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Sample records for pd nanoparticles supported

  1. Supported Pd-Cu bimetallic nanoparticles that have high activity for the electrochemical oxidation of methanol.

    PubMed

    Yin, Zhen; Zhou, Wu; Gao, Yongjun; Ma, Ding; Kiely, Christopher J; Bao, Xinhe

    2012-04-16

    Monodisperse bimetallic Pd-Cu nanoparticles with controllable size and composition were synthesized by a one-step multiphase ethylene glycol (EG) method. Adjusting the stoichiometric ratio of the Pd and Cu precursors afforded nanoparticles with different compositions, such as Pd(85)-Cu(15), Pd(56)-Cu(44), and Pd(39)-Cu(61). The nanoparticles were separated from the solution mixture by extraction with non-polar solvents, such as n-hexane. Monodisperse bimetallic Pd-Cu nanoparticles with narrow size-distribution were obtained without the need for a size-selection process. Capping ligands that were bound to the surface of the particles were removed through heat treatment when the as-prepared nanoparticles were loaded onto a Vulcan XC-72 carbon support. Supported bimetallic Pd-Cu nanoparticles showed enhanced electrocatalytic activity towards methanol oxidation compared with supported Pd nanoparticles that were fabricated according to the same EG method. For a bimetallic Pd-Cu catalyst that contained 15 % Cu, the activity was even comparable to the state-of-the-art commercially available Pt/C catalysts. A STEM-HAADF study indicated that the formation of random solid-solution alloy structures in the bimetallic Pd(85)-Cu(15)/C catalysts played a key role in improving the electrochemical activity. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Accessing stable zirconium carboxy-aminophosphonate nanosheets as support for highly active Pd nanoparticles.

    PubMed

    Costantino, Ferdinando; Vivani, Riccardo; Bastianini, Maria; Ortolani, Luca; Piermatti, Oriana; Nocchetti, Morena; Vaccaro, Luigi

    2015-11-14

    Thin nanosheets from a layered zirconium phosphate-carboxyphosphonate is reported here. Small Pd nanoparticles have been supported on these nanosheets by an efficient method. The resulting Pd-catalyst was fully characterized and tested in the Suzuki-Miyaura coupling. The catalytic system proved its efficiency as it was reused for several cycles and showed low Pd leaching.

  3. Carbon nanofiber supported bimetallic PdAu nanoparticles for formic acid electrooxidation

    NASA Astrophysics Data System (ADS)

    Qin, Yuan-Hang; Jiang, Yue; Niu, Dong-Fang; Zhang, Xin-Sheng; Zhou, Xing-Gui; Niu, Li; Yuan, Wei-Kang

    2012-10-01

    Carbon nanofiber (CNF) supported PdAu nanoparticles are synthesized with sodium citrate as the stabilizing agent and sodium borohydride as the reducing agent. High resolution transmission electron microscopy (HRTEM) characterization indicates that the synthesized PdAu particles are well dispersed on the CNF surface and X-ray diffraction (XRD) characterization indicates that the alloying degree of the synthesized PdAu nanoparticles can be improved by adding tetrahydrofuran to the synthesis solution. The results of electrochemical characterization indicate that the addition of Au can promote the electrocatalytic activity of Pd/C catalyst for formic acid oxidation and the CNF supported high-alloying PdAu catalyst possesses better electrocatalytic activity and stability for formic acid oxidation than either the CNF supported low-alloying PdAu catalyst or the CNF supported Pd catalyst.

  4. Microbially supported synthesis of catalytically active bimetallic Pd-Au nanoparticles.

    PubMed

    Hosseinkhani, Baharak; Søbjerg, Lina Sveidal; Rotaru, Amelia-Elena; Emtiazi, Giti; Skrydstrup, Troels; Meyer, Rikke Louise

    2012-01-01

    Bimetallic nanoparticles are considered the next generation of nanocatalysts with increased stability and catalytic activity. Bio-supported synthesis of monometallic nanoparticles has been proposed as an environmentally friendly alternative to the conventional chemical and physical protocols. In this study we synthesize bimetallic bio-supported Pd-Au nanoparticles for the first time using microorganisms as support material. The synthesis involved two steps: (1) Formation of monometallic bio-supported Pd(0) and Au(0) nanoparticles on the surface of Cupriavidus necator cells, and (2) formation of bimetallic bio-supported nanoparticles by reduction of either Au(III) or Pd(II) on to the nanoparticles prepared in step one. Bio-supported monometallic Pd(0) or Au(0) nanoparticles were formed on the surface of C. necator by reduction of Pd(II) or Au(III) with formate. Addition of Au(III) or Pd(II) to the bio-supported particles resulted in increased particle size. UV-Vis spectrophotometry and HR-TEM analyses indicated that the previously monometallic nanoparticles had become fully or partially covered by Au(0) or Pd(0), respectively. Furthermore, Energy Dispersive Spectrometry (EDS) and Fast Fourier Transformation (FFT) analyses confirmed that the nanoparticles indeed were bimetallic. The bimetallic nanoparticles did not have a core-shell structure, but were superior to monometallic particles at reducing p-nitrophenol to p-aminophenol. Hence, formation of microbially supported nanoparticles may be a cheap and environmentally friendly approach for production of bimetallic nanocatalysts. Copyright © 2011 Wiley Periodicals, Inc.

  5. Effect of metal support interaction on surface segregation in Pd Pt nanoparticles

    NASA Astrophysics Data System (ADS)

    De Sarkar, A.; Menon, Mahesh; Khanra, Badal C.

    2001-10-01

    In this work, we present the results of our Monte Carlo (MC) simulation studies for the segregation behavior of supported, clean and gas-covered Pd-Pt nanoparticles as a function of the metal-support interaction. For preferential Pd-support interaction, the base of the nanoparticle is found to get enriched with Pd atoms; while for preferential interaction of Pt atoms with the support the base gets enriched in Pt. The composition of the rest of the particle changes slightly with the metal-support interaction. The presence of oxygen and hydrogen atoms does not influence the role of the metal-support interaction on the surface composition of Pd-Pt nanoparticles. The simulation results are found to be in total agreement with the known experimental results.

  6. Laser synthesis of Pt, Pd, CoO and Pd-CoO nanoparticle catalysts supported on graphene

    NASA Astrophysics Data System (ADS)

    Moussa, Sherif; Abdelsayed, Victor; Samy El-Shall, M.

    2011-07-01

    We have developed a facile laser reduction method for the synthesis of transition metal nanoparticle catalysts supported on reduced graphene oxide (RGO) sheets. Using 532 or 355 nm laser irradiation of a mixture of graphene oxide and metal ion precursors in water, we report the photocatalytic reduction of the metal ions simultaneously with the partial reduction of GO, and the synthesis of metal nanoparticle catalysts well-dispersed and supported on the reduced GO. The Pd-CoO composite nanoparticles were found to have significantly enhanced activity for CO oxidation over both the Pd and the CoO catalysts. The simple synthesis method without chemical reducing agents, the formation of alloy nanoparticles with variable catalyst loading and composition, and the low cost of GO could enhance the commercial viability of these supported catalysts.

  7. Large faceted Pd nanocrystals supported small Pt nanoparticles as highly durable electrocatalysts for oxygen reduction

    NASA Astrophysics Data System (ADS)

    Zhang, Geng; Lu, Wangting; Cao, Longsheng; Qin, Xiaoping; Ding, Fei; Tang, Shun; Shao, Zhi-Gang; Yi, Baolian

    2016-09-01

    The reduction of Pt content together with the improvement of the durability of the catalyst for oxygen reduction reaction (ORR) is required to the large-scale commercialization of proton exchange membrane fuel cells. In this work, a novel ORR catalyst consisting of large Pd nanocrystal as the core with small Pt nanoparticles supported on the Pd core is prepared by a facile one-step synthesis method. The Pd substrate is presented in the form of well-defined cuboctahedrons and icosahedrons. The type of metal precursors and Pt/Pd molar ratio are important factors to obtain this Pd-supporting-Pt structure. The Pd2-s-Pt1 catalyst with a nominal Pt/Pd atomic ratio at 1/2 shows improved ORR activity: its mass specific activity and area specific activity is 2.5 and 3.5 times that of commercial Pt/C, respectively. More importantly, the Pd2-s-Pt1 catalyst demonstrates outstanding durability against potential cycling which can be ascribed to the slow dissolution of Pd core and the structure transformation from Pd@Pt to hollow PdPt alloyed nanocages. This exciting result provides a new pathway to the design of ORR catalyst with excellent durability.

  8. High-performance PdRu bimetallic catalyst supported on mesoporous silica nanoparticles for phenol hydrogenation

    NASA Astrophysics Data System (ADS)

    Huang, Chao; Yang, Xu; Yang, Hui; Huang, Peiyan; Song, Huiyu; Liao, Shijun

    2014-10-01

    A high-performance PdRu bimetallic catalyst supported on mesoporous silica nanoparticles (MSN), PdRu/MSN, was prepared by a facile impregnation-hydrogen reduction method. It was found that PdRu/MSN showed 5 times higher activity than that of Pd/MSN towards the liquid-phase hydrogenation of phenol. The catalysts were characterized comprehensively by multiple techniques, X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and hydrogen temperature program reduction (TPR). It was revealed that adding Ru could effectively improve the Pd dispersion and promote the electronic interaction between the Pd and Ru, both of which contribute to enhancing the catalytic activity.

  9. The role of surface functionalities in fabricating supported Pd-P nanoparticles for efficient formic acid oxidation

    NASA Astrophysics Data System (ADS)

    Yu, Weizhen; Xin, Zhiling; Zhang, Wei; Xie, Yanan; Wang, Juan; Niu, Shuo; Wu, Yifei; Shao, Lidong

    2017-10-01

    In the present work, O-functionalized carbon nanotubes (OCNTs) supported Pd-P nanoparticles (Pd-P/OCNTs) were prepared by using sodium hypophosphite (NaH2PO2) as the P source and the reducing agent. The presence of O-functionalities on the carbon surface provide a microenvironment of the reaction system which favors the anchorage of P precursors and Pd salt ions through the electrostatic interaction and the formation of chemical bonds on the carbon support. Thus, Pd nanoparticles supported on the OCNTs could be efficiently incorporated with P. Pd with the modified outer electron structure enhanced the electrocatalytic performance for formic acid oxidation (FAO).

  10. Synthesis of graphene-supported monodisperse AuPd bimetallic nanoparticles for electrochemical oxidation of methanol

    NASA Astrophysics Data System (ADS)

    Xiao, Hong-Jun; Shen, Cheng-Min; Shi, Xue-Zhao; Yang, Su-Dong; Tian, Yuan; Lin, Shao-Xiong; Gao, Hong-Jun

    2015-07-01

    Monodisperse AuPd bimetallic nanoparticles (NPs) with different compositions are synthesized by using oleylamine (OAm) as reducing reagent, stabilizer, and solvent. To obtain AuPd solid solution NPs, Pd-OAm and Au-OAm precursors are firstly prepared by mixing OAm with Palladium (II) acetylacetonate (Pd(acac)2) and HAuCl4, respectively. Then Pd-OAm and Au-OAm precursor solutions are injected into a hot oleylamine solution to form AuPd NPs. The size of these NPs ranges from 6.0 to 8.0 nm and the composition is controlled by varying the precursor ratio. The AuPd NPs are loaded onto reduced graphene oxide (RGO) sheets to make catalysts. Alloy NPs show high electrocatalytic activity and stability toward methanol oxidation in the alkaline media. Their catalytic activity for methanol oxidation is found to be dependent on the NP composition. As the Pd component increases, the peak current densities during the forward scan gradually increase and reach the maximum at AuPd2. The enhancement of alloy NPs for methanol oxidation can be attributed to a synergistic effect of Au and Pd on the surface of alloy NPs. Project supported by the National Natural Science Foundation of China (Grant No. 61335006) and the National Basic Research Program of China (Grant No. 2013CBA01603).

  11. Controlled synthesis and synergistic effects of graphene-supported PdAu bimetallic nanoparticles with tunable catalytic properties.

    PubMed

    Liu, Chang-Hai; Liu, Rui-Hua; Sun, Qi-Jun; Chang, Jian-Bing; Gao, Xu; Liu, Yang; Lee, Shuit-Tong; Kang, Zhen-Hui; Wang, Sui-Dong

    2015-04-14

    Graphene-supported bimetallic nanoparticles are promising nanocatalysts, which can show strong and tunable catalytic activity and selectivity. Herein room-temperature-ionic-liquid-assisted metal sputtering is utilized to synthesize PdAu bimetallic nanoparticles on graphene with bare surface, small size, high surface density and controlled Pd-to-Au ratio. This controllable synthetic approach is green-chemistry compatible and totally free of additives and byproducts. The supported PdAu nanoparticles show excellent catalytic capabilities for both oxidation and reduction reactions, strongly dependent on the Pd-to-Au ratio. A strong correlation among catalytic performance, bimetallic composition and charge redistribution in the PdAu nanoparticles has been demonstrated. The results suggest that sufficient Au d-holes appear to be significant to the catalysis of oxidation reaction, and a metallic Pd surface is critical to the catalysis of reduction reaction. By the present method, the bimetallic combination can be tailored for distinct types of catalytic reactions.

  12. Plasma Syntheses of Carbon Nanotube-Supported Pt-Pd Nanoparticles

    NASA Astrophysics Data System (ADS)

    Song, Ye; Wang, Qi; Meng, Yuedong

    2016-04-01

    It is reported that the highly dispersed Pt nanoparticles on carbon nanotubes can be synthesized under mild conditions by in situ plasma treatment. The carbon nanotube was pretreated by O2 plasma to transform into oxide carbon nanotubes (O-CNTs), and then it was mixed with the precursors (the mixture of H2PtCl6 and PdCl6). After that, the O-CNTs and the precursors were simultaneously treated by H2 plasma. The precursors were transformed into Pt-Pd nanoparticles (NPs) and the O-CNTs transformed into CNT. The synthesized CNT-based Pt-Pd nanoparticles were characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction and X-ray photoelectron spectroscopy. All the analysis showed that the Pt-Pd nanoparticles were deposited on CNT as a form of face-centered cubical structure. supported by National Natural Science Foundation of China (Nos. 11305218,11575253), the Youth Innovation Promotion Association of the Chinese Academy of Sciences (No. 2015262), the CASHIPS Director's Fund (No. YZJJ201505) and Anhui Provincial Natural Science Foundation for Distinguished Young Scholars of China (No. 1608085J03)

  13. Thermodynamics of hydride formation and decomposition in supported sub-10 nm Pd nanoparticles of different sizes

    NASA Astrophysics Data System (ADS)

    Wadell, Carl; Pingel, Torben; Olsson, Eva; Zorić, Igor; Zhdanov, Vladimir P.; Langhammer, Christoph

    2014-05-01

    Hydrogen storage properties of supported Pd nanoparticles with average sizes in the range 2.7-7.6 nm were studied using indirect nanoplasmonic sensing. For each particle size, a series of isotherms was measured and, through Van't Hoff analysis, the changes in enthalpy upon hydride formation/decomposition were determined. Contrary to the expected decrease of the enthalpy, due to increasing importance of surface tension in smaller particles, we observe a very weak size dependence in the size range under consideration. We attribute this to a compensation effect due to an increased fraction of hydrogen atoms occupying energetically favorable subsurface sites in smaller nanoparticles.

  14. 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.

  15. A remarkable difference in CO2 hydrogenation to methanol on Pd nanoparticles supported inside and outside of carbon nanotubes.

    PubMed

    Wang, Jijie; Lu, Sheng-mei; Li, Jun; Li, Can

    2015-12-25

    An obvious difference was found in CO2 hydrogenation to methanol on Pd nanoparticles (NPs) supported inside and outside of carbon nanotubes (CNTs). The turnover frequency of methanol synthesis on the Pd NPs supported inside of CNTs was 3.7 times those supported outside of CNTs. It was found that the amount of Pd(δ+) species inside of CNTs was much higher than that outside of CNTs. We proposed that one of the major reasons for the difference in CO2 hydrogenation to methanol might be relative to the concentration of the Pd(δ+) species.

  16. Controlled synthesis and synergistic effects of graphene-supported PdAu bimetallic nanoparticles with tunable catalytic properties

    NASA Astrophysics Data System (ADS)

    Liu, Chang-Hai; Liu, Rui-Hua; Sun, Qi-Jun; Chang, Jian-Bing; Gao, Xu; Liu, Yang; Lee, Shuit-Tong; Kang, Zhen-Hui; Wang, Sui-Dong

    2015-03-01

    Graphene-supported bimetallic nanoparticles are promising nanocatalysts, which can show strong and tunable catalytic activity and selectivity. Herein room-temperature-ionic-liquid-assisted metal sputtering is utilized to synthesize PdAu bimetallic nanoparticles on graphene with bare surface, small size, high surface density and controlled Pd-to-Au ratio. This controllable synthetic approach is green-chemistry compatible and totally free of additives and byproducts. The supported PdAu nanoparticles show excellent catalytic capabilities for both oxidation and reduction reactions, strongly dependent on the Pd-to-Au ratio. A strong correlation among catalytic performance, bimetallic composition and charge redistribution in the PdAu nanoparticles has been demonstrated. The results suggest that sufficient Au d-holes appear to be significant to the catalysis of oxidation reaction, and a metallic Pd surface is critical to the catalysis of reduction reaction. By the present method, the bimetallic combination can be tailored for distinct types of catalytic reactions.Graphene-supported bimetallic nanoparticles are promising nanocatalysts, which can show strong and tunable catalytic activity and selectivity. Herein room-temperature-ionic-liquid-assisted metal sputtering is utilized to synthesize PdAu bimetallic nanoparticles on graphene with bare surface, small size, high surface density and controlled Pd-to-Au ratio. This controllable synthetic approach is green-chemistry compatible and totally free of additives and byproducts. The supported PdAu nanoparticles show excellent catalytic capabilities for both oxidation and reduction reactions, strongly dependent on the Pd-to-Au ratio. A strong correlation among catalytic performance, bimetallic composition and charge redistribution in the PdAu nanoparticles has been demonstrated. The results suggest that sufficient Au d-holes appear to be significant to the catalysis of oxidation reaction, and a metallic Pd surface is critical

  17. Using supported Au nanoparticles as starting material for preparing uniform Au/Pd bimetallic catalysts.

    PubMed

    Villa, Alberto; Wang, Di; Su, Dangsheng; Veith, Gabriel M; Prati, Laura

    2010-03-07

    One of the best methods for producing bulk homogeneous (composition) supported bimetallic AuPd clusters involves the immobilization of a protected Au seed followed by the addition of Pd. This paper investigates the importance of this gold seed in controlling the resulting bimetallic AuPd clusters structures, sizes and catalytic activities by investigating three different gold seeds. Uniform Au-Pd alloy were obtained when a steric/electrostatic protecting group, poly(vinyl alcohol) (PVA), was used to form the gold clusters on activated carbon (AC). In contrast Au/AC precursors prepared using Au nanoparticles with only electrostatic stabilization (tetrakis(hydroxypropyl)phosphonium chloride (THPC)), or no stabilization (magnetron sputtering) produced inhomogeneous alloys and segregation of the gold and palladium. The uniform alloyed catalyst (Pd@Au(PVA)/AC) is the most active and selective catalyst, while the inhomogenous catalysts are less active and selective. Further study of the PVA protected Au clusters revealed that the amount of PVA used is also critical for the preparation of uniform alloyed catalyst, their stability, and their catalytic activity.

  18. Using supported Au nanoparticles as starting material for preparing uniform Au/Pd bimetallic catalysts

    SciTech Connect

    Villa, Alberto; Prati, Laura; Su, Dangshen; Wang, Di; Veith, Gabriel M

    2010-01-01

    One of the best methods for producing bulk homogeneous (composition) supported bimetallic AuPd clusters involves the immobilization of a protected Au seed followed by the addition of Pd. This paper investigates the importance of this gold seed in controlling the resulting bimetallic AuPd clusters structures, sizes and catalytic activities by investigating three different gold seeds. Uniform Au-Pd alloy were obtained when a steric/electrostatic protecting group, poly(vinyl alcohol) (PVA), was used to form the gold clusters on activated carbon (AC). In contrast Au/AC precursors prepared using Au nanoparticles with only electrostatic stabilization (tetrakis(hydroxypropyl)phosphonium chloride (THPC)), or no stabilization (magnetron sputtering) produced inhomogeneous alloys and segregation of the gold and palladium. The uniform alloyed catalyst (Pd{at}Au{sub PVA}/AC) is the most active and selective catalyst, while the inhomogenous catalysts are less active and selective. Further study of the PVA protected Au clusters revealed that the amount of PVA used is also critical for the preparation of uniform alloyed catalyst, their stability, and their catalytic activity.

  19. In situ spectroscopy of complex surface reactions on supported Pd-Zn, Pd-Ga, and Pd(Pt)-Cu nanoparticles.

    PubMed

    Föttinger, Karin; Rupprechter, Günther

    2014-10-21

    It is well accepted that catalytically active surfaces frequently adapt to the reaction environment (gas composition, temperature) and that relevant "active phases" may only be created and observed during the ongoing reaction. Clearly, this requires the application of in situ spectroscopy to monitor catalysts at work. While changes in structure and composition may already occur for monometallic single crystal surfaces, such changes are typically more severe for oxide supported nanoparticles, in particular when they are composed of two metals. The metals may form ordered intermetallic compounds (e.g. PdZn on ZnO, Pd2Ga on Ga2O3) or disordered substitutional alloys (e.g. PdCu, PtCu on hydrotalcite). We discuss the formation and stability of bimetallic nanoparticles, focusing on the effect of atomic and electronic structure on catalytic selectivity for methanol steam reforming (MSR) and hydrodechlorination of trichloroethylene. Emphasis is placed on the in situ characterization of functioning catalysts, mainly by (polarization modulated) infrared spectroscopy, ambient pressure X-ray photoelectron spectroscopy, X-ray absorption near edge structure, and X-ray diffraction. In the present contribution, we pursue a two-fold, fundamental and applied, approach investigating technologically applied catalysts as well as model catalysts, which provides comprehensive and complementary information of the relevant surface processes at the atomic or molecular level. Comparison to results of theoretical simulations yields further insight. Several key aspects were identified that control the nanoparticle functionality: (i) alloying (IMC formation) leads to site isolation of specific (e.g. Pd) atoms but also yields very specific electronic structure due to the (e.g. Zn or Ga or Cu) neighboring atoms; (i) for intermetallic PdZn, the thickness of the surface alloy, and its resulting valence band structure and corrugation, turned out to be critical for MSR selectivity; (ii) the limited

  20. Pd and PdCo alloy nanoparticles supported on polypropylenimine dendrimer-grafted graphene: A highly efficient anodic catalyst for direct formic acid fuel cells

    NASA Astrophysics Data System (ADS)

    Hosseini, Hadi; Mahyari, Mojtaba; Bagheri, Akbar; Shaabani, Ahmad

    2014-02-01

    For the first time, Pd and PdCo alloy nanoparticles supported on polypropylenimine dendrimer-grafted graphene (Pd and PdCo/PPI-g-G) are prepared and characterized with Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance spectroscopy (NMR), thermogravimetric analysis (TGA), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM). The electrocatalytic activity of Pd and PdCo/PPI-g-G are investigated in terms of formic acid electrooxidation in H2SO4 aqueous solution. The PdCo/PPI-g-G shows much higher formic acid oxidation activities in comparison with Pd/PPI-g-G, and it is more resistant to the surface poisoning. This improved electrocatalytic performance may be due to the fine dispersion of PdCo alloy nanoparticles and bi-functional effect. The kinetic parameters such as charge transfer coefficient and the diffusion coefficient of formic acid are estimated under the quasi steady-state conditions.

  1. Metal-organic-framework-derived carbons: Applications as solid-base catalyst and support for Pd nanoparticles in tandem catalysis

    DOE PAGES

    Li, Xinle; Zhang, Biying; Fang, Yuhui; ...

    2017-02-11

    Here, the facile pyrolysis of a bipyridyl metal-organic framework, MOF-253, produces N-doped porous carbons (Cz-MOF-253), which exhibit excellent catalytic activity in the Knoevenagel condensation reaction and outperform other nitrogen-containing MOF-derived carbons. More importantly, by virtue of their high Lewis basicity and porous nature, Cz-MOF-253-supported Pd nanoparticles (Pd/Cz-MOF-253-800) show excellent performance in a one-pot sequential Knoevenagel condensation-hydrogenation reaction.

  2. One-pot synthesis of graphene-supported monodisperse Pd nanoparticles as catalyst for formic acid electro-oxidation.

    PubMed

    Yang, Sudong; Dong, Jing; Yao, Zhaohui; Shen, Chengmin; Shi, Xuezhao; Tian, Yuan; Lin, Shaoxiong; Zhang, Xiaogang

    2014-03-28

    To synthesize monodisperse palladium nanoparticles dispersed on reduced graphene oxide (RGO) sheets, we have developed an easy and scalable solvothermal reduction method from an organic solution system. The RGO-supported palladium nanoparticles with a diameter of 3.8 nm are synthesized in N-methyl-2-pyrrolidone (NMP) and in the presence of oleylamine and trioctylphosphine, which facilitates simultaneous reduction of graphene oxide and formation of Pd nanocrystals. So-produced Pd/RGO was tested for potential use as electrocatalyst for the electro-oxidation of formic acid. Pd/RGO catalyzes formic acid oxidation very well compared to Pd/Vulcan XC-72 catalyst. This synthesis method is a new way to prepare excellent electrocatalysts, which is of great significance in energy-related catalysis.

  3. One-Pot Synthesis of Graphene-Supported Monodisperse Pd Nanoparticles as Catalyst for Formic Acid Electro-oxidation

    NASA Astrophysics Data System (ADS)

    Yang, Sudong; Dong, Jing; Yao, Zhaohui; Shen, Chengmin; Shi, Xuezhao; Tian, Yuan; Lin, Shaoxiong; Zhang, Xiaogang

    2014-03-01

    To synthesize monodisperse palladium nanoparticles dispersed on reduced graphene oxide (RGO) sheets, we have developed an easy and scalable solvothermal reduction method from an organic solution system. The RGO-supported palladium nanoparticles with a diameter of 3.8 nm are synthesized in N-methyl-2-pyrrolidone (NMP) and in the presence of oleylamine and trioctylphosphine, which facilitates simultaneous reduction of graphene oxide and formation of Pd nanocrystals. So-produced Pd/RGO was tested for potential use as electrocatalyst for the electro-oxidation of formic acid. Pd/RGO catalyzes formic acid oxidation very well compared to Pd/Vulcan XC-72 catalyst. This synthesis method is a new way to prepare excellent electrocatalysts, which is of great significance in energy-related catalysis.

  4. One-Pot Synthesis of Graphene-Supported Monodisperse Pd Nanoparticles as Catalyst for Formic Acid Electro-oxidation

    PubMed Central

    Yang, Sudong; Dong, Jing; Yao, Zhaohui; Shen, Chengmin; Shi, Xuezhao; Tian, Yuan; Lin, Shaoxiong; Zhang, Xiaogang

    2014-01-01

    To synthesize monodisperse palladium nanoparticles dispersed on reduced graphene oxide (RGO) sheets, we have developed an easy and scalable solvothermal reduction method from an organic solution system. The RGO-supported palladium nanoparticles with a diameter of 3.8 nm are synthesized in N-methyl-2-pyrrolidone (NMP) and in the presence of oleylamine and trioctylphosphine, which facilitates simultaneous reduction of graphene oxide and formation of Pd nanocrystals. So-produced Pd/RGO was tested for potential use as electrocatalyst for the electro-oxidation of formic acid. Pd/RGO catalyzes formic acid oxidation very well compared to Pd/Vulcan XC-72 catalyst. This synthesis method is a new way to prepare excellent electrocatalysts, which is of great significance in energy-related catalysis. PMID:24675779

  5. Ni-Supported Pd Nanoparticles with Ca Promoter: A New Catalyst for Low-Temperature Ammonia Cracking

    PubMed Central

    Polanski, Jaroslaw; Bartczak, Piotr; Ambrozkiewicz, Weronika; Sitko, Rafal; Siudyga, Tomasz; Mianowski, Andrzej; Szade, Jacek; Balin, Katarzyna; Lelątko, Józef

    2015-01-01

    In this paper we report a new nanometallic, self-activating catalyst, namely, Ni-supported Pd nanoparticles (PdNPs/Ni) for low temperature ammonia cracking, which was prepared using a novel approach involving the transfer of nanoparticles from the intermediate carrier, i.e. nano-spherical SiO2, to the target carrier technical grade Ni (t-Ni) or high purity Ni (p-Ni) grains. The method that was developed allows a uniform nanoparticle size distribution (4,4±0.8 nm) to be obtained. Unexpectedly, the t-Ni-supported Pd NPs, which seemed to have a surface Ca impurity, appeared to be more active than the Ca-free (p-Ni) system. A comparison of the novel PdNPs/Ni catalyst with these reported in the literature clearly indicates the much better hydrogen productivity of the new system, which seems to be a highly efficient, flexible and durable catalyst for gas-phase heterogeneous ammonia cracking in which the TOF reaches a value of 2615 mmolH2/gPd min (10,570 molNH3/molPd(NP) h) at 600°C under a flow of 12 dm3/h (t-Ni). PMID:26308929

  6. Ni-Supported Pd Nanoparticles with Ca Promoter: A New Catalyst for Low-Temperature Ammonia Cracking.

    PubMed

    Polanski, Jaroslaw; Bartczak, Piotr; Ambrozkiewicz, Weronika; Sitko, Rafal; Siudyga, Tomasz; Mianowski, Andrzej; Szade, Jacek; Balin, Katarzyna; Lelątko, Józef

    2015-01-01

    In this paper we report a new nanometallic, self-activating catalyst, namely, Ni-supported Pd nanoparticles (PdNPs/Ni) for low temperature ammonia cracking, which was prepared using a novel approach involving the transfer of nanoparticles from the intermediate carrier, i.e. nano-spherical SiO2, to the target carrier technical grade Ni (t-Ni) or high purity Ni (p-Ni) grains. The method that was developed allows a uniform nanoparticle size distribution (4,4±0.8 nm) to be obtained. Unexpectedly, the t-Ni-supported Pd NPs, which seemed to have a surface Ca impurity, appeared to be more active than the Ca-free (p-Ni) system. A comparison of the novel PdNPs/Ni catalyst with these reported in the literature clearly indicates the much better hydrogen productivity of the new system, which seems to be a highly efficient, flexible and durable catalyst for gas-phase heterogeneous ammonia cracking in which the TOF reaches a value of 2615 mmolH2/gPd min (10,570 molNH3/molPd(NP) h) at 600°C under a flow of 12 dm3/h (t-Ni).

  7. Carbon nanotube supported PdAg nanoparticles for electrocatalytic oxidation of glycerol in anion exchange membrane fuel cells

    DOE PAGES

    Benipal, Neeva; Qi, Ji; Dalian Univ. of Technology, Dalian; ...

    2017-03-10

    Electro-oxidation of alcohol is the key reaction occurring at the anode of a direct alcohol fuel cell (DAFC), in which both reaction kinetics (rate) and selectivity (to deep oxidation products) need improvement to obtain higher power density and fuel utilization for a more efficient DAFC. We recently found that a PdAg bimetallic nanoparticle catalyst is more efficient than Pd for alcohol oxidation: Pd can facilitate deprotonation of alcohol in a base electrolyte, while Ag can promote intermediate aldehyde oxidation and cleavage of C-single bondC bond of C3 species to C2 species. Furthermore, a combination of the two active sites (Pdmore » and Ag) with two different functions, can simultaneously improve the reaction rates and deeper oxidation products of alcohols. In this continuing work, Pd, Ag mono, and bimetallic nanoparticles supported on carbon nanotubes (Ag/CNT, Pd/CNT, Pd1Ag1/CNT, and Pd1Ag3/CNT) were prepared using an aqueous-phase reduction method; they served as working catalysts for studying electrocatalytic oxidation of glycerol in an anion-exchange membrane-based direct glycerol fuel cell. Combined XRD, TEM, and HAADF-STEM analyses performed to fully characterize as-prepared catalysts suggested that they have small particle sizes: 2.0 nm for Pd/CNT, 2.3 nm for PdAg/CNT, 2.4 nm for PdAg3/CNT, and 13.9 nm for Ag/CNT. XPS further shows that alloying with Ag results in more metal state Pd presented on the surface, and this may be related to their higher direct glycerol fuel cell (DGFC) performances. Single DGFC performance and product analysis results show that PdAg bimetallic nanoparticles can not only improve the glycerol reaction rate so that higher power output can be achieved, but also facilitate deep oxidation of glycerol so that a higher faradaic efficiency and fuel utilization can be achieved along with optimal reaction conditions (increased base-to-fuel ratio). Half-cell electrocatalytic activity measurement and single fuel cell product analysis

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

    PubMed

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

    2015-09-07

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

  9. Enhanced activity of Pd nanoparticles supported on Vulcan XC72R carbon pretreated via a modified Hummers method for formic acid electrooxidation

    NASA Astrophysics Data System (ADS)

    Cao, Jianyu; Song, Lingzheng; Tang, Jiali; Xu, Juan; Wang, Wenchang; Chen, Zhidong

    2013-06-01

    Vulcan XC72R carbons were pretreated using a modified Hummers method and adopted as the support of palladium nanoparticles for formic acid electrooxidation. XPS analysis was used to investigate the surface species of the pretreated XC72R (XC72R-O), indicating a significant increase in the content of surface carboxyl groups. The structural properties of Pd nanoparticles deposited on the XC72R-O (Pd/XC72R-O) were determined by X-ray diffraction (XRD) and transmission electron microscopy (TEM), and their electrochemical performance was evaluated by cyclic voltammetry (CV) and chronoamperometry. Pd nanoparticles in the Pd/XC72R-O display an average size of ~6.7 nm with narrow size distribution. Electrochemical studies for formic acid oxidation reveal that the Pd/XC72R-O presents much higher electrocatalytic activity than that of the Pd/XC72R and commercial Pd/C, which may be due to the formation of carboxyl groups enhanced the interaction between the Pd particles and the carbon support, facilitating the dispersion of Pd particles and the formation of preferred plane orientation available for electrocatalytic reaction.

  10. Pd Particle Size Effects on Methane Dissociation on MgO-supported Pd Nanoparticles and Desorption Kinetics of Small Alkane Molecules on MgO(100)

    NASA Astrophysics Data System (ADS)

    Tait, Steven L., Jr.; Dohnalek, Zdenek; Kay, Bruce D.; Campbell, Charles T.

    2004-03-01

    Oxide-supported Pd nanoparticle catalysts are active in a variety of reactions involving small alkanes, including low-temperature methane combustion. Temperature programmed desorption (TPD) was used to study the adsorption of small alkane molecules, C_nH_2n+2 (n=1-10), on the MgO(100) surface at low temperatures (24 K). Hydrocarbon molecules are deposited on the surface by a highly collimated molecular beam with a well-defined kinetic energy. The sample is heated at a controlled rate and desorption products are observed by QMS. Adsorption energy increases linearly with alkane chain length with a small y-intercept. Dissociative adsorption probability of methane on MgO-supported Pd particles (<5 nm dia.) is measured by titration of C fragments with molecular oxygen beam. Dissociation probability is observed to increase with decreasing Pd particle size. PNNL is a multiprogram National Laboratory operated for the U.S. Department of Energy by Battelle Memorial Institute under contract DE-AC06-76RLO 1830. SLT supported by a UW/PNNL Joint Institute for Nanotechnology fellowship.

  11. Remarkable activity of PdIr nanoparticles supported on the surface of carbon nanotubes pretreated via a sonochemical process for formic acid electro-oxidation

    NASA Astrophysics Data System (ADS)

    Chen, Jinwei; Li, Yuanjie; Liu, Shuangren; Wang, Gang; Tian, Jing; Jiang, Chunping; Zhu, Shifu; Wang, Ruilin

    2013-12-01

    It was reported for the first time that the surface treated multi-walled carbon nanotubes supported PdIr (PdIr/CNT-SCP) catalyst presents remarkable electrocatalytic activity and stability for formic acid electro-oxidation (FAEO). The surface of CNTs was functionalized by a sonochemical process for the deposition of PdIr nanoparticles (NPs). The XRD and TEM characterizations show that the prepared PdIr/CNT-SCP catalyst has small mean size and good dispersion of PdIr NPs on CNTs. The electrochemical measurements show that the onset and anodic peak potentials of FAEO on PdIr/CNT-SCP catalyst are 60 and 50 mV more negative than that on the commercial Pd/C catalyst. The mass-normalized peak current density of PdIr/CNT-SCP is 3365 mA mg-1Pd, which is 4.5, 1.4 and 2.7 times higher than that of PdIr/CNT-Untreated, PdIr/C-SCP and commercial Pd/C, respectively. It demonstrates the promotion of Ir and functionalized CNTs to Pd for FAEO.

  12. Evaluation of carbon-supported Pt and Pd nanoparticles for the hydrogen evolution reaction in PEM water electrolysers

    NASA Astrophysics Data System (ADS)

    Grigoriev, S. A.; Millet, P.; Fateev, V. N.

    Carbon-supported Pt and Pd nanoparticles (CSNs) were synthesized and electrochemically characterized in view of potential application in proton exchange membrane (PEM) water electrolysers. Electroactive metallic nanoparticles were obtained by chemical reduction of precursor salts adsorbed to the surface of Vulcan XC-72 carbon carrier, using ethylene glycol as initial reductant and with final addition of formaldehyde. CSNs were then coated over the surface of electron-conducting working electrodes using an alcoholic solution of perfluorinated polymer. Their electrocatalytic activities with regard to the hydrogen evolution reaction (HER) were measured in sulfuric acid solution using cyclic voltammetry, and in a PEM cell during water electrolysis. Results obtained show that palladium can be advantageously used as an alternative electrocatalyst to platinum for the HER in PEM water electrolysers. Developed electrocatalysts could also be used in PEM fuel cells.

  13. Highly dispersed Pd nanoparticles supported on 1,10-phenanthroline-functionalized multi-walled carbon nanotubes for electrooxidation of formic acid

    NASA Astrophysics Data System (ADS)

    Bai, Zhengyu; Guo, Yuming; Yang, Lin; Li, Lei; Li, Wujv; Xu, Pengle; Hu, Chuangang; Wang, Kui

    2011-08-01

    Functionalization step is generally prerequisite to immobilize metal nanoparticles on multi-walled carbon nanotubes (MWCNTs) for production of a high efficient electrocatalyst. We herein report a novel method to functionalize MWCNTs with 1,10-phenanthroline (phen-MWCNTs) as a catalyst support for Pd nanoparticles. Raman spectroscopic analysis results reveal that this phen functionalization method can preserve the integrity and electronic structure of MWCNTs and provide the highly effective functional groups on the surface for Pd nanoparticles. According to the transmission electron microscopy (TEM) measurements, the as-prepared Pd nanop articles are evenly deposited on the surface of the phen-MWCNTs without obvious agglomeration, and the average particle size of the Pd nanoparticles is 2.3 nm. Electrochemical measurements demonstrate that the as-prepared Pd/phen-MWCNTs catalyst has a better electrocatalytic activity and stability for the oxidation of formic acid than Pd catalyst on acid-treated MWCNTs. It is concluded that the as-prepared Pd/phen-MWCNTs would be a potential candidate as an anode electrocatalyst in direct formic acid fuel cell (DFAFC).

  14. Switching-off toluene formation in the solvent-free oxidation of benzyl alcohol using supported trimetallic Au-Pd-Pt nanoparticles.

    PubMed

    He, Qian; Miedziak, Peter J; Kesavan, Lokesh; Dimitratos, Nikolaos; Sankar, Meenakshisundaram; Lopez-Sanchez, Jose Antonio; Forde, Michael M; Edwards, Jennifer K; Knight, David W; Taylor, Stuart H; Kiely, Christopher J; Hutchings, Graham J

    2013-01-01

    Trimetallic Au-Pd-Pt nanoparticles have been supported on activated carbon by the sol-immobilisation method. They are found to be highly active and selective catalysts for the solvent-free aerobic oxidation of benzyl alcohol. The addition of Pt promotes the selectivity to the desired product benzaldehyde at the expense of toluene formation. Detailed aberration corrected STEM-XEDS analysis confirmed that the supported particles are indeed Au-Pd-Pt ternary alloys, but also identified composition fluctuations from particle-to-particle which vary systematically with nanoparticle size.

  15. Synthesis of carbon-supported PdSn-SnO2 nanoparticles with different degrees of interfacial contact and enhanced catalytic activities for formic acid oxidation.

    PubMed

    Wang, Hui; Liu, Ziyue; Ma, Yanjiao; Julian, Key; Ji, Shan; Linkov, Vladimir; Wang, Rongfang

    2013-09-07

    The conjunction of the PdSn alloy and SnO2 is of interest for improving catalytic activity in formic acid oxidation (FAO). Here, we report the synthesis of PdSn-SnO2 nanoparticles and a study of their catalytic FAO activity. Different degrees of interfacial contact between SnO2 and PdSn were obtained using two different stabilizers (sodium citrate and EDTA) during the reduction process in catalyst preparation. Compared to the PdSn alloy, PdSn-SnO2 supported on carbon black showed enhanced FAO catalytic activity due to the presence of SnO2 species. It was also found that interfacial contact between the PdSn alloy and the SnO2 phase has an impact on the activity towards CO oxidation and FAO.

  16. Selective photocatalytic oxidation of benzene for the synthesis of phenol using engineered Au-Pd alloy nanoparticles supported on titanium dioxide.

    PubMed

    Su, Ren; Kesavan, Lokesh; Jensen, Mads M; Tiruvalam, Ramchandra; He, Qian; Dimitratos, Nikolaos; Wendt, Stefan; Glasius, Marianne; Kiely, Christopher J; Hutchings, Graham J; Besenbacher, Flemming

    2014-10-28

    The selectivity of photocatalytic phenol production from the direct oxidation of benzene can be enhanced by fine adjustment of the morphology and composition of Au-Pd metal nanoparticles supported on titanium dioxide thereby suppressing the decomposition of benzene and evolution of phenolic compounds.

  17. Phenylamine-functionalized mesoporous silica supported PdAg nanoparticles: a dual heterogeneous catalyst for formic acid/CO2-mediated chemical hydrogen delivery/storage.

    PubMed

    Mori, Kohsuke; Masuda, Shinya; Tanaka, Hiromasa; Yoshizawa, Kazunari; Che, Michel; Yamashita, Hiromi

    2017-04-25

    A PdAg-based nanoparticle catalyst supported on the mesoporous silica material, SBA-15, modified with a weakly basic phenylamine functional group has been developed as a dual heterogeneous catalyst for the H2 delivery and H2 storage reactions mediated by formic acid and carbon dioxide.

  18. Electrocatalytic Oxidation of Formic Acid in an Alkaline Solution with Graphene-Oxide- Supported Ag and Pd Alloy Nanoparticles.

    PubMed

    Han, Hyoung Soon; Yun, Mira; Jeong, Haesang; Jeon, Seungwon

    2015-08-01

    The electrocatalytic activities of metal-decorated graphene oxide (GO) catalysts were investigated. Electrochemically reduced GO-S-(CH2)4-S-Pd [ERGO-S-(CH2)4-S-Pd] and GO-S-(CH2)4-S-PdAg alloy [ERGO-S-(CH2)4-S-PdAg] were obtained through the electrochemical reduction of GO-S-(CH2)4-S-Pd and GO-S-(CH2)4-S-PdAg in a pH 5 PBS solution. It was demonstrated that the application of ERGO-S-(CH2)4-S-Pd and ERGO-S-(CH2)4-S-PdAg used in a modified GCE improves the electrocatalytic oxidation of formic acid. The addition of an Ag nanoparticle with a carbon chain-Pd in the electrode provides an electrode with very interesting properties for the electrocatalytic oxidation of formic acid. The ERGO-S-(CH2)4-S-Pd and ERGO-S-(CH2)4-S-PdAg were characterized via X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). ERGO-S-(CH2)4-S-Pd and ERGO-S-(CH2)4-S-PdAg can be employed for the electrocatalytic oxidation of formic acid. The electrochemical behaviors of this electrode were investigated using cyclic voltammetry (CV), chronoamperometry (CA) and electrochemical impedance spectroscopy (EIS).

  19. Montmorillonite-supported Pd0, Fe0, Cu0 and Ag0 nanoparticles: Properties and affinity towards CO2

    NASA Astrophysics Data System (ADS)

    Bouazizi, Nabil; Barrimo, Diana; Nousir, Saadia; Ben Slama, Romdhane; Roy, René; Azzouz, Abdelkrim

    2017-04-01

    This study reports the carbon dioxide (CO2) adsorption on montmorillonite (NaMt) incorporating Cu0, Fe0, Pd0 and Ag0 as metallic nanoparticles (MNPs). The changes in structural, textural, morphological and adsorption properties of the resulting materials (NaMt-MNPs) were investigated. Electron microscopy and X-ray diffraction showed that dispersion of fine MNPs occurs mainly within the interlayer space of NaMt, producing a slight structure expansion. This was accompanied by a visible enhancement of the affinity towards CO2, as supported by thermal programmed desorption measurements. NaMt-MNPs displayed high CO2 retention capacity (CRC) of ca. 657 μmol/g for NaMt-Cu as compared to NaMt. This was explained in terms of increased number of available adsorption sites due to enlarged interlayer spaces caused by MNP insertion. The differences in CO2 adsorption capacities clearly demonstrate the key role of MNPs in improving the surface properties and adsorption capacity. The results reported herein open new prospects for clay supported metal nanoparticles as efficient adsorbents for CO2.

  20. 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 1

    NASA Astrophysics Data System (ADS)

    Pech-Pech, I. E.; Gervasio, Dominic F.; Godínez-Garcia, A.; Solorza-Feria, O.; Pérez-Robles, J. F.

    2015-02-01

    Silver (Ag) nanoparticles enriched with platinum (Pt) and palladium (Pd) on their surfaces (Ag@Pt0.1Pd0.1) are supported on Vulcan XC-72 carbon (C) to form a new catalyst (Ag@Pt0.1Pd0.1/C) for the oxygen reduction reaction (ORR) in acid electrolytes. This catalyst is prepared in one pot by reducing Ag and then Pt and Pd metal salts with sodium borohydride in the presence of trisodium citrate then adding XC-72 while applying intense ultrasound. The metallic Ag@Pt0.1Pd0.1 nanoparticles contain 2 weight percent of Pt, are spherical and have an average size less than 10 nm as determined by X-ray diffraction (XRD) and transmission electron microscopy (TEM). At the ORR potentials, Ag nanoparticles on carbon (Ag/C) rapidly lose Ag by dissolution and show no more catalytic activity for the ORR than the carbon support, whereas Ag@Pt0.1Pd0.1/C is a stable catalyst and exhibits 1.4 and 1.6 fold greater specific activity, also 3.6 and 2.8 fold greater mass activity for ORR in 0.5 M H2SO4 solution than comparable Pt/C and Pt0.5Pd0.5/C catalysts with the same Pt loading as determined for thin-films of these catalysts on a rotating-disk electrode (TF-RDE). Using silver nanoparticles increases Pt utilization and therefore decreases Pt-loading and cost of a catalyst for a proton exchange membrane fuel cell (PEMFC) electrode.

  1. Study of supported PtCu and PdAu bimetallic nanoparticles using in-situ x-ray tools.

    SciTech Connect

    Oxford, S. M.; Lee, P. L.; Chupas, P. J.; Chapman, K. W.; Kung, M. C.; Kung, H. H.; Northwestern Univ.

    2010-01-01

    A combination of two synchrotron X-ray techniques, X-ray absorption spectroscopy (XAS), and pair distribution function analysis (PDF) with complementary Fourier transform infrared (FTIR) spectroscopy measurement, was used to characterize the composition distributions of PdAu and PtCu bimetallic particles after treatment in H{sub 2} or CO and in the presence of these gases. This is the first reported application of PDF to the study of supported bimetallic nanoparticles. We found that XAS was informative in determining the component distribution of an initial sample, but PDF was better suited to following changes in the distribution upon changing the gas environment. Thus, the surface of a PtCu bimetallic particle of about 2.5 nm after treatment in H{sub 2} was found to be enriched in Cu, while the core was bimetallic. There was no evidence of a component-segregated core?shell structure. Treatment in CO caused enrichment of Pt to the surface layer, with a concomitant migration of Cu to the core. The average particle size remained the same. For the PdAu bimetallic particles, the surface and core compositions were similar after H{sub 2} treatment, and Pd was enriched in the surface after CO treatment. The X-ray results compared favorably to infrared spectroscopy results. The results demonstrated that the two X-ray techniques in combination can generate new information not available with either technique alone or other techniques, about the elemental distribution of bimetallic particles under conditions relevant to catalysis. They could provide new insight into structure-function relationships and time-on-stream behavior of bimetallic catalysts.

  2. Application of aluminum-supported Pd, Rh, and Rh-Pd nanoparticles in supercritical carbon dioxide system for hydrodebromination of polybrominated diphenyl ethers.

    PubMed

    Wu, Ben-Zen; Sun, Yu-Jie; Chen, Yan-Hua; Yak, Hwa Kwang; Yu, Jya-Jyun; Liao, Weisheng; Chiu, KongHwa; Peng, Shie-Ming

    2016-08-01

    Al-powder-supported Pd, Rh, and Rh-Pd catalysts were synthesized through a spontaneous redox reaction in aqueous solutions. These catalysts hydrodebrominated 4- and 4,4'-bromodiphenyl ethers in supercritical carbon dioxide at 200 atm CO2 containing 10 atm H2 and 80 °C in 1 h. Diphenyl ether was the major product of Pd/Al. Rh/Al and Rh-Pd/Al further hydrogenated two benzene rings of diphenyl ether to form dicyclohexyl ether. The hydrogenolysis of CO bonds on diphenyl ether over Rh/Al and Rh-Pd/Al was observed to generate cyclohexanol and cyclohexane (<1%). With respect to hydrodebromination efficiency and catalyst stability, Rh-Pd/Al among three catalysts is suggested to be used for ex situ degradation of polybrominated diphenyl ethers in supercritical carbon dioxide. Copyright © 2016 Elsevier Ltd. All rights reserved.

  3. Highly efficient hydrogen generation from formic acid using a reduced graphene oxide-supported AuPd nanoparticle catalyst.

    PubMed

    Yang, Xinchun; Pachfule, Pradip; Chen, Yao; Tsumori, Nobuko; Xu, Qiang

    2016-03-18

    Highly dispersed AuPd alloy nanoparticles have been successfully immobilized on reduced graphene oxide (rGO) using a facile non-noble metal sacrificial method, which exhibit the highest activity at 323 K (turnover frequency, 4840 h(-1)) for hydrogen generation without CO impurity from the formic acid/sodium formate system.

  4. Electro-oxidation of methanol in alkaline conditions using Pd-Ni nanoparticles prepared from organometallic precursors and supported on carbon vulcan

    NASA Astrophysics Data System (ADS)

    Manzo-Robledo, A.; Costa, Natália J. S.; Philippot, K.; Rossi, Liane M.; Ramírez-Meneses, E.; Guerrero-Ortega, L. P. A.; Ezquerra-Quiroga, S.

    2015-12-01

    Oxidation of low-molecular weight alcohols as energy sources using metal nanoparticles has attracted considerable interest for use as a power source in portable electronic devices. In this work, a series of mono- and bimetallic nanoparticles based on palladium and nickel (Pd, Pd90Ni10, Pd50Ni50, Pd10Ni90, and Ni) have been synthesized from organometallic precursors, namely tris(dibenzylideneacetone) dipalladium(0), Pd2(dba)3, and bis(1,5-cyclooctadiene)nickel(0), Ni(cod)2. Well-defined metal particles in the nanometric scale from 4.2 to 6.3 nm were observed by transmission electron microscopy. The as-prepared nanoparticles were mixed with a carbon Vulcan matrix (10 % wt. of the catalyst in turn) for investigation as electrocatalysts in methanol oxidation reaction (MOR) in alkaline conditions. The i- E profiles from cyclic voltammetry for the monometallic systems indicated a redox process attributed only to palladium or nickel, as expected. With the bimetallic nanomaterials, the redox process and the i- E characteristics are functions of the amount of nickel associated to palladium. From a fundamental point of view, it has been established that the OH ions' interfacial interaction and the MOR kinetics are affected by the presence of nickel (decreasing the faradic current) as supported by the current versus potential profiles obtained as a function of methanol concentration and with temperature variation.

  5. Pd nanoparticles supported on functionalized multi-walled carbon nanotubes (MWCNTs) and electrooxidation for formic acid

    NASA Astrophysics Data System (ADS)

    Yang, Sudong; Zhang, Xiaogang; Mi, Hongyu; Ye, Xiangguo

    To improve the utilization and activity of anodic catalysts for formic acid electrooxidation, palladium (Pd) particles were loaded on the MWCNTs, which were functionalized in a mixture of 96% sulfuric acid and 4-aminobenzenesulfonic acid, using sodium nitrite to produce intermediate diazonium salts from substituted anilines. The composition, particle size, and crystallinity of the Pd/f-MWCNTs catalysts were characterized by X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM) and energy dispersive spectroscopy (EDS) measurements. The electrocatalytic properties of the Pd/f-MWCNTs catalysts for formic acid oxidation were investigated by cyclic voltammetry (CV) and linear sweep voltammetry (LSV) in 0.5 mol L -1 H 2SO 4 solution. The results demonstrated that the catalytic activity was greatly enhanced due to the improved water-solubility and dispersion of the f-MWCNTs, which were facile to make the small particle size (3.8 nm) and uniform dispersion of Pd particles loading on the surface of the MWCNTs. In addition, the functionalized MWCNTs with benzenesulfonic group can provide benzenesulfonic anions in aqueous solution, which may combine with hydrogen cation and then promote the oxidation of formic acid reactive intermediates. So the Pd/f-MWCNTs composites showed excellent electrocatalytic activity for formic acid oxidation.

  6. Bifunctional nanocatalyst based on three-dimensional carbon nanotube-graphene hydrogel supported Pd nanoparticles: one-pot synthesis and its catalytic properties.

    PubMed

    Zhang, Zheye; Sun, Tai; Chen, Chen; Xiao, Fei; Gong, Zheng; Wang, Shuai

    2014-12-10

    We reported the development of a new type of bifunctional nanocatalyst based on three-dimensional (3D) macroscopic carbon nanotube (CNT)-graphene hydrogel (GH) supported Pd nanoparticles (i.e., Pd-CNT-GH) and explored its practical application in catalytic reduction of p-nitrophenol to p-aminophenol. The 3D Pd-CNT-GH was synthesized by a facile one-pot self-assembled approach through hydrothermal treatment of a mixed aqueous precursor solution of PdCl4(2-), CNT, and graphene oxide (GO). Under the appropriate condition, the spontaneous redox reaction between precursor PdCl4(2-) and CNT-GO as well as the self-assembly of macroscopic CNT-GH occurs simultaneously, leading to the formation of 3D Pd-CNT-GH. Because of the unique structural and functional properties of different components in the nanocatalyst and the synergistic effect between them, the as-prepared Pd-CNT-GH exhibits superior catalytic performance toward the reduction of p-nitrophenol to p-aminophenol, with 100% conversion within 30 s, even when the content of Pd in it is as low as 2.98 wt %. Moreover, after 20 successive cycles of reactions, the reaction time still keeps within 46 s. Therefore, the rational design of 3D macroscopic graphene-based nanohybrid material supported highly catalytically active nanoparticles, combined with the facile one-pot self-assembled strategy, provide a universal platform to fabricate desired 3D multifunctional nanomaterials that can be used in a broad range of catalysis, environmental protection, energy storage and conversation, drug delivery, chemical and biological sensing, and so forth.

  7. Pd nanoparticle concentration dependent self-assembly of Pd@SiO₂ nanoparticles into leaching resistant microcubes.

    PubMed

    Datta, Abheek; Sadhu, Anustup; Santra, Subhankar; Shivaprasad, S M; Mandal, Swadhin K; Bhattacharyya, Sayan

    2014-09-18

    Pd NP concentration guided the self-assembly of core-shell Pd@SiO2 nanoparticles (NPs) into microcubes. The Pd NPs were stacked by molten dodecyltrimethylammonium bromide (DTAB) to create the SiO2 envelope. The microcubes demonstrated improved leaching resistance in heterogeneous catalysis over a conventional porous support.

  8. Electrochemical post-treatment of infinite coordination polymers: an effective route to preparation of Pd nanoparticles supported onto carbon nanotubes with enhanced electrocatalytic activity toward ethanol oxidation.

    PubMed

    Ren, Lin; Yang, Lifen; Yu, Ping; Wang, Yuexiang; Mao, Lanqun

    2013-11-13

    This study describes an effective method to prepare highly dispersed palladium nanoparticles supported onto single-walled carbon nanotubes (SWNTs) with high electrocatalytic activity toward the oxidation of ethanol. This method is essentially based on electrochemical post-treatment of Pd-based infinite coordination polymer (ICP). The Pd-based ICP is synthesized through the coordination reaction between Zn(2+) and metallo-Schiff base (MSB) to form Zn-MSB-Zn (ZMZ) ICP that precipitates from ethyl ether. The as-formed Zn-MSB-Zn ICP is then subjected to an ion-exchange reaction with Pd(2+) to obtain the Zn-MSB-Pd (ZMP) ICP. To prepare Pd/SWNT nanocomposite, the ZMP ICP is mixed into the SWNT dispersion in N-dimethylformamide (DMF) to form a homogeneous dispersion that is then drop-coated onto a glassy carbon (GC) electrode. Electrochemical post-treatment of ZMP ICP to form Pd/SWNT nanocomposite is thus performed by polarizing the coated electrode at -0.2 V for 600 s in 0.5 M H2SO4. The results obtained with scanning electron microscopy (SEM) and transmission electron microscopy (TEM) reveal that the resulting Pd nanoparticles are highly dispersed onto SWNTs and the particles size are small and narrowly distributed (2.12 ± 0.32 nm). X-ray photoelectron spectroscopy (XPS) analysis shows that, after the electrochemical post-treatment, no detectable ZMP ICP precursors are left on the surface of SWNTs. The electrocatalytic activity of the as-formed Pd/SWNT nanocomposite toward ethanol oxidation is investigated by cyclic voltammetry and chronoamperometry. The results show that the Pd/SWNT nanocomposite prepared here shows a more negative potential and higher mass catalytic activity, as well as higher stability for the oxidation of ethanol than the commercial Pd/C catalyst. This work demonstrates a novel approach to the formation of ultrasmall and highly dispersed Pd/SWNT nanocomposite with enhanced electrocatalytic activity toward ethanol oxidation.

  9. Highly efficient hydrogen release from formic acid using a graphitic carbon nitride-supported AgPd nanoparticle catalyst

    NASA Astrophysics Data System (ADS)

    Yao, Fang; Li, Xiao; Wan, Chao; Xu, Lixin; An, Yue; Ye, Mingfu; Lei, Zhao

    2017-12-01

    Bimetallic AgPd nanoparticles with various molar ratios immobilized on graphitic carbon nitride (g-C3N4) were successfully synthesized via a facile co-reduction approach. The powder XRD, XPS, TEM, EDX, ICP-AES and BET were employed to characterize the structure, size, composition and loading metal electronic states of the AgPd/g-C3N4 catalysts. The catalytic property of as-prepared catalysts for the dehydrogenation of formic acid (FA) with sodium formate (SF) as the additive was investigated. The performance of these catalysts, as indicated by the turnover frequency (TOF), depended on the composition of the prepared catalysts. Among all the AgPd/g-C3N4 catalysts tested, Ag9Pd91/g-C3N4 was found to be an exceedingly high activity for decomposing FA into H2 with TOF up to 480 h-1 at 323 K. The prepared catalyst is thus a potential candidate for triggering the widespread use of FA for H2 storage.

  10. Nanoparticle-supported and magnetically recoverable palladium (Pd) catalyst: a selective and sustainable oxidation protocol with high turnover number

    EPA Science Inventory

    A magnetic nanoparticle-supported ruthenium hydroxide catalyst was readily prepared from inexpensive starting materials and shown to catalyze hydration of nitriles with excellent yield in benign aqueous medium. Catalyst recovery using an external magnetic field, superior activity...

  11. Nanoparticle-supported and magnetically recoverable palladium (Pd) catalyst: a selective and sustainable oxidation protocol with high turnover number

    EPA Science Inventory

    A magnetic nanoparticle-supported ruthenium hydroxide catalyst was readily prepared from inexpensive starting materials and shown to catalyze hydration of nitriles with excellent yield in benign aqueous medium. Catalyst recovery using an external magnetic field, superior activity...

  12. Pd nanoparticles supported on MIL-101/reduced graphene oxide photocatalyst: an efficient and recyclable photocatalyst for triphenylmethane dye degradation.

    PubMed

    Wu, Yan; Luo, Hanjin; Zhang, Li

    2015-11-01

    To improve the photocatalytic efficiency of chromium-based metal-organic framework (MIL-101) photocatalyst, Pd nanoparticles and reduced graphene oxide were used to modify the MIL-101 via a facile method. The resulting novel photocatalyst was characterized by UV-vis diffuse reflectance spectra (DRS), powder X-ray diffraction (XRD), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS). It was indicated that the photocatalyst afforded high photocatalytic efficiency for degradation of two triphenylmethane dyes, brilliant green and acid fuchsin, under exposure to visible light irradiation. Cyclic experiments demonstrated that the photocatalyst showed good reusability and stability for the dye degradation.

  13. Poly(sodium-p-styrenesulfonate) assisted microwave synthesis of ordered mesoporous carbon supported Pd nanoparticles for formic acid electro-oxidation

    NASA Astrophysics Data System (ADS)

    Sun, Zhi-Peng; Zhang, Xiao-Gang; Tong, Hao; Xue, Rui-Li; Liang, Yan-Yu; Li, Hu-Lin

    2009-10-01

    Pd nanoparticles highly dispersed onto the surface of ordered mesoporous carbons (OMCs) were synthesized successfully by poly(sodium-p-styrenesulfonate) (PSS) assisted microwave synthesis. Here, PSS served as a bifunctional molecule both for solubilizing and dispersing OMCs into aqueous solution and for jointing Pd 2+ to facilitate the subsequent uniform formation of Pd nanoparticles on their surfaces. The effects of PSS on structural and electrochemical properties of Pd/OMCs were investigated. It was found that the addition of PSS facilitated Pd nanoparticles to disperse on the carbon surface. Electrochemical properties showed that Pd catalysts prepared with addition of PSS displayed better electrochemical activity and stability for formic acid electro-oxidation than those without PSS.

  14. Sensitive Electrochemical Immunosensor for Detection of Nuclear Matrix Protein-22 based on NH2-SAPO-34 Supported Pd/Co Nanoparticles

    PubMed Central

    Wu, Dan; Wang, Yaoguang; Zhang, Yong; Ma, Hongmin; Yan, Tao; Du, Bin; Wei, Qin

    2016-01-01

    A novel sandwich-type electrochemical immunosensor using the new amino group functionalized silicoaluminophosphates molecular sieves (NH2-SAPO-34) supported Pd/Co nanoparticles (NH2-SAPO-34-Pd/Co NPs) as labels for the detection of bladder cancer biomarker nuclear matrix protein-22 (NMP-22) was developed in this work. The reduced graphene oxide-NH (rGO-NH) with good conductivity and large surface area was used to immobilize primary antibody (Ab1). Due to the excellent catalytic activity toward hydrogen peroxide, NH2-SAPO-34-Pd/Co NPs were used as labels and immobilized secondary antibody (Ab2) through adsorption capacity of Pd/Co NPs to protein. The immunosensor displayed a wide linear range (0.001–20 ng/mL) and low detection limit (0.33 pg/mL). Good reproducibility and stability have showed satisfying results in the analysis of clinical urine samples. This novel and ultrasensitive immunosensor may have the potential application in the detection of different tumor markers. PMID:27086763

  15. Sensitive Electrochemical Immunosensor for Detection of Nuclear Matrix Protein-22 based on NH2-SAPO-34 Supported Pd/Co Nanoparticles.

    PubMed

    Wu, Dan; Wang, Yaoguang; Zhang, Yong; Ma, Hongmin; Yan, Tao; Du, Bin; Wei, Qin

    2016-04-18

    A novel sandwich-type electrochemical immunosensor using the new amino group functionalized silicoaluminophosphates molecular sieves (NH2-SAPO-34) supported Pd/Co nanoparticles (NH2-SAPO-34-Pd/Co NPs) as labels for the detection of bladder cancer biomarker nuclear matrix protein-22 (NMP-22) was developed in this work. The reduced graphene oxide-NH (rGO-NH) with good conductivity and large surface area was used to immobilize primary antibody (Ab1). Due to the excellent catalytic activity toward hydrogen peroxide, NH2-SAPO-34-Pd/Co NPs were used as labels and immobilized secondary antibody (Ab2) through adsorption capacity of Pd/Co NPs to protein. The immunosensor displayed a wide linear range (0.001-20 ng/mL) and low detection limit (0.33 pg/mL). Good reproducibility and stability have showed satisfying results in the analysis of clinical urine samples. This novel and ultrasensitive immunosensor may have the potential application in the detection of different tumor markers.

  16. Development of a Sulfur-Modified Glass-Supported Pd Nanoparticle Catalyst for Suzuki-Miyaura Coupling.

    PubMed

    Xiao, Mincen; Hoshiya, Naoyuki; Fujiki, Katsumasa; Honma, Tetsuo; Tamenori, Yusuke; Shuto, Satoshi; Fujioka, Hiromichi; Arisawa, Mitsuhiro

    2016-01-01

    A safe, facile and low-leaching (up to 0.17 ppm) sulfur-modified glass-supported palladium nanoparticle catalyst has been developed for the Suzuki-Miyaura coupling of aryl halides with aryl boronic acids. Most notably, this catalyst was highly recyclable and could be used up to 10 times without any discernible decrease in its activity.

  17. State of Supported Pd during Catalysis in Water

    SciTech Connect

    Chase, Zizwe; Fulton, John L.; Camaioni, Donald M.; Mei, Donghai; Balasubramanian, Mahalingam; Pham, Van Thai; Zhao, Chen; Weber, Robert S.; Wang, Yong; Lercher, Johannes A.

    2013-08-29

    In operando X-ray absorption was used to measure the structure and chemical state of supported Pd nanoparticles with 3 -10 nm diameter in contact with H2 saturated water at 298-473 K. The Pd-Pd distances determined were consistent with the presence of subsurface hydrogen, i.e., longer than those measured by others for bare, reduced Pd particles, and within the range of distances for Pd hydrides. During the Pd-catalyzed hydrogenation of phenol, cyclohexanone, cyclohexanol or cyclohexene in the presence of water, the Pd nanoparticles exhibited a lengthening of the Pd-Pd bond that we attribute to a change in the concentration of sorbed H related to the steady state of H at the surface of the Pd particles. This steady state is established by all reactions involving H2, i.e., the sorption/desorption into the bulk, the sorption at the surface, and the reaction with adsorbed unsaturated reactants. Thus, first insight into the chemical state of Pd and the H/Pd ratio during catalysis in water is provided. The Pd particles did not change upon their exposure to water or reactants; nor did the spectra show any effect from the interaction of the Pd particles with various supports. The experimental results are consistent with ab initio molecular dynamic simulations, which indicate that Pd-water interactions are relatively weak for Pd metal and that these interactions become even weaker, when hydrogen is incorporated into the metal particles. This work was supported by the US Department of Energy (DOE), Office of Basic Energy Sciences (BES), Division of Chemical Sciences, Geosciences & Biosciences. Pacific Northwest National Laboratory is a multi-program national laboratory operated for DOE by Battelle through Contract DE-AC05-76RL01830.

  18. Enhanced stability and activity with Pd-O junction formation and electronic structure modification of palladium nanoparticles supported on exfoliated montmorillonite for the oxygen reduction reaction.

    PubMed

    Ding, W; Xia, M-R; Wei, Z-D; Chen, S-G; Hu, J-S; Wan, L-J; Qi, X-Q; Hu, X-H; Li, L

    2014-06-25

    Palladium has been the focus of recent research on alternative Pt catalysts for the oxygen reduction reaction (ORR). We show that the activity and stability of Pd toward the ORR can be enhanced by Pd-O-oxide covalent bonding when Pd is supported on exfoliated montmorillonite (ex-MMT) nanoplatelets.

  19. 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

  20. Effect of MgO(100) support on structure and properties of Pd and Pt nanoparticles with 49-155 atoms.

    PubMed

    Kozlov, Sergey M; Aleksandrov, Hristiyan A; Goniakowski, Jacek; Neyman, Konstantin M

    2013-08-28

    Presently, density functional computational studies of nanostructures in heterogeneous catalysts consider either sufficiently big ("scalable with size") unsupported metal nanoparticles (NPs) or small supported metal clusters. Both models may not be sufficiently representative of a few nm in size supported transition metal NPs dealt with in experiment. As a first step in closing the gap between theoretical models and prepared systems, we investigate the effect of a rather chemically inert oxide support, MgO(100), on relative energies and various properties of Pd and Pt NPs that consist of 49-155 atoms (1.2-1.6 nm in size) and exhibit bulk-like fcc structural arrangements. Shapes and interface configurations of metal NPs on MgO were obtained as a result of thorough optimization within the fcc motif using interatomic potentials. Then the stability and properties of the NPs were studied with a density functional method. We comprehensively characterize interaction between the NPs and MgO(100) support, their interface and effect of the support on NP properties. While the effect of MgO on relative stabilities of NPs with different shapes is found to be significant, other properties of the NPs such as electronic structure and interatomic distances within NP do not notably change upon deposition. This work paves the way to large-scale first-principles computational studies of more realistic models of oxide-supported metal catalysts.

  1. Novel Hybrid Catalyst for the Oxidation of Organic Acids: Pd Nanoparticles Supported on Mn-N-3D-Graphene Nanosheets

    DOE PAGES

    Perry, Albert; Kabir, Sadia; Matanovic, Ivana; ...

    2017-06-16

    This paper reports the fabrication and electrochemical performance of a hybrid catalyst composed of Pd nanoparticles and atomically dispersed Mn active centers integrated into the nitrogen-doped three-dimensional graphene nanosheets (Pd/Mn-N-3D-GNS). Our results show that the synergistic integration of both Pd nanoparticles and atomically dispersed Mn can be used to enhance the activity toward the electrochemical oxidation of organic acids at biologically relevant pH values. The hybrid catalyst (Pd/Mn-N-3D-GNS) showed increased maximum currents toward the oxidation of oxalic acid when compared to its individual catalysts, namely, Pd/3D-GNS and Mn N-3D-GNS catalysts. The hybrid also showed a decreased onset potential for oxidationmore » of mesoxalic acid as compared to Mn-N-3D-GNS and decreased onset potentials for the oxidation of glyoxalic acid when compared to both of its constituent catalysts. Oxidation of formic acid was also tested and the hybrid was shown to catalyze both dehydration and dehydrogenation mechanisms of formic acid electro-oxidation. Using density functional theory calculations, it was elucidated that a two-site catalysis most likely promotes dehydrogenation reaction for formic acid oxidation, which can explain the selectivity of Pd nanoparticles and atomically dispersed Mn towards the dehydrogenation/ dehydration pathway.« less

  2. Hydrogen catalysis and scavenging action of Pd-POSS nanoparticles

    SciTech Connect

    Maiti, A; Gee, R H; Maxwell, R; Saab, A

    2007-02-01

    Prompted by the need for a self-supported, chemically stable, and functionally flexible catalytic nanoparticle system, we explore a system involving Pd clusters coated with a monolayer of polyhedral oligomeric silsesquioxane (POSS) cages. With an initial theoretical focus on hydrogen catalysis and sequestration in the Pd-POSS system, we report Density Functional Theory (DFT) results on POSS binding energies to the Pd(110) surface, hydrogen storing ability of POSS, and possible pathways of hydrogen radicals from the catalyst surface to unsaturated bonds away from the surface.

  3. CO adsorption over Pd nanoparticles: A general framework for IR simulations on nanoparticles

    NASA Astrophysics Data System (ADS)

    Zeinalipour-Yazdi, Constantinos D.; Willock, David J.; Thomas, Liam; Wilson, Karen; Lee, Adam F.

    2016-04-01

    CO vibrational spectra over catalytic nanoparticles under high coverages/pressures are discussed from a DFT perspective. Hybrid B3LYP and PBE DFT calculations of CO chemisorbed over Pd4 and Pd13 nanoclusters, and a 1.1 nm Pd38 nanoparticle, have been performed in order to simulate the corresponding coverage dependent infrared (IR) absorption spectra, and hence provide a quantitative foundation for the interpretation of experimental IR spectra of CO over Pd nanocatalysts. B3LYP simulated IR intensities are used to quantify site occupation numbers through comparison with experimental DRIFTS spectra, allowing an atomistic model of CO surface coverage to be created. DFT adsorption energetics for low CO coverage (θ → 0) suggest the CO binding strength follows the order hollow > bridge > linear, even for dispersion-corrected functionals for sub-nanometre Pd nanoclusters. For a Pd38 nanoparticle, hollow and bridge-bound are energetically similar (hollow ≈ bridge > atop). It is well known that this ordering has not been found at the high coverages used experimentally, wherein atop CO has a much higher population than observed over Pd(111), confirmed by our DRIFTS spectra for Pd nanoparticles supported on a KIT-6 silica, and hence site populations were calculated through a comparison of DFT and spectroscopic data. At high CO coverage (θ = 1), all three adsorbed CO species co-exist on Pd38, and their interdiffusion is thermally feasible at STP. Under such high surface coverages, DFT predicts that bridge-bound CO chains are thermodynamically stable and isoenergetic to an entirely hollow bound Pd/CO system. The Pd38 nanoparticle undergoes a linear (3.5%), isotropic expansion with increasing CO coverage, accompanied by 63 and 30 cm- 1 blue-shifts of hollow and linear bound CO respectively.

  4. Assembling formation of highly dispersed Pd nanoparticles supported 1D carbon fiber electrospun with excellent catalytic active and recyclable performance for Suzuki reaction

    NASA Astrophysics Data System (ADS)

    Yu, Dongdong; Bai, Jie; Wang, Junzhong; Liang, Haiou; Li, Chunping

    2017-03-01

    In this work, the preparation of the palladium nanoparticles with carbon nanofibers (Pd NPs/CNFs) catalyst for the Suzuki reaction was described. In the process, palladium nanoparticles were formed in the reaction of palladium chloride and glucose. The Pd NPs/CNFs complex catalyst was prepared in subsequent calcination processes, a series of characterization revealed that the Pd NPs were well-dispersed on the surfaces of the carbon nanofibers or embedded in the carbon nanofibers. This catalyst showed high catalytic activity for the Suzuki reaction of aryl halide and aryl boronic acid in the ethanol/water (v/v = 4/3) solution, and the catalyst still had good stability after 10 cycles.

  5. Green synthesis of the Pd nanoparticles supported on reduced graphene oxide using barberry fruit extract and its application as a recyclable and heterogeneous catalyst for the reduction of nitroarenes.

    PubMed

    Nasrollahzadeh, Mahmoud; Sajadi, S Mohammad; Rostami-Vartooni, Akbar; Alizadeh, Mohammad; Bagherzadeh, Mojtaba

    2016-03-15

    Through this manuscript the green synthesis of palladium nanoparticles supported on reduced graphene oxide (Pd NPs/RGO) under the mild conditions through reduction of the graphene oxide and Pd(2+) ions using barberry fruit extract as reducing and stabilizing agent is reported. The as-prepared Pd NPs/RGO was characterized by UV-vis spectroscopy, X-ray diffraction (XRD), Fourier transformed infrared spectroscopy (FT-IR), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM) and energy dispersive X-ray spectroscopy (EDS). The Pd NPs/RGO could be used as an efficient and heterogeneous catalyst for reduction of nitroarenes using sodium borohydride in an environmental friendly medium. Excellent yields of products were obtained with a wide range of substrates and the catalyst was recycled multiple times without any significant loss of its catalytic activity. Copyright © 2015 Elsevier Inc. All rights reserved.

  6. Oleylamine-mediated synthesis of Pd nanoparticles for catalytic formic acid oxidation.

    PubMed

    Mazumder, Vismadeb; Sun, Shouheng

    2009-04-08

    We report a facile synthesis of monodisperse Pd nanoparticles by the reduction of Pd(acac)(2) with oleylamine and borane tributylamine complex. The oleylamine-coated Pd nanoparticles are readily "cleaned" with a 99% acetic acid wash, and the Pd particles supported on Ketjen carbon are catalytically active for formic acid oxidation in HClO(4) solution. The catalyst shows no obvious activity degradation after 1500 cyclic voltammetry cycles under ambient conditions. These Pd particles hold promise as a highly active non-Pt catalyst for fuel cell applications.

  7. An efficient photochemical route to Pd nanoparticles; application to the one-step synthesis of Pd@polymer nanocomposite films

    NASA Astrophysics Data System (ADS)

    Wolak, Séverine; Vidal, Loïc; Becht, Jean-Michel; Michelin, Laure; Balan, Lavinia

    2016-08-01

    We have developed a facile, efficient, low cost and ‘green’ photochemical approach to preparing surfactant-free Pd nanoparticles and Pd-immobilized@acrylate photo-polymer films at room temperature, under air and without any additional treatment. The reaction system only includes a photo-initiator used as a generator of free radicals and a Pd(II) salt. In ethanol solution, the photochemical reduction of Pd(II) to Pd(0) generates very small metal particles with a narrow size distribution (2-4 nm). Furthermore, we have shown that the formation of Pd nanoparticles from a Pd(II) salt can be reversible thus allowing easy handling and safe storage with the possibility of generating the nanoparticles just before use. In the presence of an acrylate bifunctional monomer, Pd@polymer film was obtained through a ‘one-pot, one-step’ process resulting from a simultaneous photo-reduction of Pd(II) and photo-polymerization of acrylate units. The simultaneous generation of a 3D polymer network and of metal particles leads to a homogeneous distribution of Pd nanoparticles in the photo-polymer matrix with an average diameter of approximately 3.7 ± 1.1 nm. Such as-prepared Pd@polymer films were found to efficiently catalyze the Mizoroki-Heck reaction in the presence of only 0.9 mequiv. of supported palladium. The major interest of this arrangement is its recoverability and reusability, which makes it very attractive both from a practical and economical viewpoint. Finally, it is worth noting that this innovation offers a great advantage over concurrent methods in that it is simply generated within minutes, it is highly stable, and there is sharp monodispersity in the size of the Pd nanoparticles that can be stored for months without alteration of their physico-chemical properties and catalytic activity.

  8. PLGA-PEG-supported Pd Nanoparticles as Efficient Catalysts for Suzuki-Miyaura Coupling Reactions in Water.

    PubMed

    Dumas, Anaëlle; Peramo, Arnaud; Desmaële, Didier; Couvreur, Patrick

    2016-01-01

    Chemical transformations that can be performed selectively under physiological conditions are highly desirable tools to track biomolecules and manipulate complex biological processes. Here, we report a new nanocatalyst consisting of small palladium nanoparticles stabilized on the surface of PLGA-PEG nanoparticles that show excellent catalytic activity for the modification of biological building blocks through Suzuki-Miyaura cross-coupling reactions in water. Brominated or iodinated amino acids were coupled with aryl boronic acids in phosphate buffer in good yields. Interestingly, up to 98% conversion into the coupled amino acid could be achieved in 2 h at 37 °C using the stable, water-soluble cyclic triolborate as organometallic partner in the presence of only 1 mol% of palladium. These results pave the way for the modification of biomolecules in complex biological systems such as the intracellular space.

  9. 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.

  10. Electrochemical sensor for detection of hydrazine based on Au@Pd core-shell nanoparticles supported on amino-functionalized TiO2 nanotubes.

    PubMed

    Chen, Xianlan; Liu, Wei; Tang, Lele; Wang, Jian; Pan, Haibo; Du, Min

    2014-01-01

    In this paper, we reported a simple strategy for synthesizing well-defined TiO2NTs-Au@Pd hybrid nanostructures with prior TiO2 nanotube functionalization (F-TiO2NTs). TiO2NTs with larger surface area (BET surface area is 184.9m(2)g(-1)) were synthesized by hydrothermal method, and the NTs are anatase phase with a range of 2-3μm in length and 30-50nm in diameter after calcined at 400°C for 3h. 3-Aminopropyl-trimethoxysilane (APTMS) as a coupling agent was reacted with the surface hydroxyl groups as anchoring sites for flower-shaped bimetallic Au@Pd nanostructures, self-assembling amine functionality on the surface of TiO2NTs. Note that two faces at the interface between F-TiO2NTs with (004) plane and Au@Pd nanostructures with (111) one of cubic Au and Pd nanoparticles are compatible, benefiting to the charge transfer between two components due to their crystalline coordination. The results showed that as-prepared F-TiO2NTs-Au@Pd hybrid nanostructures modified glassy carbon electrode (GCE) exhibits high electrocatalytic activity toward hydrazine (N2H4) at low potential and a linear response from 0.06 to 700μM with the detection limit for N2H4 was found to be 1.2×10(-8)M (S/N=3). Based on scan rate effect during the hydrazine oxidation, it indicates that the number of electrons transferred in the rate-limiting step is 1, and a transfer coefficient (α) is estimated as 0.73. The self-assembled F-TiO2NTs-Au@Pd hybrid nanostructures as enhanced materials present excellent electrocatalytic activity, fast response, highly sensitive and have a promising application potential in nonenzymatic sensing.

  11. 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.

  12. Synthesis and composition evolution of bimetallic Pd Pt alloy nanoparticles

    NASA Astrophysics Data System (ADS)

    Ren, Guoqiang; Shi, Honglan; Xing, Yangchuan

    2007-09-01

    This paper reports a study on the synthesis of Pd-Pt alloy nanoparticles and composition evolution of the alloys. The synthesis involves Pd and Pt acetylacetonate as the metal precursors and trioctylphosphine (TOP) as the solvent. Thermal decomposition of the Pd-TOP complex resulted in Pd nanoparticles, while substitution of Pt in the Pt-TOP complex by Pd allowed formation of the Pd-Pt alloys. It was observed that the Pd-Pt nanoparticles formed at the very beginning in the synthesis process are Pd rich with various nanoparticle sizes ranging from 1.5 to 25 nm in diameter. These nanoparticles averaged out through a digestive ripening process and reached a final size of 3.5 nm in about 10 min. The alloy compositions evolved throughout the synthesis process and only reached the preset Pd to Pt ratio of the precursors in 120 min. It was found that Pt acetylacetonate alone in TOP cannot produce Pt nanoparticles, which was attributed to the formation of a Pt-TOP complex and a strong coordination of Pt to the phosphine. This observation led us to propose an atomic exchange process between the Pt-TOP complex and the Pd atoms at the nanoparticle surface. As a result, the alloy formation process is limited by a substitution and diffusion rate of the Pt atoms at the surface of the alloy nanoparticles.

  13. Enhanced CO photocatalytic oxidation in the presence of humidity by tuning composition of Pd-Pt bimetallic nanoparticles supported on TiO2.

    PubMed

    Rosseler, Olivier; Louvet, Alain; Keller, Valérie; Keller, Nicolas

    2011-05-14

    Here we put forward for the first time that the negative effect of humidity on CO photooxidation at room temperature can be overcome by adjusting the composition of Pd-Pt bimetallic particles supported on TiO(2). Consequently, optimized Pd(x)Pt(1-x)/TiO(2) materials can be considered as common and efficient photocatalysts for simultaneous elimination of CO and VOCs in the presence of humidity, i.e. for real indoor air treatment. © The Royal Society of Chemistry 2011

  14. Monodispersed bimetallic PdAg nanoparticles with twinned structures: Formation and enhancement for the methanol oxidation

    PubMed Central

    Yin, Zhen; Zhang, Yining; Chen, Kai; Li, Jing; Li, Wenjing; Tang, Pei; Zhao, Huabo; Zhu, Qingjun; Bao, Xinhe; Ma, Ding

    2014-01-01

    Monodispersed bimetallic PdAg nanoparticles can be fabricated through the emulsion-assisted ethylene glycol (EG) ternary system. Different compositions of bimetallic PdAg nanoparticles, Pd80Ag20, Pd65Ag35 and Pd46Ag54 can be obtained via adjusting the reaction parameters. For the formation process of the bimetallic PdAg nanoparticles, there have two-stage growth processes: firstly, nucleation and growth of the primary nanoclusters; secondly, formation of the secondary nanoparticles with the size-selection and relax process via the coalescence or aggregation of the primary nanoclusters. The as-prepared PdAg can be supported on the carbon black without any post-treatment, which exhibited high electro-oxidation activity towards methanol oxidation under alkaline media. More importantly, carbon-supported Pd80Ag20 nanoparticles reveal distinctly superior activities for the methanol oxidation, even if compared with commercial Pt/C electro-catalyst. It is concluded that the enhanced activity is dependant on the unique twinning structure with heterogeneous phase due to the dominating coalescence growth in EG ternary system. PMID:24608736

  15. Atomic layer deposition of Pd and Pt nanoparticles for catalysis: on the mechanisms of nanoparticle formation

    NASA Astrophysics Data System (ADS)

    Mackus, Adriaan J. M.; Weber, Matthieu J.; Thissen, Nick F. W.; Garcia-Alonso, Diana; Vervuurt, René H. J.; Assali, Simone; Bol, Ageeth A.; Verheijen, Marcel A.; Kessels, Wilhelmus M. M.

    2016-01-01

    The deposition of Pd and Pt nanoparticles by atomic layer deposition (ALD) has been studied extensively in recent years for the synthesis of nanoparticles for catalysis. For these applications, it is essential to synthesize nanoparticles with well-defined sizes and a high density on large-surface-area supports. Although the potential of ALD for synthesizing active nanocatalysts for various chemical reactions has been demonstrated, insight into how to control the nanoparticle properties (i.e. size, composition) by choosing suitable processing conditions is lacking. Furthermore, there is little understanding of the reaction mechanisms during the nucleation stage of metal ALD. In this work, nanoparticles synthesized with four different ALD processes (two for Pd and two for Pt) were extensively studied by transmission electron spectroscopy. Using these datasets as a starting point, the growth characteristics and reaction mechanisms of Pd and Pt ALD relevant for the synthesis of nanoparticles are discussed. The results reveal that ALD allows for the preparation of particles with control of the particle size, although it is also shown that the particle size distribution is strongly dependent on the processing conditions. Moreover, this paper discusses the opportunities and limitations of the use of ALD in the synthesis of nanocatalysts.

  16. Electronic Structure and Phase Stability of PdPt Nanoparticles.

    PubMed

    Ishimoto, Takayoshi; Koyama, Michihisa

    2016-03-03

    To understand the origin of the physicochemical nature of bimetallic PdPt nanoparticles, we theoretically investigated the phase stability and electronic structure employing the PdPt nanoparticles models consisting of 711 atoms (ca. 3 nm). For the Pd-Pt core-shell nanoparticle, the PdPt solid-solution phase was found to be a thermodynamically stable phase in the nanoparticle as the result of difference in surface energy of Pd and Pt nanoparticles and configurational entropy effect, while it is well known that the Pd and Pt are the immiscible combination in the bulk phase. The electronic structure of nanoparticles is conducted to find that the electron transfer occurs locally within surface and subsurface layers. In addition, the electron transfer from Pd to Pt at the interfacial layers in core-shell nanoparticles is observed, which leads to unique geometrical and electronic structure changes. Our results show a clue for the tunability of the electronic structure of nanoparticles by controlling the arrangement in the nanoparticles.

  17. Hydrogen storage and phase transformations in Mg-Pd nanoparticles

    NASA Astrophysics Data System (ADS)

    Callini, E.; Pasquini, L.; Rude, L. H.; Nielsen, T. K.; Jensen, T. R.; Bonetti, E.

    2010-10-01

    Microstructure refinement and synergic coupling among different phases are currently explored strategies to improve the hydrogen storage properties of traditional materials. In this work, we apply a combination of these methods and synthesize Mg-Pd composite nanoparticles by inert gas condensation of Mg vapors followed by vacuum evaporation of Pd clusters. Irreversible formation of the Mg6Pd intermetallic phase takes place upon vacuum annealing, resulting in Mg/Mg6Pd composite nanoparticles. Their hydrogen storage properties are investigated and connected to the undergoing phase transformations by gas-volumetric techniques and in situ synchrotron radiation powder x-ray diffraction. Mg6Pd transforms reversibly into different Mg-Pd intermetallic compounds upon hydrogen absorption, depending on temperature and pressure. In particular, at 573 K and 1 MPa hydrogen pressure, the metal-hydride transition leads to the formation of Mg3Pd and Mg5Pd2 phases. By increasing the pressure to 5 MPa, the Pd-richer MgPd intermetallic is obtained. Upon hydrogen desorption, the Mg6Pd phase is reversibly recovered. These phase transformations result in a specific hydrogen storage capacity associated with Mg-Pd intermetallics, which attain the maximum value of 3.96 wt % for MgPd and influence both the thermodynamics and kinetics of hydrogen sorption in the composite nanoparticles.

  18. 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.

  19. Temperature and composition dependent structural evolution of AgPd bimetallic nanoparticle: phase diagram of (AgPd)151 nanoparticle.

    PubMed

    Kim, Hyun You; Kim, Da Hye; Lee, Hyuck Mo

    2011-03-01

    We study the structural evolution of a 151 atom Ag-Pd bimetallic nanoparticle with composition and temperature. The solid-to-liquid transition region was investigated using molecular dynamics simulations with an improved collision method, and the solid-state structure of the nanoparticle was explored with a combination of molecular dynamics and density functional theory. Results show that an fcc-to-icosahedron transformation occurs at high temperature in all composition range and that a composition of nanoparticles concerns the atomic distribution of the (AgPd)151 nanoparticle. As a result, we constructed a phase diagram of the (AgPd)151 nanoparticle. Our phase diagram offers guidance on the application of Ag-Pd nanoparticles.

  20. Catalytic oxidation of carbon monoxide over supported palladium nanoparticles

    NASA Astrophysics Data System (ADS)

    Soni, Keshav Chand; Krishna, R.; Chandra Shekar, S.; Singh, Beer

    2016-01-01

    Catalytic oxidation of CO with ozone had been studied over Al2O3 and SiO2 supported Pd nanoparticles which was synthesized by two different methods. The polyol method mainly resulted in highly dispersed Pd particles on the support, while the impregnation method resulted in agglomeration Pd particles on the support. Supported Pd nanoparticles synthesized from PdCl2 in the presence of poly ( N-vinylpyrrolidone) (PVP) by chemical reduction. The catalysts were characterized by X-ray diffraction, N2 BET surface area, pore size distributions, CO chemisorption, TEM and H2-temperature programmed reduction. The physico-chemical properties were well correlated with activity data. Characterizations of XRD and TEM show that the surface Pd nanoparticles are highly dispersed over Al2O3 and SiO2. The catalytic activity was dependent upon ozone/CO ratio, contact times, and the reaction temperature. The extent of carbon monoxide oxidation was proportional to the catalytically ozone decomposition. The PVP synthesized Pd/A2O3 catalyst had been found to be highly active for complete CO removal at room temperature. The higher activity of the nanocatalyst was attributed to small particle size and higher dispersion of Pd over support.

  1. Enhanced hydrogenation and reduced lattice distortion in size selected Pd-Ag and Pd-Cu alloy nanoparticles

    SciTech Connect

    Sengar, Saurabh K.; Mehta, B. R.; Kulriya, P. K.; Khan, S. A.

    2013-10-21

    Important correlation between valence band spectra and hydrogenation properties in Pd alloy nanoparticles is established by studying the properties of size selected and monocrystalline Pd, Ag, Cu, Pd-Ag, and Pd-Cu nanoparticles. The X-ray photoelectron spectroscopy and elastic recoil detection analysis show that size induced Pd4d centroid shift is related to enhanced hydrogenation with H/Pd ratio of 0.57 and 0.49 in Pd-Ag and Pd-Cu nanoparticles in comparison to reported bulk values of 0.2 and 0.1, respectively. Pd-alloy nanoparticles show lower hydrogen induced lattice distortion. The reduced distortion and higher hydrogen reactivity of Pd-alloy nanoparticles is important for numerous hydrogen related applications.

  2. Enhanced formic acid oxidation on Cu-Pd nanoparticles

    NASA Astrophysics Data System (ADS)

    Dai, Lin; Zou, Shouzhong

    Developing catalysts with high activity and high resistance to surface poisoning remains a challenge in direct formic acid fuel cell research. In this work, copper-palladium nanoparticles were formed through a galvanic replacement process. After electrochemically selective dissolution of surface Cu, Pd-enriched Cu-Pd nanoparticles were formed. These particles exhibit much higher formic acid oxidation activities than that on pure Pd nanoparticles, and they are much more resistant to the surface poisoning. Possible mechanisms of catalytic activity enhancement are briefly discussed.

  3. In situ oxidation study of Pd-Rh nanoparticles on MgAl₂O₄(001).

    PubMed

    Müller, Patrick; Hejral, Uta; Rütt, Uta; Stierle, Andreas

    2014-07-21

    Alloy nanoparticles on oxide supports are widely used as heterogeneous catalysts in reactions involving oxygen. Here we discuss the oxidation behavior of Pd-Rh alloy nanoparticles on MgAl2O4(001) supports with a particle diameter from 6-11 nm. As an In situ tool, we employed high energy grazing incidence X-ray diffraction at a photon energy of 85 keV. We find that physical vapor deposited Pd-Rh nanoparticles grow epitaxially on MgAl2O4(001) with a truncated octahedral shape over the whole concentration range. During our systematic oxidation experiments performed at 670 K in the pressure range from 10(-3) to 0.1 mbar, we observe for Rh containing nanoparticles the formation of two different Rh oxide phases, namely RhO2 and a spinel-like Rh3O4 phase. PdO formation is only observed for pure Pd nanoparticles. This oxidation induced segregation behavior is also reflected in the oxidation induced enlargement of the average nanoparticle lattice parameter towards to value for pure Pd. Our results have ramifications for the phase separation behavior of alloy nanocatalysts under varying reducing and oxidizing environments.

  4. Reaction-Driven Restructuring of Rh-Pd and Pt-Pd Core-Shell Nanoparticles

    SciTech Connect

    Tao, Feng; Grass, Michael E.; Zhang, Yawen; Butcher, Derek R.; Renzas, James R.; Liu, Zhi; Chung, Jen Y.; Mun, Bongjin S.; Salmeron, Miquel; Somorjai, Gabor A.

    2009-06-17

    The structure and composition of core-shell Rh{sub 0.5}Pd{sub 0.5} and Pt{sub 0.5}Pd{sub 0.5} nanoparticle catalysts were studied in situ, during oxidizing, reducing, and catalytic reactions involving NO, O{sub 2}, CO, and H{sub 2} using X-ray photoelectron spectroscopy in the Torr pressure range. The Rh{sub 0.5}Pd{sub 0.5} nanoparticles undergo dramatic and reversible changes in composition and chemical state in response to oxidizing or reducing conditions. Under oxidizing conditions the Rh atoms segregate to the shell region while in reducing atmospheres the Pd atoms diffuse to the shell region. In contrast no significant segregation of Pd or Pt atoms was found in Pt{sub 0.5}Pd{sub 0.5} nanoparticles. The distinct behavior in restructuring and chemical response of Rh{sub 0.5}Pd{sub 0.5} and Pt{sub 0.5}Pd{sub 0.5} nanoparticle catalysts under the same reaction conditions illustrates the flexibility and tunability of the structure of bimetallic nanoparticle catalysts during catalytic reactions.

  5. Nanoalloying and phase transformations during thermal treatment of physical mixtures of Pd and Cu nanoparticles

    PubMed Central

    Mukundan, Vineetha; Yin, Jun; Joseph, Pharrah; Luo, Jin; Shan, Shiyao; Zakharov, Dmitri N; Zhong, Chuan-Jian; Malis, Oana

    2014-01-01

    Nanoscale alloying and phase transformations in physical mixtures of Pd and Cu ultrafine nanoparticles are investigated in real time with in situ synchrotron-based x-ray diffraction complemented by ex situ high-resolution transmission electron microscopy. The combination of metal–support interaction and reactive/non-reactive environment was found to determine the thermal evolution and ultimate structure of this binary system. At 300 °C, the nanoparticles supported on silica and carbon black intermix to form a chemically ordered CsCl-type (B2) alloy phase. The B2 phase transforms into a disordered fcc alloy at higher temperature (> 450 °C). The alloy nanoparticles supported on silica and carbon black are homogeneous in volume, but evidence was found of Pd surface enrichment. In sharp contrast, when supported on alumina, the two metals segregated at 300 °C to produce almost pure fcc Cu and Pd phases. Upon further annealing of the mixture on alumina above 600 °C, the two metals interdiffused, forming two distinct disordered alloys of compositions 30% and 90% Pd. The annealing atmosphere also plays a major role in the structural evolution of these bimetallic nanoparticles. The nanoparticles annealed in forming gas are larger than the nanoparticles annealing in helium due to reduction of the surface oxides that promotes coalescence and sintering. PMID:27877663

  6. Enhanced activity and selectivity of carbon nanofiber supported Pd catalysts for nitrite reduction.

    PubMed

    Shuai, Danmeng; Choe, Jong Kwon; Shapley, John R; Werth, Charles J

    2012-03-06

    Pd-based catalyst treatment represents an emerging technology that shows promise to remove nitrate and nitrite from drinking water. In this work we use vapor-grown carbon nanofiber (CNF) supports in order to explore the effects of Pd nanoparticle size and interior versus exterior loading on nitrite reduction activity and selectivity (i.e., dinitrogen over ammonia production). Results show that nitrite reduction activity increases by 3.1-fold and selectivity decreases by 8.0-fold, with decreasing Pd nanoparticle size from 1.4 to 9.6 nm. Both activity and selectivity are not significantly influenced by Pd interior versus exterior CNF loading. Consequently, turnover frequencies (TOFs) among all CNF catalysts are similar, suggesting nitrite reduction is not sensitive to Pd location on CNFs nor Pd structure. CNF-based catalysts compare favorably to conventional Pd catalysts (i.e., Pd on activated carbon or alumina) with respect to nitrite reduction activity and selectivity, and they maintain activity over multiple reduction cycles. Hence, our results suggest new insights that an optimum Pd nanoparticle size on CNFs balances faster kinetics with lower ammonia production, that catalysts can be tailored at the nanoscale to improve catalytic performance for nitrite, and that CNFs hold promise as highly effective catalyst supports in drinking water treatment.

  7. A combined experimental and computational study of AuPd nanoparticles

    NASA Astrophysics Data System (ADS)

    Bruma, Alina

    The thesis is focused on the investigation of structural properties of AuPd nanoparticles via theoretical and experimental studies. For the first system, the 98-atom AuPd nanoclusters, a theoretical analysis has been employed to study the energetics and segregation effects and to assess how typical is the Leary Tetrahedron (LT). Although this motif is the most stable at the empirical level, it loses stability at the DFT level against FCC or Marks Decahedron. The second system is the Au24Pd1 nanoclusters. Theoretically, by performing a search at the DFT level using Basin Hopping Monte Carlo, we identified pyramidal cage structures as putative global minima, where Pd sits in the core and Au occupies surface positions. The Lowdin analysis emphasized charge transfer between Pd and Au, explaining the enhanced catalytic activity with respect to Au25 clusters. Experimentally, STEM has been employed for the structural characterization of Au24Pd1 clusters supported on Multiwall Carbon Nanotubes. Whenever possible, we have tried to link the experimental analysis to the theoretical findings. The third system has been the evaporated AuPd nanoparticles. We observed that the annealing process led to the formation of L12 ordered phases as well as layered and core-shell structures. This study aimed to bring an insight on the segregation and energetics effects of AuPd nanoparticles with potential applications in nanocatalysis.

  8. One step electrochemical synthesis of bimetallic PdAu supported on nafion–graphene ribbon film for ethanol electrooxidation

    SciTech Connect

    Shendage, Suresh S. Singh, Abilash S.; Nagarkar, Jayashree M.

    2015-10-15

    Highlights: • Electrochemical deposition of bimetallic PdAu NPs. • Highly loaded PdAu NPs are obtained. • Nafion–graphene supported PdAu NPs shows good activity for ethanol electrooxidation. - Abstract: A nafion–graphene ribbon (Nf–GR) supported bimetallic PdAu nanoparticles (PdAu/Nf–GR) catalyst was prepared by electrochemical codeposition of Pd and Au at constant potential. The prepared catalyst was characterized by scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDAX), transmission electron microscopy (TEM) and X-ray diffraction analysis (XRD). The average particle size of PdAu nanoparticles (NPs) determined from XRD was 3.5 nm. The electrocatalytic activity of the PdAu/Nf–GR catalyst was examined by cyclic voltametry. It was observed that the as prepared catalyst showed efficient activity and good stability for ethanol electrooxidation in alkaline medium.

  9. Theoretical insights into the energetics and electronic properties of MPt12 (M = Fe, Co, Ni, Cu, and Pd) nanoparticles supported by N-doped defective graphene

    NASA Astrophysics Data System (ADS)

    Wang, Qing; Tian, Yu; Chen, Guangju; Zhao, Jingxiang

    2017-03-01

    Enhancing the catalytic activity and decreasing the usage of Pt catalysts has been a major target in widening their applications for developing proton-exchange membrane fuel cells. In this work, the adsorption energetics, structural features, and electronic properties of several MPt12 (M = Fe, Co, Ni, Cu, and Pd) nanoparticles (NPs) deposited on N-doped defective graphene were systemically explored by means of comprehensive density functional theory (DFT) computations. The computations revealed that the defective N-doped graphene substrate can provide anchoring site for these Pt-based alloying NPs due to their strong hybridization with the sp2 dangling bonds at the defect sites of substrate. Especially, these deposited MPt12 NPs exhibit reduced magnetic moment and their average d-band centers are shifted away from the Fermi level, as compared with the freestanding NPs, leading to the reduction of the adsorption energies of the O species. Thus, the defective N-doped graphene substrate not only enhances the stability of the deposited MPt12 NPs, but also endows them higher catalytic performance for the oxygen reduction reaction.

  10. Direct synthesis of graphene nanosheets support Pd nanodendrites for electrocatalytic formic acid oxidation

    NASA Astrophysics Data System (ADS)

    Yang, Su-Dong; Chen, Lin

    2015-11-01

    We report a solvothermal method preparation of dendritic Pd nanoparticles (DPNs) and spherical Pd nanoparticles (SPNs) supported on reduced graphene oxide (RGO). Drastically different morphologies of Pd NPs with nanodendritic structures or spherical structures were observed on graphene by controlling the reduction degree of graphene oxide (GO) under mild conditions. In addition to being a commonplace substrate, GO plays a more important role that relies on its surface groups, which serves as a shape-directing agent to direct the dendritic growth. As a result, the obtained DPNs/RGO catalyst exhibits a significantly enhanced electro-catalytic behavior for the oxidation of formic acid compared to the SPNs/RGO catalyst.

  11. Thermally stable nanoparticles on supports

    DOEpatents

    Roldan Cuenya, Beatriz; Naitabdi, Ahmed R.; Behafarid, Farzad

    2012-11-13

    An inverse micelle-based method for forming nanoparticles on supports includes dissolving a polymeric material in a solvent to provide a micelle solution. A nanoparticle source is dissolved in the micelle solution. A plurality of micelles having a nanoparticle in their core and an outer polymeric coating layer are formed in the micelle solution. The micelles are applied to a support. The polymeric coating layer is then removed from the micelles to expose the nanoparticles. A supported catalyst includes a nanocrystalline powder, thin film, or single crystal support. Metal nanoparticles having a median size from 0.5 nm to 25 nm, a size distribution having a standard deviation .ltoreq.0.1 of their median size are on or embedded in the support. The plurality of metal nanoparticles are dispersed and in a periodic arrangement. The metal nanoparticles maintain their periodic arrangement and size distribution following heat treatments of at least 1,000.degree. C.

  12. CH4 combustion cycles at Pd/Al2O3--important role of support and oxygen access.

    PubMed

    Czekaj, Izabela; Kacprzak, Katarzyna A; Mantzaras, John

    2013-07-21

    This research is focused on the analysis of adsorbed CH4 intermediates at oxidized Pd9 nanoparticles supported on γ-alumina. From first-principle density functional theory calculations, several configurations, charge transfer and electronic density of states have been analyzed in order to determine feasible paths for the oxidation process. Methane oxidation cycles have been considered as a further step at differently oxidized Pd nanoparticles. For low oxidized Pd nanoparticles, activation of methane is observed, whereby hydrogen from methane is adsorbed at one oxygen atom. This reaction is exothermic with adsorption energy equal to -0.38 eV. In a subsequent step, desorption of two water molecules is observed. Additionally, a very interesting structural effect is evident, mainly Pd-carbide formation, which is also an exothermic reaction with an energy of -0.65 eV. Furthermore, oxidation of such carbidized Pd nanoparticles leads to CO2 formation, which is an endothermic reaction. Important result is that the support is involved in CO2 formation. A different mechanism of methane oxidation has been found for highly oxidized Pd nanoparticles. When the Pd nanoparticle is more strongly exposed to oxidative conditions, adsorption of methane is also possible, but it will proceed with carbonic acid production at the interface between Pd nanoparticles and support. However, this step is endothermic.

  13. Coarsening of Pd nanoparticles in an oxidizing atmosphere studied by in situ TEM

    NASA Astrophysics Data System (ADS)

    Simonsen, Søren Bredmose; Chorkendorff, Ib; Dahl, Søren; Skoglundh, Magnus; Helveg, Stig

    2016-06-01

    The coarsening of supported palladium nanoparticles in an oxidizing atmosphere was studied in situ by means of transmission electron microscopy (TEM). Specifically, the Pd nanoparticles were dispersed on a planar and amorphous Al2O3 support and were observed during the exposure to 10 mbar technical air at 650 °C. Time-resolved TEM image series reveal that the Pd nanoparticles were immobile and that a few percent of the nanoparticles grew or shrank, indicating a coarsening process mediated by the Ostwald ripening mechanism. The TEM image contrast suggests that the largest nanoparticles tended to wet the Al2O3 support to a higher degree than the smaller nanoparticles and that the distribution of projected particle sizes consequently broadens by the appearance of an asymmetric tail toward the larger particle sizes. A comparison with computer simulations based on a simple mean-field model for the Ostwald ripening process indicates that the observed change in the particle size distribution can be accounted for by wetting of the Al2O3 support by the larger Pd nanoparticles.

  14. The irreversible formation of palladium carbide during hydrogenation of 1-pentyne over silica-supported palladium nanoparticles: in situ Pd K and L3 edge XAS.

    PubMed

    Tew, Min Wei; Nachtegaal, Maarten; Janousch, Markus; Huthwelker, Thomas; van Bokhoven, Jeroen A

    2012-04-28

    The catalytically active phase of silica-supported palladium catalysts in the selective and non-selective hydrogenation of 1-pentyne was determined using in situ X-ray absorption spectroscopy at the Pd K and L(3) edges. Upon exposure to alkyne, a palladium carbide-like phase rapidly forms, which prevents hydrogen to diffuse into the bulk of the nano-sized particles. Both selective and non-selective hydrogenation occur over carbided particles. The palladium carbide-like phase is stable under reaction conditions and only partially decomposes under high hydrogen partial pressure. Non-selective hydrogenation to pentane is not indicative of hydride formation. The palladium carbide phase was detected in the EXAFS analysis and the K edge XANES showed representative features. This journal is © the Owner Societies 2012

  15. Support and Oxidation Effects on Subnanometer Palladium Nanoparticles

    SciTech Connect

    Heard, Christopher J.; Vajda, Stefan; Johnston, Roy L.

    2014-01-30

    The effect of cluster size, oxidation state, and the support upon the structures and energetics of subnanometer palladium nanoparticles is investigated within a density functional framework. Gas phase global minima of Pd-4 and Pd-10 along with their suboxide counterparts are determined using a genetic algorithm and deposited upon MgO (001) and a high-index alumina surface. It is observed that there is an oxidation-dependent transition in the smaller clusters from three-dimensional to two-dimensional structures both in the gas phase and when supported by a surface. MgO strongly promotes a change from tetrahedral- and icosahedral-based structures toward cubic forms, while alumina induces significant distortion of the cluster and the breaking of Pd-Pd bonds. Increased oxygenation contributes cooperatively to these effects, causing disruption of the Pd-Pd bond network, favoring the incorporation of oxygen into the cluster structure, further complicating unambiguous structure prediction.

  16. Structural Rearrangement of Au-Pd Nanoparticles under Reaction Conditions: An ab Initio Molecular Dynamics Study.

    PubMed

    Xu, Cong-Qiao; Lee, Mal-Soon; Wang, Yang-Gang; Cantu, David C; Li, Jun; Glezakou, Vassiliki-Alexandra; Rousseau, Roger

    2017-02-28

    The structure, composition, and atomic distribution of nanoalloys under operating conditions are of significant importance for their catalytic activity. In the present work, we use ab initio molecular dynamics simulations to understand the structural behavior of Au-Pd nanoalloys supported on rutile TiO2 under different conditions. We find that the Au-Pd structure is strongly dependent on the redox properties of the support, originating from strong metal-support interactions. Under reducing conditions, Pd atoms are inclined to move toward the metal/oxide interface, as indicated by a significant increase of Pd-Ti bonds. This could be attributed to the charge localization at the interface that leads to Coulomb attractions to positively charged Pd atoms. In contrast, under oxidizing conditions, Pd atoms would rather stay inside or on the exterior of the nanoparticle. Moreover, Pd atoms on the alloy surface can be stabilized by hydrogen adsorption, forming Pd-H bonds, which are stronger than Au-H bonds. Our work offers critical insights into the structure and redox properties of Au-Pd nanoalloy catalysts under working conditions.

  17. Catalytic hydrodechlorination of trichloroethylene in water with supported CMC-stabilized palladium nanoparticles.

    PubMed

    Zhang, Man; Bacik, Deborah B; Roberts, Christopher B; Zhao, Dongye

    2013-07-01

    In this work, we developed and tested a new class of supported Pd catalysts by immobilizing CMC (carboxymethyl cellulose) stabilized Pd nanoparticles onto alumina support. The alumina supported Pd nanoparticles were able to facilitate rapid and complete hydrodechlorination of TCE (trichloroethylene) without intermediate by-products detected. With a Pd mass loading of 0.33 wt% of the alumina mass, the observed pseudo first order reaction rate constant, k(obs), for the catalyst was increased from 28 to 109 L/min/g when CMC concentration was raised from 0.005 to 0.15 wt%. The activity increase was in accord with an increase of the Pd dispersion (measured via CO chemisorption) from 30.4% to 45.1%. Compared to the commercial alumina supported Pd, which has a lower Pd dispersion of 21%, our CMC-stabilized Pd nanoparticles offered more than 7 times greater activity. Pre-calcination treatment of the supported catalyst resulted in minor drop in activity, yet greatly reduced bleeding (<6%) of the Pd nanoparticles from the support during multiple cycles of applications. The presence of DOM (dissolved organic matter) at up to 10 mg/L as TOC had negligible effect on the catalytic activity. The alumina supported CMC-stabilized Pd nanoparticles may serve as a class of more effective catalysts for water treatment uses.

  18. Ternary Pd-Ni-P hybrid electrocatalysts derived from Pd-Ni core-shell nanoparticles with enhanced formic acid oxidation activity.

    PubMed

    Liang, Xin; Liu, Bo; Zhang, Juntao; Lu, Siqi; Zhuang, Zhongbin

    2016-09-25

    Ternary Pd-Ni-P hybrid electrocatalysts were synthesized through low temperature phosphidation of Pd-Ni core-shell nanoparticles. They show enhanced formic acid electro-oxidation activity compared to Pd, Pd-Ni and Pd-P nanoparticles, which is ascribed to the synergistic effect of the Ni and P components with Pd.

  19. Size and alloying induced shift in core and valence bands of Pd-Ag and Pd-Cu nanoparticles

    SciTech Connect

    Sengar, Saurabh K.; Mehta, B. R.; Govind

    2014-03-28

    In this report, X-ray photoelectron spectroscopy studies have been carried out on Pd, Ag, Cu, Pd-Ag, and Pd-Cu nanoparticles having identical sizes corresponding to mobility equivalent diameters of 60, 40, and 20 nm. The nanoparticles were prepared by the gas phase synthesis method. The effect of size on valence and core levels in metal and alloy nanoparticles has been studied by comparing the values to those with the 60 nm nanoparticles. The effect of alloying has been investigated by comparing the valence and core level binding energies of Pd-Cu and Pd-Ag alloy nanoparticles with the corresponding values for Pd, Ag, and Cu nanoparticles of identical sizes. These effects have been explained in terms of size induced lattice contractions, alloying induced charge transfer, and hybridization effects. The observation of alloying and size induced binding energy shifts in bimetallic nanoparticles is important from the point of view of hydrogen reactivity.

  20. Size and alloying induced shift in core and valence bands of Pd-Ag and Pd-Cu nanoparticles

    NASA Astrophysics Data System (ADS)

    Sengar, Saurabh K.; Mehta, B. R.; Govind

    2014-03-01

    In this report, X-ray photoelectron spectroscopy studies have been carried out on Pd, Ag, Cu, Pd-Ag, and Pd-Cu nanoparticles having identical sizes corresponding to mobility equivalent diameters of 60, 40, and 20 nm. The nanoparticles were prepared by the gas phase synthesis method. The effect of size on valence and core levels in metal and alloy nanoparticles has been studied by comparing the values to those with the 60 nm nanoparticles. The effect of alloying has been investigated by comparing the valence and core level binding energies of Pd-Cu and Pd-Ag alloy nanoparticles with the corresponding values for Pd, Ag, and Cu nanoparticles of identical sizes. These effects have been explained in terms of size induced lattice contractions, alloying induced charge transfer, and hybridization effects. The observation of alloying and size induced binding energy shifts in bimetallic nanoparticles is important from the point of view of hydrogen reactivity.

  1. Pd nanoparticles formation inside porous polymeric scaffolds followed by in situ XANES/SAXS

    NASA Astrophysics Data System (ADS)

    Longo, A.; Lamberti, C.; Agostini, G.; Borfecchia, E.; Lazzarini, A.; Liu, W.; Giannici, F.; Portale, G.; Groppo, E.

    2016-05-01

    Simultaneous time-resolved SAXS and XANES techniques were employed to follow in situ the formation of Pd nanoparticles from palladium acetate precursor in two porous polymeric supports: polystyrene (PS) and poly(4-vinyl-pyridine) (P4VP). In this study we have investigated the effect of the use of different reducing agents (H2 and CO) from the gas phase. These results, in conjunction with data obtained by diffuse reflectance IR (DRIFT) spectroscopy and TEM measurements, allowed us to unravel the different roles played by gaseous H2 and CO in the formation of the Pd nanoparticles for both PS and P4VP hosting scaffolds.

  2. Hydrodechlorination Catalysis of Pd-on-Au Nanoparticles Varies with Particle Size

    SciTech Connect

    Pretzer, Lori A.; Song, Hyun J.; Fang, Yu-Lun; Zhao, Zhun; Guo, Neng; Wu, Tianpin; Arslan, Ilke; Miller, Jeffrey T.; Wong, Michael S.

    2013-02-01

    The dependence of bimetallic PdAu catalytic activity on the relative ratios of Pd and Au has been theoretically predicted and experimentally observed for a number of reactions. Trichloroethene (TCE), a common carcinogenic solvent that is difficult to remove from contaminated groundwater in many industrialized nations, can be chemically degraded especially rapidly with Au nanoparticles partially coated with Pd ("Pd-on-Au NPs"). These NPs catalyze the room-temperature water-phase TCE hydrodechlorination (HDC) reaction with activities that follow a volcano-shape dependence on Pd surface coverage. The effect of particle size is not known, though. Pd-on-Au NPs synthesized with 3, 7, and 10 nm Au NPs and Pd surface coverages between 0 and 150% were studied in detail. Volcano-shape dependence on Au particle size and Pd surface coverage was observed, with 7 nm Au NPs with a Pd coverage of 60-70% having the highest TCE HDC activity. Extended x-ray absorption fine-structure spectroscopy (EXAFS) revealed the correlation was strongest between catalytic activity and the presence of non-oxidized Pd ensembles of ~2-3 atoms in contact with ~8-10 Au atoms. Isolated Pd atoms and Pd ensembles were visualized for the first time through aberration-corrected scanning transmission electron microscopy (STEM). This study provides the most direct evidence yet for Pd-on-Au NPs containing 2-dimensional Pd ensembles as the active sites for TCE HDC and likely for other chemical reactions. A portion of the research was performed using EMSL, 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. This research was supported by the Laboratory Directed Research and Development program at Pacific Northwest National Laboratory. The Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.

  3. Monodispersed bimetallic PdAg nanoparticles with twinned structures: formation and enhancement for the methanol oxidation.

    PubMed

    Yin, Zhen; Zhang, Yining; Chen, Kai; Li, Jing; Li, Wenjing; Tang, Pei; Zhao, Huabo; Zhu, Qingjun; Bao, Xinhe; Ma, Ding

    2014-03-10

    Monodispersed bimetallic PdAg nanoparticles can be fabricated through the emulsion-assisted ethylene glycol (EG) ternary system. Different compositions of bimetallic PdAg nanoparticles, Pd₈₀Ag₂₀, Pd₆₅Ag₃₅ and Pd₄₆Ag₅₄ can be obtained via adjusting the reaction parameters. For the formation process of the bimetallic PdAg nanoparticles, there have two-stage growth processes: firstly, nucleation and growth of the primary nanoclusters; secondly, formation of the secondary nanoparticles with the size-selection and relax process via the coalescence or aggregation of the primary nanoclusters. The as-prepared PdAg can be supported on the carbon black without any post-treatment, which exhibited high electro-oxidation activity towards methanol oxidation under alkaline media. More importantly, carbon-supported Pd₈₀Ag₂₀ nanoparticles reveal distinctly superior activities for the methanol oxidation, even if compared with commercial Pt/C electro-catalyst. It is concluded that the enhanced activity is dependant on the unique twinning structure with heterogeneous phase due to the dominating coalescence growth in EG ternary system.

  4. Enhanced formic acid electro-oxidation on PdIr nanoparticles prepared by ethylene glycol-assisted NaBH4 reduction process.

    PubMed

    Chen, Jinwei; Wang, Gang; Wang, Xueqin; Tian, Jing; Zhu, Shifu; Wang, Ruilin

    2013-10-01

    The carbon supported PdIr nanoparticles were synthesized by an ethylene glycol-assisted NaBH4 reduction method, and the mass ratio of Pd to Ir was optimized. Then, their performances for formic acid electro-oxidation (FAEO) were investigated. The XRD and TEM characterizations show that the prepared PdIr/C catalysts have small mean size and good dispersion of PdIr nanoparticles. The electrochemical measurements demonstrate that the PdIr/C catalysts have greatly enhanced performance for FAEO compared with the Pd/C catalyst. The PdIr/C catalysts show higher current density and more than 50 mV negative shift of onset and peak potential than that of the Pd/C catalyst. With the optimal mass ratio of Pd to Ir, the PdIr/C-5 catalyst presents the highest catalytic activity for FAEO.

  5. Polyethersulfone hollow fiber modified with poly(styrenesulfonate) and Pd nanoparticles for catalytic reaction

    NASA Astrophysics Data System (ADS)

    Emin, C.; Gu, Y.; Remigy, J.-C.; Lahitte, J.-F.

    2015-07-01

    The aim of this work is the synthesis of polymer-stabilized Pd nanoparticles (PdNP) inside a functionalized polymeric porous membrane in order to develop hybrid catalytic membrane reactors and to test them in model metal-catalyzed organic reactions. For this goal, a polymeric membrane support (Polyethersulfone hollow fiber-shaped) was firstly functionalized with an ionogenic polymer (i.e. poly(styrenesulfonate) capable to retain PdNP precursors using an UV photo-grafting method. PdNP were then generated inside the polymeric matrix by chemical reduction of precursor salts (intermatrix synthesis). The catalytic performance of the PdNP catalytic membranes was evaluated using reduction of nitrophenol by sodium borohydride (NaBH4) in water.

  6. Nanoparticles alloying in liquids: Laser-ablation-generated Ag or Pd nanoparticles and laser irradiation-induced AgPd nanoparticle alloying.

    PubMed

    Semaltianos, N G; Chassagnon, R; Moutarlier, V; Blondeau-Patissier, V; Assoul, M; Monteil, G

    2017-04-18

    Laser irradiation of a mixture of single-element micro/nanomaterials may lead to their alloying and fabrication of multi-element structures. In addition to the laser induced alloying of particulates in the form of micro/nanopowders in ambient atmosphere (which forms the basis of the field of additive manufacturing technology), another interesting problem is the laser-induced alloying of a mixture of single-element nanoparticles in liquids since this process may lead to the direct fabrication of alloyed-nanoparticle colloidal solutions. In this work, bare-surface ligand-free Ag and Pd nanoparticles in solution were prepared by laser ablation of the corresponding bulk target materials, separately in water. The two solutions were mixed and the mixed solution was laser irradiated for different time durations in order to investigate the laser-induced nanoparticles alloying in liquid. Nanoparticles alloying and the formation of AgPd alloyed nanoparticles takes place with a decrease of the intensity of the surface-plasmon resonance peak of the Ag nanoparticles (at ∼405 nm) with the irradiation time while the low wavelength interband absorption peaks of either Ag or Pd nanoparticles remain unaffected by the irradiation for a time duration even as long as 30 min. The nanoalloys have lattice constants with values between those of the pure metals, which indicates that they consist of Ag and Pd in an approximately 1:1 ratio similar to the atomic composition of the starting mixed-nanoparticle solution. Formation of nanoparticle networks consisting of bimetallic alloyed nanoparticles and nanoparticles that remain as single elements (even after the end of the irradiation), joining together, are also formed. The binding energies of the 3d core electrons of both Ag and Pd nanoparticles shift to lower energies with the irradiation time, which is also a typical characteristic of AgPd alloyed nanoparticles. The mechanisms of nanoparticles alloying and network formation are also

  7. Nanoparticles alloying in liquids: Laser-ablation-generated Ag or Pd nanoparticles and laser irradiation-induced AgPd nanoparticle alloying

    NASA Astrophysics Data System (ADS)

    Semaltianos, N. G.; Chassagnon, R.; Moutarlier, V.; Blondeau-Patissier, V.; Assoul, M.; Monteil, G.

    2017-04-01

    Laser irradiation of a mixture of single-element micro/nanomaterials may lead to their alloying and fabrication of multi-element structures. In addition to the laser induced alloying of particulates in the form of micro/nanopowders in ambient atmosphere (which forms the basis of the field of additive manufacturing technology), another interesting problem is the laser-induced alloying of a mixture of single-element nanoparticles in liquids since this process may lead to the direct fabrication of alloyed-nanoparticle colloidal solutions. In this work, bare-surface ligand-free Ag and Pd nanoparticles in solution were prepared by laser ablation of the corresponding bulk target materials, separately in water. The two solutions were mixed and the mixed solution was laser irradiated for different time durations in order to investigate the laser-induced nanoparticles alloying in liquid. Nanoparticles alloying and the formation of AgPd alloyed nanoparticles takes place with a decrease of the intensity of the surface-plasmon resonance peak of the Ag nanoparticles (at ∼405 nm) with the irradiation time while the low wavelength interband absorption peaks of either Ag or Pd nanoparticles remain unaffected by the irradiation for a time duration even as long as 30 min. The nanoalloys have lattice constants with values between those of the pure metals, which indicates that they consist of Ag and Pd in an approximately 1:1 ratio similar to the atomic composition of the starting mixed-nanoparticle solution. Formation of nanoparticle networks consisting of bimetallic alloyed nanoparticles and nanoparticles that remain as single elements (even after the end of the irradiation), joining together, are also formed. The binding energies of the 3d core electrons of both Ag and Pd nanoparticles shift to lower energies with the irradiation time, which is also a typical characteristic of AgPd alloyed nanoparticles. The mechanisms of nanoparticles alloying and network formation are also

  8. Thermal induced structural transformation of bimetallic AuPd nanoparticles

    NASA Astrophysics Data System (ADS)

    Bruma, A.; Li, Z. Y.

    2014-06-01

    High Angle Annular Dark Field Scanning Transmission Electron Microscope (HAADF-STEM) has been employed for the study of thermal effects of structural transformation of AuPd nanoparticles produced by physical vapour deposition. Depending on the duration of annealing at a temperature of 500 K, atomic resolved imaging analysis reveals the formation of various structure morphologies from the ordered L12 superlattice to the core-shell structure. The effects of Pd-oxides are also discussed.

  9. Photodeposited Pd Nanoparticles with Disordered Structure for Phenylacetylene Semihydrogenation

    NASA Astrophysics Data System (ADS)

    Fan, Qining; He, Sha; Hao, Lin; Liu, Xin; Zhu, Yue; Xu, Sailong; Zhang, Fazhi

    2017-02-01

    Developing effective heterogeneous metal catalysts with high selectivity and satisfactory activity for chemoselective hydrogenation of alkyne to alkene is of great importance in the chemical industry. Herein, we report our efforts to fabricate TiO2-supported Pd catalysts by a photodeposition method at room temperature for phenylacetylene semihydrogenation to styrene. The resulting Pd/TiO2 catalyst, possessing smaller Pd ensembles with ambiguous lattice fringes and more low coordination Pd sites, exhibits higher styrene selectivity compared to two contrastive Pd/TiO2 samples with larger ensembles and well-organized crystal structure fabricated by deposition-precipitation or photodeposition with subsequent thermal treatment at 300 °C. The sample derived from photodeposition exhibits greatly slow styrene hydrogenation in kinetic evaluation because the disordered structure of Pd particles in photodeposited Pd/TiO2 may prevent the formation of β-hydride phases and probably produce more surface H atoms, which may favor high styrene selectivity.

  10. Development of supported palladium particles in Pd/C catalysts

    SciTech Connect

    Semikolenov, V.A.; Lavrenko, S.P.; Zaikovskii, V.I.

    1994-07-01

    A series of Pd/C catalysts characterized by different morphology of supported Pd particles is prepared by deposition from aqueous H{sub 2}PdCl{sub 4} solutions. The development of palladium particles on the surface of a carbonaceous support is studied by high-resolution electron microscopy. Soluble Pd compounds are shown to be involved in the development of supported particles in the course of catalyst reduction. A scheme that accounts for the formation of round-shaped particles, grapelike clusters, and Pd microcrystallites is proposed.

  11. N-doped graphene-supported binary PdBi networks for formic acid oxidation

    NASA Astrophysics Data System (ADS)

    Xu, Hui; Yan, Bo; Zhang, Ke; Wang, Jin; Li, Shumin; Wang, Caiqin; Du, Yukou; Yang, Ping; Jiang, Shujuan; Song, Shaoqing

    2017-09-01

    As advanced electrodes for direct formic acid cells, nitrogen-doped graphene (NG) supported palladium-bismuth nanoparticles have been successfully fabricated through typical wet-chemical method. In studying the effects of NG support on PdBi nanoparticles for the electrooxidation of formic acid, we find that the as-prepared Pd1Bi1/NG network-like electrocatalysts exhibit much higher electrocatalytic activities than the Pd1Bi1/RGO, Pd1Bi1 and commercially available Pd/C catalysts in term of mass activity (1.69, 4.33 and 15.5times higher, respectively). The remarkably enhanced performances are associated with the electron transport between Bi and N, bi-functional effect between Pd, Bi and NG hybrids as well as the well-dispersed network-like structure on the surface of NG. The investigations of PdBi/NG in this work for promoting the electrocatalytic performances and the electron effect between Bi and N will accelerate the development for the field of direct formic acid fuel cells.

  12. Selective Oxidation of Glycerol over Carbon-Supported AuPd Catalysts

    SciTech Connect

    Ketchie,W.; Murayama, M.; Davis, R.

    2007-01-01

    Carbon-supported AuPd bimetallic nanoparticles were synthesized, characterized, and evaluated as catalysts in the aqueous-phase selective oxidation of glycerol. The bimetallic catalysts were synthesized by two different methods. The first method involved the deposition of Au onto the surface of 3-nm supported Pd particles by catalytic reduction of HAuCl{sub 4} in aqueous solution by H{sub 2}. The second method used the formation of a AuPd sol that was subsequently deposited onto a carbon support. Characterization of the catalysts using analytical transmission electron microscopy, H{sub 2} titration, and X-ray absorption spectroscopy at the Au L{sub III} and Pd K-edges confirmed that the first synthesis method successfully deposited Au onto the Pd particles. Results from the AuPd sol catalyst also revealed that Au was preferentially located on the surface. Measurement of glycerol oxidation rates (0.3 M glycerol, 0.6 M NaOH, 10 atm O{sub 2}, 333 K) in a semibatch reactor gave a turnover frequency (TOF) of 17 s{sup -1} for monometallic Au and 1 s{sup -1} for monometallic Pd, with Pd exhibiting a higher selectivity to glyceric acid. Although the activity of the bimetallic AuPd catalysts depended on the amount of Au present, none of them had a TOF greater than that of the monometallic Au catalyst. However, the AuPd catalysts had higher selectivity to glyceric acid compared with the monometallic Au. Because a physical mixture of monometallic Au and Pd catalysts also gave higher selectivity to glyceric acid, the Pd is proposed to catalyze the decomposition of the side product H{sub 2}O{sub 2} that is also formed over the Au but is detrimental to the selectivity toward glyceric acid.

  13. A pathway for the growth of core-shell Pt-Pd nanoparticles

    SciTech Connect

    Narula, Chaitanya Kumar; Yang, Xiaofan; Li, Chen; Pennycook, Stephen J; Lupini, Andrew R

    2015-10-12

    In this study, the aging of both Pt-Pd nanoparticles and core-shell Pt-Pd nanoparticles has been reported to result in alloying of Pt with Pd. In comparison to monometallic Pt catalysts, the growth of Pd-Pt bimetallics is slower; however, the mechanism of growth of particles and the mechanism by which Pd improves the hydrothermal durability of bimetallic Pd-Pt particles remains uncertain. In our work on hydrothermal aging of core-shell Pt-Pd nanoparticles, synthesized by solution methods, with varying Pd:Pt ratio of 1:4, 1:1, and 4:1, we compare the growth of core-shell Pt-Pd nanoparticles and find that particles grow by migrating and joining together. The unique feature of the observed growth is that Pd shells from both particles open up and join, allowing the cores to merge. At high temperatures, alloying occurs in good agreement with reports by other workers.

  14. Patchy multishell segregation in Pd-Pt alloy nanoparticles.

    PubMed

    Barcaro, Giovanni; Fortunelli, Alessandro; Polak, Micha; Rubinovich, Leonid

    2011-04-13

    Chemical ordering in face-centered-cubic-like PdPt nanoparticles consisting of 38-201 atoms is studied via density-functional calculations combined with a symmetry orbit approach. It is found that for larger particles in the Pd-rich regime, Pt atoms can segregate at the center of the nanoparticle (111) surface facets, in contrast with extended systems in which Pd is known to segregate at the surface of alloy planar surfaces. In a range of compositions around 1:1, a novel multishell chemical ordering pattern was favored, in which each shell is a patchwork of islands of atoms of the two elements, but the order of the patchwork is reversed in the alternating shells. These findings are rationalized in terms of coordination-dependent bond-energy variations in the metal-metal interactions, and their implications in terms of properties and applications of nanoscale alloy particles are discussed.

  15. Nitrogen-doped carbon-TiO2 composite as support of Pd electrocatalyst for formic acid oxidation

    NASA Astrophysics Data System (ADS)

    Qin, Yuan-Hang; Li, Yunfeng; Lam, Thomas; Xing, Yangchuan

    2015-06-01

    We report Pd nanoparticles supported on a composite consisting of oxide TiO2 and nitrogen-doped carbon for formic acid oxidation (FAO). The nitrogen-doped carbon-TiO2 (NCx-TiO2) composite support was prepared by a simple polymerization-pyrolysis process using commercial TiO2 nanoparticles (P25). Surface analysis showed that elements of Ti, C, O, and N were present on the composite surface, on which nitrogen existed in both pyridinic and quaternary forms. Pd nanoparticles with a mean size of ca. 4 nm were uniformly deposited on the composite via a polyol process. Electrochemical characterizations showed that the NCx-TiO2-supported Pd particles (Pd/NCx-TiO2) exhibited an electrocatalytic activity towards FAO that almost doubled that of the carbon black-supported Pd particles (Pd/C) with much enhanced electrocatalytic stability. The better performance of the composite supported Pd was attributed to a possible electronic structure modification in the metallic Pd particles and bifunctional effect produced by the NCx-TiO2 composite.

  16. Degradation photocatalysis of tetrodotoxin as a poison by gold doped PdO nanoparticles supported on reduced graphene oxide nanocomposites and evaluation of its antibacterial activity.

    PubMed

    Fakhri, Ali; Naji, Mahsa

    2017-02-01

    In this project, synthesis of pure and gold doped PdO-reduced graphene oxide nanocomposites by sonochemical and deposition-precipitation process was performed and characterized using X-ray diffraction (XRD), transmission electronic microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. The specific surface area of synthesized un-doped and Au doped PdO-RGO nanocomposites is 83.2, 109.1m(2)g(-1) and total pore volume is 0.31, 0.40cm(3)g(-1), respectively. With Tetrodotoxin as a target pollutant, photocatalytic system of UV+photocatalyst+H2O2 was set up. Some influencing parameters, including H2O2 dosage and initial pH value were investigated and the stability of the photocatalyst was also studied during the photocatalysis. The optimum values of operating parameters were found at an initial pH value of 5.0, a H2O2 dosage of 0.15mmol/L(-1) and photocatalyst dosage of 0.08g. Under the optimal conditions, the highest removal rate of Tetrodotoxin achieved 95%. Compared with the traditional photo-Fenton system, the UV+photocatalyst+H2O2 system can not only improve the degradation efficiency of Tetrodotoxin, but also reduce the dosage of H2O2 and thus reduce the processing cost. Antibacterial properties of un-doped and Au doped PdO-RGO nanocomposites were investigated by gram negative bacteria Escherichia coli and gram positive Staphylococcus aureus. The results showed that the antibacterial activity enhanced by Au PdO-RGO nanocomposites. Copyright © 2016 Elsevier B.V. All rights reserved.

  17. Electrocatalytic reduction of bromate based on Pd nanoparticles uniformly anchored on polyaniline/SBA-15.

    PubMed

    Sun, Chencheng; Deng, Ning; An, Hao; Cui, Hao; Zhai, Jianping

    2015-12-01

    A nano-composite electrocatalyst of Pd nanoparticles (Pd-NPs) anchored on polyaniline (PANI) supported by mesoporous SBA-15 (Pd-NPs/PANI/SBA-15), was synthesized using an in situ chemical method. Transmission electron microscopy showed that the Pd-NPs were homogeneously dispersed. Fourier-transform infrared and X-ray photoelectron spectroscopies confirmed that the Pd-NPs in the metallic state (Pd(0)) were predominantly immobilized on nitrogen sites in the PANI chains. The electrochemical performance of Pd-NPs/PANI/SBA-15 for electrocatalytic reduction of bromate (BrO3(-)) in an acidic medium was investigated by cyclic voltammetry (CV) and amperometric measurement. The reduction peak in the CV curves in the region 0.12 to -0.22V (vs. SCE) corresponded to response of BrO3(-) electroreduction, and the reduction peak current was well fitted linearly to the BrO3(-) concentration. It is proposed that the bromate ions diffuse to the Pd-NPs active sites and then the electrocatalytic reduction occurred with the H(+) doped in PANI. Furthermore, by amperometric measurement, Pd-NPs/PANI/SBA-15 showed relatively high sensitivity with respect to BrO3(-) concentration in the range of 8μmolL(-1) to 40mmolL(-1). Continuous CV for 200 cycles proved that Pd-NPs/PANI/SBA-15 had excellent electrocatalytic stability. These results show that Pd-NPs/PANI/SBA-15 is effective for electrocatalytic reduction of BrO3(-) and has great potential for the fabrication of BrO3(-) electrochemical sensor. Copyright © 2015 Elsevier Ltd. All rights reserved.

  18. Pt skin on Pd-Co-Zn/C ternary nanoparticles with enhanced Pt efficiency toward ORR

    NASA Astrophysics Data System (ADS)

    Xiao, Weiping; Zhu, Jing; Han, Lili; Liu, Sufen; Wang, Jie; Wu, Zexing; Lei, Wen; Xuan, Cuijuan; Xin, Huolin L.; Wang, Deli

    2016-08-01

    Exploring highly active, stable and relatively low-cost nanomaterials for the oxygen reduction reaction (ORR) is of vital importance for the commercialization of proton exchange membrane fuel cells (PEMFCs). Herein, a highly active, durable, carbon supported, and monolayer Pt coated Pd-Co-Zn nanoparticle is synthesized via a simple impregnation-reduction method, followed by spontaneous displacement of Pt. By tuning the atomic ratios, we obtain the composition-activity volcano curve for the Pd-Co-Zn nanoparticles and determined that Pd : Co : Zn = 8 : 1 : 1 is the optimal composition. Compared with pure Pd/C, the Pd8CoZn/C nanoparticles show a substantial enhancement in both the catalytic activity and the durability toward the ORR. Moreover, the durability and activity are further enhanced by forming a Pt skin on Pd8CoZn/C nanocatalysts. Interestingly, after 10 000 potential cycles in N2-saturated 0.1 M HClO4 solution, Pd8CoZn@Pt/C shows improved mass activity (2.62 A mg-1Pt) and specific activity (4.76 A m-2total), which are about 1.4 and 4.4 times higher than the initial values, and 37.4 and 5.5 times higher than those of Pt/C catalysts, respectively. After accelerated stability testing in O2-saturated 0.1 M HClO4 solution for 30 000 potential cycles, the half-wave potential negatively shifts about 6 mV. The results show that the Pt skin plays an important role in enhancing the activity as well as preventing degradation.Exploring highly active, stable and relatively low-cost nanomaterials for the oxygen reduction reaction (ORR) is of vital importance for the commercialization of proton exchange membrane fuel cells (PEMFCs). Herein, a highly active, durable, carbon supported, and monolayer Pt coated Pd-Co-Zn nanoparticle is synthesized via a simple impregnation-reduction method, followed by spontaneous displacement of Pt. By tuning the atomic ratios, we obtain the composition-activity volcano curve for the Pd-Co-Zn nanoparticles and determined that Pd : Co : Zn = 8

  19. Controlled decoration of Pd on Ni(OH)2 nanoparticles by atomic layer deposition for high ethanol oxidation activity

    NASA Astrophysics Data System (ADS)

    Jiang, Yiwu; Chen, Jinwei; Zhang, Jie; Zeng, Yaping; Wang, Yichun; Zhou, Feilong; Kiani, Maryam; Wang, Ruilin

    2017-10-01

    A new catalysts electrode was prepared by in situ controllable deposition of Pd shell layer on the gas diffusion layer (GDL) supported Ni(OH)2 nanoparticles using atomic layer deposition (ALD) technology. High resolution transmission electron microscope confirmed that the Ni(OH)2 core was coated by several atomic layers of Pd. The core-shell Ni(OH)2@Pd catalysts with different thickness of Pd shell are easily prepared by controlling ALD cycle. Electrochemical tests showed that the 100-Ni(OH)2@Pd/GDL catalyst prepared via 100 ALD cycles presented the highest catalytic activity for ethanol electro-oxidation reaction (EOR). The peaking current density of Ni(OH)2@Pd/GDL was 1439 mA mgPd-1, which was about 2.75 times as high as that of Pd/GDL (522 mA mgPd-1). The shift in binding energy of the XPS peak of Pd in Ni(OH)2@Pd catalyst confirmed the strong interaction between the Pd shell and the Ni(OH)2 core. We suggested that the high catalytic activity of Ni(OH)2@Pd/GDL catalyst layer may be due to following factors: high Pd dispersion arising from the core-shell structure, high Pd utilization because of the in situ deposition of Pd on catalyst layer and the interaction between the Pd shell and the Ni(OH)2 core. Herein, the ALD technology exhibits a promising application prospect for preparing core-shell structure and precisely controlling shell thickness of nano-composite as an electro-catalyst toward EOR.

  20. Pd-Pt and Fe-Ni nanoparticles formed by covalent molecular assembly in supercritical carbon dioxide.

    PubMed

    Puniredd, Sreenivasa Reddy; Weiyi, Seah; Srinivasan, M P

    2008-04-01

    We report the formation of Pd-Pt nanoparticles within a dendrimer-laden ultrathin film matrix immobilized on a solid support and constructed by covalent layer-by-layer (LbL) assembly using supercritical carbon dioxide (SCCO2) as the processing medium. Particle size distribution and composition were controlled by precursor composition. The precursor compositions are optimized for Pd-Pt nanoparticles and later extended to the formation of Fe-Ni nanoparticles. As an example of the application of nanoparticles in tribology, Fe-Ni nanoparticle-laden films were observed to exhibit better tribological properties than those containing the monometallic species, thereby suggesting that combination of nanoparticles can be used to derive greater benefits.

  1. Highly dispersed Pd nanoparticles on chemically modified graphene with aminophenyl groups for formic acid oxidation

    NASA Astrophysics Data System (ADS)

    Yang, Su-Dong; Shen, Cheng-Min; Tong, Hao; He, Wei; Zhang, Xiao-Gang; Gao, Hong-Jun

    2011-11-01

    A novel electrode material based on chemically modified graphene (CMG) with aminophenyl groups is covalently functionalized by a nucleophilic ring-opening reaction between the epoxy groups of graphene oxide and the aminophenyl groups of p-phenylenediamine. Palladium nanoparticles with an average diameter of 4.2 nm are deposited on the CMG by a liquid-phase borohydride reduction. The electrocatalytic activity and stability of the Pd/CMG composite towards formic acid oxidation are found to be higher than those of reduced graphene oxide and commercial carbon materials such as Vulcan XC-72 supported Pd electrocatalysts.

  2. Support Morphology-Dependent Catalytic Activity of Pd/CeO₂ for Formaldehyde Oxidation.

    PubMed

    Tan, Hongyi; Wang, Jin; Yu, Shuzhen; Zhou, Kebin

    2015-07-21

    To eliminate indoor formaldehyde (HCHO) pollution, Pd/CeO2 catalysts with different morphologies of ceria support were employed. The palladium nanoparticles loaded on {100}-faceted CeO2 nanocubes exhibited much higher activity than those loaded on {111}-faceted ceria nanooctahedrons and nanorods (enclosed by {100} and {111} facets). The HCHO could be fully converted into CO2 over the Pd/CeO2 nanocubes at a GHSV of 10,000 h(-1) and a HCHO inlet concentration of 600 ppm at ambient temperature. The prepared catalysts were characterized by a series of techniques. The HRTEM, ICP-MS and XRD results confirmed the exposed facets of the ceria and the sizes (1-2 nm) of the palladium nanoparticles with loading amounts close to 1%. According to the Pd 3d XPS and H2-TPR results, the status of the Pd-species was dependent on the morphologies of the supports. The {100} facets of ceria could maintain the metallic Pd species rather than the {111} facets, which promoted HCHO catalytic combustion. The Raman and O 1s XPS results revealed that the nanorods with more defect sites and oxygen vacancies were responsible for the easy oxidation of the Pd-species and low catalytic activity.

  3. Heterostructured Au/Pd-M (M = Au, Pd, Pt) nanoparticles with compartmentalized composition, morphology, and electrocatalytic activity.

    PubMed

    Lutz, Patrick S; Bae, In-Tae; Maye, Mathew M

    2015-10-14

    The synthesis, processing, and galvanic exchange of three heterostructured nanoparticle systems is described. The surface accessibility and redox potential of a Au/Pd-Ag dumbbell nanoparticle, where a Au/Pd core/shell region, and a silver region make up the domains, was used to prepare the new nanostructures with controlled composition, morphology, and microstructure. Results indicate that the silver domain was particularly susceptible to galvanic displacement, and was exchanged to Au/Pd-M (M = Au, Pd, Pt). Interestingly, the dumbbell morphology remained after exchange, and the silver region was transformed to hollow, parachute, or concentric domains respectively. The morphology and microstructure change was visualized via TEM and HRTEM, and the composition changes were probed via STEM-EDS imaging and XPS. The electrocatalytic activity of the Au/Pd-M towards methanol oxidation was studied, with results indicating that the Au/Pd-Pt nanoparticles had high activity attributed to the porous nature of the platinum domains.

  4. Synthesis and assembly of Pd nanoparticles on graphene for enhanced electrooxidation of formic acid

    NASA Astrophysics Data System (ADS)

    Jin, Tao; Guo, Shaojun; Zuo, Jing-Lin; Sun, Shouheng

    2012-12-01

    Monodisperse 4.5 nm Pd nanoparticles (NPs) were synthesized by solution phase reduction of palladium acetylacetonate with morpholine borane in a mixture of oleylamine and 1-octadecene. These NPs were assembled on graphene uniformly in the form of a monolayer, and showed much enhanced catalysis for electrooxidation of formic acid. The work demonstrates the great potential of graphene as a support to enhance NP catalysis and stability for important chemical oxidation reactions.Monodisperse 4.5 nm Pd nanoparticles (NPs) were synthesized by solution phase reduction of palladium acetylacetonate with morpholine borane in a mixture of oleylamine and 1-octadecene. These NPs were assembled on graphene uniformly in the form of a monolayer, and showed much enhanced catalysis for electrooxidation of formic acid. The work demonstrates the great potential of graphene as a support to enhance NP catalysis and stability for important chemical oxidation reactions. Electronic supplementary information (ESI) available. See DOI: 10.1039/c2nr33060a

  5. Enhanced electroactivity of Pd nanocrystals supported on H3PMo12O40/carbon for formic acid electrooxidation

    NASA Astrophysics Data System (ADS)

    Zhao, Xiao; Zhu, Jianbing; Liang, Liang; Liu, Changpeng; Liao, Jianhui; Xing, Wei

    2012-07-01

    The preparation of highly dispersed precious metal catalysts is an important subject for fuel cell applications. Here, using a phosphomolybdic acid (PMo12)-assisted method, a Pd-PMo12/C catalyst with uniform Pd nanoparticles is prepared. The TEM results show that the presence of PMo12 facilitates the formation of uniform Pd particles with an average particle size of 3.2 nm. More importantly, the Pd-PMo12/C catalyst displays an enhanced activity and stability for formic acid electro-oxidation and a better tolerance toward CO poisoning than Pd nanocatalysts prepared with sodium citrate as a stabilizer. A combination of the composition and structure analyses show that the reasons for the improved electro-catalytic activity of the Pd-PMo12/C catalyst involve the metal-support interaction, the richer Pd oxide/hydrous oxide content and the inherent properties of PMo12.

  6. Synthesis and assembly of Pd nanoparticles on graphene for enhanced electrooxidation of formic acid.

    PubMed

    Jin, Tao; Guo, Shaojun; Zuo, Jing-lin; Sun, Shouheng

    2013-01-07

    Monodisperse 4.5 nm Pd nanoparticles (NPs) were synthesized by solution phase reduction of palladium acetylacetonate with morpholine borane in a mixture of oleylamine and 1-octadecene. These NPs were assembled on graphene uniformly in the form of a monolayer, and showed much enhanced catalysis for electrooxidation of formic acid. The work demonstrates the great potential of graphene as a support to enhance NP catalysis and stability for important chemical oxidation reactions.

  7. Highly efficient hydrogen generation from methanolysis of ammonia borane on CuPd alloy nanoparticles

    NASA Astrophysics Data System (ADS)

    Li, Pengyao; Xiao, Zhengli; Liu, Zhaoyan; Huang, Jiale; Li, Qingbiao; Sun, Daohua

    2015-01-01

    A low-cost and facile route has been developed for the synthesis of monodisperse CuPd nanoparticles with tunable composition. (Scanning transmission electron microscopy-energy-dispersive x-ray spectroscopy) STEM-EDX results verified the structure of the alloy for the obtained nanoparticles. These CuPd nanoparticles supported on carbon were active catalysts for hydrogen generation from the methanolysis of ammonia borane (AB) at room temperature, and their activities were closely related with the compositions. Cu48Pd52 NPs exhibited the highest activity among the tested catalysts. Moreover, their activity can be further improved by thermal annealing at 300 °C under nitrogen flow, with a very high total turnover frequency value of 53.2 min-1. The reusability test indicated that the Cu48Pd52/C catalyst retains 86% of its initial activity and 100% conversion after 8 cycles. The catalyst, which features lost cost and high efficiency, may help move forward the practical application of AB as a sustainable hydrogen storage material.

  8. Enhanced ethanol electro-oxidation reaction on carbon supported Pd-metal oxide electrocatalysts.

    PubMed

    Abdel Hameed, R M

    2017-11-01

    Various Pd-metal oxide/C electrocatalysts were fabricated using ethylene glycol as a reducing agent in modified microwave-assisted polyol process. The crystal structure and surface morphology were studied using X-ray diffraction and transmission electron microscopy. All prepared Pd-metal oxide/C electrocatalysts exhibited a shift of Pd diffraction planes in the positive direction in relation to that of Pd/C. Highly dispersed palladium nanoparticles were formed on different metal oxide/C supports. The electrocatalytic performance of these electrocatalysts for ethanol oxidation was examined in NaOH solution using cyclic voltammetry, chronoamperometry and electrochemical impedance spectroscopy. An improvement in electrochemical parameters including onset potential, oxidation current density and If/Ib values was recorded at different Pd-metal oxide/C electrocatalysts, especially Pd-NiO/C. Three folds increment in steady state oxidation current density value was also displayed by investigated Pd-metal oxide/C electrocatalysts when contrasted to that of Pd/C to reflect their enhanced stability behavior. Copyright © 2017 Elsevier Inc. All rights reserved.

  9. Counting electrons on supported nanoparticles.

    PubMed

    Lykhach, Yaroslava; Kozlov, Sergey M; Skála, Tomáš; Tovt, Andrii; Stetsovych, Vitalii; Tsud, Nataliya; Dvořák, Filip; Johánek, Viktor; Neitzel, Armin; Mysliveček, Josef; Fabris, Stefano; Matolín, Vladimír; Neyman, Konstantin M; Libuda, Jörg

    2016-03-01

    Electronic interactions between metal nanoparticles and oxide supports control the functionality of nanomaterials, for example, the stability, the activity and the selectivity of catalysts. Such interactions involve electron transfer across the metal/support interface. In this work we quantify this charge transfer on a well-defined platinum/ceria catalyst at particle sizes relevant for heterogeneous catalysis. Combining synchrotron-radiation photoelectron spectroscopy, scanning tunnelling microscopy and density functional calculations we show that the charge transfer per Pt atom is largest for Pt particles of around 50 atoms. Here, approximately one electron is transferred per ten Pt atoms from the nanoparticle to the support. For larger particles, the charge transfer reaches its intrinsic limit set by the support. For smaller particles, charge transfer is partially suppressed by nucleation at defects. These mechanistic and quantitative insights into charge transfer will help to make better use of particle size effects and electronic metal-support interactions in metal/oxide nanomaterials.

  10. 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.

  11. Pt skin on Pd-Co-Zn/C ternary nanoparticles with enhanced Pt efficiency toward ORR.

    PubMed

    Xiao, Weiping; Zhu, Jing; Han, Lili; Liu, Sufen; Wang, Jie; Wu, Zexing; Lei, Wen; Xuan, Cuijuan; Xin, Huolin L; Wang, Deli

    2016-08-21

    Exploring highly active, stable and relatively low-cost nanomaterials for the oxygen reduction reaction (ORR) is of vital importance for the commercialization of proton exchange membrane fuel cells (PEMFCs). Herein, a highly active, durable, carbon supported, and monolayer Pt coated Pd-Co-Zn nanoparticle is synthesized via a simple impregnation-reduction method, followed by spontaneous displacement of Pt. By tuning the atomic ratios, we obtain the composition-activity volcano curve for the Pd-Co-Zn nanoparticles and determined that Pd : Co : Zn = 8 : 1 : 1 is the optimal composition. Compared with pure Pd/C, the Pd8CoZn/C nanoparticles show a substantial enhancement in both the catalytic activity and the durability toward the ORR. Moreover, the durability and activity are further enhanced by forming a Pt skin on Pd8CoZn/C nanocatalysts. Interestingly, after 10 000 potential cycles in N2-saturated 0.1 M HClO4 solution, Pd8CoZn@Pt/C shows improved mass activity (2.62 A mg(-1)Pt) and specific activity (4.76 A m(-2)total), which are about 1.4 and 4.4 times higher than the initial values, and 37.4 and 5.5 times higher than those of Pt/C catalysts, respectively. After accelerated stability testing in O2-saturated 0.1 M HClO4 solution for 30 000 potential cycles, the half-wave potential negatively shifts about 6 mV. The results show that the Pt skin plays an important role in enhancing the activity as well as preventing degradation.

  12. Development of ferromagnetism in Pd nanoparticles with reduction in size

    NASA Astrophysics Data System (ADS)

    Seehra, Mohindar; Rall, James; Liu, J.; Roberts, C.

    2009-03-01

    Bulk fcc Pd is a paramagnet just missing the Stoner criterion for ferromagnetism (N(EF)I > 1) [1]. Several groups have reported weak ferromagnetism in 2-4 nm Pd nanoparticles (NPs) [2]. We report systematic development of weak ferromagnetism in Pd NPs with reduction in size. Magnetic measurements (M vs. T) are compared for bulk Pd with those of size D 50nm, 7nm, and 6nm. The samples of size D = 7 nm and 6 nm were prepared by an aqueous seed-mediated growth and characterized by TEM and x-ray diffraction with the latter showing expansion of the lattice with decrease in size. Compared with the low-field magnetic susceptibility χ of bulk Pd, χ for the 7 and 6 nm NPs are enhanced by an order of magnitude. For the 50 nm NPs, χ follows nearly the Curie law. The hysteresis loops (M vs. H) for the 7 and 6 nm NPs shows a decrease in coercivity and remanence from 2K to 300K suggesting TC> 300K. Origin of this ferromagnetism in terms of surface magnetism and lattice expansion is discussed. [1] W. Gerhardt et al, Phys. Rev. B 24, 6744 (1981); [2] T. Shinohara et al, Phys. Rev. B 91, 197201 (2003); Jeon et al, J. Appl. Phys. 103, 09413 (2008); Litran et al, Phys. Rev. B 73, 054404 (2006).

  13. Catalytic reduction of 4-nitrophenol over Ni-Pd nanodimers supported on nitrogen-doped reduced graphene oxide.

    PubMed

    Liu, Lijun; Chen, Ruifen; Liu, Weikai; Wu, Jiamin; Gao, Di

    2016-12-15

    Catalytic reduction of toxic 4-nitrophenol to 4-aminophenol over magnetically recoverable nanocatalysts has attracted much attention. Herein, we report a Ni-Pd/NrGO catalyst through the growth of Ni-Pd nanodimers (NDs) on nitrogen-doped reduced graphene oxide (NrGO). The Ni-Pd NDs show a heterogeneous nanostructure with Ni and Pd subparts contacting with each other, remarkably different from the frequently-observed core/shell nanoparticles (NPs) or nanoalloy. The formation of Ni-Pd NDs follows an initial deposition of Pd NPs on the graphene and in-situ catalytic generation of Ni subparts over the newly-generated Pd NPs. The resulting Ni-Pd/NrGO exhibits a superior catalytic activity towards the reduction of 4-nitrophenol at room temperature with a high rate constant (3400s(-1)g(-1)) and a low activated energy (29.1kJmol(-1)) as compared to unsupported Ni-Pd NDs and supported monometallic catalysts. The conversion rate of 4-NP is calculated to be 99.5% and the percent yield (%) of 4-AP is as high as 99.1%. A synergistic catalysis mechanism is rationally proposed, which is ascribed to the electronic modification of Ni-Pd metals due to the strong metal/support interaction (SMSI) effect as well as the electron transfer between Ni and Pd. The hybrid catalyst shows soft ferromagnetic properties and can be magnetically separated and recycled without obvious loss of activity.

  14. Structure and magnetism in Fe/FexPd1-x core/shell nanoparticles formed by alloying in Pd-embedded Fe nanoparticles.

    PubMed

    Baker, S H; Lees, M; Roy, M; Binns, C

    2013-09-25

    We have investigated atomic structure and magnetism in Fe nanoparticles with a diameter of 2 nm embedded in a Pd matrix. The samples for these studies were prepared directly from the gas phase by co-deposition, using a gas aggregation source and an MBE-type source for the Fe nanoparticles and Pd matrix respectively. Extended absorption fine structure (EXAFS) measurements indicate that there is an appreciable degree of alloying at the nanoparticle/matrix interface; at dilute nanoparticle concentrations, more than half of the Fe atoms are alloyed with Pd. This leads to a core/shell structure in the embedded nanoparticles, with an FexPd1-x shell surrounding a reduced pure Fe core. Magnetism in the nanocomposite samples was probed by means of magnetometry measurements, which were interpreted in the light of their atomic structure. These point to a magnetized cloud of Pd atoms surrounding the embedded nanoparticles which is significantly larger than around single Fe atoms in Pd. The coercivities in the Fe/Pd nanocomposite samples are larger than in FexPd1-x atomic alloys of corresponding composition, which is consistent with exchange coupling between the magnetically harder and softer regions in the nanocomposite samples.

  15. Photodeposited Pd Nanoparticles with Disordered Structure for Phenylacetylene Semihydrogenation

    PubMed Central

    Fan, Qining; He, Sha; Hao, Lin; Liu, Xin; Zhu, Yue; Xu, Sailong; Zhang, Fazhi

    2017-01-01

    Developing effective heterogeneous metal catalysts with high selectivity and satisfactory activity for chemoselective hydrogenation of alkyne to alkene is of great importance in the chemical industry. Herein, we report our efforts to fabricate TiO2-supported Pd catalysts by a photodeposition method at room temperature for phenylacetylene semihydrogenation to styrene. The resulting Pd/TiO2 catalyst, possessing smaller Pd ensembles with ambiguous lattice fringes and more low coordination Pd sites, exhibits higher styrene selectivity compared to two contrastive Pd/TiO2 samples with larger ensembles and well-organized crystal structure fabricated by deposition-precipitation or photodeposition with subsequent thermal treatment at 300 °C. The sample derived from photodeposition exhibits greatly slow styrene hydrogenation in kinetic evaluation because the disordered structure of Pd particles in photodeposited Pd/TiO2 may prevent the formation of β-hydride phases and probably produce more surface H atoms, which may favor high styrene selectivity. PMID:28176843

  16. Two-stage melting of Au-Pd nanoparticles.

    PubMed

    Mejía-Rosales, Sergio J; Fernandez-Navarro, Carlos; Pérez-Tijerina, Eduardo; Montejano-Carrizales, Juan Martín; José-Yacamán, Miguel

    2006-07-06

    Several series of molecular dynamics runs were performed to simulate the melting transition of bimetallic cuboctahedral nanoparticles of gold-palladium at different relative concentrations to study their structural properties before, in, and after the transition. The simulations were made in the canonical ensemble, each series covering a range of temperatures from 300 to 980 K, using the Rafii-Tabar version of the Sutton and Chen interatomic potential for metallic alloys. We found that the melting transition temperature has a strong dependence on the relative concentrations of the atomic species. We also found that, previous to the melting transition, the outer layer of the nanoparticle gets disordered in what can be thought as a premelting stage, where Au atoms near the surface migrate to the surface and remain there after the particle melts as a whole. The melting of the surface below Tm is consistent with studies of the interaction of a TEM electron beam with Au and Au-Pd nanoparticles.

  17. One-Pot Synthesis of Hierarchical Flower-Like Pd-Cu Alloy Support on Graphene Towards Ethanol Oxidation.

    PubMed

    Zhang, Jingyi; Feng, Anni; Bai, Jie; Tan, Zhibing; Shao, Wenyao; Yang, Yang; Hong, Wenjing; Xiao, Zongyuan

    2017-09-02

    The synergetic effect of alloy and morphology of nanocatalysts play critical roles towards ethanol electrooxidation. In this work, we developed a novel electrocatalyst fabricated by one-pot synthesis of hierarchical flower-like palladium (Pd)-copper (Cu) alloy nanocatalysts supported on reduced graphene oxide (Pd-Cu(F)/RGO) for direct ethanol fuel cells. The structures of the catalysts were characterized by using scanning electron microscopy (SEM), transmission electron microscope (TEM), X-ray diffraction (XRD), and X-ray photoelectron spectrometer (XPS). The as-synthesized Pd-Cu(F)/RGO nanocatalyst was found to exhibit higher electrocatalytic performances towards ethanol electrooxidation reaction in alkaline medium in contrast with RGO-supported Pd nanocatalyst and commercial Pd black catalyst in alkaline electrolyte, which could be attributed to the formation of alloy and the morphology of nanoparticles. The high performance of nanocatalyst reveals the great potential of the structure design of the supporting materials for the future fabrication of nanocatalysts.

  18. One-Pot Synthesis of Hierarchical Flower-Like Pd-Cu Alloy Support on Graphene Towards Ethanol Oxidation

    NASA Astrophysics Data System (ADS)

    Zhang, Jingyi; Feng, Anni; Bai, Jie; Tan, Zhibing; Shao, Wenyao; Yang, Yang; Hong, Wenjing; Xiao, Zongyuan

    2017-09-01

    The synergetic effect of alloy and morphology of nanocatalysts play critical roles towards ethanol electrooxidation. In this work, we developed a novel electrocatalyst fabricated by one-pot synthesis of hierarchical flower-like palladium (Pd)-copper (Cu) alloy nanocatalysts supported on reduced graphene oxide (Pd-Cu(F)/RGO) for direct ethanol fuel cells. The structures of the catalysts were characterized by using scanning electron microscopy (SEM), transmission electron microscope (TEM), X-ray diffraction (XRD), and X-ray photoelectron spectrometer (XPS). The as-synthesized Pd-Cu(F)/RGO nanocatalyst was found to exhibit higher electrocatalytic performances towards ethanol electrooxidation reaction in alkaline medium in contrast with RGO-supported Pd nanocatalyst and commercial Pd black catalyst in alkaline electrolyte, which could be attributed to the formation of alloy and the morphology of nanoparticles. The high performance of nanocatalyst reveals the great potential of the structure design of the supporting materials for the future fabrication of nanocatalysts.

  19. Support and Oxidation Effects on Subnanometer Palladium Nanoparticles

    DOE PAGES

    Heard, Christopher J.; Vajda, Stefan; Johnston, Roy L.

    2014-01-30

    The effect of cluster size, oxidation state, and the support upon the structures and energetics of subnanometer palladium nanoparticles is investigated within a density functional framework. Gas phase global minima of Pd-4 and Pd-10 along with their suboxide counterparts are determined using a genetic algorithm and deposited upon MgO (001) and a high-index alumina surface. It is observed that there is an oxidation-dependent transition in the smaller clusters from three-dimensional to two-dimensional structures both in the gas phase and when supported by a surface. MgO strongly promotes a change from tetrahedral- and icosahedral-based structures toward cubic forms, while alumina inducesmore » significant distortion of the cluster and the breaking of Pd-Pd bonds. Increased oxygenation contributes cooperatively to these effects, causing disruption of the Pd-Pd bond network, favoring the incorporation of oxygen into the cluster structure, further complicating unambiguous structure prediction.« less

  20. 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

  1. Identifying low-coverage surface species on supported noble metal nanoparticle catalysts by DNP-NMR.

    PubMed

    Johnson, Robert L; Perras, Frédéric A; Kobayashi, Takeshi; Schwartz, Thomas J; Dumesic, James A; Shanks, Brent H; Pruski, Marek

    2016-01-31

    DNP-NMR spectroscopy has been applied to enhance the signal for organic molecules adsorbed on γ-Al2O3-supported Pd nanoparticle catalysts. By offering >2500-fold time savings, the technique enabled the observation of (13)C-(13)C cross-peaks for low coverage species, which were assigned to products from oxidative degradation of methionine adsorbed on the nanoparticle surface.

  2. A highly active Pd-P nanoparticle electrocatalyst for enhanced formic acid oxidation synthesized via stepwise electroless deposition.

    PubMed

    Poon, Kee Chun; Khezri, Bahareh; Li, Yao; Webster, Richard D; Su, Haibin; Sato, Hirotaka

    2016-02-28

    A highly active Pd-P nanoparticle electrocatalyst for formic acid oxidation was synthesized using NaH2PO2 as the reducing agent. The Pd-P nanoparticles were amorphous and exhibited higher specific and mass activity values compared to commercial Pd/C electrocatalyts and reported literature values. Furthermore, the Pd-P nanoparticles were found to be more durable than Pd/C electrocatalyts.

  3. Electrodeposition of Pd Nanowires and Nanorods on Carbon Nanoparticles

    SciTech Connect

    Bliznakov, S.; Vukmirovic, M.; Sutter, E.; Adzic, R.

    2011-06-01

    We report on the method for synthesizing palladium nanowires and nanorods involving the electrodeposition on oxidized amorphous carbon nanoparticles from chloride containing solutions. The effect of the deposition overpotential and the concentration of palladium ions on the morphology of the Pd electrodeposits have been established. Palladium grows predominately in the shape of nanowires if electrodeposited at potentials in the H underpotential deposition potential (UPD) range, where chloride ions are adsorbed only at the edges of nucleated monolayer-thick clusters on the carbon surface. The effect of the concentration of palladium ions on deposits morphology is also discussed. The mechanism of electrodeposition of Pd nanowires and nanorods in the H UPD potential range has been proposed.

  4. Linear polystyrene-stabilized PdO nanoparticle-catalyzed Mizoroki-Heck reactions in water.

    PubMed

    Ohtaka, Atsushi; Yamaguchi, Tomohiro; Teratani, Takuto; Shimomura, Osamu; Nomura, Ryôki

    2011-10-27

    Linear polystyrene-stabilized PdO nanoparticles (PS-PdONPs) were prepared by thermal decomposition of Pd(OAc)(2) in the presence of polystyrene. X-ray diffraction (XRD) and transmission electron microscopy (TEM) indicated the production of PdO nanoparticles. The loading of palladium was determined by inductively coupled plasma-atomic emission spectroscopy (ICP-AES). PS-PdONPs exhibited high catalytic activity for Mizoroki-Heck reactions under air in water and could be recycled without loss of activity.

  5. Palladium nanoparticles supported on titanium doped graphitic carbon nitride for formic acid dehydrogenation.

    PubMed

    Wu, Yongmei; Wen, Meicheng; Navlani-García, Miriam; Kuwahara, Yasutaka; Mori, Kohsuke; Yamashita, Hiromi

    2017-02-28

    Pd nanoparticles (NPs) supported on Ti-doped graphitic carbon nitride (g-C₃N₄) were synthetised by a deposition-precipitation route and a subsequent reduction with NaBH₄. The features of Pd supported Ti-doped g-C₃N₄ were studied by XRD, TEM, FT-IR, XPS, EXAFS and N₂ physisorption measurements. It was found that the NPs had an average size of 2.9 nm and presented a high dispersion on the surface of Ti-doped g-C₃N₄. Compared with Pd loaded on pristine g-C₃N₄, Pd NPs supported Ti-doped g-C₃N₄ catalyst exhibited a high activity in formic acid dehydrogenation in water at room temperature. The enhanced activity can be attributed to the small Pd NPs size as well as the strong interaction between Pd NPs and Ti-doped g-C₃N₄.

  6. Water-soluble Pd nanoparticles capped with glutathione: synthesis, characterization, and magnetic properties.

    PubMed

    Sharma, Sachil; Kim, Bit; Lee, Dongil

    2012-11-13

    The synthesis, characterization, and magnetic properties of water-soluble Pd nanoparticles capped with glutathione are described. The glutathione-capped Pd nanoparticles were synthesized under argon and air atmospheres at room temperature. Whereas the former exhibits a bulklike lattice parameter, the lattice parameter of the latter is found to be considerably greater, indicating anomalous lattice expansion. Comparative structural and compositional studies of these nanoparticles suggest the presence of oxygen in the core lattice when Pd nanoparticles are prepared under an air atmosphere. Both Pd nanoparticles prepared under argon and air show ferromagnetism at 5 K, but the latter exhibits significantly greater coercivity (88 Oe) and magnetization (0.09 emu/g at 50 kOe). The enhanced ferromagnetic properties are explained by the electronic effect of the incorporated oxygen that increases the 4d density of holes at the Pd site and localizes magnetic moments.

  7. The influence of N-doped carbon materials on supported Pd: enhanced hydrogen storage and oxygen reduction performance.

    PubMed

    Kong, Xiang-Kai; Chen, Qian-Wang; Lun, Zheng-Yan

    2014-02-03

    N-doped graphene has become an important support for Pd in both hydrogen storage and catalytic reactions. The molecular orbitals of carbon materials (including graphene, fullerene, and small carbon clusters) and those of the supported Pd species will hybrid much stronger as N dopants are introduced, owing to the increased electrostatic attraction at the interface. This enhances the carbon substrates' catching force for the supported Pd, preventing its leaching and aggregation in many practical applications. The better dispersion and stabilization of Pd nanoparticles, which are induced by various carbon supports with N-doping, are pleasing to us and could increase their efficiency and facilitate their recycling during various reaction processes in several fields. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Chemical and structural properties of Pd nanoparticle-decorated graphene-Electron spectroscopic methods and QUASES

    NASA Astrophysics Data System (ADS)

    Lesiak, B.; Jiricek, P.; Bieloshapka, I.

    2017-05-01

    Graphite (Gr) and carbon nanomaterials such as graphene oxide (GO) and reduced graphene oxide (RGO) and those decorated with Pd nanoparticles were investigated by photoelectron spectroscopy (XPS) aided with Quantitative Analysis of Surfaces by Electron Spectroscopy (QUASES) and reflected electron energy loss spectroscopy (REELS). Oxidation of Gr decreased the C/O ratio from 10 (Gr) to 2.2 (GO), whereas reduction of GO by N2H4 increased this ratio to 6.6 (RGO) due to decreasing number of oxygen groups (hydroxyl, epoxy, carbonyl and hydroxyl). Graphene materials and those after Pd decoration had 6-11 average number of layers in stacked nanostructures. Pd decoration using NaBH4-reducing agents formed nanoparticles of size 6.9 nm (Pd/Gr) > 5.3 nm (Pd/RGO) > 4.25 nm (Pd/GO), with PdOx overlayer thickness of 2.20 nm (Pd/GO) > 1.42 nm (Pd/Gr) > 1.20 nm (Pd/RGO), decreased number of oxygen groups and average number of layers. Smaller Pd nanoparticles of larger PdOx overlayer thickness were observed on highly hydrophilic substrates (functional oxygen groups content). Decoration accompanied by reduction using NaBH4 led to the removal of water attached by hydrogen bonding to graphene interplanes and the formation of PdOx overlayer from oxygen functional groups. Nanoparticle size obtained from QUASES was confirmed by Pd 3d5/2 spectra binding energy and full-width at half maximum. Various chemistry and mechanisms of graphene reduction using N2H4 and NaBH4 were observed, where NaBH4 was more efficient to remove water bonded by hydrogen bonding to oxygen groups and thus further graphene exfoliation. A substantial influence of substrate, functional group content on nanoparticle coverage, size and Pd oxide overlayer thickness was observed.

  9. Cyanogel-derived N-doped C nanosheets immobilizing Pd-P nanoparticles: One-pot synthesis and enhanced hydrogenation catalytic performance

    NASA Astrophysics Data System (ADS)

    Zhang, Hao; Yan, Xiaohong; Huang, Yundi; Zhang, Mengru; Tang, Yawen; Sun, Dongmei; Xu, Lin; Wei, Shaohua

    2017-02-01

    For Pd-based nanocatalysts, stabilization of Pd nanoparticles on carbon support could not only effectively avoid particle aggregation and maintain catalytic stability during catalytic processes, but also facilitate enhancing the catalytic activity due to the synergy between Pd nanoparticles and carbon support. Furthermore, the incorporation of non-metal of phosphorus (P) into Pd could effectively modulate the electronic structure of Pd and thus help to boost the catalytic properties. However, one-pot synthesis of such nanohybrids remains a great challenge due to the distinct physiochemical properties of Pd, P and C components. Herein, we demonstrate a one-pot and scalable synthesis of highly dispersed PdP alloy nanoparticle-immobilized on N-doped graphitic carbon nanosheets (abbreviated as Pd-P@N-C nanosheets) by using inorganic-organic hybrid cyanogel as a reaction precursor. In virtue of both compositional and structural advantages, the as-synthesized Pd-P@N-C nanosheets manifest a superior catalytic activity and stability toward the hydrogenation of 4-nitrophenol (4-NP). We believe that the present work will provide a feasible and versatile strategy for the development of efficient catalysts for environmental remediation and can also be extendable to other carbon-based nanohybrids with desirable functionalities.

  10. Coalescence-induced crystallisation wave in Pd nanoparticles

    PubMed Central

    Grammatikopoulos, Panagiotis; Cassidy, Cathal; Singh, Vidyadhar; Sowwan, Mukhles

    2014-01-01

    Palladium nanoparticles offer an attractive alternative to bulk palladium for catalysis, hydrogen storage and gas sensing applications. Their performance depends strongly on surface structure; therefore, nanoparticle coalescence can play an important role, as it determines the resultant structure of the active sites where reactions (e.g. catalysis) actually take place, i.e. facets, edges, vertices or protrusions. With this in mind, we performed classical molecular dynamics (MD) simulations and magnetron-sputtering inert gas condensation depositions of palladium nanoparticles, supported by high-resolution transmission electron microscopy (HRTEM), to study the mechanisms that govern their coalescence. Surface energy minimisation drove the interactions initially, leading to the formation of an interface/neck, as expected. Intriguingly, at a later stage, atomic rearrangements triggered a crystallisation wave propagating through the amorphous nanoparticles, leading to mono- or polycrystalline fcc structures. In the case of crystalline nanoparticles, almost-epitaxial alignment occurred and the formation of twins and surface protrusions were observed. PMID:25047807

  11. Coalescence-induced crystallisation wave in Pd nanoparticles.

    PubMed

    Grammatikopoulos, Panagiotis; Cassidy, Cathal; Singh, Vidyadhar; Sowwan, Mukhles

    2014-07-22

    Palladium nanoparticles offer an attractive alternative to bulk palladium for catalysis, hydrogen storage and gas sensing applications. Their performance depends strongly on surface structure; therefore, nanoparticle coalescence can play an important role, as it determines the resultant structure of the active sites where reactions (e.g. catalysis) actually take place, i.e. facets, edges, vertices or protrusions. With this in mind, we performed classical molecular dynamics (MD) simulations and magnetron-sputtering inert gas condensation depositions of palladium nanoparticles, supported by high-resolution transmission electron microscopy (HRTEM), to study the mechanisms that govern their coalescence. Surface energy minimisation drove the interactions initially, leading to the formation of an interface/neck, as expected. Intriguingly, at a later stage, atomic rearrangements triggered a crystallisation wave propagating through the amorphous nanoparticles, leading to mono- or polycrystalline fcc structures. In the case of crystalline nanoparticles, almost-epitaxial alignment occurred and the formation of twins and surface protrusions were observed.

  12. Microbial synthesis of bimetallic PdPt nanoparticles for catalytic reduction of 4-nitrophenol.

    PubMed

    Tuo, Ya; Liu, Guangfei; Dong, Bin; Yu, Huali; Zhou, Jiti; Wang, Jing; Jin, Ruofei

    2017-02-01

    Bimetallic nanoparticles are generally believed to have improved catalytic activity and stability due to geometric and electronic changes. In this work, biogenic-Pd (bio-Pd), biogenic-Pt (bio-Pt), and biogenic-PdPt (bio-PdPt) nanoparticles were synthesized by Shewanella oneidensis MR-1 in the absence or presence of quinone. Compared with direct microbial reduction process, the addition of anthraquinone-2,6-disulfonate (AQDS) could promote the reduction efficiency of Pd(II) or/and Pt(IV) and result in decrease of particles size. All kinds of nanoparticles could catalyze 4-nitrophenol reduction by NaBH4 and their catalytic activities took the following order: bio-PdPt (AQDS) ∼ bio-PdPt > bio-Pd (AQDS) > bio-Pd > bio-Pt (AQDS) ∼ bio-Pt. Moreover, the bio-PdPt (AQDS) nanoparticles could be reused for 6 cycles. We believe that this simple and efficient biosynthesis approach for synthesizing bimetallic bio-PdPt nanocatalysts is important for preparing active and stable catalysts.

  13. Heterostructured Au/Pd-M (M = Au, Pd, Pt) nanoparticles with compartmentalized composition, morphology, and electrocatalytic activity

    NASA Astrophysics Data System (ADS)

    Lutz, Patrick S.; Bae, In-Tae; Maye, Mathew M.

    2015-09-01

    The synthesis, processing, and galvanic exchange of three heterostructured nanoparticle systems is described. The surface accessibility and redox potential of a Au/Pd-Ag dumbbell nanoparticle, where a Au/Pd core/shell region, and a silver region make up the domains, was used to prepare the new nanostructures with controlled composition, morphology, and microstructure. Results indicate that the silver domain was particularly susceptible to galvanic displacement, and was exchanged to Au/Pd-M (M = Au, Pd, Pt). Interestingly, the dumbbell morphology remained after exchange, and the silver region was transformed to hollow, parachute, or concentric domains respectively. The morphology and microstructure change was visualized via TEM and HRTEM, and the composition changes were probed via STEM-EDS imaging and XPS. The electrocatalytic activity of the Au/Pd-M towards methanol oxidation was studied, with results indicating that the Au/Pd-Pt nanoparticles had high activity attributed to the porous nature of the platinum domains.The synthesis, processing, and galvanic exchange of three heterostructured nanoparticle systems is described. The surface accessibility and redox potential of a Au/Pd-Ag dumbbell nanoparticle, where a Au/Pd core/shell region, and a silver region make up the domains, was used to prepare the new nanostructures with controlled composition, morphology, and microstructure. Results indicate that the silver domain was particularly susceptible to galvanic displacement, and was exchanged to Au/Pd-M (M = Au, Pd, Pt). Interestingly, the dumbbell morphology remained after exchange, and the silver region was transformed to hollow, parachute, or concentric domains respectively. The morphology and microstructure change was visualized via TEM and HRTEM, and the composition changes were probed via STEM-EDS imaging and XPS. The electrocatalytic activity of the Au/Pd-M towards methanol oxidation was studied, with results indicating that the Au/Pd-Pt nanoparticles had

  14. Core-shell Au@Pd nanoparticles with enhanced catalytic activity for oxygen reduction reaction via core-shell Au@Ag/Pd constructions

    PubMed Central

    Chen, Dong; Li, Chengyin; Liu, Hui; Ye, Feng; Yang, Jun

    2015-01-01

    Core-shell nanoparticles often exhibit improved catalytic properties due to the lattice strain created in these core-shell particles. Herein, we demonstrate the synthesis of core-shell Au@Pd nanoparticles from their core-shell Au@Ag/Pd parents. This strategy begins with the preparation of core-shell Au@Ag nanoparticles in an organic solvent. Then, the pure Ag shells are converted into the shells made of Ag/Pd alloy by galvanic replacement reaction between the Ag shells and Pd2+ precursors. Subsequently, the Ag component is removed from the alloy shell using saturated NaCl solution to form core-shell Au@Pd nanoparticles with an Au core and a Pd shell. In comparison with the core-shell Au@Pd nanoparticles upon directly depositing Pd shell on the Au seeds and commercial Pd/C catalysts, the core-shell Au@Pd nanoparticles via their core-shell Au@Ag/Pd templates display superior activity and durability in catalyzing oxygen reduction reaction, mainly due to the larger lattice tensile effect in Pd shell induced by the Au core and Ag removal. PMID:26144550

  15. Atomic Layer Deposition of Pd Nanoparticles on TiO₂ Nanotubes for Ethanol Electrooxidation: Synthesis and Electrochemical Properties.

    PubMed

    Assaud, Loïc; Brazeau, Nicolas; Barr, Maïssa K S; Hanbücken, Margrit; Ntais, Spyridon; Baranova, Elena A; Santinacci, Lionel

    2015-11-11

    Palladium nanoparticles are grown on TiO2 nanotubes by atomic layer deposition (ALD), and the resulting three-dimensional nanostructured catalysts are studied for ethanol electrooxidation in alkaline media. The morphology, the crystal structure, and the chemical composition of the Pd particles are fully characterized using scanning and transmission electron microscopies, X-ray diffraction, and X-ray photoelectron spectroscopy. The characterization revealed that the deposition proceeds onto the entire surface of the TiO2 nanotubes leading to the formation of well-defined and highly dispersed Pd nanoparticles. The electrooxidation of ethanol on Pd clusters deposited on TiO2 nanotubes shows not only a direct correlation between the catalytic activity and the particle size but also a steep increase of the response due to the enhancement of the metal-support interaction when the crystal structure of the TiO2 nanotubes is modified by annealing at 450 °C in air.

  16. Interfacial electronic structure and ion beam induced effect of anatase TiO 2 surface modified by Pd nanoparticles

    NASA Astrophysics Data System (ADS)

    Sohn, Youngku

    2010-12-01

    Anatase TiO 2 surface could be modified by Pd nanoparticles using an electrochemical deposition method. Surface morphology, light absorption and interfacial electronic structures were studied by field emission scanning electron microscopy (FE-SEM), UV-visible reflectance absorption, X-ray diffraction (XRD) crystallography, and depth-profiling X-ray photoelectron spectroscopy (XPS). On the basis of XRD patterns, Pd 3d XPS and valance band spectra, the as-deposited overlayer Pd is metallic, with no detectable Pd oxides. The optical band gap of TiO 2 decreases from 3.25 to 3.14 eV upon Pd deposition. The XPS spectra with Ar + ion sputtering show that 4+ oxidation state of Ti dramatically changes to lower (3+ and 2+) oxidation states. As a result of this, oxygen defects are created in the bulk while the oxygen diffuses outward to likely form hydroxyl group on the surface. The Pd 3d XPS peak shifts by +0.6 eV to a higher BE position, and the density of state at the Fermi level is more or less reduced. It appears that the overlayer Pd becomes less metallic, plausibly due to TiO 2 support and/or size effect. No critical interfacial interaction between Pd and TiO 2 was observed by XPS.

  17. A pathway for the growth of core-shell Pt-Pd nanoparticles

    DOE PAGES

    Narula, Chaitanya Kumar; Yang, Xiaofan; Li, Chen; ...

    2015-10-12

    In this study, the aging of both Pt-Pd nanoparticles and core-shell Pt-Pd nanoparticles has been reported to result in alloying of Pt with Pd. In comparison to monometallic Pt catalysts, the growth of Pd-Pt bimetallics is slower; however, the mechanism of growth of particles and the mechanism by which Pd improves the hydrothermal durability of bimetallic Pd-Pt particles remains uncertain. In our work on hydrothermal aging of core-shell Pt-Pd nanoparticles, synthesized by solution methods, with varying Pd:Pt ratio of 1:4, 1:1, and 4:1, we compare the growth of core-shell Pt-Pd nanoparticles and find that particles grow by migrating and joiningmore » together. The unique feature of the observed growth is that Pd shells from both particles open up and join, allowing the cores to merge. At high temperatures, alloying occurs in good agreement with reports by other workers.« less

  18. Composition and size dependence of hydrogen interaction with carbon supported bulk-immiscible Pd-Rh nanoalloys.

    PubMed

    Oumellal, Yassine; Provost, Karine; Ghimbeu, Camelia Matei; de Yuso, Alicia Martinez; Zlotea, Claudia

    2016-11-18

    In-depth clarification of hydrogen interaction with noble metal nanoparticles and nanoalloys is essential for further development and design of efficient catalysts and hydrogen storage nanomaterials. This issue becomes even more challenging for nanoalloys of bulk-immiscible metals. The hydrogen interaction with bulk-immiscible Pd-Rh nanoalloys (3-6 nm) supported on mesoporous carbon is studied by both laboratory and large scale facility techniques. X-ray diffraction (XRD) reveals a single phase fcc structure for all nanoparticles confirming the formation of nanoalloys in the whole composition range. In situ extended x-ray absorption fine structure (EXAFS) experiments suggest segregated local structures into Pd-rich surface and Rh-rich core coexisting within the nanoparticles. Hydrogen sorption can be tuned by chemical composition: Pd-rich nanoparticles form a hydride phase, whereas Rh-rich phases do not absorb hydrogen under ambient temperature and pressure conditions. The thermodynamics of hydride formation can be tailored by the composition without affecting hydrogen capacity at full hydrogenation. Furthermore, for hydrogen absorbing nanoalloys, in situ EXAFS reveals a preferential occupation of hydrogen for the interstitial sites around Pd atoms. To our knowledge, this is the first study providing insights into the hydrogen interaction mechanism with Pd-Rh nanoalloys that can guide the design of catalysts for hydrogenation reactions and the development of nanomaterials for hydrogen storage.

  19. Composition and size dependence of hydrogen interaction with carbon supported bulk-immiscible Pd-Rh nanoalloys

    NASA Astrophysics Data System (ADS)

    Oumellal, Yassine; Provost, Karine; Matei Ghimbeu, Camelia; Martinez de Yuso, Alicia; Zlotea, Claudia

    2016-11-01

    In-depth clarification of hydrogen interaction with noble metal nanoparticles and nanoalloys is essential for further development and design of efficient catalysts and hydrogen storage nanomaterials. This issue becomes even more challenging for nanoalloys of bulk-immiscible metals. The hydrogen interaction with bulk-immiscible Pd-Rh nanoalloys (3-6 nm) supported on mesoporous carbon is studied by both laboratory and large scale facility techniques. X-ray diffraction (XRD) reveals a single phase fcc structure for all nanoparticles confirming the formation of nanoalloys in the whole composition range. In situ extended x-ray absorption fine structure (EXAFS) experiments suggest segregated local structures into Pd-rich surface and Rh-rich core coexisting within the nanoparticles. Hydrogen sorption can be tuned by chemical composition: Pd-rich nanoparticles form a hydride phase, whereas Rh-rich phases do not absorb hydrogen under ambient temperature and pressure conditions. The thermodynamics of hydride formation can be tailored by the composition without affecting hydrogen capacity at full hydrogenation. Furthermore, for hydrogen absorbing nanoalloys, in situ EXAFS reveals a preferential occupation of hydrogen for the interstitial sites around Pd atoms. To our knowledge, this is the first study providing insights into the hydrogen interaction mechanism with Pd-Rh nanoalloys that can guide the design of catalysts for hydrogenation reactions and the development of nanomaterials for hydrogen storage.

  20. Cytotoxicity of Pd nanostructures supported on PEN: Influence of sterilization on Pd/PEN interface.

    PubMed

    Polívková, M; Siegel, J; Rimpelová, S; Hubáček, T; Kolská, Z; Švorčík, V

    2017-01-01

    Non-conventional antimicrobial agents, such as palladium nanostructures, have been increasingly used in the medicinal technology. However, experiences uncovering their harmful and damaging effects to human health have begun to appear. In this study, we have focused on in vitro cytotoxicity assessment of Pd nanostructures supported on a biocompatible polymer. Pd nanolayers of variable thicknesses (ranging from 1.1 to 22.4nm) were sputtered on polyethylene naphthalate (PEN). These nanolayers were transformed by low-temperature post-deposition annealing into discrete nanoislands. Samples were characterized by AFM, XPS, ICP-MS and electrokinetic analysis before and after annealing. Sterilization of samples prior to cytotoxicity testing was done by UV irradiation, autoclave and/or ethanol. Among the listed sterilization techniques, we have chosen the gentlest one which had minimal impact on sample morphology, Pd dissolution and overall Pd/PEN interface quality. Cytotoxic response of Pd nanostructures was determined by WST-1 cell viability assay in vitro using three model cell lines: mouse macrophages (RAW 264.7) and two types of mouse embryonic fibroblasts (L929 and NIH 3T3). Finally, cell morphology in response to Pd/PEN was evaluated by means of fluorescence microscopy. Copyright © 2016 Elsevier B.V. All rights reserved.

  1. Electrocatalytic oxidation of hydrazine and hydroxylamine by graphene oxide-Pd nanoparticle-modified glassy carbon electrode.

    PubMed

    Lee, Eunhee; Kim, Daekun; You, Jung-Min; Kim, Seul Ki; Yun, Mira; Jeon, Seungwon

    2012-12-01

    Pd nanoparticle catalysts supported by thiolated graphene oxide (tGO) on a glassy carbon electrode (GCE), and denoted as tGO-Pd/GCE, are used in this study for the electrochemical determination of hydroxylamine and hydrazine. The physicochemical properties of tGO-Pd were characterized by transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and electrochemical impedance spectroscopy (EIS). They showed strong catalytic activity toward the oxidation of hydroxylamine and hydrazine. Cyclic voltammetry (CV) and amperometry were used to characterize the sensors' performances. The detection limits of hydroxylamine and hydrazine by tGO-Pd/GCE were 0.31 and 0.25 microM (s/n = 3), respectively. The sensors' sensitivity, selectivity, and stability were also investigated.

  2. Carbon-Supported Pd and PdFe Alloy Catalysts for Direct Methanol Fuel Cell Cathodes

    PubMed Central

    Rivera Gavidia, Luis M.; Sebastián, David; Pastor, Elena; Aricò, Antonino S.; Baglio, Vincenzo

    2017-01-01

    Direct methanol fuel cells (DMFCs) are electrochemical devices that efficiently produce electricity and are characterized by a large flexibility for portable applications and high energy density. Methanol crossover is one of the main obstacles for DMFC commercialization, forcing the search for highly electro-active and methanol tolerant cathodes. In the present work, carbon-supported Pd and PdFe catalysts were synthesized using a sodium borohydride reduction method and physico-chemically characterized using transmission electron microscopy (TEM) and X-ray techniques such as photoelectron spectroscopy (XPS), diffraction (XRD) and energy dispersive spectroscopy (EDX). The catalysts were investigated as DMFC cathodes operating at different methanol concentrations (up to 10 M) and temperatures (60 °C and 90 °C). The cell based on PdFe/C cathode presented the best performance, achieving a maximum power density of 37.5 mW·cm−2 at 90 °C with 10 M methanol, higher than supported Pd and Pt commercial catalysts, demonstrating that Fe addition yields structural changes to Pd crystal lattice that reduce the crossover effects in DMFC operation. PMID:28772937

  3. Carbon-Supported Pd and PdFe Alloy Catalysts for Direct Methanol Fuel Cell Cathodes.

    PubMed

    Rivera Gavidia, Luis M; Sebastián, David; Pastor, Elena; Aricò, Antonino S; Baglio, Vincenzo

    2017-05-25

    Direct methanol fuel cells (DMFCs) are electrochemical devices that efficiently produce electricity and are characterized by a large flexibility for portable applications and high energy density. Methanol crossover is one of the main obstacles for DMFC commercialization, forcing the search for highly electro-active and methanol tolerant cathodes. In the present work, carbon-supported Pd and PdFe catalysts were synthesized using a sodium borohydride reduction method and physico-chemically characterized using transmission electron microscopy (TEM) and X-ray techniques such as photoelectron spectroscopy (XPS), diffraction (XRD) and energy dispersive spectroscopy (EDX). The catalysts were investigated as DMFC cathodes operating at different methanol concentrations (up to 10 M) and temperatures (60 °C and 90 °C). The cell based on PdFe/C cathode presented the best performance, achieving a maximum power density of 37.5 mW·cm(-2) at 90 °C with 10 M methanol, higher than supported Pd and Pt commercial catalysts, demonstrating that Fe addition yields structural changes to Pd crystal lattice that reduce the crossover effects in DMFC operation.

  4. In-situ deposition of Pd nanoparticles on tubular halloysite template for initiation of metallization.

    PubMed

    Fu, Yubin; Zhang, Lide; Zheng, Jiyong

    2005-04-01

    Halloysite template has a tubular microstructure; its wall has a multi-layer aluminosilicate structure. A new catalytic method is adopted here, through the in-situ reduction of Pd ions on the surface of tubular halloysite by methanol to initiate electroless plating; the detailed deposition features of Pd nanoparticles are investigated for the first time. The results indicate that an in-situ reduction and deposition of Pd occurs at room temperature, in which the halloysite template plays an important role. Impurities in halloysite (such as ferric oxide) influence the formation and distribution of the Pd nanoparticles. The Pd nanoparticles are of a non-spherical shape in most cases, which would be caused by the irregular appearance of halloysite. No intercalation of the nanoparticles occurs between the aluminosilicate layers in the halloysite. The diameter of Pd nanoparticles increases with time; the average diameter ranges from 1 nm to 4 nm. Pd nanoparticles on a halloysite template can catalyze electroless deposition of Ni to prepare a novel nano-sized cermet at low cost. This practicable catalytic method could also be used on other clay substrates for the initiation of metallization.

  5. Pd Nanoparticles Coupled to WO2.72 Nanorods for Enhanced Electrochemical Oxidation of Formic Acid.

    PubMed

    Xi, Zheng; Erdosy, Daniel P; Mendoza-Garcia, Adriana; Duchesne, Paul N; Li, Junrui; Muzzio, Michelle; Li, Qing; Zhang, Peng; Sun, Shouheng

    2017-04-12

    We synthesize a new type of hybrid Pd/WO2.72 structure with 5 nm Pd nanoparticles (NPs) anchored on 50 × 5 nm WO2.72 nanorods. The strong Pd/WO2.72 coupling results in the lattice expansion of Pd from 0.23 to 0.27 nm and the decrease of Pd surface electron density. As a result, the Pd/WO2.72 shows much enhanced catalysis toward electrochemical oxidation of formic acid in 0.1 M HClO4; it has a mass activity of ∼1600 mA/mgPd in a broad potential range of 0.4-0.85 V (vs RHE) and shows no obvious activity loss after a 12 h chronoamperometry test at 0.4 V. Our work demonstrates an important strategy to enhance Pd NP catalyst efficiency for energy conversion reactions.

  6. Leading Learning: Theorizing Principals' Support for Teacher PD in Ontario

    ERIC Educational Resources Information Center

    Hardy, Ian J.

    2010-01-01

    This paper describes and theorizes principals' support for teacher professional development ("PD") during a time of strong provincial pressure for an increased focus upon literacy, numeracy, and improvements in standardized test scores in elementary schools in Ontario, Canada. The paper draws upon semi-structured interviews with 12…

  7. A sensitive bisphenol A voltammetric sensor relying on AuPd nanoparticles/graphene composites modified glassy carbon electrode.

    PubMed

    Su, Bingyuan; Shao, Huilin; Li, Na; Chen, Xiaomei; Cai, Zhixiong; Chen, Xi

    2017-05-01

    In this work, a sensitive bisphenol A (BPA) electrochemical sensor was assembled using a surfactant-free AuPd nanoparticles-loaded graphene nanosheets (AuPdNPs/GNs) modified electrode. The AuPdNPs monodispersed on GNs were successfully prepared by the spontaneous redox reaction between bimetallic precursors and GNs. Because no surfactant or halide ions were involved in the proposed synthesis, the prepared composite was enabled to directly modify a glassy carbon electrode without any pre-treatments. Moreover, due to the synergetic effect of Au and Pd, AuPdNPs/GNs displayed high electrochemical activity with well-defined voltammetric peaks of BPA oxidation and lower overpotential compared with monometallic PdNPs and AuNPs supported GNs. According to the results of differential pulse voltammetry (DPV), under optimized conditions, a good linear response was observed for the concentration of BPA in the range of 0.05-10μM with a detection limit of 8nM. The developed electrochemical sensor was successfully applied to determine BPA in food package. This study indicated that AuPdNPs/GNs based electrochemical sensor can be a promising and reliable tool for rapid analysis of emergency pollution affairs of BPA.

  8. Vibrational spectroscopy of cinnamaldehyde on graphite and supported Pd islands

    NASA Astrophysics Data System (ADS)

    Grimaud, C.-M.; Radosavkic, D.; Ustaze, S.; Palmer, R. E.

    2001-07-01

    We report the first experimental study of the adsorption of cinnamaldehyde on surfaces under ultra high vacuum (UHV) conditions. Cinnamaldehyde is an α,β-unsaturated aldehyde with important applications in the fine chemicals sector. High-resolution electron energy loss spectroscopy (HREELS) is employed to investigate the vibrational modes of cinnamaldehyde condensed on graphite at 100 K and absorbed on the surface of a Pd islands film (supported on graphite), also at 100 K. In the case of the Pd film, we find strong evidence for a parallel orientation of the phenyl ring consistent with theoretical calculations.

  9. Solid phase metallurgy strategy to sub-5 nm Au-Pd and Ni-Pd bimetallic nanoparticles with controlled redox properties.

    PubMed

    Tang, Yu; Xu, Shaodan; Dai, Yihu; Yan, Xiaoqing; Li, Renhong; Xiao, Liping; Fan, Jie

    2014-01-07

    A solid phase metallurgy strategy is applied to synthesize Au-Pd and Ni-Pd bimetallic nanoparticles (BMNPs) with a tight sub-5 nm particle size distribution. The near-surface elemental composition and redox properties of Au-Pd BMNPs can be well tailored, which leads to an optimized catalytic performance in n-hexane combustion.

  10. Predicting catalyst-support interactions between metal nanoparticles and amorphous silica supports

    NASA Astrophysics Data System (ADS)

    Ewing, Christopher S.; Veser, Götz; McCarthy, Joseph J.; Lambrecht, Daniel S.; Johnson, J. Karl

    2016-10-01

    Metal-support interactions significantly affect the stability and activity of supported catalytic nanoparticles (NPs), yet there is no simple and reliable method for estimating NP-support interactions, especially for amorphous supports. We present an approach for rapid prediction of catalyst-support interactions between Pt NPs and amorphous silica supports for NPs of various sizes and shapes. We use density functional theory calculations of 13 atom Pt clusters on model amorphous silica supports to determine linear correlations relating catalyst properties to NP-support interactions. We show that these correlations can be combined with fast discrete element method simulations to predict adhesion energy and NP net charge for NPs of larger sizes and different shapes. Furthermore, we demonstrate that this approach can be successfully transferred to Pd, Au, Ni, and Fe NPs. This approach can be used to quickly screen stability and net charge transfer and leads to a better fundamental understanding of catalyst-support interactions.

  11. Carbon Nano Tube Supported Pd Catalyst: Effect of Support Textual Properties with Pre-Treatment Method of Pd Particle.

    PubMed

    Ryu, Young Bok; Kim, Ji Sun; Baek, Jae Ho; Kim, Myung Hwan; Kim, Yangdo; Lee, Man Sig

    2015-11-01

    The aim of this work is to be compared the effect of supports textural properties with pre-treatment method on dispersion of Pd particle. The CNTs were functionalized by different concentration of acid in order to obtain materials with different chemical and physical properties. The characteristics of functionalized CNTs were investigated by FT-IR and Rama spectropy. The Pd/CNTs catalysts prepared on support having the different surface properties were characterized by XRD, FE-TEM and CO-chemisorption. When pretreated 8M concentration, the CNTs has the highest amount of oxygen functional group and ID/IG ratio, in this study. Pd/CNT8M has high dispersion and small particle size. From these results, we confirmed that characteristics of Pd/CNTs catalyst such as particle size and dispersion of Pd are influenced by density of oxygen functional group and disorder of CNTs. And we have observed that acid treatment concentration of 8M is sufficient to functionalize the CNTs by introducing -COOH group of CNTs surfaces.

  12. Shape-directional growth of Pt and Pd nanoparticles

    NASA Astrophysics Data System (ADS)

    Leong, G. Jeremy; Ebnonnasir, Abbas; Schulze, Maxwell C.; Strand, Matthew B.; Ngo, Chilan; Maloney, David; Frisco, Sarah L.; Dinh, Huyen N.; Pivovar, Bryan; Gilmer, George H.; Kodambaka, Suneel; Ciobanu, Cristian V.; Richards, Ryan M.

    2014-09-01

    The design and synthesis of shape-directed nanoscale noble metal particles have attracted much attention due to their enhanced catalytic properties and the opportunities to study fundamental aspects of nanoscale systems. As such, numerous methods have been developed to synthesize crystals with tunable shapes, sizes, and facets by adding foreign species that promote or restrict growth on specific sites. Many hypotheses regarding how and why certain species direct growth have been put forward, however there has been no consensus on a unifying mechanism of nanocrystal growth. Herein, we develop and demonstrate the capabilities of a mathematical growth model for predicting metal nanoparticle shapes by studying a well known procedure that employs AgNO3 to produce {111} faceted Pt nanocrystals. The insight gained about the role of auxiliary species is then utilized to predict the shape of Pd nanocrystals and to corroborate other shape-directing syntheses reported in literature. The fundamental understanding obtained herein by combining modeling with experimentation is a step toward computationally guided syntheses and, in principle, applicable to predictive design of the growth of crystalline solids at all length scales (nano to bulk).The design and synthesis of shape-directed nanoscale noble metal particles have attracted much attention due to their enhanced catalytic properties and the opportunities to study fundamental aspects of nanoscale systems. As such, numerous methods have been developed to synthesize crystals with tunable shapes, sizes, and facets by adding foreign species that promote or restrict growth on specific sites. Many hypotheses regarding how and why certain species direct growth have been put forward, however there has been no consensus on a unifying mechanism of nanocrystal growth. Herein, we develop and demonstrate the capabilities of a mathematical growth model for predicting metal nanoparticle shapes by studying a well known procedure that

  13. Bimetallic PdAg nanoparticle arrays from monolayer films of diblock copolymer micelles

    NASA Astrophysics Data System (ADS)

    Ehret, E.; Beyou, E.; Mamontov, G. V.; Bugrova, T. A.; Prakash, S.; Aouine, M.; Domenichini, B.; Cadete Santos Aires, F. J.

    2015-07-01

    The self-assembly technique provides a highly efficient route to generate well-ordered structures on a nanometer scale. In this paper, well-ordered arrays of PdAg alloy nanoparticles on flat substrates with narrow distributions of particle size (6-7 nm) and interparticle spacing (about 60 nm) were synthesized by the block copolymer micelle approach. A home-made PS-b-P4VP diblock copolymer was prepared to obtain a micellar structure in toluene. Pd and Ag salts were then successfully loaded in the micellar core of the PS-b-P4VP copolymer. A self-assembled monolayer of the loaded micelles was obtained by dipping the flat substrate in the solution. At this stage, the core of the micelles was still loaded with the metal precursor rather than with a metal. Physical and chemical reducing methods were used to reduce the metal salts embedded in the P4VP core into PdAg nanoparticles. HRTEM and EDX indicated that Pd-rich PdAg alloy nanoparticles were synthesized by chemical or physical reduction; UV-visible spectroscopy observations confirmed that metallic PdAg nanoparticles were quickly formed after chemical reduction; XPS measurements revealed that the PdAg alloy nanoparticles were in a metallic state after a short time of exposure to O2 plasma and after hydrazine reduction.

  14. Surface enhanced Raman scattering of pyridine adsorbed on Au@Pd core/shell nanoparticles

    NASA Astrophysics Data System (ADS)

    Yang, Zhilin; Li, Yan; Li, Zhipeng; Wu, Deyin; Kang, Junyong; Xu, Hongxing; Sun, Mengtao

    2009-06-01

    Surface enhanced Raman scattering (SERS) of pyridine adsorbed on Au@Pd core/shell nanoparticles has been investigated theoretically with quantum chemical method, generalized Mie theory and three-dimensional finite-difference time domain (3D-FDTD) method. We first studied the influence of the coated Pd on the electronic structure of Au nanoparticle, and compared the electronic structure of Au20 cluster with that of Au10Pd10 (core/shell) cluster. Second, we studied SERS spectroscopy of pyridine on Au@Pd core/shell nanoparticles, which revealed the rate of static chemical enhancement and electromagnetic enhancement in the experimental reports. Third, the influence of the Pd shell thickness to the optical absorption of Au@Pd core/shell nanoparticles was investigated with generalized Mie theory. Fourth, we studied the influence of the shell thickness to the local electric field enhancement with 3D-FDTD method. The theoretical results reveal that the static chemical enhancement and electromagnetic enhancement are in the order of 10 and 103, respectively. These theoretical studies promote the deeper understanding of the electronic structure and optical absorption properties of Au@Pd, and the mechanisms for SERS of molecule adsorbed on Au@Pd.

  15. Fabrication of Au–Pd nanoparticles/graphene oxide and their excellent catalytic performance

    SciTech Connect

    He, Yongqiang; Zhang, Nana; Zhang, Lei; Gong, Qiaojuan; Yi, Maocong; Wang, Wei; Qiu, Haixia; Gao, Jianping

    2014-03-01

    Graphical abstract: - Highlights: • Au and Pd nanoparticles loaded on GO were fabricated without adding any reducing agents. • The Au–Pd NPs/GO were excellent catalysts for the reduction of 4-nitrophenol. • The Au–Pd NPs/GO showed superior catalytic activity for the Suzuki reaction. • The Au–Pd NPs/GO exhibit good reusability. - Abstract: A simple method to fabricate clean Au–Pd nanoparticles on graphene oxide (Au–Pd NPs/GO) without using any reducing agent or surfactant has been developed. GO simultaneously reduced the Au and Pd precursors to form a stable suspension of the Au–Pd NPs/GO. The nanoparticles were characterized by transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy and inductively coupled plasma. The Au–Pd NPs/GO exhibited catalytic activity for the reduction of 4-nitrophenol to 4-aminophenol and for the Suzuki–Miyaura coupling reaction of chlorobenzene and phenylboronic acid in aqueous media.

  16. Sulfonation of ordered mesoporous carbon supported Pd catalysts for formic acid electrooxidation.

    PubMed

    Sun, Zhi-Peng; Zhang, Xiao-Gang; Tong, Hao; Liang, Yan-Yu; Li, Hu-Lin

    2009-09-15

    A novel supporting material containing benzenesulfonic acid (BSA) groups and ordered mesoporous carbons (OMCs) was first prepared by in situ radical polymerization of 4-styrenesulfonate and isoamyl nitrite under ambient conditions. Then, Pd nanoparticles were deposited on as-produced OMCs (f-OMCs) by the NaBH(4) reduction method. The structure and nature of the resulting composites were characterized by transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), and nitrogen adsorption-desorption. The results show that BSA groups are created and the texture and surface chemistry are altered, whereas the ordered porous structure is maintained. The electrocatalytic properties of the Pd/f-OMCs catalysts for formic acid oxidation (HCOOH) have been investigated by cyclic voltammetry and chronoamperometry methods, and excellent electrocatalytic activity can be observed.

  17. Perpendicular magnetic anisotropy in granular multilayers of CoPd alloyed nanoparticles

    NASA Astrophysics Data System (ADS)

    Vivas, L. G.; Rubín, J.; Figueroa, A. I.; Bartolomé, F.; García, L. M.; Deranlot, C.; Petroff, F.; Ruiz, L.; González-Calbet, J. M.; Pascarelli, S.; Brookes, N. B.; Wilhelm, F.; Chorro, M.; Rogalev, A.; Bartolomé, J.

    2016-05-01

    Co-Pd multilayers obtained by Pd capping of pre-deposited Co nanoparticles on amorphous alumina are systematically studied by means of high-resolution transmission electron microscopy, x-ray diffraction, extended x-ray absorption fine structure, SQUID-based magnetometry, and x-ray magnetic circular dichroism. The films are formed by CoPd alloyed nanoparticles self-organized across the layers, with the interspace between the nanoparticles filled by the non-alloyed Pd metal. The nanoparticles show atomic arrangements compatible with short-range chemical order of L 10 strucure type. The collective magnetic behavior is that of ferromagnetically coupled particles with perpendicular magnetic anisotropy, irrespective of the amount of deposited Pd. For increasing temperature three magnetic phases are identified: hard ferromagnetic with strong coercive field, soft-ferromagnetic as in an amorphous asperomagnet, and superparamagnetic. Increasing the amount of Pd in the system leads to both magnetic hardness increment and higher transition temperatures. Magnetic total moments of 1.77(4) μB and 0.45(4) μB are found at Co and Pd sites, respectively, where the orbital moment of Co, 0.40(2) μB, is high, while that of Pd is negligible. The effective magnetic anisotropy is the largest in the capping metal series (Pd, Pt, W, Cu, Ag, Au), which is attributed to the interparticle interaction between de nanoparticles, in addition to the intraparticle anisotropy arising from hybridization between the 3 d -4 d bands associated to the Co and Pd chemical arrangement in a L 10 structure type.

  18. Effect of the dispersants on Pd species and catalytic activity of supported palladium catalyst

    NASA Astrophysics Data System (ADS)

    Hu, Yue; Yang, Xiaojun; Cao, Shuo; Zhou, Jie; Wu, Yuanxin; Han, Jinyu; Yan, Zhiguo; Zheng, Mingming

    2017-04-01

    A series of supported palladium catalysts has been prepared through the precipitation method and the reduction method, using polyvinyl alcohol (PVA) and polyvinylpyrrolidone (PVP) as dispersants. The effects of the dispersants on the properties of catalysts were evaluated and the catalytic performance of the new materials was investigated for the oxidative carbonylation of phenol to diphenyl carbonate (DPC). The catalysts as prepared were also characterized by the X-ray diffraction (XRD), transmission electron microscope (TEM), Brunner-Emmet-Teller (BET) measurements and X-ray photoelectron spectroscopy (XPS) techniques. The results show that the addition of the dispersants had no effect on the crystal phase of the catalysts. However, the dispersion of Pd particles was improved when the dispersants were used. Moreover, the particle sizes of Pd nanoparticles modified by PVA were smaller than those modified by PVP. The catalysts prepared using the dispersants gave better yields of DPC than the catalysts prepared without the dispersants. The highest yield of DPC was 17.9% with the PVA-Red catalyst. The characterization results for the used catalysts showed that the Pd species in the PVA-Red catalyst remained mostly divalent and the lattice oxygen species were consumed during the reaction, which could lead to the higher catalytic activity of the PVA-Red catalyst. The experimental results confirm that PVA effectively inhibited the sintering and reduction of active Pd species in the oxidative carbonylation of phenol.

  19. 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.

  20. Identifying low-coverage surface species on supported noble metal nanoparticle catalysts by DNP-NMR

    SciTech Connect

    Johnson, Robert L.; Perras, Frédéric A.; Kobayashi, Takeshi; Schwartz, Thomas J.; Dumesic, James A.; Shanks, Brent H.; Pruski, Marek

    2015-11-20

    DNP-NMR spectroscopy has been applied to enhance the signal for organic molecules adsorbed on γ-Al2O3-supported Pd nanoparticles. In addition, by offering >2500-fold time savings, the technique enabled the observation of 13C-13C cross-peaks for low coverage species, which were assigned to products from oxidative degradation of methionine adsorbed on the nanoparticle surface.

  1. Identifying low-coverage surface species on supported noble metal nanoparticle catalysts by DNP-NMR

    DOE PAGES

    Johnson, Robert L.; Perras, Frédéric A.; Kobayashi, Takeshi; ...

    2015-11-20

    DNP-NMR spectroscopy has been applied to enhance the signal for organic molecules adsorbed on γ-Al2O3-supported Pd nanoparticles. In addition, by offering >2500-fold time savings, the technique enabled the observation of 13C-13C cross-peaks for low coverage species, which were assigned to products from oxidative degradation of methionine adsorbed on the nanoparticle surface.

  2. Preparation of PdAg and PdAu nanoparticle-loaded carbon black catalysts and their electrocatalytic activity for the glycerol oxidation reaction in alkaline medium

    NASA Astrophysics Data System (ADS)

    Lam, Binh Thi Xuan; Chiku, Masanobu; Higuchi, Eiji; Inoue, Hiroshi

    2015-11-01

    PdAg and PdAu alloy nanoparticle catalysts for the glycerol oxidation reaction (GOR) were prepared at room temperature by a wet method. The molar ratio of the precursors controlled the bulk composition of the PdAg and PdAu alloys, and their surface composition was Ag-enriched and Pd-enriched, respectively. On PdAg-loaded carbon black (PdAg/CB) electrodes, the onset potential of GOR was 0.10-0.15 V more negative than on the Pd/CB electrode due to the electronic effect. The ratio of GOR peak current densities in the backward and forward sweeps of CVs (ib/if) was smaller because of the improved tolerance to the poisoning species. The ratio of the GOR current density at 60 and 5 min (i60/i5) for the PdAg/CB electrodes was higher for more negative potentials than the Pd/CB electrode. In contrast, the PdAu-loaded CB (PdAu/CB) electrodes had an onset potential of GOR similar to the Pd/CB electrode and a higher GOR peak current density owing to the bi-functional effect. However, the ib/if ratio was higher for PdAu/CB because of the increase in ib as the Pd surface was recovered, and the i60/i5 ratio was higher for more positive potentials, similar to the Pd/CB electrode.

  3. Tailoring the local structure and electronic property of AuPd nanoparticles by selecting capping molecules

    NASA Astrophysics Data System (ADS)

    Liu, Feng; Zhang, Peng

    2010-01-01

    Nine AuPd nanoparticle samples selectively capped with tetraoctylphosphonium bromide, primary amine and tertiary amine molecules were studied with the Au L3-edge x-ray absorption spectroscopy (XAS). The AuPd mixing patterns were analyzed by comparing the XAS results with the theoretical coordination numbers of 24 AuPd model clusters of varied size, Au concentration, and bimetal mixing pattern. It was found that the use of amines, particularly tertiary amine, produced a more homogeneous AuPd mixing pattern and the Au d-electron density was fine-tunable by tailoring the density of Au-Pd bonds. Mechanisms for the tailored structural and electronic properties of these nanoparticles were proposed.

  4. Influence of support morphology on the bonding of molecules to nanoparticles

    PubMed Central

    Yim, Chi Ming; Pang, Chi L.; Hermoso, Diego R.; Dover, Coinneach M.; Muryn, Christopher A.; Maccherozzi, Francesco; Dhesi, Sarnjeet S.; Pérez, Rubén; Thornton, Geoff

    2015-01-01

    Supported metal nanoparticles form the basis of heterogeneous catalysts. Above a certain nanoparticle size, it is generally assumed that adsorbates bond in an identical fashion as on a semiinfinite crystal. This assumption has allowed the database on metal single crystals accumulated over the past 40 years to be used to model heterogeneous catalysts. Using a surface science approach to CO adsorption on supported Pd nanoparticles, we show that this assumption may be flawed. Near-edge X-ray absorption fine structure measurements, isolated to one nanoparticle, show that CO bonds upright on the nanoparticle top facets as expected from single-crystal data. However, the CO lateral registry differs from the single crystal. Our calculations indicate that this is caused by the strain on the nanoparticle, induced by carpet growth across the substrate step edges. This strain also weakens the CO–metal bond, which will reduce the energy barrier for catalytic reactions, including CO oxidation. PMID:26080433

  5. High-performance flexible hydrogen sensor made of WS₂ nanosheet-Pd nanoparticle composite film.

    PubMed

    Kuru, Cihan; Choi, Duyoung; Kargar, Alireza; Liu, Chin Hung; Yavuz, Serdar; Choi, Chulmin; Jin, Sungho; Bandaru, Prabhakar R

    2016-05-13

    We report a flexible hydrogen sensor, composed of WS2 nanosheet-Pd nanoparticle composite film, fabricated on a flexible polyimide substrate. The sensor offers the advantages of light-weight, mechanical durability, room temperature operation, and high sensitivity. The WS2-Pd composite film exhibits sensitivity (R 1/R 2, the ratio of the initial resistance to final resistance of the sensor) of 7.8 to 50,000 ppm hydrogen. Moreover, the WS2-Pd composite film distinctly outperforms the graphene-Pd composite, whose sensitivity is only 1.14. Furthermore, the ease of fabrication holds great potential for scalable and low-cost manufacturing of hydrogen sensors.

  6. Boron Nitride Nanosheet-Anchored Pd-Fe Core-Shell Nanoparticles as Highly Efficient Catalysts for Suzuki-Miyaura Coupling Reactions.

    PubMed

    Fu, Qinrui; Meng, Yuan; Fang, Zilin; Hu, Quanqin; Xu, Liang; Gao, Wenhua; Huang, Xiaochun; Xue, Qiao; Sun, Ya-Ping; Lu, Fushen

    2017-01-25

    Boron nitride nanosheets (BNNS) were used to anchor bimetallic Pd-Fe nanoparticles for Suzuki-Miyaura coupling catalysts. The bimetallic nanoparticles were found to be core-shell in structure, and their formation was likely facilitated by their interactions with the BNNS. The Pd-Fe/BNNS catalysts were highly effective in representative Suzuki-Miyaura reactions, with performances matching or exceeding those of the state-of-the-art methods. Specifically, the superior catalytic activities were characterized by generally shortened reaction times, minimal Pd usage, excellent reusability of the catalysts and high or nearly quantitative conversion yields in a benign solvent system without the need for any special conditions, such as ligands and surfactants or inert gas protection. The obvious advantages of the Pd-Fe/BNNS over similar catalysts based on other supports, such as reduced graphene oxide (rGO), suggest that BNNS may be developed into a versatile platform for many other important catalytic reactions.

  7. PdM nanoparticles (M = Ni, Co, Fe, Mn) with high activity and stability in formic acid oxidation synthesized by sonochemical reactions

    NASA Astrophysics Data System (ADS)

    Matin, Md. Abdul; Jang, Ji-Hoon; Kwon, Young-Uk

    2014-09-01

    Bimetallic alloy PdnM (n = 1 for M = Mn, Fe, and Co; n = 1, 2, and 3 for M = Ni) nanoparticles (NPs) are synthesized on carbon supports by sonochemical reactions of Pd(acac)2 (acac = acetylacetonate) with M(acac)2 (M = Ni, Co, Mn) or Fe(acac)3 in ethylene glycol. The NPs are characterized by powder X-ray diffractometry, transmission electron microscopy (TEM), and inductively coupled plasma-atomic emission spectroscopy to determine their crystal structures, particle sizes, morphology, and elemental compositions. Alloy formation of the NPs is proven by energy dispersive X-ray spectroscopy line profiles using scanning TEM. The electronic structures and the surface compositions of NPs are analyzed using X-ray photoelectron spectroscopy, and Fourier-transform infrared spectroscopy, respectively. PdnM NPs are applied as electrocatalysts for formic acid oxidation. The incorporation of M in Pd reduces the poisoning by surface hydroxyl groups. Activities based on the current densities are in the order of PdNi > PdFe > PdCo > PdMn. Within the PdnNi series, the activity is in the order of PdNi > Pd2Ni > Pd3Ni. The PdnM NP electrocatalysts show higher activity by a factor of 2-3.5 and improved durability than similarly prepared Pd NP electrocatalyst.

  8. Maghemite decorated with ultra-small palladium nanoparticles (γ-Fe2O3–Pd): applications in the Heck–Mizoroki olefination, Suzuki reaction and allylic oxidation of alkenes

    EPA Science Inventory

    A nanocatalyst comprising ultra-small Pd/PdO nanoparticles (<5 nm) supported on maghemite was prepared by a co-precipitation protocol using inexpensive raw materials and was deployed successfully in various significant synthetic transformations, namely the Heck–Mizoroki olefinati...

  9. Maghemite decorated with ultra-small palladium nanoparticles (γ-Fe2O3–Pd): applications in the Heck–Mizoroki olefination, Suzuki reaction and allylic oxidation of alkenes

    EPA Science Inventory

    A nanocatalyst comprising ultra-small Pd/PdO nanoparticles (<5 nm) supported on maghemite was prepared by a co-precipitation protocol using inexpensive raw materials and was deployed successfully in various significant synthetic transformations, namely the Heck–Mizoroki olefinati...

  10. Atomic-scale insights into structural and thermodynamic stability of Pd-Ni bimetallic nanoparticles.

    PubMed

    Huang, Rao; Wen, Yu-Hua; Zhu, Zi-Zhong; Sun, Shi-Gang

    2016-04-14

    Atomic-scale understanding of structures and thermodynamic stability of core-shell nanoparticles is important for both their synthesis and application. In this study, we systematically investigated the structural stability and thermodynamic evolution of core-shell structured Pd-Ni nanoparticles by molecular dynamics simulations. It has been revealed that dislocations and stacking faults occur in the shell and their amounts are strongly dependent on the core/shell ratio. The presence of these defects lowers the structural and thermal stability of these nanoparticles, resulting in even lower melting points than both Pd and Ni monometallic nanoparticles. Furthermore, different melting behaviors have been disclosed in Pd-core/Ni-shell and Ni-core/Pd-shell nanoparticles. These diverse behaviors cause different relationships between the melting temperature and the amount of stacking faults. Our results display direct evidence for the tunable stability of bimetallic nanoparticles. This study provides a fundamental perspective on core-shell structured nanoparticles and has important implications for further tailoring their structural and thermodynamic stability by core/shell ratio or composition controlling.

  11. Influence of shell thickness on thermal stability of bimetallic Al-Pd nanoparticles

    NASA Astrophysics Data System (ADS)

    Wen, John Z.; Nguyen, Ngoc Ha; Rawlins, John; Petre, Catalin F.; Ringuette, Sophie

    2014-07-01

    Aluminum-based bimetallic core-shell nanoparticles have shown promising applications in civil and defense industries. This study addresses the thermal stability of aluminum-palladium (Al-Pd) core/shell nanoparticles with a varying shell thickness of 5, 6, and 7 Å, respectively. The classic molecular dynamics (MD) simulations are performed in order to investigate the effects of the shell thickness on the ignition mechanism and subsequent energetic processes of these nanoparticles. The histograms of temperature change and structural evolution clearly show the inhibition role of the Pd shell during ignition. While the nanoparticle with a thicker shell is more thermally stable and hence requires more excess energy, stored as the potential energy of the nanoparticle and provided through numerically heating, to initiate the thermite reaction, a higher adiabatic temperature can be produced from this nanoparticle, thanks to its greater content of Pd. The two-stage thermite reactions are discussed with their activation energy based on the energy balance processes during MD heating and production. Analyses of the simulation results reveal that the inner pressure of the core-shell nanoparticle increases with both temperature and the absorbed thermal energy during heating, which may result in a breakup of the Pd shell.

  12. Tungsten carbide promoted Pd and Pd-Co electrocatalysts for formic acid electrooxidation

    NASA Astrophysics Data System (ADS)

    Yin, Min; Li, Qingfeng; Jensen, Jens Oluf; Huang, Yunjie; Cleemann, Lars N.; Bjerrum, Niels J.; Xing, Wei

    2012-12-01

    Tungsten carbide (WC) promoted palladium (Pd) and palladium-cobalt (Pd-Co) nanocatalysts are prepared and characterized for formic acid electrooxidation. The WC as the dopant to carbon supports is found to enhance the CO tolerance and promote the activity of the Pd-based catalysts for formic acid oxidation. Alloying of Pd with Co further improves the electrocatalytic activity and stability of the WC supported catalysts, attributable to a synergistic effect of the carbide support and PdCo alloy nanoparticles.

  13. Chemisorption of CO on Pd particles supported on mica

    NASA Technical Reports Server (NTRS)

    Thomas, M.; Poppa, H.; Dickinson, J. T.; Pound, G. M.

    1978-01-01

    A UHV technique is presented for evaluating the adsorption-desorption properties of UHV vapor-deposited metal particles supported on insulating substrates. Desorption studies of CO from particulate and continuous Pd films supported on mica were performed. The desorption results indicate that: the CO desorption energies from the deposited metals are much lower than those from bulk single crystals; two desorption states exist for the vapor-deposited films; and the lower energy desorption peak of the vapor-deposited films is coverage dependent. Possible reasons for the difference between previously reported CO desorption studies on bulk substrates and the present results are discussed.

  14. Laser-induced in situ synthesis of Pd and Pt nanoparticles on polymer films

    NASA Astrophysics Data System (ADS)

    Mehrabanian, Mehran; Morselli, Davide; Caputo, Gianvito; Scarpellini, Alice; Palazon, Francisco; Athanassiou, Athanassia; Fragouli, Despina

    2016-12-01

    We present the localized in situ formation of Pd and Pt nanoparticles embedded in chitosan solid films. This is achieved by the photo-induced reduction of metallic precursors, previously incorporated in chitosan films, through controlled UV pulsed laser irradiation. Interestingly, at high number of laser pulses, Pd and Pt follow different formation pathways, contrary to their common photoreduction mechanism occurring at low irradiation pulses. Specifically, in the case of the Pd, a photofragmentation process takes place fracturing the previously formed nanoparticles into smaller ones; whereas in the case of Pt, the prolonged irradiation promotes the nanoparticles agglomeration. The combination of both precursors in a binary solid system results in the combined formation of both Pd and Pt nanoparticles in the polymer film upon laser irradiation. The herein reported approach is an efficient and precise tool to generate size- and density-controlled Pd and Pt nanoparticles in desired areas of polymeric films, rendering this method a potential candidate for the fabrication of flexible polymeric devices for gas-sensing or electro-catalysis applications.

  15. Study of coordination environments around Pd and Pt in a Pd-core Pt-shell nanoparticle during heating

    NASA Astrophysics Data System (ADS)

    Nishimura, Y. F.; Hamaguchi, T.; Yamaguchi, S.; Takagi, H.; Dohmae, K.; Nonaka, T.; Nagai, Y.

    2016-05-01

    Local coordination environments around Pd and Pt in a Pd-core Pt-shell nanoparticle (NP) at temperatures ranging from 473 to 873 K was evaluated by utilizing in situ XAFS measurement technique to investigate the temperature range in which a core-shell structure is preserved. The core-shell structure was considered to be kept up to 673 K and start to change at about 773 K. Heating to 873 K accelerated atomic mixing in the core-shell NPs. Catalytic properties of the present Pd-core Pt-shell NP are available in the stoichiometric C3H6-O2 atmosphere at temperatures less than 773 K at most.

  16. Green Synthesis of Fe and Fe/Pd Bimetallic Nanoparticles in Membranes for Reductive Degradation of Chlorinated Organics

    PubMed Central

    Smuleac, V.; Varma, R.; Sikdar, S.; Bhattacharyya, D.

    2011-01-01

    Membranes containing reactive nanoparticles (Fe and Fe/Pd) immobilized in a polymer film (polyacrylic acid, PAA-coated polyvinylidene fluoride, PVDF membrane) are prepared by a new method. In the present work a biodegradable, non-toxic -“green” reducing agent, green tea extract was used for nanoparticle (NP) synthesis, instead of the well-known sodium borohydride. Green tea extract contains a number of polyphenols that can act as both chelating/reducing and capping agents for the nanoparticles. Therefore, the particles are protected from oxidation and aggregation, which increases their stability and longevity. The membrane supported NPs were successfully used for the degradation of a common and highly important pollutant, trichloroethylene (TCE). The rate of TCE degradation was found to increase linearly with the amount of Fe immobilized on the membrane, the surface normalized rate constant (kSA) being 0.005 L/m2h. The addition of a second catalytic metal, Pd, to form bimetallic Fe/Pd increased the kSA value to 0.008 L/m2h. For comparison purposes, Fe and Fe/Pd nanoparticles were synthesized in membranes using sodium borohydride as a reducing agent. Although the initial kSA values for this case (for Fe) are one order of magnitude higher than the tea extract synthesized NPs, the rapid oxidation reduced their reactivity to less than 20 % within 4 cycles. For the green tea extract NPs, the initial reactivity in the membrane domain was preserved even after 3 months of repeated use. The reactivity of TCE was verified with “real” water system. PMID:22228920

  17. DNA-Mediated Morphological Control of Pd-Au Bimetallic Nanoparticles.

    PubMed

    Satyavolu, Nitya Sai Reddy; Tan, Li Huey; Lu, Yi

    2016-12-21

    Recent reports have shown that different DNA sequences can mediate the control of shapes and surface properties of nanoparticles. However, all previous studies have involved only monometallic particles, most of which were gold nanoparticles. Controlling the shape of bimetallic nanoparticles is more challenging, and there is little research into the use of DNA-based ligands for their morphological control. We report the DNA-templated synthesis of Pd-Au bimetallic nanoparticles starting from palladium nanocube seeds. The presence of different homo-oligomer DNA sequences containing 10 deoxy-ribonucleotides of thymine, adenine, cytosine, or guanine results in the growth of four distinct morphologies. Through detailed kinetic studies by absorption spectroscopy, scanning electron microscopy (SEM) and scanning transmission electron microscopy (STEM), we have determined the role of DNA in controlling Pd-Au nanoparticle growth morphologies. One major function of DNA is affecting various properties of the incoming metal atoms, including their diffusion and deposition on the Pd nanocube seed. Interestingly, nanoparticle growth in the presence of A10 follows an aggregative growth mechanism that is unique when compared to the other base oligomers. These findings demonstrate that DNA can allow for programmable control of bimetallic nanoparticle morphologies, resulting in more complex hybrid materials with different plasmonic properties. The capability to finely tune multimetallic nanoparticle morphology stems from the versatile structure that is unique to DNA in comparison to conventionally used capping agents in colloidal nanomaterial synthesis.

  18. The influence of nano-architectured CeOx supports in RhPd/CeO₂ for the catalytic ethanol steam reforming reaction

    SciTech Connect

    Divins, N. J.; Senanayake, S. D.; Casanovas, A.; Xu, W.; Trovarelli, A.; Llorca, J.

    2015-01-19

    The ethanol steam reforming (ESR) reaction has been tested over RhPd supported on polycrystalline ceria in comparison to structured supports composed of nanoshaped CeO₂ cubes and CeO₂ rods tailored towards the production of hydrogen. At 650-700 K the hydrogen yield follows the trend RhPd/CeO₂-cubes > RhPd/CeO₂ -rods > RhPd/CeO₂- polycrystalline, whereas at temperatures higher than 800 K the catalytic performance of all samples is similar and close to the thermodynamic equilibrium. The improved performance of RhPd/CeO₂-cubes and RhPd/CeO₂ -rods for ESR at low temperature is mainly ascribed to higher water-gas shift activity and a strong interaction between the bimetallic - oxide support interaction. STEM analysis shows the existence of RhPd alloyed nanoparticles in all samples, with no apparent relationship between ESR performance and RhPd particle size. X-ray diffraction under operating conditions shows metal reorganization on {100} and {110} ceria crystallographic planes during catalyst activation and ESR, but not on {111} ceria crystallographic planes. The RhPd reconstructing and tuned activation over ceria nanocubes and nanorods is considered the main reason for better catalytic activity with respect to conventional catalysts based on polycrystalline ceria

  19. The influence of nano-architectured CeOx supports in RhPd/CeO₂ for the catalytic ethanol steam reforming reaction

    DOE PAGES

    Divins, N. J.; Senanayake, S. D.; Casanovas, A.; ...

    2015-01-19

    The ethanol steam reforming (ESR) reaction has been tested over RhPd supported on polycrystalline ceria in comparison to structured supports composed of nanoshaped CeO₂ cubes and CeO₂ rods tailored towards the production of hydrogen. At 650-700 K the hydrogen yield follows the trend RhPd/CeO₂-cubes > RhPd/CeO₂ -rods > RhPd/CeO₂- polycrystalline, whereas at temperatures higher than 800 K the catalytic performance of all samples is similar and close to the thermodynamic equilibrium. The improved performance of RhPd/CeO₂-cubes and RhPd/CeO₂ -rods for ESR at low temperature is mainly ascribed to higher water-gas shift activity and a strong interaction between the bimetallic -more » oxide support interaction. STEM analysis shows the existence of RhPd alloyed nanoparticles in all samples, with no apparent relationship between ESR performance and RhPd particle size. X-ray diffraction under operating conditions shows metal reorganization on {100} and {110} ceria crystallographic planes during catalyst activation and ESR, but not on {111} ceria crystallographic planes. The RhPd reconstructing and tuned activation over ceria nanocubes and nanorods is considered the main reason for better catalytic activity with respect to conventional catalysts based on polycrystalline ceria« less

  20. Energetic and structural analysis of 102-atom Pd-Pt nanoparticles

    NASA Astrophysics Data System (ADS)

    Pacheco-Contreras, Rafael; Arteaga-Guerrero, Alvaro; Borbon-Gonzalez, Dora Julia; Posada-Amarillas, Alvaro; Schoen, J. Christian; Johnston, Roy L.

    2009-03-01

    We present an extensive study of the structural and energetic changes of 102-atom PdmPt102-m nanoparticles as a function of composition m, where the interatomic interactions are modeled with the many-body Gupta potential. The minimum energy structures are obtained through a genetic algorithm. The excess energy is calculated, as well as the pair distribution function g(r). The radial distribution of the atoms is computed for each composition; the result indicates a multi-layer segregation for some compositions, with a shell growth sequence as follows: a core with a small number of Pd atoms is followed by an intermediate shell of Pt atoms and the external shell consists of Pd atoms. A region where Pd and Pt atoms are mixed is observed between the outermost and intermediate shells. Furthermore, the pure Pd102 and Pt102 nanoparticles have the same structure, while a variety of different structures are observed for the bimetallic clusters.

  1. Synthesis of cubic PtPd alloy nanoparticles as anode electrocatalysts for methanol and formic acid oxidation reactions.

    PubMed

    Lee, Jin-Yeon; Kwak, Da-Hee; Lee, Young-Woo; Lee, Seul; Park, Kyung-Won

    2015-04-14

    The electrocatalytic properties for electro-oxidation reactions of shape-controlled Pt-based catalysts have been improved by alloying with 2nd elements. In this study, we demonstrate cubic PtPd alloy nanoparticles synthesized using a thermal decomposition method. The cubic PtPd nanoparticles exhibit a homogeneous distribution of alloy nanostructures in the presence of Pt and Pd metallic phases. The improved electrocatalytic activity for the electro-oxidation reactions of methanol and formic acid as chemical fuels might be attributed to the cubic alloy nanostructures. Furthermore, the cubic PtPd alloy nanoparticles as electrocatalysts exhibit excellent stability for electro-oxidation reactions.

  2. A general strategy for the preparation of carbon nanotubes and graphene oxide decorated with PdO nanoparticles in water.

    PubMed

    He, Hongkun; Gao, Chao

    2010-07-02

    The preparation of carbon nanotube (CNT)/PdO nanoparticles and graphene oxide (GO)/PdO nanoparticle hybrids via a general aqueous solution strategy is reported. The PdO nanoparticles are generated in situ on the CNTs and GO by a one-step "green" synthetic approach in aqueous Pd(NO(3))(2) solution under ambient conditions without adding any additional chemicals. The production of PdO is confirmed by energy dispersive X-ray spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, Raman spectroscopy, and thermal gravimetric analysis. The morphologies of the resulting CNT/PdO and GO/PdO nanohybrids are characterized by transmission and/or scanning transmission electron microscopy. PdO nanoparticles with an average size of 2-3 nm in diameter are decorated evenly along the surfaces of CNTs and GO. This synthesis strategy is demonstrated to be compatible for 1) CNTs with different modifications, including pristine, oxidized, and polymer-functionalized CNTs; 2) different types of CNTs, including single-walled carbon nanotubes (SWCNTs), double-walled carbon nanotubes (DWCNTs), and multiwalled carbon nanotubes (MWCNTs); and 3) different shapes of carbon materials, including tubular CNTs and planar GO. The as-prepared CNT/PdO and GO/PdO nanohybrids can be transformed into CNT/Pd and GO/Pd nanohybrids by reduction with NaBH(4), and can then be used as a heterogeneous catalyst in the catalytic reduction of 4-nitrophenol.

  3. Fast response and recovery of hydrogen sensing in Pd-Pt nanoparticle-graphene composite layers.

    PubMed

    Kumar, Rakesh; Varandani, Deepak; Mehta, B R; Singh, V N; Wen, Zhenhai; Feng, Xinliang; Müllen, Klaus

    2011-07-08

    This study reports the fast response and recovery of hydrogen sensing in nanoparticle-graphene composite layers fabricated using chemical methods and comprising of isolated Pd alloy nanoparticles dispersed onto graphene layers. For 2% hydrogen at 40 °C and 1 atm pressure, a response time of <2 s and a recovery time of 18 s are observed. The fast response and recovery observed during sensing are due to hydrogen-induced changes in the work function of the Pd alloy and modification in the distribution of defect states in the graphene band gap due to gas adsorption. The results of hydrogen sensing in the new class of Pd-Pt nanoparticle-graphene composite material are important for understanding the effect of gas adsorption on electronic conduction in graphene layers and for developing a new type of gas sensor based on changes in the electronic properties of the interface.

  4. Fast response and recovery of hydrogen sensing in Pd-Pt nanoparticle-graphene composite layers

    NASA Astrophysics Data System (ADS)

    Kumar, Rakesh; Varandani, Deepak; Mehta, B. R.; Singh, V. N.; Wen, Zhenhai; Feng, Xinliang; Müllen, Klaus

    2011-07-01

    This study reports the fast response and recovery of hydrogen sensing in nanoparticle-graphene composite layers fabricated using chemical methods and comprising of isolated Pd alloy nanoparticles dispersed onto graphene layers. For 2% hydrogen at 40 °C and 1 atm pressure, a response time of < 2 s and a recovery time of 18 s are observed. The fast response and recovery observed during sensing are due to hydrogen-induced changes in the work function of the Pd alloy and modification in the distribution of defect states in the graphene band gap due to gas adsorption. The results of hydrogen sensing in the new class of Pd-Pt nanoparticle-graphene composite material are important for understanding the effect of gas adsorption on electronic conduction in graphene layers and for developing a new type of gas sensor based on changes in the electronic properties of the interface.

  5. PdNi hollow nanoparticles for improved electrocatalytic oxygen reduction in alkaline environments.

    PubMed

    Wang, Meng; Zhang, Weimin; Wang, Jiazhao; Wexler, David; Poynton, Simon D; Slade, Robert C T; Liu, Huakun; Winther-Jensen, Bjorn; Kerr, Robert; Shi, Dongqi; Chen, Jun

    2013-12-11

    Palladium-nickel (PdNi) hollow nanoparticles were synthesized via a modified galvanic replacement method using Ni nanoparticles as sacrificial templates in an aqueous medium. X-ray diffraction and transmission electron microscopy show that the as-synthesized nanoparticles are alloyed nanostructures and have hollow interiors with an average particle size of 30 nm and shell thickness of 5 nm. Compared with the commercially available Pt/C or Pd/C catalysts, the synthesized PdNi/C has superior electrocatalytic performance towards the oxygen reduction reaction, which makes it a promising electrocatalyst for alkaline anion exchange membrane fuel cells and alkali-based air-batteries. The electrocatalyst is finally examined in a H2/O2 alkaline anion exchange membrane fuel cell; the results show that such electrocatalysts could work in a real fuel cell application as a more efficient catalyst than state-of-the-art commercially available Pt/C.

  6. Au-Rh and Au-Pd nanocatalysts supported on rutile titania nanorods: structure and chemical stability.

    PubMed

    Konuspayeva, Zere; Afanasiev, Pavel; Nguyen, Thanh-Son; Di Felice, Luca; Morfin, Franck; Nguyen, Nhat-Tai; Nelayah, Jaysen; Ricolleau, Christian; Li, Z Y; Yuan, Jun; Berhault, Gilles; Piccolo, Laurent

    2015-11-14

    Au, Rh, Pd, Au-Rh and Au-Pd nanoparticles (NPs) were synthesized by colloidal chemical reduction and immobilized on hydrothermally-prepared rutile titania nanorods. The catalysts were characterized by aberration-corrected TEM/STEM, XPS, and FTIR, and were evaluated in the hydrogenation of tetralin in the presence of H2S. Oxidizing and reducing thermal treatments were employed to remove the polyvinyl alcohol (PVA) surfactant. Reduction in H2 at 350 °C was found efficient for removing the PVA while preserving the size (ca. 3 nm), shape and bimetallic nature of the NPs. While Au-Pd NPs are alloyed at the atomic scale, Au-Rh NPs contain randomly distributed single-phase domains. Calcination-reduction of Au-Rh NPs mostly leads to separated Au and Rh NPs, while pre-reduction generates a well-defined segregated structure with Rh located at the interface between Au and TiO2 and possibly present around the NPs as a thin overlayer. Both the titania support and gold increase the resistance of Rh and Pd to oxidation. Furthermore, although detrimental to tetralin hydrogenation initial activity, gold stabilizes the NPs against surface sulfidation in the presence of 50 ppm H2S, leading to increased catalytic performances of the Au-Rh and Au-Pd systems as compared to their Rh and Pd counterparts.

  7. Characterization of Na+- beta-Zeolite Supported Pd and Pd Ag Bimetallic Catalysts using EXAFS, TEM and Flow Reactor

    SciTech Connect

    Huang,W.; Lobo, R.; Chen, J.

    2008-01-01

    Flow reactor studies of the selective hydrogenation of acetylene in the presence of ethylene have been performed on Na+ exchanged {beta}-zeolite supported Pd, Ag and PdAg catalysts, as an extension of our previous batch reactor studies [W. Huang, J.R. McCormick, R.F. Lobo, J.G. Chen, J. Catal. 246 (2007) 40-51]. Results from flow reactor studies show that the PdAg/Na+-{beta}-zeolite bimetallic catalyst has lower activity than Pd/Na+-{beta}-zeolite monometallic catalyst, while Ag/Na+-{beta}-zeolite does not show any activity for acetylene hydrogenation. However, the selectivity for the PdAg bimetallic catalyst is much higher than that for either the Pd catalyst or Ag catalyst. The selectivity to byproduct (ethane) is greatly inhibited on the PdAg bimetallic catalyst as well. The results from the current flow reactor studies confirmed the pervious results from batch reactor studies [W. Huang, J.R. McCormick, R.F. Lobo, J.G. Chen, J. Catal. 246 (2007) 40-51]. In addition, we used transmission electron microscope (TEM), extended X-ray absorption fine structure (EXAFS), and FTIR of CO adsorption to confirm the formation of Pd-Ag bimetallic alloy in the PdAg/Na+-{beta}-zeolite catalyst.

  8. Core-shell Au-Pd nanoparticles as cathode catalysts for microbial fuel cell applications

    NASA Astrophysics Data System (ADS)

    Yang, Gaixiu; Chen, Dong; Lv, Pengmei; Kong, Xiaoying; Sun, Yongming; Wang, Zhongming; Yuan, Zhenhong; Liu, Hui; Yang, Jun

    2016-10-01

    Bimetallic nanoparticles with core-shell structures usually display enhanced catalytic properties due to the lattice strain created between the core and shell regions. In this study, we demonstrate the application of bimetallic Au-Pd nanoparticles with an Au core and a thin Pd shell as cathode catalysts in microbial fuel cells, which represent a promising technology for wastewater treatment, while directly generating electrical energy. In specific, in comparison with the hollow structured Pt nanoparticles, a benchmark for the electrocatalysis, the bimetallic core-shell Au-Pd nanoparticles are found to have superior activity and stability for oxygen reduction reaction in a neutral condition due to the strong electronic interaction and lattice strain effect between the Au core and the Pd shell domains. The maximum power density generated in a membraneless single-chamber microbial fuel cell running on wastewater with core-shell Au-Pd as cathode catalysts is ca. 16.0 W m-3 and remains stable over 150 days, clearly illustrating the potential of core-shell nanostructures in the applications of microbial fuel cells.

  9. Core-shell Au-Pd nanoparticles as cathode catalysts for microbial fuel cell applications

    PubMed Central

    Yang, Gaixiu; Chen, Dong; Lv, Pengmei; Kong, Xiaoying; Sun, Yongming; Wang, Zhongming; Yuan, Zhenhong; Liu, Hui; Yang, Jun

    2016-01-01

    Bimetallic nanoparticles with core-shell structures usually display enhanced catalytic properties due to the lattice strain created between the core and shell regions. In this study, we demonstrate the application of bimetallic Au-Pd nanoparticles with an Au core and a thin Pd shell as cathode catalysts in microbial fuel cells, which represent a promising technology for wastewater treatment, while directly generating electrical energy. In specific, in comparison with the hollow structured Pt nanoparticles, a benchmark for the electrocatalysis, the bimetallic core-shell Au-Pd nanoparticles are found to have superior activity and stability for oxygen reduction reaction in a neutral condition due to the strong electronic interaction and lattice strain effect between the Au core and the Pd shell domains. The maximum power density generated in a membraneless single-chamber microbial fuel cell running on wastewater with core-shell Au-Pd as cathode catalysts is ca. 16.0 W m−3 and remains stable over 150 days, clearly illustrating the potential of core-shell nanostructures in the applications of microbial fuel cells. PMID:27734945

  10. Core-shell Au-Pd nanoparticles as cathode catalysts for microbial fuel cell applications.

    PubMed

    Yang, Gaixiu; Chen, Dong; Lv, Pengmei; Kong, Xiaoying; Sun, Yongming; Wang, Zhongming; Yuan, Zhenhong; Liu, Hui; Yang, Jun

    2016-10-13

    Bimetallic nanoparticles with core-shell structures usually display enhanced catalytic properties due to the lattice strain created between the core and shell regions. In this study, we demonstrate the application of bimetallic Au-Pd nanoparticles with an Au core and a thin Pd shell as cathode catalysts in microbial fuel cells, which represent a promising technology for wastewater treatment, while directly generating electrical energy. In specific, in comparison with the hollow structured Pt nanoparticles, a benchmark for the electrocatalysis, the bimetallic core-shell Au-Pd nanoparticles are found to have superior activity and stability for oxygen reduction reaction in a neutral condition due to the strong electronic interaction and lattice strain effect between the Au core and the Pd shell domains. The maximum power density generated in a membraneless single-chamber microbial fuel cell running on wastewater with core-shell Au-Pd as cathode catalysts is ca. 16.0 W m(-3) and remains stable over 150 days, clearly illustrating the potential of core-shell nanostructures in the applications of microbial fuel cells.

  11. Green synthesis of Pd nanoparticles at Apricot kernel shell substrate using Salvia hydrangea extract: Catalytic activity for reduction of organic dyes.

    PubMed

    Khodadadi, Bahar; Bordbar, Maryam; Nasrollahzadeh, Mahmoud

    2017-03-15

    For the first time the extract of the plant of Salvia hydrangea was used to green synthesis of Pd nanoparticles (NPs) supported on Apricot kernel shell as an environmentally benign support. The Pd NPs/Apricot kernel shell as an effective catalyst was prepared through reduction of Pd(2+) ions using Salvia hydrangea extract as the reducing and capping agent and Pd NPs immobilization on Apricot kernel shell surface in the absence of any stabilizer or surfactant. According to FT-IR analysis, the hydroxyl groups of phenolics in Salvia hydrangea extract as bioreductant agents are directly responsible for the reduction of Pd(2+) ions and formation of Pd NPs. The as-prepared catalyst was characterized by Fourier transform infrared (FT-IR) and UV-Vis spectroscopy, field emission scanning electron microscopy (FESEM) equipped with an energy dispersive X-ray spectroscopy (EDS), Elemental mapping, X-ray diffraction analysis (XRD) and transmittance electron microscopy (TEM). The synthesized catalyst was used in the reduction of 4-nitrophenol (4-NP), Methyl Orange (MO), Methylene Blue (MB), Rhodamine B (RhB), and Congo Red (CR) at room temperature. The Pd NPs/Apricot kernel shell showed excellent catalytic activity in the reduction of these organic dyes. In addition, it was found that Pd NPs/Apricot kernel shell can be recovered and reused several times without significant loss of catalytic activity. Copyright © 2016 Elsevier Inc. All rights reserved.

  12. Core/shell face-centered tetragonal FePd/Pd nanoparticles as an efficient non-Pt catalyst for the oxygen reduction reaction

    SciTech Connect

    Zhu, Huiyuan; Jiang, Guangming; Zhang, Xu; Shen, Bo; Wu, Liheng; Zhang, Sen; Lu, Gang; Wu, Zhongbiao; Sun, Shouheng

    2015-10-04

    We report the synthesis of core/shell face-centered tetragonal (fct)-FePd/Pd nanoparticles (NPs) via reductive annealing of core/shell Pd/Fe3O4 NPs followed by temperature-controlled Fe etching in acetic acid. Among three different kinds of core/shell FePd/Pd NPs studied (FePd core at similar to 8 nm and Pd shell at 0.27, 0.65, or 0.81 nm), the fct-FePd/Pd-0.65 NPs are the most efficient catalyst for the oxygen reduction reaction (ORR) in 0.1 M HClO4 with Pt-like activity and durability. This enhanced ORR catalysis arises from the desired Pd lattice compression in the 0.65 nm Pd shell induced by the fct-FePd core. Lastly, our study offers a general approach to enhance Pd catalysis in acid for ORB.

  13. Core/shell face-centered tetragonal FePd/Pd nanoparticles as an efficient non-Pt catalyst for the oxygen reduction reaction

    DOE PAGES

    Zhu, Huiyuan; Jiang, Guangming; Zhang, Xu; ...

    2015-10-04

    We report the synthesis of core/shell face-centered tetragonal (fct)-FePd/Pd nanoparticles (NPs) via reductive annealing of core/shell Pd/Fe3O4 NPs followed by temperature-controlled Fe etching in acetic acid. Among three different kinds of core/shell FePd/Pd NPs studied (FePd core at similar to 8 nm and Pd shell at 0.27, 0.65, or 0.81 nm), the fct-FePd/Pd-0.65 NPs are the most efficient catalyst for the oxygen reduction reaction (ORR) in 0.1 M HClO4 with Pt-like activity and durability. This enhanced ORR catalysis arises from the desired Pd lattice compression in the 0.65 nm Pd shell induced by the fct-FePd core. Lastly, our study offersmore » a general approach to enhance Pd catalysis in acid for ORB.« less

  14. Composition-dependent electrocatalytic activity of palladium-iridium binary alloy nanoparticles supported on the multiwalled carbon nanotubes for the electro-oxidation of formic acid.

    PubMed

    Bao, Jianming; Dou, Meiling; Liu, Haijing; Wang, Feng; Liu, Jingjun; Li, Zhilin; Ji, Jing

    2015-07-22

    Surface-functionalized multiwalled carbon nanotubes (MWCNTs) supported Pd100-xIrx binary alloy nanoparticles (Pd100-xIrx/MWCNT) with tunable Pd/Ir atomic ratios were synthesized by a thermolytic process at varied ratios of bis(acetylacetonate) palladium(II) and iridium(III) 2,4-pentanedionate precursors and then applied as the electrocatalyst for the formic acid electro-oxidation. The X-ray diffraction pattern (XRD) and transmission electron microscope (TEM) analysis showed that the Pd100-xIrx alloy nanoparticles with the average size of 6.2 nm were uniformly dispersed on the MWCNTs and exhibited a single solid solution phase with a face-centered cubic structure. The electrocatalytic properties were evaluated through the cyclic voltammetry and chronoamperometry tests, and the results indicated that both the activity and stability of Pd100-xIrx/MWCNT were strongly dependent on the Pd/Ir atomic ratios: the best electrocatalytic performance in terms of onset potential, current density, and stability against CO poisoning was obtained for the Pd79Ir21/MWCNT. Moreover, compared with pure Pd nanoparticles supported on MWCNTs (Pd/MWCNT), the Pd79Ir21/MWCNT exhibited enhanced steady-state current density and higher stability, as well as maintained excellent electrocatalytic activity in high concentrated formic acid solution, which was attributed to the bifunctional effect through alloying Pd with transition metal.

  15. N-Methylimidazole functionalized carboxymethycellulose-supported Pd catalyst and its applications in Suzuki cross-coupling reaction.

    PubMed

    Dong, Yahao; Wu, Xiaotian; Chen, Xiaofeng; Wei, Yuping

    2017-03-15

    In this paper, N-Methylimidazole functionalized carboxymethylcellulose-supported palladium nanoparticles (CMC-NHC-Pd) was synthesized and characterized by TEM, SEM, EDX, CP/MAS (13)C NMR, FT-IR, TGA, XRD, and XPS analysis. The prepared nanoparticles can be used as an environmentally-friendly and trifunctional catalyst. The well-designed CMC supported palladium nanoparticles catalyst with polydentate ligands is also stable and efficient for Suzuki cross-coupling reactions under mild conditions through the cooperative interaction of trifunctional capturing sites with palladium, -COO(-), -OH and N-Methylimidazole. This catalyst can be readily recovered by a few cycles of simple filtration. This work proposes a plausible trifunctional catalyst complex. Copyright © 2016 Elsevier Ltd. All rights reserved.

  16. Synthesis, characterization, and electrochemical behavior of Au@Pd core shell nanoparticles

    NASA Astrophysics Data System (ADS)

    Wicaksono, W. P.; Ivandini, T. A.

    2017-04-01

    Au@Pd core shell nanoparticles (Au@Pd CSNPs) were successfully synthesized using a seed-mediated growth method. Firstly, a pale pink gold seed solution was used to produce a pale purple gold nanoparticles (AuNPs) core solution. Then, three series of Pd shell thickness using 20μ, 100 μL, and 500 μL of PdCl2 produced purple, brown, and deep brown of Au@Pd CSNPs respectively. A strong absorbance UV-Visible spectrum with peaks at 285 nm and 535 nm was identified for AuNPs formation. The disappearance of the peak at 535 nm was indicated the Au@Pd CSNPs formation. The electrochemical properties were examined in phosphate buffer pH 7 using cyclic voltammetry technique with boron-doped diamond (BDD) as working electrode showed a couple oxidation and reduction peak of gold at 0.67 V and at 0.33 V, respectively. The Au@Pd CNPs will be used for modification of BDD electrodes.

  17. Structural characterization of Pt–Pd core–shell nanoparticles by Cs-corrected STEM

    PubMed Central

    Esparza, R.; García-Ruiz, Amado F.; Salazar, J. J. Velázquez; Pérez, R.; José-Yacamán, M.

    2013-01-01

    Pt–Pd core–shell nanoparticles were synthesized using a modified polyol method. A thermal method under refluxing, carrying on the reaction up to 285 °C, has been performed to reduce metallic salts using ethylene glycol as reducer and poly(N-vinyl-2-pyrrolidone) as protective reagent of the formed bimetallic nanoparticles. According to other works, this type of structure has been studied and utilized to successfully increase the catalytic properties of monometallic nanoparticles Pt or Pd. Core–shell bimetallic nanoparticles were structurally characterized using aberration-corrected scanning transmission electron microscopy (Cs-STEM) equipped with a high-angle annular dark field detector, energy-dispersive X-ray spectrometry (EDS), and electron energy-loss spectroscopy (EELS). The high-resolution elemental line scan and mappings were carried out using a combination of STEM–EDS and STEM–EELS. The obtained results show the growth of the Pd shell on the Pt core with polyhedral morphology. The average size of the bimetallic nanoparticles was 13.5 nm and the average size of the core was 8.5 nm; consequently, the thickness of the shell was around 2.5 nm. The growth of the Pd shell on the Pt core is layer by layer, suggesting a Frank-van der Merwe growth mechanism. PMID:24991190

  18. Structural characterization of Pt-Pd core-shell nanoparticles by Cs-corrected STEM.

    PubMed

    Esparza, R; García-Ruiz, Amado F; Salazar, J J Velázquez; Pérez, R; José-Yacamán, M

    2012-12-01

    Pt-Pd core-shell nanoparticles were synthesized using a modified polyol method. A thermal method under refluxing, carrying on the reaction up to 285 °C, has been performed to reduce metallic salts using ethylene glycol as reducer and poly(N-vinyl-2-pyrrolidone) as protective reagent of the formed bimetallic nanoparticles. According to other works, this type of structure has been studied and utilized to successfully increase the catalytic properties of monometallic nanoparticles Pt or Pd. Core-shell bimetallic nanoparticles were structurally characterized using aberration-corrected scanning transmission electron microscopy (Cs-STEM) equipped with a high-angle annular dark field detector, energy-dispersive X-ray spectrometry (EDS), and electron energy-loss spectroscopy (EELS). The high-resolution elemental line scan and mappings were carried out using a combination of STEM-EDS and STEM-EELS. The obtained results show the growth of the Pd shell on the Pt core with polyhedral morphology. The average size of the bimetallic nanoparticles was 13.5 nm and the average size of the core was 8.5 nm; consequently, the thickness of the shell was around 2.5 nm. The growth of the Pd shell on the Pt core is layer by layer, suggesting a Frank-van der Merwe growth mechanism.

  19. Structural studies of Au-Pd bimetallic nanoparticles by a genetic algorithm method

    NASA Astrophysics Data System (ADS)

    Shao, Gui-Fang; Tu, Na-Na; Liu, Tun-Dong; Xu, Liang-You; Wen, Yu-Hua

    2015-06-01

    Metallic nanoparticles have attracted particular interests due to their excellent electronic, catalytic and optical properties over the past decades. Atomic-level understanding of structural characteristics of metallic nanoparticles is of great importance for their syntheses and applications because the structural characteristics strongly determine their chemical and physical properties. In this article, we systematically investigated the structural stability and structural features of Au-Pd nanoparticles by using the genetic algorithm with the quantum correction Sutton-Chen potentials. Layered coordinate ranking method and an effective fitness function have been introduced into the genetic algorithm to enhance its searching ability of low-energy configurations. Here were addressed eight representative nanoshapes including single-crystalline and multiple-twinned structures. The results reveal that the developed genetic algorithm exhibits superior searching ability. In all polyhedra, the truncated octahedron possessed the best stability, while the icosahedron did the worst. Moreover, segregation of Au to the surface and that of Pd to the core were disclosed in these polyhedral Au-Pd nanoparticles. Particularly, for Au composition of 50%, the optimized structures of Au-Pd nanoparticles were predicted to exhibit core-shell structures.

  20. The effect of external magnetic fields on the catalytic activity of Pd nanoparticles in Suzuki cross-coupling reactions

    NASA Astrophysics Data System (ADS)

    Gao, Lei; Wang, Changlai; Li, Ren; Li, Ran; Chen, Qianwang

    2016-04-01

    Pd nanoparticles supported on Co3[Co(CN)6]2 nanoparticles (marked as Pd@Co3[Co(CN)6]2 nanoparticles) were prepared as catalysts for the Suzuki cross-coupling reaction under external magnetic fields (MFs). It is shown that a weak external MF can increase the rate of the Suzuki cross-coupling reaction at room temperature, and with the increase of the strength of external MFs the reaction rate also increased. At 30 °C, the yield was increased by nearly 50% under a 0.5 T external MF after 24 hours compared to that without a MF applied. Theoretical calculations revealed that the adsorption energy changed from -1.07 to -1.12 eV in the presence of MFs, which increased by 5% compared with the absence of MFs, leading to a lower total energy of the adsorption system, which is beneficial to the reaction. From the analysis of the partial density states, it could be seen that the 2p orbital of the carbon atom in bromobenzene and the 4d orbital of the Pd atom overlap more closely in the presence of MFs, which is beneficial for the electron transfer from the Pd substrate to the bromobenzene molecule. This study is helpful in understanding the interaction between MFs and catalysts and regulating the process of catalytic reactions via MFs.Pd nanoparticles supported on Co3[Co(CN)6]2 nanoparticles (marked as Pd@Co3[Co(CN)6]2 nanoparticles) were prepared as catalysts for the Suzuki cross-coupling reaction under external magnetic fields (MFs). It is shown that a weak external MF can increase the rate of the Suzuki cross-coupling reaction at room temperature, and with the increase of the strength of external MFs the reaction rate also increased. At 30 °C, the yield was increased by nearly 50% under a 0.5 T external MF after 24 hours compared to that without a MF applied. Theoretical calculations revealed that the adsorption energy changed from -1.07 to -1.12 eV in the presence of MFs, which increased by 5% compared with the absence of MFs, leading to a lower total energy of the

  1. Evolution of the Structure and Chemical State of Pd Nanoparticles During the in Situ Catalytic Reduction of NO with H2

    SciTech Connect

    K Paredis; L Ono; F Behafarid; Z Zhang; J Yang; A Frenkel; B Roldan Cuenya

    2011-12-31

    An in-depth understanding of the fundamental structure of catalysts during operation is indispensable for tailoring future efficient and selective catalysts. We report the evolution of the structure and oxidation state of ZrO{sub 2}-supported Pd nanocatalysts (5 nm) during the in situ reduction of NO with H{sub 2} using X-ray absorption fine-structure spectroscopy and X-ray photoelectron spectroscopy. Prior to the onset of the reaction ({le}120 C), a NO-induced redispersion of our initial metallic Pd nanoparticles over the ZrO{sub 2} support was observed, and Pd{sup {delta}+} species were detected. This process parallels the high production of N{sub 2}O observed at the onset of the reaction (>120 C), while at higher temperatures ({ge}150 C) the selectivity shifts mainly toward N{sub 2} ({approx}80%). Concomitant with the onset of N{sub 2} production, the Pd atoms aggregate again into large (6.5 nm) metallic Pd nanoparticles, which were found to constitute the active phase for the H{sub 2}-reduction of NO. Throughout the entire reaction cycle, the formation and stabilization of PdO{sub x} was not detected. Our results highlight the importance of in situ reactivity studies to unravel the microscopic processes governing catalytic reactivity.

  2. Pd-Pt Catalysts on Fluorinated Alumina Support Studied by X-Ray Absorption Fine Structure

    NASA Astrophysics Data System (ADS)

    Yan, Wensheng; Li, Zhongrui; Wei, Zheng; Wei, Shiqiang

    2007-02-01

    A series of bi-metallic Pd-Pt catalysts supported on both pristine and fluorinated alumina supports were investigated with x-ray absorption spectroscopy. It was found that Pd and Pt form small alloy particles on the pristine alumina support; the composition and the cluster size of the PdPt bimetallic alloys, and the electronic properties of the metals were significantly altered on the fluorinated support. The remarkable increase in sulfur tolerance of the PdPt metallic clusters supported on the fluorine pretreated alumina can be attributed to an electronic depletion of the metals, large particle size and direct participation of the acid sites in the reaction.

  3. Aerobic dehydrogenation of cyclohexanone to phenol catalyzed by Pd(TFA)2/2-dimethylaminopyridine: evidence for the role of Pd nanoparticles.

    PubMed

    Pun, Doris; Diao, Tianning; Stahl, Shannon S

    2013-06-05

    We have carried out a mechanistic investigation of aerobic dehydrogenation of cyclohexanones and cyclohexenones to phenols with a Pd(TFA)2/2-dimethylaminopyridine catalyst system. Numerous experimental methods, including kinetic studies, filtration tests, Hg poisoning experiments, transmission electron microscopy, and dynamic light scattering, provide compelling evidence that the initial Pd(II) catalyst mediates the first dehydrogenation of cyclohexanone to cyclohexenone, after which it evolves into soluble Pd nanoparticles that retain catalytic activity. This nanoparticle formation and stabilization is facilitated by each of the components in the catalytic reaction, including the ligand, TsOH, DMSO, substrate, and cyclohexenone intermediate.

  4. G6PD testing in support of treatment and elimination of malaria: recommendations for evaluation of G6PD tests

    PubMed Central

    2013-01-01

    Malaria elimination will be possible only with serious attempts to address asymptomatic infection and chronic infection by both Plasmodium falciparum and Plasmodium vivax. Currently available drugs that can completely clear a human of P. vivax (known as “radical cure”), and that can reduce transmission of malaria parasites, are those in the 8-aminoquinoline drug family, such as primaquine. Unfortunately, people with glucose-6-phosphate dehydrogenase (G6PD) deficiency risk having severe adverse reactions if exposed to these drugs at certain doses. G6PD deficiency is the most common human enzyme defect, affecting approximately 400 million people worldwide. Scaling up radical cure regimens will require testing for G6PD deficiency, at two levels: 1) the individual level to ensure safe case management, and 2) the population level to understand the risk in the local population to guide Plasmodium vivax treatment policy. Several technical and operational knowledge gaps must be addressed to expand access to G6PD deficiency testing and to ensure that a patient’s G6PD status is known before deciding to administer an 8-aminoquinoline-based drug. In this report from a stakeholder meeting held in Thailand on October 4 and 5, 2012, G6PD testing in support of radical cure is discussed in detail. The focus is on challenges to the development and evaluation of G6PD diagnostic tests, and on challenges related to the operational aspects of implementing G6PD testing in support of radical cure. The report also describes recommendations for evaluation of diagnostic tests for G6PD deficiency in support of radical cure. PMID:24188096

  5. One-step green synthesis of bimetallic Fe/Pd nanoparticles used to degrade Orange II.

    PubMed

    Luo, Fang; Yang, Die; Chen, Zuliang; Megharaj, Mallavarapu; Naidu, Ravendra

    2016-02-13

    To reduce cost and enhance reactivity, bimetallic Fe/Pd nanoparticles (NPs) were firstly synthesized using grape leaf aqueous extract to remove Orange II. Green synthesized bimetallic Fe/Pd NPs (98.0%) demonstrated a far higher ability to remove Orange II in 12h compared to Fe NPs (16.0%). Meanwhile, all precursors, e.g., grape leaf extract, Fe(2+) and Pd(2+), had no obvious effect on removing Orange II since less than 2.0% was removed. Kinetics study revealed that the removal rate fitted well to the pseudo-first-order reduction and pseudo-second-order adsorption model, meaning that removing Orange II via Fe/Pd NPs involved both adsorption and catalytic reduction. The remarkable stability of Fe/Pd NPs showed the potential application for removing azo dyes. Furthermore, Scanning Electron Microscopy (SEM) and Fourier Transform Infrared Spectroscopy (FTIR) confirmed the changes in Fe/Pd NPs before and after reaction with Orange II. High Performance Liquid Chromatography-Mass Spectrum (HPLC-MS) identified the degraded products in the removal of Orange II, and finally a removal mechanism was proposed. This one-step strategy using grape leaf aqueous extract to synthesize Fe/Pd NPs is simple, cost-effective and environmentally benign, making possible the large-scale production of Fe/Pd NPs for field remediation. Copyright © 2015 Elsevier B.V. All rights reserved.

  6. In Situ Generation of Pd-Pt Core-Shell Nanoparticles on Reduced Graphene Oxide (Pd@Pt/rGO) Using Microwaves: Applications in Dehalogenation Reactions and Reduction of Olefins.

    PubMed

    Goswami, Anandarup; Rathi, Anuj K; Aparicio, Claudia; Tomanec, Ondrej; Petr, Martin; Pocklanova, Radka; Gawande, Manoj B; Varma, Rajender S; Zboril, Radek

    2017-01-25

    Core-shell nanocatalysts are a distinctive class of nanomaterials with varied potential applications in view of their unique structure, composition-dependent physicochemical properties, and promising synergism among the individual components. A one-pot microwave (MW)-assisted approach is described to prepare the reduced graphene oxide (rGO)-supported Pd-Pt core-shell nanoparticles, (Pd@Pt/rGO); spherical core-shell nanomaterials (∼95 nm) with Pd core (∼80 nm) and 15 nm Pt shell were nicely distributed on the rGO matrix in view of the choice of reductant and reaction conditions. The well-characterized composite nanomaterials, endowed with synergism among its components and rGO support, served as catalysts in aromatic dehalogenation reactions and for the reduction of olefins with high yield (>98%), excellent selectivity (>98%) and recyclability (up to 5 times); both Pt/rGO and Pd/rGO and even their physical mixtures showed considerably lower conversions (20 and 57%) in dehalogenation of 3-bromoaniline. Similarly, in the reduction of styrene to ethylbenzene, Pd@Pt core-shell nanoparticles (without rGO support) possess considerably lower conversion (60%) compared to Pd@Pt/rGO. The mechanism of dehalogenation reactions with Pd@Pt/rGO catalyst is discussed with the explicit premise that rGO matrix facilitates the adsorption of the reducing agent, thus enhancing its local concentration and expediting the hydrazine decomposition rate. The versatility of the catalyst has been validated via diverse substrate scope for both reduction and dehalogenation reactions.

  7. Shape-dependent electrocatalysis: formic acid electrooxidation on cubic Pd nanoparticles.

    PubMed

    Vidal-Iglesias, Francisco J; Arán-Ais, Rosa M; Solla-Gullón, José; Garnier, Emmanuel; Herrero, Enrique; Aldaz, Antonio; Feliu, Juan M

    2012-08-07

    The electrocatalytic properties of palladium nanocubes towards the electrochemical oxidation of formic acid were studied in H(2)SO(4) and HClO(4) solutions and compared with those of spherical Pd nanoparticles. The spherical and cubic Pd nanoparticles were characterized by transmission electron microscopy (TEM) and X-ray diffraction (XRD). The intrinsic electrocatalytic properties of both nanoparticles were shown to be strongly dependent on the amount of metal deposited on the gold substrate. Thus, to properly compare the activity of both systems (spheres and nanocubes), the amount of sample has to be optimized to avoid problems due to a lower diffusion flux of reactants in the internal parts of the catalyst layer resulting in a lower apparent activity. Under the optimized conditions, the activity of the spheres and nanocubes was very similar between 0.1 and 0.35 V. From this potential value, the activity of the Pd nanocubes was remarkably higher. This enhanced electrocatalytic activity was attributed to the prevalence of Pd(100) facets in agreement with previous studies with Pd single crystal electrodes. The effect of HSO(4)(-)/SO(4)(2-) desorption-adsorption was also evaluated. The activity found in HClO(4) was significantly higher than that obtained in H(2)SO(4) in the whole potential range.

  8. Reversible formation of a PdC(x) phase in Pd nanoparticles upon CO and O2 exposure.

    PubMed

    Balmes, Olivier; Resta, Andrea; Wermeille, Didier; Felici, Roberto; Messing, Maria E; Deppert, Knut; Liu, Zhi; Grass, Michael E; Bluhm, Hendrik; van Rijn, Richard; Frenken, Joost W M; Westerström, Rasmus; Blomberg, Sara; Gustafson, Johan; Andersen, Jesper N; Lundgren, Edvin

    2012-04-14

    The structure and chemical composition of Pd nanoparticles exposed to pure CO and mixtures of CO and O(2) at elevated temperatures have been studied in situ by a combination of X-ray Diffraction and X-ray Photoelectron Spectroscopy in pressures ranging from ultra high vacuum to 10 mbar and from room temperature to a few hundred degrees celsius. Our investigation shows that under CO exposure, above a certain temperature, carbon dissolves into the Pd particles forming a carbide phase. Upon exposure to CO and O(2) mixtures, the carbide phase forms and disappears reversibly, switching at the stoichiometric ratio for CO oxidation. This finding opens new scenarios for the understanding of catalytic oxidation of C-based molecules.

  9. A facile synthesis of palladium nanoparticles supported on functional carbon nanotubes and its novel catalysis for ethanol electrooxidation.

    PubMed

    Chen, Xiao-mei; Lin, Zhi-jie; Jia, Tian-tian; Cai, Zhi-min; Huang, Xiao-li; Jiang, Ya-qi; Chen, Xi; Chen, Guo-nan

    2009-09-14

    In this study, a novel material, palladium nanoparticles-carboxylic functional carbon nanotubes (PdNPs-CFCNTs), based on PdNPs supported on CFCNTs was synthesized by a facile spontaneous redox method. The material reveals high electrochemical activity and excellent catalytic characteristic for alcohol electrooxidation on a glassy carbon electrode (GCE) in an alkaline medium. The preparation mechanism was studied by the galvanic cell effect between PdCl(4)(2-) and functional defect sites on CFCNTs. Results from UV-visible absorption spectroscopy and electrochemical impedance spectroscopy revealed that the reduction of PdCl(4)(2-) to metallic Pd was successfully achieved. Morphologies of PdNPs supporting on CFCNTs (PdNPs-CFCNTs) were also characterized by transmission electron micrograph. PdNPs-CFCNTs with the best electrocatalytic characteristics were obtained under the condition as: the weight ratio of Pd to CFCNTs was kept at 2:1, the temperature was kept at 70 degrees C in the synthesis, and the scan rate of the applied potential was selected at 60 mV s(-1). The results indicate that PdNPs-CFCNTs could be a great potential material in direct ethanol fuel cells and ethanol sensors.

  10. Behavior of Supported Palladium Oxide Nanoparticles under Reaction Conditions, Studied with near Ambient Pressure XPS.

    PubMed

    Jürgensen, Astrid; Heutz, Niels; Raschke, Hannes; Merz, Klaus; Hergenröder, Roland

    2015-08-04

    Near ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) is a promising method to close the "pressure gap", and thus, study the surface composition during heterogeneous reactions in situ. The specialized spectrometers necessary for this analytical technique have recently been adapted to operate with a conventional X-ray source, making it available for routine quantitative analysis in the laboratory. This is shown in the present in situ study of the partial oxidation of 2-propanol catalyzed with PdO nanoparticles supported on TiO2, which was investigated under reaction conditions as a function of gas composition (alcohol-to-oxygen ratio) and temperature. Exposure of the nanoparticles to 2-propanol at 30 °C leads to immediate partial reduction of the PdO, followed by a continuous reduction of the remaining PdO during heating. However, gaseous oxygen inhibits the reduction of PdO below 90 °C, and the oxidation of 2-propanol to carboxylates only occurs in the presence of oxygen above 90 °C. These results support the theory that metallic palladium is the active catalyst material, and they show that environmental conditions affect the nanoparticles and the reaction process significantly. The study also revealed challenges and limitations of this analytical method. Specifically, the intensity and fixed photon energy of a conventional X-ray source limit the spectral resolution and surface sensitivity of lab-based NAP-XPS, which affect precision and accuracy of the quantitative analysis.

  11. Selective Semihydrogenation of Alkynes Catalyzed by Pd Nanoparticles Immobilized on Heteroatom-Doped Hierarchical Porous Carbon Derived from Bamboo Shoots.

    PubMed

    Ji, Guijie; Duan, Yanan; Zhang, Shaochun; Fei, Benhua; Chen, Xiufang; Yang, Yong

    2017-09-11

    Highly dispersed palladium nanoparticles (Pd NPs) immobilized on heteroatom-doped hierarchical porous carbon supports (N,O-carbon) with large specific surface areas are synthesized by a wet chemical reduction method. The N,O-carbon derived from naturally abundant bamboo shoots is fabricated by a tandem hydrothermal-carbonization process without assistance of any templates, chemical activation reagents, or exogenous N or O sources in a simple and ecofriendly manner. The prepared Pd/N,O-carbon catalyst shows extremely high activity and excellent chemoselectivity for semihydrogenation of a broad range of alkynes to versatile and valuable alkenes under ambient conditions. The catalyst can be readily recovered for successive reuse with negligible loss in activity and selectivity, and is also applicable for practical gram-scale reactions. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Recyclable polyurea-microencapsulated Pd(0) nanoparticles: an efficient catalyst for hydrogenolysis of epoxides.

    PubMed

    Ley, Steven V; Mitchell, Claire; Pears, David; Ramarao, Chandrashekar; Yu, Jin-Quan; Zhou, Wuzong

    2003-11-27

    [reaction: see text] Pd nanoparticles (approximately 2 nm in size) microencapsulated in polyurea is an efficient and recyclable catalyst for reductive ring-opening hydrogenolysis of epoxides, using either HCOOH/Et(3)N or H(2) as a hydrogen donor.

  13. Long-range chemical orders in Au-Pd nanoparticles revealed by aberration-corrected electron microscopy

    NASA Astrophysics Data System (ADS)

    Nelayah, Jaysen; Nguyen, Nhat Tai; Alloyeau, Damien; Wang, Guillaume Yangshu; Ricolleau, Christian

    2014-08-01

    Despite the importance of gold-palladium nanoalloys in heterogeneous catalysis, the phase stability of Au-Pd alloys still remains unclear. We report here on the alloying and chemical ordering in epitaxially-grown and post-annealed gold-palladium nanoparticles (NPs) using aberration-corrected transmission electron microscopy. Au-Pd NPs with a controlled size, composition and structure were grown by pulsed laser deposition on freshly-cleaved NaCl(001) single crystals heated at 300 °C. After transfer to an amorphous carbon support, the NPs were annealed in vacuum at elevated temperatures above 400 °C for a few hours (6-10 hours) to promote chemical ordering. The as-grown NPs were mostly monocrystalline with a chemically-disordered face-centered cubic structure. Upon high-temperature annealing, a high degree of chemical ordering was observed in nanometer-sized NPs. Electron microscopy measurements showed that both L10 and L12 orders are stabilized in the Au-rich region of the Au-Pd phase diagram. These ordered phases exist at temperatures as high as 600 °C. Moreover, compositional analysis of single annealed particles revealed that the observed chemical ordering occurs in parallel to a two-tiered Ostwald ripening process. Due to this ripening process, a clear dependence between chemical composition and particle size is established during annealing with an enrichment in Pd as the NPs grow in size. Our results, besides clarifying some controversial aspects about long-range order in Au-Pd alloys, shed light on the structural stability of Au-Pd nanoalloys at elevated temperatures.Despite the importance of gold-palladium nanoalloys in heterogeneous catalysis, the phase stability of Au-Pd alloys still remains unclear. We report here on the alloying and chemical ordering in epitaxially-grown and post-annealed gold-palladium nanoparticles (NPs) using aberration-corrected transmission electron microscopy. Au-Pd NPs with a controlled size, composition and structure were grown

  14. Carbon-supported Pd-Ir catalyst as anodic catalyst in direct formic acid fuel cell

    NASA Astrophysics Data System (ADS)

    Wang, Xin; Tang, Yawen; Gao, Ying; Lu, Tianhong

    It was reported for the first time that the electrocatalytic activity of the Carbon-supported Pd-Ir (Pd-Ir/C) catalyst with the suitable atomic ratio of Pd and Ir for the oxidation of formic acid in the direct formic acid fuel cell (DFAFC) is better than that of the Carbon-supported Pd (Pd/C) catalyst, although Ir has no electrocatalytic activity for the oxidation of formic acid. The potential of the anodic peak of formic acid at the Pd-Ir/C catalyst electrode with the atomic ratio of Pd and Ir = 5:1 is 50 mV more negative than that and the peak current density is 13% higher than that at the Pd/C catalyst electrode. This is attributed to that Ir can promote the oxidation of formic acid at Pd through the direct pathway because Ir can decrease the adsorption strength of CO on Pd. However, when the content of Ir in the Pd-Ir/C catalyst is too high the electrocatalytic activity of the Pd-Ir/C catalyst would be decreased because Ir has no electrocatalytic activity for the oxidation of formic acid.

  15. Long-range chemical orders in Au-Pd nanoparticles revealed by aberration-corrected electron microscopy.

    PubMed

    Nelayah, Jaysen; Nguyen, Nhat Tai; Alloyeau, Damien; Wang, Guillaume Yangshu; Ricolleau, Christian

    2014-09-07

    Despite the importance of gold-palladium nanoalloys in heterogeneous catalysis, the phase stability of Au-Pd alloys still remains unclear. We report here on the alloying and chemical ordering in epitaxially-grown and post-annealed gold-palladium nanoparticles (NPs) using aberration-corrected transmission electron microscopy. Au-Pd NPs with a controlled size, composition and structure were grown by pulsed laser deposition on freshly-cleaved NaCl(001) single crystals heated at 300 °C. After transfer to an amorphous carbon support, the NPs were annealed in vacuum at elevated temperatures above 400 °C for a few hours (6-10 hours) to promote chemical ordering. The as-grown NPs were mostly monocrystalline with a chemically-disordered face-centered cubic structure. Upon high-temperature annealing, a high degree of chemical ordering was observed in nanometer-sized NPs. Electron microscopy measurements showed that both L10 and L12 orders are stabilized in the Au-rich region of the Au-Pd phase diagram. These ordered phases exist at temperatures as high as 600 °C. Moreover, compositional analysis of single annealed particles revealed that the observed chemical ordering occurs in parallel to a two-tiered Ostwald ripening process. Due to this ripening process, a clear dependence between chemical composition and particle size is established during annealing with an enrichment in Pd as the NPs grow in size. Our results, besides clarifying some controversial aspects about long-range order in Au-Pd alloys, shed light on the structural stability of Au-Pd nanoalloys at elevated temperatures.

  16. The complex behavior of the Pd 7 cluster supported on TiO 2 (110) during CO oxidation: adsorbate-driven promoting effect

    SciTech Connect

    An, Wei; Liu, Ping

    2016-09-07

    When using the TiO2(110)-supported Pd7 cluster as a model catalyst, we identified the dynamics of supported metal nanoparticles using density functional theory calculations, at the sub-nanometer scale and under reactive environments. Increasing the CO coverage can induce a structural transformation from Pd7-3D/TiO2(110) at low coverage to Pd7-2D/TiO2(110) at the saturation coverage wherein CO saturation-driven Pd7-2D/TiO2(110) structure displays superior CO oxidation activity at the interfacial sites, which are highly active for catalyzing O2 dissociation and CO oxidation via bifunctional synergy.

  17. The complex behavior of the Pd 7 cluster supported on TiO 2 (110) during CO oxidation: adsorbate-driven promoting effect

    DOE PAGES

    An, Wei; Liu, Ping

    2016-09-07

    When using the TiO2(110)-supported Pd7 cluster as a model catalyst, we identified the dynamics of supported metal nanoparticles using density functional theory calculations, at the sub-nanometer scale and under reactive environments. Increasing the CO coverage can induce a structural transformation from Pd7-3D/TiO2(110) at low coverage to Pd7-2D/TiO2(110) at the saturation coverage wherein CO saturation-driven Pd7-2D/TiO2(110) structure displays superior CO oxidation activity at the interfacial sites, which are highly active for catalyzing O2 dissociation and CO oxidation via bifunctional synergy.

  18. The complex behavior of the Pd 7 cluster supported on TiO 2 (110) during CO oxidation: adsorbate-driven promoting effect

    SciTech Connect

    An, Wei; Liu, Ping

    2016-09-07

    When using the TiO2(110)-supported Pd7 cluster as a model catalyst, we identified the dynamics of supported metal nanoparticles using density functional theory calculations, at the sub-nanometer scale and under reactive environments. Increasing the CO coverage can induce a structural transformation from Pd7-3D/TiO2(110) at low coverage to Pd7-2D/TiO2(110) at the saturation coverage wherein CO saturation-driven Pd7-2D/TiO2(110) structure displays superior CO oxidation activity at the interfacial sites, which are highly active for catalyzing O2 dissociation and CO oxidation via bifunctional synergy.

  19. Size and alloying induced changes in lattice constant, core, and valance band binding energy in Pd-Ag, Pd, and Ag nanoparticles: Effect of in-flight sintering temperature

    NASA Astrophysics Data System (ADS)

    Sengar, Saurabh K.; Mehta, B. R.; Govind

    2012-07-01

    In the present study, we report the growth of size selected Pd, Ag, and Pd-Ag alloy nanoparticles by an integrated method comprising of the gas phase synthesis, electrical mobility size selection, and in-flight sintering steps. Effect of temperature during in-flight sintering on nanoparticle size, crystal structure, and electronic properties has been studied. XRD studies show lattice expansion in Pd and Ag nanoparticles and lattice contraction in Pd-Ag alloy nanoparticles on increasing the sintering temperatures. In case of Pd and Ag nanoparticles, size induced changes in lattice constants are consistent with the changes in the binding energy positions with respect to bulk values. In case of Pd-Ag alloy nanoparticles, change in nanoparticle size and composition on sintering affect the lattice constant and binding energy positions. Large changes in Pd4d valance band centroid in Pd-Ag nanoparticles are due to size and alloying effects. The results of this study are important for understanding the correlation between electronic properties and Pd-H interaction in Pd alloy nanoparticles.

  20. Palladium Nanoparticles Supported on Ce-Metal-Organic Framework for Efficient CO Oxidation and Low-Temperature CO2 Capture.

    PubMed

    Lin, Andrew; Ibrahim, Amr Awad; Arab, Pezhman; El-Kaderi, Hani M; El-Shall, M Samy

    2017-05-31

    In this article, we report the lowest-temperature CO oxidation catalyst supported on metal-organic frameworks (MOFs). We have developed a facile, general, and effective approach based on microwave irradiation for the incorporation of Pd nanoparticle catalyst within Ce-MOF. The resulting Pd/Ce-MOF material is a unique catalyst that is capable of CO oxidation at modest temperatures and also of efficient uptake of the product CO2 gas at low temperatures. The observed catalytic activity of this material toward CO oxidation is significantly higher than those of other reported metal nanoparticles supported on MOFs. The high activity of the Pd/Ce-MOF catalyst is due to the presence of Ce(III) and Ce(IV) ions within the metal-organic framework support. The Pd nanoparticles supported on the Ce-MOF store oxygen in the form of a thin palladium oxide layer at the particle-support interface, in addition to the oxygen stored on the Ce(III)/Ce(IV) centers. Oxygen from these reservoirs can be released during CO oxidation at 373 K. At lower temperatures (273 K), the Pd/Ce-MOF has a significant CO2 uptake of 3.5 mmol/g.

  1. Porous Pd nanoparticles with high photothermal conversion efficiency for efficient ablation of cancer cells.

    PubMed

    Xiao, Jia-Wen; Fan, Shi-Xuan; Wang, Feng; Sun, Ling-Dong; Zheng, Xiao-Yu; Yan, Chun-Hua

    2014-04-21

    Nanoparticle (NP) mediated photothermal effect shows great potential as a noninvasive method for cancer therapy treatment, but the development of photothermal agents with high photothermal conversion efficiency, small size and good biocompatibility is still a big challenge. Herein, we report Pd NPs with a porous structure exhibiting enhanced near infrared (NIR) absorption as compared to Pd nanocubes with a similar size (almost two-fold enhancement with a molar extinction coefficient of 6.3 × 10(7) M(-1) cm(-1)), and the porous Pd NPs display monotonically rising absorbance from NIR to UV-Vis region. When dispersed in water and illuminated with an 808 nm laser, the porous Pd NPs give a photothermal conversion efficiency as high as 93.4%, which is comparable to the efficiency of Au nanorods we synthesized (98.6%). As the porous Pd NPs show broadband NIR absorption (650-1200 nm), this allows us to choose multiple laser wavelengths for photothermal therapy. In vitro photothermal heating of HeLa cells in the presence of porous Pd NPs leads to 100% cell death under 808 nm laser irradiation (8 W cm(-2), 4 min). For photothermal heating using 730 nm laser, 70% of HeLa cells were killed after 4 min irradiation at a relative low power density of 6 W cm(-2). These results demonstrated that the porous Pd nanostructure is an attractive photothermal agent for cancer therapy.

  2. Synergistic Effects in CNTs-PdAu/Pt Trimetallic Nanoparticles with High Electrocatalytic Activity and Stability

    NASA Astrophysics Data System (ADS)

    Cai, Xin-Lei; Liu, Chang-Hai; Liu, Jie; Lu, Ying; Zhong, Ya-Nan; Nie, Kai-Qi; Xu, Jian-Long; Gao, Xu; Sun, Xu-Hui; Wang, Sui-Dong

    2017-10-01

    We present a straightforward physical approach for synthesizing multiwalled carbon nanotubes (CNTs)-PdAu/Pt trimetallic nanoparticles (NPs), which allows predesign and control of the metal compositional ratio by simply adjusting the sputtering targets and conditions. The small-sized CNTs-PdAu/Pt NPs ( 3 nm, Pd/Au/Pt ratio of 3:1:2) act as nanocatalysts for the methanol oxidation reaction (MOR), showing excellent performance with electrocatalytic peak current of 4.4 A mg Pt -1 and high stability over 7000 s. The electrocatalytic activity and stability of the PdAu/Pt trimetallic NPs are much superior to those of the corresponding Pd/Pt and Au/Pt bimetallic NPs, as well as a commercial Pt/C catalyst. Systematic investigation of the microscopic, crystalline, and electronic structure of the PdAu/Pt NPs reveals alloying and charge redistribution in the PdAu/Pt NPs, which are responsible for the promotion of the electrocatalytic performance.

  3. Au/Pd core-shell nanoparticles with varied hollow Au cores for enhanced formic acid oxidation.

    PubMed

    Hsu, Chiajen; Huang, Chienwen; Hao, Yaowu; Liu, Fuqiang

    2013-03-01

    A facile method has been developed to synthesize Au/Pd core-shell nanoparticles via galvanic replacement of Cu by Pd on hollow Au nanospheres. The unique nanoparticles were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy, ultraviolet-visible spectroscopy, and electrochemical measurements. When the concentration of the Au solution was decreased, grain size of the polycrystalline hollow Au nanospheres was reduced, and the structures became highly porous. After the Pd shell formed on these Au nanospheres, the morphology and structure of the Au/Pd nanoparticles varied and hence significantly affected the catalytic properties. The Au/Pd nanoparticles synthesized with reduced Au concentrations showed higher formic acid oxidation activity (0.93 mA cm-2 at 0.3 V) than the commercial Pd black (0.85 mA cm-2 at 0.3 V), suggesting a promising candidate as fuel cell catalysts. In addition, the Au/Pd nanoparticles displayed lower CO-stripping potential, improved stability, and higher durability compared to the Pd black due to their unique core-shell structures tuned by Au core morphologies.

  4. Au/Pd core-shell nanoparticles with varied hollow Au cores for enhanced formic acid oxidation

    NASA Astrophysics Data System (ADS)

    Hsu, Chiajen; Huang, Chienwen; Hao, Yaowu; Liu, Fuqiang

    2013-03-01

    A facile method has been developed to synthesize Au/Pd core-shell nanoparticles via galvanic replacement of Cu by Pd on hollow Au nanospheres. The unique nanoparticles were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy, ultraviolet-visible spectroscopy, and electrochemical measurements. When the concentration of the Au solution was decreased, grain size of the polycrystalline hollow Au nanospheres was reduced, and the structures became highly porous. After the Pd shell formed on these Au nanospheres, the morphology and structure of the Au/Pd nanoparticles varied and hence significantly affected the catalytic properties. The Au/Pd nanoparticles synthesized with reduced Au concentrations showed higher formic acid oxidation activity (0.93 mA cm-2 at 0.3 V) than the commercial Pd black (0.85 mA cm-2 at 0.3 V), suggesting a promising candidate as fuel cell catalysts. In addition, the Au/Pd nanoparticles displayed lower CO-stripping potential, improved stability, and higher durability compared to the Pd black due to their unique core-shell structures tuned by Au core morphologies.

  5. Au/Pd core-shell nanoparticles with varied hollow Au cores for enhanced formic acid oxidation

    PubMed Central

    2013-01-01

    A facile method has been developed to synthesize Au/Pd core-shell nanoparticles via galvanic replacement of Cu by Pd on hollow Au nanospheres. The unique nanoparticles were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy, ultraviolet–visible spectroscopy, and electrochemical measurements. When the concentration of the Au solution was decreased, grain size of the polycrystalline hollow Au nanospheres was reduced, and the structures became highly porous. After the Pd shell formed on these Au nanospheres, the morphology and structure of the Au/Pd nanoparticles varied and hence significantly affected the catalytic properties. The Au/Pd nanoparticles synthesized with reduced Au concentrations showed higher formic acid oxidation activity (0.93 mA cm-2 at 0.3 V) than the commercial Pd black (0.85 mA cm-2 at 0.3 V), suggesting a promising candidate as fuel cell catalysts. In addition, the Au/Pd nanoparticles displayed lower CO-stripping potential, improved stability, and higher durability compared to the Pd black due to their unique core-shell structures tuned by Au core morphologies. PMID:23452438

  6. Synthesis of porous carbon supported palladium nanoparticle catalysts by atomic layer deposition: application for rechargeable lithium-O2 battery.

    PubMed

    Lei, Yu; Lu, Jun; Luo, Xiangyi; Wu, Tianpin; Du, Peng; Zhang, Xiaoyi; Ren, Yang; Wen, Jianguo; Miller, Dean J; Miller, Jeffrey T; Sun, Yang-Kook; Elam, Jeffrey W; Amine, Khalil

    2013-09-11

    In this study, atomic layer deposition (ALD) was used to deposit nanostructured palladium on porous carbon as the cathode material for Li-O2 cells. Scanning transmission electron microscopy showed discrete crystalline nanoparticles decorating the surface of the porous carbon support, where the size could be controlled in the range of 2-8 nm and depended on the number of Pd ALD cycles performed. X-ray absorption spectroscopy at the Pd K-edge revealed that the carbon supported Pd existed in a mixed phase of metallic palladium and palladium oxide. The conformality of ALD allowed us to uniformly disperse the Pd catalyst onto the carbon support while preserving the initial porous structure. As a result, the charging and discharging performance of the oxygen cathode in a Li-O2 cell was improved. Our results suggest that ALD is a promising technique for tailoring the surface composition and structure of nanoporous supports in energy storage devices.

  7. Energy-efficient green catalysis: supported gold nanoparticle-catalyzed aminolysis of esters with inert tertiary amines by C-O and C-N bond activations.

    PubMed

    Bao, Yong-Sheng; Baiyin, Menghe; Agula, Bao; Jia, Meilin; Zhaorigetu, Bao

    2014-07-18

    Catalyzed by supported gold nanoparticles, an aminolysis reaction between various aryl esters and inert tertiary amines by C-O and C-N bond activations has been developed for the selective synthesis of tertiary amides. Comparison studies indicated that the gold nanoparticles could perform energy-efficient green catalysis at room temperature, whereas Pd(OAc)2 could not.

  8. Porous Pd nanoparticles with high photothermal conversion efficiency for efficient ablation of cancer cells

    NASA Astrophysics Data System (ADS)

    Xiao, Jia-Wen; Fan, Shi-Xuan; Wang, Feng; Sun, Ling-Dong; Zheng, Xiao-Yu; Yan, Chun-Hua

    2014-03-01

    Nanoparticle (NP) mediated photothermal effect shows great potential as a noninvasive method for cancer therapy treatment, but the development of photothermal agents with high photothermal conversion efficiency, small size and good biocompatibility is still a big challenge. Herein, we report Pd NPs with a porous structure exhibiting enhanced near infrared (NIR) absorption as compared to Pd nanocubes with a similar size (almost two-fold enhancement with a molar extinction coefficient of 6.3 × 107 M-1 cm-1), and the porous Pd NPs display monotonically rising absorbance from NIR to UV-Vis region. When dispersed in water and illuminated with an 808 nm laser, the porous Pd NPs give a photothermal conversion efficiency as high as 93.4%, which is comparable to the efficiency of Au nanorods we synthesized (98.6%). As the porous Pd NPs show broadband NIR absorption (650-1200 nm), this allows us to choose multiple laser wavelengths for photothermal therapy. In vitro photothermal heating of HeLa cells in the presence of porous Pd NPs leads to 100% cell death under 808 nm laser irradiation (8 W cm-2, 4 min). For photothermal heating using 730 nm laser, 70% of HeLa cells were killed after 4 min irradiation at a relative low power density of 6 W cm-2. These results demonstrated that the porous Pd nanostructure is an attractive photothermal agent for cancer therapy.Nanoparticle (NP) mediated photothermal effect shows great potential as a noninvasive method for cancer therapy treatment, but the development of photothermal agents with high photothermal conversion efficiency, small size and good biocompatibility is still a big challenge. Herein, we report Pd NPs with a porous structure exhibiting enhanced near infrared (NIR) absorption as compared to Pd nanocubes with a similar size (almost two-fold enhancement with a molar extinction coefficient of 6.3 × 107 M-1 cm-1), and the porous Pd NPs display monotonically rising absorbance from NIR to UV-Vis region. When dispersed in water

  9. Aqueous Co-precipitation of Pd-doped Cerium Oxide Nanoparticles: Chemistry Structure and Particle Growth

    SciTech Connect

    Liang H.; Zhang L.; Raitano J.M.; He G.; Akey A.J.; Herman I.P.; Chan S.-W.

    2012-01-01

    Nanoparticles of palladium-doped cerium oxide (Pd-CeO{sub 2}) have been prepared by aqueous co-precipitation resulting in a single phase cubic structure after calcination according to X-ray diffraction (XRD). Inhomogeneous strain, calculated using the Williamson-Hall method, was found to increase with palladium content, and the lattice contracts slightly, relative to nano-cerium oxide, as palladium content is increased. Moreover, high resolution transmission electron microscopy reveals some instances of defective microstructure. These factors combined imply that palladium is in solid solution with CeO{sub 2} in these nanoparticles, but palladium (II) oxide (PdO) peaks in the Raman spectra indicate that solid solution formation is partial and that highly dispersed PdO is present as well as the solid solution. Nevertheless, the addition of palladium to the CeO{sub 2} lattice inhibits the growth of the 6% Pd-CeO{sub 2} particles compared to pure CeO{sub 2} between 600 and 850 C. Activation energies for grain growth of 54 {+-} 7 and 79 {+-} 8 kJ/mol were determined for 6% Pd-CeO{sub 2} and pure CeO{sub 2}, respectively, along with pre-exponential Arrhenius factors of 10 for the doped sample and 600 for pure cerium oxide.

  10. An experimental and theoretical investigation of the inversion of pd@pt core@shell dendrimer-encapsulated nanoparticles.

    PubMed

    Anderson, Rachel M; Zhang, Liang; Loussaert, James A; Frenkel, Anatoly I; Henkelman, Graeme; Crooks, Richard M

    2013-10-22

    Bimetallic PdPt dendrimer-encapsulated nanoparticles (DENs) having sizes of about 2 nm were synthesized by a homogeneous route that involved (1) formation of a Pd core, (2) deposition of a Cu shell onto the Pd core in the presence of H2 gas, and (3) galvanic exchange of Pt for the Cu shell. Under these conditions, a Pd@Pt core@shell DEN is anticipated, but detailed characterization by in-situ extended X-ray absorption fine structure (EXAFS) spectroscopy and other analytical methods indicate that the metals invert to yield a Pt-rich core with primarily Pd in the shell. The experimental findings correlate well with density functional theoretical (DFT) calculations. Theory suggests that the increased disorder associated with <~2 nm diameter nanoparticles, along with the relatively large number of edge and corner sites, drives the structural rearrangement. This type of rearrangement is not observed on larger nanoparticles or in bulk metals.

  11. SnO2 nanospheres supported Pd catalyst with enhanced performance for formic acid oxidation

    NASA Astrophysics Data System (ADS)

    Lu, Haiting; Fan, Yang; Huang, Ping; Xu, Dongli

    2012-10-01

    SnO2 nanospheres were employed as the support material for Pd catalyst. The as-prepared Pd/SnO2 catalyst exhibited remarkably improved electrocatalytic activity and stability towards formic acid oxidation, in comparison with that of the Vulcan XC-72 carbon black and the commercial SnO2 nanopowder supported Pd catalyst. The enhanced catalytic performance may arise from the unique structure and surface properties of the SnO2 nanospheres, which process extraordinary promotional effect on Pd catalyst.

  12. Chemical order and magnetic behavior of Fe-dilute fcc Fe-Pd nanoparticles

    NASA Astrophysics Data System (ADS)

    Guirado-López, R. A.; Desjonquères, M. C.; Spanjaard, D.

    2006-08-01

    The chemical order and magnetic behavior of Fe-dilute fcc Fe-Pd nanoparticles are theoretically investigated using many-body potentials derived in the framework of the generalized second moment approximation (SMA) and self-consistent spin-polarized tight-binding electronic structure calculations, respectively. The SMA total energy calculations reveal that surface sites and the core region are not favorable positions for the Fe impurities and that they prefer to accumulate in the subsurface region of the particles, showing a very strong tendency to separate. However, additional contrasting atomic configurations close in energy are also found which could imply the coexistence in real samples of several Fe-Pd nanoparticles with a well-defined composition, but having different chemical orderings. Magnetic properties are first investigated for a single Fe impurity in bulk Pd, allowing an extension of the polarization cloud around the Fe atom much larger than in an ab initio calculation. The results are in good agreement with experiments and serve as a reference to identify surface and size effects in FePd nanoparticles. Nanoparticles containing from 135 to 561 atoms with up to three Fe substitutional impurities are then investigated, as well as more concentrated ( ≃10% Fe content) shell structures. The extension and magnetic structure of the Fe-induced polarization cloud is studied in detail as a function of the size, surface termination, and the precise location and number of the iron impurities in the particles. The local electronic structure at the Pd sites located at the outermost atomic shell is considerably perturbed by the subsurface position of the Fe atoms and could modify the catalytic properties of palladium nanoparticles. Finally, we show that the value of the orbital-to-spin ratio in our Fe-Pd clusters is very sensitive to the changes in the internal position of the Fe impurities, a result that suggests that x-ray magnetic circular dichroism experiments

  13. Oxidation of CO and Methanol on Pd-Ni Catalysts Supported on Different Chemically-Treated Carbon Nanofibers

    PubMed Central

    Calderón, Juan Carlos; Rios Ráfales, Miguel; Nieto-Monge, María Jesús; Pardo, Juan Ignacio; Moliner, Rafael; Lázaro, María Jesús

    2016-01-01

    In this work, palladium-nickel nanoparticles supported on carbon nanofibers were synthesized, with metal contents close to 25 wt % and Pd:Ni atomic ratios near to 1:2. These catalysts were previously studied in order to determine their activity toward the oxygen reduction reaction. Before the deposition of metals, the carbon nanofibers were chemically treated in order to generate oxygen and nitrogen groups on their surface. Transmission electron microscopy analysis (TEM) images revealed particle diameters between 3 and 4 nm, overcoming the sizes observed for the nanoparticles supported on carbon black (catalyst Pd-Ni CB 1:2). From the CO oxidation at different temperatures, the activation energy Eact for this reaction was determined. These values indicated a high tolerance of the catalysts toward the CO poisoning, especially in the case of the catalysts supported on the non-chemically treated carbon nanofibers. On the other hand, apparent activation energy Eap for the methanol oxidation was also determined finding—as a rate determining step—the COads diffusion to the OHads for the catalysts supported on carbon nanofibers. The results here presented showed that the surface functional groups only play a role in the obtaining of lower particle sizes, which is an important factor in the obtaining of low CO oxidation activation energies. PMID:28335315

  14. Oxidation of CO and Methanol on Pd-Ni Catalysts Supported on Different Chemically-Treated Carbon Nanofibers.

    PubMed

    Calderón, Juan Carlos; Rios Ráfales, Miguel; Nieto-Monge, María Jesús; Pardo, Juan Ignacio; Moliner, Rafael; Lázaro, María Jesús

    2016-10-18

    In this work, palladium-nickel nanoparticles supported on carbon nanofibers were synthesized, with metal contents close to 25 wt % and Pd:Ni atomic ratios near to 1:2. These catalysts were previously studied in order to determine their activity toward the oxygen reduction reaction. Before the deposition of metals, the carbon nanofibers were chemically treated in order to generate oxygen and nitrogen groups on their surface. Transmission electron microscopy analysis (TEM) images revealed particle diameters between 3 and 4 nm, overcoming the sizes observed for the nanoparticles supported on carbon black (catalyst Pd-Ni CB 1:2). From the CO oxidation at different temperatures, the activation energy Eact for this reaction was determined. These values indicated a high tolerance of the catalysts toward the CO poisoning, especially in the case of the catalysts supported on the non-chemically treated carbon nanofibers. On the other hand, apparent activation energy Eap for the methanol oxidation was also determined finding-as a rate determining step-the COads diffusion to the OHads for the catalysts supported on carbon nanofibers. The results here presented showed that the surface functional groups only play a role in the obtaining of lower particle sizes, which is an important factor in the obtaining of low CO oxidation activation energies.

  15. High Loading of Pd Nanoparticles by Interior Functionalization of MOFs for Heterogeneous Catalysis.

    PubMed

    Gole, Bappaditya; Sanyal, Udishnu; Banerjee, Rahul; Mukherjee, Partha Sarathi

    2016-03-07

    In this report, the issue related to nanoparticle (NP) agglomeration upon increasing their loading amount into metal-organic frameworks (MOFs) has been addressed by functionalization of MOFs with alkyne groups. The alkynophilicity of the Pd(2+) (or other noble metals) ions has been utilized successfully for significant loading of Pd NPs into alkyne functionalized MOFs. It has been shown here that the size and loading amount of Pd NPs are highly dependent on the surface area and pore width of the MOFs. The loading amount of Pd NPs was increased monotonically without altering their size distribution on a particular MOF. Importantly, the distinct role of alkyne groups for Pd(2+) stabilization has also been demonstrated by performing a control experiment considering a MOF without an alkyne moiety. The preparation of NPs involved two distinct steps viz. adsorption of metal ions inside MOFs and reduction of metal ions. Both of these steps were monitored by microscopic techniques. This report also demonstrates the applicability of Pd@MOF NPs as extremely efficient heterogeneous catalysts for Heck-coupling and hydrogenation reactions of aryl bromides or iodides and alkenes, respectively.

  16. PdPt bimetallic nanoparticles enabled by shape control with halide ions and their enhanced catalytic activities.

    PubMed

    Zhang, Jinfeng; Wan, Lei; Liu, Lei; Deng, Yida; Zhong, Cheng; Hu, Wenbin

    2016-02-21

    In this study, a new and convenient one step approach is described for synthesizing shape controlled PdPt bimetallic nanoparticles. It is found that the resultant morphologies of these PdPt nanoparticles can be well controlled by simply altering the participation of different halide ions that serve as shape controlling agents in the reaction solution. The dendritic core-shell PdPt bimetallic nanoparticles generated with Pt atoms adopt usual island growth pattern in the presence of Cl(-) ions, whereas the introduction of Br(-) ions with a relatively strong adsorption effect facilitate the formation of a layered core-shell structure due to the layered growth mode of Pt atoms on the exterior surface of the central Pd core. Moreover, the stronger adsorption function of I(-) ions and the resulting fast atomic diffusion promoted the generation of mesoporous core-shell PdPt bimetallic nanoparticles with many pore channels. In addition, the size of these synthesized PdPt nanoparticles exhibited a significant dependence on the concentration of the halide ions involved. Due to their specific structural features and synergistic effects, these PdPt catalysts exhibited shape-dependent catalytic performance and drastically enhanced electrocatalytic activities relative to that of commercial Pt black and Pt/C toward methanol oxidation.

  17. Pd@Pt Core–Shell Nanoparticles with Branched Dandelion-like Morphology as Highly Efficient Catalysts for Olefin Reduction

    EPA Science Inventory

    A facile synthesis based on the addition of ascorbic acid to a mixture of Na2PdCl4, K2PtCl6, and Pluronic P123 results in highly branched core–shell nanoparticles (NPs) with a micro–mesoporous dandelion-like morphology comprising Pd core and Pt shell. The slow reduction kinetics ...

  18. Pd@Pt Core–Shell Nanoparticles with Branched Dandelion-like Morphology as Highly Efficient Catalysts for Olefin Reduction

    EPA Science Inventory

    A facile synthesis based on the addition of ascorbic acid to a mixture of Na2PdCl4, K2PtCl6, and Pluronic P123 results in highly branched core–shell nanoparticles (NPs) with a micro–mesoporous dandelion-like morphology comprising Pd core and Pt shell. The slow reduction kinetics ...

  19. MoS2 Nanosheet-Pd Nanoparticle Composite for Highly Sensitive Room Temperature Detection of Hydrogen.

    PubMed

    Kuru, Cihan; Choi, Chulmin; Kargar, Alireza; Choi, Duyoung; Kim, Young Jin; Liu, Chin Hung; Yavuz, Serdar; Jin, Sungho

    2015-04-01

    Highly sensitive hydrogen detection at room temperature can be realized by employing solution-processed MoS2 nanosheet-Pd nanoparticle composite. A MoS2-Pd composite exhibits greater sensing performance than its graphene counterpart, indicating that solvent exfoliated MoS2 holds great promise for inexpensive and scalable fabrication of highly sensitive chemical sensors.

  20. Functionalized magnetic nanoparticles: A novel heterogeneous catalyst support

    EPA Science Inventory

    Functionalized magnetic nanoparticles have emerged as viable alternatives to conventional materials, as robust, high-surface-area heterogeneous catalyst supports. Post-synthetic surface modification protocol for magnetic nanoparticles has been developed that imparts desirable che...

  1. Functionalized magnetic nanoparticles: A novel heterogeneous catalyst support

    EPA Science Inventory

    Functionalized magnetic nanoparticles have emerged as viable alternatives to conventional materials, as robust, high-surface-area heterogeneous catalyst supports. Post-synthetic surface modification protocol for magnetic nanoparticles has been developed that imparts desirable che...

  2. Exploring the hydrogen absorption into Pd-Ir nanoalloys supported on carbon

    NASA Astrophysics Data System (ADS)

    Malouche, Abdelmalek; Oumellal, Yassine; Ghimbeu, Camelia Matei; de Yuso, Alicia Martínez; Zlotea, Claudia

    2017-08-01

    Comprehensive understanding of the hydrogen gas interaction with metal nanoparticles is crucial for the development of multifunctional materials. The hydrogen absorption properties of well-dispersed Pd-Ir nanoalloys on a mesoporous carbon are reported here. The average size of nanoalloys depends on the composition and is comprised between 2.7 and 3.5 nm with decreasing Ir content. Structural analysis evidences a single phase FCC structure for all nanoparticles and a linear variation of the lattice parameter with composition confirming the formation of nanoalloys in this bulk-immiscible system. The hydrogen absorption properties can be tuned by the chemical composition: Pd-rich nanoparticles form hydride phases, whereas Ir-rich phases do not absorb hydrogen under ambient temperature and pressure conditions. The thermodynamic properties of hydride formation in Pd-rich phases are altered relative to the bulk counterparts. Moreover, the hydrogen absorption capacity in Pd-rich nanoalloys is larger as compared to bulk alloys. This might be explained by an important finite size effect that increases the hydrogen absorption capability of Pd-Ir alloys at nanoscale.

  3. Ag/Pd core-shell nanoparticles by a successive method: Pulsed laser ablation of Ag in water and reduction reaction of PdCl2

    NASA Astrophysics Data System (ADS)

    Mottaghi, N.; Ranjbar, M.; Farrokhpour, H.; Khoshouei, M.; Khoshouei, A.; Kameli, P.; Salamati, H.; Tabrizchi, M.; Jalilian-Nosrati, M.

    2014-02-01

    In this study Ag/Pd nanoparticles (NPs) have been fabricated by a successive method; first, colloids of Ag nanoparticles (NPs) have been prepared in water by pulsed laser ablation in liquid (PLAL) method. Then PdCl2 solution (up to 0.2 g/l) were added to the as-prepared or aged colloidal Ag NPs. Characterizations were done using UV-vis spectroscopy, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and transmissions electron microscopy (TEM) techniques. Spectroscopy data showed that surface plasmon resonance (SPR) peaks of as-prepared Ag NPs at about λ = 400 nm were completely extinguished after addition of PdCl2 solution while this effect was not observed when aged Ag NPs are used. XRD and XPS results revealed that by addition of the PdCl2 solution into the as-prepared Ag NPs, metallic palladium, and silver chloride composition products are generated. TEM images revealed that as a result of this reaction, single and core-shell nanoparticles are obtained and their average sizes are 2.4 nm (Ag) and 3.2 nm (Ag/Pd). The calculated d-spacing values form XRD data with observations on high magnification TEM images were able to explain the chemical nature of different parts of Ag/Pd NPs.

  4. Volcano-like Behavior of Au-Pd Core-shell Nanoparticles in the Selective Oxidation of Alcohols

    PubMed Central

    Silva, Tiago A. G.; Teixeira-Neto, Erico; López, Núria; Rossi, Liane M.

    2014-01-01

    Gold-palladium (AuPd) nanoparticles have shown significantly enhanced activity relative to monometallic Au and Pd catalysts. Knowledge of composition and metal domain distributions is crucial to understanding activity and selectivity, but these parameters are difficult to ascertain in catalytic experiments that have primarily been devoted to equimolar nanoparticles. Here, we report AuPd nanoparticles of varying Au:Pd molar ratios that were prepared by a seed growth method. The selective oxidation of benzyl alcohol was used as a model reaction to study catalytic activity and selectivity changes that occurred after varying the composition of Pd in bimetallic catalysts. We observed a remarkable increase in catalytic conversion when using a 10:1 Au:Pd molar ratio. This composition corresponds to the amount of Pd necessary to cover the existing Au cores with a monolayer of Pd as a full-shell cluster. The key to increased catalytic activity derives from the balance between the number of active sites and the ease of product desorption. According to density functional theory calculations, both parameters are extremely sensitive to the Pd content resulting in the volcano-like activity observed. PMID:25042537

  5. Volcano-like Behavior of Au-Pd Core-shell Nanoparticles in the Selective Oxidation of Alcohols

    NASA Astrophysics Data System (ADS)

    Silva, Tiago A. G.; Teixeira-Neto, Erico; López, Núria; Rossi, Liane M.

    2014-07-01

    Gold-palladium (AuPd) nanoparticles have shown significantly enhanced activity relative to monometallic Au and Pd catalysts. Knowledge of composition and metal domain distributions is crucial to understanding activity and selectivity, but these parameters are difficult to ascertain in catalytic experiments that have primarily been devoted to equimolar nanoparticles. Here, we report AuPd nanoparticles of varying Au:Pd molar ratios that were prepared by a seed growth method. The selective oxidation of benzyl alcohol was used as a model reaction to study catalytic activity and selectivity changes that occurred after varying the composition of Pd in bimetallic catalysts. We observed a remarkable increase in catalytic conversion when using a 10:1 Au:Pd molar ratio. This composition corresponds to the amount of Pd necessary to cover the existing Au cores with a monolayer of Pd as a full-shell cluster. The key to increased catalytic activity derives from the balance between the number of active sites and the ease of product desorption. According to density functional theory calculations, both parameters are extremely sensitive to the Pd content resulting in the volcano-like activity observed.

  6. Volcano-like behavior of Au-Pd core-shell nanoparticles in the selective oxidation of alcohols.

    PubMed

    Silva, Tiago A G; Teixeira-Neto, Erico; López, Núria; Rossi, Liane M

    2014-07-21

    Gold-palladium (AuPd) nanoparticles have shown significantly enhanced activity relative to monometallic Au and Pd catalysts. Knowledge of composition and metal domain distributions is crucial to understanding activity and selectivity, but these parameters are difficult to ascertain in catalytic experiments that have primarily been devoted to equimolar nanoparticles. Here, we report AuPd nanoparticles of varying Au:Pd molar ratios that were prepared by a seed growth method. The selective oxidation of benzyl alcohol was used as a model reaction to study catalytic activity and selectivity changes that occurred after varying the composition of Pd in bimetallic catalysts. We observed a remarkable increase in catalytic conversion when using a 10:1 Au:Pd molar ratio. This composition corresponds to the amount of Pd necessary to cover the existing Au cores with a monolayer of Pd as a full-shell cluster. The key to increased catalytic activity derives from the balance between the number of active sites and the ease of product desorption. According to density functional theory calculations, both parameters are extremely sensitive to the Pd content resulting in the volcano-like activity observed.

  7. Pd nanoparticles on ZnO-passivated porous carbon by atomic layer deposition: an effective electrochemical catalyst for Li-O2 battery.

    PubMed

    Luo, Xiangyi; Piernavieja-Hermida, Mar; Lu, Jun; Wu, Tianpin; Wen, Jianguo; Ren, Yang; Miller, Dean; Zak Fang, Zhigang; Lei, Yu; Amine, Khalil

    2015-04-24

    Uniformly dispersed Pd nanoparticles on ZnO-passivated porous carbon were synthesized via an atomic layer deposition (ALD) technique, which was tested as a cathode material in a rechargeable Li-O2 battery, showing a highly active catalytic effect toward the electrochemical reactions-in particular, the oxygen evolution reaction. Transmission electron microscopy (TEM) showed discrete crystalline nanoparticles decorating the surface of the ZnO-passivated porous carbon support in which the size could be controlled in the range of 3-6 nm, depending on the number of Pd ALD cycles performed. X-ray absorption spectroscopy (XAS) at the Pd K-edge revealed that the carbon-supported Pd existed in a mixed phase of metallic palladium and palladium oxide. The ZnO-passivated layer effectively blocks the defect sites on the carbon surface, minimizing the electrolyte decomposition. Our results suggest that ALD is a promising technique for tailoring the surface composition and structure of nanoporous supports for Li-O2 batteries.

  8. Pd Nanoparticles on ZnO-passivated Porous Carbon by Atomic Layer Deposition: an Effective Electrochemical Catalyst for Li-O2 Battery

    SciTech Connect

    Luo, Xiangyi; Piernavieja-Hermida, Mar; Lu, Jun; Wu, Tianpin; Wen, Jianguo; Ren, Yang; Miller, Dean J.; Fang, Zhigang Zak; Lei, Yu; Amine, Khalil

    2015-04-24

    Uniformly dispersed Pd nanoparticles on ZnO-passivated porous carbon were synthesized via an atomic layer deposition (ALD) technique, which was tested as a cathode material in a rechargeable Li-O-2 battery, showing a highly active catalytic effect toward the electrochemical reactions-in particular, the oxygen evolution reaction. Transmission electron microscopy (TEM) showed discrete crystalline nanoparticles decorating the surface of the ZnO-passivated porous carbon support in which the size could be controlled in the range of 3-6 nm, depending on the number of Pd ALD cycles performed. X-ray absorption spectroscopy (XAS) at the Pd Kedge revealed that the carbon-supported Pd existed in a mixed phase of metallic palladium and palladium oxide. The ZnO-passivated layer effectively blocks the defect sites on the carbon surface, minimizing the electrolyte decomposition. Our results suggest that ALD is a promising technique for tailoring the surface composition and structure of nanoporous supports for Li-O-2 batteries.

  9. Autoprogrammed synthesis of triple-layered Au@Pd@Pt core-shell nanoparticles consisting of a Au@Pd bimetallic core and nanoporous Pt shell.

    PubMed

    Wang, Liang; Yamauchi, Yusuke

    2010-10-06

    Here we report an autoprogrammed synthesis of unique Au@Pd@Pt triple-layered core-shell structured nanoparticles consisting of a Au core, Pd inner layer, and nanoporous Pt outer shell. The proposed synthesis rationally utilizes the temporal separations of the depositions of Au, Pd, and Pt which affords spontaneously step-by-step formation of triple-layered core-shell colloids. The proposed one-step method is unique in its simplicity and is a significant finding for the facile creation of multilayered nanoarchitectures with designed compositions and desired functions.

  10. Transformation of Sodium Bicarbonate and CO2 into Sodium Formate over NiPd Nanoparticle Catalyst

    NASA Astrophysics Data System (ADS)

    Wang, Mengnan; Zhang, Jiaguang; Yan, Ning

    2013-09-01

    The present research systematically investigated, for the first time, the transformation of sodium bicarbonate and CO2 into sodium formate over a series of Ni based metal nanoparticles (NPs). Ni NPs and eight NiM (M stands for a second metal) NPs were prepared by a facile wet chemical process and then their catalytic performance were evaluated in sodium bicarbonate hydrogenation. Bimetallic NiPd NPs with a composition of 7:3 were found to be superior for this reaction, which are more active than both pure Ni and Pd NPs. Hot filtration experiment suggested the NPs to be the truly catalytic active species and kinetic analysis indicated the reaction mechanism to be different than most homogeneous catalysts. The enhanced activity of the bimetallic nanoparticles may be attributed to their smaller size and improved stability.

  11. Transformation of sodium bicarbonate and CO2 into sodium formate over NiPd nanoparticle catalyst

    PubMed Central

    Wang, Mengnan; Zhang, Jiaguang; Yan, Ning

    2013-01-01

    The present research systematically investigated, for the first time, the transformation of sodium bicarbonate and CO2 into sodium formate over a series of Ni based metal nanoparticles (NPs). Ni NPs and eight NiM (M stands for a second metal) NPs were prepared by a facile wet chemical process and then their catalytic performance were evaluated in sodium bicarbonate hydrogenation. Bimetallic NiPd NPs with a composition of 7:3 were found to be superior for this reaction, which are more active than both pure Ni and Pd NPs. Hot filtration experiment suggested the NPs to be the truly catalytic active species and kinetic analysis indicated the reaction mechanism to be different than most homogeneous catalysts. The enhanced activity of the bimetallic nanoparticles may be attributed to their smaller size and improved stability. PMID:24790945

  12. Transformation of sodium bicarbonate and CO2 into sodium formate over NiPd nanoparticle catalyst.

    PubMed

    Wang, Mengnan; Zhang, Jiaguang; Yan, Ning

    2013-01-01

    The present research systematically investigated, for the first time, the transformation of sodium bicarbonate and CO2 into sodium formate over a series of Ni based metal nanoparticles (NPs). Ni NPs and eight NiM (M stands for a second metal) NPs were prepared by a facile wet chemical process and then their catalytic performance were evaluated in sodium bicarbonate hydrogenation. Bimetallic NiPd NPs with a composition of 7:3 were found to be superior for this reaction, which are more active than both pure Ni and Pd NPs. Hot filtration experiment suggested the NPs to be the truly catalytic active species and kinetic analysis indicated the reaction mechanism to be different than most homogeneous catalysts. The enhanced activity of the bimetallic nanoparticles may be attributed to their smaller size and improved stability.

  13. Exchange-coupled fct-FePd/α-Fe nanocomposite magnets converted from Pd/Fe3O4 core/shell nanoparticles.

    PubMed

    Liu, Fei; Dong, Yunhe; Yang, Wenlong; Yu, Jing; Xu, Zhichuan; Hou, Yanglong

    2014-11-10

    We report the controlled synthesis of exchange-coupled face-centered tetragonal (fct) FePd/α-Fe nanocomposite magnets with variable Fe concentration. The composite was converted from Pd/Fe3O4 core/shell nanoparticles through a high-temperature annealing process in a reducing atmosphere. The shell thickness of core/shell Pd/Fe3O4 nanoparticles could be readily tuned, and subsequently the concentration of Fe in nanocomposite magnets was controlled. Upon annealing reduction, the hard magnetic fct-FePd phase was formed by the interdiffusion between reduced α-Fe and face-centered cubic (fcc) Pd, whereas the excessive α-Fe remained around the fct-FePd grains, realizing exchange coupling between the soft magnetic α-Fe and hard magnetic fct-FePd phases. Magnetic measurements showed variation in the magnetic properties of the nanocomposite magnets with different compositions, indicating distinct exchange coupling at the interfaces. The coercivity of the exchange-coupled nanocomposites could be tuned from 0.7 to 2.8 kOe and the saturation magnetization could be controlled from 93 to 160 emu g(-1). This work provides a bottom-up approach using exchange-coupled nanocomposites for engineering advanced permanent magnets with controllable magnetic properties.

  14. Sensitive voltammetric determination of vanillin with an AuPd nanoparticles-graphene composite modified electrode.

    PubMed

    Shang, Lei; Zhao, Faqiong; Zeng, Baizhao

    2014-05-15

    In this work, graphene oxide was reduced to graphene with an endogenous reducing agent from dimethylformamide, and then AuPd alloy nanoparticles were electrodeposited on the graphene film. The obtained AuPd-graphene hybrid film was characterized by scanning electron microscopy, energy dispersive X-ray spectroscopy, X-ray diffraction and voltammetry. The electrochemical behavior of vanillin was studied using the AuPd-graphene hybrid based electrode. It presented high electrocatalytic activity and vanillin could produce a sensitive oxidation peak at it. Under the optimal conditions, the peak current was linear to the concentration of vanillin in the ranges of 0.1-7 and 10-40 μM. The sensitivities were 1.60 and 0.170 mA mM(-1) cm(-2), respectively; the detection limit was 20 nM. The electrode was successfully applied to the detection of vanillin in vanilla bean, vanilla tea and biscuit samples.

  15. Encapsulating Pd nanoparticles in double-shelled graphene@carbon hollow spheres for excellent chemical catalytic property.

    PubMed

    Zhang, Zheye; Xiao, Fei; Xi, Jiangbo; Sun, Tai; Xiao, Shuang; Wang, Hairong; Wang, Shuai; Liu, Yunqi

    2014-02-11

    Double-shelled hollow carbon spheres with reduced graphene oxide (RGO) as inner shell and carbon (C) layer as outer shell have been successfully designed and prepared. This tailor-making structure acts as an excellent capsule for encapsulating with ultrafine Pd nanoparticles (Pd NPs), which could effectively prevent Pd NPs from aggregation and leaching. As a result, the as-obtained RGO@Pd@C nanohybid exhibits superior and stable catalytic performance. With the aid of RGO@Pd@C, the reduction reaction of 4-nitrophenol (4-NP) to 4-aminophenol with NaBH4 as reducing agent can be finished within only 30 s, even the content of Pd is as low as 0.28 wt%. As far as we know, RGO@Pd@C is one of the most effective catalyst for 4-NP reducing reaction up to now.

  16. Method for forming thermally stable nanoparticles on supports

    DOEpatents

    Roldan Cuenya, Beatriz; Naitabdi, Ahmed R.; Behafarid, Farzad

    2013-08-20

    An inverse micelle-based method for forming nanoparticles on supports includes dissolving a polymeric material in a solvent to provide a micelle solution. A nanoparticle source is dissolved in the micelle solution. A plurality of micelles having a nanoparticle in their core and an outer polymeric coating layer are formed in the micelle solution. The micelles are applied to a support. The polymeric coating layer is then removed from the micelles to expose the nanoparticles. A supported catalyst includes a nanocrystalline powder, thin film, or single crystal support. Metal nanoparticles having a median size from 0.5 nm to 25 nm, a size distribution having a standard deviation .ltoreq.0.1 of their median size are on or embedded in the support. The plurality of metal nanoparticles are dispersed and in a periodic arrangement. The metal nanoparticles maintain their periodic arrangement and size distribution following heat treatments of at least 1,000.degree. C.

  17. C-O hydrogenolysis catalyzed by Pd-PMHS nanoparticles in the company of chloroarenes.

    PubMed

    Rahaim, Ronald J; Maleczka, Robert E

    2011-02-18

    Catalytic Pd(OAc)(2) and polymethylhydrosiloxane (PMHS), in conjunction with aqueous KF, and a catalytic amount of an aromatic chloride, effects the chemo-, regio-, and stereoselective deoxygenation of benzylic oxygenated substrates at room temperature in THF. Preliminary mechanistic experiments suggest the process to involve palladium-nanoparticle-catalyzed hydrosilylation followed by C-O reduction. The chloroarene additive appears to facilitate the hydrogenolysis process through the slow controlled release of HCl.

  18. Catalytic oxidation of low-concentration CO at ambient temperature over supported Pd-Cu catalysts.

    PubMed

    Wang, Fagen; Zhang, Haojie; He, Dannong

    2014-01-01

    The CO catalytic oxidation at ambient temperature and high space velocity was studied over the Pd-Cu/MOx (MOx = TiO2 and AI203) catalysts. The higher Brunauer-Emmett-Teller area surface of the A1203 support facilitates the dispersion of Pd2+ species, and the presence of Cu2Cl(OH)3 accelerates the re-oxidation of Pd0 to Pd2+ over the Pd-Cu/Al203 catalyst, which contributed to better performance of CO catalytic oxidation. The poorer activity of the Pd-Cu/TiO2 catalyst was attributed to the lower dispersion of Pd2+ species because of the less surface area and the non-formation of Cu2CI(OH)3 species. The presence of saturated moisture showed a negative effect on CO conversion over the two catalysts. This might be because of the competitive adsorption, the formation of carbonate species and the transformation of Cu2CI(OH)3 to inactive CuCI over the Pd-Cu/AI2O3 catalyst, which facilitates the aggregation of PdO species over the Pd-Cu/TiO2 catalyst under the moisture condition.

  19. Ti(3+)-Promoted High Oxygen-Reduction Activity of Pd Nanodots Supported by Black Titania Nanobelts.

    PubMed

    Yuan, Xiaotao; Wang, Xin; Liu, Xiangye; Ge, Hongxin; Yin, Guoheng; Dong, Chenlong; Huang, Fuqiang

    2016-10-04

    One-dimensional nanocrystals favoring efficient charge transfer have attracted enormous attentions, and conductive nanobelts of black titania with a unique band structure and high electrical conductivity would be interestingly used in electrocatalysis. Here, Pd nanodots supported by two kinds of black titania, the oxygen-deficient titania (TiO2-x) and nitrogen-doped titania (TiO2-x:N), were synthesized as efficient composite catalysts for oxygen-reduction reaction (ORR). These composite catalysts show improved catalytic activity with lower overpotential and higher limited current, compared to the Pd nanodots supported on the white titania (Pd/TiO2). The improved activity is attributed to the relatively high conductivity of black titania nanobelts for efficient charge transfer (CT) between Ti(3+) species and Pd nanodots. The CT process enhances the strong metal-support interaction (SMSI) between Pd and TiO2, which lowers the absorption energy of O2 on Pd and makes it more suitable for oxygen reduction. Because of the stronger interaction between Pd and support, the Pd/TiO2-x:N also shows excellent durability and immunity to methanol poisoning.

  20. Catalytic property of fiber media supported palladium containing alloy nanoparticles and electrospun ceramic fibers biodurability study

    NASA Astrophysics Data System (ADS)

    Shin, Hyeon Ung

    The nanoscale of the supporting fibers may provide enhancements such as restricting the migration of metal catalyst particles. In this work, palladium nanoparticle doped alumina fibers were electrospun into template submicron fibers. These fibers were calcined at temperatures between 650°C and 1150°C to vary the crystal structures of the calcined fibers with the Pd particle size. Higher calcination temperatures led to higher reaction temperatures from 250 to about 450°C for total conversion, indicating the effective reactivity of the fiber-supported catalysts decreased with increase in calcination temperature. Pd-Au alloy nanoparticle doped titania fibers were also fabricated using an electrospinning method and assembled into a fibrous porous medium structure by a vacuum molding process. In reactor tests, the fiber media with Pd-Au alloy nanoparticle catalyst had greater reactivity in conversion of NO and CO gases than that of fiber media with Pd monometallic catalyst alone, attributed to a lower activation energy of the Pd-Au catalyst particles. In carbon monoxide oxidation reaction tests, the results showed that the performance was optimal for a catalyst of composition Pd2Au1 molar ratio that was active at 125°C, which had higher dispersion of active components and better catalytic performance compared to monometallic particle Au/TiO 2 and Pd/TiO2 fiber media. Moreover, the improved reaction activity of Pd2Au1/TiO2 fiber medium was attributed to a decreased in the activation energy. Further experiments were conducted using the electrospun ceramic fibers biodurability study. The properties of nano-sized fiber structures have attracted the attention of recent research on ceramic nanostructures as nonwoven media for applications in hazardous chemical and high temperature environments. However, health and safety concerns of micro and nano scale ceramic materials have not been fully investigated. Little is known about the physicochemical effects of the properties

  1. Alumina-supported Pd-Ag catalysts for low-temperature CO and methanol oxidation

    NASA Technical Reports Server (NTRS)

    Mccabe, R. W.

    1987-01-01

    Pd-Ag bimetallic catalysts, supported on gamma-Al2O3, have been evaluated as exhaust catalysts for methanol-fueled vehicles. Laboratory studies have shown that a 0.01% Pd-5% Ag catalyst has greater CO and CH3OH oxidation activity than either 0.01% Pd or 5% Ag catalysts alone. Moreover, Pd and Ag interact synergistically in the bimetallic catalyst to produce greater CO and CH3OH oxidation rates and lower yields of methanol partial oxidation products than expected from a mixture of the single-component catalysts. The Pd-Ag synergism results from Pd promoting the rate of O2 adsorption and reaction with CO and CH3OH on Ag. Rate enhancement by the bimetallic catalyst is greatest at short reactor residence times where the oxygen adsorption rate limits the overall reaction rate.

  2. In situ-generated metal oxide catalyst during CO oxidation reaction transformed from redox-active metal-organic framework-supported palladium nanoparticles

    PubMed Central

    2012-01-01

    The preparation of redox-active metal-organic framework (ra-MOF)-supported Pd nanoparticles (NPs) via the redox couple-driven method is reported, which can yield unprotected metallic NPs at room temperature within 10 min without the use of reducing agents. The Pd@ra-MOF has been exploited as a precursor of an active catalyst for CO oxidation. Under the CO oxidation reaction condition, Pd@ra-MOF is transformed into a PdOx-NiOy/C nanocomposite to generate catalytically active species in situ, and the resultant nanocatalyst shows sustainable activity through synergistic stabilization. PMID:22898143

  3. Inhibition of carbon monoxide on methanol oxidation over γ-alumina supported Ag, Pd and Ag Pd catalysts

    NASA Astrophysics Data System (ADS)

    Wang, Jin-an; Aguilar-Ríos, G.; Wang, Ren

    1999-05-01

    The activities of CH 3OH and CO oxidative reactions over the γ-alumina supported Ag, Pd and Ag-Pd catalysts were measured with the MR-GC method. The CO-temperature-programmed desorption (CO-TPD) and in situ IR techniques were used to characterize the CO adsorption behavior on the surface of the catalysts. The oxidative activity for CO to CO 2 increased in the following sequence: 5% Ag/γ-Al 2O 3<0.1% Pd/γ-Al 2O 3<5% Ag-0.1% Pd/γ-Al 2O 3. An inhibition action of CO to CH 3OH oxidation, that is dependent of the active components of the catalysts, was observed when CO was present in the methanol-fed stream. The results of IR and CO-TPD showed that the poor oxidative activity of CO over Ag catalyst was due to its low adsorption capacity on this catalyst. The very strong adsorption ability of CO on the Pd catalyst was responsible for the strong inhibition of CO to CH 3OH oxidation activity. The plausible mechanisms of CO strong inhibition behavior on methanol oxidation over the different catalysts are discussed in detail from the viewpoints of both electronic and geometric effects.

  4. Highly Active Carbon Supported Pd-Ag Nanofacets Catalysts for Hydrogen Production from HCOOH.

    PubMed

    Wang, Wenhui; He, Ting; Liu, Xuehua; He, Weina; Cong, Hengjiang; Shen, Yangbin; Yan, Liuming; Zhang, Xuetong; Zhang, Jinping; Zhou, Xiaochun

    2016-08-17

    Hydrogen is regarded as a future sustainable and clean energy carrier. Formic acid is a safe and sustainable hydrogen storage medium with many advantages, including high hydrogen content, nontoxicity, and low cost. In this work, a series of highly active catalysts for hydrogen production from formic acid are successfully synthesized by controllably depositing Pd onto Ag nanoplates with different Ag nanofacets, such as Ag{111}, Ag{100}, and the nanofacet on hexagonal close packing Ag crystal (Ag{hcp}). Then, the Pd-Ag nanoplate catalysts are supported on Vulcan XC-72 carbon black to prevent the aggregation of the catalysts. The research reveals that the high activity is attributed to the formation of Pd-Ag alloy nanofacets, such as Pd-Ag{111}, Pd-Ag{100}, and Pd-Ag{hcp}. The activity order of these Pd-decorated Ag nanofacets is Pd-Ag{hcp} > Pd-Ag{111} > Pd-Ag{100}. Particularly, the activity of Pd-Ag{hcp} is up to an extremely high value, i.e., TOF{hcp} = 19 000 ± 1630 h(-1) at 90 °C (lower limit value), which is more than 800 times higher than our previous quasi-spherical Pd-Ag alloy nanocatalyst. The initial activity of Pd-Ag{hcp} even reaches (3.13 ± 0.19) × 10(6) h(-1) at 90 °C. This research not only presents highly active catalysts for hydrogen generation but also shows that the facet on the hcp Ag crystal can act as a potentially highly active catalyst.

  5. The effect of microemulsion composition on the morphology of Pd nanoparticles deposited at the surface of TiO2 and photoactivity of Pd-TiO2

    NASA Astrophysics Data System (ADS)

    Długokęcka, Marta; Łuczak, Justyna; Polkowska, Żaneta; Zaleska-Medynska, Adriana

    2017-05-01

    A series of microemulsion (ME) system, constituted by different water to surfactant molar ratios (Wo) and oil to surfactant mass ratios (S), have been applied for Pd-TiO2 preparation. The effect of ME properties on the morphology of Pd nanoparticles formed at TiO2 surface and an effect of Pd size and distribution on the surface and photocatalytic properties of Pd-TiO2 were investigated. Microemulsion systems were characterized by means of viscosity, density, dynamic light scattering as well as surface tension measurements to find a correlation between the conditions of Pd nanoparticles formation, their morphology and photocatalyst features. The photocatalysts were characterized by transmission electron microscopy (TEM), X-ray diffraction analysis (XRD), UV-vis diffuse-reflectance spectroscopy (DRS), BET surface area and elemental analysis. The photocatalytic properties of Pd-modified TiO2 particles were studied in a model reaction of phenol photodegradation under Vis irradiation, as well as active species involved in the photocatalytic reaction were determined. Microemulsion composition was found to be a crucial parameter in determining the features of the TiO2-based photocatalysts covered by metallic nanoparticles. The highest photocatalytic activity under Vis radiation was observed for the Pd-TiO2 sample (average diameter 2.4 nm) obtained using 0.1 mol% Pd in the ME system containing 1.5 wt% of water and 82.8 wt% of cyclohexane with average droplet size of 2.83 ± 0.18 nm. In this regard, synthesis of such metal-semiconductor composites through the microemulsion route should always be preceded by investigation of ME properties in order to the eliminate the inhibitory effect of ME internal structure.

  6. Beet juice utilization: Expeditious green synthesis of nobel metal nanoparticles (Ag, Au, Pt, and Pd) using microwaves

    EPA Science Inventory

    Metal nanoparticles of Ag, Au, Pt, and Pd were prepared in aqueous solutions via a rapid microwave-assisted green method using beet juice, an abundant sugar-rich agricultural produce, served as both a reducing and a capping reagent. The Ag nanoparticles with capping prepared by b...

  7. Beet juice utilization: Expeditious green synthesis of nobel metal nanoparticles (Ag, Au, Pt, and Pd) using microwaves

    EPA Science Inventory

    Metal nanoparticles of Ag, Au, Pt, and Pd were prepared in aqueous solutions via a rapid microwave-assisted green method using beet juice, an abundant sugar-rich agricultural produce, served as both a reducing and a capping reagent. The Ag nanoparticles with capping prepared by b...

  8. Temperature dependent carrier mobility in graphene: Effect of Pd nanoparticle functionalization and hydrogenation

    NASA Astrophysics Data System (ADS)

    Zhong, Bochen; Uddin, Md Ahsan; Singh, Amol; Webb, Richard; Koley, Goutam

    2016-02-01

    The two dimensional nature of graphene, with charge carriers confined within one atomic layer thickness, causes its electrical, optical, and sensing properties to be strongly influenced by the surrounding media and functionalization layers. In this study, the effect of catalytically active Pd nanoparticle (NP) functionalization and subsequent hydrogenation on the hall mobility and carrier density of chemical vapor deposition synthesized graphene has been investigated as a function of temperature. Prior to functionalization, the mobility decreased monotonically as the temperature was reduced from 298 to 10 K, indicating coulomb scattering as the dominant scattering mechanism as expected for bilayer graphene. Similar decreasing trend with temperature was also observed after 2 nm Pd deposition, however, hydrogenation of the Pd NP led to significant enhancement in mobility from ˜2250 to 3840 cm2/V s at room temperature, which further monotonically increased to 5280 cm2/V s at 10 K. We attribute this contrasting trend in temperature dependent mobility to a switch in the dominant scattering mechanism from coulomb to surface optical (SO) phonon scattering due to higher dielectric constant and polar nature of PdHx formed upon hydrogenation of the Pd NPs.

  9. Local structure at interfaces between hydride-forming metals: A case study of Mg-Pd nanoparticles by x-ray spectroscopy

    NASA Astrophysics Data System (ADS)

    Pasquini, L.; Boscherini, F.; Callini, E.; Maurizio, C.; Pasquali, L.; Montecchi, M.; Bonetti, E.

    2011-05-01

    The structure at the interface between elements or phases that exhibit different hydrogen (H) binding energies exerts a profound influence on the thermodynamics of H in nanophase materials. In this paper, we study the local structure at the Mg/Pd interface in Mg nanoparticles with partial Pd coating, and we map its evolution in response to annealing and H sorption. This task is accomplished by x-ray photoelectron spectroscopy and x-ray absorption spectroscopy, also including in situ experiments, with the support of crystallographic information from x-ray diffraction. It is shown that the initial Pd surface layer reacts with Mg at relatively low temperatures, leading to irreversible formation of a Mg-rich intermetallic phase Mg6Pd. Due to the high Mg-H binding energy, this phase reversibly transforms, upon H absorption, into a nanophase mixture of magnesium hydride and a Pd-rich intermetallic with H in solid solution, MgPdHδ. These reversible structural changes are discussed with reference to recent calculations that highlight their relevance to the thermodynamics of the metal-hydride transition. The picture drawn here might be relevant to other multiphase materials presently investigated in the field of hydrogen-related science and technology.

  10. Reducing-Agent-Free Instant Synthesis of Carbon-Supported Pd Catalysts in a Green Leidenfrost Droplet Reactor and Catalytic Activity in Formic Acid Dehydrogenation

    PubMed Central

    Lee, Dong-Wook; Jin, Min-Ho; Lee, Young-Joo; Park, Ju-Hyoung; Lee, Chun-Boo; Park, Jong-Soo

    2016-01-01

    The development of green synthesis methods for supported noble metal catalysts remains important challenges to improve their sustainability. Here we first synthesized carbon-supported Pd catalysts in a green Leidenfrost droplet reactor without reducing agents, high-temperature calcination and reduction procedures. When the aqueous solution containing Pd nitrate precursor, carbon support, and water is dripped on a hot plate, vapor layer is formed between a solution droplet and hot surface, which allow the solution droplet to be levitated on the hot surface (Leidenfrost phenomena). Subsequently, Pd nanoparticles can be prepared without reducing agents in a weakly basic droplet reactor created by the Leidenfrost phenomena, and then the as-prepared Pd nanoparticles are loaded on carbon supports during boiling down the droplet on hot surface. Compared to conventional incipient wetness and chemical synthetic methods, the Leidenfrost droplet reactor does not need energy-consuming, time-consuming, and environmentally unfriendly procedures, which leads to much shorter synthesis time, lower carbon dioxide emission, and more ecofriendly process in comparison with conventional synthesis methods. Moreover, the catalysts synthesized in the Leidenfrost droplet reactor provided much better catalytic activity for room-temperature formic acid decomposition than those prepared by the incipient wetness method. PMID:27198855

  11. Reducing-Agent-Free Instant Synthesis of Carbon-Supported Pd Catalysts in a Green Leidenfrost Droplet Reactor and Catalytic Activity in Formic Acid Dehydrogenation

    NASA Astrophysics Data System (ADS)

    Lee, Dong-Wook; Jin, Min-Ho; Lee, Young-Joo; Park, Ju-Hyoung; Lee, Chun-Boo; Park, Jong-Soo

    2016-05-01

    The development of green synthesis methods for supported noble metal catalysts remains important challenges to improve their sustainability. Here we first synthesized carbon-supported Pd catalysts in a green Leidenfrost droplet reactor without reducing agents, high-temperature calcination and reduction procedures. When the aqueous solution containing Pd nitrate precursor, carbon support, and water is dripped on a hot plate, vapor layer is formed between a solution droplet and hot surface, which allow the solution droplet to be levitated on the hot surface (Leidenfrost phenomena). Subsequently, Pd nanoparticles can be prepared without reducing agents in a weakly basic droplet reactor created by the Leidenfrost phenomena, and then the as-prepared Pd nanoparticles are loaded on carbon supports during boiling down the droplet on hot surface. Compared to conventional incipient wetness and chemical synthetic methods, the Leidenfrost droplet reactor does not need energy-consuming, time-consuming, and environmentally unfriendly procedures, which leads to much shorter synthesis time, lower carbon dioxide emission, and more ecofriendly process in comparison with conventional synthesis methods. Moreover, the catalysts synthesized in the Leidenfrost droplet reactor provided much better catalytic activity for room-temperature formic acid decomposition than those prepared by the incipient wetness method.

  12. Reducing-Agent-Free Instant Synthesis of Carbon-Supported Pd Catalysts in a Green Leidenfrost Droplet Reactor and Catalytic Activity in Formic Acid Dehydrogenation.

    PubMed

    Lee, Dong-Wook; Jin, Min-Ho; Lee, Young-Joo; Park, Ju-Hyoung; Lee, Chun-Boo; Park, Jong-Soo

    2016-05-20

    The development of green synthesis methods for supported noble metal catalysts remains important challenges to improve their sustainability. Here we first synthesized carbon-supported Pd catalysts in a green Leidenfrost droplet reactor without reducing agents, high-temperature calcination and reduction procedures. When the aqueous solution containing Pd nitrate precursor, carbon support, and water is dripped on a hot plate, vapor layer is formed between a solution droplet and hot surface, which allow the solution droplet to be levitated on the hot surface (Leidenfrost phenomena). Subsequently, Pd nanoparticles can be prepared without reducing agents in a weakly basic droplet reactor created by the Leidenfrost phenomena, and then the as-prepared Pd nanoparticles are loaded on carbon supports during boiling down the droplet on hot surface. Compared to conventional incipient wetness and chemical synthetic methods, the Leidenfrost droplet reactor does not need energy-consuming, time-consuming, and environmentally unfriendly procedures, which leads to much shorter synthesis time, lower carbon dioxide emission, and more ecofriendly process in comparison with conventional synthesis methods. Moreover, the catalysts synthesized in the Leidenfrost droplet reactor provided much better catalytic activity for room-temperature formic acid decomposition than those prepared by the incipient wetness method.

  13. Direct hydrogenation and one-pot reductive amidation of nitro compounds over Pd/ZnO nanoparticles as a recyclable and heterogeneous catalyst

    NASA Astrophysics Data System (ADS)

    Hosseini-Sarvari, Mona; Razmi, Zahra

    2015-01-01

    A novel Pd supported on ZnO nanoparticles was readily synthesized and characterized. The amount of palladium on ZnO is 9.84 wt% which was determined by ICP analysis and atomic absorption spectroscopy (AAS). Percentage of accessible Pd as active catalyst is also estimated to 2.72% based on the thermogravimetric (TG) analysis. This nano-sized Pd/ZnO with an average particle size of 20-25 nm and specific surface area 40.61 m2 g-1 was used as a new reusable heterogeneous catalyst for direct hydrogenation and one-pot reductive amidation of nitro compounds without the use of any ligands under atmospheric pressure. The catalyst can be recovered and recycled several times without marked loss of activity.

  14. Dendrimer-templated Pd nanoparticles and Pd nanoparticles synthesized by reverse microemulsions as efficient nanocatalysts for the Heck reaction: A comparative study.

    PubMed

    Noh, Ji-Hyang; Meijboom, Reinout

    2014-02-01

    Palladium nanoparticles (NPs) were prepared using a dendrimer-templated method using G4, G5 and G6 PAMAM-OH dendrimers as well as a reverse microemulsion method using the water/dioctyl sulfosuccinate sodium salt (aerosol-OT, AOT) surfactant/isooctane system with water to surfactant ratios (ω0) of 5, 10 and 13. These 6 catalysts were characterized by UV-Vis spectroscopy, TEM, EDX, and XRD. TEM micrographs showed that the average sizes of 2.74-3.32nm with narrower size distribution were achieved by using dendrimer-templated synthetic methods, whereas the reverse microemulsion method resulted in broad size distribution with an average size of 3.87-5.06nm. The influence of various reaction parameters such as base, catalyst dosing, alkene, aryl halide and temperature on the Heck C-C coupling reaction was evaluated. The activation parameters were derived from the reaction rate of each catalyst obtained at various temperatures. A correlation of catalytic activity, enthalpy of activation and particle size is discussed. Particle size changes of each catalyst were investigated after the catalytic reaction. Overall results indicated that dendrimer-templated Pd NP catalysts showed superior activity as compared to the Pd NPs synthesized by reverse microemulsions, with the dendrimer-templated G5-OH(Pd80) showing the best activity. These catalysts were also reusable for 3 cycles, retaining high yield and showing excellent yields under mild conditions. Therefore, the dendrimer-templated Pd NPs are efficient catalyst systems for the ligand-free Heck C-C coupling reaction.

  15. New Insights into the structure of Pd-Au nanoparticles as revealed by aberration-corrected STEM

    PubMed Central

    Deepak, Francis Leonard; Casillas-Garcia, Gilberto; Esparza, Rodrigo; Barron, H.; Jose-Yacaman, Miguel

    2011-01-01

    Bimetallic nanoparticles of Au-Pd find important applications in catalysis. Their catalytic performance is directly related to the structure, alloy formation and variation of composition in the structure. A standard idea is that bimetallic nanoparticles can be either an alloy or a core shell structure. Our group has investigated the structure and composition of Pd-Au nanoparticles by using aberration corrected high angle annular dark field scanning transmission electron microscopy (HAADF-STEM). We reported previously that the nanoparticles are composed of an evenly alloyed inner core, an Au-rich intermediate layer, and a Pd-rich outer shell. The structure is more complicated than what simple models can predict. In this paper we report additional studies of this system wherein by carrying out spectral and chemical analysis (STEM*-EDAX, STEM-EELS) the interface structure can now be better identified and understood. Apart from the three-layered core-shell structures we have also been able to observe in some cases a four-layered core-shell structure as well. The entire core-shell structure is not rigid and there is indeed intercalation of Au-Pd into the other layers as well. In addition we have been able to locate stacking faults present in the nanoparticles. We also address the problem of the interface structure between the layers. By using nanodiffraction we have found that the whole structure of the nanoparticles becomes hcp in contrast to the bulk structure of Au or Pd. PMID:21804646

  16. Trimetallic nanostructures: the case of AgPd/Pt multiply twinned nanoparticles

    PubMed Central

    Khanal, Subarna; Bhattarai, Nabraj; Velázquez-Salazar, J. Jesús; Bahena, Daniel; Soldano, German; Ponce, Arturo; Mariscal, Marcelo M.; Mejía-Rosales, Sergio; José-Yacamán, Miguel

    2013-01-01

    We report the synthesis, structural characterization, and atomistic simulations of AgPd/Pt trimetallic (TM) nanoparticles. Two types of structure were synthesized using a relatively facile chemical method: multiply twinned core-shell, and hollow particles. The nanoparticles were small in size, with an average diameter of 11 nm and a narrow distribution, and their characterization by aberration corrected scanning transmission electron microscopy allowed us to probe the structure of the particles at atomistic level. In some nanoparticles, the formation of a hollow structure was also observed, that facilitates the alloying of Ag and Pt in the shell region and the segregation of Ag atoms in the surface, affecting the catalytic activity and stability. We also investigated the growth mechanism of the nanoparticles using grand canonical Monte Carlo simulations, and we have found that Pt regions grow at overpotentials on the AgPd nanoalloys, forming 3D islands at the early stages of the deposition process. We found very good agreement between the simulated structures and those observed experimentally. PMID:24165796

  17. Synthesis of Monometallic (Au and Pd) and Bimetallic (AuPd) Nanoparticles Using Carbon Nitride (C3N4) Quantum Dots via the Photochemical Route for Nitrophenol Reduction.

    PubMed

    Fageria, Pragati; Uppala, Shravan; Nazir, Roshan; Gangopadhyay, Subhashis; Chang, Chien-Hsiang; Basu, Mrinmoyee; Pande, Surojit

    2016-10-04

    In this study, we report the synthesis of monometallic (Au and Pd) and bimetallic (AuPd) nanoparticles (NPs) using graphitic carbon nitride (g-C3N4) quantum dots (QDs) and photochemical routes. Eliminating the necessity of any extra stabilizer or reducing agent, the photochemical reactions have been carried out using a UV light source of 365 nm where C3N4 QD itself functions as a suitable stabilizer as well as a reducing agent. The g-C3N4 QDs are excited upon irradiation with UV light and produce photogenerated electrons, which further facilitate the reduction of metal ions. The successful formation of Au, Pd, and AuPd alloy nanoparticles is evidenced by UV-vis, powder X-ray diffraction, X-ray photon spectroscopy, and energy-dispersive spectroscopy techniques. The morphology and distribution of metal nanoparticles over the C3N4 QD surface has been systematically investigated by high-resolution transmission electron microscopy (HRTEM) and SAED analysis. To explore the catalytic activity of the as-prepared samples, the reduction reaction of 4-nitrophenol with excellent performance is also investigated. It is noteworthy that the synthesis of both monometallic and bimetallic NPs can be accomplished by using a very small amount of g-C3N4, which can be used as a promising photoreducing material as well as a stabilizer for the synthesis of various metal nanoparticles.

  18. An ordered bcc CuPd nanoalloy synthesised via the thermal decomposition of Pd nanoparticles covered with a metal-organic framework under hydrogen gas.

    PubMed

    Li, Guangqin; Kobayashi, Hirokazu; Kusada, Kohei; Taylor, Jared M; Kubota, Yoshiki; Kato, Kenichi; Takata, Masaki; Yamamoto, Tomokazu; Matsumura, Syo; Kitagawa, Hiroshi

    2014-11-18

    Presented here is the synthesis of an ordered bcc copper-palladium nanoalloy, via the decomposition of a Pd nanoparticle@metal-organic framework composite material. In situ XRD measurements were performed in order to understand the mechanism of the decomposition process. This result gives a further perspective into the synthesis of new nanomaterials via metal-organic framework decomposition.

  19. Synthesis of PD particles by alcohols-assisted photoreduction for use in supported catalysts

    DOEpatents

    Burton, Patrick David; Boyle, Timothy J; Datye, Abhaya

    2015-02-24

    The present disclosure provides a novel synthesis method for palladium nanoparticles and palladium nanoparticles made using the method. The nanoparticles resulting from the method are highly reactive and, when deposited on a support, are highly suitable for use as catalytic material.

  20. Water-Soluble Pd Nanoparticles Synthesized from ω-Carboxyl-S-Alkanethiosulfate Ligand Precursors as Unimolecular Micelle Catalysts

    PubMed Central

    Gavia, Diego J.; Maung, May S.; Shon, Young-Seok

    2014-01-01

    This report describes a two-phase synthesis of water-soluble carboxylate-functionalized alkanethiolate-capped Pd nanoparticles from ω-carboxyl-S-alkanethiosulfate sodium salts. The two-phase methodology using the thiosulfate ligand passivation protocol allowed a highly specific control over the surface ligand coverage of these nanoparticles, which are lost in a one-phase aqueous system because of the base-catalyzed hydrolysis of thiosulfate to thiolate. Systematic synthetic variations investigated in this study included the concentration of ω-carboxyl-S-alkanethiosulfate ligand precursors and reducing agent, NaBH4, and the overall ligand chain length. The resulting water-soluble Pd nanoparticles were isolated and characterized by transmission electron microscopy (TEM), thermogravimetric analysis (TGA), 1H NMR, UV–vis, and FT-IR spectroscopy. Among different variations, a decrease in the molar equivalent of NaBH4 resulted in a reduction in the surface ligand density while maintaining a similar particle core size. Additionally, reducing the chain length of the thiosulfate ligand precursor also led to the formation of stable nanoparticles with a lower surface coverage. Since the metal core size of these Pd nanoparticle variations remained quite consistent, direct correlation studies between ligand properties and catalytic activities against hydrogenation/isomerization of allyl alcohol could be performed. Briefly, Pd nanoparticles dissolved in water favored the hydrogenation of allyl alcohol to 1-propanol whereas Pd nanoparticles heterogeneously dispersed in chloroform exhibited a rather high selectivity towards the isomerization product (propanal). The results suggested that the surrounding ligand environments, such as the ligand structure, conformation, and surface coverage, were crucial in determining the overall activity and selectivity of the Pd nanoparticle catalysts. PMID:24246150

  1. Newly developed stepwise electroless deposition enables a remarkably facile synthesis of highly active and stable amorphous Pd nanoparticle electrocatalysts for oxygen reduction reaction.

    PubMed

    Poon, Kee Chun; Tan, Desmond C L; Vo, Thang D T; Khezri, Bahareh; Su, Haibin; Webster, Richard D; Sato, Hirotaka

    2014-04-09

    This paper reports on highly active and stable amorphous Pd nanoparticle electrocatalysts for the oxygen reduction reaction. The amorphous catalysts were synthesized by a remarkably facile and quick electroless deposition process newly developed in this study (process time <5 min). An electrode substrate (glassy carbon, carbon cloth) was sequentially dipped for 10 s into two separate solutions of a reducing agent (sodium hypophosphite (NaH2PO2)) and Pd ions to deposit amorphous Pd nanoparticles containing phosphorus (Pd-P). By repeating the deposition cycles, the specific and mass activities of the Pd nanoparticles can be actively tuned. Owing to the nanoscale amorphous nature, the obtained Pd-P nanoparticle electrocatalysts exhibited superior specific and mass activities compared with crystalline Pd nanoparticles synthesized by another reducing agent (N2H4) and commercial Pt-loaded carbon (Pt/C) and Pd-loaded carbon (Pd/C). The specific and mass activities of the amorphous Pd-P nanoparticles were over 4.5 times and 2.6 times higher than previously reported values of Pd and Pt catalysts.

  2. Synthesis of cubic and spherical Pd nanoparticles on graphene and their electrocatalytic performance in the oxidation of formic acid.

    PubMed

    Yang, Sudong; Shen, Chengmin; Tian, Yuan; Zhang, Xiaogang; Gao, Hong-Jun

    2014-11-07

    Single-crystal palladium nanoparticles (NPs) with controllable morphology were synthesized on the surface of reduced graphene oxide (RGO) by a novel procedure, namely reducing palladium acetylacetonate [Pd(acac)2] with the N-methylpyrrolidone (NMP) solvent in the presence of poly(vinylpyrrolidone) (PVP). The resulting Pd nanocrystals (8 nm in diameter) were uniformly distributed on the RGO. A possible formation mechanism is discussed. The electrocatalytic performance of Pd nanocrystal/RGO catalysts during formic acid oxidation was investigated, which revealed that the cubic Pd/RGO catalyst performed significantly better than the spherical Pd/RGO catalyst. The shape of Pd nanocrystals on the surface of graphene nanosheets can be easily controlled via tuning the synthesis parameters, resulting in tunable catalytic properties. Moreover, this method can be easily extended to fabricate other noble metal nanostructures.

  3. Synthesis of cubic and spherical Pd nanoparticles on graphene and their electrocatalytic performance in the oxidation of formic acid

    NASA Astrophysics Data System (ADS)

    Yang, Sudong; Shen, Chengmin; Tian, Yuan; Zhang, Xiaogang; Gao, Hong-Jun

    2014-10-01

    Single-crystal palladium nanoparticles (NPs) with controllable morphology were synthesized on the surface of reduced graphene oxide (RGO) by a novel procedure, namely reducing palladium acetylacetonate [Pd(acac)2] with the N-methylpyrrolidone (NMP) solvent in the presence of poly(vinylpyrrolidone) (PVP). The resulting Pd nanocrystals (8 nm in diameter) were uniformly distributed on the RGO. A possible formation mechanism is discussed. The electrocatalytic performance of Pd nanocrystal/RGO catalysts during formic acid oxidation was investigated, which revealed that the cubic Pd/RGO catalyst performed significantly better than the spherical Pd/RGO catalyst. The shape of Pd nanocrystals on the surface of graphene nanosheets can be easily controlled via tuning the synthesis parameters, resulting in tunable catalytic properties. Moreover, this method can be easily extended to fabricate other noble metal nanostructures.

  4. Synthesis of Pd9Ru@Pt nanoparticles for oxygen reduction reaction in acidic electrolytes

    DOE PAGES

    Sun, Yu; Hsieh, Yu -Chi; Chang, Li -Chung; ...

    2014-11-22

    Nanoparticles of PdRu, Pd₃Ru, and Pd₉Ru are synthesized and impregnated on carbon black via a wet chemical reflux process. X-ray diffraction patterns of the as-synthesized samples, PdxRu/C (x=1/3/9), suggest succesful formation of alloy without presence of individual Pd and Ru nanoparticles. Images from transmission electron microscope confirm irregularly-shaped nanoparticles with average size below 3 nm. Analysis from extended X-ray absorption fine structure on both Pd and Ru K-edge absorption profiles indicate the Ru atoms are enriched on the surface of PdxRu/C. Among these samples, the Pd₉Ru/C exhibits the strongest electrocatalytic activity for oxygen reduction reaction (ORR) in an oxygen-saturated 0.1more » M aqueous HClO₄ solution. Subsequently, the Pd₉Ru/C undegoes Cu under potential deposition, followed by a galvanic displacement reaction to deposit a Pt monolayer on the Pd₉Ru surface (Pd₉Ru@Pt). The Pd₉Ru@Pt reveals better ORR performance than that of Pt, reaching a mass activity of 0.38 mA μg⁻¹ Pt, as compared to that of commercially available Pt nanoparticles (0.107 mA μg⁻¹ Pt). Thus, the mechanisms responsible for the ORR enhancement are attributed to the combined effects of lattice strain and ligand interaction. In addition, this core-shell Pd₉Ru@Pt electrocatalyst represents a substantial reduction in the amount of Pt consumption and raw material cost.« less

  5. One-pot synthesis of CeO₂-supported Pd-Cu-alloy nanocubes with high catalytic activity.

    PubMed

    Park, Kyu-Hwan; Lee, Young Wook; Kim, Yena; Kang, Shin Wook; Han, Sang Woo

    2013-06-17

    Cerium and nanocubes: CeO₂-supported Pd-Cu-alloy nanocubes (Pd-Cu NCs/CeO₂) with high content and good dispersion of the Pd-Cu NCs were prepared in high yields by heating a solution containing Pd, Cu, and Ce precursors. The prepared Pd-Cu NCs/CeO₂ have excellent catalytic activity and stability toward formic acid electro-oxidation due to the synergism between the Pd-Cu-alloy catalysts and the CeO₂ support. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Enhanced dechlorination of m-DCB using iron@graphite/palladium (Fe@C/Pd) nanoparticles produced by pulsed laser ablation in liquid.

    PubMed

    Yu, Yiseul; Jung, Hyeon Jin; Je, Mingyu; Choi, Hyun Chul; Choi, Myong Yong

    2016-07-01

    In this work, the zero valent Fe (ZVI) and graphite-encapsulated Fe (Fe@C) nanoparticles (NPs) were easily and selectively prepared by a pulsed laser ablation (PLA) method in an aqueous sodium borohydride solution and ascorbic acid dissolved in methanol, respectively. Here, the Fe@C NPs were uniquely synthesized by PLA in methanol, where the solvent is used as both a carbon source for the graphitic layers and solvent, which is very unique. Furthermore, Pd NPs were loaded onto the surface of the Fe@C NPs to prepare bimetallic (Fe@C/Pd) NPs for the enhancement of the degradation efficiency of m-dichlorobenzene (m-DCB). The morphology, crystallinity, and surface composition of the prepared NPs were carefully characterized by high-resolution transmission electron microscopy (HRTEM), energy dispersive x-ray spectrometer (EDS), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). The degradation rate of m-DCB using single (Fe and Pd) or bimetallic (Fe/Pd and Fe@C/Pd) NPs were compared by using gas chromatography. Among these NPs produced in this work, the Fe@C/Pd NPs with 1.71 wt % of Pd showed an excellent dechlorination efficiency for m-DCB with 100% degradation within 75 min. The graphitic layer on the Fe NPs played as not only an oxidation resistant for the Fe NPs to surroundings, but also a supporter of the Pd NPs for the enhanced degradation efficiency of m-DCB. Copyright © 2016 Elsevier Ltd. All rights reserved.

  7. Pulse-driven micro gas sensor fitted with clustered Pd/SnO2 nanoparticles.

    PubMed

    Suematsu, Koichi; Shin, Yuka; Ma, Nan; Oyama, Tokiharu; Sasaki, Miyuki; Yuasa, Masayoshi; Kida, Tetsuya; Shimanoe, Kengo

    2015-08-18

    Real-time monitoring of specific gas concentrations with a compact and portable gas sensing device is required to sense potential health risk and danger from toxic gases. For such purposes, we developed an ultrasmall gas sensor device, where a micro sensing film was deposited on a micro heater integrated with electrodes fabricated by the microelectromechanical system (MEMS) technology. The developed device was operated in a pulse-heating mode to significantly reduce the heater power consumption and make the device battery-driven and portable. Using clustered Pd/SnO2 nanoparticles, we succeeded in introducing mesopores ranging from 10 to 30 nm in the micro gas sensing film (area: ϕ 150 μm) to detect large volatile organic compounds (VOCs). The micro sensor showed quick, stable, and high sensor responses to toluene at ppm (parts per million) concentrations at 300 °C even by operating the micro heater in a pulse-heating mode where switch-on and -off cycles were repeated at one-second intervals. The high performance of the micro sensor should result from the creation of efficient diffusion paths decorated with Pd sensitizers by using the clustered Pd/SnO2 nanoparticles. Hence we demonstrate that our pulse-driven micro sensor using nanostructured oxide materials holds promise as a battery-operable, portable gas sensing device.

  8. Large Marks-decahedral Pd nanoparticles synthesized by a modified hydrothermal method using a homogeneous reactor

    NASA Astrophysics Data System (ADS)

    Zhao, Haiqiang; Qi, Weihong; Ji, Wenhai; Wang, Tianran; Peng, Hongcheng; Wang, Qi; Jia, Yanlin; He, Jieting

    2017-05-01

    Fivefold symmetry appears only in small particles and quasicrystals because internal stress in the particles increases with the particle size. However, a typical Marks decahedron with five re-entrant grooves located at the ends of the twin boundaries can further reduce the strain energy. During hydrothermal synthesis, it is difficult to stir the reaction solution contained in a digestion high-pressure tank because of the relatively small size and high-temperature and high-pressure sealed environment. In this work, we optimized a hydrothermal reaction system by replacing the conventional drying oven with a homogeneous reactor to shift the original static reaction solution into a full mixing state. Large Marks-decahedral Pd nanoparticles ( 90 nm) have been successfully synthesized in the optimized hydrothermal synthesis system. Additionally, in the products, round Marks-decahedral Pd particles were also found for the first time. While it remains a challenge to understand the growth mechanism of the fivefold twinned structure, we proposed a plausible growth-mediated mechanism for Marks-decahedral Pd nanoparticles based on observations of the synthesis process.

  9. Plasmonic Pd Nanoparticle- and Plasmonic Pd Nanorod-Decorated BiVO4 Electrodes with Enhanced Photoelectrochemical Water Splitting Efficiency Across Visible-NIR Region

    NASA Astrophysics Data System (ADS)

    Yang, Weiwei; Xiong, Yunjie; Zou, Liangliang; Zou, Zhiqing; Li, Dongdong; Mi, Qixi; Wang, Yanshan; Yang, Hui

    2016-06-01

    The photoelectrochemical (PEC) water splitting performance of BiVO4 is partially hindered by insufficient photoresponse in the spectral region with energy below the band gap. Here, we demonstrate that the PEC water splitting efficiency of BiVO4 electrodes can be effectively enhanced by decorating Pd nanoparticles (NPs) and nanorods (NRs). The results indicate that the Pd NPs and NRs with different surface plasmon resonance (SPR) features delivered an enhanced PEC water splitting performance in the visible and near-infrared (NIR) regions, respectively. Considering that there is barely no absorption overlap between Pd nanostructures and BiVO4 and the finite-difference time domain (FDTD) simulation indicating there are substantial energetic hot electrons in the vicinity of Pd nanostructures, the enhanced PEC performance of Pd NP-decorated BiVO4 and Pd NR-decorated BiVO4 could both benefit from the hot electron injection mechanism instead of the plasmon resonance energy transfer process. Moreover, a combination of Pd NPs and NRs decorated on the BiVO4 electrodes leads to a broad-band enhancement across visible-NIR region.

  10. Plasmonic Pd Nanoparticle- and Plasmonic Pd Nanorod-Decorated BiVO4 Electrodes with Enhanced Photoelectrochemical Water Splitting Efficiency Across Visible-NIR Region.

    PubMed

    Yang, Weiwei; Xiong, Yunjie; Zou, Liangliang; Zou, Zhiqing; Li, Dongdong; Mi, Qixi; Wang, Yanshan; Yang, Hui

    2016-12-01

    The photoelectrochemical (PEC) water splitting performance of BiVO4 is partially hindered by insufficient photoresponse in the spectral region with energy below the band gap. Here, we demonstrate that the PEC water splitting efficiency of BiVO4 electrodes can be effectively enhanced by decorating Pd nanoparticles (NPs) and nanorods (NRs). The results indicate that the Pd NPs and NRs with different surface plasmon resonance (SPR) features delivered an enhanced PEC water splitting performance in the visible and near-infrared (NIR) regions, respectively. Considering that there is barely no absorption overlap between Pd nanostructures and BiVO4 and the finite-difference time domain (FDTD) simulation indicating there are substantial energetic hot electrons in the vicinity of Pd nanostructures, the enhanced PEC performance of Pd NP-decorated BiVO4 and Pd NR-decorated BiVO4 could both benefit from the hot electron injection mechanism instead of the plasmon resonance energy transfer process. Moreover, a combination of Pd NPs and NRs decorated on the BiVO4 electrodes leads to a broad-band enhancement across visible-NIR region.

  11. Anomalous Structural Disorder in Supported Pt Nanoparticles

    DOE PAGES

    Vila, Fernando D.; Rehr, John J.; Nuzzo, Ralph G.; ...

    2017-07-02

    Supported Pt nanocatalysts generally exhibit anomalous behavior, including negative thermal expansion and large structural disorder. Finite temperature DFT/MD simulations reproduce these properties, showing that they are largely explained by a combination of thermal vibrations and low-frequency disorder. We show in this paper that a full interpretation is more complex and that the DFT/MD mean-square relative displacements (MSRD) can be further separated into vibrational disorder, “dynamic structural disorder” (DSD), and long-time equilibrium fluctuations of the structure dubbed “anomalous structural disorder” (ASD). We find that the vibrational and DSD components behave normally, increasing linearly with temperature while the ASD decreases, reflecting themore » evolution of mean nanoparticle geometry. Finally, as a consequence the usual procedure of fitting the MSRD to normal vibrations plus temperature-independent static disorder results in unphysical bond strengths and Grüneisen parameters.« less

  12. Electrochemical promotion of catalysis over Pd nanoparticles for CO2 reduction.

    PubMed

    Cai, Fan; Gao, Dunfeng; Zhou, Hu; Wang, Guoxiong; He, Ting; Gong, Huimin; Miao, Shu; Yang, Fan; Wang, Jianguo; Bao, Xinhe

    2017-04-01

    Electrochemical promotion of catalysis (EPOC) has been shown to accelerate the rate of many heterogeneous catalytic reactions; however, it has rarely been reported in low-temperature aqueous electrochemical reactions. Herein, we report a significant EPOC effect for the CO2 reduction to generate formate over Pd nanoparticles (NPs) in a 1 M KHCO3 aqueous solution. By applying a negative potential over differently-sized Pd NPs, the rate of formate production is greatly improved as compared to that at an open-circuit voltage, with a rate enhancement ratio ranging from 10 to 143. The thermocatalytic and electrocatalytic reduction of CO2 compete with each other and are promoted by the applied negative potential and H2 in the feeds, respectively. Inspired by the EPOC effect, a composite electrode containing Pd/C and Pt/C catalysts on different sides of a carbon paper was constructed for catalyzing the CO2 reduction without adding H2 to the feeds. Water electrolysis over Pt NPs generates H2, which then effectively promotes formate production over Pd NPs.

  13. Electrochemical synthesis of reduced graphene sheet-AuPd alloy nanoparticle composites for enzymatic biosensing.

    PubMed

    Yang, Jiang; Deng, Shengyuan; Lei, Jianping; Ju, Huangxian; Gunasekaran, Sundaram

    2011-11-15

    A simple, fast, green and controllable approach was developed for electrochemical synthesis of a novel nanocomposite of electrochemically reduced graphene oxide (ERGO) and gold-palladium (1:1) bimetallic nanoparticles (AuPdNPs), without the aid of any reducing reagent. The electrochemical reduction efficiently removed oxygen-containing groups in ERGO, which was then modified with homogeneously dispersed AuPdNPs in a good size distribution. ERGO-AuPdNPs nanocomposite showed excellent biocompatibility, enhanced electron transfer kinetics and large electroactive surface area, and were highly sensitive and stable towards oxygen reduction. A biosensor was constructed by immobilizing glucose oxidase as a model enzyme on the nanocomposites for glucose detection through oxygen consumption during the enzymatic reaction. The biosensor had a detection limit of 6.9μM, a linear range up to 3.5mM and a sensitivity of 266.6μAmM(-1)cm(-2). It exhibited acceptable reproducibility and good accuracy with negligible interferences from common oxidizable interfering species. These characteristics make ERGO-AuPdNPs nanocomposite highly suitable for oxidase-based biosensing.

  14. Green and Facile Synthesis of Pd-Pt Alloy Nanoparticles by Laser Irradiation of Aqueous Solution.

    PubMed

    Nakamura, Takahiro; Sato, Shunichi

    2015-01-01

    Solid-solution palladium-platinum (Pd-Pt) alloy nanoparticles (NPs) with fully tunable compositions were directly fabricated through high-intensity laser irradiation of an aqueous solution of palladium and platinum ions without using any reducing agents or thermal processes. Transmission electron microscopy (TEM) observations showed that nanometer-sized particles were fabricated by laser irradiation of mixed aqueous solutions of palladium and platinum ions with different feeding ratios. The crystalline nature of the NPs was precisely characterized by X-ray diffraction (XRD). Despite the fact that, for the bulk systems, a pair of XRD peak was detected between the palladium and platinum peaks because of the large miscibility gap in the Pd-Pt binary phase diagram, only a single XRD peak was seen for the Pd-Pt NPs fabricated in the present study. Moreover, the peak position shifted from that of pure palladium towards platinum with increasing fraction of platinum ions in solution. Consequently, the interplanar spacings of the alloy NPs agreed well with the estimated values obtained from Vegard's law. These observations strongly indicate the formation of solid-solution Pd-Pt alloy NPs with fully tunable compositions. This technique is not only a "green" (environmentally-friendly) and facile process, but is also widely applicable to other binary and ternary systems.

  15. Pd Nanoparticles and MOFs Synergistically Hybridized Halloysite Nanotubes for Hydrogen Storage.

    PubMed

    Jin, Jiao; Ouyang, Jing; Yang, Huaming

    2017-12-01

    Natural halloysite nanotubes (HNTs) were hybridized with metal-organic frameworks (MOFs) to prepare novel composites. MOFs were transformed into carbon by carbonization calcination, and palladium (Pd) nanoparticles were introduced to build an emerging ternary compound system for hydrogen adsorption. The hydrogen adsorption capacities of HNT-MOF composites were 0.23 and 0.24 wt%, while those of carbonized products were 0.24 and 0.27 wt% at 25 °C and 2.65 MPa, respectively. Al-based samples showed higher hydrogen adsorption capacities than Zn-based samples on account of different selectivity between metal and hydrogen and approximate porous characteristics. More pore structures are generated by the carbonization reaction from metal-organic frameworks into carbon; high specific surface area, uniform pore size, and large pore volume benefited the hydrogen adsorption ability of composites. Moreover, it was also possible to promote hydrogen adsorption capacity by incorporating Pd. The hydrogen adsorption capacity of ternary compound, Pd-C-H3-MOFs(Al), reached 0.32 wt% at 25 °C and 2.65 MPa. Dissociation was assumed to take place on the Pd particles, then atomic and molecule hydrogen spilled over to the structure of carboxylated HNTs, MOFs, and the carbon products for enhancing the hydrogen adsorption capacity.

  16. Pd Nanoparticles and MOFs Synergistically Hybridized Halloysite Nanotubes for Hydrogen Storage

    NASA Astrophysics Data System (ADS)

    Jin, Jiao; Ouyang, Jing; Yang, Huaming

    2017-03-01

    Natural halloysite nanotubes (HNTs) were hybridized with metal-organic frameworks (MOFs) to prepare novel composites. MOFs were transformed into carbon by carbonization calcination, and palladium (Pd) nanoparticles were introduced to build an emerging ternary compound system for hydrogen adsorption. The hydrogen adsorption capacities of HNT-MOF composites were 0.23 and 0.24 wt%, while those of carbonized products were 0.24 and 0.27 wt% at 25 °C and 2.65 MPa, respectively. Al-based samples showed higher hydrogen adsorption capacities than Zn-based samples on account of different selectivity between metal and hydrogen and approximate porous characteristics. More pore structures are generated by the carbonization reaction from metal-organic frameworks into carbon; high specific surface area, uniform pore size, and large pore volume benefited the hydrogen adsorption ability of composites. Moreover, it was also possible to promote hydrogen adsorption capacity by incorporating Pd. The hydrogen adsorption capacity of ternary compound, Pd-C-H3-MOFs(Al), reached 0.32 wt% at 25 °C and 2.65 MPa. Dissociation was assumed to take place on the Pd particles, then atomic and molecule hydrogen spilled over to the structure of carboxylated HNTs, MOFs, and the carbon products for enhancing the hydrogen adsorption capacity.

  17. Composition-dependent electrocatalytic activity of AuPd alloy nanoparticles prepared via simultaneous sputter deposition into an ionic liquid.

    PubMed

    Hirano, Masanori; Enokida, Kazuki; Okazaki, Ken-ichi; Kuwabata, Susumu; Yoshida, Hisao; Torimoto, Tsukasa

    2013-05-21

    Homogeneously alloyed bimetallic particles of AuPd with an average size of ca. 2 nm were successfully prepared by simultaneous sputter deposition of Au and Pd in an ionic liquid in the absence of any additional stabilizing agents. The chemical composition of the AuPd alloy was tunable depending on the area fraction of Au plates in the Au-Pd binary targets for sputtering. The particles were immobilized on an HOPG surface by heat treatment along with the increase in the average size of particles from ca. 2 nm to ca. 7 nm. Ionic liquid species adsorbed on the as-prepared AuPd nanoparticle films on HOPG caused the prevention of electrocatalytic reactions, but repetition of potential sweep cycling in a basic aqueous solution removed the adsorbed ionic species, resulting in electrocatalytic oxidation of ethanol at the AuPd alloy nanoparticle-immobilized HOPG electrode. The electrocatalytic activity of AuPd nanoalloy particles varied upon changing the fraction of Au and Pd in the particles, and alloy particles having an Au fraction of ca. 0.61 exhibited the maximum activity against ethanol oxidation, being higher than the activity of the pure Pt surface.

  18. Spatial scanning spectroelectrochemistry. Study of the electrodeposition of Pd nanoparticles at the liquid/liquid interface.

    PubMed

    Izquierdo, Daniel; Martinez, Alberto; Heras, Aranzazu; Lopez-Palacios, Jesus; Ruiz, Virginia; Dryfe, Robert A W; Colina, Alvaro

    2012-07-03

    Spatial scanning spectroelectrochemistry is a new analytical technique that provides spectral information at different distances from an electrified liquid/liquid interface where an electrochemical process takes place. As a proof of concept, we have studied two different electrochemical processes at the electrified liquid/liquid interface: (1) Ru(bpy)(3)(2+) transfer through the water/1,2-dichloroethane interface and (2) electrodeposition of Pd nanoparticles at the water/1,2-dichloroethane interface. The instrumental setup developed consists of a movable slit for the light beam to sample at well-defined positions on both sides of the interface, providing important information about the chemical process occurring. If the slit is scanned at different distances from the interface during an electrochemical experiment, a complete picture of the reactions and equilibria in the diffusion layer can be obtained. For example, in the case of the Ru(bpy)(3)(2+), the experiments show clearly how the complex is transferred from one phase to the other. In the case of electrosynthesis of Pd nanoparticles, it is demonstrated that nanoparticles are not only deposited at the interface but diffuse to the aqueous bulk solution. These in situ observations were confirmed by ex situ experiments using transmission electron microscopy.

  19. A surfactant-free strategy for synthesizing reduced graphene oxide supported palladium nanoparticles with enhanced electrocatalytic performance towards formic acid oxidation

    NASA Astrophysics Data System (ADS)

    Gao, Xueqing; Li, Fumin; Li, Yumei; Li, Shuni; Chen, Yu; Lee, Jong-Min

    2015-04-01

    A simple noncovalent method is used to graft sulfonate (-SO3H) groups on a graphene oxide (GO) surface by the π-π stacking interaction between 1-propylsulfonic-3-methylimidazolium chloride and GO. The immobilization of sulfonate groups on the GO surface is confirmed by various physical techniques, such as X-ray photoelectron spectroscopy, ultraviolet and visible spectroscopy, and zeta potential analysis, etc. The as-prepared sulfonate functionalized GO composites (GO-SO3H) are further used as supporting material to anchor PdO·H2O nanoparticles through the slow hydrolysis of PdCl2. The sulfonate functionalized reduced GO composites (rGO-SO3H) supported Pd nanoparticles composites (Pd/rGO-SO3H) are obtained through the simultaneous reduction of PdO·H2O and the GO-SO3H with sodium borohydride. As shown by transmission electron microscopy, Pd nanoparticles with good dispersity effectively anchor on the rGO-SO3H surface. The as-prepared Pd/rGO-SO3H composites display the improved electrocatalytic activity and long-term stability towards the formic acid oxidation reaction compared to the un-sulfonated counterpart.

  20. Enhanced electrocatalytic performance of processed, ultrathin, supported Pd-Pt core-shell nanowire catalysts for the oxygen reduction reaction.

    PubMed

    Koenigsmann, Christopher; Santulli, Alexander C; Gong, Kuanping; Vukmirovic, Miomir B; Zhou, Wei-ping; Sutter, Eli; Wong, Stanislaus S; Adzic, Radoslav R

    2011-06-29

    We report on the synthesis, characterization, and electrochemical performance of novel, ultrathin Pt monolayer shell-Pd nanowire core catalysts. Initially, ultrathin Pd nanowires with diameters of 2.0 ± 0.5 nm were generated, and a method has been developed to achieve highly uniform distributions of these catalysts onto the Vulcan XC-72 carbon support. As-prepared wires are activated by the use of two distinctive treatment protocols followed by selective CO adsorption in order to selectively remove undesirable organic residues. Subsequently, the desired nanowire core-Pt monolayer shell motif was reliably achieved by Cu underpotential deposition followed by galvanic displacement of the Cu adatoms. The surface area and mass activity of the acid and ozone-treated nanowires were assessed, and the ozone-treated nanowires were found to maintain outstanding area and mass specific activities of 0.77 mA/cm(2) and 1.83 A/mg(Pt), respectively, which were significantly enhanced as compared with conventional commercial Pt nanoparticles, core-shell nanoparticles, and acid-treated nanowires. The ozone-treated nanowires also maintained excellent electrochemical durability under accelerated half-cell testing, and it was found that the area-specific activity increased by ~1.5 fold after a simulated catalyst lifetime.

  1. Carbon-supported Pd-Pt cathode electrocatalysts for proton exchange membrane fuel cells

    NASA Astrophysics Data System (ADS)

    Tang, Yongfu; Zhang, Huamin; Zhong, Hexiang; Xu, Ting; Jin, Hong

    A series of carbon-supported Pd-Pt alloy (Pd-Pt/C) catalysts for oxygen reduction reaction (ORR) with low-platinum content are synthesized via a modified sodium borohydride reduction method. The structure of as-prepared catalysts is characterized by powder X-ray diffraction (XRD) and transmission electron microscope (TEM) measurements. The prepared Pd-Pt/C catalysts with alloy form show face-centered-cubic (FCC) structure. The metal particles of Pd-Pt/C catalysts with mean size of around 4-5 nm are uniformly dispersed on the carbon support. The electrocatalytic activities for ORR of these catalysts are investigated by rotating disk electrode (RDE), cyclic voltammetry (CV), single cell measurements and electrochemical impedance spectra (EIS) measurements. The results suggest that the electrocatalytic activities of Pd-Pt/C catalysts with low platinum are comparable to that of the commercial Pt/C with the same metal loading. The maximum power density of MEA with a Pd-Pt/C catalyst, the Pd/Pt mass ratio of which is 7:3, is about 1040 mW cm -2.

  2. Continuous flow room temperature reductive aqueous homo-coupling of aryl halides using supported Pd catalysts

    PubMed Central

    Feiz, Afsaneh; Bazgir, Ayoob; Balu, Alina M.; Luque, Rafael

    2016-01-01

    A convenient and environmentally friendly protocol for the preparation of biaryls at room temperature under continuous flow conditions is reported. A simple reductive homo-coupling Ullmann-type reaction was performed in an H-Cube mini using commercially available supported Pd catalysts under mild reaction conditions, with quantitative conversion to target products. Commercial Pd catalysts were found to be highly stable under the investigated reaction conditions, with a minimum Pd leaching into solution after several reaction runs (ca. 20 h on stream). PMID:27600989

  3. Selective aerobic oxidation of 1,3-propanediol to 3-hydroxypropanoic acid using hydrotalcite supported bimetallic gold nanoparticle catalyst in water

    NASA Astrophysics Data System (ADS)

    Mohammad, Mujahid; Nishimura, Shun; Ebitani, Kohki

    2015-02-01

    Selective oxidation of 1,3-propanediol (1,3-PD) to 3-hydroxypropanoic acid (3-HPA), an important industrial building block, was successfully achieved using hydrotalcite-supported bimetallic Au nanoparticle catalysts in water at 343 K under aerobic and base-free conditions. The highest yield of 42% with 73% selectivity towards 3-HPA was afforded by 1wt% Au0.8Pd0.2-PVP/HT catalyst.

  4. Electrocatalytic synthesis of hydrogen peroxide on Au-Pd nanoparticles: From fundamentals to continuous production

    NASA Astrophysics Data System (ADS)

    Pizzutilo, Enrico; Kasian, Olga; Choi, Chang Hyuck; Cherevko, Serhiy; Hutchings, Graham J.; Mayrhofer, Karl J. J.; Freakley, Simon J.

    2017-09-01

    The electrochemical synthesis of hydrogen peroxide (H2O2) represents a promising alternative to the anthraquinone process, as it combines on-site chemical and electrical production. The design of selective electrocatalysts is challenging and is commonly based on the alloying of elements to generate a synergistic effect and increase activity. In the present work, we report the electrochemical activity of Au-Pd nanoparticles immobilized directly onto an electrode as a model to study H2O2 electrochemical synthesis from fundamentals to continuous production. The impact of composition on the oxygen reduction reaction (ORR), the selectivity, as well as the peroxide reduction and oxidation reactions (PROR) are studied.

  5. Carbon supported Pd-Ni-P nanoalloy as an efficient catalyst for ethanol electro-oxidation in alkaline media

    NASA Astrophysics Data System (ADS)

    Wang, Ye; Shi, Fei-Fei; Yang, Yao-Yue; Cai, Wen-Bin

    2013-12-01

    Carbon-supported well-dispersed Pd-Ni-P ternary catalyst targeted for ethanol oxidation reaction (EOR) in alkaline media is synthesized in a simple aqueous bath containing Pd(II) and Ni(II) salts with sodium hypophosphite as the reducing agent and the source for P and sodium citrate as the complexing agent. XRD analysis on the as-prepared Pd-Ni-P/C reveals that Ni shrinks while P expands the Pd lattice structure, and XPS measurement suggests different electronic effects of the two alloying elements on Pd. Cyclic voltammetry and chronoamperometry indicate that the Pd-Ni-P/C presents a remarkably higher electrocatalytic activity than the state-of-the-art Pd/C, Pd-P/C and Pd-Ni/C catalysts. This may be ascribed to the unique electronic, geometric and bifunctional effects involved in this ternary nanoalloy.

  6. Atomic-scale identification of Pd leaching in nanoparticle catalyzed C–C coupling: Effects of particle surface disorder

    DOE PAGES

    Briggs, Beverly D.; Bedford, Nicholas M.; Seifert, Soenke; ...

    2015-07-23

    C–C coupling reactions are of great importance in the synthesis of numerous organic compounds, where Pd nanoparticle catalyzed systems represent new materials to efficiently drive these reactions. Despite their pervasive utility, the catalytic mechanism of these particle-based reactions remains highly contested. Herein we present evidence of an atom leaching mechanism for Stille coupling under aqueous conditions using peptide-capped Pd nanoparticles. EXAFS analysis revealed Pd coordination changes in the nanoparticle consistent with Pd atom abstraction, where sizing analysis by SAXS confirmed particle size changes associated with a leaching process. It is likely that recently discovered highly disordered surface Pd atoms aremore » the favored catalytic active sites and are leached during oxidative addition, resulting in smaller particles. Thus, probing the mechanism of nanoparticle-driven C–C coupling reactions through structural analyses provides fundamental information concerning these active sites and their reactivity at the atomic-scale, which can be used to improve catalytic performance to meet important sustainability goals.« less

  7. Atomic-scale identification of Pd leaching in nanoparticle catalyzed C–C coupling: Effects of particle surface disorder

    SciTech Connect

    Briggs, Beverly D.; Bedford, Nicholas M.; Seifert, Soenke; Koerner, Hilmar; Ramezani-Dakhel, Hadi; Heinz, Hendrik; Naik, Rajesh R.; Frenkel, Anatoly I.; Knecht, Marc R.

    2015-07-23

    C–C coupling reactions are of great importance in the synthesis of numerous organic compounds, where Pd nanoparticle catalyzed systems represent new materials to efficiently drive these reactions. Despite their pervasive utility, the catalytic mechanism of these particle-based reactions remains highly contested. Herein we present evidence of an atom leaching mechanism for Stille coupling under aqueous conditions using peptide-capped Pd nanoparticles. EXAFS analysis revealed Pd coordination changes in the nanoparticle consistent with Pd atom abstraction, where sizing analysis by SAXS confirmed particle size changes associated with a leaching process. It is likely that recently discovered highly disordered surface Pd atoms are the favored catalytic active sites and are leached during oxidative addition, resulting in smaller particles. Thus, probing the mechanism of nanoparticle-driven C–C coupling reactions through structural analyses provides fundamental information concerning these active sites and their reactivity at the atomic-scale, which can be used to improve catalytic performance to meet important sustainability goals.

  8. Understanding the atomic-level process of CO-adsorption-driven surface segregation of Pd in (AuPd)147 bimetallic nanoparticles.

    PubMed

    An, Hyesung; Ha, Hyunwoo; Yoo, Mi; Kim, Hyun You

    2017-08-24

    When the elements that compose bimetallic catalysts interact asymmetrically with reaction feedstock, the surface concentration of the bimetallic catalysts and the morphology of the reaction center evolve dynamically as a function of environmental factors such as the partial pressure of the triggering molecule. Relevant experimental and theoretical findings of the dynamic structural evolution of bimetallic catalysts under the reaction conditions are emerging, thus enabling the design of more consistent, reliable, and efficient bimetallic catalysts. In an initial attempt to provide an atomic-level understanding of the adsorption-induced structural evolution of bimetallic nanoparticles (NPs) under CO oxidation conditions, we used density functional theory to study the details of CO-adsorption-driven Pd surface segregation in (AuPd)147 bimetallic NPs. The strong CO affinity of Pd provides a driving force for Pd surface segregation. We found that the vertex site of the NP becomes a gateway for the initial Pd-Au swapping and the subsequent formation of an internal vacancy. This self-generated internal vacancy easily diffuses inside the NP and activates Pd-Au swapping pathways in the (100) NP facet. Our results reveal how the surface and internal concentrations of bimetallic NPs respond immediately to changes in the reaction conditions. Our findings should aid in the rational design of highly active and versatile bimetallic catalysts by considering the environmental factors that systematically affect the structure of bimetallic catalysts under the reaction conditions.

  9. In situ XAS studies of Pt{sub x}Pd{sub 1-x} nanoparticles under thermal annealing

    SciTech Connect

    Bernardi, F.; Morais, J.; Alves, M. C. M.

    2009-01-29

    In this work, we have studied Pt{sub x}Pd{sub 1-x}(x = 1, 0.7 or 0.5) nanoparticles subjected to H{sub 2} reduction and sulfidation under H{sub 2}S atmosphere, both at 300 deg. C. The system was studied by in-situ x-ray absorption spectroscopy (in-situ XAS). We observed that the efficiency of sulfidation is directly proportional to the quantity of Pd atoms in the nanoparticle, provided the reduction process has been achieved.

  10. Influence of preparation conditions on the depth-dependent composition of AuPd nanoparticles grown on planar oxide surfaces

    NASA Astrophysics Data System (ADS)

    Haire, Andrew R.; Gustafson, Johan; Trant, Aoife G.; Jones, Timothy E.; Noakes, Timothy C. Q.; Bailey, Paul; Baddeley, Christopher J.

    2011-01-01

    The high resolution depth profiling capabilities of medium energy ion scattering are employed to determine the depth dependent composition of Au/Pd nanoparticles grown on thin silica films on Si(100) as functions of Au/Pd composition, total metal loading and annealing temperature. We show that, despite the fact that Au is deposited prior to Pd, the surface of the particles is generally enriched in Au compared to the bulk composition. The extent of this Au enrichment decreases with annealing temperature. In addition, we examine the influence of the adsorption of acetic acid on the surface composition of Au/Pd particles grown on thin alumina films on NiAl(110). We find that acetic acid causes limited segregation of Pd to the bimetallic surface of relatively Au-rich particles.

  11. The influence of carbon surface chemistry on supported palladium nanoparticles in heterogeneous reactions.

    PubMed

    Ding, Yuxiao; Zhang, Liyun; Wu, Kuang-Hsu; Feng, Zhenbao; Shi, Wen; Gao, Qiang; Zhang, Bingsen; Su, Dang Sheng

    2016-10-15

    The surface chemistry of nanocarbon support can tailor chemical properties of precious metal nanoparticle/nanocarbon hybrid catalyst in heterogeneous reactions. We report on modified reduced graphene oxide (rGO) support with ionic liquid-derived carbonaceous surface for palladium nanoparticle (Pd NPs) decoration and their actions in different heterogeneous reactions. The surface chemistry of support materials was characterized in detail, and the influence of which on the formation and distribution of metal particles was further investigated. Three different types of reactions including Suzuki-Miyaura coupling reaction, CO oxidation and phenol reduction were examined in terms of reactivity and selectivity. The roles of substituted nitrogen in graphitic lattice and grafted groups on the carbon surface were exploited. Nitrogen-doping can give rise to changes in electronic properties of supported metals, and the Lewis basicity of the doped nitrogen atoms can favor the adsorption of acidic reactants in phenol reduction. The grafted groups derived a negative impact to the Suzuki-Miyaura coupling reaction, due to the involvement of larger reactant molecules, despite that they could prevent significant sintering of Pd NPs in the CO oxidation.

  12. CO ppb sensors based on monodispersed SnOx:Pd mixed nanoparticle layers: Insight into dual conductance response

    NASA Astrophysics Data System (ADS)

    Aruna, I.; Kruis, F. E.; Kundu, S.; Muhler, M.; Theissmann, R.; Spasova, M.

    2009-03-01

    This study reports the modifications in CO sensing of SnOx nanoparticle layers by utilizing monodispersed Pd nanoparticles. The distinct advantage of monosized particles and contaminant-free samples with open porosity in addition to size effects resulted in improved CO sensing with decrease in Pd nanoparticle size to 5 nm, decreasing the lowest detection levels of CO using SnOx-based sensor technology down to 10 ppb (parts per billion) in dry synthetic air. The homogeneously mixed nanoparticle layers also exhibit discrimination capability between CO and ethanol in dry air as a manifestation of the dual conductance response. Detailed x-ray photoelectron spectroscopy studies clearly reveal "Mars-van Krevelen" as the key mechanism responsible for the observed sensing in mixed nanoparticle layers. The interfacial/surface PdO formed upon pretreatment in air is continuously "consumed" and "reformed" upon exposure, respectively, to CO and synthetic air. In contrast to the case of ethanol exposure with n-type response, the Pd aided reduction of tin oxide surface in CO ambient leads to p-type response. The sensors of the present study have a wide range of promising applications from air quality control to food and fuel industries.

  13. Supported catalysts using nanoparticles as the support material

    DOEpatents

    Wong, Michael S.; Wachs, Israel E.; Knowles, William V.

    2010-11-02

    A process for making a porous catalyst, comprises a) providing an aqueous solution containing a nanoparticle precursor, b) forming a composition containing nanoparticles, c) adding a first catalytic component or precursor thereof and a pore-forming agent to the composition containing nanoparticles and allowing the first catalytic component, the pore-forming agent, and the nanoparticles form an organic-inorganic structure, d) removing water from the organic-inorganic structure; and e) removing the pore-forming agent from the organic-inorganic structure so as to yield a porous catalyst.

  14. Highly size-controlled synthesis of Au/Pd nanoparticles by inert-gas condensation.

    PubMed

    Pérez-Tijerina, E; Pinilla, M Gracia; Mejía-Rosales, S; Ortiz-Méndez, U; Torres, A; José-Yacamán, M

    2008-01-01

    Gold/Palladium nanoparticles were fabricated by inert-gas condensation on a sputtering reactor. With this method, by controlling both the atmosphere on the condensation chamber and the magnetron power, it was possible to produce nanoparticles with a high degree of monodispersity in size. The structure and size of the Au/Pd nanoparticles were determined by mass spectroscopy, and confirmed by atomic force microscopy and electron transmission microscopy measurements. The chemical composition was analyzed by X-ray microanalysis. From these measurements we confirmed that with the sputtering technique we are able to produce particles of 1, 3, and 5 nm on size, depending on the choice of the synthesis conditions. From TEM measurements made both in the regular HREM, as well as in STEM-HAADF mode, we found that the particles are icosahedral in shape, and the micrographs show no evidence of a core-shell structure, in contrast to what is observed in the case of nanoparticles prepared by chemical synthesis.

  15. Diatomite-supported Pd-M (M=Cu, Co, Ni) bimetal nanocatalysts for selective hydrogenation of long-chain aliphatic esters.

    PubMed

    Huang, Changliang; Zhang, Hongye; Zhao, Yanfei; Chen, Sha; Liu, Zhimin

    2012-11-15

    Diatomite supported Pd-M (M=Cu, Co, Ni) bimetal nanocatalysts with various metal compositions were prepared and characterized by means of X-ray diffraction, transmission electron microscopy, and X-ray photoelectron spectroscopy. It was demonstrated that the metal nanoparticles were uniformly distributed on the support, and their size was centered around 8 nm with a relatively narrow size distribution. The catalysts were used to catalyze hydrogenation of long-chain aliphatic esters, including methyl palmitate, methyl stearate, and methyl laurate. It was indicated that the all diatomite-supported Pd-based bimetal catalysts were active to the selective hydrogenation of long-chain esters to corresponding alcohols at 270°C, originated from the synergistic effect between the metal particles and the diatomite support. For the selective hydrogenation of methyl palmitate, Pd-Cu/diatomite with metal loading of 1% and Pd/Cu=3 displayed the highest performance, giving a 1-hexadecanol yield of 82.9% at the substrate conversion of 98.8%. Copyright © 2012 Elsevier Inc. All rights reserved.

  16. Carbon-supported base metal nanoparticles: cellulose at work.

    PubMed

    Hoekstra, Jacco; Versluijs-Helder, Marjan; Vlietstra, Edward J; Geus, John W; Jenneskens, Leonardus W

    2015-03-01

    Pyrolysis of base metal salt loaded microcrystalline cellulose spheres gives a facile access to carbon-supported base metal nanoparticles, which have been characterized with temperature-dependent XRD, SEM, TEM, ICP-MS and elemental analysis. The role of cellulose is multifaceted: 1) it facilitates a homogeneous impregnation of the aqueous base metal salt solutions, 2) it acts as an efficacious (carbonaceous) support material for the uniformly dispersed base metal salts, their oxides and the metal nanoparticles derived therefrom, and 3) it contributes as a reducing agent via carbothermal reduction for the conversion of the metal oxide nanoparticles into the metal nanoparticles. Finally, the base metal nanoparticles capable of forming metastable metal carbides catalytically convert the carbonaceous support into a mesoporous graphitic carbon material.

  17. 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.

  18. Nitrogen-Doped Carbon Nanotube-Supported Pd Catalyst for Improved Electrocatalytic Performance toward Ethanol Electrooxidation

    NASA Astrophysics Data System (ADS)

    Wei, Ying; Zhang, Xinyuan; Luo, Zhiyong; Tang, Dian; Chen, Changxin; Zhang, Teng; Xie, Zailai

    2017-07-01

    In this study, hydrothermal carbonization (HTC) was applied for surface functionalization of carbon nanotubes (CNTs) in the presence of glucose and urea. The HTC process allowed the deposition of thin nitrogen-doped carbon layers on the surface of the CNTs. By controlling the ratio of glucose to urea, nitrogen contents of up to 1.7 wt% were achieved. The nitrogen-doped carbon nanotube-supported Pd catalysts exhibited superior electrochemical activity for ethanol oxidation relative to the pristine CNTs. Importantly, a 1.5-fold increase in the specific activity was observed for the Pd/HTC-N1.67%CNTs relative to the catalyst without nitrogen doping (Pd/HTC-CNTs). Further experiments indicated that the introduction of nitrogen species on the surface of the CNTs improved the Pd(0) loading and increased the binding energy.

  19. In situ X-ray Scattering and Dynamical Modeling of Pd Catalyst Nanoparticles Formed in Flames

    SciTech Connect

    Wang, Juan; Seifert, Sönke; Winans, Randall E.; Tolmachoff, Erik; Xin, Yuxuan; Chen, Dongping; Wang, Hai; Anderson, Scott L.

    2015-08-20

    It has previously been demonstrated that organopalladium precursors can break down under combustion conditions, forming nanoparticles that catalyze ignition. Here, we use in situ small-angle X-ray scattering (SAXS) to probe the formation and growth of palladium nanoparticles in an ethylene fl ame doped with 28 ppm (mol) of Pd(acetate) 2 . The particles appear to nucleate in the fl ame front and are observed by SAXS to grow in size and mass in the high-temperature region of the fl ame ( ~ 2200 K) with median diameters that evolve from 1.5 to 3.0 nm. Transmission electron microscopy of particles collected on a grid located outside the fl ame shows that the particles are metallic palladium with sizes comparable to those determined by SAXS. Molecular dynamics simulation of particles of selected sizes indicates that at the fl ame temperature the particles are molten and the average mass density of the particle material is notably smaller than that of bulk, liquid Pd at the melting point. Both experimental and computational results point to homogeneous nucleation and particle - particle coalescence as mechanisms for particle formation and growth. Aerosol dynamics simulation reproduces the time evolution of the particle size distribution and suggests that a substantial fraction of the particles must be electrically charged during their growth process.

  20. Gas sensing properties of MWCNT layers electrochemically decorated with Au and Pd nanoparticles

    PubMed Central

    Alvisi, Marco; Rossi, Riccardo; Cassano, Gennaro; Di Franco, Cinzia; Palmisano, Francesco; Torsi, Luisa

    2017-01-01

    Multiwalled carbon nanotube (MWCNT)-based chemiresistors were electrochemically decorated with Au and Pd nanoparticles (NPs), resulting in an improvement in the detection of gaseous pollutants as compared to sensors based on pristine MWCNTs. Electrophoresis was used to decorate MWCNTs with preformed Au or Pd NPs, thus preserving their nanometer-sized dimensions and allowing the metal content to be tuned by simply varying the deposition time. The sensing response of unmodified and metal-decorated MWCNTs was evaluated towards different gaseous pollutants (e.g., NO2, H2S, NH3 and C4H10) at a wide range of concentrations in the operating temperature range of 45–200 °C. The gas sensing results were related to the presence, type and loading of metal NPs used in the MWCNT functionalization. Compared to pristine MWCNTs, metal-decorated MWCNTs revealed a higher gas sensitivity, a faster response, a better stability, reversibility and repeatability, and a low detection limit, where all of these sensing properties were controlled by the type and loading of the deposited metal catalytic NPs. Specifically, in the NO2 gas sensing experiments, MWCNTs decorated with the lowest Au content revealed the highest sensitivity at 150 °C, while MWCNTs with the highest Pd loading showed the highest sensitivity when operated at 100 °C. Finally, considering the reported gas sensing results, sensing mechanisms have been proposed, correlating the chemical composition and gas sensing responses. PMID:28382249

  1. Controlled Synthesis of Pd/Pt Core Shell Nanoparticles Using Area-selective Atomic Layer Deposition

    PubMed Central

    Cao, Kun; Zhu, Qianqian; Shan, Bin; Chen, Rong

    2015-01-01

    We report an atomic scale controllable synthesis of Pd/Pt core shell nanoparticles (NPs) via area-selective atomic layer deposition (ALD) on a modified surface. The method involves utilizing octadecyltrichlorosilane (ODTS) self-assembled monolayers (SAMs) to modify the surface. Take the usage of pinholes on SAMs as active sites for the initial core nucleation, and subsequent selective deposition of the second metal as the shell layer. Since new nucleation sites can be effectively blocked by surface ODTS SAMs in the second deposition stage, we demonstrate the successful growth of Pd/Pt and Pt/Pd NPs with uniform core shell structures and narrow size distribution. The size, shell thickness and composition of the NPs can be controlled precisely by varying the ALD cycles. Such core shell structures can be realized by using regular ALD recipes without special adjustment. This SAMs assisted area-selective ALD method of core shell structure fabrication greatly expands the applicability of ALD in fabricating novel structures and can be readily applied to the growth of NPs with other compositions. PMID:25683469

  2. Pt-Pd bimetallic nanoparticles on MWCNTs: catalyst for hydrogen peroxide electrosynthesis

    NASA Astrophysics Data System (ADS)

    Félix-Navarro, R. M.; Beltrán-Gastélum, M.; Salazar-Gastélum, M. I.; Silva-Carrillo, C.; Reynoso-Soto, E. A.; Pérez-Sicairos, S.; Lin, S. W.; Paraguay-Delgado, F.; Alonso-Núñez, G.

    2013-08-01

    Bimetallic nanoparticles of Pt-Pd were deposited by the microemulsion method on a multiwall carbon nanotube (MWCNTs) to obtain a Pt-Pd/MWCNTs for electrocatalytic reduction of O2 to H2O2. The activity and selectivity of the catalyst was determined qualitatively by the rotating disk electrode method in acidic medium. The catalyst was spray-coated onto a reticulated vitreous carbon substrate and quantitatively was tested in bulk electrolysis for 20 min under potentiostatic conditions (0.5 V vs Ag/AgCl) in a 0.5 M H2SO4 electrolyte using dissolved O2. The bulk electrolysis experiments show that the Pt-Pd/MWCNTs catalyst is more efficient for H2O2 electrogeneration than a MWCNTs catalyst. Nitrobenzene degradation by electrogenerated H2O2 alone and Electro-Fenton process were also tested. Our results show that both processes decompose nitrobenzene, but the Electro-Fenton process does it more efficiently. The prepared nanoparticulated catalyst shows a great potential in environmental applications.

  3. Controlled Synthesis of Pd/Pt Core Shell Nanoparticles Using Area-selective Atomic Layer Deposition.

    PubMed

    Cao, Kun; Zhu, Qianqian; Shan, Bin; Chen, Rong

    2015-02-16

    We report an atomic scale controllable synthesis of Pd/Pt core shell nanoparticles (NPs) via area-selective atomic layer deposition (ALD) on a modified surface. The method involves utilizing octadecyltrichlorosilane (ODTS) self-assembled monolayers (SAMs) to modify the surface. Take the usage of pinholes on SAMs as active sites for the initial core nucleation, and subsequent selective deposition of the second metal as the shell layer. Since new nucleation sites can be effectively blocked by surface ODTS SAMs in the second deposition stage, we demonstrate the successful growth of Pd/Pt and Pt/Pd NPs with uniform core shell structures and narrow size distribution. The size, shell thickness and composition of the NPs can be controlled precisely by varying the ALD cycles. Such core shell structures can be realized by using regular ALD recipes without special adjustment. This SAMs assisted area-selective ALD method of core shell structure fabrication greatly expands the applicability of ALD in fabricating novel structures and can be readily applied to the growth of NPs with other compositions.

  4. Size-dependent electrocatalytic reduction of CO2 over Pd nanoparticles.

    PubMed

    Gao, Dunfeng; Zhou, Hu; Wang, Jing; Miao, Shu; Yang, Fan; Wang, Guoxiong; Wang, Jianguo; Bao, Xinhe

    2015-04-08

    Size effect has been regularly utilized to tune the catalytic activity and selectivity of metal nanoparticles (NPs). Yet, there is a lack of understanding of the size effect in the electrocatalytic reduction of CO2, an important reaction that couples with intermittent renewable energy storage and carbon cycle utilization. We report here a prominent size-dependent activity/selectivity in the electrocatalytic reduction of CO2 over differently sized Pd NPs, ranging from 2.4 to 10.3 nm. The Faradaic efficiency for CO production varies from 5.8% at -0.89 V (vs reversible hydrogen electrode) over 10.3 nm NPs to 91.2% over 3.7 nm NPs, along with an 18.4-fold increase in current density. Based on the Gibbs free energy diagrams from density functional theory calculations, the adsorption of CO2 and the formation of key reaction intermediate COOH* are much easier on edge and corner sites than on terrace sites of Pd NPs. In contrast, the formation of H* for competitive hydrogen evolution reaction is similar on all three sites. A volcano-like curve of the turnover frequency for CO production within the size range suggests that CO2 adsorption, COOH* formation, and CO* removal during CO2 reduction can be tuned by varying the size of Pd NPs due to the changing ratio of corner, edge, and terrace sites.

  5. Synergistic effect in the oxidation of benzyl alcohol using citrate-stabilized gold bimetallic nanoparticles supported on alumina

    NASA Astrophysics Data System (ADS)

    Gómez-Villarraga, Fernando; Radnik, Jörg; Martin, Andreas; Köckritz, Angela

    2016-06-01

    Bimetallic nanoparticles (NPs) containing gold and various second metals ( M = Pd, Pt, Cu, and Ag) supported on alumina (AuM/Alumina) were prepared using sodium citrate as stabilizer. In addition, supported monometallic Au/Alumina and Pd/Alumina were synthesized and tested to reveal synergistic effects in the catalytic evaluation of the bimetallic catalysts. The monometallic and bimetallic NPs revealed average sizes below 10 nm. The oxidation of benzyl alcohol with molecular oxygen as oxidant at mild conditions in liquid phase in the absence and presence (toluene or NaOH aqueous solution, 0.2 M) of a solvent was selected as test reaction to evaluate the catalytic properties of the above-mentioned solids. AuPd/Alumina exhibited the best catalytic activity among all bimetallic catalysts using toluene as solvent and under solvent-free conditions, respectively. In comparison to the monometallic catalysts, a synergistic effect with AuPd/Alumina was only evident in the solvent-free reaction. The AuPd/Alumina catalyst was able to oxidize benzyl alcohol selectively depending on the reaction medium into benzaldehyde (toluene or solvent-free) or benzoic acid (NaOH aqueous solution, 0.2 M). However, the catalyst deactivated due to particle growth of the bimetallic AuPd NPs by Ostwald ripening and leaching was not observed in the oxidation using toluene as solvent. The size of the catalytically active NPs, the metal composition of the particles, and the reaction conditions greatly influenced the catalytic oxidation results.

  6. Synthesis of AuPd alloyed nanoparticles via room-temperature electron reduction with argon glow discharge as electron source

    NASA Astrophysics Data System (ADS)

    Yang, Manman; Wang, Zongyuan; Wang, Wei; Liu, Chang-jun

    2014-08-01

    Argon glow discharge has been employed as a cheap, environmentally friendly, and convenient electron source for simultaneous reduction of HAuCl4 and PdCl2 on the anodic aluminum oxide (AAO) substrate. The thermal imaging confirms that the synthesis is operated at room temperature. The reduction is conducted with a short time (30 min) under the pressure of approximately 100 Pa. This room-temperature electron reduction operates in a dry way and requires neither hydrogen nor extra heating nor chemical reducing agent. The analyses using X-ray photoelectron spectroscopy (XPS) confirm all the metallic ions have been reduced. The characterization with X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM) shows that AuPd alloyed nanoparticles are formed. There also exist some highly dispersed Au and Pd monometallic particles that cannot be detected by XRD and transmission electron microscopy (TEM) because of their small particle sizes. The observed AuPd alloyed nanoparticles are spherical with an average size of 14 nm. No core-shell structure can be observed. The room-temperature electron reduction can be operated in a larger scale. It is an easy way for the synthesis of AuPd alloyed nanoparticles.

  7. Synthesis of AuPd alloyed nanoparticles via room-temperature electron reduction with argon glow discharge as electron source.

    PubMed

    Yang, Manman; Wang, Zongyuan; Wang, Wei; Liu, Chang-Jun

    2014-01-01

    Argon glow discharge has been employed as a cheap, environmentally friendly, and convenient electron source for simultaneous reduction of HAuCl4 and PdCl2 on the anodic aluminum oxide (AAO) substrate. The thermal imaging confirms that the synthesis is operated at room temperature. The reduction is conducted with a short time (30 min) under the pressure of approximately 100 Pa. This room-temperature electron reduction operates in a dry way and requires neither hydrogen nor extra heating nor chemical reducing agent. The analyses using X-ray photoelectron spectroscopy (XPS) confirm all the metallic ions have been reduced. The characterization with X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM) shows that AuPd alloyed nanoparticles are formed. There also exist some highly dispersed Au and Pd monometallic particles that cannot be detected by XRD and transmission electron microscopy (TEM) because of their small particle sizes. The observed AuPd alloyed nanoparticles are spherical with an average size of 14 nm. No core-shell structure can be observed. The room-temperature electron reduction can be operated in a larger scale. It is an easy way for the synthesis of AuPd alloyed nanoparticles.

  8. Synthesis of AuPd alloyed nanoparticles via room-temperature electron reduction with argon glow discharge as electron source

    PubMed Central

    2014-01-01

    Argon glow discharge has been employed as a cheap, environmentally friendly, and convenient electron source for simultaneous reduction of HAuCl4 and PdCl2 on the anodic aluminum oxide (AAO) substrate. The thermal imaging confirms that the synthesis is operated at room temperature. The reduction is conducted with a short time (30 min) under the pressure of approximately 100 Pa. This room-temperature electron reduction operates in a dry way and requires neither hydrogen nor extra heating nor chemical reducing agent. The analyses using X-ray photoelectron spectroscopy (XPS) confirm all the metallic ions have been reduced. The characterization with X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM) shows that AuPd alloyed nanoparticles are formed. There also exist some highly dispersed Au and Pd monometallic particles that cannot be detected by XRD and transmission electron microscopy (TEM) because of their small particle sizes. The observed AuPd alloyed nanoparticles are spherical with an average size of 14 nm. No core-shell structure can be observed. The room-temperature electron reduction can be operated in a larger scale. It is an easy way for the synthesis of AuPd alloyed nanoparticles. PMID:25177221

  9. Solid solution alloy nanoparticles of immiscible Pd and Ru elements neighboring on Rh: changeover of the thermodynamic behavior for hydrogen storage and enhanced CO-oxidizing ability.

    PubMed

    Kusada, Kohei; Kobayashi, Hirokazu; Ikeda, Ryuichi; Kubota, Yoshiki; Takata, Masaki; Toh, Shoichi; Yamamoto, Tomokazu; Matsumura, Syo; Sumi, Naoya; Sato, Katsutoshi; Nagaoka, Katsutoshi; Kitagawa, Hiroshi

    2014-02-05

    Pd(x)Ru(1-x) solid solution alloy nanoparticles were successfully synthesized over the whole composition range through a chemical reduction method, although Ru and Pd are immiscible at the atomic level in the bulk state. From the XRD measurement, it was found that the dominant structure of Pd(x)Ru(1-x) changes from fcc to hcp with increasing Ru content. The structures of Pd(x)Ru(1-x) nanoparticles in the Pd composition range of 30-70% consisted of both solid solution fcc and hcp structures, and both phases coexist in a single particle. In addition, the reaction of hydrogen with the Pd(x)Ru(1-x) nanoparticles changed from exothermic to endothermic as the Ru content increased. Furthermore, the prepared Pd(x)Ru(1-x) nanoparticles demonstrated enhanced CO-oxidizing catalytic activity; Pd0.5Ru0.5 nanoparticles exhibit the highest catalytic activity. This activity is much higher than that of the practically used CO-oxidizing catalyst Ru and that of the neighboring Rh, between Ru and Pd.

  10. Continuous syntheses of Pd@Pt and Cu@Ag core-shell nanoparticles using microwave-assisted core particle formation coupled with galvanic metal displacement.

    PubMed

    Miyakawa, Masato; Hiyoshi, Norihito; Nishioka, Masateru; Koda, Hidekazu; Sato, Koichi; Miyazawa, Akira; Suzuki, Toshishige M

    2014-08-07

    Continuous synthesis of Pd@Pt and Cu@Ag core-shell nanoparticles was performed using flow processes including microwave-assisted Pd (or Cu) core-nanoparticle formation followed by galvanic displacement with a Pt (or Ag) shell. The core-shell structure and the nanoparticle size were confirmed using high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) observation and EDS elemental mapping. The Pd@Pt nanoparticles with a particle size of 6.5 ± 0.6 nm and a Pt shell thickness of ca. 0.25 nm were synthesized with appreciably high Pd concentration (Pd 100 mM). This shell thickness corresponds to one atomic layer thickness of Pt encapsulating the Pd core metal. The particle size of core Pd was controlled by tuning the initial concentrations of Na2[PdCl4] and PVP. Core-shell Cu@Ag nanoparticles with a particle size of 90 ± 35 nm and an Ag shell thickness of ca. 3.5 nm were obtained using similar sequential reactions. Oxidation of the Cu core was suppressed by the coating of Cu nanoparticles with the Ag shell.

  11. Pd-Au nanoparticle decorated carbon nanotube as a sensing layer on the surface of glassy carbon electrode for electrochemical determination of ceftazidime.

    PubMed

    Shahrokhian, Saeed; Salimian, Razieh; Rastgar, Shokoufeh

    2014-01-01

    A simple electrodeposition method is employed to construct a thin film modifier of palladium-gold nanoparticles (Pd-AuNPs) decorated multi-walled carbon nanotube (MWCNT) on the surface of glassy carbon electrode (GCE). Morphology and property of Pd-AuNPs-MWCNT have been examined by scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS). Electrochemical performance of Pd-AuNPs-MWCNT/GCE for detection of ceftazidime (CFZ) has been investigated by cyclic voltammetry (CV). This nanostructured film modified electrode effectively exhibited enhanced properties for detection of ceftazidime (CFZ). The effects of various experimental variables such as, the amount of casted MWCNT, time and potential of deposition of metal nanoparticles and the pH of the buffered solution on the electrode response are optimized. The proposed electrode showed a linear dynamic range of 0.05-50μM and the detection limit of 1nM for the CFZ. The modified electrode successfully supports the sensitive detection of trace amounts of the CFZ in pharmaceutical and clinical preparations.

  12. In situ fabrication of a perfect Pd/ZnO@ZIF-8 core-shell microsphere as an efficient catalyst by a ZnO support-induced ZIF-8 growth strategy.

    PubMed

    Lin, Lu; Zhang, Tong; Liu, Haiou; Qiu, Jieshan; Zhang, Xiongfu

    2015-05-07

    Controllable encapsulation of nanoparticles with metal organic frameworks (MOFs) has been an efficient way to impart the unique chemical and physical properties of the nanoparticles to metal organic frameworks and create new types of multifunctional MOF core-shell materials with enhanced properties. Here, a novel ZnO support-induced encapsulation strategy is reported to efficiently fabricate a Pd/ZnO@ZIF-8 core-shell catalyst, with Pd/ZnO as the core and ZIF-8 as the shell. The novel synthesis procedure involves first loading Pd nanoparticles onto the surface of the ZnO microsphere to form a Pd/ZnO core and then coating the core with a layer of defect-free ZIF-8 shell via ZnO-induced in situ ZIF-8 growth to obtain the Pd/ZnO@ZIF-8 core-shell catalyst. It was crucial that the ZIF-8 was in situ formed from the ZnO core in an ethanol solution only containing 2-methylimidazole under mild conditions. This strategy allowed for the growth of ZIF-8 right on the surface of Pd/ZnO via the reaction between ZnO and the 2-methylimidazole ligands, and thus avoided the random deposition of ZIF-8 crystals on the Pd/ZnO core as in the case of the conventional ZIF-8 synthesis solution. Furthermore, use of ethanol as the solvent also favored achievement of the well-defined Pd/ZnO@ZIF-8 structure, since the ethanol solution of 2-methylimidazole was able to keep the balance between ZnO dissolution and ZIF-8 formation. The as-prepared Pd/ZnO@ZIF-8 core-shell microsphere as an efficient catalyst displayed excellent performance in terms of size-selectivity, stability and anti-poisoning in the liquid hydrogenations of alkenes.

  13. In situ fabrication of a perfect Pd/ZnO@ZIF-8 core-shell microsphere as an efficient catalyst by a ZnO support-induced ZIF-8 growth strategy

    NASA Astrophysics Data System (ADS)

    Lin, Lu; Zhang, Tong; Liu, Haiou; Qiu, Jieshan; Zhang, Xiongfu

    2015-04-01

    Controllable encapsulation of nanoparticles with metal organic frameworks (MOFs) has been an efficient way to impart the unique chemical and physical properties of the nanoparticles to metal organic frameworks and create new types of multifunctional MOF core-shell materials with enhanced properties. Here, a novel ZnO support-induced encapsulation strategy is reported to efficiently fabricate a Pd/ZnO@ZIF-8 core-shell catalyst, with Pd/ZnO as the core and ZIF-8 as the shell. The novel synthesis procedure involves first loading Pd nanoparticles onto the surface of the ZnO microsphere to form a Pd/ZnO core and then coating the core with a layer of defect-free ZIF-8 shell via ZnO-induced in situ ZIF-8 growth to obtain the Pd/ZnO@ZIF-8 core-shell catalyst. It was crucial that the ZIF-8 was in situ formed from the ZnO core in an ethanol solution only containing 2-methylimidazole under mild conditions. This strategy allowed for the growth of ZIF-8 right on the surface of Pd/ZnO via the reaction between ZnO and the 2-methylimidazole ligands, and thus avoided the random deposition of ZIF-8 crystals on the Pd/ZnO core as in the case of the conventional ZIF-8 synthesis solution. Furthermore, use of ethanol as the solvent also favored achievement of the well-defined Pd/ZnO@ZIF-8 structure, since the ethanol solution of 2-methylimidazole was able to keep the balance between ZnO dissolution and ZIF-8 formation. The as-prepared Pd/ZnO@ZIF-8 core-shell microsphere as an efficient catalyst displayed excellent performance in terms of size-selectivity, stability and anti-poisoning in the liquid hydrogenations of alkenes.

  14. Magnetic nanoparticle-supported glutathione: a conceptually sustainable organocatalyst

    EPA Science Inventory

    A conceptually novel nanoparticle-supported and magnetically recoverable organocatalyst has been developed, which is readily prepared from inexpensive starting materials in a truly sustainable manner; which catalyzes Paal-Knorr reaction with high yield in pure aqueous medium that...

  15. Green Synthesis of Fe and Fe/Pd Bimetallic Nanoparticles in Membranes for Reductive Degradation of Chlorinated Organics

    EPA Science Inventory

    Membranes containing reactive nanoparticles (Fe and Fe/Pd) immobilized in a polymer film (polyacrylic acid, PAA-coated polyvinylidene fluoride, PVDF membrane) are prepared by a new method. In the present work a biodegradable, non-toxic -“green” reducing agent, green tea extract ...

  16. Green Synthesis of Fe and Fe/Pd Bimetallic Nanoparticles in Membranes for Reductive Degradation of Chlorinated Organics

    EPA Science Inventory

    Membranes containing reactive nanoparticles (Fe and Fe/Pd) immobilized in a polymer film (polyacrylic acid, PAA-coated polyvinylidene fluoride, PVDF membrane) are prepared by a new method. In the present work a biodegradable, non-toxic -“green” reducing agent, green tea extract ...

  17. Effect of Pd ion doping in the band gap of SnO2 nanoparticles: structural and optical studies

    NASA Astrophysics Data System (ADS)

    Nandan, Brajesh; Venugopal, B.; Amirthapandian, S.; Panigrahi, B. K.; Thangadurai, P.

    2013-10-01

    Pd ion doping has influenced the band gap of SnO2 nanoparticles. Undoped and Pd ion-doped SnO2 nanoparticles were synthesized by chemical co-precipitation method. A tetragonal phase of SnO2 with a grain size range of 7-13 nm was obtained (studied by X-ray diffraction and transmission electron microscopy). A decreasing trend in the particle size with increasing doping concentration was observed. The presence of Pd in doped SnO2 was confirmed by chemical analysis carried out by energy-dispersive spectroscopy in the transmission electron microscope. Diffuse reflectance spectra showed a blue shift in absorption with increasing palladium concentration. Band gap of SnO2 nanoparticles was estimated from the diffuse reflectance spectra using Kubelka-Munk function and it was increasing with the increase of Pd ion concentration from 3.73 to 4.21 eV. The variation in band gap is attributed predominantly to the lattice strain and particle size. All the samples showed a broad photoluminescence emission centered at 375 nm when excited at 270 nm. A systematic study on the structural and optical properties of SnO2 nanoparticles is presented.

  18. Selective hydrogenation of 2-methyl-3-butyn-2-ol catalyzed by embedded polymer-protected PdZn nanoparticles

    NASA Astrophysics Data System (ADS)

    Okhlopkova, Lyudmila B.; Matus, Ekaterina V.; Prosvirin, Igor P.; Kerzhentsev, Michail A.; Ismagilov, Zinfer R.

    2015-12-01

    PdZn/TiO2 catalysts were synthesized by sol-gel method using a template Pluronic F127. PdZn nanoparticles with the size ranging from 1.7 to 2 nm were prepared by ethylene glycol reduction of ZnCl2 and Pd(CH3COO)2 in the presence of stabilizer and introduced into the matrix by addition into TiO2 sol, followed by different activation procedures. The structure, particles size, and chemical composition of nanoparticles and catalysts were characterized by transmission electron microscopy, X-ray photoelectron spectroscopy, X-ray fluorescence spectroscopy, and energy dispersive spectroscopy. The prepared catalysts have been tested in the selective hydrogenation of 2-methyl-3-butyn-2-ol, and the results have been compared with catalysts prepared by conventional impregnation. The results indicate that bimetallic PdZn nanoparticles-based catalysts show higher selectivity than corresponding monometallic Pd/TiO2. Embedded on titania, bimetallic nanoparticles stabilized with polyvinylpyrrolidone exhibit good activity (1.1-1.8 mol MBY/mol Pd/s-1) and high selectivity to 2-methyl-3-buten-2-ol (81.5-88.9 % at 95 % conversion). The influence of the nature of the stabilizer, the stabilizer/metal molar ratio, and activation conditions on the catalytic behavior of the samples was analyzed. It is shown that the particle size does not significantly affect the catalytic properties in the range of 4.4-6.5 nm. The nature and amount of stabilizer seem to be crucial to prepare efficient catalyst.

  19. Supported Pd-Au Membrane Reactor for Hydrogen Production: Membrane Preparation, Characterization and Testing.

    PubMed

    Iulianelli, Adolfo; Alavi, Marjan; Bagnato, Giuseppe; Liguori, Simona; Wilcox, Jennifer; Rahimpour, Mohammad Reza; Eslamlouyan, Reza; Anzelmo, Bryce; Basile, Angelo

    2016-05-09

    A supported Pd-Au (Au 7wt%) membrane was produced by electroless plating deposition. Permeation tests were performed with pure gas (H₂, H₂, N₂, CO₂, CH₄) for long time operation. After around 400 h under testing, the composite Pd-Au membrane achieved steady state condition, with an H₂/N₂ ideal selectivity of around 500 at 420 °C and 50 kPa as transmembrane pressure, remaining stable up to 1100 h under operation. Afterwards, the membrane was allocated in a membrane reactor module for methane steam reforming reaction tests. As a preliminary application, at 420 °C, 300 kPa of reaction pressure, space velocity of 4100 h(-1), 40% methane conversion and 35% hydrogen recovery were reached using a commercial Ni/Al₂O₃ catalyst. Unfortunately, a severe coke deposition affected irreversibly the composite membrane, determining the loss of the hydrogen permeation characteristics of the supported Pd-Au membrane.

  20. Nanocrystaline tungsten carbide supported Au-Pd electrocatalyst for oxygen reduction

    NASA Astrophysics Data System (ADS)

    Nie, Ming; Shen, Pei Kang; Wei, Zidong

    Au-Pd nanobimetallic particles supported on nanocrystaline tungsten carbide as electrocatalysts for oxygen reduction were prepared by an intermittent microwave heating (IMH) method. XRD measurement revealed that AuPd alloy formed during the IMH process. We showed these novel electrocatalysts could offer the activities that surpass that of the state-of-the-art Pt-based electrocatalysts for oxygen reduction reaction. The AuPd-WC/C electrode showed an over 70 mV shift towards more positive potentials compared to Pt/C electrode for ORR. The advantage seemed to come from the novel support of tungsten carbide which itself has the catalytic activity to enhance the catalytic activity of the metal electrocatalysts.

  1. Novel yolk-shell-structured Fe3O4@γ-AlOOH nanocomposite modified with Pd nanoparticles as a recyclable catalyst with excellent catalytic activity

    NASA Astrophysics Data System (ADS)

    Cui, Xueliang; Zheng, Yunfeng; Tian, Meng; Dong, Zhengping

    2017-09-01

    A novel yolk-shell-structured material (Fe3O4@γ-AlOOH-YSMs) with hierarchical γ-AlOOH flakes as the mesoporous shell and Fe3O4 nanoparticles (NPs) in the hollow core was prepared by using Fe3O4@SiO2 NPs as the seeds as well as NaAlO2 and urea as the precursor. The prepared Fe3O4@γ-AlOOH-YSMs were used as a catalyst support for fabricating a Pd/Fe3O4@γ-AlOOH-YSMs nanocatalyst with no obvious aggregation of the Pd NPs. The Pd/Fe3O4@γ-AlOOH-YSMs nanocatalyst was utilized for the catalytic reduction of the widely used and highly toxic 4-nitrophenol, rhodamine B, methylene blue, and methyl orange; and showed excellent catalytic activity as compared with other noble-metal-based catalysts. Furthermore, the Pd/Fe3O4@γ-AlOOH-YSMs nanocatalyst also can be easily separated from the reaction mixture and reused for at least ten times without any obvious decrease in the catalytic activity, indicating its reusability and stability.

  2. Ecotoxicity of halloysite nanotube-supported palladium nanoparticles in Raphanus sativus L.

    PubMed

    Bellani, Lorenza; Giorgetti, Lucia; Riela, Serena; Lazzara, Giuseppe; Scialabba, Anna; Massaro, Marina

    2016-10-01

    Halloysite nanotubes (HNTs) are natural nanomaterials that are biocompatible and available in large amounts at low prices. They are emerging nanomaterials with appealing properties for applications like support for metal nanoparticles (NPs). The potential environmental impacts of NPs can be understood in terms of phytotoxicity. Current research has been focusing on HNT applications in cell or animal models, while their use in plants is limited so their ecotoxicological impact is poorly documented. To date there are no studies on the phytotoxic effects of functionalized halloysites (functionalized-HNTs). To develop a quantitative risk assessment model for predicting the potential impact of HNT-supported palladium nanoparticles (HNT-PdNPs) on plant life, an investigation was undertaken to explore their effects on seed germination, seedling development, and mitotic division in root tip cells of 2 lots of Raphanus sativus L. with different vigor. The results showed that exposure to 1500 mg/L of HNTs, functionalized-HNTs, and HNT-PdNPs had no significant influence on germination, seedling development, xylem differentiation, or mitotic index in both lots. Cytogenetic analyses revealed that treatments with functionalized-HNT significantly increased the number of aberrations in low-vigor seeds. These results suggest that low-vigor seeds represent a model for a stress test that would be useful to monitor the effects of NPs. Moreover the present study offers scientific evidence for the use of halloysite for environmental purposes, supporting the biological safety of HNT-PdNPs. Environ Toxicol Chem 2016;35:2503-2510. © 2016 SETAC.

  3. Methane catalytic combustion on Pd9/gamma-Al2O3 with different degrees of Pd oxidation.

    PubMed

    Czekaj, Izabela; Kacprzak, Katarzyna A; Mantzaras, John

    2013-01-01

    This research is focused on the analysis of adsorbed CH4 intermediates at oxidized Pd9 nanoparticles supported on gamma-alumina. From first-principle density functional theory (DFT) calculations, several configurations, charge transfer and electronic density of states have been analyzed in order to determine feasible paths for the oxidation process. Furthermore methane oxidation cycles have been investigated on Pd nanoparticles with different degrees of oxidation. In case of low oxidized Pd nanoparticles, activation of methane is observed, whereby hydrogen from methane is adsorbed at one oxygen atom. This reaction is exothermic. In a subsequent step, two water molecules desorb. Additionally, a very interesting structural effect becomes evident; Pd-carbide formation, which is also an exothermic reaction. Furthermore, oxidation of such carbidized Pd-nanoparticles leads to CO2 formation, which is an endothermic reaction. One important result is that the support is involved in the CO2 formation. A different mechanism of methane oxidation was discovered for highly oxidized Pd nanoparticles. When the Pd nanoparticle is more strongly exposed to oxidative conditions, adsorption of methane is also possible, but it leads to carbonic acid production at the interface between the Pd nanoparticles and support. This process is endothermic.

  4. One-step electrochemical synthesis of preferentially oriented (111) Pd nanocrystals supported on graphene nanoplatelets for formic acid electrooxidation

    NASA Astrophysics Data System (ADS)

    Chen, Qing-Song; Xu, Zhong-Ning; Peng, Si-Yan; Chen, Yu-Min; Lv, Dong-Mei; Wang, Zhi-Qiao; Sun, Jing; Guo, Guo-Cong

    2015-05-01

    Pd nanocrystals supported on graphene nanoplatelets (Pd/GNP) have been successfully synthesized by simultaneously electrochemical milling of Pd wire and graphite rod. It should be stressed that without the assistance of graphite rod, the Pd nanocrystals are unable to be obtained individually from Pd wire under the same conditions. Investigations of SEM and TEM demonstrate that Pd/GNP are preferentially decorated with (111) faceted nanocrystals. XPS studies confirm the strong metal-support interaction in Pd/GNP and reveal the surface is almost composed of Pd(0) species. Electrochemical measurements show that the prepared Pd based catalyst exhibits superior electrocatalytic activity towards formic acid oxidation, which may be attributed to the combined effects involving the preferentially oriented (111) surface structure, specific electronic structure and high dispersion of Pd nanocrystals as well as the support effects of graphene nanoplatelets. The synthesis method is simple and effective to prepare excellent new carbon-supported electrocatalysts, which is of great significance for direct organic molecule fuel cell.

  5. In situ control of phenol adsorption on conductive Pd-fluorine-doped tin dioxide-supported and Pd-alumina-supported catalysts in electrocatalytic hydrogenation.

    PubMed

    Tountian, Dihourahouni; Brisach-Wittmeyer, Anne; Nkeng, Paul; Poillerat, Gérard; Ménard, Hugues

    2009-09-15

    In the context of the electrocatalytic hydrogenation (ECH) process of unsaturated organic molecules, we have shown using infrared spectroscopy and water contact angle measurements that catalysts powders made of palladium on conductive tin dioxide (10% Pd/SnO2:F) and on alumina (10% Pd/Al2O3) are functionalized with organic chains when they were dipped in supporting electrolyte aqueous solutions containing different carboxylic acids. The carboxylic acids are bound to the supports (SnO2:F and Al2O3) through either the carboxyl or carboxylate groups. The measurement of contact angles confirmed that the support surface is functionalized by the carboxylic acids but also indicated the hydrophobic or hydrophilic character of the resultant surface. With these functionalized catalysts, the effectiveness of electrocatalytic hydrogenation of phenol could be modulated by controlling the adsorption of phenol. The adsorption depends mainly on the functionalization agent (carboxylic acid) and to a lesser extent on the identity of the support material (SnO2:F or Al2O3). Because adsorption is the step that induces the selectivity of the ECH process, controlling this phenomenon by functionalizing the catalyst support in situ is promising for obtaining molecules of choice.

  6. Pd@Pt Core-Shell Nanoparticles with Branched Dandelion-like Morphology as Highly Efficient Catalysts for Olefin Reduction.

    PubMed

    Datta, Kasibhatta Josena; Datta, Kasibhatta Kumara Ramanatha; Gawande, Manoj B; Ranc, Vaclav; Čépe, Klára; Malgras, Victor; Yamauchi, Yusuke; Varma, Rajender S; Zboril, Radek

    2016-01-26

    A facile synthesis based on the addition of ascorbic acid to a mixture of Na2 PdCl4, K2 PtCl6, and Pluronic P123 results in highly branched core-shell nanoparticles (NPs) with a micro-mesoporous dandelion-like morphology comprising Pd core and Pt shell. The slow reduction kinetics associated with the use of ascorbic acid as a weak reductant and suitable Pd/Pt atomic ratio (1:1) play a principal role in the formation mechanism of such branched Pd@Pt core-shell NPs, which differs from the traditional seed-mediated growth. The catalyst efficiently achieves the reduction of a variety of olefins in good to excellent yields. Importantly, higher catalytic efficiency of dandelion-like Pd@Pt core-shell NPs was observed for the olefin reduction than commercially available Pt black, Pd NPs, and physically admixed Pt black and Pd NPs. This superior catalytic behavior is not only due to larger surface area and synergistic effects but also to the unique micro-mesoporous structure with significant contribution of mesopores with sizes of several tens of nanometers. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Rational synthesis of Pd nanoparticle-embedded reduced graphene oxide frameworks with enhanced selective catalysis in water

    NASA Astrophysics Data System (ADS)

    Liu, Jian; Hu, Guowen; Yang, Yanmei; Zhang, Haoli; Zuo, Wei; Liu, Weisheng; Wang, Baodui

    2016-01-01

    A three-dimensional (3D) Pd-reduced graphene oxide framework (Pd-rGOF) with hierarchical macro- and mesoporous structures has been developed via covalence- and coordination-assisted self-assembly approach. In this facile fabrication process, GO was first cross-linked with triethylene tetramine (TETA) to form 3D GOF, in which well-dispersed and ultrasmall Pd nanoparticles (NPs) in situ grew and embedded the framework. The obtained nanopores, 3D Pd-rGOF, can act as nanoreactors to help the reaction substrates thoroughly contact with the surface of Pd NPs, thereby exhibiting high activity and selectivity toward the Tsuji-Trost reaction in water, with 99% conversion and selectivity for most substrates. Moreover, the 3D Pd-rGOF catalyst can be reused more than ten times without significant loss of activity, rendering this catalyst long-term stability. The abovementioned observations make the rGOF a universal platform to coordinate other noble metal ions (NM) to construct desired NM-rGOF nanocatalysts with improved activity, selectivity, and durability that can be used in a broad range of practical applications.A three-dimensional (3D) Pd-reduced graphene oxide framework (Pd-rGOF) with hierarchical macro- and mesoporous structures has been developed via covalence- and coordination-assisted self-assembly approach. In this facile fabrication process, GO was first cross-linked with triethylene tetramine (TETA) to form 3D GOF, in which well-dispersed and ultrasmall Pd nanoparticles (NPs) in situ grew and embedded the framework. The obtained nanopores, 3D Pd-rGOF, can act as nanoreactors to help the reaction substrates thoroughly contact with the surface of Pd NPs, thereby exhibiting high activity and selectivity toward the Tsuji-Trost reaction in water, with 99% conversion and selectivity for most substrates. Moreover, the 3D Pd-rGOF catalyst can be reused more than ten times without significant loss of activity, rendering this catalyst long-term stability. The

  8. Development of Pd and Pd-Co catalysts supported on multi-walled carbon nanotubes for formic acid oxidation

    NASA Astrophysics Data System (ADS)

    Morales-Acosta, D.; Ledesma-Garcia, J.; Godinez, Luis A.; Rodríguez, H. G.; Álvarez-Contreras, L.; Arriaga, L. G.

    Pd-Co and Pd catalysts were prepared by the impregnation synthesis method at low temperature on multi-walled carbon nanotubes (MWCNTs). The nanotubes were synthesized by spray pyrolysis technique. Both catalysts were obtained with high homogeneous distribution and particle size around 4 nm. The morphology, composition and electrocatalytic properties were investigated by transmission electron microscopy, scanning electron microscopy-energy dispersive X-ray analysis, X-ray diffraction and electrochemical measurements, respectively. The electrocatalytic activity of Pd and PdCo/MWCNTs catalysts was investigated in terms of formic acid electrooxidation at low concentration in H 2SO 4 aqueous solution. The results obtained from voltamperometric studies showed that the current density achieved with the PdCo/MWCNTs catalyst is 3 times higher than that reached with the Pd/MWCNTs catalyst. The onset potential for formic acid electrooxidation on PdCo/MWCNTs electrocatalyst showed a negative shift ca. 50 mV compared with Pd/MWCNTs.

  9. Investigation of Supported Pd-Based Electrocatalysts for the Oxygen Reduction Reaction: Performance, Durability and Methanol Tolerance

    PubMed Central

    Lo Vecchio, Carmelo; Alegre, Cinthia; Sebastián, David; Stassi, Alessandro; Aricò, Antonino S.; Baglio, Vincenzo

    2015-01-01

    Next generation cathode catalysts for direct methanol fuel cells (DMFCs) must have high catalytic activity for the oxygen reduction reaction (ORR), a lower cost than benchmark Pt catalysts, and high stability and high tolerance to permeated methanol. In this study, palladium catalysts supported on titanium suboxides (Pd/TinO2n–1) were prepared by the sulphite complex route. The aim was to improve methanol tolerance and lower the cost associated with the noble metal while enhancing the stability through the use of titanium-based support; 30% Pd/Ketjenblack (Pd/KB) and 30% Pd/Vulcan (Pd/Vul) were also synthesized for comparison, using the same methodology. The catalysts were ex-situ characterized by physico-chemical analysis and investigated for the ORR to evaluate their activity, stability, and methanol tolerance properties. The Pd/KB catalyst showed the highest activity towards the ORR in perchloric acid solution. All Pd-based catalysts showed suitable tolerance to methanol poisoning, leading to higher ORR activity than a benchmark Pt/C catalyst in the presence of low methanol concentration. Among them, the Pd/TinO2n–1 catalyst showed a very promising stability compared to carbon-supported Pd samples in an accelerated degradation test of 1000 potential cycles. These results indicate good perspectives for the application of Pd/TinO2n–1 catalysts in DMFC cathodes. PMID:28793693

  10. Density functional calculations of Pd nanoparticles using a plane-wave method.

    PubMed

    Viñes, Francesc; Illas, Francesc; Neyman, Konstantin M

    2008-09-25

    We deal with usage of plane-wave density functional calculations of crystallites formed of 100-200 transition metal atoms to mimic larger experimentally treated particles. A series of model Pd clusters containing up to 225 atoms is chosen as an example. We focused on the description of size-dependent geometric parameters and binding energies of these clusters as compared with previous benchmark calculations; evolution of the particle electronic structure with increasing size has also been addressed. The high performance of the plane-wave calculations for transition-metal nanoparticles has been documented. Implications of this work on broadening opportunities to design and study realistic models of catalytic systems are outlined.

  11. Developing electrochemical sensor for point-of-care diagnostics of oxidative stress marker using imprinted bimetallic Fe/Pd nanoparticle.

    PubMed

    Roy, Ekta; Patra, Santanu; Madhuri, Rashmi; Sharma, Prashant K

    2015-01-01

    A novel electrochemical-sensing platform based on imprinted bimetallic Fe/Pd (BI-Fe/Pd) nanoparticle has been fabricated for point-of-care diagnostics of oxidative stress marker (3-nitrotyrosine) in biological fluids. Herein, BI-Fe/Pd nanoparticles are used as a platform on which 3-nitrotyrosine imprinted cavities are created using acrylamide as monomer and N-N'-methylene bisacrylamide as cross-linker. The performance of the obtained imprinted sensor is investigated by cyclic, differential pulse, and square wave voltammetry in stripping mode. The imprinted sensor exhibits high recognition ability and affinity for 3-nitrotyrosine in comparison with the non-imprinted one. In addition, the proposed sensor is capable of measuring 3-nitrotyrosine in aqueous as well as in human blood serum, plasma, and urine samples within the range of 4.90-867.57 µg L(-1) and 9.90-867.57 µg L(-1) with detection limit of 1.20 µg L(-1) and 3.25 µg L(-1) by square wave and differential pulse stripping voltammetry, respectively. Imprinted BI-Fe/Pd nanoparticle modified sensor shows high affinity and no interference from blood or urine components. Modified sensor was stored for 45 days at room temperature without any detrimental effects to their binding properties. The high affinity of proposed sensor and the lack of requirement for cold chain logistics make them an attractive alternative to the enzyme-linked immunosorbent assay (ELISA) technique.

  12. Anionic solid lipid nanoparticles supported on protamine/DNA complexes

    NASA Astrophysics Data System (ADS)

    Ye, Jiesheng; Wang, Aihua; Liu, Chunxi; Chen, Zhijin; Zhang, Na

    2008-07-01

    The objective of this study was to design novel anionic ternary nanoparticles for gene delivery. These ternary nanoparticles were equipped with protamine/DNA binary complexes (150-200 nm) as the support, and the anionic formation was achieved by absorption of anionic solid lipid nanoparticles (<=20 nm) onto the surface of the binary complexes. The small solid lipid nanoparticles (SLNs) were prepared by a modified film dispersion-ultrasonication method, and adsorption of the anionic SLNs onto the binary complexes was typically carried out in water via electrostatic interaction. The formulated ternary nanoparticles were found to be relatively uniform in size (257.7 ± 10.6 nm) with a 'bumpy' surface, and the surface charge inversion from 19.28 ± 1.14 mV to -17.16 ± 1.92 mV could be considered as evidence of the formation of the ternary nanoparticles. The fluorescence intensity measurements from three batches of the ternary nanoparticles gave a mean adsorption efficiency of 96.75 ± 1.13%. Circular dichroism spectra analysis showed that the protamine/DNA complexes had been coated by small SLNs, and that the anionic ternary nanoparticles formed did not disturb the construction of the binary complexes. SYBR Green I analysis suggested that the ternary nanoparticles could protect the DNA from nuclease degradation, and cell viability assay results showed that they exhibit lower cytotoxicity to A549 cells compared with the binary complexes and lipofectamine. The transfection efficiency of the ternary nanoparticles was better than that of naked DNA and the binary complexes, and almost equal to that of lipofectamine/DNA complexes, as revealed by inversion fluorescence microscope observation. These results indicated that the anionic ternary nanoparticles could facilitate gene transfer in cultured cells, and might alleviate the drawbacks of the conventional cationic vector/DNA complexes for gene delivery in vivo.

  13. PdCo alloy nanoparticle-embedded carbon nanofiber for ultrasensitive nonenzymatic detection of hydrogen peroxide and nitrite.

    PubMed

    Liu, Dong; Guo, Qiaohui; Zhang, Xueping; Hou, Haoqing; You, Tianyan

    2015-07-15

    PdCo alloy nanoparticle-embedded carbon nanofiber (PdCo/CNF) prepared by electrospinning and thermal treatment was employed as a high-performance platform for the determination of hydrogen peroxide and nitrite. The as-obtained PdCo/CNF were characterized by transmission electron microscopy, energy-dispersive X-ray spectroscopy and X-ray diffraction. Electrochemical impedance spectroscopy, cyclic voltammetry and differential pulse voltammetry were employed to investigate the electrochemical behaviors of the resultant biosensor. The proposed PdCo/CNF-based biosensor showed excellent analytical performances toward hydrogen peroxide (detection limit: 0.1 μM; linear range: 0.2 μM-23.5 mM) and nitrite (detection limit: 0.2 μM; linear range: 0.4-30 μM and 30-400 μM). The superior analytical properties could be attributed to the synergic effect and firmly embedment of well-dispersed PdCo alloy nanoparticles. These attractive electrochemical properties make this robust electrode material promising for the development of effective electrochemical sensors. Copyright © 2015 Elsevier Inc. All rights reserved.

  14. Carbon-supported palladium and ruthenium nanoparticles: application as catalysts in alcohol oxidation, cross-coupling and hydrogenation reactions.

    PubMed

    García-Suárez, Eduardo J; Lara, Patricia; García, Ana B; Philippot, Karine

    2013-11-01

    In the last fifteen-years, the application of metal nanoparticles as catalysts in organic synthesis has received a renewed interest. Therefore, much attention is currently being paid to the synthesis of metal nanoparticles in order to achieve the control of their characteristics in terms of size, shape and surface chemistry. Besides this, the recyclability as well as the recovery from the reaction medium still remain the major drawbacks to widespread the use of nanoparticles in catalysis. To overcome these problems, the immobilization of metal nanoparticles on solid supports appears as a promising alternative. In that context, carbon materials offer several advantages as solid supports such as availability, relatively low cost, high mechanical strength, chemical stability, and a pore structure along with an attractive surface chemistry which allows easy modifications, such as its functionalization, to suit the nanoparticles immobilization needs. Among the transition metals Palladium and Ruthenium are widely employed as efficient catalysts in many reactions. Herein, the most recent advances, from recent papers and patents, in relation to the preparation of carbon-supported Pd or Ru nanoparticles systems as well as their application as catalysts in alcohol oxidation, cross-coupling or hydrogenation reactions, are reviewed.

  15. Catalytic dechlorination of 2,4-dichlorophenol by Pd/Fe bimetallic nanoparticles in the presence of humic acid.

    PubMed

    Zhang, Zhen; Shen, Qiaohui; Cissoko, Naman; Wo, Jingjing; Xu, Xinhua

    2010-10-15

    Pd/Fe bimetallic nanoparticles were synthesized for treatment of 2,4-dichlorophenol (2,4-DCP) in the presence of humic acid (HA), in order to understand their applicability for in situ remediation of groundwater. In this case, 2,4-DCP was catalytically dechlorinated to form the final products--phenol (P) via two intermediates, namely o-chlorophenol (o-CP) and p-chlorophenol (p-CP). We demonstrated that the carbon mass balances during the dechlorination were in the range of 82-91%, and other carbons were absorbed on the surface of Pd/Fe bimetallic nanoparticles. Our results suggest the dechlorination reaction of 2,4-DCP by Pd/Fe bimetallic nanoparticles in the presence of HA followed pseudo-first-order kinetics. HA competed for reaction sites on the Pd/Fe bimetallic nanoparticles with 2,4-DCP, and thus reduced the efficiency and rate of the dechlorination of 2,4-DCP. Efficiencies of dechlorination and phenol formations increased significantly as the Pd content increased from 0.10 wt.%, 0.15 wt.% to 0.20 wt.%, the removal percentage of 2,4-DCP increased from 70.4%, 98.4% to 99.4% within 300 min, respectively, the nitrate (NO(3)(-)) content in water also has a significant impact on 2,4-DCP dechlorination efficiency. Our results show that no other intermediates were generated besides Cl(-), o-CP, p-CP and phenol during the catalytic dechlorination of 2,4-DCP. 2010 Elsevier B.V. All rights reserved.

  16. Catalytic activity of Pd-doped Cu nanoparticles for hydrogenation as a single-atom-alloy catalyst.

    PubMed

    Cao, Xinrui; Fu, Qiang; Luo, Yi

    2014-05-14

    The single atom alloy of extended surfaces is known to provide remarkably enhanced catalytic performance toward heterogeneous hydrogenation. Here we demonstrate from first principles calculations that this approach can be extended to nanostructures, such as bimetallic nanoparticles. The catalytic properties of the single-Pd-doped Cu55 nanoparticles have been systemically examined for H2 dissociation as well as H atom adsorption and diffusion, following the concept of single atom alloy. It is found that doping a single Pd atom at the edge site of the Cu55 shell can considerably reduce the activation energy of H2 dissociation, while the single Pd atom doped at the top site or in the inner layers is much less effective. The H atom adsorption on Cu55 is slightly stronger than that on the Cu(111) surface; however, a larger nanoparticle that contains 147 atoms could effectively recover the weak binding of the H atoms. We have also investigated the H atom diffusion on the 55-atom nanoparticle and found that spillover of the produced H atoms could be a feasible process due to the low diffusion barriers. Our results have demonstrated that facile H2 dissociation and weak H atom adsorption could be combined at the nanoscale. Moreover, the effects of doping one more Pd atom on the H2 dissociation and H atom adsorption have also been investigated. We have found that both the doping Pd atoms in the most stable configuration could independently exhibit their catalytic activity, behaving as two single-atom-alloy catalysts.

  17. Synthesis of Pd9Ru@Pt nanoparticles for oxygen reduction reaction in acidic electrolytes

    SciTech Connect

    Sun, Yu; Hsieh, Yu -Chi; Chang, Li -Chung; Wu, Pu -Wei; Lee, Jyh -Fu

    2014-11-22

    Nanoparticles of PdRu, Pd₃Ru, and Pd₉Ru are synthesized and impregnated on carbon black via a wet chemical reflux process. X-ray diffraction patterns of the as-synthesized samples, PdxRu/C (x=1/3/9), suggest succesful formation of alloy without presence of individual Pd and Ru nanoparticles. Images from transmission electron microscope confirm irregularly-shaped nanoparticles with average size below 3 nm. Analysis from extended X-ray absorption fine structure on both Pd and Ru K-edge absorption profiles indicate the Ru atoms are enriched on the surface of PdxRu/C. Among these samples, the Pd₉Ru/C exhibits the strongest electrocatalytic activity for oxygen reduction reaction (ORR) in an oxygen-saturated 0.1 M aqueous HClO₄ solution. Subsequently, the Pd₉Ru/C undegoes Cu under potential deposition, followed by a galvanic displacement reaction to deposit a Pt monolayer on the Pd₉Ru surface (Pd₉Ru@Pt). The Pd₉Ru@Pt reveals better ORR performance than that of Pt, reaching a mass activity of 0.38 mA μg⁻¹ Pt, as compared to that of commercially available Pt nanoparticles (0.107 mA μg⁻¹ Pt). Thus, the mechanisms responsible for the ORR enhancement are attributed to the combined effects of lattice strain and ligand interaction. In addition, this core-shell Pd₉Ru@Pt electrocatalyst represents a substantial reduction in the amount of Pt consumption and raw material cost.

  18. Impact of bio-palladium nanoparticles (bio-Pd NPs) on the activity and structure of a marine microbial community.

    PubMed

    Nuzzo, Andrea; Hosseinkhani, Baharak; Boon, Nico; Zanaroli, Giulio; Fava, Fabio

    2017-01-01

    Biogenic palladium nanoparticles (bio-Pd NPs) represent a promising catalyst for organohalide remediation in water and sediments. However, the available information regarding their possible impact in case of release into the environment, particularly on the environmental microbiota, is limited. In this study the toxicity of bio-Pd NPs on the model marine bacterium V. fischeri was assessed. The impacts of different concentrations of bio-Pd NPs on the respiratory metabolisms (i.e. organohalide respiration, sulfate reduction and methanogenesis) and the structure of a PCB-dechlorinating microbial community enriched form a marine sediment were also investigated in microcosms mimicking the actual sampling site conditions. Bio-Pd NPs had no toxic effect on V. fischeri. In addition, they had no significant effects on PCB-dehalogenating activity, while showing a partial, dose-dependent inhibitory effect on sulfate reduction as well as on methanogenesis. No toxic effects by bio-Pd NPs could be also observed on the total bacterial community structure, as its biodiversity was increased compared to the not exposed community. In addition, resilience of the microbial community to bio-Pd NPs exposure was observed, being the final community organization (Gini coefficient) of samples exposed to bio-Pd NPs similar to that of the not exposed one. Considering all the factors evaluated, bio-Pd NPs could be deemed as non-toxic to the marine microbiota in the conditions tested. This is the first study in which the impact of bio-Pd NPs is extensively evaluated over a microbial community in relevant environmental conditions, providing important information for the assessment of their environmental safety. Copyright © 2016 Elsevier Ltd. All rights reserved.

  19. Plant-Mediated Fabrication and Surface Enhanced Raman Property of Flower-Like Au@Pd Nanoparticles

    PubMed Central

    Sun, Daohua; Zhang, Genlei; Huang, Jiale; Wang, Haitao; Li, Qingbiao

    2014-01-01

    The flower-like nanostructures of an Au core and Pd petals with the average size of 47.8 nm were fabricated through the successive reduction of HAuCl4 and Na2PdCl4 at room temperature. During the synthesis, Cacumen Platycladi leaf extract served as weak reductant and capping agent. Characterization techniques such as Energy-dispersive X-ray spectroscopy, UV-Vis spectroscopy, and X-ray diffraction characterizations were employed to confirm that the as-synthesized nanoparticles have the structure of core-shell. The obtained core-shell nanoflowers exhibited good surface enhanced Raman spectroscopic activity with Rhodamine 6G. PMID:28788518

  20. Outstanding H2 sensing performance of Pd nanoparticle-decorated ZnO nanorod arrays and the temperature-dependent sensing mechanisms.

    PubMed

    Chang, Chia-Ming; Hon, Min-Hsiung; Leu, Ing-Chi

    2013-01-01

    The nearly monodispersed Pd nanoparticles with controllable density on ZnO nanorod arrays were prepared by the unique PVP-mediated photochemical deposition (PCD). The changes in morphology and dispersion of Pd on ZnO surface are ascribed to the stabilizing property and self-assembly characteristic of PVP being exploited during PCD. There are three temperature-dependent H(2) sensing mechanisms in those Pd/ZnO NRs, including general oxygen adsorption/desorption mode within 200-300 °C, surface conductivity mode at 60-120 °C and palladium hydride (PdH(x)) formation at room temperature, which causes a significant discrepancy in sensitivity variations as a function of Pd density. It is also verified that the electronic sensitization related to the transition of Pd(2+)/Pd(0) redox couple predominates the promoting mechanism in Pd/ZnO NRs used for sensing H(2) at 200-300 °C. Therefore, the gas sensitivity to 500 ppm H(2) of Pd/ZnO NRs can be significantly improved by around 553-fold (S, R(a)/R(g) = 1106) at 260 °C through decorating an adequate amount of discrete Pd nanoparticles instead of the Pd clusters, moreover, the corresponding sensitivity at room temperature is 16.9 that is superior to some promising devices reported in the literatures.

  1. Silica supported palladium nanoparticles for the decarboxylation of high-acid feedstocks: Design, deactivation and regeneration

    NASA Astrophysics Data System (ADS)

    Ping, Eric Wayne

    2011-12-01

    The major goals of this thesis were to (1) design and synthesize a supported catalyst with well-defined monodisperse palladium nanoparticles evenly distributed throughout an inorganic oxide substrate with tunable porosity characteristics, (2) demonstrate the catalytic activity of this material in the decarboxylation of long chain fatty acids and their derivatives to make diesel-length hydrocarbons, (3) elucidate the deactivation mechanism of supported palladium catalysts under decarboxylation conditions via post mortem catalyst characterization and develop a regeneration methodology thereupon, and (4) apply this catalytic system to a real low-value biofeedstock. Initial catalyst designs were based on the SBA-15 silica support, but in an effort to maximize loading and minimize mass transfer limitations, silica MCF was synthesized as catalyst support. Functionalization with various silane ligands yielded a surface that facilitated even distribution of palladium precursor salts throughout the catalyst particle, and, after reduction, monodisperse palladium nanoparticles approximately 2 nm in diameter. Complete characterization was performed on this Pd-MCF catalyst. The Pd-MCF catalyst showed high one-time activity in the decarboxylation of fatty acids to hydrocarbons in dodecane at 300°C. Hydrogen was found to be an unnecessary reactant in the absence of unsaturations, but was required in their presence---full hydrogenation of the double bonds occurs before any decarboxylation can take place. The Pd-MCF also exhibited good activity for alkyl esters and glycerol, providing a nice hypothetical description of a stepwise reaction pathway for catalytic decarboxylation of acids and their derivatives. As expected, the Pd-MCF catalyst experienced severe deactivation after only one use. Substantial effort was put into elucidating the nature of this deactivation via post mortem catalyst characterization. H2 chemisorption confirmed a loss of active surface area, but TEM and

  2. Fabrication of novel nitrogen-doped graphene-hollow AuPd nanoparticle hybrid films for the highly efficient electrocatalytic reduction of H2O2.

    PubMed

    Shang, Lei; Zeng, Baizhao; Zhao, Faqiong

    2015-01-14

    Hollow AuPd (hAuPd) alloy nanoparticles (NPs) were prepared through simultaneous reduction of HAuCl4 and Na2PdCl4 using Co NPs as sacrificial template (i.e., reductant). Then, the hAuPd NPs were assembled on nitrogen-doped graphene (NG) to prepare an NG-hAuPd hybrid film. The obtained NG-hAuPd composite showed higher electrocatalytic activity toward the reduction of H2O2, compared with graphene-hAuPd hybrid, NG-solid AuPd hybrid, and hAuPd NPs. The enhanced performance was related to the hollow structure of hAuPd NPs and the synergistic effect between NG and hAuPd NPs. Under optimum conditions, the NG-hAuPd hybrid film showed a linear response to H2O2 in the range of 0.1-20 μM, with a sensitivity of 5095.5 μA mM(-1) cm(-2)and a comparable detection limit of 0.02 μM (S/N = 3). These results demonstrated that the NG-hAuPd composite was a promising electrocatalytic material for constructing sensors, etc.

  3. Impact of surface roughness of Au core in Au/Pd core-shell nanoparticles toward formic acid oxidation - Experiment and simulation

    NASA Astrophysics Data System (ADS)

    Hsu, Chiajen; Huang, Chienwen; Hao, Yaowu; Liu, Fuqiang

    2013-12-01

    The Au/Pd core-shell nanoparticles (NPs) were synthesized via galvanic replacement of Cu by Pd on hollow Au cores by adding different concentrations of Na2SO3 solution. It was found that the higher concentration of Na2SO3 that was used, the rougher the Au nanospheres became. However, the rougher Au surface may cause more defects in the Pd layers and decrease the catalytic abilities. The Au/Pd NPs synthesized using 0 M Na2SO3 (denoted as 0 M-Au/Pd NPs) have the smoothest Pd surface and demonstrate higher formic acid oxidation (FAO) activity (0.714 mA cm-2, normalized to the surface area of Pd) than other Au/Pd NPs and commercial Pd black (0.47 mA cm-2). Additional electrochemical characterization of the 0 M-Au/Pd NPs also demonstrated lower CO-stripping onset and peak potentials, higher stability (8× improvement in stabilized oxidation current), and superior durability (by 1.6×) than the Pd black. In addition, a simple simulation of FAO was adopted to predict the anodic curve by including reaction intermediates of formate and hydroxyl. The 0 M-Au/Pd NPs were found to show higher formate and lower hydroxyl coverage than the Pd black.

  4. Electron to Adsorbate Energy Transfer in Nanoparticles: Adsorption Site, Size, and Support Matter.

    PubMed

    Ghalgaoui, Ahmed; Ouvrard, Aimeric; Wang, Jijin; Carrez, Serge; Zheng, Wanquan; Bourguignon, Bernard

    2017-06-15

    Confinement of hot electrons in metal nanoparticles (NPs) is expected to lead to increased reactivity in heterogeneous catalysis. NP size as well as support may influence molecule-NP coupling. Here, we use ultrafast nonlinear vibrational spectroscopy to follow energy transfer from hot electrons generated in Pd NP/MgO/Ag(100) to chemisorbed CO. Photoexcitation and photodesorption occur on an ultrashort time scale and are selective according to adsorption site. When the MgO layer is thick enough, it becomes NP size-dependent. Hot electron confinement within NPs is unfavorable for photodesorption, presumably because its dominant effect is to increase relaxation to phonons. An avenue of research is open where NP size and support thickness, photon energy, and molecular electronic structure will be tuned to obtain either molecular stability or reactivity in response to photon excitation.

  5. Catalytic behavior of nickel nanoparticles: gasborne vs. supported state

    NASA Astrophysics Data System (ADS)

    Weber, Alfred P.; Davoodi, Parisa; Seipenbusch, Martin; Kasper, Gerhard

    2006-08-01

    To study the pure catalytic activity of metallic nanoparticles, the formation of methane on gasborne Ni nanoparticles, so called aerosol catalysis experiments, were performed. Beside effects typical for the methanation such as poisoning of the particle surface at temperatures above 385°C, the maximum of the catalytic activity was observed for Ni particles of about 14 nm, i.e. in a size range, which is quite uncommon for typical nanoeffects of metallic particles. To clarify, which catalytic phenomena are related to the aerosol state, the same reaction was performed on supported Ni nanoparticles, which were also generated and conditioned in the gas phase and deposited on a SiO2 surface by thermophoresis. For these supported particles, the same reaction conditions were established as before for the gasborne Ni nanoparticles. However, differences in the mass transport characteristics of educt and product molecules to the particles were encountered and led to lower overall reaction rates. While qualitatively poisoning kinetics and activation energies agreed for both cases, significant differences were observed for the size dependence of the catalytic activity and for the sintering kinetics. The observed shift of the optimum size for the methanation from 14 nm (aerosol) to 25 nm (on support) can be explained by different adsorption enthalpies of the educt gases on aerosol and supported Ni nanoparticles, respectively.

  6. Seed-mediated growth of MOF-encapsulated Pd@Ag core–shell nanoparticles: toward advanced room temperature nanocatalysts† †Electronic supplementary information (ESI) available: Experimental details and catalysts characterization. See DOI: 10.1039/c5sc02925b Click here for additional data file.

    PubMed Central

    Chen, Liyu; Huang, Binbin; Qiu, Xuan; Wang, Xi

    2016-01-01

    The possibility of using inner cavities within metal–organic frameworks (MOFs) as templates for the fabrication of tiny metal nanoparticles (NPs) was attempted in this work. An unprecedented design of Pd@Ag core–shell NPs on MOFs via a seed mediated growth strategy is reported and attributed to the presence of activated physisorbed hydrogen atoms on embedded Pd NPs as reducing agents to selectively direct the deposition of Ag onto Pd while minimizing the Ag self-nucleation. The obtained Pd@Ag core–shell NPs exhibited a significant increase in selectivity in the partial hydrogenation of phenylacetylene as compared to their monometallic counterparts, due to the surface dilution and electron modification of the surface Pd sites by Ag deposition. Pd@Ag NPs also possessed an unprecedented high stability and recyclability in the catalytic reactions, related to the nano-confinement effect and the strong metal–support interaction offered by the MOF framework. PMID:28758001

  7. Formation of catalytic silver nanoparticles supported on branched polyethyleneimine derivatives.

    PubMed

    Signori, Aline M; Santos, Kelly de O; Eising, Renato; Albuquerque, Brunno L; Giacomelli, Fernando C; Domingos, Josiel B

    2010-11-16

    A new and straightforward method for screening highly catalytically active silver nanoparticle-polymer composites derived from branched polyethyleneimine (PEI) is reported. The one-step systematic derivatization of the PEI scaffold with alkyl (butyl or octyl) and ethanolic groups led to a structural diversity correlated to the stabilization of silver nanoparticles and catalysis. Analysis of PEI derivative libraries identified a silver nanoparticle-polymer composite that was able to efficiently catalyze the p-nitrophenol reduction by NaBH(4) in water with a rate constant normalized to the surface area of the nanoparticles per unit volume (k(1)) of 0.57 s(-1) m(-2) L. Carried out in the presence of excess NaBH(4), the catalytic reaction was observed to follow pseudo-first-order kinetics and the apparent rate constant was linearly dependent on the total surface area of the silver nanoparticles (Ag-NPs), indicating that catalysis takes place on the surface of the nanoparticles. All reaction kinetics presented induction periods, which were dependent on the concentration of substrates, the total surface of the nanoparticles, and the polymer composition. All data indicated that this induction time is related to the resistance to substrate diffusion through the polymer support. Hydrophobic effects are also assumed to play an important role in the catalysis, through an increase in the local substrate concentration.

  8. Antimicrobial activity of metal oxide nanoparticles supported onto natural clinoptilolite.

    PubMed

    Hrenovic, Jasna; Milenkovic, Jelena; Daneu, Nina; Kepcija, Renata Matonickin; Rajic, Nevenka

    2012-08-01

    The antimicrobial activity of Cu(2)O, ZnO and NiO nanoparticles supported onto natural clinoptilolite was investigated in the secondary effluent under dark conditions. After 24h of contact the Cu(2)O and ZnO nanoparticles reduced the numbers of viable bacterial cells of Escherichia coli and Staphylococcus aureus in pure culture for four to six orders of magnitude and showed consistent 100% of antibacterial activity against native E. coli after 1h of contact during 48 exposures. The antibacterial activity of NiO nanoparticles was less efficient. The Cu(2)O and NiO nanoparticles showed 100% of antiprotozoan activity against Paramecium caudatum and Euplotes affinis after 1h of contact, while ZnO nanoparticles were less efficient. The morphology and crystallinity of the nanoparticles were not affected by microorganisms. The metal oxide nanoparticles could find a novel application in the disinfection of secondary effluent and removal of pathogenic microorganisms in the tertiary stage of wastewater treatment. Copyright © 2012 Elsevier Ltd. All rights reserved.

  9. Effects of functionalization of TiO2 nanotube array sensors with Pd nanoparticles on their selectivity.

    PubMed

    Park, Sunghoon; Kim, Soohyun; Park, Suyoung; Lee, Wan In; Lee, Chongmu

    2014-08-27

    This study compared the responses of Pd-functionalized and pristine titanate (TiO2) nanotube arrays to ethanol with those to acetone to determine the effects of functionalization of TiO2 nanotubes with Pd nanoparticles on the sensitivity and selectivity. The responses of pristine and Pd-functionalized TiO2 nanotube arrays to ethanol gas at 200 °C were ~2877% and ~21,253%, respectively. On the other hand, the responses of pristine and Pd-functionalized TiO2 nanotube arrays to acetone gas at 250 °C were ~1636% and 8746% respectively. In the case of ethanol sensing, the response and recovery times of Pd-functionalized TiO2 nanotubes (10.2 and 7.1 s) were obviously shorter than those of pristine TiO2 nanotubes (14.3 and 8.8 s), respectively. In contrast, in the case of acetone sensing the response and recovery times of Pd-functionalized TiO2 nanotubes (42.5 and 19.7 s) were almost the same as those of pristine TiO2 nanotubes (47.2 and 17.9 s). TiO2 nanotube arrays showed the strongest response to ethanol and Pd functionalization was the most effective in improving the response of TiO2 nanotubes to ethanol among six different types of gases: ethanol, acetone, CO, H2, NH3 and NO2. The origin of the superior sensing properties of Pd-functionalized TiO2 nanotubes toward ethanol to acetone is also discussed.

  10. Effects of Functionalization of TiO2 Nanotube Array Sensors with Pd Nanoparticles on Their Selectivity

    PubMed Central

    Park, Sunghoon; Kim, Soohyun; Park, Suyoung; Lee, Wan In; Lee, Chongmu

    2014-01-01

    This study compared the responses of Pd-functionalized and pristine titanate (TiO2) nanotube arrays to ethanol with those to acetone to determine the effects of functionalization of TiO2 nanotubes with Pd nanoparticles on the sensitivity and selectivity. The responses of pristine and Pd-functionalized TiO2 nanotube arrays to ethanol gas at 200 °C were ∼2877% and ∼21,253%, respectively. On the other hand, the responses of pristine and Pd-functionalized TiO2 nanotube arrays to acetone gas at 250 °C were ∼1636% and 8746% respectively. In the case of ethanol sensing, the response and recovery times of Pd-functionalized TiO2 nanotubes (10.2 and 7.1 s) were obviously shorter than those of pristine TiO2 nanotubes (14.3 and 8.8 s), respectively. In contrast, in the case of acetone sensing the response and recovery times of Pd-functionalized TiO2 nanotubes (42.5 and 19.7 s) were almost the same as those of pristine TiO2 nanotubes (47.2 and 17.9 s). TiO2 nanotube arrays showed the strongest response to ethanol and Pd functionalization was the most effective in improving the response of TiO2 nanotubes to ethanol among six different types of gases: ethanol, acetone, CO, H2, NH3 and NO2. The origin of the superior sensing properties of Pd-functionalized TiO2 nanotubes toward ethanol to acetone is also discussed. PMID:25166499

  11. Coarsening of carbon black supported Pt nanoparticles in hydrogen.

    PubMed

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

    2017-10-06

    This study addresses coarsening mechanisms of Pt nanoparticles supported on carbon black in hydrogen. By means of in situ transmission electron microscopy (TEM), Pt nanoparticle coarsening was monitored in 6 mbar 20 % H2/Ar while ramping up the temperature to almost 1000 °C. Time-resolved TEM images directly reveal that separated ca. 3 nm sized Pt nanoparticles in a hydrogen environment are stable up to ca. 800 °C at a heating rate of 10 °C/min. The coarsening above this temperature is dominated by the particle migration and coalescence mechanism. However, for agglomerated Pt nanoparticles, coalescence events were observed already above 200 °C. The temperature-dependency of particle sizes and the observed migration distances are described and found to be consistent with simple early models for the migration and coalescence. © 2017 IOP Publishing Ltd.

  12. Complete oxidation of ethylene over supported gold nanoparticle catalysts.

    PubMed

    Ahn, Ho-Geun; Choi, Byoung-Min; Lee, Do-Jin

    2006-11-01

    Complete oxidation of ethylene was performed over supported noble metals or transition metals oxide catalysts and on monoliths under atmospheric pressure. Gold nanoparticles on Al2O3 or MxOy(M = Mo, Fe, Mn) were prepared by impregnation, coprecipitation, deposition, and dispersion methods. Nanoparticles prepared by impregnation method were irregular and very large above 25 nm, but those by coprecipitation and deposition method were uniformly nanosized at 4-5 nm. The gold nanoparticle were outstandingly active in catalyzing oxidation of ethylene. The activity order of these catalysts with preparation methods was deposition > coprecipitation > impregnation, and Au/Co3O4 prepared by deposition method showed the best performance in ethylene oxidation. The addition of gold particles to MxOy/Al2O3 catalyst enhanced the ethylene oxidation activity significantly. The main role of the gold nanoparticles apparently was to promote dissociative adsorption of oxygen and to enhance the reoxidation of the catalyst.

  13. Study of Alginate-Supported Ionic Liquid and Pd Catalysts

    PubMed Central

    Jouannin, Claire; Vincent, Chloë; Dez, Isabelle; Gaumont, Annie-Claude; Vincent, Thierry; Guibal, Eric

    2012-01-01

    New catalytic materials, based on palladium immobilized in ionic liquid supported on alginate, were elaborated. Alginate was associated with gelatin for the immobilization of ionic liquids (ILs) and the binding of palladium. These catalytic materials were designed in the form of highly porous monoliths (HPMs), in order to be used in a column reactor. The catalytic materials were tested for the hydrogenation of 4-nitroaniline (4-NA) in the presence of formic acid as hydrogen donor. The different parameters for the elaboration of the catalytic materials were studied and their impact analyzed in terms of microstructures, palladium sorption properties and catalytic performances. The characteristics of the biopolymer (proportion of β-D-mannuronic acid (M) and α-L-guluronic acid (G) in the biopolymer defined by the M/G ratio), the concentration of the porogen agent, and the type of coagulating agent significantly influenced catalytic performances. The freezing temperature had a significant impact on structural properties, but hardly affected the catalytic rate. Cellulose fibers were incorporated as mechanical strengthener into the catalytic materials, and allowed to enhance mechanical properties and catalytic efficiency but required increasing the amount of hydrogen donor for catalysis.

  14. DFT global optimisation of gas-phase and MgO-supported sub-nanometre AuPd clusters.

    PubMed

    Hussein, Heider A; Davis, Jack B A; Johnston, Roy L

    2016-09-21

    The Birmingham Parallel Genetic Algorithm (BPGA) has been adopted for the global optimization of free and MgO(100)-supported Pd, Au and AuPd nanocluster structures, over the size range N = 4-10. Structures were evaluated directly using density functional theory, which has allowed the identification of Pd, Au and AuPd global minima. The energetics, structures, and tendency of segregation have been evaluated by different stability criteria such as binding energy, excess energy, second difference in energy, and adsorption energy. The ability of the approach in searching for putative global minimum has been assessed against a systematic homotop search method, which shows a high degree of success.

  15. Thiolated graphene oxide-supported palladium cobalt alloyed nanoparticles as high performance electrocatalyst for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Yun, Mira; Ahmed, Mohammad Shamsuddin; Jeon, Seungwon

    2015-10-01

    Thiolated graphene oxide-supported palladium cobalt alloyed catalyst has been synthesized by an electrochemical reduction method (denoted as ER/PdCo-tGO) for electrocatalytic oxygen reduction reaction (ORR). The polyethylene glycol (PEG) has been used as stabilizer for PdCo nanoparticles (NPs) stabilization. This material has been characterized by various instrumental methods. The morphological analysis shows the PdCo alloyed NPs are well set on to the thiolated graphene with better dispersion. The X-ray photoelectron spectroscopy (XPS) shows electrochemical reduction has been done successfully with the increasing C/O ratio from 0.88 to 2.14. Also, the X-ray diffraction (XRD) data reveals that the Co is presents with the oxidized form. The electrocatalytic activities have been verified using cyclic voltammetry (CV) and hydrodynamic voltammetry techniques in 0.1 M KOH electrolyte. The as prepared catalyst has shown better ORR onset potential (0.95 V vs. RHE) and superior mass activity (329 mA mgPd-1 at 0.8 V) which is 3.1 times higher than that of 20wt% Pt/C. The reaction kinetics have confirmed that the ORR at ER/PdCo-tGO catalyst follows a four electron transfer reaction process.

  16. Pulsed laser deposition of ZnO thin films decorated with Au and Pd nanoparticles with enhanced acetone sensing performance

    NASA Astrophysics Data System (ADS)

    Alexiadou, M.; Kandyla, M.; Mousdis, G.; Kompitsas, M.

    2017-04-01

    We fabricate and compare nanocomposite thin-film ZnO chemoresistive acetone sensors with gold or palladium nanoparticles on the surface, at low operating temperatures. The sensors are fabricated by pulsed laser deposition and operate in the temperature range 159-200 °C. The ZnO films are polycrystalline, crystallizing mainly at the (002) and (101) orientations of the hexagonal phase. The nanocomposite ZnO:Au and ZnO:Pd sensors have a lower detection limit and show a response enhancement factor between 2 and 7, compared with pure ZnO sensors. The ZnO:Pd sensor performs better than the ZnO:Au sensor. The ZnO:Pd sensor sensitivity increases with the amount of palladium on the surface, while it remains roughly unchanged with the ZnO thickness. The lowest acetone concentration we detect is 26 ppm for the operating temperature of 200 °C.

  17. Synthetically Tuned Atomic Ordering in PdCu Nanoparticles with Enhanced Catalytic Activity toward Solvent-Free Benzylamine Oxidation.

    PubMed

    Marakatti, Vijaykumar S; Sarma, Saurav Ch; Joseph, Boby; Banerjee, Dipanjan; Peter, Sebastian C

    2017-02-01

    Synthesis of ordered compounds with nano size is of particular interest for tuning the surface properties with enhanced activity and selectivity toward various important industrial catalytic processes. In this work, we synthesized ordered PdCu nanoparticles as highly efficient catalyst for the solvent-free aerobic oxidation of benzylamine. The PdxCu1-x catalysts with different chemical compositions (x = 0, 0.25, 0.4, 0.5, 0.6, 0.75, 1) were prepared by polyol method using NaBH4 as a reducing agent and were well-characterized by X-ray diffraction (XRD), inductively coupled plasma optical emission spectroscopy, X-ray photoelectron spectroscopy, transmission electron microscopy (TEM) energy-dispersive analysis of X-rays, and X-ray absorption fine structure. The effect of different metal concentrations of Pd and Cu on the formation of PdxCu1-x nanoparticles was investigated. The XRD and TEM confirmed the formation of ordered PdCu intermetallic phase with body-centered cubic (BCC) structure for the synthetic composition of Pd/Cu = 1:1. For compositions x = 0, 0.25, 0.75, and 1, PdxCu1-x alloy with face-centered cubic (FCC) structure was observed, whereas mixed phase of BCC and FCC was observed for x = 0.4 and 0.6. The use of strong reducing agent (NaBH4) was essential to synthesize PdCu ordered phase compared to weak reducing agents such as oleylamine and ascorbic acid. The PdCu nanocatalyst with ordered structure (BCC) showed excellent catalytic activity compared to PdxCu1-x alloy nanoparticles with FCC structure. The atomic ordering in the PdCu intermetallic was the driving force for the enhancement in the catalytic activity with high benzylamine conversion of 94.0% and dibenzylimine selectivity of 92.2% compared to its monometallic and alloy counterparts. Moreover, ordered PdCu alloy showed good recyclability and activity toward the oxidation of different amines.

  18. Pt@Ag and Pd@Ag core/shell nanoparticles for catalytic degradation of Congo red in aqueous solution.

    PubMed

    Salem, Mohamed A; Bakr, Eman A; El-Attar, Heba G

    2018-01-05

    Platinum/silver (Pt@Ag) and palladium/silver (Pd@Ag) core/shell NPs have been synthesized in two steps reaction using the citrate method. The progress of nanoparticle formation was followed by the UV/Vis spectroscopy. Transmission electron microscopy revealed spherical shaped core/shell nanoparticles with average particle diameter 32.17nm for Pt@Ag and 8.8nm for Pd@Ag. The core/shell NPs were further characterized by FT-IR and XRD. Reductive degradation of the Congo red dye was chosen to demonstrate the excellent catalytic activity of these core/shell nanostructures. The nanocatalysts act as electron mediators for the transfer of electrons from the reducing agent (NaBH4) to the dye molecules. Effect of reaction parameters such as nanocatalyst dose, dye and NaBH4 concentrations on the dye degradation was investigated. A comparison between the catalytic activities of both nanocatalysts was made to realize which of them the best in catalytic performance. Pd@Ag was the higher in catalytic activity over Pt@Ag. Such greater activity is originated from the smaller particle size and larger surface area. Pd@Ag nanocatalyst was catalytically stable through four subsequent reaction runs under the utilized reaction conditions. These findings can thus be considered as possible economical alternative for environmental safety against water pollution by dyes. Copyright © 2017. Published by Elsevier B.V.

  19. Transmetallation as an effective strategy for the preparation of bimetallic CoPd and CuPd nanoparticles

    NASA Astrophysics Data System (ADS)

    Bersani, Marco; Conte, Luca; Martucci, Alessandro; Guglielmi, Massimo; Mattei, Giovanni; Bello, Valentina; Rosei, Renzo; Centazzo, Massimo

    2014-01-01

    The preparation of palladium alloy nanoparticles is of great interest for many applications, especially in catalysis. Starting from presynthesized nanoparticles of a less noble metal, a transmetallation reaction involving a redox process at the nanoparticle surface can be exploited to modify the nanoparticle composition and crystalline phase. As an example, monodispersed ε-cobalt and face-centered cubic copper nanoparticles were synthesized in organic solvents at high temperature and the as-formed nanoparticles were reacted with palladium(ii) hexafluoroacetylacetonate resulting in the formation of alloyed nanoparticles whose composition closely follows the reactant ratio. The oxidative state of the nanoparticle surface greatly affects the success of the transmetallation reaction and a reduction treatment was necessary to achieve the desired final product. Electron microscopy and X-ray diffraction showed that for cobalt a limiting palladium content for the ε-phase alloy is found, above which an fcc alloy nucleates, while for copper the fcc crystalline phase is preserved throughout the whole composition range.

  20. Pd clusters supported on amorphous, low-porosity carbon spheres for hydrogen production from formic acid.

    PubMed

    Bulushev, Dmitri A; Bulusheva, Lyubov G; Beloshapkin, Sergey; O'Connor, Thomas; Okotrub, Alexander V; Ryan, Kevin M

    2015-04-29

    Amorphous, low-porosity carbon spheres on the order of a few micrometers in size were prepared by carbonization of squalane (C30H62) in supercritical CO2 at 823 K. The spheres were characterized and used as catalysts' supports for Pd. Near-edge X-ray absorption fine structure studies of the spheres revealed sp(2) and sp(3) hybridized carbon. To activate carbons for interaction with a metal precursor, often oxidative treatment of a support is needed. We showed that boiling of the obtained spheres in 28 wt % HNO3 did not affect the shape and bulk structure of the spheres, but led to creation of a considerable amount of surface oxygen-containing functional groups and increase of the content of sp(2) hybridized carbon on the surface. This carbon was seen by scanning transmission electron microscopy in the form of waving graphene flakes. The H/C atomic ratio in the spheres was relatively high (0.4) and did not change with the HNO3 treatment. Palladium was deposited by impregnation with Pd acetate followed by reduction in H2. This gave uniform Pd clusters with a size of 2-4 nm. The Pd supported on the original C spheres showed 2-3 times higher catalytic activity in vapor phase formic acid decomposition and higher selectivity for H2 formation (98-99%) than those for the catalyst based on the HNO3 treated spheres. Using of such low-porosity spheres as a catalyst support should prevent mass transfer limitations for fast catalytic reactions.

  1. Graphene-supported PtPd Bimetallic Gathered Nanocrystals for Non-enzymatic Sensing of Oxalic Acid.

    PubMed

    Cai, Zhixiong; Zhao, Li; Zhao, Tingting; Wang, Yiru; Chen, Xi

    2015-01-01

    A novel non-enzymatic oxalic acid (OA) sensor was developed using a nanocrystal PtPd loaded reduced graphene nanosheets (PtPdNCs/RGO)-modified electrode. PtPdNCs/RGO were successfully achieved by a facile, one-step and template-free method, in which PtPd nanoparticles with 100 nm-scale were assembled from polyhedral PtPd nanocrystals of various shapes and dispersed on the graphene nanosheets. Resulting PtPdNCs/RGO were characterized and used for PtPdNCs/RGO-modified electrodes. Electrochemical oxidation of OA on the modified electrode was investigated by cyclic voltammetry and differential pulse voltammetry (DPV). Well-defined peaks of OA oxidation could be obtained using an electrode that indicated its high electrochemical activity. The concentration of OA and the current responses could be obtained in the ranges of 0.5 - 10 and 10 - 35 mM with correlation coefficients of 0.9994 and 0.9952; the detection limit (S/N = 3) was found to be 0.05 mM. The modified electrode presented good characteristics in terms of both stability and reproducibility, promising its applicability in practical analysis.

  2. Characterization and Reactivity of Iron Nanoparticles Prepared with Added Cu, Pd, and Ni

    SciTech Connect

    Chun, Chan Lan; Baer, Donald R.; Matson, Dean W.; Amonette, James E.; Penn, Ryland L.

    2010-07-01

    The presence of a secondary metal on iron particles affects redox reactivity in engineered remediation systems. However, the structural characteristics of the metal additives and mechanism responsible for changes in reactivity have not been fully elucidated. Here, we synthesized iron nanoparticles with Cu, Pd, and Ni content ranging from 0-2 mol% via a solution deposition process (SDP), hydrogen reduction process (HRP), or hydrogen reduction of ferrihydrite coprecipitated with the metal cations (HRCO). Results from solid-state characterization show that the synthetic methods produced similar iron core/magnetite shell particles but produced substantial differences in terms of the distribution of the metal additive. In SDP, the metal additives were heterogeneous distributed on the surface of the particles. The metal additives were clearly discernable in TEM images as spherical nanoparticles (2-4 nm) on the HRP and HRCO particles. In addition, we hypothesize that the metal additive is also present as solute within the iron core of the HRCO particles. Kinetic batch experiments of carbon tetrachloride (CT) degradation were performed to quantitatively compare the redox reactivity of the particles. Overall, metal additives resulted in enhanced overall pseudo-first order rate constants of CT degradation (kO,CT) compared to that of the iron nanoparticles. For the bimetallic iron nanoparticles prepared by SDP and HRP, kO,CT increased with the concentration of metal additives. The values of chloroform yield (YCF) were independent of the identity and amount of metal additives. However, both kO,CT and YCF of the HRCO iron particles were significantly greater. Results suggest that it is the distribution of the metal additives that most strongly impacts reactivity and product distribution. For example, for materials with ca. 0.9 50 mol% Ni, reactivity and YCF varied substantially (HRCO>SDP>HRP), and HRCO-NiFe resulted in the lowest final chloroform concentration because the

  3. Plasmon-mediated Photoelectron Emission from Single, Supported Metal Nanoparticles

    NASA Astrophysics Data System (ADS)

    Grubisic, Andrej; Nesbitt, David

    2014-03-01

    Coherent multiphoton photoelectron emission (MPPE) from supported metal nanoparticles/structures has been studied at a single-particle level via scanning photoemission imaging microscopy (SPIM). Resonant excitation of localized surface plasmons (LSPs) with ultrafast laser pulses is shown to greatly amplify the photoelectron emission rate from metallic nanoparticles. In the limit of a large number of plasmon excitations, the n-photon photoelectron current scales rapidly with the electromagnetic near-field enhancement factor (|E|/|E0|)2n, indicating coherent MPPE as an extremely sensitive probe of the particle near-field. Additionally, our velocity map imaging (VMI) measurements of angle- and energy- resolved photoelectron distributions emitted from single plasmonic nanoparticles will be highlighted, with results shedding light into the complex dynamics of plasmon-induced photoelectron emission. We gratefully acknowledge Air Force Office of Scientific Research, National Science Foundation, and the National Institute of Standards and Technology for support of this work.

  4. Magnetic nanoparticles supported ionic liquids improve firefly luciferase properties.

    PubMed

    Noori, Ali Reza; Hosseinkhani, Saman; Ghiasi, Parisa; Akbari, Jafar; Heydari, Akbar

    2014-03-01

    Ionic liquids as neoteric solvents, microwave irradiation, and alternative energy source are becoming as a solvent for many enzymatic reactions. We recently showed that the incubation of firefly luciferase from Photinus pyralis with various ionic liquids increased the activity and stability of luciferase. Magnetic nanoparticles supported ionic liquids have been obtained by covalent bonding of ionic liquids-silane on magnetic silica nanoparticles. In the present study, the effects of [γ-Fe2O3@SiO2][BMImCl] and [γ-Fe2O3@SiO2][BMImI] were investigated on the structural properties and function of luciferase using circular dichroism, fluorescence spectroscopy, and bioluminescence assay. Enzyme activity and structural stability increased in the presence of magnetic nanoparticles supported ionic liquids. Furthermore, the effect of ingredients which were used was not considerable on K(m) value of luciferase for adenosine-5'-triphosphate and also K(m) value for luciferin.

  5. Fabrication of Pd Micro-Membrane Supported on Nano-Porous Anodized Aluminum Oxide for Hydrogen Separation.

    PubMed

    Kim, Taegyu

    2015-08-01

    In the present study, nano-porous anodized aluminum oxide (AAO) was used as a support of the Pd membrane. The AAO fabrication process consists of an electrochemical polishing, first/second anodizing, barrier layer dissolving and pores widening. The Pd membrane was deposited on the AAO support using an electroless plating with ethylenediaminetetraacetic acid (EDTA) as a plating agent. The AAO had the regular pore structure with the maximum pore diameter of ~100 nm so it had a large opening area but a small free standing area. The 2 µm-thick Pd layer was obtained by the electroless plating for 3 hours. The Pd layer thickness increased with increasing the plating time. However, the thickness was limited to ~5 µm in maximum. The H2 permeation flux was 0.454 mol/m2-s when the pressure difference of 66.36 kPa0.5 was applied at the Pd membrane under 400 °C.

  6. A Synthetic Pseudo-Rh: NOx Reduction Activity and Electronic Structure of Pd-Ru Solid-solution Alloy Nanoparticles.

    PubMed

    Sato, Katsutoshi; Tomonaga, Hiroyuki; Yamamoto, Tomokazu; Matsumura, Syo; Zulkifli, Nor Diana Binti; Ishimoto, Takayoshi; Koyama, Michihisa; Kusada, Kohei; Kobayashi, Hirokazu; Kitagawa, Hiroshi; Nagaoka, Katsutoshi

    2016-06-24

    Rh is one of the most important noble metals for industrial applications. A major fraction of Rh is used as a catalyst for emission control in automotive catalytic converters because of its unparalleled activity toward NOx reduction. However, Rh is a rare and extremely expensive element; thus, the development of Rh alternative composed of abundant elements is desirable. Pd and Ru are located at the right and left of Rh in the periodic table, respectively, nevertheless this combination of elements is immiscible in the bulk state. Here, we report a Pd-Ru solid-solution-alloy nanoparticle (PdxRu1-x NP) catalyst exhibiting better NOx reduction activity than Rh. Theoretical calculations show that the electronic structure of Pd0.5Ru0.5 is similar to that of Rh, indicating that Pd0.5Ru0.5 can be regarded as a pseudo-Rh. Pd0.5Ru0.5 exhibits better activity than natural Rh, which implies promising applications not only for exhaust-gas cleaning but also for various chemical reactions.

  7. 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. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Catalytic reduction of hexavalent chromium by a novel nitrogen-functionalized magnetic ordered mesoporous carbon doped with Pd nanoparticles.

    PubMed

    Li, Sisi; Tang, Lin; Zeng, Guangming; Wang, Jiajia; Deng, Yaocheng; Wang, Jingjing; Xie, Zhihong; Zhou, Yaoyu

    2016-11-01

    Hexavalent chromium Cr(VI) is a toxic water pollutant which can cause serious influence to the health of the human and animals. Therefore, developing new methods to remove hexavalent chromium in water attracts great attention of scholars. In our research, we successfully synthesized a new type of magnetic mesoporous carbon hybrid nitrogen (Fe-NMC) loaded with catalyst Pd nanoparticles (NPs), which performed excellent catalytic reduction efficiency toward Cr(VI). The characterization of Pd/Fe-NMC composite was investigated in detail using scanning electron microscope (SEM), high-resolution transmission electron microscopy (HRTEM), Fourier transform infrared spectroscopy (FTIR), and nitrogen adsorption-desorption measurements. According to the experimental results, we dealt with in-depth discussion and studied on the mechanism of hexavalent chromium removed by Pd/Fe-NMC composite. Furthermore, the batch experiments were conducted to investigate the catalytic reduction ability of composite. It was found that the chromium reduction process conforms to pseudo-first-order reaction kinetics model when the concentrations of chromium and sodium formate were low. It took only 20 min for the Pd/Fe-NMC composite to reach 99.8 % reduction of Cr(VI) (50 mg/L). The results suggested that the Pd/Fe-NMC composite may exhibit significantly improved catalytic activity for the hexavalent chromium reduction at industrial wastewater.

  9. A Synthetic Pseudo-Rh: NOx Reduction Activity and Electronic Structure of Pd-Ru Solid-solution Alloy Nanoparticles

    NASA Astrophysics Data System (ADS)

    Sato, Katsutoshi; Tomonaga, Hiroyuki; Yamamoto, Tomokazu; Matsumura, Syo; Zulkifli, Nor Diana Binti; Ishimoto, Takayoshi; Koyama, Michihisa; Kusada, Kohei; Kobayashi, Hirokazu; Kitagawa, Hiroshi; Nagaoka, Katsutoshi

    2016-06-01

    Rh is one of the most important noble metals for industrial applications. A major fraction of Rh is used as a catalyst for emission control in automotive catalytic converters because of its unparalleled activity toward NOx reduction. However, Rh is a rare and extremely expensive element; thus, the development of Rh alternative composed of abundant elements is desirable. Pd and Ru are located at the right and left of Rh in the periodic table, respectively, nevertheless this combination of elements is immiscible in the bulk state. Here, we report a Pd-Ru solid-solution-alloy nanoparticle (PdxRu1-x NP) catalyst exhibiting better NOx reduction activity than Rh. Theoretical calculations show that the electronic structure of Pd0.5Ru0.5 is similar to that of Rh, indicating that Pd0.5Ru0.5 can be regarded as a pseudo-Rh. Pd0.5Ru0.5 exhibits better activity than natural Rh, which implies promising applications not only for exhaust-gas cleaning but also for various chemical reactions.

  10. High-efficiency palladium catalysts supported on ppy-modified C60 for formic acid oxidation.

    PubMed

    Bai, Zhengyu; Yang, Lin; Guo, Yuming; Zheng, Zhi; Hu, Chuangang; Xu, Pengle

    2011-02-14

    A facile preparation of polypyrrole-modified fullerene supported Pd nanoparticles catalyst is introduced; electrochemical measurements demonstrate that the obtained Pd/ppy-C(60) catalyst shows a good electrocatalytic activity and stability for the oxidation of formic acid.

  11. Capability of defective graphene-supported Pd13 and Ag13 particles for mercury adsorption

    NASA Astrophysics Data System (ADS)

    Meeprasert, Jittima; Junkaew, Anchalee; Rungnim, Chompoonut; Kunaseth, Manaschai; Kungwan, Nawee; Promarak, Vinich; Namuangruk, Supawadee

    2016-02-01

    Reactivity of single-vacancy defective graphene (DG) and DG-supported Pdn and Agn (n = 1, 13) for mercury (Hg0) adsorption has been studied using density functional theory calculation. The results show that Pdn binds defective site of DG much stronger than the Agn, while metal nanocluster binds DG stronger than single metal atom. Metal clustering affects the adsorption ability of Pd composite while that of Ag is comparatively less. The binding strength of -8.49 eV was found for Pd13 binding on DG surface, indicating its high stability. Analyses of structure, energy, partial density of states, and d-band center (ɛd) revealed that the adsorbed metal atom or cluster enhances the reactivity of DG toward Hg adsorption. In addition, the Hg adsorption ability of Mn-DG composite is found to be related to the ɛd of the deposited Mn, in which the closer ɛd of Mn to the Fermi level correspond to the higher adsorption strength of Hg on Mn-DG composite. The order of Hg adsorption strength on Mn-DG composite are as follows: Pd13 (-1.68 eV) >> Ag13 (-0.67 eV) ∼ Ag1 (-0.69 eV) > Pd1 (-0.62 eV). Pd13-DG composite is therefore more efficient sorbent for Hg0 removal in terms of high stability and high adsorption reactivity compared to the Ag13. Further design of highly efficient carbon based sorbents should be focused on tailoring the ɛd of deposited metals.

  12. Supported Membranes Embedded with Fixed Arrays of Gold Nanoparticles

    PubMed Central

    2011-01-01

    We present a supported membrane platform consisting of a fluid lipid bilayer membrane embedded with a fixed array of gold nanoparticles. The system is realized by preforming a hexagonal array of gold nanoparticles (∼5–7 nm) with controlled spacing (∼50–150 nm) fixed to a silica or glass substrate by block copolymer lithography. Subsequently, a supported membrane is assembled over the intervening bare substrate. Proteins or other ligands can be associated with the fluid lipid component, the fixed nanoparticle component, or both, providing a hybrid interface consisting of mobile and immobile components with controlled geometry. We test different biochemical coupling strategies to bind individual proteins to the particles surrounded by a fluid lipid membrane. The coupling efficiency to nanoparticles and the influence of nanoparticle arrays on the surrounding membrane integrity are characterized by fluorescence imaging, correlation spectroscopy, and super-resolution fluorescence microscopy. Finally, the functionality of this system for live cell experiments is tested using the ephrin-A1–EphA2 juxtacrine signaling interaction in human breast epithelial cells. PMID:21967595

  13. Reduced graphene oxide: firm support for catalytically active palladium nanoparticles and game changer in selective hydrogenation reactions.

    PubMed

    Cano, Manuela; Benito, Ana M; Urriolabeitia, Esteban P; Arenal, Raul; Maser, Wolfgang K

    2013-11-07

    Simultaneous decomposition and reduction of a Pd(2+) complex in the presence of graphene oxide (GO) lead to the formation of Pd(0)-nanoparticles (Pd-NPs) with average sizes of 4 nm firmly anchored on reduced graphene oxide (RGO) sheets. The Pd-NP/RGO hybrids exhibited remarkable catalytic activity and selectivity in mild hydrogenation reactions where the acidic properties of RGO play an active role and may act as an important game-changer.

  14. Achieving independent control of core diameter and carbon shell thickness in Pd-C core-shell nanoparticles by gas phase synthesis

    NASA Astrophysics Data System (ADS)

    Singh, Vinod; Mehta, B. R.; Sengar, Saurabh K.; Karakulina, Olesia M.; Hadermann, Joke; Kaushal, Akshey

    2017-07-01

    Pd-C core-shell nanoparticles with independently controllable core size and shell thickness are grown by gas phase synthesis. First, the core size is selected by electrical mobility values of charged particles, and second, the shell thickness is controlled by the concentration of carbon precursor gas. The carbon shell grows by adsorption of carbon precursor gas molecules on the surface of nanoparticles, followed by sintering. The presence of a carbon shell on Pd nanoparticles is potentially important in hydrogen-related applications operating at high temperatures or in catalytic reactions in acidic/aqueous environments.

  15. Effective adsorption/electrocatalytic degradation of perchlorate using Pd/Pt supported on N-doped activated carbon fiber cathode.

    PubMed

    Yao, Fubing; Zhong, Yu; Yang, Qi; Wang, Dongbo; Chen, Fei; Zhao, Jianwei; Xie, Ting; Jiang, Chen; An, Hongxue; Zeng, Guangming; Li, Xiaoming

    2017-02-05

    In this work, Pd/Pt supported on N-doped activated carbon fiber (Pd/Pt-NACF) was employed as the electrode for electrocatalytic degradation of perchlorate through adsorption/electroreduction process. Perchlorate in solution was firstly adsorbed on Pd/Pt-NACF and then reduced to non-toxic chloride by the catalytic function of Pd/Pt at a constant current (20mA). Compared with Pd/Pt-ACF, the adsorption capacity and electrocatalytic degradation efficiency of Pd/Pt-NACF for perchlorate increased 161% and 28%, respectively. Obviously, positively charged N-functional groups on NACF surface enhanced the adsorption capacity of Pd/Pt-NACF, and the dissociation of hydrogen to atomic H* by the Pd/Pt nanostructures on the cathode might drastically promote the electrocatalytic reduction of perchlorate. The role of atomic H* in the electroreduction process was identified by tertiary butanol inhibition test. Meanwhile, the perchlorate degradation performance was not substantially lower after three successive adsorption/electrocatalytic degradation experiments, demonstrating the electrochemical reusability and stability of the as-prepared electrode. These results showed that Pd/Pt-NACF was effective for electrocatalytic degradation of perchlorate and had great potential in perchlorate removal from water. Copyright © 2016. Published by Elsevier B.V.

  16. Structure and Hydrogen Adsorption Properties of SBA-15 Doped with Pd Nanoparticles.

    PubMed

    Lee, Sang-Hwa; Park, Taehee; Yi, Whikun; Kim, Jaeyong

    2015-11-01

    Hydrogen adsorption properties of Pd-doped Santa Barbara amorphous No. 15 (Pd-SBA-15) were investigated and the results were compared with pure SBA-15 ones in terms of change of its structure and Pd concentration. Pd-SBA-15 samples were prepared by a hydrothermal reaction, using mixture of PEO20PPO70PEO20 (P123) and tetraethyl orthosilicate (TEOS). For the doping of Pd on SBA-15, PdC2 solution was added into the mixture of P123 and TEOS, and the solution was annealed at 80 degrees C for 2 hours under 800 Torr of hydrogen atmosphere. According to the X-ray diffraction and transmission electron microscope data, Pd-doped SBA-15 samples form a hexagonal array of mesoporous structure with 20-30 nm size of Pd particles. Values of specific surface area decreased from 630 to 414 m2/g as increasing the Pd doping level due to the increasing of the volume density. In fact, the volume density increased from 0.103 to 0.276 g/cc as increasing the mass ratio of PdCl2 to TEOS from 0 to 0.5. For the Pd-doped SBA-15, the amount of adsorbed hydrogen significantly increased from 0.49 to 0.99 wt% as increasing the Pd doping level from 0 to 0.5 demonstrating that Pd doping is an effect method for SBA-1 5 as a potential use of hydrogen storage application.

  17. H2 dissociation on γ-Al2O3 supported Cu/Pd atoms: A DFT investigation

    NASA Astrophysics Data System (ADS)

    Wang, Hongtao; Chen, Lijuan; Lv, Yongkang; Ren, Ruipeng

    2014-01-01

    The density functional theory (DFT) was applied to investigate the promotion effects of single Cu and Pd atoms deposition on γ-Al2O3 surface for the adsorption and dissociation of H2 molecule, which is of importance for many catalysis reactions. Due to its strong Lewis acidity, the tri-coordinated surface Al site was identified to be the most preferable site for both Cu and Pd location. The inner surface electrons rearrangement from O to Al of alumina was found to be a key factor to stabilize the Cu/Pd adsorption configurations, rather than the total electrons transfer between Cu/Pd and the surface. It was found that the supported Cu and Pd atoms are more active for H2 dissociation than the clean γ-Al2O3 surface. The supported Pd is more active than Cu for H2 dissociation. In addition, the metal-support interaction of the γ-Al2O3 supported Cu/Pd atoms are more favored than the metal-metal interaction of the metal clusters for the H2 dissociated adsorption.

  18. Primary charge carrier dynamics of water-solubilized CdZnS/ZnS core/shell and CdZnS/ZnS·Pd nanoparticle adducts

    NASA Astrophysics Data System (ADS)

    Busby, Erik; Thibert, Arthur; Page, Leah E.; Jawaid, Ali M.; Snee, Preston T.; Larsen, Delmar S.

    2013-06-01

    The primary photodynamics of 5-nm CdZnS core, CdZnS/ZnS core/shell, and CdZnS/ZnS·Pd nanoparticle adducts are characterized with broadband ultrafast transient absorption spectroscopy. Photogenerated excitons in the CdZnS and CdZnS/ZnS nanoparticles exhibit long-lived (>20 ns) lifetimes and further functionalizing of the type-I CdZnS/ZnS core/shells with Pd nanoparticles resulted in rapid exciton quenching (<250 ps) due to the transfer of electrons from the CdZnS core into the Pd nanocrystals via tunneling through the insulating ZnS shell. The shell-induced surface trap passivation and near-unity charge carrier injection efficiency into a platinum-group metal nanoparticle shows potential for enhanced colloidal photocatalytic applications, while enhancing photostability.

  19. Simple preparation of Pd-Pt nanoalloy catalysts for methanol-tolerant oxygen reduction

    NASA Astrophysics Data System (ADS)

    He, Wei; Liu, Juanying; Qiao, Yongjin; Zou, Zhiqing; Zhang, Xiaogang; Akins, Daniel L.; Yang, Hui

    Carbon-supported Pd-Pt bimetallic nanoparticles of different atomic ratios (Pd-Pt/C) have been prepared by a simple procedure involving the complexing of Pd and Pt species with sodium citrate followed by ethylene glycol reduction. As-prepared Pd-Pt alloy nanoparticles evidence a single-phase fcc disordered structure, and the degree of alloying is found to increase with Pd content. Both X-ray diffraction and transmission electron microscopy characterizations indicate that all the Pd-Pt/C catalysts possess a similar mean particle size of ca. 2.8 nm. The highest mass and specific activity of the oxygen reduction reaction (ORR) using the Pd-Pt/C catalysts are found with a Pd:Pt atomic ratio of 1:2. Moreover, all Pd-Pt alloy catalysts exhibit significantly enhanced methanol tolerance during the ORR than the Pt/C catalyst, ensuring a higher ORR performance while diminishing Pt utilization.

  20. Geometric Stability and Elastic Response of a Supported Nanoparticle Film

    SciTech Connect

    Leahy, Brian D.; Pocivavsek, Luka; Meron, Mati; Lam, Kin Lok; Salas, Desiree; Viccaro, P. James; Lee, Ka Yee C.; Lin, Binhua

    2011-09-16

    The mechanical response to compression of a self-assembled gold nanoparticle monolayer and trilayer at the air-liquid interface is examined. Analysis of the film's buckling morphology under compression reveals an anomalously low bending rigidity for both the monolayer and the trilayer, in contrast with continuum elastic plates. We attribute this to the spherical geometry of the nanoparticles and poor coupling between layers, respectively. The elastic energy of the trilayers is first delocalized in wrinkles and then localized into folds, as predicted by linear and nonlinear elastic theory for an inextensible thin film supported on a fluid.

  1. Characterization and reactivity of Pd Pt bimetallic supported catalysts obtained by laser vaporization of bulk alloy

    NASA Astrophysics Data System (ADS)

    Rousset, J. L.; Cadete Santos Aires, F. J.; Bornette, F.; Cattenot, M.; Pellarin, M.; Stievano, L.; Renouprez, A. J.

    2000-09-01

    Bimetallic Pd-Pt clusters produced by laser vaporization of bulk alloy have been deposited on high surface alumina. Energy dispersive X-ray (EDX) analysis and transmission electron microscopy (TEM) show that they have a perfectly well-defined stoichiometry and a narrow range of size. Therefore, they constitute ideal systems to investigate alloying effects towards reactivity. Pd-Pt alloys are already known for their applications in the hydrogenation of unsaturated hydrocarbons, especially aromatics, because this system is highly resistant to sulfur and nitrogen poisoning. In this context, the catalytic properties of this system have been investigated in the hydrogenation of tetralin in the presence of hydrogen sulfide. Preliminary results show that this model catalyst is more sulfur-resistant than each of the pure supported metals prepared by chemical methods.

  2. Structuring Pd Nanoparticles on 2H-WS2 Nanosheets Induces Excellent Photocatalytic Activity for Cross-Coupling Reactions under Visible Light.

    PubMed

    Raza, Faizan; Yim, DaBin; Park, Jung Hyun; Kim, Hye-In; Jeon, Su-Ji; Kim, Jong-Ho

    2017-10-05

    Effective photocatalysts and their surface engineering are essential for the efficient conversion of solar energy into chemical energy in photocatalyzed organic transformations. Herein, we report an effective approach for structuring Pd nanoparticles (NPs) on exfoliated 2H-WS2 nanosheets (WS2/PdNPs), resulting in hybrids with extraordinary photocatalytic activity in Suzuki reactions under visible light. Pd NPs of different sizes and densities, which can modulate the photocatalytic activity of the as-prepared WS2/PdNPs, were effectively structured on the basal plane of 2H-WS2 nanosheets via a sonic wave-assisted nucleation method without any reductants at room temperature. As the size of Pd NPs on WS2/PdNPs increased, their photocatalytic activity in Suzuki reactions at room temperature increased substantially. In addition, it was found that protic organic solvents play a crucial role in activating WS2/PdNPs catalysts in photocatalyzed Suzuki reactions, although these solvents are generally considered much less effective than polar aprotic ones in the conventional Suzuki reactions promoted by heterogeneous Pd catalysts. A mechanistic investigation suggested that photogenerated holes are transferred to protic organic solvents, whereas photogenerated electrons are transferred to Pd NPs. This transfer makes the Pd NPs electron-rich and accelerates the rate-determining step, i.e., the oxidative addition of aryl halides under visible light. WS2/PdNPs showed the highest turnover frequency (1244 h(-1)) for photocatalyzed Suzuki reactions among previously reported photocatalysts.

  3. A bio-inspired sensor based on surfactant film and Pd nanoparticles.

    PubMed

    Zapp, Eduardo; Souza, Franciane D; Souza, Bruno S; Nome, Faruk; Neves, Ademir; Vieira, Iolanda C

    2013-01-21

    A bio-inspired complex, [(bpbpmp)Fe(III)(m-OAc)(2)Cu(II)](ClO(4)), was combined with a zwitterionic surfactant (ImS3-14) stabilizing pre-formed palladium nanoparticles and coated on a glassy carbon electrode (GCE). This bio-inspired surfactant film was capable of catalyzing redox reactions of dihydroxybenzenes, thus allowing the simultaneous electrochemical quantification of CC and HQ in cigarette residue samples by square-wave voltammetry (SWV). The best experimental conditions were obtained using phosphate buffer solution (0.1 mol L(-1), pH 7.0), with 1.3 nmol of the bio-inspired complex, 0.15 μmol of the surfactant and 1.08 nmol of Pd. The best voltammetric parameters were: frequency 100 Hz, pulse amplitude 40 mV and step potential 8 mV. The limits of detection calculated from simultaneous curves were found to be 2.2 × 10(-7) and 2.1 × 10(-7) mol L(-1) for HQ and CC respectively.

  4. Improvement of electrocatalytic performance of carbon supported Pd anodic catalyst in direct formic acid fuel cell by ethylenediamine-tetramethylene phosphonic acid

    NASA Astrophysics Data System (ADS)

    Lu, Liang; Li, Huanzhi; Hong, Yujie; Luo, Yafen; Tang, Yawen; Lu, Tianhong

    2012-07-01

    The direct formic acid fuel cell (DFAFC) has two major shortcomings that limit its lifespan and performance: (i) the poor electrocatalytic stability of the carbon supported Pd (Pd/C) catalyst for the oxidation of formic acid and (ii) rapid decomposition of formic acid over the Pd/C catalyst. To solve the problems, the Pd/C catalyst is modified with ethylenediamine-tetramethylene phosphonic acid (EDTMP). The resulting catalyst is designated as Pd/C-E catalyst. It is found that the Pd/C-E catalyst can inhibit the decomposition of formic acid and promote the oxidation of formic acid through the direct pathway. Consistently, the Pd/C-E catalyst is significantly protected from CO poisoning. As compared to the Pd/C catalyst, the electrocatalytic performance of the Pd/C-E catalyst is significantly superior. These results provide the first proof of the concept that DFAFC can be significantly improved by Pd/C-E catalyst.

  5. Supported Palladium Nanoparticle-Catalyzed Carboxylation of Aryl Halides, Alkenylsilanes, and Organoboronic Acids Employing Oxalic Acid as the C1 Source.

    PubMed

    Shil, Arun K; Kumar, Sandeep; Reddy, C Bal; Dadhwal, Sumit; Thakur, Vandna; Das, Pralay

    2015-11-06

    Polystyrene-supported palladium(0) (Pd@PS) nanoparticles as a heterogeneous catalyst have been developed for caboxylation of aryl halides, alkenylsilanes, and organoboronic acids to produce the corresponding carboxylic acids with minor quantities of corresponding aldehydes using bench-stable and inexpensive oxalic acid as the C1 source under focused microwave irradiation. The close vicinity of oxalic acid to Pd@PS maintained through ionic bonding helped to produce CO2 over the catalytic surface that concurrently participated in the carboxylation reaction.

  6. Understanding the effect of ultrathin AuPd alloy shells of irregularly shaped Au@AuPd nanoparticles with high-index facets on enhanced performance of ethanol oxidation.

    PubMed

    Bi, Cuixia; Feng, Cong; Miao, Tingting; Song, Yahui; Wang, Dayang; Xia, Haibing

    2015-12-21

    In this study, irregularly shaped, concave cuboidal Au@AuPd nanoparticles (ISCC-Au@AuPd NPs) with high-index facets were synthesized via Pd overgrowth on pre-formed ISCC-Au NPs with a concentration of Pd precursors as low as 2%. The AuPd alloy nature of the resulting shells was confirmed by X-ray photoelectron spectroscopy, cyclic voltammogram analysis, and energy dispersive X-ray spectroscopy. Among the irregularly shaped NPs obtained, the ISCC-Au97.5@Au0.5Pd2.0 NPs display the largest electrochemically active surface area (up to 92.11 m(2) g(-1)), as their closed-packed agglomeration was prevented, and the best long-term stability with respect to ethanol oxidation (0.50 M) in alkaline media (0.30 KOH) by efficiently removing intermediates. Their mass- and ECSA-normalized current densities (4.15 A mgPd(-1) and 4.51 mA cm(-2)) are about 20.7 times and 6.9 times higher than those of commercial Pd/C catalysts (0.20 A mgPd(-1) and 0.65 mA cm(-2)), respectively.

  7. Ostwald ripening of charged supported metal nanoparticles: Schottky model

    NASA Astrophysics Data System (ADS)

    Zhdanov, Vladimir P.

    2015-07-01

    Due to high surface area, supported metal nanoparticles are thermodynamically prone to sintering. The experimental studies of this process exhibit sometimes transient bimodal particle size distributions. Such observations may result from the support heterogeneity. Looking retrospectively, one can also find the prediction that in the case of Ostwald ripening this feature can be related to charge of metal nanoparticles. In real systems, this charge is often associated with the metal-support interaction and can be interpreted in the framework of the Schottky model. Using this model, the author shows that the charge redistribution cannot be behind bimodal particle size distributions. Moreover, the corresponding contribution to the driving force for Ostwald ripening is typically much smaller than the conventional one.

  8. Synthesis of biogenic Ag@Pd Core-shell nanoparticles having anti-cancer/anti-microbial functions.

    PubMed

    Abdel-Fattah, Wafa I; Eid, M M; Abd El-Moez, Sh I; Mohamed, E; Ali, Ghareib W

    2017-08-15

    Biogenic Ag@Pd core-shell nanoparticles were greenly synthesized within two plant extracts aiming at enhanced anticancer/bactericidal functions. These functions were verified for the two Pd@Ag biogenic core-shell nanoparticles (BCSnp) with constant Pd to several Ag contents. BCSnp were synthesized within two extracts of Almond nuts and Black Berry fruits, four samples each, through simple, low cost and echo friendly microwave route. The BCSnp Surface Plasmon Resonance (SPR) was detected via UV/visible spectrophotometer. Their morphology was assessed using High-Resolution Transmission Electron Microscope and Field Emission Scanning Electron Microscope supplemented with EDAX. Particle size/zeta potential of the achieved nanoparticles was measured. The active reducing groups were depicted by FTIR while XRD assessed nanoparticles crystallinity. The enhanced particle size distribution as proved by UV and band gap energies, imparted better functionality by the Almond extract compared to the berry one due to its protein content. Cytotoxicity against human breast cancer (MCF7) and liver cancer (HEPG2) cell lines were followed and compared to the normal Wish cells. The antimicrobial impact against gram-negative (G(-)veo) E. coli, gram-positive (G(+)ve) S. aureus bacteria and mycotic strain C. albicans species were verified and compared to antibiotics. A significant inhibition of cancer cell growth of MCF 7 and HEPG2 compared to Wish normal cells and doxorubicin is assessed. A discriminative effect was recorded for G(-)ve compared to G(+)ve, along with Mycotic strain C. albicans is achieved. The obtained BCSnp are proposed for cancer therapy and bactericidal applications with improved efficiency applying the nanomedicine approach. Tailorable properties can be obtained by tuning the individual structures. Copyright © 2017 Elsevier Inc. All rights reserved.

  9. Magnetite nanoparticle-supported coordination polymer nanofibers: synthesis and catalytic application in Suzuki-Miyaura coupling.

    PubMed

    Liao, Yetong; He, Lisi; Huang, Jing; Zhang, Jianyong; Zhuang, Lin; Shen, Hui; Su, Cheng-Yong

    2010-08-01

    Functional nanoscale coordination polymers are receiving growing scientific interest because of their potential applications in many domains. In this paper, we demonstrated that a nanofibrous networked metal-organic gel (G1-MNPs) was formed by simply mixing 4,4',4''-(1,3,5-triazine-2,4,6-triyl)tris(N-(pyridin-3-ylmethyl)benzamide) (L) and Pd(COD)(NO(3))(2) in CHCl(3)-MeOH with a Pd/L molar ratio of 1:1 in the presence of magnetite nanoparticle (MNPs). The self-assembly behavior of nanofibers was not significantly effected by the introduction of magnetite nanoparticles. The xerogel of G1-MNPs was superparamagnetic and showed catalytic activity in Suzuki-Miyaura C-C coupling reactions. The Pd(II) xerogel could be magnetically isolated and recycled with a permanent magnet. It represents a novel strategy to introduce nanoparticles into functional coordination polymers for multifunctional materials.

  10. Direct C-H arene homocoupling over gold nanoparticles supported on metal oxides.

    PubMed

    Ishida, Tamao; Aikawa, Shohei; Mise, Yoshiyuki; Akebi, Ryota; Hamasaki, Akiyuki; Honma, Tetsuo; Ohashi, Hironori; Tsuji, Tetsuro; Yamamoto, Yasushi; Miyasaka, Mitsuru; Yokoyama, Takushi; Tokunaga, Makoto

    2015-02-01

    The direct CH/CH bond coupling of dimethyl phthalate was performed successfully over supported gold nanoparticle catalysts. Gold on reducible metal oxides, such as Co3 O4 , and on inert oxides that have an oxygen-releasing capacity, such as ZrO2 , showed the highest catalytic activity for the production of biphenyl tetracarboxylate using O2 as the sole oxidant. Supported Pd(OH)2 also catalyzed the reaction, but the catalytic activity was inferior to that of gold. Moreover, the gold catalysts exhibited excellent regioselectivity for the synthesis of valuable 3,3',4,4'-tetrasubstituted biphenyls by coupling with each other at the 4-position without the need for additional ligands. Gold catalysts also promoted the oxidative homocoupling of arenes including o-xylene to give symmetrical biaryls with high regioselectivity. X-ray absorption fine structure measurements revealed that the catalytically active species was Au(0) and that the lattice oxygen of Co3 O4 played an important role in the gold-catalyzed oxidative coupling. The results of the kinetic studies were consistent with an electrophilic aromatic substitution pathway. Regioselectivity is not controlled by directing groups or the electronic character of the substituents but by steric hindrance, which suggests that gold nanoparticles not only catalyze the oxidative coupling but also act as bulky ligands to control the regioselectivity.

  11. Surfactant-Free Synthesis of Carbon-Supported Palladium Nanoparticles and Size-Dependent Hydrogen Production from Formic Acid-Formate Solution.

    PubMed

    Zhang, Shuo; Jiang, Bei; Jiang, Kun; Cai, Wen-Bin

    2017-07-26

    Steerable hydrogen generation from the hydrogen storage chemical formic acid via heterogeneous catalysis has attracted considerable interest given the safety and efficiency concerns in handling H2. Herein, a series of carbon-supported capping-agent-free Pd nanoparticles (NPs) with mean sizes tunable from 2.0 to 5.2 nm are developed due to the demand for more efficient dehydrogenation from a formic acid-formate solution of pH 3.5 at room temperature. The trick for the facile size-controlled synthesis of Pd/C catalysts is the selective addition of Na2CO3, NH3·H2O, or NaOH to a Pd(II) solution to attain initial pH values of 7-9.5. For comparison, cuboctahedron modeling and electrochemical COads stripping methods are applied to evaluate active surface Pd sites for turnover frequency (TOF) calculation. Both mass activity and specific activity (TOF) of hydrogen production are not only time-dependent but also Pd-size-dependent. An initial H2 production rate of 246 L·h(-1)·gPd(-1) is achieved on 2.0 nm Pd/C at 303 K, together with a TOF of 1815 h(-1) on the basis of cuboctahedron modeling of surface-active Pd sites. The initial TOF exhibits a significant rise from 3.5 down to 2.8 nm and then levels off below 2.8 nm and even shows a maxima at ca. 2.2 nm using the electrochemical surface area for calculation. The volcano-shaped dependence of TOF on Pd NP size may be better attributed to the changing ratios of terrace sites to defect sites on Pd NPs.

  12. Synthesis, characterization, and catalytic activity in Suzuki coupling and catalase-like reactions of new chitosan supported Pd catalyst.

    PubMed

    Baran, Talat; Inanan, Tülden; Menteş, Ayfer

    2016-07-10

    The aim of this study is to analyze the synthesis of a new chitosan supported Pd catalyst and examination of its catalytic activity in: Pd catalyst was synthesized using chitosan as a biomaterial and characterized with FTIR, TG/DTG, XRD, (1)H NMR, (13)C NMR, SEM-EDAX, ICP-OES, Uv-vis spectroscopies, and magnetic moment, along with molar conductivity analysis. Biomaterial supported Pd catalyst indicated high activity and long life time as well as excellent turnover number (TON) and turnover frequency (TOF) values in Suzuki reaction. Biomaterial supported Pd catalyst catalyzed H2O2 decomposition reaction with considerable high activity using comparatively small loading catalyst (10mg). Redox potential of biomaterial supported Pd catalyst was still high without negligible loss (13% decrease) after 10 cycles in reusability tests. As a consequence, eco-friendly biomaterial supported Pd catalyst has superior properties such as high thermal stability, long life time, easy removal from reaction mixture and durability to air, moisture and high temperature. Copyright © 2016 Elsevier Ltd. All rights reserved.

  13. Pd nanoparticles formation by femtosecond laser irradiation and the nonlinear optical properties at 532 nm using nanosecond laser pulses

    SciTech Connect

    Fan Guanghua; Qu Shiliang; Wang Qiang; Zhao Chongjun; Zhang Lei; Li Zhongguo

    2011-01-15

    Pd nanoparticles (NPs) were prepared by focused femtosecond laser irradiation of PdCl{sub 2} dissolved in ethanol. Transmission electron microscopy (TEM) analysis revealed that Pd NPs show certain crystalline microstructure, and the average diameter is 3.4 nm with narrow size distribution from 2.0 to 6.0 nm. The nonlinear optical absorption and refraction of Pd NPs solution were investigated with nanosecond laser pulses at 532 nm. The nonlinear absorption of Pd NPs is saturable at low intensity of 3.28x10{sup 11} W/m{sup 2} but it is changed to reverse saturable with the intensity increased to 7.96x10{sup 11} W/m{sup 2}, which accordingly indicates the nonlinear refraction is changed from self-defocusing to self-focusing. The transition of the nonlinear absorption with the increase in pulse intensity is analyzed by an empirical model which includes mostly saturable absorption (SA) and two-photon absorption (TPA). The intensity of saturable I{sub s} is obtained, along with TPA coefficient {beta}. SA and TPA are both originated from the interband transition between the d band and s-p conduction band. The SA possess less occupied density of states in the ground state and less unoccupied density of states in the excited state than that of TPA, so the TPA dominates the nonlinear absorption when the pulse intensity is high, leading to as-observed transition from SA to TPA. The refraction variation with increase in pulse intensity is attributed to the interband transition of electrons from d band to s-p conduction band in the Pd NPs.

  14. Selective Cu4Pd alloy nanoparticles anchoring on amine functionalized graphite nanosheets and their use as reusable catalysts for a C-C coupling reaction with the sacrificial role of Cu for Pd-regeneration.

    PubMed

    Chakravarty, Amrita; De, Goutam

    2016-08-02

    A facile method for the synthesis of phase selective alloy nanoparticles (NPs), Cu4Pd and their in situ anchoring on the surface of amine functionalized graphite nanosheets (AFGNS) by solvothermal process has been demonstrated. It has been seen that upon adding CuCl2·H2O and PdCl2 into the reaction medium containing AFGNS, the -NH2 group initially helps to immobilize Cu(2+) ions from CuCl2·H2O. During the solvothermal reaction in presence of N,N-dimethylformamide (DMF; solvent cum reducing agent) Pd(2+) gets reduced first due to its higher reduction potential. These Pd NPs in turn help in the reduction of Cu(2+) to Cu in an epitaxial manner. Finally at high temperature and long reaction time Cu and Pd combine to form the Cu4Pd alloy NPs along with a small fraction of Cu NPs. The conditions to obtain Cu4Pd NPs have been optimized through controlled reactions. The as prepared Cu4Pd@AFGNS composite has been successfully used for Suzuki-Miyuara C-C coupling reaction with sufficiently high yield and reusability of up to five cycles. The progress of the reaction was monitored using a fluorimeter. Interestingly, it has been observed that the small fraction of the Cu NPs present in the system played a sacrificial role in regenerating metallic Pd NPs in the first and second reaction cycles, followed by Cu from the Cu4Pd alloy itself from the third cycle onwards which played the sacrificial role to regenerate Pd(0). A probable reaction mechanism of the catalytic reaction with Cu4Pd@AFGNS has been suggested.

  15. Multimodal Study of the Speciations and Activities of Supported Pd Catalysts During the Hydrogenation of Ethylene

    DOE PAGES

    Zhao, Shen; Li, Yuanyuan; Liu, Deyu; ...

    2017-08-07

    In this paper we describe a multimodal exploration of the atomic structure and chemical state of silica-supported palladium nanocluster catalysts during the hydrogenation of ethylene in operando conditions that variously transform the metallic phases between hydride and carbide speciations. The work exploits a microreactor that allows combined multiprobe investigations by high-resolution transmission electron microscopy (HR-TEM), X-ray absorption fine structure (XAFS), and microbeam IR (μ-IR) analyses on the catalyst under operando conditions. The work specifically explores the reaction processes that mediate the interconversion of hydride and carbide phases of the Pd clusters in consequence to changes made in the composition ofmore » the gas-phase reactant feeds, their stability against coarsening, the reversibility of structural/compositional transformations, and the role that oligomeric/waxy byproducts (here forming under hydrogen-limited reactant compositions) might play in modifying activity. The results provide new insights into structural features of the chemistry/mechanisms of Pd catalysis during the selective hydrogenation of acetylene in ethylene—a process simplified here in the use of binary ethylene/hydrogen mixtures. Finally, these explorations, performed in operando conditions, provide new understandings of structure–activity relationships for Pd catalysis in regimes that actively transmute important attributes of electronic and atomic structures.« less

  16. Growth and decomposition of aligned and ordered PdO nanoparticles

    NASA Astrophysics Data System (ADS)

    Penner, Simon; Wang, Di; Jenewein, Bernd; Gabasch, Harald; Klötzer, Bernhard; Knop-Gericke, Axel; Schlögl, Robert; Hayek, Konrad

    2006-09-01

    The formation, thermal decomposition, and reduction of small PdO particles were studied by high-resolution transmission electron microscopy and selected area electron diffraction. Well-defined Pd particles (mean size of 5-7nm) were grown epitaxially on NaCl (001) surfaces and subsequently covered by a layer of amorphous SiO2 (25nm ), prepared by reactive deposition of SiO in 10-2Pa O2. The resulting films were exposed to molecular O2 in the temperature range of 373-673K, and the growth of PdO was studied. The formation of a PdO phase starts at 623K and is almost completed at 673K. The high-resolution experiments suggest a topotactic growth of PdO crystallites on top of the original Pd particles. Subsequent reaction of the PdO in 10mbar CO for 15min and thermal decomposition in 1bar He for 1h were also investigated in the temperature range from 373to573K. Reductive treatments in CO up to 493K do not cause a significant change in the PdO structure. The reduction of PdO starts at 503K and is completed at 523K. In contrast, PdO decomposes in 1bar He at around 573K. The mechanism of PdO growth and decay is discussed and compared to results of previous studies on other metals, e.g., on rhodium.

  17. Electrocatalytic performance of carbon supported Pd catalyst modified with Keggin type of Sn-substituted polyoxometalatate for formic acid oxidization

    NASA Astrophysics Data System (ADS)

    Ji, Yun; Shen, Liping; Wang, Anxing; Wu, Min; Tang, Yawen; Chen, Yu; Lu, Tianhong

    2014-08-01

    The carbon supported Pd(Pd/C) catalyst modified by the new polyoxometalate with Keggin type of Sn-Substituted structure K7CoIIW11O39SnIVOH (Pd/C-K7) catalyst is prepared with the simple impregnation-reduction method. This work investigates the effects of Pd/C-K7 catalyst for direct formic acid fuel cells (DFAFCs). The morphology, structure, size and composition of the Pd/C-K7 catalyst are characterized by transmission electron microscopy (TEM) energy dispersive spectrum (EDS), X-ray diffraction (XRD). Cyclic voltammetry, chronoamperometry and CO-stripping voltammetry tests demonstrate the Pd/C-K7 catalyst have higher electrocatalytic activity, better electrochemical stability, and higher resistance to CO poisoning over the unmodified Pd/C catalyst for the formic acid oxidation reaction (FAOR) owing to K7CoIIW11O39SnIVOH with Keggin structure. Therefore, the Pd/C-K7 catalyst could be used as the excellent anodic catalyst in DFAFCs.

  18. Natural DNA-modified graphene/Pd nanoparticles as highly active catalyst for formic acid electro-oxidation and for the Suzuki reaction.

    PubMed

    Qu, Konggang; Wu, Li; Ren, Jinsong; Qu, Xiaogang

    2012-09-26

    Natural DNA has been considered as a building block for developing novel functional materials. It is abundant, renewable, and biodegradable and has a well-defined structure and conformation with many unique features, which are difficult to find in other polymers. Herein, calf thymus DNA modified graphene/Pd nanoparticle (DNA-G-Pd) hybrid materials are constructed for the first time using DNA as a mediator, and the prepared DNA-G-Pd hybrid shows high catalytic activity for fuel cell formic acid electro-oxidation and for organic Suzuki reaction. The main advantages of using DNA are not only because the aromatic nucleobases in DNA can interact through π-π stacking with graphene basal surface but also because they can chelate Pd via dative bonding in such defined sites along the DNA lattice. Our results indicate that isolated, homogeneous, and ultrafine spherical Pd nanoparticles are densely in situ decorated on DNA-modified graphene surfaces with high stability and dispersibility. The prepared DNA-G-Pd hybrid has much greater activity and durability for formic acid electro-oxidation than the commercial Pd/C catalyst and polyvinylpyrrolidone-mediated graphene/Pd nanoparticle (PVP-G-Pd) hybrid used for direct formic acid fuel cells (DFAFCs). Besides, the DNA-G-Pd hybrid can also be an efficient and recyclable catalyst for the organic Suzuki reaction in aqueous solution under aerobic conditions without any preactivation. Since DNA can chelate various transition metal cations, this proof-of-concept protocol provides the possibility for the tailored design of other novel catalytic materials based on graphene with full exploitation of their properties.

  19. Synthesis of Superparamagnetic Core-Shell Structure Supported Pd Nanocatalysts for Catalytic Nitrite Reduction with Enhanced Activity, No Detection of Undesirable Product of Ammonium, and Easy Magnetic Separation Capability.

    PubMed

    Sun, Wuzhu; Yang, Weiyi; Xu, Zhengchao; Li, Qi; Shang, Jian Ku

    2016-01-27

    Superparamagnetic nanocatalysts could minimize both the external and internal mass transport limitations and neutralize OH(-) produced in the reaction more effectively to enhance the catalytic nitrite reduction efficiency with the depressed product selectivity to undesirable ammonium, while possess an easy magnetic separation capability. However, commonly used qusi-monodispersed superparamagnetic Fe3O4 nanosphere is not suitable as catalyst support for nitrite reduction because it could reduce the catalytic reaction efficiency and the product selectivity to N2, and the iron leakage could bring secondary contamination to the treated water. In this study, protective shells of SiO2, polymethylacrylic acid, and carbon were introduced to synthesize Fe3O4@SiO2/Pd, Fe3O4@PMAA/Pd, and Fe3O4@C/Pd catalysts for catalytic nitrite reduction. It was found that SiO2 shell could provide the complete protection to Fe3O4 nanosphere core among these shells. Because of its good dispersion, dense structure, and complete protection to Fe3O4, the Fe3O4@SiO2/Pd catalyst demonstrated the highest catalytic nitrite reduction activity without the detection of NH4(+) produced. Due to this unique structure, the activity of Fe3O4@SiO2/Pd catalysts for nitrite reduction was found to be independent of the Pd nanoparticle size or shape, and their product selectivity was independent of the Pd nanoparticle size, shape, and content. Furthermore, their superparamagnetic nature and high saturation magnetization allowed their easy magnetic separation from treated water, and they also demonstrated a good stability during the subsequent recycling experiment.

  20. α-Alkylation of ketones with primary alcohols driven by visible light and bimetallic gold and palladium nanoparticles supported on transition metal oxide

    NASA Astrophysics Data System (ADS)

    Bai, Meifen; Xin, Hui; Guo, Zhi; Guo, Dapeng; Wang, Yan; Zhao, Peng; Li, Jingyi

    2017-01-01

    The direct α-alkylation of ketones with primary alcohols to obtain the corresponding saturated coupled ketones was achieved with bimetallic gold(Au)-palladium(Pd) nanoparticles(NPs) supported on a transition metal oxide (such as CeO2). This system demonstrated a higher catalytic property than Au/CeO2 and Pd/CeO2 under visible light irradiation at 40 ± 3 °C in an Ar atmosphere. Such phenomenon was caused by the synergistic effect between Au and Pd. Isopropyl alcohol was used as the solvent and CH3ONa as the base. The effect of the bimetallic Au-Pd mass ratio and the two different transition metal oxide supports (such as CeO2 or ZrO2) during the reaction process was studied. The highest catalytic activity of those examined happened with the 1.5 wt% Au-1.5 wt% Pd (Au and Pd mass ratio 1:1)/CeO2 photo-catalyst. The intensity and wavelength of the visible light had a strong influence on the system. The catalyst can be reused for four times. A reaction mechanism was proposed for the α-alkylation of ketones with primary alcohols.

  1. Facile synthesis of porous Pt-Pd nanospheres supported on reduced graphene oxide nanosheets for enhanced methanol electrooxidation

    NASA Astrophysics Data System (ADS)

    Li, Shan-Shan; Lv, Jing-Jing; Hu, Yuan-Yuan; Zheng, Jie-Ning; Chen, Jian-Rong; Wang, Ai-Jun; Feng, Jiu-Ju

    2014-02-01

    In this study, a simple, facile, and effective wet-chemical strategy was developed in the synthesis of uniform porous Pt-Pd nanospheres (Pt-Pd NSs) supported on reduced graphene oxide nanosheets (RGOs) under ambient temperature, where octylphenoxypolye thoxyethanol (NP-40) is used as a soft template, without any seed, organic solvent or special instruments. The as-prepared nanocomposites display enhanced electrocatalytic activity and good stability toward methanol oxidation, compared with commercial Pd/C and Pt/C catalysts. This strategy may open a new route to design and prepare advanced electrocatalysts for fuel cells.

  2. Study of bimetallic Pd-Pt clusters in both free and supported phases

    NASA Astrophysics Data System (ADS)

    Rousset, J. L.; Cadrot, A. M.; Cadete Santos Aires, F. J.; Renouprez, A.; Mélinon, P.; Perez, A.; Pellarin, M.; Vialle, J. L.; Broyer, M.

    1995-06-01

    We study PdPt bimetallic clusters in both free and supported phases. These clusters have been produced with a laser vaporization source. Free clusters directly produced by the source are studied by time of flight mass spectrometry and photofragmentation technique. We observed a sequential evaporation of Pd atoms in the mixed clusters consistent with a palladium segregation process. This tendency has been also observed on supported particles from which the structure and the composition are determined by high resolution transmission electron microscopy and energy dispersive x-ray analysis. A main result is that each particle has the composition of the massic rod vaporized in the source. The supported particles are well crystallized and exhibit truncated octahedron shapes. Experimental observations are well explained using a modified tight binding model. Indeed, within this model, we found that the equilibrium shape is strongly related to the variation of the cohesive energy with atomic coordination number. Also, some preliminary results on the specific reactivity of these bimetallic clusters are presented.

  3. Efficient synthesis of PtPd/Fe3O4 nanoparticles and its magnetic recoverability and stable recyclability for the Heck and Suzuki reactions

    NASA Astrophysics Data System (ADS)

    Sun, Yuanxu; Zhu, Xiaoqing; Guo, Dandan; Chen, Xiao; Dai, Jingtao

    2017-07-01

    Platinum and palladium bimetal nanoparticles on ferroferric oxide (PtPd/Fe3O4 NPs) nanocomposite catalysts were successfully synthesized with polyvinyl pyrrolidone as a stabilizing agent. The resultant samples were characterized by x-ray diffraction, x-ray photoelectron spectroscopy, transmission electron microscopy, high-resolution transmission electron microscopy, inductively coupled plasma, and magnetic studies. The catalytic performance of the PtPd/Fe3O4 NPs in the Heck and Suzuki coupling reactions was evaluated. Results showed that the cubic phase of Pt and Pd bimetal nanoparticles coexists with that of Fe3O4. The PtPd/Fe3O4 NP catalysts, which were approximately 22 nm in size, showed excellent catalytic activity in the Heck and Suzuki reactions. Moreover, the catalyst can be recovered with a magnet and reused several times without the significant loss of catalytic activity.

  4. Simultaneous removal of co-contaminants: acid brilliant violet and Cu2+ by functional bimetallic Fe/Pd nanoparticles

    NASA Astrophysics Data System (ADS)

    Jin, Xiaoying; Chen, Zhengxian; Wang, Ting; Chen, Zuliang; Megharaj, Mallavarapu; Naidu, Ravendra

    2014-10-01

    Effluents from the textile industry often contain dyes and metals that are a serious environmental concern. It is a challenge to develop a method for simultaneous removal of mixed contaminants. In this study, kaolinite supported bimetallic Fe/Pd (K-Fe/Pd) is firstly reported to be used for simultaneous catalytic removal of acid brilliant violet (ABV) and Cu2+ in aqueous solution, where the presence of kaolinite as a stable supporter and disperser maintains the reactivity of Fe0 as a reductant, while Pd0 as a catalyst accelerates the reaction. This was confirmed by scanning electron microscopy (SEM), X-ray diffraction (XRD), and batch experiments. 96.23 % of ABV and 100 % of Cu2+ was removed using K-Fe/Pd within 60 min, while only 77.50 % of ABV and 99.45 % of Cu2+ using K-Fe, and 19.75 % of ABV and 4.00 % of Cu2+ using kaolinite was removed, respectively. However, both efficiency and rate of removal in the mixed solution were higher than that of the single one regarding both ABV and Cu2+, which is attributable to the formation of in situ trimetallic Cu/Fe/Pd in the mixed solution. Different factors impacting on the removal of ABV-Cu2+ using K-Fe/Pd showed that the catalytic reduction decreased when pH, initial concentration, and temperature increased. Finally, the reuse and application of K-Fe/Pd in dyeing wastewater led to a removal efficiency of 96.35 % for ABV and 100 % for Cu2+, respectively.

  5. Synthesis, characterization, and debromination reactivity of cellulose-stabilized Pd/Fe nanoparticles for 2,2',4,4'-tretrabromodiphenyl ether

    PubMed Central

    Huang, Guofu; Wang, Mianmian; Hu, Yongyou; Lv, Sihao; Li, Changfang

    2017-01-01

    In this study, two kinds of cellulose derivatives (polyanionic cellulose (PAC) and hydroxypropylmethyl cellulose (HPMC)) were selected as stabilizers of Pd/Fe nanoparticles (NPs) to investigate their influences on the debromination performances of 2,2',4,4'-tretrabromodiphenyl ether (BDE47). Field emission scanning electron microscope (FE-SEM) images revealed that the cellulose-stabilized Pd/Fe NPs were smaller and more uniform than the bare-Pd/Fe NPs. X-ray diffractometer (XRD) and X-ray photoelectron spectroscopy (XPS) results suggested that cellulose coatings found on Pd/Fe NPs surfaces featured some antioxidation abilities, which followed the order of HPMC < PAC. Sedimentation tests demonstrated that the stabilizing power of PAC for Pd/Fe NPs was higher than that of HPMC. Fourier transfer infrared spectrometer (FTIR) results indicated that PAC molecules were bound to the Pd/Fe NPs surfaces by polar covalent bonds and hydrogen bonds, while HPMC molecules interacted with the nanoparticles by hydrogen bonds. Batch debromination test for BDE47 demonstrated that the catalytic debromination rate with cellulose-stabilized Pd/Fe NPs was higher than that with bare-Pd/Fe NPs during reaction period of 15 min. Overall, this study indicated that both celluloses are beneficial to forming smaller, more regular, stable and antioxidative Pd/Fe NPs, leading to higher debromination reactivity for BDE47 compared with the bare-Pd/Fe NPs. Therefore Pd/Fe NPs can be utilized as a promising remediation technology for the contaminated groundwater and soils. PMID:28355273

  6. Synthesis, characterization, and debromination reactivity of cellulose-stabilized Pd/Fe nanoparticles for 2,2',4,4'-tretrabromodiphenyl ether.

    PubMed

    Huang, Guofu; Wang, Mianmian; Hu, Yongyou; Lv, Sihao; Li, Changfang

    2017-01-01

    In this study, two kinds of cellulose derivatives (polyanionic cellulose (PAC) and hydroxypropylmethyl cellulose (HPMC)) were selected as stabilizers of Pd/Fe nanoparticles (NPs) to investigate their influences on the debromination performances of 2,2',4,4'-tretrabromodiphenyl ether (BDE47). Field emission scanning electron microscope (FE-SEM) images revealed that the cellulose-stabilized Pd/Fe NPs were smaller and more uniform than the bare-Pd/Fe NPs. X-ray diffractometer (XRD) and X-ray photoelectron spectroscopy (XPS) results suggested that cellulose coatings found on Pd/Fe NPs surfaces featured some antioxidation abilities, which followed the order of HPMC < PAC. Sedimentation tests demonstrated that the stabilizing power of PAC for Pd/Fe NPs was higher than that of HPMC. Fourier transfer infrared spectrometer (FTIR) results indicated that PAC molecules were bound to the Pd/Fe NPs surfaces by polar covalent bonds and hydrogen bonds, while HPMC molecules interacted with the nanoparticles by hydrogen bonds. Batch debromination test for BDE47 demonstrated that the catalytic debromination rate with cellulose-stabilized Pd/Fe NPs was higher than that with bare-Pd/Fe NPs during reaction period of 15 min. Overall, this study indicated that both celluloses are beneficial to forming smaller, more regular, stable and antioxidative Pd/Fe NPs, leading to higher debromination reactivity for BDE47 compared with the bare-Pd/Fe NPs. Therefore Pd/Fe NPs can be utilized as a promising remediation technology for the contaminated groundwater and soils.

  7. CO2 as a regulator for the controllable preparation of highly dispersed chitosan-supported Pd catalysts in ionic liquids.

    PubMed

    Xue, Zhimin; Sun, Xiaofu; Li, Zhonghao; Mu, Tiancheng

    2015-07-11

    A controllable synthetic route has been developed for the preparation of chitosan supported Pd catalysts in an ionic liquid, 1-butyl-3-methylimidazolium acetate ([Bmim]OAc), by using compressed CO2 as the anti-solvent and regulator. It was found that the dispersion of Pd particles on chitosan and the catalytic activity of the as-prepared catalysts for the hydrogenation of styrene could be tuned by changing the pressure of CO2.

  8. Simultaneous electrochemical detection of ascorbic acid, dopamine and uric acid based on graphene anchored with Pd-Pt nanoparticles.

    PubMed

    Yan, Jun; Liu, Shi; Zhang, Zhenqin; He, Guangwu; Zhou, Ping; Liang, Haiying; Tian, Lulu; Zhou, Xuemin; Jiang, Huijun

    2013-11-01

    Pd-Pt bimetallic nanoparticles anchored on functionalized reduced graphene oxide (RGO) nanomaterials were synthesized via a one-step in situ reduction process, in which Pt and Pd ions were first attached to poly(diallyldimethylammonium chloride) (PDDA) functionalized graphene oxide (GO) sheets, and then the encased metal ions and GO were subjected to simultaneous reduction by ethylene glycol. The as-prepared Pd3Pt1/PDDA-RGO nanocomposites were characterized by transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy and electrochemical methods. In addition, an electrochemical sensor based on the graphene nanocomposites was fabricated for the simultaneous detection of ascorbic acid (AA), dopamine (DA) and uric acid (UA) in their ternary mixture. Three well-separated voltammetric peaks along with remarkable increasing electro-oxidation currents were obtained in differential pulse voltammetry (DPV) measurements. Under the optimized conditions, there were linear relationships between the peak currents and the concentrations in the range of 40-1200 μM for AA, 4-200 μM for DA and 4-400 μM for UA, with the limit of detection (LOD) (based on S/N=3) of 0.61, 0.04 and 0.10 μM for AA, DA and UA, respectively. This improved electrochemical performance can be attributed to the synergistic effect of metallic nanoparticles and RGO and the combination of the bimetallic nanoparticles. Furthermore, the practical electroanalytical utility of the sensor was demonstrated by the determination of AA, DA and together with UA in human urine and blood serum samples with satisfactory results. Copyright © 2013 Elsevier B.V. All rights reserved.

  9. Atomic-level Pd-Pt alloying and largely enhanced hydrogen-storage capacity in bimetallic nanoparticles reconstructed from core/shell structure by a process of hydrogen absorption/desorption.

    PubMed

    Kobayashi, Hirokazu; Yamauchi, Miho; Kitagawa, Hiroshi; Kubota, Yoshiki; Kato, Kenichi; Takata, Masaki

    2010-04-28

    We have achieved the creation of a solid-solution alloy where Pd and Pt are homogeneously mixed at the atomic level, by a process of hydrogen absorption/desorption as a trigger for core (Pd)/shell (Pt) nanoparticles. The structural change from core/shell to solid solution has been confirmed by in situ powder X-ray diffraction, energy dispersive spectra, solid-state (2)H NMR measurement, and hydrogen pressure-composition isotherms. The successfully obtained Pd-Pt solid-solution nanoparticles with a Pt content of 8-21 atom % had a higher hydrogen-storage capacity than Pd nanoparticles. Moreover, the hydrogen-storage capacity of Pd-Pt solid-solution nanoparticles can be tuned by changing the composition of Pd and Pt.

  10. Pd nanoparticles encapsulated in magnetic carbon nanocages: an efficient nanoenzyme for the selective detection and multicolor imaging of cancer cells

    NASA Astrophysics Data System (ADS)

    Chen, Gaosong; Song, Jingjing; Zhang, Haoli; Jiang, Yuntian; Liu, Weisheng; Zhang, Wei; Wang, Baodui

    2015-08-01

    Rapid and simple molecular recognition based techniques for the identification of the subtypes of cancer cells are essential in molecular medicine. However, improving the sensitivity and accuracy of the early diagnosis of this disease remains a major challenge. Herein, we develop a novel approach for the in situ growth of palladium nanoparticles in magnetic carbon nanocages (PdNPs/MCNCs). The confined Pd NPs, which have excellent dispersion in magnetic carbon nanocages, show superior catalytic performance for the cleavage reaction of N-butyl-4-NHAlloc-1,8-naphthalimide (NNPH), thereby producing significant changes in both color (from colorless to jade-green) and fluorescence (from blue to green) through the ICT process. Based on the abovementioned results, a novel sensing platform utilizing the PdNPs/MCNC nanocatalyst as an artificial enzyme and NNPH as a fluorescent and color change reporter molecule for the multicolor imaging and colorimetric detection of cancer cells was developed. We envision that this nanomaterial can be used as a power tool for a wide range of potential applications in biotechnology and medicine.Rapid and simple molecular recognition based techniques for the identification of the subtypes of cancer cells are essential in molecular medicine. However, improving the sensitivity and accuracy of the early diagnosis of this disease remains a major challenge. Herein, we develop a novel approach for the in situ growth of palladium nanoparticles in magnetic carbon nanocages (PdNPs/MCNCs). The confined Pd NPs, which have excellent dispersion in magnetic carbon nanocages, show superior catalytic performance for the cleavage reaction of N-butyl-4-NHAlloc-1,8-naphthalimide (NNPH), thereby producing significant changes in both color (from colorless to jade-green) and fluorescence (from blue to green) through the ICT process. Based on the abovementioned results, a novel sensing platform utilizing the PdNPs/MCNC nanocatalyst as an artificial enzyme and NNPH

  11. Supported Pd nanoclusters with enhanced hydrogen spillover for NOx removal via H2-SCR: the elimination of "volcano-type" behaviour.

    PubMed

    Peng, Zhezhe; Li, Zongyuan; Liu, Yun-Quan; Yan, Shuai; Tong, Jianing; Wang, Duo; Ye, Yueyuan; Li, Shuirong

    2017-05-30

    A rational design of a Pd catalyst with highly dispersed Pd nanoclusters on an Al doped ceria-based oxide for low temperature selective catalytic reduction of NOx by hydrogen with excess O2 was achieved. The supported Pd nanocluster shows a high hydrogen spillover ability and a NOx conversion of >84% within 100-300 °C.

  12. A general mechanism for stabilizing the small sizes of precious metal nanoparticles on oxide supports

    SciTech Connect

    Li, Wei-Zhen; Kovarik, Libor; Mei, Donghai; Engelhard, Mark H.; Gao, Feng; Liu, Jun; Wang, Yong; Peden, Charles HF

    2014-09-02

    We recently discovered that MgAl2O4 spinel {111} nano-facets optimally stabilize the small sizes of platinum nanoparticles even after severe high temperature aging treatments. Here we report the thermal stabilities of other precious metals with various physical and chemical properties on the MgAl2O4 spinel {111} facets, providing important new insights into the stabilization mechanisms. Besides Pt, Rh and Ir can also be successfully stabilized as small (1-3 nm) nanoparticles and even as single atomic species after extremely severe (800 °C, 1 week) oxidative aging. However, other metals either aggregate (Ru, Pd, Ag, and Au) or sublimate (Os) even during initial catalyst synthesis. On the basis of ab initio theoretical calculations and experimental observations, we rationalize that the exceptional stabilization originates from lattice matching, and the correspondingly strong attractive interactions at interfaces between the spinel {111} surface oxygens and epitaxial metals\\metal oxides. On this basis, design principles for catalyst support oxide materials that are capable in stabilizing precious metals are proposed.

  13. Enhancing the cyclability of Li-O2 batteries using PdM alloy nanoparticles anchored on nitrogen-doped reduced graphene as the cathode catalyst

    NASA Astrophysics Data System (ADS)

    Leng, Limin; Li, Jing; Zeng, Xiaoyuan; Song, Huiyu; Shu, Ting; Wang, Haishui; Liao, Shijun

    2017-01-01

    An efficient ORR/OER catalyst was developed by anchoring highly dispersed bimetallic PdM (M = Fe, Co, Ni) alloy nanoparticles on nitrogen-doped reduced graphene oxide (N-rGO). This new type of catalyst exhibited excellent ORR/OER activity, and the addition of transition metals also significantly improved catalytic stability, with the catalyst containing Fe (PdFe/N-rGO) exhibiting the best stability. A battery using this PdFe/N-rGO catalyst was capable of long-term stable cycling for 400 cycles (2000 h) with a limited capacity of 1000 mAh g-1 at 400 mA g-1, which was much longer than a battery with Pd/N-rGO as the catalyst (only 80 cycles, 400 h). We attribute the high performance of these catalysts to the high surface area of N-rGO, the anchoring of highly dispersed Pd alloy nanoparticles, and the prevention of Pd alloy nanoparticle aggregation and dissolution by the presence of the transition metals.

  14. Monodisperse Ag/Pd core/shell nanoparticles assembled on reduced graphene oxide as highly efficient catalysts for the transfer hydrogenation of nitroarenes.

    PubMed

    Metin, Önder; Can, Hasan; Şendil, Kıvılcım; Gültekin, Mehmet Serdar

    2017-07-15

    Addressed herein is a facile seed-mediated synthesis of Ag/Pd core/shell nanoparticles (NPs) and their assembly on reduced graphene oxide (rGO) to catalyze the transfer hydrogenation of nitroarenes to anilines using ammonia borane (AB) as a hydrogen donor under ambient conditions. Monodisperse Ag/Pd core/shell NPs with controllable Pd shell-thickness were synthesized by the means of thermal decomposition of palladium(II) bromide over as-prepared Ag NPs in the mixture of oleylamine and oleic acid at 220°C. As-synthesized Ag/Pd core/shell NPs were characterized by TEM, HR-TEM, XRD, XPS, UV-Vis spectroscopy and ICP-MS and then they were assembled on reduced graphene oxide (rGO). Next, rGO@Ag/Pd catalysts were tested in the transfer hydrogenation of nitroarenes in which ammonia borane (AB) was used as a hydrogen donor at room temperature. It was demonstrated that the thickness of the Pd shell has a significant effect on the catalytic activity of rGO@Ag/Pd catalysts and the 1.75nm Pd shell provided the highest performance in the transfer hydrogenation reactions. The rGO@Ag/Pd catalyzed transfer hydrogenation reactions were tested over a variety of nitroarenes (total 16 examples) and they were all converted to the corresponding aniline derivatives with high yields in 5-15min under ambient conditions. Copyright © 2017 Elsevier Inc. All rights reserved.

  15. Synergistic catalysis of metal-organic framework-immobilized Au-Pd nanoparticles in dehydrogenation of formic acid for chemical hydrogen storage.

    PubMed

    Gu, Xiaojun; Lu, Zhang-Hui; Jiang, Hai-Long; Akita, Tomoki; Xu, Qiang

    2011-08-10

    Bimetallic Au-Pd nanoparticles (NPs) were successfully immobilized in the metal-organic frameworks (MOFs) MIL-101 and ethylenediamine (ED)-grafted MIL-101 (ED-MIL-101) using a simple liquid impregnation method. The resulting composites, Au-Pd/MIL-101 and Au-Pd/ED-MIL-101, represent the first highly active MOF-immobilized metal catalysts for the complete conversion of formic acid to high-quality hydrogen at a convenient temperature for chemical hydrogen storage. Au-Pd NPs with strong bimetallic synergistic effects have a much higher catalytic activity and a higher tolerance with respect to CO poisoning than monometallic Au and Pd counterparts. © 2011 American Chemical Society

  16. Titania-supported silver-based bimetallic nanoparticles as photocatalysts.

    PubMed

    Barakat, M A; Al-Hutailah, R I; Hashim, M H; Qayyum, E; Kuhn, J N

    2013-06-01

    Photocatalytic process has shown recently a great potential as an environmental friendly and clean remediation technology for organic pollutants in wastewater. This work described the synthesis of silver-based bimetallic nanoparticles using colloid chemistry and the subsequent immobilization onto titania to form composite photocatalytic materials (titania-supported Ag-Pt nanoparticles). The photocatalysts were characterized by X-ray diffraction, electron microscopy, and nitrogen physisorption. The catalytic activity of the photocatalysts was evaluated by photocatalytic degradation of phenol and 2-chlorophenol (2-CP) in synthetic wastewater solutions. The photocatalytic processes were conducted in a batch photoreactor containing appropriate solutions of phenol and 2-CP with UV irradiation of 450 W. UV-visible spectrophotometer was used for analyzing the concentration of phenol and 2-CP in solutions. Parameters affecting the photocatalytic process such as the solution pH, phenol and 2-CP concentrations, and catalyst concentration were investigated. The results obtained revealed that TiO(2)-supported Ag/Pt nanoparticles showed a higher activity for UV-photocatalytic degradation of both phenol and 2-CP pollutants in the solution (as compared to the plain rutile TiO(2)). The photodegradation processes were optimized by the 0.5-g/L catalyst with a pollutant concentration of 50 mg/L for all the samples. Complete degradation for both phenol and 2-CP was achieved after 120 min.

  17. All-metal mesoporous nanocolloids: solution-phase synthesis of core-shell Pd@Pt nanoparticles with a designed concave surface.

    PubMed

    Ataee-Esfahani, Hamed; Imura, Masataka; Yamauchi, Yusuke

    2013-12-16

    Colloidal Pd@Pt nanoparticles with uniform mesopores can be synthesized in one step by a facile solution-phase method involving slow reduction of metal species in strong acidic media. In this system, F127 micelles can directly act as a template to form the mesopores in the product, and the greater reducibility of the Pd species leads to the desired core-shell Pd@Pt nanocolloids. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Support nanostructure boosts oxygen transfer to catalytically active platinum nanoparticles.

    PubMed

    Vayssilov, Georgi N; Lykhach, Yaroslava; Migani, Annapaola; Staudt, Thorsten; Petrova, Galina P; Tsud, Nataliya; Skála, Tomáš; Bruix, Albert; Illas, Francesc; Prince, Kevin C; Matolín, Vladimír; Neyman, Konstantin M; Libuda, Jörg

    2011-04-01

    Interactions of metal particles with oxide supports can radically enhance the performance of supported catalysts. At the microscopic level, the details of such metal-oxide interactions usually remain obscure. This study identifies two types of oxidative metal-oxide interaction on well-defined models of technologically important Pt-ceria catalysts: (1) electron transfer from the Pt nanoparticle to the support, and (2) oxygen transfer from ceria to Pt. The electron transfer is favourable on ceria supports, irrespective of their morphology. Remarkably, the oxygen transfer is shown to require the presence of nanostructured ceria in close contact with Pt and, thus, is inherently a nanoscale effect. Our findings enable us to detail the formation mechanism of the catalytically indispensable Pt-O species on ceria and to elucidate the extraordinary structure-activity dependence of ceria-based catalysts in general.

  19. Porous Nanoparticle Supported Lipid Bilayers (Protocells) as Delivery Vehicles

    PubMed Central

    Liu, Juewen; Stace-Naughton, Alison; Jiang, Xingmao; Brinker, C. Jeffrey

    2009-01-01

    Mixing liposomes with hydrophilic particles will induce fusion of the liposome onto the particle surface. Such supported bilayers have been extensively studied as a model for the cell membrane, while its application in drug delivery has not been pursued. In this communication, we report the use of phospholipids to achieve synergistic loading and encapsulating of a fluorescent dye (calcein) in mesoporous silica nanoparticles, and its delivery into mammalian cells. We found that cationic lipid DOTAP provides the highest calcein loading with the concentration inside silica ∼110× higher than that in the solution under experimental conditions. Compared to some other nanoparticle systems, protocells provide a simple construct for loading, sealing, delivering and releasing, and should serve as a useful system in nanomedicine. PMID:19173660

  20. Folic acid-functionalized polyethylenimine superparamagnetic iron oxide nanoparticles as theranostic agents for magnetic resonance imaging and PD-L1 siRNA delivery for gastric cancer.

    PubMed

    Luo, Xin; Peng, Xia; Hou, Jingying; Wu, Shuyun; Shen, Jun; Wang, Lingyun

    2017-01-01

    Programmed death ligand-1 (PD-L1), which is highly expressed in gastric cancers, interacts with programmed death-1 (PD-1) on T cells and is involved in T-cell immune resistance. To increase the therapeutic safety and accuracy of PD-1/PD-L1 blockade, RNA interference through targeted gene delivery was performed in our study. We developed folic acid (FA)- and disulfide (SS)-polyethylene glycol (PEG)-conjugated polyethylenimine (PEI) complexed with superparamagnetic iron oxide Fe3O4 nanoparticles (SPIONs) as a siRNA-delivery system for PD-L1 knockdown. The characterization, binding ability, cytotoxicity, transfection efficiency, and cellular internalization of the polyplex were determined. At nitrogen:phosphate (N:P) ratios of 10 or above, the FA-PEG-SS-PEI-SPIONs bound to PD-L1 siRNA to form a polyplex with a diameter of approximately 120 nm. Cell-viability assays showed that the polyplex had minimal cytotoxicity at low N:P ratios. The FA-conjugated polyplex showed higher transfection efficiency and cellular internalization in the folate receptor-overexpressing gastric cancer cell line SGC-7901 than a non-FA-conjugated polyplex. Subsequently, we adopted the targeted FA-PEG-SS-PEI-SPION/siRNA polyplexes at an N:P ratio of 10 for function studies. Cellular magnetic resonance imaging (MRI) showed that the polyplex could also act as a T2-weighted contrast agent for cancer MRI. Furthermore, one of four PD-L1 siRNAs exhibited effective PD-L1 knockdown in PD-L1-overexpressing SGC-7901. To determine the effects of the functionalized polyplex on T-cell function, we established a coculture model of activated T cells and SGC-7901 cells and demonstrated changes in secreted cytokines. Our findings highlight the potential of this class of multifunctional theranostic nanoparticles for effective targeted PD-L1-knockdown therapy and MRI diagnosis in gastric cancers.

  1. Palladium Nanoparticles Supported on Nitrogen and Sulfur Dual-Doped Graphene as Highly Active Electrocatalysts for Formic Acid and Methanol Oxidation.

    PubMed

    Zhang, Xin; Zhu, Jixin; Tiwary, Chandra Sekhar; Ma, Zhongyuan; Huang, Huajie; Zhang, Jianfeng; Lu, Zhiyong; Huang, Wei; Wu, Yuping

    2016-05-04

    Optimized designing of highly active electrocatalysts has been regarded as a critical point to the development of portable fuel cell systems with high power density. Here we report a facile and cost-effective strategy to synthesis of ultrafine Pd nanoparticles (NPs) supported on N and S dual-doped graphene (NS-G) nanosheets as multifunctional electrocatalysts for both direct formic acid fuel cell and direct methanol fuel cell. The incorporation of N and S atoms into graphene frameworks is achieved by a thermal treatment process, followed by the controlled growth of Pd NPs via a solvothermal approach. Owning to the unique structural features as well as the strong synergistic effects, the resulting Pd/NS-G hybrid exhibits outstanding electrocatalytic performance toward both formic acid and methanol electro-oxidation, such as higher anodic peak current densities and more exceptional catalytic stability than those of Pd/Vulcan XC-72R and Pd/undoped graphene catalysts. These findings open up new possibility in the construction of advanced Pd-based catalysts, which is conducive to solving the current bottlenecks of fuel cell technologies.

  2. Surface Atomic Structure and Functionality of Metallic Nanoparticles: A Case Study of Au–Pd Nanoalloy Catalysts

    DOE PAGES

    Petkov, Valeri; Prasai, Binay; Shastri, Sarvjit; ...

    2017-03-23

    The surface atomic structure of metallic nanoparticles (NPs) plays a key role in shaping their physicochemical properties and response to external stimuli. Not surprisingly, current research increasingly focuses on exploiting its prime characteristics, including the amount, location, coordination, and electronic configuration of distinct surface atomic species, as tunable parameters for improving the functionality of metallic NPs in practical applications. The effort requires clear understanding of the extent to which changes in each of these characteristics would contribute to achieving the targeted functionality. This, in the first place, requires good knowledge of the actual surface of metallic NPs at atomic level.more » Through a case study on Au–Pd nanoalloy catalysts of industrial and environmental importance, we demonstrate that the surface atomic structure of metallic NPs can be determined in good detail by resonant high-energy X-ray diffraction (HE-XRD). Furthermore, using our experimental surface structure and CO oxidation activity data, we shed new light on the elusive origin of the remarkable catalytic synergy between surface Au and Pd atoms in the nanoalloys. In particular, we show that it arises from the formation of a specific “skin” on top of the nanoalloys that involves as many unlike, i.e., Au–Pd and Pd–Au, atomic pairs as possible given the overall chemical composition of the NPs. Moreover, unlike atoms from the “skin” interact strongly, including both changing their size and electronic structure in inverse proportions. That is, Au atoms shrink and acquire a partial positive charge of 5d-character whereas Pd atoms expand and become somewhat 4d-electron deficient. Accordingly, the reactivity of Au increases whereas Pd atoms become less reactive, as compared to atoms at the surface of pure Au and Pd NPs, respectively. Ultimately, this renders Au–Pd alloy NPs superb catalysts for CO oxidation reaction over a broad range of alloy

  3. Facile synthesis of hierarchical dendritic PtPd nanogarlands supported on reduced graphene oxide with enhanced electrocatalytic properties

    NASA Astrophysics Data System (ADS)

    Li, Shan-Shan; Zheng, Jie-Ning; Ma, Xiaohong; Hu, Yuan-Yuan; Wang, Ai-Jun; Chen, Jian-Rong; Feng, Jiu-Ju

    2014-05-01

    A simple and facile method is developed for one-pot preparation of hierarchical dendritic PtPd nanogarlands supported on reduced graphene oxide (PtPd/RGO) at room temperature, without using any seed, organic solvent, or complex apparatus. It is found that octylphenoxypolyethoxyethanol (NP-40) as a soft template and its amount are critical to the formation of PtPd garlands. The as-prepared nanocomposites are further applied to methanol and ethanol oxidation with significantly enhanced electrocatalytic activity and better stability in alkaline media.A simple and facile method is developed for one-pot preparation of hierarchical dendritic PtPd nanogarlands supported on reduced graphene oxide (PtPd/RGO) at room temperature, without using any seed, organic solvent, or complex apparatus. It is found that octylphenoxypolyethoxyethanol (NP-40) as a soft template and its amount are critical to the formation of PtPd garlands. The as-prepared nanocomposites are further applied to methanol and ethanol oxidation with significantly enhanced electrocatalytic activity and better stability in alkaline media. Electronic supplementary information (ESI) available: Experimental section, Fig. S1-S12 and Tables S1 and S2. See DOI: 10.1039/c3nr06808k

  4. Acetylene hydrogenation on anatase TiO2(101) supported Pd4 cluster: oxygen deficiency effect.

    PubMed

    Yang, Jie; Cao, Li-Xin; Wang, Gui-Chang

    2012-07-01

    Acetylene hydrogenation on both the perfect and oxygen defective anatase TiO(2)(101) surfaces supported Pd(4) cluster has been studied using density functional theory calculations with a Hubbard U correction (DFT + U). The adsorbed Pd(4) cluster on the perfect surface prefers to form a tetrahedral structure, while it likely moves to the oxygen defective site to form a distorted tetrahedral structure by removing a bridging oxygen atom. For the defective surface, it exhibits a stronger ability to capture Pd(4) cluster as charge transfer is significantly performed due to the oxygen deficiency. Moreover, it is found that the oxygen defective surface shows higher activity for acetylene hydrogenation, and the possible reason may lie in the weaker adsorption strength between the Pd cluster and the adsorbed molecules on the defective surface as compared to the case on the perfect surface.

  5. Intracellular biogenic silver nanoparticles for the generation of carbon supported antiviral and sustained bactericidal agents.

    PubMed

    Vijayakumar, P S; Prasad, B L V

    2009-10-06

    Intracellular silver nanoparticles produced by exposing silver ions to the fungus Aspergillus ochraceus were heat-treated in nitrogen environment to yield silver nanoparticles embedded in carbonaceous supports. This carbonaceous matrix embedded silver nanoparticles showed antimicrobial properties against both bacteria (Gram-positive and Gram-negative) and virus (M 13 phage virus). The bactericidal effects were noticed even after washing and repeated exposure of these carbon supported silver nanoparticles to fresh bacterial cultures, revealing their sustained activity.

  6. Preparation of ceria-zirconia by modified coprecipitation method and its supported Pd-only three-way catalyst.

    PubMed

    Lan, Li; Chen, Shanhu; Cao, Yi; Zhao, Ming; Gong, Maochu; Chen, Yaoqiang

    2015-07-15

    A CeO2-ZrO2 compound with mixed phase composition (CZ4) was prepared by modified co-precipitation method, and for comparison, single-phase Ce(0.2)Zr(0.8)O2, Ce(0.5)Zr(0.5)O2 and Ce(0.8)Zr(0.2)O2 were synthesized via simultaneous co-precipitation method. The textural, structural and redox properties, together with the catalytic performance of the supported Pd-only three-way catalysts were investigated systematically. The results revealed that the generation of numerous interface sites in Pd/CZ4 due to its mixed phase composition (as confirmed by TEM observation) had a positive influence on modifying its structural, redox properties and thermal stability. The XRD and Raman results revealed that the highest structural stability was obtained by Pd/CZ4 with negligible lattice variation and slightest grain growth after aging treatment. The XPS analysis demonstrated that the compositional heterogeneity of Pd/CZ4 could facilitate the formation of Ce(3+), and was beneficial to preserve high dispersion of Pd as well as maintain Pd at a more oxidized state. The H2-TPR and oxygen storage capacity measurements indicated that Pd/CZ4 possessed highest reduction ability as well as largest oxygen storage capacity regardless of thermal aging treatment. And consequently Pd/CZ4 exhibited improved three-way catalytic activity compared with the catalysts supported on single-phase Ce(x)Zr(1-x)O2 both before and after thermal aging treatment. Copyright © 2015 Elsevier Inc. All rights reserved.

  7. Understanding the Solution and Solid-State Structures of Pd and Pt PSiP Pincer-Supported Hydrides.

    PubMed

    Suh, Hee-Won; Balcells, David; Edwards, Alison J; Guard, Louise M; Hazari, Nilay; Mader, Elizabeth A; Mercado, Brandon Q; Repisky, Michal

    2015-12-07

    The PSiP pincer-supported complex ((Cy)PSiP)PdH [(Cy)PSiP = Si(Me)(2-PCy2-C6H4)2] has been implicated as a crucial intermediate in carboxylation of both allenes and boranes. At this stage, however, there is uncertainty regarding the exact structure of ((Cy)PSiP)PdH, especially in solution. Previously, both a Pd(II) structure with a terminal Pd hydride and a Pd(0) structure featuring an η(2)-silane have been proposed. In this contribution, a range of techniques were used to establish that ((Cy)PSiP)PdH and the related Pt species, ((Cy)PSiP)PtH, are true M(II) hydrides in both the solid state and solution. The single-crystal X-ray structures of ((Cy)PSiP)MH (M = Pd and Pt) and the related species ((iPr)PSiP)PdH [(iPr)PSiP = Si(Me)(2-P(i)Pr2-C6H4)2] are in agreement with the presence of a terminal metal hydride, and the exact geometry of ((Cy)PSiP)PtH was confirmed using neutron diffraction. The (1)H and (29)Si{(1)H}NMR chemical shifts of ((Cy)PSiP)MH (M = Pd and Pt) are consistent with a structure containing a terminal hydride, especially when compared to the chemical shifts of related pincer-supported complexes. In fact, in this work, two general trends relating to the (1)H NMR chemical shifts of group 10 pincer-supported terminal hydrides were elucidated: (i) the hydride shift moves downfield from Ni to Pd to Pt and (ii) the hydride shift moves downfield with more trans-influencing pincer central donors. DFT calculations indicate that structures containing a M(II) hydride are lower in energy than the corresponding η(2)-silane isomers. Furthermore, the calculated NMR chemical shifts of the M(II) hydrides using a relativistic four-component methodology incorporating all significant scalar and spin-orbit corrections are consistent with those observed experimentally. Finally, in situ X-ray absorption spectroscopy (XAS) was used to provide further support that ((Cy)PSiP)MH exist as M(II) hydrides in solution.

  8. PD-PK evaluation of freeze-dried atorvastatin calcium-loaded poly-ε-caprolactone nanoparticles.

    PubMed

    Ahmed, Iman S; El-Hosary, Rania; Shalaby, Samia; Abd-Rabo, Marwa M; Elkhateeb, Dalia G; Nour, Samia

    2016-05-17

    In this work lyophilized poly-ε-caprolactone nanoparticles (NPs) loaded with atorvastatin calcium (AC) were developed in an attempt to improve the in-vivo performance of AC following oral administration. The individual and combined effects of several formulation variables were previously investigated using step-wise full factorial designs in order to produce optimized AC-NPs with predetermined characteristics including particle size, drug loading capacity, drug release profile and physical stability. Four optimized formulations were further subjected in this work to lyophilization to promote their long-term physical stability and were fully characterized. The pharmacodynamics (PD)/pharmacokinetics (PK) properties of two optimized freeze-dried AC-NPs formulations showing acceptable long-term stability were determined and compared to a marketed AC immediate release tablet (Lipitor(®)) in albino rats. PD results revealed that the two tested formulations were equally effective in reducing low density lipoproteins (LDL) and triglycerides (TG) levels when given in reduced doses compared to Lipitor(®) and showed no adverse effects. PK results, on the other hand, revealed that the two freeze-dried AC-NPs formulations were of significantly lower bioavailability compared to Lipitor(®). Taken together the PD and PK results demonstrate that the improved efficacy obtained at reduced doses from the freeze-dried AC-NPs could be due to increased concentration of AC in the liver rather than in the plasma.

  9. Combinatorial PtSnM (M = Fe, Ni, Ru and Pd) nanoparticle catalyst library toward ethanol electrooxidation

    NASA Astrophysics Data System (ADS)

    Almeida, T. S.; Van Wassen, A. R.; VanDover, R. B.; de Andrade, A. R.; Abruña, H. D.

    2015-06-01

    Electrode arrays containing 91 combinations of Pt-Sn-M (M = Fe, Ni, Pd, and Ru) were prepared by borohydride reduction of aqueous metal salts on carbon paper, and screened by fluorescence assay for activity as ethanol electrooxidation catalysts. Catalysts that showed high activity for this reaction were identified as being Pt(80)Sn(10)Fe(10), Pt(80)Sn(10)Ni(10), Pt(70)Sn(20)Pd(10), and Pt(70)Sn(10)Ru(20) (numbers in parenthesis indicate atomic percent). These were significantly more active than Pt or PtSn catalysts, also present in the electrode arrays. These 4 compositions were synthesized as nanoparticles and characterized physically and electrochemically. X-ray diffraction showed a Pt face-centered cubic (fcc) structure with an average crystallite size of about 2.0 nm for all catalysts. The electrochemical tests for the oxidation of ethanol revealed excellent electrocatalytic activity and single cell (fuel cell) power density for all four catalyst formulations. Fe-containing catalysts exhibited the highest activity (13 A gPt-1) and single-cell performance (50 mW cm-2) followed by Ni- and Pd-containing materials with similar results; electrocatalytic activity around 10 A gPt-1 and power densities of 43 mW cm-2. The lowest performance was observed for the Ru-containing catalyst. However, its single-cell performance (30 mW cm-2) was still comparable to that of the commercial PtSn-Etek electrocatalyst.

  10. Pd nanoparticles encapsulated in magnetic carbon nanocages: an efficient nanoenzyme for the selective detection and multicolor imaging of cancer cells.

    PubMed

    Chen, Gaosong; Song, Jingjing; Zhang, Haoli; Jiang, Yuntian; Liu, Weisheng; Zhang, Wei; Wang, Baodui

    2015-09-14

    Rapid and simple molecular recognition based techniques for the identification of the subtypes of cancer cells are essential in molecular medicine. However, improving the sensitivity and accuracy of the early diagnosis of this disease remains a major challenge. Herein, we develop a novel approach for the in situ growth of palladium nanoparticles in magnetic carbon nanocages (PdNPs/MCNCs). The confined Pd NPs, which have excellent dispersion in magnetic carbon nanocages, show superior catalytic performance for the cleavage reaction of N-butyl-4-NHAlloc-1,8-naphthalimide (NNPH), thereby producing significant changes in both color (from colorless to jade-green) and fluorescence (from blue to green) through the ICT process. Based on the abovementioned results, a novel sensing platform utilizing the PdNPs/MCNC nanocatalyst as an artificial enzyme and NNPH as a fluorescent and color change reporter molecule for the multicolor imaging and colorimetric detection of cancer cells was developed. We envision that this nanomaterial can be used as a power tool for a wide range of potential applications in biotechnology and medicine.

  11. MoS2-supported gold nanoparticle for CO hydrogenation

    NASA Astrophysics Data System (ADS)

    Rawal, Takat B.; Le, Duy; Rahman, Talat S.

    2017-10-01

    Employing dispersion-corrected density functional theory, we examine the geometry, electronic structure, and reactivity of 13-atom Au nanoparticle supported on defect-laden single-layer MoS2. The planar structure of Au13 favored in isolated phase, transforms into the three-dimensional structure when supported on MoS2. We find that charge is transferred from MoS2 to Au13, and that the electron density is also distributed away from the Au13/MoS2 interfacial region—making Au sites away from the interface catalytically active. Owing to effect of the support, the Au d states become narrower, and the frontier states appear close to the Fermi level. Consequently, in contrast to the reactivity of Au13/TiO2 toward methanol decomposition, Au13/MoS2 offers excellent activity toward methanol synthesis, as demonstrated here, via CO hydrogenation.

  12. Pd and Pt-Ru anode electrocatalysts supported on multi-walled carbon nanotubes and their use in passive and active direct alcohol fuel cells with an anion-exchange membrane (alcohol = methanol, ethanol, glycerol)

    NASA Astrophysics Data System (ADS)

    Bambagioni, Valentina; Bianchini, Claudio; Marchionni, Andrea; Filippi, Jonathan; Vizza, Francesco; Teddy, Jacques; Serp, Philippe; Zhiani, Mohammad

    Palladium and platinum-ruthenium nanoparticles supported on multi-walled carbon nanotubes (MWCNT) are prepared by the impregnation-reduction procedure. The materials obtained, Pd/ MWCNT and Pt-Ru/ MWCNT, are characterized by TEM, ICP-AES and XRPD. Electrodes coated with Pd/ MWCNT are scrutinized for the oxidation of methanol, ethanol or glycerol in 2 M KOH solution in half cells. The catalyst is very active for the oxidation of all alcohols, with glycerol providing the best performance in terms of specific current density and ethanol showing the lowest onset potential. Membrane-electrode assemblies have been fabricated using Pd/ MWCNT anodes, commercial cathodes and anion-exchange membrane and evaluated in both single passive and active direct alcohol fuel cells fed with aqueous solutions of 10 wt.% methanol, 10 wt.% ethanol or 5 wt.% glycerol. Pd/ MWCNT exhibits unrivalled activity as anode electrocatalyst for alcohol oxidation. The analysis of the anode exhausts shows that ethanol is selectively oxidized to acetic acid, detected as acetate ion in the alkaline media of the reaction, while methanol yields carbonate and formate. A much wider product distribution, including glycolate, glycerate, tartronate, oxalate, formate and carbonate, is obtained from the oxidation of glycerol. The results obtained with Pt-Ru/ MWCNT anodes in acid media are largely inferior to those provided by Pd/ MWCNT electrodes in alkaline media.

  13. Vapor phase synthesis and characterization of bimetallic alloy and supported nanoparticle catalysts

    NASA Astrophysics Data System (ADS)

    Abdelsayed, V.; Saoud, K. M.; El-Shall, M. Samy

    2006-08-01

    The laser vaporization controlled condensation (LVCC) technique coupled with a differential mobility analyzer (DMA) is used to synthesize size-selected alloy nanoparticles and nanoparticle catalyst systems. The formation of Au-Ag alloy nanoparticles is concluded from the observation of only one plasmon band. The maximum of the plasmon absorption is found to vary linearly with the gold mole fraction. For the Au-Pd system, the XRD data confirms the formation of the alloy nanoparticles with no evidence of any of the pure components. The Au/CeO2 nanoparticle catalyst prepared by the LVCC method is a promising catalyst for low temperature CO oxidation due to its high activity and stability.

  14. Scalable Synthesis of Ag Networks with Optimized Sub-monolayer Au-Pd Nanoparticle Covering for Highly Enhanced SERS Detection and Catalysis

    NASA Astrophysics Data System (ADS)

    Li, Tianyu; Vongehr, Sascha; Tang, Shaochun; Dai, Yuming; Huang, Xiao; Meng, Xiangkang

    2016-11-01

    Highly porous tri-metallic AgxAuyPdz networks with a sub-monolayer bimetallic Au-Pd nanoparticle coating were synthesized via a designed galvanic replacement reaction of Ag nanosponges suspended in mixed solutions of HAuCl4 and K2PdCl4. The resulting networks’ ligaments have a rough surface with bimetallic nanoparticles and nanopores due to removal of Ag. The surface morphology and composition are adjustable by the temperature and mixed solutions’ concentration. Very low combined Au and Pd atomic percentage (1‑x) where x is atomic percentage of Ag leads to sub-monolayer nanoparticle coverings allowing a large number of active boundaries, nanopores, and metal-metal interfaces to be accessible. Optimization of the Au/Pd atomic ratio y/z obtains large surface-enhanced Raman scattering detection sensitivity (at y/z = 5.06) and a higher catalytic activity (at y/z = 3.55) toward reduction reactions as benchmarked with 4-nitrophenol than for most bimetallic catalysts. Subsequent optimization of x (at fixed y/z) further increases the catalytic activity to obtain a superior tri-metallic catalyst, which is mainly attributed to the synergy of several aspects including the large porosity, increased surface roughness, accessible interfaces, and hydrogen absorption capacity of nanosized Pd. This work provides a new concept for scalable synthesis and performance optimization of tri-metallic nanostructures.

  15. Scalable Synthesis of Ag Networks with Optimized Sub-monolayer Au-Pd Nanoparticle Covering for Highly Enhanced SERS Detection and Catalysis

    PubMed Central

    Li, Tianyu; Vongehr, Sascha; Tang, Shaochun; Dai, Yuming; Huang, Xiao; Meng, Xiangkang

    2016-01-01

    Highly porous tri-metallic AgxAuyPdz networks with a sub-monolayer bimetallic Au-Pd nanoparticle coating were synthesized via a designed galvanic replacement reaction of Ag nanosponges suspended in mixed solutions of HAuCl4 and K2PdCl4. The resulting networks’ ligaments have a rough surface with bimetallic nanoparticles and nanopores due to removal of Ag. The surface morphology and composition are adjustable by the temperature and mixed solutions’ concentration. Very low combined Au and Pd atomic percentage (1−x) where x is atomic percentage of Ag leads to sub-monolayer nanoparticle coverings allowing a large number of active boundaries, nanopores, and metal-metal interfaces to be accessible. Optimization of the Au/Pd atomic ratio y/z obtains large surface-enhanced Raman scattering detection sensitivity (at y/z = 5.06) and a higher catalytic activity (at y/z = 3.55) toward reduction reactions as benchmarked with 4-nitrophenol than for most bimetallic catalysts. Subsequent optimization of x (at fixed y/z) further increases the catalytic activity to obtain a superior tri-metallic catalyst, which is mainly attributed to the synergy of several aspects including the large porosity, increased surface roughness, accessible interfaces, and hydrogen absorption capacity of nanosized Pd. This work provides a new concept for scalable synthesis and performance optimization of tri-metallic nanostructures. PMID:27845400

  16. Structural stability of 1100[degree]C heated Pd/k during absorption cycling in protium. [Palladium supported on kieselguhr

    SciTech Connect

    Fisher, I.A.

    1993-03-12

    Pd/k is a hydride forming packing material which is used in the Thermal Cycling Absorption Process (TCAP). Palladium is supported on kieselguhr to create a packing material which will provide adequate void space to prevent excessive pressure drops and flow restrictions. The use of unsupported palladium would result in blockage of columns and clogging of filters due to the small particle size of unsupported palladium hydride powder. During pilot scale demonstrations, it was noted that the Pd/k packing material had degraded causing severe flow restrictions within the TCAP column. A solution to the problem involved the heating of Pd/k at 1,110[degree]C to strengthen the packing material, and render it more resistant to breakdown. The 1, 100[degree]C heated Pd/k has been shown to be more resistant to mechanical breakdown than the Pd/k prior to heat treatment. Two primary modes of Pd/k particle degradation have been identified: mechanical breakdown caused by particle fluidization and degradation caused by absorption/desorption cycling. Absorption/desorption cycling causes the palladium particles within the packing to expanded and contract upon formation and decomposition of the hydride, respectively. This expansion and contraction causes large localized stresses within the packing material, which if these stresses can not be accommodated within the packing will cause the material to crack and degrade. The purpose of this report is to document the results of the absorption/desorption cycling of 1,100[degree]C heated Pd/k and compare these results to the results obtained from the absorption/desorption cycling of Pd/k which had not been heated at 1, 100[degree]C.

  17. Highly dispersed encapsulated AuPd nanoparticles on ordered mesoporous carbons for the direct synthesis of H2O2 from molecular oxygen and hydrogen.

    PubMed

    García, Tomás; Murillo, Ramón; Agouram, Said; Dejoz, Ana; Lázaro, María J; Torrente-Murciano, Laura; Solsona, Benjamín

    2012-05-28

    AuPd nanoparticles (<3 nm) have been encapsulated on the pores of a nanostructured CMK-3 carbon prepared by a nanocasting procedure. This material has been shown to be an excellent catalyst for the direct synthesis of hydrogen peroxide from molecular hydrogen and oxygen.

  18. Pd size effect on the gas sensing properties of Pd-loaded SnO2 in humid atmosphere.

    PubMed

    Ma, Nan; Suematsu, Koichi; Yuasa, Masayoshi; Shimanoe, Kengo

    2015-07-22

    Pd particles of different nanosizes were loaded on the SnO2 surface by using different Pd precursors for the purpose of investigating the Pd size effect on gas sensing properties in humid atmosphere. One kind of Pd-loaded SnO2 nanoparticle was characterized by smaller Pd particles (2.6 nm) with high dispersion, while another kind was characterized by larger Pd particles (5-10 nm) with low dispersion. It was found that both kinds of Pd on the SnO2 surface let the mainly adsorbed oxygen species change from O(-) to O(2-) in humid atmosphere at 350 °C. In addition, the water vapor poisoning effect on electric resistance and sensor response was greatly reduced by loading Pd. Interestingly, for the CO response at 350 °C, Pd-SnO2 with small Pd size showed almost constant sensor response with varying humidity (0.5-4 vol % H2O). While the CO response of Pd-SnO2 with large Pd size even increased with increasing amount of water vapor. Moreover, the former CO response was increased from 300 to 350 °C, but the later response decreased with increase in operating temperature. These behaviors were analyzed by temperature programed reduction (TPR) in H2 and CO atmospheres, and they were supported by the different catalytic activities of different nanosized Pd particles.

  19. Plasmonics: Heat transfer between metal nanoparticles and supporting nanolayers

    NASA Astrophysics Data System (ADS)

    Zhdanov, Vladimir P.; Zorić, Igor; Kasemo, Bengt

    2012-09-01

    Due to plasmon-related local field enhancement, metal nanoparticles can be used in conventional surface photochemistry and also in numerous applications, e.g., for optimization of the performance of thin film solar cells and photo-electrochemical cells employed for solar-to-fuel energy conversion. In the experimental model studies related to such cells, metal nanoparticles are located on or embedded into a 40-100 nm thick active photoabsorbing material (e.g., Si or Fe2O3), supported underneath by a ∼1 mm thick glass layer. We present general equations describing heat transport in the layered systems of this type. The equations contain the coefficients of heat transfer between different nanophases. Using the Debye model, we derive an analytical expression for these coefficients. Our calculations show that for the energy flux corresponding to solar light the overheating is practically negligible. In more conventional surface photochemistry, the effect may be more appreciable with increasing the energy flux and support thickness.

  20. Enhancing low-temperature activity and durability of Pd-based diesel oxidation catalysts using ZrO2 supports

    DOE PAGES

    Kim, Mi -Young; Kyriakidou, Eleni A.; Choi, Jae -Soon; ...

    2016-01-18

    In this study, we investigated the impact of ZrO2 on the performance of palladium-based oxidation catalysts with respect to low-temperature activity, hydrothermal stability, and sulfur tolerance. Pd supported on ZrO2 and SiO2 were synthesized for a comparative study. Additionally, in an attempt to maximize the ZrO2 surface area and improve sulfur tolerance, a Pd support with ZrO2-dispersed onto SiO2 was studied. The physicochemical properties of the catalysts were examined using ICP, N2 sorption, XRD, SEM, TEM, and NH3-, CO2-, and NOx-TPD. The activity of the Pd catalysts were measured from 60 to 600 °C in a flow of 4000 ppmmore » CO, 500 ppm NO, 1000 ppm C3H6, 4% O2, 5% H2O, and Ar balance. The Pd catalysts were evaluated in fresh, sulfated, and hydrothermally aged states. Overall, the ZrO2-containing catalysts showed considerably higher CO and C3H6 oxidation activity than Pd/SiO2 under the reaction conditions studied.« less

  1. Magnetic Carbon Supported Palladium Nanoparticles: An Efficient and Sustainable Catalyst for Hydrogenation Reactions

    EPA Science Inventory

    Magnetic carbon supported Pd catalyst has been synthesized via in situ generation of nanoferrites and incorporation of carbon from renewable cellulose via calcination; the catalyst can be used for the hydrogenation of alkenes and reduction of aryl nitro compounds.

  2. Magnetic Carbon Supported Palladium Nanoparticles: An Efficient and Sustainable Catalyst for Hydrogenation Reactions

    EPA Science Inventory

    Magnetic carbon supported Pd catalyst has been synthesized via in situ generation of nanoferrites and incorporation of carbon from renewable cellulose via calcination; the catalyst can be used for the hydrogenation of alkenes and reduction of aryl nitro compounds.

  3. Gallium-rich Pd-Ga phases as supported liquid metal catalysts

    NASA Astrophysics Data System (ADS)

    Taccardi, N.; Grabau, M.; Debuschewitz, J.; Distaso, M.; Brandl, M.; Hock, R.; Maier, F.; Papp, C.; Erhard, J.; Neiss, C.; Peukert, W.; Görling, A.; Steinrück, H.-P.; Wasserscheid, P.

    2017-09-01

    A strategy to develop improved catalysts is to create systems that merge the advantages of heterogeneous and molecular catalysis. One such system involves supported liquid-phase catalysts, which feature a molecularly defined, catalytically active liquid film/droplet layer adsorbed on a porous solid support. In the past decade, this concept has also been extended to supported ionic liquid-phase catalysts. Here we develop this idea further and describe supported catalytically active liquid metal solutions (SCALMS). We report a liquid mixture of gallium and palladium deposited on porous glass that forms an active catalyst for alkane dehydrogenation that is resistant to coke formation and is thus highly stable. X-ray diffraction and X-ray photoelectron spectroscopy, supported by theoretical calculations, confirm the liquid state of the catalytic phase under the reaction conditions. Unlike traditional heterogeneous catalysts, the supported liquid metal reported here is highly dynamic and catalysis does not proceed at the surface of the metal nanoparticles, but presumably at homogeneously distributed metal atoms at the surface of a liquid metallic phase.