Effect of atomic composition on the compressive strain and electrocatalytic activity of PtCoFe/sulfonated graphene

Energy Technology Data Exchange (ETDEWEB)

Lohrasbi, Elaheh [Department of Chemistry, Amirkabir University of Technology, Tehran (Iran, Islamic Republic of); Javanbakht, Mehran, E-mail: mehranjavanbakht@gmail.com [Department of Chemistry, Amirkabir University of Technology, Tehran (Iran, Islamic Republic of); Fuel and Solar Cell Lab, Renewable Energy Research Center, Amirkabir University of Technology, Tehran (Iran, Islamic Republic of); Mozaffari, Sayed Ahmad [Fuel and Solar Cell Lab, Renewable Energy Research Center, Amirkabir University of Technology, Tehran (Iran, Islamic Republic of); Thin Layer and Nanotechnology Laboratory, Department of Chemical Technology, Iranian Research Organization for Science and Technology (IROST), Tehran (Iran, Islamic Republic of)

2017-06-15

Highlights: • SO{sub 3}H-graphene supported PtFeCo alloy nanoparticles were prepared. • Co:Fe atomic ratio plays important role in the electrocatalytic performance. • PtCoFe/SG with 7:3 Co:Fe atomic ratio is optimized for PEMFCs. • Power density of 530 mW cm{sup −2} with 0.1 mg cm{sup −2} Pt loading was obtained at 75 °C. - Abstract: The aim of this work is improvement of the stability and durability of sulfonated graphene supported PtCoFe electrocatalyst (PtCoFe/SG) for application in proton exchange membrane fuel cells (PEMFCs). The durability investigation of PtCoFe/SG is evaluated by a repetitive potential cycling test. The compressive strain in the lattice of PtCoFe/SG towards the electrocatalytic oxygen reduction reaction is studied. The synthesized electrocatalysts are examined physically and electrochemically for their structure, morphology and electrocatalytic performance. It is shown that presence of SO{sub 3}− groups on the graphene cause better adsorption of PtCoFe nanoparticles on the support and increase stability of electrocatalysts. Also, it is shown that Co:Fe atomic ratio in the synthesized electrocatalysts plays important role in their electrocatalytic performance. In the optimum Co:Fe atomic ratio, the compressive strain goes through the ideal value of the binding energy; further increase in Co/Fe atomic fraction introduces the excessive compressive strain and the activity of electrocatalyst decreases. The electrocatalyst synthesized in the optimum conditions is utilized as cathode in PEMFC. The power density of the PEMFC in low metal loading (0.1 mg cm{sup −2} Pt) reaches to a maximum of 530 mW cm{sup −2} at 75 °C. It suggests that PtCoFe/SG with 7:3 Co:Fe atomic ratio promises to improve the power density of PEMFCs.

Effect of atomic composition on the compressive strain and electrocatalytic activity of PtCoFe/sulfonated graphene

International Nuclear Information System (INIS)

Lohrasbi, Elaheh; Javanbakht, Mehran; Mozaffari, Sayed Ahmad

2017-01-01

Highlights: • SO_3H-graphene supported PtFeCo alloy nanoparticles were prepared. • Co:Fe atomic ratio plays important role in the electrocatalytic performance. • PtCoFe/SG with 7:3 Co:Fe atomic ratio is optimized for PEMFCs. • Power density of 530 mW cm"−"2 with 0.1 mg cm"−"2 Pt loading was obtained at 75 °C. - Abstract: The aim of this work is improvement of the stability and durability of sulfonated graphene supported PtCoFe electrocatalyst (PtCoFe/SG) for application in proton exchange membrane fuel cells (PEMFCs). The durability investigation of PtCoFe/SG is evaluated by a repetitive potential cycling test. The compressive strain in the lattice of PtCoFe/SG towards the electrocatalytic oxygen reduction reaction is studied. The synthesized electrocatalysts are examined physically and electrochemically for their structure, morphology and electrocatalytic performance. It is shown that presence of SO_3− groups on the graphene cause better adsorption of PtCoFe nanoparticles on the support and increase stability of electrocatalysts. Also, it is shown that Co:Fe atomic ratio in the synthesized electrocatalysts plays important role in their electrocatalytic performance. In the optimum Co:Fe atomic ratio, the compressive strain goes through the ideal value of the binding energy; further increase in Co/Fe atomic fraction introduces the excessive compressive strain and the activity of electrocatalyst decreases. The electrocatalyst synthesized in the optimum conditions is utilized as cathode in PEMFC. The power density of the PEMFC in low metal loading (0.1 mg cm"−"2 Pt) reaches to a maximum of 530 mW cm"−"2 at 75 °C. It suggests that PtCoFe/SG with 7:3 Co:Fe atomic ratio promises to improve the power density of PEMFCs.

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

KAUST Repository

Liu, Xin; Sui, Yanhui; Duan, Ting; Meng, Changgong; Han, Yu

2015-01-01

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

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

NARCIS (Netherlands)

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

2014-01-01

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2017-12-14

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

Atomic layer deposition synthesis and evaluation of core–shell Pt-WC electrocatalysts

International Nuclear Information System (INIS)

Hsu, Irene J.; Chen, Jingguang G.; Jiang, Xiaoqiang; Willis, Brian G.

2015-01-01

Pt-WC core shell particles were produced using atomic layer deposition (ALD) to deposit Pt layers onto WC particle substrates. A range of Pt depositions were used to determine the growth mechanism for the Pt-WC powder system. TEM imaging and Cu stripping voltammetry found that Pt ALD growth on WC powder substrates was similar to that on WC thin films. However, excess free carbon was found to affect Pt ALD by blocking adsorption sites on WC. The Pt-WC samples were evaluated for the oxygen reduction reaction using a rotating disk electrode to obtain quantitative activity information. The mass and specific activities for the 30 and 50 ALD cycle samples were found to be comparable to a 10 wt. % Pt/C catalyst. However, higher overpotentials and lower limiting currents were observed with ALD Pt-WC compared to Pt/C catalysts, indicating that the oxygen reduction mechanism is not as efficient on Pt-WC as on bulk Pt. Additionally, these Pt-WC catalysts were used to demonstrate hydrogen evolution reaction activity and were found to perform as well as bulk Pt catalyst but with a fraction of the Pt loading, in agreement with the previous work on Pt-WC thin film catalysts

Pt/Cu single-atom alloys as coke-resistant catalysts for efficient C-H activation

Science.gov (United States)

Marcinkowski, Matthew D.; Darby, Matthew T.; Liu, Jilei; Wimble, Joshua M.; Lucci, Felicia R.; Lee, Sungsik; Michaelides, Angelos; Flytzani-Stephanopoulos, Maria; Stamatakis, Michail; Sykes, E. Charles H.

2018-03-01

The recent availability of shale gas has led to a renewed interest in C-H bond activation as the first step towards the synthesis of fuels and fine chemicals. Heterogeneous catalysts based on Ni and Pt can perform this chemistry, but deactivate easily due to coke formation. Cu-based catalysts are not practical due to high C-H activation barriers, but their weaker binding to adsorbates offers resilience to coking. Using Pt/Cu single-atom alloys (SAAs), we examine C-H activation in a number of systems including methyl groups, methane and butane using a combination of simulations, surface science and catalysis studies. We find that Pt/Cu SAAs activate C-H bonds more efficiently than Cu, are stable for days under realistic operating conditions, and avoid the problem of coking typically encountered with Pt. Pt/Cu SAAs therefore offer a new approach to coke-resistant C-H activation chemistry, with the added economic benefit that the precious metal is diluted at the atomic limit.

Pt/Cu single-atom alloys as coke-resistant catalysts for efficient C–H activation

Energy Technology Data Exchange (ETDEWEB)

Marcinkowski, Matthew D.; Darby, Matthew T.; Liu, Jilei; Wimble, Joshua M.; Lucci, Felicia R.; Lee, Sungsik; Michaelides, Angelos; Flytzani-Stephanopoulos, Maria; Stamatakis, Michail; Sykes, E. Charles H.

2018-01-08

The recent availability of shale gas has led to a renewed interest in C-H bond activation as the first step towards synthesis of fuels and fine chemicals. Heterogeneous catalysts based on Ni and Pt can perform this chemistry, but deactivate easily due to coke formation. Cu- based catalysts are not practical for this chemistry due to high C-H activation barriers, but their weaker binding to adsorbates offers resilience to coking. Utilizing Pt/Cu single atom alloys (SAAs) we examine C-H activation in a number of systems including methyl groups, methane, and butane using a combination of simulations, surface science, and catalysis studies. We find that Pt/Cu SAAs activate C-H bonds more efficiently than Cu, are stable for days under realistic operating conditions, and avoid the problem of coking typically encountered with Pt. Pt/Cu SAAs therefore offer a new approach to coke resistant C-H activation chemistry with the added economic benefit that the precious metal is diluted at the atomic limit.

High quality atomically thin PtSe2 films grown by molecular beam epitaxy

Science.gov (United States)

Yan, Mingzhe; Wang, Eryin; Zhou, Xue; Zhang, Guangqi; Zhang, Hongyun; Zhang, Kenan; Yao, Wei; Lu, Nianpeng; Yang, Shuzhen; Wu, Shilong; Yoshikawa, Tomoki; Miyamoto, Koji; Okuda, Taichi; Wu, Yang; Yu, Pu; Duan, Wenhui; Zhou, Shuyun

2017-12-01

Atomically thin PtSe2 films have attracted extensive research interests for potential applications in high-speed electronics, spintronics and photodetectors. Obtaining high quality thin films with large size and controlled thickness is critical. Here we report the first successful epitaxial growth of high quality PtSe2 films by molecular beam epitaxy. Atomically thin films from 1 ML to 22 ML have been grown and characterized by low-energy electron diffraction, Raman spectroscopy and x-ray photoemission spectroscopy. Moreover, a systematic thickness dependent study of the electronic structure is revealed by angle-resolved photoemission spectroscopy (ARPES), and helical spin texture is revealed by spin-ARPES. Our work provides new opportunities for growing large size single crystalline films to investigate the physical properties and potential applications of PtSe2.

Stability investigation of a high number density Pt1/Fe2O3 single-atom catalyst under different gas environments by HAADF-STEM

Science.gov (United States)

Duan, Sibin; Wang, Rongming; Liu, Jingyue

2018-05-01

Catalysis by supported single metal atoms has demonstrated tremendous potential for practical applications due to their unique catalytic properties. Unless they are strongly anchored to the support surfaces, supported single atoms, however, are thermodynamically unstable, which poses a major obstacle for broad applications of single-atom catalysts (SACs). In order to develop strategies to improve the stability of SACs, we need to understand the intrinsic nature of the sintering processes of supported single metal atoms, especially under various gas environments that are relevant to important catalytic reactions. We report on the synthesis of high number density Pt1/Fe2O3 SACs using a facial strong adsorption method and the study of the mobility of these supported Pt single atoms at 250 °C under various gas environments that are relevant to CO oxidation, water–gas shift, and hydrogenation reactions. Under the oxidative gas environment, Fe2O3 supported Pt single atoms are stable even at high temperatures. The presence of either CO or H2 molecules in the gas environment, however, facilitates the movement of the Pt atoms. The strong interaction between CO and Pt weakens the binding between the Pt atoms and the support, facilitating the movement of the Pt single atoms. The dissociation of H2 molecules on the Pt atoms and their subsequent interaction with the oxygen species of the support surfaces dislodge the surface oxygen anchored Pt atoms, resulting in the formation of Pt clusters. The addition of H2O molecules to the CO or H2 significantly accelerates the sintering of the Fe2O3 supported Pt single atoms. An anchoring-site determined sintering mechanism is further proposed, which is related to the metal–support interaction.

Growth of AlN/Pt heterostructures on amorphous substrates at low temperatures via atomic layer epitaxy

International Nuclear Information System (INIS)

Nepal, N.; Goswami, R.; Qadri, S.B.; Mahadik, N.A.; Kub, F.J.; Eddy, C.R.

2014-01-01

Recent results on atomic layer epitaxy (ALE) growth and characterization of (0 0 0 1)AlN on highly oriented (1 1 1)Pt layers on amorphous HfO 2 /Si(1 0 0) are reported. HfO 2 was deposited by atomic layer deposition on Si(1 0 0) followed by ALE growth of Pt(15 nm) and, subsequently, AlN(60 nm) at 500 °C. Based on the X-ray diffraction and transmission electron microscopy measurements, the Pt and AlN layers are highly oriented along the (1 1 1) and (0 0 0 2) directions, respectively. Demonstrations of AlN/Pt heterostructures open up the possibility of new state-of-the-art microelectromechanical systems devices

Pt thermal atomic layer deposition for silicon x-ray micropore optics.

Science.gov (United States)

Takeuchi, Kazuma; Ezoe, Yuichiro; Ishikawa, Kumi; Numazawa, Masaki; Terada, Masaru; Ishi, Daiki; Fujitani, Maiko; Sowa, Mark J; Ohashi, Takaya; Mitsuda, Kazuhisa

2018-04-20

We fabricated a silicon micropore optic using deep reactive ion etching and coated by Pt with atomic layer deposition (ALD). We confirmed that a metal/metal oxide bilayer of Al 2 O 3 ∼10  nm and Pt ∼20  nm was successfully deposited on the micropores whose width and depth are 20 μm and 300 μm, respectively. An increase of surface roughness of sidewalls of the micropores was observed with a transmission electron microscope and an atomic force microscope. X-ray reflectivity with an Al Kα line at 1.49 keV before and after the deposition was measured and compared to ray-tracing simulations. The surface roughness of the sidewalls was estimated to increase from 1.6±0.2  nm rms to 2.2±0.2  nm rms. This result is consistent with the microscope measurements. Post annealing of the Pt-coated optic at 1000°C for 2 h showed a sign of reduced surface roughness and better angular resolution. To reduce the surface roughness, possible methods such as the annealing after deposition and a plasma-enhanced ALD are discussed.

Surface reactions during atomic layer deposition of Pt derived from gas phase infrared spectroscopy

NARCIS (Netherlands)

Kessels, W.M.M.; Knoops, H.C.M.; Dielissen, S.A.F.; Mackus, A.J.M.; Sanden, van de M.C.M.

2009-01-01

Infrared spectroscopy was used to obtain absolute number information on the reaction products during atomic layer deposition of Pt from (methylcyclopentadienyl)trimethylplatinum [(MeCp)PtMe3] and O2. From the detection of CO2 and H2O it was established that the precursor ligands are oxidatively

Atomically thin Pt shells on Au nanoparticle cores: facile synthesis and efficient synergetic catalysis

DEFF Research Database (Denmark)

Engelbrekt, Christian; Seselj, Nedjeljko; Poreddy, Raju

2016-01-01

in electrooxidation of sustainable fuels (i.e. formic acid, methanol and ethanol), and selective hydrogenation of benzene derivatives. Especially high activity was achieved for formic acid oxidation, 549 mA (mgPt)−1 (at 0.6 V vs. SCE), which is 3.5 fold higher than a commercial ... properties were thoroughly characterized by ultraviolet-visible light spectrophotometry, transmission electron microscopy, nanoparticle tracking analysis and electrochemistry. The 8 ± 2 nm Au@PtNPs contained 24 ± 1 mol% Pt and 76 ± 1 mol% Au corresponding to an atomically thin Pt shell. Electrochemical data...

Direct versus ligand-exchange synthesis of [PtAg28(BDT)12(TPP)4]4− nanoclusters: effect of a single-atom dopant on the optoelectronic and chemical properties

KAUST Repository

Bootharaju, Megalamane Siddaramappa

2017-06-07

Heteroatom doping of atomically precise nanoclusters (NCs) often yields a mixture of doped and undoped products of single-atom difference, whose separation is extremely difficult. To overcome this challenge, novel synthesis methods are required to offer monodisperse doped NCs. For instance, the direct synthesis of PtAg28 NCs produces a mixture of [Ag29(BDT)12(TPP)4]3- and [PtAg28(BDT)12(TPP)4]4- NCs (TPP: triphenylphosphine; BDT: 1,3-benzenedithiolate). Here, we designed a ligand-exchange (LE) strategy to synthesize single-sized, Pt-doped, superatomic Ag NCs [PtAg28(BDT)12(TPP)4]4- by LE of [Pt2Ag23Cl7(TPP)10] NCs with BDTH2 (1,3-benzenedithiol). The doped NCs were thoroughly characterized by optical and photoelectron spectroscopy, mass spectrometry, total electron count, and time-dependent density functional theory (TDDFT). We show that the Pt dopant occupies the center of the PtAg28 cluster, modulates its electronic structure and enhances its photoluminescence intensity and excited-state lifetime, and also enables solvent interactions with the NC surface. Furthermore, doped NCs showed unique reactivity with metal ions - the central Pt atom of PtAg28 could not be replaced by Au, unlike the central Ag of Ag29 NCs. The achieved synthesis of single-sized PtAg28 clusters will facilitate further applications of the LE strategy for the exploration of novel multimetallic NCs.

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

KAUST Repository

Liu, Xin; Zhu, Hongdan; Linguerri, Roberto; Han, Yu; Chambaud, Gilberte; Meng, Changgong

2017-01-01

We compared the electronic structure and CO oxidation mechanisms over Pt atoms immobilized by both B-vacancies and N-vacancies on gas-exfoliated hexagonal boron nitride. We showed that chemical bonds are formed between the B atoms associated

Formic acid decomposition on Pt1/Cu (111) single platinum atom catalyst: Insights from DFT calculations and energetic span model analysis

Science.gov (United States)

Wang, Ying-Fan; Li, Kun; Wang, Gui-Chang

2018-04-01

Inspired by the recent surface experimental results that the monatomic Pt catalysts has more excellent hydrogen production that Cu(111) surface, the mechanism of decomposition of formic acid on Cu(111) and single atom Pt1/Cu(111) surface was studied by periodic density functional theory calculations in the present work. The results show that the formic acid tends to undergo dehydrogenation on both surfaces to obtain the hydrogen product of the target product, and the selectivity and catalytic activity of Pt1/Cu (111) surface for formic acid dehydrogenation are better. The reason is that the single atom Pt1/Cu(111) catalyst reduces the reaction energy barrier (i.e., HCOO → CO2 + H) of the critical step of the dehydrogenation reaction due to the fact that the single atom Pt1/Cu(111) catalyst binds formate weakly compared to that of Cu (111) one. Moreover, it was found that the Pt1/Cu (111) binds CO more strongly than that of Cu (111) one and thus leading to the difficult for the formation of CO. These two factors would make the single Pt atom catalyst had the high selectivity for the H2 production. It is hoped that the present work may help people to design the efficient H2 production from HCOOH decomposition by reduce the surface binding strength of HCOO species, for example, using the low coordination number active site like single atom or other related catalytic system.

From Single Atoms to Nanoparticles: Autocatalysis and Metal Aggregation in Atomic Layer Deposition of Pt on TiO2 Nanopowder.

Science.gov (United States)

Grillo, Fabio; Van Bui, Hao; La Zara, Damiano; Aarnink, Antonius A I; Kovalgin, Alexey Y; Kooyman, Patricia; Kreutzer, Michiel T; van Ommen, Jan Rudolf

2018-05-10

A fundamental understanding of the interplay between ligand-removal kinetics and metal aggregation during the formation of platinum nanoparticles (NPs) in atomic layer deposition of Pt on TiO 2 nanopowder using trimethyl(methylcyclo-pentadienyl)platinum(IV) as the precursor and O 2 as the coreactant is presented. The growth follows a pathway from single atoms to NPs as a function of the oxygen exposure (P O2 × time). The growth kinetics is modeled by accounting for the autocatalytic combustion of the precursor ligands via a variant of the Finke-Watzky two-step model. Even at relatively high oxygen exposures ( 120 mbar s. The deposition of more Pt leads to the formation of NPs that can be as large as 6 nm. Crucially, high P O2 (≥5 mbar) hinders metal aggregation, thus leading to narrow particle size distributions. The results show that ALD of Pt NPs is reproducible across small and large surface areas if the precursor ligands are removed at high P O2 . © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ambient-temperature diffusion and gettering of Pt atoms in GaN with surface defect region under 60Co gamma or MeV electron irradiation

Science.gov (United States)

Hou, Ruixiang; Li, Lei; Fang, Xin; Xie, Ziang; Li, Shuti; Song, Weidong; Huang, Rong; Zhang, Jicai; Huang, Zengli; Li, Qiangjie; Xu, Wanjing; Fu, Engang; Qin, G. G.

2018-01-01

Generally, the diffusion and gettering of impurities in GaN needs high temperature. Calculated with the ambient-temperature extrapolation value of the high temperature diffusivity of Pt atoms in GaN reported in literature, the time required for Pt atoms diffusing 1 nm in GaN at ambient temperature is about 19 years. Therefore, the ambient-temperature diffusion and gettering of Pt atoms in GaN can hardly be observed. In this work, the ambient-temperature diffusion and gettering of Pt atoms in GaN is reported for the first time. It is demonstrated by use of secondary ion mass spectroscopy that in the condition of introducing a defect region on the GaN film surface by plasma, and subsequently, irradiated by 60Co gamma-ray or 3 MeV electrons, the ambient-temperature diffusion and gettering of Pt atoms in GaN can be detected. It is more obvious with larger irradiation dose and higher plasma power. With a similar surface defect region, the ambient-temperature diffusion and gettering of Pt atoms in GaN stimulated by 3 MeV electron irradiation is more marked than that stimulated by gamma irradiation. The physical mechanism of ambient-temperature diffusion and gettering of Pt atoms in a GaN film with a surface defect region stimulated by gamma or MeV electron irradiation is discussed.

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

KAUST Repository

Liu, Xin; Duan, Ting; Meng, Changgong; Han, Yu

2015-01-01

Taking CO oxidation as a probe, we investigated the electronic structure and reactivity of Pt atoms stabilized by vacancy defects on hexagonal boron nitride (h-BN) by first-principles-based calculations. As a joint effect of the high reactivity

A low-temperature synthesis of electrochemical active Pt nanoparticles and thin films by atomic layer deposition on Si(111) and glassy carbon surfaces

Energy Technology Data Exchange (ETDEWEB)

Liu, Rui [Joint Center for Artificial Photosynthesis, California Institute of Technology, Pasadena, CA 91125 (United States); Han, Lihao [Joint Center for Artificial Photosynthesis, California Institute of Technology, Pasadena, CA 91125 (United States); Photovoltaic Materials and Devices (PVMD) Laboratory, Delft University of Technology, P.O. Box 5031, GA Delft 2600 (Netherlands); Huang, Zhuangqun; Ferrer, Ivonne M. [Joint Center for Artificial Photosynthesis, California Institute of Technology, Pasadena, CA 91125 (United States); Division of Chemistry and Chemical Engineering, California Institute of Technology, 210 Noyes Laboratory 127-72, Pasadena, CA 91125 (United States); Smets, Arno H.M.; Zeman, Miro [Photovoltaic Materials and Devices (PVMD) Laboratory, Delft University of Technology, P.O. Box 5031, GA Delft 2600 (Netherlands); Brunschwig, Bruce S., E-mail: bsb@caltech.edu [Beckman Institute, California Institute of Technology, Pasadena, CA 91125 (United States); Lewis, Nathan S., E-mail: nslewis@caltech.edu [Joint Center for Artificial Photosynthesis, California Institute of Technology, Pasadena, CA 91125 (United States); Beckman Institute, California Institute of Technology, Pasadena, CA 91125 (United States); Division of Chemistry and Chemical Engineering, California Institute of Technology, 210 Noyes Laboratory 127-72, Pasadena, CA 91125 (United States); Kavli Nanoscience Institute, California Institute of Technology, Pasadena, CA 91125 (United States)

2015-07-01

Atomic layer deposition (ALD) was used to deposit nanoparticles and thin films of Pt onto etched p-type Si(111) wafers and glassy carbon discs. Using precursors of MeCpPtMe{sub 3} and ozone and a temperature window of 200–300 °C, the growth rate was 80–110 pm/cycle. X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and scanning electron microscopy (SEM) were used to analyze the composition, structure, morphology, and thickness of the ALD-grown Pt nanoparticle films. The catalytic activity of the ALD-grown Pt for the hydrogen evolution reaction was shown to be equivalent to that of e-beam evaporated Pt on glassy carbon electrode. - Highlights: • Pure Pt films were grown by atomic layer deposition (ALD) using MeCpPtMe3 and ozone. • ALD-grown Pt thin films had high growth rates of 110 pm/cycle. • ALD-grown Pt films were electrocatalytic for hydrogen evolution from water. • Electrocatalytic activity of the ALD Pt films was equivalent to e-beam deposited Pt. • No carbon species were detected in the ALD-grown Pt films.

A low-temperature synthesis of electrochemical active Pt nanoparticles and thin films by atomic layer deposition on Si(111) and glassy carbon surfaces

International Nuclear Information System (INIS)

Liu, Rui; Han, Lihao; Huang, Zhuangqun; Ferrer, Ivonne M.; Smets, Arno H.M.; Zeman, Miro; Brunschwig, Bruce S.; Lewis, Nathan S.

2015-01-01

Atomic layer deposition (ALD) was used to deposit nanoparticles and thin films of Pt onto etched p-type Si(111) wafers and glassy carbon discs. Using precursors of MeCpPtMe 3 and ozone and a temperature window of 200–300 °C, the growth rate was 80–110 pm/cycle. X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and scanning electron microscopy (SEM) were used to analyze the composition, structure, morphology, and thickness of the ALD-grown Pt nanoparticle films. The catalytic activity of the ALD-grown Pt for the hydrogen evolution reaction was shown to be equivalent to that of e-beam evaporated Pt on glassy carbon electrode. - Highlights: • Pure Pt films were grown by atomic layer deposition (ALD) using MeCpPtMe3 and ozone. • ALD-grown Pt thin films had high growth rates of 110 pm/cycle. • ALD-grown Pt films were electrocatalytic for hydrogen evolution from water. • Electrocatalytic activity of the ALD Pt films was equivalent to e-beam deposited Pt. • No carbon species were detected in the ALD-grown Pt films

Magnetic properties of Co and Fe on Pt(111), Rh(111) and Pd(111): From single atoms to ultrathin films

Energy Technology Data Exchange (ETDEWEB)

Lehnert, Anne; Rusponi, Stefano; Etzkorn, Markus; Moulas, Geraud; Brune, Harald [IPN, EPF-Lausanne (Switzerland); Gambardella, Pietro [CREA, Catalan Institute of Nanotechnology (Spain); Bencok, Peter [ESRF, Grenoble (France)

2009-07-01

Single atoms of Co on Pt(111) are known to have a giant magnetic anisotropy energy (MAE) of 9.3 meV/atom. This is due to the reduced coordination and the strong spin-orbit coupling of the Pt 5d-states. In order to study the contribution of a highly polarizable substrate to the MAE, we investigated single Co atoms on Pd(111) and Rh(111) using X-ray magnetic circular dichroism (XMCD). We find a decreasing MAE moving from a 5d-substrate (Pt) to 4d-substrates (Pd and Rh). Co has a large orbital moment L of about 0.7 independent of the substrate. The easy axis is out-of-plane for Pt(111) and Pd(111) whereas it is in-plane for Co/Rh(111). Fe has on all substrates an out-of-plane easy axis, a very small anisotropy energy, and a L/S ratio of about 0.1. With increasing coverage the coordination number of the adatom increases and generally leads to a reduced MAE and orbital moment compared to the single atom. We measure one monolayer of Co and Fe on Pt(111) and Rh(111) and find MAE values <0.5 meV/atom. For 1 ML Co we find a substantial decrease in the L/S ratio to 0.19. However, the L/S ratio for 1 ML Fe on both substrates does not change much compared with the Fe single atom.

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

Energy Technology Data Exchange (ETDEWEB)

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

2012-02-15

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

Study the Polyol Process of Preparing the ru Doped FePt Nanoparticles

Science.gov (United States)

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

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

Influence of multi-hit capability on quantitative measurement of NiPtSi thin film with laser-assisted atom probe tomography

International Nuclear Information System (INIS)

Kinno, T.; Akutsu, H.; Tomita, M.; Kawanaka, S.; Sonehara, T.; Hokazono, A.; Renaud, L.; Martin, I.; Benbalagh, R.; Sallé, B.; Takeno, S.

2012-01-01

Highlights: ► Laser-assisted atom probe tomography was applied to NiPtSi films on Si substrates. ► Comparison of depth profiles of single-hit events and those of multi-hit events. ► ∼80% of Pt atoms were detected in multi-hit events. ► Multiple-ion detection is important for Laser-assisted atom probe tomography. - Abstract: Laser-assisted atom probe tomography (LA-APT) was applied to NiPtSi (0, 30, and 50% Pt contents) thin films on Si substrates. Consistent results with those of high-resolution Rutherford backscattering spectrometry (HR-RBS) were obtained. Based on the obtained data sets, the composition profiles from only the signals of single-hit events, meaning detection of one ion by one laser pulse, were compiled. The profiles from only the signals of multi-hit events, meaning detection of multiple ions by one laser pulse, were also compiled. There were large discrepancies with respect to Ni and Pt concentrations among the compiled profiles and the original profiles including the signals of both types of detection events. Additionally, the profiles compiled from single-hit events showed that Si concentration in NiPtSi layer became smaller toward the surface, differing from the original profiles and the multi-hit profiles. These results suggest that capability of simultaneous multiple-ion detection is important for appropriate LA-APT analyses.

Atomic Structure Control of Silica Thin Films on Pt(111)

KAUST Repository

Crampton, Andrew S

2015-05-27

Metal oxide thin films grown on metal single crystals are commonly used to model heterogeneous catalyst supports. The structure and properties of thin silicon dioxide films grown on metal single crystals have only recently been thoroughly characterized and their spectral properties well established. We report the successful growth of a three- dimensional, vitreous silicon dioxide thin film on the Pt(111) surface and reproduce the closed bilayer structure previously reported. The confirmation of the three dimensional nature of the film is unequivocally shown by the infrared absorption band at 1252 cm−1. Temperature programmed desorption was used to show that this three-dimensional thin film covers the Pt(111) surface to such an extent that its application as a catalyst support for clusters/nanoparticles is possible. The growth of a three-dimensional film was seen to be directly correlated with the amount of oxygen present on the surface after the silicon evaporation process. This excess of oxygen is tentatively attributed to atomic oxygen being generated in the evaporator. The identification of atomic oxygen as a necessary building block for the formation of a three-dimensional thin film opens up new possibilities for thin film growth on metal supports, whereby simply changing the type of oxygen enables thin films with different atomic structures to be synthesized. This is a novel approach to tune the synthesis parameters of thin films to grow a specific structure and expands the options for modeling common amorphous silica supports under ultra high vacuum conditions.

The Electrochemical Atomic Layer Deposition of Pt and Pd nanoparticles on Ni foam for the electrooxidation of alcohols

CSIR Research Space (South Africa)

Modibedi, RM

2012-10-01

Full Text Available Electrodeposition of Pt and Pd metal by surface limited redox replacement reactions was performed using the electrochemical atomic layer deposition. Carbon paper and Ni foam were used as substrates for metal deposition. Supported Pt and Pd...

Understanding Pt-ZnO:In Schottky nanocontacts by conductive atomic force microscopy

Science.gov (United States)

Chirakkara, Saraswathi; Choudhury, Palash Roy; Nanda, K. K.; Krupanidhi, S. B.

2016-04-01

Undoped and In doped ZnO (IZO) thin films are grown on Pt coated silicon substrates Pt/Si by pulsed laser deposition to fabricate Pt/ZnO:In Schottky diodes. The Schottky diodes were investigated by conventional two-probe current-voltage (I-V) measurements and by the I-V spectroscopy tool of conductive atomic force microscopy (C-AFM). The large deviation of the ideality factor from unity and the temperature dependent Schottky barrier heights (SBHs) obtained from the conventional method imply the presence of inhomogeneous interfaces. The inhomogeneity of SBHs is confirmed by C-AFM. Interestingly, the I-V curves at different points are found to be different, and the SBHs deduced from the point diodes reveal inhomogeneity at the nanoscale at the metal-semiconductor interface. A reduction in SBH and turn-on voltage along with enhancement in forward current are observed with increasing indium concentration.

Examining the rudimentary steps of the oxygen reduction reaction on single-atomic Pt using Ti-based non-oxide supports

DEFF Research Database (Denmark)

Tak, Young Joo; Yang, Sungeun; Lee, Hyunjoo

2018-01-01

C(100)-supported single Pt atoms. The O2 and OOH* dissociation processes on Pt/TiN(100) are determined to be non-activated (i.e. "barrier-less" dissociation) while an activation energy barrier of 0.19 and 0.51eV is found for these dissociation processes on Pt/TiC(100), respectively. Moreover, the series...

From Single Atoms to Nanoparticles : Autocatalysis and Metal Aggregation in Atomic Layer Deposition of Pt on TiO2 Nanopowder

NARCIS (Netherlands)

Grillo, Fabio; Van Bui, Hao; La Zara, Damiano; Aarnink, Antonius A.I.; Kovalgin, Alexey Y.; Kooyman, Patricia; Kreutzer, Michiel T.; van Ommen, Jan Rudolf

2018-01-01

A fundamental understanding of the interplay between ligand-removal kinetics and metal aggregation during the formation of platinum nanoparticles (NPs) in atomic layer deposition of Pt on TiO2 nanopowder using trimethyl(methylcyclo-pentadienyl)platinum(IV) as the precursor and O2 as the coreactant

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

Science.gov (United States)

Liu, Zhenyu; Wang, Guofeng

2017-12-01

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

Evidence for non-conservative current-induced forces in the breaking of Au and Pt atomic chains

OpenAIRE

Sabater, Carlos; Untiedt, Carlos; van Ruitenbeek, Jan M

2015-01-01

This experimental work aims at probing current-induced forces at the atomic scale. Specifically it addresses predictions in recent work regarding the appearance of run-away modes as a result of a combined effect of the non-conservative wind force and a ‘Berry force’. The systems we consider here are atomic chains of Au and Pt atoms, for which we investigate the distribution of break down voltage values. We observe two distinct modes of breaking for Au atomic chains. The breaking at high volta...

Density functional theory studies of the adsorption of ethylene and oxygen on Pt(111) and Pt3Sn(111)

DEFF Research Database (Denmark)

Watwe, R.M.; Cortright, R.D.; Mavrikakis, Manos

2001-01-01

Density functional theory, employing periodic slab calculations, was used to investigate the interactions of ethylene and oxygen with Pt(111) and Pt3Sn(111). The predicted energetics and structures of adsorbed species on Pt(111) are in good agreement with experimental data. The binding energies...... more than adsorption on two-fold and one-fold sites. Oxygen atoms bond as strongly on Pt3Sn(111) as on Pt(111), and these atoms prefer to adsorb near Sn atoms on the surface. The addition of Sn to Pt(111) leads to a surface heterogeneity, wherein ethylidyne species prefer to adsorb away from Sn atoms...

Correlação entre a estrutura atômica superficial e o processo de adsorção-dessorção reversível de hidrogênio em eletrodos monocristalinos Pt(111, Pt(100 e Pt(110 The correlation between the atomic surface structure and the reversible adsorption-desorption of hydrogen on single crystal Pt (111, Pt (100 and Pt (110 electrodes

Directory of Open Access Journals (Sweden)

Valderi Pacheco dos Santos

2001-12-01

Full Text Available Platinum is widely used as electrode in electrocatalytic processes, however the use of polycrystalline electrodes introduces a series of variables in the electrochemical system due to the aleatory contribution of all the crystallographic orientations with different surface packing of atoms. Single crystal platinum electrodes of low Miller index present surface structure of high regularity and serve as model to establish a correlation among the macroscopic and microscopic properties of the electrochemical interface. Therefore, the main aim of this work is the study of the voltammetric profiles of the reversible adsorption-desorption of hydrogen on Pt(100, Pt(110 and Pt(111, in order to correlate the electrochemical properties of each different orientation with the surface atomic structure.

In-situ observation of Cu-Pt core-shell nanoparticles in the atomic scale by XAFS

International Nuclear Information System (INIS)

Zheng, Xusheng; Liu, Shoujie; Chen, Xing; Cheng, Jie; Ye, Qing; Pan, Zhiyun; Chu, Wangsheng; Wu, Ziyu; Marcelli, Augosto

2013-01-01

Bimetallic nanoparticles play an important role in potential industrial applications, such as catalysis, optoelectronics, information storage and biological labeling. Herein, homogeneous Cu-Pt core-shell nanoparticles with the averaged size of 8 nm have been synthesized by chemical methods. Cu atoms diffusion process, which motivated by heating, was observed in-situ by using temperature-dependent x-ray absorption fine-structure (XAFS) spectroscopy. Results show that Cu diffuse gradually from Cu core to Pt shell in these nanoparticles with increasing temperature. We also found the surface ligand (O) bonded Pt at the room temperature and were removed gradually by heating the sample. The analysis of the diffusion process in bimetallic nanoparticles will provide important guideline for their designing and tuning.

Exploration for atomic minerals, Pt. 4: training course handbook, V. 3, 1997

International Nuclear Information System (INIS)

Singh, Rajendra; Dwivedy, K.K.

1997-01-01

The training course handbook containing four parts was prepared by scientists of Atomic Minerals Division who have put in several years of work and gained expertise in their respective fields. Pt. 4 contains a variety of articles on practical aspects of geological mapping, sampling, and ore reserves estimations and laboratory techniques in ore extraction and chemical analysis of geological samples. Papers relevant to INIS are indexed separately

Enhanced creation of dispersive monolayer phonons in Xe/Pt(111) by inelastic helium atom scattering at low energies

DEFF Research Database (Denmark)

Hansen, Flemming Yssing; Bruch, Ludwig Walter

2007-01-01

Conditions likely to lead to enhanced inelastic atomic scattering that creates shear horizontal (SH) and longitudinal acoustic (LA) monolayer phonons are identified, specifically examining the inelastic scattering of He-4 atoms by a monolayer solid of Xe/Pt(111) at incident energies of 2-25 meV. ...

The Pt site reactivity of the molecular graphs of Au6Pt isomers

Science.gov (United States)

Xu, Tianlv; Jenkins, Samantha; Xiao, Chen-Xia; Maza, Julio R.; Kirk, Steven R.

2013-12-01

Within the framework of the theory of atoms in molecules (QTAIM), in an exploratory study we propose a new measure of site reactivity equivalent to the atomic coordination number based purely on the electronic structure. It was found that the number of ring critical points (NNRCPs) positioned on the boundary of the atomic basin of the dopant (Pt) nucleus correlated very well with the relative zero point energy (ZPE) corrected energies. A weaker condition (i.e. than the number of associated bond paths) for the association of the dopant Pt nucleus with the Au6Pt molecular graph is found for NNRCP = 0.

Theoretical simulations of the structural stabilities, elastic, thermodynamic and electronic properties of Pt3Sc and Pt3Y compounds

Science.gov (United States)

Boulechfar, R.; Khenioui, Y.; Drablia, S.; Meradji, H.; Abu-Jafar, M.; Omran, S. Bin; Khenata, R.; Ghemid, S.

2018-05-01

Ab-initio calculations based on density functional theory have been performed to study the structural, electronic, thermodynamic and mechanical properties of intermetallic compounds Pt3Sc and Pt3Y using the full-potential linearized augmented plane wave(FP-LAPW) method. The total energy calculations performed for L12, D022 and D024 structures confirm the experimental phase stability. Using the generalized gradient approximation (GGA), the values of enthalpies formation are -1.23 eV/atom and -1.18 eV/atom for Pt3Sc and Pt3Y, respectively. The densities of states (DOS) spectra show the existence of a pseudo-gap at the Fermi level for both compounds which indicate the strong spd hybridization and directing covalent bonding. Furthermore, the density of states at the Fermi level N(EF), the electronic specific heat coefficient (γele) and the number of bonding electrons per atom are predicted in addition to the elastic constants (C11, C12 and C44). The shear modulus (GH), Young's modulus (E), Poisson's ratio (ν), anisotropy factor (A), ratio of B/GH and Cauchy pressure (C12-C44) are also estimated. These parameters show that the Pt3Sc and Pt3Y are ductile compounds. The thermodynamic properties were calculated using the quasi-harmonic Debye model to account for their lattice vibrations. In addition, the influence of the temperature and pressure was analyzed on the heat capacities (Cp and Cv), thermal expansion coefficient (α), Debye temperature (θD) and Grüneisen parameter (γ).

Measurement of Young’s modulus and residual stress of atomic layer deposited Al2O3 and Pt thin films

Science.gov (United States)

Purkl, Fabian; Daus, Alwin; English, Timothy S.; Provine, J.; Feyh, Ando; Urban, Gerald; Kenny, Thomas W.

2017-08-01

The accurate measurement of mechanical properties of thin films is required for the design of reliable nano/micro-electromechanical devices but is increasingly challenging for thicknesses approaching a few nanometers. We apply a combination of resonant and static mechanical test structures to measure elastic constants and residual stresses of 8-27 nm thick Al2O3 and Pt layers which have been fabricated through atomic layer deposition. Young’s modulus of poly-crystalline Pt films was found to be reduced by less than 15% compared to the bulk value, whereas for amorphous Al2O3 it was reduced to about half of its bulk value. We observed no discernible dependence of the elastic constant on thickness or deposition method for Pt, but the use of plasma-enhanced atomic layer deposition was found to increase Young’s modulus of Al2O3 by 10% compared to a thermal atomic layer deposition. As deposited, the Al2O3 layers had an average tensile residual stress of 131 MPa. The stress was found to be higher for thinner layers and layers deposited without the help of a remote plasma. No residual stress values could be extracted for Pt due to insufficient adhesion of the film without an underlying layer to promote nucleation.

IMPLEMENTASI TOTAL PRODUCTIVE MAINTENANCE DI DEPARTEMEN NON JAHIT PT. KERTA RAJASA RAYA

Directory of Open Access Journals (Sweden)

Ronald E. Stok

2001-01-01

Full Text Available The effectivity improvement of production facility in factory is not only on facility manitenance but also on human resources. Total Productive Maintenance (TPM gives an optimal solution to effectivity improvement. A case study of TPM implementation have done in non sewing department of PT Kerta Rajasa Raya. Abstract in Bahasa Indonesia : Peningkatan efektivitas dari fasilitas produksi di suatu perusahaan bukan hanya terbatas pada perawatan fasilitas kerja saja tetapi juga sumber daya manusia. Total Productive Maintenance (TPM memberikan suatu solusi optimal terhadap peningkatan efektivitas dengan melibatkan semua sumber daya manusia yang bertanggung jawab terhadap fasilitas produksi. Suatu studi kasus terhadap pengimplementasian TPM dilakukan di departemen non jahit PT. Kerta Rajasa Raya. Kata kunci : TPM, MTTF, Autonomous Maintenance.

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

KAUST Repository

Zhang, Zailei; Zhu, Yihan; Asakura, Hiroyuki; Zhang, Bin; Zhang, Jiaguang; Zhou, Maoxiang; Han, Yu; Tanaka, Tsunehiro; Wang, Aiqin; Zhang, Tao; Yan, Ning

2017-01-01

with outstanding stability in several reactions under demanding conditions. The Pt atoms are firmly anchored in the internal surface of mesoporous Al2O3, likely stabilized by coordinatively unsaturated pentahedral Al3+ centres. The catalyst keeps its structural

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

Energy Technology Data Exchange (ETDEWEB)

Dias, Ricardo Rodrigues

2009-07-01

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

Current-voltage curves of atomic-sized transition metal contacts: An explanation of why Au is ohmic and Pt is not

DEFF Research Database (Denmark)

Nielsen, S.K.; Brandbyge, Mads; Hansen, K.

2002-01-01

We present an experimental study of current-voltage (I-V) curves on atomic-sized Au and Pt contacts formed under cryogenic vacuum (4.2 K). Whereas I-V curves for Au are almost Ohmic, the conductance G=I/V for Pt decreases with increasing voltage, resulting in distinct nonlinear I-V behavior...

Atomic Layer Deposition of Pt Nanoparticles within the Cages of MIL-101: A Mild and Recyclable Hydrogenation Catalyst

Directory of Open Access Journals (Sweden)

Karen Leus

2016-03-01

Full Text Available We present the in situ synthesis of Pt nanoparticles within MIL-101-Cr (MIL = Materials Institute Lavoisier by means of atomic layer deposition (ALD. The obtained Pt@MIL-101 materials were characterized by means of N2 adsorption and X-ray powder diffraction (XRPD measurements, showing that the structure of the metal organic framework was well preserved during the ALD deposition. X-ray fluorescence (XRF and transmission electron microscopy (TEM analysis confirmed the deposition of highly dispersed Pt nanoparticles with sizes determined by the MIL-101-Cr pore sizes and with an increased Pt loading for an increasing number of ALD cycles. The Pt@MIL-101 material was examined as catalyst in the hydrogenation of different linear and cyclic olefins at room temperature, showing full conversion for each substrate. Moreover, even under solvent free conditions, full conversion of the substrate was observed. A high concentration test has been performed showing that the Pt@MIL-101 is stable for a long reaction time without loss of activity, crystallinity and with very low Pt leaching.

Exotic high activity surface patterns in PtAu nanoclusters

KAUST Repository

Mokkath, Junais Habeeb

2013-05-09

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

Preparation of PtSn/C, PtRu/C, PtRh/C, PtRuRh/C and PtSnRh/C electrocatalysts using an alcohol-reduction process for methanol and ethanol oxidation

International Nuclear Information System (INIS)

Dias, Ricardo Rodrigues

2009-01-01

In this work, Pt/C, PtRh (90:10), PtRh/C (50:50), PtSn/C (50:50), PtRu (50:50)/C, PtRuRh/C (50:40:10) and PtSnRh/C (50:40:10) were prepared by an alcohol-reduction process with metal loading of 20 wt.% using H 2 PtCl 6 .6H 2 O (Aldrich), SnCl 2 .2H 2 O (Aldrich),and RhCl 2 .XH 2 O (Aldrich) as metals sources and Vulcan XC72 as support. The electrocatalysts were characterized by EDX, XRD and cyclic voltammetry (CV). The electro-oxidation of ethanol was studied by CV, chronoamperomety at room temperature in acid medium and tests at 100 deg C on a single cell of a direct methanol or ethanol fuel cell. The EDX analysis showed that the metal atomic ratios of the obtained electrocatalysts were similar to the nominal atomic ratios used in the preparation. The diffractograms of electrocatalysts prepared showed four peaks at approximately 2θ = 40 0 , 47 0 , 67 0 and 82 0 , which are associated with the (111), (200), (220) and (311) planes, respectively, of a face cubic-centered (fcc) structure characteristic of platinum and platinum alloys. The average crystallite sizes using the Scherrer equation and the calculated values were in the range of 2–3 nm. For PtSn/C and PtSnRh/C two additional peaks were observed at 2θ = 34 0 and 52 0 that were identified as a SnO 2 phase. PtSn/C (50:50) and PtSnRh/C (50:40:10) electrocatalyst showed the best performance for ethanol oxidation at room temperature. For methanol oxidation at room temperature PtRu/C, PtSn/C and PtRuRh/C electrocatalysts showed the best performance. Tests at 100 deg C on a single cell of a direct ethanol fuel cell PtSnRh/C showed the best performance, for methanol oxidation PtRuRh/C showed the best performance. (author)

Atomic mass and characteristic constant of nuclear ground state (CENPL.MCC). Pt. 1

International Nuclear Information System (INIS)

Su Zongdi; Ma Lizhen; Zhou Chunmei; Ge Zhigang

1994-01-01

Atomic mass and characteristic constants for nuclear ground states are basic data for nuclear physics, and necessary ones for basic researches, theoretical calculations, as well as many applied researches. The atomic mass of exotic nuclei quite far from the valley stability are also very important for astrophysics researches. The above-requirement is paid attention to in our setting up this file. The recent and as many as possible data (such as the half-lives of the new nuclides 202 Pt, 208 Hg and 185 Hf and the mass excess of 199 Ir, which were produced and distinguished by Chinese scientists) have been collected, and put into the computer-based data file in brief table format. (1 fig.)

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

Energy Technology Data Exchange (ETDEWEB)

Dias, Ricardo Rodrigues

2009-07-01

In this work, Pt/C, PtRh (90:10), PtRh/C (50:50), PtSn/C (50:50), PtRu (50:50)/C, PtRuRh/C (50:40:10) and PtSnRh/C (50:40:10) were prepared by an alcohol-reduction process with metal loading of 20 wt.% using H{sub 2}PtCl{sub 6}.6H{sub 2}O (Aldrich), SnCl{sub 2}.2H{sub 2}O (Aldrich),and RhCl{sub 2}.XH{sub 2}O (Aldrich) as metals sources and Vulcan XC72 as support. The electrocatalysts were characterized by EDX, XRD and cyclic voltammetry (CV). The electro-oxidation of ethanol was studied by CV, chronoamperomety at room temperature in acid medium and tests at 100 deg C on a single cell of a direct methanol or ethanol fuel cell. The EDX analysis showed that the metal atomic ratios of the obtained electrocatalysts were similar to the nominal atomic ratios used in the preparation. The diffractograms of electrocatalysts prepared showed four peaks at approximately 2θ = 40{sup 0}, 47{sup 0}, 67{sup 0} and 82{sup 0}, which are associated with the (111), (200), (220) and (311) planes, respectively, of a face cubic-centered (fcc) structure characteristic of platinum and platinum alloys. The average crystallite sizes using the Scherrer equation and the calculated values were in the range of 2–3 nm. For PtSn/C and PtSnRh/C two additional peaks were observed at 2θ = 34{sup 0} and 52{sup 0} that were identified as a SnO{sub 2} phase. PtSn/C (50:50) and PtSnRh/C (50:40:10) electrocatalyst showed the best performance for ethanol oxidation at room temperature. For methanol oxidation at room temperature PtRu/C, PtSn/C and PtRuRh/C electrocatalysts showed the best performance. Tests at 100 deg C on a single cell of a direct ethanol fuel cell PtSnRh/C showed the best performance, for methanol oxidation PtRuRh/C showed the best performance. (author)

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

KAUST Repository

Liu, Xin; Sui, Yanhui; Duan, Ting; Meng, Changong; Han, Yu

2014-01-01

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

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

Energy Technology Data Exchange (ETDEWEB)

Molina, J.; Fernandez, J.; Rio, A.I. del; Bonastre, J. [Departamento de Ingenieria Textil y Papelera, EPS de Alcoy, Universitat Politecnica de Valencia, Plaza Ferrandiz y Carbonell s/n, 03801 Alcoy (Spain); Cases, F., E-mail: fjcases@txp.upv.es [Departamento de Ingenieria Textil y Papelera, EPS de Alcoy, Universitat Politecnica de Valencia, Plaza Ferrandiz y Carbonell s/n, 03801 Alcoy (Spain)

2012-06-15

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

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

International Nuclear Information System (INIS)

Silva, Dionisio Furtunato da

2009-01-01

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

Electronic structure, thermodynamic properties and hydrogenation of LaPtIn and CePtIn compounds by ab-initio methods

International Nuclear Information System (INIS)

Jezierski, Andrzej; Szytuła, Andrzej

2016-01-01

The electronic structures and thermodynamic properties of LaPtIn and CePtIn are studied by means of ab-initio full-relativistic full-potential local orbital basis (FPLO) method within densities functional (DFT) methodologies. We have also examined the influence of hydrogen on the electronic structure and stability of CePtInH and LaPtInH systems. The positions of the hydrogen atoms have been found from the minimum of the total energy. Our calculations have shown that band structure and topology of the Fermi surfaces changed significantly during the hydrogenation. The thermodynamic properties (bulk modulus, Debye temperatures, constant pressure heat capacity) calculated in quasi-harmonic Debye-Grüneisen model are in a good agreement with the experimental data. We have applied different methods of the calculation of the equation of states (EOS) (Murnaghan, Birch-Murnaghan, Poirier–Tarantola, Vinet). The thermodynamic properties are presented for the pressure 0< P<9 GPa and the temperature range 0< T<300 K. - Highlights: • Full relativistic band structure of LaPtIn and CePtIn. • Fermi surface of LaPtIn, LaPtInH, CePtIn, CePtInH. • Effect of hydrogenation on the electronic structure of LaPtIn and CePtIn. • Thermodynamic properties in the quasi-harmonic Debye-Grüneisen model.

The role of the anionic and cationic pt sites in the adsorption site preference of water and ethanol on defected Pt4/Pt(111) substrates: A density functional theory investigation within the D3 van der waals corrections

Science.gov (United States)

Seminovski, Yohanna; Amaral, Rafael C.; Tereshchuk, Polina; Da Silva, Juarez L. F.

2018-01-01

Platinum (Pt) atoms in the bulk face-centered cubic structure have neutral charge because they are equivalent by symmetry, however, in clean Pt surfaces, the effective charge on Pt atoms can turn slightly negative (anionic) or positive (cationic) while increasing substantially in magnitude for defected (low-coordinated) Pt sites. The effective charge affect the adsorption properties of molecular species on Pt surfaces and it can compete in importance with the coupling of the substrate-molecule electronic states. Although several studies have been reported due to the importance of Pt for catalysis, our understanding of the role played by low-coordinated sites is still limited. Here, we employ density functional theory within the Perdew-Burke-Ernzerhof exchange-correlation functional and the D3 van der Waals (vdW) correction to investigate the role of the cationic and anionic Pt sites on the adsorption properties of ethanol and water on defected Pt4/Pt(111) substrates. Four substrates were carefully selected, namely, two two-dimensional (2D) Pt4 configurations (2D-strand and 2D-island) and two tri-dimensional (3D) Pt4 (3D-fcc and 3D-hcp), to understand the role of coordination, effective charge, and coupling of the electronic states in the adsorption properties. From the Bader charge analysis, we identified the cationic and anionic sites among the Pt atoms exposed to the vacuum region in the Pt4/Pt(111) substrates. We found that ethanol and water bind via the anionic O atoms to the low-coordinated defected Pt sites of the substrates, where the angle PtOH is nearly 100° for most configurations. In the 3D-fcc or 3D-hcp defected configurations, the lowest-coordinated Pt atoms are anionic, hence, those Pt sites are not preferable for the adsorption of O atoms. The charge transfer from water and ethanol to the Pt substrates has similar magnitude for all cases, which implies similar Coulomb contribution to the adsorption energy. Moreover, we found a correlation of the

Reversibility of Pt-Skin and Pt-Skeleton Nanostructures in Acidic Media.

Science.gov (United States)

Durst, Julien; Lopez-Haro, Miguel; Dubau, Laetitia; Chatenet, Marian; Soldo-Olivier, Yvonne; Guétaz, Laure; Bayle-Guillemaud, Pascale; Maillard, Frédéric

2014-02-06

Following a well-defined series of acid and heat treatments on a benchmark Pt3Co/C sample, three different nanostructures of interest for the electrocatalysis of the oxygen reduction reaction were tailored. These nanostructures could be sorted into the "Pt-skin" structure, made of one pure Pt overlayer, and the "Pt-skeleton" structure, made of 2-3 Pt overlayers surrounding the Pt-Co alloy core. Using a unique combination of high-resolution aberration-corrected STEM-EELS, XRD, EXAFS, and XANES measurements, we provide atomically resolved pictures of these different nanostructures, including measurement of the Pt-shell thickness forming in acidic media and the resulting changes of the bulk and core chemical composition. It is shown that the Pt-skin is reverted toward the Pt-skeleton upon contact with acid electrolyte. This change in structure causes strong variations of the chemical composition.

Segregation and stability at Pt3Ni(1 1 1) surfaces and Pt75Ni25 nanoparticles

International Nuclear Information System (INIS)

Fowler, Ben; Lucas, Christopher A.; Omer, Ahmed; Wang, Guofeng; Stamenkovic, Vojislav R.; Markovic, Nenad M.

2008-01-01

Using in situ surface X-ray diffraction we have determined the atomic structure and stability of a Pt 3 Ni(1 1 1) surface in the electrochemical environment. Surface segregation leads to a pure Pt(1 1 1) skin with enrichment of Ni in the sub-surface atomic layer that determines the surface electronic structure. The Pt-skin surface exhibits inward relaxation upon the adsorption of oxygenated species and this explains the surface stability compared to pure Pt(1 1 1). Using Monte Carlo calculations it is shown that nanoparticles with the same surface composition and stochiometry are energetically stable

Structure of the cobalt-filled missing-row reconstruction of Pt(110)

International Nuclear Information System (INIS)

Klein, C.; Koller, R.; Schmid, M.; Varga, P.; Lundgren, E.; Maca, F.; Redinger, J.

2004-01-01

The atomic structure of 0.5 monolayer (ML) Co deposited on Pt(110) was investigated by quantitative low-energy electron diffraction and ab initio density functional theory calculations, showing a pronounced inward relaxation and a filling of the missing-row sites of the Pt(110) substrate by Co atoms. Up to this Co coverage no significant intermixing of Pt atoms with Co atoms was observed by scanning tunneling microscopy, resulting in an alternating arrangement of pure Co and Pt rows

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

International Nuclear Information System (INIS)

Carballo, Luis M; Zea, Hugo R

1999-01-01

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

Synthesis of Pt@TiO2@CNTs Hierarchical Structure Catalyst by Atomic Layer Deposition and Their Photocatalytic and Photoelectrochemical Activity.

Science.gov (United States)

Liao, Shih-Yun; Yang, Ya-Chu; Huang, Sheng-Hsin; Gan, Jon-Yiew

2017-04-29

Pt@TiO2@CNTs hierarchical structures were prepared by first functionalizing carbon nanotubes (CNTs) with nitric acid at 140 °C. Coating of TiO2 particles on the CNTs at 300 °C was then conducted by atomic layer deposition (ALD). After the TiO2@CNTs structure was fabricated, Pt particles were deposited on the TiO2 surface as co-catalyst by plasma-enhanced ALD. The saturated deposition rates of TiO2 on a-CNTs were 1.5 Å/cycle and 0.4 Å/cycle for substrate-enhanced process and linear process, respectively. The saturated deposition rate of Pt on TiO2 was 0.39 Å/cycle. The photocatalytic activities of Pt@TiO2@CNTs hierarchical structures were higher than those without Pt co-catalyst. The particle size of Pt on TiO2@CNTs was a key factor to determine the efficiency of methylene blue (MB) degradation. The Pt@TiO2@CNTs of 2.41 ± 0.27 nm exhibited the best efficiency of MB degradation.

Total cross section for relativistic positronium interaction with atom

International Nuclear Information System (INIS)

Pak, A.S.; Tarasov, A.V.

1985-01-01

Total cross sections of interaction of positronium relativistic atoms with atoms are calculated. Calculations are conducted within the framework of potential theory in Born approximaton. Contributions in total cross section of coherent (σsub(coh)) and incoherent (σsub(inc)) parts are analyzed. It is shown that for light elements σsub(inc) value is comparable with σsub(coh), and for heavy ones the ratio σsub(inc)/σsub(coh) sufficiently exceeds Zsup(-1) (Z-charge of the atomic nucleus. Numerical calculation results are presented. A conclusion is made on importance of the coherent part account during the calculation of total cross sections

Preparation of PtSnCu/C and PtSn/C electrocatalysts and activation by dealloying processes for ethanol electrooxidation; Preparacao de eletrocatalisadores PtSnCu/C e PtSn/C e ativacao por processos de dealloying para aplicacao na oxidacao eletroquuimica do etanol

Energy Technology Data Exchange (ETDEWEB)

Crisafulli, Rudy

2013-06-01

PtSnCu/C (with different Pt:Sn:Cu atomic ratios) and PtSn/C (50:50) electrocatalysts were prepared by borohydride (BR) and alcohol-reduction (AR) processes using H{sub 2}PtCl{sub 6}.6H{sub 2}O, SnCl{sub 2}.2H{sub 2}O and CuCl{sub 2}.2H{sub 2}O as metal sources, NaBH{sub 4} and ethylene glycol as reducing agents, 2-propanol and ethylene glycol/water as solvents and carbon black as support. In a further step, these electrocatalysts were activated by chemical (CD) and electrochemical (ED) dealloying processes through acid treatment and thin porous coating technique, respectively. These materials were characterized by energy dispersive X-ray, Xray diffraction, transmission electron microscopy, line scan energy dispersive Xray and cyclic voltammetry. Electrochemical studies for ethanol electro-oxidation were performed by cyclic voltammetry, chronoamperometry and in single Direct Ethanol Fuel Cell using Membrane Electrode Assembly (MEA). The anodic effluents were analysed by gas chromatography. The X-ray diffractograms of the as-synthesized electrocatalysts showed the typical face-centered cubic structure (FCC) of platinum and its alloys. After dealloying, the X-ray diffractograms showed that the Pt FCC structure was preserved. The crystallite sizes of the assynthesized electrocatalysts were in the range of <=2 nm to 3 nm and after dealloying there were no significant variations in sizes. The energy dispersive Xray analysis of the as-synthesized electrocatalysts showed a Pt:Sn and Pt:Sn:Cu atomic ratios similar to the nominal values. After chemical and electrochemical dealloying of the electrocatalysts the ranged Pt:Sn and Pt:Sn:Cu atomic ratios showed that Cu and Sn atoms were removed. However, chemical dealloying process proved to be more efficient for removing Cu and electrochemical dealloying for removing Sn. The line scan energy dispersive X-ray analysis showed that acid and electrochemical treatments were efficient to dealloying Cu and/or Sn superficial atoms of

Critical assessment of Pt surface energy - An atomistic study

Science.gov (United States)

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

2018-04-01

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

Evidence for non-conservative current-induced forces in the breaking of Au and Pt atomic chains.

Science.gov (United States)

Sabater, Carlos; Untiedt, Carlos; van Ruitenbeek, Jan M

2015-01-01

This experimental work aims at probing current-induced forces at the atomic scale. Specifically it addresses predictions in recent work regarding the appearance of run-away modes as a result of a combined effect of the non-conservative wind force and a 'Berry force'. The systems we consider here are atomic chains of Au and Pt atoms, for which we investigate the distribution of break down voltage values. We observe two distinct modes of breaking for Au atomic chains. The breaking at high voltage appears to behave as expected for regular break down by thermal excitation due to Joule heating. However, there is a low-voltage breaking mode that has characteristics expected for the mechanism of current-induced forces. Although a full comparison would require more detailed information on the individual atomic configurations, the systems we consider are very similar to those considered in recent model calculations and the comparison between experiment and theory is very encouraging for the interpretation we propose.

Evidence for non-conservative current-induced forces in the breaking of Au and Pt atomic chains

Directory of Open Access Journals (Sweden)

Carlos Sabater

2015-12-01

Full Text Available This experimental work aims at probing current-induced forces at the atomic scale. Specifically it addresses predictions in recent work regarding the appearance of run-away modes as a result of a combined effect of the non-conservative wind force and a ‘Berry force’. The systems we consider here are atomic chains of Au and Pt atoms, for which we investigate the distribution of break down voltage values. We observe two distinct modes of breaking for Au atomic chains. The breaking at high voltage appears to behave as expected for regular break down by thermal excitation due to Joule heating. However, there is a low-voltage breaking mode that has characteristics expected for the mechanism of current-induced forces. Although a full comparison would require more detailed information on the individual atomic configurations, the systems we consider are very similar to those considered in recent model calculations and the comparison between experiment and theory is very encouraging for the interpretation we propose.

Pt-Al2O3 dual layer atomic layer deposition coating in high aspect ratio nanopores

Science.gov (United States)

Pardon, Gaspard; Gatty, Hithesh K.; Stemme, Göran; van der Wijngaart, Wouter; Roxhed, Niclas

2013-01-01

Functional nanoporous materials are promising for a number of applications ranging from selective biofiltration to fuel cell electrodes. This work reports the functionalization of nanoporous membranes using atomic layer deposition (ALD). ALD is used to conformally deposit platinum (Pt) and aluminum oxide (Al2O3) on Pt in nanopores to form a metal-insulator stack inside the nanopore. Deposition of these materials inside nanopores allows the addition of extra functionalities to nanoporous materials such as anodic aluminum oxide (AAO) membranes. Conformal deposition of Pt on such materials enables increased performances for electrochemical sensing applications or fuel cell electrodes. An additional conformal Al2O3 layer on such a Pt film forms a metal-insulator-electrolyte system, enabling field effect control of the nanofluidic properties of the membrane. This opens novel possibilities in electrically controlled biofiltration. In this work, the deposition of these two materials on AAO membranes is investigated theoretically and experimentally. Successful process parameters are proposed for a reliable and cost-effective conformal deposition on high aspect ratio three-dimensional nanostructures. A device consisting of a silicon chip supporting an AAO membrane of 6 mm diameter and 1.3 μm thickness with 80 nm diameter pores is fabricated. The pore diameter is reduced to 40 nm by a conformal deposition of 11 nm Pt and 9 nm Al2O3 using ALD.

Interface architecture determined electrocatalytic activity of Pt on vertically oriented TiO(2) nanotubes.

Science.gov (United States)

Rettew, Robert E; Allam, Nageh K; Alamgir, Faisal M

2011-02-01

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

Positron total scattering cross-sections for alkali atoms

Science.gov (United States)

Sinha, Nidhi; Singh, Suvam; Antony, Bobby

2018-01-01

Positron-impact total scattering cross-sections for Li, Na, K, Rb, Cs and Fr atoms are calculated in the energy range from 5-5000 eV employing modified spherical complex optical potential formalism. The main aim of this work is to apply this formalism to the less studied positron-target collision systems. The results are compared with previous theoretical and experimental data, wherever available. In general, the present data show overall agreement and consistency with other results. Furthermore, we have done a comparative study of the results to investigate the effect of atomic size on the cross-sections as we descend through the group in the periodic table. We have also plotted a correlation graph of the present total cross-sections with polarizability and number of target electrons. The two correlation plots confirm the credibility and consistency of the present results. Besides, this is the first theoretical attempt to report positron-impact total cross-sections of alkali atoms over such a wide energy range.

Magnetic and electronic properties of a Pt-Co bilayer on Pt(1 1 1)

International Nuclear Information System (INIS)

Giovanelli, L.; De Santis, M.; Panaccione, G.; Sirotti, F.; Torelli, P.; Vobornik, I.; Larcipretea, R.; Egger, S.; Saint-Lager, M.C.; Dolle, P.; Rossi, G.

2005-01-01

Atomically thin Co/Pt(1 1 1) interfaces grown at different temperatures are characterized by very different values of perpendicular magnetic anisotropy as a consequence of the local structure and coordination. Here we present a study of the structural, magnetic and electronic properties for interfaces grown in UHV onto clean Pt(1 1 1) in different kinetic conditions. When one monolayer of Co is deposited at 540 K a thermally activated exchange reaction leads to a sharp Pt-Co double interface giving rise to a strong increase of the magneto-optical response with respect to the Co monolayer deposited at room temperature. The results are interpreted in terms of atomic hybridization as detected by valence band photoelectron spectroscopy

Direct methanol fuel cell with extended reaction zone anode: PtRu and PtRuMo supported on graphite felt

Energy Technology Data Exchange (ETDEWEB)

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

2007-05-15

Pressed graphite felt (thickness {proportional_to}350 {mu}m) with electrodeposited PtRu (43 g m{sup -2}, 1.4:1 atomic ratio) or PtRuMo (52 g m{sup -2}, 1:1:0.3 atomic ratio) nanoparticle catalysts was investigated as an anode for direct methanol fuel cells. At temperatures above 333 K the fuel cell performance of the PtRuMo catalyst was superior compared to PtRu. The power density was 2200 W m{sup -2} with PtRuMo at 5500 A m{sup -2} and 353 K while under the same conditions PtRu yielded 1925 W m{sup -2}. However, the degradation rate of the Mo containing catalyst formulation was higher. Compared to conventional gas diffusion electrodes with comparable PtRu catalyst composition and load, the graphite felt anodes gave higher power densities mainly due to the extended reaction zone for methanol oxidation. (author)

Direct methanol fuel cell with extended reaction zone anode: PtRu and PtRuMo supported on graphite felt

Science.gov (United States)

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

Pressed graphite felt (thickness ∼350 μm) with electrodeposited PtRu (43 g m -2, 1.4:1 atomic ratio) or PtRuMo (52 g m -2, 1:1:0.3 atomic ratio) nanoparticle catalysts was investigated as an anode for direct methanol fuel cells. At temperatures above 333 K the fuel cell performance of the PtRuMo catalyst was superior compared to PtRu. The power density was 2200 W m -2 with PtRuMo at 5500 A m -2 and 353 K while under the same conditions PtRu yielded 1925 W m -2. However, the degradation rate of the Mo containing catalyst formulation was higher. Compared to conventional gas diffusion electrodes with comparable PtRu catalyst composition and load, the graphite felt anodes gave higher power densities mainly due to the extended reaction zone for methanol oxidation.

Atomically flat surface of (0 0 1) textured FePt thin films by residual stress control

Energy Technology Data Exchange (ETDEWEB)

Liu, S.H. [Department of Materials Science and Engineering, Feng Chia University, Taichung 407, Taiwan (China); Hsiao, S.N., E-mail: pmami.hsiao@gmail.com [Department of Materials Science and Engineering, Feng Chia University, Taichung 407, Taiwan (China); Department of Power Mechanical Engineering, National Tsing Hua University, Hsinchu 300, Taiwan (China); Chou, C.L.; Chen, S.K. [Department of Materials Science and Engineering, Feng Chia University, Taichung 407, Taiwan (China); Lee, H.Y. [National Synchrotron Radiation Research Center, Hsinchu 300, Taiwan (China); Department of Applied Science, National Hsinchu University of Education, Hsinchu 300, Taiwan (China)

2015-11-01

Highlights: • We demonstrate crystallographic structure, (0 0 1) texture, surface roughness, and residual stress in the single-layered FePt thin films annealed at various heating rates (10–110 K/s). • Texture coefficient of (0 0 1)-plane of the samples increases with increasing heating rate from 10 to 40 K/s, which is correlated with perpendicular magnetic anisotropy and in-plane tensile stress. • Dewetting phenomenon due to stress relaxation leads to the broadening of [0 0 1] easy axis and degradation of perpendicular magnetic anisotropy. • A strong dependence of surface roughness on in-plane residual stress was revealed. • When the samples are RTA at 40 K/s, the enhanced perpendicular magnetic anisotropy and atomically surface roughness are achieved. - Abstract: Single-layered Fe{sub 52}Pt{sub 48} films with thickness of 10 nm were sputter-deposited on glass substrates. Rapid thermal annealing with different heating rates (10–110 K/s) was applied to transform as-deposited fcc phase into L1{sub 0} phase and meanwhile to align [0 0 1]-axis of L1{sub 0} crystal along plane normal direction. Based on X-ray diffractometry using synchrotron radiation source, the texture coefficient of (0 0 1)-plane increases with increasing heating rate from 10 to 40 K/s, which is correlated with perpendicular magnetic anisotropy and in-plane tensile stress analyzed by asymmetric sin{sup 2} ψ method. Furthermore, it was revealed by atomic force microscopy that the dewetting process occurred as heating rate was raised up to 80 K/s and higher. The change in the microstructure due to stress relaxation leads to the degradation of (0 0 1) orientation and magnetic properties. Surface roughness is closely related to the in-plane tensile stress. Enhanced perpendicular magnetic anisotropy and atomically flat surface were achieved for the samples annealed at 40 K/s, which may be suitable for further practical applications. This work also suggests a feasible way for surface

In Situ PDF Study of the Nucleation and Growth of Intermetallic PtPb Nanocrystals

DEFF Research Database (Denmark)

Saha, Dipankar; Bojesen, Espen D.; Mamakhel, Mohammad Aref Hasen

2017-01-01

The mechanism of Pt and PtPb nanocrystal formation under supercritical ethanol conditions has been investigated by means of in situ X-ray total scattering and pair distribution function (PDF) analysis. The metal complex structures of two different platinum precursor solutions, chloroplatinic acid...... supercritical ethanol process for obtaining phase-pure hexagonal PtPb nanocrystals. The study thus highlights the importance of in situ studies in revealing atomic-scale information about nucleation mechanisms, which can be used in design of specific synthesis pathways, and the new continuous-flow process...

Exotic high activity surface patterns in PtAu nanoclusters

KAUST Repository

Mokkath, Junais Habeeb; Schwingenschlö gl, Udo

2013-01-01

of the truncated octahedron cluster motif. Exotic surface patterns are obtained particularly for Pt-rich compositions, where Pt atoms are being surrounded by Au atoms. These surface arrangements boost the catalytic activity by creating a large number of active

Functionalized graphene-Pt composites for fuel cells and photoelectrochemical cells

Science.gov (United States)

Diankov, Georgi; An, Jihwan; Park, Joonsuk; Goldhaber, David J. K.; Prinz, Friedrich B.

2017-08-29

A method of growing crystals on two-dimensional layered material is provided that includes reversibly hydrogenating a two-dimensional layered material, using a controlled radio-frequency hydrogen plasma, depositing Pt atoms on the reversibly hydrogenated two-dimensional layered material, using Atomic Layer Deposition (ALD), where the reversibly hydrogenated two-dimensional layered material promotes loss of methyl groups in an ALD Pt precursor, and forming Pt-O on the reversibly hydrogenated two-dimensional layered material, using combustion by O.sub.2, where the Pt-O is used for subsequent Pt half-cycles of the ALD process, where growth of Pt crystals occurs.

Further insights into the durability of Pt3Co/C electrocatalysts: Formation of “hollow” Pt nanoparticles induced by the Kirkendall effect

International Nuclear Information System (INIS)

Dubau, L.; Durst, J.; Maillard, F.; Guétaz, L.; Chatenet, M.; André, J.; Rossinot, E.

2011-01-01

Highlights: ► Pt 3 Co/C electrocatalysts for the oxygen reduction reaction. ► During operation in a PEMFC, Co atoms are depleted from the mother electrocatalyst. ► The structure of the Pt–Co/C electrocatalysts in the long-term is determined by a balance between Co surface segregation and formation of oxygenated species from water. ► The presence of Co atoms in the subsurface region severely depreciates the oxygen reduction reaction activity. ► “Hollow” Pt nanoparticles have been detected for the first time in a PEMFC. - Abstract: This paper provides further insights into the degradation mechanisms of nanometer-sized Pt 3 Co/C particles under various proton-exchange membrane fuel cell (PEMFC) operating conditions. We confirm that Co atoms are continuously depleted from the mother Pt 3 Co/C electrocatalyst because they can diffuse from the bulk to the surface of the material. The structure of the Pt–Co/C nanoparticles in the long-term is determined by a balance between Co surface segregation and formation of oxygenated species from water splitting. When the PEMFC is operated at high current density (low cathode potential, below the onset of surface oxide formation from water), a steady-state is reached between the rate of Co dissolution at the surface and Co surface segregation. Consequently, Co and Pt atoms remain homogeneously distributed within the Pt–Co/C particles and the thickness of the Pt-shell is maintained to a small value not detectable by atomic-resolution high-angle annular dark-field scanning transmission electron microscopy. When the PEMFC is operated at low current density (high cathode potential), the formation of surface oxides from water and the resulting “place-exchange” mechanism enhance the rate of diffusion of Co atoms to the surface. Consequently, the fresh Pt 3 Co/C particles form core/shell particles with thick Pt-shells and Co content < 5 at% and, ultimately, “hollow” Pt nanoparticles (Kirkendall effect). To the

Three dimensional PtRh alloy porous nanostructures: tuning the atomic composition and controlling the morphology for the application of direct methanol fuel cells

Energy Technology Data Exchange (ETDEWEB)

Zhang, Yuan [Department of Chemistry, Shanghai University, Shanghai 200444 (China); Department of Chemical Engineering, Case Western Reserve University, Cleveland, OH 44106 (United States); Janyasupab, Metini; Liu, Chung-Chiun [Department of Chemical Engineering, Case Western Reserve University, Cleveland, OH 44106 (United States); Liu, Chen-Wei [Institute of Material Sciences and Engineering, National Central University, Chung-Li 320 (China); Li, Xinxin [State Key Laboratory of Transducer Technology, Shanghai Institute of Microsystem and Information Technology, Chinese Academy of Sciences, Shanghai 200050 (China); Xu, Jiaqiang [Department of Chemistry, Shanghai University, Shanghai 200444 (China)

2012-09-11

A strategy for the synthesis of PtRh alloy 3D porous nanostructures by controlled aggregation of nanoparticles in oleylamine is presented. The atomic ratio between the two components (Pt and Rh) is tuned by varying the concentration of precursor salts accommodating the oxidation of methanol. The morphology of PtRh alloy nanostructure is controlled by elevating the temperature of the reaction system to 240 C. The prepared 3D porous nanostructures provide a high degree of electrochemical activity and good durability toward the methanol oxidation reaction compared to those of the commercial Pt/C (E-TEK) and PtRh nanoparticles. Therefore, the 3D alloy porous nanostructures provide a good opportunity to explore their catalytic properties for methanol oxidation. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Effects of Cr underlayer and Pt buffer layer on the interfacial structure and magnetic characteristics of sputtered FePt films

International Nuclear Information System (INIS)

Sun, A.-C.; Hsu, J.-H.; Huang, H.L.; Kuo, P.C.

2006-01-01

This work develops a new method for growing L1 0 FePt(0 0 1) thin film on a Pt/Cr bilayer using an amorphous glass substrate. Semi-coherent epitaxial growth was initiated from the Cr(0 0 2) underlayer, continued through the Pt(0 0 1) buffer layer, and extended into the L1 0 FePt(0 0 1) magnetic layer. The squareness of the L1 0 FePt film in the presence of both a Cr underlayer and a Pt buffer layer was close to unity as the magnetic field was applied perpendicular to the film plane. The single L1 0 FePt(1 1 1) orientation was observed in the absence of a Cr underlayer. When a Cr underlayer is inserted, the preferred orientation switched from L1 0 FePt(1 1 1) to L1 0 FePt(0 0 1) and the magnetic film exhibited perpendicular magnetic anisotropy. However, in the absence of an Pt intermediate layer, the Cr atoms diffused directly into the FePt magnetic layer and prevented the formation of the L1 0 FePt(0 0 1) preferred orientation. When a Pt buffer layer was introduced between the FePt and Cr underlayer, the L1 0 FePt(0 0 1) peak appeared. The thickness of the Pt buffer layer also substantially affected the magnetic properties and atomic arrangement at the FePt/Pt and Pt/Cr interfaces

The anisotropy field of FePt L10 nanoparticles controlled by very thin Pt layer

International Nuclear Information System (INIS)

Okamoto, Satoshi; Kitakami, Osamu; Kikuchi, Nobuaki; Miyazaki, Takamichi; Shimada, Yutaka; Chiang, Te-Hsuan

2004-01-01

We have prepared epitaxial FePt L1 0 (001) nanoparticles covered with Pt [d Pt nm]/Ag[(4-d Pt ) nm] overlayers. The particles are oblate spheroids approximately 10 nm in diameter and 2 nm in height. The anisotropy field H k at 0 K, which is evaluated from the temperature dependences of coercivity H c , decreases from 90 to 60 kOe on increasing the Pt thickness from d Pt 0 to 1.5 nm, while the energy barrier at zero field remains unchanged. The significant reduction of H k due to the presence of the adjacent Pt layer can be attributed to an enhanced magnetic moment caused by the ferromagnetic polarization of Pt atoms at the interface. This finding suggests an effective method of controlling the switching field of FePt L1 0 nanoparticles

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

International Nuclear Information System (INIS)

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

2009-01-01

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2009-12-01

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

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

Energy Technology Data Exchange (ETDEWEB)

Silva, Dionisio Fortunato da

2006-07-01

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

Direct imaging of thermally-activated grain-boundary diffusion in Cu/Co/IrMn/Pt exchange-bias structures using atom-probe tomography

Energy Technology Data Exchange (ETDEWEB)

Letellier, F.; Lardé, R.; Le Breton, J.-M., E-mail: jean-marie.lebreton@univ-rouen.fr [Groupe de Physique des Matériaux, UMR 6634 CNRS/Université et INSA de Rouen, F-76801 Saint Etienne du Rouvray (France); Lechevallier, L. [Groupe de Physique des Matériaux, UMR 6634 CNRS/Université et INSA de Rouen, F-76801 Saint Etienne du Rouvray (France); Département de GEII, Université de Cergy-Pontoise, F-95031 Cergy-Pontoise (France); Akmaldinov, K. [SPINTEC, Univ. Grenoble-Alpes/CNRS/INAC-CEA, F-38000 Grenoble (France); CROCUS Technology, F-38025 Grenoble (France); Auffret, S.; Dieny, B.; Baltz, V., E-mail: vincent.baltz@cea.fr [SPINTEC, Univ. Grenoble-Alpes/CNRS/INAC-CEA, F-38000 Grenoble (France)

2014-11-28

Magnetic devices are often subject to thermal processing steps, such as field cooling to set exchange bias and annealing to crystallize amorphous magnetic electrodes. These processing steps may result in interdiffusion and the subsequent deterioration of magnetic properties. In this study, we investigated thermally-activated diffusion in Cu/Co/IrMn/Pt exchange biased polycrystalline thin-film structures using atom probe tomography. Images taken after annealing at 400 °C for 60 min revealed Mn diffusion into Co grains at the Co/IrMn interface and along Pt grain boundaries for the IrMn/Pt stack, i.e., a Harrison type C regime. Annealing at 500 °C showed further Mn diffusion into Co grains. At the IrMn/Pt interface, annealing at 500 °C led to a type B behavior since Mn diffusion was detected both along Pt grain boundaries and also into Pt grains. The deterioration of the films' exchange bias properties upon annealing was correlated to the observed diffusion. In particular, the topmost Pt capping layer thickness turned out to be crucial since a faster deterioration of the exchange bias properties for thicker caps was observed. This is consistent with the idea that Pt acts as a getter for Mn, drawing Mn out of the IrMn layer.

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

International Nuclear Information System (INIS)

Silva, Dionisio Fortunato da

2006-01-01

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

Local Chemical Ordering and Negative Thermal Expansion in PtNi Alloy Nanoparticles.

Science.gov (United States)

Li, Qiang; Zhu, He; Zheng, Lirong; Fan, Longlong; Wang, Na; Rong, Yangchun; Ren, Yang; Chen, Jun; Deng, Jinxia; Xing, Xianran

2017-12-13

An atomic insight into the local chemical ordering and lattice strain is particular interesting to recent emerging bimetallic nanocatalysts such as PtNi alloys. Here, we reported the atomic distribution, chemical environment, and lattice thermal evolution in full-scale structural description of PtNi alloy nanoparticles (NPs). The different segregation of elements in the well-faceted PtNi nanoparticles is convinced by extended X-ray absorption fine structure (EXAFS). Atomic pair distribution function (PDF) study evidences the coexistence of the face-centered cubic and tetragonal ordering parts in the local environment of PtNi nanoparticles. Further reverse Monte Carlo (RMC) simulation with PDF data obviously exposed the segregation as Ni and Pt in the centers of {111} and {001} facets, respectively. Layer-by-layer statistical analysis up to 6 nm for the local atomic pairs revealed the distribution of local tetragonal ordering on the surface. This local coordination environment facilitates the distribution of heteroatomic Pt-Ni pairs, which plays an important role in the negative thermal expansion of Pt 41 Ni 59 NPs. The present study on PtNi alloy NPs from local short-range coordination to long-range average lattice provides a new perspective on tailoring physical properties in nanomaterials.

A theoretical investigation of the structural and electronic properties of 55-atom nanoclusters: The examples of Y-Tc and Pt.

Science.gov (United States)

Batista, Krys E A; Piotrowski, Maurício J; Chaves, Anderson S; Da Silva, Juarez L F

2016-02-07

Several studies have found that the Pt55 nanocluster adopts a distorted reduced core structure, DRC55, in which there are 8-11 atoms in the core and 47-44 atoms in the surface, instead of the compact and high-symmetry icosahedron structure, ICO55, with 13 and 42 atoms in the core and surface, respectively. The DRC structure has also been obtained as the putative global minimum configuration (GMC) for the Zn55 (3d), Cd55 (4d), and Au55 (5d) systems. Thus, the DRC55 structure has been reported only for systems with a large occupation of the d-states, where the effects of the occupation of the valence anti-bonding d-states might play an important role. Can we observe the DRC structure for 55-atom transition-metal systems with non-occupation of the anti-bonding d-states? To address this question, we performed a theoretical investigation of the Y 55, Zr55, Nb55, Mo55, Tc55, and Pt55 nanoclusters, employing density functional theory calculations. For the putative GMCs, we found that the Y 55 adopts the ICO55 structure, while Nb55 and Mo55 adopt a bulk-like fragment based on the hexagonal close-packed structure and Tc55 adopts a face-centered cubic fragment; however, Zr55 adopts a DRC55 structure, like Zn55, Cd55, Pt55, and Au55. Thus we can conclude that the preference for DRC55 structure is not related to the occupation of the anti-bonding d-states, but to a different effect, in fact, a combination of structural and electronic effects. Furthermore, we obtained that the binding energy per atom follows the occupation of the bonding and anti-bonding model, i.e., the stability of the studied systems increases from Y to Tc with a small oscillation for Mo, which also explains the equilibrium bond lengths. We obtained a larger magnetic moment for Y 55 (31 μB) which can be explained by the localization of the d-states in Y at nanoscale, which is not observed for the remaining systems (0-1 μB).

Magnetic behavior in heterometallic one-dimensional chains or octanuclear complex regularly aligned with metal-metal bonds as -Rh-Rh-Pt-Cu-Pt

Science.gov (United States)

Uemura, Kazuhiro

2018-06-01

Heterometallic one-dimensional chains, [{Rh2(O2CCH3)4}{Pt2Cu(piam)4(NH3)4}]n(PF6)2n (1 and 2, piam = pivalamidate) and [{Rh2(O2CCH3)4}{Pt2Cu(piam)4(NH3)4}2](CF3CO2)2(ClO4)2·2H2O (3), are paramagnetic one-dimensional chains or octanuclear complexes that are either aligned as -Rh-Rh-Pt-Cu-Pt- (1 and 2) or as Pt-Cu-Pt-Rh-Rh-Pt-Cu-Pt (3) with metal-metal bonds. Compounds 1-3 have rare structures, from the standpoint of that the paramagnetic species of Cu atoms are linked by direct metal-metal bonds. Magnetic susceptibility measurements for 1-3 performed at temperatures of 2 K-300 K indicated that the unpaired electrons localize in the Cu 3dx2-y2 orbitals, where S = 1/2 Cu(II) atoms are weakly antiferromagnetically coupled with J = -0.35 cm-1 (1), -0.47 cm-1 (2), and -0.45 cm-1 (3).

Effect of gold subsurface layer on the surface activity and segregation in Pt/Au/Pt3M (where M = 3d transition metals) alloy catalyst from first-principles.

Science.gov (United States)

Kim, Chang-Eun; Lim, Dong-Hee; Jang, Jong Hyun; Kim, Hyoung Juhn; Yoon, Sung Pil; Han, Jonghee; Nam, Suk Woo; Hong, Seong-Ahn; Soon, Aloysius; Ham, Hyung Chul

2015-01-21

The effect of a subsurface hetero layer (thin gold) on the activity and stability of Pt skin surface in Pt3M system (M = 3d transition metals) is investigated using the spin-polarized density functional theory calculation. First, we find that the heterometallic interaction between the Pt skin surface and the gold subsurface in Pt/Au/Pt3M system can significantly modify the electronic structure of the Pt skin surface. In particular, the local density of states projected onto the d states of Pt skin surface near the Fermi level is drastically decreased compared to the Pt/Pt/Pt3M case, leading to the reduction of the oxygen binding strength of the Pt skin surface. This modification is related to the increase of surface charge polarization of outmost Pt skin atoms by the electron transfer from the gold subsurface atoms. Furthermore, a subsurface gold layer is found to cast the energetic barrier to the segregation loss of metal atoms from the bulk (inside) region, which can enhance the durability of Pt3M based catalytic system in oxygen reduction condition at fuel cell devices. This study highlights that a gold subsurface hetero layer can provide an additional mean to tune the surface activity toward oxygen species and in turn the oxygen reduction reaction, where the utilization of geometric strain already reaches its practical limit.

Atomic resolution structural insights into PdPt nanoparticle–carbon interactions for the design of highly active and stable electrocatalysts

International Nuclear Information System (INIS)

Slanac, Daniel A.; Li Lin; Mayoral, Alvaro; Yacaman, Miguel José; Manthiram, Arumugam; Stevenson, Keith J.; Johnston, Keith P.

2012-01-01

Graphical abstract: - Abstract: Interfacial interactions between sub-4 nm metal alloy nanoparticles and carbon supports, although not well understood at the atomic level, may be expected to have a profound influence on catalytic properties. Pd 3 Pt 2 alloy particles comprised of a disordered surface layer over a corrugated crystalline core are shown to exhibit strong interfacial interactions with a ∼20–50 nm spherical carbon support, as characterized by probe aberration corrected scanning transmission electron microscopy (pcSTEM). The disordered shells were formed from defects introduced by Pd during arrested growth synthesis of the alloy nanoparticles. The chemical and morphological changes in the catalyst, before and after cyclic stability testing (1000 cycles, 0.5–1.2 V), were probed with cyclic voltammetry (CV), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and pcSTEM. The strong metal–support interaction, along with the uniform alloy structure raised the mass activity by a factor of 1.8 versus pure Pt. The metal–support interactions also mitigated nanoparticle coalescence, dissolution, and ripening, resulting in only a 20% loss in mass activity (versus 60% for pure Pt on carbon) after the cyclic stability test. The design of alloy structure, guided by insight from atomic scale pcSTEM, for enhanced catalytic activity and stability, resulting from strong wetting with a deformable disordered shell, has the potential to be a general paradigm for improving catalytic performance.

Neighboring Hetero-Atom Assistance of Sacrificial Amines to Hydrogen Evolution Using Pt-Loaded TiO2-Photocatalyst

Directory of Open Access Journals (Sweden)

Masahide Yasuda

2014-05-01

Full Text Available Photocatalytic H2 evolution was examined using Pt-loaded TiO2-photocatalyst in the presence of amines as sacrificial agents. In the case of amines with all of the carbon attached to the hetero-atom such as 2-aminoethanol, 1,2-diamonoethane, 2-amino-1,3-propanediol, and 3-amino-1,2-propanediol, they were completely decomposed into CO2 and water to quantitatively evolve H2. On the other hand, the amines with both hetero-atoms and one methyl group at the β-positions (neighboring carbons of amino group such as 2-amino-1-propanol and 1,2-diaminopropane were partially decomposed. Also, the photocatalytic H2 evolution using amines without the hetero-atoms at the β-positions such as ethylamine, propylamine, 1-butylamine, 1,3-diaminopropane, 2-propylamine, and 2-butylamine was inefficient. Thus, it was found that the neighboring hetero-atom strongly assisted the degradation of sacrificial amines. Moreover, rate constants for H2 evolution were compared among amines. In conclusion, the neighboring hetero-atom did not affect the rate constants but enhanced the yield of hydrogen evolution.

Pt-Al{sub 2}O{sub 3} dual layer atomic layer deposition coating in high aspect ratio nanopores

Energy Technology Data Exchange (ETDEWEB)

Pardon, Gaspard; Gatty, Hithesh K; Stemme, Goeran; Wijngaart, Wouter van der; Roxhed, Niclas [KTH Royal Institute of Technology, School of Electrical Engineering, Micro and Nanosystems, Osquldas Vaeg 10, SE-10044 Stockholm (Sweden)

2013-01-11

Functional nanoporous materials are promising for a number of applications ranging from selective biofiltration to fuel cell electrodes. This work reports the functionalization of nanoporous membranes using atomic layer deposition (ALD). ALD is used to conformally deposit platinum (Pt) and aluminum oxide (Al{sub 2}O{sub 3}) on Pt in nanopores to form a metal-insulator stack inside the nanopore. Deposition of these materials inside nanopores allows the addition of extra functionalities to nanoporous materials such as anodic aluminum oxide (AAO) membranes. Conformal deposition of Pt on such materials enables increased performances for electrochemical sensing applications or fuel cell electrodes. An additional conformal Al{sub 2}O{sub 3} layer on such a Pt film forms a metal-insulator-electrolyte system, enabling field effect control of the nanofluidic properties of the membrane. This opens novel possibilities in electrically controlled biofiltration. In this work, the deposition of these two materials on AAO membranes is investigated theoretically and experimentally. Successful process parameters are proposed for a reliable and cost-effective conformal deposition on high aspect ratio three-dimensional nanostructures. A device consisting of a silicon chip supporting an AAO membrane of 6 mm diameter and 1.3 {mu}m thickness with 80 nm diameter pores is fabricated. The pore diameter is reduced to 40 nm by a conformal deposition of 11 nm Pt and 9 nm Al{sub 2}O{sub 3} using ALD. (paper)

Optically sensitive devices based on Pt nano particles fabricated by atomic layer deposition and embedded in a dielectric stack

Energy Technology Data Exchange (ETDEWEB)

Mikhelashvili, V.; Padmanabhan, R.; Eisenstein, G. [Electrical Engineering Department, Technion, Haifa 3200 (Israel); Russell Berrie Nanotechnology Institute, Technion, Haifa 3200 (Israel); Meyler, B.; Yofis, S.; Weindling, S.; Salzman, J. [Electrical Engineering Department, Technion, Haifa 3200 (Israel); Atiya, G.; Cohen-Hyams, Z.; Kaplan, W. D. [Department of Material Science and Engineering, Technion, Haifa 3200 (Israel); Russell Berrie Nanotechnology Institute, Technion, Haifa 3200 (Israel); Ankonina, G. [Russell Berrie Nanotechnology Institute, Technion, Haifa 3200 (Israel); Photovoltaic Laboratory, Technion, Haifa 3200 (Israel)

2015-10-07

We report a series of metal insulator semiconductor devices with embedded Pt nano particles (NPs) fabricated using a low temperature atomic layer deposition process. Optically sensitive nonvolatile memory cells as well as optical sensors: (i) varactors, whose capacitance-voltage characteristics, nonlinearity, and peak capacitance are strongly dependent on illumination intensity; (ii) highly linear photo detectors whose responsivity is enhanced due to the Pt NPs. Both single devices and back to back pairs of diodes were used. The different configurations enable a variety of functionalities with many potential applications in biomedical sensing, environmental surveying, simple imagers for consumer electronics and military uses. The simplicity and planar configuration of the proposed devices makes them suitable for standard CMOS fabrication technology.

Optically sensitive devices based on Pt nano particles fabricated by atomic layer deposition and embedded in a dielectric stack

International Nuclear Information System (INIS)

Mikhelashvili, V.; Padmanabhan, R.; Eisenstein, G.; Meyler, B.; Yofis, S.; Weindling, S.; Salzman, J.; Atiya, G.; Cohen-Hyams, Z.; Kaplan, W. D.; Ankonina, G.

2015-01-01

We report a series of metal insulator semiconductor devices with embedded Pt nano particles (NPs) fabricated using a low temperature atomic layer deposition process. Optically sensitive nonvolatile memory cells as well as optical sensors: (i) varactors, whose capacitance-voltage characteristics, nonlinearity, and peak capacitance are strongly dependent on illumination intensity; (ii) highly linear photo detectors whose responsivity is enhanced due to the Pt NPs. Both single devices and back to back pairs of diodes were used. The different configurations enable a variety of functionalities with many potential applications in biomedical sensing, environmental surveying, simple imagers for consumer electronics and military uses. The simplicity and planar configuration of the proposed devices makes them suitable for standard CMOS fabrication technology

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

International Nuclear Information System (INIS)

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. (paper)

Binuclear Pt-Tl bonded complex with square pyramidal coordination around Pt: a combined multinuclear NMR, EXAFS, UV-Vis, and DFT/TDDFT study in dimethylsulfoxide solution.

Science.gov (United States)

Purgel, Mihály; Maliarik, Mikhail; Glaser, Julius; Platas-Iglesias, Carlos; Persson, Ingmar; Tóth, Imre

2011-07-04

The structure and bonding of a new Pt-Tl bonded complex formed in dimethylsulfoxide (dmso), (CN)(4)Pt-Tl(dmso)(5)(+), have been studied by multinuclear NMR and UV-vis spectroscopies, and EXAFS measurements in combination with density functional theory (DFT) and time dependent density functional theory (TDDFT) calculations. This complex is formed following the equilibrium reaction Pt(CN)(4)(2-) + Tl(dmso)(6)(3+) ⇆ (CN)(4)Pt-Tl(dmso)(5)(+) + dmso. The stability constant of the Pt-Tl bonded species, as determined using (13)C NMR spectroscopy, amounts to log K = 2.9 ± 0.2. The (NC)(4)Pt-Tl(dmso)(5)(+) species constitutes the first example of a Pt-Tl bonded cyanide complex in which the sixth coordination position around Pt (in trans with respect to the Tl atom) is not occupied. The spectral parameters confirm the formation of the metal-metal bond, but differ substantially from those measured earlier in aqueous solution for complexes (CN)(5)Pt-Tl(CN)(n)(H(2)O)(x)(n-) (n = 0-3). The (205) Tl NMR chemical shift, δ = 75 ppm, is at extraordinary high field, while spin-spin coupling constant, (1)J(Pt-Tl) = 93 kHz, is the largest measured to date for a Pt-Tl bond in the absence of supporting bridging ligands. The absorption spectrum is dominated by two strong absorption bands in the UV region that are assigned to MMCT (Pt → Tl) and LMCT (dmso → Tl) bands, respectively, on the basis of MO and TDDFT calculations. The solution of the complex has a bright yellow color as a result of a shoulder present on the low energy side of the band at 355 nm. The geometry of the (CN)(4)Pt-Tl core can be elucidated from NMR data, but the particular stoichiometry and structure involving the dmso ligands are established by using Tl and Pt L(III)-edge EXAFS measurements. The Pt-Tl bond distance is 2.67(1) Å, the Tl-O bond distance is 2.282(6) Å, and the Pt-C-N entity is linear with Pt-C and Pt···N distances amounting to 1.969(6) and 3.096(6) Å, respectively. Geometry optimizations on

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

Energy Technology Data Exchange (ETDEWEB)

Kim, Chang-Eun [Fuel Cell Research Center, Korea Institute of Science and Technology (KIST), 39-1 Hawolgok, Seongbuk-gu, Seoul 136-791 (Korea, Republic of); Global E3 Institute and Department of Materials Science and Engineering, Yonsei University, 120-749 Seoul (Korea, Republic of); Lim, Dong-Hee [Fuel Cell Research Center, Korea Institute of Science and Technology (KIST), 39-1 Hawolgok, Seongbuk-gu, Seoul 136-791 (Korea, Republic of); Department of Environmental Engineering, Chungbuk National University, 1 Chungdae-ro, Seowon-Gu, Cheongju, Chungbuk 362-763 (Korea, Republic of); Jang, Jong Hyun; Kim, Hyoung Juhn; Yoon, Sung Pil; Han, Jonghee; Nam, Suk Woo [Fuel Cell Research Center, Korea Institute of Science and Technology (KIST), 39-1 Hawolgok, Seongbuk-gu, Seoul 136-791 (Korea, Republic of); Hong, Seong-Ahn [Fuel Cell Research Center, Korea Institute of Science and Technology (KIST), 39-1 Hawolgok, Seongbuk-gu, Seoul 136-791 (Korea, Republic of); Department of Advanced Materials Chemistry, Korea University, Sejong-city 339-700 (Korea, Republic of); Soon, Aloysius, E-mail: aloysius.soon@yonsei.ac.kr, E-mail: hchahm@kist.re.kr [Global E3 Institute and Department of Materials Science and Engineering, Yonsei University, 120-749 Seoul (Korea, Republic of); Ham, Hyung Chul, E-mail: aloysius.soon@yonsei.ac.kr, E-mail: hchahm@kist.re.kr [Fuel Cell Research Center, Korea Institute of Science and Technology (KIST), 39-1 Hawolgok, Seongbuk-gu, Seoul 136-791 (Korea, Republic of); Clean Energy and Chemical Engineering, University of Science and Technology (UST), 217 Gajungro, Yuseong-gu, Daejeon 305-333 (Korea, Republic of)

2015-01-21

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

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

Energy Technology Data Exchange (ETDEWEB)

Tusi, M.M.; Ayoub, J.M.S.; Costa, T.C.; Spinace, E.V.; Neto, A.O., E-mail: aolivei@ipen.b, E-mail: espinace@ipen.b [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil)

2010-07-01

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

Au@AuPt nanoparticles embedded in B-doped graphene: A superior electrocatalyst for determination of rutin

Energy Technology Data Exchange (ETDEWEB)

Chen, Xianlan; Yang, Guangming; Feng, Shaoping; Shi, Ling; Huang, Zhaolong [School of Science, Honghe University (China); Key Laboratory of Natural Pharamaceutical & Chemical Biology of Yunnan Province Mengzi, Yunnan 661100 (China); Pan, Haibo [Fujian Key Lab of Medical Instrument & Pharmaceutical Technology, Yishan Campus, Fuzhou University, Fuzhou, Fujian 350002 (China); Liu, Wei, E-mail: liuwei4728@126.com [School of Science, Honghe University (China); Key Laboratory of Natural Pharamaceutical & Chemical Biology of Yunnan Province Mengzi, Yunnan 661100 (China)

2017-04-30

Highlights: • The formation of B-doped graphene (BG) with high content of a total B species use hydrothermal method with B{sub 2}O{sub 3} as reducing agent and boron source. • BG was exfoliated into monolayer nanosheet impregnated by Au@AuPt NPs because B atom creates a net positive charge to facilitate NPs adsorption. • The dispersed carboxyl units of BG can form hydrogen bonding with the phenolic hydroxyl groups of rutin, making more rutin participate in reaction. • Au@AuPt NPs can form charge accumulation or valence change on prominent part of the surface, improving the catalytic effect to rutin. • More electroactive sites were generated by doping B atoms into graphene structures, which act as multidimensional electron transport pathways. - Abstract: A hydrothermal approach was used to prepare B-doped graphene with B{sub 2}O{sub 3} as reductant and boron source. Results reveal that the boron atoms have been successfully embedded into graphene with a high content of a total B species (2.85 at.%). Then, B-doped graphene was exfoliated further into monolayer nanosheet by impregnating Au@AuPt core-shell nanoparticles (Au@AuPt NPs) because boron atom creates a net positive charge, which facilitates Au@AuPt NPs adsorption to form Au@AuPt NPs/B-doped graphene hybrid nanocatalysts. After that, the Au@AuPt NPs/B-doped hybrid suspension was dropped on glassy carbon electrode for sensing rutin. In this way, the dispersed carboxyl units of B-doped graphene can form hydrogen bonding with the phenolic hydroxyl groups of rutin, making rutin enrich easily on modified electrode surface to enhance the electrochemical response. At the same time, its electrochemical mechanism on the modified electrode was elucidated using cyclic voltammetry. It was found that its electrochemical behavior on modified electrode surface was a surface-controlled quasi-reversible process, and the charge transfer coefficient (α) and electron transfer number (n) were 0.296 and 2, respectively

Highly Durable Platinum Single-Atom Alloy Catalyst for Electrochemical Reactions

DEFF Research Database (Denmark)

Kim, Jiwhan; Roh, Chi-Woo; Sahoo, Suman Kalyan

2018-01-01

Single atomic Pt catalyst can offer efficient utilization of the expensive platinum and provide unique selectivity because it lacks ensemble sites. However, designing such a catalyst with high Pt loading and good durability is very challenging. Here, single atomic Pt catalyst supported on antimony...... functional theory calculations show that replacing Sb sites with Pt atoms in the bulk phase or at the surface of SbSn or ATO is energetically favorable. The Pt1/ATO shows superior activity and durability for formic acid oxidation reaction, compared to a commercial Pt/C catalyst. The single atomic Pt...... structure is retained even after a harsh durability test, which is performed by repeating cyclic voltammetry in the range of 0.05–1.4 V for 1800 cycles. A full cell is fabricated for direct formic acid fuel cell using the Pt1/ATO as an anode catalyst, and an order of magnitude higher cell power is obtained...

Relativistic total energy and chemical potential of heavy atoms and positive ions

International Nuclear Information System (INIS)

Hill, S.H.; Grout, P.J.; March, N.H.

1984-01-01

The relativistic Thomas-Fermi theory, with a finite nucleus, is used to study the variation of the chemical potential μ with atomic number Z and number of electrons N (N <= Z). The difference between the total energy of positive ions and that of the corresponding neutral atom has been obtained. The scaling predictions are confirmed by numerical calculations. The first principles calculation of the relativistic Thomas-Fermi total energy of neutral atoms is also studied. (author)

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

Science.gov (United States)

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

2017-08-01

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

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

DEFF Research Database (Denmark)

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

2013-01-01

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

A theoretical investigation of the structural and electronic properties of 55-atom nanoclusters: The examples of Y–Tc and Pt

Energy Technology Data Exchange (ETDEWEB)

Batista, Krys E. A.; Piotrowski, Maurício J., E-mail: mauriciomjp@gmail.com [Department of Physics, Federal University of Pelotas, P.O. Box 354, 96010 − 900, Pelotas, RS (Brazil); Chaves, Anderson S.; Da Silva, Juarez L. F., E-mail: juarez-dasilva@iqsc.usp.br [São Carlos Institute of Chemistry, University of São Paulo, P.O. Box 780, 13560 − 970, São Carlos, SP (Brazil)

2016-02-07

Several studies have found that the Pt{sub 55} nanocluster adopts a distorted reduced core structure, DRC{sub 55}, in which there are 8–11 atoms in the core and 47–44 atoms in the surface, instead of the compact and high-symmetry icosahedron structure, ICO{sub 55}, with 13 and 42 atoms in the core and surface, respectively. The DRC structure has also been obtained as the putative global minimum configuration (GMC) for the Zn{sub 55} (3d), Cd{sub 55} (4d), and Au{sub 55} (5d) systems. Thus, the DRC{sub 55} structure has been reported only for systems with a large occupation of the d-states, where the effects of the occupation of the valence anti-bonding d-states might play an important role. Can we observe the DRC structure for 55-atom transition-metal systems with non-occupation of the anti-bonding d-states? To address this question, we performed a theoretical investigation of the Y {sub 55}, Zr{sub 55}, Nb{sub 55}, Mo{sub 55}, Tc{sub 55}, and Pt{sub 55} nanoclusters, employing density functional theory calculations. For the putative GMCs, we found that the Y {sub 55} adopts the ICO{sub 55} structure, while Nb{sub 55} and Mo{sub 55} adopt a bulk-like fragment based on the hexagonal close-packed structure and Tc{sub 55} adopts a face-centered cubic fragment; however, Zr{sub 55} adopts a DRC{sub 55} structure, like Zn{sub 55}, Cd{sub 55}, Pt{sub 55}, and Au{sub 55}. Thus we can conclude that the preference for DRC{sub 55} structure is not related to the occupation of the anti-bonding d-states, but to a different effect, in fact, a combination of structural and electronic effects. Furthermore, we obtained that the binding energy per atom follows the occupation of the bonding and anti-bonding model, i.e., the stability of the studied systems increases from Y to Tc with a small oscillation for Mo, which also explains the equilibrium bond lengths. We obtained a larger magnetic moment for Y {sub 55} (31 μ{sub B}) which can be explained by the localization of the d

Clarification of the mechanism of sulfur trioxide electrolysis. Evaluation of SO3 and O atom adsorbed on Pt surface

International Nuclear Information System (INIS)

Suzuki, Chikashi; Nakagiri, Toshio

2008-01-01

We developed a hybrid thermo-chemical process, which included a SO 3 electrolysis process utilizing the heat supplied by a fast breeder reactor (FBR), as a new hydrogen production process. To clarify the mechanism of SO 3 electrolysis, we evaluated the electronic states of SO 3 and O atom adsorbed on the Pt (111) surface using first-principles calculations with a slab model. Moreover, we evaluated the chemical bonding states of SO 3 and adsorbed O using molecular orbital calculation on the basis of the calculations using a slab model. We found that there were two stable adsorbed SO 3 configurations on the Pt surface. From the molecular orbital calculation, it was found that the S-O bond became weak by SO 3 absorption, and it was conjectured that SO 3 dissociation proceeded through the intermediate state of adsorbed SO 2 and adsorbed O on the Pt surface. Moreover, we derived the O coverage considering the adsorbed SO 2 and evaluated the influence of SO 3 adsorption energy on the O coverage. (author)

Ion-irradiation induced chemical ordering of FePt and FePtAu nanoparticles

Energy Technology Data Exchange (ETDEWEB)

Seetala, Naidu V. [Department of Physics, Grambling State University, RWE Jones Drive, Carver Hall 81, Grambling, LA 71245 (United States)]. E-mail: naidusv@gram.edu; Harrell, J.W. [MINT Center, University of Alabama, Tuscaloosa, AL 35487 (United States); Lawson, Jeremy [MINT Center, University of Alabama, Tuscaloosa, AL 35487 (United States); Nikles, David E. [MINT Center, University of Alabama, Tuscaloosa, AL 35487 (United States); Williams, John R. [Department of Physics, Auburn University, Auburn, AL 36849 (United States); Isaacs-Smith, Tamara [Department of Physics, Auburn University, Auburn, AL 36849 (United States)

2005-12-15

We have studied the effect of ion-beam irradiation on reducing the ordering temperature of FePt and FePtAu nanoparticles. FePt and FePt(Au14%) 4 nm particles dispersed on a Si-substrate were irradiated by 300 keV Al-ions with a dose of 1 x 10{sup 16} ions/cm{sup 2} at 43 {sup o}C using a water-cooled flange in order to minimize the vacancy migration and voids formation within the collision cascades. Partial chemical ordering has been observed in as-irradiated particles with coercivity of 60-130 Oe. Post-irradiation annealing at 220 {sup o}C enhanced chemical ordering in FePt nanoparticles with coercivity of 3500 Oe, magnetic anisotropy of 1.5 x 10{sup 7} erg/cc, and thermal stability factor of 130. A much higher 375 {sup o}C post-irradiation annealing was required in FePtAu, presumably because Au atoms were trapped at Fe/Pt lattice sites at lower temperatures. As the annealing temperature increased, anomalous features in the magnetization reversal curves were observed that disappeared at higher annealing temperatures.

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

DEFF Research Database (Denmark)

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

2011-01-01

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

Pt skin coated hollow Ag-Pt bimetallic nanoparticles with high catalytic activity for oxygen reduction reaction

Science.gov (United States)

Fu, Tao; Huang, Jianxing; Lai, Shaobo; Zhang, Size; Fang, Jun; Zhao, Jinbao

2017-10-01

The catalytic activity and stability of electrocatalyst is critical for the commercialization of fuel cells, and recent reports reveal the great potential of the hollow structures with Pt skin coat for developing high-powered electrocatalysts due to their highly efficient utilization of the Pt atoms. Here, we provide a novel strategy to prepare the Pt skin coated hollow Ag-Pt structure (Ag-Pt@Pt) of ∼8 nm size at room temperature. As loaded on the graphene, the Ag-Pt@Pt exhibits a remarkable mass activity of 0.864 A/mgPt (at 0.9 V, vs. reversible hydrogen electrode (RHE)) towards oxygen reduction reaction (ORR), which is 5.30 times of the commercial Pt/C catalyst, and the Ag-Pt@Pt also shows a better stability during the ORR catalytic process. The mechanism of this significant enhancement can be attributed to the higher Pt utilization and the unique Pt on Ag-Pt surface structure, which is confirmed by the density functional theory (DFT) calculations and other characterization methods. In conclusion, this original work offers a low-cost and environment-friendly method to prepare a high active electrocatalyst with cheaper price, and this work also discloses the correlation between surface structures and ORR catalytic activity for the hollow structures with Pt skin coat, which can be instructive for designing novel advanced electrocatalysts for fuel cells.

An improved $\\pi$K atom lifetime measurement

CERN Document Server

Yazkov, V

2016-01-01

This note describes details of analysis of data samples collected by DIRAC experiment on a Pt target in 2007 and Ni targets in 2008–2010 in order to estimate the lifetime of πK atoms. Experimental results consist of eight distinct data samples: both charge combinations ( π + K − and K + π − atoms) obtained in different experimental conditions corresponding to each year of data taking. Estimations of systematic errors are presented. Taking into account both statistical and systematic uncertainties, the lifetime of πK atoms is estimated by the maximum likelihood method. The above sample comprises the total statistics, available for the analysis, thus the improvement over the previous estimation [1,3] of the πK atom lifetime is achieved.

Sonochemical synthesis and characterization of Pt/CNT, Pt/TiO2, and Pt/CNT/TiO2 electrocatalysts for methanol electro-oxidation

International Nuclear Information System (INIS)

Bedolla-Valdez, Z.I.; Verde-Gómez, Y.; Valenzuela-Muñiz, A.M.; Gochi-Ponce, Y.; Oropeza-Guzmán, M.T.; Berhault, Gilles; Alonso-Núñez, G.

2015-01-01

Highlights: • Pt/CNT/TiO 2 electrocatalyst was successfully prepared by the sonochemical method. • The electrocatalyst Pt/CNT/TiO 2 was synthesized without heat treatments, additives or surfactants. • The TiO 2 -Pt interaction improves the CO-tolerance of Pt/CNT/TiO 2 , as well as the electrocatalyst stability. • Low amount of multi-walled carbon nanotubes increases the current density of Pt/CNT/TiO 2 significantly compared to Pt/TiO 2 . - Abstract: Pt electrocatalyst supported on composite formed of multi-walled carbon nanotubes and titanium oxide (CNT/TiO 2 ) was successfully synthesized by a sonochemical method without heat treatments, surfactants or additives. This electrocatalyst could be used for direct methanol fuel cells (DMFC) applications. For comparison, Pt/CNT and Pt/TiO 2 electrocatalysts were prepared as reference samples. Structural properties and morphology of the synthesized materials were examined by X-ray diffraction, transmission electron microscopy, Raman spectroscopy, X-ray photoelectron spectroscopy and their specific surface areas were determined by the Brunauer-Emmett-Teller method. The Pt and acid-treated CNT contents were analyzed by inductively coupled plasma atomic emission spectroscopy and thermogravimetric analysis, respectively. The electrochemical properties of the synthesized electrocatalysts were evaluated by cyclic voltammetry (CV) and chronoamperometry in a three-electrode cell at room temperature. The evaluation performed using electrochemical techniques suggests that TiO 2 promotes the CO-tolerance due to TiO 2 -Pt interaction. The CV tests demonstrated that 6 wt.% of acid-treated CNT increases significantly the current density when Pt selectively interacts with TiO 2 .

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

Energy Technology Data Exchange (ETDEWEB)

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

2007-08-01

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

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

International Nuclear Information System (INIS)

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

2007-01-01

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

Chain formation of metal atoms

DEFF Research Database (Denmark)

Bahn, Sune Rastad; Jacobsen, Karsten Wedel

2001-01-01

The possibility of formation of single-atomic chains by manipulation of nanocontacts is studied for a selection of metals (Ni, Pd, Pt, Cu, Ag, Au). Molecular dynamics simulations show that the tendency for chain formation is strongest for Au and Pt. Density functional theory calculations indicate...... that the metals which form chains exhibit pronounced many-atom interactions with strong bonding in low coordinated systems....

The binding of platinum hexahalides (Cl, Br and I) to hen egg-white lysozyme and the chemical transformation of the PtI{sub 6} octahedral complex to a PtI{sub 3} moiety bound to His15

Energy Technology Data Exchange (ETDEWEB)

Tanley, Simon W. M.; Starkey, Laurina-Victoria; Lamplough, Lucinda; Kaenket, Surasek; Helliwell, John R., E-mail: john.helliwell@manchester.ac.uk [University of Manchester, Brunswick Street, Manchester M13 9PL (United Kingdom)

2014-08-29

The platinum hexahalides have an octahedral arrangement of six halogen atoms bound to a Pt centre, thus having an octahedral shape that could prove to be useful in interpreting poor electron-density maps. In a detailed characterization, PtI{sub 6} chemically transformed to a square-planar PtI{sub 3} complex bound to the N{sup δ} atom of His15 of HEWL was also observed, which was not observed for PtBr{sub 6} or PtCl{sub 6}. This study examines the binding and chemical stability of the platinum hexahalides K{sub 2}PtCl{sub 6}, K{sub 2}PtBr{sub 6} and K{sub 2}PtI{sub 6} when soaked into pre-grown hen egg-white lysozyme (HEWL) crystals as the protein host. Direct comparison of the iodo complex with the chloro and bromo complexes shows that the iodo complex is partly chemically transformed to a square-planar PtI{sub 3} complex bound to the N{sup δ} atom of His15, a chemical behaviour that is not exhibited by the chloro or bromo complexes. Each complex does, however, bind to HEWL in its octahedral form either at one site (PtI{sub 6}) or at two sites (PtBr{sub 6} and PtCl{sub 6}). As heavy-atom derivatives of a protein, the octahedral shape of the hexahalides could be helpful in cases of difficult-to-interpret electron-density maps as they would be recognisable ‘objects’.

Synthesis and some coordination chemistry of the PSnP pincer-type stannylene Sn(NCH2PtBu2)2C6H4, attempts to prepare the PSiP analogue, and the effect of the E atom on the molecular structures of E(NCH2PtBu2)2C6H4 (E = C, Si, Ge, Sn).

Science.gov (United States)

Brugos, Javier; Cabeza, Javier A; García-Álvarez, Pablo; Pérez-Carreño, Enrique; Polo, Diego

2018-03-26

The non-donor-stabilized PSnP pincer-type stannylene Sn(NCH2PtBu2)2C6H4 (1) has been prepared by treating SnCl2 with Li2(NCH2PtBu2)2C6H4. All attempts to synthesize the analogous PSiP silylene by reduction of the (previously unknown) silanes SiCl2(NCH2PtBu2)2C6H4 (2), SiHCl(NCH2PtBu2)2C6H4 (3) and SiH(HMDS)(NCH2PtBu2)2C6H4 (4; HMDS = N(SiMe3)2) have been unsuccessful. The almost planar (excluding the tert-butyl groups) molecular structure of stannylene 1 (determined by X-ray crystallography) has been rationalized with the help of DFT calculations, which have shown that, in the series of diphosphanetetrylenes E(NCH2PtBu2)2C6H4 (E = C, Si, Ge, Sn), the most stable conformation of the compounds with E = Ge and Sn has both P atoms very close to the EN2C6H4 plane, near (interacting with) the E atom, whereas for the compounds with E = C and Si, both phosphane groups are located at one side of the EN2C6H4 plane and far away from the E atom. The size of the E atom and the strength of stabilizing donor-acceptor PE interactions (both increase on going down in group 14) are key factors in determining the molecular structures of these diphosphanetetrylenes. The syntheses of the chloridostannyl complexes [Rh{κ2Sn,P-SnCl(NCH2PtBu2)2C6H4}(η4-cod)] (5), [RuCl{κ2Sn,P-SnCl(NCH2PtBu2)2C6H4}(η6-cym)] (6) and [IrCl{κ2Sn,P-SnCl(NCH2PtBu2)2C6H4}(η5-C5Me5)] (7) have demonstrated the tendency of stannylene 1 to insert its Sn atom into M-Cl bonds of transition metal complexes and the preference of the resulting PSnP chloridostannyl group to act as a κ2Sn,P-chelating ligand, maintaining an uncoordinated phosphane fragment. X-ray diffraction data (of 6), 31P{1H} NMR data (of 5-7) and DFT calculations (on 6) are consistent with the existence of a weak PSn interaction involving the non-coordinated P atom of complexes 5-7, similar to that found in stannylene 1.

α-NiPt(Al) and phase equilibria in the Ni-Al-Pt system at 1150 deg C

International Nuclear Information System (INIS)

Hayashi, S.; Ford, S.I.; Young, D.J.; Sordelet, D.J.; Besser, M.F.; Gleeson, B.

2005-01-01

The α-NiPt(Al) phase and its associated equilibria in the Ni-Al-Pt system at 1150 deg C were investigated by analyzing equilibrated bulk alloys and the interdiffusion zones of diffusion couples. Phase constitutions, tie-lines and microstructures were determined using a combination of techniques, including high-energy synchrotron X-ray diffraction, scanning electron microscopy and electron probe microanalysis. A large Pt solubility limit was found to exist in the β-NiAl, ∼42 at.%, and in γ'-Ni 3 Al, ∼32 at.%. The α-NiPt(Al) phase was found to have wide Pt solubility range of about 33-60 at.% and to skew along an almost constant Pt/Al ratio of 1.5. The α-NiPt(Al) has an ordered face-centered tetragonal L1 0 crystal structure, with the Al and Pt atoms found to be preferentially located in the corners and prismatic faces, respectively. The temperature dependence of the lattice parameters and unit cell volume of the α phase were also determined

Point-Defect Mediated Bonding of Pt Clusters on (5,5) Carbon Nanotubes

DEFF Research Database (Denmark)

Wang, J. G.; Lv, Y. A.; Li, X. N.

2009-01-01

The adhesion of various sizes of Pt clusters on the metallic (5,5) carbon nanotubes (CNTs) with and without the point defect has been investigated by means of density functional theory (DFT). The calculations show that the binding energies of Pt-n (n = 1-6) clusters on the defect free CNTs are more......). The stronger orbital hybridization between the Pt atom and the carbon atom shows larger charge transfers on the defective CNTs than on the defect free CNTs, which allows the strong interaction between Pt clusters and CNTs. On the basis of DFT calculations, CNTs with point defect can be used as the catalyst...

ANALISIS TOTAL PRODUCTIVE MAINTENANCE PADA LINE 8/CARBONATED SOFT DRINK PT COCA-COLA BOTTLING INDONESIA CENTRAL JAVA

Directory of Open Access Journals (Sweden)

Darminto Pujotomo

2012-02-01

Full Text Available PT. Coca-Cola Bottling Indonesia (CCBI Central Java merupakan salah satu perusahaan produsen minuman ringan yang terkemuka di Indonesia, dengan dua jenis kelompok produk yang dihasilkan yaitu minuman karbonasi/Carbonated Soft Drink (Coca-Cola, Sprite, dan Fanta dan non-karbonasi (Frestea dan Ades. Dalam usaha untuk mempertahankan mutu dan meningkatkan produktifitas, salah satu faktor yang harus diperhatikan adalah masalah perawatan fasilitas/mesin produksi.  Makalah ini membahas mengenai penyebab dan akibat yang ditimbulkan oleh breakdown mesin terjadi pada Line 8/Carbonated Soft Drink, khususnya pada conveyor, filler machine, dan bottle washer machine. Untuk mendapatkan mesin yang dapat terjaga keterandalannya dibutuhkan suatu konsep yang baik. Total Productive Maintenance (TPM merupakan sebuah konsep yang baik untuk merealisasikan hal tersebut. Konsep ini, selain melibatkan semua personil dalam perusahaan, juga bertujuan untuk merawat semua fasilitas produksi yang dimiliki perusahaan.Data yang digunakan merupakan data breakdown conveyor, filler machine, dan bottle washer machine dari ME Monthly Report PT.CCBI selama bulan Januari-Desember 2005 khususnya line 8. Selain itu makalah ini juga membahas performance maintenance PT. Coca-Cola Bottling Indonesia-Central Java, dengan memperhitungkan nilai Mean Time Beetwen Failure (MTBF, Mean Time To Repair (MTTR, serta Availability mesin, dengan menggunakan data record Line 8 selama bulan Mei 2006 sampai bulan Juli 2006. Sehingga nantinya akan diketahui informasi keadaan aktual dari perusahaan tentang sistem perawatannya, khususnya pada Line 8/Carbonated Soft Drink apakah baik atau buruk. Kata kunci : Total Production Maintenance, Conveyor, Filler Machine, Bottle Washer Machine, Performance Maintenance   PT. Coca-Cola Bottling Indonesia (CCBI-Central Java represent one of notable light beverage producer company in Indonesia, with two product group type yielded is carbonated beverage/Carbonated Soft

Transition voltages of vacuum-spaced and molecular junctions with Ag and Pt electrodes

KAUST Repository

Wu, Kunlin

2014-07-07

The transition voltage of vacuum-spaced and molecular junctions constructed with Ag and Pt electrodes is investigated by non-equilibrium Green\\'s function formalism combined with density functional theory. Our calculations show that, similarly to the case of Au-vacuum-Au previously studied, the transition voltages of Ag and Pt metal-vacuum-metal junctions with atomic protrusions on the electrode surface are determined by the local density of states of the p-type atomic orbitals of the protrusion. Since the energy position of the Pt 6p atomic orbitals is higher than that of the 5p/6p of Ag and Au, the transition voltage of Pt-vacuum-Pt junctions is larger than that of both Ag-vacuum-Ag and Au-vacuum-Au junctions. When one moves to analyzing asymmetric molecular junctions constructed with biphenyl thiol as central molecule, then the transition voltage is found to depend on the specific bonding site for the sulfur atom in the thiol group. In particular agreement with experiments, where the largest transition voltage is found for Ag and the smallest for Pt, is obtained when one assumes S binding at the hollow-bridge site on the Ag/Au(111) surface and at the adatom site on the Pt(111) one. This demonstrates the critical role played by the linker-electrode binding geometry in determining the transition voltage of devices made of conjugated thiol molecules. © 2014 AIP Publishing LLC.

Alloy formation and chemisorption at Zn/Pt(111) bimetallic surfaces using alkali ISS, XPD, and TPD.

Science.gov (United States)

Ho, Chih-Sung; Martono, Eddie; Banerjee, Santanu; Roszell, John; Vohs, John; Koel, Bruce E

2013-11-21

Alloy formation and chemisorption at bimetallic surfaces formed by vapor-depositing Zn on a Pt(111) single crystal were investigated primarily by using X-ray photoelectron diffraction (XPD), X-ray photoelectron spectroscopy (XPS), low-energy alkali ion scattering spectroscopy (ALISS), low electron energy diffraction (LEED), and temperature programmed desorption (TPD). A wide range of conditions were investigated to explore whether deposition and annealing of Zn films could produce well-defined, ordered alloy surfaces, similar to those encountered for Sn/Pt(111) surface alloys. These attempts were unsuccessful, although weak, diffuse (2 × 2) spots were observed under special conditions. The particular PtZn bimetallic alloy created by annealing one monolayer of Zn on Pt(111) at 600 K, which has a Zn composition in the surface layer of about 5 at. %, was investigated in detail by using XPD and ALISS. Only a diffuse (1 × 1) pattern was observed from this surface by LEED, suggesting that no long-range, ordered alloy structure was formed. Zn atoms were substitutionally incorporated into the Pt(111) crystal to form a near-surface alloy in which Zn atoms were found to reside primarily in the topmost and second layers. The alloyed Zn atoms in the topmost layer are coplanar with the Pt atoms in the surface layer, without any "buckling" of Zn, that is, displacement in the vertical direction. This result is expected because of the similar size of Pt and Zn, based on previous studies of bimetallic Pt alloys. Zn atoms desorb upon heating rather than diffusing deep into the bulk of the Pt crystal. Temperature programmed desorption (TPD) measurements show that both CO and NO have lower desorption energies on the PtZn alloy surface compared to that on the clean Pt(111) surface.

Influence of Pt Gate Electrode Thickness on the Hydrogen Gas Sensing Characteristics of Pt/In2O3/SiC Hetero-Junction Devices

Directory of Open Access Journals (Sweden)

S. Kandasamy

2007-09-01

Full Text Available Hetero-junction Pt/In2O3/SiC devices with different Pt thickness (30, 50 and 90nm were fabricated and their hydrogen gas sensing characteristics have been studied. Pt and In2O3 thin films were deposited by laser ablation. The hydrogen sensitivity was found to increase with decreasing Pt electrode thickness. For devices with Pt thickness of 30 nm, the sensitivity gradually increased with increasing temperature and reached a maximum of 390 mV for 1% hydrogen in air at 530°C. Atomic force microscopy (AFM analysis revealed a decrease in Pt grain size and surface roughness for increasing Pt thickness. The relationship between the gas sensing performance and the Pt film thickness and surface morphology is discussed.

Electrodeposition of Isolated Platinum Atoms and Clusters on Bismuth-Characterization and Electrocatalysis.

Science.gov (United States)

Zhou, Min; Dick, Jeffrey E; Bard, Allen J

2017-12-06

We describe a method for the electrodeposition of an isolated single Pt atom or small cluster, up to 9 atoms, on a bismuth ultramicroelectrode (UME). This deposition was immediately followed by electrochemical characterization via the hydrogen evolution reaction (HER) that occurs readily on the electrodeposited Pt but not on Bi. The observed voltammetric current plateau, even for a single atom, which behaves as an electrode, allows the estimation of deposit size. Pt was plated from solutions of femtomolar PtCl 6 2- , which allowed precise control of the arrival of ions and thus the plating rate on the Bi UME, to one ion every few seconds. This allowed the atom-by-atom fabrication of isolated platinum deposits, ranging from single atoms to 9-atom clusters. The limiting currents in voltammetry gave the size and number of atoms of the clusters. Given the stochasticity of the plating process, we show that the number of atoms plated over a given time (10 and 20 s) follows a Poisson distribution. Taking the potential at a certain current density as a measure of the relative rate of the HER, we found that the potential shifted positively as the size increased, with single atoms showing the largest overpotentials compared to bulk Pt.

Crystal structure of the coordination polymer [FeIII2{PtII(CN4}3

Directory of Open Access Journals (Sweden)

Maksym Seredyuk

2015-01-01

Full Text Available The title complex, poly[dodeca-μ-cyanido-diiron(IIItriplatinum(II], [FeIII2{PtII(CN4}3], has a three-dimensional polymeric structure. It is built-up from square-planar [PtII(CN4]2− anions (point group symmetry 2/m bridging cationic [FeIIIPtII(CN4]+∞ layers extending in the bc plane. The FeII atoms of the layers are located on inversion centres and exhibit an octahedral coordination sphere defined by six N atoms of cyanide ligands, while the PtII atoms are located on twofold rotation axes and are surrounded by four C atoms of the cyanide ligands in a square-planar coordination. The geometrical preferences of the two cations for octahedral and square-planar coordination, respectively, lead to a corrugated organisation of the layers. The distance between neighbouring [FeIIIPtII(CN4]+∞ layers corresponds to the length a/2 = 8.0070 (3 Å, and the separation between two neighbouring PtII atoms of the bridging [PtII(CN4]2− groups corresponds to the length of the c axis [7.5720 (2 Å]. The structure is porous with accessible voids of 390 Å3 per unit cell.

Electrochemical stability of subnanometer Pt clusters

DEFF Research Database (Denmark)

Quinson, Jonathan; Röefzaad, Melanie; Deiana, Davide

2018-01-01

In the present work, the degradation of size-selected Pt nanoclusters is studied under electrochemical conditions. This model catalyst mimics carbon supported Pt nanoclusters and nanoparticles typically employed in proton exchange membrane fuel cells (PEMFCs). Insight into the early stage...... of degradation is given by high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) and confirmed by transmission electron microscopy (TEM). In contrast to common assumptions, it is demonstrated that even extremely small Pt clusters exhibit a remarkable stability under electrochemical...... - is observed. In light of the findings reported, developing highly-dispersed subnanometer Pt clusters as catalyst for PEMFCs is a realistic approach provided the operation conditions are suitably adjusted. Furthermore, mitigation strategies to improve the stability of few-atoms catalyst under electrochemical...

Structures of Pt clusters on graphene doped with nitrogen, boron, and silicon: a theoretical study

Institute of Scientific and Technical Information of China (English)

Dai Xian-Qi; Tang Ya-Nan; Dai Ya-Wei; Li Yan-Hui; Zhao Jian-Hua; Zhao Bao; Yang Zong-Xian

2011-01-01

The structures of Pt clusters on nitrogen-, boron-, silicon- doped graphenes are theoretically studied using densityfunctional theory. These dopants (nitrogen, boron and silicon) each do not induce a local curvature in the graphene and the doped graphenes all retain their planar form. The formation energy of the silicon-graphene system is lower than those of the nitrogen-, boron-doped graphenes, indicating that the silicon atom is easier to incorporate into the graphene.All the substitutional impurities enhance the interaction between the Pt atom and the graphene. The adsorption energy of a Pt adsorbed on the silicon-doped graphene is much higher than those on the nitrogen- and boron-doped graphenes.The doped silicon atom can provide more charges to enhance the Pt-graphene interaction and the formation of Pt clusters each with a large size. The stable structures of Pt clusters on the doped-graphenes are dimeric, triangle and tetrahedron with the increase of the Pt coverage. Of all the studied structures, the tetrahedron is the most stable cluster which has the least influence on the planar surface of doped-graphene.

Electrocatalysis of the oxidations of some organic compounds on noble-metal electrodes by foreign-metal ad-atoms

International Nuclear Information System (INIS)

Tsang, R.W.

1981-10-01

Electrochemical oxidation of formic acid was studied on Pt electrodes in acid, and that of dextrose was studied on Pt and Au in alkali. Poisoning was observed on Pt but not on Au. Several heavy-metal ad-atoms (Pb, Bi, Tl) enhance greatly the anodic currents on Pt, while transition metals (Cu, Zn) inhibit the oxidation on Pt. The enhancement effect of the metal ad-atoms is correlated with electron structure. All metal ad-atoms showed an inhibitory effect on Au. Amperometry showed that Pt electrodes are completely deactivated within 10 s during dextrose oxidation without ad-atoms, while Au retains much of its activity even after 10 min. Ad-atoms maintains the Pt activity over much more than 10 s. 50 figures, 38 tables

Atomic resonances above the total ionization energy

International Nuclear Information System (INIS)

Doolen, G.

1975-01-01

A rigorous result obtained using the theory associated with dilatation analytic potentials is that by performing a complex coordinate rotation, r/subj/ → r/subj/e/subi//sup theta/, on a Hamiltonian whose potential involves only pairwise Coulombic interactions, one can show that when theta = π/2, no complex eigenvalues (resonances) appear whose energies have a real part greater than the total ionization energy of the atomic system. This appears to conflict with experimental results of Walton, Peart, and Dolder, who find resonance behavior above the total ionization energy of the H -- system and also the theoretical stabilization results of Taylor and Thomas for the same system. A possible resolution of this apparent conflict is discussed and a calculation to check its validity is proposed

Efficient detection of total cholesterol using (ChEt–ChOx/ZnO/Pt/Si) bioelectrode based on ZnO matrix

International Nuclear Information System (INIS)

Batra, Neha; Sharma, Anjali; Tomar, Monika; Gupta, Vinay

2014-01-01

Present study highlights the importance of ZnO matrix prepared by vapour phase transport technique on platinum coated Si platform (ZnO/Pt/Si) as a potential matrix for the realization of highly sensitive and selective bioelectrode for detection of total cholesterol. Bienzymes cholesterol esterase (ChEt) and cholesterol oxidase (ChOx) have been immobilized onto the surface of ZnO thin film matrix by physical adsorption technique. The prepared bioelectrode (ChEt–ChOx/ZnO/Pt/Si) is utilized for detection of total cholesterol using the cyclic voltammetry technique. The bioelectrode (ChEt–ChOx/ZnO/Pt/Si) is found to exhibit efficient sensing response characteristics with high sensitivity of 190 μA mM −1 cm −2 ; good linearity in the range of 0.5–12 mM total cholesterol concentration, and a very low Michaelis–Menten constant of 0.68 mM which indicates high affinity of bienzymes immobilized on ZnO towards the analyte (total cholesterol). The enhanced response is attributed to the development of ZnO thin film based matrix having good electron transport property and nanoporous morphology for effective loading of enzymes with favourable orientation. - Highlights: • Fabrication of a ZnO nanostructured thin film based efficient matrix • Utilizing prepared matrix for detection of total cholesterol (free + esterified) • Cholesterol oxidase and cholesterol esterase are the corresponding selective enzymes. • Vapour phase transport technique, for the fabrication of nanostructured ZnO matrix • The bioelectrode exhibits enhanced response characteristics towards total cholesterol detection

Efficient detection of total cholesterol using (ChEt–ChOx/ZnO/Pt/Si) bioelectrode based on ZnO matrix

Energy Technology Data Exchange (ETDEWEB)

Batra, Neha; Sharma, Anjali [Department of Physics and Astrophysics, University of Delhi, Delhi 110007 (India); Tomar, Monika [Department of Physics, Miranda House, University of Delhi, Delhi 110007 (India); Gupta, Vinay, E-mail: drguptavinay@gmail.com [Department of Physics and Astrophysics, University of Delhi, Delhi 110007 (India)

2014-07-01

Present study highlights the importance of ZnO matrix prepared by vapour phase transport technique on platinum coated Si platform (ZnO/Pt/Si) as a potential matrix for the realization of highly sensitive and selective bioelectrode for detection of total cholesterol. Bienzymes cholesterol esterase (ChEt) and cholesterol oxidase (ChOx) have been immobilized onto the surface of ZnO thin film matrix by physical adsorption technique. The prepared bioelectrode (ChEt–ChOx/ZnO/Pt/Si) is utilized for detection of total cholesterol using the cyclic voltammetry technique. The bioelectrode (ChEt–ChOx/ZnO/Pt/Si) is found to exhibit efficient sensing response characteristics with high sensitivity of 190 μA mM{sup −1} cm{sup −2}; good linearity in the range of 0.5–12 mM total cholesterol concentration, and a very low Michaelis–Menten constant of 0.68 mM which indicates high affinity of bienzymes immobilized on ZnO towards the analyte (total cholesterol). The enhanced response is attributed to the development of ZnO thin film based matrix having good electron transport property and nanoporous morphology for effective loading of enzymes with favourable orientation. - Highlights: • Fabrication of a ZnO nanostructured thin film based efficient matrix • Utilizing prepared matrix for detection of total cholesterol (free + esterified) • Cholesterol oxidase and cholesterol esterase are the corresponding selective enzymes. • Vapour phase transport technique, for the fabrication of nanostructured ZnO matrix • The bioelectrode exhibits enhanced response characteristics towards total cholesterol detection.

Does one-dimensional (1D) adatom and cluster diffusion of Pt on the Pt(110)-(1 x 2) surface lead to 1D ripening?

International Nuclear Information System (INIS)

Linderoth, T R; Horch, S; Petersen, L; Laegsgaard, E; Stensgaard, I; Besenbacher, F

2005-01-01

The technique of scanning tunnelling microscopy (STM) uniquely allows dynamic processes on surfaces to be followed directly in real space and at atomic resolution. Results for the 551225 surface diffusion of Pt adatoms and clusters on the anisotropic, missing row reconstructed Pt(110)-(1 x 2) surface are briefly reviewed. Mass transport in this system is entirely one-dimensional (1D) since, at low adatom coverage, atoms and clusters are confined to the missing row troughs. In this paper, we therefore address the question if Pt/Pt(110)-(1 x 2) is a 1D model system to study late stage growth phenomena such as island ripening? From STM measurements, we quantify the morphology changes resulting from annealing a surface configuration with small 1D Pt islands in the missing row troughs to temperatures in the interval 369-395 K. Interestingly, the resulting increase in island sizes (ripening) cannot be accounted for by the known island and adatom mobilities within a 1D model. An explanation is provided from dynamic, time-resolved 'STM-movies' that directly reveal two novel island-mediated mechanisms for inter-trough mass transport which cause the Pt/Pt(110)-(1 x 2) system not to be purely 1D at the higher surface coverage used in the annealing experiments

Application of a distorted wave model to electron capture in atomic collisions

International Nuclear Information System (INIS)

Deco, G.R.; Martinez, A.E.; Rivarola, R.D.

1988-01-01

In this work, it is presented the CDW-EIS approximation applied to the description of processes of electron capture in ion-atom collisions. Differential and total cross sections are compared to results obtained by other theoretical models, as well as, to experimental data. (A.C.A.S.) [pt

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

Energy Technology Data Exchange (ETDEWEB)

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

2017-04-01

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

Formation of Surface and Quantum-Well States in Ultra Thin Pt Films on the Au(111 Surface

Directory of Open Access Journals (Sweden)

Igor V. Silkin

2017-12-01

Full Text Available The electronic structure of the Pt/Au(111 heterostructures with a number of Pt monolayers n ranging from one to three is studied in the density-functional-theory framework. The calculations demonstrate that the deposition of the Pt atomic thin films on gold substrate results in strong modifications of the electronic structure at the surface. In particular, the Au(111 s-p-type Shockley surface state becomes completely unoccupied at deposition of any number of Pt monolayers. The Pt adlayer generates numerous quantum-well states in various energy gaps of Au(111 with strong spatial confinement at the surface. As a result, strong enhancement in the local density of state at the surface Pt atomic layer in comparison with clean Pt surface is obtained. The excess in the density of states has maximal magnitude in the case of one monolayer Pt adlayer and gradually reduces with increasing number of Pt atomic layers. The spin–orbit coupling produces strong modification of the energy dispersion of the electronic states generated by the Pt adlayer and gives rise to certain quantum states with a characteristic Dirac-cone shape.

Shape resonances and EXAFS scattering in the $Pt L_{2,3}$ XANES from a Pt electrode

CERN Document Server

O'Grady, W E

1999-01-01

Atomic hydrogen and oxygen adsorption on a platinum electrode in H /sub 2/SO/sub 4/ and HClO/sub 4/ electrolytes were studied by Pt L /sub 23/ XANES. The Pt electrode was formed of highly dispersed 1.5-3.0 nm particles supported on $9 carbon. A difference procedure utilizing the L/sub 2/ and L/sub 3/ spectra at various applied voltages was used to isolate the electronic and geometric effects in the XANES spectra. At 0.54 V (relative to RHE) the Pt electrode in $9 HClO/sub 4/ is assumed to be "clean". By taking the difference between the spectra at 0.0 and 0.54 V, the Pt-H antibonding state (electronic effect) is isolated and found to have a Fano-resonance line shape. In addition, a $9 significant Pt-H EXAFS scattering (geometric effect) was found for photon energies 0 to 20 eV above the edge. The difference between the spectra at 1.14 and 0.54 V allows isolation of the Pt-O antibonding state and the Pt-O EXAFS $9 scattering. (7 refs).

EXAFS Characterization of Dendrimer-Derived Pt/γ-Al2O3

International Nuclear Information System (INIS)

Siani, A.; Alexeev, O. S.; Williams, C. T.; Ploehn, H. J.; Amiridis, M. D.

2007-01-01

The various steps involved in the preparation of a Pt/γ-Al2O3 material using hydroxyl-terminated generation four (G4OH) PAMAM dendrimers as templates were monitored by EXAFS. The results indicate that Cl ligands in the Pt precursors (H2PtCl6 and K2PtCl4) were partially replaced by aquo ligands upon hydrolysis to form [PtCl3(H2O)3]+ and [PtCl2(H2O)2] species. After interaction of such species with G4OH, Cl ligands from the first coordination shell of Pt were further replaced by nitrogen atoms from the dendrimer interior, indicating the complexation of Pt with the dendrimer. This process was accompanied by a transfer of the electron density from the dendrimer to Pt, indicating that the former plays the role of a ligand. Following treatment of the H2PtCl6/G4OH and K2PtCl4/G4OH composites with NaBH4, no substantial changes were detecteded in the electronic or coordination environment of Pt, and no formation of metal nanoparticles was observed. However, when the reduction treatment was performed with H2, the formation of extremely small Pt clusters incorporating no more than 4 Pt atoms was observed. These Pt species remained strongly bonded to the dendrimer and their nuclearity depends on the length of the H2 treatment. Formation of Pt nanoparticles with an average diameter of approximately 10 A was finally observed after the deposition of H2PtCl6/G4OH on γ-Al2O3 and drying, suggesting that their formation may be related to the collapse of the dendrimer structure. The Pt nanoparticles formed appear to have high mobility, since subsequent thermal treatment in O2/H2 led to further sintering

Synthesis and characterization of Pd-on-Pt and Au-on-Pt bimetallic nanosheaths on multiwalled carbon nanotubes

International Nuclear Information System (INIS)

Wang Shuangyin; Jiang, San Ping; Wang Xin

2011-01-01

The authors have successfully synthesized Pd-on-Pt (thickness: 12 nm) and Au-on-Pt bimetallic nanosheaths on multiwalled carbon nanotubes (MWCNTs) via a seed-mediated growth approach. Pt nanoparticles as seeds were pre-deposited on MWCNTs with uniform distribution followed by the successive seed-mediated growth of metal atoms reduced by a weak reducing agent, ascorbic acid. The essential role of pre-deposited nanoseed particles on MWCNTs was demonstrated. The as-prepared materials were characterization by transition electron microscopy, energy-dispersive X-ray spectroscopy, and element mapping tools. The current strategy extends the classical seed-mediated growth method to prepare bimetallic nanosheath on MWCNT support.

Facile fabrication of ultrathin Pt overlayers onto nanoporous metal membranes via repeated Cu UPD and in situ redox replacement reaction.

Science.gov (United States)

Liu, Pengpeng; Ge, Xingbo; Wang, Rongyue; Ma, Houyi; Ding, Yi

2009-01-06

Ultrathin Pt films from one to several atomic layers are successfully decorated onto nanoporous gold (NPG) membranes by utilizing under potential deposition (UPD) of Cu onto Au or Pt surfaces, followed by in situ redox replacement reaction (RRR) of UPD Cu by Pt. The thickness of Pt layers can be controlled precisely by repeating the Cu-UPD-RRR cycles. TEM observations coupled with electrochemical testing suggest that the morphology of Pt overlayers changes from an ultrathin epitaxial film in the case of one or two atomic layers to well-dispersed nanoislands in the case of four and more atomic layers. Electron diffraction (ED) patterns confirm that the as-prepared NPG-Pt membranes maintain a single-crystalline structure, even though the thickness of Pt films reaches six atomic layers, indicating the decorated Pt films hold the same crystallographic relationship to the NPG substrate during the entire fabrication process. Due to the regular modulation of Pt utilization, the electrocatalytic activity of NPG-Pt exhibits interesting surface structure dependence in methanol, ethanol, and CO electrooxidation reactions. These novel bimetallic nanocatalysts show excellent electrocatalytic activity and much enhanced poison tolerance as compared to the commercial Pt/C catalysts. The success in the fabrication of NPG-Pt-type materials provides a new path to prepare electrocatalysts with ultralow Pt loading and high Pt utilization, which is of great significance in energy-related applications, such as direct alcohol fuel cells (DAFCs).

Reactivity of chemisorbed oxygen atoms and their catalytic consequences during CH4-O2 catalysis on supported Pt clusters.

Science.gov (United States)

Chin, Ya-Huei Cathy; Buda, Corneliu; Neurock, Matthew; Iglesia, Enrique

2011-10-12

absence of CH(4) show that O(2) activation steps are quasi-equilibrated during catalysis. Measured and DFT-derived C-H bond activation barriers are large, because of the weak stabilization of the CH(3) fragments at transition states, but are compensated by the high entropy of these radical-like species. Turnover rates in this regime decrease with increasing Pt dispersion, because low-coordination exposed Pt atoms on small clusters bind O* more strongly than those that reside at low-index facets on large clusters, thus making O* less effective in H-abstraction. As vacancies (*, also exposed Pt atoms) become available on O*-covered surfaces, O*-* site pairs activate C-H bonds via concerted oxidative addition and H-abstraction in transition states effectively stabilized by CH(3) interactions with the vacancies, which lead to much higher turnover rates than on O*-O* pairs. In this regime, O(2) activation becomes irreversible, because fast C-H bond activation steps scavenge O* as it forms. Thus, O* coverages are set by the prevalent O(2)/CH(4) ratios instead of the O(2) pressures. CH(4)/CD(4) kinetic isotope effects are much larger for turnovers mediated by O*-* than by O*-O* site pairs, because C-H (and C-D) activation steps are required to form the * sites involved in C-H bond activation. Turnover rates for CH(4)-O(2) reactions mediated by O*-* pairs decrease with increasing Pt dispersion, as in the case of O*-O* active structures, because stronger O* binding on small clusters leads not only to less reactive O* atoms, but also to lower vacancy concentrations at cluster surfaces. As O(2)/CH(4) ratios and O* coverages become smaller, O(2) activation on bare Pt clusters becomes the sole kinetically relevant step; turnover rates are proportional to O(2) pressures and independent of CH(4) pressure and no CH(4)/CD(4) kinetic isotope effects are observed. In this regime, turnover rates become nearly independent of Pt dispersion, because the O(2) activation step is essentially

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

International Nuclear Information System (INIS)

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

2017-01-01

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

Evidence of surface migration and formation of catalytically inactive Pt in corrosion studies of Pt+ implanted Ti

International Nuclear Information System (INIS)

Appleton, B.R.; Kelly, E.J.; White, C.W.; Thompson, N.G.; Lichter, B.D.

1980-08-01

This investigation is part of an ongoing research project directed at applying the techniques of ion implantation doping and ion scattering analysis to identify the mechanisms associated with the anodic dissolution of Ti-Pt alloys. The Ti-Pt alloys produced by ion implantation were electrochemically examined in hydrogen saturated 1 N H 2 SO 4 by both potentiostatic polarization and open-circuit potential methods. In this study, Ti samples implanted to relatively high doses (5.4 x 10 15 to 2.9 x 10 16 atoms/cm 2 ) were examined by ion scattering analysis at various stages in the electrochemical measurements. Quantitative measurements showed that the majority of the implanted Pt accumulated on the surface during anodic dissolution and underwent large scale surface migration. Evidence is also presented for the transition of the Pt on the surface from a catalytically active to inactive state. Possible mechanisms for the observed catalytically inactive Pt are discussed

Structural, magnetic and electronic properties of FenPt13−n clusters with n=0–13: A first-principle study

International Nuclear Information System (INIS)

Du, Xiaoli; Liu, Chuan; Zhang, Shengli; Wang, Peng; Huang, Shiping; Tian, Huiping

2014-01-01

The structural, magnetic and electronic properties of Fe n Pt 13−n (n=0–13) nanoclusters are investigated using a density functional theory. It is found that the original icosahedra structure of Fe n Pt 13−n nanoclusters with n=3–8 deforms completely and exhibits the maximum Fe–Pt bonds. Furthermore, all the energetically preferable Fe n Pt 13−n (n=0–13) nanoclusters are found to be ferromagnetic coupling, and the magnetic moments of both Fe and Pt are enhanced. The large exchange splitting between the majority and the minority spin states indicates high magnetic moments based on the analysis of electronic density of states. In addition, electrons transfer from Fe to Pt atoms enhances the local atomic magnetic moments of Fe and Pt in Fe n Pt 13−n nanoclusters. - Highlights: • Magnetic properties of Fe n Pt 13−n are investigated using the density functional theory. • Structure of Fe n Pt 13−n nanoclusters with n=3–8 deforms completely. • Electron transfer from Fe to Pt atoms enhances local atomic magnetic moments. • The large exchange splitting in the spin states indicates high magnetic moments

Ethanol electrooxidation on novel carbon supported Pt/SnOx/C catalysts with varied Pt:Sn ratio

International Nuclear Information System (INIS)

Jiang, L.; Colmenares, L.; Jusys, Z.; Sun, G.Q.; Behm, R.J.

2007-01-01

Novel carbon supported Pt/SnO x /C catalysts with Pt:Sn atomic ratios of 5:5, 6:4, 7:3 and 8:2 were prepared by a modified polyol method and characterized with respect to their structural properties (X-ray diffraction (XRD) and transmission electron microscopy (TEM)), chemical composition (XPS), their electrochemical properties (base voltammetry, CO ad stripping) and their electrocatalytic activity and selectivity for ethanol oxidation (ethanol oxidation reaction (EOR)). The data show that the Pt/SnO x /C catalysts are composed of Pt and tin oxide nanoparticles with an average Pt particle diameter of about 2 nm. The steady-state activity of the Pt/SnO x /C catalysts towards the EOR decreases with tin content at room temperature, but increases at 80 deg. C. On all Pt/SnO x /C catalysts, acetic acid and acetaldehyde represent dominant products, CO 2 formation contributes 1-3% for both potentiostatic and potentiodynamic reaction conditions. With increasing potential, the acetaldehyde yield decreases and the acetic acid yield increases. The apparent activation energies of the EOR increase with tin content (19-29 kJ mol -1 ), but are lower than on Pt/C (32 kJ mol -1 ). The somewhat better performance of the Pt/SnO x /C catalysts compared to alloyed PtSn x /C catalysts is attributed to the presence of both sufficiently large Pt ensembles for ethanol dehydrogenation and C-C bond splitting and of tin oxide for OH generation. Fuel cell measurements performed for comparison largely confirm the results obtained in model studies

Preparation of Pt Au/C and Pt Au Bi/C electrocatalysts using electron beam irradiation for ethanol electro-oxidation in alkaline medium

International Nuclear Information System (INIS)

Silva, Dionisio F.; Geraldes, Adriana N.; Cardoso, Elisangela S.Z.; Gomes, Thiago B.; Linardi, Marcelo; Oliveira Neto, Almir; Spinace, Estevam V.

2011-01-01

Pt Au/C (50:50) and PtAuBi/C electrocatalysts with Pt:Au:Bi atomic ratios of 50:40:10, 50:30:20 and 50:10:40 were prepared in water/2-propanol using electron beam irradiation. The materials were characterized by X-ray diffraction (XRD) and the electro-oxidation of ethanol was studied by chronoamperometry at room temperature. The X-ray diffraction measurements for all electrocatalysts prepared showed four peaks, which are associated with the planes of the face-centered cubic (fcc) structure characteristic of Pt and Pt alloys. For PtAuBi/C it was also observed the presence of a mixture of BiPt alloys and bismuth phases. The average crystallite sizes for Pt/C, PtAu/C, PtAuBi/C (50:40:10), PtAuBi/C (50:30:20) and PtAuBi/C (50:10:40) were in the range of 2.0 - 4.0 nm. The activity of the electrocatalysts for ethanol oxidation in alkaline medium showed that PtAuBi/C (50:40:10) had a higher performance for ethanol oxidation compared to others electrocatalysts prepared. (author)

Preparation of Pt Au/C and Pt Au Bi/C electrocatalysts using electron beam irradiation for ethanol electro-oxidation in alkaline medium

Energy Technology Data Exchange (ETDEWEB)

Silva, Dionisio F.; Geraldes, Adriana N.; Cardoso, Elisangela S.Z.; Gomes, Thiago B.; Linardi, Marcelo; Oliveira Neto, Almir; Spinace, Estevam V., E-mail: dfsilva@ipen.b [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil)

2011-07-01

Pt Au/C (50:50) and PtAuBi/C electrocatalysts with Pt:Au:Bi atomic ratios of 50:40:10, 50:30:20 and 50:10:40 were prepared in water/2-propanol using electron beam irradiation. The materials were characterized by X-ray diffraction (XRD) and the electro-oxidation of ethanol was studied by chronoamperometry at room temperature. The X-ray diffraction measurements for all electrocatalysts prepared showed four peaks, which are associated with the planes of the face-centered cubic (fcc) structure characteristic of Pt and Pt alloys. For PtAuBi/C it was also observed the presence of a mixture of BiPt alloys and bismuth phases. The average crystallite sizes for Pt/C, PtAu/C, PtAuBi/C (50:40:10), PtAuBi/C (50:30:20) and PtAuBi/C (50:10:40) were in the range of 2.0 - 4.0 nm. The activity of the electrocatalysts for ethanol oxidation in alkaline medium showed that PtAuBi/C (50:40:10) had a higher performance for ethanol oxidation compared to others electrocatalysts prepared. (author)

Atomic probes of surface structure and dynamics

International Nuclear Information System (INIS)

Heller, E.J.; Jonsson, H.

1992-01-01

Progress for the period Sept. 15, 1992 to Sept. 14, 1993 is discussed. Semiclassical methods that will allow much faster and more accurate three-dimensional atom--surface scattering calculations, both elastic and inelastic, are being developed. The scattering of He atoms from buckyballs is being investigated as a test problem. Somewhat more detail is given on studies of He atom scattering from defective Pt surfaces. Molecular dynamics simulations of He + and Ar + ion sputtering of Pt surfaces are also being done. He atom scattering from Xe overlayers on metal surfaces and the thermalized dissociation of H 2 on Cu(110) are being studied. (R.W.R.) 64 refs

Fuel cycle integration issues associated with P/T technology

International Nuclear Information System (INIS)

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

1992-01-01

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

Optimization of Pt-Ir on carbon fiber paper for the electro-oxidation of ammonia in alkaline media

International Nuclear Information System (INIS)

Boggs, Bryan K.; Botte, Gerardine G.

2010-01-01

Plating bath concentrations of Pt(IV) and Ir(III) have been optimized as well as the total catalytic loading of bimetallic Pt-Ir alloy for the electro-oxidation of ammonia in alkaline media at standard conditions. This was accomplished using cyclic voltammetry, scanning electron microscopy (SEM), energy dispersive X-ray (EDX), and statistical optimization tools. Concentrations of Pt(IV) and Ir(III) of the plating bath strongly influence electrode surface atomic compositions of the Pt-Ir alloy directly affecting the electro-oxidation behavior of ammonia. Several anode materials were studied using cyclic voltammetry, which demonstrated that Pt-Ir was the most active catalyst for the electro-oxidation of ammonia. Criteria for optimization were minimizing the climatic oxidation overpotential for ammonia and maximizing the exchange current density. Optimized bath composition was found to be 8.844 ± 0.001 g L -1 Pt(IV) and 4.112 ± 0.001 g L -1 Ir(III) based on electrochemical techniques. Physical characterization of the electrodes by SEM indicates that the plating bath concentrations of Pt and Ir influence the growth and deposition behavior of the alloy.

PLD prepared nanostructured Pt-CeO{sub 2} thin films containing ionic platinum

Energy Technology Data Exchange (ETDEWEB)

Vorokhta, M., E-mail: vorohtam@gmail.com [Charles University in Prague, Faculty of Mathematics and Physics, Department of Surface and Plasma Science, V Holešovičkách 2, 18000 Prague 8 (Czech Republic); Khalakhan, I.; Matolínová, I.; Nováková, J.; Haviar, S. [Charles University in Prague, Faculty of Mathematics and Physics, Department of Surface and Plasma Science, V Holešovičkách 2, 18000 Prague 8 (Czech Republic); Lančok, J.; Novotný, M. [Institute of Physics, Academy of Sciences of the Czech Republic, Na Slovance 2, 182 21 Prague, Czhech Republic (Czech Republic); Yoshikawa, H. [National Institute for Materials Science, Sengen 1-2-1, Tsukuba, Ibaraki 305-0047 (Japan); Matolín, V. [Charles University in Prague, Faculty of Mathematics and Physics, Department of Surface and Plasma Science, V Holešovičkách 2, 18000 Prague 8 (Czech Republic)

2017-02-28

Highlights: • Nanostructured Pt-CeO{sub 2} thin catalyst films were grown on plasma etched and non-etched carbon substrates by pulsed laser deposition. • The surface composition of the nanostructured Pt-CeO{sub 2} films was investigated by surface analysis techniques. • The effect of film roughening was separated from the effect of platinum-ceria atomic interactions. - Abstract: The composition of nanostructured Pt-CeO{sub 2} films on graphite substrates prepared by pulsed laser deposition has been investigated by means of hard X-ray photoelectron spectroscopy, scanning electron microscopy, high resolution transmission electron microscopy, and atomic force microscopy. The influence of morphology of the graphite substrates was investigated with respect to the relative concentrations of ionic and metallic Pt species in the films. It was found that the degree of Pt{sup 2+} enrichment is directly related to the surface morphology of graphite substrates. In particular, the deposition of Pt-CeO{sub 2} films on rough graphite substrate etched in oxygen plasma yielded nanostructured Pt-CeO{sub 2} catalyst films with high surface area and high Pt{sup 2+}/Pt{sup 0} ratio. The presented results demonstrate that PLD is a suitable method for the preparation of thin Pt-CeO{sub 2} catalyst films for fuel cell applications.

Photoelectrocatalytic reduction of CO2 into chemicals using Pt-modified reduced graphene oxide combined with Pt-modified TiO2 nanotubes.

Science.gov (United States)

Cheng, Jun; Zhang, Meng; Wu, Gai; Wang, Xin; Zhou, Junhu; Cen, Kefa

2014-06-17

The photoelectrocatalytic (PEC) reduction of CO2 into high-value chemicals is beneficial in alleviating global warming and advancing a low-carbon economy. In this work, Pt-modified reduced graphene oxide (Pt-RGO) and Pt-modified TiO2 nanotubes (Pt-TNT) were combined as cathode and photoanode catalysts, respectively, to form a PEC reactor for converting CO2 into valuable chemicals. XRD, XPS, TEM, AFM, and SEM were employed to characterize the microstructures of the Pt-RGO and Pt-TNT catalysts. Reduction products, such as C2H5OH and CH3COOH, were obtained from CO2 under band gap illumination and biased voltage. A combined liquid product generation rate (CH3OH, C2H5OH, HCOOH, and CH3COOH) of approximately 600 nmol/(h·cm(2)) was observed. Carbon atom conversion rate reached 1,130 nmol/(h·cm(2)), which were much higher than those achieved using Pt-modified carbon nanotubes and platinum carbon as cathode catalysts.

(Pt1-xCux)3Cu2B and Pt9Cu3B5, the first examples of copper platinum borides. Observation of superconductivity in a novel boron filled β-Mn-type compound

Science.gov (United States)

Salamakha, Leonid P.; Sologub, Oksana; Stöger, Berthold; Michor, Herwig; Bauer, Ernst; Rogl, Peter F.

2015-09-01

New ternary copper platinum borides have been synthesized by arc melting of pure elements followed by annealing at 600 °C. The structures have been studied by X-ray single crystal and powder diffraction. (Pt1-xCux)3Cu2B (x=0.33) forms a B-filled β-Mn-type structure (space group P4132; a=0.6671(1) nm). Cu atoms are distributed preferentially on the 8c atom sites, whereas the 12d site is randomly occupied by Pt and Cu atoms (0.670(4) Pt±0.330(4) Cu). Boron is located in octahedral voids of the parent β-Mn-type structure. Pt9Cu3B5 (space group P-62m; a=0.9048(3) nm, c=0.2908(1) nm) adopts the Pt9Zn3B5-δ-type structure. It has a columnar architecture along the short translation vector exhibiting three kinds of [Pt6] trigonal prism columns (boron filled, boron semi-filled and empty) and Pt channels with a pentagonal cross section filled with Cu atoms. The striking structural feature is a [Pt6] cluster in form of an empty trigonal prism at the origin of the unit cell, which is surrounded by coupled [BPt6] and [Pt6] trigonal prisms, rotated perpendicularly to the central one. There is no B-B contact as well as Cu-B contact in the structure. The relationships of Pt9Cu3B5 structure with the structure of Ti1+xOs2-xRuB2 as well as with the structure families of metal sulfides and aluminides have been elucidated. (Pt1-xCux)3Cu2B (x=0.3) (B-filled β-Mn-type structure) is a bulk superconductor with a transition temperature of about 2.06 K and an upper critical field μ0HC2(0)WHH of 1.2 T, whereas no superconducting transition has been observed up to 0.3 K in Pt9Cu3B5 (Pt9Zn3B5-δ-type structure) from electrical resistivity measurements.

Reactivity of hydrogen with uranium in the presence of Pt

International Nuclear Information System (INIS)

Balooch, M.; Siekhaus, W.J.

1997-07-01

The surface-reaction of di-hydrogen with uranium in the presence of Pt clusters has been studied using scanning tunneling microscopy (STM). Uranium was deposited on highly oriented pyrolytic graphite (HOPG) and annealed at temperatures up to 1200 degrees C to obtain atomically pyrolytic flat surfaces. Pt clusters were then formed using evaporation from a Pt source onto the surface and subsequent annealing. Hydrogen mainly attacked uranium in the vicinity of Pt clusters and formed hydride. The hydride formation probability is almost constant at 2.3x10 -4 over the range of exposures studied

A bonding study of c-C5H8 adsorption on Pt(111)

International Nuclear Information System (INIS)

Simonetti, S.; Jasen, P.; Gonzalez, E.; Juan, A.; Brizuela, G.

2006-01-01

The chemisorption of cyclopentane (c-C 5 H 8 ) on Pt(111) has been studied using a qualitative band-structure calculations in the framework of tight-binding implementation with the YAeHMOP package. We modeled the metal surface by a two-dimensional slab of finite thickness with an overlayer of c-C 5 H 8 , in a (3x3) di-σ geometry. The c-C 5 H 8 molecule is attached to the surface with its C?C atoms bonded mainly with two Pt atoms while the opposite CH 2 bends towards the surface. The Pt?Pt bonds in the underlying surface and the C?C bonds of c-C 5 H 8 are weakened upon the chemisorption. A noticeable Pt-H and Pt-C interactions has been observed. We found that of Pt 5d z 2 band plays an important role in the bonding between c-C 5 H 8 and the surface, as do the Pt 6s and 6p z bands. The HOMO-LUMO bands of c-C 5 H 8 are very dispersed, indicative of a strong interaction with the metal surface

Significance of lymphadenectomy with splenectomy in radical surgery for advanced (pT3/pT4) remnant gastric cancer.

Science.gov (United States)

Sugita, Hiroki; Oda, Eri; Hirota, Masahiko; Ishikawa, Shinji; Tomiyasu, Shinjiro; Tanaka, Hiroshi; Arita, Tetsumasa; Yagi, Yasushi; Baba, Hideo

2016-04-01

To date, the optimal surgical strategy for remnant gastric cancer has not been determined. The purpose of this study was to clarify the significance of lymphadenectomy with splenectomy in remnant gastric cancer surgery. This retrospective cohort study was conducted at the Kumamoto Regional Medical Center. The primary endpoint was overall survival after surgery. We retrospectively analyzed the clinicopathologic features, surgical treatments, and long-term prognosis of remnant gastric cancer patients treated with total gastrectomy. A total of 80 patients with gastric cancer in the remnant stomach after distal gastrectomy and who underwent total gastrectomy were enrolled in the study. Splenectomy was performed in 38 patients. Lymph node metastasis in the splenic hilum was not observed in the patients with pT1/pT2 tumors, whereas nodal metastasis at the splenic hilum was detected in 30.4% of the patients with pT3/pT4 tumors. The survival rate of the patients with pT3/pT4 tumors who underwent splenectomy was significantly higher than that of the patients who did not undergo splenectomy, although there was no difference in the patients with pT1/pT2 tumors. Among the patients classified as R0, the survival rate of the patients with pT3/pT4 tumors who underwent splenectomy was significantly higher than that of the patients who did not undergo splenectomy. Lymphadenectomy with splenectomy in radical surgery is beneficial for patients with advanced (pT3/pT4) remnant gastric cancer. Copyright © 2016 Elsevier Inc. All rights reserved.

Experimental and Theoretical Structural Investigation of AuPt Nanoparticles Synthesized Using a Direct Electrochemical Method.

Science.gov (United States)

Lapp, Aliya S; Duan, Zhiyao; Marcella, Nicholas; Luo, Long; Genc, Arda; Ringnalda, Jan; Frenkel, Anatoly I; Henkelman, Graeme; Crooks, Richard M

2018-05-11

In this report, we examine the structure of bimetallic nanomaterials prepared by an electrochemical approach known as hydride-terminated (HT) electrodeposition. It has been shown previously that this method can lead to deposition of a single Pt monolayer on bulk-phase Au surfaces. Specifically, under appropriate electrochemical conditions and using a solution containing PtCl 4 2- , a monolayer of Pt atoms electrodeposits onto bulk-phase Au immediately followed by a monolayer of H atoms. The H atom capping layer prevents deposition of Pt multilayers. We applied this method to ∼1.6 nm Au nanoparticles (AuNPs) immobilized on an inert electrode surface. In contrast to the well-defined, segregated Au/Pt structure of the bulk-phase surface, we observe that HT electrodeposition leads to the formation of AuPt quasi-random alloy NPs rather than the core@shell structure anticipated from earlier reports relating to deposition onto bulk phases. The results provide a good example of how the phase behavior of macro materials does not always translate to the nano world. A key component of this study was the structure determination of the AuPt NPs, which required a combination of electrochemical methods, electron microscopy, X-ray absorption spectroscopy, and theory (DFT and MD).

Determination of the photoeffect cross section and the K- absorption edge energy of Dy, Ta, Pt and Au atoms using Bremsstrahlung

International Nuclear Information System (INIS)

Garcia-Alvarez, J. A.; Lopez-Pino, N.; Diaz Rizo, O.; Corrales, Y.; Padilla-Cabal, F.; Perez-Liva, M.; D' Alessandro, K.; Maidana, N. L.

2011-01-01

An experiment to determine the K-shell photoelectric cross-section (CS) of Dy, Ta, Pt and Au atoms was implemented at the Nuclear Analytical Laboratory (LAN) of the InSTEC. Bremsstrahlung photons, produced by 90 Sr- 90 Y beta particles hitting a thin Ni converter, were used to irradiate the foils target of the elements under study. A HPGe detector, coupled to standard nuclear instrumentation, collected the incident and transmitted spectra. A sharp decrease in intensity at the K-shell binding energy was observed in the transmitted spectra. The photon beam divergence effects were corrected with a calibration curve calculated by means of Monte Carlo simulations (MCNPX 2.6). In order to establish accurately the CS at the K-edge energy, the obtained data was processed by two methods: fitting the total CS to a sigmoidal function, as well as the CS branches around the K edge to the empirical law σ=(A/E) n . The results were compared with experimental and theoretical values showing the best agreement when the thinner foils were used. (Author)

Preparation and characterization of PT-rare earth/C electrocatalysts for PEM fuel cells

International Nuclear Information System (INIS)

Santoro, Thais Aranha de Barros

2009-01-01

Pt-rare earth/C electrocatalysts (rare earth = La, Ce, Pr, Nd, Sm, Tb, Dy, Ho, Er, Tm, and Lu) were prepared (20 wt.% and Pt-to-RE atomic ratio of 50:50) by an alcohol reduction process using H 2 PtCl 6 .6H 2 O (Aldrich) and rare earth (III) chlorides (Aldrich) as metal sources, ethylene glycol as solvent and reducing agent, and Vulcan XC72 as support. The electrocatalysts were characterized by Energy Dispersive X-ray Spectroscopy (EDX), X-Ray Diffractometry (XRD) and Transmission Electron Microscopy (TEM). The energy dispersive x-ray spectroscopy analysis showed that the Pt-Rare Earth atomic ratios obtained for all electrocatalysts were similar to those used in the preparations. In all diffractograms, it was observed a broad peak at about 25 degree which was associated to the Vulcan XC72 support material and four peaks at approximately 28=40 degree, 47 degree, 67 degree and 82 degree, which were associated to the (111), (200), (220), (311), and (222) planes, respectively, of the face-centered cubic (fcc) structure characteristic of platinum and platinum alloys. For the Pt-Rare Earth/C electrocatalysts, it was also observed peaks related to the rare earth oxides on the X ray diffractograms. PtLa/C electrocatalysts were prepared at different atomic ratio. Transmission electronic microscopy micrographs of electrocatalysts showed a reasonable distribution of the Pt particles on the carbon support with some agglomerations, which is in agreement with x-ray diffractometry result. The performance for CO, methanol and ethanol oxidation was investigated by cyclic voltammetry, chronoamperometry and Fourier transform infrared spectroscopy spectroscopy. The electrocatalytic activity of the Pt-Rare Earth/C electro catalyst, specially PtLa/C, were higher than that of the Pt/C electrocatalyst. Fourier transform infrared spectroscopy studies for ethanol oxidation on Pt-Rare Earth/C electrocatalyst showed that acetaldehyde and acetic acid were the main products. The PtLa/C (30

Total quality approach at ABB Atom Nuclear Fuel - winner of the Swedish quality award 1994

International Nuclear Information System (INIS)

Moorlin, K.; Olsson, S.

1995-01-01

ABB Atom Nuclear Fuel Division received the Swedish Quality Award 1994. The company has since many years a reputation for high product quality and a well implemented quality assurance system. Since some years a total quality approach is applied. For ABB Atom, total quality means continuous improvement of all business processes keeping the customer in focus. This paper elaborates on the improvement tools used at the ABB Atom Nuclear Fuel Division and gives some detailed information of the experience. (author) 6 figs

[μ-Bis(diphenylphosphanylmethane]tricarbonyl(μ-p-toluenesulfonylmethyl isocyanato(triphenylphosphaneironplatinum(Fe—Pt

Directory of Open Access Journals (Sweden)

Carsten Strohmann

2012-03-01

Full Text Available The title compound, [FePt(C9H9NO2S(C18H15P(C25H22P2(CO3], represents a rare example of an isonitrile-bridged heterobimetallic complex (here Pt and Fe and is an interesting precursor for the preparation of heterodinuclear μ-aminocarbyne complexes, since the basic imine-type N atom of the μ2-C=N–R ligand readily undergoes addition with various electrophiles to afford iminium-like salts. In the crystal, the almost symmetrically bridging μ2-C=N-R ligand (neglecting the different atomic radii of Fe and Pt is strongly bent towards the Fe(CO3 fragment, with a C=N-R angle of only 121.1 (4°.

CO and ethanol electro-oxidation on Pt-Rh/C

OpenAIRE

Calderón-Cárdenas, Alfredo; Ortiz-Restrepo, John E.; Mancilla-Valencia, Nelson D.; Torres-Rodriguez, Gerardo A.; Lima, Fabio H. B.; Bolaños-Rivera, Alberto; Gonzalez, Ernesto R.; Lizcano-Valbuena, William H.

2014-01-01

In this work we studied the effect of the composition and thermal treatment in H2 of Pt-Rh/C materials with atomic ratios close to Pt:Rh 3:1, 1:1 and 1:3 and metal loading of 40 wt. %, for the COads and ethanol oxidation. Catalysts were prepared by chemical reduction with formic acid and physically characterized by energy dispersive X-rays spectroscopy (EDX), electron backscattering (EBS) and transmission electron microscopy (TEM), showing Pt:Rh ratios close to the nominals values, similar av...

The total Hartree-Fock energy-eigenvalue sum relationship in atoms

International Nuclear Information System (INIS)

Sen, K.D.

1979-01-01

Using the well known relationships for the isoelectronic changes in the total Hartree-Fock energy, nucleus-electron attraction energy and electron-electron repulsion energy in atoms a simple polynomial expansion in Z is obtained for the sum of the eigenvalues which can be used to calculate the total Hartree-Fock energy. Numerical results are presented for 2-10 electron series to show that the present relationship is a better approximation than the other available energy-eigenvalue relationships. (author)

Mechanical properties of non-centrosymmetric CePt3Si and CePt3B

Science.gov (United States)

Rogl, G.; Legut, D.; Sýkora, R.; Müller, P.; Müller, H.; Bauer, E.; Puchegger, S.; Zehetbauer, M.; Rogl, P.

2017-05-01

Elastic moduli, hardness (both at room temperature) and thermal expansion (4.2-670 K) have been experimentally determined for polycrystalline CePt3Si and its prototype compound CePt3B as well as for single-crystalline CePt3Si. Resonant ultrasound spectroscopy was used to determine elastic properties (Young’s modulus E and Poisson’s ratio ν) via the eigenfrequencies of the sample and the knowledge of sample mass and dimensions. Bulk and shear moduli were calculated from E and ν, and the respective Debye temperatures were derived. In addition, ab initio DFT calculations were carried out for both compounds. A comparison of parameters evaluated from DFT with those of experiments revealed, in general, satisfactory agreement. Positive and negative thermal expansion values obtained from CePt3Si single crystal data are fairly well explained in terms of the crystalline electric field model, using CEF parameters derived recently from inelastic neutron scattering. DFT calculations, in addition, demonstrate that the atomic vibrations keep almost unaffected by the antisymmetric spin-orbit coupling present in systems with crystal structures having no inversion symmetry. This is opposite to electronic properties, where the antisymmetric spin-orbit interaction has shown to distinctly influence features like the superconducting condensate of CePt3Si.

Dynamics of the YSZ-Pt Interface

DEFF Research Database (Denmark)

Bay, Lasse; Jacobsen, Torben

1997-01-01

Yttria stabilized zirconia (YSZ)-Pt point electrodes were examined by linear potential sweep, potential step and impedance measurements at 1000 degrees C in air. Inductive loops and hysteresis phenomena with long relaxation times were found. Atomic force microscopy showed changes of the interface...

Non-Hermitian optics in atomic systems

Science.gov (United States)

Zhang, Zhaoyang; Ma, Danmeng; Sheng, Jiteng; Zhang, Yiqi; Zhang, Yanpeng; Xiao, Min

2018-04-01

A wide class of non-Hermitian Hamiltonians can possess entirely real eigenvalues when they have parity-time (PT) symmetric potentials. Recently, this family of non-Hermitian systems has attracted considerable attention in diverse areas of physics due to their extraordinary properties, especially in optical systems based on solid-state materials, such as coupled gain-loss waveguides and microcavities. Considering the desired refractive index can be effectively manipulated through atomic coherence, it is important to realize such non-Hermitian optical potentials and further investigate their distinct properties in atomic systems. In this paper, we review the recent theoretical and experimental progress of non-Hermitian optics with coherently prepared multi-level atomic configurations. The realizations of (anti-) PT symmetry with different schemes have extensively demonstrated the special optical properties of non-Hermitian optical systems with atomic coherence.

Crystal structure and chemical bonding analysis of BaPtCd{sub 2}

Energy Technology Data Exchange (ETDEWEB)

Gulo, Fakhili [Department of Chemical Education, Sriwijaya University, Inderalaya 30662, South Sumatra (Indonesia); Koehler, Juergen [Max Planck Institut fuer Festkoerperforschung, Heisenbergstrasse 1, 70569 Stuttgart (Germany)

2015-03-15

The new ternary intermetallic phase, BaPtCd{sub 2}, was synthesized by solid-state reaction from direct combination of the elements in a stoichiometric mixture. The reaction was done at 850 C for 15 h, followed by an equilibration at 600 C for 4 d. The crystal structure was determined by X-ray diffraction method on a single crystal. BaPtCd{sub 2} is isotypic to MgCuAl{sub 2} and crystallizes in the orthorhombic space group Cmcm [a = 4.467(2), b = 11.143(4), c = 8.240(3) Aa, V = 410.2(3) Aa{sup 3}, and Z = 4]. Barium atoms are linked together forming zigzag chains. Cadmium atoms are bonded to each other forming six-membered rings of platinum centered boat and anti-boat conformations. BaPtCd{sub 2} contains 16 electrons per formula unit and belongs to the electron poorest compounds with MgCuAl{sub 2} type structure. Calculations based on the linear muffin-tin orbitals method in the atomic spheres approximation show that significant bonding states in BaPtCd{sub 2} are unoccupied. (Copyright copyright 2015 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Understanding the structural properties and thermal stabilities of Au–Pd–Pt trimetallic clusters

International Nuclear Information System (INIS)

Zhao, Zheng; Li, Mingjiang; Cheng, Daojian; Zhu, Jiqin

2014-01-01

Highlights: • Structural properties of Au–Pd–Pt clusters are studied by Monte Carlo simulation. • Melting of Au–Pd–Pt clusters is studied by molecular dynamics simulation. • Au atoms are systematically segregated on the surface of the Au–Pd–Pt clusters. • Linear decrease in cluster melting point with the inverse cluster diameter. - Abstract: In this work, surface segregation phenomena of Au–Pd–Pt trimetallic clusters are investigated by using semi-grand Monte Carlo simulations based on the Gupta potential. It is found that Au atoms are systematically segregated on the surface of the Au–Pd–Pt clusters (6–24 at.% higher than the overall Au concentration), due to the competition among the surface energies of Au, Pd, and Pt. The melting properties of Au–Pd–Pt trimetallic clusters with different composition and size are investigated by using molecular dynamics simulations, based on the same Gupta potential. It is found that the Au–Pd–Pt trimetallic cluster with the highest melting point corresponds to the one with the most stable structure. In addition, linear decrease in cluster melting point with the inverse cluster diameter is predicted for both pure and trimetallic clusters, which is well-known as the Pawlow’s law

Co on Pt(111) studied by spin-polarized scanning tunneling microscopy and spectroscopy

Energy Technology Data Exchange (ETDEWEB)

Meier, F.K.

2006-07-01

In this thesis the electronic properties of the bare Pt(111) surface, the structural, electronic, and magnetic properties of monolayer and double-layer high Co nanostructures as well as the spin-averaged electronic structure of single Co atoms on Pt(111) were studied by low-temperature scanning tunneling microscopy (STM) and spectroscopy (STS). The experiments on the bare Pt(111) surface and on single Co atoms have been performed in an STM facility operating at temperatures of down to 0.3 K and at magnetic fields of up to 14 T under ultra-high vacuum conditions. The facility has been taken into operation within the time period of this thesis and its specifications were tested by STS measurements. These characterization measurements show a very high stability of the tunneling junction and an energy resolution of about 100 {mu}eV, which is close to the thermal limit. The investigation of the electronic structure of the bare Pt(111) surface reveals the existence of an unoccupied surface state. By a comparison of the measured dispersion to first-principles electronic structure calculations the state is assigned to an sp-derived surface band at the lower boundary of the projected bulk band gap. The surface state exhibits a strong spin-orbit coupling induced spin splitting. The close vicinity to the bulk bands leads to a strong linear contribution to the dispersion and thus to a deviant appearance in the density of states in comparison to the surface states of the (111) surfaces of noble metals. A detailed study of Co monolayer and double-layer nanostructures on the Pt(111) surface shows that both kinds of nanostructures exhibit a highly inhomogeneous electronic structure which changes at the scale of only a few Aa due to a strong stacking dependence with respect to the Pt(111) substrate. With the help of first principles calculations the different spectroscopic appearance for Co atoms within the Co monolayer is assigned to a stacking dependent hybridization of Co states

A new method for mapping the three-dimensional atomic distribution within nanoparticles by atom probe tomography (APT).

Science.gov (United States)

Kim, Se-Ho; Kang, Phil Woong; Park, O Ok; Seol, Jae-Bok; Ahn, Jae-Pyoung; Lee, Ji Yeong; Choi, Pyuck-Pa

2018-07-01

We present a new method of preparing needle-shaped specimens for atom probe tomography from freestanding Pd and C-supported Pt nanoparticles. The method consists of two steps, namely electrophoresis of nanoparticles on a flat Cu substrate followed by electrodeposition of a Ni film acting as an embedding matrix for the nanoparticles. Atom probe specimen preparation can be subsequently carried out by means of focused-ion-beam milling. Using this approach, we have been able to perform correlative atom probe tomography and transmission electron microscopy analyses on both nanoparticle systems. Reliable mass spectra and three-dimensional atom maps could be obtained for Pd nanoparticle specimens. In contrast, atom probe samples prepared from C-supported Pt nanoparticles showed uneven field evaporation and hence artifacts in the reconstructed atom maps. Our developed method is a viable means of mapping the three-dimensional atomic distribution within nanoparticles and is expected to contribute to an improved understanding of the structure-composition-property relationships of various nanoparticle systems. Copyright © 2018 Elsevier B.V. All rights reserved.

Enhanced methanol electro-oxidation reaction on Pt-CoOx/MWCNTs hybrid electro-catalyst

International Nuclear Information System (INIS)

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

2015-01-01

Highlights: • Promoting effects of Cobalt oxide on methanol electro-oxidation over Pt/MWCNTs are investigated. • Higher activity, about 2.9 times, and enhanced stability are observed on Pt-CoO x /MWCNTs. • Electrochemical active surface area of Pt nanoparticles is significantly improved upon CoO x addition. • Bi-functional mechanism is facilitated in presence of CoO x . - Abstract: The electro-catalytic behavior of Pt-CoO x /MWCNTs in methanol electro-oxidation reaction (MOR) is investigated and compared to that of Pt/MWCNTs. The electro-catalysts were synthesized by an impregnation method using NaBH 4  as the reducing agent. The morphological and physical characteristics of samples are examined by XRD, TEM, ICP and EDS techniques. In the presence of CoO x , Pt nanoparticles were highly distributed on the support with an average particle size of 2 nm, an obvious decrease from 5.1 nm for Pt/MWCNTs. Cyclic voltammetry, CO-stripping, Chronoamperometry, and electrochemical impedance spectroscopy (EIS) measurements are used to study the electrochemical behavior of the electro-catalysts. The results revealed a considerable enhancement in the oxidation kinetics of CO ads on Pt active sites by the participation of CoO x . Compared to Pt/MWCNTs, Pt-CoO x /MWCNTs sample has a larger electrochemical active surface area (ECSA) and higher electro-catalytic activity and stability toward methanol electro-oxidation. According to the results of cyclic voltammetry, the forward anodic peak current density enhances more than 89% at the optimum atomic ratio of Pt:Co = 2:1. Furthermore, inclusion of cobalt oxide species causes the onset potential of methanol electro-oxidation reaction to shift 84 mV to negative values compared to that on Pt/MWCNTs. Based on EIS data, dehydrogenation of methanol is the rate-determining step of MOR on both Pt/MWCNTs and Pt-CoO x /MWCNTs, at small overpotentials. However, at higher overpotentials, the oxidation of adsorbed oxygen-containing groups

Platinum atom location on the internal walls of nanocavities investigated by ion channeling analysis

International Nuclear Information System (INIS)

Kinomura, A.; Williams, J.S.; Tsubouchi, N.; Horino, Y.

2002-01-01

Atomic locations of Pt trapped at hydrogen-induced cavities in Si have been investigated by ion channeling analysis. A Pt dose of 1x10 14 cm -2 , corresponding to a monolayer coverage of the internal walls of cavities, was implanted into cavity-containing samples. The gettering of Pt to the cavities was induced by annealing at 850 deg. C for 1 h. Clear channeling effects were observed in aligned and random backscattering spectra for the , and axes. Angular yield profiles for three crystalline axes exhibited dips with a narrowing of Pt signal half width compared with the Si matrix. Results suggested that the Pt atoms trapped at the cavities are closely aligned with the Si atomic strings bounding axial channels in Si

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

Energy Technology Data Exchange (ETDEWEB)

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

2010-07-01

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

Atomistic nucleation sites of Pt nanoparticles on N-doped carbon nanotubes.

Science.gov (United States)

Sun, Chia-Liang; Pao, Chih-Wen; Tsai, Huang-Ming; Chiou, Jau-Wern; Ray, Sekhar C; Wang, Houng-Wei; Hayashi, Michitoshi; Chen, Li-Chyong; Lin, Hong-Ji; Lee, Jyh-Fu; Chang, Li; Tsai, Min-Hsiung; Chen, Kuei-Hsien; Pong, Way-Faung

2013-08-07

The atomistic nucleation sites of Pt nanoparticles (Pt NPs) on N-doped carbon nanotubes (N-CNTs) were investigated using C and N K-edge and Pt L3-edge X-ray absorption near-edge structure (XANES)/extended X-ray absorption fine structure (EXAFS) spectroscopy. Transmission electron microscopy and XANES/EXAFS results revealed that the self-organized Pt NPs on N-CNTs are uniformly distributed because of the relatively high binding energies of the adsorbed Pt atoms at the imperfect sites. During the atomistic nucleation process of Pt NPs on N-CNTs, stable Pt-C and Pt-N bonds are presumably formed, and charge transfer occurs at the surface/interface of the N-CNTs. The findings in this study were consistent with density functional theory calculations performed using cluster models for the undoped, substitutional-N-doped and pyridine-like-N-doped CNTs.

Classical calculation of the total ionization energy of helium-like atoms

International Nuclear Information System (INIS)

Karastoyanov, A.

1990-01-01

Quantum mechanics rejects the classical modelling of microworld. One of the reasons is that the Bohr's rules can not be applied for many-electron atoms and molecules. But the many-body problem in classical mechanics has no analytical solution even for 3 particles. Numerical solutions should be used. The quantum Bohr's rule expressing the moment of momentum conservation for two particles is invalid in more complicated cases. Yet Bohr reached some success for helium-like atoms. The Bohr's formula concerning helim-like atoms is deduced again in this paper and its practical reliability is analyzed with contemporary data. The binding energy of the system is obtained in the simple form E=(Z-1/4) 2 α 2 mc 2 , where Z is the atomic number, α - the fine structure constant, M - the electron mass and c - the light speed in vacuum. The calculated values are compared with experimental data on the total ionization energy of the helium-like atoms from 2 He 4 to 29 Cu 64 . The error decreases quickly with the increasing of atomic mass, reaching zero for Cu. This indicated that the main source of error is the nucleus motion. The role of other possible causes is analyzed and proves negligible. (author). 1 tab, 4 refs

Atomic probes of surface structure and dynamics

International Nuclear Information System (INIS)

Heller, E.J.; Jonsson, H.

1992-01-01

The following were studied: New semiclassical method for scattering calculations, He atom scattering from defective Pt surfaces, He atom scattering from Xe overlayers, thermal dissociation of H 2 on Cu(110), spin flip scattering of atoms from surfaces, and Car-Parrinello simulations of surface processes

Reduction of Pt{sup 2+} species in model Pt–CeO{sub 2} fuel cell catalysts upon reaction with methanol

Energy Technology Data Exchange (ETDEWEB)

Neitzel, Armin [Lehrstuhl für Physikalische Chemie II, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstrasse 3, 91058 Erlangen (Germany); Johánek, Viktor [Charles University, Faculty of Mathematics and Physics, Department of Surface and Plasma Science, V Holešovičkách 2, 18000 Prague (Czech Republic); Lykhach, Yaroslava, E-mail: yaroslava.lykhach@fau.de [Lehrstuhl für Physikalische Chemie II, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstrasse 3, 91058 Erlangen (Germany); Skála, Tomáš; Tsud, Nataliya; Vorokhta, Mykhailo; Matolín, Vladimír [Charles University, Faculty of Mathematics and Physics, Department of Surface and Plasma Science, V Holešovičkách 2, 18000 Prague (Czech Republic); Libuda, Jörg [Lehrstuhl für Physikalische Chemie II, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstrasse 3, 91058 Erlangen (Germany); Erlangen Catalysis Resource Center, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstrasse 3, 91058 Erlangen (Germany)

2016-11-30

Highlights: • Pt{sup 2+} species are reduced upon reaction with methanol. • Reduction of one Pt{sup 2+} requires presence of two oxygen vacancies. • Reduction of Pt{sup 2+} species leads to formation of ultra-small Pt particles. • Ultra-small Pt particles (around 25 atoms or less) are resistant to sintering. - Abstract: The stability of atomically dispersed Pt{sup 2+} species on the surface of nanostructured CeO{sub 2} films during the reaction with methanol has been investigated by means of synchrotron radiation photoelectron spectroscopy and resonant photoemission spectroscopy. The isolated Pt{sup 2+} species were prepared at low Pt concentration in Pt–CeO{sub 2} film. Additionally, Pt{sup 2+} species coexisting with metallic Pt particles were prepared at high Pt concentration. We found that adsorption of methanol yields similar decomposition products regardless of Pt concentration in Pt–CeO{sub 2} films. A small number of oxygen vacancies formed during the methanol decomposition can be replenished in the Pt–CeO{sub 2} film with low Pt concentration by diffusion of oxygen from the bulk. In the presence of supported Pt particles, a higher number of oxygen vacancies leads to a partial reduction of the Pt{sup 2+} species. The isolated Pt{sup 2+} species are reduced under rather strongly reducing conditions only, i.e. during annealing under continuous exposure to methanol. Reduction of isolated Pt{sup 2+} species results in the formation of ultra-small Pt particles containing around 25 atoms per particle or less. Such ultra-small Pt particles demonstrate excellent stability against sintering during annealing of Pt–CeO{sub 2} film with low Pt concentration under reducing conditions.

Tuning the chemical activity through PtAu nanoalloying: a first principles study

KAUST Repository

Mokkath, Junais Habeeb

2013-06-21

The electronic structure and adsorption properties of 1.5 nm sized Pt, Au, and PtAu nanoclusters are studied by density functional theory. We explain the recent experimental finding that 20% Au content in PtAu nanoparticles is optimal to induce a dramatically different catalytic behavior. Our results show that the d-band center together with the density of states at the Fermi energy can be used as an indicator of the chemical activity of PtAu nanoclusters. The most favorable adsorption sites on the cluster surfaces as a function of the Pt/Au ratio are identified using atomic H as a probe.

Tuning the chemical activity through PtAu nanoalloying: a first principles study

KAUST Repository

Mokkath, Junais Habeeb; Schwingenschlö gl, Udo

2013-01-01

The electronic structure and adsorption properties of 1.5 nm sized Pt, Au, and PtAu nanoclusters are studied by density functional theory. We explain the recent experimental finding that 20% Au content in PtAu nanoparticles is optimal to induce a dramatically different catalytic behavior. Our results show that the d-band center together with the density of states at the Fermi energy can be used as an indicator of the chemical activity of PtAu nanoclusters. The most favorable adsorption sites on the cluster surfaces as a function of the Pt/Au ratio are identified using atomic H as a probe.

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

Directory of Open Access Journals (Sweden)

Colle Vinicius D.

2003-01-01

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2016-03-01

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

Propylene oxidation on catalytic Pt-Cu/y alumina. (Part II) chemical Kinetics of catalysts of Pt-Cu/y-alumina in the propylene oxidation

International Nuclear Information System (INIS)

Carballo, Luis M; Zea, Hugo R

1999-01-01

In this work is treated the effect of the composition of catalysts of Pt-Cu/y - alumina on the specific superficial activity corresponding to the total oxidation of propylene. Although the catalyst activity of the Cu in the operation conditions went practically null the specific activity of the catalytic Pt-Cu it incremented with the increase of the contained proportion of Cu in the catalyst. The total global speed by gram of catalyst was also increased with the introduction of Cu, but only to medium and high concentrations of propylene. The specific superficial activity was bigger for the sinterizated catalyst, for a given composition of the bimetallic catalyst, compared with that of the fresh catalyst (non-sinterizated). To explain, the catalytic behavior of the propylene oxidation, on the catalysts here studied, it is postulated that the propylene molecule it absorb with less force on the faces than in the corners or borders of the crystals of the catalyst and that the connection of adsorption on a place of given Pt is affected by the atoms of neighboring Cu on the surface causing changes in the mobility of the absorbed species. The kinetic results reveal a complex dependence between the reaction speed and the concentration of the propylene. In low concentrations of propylene the reaction speed was increased until to reach a maximum, and then to continue with a marked decreasing; and to concentrations. In bigger propylene concentrations, the reaction kinetics is presented as zero order with regard to the propylene, for some given concentrations of oxygen

Symmetrical metallic and magnetic edge states of nanoribbon from semiconductive monolayer PtS2

Science.gov (United States)

Liu, Shan; Zhu, Heyu; Liu, Ziran; Zhou, Guanghui

2018-03-01

Transition metal dichalcogenides (TMD) MoS2 or graphene could be designed to metallic nanoribbons, which always have only one edge show metallic properties due to symmetric protection. In present work, a nanoribbon with two parallel metallic and magnetic edges was designed from a noble TMD PtS2 by employing first-principles calculations based on density functional theory (DFT). Edge energy, bonding charge density, band structure, density of states (DOS) and simulated scanning tunneling microscopy (STM) of four possible edge states of monolayer semiconductive PtS2 were systematically studied. Detailed calculations show that only Pt-terminated edge state among four edge states was relatively stable, metallic and magnetic. Those metallic and magnetic properties mainly contributed from 5d orbits of Pt atoms located at edges. What's more, two of those central symmetric edges coexist in one zigzag nanoribbon, which providing two atomic metallic wires thus may have promising application for the realization of quantum effects, such as Aharanov-Bohm effect and atomic power transmission lines in single nanoribbon.

Magnetic properties in the vortex state of Pr1-xNdxPt4Ge12 and PrPt3.88Fe0.12Ge12 superconductors

Science.gov (United States)

Chandra, L. S. Sharath; Chattopadhyay, M. K.

2018-03-01

We report the temperature and magnetic field dependence of magnetization of Pr1-xNdxPt4Ge12 (x = 0, 0.05 and 0.1) and PrPt3.88Fe0.12Ge12 below 10 K and up to 2 T magnetic field. When compared to the parent PrPt4Ge12, while the critical current density and flux pinning properties are enhanced in the Pr1-xNdxPt4Ge12 samples, they are considerably diminished in the PrPt3.88Fe0.12Ge12 sample. We argue that the observed changes are related to the way the substituting atoms at different crystallographic sites influence the superconductivity in these Germanide skutterudites.

Ethanol electrooxidation on novel carbon supported Pt/SnO{sub x}/C catalysts with varied Pt:Sn ratio

Energy Technology Data Exchange (ETDEWEB)

Jiang, L. [Institute of Surface Chemistry and Catalysis, Ulm University, D-89069 Ulm (Germany); Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 116023 Dalian (China); Colmenares, L.; Jusys, Z. [Institute of Surface Chemistry and Catalysis, Ulm University, D-89069 Ulm (Germany); Sun, G.Q. [Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 116023 Dalian (China)], E-mail: gqsun@dicp.ac.cn; Behm, R.J. [Institute of Surface Chemistry and Catalysis, Ulm University, D-89069 Ulm (Germany)], E-mail: juergen.behm@uni-ulm.de

2007-12-01

Novel carbon supported Pt/SnO{sub x}/C catalysts with Pt:Sn atomic ratios of 5:5, 6:4, 7:3 and 8:2 were prepared by a modified polyol method and characterized with respect to their structural properties (X-ray diffraction (XRD) and transmission electron microscopy (TEM)), chemical composition (XPS), their electrochemical properties (base voltammetry, CO{sub ad} stripping) and their electrocatalytic activity and selectivity for ethanol oxidation (ethanol oxidation reaction (EOR)). The data show that the Pt/SnO{sub x}/C catalysts are composed of Pt and tin oxide nanoparticles with an average Pt particle diameter of about 2 nm. The steady-state activity of the Pt/SnO{sub x}/C catalysts towards the EOR decreases with tin content at room temperature, but increases at 80 deg. C. On all Pt/SnO{sub x}/C catalysts, acetic acid and acetaldehyde represent dominant products, CO{sub 2} formation contributes 1-3% for both potentiostatic and potentiodynamic reaction conditions. With increasing potential, the acetaldehyde yield decreases and the acetic acid yield increases. The apparent activation energies of the EOR increase with tin content (19-29 kJ mol{sup -1}), but are lower than on Pt/C (32 kJ mol{sup -1}). The somewhat better performance of the Pt/SnO{sub x}/C catalysts compared to alloyed PtSn{sub x}/C catalysts is attributed to the presence of both sufficiently large Pt ensembles for ethanol dehydrogenation and C-C bond splitting and of tin oxide for OH generation. Fuel cell measurements performed for comparison largely confirm the results obtained in model studies.

Very high coercivities of top-layer diffusion Au/FePt thin films

International Nuclear Information System (INIS)

Yuan, F.T.; Chen, S.K.; Liao, W.M.; Hsu, C.W.; Hsiao, S.N.; Chang, W.C.

2006-01-01

The Au/FePt samples were prepared by depositing a gold cap layer at room temperature onto a fully ordered FePt layer, followed by an annealing at 800 deg. C for the purpose of interlayer diffusion. After the deposition of the gold layer and the high-temperature annealing, the gold atoms do not dissolve into the FePt Ll 0 lattice. Compared with the continuous FePt film, the TEM photos of the bilayer Au(60 nm)/FePt(60 nm) show a granular structure with FePt particles embedded in Au matrix. The coercivity of Au(60 nm)/FePt(60 nm) sample is 23.5 kOe, which is 85% larger than that of the FePt film without Au top layer. The enhancement in coercivity can be attributed to the formation of isolated structure of FePt ordered phase

Electronic Structure of the fcc Transition Metals Ir, Rh, Pt, and Pd

DEFF Research Database (Denmark)

Andersen, O. Krogh

1970-01-01

We give a complete description of a relativistic augmented-plane-wave calculation of the band structures of the paramagnetic fcc transition metals Ir, Rh, Pt, and Pd. The width and position of the d band decrease in the sequence Ir, Pt, Rh, Pd; and N(EF)=13.8,23.2,18.7, and 32.7 (states/atom)/Ry,......We give a complete description of a relativistic augmented-plane-wave calculation of the band structures of the paramagnetic fcc transition metals Ir, Rh, Pt, and Pd. The width and position of the d band decrease in the sequence Ir, Pt, Rh, Pd; and N(EF)=13.8,23.2,18.7, and 32.7 (states....../atom)/Ry, respectively. Spin-orbit coupling is important for all four metals and the coupling parameter varies by 30% over the d bandwidth. Detailed comparisons with de Haas—van Alphen Fermi-surface dimensions have previously been presented and the agreement was very good. Comparison with measured electronic specific...

First-principles study on the phase transition, elastic properties and electronic structure of Pt3Al alloys under high pressure

International Nuclear Information System (INIS)

Liu, Yanjun; Huang, Huawei; Pan, Yong; Zhao, Guanghui; Liang, Zheng

2014-01-01

Highlights: • The phase transition of Pt 3 Al alloys occurs at 60 GPa. • The elastic modulus of Pt 3 Al alloys increase with increasing pressure. • The cubic structure has good resistance to volume deformation under high pressure. • The pressure enhances the hybridization between Pt atom and Al atom. - Abstract: The phase transition, formation enthalpies, elastic properties and electronic structure of Pt 3 Al alloys are studied using first-principle approach. The calculated results show that the pressure leads to phase transition from tetragonal structure to cubic structure at 60 GPa. With increasing pressure, the elastic constants, bulk modulus and shear modulus of these Pt 3 Al alloys increase linearly and the bond lengths of Pt–Al metallic bonds and the peak at E F decrease. The cubic Pt 3 Al alloy has excellent resistance to volume deformation under high pressure. We suggest that the phase transition is derived from the hybridization between Pt and Al atoms for cubic structure is stronger than that of tetragonal structure and forms the strong Pt–Al metallic bonds under high pressure

Methanol oxidation catalysis and substructure of PtRu bimetallic nanoparticles

Energy Technology Data Exchange (ETDEWEB)

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

2007-07-15

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

Preparation of PtSnCu/C and PtSn/C electrocatalysts and activation by dealloying processes for ethanol electrooxidation

International Nuclear Information System (INIS)

Crisafulli, Rudy

2013-01-01

PtSnCu/C (with different Pt:Sn:Cu atomic ratios) and PtSn/C (50:50) electrocatalysts were prepared by borohydride (BR) and alcohol-reduction (AR) processes using H 2 PtCl 6 .6H 2 O, SnCl 2 .2H 2 O and CuCl 2 .2H 2 O as metal sources, NaBH 4 and ethylene glycol as reducing agents, 2-propanol and ethylene glycol/water as solvents and carbon black as support. In a further step, these electrocatalysts were activated by chemical (CD) and electrochemical (ED) dealloying processes through acid treatment and thin porous coating technique, respectively. These materials were characterized by energy dispersive X-ray, Xray diffraction, transmission electron microscopy, line scan energy dispersive Xray and cyclic voltammetry. Electrochemical studies for ethanol electro-oxidation were performed by cyclic voltammetry, chronoamperometry and in single Direct Ethanol Fuel Cell using Membrane Electrode Assembly (MEA). The anodic effluents were analysed by gas chromatography. The X-ray diffractograms of the as-synthesized electrocatalysts showed the typical face-centered cubic structure (FCC) of platinum and its alloys. After dealloying, the X-ray diffractograms showed that the Pt FCC structure was preserved. The crystallite sizes of the assynthesized electrocatalysts were in the range of PtSnCu/C (50:40:10) AR/ED > PtSnCu/C (50:10:40) BR/CD. PtSn/C (50:50) BR/CD, PtSnCu/C (50:10:40) BR/CD, PtSnCu/C (50:40:10) AR/CD electrocatalysts and Pt/C BASF, PtSn/C (75:25) BASF commercial electrocatalysts were tested in single Direct Ethanol Fuel Cell. The results showed the following performance for ethanol electro-oxidation: PtSn/C (50:50) BR/CD > PtSnCu/C (50:40:10) AR/CD > PtSnCu/C > PtSn/C (75:25) BASF > PtSnCu/C (50:10:40) BR/CD > Pt/C BASF. (author)

Particle swarm optimization of the stable structure of tetrahexahedral Pt-based bimetallic nanoparticles

Energy Technology Data Exchange (ETDEWEB)

Liu, Tun-Dong; Fan, Tian-E [Center for Cloud Computing and Big Data, Department of Automation, Xiamen University, Xiamen 361005 (China); Shao, Gui-Fang, E-mail: gfshao@xmu.edu.cn [Center for Cloud Computing and Big Data, Department of Automation, Xiamen University, Xiamen 361005 (China); Zheng, Ji-Wen [Center for Cloud Computing and Big Data, Department of Automation, Xiamen University, Xiamen 361005 (China); Wen, Yu-Hua [Institute of Theoretical Physics and Astrophysics, Department of Physics, Xiamen University, Xiamen 361005 (China)

2014-08-14

Bimetallic nanoparticles, enclosed by high-index facets, have great catalytic activity and selectivity owing to the synergy effects of high-index facets and the electronic structures of alloy. In this paper, a discrete particle swarm optimization algorithm was employed to systematically investigate the structural stability and features of tetrahexahedral Pt-based bimetallic nanoparticles with high-index facets. Different Pt/Ag, Pt/Cu, Pt/Pd atom ratios and particle sizes were considered in this work. The simulation results reveal that these alloy nanoparticles exhibit considerably different structural characteristics. Pt–Ag nanoparticles tend to form Pt–Ag core–shell structure. Pt–Cu nanoparticles are preferred to take multi-shell structure with Cu on the outer surface while Pt–Pd nanoparticles present a mixing structure in the interior and Pd-dominated surface. Atomic distribution and bonding characteristics were applied to further characterize the structural features of Pt-based nanoparticles. This study provides an important insight into the structural stability and features of Pt-based nanoparticles with different alloys. - Highlights: • We explore the structural stability of Pt-based alloy NPs by a discrete PSO. • Our study discovers the different structural characteristics for Pt-based NPs. • Alloy composition and size have important effects on the surface segregation. • Our work shows strong phase separation for Pt–Ag NPs while weak for Pt–Pd NPs.

Particle swarm optimization of the stable structure of tetrahexahedral Pt-based bimetallic nanoparticles

International Nuclear Information System (INIS)

Liu, Tun-Dong; Fan, Tian-E; Shao, Gui-Fang; Zheng, Ji-Wen; Wen, Yu-Hua

2014-01-01

Bimetallic nanoparticles, enclosed by high-index facets, have great catalytic activity and selectivity owing to the synergy effects of high-index facets and the electronic structures of alloy. In this paper, a discrete particle swarm optimization algorithm was employed to systematically investigate the structural stability and features of tetrahexahedral Pt-based bimetallic nanoparticles with high-index facets. Different Pt/Ag, Pt/Cu, Pt/Pd atom ratios and particle sizes were considered in this work. The simulation results reveal that these alloy nanoparticles exhibit considerably different structural characteristics. Pt–Ag nanoparticles tend to form Pt–Ag core–shell structure. Pt–Cu nanoparticles are preferred to take multi-shell structure with Cu on the outer surface while Pt–Pd nanoparticles present a mixing structure in the interior and Pd-dominated surface. Atomic distribution and bonding characteristics were applied to further characterize the structural features of Pt-based nanoparticles. This study provides an important insight into the structural stability and features of Pt-based nanoparticles with different alloys. - Highlights: • We explore the structural stability of Pt-based alloy NPs by a discrete PSO. • Our study discovers the different structural characteristics for Pt-based NPs. • Alloy composition and size have important effects on the surface segregation. • Our work shows strong phase separation for Pt–Ag NPs while weak for Pt–Pd NPs

Dehydrogenation of benzene on Pt(111) surface

Science.gov (United States)

Gao, W.; Zheng, W. T.; Jiang, Q.

2008-10-01

The dehydrogenation of benzene on Pt(111) surface is studied by ab initio density functional theory. The minimum energy pathways for benzene dehydrogenation are found with the nudge elastic band method including several factors of the associated barriers, reactive energies, intermediates, and transient states. The results show that there are two possible parallel minimum energy pathways on the Pt(111) surface. Moreover, the tilting angle of the H atom in benzene can be taken as an index for the actual barrier of dehydrogenation. In addition, the properties of dehydrogenation radicals on the Pt(111) surface are explored through their adsorption energy, adsorption geometry, and electronic structure on the surface. The vibrational frequencies of the dehydrogenation radicals derived from the calculations are in agreement with literature data.

Stabilization of 200-atom platinum nanoparticles by organosilane fragments

KAUST Repository

Pelzer, Katrin

2011-04-19

Three\\'s a charm: Platinum nanoparticles of 2 nm diameter and containing approximately 200 atoms covered with n-octylsilyl groups (see picture, right; Pt blue, Si red, C gray, H turquoise) form when [Pt(dba)2] (dba=dibenzylideneacetone) decomposes in the presence of n-octylsilane. The particles adopt a cuboctahedral structure with an edge length of three atoms. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Stabilization of 200-atom platinum nanoparticles by organosilane fragments

KAUST Repository

Pelzer, Katrin; Hä vecker, Michael; Boualleg, Malika; Candy, Jean Pierre; Basset, Jean-Marie

2011-01-01

Three's a charm: Platinum nanoparticles of 2 nm diameter and containing approximately 200 atoms covered with n-octylsilyl groups (see picture, right; Pt blue, Si red, C gray, H turquoise) form when [Pt(dba)2] (dba=dibenzylideneacetone) decomposes in the presence of n-octylsilane. The particles adopt a cuboctahedral structure with an edge length of three atoms. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

DEFF Research Database (Denmark)

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

2015-01-01

and storage. Here we report on Pt-Si bulk samples prepared by arc-melting, for the first time, with high activities toward the electro-oxidation of CO and methanol. Increasing the Si concentration on the surface was correlated with the shifts of onset oxidation potentials to lower values and higher activities...... for CO and methanol electro-oxidation. It is proposed that the reaction on the Pt-Si catalyst could follow a Langmuir-Hinshelwood type of mechanism, where substantially enhanced catalytic activity is attributed to the fine-tuning of the surface Pt-Si atomic structure....

Structural studies of precursor and partially oxidized conducting complexes. 19. Synthesis and crystal structure of Cs2[Pt(CN)4]Cl/sub 0.30, the first anhydrous one-dimensional tetracyanoplatinate chloride complex

International Nuclear Information System (INIS)

Brown, R.K.; Williams, J.M.

1978-01-01

The preparation and single-crystal x-ray structural characterization of a new, partially oxidized tetracyanoplatinate (POTCP), Cs 2 [Pt(CN) 4 ]Cl/sub 0.30/, CsCP(Cl), has been carried out. This one-dimensional conducting salt crystallizes with four formula units in the tetragonal unit cell I4/mcm, with cell constants a = 13.176 (2) A, c = 5.718 (1) A, and V = 992.7 A 3 . A total of 3112 observed data were averaged to yield 427 independent reflections. The structure was solved by standard heavy-atom methods and was refined by full-matrix least squares to a final R(F 0 2 ) = 0.045 and R/sub w/(F 0 2 ) = 0.059. Pertinent structural features include perfectly linear chains of Pt atoms with Pt-Pt separations crystallographically constrained to a value of (c/2) = 2.859 (2) A and interchain Pt-Pt distances of 9.317 A. Separations between the Cs + and Cl - ions are significantly shorter than the sum of the ionic radii. A discussion of these unusually short interionic distances and the absence of hydration as determined from the structural study and themogravimetric analyses is given. 2 figures, 2 tables

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

Science.gov (United States)

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

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

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

International Nuclear Information System (INIS)

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

2010-01-01

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

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

CERN Document Server

Alshamaileh, E; Wander, A

2003-01-01

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

Hydrogen adsorption-mediated synthesis of concave Pt nanocubes and their enhanced electrocatalytic activity

Science.gov (United States)

Lu, Bang-An; Du, Jia-Huan; Sheng, Tian; Tian, Na; Xiao, Jing; Liu, Li; Xu, Bin-Bin; Zhou, Zhi-You; Sun, Shi-Gang

2016-06-01

Concave nanocubes are enclosed by high-index facets and have negative curvature; they are expected to have enhanced reactivity, as compared to nanocubes with flat surfaces. Herein, we propose and demonstrate a new strategy for the synthesis of concave Pt nanocubes with {hk0} high-index facets, by using a hydrogen adsorption-mediated electrochemical square-wave potential method. It was found that Pt atoms prefer to deposit on edge sites rather than terrace sites on Pt surfaces with intensive hydrogen adsorption, resulting in the formation of concave structures. The as-prepared concave Pt nanocubes exhibit enhanced catalytic activity and stability towards oxidation of ethanol and formic acid in acidic solutions, compared to commercial Pt/C catalysts.Concave nanocubes are enclosed by high-index facets and have negative curvature; they are expected to have enhanced reactivity, as compared to nanocubes with flat surfaces. Herein, we propose and demonstrate a new strategy for the synthesis of concave Pt nanocubes with {hk0} high-index facets, by using a hydrogen adsorption-mediated electrochemical square-wave potential method. It was found that Pt atoms prefer to deposit on edge sites rather than terrace sites on Pt surfaces with intensive hydrogen adsorption, resulting in the formation of concave structures. The as-prepared concave Pt nanocubes exhibit enhanced catalytic activity and stability towards oxidation of ethanol and formic acid in acidic solutions, compared to commercial Pt/C catalysts. Electronic supplementary information (ESI) available: Details of DFT calculation, SEM images of concave Pt nanocubes, mass activity and stability characterization of the catalysts. See DOI: 10.1039/c6nr02349e

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

DEFF Research Database (Denmark)

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

2017-01-01

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

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

Directory of Open Access Journals (Sweden)

Athanasios ePapaderakis

2014-06-01

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

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

Science.gov (United States)

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

2009-05-27

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2015-11-15

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

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

International Nuclear Information System (INIS)

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

2012-01-01

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

Impurities in semiconductors: total energy and infrared absorption calculations

International Nuclear Information System (INIS)

Yndurain, F.

1987-01-01

A new method to calculate the electronic structure of infinite nonperiodic system is discussed. The calculations are performed using atomic pseudopotentials and a basis of atomic Gaussiam wave functions. The Hartree-Fock self consistent equations are solved in the cluster-Bethe lattice system. Electron correlation is partially included in second order pertubation approximation. The formalism is applied to hydrogenated amorphous silicon. Total energy calculations of finite clusters of silicon atom in the presence of impurities, are also presented. The results show how atomic oxygen breaks the covalent silicon silicon bond forming a local configuration similar to that of SiO 2 . Calculations of the infrared absorption due to the presence of atomic oxygen in cristalline silicon are presented. The Born Hamiltonian to calculate the vibrational modes of the system and a simplied model to describe the infrared absorption mechanism are used. The interstitial and the the substitutional cases are considered and analysed. The position of the main infrared absorption peak, their intensities and their isotope shifts are calculated. The results are satisfactory agreement with the available data. (author) [pt

Structures of 38-atom gold-platinum nanoalloy clusters

Energy Technology Data Exchange (ETDEWEB)

Ong, Yee Pin; Yoon, Tiem Leong [School of Physics, Universiti Sains Malaysia, 11800 USM, Penang (Malaysia); Lim, Thong Leng [Faculty of Engineering and Technology, Multimedia University, Melaka Campus, 75450 Melaka (Malaysia)

2015-04-24

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

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

International Nuclear Information System (INIS)

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

2005-01-01

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

How a gold substrate can increase the reactivity of a Pt overlayer

DEFF Research Database (Denmark)

Pedersen, Morten Ø.; Helveg, Stig; Ruban, Andrei

1999-01-01

The growth and chemical reactivity of Pt on Au(111) have been studied using scanning tunneling microscopy (STM) and temperature programmed desorption (TPD). Deposition of Pt at coverages from 0.02 ML up to 2.5 ML on Au(111) at room temperature initially leads to the formation of a surface alloy......, in which 3% of the Au atoms are replaced by Pt. Subsequent Pt evaporation leads to island growth with a mixed Pt-Au island composition. The reactivity of the Pt/Au system is studied using CO as a probe molecule. We show that a stronger bonding of CO to the first layer of Pt on Au(111) exists compared...... with the binding of CO on clean Pt. The Au substrate therefore very surprisingly increases the Pt overlayer reactivity. The results can be understood in a simple model, in which the change in the CO binding energy is directly proportional to the shift of the d-band center of the metal overlayer. According...

Enhanced methanol electro-oxidation reaction on Pt-CoO{sub x}/MWCNTs hybrid electro-catalyst

Energy Technology Data Exchange (ETDEWEB)

Nouralishahi, Amideddin, E-mail: Nouralishahi@ut.ac.ir [Catalysis and Nanostructured Materials Research Laboratory, School of Chemical Engineering, University of Tehran, P.O. Box 11155/4563, Tehran (Iran, Islamic Republic of); Caspian Faculty of Engineering, University of Tehran, P.O. Box 43841-119, Rezvanshahr (Iran, Islamic Republic of); Catalysis and Nanotechnology Research Division, Research Institute of Petroleum Industry (RIPI), P.O. Box 14665-1998, Tehran (Iran, Islamic Republic of); Rashidi, Ali Morad, E-mail: Rashidiam@ripi.ir [Catalysis and Nanotechnology Research Division, Research Institute of Petroleum Industry (RIPI), P.O. Box 14665-1998, Tehran (Iran, Islamic Republic of); Mortazavi, Yadollah, E-mail: Mortazav@ut.ac.ir [Catalysis and Nanostructured Materials Research Laboratory, School of Chemical Engineering, University of Tehran, P.O. Box 11155/4563, Tehran (Iran, Islamic Republic of); Khodadadi, Abbas Ali, E-mail: Khodadad@ut.ac.ir [Catalysis and Nanostructured Materials Research Laboratory, School of Chemical Engineering, University of Tehran, P.O. Box 11155/4563, Tehran (Iran, Islamic Republic of); Choolaei, Mohammadmehdi, E-mail: Choolaeimm@ripi.ir [Catalysis and Nanotechnology Research Division, Research Institute of Petroleum Industry (RIPI), P.O. Box 14665-1998, Tehran (Iran, Islamic Republic of)

2015-04-30

Highlights: • Promoting effects of Cobalt oxide on methanol electro-oxidation over Pt/MWCNTs are investigated. • Higher activity, about 2.9 times, and enhanced stability are observed on Pt-CoO{sub x}/MWCNTs. • Electrochemical active surface area of Pt nanoparticles is significantly improved upon CoO{sub x} addition. • Bi-functional mechanism is facilitated in presence of CoO{sub x}. - Abstract: The electro-catalytic behavior of Pt-CoO{sub x}/MWCNTs in methanol electro-oxidation reaction (MOR) is investigated and compared to that of Pt/MWCNTs. The electro-catalysts were synthesized by an impregnation method using NaBH{sub 4} as the reducing agent. The morphological and physical characteristics of samples are examined by XRD, TEM, ICP and EDS techniques. In the presence of CoO{sub x}, Pt nanoparticles were highly distributed on the support with an average particle size of 2 nm, an obvious decrease from 5.1 nm for Pt/MWCNTs. Cyclic voltammetry, CO-stripping, Chronoamperometry, and electrochemical impedance spectroscopy (EIS) measurements are used to study the electrochemical behavior of the electro-catalysts. The results revealed a considerable enhancement in the oxidation kinetics of CO{sub ads} on Pt active sites by the participation of CoO{sub x}. Compared to Pt/MWCNTs, Pt-CoO{sub x}/MWCNTs sample has a larger electrochemical active surface area (ECSA) and higher electro-catalytic activity and stability toward methanol electro-oxidation. According to the results of cyclic voltammetry, the forward anodic peak current density enhances more than 89% at the optimum atomic ratio of Pt:Co = 2:1. Furthermore, inclusion of cobalt oxide species causes the onset potential of methanol electro-oxidation reaction to shift 84 mV to negative values compared to that on Pt/MWCNTs. Based on EIS data, dehydrogenation of methanol is the rate-determining step of MOR on both Pt/MWCNTs and Pt-CoO{sub x}/MWCNTs, at small overpotentials. However, at higher overpotentials, the

The adsorption of NO on an oxygen pre-covered Pt(1 1 1) surface: in situ high-resolution XPS combined with molecular beam studies

Science.gov (United States)

Zhu, J. F.; Kinne, M.; Fuhrmann, T.; Tränkenschuh, B.; Denecke, R.; Steinrück, H.-P.

2003-12-01

Adsorption of NO on a Pt(1 1 1) surface pre-covered with a p(2 × 2) atomic oxygen layer has been studied in situ by high-resolution X-ray photoelectron spectroscopy and temperature-programmed XPS using third-generation synchrotron radiation at BESSY II, Berlin, combined with molecular beam techniques and ex situ by low energy electron diffraction and temperature-programmed desorption. O 1s XP spectra reveal that an ordered p(2 × 2)-O layer dramatically changes the adsorption behavior of NO as compared to the clean surface. The atomic oxygen occupies fcc hollow sites, and therefore blocks NO adsorption on these sites, which are energetically preferred on clean Pt(1 1 1). As a consequence, NO populates on-top sites at low coverage. At 110 K for higher coverages, NO can additionally adsorb on hcp hollow sites, thereby inducing a shift of the O 1s binding energy of atomic oxygen towards lower energies by about 0.25 eV. The bond strength of the hcp hollow NO species to the substrate is weakened by the presence of atomic oxygen. A sharp p(2 × 2) LEED pattern is observed for NO adsorption on the oxygen pre-covered surface, up to saturation coverage. The total saturation coverage of NO on Pt(1 1 1) pre-covered with varying amounts of oxygen (below 0.25 ML) decreases linearly with the coverage of oxygen. The initial sticking coefficient of NO is reduced from 0.96 on clean Pt(1 1 1) to 0.88 on a p(2 × 2) oxygen pre-covered surface.

Chemical reactions of recoil atoms and thermal atoms of tritium with haloid benzenes

International Nuclear Information System (INIS)

Simirskij, Yu.N.; Firsova, L.P.

1978-01-01

Radiochemical yields have been determined for the products of substitution of hydrogen atoms and halides in Cl-, Br-, and I-benzenes with tritium atoms obtained during thermal dissociation of T 2 and with recoil atoms T arising in nuclear reaction 6 Li(n, P)T. It is shown that in the series of Cl-, Br-, and I-benzenes yields of the products of substitution of halides atoms with tritium grow, whereas those of hydrogen atom substitution change only little. The correlation nature of the yields of substitution products of halide atoms with tritium remains constant in a wide range of the initial kinetic energies of T atoms for the recoil atoms with E 0 =2.7 MeV and for the completely thermolized atoms during thermal dissociation of T 2

Synthesis of SWNT/Pt nanocomposites for their effective role in hydrogen storage applications

Science.gov (United States)

Sharma, Anshu; Andreas, Rossos; Nehra, S. P.

2018-05-01

Single Wall Carbon Nanotubes (SWNTs) decorated with platinum were synthesized for hydrogen storage applications. Platinum was deposited on the nanotubes using hexachloroplatinic acid (H2PtCl6.6H2O) as a precursor. Commercial SWNTs were also used to compare the results. The obtained SWNTs/Pt nanocomposite was characterized by various techniques such as powder X-ray diffractrometry (XRD), Raman Spectroscopy and Scanning Electron Microscopy (SEM). Furthermore, in the case of SWNTs/Pt, Pt nanoparticles are found to be uniformly dispersed and bound to the SWNTs acting like a single atom catalyst.

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

Science.gov (United States)

Altarawneh, Rakan M.; Pickup, Peter G.

2017-10-01

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

Partial and total electronic stopping cross sections of atoms and solids for protons

International Nuclear Information System (INIS)

Kaneko, Toshiaki.

1990-12-01

Based on a wave packet theory (Phys. Rev. A40, 2188(1989); Phys. Stat. Sol. (B)156,49(1989)), partial and total electronic cross sections of target elements in atomic and solid phases with atomic number Z ranging from 2 (He) to 92 (U) are tabulated shell by shell for protons with velocity v from 0.2V 0 to 2OV 0 (V 0 =2.18 x 10 8 cm/s). (author)

Metal Phosphate-Supported Pt Catalysts for CO Oxidation

Directory of Open Access Journals (Sweden)

Xiaoshuang Qian

2014-12-01

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

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

Directory of Open Access Journals (Sweden)

Lović Jelena D.

2012-01-01

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

Atomic diffusion induced degradation in bimetallic layer coated cemented tungsten carbide

International Nuclear Information System (INIS)

Peng, Zirong; Rohwerder, Michael; Choi, Pyuck-Pa; Gault, Baptiste; Meiners, Thorsten; Friedrichs, Marcel; Kreilkamp, Holger; Klocke, Fritz; Raabe, Dierk

2017-01-01

Highlights: • We study the temporal degradation of PtIr/Cr/WC and PtIr/Ni/WC systems. • Short cut diffusion, segregation, oxidation and interdiffusion reactions occurred. • Outward diffusion of Cr (Ni) via PtIr grain boundaries triggered the degradation. • The microstructure of the PtIr layer controlled the systems stability. • We propose an atomic diffusion induced degradation mechanism. - Abstract: We investigated the temporal degradation of glass moulding dies, made of cemented tungsten carbide coated with PtIr on an adhesive Cr or Ni interlayer, by electron microscopy and atom probe tomography. During the exposure treatments at 630 °C under an oxygen partial pressure of 1.12 × 10"−"2"3 bar, Cr (Ni) was found to diffuse outwards via grain boundaries in the PtIr, altering the surface morphology. Upon dissolution of the interlayer, the WC substrate also started degrading. Extensive interdiffusion processes involving PtIr, Cr (Ni) and WC took place, leading to the formation of intermetallic phases and voids, deteriorating the adhesion of the coating.

First-principles study on the phase transition, elastic properties and electronic structure of Pt{sub 3}Al alloys under high pressure

Energy Technology Data Exchange (ETDEWEB)

Liu, Yanjun [Key Laboratory of Oil and Gas Equipment of Ministry of Education, Southwest Petroleum University, Chengdu, Sichuan 610500 (China); Huang, Huawei [National Key Laboratory for Nuclear Fuel and Materials, Nuclear Power of China, Chengdu, Sichuan 610041 (China); Pan, Yong, E-mail: yongpanyn@163.com [State Key Laboratory of Advanced Technologies for Comprehensive Utilization of Platinum Metals, Kunming 650106 (China); Zhao, Guanghui; Liang, Zheng [Key Laboratory of Oil and Gas Equipment of Ministry of Education, Southwest Petroleum University, Chengdu, Sichuan 610500 (China)

2014-06-01

Highlights: • The phase transition of Pt{sub 3}Al alloys occurs at 60 GPa. • The elastic modulus of Pt{sub 3}Al alloys increase with increasing pressure. • The cubic structure has good resistance to volume deformation under high pressure. • The pressure enhances the hybridization between Pt atom and Al atom. - Abstract: The phase transition, formation enthalpies, elastic properties and electronic structure of Pt{sub 3}Al alloys are studied using first-principle approach. The calculated results show that the pressure leads to phase transition from tetragonal structure to cubic structure at 60 GPa. With increasing pressure, the elastic constants, bulk modulus and shear modulus of these Pt{sub 3}Al alloys increase linearly and the bond lengths of Pt–Al metallic bonds and the peak at E{sub F} decrease. The cubic Pt{sub 3}Al alloy has excellent resistance to volume deformation under high pressure. We suggest that the phase transition is derived from the hybridization between Pt and Al atoms for cubic structure is stronger than that of tetragonal structure and forms the strong Pt–Al metallic bonds under high pressure.

Effective adsorption/electrocatalytic degradation of perchlorate using Pd/Pt supported on N-doped activated carbon fiber cathode

Energy Technology Data Exchange (ETDEWEB)

Yao, Fubing; Zhong, Yu [College of Environmental Science and Engineering, Hunan University, Changsha 410082 (China); Key Laboratory of Environmental Biology and Pollution Control, Hunan University, Ministry of Education, Changsha 410082 (China); Yang, Qi, E-mail: yangqi@hnu.edu.cn [College of Environmental Science and Engineering, Hunan University, Changsha 410082 (China); Key Laboratory of Environmental Biology and Pollution Control, Hunan University, Ministry of Education, Changsha 410082 (China); Wang, Dongbo, E-mail: dongbowang@hnu.edu.cn [College of Environmental Science and Engineering, Hunan University, Changsha 410082 (China); Key Laboratory of Environmental Biology and Pollution Control, Hunan University, Ministry of Education, Changsha 410082 (China); Chen, Fei; Zhao, Jianwei; Xie, Ting; Jiang, Chen; An, Hongxue; Zeng, Guangming; Li, Xiaoming [College of Environmental Science and Engineering, Hunan University, Changsha 410082 (China); Key Laboratory of Environmental Biology and Pollution Control, Hunan University, Ministry of Education, Changsha 410082 (China)

2017-02-05

Highlights: • Pd/Pt-NACF served as an adsorption/electrocatalysis electrode to reduce perchlorate. • The possible mechanisms involved in the reaction process were explained. • The reusability and stability of Pd/Pt-NACF bifunctional material was evaluated. - Abstract: 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 (20 mA). 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.

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

Science.gov (United States)

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

2017-03-22

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2008-07-01

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

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

Science.gov (United States)

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

2018-06-01

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

Evaluation of the behavior of PtPd/MWCNT electrocatalysts as ethylene glycol-tolerant electrodes for oxygen oxidation reaction (ORR); Evaluacion del comportamiento de electrocatalizadores tipo PtPd/MWCNT como electrodos para la reaccion de oxidacion del oxigeno (ORR) tolerantes al etilenglicol

Energy Technology Data Exchange (ETDEWEB)

Morales-Acosta, D.; Arriaga, L.G. [Centro de Investigacion y Desarrollo Tecnologico en Electroquimica, Pedro Escobedo, Queretaro (Mexico)]. E-mail: dmorales@cideteq.mx; Alvarez-Contreras, L. [Centro de Investigacion en Materiales Avanzados S. C., Chihuahua, Chihuahua (Mexico); Fraire Luna, S.; Rodriguez Varela, F.J. [Cinvestav, Unidad Saltillo, Ramos Arizpe, Coahuila, (Mexico)

2009-09-15

Pt-Pd/MWCNTs (atomic ratio Pt:Pd 43:57) and Pt/MWCNTs electrocatalysts were synthesized and evaluated as cathodes for oxygen reduction reaction (ORR) with the application of direct ethylene glycol fuel cells (DEGFC). A commercial PtC material was also evaluated as a reference. It was found that Pt-Pd/MWCNT has a capability for high tolerance to ethylene glycol (EG) and higher selectivity for ORR compared to a single Pt- cathode. As a result, the change in onset potential of the ORR, Eonset, in Pt-Pd/MWCNTs was considerably less than the change in Pt/MWCNTs or Pt/C. The average particle size (XRD) was 3.5nm and 4nm for Pt/MWCNTs and Pt-Pd/MWCNTs, respectively. A moderate degree of alloying was determined for the material. The application of Pt-Pd electrocatalysts in DEGFCs should be advantageous. [Spanish] Electrocatalizadores Pt-Pd/MWCNTs (relacion atomic Pt:Pd 43:57) y Pt/MWCNTs fueron sintetizados y evaluados como catodos para la reaccion de reduccion del oxigeno (ORR) con aplicacion del celdas de consumo directo de etilenglicol (Direct Ethylene Glycol Fuel Cells, o DEGFC). Como referencia, un material comercial tipo Pt/C fue tambien evaluado. Se encontro que Pt-Pd/MWCNTs tiene una alta capacidad de tolerancia al etilenglicol (EG) y una selectividad mayor hacia la ORR comparado con el catodo basado en Pt-solo. Como resultado, el cambio en potencial de inicio de la ORR, Eonset, en Pt-Pd/MWCNTs fue considerablemente menor que el cambio en Pt/MWCNTs o Pt/C. La talla de particula promedio (de XRD) fue 3.5 nm y 4 nm para Pt/MWCNTs y Pt-Pd/MWCNTs, respectivamente. Un moderado grado de aleacion fue determinado para el material. Una aplicacion ventajosa para electrocatalizadores tipo Pt-Pd debe ser en DEGFCs.

Molecular invariants: atomic group valence

International Nuclear Information System (INIS)

Mundim, K.C.; Giambiagi, M.; Giambiagi, M.S. de.

1988-01-01

Molecular invariants may be deduced in a very compact way through Grassman algebra. In this work, a generalized valence is defined for an atomic group; it reduces to the Known expressions for the case of an atom in a molecule. It is the same of the correlations between the fluctions of the atomic charges qc and qd (C belongs to the group and D does not) around their average values. Numerical results agree with chemical expectation. (author) [pt

An XAS experimental approach to study low Pt content electrocatalysts operating in PEM fuel cells.

Science.gov (United States)

Principi, Emiliano; Witkowska, Agnieszka; Dsoke, Sonia; Marassi, Roberto; Di Cicco, Andrea

2009-11-21

We present an X-ray absorption spectroscopy (XAS) study of a low Pt content catalyst layer (Pt loading 0.1 mg cm(-2)) operating at the cathode of a proton exchange membrane fuel cell (PEMFC). This catalyst is based on the use of a mesoporous inorganic matrix as a support for the catalyst Pt nanoparticles. Due to the high Pt dilution, in situ measurements of its structural properties by XAS are challenging and suitable experimental strategies must be devised for this purpose. In particular, we show that accurate XAS in situ fluorescence measurements can be obtained using an optimized fuel cell, suitable protocols for alignment of a focused X-ray beam and an appropriate filter for the background signal of the other atomic species contained in the electrodes. Details, advantages and limitations of the XAS technique for in situ measurements are discussed. Analysis of the near-edge XAS and EXAFS (extended X-ray absorption fine structure) data, corroborated by a HRTEM (high-resolution transmission electron microscopy) study, shows that the Pt particles have a local structure compatible with that of bulk Pt (fcc) and coordination numbers match those expected for particles with typical sizes in the 1.5-2.0 nm range. Substantial changes in the oxidation state and in local atomic arrangement of the Pt particles are found for different applied potentials. The catalyst support, containing W atoms, exhibits a partial reduction upon PEMFC activation, thus mimicking the catalyst behavior. This indicates a possible role of the mesoporous matrix in favouring the oxygen reduction reaction (ORR) and stimulates further research on active catalyst supports.

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

Energy Technology Data Exchange (ETDEWEB)

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

2006-09-29

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

Balance of Nanostructure and Bimetallic Interactions in Pt Model Fuel Cell Catalysts

DEFF Research Database (Denmark)

Friebel, Daniel; Viswanathan, Venkatasubramanian; Miller, Daniel J.

2012-01-01

We have studied the effect of nanostructuring in Pt monolayer model electrocatalysts on a Rh(111) single-crystal substrate on the adsorption strength of chemisorbed species. In situ high energy resolution fluorescence detection X-ray absorption spectroscopy at the Pt L3 edge reveals characteristic...... changes of the shape and intensity of the “white-line” due to chemisorption of atomic hydrogen (Had) at low potentials and oxygen-containing species (O/OHad) at high potentials. On a uniform, two-dimensional Pt monolayer grown by Pt evaporation in ultrahigh vacuum, we observe a significant destabilization...... of both Had and O/OHad due to strain and ligand effects induced by the underlying Rh(111) substrate. When Pt is deposited via a wet-chemical route, by contrast, three-dimensional Pt islands are formed. In this case, strain and Rh ligand effects are balanced with higher local thickness of the Pt islands...

(Pt{sub 1–x}Cu{sub x}){sub 3}Cu{sub 2}B and Pt{sub 9}Cu{sub 3}B{sub 5}, the first examples of copper platinum borides. Observation of superconductivity in a novel boron filled β-Mn-type compound

Energy Technology Data Exchange (ETDEWEB)

Salamakha, Leonid P. [Institute of Solid State Physics, TU Wien, A-1040 Wien (Austria); Sologub, Oksana, E-mail: oksana.sologub@univie.ac.at [Institute of Solid State Physics, TU Wien, A-1040 Wien (Austria); Stöger, Berthold [Institute of Chemical Technologies and Analytics, TU Wien, A-1040 Wien (Austria); Michor, Herwig; Bauer, Ernst [Institute of Solid State Physics, TU Wien, A-1040 Wien (Austria); Rogl, Peter F. [Institute of Physical Chemistry, University of Vienna, A-1090 Wien (Austria)

2015-09-15

New ternary copper platinum borides have been synthesized by arc melting of pure elements followed by annealing at 600 °C. The structures have been studied by X-ray single crystal and powder diffraction. (Pt{sub 1−x}Cu{sub x}){sub 3}Cu{sub 2}B (x=0.33) forms a B-filled β-Mn-type structure (space group P4{sub 1}32; a=0.6671(1) nm). Cu atoms are distributed preferentially on the 8c atom sites, whereas the 12d site is randomly occupied by Pt and Cu atoms (0.670(4) Pt±0.330(4) Cu). Boron is located in octahedral voids of the parent β-Mn-type structure. Pt{sub 9}Cu{sub 3}B{sub 5} (space group P-62m; a=0.9048(3) nm, c=0.2908(1) nm) adopts the Pt{sub 9}Zn{sub 3}B{sub 5–δ}-type structure. It has a columnar architecture along the short translation vector exhibiting three kinds of [Pt{sub 6}] trigonal prism columns (boron filled, boron semi-filled and empty) and Pt channels with a pentagonal cross section filled with Cu atoms. The striking structural feature is a [Pt{sub 6}] cluster in form of an empty trigonal prism at the origin of the unit cell, which is surrounded by coupled [BPt{sub 6}] and [Pt{sub 6}] trigonal prisms, rotated perpendicularly to the central one. There is no B–B contact as well as Cu–B contact in the structure. The relationships of Pt{sub 9}Cu{sub 3}B{sub 5} structure with the structure of Ti{sub 1+x}Os{sub 2−x}RuB{sub 2} as well as with the structure families of metal sulfides and aluminides have been elucidated. (Pt{sub 1–x}Cu{sub x}){sub 3}Cu{sub 2}B (x=0.3) (B-filled β-Mn-type structure) is a bulk superconductor with a transition temperature of about 2.06 K and an upper critical field μ{sub 0}H{sub C2}(0){sup WHH} of 1.2 T, whereas no superconducting transition has been observed up to 0.3 K in Pt{sub 9}Cu{sub 3}B{sub 5} (Pt{sub 9}Zn{sub 3}B{sub 5–δ}-type structure) from electrical resistivity measurements. - Highlights: • First two copper platinum borides, (Pt{sub 0.67}Cu{sub 0.33}){sub 3}Cu{sub 2}B and Pt{sub 9}Cu{sub 3}B

Controlled damaging and repair of self-organized nanostructures by atom manipulation at room temperature

International Nuclear Information System (INIS)

Gurlu, O; Houselt, A van; Thijssen, W H A; Ruitenbeek, J M van; Poelsema, B; Zandvliet, H J W

2007-01-01

The possibility of controlled local demolition and repair of the recently discovered self-organized Pt nanowires on Ge(001) surfaces has been explored. These nanowires are composed of Pt dimers, which are found to be rather weakly bound to the underlying substrate. Using this property, we demonstrate the possibility of carrying the constituting dimers of the Pt nanowires from point to point with atomic precision at room temperature. Pt dimers can be picked-up in two configurations: (i) a horizontal configuration at the tip apex, resulting in double tip images and (ii) a configuration where the Pt dimer is attached to the side of the tip apex, resulting in well-defined atomically resolved images

Synthesis and characterization of Pt-Sn-Ni alloys to application as catalysts for direct ethanol fuel cells; Sintese e caracterizacao de ligas de Pt-Sn-Ni para aplicacao como caztalisadores em celulas a combustivel do tipo DEFC

Energy Technology Data Exchange (ETDEWEB)

Silva, E.L. da; Correa, P.S.; Oliveira, E.L. de; Takimi, A.S.; Malfatti, C.F., E-mail: celia.malfatti@ufrgs.b [Universidade Federal do Rio Grande do Sul (LAPEC/UFRGS), Porto Alegre, RS (Brazil). Programa de Pos-Graduacao em Engenharia Mecanica. Lab. de Pesquisa em Corrosao; Radtke, C. [Universidade Federal do Rio Grande do Sul (IQ/UFRGS), Porto Alegre, RS (Brazil). Inst. de Quimica

2010-07-01

Direct ethanol fuel cells (DEFCs) have been the focus of recent research due its application in mobile energy sources. In order to obtain the maximum efficiency from these systems, it is necessary the total ethanol oxidation, which implies in C-C bond break. Different catalysts described in literature are employed with this intent. This work consists in studying PtSnNi catalysts supported on carbon Vulcan XC72R, to application in DEFCs. Thus, it was used the impregnation/reduction method, varying the atomic proportion among Pt, Sn and Ni. The alloys were characterized by X-Ray Diffraction, Cyclic Voltammetry and Transmission Microscopy. Preliminary results show that predominant structure on the catalysts is the face centered cubic platinum and the densities currents are dependent on the platinum amount. (author)

Halogen poisoning effect of Pt-TiO{sub 2} for formaldehyde catalytic oxidation performance at room temperature

Energy Technology Data Exchange (ETDEWEB)

Zhu, Xiaofeng; Cheng, Bei [State Key Laboratory of Advanced Technology for Material Synthesis and Processing, Wuhan University of Technology, Luoshi Road 122#, Wuhan 430070 (China); Yu, Jiaguo, E-mail: jiaguoyu@yahoo.com [State Key Laboratory of Advanced Technology for Material Synthesis and Processing, Wuhan University of Technology, Luoshi Road 122#, Wuhan 430070 (China); Department of Physics, Faculty of Science, King Abdulaziz University, Jeddah 21589 (Saudi Arabia); Ho, Wingkei, E-mail: keithho@ied.edu.hk [Department of Science and Environmental Studies and Centre for Education in Environmental Sustainability, The Hong Kong Institute of Education, Tai Po, N.T. Hong Kong (China)

2016-02-28

Graphical abstract: - Highlights: • The Pt-TiO{sub 2} catalyst is deactivated by adsorption of halogen ions. • The halogen poison is mainly attributed to the active site blocking of the Pt surface. • Halogen ions and Pt form Pt−X coordination bonds. • Large halogen diameter exhibits severe poisoning effect. - Abstract: Catalytic decomposition of formaldehyde (HCHO) at room temperature is an important method for HCHO removal. Pt-based catalysts are the optimal catalyst for HCHO decomposition at room temperature. However, the stability of this catalyst remains unexplored. In this study, Pt-TiO{sub 2} (Pt-P25) catalysts with and without adsorbed halogen ions (including F{sup −}, Cl{sup −}, Br{sup −}, and I{sup −}) were prepared through impregnation and ion modification. Pt-TiO{sub 2} samples with adsorbed halogen ions exhibited reduced catalytic activity for formaldehyde decomposition at room temperature compared with the Pt-TiO{sub 2} sample; the catalytic activity followed the order of F-Pt-P25, Cl-Pt-P25, Br-Pt-P25, and I-Pt-P25. Characterization results (including XRD, TEM, HRTEM, BET, XPS, and metal dispersion) showed that the adsorbed halogen ions can poison Pt nanoparticles (NPs), thereby reducing the HCHO oxidation activity of Pt-TiO{sub 2}. The poison mechanism is due to the strong adsorption of halogen ions on the surface of Pt NPs. The adsorbed ions form coordination bonds with surface Pt atoms by transferring surplus electrons into the unoccupied 5d orbit of the Pt atom, thereby inhibiting oxygen adsorption and activation of the Pt NP surface. Moreover, deactivation rate increases with increasing diameter of halogen ions. This study provides new insights into the fabrication of high-performance Pt-based catalysts for indoor air purification.

Synthesis and characterization of FePt/Au core-shell nanoparticles

International Nuclear Information System (INIS)

Presa, P. de la; Multigner, M.; Morales, M.P.; Rueda, T.; Fernandez-Pinel, E.; Hernando, A.

2007-01-01

In this work, the structural and magnetic properties of the gold-coated FePt nanoparticles synthesized from high-temperature solution phase are presented. The amount of gold was optimized to obtain most of the FePt particles coated. The particle diameter increases from 4 to 10 nm as observed by TEM. The magnetic properties are largely affected by the coating. At low temperature, the coercive field Hc of the coated nanoparticles decreases about three times respect to the uncoated and the blocking temperature reduces to the half. The changes of the magnetic behavior are discussed in terms of the effect of the gold atoms at the FePt core surface

Comparison of 4 analytical techniques based on atomic spectrometry for the determination of total tin in canned foodstuffs

OpenAIRE

2011-01-01

Abstract Different techniques for the determination of total tin in beverage and canned food by atomic spectrometry were compared. The performance characteristics of Inductively Coupled Plasma Mass Spectrometry (ICP-MS), Hydride Generation Inductively Coupled Plasma Atomic Emission Spectrometry (HG-ICP-AES), Electrothermal Atomization Atomic Absorption Spectrometry (ETA-AAS) and Inductively Coupled Plasma Atomic Emission Spectrometry (ICP-AES) were determined in term of linearity, ...

Fast Synthesis of Pt Nanocrystals and Pt/Microporous La2O3 Materials Using Acoustic Levitation

Science.gov (United States)

Yu, Yinkai; Qu, Shaohua; Zang, Duyang; Wang, Liuding; Wu, Hongjing

2018-02-01

Usually, we must use an appropriate support material to keep the metal species stable and finely dispersed as supported metal nanoparticles for industry application. Therefore, the choice of support material is a key factor in determining the dispersion and particle size of the noble metal species. Here, we report the synthesis of a single-atom Pt material in the solution and supported Pt nanoclusters on microporous La2O3 by a one-step acoustic levitation method without any pretreatment/modification of raw oxide. We have strongly contributed to the synthetic methodology of the surface/interfacial heterogeneous catalysts in this study, and this finding could open another door for synthesis of supported metal nanoparticles on porous materials for environmental catalysis.

Pt-Ag cubic nanocages with wall thickness less than 2 nm and their enhanced catalytic activity toward oxygen reduction.

Science.gov (United States)

Sun, Xiaojun; Yang, Xuan; Zhang, Yun; Ding, Yong; Su, Dong; Qin, Dong

2017-10-12

We report a facile synthesis of Pt-Ag nanocages with walls thinner than 2 nm by depositing a few atomic layers of Pt as conformal shells on Ag nanocubes and then selectively removing the Ag template via wet etching. In a typical process, we inject a specific volume of aqueous H 2 PtCl 6 into a mixture of Ag nanocubes, ascorbic acid (H 2 Asc), NaOH, and poly(vinylpyrrolidone) in water under ambient conditions. At an initial pH of 11.9, the Pt(iv) precursor is quickly reduced by an ascorbate monoanion, a strong reducing agent derived from the neutralization of H 2 Asc with NaOH. The newly formed Pt atoms are deposited onto the edges and then corners and side faces of Ag nanocubes, leading to the generation of Ag@Pt core-shell nanocubes with a conformal Pt shell of approximately three atomic layers (or, about 0.6 nm in thickness) when 0.4 mL of 0.2 mM H 2 PtCl 6 is involved. After the selective removal of Ag in the core using an etchant based on a mixture of Fe(NO 3 ) 3 and HNO 3 , we transform the core-shell nanocubes into Pt-Ag alloy nanocages with an ultrathin wall thickness of less than 2 nm. We further demonstrate that the as-obtained nanocages with a composition of Pt 42 Ag 58 exhibit an enhanced catalytic activity toward the oxygen reduction reaction, with a mass activity of 0.30 A mg -1 and a specific activity of 0.93 mA cm -2 , which are 1.6 and 2.5 times, respectively, greater than those of a commercial Pt/C catalyst.

Density Functional Theory plus Hubbard U Study of the Segregation of Pt to the CeO2- x Grain Boundary.

Science.gov (United States)

Zhou, Guoli; Li, Pan; Ma, Qingmin; Tian, Zhixue; Liu, Ying

2018-03-14

Grain boundaries (GBs) can be used as traps for solute atoms and defects, and the interaction between segregants and GBs is crucial for understanding the properties of nanocrystalline materials. In this study, we have systematically investigated the Pt segregation and Pt-oxygen vacancies interaction at the ∑3 (111) GB in ceria (CeO 2 ). The Pt atom has a stronger tendency to segregate to the ∑3 (111) GB than to the (111) and (110) free surfaces, but the tendency is weaker than to (112) and (100). Lattice distortion plays a dominant role in Pt segregation. At the Pt-segregated-GB (Pt@GB), oxygen vacancies prefer to form spontaneously near Pt in the GB region. However, at the pristine GB, oxygen vacancies can only form under O-poor conditions. Thus, Pt segregation to the GB promotes the formation of oxygen vacancies, and their strong interactions enhance the interfacial cohesion. We propose that GBs fabricated close to the surfaces of nanocrystalline ceria can trap Pt from inside the grains or other types of surface, resulting in the suppression of the accumulation of Pt on the surface under redox reactions, especially under O-poor conditions.

Exploring the Potential of Different-Sized Supported Subnanometer Pt Clusters as Catalysts for Wet Chemical Applications

KAUST Repository

Rondelli, Manuel; Zwaschka, Gregor; Krause, Maximilian; Rö tzer, Marian D.; Hedhili, Mohamed N.; Hogerl, Manuel Peter; D’ Elia, Valerio; Schweinberger, Florian F.; Basset, Jean-Marie; Heiz, Ueli

2017-01-01

as catalysts for organic chemistry transformations in solution has not been explored. To this end, single Pt atoms and Pt clusters with two narrow size distributions were prepared in the UHV and applied for the hydrogenation of p-chloronitrobenzene to p

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

CSIR Research Space (South Africa)

Motsoeneng, RG

2015-09-01

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

Synthesis and characterization of Pt-Sn-Ni alloys to application as catalysts for direct ethanol fuel cells

International Nuclear Information System (INIS)

Silva, E.L. da; Correa, P.S.; Oliveira, E.L. de; Takimi, A.S.; Malfatti, C.F.; Radtke, C.

2010-01-01

Direct ethanol fuel cells (DEFCs) have been the focus of recent research due its application in mobile energy sources. In order to obtain the maximum efficiency from these systems, it is necessary the total ethanol oxidation, which implies in C-C bond break. Different catalysts described in literature are employed with this intent. This work consists in studying PtSnNi catalysts supported on carbon Vulcan XC72R, to application in DEFCs. Thus, it was used the impregnation/reduction method, varying the atomic proportion among Pt, Sn and Ni. The alloys were characterized by X-Ray Diffraction, Cyclic Voltammetry and Transmission Microscopy. Preliminary results show that predominant structure on the catalysts is the face centered cubic platinum and the densities currents are dependent on the platinum amount. (author)

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

International Nuclear Information System (INIS)

Yang Jianyu; Hu Wangyu; Chen Shuguang

2010-01-01

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

Synthesis of bimetallic Pt-Pd core-shell nanocrystals and their high electrocatalytic activity modulated by Pd shell thickness

Science.gov (United States)

Li, Yujing; Wang, Zhi Wei; Chiu, Chin-Yi; Ruan, Lingyan; Yang, Wenbing; Yang, Yang; Palmer, Richard E.; Huang, Yu

2012-01-01

Bimetallic Pt-Pd core-shell nanocrystals (NCs) are synthesized through a two-step process with controlled Pd thickness from sub-monolayer to multiple atomic layers. The oxygen reduction reaction (ORR) catalytic activity and methanol oxidation reactivity of the core-shell NCs for fuel cell applications in alkaline solution are systematically studied and compared based on different Pd thickness. It is found that the Pd shell helps to reduce the over-potential of ORR by up to 50mV when compared to commercial Pd black, while generating up to 3-fold higher kinetic current density. The carbon monoxide poisoning test shows that the bimetallic NCs are more resistant to the CO poisoning than Pt NCs and Pt black. It is also demonstrated that the bimetallic Pt-Pd core-shell NCs can enhance the current density of the methanol oxidation reaction, lowering the over-potential by 35 mV with respect to the Pt core NCs. Further investigation reveals that the Pd/Pt ratio of 1/3, which corresponds to nearly monolayer Pd deposition on Pt core NCs, gives the highest oxidation current density and lowest over-potential. This study shows for the first time the systematic investigation of effects of Pd atomic shells on Pt-Pd bimetallic nanocatalysts, providing valuable guidelines for designing high-performance catalysts for fuel cell applications.Bimetallic Pt-Pd core-shell nanocrystals (NCs) are synthesized through a two-step process with controlled Pd thickness from sub-monolayer to multiple atomic layers. The oxygen reduction reaction (ORR) catalytic activity and methanol oxidation reactivity of the core-shell NCs for fuel cell applications in alkaline solution are systematically studied and compared based on different Pd thickness. It is found that the Pd shell helps to reduce the over-potential of ORR by up to 50mV when compared to commercial Pd black, while generating up to 3-fold higher kinetic current density. The carbon monoxide poisoning test shows that the bimetallic NCs are more

Sulfur-tolerant Pt-supported catalysts for benzene hydrogenation. II. Influence of cation exchange level for Pt/MOR-based catalysts

NARCIS (Netherlands)

Simon, L.; van Ommen, J.G.; Jentys, A.; Lercher, J.A.

2001-01-01

Two reaction pathways are described for the hydrogenation of benzene over Pt/MOR, i.e., (i) on the metal particles and (ii) on Brønsted acid sites of MOR at the boundary to the metal, with atomic hydrogen being dissociated on the metal. The ratio between the two pathways depends on the zeolite acid

An in-situ X-ray diffraction study on the electrochemical formation of PtZn alloys on Pt(1 1 1) single crystal electrode

Energy Technology Data Exchange (ETDEWEB)

Drnec, J., E-mail: drnec@esrf.fr [ESRF, Grenoble (France); Bizzotto, D. [Department of Chemistry, AMPEL, University of British Columbia, Vancouver, BC (Canada); Carlà, F. [ESRF, Grenoble (France); Fiala, R. [Charles University, Faculty of Mathematics and Physics, Prague (Czech Republic); Sode, A. [Ruhr-Universität Bochum, Bochum (Germany); Balmes, O.; Detlefs, B.; Dufrane, T. [ESRF, Grenoble (France); Felici, R., E-mail: felici@esrf.fr [ESRF, Grenoble (France)

2015-11-01

Highlights: • PtZn electrochemical alloying is observed on single crystal Pt electrodes. • In-situ X-ray characterization during alloy formation and dissolution is provided. • Structural model of the surface during alloying and dissolution is discussed. • X-ray based techniques can be used in in-operando studies of bimetallic fuel cell catalysts. - Abstract: The electrochemical formation and dissolution of the oxygen reduction reaction (ORR) PtZn catalyst on Pt(1 1 1) surface is followed by in-situ X-ray diffraction (XRD) and X-ray reflectivity (XRR) measurements. When the crystalline Pt surface is polarized to sufficiently negative potential values, with respect to an Ag/AgCl|KCl reference electrode, the electrodeposited zinc atoms diffuse into the bulk and characteristic features are observed in the X-ray patterns. The surface structure and composition during deposition and dissolution is determined from analysis of XRR curves and measurements of crystal truncation rods. Thin Zn-rich surface layer is present during the alloy formation while a Zn-depleted layer forms during dissolution.

Phase diagrams of two dimensional Pd{sub x}Ag{sub 1-x}/Pd(111) and Pt{sub x}Ag{sub 1-x}/Pt(111) surface alloys

Energy Technology Data Exchange (ETDEWEB)

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

2011-07-01

The distribution of Ag and Pd or Pt in Ag{sub x}Pd{sub 1-x}/Pd(111) and Ag{sub x}Pt{sub 1-x}/Pt(111) surface alloys was studied by high resolution UHV-STM. The alloys were prepared by evaporating Ag on the respective substrate and subsequent annealing to 800 K. From quantitative 2D atom distributions we can show that AgPt tends towards two dimensional clustering and AgPd towards a 'quasi' random distribution, with small deviations for low and high coverages. From effective pair interactions, we are able to calculate the surface mixing energy and determine 2D phase diagrams. Furthermore we will elucidate whether the size mismatch or the differences in the intermetallic bonding are the dominant factor for the respective distribution in the surface alloy.

Theoretical evidence of PtSn alloy efficiency for CO oxidation.

Science.gov (United States)

Dupont, Céline; Jugnet, Yvette; Loffreda, David

2006-07-19

The efficiency of PtSn alloy surfaces toward CO oxidation is demonstrated from first-principles theory. Oxidation kinetics based on atomistic density-functional theory calculations shows that the Pt3Sn surface alloy exhibits a promising catalytic activity for fuel cells. At room temperature, the corresponding rate outstrips the activity of Pt(111) by several orders of magnitude. According to the oxidation pathways, the activation barriers are actually lower on Pt3Sn(111) and Pt3Sn/Pt(111) surfaces than on Pt(111). A generalization of Hammer's model is proposed to elucidate the key role of tin on the lowering of the barriers. Among the energy contributions, a correlation is evidenced between the decrease of the barrier and the strengthening of the attractive interaction energy between CO and O moieties. The presence of tin modifies also the symmetry of the transition states which are composed of a CO adsorbate on a Pt near-top position and an atomic O adsorption on an asymmetric mixed PtSn bridge site. Along the reaction pathways, a CO2 chemisorbed surface intermediate is obtained on all the surfaces. These results are supported by a thorough vibrational analysis including the coupling with the surface phonons which reveals the existence of a stretching frequency between the metal substrate and the CO2 molecule.

Collisional alignment and orientation of atomic outer shells. Pt. 1

International Nuclear Information System (INIS)

Andersen, N.; Gallagher, J.W.; Hertel, I.V.

1988-01-01

The study of polarization of atomic radiation emitted after impact excitation has yielded an enormous wealth of detailed information on the mechanism and dynamics of collisional excitation and energy transfer, both in electron and heavy particle impact studies. In these studies, the beam of electrons, ions or fast atoms used to excite the target atoms provides a suitable quantization axis with respect to which the polarization of the fluorescent light of the excited atoms is detected. From these data information on the cross sections for the different magnetic substates of the excited atom is extracted, imparting a great deal of insight into impact mechanisms for both outer and inner shell excitation. It is our aim to provide a comprehensive review including all data available in the literature presented in a standardized and easily accessible fashion. In this review we include only alignment and orientation studies, which have a well-defined planar symmetry, i.e., in which the initial and final relative momentum of the interacting particles are well defined by differential scattering techniques. We do not make a major distinction between heavy-particle and electron impact excitation: In fact, one of our aims is to demonstrate similarities between the two fields from a technical as well as from a conceptual point of view. The review is divided into three parts: This first part (I) deals with direct excitation of atoms by electrons and fast atoms or ions. Section 2 gives an introduction to the general concepts and ideas behind this kind of study and a description of typical experimental setups. Section 3 deals with electron impact excitation of atoms, starting with the simplest case of electron-helium collisions which may be fully described by two parameters, followed by more complex cases such as electron impact excitation of hydrogen and the heavy rare gases. Section 4 describes the results for direct excitation by atomic impact. (orig./AH)

Multi-center vs. two-center bonding within the hetero-polyanion in Eu{sub 2}GaPt{sub 2} and its prototype Ca{sub 2}SiIr{sub 2}

Energy Technology Data Exchange (ETDEWEB)

Poettgen, Rainer [Institut fuer Anorganische und Analytische Chemie, Universitaet Muenster (Germany); Borrmann, Horst; Grin, Yuri [Max-Planck-Institut fuer Chemische Physik fester Stoffe, Dresden (Germany)

2017-11-17

The compound Eu{sub 2}GaPt{sub 2} was synthesized from the elements in a sealed tantalum tube. Its Ca{sub 2}SiIr{sub 2}-type crystal structure was refined from single-crystal X-ray diffraction data: space group C2/c, a = 9.8775(6), b = 5.8621(6), c = 7.9677(5) Aa, β = 102.257(4) , R{sub F} = 0.039, 1344 observed reflections, and 25 variable parameters. The platinum (iridium) atoms in Eu{sub 2}GaPt{sub 2} and Ca{sub 2}SiIr{sub 2} form linear chains of dumbbells [2c(Pt-Pt) or 2c(Ir-Ir) bonds, respectively]. These chains are interconnected to 2D polyanions in Eu{sub 2}GaPt{sub 2} by the gallium atoms forming 4c(Ga-Pt-Ga-Pt) or by silicon atoms forming 2c(Si-Ir) bonds in Ca{sub 2}SiIr{sub 2}. The polyanion bonds to the europium (calcium) matrix via the pseudo lone-pairs at the gallium (silicon) atoms. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

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

Science.gov (United States)

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

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

Electrons and atoms in intense laser fields

International Nuclear Information System (INIS)

Davidovich, L.

1982-11-01

Several non-linear effects that show up when electrons and atoms interact with strong laser fields are considered. Thomson scattering, electron potential scattering in the presence of a laser beam, atomic ionization by strong laser fields, the refraction of electrons by laser beams and the Kapitza-Dirac effect are discussed. (Author) [pt

Electrons and atoms in intense laser fields

International Nuclear Information System (INIS)

Davidovich, L.

1982-01-01

Several non-linear effects that show up when electrons and atoms interact with strong laser fields are considered. Thomson scattering, electron potential scattering in the presence of a laser beam, atomic ionization by strong laser fields, the refraction of electrons by laser beams and the Kapitza-Dirac effect are discussed. (Author) [pt

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

Energy Technology Data Exchange (ETDEWEB)

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

2012-07-16

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

Self-lacing atom chains

International Nuclear Information System (INIS)

Zandvliet, Harold J W; Van Houselt, Arie; Poelsema, Bene

2009-01-01

The structural and electronic properties of self-lacing atomic chains on Pt modified Ge(001) surfaces have been studied using low-temperature scanning tunnelling microscopy and spectroscopy. The self-lacing chains have a cross section of only one atom, are perfectly straight, thousands of atoms long and virtually defect free. The atomic chains are composed of dimers that have their bonds aligned in a direction parallel to the chain direction. At low temperatures the atomic chains undergo a Peierls transition: the periodicity of the chains doubles from a 2 x to a 4 x periodicity and an energy gap opens up. Furthermore, at low temperatures (T<80 K) novel quasi-one-dimensional electronic states are found. These quasi-one-dimensional electronic states originate from an electronic state of the underlying terrace that is confined between the atomic chains.

Pt, Co–Pt and Fe–Pt alloy nanoclusters encapsulated in virus capsids

International Nuclear Information System (INIS)

Okuda, M; Eloi, J-C; Jones, S E Ward; Schwarzacher, W; Verwegen, M; Cornelissen, J J L M

2016-01-01

Nanostructured Pt-based alloys show great promise, not only for catalysis but also in medical and magnetic applications. To extend the properties of this class of materials, we have developed a means of synthesizing Pt and Pt-based alloy nanoclusters in the capsid of a virus. Pure Pt and Pt-alloy nanoclusters are formed through the chemical reduction of [PtCl 4 ] − by NaBH 4 with/without additional metal ions (Co or Fe). The opening and closing of the ion channels in the virus capsid were controlled by changing the pH and ionic strength of the solution. The size of the nanoclusters is limited to 18 nm by the internal diameter of the capsid. Their magnetic properties suggest potential applications in hyperthermia for the Co–Pt and Fe–Pt magnetic alloy nanoclusters. This study introduces a new way to fabricate size-restricted nanoclusters using virus capsid. (paper)

Encapsulation method for atom probe tomography analysis of nanoparticles

International Nuclear Information System (INIS)

Larson, D.J.; Giddings, A.D.; Wu, Y.; Verheijen, M.A.; Prosa, T.J.; Roozeboom, F.; Rice, K.P.; Kessels, W.M.M.; Geiser, B.P.; Kelly, T.F.

2015-01-01

Open-space nanomaterials are a widespread class of technologically important materials that are generally incompatible with analysis by atom probe tomography (APT) due to issues with specimen preparation, field evaporation and data reconstruction. The feasibility of encapsulating such non-compact matter in a matrix to enable APT measurements is investigated using nanoparticles as an example. Simulations of field evaporation of a void, and the resulting artifacts in ion trajectory, underpin the requirement that no voids remain after encapsulation. The approach is demonstrated by encapsulating Pt nanoparticles in an ZnO:Al matrix created by atomic layer deposition, a growth technique which offers very high surface coverage and conformality. APT measurements of the Pt nanoparticles are correlated with transmission electron microscopy images and numerical simulations in order to evaluate the accuracy of the APT reconstruction. - Highlights: • Pt nanoparticles were analyzed using atom probe tomography and TEM. • The particles were prepared by encapsulation using atomic layer deposition. • Simulation of field evaporation near a void results in aberrations in ion trajectories. • Apparent differences between TEM and APT analyses are reconciled through simulation of field evaporation from a low-field matrix containing high-field NPs; ion trajectory aberrations are shown to lead to an apparent mixing of the matrix into the NPs.

Area-selective atomic layer deposition of platinum using photosensitive polyimide

NARCIS (Netherlands)

Vervuurt, R.H.J.; Sharma, A.; Jiao, Y.; Kessels, W.M.M.; Bol, A.A.

2016-01-01

Area-selective atomic layer deposition (AS-ALD) of platinum (Pt) was studied using photosensitive polyimide as a masking layer. The polyimide films were prepared by spin-coating and patterned using photolithography. AS-ALD of Pt using poly(methyl-methacrylate) (PMMA) masking layers was used as a

Determination of intrinsic spin Hall angle in Pt

Energy Technology Data Exchange (ETDEWEB)

Wang, Yi; Deorani, Praveen; Qiu, Xuepeng; Kwon, Jae Hyun; Yang, Hyunsoo, E-mail: eleyang@nus.edu.sg [Department of Electrical and Computer Engineering, National University of Singapore, 117576 (Singapore)

2014-10-13

The spin Hall angle in Pt is evaluated in Pt/NiFe bilayers by spin torque ferromagnetic resonance measurements and is found to increase with increasing the NiFe thickness. To extract the intrinsic spin Hall angle in Pt by estimating the total spin current injected into NiFe from Pt, the NiFe thickness dependent measurements are performed and the spin diffusion in the NiFe layer is taken into account. The intrinsic spin Hall angle of Pt is determined to be 0.068 at room temperature and is found to be almost constant in the temperature range of 13–300 K.

Determination of intrinsic spin Hall angle in Pt

International Nuclear Information System (INIS)

Wang, Yi; Deorani, Praveen; Qiu, Xuepeng; Kwon, Jae Hyun; Yang, Hyunsoo

2014-01-01

The spin Hall angle in Pt is evaluated in Pt/NiFe bilayers by spin torque ferromagnetic resonance measurements and is found to increase with increasing the NiFe thickness. To extract the intrinsic spin Hall angle in Pt by estimating the total spin current injected into NiFe from Pt, the NiFe thickness dependent measurements are performed and the spin diffusion in the NiFe layer is taken into account. The intrinsic spin Hall angle of Pt is determined to be 0.068 at room temperature and is found to be almost constant in the temperature range of 13–300 K.

High activity of cubic PtRh alloys supported on graphene towards ethanol electrooxidation.

Science.gov (United States)

Rao, Lu; Jiang, Yan-Xia; Zhang, Bin-Wei; Cai, Yuan-Rong; Sun, Shi-Gang

2014-07-21

Cubic PtRh alloys supported on graphene (PtxRhy/GN) with different atomic ratio of Pt and Rh were directly synthesized for the first time using the modified polyol method with Br(-) for the shape-directing agents. The process didn't use surface-capping agents such as PVP that easily occupy the active sites of electrocatalysts and are difficult to remove. Graphene is the key factor for cubic shape besides Br(-) and keeping catalysts high-dispersed. The X-ray diffraction (XRD), scanning electron microscope (SEM) and transmission electron microscope (TEM) were used to characterize the structure and morphology of these electrocatalysts. The results showed that they were composed of homogeneous cubic PtRh alloys. Traditional electrochemical methods, such as cyclic voltammetry and chronoamperometry, were used to investigate the electrocatalytic properties of PtxRhy/GN towards ethanol electrooxidation. It can be seen that PtxRhy/GN with all atomic ratios exhibited high catalytic activity, and the most active one has a composition with Pt : Rh = 9 : 1 atomic ratio. Electrochemical in situ FTIR spectroscopy was used to evaluate the cleavage of C-C bond in ethanol at room temperature in acidic solutions, the results illustrated that Rh in an alloy can promote the split of C-C bond in ethanol, and the alloy catalyst with atomic ratio Pt : Rh = 1 : 1 showed obviously better performance for the C-C bond breaking in ethanol and higher selectivity for the enhanced activity of ethanol complete oxidation to CO2 than alloys with other ratios of Pt and Rh. The investigation indicates that high activity of PtxRhy/GN electrocatalyst towards ethanol oxidation is due to the specific shape of alloys and the synergistic effect of two metal elements as well as graphene support.

Selective hydrogen atom abstraction by hydrogen atoms in photolysis of cyclohexane-normal pentane mixtures at 77 K

International Nuclear Information System (INIS)

Miyazaky, T.; Guedes, S.M.L.; Andrade e Silva, L.G. de; Fernandes, L.

1977-01-01

The reaction of H atoms, produced by the photolysis of HI, has been studied in c-C 6 H 12 -n-C 5 H 12 mixtures at 77K. H atoms in c-C 6 H 12 matrix react more effectively with solute n-C 5 H 12 than solvent c-C 6 H 12 , while H atoms in n-C 5 H 12 matrix react more effectively with solute c-C 6 H 12 than solvent n-C 5 H 12 [pt

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

International Nuclear Information System (INIS)

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

2013-01-01

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

Ferromagnetism regulated by edged cutting and optical identification in monolayer PtSe2 nanoribbons

Science.gov (United States)

Meng, Ming; Zhang, QiZhen; Wang, Lifen; Shan, Yun; Du, Yuandong; Qin, Nan; Liu, Lizhe

2018-06-01

Regulation of ferromagnetism and electronic structure in PtSe2 nanostructures has attracted much attention because of its potential in spintronics. The magnetic and optical properties of PtSe2 nanoribbons with different edge reconstruction and external deformations are calculated by density function theory. In 1 T phase PtSe2 nanoribbons, the ferromagnetism induced by spin polarization of exposed Pt or Se atoms is decreased with the reducing nanoribbon width. For smaller nanoribbon, the magnetism can be regulated by external strain more easily. However, the magnetism cannot occur in 1 H phase PtSe2 nanoribbon. The absorption spectra are suggested to identify the nanoribbon structural changes in detail. Our results suggest the use of edge reconstruction and strain engineering in spintronics applications.

Investigation of Au-Pt/C electro-catalysts for oxygen reduction reaction

International Nuclear Information System (INIS)

Lin Rui; Zhang Haiyan; Zhao Tiantian; Cao Chunhui; Yang Daijun; Ma Jianxin

2012-01-01

Highlights: ► Au-Pt core shell catalyst. ► Seed-mediated growth method. ► Au-Pt (2:4)/C best activity toward ORR. ► Four-electron pathway in acid solution. ► Single cell performance. - Abstract: Carbon-supported Au-Pt core shell nano-structured catalysts were synthesized by the seed-mediated growth method. The nano-structured catalysts were characterized by UV–vis spectroscopy, X-ray photoelectron spectra (XPS) and transmission electron microscopy (TEM) techniques. The oxygen reduction reaction (ORR) activity of the Au-Pt/C was tested by means of linear sweep voltammetry (LSV) by employing rotating disk electrode (RDE). It revealed that Au-Pt (2:4)/C (atomic ratio) catalyst exhibited the best catalytic activity toward ORR. Au-Pt (2:4)/C proceeded by an approximately four-electron pathway in acid solution, through which molecular oxygen was directly reduced to water. The stability of Au-Pt (2:4)/C is tested by cyclic voltammetry for 500 cycles. The performance of the membrane electrode assembly (MEA) prepared by Au-Pt (2:4)/C as the cathode catalyst in a single proton exchange membrane fuel cell (PEMFC) generated a maximum power density of 479 mW cm −2 at 0.431 V using H 2 and O 2 at 80 °C.

Cell-killing efficiency and number of platinum atoms binding to DNA, RNA and protein molecules of HeLa cells treated with combinations of hyperthermia and carboplatin

International Nuclear Information System (INIS)

Akaboshi, M.; Kawai, K.; Tanaka, Y.; Takada, J.; Sumino, T.

1999-01-01

The effect of hyperthermia on the cell killing efficiency of Pt atoms binding to DNA, RNA and protein molecules of HeLa cells treated with cis-diamine(1,1-cyclobutanedicarboxylato)platinum(II) (CBDCA) was examined. HeLa S-3 cells were treated with 195m Pt-radiolabeled CBDCA for 60 minutes at various temperatures, and the relationship between the lethal effect and the number of Pt atoms binding to DNA, RNA and proteins was examined. The mean lethal concentration (D 0 ) of carboplatin for a 60 min-treatment at 0, 25, 37, 40, 42 and 44 deg C was 671.2, 201.5, 67.3, 33.4, 20.2 and 15.6 μM, respectively. By using identically treated cells, the number of Pt-atoms combined with DNA, RNA and protein molecules were determined in the subcellular fractions. Thus, the D 0 's given as the drug concentrations were replaced with the number of Pt-atoms combined in each fraction. Then, the cell-killing efficiency of the Pt atom was expressed as the reciprocal of the number of Pt-atoms combined and was calculated for each molecule. The efficiency for DNA molecules was 0.699, 1.42, 2.65, 4.84, 7.74 and 8.28x10 4 nucleotides, respectively, for the conditions described above. From 0 to 44 deg C, the cell-killing efficiency of Pt atoms increased by a factor of 11.9. (author)

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

Directory of Open Access Journals (Sweden)

Sintaro Hinata

2018-05-01

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

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

Science.gov (United States)

Hinata, Sintaro; Jo, Shin; Saito, Shin

2018-05-01

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

The role of charge transfer in the oxidation state change of Ce atoms in the TM13-CeO2(111) systems (TM = Pd, Ag, Pt, Au): a DFT + U investigation.

Science.gov (United States)

Tereshchuk, Polina; Freire, Rafael L H; Ungureanu, Crina G; Seminovski, Yohanna; Kiejna, Adam; Da Silva, Juarez L F

2015-05-28

Despite extensive studies of transition metal (TM) clusters supported on ceria (CeO2), fundamental issues such as the role of the TM atoms in the change in the oxidation state of Ce atoms are still not well understood. In this work, we report a theoretical investigation based on static and ab initio molecular dynamics density functional theory calculations of the interaction of 13-atom TM clusters (TM = Pd, Ag, Pt, Au) with the unreduced CeO2(111) surface represented by a large surface unit cell and employing Hubbard corrections for the strong on-site Coulomb correlation in the Ce f-electrons. We found that the TM13 clusters form pyramidal-like structures on CeO2(111) in the lowest energy configurations with the following stacking sequence, TM/TM4/TM8/CeO2(111), while TM13 adopts two-dimensional structures at high energy structures. TM13 induces a change in the oxidation state of few Ce atoms (3 of 16) located in the topmost Ce layer from Ce(IV) (itinerant Ce f-states) to Ce(III) (localized Ce f-states). There is a charge flow from the TM atoms to the CeO2(111) surface, which can be explained by the electronegativity difference between the TM (Pd, Ag, Pt, Au) and O atoms, however, the charge is not uniformly distributed on the topmost O layer due to the pressure induced by the TM13 clusters on the underlying O ions, which yields a decrease in the ionic charge of the O ions located below the cluster and an increase in the remaining O ions. Due to the charge flow mainly from the TM8-layer to the topmost O-layer, the charge cannot flow from the Ce(IV) atoms to the O atoms with the same magnitude as in the clean CeO2(111) surface. Consequently, the effective cationic charge decreases mainly for the Ce atoms that have a bond with the O atoms not located below the cluster, and hence, those Ce atoms change their oxidation state from IV to III. This increases the size of the Ce(III) compared with the Ce(IV) cations, which builds-in a strain within the topmost Ce layer, and

The role of total-reflection x-ray fluorescence in atomic spectroscopy

International Nuclear Information System (INIS)

Toelg, G.; Klockenkaemper, R.

1993-01-01

Total-reflection X-ray fluorescence (TXRF) is a universal and economic method for the simultaneous determination of elements with atomic numbers > 11 down to the lower pg-level. It is a microanalytical tool for the analysis of small sample amounts placed on flat carriers and for contaminations on flat sample surfaces. Analyses of stratified near-surface layers are made possible by varying the incident angle of the primary beam in the region of total-reflection. This non-destructive method is especially suitable for thin layers of a few nanometres, deposited on wafer material although not usable as a microprobe method with a high lateral resolution. Furthermore, depth profiles of biological samples can be recorded by means of microtome sectioning of only a few micrometres, as, for example in the gradient analysis of human organs. In addition to micro- and surface-layer analysis, TXRF is effectively applied to element trace analysis. Homogeneous solutions, for example aqueous solutions, high-purity acids or body fluids, are pipetted onto carriers and, after evaporation, the dry residues are analyzed directly down to the pg/ml region. Particularly advantageous is the absence of matrix effects, so that an easy calibration can be carried out by adding a single internal standard element. A digestion or separation step preceding the actual determination becomes necessary if a more complex matrix is to be analysed or especially low detection limits have to be reached. A critical evaluation of the recent developments in atomic spectroscopy places TXRF in a leading position. Its outstanding features compete with those of e.g. electrothermal atomic absorption spectrometry (ETAAS), microwave induced plasma optical emission spectroscopy (MIP-OES) and inductively coupled plasma mass spectrometry (ICP-MS) in the field of micro- and trace analysis and with Rutherford backscattering (RBS) and secondary ion mass spectrometry (SIMS) in the surface-layer analysis. (author)

Structural and magnetic properties of FePt nanoparticles from the gas phase; Strukturelle und magnetische Eigenschaften von FePt-Nanopartikeln aus der Gasphase

Energy Technology Data Exchange (ETDEWEB)

Dmitrieva, O.

2007-09-21

In this work, we present the structural and magnetic characterization of FePt nanoparticles. The nanoparticles with mean size of about 6 nm were prepared by sputtering in the gas and subsequent inert gas condensation. The particles are annealed in the furnace during their flight prior to deposition on a substrate. The aim of this work is to prepare magnetically hard FePt nanoparticles in the L1{sub 0}-ordered phase. The structure of the particles was investigated by high-resolution transmission electron microscopy, and the investigations were supported by contrast simulations. The morphology of the particles varies with the sputter-gas pressure and with the annealing temperature. At a pressure of 0.5 mbar, the FePt-nanoparticles are multiply-twinned with an icosahedral structure and exhibit no formation of the L1{sub 0}-ordered phase. At a higher pressure of 1 mbar and an annealing temperature of 1000 C, the particles are partially single-crystalline. About 36 % of the particles are found to be in the L1{sub 0}-ordered state as was estimated by statistical counting supported by simulations. In order to activate the volume diffusion in the particles and to stabilize the formation of the L1{sub 0}-ordered state, the addition of nitrogen was used during the sputtering phase. In this phase, atomic nitrogen is incorporated interstitially into the structure of the primary particles. After annealing nitrogen effuses out of the particles and, thereby, increases the volume diffusion of the Fe and Pt atoms. The incorporation of nitrogen atoms during nucleation and their effusion at an annealing temperature of 1000 C was verified by electron energy loss spectroscopy (EELS) and X-ray absorption spectroscopy (XAS). Structural investigations on particles prepared in the presence of nitrogen shows that most of the particles are single-crystalline and about 70 % of them are L1{sub 0}-ordered. Detailed structural analysis of the nanoparticles was done by the exit wave

Observation of Pt-{100}-p(2×2-O reconstruction by an environmental TEM

Directory of Open Access Journals (Sweden)

Hengbo Li

2016-06-01

Full Text Available The surface structure of noble metal nanoparticles usually plays a crucial role during the catalytic process in the fields of energy and environment. It has been studied extensively by surface analytic methods, such as scanning tunneling microscopy. However, it is still challenging to secure a direct observation of the structural evolution of surfaces of nanocatalysts in reaction (gas and heating conditions at the atomic scale. Here we report an in-situ observation of atomic reconstruction on Pt {100} surfaces exposed to oxygen in an environmental transmission electron microscope (TEM. Our high-resolution TEM images revealed that Pt-{100}-p(2×2-O reconstruction occurs during the reaction between oxygen atoms and {100} facets. A reconstruction model was proposed, and TEM images simulated according to this model with different defocus values match the experimental results well.

[Pt(O,O'-acac)(gamma-acac)(DMS)], a new Pt compound exerting fast cytotoxicity in MCF-7 breast cancer cells via the mitochondrial apoptotic pathway.

Science.gov (United States)

Muscella, A; Calabriso, N; Fanizzi, F P; De Pascali, S A; Urso, L; Ciccarese, A; Migoni, D; Marsigliante, S

2008-01-01

We showed previously that a new Pt complex containing an O,O'-chelated acetylacetonate ligand (acac) and a dimethylsulphide in the Pt coordination sphere, [Pt(O,O'-acac)(gamma-acac)(DMS)], induces apoptosis in HeLa cells. The objective of this study was to investigate the hypothesis that [Pt(O,O'-acac)(gamma-acac)(DMS)] is also cytotoxic in a MCF-7 breast cancer cell line relatively insensitive to cisplatin, and to gain a more detailed analysis of the cell death pathways. Cells were treated with Pt compounds and cytotoxicity tests were performed, together with Western blotting of various proteins involved in apoptosis. The mitochondrial membrane potential was assessed by fluorescence microscopy and spectrofluorometry and the Pt bound to cell fractions was measured by atomic absorption spectrometry. In contrast to cisplatin, the cytotoxicity of [Pt(O,O'-acac)(gamma-acac)(DMS)] correlated with cellular accumulation but not with DNA binding. Also, the Pt content in DNA bases was considerably higher for cisplatin than for [Pt(O,O'-acac)(gamma-acac)(DMS)], thus excluding DNA as a target of [Pt(O,O'-acac)(gamma-acac)(DMS)]. [Pt(O,O'-acac)(gamma-acac)(DMS)] exerted high and fast apoptotic processes in MCF-7 cells since it provoked: (a) mitochondria depolarization; (b) cytochrome c accumulation in the cytosol; (c) translocation of Bax and truncated-Bid from cytosol to mitochondria and decreased expression of Bcl-2; (d) cleavage of caspases -7 and -9, and PARP degradation; (e) chromatin condensation and DNA fragmentation. [Pt(O,O'-acac)(gamma-acac)(DMS)] is highly cytotoxic for MCF-7 cells, cells relatively resistant to many chemotherapeutic agents, as it activates the mitochondrial apoptotic pathway. Hence, [Pt(O,O'-acac)(gamma-acac)(DMS)] has the potential to provide us with new opportunities for therapeutic intervention.

Z-Contrast STEM Imaging of Long-Range Ordered Structures in Epitaxially Grown CoPt Nanoparticles

Directory of Open Access Journals (Sweden)

Kazuhisa Sato

2013-01-01

Full Text Available We report on atomic structure imaging of epitaxial L10 CoPt nanoparticles using chemically sensitive high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM. Highly ordered nanoparticles formed by annealing at 973 K show single-variant structure with perpendicular c-axis orientation, while multivariant ordered domains are frequently observed for specimens annealed at 873 K. It was found that the (001 facets of the multivariant particles are terminated by Co atoms rather than by Pt, presumably due to the intermediate stage of atomic ordering. Coexistence of single-variant particles and multivariant particles in the same specimen film suggests that the interfacial energy between variant domains be small enough to form such structural domains in a nanoparticle as small as 4 nm in diameter.

First principles studies of the electronic properties and catalytic activity of single-walled carbon nanotube doped with Pt clusters and chains

International Nuclear Information System (INIS)

Hayes, Kayla E.; Lee, Hee-Seung

2012-01-01

Highlights: ► Electronic and magnetic properties of (5, 5)-SWNT doped with Pt clusters and chains. ► Pt-doping can change metallic (5, 5)-SWNT to semiconducting CNT. ► Oxygen adsorption on Pt-doped (5, 5)-SWNT is barrierless process. ► Pt-doping reduces the activation barrier of oxygen dissociation reaction. ► Adsorbed oxygen has 2 O 2 - – character. - Abstract: We report the results of density functional theory calculations on the electronic structures, geometrical parameters, and magnetic properties of a wide variety of Pt clusters/chains adsorbed on metallic (5,5) single-walled carbon nanotube (SWNT). It was found that the electronic band structures of Pt/CNT systems are very sensitive to the small changes in the geometries of Pt clusters and chains. In some cases, metallic (5, 5)-SWNT becomes a small-gap semiconducting nanotube with adsorbed Pt clusters and chains. We also investigated the dissociation of molecular oxygen on the (5, 5)-SWNT doped with a single Pt atom via the nudged elastic band (NEB) method. The NEB results showed that the activation barrier is lowered even with a single Pt atom compared to that of pristine SWNT. It was found that the electronic structure of molecular oxygen adsorbed on Pt-doped CNT resembles that of 2 O 2 - , which should facilitate the dissociation process.

Cooling and trapping neutral atoms with radiative forces

International Nuclear Information System (INIS)

Bagnato, V.S.; Castro, J.C.; Li, M.S.; Zilio, S.C.

1988-01-01

Techniques to slow and trap neutral atoms at high densities with radiative forces are discussed in this review articles. Among several methods of laser cooling, it is emphasized Zeeman Tuning of the electronic levels and frequency-sweeping techniques. Trapping of neutral atoms and recent results obtained in light and magnetic traps are discussed. Techniques to further cool atoms inside traps are presented and the future of laser cooling of neutral atoms by means of radiation pressure is discussed. (A.C.A.S.) [pt

PtNi alloy nanoparticles supported on carbon-doped TiO2 nanotube arrays for photo-assisted methanol oxidation

International Nuclear Information System (INIS)

He, Huichao; Xiao, Peng; Zhou, Ming; Liu, Feila; Yu, Shujuan; Qiao, Lei; Zhang, Yunhuai

2013-01-01

To develop anode catalysts for photo-assisted direct methanol fuel cell (PDMFC), carbon-doped TiO 2 nanotube arrays-supported PtNi alloy nanoparticles with different Pt/Ni atomic ratio (PtNi/C-TiO 2 NTs) prepared by pulsed electrodeposition method are evaluated as catalysts for photo-assisted methanol oxidation. The cyclic voltammetry (CV) and chronoamperometry results show that the PtNi/C-TiO 2 NTs prepared at t onPt :t onNi : = 10:7 (t on is the current-on time) with a Pt:Ni atomic ratio of 6.1:5.7 presents the highest catalytic activity for methanol oxidation both in the dark and under illumination. In addition, according to the results obtained from the CO stripping voltammetry and electrochemical impedance spectroscopy (EIS) tests, it was found that the light play an accelerative role in the oxidation of methanol on PtNi/C-TiO 2 NTs under illumination. The effect of illumination which enhancing the catalytic activity of PtNi/C-TiO 2 NTs are attributed to (1) methanol and the intermediates be oxidized directly on C-TiO 2 NTs for the light-induced catalytic effect; (2) more abundant oxygen-donating species be produced on C-TiO 2 NTs in the presence of light; (3) less CO ads adsorbing on catalysts due to the presence of stronger metal–support interactions between PtNi alloy nanoparticles and C-TiO 2 NTs under illumination

A diffusion-limited reaction model for self-propagating Al/Pt multilayers with quench limits

Science.gov (United States)

Kittell, D. E.; Yarrington, C. D.; Hobbs, M. L.; Abere, M. J.; Adams, D. P.

2018-04-01

A diffusion-limited reaction model was calibrated for Al/Pt multilayers ignited on oxidized silicon, sapphire, and tungsten substrates, as well as for some Al/Pt multilayers ignited as free-standing foils. The model was implemented in a finite element analysis code and used to match experimental burn front velocity data collected from several years of testing at Sandia National Laboratories. Moreover, both the simulations and experiments reveal well-defined quench limits in the total Al + Pt layer (i.e., bilayer) thickness. At these limits, the heat generated from atomic diffusion is insufficient to support a self-propagating wave front on top of the substrates. Quench limits for reactive multilayers are seldom reported and are found to depend on the thermal properties of the individual layers. Here, the diffusion-limited reaction model is generalized to allow for temperature- and composition-dependent material properties, phase change, and anisotropic thermal conductivity. Utilizing this increase in model fidelity, excellent overall agreement is shown between the simulations and experimental results with a single calibrated parameter set. However, the burn front velocities of Al/Pt multilayers ignited on tungsten substrates are over-predicted. Possible sources of error are discussed and a higher activation energy (from 41.9 kJ/mol.at. to 47.5 kJ/mol.at.) is shown to bring the simulations into agreement with the velocity data observed on tungsten substrates. This higher activation energy suggests an inhibited diffusion mechanism present at lower heating rates.

An interface between the nuclear physics and the atomic physics; how to measure nuclear times observing atomic transitions

International Nuclear Information System (INIS)

Pinho, A.G. de

1985-01-01

Recent observations are related in which processes resulting from the ionization in ion-atom collisions are observed in coincidence with nuclear processes (where the incidence ion nucleus hits the target atom nucleus). The delay introduced by the nuclear reaction contaminates the results of the atomic collision and manifest itself either in the X rays (positrons) emitted in the joined atom system or in the X rays (Auger electrons) emitted by separeted atoms, after the collision. Both effects serve to obtain information on the reaction times (in general much less then 10 -16 sec). Following this line, other experimental possibilities are discussed. (L.C.) [pt

Structural and magnetic properties of Fe{sub 7−n}Pt{sub n} with n = 0, 1, 2, . . . 7, bimetallic clusters

Energy Technology Data Exchange (ETDEWEB)

Ponce-Tadeo, A. P.; Morán-López, J. L., E-mail: joseluis.moran@ipicyt.edu.mx [Instituto Potosino de Investigación Científica y Tenológica, División de Materiales Avanzados (Mexico); Ricardo-Chavez, J. L. [Benemérita Universidad Autónoma de Puebla, Laboratorio Nacional de Supercómputo (Mexico)

2016-11-15

An exhaustive study of the structural and magnetic properties of Fe{sub 7−n}Pt{sub n} with n = 0, 1, 2, …7, bimetallic clusters is presented. Based on ab initio density functional theory that includes spin-orbit coupling (SOC) and graph theory, the ground state geometry, the local chemical order, and the orbital and spin magnetic moments are calculated. We show how the systems evolves from the 3-d Fe to the quasi-planar Pt clusters. These calculations show that SOC are necessary to describe correctly the composition dependence of the binding energy of these nanoalloys. We observe that the ground state geometries on the Fe rich side resemble the fcc structure adopted by bulk samples. Furthermore, we observe how the spin and orbital magnetic moments depend on the chemical concentration and chemical order. Based on these results, we estimated the magnetic anisotropy energy and found that the largest values correspond to some of the most symmetric structures, Fe{sub 5}Pt{sub 2} and FePt{sub 6}. To determine the degree of non-collinearity, we define an index that shows that in FePt{sub 6} the total magnetic moments, on each atom, are the less collinear.

Structure and chemical composition of supported Pt-Sn electrocatalysts for ethanol oxidation

International Nuclear Information System (INIS)

Jiang Luhua; Sun Gongquan; Sun Shiguo; Liu Jianguo; Tang Shuihua; Li Huanqiao; Zhou Bing; Xin Qin

2005-01-01

Carbon supported PtSn alloy and PtSnO x particles with nominal Pt:Sn ratios of 3:1 were prepared by a modified polyol method. High resolution transmission electron microscopy (HRTEM) and X-ray microchemical analysis were used to characterize the composition, size, distribution, and morphology of PtSn particles. The particles are predominantly single nanocrystals with diameters in the order of 2.0-3.0 nm. According to the XRD results, the lattice constant of Pt in the PtSn alloy is dilated due to Sn atoms penetrating into the Pt crystalline lattice. While for PtSnO x nanoparticles, the lattice constant of Pt only changed a little. HRTEM micrograph of PtSnO x clearly shows that the change of the spacing of Pt (1 1 1) plane is neglectable, meanwhile, SnO 2 nanoparticles, characterized with the nominal 0.264 nm spacing of SnO 2 (1 0 1) plane, were found in the vicinity of Pt particles. In contrast, the HRTEM micrograph of PtSn alloy shows that the spacing of Pt (1 1 1) plane extends to 0.234 nm from the original 0.226 nm. High resolution energy dispersive X-ray spectroscopy (HR-EDS) analyses show that all investigated particles in the two PtSn catalysts represent uniform Pt/Sn compositions very close to the nominal one. Cyclic voltammograms (CV) in sulfuric acid show that the hydrogen ad/desorption was inhibited on the surface of PtSn alloy compared to that on the surface of the PtSnO x catalyst. PtSnO x catalyst showed higher catalytic activity for ethanol electro-oxidation than PtSn alloy from the results of chronoamperometry (CA) analysis and the performance of direct ethanol fuel cells (DEFCs). It is deduced that the unchanged lattice parameter of Pt in the PtSnO x catalyst is favorable to ethanol adsorption and meanwhile, tin oxide in the vicinity of Pt nanoparticles could offer oxygen species conveniently to remove the CO-like species of ethanolic residues to free Pt active sites

DFT calculations of strain and interface effects on electronic structures and magnetic properties of L10-FePt/Ag heterojunction of GMR applications

Science.gov (United States)

Pramchu, Sittichain; Jaroenjittichai, Atchara Punya; Laosiritaworn, Yongyut

2018-03-01

In this work, density functional theory (DFT) was employed to investigate the effect of strain and interface on electronic structures and magnetic properties of L10-FePt/Ag heterojunction. Two possible interface structures of L10-FePt(001)/Ag(001), that is, interface between Fe and Ag layers (Fe/Ag) and between Pt and Ag layers (Pt/Ag), were inspected. It was found that Pt/Ag interface is more stable than Fe/Ag interface due to its lower formation energy. Further, under the lattice mismatch induced tensile strain, the enhancement of magnetism for both Fe/Ag and Pt/Ag interface structures has been found to have progressed, though the magnetic moments of "interfacial" Fe and Pt atoms have been found to have decreased. To explain this further, the local density of states (LDOS) analysis suggests that interaction between Fe (Pt) and Ag near Fe/Ag (Pt/Ag) interface leads to spin symmetry breaking of the Ag atom and hence induces magnetism magnitude. In contrast, the magnetic moments of interfacial Fe and Pt atoms reduce because of the increase in the electronic states near the Fermi level of the minority-spin electrons. In addition, the significant enhancements of the LDOS near the Fermi levels of the minority-spin electrons signify the boosting of the transport properties of the minority-spin electrons and hence the spin-dependent electron transport at this ferromagnet/metal interface. From this work, it is expected that this clarification of the interfacial magnetism may inspire new innovation on how to improve spin-dependent electron transport for enhancing the giant magnetoresistance (GMR) ratio of potential GMR-based spintronic devices.

DFT calculations of strain and interface effects on electronic structures and magnetic properties of L10-FePt/Ag heterojunction of GMR applications

Directory of Open Access Journals (Sweden)

Sittichain Pramchu

2018-03-01

Full Text Available In this work, density functional theory (DFT was employed to investigate the effect of strain and interface on electronic structures and magnetic properties of L10-FePt/Ag heterojunction. Two possible interface structures of L10-FePt(001/Ag(001, that is, interface between Fe and Ag layers (Fe/Ag and between Pt and Ag layers (Pt/Ag, were inspected. It was found that Pt/Ag interface is more stable than Fe/Ag interface due to its lower formation energy. Further, under the lattice mismatch induced tensile strain, the enhancement of magnetism for both Fe/Ag and Pt/Ag interface structures has been found to have progressed, though the magnetic moments of “interfacial” Fe and Pt atoms have been found to have decreased. To explain this further, the local density of states (LDOS analysis suggests that interaction between Fe (Pt and Ag near Fe/Ag (Pt/Ag interface leads to spin symmetry breaking of the Ag atom and hence induces magnetism magnitude. In contrast, the magnetic moments of interfacial Fe and Pt atoms reduce because of the increase in the electronic states near the Fermi level of the minority-spin electrons. In addition, the significant enhancements of the LDOS near the Fermi levels of the minority-spin electrons signify the boosting of the transport properties of the minority-spin electrons and hence the spin-dependent electron transport at this ferromagnet/metal interface. From this work, it is expected that this clarification of the interfacial magnetism may inspire new innovation on how to improve spin-dependent electron transport for enhancing the giant magnetoresistance (GMR ratio of potential GMR-based spintronic devices.

Growth and structure of L1 sub 0 ordered FePt films on GaAs(001)

CERN Document Server

Nefedov, A; Theis-Broehl, K; Zabel, H; Doi, M; Schuster, E; Keune, W

2002-01-01

The structural properties of epitaxial L1 sub 0 ordered FePt(001) films, grown by molecular beam epitaxy (alternating deposition of Fe and Pt atomic layers) on buffer-Pt/seed-Fe/GaAs(001) have been studied by in situ reflection high-energy electron diffraction and by ex situ x-ray scattering as a function of the growth conditions. Reflection high-energy electron diffraction intensity oscillations measured during FePt layer growth provide evidence for island growth at T sub s = 200 deg. C and quasi layer-by-layer growth at T sub s = 350 deg. C. From small-angle and wide-angle x-ray scattering it was found that the degree of epitaxy depends critically on morphology of the seed layer and the substrate roughness. X-ray diffraction analysis showed that the long-range order parameter increases from near zero for films grown at 200 deg. C to 0.65 for films grown at 350 deg. C. This confirms the fact that the order parameter is mainly determined by the surface mobility of the atoms which is controlled experimentally ...

Selective hydrogen atom abstraction by hydrogen atoms in photolysis and radiolysis of alkane mixtures at 770 K

International Nuclear Information System (INIS)

Miyazaki, T.; Kinugawa, K.; Eguchi, M.; Guedes, S.M.L.

1977-01-01

Selective hydrogen atom abstraction reaction by H atoms, has been found in Isobutane, 2,2,3,3-tetramethylbutane(TMB), cyclopropane matrices besides neopentane matrix. The selective hydrogen atom abstraction reaction in neopentane-isobutane mixture is affected by the difference of kinetic energies of H atoms. The reaction occurs more favorably with decreasing the kinetic energy of H atoms. Competitive reaction between c-C 6 H 12 and Hi for H atoms has been studied in the radiolysis and photolysis of neo-C 5 H 12 HI mixture at 77 K. The rate constants of these reactions in neopentane matrix are quite different from these of thermal H atom reaction, but similar to those of hot H atom reaction. Importance of the selective hydrogen atom abstraction reaction by H atoms is pointed out in the radical formation in the radiolysis of pure TMB at 77 K [pt

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

International Nuclear Information System (INIS)

Jiang Zhongqing; Jiang Zhongjie

2011-01-01

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

High magnetic coercivity of FePt-Ag/MgO granular nanolayers

Science.gov (United States)

Roghani, R.; Sebt, S. A.; Khajehnezhad, A.

2018-06-01

L10-FePt ferromagnetic nanoparticles have a hight coercivity of Tesla order. Thus, these nanoparticles, with size of 10 to 15 nm and uniform surface distribution, are suitable in magnetic data storage technology with density of more than 1GB. In order to improve structural and magnetic properties of FePt nanoparticles, some elements and combinations have been added to compound. In this research, we show that due to the presence of the Ag, the phase transition temperature of FePt from fcc to L10-fct phase decreases. The presence of Ag as an additive in FePt-Ag nanocomposite, increases the magnetic coercivity. This nanocomposite, with 10% Ag, was deposited by magnetron sputtering on the MgO heat layer. VSM results of 10 nm nanoparticles show that coercivity has increased up to 1.4 T. XRD and FESEM results confirm that the size of the L10-FePt nanoparticles are 10 nm and their surface distribution are uniform. Ag gradually form nano scale clusters with separate lattice and FePt-Ag nanocomposite appears. The result of this process is emptiness of Ag position in FePt-fcc lattice. So, the mobility of Fe and Pt atoms in this lattice increases and it can be possible for them to move in lower temperature. This mechanism explain the effect of Ag on decreasing the transition temperature to fct-L10 phase, and hight coercivity of FePt nanoparticles.

Evidence for nanoscale two-dimensional Co clusters in CoPt{sub 3} films with perpendicular magnetic anisotropy

Energy Technology Data Exchange (ETDEWEB)

Cross, J O [Department of Physics, University of Washington, Seattle, WA 98195 (United States); Newville, M [Consortium for Advanced Radiation Sources, University of Chicago, Chicago, IL 60637 (United States); Maranville, B B; Hellman, F [Department of Physics, University of California at San Diego, La Jolla, CA 92093 (United States); Bordel, C [Department of Physics, University of California at Berkeley, CA 94720 (United States); Harris, V G, E-mail: cbordel@berkeley.ed [Department of Electrical and Computer Engineering, Northeastern University, Boston, MA 02115 (United States)

2010-04-14

The length scale of the local chemical anisotropy responsible for the growth-temperature-induced perpendicular magnetic anisotropy of face-centered cubic CoPt{sub 3} alloy films was investigated using polarized extended x-ray absorption fine structure (EXAFS). These x-ray measurements were performed on a series of four (111) CoPt{sub 3} films epitaxially grown on (0001) sapphire substrates. The EXAFS data show a preference for Co-Co pairs parallel to the film plane when the film exhibits magnetic anisotropy, and random chemical order otherwise. Furthermore, atomic pair correlation anisotropy was evidenced only in the EXAFS signal from the next neighbors to the absorbing Co atoms and from multiple scattering paths focused through the next neighbors. This suggests that the Co clusters are no more than a few atoms in extent in the plane and one monolayer in extent out of the plane. Our EXAFS results confirm the correlation between perpendicular magnetic anisotropy and two-dimensional Co segregation in CoPt{sub 3} alloy films, and establish a length scale on the order of 10 A for the Co clusters.

Electronic structures of PtCu, PtAg, and PtAu molecules: a Dirac four-component relativistic study

International Nuclear Information System (INIS)

Abe, Minori; Mori, Sayaka; Nakajima, Takahito; Hirao, Kimihiko

2005-01-01

Relativistic four-component calculations at several correlated levels have been performed for diatomic PtCu, PtAg, and PtAu molecules. The ground state spectroscopic constants of PtCu were calculated using the four-component MP2 method, and show good agreement with experiment. We also performed calculations on the experimentally unknown species, PtAg and PtAu, and the mono-cationic systems, PtCu + , PtAg + , and PtAu + . The low-lying excited states of these diatomic molecules were also investigated using the four-component multi-reference CI method

Orbital and total atomic momentum expectation values with Roothaan-Hartree-Fock wave functions

International Nuclear Information System (INIS)

De La Vega, J.M.G.; Miguel, B.

1993-01-01

Orbital and total momentum expectation values are computed using the Roothaan-Hartree-Fock wave functions of Clementi and Roetti. These values are calculated analytically and may be used to study the quality of basis sets. Tabulations for ground and excited states of atoms from Z = 2 to Z = 54 are presented. 23 refs., 1 tab

Selective hydrogenation of citral over supported Pt catalysts: insight into support effects

Energy Technology Data Exchange (ETDEWEB)

Wang, Xiaofeng [Missouri University of Science and Technology, Department of Chemical and Biochemical Engineering (United States); Hu, Weiming; Deng, Baolin [University of Missouri, Department of Civil and Environmental Engineering (United States); Liang, Xinhua, E-mail: liangxin@mst.edu [Missouri University of Science and Technology, Department of Chemical and Biochemical Engineering (United States)

2017-04-15

Highly dispersed platinum (Pt) nanoparticles (NPs) were deposited on various substrates by atomic layer deposition (ALD) in a fluidized bed reactor at 300 °C. The substrates included multi-walled carbon nanotubes (MWCNTs), silica gel (SiO{sub 2}), commercial γ-Al{sub 2}O{sub 3}, and ALD-prepared porous Al{sub 2}O{sub 3} particles (ALD-Al{sub 2}O{sub 3}). The results of TEM analysis showed that ~1.3 nm Pt NPs were highly dispersed on all different supports. All catalysts were used for the reaction of selective hydrogenation of citral to unsaturated alcohols (UA), geraniol, and nerol. Both the structure and acidity of supports affected the activity and selectivity of Pt catalysts. Pt/SiO{sub 2} showed the highest activity due to the strong acidity of SiO{sub 2} and the conversion of citral reached 82% after 12 h with a selectivity of 58% of UA. Pt/MWCNTs showed the highest selectivity of UA, which reached 65% with a conversion of 38% due to its unique structure and electronic effect. The cycling experiments indicated that Pt/MWCNTs and Pt/ALD-Al{sub 2}O{sub 3} catalysts were more stable than Pt/SiO{sub 2}, as a result of the different interactions between the Pt NPs and the supports.

L1{sub 0}-FePt films fabricated by wet-chemical route

Energy Technology Data Exchange (ETDEWEB)

Hong, Xiaoliang; Xiao, Wen; Bao, Nina; Li, Weimin; Chichvarina, Olga, E-mail: A0077107@nus.edu.sg; Ding, Jun, E-mail: msedingj@nus.edu.sg

2015-08-31

In this work, we have developed a method to fabricate FePt films by a combination of chemical deposition and post-annealing. Pt-doped Fe films were deposited on Pt(100 nm)/Ti(50 nm)/SiO{sub 2}/Si substrate using thermal deposition and the as-deposited films were subsequently annealed from 300 °C to 800 °C under 5% H{sub 2}/95% N{sub 2}. FePt films were achieved through diffusion and rearrangement of Fe and Pt atoms in post-annealing process. From X-ray diffraction results, the face-centered cubic (fcc) FePt phase appeared at 300 °C and the transformation from fcc to L1{sub 0} phase started at 400 °C. The L1{sub 0}-FePt film possessed an out-of-plane anisotropy and a coercivity of 729 kA/m after annealing at 600 °C. A further increase in annealing temperature led to lower value of coercivity, probably because of grain growth. In addition, the thickness of Pt-doped Fe films could be controlled from 150 nm to 700 nm by adjusting the amount of surfactant used. Our superconducting quantum interference device analysis showed that Pt dopant could significantly improve the chemical stability of Fe films in air. - Highlights: • We fabricated FePt film by a combination of chemical deposition and post-annealing. • L1{sub 0} FePt film was formed by Fe/Pt diffusion in annealing of Pt-doped Fe film. • L1{sub 0}-phase FePt with high coercivity and small out-of-plane anisotropy • Relatively small amount of Pt dopant can enhance chemical stability greatly. • We studied structure and magnetic property of as-deposited and annealed FePt film.

Atomic physics in the Tandar Laboratory

International Nuclear Information System (INIS)

Nemirovsky, I.B.

1987-01-01

The research activities carried out in the Tandar Laboratory of Physics Department of Argentine National Atomic Energy Comission are presented. The processes of heavy ion collisions with solids as thin lamellae investigated in the Laboratory are described. (M.C.K.) [pt

Particle size effects of sulfonated graphene supported Pt nanoparticles on ethanol electrooxidation

International Nuclear Information System (INIS)

Sun, Chia-Liang; Tang, Jui-Shiang; Brazeau, Nicolas; Wu, Jhing-Jhou; Ntais, Spyridon; Yin, Chung-Wei; Chou, Hung-Lung; Baranova, Elena A.

2015-01-01

Highlights: • Pt colloidal nanoparticles with five mean diameters are synthesized. • Size-selected Pt nanoparticles are loaded on sulfonated graphene (sG). • Sulfonic acid functional groups atop graphene donate charge to Pt. • Pt-sG catalysts are used for ethanol oxidation reaction (EOR). • Pt-sG(2.5 nm) has the highest peak current density in EOR. - Abstract: Fuel cells are promising alternative in automobile and stationary power generation. Direct ethanol fuel cells (DEFCs) offer significant advantages due to the non-toxicity and renewability of ethanol as well as its high power density. Development of the efficient catalysts for ethanol oxidation reaction (EOR) has attracted great attention and represents one of the major challenges in electrocatalysis. Graphene, one-atom thick nanocarbon materials, has attracted much attention recently in a variety of applications. The sulfonation of graphene is able to make it hydrophilic, which enhances its dispersibility in aqueous solvents. Furthermore, sulfonation increases the adsorption and uniform distribution of the Pt nanoparticles, which increases both the electrocatalytic activity and the durability. In this study, theoretical calculations demonstrated that the sulfonate functional group can donate charge to Pt, enhanced the adsorption energy of Pt, and then reduce the adsorption energy of CO on Pt. Then experimentally five kinds of Pt/sulfonated-graphene (Pt/sG) catalysts were synthesized via the control of pH values during the preparation of five-selected colloidal nanoparticles. Among all catalysts, Pt-sG(2.5 nm) has the highest peak current density in EOR

The atomistic origin of the extraordinary oxygen reduction activity of Pt3Ni7 fuel cell catalysts.

Science.gov (United States)

Fortunelli, Alessandro; Goddard Iii, William A; Sementa, Luca; Barcaro, Giovanni; Negreiros, Fabio R; Jaramillo-Botero, Andrés

2015-07-01

Recently Debe et al. reported that Pt 3 Ni 7 leads to extraordinary Oxygen Reduction Reaction (ORR) activity. However, several reports show that hardly any Ni remains in the layers of the catalysts close to the surface ("Pt-skin effect"). This paradox that Ni is essential to the high catalytic activity with the peak ORR activity at Pt 3 Ni 7 while little or no Ni remains close to the surface is explained here using large-scale first-principles-based simulations. We make the radical assumption that processing Pt-Ni catalysts under ORR conditions would leach out all Ni accessible to the solvent. To simulate this process we use the ReaxFF reactive force field, starting with random alloy particles ranging from 50% Ni to 90% Ni and containing up to ∼300 000 atoms, deleting the Ni atoms, and equilibrating the resulting structures. We find that the Pt 3 Ni 7 case and a final particle radius around 7.5 nm lead to internal voids in communication with the exterior, doubling the external surface footprint, in fair agreement with experiment. Then we examine the surface character of these nanoporous systems and find that a prominent feature in the surface of the de-alloyed particles is a rhombic structure involving 4 surface atoms which is crystalline-like but under-coordinated. Using density-functional theory, we calculate the energy barriers of ORR steps on Pt nanoporous catalysts, focusing on the O ad -hydration reaction (O ad + H 2 O ad → OH ad + OH ad ) but including the barriers of O 2 dissociation (O 2ad → O ad + O ad ) and water formation (OH ad + H ad → H 2 O ad ). We find that the reaction barrier for the O ad -hydration rate-determining-step is reduced significantly on the de-alloyed surface sites compared to Pt(111). Moreover we find that these active sites are prevalent on the surface of particles de-alloyed from a Pt-Ni 30 : 70 initial composition. These simulations explain the peak in surface reactivity at Pt 3 Ni 7 , and provide a rational guide to

DFT + U investigation on the adsorption and initial decomposition of methylamine by a Pt single-atom catalyst supported on rutile (110) TiO{sub 2}

Energy Technology Data Exchange (ETDEWEB)

Lv, Cun-Qin [College of Chemistry and Environmental Engineering, Shanxi Datong University, Datong 037009, Shanxi Province (China); Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), Nankai University, Tianjin 300071 (China); Liu, Jian-Hong, E-mail: ljh173@126.com [College of Chemistry and Environmental Engineering, Shanxi Datong University, Datong 037009, Shanxi Province (China); Guo, Yong; Li, Xue-Mei [College of Chemistry and Environmental Engineering, Shanxi Datong University, Datong 037009, Shanxi Province (China); Wang, Gui-Chang, E-mail: wangguichang@nankai.edu.cn [Department of Chemistry, Tianjin Key Lab. of Metal and Molecule-Based Material Chemistry, Nankai University, Tianjin 300071 (China)

2016-12-15

Highlights: • DFT + U is used to investigate the initial decomposition of methylamine. • The adsorption characteristics of possible intermediates involved in methylamine initial decomposition are discussed. • The energy barriers of the possible elementary reactions involved are obtained. • C−H bond scission is the most favored among the C−H, N−H and C−N bond breakings in methylamine. - Abstract: The adsorption and initial decomposition for methylamine catalyzed by a single Pt atom supported on rutile (110) titania (namely, Pt{sub 1}/TiO{sub 2}–R(110)) surface have been investigated by the density functional theory slab calculations with Hubbard corrections (DFT + U). The main purpose of the work is to better understand the role of dispersed platinum metal on the surface of rutile (110) titania in the initial decomposition of methylamine. Our calculated results show that the barriers increased with the order of C−H < N−H < C−N, which indicates that the C−H bond is the easiest to decompose and the C−N bond is the most difficult to break.

PT symmetric Aubry–Andre model

International Nuclear Information System (INIS)

Yuce, C.

2014-01-01

PT symmetric Aubry–Andre model describes an array of N coupled optical waveguides with position-dependent gain and loss. We show that the reality of the spectrum depends sensitively on the degree of quasi-periodicity for small number of lattice sites. We obtain the Hofstadter butterfly spectrum and discuss the existence of the phase transition from extended to localized states. We show that rapidly changing periodical gain/loss materials almost conserve the total intensity. - Highlights: • We show that PT symmetric Aubry–Andre model may have real spectrum. • We show that the reality of the spectrum depends sensitively on the degree of disorder. • We obtain the Hofstadter butterfly spectrum for PT symmetric Aubry–Andre model. • We discuss that phase transition from extended to localized states exists

PT symmetric Aubry–Andre model

Energy Technology Data Exchange (ETDEWEB)

Yuce, C., E-mail: cyuce@anadolu.edu.tr

2014-06-13

PT symmetric Aubry–Andre model describes an array of N coupled optical waveguides with position-dependent gain and loss. We show that the reality of the spectrum depends sensitively on the degree of quasi-periodicity for small number of lattice sites. We obtain the Hofstadter butterfly spectrum and discuss the existence of the phase transition from extended to localized states. We show that rapidly changing periodical gain/loss materials almost conserve the total intensity. - Highlights: • We show that PT symmetric Aubry–Andre model may have real spectrum. • We show that the reality of the spectrum depends sensitively on the degree of disorder. • We obtain the Hofstadter butterfly spectrum for PT symmetric Aubry–Andre model. • We discuss that phase transition from extended to localized states exists.

Tuning magnetic properties of non-collinear magnetization configuration in Pt/[Pt/Co]{sub 6}/Pt/Co/Pt multilayer structure

Energy Technology Data Exchange (ETDEWEB)

Kalaycı, Taner, E-mail: taner.kalayci@marmara.edu.tr [Department of Physics, Marmara University, 34722, Kadıköy, Istanbul (Turkey); Deger, Caner [Department of Physics, Marmara University, 34722, Kadıköy, Istanbul (Turkey); Akbulut, Salih [Department of Physics, Gebze Technical University, 41400, Gebze, Kocaeli (Turkey); Yildiz, Fikret, E-mail: fyildiz@gtu.edu.tr [Department of Physics, Gebze Technical University, 41400, Gebze, Kocaeli (Turkey)

2017-08-15

Highlights: • Effects of Pt spacer and reference layers thickness are investigated by MOKE and FMR. • Controlling of non-collinear states in multilayered thin film systems is studied. • Micromagnetic approach is used for modeling of magnetic multilayered structure. • Magnetic parameters are determined by a simulation based on metropolis algorithm. - Abstract: In this study, effects of Pt spacer and Co reference layers thickness in [Co/Pt]{sub 6}/Pt/Co multilayer have been revealed to tailor magnetization directions in non-collinear configuration. Magneto-optic Kerr effect and ferromagnetic resonance techniques were employed to investigate magnetic properties. Bilinear coupling between [Co/Pt]{sub 6} and Co layers and anisotropy constants were determined by a micromagnetic simulation based on metropolis algorithm. 3 nm spacer causes ferromagnetic coupling while the samples have 4 and 5 nm spacer are coupled anti-ferromagneticaly. Also, tuning magnetic anisotropy of [Co/Pt]{sub 6} layer was accomplished by Co reference layer. It is revealed that controlling of non-collinear states in such systems is possible by variation of thickness of spacer and reference layers and [Co/Pt]{sub 6}/t{sub Pt}/t{sub Co} trilayer system can be used in multilayered magnetic systems.

Controlling the alloy composition of PtNi nanocrystals using solid-state dewetting of bilayer films

Energy Technology Data Exchange (ETDEWEB)

Seo, Okkyun; Oh, Se An; Lee, Ji Yeon; Ha, Sung Soo; Kim, Jae Myung; Choi, Jung Won; Kim, Jin-Woo [Department of Physics and Photon Science & School of Materials Science and Engineering, Gwangju Institute of Science and Technology, Gwangju 61005 (Korea, Republic of); Kang, Hyon Chol [Department of Materials and Science Engineering, Chosun University, Gwangju 61542 (Korea, Republic of); Noh, Do Young, E-mail: dynoh@gist.ac.kr [Department of Physics and Photon Science & School of Materials Science and Engineering, Gwangju Institute of Science and Technology, Gwangju 61005 (Korea, Republic of)

2016-05-15

We demonstrate that solid-state dewetting of bilayer films is an effective way for obtaining bimetallic alloy nanocrystals of controlled composition. When a Pt–Ni bilayer film were annealed near 700 °C, Pt and Ni atoms inter-diffused to form a PtNi bimetallic alloy film. Upon annealing at higher temperatures, the bilayer films transformed into <111> oriented PtNi alloy nanocrystals in small-rhombicuboctahedron shape through solid-state dewetting process. The Pt content of the nanocrystals and the alloy films, estimated by applying the Vegard's law to the relaxed lattice constant, was closely related to the thickness of each layer in the as-grown bilayer films which can be readily controlled during bilayer deposition. - Highlights: • Composition control of PtNi nanoparticles using solid state dewetting is proposed. • PtNi alloy composition was controlled by thickness ratio of Pt–Ni bilayer films. • PtNi alloy nanocrystals were obtained in small-rhombicuboctahedron shape.

Confluent Crum-Darboux transformations in Dirac Hamiltonians with PT-symmetric Bragg gratings

Czech Academy of Sciences Publication Activity Database

Correa, F.; Jakubský, Vít

2017-01-01

Roč. 95, č. 3 (2017), č. článku 033807. ISSN 2469-9926 R&D Projects: GA ČR(CZ) GJ15-07674Y Institutional support: RVO:61389005 Keywords : PT-symmetric * quantum mechanics * bound states Subject RIV: BE - Theoretical Physics OBOR OECD: Atomic, molecular and chemical physics (physics of atoms and molecules including collision, interaction with radiation, magnetic resonances, Mössbauer effect) Impact factor: 2.925, year: 2016

On revealing the vertical structure of nanoparticle films with elemental resolution: A total external reflection X-ray standing waves study

Energy Technology Data Exchange (ETDEWEB)

Zargham, Ardalan, E-mail: zargham@ifp.uni-bremen.d [Institute of Solid State Physics, University of Bremen, Otto-Hahn-Allee 1, 28359 Bremen (Germany); Schmidt, Thomas; Flege, Jan Ingo; Sauerbrey, Marc; Hildebrand, Radowan [Institute of Solid State Physics, University of Bremen, Otto-Hahn-Allee 1, 28359 Bremen (Germany); Roehe, Sarah; Baeumer, Marcus [Applied and Physical Chemistry, University of Bremen, Leobener Str. 2, 28359, Bremen (Germany); Falta, Jens [Institute of Solid State Physics, University of Bremen, Otto-Hahn-Allee 1, 28359 Bremen (Germany)

2010-02-15

We present a promising combination of methods to precisely determine the morphology of nanostructures, drawing on the example of monodisperse CoPt{sub 3} nanoparticle films deposited by spin coating and dip coating techniques on functionalized Au substrates. Ex-situ X-ray standing waves in total external reflection combined with X-ray reflectivity measurements were employed to determine element-specific atomic-density distributions in vertical direction.

First-principles study on the gas sensing property of the Ge, As, and Br doped PtSe2

Science.gov (United States)

Zhang, Jing; Yang, Gui; Tian, Junlong; Ma, Dongwei; Wang, Yuanxu

2018-03-01

Based on first-principles calculations, the adsorption behaviors of H2, O2, CO, CO2, NH3, NO, and NO2 molecules on the Ge-, As- and Br-doped PtSe2 monolayers are theoretically investigated. The results indicate that it is viable for the dopant atoms to be filled into the Se vacancies under Pt-rich conditions. Ge and As act as p-type dopants, while Br acts as n-type dopant. For the adsorption of molecules, the geometrical structures, adsorption energies, charge transfers and the electronic and magnetic properties of the most stable configurations are presented and discussed. It is found that the Ge-doped PtSe2 monolayers exhibit greatly enhanced sensitivity toward O2, CO, NH3, NO and NO2 molecules and the As-doped PtSe2 monolayers are more sensitive toward O2, NH3, NO and NO2 molecules than the pristine ones. This is evident from large adsorption energies, charge transfers, and obvious changes of the electronic states due to the molecule adsorption. However, Br doping cannot enhance the sensing sensitivity of the PtSe2 monolayer. The possible reason is that when substituting for the Se atom, the doped Br with more 4p electrons and less empty orbitals are already chemically saturated by the two of the three neighboring Pt atoms, and thus lose the ability of charge exchange with the adsorbed molecules. On the contrary, the Ge and As as p-type dopants have sizable empty 4p orbitals near the Fermi level to exchange the electrons with the adsorbed molecules, and thus form strong bonds with them.

High performance platinum single atom electrocatalyst for oxygen reduction reaction

Science.gov (United States)

Liu, Jing; Jiao, Menggai; Lu, Lanlu; Barkholtz, Heather M.; Li, Yuping; Wang, Ying; Jiang, Luhua; Wu, Zhijian; Liu, Di-Jia; Zhuang, Lin; Ma, Chao; Zeng, Jie; Zhang, Bingsen; Su, Dangsheng; Song, Ping; Xing, Wei; Xu, Weilin; Wang, Ying; Jiang, Zheng; Sun, Gongquan

2017-07-01

For the large-scale sustainable implementation of polymer electrolyte membrane fuel cells in vehicles, high-performance electrocatalysts with low platinum consumption are desirable for use as cathode material during the oxygen reduction reaction in fuel cells. Here we report a carbon black-supported cost-effective, efficient and durable platinum single-atom electrocatalyst with carbon monoxide/methanol tolerance for the cathodic oxygen reduction reaction. The acidic single-cell with such a catalyst as cathode delivers high performance, with power density up to 680 mW cm-2 at 80 °C with a low platinum loading of 0.09 mgPt cm-2, corresponding to a platinum utilization of 0.13 gPt kW-1 in the fuel cell. Good fuel cell durability is also observed. Theoretical calculations reveal that the main effective sites on such platinum single-atom electrocatalysts are single-pyridinic-nitrogen-atom-anchored single-platinum-atom centres, which are tolerant to carbon monoxide/methanol, but highly active for the oxygen reduction reaction.

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

Energy Technology Data Exchange (ETDEWEB)

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

2010-05-03

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

Mechanism of coercivity enhancement by Ag addition in FePt-C granular films for heat assisted magnetic recording media

Energy Technology Data Exchange (ETDEWEB)

Varaprasad, B. S. D. Ch. S.; Takahashi, Y. K., E-mail: takahashi.yukiko@nims.go.jp; Wang, J.; Hono, K. [National Institute for Materials Science (NIMS), 1-2-1 Sengen, Tsukuba 305-0047 (Japan); Ina, T.; Nakamura, T.; Ueno, W.; Nitta, K.; Uruga, T. [Japan Synchrotron Radiation Research Institute (JASRI/SPring-8), 1-1-1 Kouto, Sayo, Hyogo 679-5198 (Japan)

2014-06-02

We investigated the Ag distribution in a FePtAg-C granular film that is under consideration for a heat assisted magnetic recording medium by aberration-corrected scanning transmission electron microscope-energy dispersive X-ray spectroscopy and X-ray absorption fine structure. Ag is rejected from the core of FePt grains during the deposition, forming Ag-enriched shell surrounding L1{sub 0}-ordered FePt grains. Since Ag has no solubility in both Fe and Pt, the rejection of Ag induces atomic diffusions thereby enhancing the kinetics of the L1{sub 0}-order in the FePt grains.

Fabrication of catalytically active Au/Pt/Pd trimetallic nanoparticles by rapid injection of NaBH4

International Nuclear Information System (INIS)

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 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

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

Energy Technology Data Exchange (ETDEWEB)

Han, Luyang

2011-02-15

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

Stability of Pt{sub n} cluster on free/defective graphene: A first-principles study

Energy Technology Data Exchange (ETDEWEB)

Yang, G.M. [College of Physics, Changchun Normal University, Changchun 130032 (China); College of Materials Science and Engineering, Key Laboratory of Automobile Materials of MOE, Jilin University, Changchun 130012 (China); Fan, X.F., E-mail: xffan@jlu.edu.cn [College of Materials Science and Engineering, Key Laboratory of Automobile Materials of MOE, Jilin University, Changchun 130012 (China); Shi, S.; Huang, H.H. [College of Materials Science and Engineering, Key Laboratory of Automobile Materials of MOE, Jilin University, Changchun 130012 (China); Zheng, W.T., E-mail: wtzheng@jlu.edu.cn [College of Materials Science and Engineering, Key Laboratory of Automobile Materials of MOE, Jilin University, Changchun 130012 (China)

2017-01-15

Highlights: • The single-vacancy can enhance obviously the adsorption of Pt cluster on graphene. • Pt clusters on defected graphene prefer to adopt the close-packed model, except Pt{sub 13}. • The contact way of Pt{sub n} clusters on single-vacancy changes with the size increasing. - Abstract: With first-principles methods, we investigate the stability of isolated Pt{sub n} clusters from Sutton-Chen model and close-packed model, and their adsorption on defected graphene. The single-vacancy in graphene is found to enhance obviously the adsorption energy of Pt cluster on graphene due to the introduction of localized states near Fermi level. It is found that the close-packed model is more stable than Sutton-Chen model for the adsorption of Pt{sub n} cluster on single-vacancy graphene, except the magic number n = 13. The cluster Pt{sub 13} may be the richest one for small Pt clusters on defected graphene due to the strong adsorption on single-vacancy. The larger cluster adsorbed on defected graphene is predicted with the close-packed crystal structure. The charge is found to transfer from the Pt atom/cluster to graphene with the charge accumulation at the interface and the charge polarization on Pt cluster. The strong interaction between Pt cluster and single vacancy can anchor effectively the Pt nanoparticles on graphene and is also expected that the new states introduced near Fermi level can enhance the catalytic characteristic of Pt cluster.

DETERMINATION OF TOTAL MERCURY IN FISH TISSUES USING PYROLYSIS ATOMIC ABSORPTION SPECTROMETRY WITH GOLD AMALGAMATION

Science.gov (United States)

A simple and rapid procedure for measuring total mercury in fish tissues is evaluated and compared with conventional techniques. Using an automated instrument incorporating combustion, preconcentration by amalgamation with gold, and atomic absorption spectrometry (AAS), mill...

Hydrogen spillover in Pt-single-walled carbon nanotube composites: formation of stable C-H bonds.

Science.gov (United States)

Bhowmick, Ranadeep; Rajasekaran, Srivats; Friebel, Daniel; Beasley, Cara; Jiao, Liying; Ogasawara, Hirohito; Dai, Hongjie; Clemens, Bruce; Nilsson, Anders

2011-04-13

Using in situ electrical conductivity and ex situ X-ray photoelectron spectroscopy (XPS) measurements, we have examined how the hydrogen uptake of single-walled carbon nanotubes (SWNTs) is influenced by the addition of Pt nanoparticles. The conductivity of platinum-sputtered single-walled carbon nanotubes (Pt-SWNTs) during molecular hydrogen exposure decreased more rapidly than that of the corresponding pure SWNTs, which supports a hydrogenation mechanism facilitated by "spillover" of dissociated hydrogen from the Pt nanoparticles. C 1s XPS spectra indicate that the Pt-SWNTs store hydrogen by means of chemisorption, that is, covalent C-H bond formation: molecular hydrogen charging at elevated pressure (8.27 bar) and room temperature yielded Pt-SWNTs with up to 16 ± 1.5 at. % sp(3)-hybridized carbon atoms, which corresponds to a hydrogen-storage capacity of 1.2 wt % (excluding the weight of Pt nanoparticles). Pt-SWNTs prepared by the Langmuir-Blodgett (LB) technique exhibited the highest Pt/SWNT ratio and also the best hydrogen uptake. © 2011 American Chemical Society

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

Directory of Open Access Journals (Sweden)

Krstajić Mila N.

2013-01-01

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

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

International Nuclear Information System (INIS)

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

2010-01-01

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

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

International Nuclear Information System (INIS)

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

2014-01-01

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

Magnetocrystalline Anisotropy of Magnetic Grains in Co80Pt20:Oxide Thin Films Probed by X-ray Magnetic Circular Dichroism

Energy Technology Data Exchange (ETDEWEB)

Zhang, W.; Morton, S. A.; Wong, P. K. J.; Arenholz, E.; Lu, B.; Cheng, T. Y.; Xu, Y. B.; Laan, G. van der; Hu, X.F

2011-01-12

Using angle-dependent x-ray magnetic circular dichroism, we have measured magnetic hysteresis loops at the Co L2,3 edges of oxide-doped Co80Pt20 thin films. The magnetocrystalline anisotropy energy (MAE) of the Co atoms, which is the main source of the magnetocrystalline anisotropy of the CoPt magnetic grains, has been determined directly from these element-specific hysteresis loops. When the oxide volume fraction (OVF) is increased from 16.6% to 20.7%, the Co MAE has been found to decrease from 0.117 meV/atom to 0.076 meV/atom. While a larger OVF helps one to achieve a smaller grain size, it reduces the magnetocrystalline anisotropy, as demonstrated unambiguously from the direct Co MAE measurements. Our results suggest that those Co80Pt20:oxide films with an OVF between 19.1% and 20.7% are suitable candidates for high-density magnetic recording.

Pt based anode catalysts for direct ethanol fuel cells

Energy Technology Data Exchange (ETDEWEB)

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

2003-11-10

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2008-03-15

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

Pt-decorated graphene as superior media for H2S adsorption: A first-principles study

International Nuclear Information System (INIS)

Ganji, Masoud Darvish; Sharifi, Narges; Ardjmand, Mahdi; Ahangari, Morteza Ghorbanzadeh

2012-01-01

Highlights: ► We report the first DFT study in the H 2 S/Pt–graphene system. ► The adsorption properties of H 2 S at different possible site on the surface of pristine graphene are slightly stable presenting energies from 0.02 to 0.06 eV. ► When Pt decorates the graphene sheet on the single and double sides the H 2 S adsorption energy increase to −3.2 eV. ► A single Pt atom can locate up to seven H 2 S molecules stably binded with energies from −6.73 to −0.95 eV. ► The DOS plot indicates strong hybridization between H 2 S molecules and Pt–graphene sheet. - Abstract: The adsorption mechanism of hydrogen sulfide (H 2 S) molecules on pristine and Pt-decorated graphene sheets was studied using density functional theory calculations based on local density approximation and generalized gradient approximation methods. Our calculations show that a Pt-decorated graphene system has much higher binding energy, higher net charge transfer values and shorter connecting distances than pristine graphene due to chemisorption of the H 2 S molecule. Furthermore, the calculated density of states show that orbital hybridization is visible between the H 2 S and Pt-decorated graphene sheets, while there is no evidence for hybridization between the H 2 S molecule and the pristine graphene sheet. Interestingly, we find that up to seven H 2 S molecules can stably bind to a Pt atom on each side of the graphene sheet with desirable binding energy.

In Situ Generation of Two-Dimensional Au–Pt Core–Shell Nanoparticle Assemblies

Directory of Open Access Journals (Sweden)

Khalid Madiha

2009-01-01

Full Text Available Abstract Two-dimensional assemblies of Au–Pt bimetallic nanoparticles are generated in situ on polyethyleneimmine (PEI silane functionalized silicon and indium tin oxide (ITO coated glass surfaces. Atomic force microscopy (AFM, UV–Visible spectroscopy, and electrochemical measurements reveal the formation of core–shell structure with Au as core and Pt as shell. The core–shell structure is further supported by comparing with the corresponding data of Au nanoparticle assemblies. Static contact angle measurements with water show an increase in hydrophilic character due to bimetallic nanoparticle generation on different surfaces. It is further observed that these Au–Pt core–shell bimetallic nanoparticle assemblies are catalytically active towards methanol electro-oxidation, which is the key reaction for direct methanol fuel cells (DMFCs.

Factors influencing the charge distribution on Pd x Pt y bimetallic nanoparticles

Directory of Open Access Journals (Sweden)

Carlos M. Celis-Cornejo

2013-12-01

Full Text Available We performed quantum mechanics calculations to elucidate the electronic behavior of Pd-Pt bimetallic nanoparticles, using density functional theory, in response to particle size and stoichiometric composition. Using neutrally charged nanoparticles and the Bader charge analysis, we found that external Pd atoms were positively charged, which agrees with previous XPS observations of supported Pd-Pt nanoparticles. From the calculations, unsupported nanoparticles exhibit an electron transfer from Pd to Pt. This result supports the idea that Pd electron-deficient species are possibly responsible of the hydrogenating function of these catalysts, in the hydrodesulfurization of dibenzothiophene. Additionally, it was found that the particle size does not affect the electronic charge distribution and the stoichiometric composition is the factor that greatly influences this property in nanoparticles.

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

Science.gov (United States)

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

2015-08-07

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

Pt/Au nanoalloy supported on alumina and chlorided alumina: DFT and experimental analysis

Science.gov (United States)

Sharifi, N.; Falamaki, C.; Ghorbanzadeh Ahangari, M.

2018-04-01

Density functional theory (DFT) was used to explore the adsorption of Pt/Au nanoalloy onto a pure and chlorided γ-Al2O3(110) surface, which has been applied in numerous catalytic reactions. First, we considered the adsorption properties of Pt clusters (n ≤ 5) onto the Al2O3(110) surface to determine the most stable Pt cluster on alumina surface in reforming processes. After full structural relaxations of Pt clusters at various configurations on alumina, our computed results expressed that the minimum binding energy (‑5.67 eV) is accrued for Pt4 cluster and the distance between the nearest Pt atom in the cluster to the alumina surface is equal to 1.13 Å. Then, we investigated the binding energies, geometries, and electronic properties of adsorbed Aun clusters (n ≤ 6) on the γ-Al2O3(110) surface. Our studied showed that Au5 was the most thermodynamically stable structure on γ-Al2O3. Finally, we inspected these properties for adsorbed Au clusters onto the Pt4-decorated alumina (Aun/Pt4-alumina) system. The binding energy of the Au4/Pt4-alumina system was ‑5.01 eV, and the distance between Au4 cluster and Pt4-alumina was 1.33 Å. The Au4/Pt4alumina system was found to be the most stable nanometer-sized catalyst design. At last, our first-principles calculations predicted that the best position of embedment Cl on the Au4/Pt4-alumina.

Formation of hollow atoms above a surface

Science.gov (United States)

Briand, Jean Pierre; Phaneuf, Ronald; Terracol, Stephane; Xie, Zuqi

2012-06-01

Slow highly stripped ions approaching or penetrating surfaces are known to capture electrons into outer shells of the ions, leaving the innermost shells empty, and forming hollow atoms. Electron capture occurs above and below the surfaces. The existence of hollow atoms below surfaces e.g. Ar atoms whose K and L shells are empty, with all electrons lying in the M and N shells, was demonstrated in 1990 [1]. At nm above surfaces, the excited ions may not have enough time to decay before hitting the surfaces, and the formation of hollow atoms above surfaces has even been questioned [2]. To observe it, one must increase the time above the surface by decelerating the ions. We have for the first time decelerated O^7+ ions to energies as low as 1 eV/q, below the minimum energy gained by the ions due to the acceleration by their image charge. As expected, no ion backscattering (trampoline effect) above dielectric (Ge) was observed and at the lowest ion kinetic energies, most of the observed x-rays were found to be emitted by the ions after surface contact. [4pt] [1] J. P. Briand et al., Phys.Rev.Lett. 65(1990)159.[0pt] [2] J.P. Briand, AIP Conference Proceedings 215 (1990) 513.

Molecular dynamic simulation study of plasma etching L10 FePt media in embedded mask patterning (EMP) process

OpenAIRE

Jianxin Zhu; P. Quarterman; Jian-Ping Wang

2017-01-01

Plasma etching process of single-crystal L10-FePt media [H. Wang et al., Appl. Phys. Lett. 102(5) (2013)] is studied using molecular dynamic simulation. Embedded-Atom Method [M. S. Daw and M. I. Baskes, Phy. Rev. B 29, 6443 (1984); X. W. Zhou, R. A. Johnson and H. N. G. Wadley, Phy. Rev. B 69, 144113 (2004)] is used to calculate the interatomic potential within atoms in FePt alloy, and ZBL potential [J.F. Ziegler, J. P. Biersack and U. Littmark, “The Stopping and Range of Ions in Matter,” Vol...

Understanding of the structure activity relationship of PtPd bimetallic catalysts prepared by surface organometallic chemistry and ion exchange during the reaction of iso-butane with hydrogen

KAUST Repository

Al-Shareef, Reem A.; Harb, Moussab; Saih, Youssef; Ould-Chikh, Samy; Roldan, Manuel A.; Anjum, Dalaver H.; Guyonnet, Elodie Bile; Candy, Jean-Pierre; Jan, Deng-Yang; Abdo, Suheil F.; Aguilar-Tapia, Antonio; Proux, Olivier; Hazemann, Jean-Louis; Basset, Jean-Marie

2018-01-01

Well-defined silica supported bimetallic catalysts Pt100-x Pdx were prepared by Surface Organometallic Chemistry (SOMC) and Ionic-Exchange (IE) methods. For all investigated catalysts, iso-butane reaction with hydrogen under differential conditions led to the formation of methane and propane, n-butane, and traces of iso-butylene. The total reaction rate decreased with increasing the Pd loading for both catalysts series as a result of decreasing turnover rate of both isomerization and hydrogenolysis. In the case of Pt100-x Pdx(SOMC) catalysts, the experimental results in combination with DFT calculations suggested a selective coverage of Pt (1 0 0) surface by agglomerated Pd atoms like “islands”, assuming that each metal roughly keeps its intrinsic catalytic properties with relatively small electron transfer from Pt to Pd in the case of Pt-rich sample and from Pd to Pt in the case of Pd-rich sample. For the PtPd catalysts prepared by IE, the catalytic behavior could be explained by the formation of a surface alloy between Pt and Pd in the case of Pd-rich sample and by the segregation of a small amount of Pd on the surface in the case of Pt-rich sample, as demonstrated by TEM, EXAFS and DFT. The catalytic results were explained by a structure activity relationship based on the proposed mechanism of CH bond and CC bond activation and cleavage for iso-butane hydrogenolysis, isomerization, cracking and dehydrogenation.

Understanding of the structure activity relationship of PtPd bimetallic catalysts prepared by surface organometallic chemistry and ion exchange during the reaction of iso-butane with hydrogen

KAUST Repository

Alshareef, Reem Abdul aziz Hamed

2018-04-25

Well-defined silica supported bimetallic catalysts Pt100-x Pdx were prepared by Surface Organometallic Chemistry (SOMC) and Ionic-Exchange (IE) methods. For all investigated catalysts, iso-butane reaction with hydrogen under differential conditions led to the formation of methane and propane, n-butane, and traces of iso-butylene. The total reaction rate decreased with increasing the Pd loading for both catalysts series as a result of decreasing turnover rate of both isomerization and hydrogenolysis. In the case of Pt100-x Pdx(SOMC) catalysts, the experimental results in combination with DFT calculations suggested a selective coverage of Pt (1 0 0) surface by agglomerated Pd atoms like “islands”, assuming that each metal roughly keeps its intrinsic catalytic properties with relatively small electron transfer from Pt to Pd in the case of Pt-rich sample and from Pd to Pt in the case of Pd-rich sample. For the PtPd catalysts prepared by IE, the catalytic behavior could be explained by the formation of a surface alloy between Pt and Pd in the case of Pd-rich sample and by the segregation of a small amount of Pd on the surface in the case of Pt-rich sample, as demonstrated by TEM, EXAFS and DFT. The catalytic results were explained by a structure activity relationship based on the proposed mechanism of CH bond and CC bond activation and cleavage for iso-butane hydrogenolysis, isomerization, cracking and dehydrogenation.

Single atom and-molecules chemisorption on solid surfaces

International Nuclear Information System (INIS)

Anda, E.V.; Ure, J.E.; Majlis, N.

1981-01-01

A simplified model for the microscopic interpretation of single atom and- molecules chemisorption on metallic surfaces is presented. An appropriated hamiltonian for this problem is resolved, through the Green's function formalism. (L.C.) [pt

Analytic properties of the relativistic Thomas-Fermi equation and the total energy of atomic ions

International Nuclear Information System (INIS)

March, N.H.; Senatore, G.

1985-06-01

The analytic properties of solutions of the relativistic Thomas-Fermi equation which tend to zero at infinity are first examined, the neutral atom solution being a member of this class. A new length is shown to enter the theory, proportional to the square root of the fine structure constant. This information is used to develop a perturbation expansion around the neutral atom solution, corresponding to positive atomic ions with finite but large radii. The limiting law relating ionic radius to the degree of ionization is thereby displayed in functional form, and solved explicitly to lowest order in the fine structure constant. To embrace this knowledge of heavy positive ions, as well as results from the one-electron Dirac equation, a proposal is then advanced as to the analytic form of the relativistic total energy E(Z,N) of an atomic ion with nuclear charge Ze and total number of electrons N. The fact that, for N>1, the nucleus is known only to bind Z+n electrons, where n is 1 or 2, indicates non-analyticity in the complex Z plane, represented by a circle of radius Z approx.= N. Such non-analyticity is also a property of the non-relativistic energy derived from the many-electron Schroedinger equation. The relativistic theory, however, must also embody a second type of non-analyticity associated with the known property for N=1 that the Dirac equation predicts electron-positron pair production when the electronic binding energy becomes equal to twice the electron rest mass energy. This corresponds to a second circle of non-analyticity in E(Z,N), and hence to a Taylor-Laurent expansion of this quantity in the atomic number Z. The relation of this expansion to the Layzer-Bahcall series is finally discussed. (author)

Fabrication of catalytically active Au/Pt/Pd trimetallic nanoparticles by rapid injection of NaBH{sub 4}

Energy Technology Data Exchange (ETDEWEB)

Zhang, Haijun, E-mail: zhanghaijun@wust.edu.cn [College of Materials and Metallurgy, Wuhan University of Science and Technology, Wuhan, Hubei Province 430081 (China); State Key Laboratory Breeding Base of Refractories and Ceramics, Wuhan University of Science and Technology, Wuhan 430081 (China); Lu, Lilin [College of Chemical Engineering and Technology, Wuhan University of Science and Technology, Wuhan 430081 (China); Cao, Yingnan; Du, Shuang [College of Materials and Metallurgy, Wuhan University of Science and Technology, Wuhan, Hubei Province 430081 (China); State Key Laboratory Breeding Base of Refractories and Ceramics, Wuhan University of Science and Technology, Wuhan 430081 (China); Cheng, Zhong [College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072 (China); Zhang, Shaowei [State Key Laboratory Breeding Base of Refractories and Ceramics, Wuhan University of Science and Technology, Wuhan 430081 (China)

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.

In situ atomic-level observation of the formation of platinum silicide at platinum-silicon oxide interfaces under electron irradiation

Directory of Open Access Journals (Sweden)

Takeshi Nagase

2018-05-01

Full Text Available In situ atomic-level observation of the formation of Pt2Si at Pt/SiOx interface by electronic excitation under electron irradiation was performed by using scanning transmission electron microscopy. Scanning of an electron-beam probe stimulates silicide formation at the Pt/SiOx interface; the change in the Pt column corresponding to Pt2Si formation with a crystallographic orientation of (001Pt//(001Pt2Si and [110]Pt//[110]Pt2Si was observed in high-angle annular dark-field images.

Penetapan Strategi Bisnis pada PT. Pabrik Es Siantar, Pematangsiantar

OpenAIRE

Pakpahan, Vovi Novita

2015-01-01

This research aims to identify the types of strategies used dan analyze the internal environment PT. Pabrik Es Siantar related strenghts and weaknesses and the external environment related opportunities and threats to determine the right strategy and the way it is applied in PT. Pabrik Es Siantar in the face of competition. The type of strategy adopted PT. Pabrik Es Siantar classified as a defensive strategy. The input stage of business strategy include matrix EFE,IFE and CPM. The total ...

Interaction of strong electromagnetic fields with atoms

International Nuclear Information System (INIS)

Brandi, H.S.; Davidovich, L.; Zagury, N.

1982-06-01

Several non-linear processes involvoing the interaction of atoms with strong laser fields are discussed, with particular emphasis on the ionization problem. Non-perturbative methods which have been proposed to tackle this problem are analysed, and shown to correspond to an expansion in the intra-atomic potential. The relation between tunneling and multiphoton absorption as ionization mechanisms, and the generalization of Einstein's photoelectric equation to the strong-field case are discussed. (Author) [pt

Growth of epitaxial Pt thin films on (0 0 1) SrTiO{sub 3} by rf magnetron sputtering

Energy Technology Data Exchange (ETDEWEB)

Kahsay, A. [Departament de Física Aplicada i Òptica, Universitat de Barcelona, 08028 Barcelona (Spain); Polo, M.C., E-mail: mcpolo@ub.edu [Departament de Física Aplicada i Òptica, Universitat de Barcelona, 08028 Barcelona (Spain); Ferrater, C.; Ventura, J. [Departament de Física Aplicada i Òptica, Universitat de Barcelona, 08028 Barcelona (Spain); Rebled, J.M. [Departament d’Electrònica, Universitat de Barcelona Institut de Nanociència i Nanotecnologia IN 2UB, 08028 Barcelona (Spain); Varela, M. [Departament de Física Aplicada i Òptica, Universitat de Barcelona, 08028 Barcelona (Spain)

2014-07-01

The growth of platinum thin film by rf magnetron sputtering on SrTiO{sub 3}(0 0 1) substrates for oxide based devices was investigated. Platinum films grown at temperatures higher than 750 °C were epitaxial ([1 0 0]Pt(0 0 1)//[1 0 0]STO(0 0 1)), whereas at lower temperatures Pt(1 1 1) films were obtained. The surface morphology of the Pt films showed a strong dependence on the deposition temperature as was revealed by atomic force microscopy (AFM). At elevated temperatures there is a three-dimensional (3D) growth of rectangular atomically flat islands with deep boundaries between them. On the other hand, at low deposition temperatures, a two-dimensional (2D) layered growth was observed. The transition from 2D to 3D growth modes was observed that occurs for temperatures around 450 °C. The obtained epitaxial thin films also formed an atomically sharp interface with the SrTiO{sub 3}(0 0 1) substrate as confirmed by HRTEM.

Inversion of the total cross sections for electron-molecule and electron-atom scattering

International Nuclear Information System (INIS)

Lun, D.R.; Amos, K.; Allen, L.J.

1994-01-01

Inverse scattering theory has been applied to construct the interaction potentials from total cross sections as a function of energy for electrons scattered off of atoms and molecules. The underlying potentials are assumed to be real and energy independent and are evaluated using the Eikonal approximation and with real phase shifts determined from the total cross sections. The inversion potentials have been determined using either a high energy limit approximation or by using a fixed energy inversion method at select energies. These procedures have been used to analyse e - - CH 4 , e - - SiH 4 , e - -Kr and e - -Xe scattering data in particular. 14 refs., 1 tabs., 3 figs

An Analytical Model for Adsorption and Diffusion of Atoms/Ions on Graphene Surface

Directory of Open Access Journals (Sweden)

Yan-Zi Yu

2015-01-01

Full Text Available Theoretical investigations are made on adsorption and diffusion of atoms/ions on graphene surface based on an analytical continuous model. An atom/ion interacts with every carbon atom of graphene through a pairwise potential which can be approximated by the Lennard-Jones (L-J potential. Using the Fourier expansion of the interaction potential, the total interaction energy between the adsorption atom/ion and a monolayer graphene is derived. The energy-distance relationships in the normal and lateral directions for varied atoms/ions, including gold atom (Au, platinum atom (Pt, manganese ion (Mn2+, sodium ion (Na1+, and lithium-ion (Li1+, on monolayer graphene surface are analyzed. The equilibrium position and binding energy of the atoms/ions at three particular adsorption sites (hollow, bridge, and top are calculated, and the adsorption stability is discussed. The results show that H-site is the most stable adsorption site, which is in agreement with the results of other literatures. What is more, the periodic interaction energy and interaction forces of lithium-ion diffusing along specific paths on graphene surface are also obtained and analyzed. The minimum energy barrier for diffusion is calculated. The possible applications of present study include drug delivery system (DDS, atomic scale friction, rechargeable lithium-ion graphene battery, and energy storage in carbon materials.

Ultimate temperature for laser cooling of two-level neutral atoms

International Nuclear Information System (INIS)

Bagnato, V.S.; Zilio, S.C.

1989-01-01

We present a simple pedagogical method to evaluate the minimum attainable temperature for laser cooling of two-level neutral atoms. Results are given as a function of the laser detuning and intensity. We also discuss the use of this approach to predict the minimum temperature of neutral atoms confined in magnetic traps. (author) [pt

Calculated dependence of FePt damping on external field magnitude and direction

Directory of Open Access Journals (Sweden)

N. A. Natekar

2017-05-01

Full Text Available Near the Curie temperature (Tc, magnetic parameters including magnetization, anisotropy, and damping depend strongly on both temperature and length scale. This manifestation of renormalization theory is most readily seen in the case of magnetization where the magnitude of the atomic spin is largely unaffected by temperature, but the bulk magnetization vanishes at Tc. It has been previously argued that the Landau-Lifshitz-Gilbert damping parameter alpha exhibits a similar effect owing to its dependence on both atomic effects and magnon-magnon scattering, the latter having a strong length dependence. Here, we calculate, using an anisotropic exchange description of L10 FePt (Tc = 705 K, the damping (and other magnetic properties dependence on temperature for FePt at length scales around 1.0 nm as appropriate for high temperature micromagnetic simulation. While the damping reduces as the applied field along the easy direction increases, it tends to increase as the field direction is changed to in-plane. The renormalized parameters are also calculated for higher and lower Tc (770K and 630K by invoking the linear relationship between the exchange stiffness parameter and Curie temperature. This corresponds to doped and/or non-stoichiometric FePt and allows better understanding of the effects of varying anisotropy to exchange ratio.

Structural and magnetic properties of CoO-Pt core-shell nanoparticles

Czech Academy of Sciences Publication Activity Database

Zeleňáková, A.; Zeleňák, V.; Michalik, Štefan; Kováč, J.; Meisel, M. W.

2014-01-01

Roč. 89, č. 10 (2014), "104417-1"-"104417-10" ISSN 1098-0121 Institutional support: RVO:68378271 Keywords : CoO-Pt core shell nanoparticles * superparamagnetism * superspin glass state * x-ray diffraction * x-ray absorption spectroscopy Subject RIV: BG - Nuclear, Atomic and Molecular Physics, Colliders Impact factor: 3.736, year: 2014

Potential of Transition Metal Atoms Embedded in Buckled Monolayer g-C3N4 as Single-Atom Catalysts

KAUST Repository

Li, Shu-Long; Kan, Xiang; Yin, Hui; Gan, Li-Yong; Schwingenschlö gl, Udo; Zhao, Yong

2017-01-01

We use first-principles calculations to systematically explore the potential of transition metal atoms (Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Ru, Rh, Pd, Ag, Ir, Pt, and Au) embedded in buckled monolayer g-C3N4 as single-atom catalysts. We show that clustering of Sc and Ti on g-C3N4 is thermodynamically impeded and that V, Cr, Mn, and Cu are much less susceptible to clustering than the other TM atoms under investigation. Strong bonding of the transition metal atoms in the cavities of g-C3N4 and high diffusion barriers together are responsible for single-atom fixation. Analysis of the CO oxidation process indicates that embedding of Cr and Mn in g-C3N4 gives rise to promising single-atom catalysts at low temperature.

Potential of Transition Metal Atoms Embedded in Buckled Monolayer g-C3N4 as Single-Atom Catalysts

KAUST Repository

Li, Shu-Long

2017-10-27

We use first-principles calculations to systematically explore the potential of transition metal atoms (Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Ru, Rh, Pd, Ag, Ir, Pt, and Au) embedded in buckled monolayer g-C3N4 as single-atom catalysts. We show that clustering of Sc and Ti on g-C3N4 is thermodynamically impeded and that V, Cr, Mn, and Cu are much less susceptible to clustering than the other TM atoms under investigation. Strong bonding of the transition metal atoms in the cavities of g-C3N4 and high diffusion barriers together are responsible for single-atom fixation. Analysis of the CO oxidation process indicates that embedding of Cr and Mn in g-C3N4 gives rise to promising single-atom catalysts at low temperature.

Ensemble averaged structure–function relationship for nanocrystals: effective superparamagnetic Fe clusters with catalytically active Pt skin [Ensemble averaged structure-function relationship for composite nanocrystals: magnetic bcc Fe clusters with catalytically active fcc Pt skin

Energy Technology Data Exchange (ETDEWEB)

Petkov, Valeri [Central Michigan University, Mt. Pleasant, MI (United States); Prasai, Binay [Central Michigan University, Mt. Pleasant, MI (United States); Shastri, Sarvjit [Argonne National Lab. (ANL), Argonne, IL (United States). X-ray Science Division; Park, Hyun-Uk [Sungkyunkwan University, Suwon (Korea). Department of Chemistry; Kwon, Young-Uk [Sungkyunkwan University, Suwon (Korea). Department of Chemistry; Skumryev, Vassil [Institucio Catalana de Recerca i Estudis Avançats (ICREA), Barcelona (Spain); Universitat Autònoma de Barcelona (Spain). Department of Physics

2017-09-12

Practical applications require the production and usage of metallic nanocrystals (NCs) in large ensembles. Besides, due to their cluster-bulk solid duality, metallic NCs exhibit a large degree of structural diversity. This poses the question as to what atomic-scale basis is to be used when the structure–function relationship for metallic NCs is to be quantified precisely. In this paper, we address the question by studying bi-functional Fe core-Pt skin type NCs optimized for practical applications. In particular, the cluster-like Fe core and skin-like Pt surface of the NCs exhibit superparamagnetic properties and a superb catalytic activity for the oxygen reduction reaction, respectively. We determine the atomic-scale structure of the NCs by non-traditional resonant high-energy X-ray diffraction coupled to atomic pair distribution function analysis. Using the experimental structure data we explain the observed magnetic and catalytic behavior of the NCs in a quantitative manner. Lastly, we demonstrate that NC ensemble-averaged 3D positions of atoms obtained by advanced X-ray scattering techniques are a very proper basis for not only establishing but also quantifying the structure–function relationship for the increasingly complex metallic NCs explored for practical applications.

Tunable magnetic properties by interfacial manipulation of L1(0)-FePt perpendicular ultrathin film with island-like structures.

Science.gov (United States)

Feng, C; Wang, S G; Yang, M Y; Zhang, E; Zhan, Q; Jiang, Y; Li, B H; Yu, G H

2012-02-01

Based on interfacial manipulation of the MgO single crystal substrate and non-magnetic AIN compound, a L1(0)-FePt perpendicular ultrathin film with the structure of MgO/FePt-AIN/Ta was designed, prepared, and investigated. The film is comprised of L1(0)-FePt "magnetic islands," which exhibits a perpendicular magnetic anisotropy (PMA), tunable coercivity (Hc), and interparticle exchange coupling (IEC). The MgO substrate promotes PMA of the film because of interfacial control of the FePt lattice orientation. The AIN compound is doped to increase the difference of surface energy between FePt layer and MgO substrate and to suppress the growth of FePt grains, which takes control of island growth mode of FePt atoms. The AIN compound also acts as isolator of L1(0)-FePt islands to pin the sites of FePt domains, resulting in the tunability of Hc and IEC of the films.

Pt/glassy carbon model catalysts prepared from PS-b-P2VP micellar templates.

Science.gov (United States)

Gu, Yunlong; St-Pierre, Jean; Ploehn, Harry J

2008-11-04

Poly(styrene)-block-poly(2-vinylpyridine) (PS-b-P2VP) diblock copolymer was used as a micellar template to fabricate arrays of Pt nanoparticles on mica and glassy carbon (GC) supports. Polymer micellar deposition yields Pt nanoparticles with tunable particle size and surface number density on both mica and GC. After deposition of precursor-loaded micelles onto GC, oxygen plasma etching removes the polymer shell, followed by thermal treatment with H2 gas to reduce the Pt. Etching conditions were optimized to maximize removal of the polymer while minimizing damage to the GC. Arrays of Pt nanoparticles with controlled size and surface number density can be prepared on mica (for particle size characterization) and GC to make Pt/GC model catalysts. These model catalysts were characterized by tapping mode atomic force microscopy, X-ray photoelectron spectroscopy, and cyclic voltammetry to measure activity for oxidation of carbon monoxide or methanol. Cyclic voltammetry results demonstrate the existence of a correlation between Pt particle size and electrocatalytic properties including onset potential, tolerance of carbonaceous adsorbates, and intrinsic activity (based on active Pt area from CO stripping voltammetry). Results obtained with Pt/GC model catalysts duplicate prior results obtained with Pt/porous carbon catalysts therefore validating the synthesis approach and offering a new, tunable platform to study catalyst structure and other effects such as aging on proton exchange membrane fuel cell (PEMFC) reactions.

Recent advances in platinum monolayer electrocatalysts for oxygen reduction reaction: Scale-up synthesis, structure and activity of Pt shells on Pd cores

Energy Technology Data Exchange (ETDEWEB)

Sasaki, K., E-mail: ksasaki@bnl.go [Brookhaven National Laboratory, Chemistry Department, Upton, NY 11973 (United States); Wang, J.X. [Brookhaven National Laboratory, Chemistry Department, Upton, NY 11973 (United States); Naohara, H. [Toyota Motor Corporation, Susono 410-1193 (Japan); Marinkovic, N. [University of Delaware, Department of Chemical Engineering, Newark, DE 19716 (United States); More, K. [Oak Ridge National Laboratory, Oak Ridge, TN 37831 (United States); Inada, H. [Hitachi High Technologies America, Pleasanton, CA 94588 (United States); Adzic, R.R., E-mail: adzic@bnl.go [Brookhaven National Laboratory, Chemistry Department, Upton, NY 11973 (United States)

2010-03-01

We have established a scale-up synthesis method to produce gram-quantities of Pt monolayer electrocatalysts. The core-shell structure of the Pt/Pd/C electrocatalyst has been verified using the HAADF-STEM Z-contrast images, STEM/EELS, and STEM/EDS line profile analysis. The atomic structure of this electrocatalyst and formation of a Pt monolayer on Pd nanoparticle surfaces were examined using in situ EXAFS. The Pt mass activity of the Pt/Pd/C electrocatalyst for ORR is considerably higher than that of commercial Pt/C electrocatalysts. The results with Pt monolayer electrocatalysts may significantly impact science of electrocatalysis and fuel-cell technology, as they have demonstrated an exceptionally effective way of using Pt that can resolve problems of other approaches, including electrocatalysts' inadequate activity and high Pt content.

Recent advances in platinum monolayer electrocatalysts for oxygen reduction reaction: Scale-up synthesis, structure and activity of Pt shells on Pd cores

International Nuclear Information System (INIS)

Sasaki, K.; Wang, J.X.; Naohara, H.; Marinkovic, N.; More, K.; Inada, H.; Adzic, R.R.

2010-01-01

We have established a scale-up synthesis method to produce gram-quantities of Pt monolayer electrocatalysts. The core-shell structure of the Pt/Pd/C electrocatalyst has been verified using the HAADF-STEM Z-contrast images, STEM/EELS, and STEM/EDS line profile analysis. The atomic structure of this electrocatalyst and formation of a Pt monolayer on Pd nanoparticle surfaces were examined using in situ EXAFS. The Pt mass activity of the Pt/Pd/C electrocatalyst for ORR is considerably higher than that of commercial Pt/C electrocatalysts. The results with Pt monolayer electrocatalysts may significantly impact science of electrocatalysis and fuel-cell technology, as they have demonstrated an exceptionally effective way of using Pt that can resolve problems of other approaches, including electrocatalysts' inadequate activity and high Pt content.

Evaluation of H{sub 2}O{sub 2}-generation during oxygen reduction at electrodeposited Pt particles on mask scratched electrodes

Energy Technology Data Exchange (ETDEWEB)

Kishi, Akira; Inoue, Mitsuhiro; Umeda, Minoru, E-mail: mumeda@vos.nagaokaut.ac.jp

2013-08-15

In this study, the Pt particle deposition was systematically performed by our proposed mask scratch and subsequent Pt electrodeposition in order to investigate the H{sub 2}O{sub 2}-byproduct generation efficiency during O{sub 2} reduction. By peeling a part of polymer layer coated on a glassy carbon substrate using an atomic force microscope cantilever, scratched areas are regularly made. The Pt particles are deposited only on the above-mentioned scratched areas, indicating that the controlled Pt deposition has been achieved. The background cyclic voltammetry of the prepared electrodes showed that the deposited nanoparticles are certainly composed of Pt. Moreover, the electrochemical surface area of the deposited Pt (Pt-ESA) linearly increases with the increasing scratched area, revealing that the Pt-ESAs can be controlled by the mask scratch-based Pt electrodeposition method. It should be noted that an increase in the Pt-ESA not only increases the O{sub 2} reduction currents, but also enhances the H{sub 2}O{sub 2} generation efficiency.

Atomic physics and quantum optics using superconducting circuits: from the Dynamical Casimir effect to Majorana fermions

Science.gov (United States)

Nori, Franco

2012-02-01

This talk will present an overview of some of our recent results on atomic physics and quantum optics using superconducting circuits. Particular emphasis will be given to photons interacting with qubits, interferometry, the Dynamical Casimir effect, and also studying Majorana fermions using superconducting circuits.[4pt] References available online at our web site:[0pt] J.Q. You, Z.D. Wang, W. Zhang, F. Nori, Manipulating and probing Majorana fermions using superconducting circuits, (2011). Arxiv. J.R. Johansson, G. Johansson, C.M. Wilson, F. Nori, Dynamical Casimir effect in a superconducting coplanar waveguide, Phys. Rev. Lett. 103, 147003 (2009). [0pt] J.R. Johansson, G. Johansson, C.M. Wilson, F. Nori, Dynamical Casimir effect in superconducting microwave circuits, Phys. Rev. A 82, 052509 (2010). [0pt] C.M. Wilson, G. Johansson, A. Pourkabirian, J.R. Johansson, T. Duty, F. Nori, P. Delsing, Observation of the Dynamical Casimir Effect in a superconducting circuit. Nature, in press (Nov. 2011). P.D. Nation, J.R. Johansson, M.P. Blencowe, F. Nori, Stimulating uncertainty: Amplifying the quantum vacuum with superconducting circuits, Rev. Mod. Phys., in press (2011). [0pt] J.Q. You, F. Nori, Atomic physics and quantum optics using superconducting circuits, Nature 474, 589 (2011). [0pt] S.N. Shevchenko, S. Ashhab, F. Nori, Landau-Zener-Stuckelberg interferometry, Phys. Reports 492, 1 (2010). [0pt] I. Buluta, S. Ashhab, F. Nori. Natural and artificial atoms for quantum computation, Reports on Progress in Physics 74, 104401 (2011). [0pt] I.Buluta, F. Nori, Quantum Simulators, Science 326, 108 (2009). [0pt] L.F. Wei, K. Maruyama, X.B. Wang, J.Q. You, F. Nori, Testing quantum contextuality with macroscopic superconducting circuits, Phys. Rev. B 81, 174513 (2010). [0pt] J.Q. You, X.-F. Shi, X. Hu, F. Nori, Quantum emulation of a spin system with topologically protected ground states using superconducting quantum circuit, Phys. Rev. A 81, 063823 (2010).

Ternary indides Eu{sub 2}Pd{sub 2}In and Eu{sub 2}Pt{sub 2}In

Energy Technology Data Exchange (ETDEWEB)

Muts, Ihor [Inorganic Chemistry Department, Ivan Franko National University of Lviv (Ukraine); Institut fuer Anorganische und Analytische Chemie, Westfaelische Wilhelms-Universitaet Muenster (Germany); Zaremba, Vasyl I. [Inorganic Chemistry Department, Ivan Franko National University of Lviv (Ukraine); Poettgen, Rainer [Institut fuer Anorganische und Analytische Chemie, Westfaelische Wilhelms-Universitaet Muenster (Germany)

2012-01-15

The indides Eu{sub 2}Pd{sub 2}In and Eu{sub 2}Pt{sub 2}In were synthesized from the elements in sealed tantalum tubes in an induction furnace. The samples were characterized by powder X-ray diffraction. The structures were refined on the basis of single-crystal X-ray diffractometer data: HT-Pr{sub 2}Co{sub 2}Al type, C2/c, a = 1035.7(2), b = 592.9(1), c = 823.6(2) pm, β = 104.26(1) , wR2 = 0.026, 1075 F{sup 2} values, 25 variables for Eu{sub 2}Pd{sub 2}In and a = 1017.2(2), b = 588.7(1), c = 826.5(1) pm, β = 103.76(1) , wR2 = 0.062, 706 F{sup 2} values, 25 variables for Eu{sub 2}Pt{sub 2}In. The indium atoms have four platinum (palladium) neighbors in strongly distorted tetrahedral coordination at Pt-In and Pd-In distances ranging from 273 to 275 pm. These InPd{sub 4/2} and InPt{sub 4/2} units are condensed via common edges to infinite InPd{sub 2} and InPt{sub 2} chains, which are surrounded by the europium atoms. The chains form the motif of hexagonal rod packing. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Electronic excitation in ion-atom collisions

International Nuclear Information System (INIS)

Rodriguez, V.D.; Miraglia, J.E.

1988-01-01

Theoretical calculations for excitation of hydrogen-like atoms by ion impact at high and intermediate energies, are presented. Impulsive and eikonal wave functions are employed, both normalized. It is studied the dependence on energy and projectil charge (saturation) of cross sections, compared to experimental results. (A.C.A.S.) [pt

Electrochemical synthesis of mesoporous Pt-Au binary alloys with tunable compositions for enhancement of electrochemical performance.

Science.gov (United States)

Yamauchi, Yusuke; Tonegawa, Akihisa; Komatsu, Masaki; Wang, Hongjing; Wang, Liang; Nemoto, Yoshihiro; Suzuki, Norihiro; Kuroda, Kazuyuki

2012-03-21

Mesoporous Pt-Au binary alloys were electrochemically synthesized from lyotropic liquid crystals (LLCs) containing corresponding metal species. Two-dimensional exagonally ordered LLC templates were prepared on conductive substrates from diluted surfactant solutions including water, a nonionic surfactant, ethanol, and metal species by drop-coating. Electrochemical synthesis using such LLC templates enabled the preparation of ordered mesoporous Pt-Au binary alloys without phase segregation. The framework composition in the mesoporous Pt-Au alloy was controlled simply by changing the compositional ratios in the precursor solution. Mesoporous Pt-Au alloys with low Au content exhibited well-ordered 2D hexagonal mesostructures, reflecting those of the original templates. With increasing Au content, however, the mesostructural order gradually decreased, thereby reducing the electrochemically active surface area. Wide-angle X-ray diffraction profiles, X-ray photoelectron spectra, and elemental mapping showed that both Pt and Au were atomically distributed in the frameworks. The electrochemical stability of mesoporous Pt-Au alloys toward methanol oxidation was highly improved relative to that of nonporous Pt and mesoporous Pt films, suggesting that mesoporous Pt-Au alloy films are potentially applicable as electrocatalysts for direct methanol fuel cells. Also, mesoporous Pt-Au alloy electrodes showed a highly sensitive amperometric response for glucose molecules, which will be useful in next-generation enzyme-free glucose sensors.

Er{sub 1.33}Pt{sub 3}Ga{sub 8}: A modulated variant of the Er{sub 4}Pt{sub 9}Al{sub 24}-structure type

Energy Technology Data Exchange (ETDEWEB)

Oswald, Iain W.H. [Department of Chemistry and Biochemistry, University of Texas at Dallas, Richardson, TX 75080 (United States); Gourdon, Olivier [Research and Development, ZS Pharma, Coppell, TX 75109 (United States); Bekins, Amy; Evans, Jess [Department of Chemistry and Biochemistry, University of Texas at Arlington, Arlington, TX 76019 (United States); Treadwell, LaRico J. [Department of Chemistry and Biochemistry, University of Texas at Dallas, Richardson, TX 75080 (United States); Chan, Julia Y., E-mail: Julia.Chan@utdallas.edu [Department of Chemistry and Biochemistry, University of Texas at Dallas, Richardson, TX 75080 (United States); Macaluso, Robin T., E-mail: robin.macaluso@uta.edu [Department of Chemistry and Biochemistry, University of Texas at Arlington, Arlington, TX 76019 (United States); Department of Chemistry and Biochemistry, University of Northern Colorado, Greeley, CO 80639 (United States)

2016-10-15

Single crystals of Er{sub 1.33}Pt{sub 3}Ga{sub 8} were synthesized in a molten Ga flux. Er{sub 1.33}Pt{sub 3}Ga{sub 8} can be considered to be a modulated variant of the Er{sub 4}Pt{sub 9}Al{sub 24}-structure type, where the partial occupancies are ordered. Indeed, the presence of weak satellite reflections indicates a complex organization and distribution of the Er and Ga atoms within the [ErGa] slabs. The structure has been solved based on single crystal X-ray diffraction data in the monoclinic superspace group X2/m(0β0)00 with a commensurate modulated vector q=1/3b*. Precession images also indicate diffusion in the perpendicular direction indicating a partial disorder of this arrangement from layer to layer. In addition, Er{sub 1.33}Pt{sub 3}Ga{sub 8} shows antiferromagnetic ordering at T{sub N}~5 K. - Graphical abstract: A precession image of the hk0 zone showing weak, periodic, unindexed reflections indicating modulation and representation of the commensurate [ErGa] layer showing the waving modulated occupation. - Highlights: • Single crystals of Er{sub 1.33}Pt{sub 3}Ga{sub 8} were grown from gallium flux. • The structure of Er{sub 1.33}Pt{sub 3}Ga{sub 8} is compared to Er{sub 4}Pt{sub 9}Al{sub 24}. • Structure has been solved in the monoclinic superspace group X2/m(0β0)00 with a commensurate modulated vector q=1/3b*.

Pyridine adsorption and diffusion on Pt(111) investigated with density functional theory

International Nuclear Information System (INIS)

Kolsbjerg, Esben L.; Groves, Michael N.; Hammer, Bjørk

2016-01-01

The adsorption, diffusion, and dissociation of pyridine, C 5 H 5 N, on Pt(111) are investigated with van der Waals-corrected density functional theory. An elaborate search for local minima in the adsorption potential energy landscape reveals that the intact pyridine adsorbs with the aromatic ring parallel to the surface. Piecewise interconnections of the local minima in the energy landscape reveal that the most favourable diffusion path for pyridine has a barrier of 0.53 eV. In the preferred path, the pyridine remains parallel to the surface while performing small single rotational steps with a carbon-carbon double bond hinged above a single Pt atom. The origin of the diffusion pathway is discussed in terms of the C 2 –Pt π-bond being stronger than the corresponding CN–Pt π-bond. The energy barrier and reaction enthalpy for dehydrogenation of adsorbed pyridine into an adsorbed, upright bound α-pyridyl species are calculated to 0.71 eV and 0.18 eV, respectively (both zero-point energy corrected). The calculations are used to rationalize previous experimental observations from the literature for pyridine on Pt(111).

Exotic chemical arrangements and magnetic moment evolution of NixPt1-x (0 ≤x≤ 1) nanoparticles

Science.gov (United States)

Mokkath, Junais Habeeb

2018-06-01

We present a systematic study on the chemical ordering pattern and the magnetic properties of NixPt1-x (0 ⩽ x≤ 1) nanoparticles having a size of 1.5 nm by means of an approach which combines basin hopping structure sampling technique and spin-polarized density functional theory. We found exotic chemical ordering patterns for different Ni/Pt ratios. In addition, we observed a sharp phase transition from non-magnetic to ferromagnetic behaviour around x = 67%. We show that this is a direct consequence of a unique atomic arrangement on the surface in which Ni atoms club together causing the strong Ni-Ni magnetic interaction. The observed magnetic properties are correlated to the electronic density of states.

Area-selective atomic layer deposition of platinum using photosensitive polyimide.

Science.gov (United States)

Vervuurt, René H J; Sharma, Akhil; Jiao, Yuqing; Kessels, Wilhelmus Erwin M M; Bol, Ageeth A

2016-10-07

Area-selective atomic layer deposition (AS-ALD) of platinum (Pt) was studied using photosensitive polyimide as a masking layer. The polyimide films were prepared by spin-coating and patterned using photolithography. AS-ALD of Pt using poly(methyl-methacrylate) (PMMA) masking layers was used as a reference. The results show that polyimide has excellent selectivity towards the Pt deposition, after 1000 ALD cycles less than a monolayer of Pt is deposited on the polyimide surface. The polyimide film could easily be removed after ALD using a hydrogen plasma, due to a combination of weakening of the polyimide resist during Pt ALD and the catalytic activity of Pt traces on the polyimide surface. Compared to PMMA for AS-ALD of Pt, polyimide has better temperature stability. This resulted in an improved uniformity of the Pt deposits and superior definition of the Pt patterns. In addition, due to the absence of reflow contamination using polyimide the nucleation phase during Pt ALD is drastically shortened. Pt patterns down to 3.5 μm were created with polyimide, a factor of ten smaller than what is possible using PMMA, at the typical Pt ALD processing temperature of 300 °C. Initial experiments indicate that after further optimization of the polyimide process Pt features down to 100 nm should be possible, which makes AS-ALD of Pt using photosensitive polyimide a promising candidate for patterning at the nanoscale.

Electronic structure and magnetic properties of substitutional transition-metal atoms in GaN nanotubes

International Nuclear Information System (INIS)

Zhang Min; Shi Jun-Jie