Thermodynamical and thermoelectric properties of boron doped YPd{sub 3} and YRh{sub 3}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dwivedi, Shalini; Sharma, Yamini, E-mail: sharma.yamini62@gmail.com; Sharma, Ramesh

2016-05-23

The structural, electronic, thermal, and optical properties of borides of cubic non-magnetic YX{sub 3} (X=Rh, Pd) compounds and their borides which crystallize in the AuCu{sub 3} structure have been studied using the density functional theory (DFT). The flat bands in the vicinity of E{sub F} which are associated with superconductivity appear in YPd{sub 3} and YRh{sub 3} band structures. However, the B s-states enhance the flat band only in YRh{sub 3}B. The optical properties clearly show that boron insertion modifies the absorption and transmittance. The YX{sub 3} alloys and their borides exhibit valuable changes in the thermopower and ZT. Itmore » is observed that the properties of the Y-X intermetallics change significantly for the Y-Rh and Y-Pd alloys and the presence of single boron atom modifies the properties to a great extent.« less

Traffic and catalytic converter - related atmospheric contamination in the metropolitan region of the city of Rio de Janeiro, Brazil.

PubMed

da Silva, Lílian Irene Dias; de Souza Sarkis, Jorge Eduardo; Zotin, Fátima Maria Zanon; Carneiro, Manuel Castro; Neto, Arnaldo Alcover; da Silva, Alzira dos Santos Amaral Gomes; Cardoso, Mauri José Baldini; Monteiro, Maria Inês Couto

2008-03-01

In this work, 24-h PM10 samples were collected in Rio de Janeiro, Brazil, and analysed for trace elements (Cd, Ce, Cu, La, Mo, Ni, Pb, Pd, Rh, Sb and Sn). The sampling was carried out at five locations (Bonsucesso; Centro, downtown city; Copacabana; Nova Iguaçu and Sumaré) with different traffic densities and anthropogenic activities. An analytical method based on the EPA method for the determination of trace elements in airborne particulate matter (PM), using ultrasonic-assisted extraction and inductively coupled plasma mass spectrometry (ICP-MS) was applied. Our results suggest that vehicular traffic is the most important source of environmental pollution at the studied sites. The presence of Mo, Pd and Rh in the analysed filters reflects an additional source of pollution caused by the erosion and deterioration of automotive catalytic converters.

Understanding Electrocatalytic Activity Enhancement of Bimetallic Particles to Ethanol Electro-oxidation: (1) Water Adsorption and Decomposition on PtnM (n=2,3 and 9; M=Pt, Ru, Sn)

PubMed Central

Wang, Yixuan; Mi, Yunjie; Redmon, Natalie; Holiday, Jessica

2009-01-01

The fundamental assumption of the bi-functional mechanism for PtSn alloy to catalyze ethanol electro-oxidation reaction (EER) is that Sn facilitates water dissociation and EER occurs over Pt site of the PtSn alloy. To clarify this assumption and achieve a good understanding about the EER, H2O adsorption and dissociation over bimetallic clusters PtM (M=Pt, Sn, Ru, Rh, Pd, Cu and Re) are systematically investigated in the present work. To discuss a variety of effects, PtnM (n=2, and 3; M=Pt, Sn and Ru), one-layer Pt6M (M=Pt, Sn and Ru), and two-layer (Pt6M)Pt3 (M=Pt, Sn, Ru, Rh, Pd, Cu and Re) clusters are used to model the PtM bimetallic catalysts. Water exhibits atop adsorption on Pt and Ru sites of the optimized clusters PtnM (n=2, and 3; M=Pt and Ru), yet bridge adsorption on Sn sites of Pt2Sn as well as distorted tetrahedral Pt3Sn. However, in the cases of one-layer Pt6M and two-layer Pt9M cluster models water preferentially binds to all of investigated central atom M of surface layer in atop configuration with the dipole moment of water almost parallel to the cluster surface. Water adsorption on the Sn site of PtnSn (n=2 and 3) is weaker than those on the Pt site of Ptn (n=3 and 4) and the Ru site of PtnRu (n=2 and 3), while water adsorptions on the central Sn atom of Pt6Sn and Pt9Sn are enhanced so significantly that they are even stronger than those on the central Pt and Ru atoms of PtnM (n=6 and 9; M=Pt and Ru). For all of the three cluster models, energy barrier (Ea) for the dissociation of adsorbed water over Sn is lower than over Ru and Pt atoms (e.g., Ea: 0.78 vs 0.96 and 1.07 eV for Pt9M), which also remains as external electric fields were added. It is interesting to note that the dissociation energy on Sn site is also the lowest (Ediss: 0.44 vs 0.61 and 0.67eV). The results show that from both kinetic and thermodynamic viewpoints Sn is more active to water decomposition than pure Pt and the PtRu alloy, which well supports the assumption of the bi-functional mechanism that Sn site accelerates the dissociation of H2O. The extended investigation for water behavior on the (Pt6M)Pt3 (M=Pt, Sn, Ru, Rh, Pd, Cu and Re) clusters indicate that the kinetic activity for water dissociation increases in the sequence of Cu < Pd < Rh < Pt < Ru < Sn < Re. PMID:20336187

Durable pd-based alloy and hydrogen generation membrane thereof

DOEpatents

Benn, Raymond C.; Opalka, Susanne M.; Vanderspurt, Thomas Henry

2010-02-02

A durable Pd-based alloy is used for a H.sub.2-selective membrane in a hydrogen generator, as in the fuel processor of a fuel cell plant. The Pd-based alloy includes Cu as a binary element, and further includes "X", where "X" comprises at least one metal from group "M" that is BCC and acts to stabilize the .beta. BCC phase for stability during operating temperatures. The metal from group "M" is selected from the group consisting of Fe, Cr, Nb, Ta, V, Mo, and W, with Nb and Ta being most preferred. "X" may further comprise at least one metal from a group "N" that is non-BCC, preferably FCC, that enhances other properties of the membrane, such as ductility. The metal from group "N" is selected from the group consisting of Ag, Au, Re, Ru, Rh, Y, Ce, Ni, Ir, Pt, Co, La and In. The at. % of Pd in the binary Pd--Cu alloy ranges from about 35 at. % to about 55 at. %, and the at. % of "X" in the higher order alloy, based on said binary alloy, is in the range of about 1 at. % to about 15 at. %. The metals are selected according to a novel process.

A Synthetic Pseudo-Rh: NOx Reduction Activity and Electronic Structure of Pd-Ru Solid-solution Alloy Nanoparticles

NASA Astrophysics Data System (ADS)

Sato, Katsutoshi; Tomonaga, Hiroyuki; Yamamoto, Tomokazu; Matsumura, Syo; Zulkifli, Nor Diana Binti; Ishimoto, Takayoshi; Koyama, Michihisa; Kusada, Kohei; Kobayashi, Hirokazu; Kitagawa, Hiroshi; Nagaoka, Katsutoshi

2016-06-01

Rh is one of the most important noble metals for industrial applications. A major fraction of Rh is used as a catalyst for emission control in automotive catalytic converters because of its unparalleled activity toward NOx reduction. However, Rh is a rare and extremely expensive element; thus, the development of Rh alternative composed of abundant elements is desirable. Pd and Ru are located at the right and left of Rh in the periodic table, respectively, nevertheless this combination of elements is immiscible in the bulk state. Here, we report a Pd-Ru solid-solution-alloy nanoparticle (PdxRu1-x NP) catalyst exhibiting better NOx reduction activity than Rh. Theoretical calculations show that the electronic structure of Pd0.5Ru0.5 is similar to that of Rh, indicating that Pd0.5Ru0.5 can be regarded as a pseudo-Rh. Pd0.5Ru0.5 exhibits better activity than natural Rh, which implies promising applications not only for exhaust-gas cleaning but also for various chemical reactions.

CH4 dehydrogenation on Cu(1 1 1), Cu@Cu(1 1 1), Rh@Cu(1 1 1) and RhCu(1 1 1) surfaces: A comparison studies of catalytic activity

NASA Astrophysics Data System (ADS)

Zhang, Riguang; Duan, Tian; Ling, Lixia; Wang, Baojun

2015-06-01

In the CVD growth of graphene, the reaction barriers of the dehydrogenation for hydrocarbon molecules directly decide the graphene CVD growth temperature. In this study, density functional theory method has been employed to comparatively probe into CH4 dehydrogenation on four types of Cu(1 1 1) surface, including the flat Cu(1 1 1) surface (labeled as Cu(1 1 1)) and the Cu(1 1 1) surface with one surface Cu atom substituted by one Rh atom (labeled as RhCu(1 1 1)), as well as the Cu(1 1 1) surface with one Cu or Rh adatom (labeled as Cu@Cu(1 1 1) and Rh@Cu(1 1 1), respectively). Our results show that the highest barrier of the whole CH4 dehydrogenation process is remarkably reduced from 448.7 and 418.4 kJ mol-1 on the flat Cu(1 1 1) and Cu@Cu(1 1 1) surfaces to 258.9 kJ mol-1 on RhCu(1 1 1) surface, and to 180.0 kJ mol-1 on Rh@Cu(1 1 1) surface, indicating that the adsorbed or substituted Rh atom on Cu catalyst can exhibit better catalytic activity for CH4 complete dehydrogenation; meanwhile, since the differences for the highest barrier between Cu@Cu(1 1 1) and Cu(1 1 1) surfaces are smaller, the catalytic behaviors of Cu@Cu(1 1 1) surface are very close to the flat Cu(1 1 1) surface, suggesting that the morphology of Cu substrate does not obviously affect the dehydrogenation of CH4, which accords with the reported experimental observations. As a result, the adsorbed or substituted Rh atom on Cu catalyst exhibit a better catalytic activity for CH4 dehydrogenation compared to the pure Cu catalyst, especially on Rh-adsorbed Cu catalyst, we can conclude that the potential of synthesizing high-quality graphene with the help of Rh on Cu foils may be carried out at relatively low temperatures. Meanwhile, the adsorbed Rh atom is the reaction active center, namely, the CVD growth can be controlled by manipulating the graphene nucleation position.

Confining the nucleation and overgrowth of Rh to the {111} facets of Pd nanocrystal seeds: the roles of capping agent and surface diffusion.

PubMed

Xie, Shuifen; Peng, Hsin-Chieh; Lu, Ning; Wang, Jinguo; Kim, Moon J; Xie, Zhaoxiong; Xia, Younan

2013-11-06

This article describes a systematic study of the spatially confined growth of Rh atoms on Pd nanocrystal seeds, with a focus on the blocking effect of a surface capping agent and the surface diffusion of adatoms. We initially used Pd cuboctahedrons as the seeds to illustrate the concept and to demonstrate the capabilities of our approach. Because the Pd{100} facets were selectively capped by a layer of chemisorbed Br(–) or I(–) ions, we were able to confine the nucleation and deposition of Rh atoms solely on the {111} facets of a Pd seed. When the synthesis was conducted at a relatively low temperature, the deposition of Rh atoms followed an island growth mode because of the high Rh–Rh interatomic binding energy. We also facilitated the surface diffusion of deposited Rh atoms by increasing the reaction temperature and decreasing the injection rate for the Rh precursor. Under these conditions, the deposition of Rh on the Pd{111} facets was switched to a layered growth mode. We further successfully extended this approach to a variety of other types of Pd polyhedral seeds that contained Pd{111} and Pd{100} facets in different proportions on the surface. As expected, a series of Pd–Rh bimetallic nanocrystals with distinctive elemental distributions were obtained. We could remove the Pd cores through selective chemical etching to generate Rh hollow nanoframes with different types and degrees of porosity. This study clearly demonstrates the importance of facet capping, surface diffusion, and reaction kinetics in controlling the morphologies of bimetallic nanocrystals during a seed-mediated process. It also provides a new direction for the rational design and synthesis of nanocrystals with spatially controlled distributions of elements for a variety of applications.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Not Available

The following are reported: theoretical calculations (configuration interaction, relativistic effective core potentials, polyatomics, CASSCF); proposed theoretical studies (clusters of Cu, Ag, Au, Ni, Pt, Pd, Rh, Ir, Os, Ru; transition metal cluster ions; transition metal carbide clusters; bimetallic mixed transition metal clusters); reactivity studies on transition metal clusters (reactivity with H{sub 2}, C{sub 2}H{sub 4}, hydrocarbons; NO and CO chemisorption on surfaces). Computer facilities and codes to be used, are described. 192 refs, 13 figs.

Lattice dynamics and metastability of fcc metals in the hcp structure and the crucial role of spin-orbit coupling in platinum

NASA Astrophysics Data System (ADS)

Schönecker, Stephan; Li, Xiaoqing; Richter, Manuel; Vitos, Levente

2018-06-01

We investigate the lattice dynamical properties of Ni, Cu, Rh, Pd, Ag, Ir, Pt, and Au in the nonequilibrium hcp structure by means of density-functional simulations, wherein spin-orbit coupling (SOC) was considered for Ir, Pt, and Au. The determined dynamical properties reveal that all eight elements possess a metastable hcp phase at zero temperature and pressure. The hcp Ni, Cu, Rh, Pd, and Au previously observed in nanostructures support this finding. We make evident that the inclusion of SOC is mandatory for an accurate description of the phonon dispersion relations and dynamical stability of hcp Pt. The underlying sensitivity of the interatomic force constants is ascribed to a SOC-induced splitting of degenerate band states accompanied by a pronounced reduction of electronic density of states at the Fermi level. To give further insight into the importance of SOC in Pt, we (i) focus on phase stability and examine a lattice transformation related to optical phonons in the hcp phase and (ii) focus on the generalized stacking fault energy (GSFE) of the fcc phase pertinent to crystal plasticity. We show that the intrinsic stable and unstable fault energies of the GSFE scale as in other common fcc metals, provided that the spin-orbit interaction is taken into account.

Formation and electronic properties of palladium hydrides and palladium-rhodium dihydride alloys under pressure.

PubMed

Yang, Xiao; Li, Huijian; Ahuja, Rajeev; Kang, Taewon; Luo, Wei

2017-06-14

We present the formation possibility for Pd-hydrides and Pd-Rh hydrides system by density functional theory (DFT) in high pressure upto 50 GPa. Calculation confirmed that PdH 2 in face-centered cubic (fcc) structure is not stable under compression that will decomposition to fcc-PdH and H 2 . But it can be formed under high pressure while the palladium is involved in the reaction. We also indicate a probably reason why PdH 2 can not be synthesised in experiment due to PdH is most favourite to be formed in Pd and H 2 environment from ambient to higher pressure. With Rh doped, the Pd-Rh dihydrides are stabilized in fcc structure for 25% and 75% doping and in tetragonal structure for 50% doping, and can be formed from Pd, Rh and H 2 at high pressure. The electronic structural study on fcc type Pd x Rh 1-x H 2 indicates the electronic and structural transition from metallic to semi-metallic as Pd increased from x = 0 to 1.

Modelling free and oxide-supported nanoalloy catalysts: comparison of bulk-immiscible Pd-Ir and Au-Rh systems and influence of a TiO2 support.

PubMed

Demiroglu, Ilker; Fan, Tian-E; Li, Z Y; Yuan, Jun; Liu, Tun-Dong; Piccolo, Laurent; Johnston, Roy L

2018-05-24

The relative stabilities of different chemical arrangements of Pd-Ir and Au-Rh nanoalloys (and their pure metal equivalents) are studied, for a range of compositions, for fcc truncated octahedral 38- and 79-atom nanoparticles (NPs). For the 38-atom NPs, comparisons are made of pure and alloy NPs supported on a TiO2(110) slab. The relative energies of different chemical arrangements are found to be similar for Pd-Ir and Au-Rh nanoalloys, and depend on the cohesive and surface energies of the component metals. For supported nanoalloys on TiO2, the interaction with the surface is greater for Ir (Rh) than Pd (Au): most of the pure NPs and nanoalloys preferentially bind to the TiO2 surface in an edge-on configuration. When Au-Rh nanoalloys are bound to the surface through Au, the surface binding strength is lower than for the pure Au NP, while the Pd-surface interaction is found to be greater for Pd-Ir nanoalloys than for the pure Pd NP. However, alloying leads to very little difference in Ir-surface and Rh-surface binding strength. Comparing the relative stabilities of the TiO2-supported NPs, the results for Pd-Ir and Au-Rh nanoalloys are the same: supported Janus NPs, whose Ir (Rh) atoms bind to the TiO2 surface, bind most strongly to the surface, becoming closer in energy to the core-shell configurations (Ir@Pd and Rh@Au) which are favoured for the free particles.

Platinum-group minerals in the LG and MG chromitites of the eastern Bushveld Complex, South Africa

NASA Astrophysics Data System (ADS)

Oberthür, Thomas; Junge, Malte; Rudashevsky, Nikolay; de Meyer, Eveline; Gutter, Paul

2016-01-01

The chromitites of the Bushveld Complex in South Africa contain vast resources of platinum-group elements (PGE); however, except for the economic upper group (UG)-2 chromitite seam, information on the distribution of the PGE in the ores and on the mineralogical nature, assemblages, and proportions of platinum-group minerals (PGM) is essentially missing. In the present geochemical and mineralogical study, PGE concentrates originating from the lower group (LG)-6 and middle group (MG)-1/2 chromitites were investigated with the intention to fill this gap of knowledge. Chondrite-normalized PGE patterns of bulk rock and concentrates are characterized by a positive slope from Os to Rh, a slight drop to Pt, and an increase to Pd again. The pronounced similarities of the PGE patterns indicate similar primary processes of PGE concentration in the chromitites, namely "sulfide control" of the PGE mineralization, i.e., co-precipitation of chromite and sulfide. Further, the primary control of PGE concentration in chromitites appears to be dual in character: (i) base-level concentrations of IPGE (up to ˜500 ppb) hosted within chromite and (ii) co-precipitation of chromite and sulfide, the latter containing virtually the entire remaining PGE budget. Sulfides (chalcopyrite, pentlandite, and pyrite; pyrrhotite is largely missing) are scarce within the chromitites and occur mainly interstitial to chromite grains. Pd and Rh contents in pentlandite are low and erratic. Essentially, the whole PGE inventory of the ores occurs in the form of discrete PGM. The PGM are almost always associated with sulfides. The dominant PGM are various Pt-Pd-Rh sulfides (cooperite/braggite [(Pt,Pd)S] and malanite/cuprorhodsite [CuPt2S4]/[CuRh2S4]), laurite [RuS2], the main carrier of the IPGE (Os, Ir, Ru), sulfarsenides [(Rh,Pt,Ir)AsS], sperrylite [PtAs2], Pt-Fe alloys, and a large variety of mainly Pd-rich PGM. The LG and MG chromitites have many characteristics in common and define a general, "typical" PGM spectrum of Bushveld chromitites. This PGM assemblage is characterized by the predominance of PGE-sulfides including elevated proportions of malanite, variable proportions of (sulf) arsenides, and Pt-Fe alloys in conjunction with a paucity of (bismutho)tellurides. The formation of this specific PGM spectrum is related to the distinct chromitite environment and its depositional and post-depositional history, whereby desulfurization reactions have probably played an important role. The LG-6 samples have higher contents of PGE-sulfides, including extraordinary high proportions of malanite but low PGE-arsenide and PGE-sulfarsenide contents compared to the MG-1/2 samples. This indicates a higher availability of arsenic either in the stratigraphically higher MG-1/2 samples (compared to the LG-6) or regionally in the chromitites south of the Steelpoort lineament.

Model for the Prediction of the Hydriding Thermodynamics of Pd-Rh-Co Ternary Alloys

DOE Office of Scientific and Technical Information (OSTI.GOV)

Teter, D.F.; Thoma, D.J.

1999-03-01

A dilute solution model (with respect to the substitutional alloying elements) has been developed, which accurately predicts the hydride formation and decomposition thermodynamics and the storage capacities of dilute ternary Pd-Rh-Co alloys. The effect of varying the rhodium and cobalt compositions on the thermodynamics of hydride formation and decomposition and hydrogen capacity of several palladium-rhodium-cobalt ternary alloys has been investigated using pressure-composition (PC) isotherms. Alloying in the dilute regime (<10 at.%) causes the enthalpy for hydride formation to linearly decrease with increasing alloying content. Cobalt has a stronger effect on the reduction in enthalpy than rhodium for equivalent alloying amounts.more » Also, cobalt reduces the hydrogen storage capacity with increasing alloying content. The plateau thermodynamics are strongly linked to the lattice parameters of the alloys. A near-linear dependence of the enthalpy of hydride formation on the lattice parameter was observed for both the binary Pd-Rh and Pd-Co alloys, as well as for the ternary Pd-Rh-Co alloys. The Pd-5Rh-3Co (at. %) alloy was found to have similar plateau thermodynamics as a Pd-10Rh alloy, however, this ternary alloy had a diminished hydrogen storage capacity relative to Pd-10Rh.« less

Platinum-group element geochemistry of the Forest Reef Volcanics, southeastern Australia: Implications for porphyry Au-Cu mineralisation

NASA Astrophysics Data System (ADS)

Lowczak, Jessica N.; Campbell, Ian H.; Cocker, Helen; Park, Jung-Woo; Cooke, David R.

2018-01-01

Platinum-group element concentrations in felsic to intermediate rocks from the Forest Reef Volcanics, Cadia-Neville region, southeastern Australia have been analysed by the Ni-S fire assay-isotope dilution method. The Forest Reef Volcanics are shoshonitic to calc-alkaline in composition and fractionated to produce a wide range of compositions, with MgO varying between 9.7 and 1.8 wt.%. The interest in this suite is that it is coeval with Au-Cu porphyry-style mineralisation in the Cadia mineral district. This study uses PGE geochemistry to determine the timing of sulfide saturation, relative to volatile (ore-fluid) saturation, in the magma that gave rise to the Forest Reef Volcanics and, in turn, to assess how this timing affected the mineralisation potential of the evolving magmatic system. The Forest Reef Volcanics can be subdivided, on the basis of their contrasting PGE geochemistry, into high-Mg (>6.8 wt.% MgO) and low-Mg suites (≤6.8 wt.% MgO). Platinum, Pd and Re concentrations increase in the high-Mg samples, whereas Ir and Ru decrease and Rh concentrations remain steady, with decreasing MgO. The coupled Ir, Ru and Rh depletion is attributed to the partitioning of these elements into magnetite. The rate of Pt and Pd enrichment is not possible by closed-system fractional crystallisation alone, which suggests that the parent magma was replenished by a Pt-Pd-rich melt. In contrast, the PGE concentrations in the low-Mg samples decrease with decreasing MgO indicating the onset of sulfide saturation at 6.8 wt.% MgO, which is confirmed by the presence of spheroidal sulfide inclusions in liquidus crystals (i.e. clinopyroxene, plagioclase, magnetite). The rate of Pd depletion is appreciably less than for any other sulfide saturated felsic system for which data are available. This requires either that the amount of sulfide melt to have precipitated was unusually low, or that the rate of Pd depletion was limited by the mass of silicate melt the sulfide melt reached equilibrium with, or both. In any event, the fraction of sulfide melt that precipitated was too small to have had a significant effect on the Cu and Au content of the magma so that both Cu and Au were available to enter the ore-forming fluid when the magma became volatile saturated at, or shortly after, it reached ca. 2.9 wt.% MgO.

Catalytic hydrodechlorination of trichloroethylene in a novel NaOH/2-propanol/methanol/water system on ceria-supported Pd and Rh catalysts.

PubMed

Cobo, Martha; Becerra, Jorge; Castelblanco, Miguel; Cifuentes, Bernay; Conesa, Juan A

2015-08-01

The catalytic hydrodechlorination (HDC) of high concentrations of trichloroethylene (TCE) (4.9 mol%, 11.6 vol%) was studied over 1%Pd, 1%Rh and 0.5%Pd-0.5%Rh catalysts supported on CeO2 under conditions of room temperature and pressure. For this, a one-phase system of NaOH/2-propanol/methanol/water was designed with molar percentages of 13.2/17.5/36.9/27.6, respectively. In this system, the alcohols delivered the hydrogen required for the reaction through in-situ dehydrogenation reactions. PdRh/CeO2 was the most active catalyst for the degradation of TCE among the evaluated materials, degrading 85% of the trichloroethylene, with alcohol dehydrogenation rates of 89% for 2-propanol and 83% for methanol after 1 h of reaction. Fresh and used catalysts were characterized by Transmission Electron Microscopy (TEM), X-ray Photoelectron Spectroscopy (XPS), and Thermogravimetric analysis (TGA). These results showed important differences of the active phase in each catalyst sample. Rh/CeO2 had particle sizes smaller than 1 nm and the active metal was partially oxidized (Rh(0)/Rh(+δ) ratio of 0.43). This configuration showed to be suitable for alcohols dehydrogenation. On the contrary, Pd/CeO2 showed a Pd completed oxidized and with a mean particle size of 1.7 nm, which seemed to be unfavorable for both, alcohols dehydrogenation and TCE HDC. On PdRh/CeO2, active metals presented a mean particle size of 2.7 nm and more reduced metallic species, with ratios of Rh(0)/Rh(+δ) = 0.67 and Pd(0)/Pd(+δ) = 0.28, which showed to be suitable features for the TCE HDC. On the other hand, TGA results suggested some deposition of NaCl residues over the catalyst surfaces. Thus, the new reaction system using PdRh/CeO2 allowed for the degradation of high concentrations of the chlorinated compound by using in situ hydrogen liquid donors in a reaction at room temperature and pressure. Copyright © 2015 Elsevier Ltd. All rights reserved.

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

NASA Astrophysics Data System (ADS)

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).

Measurement of excitation functions of helion-induced reactions on enriched Ru targets for production of medically important 103Pd and 101mRh and some other radionuclides.

PubMed

Skakun, Ye; Qaim, S M

2008-05-01

Excitation functions were determined by the stacked-foil and induced radioactivity measurement technique for the reactions (100)Ru(alpha,n)(103)Pd, (101)Ru(alpha,2n)(103)Pd, (101)Ru((3)He,n)(103)Pd, and (102)Ru((3)He,2n)(103)Pd, producing the therapeutic radionuclide (103)Pd, and for the reactions (101)Ru((3)He,x)(101 m)Rh(Cum) and (102)Ru((3)He,x)(101 m)Rh(Cum), producing the medically interesting radionuclide (101 m)Rh. Data were also measured for the reactions (101)Ru((3)He,pn+d)(102 m,g)Rh, (102)Ru((3)He,p2n+dn+t)(102 m,g)Rh, (101)Ru((3)He,x)(101 g)Rh(Cum), (102)Ru((3)He,x)(101 g)Rh(Cum), (101)Ru((3)He,3n)(101)Pd, (102)Ru((3)He,4n)(101)Pd, (101)Ru((3)He,4n)(100)Pd, and (101)Ru((3)He,p3n+d2n+tn)(100)Rh, producing other palladium and rhodium isotopes/isomers. The energy ranges covered were up to 25 MeV for alpha-particles and up to 34 MeV for (3)He ions. The radioactivity of the radionuclide (103)Pd induced in thin metallic foils of the enriched ruthenium isotopes was measured by high-resolution X-ray spectrometry and the radioactivities of other radionuclides by gamma-ray spectrometry. The integral thick target yields of the radionuclide (103)Pd calculated from the excitation functions of the first four of the above-named reactions amount to 960, 1050, 50, and 725 kBq/microAh, respectively, at the maximum investigated energies of the incident particles. The integral thick target yields of the radionuclide (101 m)Rh amount to 16.1 and 2.9 MBq/microAh for (101)Ru and (102)Ru targets, respectively, at 34 MeV energy of incident (3)He ions. The integral yields of the other observed radionuclides were also deduced from the excitation functions of the above-mentioned respective nuclear reactions. The excitation functions and integral yields of some rare reaction products were also determined. The experimental excitation functions of some reactions are compared with the predictions of nuclear model calculations. In general, good agreement was obtained.

Platinum-group element contents of Karelian kimberlites: Implications for the PGE budget of the sub-continental lithospheric mantle

NASA Astrophysics Data System (ADS)

Maier, W. D.; O'Brien, H.; Peltonen, P.; Barnes, Sarah-Jane

2017-11-01

We present high-precision isotope dilution data for Os, Ir, Ru, Pt, Pd and Re in Group I and Group II kimberlites from the Karelian craton, as well as 2 samples of the Premier Group I kimberlite pipe from the Kaapvaal craton. The samples have, on average, 1.38 ppb Pt and 1.33 ppb Pd, with Pt/Pd around unity. These PGE levels are markedly lower, by as much as 80%, than those reported previously for kimberlites from South Africa, Brazil and India, but overlap with PGE results reported recently from Canadian kimberlites. Primitive-mantle-normalised chalcophile element patterns are relatively flat from Os to Pt, but Cu, Ni and, somewhat less so, Au are enriched relative to the PGE (e.g., Cu/Pd > 25.000). Pd/Ir ratios are 3,6 on average, lower than in most other mantle melts. The PGE systematics can be largely explained by two components, (i) harzburgite/lherzolite detritus of the SCLM with relatively high IPGE (Os-Ir-Ru)/PPGE (Rh-Pt-Pd) ratios, and (ii) a melt component that has high PPGE/IPGE ratios. By using the concentrations of iridium in the kimberlites as a proxy for the proportion of mantle detritus in the magma, we estimate that the analysed kimberlites contain 3-27% entrained and partially dissolved detritus from the sub-continental lithospheric mantle, consistent with previous estimates of kimberlites elsewhere (Tappe S. et al., 2016, Chem. Geol. 10.1016/j.chemgeo.2016.08.019).

Structure-function relationship exists for ginsenosides in reducing cell proliferation and inducing apoptosis in the human leukemia (THP-1) cell line.

PubMed

Popovich, David G; Kitts, David D

2002-10-01

Ginsenosides of the 20(S)-protopanaxadiol and 20(S)-protopanaxatriol classifications including the aglycones, protopanaxadiol (PD), protopanaxatriol (PT), and ginsenosides Rh2 and Rh1 were shown to posses characteristic effects on the proliferation of human leukemia cells (THP-1). A similar efficacy was not apparent for ginsenoside Rg3. The concentrations to inhibit 50% of cells (LC50) for PD, Rh2, PT, and Rh1 were 13, 15, 19, and 210 microg/mL, respectively. PD and PT induced DNA fragmentation at the LC50 after 72 h of treatment, compared to Rh2, Rh1, dexamethasone, and untreated cells. Cell-cycle analysis confirmed apoptosis with PD and PT treatment of THP-1 cells resulting in a buildup of sub-G1 cells after 24, 48, and 72 h of treatment. Rh2 and dexamethasone treatments also increased apoptotic cells after 24 h, whereas Rh1 did not. After 48 and 72 h, Rh2, Rh1, and dexamethasone similarly increased apoptosis, but these effects were significantly (P<0.05) lower than those observed for both PD and PT treatments. Furthermore, treatments that produced the largest buildup of apoptotic cells were also found to have the largest release of lactate dehydrogenase. It can be concluded from these studies that the presence of sugars in PD and PT aglycone structures reduces the potency to induce apoptosis, and alternately alter membrane integrity. These cytotoxic effects were different to THP-1 cells than dexamethasone.

Growth and sacrificial oxidation of transition metal nanolayers

NASA Astrophysics Data System (ADS)

Tsarfati, Tim; Zoethout, Erwin; van de Kruijs, Robbert; Bijkerk, Fred

2009-04-01

Growth and oxidation of Au, Pt, Pd, Rh, Cu, Ru, Ni and Co layers of 0.3-4.3 nm thickness on Mo have been investigated with ARPES and AFM. Co and Ni layers oxidize while the Mo remains metallic. For nobler metals, the on top O and oxidation state of subsurface Mo increase, suggesting sacrificial e - donation by Mo. Au and Cu, in spite of their significantly lower surface free energy, grow in islands on Mo and actually promote Mo oxidation. Applications of the sacrificial oxidation in nanometer thin layers exist in a range of nanoscopic devices, such as nano-electronics and protection of e.g. multilayer X-ray optics for astronomy, medicine and lithography.

Interfacial and Alloying Effects on Activation of Ethanol from First-Principles

DOE PAGES

An, Wei; Men, Yong; Wang, Jinguo; ...

2017-02-24

Here, we present a first-principles density-functional theory study of ethanol activation at oxide/Rh(111) interface and the alloying effect on mitigating carbon deposition, which are essential to direct ethanol fuel cell (DEFC) anode reaction and steam reforming of ethanol (SRE) reaction. Our calculated results show that charge can transfer from Rh(111) substrate to MO x chain (e.g., MoO 3 and MnO 2), or from MO x chain (e.g., MgO, SnO 2, ZrO 2, and TiO 2) to Rh(111) substrate. The OH-binding strength is increased exponentially with M δ+ charge ranging from 1.4 to 2.2, which renders MnO 2/Rh(111) and MgO/Rh(111) interfacesmore » weaker OH-binding, and thereby enhanced oxidizing functionality of OH* for promoting ethanol oxidation reaction (EOR) at DEFC anode. For efficient C–C bond breaking, a large number of Rh ensemble sizes are critically needed at the interface of MO x/Rh(111). We found that Rh 1Au 3 near surface alloy has the weakest C* and CO* binding, followed by Rh 1Cu 3 and Rh 1Pd 3 near surface alloys, while Rh 1Ir 3 and Rh 1Ru 3 surface alloys have C* and CO* binding strength similar to that of pure Rh metal. The general implication of this study is that by engineering alloyed structure of weakened C* and CO* binding complemented with metal oxides of weakened OH-binding, high-performance DEFC anode or SRE catalysts can be identified.« less

Batch leaching tests of motherboards to assess environmental contamination by bromine, platinum group elements and other selected heavy metals.

PubMed

Almeida, César; Grosselli, Melina; González, Patricia; Martínez, Dante; Gil, Raúl

2016-02-01

In this study, a batch leaching test was executed to evaluate the toxicity associated with chemicals contained in motherboards. The leaching solutions used were distilled water, nitric acid, acetic acid and synthetic acid rain solution. A total of 21 elements including Ag, As, Au, Br, Cd, Co, Cr, Cu, Hf, Ir, Mn, Ni, Os, Pb, Pd, Pt, Rd, Rh, Se, U and Zn were analyzed. In this study, the pH values of all the leachates fell within the range of 2.33-4.88. The highest concentrations of metals were obtained from the acid rain solution, whilst the maximum value of bromine was achieved with solution of acetic acid. Appreciable concentrations of platinum group elements were detected with concentrations around 3.45, 1.43, 1.21 and 22.19 µg L(-1) for Ir, Pd, Pt and Rh, respectively. The different leaching of the motherboards revealed the predominant presence of the toxic substances in the leached from the e-waste. Copyright © 2015 Elsevier Ltd. All rights reserved.

For cermet inert anode containing oxide and metal phases useful for the electrolytic production of metals

DOEpatents

Ray, Siba P.; Liu, Xinghua; Weirauch, Douglas A.

2002-01-01

A cermet inert anode for the electrolytic production of metals such as aluminum is disclosed. The inert anode comprises a ceramic phase including an oxide of Ni, Fe and M, where M is at least one metal selected from Zn, Co, Al, Li, Cu, Ti, V, Cr, Zr, Nb, Ta, W, Mo, Hf and rare earths, preferably Zn and/or Co. Preferred ceramic compositions comprise Fe.sub.2 O.sub.3, NiO and ZnO or CoO. The cermet inert anode also comprises a metal phase such as Cu, Ag, Pd, Pt, Au, Rh, Ru, Ir and/or Os. A preferred metal phase comprises Cu and Ag. The cermet inert anodes may be used in electrolytic reduction cells for the production of commercial purity aluminum as well as other metals.

Phase Structure and Site Preference Behavior of Ternary Alloying Additions to PdTi and PtTi Shape-Memory Alloys

NASA Technical Reports Server (NTRS)

Bozzolo, Guillermo; Mosca, Hugo O.; Noebe, Ronald D.

2006-01-01

The phasc structure and concentration dependence of the lattice parameter and energy of formation of ternary Pd-'I-X and Pt-Ti-X alloys for a large number of ternary alloying additions X (X = Na, Mg, Al, Si, Sc. V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Ag, Cd, Hf, Ta, W, Re, Os, Ir) are investigated with an atomistic modeling approach. In addition, a detailed description of the site preference behavior of such additions showing that the elements can be grouped according to their absolute preference for a specific site, regardless of concentration, or preference for available sites in the deficient sublattice is provided.

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

NASA Astrophysics Data System (ADS)

Helmy, Hassan M.; Bragagni, Alessandro

2017-11-01

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

Behaviour of Ni-PGE-Au-Cu in mafic-ultramafic volcanic suites of the 2.7 Ga Kambalda Sequence, Kalgoorlie Terrane, Yilgarn Craton

NASA Astrophysics Data System (ADS)

Said, Nuru; Kerrich, Robert; Maier, W. D.; McCuaig, Campbell

2011-05-01

The 2.7 Ga Kambalda Sequence comprises a mafic to ultramafic dominated volcanic rock sequence of the Kalgoorlie Terrane, Yilgarn Craton, Western Australia. The Sequence is divided into Lower and Upper Units separated by the Kambalda Komatiite Formation. Five basalt suites of the Lower Unit are tholeiitic where MgO spans 5-10 wt.% MgO, with minor assimilation-fractional crystallization (AFC), whereas six volcanic suites identified in the Upper Unit are tholeiitic to komatiitic-basalts with MgO 24-5 wt.% having generally greater degrees of AFC. Upper suites plot at Al 2O 3/TiO 2 (17-26) close to the primitive mantle ratio of 21, and Pt + Pd (19-31 ppb), whereas the PGE-depleted Lower basalts plot at generally lower Al 2O 3/TiO 2 (<16) and Pt + Pd (<10 ppb). Most suites have an average Pt/Pd ratio of 1.11, despite large variations in MgO contents, broadly consistent with the Pt/Pd ratio in the primitive mantle. On primitive mantle-normalised PGE plots, Upper suites generally display less fractionated patterns of the IPGE (Os, Ir, Ru and Rh) from the PPGE (Pt and Pd) relative to the Lower basalts. Most suites exhibit patterns with positive slopes reflecting relative enrichment of Pd, Pt, Au and Cu relative to Ni and IPGE. In suites of both Units, the concentrations of Ir and Ru fall with decreasing MgO contents, indicating their broadly compatible behaviour during magmatic evolution that involved AFC. Platinum and Pd behave as incompatible elements in the high-MgO suites, whereas Pt and Pd behave compatibly during crystallisation of the Lower basalt magmas, an interpretation consistent with progressively higher Cu/Pt and Cu/Pd ratios at decreasing MgO contents, and with falling Pt/Ti, collectively due to sulphur saturation induced by AFC as recorded in an antivariance of Pd/Ir with Nb/Th, a monitor of AFC. Collectively, the data suggest that several of the Lower Basalt suites crystallised under sulphide-saturated conditions, whereas most of the Upper Basalt Sequences remained sulphur undersaturated during magmatic evolution. Alteration, and fractional crystallisation of silicate and oxide phases, can be ruled out as factors governing PGE distribution in these mafic-ultramafic suites. Instead, the data suggest that discrete PGE-bearing phase (s) fractionated from the magmas. Such phases could be platinum group minerals (PGM; e.g., laurite) and/or alloys, or discrete PGE-rich nuggets or sulphides.

Sulfide petrology and highly siderophile element geochemistry of abyssal peridotites: a coupled study of samples from the Kane Fracture Zone (45°W 23°20N, MARK area, Atlantic Ocean)

NASA Astrophysics Data System (ADS)

Luguet, Ambre; Lorand, Jean-Pierre; Seyler, Monique

2003-04-01

Nineteen samples from the Kane Fracture Zone have been studied for sulfide mineralogy and analyzed for S, Se, platinum-group elements (PGE), and Au to assess the effect of refertilization processes on the PGE systematics of abyssal peridotites. The lherzolites show broadly chondritic PGE ratios and sulfide modal abundances (0.01 to 0.03 wt%) consistent with partial melting models, although the few pyroxene-hosted sulfide inclusions and in situ LAM-ICPMS analyses provide evidence for in situ mobilization of a Cu-Ni-rich sulfide partial melt. The most refractory harzburgites (spinel Cr# > 29) are almost devoid of magmatic sulfides and show uniformly low Pd N/Ir N (<0.5) for variable Pt N/Ir N (0.8 to 1.2). The compatible behavior of Os, Ir, Ru, Rh, and Pt reflects the presence of primary Os-Ru alloys. Some harzburgites displaying petrographic evidence for refertilization by incremental melts en route to the surface are enriched in sulfides (up to 0.1 wt%). Some of these sulfides are concentrated in small veinlets of clinopyroxene and spinel crystallized from these melts. These S-rich harzburgites display superchondritic Pd N/Ir N (up to 2.04) positively correlated with sulfide modal contents. It is concluded that refertilization processes resulting in precipitation of metasomatic sulfides may significantly enhance Pd concentrations of abyssal peridotites while marginally affecting Pt (Pt N/Ir N ≤ 1.24) and Rh (Rh N/Ir N ≤ 1.23) as well. When the effects of such processes are screened out, our database suggests PGE relative abundances in the DMM (Depleted MORB Mantle; MORB: Mid-Ocean Ridge) within the uncertainty range of chondritic meteorites, without evidence of superchondritic Pt/Ir and/or Rh/Ir ratios.

Platinum-group element, Gold, Silver and Base Metal distribution in compositionally zoned sulfide droplets from the Medvezky Creek Mine, Noril'sk, Russia

USGS Publications Warehouse

Barnes, S.-J.; Cox, R.A.; Zientek, M.L.

2006-01-01

Concentrations of Ag, Au, Cd, Co, Re, Zn and Platinum-group elements (PGE) have been determined in sulfide minerals from zoned sulfide droplets of the Noril'sk 1 Medvezky Creek Mine. The aims of the study were; to establish whether these elements are located in the major sulfide minerals (pentlandite, pyrrhotite, chalcopyrite and cubanite), to establish whether the elements show a preference for a particular sulfide mineral and to investigate the model, which suggests that the zonation in the droplets is caused by the crystal fractionation of monosulfide solid solution (mss). Nickel, Cu, Ag, Re, Os, Ir, Ru, Rh and Pd, were found to be largely located in the major sulfide minerals. In contrast, less than 25% of the Au, Cd, Pt and Zn in the rock was found to be present in these sulfides. Osmium, Ir, Ru, Rh and Re were found to be concentrated in pyrrhotite and pentlandite. Palladium and Co was found to be concentrated in pentlandite. Silver, Cd and Zn concentrations are highest in chalcopyrite and cubanite. Gold and platinum showed no preference for any of the major sulfide minerals. The enrichment of Os, Ir, Ru, Rh and Re in pyrrhotite and pentlandite (exsolution products of mss) and the low levels of these elements in the cubanite and chalcopyrite (exsolution products of intermediate solid solution, iss) support the mss crystal fractionation model, because Os, Ir, Ru, Rh and Re are compatible with mss. The enrichment of Ag, Cd and Zn in chalcopyrite and cubanite also supports the mss fractionation model these minerals are derived from the fractionated liquid and these elements are incompatible with mss and thus should be enriched in the fractionated liquid. Gold and Pt do not partition into either iss or mss and become sufficiently enriched in the final fractionated liquid to crystallize among the iss and mss grains as tellurides, bismithides and alloys. During pentlandite exsolution Pd appears to have diffused from the Cu-rich portion of the droplet into pentlandite. ?? Springer-Verlag 2006.

The production of radionuclides for nuclear medicine from a compact, low-energy accelerator system.

PubMed

Webster, William D; Parks, Geoffrey T; Titov, Dmitry; Beasley, Paul

2014-05-01

The field of nuclear medicine is reliant on radionuclides for medical imaging procedures and radioimmunotherapy (RIT). The recent shut-downs of key radionuclide producers have highlighted the fragility of the current radionuclide supply network, however. To ensure that nuclear medicine can continue to grow, adding new diagnostic and therapy options to healthcare, novel and reliable production methods are required. Siemens are developing a low-energy, high-current - up to 10 MeV and 1 mA respectively - accelerator. The capability of this low-cost, compact system for radionuclide production, for use in nuclear medicine procedures, has been considered. The production of three medically important radionuclides - (89)Zr, (64)Cu, and (103)Pd - has been considered, via the (89)Y(p,n), (64)Ni(p,n) and (103)Rh(p,n) reactions, respectively. Theoretical cross-sections were generated using TALYS and compared to experimental data available from EXFOR. Stopping power values generated by SRIM have been used, with the TALYS-generated excitation functions, to calculate potential yields and isotopic purity in different irradiation regimes. The TALYS excitation functions were found to have a good agreement with the experimental data available from the EXFOR database. It was found that both (89)Zr and (64)Cu could be produced with high isotopic purity (over 99%), with activity yields suitable for medical diagnostics and therapy, at a proton energy of 10MeV. At 10MeV, the irradiation of (103)Rh produced appreciable quantities of (102)Pd, reducing the isotopic purity. A reduction in beam energy to 9.5MeV increased the radioisotopic purity to 99% with only a small reduction in activity yield. This work demonstrates that the low-energy, compact accelerator system under development by Siemens would be capable of providing sufficient quantities of (89)Zr, (64)Cu, and (103)Pd for use in medical diagnostics and therapy. It is suggested that the system could be used to produce many other isotopes currently useful to nuclear medicine. Copyright © 2014 Elsevier Inc. All rights reserved.

[Determination of ru, rh and Pd in 30% trialkyl phosphine oxide (TRPO)-kerosene by inductively coupled plasma-atomic emission spectrum (ICP-AES)].

PubMed

Wang, Jian-Chen; Zhang, Lin

2013-07-01

The determination method of Ru, Rh and Pd in 30% TRPO-kerosene ICP-AES was studied by using aqueous calibration reference solution and choosing ethanol as diluent. The effects of the contents of 30% TRPO-kerosene and aqueous solution and the concentration of HNO3 in 30% TRPO-kerosene on the intensities of Ru, Rh and Pd were described. The optimized condition for preparing samples and calibration solutions was chosen as follows: The contents of 30% TRPO-kerosene and aqueous phase were 10% (V/V) and 5% (V/V) respectively and the concentration of HNO3 30% TRPO-kerosene was 0.20 mol x L(-1). The determination method of Au, Ru and Pd was set up according to the above condition. The detection limit, precision and recovery ratio of Ru, Rh and Pd are well. The method is not only used in determination of Au, Ru and Pd in 30% TRPO-kerosene, but also used in other organic phases.

Palladium(II)-Catalyzed Annulation between ortho-Alkenylphenols and Allenes. Key Role of the Metal Geometry in Determining the Reaction Outcome.

PubMed

Casanova, Noelia; Del Rio, Karina P; García-Fandiño, Rebeca; Mascareñas, José L; Gulías, Moisés

2016-05-06

2-Alkenylphenols react with allenes, upon treatment with catalytic amounts of Pd(II) and Cu(II), to give benzoxepine products in high yields and with very good regio- and diastereoselectivities. This contrasts with the results obtained with Rh catalysts, which provided chromene-like products through a pathway involving a β-hydrogen elimination step. Computational studies suggest that the square planar geometry of the palladium is critical to favor the reductive elimination process required for the formation of the oxepine products.

Atomistic Modeling of Surface and Bulk Properties of Cu, Pd and the Cu-Pd System

NASA Technical Reports Server (NTRS)

Bozzolo, Guillermo; Garces, Jorge E.; Noebe, Ronald D.; Abel, Phillip; Mosca, Hugo O.; Gray, Hugh R. (Technical Monitor)

2002-01-01

The BFS (Bozzolo-Ferrante-Smith) method for alloys is applied to the study of the Cu-Pd system. A variety of issues are analyzed and discussed, including the properties of pure Cu or Pd crystals (surface energies, surface relaxations), Pd/Cu and Cu/Pd surface alloys, segregation of Pd (or Cu) in Cu (or Pd), concentration dependence of the lattice parameter of the high temperature fcc CuPd solid solution, the formation and properties of low temperature ordered phases, and order-disorder transition temperatures. Emphasis is made on the ability of the method to describe these properties on the basis of a minimum set of BFS universal parameters that uniquely characterize the Cu-Pd system.

Tetragonal-antiprismatic coordination of transition metals in intermetallic compounds: ω1-Mn6Ga29 and its structuralrelationships

NASA Astrophysics Data System (ADS)

Antonyshyn, Iryna; Prots, Yurii; Margiolaki, Irene; Schmidt, Marcus Peter; Zhak, Olga; Oryshchyn, Stepan; Grin, Yuri

2013-03-01

The new phase ω1-Mn6Ga29 was synthesised in single-crystal form from the elements applying the high-temperature centrifugation-aided filtration technique. The crystal structure was determined using diffraction data collected from a twinned specimen: a new prototype, space group P1¯; a=6.3114(2) Å, b=9.9557(3) Å, c=18.920(1) Å, α=90.473(1)°, β=90.847(1)°, γ=90.396(1)°; R1=0.047, wR2=0.117 for 317 variable parameters and 7346 observed reflections; twinning matrix 0 0 -1/3, 0 -1 0, -3 0 0; twin domains ratio 0.830(3):0.170. All manganese atoms in the crystal structure of ω1-Mn6Ga29 are coordinated exclusively by Ga forming distorted tetragonal antiprisms. The monocapped [MnGa8+1] antiprisms condense into pairs by sharing their pseudo-quadratic faces and are interconnected via common apexes and edges to form a 3D framework. The relationship between the crystal structures of ω1-Mn6Ga29 and CuAl2, α-, β-CoSn3, PtSn4, Ti4MnBi2, PdGa5, Rh3Ga16, Rh4Ga21, Al7FeCu2, Co2Al9, and RhBi4 is discussed.

Structure functions in decomposing CuRh systems

NASA Astrophysics Data System (ADS)

Prem, M.; Blaschko, O.; Rosta, L.

1997-02-01

The time evolution of a CuRh alloy quenched within the miscibility gap is investigated by small and wide angle neutron scattering techniques. Near fundamental Bragg reflections diffuse satellites arising from a lattice parameter modulation induced by the precipitation pattern are investigated. The results show that in CuRh the precipitation morphology and its time evolution are quite different from decomposition characteristics recently observed in the system AuPt. The results are discussed and related to the larger lattice misfit present in CuRh in comparison to AuPt.

GRAVIMETRIC DETERMINATION OF PLATINIUM, PALLADIUM, RUTHENIUM, RHODIUM AS TlPtS$sub 3$, TlPd$sub 2$S$sub 3$, TlRu$sub 2$S$sub 6$, TlRh$sub 2$S$sub 4$ (in Russian)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rudnev, N.A.; Malofeeva, G.I.

1963-07-01

Gravimetric methods were developed for the determination of microamounts of Ru, Rh, Pt, and Pd as TlRu/sub 2/S/sub 6/, TlRh/sub 2/S/sub 4/ TlPtS/sub 3/, and TlPd/sub 2/S/sub 3/. The methods are simpl e, rapid, and satisfactorily accurate. (auth)

Magmatic sulphides in Quaternary Ecuadorian arc magmas

NASA Astrophysics Data System (ADS)

Georgatou, Ariadni; Chiaradia, Massimo; Rezeau, Hervé; Wälle, Markus

2018-01-01

New petrographic and geochemical data on magmatic sulphide inclusions (MSIs) are presented and discussed for 15 Quaternary volcanic centers of the Ecuadorian frontal, main and back volcanic arc. MSIs occur mostly in Fe-Ti oxides (magnetite and/or magnetite-ilmenite pair) and to a lesser extent in silicate minerals (amphibole, plagioclase, and pyroxene). MSIs are present in all volcanic centers ranging in composition from basalt to dacite (SiO2 = 50-67 wt.%), indicating that sulphide saturation occurs at various stages of magmatic evolution and independently from the volcano location along the volcanic arc. MSIs also occur in dioritic, gabbroic and hornblenditic magmatic enclaves of the volcanic rocks. MSIs display variable sizes (1-30 μm) and shapes (globular, ellipsoidal, angular, irregular) and occur mostly as polymineralic inclusions composed of Fe-rich and Cu-poor (pyrrhotite) and Cu-rich (mostly chalcopyrite) phases. Aerial sulphide relative abundances range from 0.3 to 7 ppm in volcanic host rocks and from 13 to 24 ppm in magmatic enclaves. Electron microprobe analyses of MSIs indicate maximum metal contents of Cu = 65.7 wt.%, Fe = 65.2 wt.%, Ni = 10.1 wt.% for those hosted in the volcanic rocks and of Cu = 57.7 wt.%, Fe = 60.9 wt.%, Ni = 5.1 wt.%, for those hosted in magmatic enclaves. Relationships of the sulphide chemistry to the host whole rock chemistry show that with magmatic differentiation (e.g., increasing SiO2) the Cu and Ni content of sulphides decrease whereas the Fe and S contents increase. The opposite behavior is observed with the increase of Cu in the whole rock, because the latter is anti-correlated with the SiO2 whole rock content. Laser ablation ICP-MS analyses of MSIs returned maximum values of PGEs and noble metals of Pd = 30 ppm, Rh = 8.1 ppm, Ag = 92.8 ppm and Au = 0.6 ppm and Pd = 43 ppm, Rh = 22.6 ppm, Ag = 89 ppm and Au = 1 ppm for those hosted in volcanic rocks and magmatic enclaves, respectively. These PGE contents display a different range of values with respect to those in previously investigated magmatic sulphides. MSIs that are Cu- and PGE/Cu-rich are found in less evolved rocks (i.e., lower SiO2 contents) that also display a lower amount of sulphide inclusions. Cu-rich sulphide phases (chalcopyrite ± bornite) are mostly hosted by magnetite, whereas PGE-rich ones consist of a Cu-poor phase (pyrrhotite) hosted by plagioclase. However, no systematic changes in the chemistry of the host silicate mineral are observed in coincidence with the occurrence of MSIs. We use the results of our study to draw some implications on Cu (and other chalcophile elements) behavior during arc magmatic processes potentially associated with the formation of porphyry-type deposits.

Methods of reforming hydrocarbon fuels using hexaaluminate catalysts

DOEpatents

Gardner, Todd H [Morgantown, WV; Berry, David A [Morgantown, WV; Shekhawat, Dushyant [Morgantown, WV

2012-03-27

A metal substituted hexaaluminate catalyst for reforming hydrocarbon fuels to synthesis gas of the general formula AB.sub.yAl.sub.12-yO.sub.19-.delta., A being selected from alkali metals, alkaline earth metals and lanthanide metals or mixtures thereof. A dopant or surface modifier selected from a transitions metal, a spinel of an oxygen-ion conductor is incorporated. The dopant may be Ca, Cs, K, La, Sr, Ba, Li, Mg, Ce, Co, Fe, Ir, Rh, Ni, Ru, Cu, Pe, Os, Pd, Cr, Mn, W, Re, Sn, Gd, V, Ti, Ag, Au, and mixtures thereof. The oxygen-ion conductor may be a perovskite selected from M'RhO.sub.3, M'PtO.sub.3, M'PdO.sub.3, M'IrO.sub.3, M'RuO.sub.3 wherein M'=Mg, Sr, Ba, La, Ca; a spinel selected from MRh.sub.2O.sub.4, MPt.sub.2O.sub.4, MPd.sub.2O.sub.4, MIr.sub.2O.sub.4, MRu.sub.2O.sub.4 wherein M=Mg, Sr, Ba, La, Ca and mixtures thereof; a florite is selected from M''O.sub.2.

High-throughput screening of small-molecule adsorption in MOF-74

NASA Astrophysics Data System (ADS)

Thonhauser, T.; Canepa, P.

2014-03-01

Using high-throughput screening coupled with state-of-the-art van der Waals density functional theory, we investigate the adsorption properties of four important molecules, H2, CO2, CH4, and H2O in MOF-74-  with  = Be, Mg, Al, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Sr, Zr, Nb, Ru, Rh, Pd, La, W, Os, Ir, and Pt. We show that high-throughput techniques can aid in speeding up the development and refinement of effective materials for hydrogen storage, carbon capture, and gas separation. The exploration of the configurational adsorption space allows us to extract crucial information concerning, for example, the competition of water with CO2 for the adsorption binding sites. We find that only a few noble metals--Rh, Pd, Os, Ir, and Pt--favor the adsorption of CO2 and hence are potential candidates for effective carbon-capture materials. Our findings further reveal significant differences in the binding characteristics of H2, CO2, CH4, and H2O within the MOF structure, indicating that molecular blends can be successfully separated by these nano-porous materials. Supported by DOE DE-FG02-08ER46491.

Fast and direct screening of copper in micro-volumes of distilled alcoholic beverages by high-resolution continuum source graphite furnace atomic absorption spectrometry.

PubMed

Ajtony, Zsolt; Laczai, Nikoletta; Dravecz, Gabriella; Szoboszlai, Norbert; Marosi, Áron; Marlok, Bence; Streli, Christina; Bencs, László

2016-12-15

HR-CS-GFAAS methods were developed for the fast determination of Cu in domestic and commercially available Hungarian distilled alcoholic beverages (called pálinka), in order to decide if their Cu content exceeds the permissible limit, as legislated by the WHO. Some microliters of samples were directly dispensed into the atomizer. Graphite furnace heating programs, effects/amounts of the Pd modifier, alternative wavelengths (e.g., Cu I 249.2146nm), external calibration and internal standardization methods were studied. Applying a fast graphite furnace heating program without any chemical modifier, the Cu content of a sample could be quantitated within 1.5min. The detection limit of the method is 0.03mg/L. Calibration curves are linear up to 10-15mg/L Cu. Spike-recoveries ranged from 89% to 119% with an average of 100.9±8.5%. Internal calibration could be applied with the assistance of Cr, Fe, and/or Rh standards. The accuracy of the GFAAS results was verified by TXRF analyses. Copyright © 2016 Elsevier Ltd. All rights reserved.

The behavior of Pt, Pd, Cu and Ni in the Se-sulfide system between 1050 and 700 °C and the role of Se in platinum-group elements fractionation in sulfide melts

NASA Astrophysics Data System (ADS)

Helmy, Hassan M.; Fonseca, Raúl O. C.

2017-11-01

The behavior of Pt, Pd, Ni and Cu in Se-sulfide system and the role of Se in platinum-group elements (PGE) fractionation have been experimentally investigated at temperatures between 1050 and 700 °C in evacuated silica tubes. At 1050 °C, Se partially partitions into a vapor phase. At 980 °C, monosulfide solid solution (mss) and sulfide melt are the only stable phases. No Pt or Pd-bearing discrete selenide phases form down to 700 °C. Instead cooperite (PtS) forms at 900 °C. Both mss and sulfide melt can accommodate wt.% levels of Se over the whole temperature range covered by the experiments. The addition of Se in the sulfide system leads to an increase in the activity coefficients of Ni and Pd in sulfide melt. This is reflected by an increase in the partition coefficients of Ni and Pd between mss and sulfide melt. The Pt-Se activity coefficient in sulfide melt is lower than that of Pt-S. Owing to selenium's high solubility in sulfides, there never become oversaturated in Se to the extent that discrete selenides form. As such, base metal sulfides are expected to control the geochemical behavior of Se in natural systems. Interestingly, partition coefficients for the platinum-group elements (Os, Ir, Ru, Pt, Rh, Pd) between mss and sulfide melt are undistinguishable regardless of whether Se is present or not. These results imply that Se plays little role in the fractionation of PGE as sulfide melt cools down and crystallize. Furthermore, our experimental results provide evidence that Se is volatile at magmatic temperature and is likely to be degassed like sulfur.

High-temperature stability of Au/Pd/Cu and Au/Pd(P)/Cu surface finishes

NASA Astrophysics Data System (ADS)

Ho, C. E.; Hsieh, W. Z.; Lee, P. T.; Huang, Y. H.; Kuo, T. T.

2018-03-01

Thermal reliability of Au/Pd/Cu and Au/Pd(4-6 wt.% P)/Cu trilayers in the isothermal annealing at 180 °C were investigated by X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (TOF-SIMS), and transmission electron microscopy (TEM). The pure Pd film possessed a nanocrystalline structure with numerous grain boundaries, thereby facilitating the interdiffusion between Au and Cu. Out-diffusion of Cu through Pd and Au grain boundaries yielded a significant amount of Cu oxides (CuO and Cu2O) over the Au surface and gave rise to void formation in the Cu film. By contrast, the Pd(P) film was amorphous and served as a good diffusion barrier against Cu diffusion. The results of this study indicated that amorphous Pd(P) possessed better oxidation resistance and thermal reliability than crystalline Pd.

Effects of Pd substitution on the thermoelectric and electronic properties of delafossite Cu{sub 1−x}Pd{sub x}FeO{sub 2} (x=0.01, 0.03 and 0.05)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ruttanapun, Chesta, E-mail: chesta.ruttanapun@gmail.com

Cu{sub (1−x)}Pd{sub (x)}FeO{sub 2} (x=0.01, 0.03 and 005) delafossite was prepared by solid state reactions and was calcined/sintered at 1050 °C. The effect of Pd{sup 2+} substitution for the Cu{sup 1+} sites on the thermoelectric and electronic properties of Cu{sub (1−x)}Pd{sub (x)}FeO{sub 2} were investigated. The crystal structure, oxygen decomposition, thermoelectric and electronic properties were characterized by X-ray diffraction, thermogravimetric analysis, X-ray photoelectron spectroscopy (XPS), Seebeck coefficient, electrical conductivity and thermal conductivity measurements. The characterization showed that Cu{sub (1−x)}Pd{sub (x)}FeO{sub 2} formed a hexagonal delafossite structure with R3−m symmetry. The existence of Pd{sup 2+}, Cu{sup 1+}, Cu{sup 2+}, Fe{sup 3+},more » Fe{sup 4+} and O was revealed from the XPS results. Confirmation of Pd{sup 2+} substitution for the Cu{sup 1+} sites occurred by increasing the c-axis in the lattice parameter with a Pd content. The O content intercalated at the center of the triangular Cu acted as a support to produce Cu{sup 2+} ions and was reduced with an increasing Pd content. The mixed valencies of Cu{sup 1+}/Cu{sup 2+} and Cu{sup 1+}/Pd{sup 2+} in the Cu layer changed the electrical conductivity and the Fe{sup 3+}/Fe{sup 4+} mixed valencies in the FeO{sub 6} layer caused the Seebeck coefficient to increase. Both the electrical conductivity and Seebeck coefficient for Pd contents of x=0.01 and 0.03 were higher than that of non-doped CuFeO{sub 2}. The low thermal conductivity of Cu{sub (1−x)}Pd{sub (x)}FeO{sub 2} resulted from the substitution of Pd, which has a large atomic mass, into structure. The Jonker plot indicated that the electronic properties displayed a degenerate density of states and that Cu{sub (1−x)}Pd{sub (x)}FeO{sub 2} was a semiconductor. A high ZT value of 0.055 was obtained for a Pd content of 0.03 at 950 K. The Pd{sup 2+} substitution for the Cu{sup 1+} sites influenced the thermoelectric and electronic properties of the delafossite Cu{sub (1−x)}Pd{sub (x)}FeO{sub 2} samples. - Graphical abstract: Cu{sub (1−x)}Pd{sub (x)}FeO{sub 2} (x=0.01, 0.03 and 005) delafossite was prepared by solid state reactions. The characterization showed that Cu{sub (1−x)}Pd{sub (x)}FeO{sub 2} formed a hexagonal delafossite structure with R3−m symmetry. The existence of Pd{sup 2+}, Cu{sup 1+}, Cu{sup 2+}, Fe{sup 3+}, Fe{sup 4+} and O was revealed from the XPS results. The O content intercalated at the center of the triangular Cu acted as a support to produce Cu{sup 2+} ions and was reduced with an increasing Pd content. The mixed valencies of Cu{sup 1+}/Cu{sup 2+} and Cu{sup 1+}/Pd{sup 2+} in the Cu layer changed the electrical conductivity and the Fe{sup 3+}/Fe{sup 4+} mixed valencies in the FeO{sub 6} layer caused the Seebeck coefficient to increase. Both the electrical conductivity and Seebeck coefficient for Pd contents of x=0.01 and 0.03 were higher than that of non-doped CuFeO{sub 2}. The low thermal conductivity of Cu{sub (1−x)}Pd{sub (x)}FeO{sub 2} resulted from the substitution of Pd, which has a large atomic mass, into structure. A high ZT value of 0.055 was obtained for a Pd content of 0.03 at 950 K. The Pd{sup 2+} substitution for the Cu{sup 1+} sites influenced the thermoelectric and electronic properties of the delafossite Cu{sub (1−x)}Pd{sub (x)}FeO{sub 2} samples. - Highlights: • New compound of Cu{sub 1−x}Pd{sub x}FeO{sub 2} (x=0.01, 0.03 and 0.05) forms phase of delafossite. • The compound displays p-type thermoelectric materials. • The Pd-substituted for Cu{sup 1+} sites forms Pd{sup 2+}. • Mixed valencies of Cu{sup +}/Cu{sup 2+}, Cu{sup +}/Pd{sup 2+} and Fe{sup 3+}/Fe{sup 4+} appear in the compound. • Large atomic mass of Pd-substituted causes low thermal conductivity.« less

Toxicity of platinum, palladium and rhodium to Daphnia magna in single and binary metal exposure experiments.

PubMed

Zimmermann, Sonja; Wolff, Carolina; Sures, Bernd

2017-05-01

Mainly due to automobile traffic, but also due to other sources, the platinum group elements (PGE) platinum (Pt), palladium (Pd) and rhodium (Rh) are introduced into aquatic biotopes where they accumulate in sediments of lakes and rivers. However, the toxicity of these noble metals to aquatic organisms is not well understood and especially toxicity studies under standardized condition are lacking. Thus, the toxicity of Pt, Pd and Rh to Daphnia magna was tested in single metal exposure experiments according to OECD guideline 202. Immobility and lethality was recorded after 24 h and 48 h of exposure and EC 50 and LC 50 , respectively, were determined. As the nominal exposure concentration of Pd differed significantly from the quantified concentration, the control of the real exposure concentration by chemical analysis is mandatory, especially for Pd. The toxicity decreased in the order Pd > Pt ≫ Rh with e.g. LC 50 (48 h) values of 14 μg/L for Pd, 157 μg/L for Pt and 56,800 μg/L for Rh. The exposure period had a clear effect on the toxicity of Pt, Pd and Rh. For Pt and Rh the endpoint immobility was more sensitive than the endpoint lethality whereas Pd toxicity was similar for both endpoints. The Hill slopes, which are a measure for the steepness of the concentration-response curves, showed no significant discrepancies between the different metals. The binary metal exposure to Pt and Pd revealed a more-than-additive, i.e. a synergistic toxicity using the toxic unit approach. The present study is a start to understand the toxicity of interacting PGE. The modes of action behind the synergistic effect are unclear. Copyright © 2017 Elsevier Ltd. All rights reserved.

A first-principles study on the interaction of biogas with noble metal (Rh, Pt, Pd) decorated nitrogen doped graphene as a gas sensor: A DFT study

NASA Astrophysics Data System (ADS)

Zhao, Chunjiang; Wu, Huarui

2018-03-01

Density functional theory calculations are carried out to investigate the adsorption characteristics of methane (CH4), carbon dioxide (CO2), hydrogen (H2), hydrogen sulfide (H2S), nitrogen (N2), and oxygen (O2) on the surface of pyridine-like nitrogen doped graphene (PNG) as well as noble metal (Rh, Pt, Pd) decorated PNG to elaborate their potentials as gas sensors. The adsorption intensities of biogas on noble metal (Rh, Pt, Pd) decorated PNG are in the order of O2> H2S> N2> CH4> CO2> H2, which are corresponded to the order of their sensitivity on surface. Compared with biogas adsorption on pristine PNG, there exist higher adsorption ability, higher charge transfer and higher orbital hybridization upon adsorption on noble metal (Rh, Pt, Pd) decorated PNG. Consequently, the noble metal (Rh, Pt, Pd) decorated PNG can transform the existence of CH4, CO2, H2, H2S, N2, and O2 molecules into electrical signal and they could potentially be used as ideal sensors for detection of biogas in ambient situation.

Stabilizing CuPd Nanoparticles via CuPd Coupling to WO 2.72 Nanorods in Electrochemical Oxidation of Formic Acid

DOE PAGES

Xi, Zheng; Li, Junrui; Su, Dong; ...

2017-10-05

Stabilizing a 3d-transition metal component M from an MPd alloy structure in an acidic environment is key to the enhancement of MPd catalysis for various reactions. Here we show a strategy to stabilize Cu in 5 nm CuPd nanoparticles (NPs) by coupling the CuPd NPs with perovskite-type WO 2.72 nanorods (NRs). The CuPd NPs are prepared by controlled diffusion of Cu into Pd NPs and the coupled CuPd/WO 2.72 are synthesized by growing WO 2.72 NRs in the presence of CuPd NPs. The CuPd/WO 2.72 can stabilize Cu in 0.1 M HClO4 solution and, as a result, they show Cu,more » Pd composition dependent activity for the electrochemical oxidation of formic acid in 0.1 M HClO 4 + 0.1 M HCOOH. Among three different CuPd/WO 2.72 studied, the Cu 48Pd 52/WO 2.72 is the most efficient catalyst with its mass activity reaching 2086 mA/mgPd in a broad potential range of 0.40 to 0.80 V (vs. RHE) and staying at this value after the 12 h chronoamperometry test at 0.40 V. The synthesis can be extended to obtain other MPd/WO 2.72 (M = Fe, Co, Ni), making it possible to study MPd-WO 2.72 interactions and MPd stabilization on enhancing MPd catalysis for various chemical reactions.« less

A density functional theory study of self-regenerating catalysts LaFe(1-x)M(x)O(3-y) (M = Pd, Rh, Pt).

PubMed

Hamada, Ikutaro; Uozumi, Akifumi; Morikawa, Yoshitada; Yanase, Akira; Katayama-Yoshida, Hiroshi

2011-11-23

Periodic density functional theory was used to investigate the stability and electronic structures of precious-metal atoms in the vicinity of LaFe(1-x)M(x)O(3) (M = Pd, Rh, Pt) perovskite catalyst surfaces. It was found that the surface segregation of Pd and Pt is significantly stabilized by the introduction of O vacancies, whereas the solid-solution phase is favorable for Rh, suggesting an important role of O vacancies in the self-regeneration of Pd and Pt. On the basis of the results, we propose a possible scenario for the self-regeneration of the precious metal in the perovskite catalyst.

Nanoamorphous carbon-based photonic crystal infrared emitters

DOEpatents

Norwood, Robert A [Tucson, AZ; Skotheim, Terje [Tucson, AZ

2011-12-13

Provided is a tunable radiation emitting structure comprising: a nanoamorphous carbon structure having a plurality of relief features provided in a periodic spatial configuration, wherein the relief features are separated from each other by adjacent recessed features, and wherein the nanoamorphous carbon comprises a total of from 0 to 60 atomic percent of one or more dopants of the dopant group consisting of: transition metals, lanthanoids, electro-conductive carbides, silicides and nitrides. In one embodiment, a dopant is selected from the group consisting of: Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, La and other lanthanides, Hf, Ta, W, Rh, Os, Ir, Pt, Au, and Hg. In one embodiment, a dopant is selected from the group consisting of: electro-conductive carbides (like Mo.sub.2C), silicides (like MoSi.sub.2) and nitrides (like TiN).

Site Preference of Ternary Alloying Additions to AuTi

NASA Technical Reports Server (NTRS)

Bozzolo, Guillermo; Mosca, Hugo O.; Noebe, Ronald D.

2006-01-01

Atomistic modeling of the site substitution behavior of several alloying additions, namely. Na, Mg, Al, Si. Sc, V, Cr, Mn. Fe, Co, Ni, Cu, Zn, Y, Zr. Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Hf, Ta, W, Re, Os, Ir, and Pt in B2 TiAu is reported. The 30 elements can be grouped according to their absolute preference for a specific site, regardless of concentration, or preference for available sites in the deficient sublattice. Results of large scale simulations are also presented, distinguishing between additions that remain in solution from those that precipitate a second phase.

Nano sponge Mn₂O ₃ as a new adsorbent for the preconcentration of Pd(II) and Rh(III) ions in sea water, wastewater, rock, street sediment and catalytic converter samples prior to FAAS determinations.

PubMed

Yavuz, Emre; Tokalıoğlu, Serife; Sahan, Halil; Patat, Saban

2014-10-01

In this study, a nano sponge Mn2O3 adsorbent was synthesized and was used for the first time. Various parameters affecting the recovery values of Pd(II) and Rh(III) were examined. The tolerance limits (≥ 90 %) for both Pd(II) and Rh(III) ions were found to be 75,000 mg L(-1) Na(I), 75,000 mg L(-1) K(I), 50,000 mg L(-1) Mg(II) and 50,000 mg L(-1) Ca(II). A 30s contact time was enough for both adsorption and elution. A preconcentration factor of 100 was obtained by using 100mg of the nano sponge Mn2O3. The reusability of the adsorbent was 120 times. Adsorption capacities for Pd(II) and Rh(III) were found to be 42 and 6.2 mg g(-1), respectively. The detection limits were 1.0 µg L(-1) for Pd(II) and 0.37 µg L(-1) for Rh(III) and the relative standard deviations (RSD, %) were found to be ≤ 2.5%. The method was validated by analyzing the standard reference material, SRM 2556 (Used Auto Catalyst Pellets) and spiked real samples. The optimized method was applied for the preconcentration of Pd(II) and Rh(III) ions in water (sea water and wastewater), rock, street sediment and catalytic converter samples. Copyright © 2014 Elsevier B.V. All rights reserved.

Facile Aqueous Phase Synthesis of Pd3Cu-B/C Nanocatalyst for Glucose Electrooxidation

NASA Astrophysics Data System (ADS)

Chai, Dan; Lu, Haibin; Wang, Yaqian; Hua, Xiuwen; Ren, Na; Zhang, Xiongwen

2018-01-01

A novel Pd3Cu-B/C nanocatalyst was facilely synthesized through an aqueous phase process. And it was developed for use in the glucose electrooxidation reaction in fuel cells. Cyclic voltammetry shown that the electrochemical surface area of Pd3Cu-B/C is 2.25 times that of Pd/C. Glucose electrooxidation curves revealed that peak current on the Pd3Cu-B/C is actually 1.73 times of the Pd/C. This high performance of Pd3Cu-B/C could be ascribed to the synergistic effect between Pd, Cu and B.

Systematics of the temperature-dependent interplane resistivity in Ba(Fe 1-xM x)₂As₂ (M=Co, Rh, Ni, and Pd)

DOE PAGES

Tanatar, M. A.; Ni, N.; Thaler, A.; ...

2011-07-27

Temperature-dependent interplane resistivity ρ c(T) was measured systematically as a function of transition-metal substitution in the iron-arsenide superconductors Ba(Fe 1-xM x)₂As₂, M=Ni, Pd, Rh. The data are compared with the behavior found in Ba(Fe 1-xCo x)₂As₂, revealing resistive signatures of pseudogap. In all compounds we find resistivity crossover at a characteristic pseudogap temperature T* from nonmetallic to metallic temperature dependence on cooling. Suppression of T* proceeds very similarly in cases of Ni and Pd doping and much faster than in similar cases of Co and Rh doping. In cases of Co and Rh doping an additional minimum in the temperature-dependentmore » ρ c emerges for high dopings, when superconductivity is completely suppressed. These features are consistent with the existence of a charge gap covering part of the Fermi surface. The part of the Fermi surface affected by this gap is notably larger for Ni- and Pd-doped compositions than in Co- and Rh-doped compounds.« less

Palladium, platinum, rhodium, iridium and ruthenium in chromite- rich rocks from the Samail ophiolite, Oman.

USGS Publications Warehouse

Page, N.J.; Pallister, J.S.; Brown, M.A.; Smewing, J.D.; Haffty, J.

1982-01-01

30 samples of chromitite and chromite-rich rocks from two stratigraphic sections, 250 km apart, through the basal ultramafic member of the Samail ophiolite were spectrographically analysed for platinum-group elements (PGE) and for Co, Cu, Ni and V. These data are reported as are Cr/(Cr + Al), Mg/(Mg + Fe) and wt.% TiO2 for most samples. The chromitite occurs as pods or lenses in rocks of mantle origin or as discontinuous layers at the base of the overlying cumulus sequence. PGE abundances in both sections are similar, with average contents in chromite-rich rocks: Pd 8 ppb, Pt 14 ppb, Rh 6 ppb, Ir 48 ppb and Ru 135 ppb. The PGE data, combined with major-element and petrographic data on the chromitite, suggest: 1) relatively larger Ir and Ru contents and highest total PGE in the middle part of each section; 2) PGE concentrations and ratios do not correlate with coexisting silicate and chromite abundances or chromite compositions; 3) Pd/PGE, on average, increases upward in each section; 4) Samail PGE concentrations, particularly Rh, Pt and Pd, are lower than the average values for chromite-rich rocks in stratiform intrusions. 2) suggests that PGEs occur in discrete alloy or sulphide phases rather than in the major oxides or silicates, and 4) suggests that chromite-rich rocks from the oceanic upper mantle are depleted in PGE with respect to chondrites. L.C.C.

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

PubMed

Wang, Fagen; Zhang, Haojie; He, Dannong

2014-01-01

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

A two step method to synthesize palladium-copper nanoparticles on reduced graphene oxide and their extremely high electrocatalytic activity for the electrooxidation of methanol and ethanol

NASA Astrophysics Data System (ADS)

Na, HeYa; Zhang, Lei; Qiu, HaiXia; Wu, Tao; Chen, MingXi; Yang, Nian; Li, LingZhi; Xing, FuBao; Gao, JianPing

2015-08-01

Palladium-copper nanoparticles (Pd-Cu NPs) supported on reduced graphene oxide (RGO) with different Pd/Cu ratios (Pd-Cu/RGO) were prepared by a two step method. The Pd-Cu/RGO hybrids were characterized by transmission electron microscopy, X-ray photoelectron spectroscopy, X-ray diffraction and thermogravimetric analyses. Cyclic voltammetry and chronoamperometry were used to investigate the electrochemical activities and stabilities of the Pd-Cu/RGO catalysts for the electro-oxidation of methanol and ethanol in alkaline media. The Pd-Cu/RGO catalysts exhibited high catalytic activities and good stabilities. This is because the catalysts have a bimetallic structure consisting of a small Pd-Cu core surrounded by a thin Pd-rich shell which improves the catalytic activities of the Pd-Cu/RGO hybrids. Thus they should be useful in direct methanol and ethanol fuel cells.

Ordered PdCu-Based Nanoparticles as Bifunctional Oxygen-Reduction and Ethanol-Oxidation Electrocatalysts

DOE PAGES

Jiang, Kezhu; Wang, Pengtang; Guo, Shaojun; ...

2016-06-02

Here, the development of superior non-platinum electrocatalysts for enhancing the electrocatalytic activity and stability for the oxygen-reduction reaction (ORR) and liquid fuel oxidation reaction is very important for the commercialization of fuel cells,but still agreat challenge.Herein, we demonstrate a new colloidal chemistry technique for making structurally ordered PdCu-based nanoparticles (NPs) with composition control from PdCu to PdCuNi and PtCuCo.Under the dual tuning on the composition and intermetallic phase,the ordered PdCuCo NPs exhibit better activity and much enhanced stability for ORR and ethanol-oxidation reaction (EOR)than those of disordered PdCuM NPs,the commercial Pt/Cand Pd/C catalysts.The density functional theory (DFT)calculations reveal that themore » improved ORR activity on the PdCuM NPs stems from the catalytically active hollow sites arising from the ligand effect and the compressive strain on thePd surface owing to the smaller atomic size of Cu, Co,and Ni.« less

Comparative Reliability Studies and Analysis of Au, Pd-Coated Cu and Pd-Doped Cu Wire in Microelectronics Packaging

PubMed Central

Chong Leong, Gan; Uda, Hashim

2013-01-01

This paper compares and discusses the wearout reliability and analysis of Gold (Au), Palladium (Pd) coated Cu and Pd-doped Cu wires used in fineline Ball Grid Array (BGA) package. Intermetallic compound (IMC) thickness measurement has been carried out to estimate the coefficient of diffusion (Do) under various aging conditions of different bonding wires. Wire pull and ball bond shear strengths have been analyzed and we found smaller variation in Pd-doped Cu wire compared to Au and Pd-doped Cu wire. Au bonds were identified to have faster IMC formation, compared to slower IMC growth of Cu. The obtained weibull slope, β of three bonding wires are greater than 1.0 and belong to wearout reliability data point. Pd-doped Cu wire exhibits larger time-to-failure and cycles-to-failure in both wearout reliability tests in Highly Accelerated Temperature and Humidity (HAST) and Temperature Cycling (TC) tests. This proves Pd-doped Cu wire has a greater potential and higher reliability margin compared to Au and Pd-coated Cu wires. PMID:24244344

Stabilization of Pt monolayer catalysts under harsh conditions of fuel cells

DOE PAGES

Zhang, Xiaoming; Liu, Ping; Yu, Shansheng; ...

2015-05-21

We employed density functional theory (DFT) to explore the stability of core (M = Cu, Ru, Rh, Pd, Ag, Os, Ir, Au)-shell (Pt) catalysts under harsh conditions, including solutions and reaction intermediates involved in the oxygen reduction reaction (ORR) in fuel cells. A pseudomorphic surface alloy (PSA) with a Pt monolayer (Pt 1ML) supported on an M surface, Pt 1ML/M(111) or (001), was considered as a model system. Different sets of candidate M cores were identified to achieve a stable Pt 1ML shell depending on the conditions. In vacuum conditions, the Pt 1ML shell can be stabilized on the mostmore » of M cores except Cu, Ag, and Au. The situation varies under various electrochemical conditions. Depending on the solutions and the operating reaction pathways of the ORR, different M should be considered. Pd and Ir are the only core metals studied, being able to keep the Pt ML shell intact in perchloric acid, sulfuric acid, phosphoric acid, and alkaline solutions as well as under the ORR conditions via different pathways. Ru and Os cores should also be paid attention, which only fall during the ORR via the *OOH intermediate. Rh core works well as long as the ORR does not undergo the pathway via *O intermediate. Our results show that PSAs can behave differently from the near surface alloy, Pt 1ML/M 1ML/Pt(111), highlighting the importance of considering both chemical environments and the atomic structures in rational design of highly stable core-shell nanocatalysts. Finally, the roles that d-band center of a core M played in determining the stability of supported Pt 1ML shell were also discussed.« less

Stabilization of Pt monolayer catalysts under harsh conditions of fuel cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Xiaoming; Yu, Shansheng; Zheng, Weitao, E-mail: wtzheng@jlu.edu.cn, E-mail: pingliu3@bnl.gov

2015-05-21

We employed density functional theory to explore the stability of core (M = Cu, Ru, Rh, Pd, Ag, Os, Ir, Au)-shell (Pt) catalysts under harsh conditions, including solutions and reaction intermediates involved in the oxygen reduction reaction (ORR) in fuel cells. A pseudomorphic surface alloy (PSA) with a Pt monolayer (Pt{sub 1ML}) supported on an M surface, Pt{sub 1ML}/M(111) or (001), was considered as a model system. Different sets of candidate M cores were identified to achieve a stable Pt{sub 1ML} shell depending on the conditions. In vacuum conditions, the Pt{sub 1ML} shell can be stabilized on the most ofmore » M cores except Cu, Ag, and Au. The situation varies under various electrochemical conditions. Depending on the solutions and the operating reaction pathways of the ORR, different M should be considered. Pd and Ir are the only core metals studied, being able to keep the Pt{sub ML} shell intact in perchloric acid, sulfuric acid, phosphoric acid, and alkaline solutions as well as under the ORR conditions via different pathways. Ru and Os cores should also be paid attention, which only fall during the ORR via the *OOH intermediate. Rh core works well as long as the ORR does not undergo the pathway via *O intermediate. Our results show that PSAs can behave differently from the near surface alloy, Pt{sub 1ML}/M{sub 1ML}/Pt(111), highlighting the importance of considering both chemical environments and the atomic structures in rational design of highly stable core-shell nanocatalysts. Finally, the roles that d-band center of a core M played in determining the stability of supported Pt{sub 1ML} shell were also discussed.« less

Safety and tolerability of intracerebroventricular PDGF-BB in Parkinson’s disease patients

PubMed Central

Paul, Gesine; Zachrisson, Olof; Varrone, Andrea; Almqvist, Per; Jerling, Markus; Lind, Göran; Rehncrona, Stig; Linderoth, Bengt; Bjartmarz, Hjalmar; Shafer, Lisa L.; Coffey, Robert; Svensson, Mikael; Mercer, Katarina Jansson; Forsberg, Anton; Halldin, Christer; Svenningsson, Per; Widner, Håkan; Frisén, Jonas; Pålhagen, Sven; Haegerstrand, Anders

2015-01-01

BACKGROUND. Recombinant human PDGF-BB (rhPDGF-BB) reduces Parkinsonian symptoms and increases dopamine transporter (DAT) binding in several animal models of Parkinson’s disease (PD). Effects of rhPDGF-BB are the result of proliferation of ventricular wall progenitor cells and reversed by blocking mitosis. Based on these restorative effects, we assessed the safety and tolerability of intracerebroventricular (i.c.v.) rhPDGF-BB administration in individuals with PD. METHODS. We conducted a double-blind, randomized, placebo-controlled phase I/IIa study at two clinical centers in Sweden. Twelve patients with moderate PD received rhPDGF-BB via an implanted drug infusion pump and an investigational i.c.v. catheter. Patients were assigned to a dose cohort (0.2, 1.5, or 5 μg rhPDGF-BB per day) and then randomized to active treatment or placebo (3:1) for a 12-day treatment period. The primary objective was to assess safety and tolerability of i.c.v.-delivered rhPDGF-BB. Secondary outcome assessments included several clinical rating scales and changes in DAT binding. The follow-up period was 85 days. RESULTS. All patients completed the study. There were no unresolved adverse events. Serious adverse events occurred in three patients; however, these were unrelated to rhPDGF-BB administration. Secondary outcome parameters did not show dose-dependent changes in clinical rating scales, but there was a positive effect on DAT binding in the right putamen. CONCLUSION. At all doses tested, i.c.v. administration of rhPDGF-BB was well tolerated. Results support further clinical development of rhPDGF-BB for patients with PD. TRIAL REGISTRATION. Clinical Trials.gov NCT00866502. FUNDING. Newron Sweden AB (former NeuroNova AB) and Swedish Governmental Agency for Innovation Systems (VINNOVA). PMID:25689258

Safety and tolerability of intracerebroventricular PDGF-BB in Parkinson's disease patients.

PubMed

Paul, Gesine; Zachrisson, Olof; Varrone, Andrea; Almqvist, Per; Jerling, Markus; Lind, Göran; Rehncrona, Stig; Linderoth, Bengt; Bjartmarz, Hjalmar; Shafer, Lisa L; Coffey, Robert; Svensson, Mikael; Mercer, Katarina Jansson; Forsberg, Anton; Halldin, Christer; Svenningsson, Per; Widner, Håkan; Frisén, Jonas; Pålhagen, Sven; Haegerstrand, Anders

2015-03-02

BACKGROUND. Recombinant human PDGF-BB (rhPDGF-BB) reduces Parkinsonian symptoms and increases dopamine transporter (DAT) binding in several animal models of Parkinson's disease (PD). Effects of rhPDGF-BB are the result of proliferation of ventricular wall progenitor cells and reversed by blocking mitosis. Based on these restorative effects, we assessed the safety and tolerability of intracerebroventricular (i.c.v.) rhPDGF-BB administration in individuals with PD. METHODS. We conducted a double-blind, randomized, placebo-controlled phase I/IIa study at two clinical centers in Sweden. Twelve patients with moderate PD received rhPDGF-BB via an implanted drug infusion pump and an investigational i.c.v. catheter. Patients were assigned to a dose cohort (0.2, 1.5, or 5 μg rhPDGF-BB per day) and then randomized to active treatment or placebo (3:1) for a 12-day treatment period. The primary objective was to assess safety and tolerability of i.c.v.-delivered rhPDGF-BB. Secondary outcome assessments included several clinical rating scales and changes in DAT binding. The follow-up period was 85 days. RESULTS. All patients completed the study. There were no unresolved adverse events. Serious adverse events occurred in three patients; however, these were unrelated to rhPDGF-BB administration. Secondary outcome parameters did not show dose-dependent changes in clinical rating scales, but there was a positive effect on DAT binding in the right putamen. CONCLUSION. At all doses tested, i.c.v. administration of rhPDGF-BB was well tolerated. Results support further clinical development of rhPDGF-BB for patients with PD. TRIAL REGISTRATION. Clinical Trials.gov NCT00866502. FUNDING. Newron Sweden AB (former NeuroNova AB) and Swedish Governmental Agency for Innovation Systems (VINNOVA).

Anthrobiogeochemical platinum, palladium and rhodium cycles of earth: Emerging environmental contamination

NASA Astrophysics Data System (ADS)

Mitra, Arijeet; Sen, Indra Sekhar

2017-11-01

Anthrobiogeochemical cycles have been a subject of scientific research for many decades as they are important for identifying possible sources, sinks, and pathways of an element in the environment. In this study, we quantified global cycles for the platinum group elements (PGE; platinum (Pt), palladium (Pd) and rhodium (Rh)). We quantified the stocks of Pt, Pd, and Rh in Earth's various reservoirs, such as the core, mantle, consolidated crust, biomass, seawater, unconsolidated sediments, and atmosphere, as well as coal and petroleum deposits. We further quantified their fluxes, both natural and anthropogenic, between each reservoir, by identifying the flows across the hydrosphere, geosphere, biosphere, atmosphere and anthroposphere, including from mining activities, fossil fuel and biomass burning, construction activities, soil erosion, human contributions to net primary productivity, riverine transport, aeolian dust movement, primary production, volcanic eruption, sea-salt spray, crustal subduction, crust formation at mid ocean ridges, PGE recovery from recycling processes, and cosmic dust inputs at the Earth's surface. Stocks of PGEs were quantified by multiplying the mass of the reservoir by the average Pt, Pd and Rh concentration in the reservoir, whereas Pt, Pd and Rh fluxes were calculated by multiplying the rate of mass movement across the reservoirs with the Pt, Pd and Rh concentrations of the material. Uncertainties were explicitly incorporated in stock and flow estimations through Monte Carlo simulations. Our calculations reveal that the total surficial anthropogenic Pt, Pd, and Rh mobilizations were greater than their corresponding natural surficial mobilizations. We show that crustal subduction and crustal formation is the most important natural flow and contributes 21-42% of total PGE mobilization. When Earth's surficial processes are considered, soil erosion is the dominant flow for Rh and Pt mobilization, comprising 33% and 13%, respectively, of the total mobilization on Earth's surface, whereas NPP dominates the natural Pd mobilization. On the other hand, mining activities, fossil fuel burning and automobile emissions are the most important anthropogenic flows. Therefore, our qualitative and quantitative assessment indicates that mining activities contribute almost 60-80% of the total anthropogenic flow on Earth, and crustal subduction and production dominates the total global PGE cycle.

Time-Resolved and Operando XAS Studies on Heterogeneous Catalysts - From the Gas Phase Towards Reactions in Supercritical Fluids

DOE Office of Scientific and Technical Information (OSTI.GOV)

Grunwaldt, Jan-Dierk; Baiker, Alfons

2007-02-02

x-ray absorption spectroscopy is a well-suited technique to uncover the structure of heterogeneous catalysts under reaction conditions. Different aspects of in situ cell design suitable for dynamic and catalytic studies are discussed. In addition, criteria are presented that allow estimating the influence external and internal mass transfer. Starting with studies on gas-solid reactions, including structure-activity relationships, this concept is extended to liquid-solid reactions, reactions at high pressure and in supercritical fluids. The following examples are discussed in more detail: partial oxidation of methane over Pt-Rh/Al2O3, reduction of a Cu/ZnO catalyst, alcohol oxidation over Bi-promoted Pd/Al2O3 in liquid phase and overmore » Pd/Al2O3 in supercritical CO2, and batch reactions (e.g. CO2-fixation over zinc-based catalysts)« less

Sc–Zr–Nb–Rh–Pd and Sc–Zr–Nb–Ta–Rh–Pd High-Entropy Alloy Superconductors on a CsCl-Type Lattice

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stolze, Karoline; Tao, Jing; von Rohr, Fabian O.

We have synthesized previously unreported High-Entropy Alloys (HEAs) in the pentanary (ScZrNb) 1-x[RhPd] x and hexanary (ScZrNbTa) 1-x[RhPd] x systems. The materials have CsCl-type structures and mixed site occupancies. Both HEAs are type-II superconductors with strongly varying critical temperatures (T cs) depending on the valence electron count (VEC); the T cs increase monotonically with decreasing VEC within each series, and do not follow the trends seen for either crystalline or amorphous transition metal superconductors. The (ScZrNb) 0.65[RhPd] 0.35 HEA with the highest T c, ~9.3 K, also exhibits the largest µ 0H c2(0) = 10.7 T. The pentanary and hexanarymore » HEAs have higher superconducting transition tempera-tures than their simple binary intermetallic relatives with the CsCl-type structure and a surprisingly ductile mechanical behavior. The presence of niobium, even at the 20% level, has a positive impact on the T c. Nevertheless, niobium-free (ScZr) 0.50[RhPd] 0.50, as mother-compound of both superconducting HEAs found here, is itself superconducting, proving that superconductivity is an intrinsic feature of the bulk material.« less

Sc–Zr–Nb–Rh–Pd and Sc–Zr–Nb–Ta–Rh–Pd High-Entropy Alloy Superconductors on a CsCl-Type Lattice

DOE PAGES

Stolze, Karoline; Tao, Jing; von Rohr, Fabian O.; ...

2018-01-17

We have synthesized previously unreported High-Entropy Alloys (HEAs) in the pentanary (ScZrNb) 1-x[RhPd] x and hexanary (ScZrNbTa) 1-x[RhPd] x systems. The materials have CsCl-type structures and mixed site occupancies. Both HEAs are type-II superconductors with strongly varying critical temperatures (T cs) depending on the valence electron count (VEC); the T cs increase monotonically with decreasing VEC within each series, and do not follow the trends seen for either crystalline or amorphous transition metal superconductors. The (ScZrNb) 0.65[RhPd] 0.35 HEA with the highest T c, ~9.3 K, also exhibits the largest µ 0H c2(0) = 10.7 T. The pentanary and hexanarymore » HEAs have higher superconducting transition tempera-tures than their simple binary intermetallic relatives with the CsCl-type structure and a surprisingly ductile mechanical behavior. The presence of niobium, even at the 20% level, has a positive impact on the T c. Nevertheless, niobium-free (ScZr) 0.50[RhPd] 0.50, as mother-compound of both superconducting HEAs found here, is itself superconducting, proving that superconductivity is an intrinsic feature of the bulk material.« less

Valence-Band Electronic Structures of High-Pressure-Phase PdF2-type Platinum-Group Metal Dioxides MO2 (M = Ru, Rh, Ir, and Pt)

NASA Astrophysics Data System (ADS)

Soda, Kazuo; Kobayashi, Daichi; Mizui, Tatsuya; Kato, Masahiko; Shirako, Yuichi; Niwa, Ken; Hasegawa, Masashi; Akaogi, Masaki; Kojitani, Hiroshi; Ikenaga, Eiji; Muro, Takayuki

2018-04-01

The valence-band electronic structures of high-pressure-phase PdF2-type (HP-PdF2-type) platinum-group metal dioxides MO2 (M = Ru, Rh, Ir, and Pt) were studied by synchrotron radiation photoelectron spectroscopy and first-principles calculations. The obtained photoelectron spectra for HP-PdF2-type RuO2, RhO2, and IrO2 agree well with the calculated valence-band densities of states (DOSs) for these compounds, indicating their metallic properties, whereas the DOS of HP-PdF2-type PtO2 (calculated in the presence and absence of spin-orbit interactions) predicts that this material may be metallic or semimetallic, which is inconsistent with the electric conductivity reported to date and the charging effect observed in current photoelectron measurements. Compared with the calculated results, the valence-band spectrum of PtO2 appears to have shifted toward the high-binding-energy side and reveals a gradual intensity decrease toward the Fermi energy EF, implying a semiconductor-like electronic structure. Spin-dependent calculations predict a ferromagnetic ground state with a magnetization of 0.475 μB per formula unit for HP-PdF2-type RhO2.

First principles study of surface stability and segregation of PdRuRh ternary metal alloy system

NASA Astrophysics Data System (ADS)

Aspera, Susan Meñez; Arevalo, Ryan Lacdao; Nakanishi, Hiroshi; Kasai, Hideaki

2018-05-01

The recognized importance on the studies of alloyed materials is due to the high possibility of forming designer materials that caters to different applications. In any reaction and application, the stability and configuration of the alloy combination are important. In this study, we analyzed the surface stability and segregation of ternary metal alloy system PdRuRh through first principles calculation using density functional theory (DFT). We considered the possibility of forming phases as observed in the binary combinations of elements, i.e., completely miscible, and separating phases. With that, the model we analyzed for the ternary metal alloy slabs considers forming complete atomic miscibility, segregation of each component, and segregation of one component with mixing of the two other. Our results show that for the ternary combination of Pd, Rh and Ru, the Pd atoms have high tendency to segregate at the surface, while due to the high tendency of Ru and Rh to mix, core formation of a mixed RuRh is possible. Also, we determined that the trend of stability in the binary alloy system is a good determinant of stability in the ternary alloy system.

Segregation at the surfaces of CuxPd1-x alloys in the presence of adsorbed S

DOE Office of Scientific and Technical Information (OSTI.GOV)

Miller, James B.; Priyadarshini, Deepika; Gellman, Andrew J.

2012-10-01

The influence of adsorbed S on surface segregation in Cu{sub x}Pd{sub 1 - x} alloys (S/Cu{sub x}Pd{sub 1 - x)} was characterized over a wide range of bulk alloy compositions (x = 0.05 to 0.95) using high-throughput Composition Spread Alloy Film (CSAF) sample libraries. Top-surface and near-surface compositions of the CSAFs were measured as functions of bulk Cu composition, x, and temperature using spatially resolved low energy ion scattering spectroscopy (LEISS) and X-ray photoemission spectroscopy (XPS). Preferential segregation of Cu to the top-surface of the S/Cu{sub x}Pd{sub 1 - x} CSAF was observed at all bulk compositions, x, but themore » extent of Cu segregation to the S/Cu{sub x}Pd{sub 1 - x} surface was lower than the Cu segregation to the surface of a clean Cu{sub x}Pd{sub 1 - x} CSAF, clear evidence of an S-induced “segregation reversal.” The Langmuir–McLean formulation of the Gibbs isotherm was used to estimate the enthalpy and entropy of Cu segregation to the top-surface, ΔH{sub seg}(x) and ΔS{sub seg}(x), at saturation sulfur coverages. While Cu segregation to the top-surface of the clean Cu{sub x}Pd{sub 1 - x} is exothermic (ΔH{sub seg} < 0) for all bulk Cu compositions, it is endothermic (ΔH{sub seg} > 0) for S/Cu{sub x}Pd{sub 1 - x}. Segregation to the S/Cu{sub x}Pd{sub 1 - x} surface is driven by entropy. Changes in segregation patterns that occur upon adsorption of S onto Cu{sub x}Pd{sub 1 - x} appear to be related to formation of energetically favored Pd{single bond}S bonds at the surface, which counterbalance the enthalpic driving forces for Cu segregation to the clean surface.« less

Wetting reaction of Sn-Ag based solder systems on Cu substrates plated with Au and/or Pd layer

NASA Astrophysics Data System (ADS)

Liu, C. Y.; Li, Jian; Vandentop, G. J.; Choi, W. J.; Tu, K. N.

2001-05-01

The wetting behavior of SnAg based Pb-free solders on Cu and Cu substrates plated with Au, Pd, and Au/Pd thin films have been studied. The wetting angle and kinetics of interfacial reaction were measured. The Au-plated substrates exhibit better wetting than the Pd-plated substrates. In the case of SnAg on Pd-plated Cu, SEM observation revealed that the solder cap was surrounded by an innerring of Cu-Sn compound and an outer ring of Pd-Sn compound. This implies that the molten SnAg solder had removed the Pd and wetted the Cu directly in the equilibrium state. The effects of pre-doping Cu in the SnAg solder on wetting behavior were also investigated. We found that wettability decreases with increasing Cu content in the solder. We also observed that the SnAgCu solders have a lower Cu consumption rate than the SnAg solder.

Assessment of trends in the electrochemical CO 2 reduction and H 2 evolution reactions on metal nanoparticles

DOE PAGES

Alfonso, Dominic R.; Kauffman, Douglas R.

2017-08-14

Here, we used density functional theory to investigate the electrochemical CO 2 reduction and competing hydrogen evolution reaction on model Au, Ag, Cu, Ir, Ni, Pd, Pt, and Rh nanoparticles. On the coinage metal, the free energy of adsorbed COOH, CO, and H intermediates generally becomes more favorable with decreasing particle size. This pattern was also observed on all transition metals with the binding of the intermediates observed to be stronger on almost all of these metals. Comparative studies of the reaction profile reveal that H 2 evolution is the first reaction to be energetically allowed at zero applied bias

Assessment of trends in the electrochemical CO 2 reduction and H 2 evolution reactions on metal nanoparticles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Alfonso, Dominic R.; Kauffman, Douglas R.

Here, we used density functional theory to investigate the electrochemical CO 2 reduction and competing hydrogen evolution reaction on model Au, Ag, Cu, Ir, Ni, Pd, Pt, and Rh nanoparticles. On the coinage metal, the free energy of adsorbed COOH, CO, and H intermediates generally becomes more favorable with decreasing particle size. This pattern was also observed on all transition metals with the binding of the intermediates observed to be stronger on almost all of these metals. Comparative studies of the reaction profile reveal that H 2 evolution is the first reaction to be energetically allowed at zero applied bias

Production of an ordered (B2) CuPd nanoalloy by low-temperature annealing under hydrogen atmosphere.

PubMed

Yamauchi, Miho; Tsukuda, Tatsuya

2011-05-14

CuPd (1/1) nanoalloys composed of disordered body-centered-cubic crystals (crystal size = 1.6 nm) were prepared by synchronous reduction of Cu and Pd precursor ions with NaBH(4). In situ XRD measurement revealed that Cu and Pd atoms in the CuPd nanoalloys are arranged into an ordered B2 structure under exposure to H(2) (5 kPa) at 373 K. Ordering of Cu and Pd atoms over a longer distance (up to 3.6 nm) was achieved by annealing the nanoalloys for a longer time under a H(2) atmosphere.

Potential of transition metal atoms embedded in buckled monolayer g-C3N4 as single-atom catalysts.

PubMed

Li, Shu-Long; Yin, Hui; Kan, Xiang; Gan, Li-Yong; Schwingenschlögl, Udo; Zhao, Yong

2017-11-15

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-C 3 N 4 as single-atom catalysts. We show that clustering of Sc and Ti on g-C 3 N 4 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-C 3 N 4 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-C 3 N 4 gives rise to promising single-atom catalysts at low temperature.

Density functional theory study of structural, electronic, and thermal properties of Pt, Pd, Rh, Ir, Os and PtPd X (X = Ir, Os, and Rh) alloys

NASA Astrophysics Data System (ADS)

Shabbir, Ahmed; Muhammad, Zafar; M, Shakil; M, A. Choudhary

2016-03-01

The structural, electronic, mechanical, and thermal properties of Pt, Pd, Rh, Ir, Os metals and their alloys PtPdX (X = Ir, Os and Rh) are studied systematically using ab initio density functional theory. The groundstate properties such as lattice constant and bulk modulus are calculated to find the equilibrium atomic position for stable alloys. The electronic band structure and density of states are calculated to study the electronic behavior of metals on making their alloys. The electronic properties substantiate the metallic behavior for all studied materials. The firstprinciples density functional perturbation theory as implemented in quasi-harmonic approximation is used for the calculations of thermal properties. We have calculated the thermal properties such as the Debye temperature, vibrational energy, entropy and constant-volume specific heat. The calculated properties are compared with the previously reported experimental and theoretical data for metals and are found to be in good agreement. Calculated results for alloys could not be compared because there is no data available in the literature with such alloy composition.

Multi-mode humidity sensing with water-soluble copper phthalocyanine for increased sensitivity and dynamic range

DOE Office of Scientific and Technical Information (OSTI.GOV)

Muckley, Eric S.; Jacobs, Christopher B.; Vidal, Keith

Aqueous solubility of copper phthalocyanine-3,4',4',4"'-tetrasulfonic acid tetrasodium salt (CuPcTs) enables fabrication of flexible electronic devices by low cost inkjet printing. We (1) investigate water adsorption kinetics on CuPcTs for better understanding the effects of relative humidity (RH) on hydrophilic phthalocyanines, and (2) assess CuPcTs as a humidity-sensing material. Reaction models show that H 2O undergoes 2-site adsorption which can be represented by a pair of sequentially-occurring pseudo-first order reactions. Using high frequency (300–700 THz) and low frequency (1–8 MHz) dielectric spectroscopy combined with gravimetric measurements and principal component analysis, we observe that significant opto-electrical changes in CuPcTs occur at RHmore » ≈ 60%. The results suggest that rapid H 2O adsorption takes place at hydrophilic sulfonyl/salt groups on domain surfaces at low RH, while slow adsorption and diffusion of H 2O into CuPcTs crystallites leads to a mixed CuPcTs-H 2O phase at RH > 60%, resulting in high frequency dielectric screening of the film by water and dissociation of Na+ from CuPc(SO 3-) 4 ions. Lastly, the CuPcTs-H 2O interaction can be tracked using a combination of gravimetric, optical, and electrical sensing modes, enabling accurate ( ± 2.5%) sensing in the ~0–95% RH range with a detection limit of less than 0.1% RH.« less

Multi-mode humidity sensing with water-soluble copper phthalocyanine for increased sensitivity and dynamic range

DOE PAGES

Muckley, Eric S.; Jacobs, Christopher B.; Vidal, Keith; ...

2017-08-30

Aqueous solubility of copper phthalocyanine-3,4',4',4"'-tetrasulfonic acid tetrasodium salt (CuPcTs) enables fabrication of flexible electronic devices by low cost inkjet printing. We (1) investigate water adsorption kinetics on CuPcTs for better understanding the effects of relative humidity (RH) on hydrophilic phthalocyanines, and (2) assess CuPcTs as a humidity-sensing material. Reaction models show that H 2O undergoes 2-site adsorption which can be represented by a pair of sequentially-occurring pseudo-first order reactions. Using high frequency (300–700 THz) and low frequency (1–8 MHz) dielectric spectroscopy combined with gravimetric measurements and principal component analysis, we observe that significant opto-electrical changes in CuPcTs occur at RHmore » ≈ 60%. The results suggest that rapid H 2O adsorption takes place at hydrophilic sulfonyl/salt groups on domain surfaces at low RH, while slow adsorption and diffusion of H 2O into CuPcTs crystallites leads to a mixed CuPcTs-H 2O phase at RH > 60%, resulting in high frequency dielectric screening of the film by water and dissociation of Na+ from CuPc(SO 3-) 4 ions. Lastly, the CuPcTs-H 2O interaction can be tracked using a combination of gravimetric, optical, and electrical sensing modes, enabling accurate ( ± 2.5%) sensing in the ~0–95% RH range with a detection limit of less than 0.1% RH.« less

Multi-mode humidity sensing with water-soluble copper phthalocyanine for increased sensitivity and dynamic range.

PubMed

Muckley, Eric S; Jacobs, Christopher B; Vidal, Keith; Lavrik, Nickolay V; Sumpter, Bobby G; Ivanov, Ilia N

2017-08-30

Aqueous solubility of copper phthalocyanine-3,4',4″,4″'-tetrasulfonic acid tetrasodium salt (CuPcTs) enables fabrication of flexible electronic devices by low cost inkjet printing. We (1) investigate water adsorption kinetics on CuPcTs for better understanding the effects of relative humidity (RH) on hydrophilic phthalocyanines, and (2) assess CuPcTs as a humidity-sensing material. Reaction models show that H 2 O undergoes 2-site adsorption which can be represented by a pair of sequentially-occurring pseudo-first order reactions. Using high frequency (300-700 THz) and low frequency (1-8 MHz) dielectric spectroscopy combined with gravimetric measurements and principal component analysis, we observe that significant opto-electrical changes in CuPcTs occur at RH ≈ 60%. The results suggest that rapid H 2 O adsorption takes place at hydrophilic sulfonyl/salt groups on domain surfaces at low RH, while slow adsorption and diffusion of H 2 O into CuPcTs crystallites leads to a mixed CuPcTs-H 2 O phase at RH > 60%, resulting in high frequency dielectric screening of the film by water and dissociation of Na + from CuPc(SO 3 - ) 4 ions. The CuPcTs-H 2 O interaction can be tracked using a combination of gravimetric, optical, and electrical sensing modes, enabling accurate ( ± 2.5%) sensing in the ~0-95% RH range with a detection limit of less than 0.1% RH.

Spectroscopic and electrochemical characterization of some Schiff base metal complexes containing benzoin moiety

NASA Astrophysics Data System (ADS)

El-Shahawi, M. S.; Al-Jahdali, M. S.; Bashammakh, A. S.; Al-Sibaai, A. A.; Nassef, H. M.

2013-09-01

The ligation behavior of bis-benzoin ethylenediamine (B2ED) and benzoin thiosemicarbazone (BTS) Schiff bases towards Ru3+, Rh3+, Pd2+, Ni2+ and Cu2+ were determined. The bond length of M-N and spectrochemical parameters (10Dq, β, B and LFSE) of the complexes were evaluated. The redox characteristics of selected complexes were explored by cyclic voltammetry (CV) at Pt working electrode in non aqueous solvents. Au mesh (100 w/in.) optically transparent thin layer electrode (OTTLE) was also used for recording thin layer CV for selected Ru complex. Oxidation of some complexes occurs in a consecutive chemical reaction of an EC type mechanism. The characteristics of electron transfer process of the couples M2+/M3+ and M3+/M4+ (M = Ru3+, Rh3+) and the stability of the complexes towards oxidation and/or reduction were assigned. The nature of the electroactive species and reduction mechanism of selected electrode couples were assigned.

Nitrate removal by Fe0/Pd/Cu nano-composite in groundwater.

PubMed

Liu, Hongyuan; Guo, Min; Zhang, Yan

2014-01-01

Nitrate pollution in groundwater shows a great threat to the safety of drinking water. Chemical reduction by zero-valent iron is being considered as a promising technique for nitrate removal from contaminated groundwater. In this paper, Fe0/Pd/Cu nano-composites were prepared by the liquid-phase reduction method, and batch experiments of nitrate reduction by the prepared Fe0/Pd/Cu nano-composites under various operating conditions were carried out. It has been found that nano-Fe0/Pd/Cu composites processed dual functions: catalytic reduction and chemical reduction. The introduction of Pd and Cu not only improved nitrate removal rate, but also reduced the generation of ammonia. Nitrate removal rate was affected by the amount of Fe0/Pd/Cu, initial nitrate concentration, solution pH, dissolved oxygen (DO), reaction temperature, the presence of anions, and organic pollutant. Moreover, nitrate reduction by Fe0/Pd/Cu composites followed the pseudo-first-order reaction kinetics. The removal rate of nitrate and total nitrogen were about 85% and 40.8%, respectively, under the reaction condition of Fe-6.0%Pd-3.0%Cu amount of 0.25 g/L, pH value of 7.1, DO of 0.42 mg/L, and initial nitrate concentration of 100 mg/L. Compared with the previous studies with Fe0 alone or Fe-Cu, nano-Fe-6%Pd-3%Cu composites showed a better selectivity to N2.

Pd-Cu/poly(o-Anisidine) nanocomposite as an efficient catalyst for formaldehyde oxidation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hosseini, Sayed Reza, E-mail: r.hosseini@umz.ac.ir; Raoof, Jahan-Bakhsh; Ghasemi, Shahram

Highlights: • o-Anisidine monomer was electro-polymerized at the pCPE surface in acid medium. • Palladium/copper NPs were prepared by galvanic replacement method at the POA/pCPE. • Pd-Cu NPs showed excellent electrocatalytic activity towards formaldehyde oxidation. • The bimetallic Pd-Cu NPs/POA nanocomposite showed satisfactory long-term stability. - Abstract: In this work, for the first time, the electrocatalytic oxidation of formaldehyde in 0.5 M sulfuric acid solution at spherical bimetallic palladium-copper nanoparticles (Pd-Cu NPs) deposited on the poly (o-Anisidine) film modified electrochemically pretreated carbon paste electrode (POA/pCPE) has been investigated. Highly porous POA film prepared by electropolymerization onto the pCPE was usedmore » as a potent support for deposition of the Pd-Cu NPs. The Pd-Cu NPs were prepared through spontaneous and irreversible reaction via galvanic replacement between Pd{sup II} ions and the Cu{sup 0} particles. The prepared Pd-Cu NPs were characterized by scanning electron microscopy, energy dispersive spectroscopy and electrochemical methods. The obtained results showed that the utilization of Cu nanoparticles and pretreatment technique enhances the electrocatalytic activity of the modified electrode towards formaldehyde oxidation. The influence of several parameters on formaldehyde oxidation as well as stability of the Pd-Cu/POA/pCPE has been investigated.« less

Siderophile and chalcophile metals as tracers of the evolution of the Siberian Trap in the Noril'sk region, Russia

NASA Astrophysics Data System (ADS)

Brügmann, G. E.; Naldrett, A. J.; Asif, M.; Lightfoot, P. C.; Gorbachev, N. S.; Fedorenko, V. A.

1993-05-01

In this study Cu, Ni, and platinum-group elements (PGE) were determined in a sequence of basaltic and picritic lavas from the Siberian Trap in the Noril'sk area of Russia to constrain genetic relationships between the basalts and the petrogenesis of Ni-Cu-PGE sulfide deposits associated with the Talnakh and Noril'sk intrusions. In the most primitive basalts (8-19 wt% MgO) of the Tuklonsky (Tk) suite, Pt and Pd concentrations range from 4-13 ppb, increasing with decreasing MgO content; whereas Ir contents decrease with MgO from 0.8-0.05 ppb. The contrasting behavior of these elements, which all have very high sulfide-silicate partition coefficients, as well as the primitive mantle-like ratios of Cu/Y and Pd/Y, suggests that these magmas were not sulfide-saturated. The high PGE abundances imply that their parental magmas were also not sulfide saturated during partial melting in the mantle. Due to sulfide segregation, the overlying basalts of the Nadezhdinsky (Nd) series are low in Cu and Ni (52 and 38 ppm, respectively); highly depleted in all PGE; and have very low Cu/Y, Pd/Y, and Pd/Cu ratios. However, in stratigraphically higher levels, Cu, Ni, and PGE concentrations increase systematically through the Morongovsky (Mr) suite to reach a concentration plateau in the uppermost Mokulaevsky (Mk) suite (Pt 8 ppb; Pd: 9 ppb; Ir: 0.12 ppb; Rh: 0.4 ppb). At the same time, ratios such as Cu/Y increase and approach primitive mantle values. However, ratios involving PGE, such as Pd/Y, remain low, suggesting the removal of small amounts of sulfide (0.01-0.03%). The compositional variations in the basalts and the sulfide liquids can be quantitatively described by fractional segregation of a sulfide liquid in an open- or closed-system magma chamber. The latter model suggests that the basalts represent the eruption products of a zoned magma chamber in which light magma, with crustal components contaminated, overlies less contaminated, denser magma. Crustal contamination caused sulfide saturation, and the resulting sulfide liquids settled through a magma column and accumulated at the bottom of the chamber. In this model, the sulfide liquid is not in equilibrium with the whole magma mass, and sulfide segregation is compared with the zone-refining process of metallurgy. The sulfides become more enriched as they move through the magma; and although the magma left behind is depleted in PGE, Cu, and Ni, their concentrations also increase with depth. Eventually, the magma chamber is emptied from the top to the bottom, producing the flood basalt sequence and the associated intrusions and ore deposits. In the open-system model, sulfide saturation was initially caused by assimilation of crustal material by the Tuklonsky magma. Continuous and simultaneous replenishment, assimilation, and crystallization processes formed the lower Nd lavas. The concurrent removal of 0.5-1% sulfide strongly depleted these magmas in chalcophile and siderophile metals. Due to the continuous replenishment of the magma chamber with uncontaminated PGE-rich magma, succeeding lavas (Mr, Mk) show diminishing signs of crustal contamination and become less sulfide-saturated, as indicated by the increasing Ni, Cu, and PGE abundances. During the evolution of the chamber, the magma remained sulfur-saturated, and sulfides accumulated at the base. The composition of the sulfide ores could be regarded as a mixture consisting of low Ni-, Cu-, and PGE-sulfides derived with a low silicate/sulfide ratio (100) from the Tk-Nd magma and high Ni-, Cu-, and PGE-sulfides formed with a high ratio (10,000) from the Mr-Mk magma.

New constraints on the origin of the Skaergaard intrusion Cu-Pd-Au mineralization: Insights from high-resolution X-ray computed tomography

NASA Astrophysics Data System (ADS)

Godel, Bélinda; Rudashevsky, Nikolay S.; Nielsen, Troels F. D.; Barnes, Stephen J.; Rudashevsky, Vladimir N.

2014-03-01

This contribution presents the first detailed three-dimensional (3D) in situ analysis of samples from the Platinova Reef using high-resolution X-ray computed tomography (HRXCT) and 3D image processing and quantification coupled with microscopic and mineralogical investigations. Our HRXCT analyses reveal the complex textural relationships between Cu-rich sulfides (bulk composition close to bornite), skaergaardite (PdCu), Au-rich phases, silicates and Fe-Ti oxides and provide unequivocal textural evidences, not observed previously. The association in 3D between Cu-rich sulfide globules, PdCu alloy and ilmenite is inconsistent with a hydrothermal origin of the Cu-Pd mineralization. In contrast, our results combined with phase diagrams strongly support a primary magmatic origin for the Cu-Pd mineralization where Cu and Pd-rich, Fe-poor sulfide liquid represents a cumulus phase that forms by in-situ nucleation. These sulfide droplets and attached skaergaardite grains were trapped during the formation and crystallization of the Fe-Ti oxides. Subsequent, post-cumulus processes led to the partial to total dissolution of the sulfide not entirely enclosed by the Fe-Ti oxides (i.e., not protected from reaction) leading to the observed variability in Cu and Pd composition at the aggregate (sulfide + PdCu) scale and to the occurrence of free PdCu alloys. In contrast to the PdCu alloy, gold-bearing minerals are never observed entirely enclosed within the Fe-Ti oxide. Two hypotheses can be envisaged for the formation of the gold enriched layer in the upper part of the section. Gold may have either precipitated from high-temperature late magmatic Cl-rich fluids. Alternatively, gold may have been enriched during fractional crystallization after sulfide had been suppressed from the liquidus after the Pd layer crystallized and then deposited along redox barriers.

Evaluation of the amalgamation reaction of experimental Ag-Sn-Cu alloys containing Pd using a mercury plating technique.

PubMed

Koike, Marie; Ferracane, Jack L; Fujii, Hiroyuki; Okabe, Toru

2003-09-01

A mercury plating technique was used to determine the phases forming on experimental Ag-Sn-Cu alloy powders (with and without Pd) exposed to electrolytically deposited mercury. Four series of alloy powders were made: a) 1.5% Pd with 10-14% Cu (CU series); b) 1.0% Pd with 10-14% Cu (1PD series); c) 1.5% Pd with different ratios of Ag3Sn (gamma) to Ag4Sn (beta) with 12% Cu (AGSN series); and d) 9-13% Cu with no Pd (NOPD series). Each powder was pressed on a freshly prepared amalgam specimen made from the same powder and metallographically polished until cross sections appeared; mercury was electroplated on the alloy particles. Alloy powders, amalgams and electroplated specimens were examined using XRD and SEM/EDS. XRD confirmed the presence of gamma2 in amalgams made from alloys with Cu < 13% or with Ag3Sn/Ag4Sn > 0.8. Specimens with moderately plated Hg showed gamma1 (Ag2Hg3) polyhedra and eta' Cu6Sn5, but not gamma2. This method effectively identifies alloys prone to forming gamma2.

Microstructures of Pd-containing dispersants for admixed dental amalgams.

PubMed

Chern Lin, J H; Greener, E H

1991-10-01

Blended Pd-containing dispersants were developed by the utilization of a Ag-Cu eutectic into which Pd was substituted for Ag or Cu in concentrations of up to 20 wt%. Compositions were melted either in argon-filled sealed vycor tubes or in a graphite-linked carbon crucible of an induction furnace with an argon blanket. Ingots of approximately 1.5 cm in diameter were sectioned to 0.2 cm in thickness and polished through standard metallographic polishing procedures. The possible compounds were identified by XRD. The microstructures of the alloys were examined by SEM/EDS. XRD analysis of the alloys revealed the preferential dissolution of Pd in Cu when the Pd concentration was less than or equal to 10 wt%. When the Pd concentration exceeded 20 wt%, Pd was found to be dissolved in both Ag and Pd. No Cu3Pd x-ray diffraction peaks were found for alloys with Pd concentration of up to 20 wt%. SEM/EDS analysis confirmed XRD results; lamellae of Ag and Cu-Pd were found in alloys with Pd concentration less than or equal to 10 wt%.

Single-reactor process for producing liquid-phase organic compounds from biomass

DOEpatents

Dumesic, James A.; Simonetti, Dante A.; Kunkes, Edward L.

2015-12-08

Disclosed is a method for preparing liquid fuel and chemical intermediates from biomass-derived oxygenated hydrocarbons. The method includes the steps of reacting in a single reactor an aqueous solution of a biomass-derived, water-soluble oxygenated hydrocarbon reactant, in the presence of a catalyst comprising a metal selected from the group consisting of Cr, Mn, Fe, Co, Ni, Cu, Mo, Tc, Ru, Rh, Pd, Ag, W, Re, Os, Ir, Pt, and Au, at a temperature, and a pressure, and for a time sufficient to yield a self-separating, three-phase product stream comprising a vapor phase, an organic phase containing linear and/or cyclic mono-oxygenated hydrocarbons, and an aqueous phase.

Single-reactor process for producing liquid-phase organic compounds from biomass

DOEpatents

Dumesic, James A [Verona, WI; Simonetti, Dante A [Middleton, WI; Kunkes, Edward L [Madison, WI

2011-12-13

Disclosed is a method for preparing liquid fuel and chemical intermediates from biomass-derived oxygenated hydrocarbons. The method includes the steps of reacting in a single reactor an aqueous solution of a biomass-derived, water-soluble oxygenated hydrocarbon reactant, in the presence of a catalyst comprising a metal selected from the group consisting of Cr, Mn, Fe, Co, Ni, Cu, Mo, Tc, Ru, Rh, Pd, Ag, W, Re, Os, Ir, Pt, and Au, at a temperature, and a pressure, and for a time sufficient to yield a self-separating, three-phase product stream comprising a vapor phase, an organic phase containing linear and/or cyclic mono-oxygenated hydrocarbons, and an aqueous phase.

PD-L1 Detection in Tumors Using [(64)Cu]Atezolizumab with PET.

PubMed

Lesniak, Wojciech G; Chatterjee, Samit; Gabrielson, Matthew; Lisok, Ala; Wharram, Bryan; Pomper, Martin G; Nimmagadda, Sridhar

2016-09-21

The programmed death protein 1 (PD-1) and programmed death-ligand 1 (PD-L1) pair is a major immune checkpoint pathway exploited by cancer cells to develop and maintain immune tolerance. With recent approvals of anti-PD-1 and anti-PD-L1 therapeutic antibodies, there is an urgent need for noninvasive detection methods to quantify dynamic PD-L1 expression in tumors and to evaluate the tumor response to immune modulation therapies. To address this need, we assessed [(64)Cu]atezolizumab for the detection of PD-L1 expression in tumors. Atezolizumab (MPDL3208A) is a humanized, human and mouse cross-reactive, therapeutic PD-L1 antibody that is being investigated in several cancers. Atezolizumab was conjugated with DOTAGA and radiolabeled with copper-64. The resulting [(64)Cu]atezolizumab was assessed for in vitro and in vivo specificity in multiple cell lines and tumors of variable PD-L1 expression. We performed PET-CT imaging, biodistribution, and blocking studies in NSG mice bearing tumors with constitutive PD-L1 expression (CHO-hPD-L1) and in controls (CHO). Specificity of [(64)Cu]atezolizumab was further confirmed in orthotopic tumor models of human breast cancer (MDAMB231 and SUM149) and in a syngeneic mouse mammary carcinoma model (4T1). We observed specific binding of [(64)Cu]atezolizumab to tumor cells in vitro, correlating with PD-L1 expression levels. Specific accumulation of [(64)Cu]atezolizumab was also observed in tumors with high PD-L1 expression (CHO-hPD-L1 and MDAMB231) compared to tumors with low PD-L1 expression (CHO, SUM149). Collectively, these studies demonstrate the feasibility of using [(64)Cu]atezolizumab for the detection of PD-L1 expression in different tumor types.

What Factors Control Platinum-Group Element (PGE) Abundances in Basalts From the Ontong Java Plateau?

NASA Astrophysics Data System (ADS)

Chazey, W. J.; Neal, C. R.

2002-12-01

Eleven samples encompassing four sites drilled by Ocean Drilling Program Leg 192 to the Ontong Java Plateau (OJP) were analyzed for major, trace and platinum-group (PGEs: Ir, Ru, Rh, Pt, and Pd) elements. Based on major and trace element chemistry, these are divided into two groups: a primitive group, which was newly discovered on Leg 192, and Kwaimbaita-type basalts, which are ubiquitous on the OJP (cf. Tejada et al., 2002, J. Pet. 43:449). The primitive group is relatively enriched in MgO, Ni, and Cr and relatively depleted in incompatible elements compared to the Kwaimbaita-type basalts. Petrography indicates that the fractionating phases during emplacement of both types of basalts were olivine and Cr-spinel +/- plagioclase +/- cpx. Normalized PGE profiles are fractionated, but exhibit a flattening between Ru and Ir and occasionally an enrichment in Ir. It has been shown that chromite can preferentially incorporate Os and Ru (Kd ?150) over Ir (Kd ?100), which may account for the Ir and Ru systematics. We do not consider sulfide to be a factor in fractionating the PGEs because it is either absent or present as a trace phase in these basalts and the OJP basalts are sulfur undersaturated (Michael and Cornell, 1996, EOS 77:714). Additionally, the primitive samples from the OJP also have Cu/Pd ratios (4500-8000) that are roughly similar to primitive mantle (7300), and have a generally flat transition from Pd to Y on a primitive mantle-normalized plot. It is unlikely that these samples reached sulfur saturation. The Kwaimbaita-type basalts have slightly elevated Cu/Pd ratios (9000-14000). While there are subtle differences between the PGE profiles of basalts from the Leg 192 drill cores compared to OJP basalts from subaerial outcrops in the Solomon Islands (e.g., the former have general lower Pt/Rh and higher Rh/Ru ratios), it is apparent that silicate and oxide phases are controlling the PGE profiles and abundances. For example, the six samples analyzed from Site 1185 demonstrate a positive correlation of Ru and Ir with Cr and Ni, suggesting a close association of these elements with the observed olivine and Cr-spinel phenocrysts. For all OJP basalts for which we have PGE data, there is a general positive correlation using MgO (or Cr or Ni) as a fractionation index and PGE abundance as well as ratios such as Pt/Y. Therefore, fractional crystallization controls the PGE contents of the OJP basalts. However, as noted by Ely and Neal (2002, Chem. Geol., in press) the abundances require a source enriched in the PGEs over upper mantle and, in some cases, primitive mantle. Such sources require a PGE enriched component that could be from the outer core, although as noted by Parkinson et al. (2001, EOS 82:F1398) this component is not always required. Further work is underway to substantiate this.

Platinum-group elements, S, Se and Cu in highly depleted abyssal peridotites from the Mid-Atlantic Ocean Ridge (ODP Hole 1274A): Influence of hydrothermal and magmatic processes

NASA Astrophysics Data System (ADS)

Marchesi, Claudio; Garrido, Carlos J.; Harvey, Jason; González-Jiménez, José María; Hidas, Károly; Lorand, Jean-Pierre; Gervilla, Fernando

2013-11-01

Highly depleted harzburgites and dunites were recovered from ODP Hole 1274A, near the intersection between the Mid-Atlantic Ocean Ridge and the 15°20'N Fracture Zone. In addition to high degrees of partial melting, these peridotites underwent multiple episodes of melt-rock reaction and intense serpentinization and seawater alteration close to the seafloor. Low concentrations of Se, Cu and platinum-group elements (PGE) in harzburgites drilled at around 35-85 m below seafloor are consistent with the consumption of mantle sulfides after high degrees (>15-20 %) of partial melting and redistribution of chalcophile and siderophile elements into PGE-rich residual microphases. Higher concentrations of Cu, Se, Ru, Rh and Pd in harzburgites from the uppermost and lowest cores testify to late reaction with a sulfide melt. Dunites were formed by percolation of silica- and sulfur-undersaturated melts into low-Se harzburgites. Platinum-group and chalcophile elements were not mobilized during dunite formation and mostly preserve the signature of precursor harzburgites, except for higher Ru and lower Pt contents caused by precipitation and removal of platinum-group minerals. During serpentinization at low temperature (<250 °C) and reducing conditions, mantle sulfides experienced desulfurization to S-poor sulfides (mainly heazlewoodite) and awaruite. Contrary to Se and Cu, sulfur does not record the magmatic evolution of peridotites but was mostly added in hydrothermal sulfides and sulfate from seawater. Platinum-group elements were unaffected by post-magmatic low-temperature processes, except Pt and Pd that may have been slightly remobilized during oxidative seawater alteration.

Catalytic and electrocatalytic oxidation of ethanol over palladium-based nanoalloy catalysts.

PubMed

Yin, Jun; Shan, Shiyao; Ng, Mei Shan; Yang, Lefu; Mott, Derrick; Fang, Weiqin; Kang, Ning; Luo, Jin; Zhong, Chuan-Jian

2013-07-23

The control of the nanoscale composition and structure of alloy catalysts plays an important role in heterogeneous catalysis. This paper describes novel findings of an investigation for Pd-based nanoalloy catalysts (PdCo and PdCu) for ethanol oxidation reaction (EOR) in gas phase and alkaline electrolyte. Although the PdCo catalyst exhibits a mass activity similar to Pd, the PdCu catalyst is shown to display a much higher mass activity than Pd for the electrocatalytic EOR in alkaline electrolyte. This finding is consistent with the finding on the surface enrichment of Pd on the alloyed PdCu surface, in contrast to the surface enrichment of Co in the alloyed PdCo surface. The viability of C-C bond cleavage was also probed for the PdCu catalysts in both gas-phase and electrolyte-phase EOR. In the gas-phase reaction, although the catalytic conversion rate for CO2 product is higher over Pd than PdCu, the nanoalloy PdCu catalyst appears to suppress the formation of acetic acid, which is a significant portion of the product in the case of pure Pd catalyst. In the alkaline electrolyte, CO2 was detected from the gas phase above the electrolyte upon acid treatment following the electrolysis, along with traces of aldehyde and acetic acid. An analysis of the electrochemical properties indicates that the oxophilicity of the base metal alloyed with Pd, in addition to the surface enrichment of metals, may have played an important role in the observed difference of the catalytic and electrocatalytic activities. In comparison with Pd alloyed with Co, the results for Pd alloyed with Cu showed a more significant positive shift of the reduction potential of the oxygenated Pd species on the surface. These findings have important implications for further fine-tuning of the Pd nanoalloys in terms of base metal composition toward highly active and selective catalysts for EOR.

Magnetic and electronic properties of the Cu-substituted Weyl semimetal candidate ZrCo₂Sn.

PubMed

Kushwaha, S K; Wang, Zhijun; Kong, Tai; Cava, Robert

2018-01-04

We report that the partial substitution of Cu for Co has a significant impact on the magnetic properties of the Heusler-phase Weyl fermion candidate ZrCo₂Sn. Polycrystalline samples of ZrCo_2-<i>x</i>Cu_<i>x</i>Sn (<i>x</i> = 0.0 to 1.0) exhibited a linearly decreasing ferromagnetic transition temperature and similarly decreasing saturated magnetic moment on increasing Cu substitution x. Materials with Cu contents near <i>x</i> = 1 and several other quaternary materials synthesized at the same <i>x</i> (ZrCo<i>T</i>'Sn (<i>T</i>' = Rh, Pd, Ni)) display what appears to be non-ferromagnetic magnetization behavior with spin glass characteristics. Electronic structure calculations suggest that the half-metallic nature of unsubstituted ZrCo₂Sn is disrupted significantly by the Cu substitutions, leading to the breakdown of the magnetization vs. electron count guidelines usually followed by Heusler phases, and a more typical metallic non-spin-polarized electronic structure at high <i>x</i>. © 2018 IOP Publishing Ltd.

Simultaneous leaching of Pt, Pd and Rh from automotive catalytic converters in chloride-containing solutions

NASA Astrophysics Data System (ADS)

Hasani, M.; Khodadadi, A.; Koleini, S. M. J.; Saeedi, A. H.; Meléndez, A. M.

2017-01-01

Dissolution of platinum group metals (PGM; herein Pt, Pd and Rh) in different chloride-based leaching systems from spent auto catalysts was performed. Response surface methodology and a five-level-five-factor central composite design were used to evaluate the effects of 1) temperature, 2) liquid-to-solid ratio, 3) stirring speed, 4) acid concentration and 5) particle size on extraction yield of PGM by aqua regia. Analysis of variance was used to determine the optimum conditions and most significant factors affecting the overall metal extraction. In the optimum conditions, leaching of Pt, Pd and Rh was 91.58%, 93.49% and 60.15%, respectively. The effect of different oxidizing agents on the PGM dissolution in chloride medium was studied comparatively in the following leaching systems: a) aqua regia/sulfuric acid mixture, b) hydrogen peroxide in sulfuric acid (piranha solution), c) sodium hypochlorite and d) copper(II). Dissolution of Rh is increased in both aqua regia and hydrogen peroxide/hydrochloric acid solutions by adding sulfuric acid.

Genetic Pd, Pt, Au, Ag, and Rh mineralogy in Noril'sk sulfide ores

NASA Astrophysics Data System (ADS)

Spiridonov, E. M.; Kulagov, E. A.; Serova, A. A.; Kulikova, I. M.; Korotaeva, N. N.; Sereda, E. V.; Tushentsova, I. N.; Belyakov, S. N.; Zhukov, N. N.

2015-09-01

The undeformed ore-bearing intrusions of the Noril'sk ore field (NOF) cut through volcanic rocks of the Late Permian-Early Triassic trap association folded in brachysynclines. Due to the nonuniform load on the roof of intrusive bodies, most sulfide melts were squeezed, up to the tops of ore-bearing intrusions; readily fusible Ni-Fe-Cu sulfide melts were almost completely squeezed. In our opinion, not only one but two stages of mineralization developed at the Noril'sk deposits: (i) syntrap magmatic and (ii) epigenetic post-trap metamorphic-hydrothermal. All platinum-group minerals (PGM) and minerals of gold are metasomatic in the Noril'sk ores. They replaced sulfide solid solutions and exsolution structures. All types of PGM and Au minerals occur in the ores, varying in composition from pyrrhotite to chalcopyrite, talnakhite, mooihoekite, and rich in galena; they are localized in the inner and outer contact zones and differ only in the quantitative proportions of ore minerals. The aureoles of PGM and Au-Ag minerals are wider than the contours of sulfide bodies and coincide with halos of fluid impact on orebodies and adjacent host rocks. The pneumatolytic PGM and Au-Ag minerals are correlated in abundance with the dimensions of sulfide bodies. Their amounts are maximal in veins of late fusible ore composed of eutectic PbS ss and iss intergrowths, as well as at their contacts. The Pd and Pt contents in eutectic sulfide ores of NOF are the world's highest. In the process of noble-metal mineral formation, the fluids supply Pd, Pt, Au, As, Sb, Sn, Bi, and a part of Te, whereas Fe, Ni, Cu, Pb, Ag, Rh, a part of Te and Pd are leached from the replaced sulfide minerals. The pneumatolytic PGM of the early stage comprises Pd and Pt intermetallic compounds enriched in Au along with Pd-Pt-Fe-Ni-Cu-Sn-Pb(As) and (Pd,Pt,Au)(Sn,Sb,Bi,Te,As) solid solutions. Pneumatolytic PGM and Au minerals of the middle stage are products of solid-phase transformation and recrystallization of early PGM in combination with the newly formed mineral species Sb-paolovite-insizwaite-geversite-maslovite, niggliite, tetraferroplatinum, rustenburgite-atokite-zvyagintsevite, moncheite, majakite, plumbopalladinite, polarite in association with altaite. The late minerals of the middle stage include stannopalladinite, tatianaite-taimyrite, Ag-Pd-Pt tetraauricupride, and cuproauride. PGM and Au-Ag minerals of the late stage are represented by sobolevskite-sudburyite-kotulskite, maslovite-michenerite, low-Sb paolovite, hessite, cabriite, Au-Ag minerals with fineness of 870-003, froodite, Sb-free insizwaite, Bi-free geversite, and Sb-free niggliite. Electrum and küstelite in PGM aggregates are not zoned. Crystals of Au-Ag minerals that grow over PGM minerals are smoothly zoned. Their zoning may be direct (crystal margins are enriched in Ag), inverse, oscillatory, and complex. Despite favorable annealing conditions, exsolution structures are not identified in Au-Ag minerals from the Noril'sk ores. Sperrylite—the latest of pneumatolytic PGM—occurs as metacrysts up to 14 cm in size. Sperrylite, which replaces high-Sb minerals, contains up to 11 wt % Sb. Pneumatolytic noble-metal minerals originated under the effect of the fluids released during crystallization of sulfide melts in an extremely reductive setting and at extremely low fS2; temperature drops from ~450 to ~350°C. Metamorphic-hydrothermal Ag mineralization (native silver, Hg-silver, sulfides and selenides, chalcopyrite-lenaite solid solutions, argentopentlandite), Pd mineralization (vysotskite, palladoarsenide, vincentite, Sb-free Ag-paolovite, malyshevite, native palladium), and Pt mineralization (kharaelakhite, cooperite, native platinum) develop in those parts of orebodies that are affected by low-grade metamorphism.

Biomonitoring of 30 trace elements in urine of children and adults by ICP-MS.

PubMed

Heitland, Peter; Köster, Helmut D

2006-03-01

The paper provides physicians and clinical chemists with statistical data (concentration ranges, geometric mean values, selected percentiles, etc.) about 30 urinary trace elements in order to determine whether people have trace element deficiencies or have been exposed to higher elemental concentrations. Morning urine samples of 72 children and 87 adults from two geographical areas of Germany were collected and the elements Li, Be, V, Cr, Mn, Ni, Co, Cu, Zn, Ga, As, Se, Rb, Sr, Mo, Rh, Pd, Ag, Cd, In, Sn, Sb, Cs, Ba, Pt, Au, Pb, Tl, Bi and U were determined by inductively coupled plasma mass spectrometry (ICP-MS) with a new octopole based collision/reaction cell. The urine samples were analysed directly after a simple 1/5 (V/V) dilution with deionised water and nitric acid. Information on exposure conditions of all human subjects were collected by questionnaire-based interviews. The described concentration data down to the ng/l range are very useful for the formulation of reference values. For some elements either new data are described (e.g., for V, Ga, In, Bi, Rh, Mn) or differences to earlier studies were found (e.g., for Be, As). For other elements (e.g., Sb, Se, Mo, Ba, Cu, Zn, Li) our results are in good correlation with previous studies and also complemented with urinary trace element concentrations for children.

Chalcophile element geochemistry of the Boggy Plain zoned pluton, southeastern Australia: a S-saturated barren compositionally diverse magmatic system

NASA Astrophysics Data System (ADS)

Park, Jung-Woo; Campbell, Ian H.; Ickert, Ryan B.; Allen, Charlotte M.

2013-02-01

The behavior of the platinum group elements (PGE) and Re in felsic magmas is poorly understood due to scarcity of data. We report the concentrations of Ni, Cu, Re, and PGE in the compositionally diverse Boggy Plain zoned pluton (BPZP), which shows a variation of rock type from gabbro through granodiorite and granite to aplite with a SiO2 range from 52 to 74 wt %. In addition, major silicate and oxide minerals were analyzed for Ni, Cu, and Re, and a systematic sulfide study was carried out to investigate the role of silicate, oxide, and sulfide minerals on chalcophile element geochemistry of the BPZP. Mass balance calculation shows that the whole rock Cu budget hosted by silicate and oxide minerals is <13 wt % and that Cu is dominantly located in sulfide phases, whereas most of the whole rock Ni budget (>70 wt %) is held in major silicate and oxide minerals. Rhenium is dominantly hosted by magnetite and ilmenite. Ovoid-shaped sulfide blebs occur at the boundary between pyroxene phenocrysts and neighboring interstitial phases or within interstitial minerals in the gabbro and the granodiorite. The blebs are composed of pyrrhotite, pyrite, chalcopyrite, and S-bearing Fe-oxide, which contain total trace metals (Co, Ni, Cu, Ag, Pb) up to ~16 wt %. The mineral assemblage, occurrence, shape, and composition of the sulfide blebs are a typical of magmatic sulfide. PGE concentrations in the BPZP vary by more than two orders of magnitude from gabbro (2.7-7.8 ppb Pd, 0.025-0.116 ppb Ir) to aplite (0.05 ppb Pd, 0.001 ppb Ir). Nickel, Cu, Re, and PGE concentrations are positively correlated with MgO in all the rock types although there is a clear discontinuity between the granodiorite and the granite in the trends for Ni, Rh, and Ir when plotted against MgO. Cu/Pd values gradually increase from 6,100 to 52,600 as the MgO content decreases. The sulfide petrology and chalcophile element geochemistry of the BPZP show that sulfide saturation occurred in the late gabbroic stage of magma differentiation. Segregation and distribution of these sulfide blebs controlled Cu and PGE variations within the BPZP rocks although the magma of each rock type may have experienced a different magma evolution history in terms of crustal assimilation and crystal fractionation. The sulfide melt locked in the cumulate rocks must have sequestered a significant portion of the chalcophile elements, which restricted the availability of these metals to magmatic-hydrothermal ore fluids. Therefore, we suggest that the roof rocks that overlay the BPZP were not prospective for magmatic-hydrothermal Cu, Au, or Cu-Au deposits.

Small-sized PdCu nanocapsules on 3D graphene for high-performance ethanol oxidation

NASA Astrophysics Data System (ADS)

HuThese Authors Contributed Equally To This Work., Chuangang; Zhai, Xiangquan; Zhao, Yang; Bian, Ke; Zhang, Jing; Qu, Liangti; Zhang, Huimin; Luo, Hongxia

2014-02-01

A one-pot solvothermal process has been developed for direct preparation of PdCu nanocapsules (with a size of ca. 10 nm) on three-dimensional (3D) graphene. Due to the 3D pore-rich network of graphene and the unique hollow structure of PdCu nanocapsules with a wall thickness of ca. 3 nm, the newly-prepared PdCu/3D graphene hybrids activated electrochemically have great electrocatalytic activity towards ethanol oxidation in alkaline media, much better than single-phase Pd and commercial E-TEK 20% Pt/C catalysts promising for application in direct ethanol fuel cells.A one-pot solvothermal process has been developed for direct preparation of PdCu nanocapsules (with a size of ca. 10 nm) on three-dimensional (3D) graphene. Due to the 3D pore-rich network of graphene and the unique hollow structure of PdCu nanocapsules with a wall thickness of ca. 3 nm, the newly-prepared PdCu/3D graphene hybrids activated electrochemically have great electrocatalytic activity towards ethanol oxidation in alkaline media, much better than single-phase Pd and commercial E-TEK 20% Pt/C catalysts promising for application in direct ethanol fuel cells. Electronic supplementary information (ESI) available. See DOI: 10.1039/c3nr05722d

MOF-derived Cu-Pd/nanoporous carbon composite as an efficient catalyst for hydrogen evolution reaction: A comparison between hydrothermal and electrochemical synthesis

NASA Astrophysics Data System (ADS)

Mandegarzad, Sakineh; Raoof, Jahan Bakhsh; Hosseini, Sayed Reza; Ojani, Reza

2018-04-01

In this study, a novel catalyst based on Cu-Pd bimetallic nanoparticles supported on nanoporous carbon composite (NPCC) is successfully fabricated through three-step process and used as an electrocatalyst towards hydrogen evolution reaction (HER). At the first step, MOF-199 is synthesized via two distinct strategies; (1) hydrothermal (HT) and (2) electrochemical (EC). Next, the synthesized MOF-199 is used as a template in order to prepare Cu/NPCC by direct carbonization under N2 atmosphere followed by galvanic replacement reaction of Cu metals by PdII ions. All the prepared materials are characterized by X-ray diffraction (XRD), energy-dispersive X-ray spectroscopy (EDS), scanning electron microscopy (SEM), and nitrogen adsorption/desorption measurements. The effect of synthesis method of MOF-199 on the electrocatalytic activity of the final product towards HER is investigated. The electrochemical measurements indicate that Cu-Pd/NPCC derived from the MOF prepared by EC method (Cu-Pd/NPCC/EC) exhibits an enhanced catalytic activity towards HER in H2SO4 solution than the Cu-Pd/NPCC/HT. This improvement may be attributed to using of supporting electrolyte in the preparation of Cu-Pd/NPCC/EC.

Temperature-dependent Study of Isobutanol Decomposition

DTIC Science & Technology

2012-11-01

dimensional Al2O3 alumina CO2 carbon dioxide FTIR Fourier transform infrared Pd palladium Rh rhodium TPD temperature-programmed desorption TPO...that increasing temperature promotes aldehyde formation on the surface of each catalyst. In addition, it is shown that palladium (Pd) activates the...formation of aldehydes and CO2 at a lower temperature than a rhodium (Rh) catalyst. 15. SUBJECT TERMS Isobutanol, FTIR, spectroscopy 16. SECURITY

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

NASA Technical Reports Server (NTRS)

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

2002-01-01

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

London penetration depth measurements in Ba (Fe 1-xT x) 2As 2(T=Co,Ni,Ru,Rh,Pd,Pt,Co+Cu) superconductors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gordon, Ryan T.

2011-01-01

The London penetration depth has been measured in various doping levels of single crystals of Ba(Fe 1-xT x) 2As 2 (T=Co,Ni,Ru,Rh,Pd,Pt,Co+Cu) superconductors by utilizing a tunnel diode resonator (TDR) apparatus. All in-plane penetration depth measurements exhibit a power law temperature dependence of the form Δλ ab(T) = CT n, indicating the existence of low-temperature, normal state quasiparticles all the way down to the lowest measured temperature, which was typically 500 mK. Several different doping concentrations from the Ba(Fe 1-xT x) 2As 2 (T=Co,Ni) systems have been measured and the doping dependence of the power law exponent, n, is compared tomore » results from measurements of thermal conductivity and specific heat. In addition, a novel method has been developed to allow for the measurement of the zero temperature value of the in-plane penetration depth, λ ab(0), by using TDR frequency shifts. By using this technique, the doping dependence of λ ab(0) has been measured in the Ba(Fe 1-xCo x) 2As 2 series, which has allowed also for the construction of the doping-dependent superfluid phase stiffness, ρ s(T) = [λ(0)/λ(T)] 2. By studying the effects of disorder on these superconductors using heavy ion irradiation, it has been determined that the observed power law temperature dependence likely arises from pair-breaking impurity scattering contributions, which is consistent with the proposed s±-wave symmetry of the superconducting gap in the dirty scattering limit. This hypothesis is supported by the measurement of an exponential temperature dependence of the penetration depth in the intrinsically clean LiFeAs, indicative of a nodeless superconducting gap.« less

First-Principles Mechanistic Analysis of Dimethyl Ether Electro-Oxidation on Monometallic Single-Crystal Surfaces

DOE PAGES

Herron, Jeffrey A.; Ferrin, Peter; Mavrikakis, Manos

2014-08-27

Dimethyl ether is an attractive alternative to petroleum fuels due to its physical properties, comparable energy density to methanol and ethanol, and minimal deleterious environmental/toxicological effects. For direct fuel cells, it has a number of advantages over other prominent fuels, including easier storage with respect to hydrogen, lower toxicity and crossover when compared to methanol, and more facile complete oxidation as compared to ethanol (which includes a relatively difficult to break C–C bond). However, the dimethyl ether electro-oxidation reaction is poorly understood, hindering the development of improved electrocatalysts. Using periodic, self-consistent (PW91-GGA) density functional theory calculations, we evaluate the thermochemistrymore » of dimethyl ether (DME) electro-oxidation, at the elementary step level, on 12 model, closed-packed facets of pure transition metals: Au, Ag, Cu, Pt, Pd, Ni, Ir, Rh, Co, Os, Ru, and Re. From the calculated thermochemistry, we determine the most probable reaction paths on each of these surfaces, focusing on Pt as a model system. Our results predict two key electro-oxidation peaks. At lower potentials, there is a peak corresponding to partial oxidation of DME to CO (and other surface poisoning species) or complete oxidation to CO 2 via formic acid as a key intermediate. A second, higher-potential peak is due to complete oxidation of adsorbed CO (and other surface poisoning species) to CO 2. Assuming the catalysts remain in their metallic state during the DME electro-oxidation process, our results suggest that the onset potential of the surfaces increases in the order Cu < Ni < Os < Rh < Ir < Co < Ru < Pt < Ag < Pd < Re < Au. Using our results, we construct a theoretical phase diagram showing predicted catalyst activity based on two key reactivity descriptors, the free energies of adsorbed CO and OH. Here, we compare all results to methanol electro-oxidation to understand key mechanistic differences and their impacts on optimal catalyst design for direct DME fuel cells.« less

Simultaneous introduction of various palladium active sites into MOF via one-pot synthesis: Pd@[Cu3-xPdx(BTC)2]n.

PubMed

Zhang, Wenhua; Chen, Zhihao; Al-Naji, Majd; Guo, Penghu; Cwik, Stefan; Halbherr, Olesia; Wang, Yuemin; Muhler, Martin; Wilde, Nicole; Gläser, Roger; Fischer, Roland A

2016-10-14

Simultaneous incorporation of palladium within Pd-Pd and/or Pd-Cu paddlewheels as framework-nodes and Pd nanoparticle (NP) dispersion into MOF have been achieved for the first time via one-pot synthesis. In particular, the framework substitution of Cu(2+) by Pd(2+) as well as the pore loading with PdNPs have been confirmed and characterized by XPS. The obtained solids featuring such multiple Pd-sites show enhanced catalytic activity in the aqueous-phase hydrogenation of p-nitrophenol (PNP) with NaBH4 to p-aminophenol (PAP).

Population pharmacokinetic/pharmacodynamic (PK/PD) modelling of the hypothalamic–pituitary–gonadal axis following treatment with GnRH analogues

PubMed Central

Tornøe, Christoffer W; Agersø, Henrik; Senderovitz, Thomas; Nielsen, Henrik A; Madsen, Henrik; Karlsson, Mats O; Jonsson, E Niclas

2007-01-01

Aims To develop a population pharmacokinetic/pharmacodynamic (PK/PD) model of the hypothalamic–pituitary–gonadal (HPG) axis describing the changes in luteinizing hormone (LH) and testosterone concentrations following treatment with the gonadotropin-releasing hormone (GnRH) agonist triptorelin and the GnRH receptor blocker degarelix. Methods Fifty-eight healthy subjects received single subcutaneous or intramuscular injections of 3.75 mg of triptorelin and 170 prostate cancer patients received multiple subcutaneous doses of degarelix of between 120 and 320 mg. All subjects were pooled for the population PK/PD data analysis. A systematic population PK/PD model-building framework using stochastic differential equations was applied to the data to identify nonlinear dynamic dependencies and to deconvolve the functional feedback interactions of the HPG axis. Results In our final PK/PD model of the HPG axis, the half-life of LH was estimated to be 1.3 h and that of testosterone 7.69 h, which corresponds well with literature values. The estimated potency of LH with respect to testosterone secretion was 5.18 IU l−1, with a maximal stimulation of 77.5 times basal testosterone production. The estimated maximal triptorelin stimulation of the basal LH pool release was 1330 times above basal concentrations, with a potency of 0.047 ng ml−1. The LH pool release was decreased by a maximum of 94.2% by degarelix with an estimated potency of 1.49 ng ml−1. Conclusions Our model of the HPG axis was able to account for the different dynamic responses observed after administration of both GnRH agonists and GnRH receptor blockers, suggesting that the model adequately characterizes the underlying physiology of the endocrine system. PMID:17096678

Structural and magnetic phase transitions in CeCu 6-xT x (T = Ag,Pd)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Poudel, Lekhanath N.; De la cruz, Clarina; Payzant, E. Andrew

The structural and the magnetic properties of CeCu 6-xAg x (0 ≤ x ≤ 0.85) and CeCu 6-xPd x (0 ≤ x ≤ 0.4) have been studied using neutron diffraction, resonant ultrasound spectroscopy (RUS), x-ray diffraction measurements, and first principles calculations. The structural and magnetic phase diagrams of CeCu 6-xAg x and CeCu 6-xPd x as a function of Ag/Pd composition are reported. The end member, CeCu 6, undergoes a structural phase transition from an orthorhombic ( Pnma) to a monoclinic (P2 1/c) phase at 240 K. In CeCu 6-xAg x, the structural phase transition temperature (T s) decreases linearlymore » with Ag concentration and extrapolates to zero at x S ≈ 0.1. The structural transition in CeCu 6-xPd x remains unperturbed with Pd substitution within the range of our study. The lattice constant b slightly decreases with Ag/Pd doping, whereas a and c increase with an overall increase in the unit cell volume. Both systems, CeCu 6-xAg x and CeCu 6-xPd x, exhibit a magnetic quantum critical point (QCP), at x ≈ 0.2 and x ≈ 0.05, respectively. Near the QCP, long range antiferromagnetic ordering takes place at an incommensurate wave vector (δ 1 0 δ 2), where δ 1 ~ 0.62, δ 2 ~ 0.25, x = 0.125 for CeCu 6-xPd x and δ 1 ~ 0.64, δ 2 ~ 0.3, x = 0.3 for CeCu 6-xAg x. As a result, the magnetic structure consists of an amplitude modulation of the Ce moments which are aligned along the c axis of the orthorhombic unit cell.« less

Structural and magnetic phase transitions in CeCu 6-xT x (T = Ag,Pd)

DOE PAGES

Poudel, Lekhanath N.; De la cruz, Clarina; Payzant, E. Andrew; ...

2015-12-15

The structural and the magnetic properties of CeCu 6-xAg x (0 ≤ x ≤ 0.85) and CeCu 6-xPd x (0 ≤ x ≤ 0.4) have been studied using neutron diffraction, resonant ultrasound spectroscopy (RUS), x-ray diffraction measurements, and first principles calculations. The structural and magnetic phase diagrams of CeCu 6-xAg x and CeCu 6-xPd x as a function of Ag/Pd composition are reported. The end member, CeCu 6, undergoes a structural phase transition from an orthorhombic ( Pnma) to a monoclinic (P2 1/c) phase at 240 K. In CeCu 6-xAg x, the structural phase transition temperature (T s) decreases linearlymore » with Ag concentration and extrapolates to zero at x S ≈ 0.1. The structural transition in CeCu 6-xPd x remains unperturbed with Pd substitution within the range of our study. The lattice constant b slightly decreases with Ag/Pd doping, whereas a and c increase with an overall increase in the unit cell volume. Both systems, CeCu 6-xAg x and CeCu 6-xPd x, exhibit a magnetic quantum critical point (QCP), at x ≈ 0.2 and x ≈ 0.05, respectively. Near the QCP, long range antiferromagnetic ordering takes place at an incommensurate wave vector (δ 1 0 δ 2), where δ 1 ~ 0.62, δ 2 ~ 0.25, x = 0.125 for CeCu 6-xPd x and δ 1 ~ 0.64, δ 2 ~ 0.3, x = 0.3 for CeCu 6-xAg x. As a result, the magnetic structure consists of an amplitude modulation of the Ce moments which are aligned along the c axis of the orthorhombic unit cell.« less

Copper amplification of prostaglandin E/sub 2/ stimulation of the release of luteinizing hormone-releasing hormone is a postreceptor event

DOE Office of Scientific and Technical Information (OSTI.GOV)

Barnea, A.; Cho, G.

1987-01-01

The authors have shown that copper amplifies prostaglandin E/sub 2/ (PGE/sub 2/) stimulation of luteinizing hormone-releasing hormone (LH-RH) from explants of the median eminence area (MEA) and that this process is calcium-dependent. Since a Ca-cAMP pathway has been implicated in PGE/sub 2/ action on the LH-RH neuron, in this study the authors wished to ascertain if copper exerts its effect on the PGE/sub 2/ receptor or on a postreceptor component involved in PGE/sub 2/ action. MEA of adult male rats were incubated for 5 min with 200 ..mu..M Cu/histidine and then incubated for 15 min either with 10 ..mu..M PGE/submore » 2/ (Cu/PGE/sub 2/), 100 ..mu..M forskolin (Cu/forskolin), or 1 mM 8-bromoadenosine 3',5'-cyclic monophosphate (Cu/cAMP). Basal release of LH-RH was 4.6 +/- 0.45 pg/15 min per MEA determined by radioimmunoassay. Net stimulated release during the 15-min exposure to PGE/sub 2/, forskolin, or 8-bromoadenosine 3',5'-cyclic monophosphate was 3.6 +/- 0.52, 3.1 +/- 0.39, and 1.6 +/- 0.42 pg/15 min per MEA, respectively. Net stimulated release after exposure to Cu/PGE/sub 2/, Cu/forskolin, or Cu/cAMP indicated that copper amplifies the action of PGE/sub 2/ and forskolin but not cAMP action. When MEA were exposed to a mixture of PGE/sub 2/ and forskolin for 15 min, the effects of these two secretagogues on LH-RH release were not additive. In contrast to PGE/sub 2/ and forskolin, copper did not amplify K/sup +/ stimulation of OH-RH release. These results are supportive of the proposition that PGE/sub 2/ stimulation of OH-RH release is mediated by the Ca-cAMP pathway and that copper amplification of PGE/sub 2/ action is a postreceptor event.« less

Composition-Dependent Morphology of Bi- and Trimetallic Phosphides: Construction of Amorphous Pd-Cu-Ni-P Nanoparticles as a Selective and Versatile Catalyst.

PubMed

Zhao, Ming; Ji, Yuan; Wang, Mengyue; Zhong, Ning; Kang, Zinan; Asao, Naoki; Jiang, Wen-Jie; Chen, Qiang

2017-10-11

Amorphous materials have been widely researched in heterogeneous catalysis and for next-generation batteries. However, the well-defined production of high-quality (e.g., monodisperse and high surface area) amorphous alloy nanomaterials has rarely been reported. In this work, we investigated the correlations among the composition, morphology, and catalysis of various Pd-M-P nanoparticles (NPs) (M = Cu or Ni), which indicated that less Cu (≤20 atom %) was necessary for the formation of an amorphous morphology. The amorphous Pd-Cu-Ni-P NPs were fabricated with a controllable size and characterized carefully, which show excellent selective catalysis in the semihydrogenation of alkynes, hydrogenation of quinoline, and oxidation of primary alcohols. The uniqueness of the catalytic performance was confirmed by control experiments with monometallic Pd, amorphous Pd-Ni-P NPs, crystalline Pd-Cu-P NPs, and a crystalline counterpart of Pd-Cu-Ni-P catalyst. The catalytic selectivity likely arose from improved Pd-M (M = Cu or Ni) synergistic effects in the amorphous phase and the electron deficiency of Pd. The model reactions proceeded under H 2 or O 2 gas without any additives, bases, or metal oxide supports, and the catalyst could be reused several times. This report is expected to shed light on the design of amorphous alloy nanomaterials as green and inexpensive catalysts for atom-economic and selective reactions.

Reliability Assessment and Activation Energy Study of Au and Pd-Coated Cu Wires Post High Temperature Aging in Nanoscale Semiconductor Packaging.

PubMed

Gan, C L; Hashim, U

2013-06-01

Wearout reliability and high temperature storage life (HTSL) activation energy of Au and Pd-coated Cu (PdCu) ball bonds are useful technical information for Cu wire deployment in nanoscale semiconductor device packaging. This paper discusses the influence of wire type on the wearout reliability performance of Au and PdCu wire used in fine pitch BGA package after HTSL stress at various aging temperatures. Failure analysis has been conducted to identify the failure mechanism after HTSL wearout conditions for Au and PdCu ball bonds. Apparent activation energies (Eaa) of both wire types are investigated after HTSL test at 150 °C, 175 °C and 200 °C aging temperatures. Arrhenius plot has been plotted for each ball bond types and the calculated Eaa of PdCu ball bond is 0.85 eV and 1.10 eV for Au ball bond in 110 nm semiconductor device. Obviously Au ball bond is identified with faster IMC formation rate with IMC Kirkendall voiding while PdCu wire exhibits equivalent wearout and or better wearout reliability margin compare to conventional Au wirebond. Lognormal plots have been established and its mean to failure (t 50 ) have been discussed in this paper.

Geochemistry and mineralogy of Pd in the magnetitite layer within the upper gabbro of the Mesoarchean Nuasahi Massif (Orissa, India)

NASA Astrophysics Data System (ADS)

Prichard, Hazel M.; Mondal, Sisir K.; Mukherjee, Ria; Fisher, Peter C.; Giles, Nicolas

2018-04-01

Palladium concentrations of 1-3 ppm with an average Pt/Pd ratio of 0.15 have been located for the first time in a magnetitite layer in the Nuasahi Massif in Orissa India. This layer occurs at a high stratigraphic level in the complex and is nearly 4-km long and 5-12-m thick. The sections of the Pd-rich zone identified to date extend over a distance of 1 km at the southern end of the layer. Several phases of mineralization are evident. The first, primary assemblage of platinum-group minerals (PGM) contains Pd-sulfides (vysotskite), Pd-Pb alloys (zvyagintsevite), and a Pd-In alloy, a mineral probably new to mineralogy. These PGM are confined to central magnetite grains in the magnetitites. The magnetite grains with exsolved fine laths of ilmenite at centers are referred to as central magnetite grains. These central magnetite grains are commonly surrounded by blebs of ilmenite and magnetite that contain the majority of the PGM. These are dominated by Pd-antimonides, variably altered to Pd-oxides, and other PGM including PtAs2 (sperrylite), RuS2 (laurite), and IrRhAsS (irarsite/hollingwothite). Many of these PGM also occur in the interstitial silicates, with rare occurrences in the central magnetite grains. We propose that the platinum-group elements (PGE) crystallized during a minor sulfide saturation event that occurred as the magnetitites crystallized. This event produced the minor Cu-sulfides in these magnetitites. Later introduction of antimony and arsenic, during the alteration event that produced the blebby ilmenite and magnetite, led to the more primary PGM being succeeded by the main PGM assemblage, dominated by Pd-antimonides. These are associated with secondary Cu minerals and sperrylite. Subsequent oxidation during weathering in the hot wet Indian climate produced the Pd-oxides. The Nuasahi Massif is a sill-like Archean layered ultramafic-mafic intrusion genetically linked to high-Mg siliceous basalt or boninites and is characterized by unusually thick layers of chromitite. PGE are concentrated in these chromitites and in the base metal sulfide-bearing breccias in the overlying gabbro. The Pd in the magnetitites described here indicates the presence of a third level where PGE are concentrated and a magma that crystallized to produce PGE concentrations at three stratigraphic levels in the massif. This indicates that similar thin sill-like intrusions, hosting unusually thick chromitites, may also have PGE concentrations at a number of stratigraphic levels.

Preparation of PdCu Alloy Nanocatalysts for Nitrate Hydrogenation and Carbon Monoxide Oxidation

DOE PAGES

Cai, Fan; Yang, Lefu; Shan, Shiyao; ...

2016-06-30

Alloying Pd with Cu is important for catalytic reactions such as denitrification reaction and CO oxidation reaction, but understanding of the catalyst preparation and its correlation with the catalyst’s activity and selectivity remains elusive. Herein, we report the results of investigations of the preparation of PdCu alloy nanocatalysts using different methods and the catalytic properties of the catalysts in catalytic denitrification reaction and CO oxidation reaction. PdCu alloy nanocatalysts were prepared by conventional dry impregnation method and ligand-capping based wet chemical synthesis method, and subsequent thermochemical activation as well. The alloying characteristics depend on the bimetallic composition. PdCu/Al 2O 3more » with a Pd/Cu ratio of 50:50 was shown to exhibit an optimized hydrogenation activity for the catalytic denitrification reaction. The catalytic activity of the PdCu catalysts was shown to be highly dependent on the support, as evidenced by the observation of an enhanced catalytic activity for CO oxidation reaction using TiO 2 and CeO 2 supports with high oxygen storage capacity. Lastly, we discussed the implications of the results to the refinement of the preparation of the alloy nanocatalysts.« less

Metal-insulator transition and superconductivity in the spinel-type Cu(Ir1-xRhx)2S4 system

NASA Astrophysics Data System (ADS)

Matsumoto, Nobuhiro; Endoh, Ryo; Nagata, Shoichi; Furubayashi, Takao; Matsumoto, Takehiko

1999-08-01

The normal thiospinel CuIr2S4 exhibits a temperature-induced metal-insulator (M-I) transition around 226 K with structural transformation, showing hysteresis on heating and cooling. It has been verified that d electrons of Ir atom on the octahedral B sites have a significant role for the M-I transition. On the other hand, CuRh2S4 is a superconductor with the transition temperature Tc=4.70 K, which is well understood on the basis of the BCS theory. It is important to investigate the effect on the M-I transition by substitution of Rh for Ir. We have systematically studied structural transformation and electrical and magnetic properties of Cu(Ir1-xRhx)2S4. The features of the M-I transition change with Rh concentration x. A phase diagram of temperature versus x will be proposed for the Cu(Ir1-xRhx)2S4 system. The sharp M-I transition temperature varies drastically from 226 to 93 K with x from 0.00 to 0.17 and disappears around x=0.20. In a region of 0.00<=x<=0.20, the magnetic susceptibility begins decreasing at a constant onset temperature 226 K on cooling process and shows rather broad temperature variation, even though the metallic state is kept in the resistivity. The sharp M-I transition can take place after the suppression of magnitude in the susceptibility has sufficiently developed far below 226 K. These experimental results are discussed with emphasis on the intrinsic difference between Cu(Ir1-xRhx)2S4 and CuIr2(S1-xSex)4 systems. Furthermore, we will mention the superconductivity for both systems of Cu(Ir1-xRhx)2S4 with high-Rh concentration region and Cu1-xNixRh2S4.

Spectroscopic and electrochemical characterization of some Schiff base metal complexes containing benzoin moiety.

PubMed

El-Shahawi, M S; Al-Jahdali, M S; Bashammakh, A S; Al-Sibaai, A A; Nassef, H M

2013-09-01

The ligation behavior of bis-benzoin ethylenediamine (B2ED) and benzoin thiosemicarbazone (BTS) Schiff bases towards Ru(3+), Rh(3+), Pd(2+), Ni(2+) and Cu(2+) were determined. The bond length of M-N and spectrochemical parameters (10Dq, β, B and LFSE) of the complexes were evaluated. The redox characteristics of selected complexes were explored by cyclic voltammetry (CV) at Pt working electrode in non aqueous solvents. Au mesh (100 w/in.) optically transparent thin layer electrode (OTTLE) was also used for recording thin layer CV for selected Ru complex. Oxidation of some complexes occurs in a consecutive chemical reaction of an EC type mechanism. The characteristics of electron transfer process of the couples M(2+)/M(3+) and M(3+)/M(4+) (M=Ru(3+), Rh(3+)) and the stability of the complexes towards oxidation and/or reduction were assigned. The nature of the electroactive species and reduction mechanism of selected electrode couples were assigned. Copyright © 2013 The Authors. Published by Elsevier B.V. All rights reserved.

Testing Room-Temperature Ionic Liquid Solutions for Depot Repair of Aluminum Coatings

DTIC Science & Technology

2011-05-01

Ne 3 Na Mg IIIB IVB VB VIB VIIB ------ VIIIB ------ IB IIB Al Si P S Cl Ar 4 K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr 5 Rb Sr Y Zr Nb Mo Tc...Ru Rh Pd Ag Cd In Sn Sb Te I Xe 6 Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn 7 Fr Ra Ac Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu Th Pa U Np...Electroplating Bath Lid Arrangement ;:::::::::::=== Thermometer Purge gas vent Anode lead Cathode lead (Extractable from the lid) Purge feed gas

Statistical physics of multicomponent alloys using KKR-CPA

DOE PAGES

Khan, Suffian N.; Staunton, Julie B.; Stocks, George Malcolm

2016-02-16

We apply variational principles from statistical physics and the Landau theory of phase transitions to multicomponent alloys using the multiple-scattering theory of Korringa-Kohn-Rostoker (KKR) and the coherent potential approximation (CPA). This theory is a multicomponent generalization of the S( 2) theory of binary alloys developed by G. M. Stocks, J. B. Staunton, D. D. Johnson and others. It is highly relevant to the chemical phase stability of high-entropy alloys as it predicts the kind and size of finite-temperature chemical fluctuations. In doing so it includes effects of rearranging charge and other electronics due to changing site occupancies. When chemical fluctuationsmore » grow without bound an absolute instability occurs and a second-order order-disorder phase transition may be inferred. The S( 2) theory is predicated on the fluctuation-dissipation theorem; thus we derive the linear response of the CPA medium to perturbations in site-dependent chemical potentials in great detail. The theory lends itself to a natural interpretation in terms of competing effects: entropy driving disorder and favorable pair interactions driving atomic ordering. Moreover, to further clarify interpretation we present results for representative ternary alloys CuAgAu, NiPdPt, RhPdAg, and CoNiCu within a frozen charge (or band-only) approximation. These results include the so-called Onsager mean field correction that extends the temperature range for which the theory is valid.« less

Small-sized PdCu nanocapsules on 3D graphene for high-performance ethanol oxidation.

PubMed

Hu, Chuangang; Zhai, Xiangquan; Zhao, Yang; Bian, Ke; Zhang, Jing; Qu, Liangti; Zhang, Huimin; Luo, Hongxia

2014-03-07

A one-pot solvothermal process has been developed for direct preparation of PdCu nanocapsules (with a size of ca. 10 nm) on three-dimensional (3D) graphene. Due to the 3D pore-rich network of graphene and the unique hollow structure of PdCu nanocapsules with a wall thickness of ca. 3 nm, the newly-prepared PdCu/3D graphene hybrids activated electrochemically have great electrocatalytic activity towards ethanol oxidation in alkaline media, much better than single-phase Pd and commercial E-TEK 20% Pt/C catalysts promising for application in direct ethanol fuel cells.

Attosecond nanotechnology: NEMS of energy storage and nanostructural transformations in materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Beznosyuk, Sergey A., E-mail: bsa1953@mail.ru; Maslova, Olga A., E-mail: maslova-o.a@mail.ru; Zhukovsky, Mark S., E-mail: zhukovsky@list.ru

2015-10-27

The attosecond technology of the nanoelectromechanical system (NEMS) energy storage as active center fast transformation of nanostructures in materials is considered. The self-organizing relaxation of the NEMS active center containing nanocube of 256-atoms limited by planes (100) in the FCC lattice matrix of 4d-transition metals (Ru, Rh, Pd) is described by the quantum NEMS-kinetics (NK) method. Typical for these metals change of the NEMS active center physicochemical characteristics during the time of relaxation is presented. There are three types of intermediate quasistationary states of the NEMS active center. Their forms are plainly distinguishable. The full relaxed NEMS active centers (Ru{submore » 256}, Rh{sub 256}, Pd{sub 256}) accumulate next storage energies: E{sub Ru} = 2.27 eV/at, E{sub Rh} = 1.67 eV/at, E{sub Pd} = 3.02 eV/at.« less

Study of submonolayer films of Au/Cu(100) and Pd/Cu(100) using positron annihilation induced auger electron spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lee, K.D.

1992-01-01

Positron Annihilation induced Auger Electron Spectroscopy (PAES), electron induced Auger Electron Spectroscopy (EAES), and Low Energy Electron Diffraction (LEED) have been used to study the surface composition, surface alloying and overlayer formation of ultrathin films of Au and Pd on Cu(100). This is the first systematic application of PAES to the study of the surface properties of ultrathin layers of metals on metal substrates. Temperature induced changes in the top layer surface compositions in Au/Cu(100) and Pd/Cu(100) are directly observed using PAES, while EAES spectra indicate only minor changes. The surface alloying of the Au/Cu(100) and Pd/Cu(100) systems are demonstratedmore » using PAES in conjunction with LEED. The PAES intensity measurements also provide evidence for positron trapping at surface defects such as steps, kinks and isolated adatoms. The PAES intensity was found to be strongly dependent on surface effects introduced by ion sputtering. The surface defect dependence of the PAES intensity is interpreted in terms of the surface atomic diffusion and positron trapping at surface defects in Au/Cu(100) and Pd/Cu(100). In both systems the shapes of the PAES intensity versus coverage curves for submonolayer coverages at 173K are quite distinct indicating differences in overlayer growth and diffusion behavior of Au and Pd adatoms on the Cu(100) surface. PAES intensities for both Au and Pd are saturated at 1 monolayer demonstrating the extreme surface selectivity of PAES.« less

Investigation of Pd-Modified Ag-CuO Air Braze Filler Metals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Darsell, Jens T.; Hardy, John S.; Kim, Jin Yong

2006-01-10

Palladium was added as a ternary component to a series of silver - copper oxide alloys in an effort to increase the use temperature of these materials for potential ceramic air brazing applications. Large portions of the silver component of the Ag-CuO system were substituted by palladium forming the following alloys: (100-y)[(100-z)Pd - (z)Ag] - (y)CuOx where y = 0 - 34 mol% CuOx, z = 50 - 100 mol% silver, and x = 0, 0.5, and 1, denoting copper metal, Cu2O, or CuO. From differential scanning calorimetry, it was determined that the addition of palladium causes an increase inmore » the solidus and liquidus temperatures of the resulting Pd-Ag-CuO brazes. In general, the liquidus was found to increase by approximately 220°C for the (100-y)(25Pd - 75Ag) - (z)CuOx filler metal compositions relative to comparable Ag-CuOx alloys. Likewise, the solidus was found to increase for these alloys, respectively by 185°C and 60°C, respectively for CuOx contents of y = 0 - 1mol% and 4 - 10 mol%. For the (100-y)(50Pd - 50Ag) - (y)CuOx alloys, the solidus increased between 280 - 390°C over a copper oxide compositional range of x = 0 to 8 mol%. It was determined from sessile drop experiments that palladium causes an increase in the wetting angle for all of the samples tested. Alloy compositions of (100-y)(25Pd - 75Ag) - (y)CuOx displayed increased wetting angles of 5-20° relative to comparable binary compositions. (100-y)(50Pd - 50Ag) - (y)CuOx alloys exhibited an increase in contact angle of 10-60° and compositions containing less than 10 mol% CuOx were not able to wet the substrate. Scanning electron microscopy indicates that the microstructure of the braze consists of Ag-Pd solid solution with CuOx precipitates. In general, a reaction layer consisting of CuAlO2 forms adjacent to the alumina substrate. However, the formation of this layer is apparently hindered by the addition of large amounts of palladium, causing poor wetting behavior, as denoted by substantial porosity found along the braze/substrate interface. The reduction in wettability can be compensated by increasing the CuO content slightly.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xie, Chao; Chen, Yongsheng; Engelhard, Mark H.

This work was conducted to clarify the influence of the type of metal and support on the sulfur tolerance and carbon resistance of supported noble metal catalysts in steam reforming of liquid hydrocarbons. Al2O3-supported noble metal catalysts (Rh, Ru, Pt, and Pd), Rh catalysts on different supports (Al2O3, CeO2, SiO2, and MgO), and Pt catalyst supported on CeO2 and Al2O3, were examined for steam reforming of a liquid hydrocarbon fuel (Norpar13 from Exxon Mobil) at 800 C for 55 h. The results indicate that (1) Rh/Al2O3 shows higher sulfur tolerance than the Ru, Pt, and Pd catalysts on the samemore » support; (2) both Al2O3 and CeO2 are promising supports for Rh catalyst to process sulfur-containing hydrocarbons; and (3) Pt/CeO2 exhibits better catalytic performance than Pt/Al2O3 in the reaction with sulfur. TEM results demonstrate that the metal particles in Rh/Al2O3 were better dispersed (mostly in 1-3 nm) compared with the other catalysts after reforming the sulfur-containing feed. As revealed by XPS, the binding energy of Rh 3d for Rh/Al2O3 is notably higher than that for Rh/CeO2, implying the formation of electron-deficient Rh particles in the former. The strong sulfur tolerance of Rh/Al2O3 may be related to the formation of well-dispersed electron-deficient Rh particles on the Al2O3 support. Sulfur K-edge XANES illustrates the preferential formation of sulfonate and sulfate on Rh/Al2O3, which is believed to be beneficial for improving its sulfur tolerance as their oxygen-shielded sulfur structure may hinder direct Rh-S interaction. Due to its strong sulfur tolerance, the carbon deposition on Rh/Al2O3 was significantly lower than that on the Al2O3-supported Ru, Pt, and Pd catalysts after the reaction with sulfur. The superior catalytic performance of CeO2-supported Rh and Pt catalysts in the presence of sulfur can be ascribed mainly to the promotion effect of CeO2 on carbon gasification, leading to much lower carbon deposition compared with the Rh/Al2O3, Rh/MgO, Rh/SiO2 and Pt/Al2O3 catalysts.« less

Size-dependent disorder-order transformation in the synthesis of monodisperse intermetallic PdCu nanocatalysts

DOE PAGES

Wang, Chenyu; Chen, Dennis P.; Unocic, Raymond R.; ...

2016-05-23

The high performance of Pd-based intermetallic nanocatalysts has the potential to replace Pt-containing catalysts for fuel-cell reactions. Conventionally, intermetallic particles are obtained through the annealing of nanoparticles of a random alloy distribution. However, this method inevitably leads to sintering of the nanoparticles and generates polydisperse samples. Here, monodisperse PdCu nanoparticles with the ordered B2 phase were synthesized by seed-mediated co-reduction using PdCu nanoparticle seeds with a random alloy distribution (A1 phase). A time-evolution study suggests that the particles must overcome a size-dependent activation barrier for the ordering process to occur. Characterization of the as-prepared PdCu B2 nanoparticles by electron microscopymore » techniques revealed surface segregation of Pd as a thin shell over the PdCu core. The ordered nanoparticles exhibit superior activity and durability for the oxygen reduction reaction in comparison with PdCu A1 nanoparticles. This seed-mediated co-reduction strategy produced monodisperse nanoparticles ideally suited for structure–activity studies. Furthermore, the study of their growth mechanism provides insights into the size dependence of disorder–order transformations of bimetallic alloys at the nanoscale, which should enable the design of synthetic strategies toward other intermetallic systems.« less

Walking economy during cued versus non-cued treadmill walking in persons with Parkinson's disease.

PubMed

Gallo, Paul M; McIsaac, Tara L; Garber, Carol Ewing

2013-01-01

Gait impairment is common in Parkinson's disease (PD) and may result in greater energy expenditure, poorer walking economy, and fatigue during activities of daily living. Auditory cueing is an effective technique to improve gait; but the effects on energy expenditure are unknown. To determine whether energy expenditure differs in individuals with PD compared with healthy controls and if auditory cueing improves walking economy in PD. Twenty participants (10 PD and 10 controls) came to the laboratory for three sessions. Participants performed two, 6-minute bouts of treadmill walking at two speeds (1.12 m·sec-1 and 0.67 m·sec-1). One session used cueing and the other without cueing. A metabolic cart measured energy expenditure and walking economy was calculated (energy expenditure/power). PD had worse walking economy and higher energy expenditure than control participants during cued and non-cued walking at the 0.67 m·sec-1 speed and during non-cued walking at the 1.12 m·sec-1. With auditory cueing, energy expenditure and walking economy worsened in both participant groups. People with PD use more energy and have worse walking economy than adults without PD. Walking economy declines further with auditory cuing in persons with PD.

Multi-functional ultrathin Pd xCu 1-x and Pt~Pd xCu 1-x one-dimensional nanowire motifs for various small molecule oxidation reactions

DOE PAGES

Liu, Haiqing; Wong, Stanislaus S.; Adzic, Radoslav R.

2015-11-18

Developing novel electrocatalysts for small molecule oxidation processes, including formic acid oxidation (FAOR), methanol oxidation reaction (MOR), and ethanol oxidation reaction (EOR), denoting the key anodic reactions for their respective fuel cell configurations, is a significant and relevant theme of recent efforts in the field. Herein, in this report, we demonstrated a concerted effort to couple and combine the benefits of small size, anisotropic morphology, and tunable chemical composition in order to devise a novel “family” of functional architectures. In particular, we have fabricated not only ultrathin 1-D Pd 1–xCu x alloys but also Pt-coated Pd 1–xCu x (i.e., Pt~Pdmore » 1–xCu x; herein the ~ indicates an intimate association, but not necessarily actual bond formation, between the inner bimetallic core and the Pt outer shell) core–shell hierarchical nanostructures with readily tunable chemical compositions by utilizing a facile, surfactant-based, wet chemical synthesis coupled with a Cu underpotential deposition technique. Our main finding is that our series of as-prepared nanowires are functionally flexible. More precisely, we demonstrate that various examples within this “family” of structural motifs can be tailored for exceptional activity with all 3 of these important electrocatalytic reactions. In particular, we note that our series of Pd 1–xCu x nanowires all exhibit enhanced FAOR activities as compared with not only analogous Pd ultrathin nanowires but also commercial Pt and Pd standards, with Pd 9Cu representing the “optimal” composition. Moreover, our group of Pt~Pd 1–xCu x nanowires consistently outperformed not only commercial Pt NPs but also ultrathin Pt nanowires by several fold orders of magnitude for both the MOR and EOR reactions in alkaline media. As a result, the variation of the MOR and EOR performance with the chemical composition of our ultrathin Pt~Pd 1–xCu x nanowires was also discussed.« less

p-Type CuRhO 2 as a Self-Healing Photoelectrode for Water Reduction under Visible Light

DOE PAGES

Gu, Jing; Krizan, Jason W.; Gibson, Quinn D.; ...

2013-12-30

Polycrystalline CuRhO 2 is investigated as a photocathode for the splitting of water under visible irradiation. The band edge positions of this material straddle the water oxidation and reduction redox potentials. Thus, photogenerated conduction band electrons are sufficiently energetic to reduce water, while the associated valence band holes are energetically able to oxidize water to O 2. Under visible illumination, H 2 production is observed with ~0.2 V underpotential in an air-saturated solution. In contrast, H 2 production in an Ar-saturated solution was found to be unstable. This instability is associated with the reduction of the semiconductor forming Cu(s). However,more » in the presence of air or O 2, bulk Cu(s) was not detected, implying that CuRhO 2 is self-healing when air is present. Here, this property allows for the stable formation of H 2 with ca. 80% Faradaic efficiency.« less

p-Type CuRhO 2 as a Self-Healing Photoelectrode for Water Reduction under Visible Light

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gu, Jing; Krizan, Jason W.; Gibson, Quinn D.

Polycrystalline CuRhO 2 is investigated as a photocathode for the splitting of water under visible irradiation. The band edge positions of this material straddle the water oxidation and reduction redox potentials. Thus, photogenerated conduction band electrons are sufficiently energetic to reduce water, while the associated valence band holes are energetically able to oxidize water to O 2. Under visible illumination, H 2 production is observed with ~0.2 V underpotential in an air-saturated solution. In contrast, H 2 production in an Ar-saturated solution was found to be unstable. This instability is associated with the reduction of the semiconductor forming Cu(s). However,more » in the presence of air or O 2, bulk Cu(s) was not detected, implying that CuRhO 2 is self-healing when air is present. Here, this property allows for the stable formation of H 2 with ca. 80% Faradaic efficiency.« less

Functional toxicity and tolerance patterns of bioavailable Pd(II), Pt(II), and Rh(III) on suspended Saccharomyces cerevisiae cells assayed in tandem by a respirometric biosensor.

PubMed

Frazzoli, Chiara; Dragone, Roberto; Mantovani, Alberto; Massimi, Cristiana; Campanella, Luigi

2007-12-01

Toxicological implications of exposure to bioavailable platinum group metals, here Pd, Pt, and Rh, are still to be clarified. This study obtained by a biosensor-based method preliminary information on potential effects on cellular metabolism as well as on possible tolerance mechanisms. Aerobic respiration was taken as the toxicological end point to perform tandem tests, namely functional toxicity test and tolerance test. Cells were suspended in the absence of essential constituents for growth. The dose-response curves obtained by exposure (2 h) to the metals (nanogram per gram range) suggested the same mechanisms of action, with Rh showing the greatest curve steepness and the lowest EC50 value. Conservative (95% lower confidence interval) EC10 values were 187, 85 and 51 ng g(-1) for Pt, Pd, and Rh respectively. Tolerance patterns were tested during the same runs. The full tolerance obtained after 12 h of exposure to each metal suggested mitochondrial inhibition of aerobic respiration as a target effect. The hazard rating of the metals in the tolerance test changed in the Rh EC50 range, where Rh showed the lowest toxicity. The observed tolerance might suggest a protective mechanism such as metallothionein induction at concentrations around the EC50 values. The performance of the bioassay was satisfactory, in terms of the limit of detection, repeatability, reproducibility, roboustness, sensibility, and stability; the method's critical uncertainty sources were identified for improvements.

Pd-catalytic in situ generation of H2O2 from H2 and O2 produced by water electrolysis for the efficient electro-fenton degradation of rhodamine B.

PubMed

Yuan, Songhu; Fan, Ye; Zhang, Yucheng; Tong, Man; Liao, Peng

2011-10-01

A novel electro-Fenton process was developed for wastewater treatment using a modified divided electrolytic system in which H2O2 was generated in situ from electro-generated H2 and O2 in the presence of Pd/C catalyst. Appropriate pH conditions were obtained by the excessive H+ produced at the anode. The performance of the novel process was assessed by Rhodamine B (RhB) degradation in an aqueous solution. Experimental results showed that the accumulation of H2O2 occurred when the pH decreased and time elapsed. The maximum concentration of H2O2 reached 53.1 mg/L within 120 min at pH 2 and a current of 100 mA. Upon the formation of the Fenton reagent by the addition of Fe2+, RhB degraded completely within 30 min at pH 2 with a pseudo first order rate constant of 0.109 ± 0.009 min(-1). An insignificant decline in H2O2 generation and RhB degradation was found after six repetitions. RhB degradation was achieved by the chemisorption of H2O2 on the Pd/C surface, which subsequently decomposed into •OH upon catalysis by Pd0 and Fe2+. The catalytic decomposition of H2O2 to •OH by Fe2+ was more powerful than that by Pd0, which was responsible for the high efficiency of this novel electro-Fenton process.

Adsorption of Rh(III) complexes from chloride solutions obtained by leaching chlorinated spent automotive catalysts on ion-exchange resin Diaion WA21J.

PubMed

Shen, Shaobo; Pan, Tonglin; Liu, Xinqiang; Yuan, Lei; Wang, Jinchao; Zhang, Yongjian; Guo, Zhanchen

2010-07-15

It was found that Rh, Pd and Pt contained in the spent ceramic automotive catalysts could be effectively extracted by dry chlorination with chlorine. In order to concentrate Rh(III) ions contained in the chloride solutions obtained, thermodynamic and kinetics studies for adsorption of Rh(III) complexes from the chloride solutions on an anionic exchange resin Diaion WA21J were carried out. Rh, Pd, Pt, Al, Fe, Si, Zn and Pb from the chloride solution could be adsorbed on the resin. The distribution coefficients (K(d)) of Rh(III) decreased with the increase in initial Rh(III) concentration or in adsorption temperature. The isothermal adsorption of Rh(III) was found to fit Langmuir, Freundlich and Dubinin-Kaganer-Radushkevich models under the adsorption conditions. The maximum monolayer adsorption capacities Q(max) based on Langmuir adsorption isotherms were 6.39, 6.61 and 5.81 mg/g for temperatures 18, 28 and 40 degrees C, respectively. The apparent adsorption energy of Rh was about -7.6 kJ/mol and thus Rh(III) adsorption was a physical type. The experimental data obtained could be better simulated by pseudo-first-order kinetic model and the activation energy obtained was 6.54 J/mol. The adsorption rate of Rh(III) was controlled by intraparticle diffusion in most of time of adsorption process. 2010 Elsevier B.V. All rights reserved.

Cu assisted synthesis of self-supported PdCu alloy nanowires with enhanced performances toward ethylene glycol electrooxidation

NASA Astrophysics Data System (ADS)

Yan, Bo; Xu, Hui; Zhang, Ke; Li, Shujin; Wang, Jin; Shi, Yuting; Du, Yukou

2018-03-01

Self-supported PdCu alloy nanowires fabricated by a facile one-pot method have been reported, which copper assists in the morphological transformation from graininess to nanowires. The copper incorporated with palladium to form alloy structures cannot only cut down the usage of noble metal but also enhance their catalytic performances. The catalysts with self-supported structure and proper ratio of palladium to copper show great activity and long-term stability for the electrooxidation of ethylene glycol in alkaline solution. Especially for Pd43Cu57, its mass activity reaches to 5570.83 mA mg-1, which is 3.12 times as high as commercial Pd/C. This study highlights an accessible strategy to prepare self-supported PdCu alloy nanowires and their potential applications in renewable energy fields.

Pyridine synthesis by reactions of allyl amines and alkynes proceeding through a Cu(OAc)2 oxidation and Rh(III)-catalyzed N-annulation sequence.

PubMed

Kim, Dong-Su; Park, Jung-Woo; Jun, Chul-Ho

2012-11-28

A new methodology has been developed for the synthesis of pyridines from allyl amines and alkynes, which involves sequential Cu(II)-promoted dehydrogenation of the allylamine and Rh(III)-catalyzed N-annulation of the resulting α,β-unsaturated imine and alkyne.

Local structure order in Pd 78Cu 6Si 16 liquid

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yue, G. Q.; Zhang, Y.; Sun, Y.

2015-02-05

The short-range order (SRO) in Pd 78Cu 6Si 16 liquid was studied by high energy x-ray diffraction and ab initio molecular dynamics (MD) simulations. The calculated pair correlation functions at different temperatures agree well with the experimental results. The partial pair correlation functions from ab intio MD simulations indicate that Si atoms prefer to be uniformly distributed while Cu atoms tend to aggregate. By performing structure analysis using Honeycutt-Andersen index, Voronoi tessellation, and atomic cluster alignment method, we show that the icosahedron and face-centered cubic SRO increase upon cooling. The dominant SRO is the Pd-centered Pd 9Si 2 motif, namelymore » the structure of which motif is similar to the structure of Pd-centered clusters in the Pd 9Si 2 crystal. The study further confirms the existence of trigonal prism capped with three half-octahedra that is reported as a structural unit in Pd-based amorphous alloys. The majority of Cu-centered clusters are icosahedra, suggesting that the presence of Cu is benefit to promote the glass forming ability.« less

Origin of the world-class PGE-Au mineralisation in the Skaergaard intrusion by bulk S-saturation, accumulation, partial dissolution, and secondary reef formation.

NASA Astrophysics Data System (ADS)

Daugaard Nielsen, Troels Frederik

2013-04-01

The Skaergaard intrusion is the type locality for stratiform "Skaergaard-type" PGE-Au mineralisations with layers rich in PGE, followed by Au and Cu. Models for stratiform PGE mineralisations divide into uppers and downers models. Downers models assume bulk liquid S-saturation followed by a variety of accumulation processes and the second model the scavenging of metals by fluids deep in intrusions and deposition in chemical traps above. This investigation is based on continuous profiling in roof, walls and floor. Cu anomalies in roof, walls and floor are contemporaneous and systematics in Pd/Pt and Pd/Au ratios document bulk liquid S-saturation, no loss of precious metal below the mineralisation and no obvious chemical traps. A classic downers process is documented. The timing of the mineralisation is controlled by composition of liquidus plagioclase and fraction of residual magma (F). PGE concentrations are an order of magnitude higher in the floor mineralisation due to accumulation. Systematics across the mineralisation shows in the centre of the intrusion 5 main levels of Pd-concentration followed by an Au and a Cu-level. All levels PGE and Au levels have c. 100 ppm Cu and show no correlation to PGE and Au. 90% of all PGE is contained in one phase, skaergaardite (PdCu).The lower and main PGE concentration has moderate Pd/Pt ratios. Overlying secondary reefs have high, basal Pd/Pt and show local S-saturation reflecting d-values of PGE between sulphide and silicate liquid. No basal high Pd/Pt anomaly occurs at Au and Cu levels and the floor shows four types of mineralisation. The main PGE reef (Pd5) has gradual increase and decrease in PGE and Pd/Pt, dissolution of sulphide, increasing PGE+Au/Cu due to reaction between interstial and documented reactive Fe-rich silicate melt and the bulk magma sulfides. Dissolution of Cu-sulfide increases PGE/Cu, reduces the size of droplets to 30µ (av.) and provides metals for secondary reefs above - formed by migration of interstitial melt - and show expected decrease in Pd/Pt and increase in Au/Pd due to fractionation and substitutions in Skaergaardite (PdCu) and tetra-auricupride (AuCu). The main Au level is elevated relative to the top Pd-level (Pd1). High resolution X-ray tomography and petrography shows the precious metal phases on grain boundaries. The paragenesis is complex with many tellurides, arsenite and sulfides, and primary hydrous phases including amphiboles, ferrosaponite and chlorite. The Au mineralisation level is the residual of the Fe-rich interstitial silicate melt trapped by the layering of the gabbros. The Cu levels above are like the secondary Pd-levels secondary mineralisation levels caused by reaction between primary sulphide and Fe-rich melt. The Skaergaard-type mineralisation owes its characteristics to the concentration of Fe-rich interstitial melt and loss of immiscible granophyric melt from the mush zone at the floor of the residual bulk magma and a continuum of dissolution and S-saturation in an ever changing interstitial melt environment.

The mechanism of transition-metal (Cu or Pd)-catalyzed synthesis of benzimidazoles from amidines: theoretical investigation.

PubMed

Li, Juan; Gu, Honghong; Wu, Caihong; Du, Lijuan

2014-11-28

In this study, the Cu(OAc)2- and [PdCl2(PhCN)2]-catalyzed syntheses of benzimidazoles from amidines were theoretically investigated using density functional theory calculations. For the Cu-catalyzed system, our calculations supported a four-step-pathway involving C-H activation of an arene with Cu(II) via concerted metalation-deprotonation (CMD), followed by oxidation of the Cu(II) intermediate and deprotonation of the imino group by Cu(III), and finally reductive elimination from Cu(III). In our calculations, the barriers for the CMD step and the oxidation step are the same. The results are different from the ones reported by Fu et al. in which the whole reaction mechanism includes three steps and the CMD step is rate determining. On the basis of the calculation results for the [PdCl2(PhCN)2]-catalyzed system, C-H bond breaking by CMD occurs first, followed by the rate-determining C-N bond formation and N-H deprotonation. Pd(III) species is not involved in the [PdCl2(PhCN)2]-catalyzed syntheses of benzimidazoles from amidines.

Growth and Magnetotransport Properties of Dirac Semimetal Candidate Cu3PdN

NASA Astrophysics Data System (ADS)

Quintela, C. X.; Campbell, N.; Harris, D. T.; Shao, D. F.; Xie, L.; Pan, X. Q.; Tsymbal, E. Y.; Rzchowski, M. S.; Eom, C. B.

Since the discovery of three-dimensional Dirac semimetals (DSM) Cd3As2 and Na3Bi, many efforts have been made to identify new DSM materials. Recently, nitride antiperovskite Cu3PdN has been proposed by two different groups as a new DSM candidate. However, until now, the experimental realization of bulk Cu3PdN and the study of its electronic properties has been hindered due to the difficulty of synthesizing bulk single crystals of this material. Here, we report the first growth and magnetotransport characterization of epitaxial Cu3PdN thin films on (001) SrTiO3 substrates. Magnetotransport measurements reveal p-type metallic conduction with very low temperature coefficient of the resistance and small non-linear magnetoresistance at low temperatures. The successful growth of Cu3PdN thin films opens the path to investigating the unknown electronic properties of this material, and provides a template for further research on other antiperovskite DSM candidates such as Cu3ZnN.

X-ray absorption fine structure and x-ray diffraction studies of crystallographic grains in nanocrystalline FePd:Cu thin films

NASA Astrophysics Data System (ADS)

Krupinski, M.; Perzanowski, M.; Polit, A.; Zabila, Y.; Zarzycki, A.; Dobrowolska, A.; Marszalek, M.

2011-03-01

FePd alloys have recently attracted considerable attention as candidates for ultrahigh density magnetic storage media. In this paper we investigate FePd thin alloy film with a copper admixture composed of nanometer-sized grains. [Fe(0.9 nm)/Pd(1.1 nm)/Cu(d nm)]×5 multilayers were prepared by thermal deposition at room temperature in UHV conditions on Si(100) substrates covered by 100 nm SiO2. The thickness of the copper layer has been changed from 0 to 0.4 nm. After deposition, the multilayers were rapidly annealed at 600 °C in a nitrogen atmosphere, which resulted in the creation of the FePd:Cu alloy. The structure of alloy films obtained this way was determined by x-ray diffraction (XRD), glancing angle x-ray diffraction, and x-ray absorption fine structure (EXAFS). The measurements clearly showed that the L10 FePd:Cu nanocrystalline phase has been formed during the annealing process for all investigated copper compositions. This paper concentrates on the crystallographic grain features of FePd:Cu alloys and illustrates that the EXAFS technique, supported by XRD measurements, can help to extend the information about grain size and grain shape of poorly crystallized materials. We show that, using an appropriate model of the FePd:Cu grains, the comparison of EXAFS and XRD results gives a reasonable agreement.

The applicability of the catalytic wet-oxidation to CELSS

NASA Technical Reports Server (NTRS)

Takahashi, Y.; Nitta, K.; Ohya, H.; Oguchi, M.

1987-01-01

The wet oxidation catalysis of Au, Pd, Pt, Rh or Ru on a ceramic honeycomb carrier was traced in detail by 16 to 20 repetitive batch tests each. As a result, Pt or Pd on a honeycomb carrier was shown to catalyze complete nitrogen gasification as N2. Though the catalysts which realize both complete nitrogen gasification and complete oxidation could not be found, the Ru+Rh catalyst was found to be most promising. Ru honeycomb catalyzed both nitrification and nitrogen gasification.

Platinum, palladium, and rhodium analyses of ultramafic and mafic rocks from the Stillwater Complex, Montana

USGS Publications Warehouse

Page, Norman J; Riley, Leonard Benjamin; Haffty, Joseph

1969-01-01

Analyses by a combination fire- assay-solution-optical-emission spectrographic method of 137 rocks from the Stillwater Complex, Mont., indicate that platinum, palladium, and rhodium are preferentially concentrated in chromitite zones. The A chromitite zone (21 samples) has an average of 988.9 ppb (pans per billion, 10-9) Pt, 2290.2 ppb Pd, and 245.9 ppb Rh and reaches a maximum (to date) of 8,000 ppb Pt, 11,000 ppb Pd, and 1,700 ppb Rh.

Epitaxial thin films of Dirac semimetal antiperovskite Cu3PdN

NASA Astrophysics Data System (ADS)

Quintela, C. X.; Campbell, N.; Shao, D. F.; Irwin, J.; Harris, D. T.; Xie, L.; Anderson, T. J.; Reiser, N.; Pan, X. Q.; Tsymbal, E. Y.; Rzchowski, M. S.; Eom, C. B.

2017-09-01

The growth and study of materials showing novel topological states of matter is one of the frontiers in condensed matter physics. Among this class of materials, the nitride antiperovskite Cu3PdN has been proposed as a new three-dimensional Dirac semimetal. However, the experimental realization of Cu3PdN and the consequent study of its electronic properties have been hindered due to the difficulty of synthesizing this material. In this study, we report fabrication and both structural and transport characterization of epitaxial Cu3PdN thin films grown on (001)-oriented SrTiO3 substrates by reactive magnetron sputtering and post-annealed in NH3 atmosphere. The structural properties of the films, investigated by x-ray diffraction and scanning transmission electron microscopy, establish single phase Cu3PdN exhibiting cube-on-cube epitaxy (001)[100]Cu3PdN||(001)[100]SrTiO3. Electrical transport measurements of as-grown samples show metallic conduction with a small temperature coefficient of the resistivity of 1.5 × 10-4 K-1 and a positive Hall coefficient. Post-annealing in NH3 results in the reduction of the electrical resistivity accompanied by the Hall coefficient sign reversal. Using a combination of chemical composition analyses and ab initio band structure calculations, we discuss the interplay between nitrogen stoichiometry and magneto-transport results in the framework of the electronic band structure of Cu3PdN. Our successful growth of thin films of antiperovskite Cu3PdN opens the path to further investigate its physical properties and their dependence on dimensionality, strain engineering, and doping.

Synthesis of nanoporous CuO/TiO2/Pd-NiO composite catalysts by chemical dealloying and their performance for methanol and ethanol electro-oxidation

NASA Astrophysics Data System (ADS)

Niu, Mengying; Xu, Wence; Zhu, Shengli; Liang, Yanqin; Cui, Zhenduo; Yang, Xianjin; Inoue, Akihisa

2017-09-01

Nanoporous CuO/TiO2/Pd-NiO-x (x = 0, 1, 3, 5, 7 at%) catalysts have been synthesized by dealloying Cu-Ti-Pd-Ni alloy ribbons in acid solution. The nanoporous structure and chemical composition of the catalysts distribute uniformly. Based on the electrochemical active area (EASA), electrocatalytic activity and stability, the np-CuO/TiO2/Pd-NiO-3 catalyst possesses the best performance for methanol and ethanol electro-oxidation. For methanol and ethanol electro-oxidation, the anodic current densities in forward scan of the np-CuO/TiO2/Pd-NiO-3 catalyst are about 5.6 times and 2.1 times larger than that of the np-CuO/TiO2/Pd catalyst, respectively. The introduction of NiO provides more electrochemical active sites due to the improved geometrical and bifunctional mechanism. NiO promotes the adsorption of oxygen-containing species (OHads) on the catalyst surface, and electron effect between Pd and Ni is favorable for charge transfer. This accelerates the removal of intermediate products during the oxidation process. The electrocatalytic processes of methanol and ethanol oxidation in alkaline solution are controlled by both charge transfer and diffusion.

Synthesis, Crystal Chemistry, and Physical Properties of Ternary Intermetallic Compounds An2T2X( An=Pu, Am; X=ln, Sn; T=Co, Ir, Ni, Pd, Pt, Rh)

NASA Astrophysics Data System (ADS)

Pereira, L. C. J.; Wastin, F.; Winand, J. M.; Kanellakopoulos, B.; Rebizant, J.; Spirlet, J. C.; Almeida, M.

1997-11-01

The synthesis, structural, and physical characterization of nine new ternary intermetallic compounds belonging to the isostructural An2T2Xfamily with the transuranium Pu and Am elements, namely, Pu 2Ni 2In, Pu 2Pd 2In, Pu 2Pt 2In, Pu 2Rh 2In, Pu 2Ni 2Sn, Pu 2Pd 2Sn, Pu 2Pt 2Sn, Am 2Ni 2Sn, and Am 2Pd 2Sn, are reported. From these compounds only Pu 2Rh 2In, Am 2Ni 2Sn, and Am 2Pd 2Sn melt incongruently. All of these compounds crystallize in a tetragonal U 3Si 2-type structure, with the space group P4/ mbm, ( Z=2) as most of the U and Np 2-2-1 compounds already found. In this structure, Anatoms occupy the 4 h( x1, x1+0.5, 0.5), Tthe 4 g( x2, x2+0.5, 0), and Xthe 2 a(0, 0, 0) positions. The average values of x1and x2are, respectively, 0.17 and 0.37. Single-crystal X-ray data were refined to R/ RW=0.045/0.066, 0.043/0.072, 0.066/0.080, 0.070/0.098, 0.029/0.048, 0.055/0.080, 0.073/0.096, 0.048/0.086, 0.048/0.065 for Pu 2Ni 2In, Pu 2Pd 2In, Pu 2Pt 2In, Pu 2Rh 2In, Pu 2Ni 2Sn, Pu 2Pd 2Sn, Pu 2Pt 2Sn, Am 2Ni 2Sn, and Am 2Pd 2Sn, respectively, for seven variables. The variation of the lattice parameters and the range of stability of the 2-2-1 phase are discussed in terms of the substitution of different An(actinide), T(transition metal), and X( p-electron) elements in their crystal structure. The possible role of spin fluctuations in the low-temperature behavior of the Pu samples is indicated by magnetic and electrical resistivity measurements.

Palladium Coated Copper Nanowires as a Hydrogen Oxidation Electrocatalyst in Base

DOE PAGES

Alia, Shaun M.; Yan, Yushan

2015-05-09

The palladium (Pd) nanotubes we synthesized by the spontaneous galvanic displacement of copper (Cu) nanowires, are forming extended surface nanostructures highly active for the hydrogen oxidation reaction (HOR) in base. The synthesized catalysts produce specific activities in rotating disk electrode half-cells 20 times greater than Pd nanoparticles and about 80% higher than polycrystalline Pd. Although the surface area of the Pd nanotubes was low compared to conventional catalysts, partial galvanic displacement thrifted the noble metal layer and increased the Pd surface area. Moreover, the use of Pd coated Cu nanowires resulted in a HOR mass exchange current density 7 timesmore » greater than the Pd nanoparticles. The activity of the Pd coated Cu nanowires further nears Pt/C, producing 95% of the mass activity.« less

Environmental application of millimeter-scale sponge iron (s-Fe(0)) particles (II): the effect of surface copper.

PubMed

Ju, Yongming; Liu, Xiaowen; Liu, Runlong; Li, Guohua; Wang, Xiaoyan; Yang, Yanyan; Wei, Dongyang; Fang, Jiande; Dionysiou, Dionysios D

2015-04-28

To enhance the catalytic reactivity of millimeter-scale particles of sponge iron (s-Fe(0)), Cu(2+) ions were deposited on the surface of s-Fe(0) using a simple direct reduction reaction, and the catalytic properties of the bimetallic system was tested for removal of rhodamine B (RhB) from an aqueous solution. The influence of Cu(0) loading, catalyst dosage, particle size, initial RhB concentration, and initial pH were investigated, and the recyclability of the catalyst was also assessed. The results demonstrate that the 3∼5 millimeter s-Fe(0) particles (s-Fe(0)(3∼5mm)) with 5wt% Cu loading gave the best results. The removal of RhB followed two-step, pseudo-first-order reaction kinetics. Cu(0)-s-Fe(0) showed excellent stability after five reuse cycles. Cu(0)-s-Fe(0) possesses great advantages compared to nanoscale zero-valent iron, iron power, and iron flakes as well as its bimetals. The surface Cu(0) apparently catalyzes the production of reactive hydrogen atoms for indirect reaction and generates Fe-Cu galvanic cells that enhance electron transfer for direct reaction. This bimetallic catalyst shows great potential for the pre-treatment of recalcitrant wastewaters. Additionally, some oxides containing iron element are selected to simulate the adsorption process. The results prove that the adsorption process of FeOOH, Fe2O3 and Fe3O4 played minor role for the removal of RhB. Copyright © 2015 Elsevier B.V. All rights reserved.

New Data on Some Short-Lived Isotopes of Ruthenium and Rhodium; NUEVOS DATOS SOBRE ALGUNOS ISOTOPOS DE RUTENIO Y RODIO DE VIDA CORTA

DOE Office of Scientific and Technical Information (OSTI.GOV)

Baumgartner, F.; Bedmar, A.P.

1961-01-01

BS>Ru and Rh isotopes with mass numbers 107 and 108 and Rh/sup 109/ were obtained from fission products. Ru/sup 107/ was also prepared by the nuclear process Pd/sup 110/ (n, alpha ) Ru/sup 107/. Beta and gamma energies of these nuclides were studied spectrometrically and the gamma lines found for Ru/sup 107/ and Ru/sup 108/ (and daughter) were useful for the precise determination of their half lives. Rh/sup 109/ was identified through its daughter Pd/sup 109/ in the mixture of rhodium isotopes from fission products. lrradiation of natural paladium with fast neutrons led to an activity that may only bemore » attributed to Rh/ sup 110/. Neither its half life nor its decay energy was determined accurately. (auth)« less

Structural Characterization of Bimetallic Nanocrystal Electrocatalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cullen, David A

2016-01-01

Late transition metal nanocrystals find applications in heterogeneous catalysis such as plasmon-enhanced catalysis and as electrode materials for fuel cells, a zero-emission and sustainable energy technology. Their commercial viability for automotive transportation has steadily increased in recent years, almost exclusively due to the discovery of more efficient bimetallic nanocatalysts for the oxygen reduction reaction (ORR) at the cathode. Despite improvements to catalyst design, achieving high activity while maintaining durability is essential to further enhance their performance for this and other important applications in catalysis. Electronic effects arising from the generation of metal-metal interfaces, from plasmonic metals, and from lattice distortions,more » can vastly improve sorption properties at catalytic surfaces, while increasing durability.[1] Multimetallic lattice-strained nanoparticles are thus an interesting opportunity for fundamental research.[2,3] A colloidal synthesis approach is demonstrated to produce AuPd alloy and Pd@Au core-shell nanoicosahedra as catalysts for electro-oxidations. The nanoparticles are characterized using aberration-corrected scanning transmission electron microscopy (ac-STEM) and large solid angle energy dispersive X-ray spectroscopy (EDS) on an FEI Talos 4-detector STEM/EDS system. Figure 1 shows bright-field (BF) and high-angle annular dark-field (HAADF) ac-STEM images of the alloy and core-shell nanoicosahedra together with EDS line-scans and elemental maps. These structures are unique in that the presence of twin boundaries, alloying, and core-shell morphology could create highly strained surfaces and interfaces. The shell thickness of the core-shell structures observed in HAADF-STEM images is tuned by adjusting the ratio between metal precursors (Figure 2a-f) to produce shells ranging from a few to several monolayers. Specific activity was measured in ethanol electro-oxidation to examine the effect of shell thickness on catalytic activity. A volcano relationship was observed for the core-shell nanoicosahedra having different Pd-shell thicknesses as Pd content is increased (Figure 2g). Durability tests are ongoing for the AuPd system; however, promising ORR materials and morphologies have also been synthesized for a more cost-effective Cu-based system of Cu-CuM (M = Pd, Rh, Pt) core-alloy-shell nanocrystals. The synthesis, characterization, and catalytic behavior of different high-index faceted morphologies of Cu-based materials towards ORR and methanol oxidation catalysis will be discussed, where we show how they exceed the performance of commercial Pd- and Pt- based catalysts. The development of new materials and their characterization is critical to understanding the effects of structure and composition on catalysis. Future efforts are directed at resolving these structures and more industrially relevant fuel cell catalysts in 3D through electron tomography.[4] References: [1] X. Huang, et al., Science 348 (2015) p. 1230. [2] P. Strasser, et al., Nat. Chem. 2 (2010) p. 454. [3] C. Chen, et al., Science 343 (2014) p. 1339. [4] Microscopy performed as part of a user project through ORNL s Center for Nanophase Materials Sciences, which is a U.S. DOE Office of Science User Facility, and instrumentation provided by the U.S. DOE Office of Nuclear Energy, Fuel Cycle R&D Program, and the Nuclear Science User Facilities.« less

Tailoring the synthesis of supported Pd catalysts towards desired structure and size of metal particles.

PubMed

Suresh, Gatla; Radnik, Jörg; Kalevaru, Venkata Narayana; Pohl, Marga-Martina; Schneider, Matthias; Lücke, Bernhard; Martin, Andreas; Madaan, Neetika; Brückner, Angelika

2010-05-14

In a systematic study, the influence of different preparation parameters on phase composition and size of metal crystallites and particles in Pd-Cu/TiO(2) and Pd-Sb/TiO(2) catalyst materials has been explored. Temperature and atmosphere of thermal pretreatment (pure He or 10% H(2)/He), nature of metal precursors (chlorides, nitrates or acetates) as well as of ammonium additives (ammonium sulfate, nitrate, carbonate) and urea were varied with the aim of tailoring the synthesis procedure for the preferential formation of metal particles with similar size and structure as observed recently in active catalysts after long-term equilibration under catalytic reaction conditions in acetoxylation of toluene to benzylacetate. Among the metal precursors and additives, the chloride metal precursors and (NH(4))(2)SO(4) were most suitable. Upon thermal pretreatment of Pd-Sb or Pd-Cu precursors, chloroamine complexes of Pd and Cu are formed, which decompose above 220 degrees C to metallic phases independent of the atmosphere. In He, metallic Pd particles were formed with both the co-components. In H(2)/He flow, Pd-Cu precursors were converted to core-shell particles with a Cu shell and a Pd core, while Sb(1)Pd(1) and Sb(7)Pd(20) alloy phases were formed in the presence of Sb. Metal crystallites of about 40 nm agglomerate to particles of up to 150 nm in He and to even larger size in H(2)/He.

LA-ICP-MS Study of Trace Elements in the Chanuskij Metal

NASA Technical Reports Server (NTRS)

Petaev, Michail I.

2005-01-01

This progress report covers work done during the second year of the 3-year proposal. During this year we resolved many issues relevant to the analytical technique developed by us for measuring trace elements in meteoritic metals. This technique was used to measure concentrations of Fe, Ni, Co, Cr, Cu, Ga, Ge, As, Mo, Ru, Rh, Pd, Sb, W, Re, Os, Ir, Pt, and Au in eight large (120 - 160 microns) metal grains from both "igneous" and "metamorphic" lithologies of the Chanuskij silicate inclusions. The first application of OUT technique to metal grains from thin sections showed some limitations. Small thickness of metal grains in the thin section limited the signal to 3-4 time-slices instead of 10- 1 1 ones in polished sections of iron meteorites studied before.

Self-Lubricating Composite Containing Chromium Oxide

NASA Technical Reports Server (NTRS)

Dellacorte, Christopher (Inventor); Edmonds, Brian J. (Inventor)

1999-01-01

A self lubricating. friction and wear reducing composite material useful over a wide temperature range of from cryogenic temperature up to about 900 C. contains 60 80 wt. % of particulate Cr2O3, dispersed in a metal binder of a metal alloy containing Cr and at least 50 wt. % of Ni, Cr or a mature of Ni and Cr. It also contains 5-20 wt. % of a fluoride of at least one Group I, Group II or rare earth metal and. optionally, 5-20 wt. % of a low temperature lubricant metal, such as Ag. Au, Pt, Pd, Rh and Cu. This composite exhibits less oxidation instability and less abrasiveness than composites containing chromium carbide, is readily applied using plasma spray and can be ground and polished with a silicon carbide abrasive.

Ferromagnetism and spin glass ordering in transition metal alloys (invited)

NASA Astrophysics Data System (ADS)

Crane, S.; Carnegie, D. W., Jr.; Claus, H.

1982-03-01

Magnetic properties of transition metal alloys near the percolation threshold are often complicated by metallurgical effects. Alloys like AuFe, VFe, CuNi, RhNi, and PdNi are in general not random solid solutions but have various degrees of atomic clustering or short-range order (SRO), depending on the heat treatment. First, it is shown how the magnetic ordering temperature of these alloys varies with the degree of clustering or SRO. Second, by systematically changing this degree of clustering or SRO, important information can be obtained about the magnetic phase diagram. In all these alloys below the percolation limit, the onset of ferromagnetic order is probably preceded by a spin glass-type ordering. However, details of the magnetic phase diagram near the critical point can be quite different alloy systems.

Ternary oxide nanostructures and methods of making same

DOEpatents

Wong, Stanislaus S [Stony Brook, NY; Park, Tae-Jin [Port Jefferson, NY

2009-09-08

A single crystalline ternary nanostructure having the formula A.sub.xB.sub.yO.sub.z, wherein x ranges from 0.25 to 24, and y ranges from 1.5 to 40, and wherein A and B are independently selected from the group consisting of Ag, Al, As, Au, B, Ba, Br, Ca, Cd, Ce, Cl, Cm, Co, Cr, Cs, Cu, Dy, Er, Eu, F, Fe, Ga, Gd, Ge, Hf, Ho, I, In, Ir, K, La, Li, Lu, Mg, Mn, Mo, Na, Nb, Nd, Ni, Os, P, Pb, Pd, Pr, Pt, Rb, Re, Rh, Ru, S, Sb, Sc, Se, Si, Sm, Sn, Sr, Ta, Tb, Tc, Te, Ti, Tl, Tm, U, V, W, Y, Yb, and Zn, wherein the nanostructure is at least 95% free of defects and/or dislocations.

Dynamic stabilities of icosahedral-like clusters and their ability to form quasicrystals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liang, Xiaogang; Hamid, Ilyar; Duan, Haiming, E-mail: dhm@xju.edu.cn

2016-06-15

The dynamic stabilities of the icosahedral-like clusters containing up to 2200 atoms are investigated for 15 metal elements. The clusters originate from five different initial structures (icosahedron, truncated decahedron, octahedron, closed-shell fragment of an HCP structure, and non-closed-shell fragment of an HCP structure). The obtained order of the dynamic stabilities of the icosahedral-like clusters can be assigned to three groups, from stronger to weaker, according to the size ranges involved: (Zr, Al, Ti) > (Cu, Fe, Co, Ni, Mg, Ag) > (Pb, Au, Pd, Pt, Rh, Ir), which correspond to the predicted formation ability of the quasicrystals. The differences ofmore » the sequences can be explained by analyzing the parameters of the Gupta-type many-body inter-atomic potentials.« less

Recommended values of clean metal surface work functions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Derry, Gregory N., E-mail: gderry@loyola.edu; Kern, Megan E.; Worth, Eli H.

2015-11-15

A critical review of the experimental literature for measurements of the work functions of clean metal surfaces of single-crystals is presented. The tables presented include all results found for low-index crystal faces except cases that were known to be contaminated surfaces. These results are used to construct a recommended value of the work function for each surface examined, along with an uncertainty estimate for that value. The uncertainties are based in part on the error distribution for all measured work functions in the literature, which is included here. The metals included in this review are silver (Ag), aluminum (Al), goldmore » (Au), copper (Cu), iron (Fe), iridium (Ir), molybdenum (Mo), niobium (Nb), nickel (Ni), palladium (Pd), platinum (Pt), rhodium (Rh), ruthenium (Ru), tantalum (Ta), and tungsten (W)« less

Tight-binding study of stacking fault energies and the Rice criterion of ductility in the fcc metals

NASA Astrophysics Data System (ADS)

Mehl, Michael J.; Papaconstantopoulos, Dimitrios A.; Kioussis, Nicholas; Herbranson, M.

2000-02-01

We have used the Naval Research Laboratory (NRL) tight-binding (TB) method to calculate the generalized stacking fault energy and the Rice ductility criterion in the fcc metals Al, Cu, Rh, Pd, Ag, Ir, Pt, Au, and Pb. The method works well for all classes of metals, i.e., simple metals, noble metals, and transition metals. We compared our results with full potential linear-muffin-tin orbital and embedded atom method (EAM) calculations, as well as experiment, and found good agreement. This is impressive, since the NRL-TB approach only fits to first-principles full-potential linearized augmented plane-wave equations of state and band structures for cubic systems. Comparable accuracy with EAM potentials can be achieved only by fitting to the stacking fault energy.

A Facile Synthesis of MPd (M=Co, Cu) Nanoparticles and Their Catalysis for Formic Acid Oxidation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mazumder, Vismadeb; Chi, Miaofang; Mankin, Max

2012-01-01

Monodisperse CoPd nanoparticles (NPs) were synthesized and studied for catalytic formic acid (HCOOH) oxidation (FAO). The NPs were prepared by coreduction of Co(acac)2 (acac = acetylacetonate) and PdBr2 at 260 C in oleylamine and trioctylphosphine, and their sizes (5-12 nm) and compositions (Co10Pd90 to Co60Pd40) were controlled by heating ramp rate, metal salt concentration, or metal molar ratios. The 8 nm CoPd NPs were activated for HCOOH oxidation by a simple ethanol wash. In 0.1 M HClO4 and 2 M HCOOH solution, their catalytic activities followed the trend of Co50Pd50 > Co60Pd40 > Co10Pd90 > Pd. The Co50Pd50 NPs hadmore » an oxidation peak at 0.4 V with a peak current density of 774 A/gPd. As a comparison, commercial Pd catalysts showed an oxidation peak at 0.75 V with peak current density of only 254 A/gPd. The synthesis procedure could also be extended to prepare CuPd NPs when Co(acac)2 was replaced by Cu(ac)2 (ac = acetate) in an otherwise identical condition. The CuPd NPs were less active catalysts than CoPd or even Pd for FAO in HClO4 solution. The synthesis provides a general approach to Pd-based bimetallic NPs and will enable further investigation of Pd-based alloy NPs for electro-oxidation and other catalytic reactions.« less

Palladium and gold removal and recovery from precious metal solutions and electronic scrap leachates by Desulfovibrio desulfuricans.

PubMed

Creamer, Neil J; Baxter-Plant, Victoria S; Henderson, John; Potter, M; Macaskie, Lynne E

2006-09-01

Biomass of Desulfovibrio desulfuricans was used to recover Au(III) as Au(0) from test solutions and from waste electronic scrap leachate. Au(0) was precipitated extracellularly by a different mechanism from the biodeposition of Pd(0). The presence of Cu(2+) ( approximately 2000 mg/l) in the leachate inhibited the hydrogenase-mediated removal of Pd(II) but pre-palladisation of the cells in the absence of added Cu(2+) facilitated removal of Pd(II) from the leachate and more than 95% of the Pd(II) was removed autocatalytically from a test solution supplemented with Cu(II) and Pd(II). Metal recovery was demonstrated in a gas-lift electrobioreactor with electrochemically generated hydrogen, followed by precipitation of recovered metal under gravity. A 3-stage bioseparation process for the recovery of Au(III), Pd(II) and Cu(II) is proposed.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Chenyu; Chen, Dennis P.; Unocic, Raymond R.

The high performance of Pd-based intermetallic nanocatalysts has the potential to replace Pt-containing catalysts for fuel-cell reactions. Conventionally, intermetallic particles are obtained through the annealing of nanoparticles of a random alloy distribution. However, this method inevitably leads to sintering of the nanoparticles and generates polydisperse samples. Here, monodisperse PdCu nanoparticles with the ordered B2 phase were synthesized by seed-mediated co-reduction using PdCu nanoparticle seeds with a random alloy distribution (A1 phase). A time-evolution study suggests that the particles must overcome a size-dependent activation barrier for the ordering process to occur. Characterization of the as-prepared PdCu B2 nanoparticles by electron microscopymore » techniques revealed surface segregation of Pd as a thin shell over the PdCu core. The ordered nanoparticles exhibit superior activity and durability for the oxygen reduction reaction in comparison with PdCu A1 nanoparticles. This seed-mediated co-reduction strategy produced monodisperse nanoparticles ideally suited for structure–activity studies. Furthermore, the study of their growth mechanism provides insights into the size dependence of disorder–order transformations of bimetallic alloys at the nanoscale, which should enable the design of synthetic strategies toward other intermetallic systems.« less

Platinum group elements in stream sediments of mining zones: The Hex River (Bushveld Igneous Complex, South Africa)

NASA Astrophysics Data System (ADS)

Almécija, Clara; Cobelo-García, Antonio; Wepener, Victor; Prego, Ricardo

2017-05-01

Assessment of the environmental impact of platinum group elements (PGE) and other trace elements from mining activities is essential to prevent potential environmental risks. This study evaluates the concentrations of PGE in stream sediments of the Hex River, which drains the mining area of the Bushveld Igneous Complex (South Africa), at four sampling points. Major, minor and trace elements (Fe, Ca, Al, Mg, Mn, V, Cr, Zn, Cu, As, Co, Ni, Cd, and Pb) were analyzed by FAAS and ETAAS in suspended particulate matter and different sediment fractions (<63, 63-500 and 500-2000 μm), and Pt, Pd, Rh, and Ir were measured by ICP-MS after removal of interfering elements (cation exchange resin 50W-DOWEX-X8). Procedures were blank-corrected and accuracy checked using reference materials. Nickel, Cr, Pt, Pd, Rh and Ir show concentrations 3-, 13- 18-, 28-, 48- and 44- fold the typical upper continental crust levels, respectively, although lower than concentrations reported for the parent rocks. The highest concentrations were observed closer to the mining area, decreasing with distance and in the <63 μm fraction, probably derived from atmospheric deposition and surface runoff of PGE-rich particles released from mining activities. Thus, mining activities are causing some disturbance of the surface PGE geochemical cycle, increasing the presence of PGE in the fine fraction of river sediments. We propose that indicators such as airborne particulate matter, and soil and river sediment quality, should be added to the protocols for evaluating the sustainability of mining activities.

Recombinant Human Factor IX Produced from Transgenic Porcine Milk

PubMed Central

Lee, Meng-Hwan; Lin, Yin-Shen; Tu, Ching-Fu; Yen, Chon-Ho

2014-01-01

Production of biopharmaceuticals from transgenic animal milk is a cost-effective method for highly complex proteins that cannot be efficiently produced using conventional systems such as microorganisms or animal cells. Yields of recombinant human factor IX (rhFIX) produced from transgenic porcine milk under the control of the bovine α-lactalbumin promoter reached 0.25 mg/mL. The rhFIX protein was purified from transgenic porcine milk using a three-column purification scheme after a precipitation step to remove casein. The purified protein had high specific activity and a low ratio of the active form (FIXa). The purified rhFIX had 11.9 γ-carboxyglutamic acid (Gla) residues/mol protein, which approached full occupancy of the 12 potential sites in the Gla domain. The rhFIX was shown to have a higher isoelectric point and lower sialic acid content than plasma-derived FIX (pdFIX). The rhFIX had the same N-glycosylation sites and phosphorylation sites as pdFIX, but had a higher specific activity. These results suggest that rhFIX produced from porcine milk is physiologically active and they support the use of transgenic animals as bioreactors for industrial scale production in milk. PMID:24955355

Separation and preconcentration of platinum-group metals from spent autocatalysts solutions using a hetero-polymeric S, N-containing sorbent and determination by high-resolution continuum source graphite furnace atomic absorption spectrometry.

PubMed

Eskina, Vasilina V; Dalnova, Olga A; Filatova, Daria G; Baranovskaya, Vasilisa B; Karpov, Yuri A

2016-10-01

This paper describes the potential of high-resolution continuum source graphite furnace atomic absorption spectrometry for determination of Pt, Pd and Rh after separation and concentration by original in-house developed heterochain polymer S, N-containing sorbent. The methods of sample preparation of spent ceramic-based autocatalysts were considered, two of which were used: autoclave decomposition in mixture of acids HCl:HNO3 (3:1) and high-temperature melting with K2S2O7. Both methods anyway limit the direct determination of analytes by HR CS GFAAS. Using the first method it is an incomplete digestion of spent autocatalysts samples, since the precipitate is Si, and the rhodium metal dissolves with difficulty and partially passes into solution. In contrast to the first method, the second method allow to completely transfer analytes into solution, however, the background signal produced by the chemical composition of the flux, overlaps the analytical zone. It was found, that Pt, Pd and Rh contained in the spent ceramic automotive catalysts could be effectively separated and concentrated by heterochain polymer S, N-containing sorbent, which has high sorption capacity, selectivity and resistant to dilute acids. The chosen HR CS GFAAS analysis conditions enable us to determine Pt, Pd and Rh with good metrological characteristics. The concentrations of Pt, Pd and Rh in two samples of automobile exhaust catalysts were found in range of 0.00015-0.00050; 0.170-0.189; 0.0180-0.0210wt%, respectively. The relative standard deviation obtained by HR CS GFAAS was not more than 5%. Limits of detection by HR CS GFAAS achieved were 6.2·10(-6)wt% for Pt, 1.8·10(-6)wt% for Pd, and 3.4·10(-6)wt% for Rh. Limits of determination achieved by HR CS GFAAS were 1.1·10(-5)wt% for Pt, 6.9·10(-5)wt% for Pd, and 8.3·10(-5)wt% for Rh. To control the accuracy of PGM in sorption concentrates by HR CS GFAAS method, it was appropriate to conduct an inter-method comparative experiment. The researches on the application of atomic-emission spectroscopy method with inductively coupled plasma as a comparative method were conducted. In addition, the trueness control of the obtained results is confirmed by added-found method. Copyright © 2016 Elsevier B.V. All rights reserved.

Mean glandular dose coefficients (D(g)N) for x-ray spectra used in contemporary breast imaging systems.

PubMed

Nosratieh, Anita; Hernandez, Andrew; Shen, Sam Z; Yaffe, Martin J; Seibert, J Anthony; Boone, John M

2015-09-21

To develop tables of normalized glandular dose coefficients D(g)N for a range of anode-filter combinations and tube voltages used in contemporary breast imaging systems. Previously published mono-energetic D(g)N values were used with various spectra to mathematically compute D(g)N coefficients. The tungsten anode spectra from TASMICS were used; molybdenum and rhodium anode-spectra were generated using MCNPX Monte Carlo code. The spectra were filtered with various thicknesses of Al, Rh, Mo or Cu. An initial half value layer (HVL) calculation was made using the anode and filter material. A range of the HVL values was produced with the addition of small thicknesses of polymethyl methacrylate (PMMA) as a surrogate for the breast compression paddle, to produce a range of HVL values at each tube voltage. Using a spectral weighting method, D(g)N coefficients for the generated spectra were calculated for breast glandular densities of 0%, 12.5%, 25%, 37.5%, 50% and 100% for a range of compressed breast thicknesses from 3 to 8 cm. Eleven tables of normalized glandular dose (D(g)N) coefficients were produced for the following anode/filter combinations: W + 50 μm Ag, W + 500 μm Al, W + 700 μm Al, W + 200 μm Cu, W + 300 μm Cu, W + 50 μm Rh, Mo + 400 μm Cu, Mo + 30 μm Mo, Mo + 25 μm Rh, Rh + 400 μm Cu and Rh + 25 μm Rh. Where possible, these results were compared to previously published D(g)N values and were found to be on average less than 2% different than previously reported values.Over 200 pages of D(g)N coefficients were computed for modeled x-ray system spectra that are used in a number of new breast imaging applications. The reported values were found to be in excellent agreement when compared to published values.

Mean Glandular dose coefficients (DgN) for x-ray spectra used in contemporary breast imaging systems

PubMed Central

Nosratieh, Anita; Hernandez, Andrew; Shen, Sam Z.; Yaffe, Martin J.; Seibert, J. Anthony; Boone, John M.

2015-01-01

Purpose To develop tables of normalized glandular dose coefficients DgN for a range of anode–filter combinations and tube voltages used in contemporary breast imaging systems. Methods Previously published mono-energetic DgN values were used with various spectra to mathematically compute DgN coefficients. The tungsten anode spectra from TASMICS were used; Molybdenum and Rhodium anode-spectra were generated using MCNPx Monte Carlo code. The spectra were filtered with various thicknesses of Al, Rh, Mo or Cu. An initial HVL calculation was made using the anode and filter material. A range of the HVL values was produced with the addition of small thicknesses of polymethyl methacrylate (PMMA) as a surrogate for the breast compression paddle, to produce a range of HVL values at each tube voltage. Using a spectral weighting method, DgN coefficients for the generated spectra were calculated for breast glandular densities of 0%, 12.5%, 25%, 37.5%, 50% and 100% for a range of compressed breast thicknesses from 3 to 8 cm. Results Eleven tables of normalized glandular dose (DgN) coefficients were produced for the following anode/filter combinations: W + 50 μm Ag, W + 500 μm Al, W + 700 μm Al, W + 200 μm Cu, W + 300 μm Cu, W + 50 μm Rh, Mo + 400 μm Cu, Mo + 30 μm Mo, Mo + 25 μm Rh, Rh + 400 μm Cu and Rh + 25 μm Rh. Where possible, these results were compared to previously published DgN values and were found to be on average less than 2% different than previously reported values. Conclusion Over 200-pages of DgN coefficients were computed for modeled x-ray system spectra that are used in a number of new breast imaging applications. The reported values were found to be in excellent agreement when compared to published values. PMID:26348995

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Sufen; Xiao, Weiping; Wang, Jie

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

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

DOE PAGES

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

2016-08-01

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

Study of Sn and SnAgCu Solders Wetting Reaction on Ni/Pd/Au Substrates

NASA Astrophysics Data System (ADS)

Liu, C. Y.; Wei, Y. S.; Lin, E. J.; Hsu, Y. C.; Tang, Y. K.

2016-12-01

Wetting reactions of pure Sn and Sn-Ag-Cu solder balls on Au(100 Å and 1000 Å)/Pd(500 Å)/Ni substrates were investigated. The (Au, Pd)Sn4 phase formed in the initial interfacial reaction between pure Sn and Au(100 Å and 1000 Å)/Pd(500 Å)/Ni substrates. Then, the initially formed (Au, Pd)Sn4 compound layer either dissolved or spalled into the molten Sn solder with 3 s of reflowing. The exposed Ni under-layer reacted with Sn solder and formed an interfacial Ni3Sn4 compound. We did not observe spalling compound in the Sn-Ag-Cu case, either on the thin Au (100 Å) or the thick Au (1000 Å) substrates. This implies that the Cu content in the Sn-Ag-Cu solder can efficiently suppress the spalling effect and really stabilize the interfacial layer. Sn-Ag-Cu solder has a better wetting than that of the pure Sn solder, regardless of the Au thickness of the Au/Pd/Ni substrate. For both cases of pure Sn and Sn-Ag-Cu, the initial wetting (<3-s reflowing) on the thin Au (100 Å) substrate is better than that of the thick Au (1000 Å) substrate. Over 3-s reflowing, the wetting on the thicker Au layer (1000 Å) substrate becomes better than the wetting on the thinner Au layer (100 Å) substrate.

Structure and magnetic properties of Fe12X clusters

NASA Astrophysics Data System (ADS)

Gutsev, G. L.; Johnson, L. E.; Belay, K. G.; Weatherford, C. A.; Gutsev, L. G.; Ramachandran, B. R.

2014-02-01

The electronic and geometrical structures of a Fe12X family of binary clusters Fe12Al, Fe12Sc, Fe12Ti, Fe12V, Fe12Cr, Fe12Mn, Fe12Co, Fe12Ni, Fe12Cu, Fe12Zn, Fe12Y, Fe12Zr, Fe12Nb, Fe12Mo, Fe12Tc, Fe12Ru, Fe12Rh, Fe12Pd, Fe12Ag, Fe12Cd, and Fe12Gd are studied using density functional theory within generalized gradient approximation. It is found that the geometrical structures corresponding to the lowest total energy states found for the Fe12X clusters possess icosahedral shape with the substituent atom occupying the central or a surface site. The only exception presents Fe12Nb where a squeezed cage structure is the energetically most favorable. The substitution of an atom in the Fe13 cluster results in the decrease of its total spin magnetic moment of 44 μB, except for Fe12Mn and Fe12Gd. The Fe12X clusters are more stable than the parent Fe13 cluster when X = Al, Sc, Ti, V, Co, Y, Zr, Nb, Mo, Tc, Ru, and Rh.

Highly Active and Selective Hydrogenation of CO2 to Ethanol by Ordered Pd-Cu Nanoparticles.

PubMed

Bai, Shuxing; Shao, Qi; Wang, Pengtang; Dai, Qiguang; Wang, Xingyi; Huang, Xiaoqing

2017-05-24

Carbon dioxide (CO 2 ) hydrogenation to ethanol (C 2 H 5 OH) is considered a promising way for CO 2 conversion and utilization, whereas desirable conversion efficiency remains a challenge. Herein, highly active, selective and stable CO 2 hydrogenation to C 2 H 5 OH was enabled by highly ordered Pd-Cu nanoparticles (NPs). By tuning the composition of the Pd-Cu NPs and catalyst supports, the efficiency of CO 2 hydrogenation to C 2 H 5 OH was well optimized with Pd 2 Cu NPs/P25 exhibiting high selectivity to C 2 H 5 OH of up to 92.0% and the highest turnover frequency of 359.0 h -1 . Diffuse reflectance infrared Fourier transform spectroscopy results revealed the high C 2 H 5 OH production and selectivity of Pd 2 Cu NPs/P25 can be ascribed to boosting *CO (adsorption CO) hydrogenation to *HCO, the rate-determining step for the CO 2 hydrogenation to C 2 H 5 OH.

Metal organic frameworks enhanced graphene oxide electrode for humidity sensor

NASA Astrophysics Data System (ADS)

Zhang, Wen; Meng, Siyu; Wang, Hui; He, Yongning

2018-03-01

Copper benzene-1,3,5-tricarboxylate (Cu-BTC), a typical metal organic framework, is deposited on the graphene oxide (GO) film to prepare a resistance humidity sensor (Cu- BTC/GO) for improving humidity sensing. The characteristics of Cu-BTC, GO and Cu- BTC/GO were measured by scanning electron microscopy (SEM), X-ray diffraction (XRD), nitrogen isotherm adsorption and electrochemical impedance spectroscopy (EIS). The humidity sensing properties of the Cu-BTC/GO were investigated in detail. The obtained Cu-BTC/GO demonstrates good sensitivity and repeatability over 11%-85% relative humidity (RH) measurements. The Cu-BTC/GO coated device shows high normalized response (S) value (6200%), which is much higher than that of pure GO coated device. Sensing mechanism of Cu- BTC/GO is discussed based on different RH and the results indicate that moderate amounts of Cu-BTC deposition can enhance sensing abilities of GO. High specific surface area and interfacial conductivity are crucial factors to fabricate humidity sensors with high performance.

Electrochemical immunoassay for carcinoembryonic antigen based on signal amplification strategy of nanotubular mesoporous PdCu alloy.

PubMed

Cai, Yanyan; Li, He; Li, Yuyang; Zhao, Yanfang; Ma, Hongmin; Zhu, Baocun; Xu, Caixia; Wei, Qin; Wu, Dan; Du, Bin

2012-01-01

Interests in using nanoporous metals for biosensing applications have been increasing. Herein, nanotubular mesoporous PdCu (NM-PdCu) alloy is used to fabricate a novel label-free electrochemical immunosensor for cancer biomarker carcinoembryonic antigen (CEA). It operates through physisorption of anti-CEA on NM-PdCu and the mixture of sulfonated graphene sheets (HSO(3)-GS) and thionine (TH) functionalized glassy carbon electrode interface as the detection platform. In this study, chitosan (CS)-PdCu is bound very strongly to carcinoembryonic antibody (anti-CEA), because of the good electron conductivity, high surface area, and good biocompatibility. CS-PdCu is immobilized on electrodes by electrostatic interactions between the negatively charged sulfo group of HSO(3)-GS and the abundant positively charged amino groups of chitosan. TH acts as the redox probe. Under the optimized conditions, the electrochemical immunosensor exhibits a wide working range from 0.01 to 12 ng/mL with a low detection limit of 4.86 pg/mL. The accuracy, reproducibility, and stability of the immunosensor are acceptable. The assay is evaluated for real serum samples, receiving satisfactory results. The nanoporous metal materials-based immunoassay provides a promising approach in clinical application and thus represents a versatile detection method. Copyright © 2012 Elsevier B.V. All rights reserved.

Hydrogen sorption characteristics of nanostructured Pd–10Rh processed by cryomilling

DOE PAGES

Yang, Nancy; Yee, Joshua K.; Zhang, Zhihui; ...

2014-10-03

Palladium and its alloys are model systems for studying solid-state storage of hydrogen. Mechanical milling is commonly used to process complex powder systems for solid-state hydrogen storage; however, milling can also be used to evolve nanostructured powder to modify hydrogen sorption characteristics. In the present study, cryomilling (mechanical attrition milling in a cryogenic liquid) is used to produce nanostructured palladium-rhodium alloy powder. Characterization of the cryomilled Pd-10Rh using electron microscopy, X-ray diffraction, and surface area analysis reveals that (i) particle morphology evolves from spherical to flattened disk-like particles; while the (ii) crystallite size decreases from several microns to less thanmore » 100 nm and (iii) dislocation density increases with increased cryomilling time. Hydrogen absorption and desorption isotherms as well as the time scales for absorption were measured for cryomilled Pd-10Rh, and correlated with observed microstructural changes induced by the cryomilling process. In short, as the microstructure of the Pd-10Rh alloy is refined by cryomilling: (i) the maximum hydrogen concentration in the α-phase increases, (ii) the pressure plateau becomes flatter, and (iii) the equilibrium hydrogen capacity at 760 Torr increases. In addition, the rate of hydrogen absorption was reduced by an order of magnitude compared to non-cryomilled (atomized) powder.« less

The pH-dependent release of platinum group elements (PGEs) from gasoline and diesel fuel catalysts: Implication for weathering in soils.

PubMed

Suchá, Veronika; Mihaljevič, Martin; Ettler, Vojtěch; Strnad, Ladislav

2016-04-15

Powdered samples of new and old gasoline catalysts (Pt, Pd, Rh) and new and old diesel (Pt) catalysts were subjected to a pH-static leaching procedure (pH 2-9) coupled with thermodynamic modeling using PHREEQC-3 to verify the release and mobility of PGEs (platinum group elements). PGEs were released under acidic conditions, mostly exhibiting L-shaped leaching patterns: diesel old: 5.47, 0.005, 0.02; diesel new: 68.5, 0.23, 0.11; gasoline old: 0.1, 11.8, 4.79; gasoline new 2.6, 25.2, 35.9 in mg kg(-1) for Pt, Pd and Rh, respectively. Only the new diesel catalyst had a strikingly different leaching pattern with elevated concentrations at pH 4, probably influenced by the dissolution of the catalyst carrier and washcoat. The pH-static experiment coupled with thermodynamic modeling was found to be an effective instrument for understanding the leaching behavior of PGEs under various environmental conditions, and indicated that charged Pt and Rh species may be adsorbed on the negatively charged surface of kaolinite or Mn oxides in the soil system, whereas uncharged Pd and Rh species may remain mobile in soil solutions. Copyright © 2016 Elsevier Ltd. All rights reserved.

Pd/Cu-Oxide Nanoconjugate at Zeolite-Y Crystallite Crafting the Mesoporous Channels for Selective Oxidation of Benzyl-Alcohols.

PubMed

Sharma, Mukesh; Das, Biraj; Sharma, Mitu; Deka, Biplab K; Park, Young-Bin; Bhargava, Suresh K; Bania, Kusum K

2017-10-11

Solid-state grinding of palladium and copper salts allowed the growth of palladium/copper oxide interface at the zeolite-Y surface. The hybrid nanostructured material was used as reusable heterogeneous catalyst for selective oxidation of various benzyl alcohols. The large surface area provided by the zeolite-Y matrix highly influenced the catalytic activity, as well as the recyclability of the synthesized catalyst. Impregnation of PdO-CuO nanoparticles on zeolite crystallite leads to the generation of mesoporous channel that probably prevented the leaching of the metal-oxide nanoparticles and endorsed high mass transfer. Formation of mesoporous channel at the external surface of zeolite-Y was evident from transmission electron microscopy and surface area analysis. PdO-CuO nanoparticles were found to be within the range of 2-5 nm. The surface area of PdO-CuO-Y catalyst was found to be much lower than parent zeolite-Y. The decrease in surface area as well as the presence of hysteresis loop in the N 2 -adsoprtion isotherm further suggested successful encapsulation of PdO-CuO nanoparticles via the mesoporous channel formation. The high positive shifting in binding energy in both Pd and Cu was attributed to the influence of zeolite-Y framework on lattice contraction of metal oxides via confinement effect. PdO-CuO-Y catalyst was found to oxidize benzyl alcohol with 99% selectivity. On subjecting to microwave irradiation the same oxidation reaction was found to occur at ambient condition giving same conversion and selectivity.

Major and trace elements in organically or conventionally produced milk.

PubMed

Hermansen, John E; Badsberg, Jens H; Kristensen, Troels; Gundersen, Vagn

2005-08-01

A total of 480 samples of milk from 10 organically and 10 conventionally producing dairy farms in Denmark and covering 8 sampling periods over 1 year (triplicate samplings) were analysed for 45 trace elements and 6 major elements by high-resolution inductively coupled plasma mass spectrometry and inductively coupled plasma atomic emission spectrometry. Sampling, sample preparation, and analysis of the samples were performed under carefully controlled contamination-free conditions. The dairy cattle breeds were Danish-Holstein or Jersey. Sources of variance were quantified, and differences between production systems and breeds were tested. The major source of variation for most elements was week of sampling. Concentrations of Al, Cu, Fe, Mo, Rb, Se, and Zn were within published ranges. Concentrations of As, Cd, Cr, Mn and Pb were lower, and concentrations of Co and Sr were higher than published ranges. Compared with Holsteins, Jerseys produced milk with higher concentrations of Ba, Ca, Cu, Fe, Mg, Mn, Mo, P, Rh, and Zn and with a lower concentration of Bi. The organically produced milk, compared with conventionally produced milk, contained a significantly higher concentration of Mo (48 v. 37 ng/g) and a lower concentration of Ba (43 v. 62 ng/g), Eu (4 v. 7 ng/g), Mn (16 v. 20 ng/g) and Zn (4400 v. 5150 ng/g respectively). The investigation yielded typical concentrations for the following trace elements in milk, for which no or very few data are available: Ba, Bi, Ce, Cs, Eu, Ga, Gd, In, La, Nb, Nd, Pd, Pr, Rh, Sb, Sm, Tb, Te, Th, Ti, Tl, U, V, Y, and Zr.

Interference from retrieval cues in Parkinson's disease.

PubMed

Crescentini, Cristiano; Marin, Dario; Del Missier, Fabio; Biasutti, Emanuele; Shallice, Tim

2011-11-01

Existing studies on memory interference in Parkinson's disease (PD) patients have provided mixed results and it is unknown whether PD patients have problems in overcoming interference from retrieval cues. We investigated this issue by using a part-list cuing paradigm. In this paradigm, after the study of a list of items, the presentation of some of these items as retrieval cues hinders the recall of the remaining ones. We tested PD patients' (n = 19) and control participants' (n = 16) episodic memory in the presence and absence of part-list cues, using initial-letter probes, and following either weak or strong serial associative encoding of list items. Both PD patients and control participants showed a comparable and significant part-list cuing effect after weak associative encoding (13% vs. 12% decrease in retrieval in part-list cuing vs. no part-list cuing -control- conditions in PD patients and control participants, respectively), denoting a similar effect of cue-driven interference in the two populations when a serial retrieval strategy is hard to develop. However, only PD patients showed a significant part-list cuing effect after strong associative encoding (20% vs. 5% decrease in retrieval in patients and controls, respectively). When encoding promotes the development of an effective serial retrieval strategy, the presentation of part-list cues has a specifically disruptive effect in PD patients. This indicates problems in strategic retrieval, probably related to PD patients' increased tendency to rely on external cues. Findings in control conditions suggest that less effective encoding may have contributed to PD patients' memory performance.

Pharmacokinetics, pharmacodynamics and safety of recombinant canine FVIIa in a study dosing one haemophilia A and one haemostatically normal dog.

PubMed

Knudsen, T; Kristensen, A T; Nichols, T C; Agersø, H; Jensen, A L; Kjalke, M; Ezban, M; Tranholm, M

2011-11-01

Recombinant human FVIIa (rhFVIIa) corrects the coagulopathy in hemophilia A and B as well as FVII deficiency. This is also the case in dogs until canine anti-human FVIIa antibodies develop (~2 weeks). Recombinant canine factor VIIa (rcFVIIa), successfully over-expressed by gene transfer in haemophilia dogs, has provided long-term haemostasis (>2 years). However, pharmacokinetics (PK), pharmacodynamics (PD) and safety of rcFVIIa after pharmacological administration have not been reported. We therefore wanted to explore the safety, PK and PD of rcFVIIa in dogs. A pilot study was set up to evaluate the safety as well as PK and PD of rcFVIIa after a single intravenous dose of 270 μg kg(-1) to one HA and one haemostatically normal dog and to directly compare rcFVIIa with rhFVIIa in these two dogs. Single doses of rcFVIIa and rhFVIIa were well tolerated. No adverse events were observed. Pharmacokinetic characteristics including half-life (FVIIa activity: 1.2-1.8 h; FVIIa antigen 2.8-3.7 h) and clearance were comparable for rcFVIIa and rhFVIIa. Kaolin-activated thromboelastography approached normal in the HA dog with the improvement being most pronounced after rcFVIIa. This study provided the first evidence that administering rcFVIIa intravenously is feasible, safe, well tolerated and efficacious in correcting the haemophilic coagulopathy in canine HA and that rcFVIIa exhibits pharmacokinetic characteristics comparable to rhFVIIa in haemophilic and haemostatically competent dogs. This strengthens the hypothesis that rcFVIIa can be administered to dogs to mimic the administration of rhFVIIa to humans. © 2011 Blackwell Publishing Ltd.

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

NASA Astrophysics Data System (ADS)

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

2017-09-01

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

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

PubMed

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

2017-09-02

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

FAST TRACK COMMUNICATION: Reinterpreting the Cu Pd phase diagram based on new ground-state predictions

NASA Astrophysics Data System (ADS)

Bärthlein, S.; Hart, G. L. W.; Zunger, A.; Müller, S.

2007-01-01

Our notions of the phase stability of compounds rest to a large extent on the experimentally assessed phase diagrams. Long ago, it was assumed that in the Cu-Pd system for xPd<=25% there are at least two phases at high temperature (L12 and a L12-based superstructure), which evolve into a single L12-ordered phase at low temperature. By constructing a first-principles Hamiltonian, we predict a yet undiscovered Cu7Pd ground state at xPd = 12.5% (referred to as S1 below) and an L12-like Cu9Pd3 superstructure at 25% (referred to as S2). We find that in the low-temperature regime, a single L12 phase cannot be stable, even with the addition of anti-sites. Instead we find that an S2-phase with S1-like ordering tendency will form. Previous short-range order diffraction data are quantitatively consistent with these new predictions.

Growth and Doping of Al(x)Ga(1-x)N Films by Electron Cyclotron Resonance Assisted Molecular Beam Epitaxy

DTIC Science & Technology

1993-05-30

shown in Figures 9a and 9b. The carrier concentration was computed from the measured values of the Hall coefficient, RH , using the equation n (5) eRH...The electron concentrations in Figure 1 were calculated from the expression 1 (1) eRjj where RH is the Hall constant. Equation (1) assumes electron...expressions: 2 2RH fcP + ,’dP• (2) RH = (ncp + nd/pd) 2 e 1 p 1 (3) ncelc + ndel.d where nc and nd are the concentrations of conducting carriers in the

Movement Activation and Inhibition in Parkinson’s Disease: a Functional Imaging Study

PubMed Central

Disbrow, E. A.; Sigvardt, K. A.; Franz, E. A.; Turner, R. S.; Russo, K. A.; Hinkley, L.B.; Herron, T. J.; Ventura, M. I.; Zhang, L.; Malhado-Chang, N.

2015-01-01

Background Parkinson’s disease (PD), traditionally considered a movement disorder, has been shown to affect executive function such as the ability to adapt behavior in response to new environmental situations. Objective to identify the impact of PD on neural substrates subserving two specific components of normal movement which we refer to as activation (initiating an un-cued response) and inhibition (suppressing a cued response). Methods We used fMRI to measure pre-movement processes associated with activating an un-cued response and inhibiting a cued response plan in 13 PD (ON anti-parkinsonian medications) and 13 control subjects. Subjects were shown a visual arrow cue followed by a matched or mismatched response target that instructed them to respond with a right, left, or bilateral button press. In mismatched trials, an un-cued (new) response was initiated, or the previously cued response was suppressed. Results We were able to isolate pre-movement responses in dorsolateral prefrontal cortex, specifically in the right hemisphere. During the activation of an un-cued movement, PD subjects showed decreased activity in the putamen and increased cortical activity in bilateral DLPFC, SMA, subcentral gyrus and inferior frontal operculum. During inhibition of a previously cued movement, the PD group showed increased activation in SMA, S1/M1, premotor and superior parietal areas. Conclusion Right DLPFC plays a role in pre-movement processes, and DLPFC activity is abnormal in PD. Decreased specificity of responses was observed in multiple ROI’s. The basal ganglia are involved in circuits that coordinate activation and inhibition involved in action selection as well as execution. PMID:23938347

Penta-Twinned Copper Nanorods: Facile Synthesis via Seed-Mediated Growth and Their Tunable Plasmonic Properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Luo, Ming; Ruditskiy, Aleksey; Peng, Hsin-Chieh

When seed-mediated growth is used as a versatile approach to the synthesis of penta-twinned Cu nanorods with uniform diameters and controllable aspect ratios is reported. The success of this approach relies on our recent synthesis of uniform Pd decahedra, with sizes in the range of 6–20 nm. The Pd decahedral seeds can direct the heterogeneous nucleation and growth of Cu along the fivefold axis to produce nanorods with uniform diameters defined by the lateral dimension of the original seeds. Due to a large mismatch in the lattice constants between Cu and Pd (7.1%), the deposited Cu is forced to growmore » along one side of the Pd decahedral seed, generating a nanorod with an asymmetric distribution of Cu, with the Pd seed situated at one of the two ends. According to extinction spectra, the as-obtained Cu nanorods can be stored in water under the ambient conditions for at least six months without noticeable degradation. The resulting stability allows us to systematically investigate the size-dependent surface plasmon resonance properties of the penta-twinned Cu nanorods. With the nanorod transverse modes positioned at 560 nm, the longitudinal modes can be readily tuned from the visible to the near-infrared region by controlling the aspect ratio.« less

Penta-Twinned Copper Nanorods: Facile Synthesis via Seed-Mediated Growth and Their Tunable Plasmonic Properties

DOE PAGES

Luo, Ming; Ruditskiy, Aleksey; Peng, Hsin-Chieh; ...

2016-01-07

When seed-mediated growth is used as a versatile approach to the synthesis of penta-twinned Cu nanorods with uniform diameters and controllable aspect ratios is reported. The success of this approach relies on our recent synthesis of uniform Pd decahedra, with sizes in the range of 6–20 nm. The Pd decahedral seeds can direct the heterogeneous nucleation and growth of Cu along the fivefold axis to produce nanorods with uniform diameters defined by the lateral dimension of the original seeds. Due to a large mismatch in the lattice constants between Cu and Pd (7.1%), the deposited Cu is forced to growmore » along one side of the Pd decahedral seed, generating a nanorod with an asymmetric distribution of Cu, with the Pd seed situated at one of the two ends. According to extinction spectra, the as-obtained Cu nanorods can be stored in water under the ambient conditions for at least six months without noticeable degradation. The resulting stability allows us to systematically investigate the size-dependent surface plasmon resonance properties of the penta-twinned Cu nanorods. With the nanorod transverse modes positioned at 560 nm, the longitudinal modes can be readily tuned from the visible to the near-infrared region by controlling the aspect ratio.« less

Yolk-like Fe3O4@C-Au@void@TiO2-Pd hierarchical microspheres with visible light-assisted enhanced photocatalytic degradation of dye

NASA Astrophysics Data System (ADS)

Chen, Suqing; Liang, Huading; Shen, Mao; Jin, Yanxian

2018-04-01

In this paper, we present the design and implementation of a type of yolk-like Fe3O4@C-Au@void@TiO2-Pd hierarchical microspheres with visible light-assisted enhanced photocatalytic degradation of dye and rapid magnetic separation. The resulting composite microspheres exhibited yolk-like hierarchical structures with a 236.3 m2 g-1 surface area and a high-saturation magnetization of 31.5 emu g-1. As an example of applications, the photodegradation of Rhodamine B (RhB) in the presence of NaBH4 was investigated under simulated sunlight irradiation. The results show that the photocatalytic activity of the yolk-like Fe3O4@C-Au@void@TiO2-Pd microcomposites in the RhB photodegradation is higher than the Fe3O4@C-Au@void@TiO2 and Fe3O4@C@TiO2 microcomposites, as they can degrade RhB with 40 min of irradiation time. In addition, by magnetic separation, the as-prepared yolk-like Fe3O4@C-Au@void@TiO2-Pd hierarchical microcomposites can be completely separated and reused for four times.

Perpendicular magnetic anisotropy of Pd-Co alloy films and related multilayers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tsunashima, S.; Nagase, K.; Nakamura, K.

1989-09-01

Magnetic anisotropy of Pd/sub x/Co/sub 1-x/alloy films and Pd/sub 67/Co/sub 33/, Pd/sub 67/Co/sub 33/, Pd/sub 67/Co/sub 33//Cu multilayers are investigated. Vacuum deposited PdCo alloy films exhibit uniaxial anisotropy Ku with the easy axis perpendicular to the film plane. The maximum Ku is about 5X10/sup 6/erg/cm/sup 3/ for x=0.35 to 0.50. Compositional dependence of Ku is similar to that of the magnetostriction constant {lambda}/sub 111/, which suggests magnetostrictive origin. In multilayer films, PdCo/Pt and PdCo/Pd showed positive Ku while PdCo/Cu showed negative.

Pd-Catalyzed Aerobic Oxidative Biaryl Coupling: Non-Redox Cocatalysis by Cu(OTf)2 and Discovery of Fe(OTf)3 as a Highly Effective Cocatalyst.

PubMed

Wang, Dian; Stahl, Shannon S

2017-04-26

Copper salts find widespread use in Pd-catalyzed oxidation reactions, and they are typically used as oxidants or redox-active cocatalysts. Here, we probe the origin of a dramatic acceleration effect of Cu(OTf) 2 in the C-H/C-H aerobic oxidative coupling of o-xylene. NMR spectroscopic analysis of the Pd II catalyst in the presence of Cu(OTf) 2 , together with other experimental and DFT computational studies of the catalytic reaction, show that Cu(OTf) 2 activates the Pd II catalyst for C-H activation via a non-redox pathway and has negligible impact on catalyst reoxidation. These observations led to the testing of other metal triflate salts as cocatalysts, the results of which show that Fe(OTf) 3 is even more effective than Cu(OTf) 2 .

Inert anode containing oxides of nickel iron and cobalt useful for the electrolytic production of metals

DOEpatents

Ray, Siba P.; Liu, Xinghua; Weirauch, Jr., Douglas A.

2002-01-01

An inert anode for the electrolytic production of metals such as aluminum is disclosed. The inert anode includes a ceramic oxide material preferably made from NiO, Fe.sub.2 O.sub.3 and CoO. The inert anode composition may comprise the following mole fractions of NiO, Fe.sub.2 O.sub.3 and CoO: 0.15 to 0.99 NiO; 0.0001 to 0.85 Fe.sub.2 O.sub.3 ; and 0.0001 to 0.45 CoO. The inert anode may optionally include other oxides and/or at least one metal phase, such as Cu, Ag, Pd, Pt, Au, Rh, Ru, Ir and/or Os. The Ni--Fe--Co--O ceramic material exhibits very low solubility in Hall cell baths used to produce aluminum.

Platinum group metals as flux pinning additions in screen printed superconducting YBa 2Cu 3O 7-δ thick films

NASA Astrophysics Data System (ADS)

Langhorn, J.; Bi, Y. J.; Abell, J. S.

1996-02-01

Platinum group metal additions made to thick films of YBCO have induced significant improvements in the superconducting properties, in particular critical current densities ( Jc). Values in excess of 7 × 10 3 A cm -2 at 77 K and zero applied field have been measured. Optical and transmission electron microscopy have shown a homogeneous distribution of sub-micron sized, and larger highly anisotropic 211, believed to result from a reaction between Pt and YBCO to create nucleation sites for 211 precipitates. Indirect supporting thermal analysis evidence for this reaction is presented. An increased density of dislocations associated with the {123}/{211} interface suggests that refined 211 precipitates may act as heterogeneous nucleation sites for flux pinning defects. Similar effects have been observed for additions of other platinum group metals (Rh, Pd).

Inert anode containing oxides of nickel, iron and zinc useful for the electrolytic production of metals

DOEpatents

Ray, Siba P.; Weirauch, Jr., Douglas A.; Liu, Xinghua

2002-01-01

An inert anode for the electrolytic production of metals such as aluminum is disclosed. The inert anode includes a ceramic oxide material preferably made from NiO, Fe.sub.2 O.sub.3 and ZnO. The inert anode composition may comprise the following mole fractions of NiO, Fe.sub.2 O.sub.3 and ZnO: 0.2 to 0.99 NiO; 0.0001 to 0.8 Fe.sub.2 O.sub.3 ; and 0.0001 to 0.3 ZnO. The inert anode may optionally include other oxides and/or at least one metal phase, such as Cu, Ag, Pd, Pt, Au, Rh, Ru, Ir and/or Os. The Ni--Fe--Co--O ceramic material exhibits very low solubility in Hall cell baths used to produce aluminum.

Assessment of exposure to platinum-group metals in urban children

NASA Astrophysics Data System (ADS)

Caroli, S.; Alimonti, A.; Petrucci, F.; Bocca, B.; Krachler, M.; Forastiere, F.; Sacerdote, M. T.; Mallone, S.

2001-07-01

Catalytic converters for automotive traction raise some concern for human health and the environment, due to the release of Pd, Pt and Rh (Pt-Group Metals, PGMs). In fact, the thermal and mechanical conditions under which such devices work (including abrasion effects and hot-temperature chemical reactions with oil fumes) can cause significant release of the PGMs to the environment and eventually affect human health. A pilot investigation was performed to assess the exposure to these metals of 310 schoolchildren aged between 6 and 10 years from the urban and suburban area of Rome. All determinations were performed by high-resolution magnetic-sector inductively-coupled plasma-mass spectrometry after UV irradiation of the samples. The mean concentration values of these metals in urine were found to be (in ng/g creatinine) 7.5±5.4 for Pd, 0.9±1.1 for Pt and 8.5±8.0 for Rh. Urine concentrations of Pd and Rh (but not Pt) were found to be strongly associated with traffic density in the area of residence.

Development of low cost contacts to silicon solar cells

NASA Technical Reports Server (NTRS)

Tanner, D. P.

1980-01-01

The results of the second phase of the program of developing low cost contacts to silicon solar cells using copper are presented. Phase 1 yielded the development of a plated Pd-Cr-Cu contact system. This process produced cells with shunting problems when they were heated to 400 C for 5 minutes. Means of stopping the identified copper diffusion which caused the shunting were investigated. A contact heat treatment study was conducted with Pd-Ag, Ci-Ag, Pd-Cu, Cu-Cr, and Ci-Ni-Cu. Nickel is shown to be an effective diffusion barrier to copper.

Platinum Group Elements (PGE) geochemistry of komatiites and boninites from Dharwar Craton, India: Implications for mantle melting processes

NASA Astrophysics Data System (ADS)

Saha, Abhishek; Manikyamba, C.; Santosh, M.; Ganguly, Sohini; Khelen, Arubam C.; Subramanyam, K. S. V.

2015-06-01

High MgO volcanic rocks having elevated concentrations of Ni and Cr are potential hosts for platinum group elements (PGE) owing to their primitive mantle origin and eruption at high temperatures. Though their higher PGE abundance is economically significant in mineral exploration studies, their lower concentrations are also valuable geochemical tools to evaluate petrogenetic processes. In this paper an attempt has been made to evaluate the PGE geochemistry of high MgO volcanic rocks from two greenstone belts of western and eastern Dharwar Craton and to discuss different mantle processes operative at diverse geodynamic settings during the Neoarchean time. The Bababudan greenstone belt of western and Gadwal greenstone belt of eastern Dharwar Cratons are dominantly composed of high MgO volcanic rocks which, based on distinct geochemical characteristics, have been identified as komatiites and boninites respectively. The Bababudan komatiites are essentially composed of olivine and clinopyroxene with rare plagioclase tending towards komatiitic basalts. The Gadwal boninites contain clinopyroxene, recrystallized hornblende with minor orthopyroxene, plagioclase and sulphide minerals. The Bababudan komatiites are Al-undepleted type (Al2O3/TiO2 = 23-59) with distinctly high MgO (27.4-35.8 wt.%), Ni (509-1066 ppm) and Cr (136-3036 ppm) contents. These rocks have low ΣPGE (9-42 ppb) contents with 0.2-2.4 ppb Iridium (Ir), 0.2-1.4 ppb Osmium (Os) and 0.4-4.4 ppb Ruthenium (Ru) among Iridium group PGE (IPGE); and 1.4-16.2 ppb Platinum (Pt), 2.8-19 ppb Palladium (Pd) and 0.2-9.8 ppb Rhodium (Rh) among Platinum group PGE (PPGE). The Gadwal boninites are high-Ca boninites with CaO/Al2O3 ratios varying between 0.8 and 1.0, with 12-24 wt.% MgO, 821-1168 ppm Ni and 2307-2765 ppm Cr. They show higher concentration of total PGE (82-207 ppb) with Pt concentration ranging from 13 to 19 ppb, Pd between 65 and 180 ppb and Rh in the range of 1.4-3 ppb compared to the Bababudan komatiites. Ir, Os and Ru concentrations range from 0.6 to 2.2 ppb, 0.2 to 0.6 ppb and 1.4 to 2.6 ppb respectively in IPGE. The PGE abundances in Bababudan komatiites were controlled by olivine fractionation whereas that in Gadwal boninites were influenced by fractionation of chromite and sulphides. The Al-undepleted Bababudan komatiites are characterized by low CaO/Al2O3, (Gd/Yb)N, (La/Yb)N, with positive Zr, Hf, Ti anomalies and high Cu/Pd, Pd/Ir ratios at low Pd concentrations suggesting the derivation of parent magma by high degrees (>30%) partial melting of mantle under anhydrous conditions at shallow depth with garnet as a residual phase in the mantle restite. The komatiites are geochemically analogous to Al-undepleted Munro type komatiites and their PGE compositions are consistent with Alexo and Gorgona komatiites. The S-undersaturated character of Bababudan komatiites is attributed to decompression and assimilation of lower crustal materials during magma ascent and emplacement. In contrast, the higher Al2O3/TiO2, lower (Gd/Yb)N, for Gadwal boninites in combination with negative Nb, Zr, Hf, Ti anomalies and lower Cu/Pd at relatively higher Pd/Ir and Pd concentrations reflect high degree melting of refractory mantle wedge under hydrous conditions in an intraoceanic subduction zone setting. Higher Pd/Ir ratios and S-undersaturation of these boninites conform to influx of fluids derived by dehydration of subducted slab resulting into high fluid pressure and metasomatism of mantle wedge.

Intermetallic Compound Growth between Electroless Nickel/Electroless Palladium/Immersion Gold Surface Finish and Sn-3.5Ag or Sn-3.0Ag-0.5Cu Solder

NASA Astrophysics Data System (ADS)

Oda, Yukinori; Fukumuro, Naoki; Yae, Shinji

2018-04-01

Using an electroless nickel/electroless palladium/immersion gold (ENEPIG) surface finish with a thick palladium-phosphorus (Pd-P) layer of 1 μm, the intermetallic compound (IMC) growth between the ENEPIG surface finish and lead-free solders Sn-3.5Ag (SA) or Sn-3.0Ag-0.5Cu (SAC) after reflow soldering and during solid-state aging at 150°C was investigated. After reflow soldering, in the SA/ENEPIG and SAC/ENEPIG interfaces, thick PdSn4 layers of about 2 μm to 3 μm formed on the residual Pd-P layers ( 0.5 μm thick). On the SA/ENEPIG interface, Sn was detected on the upper side of the residual Pd-P layer. On the SAC/ENEPIG interface, no Sn was detected in the residual Pd-P layer, and Cu was detected in the interface between the Pd-P and PdSn4 layers. After 300 h of aging at 150°C, the residual Pd-P layers had diffused completely into the solders. In the SA/ENEPIG interface, an IMC layer consisting of Ni3Sn4 and Ni3SnP formed between the PdSn4 layer and the nickel-phosphorus (Ni-P) layer, and a (Pd,Ni)Sn4 layer formed on the lower side of the PdSn4 layer. On the SAC/ENEPIG interface, a much thinner (Pd,Ni)Sn4 layer was observed, and a (Cu,Ni)6Sn5 layer was observed between the PdSn4 and Ni-P layers. These results indicate that Ni diffusion from the Ni-P layer to the PdSn4 layer produced a thick (Pd,Ni)Sn4 layer in the SA solder case, but was prevented by formation of (Cu,Ni)6Sn5 in the SAC solder case. This causes the difference in solder joint reliability between SA/ENEPIG and SAC/ENEPIG interfaces in common, thin Pd-P layer cases.

Low Pt-content ternary PdCuPt nanodendrites: an efficient electrocatalyst for oxygen reduction reaction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fu, Shaofang; Zhu, Chengzhou; Song, Junhua

2017-01-01

Dendritic nanostructures are capturing increasing attentions in electrocatalysis owing to their unique structural features and low density. Herein, we report for the first time bromide ions mediated synthesis of low-Pt-content PdCuPt ternary nanodendrites via galvanic replacement reaction between Pt precursor and PdCu template in aqueous solution. The experimental results show that the ternary PdCuPt nanodendrites present enhanced electrocatalytic performance for oxygen reduction reaction in acid solution compared with commercial Pt/C as well as some state-of-the-art catalysts. In details, the mass activity of the PdCuPt catalyst with optimized composition is 1.73 A/mgPt at 0.85 V vs RHE, which is 14 timesmore » higher than that of commercial Pt/C catalyst. Moreover, the long-term stability test demonstrates its better durability in acid solution. After 5k cycles, there is still 70% electrochemical surface area maintained. This method provides an efficient way to synthesize trimetallic alloys with controllable composition and specific structure for oxygen reduction reaction.« less

Catalysis beyond frontier molecular orbitals: Selectivity in partial hydrogenation of multi-unsaturated hydrocarbons on metal catalysts

PubMed Central

Liu, Wei; Jiang, Yingda; Dostert, Karl-Heinz; O’Brien, Casey P.; Riedel, Wiebke; Savara, Aditya; Schauermann, Swetlana; Tkatchenko, Alexandre

2017-01-01

The mechanistic understanding and control over transformations of multi-unsaturated hydrocarbons on transition metal surfaces remains one of the major challenges of hydrogenation catalysis. To reveal the microscopic origins of hydrogenation chemoselectivity, we performed a comprehensive theoretical investigation on the reactivity of two α,β-unsaturated carbonyls—isophorone and acrolein—on seven (111) metal surfaces: Pd, Pt, Rh, Ir, Cu, Ag, and Au. In doing so, we uncover a general mechanism that goes beyond the celebrated frontier molecular orbital theory, rationalizing the C═C bond activation in isophorone and acrolein as a result of significant surface-induced broadening of high-energy inner molecular orbitals. By extending our calculations to hydrogen-precovered surface and higher adsorbate surface coverage, we further confirm the validity of the “inner orbital broadening mechanism” under realistic catalytic conditions. The proposed mechanism is fully supported by our experimental reaction studies for isophorone and acrolein over Pd nanoparticles terminated with (111) facets. Although the position of the frontier molecular orbitals in these molecules, which are commonly considered to be responsible for chemical interactions, suggests preferential hydrogenation of the C═O double bond, experiments show that hydrogenation occurs at the C═C bond on Pd catalysts. The extent of broadening of inner molecular orbitals might be used as a guiding principle to predict the chemoselectivity for a wide class of catalytic reactions at metal surfaces. PMID:28782033

PALLADIUM, PLATINUM, RHODIUM, RUTHENIUM AND IRIDIUM IN PERIDOTITES AND CHROMITITES FROM OPHIOLITE COMPLEXES IN NEWFOUNDLAND.

USGS Publications Warehouse

Page, Norman J; Talkington, Raymond W.

1984-01-01

Samples of spinel lherzolite, harzburgite, dunite, and chromitite from the Bay of Islands, Lewis Hills, Table Mountain, Advocate, North Arm Mountain, White Hills Periodite Point Rousse, Great Bend and Betts Cove ophiolite complexes in Newfoundland were analyzed for the platinum-group elements (PGE) Pd, Pt, Rh, Ru and Ir. The ranges of concentration (in ppb) observed for all rocks are: less than 0. 5 to 77 (Pd), less than 1 to 120 (Pt), less than 0. 5 to 20 (Rh), less than 100 to 250 (Ru) and less than 20 to 83 (Ir). Chondrite-normalized PGE ratios suggest differences between rock types and between complexes. Samples of chromitite and dunite show relative enrichment in Ru and Ir and relative depletion in Pt and Pd.

Etude de l'electrocatalyse de la reduction de l'oxygene sur des alliages de palladium cuivre

NASA Astrophysics Data System (ADS)

Fouda-Onana, Frederic

This thesis is on the development of the ORR on Pd-Cu alloys in acid medium. Density Functional Theory (DFT) was used to determine the intrinsic properties of the alloys. The alloys were fabricated by RF sputtering on glassy carbon support and chemical salt reduction on carbon support. They characterised by electrochemical methods and correlations were made between the intrinsic properties and the experimental electrochemical parameters. These correlations were used to explain the electrocatalytic performance of the ORR on these aklooys and to determine the mechanism of this reaction on these electrocatalysts. Accordingly the following aspects were studied in details. In the first step, ab initio investigations of the effect of the intermediate adsorption on the variation of the reversible potential of the ORR on Pt(100) was shown. Density Functional Theory (DFT) was used to determine the energies and the geometry parameters of the intermediates which can be adsorbed on Pt(100) during the oxygen reduction reaction (ORR) and their effect on the . The Comparison of these energies and parameters using the Bridge or the Griffiths sites adsorption mechanism suggests that the two paths are feasible. In both mechanisms, the total adsorption energies of the intermediates species continuously decrease. Moreover, according to the geometry analysis, the O-O bond distance in H2O2 is higher in both (Bridge and Griffiths) processes compared to the gas phase. Such a result suggests a dissociative H2O2 adsorption whatever the type of the involved mechanism involved. In the second step, the Oxygen reduction reaction (ORR) on palladium-copper alloys was studied through two approaches. The first one is based on the correlations between the surface chemical composition and the kinetics parameters of the ORR. The second approach is focused on the correlations between the adsorption energies of O2 and OH of Pd-Cu(111) surfaces and the electronic properties of the alloys. The adsorbtion energy calculations are based on on ab initio calculation using the program VASP (Vienna ab initio program) in a MeDeA environnement (software purchased from Materials Design, Inc. The studies of the oxygen reduction reaction were performed in an acidic media on Palladium-Copper alloys as catalyst. The variation of the intrinsic metal surface properties (lattice parameter, binding energy, work function (Wf), d-band filling and d-band center epsilond) and O2 and OH adsorption energies of on (111) Pd-Cu surface alloys were determined using ab initio program. Calculations of these parameters were based on plane waves approach on slab system with density functional theory (DFT) using the Vienna ab initio simulation program (VASP). It was shown that insertion of Cu atoms in Pd lattice affects geometric and electronic properties of Pd. These changes influence significantly O2 and OH adsorption. In the third step, the oxygen reduction reaction (ORR) on Pd-Cu catalyst has been studied in acidic media. The palladium alloys were prepared by RF magnetron using a palladium and a copper wafer as targets on the glassy carbon substrate. The dual sputtering we used allowed the deposition of about 1micrometer thin film of Pd-Cu on glassy carbon (GC). The ORR kinetics was studied on these catalysts in 0,1M HClO4. Cyclic voltammetry (CV) was used to determine the electrochemical active surface area (Sa). An increase in Sa with the Cu content in the alloy was observed for the alloys containing more than 50% in Cu. The Pd-Cu alloys containing more than 50% in Cu exhibits a constant value of 23 cm2 for Sa. It was further shown that the ORR on the Pd-Cu alloys proceeds through the 4 electrons transfer mechanism and a Tafel slope of 60 mV/dec. The Pd 50Cu50 exhibits the highest activity for this reaction. The enhancement of the electro catalytic activity is attributed to an optimal d band property that makes easier the OOH dissociative adsorption which is considered as chemical rate determining step (RDS) for the ORR. It was also found that all the Pd-Cu alloys exhibited better electrocatalystic performances for the ORR than Pd or Cu alone. From the polarisation of the ORR in 0,1 M HClO4 it was shown that the curve of the Pd electrode was shifted to the lower potentials than those of the Pd-Cu alooys. In addition, the variation of the kinetic current of the ORR at 0,6 V vs. SCE (0,841 V vs. RHE) on the Pd-Cu alloys with the composition of in Cu content exhibited a volcano-shape. (Abstract shortened by UMI.)

Corrosion analysis of NiCu and PdCo thermal seed alloys used as interstitial hyperthermia implants.

PubMed

Paulus, J A; Parida, G R; Tucker, R D; Park, J B

1997-12-01

Ferromagnetic materials with low Curie temperatures are being investigated for use as interstitial implants for fractionated hyperthermia treatment of prostatic disease. Previous investigations of the system have utilized alloys, such as NiCu, with inadequate corrosion resistance, requiring the use of catheters for removal of the implants following treatment or inert surface coatings which may interfere with thermal characteristics of the implants. We are evaluating a palladium-cobalt (PdCo) binary alloy which is very similar to high palladium alloys used in dentistry. Electrochemical corrosion tests and immersion tests at 37 degrees C for both NiCu and PdCo alloy samples in mammalian Ringer's solution were performed. Long-term corrosion rates are 5.8 x 10(-5) microm per year (NiCu) and 7.7 x 10(-8) microm per year (PdCo) from average immersion test results, indicating higher corrosion resistance of PdCo (P < 0.02); immersion corrosion rates were much lower than initial corrosion rates found electrochemically. Both alloys had significantly lower corrosion rates than standard surgical implant rates of 0.04 microm per year (P < 0.001 for both alloys). Scanning electron microscopy illustrates changes in the NiCu alloy surface due to pitting corrosion; no difference is observed for PdCo. The data indicate that the PdCo alloy may be suitable as a long-term implant for use in fractionated hyperthermia.

Graphene wrapped Copper Phthalocyanine nanotube: Enhanced photocatalytic activity for industrial waste water treatment

NASA Astrophysics Data System (ADS)

Mukherjee, Moumita; Ghorai, Uttam Kumar; Samanta, Madhupriya; Santra, Angshuman; Das, Gour P.; Chattopadhyay, Kalyan K.

2017-10-01

To improve the photocatalytic performance of metal phthalocyanine based catalyst, Copper Phthalocyanine (CuPc) functionalized reduced graphene oxide (RGO) nanocomposite has been synthesized through a simple chemical approach. The obtained product was characterized by X-ray diffraction technique (XRD), Fourier transform infrared (FTIR) spectroscopy, Ultraviolet-visible spectroscopy (UV-vis) and High resolution transmission electron microscopy (HRTEM). The photocatalytic activity of the RGO/CuPc nanocomposite was performed by the degradation of Rhodamine B (RhB) under visible light irradiation. The photocatalytic studies revealed that the RGO/CuPc nanocomposite exhibits much stronger catalytic behavior than the pristine CuPc nanotube. A plausible mechanism for the photodegradation of Rhodamine B (RhB) was suggested. The RGO wrapped CuPc nanotube composite materials offer great potential as active photocatalysts for degradation of organic pollutions in industrial waste water.

Nuclear and Fluorescent Labeled PD-1-Liposome-DOX-64Cu/IRDye800CW Allows Improved Breast Tumor Targeted Imaging and Therapy.

PubMed

Du, Yang; Liang, Xiaolong; Li, Yuan; Sun, Ting; Jin, Zhengyu; Xue, Huadan; Tian, Jie

2017-11-06

The overexpression of programmed cell death-1 (PD-1) in tumors as breast cancer makes it a possible target for cancer imaging and therapy. Advances in molecular imaging, including radionuclide imaging and near-infrared fluorescence (NIRF) imaging, enable the detection of tumors with high sensitivity. In this study, we aim to develop a novel PD-1 antibody targeted positron emission tomography (PET) and NIRF labeled liposome loaded with doxorubicin (DOX) and evaluate its application for in vivo cancer imaging and therapy. IRDye800CW and 64 Cu were conjugated to liposomes with PD-1 antibody labeling, and DOX was inside the liposomes to form theranostic nanoparticles. The 4T1 tumors were successfully visualized with PD-1-Liposome-DOX- 64 Cu/IRDye800CW using NIRF/PET imaging. The bioluminescent imaging (BLI) results showed that tumor growth was significantly inhibited in the PD-1-Liposome-DOX-treated group than the IgG control. Our results highlight the potential of using dual-labeled theranostic PD-1 mAb-targeted Liposome-DOX- 64 Cu/IRDye800CW for the management of breast tumor.

Cu-modified alkalinized g-C3N4 as photocatalytically assisted heterogeneous Fenton-like catalyst

NASA Astrophysics Data System (ADS)

Dong, Qimei; Chen, Yingying; Wang, Lingli; Ai, Shasha; Ding, Hanming

2017-12-01

Alkalinized graphitic carbon nitride (CNK-OH) has been synthesized by one-step thermal poly-condensation method, and Cu-modified alkalinized g-C3N4 (Cu-CNK-OH) has been prepared by impregnation approach over CNK-OH. These copper species in Cu-CNK-OH are embedded in the frame of CNK-OH mostly via the Cu-N bonds. Cu-CNK-OH has been employed as a heterogeneous Fenton-like catalyst to degrade rhodamine B (RhB). Both the production efficiency of hydroxyl radicals and the transformation rate of Cu(II)/Cu(I) redox pair increase under visible-light irradiation. As a result, Cu-CNK-OH exhibits improved Fenton-like catalytic activity on the degradation of RhB. The synergetic interaction between Fenton-like process and photocatalytic process also contributes such improvement. The hydroxyl radicals and holes are the major reactive species in the photocatalytically assisted Fenton-like process. This study provides a valuable strategy for metal modification of alkalinized g-C3N4 with enhanced Fenton-like catalytic performance for the degradation of organic contaminants.

Electrical properties of palladium-doped CaCu3Ti4O12 ceramics

NASA Astrophysics Data System (ADS)

Singh, Arashdeep; Md Mursalin, Sk.; Rana, P.; Sen, Shrabanee

2015-09-01

The effect of doping palladium (Pd) at the Cu site of CaCu3Ti4O12 powders (CCPTO) synthesized by sol-gel technique on electrical properties was studied. XRD analysis revealed the formation of CCTO and CCPTO ceramics with some minor quantities of impurities. SEM micrographs revealed that the grain size decreased with Pd doping. TEM micrographs of CCPTO powder showed the formation of irregular-shaped particles of ~40 nm. The dielectric constant and dielectric loss showed a significant enhancement with Pd doping. A significant decrease in grain-boundary resistance with Pd doping was ascertained by impedance spectroscopy study.

The protective effects of ginsenosides on human erythrocytes against hemin-induced hemolysis.

PubMed

Li, Guo-Xiang; Liu, Zai-Qun

2008-03-01

Panax ginseng has been used in traditional Chinese medicine to enhance stamina and capacity to deal with fatigue and physical stress. Many reports have been devoted to the effects of ginsenosides on many in vitro or in vivo experimental systems. The major aim of this work is to investigate the protective effects of 12 individual ginsenosides including Rb1, Rb3, Rc, Rd, Re, Rg1, Rg2, Rg3, Rh1, Rh2, R1 and pseudoginsenoside F11, together with the central structures of aforementioned ginsenosides, 20(S)-protopanaxadiol (PD) and 20(S)-protopanaxatriol (PT), on hemin-induced hemolysis of human erythrocytes. This is because hemin can induce hemolysis by accelerating the potassium leakage, dissociating skeletal proteins and prohibiting some enzymes in the membrane of erythrocyte. Thus, the structure-activity-relationship (SAR) between ginsenosides and protective effects has been screened in this in vitro experimental system. It is found that Rh2 and Rg3 intensify hemolysis in the presence of hemin, and initiate hemolysis even in the absence of hemin. All the other ginsenosides protect human erythrocytes against hemin-induced hemolysis more or less. The overall sequence is Rc>Rd>Re approximately Rb1>Rg1 approximately Rh1>Rb3 approximately Rg2 approximately R1 approximately F11 approximately PT. In addition, the protective effects of PD and PT have been detected, and found that PD promotes hemolysis appreciably, whereas PT protects erythrocytes efficiently. Moreover, the protective effects of PT ginsenosides are similar to PT itself, and the protective effects of PD ginsenosides vary remarkably, demonstrating that the positions of the sugar moieties make the protective activities of ginsenosides complicated. Especially, sugar moiety at 20-position is critical for PD ginsenosides to inhibit hemolysis, whereas hydroxyl group at 3-position is important for PT ginsenosides. The present result may be useful for understanding the SAR of ginsenosides.

Electrochemical performance and carbon deposition resistance of M-BaZr0.1Ce0.7Y0.1Yb0.1O3-δ (M = Pd, Cu, Ni or NiCu) anodes for solid oxide fuel cells

PubMed Central

Li, Meng; Hua, Bin; Pu, Jian; Chi, Bo; Jian, Li

2015-01-01

Pd-, Cu-, Ni- and NiCu-BaZr0.1Ce0.7Y0.1Yb0.1O3-δ anodes, designated as M-BZCYYb, were prepared by impregnating M-containing solution into BZCYYb scaffold, and investigated in the aspects of electrocatalytic activity for the reactions of H2 and CH4 oxidation and the resistance to carbon deposition. Impregnation of Pd, Ni or NiCu significantly reduced both the ohmic (RΩ) and polarization (RP) losses of BZCYYb anode exposed to H2 or CH4, while Cu impregnation decreased only RΩ in H2 and the both in CH4. Pd-, Ni- and NiCu-BZCYYb anodes were resistant to carbon deposition in wet (3 mol. % H2O) CH4 at 750°C. Deposited carbon fibers were observed in Pd- and Ni-BZCYYb anodes exposed to dry CH4 at 750°C for 12 h, and not observed in NiCu-BZCYYb exposed to dry CH4 at 750°C for 24 h. The performance of a full cell with NiCu-BZCYYb anode, YSZ electrolyte and La0.6Sr0.4Co0.2Fe0.8O3-δ-Gd doped CeO2 (LSCF-GDC) cathode was stable at 750°C in wet CH4 for 130 h, indicating that NiCu-BZCYYb is a promising anode for direct CH4 solid oxide fuel cells (SOFCs). PMID:25563843

The microstructure, mechanical stress, texture, and electromigration behavior of Al-Pd alloys

NASA Astrophysics Data System (ADS)

Rodbell, K. P.; Knorr, D. B.; Mis, J. D.

1993-06-01

As the minimum feature size of interconnect lines decreases below 0.5 urn, the need to control the line microstructure becomes increasingly important. The alloy content, deposition process, fabrication method, and thermal history all determine the microstructure of an interconnect, which, in turn, affects its performance and reliability. The motivation for this work was to characterize the microstructure of various sputtered Al-Pd alloys (Al-0.3wt.%Pd, Al-2Cu-0.3Pd, and Al-0.3Nb-0.3Pd) vs sputtered Al-Cu control samples (Al-0.5Cu and Al-2Cu) and to assess the role of grain size, mechanical stress, and crystallographic texture on the electromigration behavior of submicrometer wide lines. The grain size, mechanical stress, and texture of blanket films were measured as a function of annealing. The as-deposited film stress was tensile and followed a similar stress history on heating for all of the films; on cooling, however, significant differences were observed between the Al-Pd and Al-Cu films in the shape of their stress-temperature-curves. A strong (111) crystallographic texture was typically found for Al-Cu films deposited on SiO2. A stronger (111) texture resulted when Al-Cu was deposited on 25 nm titanium. Al-0.3Pd films, however, exhibited either a weak (111) or (220) texture when deposited on SiO2, which reverted to a strong (111) texture when deposited on 25 nm titanium. The electromigration lifetimes of passivated, ≈0.7 μm wide lines at 250°C and 2.5 × 106 A/cm2 for both single and multi-level samples (separated with W studs) are reported. The electromigration behavior of Al-0.3Pd was found to be less dependent on film microstructure than on the annealing atmosphere used, i.e. forming gas (90% N2-10%H2) annealed Al-0.3Pd films were superior to all of the alloys investigated, while annealing in only N2 resulted in poor lifetimes.

Nanoscale electrical characteristics of metal (Au, Pd)-graphene-metal (Cu) contacts

NASA Astrophysics Data System (ADS)

Ruffino, F.; Meli, G.; Grimaldi, M. G.

2016-01-01

Free-standing graphene presents exceptional physical properties (as a high carrier mobility) making it the ideal candidate for the next generation nanoelectronics. However, when graphene layers are inserted in real electronics devices, metal contacting is required. The metal-graphene interaction significantly affects the graphene electrical properties, drastically changing its behavior with respect to the free-standing configuration. So, this work presents an experimental study on the nanoscale electric characteristics of metal/graphene/metal contacts. In particular, starting from single-layer graphene grown on Cu foil we deposited on the graphene surface two different metal films (Au or Pd) and the Au/graphene/Cu and Pd/graphene/Cu current-voltage characteristics are acquired, on the nanometric scale, by the conductive atomic force microscopy. Both systems presented a current voltage rectifying behavior. However, the Au/graphene/Cu system conducts significantly at negative applied bias (graphene behaves as a p-type semiconductor in a meta/semiconductor contact), while in the Pd/graphene/Cu at positive applied bias (graphene behaves as a n-type semiconductor in a metal/semiconductor contact). This difference is discussed on the basis of the band energy diagram at the metal/graphene interface and the modification of the graphene Fermi level due to the Au/graphene or Pd/graphene interaction.

Optimization of pyrochlore catalysts for the dry reforming of methane

NASA Astrophysics Data System (ADS)

Polo Garzon, Felipe

The conversion of methane into syngas (a mixture of CO and H2), which can be further converted into a variety of chemicals and particularly liquid fuels, is of growing importance given recent increases in methane production world-wide. Furthermore, since using CO2 as the co-feed offers many environmental advantages, dry reforming of methane (DRM, CH4 + CO2 [special character omitted] 2CO + 2H 2) has received renewed attention. In recent years, experimentalists have shown that the Rh-substituted lanthanum zirconate pyrochlore (LRhZ) material is catalytically active for DRM, exhibits long-term thermal stability and resists deactivation; however, previous to this doctoral work, a detailed understanding of the reaction mechanism on pyrochlore catalyst surfaces was still scarce, making it difficult to optimize this material. In this work, initial computational efforts employing density functional theory (DFT) showed the plane (111) of the LRhZ crystal structure as the one catalytically active for DRM. In addition, the primary reaction pathway was identified, along with two rate determining steps (RDSs), the CH2 oxygenation step and the CHO dehydrogenation step, which lie on the CH 4 dehydrogenation/oxygenation path. The mechanistic understanding of DRM over LRhZ was further developed using steady-state isotopic transient kinetic analysis (SSITKA). Reversible adsorption of CO2 on the surface was observed, along with short surface residence times (< 0.6 s) at 650 and 800 °C, and increasing turnover frequencies with temperature. Comparisons between isotopic responses supported the DFT-derived reaction mechanism. Furthermore, isotopic transient kinetics confirmed that all metal atoms (Rh, Zr and La) on the surface are involved in the reaction mechanism, as previously pointed by DFT calculations. A DFT-based microkinetic model that predicts the reaction performance at different conditions was built. The model was validated against experimental data, showing remarkable agreement, which further confirmed the reliability of the DFT data. Computational analysis of one of the RDSs (the CHO dehydrogenation step) suggested Pd as an effective co-dopant to reduce the activation barrier of this step. This bimetallic Rh-Pd-substituted lanthanum zirconate pyrochlore (Rh-Pd-LZ) was synthesized, characterized and tested. The Rh-Pd-LZ catalyst successfully increased conversions at high temperatures while providing H 2 to CO ratios close to unity; thus fostering DRM and inhibiting the competing reaction, the reverse water gas shift reaction (RWGS, CO2 + H2 [special character omitted] CO + H2O). The Rh-Pd-LZ catalyst outperformed the initial catalyst, the LRhZ, at high temperatures.

Rapid PD-L1 detection in tumors with PET using a highly specific peptide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chatterjee, Samit; Lesniak, Wojciech G.; Miller, Michelle S.

Molecular imaging can report on the status of the tumor immune microenvironment and guide immunotherapeutic strategies to enhance the efficacy of immune modulation therapies. Imaging agents that can rapidly report on targets of immunomodulatory therapies are few. The programmed death ligand 1 (PD-L1) is an immune checkpoint protein over-expressed in several cancers and contributes to tumor immune suppression. Tumor PD-L1 expression is indicative of tumor response to PD-1 and PD-L1 targeted therapies. Herein, we report a highly specific peptide-based positron emission tomography (PET) imaging agent for PD-L1. We assessed the binding modes of the peptide WL12 to PD-L1 by dockingmore » studies, developed a copper-64 labeled WL12 ([{sup 64}Cu]WL12), and performed its evaluation in vitro, and in vivo by PET imaging, biodistribution and blocking studies. Our results show that [{sup 64}Cu]WL12 can be used to detect tumor PD-L1 expression specifically and soon after injection of the radiotracer, to fit within the standard clinical workflow of imaging within 60 min of administration. - Highlights: • A highly specific PD-L1 binding peptide, WL12, was developed as a PET imaging agent. • [{sup 64}Cu]WL12 demonstrates specific binding to PD-L1 in vitro and in vivo. • [{sup 64}Cu]WL12-PET allows PD-L1 detection in cancers within 60 min of administration. • WL12 binding interactions with PD-L1 overlaps with that of PD-1.« less

Kinetics of oxygen-enhanced water gas shift on bimetallic catalysts and the roles of metals and support

NASA Astrophysics Data System (ADS)

Kugai, Junichiro

The post-processing of reformate is an important step in producing hydrogen (H2) with low carbon monoxide (CO) for low temperature fuel cells from syn-gas. However, the conventional process consists of three steps, i.e. two steps of water gas shift (WGS) and preferential oxidation (PROX) of CO, and it is not suitable for mobile applications due to the large volume of water gas shift (WGS) catalysts and conditioning and/or regeneration necessary for these catalysts. Aiming at replacing those three steps by a simple one-step process, small amount of oxygen was added to WGS (the reaction called oxygen-enhanced water gas shift or OWGS) to promote the reaction kinetics and low pyrophoric ceria-supported bimetallic catalysts were employed for stable performance in this reaction. Not only CO conversion, but also H2 yield was found to increase by the O2 addition on CeO2-supported catalysts. The characteristics of OWGS, high H2 production rate at 200 to 300°C at short contact time where unreacted O2 exists, evidenced the impact of O2 addition on surface species on the catalyst. Around 1.5 of reaction order in CO for various CeO2-supported metal catalysts for OWGS compared to reaction orders in CO ranging from -0.1 to 0.6 depending on metal species for WGS shows O2 addition decreases CO coverage to free up the active sites for co-reactant (H2O) adsorption and activation. Among the monometallic and bimetallic catalysts, Pt-Cu and Pd-Cu bimetallic catalysts were superior to monometallic catalysts in OWGS. These bimetallic components were found to form alloys where noble metal is surrounded mainly by Cu to have strong interaction between noble metal and copper resulting in high OWGS activity and low pyrophoric property. The metal loadings were optimized for CeO2-supported Pd-Cu bimetallic system and 2 wt% Pd with 5 -- 10 wt% Cu were found to be the optimum for the present OWGS condition. In the kinetic study, Pd in Pd-Cu was shown to increase the active sites for H2O dissociation and/or the subsequent reaction with chemisorbed CO as well as Pd keeps Cu in reduced state. Cu was found to keep Pd dispersed, suppress H2 activation on Pd, and facilitate CO 2 desorption from catalyst surface. While composition and structure of metal have large impacts on OWGS performance, CeO2 was shown to create new sites for H2O activation at metal-ceria interfacial region in concert with metal. These new sites strongly activate H2O to drive OWGS and WGS compared to the pure metallic sites which are present in majority on Al2O3-supported catalyst. The observed two regimes of turnover rate, the one dependent on catalyst surface area and the other independent of surface area, strongly suggested bifunctional reaction pathway where the reaction rate is determined by activation of H2O and by association of chemisorbed CO and H 2O. The associative route was also evidenced by pulse response study where the reaction occurs only when CO and H2O pulses are supplied together, and thus pre-adsorbed species such as formate and carbonate identified by FT-IR are proven to be spectators. No correlation between WGS rate and isotopic exchange rate of molecularly adsorbed D2O with H 2 showed H2O dissociation is necessary for WGS to occur. Long duration tests revealed CeO2-supported Pd-Cu, Pt-Cu and Cu catalysts are stable in OWGS condition compared to Pt, Pd, and Al 2O3-supported Pd-Cu catalysts which exhibited continuous deactivation during about 70 hours of test. The addition of Cu prevents agglomeration of monometallic Pd and carbonate formation on monometallic Pt during the reaction. The better activity and stability of Pd-Cu and Pt-Cu bimetallic catalysts in the realistic OWGS condition were ascribed to the unique active sites consisting of highly dispersed Pd in Cu or Pt in Cu on CeO2, which are good for H2O activation with low reaction inhibition by the product gases. Pt monometallic catalyst showed and highest activity in OWGS in the absence of product gases, but this was found vulnerable in the presence of product gases due to strong adsorption of H2 and CO2 on this catalyst. (Abstract shortened by UMI.)

[Pollution characteristics of platinum group elements in road rust in Xiamen].

PubMed

Hong, Zhen-yu; Hong, You-wei; Yin, Li-qian; Chen, Jin-sheng; Chen, Yan-ting; Xu, Ling-ling

2015-01-01

With the potential risks for the environment and human health, the concentration and distribution characteristics of platinum group element(PGEs) in road dust in Xiamen city were investigated. Road dust samples were collected from the traffic trunk road, tunnel, tourism area, and industrial area of Xiamen on October 2012. The samples were digested with aqua regia in a microwave assisted digestion system under high pressure condition, separated and purified with cation exchange resin( Dowex AG50W-X8), and the resulting solutions were analyzed by inductively coupled plasma mass spectrometry (ICP-MS). The results showed that the average concentrations(range) of Pd, Pt and Rh in road dust were 246.82 (58.68-765.52) ng x g(-1), 95.45 (42.14-371.36) ng x g(-1) and 51.76 (21.04-119.72) ng x g(-1), respectively, which were two orders of magnitude higher than the background values. Compared with other cities worldwide, the concentrations of Pd, Pt and Rh in road dust in Xiamen were at higher levels. Theconcentrations of PGEs for different functional areas were listed in the following order: tunnel > urban district > industrial area > tourism area, which indicated that their spatial distributions were mainly affected by the traffic intensity. Correlation analysis results showed that concentration of Pd in the urban traffic artery was significantly correlated with Rh, while Pt was not so correlated with Pd and Rh, suggesting that other sources contributed to PGEs in road dust in addition to the vehicle emission. Although motor vehicle traveling was banned in tourist area, the concentration of PGEs was still at a high level. Some of them might originate from the road dust in surrounding area by atmosphere diffusion.

Humidity sensitive polymers In solution processed adjustable pore-volume Cu(In,Ga)S2 photocathodes for solar hydrogen production

NASA Astrophysics Data System (ADS)

Zhang, Chuan; Luo, Wenjun; Wen, Xin; Guan, Zhongjie; Zou, Zhigang

2017-11-01

P-type Cu(In,Ga)S2 semiconductors are promising candidates to be used as photocathodes for solar water splitting. Porous structures have been widely used to improve the performances of photoelectrodes due to good minority carrier transport. However, a porous photoelectrode has longer transport distance of majority carriers, which limits its performance. Controlling pore volume of a photoelectrode can balance minority and majority carrier transport and improve the performance. Here, a porous Cu(In,Ga)S2 film is prepared by facile spin-coating method. The pore volume of Cu(In,Ga)S2 film is controlled by adjusting relative humidity (RH) of air during spin-coating process. Further studies suggest that polyvinyl acetate (PVAc) in precursor solution is a humidity sensitive polymer and plays a key role to form different pore volume. The 40% RH sample has the best performance due to its optimum pore volume. After further coated with CdS surface passivation layer and Pt electrocatalyst on the surface, a 40% RH Cu(In,Ga)S2 photocathode indicates a photocurrent density of 8.6 mA cm-2 at 0 V RHE, which is one of the highest photocurrents of Cu(In,Ga)S2 photocathodes. This new strategy for adjusting pore volume is also suitable to prepare other solution-processed inorganic materials.

Bimetallic poly- and oligo-nuclear complexes based on a rhodium(III) metalloligand

NASA Astrophysics Data System (ADS)

Vasilchenko, Danila B.; Venediktov, Anatoliy B.; Korenev, Sergey V.; Filatov, Evgeniy Yu.; Baidina, Iraida A.; Nadolinnyi, Vladimir A.

2012-10-01

Interaction of trans-[Rh(i-Nic)4Cl2]3- anions (i-Nic- - isonicotinate anion) with Cuaq2+ and Coaq2+ cations in water has afforded complex salts Co3[Rh(i-Nic)4Cl2]2·17H2O (1) and Cu3[Rh(i-Nic)4Cl2]2·14H2O (2). Oligonuclear character of 1 and 2 has been established. A coordination polymer Cu5[Rh(i-Nic)4Cl2]2(i-Nic)2(OH)2·2H2O (3) has been crystallized by hydrothermal treatment of 2 at 160 °C, and its structure was determined by X-ray structural analysis. EPR data for the complexes has been collected and interpreted. Thermal decomposition of the salts was studied by c-DTA. Bimetallic alloys rhodium-copper and rhodium-cobalt have been obtained as final products of thermal decomposition.

Facile solvothermal synthesis of highly active and robust Pd1.87Cu0.11Sn electrocatalyst towards direct ethanol fuel cell applications

NASA Astrophysics Data System (ADS)

Jana, Rajkumar; Dhiman, Shikha; Peter, Sebastian C.

2016-08-01

Ordered intermetallic Pd1.87Cu0.11Sn ternary electrocatalyst has been synthesized by sodium borohydride reduction of precursor salts Pd(acac)2, CuCl2.2H2O and SnCl2 using one-pot solvothermal synthesis method at 220 °C with a reaction time of 24 h. To the best of our knowledge, here for the first time we report surfactant free synthesis of a novel ordered intermetallic ternary Pd1.87Cu0.11Sn nanoparticles. The ordered structure of the catalyst has been confirmed by powder x-ray diffraction, transmission electron microscopy (TEM). Composition and morphology of the nanoparticles have been confirmed through field emission scanning electron microscopy, energy-dispersive spectrometry and TEM. The electrocatalytic activity and stability of the ternary electrocatalyst towards ethanol oxidation in alkaline medium was investigated by cyclic voltammetry and chronoamperometry techniques. The catalyst is proved to be highly efficient and stable upto 500th cycle and even better than commercially available Pd/C (20 wt%) electrocatalysts. The specific and mass activity of the as synthesized ternary catalyst are found to be ∼4.76 and ∼2.9 times better than that of commercial Pd/C. The enhanced activity and stability of the ordered ternary Pd1.87Cu0.11Sn catalyst can make it as a promising candidate for the alkaline direct ethanol fuel cell application.

Effect of Precursors on the Synthesis of CuO Nanoparticles Under Microwave for Photocatalytic Activity Towards Methylene Blue and Rhodamine B Dyes.

PubMed

Sanjini, N S; Winston, B; Velmathi, S

2017-01-01

Copper oxide nanoparticles have been successfully synthesized by microwave assisted precipitation method. Different precursors like copper chloride, copper nitrate and copper sulphate were used for synthesis of CuO nanoparticles with different shape, size and catalytic activity. Sodium hydroxide acts as a capping agent and ethanol as solvent for the synthesis. The XRD study was conducted to confirm the single phase monoclinic structure of as-synthesized and annealed CuO nano particles. The morphology of the as-synthesized and annealed CuO samples was analyzed by high resolution field emission scanning electron microscope. Fourier transform infrared spectroscopy was done for all the synthesized CuO nanoparticles for functional group characterization. The wide band gap and photocatalytic activity were studied by UV-Visible spectroscopy. The photocatalytic degradation of Methylene blue (MB) and Rhodamine B (RhB) dyes in aqueous solution were investigated under UV light (254 nm). In all the cases annealed samples showed good catalytic activity compared to as-synthesized CuO nanoparticles. The CuO nanoparticles from CuCl2 precursor act as excellent photocatalyst for both MB and RhB compared to CuNO₃ and CuSO₄.

Electronic structure of disordered CuPd alloys: A two-dimensional positron-annihilation study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Smedskjaer, L.C.; Benedek, R.; Siegel, R.W.

1987-11-23

Two-dimensional--angular-correlation experiments using posi- tron-annihilation spectroscopy were performed on a series of disordered Cu-rich CuPd-alloy single crystals. The results are compared with theoretical calculations based on the Korringa-Kohn-Rostoker coherent-potential approximation. Our experiments confirm the theoretically predicted flattening of the alloy Fermi surface near (110) with increasing Pd concentration. The momentum densities and the two-dimensional--angular-correlation spectra around zero momentum exhibit a characteristic signature of the electronic states near the valence-band edge in the alloy.

Electrocatalytic Oxidation of Ammonia on Transition-Metal Surfaces: A First-Principles Study

DOE PAGES

Herron, Jeffrey A.; Ferrin, Peter; Mavrikakis, Manos

2015-02-20

Here, we investigate the catalytic electro-oxidation of ammonia on model close-packed surfaces of Au, Ag, Cu, Pd, Pt, Ni, Ir, Co, Rh, Ru, Os, and Re to derive insights for the reaction mechanism and evaluate the catalysts based on their energy efficiency and activity in the context of their application in fuel cells. Two mechanisms, which are differentiated by their N–N bond formation step, are compared: (1) a mechanism proposed by Gerischer and Mauerer, whereby the N–N bond formation occurs between hydrogenated NH x adsorbed species, and (2) a mechanism in which N–N bond formation occurs between N adatoms. Themore » results of our study show that the mechanism proposed by Gerischer and Mauerer is kinetically preferred and that the formation of N adatoms poisons the surface of the catalyst. On the basis of a simple Sabatier analysis, we predict that Pt is the most active monometallic catalyst followed by Ir and Cu, whereas all other metal surfaces studied here have significantly lower activity. We conclude by outlining some design principles for bimetallic alloy catalysts for NH 3 electro-oxidation.« less

Coordination behavior of tetraaza [N4] ligand towards Co(II), Ni(II), Cu(II), Cu(I) and Pd(II) complexes: Synthesis, spectroscopic characterization and anticancer activity

NASA Astrophysics Data System (ADS)

El-Boraey, Hanaa A.

2012-11-01

Novel eight Co(II), Ni(II), Cu(II), Cu(I) and Pd(II) complexes with [N4] ligand (L) i.e. 2-amino-N-{2-[(2-aminobenzoyl)amino]ethyl}benzamide have been synthesized and structurally characterized by elemental analysis, spectral, thermal (TG/DTG), magnetic, and molar conductivity measurements. On the basis of IR, mass, electronic and EPR spectral studies an octahedral geometry has been proposed for Co(II), Ni(II) complexes and Cu(II) chloride complex, square-pyramidal for Cu(I) bromide complex. For Cu(II) nitrate complex (6), Pd(II) complex (8) square planar geometry was proposed. The EPR data of Cu(II) complexes in powdered form indicate dx2-y2 ground state of Cu(II) ion. The antitumor activity of the synthesized ligand and some selected metal complexes has been studied. The palladium(II) complex (8) was found to display cytotoxicity (IC50 = 25.6 and 41 μM) against human breast cancer cell line MCF-7 and human hepatocarcinoma HEPG2 cell line.

Charting the relationship between phase type-surface area-interactions between the constituent atoms and oxygen reduction activity of Pd–Cu nanocatalysts inside fuel cells by in operando high-energy X-ray diffraction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Maswadeh, Yazan; Shan, Shiyao; Prasai, Binay

The activity and stability of nanoalloy catalysts for chemical reactions driving devices for clean energy conversion, in particular the oxygen reduction reaction (ORR), depend critically on optimizing major structural characteristics of the nanoalloys, such as the phase composition, surface area and bonding interactions between the constituent atoms, for the harsh operating conditions inside the devices. The effort requires good knowledge of the potential effect of changes in these characteristics on the catalytic functionality of the nanoalloys and, hence, on the devices' performance. We present the results from an in operando high-energy X-ray diffraction (HE-XRD) study on the concurrent changes inmore » the structural characteristics and ORR activity of Pd–Cu nanoalloy catalysts as they function at the cathode of a proton exchange membrane fuel cell (PEMFC). We find that the as-prepared Pd–Cu nanoalloys with a chemical composition close to Pd1Cu1 are better ORR catalysts in comparison with Pd1Cu2, i.e. Pd-poor, and Pd3Cu1, i.e. Pd-rich, nanoalloys. Under operating conditions though, the former suffers a big loss in ORR activity appearing as a slow-mode oscillation in the current output of the PEMFC. Losses in ORR activity suffered by the latter also exhibit sudden drops and rises during the PEMFC operation. Through atomic pair distribution function (PDF) analysis of the in operando HE-XRD data, we identify the structural changes of Pd–Cu alloy NPs that are behind the peculiar decay of their ORR activity. The results uncover the instant link between the ever-adapting structural state of ORR nanocatalysts inside an operating PEMFC and the performance of the PEMFC. Besides, our results indicate that, among others, taking control over the intra-particle diffusion of metallic species in nanoalloy catalysts may improve the performance of PEMFCs significantly and, furthermore, in operando HE-XRD can be an effective tool to guide the effort. Finally, we argue that, though showing less optimal ORR activity in the as-prepared state, monophase Pd–Cu alloy catalysts with a composition ranging between Pd1Cu1 and Pd3Cu1 may deliver optimal performance inside operating PEMFCs.« less

Platinum-Group Elements in Soils and Street Dust of the Southeastern Administrative District of Moscow

NASA Astrophysics Data System (ADS)

Ladonin, D. V.

2018-03-01

The contents of five platinum-group metals (Ru, Rh, Pd, Ir, and Pt) in soils and street dust of the Southeastern administrative district (SEAD) of Moscow have been determined. The contents of these elements in soils may considerably exceed their natural abundances in the lithosphere and are characterized by considerable variability and asymmetric frequency distribution. A close correlation between Rh, Pd, and Pt contents in soils and street dust has been shown. The data on the contents of the elements and the ratios between them suggest that motor vehicles are the major source of pollution of soils and street dust in the studied district.

Determination of Pd, Pt and Rh in vehicles escape fumes by GF-AAS and ICP-OES.

PubMed

Goncalves, Antonio; Domínguez, José R; Alvarado, José

2008-04-15

Automotive exhaust gases from vehicles using catalytic converters were filtered through cellulose filter papers to collect suspended particles expulsed along with the engine's escape fumes. A specially designed sample collector was used for supporting the filter papers during collection. The collector was manufactured from a new car's exhaust pipe. A cellulose circular paper filter, 11 cm diameter, was attached to one end of the pipe and kept centered by pressing it against the borders of the pipe by means of a perforated aluminum cap, slightly wider than the pipe, used to cover this end of the collector. Filter papers loaded with the solid particles were acid-digested using a modified domestic microwave oven to bring the solid material into solution. The resulting solutions were analyzed for Pt by graphite furnace atomic absorption spectrometry (GF-AAS) and for Pd and Rh by inductively coupled plasma (ICP-OES). Results indicate that concentration of these analytes in the particulate is higher for new vehicles, having new catalytic converters, than for old ones. Maximum Pd, Pt and Rh in the samples analyzed were found to be 5.36, 12.60 and 1.03 microg g(-1), respectively.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kumar, S.; Sihotra, S.; Singh, K.

The level structures in {sup 98,99}Rh, and {sup 99}Pd nuclei have been investigated through in beam γ-ray spectroscopic techniques following the {sup 75}As({sup 28}Si, xpyn) fusion-evaporation reaction at E{sub lab} = 120 MeV. These investigations were carried out using Indian-National-Gamma-Array (INGA) consisting of Compton-suppressed clover detectors at the Inter-University Accelerator Centre, New Delhi. The level structures observed in {sup 99}Pd, and {sup 98,99}Rh have been established up to ∼ 11 MeV, 10 MeV and 16 MeV excitation energy and spin ∼ 23ħ, 23ħ, and 28ħ respectively. In the doubly-odd {sup 98}Rh nucleus, new band structures and isomeric states have beenmore » identified at lower spins and new states below the previously identified 2{sup +} ground state (T{sub 1/2} = 8.5 m) are identified. In the present work {sup 99}Rh structure have been observed similar to {sup 101}Rh which is based on p{sub 1/2} and g{sub 9/2} orbitals. Various positive and negative parity states in these nuclei are observed to be energetically more favored with respect to the neighboring ones, and are likely to be the maximally aligned states obtained by angular momentum coupling of the valence particles (holes). The level structures observed in {sup 99}Pd have been interpreted in the framework of a microscopic theory based on the deformed Hartree-Fock (HF) and angular momentum projection techniques. Band structures at low excitation energy are based on the low-Ω νg{sub 7/2} and νd{sub 5/2} orbitals, have been observed in {sup 99}Pd. Band structure at higher spins are reproduced with the ν(g{sub 7/2}){sup 2}⊗ν(g{sub 9/2}){sup −1}⊗ν(h{sub 11/2}){sup 2}⊗π(g{sub 9/2}){sup 6} configurations. Observation of new E1 transitions linking the opposite parity νh{sub 11/2} and νd{sub 5/2} bands provide fingerprints of possible octupole correlations in {sup 99}Pd. The extracted values of the B(E1)/B(E2) ratios for the lower levels in the νh{sub 11/2} band are ∼ 10{sup −7} [fm]{sup −2}.« less

Creation of Novel Solid-Solution Alloy Nanoparticles on the Basis of Density-of-States Engineering by Interelement Fusion.

PubMed

Kobayashi, Hirokazu; Kusada, Kohei; Kitagawa, Hiroshi

2015-06-16

Currently 118 known elements are represented in the periodic table. Of these 118 elements, only about 80 elements are stable, nonradioactive, and widely available for our society. From the viewpoint of the "elements strategy", we need to make full use of the 80 elements to bring out their latent ability and create innovative materials. Furthermore, there is a strong demand that the use of rare or toxic elements be reduced or replaced while their important properties are retained. Advanced science and technology could create higher-performance materials even while replacing or reducing minor or harmful elements through the combination of more abundant elements. The properties of elements are correlated directly with their electronic states. In a solid, the magnitude of the density of states (DOS) at the Fermi level affects the physical and chemical properties. In the present age, more attention has been paid to improving the properties of materials by means of alloying elements. In particular, the solid-solution-type alloy is advantageous because the properties can be continuously controlled by tuning the compositions and/or combinations of the constituent elements. However, the majority of bulk alloys are of the phase-separated type under ambient conditions, where constituent elements are immiscible with each other. To overcome the challenge of the bulk-phase metallurgical aspects, we have focused on the nanosize effect and developed methods involving "nonequilibrium synthesis" or "a process of hydrogen absorption/desorption". We propose a new concept of "density-of-states engineering" for the design of materials having the most desirable and suitable properties by means of "interelement fusion". In this Account, we describe novel solid-solution alloys of Pd-Pt, Ag-Rh, and Pd-Ru systems in which the constituent elements are immiscible in the bulk state. The homogeneous solid-solution alloys of Pd and Pt were created from Pd core/Pt shell nanoparticles using a hydrogen absorption/desorption process as a trigger. Several atom percent replacements of Pd with Pt atoms resulted in a significantly enhanced hydrogen absorption capacity compared with Pd nanoparticles. AgxRh1-x and PdxRu1-x solid-solution alloy nanoparticles were also developed by nonequilibrium synthesis based on a polyol method. The AgxRh1-x nanoparticles demonstrated hydrogen storage properties, although pure metal nanoparticles of each constituent element do not adsorb hydrogen. AgxRh1-x is therefore considered to possess a similar electronic structure to Pd as a synthetic pseudo-palladium. The PdxRu1-x nanoparticles showed enhanced catalytic activity for CO oxidation, with the highest catalytic activity found using the equimolar Pd0.5Ru0.5 nanoparticles. The catalytic activity of the Pd0.5Ru0.5 nanoparticles exceeds that of the widely used and best-performing Ru catalysts for CO oxidation and is also higher than that of neighboring Rh on the periodic table. Our present work provides a guiding principle for the design of a suitable DOS shape according to the intended physical and/or chemical properties and a method for the development of novel solid-solution alloys.

An inorganic capping strategy for the seeded growth of versatile bimetallic nanostructures

DOE PAGES

Pei, Yuchen; Maligal-Ganesh, Raghu V.; Xiao, Chaoxian; ...

2015-09-11

Metal nanostructures have attracted great attention in various fields due to their tunable properties through precisely tailored sizes, compositions and structures. Using mesoporous silica (mSiO 2) as the inorganic capping agent and encapsulated Pt nanoparticles as the seeds, we developed a robust seeded growth method to prepare uniform bimetallic nanoparticles encapsulated in mesoporous silica shells (PtM@mSiO 2, M = Pd, Rh, Ni and Cu). Unexpectedly, we found that the inorganic silica shell is able to accommodate an eight-fold volume increase in the metallic core by reducing its thickness. The bimetallic nanoparticles encapsulated in mesoporous silica shells showed enhanced catalytic propertiesmore » and thermal stabilities compared with those prepared with organic capping agents. As a result, this inorganic capping strategy could find a broad application in the synthesis of versatile bimetallic nanostructures with exceptional structural control and enhanced catalytic properties.« less

Producing carbon-based boundary films from catalytically active lubricant additives

DOE Office of Scientific and Technical Information (OSTI.GOV)

Erdemir, Ali; Mane, Anil U.; Elam, Jeffrey W.

A lubricant composition includes an oil including a plurality of long-chain hydrocarbon molecules. A quantity of a catalytically active metal-organic additive is mixed with the oil. The metal-organic additive is formulated to fragment the long-chain hydrocarbon molecules of the oil into at least one of dimers and trimers under the influence of at least one of a mechanical loading and a thermal loading. In some embodiments, the metal-organic additive includes a compound of formula II: ##STR00001## where: X is Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Hf,more » Ta, W, Re, Os, Ir, Pt, Au, Hg, Rf, Db, Sg, Bh, Hs, Mt, Ds, Rg or Cn, and R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are alkyl or alkyl halide.« less

The Effect of Palladium Additions on the Solidus/Liquidus Temperatures and Wetting Properties of Ag-CuO Based Air Brazes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Darsell, Jens T.; Weil, K. Scott

2007-05-16

As a means of increasing the use temperature of ceramic-ceramic and ceramic-metal air brazes, palladium was investigated as possible ternary addition to the currently employed silver - copper oxide system. The silver component was directly substituted with palladium to form the following series of alloys: (100-y)[(100-z)Pd - (z)Ag] - (y)CuOx where y = 0 - 34 mol% CuOx, z = 50 - 100 mol% silver, and x = 0, 0.5, and 1, denoting copper metal, Cu2O, or CuO. From differential scanning calorimetry, it was determined that the addition of palladium causes an increase in the solidus and liquidus temperatures ofmore » the resulting Pd-Ag-CuO brazes. In general, the liquidus was found to increase by approximately 220°C for the (100-y)(25Pd - 75Ag) - (z)CuOx filler metal compositions relative to comparable Ag-CuOx alloys. Likewise, the solidus was found to increase for these alloys, respectively by 185°C and 60°C, respectively for CuOx contents of y = 0 - 1mol% and 4 - 10 mol%. For the (100-y)(50Pd - 50Ag) - (y)CuOx alloys, the solidus increased between 280 - 390°C over a copper oxide compositional range of x = 0 to 8 mol%. It was determined from sessile drop experiments conducted on alumina substrates that in all cases the palladium causes an increase in the wetting angle relative to the corresponding binary braze. Alloy compositions of (100-y)(25Pd - 75Ag) - (y)CuOx displayed increased wetting angles of 5-20° relative to comparable binary compositions. (100-y)(50Pd - 50Ag) - (y)CuOx alloys exhibited an increase in contact angle of 10-60° and compositions containing less than 10 mol% CuOx were not able to wet the substrate. Scanning electron microscopy indicated that the microstructure of the braze consists of discrete CuOx precipitates in an alloyed silver-palladium matrix. In both the binary and ternary filler metal formulations, a reaction layer consisting of CuAlO2 was observed along the interface with the alumina substrate. This reaction product appears to be beneficial in promoting wetting by the remaining braze filler metal. However the formation of this layer is hindered as the concentration of palladium in the filler metal is increased, which appears to be the primary cause of poor wettability in these compositions, as indicated by the substantial amount of porosity found along the braze/substrate interface.« less

Characterization of recombinant human C1 inhibitor secreted in milk of transgenic rabbits.

PubMed

van Veen, Harrie A; Koiter, Jaco; Vogelezang, Carla J M; van Wessel, Noucha; van Dam, Tijtje; Velterop, Ingeborg; van Houdt, Kristina; Kupers, Luc; Horbach, Danielle; Salaheddine, Mourad; Nuijens, Jan H; Mannesse, Maurice L M

2012-12-31

C1 inhibitor (C1INH) is a single-chain glycoprotein that inhibits activation of the contact system of coagulation and the complement system. C1INH isolated from human blood plasma (pd-hC1INH) is used for the management of hereditary angioedema (HAE), a disease caused by heterozygous deficiency of C1INH, and is a promise for treatment of ischemia-reperfusion injuries like acute myocardial or cerebral infarction. To obtain large quantities of C1INH, recombinant human C1INH (rhC1INH) was expressed in the milk of transgenic rabbits (12 g/l) harboring genomic human C1INH sequences fused to 5' bovine αS(1) casein promoter sequences. Recombinant hC1INH was isolated from milk to a specific activity of 6.1 U/mg and a purity of 99%; by size-exclusion chromatography the 1% impurities consisted of multimers and N-terminal cleaved C1INH species. Mass spectrometric analysis of purified rhC1INH revealed a relative molecular mass (M(r)) of 67,200. Differences in M(r) on SDS PAGE and mass spectrometric analysis between rhC1INH and pd-hC1INH are explained by differential glycosylation (calculated carbohydrate contents of 21% and 28%, respectively), since protein sequencing analysis of rhC1INH revealed intact N- and C-termini. Host-related impurity analysis by ELISA revealed trace amounts of rabbit protein (approximately 10 ppm) in purified batches, but not endogenous rabbit C1INH. The kinetics of inhibition of the target proteases C1s, Factor XIIa, kallikrein and Factor XIa by rhC1INH and pd-hC1INH, indicated comparable inhibitory potency and specificity. Recently, rhC1INH (Ruconest(®)) has been approved by the European Medicines Agency for the treatment of acute attacks of HAE. Copyright © 2012 Elsevier B.V. All rights reserved.

To rise and to fall: functional connectivity in cognitively normal and cognitively impaired patients with Parkinson's disease.

PubMed

Gorges, Martin; Müller, Hans-Peter; Lulé, Dorothée; Pinkhardt, Elmar H; Ludolph, Albert C; Kassubek, Jan

2015-04-01

Cognitive decline is a burdensome extra-motor symptom associated with Parkinson's disease (PD). This study aimed at investigating intrinsic functional connectivity (iFC) of the brain in cognitively unimpaired (PD-CU) and impaired PD patients (PD-CI) compared with age-matched healthy controls. "Resting-state" functional magnetic resonance imaging was acquired in 53 subjects, that is, 14 PD-CU patients, 17 PD-CI patients, and 22 control subjects. Cognition and cognitive status for patient classification were assessed using detailed neuropsychological testing. In PD-CU patients versus controls, we demonstrated significantly increased iFC (hyperconnectivity) presenting as network expansions in cortical, limbic, and basal ganglia-thalamic areas. Significantly, decreased iFC in PD-CI patients compared with control subjects was observed, predominantly between major nodes of the default mode network. In conclusion, the increased iFC might be the initial manifestation of altered brain function preceding cognitive deficits. Hyperconnectivity could be an adaptive (compensatory) mechanism by recruiting additional resources to maintain normal cognitive performance. As PD-related pathology progresses, functional disruptions within the default mode networks seem to be considerably associated with cognitive decline. Copyright © 2015 Elsevier Inc. All rights reserved.

Hydrogen in thin Pd-based layers deposited on reticulated vitreous carbon-A new system for electrochemical capacitors

NASA Astrophysics Data System (ADS)

Łukaszewski, M.; Żurowski, A.; Czerwiński, A.

Reticulated vitreous carbon (RVC) has been used as a matrix for electrodeposition of thin layers of Pd and Pd-rich Pd-Rh alloys. It was found that RVC substrate does not affect qualitatively hydrogen absorption behavior of Pd-based deposits. Similarly to thin Pd or Pd alloy layers deposited on Au wires, the α-β phase transition controls the overall rate of hydrogen absorption and desorption into/from Pd-based/RVC electrodes. The possibility of the application of these materials as phase charging-discharging systems was investigated. The values of specific pseudocapacitance, specific power and specific energy were comparable with those for supercapacitors utilizing various redox reactions.

Isolation of Cu Atoms in Pd Lattice: Forming Highly Selective Sites for Photocatalytic Conversion of CO2 to CH4.

PubMed

Long, Ran; Li, Yu; Liu, Yan; Chen, Shuangming; Zheng, Xusheng; Gao, Chao; He, Chaohua; Chen, Nanshan; Qi, Zeming; Song, Li; Jiang, Jun; Zhu, Junfa; Xiong, Yujie

2017-03-29

Photocatalytic conversion of CO 2 to CH 4 , a carbon-neutral fuel, represents an appealing approach to remedy the current energy and environmental crisis; however, it suffers from the large production of CO and H 2 by side reactions. The design of catalytic sites for CO 2 adsorption and activation holds the key to address this grand challenge. In this Article, we develop highly selective sites for photocatalytic conversion of CO 2 to CH 4 by isolating Cu atoms in Pd lattice. According to our synchrotron-radiation characterizations and theoretical simulations, the isolation of Cu atoms in Pd lattice can play dual roles in the enhancement of CO 2 -to-CH 4 conversion: (1) providing the paired Cu-Pd sites for the enhanced CO 2 adsorption and the suppressed H 2 evolution; and (2) elevating the d-band center of Cu sites for the improved CO 2 activation. As a result, the Pd 7 Cu 1 -TiO 2 photocatalyst achieves the high selectivity of 96% for CH 4 production with a rate of 19.6 μmol g cat -1 h -1 . This work provides fresh insights into the catalytic site design for selective photocatalytic CO 2 conversion, and highlights the importance of catalyst lattice engineering at atomic precision to catalytic performance.

Information Requirements for the VIMS (Vehicle Integrated Management System).

DTIC Science & Technology

1983-09-01

flj the decision setting and the...rl 4-1 -o to SH 0 en X r4 4J <D +J (U 4-1 3 s <u 3 a) r-\\ X 0 U H Jo (0 T3 (Ö TD <tf 0 +J c X i. 1 tt a C" rtJ rH XI x; X CO (0 Cn -4-1 i...tr •H CO en (0 CO •H <u rH O •H a CU > CU x: +j Ä O •H JC O 4J c o •P 4J td N •H C (TJ Oi P o P O CU CT> CO CO

Lack of association of programmed cell death 1 gene (PDCD1) polymorphisms with susceptibility to chronic urticaria in patients with positive autologous serum skin test.

PubMed

Brzoza, Z; Grzeszczak, W; Trautsolt, W; Moczulski, D

2012-01-01

Autoimmune mechanisms play an important role in the pathophysiology of chronic urticaria (CU), and the autologous serum skin test (ASST) helps to identify patients with autoreactive CU. One of the factors involved in autoreactive mechanisms is the cell surface receptor programmed death-1 which is encoded by the programmed cell death 1 gene (PDCD1). To investigate whether PDCD1 polymorphisms influence susceptibility to CU. We enrolled 93 ASST-positive patients with CU and a control group consisting of 105 healthy volunteers. In all individuals, PD1.3 (7146 A/G; rs 11568821) and PD1.5 (7785 C/T; rs 2227981) polymorphisms were analyzed. No statistically significant differences were found between CU patients and controls for allele or genotype distribution. We also did not observe any association between PDCD1 genotypes and severity of urticaria or age of disease onset. PD1.3 and PD1.5 polymorphisms were not proven to be implicated in susceptibility to ASST-positive CU in the Polish population. A more comprehensive analysis of the 2q33-2q37 genomic region might reveal whether variants of 1 or more of the genes in this region are involved in susceptibility to CU.

A DFT study and micro-kinetic analysis of acetylene selective hydrogenation on Pd-doped Cu(111) surfaces

NASA Astrophysics Data System (ADS)

Ma, Ling-Ling; Lv, Cun-Qin; Wang, Gui-Chang

2017-07-01

Semi-hydrogenation of acetylene in a hydrogen-rich stream is an industrially important process. Inspired by the recent experiments that Cu(111) surface doped by a small number of Pd atoms can exhibit excellent catalytic performance toward the dissociation of H2 molecule as well as the high selective hydrogenation of acetylene as compared with pure Cu and Pd metal alone at low-temperature, here we performed systematic first-principles calculations to investigate the corresponding reaction mechanism related to the acetylene hydrogenation processes on single atom alloys (SAAs) and monolayer Pd/Cu(111) (i.e.,1.00 ML Pd/Cu(111)) model catalysts in detail, and to explore the possible factors controlling the high selectivity on SAAs. Our results clearly demonstrate that the SAA catalyst has higher selectivity for the ethylene formation than that of 1.00 ML Pd/Cu(111), and lower activity for the acetylene conversion compared with that of 1.00 ML Pd/Cu(111). The relatively high selectivity on SAA is mainly due to the facile desorption of ethylene and moderate activity in the dissociation of molecular H2. The main factor which lowers the selectivity towards the ethylene formation on 1.00 ML Pd/Cu(111) is that this system has a higher capacity to promote the breaking of Csbnd H/Csbnd C bonds, which leads to the formation of carbonaceous deposits and polymers such as benzene, and thus reduces the selectivity for the ethylene formation. Meanwhile, it was found that the desorption energy of ethylene on these two surfaces was smaller than the energy barrier of further hydrogenation, which results in the absence of ethane on these two systems. Micro-kinetic model analysis provides a further valuable insight into the evidence for the key factors controlling the catalytic activity and selectivity towards the selective hydrogenation of acetylene. Our findings may help people to design a highly selective hydrogenation catalyst by controlling the balance between the H2 dissociation and Csbnd H/Csbnd C bond broken processes, and a good catalyst should be the one with the modest catalytic activity in the activation of molecular H2. At the same time, the present work provides an extremely significant mechanism of acetylene trimerization to form benzene and carbon formation.

Stable and Efficient CuO Based Photocathode through Oxygen-Rich Composition and Au-Pd Nanostructure Incorporation for Solar-Hydrogen Production.

PubMed

Masudy-Panah, Saeid; Siavash Moakhar, Roozbeh; Chua, Chin Sheng; Kushwaha, Ajay; Dalapati, Goutam Kumar

2017-08-23

Enhancing stability against photocorrosion and improving photocurrent response are the main challenges toward the development of cupric oxide (CuO) based photocathodes for solar-driven hydrogen production. In this paper, stable and efficient CuO-photocathodes have been developed using in situ materials engineering and through gold-palladium (Au-Pd) nanoparticles deposition on the CuO surface. The CuO photocathode exhibits a photocurrent generation of ∼3 mA/cm 2 at 0 V v/s RHE. Time-of-flight secondary ion mass spectrometry (TOF-SIMS) analysis and X-ray spectroscopy (XPS) confirm the formation of oxygen-rich (O-rich) CuO film which demonstrates a highly stable photocathode with retained photocurrent of ∼90% for 20 min. The influence of chemical composition on the photocathode performance and stability has been discussed in detail. In addition, O-rich CuO photocathodes deposited with Au-Pd nanostructures have shown enhanced photoelectrochemical performance. Linear scan voltammetry characteristic shows ∼25% enhancement in photocurrent after Au-Pd deposition and reaches ∼4 mA/cm 2 at "0" V v/s RHE. Hydrogen evolution rate significantly depends on the elemental composition of CuO and metal nanostructure. The present work has demonstrated a stable photocathode with high photocurrent for visible-light-driven water splitting and hydrogen production.

Diatomite-supported Pd-M (M=Cu, Co, Ni) bimetal nanocatalysts for selective hydrogenation of long-chain aliphatic esters.

PubMed

Huang, Changliang; Zhang, Hongye; Zhao, Yanfei; Chen, Sha; Liu, Zhimin

2012-11-15

Diatomite supported Pd-M (M=Cu, Co, Ni) bimetal nanocatalysts with various metal compositions were prepared and characterized by means of X-ray diffraction, transmission electron microscopy, and X-ray photoelectron spectroscopy. It was demonstrated that the metal nanoparticles were uniformly distributed on the support, and their size was centered around 8 nm with a relatively narrow size distribution. The catalysts were used to catalyze hydrogenation of long-chain aliphatic esters, including methyl palmitate, methyl stearate, and methyl laurate. It was indicated that the all diatomite-supported Pd-based bimetal catalysts were active to the selective hydrogenation of long-chain esters to corresponding alcohols at 270°C, originated from the synergistic effect between the metal particles and the diatomite support. For the selective hydrogenation of methyl palmitate, Pd-Cu/diatomite with metal loading of 1% and Pd/Cu=3 displayed the highest performance, giving a 1-hexadecanol yield of 82.9% at the substrate conversion of 98.8%. Copyright © 2012 Elsevier Inc. All rights reserved.

Structural characterization of multimetallic nanoparticles

NASA Astrophysics Data System (ADS)

Mukundan, Vineetha

Bimetallic and trimetallic alloy nanoparticles have enhanced catalytic activities due to their unique structural properties. Using in situ time-resolved synchrotron based x-ray diffraction, we investigated the structural properties of nanoscale catalysts undergoing various heat treatments. Thermal treatment brings about changes in particle size, morphology, dispersion of metals on support, alloying, surface electronic properties, etc. First, the mechanisms of coalescence and grain growth in PtNiCo nanoparticles supported on planar silica on silicon were examined in detail in the temperature range 400-900°C. The sintering process in PtNiCo nanoparticles was found to be accompanied by lattice contraction and L10 chemical ordering. The mass transport involved in sintering is attributed to grain boundary diffusion and its corresponding activation energy is estimated from the data analysis. Nanoscale alloying and phase transformations in physical mixtures of Pd and Cu ultrafine nanoparticles were also investigated in real time with in situ synchrotron based x-ray diffraction complemented by ex situ high-resolution transmission electron microscopy. PdCu nanoparticles are interesting because they are found to be more efficient as catalysts in ethanol oxidation reaction (EOR) than monometallic Pd catalysts. The combination of metal support interaction and reactive/non-reactive environment was found to determine the thermal evolution and ultimate structure of this binary system. The composition of the as prepared Pd:Cu mixture in this study was 34% Pd and 66% Cu. At 300°C, the nanoparticles supported on silica and carbon black intermix to form a chemically ordered CsCl-type (B2) alloy phase. The B2 phase transforms into a disordered fcc alloy at higher temperature (>450°C). The alloy nanoparticles supported on silica and carbon black are homogeneous in volume, but evidence was found of Pd surface enrichment. In sharp contrast, when supported on alumina, the two metals segregated at 300°C to produce almost pure fcc Cu and Pd phases. Upon further annealing of the mixture on alumina above 600°C, the two metals interdiffused, forming two distinct disordered alloys of compositions 30% and 90% Pd. The annealing atmosphere also plays a major role in the structural evolution of these bimetallic nanoparticles. The nanoparticles annealed in forming gas are larger than the nanoparticles annealed in helium due to reduction of the surface oxides that promotes coalescence and sintering. The nanoscale composition and structure of alloy catalysts affect heterogeneous catalysis. We also studied Pd:Cu nanoparticle mixtures of different compositions. In Pd:Cu of composition ratio 1:1, ordered B2 phase is formed during annealing at 450C. During the ramped annealing from 450°C to 750°C, the B2 phase transforms into two different alloys, one alloy rich in copper and the other rich in Pd. This structural evolution is different from that of Pd-Cu system in bulk. In the 3:1 composition, the B2 phase dominates in the isothermal anneal at 450C but a disordered alloy fcc phase is also formed. On annealing to 750°C, the disordered fcc phase grows at the expense of the B2 phase. These findings have important applications for the thermal activation of Pd-Cu nanocatalysts for EOR reactions.

Tuned sensitivity towards H{sub 2}S and NH{sub 3} with Cu doped barium strontium titanate materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Simion, C. E., E-mail: simion@infim.ro; Teodorescu, V. S.; Stănoiu, A.

2014-11-05

The different amount of Cu-doped Barium Strontium Titanate (BST) thick film materials have been tested for their gas-sensing performances towards NH{sub 3} and H{sub 2}S under dry and 50% relative humidity (RH) background conditions. The optimum NH{sub 3} sensitivity was attained with 0.1mol% Cu-doped BST whereas the selective detection of H{sub 2}S was highlighted using 5mol% Cu-doped BST material. No cross-sensitivity effects to CO, NO{sub 2}, CH{sub 4} and SO{sub 2} were observed for all tested materials operated at their optimum temperature (200°C) under humid conditions (50% RH). The presence of humidity clearly enhances the gas sensitivity to NH{sub 3}more » and H{sub 2}S detection.« less

Electronic transport properties of intermediately coupled superconductors: PdTe2 and Cu0.04PdTe2

NASA Astrophysics Data System (ADS)

Hooda, M. K.; Yadav, C. S.

2018-01-01

We have investigated the electrical resistivity (1.8-480 K), Seebeck coefficient (2.5-300 K) and thermal conductivity (2.5-300 K) of PdTe2 and 4% Cu intercalated PdTe2 compounds. The electrical resistivity for the compounds shows a Bloch-Gruneisen-type linear temperature (T) dependence for 100 \\text{K}, and Fermi liquid behavior (ρ (T) \\propto T2) for T<50 \\text{K} . Seebeck coefficient data exhibit a strong competition between Normal (N) and Umklapp (U) scattering processes at low T. The low-T, thermal conductivity (κ) of the compounds is strongly dominated by the electronic contribution, and exhibits a rare linear T-dependence below 10 K. However, high-T, κ (T) shows the usual 1/T -dependence, dominated by the U-scattering process. The electron-phonon coupling parameters, estimated from the low-T, specific-heat data and first-principle electronic structure calculations suggest that PdTe2 and Cu0.04PdTe2 are intermediately coupled superconductors.

Near-Infrared Plasmonic-Enhanced Solar Energy Harvest for Highly Efficient Photocatalytic Reactions.

PubMed

Cui, Jiabin; Li, Yongjia; Liu, Lei; Chen, Lin; Xu, Jun; Ma, Jingwen; Fang, Gang; Zhu, Enbo; Wu, Hao; Zhao, Lixia; Wang, Leyu; Huang, Yu

2015-10-14

We report a highly efficient photocatalyst comprised of Cu7S4@Pd heteronanostructures with plasmonic absorption in the near-infrared (NIR)-range. Our results indicated that the strong NIR plasmonic absorption of Cu7S4@Pd facilitated hot carrier transfer from Cu7S4 to Pd, which subsequently promoted the catalytic reactions on Pd metallic surface. We confirmed such enhancement mechanism could effectively boost the sunlight utilization in a wide range of photocatalytic reactions, including the Suzuki coupling reaction, hydrogenation of nitrobenzene, and oxidation of benzyl alcohol. Even under irradiation at 1500 nm with low power density (0.45 W/cm(2)), these heteronanostructures demonstrated excellent catalytic activities. Under solar illumination with power density as low as 40 mW/cm(2), nearly 80-100% of conversion was achieved within 2 h for all three types of organic reactions. Furthermore, recycling experiments showed the Cu7S4@Pd were stable and could retain their structures and high activity after five cycles. The reported synthetic protocol can be easily extended to other Cu7S4@M (M = Pt, Ag, Au) catalysts, offering a new solution to design and fabricate highly effective photocatalysts with broad material choices for efficient conversion of solar energy to chemical energy in an environmentally friendly manner.

Bimetallic Nanoparticles as Efficient Catalysts: Facile and Green Microwave Synthesis

PubMed Central

Blosi, Magda; Ortelli, Simona; Costa, Anna Luisa; Dondi, Michele; Lolli, Alice; Andreoli, Sara; Benito, Patricia; Albonetti, Stefania

2016-01-01

This work deals with the development of a green and versatile synthesis of stable mono- and bi-metallic colloids by means of microwave heating and exploiting ecofriendly reagents: water as the solvent, glucose as a mild and non-toxic reducer and polyvinylpirrolidone (PVP) as the chelating agent. Particle size-control, total reaction yield and long-term stability of colloids were achieved with this method of preparation. All of the materials were tested as effective catalysts in the reduction of p-nitrophenol in the presence of NaBH4 as the probe reaction. A synergistic positive effect of the bimetallic phase was assessed for Au/Cu and Pd/Au alloy nanoparticles, the latter showing the highest catalytic performance. Moreover, monoand bi-metallic colloids were used to prepare TiO2- and CeO2-supported catalysts for the liquid phase oxidation of 5-hydroxymethylfufural (HMF) to 2,5-furandicarboxylic acid (FDCA). The use of Au/Cu and Au/Pd bimetallic catalysts led to an increase in FDCA selectivity. Finally, preformed Pd/Cu nanoparticles were incorporated into the structure of MCM-41-silica. The resulting Pd/Cu MCM-41 catalysts were tested in the hydrodechlorination of CF3OCFClCF2Cl to CF3OCF=CF2. The effect of Cu on the hydrogenating properties of Pd was demonstrated. PMID:28773672

How the toughness in metallic glasses depends on topological and chemical heterogeneity

PubMed Central

An, Qi; Samwer, Konrad; Demetriou, Marios D.; Floyd, Michael C.; Duggins, Danielle O.; Johnson, William L.; Goddard, William A.

2016-01-01

To gain insight into the large toughness variability observed between metallic glasses (MGs), we examine the origin of fracture toughness through bending experiments and molecular dynamics (MD) simulations for two binary MGs: Pd82Si18 and Cu46Zr54. The bending experiments show that Pd82Si18 is considerably tougher than Cu46Zr54, and the higher toughness of Pd82Si18 is attributed to an ability to deform plastically in the absence of crack nucleation through cavitation. The MD simulations study the initial stages of cavitation in both materials and extract the critical factors controlling cavitation. We find that for the tougher Pd82Si18, cavitation is governed by chemical inhomogeneity in addition to topological structures. In contrast, no such chemical correlations are observed in the more brittle Cu46Zr54, where topological low coordination number polyhedra are still observed around the critical cavity. As such, chemical inhomogeneity leads to more difficult cavitation initiation in Pd82Si18 than in Cu46Zr54, leading to a higher toughness. The absence of chemical separation during cavitation initiation in Cu46Zr54 decreases the energy barrier for a cavitation event, leading to lower toughness. PMID:27307438

Facile preparation of dendritic Ag-Pd bimetallic nanostructures on the surface of Cu foil for application as a SERS-substrate

NASA Astrophysics Data System (ADS)

Yi, Zao; Tan, Xiulan; Niu, Gao; Xu, Xibin; Li, Xibo; Ye, Xin; Luo, Jiangshan; Luo, Binchi; Wu, Weidong; Tang, Yongjian; Yi, Yougen

2012-05-01

Dendritic Ag-Pd bimetallic nanostructures have been synthesized on the surface of Cu foil via a multi-stage galvanic replacement reaction (MGRR) of Ag dendrites in a Na2PdCl4 solution. After five stages of replacement reaction, one obtained structures with protruding Ag-Pd flakes; these will mature into many porous structures with a few Ag atoms that are left over dendrites. The dendritic Ag-Pd bimetallic nanostructures were characterized by transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), field emission scanning electron microscopy (FESEM), energy-dispersive X-ray (EDX), selected area electron diffraction (SAED) and X-ray photoelectron spectroscopy (XPS). The morphology of the products strongly depended on the stage of galvanic replacement reaction and reaction temperature. The morphology and composition-dependent surface-enhanced Raman scattering (SERS) of the as-synthesized Ag-Pd bimetallic nanostructures were investigated. The effectiveness of these dendritic Ag-Pd bimetallic nanostructures on the surface of Cu foil as substrates toward SERS detection was evaluated by using rhodamine 6G (R6G) as a probe molecule. The results indicate that as-synthesized dendritic Ag-Pd bimetallic nanostructures are good candidates for SERS spectroscopy.

Synthesis, crystal structure and electronic structure of the binary phase Rh2Cd5

NASA Astrophysics Data System (ADS)

Koley, Biplab; Chatterjee, S.; Jana, Partha P.

2017-02-01

A new phase in the Rh-Cd binary system - Rh2Cd5 has been identified and characterized by single crystal X-ray diffraction and Energy dispersive X-ray analysis. The stoichiometric compound Rh2Cd5 crystallizes with a unit cell containing 14 atoms, in the orthorhombic space group Pbam (55). The crystal structure of Rh2Cd5 can be described as a defect form of the In3Pd5 structure with ordered vacancies, formed of two 2D atomic layers with the stacking sequence: ABAB. The A type layers consist of (3.6.3.6)-Kagomé nets of Cd atoms while the B type layers consist of (35) (37)- nets of both Cd and Rh atoms. The stability of this line phase is investigated by first principle electronic structure calculations on the model of ordered Rh2Cd5.

The Synthesis and Characterization of a Group of Transition Metal Octabutoxynaphthalocyanines and the Absorption and Emission Properties of the Co, Rh, Ir, Ni, Pd and Pt Members of This Group

PubMed Central

Kim, Junhwan; Soldatova, Alexandra V.; Rodgers, Michael A. J.; Kenney, Malcolm E.

2013-01-01

The synthesis and photophysical properties of new metallo-octabutoxynaphthalocyanines with Rh(III), Ir(III), and Pt(II) are reported. Various metals were inserted into the metal-free octabutoxynaphthalocyanine and the resultant metal complexes were fully characterized by NMR, UV-vis spectroscopy, and mass spectrometry. The absorption and emission properties of these new complexes were also examined and compared to those of Co(II), Ni(II), and Pd(II) octabutoxynaphthalocyanines. The results provide useful information to understand the effect of these transition metals on the properties of this macrocyclic ring. PMID:23745014

Synthesis and spectral studies of platinum metal complexes of benzoin thiosemicarbazone

NASA Astrophysics Data System (ADS)

Offiong, Offiong E.

1994-11-01

The platinum metal chelates of benzoin thiosemicarbazone obtained with Ru(III), Rh(III), Ir(III), Pd(II) and Pt(II) were prepared from their corresponding halide salts. The complexes were characterized by elemental analysis, conductance measurement, IR, Raman, 1H-NMR, 13C-NMR and UV-visible spectra studies. Various ligand field parameters and nephelauxetic parameters were also calculated. The mode of bonding and the geometry of the ligand environment around the metal ion have been discussed in the light of the available data obtained. Complexes of Ru(III), Rh(III) and Ir(III) are six-coordinate octahedral, while Pd(II) and Pt(II) halide complexes are four-coordinated with halides bridging.

Flower-like Rh/Cu superhydrophobic coating via electrodeposition and its self-cleaning property

NASA Astrophysics Data System (ADS)

Zhao, N.; Lu, S. X.; Xu, W. G.; Cheng, X. L.

2017-01-01

Rh/Cu superhydrophobic coatings with textured flower-like dual micro-nano structures were fabricated on copper substrates via electrodesposition of Rh followed by annealing treatment. The scanning electron microscopy and X-ray diffraction pattern were conducted to analyse the morphology and chemical composition of the coating surfaces, respectively. The water drops exhibited a water contact angle of 168±1° and a sliding angle of 0±1° on the coating surfaces which were obtained by etching in concentrated hydrochloric acid and nitric acid, electrodeposited at -1.0 V for 30 min and annealing in an oven at 180°C for 60 min. The prepared superhydrophobic coatings showed excellent water repellence and self-cleaning property due to its extremely high water contact angle.

Displacement-dispersive liquid-liquid microextraction based on solidification of floating organic drop of trace amounts of palladium in water and road dust samples prior to graphite furnace atomic absorption spectrometry determination.

PubMed

Ghanbarian, Maryam; Afzali, Daryoush; Mostafavi, Ali; Fathirad, Fariba

2013-01-01

A new displacement-dispersive liquid-liquid microextraction method based on the solidification of floating organic drop was developed for separation and preconcentration of Pd(ll) in road dust and aqueous samples. This method involves two steps of dispersive liquid-liquid microextraction based on solidification. In Step 1, Cu ions react with diethyldithiocarbamate (DDTC) to form Cu-DDTC complex, which is extracted by dispersive liquid-liquid microextraction based on a solidification procedure using 1-undecanol (extraction solvent) and ethanol (dispersive solvent). In Step 2, the extracted complex is first dispersed using ethanol in a sample solution containing Pd ions, then a dispersive liquid-liquid microextraction based on a solidification procedure is performed creating an organic drop. In this step, Pd(ll) replaces Cu(ll) from the pre-extracted Cu-DDTC complex and goes into the extraction solvent phase. Finally, the Pd(ll)-containing drop is introduced into a graphite furnace using a microsyringe, and Pd(ll) is determined using atomic absorption spectrometry. Several factors that influence the extraction efficiency of Pd and its subsequent determination, such as extraction and dispersive solvent type and volume, pH of sample solution, centrifugation time, and concentration of DDTC, are optimized.

Initial Reduction of CO2 on Pd-, Ru-, and Cu-Doped CeO2(111) Surfaces: Effects of Surface Modification on Catalytic Activity and Selectivity.

PubMed

Guo, Chen; Wei, Shuxian; Zhou, Sainan; Zhang, Tian; Wang, Zhaojie; Ng, Siu-Pang; Lu, Xiaoqing; Wu, Chi-Man Lawrence; Guo, Wenyue

2017-08-09

Surface modification by metal doping is an effective treatment technique for improving surface properties for CO 2 reduction. Herein, the effects of doped Pd, Ru, and Cu on the adsorption, activation, and reduction selectivity of CO 2 on CeO 2 (111) were investigated by periodic density functional theory. The doped metals distorted the configuration of a perfect CeO 2 (111) by weakening the adjacent Ce-O bond strength, and Pd doping was beneficial for generating a highly active O vacancy. The analyses of adsorption energy, charge density difference, and density of states confirmed that the doped metals were conducive for enhancing CO 2 adsorption, especially for Cu/CeO 2 (111). The initial reductive dissociation CO 2 → CO* + O* on metal-doped CeO 2 (111) followed the sequence of Cu- > perfect > Pd- > Ru-doped CeO 2 (111); the reductive hydrogenation CO 2 + H → COOH* followed the sequence of Cu- > perfect > Ru- > Pd-doped CeO 2 (111), in which the most competitive route on Cu/CeO 2 (111) was exothermic by 0.52 eV with an energy barrier of 0.16 eV; the reductive hydrogenation CO 2 + H → HCOO* followed the sequence of Ru- > perfect > Pd-doped CeO 2 (111). Energy barrier decomposition analyses were performed to identify the governing factors of bond activation and scission along the initial CO 2 reduction routes. Results of this study provided deep insights into the effect of surface modification on the initial reduction mechanisms of CO 2 on metal-doped CeO 2 (111) surfaces.

PdCuPt Nanocrystals With Multi-branches for Enzyme-free Glucose Detection

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fu, Shaofang; Zhu, Chengzhou; Song, Junhua

By carefully controlling the synthesis condition, branched PtCu bimetallic templates were synthesized in aqueous solution. After the galvanic replacement reaction between PtCu templates and the Pt precursors, PdCuPt trimetallic nanocrystals with branched structures were obtained. Owing to the open structure and the optimized composition, the electrochemical experimental results reveal that the PdCuPt trimetallic nanocrystals exhibit high electrocatalytic activity, selectivity and stability for the oxidation of glucose in alkaline solution. In details, a sensitivity of 378 μA/mM/cm2 and a detection limit of 1.29 μM can be achieved. The good electrocatalytic performance should be attributed to the unique branched nanostructure as wellmore » as the synergistic effect among metals. The superior catalytic properties suggest that these nanocrystals are promising for enzyme-free detection of glucose.« less

Platinum-Group Elements in Basalts Derived From the Icelandic Mantle Plume -Past and Present.

NASA Astrophysics Data System (ADS)

Momme, P.; Oskarsson, N.; Gronvold, K.; Tegner, C.; Brooks, K.; Keays, R.

2001-12-01

Paleogene basalts ( ~55Ma) derived from the ancestral Iceland mantle plume and extruded during continental rifting are exposed along the Blosseville Kyst in central East Greenland. These basalts comprise three intercalated series, viz: a low-Ti, high-Ti and a very high-Ti series. The two Ti-rich series are interpreted to represent continental flood basalts formed by low degrees of partial melting (degree of melting F=3-9%) while the low-Ti series are believed to have formed by higher degrees of partial melting (F:15-25%). All three of the East Greenland basalt series are enriched in the PGE, relative to normal MORB. During differentiation of the low-Ti series, Pd increase from 11 to 24 ppb whereas Pt and Ir decrease from 12 and 0.6 ppb to 3 and <0.05 ppb respectively. The primitive basalts (molar Mg#60) of the dominant high-Ti series contain ~6-10 ppb Pd, ~7-10 ppb Pt and ~0.2 ppb Ir whereas the most evolved basalts (Mg#43) contain 25 ppb Pd, 5 ppb Pt and <0.05 ppb Ir. The PGE-rich nature of these basalts is surprising because low degree partial melts are generally S-saturated and hence strongly depleted in the PGE (cf, Keays, 1995). However, our data indicates that all of the East Greenland magmas were S-undersaturated and as they underwent differentiation, Pd behaved incompatibly while Ir and Pt behaved compatibly. Primitive Holocene Icelandic olivine tholeiites contain 120 ppm Cu, 6 ppb Pd, 4 ppb Pt and 0.2 ppb Ir while their picritic counterparts contain 74 ppm Cu, 17 ppb Pd, 7 ppb Pt and 0.3 ppb Ir. Both the olivine tholeiites and the picrites are believed to have formed by high degrees of partial melting (15-25%) which would have exhausted all of the sulphides in the mantle source region and produced S-undersaturated magmas. In Icelandic samples with 10-14wt% MgO, Cu and the PGEs vary systematically between the primitive picrite and olivine tholeiite compositions given above i.e there is an inverse correlation between Cu and the PGEs. This is best explained by mixing between parental olivine tholeiite and picrite magmas. The low Cu/Pd ratio in the most primitive picrite probably reflect derivation from a depleted mantle where Cu was less efficiently retained in sulphides compared to Pd during previous melt extraction episodes. Whithin the analysed suite of olivine tholeiites, Ir decreases from 0.15 to 0.06 ppb, Pd increases from ~6 to ~15 ppb and Pt/Pd ratio decreases from 0.8-0.2 during differentiation (7-4wt% MgO); these variations provide further evidence that the olivine tholeiite magmas remained S-undersaturated throughout their differentiation. To summarize, (1) Continental flood basalts and low-Ti tholeiites in the Paleogene East Greenland flood basalt sequence, as well as Holocene Icelandic olivine tholeiites are PGE-rich relative to normal MORB. (2) Their PGE-contents vary as a function of S-undersaturated differentiation. (3) Cu-PGE variations in Icelandic samples with 10-14 wt% MgO suggest that they represent mixtures between distinct tholeiitic (Cu/Pd: 20000) and depleted picritic (Cu/Pd: 4400) parental liquids. Reference: Keays RR (1995) The role of komatiitic magmatism and S-saturation in the formation of ore deposits. Lithos 34:1-18.

Carbon Dioxide Gas Sensors and Method of Manufacturing and Using Same

NASA Technical Reports Server (NTRS)

Hunter, Gary W. (Inventor); Xu, Jennifer C. (Inventor)

2014-01-01

A gas sensor comprises a substrate layer; a pair of interdigitated metal electrodes, said electrodes include upper surfaces, the electrodes selected from the group consisting of Pt, Pd, Au, Ir, Ag, Ru, Rh, In, Os, and their alloys. A first layer of solid electrolyte staying in between electrode fingers and partially on said upper surfaces of said electrodes, said first layer selected from NASICON, LISICON, KSICON and.beta.''-Alumina. A second layer of metal carbonate(s) as an auxiliary electrolyte engaging said upper surfaces of the electrodes and the first solid electrolyte. The metal carbonates selected from the group consisting of the following ions Na.sup.+, K.sup.+, Li.sup.+, Ag.sup.+, H.sup.+, Pb.sup.2+, Sr.sup.2+, Ba.sup.2+, and any combination thereof. An extra layer of metal oxide selected from the group consisting of SnO.sub.2, In.sub.2O.sub.3, TiO.sub.2, WO.sub.3, ZnO, Fe.sub.2O.sub.3, ITO, CdO, U.sub.3O.sub.8, Ta.sub.2O.sub.5, BaO, MoO.sub.2, MoO.sub.3, V.sub.2O.sub.5, Nb.sub.2O.sub.5, CuO, Cr.sub.2O.sub.3, La.sub.2O.sub.3, RuO.sub.3, RuO.sub.2, ReO.sub.2, ReO.sub.3, Ag.sub.2O, CoO, Cu.sub.2O, SnO, NiO, Pr.sub.2O.sub.3, BaO, PdO.sub.2, HfO.sub.3, HfO.sub.3 or other metal oxide and their mixtures residing above and in engagement with the second electrolyte to improve sensor performance and/or to reduce sensor heating power consumption.

Effect of counterpart metals in carbon-supported Pt-based catalysts prepared using radiation chemical method

NASA Astrophysics Data System (ADS)

Okazaki, Tomohisa; Seino, Satoshi; Matsuura, Yoshiyuki; Otake, Hiroaki; Kugai, Junichiro; Ohkubo, Yuji; Nitani, Hiroaki; Nakagawa, Takashi; Yamamoto, Takao A.

2017-04-01

The process of nanoparticle formation by radiation chemical synthesis in a heterogeneous system has been investigated. Carbon-supported Pt-based bimetallic nanoparticles were synthesized using a high-energy electron beam. Rh, Cu, Ru, and Sn were used as counterpart metals. The nanoparticles were characterized by inductively coupled plasma atomic emission spectrometry, transmission electron microscopy, X-ray diffraction, and X-ray absorption spectroscopy. PtRh formed a uniform random alloy nanoparticle, while Cu partially formed an alloy with Pt and the remaining Cu existed as CuO. PtRu formed an alloy structure with a composition distribution of a Pt-rich core and Ru-rich shell. No alloying was observed in PtSn, which had a Pt-SnO2 structure. The alloy and oxide formation mechanisms are discussed considering the redox potentials, the standard enthalpy of oxide formation, and the solid solubilities of Pt and the counterpart metals.

Viscous flow of the Pd43Ni10Cu27P20 bulk metallic glass-forming liquid

NASA Astrophysics Data System (ADS)

Fan, G. J.; Fecht, H.-J.; Lavernia, E. J.

2004-01-01

The equilibrium viscosity of the Pd43Ni10Cu27P20 bulk metallic glass-forming liquid was measured over a wide temperature range from the equilibrium supercooled liquid state to the glass transition region using parallel-plate rheometry and three-point beam bending. Based on the measured viscosity data, the fragility of this liquid was quantitatively determined. The Pd43Ni10Cu27P20 alloy, despite exhibiting the best glass-forming ability reported thus far, is relatively fragile compared with other bulk glass-forming liquids, such as Vit 1 and Vit 4.

Characterization, Recovery Opportunities, and Valuation of Metals in Municipal Sludges from U.S. Wastewater Treatment Plants Nationwide.

PubMed

Westerhoff, Paul; Lee, Sungyun; Yang, Yu; Gordon, Gwyneth W; Hristovski, Kiril; Halden, Rolf U; Herckes, Pierre

2015-08-18

U.S. sewage sludges were analyzed for 58 regulated and nonregulated elements by ICP-MS and electron microscopy to explore opportunities for removal and recovery. Sludge/water distribution coefficients (KD, L/kg dry weight) spanned 5 orders of magnitude, indicating significant metal accumulation in biosolids. Rare-earth elements and minor metals (Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) detected in sludges showed enrichment factors (EFs) near unity, suggesting dust or soils as likely dominant sources. In contrast, most platinum group elements (i.e., Ru, Rh, Pd, Pt) showed high EF and KD values, indicating anthropogenic sources. Numerous metallic and metal oxide colloids (<100-500 nm diameter) were detected; the morphology of abundant aggregates of primary particles measuring <100 nm provided clues to their origin. For a community of 1 million people, metals in biosolids were valued at up to US$13 million annually. A model incorporating a parameter (KD × EF × $Value) to capture the relative potential for economic value from biosolids revealed the identity of the 13 most lucrative elements (Ag, Cu, Au, P, Fe, Pd, Mn, Zn, Ir, Al, Cd, Ti, Ga, and Cr) with a combined value of US $280/ton of sludge.

Anticipatory Postural Adjustment During Self-Initiated, Cued, and Compensatory Stepping in Healthy Older Adults and Patients With Parkinson Disease.

PubMed

Schlenstedt, Christian; Mancini, Martina; Horak, Fay; Peterson, Daniel

2017-07-01

To characterize anticipatory postural adjustments (APAs) across a variety of step initiation tasks in people with Parkinson disease (PD) and healthy subjects. Cross-sectional study. Step initiation was analyzed during self-initiated gait, perceptual cued gait, and compensatory forward stepping after platform perturbation. People with PD were assessed on and off levodopa. University research laboratory. People (N=31) with PD (n=19) and healthy aged-matched subjects (n=12). Not applicable. Mediolateral (ML) size of APAs (calculated from center of pressure recordings), step kinematics, and body alignment. With respect to self-initiated gait, the ML size of APAs was significantly larger during the cued condition and significantly smaller during the compensatory condition (P<.001). Healthy subjects and patients with PD did not differ in body alignment during the stance phase prior to stepping. No significant group effect was found for ML size of APAs between healthy subjects and patients with PD. However, the reduction in APA size from cued to compensatory stepping was significantly less pronounced in PD off medication compared with healthy subjects, as indicated by a significant group by condition interaction effect (P<.01). No significant differences were found comparing patients with PD on and off medications. Specific stepping conditions had a significant effect on the preparation and execution of step initiation. Therefore, APA size should be interpreted with respect to the specific stepping condition. Across-task changes in people with PD were less pronounced compared with healthy subjects. Antiparkinsonian medication did not significantly improve step initiation in this mildly affected PD cohort. Copyright © 2016 American Congress of Rehabilitation Medicine. Published by Elsevier Inc. All rights reserved.

Green Synthesis of Metal and Metal Oxide Nanoparticles and Their Effect on the Unicellular Alga Chlamydomonas reinhardtii

NASA Astrophysics Data System (ADS)

Nguyen, Nhung H. A.; Padil, Vinod Vellora Thekkae; Slaveykova, Vera I.; Černík, Miroslav; Ševců, Alena

2018-05-01

Recently, the green synthesis of metal nanoparticles has attracted wide attention due to its feasibility and very low environmental impact. This approach was applied in this study to synthesise nanoscale gold (Au), platinum (Pt), palladium (Pd), silver (Ag) and copper oxide (CuO) materials in simple aqueous media using the natural polymer gum karaya as a reducing and stabilising agent. The nanoparticles' (NPs) zeta-potential, stability and size were characterised by Zetasizer Nano, UV-Vis spectroscopy and by electron microscopy. Moreover, the biological effect of the NPs (concentration range 1.0-20.0 mg/L) on a unicellular green alga ( Chlamydomonas reinhardtii) was investigated by assessing algal growth, membrane integrity, oxidative stress, chlorophyll ( Chl) fluorescence and photosystem II photosynthetic efficiency. The resulting NPs had a mean size of 42 (Au), 12 (Pt), 1.5 (Pd), 5 (Ag) and 180 (CuO) nm and showed high stability over 6 months. At concentrations of 5 mg/L, Au and Pt NPs only slightly reduced algal growth, while Pd, Ag and CuO NPs completely inhibited growth. Ag, Pd and CuO NPs showed strong biocidal properties and can be used for algae prevention in swimming pools (CuO) or in other antimicrobial applications (Pd, Ag), whereas Au and Pt lack these properties and can be ranked as harmless to green alga.

MgO buffer layers on rolled nickel or copper as superconductor substrates

DOEpatents

Paranthaman, Mariappan; Goyal, Amit; Kroeger, Donald M.; List, III, Frederic A.

2001-01-01

Buffer layer architectures are epitaxially deposited on biaxially-textured rolled-Ni and/or Cu substrates for high current conductors, and more particularly buffer layer architectures such as MgO/Ag/Pt/Ni, MgO/Ag/Pd/Ni, MgO/Ag/Ni, MgO/Ag/Pd/Cu, MgO/Ag/Pt/Cu, and MgO/Ag/Cu. Techniques used to deposit these buffer layers include electron beam evaporation, thermal evaporation, rf magnetron sputtering, pulsed laser deposition, metal-organic chemical vapor deposition (MOCVD), combustion CVD, and spray pyrolysis.

Method for making MgO buffer layers on rolled nickel or copper as superconductor substrates

DOEpatents

Paranthaman, Mariappan; Goyal, Amit; Kroeger, Donald M.; List, III, Frederic A.

2002-01-01

Buffer layer architectures are epitaxially deposited on biaxially-textured rolled-Ni and/or Cu substrates for high current conductors, and more particularly buffer layer architectures such as MgO/Ag/Pt/Ni, MgO/Ag/Pd/Ni, MgO/Ag/Ni, MgO/Ag/Pd/Cu, MgO/Ag/Pt/Cu, and MgO/Ag/Cu. Techniques used to deposit these buffer layers include electron beam evaporation, thermal evaporation, rf magnetron sputtering, pulsed laser deposition, metal-organic chemical vapor deposition (MOCVD), combustion CVD, and spray pyrolysis.

Catalytic activity of Pd-doped Cu nanoparticles for hydrogenation as a single-atom-alloy catalyst.

PubMed

Cao, Xinrui; Fu, Qiang; Luo, Yi

2014-05-14

The single atom alloy of extended surfaces is known to provide remarkably enhanced catalytic performance toward heterogeneous hydrogenation. Here we demonstrate from first principles calculations that this approach can be extended to nanostructures, such as bimetallic nanoparticles. The catalytic properties of the single-Pd-doped Cu55 nanoparticles have been systemically examined for H2 dissociation as well as H atom adsorption and diffusion, following the concept of single atom alloy. It is found that doping a single Pd atom at the edge site of the Cu55 shell can considerably reduce the activation energy of H2 dissociation, while the single Pd atom doped at the top site or in the inner layers is much less effective. The H atom adsorption on Cu55 is slightly stronger than that on the Cu(111) surface; however, a larger nanoparticle that contains 147 atoms could effectively recover the weak binding of the H atoms. We have also investigated the H atom diffusion on the 55-atom nanoparticle and found that spillover of the produced H atoms could be a feasible process due to the low diffusion barriers. Our results have demonstrated that facile H2 dissociation and weak H atom adsorption could be combined at the nanoscale. Moreover, the effects of doping one more Pd atom on the H2 dissociation and H atom adsorption have also been investigated. We have found that both the doping Pd atoms in the most stable configuration could independently exhibit their catalytic activity, behaving as two single-atom-alloy catalysts.

Anomalous Change of Hall Coefficient in Overdoped La2-xSrxCu1-yZnyO4 around x = 0.2

NASA Astrophysics Data System (ADS)

Tonishi, Jun; Suzuki, Takao; Goto, Takayuki

2006-09-01

The Hall coefficient (RH) has been measured in 0.5% Zn-doped La2-xSrxCu0.995Zn0.005O4 under high magnetic fields up to 12 T. With decreasing temperature, RH increases and begins to decrease below a temperature TRH. This characteristic temperature TRH has the local maximum around x = 0.195, and this Sr-concentration coincides with that the superconducting transition temperature is slightly suppressed. This behavior is quite similar to the phenomena observed in the stripe phase in x ˜ 0.12. These results suggest that the anomalous decrease of RH around x = 0.195 observed in this study is responsible for the "1/4"-anomaly [as reported by Kakinuma et al., Phys. Rev. B 59, 1491 (1999).].

Electrochemical Growth of Single-Crystal Metal Nanowires via a Two-Dimensional Nucleation and Growth Mechanism.

PubMed

Tian, Mingliang; Wang, Jinguo; Kurtz, James; Mallouk, Thomas E; Chan, M H W

2003-07-01

Metallic nanowires (Au, Ag, Cu, Ni, Co, and Rh) with an average diameter of 40 nm and a length of 3-5 μm have been fabricated by electrodeposition in the pores of track-etched polycarbonate membranes. Structural characterizations by transmission electron microscopy (TEM) and electron diffraction showed that nanowires of Au, Ag, and Cu are single-crystalline with a preferred [111] orientation, whereas Ni, Co, and Rh wires are polycrystalline. Possible mechanisms responsible for nucleation and growth for single-crystal noble metals versus polycrystalline group VIII-B metals are discussed.

Diazo compounds and N-tosylhydrazones: novel cross-coupling partners in transition-metal-catalyzed reactions.

PubMed

Xiao, Qing; Zhang, Yan; Wang, Jianbo

2013-02-19

Transition-metal-catalyzed carbene transformations and cross-couplings represent two major reaction types in organometallic chemistry and organic synthesis. However, for a long period of time, these two important areas have evolved separately, with essentially no overlap or integration. Thus, an intriguing question has emerged: can cross-coupling and metal carbene transformations be merged into a single reaction cycle? Such a combination could facilitate the development of novel carbon-carbon bond-forming methodologies. Although this concept was first explored about 10 years ago, rapid developments inthis area have been achieved recently. Palladium catalysts can be used to couple diazo compounds with a wide variety of organic halides. Under oxidative coupling conditions, diazo compounds can also react with arylboronic acids and terminal alkynes. Both of these coupling reactions form carbon-carbon double bonds. As the key step in these catalytic processes, Pd carbene migratory insertion plays a vital role in merging the elementary steps of Pd intermediates, leading to novel carbon-carbon bond formations. Because the diazo substrates can be generated in situ from N-tosylhydrazones in the presence of base, the N-tosylhydrazones can be used as reaction partners, making this type of cross-coupling reaction practical in organic synthesis. N-Tosylhydrazones are easily derived from the corresponding aldehydes or ketones. The Pd-catalyzed cross-coupling of N-tosylhydrazones is considered a complementary reaction to the classic Shapiro reaction for converting carbonyl functionalities into carbon-carbon double bonds. It can also serve as an alternative approach for the Pd-catalyzed cross-coupling of carbonyl compounds, which is usually achieved via triflates. The combination of carbene formation and cross-coupling in a single catalytic cycle is not limited to Pd-catalyzed reactions. Recent studies of Cu-, Rh-, Ni-, and Co-catalyzed cross-coupling reactions with diazo compounds or N-tosylhydrazones show that these transformations also work with other transition metals, demonstrating the generality of the diazo compounds as new cross-coupling partners in transition-metal-catalyzed coupling reactions.

Historical record of European emissions of heavy metals to the atmosphere since the 1650s from alpine snow/ice cores drilled near Monte Rosa.

PubMed

Barbante, Carlo; Schwikowski, Margit; Döring, Thomas; Gäggeler, Heinz W; Schotterer, Ulrich; Tobler, Leo; van de Velde, Katja; Ferrari, Christophe; Cozzi, Giulio; Turetta, Andrea; Rosman, Kevin; Bolshov, Michael; Capodaglio, Gabriele; Cescon, Paolo; Boutron, Claude

2004-08-01

Cr, Cu, Zn, Co, Ni, Mo, Rh, Pd, Ag, Cd, Sb, Pt, Au, and U have been determined in clean room conditions by inductively coupled plasma sector field mass spectrometry and other analytical techniques, in various sections of two dated snow/ice cores from the high-altitude (4450 m asl) glacier saddle Colle Gnifetti, Monte Rosa massif, located in the Swiss-Italian Alps. These cores cover a 350-year time period, from 1650 to 1994. The results show highly enhanced concentrations for most metals in snow/ice dated from the second half of the 20th century, compared with concentrations in ancient ice dated from the 17th and 18th centuries. The highest increase factors from the pre-1700 period to the post-1970 period are observed for Cd (36), Zn (19), Bi (15), Cu (11), and Ni (9), confirming the importance of atmospheric pollution by heavy metals in Europe. Metal concentrations observed in Colle Gnifetti snow around 1980 appear to be quantitatively related to metal emissions from Italy, Switzerland, Germany, France, Belgium, and Austria at that time, making it possible to reconstruct past changes in metal emission in these countries during the last centuries.

The Role of Citric Acid in Perfecting Platinum Monolayer on Palladium Nanoparticles during the Surface Limited Redox Replacement Reaction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhu, Shangqian; Yue, Jeffrey; Qin, Xueping

Cu-mediated-Pt-displacement method that involves the displacement of an underpotentially deposited (UPD) Cu monolayer by Pt has been extensively studied to prepare core-shell catalysts. It has been found that Pt clusters instead of a uniform Pt monolayer were formed in the gram batch synthesis. With a suitable surfactant, such as citric acid, the Pt shell could be much more uniform. In this study, the role of citric acid in controlling the Cu-Pt displacement reaction kinetics was studied by electrochemical techniques and theoretical approaches. It was found that citric acid strongly adsorbed on Pd, Pt, Cu/Pd, and Pt/Pd surfaces, especially in themore » double layer region in acid solutions. The strong adsorption of citric acid slowed down the Cu-Pt displacement reaction. The main characteristics of such strong interaction most likely arises from the OH groups in the citric acid molecule according to the molecular dynamics simulation results.« less

The Role of Citric Acid in Perfecting Platinum Monolayer on Palladium Nanoparticles during the Surface Limited Redox Replacement Reaction

DOE PAGES

Zhu, Shangqian; Yue, Jeffrey; Qin, Xueping; ...

2016-07-28

Cu-mediated-Pt-displacement method that involves the displacement of an underpotentially deposited (UPD) Cu monolayer by Pt has been extensively studied to prepare core-shell catalysts. It has been found that Pt clusters instead of a uniform Pt monolayer were formed in the gram batch synthesis. With a suitable surfactant, such as citric acid, the Pt shell could be much more uniform. In this study, the role of citric acid in controlling the Cu-Pt displacement reaction kinetics was studied by electrochemical techniques and theoretical approaches. It was found that citric acid strongly adsorbed on Pd, Pt, Cu/Pd, and Pt/Pd surfaces, especially in themore » double layer region in acid solutions. The strong adsorption of citric acid slowed down the Cu-Pt displacement reaction. The main characteristics of such strong interaction most likely arises from the OH groups in the citric acid molecule according to the molecular dynamics simulation results.« less

Noninferiority of glucose-6-phosphate dehydrogenase deficiency diagnosis by a point-of-care rapid test vs the laboratory fluorescent spot test demonstrated by copper inhibition in normal human red blood cells.

PubMed

Baird, J Kevin; Dewi, Mewahyu; Subekti, Decy; Elyazar, Iqbal; Satyagraha, Ari W

2015-06-01

Tens of millions of patients diagnosed with vivax malaria cannot safely receive primaquine therapy against repeated attacks caused by activation of dormant liver stages called hypnozoites. Most of these patients lack access to screening for glucose-6-phosphate dehydrogenase (G6PD) deficiency, a highly prevalent disorder causing serious acute hemolytic anemia with primaquine therapy. We optimized CuCl inhibition of G6PD in normal red blood cells (RBCs) to assess G6PD diagnostic technologies suited to point of care in the impoverished rural tropics. The most widely applied technology for G6PD screening-the fluorescent spot test (FST)-is impractical in that setting. We evaluated a new point-of-care G6PD screening kit (CareStart G6PD, CSG) against FST using graded CuCl treatments to simulate variable hemizygous states, and varying proportions of CuCl-treated RBC suspensions to simulate variable heterozygous states of G6PD deficiency. In experiments double-blinded to CuCl treatment, technicians reading FST and CSG test (n = 269) classified results as positive or negative for deficiency. At G6PD activity ≤40% of normal (n = 112), CSG test was not inferior to FST in detecting G6PD deficiency (P = 0.003), with 96% vs 90% (P = 0.19) sensitivity and 75% and 87% (P = 0.01) specificity, respectively. The CSG test costs less, requires no specialized equipment, laboratory skills, or cold chain for successful application, and performs as well as the FST standard of care for G6PD screening. Such a device may vastly expand access to primaquine therapy and aid in mitigating the very substantial burden of morbidity and mortality imposed by the hypnozoite reservoir of vivax malaria. Copyright © 2015 Elsevier Inc. All rights reserved.

Immunogenicity assessment of recombinant human c1-inhibitor: an integrated analysis of clinical studies.

PubMed

Hack, C Erik; Mannesse, Maurice; Baboeram, Aartie; Oortwijn, Beatrijs; Relan, Anurag

2012-10-01

Recombinant human C1-inhibitor (rhC1INH) is used to treat acute angioedema attacks in hereditary angioedema (HAE) due to a genetic C1INH deficiency. Recombinant proteins in general may induce antibody responses and therefore evaluation of such responses in the target population is an essential step in the clinical development program of a recombinant protein. Here we report the assessment of the immunogenicity of rhC1INH in symptomatic HAE patients. Blood samples collected before and after administration of rhC1INH were tested for antibodies against plasma-derived (pd) or rhC1INH, or against host-related impurities (HRI). Above cut-off screening results were confirmed with displacement assays, and also tested for neutralizing anti-C1INH antibodies. Finally, the relation of antibodies to clinical efficacy and safety of rhC1INH was analyzed. Data from 155 HAE patients who received 424 treatments with rhC1INH were analyzed. 1.5% of all pre-exposure tests and 1.3% of all post-exposure tests were above the cut-off level in the screening assay for anti-C1INH antibodies. Six patients (3.9%) had anti-rhC1INH antibodies positive in the confirmatory assay. In two patients, confirmed antibodies were pre-existing with no increase post-exposure; in three patients, the antibodies occurred on a single occasion post-exposure; and in one patient, on subsequent occasions post-exposure. Neutralizing anti-pdC1INH antibodies were not found. Anti-HRI antibodies in the screening assay occurred in <0.7% of the tests before exposure to rhC1INH, in <1.9% after first exposure and in <3.1% after repeat treatment with rhC1INH. Five patients had anti-HRI antibodies positive in the confirmatory assay. In one patient, the antibodies were pre-existing, whereas in three of the 155 rhC1INH-treated patients (1.9%), confirmed anti-HRI antibodies occurred at more time points. Antibody findings were not associated with altered efficacy of rhC1INH or adverse events. These results indicate a reassuring immunosafety profile of rhC1INH as a treatment for acute HAE attacks.

"Invisible" gold and PGE elements in synthetic crystals of sphalerite and covellite: A EPMA, LA-ICP-MS and XAFS study

NASA Astrophysics Data System (ADS)

Tonkacheev, Dmitry; Chareev, Dmitry; Abramova, Vera; Tagirov, Boris

2016-04-01

Sphalerite and covellite are widespread minerals in the different genetic types of deposits and forms under the various conditions. The purpose of this work is to determine the possible range of concentration and chemical state of Au and PGE (Pt, Pd, Rh) in sphalerite (Zn,Fe) S and covellite (CuS). These minerals were synthesized using gas transport and salt flux techniques. The crystals of ZnS were grown using the gas transport method at 850°C and the salt flux one using NaCl/KCl, CsCl/NaCl/KCl, and LiCl/RbCl eutectic mixtures at 850, 645 and 470°C, respectively. CuS crystals were synthesized using the salt flux method in RbCl/LiCl melt at 470 and 340°C. The trace metal activity was always controlled by the presence of pure metal or its sulfide, and, therefore, the concentration of these elements in synthesized phases represent the maximum possible value for given T/f(S2) synthesis parameters. The LA-ICP-MS and/or EPMA techniques were used to determine the Au concentration in synthesized phases. The concentration of Au in sphalerite, synthesized at 850°C with admixture of Cd, Se, In, Fe, and Mn, reached 0.3wt%, whereas the sphalerite cell parameter extremely increased up to 5.4161Å relatively to 5.4060 Å for pure ZnS. It was found that the observed high Au concentration is caused by the presence of In (2091±46 ppm Au in sample with Fe and In in comparison with 14±7 for Se-bearing ZnS, 94±12 ppm for Fe-Mn-bearing sphalerite, and 96±46 for Fe-bearing sphalerite. The concentration of Au in Fe-bearing sphalerite synthesized at 645°C does not exceed 5 ppm. Therefore, increase of temperature results in the increase of Au concentration in sphalerite. The concentration of Au in another Fe-bearing-sphalerite series synthesized using gas transport method at 850°C various from 200 to 500 ppm and depends on the iron content. This fact could be related to the oxidation state or Fe in ZnS-FeS solid solution series. The concentration of Pt and Pd, Rh in sphalerite is below the detection limit of LA-ICP-MS (~30 ppb). However, these trace elements change the cathodoluminescence properties of ZnS. The concentration or gold in covellite was determined by both LA-ICP-MS and EPMA techniques and the final values clearly fit together. The maximum concentration can be observed at 450° and equal to 0.3wt%. This value changes minor due to the increasing of the temperature. In principle, adding admixtures of In, Zn, Se, Cu, Sb, Bi did not affect on the concentration of Au. However, in experiment where sulfur is excessive and a mixture of In, Zn, Se, Cu, Sb, Bi, were added the concentration of Au is equal 0.128+0.028 ppm. The gold distribution in covellite and sphalerite is always homogeneous. According to XANES data, atoms of Au in the crystal structure covellite is in triangles, formed by the atoms of Cu. In sphalerite gold is in "invisible" state too.

Effect of thione primers on adhesive bonding between an indirect composite material and Ag-Pd-Cu-Au alloy.

PubMed

Imai, Hideyuki; Koizumi, Hiroyasu; Shimoe, Saiji; Hirata, Isao; Matsumura, Hideo; Nikawa, Hiroki

2014-01-01

The current study evaluated the effect of primers on the shear bond strength of an indirect composite material joined to a silverpalladium-copper-gold (Ag-Pd-Cu-Au) alloy (Castwell). Disk specimens were cast from the alloy and were air-abraded with alumina. Eight metal primers were applied to the alloy surface. A light-polymerized indirect composite material (Solidex) was bonded to the alloy. Shear bond strength was determined both before and after the application of thermocycling. Two groups primed with Metaltite (thione) and M. L. Primer (sulfide) showed the greatest post-thermocycling bond strength (8.8 and 6.5 MPa). The results of the X-ray photoelectron spectroscopic (XPS) analysis suggested that the thione monomer (MTU-6) in the Metaltite primer was strongly adsorbed onto the Ag-Pd-Cu-Au alloy surface even after repeated cleaning with acetone. The application of either the thione (MTU-6) or sulfide primer is effective for enhancing the bonding between a composite material and Ag-Pd-Cu-Au alloy.

Preparation, Iodometric Analysis, and Classroom Demonstration of Superconductivity in YBa2Cu3O8-x.

ERIC Educational Resources Information Center

Harris, Daniel C.; And Others

1987-01-01

Described is a student preparation of YBa2Cu3O8-x, a classroom demonstration of its superconductivity, and an analytical chemistry experiment dealing with the oxidation state of copper in the material. (RH)

Development of Ag-Pd-Au-Cu alloy for multiple dental applications. Part 1. Effects of Pd and Cu contents, and addition of Ga or Sn on physical properties and bond with ultra-low fusing ceramic.

PubMed

Goto, S; Miyagawa, Y; Ogura, H

2000-09-01

Ag-Pd-Au-Cu quaternary alloys consisting of 30-50% Ag, 20-40% Pd, 10-20% Cu and 20% Au (mother alloys) were prepared. Then 5% Sn or 5% Ga was added to the mother alloy compositions, and another two alloy systems (Sn-added alloys and Ga-added alloys) were also prepared. The bond between the prepared alloys and an ultra-low fusing ceramic as well as their physical properties such as the solidus point, liquidus point and the coefficient of thermal expansion were evaluated. The solidus point and liquidus point of the prepared alloys ranged from 802 degrees C to 1142 degrees C and from 931 degrees C to 1223 degrees C, respectively. The coefficient of thermal expansion ranged from 14.6 to 17.1 x 10(-6)/degrees C for the Sn- and Ga-added alloys. In most cases, the Pd and Cu contents significantly influenced the solidus point, liquidus point and coefficient of thermal expansion. All Sn- and Ga-added alloys showed high area fractions of retained ceramic (92.1-100%), while the mother alloy showed relatively low area fractions (82.3%) with a high standard deviation (20.5%). Based on the evaluated properties, six Sn-added alloys and four Ga-added alloys among the prepared alloys were suitable for the application of the tested ultra-low fusing ceramic.

Solid state amorphization of metastable Al 0.5TiZrPdCuNi high entropy alloy investigated by high voltage electron microscopy

DOE PAGES

Nagase, Takeshi; Takeuchi, Akira; Amiya, Kenji; ...

2017-07-18

Here, the phase stability of high entropy alloy (HEA), Al 0.5TiZrPdCuNi, under fast electron irradiation was studied by in-situ high voltage electron microscopy (HVEM). The initial phase of this alloy quenched from the melt was dependent on cooling rate. At high cooling rates an amorphous phase was obtained, whereas a body-centered cubic ( b.c.c.) phase were obtained at low cooling rates. By thermal crystallization of the amorphous phase b.c.c. phase nano-crystals were formed. Upon fast electron irradiation solid state amorphization (SSA) was observed in b.c.c. phase regardless of the initial microstructure (i.e., “coarse crystalline structure” or “nano-crystalline structure with grainmore » boundaries as a sink for point defects”). SSA behavior in the Al 0.5TiZrPdCuNi HEAs was investigated by in-situ transmission electron microscopy observations. Because the amorphization is very rarely achieved in a solid solution phase under fast electron irradiation in common metallic materials, this result suggests that the Al 0.5TiZrPdCuNi HEA from other common alloys and the other HEAs. The differences in phase stability against the irradiation between the Al 0.5TiZrPdCuNi HEA and the other HEAs were discussed. This is the first experimental evidence of SSA in HEAs stimulated by fast electron irradiation.« less

Density-functional theory study of the initial oxygen incorporation in Pd(111)

NASA Astrophysics Data System (ADS)

Todorova, Mira; Reuter, Karsten; Scheffler, Matthias

2005-05-01

Pd(111) has recently been shown to exhibit a propensity to form a subnanometer thin surface oxide film already well before a full monolayer coverage of adsorbed O atoms is reached on the surface. Aiming at an atomic-scale understanding of this finding, we study the initial oxygen incorporation into the Pd(111) surface using density-functional theory. We find that oxygen incorporation into the sub-surface region starts at essentially the same coverage as formation of the surface oxide. This implies that the role of sub-surface oxygen should be considered as that of a metastable precursor in the oxidation process of the surface. The mechanisms found to play a role towards the ensuing stabilization of an ordered oxidic structure with a mixed on-surface/sub-surface site occupation follow a clear trend over the late 4d transition metal series, as seen by comparing our data to previously published studies concerned with oxide formation at the basal surface of Ru, Rh, and Ag. The formation of a linearly aligned O-TM-O trilayered structure (TM=Ru,Rh,Pd,Ag) , together with an efficient coupling to the underlying substrate seem to be key ingredients in this respect.

Sensitization of TiO₂ nanosheets with Cu-biphenylamine frame work to enhance photocatalytic degradation performance of toxic organic contaminants: Synthesis, mechanism and kinetic studies.

PubMed

Khan, Muhammad Asim; Mutahir, Sadaf; Wang, Fengyun; Lei, Wu; Xia, Mingzhu

2018-06-25

TNS/Cu(X) composite materials were firstly synthesized via simple overnight stirring of TNS in the methanolic solution of Cu complexes. The developed TNS/Cu(X) composites having a well-designed nanostructure, in which TNS and Cu complexes were closely bounded with each other. Biphenylamine complexes fixed on TNS surface in form of Nano-capsules, which were confirmed by TEM and SEM, thus improving the surface area and subsequently charge separation. Innovatively merged photocatalysts of Cu complexes with TNS were successfully verified for photocatalytic mineralization of colored and colorless organic contaminants under the visible light degradation. As compared to original TNS, TNS/Cu(BA) showed prominent improvement in the catalytic actions. Kinetics i.e. t1/2 (half-life times period), Kapp, and R2 (linear regression co-efficient) were also studied. The amended materials created charge separation, by means of electrons gathering at the higher CB, and holes gathering at lower level VB of Cu complex, therefore improving mineralization efficiency of electrons and holes. TNS/Cu(BA) degrade 99% to 99.6% of MO & RhB dyes in 120 min, and 160 min, respectively, and 68 % of phenol and 53% of TCP were destroyed in 180 min. The resilient holes can directly destroy MO, RhB, phenol, and TCP. © 2018 IOP Publishing Ltd.

Enhanced performance of direct Z-scheme CuS-WO3 system towards photocatalytic decomposition of organic pollutants under visible light

NASA Astrophysics Data System (ADS)

Song, Chundong; Wang, Xiang; Zhang, Jing; Chen, Xuebing; Li, Can

2017-12-01

CuS-WO3 composites were synthesized by an in situ solution method at low temperature. The crystalline phase, morphology, particle size, and the optical properties of CuS-WO3 samples were characterized by XRD, SEM, XPS, and UV-vis diffuse reflectance spectra. CuS-WO3 composites showed much higher activity for photocatalytic degradation of RhB as compared with WO3 and CuS. The degradation rate constant over 1 wt% CuS-WO3 catalyst was 4.4 times and 9.2 times higher than that of WO3 and CuS, respectively. It is found that holes (h+) and superoxide radical anions (rad O2-) are the dominant reactive species by using methanol, disodium ethylenediaminetetraacetate (EDTA) and ascorbic acid as scavengers. Band structure analysis shows that bottom of CB of WO3 is very similar with and higher (ca. 0.01 eV) than the top of VB of CuS. The results of PL showed that the similarity renders the recombination between photogenerated holes on the VB of CuS and photogenerated electrons on the CB of WO3 possible and easy, forming a direct Z-scheme in CuS-WO3. This result in that more electrons in the CB of CuS and holes in the VB of WO3 survived, and then participated in the photocatalytic degradation of RhB, showing an increased activity.

Enhanced performance of direct Z-scheme CuS-WO 3 system towards photocatalytic decomposition of organic pollutants under visible light

DOE Office of Scientific and Technical Information (OSTI.GOV)

Song, Chundong; Wang, Xiang; Zhang, Jing

CuS-WO 3 composites were synthesized by an in situ solution method at low temperature. The crystalline phase, morphology, particle size, and the optical properties of CuS-WO 3 samples were characterized by XRD, SEM, XPS, and UV–vis diffuse reflectance spectra. CuS-WO 3 composites showed much higher activity for photocatalytic degradation of RhB as compared with WO 3 and CuS. The degradation rate constant over 1 wt% CuS-WO 3 catalyst was 4.4 times and 9.2 times higher than that of WO 3 and CuS, respectively. It is found that holes (h+) and superoxide radical anions (O2-) are the dominant reactive species bymore » using methanol, disodium ethylenediaminetetraacetate (EDTA) and ascorbic acid as scavengers. Band structure analysis shows that bottom of CB of WO 3 is very similar with and higher (ca. 0.01 eV) than the top of VB of CuS. The results of PL showed that the similarity renders the recombination between photogenerated holes on the VB of CuS and photogenerated electrons on the CB of WO 3 possible and easy, forming a direct Z-scheme in CuS-WO 3. This result in that more electrons in the CB of CuS and holes in the VB of WO 3 survived, and then participated in the photocatalytic degradation of RhB, showing an increased activity.« less

Effect of Pd Interlayer on Electrochemical Properties of ENIG Surface Finish in 3.5 wt.% NaCl Solution

NASA Astrophysics Data System (ADS)

Nam, N. D.; Bui, Q. V.; Nhan, H. T.; Phuong, D. V.; Bian, M. Z.

2014-09-01

The corrosion resistance of a multilayered (NiP-Pd-Au) coating with various thicknesses of palladium (Pd) interlayer deposited on copper by an electroless method was investigated using electrochemical techniques including potentiodynamic polarization and electrochemical impedance spectroscopy. In addition, the surface finish was examined by x-ray diffraction analysis and scanning electron microscopy, and the contact angle of the liquid-solid interface was recorded. The corrosion resistance of the copper substrate was considerably improved by Pd interlayer addition. Increase of the thickness of the Pd interlayer enhanced the performance of the Cu-NiP-Pd-Au coating due to low porosity, high protective efficiency, high charge-transfer resistance, and contact angle. These are attributed to the diffusion of layers in the Cu-NiP-Pd-Au coating acting as a physical barrier layer, leading to the protection provided by the coating.

Mechanism of abnormally slow crystal growth of CuZr alloy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yan, X. Q.; Lü, Y. J., E-mail: yongjunlv@bit.edu.cn; State Key Laboratory of Silicon Materials, Zhejiang University, Hangzhou 310027

2015-10-28

Crystal growth of the glass-forming CuZr alloy is shown to be abnormally slow, which suggests a new method to identify the good glass-forming alloys. The crystal growth of elemental Cu, Pd and binary NiAl, CuZr alloys is systematically studied with the aid of molecular dynamics simulations. The temperature dependence of the growth velocity indicates the different growth mechanisms between the elemental and the alloy systems. The high-speed growth featuring the elemental metals is dominated by the non-activated collision between liquid-like atoms and interface, and the low-speed growth for NiAl and CuZr is determined by the diffusion across the interface. Wemore » find that, in contrast to Cu, Pd, and NiAl, a strong stress layering arisen from the density and the local order layering forms in front of the liquid-crystal interface of CuZr alloy, which causes a slow diffusion zone. The formation of the slow diffusion zone suppresses the interface moving, resulting in much small growth velocity of CuZr alloy. We provide a direct evidence of this explanation by applying the compressive stress normal to the interface. The compression is shown to boost the stress layering in CuZr significantly, correspondingly enhancing the slow diffusion zone, and eventually slowing down the crystal growth of CuZr alloy immediately. In contrast, the growth of Cu, Pd, and NiAl is increased by the compression because the low diffusion zones in them are never well developed.« less

Determination of palladium, platinum and rhodium in used automobile catalysts and active pharmaceutical ingredients using high-resolution continuum source graphite furnace atomic absorption spectrometry and direct solid sample analysis

NASA Astrophysics Data System (ADS)

Resano, Martín; Flórez, María del Rosario; Queralt, Ignasi; Marguí, Eva

2015-03-01

This work investigates the potential of high-resolution continuum source graphite furnace atomic absorption spectrometry for the direct determination of Pd, Pt and Rh in two samples of very different nature. While analysis of active pharmaceutical ingredients is straightforward and it is feasible to minimize matrix effects, to the point that calibration can be carried out against aqueous standard solutions, the analysis of used automobile catalysts is more challenging requiring the addition of a chemical modifier (NH4F·HF) to help in releasing the analytes, a more vigorous temperature program and the use of a solid standard (CRM ERM®-EB504) for calibration. However, in both cases it was possible to obtain accurate results and precision values typically better than 10% RSD in a fast and simple way, while only two determinations are needed for the three analytes, since Pt and Rh can be simultaneously monitored in both types of samples. Overall, the methods proposed seem suited for the determination of these analytes in such types of samples, offering a greener and faster alternative that circumvents the traditional problems associated with sample digestion, requiring a small amount of sample only (0.05 mg per replicate for catalysts, and a few milligrams for the pharmaceuticals) and providing sufficient sensitivity to easily comply with regulations. The LODs achieved were 6.5 μg g- 1 (Pd), 8.3 μg g- 1 (Pt) and 9.3 μg g- 1 (Rh) for catalysts, which decreased to 0.08 μg g- 1 (Pd), 0.15 μg g- 1 (Pt) and 0.10 μg g- 1 (Rh) for pharmaceuticals.

Derivation of the P2T Criterion (in Closed Form) Based on the Frey Shear Band Mechanism

DTIC Science & Technology

1984-01-01

max 6d/d = G (12) max o u Pil < o .tlllilltt, >. X !5 < Q: o W) TJ C rH CU •H ed •P in -H 03 W 4-" FH cd C 03 Cu <U P...C 3 -H 10 T3 cd T3 O H s h ♦J 03 PH If) X3 -d rH fH ^H ed 03 OJ -H (1) •H -t-i Xi MH -H in c X’H <D ■M 43 • H 0 +J O...P o c a> rH X! 0 M 03 w C M •H O 03 u S & K <u TO S 0) +-> FH O ^—^ o3 W) y ^ cd i S: •H -H O -d T3 T3 iH CD *W P O nj

Study of the influence of platinum, palladium and rhodium on duckweed (Lemna minor).

PubMed

Bednarova, Ivana; Mikulaskova, Hana; Havelkova, Barbora; Strakova, Lenka; Beklova, Miroslava; Sochor, Jiri; Hynek, David; Adam, Vojtech; Kizek, Rene

2014-01-01

Road traffic pollutants and the residues of cytostatics that are widely used in anti-cancer therapy are a significant sources of platinum group elements (PGE; Pt, Pd and Rh) in environment. These metals can migrate into sewage and thus pollute surface waters. The purpose of our study was to evaluate the effect of PtCl4 on the antioxidant and enzymatic activity of duckweed (Lemna minor), a bioindicator of the aquatic environment. The study was performed using a 7-day conventional test based on the OECD 221 (CSN EN ISO 20079)--Lemna sp. Growth Inhibition Test. We also conducted a microbiotest to analyse the effects of PtC4, PdCl2 and RhCl3 on the morphology and vegetative growth of colonies of this plant and compared their inhibitory effects during the microbiotest. We observed inhibition of colony growth and clear morphological changes. Antioxidant and enzymatic activities increased with platinum doses increased. The 168hEC50 of PtCl4 was 12.16 μM (95% confidence interval = 9.88-14.44) and the 168hEC50 of PdCl2 was 50.39 (95% confidence interval = 23.83-76.96). The greatest inhibition of growth by RhCl3 was observed at 25 μM. The obtained results suggest that L. minor phytotoxicity tests should be widely used in the biomonitoring.

Synthesis of amino-functionalized silica nanoparticles for preparation of new laboratory standards

NASA Astrophysics Data System (ADS)

Alvarez-Toral, Aitor; Fernández, Beatriz; Malherbe, Julien; Claverie, Fanny; Pecheyran, Christophe; Pereiro, Rosario

2017-12-01

Platinum group elements (PGEs) are particularly interesting analytes in different fields, including environmental samples as well as high cost materials that contain them, such as for example automotive catalysts. This type of solid samples could be analysed by laser ablation (LA) coupled to ICP-MS, which allow to significantly reducing the analysis time since the time-consuming processes for sample preparation are not required. There is a considerable demand of standards with high PGEs concentration for quantification purposes, which cannot be carried out easily using LA-ICP-MS because the available standards (i.e. NIST SRM 61 × series) do not have such analytes in the same concentration range. In this paper, a new strategy is proposed for the synthesis of homogeneous laboratory standards with Pt, Pd and Rh concentrations that range from 77 μg/g of Pd up to 2035 μg/g of Rh. The proposed strategy is based on the synthesis of monodisperse amino-functionalized amorphous silica nanoparticles, which can retain metal ions. In addition to Pt, Pd and Rh, three lanthanides were also added to the nanoparticles (La, Ce, Nd). Sturdy pressed pellets can be made from the resulting nanopowder without the use of any binder. Elemental composition of standards made of nanoparticles was analysed by conventional nebulization ICP-MS and their homogeneity was successfully evaluated by LA-ICP-MS.

Determination of crystal-field energy levels and temperature dependence of magnetic susceptibility for Dy3+ in [Dy2Pd] heterometallic complex.

PubMed

Karbowiak, Mirosław; Rudowicz, Czesław; Ishida, Takayuki

2013-11-18

This study is the first in a series of experimental and theoretical investigations of the crystal-field (CF) energy levels obtained from optical electronic spectra for selected heterometallic 4f-3d compounds intensively studied for the development of novel single-molecule magnets (SMMs). An intriguing question is why the [{Dy(III)(hfac)3}2Cu(II)(dpk)2] (abbreviated as [Dy2Cu]; Hhfac = 1,1,1,5,5,5-hexafluoropentane-2,4-dione, Hdpk = di-2-pyridyl ketoxime) has antiferromagnetic coupling, whereas [Gd2Cu] and heavy [Ln2Cu] systems usually show ferromagnetic coupling. As the first step to explain this peculiarity, the recently synthesized complex, [Dy2Pd], is investigated. This complex is isostructural with [Dy2Cu] yet contains the diamagnetic Pd ion instead of the magnetic Cu(II) ion. Experimental energy levels of Dy(3+) ions in the powder [Dy2Pd] sample were determined from the 4.2 K absorption spectra. CF analysis was performed yielding the fitted free ion and CF parameters. The number of freely varied parameters was restricted using the superposition model. The fittings yield very satisfactory agreement between the experimental and the calculated energy levels (rms = 12.0 cm(-1)). The energies and exact composition of the state vector for the ground multiplet (6)H(15/2) of Dy(3+) are determined. These results are used for the simulation of the temperature dependence of the magnetic susceptibility, which enables the theoretical interpretation of the experimentally measured magnetic susceptibility in the range 1.8-300 K for the [Dy2Pd] complex. This study provides background for the subsequent investigation of the magnetic exchange interactions in the pertinent heterometallic complexes.

High resolution positron annihilation induced Auger electron spectroscopy of the CuM 2,3VV-transition and of Cu sub-monolayers on Pd and Fe

NASA Astrophysics Data System (ADS)

Mayer, J.; Hugenschmidt, C.; Schreckenbach, K.

2010-09-01

We present a high resolution positron annihilation induced Auger Electron Spectroscopy (PAES) of the CuM 2,3VV-transition with the unprecedented energy resolution of Δ/EE <1%. This energy resolution and the highly intense positron source NEPOMUC enabled us to resolve the double peak structure with PAES for the first time within a measurement time of only 5.5 h. In addition, sub-monolayers of Cu were deposited on Fe- and Pd-samples in order to investigate the surface selectivity of PAES in comparison with EAES. The extremely high surface selectivity of PAES due to the different positron affinity of Cu and Fe lead to the result that with only 0.96 monolayer of Cu on Fe more than 55% of the emitted Auger electrons stem from Cu, whereas with EAES the Cu Auger fraction amounted to less than 6%.

Monte Carlo Simulation of X-Ray Spectra in Mammography and Contrast-Enhanced Digital Mammography Using the Code PENELOPE

NASA Astrophysics Data System (ADS)

Cunha, Diego M.; Tomal, Alessandra; Poletti, Martin E.

2013-04-01

In this work, the Monte Carlo (MC) code PENELOPE was employed for simulation of x-ray spectra in mammography and contrast-enhanced digital mammography (CEDM). Spectra for Mo, Rh and W anodes were obtained for tube potentials between 24-36 kV, for mammography, and between 45-49 kV, for CEDM. The spectra obtained from the simulations were analytically filtered to correspond to the anode/filter combinations usually employed in each technique (Mo/Mo, Rh/Rh and W/Rh for mammography and Mo/Cu, Rh/Cu and W/Cu for CEDM). For the Mo/Mo combination, the simulated spectra were compared with those obtained experimentally, and for spectra for the W anode, with experimental data from the literature, through comparison of distribution shape, average energies, half-value layers (HVL) and transmission curves. For all combinations evaluated, the simulated spectra were also compared with those provided by different models from the literature. Results showed that the code PENELOPE provides mammographic x-ray spectra in good agreement with those experimentally measured and those from the literature. The differences in the values of HVL ranged between 2-7%, for anode/filter combinations and tube potentials employed in mammography, and they were less than 5% for those employed in CEDM. The transmission curves for the spectra obtained also showed good agreement compared to those computed from reference spectra, with average relative differences less than 12% for mammography and CEDM. These results show that the code PENELOPE can be a useful tool to generate x-ray spectra for studies in mammography and CEDM, and also for evaluation of new x-ray tube designs and new anode materials.

Heterogeneity in ultrathin films simulated by Monte Carlo method

NASA Astrophysics Data System (ADS)

Sun, Jiebing; Hannon, James B.; Kellogg, Gary L.; Pohl, Karsten

2007-03-01

The 3D composition profile of ultra-thin Pd films on Cu(001) has been experimentally determined using low energy electron microscopy (LEEM).^[1] Quantitative measurements of the alloy concentration profile near steps show that the Pd distribution in the 3^rd layer is heterogeneous due to step overgrowth during Pd deposition. Interestingly, the Pd distribution in the 2^nd layer is also heterogeneous, and appears to be correlated with the distribution in the 1^st layer. We describe Monte Carlo simulations that show that correlation is due to Cu-Pd attraction, and that the 2^nd layer Pd is, in fact, laterally equilibrated. By comparing measured and simulated concentration profiles, we can estimate this attraction within a simple bond counting model. [1] J. B. Hannon, J. Sun, K. Pohl, G. L. Kellogg, Phys. Rev. Lett. 96, 246103 (2006)

Poly(ethylene glycol)-based ionic liquids: properties and uses as alternative solvents in organic synthesis and catalysis.

PubMed

Cecchini, Martina Maya; Charnay, Clarence; De Angelis, Francesco; Lamaty, Frédéric; Martinez, Jean; Colacino, Evelina

2014-01-01

PEG-based ionic liquids are a new appealing group of solvents making the link between two distinct but very similar fluids: ionic liquids and poly(ethylene glycol)s. They find applications across a range of innumerable disciplines in science, technology, and engineering. In the last years, the possibility to use these as alternative solvents for organic synthesis and catalysis has been increasingly explored. This Review highlights strategies for their synthesis, their physical properties (critical point, glass transition temperature, density, rheological properties), and their application in reactions catalyzed by metals (such as Pd, Cu, W, or Rh) or as organic solvent (for example for multicomponent reactions, organocatalysis, CO2 transformation) with special emphasis on their toxicity, environmental impact, and biodegradability. These aspects, very often neglected, need to be considered in addition to the green criteria usually considered to establish ecofriendly processes. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Theoretical study of adsorption of organic phosphines on transition metal surfaces

NASA Astrophysics Data System (ADS)

Lou, Shujie; Jiang, Hong

2018-04-01

The adsorption properties of organic phosphines on transition metal (TM) surfaces (Fe, Co, Ni, Cu, Ru, Rh, Pd, Ag, Ir, Pt, and Au) have been studied to explore the possibility of building novel heterogeneous chiral catalytic systems based on organic phosphines. Preferred adsorption sites, adsorption energies and surface electronic structures of a selected set of typical organic phosphines adsorbed on TM surfaces are calculated with density-functional theory to obtain a systematic understanding on the nature of adsorption interactions. All organic phosphines considered are found to chemically adsorb on these TM surfaces with the atop site as the most preferred one, and the TM-P bond is formed via the lone-pair electrons of the P atom and the directly contacted TM atom. These findings imply that it is indeed possible to build heterogeneous chiral catalytic systems based on organic phosphines adsorbed on TM surfaces, which, however, requires a careful design of molecular structure of organic phosphines.

On the electron density localization in elemental cubic ceramic and FCC transition metals by means of a localized electrons detector.

PubMed

Aray, Yosslen; Paredes, Ricardo; Álvarez, Luis Javier; Martiz, Alejandro

2017-06-14

The electron density localization in insulator and semiconductor elemental cubic materials with diamond structure, carbon, silicon, germanium, and tin, and good metallic conductors with face centered cubic structure such as α-Co, Ni, Cu, Rh, Pd, Ag, Ir, Pt, and Au, was studied using a localized electrons detector defined in the local moment representation. Our results clearly show an opposite pattern of the electron density localization for the cubic ceramic and transition metal materials. It was found that, for the elemental ceramic materials, the zone of low electron localization is very small and is mainly localized on the atomic basin edges. On the contrary, for the transition metals, there are low-valued localized electrons detector isocontours defining a zone of highly delocalized electrons that extends throughout the material. We have found that the best conductors are those in which the electron density at this low-value zone is the lowest.

Radiosondes Corrected for Inaccuracy in RH Measurements

DOE Data Explorer

Miloshevich, Larry

2008-01-15

Corrections for inaccuracy in Vaisala radiosonde RH measurements have been applied to ARM SGP radiosonde soundings. The magnitude of the corrections can vary considerably between soundings. The radiosonde measurement accuracy, and therefore the correction magnitude, is a function of atmospheric conditions, mainly T, RH, and dRH/dt (humidity gradient). The corrections are also very sensitive to the RH sensor type, and there are 3 Vaisala sensor types represented in this dataset (RS80-H, RS90, and RS92). Depending on the sensor type and the radiosonde production date, one or more of the following three corrections were applied to the RH data: Temperature-Dependence correction (TD), Contamination-Dry Bias correction (C), Time Lag correction (TL). The estimated absolute accuracy of NIGHTTIME corrected and uncorrected Vaisala RH measurements, as determined by comparison to simultaneous reference-quality measurements from Holger Voemel's (CU/CIRES) cryogenic frostpoint hygrometer (CFH), is given by Miloshevich et al. (2006).

Atom Probe Analysis of Ex Situ Gas-Charged Stable Hydrides.

PubMed

Haley, Daniel; Bagot, Paul A J; Moody, Michael P

2017-04-01

In this work, we report on the atom probe tomography analysis of two metallic hydrides formed by pressurized charging using an ex situ hydrogen charging cell, in the pressure range of 200-500 kPa (2-5 bar). Specifically we report on the deuterium charging of Pd/Rh and V systems. Using this ex situ system, we demonstrate the successful loading and subsequent atom probe analysis of deuterium within a Pd/Rh alloy, and demonstrate that deuterium is likely present within the oxide-metal interface of a native oxide formed on vanadium. Through these experiments, we demonstrate the feasibility of ex situ hydrogen analysis for hydrides via atom probe tomography, and thus a practical route to three-dimensional imaging of hydrogen in hydrides at the atomic scale.

Compositional effects in Ru, Pd, Pt, and Rh-doped mesoporous tantalum oxide catalysts for ammonia synthesis.

PubMed

Yue, Chaoyang; Qiu, Longhui; Trudeau, Michel; Antonelli, David

2007-06-11

A series of early metal-promoted Ru-, Pd-, Pt-, and Rh-doped mesoporous tantalum oxide catalysts were synthesized using a variety of dopant ratios and dopant precursors, and the effects of these parameters on the catalytic activity of NH3 synthesis from H2 and N2 were explored. Previous studies on this system supported an unprecedented mechanism in which N-N cleavage occurred at the Ta sites rather than on Ru. The results of the present study showed, for all systems, that Ba is a better promoter than Cs or La and that the nitrate is a superior precursor for Ba than the isopropoxide or the hydroxide. 15N-labeling studies showed that residual nitrate functions as the major ammonia source in the first hour but that it does not account for the ammonia produced after the nitrate is completely consumed. Ru3(CO)12 proved to be a better Ru precursor than RuCl(3).3H2O, and an almost linear increase in activity with increasing Ru loading level was observed at 350 degrees C (623 K). However, at 175 degrees C (448 K), the increase in Ru had no effect on the reaction rate. Pd functioned with comparable rates to Ru, while Pt and Rh functioned far less efficiently. The surprising activities for the Pd-doped catalysts, coupled with XPS evidence for low-valent Ta in this catalyst system, support a mechanism in which cleavage of the N-N triple bond occurs on Ta rather than the precious metal because the Ea value for N-N cleavage on Pd is 2.5 times greater than that for Ru, and the 9.3 kJ mol-1 Ea value measured previously for the Ru system suggests that N-N cleavage cannot occur at the Ru surface.

Metal-Diazo Radicals of α-Carbonyl Diazomethanes

PubMed Central

Li, Feifei; Xiao, Longqiang; Liu, Lijian

2016-01-01

Metal-diazo radicals of α-carbonyl diazomethanes are new members of the radical family and are precursors to metal-carbene radicals. Herein, using electron paramagnetic resonance spectroscopy with spin-trapping, we detect diazo radicals of α-carbonyl diazomethanes, induced by [RhICl(cod)]2, [CoII(por)] and PdCl2, at room temperature. The unique quintet signal of the Rh-diazo radical was observed in measurements of α-carbonyl diazomethane adducts of [RhICl(cod)]2 in the presence of 5,5-dimethyl-pyrroline-1-N-oxide (DMPO). DFT calculations indicated that 97.2% of spin density is localized on the diazo moiety. Co- and Pd-diazo radicals are EPR silent but were captured by DMPO to form spin adducts of DMPO-N∙ (triplet-of-sextets signal). The spin-trapping also provides a powerful tool for detection of metal-carbene radicals, as evidenced by the DMPO-trapped carbene radicals (DMPO-C∙, sextet signal) and 2-methyl-2-nitrosopropane-carbene adducts (MNP-C∙, doublet-of-triplets signal). The transformation of α-carbonyl diazomethanes to metal-carbene radicals was confirmed to be a two-step process via metal-diazo radicals. PMID:26960916

Metal-Diazo Radicals of α-Carbonyl Diazomethanes

NASA Astrophysics Data System (ADS)

Li, Feifei; Xiao, Longqiang; Liu, Lijian

2016-03-01

Metal-diazo radicals of α-carbonyl diazomethanes are new members of the radical family and are precursors to metal-carbene radicals. Herein, using electron paramagnetic resonance spectroscopy with spin-trapping, we detect diazo radicals of α-carbonyl diazomethanes, induced by [RhICl(cod)]2, [CoII(por)] and PdCl2, at room temperature. The unique quintet signal of the Rh-diazo radical was observed in measurements of α-carbonyl diazomethane adducts of [RhICl(cod)]2 in the presence of 5,5-dimethyl-pyrroline-1-N-oxide (DMPO). DFT calculations indicated that 97.2% of spin density is localized on the diazo moiety. Co- and Pd-diazo radicals are EPR silent but were captured by DMPO to form spin adducts of DMPO-N• (triplet-of-sextets signal). The spin-trapping also provides a powerful tool for detection of metal-carbene radicals, as evidenced by the DMPO-trapped carbene radicals (DMPO-C•, sextet signal) and 2-methyl-2-nitrosopropane-carbene adducts (MNP-C•, doublet-of-triplets signal). The transformation of α-carbonyl diazomethanes to metal-carbene radicals was confirmed to be a two-step process via metal-diazo radicals.

Metal-Diazo Radicals of α-Carbonyl Diazomethanes.

PubMed

Li, Feifei; Xiao, Longqiang; Liu, Lijian

2016-03-10

Metal-diazo radicals of α-carbonyl diazomethanes are new members of the radical family and are precursors to metal-carbene radicals. Herein, using electron paramagnetic resonance spectroscopy with spin-trapping, we detect diazo radicals of α-carbonyl diazomethanes, induced by [Rh(I)Cl(cod)]2, [Co(II)(por)] and PdCl2, at room temperature. The unique quintet signal of the Rh-diazo radical was observed in measurements of α-carbonyl diazomethane adducts of [Rh(I)Cl(cod)]2 in the presence of 5,5-dimethyl-pyrroline-1-N-oxide (DMPO). DFT calculations indicated that 97.2% of spin density is localized on the diazo moiety. Co- and Pd-diazo radicals are EPR silent but were captured by DMPO to form spin adducts of DMPO-N∙ (triplet-of-sextets signal). The spin-trapping also provides a powerful tool for detection of metal-carbene radicals, as evidenced by the DMPO-trapped carbene radicals (DMPO-C∙, sextet signal) and 2-methyl-2-nitrosopropane-carbene adducts (MNP-C∙, doublet-of-triplets signal). The transformation of α-carbonyl diazomethanes to metal-carbene radicals was confirmed to be a two-step process via metal-diazo radicals.

Infrared photorefractive effect in doped KNbO3 crystals

NASA Astrophysics Data System (ADS)

Medrano, C.; Zgonik, M.; Liakatas, I.; Günter, P.

1996-11-01

The photorefractive sensitivity of potassium niobate crystals doped with Ce, Co, Cu, Fe, Mn, Ni, and Rh and double-doped with Mn and Rh is investigated over an extended spectral range. We present experimental evidence on extrinsic properties important for the photorefractive effect, such as absorption and effective trap density. Photorefractive gratings are investigated with two-wave mixing experiments. Results on exponential gain, response time, and photorefractive sensitivity at near-infrared wavelengths are reported. The best photorefractive sensitivities at 860 and 1064 nm were obtained in crystals doped with Rh, Fe, Mn, and Mn-Rh. This makes them suitable for applications at laser-diode wavelengths; at 1064 nm, however, Rh:KNbO3 shows a better photorefractive sensitivity than the others. .

Assessment of sublethal endpoints after chronic exposure of the nematode Caenorhabditis elegans to palladium, platinum and rhodium.

PubMed

Schertzinger, Gerhard; Zimmermann, Sonja; Grabner, Daniel; Sures, Bernd

2017-11-01

The aim of this study was to investigate chronic effects of the platinum-group elements (PGE) palladium (Pd), platinum (Pt) and rhodium (Rh) on the nematode Caenorhabditis elegans. Aquatic toxicity testing was carried out according to ISO 10872 by determining 96 h EC 50 values for sublethal endpoints, including growth, fertility and reproduction. Single PGE standard solutions were used as metal source. Based on the EC 50 values for Pt, reproduction (96 h EC 50  = 497 μg/L) was the most sensitive endpoint followed by fertility (96 h EC 50  = 726 μg/L) and growth (96 h EC 50  = 808 μg/L). For Pd, no precise EC 50 values could be calculated due to bell-shaped concentration response curves, but the 96 h EC 50 for reproduction ranged between 10 and 100 μg/L. Pd and Pt had effects on all endpoints. With raising element concentrations reproduction was inhibited first. At a certain concentration, fertility was also affected, which in turn had an additional effect on reproduction. Growth inhibition can also lead to a loss of fertility if the worms do not reach an appropriate body size to become fertile. Rhodium showed no inhibition of any endpoint between concentrations of 100 to 10,000 μg Rh/L. The results of this study allow the following order of PGE with respect to decreasing toxicity to C. elegans: Pd > Pt » Rh. Copyright © 2017 Elsevier Ltd. All rights reserved.

Kinetic and catalytic analysis of mesoporous metal oxides on the oxidation of Rhodamine B

NASA Astrophysics Data System (ADS)

Xaba, Morena S.; Noh, Ji-Hyang; Mokgadi, Keabetswe; Meijboom, Reinout

2018-05-01

In this study, we demonstrate the synthesis and catalytic activity of different mesoporous transition metal oxides, silica (SiO2), copper oxide (CuO), chromium oxide (Cr2O3), iron oxide (Fe2O3) cobalt oxide (Co3O4), cerium oxide (CeO2) and nickel oxide (NiO), on the oxidation of a pollutant dye, Rhodamine B (RhB). These metal oxides were synthesized by inverse micelle formation method and characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray diffraction (XRD), adsorption-desorption isotherms (BET) and H2-temperature programmed reduction (TPR). UV-vis spectrophotometry was used to monitor the time-resolved absorbance of RhB at λmax = 554 nm. Mesoporous copper oxide was calcined at different final heating temperatures of 250, 350, 450 and 550 °C, and each mesoporous copper oxide catalyst showed unique physical properties and catalytic behavior. Mesoporous CuO-550 with the smallest characteristic path length δ, proved to be the catalyst of choice for the oxidation of RhB in aqueous media. We observed that the oxidation of RhB in aqueous media is dependent on the crystallite size and characteristic path length of the mesoporous metal oxide. The Langmuir-Hinshelwood model was used to fit the experimental data and to prove that the reaction occurs on the surface of the mesoporous CuO. The thermodynamic parameters, EA, ΔH#, ΔS# and ΔG# were calculated and catalyst recycling and reusability were demonstrated.

75 FR 6854 - Airworthiness Directives; Dassault-Aviation Model Falcon 900EX Airplanes

Federal Register 2010, 2011, 2012, 2013, 2014

2010-02-12

... and passenger Right-Hand (RH) oxygen lines may both interfere with the frame 8 of the aeroplane structure. A subsequent design review of the oxygen lines routing has confirmed that, on certain aeroplanes, equipped in RH mid-cabin with a 115 cu-ft oxygen cylinder, the installation of the line support assembly at...

Adsorption of Pd(II) complexes from chloride solutions obtained by leaching chlorinated spent automotive catalysts on ion exchange resin Diaion WA21J.

PubMed

Shen, Shaobo; Pan, Tonglin; Liu, Xinqiang; Yuan, Lei; Zhang, Yongjian; Wang, Jinchao; Guo, Zhanchen

2010-05-01

It was found that Rh, Pd and Pt contained in the spent ceramic automotive catalysts could be effectively extracted by dry chlorination with chlorine. In order to concentrate Pd(II) contained in the chloride solution obtained from the dry chlorination process, thermodynamic and kinetics studies for adsorption of Pd(II) complexes from the chloride solutions on anionic exchange resin Diaion WA21J were carried out. It was found that Pd, Pt, Rh, Al, Fe, Si, Zn and Pb from the chloride solution could be adsorbed on the resin. The isothermal adsorption of Pd(II) was found to fit Freundlich, Langmuir and Dubinin-Kaganer-Radushkevich models under the adsorption conditions. The adsorption of Pd(II) on the resin was favorable according to the values of 1/n and R(L) from Freundlich and Langmuir adsorption isotherms, respectively. The maximum monolayer adsorption capacities Q(max) based on Langmuir adsorption isotherms were 5.70, 4.84 and 4.05 mg/g and the corresponding value X(m) based on Dubinin-Kaganer-Radushkevich were 5.55, 4.69 and 4.01 mg/g at temperatures 18 degrees C, 28 degrees C and 40 degrees C, respectively. The apparent adsorption energies (E(ad)) based on Dubinin-Kaganer-Radushkevich isotherm were -15.43, -16.22 and -23.57 kJ/mol for the temperatures 18 degrees C, 28 degrees C and 40 degrees C, respectively. Chemical adsorption was a main mechanism involved in the adsorption process. Pd(II) adsorption on the resin could be accelerated by increasing the adsorption temperature. The adsorption of Pd(II) from the chloride solution on the resin underwent pseudo-first order kinetic process and the apparent adsorption activation energy E(a) was 15.0 kJ/mol. The intra-particle diffusion was a main rate controlling step in the Pd(II) adsorption process under the adsorption conditions. Copyright 2010 Elsevier Inc. All rights reserved.

Dosimetry Prediction for Clinical Translation of 64Cu-Pembrolizumab ImmunoPET Targeting Human PD-1 Expression.

PubMed

Natarajan, Arutselvan; Patel, Chirag B; Habte, Frezghi; Gambhir, Sanjiv S

2018-01-12

The immune checkpoint programmed death 1 receptor (PD-1) expressed on some tumor-infiltrating lymphocytes, and its ligand (PD-L1) expressed on tumor cells, enable cancers to evade the immune system. Blocking PD-1 with the monoclonal antibody pembrolizumab is a promising immunotherapy strategy. Thus, noninvasively quantifying the presence of PD-1 expression in the tumor microenvironment prior to initiation of immune checkpoint blockade may identify the patients likely to respond to therapy. We have developed a 64 Cu-pembrolizumab radiotracer and evaluated human dosimetry. The tracer was utilized to image hPD-1 levels in two subcutaneous mouse models: (a) 293 T/hPD-1 cells xenografted into NOD-scid IL-2Rγnull mice (NSG/293 T/hPD-1) and (b) human peripheral blood mononuclear cells engrafted into NSG bearing A375 human melanoma tumors (hNSG/A375). In each mouse model two cohorts were evaluated (hPD-1 blockade with pembrolizumab [blk] and non-blocked [nblk]), for a total of four groups (n = 3-5/group). The xenograft-to-muscle ratio in the NSG/293 T/hPD-1 model at 24 h was significantly increased in the nblk group (7.0 ± 0.5) compared to the blk group (3.4 ± 0.9), p = 0.01. The radiotracer dosimetry evaluation (PET/CT ROI-based and ex vivo) in the hNSG/A375 model revealed the highest radiation burden to the liver. In summary, we validated the 64 Cu-pembrolizumab tracer's specific hPD-1 receptor targeting and predicted human dosimetry.

Geochemical behaviour of palladium in soils and Pd/PdO model substances in the presence of the organic complexing agents L-methionine and citric acid.

PubMed

Zereini, Fathi; Wiseman, Clare L S; Vang, My; Albers, Peter; Schneider, Wolfgang; Schindl, Roland; Leopold, Kerstin

2016-01-01

Risk assessments of platinum group metal (PGE) emissions, notably those of platinum (Pt), palladium (Pd) and rhodium (Rh), have been mostly based on data regarding the metallic forms used in vehicular exhaust converters, known to be virtually biologically inert and immobile. To adequately assess the potential impacts of PGE, however, data on the chemical behaviour of these metals under ambient conditions post-emission is needed. Complexing agents with a high affinity for metals in the environment are hypothesized to contribute to an increased bioaccessibility of PGE. The purpose of this study is to examine the modulating effects of the organic complexing agents, L-methionine and citric acid, on the geochemical behavior of Pd in soils and model substances (Pd black and PdO). Batch experimental tests were conducted with soils and model substances to examine the impacts of the concentration of complexing agents, pH and length of extraction period on Pd solubility and its chemical transformation. Particle surface chemistry was examined using X-ray photoelectron spectroscopy (XPS) on samples treated with solutions under various conditions, including low and high O2 levels. Pd was observed to be more soluble in the presence of organic complexing agents, compared to Pt and Rh. Pd in soils was more readily solubilized with organic complexing agents compared to the model substances. After 7 days of extraction, L-methionine (0.1 M) treated soil and Pd black samples, for instance, had mean soluble Pd fractions of 12.4 ± 5.9% and 0.554 ± 0.024%, respectively. Surface chemistry analyses (XPS) confirmed the oxidation of metallic Pd surfaces when treated with organic complexing agents. The type of organic complexing agent used for experimental purposes was observed to be the most important factor influencing solubility, followed by solution pH and time of extraction. The results demonstrate that metallic Pd can be transformed into more bioaccessible species in the presence of organic complexing agents which are ubiquitous in the environment.

Free and Cued Recall Memory in Parkinson’s Disease Associated with Amnestic Mild Cognitive Impairment

PubMed Central

Costa, Alberto; Monaco, Marco; Zabberoni, Silvia; Peppe, Antonella; Perri, Roberta; Fadda, Lucia; Iannarelli, Francesca; Caltagirone, Carlo; Carlesimo, Giovanni A.

2014-01-01

The hypothesis has been advanced that memory disorders in individuals with Parkinson’s disease (PD) are related to either retrieval or consolidation failure. However, the characteristics of the memory impairments of PD patients with amnestic mild cognitive impairment have not been clarified. This study was aimed at investigating whether memory deficits in PD patients with amnestic mild cognitive impairment (PDaMCI) are due to failure of retrieval or consolidation processes. Sixteen individuals with PDaMCI, 20 with amnestic mild cognitive impairment without PD (aMCINPD), and 20 healthy controls were recruited. Participants were administered the Free and Cued Selective Reminding Test. An index of cueing was computed for each subject to capture the advantage in retrieval of cued compared to free recall. Individuals with PDaMCI performed worse than healthy controls on the free recall (p<0.01) but not the cued recall (p>0.10) task, and they performed better than aMCINPD subjects on both recall measures (p<0.01). The index of cueing of subjects with PD was comparable to that of healthy controls (p>0.10) but it was significantly higher than that of the aMCINPD sample (p<0.01). Moreover, PD patients’ performance on free recall trials was significantly predicted by scores on a test investigating executive functions (i.e., the Modified Card Sorting Test; p = 0.042). Findings of the study document that, in subjects with amnestic mild cognitive impairment associated to PD, episodic memory impairment is related to retrieval rather than to consolidation failure. The same data suggest that, in these individuals, memory deficits might be due to altered frontal-related executive functioning. PMID:24465977

Free and cued recall memory in Parkinson's disease associated with amnestic mild cognitive impairment.

PubMed

Costa, Alberto; Monaco, Marco; Zabberoni, Silvia; Peppe, Antonella; Perri, Roberta; Fadda, Lucia; Iannarelli, Francesca; Caltagirone, Carlo; Carlesimo, Giovanni A

2014-01-01

The hypothesis has been advanced that memory disorders in individuals with Parkinson's disease (PD) are related to either retrieval or consolidation failure. However, the characteristics of the memory impairments of PD patients with amnestic mild cognitive impairment have not been clarified. This study was aimed at investigating whether memory deficits in PD patients with amnestic mild cognitive impairment (PDaMCI) are due to failure of retrieval or consolidation processes. Sixteen individuals with PDaMCI, 20 with amnestic mild cognitive impairment without PD (aMCINPD), and 20 healthy controls were recruited. Participants were administered the Free and Cued Selective Reminding Test. An index of cueing was computed for each subject to capture the advantage in retrieval of cued compared to free recall. Individuals with PDaMCI performed worse than healthy controls on the free recall (p<0.01) but not the cued recall (p>0.10) task, and they performed better than aMCINPD subjects on both recall measures (p<0.01). The index of cueing of subjects with PD was comparable to that of healthy controls (p>0.10) but it was significantly higher than that of the aMCINPD sample (p<0.01). Moreover, PD patients' performance on free recall trials was significantly predicted by scores on a test investigating executive functions (i.e., the Modified Card Sorting Test; p = 0.042). Findings of the study document that, in subjects with amnestic mild cognitive impairment associated to PD, episodic memory impairment is related to retrieval rather than to consolidation failure. The same data suggest that, in these individuals, memory deficits might be due to altered frontal-related executive functioning.

Mesoporous metallic rhodium nanoparticles

NASA Astrophysics Data System (ADS)

Jiang, Bo; Li, Cuiling; Dag, Ömer; Abe, Hideki; Takei, Toshiaki; Imai, Tsubasa; Hossain, Md. Shahriar A.; Islam, Md. Tofazzal; Wood, Kathleen; Henzie, Joel; Yamauchi, Yusuke

2017-05-01

Mesoporous noble metals are an emerging class of cutting-edge nanostructured catalysts due to their abundant exposed active sites and highly accessible surfaces. Although various noble metal (e.g. Pt, Pd and Au) structures have been synthesized by hard- and soft-templating methods, mesoporous rhodium (Rh) nanoparticles have never been generated via chemical reduction, in part due to the relatively high surface energy of rhodium (Rh) metal. Here we describe a simple, scalable route to generate mesoporous Rh by chemical reduction on polymeric micelle templates [poly(ethylene oxide)-b-poly(methyl methacrylate) (PEO-b-PMMA)]. The mesoporous Rh nanoparticles exhibited a ~2.6 times enhancement for the electrocatalytic oxidation of methanol compared to commercially available Rh catalyst. Surprisingly, the high surface area mesoporous structure of the Rh catalyst was thermally stable up to 400 °C. The combination of high surface area and thermal stability also enables superior catalytic activity for the remediation of nitric oxide (NO) in lean-burn exhaust containing high concentrations of O2.

1D cyanide complexes with 2-pyridinemethanol: Synthesis, crystal structures and spectroscopic properties

NASA Astrophysics Data System (ADS)

Sayın, Elvan; Kürkçüoğlu, Güneş Süheyla; Yeşilel, Okan Zafer; Hökelek, Tuncer

2015-12-01

Two new one-dimensional coordination polymers, [Cu(hmpH)2Pd(μ-CN)2(CN)2]n (1) and [Cu(hmpH)2Pt(μ-CN)2(CN)2]n (2), (hmpH = 2-pyridinemethanol), have been synthesized and characterized by vibrational (FT-IR and Raman) spectroscopy, single crystal X-ray diffraction, thermal and elemental analyses techniques. Single crystal X-ray diffraction analysis indicates that complexes 1 and 2 are isomorphous and isostructural, and crystallize in the triclinic system and P-1 space group. The Pd(II) or Pt(II) ions are four coordinated with four cyanide-carbon atoms in a square planar geometry. Cu(II) ion displays a distorted octahedral coordination by two N-atoms and two O-atoms of hmpH ligands, two bridging cyanide groups. In one dimensional structure of the complexes, [M(CN)4]2- (M = Pd(II) or Pt(II)) anions and [Cu(hmpH)2]2+ cations are linked via bridging cyanide ligands. In the complexes, the presence of intramolecular C-H⋯M (M = Pd(II) or Pt(II)) interactions with distance values of 3.00-2.95 Å are established, respectively.

Enhanced Photocatalytic Property of Cu Doped Sodium Niobate

DOE PAGES

Xu, Jianbin; Zhang, Feng; Sun, Bingyang; ...

2015-01-01

Here, we investigate the photocatalytic activity of Cu doped NaNbO 3 powder sample prepared by the modified polymer complex method. The photocatalytic activity of hydrogen evolution from methanol aqueous solution was improved by Cu 2.6 at% doping. The photocatalytic degradation of rhodamine B (RhB) under visible light irradiation was enhanced in comparison with pristine NaNbO 3. Cu introduction improved the adsorption property of NaNbO 3, judging from the Fourier transform infrared spectra. Moreover, the ultraviolet light excitation in Cu doped sample would accelerate the mineralized process.

A versatile in situ spectroscopic cell for fluorescence/transmission EXAFS and X-ray diffraction of heterogeneous catalysts in gas and liquid phase.

PubMed

Hannemann, Stefan; Casapu, Maria; Grunwaldt, Jan Dierk; Haider, Peter; Trüssel, Philippe; Baiker, Alfons; Welter, Edmund

2007-07-01

A new spectroscopic cell suitable for the analysis of heterogeneous catalysts by fluorescence EXAFS (extended X-ray absorption fine structure), transmission EXAFS and X-ray diffraction during in situ treatments and during catalysis is described. Both gas-phase and liquid-phase reactions can be investigated combined with on-line product analysis performed either by mass spectrometry or infrared spectroscopy. The set-up allows measurements from liquid-nitrogen temperature to 973 K. The catalysts are loaded preferentially as powders, but also as self-supporting wafers. The reaction cell was tested in various case studies demonstrating its flexibility and its wide applicability from model studies at liquid-nitrogen temperature to operando studies under realistic reaction conditions. Examples include structural studies during (i) the reduction of alumina-supported noble metal particles prepared by flame-spray pyrolysis and analysis of alloying in bimetallic noble metal particles (0.1%Pt-0.1%Pd/Al(2)O(3), 0.1%Pt-0.1%Ru/Al(2)O(3), 0.1%Pt-0.1%Rh/Al(2)O(3), 0.1%Au-0.1%Pd/Al(2)O(3)), (ii) reactivation of aged 0.8%Pt-16%BaO-CeO(2) NO(x) storage-reduction catalysts including the NO(x) storage/reduction cycle, and (iii) alcohol oxidation over gold catalysts (0.6%Au-20%CuO-CeO(2)).

Comparative tissue distribution of metals in birds in Sweden using ICP-MS and laser ablation ICP-MS.

PubMed

Ek, Kristine H; Morrison, Gregory M; Lindberg, Peter; Rauch, Sébastien

2004-08-01

Cadmium, copper, lead, palladium, platinum, rhodium, and zinc profiles were investigated along feather shafts of raptor and other bird species by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). The distribution of external versus internal metal contamination of feathers was investigated. The species examined were peregrine falcon (Falco peregrinus), sparrowhawk ( Accipiter nisus), willow grouse (Lagopus lagopus), and house sparrow (Passer domesticus) in Sweden. For habitat comparisons, total Cu, Pb, Zn, and Cd concentrations were analyzed by ICP-MS in feathers of the examined species as well as captive peregrine falcon. For investigation of metal distribution and correlation in different biological materials of raptors, total concentrations of Cu, Pb, Cd, and Zn were also investigated by ICP-MS in feathers, eggs, blood, feces, liver, and kidney of wild peregrine falcon from southwestern Sweden. Laser ablation of feathers revealed that Pb contamination is both external and internal, Zn contamination is internal, and Cd and Cu contamination is predominantly internal, with a few externally attached particles of high concentration. Pb, Cu, and Cd signal intensities were highest in urban habitats and contamination was mainly external in feathers. The background signal intensity of Zn was also higher in birds from urban habitats. The laser ablation profile of PGE (Pt, Pd, Rh) demonstrated that PGE contamination of feathers consists almost exclusively of externally attached PGE-containing particles, with little evidence of internally deposited PGE.Generally, total metal concentrations in feathers were highest in sparrowhawk and house sparrow due to their urban habitat. Total Cu, Zn, and Cd concentrations were highest in liver and kidney due to binding to metallothionein, while the total Pb concentration was highest in feces due to the high excretion rate of Pb. A decreasing temporal trend for Pb in feathers, showing that Pb levels in feathers have decreased since the introduction of nonleaded petrol, is also discussed.

Heterobimetallic Dioxygen Activation

PubMed Central

York, John T.; Llobet, Antoni; Cramer, Christopher J.; Tolman, William B.

2008-01-01

Heterobimetallic CuPd and CuPt bis(μ-oxo) complexes have been prepared by the reaction of (PPh3)2MO2 (M = Pd, Pt) with LCu(I) precursors (L = β-diketiminate and di- and triamine ligands) and characterized by low-temperature UV-vis, resonance Raman, and 1H and 31P{1H} NMR spectroscopy in conjunction with DFT calculations. The complexes decompose upon warming to yield OPPh3, and in one case this was shown to occur by an intramolecular process through crossover experiments using double-labeling (oxo and phosphine). The reactivity of one of the complexes, LMe2Cu(μ-O)2Pt(PPh3)2 (LMe2 = β-diketiminate), with a variety of reagents including CO2, 2,4-di-tert-butylphenol, 2,4-di-tert-butylphenolate, [NH4][PF6], and dihydroanthracene, was compared to that of homometallic Pt2 and Cu2 counterparts. Unlike typical [Cu2(μ-O)2]2+ cores which have electrophilic oxo groups, the oxo groups in the [Cu(μ-O)2Pt]+ core behave as bases and nucleophiles, similar to previously described Pt2 compounds. In addition, however, the [Cu(μ-O)2Pt]+ core is capable of oxidatively coupling 2,4-di-tert-butylphenol and 2,4-di-tert-butylphenolate. Theoretical evaluation of the electron affinities, basicities, and H-atom transfer kinetics and thermodynamics of the Cu2 and CuM (M = Pd, Pt) cores showed that the latter are more basic and form stronger O-H bonds. PMID:17550254

Measurement of activation cross-section of long-lived products in deuteron induced nuclear reactions on palladium in the 30-50MeV energy range.

PubMed

Ditrói, F; Tárkányi, F; Takács, S; Hermanne, A; Ignatyuk, A V

2017-10-01

Excitation functions were measured in the 31-49.2MeV energy range for the nat Pd(d,xn) 111,110m,106m,105,104g,103 Ag, nat Pd(d,x) 111m,109,101,100 Pd, nat Pd(d,x), 105,102m,102g,101m,101g,100,99m,99g Rh and nat Pd(d,x) 103,97 Ru nuclear reactions by using the stacked foil irradiation technique. The experimental results are compared with our previous results and with the theoretical predictions calculated with the ALICE-D, EMPIRE-D and TALYS (TENDL libraries) codes. Copyright © 2017 Elsevier Ltd. All rights reserved.

Growth of Pd Nanoclusters on Single-Layer Graphene on Cu(111)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Soy, Esin; Guisinger, Nathan P.; Trenary, Michael

We report scanning tunneling microscopy results on the nucleation and growth of Pd nanoclusters on a single layer of graphene on the Cu(111) surface. The shape, organization, and structural evolution of the Pd nanoclusters were investigated using two different growth methods, continuous and stepwise. The size and shape of the formed nanoclusters were found to greatly depend on the growth technique used. The size and density of spherical Pd nanoclusters increased with increasing coverage during stepwise deposition as a result of coarsening of existing clusters and continued nucleation of new clusters. In contrast, continuous deposition gave rise to well-defined triangularmore » Pd clusters as a result of anisotropic growth on the graphene surface. Exposure to ethylene caused a decrease in the size of the Pd clusters. As a result, this is attributed to the exothermic formation of ethylidyne on the cluster surfaces and an accompanying weakening of the Pd–Pd bonding.« less

Growth of Pd Nanoclusters on Single-Layer Graphene on Cu(111)

DOE PAGES

Soy, Esin; Guisinger, Nathan P.; Trenary, Michael

2017-07-05

We report scanning tunneling microscopy results on the nucleation and growth of Pd nanoclusters on a single layer of graphene on the Cu(111) surface. The shape, organization, and structural evolution of the Pd nanoclusters were investigated using two different growth methods, continuous and stepwise. The size and shape of the formed nanoclusters were found to greatly depend on the growth technique used. The size and density of spherical Pd nanoclusters increased with increasing coverage during stepwise deposition as a result of coarsening of existing clusters and continued nucleation of new clusters. In contrast, continuous deposition gave rise to well-defined triangularmore » Pd clusters as a result of anisotropic growth on the graphene surface. Exposure to ethylene caused a decrease in the size of the Pd clusters. As a result, this is attributed to the exothermic formation of ethylidyne on the cluster surfaces and an accompanying weakening of the Pd–Pd bonding.« less

Sub-Saharan red cell antigen phenotypes and glucose-6-phosphate dehydrogenase deficiency variants in French Guiana.

PubMed

Petit, Florence; Bailly, Pascal; Chiaroni, Jacques; Mazières, Stéphane

2016-06-07

The treatment of Plasmodium vivax infections requires the use of primaquine, which can lead to severe haemolysis in glucose-6-phosphate dehydrogenase (G6PD)-deficient individuals. However, most of the Latin American countries, which are still endemic for vivax malaria, lack information on the distribution of G6PD deficiency (G6PDd). No survey has been performed so far in French Guiana. Herein, 80 individuals of the French Guianan Noir Marron population were scrutinized for red cell surface antigens of six blood group systems (ABO, Rh, Kell, Kidd, Duffy and MNS) and G6PD genetic polymorphisms. First, the sub-Saharan origin of the red cell phenotypes was assessed in relation with the literature. Then, given that the main sub-Saharan G6PDd variants are expected to be encountered, only the G6PD sequences of exons 4, 5, 6 and 9 were screened. This work aims at appraising the G6PD gene variation in this population, and thus, contributing to the G6PD piecemeal information in Latin America. Ninety-seven percent (97 %) of the red cells are Fy(a- b-), either D+ C- E- c+ e+ or D+ C+ E- c+ e+ and 44 % exhibited the Fya-/Jkb-/S- combined phenotype. Noteworthy is the detection of the G6PD(Val68Met) variant characterized by c.202G > A transition, G6PD(Asn126Asp) variant characterized by c.376A>G transition and G6PD(Asp181Val) variant characterized by c.542A>T transversion of the G6PD gene in 22.5 % of the sample, characteristic of the A(-(202)), A and Santamaria G6PDd variants, respectively. French Guianan Noir Marron population represents a pool of Rh-D antigen positive, Duffy-negative and G6PD-deficient erythrocytes, the latter accounting for one in every eight persons. The present study provides the first community-based estimation of the frequency of G6PDd polymorphisms in French Guiana. These results contribute to the G6PD genetic background information puzzle in Latin America.

One-step synthesis of three-dimensional Pd polyhedron networks with enhanced electrocatalytic performance.

PubMed

Xu, You; Xu, Rui; Cui, Jianhua; Liu, Yang; Zhang, Bin

2012-04-21

Three-dimensional Pd polyhedron networks (Pd PNs) have been fabricated for the first time through a one-step, Cu(2+)-assisted, solution-chemical approach. These as-prepared 3D Pd PNs exhibit high stability and remarkably improved electrocatalytic activity toward formic acid oxidation over commercially available Pd black. This journal is © The Royal Society of Chemistry 2012

A study of the vacancy loop formation probability in Ni-Cu and Ag-Pd alloys. [50-keV Kr sup + ions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Smalinskas, K.; Chen, Gengsheng; Haworth, J.

1992-04-01

The molten-zone model of vacancy loop formation from a displacement cascade predicts that the loop formation probability should scale with the melting temperature. To investigate this possibility the vacancy loop formation probability has been determined in a series of Cu-Ni and Ag-Pd alloys. The irradiations were performed at room temperature with 50 keV Kr+ ions and the resulting damage structure was examined by using transmission electron microscopy. In the Cu-Ni alloy series, the change in loop formation probability with increasing Ni concentration was complex, and at low- and high- nickel concentrations, the defect yield did not change in the predictedmore » manner. The defect yield was higher in the Cu-rich alloys than in the Ni-rich alloys. In the Ag-Pd alloy the change in the loop formation probability followed more closely the change in melting temperature, but no simple relationship was determined.« less

Novel porous CuO microrods: synthesis, characterization, and their photocatalysis property

NASA Astrophysics Data System (ADS)

Huang, Jiarui; Fu, Guijun; Shi, Chengcheng; Wang, Xinyue; Zhai, Muheng; Gu, Cuiping

2014-09-01

Porous copper oxide microrods have been synthesized via calcining copper glycinate monohydrate microrod precursor which was prepared in mild conditions without any template or additive. Several techniques, such as X-ray diffraction, field emission scanning electron microscopy, thermogravimetric analysis, Fourier transform infrared spectroscopy, and Brunauer-Emmett-Teller (BET) N2 adsorption-desorption analyses, were used to characterize the structure and morphology of the products. Scanning electron microscopy (SEM) analyses show that the precursor consists of a large quantity of uniform rod-like micro/nanostructures with typical lengths in the range of 25-40 μm and diameters in the range of 0.1-0.35 μm. The microrod-like precursors transformed into porous microrod products after calcination at 450 °C in flow air for 2 h. The BET surface area of the porous CuO microrods was calculated to be 8.5 m² g-1. In addition, the obtained porous CuO microrods were used as catalysts to photodegrade rhodamine B (RhB), methyl orange, methylene blue, eosin B, and p-nitrophenol. Compared with commercial CuO powders, the as-prepared porous CuO microrods exhibit superior properties on photocatalytic decomposition of RhB due to their porous hierarchical structures.

Chemical composition and reactivity of water on hexagonal Pt-group metal surfaces.

PubMed

Shavorskiy, A; Gladys, M J; Held, G

2008-10-28

The dissociation behaviour and valence-electronic structure of water adsorbed on clean and oxygen-covered Ru{0001}, Rh{111}, Pd{111}, Ir{111} and Pt{111} surfaces has been studied by high-resolution X-ray photoelectron spectroscopy with the aim of identifying similarities and trends within the Pt-group metals. On average, we find higher reactivity for the 4d metals (Ru, Rh, Pd) as compared to 5d (Ir, Pt), which is correlated with characteristic shifts in the 1b(1) and 3a(1) molecular orbitals of water. Small amounts of oxygen (< 0.2 ML) induce dissociation of water on all five surfaces, for higher coverages (> 0.25 ML) only intact water is observed. Under UHV conditions these higher coverages can only be reached on the 4d metals, the 5d metals are, therefore, not passivated.

Metal phosphide catalysts and methods for making the same and uses thereof

DOEpatents

Habas, Susan Ellen; Wang, Jun; Ruddy, Daniel A.; Baddour, Frederick Raymond Gabriel; Schaidle, Joshua

2017-05-02

The present disclosure relates to a method that includes heating a mixture that includes a metal phenylphosphine-containing precursor that includes at least one of Mo(PPh.sub.3).sub.2(CO).sub.4, Pd(PPh.sub.3).sub.4, Ru(PPh.sub.3).sub.3Cl.sub.2, Ru(PPh.sub.3).sub.2(CO).sub.2Cl.sub.2, Co(PPh.sub.3)(CO).sub.2(NO), and/or Rh(PPh.sub.3).sub.2(CO)Cl, a surfactant, and a solvent. The heating is to a target temperature to form a heated mixture containing a metal phosphide nanoparticle that includes at least one of MoP, Ru.sub.2P, Co.sub.2P, Rh.sub.2P, and/or Pd.sub.3P, and the metal phosphide nanoparticle is not hollow.

Pressure-induced structural phase transition in transition metal carbides TMC (TM = Ru, Rh, Pd, Os, Ir, Pt): a DFT study

NASA Astrophysics Data System (ADS)

Manikandan, M.; Rajeswarapalanichamy, R.; Iyakutti, K.

2018-03-01

First-principles calculations based on density functional theory was performed to analyse the structural stability of transition metal carbides TMC (TM = Ru, Rh, Pd, Os, Ir, Pt). It is observed that zinc-blende phase is the most stable one for these carbides. Pressure-induced structural phase transition from zinc blende to NiAs phase is predicted at the pressures of 248.5 GPa, 127 GPa and 142 GPa for OsC, IrC and PtC, respectively. The electronic structure reveals that RuC exhibits a semiconducting behaviour with an energy gap of 0.7056 eV. The high bulk modulus values of these carbides indicate that these metal carbides are super hard materials. The high B/G value predicts that the carbides are ductile in their most stable phase.

Significance of β-dehydrogenation in ethanol electro-oxidation on platinum doped with Ru, Rh, Pd, Os and Ir.

PubMed

Sheng, Tian; Lin, Wen-Feng; Hardacre, Christopher; Hu, P

2014-07-14

In the exploration of highly efficient direct ethanol fuel cells (DEFCs), how to promote the CO2 selectivity is a key issue which remains to be solved. Some advances have been made, for example, using bimetallic electrocatalysts, Rh has been found to be an efficient additive to platinum to obtain high CO2 selectivity experimentally. In this work, the mechanism of ethanol electrooxidation is investigated using the first principles method. It is found that CH3CHOH* is the key intermediate during ethanol electrooxidation and the activity of β-dehydrogenation is the rate determining factor that affects the completeness of ethanol oxidation. In addition, a series of transition metals (Ru, Rh, Pd, Os and Ir) are alloyed on the top layer of Pt(111) in order to analyze their effects. The elementary steps, α-, β-C-H bond and C-C bond dissociations, are calculated on these bimetallic M/Pt(111) surfaces and the formation potential of OH* from water dissociation is also calculated. We find that the active metals increase the activity of β-dehydrogenation but lower the OH* formation potential resulting in the active site being blocked. By considering both β-dehydrogenation and OH* formation, Ru, Os and Ir are identified to be unsuitable for the promotion of CO2 selectivity and only Rh is able to increase the selectivity of CO2 in DEFCs.

Greenland snow evidence of large scale atmospheric contamination for platinum, palladium, and rhodium.

PubMed

Barbante, C; Veysseyre, A; Ferrari, C; van de Velde, K; Morel, C; Capodaglio, G; Cescon, P; Scarponi, G; Boutron, C

2001-03-01

Since 1976 in the United States, Canada, and Japan, and later in other countries, the exhaust system of gasoline powered cars has been equipped with catalytic converters containing Pt and/or Pd and/or Rh. This has resulted in a very significant decrease in urban air pollution for various chemical species such as NOx, CO, and hydrocarbons. There has however been concern that their ever increasing use might lead to Platinum Group Metals (PGMs) becoming widely dispersed in the environment. From the analysis of Pt, Pd, and Rh in central Greenland recent snow and ancient ice using the ultrasensitive inductively coupled plasma sector field mass spectrometry technique, we show here that the concentrations of these metals in snow dated from the mid 1990s are indeed approximately 40-120 times higher than in ice dated from 7000 years ago. The fact that such an increase is observed far away from populated areas at a high altitude location indicates there is now a large scale contamination of the troposphere of the Northern Hemisphere for PGMs. Pt/Rh mass ratio in the most recent snow samples is close to the same ratio documented for catalytic converter exhausts in a recent study, which suggests that a large fraction of the recent increase for Pt and Rh might originate from automobile catalytic converters.

Bismuth oxychloride (BiOCl)/copper phthalocyanine (CuTNPc) heterostructures immobilized on electrospun polyacrylonitrile nanofibers with enhanced activity for floating photocatalysis.

PubMed

Guo, Xiaohui; Zhou, Xuejiao; Li, Xinghua; Shao, Changlu; Han, Chaohan; Li, Xiaowei; Liu, Yichun

2018-09-01

The 2,9,16,23-tetranitro phthalocyanine copper (II) nanostructures and bismuth oxychloride nanosheets were grown on electrospun polyacrylonitrile (PAN) nanofibers in sequence by solvothermal method. As a result, the BiOCl/CuTNPc heterostructures were uniformly immobilized on the PAN nanofibers. The obtained BiOCl/CuTNPc/PAN nanofibers had excellent photocatalytic activity for the degradation of rhodamine B (RhB) under UV-vis light irradiation. The first-order rate constant of the BiOCl/CuTNPc/PAN nanofibers was 5.86 and 6.31 times as much as CuTNPc/PAN and BiOCl/PAN nanofibers, respectively. The high photocatalytic activity could be attributed to the formation of BiOCl/CuTNPc heterostructures, which helped the separation of the photogenerated electron-hole pairs. Concurrently, the marcoporous structure of the BiOCl/CuTNPc/PAN nanofibers improved the photocatalytic activity due to the increased interface contacts between the photocatalyst and the RhB solution. The BiOCl/CuTNPc/PAN nanofibers did not need to be separated for reuse due to their flexible self-supporting properties originating from the PAN nanofibers. Moreover, the film-like BiOCl/CuTNPc/PAN nanofibers could float easily on the liquid and maximize the absorption of sunlight during photocatalysis. It was expected that the BiOCl/CuTNPc/PAN nanofibers with high photocatalytic activity and easily separable property will possess great potential in the field of industrial applications and environmental remediation. Copyright © 2018. Published by Elsevier Inc.

Corrosion resistance evaluation of Pd-free Ag-Au-Pt-Cu dental alloys.

PubMed

Fujita, Takeshi; Shiraishi, Takanobu; Takuma, Yasuko; Hisatsune, Kunihiro

2011-01-01

The corrosion resistance of nine experimental Pd-free Ag-Au-Pt-Cu dental alloys in a 0.9% NaCl solution was investigated using cyclic voltammetry (CV), optical microscopy, and scanning electron microscopy (SEM). CV measurements revealed that the breakdown potential (E(bd)) and zero current potential (E(zc)) increased with increasing Au/(Au+Ag) atomic ratio. Thus, the Au/(Au+Ag) atomic ratio, but not the Cu content, influenced the corrosion resistance of Ag-Au-Pt-Cu alloys. After the forward scan of CV, both optical and scanning electron microscope images showed that in all the experimental alloys, the matrix phase was corroded but not the second phase. From corrosion resistance viewpoint, the Ag-Au-Pt-Cu alloys seemed to be suitable for clinical application.

Redox reactions of the α-synuclein-Cu(2+) complex and their effects on neuronal cell viability.

PubMed

Wang, Chengshan; Liu, Lin; Zhang, Lin; Peng, Yong; Zhou, Feimeng

2010-09-21

α-Synuclein (α-syn), a presynaptic protein believed to play an important role in neuropathology in Parkinson's disease (PD), is known to bind Cu(2+). Cu(2+) has been shown to accelerate the aggregation of α-syn to form various toxic aggregates in vitro. Copper is also a redox-active metal whose complexes with amyloidogenic proteins/peptides have been linked to oxidative stress in major neurodegenerative diseases. In this work, the formation of the Cu(2+) complex with α-syn or with an N-terminal peptide, α-syn(1-19), was confirmed with electrospray-mass spectrometry (ES-MS). The redox potentials of the Cu(2+) complex with α-syn (α-syn-Cu(2+)) and α-syn(1-19) were determined to be 0.018 and 0.053 V, respectively. Furthermore, the Cu(2+) center(s) can be readily reduced to Cu(+), and possible reactions of α-syn-Cu(2+) with cellular species (e.g., O(2), ascorbic acid, and dopamine) were investigated. The occurrence of a redox reaction can be rationalized by comparing the redox potential of the α-syn-Cu(2+) complex to that of the specific cellular species. For example, ascorbic acid can directly reduce α-syn-Cu(2+) to α-syn-Cu(+), setting up a redox cycle in which O(2) is reduced to H(2)O(2) and cellular redox species is continuously exhausted. In addition, the H(2)O(2) generated was demonstrated to reduce viability of the neuroblastoma SY-HY5Y cells. Although our results ruled out the direct oxidation of dopamine by α-syn-Cu(2+), the H(2)O(2) generated in the presence of α-syn-Cu(2+) can oxidize dopamine. Our results suggest that oxidative stress is at least partially responsible for the loss of dopaminergic cells in PD brain and reveal the multifaceted role of the α-syn-Cu(2+) complex in oxidative stress associated with PD symptoms.

Embedded cluster calculations for hydrogen chemisorption on the (111) surfaces of fcc Co, Ni, Cu, Rh, Pd and Ag

NASA Astrophysics Data System (ADS)

Muscat, J. P.; Newns, D. M.

1980-10-01

We present a muffin tin based calculation on (TM) 3H, (TM) 7H and (TM) 19H clusters embedded at the surface of an effective jellium-like medium whose potential is treated in scattering length approximation. We consider the changes occurring when the d-like perturbation of the TM muffin tins is switched on. The broad chemisorption-induced resonance seen for H on the effective jellium surface is narrowed and shifted down in energy. Furthermore the occupation of this resonance is increased from about 1.1 electrons to about 1.4 (on 3d metals) or 1.8 (on 4d metals), due to d-like states dropping down from the d band to form a relatively welldefined "bonding state". An antibonding state containing about 0.4 electrons is formed at the top of the d band. The results are compared with other calculations and with photoemission data. Implications for the metal-hydrogen distance and (for Ni) the demagnetizing effect of hydrogen chemisorption are discussed. We use the change in total single particle energy when the d-like perturbation is switched on to estimate trends in chemisorption energy along the 3d and 4d series. In the 3d case experimental data is available on the difference in chemisorption energy between Ni and Cu which is in reasonable agreement with our estimate.

Electrochemical Migration Behavior of Copper-Clad Laminate and Electroless Nickel/Immersion Gold Printed Circuit Boards under Thin Electrolyte Layers

PubMed Central

Yi, Pan; Xiao, Kui; Ding, Kangkang; Dong, Chaofang; Li, Xiaogang

2017-01-01

The electrochemical migration (ECM) behavior of copper-clad laminate (PCB-Cu) and electroless nickel/immersion gold printed circuit boards (PCB-ENIG) under thin electrolyte layers of different thicknesses containing 0.1 M Na2SO4 was studied. Results showed that, under the bias voltage of 12 V, the reverse migration of ions occurred. For PCB-Cu, both copper dendrites and sulfate precipitates were found on the surface of FR-4 (board material) between two plates. Moreover, the Cu dendrite was produced between the two plates and migrated toward cathode. Compared to PCB-Cu, PCB-ENIG exhibited a higher tendency of ECM failure and suffered from seriously short circuit failure under high relative humidity (RH) environment. SKP results demonstrated that surface potentials of the anode plates were greater than those of the cathode plates, and those potentials of the two plates exhibited a descending trend as the RH increased. At the end of the paper, an electrochemical migration corrosion failure model of PCB was proposed. PMID:28772497

Superelectrophilic tetrakis(carbonyl)palladium(II)- and -platinum(II) undecafluorodiantimonate(V), [Pd(CO)4][Sb(2)F(11)]2 and [Pt(CO)4][Sb(2)F(11)]2: syntheses, physical and spectroscopic properties, their crystal, molecular, and extended structures, and density functional calculations: an experimental, computational, and comparative study .

PubMed

Willner, H; Bodenbinder, M; Bröchler, R; Hwang, G; Rettig, S J; Trotter, J; von Ahsen, B; Westphal, U; Jonas, V; Thiel, W; Aubke, F

2001-01-31

The salts [M(CO)(4)][Sb(2)F(11)](2), M = Pd, Pt, are prepared by reductive carbonylation of Pd[Pd(SO(3)F)(6)], Pt(SO(3)F)(4) or PtF(6) in liquid SbF(5), or HF-SbF(5). The resulting moisture-sensitive, colorless solids are thermally stable up to 140 degrees C (M = Pd) or 200 degrees C (M = Pt). Their thermal decompositions are studied by differential scanning calorimetry (DSC). Single crystals of both salts are suitable for an X-ray diffraction study at 180 K. Both isostructural salts crystallize in the monoclinic space group P2(1)/c (No. 14). The unit cell volume of [Pt(CO)(4)][Sb(2)F(11)](2) is smaller than that of [Pd(CO)(4)][Sb(2)F(11)](2) by about 0.4%. The cations [M(CO)(4)](2+), M = Pd, Pt, are square planar with only very slight angular and out-of-plane deviations from D(4)(h)() symmetry. The interatomic distances and bond angles for both cations are essentially identical. The [Sb(2)F(11)](-) anions in [M(CO)(4)][Sb(2)F(11)](2,) M = Pd, Pt, are not symmetry-related, and both pairs differ in their Sb-F-Sb bridge angles and their dihedral angles. There are in each salt four to five secondary interionic C- -F contacts per CO group. Of these, two contacts per CO group are significantly shorter than the sum of the van der Waals radii by 0.58 - 0.37 A. In addition, structural, and spectroscopic details of recently synthesized [Rh(CO)(4)][Al(2)Cl(7)] are reported. The cations [Rh(CO)(4)](+) and [M(CO)(4)](2+), M = Pd, Pt, are characterized by IR and Raman spectroscopy. Of the 16 vibrational modes (13 observable, 3 inactive) 10 (Pd, Pt) or 9 (Rh), respectively, are found experimentally. The vibrational assignments are supported by DFT calculations, which provide in addition to band positions also intensities of IR bands and Raman signals as well as internal force constants for the cations. (13)C NMR measurements complete the characterization of the square planar metal carbonyl cations. The extensive characterization of [M(CO)(4)][Sb(2)F(11)](2), M = Pd, Pt, reported here, allows a comparison to linear and octahedral [M(CO)(n)()][Sb(2)F(11)](2) salts [M = Hg (n = 2); Fe, Ru, Os (n = 6)] and their derivatives, which permit a deeper understanding of M-CO bonding in the solid state for superelectrophilic cations with [Sb(2)F(11)](-) or [SbF(6)](-) as anions.

The preparation and hydrogen brittleness resistance of Pd71.5Cu12Si16.5 metallic glass ribbons

NASA Astrophysics Data System (ADS)

Du, Xiaoqing; Ye, Xiaoqiu; Ren, Qingbo

2017-12-01

Pd71.5Cu12Si16.5 metallic glass ribbons as wide as 10mm were prepared by splat quenching. Structure was identified with X-ray diffraction (XRD) spectrums from the conventional X-ray diffractometer and also short wavelength X-ray stress analyzer. The results confirm fully amorphous structure of the ribbons. Multiple H2 adsorption and desorption cycles under a pressure of 100kPa were carried out in the metallic glass ribbon and also pure palladium membrane for comparison. The former didn’t show any cracks after more than 10 cycles, and thermal desorption spectroscopy (TDS) measurement confirms that hydrogen was adsorbed abundantly in the metallic glass ribbon. Pd71.5Cu12Si16.5 metallic glass ribbons demonstrate excellent hydrogen brittleness resistance.

Effect of different high-palladium metal-ceramic alloys on the color of opaque and dentin porcelain.

PubMed

Stavridakis, Minos M; Papazoglou, Efstratios; Seghi, Robert R; Johnston, William M; Brantley, William A

2004-08-01

The color of dental porcelain depends on the type of metal substrate. Little research has been done to document the effects of different types of high-palladium alloys on the color of dental porcelain. The purpose of this in vitro study was to evaluate the effects of different high-palladium alloys on the resulting color of dentin porcelain, as well as on that of opaque porcelain after simulated dentin and glazing firing cycles. Three Pd-Cu-Ga alloys, Spartan Plus (S), Liberty (B), and Freedom Plus (F), and 5 Pd-Ga alloys, Legacy (L), IS 85 (I), Protocol (P), Legacy XT (X), and Jelenko No.1 (N), were examined. A Pd-Ag alloy, Super Star (T), was included for comparison to the high-palladium alloys, and the Au-Pd alloy, Olympia (O), served as the control. Six cast discs (16 x 1 mm) were prepared from each of the alloys. Shade B1 opaque porcelain (Vita-Omega) was applied at a final thickness of 0.1 mm. After 2 opaque porcelain firing cycles, the surfaces were airborne-particle abraded, and the specimens were divided into 2 groups. In the first group, 0.9 mm of B1 dentin porcelain was applied. The other group of specimens with only opaque porcelain underwent the same dentin porcelain and glazing firing cycles. Color differences (DeltaE) were determined with a colorimeter between the control and each experimental group, after the second opaque porcelain, second dentin porcelain, and glazing firing cycles. One-way analysis of variance and Dunnett's multiple range test were performed on the DeltaE data (alpha=.05). After the application of dentin porcelain, the 3 Pd-Cu-Ga alloys showed significantly different (P<.05) DeltaE values (S=2.3 +/- 0.5, B=1.4 +/- 0.3, and F=1.3 +/- 0.7) than the control group. After the glazing cycle of this group, the 3 Pd-Cu-Ga alloys and the Pd-Ag alloy exhibited significantly different (P<.05) DeltaE values (S=2.8 +/- 0.8, B=2.2 +/- 0.3, F=1.9 +/- 1.0, and T=1.4 +/- 0.5) than the control group. After the simulated dentin porcelain firing cycles, the specimens with only opaque porcelain exhibited significantly different (P<.05) DeltaE values (S=5.2 +/- 1.4, B=5.4 +/- 0.6, and F=3.9 +/- 0.2) than the control group. The color difference between the 3 Pd-Cu-Ga alloys with only opaque porcelain and the control group increased more after the simulated glazing cycle (S=6.6 +/- 1.5, B=6.3 +/- 0.5, and F=4.6 +/- 0.1). The observed color differences between the Pd-Ga alloys and the control group were not statistically significant at any point. The Pd-Cu-Ga alloys with only opaque porcelain, after the simulated dentin porcelain and glazing firing cycles, exhibited clinically unacceptable color differences. The application of dentin porcelain to the Pd-Cu-Ga alloys resulted in clinically acceptable color differences. The application of dentin porcelain to the Pd-Ag alloy, after the glazing firing cycle, resulted in clinically acceptable color differences (approximately 2.8 to 3.7 DeltaE CIELAB units). The Pd-Ag alloy specimens with only opaque porcelain did not exhibit significant color differences from the control group, whereas significant color differences from the control group after the dentin porcelain and glazing firing cycles were still clinically acceptable.

Synthesis of Ag-Cu-Pd alloy thin films by DC-magnetron sputtering: Case study on microstructures and optical properties

NASA Astrophysics Data System (ADS)

Rezaee, Sahar; Ghobadi, Nader

2018-06-01

The present study aims to investigate optical properties of Ag-Cu-Pd alloy thin films synthesized by DC-magnetron sputtering method. The thin films are deposited on the glass and silicon substrates using Argon gas and Ag-Cu-Pd target. XRD analysis confirms the successful growth of Ag, Cu, and Pd NPs with FCC crystalline structure. Moreover, UV-visible absorption spectroscopy is applied to determine optical properties of the prepared samples which are affected by changes in surface morphology. The existence of single surface plasmon resonance (SPR) peak near 350 nm proves the formation of silver nanoparticles with a slight red shift through increasing deposition time. Ineffective thickness method (ITM) and Derivation of ineffective thickness method (DITM) are applied to extract optical band gap and transition type via absorption spectrum. SEM and AFM analyses show the distribution of near-spherical nanoparticles covering the surface of thin films. Furthermore, thickness variation affects the grain size. In addition, TEM image reveals the uniform size distribution of nanoparticles with an average particle size of about 15 nm. The findings show that increasing grain size and crystallite order along with the decrease of structural defect and disorders decrease optical band gap from 3.86 eV to 2.58 eV.

Oxidation-induced spin reorientation in Co adatoms and CoPd dimers on Ni/Cu(100)

NASA Astrophysics Data System (ADS)

Chen, K.; Beeck, T.; Fiedler, S.; Baev, I.; Wurth, W.; Martins, M.

2016-04-01

Ultrasmall magnetic clusters and adatoms are of strong current interest because of their possible use in future technological applications. Here, we demonstrate that the magnetic coupling between the adsorbates and the substrate can be significantly changed through oxidation. The magnetic properties of Co adatoms and CoPd dimers deposited on a remanently magnetized Ni/Cu(100) substrate have been investigated by x-ray absorption and x-ray magnetic circular dichroism spectroscopy at the Co L2 ,3 edges. Using spectral differences, pure and oxidized components are distinguished, and their respective magnetic moments are determined. The Co adatoms and the CoPd dimers are coupled ferromagnetically to the substrate, while their oxides, Co-O and CoPd-O, are coupled antiferromagnetically to the substrate. Along with the spin reorientation from the pure to the oxidized state, the magnetic moment of the adatom is highly reduced from Co to Co-O. In contrast, the magnetic moment of the dimer is of similar order for CoPd and CoPd-O.

Alternating verbal fluency performance following bilateral subthalamic nucleus deep brain stimulation for Parkinson's disease.

PubMed

Marshall, D F; Strutt, A M; Williams, A E; Simpson, R K; Jankovic, J; York, M K

2012-12-01

Despite common occurrences of verbal fluency declines following bilateral subthalamic nucleus deep brain stimulation (STN-DBS) for the treatment of Parkinson's disease (PD), alternating fluency measures using cued and uncued paradigms have not been evaluated. Twenty-three STN-DBS patients were compared with 20 non-surgical PD patients on a comprehensive neuropsychological assessment, including cued and uncued intradimensional (phonemic/phonemic and semantic/semantic) and extradimensional (phonemic/semantic) alternating fluency measures at baseline and 6-month follow-up. STN-DBS patients demonstrated a greater decline on the cued phonemic/phonemic fluency and the uncued phonemic/semantic fluency tasks compared to the PD patients. For STN-DBS patients, verbal learning and information processing speed accounted for a significant proportion of the variance in declines in alternating phonemic/phonemic and phonemic/semantic fluency scores, respectively, whilst only naming was related to uncued phonemic/semantic performance for the PD patients. Both groups were aided by cueing for the extradimensional task at baseline and follow-up, and the PD patients were also aided by cueing for the phonemic/phonemic task on follow-up. These findings suggest that changes in alternating fluency are not related to disease progression alone as STN-DBS patients demonstrated greater declines over time than the PD patients, and this change was related to declines in information processing speed. © 2012 The Author(s) European Journal of Neurology © 2012 EFNS.

Changing Bureaucratic Behavior Acquisition Reform in the United States Army

DTIC Science & Technology

2000-01-01

I . Title. UC263.S32 2000 355.6��—dc21 99-39065 CIP RAND is a nonprofit...1 CO cu u a cu ■ä cu u a 1 2 a a .—1 CN i — I tN m •* in CO r~ 00 CT> rH l-H i —t 8 a o W CO CO. 1 cu cu ŗ J3 cu cu UJ E E ■S CU...p cu > äj § S3 ■43 ■n J3 X. CO cO rrl ■§ cu cu cu i o CO a CO a co a T3 O ■a ft o o o M 1*1 ■g ■g CO ’g ft ft) X II a a a. X V a E

Development of a novel immunoPET tracer to image human PD-1 checkpoint expression on tumor infiltrating lymphocytes in a humanized mouse model

PubMed Central

Natarajan, Arutselvan; Mayer, Aaron T; Reeves, Robert E; Nagamine, Claude M; Gambhir, Sanjiv S.

2017-01-01

Purpose It is well known that cancers exploit immune checkpoints (programmed death 1 receptor (PD-1) and its ligand (PD-L1)) to evade anti-tumor immune responses. Although immune checkpoint (IC) blockade is a promising approach, not all patients respond. Hence, the purpose of this study is imaging of tumor infiltrating lymphocytes (TILs), as they are known to express PD-1 during activation and subsequent exhaustion in the tumor microenvironment and are thought to be potentially predictive of therapeutic responses to IC blockade. Procedures We developed immunoPET tracers to image hPD-1 status of human peripheral blood mononuclear cells (hPBMC) adoptively transferred to NOD-scid IL-2Rγnull (NSG) mice (hNSG) bearing A375 human skin melanoma tumors. The anti-PD-1 human antibody (IgG; keytruda) labeled with either [89Zr]- or [64Cu]- radiometals to image PD-1 expressing human TILs in vivo. Results [89Zr]keytruda (groups = 2; NSG-ctl [control] and hNSG-nblk [non-blocking], n=3-5, 3.2 ± 0.4 MBq/15-16 μg/200 μL, and [64Cu]keytruda (groups = 3; NSG-ctl, NSG-blk [blocking], and hNSG-nblk) n=4, 7.4 ± 0.4 MBq /20-25μg/200 μL) were administered in mice. PET-CT scans were performed over 1-144 h ([89Zr]keytruda) and 1-48 h ([64Cu]keytruda) on mice. hNSG mice exhibited a high tracer uptake in the spleen lymphoid organs and tumors. At 24h, human TILs homing into melanoma of hNSG-nblk mice exhibited high signal (mean %ID/g ± SD) of 3.8 ± 0.4 ([89Zr]keytruda), and 6.4 ± 0.7 ([64Cu]keytruda), which was 1.5- and 3-fold higher uptake compared to NSG-ctl mice (p = 0.01), respectively. Biodistribution measurements of hNSG-nblk mice performed at 144 h ([89Zr]keytruda), and 48 h ([64Cu]keytruda) p.i. revealed tumor to muscle ratios as high as 45 and 12-fold, respectively. Conclusion This study clearly demonstrates specific imaging of human PD-1 expressing TILs within the tumor and lymphoid tissues. This suggests anti-human-PD-1 tracer could be clinically translatable to monitor cancer treatment response to IC blockade therapy. PMID:28247187

cis,cis-Muconic acid: separation and catalysis to bio-adipic acid for nylon-6,6 polymerization

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vardon, Derek R.; Rorrer, Nicholas A.; Salvachúa, Davinia

cis,cis-Muconic acid is a polyunsaturated dicarboxylic acid that can be produced renewably via the biological conversion of sugars and lignin-derived aromatic compounds. Subsequently, muconic acid can be catalytically converted to adipic acid -- the most commercially significant dicarboxylic acid manufactured from petroleum. Nylon-6,6 is the major industrial application for adipic acid, consuming 85% of market demand; however, high purity adipic acid (99.8%) is required for polymer synthesis. As such, process technologies are needed to effectively separate and catalytically transform biologically derived muconic acid to adipic acid in high purity over stable catalytic materials. To that end, this study: (1) demonstratesmore » bioreactor production of muconate at 34.5 g L-1 in an engineered strain of Pseudomonas putida KT2440, (2) examines the staged recovery of muconic acid from culture media, (3) screens platinum group metals (e.g., Pd, Pt, Rh, Ru) for activity and leaching stability on activated carbon (AC) and silica supports, (4) evaluates the time-on-stream performance of Rh/AC in a trickle bed reactor, and (5) demonstrates the polymerization of bio-adipic acid to nylon-6,6. Separation experiments confirmed AC effectively removed broth color compounds, but subsequent pH/temperature shift crystallization resulted in significant levels of Na, P, K, S and N in the crystallized product. Ethanol dissolution of muconic acid precipitated bulk salts, achieving a purity of 99.8%. Batch catalysis screening reactions determined that Rh and Pd were both highly active compared to Pt and Ru, but Pd leached significantly (1-9%) from both AC and silica supports. Testing of Rh/AC in a continuous trickle bed reactor for 100 h confirmed stable performance after 24 h, although organic adsorption resulted in reduced steady-state activity. Lastly, polymerization of bio-adipic acid with hexamethyldiamine produced nylon-6,6 with comparable properties to its petrochemical counterpart, thereby demonstrating a path towards bio-based nylon production via muconic acid.« less

Magneto-optical properties of PdCo based multilayered films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nakamura, K.; Tsunashima, S.; Iwata, S.

1989-09-01

Magneto-optical and magnetic properties of multilayered films composed of PdCo alloy and other noble metal (Pd, Pt or Cu) layers are investigated. Multilayered films were prepared by RF magnetron sputtering method. Kerr rotation spectra (275nm-800nm) of Pd/Co multilayered films resemble those of PdCo alloys. In the films composed of PdCo alloy and Pt bilayers, the Kerr rotation increases with increasing Pt content while the perpendicular anisotropy decreases.

Electronic Structure, Mechanical and Dynamical Stability of Hexagonal Subcarbides M2C (M = Tc, Ru, Rh, Pd, Re, Os, Ir, and Pt): Ab Initio Calculations

NASA Astrophysics Data System (ADS)

Suetin, D. V.; Shein, I. R.

2018-02-01

Ab initio calculations were used to study the properties of a series of hexagonal (Fe2N-like) subcarbides M2C, where M = Tc, Ru, Rh, Pd, Re, Os, Ir, and Pt, and to calculate their equilibrium structural parameters, electronic properties, phase stability, elastic constants, compression modulus, shear modulus, Young's modulus, compressibility, Pugh's indicator, Poisson ratio, elastic anisotropy indices, and also hardness, Debye temperature, sound velocity, and low-temperature heat capacity. It is found based on these results that all the subcarbides are mechanically stable; however, their formation energies E form are positive with respect to a mixture of d-metal and graphite. In addition, the calculation of the phonon spectra of these subcarbides shows the existence of negative modes, which indicates their dynamical instability. Thus, a successful synthesis of these subcarbides at normal conditions is highly improbable.

Noble metal catalyzed aqueous phase hydrogenation and hydrodeoxygenation of lignin-derived pyrolysis oil and related model compounds.

PubMed

Mu, Wei; Ben, Haoxi; Du, Xiaotang; Zhang, Xiaodan; Hu, Fan; Liu, Wei; Ragauskas, Arthur J; Deng, Yulin

2014-12-01

Aqueous phase hydrodeoxygenation of lignin pyrolysis oil and related model compounds were investigated using four noble metals supported on activated carbon. The hydrodeoxygenation of guaiacol has three major reaction pathways and the demethylation reaction, mainly catalyzed by Pd, Pt and Rh, produces catechol as the products. The presence of catechol and guaiacol in the reaction is responsible for the coke formation and the catalysts deactivation. As expected, there was a significant decrease in the specific surface area of Pd, Pt and Rh catalysts during the catalytic reaction because of the coke deposition. In contrast, no catechol was produced from guaiacol when Ru was used so a completely hydrogenation was accomplished. The lignin pyrolysis oil upgrading with Pt and Ru catalysts further validated the reaction mechanism deduced from model compounds. Fully hydrogenated bio-oil was produced with Ru catalyst. Copyright © 2014 Elsevier Ltd. All rights reserved.

Tunable resistivity due to kinetic arrest of antiferro-ferromagnetic transition in FeRh0.46Pd0.54

NASA Astrophysics Data System (ADS)

Saha, Pampi; Rawat, R.

2018-05-01

We show a large negative magnetoresistance (MR) of ≈10% near room temperature in FeRh0.46Pd0.54, which increases to more than 60% at low temperatures. The magnitude of resistivity and, hence, MR depend on the history of the sample in HT (magnetic field-temperature) space, e.g., resistivity at 5 K changes by more than 70% with thermal cycling. These results are explained due to slow kinetics of the transformation from austenite antiferromagnetic (AF) to martensite ferromagnetic (FM) state with the decrease in temperature. As a result, AF to FM transformation remains incomplete on experimental time scales and non-ergodic AF phase co-exists with a low temperature equilibrium FM phase. In the present system, the kinetics of the transition is shown to dominate up to 150 K, which is significantly high in comparison to other kinetically arrested systems.

Cu3(BTC)2: CO oxidation over MOF based catalysts.

PubMed

Ye, Jing-yun; Liu, Chang-jun

2011-02-21

Crystalline and amorphized MOFs (Cu(3)(BTC)(2)) have been demonstrated to be excellent catalysts for CO oxidation. The catalytic activity can be further improved by loading PdO(2) nanoparticles onto the amorphized Cu(3)(BTC)(2).

Polymer-Supported Optically Active fac(S)-Tris(thiotato)rhodium(III) Complex for Sulfur-Bridging Reaction With Precious Metal Ions.

PubMed

Aizawa, Sen-Ichi; Tsubosaka, Soshi

2016-01-01

The optically active mixed-ligand fac(S)-tris(thiolato)rhodium(III) complexes, ΔL -fac(S)-[Rh(aet)2 (L-cys-N,S)](-) (aet = 2-aminoethanethiolate, L-cys = L-cysteinate) () and ΔLL -fac(S)-[Rh(aet)(L-cys-N,S)2 ](2-) were newly prepared by the equatorial preference of the carboxyl group in the coordinated L-cys ligand. The amide formation reaction of with 1,10-diaminodecane and polyallylamine gave the diamine-bridged dinuclear Rh(III) complex and the single-chain polymer-supported Rh(III) complex with retention of the ΔL configuration of , respectively. These Rh(III) complexes reacted with Co(III) or Co(II) to give the linear-type trinuclear structure with the S-bridged Co(III) center and the two Δ-Rh(III) terminal moieties. The polymer-supported Rh(III) complex was applied not only to the CD spectropolarimetric detection and determination of a trace of precious metal ions such as Au(III), Pt(II), and Pd(II) but also to concentration and extraction of these metal ions into the solid polymer phase. Chirality 28:85-91, 2016. © 2015 Wiley Periodicals, Inc. © 2015 Wiley Periodicals, Inc.

Rh-Catalyzed Annulations of N-Methoxybenzamides and Ketenimines: Sterically and Electronically Controlled Synthesis of Isoquinolinones and Isoindolinones.

PubMed

Zhou, Xiaorong; Zhang, Zhiyin; Zhao, Hongyang; Lu, Ping; Wang, Yanguang

2017-04-07

Rhodium-catalyzed C-H activation/annulation reactions of ketenimines with N-methoxybenzamides are reported. The outcome of reactions is dependent on the structure of ketenimines. The β-alkyl-substituted ketenimines furnish 3-iminoisoquinolin-1(2H)-ones in a formal [4 + 2] annulation manner, while the β-ester substituted ketenimines afford 3-aminoisoindolin-1-ones in a formal [4 + 1] annulation manner. The synthesized [4 + 2] products undergo an intramolecular Cu-catalyzed C-N coupling to be converted to benzo[4,5]imidazo[1,2-b]isoquinolin-11-ones, which can be directly prepared from ketenimines and N-methoxybenzamides by a one-pot Rh-catalyzed annulation/Cu-catalyzed C-N coupling sequence.

High performance fuel electrodes fabricated by electroless plating of copper on BaZr0.8Ce0.1Y0.1O3-δ proton-conducting ceramic

NASA Astrophysics Data System (ADS)

Patki, Neil S.; Way, J. Douglas; Ricote, Sandrine

2017-10-01

The stability of copper at high temperatures in reducing and hydrocarbon-containing atmospheres makes it a good candidate for fabricating fuel electrodes on proton-conducting ceramics, such as BaZr0.9-xCexY0.1O3-δ (BZCY). In this work, the electrochemical performance of Cu-based electrodes fabricated by electroless plating (ELP) on BaZr0.8Ce0.1Y0.1O3-δ is studied with impedance spectroscopy. Three activation catalysts (Pd, Ru, and Cu) are investigated and ELP is compared to a commercial Cu paste (ESL 2312-G) for electrode fabrication. The area specific resistances (ASR) for Pd, Ru, and Cu activations at 700 °C in moist 5% H2 in Ar are 2.1, 3.2, and 13.4 Ω cm2, respectively. That is a 1-2 orders of magnitude improvement over the commercial Cu paste (192 Ω cm2). Furthermore, the ASR has contributions from electrode processes and charge transfer at the electrode/electrolyte interface. Additionally, the morphology of the as-fabricated electrode is unaffected by the activation catalyst. However, heat treatment at 750 °C in H2 for 24 h leads to sintering and large reorganization of the electrode fabricated with Cu activation (micron sized pores seen in the tested sample), while Pd and Ru activations are immune to such reorganization. Thus, Pd and Ru are identified as candidates for future work with improvements to charge transfer required for the former, and better electrode processes required for the latter.

Ab initio study on the dynamics of furfural at the liquid-solid interfaces

NASA Astrophysics Data System (ADS)

Dang, Hongli; Xue, Wenhua; Shields, Darwin; Liu, Yingdi; Jentoft, Friederike; Resasco, Daniel; Wang, Sanwu

2013-03-01

Catalytic biomass conversion sometimes occurs at the liquid-solid interfaces. We report ab initio molecular dynamics simulations at finite temperatures for the catalytic reactions involving furfural at the water-Pd and water-Cu interfaces. We found that, during the dynamic process, the furan ring of furfural prefers to be parallel to the Pd surface and the aldehyde group tends to be away from the Pd surface. On the other hand, at the water-Cu(111) interface, furfural prefers to be tilted to the Cu surface while the aldehyde group is bonded to the surface. In both cases, interaction of liquid water and furfural is identified. The difference of dynamic process of furfural at the two interfaces suggests different catalytic reaction mechanisms for the conversion of furfural, consistent with the experimental investigations. Supported by DOE (DE-SC0004600). Simulations and calculations were performed on XSED's and NERSC's supercomputers

Direct Observation of the Surface Segregation of Cu in Pd by Time-Resolved Positron-Annihilation-Induced Auger Electron Spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mayer, J.; Hugenschmidt, C.; Schreckenbach, K.

2010-11-12

Density functional theory calculations predict the surface segregation of Cu in the second atomic layer of Pd which has not been unambiguously confirmed by experiment so far. We report measurements on Pd surfaces covered with three and six monolayers of Cu using element selective positron-annihilation-induced Auger electron spectroscopy (PAES) which is sensitive to the topmost atomic layer. Moreover, time-resolved PAES, which was applied for the first time, enables the investigation of the dynamics of surface atoms and hence the observation of the segregation process. The time constant for segregation was experimentally determined to {tau}=1.38(0.21) h, and the final segregated configurationmore » was found to be consistent with calculations. Time-dependent PAES is demonstrated to be a novel element selective technique applicable for the investigation of, e.g., heterogeneous catalysis, corrosion, or surface alloying.« less

Direct Observation of the Surface Segregation of Cu in Pd by Time-Resolved Positron-Annihilation-Induced Auger Electron Spectroscopy

NASA Astrophysics Data System (ADS)

Mayer, J.; Hugenschmidt, C.; Schreckenbach, K.

2010-11-01

Density functional theory calculations predict the surface segregation of Cu in the second atomic layer of Pd which has not been unambiguously confirmed by experiment so far. We report measurements on Pd surfaces covered with three and six monolayers of Cu using element selective positron-annihilation-induced Auger electron spectroscopy (PAES) which is sensitive to the topmost atomic layer. Moreover, time-resolved PAES, which was applied for the first time, enables the investigation of the dynamics of surface atoms and hence the observation of the segregation process. The time constant for segregation was experimentally determined to τ=1.38(0.21)h, and the final segregated configuration was found to be consistent with calculations. Time-dependent PAES is demonstrated to be a novel element selective technique applicable for the investigation of, e.g., heterogeneous catalysis, corrosion, or surface alloying.

Synthesis, crystal structure and electronic structure of the binary phase Rh{sub 2}Cd{sub 5}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Koley, Biplab; Chatterjee, S.; Jana, Partha P., E-mail: ppj@chem.iitkgp.ernet.in

2017-02-15

A new phase in the Rh-Cd binary system - Rh{sub 2}Cd{sub 5} has been identified and characterized by single crystal X-ray diffraction and Energy dispersive X-ray analysis. The stoichiometric compound Rh{sub 2}Cd{sub 5} crystallizes with a unit cell containing 14 atoms, in the orthorhombic space group Pbam (55). The crystal structure of Rh{sub 2}Cd{sub 5} can be described as a defect form of the In{sub 3}Pd{sub 5} structure with ordered vacancies, formed of two 2D atomic layers with the stacking sequence: ABAB. The A type layers consist of (3.6.3.6)-Kagomé nets of Cd atoms while the B type layers consist ofmore » (3{sup 5}) (3{sup 7})- nets of both Cd and Rh atoms. The stability of this line phase is investigated by first principle electronic structure calculations on the model of ordered Rh{sub 2}Cd{sub 5}. - Graphical abstract: (3.6.3.6)-Kagomé nets of cadmium atoms (top) and (3{sup 5}) (3{sup 7})- nets of both cadmium and rhodium atoms (bottom) in the structure of Rh{sub 2}Cd{sub 5}.« less

A highly sensitive hydrogen sensor with gas selectivity using a PMMA membrane-coated Pd nanoparticle/single-layer graphene hybrid.

PubMed

Hong, Juree; Lee, Sanggeun; Seo, Jungmok; Pyo, Soonjae; Kim, Jongbaeg; Lee, Taeyoon

2015-02-18

A polymer membrane-coated palladium (Pd) nanoparticle (NP)/single-layer graphene (SLG) hybrid sensor was fabricated for highly sensitive hydrogen gas (H2) sensing with gas selectivity. Pd NPs were deposited on SLG via the galvanic displacement reaction between graphene-buffered copper (Cu) and Pd ion. During the galvanic displacement reaction, graphene was used as a buffer layer, which transports electrons from Cu for Pd to nucleate on the SLG surface. The deposited Pd NPs on the SLG surface were well-distributed with high uniformity and low defects. The Pd NP/SLG hybrid was then coated with polymer membrane layer for the selective filtration of H2. Because of the selective H2 filtration effect of the polymer membrane layer, the sensor had no responses to methane, carbon monoxide, or nitrogen dioxide gas. On the contrary, the PMMA/Pd NP/SLG hybrid sensor exhibited a good response to exposure to 2% H2: on average, 66.37% response within 1.81 min and recovery within 5.52 min. In addition, reliable and repeatable sensing behaviors were obtained when the sensor was exposed to different H2 concentrations ranging from 0.025 to 2%.

Level, source identification, and risk analysis of heavy metal in surface sediments from river-lake ecosystems in the Poyang Lake, China.

PubMed

Zhang, Hua; Jiang, Yinghui; Ding, Mingjun; Xie, Zhenglei

2017-09-01

The concentrations, sources, and risks of heavy metals (Fe, Al, Mn, Cr, Co, Ni, Cu, Zn, As, Cd, W, Pb, and Tl) in sediments in five river-lake ecosystems in the Poyang Lake region were studied. The concentrations of the heavy metals varied spatially, with most of the highest concentrations in the Raohe river-lake ecosystem (RH). All heavy metals except As, Cd, W, and Tl were enriched in sediments possessing high total organic carbon contents or in finer sediments. Based on enrichment factors and statistical methods, it was found that Cd in sediments in the Xiushui (XS), Ganjiang (GJ), Xinjiang (XJ) river-lake ecosystems, and RH; Mn in the XS, GJ, and RH; and W in the XS and GJ were greatly affected by anthropogenic inputs. Moreover, the origins of Cu, Zn, and As require more attention due to the high concentrations found. The high enrichment factor of Cd in the sediments indicated that this metal might cause significant pollution in the environment. The results of the modified potential ecological risk index revealed that the XS, GJ, RH, and XJ were at considerable ecological risk, while the sediments in the Fuhe river-lake ecosystem (FH) were at moderate ecological risk, with Cd contributing the highest proportion of risk. The hazard score fundamentally validated the modified potential ecological risk analysis and revealed a mean toxicity of 57.80% to the benthic organisms in the RH.

Enhancement of Sn-Bi-Ag Solder Joints with ENEPIG Surface Finish for Low-Temperature Interconnection

NASA Astrophysics Data System (ADS)

Pun, Kelvin P. L.; Islam, M. N.; Rotanson, Jason; Cheung, Chee-wah; Chan, Alan H. S.

2018-05-01

Low-temperature soldering constitutes a promising solution in interconnect technology with the increasing trend of heat-sensitive materials in integrated circuit packaging. Experimental work was carried out to investigate the effect of electroless Ni/electroless Pd/immersion gold (ENEPIG) layer thicknesses on Sn-Bi-Ag solder joint integrity during extended reflow at peak temperatures as low as 175°C. Optimizations are proposed to obtain reliable solder joints through analysis of interfacial microstructure with the resulting joint integrity under extended reflow time. A thin Ni(P) layer with thin Pd led to diffusion of Cu onto the interface resulting in Ni3Sn4 intermetallic compound (IMC) spalling with the formation of thin interfacial (Ni,Cu)3Sn4 IMCs which enhance the robustness of the solder after extended reflow, while thick Ni(P) with thin Pd resulted in weakened solder joints with reflow time due to thick interfacial Ni3Sn4 IMCs with the entrapped brittle Bi-phase. With a suitable thin Ni(P), the Pd thickness has to be optimized to prevent excessive Ni-P consumption and early Cu outward diffusion to enhance the solder joint during extended reflow. Based on these findings, suitable Ni(P) and Pd thicknesses of ENEPIG are recommended for the formation of robust low-temperature solder joints.

Study on separation of platinum group metals from high level liquid waste using macroporous (MOTDGA-TOA)/SiO{sub 2}-P silica-based absorbent

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ito, Tatsuya; Japan Atomic Energy Agency, Tokai-mura Naka-gun, Ibarak319-1195; Kim, Seong-Yun

2013-07-01

The recovery of platinum group metals (PGMs) from high level liquid waste (HLLW) by macroporous silica-based adsorbent, (MOTDGA-TOA)/SiO{sub 2}-P has been developed by impregnating two extractants of N,N'-dimethyl-N,N'-di-n-octyl-thio-diglycolamide (MOTDGA) and tri-n-octylamine (TOA) into a silica/polymer composite support (SiO{sub 2}-P). The adsorption of Ru(III), Rh(III) and Pd(II) have been investigated in simulated HLLW by batch method. The adsorbent has shown good uptake property for Pd(II). In addition, the combined use of MOTDGA and TOA improved the adsorption of Ru(III) and Rh(III) better than the individual use of them. The usability of adsorbent in radiation fields was further confirmed by irradiation experiments.more » The adsorbent remained to have the uptake capability for PGMs over the absorbed dose of 100 kGy, corresponding with one really adsorbed by the adsorbent, and showed good retention capability for Pd(II) even at the absorbed dose of 800 kGy. The chromatographic separation of metal ions was demonstrated with the adsorbent packed column, there is no influence of Re(VII) (instead of Tc) on the excellent separation behavior of Pd(II). (authors)« less

Weathering of PGE sulfides and Pt-Fe alloys in the Freetown Layered Complex, Sierra Leone

NASA Astrophysics Data System (ADS)

Bowles, John F. W.; Suárez, Saioa; Prichard, Hazel M.; Fisher, Peter C.

2017-12-01

Fresh and weathered rocks and saprolite from Horizon B of the Freetown Layered Complex contain platinum-group minerals (PGM). The PGM in the fresh rocks are 1-7 μm across, including cooperite (PtS), isoferroplatinum (Pt3Fe), minor tetraferroplatinum (PtFe), tulameenite (Pt2FeCu), Os-bearing laurite (RuS2), and other base metal-sulfide (BMS)-bearing PGM. The weathered rocks contain fewer of those PGM but a high proportion of disordered Cu-(±Pd)-bearing Pt-Fe alloys. The saprolite hosts scarce, smaller (1-3 μm) ordered PtFe and disordered PtFe3. The Pt-Fe alloys became increasingly Fe rich as weathering proceeded. Pt-Fe oxides appeared during weathering. Copper sulfides associated with the primary PGM and cooperite (with <3% Pd) were destroyed to provide the minor Cu and Pd found in some of the disordered Pt-Fe alloys. Platinum- and Pd-bearing saprolites have retained the original rock fabric and, to a depth of about 2 m, surround residual rocks that show progressive weathering (corestones). Ground water passing through the saprolite has transported Pt and Pd (and probably Au) in solution down slope into saprolite over unmineralized rocks. Transport is marked by changes in the Pt/Pd ratio indicating that the metals have moved independently. Palladium is present in marginally higher concentrations in the deeper saprolite than in the corestones suggesting some retention of Pd in the deeper saprolite. Platinum and Pd are less concentrated in the upper saprolite than the deeper saprolite indicating surface leaching. Alteration occurred over a long period in an organic and microbial rich environment that may have contributed to the leaching and transport of PGE.

Inductively coupled plasma-mass spectroscopy measurements of elemental release from 2 high-palladium dental casting alloys into a corrosion testing medium.

PubMed

Tufekci, Eser; Mitchell, John C; Olesik, John W; Brantley, William A; Papazoglou, Efstratios; Monaghan, Peter

2002-01-01

The biocompatibility of high-palladium alloy restorations has been of some concern due to the release of palladium into the oral environment and sensitivity reactions in patients. This study measured the in vitro elemental release from a Pd-Cu-Ga alloy and a Pd-Ga alloy into a corrosion testing medium. Both alloys were cast into 12-mm-diameter x 1-mm-thick disks, subjected to heat treatment that simulated porcelain firing cycles, polished to a 0.05-mm surface finish, and ultrasonically cleaned in ethanol. Two specimens of each alloy were immersed 3 times (at 7, 70, and 700 hours) in an aqueous lactic acid/NaCl solution used for in vitro corrosion testing and maintained at 37 degrees C. The specimens were removed after each immersion time, and the elemental compositions of the solutions were analyzed with inductively coupled plasma-mass spectroscopy (ICP-MS). Elemental concentrations for the 2 alloys at each immersion time were compared with Student t test (alpha=.05). No significant differences in palladium release were found for the 7- and 70-hour solutions, but significant differences were found for the 700-hour solutions. Mean concentrations of palladium and gallium in the 700-hour solutions, expressed as mass per unit area of alloy surface, were 97 (Pd) and 46 (Ga) microg/cm(2) for the Pd-Cu-Ga alloy and 5 (Pd) and 18 (Ga) microg/cm(2) for the Pd-Ga alloy. Relative proportions of the elements in the solutions were consistent with the release of palladium and breakdown of microstructural phases found in the alloys. The results suggest that there may be a lower risk of adverse biological reactions with the Pd-Ga alloy than with the Pd-Cu-Ga alloy tested.

Geostatistical interpolation of available copper in orchard soil as influenced by planting duration.

PubMed

Fu, Chuancheng; Zhang, Haibo; Tu, Chen; Li, Lianzhen; Luo, Yongming

2018-01-01

Mapping the spatial distribution of available copper (A-Cu) in orchard soils is important in agriculture and environmental management. However, data on the distribution of A-Cu in orchard soils is usually highly variable and severely skewed due to the continuous input of fungicides. In this study, ordinary kriging combined with planting duration (OK_PD) is proposed as a method for improving the interpolation of soil A-Cu. Four normal distribution transformation methods, namely, the Box-Cox, Johnson, rank order, and normal score methods, were utilized prior to interpolation. A total of 317 soil samples were collected in the orchards of the Northeast Jiaodong Peninsula. Moreover, 1472 orchards were investigated to obtain a map of planting duration using Voronoi tessellations. The soil A-Cu content ranged from 0.09 to 106.05 with a mean of 18.10 mg kg -1 , reflecting the high availability of Cu in the soils. Soil A-Cu concentrations exhibited a moderate spatial dependency and increased significantly with increasing planting duration. All the normal transformation methods successfully decreased the skewness and kurtosis of the soil A-Cu and the associated residuals, and also computed more robust variograms. OK_PD could generate better spatial prediction accuracy than ordinary kriging (OK) for all transformation methods tested, and it also provided a more detailed map of soil A-Cu. Normal score transformation produced satisfactory accuracy and showed an advantage in ameliorating smoothing effect derived from the interpolation methods. Thus, normal score transformation prior to kriging combined with planting duration (NSOK_PD) is recommended for the interpolation of soil A-Cu in this area.

Tin Whisker Growth and Mitigation with a Nanocrysytalline Nickel Coating

NASA Astrophysics Data System (ADS)

Janiuk, Szymon

Tin whiskers are a problem in the electronics industry since the EU banned the use of lead in Pb-Sn solders as part of the Restriction of Hazardous Substances (RoHS). The biggest concern with Sn whiskers is their ability to short-circuit electronics. High reliability applications such as the aerospace, defense, healthcare, and automotive industries are at most risk. This project explores Sn whisker mitigation and prevention with the use of nanocrystalline nickel coating over Sn surfaces. Sn was plated onto a pure Cu substrate using electroplating. A high temperature and high humidity condition, at 85°C and 85% RH, was effective at growing whiskers. A nNi coating was plated over Sn/Cu coupons. After subjecting the nNi/ Sn/Cu samples through 85°C/85% RH testing conditions, no whiskers were observed penetrating the surface. These results make nNi a viable material to use as a coating to prevent the growth of Sn whiskers in electronic assemblies.

Reliability and Validity of Nonradiologic Measures of Forward Flexed Posture in Parkinson Disease.

PubMed

Nair, Prajakta; Bohannon, Richard W; Devaney, Laurie; Maloney, Catherine; Romano, Alexis

2017-03-01

To examine the intertester reliability and validity of 5 nonradiologic measures of forward flexed posture in individuals with Parkinson disease (PD). Cross-sectional observational study. University outpatient facility and community centers. Individuals (N=28) with PD with Hoehn and Yahr scores of 1 through 4. Not applicable. Occiput to wall status, tragus to wall distance, C7 to wall distance, photographically derived trunk flexion angle, and inclinometric kyphosis measure. Participants were older adults (mean, 69.7±10.6y) with a 14-month to 15-year (mean, 5.9±3.5y) history of PD. Intertester reliability was excellent for all measures (κ=.89 [cued condition] and 1.0 [relaxed condition] for occiput to wall status; intraclass correlation coefficients, .779-.897 for tragus to wall distance, C7 to wall distance, flexion angle, and inclinometric kyphosis measure). Convergent validity was supported for all measures by significant correlations between the same measures obtained during relaxed and cued conditions (eg, occiput to wall relaxed and cued) and for most measures by significant correlations between measures obtained under the same condition (eg, occiput to wall cued and tragus to wall cued). Significant correlations between tragus to wall distance, C7 to wall distance, flexion angle, and inclinometric kyphosis measure and the Unified Parkinson Disease Rating Scale item 28 (posture) also supported convergent validity. Significant differences between tragus to wall distance, C7 to wall distance, and inclinometric kyphosis measure values under relaxed and cued conditions supported known condition validity. Known group validity was demonstrated by significant differences in tragus to wall distance, C7 to wall distance, and inclinometric kyphosis measure obtained from individuals able and individuals unable to touch their occiput to wall when cued to stand tall. Tragus to wall distance, C7 to wall distance, and inclinometric kyphosis measure are reliable and valid nonradiologic measures of forward flexed posture in PD. Copyright © 2016 American Congress of Rehabilitation Medicine. Published by Elsevier Inc. All rights reserved.

Copper isotope fractionation during partial melting and melt percolation in the upper mantle: Evidence from massif peridotites in Ivrea-Verbano Zone, Italian Alps

NASA Astrophysics Data System (ADS)

Huang, Jian; Huang, Fang; Wang, Zaicong; Zhang, Xingchao; Yu, Huimin

2017-08-01

To investigate the behavior of Cu isotopes during partial melting and melt percolation in the mantle, we have analyzed Cu isotopic compositions of a suite of well-characterized Paleozoic peridotites from the Balmuccia and Baldissero massifs in the Ivrea-Verbano Zone (IVZ, Northern Italy). Our results show that fresh lherzolites and harzburgites have a large variation of δ65Cu ranging from -0.133 to 0.379‰, which are negatively correlated with Al2O3 contents as well as incompatible platinum-group (e.g., Pd) and chalcophile element (e.g., Cu, S, Se, and Te) contents. The high δ65Cu can be explained by Cu isotope fractionation during partial melting of a sulfide-bearing peridotite source, with the light isotope (63Cu) preferentially entering the melts. The low δ65Cu can be attributed to precipitation of sulfides enriched in 63Cu during sulfur-saturated melt percolation. Replacive dunites from the Balmuccia massif display high δ65Cu from 0.544 to 0.610‰ with lower Re, Pd, S, Se, and Te contents and lower Pd/Ir ratios relative to lherzolites, which may result from dissolution of sulfides during interactions between S-undersaturated melts and lherzolites at high melt/rock ratios. Thus, our results suggest that partial melting and melt percolation largely account for the Cu isotopic heterogeneity of the upper mantle. The correlation between δ65Cu and Cu contents of the lherzolites and harzburgites was used to model Cu isotope fractionation during partial melting of a sulfide-bearing peridotite, because Cu is predominantly hosted in sulfide. The modelling results indicate an isotope fractionation factor of αmelt-peridotite = 0.99980-0.99965 (i.e., 103lnαmelt-peridotite = -0.20 to -0.35‰). In order to explain the Cu isotopic systematics of komatiites and mid-ocean ridge basalts reported previously, the estimated αmelt-peridotite was used to simulate Cu isotopic variations in melts generated by variable degrees of mantle melting. The results suggest that high degrees (>25%) of partial melting extracts nearly all source Cu and it cannot produce Cu isotope fractionation in komatiites relative to their mantle source, and that sulfide segregation during magma evolution have modified Cu isotopic compositions of mid-ocean ridge basalts.

Influence of surface topography on RBS measurements: case studies of (Cu/Fe/Pd) multilayers and FePdCu alloys nanopatterned by self-assembly

NASA Astrophysics Data System (ADS)

Krupinski, M.; Perzanowski, M.; Zabila, Y.; Zarzycki, A.; Marszałek, M.

2017-03-01

In this paper the influence of surface topography on Rutherford backscattering spectrometry (RBS) is discussed. (Cu/Fe/Pd) multilayers with total thickness of about 10 nm were deposited by physical vapor deposition on self-organized array of SiO2 nanoparticles with the size of 50 nm and 100 nm. As a reference, the multilayered systems were also prepared on flat substrates under the same conditions. After the deposition, morphology of the systems was studied by scanning electron microscopy (SEM), while chemical analysis was performed using Rutherford backscattering spectrometry. It was found that the RBS spectra and determined compositions for flat and patterned multilayers differ. The difference is discussed by taking into account the effect of additional inelastic scattering and energy straggling occurring due to developed topography of patterned systems. Then, the multilayers were annealed in 600 °C in order to obtain FePdCu alloy. The phenomenon of solid-state dewetting resulted in the formation of isolated alloy islands on the top of SiO2 nanoparticles. The SEM and RBS analysis were repeated showing correlation between the size distribution of obtained alloy islands and broadening of peaks appearing in RBS spectra. Invited talk at 8th International Workshop on Advanced Materials Science and Nanotechnology (IWAMSN2016), 8-12 November 2016, Ha Long City, Vietnam.

Hydrodeoxygenation of phenol over zirconia supported Pd bimetallic catalysts. The effect of second metal on catalyst performance

DOE Office of Scientific and Technical Information (OSTI.GOV)

Resende, Karen A.; Teles, Camila A.; Jacobs, Gary

Here, this work investigated the effect of the addition of a second metal (Cu, Ag, Zn, Sn) on the performance of Pd/ZrO 2 catalyst for HDO of phenol at 573 K in the gas phase. The incorporation of dopants resulted in the formation of Pd–X (Cu, Ag, Zn) alloys, which reduced the reaction rate for HDO and increased the selectivity to hydrogenation products (cyclohexanone and cyclohexanol). The lower activity of the bimetallic catalysts was due to the segregation of the second metal on the surface of the Pd particle. For PdSn/ZrO 2, alloying was also observed but tin oxide wasmore » still present on the surface after reduction at 773 K. For Pd and PdSn/ZrO 2, the oxophilic sites represented by Zr and Sn cations promotes the hydrogenation of the carbonyl group of the keto-tautomer intermediate formed, producing benzene as the main product. All catalysts significantly deactivated during the reaction but the deactivation degree depended on the type of the metal. Pd/ZrO 2 and PdZn/ZrO 2 and PdAg/ZrO 2 exhibited approximately the same deactivation degree. However, the loss of activity was less pronounced for PdSn/ZrO2 catalyst. Finally, Pd dispersion significantly decreased during the reaction, indicating that the sintering of Pd particles is one of the causes for catalyst deactivation.« less

Hydrodeoxygenation of phenol over zirconia supported Pd bimetallic catalysts. The effect of second metal on catalyst performance

DOE PAGES

Resende, Karen A.; Teles, Camila A.; Jacobs, Gary; ...

2018-03-21

Here, this work investigated the effect of the addition of a second metal (Cu, Ag, Zn, Sn) on the performance of Pd/ZrO 2 catalyst for HDO of phenol at 573 K in the gas phase. The incorporation of dopants resulted in the formation of Pd–X (Cu, Ag, Zn) alloys, which reduced the reaction rate for HDO and increased the selectivity to hydrogenation products (cyclohexanone and cyclohexanol). The lower activity of the bimetallic catalysts was due to the segregation of the second metal on the surface of the Pd particle. For PdSn/ZrO 2, alloying was also observed but tin oxide wasmore » still present on the surface after reduction at 773 K. For Pd and PdSn/ZrO 2, the oxophilic sites represented by Zr and Sn cations promotes the hydrogenation of the carbonyl group of the keto-tautomer intermediate formed, producing benzene as the main product. All catalysts significantly deactivated during the reaction but the deactivation degree depended on the type of the metal. Pd/ZrO 2 and PdZn/ZrO 2 and PdAg/ZrO 2 exhibited approximately the same deactivation degree. However, the loss of activity was less pronounced for PdSn/ZrO2 catalyst. Finally, Pd dispersion significantly decreased during the reaction, indicating that the sintering of Pd particles is one of the causes for catalyst deactivation.« less

Materials science in pre-plated leadframes for electronic packages

NASA Astrophysics Data System (ADS)

Liu, Lilin

Au/Pd/Ni pre-plated leadframes (PPF) are high performance frames for accommodating high-end electronic packages. Cost and reliability are major concerns in their wide application. The present work, from a materials science point view, deepens the understanding of PPFs, optimizes the conventional PPFs, develops a novel PPF architecture and models the residual stress relaxation in heteroepitaxial thin films. The wire pull test, the solderability test, and High-Resolution Transmission Electron Microscopy (HRTEM) were employed to characterize the PPFs in order to understand the relationship between performance and microstructure. We optimized the electroplating profiles and determined the minimum thickness of the Pd layer with the PPF performance satisfying the industry standards. Further increasing the Pd layer thickness beyond the critical thickness will not enhance the performance more, but increase the product cost. With the optimized electroplating profile, the electroplated Au layer is epitaxially deposited on the Pd layer, and so does the Pd layer on the Ni layer. Misfit dislocations and nanotwins are present at the interface between the Pd and Ni layers, which are generated to release the about 10.4% misfit strain between the Pd and Ni lattices. This work demonstrates that the electro-deposition technique can electroplate epitaxy-like Pd films on the highly (200) textured Ni films, which are grown on the Cu substrates. A novel technique for impeding Cu out-diffusion in Cu alloy based pre-plated leadframes was developed by electroplating a 3-4 nm thick Sn layer on a Cu alloy base prior to electroplating a Ni layer. A 10-14 nm thick epitaxy-like and dense (Cu,Ni)3Sn intermetallic compound (IMC) layer is automatically formed en route of diffuse reaction, which leads to a drastic reduction in Cu out-diffusion and hence improves significantly the protection of the leadframes against oxidation and corrosion attack. The oxidation behaviours were quantified by Electron Diffraction X-ray (EX) incorporated in Scanning Electron Microscopy (SEM) in the present work, which is a good complementary to the traditional weight gain test by a balance. A diffusion/oxidation model was developed to estimate the effective diffusion coefficient of Cu in the formed IMC nanolayers. The estimated Cu diffusion coefficient in the IMC interlayer is about 1.6x10 -22m2/s at 250°C, which is around 7~11 orders lower than the interdiffusion coefficients for eta- Cu6Sn5 and epsilon- Cu3Sn phases at corresponding temperatures. Based on the dislocation theory of twinning, analytical solutions by using the hybrid superposition and Fourier transformation approach were derived for the calculation of various energies involved in the misfit twinning process. For a given epilayer thickness and lattice mismatch strain, the twin formation energy should reach its minimum to determine the twin width and a zero minimum formation energy determines the critical thickness for misfit twinning. The effect of elastic mismatch between the epilayer and the substrate on the critical thickness was studied comprehensively, revealing that an elastically soft epilayer has a large critical thickness. Moreover, a misfit-twin-and-perfect-dislocation predominance chart is constructed to predict the predominant regions of misfit twinning and perfect dislocation in the mismatch strain and the specific twin boundary energy domain. Multiple misfit twins in epilayer/substrate systems were studied by summing up the stress and displacement fields of individual twins. In principle, the energy minimization approach can be applied to multiple misfit twins, although only periodic arrays of parallel and alternating twins were investigated here in detail. The equilibrium twin width and equilibrium twin spacing of a periodic array of twins represent the misfit twin morphology. The theoretical results indicate that the difference in elastic constants between an epilayer and its substrate has great effects on the morphology of equilibrium twins. The theoretical predictions agree with experimental observations.

Deactivation of Pd particles supported on Nb 2O 5/Cu 3Au(1 0 0): SFG and TPD studies from UHV to 100 mbar

NASA Astrophysics Data System (ADS)

Höbel, Frank; Bandara, Athula; Rupprechter, Günther; Freund, Hans-Joachim

2006-02-01

Structural changes that occur on Pd-Nb 2O 5/Cu 3Au(1 0 0) model catalysts upon thermal annealing were followed by sum frequency generation (SFG) and temperature-programmed desorption (TPD) using CO as probe molecule. SFG experiments were performed both under ultrahigh vacuum and mbar pressure. Heating the catalyst to temperatures above 300 K lead to an irreversible 50% decrease in the CO adsorption capacity and modified the remaining adsorption sites. Alterations of the phase between resonant and non-resonant SFG signals upon annealing indicate a change in the electronic structure of the surface, which excludes Pd sintering or migration of Nb 2O 5 over Pd particles to cause the observed effect and rather suggests the formation of "mixed Pd-NbO x" sites. The same changes in surface properties also occur during CO hydrogenation at 1 bar and high temperature, pointing to an involvement of "mixed Pd-NbO x" sites in catalytic reactions.

Gold and palladium minerals (including empirical PdCuBiSe3) from the former Roter Bär mine, St. Andreasberg, Harz Mountains, Germany: a result of low-temperature, oxidising fluid overprint

NASA Astrophysics Data System (ADS)

Cabral, Alexandre Raphael; Ließmann, Wilfried; Lehmann, Bernd

2015-10-01

At Roter Bär, a former underground mine in the polymetallic deposits of St. Andreasberg in the middle-Harz vein district, Germany, native gold and palladium minerals occur very locally in clausthalite-hematite pockets of few millimetres across in carbonate veinlets. The native gold is a Au-Ag intermetallic compound and the palladium minerals are characterised as mertieite-II [Pd8(Sb,As)3] and empirical PdCuBiSe3 with some S. The latter coexists with bohdanowiczite (AgBiSe2), a mineral that is stable below 120 °C. The geological setting of Roter Bär, underneath a post-Variscan unconformity, and its hematite-selenide-gold association suggest that oxidising hydrothermal brines of low temperature were instrumental to the Au-Pd mineralisation. The Roter Bär Au-Pd mineralisation can be explained by Permo-Triassic, red-bed-derived brines in the context of post-Variscan, unconformity-related fluid overprint.

Transformation of Unsaturated Fatty Acids/Esters to Corresponding Keto Fatty Acids/Esters by Aerobic Oxidation with Pd(II)/Lewis Acid Catalyst.

PubMed

Senan, Ahmed M; Zhang, Sicheng; Zeng, Miao; Chen, Zhuqi; Yin, Guochuan

2017-08-16

Utilization of renewable biomass to partly replace the fossil resources in industrial applications has attracted attention due to the limited fossil feedstock with the increased environmental concerns. This work introduced a modified Wacker-type oxidation for transformation of unsaturated fatty acids/esters to the corresponding keto fatty acids/esters, in which Cu 2+ cation was replaced with common nonredox metal ions, that is, a novel Pd(II)/Lewis acid (LA) catalyst. It was found that adding nonredox metal ions can effectively promote Pd(II)-catalyzed oxidation of unsaturated fatty acids/esters to the corresponding keto fatty acids/esters, even much better than Cu 2+ , and the promotional effect is highly dependent on the Lewis acidity of added nonredox metal ions. The improved catalytic efficiency is attributed to the formation of heterobimetallic Pd(II)/LA species, and the oxidation mechanism of this Pd(II)/LA catalyst is also briefly discussed.

n-Hexane hydro-isomerization over promoted Pd/HZSM-5 catalysts

NASA Astrophysics Data System (ADS)

Thoa Dao, Thi Kim; Loc Luu, Cam

2015-09-01

A series of Pd/HZSM-5 catalysts modified by various metallic species, including Co, Ni, Fe, Re, and Cu, was prepared by sequential impregnation. Contents of Pd and second metals in modified catalysts were 0.8 and 1.0 wt%, respectively. Physico-chemical characteristics of catalysts were investigated by nitrogen physi-sorption (BET), x-ray diffraction (XRD), transmission electron microscopy (TEM), ammonia temperature programmed desorption (NH3-TPD), temperature programmed reduction (TPR) and hydrogen pulse chemisorption (HPC). Coke formation was studied by the method of thermogravimetric analysis (TGA). The activities of catalysts in n-hexane isomerization were studied in a micro-flow reactor under atmospheric pressure at 250 °C, and molar ratio of H2: n-hexane of 5.92. It was found that Co, Ni, Fe, and Re additives exhibited geometric and electronic effects toward Pd/HZSM-5 catalyst, leading to an enhancement of its activity and stability. On the contrary, Cu additive caused Pd/HZSM-5 to become poorer in activity and stability.

(E)-α,β-unsaturated amides from tertiary amines, olefins and CO via Pd/Cu-catalyzed aerobic oxidative N-dealkylation.

PubMed

Shi, Renyi; Zhang, Hua; Lu, Lijun; Gan, Pei; Sha, Yuchen; Zhang, Heng; Liu, Qiang; Beller, Matthias; Lei, Aiwen

2015-02-21

A novel Pd/Cu-catalyzed chemoselective aerobic oxidative N-dealkylation/carbonylation reaction has been developed. Tertiary amines are utilized as a "reservoir" of "active" secondary amines in this transformation, which inhibits the formation of undesired by-products and the deactivation of the catalysts. This protocol allows for an efficient and straightforward construction of synthetically useful and bioactive (E)-α,β-unsaturated amide derivatives from easily available tertiary amines, olefins and CO.

A GREEN CHEMISTRY APPROACH TO PREPARATION OF CORE (FE OR CU)-SHELL (NOBLE METALS) NANOCOMPOSITES USING AQUEOUS ASCORBIC ACID

EPA Science Inventory

A greener method to fabricate novel core (Fe or Cu)-shell (noble metals) nanocomposites of transition metals such as Fe and Cu and noble metals such as Au, Pt, Pd, and Ag using aqueous ascorbic acid is described. Transition metal salts such as Cu and Fe were reduced using ascor...

Precious metal enrichment at low-redox in terrestrial native Fe-bearing basalts investigated using laser-ablation ICP-MS

NASA Astrophysics Data System (ADS)

Howarth, Geoffrey H.; Day, James M. D.; Pernet-Fisher, John F.; Goodrich, Cyrena A.; Pearson, D. Graham; Luo, Yan; Ryabov, Viktor V.; Taylor, Lawrence A.

2017-04-01

Primary native Fe is a rare crystallizing phase from terrestrial basaltic magmas, requiring highly reducing conditions (fO2

Characterization of aqueous interactions of copper-doped phosphate-based glasses by vapour sorption.

PubMed

Stähli, Christoph; Shah Mohammadi, Maziar; Waters, Kristian E; Nazhat, Showan N

2014-07-01

Owing to their adjustable dissolution properties, phosphate-based glasses (PGs) are promising materials for the controlled release of bioinorganics, such as copper ions. This study describes a vapour sorption method that allowed for the investigation of the kinetics and mechanisms of aqueous interactions of PGs of the formulation 50P2O5-30CaO-(20-x)Na2O-xCuO (x=0, 1, 5 and 10mol.%). Initial characterization was performed using (31)P magic angle spinning nuclear magnetic resonance and attenuated total reflectance-Fourier transform infrared spectroscopy. Increasing CuO content resulted in chemical shifts of the predominant Q(2) NMR peak and of the (POP)as and (PO(-)) Fourier transform infrared absorptions, owing to the higher strength of the POCu bond compared to PONa. Vapour sorption and desorption were gravimetrically measured in PG powders exposed to variable relative humidity (RH). Sorption was negligible below 70% RH and increased exponentially with RH from 70 to 90%, where it exhibited a negative correlation with CuO content. Vapour sorption in 0% and 1% CuO glasses resulted in phosphate chain hydration and hydrolysis, as evidenced by protonated Q(0)(1H) and Q(1)(1H) species. Dissolution rates in deionized water showed a linear correlation (R(2)>0.99) with vapour sorption. Furthermore, cation release rates could be predicted based on dissolution rates and PG composition. The release of orthophosphate and short polyphosphate species corroborates the action of hydrolysis and was correlated with pH changes. In conclusion, the agreement between vapour sorption and routine characterization techniques in water demonstrates the potential of this method for the study of PG aqueous reactions. Copyright © 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Siderophile trace element diffusion in Fe-Ni alloys

NASA Astrophysics Data System (ADS)

Watson, Heather C.; Watson, E. Bruce

2003-09-01

Experiments were performed in a piston cylinder apparatus to characterize the diffusion behavior of the siderophile elements, Mo, Cu, Pd, Au, and Re in solid Fe-Ni alloy (90 wt.% Fe, 10 wt.% Ni). All experiments were conducted at 1 GPa and temperatures ranging from 1175 to 1400 °C. Activation energies of all elements fall between 270 kJ/mol (Cu) and 360 kJ/mol (Mo). Mo, Cu, Pd, and Au all show similar diffusivities at the same conditions, but the diffusivity of Re was consistently close to an order of magnitude lower. Initial experiments on other refractory elements (Os, Pt, and Ir) indicate that their diffusivities are close to or slightly lower than that of Re.

Feasibility Studies of Parametric X-rays Use in a Medical Environment

NASA Astrophysics Data System (ADS)

Sones, Bryndol; Danon, Yaron; Blain, Ezekiel

2009-03-01

Parametric X-rays (PXR) are produced from the interaction of relativistic electrons with the periodic structure of crystal materials. Smooth X-ray energy tunability is achieved by rotating the crystal with respects to the electron beam direction. Experiments at the Rensselaer Polytechnic Institute 60-MeV LINAC produce quasi-monochromatic X-rays (6-35 keV) from various target crystals to include highly oriented pyrolytic graphite (HOPG), LiF, Si, Ge, Cu, and W using electron beam currents up to 6 uA. These experiments demonstrate the first PXR images and some of the merits of thin metallic crystals. Recent experiments with a 100-μm thick Cu crystal improve the Cu PXR (with energy ˜12 keV) to Cu fluorescence ratio by a factor of 20 compared to a 1 mm-thick Cu crystal. This study uses Monte Carlo techniques to investigate (1) PXR dose compared to emissions from simulated Mo, Rh, and W anodes for mammography applications and (2) electron scattering effects when considering LiF111, Si111, and Cu111 PXR production using electron beams with energies of 20-30 MeV. Advantages in using monochromatic PXR compared to X-rays from Mo and Rh anodes in mammography applications result in a dose per incident photon reduction by a factor of 2. Using 20 MeV electrons, the thinner Cu111 crystal for 15 keV PXR production results in an electron scattering angle of 30.7+/-0.2 mrad offering the best potential for PXR from lower energy electrons.

Moisture barrier properties of single-layer graphene deposited on Cu films for Cu metallization

NASA Astrophysics Data System (ADS)

Gomasang, Ploybussara; Abe, Takumi; Kawahara, Kenji; Wasai, Yoko; Nabatova-Gabain, Nataliya; Thanh Cuong, Nguyen; Ago, Hiroki; Okada, Susumu; Ueno, Kazuyoshi

2018-04-01

The moisture barrier properties of large-grain single-layer graphene (SLG) deposited on a Cu(111)/sapphire substrate are demonstrated by comparing with the bare Cu(111) surface under an accelerated degradation test (ADT) at 85 °C and 85% relative humidity (RH) for various durations. The change in surface color and the formation of Cu oxide are investigated by optical microscopy (OM) and X-ray photoelectron spectroscopy (XPS), respectively. First-principle simulation is performed to understand the mechanisms underlying the barrier properties of SLG against O diffusion. The correlation between Cu oxide thickness and SLG quality are also analyzed by spectroscopic ellipsometry (SE) measured on a non-uniform SLG film. SLG with large grains shows high performance in preventing the Cu oxidation due to moisture during ADT.

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

PubMed Central

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

2014-01-01

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

Effects of Chloride and Sulfate Salts on the Inhibition or Promotion of Sucrose Crystallization in Initially Amorphous Sucrose-Salt Blends.

PubMed

Thorat, Alpana A; Forny, Laurent; Meunier, Vincent; Taylor, Lynne S; Mauer, Lisa J

2017-12-27

The effects of salts on the stability of amorphous sucrose and its crystallization in different environments were investigated. Chloride (LiCl, NaCl, KCl, MgCl 2 , CaCl 2 , CuCl 2 , FeCl 2 , FeCl 3 , and AlCl 3 ) and sulfate salts with the same cations (Na 2 SO 4 , K 2 SO 4 , MgSO 4 , CuSO 4 , Fe(II)SO 4 , and Fe(III)SO 4 ) were studied. Samples (sucrose controls and sucrose:salt 1:0.1 molar ratios) were lyophilized, stored in controlled temperature and relative humidity (RH) conditions, and monitored for one month using X-ray diffraction. Samples were also analyzed by differential scanning calorimetry, microscopy, and moisture sorption techniques. All lyophiles were initially amorphous, but during storage the presence of a salt had a variable impact on sucrose crystallization. While all samples remained amorphous when stored at 11 and 23% RH at 25 °C, increasing the RH to 33 and 40% RH resulted in variations in crystallization onset times. The recrystallization time generally followed the order monovalent cations < sucrose < divalent cations < trivalent cations. The presence of a salt typically increased water sorption as compared to sucrose alone when stored at the same RH; however, anticrystallization effects were observed for sucrose combined with salts containing di- and trivalent cations in spite of the increased water content. The cation valency and hydration number played a major role in dictating the impact of the added salt on sucrose crystallization.

COST-EFFECTIVE METHOD FOR PRODUCING SELF SUPPORTED PALLADIUM ALLOY MEMBRANES FOR USE IN EFFICIENT PRODUCTION OF COAL DERIVED HYDROGEN

DOE Office of Scientific and Technical Information (OSTI.GOV)

B. Lanning; J. Arps

2004-04-01

Extending upon development efforts last quarter to produce ''free-standing'', copper and palladium alloy films, the goal this quarter has been to produce pinhole-free, Pd-Cu alloy films up to 5 x 5 inches in area (1-3 microns thick) using both magnetron sputtering and e-beam evaporation on PVA (Solublon) and polystyrene backing materials. A set of experiments were conducted to assess processing methods/solutions chemistry for removing the polymer backing material from the Pd-Cu film. For all of the alloy films produced to this point, we were unable to produce pinhole-free films on plastic although we were able to produce free-standing Pd-Cu filmsmore » at less than 0.5 microns thick with minimal intrinsic stress. Subsequently, to evaluate gas permeation and leakage across the films, two films were sandwiched together on top of a porous Monel support disc (25 mm in diameter) and then tested in a leak test apparatus. Using two Cu films (10 micron thickness total) in the sandwich configuration, leak rates were about 20% of the background leak rate.« less

Polymer-supported CuPd nanoalloy as a synergistic catalyst for electrocatalytic reduction of carbon dioxide to methane

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Sheng; Kang, Peng; Bakir, Mohammed

2015-12-14

Developing sustainable energy strategies based on CO2 reduction is an increasingly important issue given the world’s continued reliance on hydrocarbon fuels and the rise in CO2 concentrations in the atmosphere. An important option is electrochemical or photoelectrochemical CO2 reduction to carbon fuels. We describe here an electrodeposition strategy for preparing highly dispersed, ultrafine metal nanoparticle catalysts on an electroactive polymeric film including nanoalloys of Cu and Pd. Compared with nanoCu catalysts, which are state-of-the-art catalysts for CO2 reduction to hydrocarbons, the bimetallic CuPd nanoalloy catalyst exhibits a greater than twofold enhancement in Faradaic efficiency for CO2 reduction to methane. Themore » origin of the enhancement is suggested to arise from a synergistic reactivity interplay between Pd–H sites and Cu–CO sites during electrochemical CO2 reduction. The polymer substrate also appears to provide a basis for the local concentration of CO2 resulting in the enhancement of catalytic current densities by threefold. The procedure for preparation of the nanoalloy catalyst is straightforward and appears to be generally applicable to the preparation of catalytic electrodes for incorporation into electrolysis devices.« less

Highly reusability surface loaded metal particles magnetic catalyst microspheres (MCM-MPs) for treatment of dye-contaminated water

NASA Astrophysics Data System (ADS)

Liu, Ying; Zhang, Kun; Yin, Xiaoshuang; Yang, Wenzhong; Zhu, Hongjun

2016-04-01

The metal-deposited magnetic catalyst microspheres (MCM-MPs) were successfully synthesized by one facile, high yield and controllable approach. Here, the bare magnetic microspheres were firstly synthesized according to the solvothermal method. Then silica shell were coated on the surface of the magnetic microspheres via sol-gel method, and subsequently with surface modifying with amino in the purpose to form SiO2-NH2 shell. Thus, metal particles were easily adsorbed into the SiO2-NH2 shell and in-situ reduced by NaBH4 solution. All the obtained products (MCM-Cu, MCM-Ag, MCM-Pd) which were monodisperse and constitutionally stable were exhibited high magnetization and excellent catalytic activity towards dyes solution reduction. The catalytic rate ratio of MCM-Pd: MCM-Cu: MCM-Ag could be 10:3:1. Besides, some special coordination compound Cu2(OH)3Br had been generated in the in-situ reduced process of MCM-Cu, which produced superior cyclical stability (>20 times) than that of MCM-Ag and MCM-Pd. In all, those highly reusability and great catalytic efficiency of MCM-MPs show promising and great potential for treatment of dye-contaminated water.

Analysis of pulsed-neutron powder diffraction patterns of the icosahedral quasicrystals Pd3Siu and AlCuLiMg (three alloys) as twinned cubic crystals with large units.

PubMed Central

Pauling, L

1991-01-01

The low-Q peaks on three pulsed-neutron powder patterns (total, U differential, and Pd differential) of the icosahedral quasicrystal Pd3SiU have been indexed on the basis of an assumed cubic structure of the crystals that by icosahedral twinning form the quasicrystal. The primitive unit cube is found to have edge length 56.20 A and to contain approximately 12,100 atoms. Similar analyses of pulsed-neutron patterns of Al55Cu10Li35, Al55Cu10Li30Mg5, and Al510Cu125Li235Mg130 give values of the cube edge length 58.3, 58.5, and 58.4 A, respectively, with approximately 11,650 atoms in the unit cube. It is suggested that the unit contains eight complexes in the beta-W positions, plus some small interstitial groups of atoms, with each complex consisting of a centered icosahedron of 13 clusters, each of 116 atoms with the icosahedral structure found in the body-centered cubic crystal Mg32(Al,Zn)49. PMID:11607201

Analysis of pulsed-neutron powder diffraction patterns of the icosahedral quasicrystals Pd3Siu and AlCuLiMg (three alloys) as twinned cubic crystals with large units.

PubMed

Pauling, L

1991-08-01

The low-Q peaks on three pulsed-neutron powder patterns (total, U differential, and Pd differential) of the icosahedral quasicrystal Pd3SiU have been indexed on the basis of an assumed cubic structure of the crystals that by icosahedral twinning form the quasicrystal. The primitive unit cube is found to have edge length 56.20 A and to contain approximately 12,100 atoms. Similar analyses of pulsed-neutron patterns of Al55Cu10Li35, Al55Cu10Li30Mg5, and Al510Cu125Li235Mg130 give values of the cube edge length 58.3, 58.5, and 58.4 A, respectively, with approximately 11,650 atoms in the unit cube. It is suggested that the unit contains eight complexes in the beta-W positions, plus some small interstitial groups of atoms, with each complex consisting of a centered icosahedron of 13 clusters, each of 116 atoms with the icosahedral structure found in the body-centered cubic crystal Mg32(Al,Zn)49.

Polymer-supported CuPd nanoalloy as a synergistic catalyst for electrocatalytic reduction of carbon dioxide to methane

PubMed Central

Zhang, Sheng; Kang, Peng; Bakir, Mohammed; Lapides, Alexander M.; Dares, Christopher J.; Meyer, Thomas J.

2015-01-01

Developing sustainable energy strategies based on CO2 reduction is an increasingly important issue given the world’s continued reliance on hydrocarbon fuels and the rise in CO2 concentrations in the atmosphere. An important option is electrochemical or photoelectrochemical CO2 reduction to carbon fuels. We describe here an electrodeposition strategy for preparing highly dispersed, ultrafine metal nanoparticle catalysts on an electroactive polymeric film including nanoalloys of Cu and Pd. Compared with nanoCu catalysts, which are state-of-the-art catalysts for CO2 reduction to hydrocarbons, the bimetallic CuPd nanoalloy catalyst exhibits a greater than twofold enhancement in Faradaic efficiency for CO2 reduction to methane. The origin of the enhancement is suggested to arise from a synergistic reactivity interplay between Pd–H sites and Cu–CO sites during electrochemical CO2 reduction. The polymer substrate also appears to provide a basis for the local concentration of CO2 resulting in the enhancement of catalytic current densities by threefold. The procedure for preparation of the nanoalloy catalyst is straightforward and appears to be generally applicable to the preparation of catalytic electrodes for incorporation into electrolysis devices. PMID:26668386

Platinum group elements and gold in ferromanganese crusts from Afanasiy-Nikitin seamount, equatorial Indian Ocean: Sources and fractionation

USGS Publications Warehouse

Banakar, V.K.; Hein, J.R.; Rajani, R.P.; Chodankar, A.R.

2007-01-01

The major element relationships in ferromanganese (Fe-Mn) crusts from Afanasiy-Nikitin seamount (ANS), eastern equatorial Indian Ocean, appear to be atypical. High positive correlations (r = 0.99) between Mn/Co and Fe/Co ratios, and lack of correlation of those ratios with Co, Ce, and Ce/Co, indicate that the ANS Fe-Mn crusts are distinct from Pacific seamount Fe-Mn crusts, and reflect region-specific chemical characteristics. The platinum group elements (PGE: Ir, Ru, Rh, Pt, and Pd) and Au in ANS Fe-Mn crusts are derived from seawater and are mainly of terrestrial origin, with a minor cosmogenic component. The Ru/Rh (0.5-2) and Pt/Ru ratios (7-28) are closely comparable to ratios in continental basalts, whereas Pd/Ir ratios exhibit values ( 0.75) correlations between water depth and Mn/Co, Fe/Co, Ce/Co, Co, and the PGEs. Fractionation of the PGE-Au from seawater during colloidal precipitation of the major-oxide phases is indicated by well-defined linear positive correlations (r > 0.8) of Co and Ce with Ir, Ru, Rh, and Pt; Au/Co with Mn/Co; and by weak or no correlations of Pd with water depth, Co-normalized major-element ratios, and with the other PGE (r < 0.5). The strong enrichment of Pt (up to 1 ppm) relative to the other PGE and its positive correlations with Ce and Co demonstrate a common link for the high concentrations of all three elements, which likely involves an oxidation reaction on the Mn-oxide and Fe-oxyhydroxide surfaces. The documented fractionation of PGE-Au and their positive association with redox sensitive Co and Ce may have applications in reconstructing past-ocean redox conditions and water masses.

Production of Oxidation-Resistant Cu-Based Nanoparticles by Wire Explosion

PubMed Central

Kawamura, Go; Alvarez, Samuel; Stewart, Ian E.; Catenacci, Matthew; Chen, Zuofeng; Ha, Yoon-Cheol

2015-01-01

The low performance or high cost of commercially available conductive inks limits the advancement of printed electronics. This article studies the explosion of metal wires in aqueous solutions as a simple, low-cost, and environmentally friendly method to prepare metallic nanoparticles consisting of Cu and Cu alloys for use in affordable, highly conductive inks. Addition of 0.2 M ascorbic acid to an aqueous explosion medium prevented the formation of Cu2O shells around Cu nanoparticles, and allowed for the printing of conductive lines directly from these nanoparticles with no post-treatment. Cu alloy nanoparticles were generated from metal wires that were alloyed as purchased, or from two wires of different metals that were twisted together. Cu nanoparticles alloyed with 1% Sn, 5% Ag, 5% Ni and 30% Ni had electrical conductivities similar to Cu but unlike Cu, remained conductive after 24 hrs at 85 °C and 85% RH. PMID:26669447

Photochemical Fabrication of Transition Metal Nanoparticles Using CdS Template and Their Co-Catalysis Effects for TiO2 Photocatalysis

NASA Astrophysics Data System (ADS)

Badhwar, Nidhi; Gupta, Nidhi; Pal, Bonamali

2013-09-01

Transition metal nanoparticles were prepared by chemical dissolution of CdS template from metal photodeposited CdS nanorod (length = 70-85 nm and width = 5-6 nm) heterocomposites. Size (9-10 nm) of metal nanoparticles obtained after CdS removal was larger than the size (4-6 nm) of metal nanodeposits over CdS template. The obtained Au nanoparticles displayed a broad red shifted absorption band at 660 nm, whereas Pt, Pd and Rh nanoparticles exhibit featureless absorption spectra. Elemental analysis confirms the complete removal of CdS template from Au-CdS (Au — 2.65 at.%) and Ag-CdS (Ag — 2.06 at.%) composites showing no Cd peak. These metal nanoparticles imparted dissimilar co-catalytic activity of TiO2 for photocatalytic degradation of salicylic acid in the order Au > Pt > Pd > Ag > Rh as a function of their nature, electronegativity, redox potential and work function.

Platinum-group element geochemistry of zoned ultramafic intrusive suites, Klamath Mountains, California and Oregon.

USGS Publications Warehouse

Gray, F.; Page, N.J.; Carlson, C.A.; Wilson, S.A.; Carlson, R.R.

1986-01-01

Analyses for platinum-group elements of the varied rock suites of three Alaskan-type ultramafic to mafic multi-intrusive bodies are reported. Ir and Ru are less than analytical sensitivities of 100 and 20 ppb; Rh is less than or near 1 ppb. Average Pd assays vary among the rocks within intrusive complexes and between the three complexes (6.3, 13.7, 36.4 ppb); average Pt assays vary little among the same samples (27.9, 60.9, 34.0 ppb). Statistically adjusted Pt/(Pt + Pd) ratios increase in each suite from gabbro through clinopyroxenite to olivine-rich rocks, possibly owing to Pd fractionation.-G.J.N.

CuO-induced signal amplification strategy for multiplexed photoelectrochemical immunosensing using CdS sensitized ZnO nanotubes arrays as photoactive material and AuPd alloy nanoparticles as electron sink.

PubMed

Sun, Guoqiang; Zhang, Yan; Kong, Qingkun; Zheng, Xiaoxiao; Yu, Jinghua; Song, Xianrang

2015-04-15

In this work, multiplexed photoelectrochemical (PEC) immunoassays are introduced into an indium tin oxide (ITO) device. Firstly, the ITO device is fabricated using a simple acid etch treatment method. Secondly, AuPd alloy nanoparticles are electro-deposited on ITO working electrodes as electron sink to construct the immunosensor platform. After that, ZnO nanotubes (ZNTs) arrays are synthesized via chemical etching of ZnO nanorods that are grown on AuPd surface by electrochemical deposition method. Subsequently, CdS is electro-deposited on ZNTs arrays and used as photoactive material. Then, CuO nanoseeds are labeled with signal antibodies and firstly used as PEC signal amplification label. The introduction of CuO brings signal amplification because of the conduction band (CB) of both CuO and ZnO are lower than that of CdS, CuO will compete the photo-induced electrons in CB of CdS with ZnO, leading to the decrease of the photocurrent intensity. Using cancer antigen 125, prostate specific antigen and α-fetoprotein as model analytes, the proposed immunoassay exhibits excellent precision and sensitivity. Meanwhile, this work provides a promising, addressable and simple strategy for the multi-detection of tumor markers. Copyright © 2014 Elsevier B.V. All rights reserved.

Generalized stacking fault energies of alloys.

PubMed

Li, Wei; Lu, Song; Hu, Qing-Miao; Kwon, Se Kyun; Johansson, Börje; Vitos, Levente

2014-07-02

The generalized stacking fault energy (γ surface) provides fundamental physics for understanding the plastic deformation mechanisms. Using the ab initio exact muffin-tin orbitals method in combination with the coherent potential approximation, we calculate the γ surface for the disordered Cu-Al, Cu-Zn, Cu-Ga, Cu-Ni, Pd-Ag and Pd-Au alloys. Studying the effect of segregation of the solute to the stacking fault planes shows that only the local chemical composition affects the γ surface. The calculated alloying trends are discussed using the electronic band structure of the base and distorted alloys.Based on our γ surface results, we demonstrate that the previous revealed 'universal scaling law' between the intrinsic energy barriers (IEBs) is well obeyed in random solid solutions. This greatly simplifies the calculations of the twinning measure parameters or the critical twinning stress. Adopting two twinnability measure parameters derived from the IEBs, we find that in binary Cu alloys, Al, Zn and Ga increase the twinnability, while Ni decreases it. Aluminum and gallium yield similar effects on the twinnability.

A GREENER SYNTHESIS OF CORE (FE, CU)-SHELL (AU, PT, PD AND AG) NANOCRYSTALS USING AQUEOUS VITAMIN C

EPA Science Inventory

A greener method to fabricate the novel core (Fe and Cu)-shell (noble metals) metal nanocrystals using aqueous ascorbic acid (vitamin C) is described. Transition metal salts such as Cu and Fe were reduced using ascorbic acid, a benign naturally available antioxidant, and then add...

Synergistic effect of rice husk addition on hydrothermal treatment of sewage sludge: fate and environmental risk of heavy metals.

PubMed

Shi, Wansheng; Liu, Chunguang; Shu, Youju; Feng, Chuanping; Lei, Zhongfang; Zhang, Zhenya

2013-12-01

Hydrothermal treatment (HTT) at 200°C was applied to immobilize heavy metals (HMs) and the effect of rice husk (RH) addition was investigated based on total HMs concentration, fractionation and leaching tests. The results indicated that a synergistic effect of RH addition and HTT could be achieved on reducing the risk of HMs from medium and low risk to no risk. Metals were redistributed and transformed from weakly bounded state to stable state during the HTT process under RH addition. Notably at a RH/sludge ratio of 1/1.75 (d.w.), all the HMs showed no eco-toxicity and no leaching toxicity, with the concentrations of leachable Cr, Ni, Cu and Cd decreased by 17%, 89%, 95% and 93%, respectively. This synergistic effect of RH addition and HTT on the risk reduction of HMs implies that HTT process with RH addition could be a promising and safe disposal technology for sewage sludge treatment in practice. Copyright © 2013 Elsevier Ltd. All rights reserved.

Crystal structure, complexation, spectroscopic characterization and antimicrobial evaluation of 3,4-dihydroxybenzylidene isonicotinyl-hydrazone

NASA Astrophysics Data System (ADS)

Jeragh, Bakir; Ali, Mayada S.; El-Asmy, Ahmed A.

2015-06-01

A single crystal of 3,4-dihydroxybenzylidene isonicotinylhydrazone, HBINH, has been grown and solved by X-ray crystallography. The VO2+, Zr4+, Co2+, Ni2+, Cu2+, Zn2+, Cd2+, Hg2+ and Pd2+ complexes of HBINH have been prepared and spectroscopically characterized. The data confirmed the formulae [Co(HBINH)(H2O)Cl]Cl·H2O, [Pd(HBINH)Cl2], [Zn(HBINH)2Cl2], [Cd(HBINH)(H2O)2Cl2]·1½H2O, [(VO)2(HBINH-3H)(OH)(H2O)], [Ni2(HBINH)(H2O)6Cl2]Cl2, [Cu2(HBINH-3H)(H2O)2(OAc)]·3H2O, [Zr2(HBINH-3H)Cl4]Cl, [Hg2(HBINH)Cl4] and the dimer {[Cu(HBINH)Cl]Cl}2. Most of the complexes have intense colors and high melting points and some are electrolytes in DMSO solution. The ligand behaves as a neutral bidentate in the Co(II), Cu(II), Pd(II), Zn(II) and Cd(II) complexes; dibasic tetradentate in [Ni2(HBINH)(H2O)6Cl2]Cl2 and tribasic tetradentate in [Cu2(HBINH-3H)(OAc)]·5H2O, [(VO)2(HBINH-3H)(OH)(H2O)] and [Zr2(HBINH-3H)Cl4]Cl by the loss of 3H+ due to the deprotonation of the two hydroxyl groups and the enolization of the amide (Odbnd CNH) group. A tetrahedral geometry was proposed for the Co(II), Cu(II), Zn(II) and Hg(II) complexes; square-planar for the Pd(II) complex; square-pyramid for the VO2+ complex and octahedral for the Ni(II) and Cd(II) complexes. The complexes [Cd(HBINH)(H2O)2Cl2]·1½H2O, [(VO)2(HBINH-3H)(OH)(H2O)] and [Cu2(HBINH-3H)-(H2O)2(OAc)]·3H2O have activities against Bacillus sp. M3010, Candida albicans, Escherichia coli, Staphylococcus aureus and Slamonella sp. PA393.

Investigation of the physical properties of two Laves phase compounds HRh2 (H = Ca and La): A DFT study

NASA Astrophysics Data System (ADS)

Rahaman, Md. Zahidur; Rahman, Md. Atikur

2018-05-01

By using the first-principle calculations, the structural, elastic, electronic and optical properties of Laves phase intermetallic compounds CaRh2 and LaRh2 prototype with MgCu2 are investigated. The evaluated lattice parameters are consistent with the experimental values. The important elastic properties, such as bulk modulus B, shear modulus G, Young’s modulus Y and the Poisson’s ratio v, are computed by applying the Voigt-Reuss-Hill (VRH) approximation. The analysis of Pugh’s ratio exhibits the ductile nature of both the phases. Electronic conductivity is predicted for both the compounds. Most of the contribution comes from Rh-4d states. The study of bonding characteristics reveals the existence of ionic and metallic bonds in both intermetallics. The study of optical properties indicates that CaRh2 is a better dielectric material than LaRh2. Absorption quality of both the phases is good in the ultraviolet region.

Supramolecular self-assembly of heterobimetallic complexes: a new N,P-based, selective heteroditopic ligand.

PubMed

Hutchinson, Daniel John; Clauss, Reike; Sárosi, Menyhárt-Botond; Hey-Hawkins, Evamarie

2018-01-23

Pyrimidine-hydrazone and phosphole architectures have been combined to create a new heteroditopic ligand capable of forming heterobimetallic Zn II /Pd II , Pb II /Pd II and Cu II /Pd II complexes in high yielding stepwise or one pot reactions. The catalytic activity of these complexes in Heck coupling and Miyaura borylation reactions was investigated.

Green synthesis of Pd/CuO nanoparticles by Theobroma cacao L. seeds extract and their catalytic performance for the reduction of 4-nitrophenol and phosphine-free Heck coupling reaction under aerobic conditions.

PubMed

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

2015-06-15

We report the green synthesis of palladium/CuO nanoparticles (Pd/CuO NPs) using Theobroma cacao L. seeds extract and their catalytic activity for the reduction of 4-nitrophenol and Heck coupling reaction under aerobic conditions. The catalyst was characterized using the powder XRD, TEM, EDS, UV-vis and FT-IR. This method has the advantages of high yields, elimination of surfactant, ligand and homogeneous catalysts, simple methodology and easy work up. The catalyst can be recovered from the reaction mixture and reused several times without any significant loss of catalytic activity. Copyright © 2015 Elsevier Inc. All rights reserved.

Highly recyclable and ultra-rapid catalytic reduction of organic pollutants on Ag-Cu@ZnO bimetal nanocomposite synthesized via green technology

NASA Astrophysics Data System (ADS)

Gangarapu, Manjari; Sarangapany, Saran; Suja, Devipriya P.; Arava, Vijaya Bhaskara Rao

2018-04-01

In this study, synthesis of Ag-Cu alloy bimetal nanoparticles anchored on high surface and porous ZnO using a facile, greener and low-cost aqeous bark extract of Aglaia roxburghiana for highly active, ultra-rapid and stable catalyst is performed. The nanocomposite was scrupulously characterized using UV-Vis spectrophotometer, X-ray diffraction, Raman spectrophotometer, high-resolution transmission electron microscope, selected area (electron) diffraction, scanning electron microscope with energy dispersive X-ray spectroscopy, and Fourier-transform infrared spectroscopy. The catalytic activity of the green synthesized Ag-Cu bimetal nanocomposite was evaluated in the reduction of 4-nitrophenol (4-NP), methylene blue (MB) and rhodamine B (Rh B) dyes. The different types of dye exhibited very high and effective catalytic activity within few seconds. The theoretical investigations reveal that the unique synergistic effect of Ag-Cu nanoparticles and immobilization over ZnO assists in the reduction of 4-NP, MB and Rh B. Loading and leaching of metal nanoparticles were obtained using inductively coupled plasma atomic emission spectroscopy. Moreover, the stable and efficient recyclability of nanocomposite by centrifugation after completion of the reaction was demonstrated. The results lead to the design different possible bimetal on ZnO with boosting and an effective catalyst for the environmental applications.

Ultra-low power hydrogen sensing based on a palladium-coated nanomechanical beam resonator

NASA Astrophysics Data System (ADS)

Henriksson, Jonas; Villanueva, Luis Guillermo; Brugger, Juergen

2012-07-01

Hydrogen sensing is essential to ensure safety in near-future zero-emission fuel cell powered vehicles. Here, we present a novel hydrogen sensor based on the resonant frequency change of a nanoelectromechanical clamped-clamped beam. The beam is coated with a Pd layer, which expands in the presence of H2, therefore generating a stress build-up that causes the frequency of the device to drop. The devices are able to detect H2 concentrations below 0.5% within 1 s of the onset of the exposure using only a few hundreds of pW of power, matching the industry requirements for H2 safety sensors. In addition, we investigate the strongly detrimental effect that relative humidity (RH) has on the Pd responsivity to H2, showing that the response is almost nullified at about 70% RH. As a remedy for this intrinsic limitation, we applied a mild heating current through the beam, generating a few μW of power, whereby the responsivity of the sensors is fully restored and the chemo-mechanical process is accelerated, significantly decreasing response times. The sensors are fabricated using standard processes, facilitating their eventual mass-production.Hydrogen sensing is essential to ensure safety in near-future zero-emission fuel cell powered vehicles. Here, we present a novel hydrogen sensor based on the resonant frequency change of a nanoelectromechanical clamped-clamped beam. The beam is coated with a Pd layer, which expands in the presence of H2, therefore generating a stress build-up that causes the frequency of the device to drop. The devices are able to detect H2 concentrations below 0.5% within 1 s of the onset of the exposure using only a few hundreds of pW of power, matching the industry requirements for H2 safety sensors. In addition, we investigate the strongly detrimental effect that relative humidity (RH) has on the Pd responsivity to H2, showing that the response is almost nullified at about 70% RH. As a remedy for this intrinsic limitation, we applied a mild heating current through the beam, generating a few μW of power, whereby the responsivity of the sensors is fully restored and the chemo-mechanical process is accelerated, significantly decreasing response times. The sensors are fabricated using standard processes, facilitating their eventual mass-production. Electronic supplementary information (ESI) available. See DOI: 10.1039/c2nr30639e

First principles studies of the dependence of magnetism on the crystal phase in 4d and 5d late transition metals

NASA Astrophysics Data System (ADS)

Hüger, E.; Osuch, K.

2005-03-01

We investigate the possibility of inducing ferromagnetic order in 4d and 5d late transition metals through crystal symmetry change. First principles, self-consistent density functional theory calculations, with spin-orbit coupling included, performed at 0 K show that ferromagnetism occurs in the bulk of Rh and Pd at the optimum lattice constant if Rh is in the bcc and Pd in the hcp/dhcp phase. The ferromagnetic order originates in the d-band occupancy of Rh or Pd which locates the Fermi energy at the top of the highest peak of the respective (paramagnetic) density of states induced by the bcc or hcp/dhcp structure. This peak in the density of states is caused by flat bands which lie at the surface of the respective Brillouin zone. For a bcc crystal these flat bands have the eg character and are positioned at the surface of the bcc Brillouin zone along the N-P line. The origin of the flatness of the bands was found to be the translation symmetry of the cubic lattice which causes the bands with the eg character to be narrow along the k-lines whose k-vector directions are furthest off the directions to which the orbitals of the eg symmetry point. Due to the d-band occupancy of Rh these flat bands lie in the paramagnetic state at the Fermi energy, whereas in the ferromagnetic state they exhibit the largest energetic split. This indicates that a smaller degree of orbital overlap narrows electronic bands enhancing the tendency of the system for ferromagnetic band split. For the hcp/dhcp structure the states contributing to the high density of para-magnetic states at the Fermi level of Pd lie in the vicinity of the M-L line of the hcp Brillouin zone boundary, which possesses a high number of symmetry (M and L) points. Moreover, the M-L line is aligned with the stacking sequence direction ([0001]) which is furthest off the densest-packed atomic chain direction of an hcp-crystal and, consequently, the weakest-bond direction in the crystal. This makes the narrow bands along the M-L line flat. The instability of the bcc and the meta-stability of the hcp crystal phase modifications for metals with native close-packed crystal structures is subsequently analysed in order to find whether they can be grown as films on suitable substrates.

Facile synthesis of polyaniline-modified CuS with enhanced adsorbtion and photocatalytic activity

NASA Astrophysics Data System (ADS)

Wang, Xiufang; Chen, Shaohua; Shuai, Ying

2016-10-01

Novel hierarchical polyaniline-modified CuS (PANI-CuS) has been synthesized by simple assembling PANI on the surface of flower-like CuS spheres. The PANI modification enhances the adsorption properties of flower-like CuS. The prepared PANI-CuS composites exhibit higher visible-light-driven photocatalytic activities in degradation of rhodamine B (RhB) than that of neat CuS. The unusual photocatalytic activity could be attributed to the great adsorptivity of dyes, the extended photoresponse range, and the high migration efficiency of photoinduced electrons, which may effectively suppress the charge recombination. This work not only provides a simple strategy for fabricating highly efficient and stable CuS-based composites, but also proves that these unique structures are excellent platforms for significantly improving their visible- light-driven photoactivities, holding great promise for their applications in the field of purifying polluted water resources.

Understanding of catalyst deactivation caused by sulfur poisoning and carbon deposition in steam reforming of liquid hydrocarbon fuels

NASA Astrophysics Data System (ADS)

Xie, Chao

2011-12-01

The present work was conducted to develop a better understanding on the catalyst deactivation in steam reforming of sulfur-containing liquid hydrocarbon fuels for hydrogen production. Steam reforming of Norpar13 (a liquid hydrocarbon fuel from Exxon Mobile) without and with sulfur was performed on various metal catalysts (Rh, Ru, Pt, Pd, and Ni) supported on different materials (Al2O3, CeO2, SiO2, MgO, and CeO2- Al2O3). A number of characterization techniques were applied to study the physicochemical properties of these catalysts before and after the reactions. Especially, X-ray absorption near edge structure (XANES) spectroscopy was intensively used to investigate the nature of sulfur and carbon species in the used catalysts to reveal the catalyst deactivation mechanism. Among the tested noble metal catalysts (Rh, Ru, Pt, and Pd), Rh catalyst is the most sulfur tolerant. Al2O3 and CeO2 are much better than SiO2 and MgO as the supports for the Rh catalyst to reform sulfur-containing hydrocarbons. The good sulfur tolerance of Rh/Al2O3 can be attributed to the acidic nature of the Al2O3 support and its small Rh crystallites (1-3 nm) as these characteristics facilitate the formation of electron-deficient Rh particles with high sulfur tolerance. The good catalytic performance of Rh/CeO2 in the presence of sulfur can be ascribed to the promotion effect of CeO2 on carbon gasification, which significantly reduced the carbon deposition on the Rh/CeO2catalyst. Steam reforming of Norpar13 in the absence and presence of sulfur was further carried out over CeO2-Al2O3 supported monometallic Ni and Rh and bimetallic Rh-Ni catalysts at 550 and 800 °C. Both monometallic catalysts rapidly deactivated at 550 °C, iv and showed poor sulfur tolerance. Although ineffective for the Ni catalyst, increasing the temperature to 800 °C dramatically improved the sulfur tolerance of the Rh catalyst. Sulfur K-edge XANES revealed that metal sulfide and organic sulfide are the dominant sulfur species on the used Ni catalyst, while sulfonate and sulfate predominate on the used Rh catalyst. The superior sulfur tolerance of the Rh/CeO2-Al2O3 catalyst at 800 °C may be associated with its capability in sulfur oxidation. It is very likely that the oxygenshielded sulfur structure of sulfonate and sulfate can suppress the poisoning impact of sulfur on Rh through inhibiting direct rhodium-sulfur interaction. Although the Rh-Ni catalyst exhibited better sulfur tolerance than the monometallic ones at 550 °C, its catalytic performance was inferior compared with the Rh catalyst in the sulfur-containing reaction at 800 °C probably due to the severe carbon deposition on the bimetallic catalyst. The last part of this work focuses on the influence of sulfur on the carbon deposition in steam reforming of liquid hydrocarbon fuels over CeO2-Al2O3 supported monometallic Ni and Rh catalysts at 800 ºC. Though abundant carbon deposits can accumulate on the pure CeO2-Al2O3 support due to fuel thermal cracking, the metal addition substantially mitigated the carbon deposition in the sulfur-free reaction. The presence of sulfur increased the carbon deposition on both catalysts, which has a much more significant impact for the Ni catalyst. Our results indicate that (I) the presence of sulfur can suppress carbon gasification and promote the formation of graphitic carbon on reforming catalysts, and (II) the Rh catalyst possesses stronger capability to maintain carbon gasification activity than the Ni catalyst in the presence of sulfur.

NiCu single atom alloys catalyze the C—H bond activation in the selective non- oxidative ethanol dehydrogenation reaction

DOE PAGES

Shan, Junjun; Liu, Jilei; Li, Mengwei; ...

2017-12-29

Here, NiCu single atom alloy (SAA) nanoparticles supported on silica are reported to catalyze the non-oxidative dehydrogenation of ethanol, selectively to acetaldehyde and hydrogen products by facilitating the C—H bond cleavage. The activity and selectivity of the NiCu SAA catalysts were compared to monometallic copper and to PtCu and PdCu single atom alloys, in a flow reactor at moderate temperatures. In-situ DRIFTS showed that the silica support facilitates the O—H bond cleavage of ethanol to form ethoxy intermediates over all the supported alloy catalysts. However, these remain unreactive up to 250°C for the Cu/SiO 2 monometallic nanoparticles, while in themore » NiCu SAA, acetaldehyde is formed at much lower temperatures, below 150°C. In situ DRIFTS was also used to identify the C—H activation step as the rate determining step of this reaction on all the copper catalysts we examined. The presence of atomically dispersed Ni in Cu significantly lowers the C—H bond activation barrier, whereas Pt and Pd atoms were found less effective. This work provides direct evidence that the C—H bond cleavage is the rate determining step in ethanol dehydrogenation over this type catalyst.« less

NiCu single atom alloys catalyze the C—H bond activation in the selective non- oxidative ethanol dehydrogenation reaction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shan, Junjun; Liu, Jilei; Li, Mengwei

Here, NiCu single atom alloy (SAA) nanoparticles supported on silica are reported to catalyze the non-oxidative dehydrogenation of ethanol, selectively to acetaldehyde and hydrogen products by facilitating the C—H bond cleavage. The activity and selectivity of the NiCu SAA catalysts were compared to monometallic copper and to PtCu and PdCu single atom alloys, in a flow reactor at moderate temperatures. In-situ DRIFTS showed that the silica support facilitates the O—H bond cleavage of ethanol to form ethoxy intermediates over all the supported alloy catalysts. However, these remain unreactive up to 250°C for the Cu/SiO 2 monometallic nanoparticles, while in themore » NiCu SAA, acetaldehyde is formed at much lower temperatures, below 150°C. In situ DRIFTS was also used to identify the C—H activation step as the rate determining step of this reaction on all the copper catalysts we examined. The presence of atomically dispersed Ni in Cu significantly lowers the C—H bond activation barrier, whereas Pt and Pd atoms were found less effective. This work provides direct evidence that the C—H bond cleavage is the rate determining step in ethanol dehydrogenation over this type catalyst.« less

Walking economy during cued versus non-cued self-selected treadmill walking in persons with Parkinson's disease.

PubMed

Gallo, Paul M; McIsaac, Tara L; Garber, Carol Ewing

2014-01-01

Gait impairments related to Parkinson's disease (PD) include variable step length and decreased walking velocity, which may result in poorer walking economy. Auditory cueing is a common method used to improve gait mechanics in PD that has been shown to worsen walking economy at set treadmill walking speeds. It is unknown if auditory cueing has the same effects on walking economy at self-selected treadmill walking speeds. To determine if auditory cueing will affect walking economy at self-selected treadmill walking speeds and at speeds slightly faster and slower than self-selected. Twenty-two participants with moderate PD performed three, 6-minute bouts of treadmill walking at three speeds (self-selected and ± 0.22 m·sec-1). One session used cueing and the other without cueing. Energy expenditure was measured and walking economy was calculated (energy expenditure/power). Poorer walking economy and higher energy expenditure occurred during cued walking at a self-selected and a slightly faster walking speed, but there was no apparent difference at the slightly slower speed. These results suggest that potential gait benefits of auditory cueing may come at an energy cost and poorer walking economy for persons with PD at least at some treadmill walking speeds.

The effectiveness of external sensory cues in improving functional performance in individuals with Parkinson's disease: a systematic review with meta-analysis.

PubMed

Cassimatis, Constantine; Liu, Karen P Y; Fahey, Paul; Bissett, Michelle

2016-09-01

A systematic review with meta-analysis was performed to investigate the effect external sensory cued therapy on activities of daily living (ADL) performance that include walking and daily tasks such as dressing for individuals with Parkinson's disease (PD). A detailed computer-aided search of the literature was applied to MEDLINE, Cumulative Index to Nursing and Allied Health Literature, EMBASE and PubMed. Studies investigating the effects of external sensory cued therapy on ADL performance for individuals with PD in all stages of disease progression were collected. Relevant articles were critically reviewed and study results were synthesized by two independent researchers. A data-analysis method was used to extract data from selected articles. A meta-analysis was carried out for all randomized-controlled trials. Six studies with 243 individuals with PD were included in this review. All six studies yielded positive findings in favour of external sensory cues. The meta-analysis showed that external sensory cued therapy improved statistically after treatment (P=0.011) and at follow-up (P<0.001) for ADL performance. The results of this review provided evidence of an improvement in ADL performance in general in individuals with PD. It is recommended that clinicians incorporate external sensory into a training programme focused on improving daily task performance.

Hydrogenation of benzaldehyde via electrocatalysis and thermal catalysis on carbon-supported metals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Song, Yang; Sanyal, Udishnu; Pangotra, Dhananjai

Abstract Selective reduction of benzaldehyde to benzyl alcohol on C-supported Pt, Rh, Pd, and Ni in aqueous phase was conducted using either directly H2 (thermal catalytic hydrogenation, TCH) or in situ electrocatalytically generated hydrogen (electrocatalytic hydrogenation, ECH). In TCH, the intrinsic activity of the metals at room temperature and 1 bar H2 increased in the sequence Rh/C < Pt/C < Pd/C, while Ni/C is inactive at these conditions due to surface oxidation in the absence of cathodic potential. The reaction follows a Langmuir-Hinshelwood mechanism with the second hydrogen addition to the adsorbed hydrocarbon being the rate-determining step. All tested metalsmore » were active in ECH of benzaldehyde, although hydrogenation competes with the hydrogen evolution reaction (HER). The minimum cathodic potentials to obtain appreciable ECH rates were identical to the onset potentials of HER. Above this onset, the relative rates of H reacting to H2 and H addition to the hydrocarbon determines the selectivity to ECH and TCH. Accordingly, the selectivity of the metals towards ECH increases in the order Ni/C < Pt/C < Rh/C < Pd/C. Pd/C shows exceptionally high ECH selectivity due to its surprisingly low HER reactivity under the reaction conditions. Acknowledgements The authors would like to thank the groups of Hubert A. Gasteiger at the Technische Universität München of Jorge Gascon at the Delft University of Technology for advice and valuable discussions. The authors are grateful to Nirala Singh, Erika Ember, Gary Haller, and Philipp Rheinländer for fruitful discussions. We are also grateful to Marianne Hanzlik for TEM measurements and to Xaver Hecht and Martin Neukamm for technical support. Y.S. would like to thank the Chinese Scholarship Council for the financial support. The research described in this paper is part of the Chemical Transformation Initiative at Pacific Northwest National Laboratory (PNNL), conducted under the Laboratory Directed Research and Development Program at PNNL, a multiprogram national laboratory operated by Battelle for the U.S. Department of Energy.« less

Study of activation cross-sections of deuteron induced reactions on rhodium up to 40 MeV

NASA Astrophysics Data System (ADS)

Ditrói, F.; Tárkányi, F.; Takács, S.; Hermanne, A.; Yamazaki, H.; Baba, M.; Mohammadi, A.; Ignatyuk, A. V.

2011-09-01

In the frame of a systematic study of the activation cross-sections of deuteron induced nuclear reactions, excitation functions of the 103Rh(d,x) 100,101,103Pd, 100g,101m,101g,102m,102gRh and 103gRu reactions were determined up to 40 MeV. Cross-sections were measured with the activation method using a stacked foil irradiation technique. Excitation functions of the contributing reactions were calculated using the ALICE-IPPE, EMPIRE-II and TALYS codes. From the measured cross-section data integral production yields were calculated and compared with experimental integral yield data reported in the literature. From the measured cross-sections and previous data, activation curves were deduced to support thin layer activation (TLA) on rhodium and Rh containing alloys.

Cathodic Corrosion of a Bulk Wire to Nonaggregated Functional Nanocrystals and Nanoalloys

PubMed Central

2018-01-01

A key enabling step in leveraging the properties of nanoparticles (NPs) is to explore new, simple, controllable, and scalable nanotechnologies for their syntheses. Among “wet” methods, cathodic corrosion has been used to synthesize catalytic aggregates with some control over their size and preferential faceting. Here, we report on a modification of the cathodic corrosion method for producing a range of nonaggregated nanocrystals (Pt, Pd, Au, Ag, Cu, Rh, Ir, and Ni) and nanoalloys (Pt50Au50, Pd50Au50, and AgxAu100–x) with potential for scaling up the production rate. The method employs poly(vinylpyrrolidone) (PVP) as a stabilizer in an electrolyte solution containing nonreducible cations (Na+, Ca2+), and cathodic corrosion of the corresponding wires takes place in the electrolyte under ultrasonication. The ultrasonication not only promotes particle–PVP interactions (enhancing NP dispersion and diluting locally high NP concentration) but also increases the production rate by a factor of ca. 5. Further increase in the production rate can be achieved through parallelization of electrodes to construct comb electrodes. With respect to applications, carbon-supported Pt NPs prepared by the new method exhibit catalytic activity and durability for methanol oxidation comparable or better than the commercial benchmark catalyst. A variety of AgxAu100–x nanoalloys are characterized by ultraviolet–visible absorption spectroscopy and high-resolution transmission electron microscopy. The protocol for NP synthesis by cathodic corrosion should be a step toward its further use in academic research as well as in its practical upscaling. PMID:29446912

Effect of Surface Modifications of Ti40Zr10Cu38Pd12 Bulk Metallic Glass and Ti-6Al-4V Alloy on Human Osteoblasts In Vitro Biocompatibility

PubMed Central

Blanquer, Andreu; Hynowska, Anna; Nogués, Carme; Ibáñez, Elena; Sort, Jordi; Baró, Maria Dolors; Özkale, Berna; Pané, Salvador; Pellicer, Eva

2016-01-01

The use of biocompatible materials, including bulk metallic glasses (BMGs), for tissue regeneration and transplantation is increasing. The good mechanical and corrosion properties of Ti40Zr10Cu38Pd12 BMG and its previously described biocompatibility makes it a potential candidate for medical applications. However, it is known that surface properties like topography might play an important role in regulating cell adhesion, proliferation and differentiation. Thus, in the present study, Ti40Zr10Cu38Pd12 BMG and Ti6-Al-4V alloy were surface-modified electrochemically (nanomesh) or physically (microscratched) to investigate the effect of material topography on human osteoblasts cells (Saos-2) adhesion, proliferation and differentiation. For comparative purposes, the effect of mirror-like polished surfaces was also studied. Electrochemical treatments led to a highly interconnected hierarchical porous structure rich in oxides, which have been described to improve corrosion resistance, whereas microscratched surfaces showed a groove pattern with parallel trenches. Cell viability was higher than 96% for the three topographies tested and for both alloy compositions. In all cases, cells were able to adhere, proliferate and differentiate on the alloys, hence indicating that surface topography plays a minor role on these processes, although a clear cell orientation was observed on microscratched surfaces. Overall, our results provide further evidence that Ti40Zr10Cu38Pd12 BMG is an excellent candidate, in the present two topographies, for bone repair purposes. PMID:27243628

X-ray spectroscopy for chemistry in the 2-4 keV energy regime at the XMaS beamline: ionic liquids, Rh and Pd catalysts in gas and liquid environments, and Cl contamination in γ-Al2O3.

PubMed

Thompson, Paul B J; Nguyen, Bao N; Nicholls, Rachel; Bourne, Richard A; Brazier, John B; Lovelock, Kevin R J; Brown, Simon D; Wermeille, Didier; Bikondoa, Oier; Lucas, Christopher A; Hase, Thomas P A; Newton, Mark A

2015-11-01

The 2-4 keV energy range provides a rich window into many facets of materials science and chemistry. Within this window, P, S, Cl, K and Ca K-edges may be found along with the L-edges of industrially important elements from Y through to Sn. Yet, compared with those that cater for energies above ca. 4-5 keV, there are relatively few resources available for X-ray spectroscopy below these energies. In addition, in situ or operando studies become to varying degrees more challenging than at higher X-ray energies due to restrictions imposed by the lower energies of the X-rays upon the design and construction of appropriate sample environments. The XMaS beamline at the ESRF has recently made efforts to extend its operational energy range to include this softer end of the X-ray spectrum. In this report the resulting performance of this resource for X-ray spectroscopy is detailed with specific attention drawn to: understanding electrostatic and charge transfer effects at the S K-edge in ionic liquids; quantification of dilution limits at the Cl K- and Rh L3-edges and structural equilibria in solution; in vacuum deposition and reduction of [Rh(I)(CO)2Cl]2 to γ-Al2O3; contamination of γ-Al2O3 by Cl and its potential role in determining the chemical character of supported Rh catalysts; and the development of chlorinated Pd catalysts in `green' solvent systems. Sample environments thus far developed are also presented, characterized and their overall performance evaluated.

Transparent ITO/Ag-Pd-Cu/ITO multilayer cathode use in inverted organic solar cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, Hyo-Joong; Kim, Han-Ki, E-mail: imdlhkkim@khu.ac.kr; Lee, Hyun Hwi

2015-10-15

The characteristics of transparent ITO/Ag-Pd-Cu (APC)/ITO multilayer cathodes were investigated for use in inverted organic solar cells (IOSCs). The insertion of an APC interlayer into the ITO film effectively led to crystallization of the top ITO layer, unlike that in the Ag interlayer, and resulted in a low sheet resistance of 6.55 Ohm/square and a high optical transmittance of 84.14% without post annealing. In addition, the alloying of the Pd and Cu elements into Ag prevented agglomeration and oxidization of the metal interlayer and led to more stable ITO/APC/ITO films under ambient conditions. The microstructure and interfacial structure of themore » transparent ITO/APC/ITO cathode in the IOSCs were examined in detail by synchrotron X-ray scattering and high resolution transmission electron microscopy. Furthermore, we suggested a possible mechanism to explain the lower PCE of the IOSCs with an ITO/APC/ITO cathode than that of a reference IOSC with a crystalline ITO cathode using the external quantum efficiency of the IOSCs.« less

Development of casting investment preventing blackening of noble metal alloys part 1. Application of developed investment for Ag-Pd-Cu-Au alloy.

PubMed

Kakuta, Kiyoshi; Nakai, Akira; Goto, Shin-ichi; Wakamatsu, Yasushi; Yara, Atushi; Miyagawa, Yukio; Ogura, Hideo

2003-03-01

The objective of this study is to develop a casting investment that prevents the blackening of the cast surface of noble metal alloys. The experimental investments were prepared using a gypsum-bonded investment in which the metallic powders such as boron (B), silicon (Si), aluminum (Al) and titanium (Ti) were added as oxidizing agents. An Ag-Pd-Cu-Au alloy was cast into the mold made of the prepared investment. The effect of the addition of each metal powder was evaluated from the color difference between the as-cast surface and the polished surface of the cast specimen. The color of the as-cast surface approached that of the polished surface with increasing B and Al content. A lower mean value in the color difference was obtained at 0.25-1.00 mass% B content. B and Al are useful as an additive in a gypsum-bonded investment to prevent the blackening of an Ag-Pd-Cu-Au alloy. The effects of Si and Ti powder addition could not be found.

Transparent ITO/Ag-Pd-Cu/ITO multilayer cathode use in inverted organic solar cells

NASA Astrophysics Data System (ADS)

Kim, Hyo-Joong; Lee, Hyun Hwi; Kal, Jinha; Hahn, Jungseok; Kim, Han-Ki

2015-10-01

The characteristics of transparent ITO/Ag-Pd-Cu (APC)/ITO multilayer cathodes were investigated for use in inverted organic solar cells (IOSCs). The insertion of an APC interlayer into the ITO film effectively led to crystallization of the top ITO layer, unlike that in the Ag interlayer, and resulted in a low sheet resistance of 6.55 Ohm/square and a high optical transmittance of 84.14% without post annealing. In addition, the alloying of the Pd and Cu elements into Ag prevented agglomeration and oxidization of the metal interlayer and led to more stable ITO/APC/ITO films under ambient conditions. The microstructure and interfacial structure of the transparent ITO/APC/ITO cathode in the IOSCs were examined in detail by synchrotron X-ray scattering and high resolution transmission electron microscopy. Furthermore, we suggested a possible mechanism to explain the lower PCE of the IOSCs with an ITO/APC/ITO cathode than that of a reference IOSC with a crystalline ITO cathode using the external quantum efficiency of the IOSCs.

Polydopamine-mediated surface-functionalization of graphene oxide for heavy metal ions removal

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dong, Zhihui; University of Chinese Academy of Sciences, Chinese Academy of Sciences, Beijing 100049; Zhang, Feng

2015-04-15

By utilizing polydopamine (PD) nano-thick interlayer as mediator, polyethylenimine (PEI) brushes with abundant amine groups were grafted onto the surface of PD coated graphene oxide (GO) uniformly via a Michael-Addition reaction and produced a PEI–PD/GO composite nanosheets. The PEI–PD/GO composite exhibited an improved performance for adsorption of heavy metal ions as compared to PEI-coated GO and pure GO. The adsorption capacities for Cu{sup 2+}, Cd{sup 2+}, Pb{sup 2+}, Hg{sup 2+} are up to 87, 106, 197, and 110 mg/g, respectively. To further make the GO based composite operable, PEI–PD/RGO aerogel was prepared through hydrothermal and achieved a high surface areamore » up to 373 m{sup 2}/g. Although the adsorption capacity of PEI–PD/RGO aerogel for heavy metal ions decreases a little as compared to PEI–PD/GO composite dispersion (38, 32, 95, 113 mg/g corresponding to Cu{sup 2+}, Cd{sup 2+}, Pb{sup 2+}, and Hg{sup 2+}, respectively), it could be recycled several times in a simple way by releasing adsorbed metal ions, indicating its potential application for cleaning wastewater. - Graphical abstract: Polyethylenimine (PEI) brushes were grafted onto the surface of graphene oxide (GO) uniformly via a Michael-Addition reaction between the PEI and polydopamine interlayer coated on GO surface. The PEI–PD/GO composite exhibited an improved performance for adsorption of heavy metal ions compared to PEI-coated GO and pure GO. - Highlights: • We prepared polyethylenimine grafted polydopamine-mediated graphene oxide composites. • Introduction of PD layer increases metal ions adsorption capacity. • PEI–PD/RGO aerogel exhibited a superior adsorption performance. • PEI–PD/RGO aerogel can be recycled several times in a simple way.« less

DFT studies of hydrocarbon combustion on metal surfaces.

PubMed

Arya, Mina; Mirzaei, Ali Akbar; Davarpanah, Abdol Mahmood; Barakati, Seyed Masoud; Atashi, Hossein; Mohsenzadeh, Abas; Bolton, Kim

2018-02-02

Catalytic combustion of hydrocarbons is an important technology to produce energy. Compared to conventional flame combustion, the catalyst enables this process to operate at lower temperatures; hence, reducing the energy required for efficient combustion. The reaction and activation energies of direct combustion of hydrocarbons (CH → C + H) on a series of metal surfaces were investigated using density functional theory (DFT). The data obtained for the Ag, Au, Al, Cu, Rh, Pt, and Pd surfaces were used to investigate the validity of the Brønsted-Evans-Polanyi (BEP) and transition state scaling (TSS) relations for this reaction on these surfaces. These relations were found to be valid (R 2  = 0.94 for the BEP correlation and R 2  = 1.0 for the TSS correlation) and were therefore used to estimate the energetics of the combustion reaction on Ni, Co, and Fe surfaces. It was found that the estimated transition state and activation energies (E TS  = -69.70 eV and E a  = 1.20 eV for Ni, E TS  = -87.93 eV and E a  = 1.08 eV for Co and E TS  = -92.45 eV and E a  = 0.83 eV for Fe) are in agreement with those obtained by DFT calculations (E TS  = -69.98 eV and E a  = 1.23 eV for Ni, E TS  = -87.88 eV and E a  = 1.08 eV for Co and E TS  = -92.57 eV and E a  = 0.79 eV for Fe). Therefore, these relations can be used to predict energetics of this reaction on these surfaces without doing the time consuming transition state calculations. Also, the calculations show that the activation barrier for CH dissociation decreases in the order Ag ˃ Au ˃ Al ˃ Cu ˃ Pt ˃ Pd ˃ Ni > Co > Rh > Fe.

Charge partitioning and anomalous hole doping in Rh-doped Sr 2 IrO 4

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chikara, S.; Fabbris, G.; Terzic, J.

2017-02-01

The simultaneous presence of sizable spin-orbit interactions and electron correlations in iridium oxides has led to predictions of novel ground states including Dirac semimetals, Kitaev spin liquids, and superconductivity. Electron and hole doping studies of spin-orbit assisted Mott insulator Sr2IrO4 are being intensively pursued due to extensive parallels with the La2CuO4 parent compound of cuprate superconductors. In particular, the mechanism of charge doping associated with replacement of Ir with Rh ions remains controversial with profound consequences for the interpretation of electronic structure and transport data. Using x-ray absorption near edge structure measurements at the Rh L, K, and Ir Lmore » edges we observe anomalous evolution of charge partitioning between Rh and Ir with Rh doping. The partitioning of charge between Rh and Ir sites progresses in a way that holes are initially doped into the J(eff) = 1/2 band at low x only to be removed from it at higher x values. This anomalous hole doping naturally explains the reentrant insulating phase in the phase diagram of Sr2Ir1-x Rh-x O-4 and ought to be considered when searching for superconductivity and other emergent phenomena in iridates doped with 4d elements.« less

Charge partitioning and anomalous hole doping in Rh-doped Sr 2 IrO 4

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chikara, Shalinee; Fabbris, G.; Terzic, J.

2017-02-15

The simultaneous presence of sizable spin-orbit interactions and electron correlations in iridium oxides has led to predictions of novel ground states including Dirac semimetals, Kitaev spin liquids, and superconductivity. Electron and hole doping studies of spin-orbit assisted Mott insulator Sr 2IrO 4 are being intensively pursued due to extensive parallels with the La 2CuO 4 parent compound of cuprate superconductors. In particular, the mechanism of charge doping associated with replacement of Ir with Rh ions remains controversial with profound consequences for the interpretation of electronic structure and transport data. Using x-ray absorption near edge structure measurements at the Rh L,more » K, and Ir L edges we observe anomalous evolution of charge partitioning between Rh and Ir with Rh doping. The partitioning of charge between Rh and Ir sites progresses in a way that holes are initially doped into the J eff = 1/2 band at low x only to be removed from it at higher x values. Furthermore, this anomalous hole doping naturally explains the reentrant insulating phase in the phase diagram of Sr 2Ir 1–xRh xO 4 and ought to be considered when searching for superconductivity and other emergent phenomena in iridates doped with 4d elements.« less

A new biosensor for noninvasive determination of fetal RHD status in maternal blood of RhD negative pregnant women.

PubMed

Dündar Yenilmez, Ebru; Kökbaş, Umut; Kartlaşmış, Kezban; Kayrın, Levent; Tuli, Abdullah

2018-01-01

Prenatal detection of the fetal RHD status can be useful in the management of RhD incompatibility to identify fetuses at risk of hemolytic disease. Hemolytic disease causes morbidity and mortality of the fetus in the neonatal period. The routine use of antenatal and postnatal anti-D prophylaxis has reduced the incidence of hemolytic disease of the fetus and newborn. This study describe the detection of fetal RhD antigens in blood of RhD negative pregnant women using a nanopolymer coated electrochemical biosensor for medical diagnosis. Cell free fetal DNA in maternal plasma was also used to genotyping fetal RHD status using multiplex real-time PCR. Twenty-six RhD negative pregnant women in different gestational ages were included in the study. RhD positive fetal antibodies detected with a developed biosensor in maternal blood of RhD negative mothers. The electrochemical measurements were performed on a PalmSens potentiostat, and corundum ceramic based screen printed gold electrode combined with the reference Ag/AgCl electrode, and the auxiliary Au/Pd (98/2%) electrode. Fetal RHD genotyping performed using fluorescence-based multiplex real-time PCR exons 5 and 7 of the RHD gene. The fetal RHD status of 26 RhD negative cases were detected 21 as RhD positive and 5 as RhD negative with electrochemical biosensor. Fetal RHD status confirmed with extracted fetal DNA in maternal plasma using multiplex real-time PCR RHD genotyping and by serological test after delivery. The new method for fetal RhD detection in early pregnancy is useful and can be carry out rapidly in clinical diagnosis. Using automated biosensors are reproducible, quick and results can be generated within a few minutes compared to noninvasive fetal RHD genotyping from maternal plasma with real-time PCR-based techniques. We suggest the biosensor techniques could become an alternative part of fetal RHD genotyping from maternal plasma as a prenatal screening in the management of RhD incompatibility.

Effect of Alloying Elements on Nb-Rich Portion of Nb-Si-X Ternary Systems and In Situ Crack Observation of Nb-Si-Based Alloys

NASA Astrophysics Data System (ADS)

Miura, Seiji; Hatabata, Toru; Okawa, Takuya; Mohri, Tetsuo

2014-03-01

To find a new route for microstructure control and to find additive elements beneficial for improving high-temperature strength, a systematic investigation is performed on hypoeutectic Nb-15 at. pct Si-X ternary alloys containing a transition element, Fe, Co, Ni, Cu, Ru, Rh, Pd, Re, Os, Ir, Pt, or Au. Information on phase equilibrium is classified in terms of phase stability of silicide phases, α Nb5Si3, Nb4SiX, and Nb3Si, and the relationship between microstructure and mechanical properties both at room temperature and high temperature is investigated. All the additive elements are found to stabilize either α Nb5Si3 or Nb4SiX but destabilize Nb3Si. A microstructure of Nbss/α Nb5Si3 alloy composed of spheroidized α Nb5Si3 phase embedded in the Nbss matrix is effective for toughening, regardless of the initial as-cast microstructure. Also the plastic deformation of Nbss dendrites may effectively suppress the propagation of longer cracks. High-temperature strength of alloys is governed by the deformation of Nbss phase and increases with higher melting point additives.

Cu(II) promotes amyloid pore formation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Hangyu, E-mail: hangyuz@uw.edu; Rochet, Jean-Christophe; Stanciu, Lia A.

2015-08-14

The aggregation of α-synuclein is associated with dopamine neuron death in Parkinson's disease. There is controversy in the field over the question of which species of the aggregates, fibrils or protofibrils, are toxic. Moreover, compelling evidence suggested the exposure to heavy metals to be a risk of PD. Nevertheless, the mechanism of metal ions in promoting PD remains unclear. In this research, we investigated the structural basis of Cu(II) induced aggregation of α-synuclein. Using transmission electron microscopy experiments, Cu(II) was found to promote in vitro aggregation of α-synuclein by facilitating annular protofibril formation rather than fibril formation. Furthermore, neuroprotective baicalein disaggregatedmore » annular protofibrils accompanied by considerable decrease of β-sheet content. These results strongly support the hypothesis that annular protofibrils are the toxic species, rather than fibrils, thereby inspiring us to search novel therapeutic strategies for the suppression of the toxic annular protofibril formation. - Highlights: • Cu(II) promoted the annular protofibril formation of α-synuclein in vitro. • Cu(II) postponed the in vitro fibrillization of α-synuclein. • Neuroprotective baicalein disaggregated annular protofibrils.« less

Nitrate reduction over a Pd-Cu/MWCNT catalyst: application to a polluted groundwater.

PubMed

Soares, Olivia Salomé G P; Orfão, José J M; Gallegos-Suarez, Esteban; Castillejos, Eva; Rodríguez-Ramos, Inmaculada; Pereira, Manuel Fernando R

2012-01-01

The influence of the presence of inorganic and organic matter during the catalytic reduction of nitrate in a local groundwater over a Pd-Cu catalyst supported on carbon nanotubes was investigated. It was observed that the catalyst performance was affected by the groundwater composition. The nitrate conversion attained was higher in the experiment using only deionized water as solvent than in the case of simulated or real groundwater. With exception of sulphate ions, all the other solutes evaluated (chloride and phosphate ions and natural organic matter) had a negative influence on the catalytic activity and selectivity to nitrogen.

EPR probes with well-defined, long distances between two or three unpaired electrons

PubMed

Godt; Franzen; Veit; Enkelmann; Pannier; Jeschke

2000-11-03

The synthesis of rod- and star-shaped compounds carrying two or three spin labels as end groups is described. The unpaired electrons are 2.8-5.1 nm apart from each other. The shape-persistent scaffolds were obtained through Pd-Cu-catalyzed alkynyl-aryl coupling and Pd-Cu-catalyzed alkyne dimerization in the presence of oxygen using p-phenyleneethynylene as the basic shape-persistent building block. The spin label 1-oxyl-2,2,5,5-tetramethylpyrroline-3-carboxylic acid (4) was attached through esterification of the terminal phenolic OH groups of the scaffold.

CuI/Pd0 cooperative dual catalysis: tunable stereoselective construction of tetra-substituted alkenes.

PubMed

Vercruysse, Sébastien; Cornelissen, Loïc; Nahra, Fady; Collard, Laurent; Riant, Olivier

2014-02-10

This paper describes a tunable and stereoselective dual catalytic system that uses copper and palladium reagents. This cooperative silylcupration and palladium-catalyzed allylation readily affords trisubstituted alkenylsilanes. Fine-tuning the reaction conditions allows selective access to one stereoisomer over the other. This new methodology tolerates different substituents on both coupling partners with high levels of stereoselectivity. The one-pot reaction involving a Cu(I)/Pd(0) cooperative dual catalyst directly addresses the need to develop more time-efficient and less-wasteful synthetic pathways. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Precipitation Hardenable High Temperature Shape Memory Alloy

NASA Technical Reports Server (NTRS)

Noebe, Ronald Dean (Inventor); Draper, Susan L. (Inventor); Nathal, Michael V. (Inventor); Crombie, Edwin A. (Inventor)

2010-01-01

A composition of the invention is a high temperature shape memory alloy having high work output, and is made from (Ni+Pt+Y),Ti(100-x) wherein x is present in a total amount of 49-55 atomic % Pt is present in a total amount of 10-30 atomic %, Y is one or more of Au, Pd. and Cu and is present in a total amount of 0 to 10 atomic %. The alloy has a matrix phase wherein the total concentration of Ni, Pt, and the one or more of Pd. Au, and Cu is greater than 50 atomic %.

Solder flow over fine line PWB surface finishes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hosking, F.M.; Hernandez, C.L.

1998-08-01

The rapid advancement of interconnect technology has stimulated the development of alternative printed wiring board (PWB) surface finishes to enhance the solderability of standard copper and solder-coated surfaces. These new finishes are based on either metallic or organic chemistries. As part of an ongoing solderability study, Sandia National Laboratories has investigated the solder flow behavior of two azole-based organic solderability preservations, immersion Au, immersion Ag, electroless Pd, and electroless Pd/Ni on fine line copper features. The coated substrates were solder tested in the as-fabricated and environmentally-stressed conditions. Samples were processed through an inerted reflow machine. The azole-based coatings generally providedmore » the most effective protection after aging. Thin Pd over Cu yielded the best wetting results of the metallic coatings, with complete dissolution of the Pd overcoat and wetting of the underlying Cu by the flowing solder. Limited wetting was measured on the thicker Pd and Pd over Ni finishes, which were not completely dissolved by the molten solder. The immersion Au and Ag finishes yielded the lowest wetted lengths, respectively. These general differences in solderability were directly attributed to the type of surface finish which the solder came in contact with. The effects of circuit geometry, surface finish, stressing, and solder processing conditions are discussed.« less

Space-Based but not Object-Based Inhibition of Return is Impaired in Parkinson's Disease

PubMed Central

Possin, Katherine L.; Filoteo, J. Vincent; Song, David D.; Salmon, David P.

2009-01-01

Impairments in certain aspects of attention have frequently been reported in Parkinson's disease (PD), including reduced inhibition of return (IOR). Recent evidence suggests that IOR can occur when attention is directed at objects or locations, but previous investigations of IOR in PD have not systematically compared these two frames of reference. The present study compared the performance of 18 nondemented patients with PD and 18 normal controls on an IOR task with two conditions. In the “object-present” condition, objects surrounded the cues and targets so that attention was cued to both a spatial location and to a specific object. In the “object-absent” condition, surrounding objects were not presented so that attention was cued only to a spatial location. When participants had to rely on space-based cues, PD patients demonstrated reduced IOR compared to controls. In contrast, when objects were present in the display and participants could use object-based cues, PD patients exhibited normal IOR. These results suggest that PD patients are impaired in inhibitory aspects of space-based attention, but are able to overcome this impairment when their attention can be directed at object-based frames of reference. This dissociation supports the view that space-based and object-based components of attention involve distinct neurocognitive processes. PMID:19397864

Space-based but not object-based inhibition of return is impaired in Parkinson's disease.

PubMed

Possin, Katherine L; Filoteo, J Vincent; Song, David D; Salmon, David P

2009-06-01

Impairments in certain aspects of attention have frequently been reported in Parkinson's disease (PD), including reduced inhibition of return (IOR). Recent evidence suggests that IOR can occur when attention is directed at objects or locations, but previous investigations of IOR in PD have not systematically compared these two frames of reference. The present study compared the performance of 18 nondemented patients with PD and 18 normal controls on an IOR task with two conditions. In the "object-present" condition, objects surrounded the cues and targets so that attention was cued to both a spatial location and to a specific object. In the "object-absent" condition, surrounding objects were not presented so that attention was cued only to a spatial location. When participants had to rely on space-based cues, PD patients demonstrated reduced IOR compared to controls. In contrast, when objects were present in the display and participants could use object-based cues, PD patients exhibited normal IOR. These results suggest that PD patients are impaired in inhibitory aspects of space-based attention, but are able to overcome this impairment when their attention can be directed at object-based frames of reference. This dissociation supports the view that space-based and object-based components of attention involve distinct neurocognitive processes.

The role of sulfides in the fractionation of highly siderophile and chalcophile elements during the formation of martian shergottite meteorites

NASA Astrophysics Data System (ADS)

Baumgartner, Raphael J.; Fiorentini, Marco L.; Lorand, Jean-Pierre; Baratoux, David; Zaccarini, Federica; Ferrière, Ludovic; Prašek, Marko K.; Sener, Kerim

2017-08-01

The shergottite meteorites are ultramafic to mafic igneous rocks whose parental magmas formed from partial melting of the martian mantle. This study reports in-situ laser ablation inductively coupled plasma mass spectrometry analyses for siderophile and chalcophile major and trace elements (i.e., Co, Ni, Cu, As, Se, Ag, Sb, Te, Pb, Bi, and the highly siderophile platinum-group elements, PGE: Os, Ir, Ru, Rh, Pt and Pd) of magmatic Fe-Ni-Cu sulfide assemblages from four shergottite meteorites. They include three geochemically similar incompatible trace element- (ITE-) depleted olivine-phyric shergottites (Yamato-980459, Dar al Gani 476 and Dhofar 019) that presumably formed from similar mantle and magma sources, and one distinctively ITE-enriched basaltic shergottite (Zagami). The sulfides in the shergottites have been variably modified by alteration on Earth and Mars, as well as by impact shock-shock related melting/volatilization during meteorite ejection. However, they inherit and retain their magmatic PGE signatures. The CI chondrite-normalized PGE concentration patterns of sulfides reproduce the whole-rock signatures determined in previous studies. These similarities indicate that sulfides exerted a major control on the PGE during shergottite petrogenesis. However, depletions of Pt (and Ir) in sulfide relative to the other PGE suggest that additional phases such discrete Pt-Fe-Ir alloys have played an important role in the concentration of these elements. These alloys are expected to have enhanced stability in reduced and FeO-rich shergottite magmas, and could be a common feature in martian igneous systems. A Pt-rich PGM was found to occur in a sulfide assemblage in Dhofar 019. However, its origin may be related to impact shock-related sulfide melting and volatilisation during meteorite ejection. In the ITE-depleted olivine-phyric shergottites, positive relationships exist between petrogenetic indicators (e.g., whole-rock Mg-number) and most moderately to strongly siderophile and chalcophile elements in sulfides. These variations extend to incompatible elements like Te and Pd. The whole-rock concentrations of Pd derived from mass-balance calculations decrease by one order of magnitude in the order Y-980459, DaG 476 and Dhofar 019, and broadly overlap the trends in previously published whole-rock analyses. Mantle heterogeneities, and the timing of sulfide saturation as function of mantle melting and/or magma fractionation following ascent from the mantle, may have been the controlling factors of the siderophile and chalcophile element systematics in the analyzed shergottites.

An Experimental and Analytical Investigation of a Radial Face Seal

DTIC Science & Technology

1976-01-01

c \\]f’ n" •’ * TIMOTHY W. SWAFFORD h ; January 1976 Cjl...Vi 4J to c H Ö o Ö Ü (D M s Ö • H tfl 1-1 U a) :r^J. y^^^^^l 32 From NA iransparent tubing To seal ^xH— Globe valves Supply... c . 3 n) cNi a o cu <• C8 rH CC 1 A > o. U T-: 1 ^O J ^ ’ k 3 o a c ^ ^O TI —< r- -i! O 0) H - H rH H

Current-induced spin polarization on metal surfaces probed by spin-polarized positron beam

PubMed Central

Zhang, H. J.; Yamamoto, S.; Fukaya, Y.; Maekawa, M.; Li, H.; Kawasuso, A.; Seki, T.; Saitoh, E.; Takanashi, K.

2014-01-01

Current-induced spin polarization (CISP) on the outermost surfaces of Au, Cu, Pt, Pd, Ta, and W nanoscaled films were studied using a spin-polarized positron beam. The Au and Cu surfaces showed no significant CISP. In contrast, the Pt, Pd, Ta, and W films exhibited large CISP (3~15% per input charge current of 105 A/cm2) and the CISP of Ta and W were opposite to those of Pt and Pd. The sign of the CISP obeys the same rule in spin Hall effect suggesting that the spin-orbit coupling is mainly responsible for the CISP. The magnitude of the CISP is explained by the Rashba-Edelstein mechanism rather than the diffusive spin Hall effect. This settles a controversy, that which of these two mechanisms dominates the large CISP on metal surfaces. PMID:24776781

Ni, Cu, Au, and platinum-group element contents of sulphides associated with intraplate magmatism: A synthesis

USGS Publications Warehouse

Barnes, S.-J.; Zientek, M.L.; Severson, M.J.

1997-01-01

The tectonic setting of intraplate magmas, typically a plume intersecting a rift, is ideal for the development of Ni - Cu - platinum-group element-bearing sulphides. The plume transports metal-rich magmas close to the mantle - crust boundary. The interaction of the rift and plume permits rapid transport of the magma into the crust, thus ensuring that no sulphides are lost from the magma en route to the crust. The rift may contain sediments which could provide the sulphur necessary to bring about sulphide saturation in the magmas. The plume provides large volumes of mafic magma; thus any sulphides that form can collect metals from a large volume of magma and consequently the sulphides will be metal rich. The large volume of magma provides sufficient heat to release large quantities of S from the crust, thus providing sufficient S to form a large sulphide deposit. The composition of the sulphides varies on a number of scales: (i) there is a variation between geographic areas, in which sulphides from the Noril'sk - Talnakh area are the richest in metals and those from the Muskox intrusion are poorest in metals; (ii) there is a variation between textural types of sulphides, in which disseminated sulphides are generally richer in metals than the associated massive and matrix sulphides; and (iii) the massive and matrix sulphides show a much wider range of compositions than the disseminated sulphides, and on the basis of their Ni/Cu ratio the massive and matrix sulphides can be divided into Cu rich and Fe rich. The Cu-rich sulphides are also enriched in Pt, Pd, and Au; in contrast, the Fe-rich sulphides are enriched in Fe, Os, Ir, Ru, and Rh. Nickel concentrations are similar in both. Differences in the composition between the sulphides from different areas may be attributed to a combination of differences in composition of the silicate magma from which the sulphides segregated and differences in the ratio of silicate to sulphide liquid (R factors). The higher metal content of the disseminated sulphides relative to the massive and matrix sulphides may be due to the fact that the disseminated sulphides equilibrated with a larger volume of magma than massive and matrix sulphides. The difference in composition between the Cu- and Fe-rich sulphides may be the result of the fractional crystallization of monosulphide solid solution from a sulphide liquid, with the Cu-rich sulphides representing the liquid and the Fe-rich sulphides representing the cumulate.

Thermodynamic assessment of the rhodium-ruthenium-oxygen (Rh-Ru-O) system

NASA Astrophysics Data System (ADS)

Gossé, S.; Bordier, S.; Guéneau, C.; Brackx, E.; Domenger, R.; Rogez, J.

2018-03-01

Ruthenium (Ru) and rhodium (Rh) are abundant platinum-group metals formed during burn-up of nuclear fuels. Under normal operating conditions, Rh and Ru accumulate and predominantly form metallic precipitates with other fission products like Mo, Pd and Tc. In the framework of vitrification of high-level nuclear waste, these fission products are poorly soluble in molten glasses. They precipitate as metallic particles and oxide phases. Moreover, these Ru and Rh rich phases strongly depend on temperature and the oxygen fugacity of the glass melt. In case of severe accidental conditions with air ingress, oxidation of the Ru and Rh is possible. At low temperatures (T < 1422 K for rhodium sesquioxide and T < 1815 K for ruthenium dioxide), the formed oxides are relatively stable. On the other hand, at high temperatures (T > 1422 K for rhodium sesquioxide and T > 1815 K for ruthenium dioxide), they may decompose into (Rh)-FCC or (Ru)-HCP metallic phases and radiotoxic volatile gaseous species. A thermodynamic assessment of the Rh-Ru-O system will enable the prediction of: (1) the metallic and oxide phases that form during the vitrification of high-level nuclear wastes and (2) the release of volatile gaseous species during a severe accident. The Calphad method developed herein employs a thermodynamic approach in the investigation of the thermochemistry of rhodium and ruthenium at high temperatures. Current literature on the thermodynamic properties and phase diagram data enables preliminary thermodynamic assessments of the Rh-O and Ru-O systems. Additionally, select compositions in the ternary Rh-Ru-O system underwent experimental tests to complement data found in literature and to establish the phase equilibria in the ternary system.

Hydrogenation of 4-nitrophenol to 4-aminophenol at room temperature: Boosting palladium nanocrystals efficiency by coupling with copper via liquid phase pulsed laser ablation

NASA Astrophysics Data System (ADS)

Park, Hanbit; Reddy, D. Amaranatha; Kim, Yujin; Lee, Seunghee; Ma, Rory; Lim, Manho; Kim, Tae Kyu

2017-04-01

Ultra-dispersed bimetallic nanomaterials have attracted much attention in the hydrogenation of highly toxic aromatic nitro compounds to aromatic amines owing to their high stability, superior activity, reusability, and unique optical and electronic properties, as compared to monometalic nanocrystals. However, the lack of facile and economically controllable strategies of producing highly pure ultra-dispersed bimetallic nanocatalysts limits their practical industrial applications. Considering the above obstacles, we present a simple and effective strategy for the formation of bimetallic (PdCu) nanocrystals by liquid phase pulsed laser ablation using a bulk Pd metal plate submerged in CuCl2 solutions with different concentrations, in contrast to the complex and costly experimental methods used previously. The microstructural and optical properties of the synthesized nanocrystals indicate that the obtained bimetallic nanostructures are highly pure and monodispersed. Moreover, bimetallic PdCu nanostructures show a higher catalytic activity than monometallic Pd nanocrystals for the hydrogenation of 4-nitrophenol to 4-aminophenol at room temperature, also exhibiting high stability for up to four recycles. The mechanism of the enhanced catalytic activity and stability of bimetallic nanocrystals is discussed in detail. Finally, we believe that the presented design strategy and utilization of bimetallic nanocrystals for catalytic applications enables the development of novel bimetallic nanostructures by liquid phase pulsed laser ablation and their catalytic application for environmental remediation.

A study on electromigration-inducing intergranular fracture of fine silver alloy wires

NASA Astrophysics Data System (ADS)

Hsueh, Hao-Wen; Hung, Fei-Yi; Lui, Truan-Sheng

2017-01-01

In this study, Pd-coated Cu, Ag (purity = 4 N), and Ag alloy (Ag-8Au-3Pd) wires were employed to measure the tensile properties during current stressing using the so-called dynamic current tensile (DCT) test. Both the tensile strength and elongation of the wires decreased dramatically in the DCT test, particularly of the Ag-based wires, and the fracture morphology of the Cu-based and Ag-based wires was ductile fracture and intergranular fracture, respectively. Compared to the Cu-based wires, electromigration occurred more easily in the Ag-based wires, and it always generated voids and cracks at the grain boundaries; therefore, the fracture morphology of the Ag-based wires was intergranular fracture owing to the weakened grain boundary. Further, the results indicated that the Ag-based wires could not carry a higher current density than the Cu-based wires, primarily because their extremely low strength and elongation in current stressing might cause serious reliability problems.

Palladium, platinum, rhodium, ruthenium, and iridium in chromitites from the Massif du Sud and Tiebaghi massif, New Caledonia.

USGS Publications Warehouse

Page, N.J.; Cassard, D.; Haffty, J.

1982-01-01

The massive and disseminated podiform chromitites from 43 mines and other occurrences in the area contain up to (in ppb) Pd 9, Pt 45, Rh 31, Ir 410 and Ru 1300. The possble origins of the chromitites are discussed. -K.A.R.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jagannathan, Kaushik; Benson, David M.; Robinson, David B.

Nanofilms of Pd were grown using an electrochemical form of atomic layer deposition (E-ALD) on 100 nm evaporated Au films on glass. Multiple cycles of surface-limited redox replacement (SLRR) were used to grow deposits. Each SLRR involved the underpotential deposition (UPD) of a Cu atomic layer, followed by open circuit replacement via redox exchange with tetrachloropalladate, forming a Pd atomic layer: one E-ALD deposition cycle. That cycle was repeated in order to grow deposits of a desired thickness. 5 cycles of Pd deposition were performed on the Au on glass substrates, resulting in the formation of 2.5 monolayers of Pd.more » Those Pd films were then modified with varying coverages of Pt, also formed using SLRR. The amount of Pt was controlled by changing the potential for Cu UPD, and by increasing the number of Pt deposition cycles. Hydrogen absorption was studied using coulometry and cyclic voltammetry in 0.1 M H 2SO 4 as a function of Pt coverage. The presence of even a small fraction of a Pt monolayer dramatically increased the rate of hydrogen desorption. However, this did not reduce the films’ hydrogen storage capacity. The increase in desorption rate in the presence of Pt was over an order of magnitude.« less

Ultramafic lavas and pyroxene-spinifex high-Mg basaltic dykes from the Othris ophiolite complex, Greece

NASA Astrophysics Data System (ADS)

Baziotis, Ioannis; Economou-Eliopoulos, Maria; Asimow, Paul

2017-04-01

This study aims to constrain the physico-chemical conditions and processes associated with the origin of ultramafic lavas of the Agrilia formation and high-Mg basaltic dykes in the Pournari area within the Othris ophiolite complex, a supra-subduction zone ophiolite of Mesozoic age (Paraskevopoulos & Economou, 1986; Barth et al., 2008). Hand-sample-scale spinifex texture is lacking from the ultramafic lavas and, despite whole-rock MgO contents greater than 31 wt.%, we infer an upper bound of 17 wt.% MgO for the erupted liquid, and thus identify these lavas as picrites containing accumulated olivine. We use textural and compositional criteria to divide the crystals within the Agrilia lavas between pre-eruptive and post-eruptive growth phases. The high-Mg basaltic dyke margins display a distinctive thin-section-scale micro-spinifex texture of skeletal and plumose Al- and Fe-rich clinopyroxene surrounded by large crystals of orthopyroxene. Normally zoned clinopyroxene in the Agrilia lavas and clinopyroxene of various textures (skeletal, needle- and dendritic-like) and sizes in the Pournari dykes display anomalous enrichment in Al2O3 and FeO* with decreasing MgO that require rapid, disequilibrium growth. Quantitative characteristics of the micro-spinifex pyroxene textures (<10 μm in width and 50-100 μm in length) imply a cooling rate for the marginal parts of the Pournari dykes of at least 25 °K/hr and more likely 45-55 °K/hr (Faure et al., 2004) and rapid growth of clinopyroxene crystals at a linear rate of about 10-6 m/s (Welsch et al., 2016). MELTS models of the crystallization sequence of the Pournari dykes indicate that progressive low-pressure (500 bar) fractional crystallization of the ultramafic dyke liquid occurred under oxidized (QFM+2.0) and hydrous (at least 0.5 wt.% H2O) conditions. A hydrous magmatic parent for the Othris ophiolite as a whole is further supported by preliminary investigation of melt inclusions (5-20 μm in diameter) in fresh chromite from Agrilia samples that reveals the presence of Na, K, S, Cl, and F in microcrystalline aggregates of rhönite, clinopyroxene, amphibole, apatite, serpentine and chlorite. Ratios of Platinum Group Elements and related metals are Pd/Ir=11.5-13.0, Cu/Pd=6000-7210, Ti/Pd=22.78-31.97×103 for Agrilia lavas and Pd/Ir=4.5-14.0, Cu/Pd=3140-5550, Ti/Pd=4.66-17.32×103 for Pournari dykes; all are very close to those reported for typical komatiites (Barnes et al., 1988). Despite the absence of true komatiite lavas, a number of geochemical features of the Othris suite, including the PGE contents and ratios and the micro-spinifex, disequilibrium cpx growth, are similar to Mesozoic and Archaean komatiites. References Barnes et al., 1988. Journal of Petrology 29, 305-331. Barth et al., 2008. Lithos, 100(1), 234-254. Faure et al., 2006. Journal of Petrology 47, 1591- 1610. Paraskevopoulos, G., Economou, M., 1986. Ofioliti 11 (3), 293 - 304. Roeder et al., 2001. The Canadian Mineralogist, 39(2), 397-416. Welsch et al., 2016. Contributions to Mineralogy and Petrology 171(1), 1-19.

UV-Vis-Induced Degradation of Phenol over Magnetic Photocatalysts Modified with Pt, Pd, Cu and Au Nanoparticles

PubMed Central

Wysocka, Izabela; Trzciński, Konrad; Łapiński, Marcin; Nowaczyk, Grzegorz; Zielińska-Jurek, Anna

2018-01-01

The combination of TiO2 photocatalyst and magnetic oxide nanoparticles enhances the separation and recoverable properties of nanosized TiO2 photocatalyst. Metal-modified (Me = Pd, Au, Pt, Cu) TiO2/SiO2@Fe3O4 nanocomposites were prepared by an ultrasonic-assisted sol-gel method. All prepared samples were characterized by X-ray powder diffraction (XRD) analysis, Brunauer-Emmett-Teller (BET) method, X-ray photoelectron spectroscopy (XPS), scanning transmission electron microscopy (STEM), Mott-Schottky analysis and photoluminescence spectroscopy (PL). Phenol oxidation pathways of magnetic photocatalysts modified with Pt, Pd, Cu and Au nanoparticles proceeded by generation of reactive oxygen species, which oxidized phenol to benzoquinone, hydroquinone and catechol. Benzoquinone and maleic acid were products, which were determined in the hydroquinone oxidation pathway. The highest mineralization rate was observed for Pd-TiO2/SiO2@Fe3O4 and Cu-TiO2/SiO2@Fe3O4 photocatalysts, which produced the highest concentration of catechol during photocatalytic reaction. For Pt-TiO2/SiO2@Fe3O4 nanocomposite, a lack of catechol after 60 min of irradiation resulted in low mineralization rate (CO2 formation). It is proposed that the enhanced photocatalytic activity of palladium and copper-modified photocatalysts is related to an increase in the amount of adsorption sites and efficient charge carrier separation, whereas the keto-enol tautomeric equilibrium retards the rate of phenol photomineralization on Au-TiO2/SiO2@Fe3O4. The magnetization hysteresis loop indicated that the obtained hybrid photocatalyst showed magnetic properties and therefore could be easily separated after treatment process. PMID:29316667

Enhanced Dissolution of Platinum Group Metals Using Electroless Iron Deposition Pretreatment

NASA Astrophysics Data System (ADS)

Taninouchi, Yu-ki; Okabe, Toru H.

2017-12-01

In order to develop a new method for efficiently recovering platinum group metals (PGMs) from catalyst scraps, the authors investigated an efficient dissolution process where the material was pretreated by electroless Fe deposition. When Rh-loaded alumina powder was kept in aqua regia at 313 K (40 °C) for 30 to 60 minutes, the Rh hardly dissolved. Meanwhile, after electroless Fe plating using a bath containing sodium borohydride and potassium sodium tartrate as the reducing and complexing agents, respectively, approximately 60 pct of Rh was extracted by aqua regia at 313 K (40 °C) after 30 minutes. Furthermore, when heat treatment was performed at 1200 K (927 °C) for 60 minutes in vacuum after electroless plating, the extraction of Rh approached 100 pct for the same leaching conditions. The authors also confirmed that the Fe deposition pretreatment enhanced the dissolution of Pt and Pd. These results indicate that an effective and environmentally friendly process for the separation and extraction of PGMs from catalyst scraps can be developed utilizing this Fe deposition pretreatment.

Joining of Zirconium Diboride-Based Ceramic Composites to Metallic Systems for High-Temperature Applications

NASA Technical Reports Server (NTRS)

Asthana, R.; Singh, M.

2008-01-01

Three types of hot-pressed zirconium diboride (ZrB2)-based ultra-high-temperature ceramic composites (UHTCC), ZrB2-SiC (ZS), ZrB2-SiC-C (ZSC), and ZrB2-SCS9-SiC (ZSS), were joined to Cu-clad-Mo using two Ag-Cu brazes (Cusil-ABA and Ticusil, T(sub L) approx.1073-1173 K) and two Pd-base brazes (Palco and Palni, T(sub L) approx.1493-1513 K). Scanning Electron Microscopy (SEM) coupled with energy-dispersive spectroscopy (EDS) revealed greater chemical interaction in joints made using Pd-base brazes than in joints made using Ag-Cu based active brazes. The degree of densification achieved in hot pressed composites influenced the Knoop hardness of the UHTCC and the hardness distribution across the braze interlayer. The braze region in Pd-base system displayed higher hardness in joints made using fully-dense ZS composites than in joints made using partially-dense ZSS composites and the carbon-containing ZSC composites. Calculations indicate a small negative elastic strain energy and an increase in the UHTCC's fracture stress up to a critical clad layer thickness . Above this critical thickness, strain energy in the UHTCC is positive, and it increases with increasing clad layer thickness. Empirical projections show a reduction in the effective thermal resistance of the joints and highlight the potential benefits of joining the UHTCC to Cu-clad-Mo.

Natural sunlight irradiated flower-like CuS synthesized from DMF solvothermal treatment

NASA Astrophysics Data System (ADS)

Zhao, Wei; Wang, Zihao; Zhou, Lei; Liu, Nianqi; Wang, Hongxing

2016-09-01

Three-dimensional CuS hierarchical crystals with high catalytic activity had been successfully fabricated using a facile solvothermal process. The CuS microparticles showed different flower-like morphology and good dispersion by optimizing reaction conditions. It was found that using N,N-dimethylformamide (DMF) as the solvent reagent in the proper temperature conditions was favorable for the growth of hierarchically structured CuS. The hexagonal flower-like CuS synthesized at 170°C for 60 min displayed broad-spectrum photocatalytic properties under ultraviolet (UV) and visible irradiation. The as-prepared CuS crystals exhibited good performance to decolorize methylene blue (MB) solution under visible light irradiation. The total organic carbon (TOC) removal of rhodamine B (RhB) solution was nearly 60% after 5 h of the natural sunlight irradiation, and the property was stable after testing over four recycles, demonstrating a potential application in waster water treatment.

Comparison of National Operative Mortality in Gastroenterological Surgery Using Web-based Prospective Data Entry Systems.

PubMed

Anazawa, Takayuki; Paruch, Jennifer L; Miyata, Hiroaki; Gotoh, Mitsukazu; Ko, Clifford Y; Cohen, Mark E; Hirahara, Norimichi; Zhou, Lynn; Konno, Hiroyuki; Wakabayashi, Go; Sugihara, Kenichi; Mori, Masaki

2015-12-01

International collaboration is important in healthcare quality evaluation; however, few international comparisons of general surgery outcomes have been accomplished. Furthermore, predictive model application for risk stratification has not been internationally evaluated. The National Clinical Database (NCD) in Japan was developed in collaboration with the American College of Surgeons National Surgical Quality Improvement Program (ACS-NSQIP), with a goal of creating a standardized surgery database for quality improvement. The study aimed to compare the consistency and impact of risk factors of 3 major gastroenterological surgical procedures in Japan and the United States (US) using web-based prospective data entry systems: right hemicolectomy (RH), low anterior resection (LAR), and pancreaticoduodenectomy (PD).Data from NCD and ACS-NSQIP, collected over 2 years, were examined. Logistic regression models were used for predicting 30-day mortality for both countries. Models were exchanged and evaluated to determine whether the models built for one population were accurate for the other population.We obtained data for 113,980 patients; 50,501 (Japan: 34,638; US: 15,863), 42,770 (Japan: 35,445; US: 7325), and 20,709 (Japan: 15,527; US: 5182) underwent RH, LAR, and, PD, respectively. Thirty-day mortality rates for RH were 0.76% (Japan) and 1.88% (US); rates for LAR were 0.43% versus 1.08%; and rates for PD were 1.35% versus 2.57%. Patient background, comorbidities, and practice style were different between Japan and the US. In the models, the odds ratio for each variable was similar between NCD and ACS-NSQIP. Local risk models could predict mortality using local data, but could not accurately predict mortality using data from other countries.We demonstrated the feasibility and efficacy of the international collaborative research between Japan and the US, but found that local risk models remain essential for quality improvement.

Al and Si Alloying Effect on Solder Joint Reliability in Sn-0.5Cu for Automotive Electronics

NASA Astrophysics Data System (ADS)

Hong, Won Sik; Oh, Chulmin; Kim, Mi-Song; Lee, Young Woo; Kim, Hui Joong; Hong, Sung Jae; Moon, Jeong Tak

2016-12-01

To suppress the bonding strength degradation of solder joints in automotive electronics, we proposed a mid-temperature quaternary Pb-free Sn-0.5Cu solder alloy with minor Pd, Al, Si and Ge alloying elements. We manufactured powders and solder pastes of Sn-0.5Cu-(0.01,0.03)Al-0.005Si-(0.006-0.007)Ge alloys ( T m = 230°C), and vehicle electronic control units used for a flame-retardant-4 printed circuit board with an organic solderability preservative finish were assembled by a reflow soldering process. To investigate the degradation properties of solder joints used in engine compartments, thermal cycling tests were conducted from -40°C to 125°C (10 min dwell) for 1500 cycles. We also measured the shear strength of the solder joints in various components and observed the microstructural evolution of the solder joints. Based on these results, intermetallic compound (IMC) growth at the solder joints was suppressed by minor Pd, Al and Si additions to the Sn-0.5Cu alloy. After 1500 thermal cycles, IMC layers thicknesses for 100 parts per million (ppm) and 300 ppm Al alloy additions were 6.7 μm and 10 μm, compared to the as-reflowed bonding thicknesses of 6 μm and 7 μm, respectively. Furthermore, shear strength degradation rates for 100 ppm and 300 ppm Al(Si) alloy additions were at least 19.5%-26.2%. The cause of the improvement in thermal cycling reliability was analyzed using the (Al,Cu)-Sn, Si-Sn and Al-Sn phases dispersed around the Cu6Sn5 intermetallic at the solder matrix and bonding interfaces. From these results, we propose the possibility of a mid-temperature Sn-0.5Cu(Pd)-Al(Si)-Ge Pb-free solder for automotive engine compartment electronics.

A New Bioinspired Perchlorate Reduction Catalyst with Significantly Enhanced Stability via Rational Tuning of Rhenium Coordination Chemistry and Heterogeneous Reaction Pathway.

PubMed

Liu, Jinyong; Han, Mengwei; Wu, Dimao; Chen, Xi; Choe, Jong Kwon; Werth, Charles J; Strathmann, Timothy J

2016-06-07

Rapid reduction of aqueous ClO4(-) to Cl(-) by H2 has been realized by a heterogeneous Re(hoz)2-Pd/C catalyst integrating Re(O)(hoz)2Cl complex (hoz = oxazolinyl-phenolato bidentate ligand) and Pd nanoparticles on carbon support, but ClOx(-) intermediates formed during reactions with concentrated ClO4(-) promote irreversible Re complex decomposition and catalyst deactivation. The original catalyst design mimics the microbial ClO4(-) reductase, which integrates Mo(MGD)2 complex (MGD = molybdopterin guanine dinucleotide) for oxygen atom transfer (OAT). Perchlorate-reducing microorganisms employ a separate enzyme, chlorite dismutase, to prevent accumulation of the destructive ClO2(-) intermediate. The structural intricacy of MGD ligand and the two-enzyme mechanism for microbial ClO4(-) reduction inspired us to improve catalyst stability by rationally tuning Re ligand structure and adding a ClOx(-) scavenger. Two new Re complexes, Re(O)(htz)2Cl and Re(O)(hoz)(htz)Cl (htz = thiazolinyl-phenolato bidentate ligand), significantly mitigate Re complex decomposition by slightly lowering the OAT activity when immobilized in Pd/C. Further stability enhancement is then obtained by switching the nanoparticles from Pd to Rh, which exhibits high reactivity with ClOx(-) intermediates and thus prevents their deactivating reaction with the Re complex. Compared to Re(hoz)2-Pd/C, the new Re(hoz)(htz)-Rh/C catalyst exhibits similar ClO4(-) reduction activity but superior stability, evidenced by a decrease of Re leaching from 37% to 0.25% and stability of surface Re speciation following the treatment of a concentrated "challenge" solution containing 1000 ppm of ClO4(-). This work demonstrates the pivotal roles of coordination chemistry control and tuning of individual catalyst components for achieving both high activity and stability in environmental catalyst applications.

Evaluation of inductively heated ferromagnetic alloy implants for therapeutic interstitial hyperthermia.

PubMed

Paulus, J A; Richardson, J S; Tucker, R D; Park, J B

1996-04-01

Ferromagnetic alloys heated by magnetic induction have been investigated as interstitial hyperthermia delivery implants for over a decade, utilizing low Curie temperatures to provide thermal self-regulation. The minimally invasive method is attractive for fractionated thermal treatment of tumors which are not easily heated by focused microwave or ultrasound techniques. Past analyses of ferromagnetic seeds by other authors depict poor experimental correlation with theoretical heating predictions. Improvements in computer hardware and commercially available finite element analysis software have simplified the analysis of inductively heated thermal seeds considerably. This manuscript examines end effects of finite length implants and nonlinear magnetic material properties to account for previous inconsistencies. Two alloys, Ni-28 wt% Cu (NiCu) and Pd-6.15 wt% Co (PdCo), were used for comparison of theoretical and experimental calorimetric results. Length to diameter (L/d) ratios of over 20 for cylindrical seeds are necessary for minimization of end effects. Magnetic properties tested for alloys of NiCu and PdCo illustrate considerable nonlinearity of these materials in field strength ranges used for induction heating. Field strength dependent magnetic permeabilities and calorimetric data illustrate that more detailed material information must be included to accurately estimate induction power loss for these implants.

Metal Nanoparticles Covered with a Metal-Organic Framework: From One-Pot Synthetic Methods to Synergistic Energy Storage and Conversion Functions.

PubMed

Kobayashi, Hirokazu; Mitsuka, Yuko; Kitagawa, Hiroshi

2016-08-01

Hybrid materials composed of metal nanoparticles and metal-organic frameworks (MOFs) have attracted much attention in many applications, such as enhanced gas storage and catalytic, magnetic, and optical properties, because of the synergetic effects between the metal nanoparticles and MOFs. In this Forum Article, we describe our recent progress on novel synthetic methods to produce metal nanoparticles covered with a MOF (metal@MOF). We first present Pd@copper(II) 1,3,5-benzenetricarboxylate (HKUST-1) as a novel hydrogen-storage material. The HKUST-1 coating on Pd nanocrystals results in a remarkably enhanced hydrogen-storage capacity and speed in the Pd nanocrystals, originating from charge transfer from Pd nanocrystals to HKUST-1. Another material, Pd-Au@Zn(MeIM)2 (ZIF-8, where HMeIM = 2-methylimidazole), exhibits much different catalytic activity for alcohol oxidation compared with Pd-Au nanoparticles, indicating a design guideline for the development of composite catalysts with high selectivity. A composite material composed of Cu nanoparticles and Cr3F(H2O)2O{C6H3(CO2)3}2 (MIL-100-Cr) demonstrates higher catalytic activity for CO2 reduction into methanol than Cu/γ-Al2O3. We also present novel one-pot synthetic methods to produce composite materials including Pd/ZIF-8 and Ni@Ni2(dhtp) (MOF-74, where H4dhtp = 2,5-dihydroxyterephthalic acid).

Noble metal abundances in komatiite suites from Alexo, Ontario and Gorgona Island, Colombia

NASA Astrophysics Data System (ADS)

Brügmann, G. E.; Arndt, N. T.; Hofmann, A. W.; Tobschall, H. J.

1987-08-01

The distribution of the chalcophile and siderophile metals Cu, Ni, Au, Pd, Ir, Os and Ru in an Archaean komatiite flow from Alexo, Ontario and in a Phanerozoic komatiitic suite of Gorgona Island, Colombia, provides new information about the geochemical behaviour of these elements. Copper, Au and Pd behave as incompatible elements during the crystallization of these ultramafic magmas. In contrast, Ni, Ir, Os and Ru concentrations systematically decrease with decreasing MgO contents, a pattern characteristic of compatible elements. These trends are most probably controlled by olivine crystallization, which implies that Ir, Os and Ru are compatible in olivine. Calculated partition coefficients for Ir, Os and Ru between olivine and the melt are about 1.8. Compared to primitive mantle, parental komatiitic liquids are enriched in (incompatible) Cu, Au and Pd and depleted in (compatible) Ir, Os and Ru. Within both Archaean and Phanerozoic komatiites, noble metal ratios such as Au/Pd, Ir/Os, Os/Ru and Ru/Ir and ratios of lithophile and siderophile elements such as Ti/Pd, Ti/Au are constant and similar to primitive mantle values. This implies that Au and Pd are moderately incompatible elements and that there has been no significant fractionation of siderophile and lithophile elements since the Archaean. Platinum-group element abundances of normal MORB are highly variable and always much lower than in komatiites, because MORB magma is saturated with sulfur and a variable but minor amount of sulfide segregated during mantle melting or during the ascent of magma to the surface. Sulfide deposits associated with komatiites display similar chalcophile element patterns to those of komatiites. Noble metal ratios such as Pd/Ir, Au/Ir, Pd/Os and Pd/Ru can be used to determine the composition of the host komatiite at the time of sulfide segregation.

Environmental tests of metallization systems for terrestrial photovoltaic cells

NASA Technical Reports Server (NTRS)

Alexander, P., Jr.

1985-01-01

Seven different solar cell metallization systems were subjected to temperature cycling tests and humidity tests. Temperature cycling excursions were -50 deg C to 150 deg C per cycle. Humidity conditions were 70 deg C at 98% relative humidity. The seven metallization systems were: Ti/Ag, Ti/Pd/Ag, Ti/Pd/Cu, Ni/Cu, Pd/Ni/Solder, Cr/Pd/Ag, and thick film Ag. All metallization systems showed a slight to moderate decrease in cell efficiencies after subjection to 1000 temperature cycles. Six of the seven metallization systems also evidenced slight increases in cell efficiencies after moderate numbers of cycles, generally less than 100 cycles. The copper based systems showed the largest decrease in cell efficiencies after temperature cycling. All metallization systems showed moderate to large decreases in cell efficiencies after 123 days of humidity exposure. The copper based systems again showed the largest decrease in cell efficiencies after humidity exposure. Graphs of the environmental exposures versus cell efficiencies are presented for each metallization system, as well as environmental exposures versus fill factors or series resistance.

Copper toxicity and date palm (Phoenix dactylifera) seedling tolerance: Monitoring of related biomarkers.

PubMed

Chaâbene, Zayneb; Hakim, Imen Rekik; Rorat, Agnieszka; Elleuch, Amine; Mejdoub, Hafedh; Vandenbulcke, Franck

2018-03-01

Date palm (Phoenix dactylifera) seeds were exposed to different copper (Cu) solutions to examine plant stress responses. Low Cu concentrations (0.02 and 0.2 mM) caused an increase of seed germination, whereas higher Cu amounts (2 mM) significantly inhibited seed germination, delayed hypocotyl elongation, increased seedling mortality, and reduced the germination index by more than 90%. Metal-related toxicity symptoms appeared after 15 d of 2 mM of Cu exposure. Biochemical activities such as amylase activity and redox balance elements were examined to study the relationship between external Cu amount and internal plant response. The present study showed that amylolytic activity was dose- and time-dependent. Likewise, H 2 O 2 production increased after exposure to Cu, which was correlated with thiobarbituric acid reactive substance (TBARS) accumulation. Furthermore at low Cu concentrations, superoxide dismutase (SOD) and catalase (CAT) activities increased, suggesting that date palm seed stimulated its metal homeostasis networks. However, the highest cupric ion amounts increased cell oxidant accumulation and reduced enzyme production. Gene expression level measures of P. dactylifera phytochelatin synthase (Pdpcs) and P. dactylifera metallothionein (Pdmt) encoding genes have been carried out to investigate the implication of PdPCS and PdMT proteins in Cu homeostasis and/or its sequestration. Phoenix dactylifera metallothionein induction reached a peak after 30 d of exposure to 0.2 mM of Cu. However, it was down-regulated in plants exposed to higher Cu concentrations. In the same conditions, Pdpcs was overexpressed during 1 mo of exposure before it decreased thereafter. These observations provide a new insight into date palm cell response to Cu, a metal that can be toxic but that is also an essential element. Environ Toxicol Chem 2018;37:797-806. © 2017 SETAC. © 2017 SETAC.

Interference removals on Pd, Ru and Au with ICP-QQQ-MS in PGE RM

NASA Astrophysics Data System (ADS)

Nadeem Hussain Bokhari, Syed; Meisel, Thomas; Walkner, Christoph

2015-04-01

Gold and platinum group elements (PGE) are essential industrial precious metals with high world demand due to their unique properties. Struggle for natural exploration of PGE is on great pace and recycling from industrial wastes, electronics and catalytic convertor is on the rise for PGE supply chain. Along with these developments it is becoming more challenging for analytical chemists to determine gold and PGE out of complex matrix which causes severe interferences. The current state of art is online analysis coupled with chromatographic separation of interferences. The ICP-QQQ-MS Agilent 8800 has the capability of using multi tunes and mass shifts. We aim to remove interferences on Pd+ (for direct and isotope dilution analysis) Au+ and Ru+ in lieu of chemical separations. YO+, SrOH+, ZnAr+, NiAr+, ZrO+, CuAr+, MoO+ , Ru+and Cd+ are expected interferences on Pd+ while Au+ is interfered by TaO+, HfOH+, GdAr+ and 102Ru+ ,104Ru+ by 102Pd+ ,104Pd+ etc. Initial test were performed on pure solutions of 1mg/l (interfering elements): 1 ng/l (Pd, Ru & Au) respectively. The outcomes of initial tests were applied on PGE reference material (RM) WMG-1 and SARM-7 (digested with Na2O2 sintering). The results obtained show that YO+, SrOH+ interfere (104Pd,105Pd), 104 Ru+ on (104Pd), ZnAr+ has slight interference on (104Pd and106Pd), ZrO+, NiAr+, CuAr+ interferences are negligible, MoO+ has severe interference on (108Pd, 110Pd) and that Cd+ has severe isobaric interference on (106Pd,108Pd, 110Pd). These interference have been removed by formation of Pd(NH3)3+complex. The TaO+, HfOH+ and GdAr+ interferences on Au+ are best removed by formation of Au(NH3)+ and Au(NH3)2+ complexes. 102Pd+,104Pd+interference on 102Ru+ ,104Ru+ can be removed by formation of Ru(NH3)4+ and RuO+ compounds. The results obtained comply with certified values of RM. The developed method is being tested on low concentration PGE reference materials. References: Sugiyama, N. " Removal of complex spectral interferences on noble metal isotopes." Agilent 8800 ICP-QQQ Application Handbook, 2014, 42-46.

Magma Fertility is the First-Order Factor for the Formation of Porphyry Cu±Au Deposits

NASA Astrophysics Data System (ADS)

Park, J. W.; Campbell, I. H.; Malaviarachchi, S. P. K.; Cocker, H.; Nakamura, E.; Kay, S. M.

2017-12-01

Magma fertility, the metal abundance in magma, has been considered to be one of the key factors for the formation of porphyry Cu±Au deposits. In this study we provide clear evidence to support the hypothesis that the platinum group element (PGE) can be used to distinguish barren from ore-bearing Cu±Au felsic suites. We determined the PGE contents of three barren volcanic and subvolcanic suites from Argentina and Japan, and compare the results with two porphyry Cu-bearing subvolcanic suites from Chile and two porphyry Cu-Au-bearing suites from Australia. The barren suites are significantly depleted in PGE abundances by the time of fluid exsolution, which is attributed to early sulfide saturation at mid to lower crust depths or assimilation of chalcophile element-poor crustal materials. Barren magma, produced by melting continental crust, may have been initially deficient in chalcophile elements. In contrast, the Cu±Au ore-bearing suites contain at least an order of magnitude higher PGE contents than those of the barren suites by the time of fluid saturation. They are characterized by late sulfide saturation in a shallow magma chamber, which allows the chalcophile elements to concentrate in the fractionating magma from which they are sequestered by ore-forming fluids. We suggest the Pd/MgO and Pd/Pt ratios of igneous rocks can be used as magma fertility indicators, and to distinguish between barren, porphyry Cu and porphyry Cu-Au magmatic systems.

Isonitrile radionuclide complexes for labelling and imaging agents

DOEpatents

Jones, Alun G.; Davison, Alan; Abrams, Michael J.

1984-06-04

A coordination complex of an isonitrile ligand and radionuclide such as Tc, Ru, Co, Pt, Fe, Os, Ir, W, Re, Cr, Mo, Mn, Ni, Rh, Pd, Nb and Ta, is useful as a diagnostic agent for labelling liposomes or vesicles, and selected living cells containing lipid membranes, such as blood clots, myocardial tissue, gall bladder tissue, etc.

Concentration of some platinum-group metals in coal

USGS Publications Warehouse

Finkelman, R.B.; Aruscavage, P. J.

1981-01-01

New data on some platinum group metals in coal indicate that the concentration of Pt is generally less than about 5 ppb, that of Pd is generally less than 1 ppb, and that of Rh is generally less than 0.5 ppb. No conclusive evidence was obtained concerning the mode of occurrence of these elements in coal. ?? 1981.

Enhanced photocatalytic H2 production of Mn0.5Cd0.5S solid solution through loading transition metal sulfides XS (X = Mo, Cu, Pd) cocatalysts

NASA Astrophysics Data System (ADS)

Zhai, Huishan; Liu, Xiaolei; Wang, Peng; Huang, Baibiao; Zhang, Qianqian

2018-02-01

Development of highly efficient cocatalyst is important towards photocatalytic H2 production. Herein, a series of transition metal sulfides XS (X = Mo, Cu, Pd) as cocatalysts have been successfully grown on Mn0.5Cd0.5S photocatalyst through photo-reduction or in-situ deposition method, respectively. Among them, the maximum production of H2 obtained from MoS2/Mn0.5Cd0.5S, CuxS/Mn0.5Cd0.5S (1 ≤ x ≤ 2) and PdS/Mn0.5Cd0.5S samples were 197, 347 and 614 μmol/h, which were around 6.5, 11.5 and 20.3 times than pristine Mn0.5Cd0.5S. MoS2/Mn0.5Cd0.5S heterostructure can facilitate electron transfer from Mn0.5Cd0.5S to MoS2 and MoS2 as active site for H2 production, p-n junction constructed between Mn0.5Cd0.5S and CuxS can efficiently separate the photo-generated carriers and PdS as a hole acceptor can accelerate the consume of photo-generated holes to enhance the photocatalytic H2 production. The effective charge transfer was further proved by the weaker PL intensity and stronger photocurrent density relative to that of Mn0.5Cd0.5S alone. This work demonstrated that transition metal sulfides XS (X = Mo, Cu, Pd) are efficient cocatalysts to improve the H2 production performance of Mn0.5Cd0.5S photocatalyst.

Charge partitioning and anomalous hole doping in Rh-doped Sr2IrO4

NASA Astrophysics Data System (ADS)

Chikara, S.; Fabbris, G.; Terzic, J.; Cao, G.; Khomskii, D.; Haskel, D.

2017-02-01

The simultaneous presence of sizable spin-orbit interactions and electron correlations in iridium oxides has led to predictions of novel ground states including Dirac semimetals, Kitaev spin liquids, and superconductivity. Electron and hole doping studies of spin-orbit assisted Mott insulator Sr2Ir O4 are being intensively pursued due to extensive parallels with the La2CuO4 parent compound of cuprate superconductors. In particular, the mechanism of charge doping associated with replacement of Ir with Rh ions remains controversial with profound consequences for the interpretation of electronic structure and transport data. Using x-ray absorption near edge structure measurements at the Rh L, K, and Ir L edges we observe anomalous evolution of charge partitioning between Rh and Ir with Rh doping. The partitioning of charge between Rh and Ir sites progresses in a way that holes are initially doped into the Jeff=1 /2 band at low x only to be removed from it at higher x values. This anomalous hole doping naturally explains the reentrant insulating phase in the phase diagram of Sr2Ir1 -xRhxO4 and ought to be considered when searching for superconductivity and other emergent phenomena in iridates doped with 4 d elements.

Photo-reduced Cu/CuO nanoclusters on TiO2 nanotube arrays as highly efficient and reusable catalyst

NASA Astrophysics Data System (ADS)

Jin, Zhao; Liu, Chang; Qi, Kun; Cui, Xiaoqiang

2017-01-01

Non-noble metal nanoparticles are becoming more and more important in catalysis recently. Cu/CuO nanoclusters on highly ordered TiO2 nanotube arrays are successfully developed by a surfactant-free photoreduction method. This non-noble metal Cu/CuO-TiO2 catalyst exhibits excellent catalytic activity and stability for the reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) with the presence of sodium borohydride (NaBH4). The rate constant of this low-cost Cu/CuO based catalyst is even higher than that of the noble metal nanoparticles decorated on the same TiO2 substrate. The conversion efficiency remains almost unchanged after 7 cycles of recycling. The recycle process of this Cu/CuO-TiO2 catalyst supported by Ti foil is very simple and convenient compared with that of the common powder catalysts. This catalyst also exhibited great catalytic activity to other organic dyes, such as methylene blue (MB), rhodamine B (RhB) and methyl orange (MO). This highly efficient, low-cost and easily reusable Cu/CuO-TiO2 catalyst is expected to be of great potential in catalysis in the future.

Density-functional theory study of dimethyl carbonate synthesis by methanol oxidative carbonylation on single-atom Cu1/graphene catalyst

NASA Astrophysics Data System (ADS)

Sun, Wei; Shi, Ruina; Wang, Xuhui; Liu, Shusen; Han, Xiaoxia; Zhao, Chaofan; Li, Zhong; Ren, Jun

2017-12-01

The mechanism for dimethyl carbonate (DMC) synthesis by oxidation carbonylation of methanol on a single-atom Cu1/graphene catalyst was investigated by density-functional theory calculations. Carbon vacancies in graphene can significantly enhance the interaction between Cu atoms and graphene supports, and provide an increased transfer of electrons from Cu atoms to the graphene sheet. Compared with Cu-doped divacancy graphene (Cu/DG), Cu-doped monovacancy graphene (Cu/MG) provides a stronger interaction between adsorbents and the catalyst surface. Among the reaction processes over Cu1/graphene catalysts, CO insertion into methoxide was more favorable than dimethoxide. The rate-limiting step on the Cu/DG surface is the carbomethoxide reaction with methoxide, which is exothermic by 164.6 kJ mol-1 and has an activation barrier of 190.9 kJ mol-1 energy. Compared with that on the Cu crystal surface, Cu4 and Cu3Rh clusters, and the Cu2O(111) surface, the rate-determining step for DMC formation on Cu/MG, which is CO insertion into methoxide, needs to overcome the lowest barrier of 73.5 kJ mol-1 and is exothermic by 44.6 kJ mol-1. Therefore, Cu/MG was beneficial to the formation of DMC as a single-atom catalyst.

Silicon dendritic web material

NASA Technical Reports Server (NTRS)

Meier, D. L.; Campbell, R. B.; Sienkiewicz, L. J.; Rai-Choudhury, P.

1982-01-01

The development of a low cost and reliable contact system for solar cells and the fabrication of several solar cell modules using ultrasonic bonding for the interconnection of cells and ethylene vinyl acetate as the potting material for module encapsulation are examined. The cells in the modules were made from dendritic web silicon. To reduce cost, the electroplated layer of silver was replaced with an electroplated layer of copper. The modules that were fabricated used the evaporated Ti, Pd, Ag and electroplated Cu (TiPdAg/Cu) system. Adherence of Ni to Si is improved if a nickel silicide can be formed by heat treatment. The effectiveness of Ni as a diffusion barrier to Cu and the ease with which nickel silicide is formed is discussed. The fabrication of three modules using dendritic web silicon and employing ultrasonic bonding for interconnecting calls and ethylene vinyl acetate as the potting material is examined.

Silicon dendritic web material

NASA Astrophysics Data System (ADS)

Meier, D. L.; Campbell, R. B.; Sienkiewicz, L. J.; Rai-Choudhury, P.

1982-03-01

The development of a low cost and reliable contact system for solar cells and the fabrication of several solar cell modules using ultrasonic bonding for the interconnection of cells and ethylene vinyl acetate as the potting material for module encapsulation are examined. The cells in the modules were made from dendritic web silicon. To reduce cost, the electroplated layer of silver was replaced with an electroplated layer of copper. The modules that were fabricated used the evaporated Ti, Pd, Ag and electroplated Cu (TiPdAg/Cu) system. Adherence of Ni to Si is improved if a nickel silicide can be formed by heat treatment. The effectiveness of Ni as a diffusion barrier to Cu and the ease with which nickel silicide is formed is discussed. The fabrication of three modules using dendritic web silicon and employing ultrasonic bonding for interconnecting calls and ethylene vinyl acetate as the potting material is examined.

Ferromagnetism of Pd-Fe (abstract)

NASA Astrophysics Data System (ADS)

Griffith, G.; Carnegie, D. W., Jr.; Claus, H.

1984-03-01

We present new low field ac susceptibility measurements on Pd1-xFex alloys (0.002≤X<0.01). The Curie temperature TC, determined from these measurements, are significantly lower than those previously obtained in higher magnetic fields [G. J. Nieuwenhuys, Adv. Phys. 24, 515 (1975)]. We also found that for a given sample, TC depends very sensitively on its heat treatment. As an example, for an alloy with 0.4 at. % Fe, TC can be varied between 4 and 10 K. In other alloys, like PdNi or RhNi similar changes in TC are due to changes in the degree of atomic short-range order [S. Crane, D. W. Carnegie, Jr., and H. Claus, J. Appl. Phys. 53, 2179 (1982)]. However, for PdFe we show evidence that the changes in TC are due to absorption of small amounts of oxygen, the samples with the highest amount of oxygen having the highest TC. It thus seems that oxygen has the opposite effect from hydrogen on the exchange enhanced susceptibility of Pd [J. A. Mydosh, Phys. Rev. Lett. 33, 1562 (1974)].

Controls on ferromanganese crust composition and reconnaissance resource potential, Ninetyeast Ridge, Indian Ocean

USGS Publications Warehouse

Hein, James; Conrad, Tracey A.; Mizell, Kira; Banakar, Virupaxa K.; Frey, Frederick A.; Sager, William W.

2016-01-01

The southern third of NER has Fe-Mn crusts with the highest Co (0.91%), Ni (0.43%), ΣREY (0.33%), Cu (0.22%), Te (146 ppm), Pt (1.5 ppm), Ru (52 ppb), and Rh (99 ppb) contents. These are among the highest Pt, Ru, and Rh concentrations measured in marine Fe-Mn deposits. Because of these high metal concentrations, exploration is warranted for the southern sector of the NER, especially at shallower-water sites where the platinum group elements (PGE) and Co are likely to be even more enriched.

Charge Order and Superconductivity in Underdoped YBa2 Cu3 O7 -δ under Pressure

NASA Astrophysics Data System (ADS)

Putzke, Carsten; Ayres, Jake; Buhot, Jonathan; Licciardello, Salvatore; Hussey, Nigel E.; Friedemann, Sven; Carrington, Antony

2018-03-01

In underdoped cuprates, an incommensurate charge density wave (CDW) order is known to coexist with superconductivity. A dip in Tc at the hole doping level where the CDW is strongest (np≃0.12 ) suggests that CDW order may suppress superconductivity. We investigate the interplay of charge order with superconductivity in underdoped YBa2 Cu3 O7 -δ by measuring the temperature dependence of the Hall coefficient RH(T ) at high magnetic field and at high hydrostatic pressure. We find that, although pressure increases Tc by up to 10 K at 2.6 GPa, it has very little effect on RH(T ). This suggests that pressure, at these levels, only weakly affects the CDW and that the increase in Tc with pressure cannot be attributed to a suppression of the CDW. We argue, therefore, that the dip in Tc at np≃0.12 at ambient pressure is probably not caused by the CDW formation.

Organic chemistry. A rhodium catalyst for single-step styrene production from benzene and ethylene.

PubMed

Vaughan, Benjamin A; Webster-Gardiner, Michael S; Cundari, Thomas R; Gunnoe, T Brent

2015-04-24

Rising global demand for fossil resources has prompted a renewed interest in catalyst technologies that increase the efficiency of conversion of hydrocarbons from petroleum and natural gas to higher-value materials. Styrene is currently produced from benzene and ethylene through the intermediacy of ethylbenzene, which must be dehydrogenated in a separate step. The direct oxidative conversion of benzene and ethylene to styrene could provide a more efficient route, but achieving high selectivity and yield for this reaction has been challenging. Here, we report that the Rh catalyst ((Fl)DAB)Rh(TFA)(η(2)-C2H4) [(Fl)DAB is N,N'-bis(pentafluorophenyl)-2,3-dimethyl-1,4-diaza-1,3-butadiene; TFA is trifluoroacetate] converts benzene, ethylene, and Cu(II) acetate to styrene, Cu(I) acetate, and acetic acid with 100% selectivity and yields ≥95%. Turnover numbers >800 have been demonstrated, with catalyst stability up to 96 hours. Copyright © 2015, American Association for the Advancement of Science.

Environmental and alloying effects on corrosion of metals and alloys

NASA Astrophysics Data System (ADS)

Liang, Dong

2009-12-01

In the first part of this project, corrosion studies were carried out on 304L stainless steel samples welded with Cr-free consumables, which were developed to minimize the concentration of chromate species in the weld fume. The corrosion properties of Ni-Cu and Ni-Cu-Pd Gas Tungsten Arc (GTA) welds and Shielded Metal Arc (SMA) welds are comparable to those of welds fabricated with SS308L consumable, which is the standard consumable for welding 304L. Although the breakdown potentials of the new welds from both welding processes are lower than that of the SS308L weld, the repassivation potential of these new welds is much higher. Generally, the repassivation potential is a more conservative measure of susceptibility to localized corrosion. Our studies showed that the Ni-Cu and Ni-Cu-Pd welds are more resistant to crevice corrosion than SS308L welds, which is related to the high repassivation potential. Also, addition of Pd improved the corrosion resistance of the new welds, which is consistent with previous studies from button samples and bead-on-plate samples. Other corrosion studies such as creviced and uncreviced long time immersion, atmospheric exposure, and slow strain rate testing suggest that Ni-Cu-Pd welds can be a qualified substitute for SS308 weld. In the second part of this project, efforts are put on the connection between lab and field exposure tests because sometimes the correspondence between lab atmospheric corrosion tests (ASTM B117) and field exposures is poor as a result of differences in the critical conditions controlling chemical and electrochemical reactions on surfaces. Recent studies in atmospheric chemistry revealed the formation of extremely reactive species from interactions between UV light, chloride aerosols above oceans and oxidizing agents such as ozone or peroxide. Atmospheric corrosion of metals can be affected by these species which might be transported long distances in the atmosphere to locations far from oceans. However, these species could be missed in standard laboratory exposures such as ASTM B117. Initial efforts focused on the effects UV radiation, O3, relative humidity on the atmospheric corrosion of bare silver. Later work addressed the corrosion of silver samples deposited with NaCl particles. An exposure chamber that can simulate various environmental effects was built. The effects of UV radiation, O3, and relative humidity were varied separately while keeping the other factors the same level. The corrosion products were analyzed by the galvanostatic reduction method and characterization techniques such as SEM and EDS. It was found that both UV and O3 are necessary for fast corrosion on bare silver and this fast corrosion reaction results from atomic oxygen generated photodegradation of O3. In the presence of UV and O3, relative humidity has little effect on the atmospheric corrosion of bare silver in contrast to conventional atmospheric corrosion. The degree of corrosion is found to increase with O3 concentration. Moreover, a kinetic study of atmospheric corrosion of bare silver found that an incubation time for the atmospheric corrosion attack is needed. This incubation time is related to the chemisorption process of atomic oxygen. Though UV radiation can form reactive atomic oxygen which is more reactive than O3 alone as shown in the last chapter, the enhancement of corrosion by UV is limited for Ag with NaCl particles at low ozone concentration and high RH. The corrosion rate of silver with NaCl particles is found to increase with relative humidity, which is different than the case of bare silver. This indicates that different mechanisms control the atmospheric corrosion of silver. The incubation time for corrosion of silver with NaCl particles is shorter than for bare silver. This result from chemisorption of Cl 2 is favored over that of atomic oxygen. Interestingly, the total corrosion product of silver with NaCl particles is less than that of bare silver. This could be due to limited amount of NaCl and also higher oxidizing power of atomic oxygen. Finally, bare silver samples were exposed in salt spray chamber according to ASTM B117 up to 4 months. Very little corrosion products were detected after exposure, which is attributed to the lack of reactive species such as O and O3 in the environment. (Abstract shortened by UMI.)

Prevalence of glucose-6-phosphate dehydrogenase deficiency in jaundiced Egyptian neonates.

PubMed

M Abo El Fotoh, Wafaa Moustafa; Rizk, Mohammed Soliman

2016-12-01

The enzyme, Glucose-6-phosphate dehydrogenase (G6PD), deficiency leads to impaired production of reduced glutathione and predisposes the red cells to be damaged by oxidative metabolites, causing hemolysis. Deficient neonates may manifest clinically as hyperbilirubinemia or even kernicterus. This study was carried out to detect erythrocyte G6PD deficiency in neonatal hyperbilirubinemia. To determine the frequency and effect of G6PD deficiency, this study was conducted on 202 neonates with indirect hyperbilirubinemia. All term and preterm babies up to 13 day of age admitted with clinically evident jaundice were taken for the study. G6PD activity is measured by the UV-Kinetic Method using cellular enzyme determination reagents by spectrophotometry according to manufacturer's instructions. A total of 202 babies were enrolled in this study. Male babies outnumbered the female (71.3% versus 28.7%). Mean age of the study newborns was 3.75 ± 2.5 days. Eighteen neonates (8.9%) had G6PD deficiency, all are males. One case had combined G6PD deficiency and RH incompatibility. Mean serum total bilirubin was 17.2 ± 4.4 in G6PD deficient cases. There was significant positive correlation between the time of appearance of jaundice in days and G6PD levels in G6PD deficient cases. Neonatal hyperbilirubinemia is associated with various clinical comorbidities. G6PD deficiency is found to one important cause of neonatal jaundice developing on day 2 onwards.

Design of Co/Pd multilayer system with antiferromagnetic-to-ferromagnetic phase transition

NASA Astrophysics Data System (ADS)

Thiele, Jan-Ulrich

2009-03-01

Among the known magnetic material systems there are only very few examples of materials that undergo a temperature dependent antiferromagnetic-to-ferromagnetic phase transition, and of these only the chemically ordered alloy FeRh exhibits this transition near room temperature [1, 2]. Here we present a perpendicular anisotropy multilayer structure that mimics FeRh. The basic idea is to use two stacks of Co/Pd multilayers with large perpendicular magnetic anisotropy and high Curie temperature, TC, separated by a layer providing antiferromagnetic coupling, and a CoNi/Pd multilayer with perpendicular anisotropy with a lower TC, interlayer, in the range of the desired AF-FM transition temperature, TAF-FM. At room temperature this system behaves as two antiferromagnetically coupled layers with a low perpendicular remanent magnetic moment. As the temperature is raised to approach TC, interlayer the magnetization of the interlayer is gradually reduced to zero, and consequently its coupling strength is reduced. Eventually, the effective coupling between the two high-KU, high-TC layers becomes dominated by their dipolar fields, resulting in a parallel alignment of their moments and a net remanent magnetic moment equal to the sum of the moments of the two high-TC layers [2]. [4pt] [1] J. S. Kouvel and C. C. Hartelius, J. Appl. Phys. 33 (1962) p1343 [0pt] [2] J.-U. Thiele, E. E. Fullerton, S. Maat, Appl. Phys. Lett. 82 (2003) p2859 [0pt] [3] J.-U. Thiele. T. Hauet. O. Hellwig, Appl. Phys. Lett. 92 (2008) 242502.

New lifetime measurements in Pd 109 and the onset of deformation at N = 60

DOE PAGES

Bucher, B.; Mach, H.; Aprahamian, A.; ...

2015-12-14

We measured several new subnanosecond lifetimes in 109Pd using the fast-timing βγ γ (t ) method. Fission fragments of the A = 109 mass chain were produced by bombarding natural uranium with 30 MeV protons at the Jyväskylä Ion Guide Isotope Separator On-Line (IGISOL) facility. We obtained lifetimes for excited states in 109Pd populated following β decay of 109Rh. The new lifetimes provide some insight into the evolution of nuclear structure in this mass region. In particular, the distinct structure of the two low-lying 7/2+ states occurring systematically across the Pd isotopic chain is supported by the new lifetime measurements.more » Finally, the available nuclear data indicate a sudden increase in deformation at N = 60 which is related to the strong p-n interaction between πg 9/2 and νg 7/2 valence nucleons expected in this region.« less

Laserlight visual cueing device for freezing of gait in Parkinson's disease: a case study of the biomechanics involved.

PubMed

Egerton, C J; McCandless, P; Evans, B; Janssen, J; Richards, J D

2015-01-01

Freezing of gait (FOG) is a serious gait disorder affecting up to two-thirds of people with Parkinson's disease (PD). Cueing has been explored as a method of generating motor execution using visual transverse lines on the floor. However, the impact of a laser light visual cue remains unclear. To determine the biomechanical effect of a laser cane on FOG in a participant with PD compared to a healthy age- and gender-matched control. The participant with PD and healthy control were given a task of initiating gait from standing. Electromyography (EMG) data were collected from the tibialis anterior (TA) and the medial gastrocnemius (GS) muscles using an 8-channel system. A 10-camera system (Qualisys) recorded movement in 6 degrees of freedom and a calibrated anatomical system technique was used to construct a full body model. Center of mass (COM) and center of pressure (COP) were the main outcome measures. The uncued condition showed that separation of COM and COP took longer and was of smaller magnitude than the cued condition. EMG activity revealed prolonged activation of GS, with little to no TA activity. The cued condition showed earlier COM and COP separation. There was reduced fluctuation in GS, with abnormal, early bursts of TA activity. Step length improved in the cued condition compared to the uncued condition. Laserlight visual cueing improved step length beyond a non-cued condition for this patient indicating improved posture and muscle control.

Efficient Synthesis of MCu (M = Pd, Pt, and Au) Aerogels with Accelerated Gelation Kinetics and their High Electrocatalytic Activity.

PubMed

Zhu, Chengzhou; Shi, Qiurong; Fu, Shaofang; Song, Junhua; Xia, Haibing; Du, Dan; Lin, Yuehe

2016-10-01

To accelerate hydrogel formation and further simplify the synthetic procedure, a series of MCu (M = Pd, Pt, and Au) bimetallic aerogels is synthesized from the in situ reduction of metal precursors through enhancement of the gelation kinetics at elevated temperature. Moreover, the resultant PdCu aerogel with ultrathin nanowire networks exhibits excellent electrocatalytic performance toward ethanol oxidation, holding promise in fuel-cell applications. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Parkinson's Disease Is Associated with Goal Setting Deficits during Task Switching

ERIC Educational Resources Information Center

Meiran, Nachshon; Friedman, Gilad; Yehene, Eynat

2004-01-01

Ten Parkinson's Disease (PD) patients and 10 control participants were tested using a task-switching paradigm in which there was a random task sequence, and the task was cued in every trial. Five PD patients showed a unique error profile. Their performance approximated guessing when accuracy was dependent on correct task identification, and was…

Surfactant-free Synthesis of CuO with Controllable Morphologies and Enhanced Photocatalytic Property

NASA Astrophysics Data System (ADS)

Wang, Xing; Yang, Jiao; Shi, Liuxue; Gao, Meizhen

2016-03-01

A green synthesis for nanoleave, nanosheet, spindle-like, rugby-like, dandelion-like and flower-like CuO nanostructures (from 2D to 3D) is successfully achieved through simply hydrothermal synthetic method without the assistance of surfactant. The morphology of CuO nanostructures can be easily tailored by adjusting the amount of ammonia and the source of copper. By designing a time varying experiment, it is verified that the flower- and dandelion-like CuO structures are synthesized by the self-assembly and Ostwald ripening mechanism. Structural and morphological evolutions are investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM) and UV-visible diffuse reflectance spectra. Additionally, the CuO nanostructures with different morphologies could serve as a potential photocatalyst on the photodecomposition of rhodamine B (RhB) aqueous solutions in the presence of H2O2 under visible light irradiation.

Superconductivity and strong intrinsic defects in LaPd1-xBi2

NASA Astrophysics Data System (ADS)

Han, Fei; Malliakas, Christos D.; Stoumpos, Constantinos C.; Sturza, Mihai; Claus, Helmut; Chung, Duck Young; Kanatzidis, Mercouri G.

2013-10-01

Two new phases LaPd1-xBi2 and CePd1-xBi2 were obtained by growing single crystals in Bi flux. They adopt the tetragonal ZrCuSi2-type structure and feature Bi-square nets and PbO-type PdBi layers with significant partial Pd occupancy. Bulk superconductivity at 2.1 K and metallic behavior above Tc are observed in LaPd1-xBi2. A small residual resistance ratio (RRR) indicates a strong scattering effect induced by the Pd vacancies, which implies an s-wave pairing symmetry in LaPd1-xBi2. The broadening of the resistivity transition was measured under different magnetic fields demonstrating a high upper critical field of 3 T. Hall effect measurements reveal dominantly electron-like charge carriers and single-band transport behavior in LaPd1-xBi2. The paramagnetic CePd1-xBi2 is nonsuperconducting but shows antiferromagnetic ordering below 6 K.

Determination of boron in blood, urine and bone by electrothermal atomic absorption spectrometry using zirconium and citric acid as modifiers

NASA Astrophysics Data System (ADS)

Burguera, Marcela; Burguera, José Luis; Rondón, Carlos; Carrero, Pablo

2001-10-01

A comparative study of various potential chemical modifiers (Au, Ba, Be, Ca, Cr, Ir, La, Lu, Mg, Ni, Pd, Pt, Rh, Ru, Sr, V, W, and Zr), and different 'coating' treatments (Zr, W, and W+Rh) of the pyrolytic graphite platform of a longitudinally heated graphite tube atomizer for thermal stabilization and determination of boron was undertaken. The use of Au, Ba, Be, Cr, Ir, Pt, Rh, Ru, Sr and V as modifiers, and of W+Rh coating produced erratic, and noisy signals, while the addition of La, Ni and Pd as modifiers, and the W coating had positive effects, but with too high background absorption signals, rendering their use unsuitable for boron determination even in aqueous solutions. The atomic absorption signal for boron was increased and stabilized when the platform was coated with Zr, and by the addition of Ca, Mg, Lu, W or Zr as modifiers. Only the addition of 10 μg of Zr as a modifier onto Zr-treated platforms allowed the use of a higher pyrolysis temperature without analyte losses. The memory effect was minimized by incorporating a cleaning step with 10 μl of 50 g l -1 NH 4F HF after every three boron measurements. The addition of 10 μl of 15 g l -1 citric acid together with Zr onto Zr-treated platforms significantly improved the characteristic mass to m0=282 pg, which is adequate for biological samples such as urine and bone, although the sensitivity was still inadequate for the determination of boron in blood of subjects without supplementary diet. Under optimized conditions, the detection limit (3σ) was 60 μg l -1. The amount of boron found in whole blood, urine and femur head samples from patients with osteoporosis was in agreement with values previously reported in the literature.

Direct determination of platinum group elements and their distributions in geological and environmental samples at the ng g(-1) level using LA-ICP-IDMS.

PubMed

Boulyga, Sergei F; Heumann, Klaus G

2005-10-01

Laser ablation inductively coupled plasma isotope dilution mass spectrometry (LA-ICP-IDMS) was applied to the direct and simultaneous determination of the platinum group elements (PGEs) Pt, Pd, Ru, and Ir in geological and environmental samples. A special laser ablation system with high ablation rates was used, along with sector field ICP-MS. Special attention was paid to deriving the distributions of PGEs in the pulverized samples. IDMS could not be applied to the (mono-isotopic) Rh, but the similar ablation behavior of Ru and Rh allowed Rh to be simultaneously determined via relative sensitivity coefficients. The laser ablation process produces hardly any oxide ions (which usually cause interference in PGE analysis with liquid sample injection), so the ICP-MS can be run in its low mass resolution but high-sensitivity mode. The detection limits obtained for the geological samples were 0.16 ng g(-1), 0.14 ng g(-1), 0.08 ng g(-1), 0.01 ng g(-1) and 0.06 ng g(-1) for Ru, Rh, Pd, Ir and Pt, respectively. LA-ICP-IDMS was applied to different geological reference materials (TDB-1, WGB-1, UMT-1, WMG-1, SARM-7) and the road dust reference material BCR-723, which are only certified for some of the PGEs. Comparisons with certified values as well as with indicative values from the literature demonstrated the validity of the LA-ICP-IDMS method. The PGE concentrations in subsamples of the road dust reference material correspond to a normal distribution, whereas the distributions in the geological reference materials TDB-1, WGB-1, UMT-1, WMG-1, and SARM-7 are more complex. For example, in the case of Ru, a logarithmic normal distribution best fits the analyzed concentrations in TDB-1 subsamples, whereas a pronounced nugget effect was found for Pt in most geological samples.

Site preference of ternary alloying additions to NiTi: Fe, Pt, Pd, Au, Al, Cu, Zr and Hf

NASA Technical Reports Server (NTRS)

Bozzolo, Guillermo; Noebe, Ronald D.; Mosca, Hugo O.

2004-01-01

Atomistic modeling of the site substitution behavior of Pd in NiTi (J. Alloys and Comp. (2004), in press) has been extended to examine the behavior of several other alloying additions, namely, Fe, Pt, Au, Al, Cu, Zr and Hf in this important shape memory alloy. It was found that all elements, to a varying degree, displayed absolute preference for available sites in the deficient sublattice. How- ever, the energetics of the different substitutional schemes, coupled with large scale simulations indicate that the general trend in all cases is for the ternary addition to want to form stronger ordered structures with Ti.

The influence of external factors on the corrosion resistance of high temperature superconductor thin films against moisture

NASA Astrophysics Data System (ADS)

Murugesan, M.; Obara, H.; Yamasaki, H.; Kosaka, S.

2006-12-01

High temperature superconductor (HTS) thin films have been systematically investigated for their corrosion resistance against moisture by studying the role of external factors such as temperature (T), relative humidity (RH), and the type of substrates in the corrosion. In general, (i) the corrosion is progressed monotonously with increasing T as well as RH, (ii) a threshold level of water vapor is needed to cause degradation, and (iii) between T and RH, the influence of T is more dominant. HTS films on SrTiO3 and CeO2 buffered sapphire (cbs) substrates showed better corrosion stability and a low rate of degradation in the critical current density as compared to that of the film grown on MgO substrate. Between DyBa2Cu3Oz (DBCO) and YBa2Cu3Oz, the former is reproducibly found to have many fold higher corrosion resistance against moisture. This observed enhancement in the corrosion resistance in DBCO could be explained by the improved microstructure in the films and the better lattice matching with the substrate. Thus, the dual advantage of DBCO/cbs films, i.e., the enhanced corrosion stability of DBCO and the appropriate dielectric properties of sapphire, can be readily exploited for the use of DBCO/cbs films in the microwave and power devices.

Tunable Catalysis of Water to Peroxide with Anionic, Cationic, and Neutral Atomic Au, Ag, Pd, Rh, and Os

NASA Astrophysics Data System (ADS)

Suggs, K.; Kiros, F.; Tesfamichael, A.; Felfli, Z.; Msezane, A. Z.

2015-05-01

Fundamental anionic, cationic, and neutral atomic metal predictions utilizing density functional theory calculations validate the recent discovery identifying the interplay between Regge resonances and Ramsauer-Townsend minima obtained through complex angular momentum analysis as the fundamental atomic mechanism underlying nanoscale catalysis. Here we investigate the optimization of the catalytic behavior of Au, Ag, Pd, Rh, and Os atomic systems via polarization effects and conclude that anionic atomic systems are optimal and therefore ideal for catalyzing the oxidation of water to peroxide, with anionic Os being the best candidate. The discovery that cationic systems increase the transition energy barrier in the synthesis of peroxide could be important as inhibitors in controlling and regulating catalysis. These findings usher in a fundamental and comprehensive atomic theoretical framework for the generation of tunable catalytic systems. The ultimate aim is to design giant atomic catalysts and sensors, in the context of the recently synthesized tri-metal Ag@Au@Pt and bimetal Ag@Au nanoparticles for greatly enhanced plasmonic properties and improved chemical stability for chemical and biological sensing. Research was supported by U.S. DOE Office of Basic Energy Sciences.

Ultra-low power hydrogen sensing based on a palladium-coated nanomechanical beam resonator.

PubMed

Henriksson, Jonas; Villanueva, Luis Guillermo; Brugger, Juergen

2012-08-21

Hydrogen sensing is essential to ensure safety in near-future zero-emission fuel cell powered vehicles. Here, we present a novel hydrogen sensor based on the resonant frequency change of a nanoelectromechanical clamped-clamped beam. The beam is coated with a Pd layer, which expands in the presence of H(2), therefore generating a stress build-up that causes the frequency of the device to drop. The devices are able to detect H(2) concentrations below 0.5% within 1 s of the onset of the exposure using only a few hundreds of pW of power, matching the industry requirements for H(2) safety sensors. In addition, we investigate the strongly detrimental effect that relative humidity (RH) has on the Pd responsivity to H(2), showing that the response is almost nullified at about 70% RH. As a remedy for this intrinsic limitation, we applied a mild heating current through the beam, generating a few μW of power, whereby the responsivity of the sensors is fully restored and the chemo-mechanical process is accelerated, significantly decreasing response times. The sensors are fabricated using standard processes, facilitating their eventual mass-production.

Experimental Study of the Partitioning of Siderophile Elements in a Crystallizing Lunar Magma Ocean

NASA Technical Reports Server (NTRS)

Galenas, M.; Righter, K.; Danielson, L.; Pando, K.; Walker, R. J.

2012-01-01

The distributions of trace elements between the lunar interior and pristine crustal rocks were controlled by the composition of starting materials, lunar core formation, and crystallization of the lunar magma ocean (LMO) [1]. This study focuses on the partitioning of highly siderophile elements (HSE) including Re, Os, Ir, Ru, Pt, Rh, Pd and Au as well as the moderately siderophile elements Mo and W, and the lithophile elements of Hf and Sr. Our experiments also include Ga, which can be slightly siderophile, but is mostly considered to be chalcophile. Partitioning of these elements is not well known at the conditions of a crystallizing LMO. Previous studies of HSE partitioning in silicate systems have yielded highly variable results for differing oxygen fugacity (fO2) and pressure [2-4]. For example, under certain conditions Pt is compatible in clinopy-roxene [2] and Rh and Ru are compatible in olivine [3]. The silicate compositions used for these experiments were nominally basaltic. Ruthenium, Rh, and Pd are incompatible in plagioclase under these conditions[4]. However, this latter study was done at extremely oxidizing conditions and at atmospheric pressure, possibly limiting the applicability for consideration of conditions of a crystallizing LMO. In this study we address the effects of pressure and oxygen fugacity on the crystal/liquid partition coefficients of these trace elements. We are especially interested in the plagioclase/melt partition coefficients so that it may be possible to use reverse modeling to constrain the concentrations of these elements in the lunar mantle through their abundances in pristine crustal rocks.

Hydrogen peroxide-assisted synthesis of novel three-dimensional octagonal-like CuO nanostructures with enhanced visible-light-driven photocatalytic activity

NASA Astrophysics Data System (ADS)

Chen, Xiangyu; Chu, Deqing; Wang, Limin; Hu, Wenhui; Yang, Huifang; Sun, Jingjing; Zhu, Shaopeng; Wang, Guowei; Tao, Jian; Zhang, Songsong

2018-04-01

Novel three-dimensional octagonal-like CuO micro-/nanostructures with diameters ranging from 10 to 15 μm have been successfully prepared by hydrogen peroxide-assisted hydrothermal method and subsequent calcination. The product morphology can be changed by simply ordering the amount of hydrogen peroxide (H2O2). When the amounts of H2O2 is increased, the length of the corner portion is increased and the width is narrower. The obtained octagonal CuO nanostructures were evaluated for their ability for the degradation of hazardous organic contaminants in water under visible-light irradiation. Comparing with commercial CuO and other CuO products, the CuO octagonal nanostructures exhibit excellent performance for photocatalytic decomposition of RhB (Rhodamine B). It is well established that effective photocatalytic performance results from its unique 3D octagonal nanostructures. We believe that the present work will provide some ideas for further fabrication of other novel nanostructures and exploration of their applications.

A Reactive Oxide Overlayer on Rh Nanoparticles during CO Oxidation and Its Size Dependence Studied by in Situ Ambient Pressure XPS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Grass, Michael E.; Zhang, Yawen; Butcher, Derek R.

2008-09-15

CO oxidation is one of the most studied heterogeneous reactions, being scientifically and industrially important, particularly for removal of CO from exhaust streams and preferential oxidation for hydrogen purification in fuel cell applications. The precious metals Ru, Rh, Pd, Pt, and Au are most commonly used for this reaction because of their high activity and stability. Despite the wealth of experimental and theoretical data, it remains unclear what is the active surface for CO oxidation under catalytic conditions for these metals. In this communication, we utilize in situ synchrotron ambient pressure X-ray photoelectron spectroscopy (APXPS) to monitor the oxidation statemore » at the surface of Rh nanoparticles during CO oxidation and demonstrate that the active catalyst is a surface oxide, the formation of which is dependent on particle size. The amount of oxide formed and the reaction rate both increase with decreasing particle size.« less

The feasibility of singing to improve gait in Parkinson disease

PubMed Central

Harrison, Elinor C.; McNeely, Marie E.; Earhart, Gammon M.

2017-01-01

Brain regions important for controlling movement are also responsible for rhythmic processing. In Parkinson disease (PD), defective internal timing within the brain has been linked to impaired beat discrimination, and may contribute to a loss of ability to maintain a steady gait rhythm. Less rhythmic gait is inherently less efficient, and this may lead to gait impairment including reduced speed, cadence, and stride length, as well as increased variability. While external rhythmic auditory stimulation (e.g. a metronome beat) is well-established as an effective tool to stabilize gait in PD, little is known about whether self-generated cues such as singing have the same beneficial effect on gait in PD. Thus, we compared gait patterns of 23 people with mild to moderate PD under five cued conditions: uncued, music only, singing only, singing with music, and a verbal dual-task condition. In our single session study, singing while walking did not significantly alter velocity, cadence, or stride length, indicating that it was not excessively demanding for people with PD. In addition, walking was less variable when singing than during other cued conditions. This was further supported by the comparison between singing trials and a verbal dual-task condition. In contrast to singing, the verbal dual-task negatively affected gait performance. These findings suggest that singing holds promise as an effective cueing technique that may be as good as or better than traditional cueing techniques for improving gait among people with PD. PMID:28226309

The feasibility of singing to improve gait in Parkinson disease.

PubMed

Harrison, Elinor C; McNeely, Marie E; Earhart, Gammon M

2017-03-01

Brain regions important for controlling movement are also responsible for rhythmic processing. In Parkinson disease (PD), defective internal timing within the brain has been linked to impaired beat discrimination, and may contribute to a loss of ability to maintain a steady gait rhythm. Less rhythmic gait is inherently less efficient, and this may lead to gait impairment including reduced speed, cadence, and stride length, as well as increased variability. While external rhythmic auditory stimulation (e.g. a metronome beat) is well-established as an effective tool to stabilize gait in PD, little is known about whether self-generated cues such as singing have the same beneficial effect on gait in PD. Thus, we compared gait patterns of 23 people with mild to moderate PD under five cued conditions: uncued, music only, singing only, singing with music, and a verbal dual-task condition. In our single-session study, singing while walking did not significantly alter velocity, cadence, or stride length, indicating that it was not excessively demanding for people with PD. In addition, walking was less variable when singing than during other cued conditions. This was further supported by the comparison between singing trials and a verbal dual-task condition. In contrast to singing, the verbal dual-task negatively affected gait performance. These findings suggest that singing holds promise as an effective cueing technique that may be as good as or better than traditional cueing techniques for improving gait among people with PD. Copyright © 2017 Elsevier B.V. All rights reserved.

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

PubMed

Khodadadi, Bahar; Bordbar, Maryam; Nasrollahzadeh, Mahmoud

2017-03-15

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

Biomonitoring of 37 trace elements in blood samples from inhabitants of northern Germany by ICP-MS.

PubMed

Heitland, Peter; Köster, Helmut D

2006-01-01

The trace elements Ag, As, Au, B, Ba, Be, Bi, Cd, Ce, Co, Cs, Cu, Ga, Hf, Hg, In, La, Mn, Mo, Ni, Pb, Pd, Rb, Rh, Ru, Sb, Se, Sn, Sr, Te, Th, Tl, U, V, W, Y and Zr were determined in 130 human blood samples from occupationally non-exposed volunteers living in the greater area of Bremen in northern Germany. The blood samples were collected in lithium heparin monovettes developed for trace metal determination and were analysed by inductively coupled plasma mass spectrometry (ICP-MS) with an octopole-based collision/reaction cell. For sample introduction into the ICP, the blood samples were diluted 1/10 (V/V) with a 0.1% Triton-X-100 and 0.5% (V/V) ammonia solution. The method validation of our developed routine method is described for all 37 elements and results about internal and external quality assurance are discussed. Information on exposure conditions of all human subjects were collected by questionnaire-based interviews, including smoking habits, seafood consumption and the type of dental alloys in the teeth. Mean values, geometric mean values, ranges and selected percentiles of all elemental concentrations in human blood are presented, which helps toxicologists and clinical chemists planning research about exposition to metals and health effects caused by exposition to metals.

Quantitative Analysis of Language Production in Parkinson's Disease Using a Cued Sentence Generation Task

ERIC Educational Resources Information Center

Vanhoutte, Sarah; De Letter, Miet; Corthals, Paul; Van Borsel, John; Santens, Patrick

2012-01-01

The present study examined language production skills in Parkinson's disease (PD) patients. A unique cued sentence generation task was created in order to reduce demands on memory and attention. Differences in sentence production abilities according to disease severity and cognitive impairments were assessed. Language samples were obtained from 20…

Reactivity of Transition Metals (Pd Pt Cu Ag Au) toward Molecular Hydrogen Dissociation: Extended Surfaces versus Particles Supported on TiC(001) or Small Is Not Always Better and Large Is Not Always Bad

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rodriguez J. A.; Gomez T.; Florez E.

2011-06-16

The reactivity of Pd{sub 4}, Pt{sub 4}, Cu{sub 4}, Ag{sub 4}, and Au{sub 4} clusters supported on TiC(001) toward molecular hydrogen dissociation has been studied by means of density functional based theory and periodic models and compared to that of the (111) and (001) surfaces. Pd{sub 4} and Pt{sub 4} interact rather strongly with the TiC(001) substrate, but the interaction of molecular hydrogen with the Pd{sub 4}/TiC and Pt{sub 4}/TiC systems is also very strong. As a consequence of the substantial admetal {leftrightarrow} carbide interactions, the adsorbed H{sub 2} molecule becomes more difficult to dissociate than on the corresponding extendedmore » (111) and (001) surfaces. Here, having a small supported particle does not lead to an enhanced chemical activity. On the contrary, for the Cu{sub 4}/TiC, Ag{sub 4}/TiC, and Au{sub 4}/TiC systems the combination of the small size of the particle and the polarization induced by the underlying carbide facilitates the dissociation of the hydrogen molecule with respect to the case of the extended surfaces. Here, the reduced size effectively enhances the activity of the supported particle. Thus, our results for the M(111), M(100), and M{sub 4}/TiC(001) systems show the complex interplay that can take place among the nature of the admetal, particle size effects, and support interactions.« less

Reactivity of Transition Metals (Pd, Pt, Cu, Ag, Au) toward Molecular Hydrogen Dissociation: Extended Surfaces versus Particles Supported on TiC(001) or Small Is Not Always Better and Large Is Not Always Bad

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rodriguez, J.A.; Gomez, T.; Florez, E.

2011-05-11

The reactivity of Pd{sub 4}, Pt{sub 4}, Cu{sub 4}, Ag{sub 4}, and Au{sub 4} clusters supported on TiC(001) toward molecular hydrogen dissociation has been studied by means of density functional based theory and periodic models and compared to that of the (111) and (001) surfaces. Pd{sub 4} and Pt{sub 4} interact rather strongly with the TiC(001) substrate, but the interaction of molecular hydrogen with the Pd{sub 4}/TiC and Pt{sub 4}/TiC systems is also very strong. As a consequence of the substantial admetal {leftrightarrow} carbide interactions, the adsorbed H{sub 2} molecule becomes more difficult to dissociate than on the corresponding extendedmore » (111) and (001) surfaces. Here, having a small supported particle does not lead to an enhanced chemical activity. On the contrary, for the Cu{sub 4}/TiC, Ag{sub 4}/TiC, and Au{sub 4}/TiC systems the combination of the small size of the particle and the polarization induced by the underlying carbide facilitates the dissociation of the hydrogen molecule with respect to the case of the extended surfaces. Here, the reduced size effectively enhances the activity of the supported particle. Thus, our results for the M(111), M(100), and M{sub 4}/TiC(001) systems show the complex interplay that can take place among the nature of the admetal, particle size effects, and support interactions.« less

Summary of Available Hail Literature and the Effect of Hail on Aircraft in Flight

DTIC Science & Technology

1952-09-01

Delaware - District of Columbia area. D-58. Anon.: Estudios Superiores, Seccion de Investigaciones Meteorologicas. Observacion de la frecuencia...41 +> H d Üf"e 3 O •■» m cu -■gg p m 3 4) d CH H flü son ft o 3 cd ft Xl ■ V 41 > aj = 4) rH X! d B...d PH W lA i^o . CO CM CO * LT P * CO w CO rH w w en w O W CD *d m d EH * * CO P * &H CO E-i EH -=f LT\\ EH NO NO ON s N£> CO O