘-IE’) and wet impregnation (indicated by the added label ‘-IMP’) methods varied systematically with the cation of the MTNTs. X-ray photoelectron spectroscopy revealed that the binding energy of Pt was reduced to a low value when the support was changed from LiTNTs to CsTNTs, yielding a Ptδ- oxidation state. Thus, a space charge layer (SCL) was constructed at the interface between the Pt particle and MTNT support; the former carried the negative charge, and the alkali cation and proton in the hydroxyl group of the latter carried the positive charge. Due to a higher M/Ti atomic ratio in MTNTs, a higher electron density accumulated on Pt particles in Pt/MTNTs-IMP than on those in Pt/MTNTs-IE. Sub-ambient temperature temperature-programmed reduction and transmission electron microscopy revealed that because of the difference in reducibility of PtOx/MTNTs, the mean Pt particle size followed the order Pt/CsTNTs > Pt/KTNTs > Pt/NaTNTs > Pt/LiTNTs and Pt/MTNTs-IMP > Pt/MTNTs-IE. DRIFTS (diffuse reflectance infrared Fourier transform spectroscopy) showed that owing to its interaction with SCL, cinnamaldehyde adsorbed on Pt mainly through the C=C bond at the Pt-MTNT interfaces, and the small Pt particles in Pt/LiTNTs adsorbed three times more cinnamaldehyde than those in Pt/CsTNTs. Due to the competition between the adsorption of cinnamaldehyde and C=C activation, Pt/KTNT-IMP is the most active Pt/MTNT catalysts, achieving a conversion of 100% in the hydrogenation of cinnamaldehyde at 2 atm and 313 K. The carbonyl stretching of adsorbed cinnamaldehyde was almost unperturbed by adsorption (at 1705 cm-1), suggesting that Ptδ- and the π electrons in the carbonyl group repel each other, so the CH=O group points upward and away from the Pt surface, preventing it from being hydrogenated and

  14. The durability dependence of Pt/CNT electrocatalysts on the nanostructures of carbon nanotubes: hollow- and bamboo-CNTs

    SciTech Connect

    Shao, Yuyan; Kou, Rong; Wang, Jun; Wang, Chong M.; Vishwanathan, Vilanyur V.; Liu, Jun; Wang, Yong; Lin, Yuehe

    2009-07-01

    The electrochemical durability of Pt/CNT with hollow- and bamboo-structured carbon nanotubes as the support for PEM fuel cells was investigated using cyclic voltammetry (CV, 0.6-1.1V) accelerated degradation test method. Pt/CNT catalysts were characterized with cyclic voltammograms, rotating disk electrodes, and TEM images. The changes in the electrochemical surface area of Pt and the activity toward oxygen reduction reaction (ORR) before and after the degradation indicate that bamboo-structured carbon nanotubes supported Pt (Pt/B-CNT) catalyst exhibited much higher durability. TEM images indicate that the sintering of Pt nanoparticles was much less for Pt/B-CNT. These are attributed to the specific bamboo-like nanostructures which provide more “bamboo-knot” defects and edge plane-like defects. Pt-support interaction was therefore enhanced and the durability was improved.

  15. Enhanced reactivity for hydrogen reactions at Pt nanoislands on Au(111).

    PubMed

    Wolfschmidt, Holger; Weingarth, Daniel; Stimming, Ulrich

    2010-05-17

    We report high exchange current densities exceeding 1 A cm(-2) at Pt nanostructures on Au(111) for hydrogen-related reactions. Such activity is found at Pt nanoparticles with a coverage of less than 10 % of a monolayer on Au(111) and on single Pt particles deposited on Au(111). Potential pulse technique as well as micropolarization curves with overpotentials of +/-10 mV were used in the case of extended nanostructured surfaces to determine the activity. Single Pt particles were investigated in an in situ electrochemical scanning tunneling microscope setup using the STM tip as local sensor. The reactivity obtained on Pt nanostructured Au(111) towards hydrogen reactions were subsidized by single particle reactivity measurements. The specific activity of platinum is enhanced by more than a factor of 1000 as compared to a Pt(111) single crystal. Aspects that may explain this enhancement such as an involvement of the substrate, highly reactive defect sites and enhanced mass transport are discussed.

  16. High performance and durable nanostructured TiN supported Pt50-Ru50 anode catalyst for direct methanol fuel cell (DMFC)

    NASA Astrophysics Data System (ADS)

    Patel, Prasad Prakash; Datta, Moni Kanchan; Jampani, Prashanth H.; Hong, Daeho; Poston, James A.; Manivannan, Ayyakkannu; Kumta, Prashant N.

    2015-10-01

    The design of high performance and durable electro-catalyst has been of particular interest for DMFC anodes. Pt(Ru) has been considered the most active DMFC anode catalyst. In this work, the reaction kinetics of Pt(Ru) electro-catalyst has been improved by synthesizing high active surface area Pt50(Ru50) catalyst supported on highly conductive nanostructured titanium nitride, TiN. The Pt(Ru)/TiN has been synthesized by a complexed sol-gel (CSG) process using non-halide precursors of Pt and Ru. High surface area Pt(Ru)/TiN shows promising electrochemical performance for methanol oxidation, showing ∼52% improved catalytic activity at ∼0.65 V (vs NHE) and stability/durability in comparison with commercial JM-Pt(Ru). Single cell DMFC performance shows 56% improved maximum power density and superior electrochemical stability for CSG-Pt(Ru)/TiN compared to that of commercial JM-Pt(Ru). This is attributed to the uniform dispersion of Pt(Ru) achieved on the nanostructured TiN (support) yielding higher electrochemical active surface area and lower charge transfer resistance than commercial JM-Pt(Ru). Thus, the present study demonstrates the potential of nanostructured TiN as a support for Pt(Ru) based anode electro-catalyst for DMFC applications.

  17. The effect of thermal treatment on structure and surface composition of PtCo electro-catalysts for application in PEMFCs operating under automotive conditions

    NASA Astrophysics Data System (ADS)

    Stassi, A.; Gatto, I.; Monforte, G.; Baglio, V.; Passalacqua, E.; Antonucci, V.; Aricò, A. S.

    2012-06-01

    Structure and surface characteristics of carbon-supported PtCo cathode electro-catalysts were investigated to evaluate their performance and resistance to degradation under high temperature (∼110 °C) operation in a polymer electrolyte membrane fuel cell (PEMFC). Two different thermal treatments were investigated, i.e. 600 °C and 800 °C causing the occurrence of a disordered face-centered cubic (fcc) structure and a primitive cubic ordered (L12) phase. A specific colloidal preparation route and a carbothermal reduction allowed to obtain a similar mean crystallite size, i.e. 2.9 and 3.3 nm for the catalysts after the treatment at 600 °C and 800 °C, as well as a suitable degree of alloying. Both electrocatalysts were subjected to the same pre-leaching procedure to modulate the surface characteristics. The surface properties were investigated by X-ray photoelectron spectroscopy (XPS) and low-energy ion scattering spectroscopy (LE-ISS, 3He+ at 1 kV). A Pt segregation in the outermost surface layers and similar electronic properties for the materials were observed. Both catalysts showed good performance under PEMFC operation; however, the catalyst characterised by the disordered fcc structure performed slightly better at low temperature (80 °C) and full humidification; whereas, the primitive cubic ordered structure catalyst showed superior characteristics both in terms of performance and stability at high temperature (110 °C) and low R.H. These operating conditions are more relevant for automotive applications. The enhanced stability of the catalyst characterised by primitive cubic ordered structure was attributed to the growth of a stable Pt-oxide layer during operation at high temperature and low R.H. hindering sintering and dissolution processes at the catalyst surface.

  18. In Vitro and In Vivo Antitumor Activity of [Pt(O,O′-acac)(γ-acac)(DMS)] in Malignant Pleural Mesothelioma

    PubMed Central

    Muscella, Antonella; Vetrugno, Carla; Cossa, Luca Giulio; Antonaci, Giovanna; De Nuccio, Francesco; De Pascali, Sandra Angelica; Fanizzi, Francesco Paolo; Marsigliante, Santo

    2016-01-01

    Malignant pleural mesothelioma (MPM) is an aggressive malignancy highly resistant to chemotherapy. There is an urgent need for effective therapy inasmuch as resistance, intrinsic and acquired, to conventional therapies is common. Among Pt(II) antitumor drugs, [Pt(O,O′-acac)(γ-acac)(DMS)] (Ptac2S) has recently attracted considerable attention due to its strong in vitro and in vivo antiproliferative activity and reduced toxicity. The purpose of this study was to examine the efficacy of Ptac2S treatment in MPM. We employed the ZL55 human mesothelioma cell line in vitro and in a murine xenograft model in vivo, to test the antitumor activity of Ptac2S. Cytotoxicity assays and Western blottings of different apoptosis and survival proteins were thus performed. Ptac2S increases MPM cell death in vitro and in vivo compared with cisplatin. Ptac2S was more efficacious than cisplatin also in inducing apoptosis characterized by: (a) mitochondria depolarization, (b) increase of bax expression and its cytosol-to-mitochondria translocation and decrease of Bcl-2 expression, (c) activation of caspase-7 and -9. Ptac2S activated full-length PKC-δ and generated a PKC-δ fragment. Full-length PKC-δ translocated to the nucleus and membrane, whilst PKC-δ fragment concentrated to mitochondria. Ptac2S was also responsible for the PKC-ε activation that provoked phosphorylation of p38. Both PKC-δ and PKC-ε inhibition (by PKC–siRNA) reduced the apoptotic death of ZL55 cells. Altogether, our results confirm that Ptac2S is a promising therapeutic agent for malignant mesothelioma, providing a solid starting point for its validation as a suitable candidate for further pharmacological testing. PMID:27806086

  19. Tailored Rh surface facilitates, enhancement of Raman scattering in trimetallic AuPt core/Rh shell composites: Experimental and theoretical evidences

    NASA Astrophysics Data System (ADS)

    Loganathan, B.; Chandraboss, V. L.; Senthilvelan, S.; Karthikeyan, B.

    2016-01-01

    We present a detailed analysis of surface-enhanced Raman scattering of 7-azaindole and L-cysteine adsorbed on a tailored Rh surface by using experimental and density functional theoretical (DFT) calculations. DFT with the B3LYP/Lanl2DZ basis set was used for the optimization of the ground state geometries and simulation of the surface-enhanced Raman spectrum of probe molecules adsorbed on Rh6 cluster. 7-azaindole and L-cysteine adsorption at the shell interface was ascertained from first-principles. In addition, characterization of synthesized trimetallic AuPt core/Rh shell colloidal nanocomposites has been analyzed by UV-visible spectroscopy, high-resolution transmission and scanning electron microscopy, selected area electron diffraction pattern analysis, energy-dispersive X-ray spectroscopy, atomic force, confocal Raman microscopy, FT-Raman and surface-enhanced Raman spectroscopic analysis. This analysis serves as the first step in gaining an accurate understanding of specific interactions at the interface of organic and biomolecules and to gain knowledge on the surface composition of trimetallic Au/Pt/Rh colloidal nanocomposites.

  20. Resonant core spectroscopies of the charge transfer interactions between C60 and the surfaces of Au(111), Ag(111), Cu(111) and Pt(111)

    NASA Astrophysics Data System (ADS)

    Gibson, Andrew J.; Temperton, Robert H.; Handrup, Karsten; O'Shea, James N.

    2017-03-01

    Charge transfer interactions between C60 and the metal surfaces of Ag(111), Cu(111), Au(111) and Pt(111) have been studied using synchrotron-based photoemission, resonant photoemission and X-ray absorption spectroscopies. By placing the X-ray absorption and valence band spectra on a common binding energy scale, the energetic overlap of the unoccupied molecular orbitals with the density of states of the underlying metal surface have been assessed in the context of possible charge transfer pathways. Resonant photoemission and resonant Auger data, measuring the valence region as a function of photon energy for C60 adsorbed on Au(111) reveals three constant high kinetic energy features associated with Auger-like core-hole decay involving an electron transferred from the surface to the LUMO of the molecule and electrons from the three highest occupied molecular orbitals, respectively and in the presence of ultra-fast charge transfer of the originally photoexcited molecule to the surface. Data for the C60/Ag(111) surface reveals an additional Auger-like feature arising from a core-hole decay process involving more than one electron transferred from the surface into the LUMO. An analysis of the relative abundance of these core-hole decay channels estimates that on average 2.4 ± 0.3 electrons are transferred from the Ag(111) surface into the LUMO. A core-hole clock analysis has also been applied to assess the charge transfer coupling in the other direction, from the molecule to the Au(111) and Ag(111) surfaces. Resonant photoemission and resonant Auger data for C60 molecules adsorbed on the Pt(111) and Cu(111) surfaces are shown to exhibit no super-Auger features, which is attributed to the strong modification of the unoccupied molecular orbitals arising from stronger chemical coupling of the molecule to the surface.

  1. Oxygen vacancy promoted CO oxidation over Pt/CeO2 catalysts: A reaction at Pt-CeO2 interface

    NASA Astrophysics Data System (ADS)

    Liu, Huan-Huan; Wang, Yu; Jia, Ai-Pin; Wang, Shu-Yuan; Luo, Meng-Fei; Lu, Ji-Qing

    2014-09-01

    A series of Pt/CeO2 catalysts with different Pt contents were prepared using an incipient wetness impregnation method and tested for CO oxidation. Kinetic study on the catalysts indicated that the reaction rate was independent of the partial pressures of CO and O2 (r = kapp[CO]0[O2]0). The derived reaction pathways involved chemisorption of CO on surface Pt atoms and reacting with lattice oxygen provided by the CeO2 support at the Pt-CeO2 interface, suggesting a Mars van-Krevelen type reaction on these catalysts and the interfacial Pt-O-Ce ensembles being the active sites. Also, turnover frequencies (TOFs) calculated based on Pt dispersion and periphery Pt atoms were found to be proportional to the Pt particle size, with the large Pt particles possessing higher TOF than the small ones. Such a trend was interpreted by the important role of the oxygen vacancies via the formation of Pt-Ce-O solid solution, which could accelerate the mobility of lattice oxygen and consequently the activity.

  2. Surface-Activated Coupling Reactions Confined on a Surface.

    PubMed

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

    2015-10-20

    Chemical reactions may take place in a pure phase of gas or liquid or at the interface of two phases (gas-solid or liquid-solid). Recently, the emerging field of "surface-confined coupling reactions" has attracted intensive attention. In this process, reactants, intermediates, and products of a coupling reaction are adsorbed on a solid-vacuum or a solid-liquid interface. The solid surface restricts all reaction steps on the interface, in other words, the reaction takes place within a lower-dimensional, for example, two-dimensional, space. Surface atoms that are fixed in the surface and adatoms that move on the surface often activate the surface-confined coupling reactions. The synergy of surface morphology and activity allow some reactions that are inefficient or prohibited in the gas or liquid phase to proceed efficiently when the reactions are confined on a surface. Over the past decade, dozens of well-known "textbook" coupling reactions have been shown to proceed as surface-confined coupling reactions. In most cases, the surface-confined coupling reactions were discovered by trial and error, and the reaction pathways are largely unknown. It is thus highly desirable to unravel the mechanisms, mechanisms of surface activation in particular, of the surface-confined coupling reactions. Because the reactions take place on surfaces, advanced surface science techniques can be applied to study the surface-confined coupling reactions. Among them, scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS) are the two most extensively used experimental tools. The former resolves submolecular structures of individual reactants, intermediates, and products in real space, while the latter monitors the chemical states during the reactions in real time. Combination of the two methods provides unprecedented spatial and temporal information on the reaction pathways. The experimental findings are complemented by theoretical modeling. In particular, density

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

    SciTech Connect

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

    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.

  4. Radiolytic preparation of nanosized Pt particles in sodium zeolite A

    NASA Astrophysics Data System (ADS)

    Vijayalakshmi, R.; Kapoor, S.; Kulshreshtha, S. K.

    2002-04-01

    Nanosized platinum metal particles in zeolite NaA have been prepared by four different methods, namely, (I) γ-radiolysis of zeolite A sample exchanged with [Pt(NH 3) 4] 2+, (II) γ-radiolysis of precursor gel containing Pt 2+ ions followed by hydrothermal crystallisation to form zeolite A, (III) hydrogen reduction of Pt 2+ ions containing precursor gel followed by hydrothermal crystallisation and (IV) impregnation of zeolite A with H 2PtCl 6 solution followed by reduction at 200 °C in hydrogen flow. The size of Pt metal particles has been evaluated from X-ray line broadening and TEM and is found to be in the range of 5-15 nm for samples II, III and IV. Based on catalytic activity of these samples for hydrogenation of ethylene and cyclohexene, it is inferred that for sample I, Pt metal particles are confined to the pores of zeolite A. Unlike this, the Pt metal particles are randomly distributed in the zeolite matrix for samples II and III. For sample IV, the Pt metal particles are present over the surface of zeolite A.

  5. The seasonal activity and the effect of mechanical bending and wounding on the PtCOMT promoter in Betula pendula Roth.

    PubMed

    Tiimonen, Heidi; Häggman, Hely; Tsai, Chung-Jui; Chiang, Vincent; Aronen, Tuija

    2007-08-01

    In this study, 900-bp (signed as p including nucleotides -1 to -886) and partly deleted (signed as dp including nucleotides -1 to -414) COMT (caffeate/5-hydroxyferulate O-methyltransferase) promoters from Populus tremuloides Michx. were fused to the GUS reporter gene, and the tissue-specific expression patterns of the promoters were determined in Betula pendula Roth along the growing season, and as a response to mechanical bending and wounding. The main activity of the PtCOMTp- and PtCOMTdp-promoters, determined by the histochemical GUS assay, was found in the developing xylem of stems during the 8th-13th week and in the developing xylem of roots in the 13th week of the growing season. The GUS expression patterns did not differ among the xylem cell types. The PtCOMT promoter-induced GUS expression observed in phloem fibres suggests a need for PtCOMT expression and thus syringyl (S) lignin synthesis in fibre lignification. However, the PtCOMTdp-promoter induced GUS expression in stem trichomes, which may contribute to the biosynthesis of phenylpropanoid pathway-derived compounds other than lignin. Finally, a strong GUS expression was induced by the PtCOMT promoters in response to mechanical stem bending but not to wounding. The lack of major differences between the PtCOMTp- and PtCOMTdp-promoters suggests that the deleted promoter sequence (including nucleotides -415 to -886) did not contain a significant regulatory element contributing to the GUS expression in young B. pendula trees.

  6. Low Pt-content ternary PdCuPt nanodendrites: an efficient electrocatalyst for oxygen reduction reaction

    SciTech Connect

    Fu, Shaofang; Zhu, Chengzhou; Song, Junhua; Zhang, Peina; Engelhard, Mark H.; Xia, Haibing; Du, Dan; Lin, Yuehe

    2017-01-01

    Dendritic nanostructures are capturing increasing attentions in electrocatalysis owing to their unique structural features and low density. Herein, we report for the first time bromide ions mediated synthesis of low-Pt-content PdCuPt ternary nanodendrites via galvanic replacement reaction between Pt precursor and PdCu template in aqueous solution. The experimental results show that the ternary PdCuPt nanodendrites present enhanced electrocatalytic performance for oxygen reduction reaction in acid solution compared with commercial Pt/C as well as some state-of-the-art catalysts. In details, the mass activity of the PdCuPt catalyst with optimized composition is 1.73 A/mgPt at 0.85 V vs RHE, which is 14 times higher than that of commercial Pt/C catalyst. Moreover, the long-term stability test demonstrates its better durability in acid solution. After 5k cycles, there is still 70% electrochemical surface area maintained. This method provides an efficient way to synthesize trimetallic alloys with controllable composition and specific structure for oxygen reduction reaction.

  7. Improved oxygen reduction reaction catalyzed by Pt/Clay/Nafion nanocomposite for PEM fuel cells.

    PubMed

    Narayanamoorthy, B; Datta, K K R; Eswaramoorthy, M; Balaji, S

    2012-07-25

    A novel Pt nanoparticle (Pt NP) embedded aminoclay/Nafion (Pt/AC/N) nanocomposite catalyst film was prepared for oxygen reduction reaction by sol-gel method. The prepared nanocomposite films were surface characterized using XRD and TEM and thermal stability was studied by TGA. The prepared film has firmly bound Pt NP and could exhibit an improved electro-reduction activity compared to vulcan carbon/Nafion supported Pt NP (Pt/VC/N). Moreover, the Pt/AC/N film possessed good stability in the acidic environment. The limiting current density of the Pt/AC/N film with 35.4 μg/cm(2) of Pt loading was found to be 4.2 mA/cm(2), which is 30% higher than that of the Pt/VC/N. The maximum H2O2 intermediate formation was found to be ∼1.6% and the reaction found to follow a four electron transfer mechanism. Accelerated durability test for 2000 potential cycles showed that ca. 78% of initial limiting current was retained. The results are encouraging for possible use of the Pt/AC/N as the free-standing electrocatalyst layer for polymer electrolyte membrane fuel cells.

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

    NASA Astrophysics Data System (ADS)

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

    2012-06-01

    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.

  9. Synthesis of homogeneous Pt-bimetallic nanoparticles as highly efficient electrocatalysts.

    SciTech Connect

    Wang, C.; Chi, M.; Li, D.; van der Vliet, D.; Wang, G.; Lin, Q.; Mitchell, J.; More, K. L.; Markovic, N. M.; Stamenkovic, V. R.

    2011-01-01

    Alloying has shown enormous potential for tailoring the atomic and electronic structures, and improving the performance of catalytic materials. Systematic studies of alloy catalysts are, however, often compromised by inhomogeneous distribution of alloying components. Here we introduce a general approach for the synthesis of monodispersed and highly homogeneous Pt-bimetallic alloy nanocatalysts. Pt{sub 3}M (where M = Fe, Ni, or Co) nanoparticles were prepared by an organic solvothermal method and then supported on high surface area carbon. These catalysts attained a homogeneous distribution of elements, as demonstrated by atomic-scale elemental analysis using scanning transmission electron microscopy. They also exhibited high catalytic activities for the oxygen reduction reaction (ORR), with improvement factors of 2-3 versus conventional Pt/carbon catalysts. The measured ORR catalytic activities for Pt{sub 3}M nanocatalysts validated the volcano curve established on extended surfaces, with Pt{sub 3}Co being the most active alloy.

  10. Immobilization of Active Bacteriophages on Polyhydroxyalkanoate Surfaces.

    PubMed

    Wang, Chanchan; Sauvageau, Dominic; Elias, Anastasia

    2016-01-20

    A rapid, efficient technique for the attachment of bacteriophages (phages) onto polyhydroxyalkanoate (PHA) surfaces has been developed and compared to three reported methods for phage immobilization. Polymer surfaces were modified to facilitate phage attachment using (1) plasma treatment alone, (2) plasma treatment followed by activation by 1-ethyl-3-(3-(dimethylamino)propyl)carbodiimide hydrochloride (EDC) and N-hydroxysulfosuccinimide (sulfo-NHS), (3) plasma-initiated acrylic acid grafting, or (4) plasma-initiated acrylic acid grafting with activation by EDC and sulfo-NHS. The impact of each method on the surface chemistry of PHA was investigated using contact angle analysis and X-ray photoelectron spectroscopy. Each of the four treatments was shown to result in both increased hydrophilicity and in the modification of the surface functional groups. Modified surfaces were immersed in suspensions of phage T4 for immobilization. The highest level of phage binding was observed for the surfaces modified by plasma treatment alone. The change in chemical bond states observed for surfaces that underwent plasma treatment is suspected to be the cause of the increased binding of active phages. Plasma-treated surfaces were further analyzed through phage-staining and fluorescence microscopy to assess the surface density of immobilized phages and their capacity to capture hosts. The infective capability of attached phages was confirmed by exposing the phage-immobilized surfaces to the host bacteria Escherichia coli in both plaque and infection dynamic assays. Plasma-treated surfaces with immobilized phages displayed higher infectivity than surfaces treated with other methods; in fact, the equivalent initial multiplicity of infection was 2 orders of magnitude greater than with other methods. Control samples - prepared by immersing polymer surfaces in phage suspensions (without prior plasma treatment) - did not show any bacterial growth inhibition, suggesting they did not bind

  11. Surface passivation and protection of Pt loaded multicrystalline pn+ silicon photocathodes by atmospheric plasma oxidation for improved solar water splitting

    NASA Astrophysics Data System (ADS)

    Fan, Ronglei; Tang, Chengshuang; Xin, Yu; Su, Xiaodong; Wang, Xiaodong; Shen, Mingrong

    2016-12-01

    In the traditional methods such as atomic layer deposition and sputtering, a thin metal oxide layer was usually deposited before the loading of catalysts to protect Si photoelectrodes from oxidation during solar water splitting, and this often results in the transfer of photogenerated carriers from Si to electrolyte more or less inhibited. We here use an atmospheric plasma oxidation method to improve this. A SiO2 protective layer, also an effective passivation layer of Si to increase the life time of carriers, is fabricated on Pt loaded multicrystalline pn+-Si photocathodes. Compared with the un-protected one, the energy conversion efficiency of the plasma-treated Pt/pn+-Si photocathode increases from 6.2% to 8.9% under 100 mW/cm2 Xe lamp, and its stability improves from less than 1-22 h under continuous H2 production. This research provides a conceptual strategy to ensure the direct contact among the Si/Pt/electrolyte and protect and passivate the other part of Si simultaneously.

  12. Novel 2D RuPt core-edge nanocluster catalyst for CO electro-oxidation

    NASA Astrophysics Data System (ADS)

    Grabow, Lars C.; Yuan, Qiuyi; Doan, Hieu A.; Brankovic, Stanko R.

    2015-10-01

    A single layer, bi-metallic RuPt catalyst on Au(111) is synthesized using surface limited red-ox replacement of underpotentially deposited Cu and Pb monolayers though a two-step process. The resulting 2D RuPt monolayer nanoclusters have a unique core-edge structure with a Ru core and Pt at the edge along the perimeter. The activity of this catalyst is evaluated using CO monolayer oxidation as the probe reaction. Cyclic voltammetry demonstrates that the 2D RuPt core-edge catalyst morphology is significantly more active than either Pt or Ru monolayer catalysts. Density functional theory calculations in combination with infra-red spectroscopy data point towards oscillating variations (ripples) in the adsorption energy landscape along the radial direction of the Ru core as the origin of the observed behavior. Both, CO and OH experience a thermodynamic driving force for surface migration towards the Ru-Pt interface, where they adsorb most strongly and react rapidly. We propose that the complex interplay between epitaxial strain, ligand and finite size effects is responsible for the formation of the rippled RuPt monolayer cluster, which provides optimal conditions for a quasi-ideal bi-functional mechanism for CO oxidation, in which CO is adsorbed mainly on Pt, and Ru provides OH to the active Pt-Ru interface.

  13. Surface Patterns of Tetragonal Phase FePt Thin Films from Pt{at}Fe2O3 Core-Shell Nanoparticles Using Combined Langmuir-Blodgett and Soft Lithographic Techniques

    SciTech Connect

    Guo, Q.; Teng, X.; Yang, H.

    2003-09-30

    OAK B204 We present the fabrication of micron-sized patterns of FePt thin films from Pt{at}Fe2O3 core-shell nanoparticles. In a typical procedure, Pt@Fe2O3 core-shell nanoparticles were spread and formed a Langmuir film using water as the subphase. This film was lifted onto polydimethylsiloxane (PDMS) stamps with micron-sized patterns of lines, dots and wells, and transferred onto silicon wafers using microcontact printing (u-CP). The patterns of Pt@Fe2O3 core-shell nanoparticles were converted into face-centered tetragonal phase FePt alloy at enhanced temperatures in the presence of 5% hydrogen. Scanning electron microscopy (SEM), atomic force microscopy (AFM), powder X-ray diffraction (PXRD) and superconducting quantum interference device (SQUID) magnetometer were used to characterize the patterns and the properties of the final FePt alloy films.

  14. Tuning nanoparticle structure and surface strain for catalysis optimization.

    PubMed

    Zhang, Sen; Zhang, Xu; Jiang, Guangming; Zhu, Huiyuan; Guo, Shaojun; Su, Dong; Lu, Gang; Sun, Shouheng

    2014-05-28

    Controlling nanoparticle (NP) surface strain, i.e. compression (or stretch) of surface atoms, is an important approach to tune NP surface chemistry and to optimize NP catalysis for chemical reactions. Here we show that surface Pt strain in the core/shell FePt/Pt NPs with Pt in three atomic layers can be rationally tuned via core structural transition from cubic solid solution [denoted as face centered cubic (fcc)] structure to tetragonal intermetallic [denoted as face centered tetragonal (fct)] structure. The high activity observed from the fct-FePt/Pt NPs for oxygen reduction reaction (ORR) is due to the release of the overcompressed Pt strain by the fct-FePt as suggested by quantum mechanics-molecular mechanics (QM-MM) simulations. The Pt strain effect on ORR can be further optimized when Fe in FePt is partially replaced by Cu. As a result, the fct-FeCuPt/Pt NPs become the most efficient catalyst for ORR and are nearly 10 times more active in specific activity than the commercial Pt catalyst. This structure-induced surface strain control opens up a new path to tune and optimize NP catalysis for ORR and many other chemical reactions.

  15. Vertically aligned carbon nanotubes/carbon fiber paper composite to support Pt nanoparticles for direct methanol fuel cell application

    NASA Astrophysics Data System (ADS)

    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.

  16. Magnetic heating properties and neutron activation of tungsten-oxide coated biocompatible FePt core-shell nanoparticles.

    PubMed

    Seemann, K M; Luysberg, M; Révay, Z; Kudejova, P; Sanz, B; Cassinelli, N; Loidl, A; Ilicic, K; Multhoff, G; Schmid, T E

    2015-01-10

    Magnetic nanoparticles are highly desirable for biomedical research and treatment of cancer especially when combined with hyperthermia. The efficacy of nanoparticle-based therapies could be improved by generating radioactive nanoparticles with a convenient decay time and which simultaneously have the capability to be used for locally confined heating. The core-shell morphology of such novel nanoparticles presented in this work involves a polysilico-tungstate molecule of the polyoxometalate family as a precursor coating material, which transforms into an amorphous tungsten oxide coating upon annealing of the FePt core-shell nanoparticles. The content of tungsten atoms in the nanoparticle shell is neutron activated using cold neutrons at the Heinz Maier-Leibnitz (FRMII) neutron facility and thereby transformed into the radioisotope W-187. The sizeable natural abundance of 28% for the W-186 precursor isotope, a radiopharmaceutically advantageous gamma-beta ratio of γβ≈30% and a range of approximately 1mm in biological tissue for the 1.3MeV β-radiation are promising features of the nanoparticles' potential for cancer therapy. Moreover, a high temperature annealing treatment enhances the magnetic moment of nanoparticles in such a way that a magnetic heating effect of several degrees Celsius in liquid suspension - a prerequisite for hyperthermia treatment of cancer - was observed. A rise in temperature of approximately 3°C in aqueous suspension is shown for a moderate nanoparticle concentration of 0.5mg/ml after 15min in an 831kHz high-frequency alternating magnetic field of 250Gauss field strength (25mT). The biocompatibility based on a low cytotoxicity in the non-neutron-activated state in combination with the hydrophilic nature of the tungsten oxide shell makes the coated magnetic FePt nanoparticles ideal candidates for advanced radiopharmaceutical applications.

  17. Theophylline-assisted, eco-friendly synthesis of PtAu nanospheres at reduced graphene oxide with enhanced catalytic activity towards Cr(VI) reduction.

    PubMed

    Hu, Ling-Ya; Chen, Li-Xian; Liu, Meng-Ting; Wang, Ai-Jun; Wu, Lan-Ju; Feng, Jiu-Ju

    2017-05-01

    Theophylline as a naturally alkaloid is commonly employed to treat asthma and chronic obstructive pulmonary disorder. Herein, a facile theophylline-assisted green approach was firstly developed for synthesis of PtAu nanospheres/reduced graphene oxide (PtAu NSs/rGO), without any surfactant, polymer, or seed involved. The obtained nanocomposites were applied for the catalytic reduction and removal of highly toxic chromium (VI) using formic acid as a model reductant at 50°C, showing the significantly enhanced catalytic activity and improved recyclability when compared with commercial Pt/C (50%) and home-made Au nanocrystals supported rGO (Au NCs/rGO). It demonstrates great potential applications of the catalyst in wastewater treatment and environmental protection. The eco-friendly route provides a new platform to fabricate other catalysts with enhanced catalytic activity.

  18. Graphene/nano-porous silicon and graphene/bimetallic silicon nanostructures (Pt-M, M: Pd, Ru, Rh), efficient electrocatalysts for the hydrogen evolution reaction.

    PubMed

    Ensafi, Ali A; Jafari-Asl, Mehdi; Rezaei, Behzad

    2015-10-07

    In this work nano-porous silicon flour (Nano-PSiF) was synthesized first and then there was an investigation into its electrocatalytic activity for the electrochemical hydrogen evolution reaction (HER). The results showed that Nano-PSiF has good electrocatalytic activity for the HER when compared with PSiF. In the second section, Pt and Pt-M (M = Pd, Rh, Ru) bimetallic silicon nanostructures were prepared by a direct reduction of the metal (Pt, Pt-Pd, Pt-Rh and Pt-Ru) on the surface of the PSiF by a galvanic exchange mechanism. The electrocatalytic activity of the bimetallic silicon nanostructures (Pt-M/PSiF) were evaluated for the HER. The results showed that all of the Pt-M/PSiFs have excellent electrocatalytic activity for the HER in a 0.5 mol L(-1) H2SO4 solution. For the Pt/PSiF, the Tafel slope of Pt/PSiF was 46.9 mV dec(-1), indicating its excellent electrocatalytic activity for the HER and it is comparable with commercial Pt/C. On the other hand, the bimetallic silicon nanostructures showed better electrocatalytic activity than Pt/PSiF for the HER (lower Tafel slope, and higher α). Finally, exfoliated graphene oxide was electro-deposited on the surface of a glassy carbon electrode (eRGO/GCE) and used as a sub-layer for the Pt-M/PSiF. Then, the electrocatalytic activities of the bimetallic silicon nanostructures on the eRGO/GCE were investigated for the HER. The results showed that there was a higher electrocatalytic activity for Pt-M/PSiF-eRGO/GCE when compared with Pt-M/PSiF-GCE.

  19. Tailoring Silica-alumina Supported Pt-Pd As Poison Tolerant Catalyst For Aromatics Hydrogenation

    SciTech Connect

    Yu, Yanzhe; Gutierrez, Oliver Y.; Haller, Gary L.; Colby, Robert J.; Kabius, Bernd C.; Rob van Veen, J. A.; Jentys, Andreas; Lercher, Johannes A.

    2013-08-01

    The tailoring of the physicochemical and catalytic properties of mono- and bimetallic Pt-Pd catalysts supported on amorphous silica-alumina is studied. Electron energy loss spectroscopy and extended X-ray absorption fine structure analyses indicated that bimetallic Pt-Pd and relatively large monometallic Pd particles were formed, whereas the X-ray absorption near edge structure provided direct evidence for the electronic deficiency of the Pt atoms. The heterogeneous distribution of metal particles was also shown by high resolution transmission electron microscopy. The average structure of the bimetallic particles (Pt-rich core and Pd-rich shell) and the presence of Pd particles led to surface Pd enrichment, which was independently shown by IR spectra of adsorbed CO. The specific metal distribution, average size, and surface composition of the Pt-Pd particles depend to a large extent on the metal precursors. In the presence of NH3 ligands, Pt-Pd particles with a fairly homogeneous bulk and surface metal distribution were formed. Also high Lewis acid site concentration of the carrier leads to more homogeneous bimetallic particles. All catalysts were active for the hydrogenation of tetralin in the absence and presence of quinoline and dibenzothiophene (DBT). Monometallic Pt catalysts had the highest hydrogenation activity in poison-free and quinoline-containing feed. When DBT was present, bimetallic Pt-Pd catalysts with the most homogenous metal distribution showed the highest activity. The higher resistance of bimetallic catalysts towards sulfur poisoning compared to their monometallic Pt counterparts results from the weakened metal-sulfur bond on the electron deficient Pt atoms. Thus, increasing the fraction of electron deficient Pt on the surface of the bimetallic particles increases the efficiency of the catalyst in the presence of sulfur.

  20. Thermally Stable Nanocatalyst for High Temperature Reactions: Pt-Mesoporous Silica Core-Shell Nanoparticles

    SciTech Connect

    Joo, Sang Hoon; Park, J.Y.; Tsung, C.-K.; Yamada, Y.; Yang, P.; Somorjai, G.A.

    2008-10-25

    Recent advances in colloidal synthesis enabled the precise control of size, shape and composition of catalytic metal nanoparticles, allowing their use as model catalysts for systematic investigations of the atomic-scale properties affecting catalytic activity and selectivity. The organic capping agents stabilizing colloidal nanoparticles, however, often limit their application in high-temperature catalytic reactions. Here we report the design of a high-temperature stable model catalytic system that consists of Pt metal core coated with a mesoporous silica shell (Pt{at}mSiO{sub 2}). While inorganic silica shells encaged the Pt cores up to 750 C in air, the mesopores directly accessible to Pt cores made the Pt{at}mSiO{sub 2} nanoparticles as catalytically active as bare Pt metal for ethylene hydrogenation and CO oxidation. The high thermal stability of Pt{at}mSiO{sub 2} nanoparticles permitted high-temperature CO oxidation studies, including ignition behavior, which was not possible for bare Pt nanoparticles because of their deformation or aggregation. The results suggest that the Pt{at}mSiO{sub 2} nanoparticles are excellent nanocatalytic systems for high-temperature catalytic reactions or surface chemical processes, and the design concept employed in the Pt{at}mSiO{sub 2} core-shell catalyst can be extended to other metal-metal oxide compositions.

  1. Dehydrogenation of ethylbenzene to styrene using Pt, Mo, and Pt-Mo catalysts supported on clay nanocomposites.

    PubMed

    Morán, Cesar; González, Eduardo; Sánchez, Jorge; Solano, Roger; Carruyo, Gabriela; Moronta, Alexander

    2007-11-01

    A synthetic clay (TS-1) was modified with a nonionic surfactant (IGEPAL CO-720) and magnesium oxide. The resulting solid was used as a support of Pt, Mo, and Pt-Mo catalysts. The catalysts were prepared by wet impregnation with aqueous solutions of H(2)PtCl(6)6H(2)O and (NH(4))(6)-Mo(7)O(24)4H(2)O. In both monometallic and bimetallic catalysts, the molybdenum content was 3 wt% and the platinum content was 0.5 or 1 wt%. The surface area of the starting material was 454 m(2)/g and after the modification treatment with IGEPAL it increased up to 649 m(2)/g, while platinum and molybdenum catalysts showed surface areas between 495 and 550 m(2)/g. The reduction profiles showed different Pt and Mo species and the existence of metal-support interactions. The reduced catalysts were more active than those in the unreduced form. The most active catalysts for the ethylbenzene dehydrogenation were those of monometallic Pt (0.5 and 1 wt%) with a maximum styrene conversion around 50%. The presence of Mo species masked Pt atoms and reduced the activity.

  2. FePt nanoparticles as a potential X-ray activated chemotherapy agent for HeLa cells.

    PubMed

    Zheng, Yanhong; Tang, Yunlan; Bao, Zhirong; Wang, Hui; Ren, Feng; Guo, Mingxiong; Quan, Hong; Jiang, Changzhong

    2015-01-01

    Nanomaterials have an advantage in "personalized" therapy, which is the ultimate goal of tumor treatment. In order to investigate the potential ability of FePt nanoparticles (NPs) in the diagnosis and chemoradiotherapy treatment of malignant tumors, superparamagnetic, monodispersed FePt (~3 nm) alloy NPs were synthesized, using cysteamine as a capping agent. The NPs were characterized by means of X-ray diffraction; transmission electron microscopy, Physical Property Measurement System, and Fourier transform infrared spectroscopy. The cytotoxicity of FePt NPs on Vero cells was assessed using an MTT assay, and tumor cell proliferation inhibited by individual FePt NPs and FePt NPs combined with X-ray beams were also collected using MTT assays; HeLa human cancer cell lines were used as in vitro models. Further confirmation of the combined effect of FePt NPs and X-rays was verified using HeLa cells, after which, the cellular uptake of FePt NPs was captured by transmission electron microscopy. The results indicated that the growth of HeLa cells was significantly inhibited by FePt NPs in a concentration-dependent manner, and the growth was significantly more inhibited by FePt NPs combined with a series of X-ray beam doses; the individual NPs did not display any remarkable cytotoxicity on Vero cells at a concentration <250 μg/mL. Meanwhile, the FePt NPs showed negative/positive contrast enhancement for MRI/CT molecule imaging at the end of the study. Therefore, the combined results implied that FePt NPs might potentially serve as a promising nanoprobe for the integration of tumor diagnosis and chemoradiotherapy.

  3. FePt nanoparticles as a potential X-ray activated chemotherapy agent for HeLa cells

    PubMed Central

    Zheng, Yanhong; Tang, Yunlan; Bao, Zhirong; Wang, Hui; Ren, Feng; Guo, Mingxiong; Quan, Hong; Jiang, Changzhong

    2015-01-01

    Nanomaterials have an advantage in “personalized” therapy, which is the ultimate goal of tumor treatment. In order to investigate the potential ability of FePt nanoparticles (NPs) in the diagnosis and chemoradiotherapy treatment of malignant tumors, superparamagnetic, monodispersed FePt (~3 nm) alloy NPs were synthesized, using cysteamine as a capping agent. The NPs were characterized by means of X-ray diffraction; transmission electron microscopy, Physical Property Measurement System, and Fourier transform infrared spectroscopy. The cytotoxicity of FePt NPs on Vero cells was assessed using an MTT assay, and tumor cell proliferation inhibited by individual FePt NPs and FePt NPs combined with X-ray beams were also collected using MTT assays; HeLa human cancer cell lines were used as in vitro models. Further confirmation of the combined effect of FePt NPs and X-rays was verified using HeLa cells, after which, the cellular uptake of FePt NPs was captured by transmission electron microscopy. The results indicated that the growth of HeLa cells was significantly inhibited by FePt NPs in a concentration-dependent manner, and the growth was significantly more inhibited by FePt NPs combined with a series of X-ray beam doses; the individual NPs did not display any remarkable cytotoxicity on Vero cells at a concentration <250 μg/mL. Meanwhile, the FePt NPs showed negative/positive contrast enhancement for MRI/CT molecule imaging at the end of the study. Therefore, the combined results implied that FePt NPs might potentially serve as a promising nanoprobe for the integration of tumor diagnosis and chemoradiotherapy. PMID:26604740

  4. Increasing Stability and Activity of Core-Shell Catalysts by Preferential Segregation of Oxide on Edges and Vertexes: Oxygen Reduction on Ti-Au@Pt/C

    DOE PAGES

    Hu, J.; Wu, L.; Kuttiyiel, K.; ...

    2016-06-30

    We describe a new class of core-shell nanoparticle catalysts having edges and vertexes covered by refractory metal oxide that preferentially segregates onto these catalyst sites. The monolayer shell is deposited on the oxidefree core atoms. The oxide on edges and vertexes induces high catalyst’s stability and activity. The catalyst and synthesis are exemplified by fabrication of Au nanoparticles doped by Ti atoms that segregate as oxide onto low–coordination sites of edges and vertexes. Pt monolayer shell deposited on Au sites has the mass and specific activities for the oxygen reduction reaction about 13 and 5 times higher than those ofmore » commercial Pt/C catalysts. The durability tests show no activity loss after 10000 potential cycles from 0.6 to 1.0V. The superior activity and durability of the Ti-Au@Pt catalyst originate from protective Ti oxide located at the most dissolution-prone edge and vertex sites, and Au-supported active and stable Pt shell.« less

  5. Increasing Stability and Activity of Core-Shell Catalysts by Preferential Segregation of Oxide on Edges and Vertexes: Oxygen Reduction on Ti-Au@Pt/C

    SciTech Connect

    Hu, J.; Wu, L.; Kuttiyiel, K.; Goodman, K. R.; Zhang, C.; Zhu, Y.; Vukmirovic, M. B.; White, M. G.; Sasaki, K.; Adzic, R. R.

    2016-06-30

    We describe a new class of core-shell nanoparticle catalysts having edges and vertexes covered by refractory metal oxide that preferentially segregates onto these catalyst sites. The monolayer shell is deposited on the oxidefree core atoms. The oxide on edges and vertexes induces high catalyst’s stability and activity. The catalyst and synthesis are exemplified by fabrication of Au nanoparticles doped by Ti atoms that segregate as oxide onto low–coordination sites of edges and vertexes. Pt monolayer shell deposited on Au sites has the mass and specific activities for the oxygen reduction reaction about 13 and 5 times higher than those of commercial Pt/C catalysts. The durability tests show no activity loss after 10000 potential cycles from 0.6 to 1.0V. The superior activity and durability of the Ti-Au@Pt catalyst originate from protective Ti oxide located at the most dissolution-prone edge and vertex sites, and Au-supported active and stable Pt shell.

  6. Active micromixer using surface acoustic wave streaming

    SciTech Connect

    Branch; Darren W. , Meyer; Grant D. , Craighead; Harold G.

    2011-05-17

    An active micromixer uses a surface acoustic wave, preferably a Rayleigh wave, propagating on a piezoelectric substrate to induce acoustic streaming in a fluid in a microfluidic channel. The surface acoustic wave can be generated by applying an RF excitation signal to at least one interdigital transducer on the piezoelectric substrate. The active micromixer can rapidly mix quiescent fluids or laminar streams in low Reynolds number flows. The active micromixer has no moving parts (other than the SAW transducer) and is, therefore, more reliable, less damaging to sensitive fluids, and less susceptible to fouling and channel clogging than other types of active and passive micromixers. The active micromixer is adaptable to a wide range of geometries, can be easily fabricated, and can be integrated in a microfluidic system, reducing dead volume. Finally, the active micromixer has on-demand on/off mixing capability and can be operated at low power.

  7. Revealing chemical ordering in Pt-Co nanoparticles using electronic structure calculations and X-ray photoelectron spectroscopy.

    PubMed

    Kovács, Gábor; Kozlov, Sergey M; Matolínová, Iva; Vorokhta, Mykhailo; Matolín, Vladimír; Neyman, Konstantin M

    2015-11-14

    The high catalytic activity of Pt-Co nanoalloys in oxygen reduction and other reactions is usually attributed to their Pt-rich surfaces. However, identification of the precise near-surface structure is by no means easily achievable experimentally. In this work we systematically analyzed the chemical ordering and surface composition of PtXCo(79-X) and PtXCo(140-X) bimetallic nanoparticles by means of a recently developed method based on topological energy expressions and electronic structure calculations. Pt is found to segregate on the surface, especially on corner and edge sites, forming a one atomic layer thick skin independent of the size and composition of the nanoparticle. In turn, the subsurface shell of the particle is composed mostly of Co, whereas the core area has a mixed composition, which depends on the overall stoichiometry. The formation of an outer Pt shell is corroborated by thoroughly analyzed data of X-ray photoelectron spectroscopy experiments performed with various photon energies on annealed Pt-Co particles prepared in vacuum by magnetron sputtering. The core-shell structure of Pt-Co particles is calculated to be more stable than the respective L10 structure. The obtained topological energy expressions are shown to depend only very moderately on the nanoparticle size, which allowed us to apply them to determine the ordering in ∼4 nm big PtXCo(1463-X) species. The presented results deepen our understanding of the intrinsic structure of Pt-Co nanoparticles depending on their size and composition.

  8. Epitaxial Growth of Twinned Au-Pt Core-Shell Star-Shaped Decahedra as Highly Durable Electrocatalysts.

    PubMed

    Bian, Ting; Zhang, Hui; Jiang, Yingying; Jin, Chuanhong; Wu, Jianbo; Yang, Hong; Yang, Deren

    2015-12-09

    Pt epitaxial layer on a nanoparticle with twinned structure and well-defined shape is highly desirable in order to achieve high performance in both catalytic activity and durability toward oxygen reduction reaction (ORR). However, it remains tremendously challenging to produce conformal, heterogeneous, twinned nanostructures due to the high internal strain and surface energy of Pt. In addition, these twinned nanostructures may be subject to degradation in highly corrosive ORR environments due to the high energy of twin boundary. Here we report the synthesis of Au-Pt core-shell star-shaped decahedra bounded mainly by {111} facets, in which Pt shells with controlled thickness epitaxially grew on Au cores with a 5-fold twinned structure. The incorporation of the amine group decreases the surface energy of Pt by strong adsorption and thus facilitates the epitaxial growth of Pt on Au core instead of the dendritic growth. In addition, Br(-) ion could largely stabilize the {111} facets of Pt, which prevent the formation of spherical nanoparticles. The Au-Pt core-shell decahedra with thicker Pt shell exhibited enhanced ORR properties in terms of activity and durability. Specifically, AuPt1.03 star-shaped decahedra achieved the highest mass activity (0.94 mA/μg(Pt)) and area activity (1.09 mA/cm(2)(Pt)), which is ∼6.7 and 5 times, respectively, as high as those of the commercial Pt/C (ETEK). Significantly, such star-shaped decahedra were highly stable with ∼10% loss in area activity and ∼20% loss in mass activity after 30,000 CV cycles in O2 saturated acid solution.

  9. Green synthesis and characterization of Au@Pt core-shell bimetallic nanoparticles using gallic acid

    NASA Astrophysics Data System (ADS)

    Zhang, Guojun; Zheng, Hongmei; Shen, Ming; Wang, Lei; Wang, Xiaosan

    2015-06-01

    In this study, we developed a facile and benign green synthesis approach for the successful fabrication of well-dispersed urchin-like Au@Pt core-shell nanoparticles (NPs) using gallic acid (GA) as both a reducing and protecting agent. The proposed one-step synthesis exploits the differences in the reduction potentials of AuCl4- and PtCl62-, where the AuCl4- ions are preferentially reduced to Au cores and the PtCl62- ions are then deposited continuously onto the Au core surface as a Pt shell. The as-prepared Au@Pt NPs were characterized by transmission electron microscope (TEM); high-resolution transmission electron microscope (HR-TEM); scanning electron microscope (SEM); UV-vis absorption spectra (UV-vis); X-ray diffraction (XRD); Fourier transmission infrared spectra (FT-IR). We systematically investigated the effects of some experimental parameters on the formation of the Au@Pt NPs, i.e., the reaction temperature, the molar ratios of HAuCl4/H2PtCl6, and the amount of GA. When polyvinylpyrrolidone K-30 (PVP) was used as a protecting agent, the Au@Pt core-shell NPs obtained using this green synthesis method were better dispersed and smaller in size. The as-prepared Au@Pt NPs exhibited better catalytic activity in the reaction where NaBH4 reduced p-nitrophenol to p-aminophenol. However, the results showed that the Au@Pt bimetallic NPs had a lower catalytic activity than the pure Au NPs obtained by the same method, which confirmed the formation of Au@Pt core-shell nanostructures because the active sites on the surfaces of the Au NPs were covered with a Pt shell.

  10. Rationalization of Au concentration and distribution in AuNi@Pt core-shell nanoparticles for oxygen reduction reaction

    DOE PAGES

    An, Wei; Liu, Ping

    2015-09-18

    Improving the activity and stability of Pt-based core–shell nanocatalysts for proton exchange membrane fuel cells while lowering Pt loading has been one of the big challenges in electrocatalysis. Here, using density functional theory, we report the effect of adding Au as the third element to enhance the durability and activity of Ni@Pt core–shell nanoparticles (NPs) during the oxygen reduction reaction (ORR). Our results show that the durability and activity of a Ni@Pt NP can be finely tuned by controlling Au concentration and distribution. For a NiAu@Pt NP, the durability can be greatly promoted by thermodynamically favorable segregation of Au tomore » replace the Pt atoms at vertex, edge, and (100) facets on the shell, while still keeping the ORR activity on the active Pt(111) shell as high as that of Ni@Pt nanoparticles. Such behavior strongly depends on a direct interaction with the Ni interlayer. The results not only highlight the importance of interplay between surface strain on the shell and the interlayer–shell interaction in determining the durability and activity but also provide guidance on how to maximize the usage of Au to optimize the performance of core–shell (Pt) nanoparticles. As a result, such understanding has allowed us to discover a novel NiAu@Pt nanocatalyst for the ORR.« less

  11. Rationalization of Au concentration and distribution in AuNi@Pt core-shell nanoparticles for oxygen reduction reaction

    SciTech Connect

    An, Wei; Liu, Ping

    2015-09-18

    Improving the activity and stability of Pt-based core–shell nanocatalysts for proton exchange membrane fuel cells while lowering Pt loading has been one of the big challenges in electrocatalysis. Here, using density functional theory, we report the effect of adding Au as the third element to enhance the durability and activity of Ni@Pt core–shell nanoparticles (NPs) during the oxygen reduction reaction (ORR). Our results show that the durability and activity of a Ni@Pt NP can be finely tuned by controlling Au concentration and distribution. For a NiAu@Pt NP, the durability can be greatly promoted by thermodynamically favorable segregation of Au to replace the Pt atoms at vertex, edge, and (100) facets on the shell, while still keeping the ORR activity on the active Pt(111) shell as high as that of Ni@Pt nanoparticles. Such behavior strongly depends on a direct interaction with the Ni interlayer. The results not only highlight the importance of interplay between surface strain on the shell and the interlayer–shell interaction in determining the durability and activity but also provide guidance on how to maximize the usage of Au to optimize the performance of core–shell (Pt) nanoparticles. As a result, such understanding has allowed us to discover a novel NiAu@Pt nanocatalyst for the ORR.

  12. The durability dependence of Pt/CNT electrocatalysts on the n