Catalytic Activities of Noble Metal Phosphides for Hydrogenation and Hydrodesulfurization Reactions

Directory of Open Access Journals (Sweden)

Yasuharu Kanda

2018-04-01

Full Text Available In this work, the development of a highly active noble metal phosphide (NMXPY-based hydrodesulfurization (HDS catalyst with a high hydrogenating ability for heavy oils was studied. NMXPY catalysts were obtained by reduction of P-added noble metals (NM-P, NM: Rh, Pd, Ru supported on SiO2. The order of activities for the hydrogenation of biphenyl was Rh-P > NiMoS > Pd-P > Ru-P. This order was almost the same as that of the catalytic activities for the HDS of dibenzothiophene. In the HDS of 4,6-dimethyldibenzothiophene (4,6-DMDBT, the HDS activity of the Rh-P catalyst increased with increasing reaction temperature, but the maximum HDS activity for the NiMoS catalyst was observed at 270 °C. The Rh-P catalyst yielded fully hydrogenated products with high selectivity compared with the NiMoS catalyst. Furthermore, XRD analysis of the spent Rh-P catalysts revealed that the Rh2P phase possessed high sulfur tolerance and resistance to sintering.

Electrocatalysis of chemically synthesized noble metal nanoparticles on carbon electrodes

DEFF Research Database (Denmark)

Zhang, Ling; Ulstrup, Jens; Zhang, Jingdong

Noble metal nanoparticles (NPs), such as platinum (Pt) and palladium (Pd) NPs are promising catalysts for dioxygen reduction and oxidation of molecules such as formic acid and ethanol in fuel cells. Carbon nanomaterials are ideal supporting materials for electrochemical catalysts due to their good...... by electrochemical SPM. This study offers promise for development of new high-efficiency catalyst types with low-cost for fuel cell technology...

Integrated DWPF Melter System (IDMS) campaign report: The first two noble metals operations

International Nuclear Information System (INIS)

Hutson, N.D.; Zamecnik, J.R.; Smith, M.E.; Miller, D.H.; Ritter, J.A.

1991-01-01

The Integrated DWPF Melter System (IDMS) is designed and constructed to provide an engineering-scale representation of the DWPF melter and its associated feed preparation and off-gas systems. The facility is the first pilot-scale melter system capable of processing mercury, and flowsheet levels of halides and noble metals. In order to characterize the processing of noble metals (Pd, Rh, Ru, and Ag) on a large scale, the IDMS will be operated batchstyle for at least nine feed preparation cycles. The first two of these operations are complete. The major observation to date occurred during the second run when significant amounts of hydrogen were evolved during the feed preparation cycle. The runs were conducted between June 7, 1990 and March 8, 1991. This time period included nearly six months of ''fix-up'' time when forced air purges were installed on the SRAT MFT and other feed preparation vessels to allow continued noble metals experimentation

Development of casting investment preventing blackening of noble metal alloys part 1. Application of developed investment for Ag-Pd-Cu-Au alloy.

Science.gov (United States)

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.

NOBLE METAL CHEMISTRY AND HYDROGEN GENERATION DURING SIMULATED DWPF MELTER FEED PREPARATION

Energy Technology Data Exchange (ETDEWEB)

Koopman, D

2008-06-25

Simulations of the Defense Waste Processing Facility (DWPF) Chemical Processing Cell vessels were performed with the primary purpose of producing melter feeds for the beaded frit program plus obtaining samples of simulated slurries containing high concentrations of noble metals for off-site analytical studies for the hydrogen program. Eight pairs of 22-L simulations were performed of the Sludge Receipt and Adjustment Tank (SRAT) and Slurry Mix Evaporator (SME) cycles. These sixteen simulations did not contain mercury. Six pairs were trimmed with a single noble metal (Ag, Pd, Rh, or Ru). One pair had all four noble metals, and one pair had no noble metals. One supporting 4-L simulation was completed with Ru and Hg. Several other 4-L supporting tests with mercury have not yet been performed. This report covers the calculations performed on SRNL analytical and process data related to the noble metals and hydrogen generation. It was originally envisioned as a supporting document for the off-site analytical studies. Significant new findings were made, and many previous hypotheses and findings were given additional support as summarized below. The timing of hydrogen generation events was reproduced very well within each of the eight pairs of runs, e.g. the onset of hydrogen, peak in hydrogen, etc. occurred at nearly identical times. Peak generation rates and total SRAT masses of CO{sub 2} and oxides of nitrogen were reproduced well. Comparable measures for hydrogen were reproduced with more variability, but still reasonably well. The extent of the reproducibility of the results validates the conclusions that were drawn from the data.

Effects of halogens on interactions between a reduced TiO{sub 2} (110) surface and noble metal atoms: A DFT study

Energy Technology Data Exchange (ETDEWEB)

Tada, Kohei, E-mail: k-tada@aist.go.jp [Department of Chemistry, Graduate School of Science, Osaka University, 1-1, Machikaneyama, Toyonaka, Osaka, 560-0043 (Japan); Research Institute of Electrochemical Energy, National Institute of Advanced Industrial Science and Technology (AIST), 1-8-31, Midorigaoka, Ikeda, Osaka, 563-8577 (Japan); Koga, Hiroaki [Element Strategy Initiative for Catalysts and Batteries (ESICB), Kyoto University, 1-30 Goryo Ohara, Nishikyo, Kyoto, 615-8245 (Japan); Hayashi, Akihide; Kondo, Yudai; Kawakami, Takashi; Yamanaka, Shusuke [Department of Chemistry, Graduate School of Science, Osaka University, 1-1, Machikaneyama, Toyonaka, Osaka, 560-0043 (Japan); Okumura, Mitsutaka [Department of Chemistry, Graduate School of Science, Osaka University, 1-1, Machikaneyama, Toyonaka, Osaka, 560-0043 (Japan); Element Strategy Initiative for Catalysts and Batteries (ESICB), Kyoto University, 1-30 Goryo Ohara, Nishikyo, Kyoto, 615-8245 (Japan)

2017-07-31

Highlights: • We investigated the halogen effect on the interactions of noble metals with TiO{sub 2}. • Halogen atoms inhibit electron transfer from TiO{sub 2} to noble metals. • Iodine stabilizes the adsorption of noble metals especially for Ag and Cu. • Electron transfer from the TiO{sub 2} is effective in anchoring Au and Pt atoms. • Covalent interaction with the support is effective in anchoring Ag and Cu atoms. - Abstract: Using DFT calculation, we investigate the effects of halogens on the interactions between rutile TiO{sub 2} (110) and noble metal atoms (Au, Ag, Cu, Pt, and Pd). Fluorine, chlorine, and bromine atoms occupy the oxygen defect sites of TiO{sub 2}, decreasing the stability of noble metal atoms on the surface. This decrease occurs because the halogens inhibit electron transfer from TiO{sub 2} to the noble metal atoms; the electron transfer from reduced TiO{sub 2} to the noble metal atom stabilizes the noble metal atom adsorption. In contrast, iodine strengthens the interactions between TiO{sub 2} and some noble metal atoms, namely Ag and Cu. This stabilization occurs because of the covalent interaction between iodine-doped TiO{sub 2} and the noble metal atom. Therefore, the stabilization is explained well by chemical hardness. This result suggests that iodine-doping of a TiO{sub 2} surface would be an effective method for the preparation of highly stabilized noble metal clusters.

X-ray and magnetic studies on intermetallic phases of the type CaCu5 using noble metals and strontium

International Nuclear Information System (INIS)

Heumann, T.; Birnschein, R.R.

1976-01-01

The intermetallic phases SrAu 5 , SrAg 5 and SrPd 5 and their binary part systems with the specific noble metals as well as the pseudobinary series SrAu 5 -SrPd 5 and SrAg 5 -SrPd 5 are dealt with within the framework of this lecture. The noble metals gold, silver and palladium form AB 5 phases with strontium which cristallize in CaCu 5 structure. The atomic susceptibilities of the part systems Ag-SrAg 5 and Au-SrAu 5 as a function of the Sr concentration, of the part system Pd-SrPd 5 as a function of the temperature and the Sr concentration, of Au-Pd as a function of the Pd concentration, of the series SrAu 5 -SrPd 5 as a function of the SrPd 5 concentration, of the series SrAg 5 -SrPd 5 as function of the SrPd 5 concentration, the electrical resistance of Ag-SrAg 5 and Au-SrAu 5 as function of the Sr concentration, the lattice constants of the series SrAu 5 -SrPd 5 as a function of the SrPd 5 concentration, as well as the number of effective magnetones in the system Au-Pd as a function of the Pd concentration, were measured and evaluated. (orig./LH) [de

Effect of noble metal doping on the structural properties of lanthanum cobaltite

International Nuclear Information System (INIS)

Dharmadhikari, Dipti V.; Athawal, Anjali A.

2016-01-01

Pristine and Noble metal (Ag and Pd) doped lanthanum cobaltite samples have been synthesised by Hydrothermal method. Lanthanum in the A-Site and Co at B-site of Lanthanum cobaltite (LaCoO 3 ) perovskites were partially doped by silver and palladium (4%). Crystal structure analysis revealed that the hydrothermal synthesis led to the formation of pure nanocrystalline perovskite structure. Morphological analysis of the samples shows that the noble metal doping affects the morphology of the samples. Pristine sample shows spherical to oval shaped particles while the doping results in the formation of irregular shaped, spherical and rod shaped particles. Silver doping results in the agglomeration of particles. The particles were observed to be fused with each other to form rod shaped structures in case of palladium doped samples. (author)

Synthesis, characterization and photocatalytic activity of noble metal-modified TiO2 nanosheets with exposed {0 0 1} facets

International Nuclear Information System (INIS)

Diak, Magdalena; Grabowska, Ewelina; Zaleska, Adriana

2015-01-01

Graphical abstract: - Highlights: • TiO 2 nanosheets with exposed {0 0 1} facets were prepared by hydrothermal method. • Pd and Ag NPs-loaded enhanced the photocatalytic activity under visible irradiation. • Photodeposition is an effective method to obtain noble metal NPs on TiO 2 surface. - Abstract: Pt, Pd, Ag and Au nanoparticles were photodeposited on the {0 0 1} crystal facets of the TiO 2 anatase nanosheets. Morphological and surface characterization of the samples as well as photocatalytic activity were studied. The influence of metal precursor concentration used during photodeposition (0.05−0.5%) on size of formed metal nanoparticles together with UV and vis-mediated activity of Pt, Pd, Ag or Au−TiO 2 was investigated. Generally, samples obtained by photodeposition of noble metal nanoparticles using their 0.2% precursor solutions revealed highest activity in phenol degradation reaction under visible light (λ > 420 nm). The photoactivity of the as-prepared samples with respect to the modified metal species was ordered Ag≅Pd > Au > Pt. TEM analysis showed that photodeposited metal nanoparticles appeared only on {0 0 1} facets of TiO 2 . The average degradation rate of phenol in the presence of Pd and Ag−TiO 2 was 0.5 μmol dm −3 min −1 after 60 min of irradiation under visible light, and was five times higher than that of pure TiO 2 nanosheets

Structural energetics of noble metals

International Nuclear Information System (INIS)

Mujibur Rahman, S.M.

1982-06-01

Structural energetics of the noble metals, namely Cu, Ag, and Au are investigated by employing a single-parameter pseudopotential. The calculations show that the lowest energy for all of these metals corresponds to FCC - their observed crystal structure. The one-electron contribution to the free energy is found to dominate the structural prediction for these metals. The present investigation strongly emphasizes that the effects due to band hybridization and core-core exchange play a significant role on the structural stability of the noble metals. (author)

Expeditious Synthesis of Noble Metal Nanoparticles Using Vitamin B12 under Microwave Irradiation

Directory of Open Access Journals (Sweden)

Changseok Han

2015-08-01

Full Text Available A greener synthesis protocol for noble nanometals is developed using vitamin B12 as a reducing and capping agent in conjunction with the use of microwaves. Successful assembly of nanoparticles or microparticles with varied shapes and sizes have been demonstrated. The synthesized Ag, Au, and Pd samples were thoroughly characterized with X-ray diffraction, scanning electron microscopy, transmission electron microscopy, high resolution transmission microscopy, and UV-visible spectrophotometry, confirming that metallic Ag, Au, and Pd were synthesized by the green chemistry method.

Visible light active TiO2 films prepared by electron beam deposition of noble metals

International Nuclear Information System (INIS)

Hou Xinggang; Ma Jun; Liu Andong; Li Dejun; Huang Meidong; Deng Xiangyun

2010-01-01

TiO 2 films prepared by sol-gel method were modified by electron beam deposition of noble metals (Pt, Pd, and Ag). Effects of noble metals on the chemical and surface characteristics of the films were studied using XPS, TEM and UV-Vis spectroscopy techniques. Photocatalytic activity of modified TiO 2 films was evaluated by studying the degradation of methyl orange dye solution under visible light UV irradiation. The result of TEM reveals that most of the surface area of TiO 2 is covered by tiny particles of noble metals with diameter less than 1 nm. Broad red shift of UV-Visible absorption band of modified photocatalysts was observed. The catalytic degradation of methyl orange in aqueous solutions under visible light illumination demonstrates a significant enhancement of photocatalytic activity of these films compared with the un-loaded films. The photocatalytic efficiency of modified TiO 2 films by this method is affected by the concentration of impregnating solution.

Measuring the noble metal and iodine composition of extracted noble metal phase from spent nuclear fuel using instrumental neutron activation analysis

International Nuclear Information System (INIS)

Palomares, R.I.; Dayman, K.J.; Landsberger, S.; Biegalski, S.R.; Soderquist, C.Z.; Casella, A.J.; Brady Raap, M.C.; Schwantes, J.M.

2015-01-01

Masses of noble metal and iodine nuclides in the metallic noble metal phase extracted from spent fuel are measured using instrumental neutron activation analysis. Nuclide presence is predicted using fission yield analysis, and radionuclides are identified and the masses quantified using neutron activation analysis. The nuclide compositions of noble metal phase derived from two dissolution methods, UO 2 fuel dissolved in nitric acid and UO 2 fuel dissolved in ammonium-carbonate and hydrogen-peroxide solution, are compared. - Highlights: • The noble metal phase was chemically extracted from spent nuclear fuel and analyzed non-destructively. • Noble metal phase nuclides and long-lived iodine were identified and quantified using neutron activation analysis. • Activation to shorter-lived radionuclides allowed rapid analysis of long-lived fission products in spent fuel using gamma spectrometry

Vitrification of noble metals containing NCAW simulant with an engineering scale melter (ESM): Campaign report

Energy Technology Data Exchange (ETDEWEB)

Grunewald, W.; Roth, G.; Tobie, W.; Weisenburger, S.; Weiss, K.; Elliott, M.; Eyler, L.L.

1996-03-01

ESM has been designed as a 10th-scale model of the DWPF-type melter, currently the reference melter for nitrification of Hanford double shell tankwaste. ESM and related equipment have been integrated to the existing mockup vitrification plant VA-WAK at KfK. On June 2-July 10, 1992, a shakedown test using 2.61 m{sup 3} of NCAW (neutralized current acid waste) simulant without noble metals was performed. On July 11-Aug. 30, 1992, 14.23 m{sup 3} of the same simulant with nominal concentrations of Ru, Rh, and Pd were vitrified. Objective was to investigate the behavior of such a melter with respect to discharge of noble metals with routine glass pouring via glass overflow. Results indicate an accumulation of noble metals in the bottom area of the flat-bottomed ESM. About 65 wt% of the noble metals fed to the melter could be drained out, whereas 35 wt% accumulated in the melter, based on analysis of glass samples from glass pouring stream in to the canisters. After the melter was drained at the end of the campaign through a bottom drain valve, glass samples were taken from the residual bottom layer. The samples had significantly increased noble metals content (factor of 20-45 to target loading). They showed also a significant decrease of the specific electric resistance compared to bulk glass (factor of 10). A decrease of 10- 15% of the resistance between he power electrodes could be seen at the run end, but the total amount of noble metals accumulated was not yet sufficient enough to disturb the Joule heating of the glass tank severely.

Improved ethanol electrooxidation performance by shortening Pd-Ni active site distance in Pd-Ni-P nanocatalysts

Science.gov (United States)

Chen, Lin; Lu, Lilin; Zhu, Hengli; Chen, Yueguang; Huang, Yu; Li, Yadong; Wang, Leyu

2017-01-01

Incorporating oxophilic metals into noble metal-based catalysts represents an emerging strategy to improve the catalytic performance of electrocatalysts in fuel cells. However, effects of the distance between the noble metal and oxophilic metal active sites on the catalytic performance have rarely been investigated. Herein, we report on ultrasmall (~5 nm) Pd-Ni-P ternary nanoparticles for ethanol electrooxidation. The activity is improved up to 4.95 A per mgPd, which is 6.88 times higher than commercial Pd/C (0.72 A per mgPd), by shortening the distance between Pd and Ni active sites, achieved through shape transformation from Pd/Ni-P heterodimers into Pd-Ni-P nanoparticles and tuning the Ni/Pd atomic ratio to 1:1. Density functional theory calculations reveal that the improved activity and stability stems from the promoted production of free OH radicals (on Ni active sites) which facilitate the oxidative removal of carbonaceous poison and combination with CH3CO radicals on adjacent Pd active sites.

Visible light active TiO{sub 2} films prepared by electron beam deposition of noble metals

Energy Technology Data Exchange (ETDEWEB)

Hou Xinggang, E-mail: hou226@163.co [Department of Physics, Tianjin Normal University, Tianjin 300387 (China); Ma Jun [Department of Physics, Tianjin Normal University, Tianjin 300387 (China); Liu Andong [Key Laboratory of Beam Technology and Material Modification of Ministry of Education, Beijing Normal University, Beijing 100875 (China); Li Dejun; Huang Meidong; Deng Xiangyun [Department of Physics, Tianjin Normal University, Tianjin 300387 (China)

2010-03-15

TiO{sub 2} films prepared by sol-gel method were modified by electron beam deposition of noble metals (Pt, Pd, and Ag). Effects of noble metals on the chemical and surface characteristics of the films were studied using XPS, TEM and UV-Vis spectroscopy techniques. Photocatalytic activity of modified TiO{sub 2} films was evaluated by studying the degradation of methyl orange dye solution under visible light UV irradiation. The result of TEM reveals that most of the surface area of TiO{sub 2} is covered by tiny particles of noble metals with diameter less than 1 nm. Broad red shift of UV-Visible absorption band of modified photocatalysts was observed. The catalytic degradation of methyl orange in aqueous solutions under visible light illumination demonstrates a significant enhancement of photocatalytic activity of these films compared with the un-loaded films. The photocatalytic efficiency of modified TiO{sub 2} films by this method is affected by the concentration of impregnating solution.

Preliminary investigation of a technique to separate fission noble metals from fission-product mixtures

International Nuclear Information System (INIS)

Mellinger, G.B.; Jensen, G.A.

1982-08-01

A variation of the gold-ore fire assay technique was examined as a method for recovering Pd, Rh and Ru from fission products. The mixture of fission product oxides is combined with glass-forming chemicals, a metal oxide such as PbO (scavenging agent), and a reducing agent such as charcoal. When this mixture is melted, a metal button is formed which extracts the noble metals. The remainder cools to form a glass for nuclear waste storage. Recovery depended only on reduction of the scavenger oxide to metal. When such reduction was achieved, no difference in noble metal recovery efficiency was found among the scavengers studied (PbO, SnO, CuO, Bi 2 O 3 , Sb 2 O 3 ). Not all reducing agents studied, however, were able to reduce all scavenger oxides to metal. Only graphite would reduce SnO and CuO and allow noble metal recovery. The scavenger oxides Sb 2 O 3 , Bi 2 O 3 , and PbO, however, were reduced by all of the reducing agents tested. Similar noble metal recovery was found with each. Lead oxide was found to be the most promising of the potential scavengers. It was reduced by all of the reducing agents tested, and its higher density may facilitate the separation. Use of lead oxide also appeared to have no deterimental effect on the glass quality. Charcoal was identified as the preferred reducing agent. As long as a separable metal phase was formed in the melt, noble metal recovery was not dependent on the amount of reducing agent and scavenger oxide. High glass viscosities inhibited separation of the molten scavenger, while low viscosities allowed volatile loss of RuO 4 . A viscosity of approx. 20 poise at the processing temperature offered a good compromise between scavenger separation and Ru recovery. Glasses in which PbO was used as the scavenging agent were homogeneous in appearance. Resistance to leaching was close to that of certain waste glasses reported in the literature. 12 figures. 7 tables

4,6-Dimethyl-dibenzothiophene conversion over Al{sub 2}O{sub 3}-TiO{sub 2}-supported noble metal catalysts

Energy Technology Data Exchange (ETDEWEB)

Nunez, Sara [Departamento de Ingenieria de Procesos e Hidraulica, Universidad Autonoma Metropolitana-Iztapalapa, San Rafael Atlixco 186, Vicentina, Iztapalapa, 09340, Mexico, D.F. (Mexico); Escobar, Jose, E-mail: jeaguila@imp.mx [Instituto Mexicano del Petroleo, Eje Central Lazaro Cardenas 152, San Bartolo Atepehuacan, Gustavo A. Madero, 07730, Mexico, D.F. (Mexico); Vazquez, Armando; Reyes, Jose Antonio de los [Departamento de Ingenieria de Procesos e Hidraulica, Universidad Autonoma Metropolitana-Iztapalapa, San Rafael Atlixco 186, Vicentina, Iztapalapa, 09340, Mexico, D.F. (Mexico); Hernandez-Barrera, Melissa [Instituto Mexicano del Petroleo, Eje Central Lazaro Cardenas 152, San Bartolo Atepehuacan, Gustavo A. Madero, 07730, Mexico, D.F. (Mexico)

2011-03-15

Research highlights: {yields} Al{sub 2}O{sub 3} and Al{sub 2}O{sub 3}-TiO{sub 2} (molar ratio Al/Ti = 2, AT2) mixed oxides were pore-filling impregnated to obtain Pd, Pt and Pd-Pt catalysts with {approx}1 wt% nominal metal loading. {yields} Reduced catalysts were tested in the 4,6-dimethyl-dibenzothiophene hydrodesulfurization (HDS). {yields} In Pd-containing materials, TiO{sub 2} incorporation into the alumina support was favorable to the catalytic activity of noble metal catalysts. {yields} Enhanced intrinsic activity (per exposed metallic site) was obtained in Pt-containing catalysts supported on the AT2 mixed oxide. {yields} Yield to different products over various catalysts seemed to be strongly influenced by metallic particles dispersion. - Abstract: Al{sub 2}O{sub 3} and Al{sub 2}O{sub 3}-TiO{sub 2} (molar ratio Al/Ti = 2, AT2) mixed oxides were synthesized using a low-temperature sol-gel method and were further pore-filling impregnated to obtain Pd and Pt catalysts with {approx}1 wt% nominal metal loading. Simultaneous impregnation was used to prepare bimetallic materials at Pd:Pt = 80:20. Solids characterization was carried out by N{sub 2}-physisorption, high-resolution transmission electron microscopy (HR-TEM and E-FTEM), X-ray diffraction, temperature-programmed reduction and CO-chemisorption. Reduced (350 deg. C, H{sub 2} flow) catalysts were tested in the 4,6-dimethyl-dibenzothiophene hydrodesulfurization (HDS) (in n-dodecane, at 300 deg. C and 5.5 MPa, batch reactor). In Pd-containing materials, TiO{sub 2} incorporation into the alumina support was favorable to the catalytic activity of noble metal catalysts, where bimetallic Pd-Pt with AT2 carrier had the highest organo-S compound conversion. Enhanced intrinsic activity (per exposed metallic site) was obtained in Pt-containing catalysts supported on the AT2 mixed oxide (as compared to alumina-supported ones). Yield to different products over various catalysts seemed to be strongly influenced by

Methane oxidation over noble metal catalysts as related to controlling natural gas vehicle exhaust emissions

International Nuclear Information System (INIS)

Oh, S.H.; Mitchell, P.J.; Siewert, R.M.

1992-01-01

Natural gas has considerable potential as an alternative automotive fuel. This paper reports on methane, the principal hydrocarbon species in natural-gas engine exhaust, which has extremely low photochemical reactivity but is a powerful greenhouse gas. Therefore, exhaust emissions of unburned methane from natural-gas vehicles are of particular concern. This laboratory reactor study evaluates noble metal catalysts for their potential in the catalytic removal of methane from natural-gas vehicle exhaust. Temperature run-up experiments show that the methane oxidation activity decreases in the order Pd/Al 2 O 3 > Rh/Al 2 O 3 > Pt/Al 2 O 3 . Also, for all the noble metal catalysts studied, methane conversion can be maximized by controlling the O 2 concentration of the feedstream at a point somewhat rich (reducing) of stoichiometry

Noble Metal Nanoparticles for Biosensing Applications

Directory of Open Access Journals (Sweden)

Pedro V. Baptista

2012-02-01

Full Text Available In the last decade the use of nanomaterials has been having a great impact in biosensing. In particular, the unique properties of noble metal nanoparticles have allowed for the development of new biosensing platforms with enhanced capabilities in the specific detection of bioanalytes. Noble metal nanoparticles show unique physicochemical properties (such as ease of functionalization via simple chemistry and high surface-to-volume ratios that allied with their unique spectral and optical properties have prompted the development of a plethora of biosensing platforms. Additionally, they also provide an additional or enhanced layer of application for commonly used techniques, such as fluorescence, infrared and Raman spectroscopy. Herein we review the use of noble metal nanoparticles for biosensing strategies—from synthesis and functionalization to integration in molecular diagnostics platforms, with special focus on those that have made their way into the diagnostics laboratory.

Porous Silicon Hydrogen Sensor at Room Temperature: The Effect of Surface Modification and Noble Metal Contacts

Directory of Open Access Journals (Sweden)

Jayita KANUNGO

2009-04-01

Full Text Available Porous silicon (PS was fabricated by anodization of p-type crystalline silicon of resistivity 2-5 Ω cm. After formation, the PS surface was modified by the solution containing noble metal like Pd. Pd-Ag catalytic contact electrodes were deposited on porous silicon and on p-Silicon to fabricate Pd-Ag/PS/p-Si/Pd-Ag sensor structure to carry out the hydrogen sensing experiments. The Sensor was exposed to 1% hydrogen in nitrogen as carrier gas at room temperature (270C. Pd modified sensor showed minimum fluctuations and consistent performance with 86% response, response time and recovery time of 24 sec and 264 sec respectively. The stability experiments were studied for both unmodified and Pd modified sensor structures for a period of about 24 hours and the modified sensors showed excellent durability with no drift in response behavior.

Magneto-optical Kerr spectroscopy of noble metals

Science.gov (United States)

Uba, L.; Uba, S.; Antonov, V. N.

2017-12-01

Magneto-optical (MO) response of the noble metals Cu, Ag, and Au in the joint experimental and ab initio theoretical study is reported. The magneto-optical polar Kerr effect (MOKE) spectra of the noble-metal films were measured with the high sensitivity in the applied magnetic field of 1.5 T over the photon energy range 0.74-5.8 eV. Complete set of the optical conductivity tensor elements was determined precisely from the MOKE and the optical spectra measured at the same energy points. The importance of the off-diagonal intraband Drude-type transitions is demonstrated explicitly for each noble metal and found to be a substantial contribution to the observed spectra. It is shown that the first-principles calculations using the spin-polarized fully relativistic Dirac linear-muffin-tin-orbital method with the inclusion of correlation effects by GGA+U approach reproduce well the experimental spectra and allow to explain the microscopic origin of the noble metals' magneto-optical response in terms of interband transitions. Although the energy band structures of Cu, Ag, and Au are very similar, there are some distinctive differences in bandwidths and the energy positions of the bands (especially in X and L symmetry points), mainly due to different spin-orbit splitting and differences in the spatial extent of 3 d , 4 d , and 5 d valence wave functions of noble metals. It was found that the small differences in the band positions lead to significant differences in the MO properties of three noble metals. Although the spin-orbit interaction in Au is about six times larger than in Cu, and approximately two times larger than in Ag, the absolute value of Kerr rotation in Au is of the same magnitude as in Cu and one order of magnitude smaller as compared to Ag. The sharp Kerr effect spectral peak in Ag is not due to the electronic interband transitions, but rather to the plasma-edge splitting. The band-by-band decomposition of the Cu, Ag, and Au MO spectra is presented and the

Oxidation of tritium in packed bed of noble metal catalyst for detritiation from system gases

International Nuclear Information System (INIS)

Nishikawa, Masabumi; Takeishi, Toshiharu; Munakata, Kenzo; Kotoh, Kenji; Enoeda, Mikio

1985-01-01

Catalytic oxidation rates of tritium in the bed of the noble metal catalysts are obtained and compared with the oxidation rates observed for the packed bed of spongy copper oxide or hopcalites. Use of Pt- or Pd-aluminia catalysts is recommended in this study because they give effective oxidation rates of tritium in the ambient temperature range. The adsorption performance of tritiated water in the catalyst bed is also discussed. (orig.)

Promotion of Phenol Photodecomposition over TiO2 Using Au, Pd, and AuPd Nanoparticles

DEFF Research Database (Denmark)

Su, Ren; Tiruvalam, Ramchandra; He, Qian

2012-01-01

Noble metal nanoparticles (Au, Pd, AuPd alloys) with a narrow size distribution supported on nanocrystalline TiO2 (M/TiO2) have been synthesized via a sol-immobilization route. The effect of metal identity and size on the photocatalytic performance of M/TiO2 has been systematically investigated u...

An unsaturated metal site-promoted approach to construct strongly coupled noble metal/HNb3O8 nanosheets for efficient thermo/photo-catalytic reduction.

Science.gov (United States)

Shen, Lijuan; Xia, Yuzhou; Lin, Sen; Liang, Shijing; Wu, Ling

2017-10-05

Creating two-dimensional (2D) crystal-metal heterostructures with an ultrathin thickness has spurred increasing research endeavors in catalysis because of its fascinating opportunities in tuning the electronic state at the surface and enhancing the chemical reactivity. Here we report a novel and facile Nb 4+ -assisted strategy for the in situ growth of highly dispersed Pd nanoparticles (NPs) on monolayer HNb 3 O 8 nanosheets (HNb 3 O 8 NS) constituting a 2D Pd/HNb 3 O 8 NS heterostructure composite without using extra reducing agents and stabilizing agents. The Pd NP formation is directed via a redox reaction between an oxidative Pd salt precursor (H 2 PdCl 4 ) and reductive unsaturated surface metal (Nb 4+ ) sites induced by light irradiation on monolayer HNb 3 O 8 NS. The periodic arrangement of metal Nb nodes on HNb 3 O 8 NS leads to a homogeneous distribution of Pd NPs. Density functional theory (DFT) calculations reveal that the direct redox reaction between the Nb 4+ and Pd 2+ ions leads to a strong chemical interaction between the formed Pd metal NPs and the monolayer HNb 3 O 8 support. Consequently, the as-obtained Pd/HNb 3 O 8 composite serves as a highly efficient bifunctional catalyst in both heterogeneous thermocatalytic and photocatalytic selective reduction of aromatic nitro compounds in water under ambient conditions. The achieved high activity originates from the unique 2D nanosheet configuration and in situ Pd incorporation, which leads to a large active surface area, strong metal-support interaction and enhanced charge transport capability. Moreover, this facile Nb 4+ -assisted synthetic route has demonstrated to be general, which can be applied to load other metals such as Au and Pt on monolayer HNb 3 O 8 NS. It is anticipated that this work can extend the facile preparation of noble metal/nanosheet 2D heterostructures, as well as promote the simultaneous capture of duple renewable thermal and photon energy sources to drive an energy efficient

Catalytic pyrolysis of wheat bran for hydrocarbons production in the presence of zeolites and noble-metals by using TGA-FTIR method.

Science.gov (United States)

Lazdovica, K; Liepina, L; Kampars, V

2016-05-01

Pyrolysis of wheat bran with or without catalysts was investigated using TGA-FTIR method in order to determine the influence of zeolite and noble metal catalysts on the evolution profile and relative yield of the volatile compounds. The addition of all catalysts decreased the volatile matter of wheat bran from 76.3% to 75.9%, 73.9%, 73.5%, 69.7% and increased the solid residue from 18.0% to 18.4%, 20.4%, 20.8%, 24.6% under the catalyst of ZSM-5, 5% Pd/C, MCM-41, and 5% Pt/C. Noble-metal catalysts had higher activity for deoxygenation of compounds containing carbonyl, carboxyl, and hydroxyl groups than zeolites. Degradation of nitrogen containing compounds atom proceeded better in presence of zeolites. Noble-metal catalysts promoted formation of aromatics and changed the profiles of evolved compounds whereas zeolites advanced formation of aliphatics and olefins. Copyright © 2016 Elsevier Ltd. All rights reserved.

Evaluation of HWVP feed preparation chemistry for an NCAW simulant -- Fiscal year 1993: Effect of noble metals concentration on offgas generation and ammonia formation

International Nuclear Information System (INIS)

Patello, G.K.; Wiemers, K.D.; Bell, R.D.; Smith, H.D.; Williford, R.E.; Clemmer, R.G.

1995-03-01

The High-Level Waste Vitrification Program is developing technology for the Department of Energy to immobilize high-level and transuranic wastes as glass for permanent disposal. Pacific Northwest Laboratory (PNL) is conducting laboratory-scale melter feed preparation studies using a HWVP simulated waste slurry, Neutralized Current Acid Waste (NCAW). A FY 1993 laboratory-scale study focused on the effects of noble metals (Pd, Rh, and Ru) on feed preparation offgas generation and NH 3 production. The noble metals catalyze H 2 and NH 3 production, which leads to safety concerns. The information gained from this study is intended to be used for technology development in pilot scale testing and design of the Hanford High-Level Waste Vitrification Facility. Six laboratory-scale feed preparation tests were performed as part of the FY 1993 testing activities using nonradioactive NCAW simulant. Tests were performed with 10%, 25%, 50% of nominal noble metals content. Also tested were 25% of the nominal Rh and a repeat of 25% nominal noble metals. The results of the test activities are described. 6 refs., 28 figs., 12 tabs

Evaluation of HWVP feed preparation chemistry for an NCAW simulant -- Fiscal year 1993: Effect of noble metals concentration on offgas generation and ammonia formation

Energy Technology Data Exchange (ETDEWEB)

Patello, G.K.; Wiemers, K.D.; Bell, R.D.; Smith, H.D.; Williford, R.E.; Clemmer, R.G.

1995-03-01

The High-Level Waste Vitrification Program is developing technology for the Department of Energy to immobilize high-level and transuranic wastes as glass for permanent disposal. Pacific Northwest Laboratory (PNL) is conducting laboratory-scale melter feed preparation studies using a HWVP simulated waste slurry, Neutralized Current Acid Waste (NCAW). A FY 1993 laboratory-scale study focused on the effects of noble metals (Pd, Rh, and Ru) on feed preparation offgas generation and NH{sub 3} production. The noble metals catalyze H{sub 2} and NH{sub 3} production, which leads to safety concerns. The information gained from this study is intended to be used for technology development in pilot scale testing and design of the Hanford High-Level Waste Vitrification Facility. Six laboratory-scale feed preparation tests were performed as part of the FY 1993 testing activities using nonradioactive NCAW simulant. Tests were performed with 10%, 25%, 50% of nominal noble metals content. Also tested were 25% of the nominal Rh and a repeat of 25% nominal noble metals. The results of the test activities are described. 6 refs., 28 figs., 12 tabs.

Recovery of noble metals from HLLW using photocatalytic reduction

International Nuclear Information System (INIS)

Nishi, T.; Uetake, N.; Kawamura, F.; Yusa, H.

1987-01-01

In high-level liquid waste (HLLW) from fuel reprocessing plants, noble metals (palladium, rhodium, and ruthenium), which account for ∼ 10 wt% of fission products, exist as ions. These metals are very useful as catalytic material in automobile exhaust systems and other chemical processes, but they are rare in nature, making their recovery from fission products highly desirable. The ions of noble metals in solution have the feature that their reduction potential from ion to metal is relatively high compared with that of other fission product ions, so they can be selectively separated as a metal by a reduction process. The authors think a photoreduction process using a photocatalysts, which functions as photon-electron conversion agent, is suitable for the recovery of noble metals from HLLW for three reasons: (1) this process uses no reduction agents, which usually degrade the nitric acid, so that coprecipitation of other fission products does not occur. (2) The reactions are induced by light, which does not contaminate the reaction system, and in contrast with ordinary photo-redox reactions, the quantum yield is quite high. (3) As the photocatalyst does not change in the reaction, it can be used again and again. The report shows the results of fundamental experiments on the application of photocatalytic reduction to the recovery of noble metal ions in nitric acid solution

Noble Metal/Ceramic Composites in Flame Processes

DEFF Research Database (Denmark)

Schultz, Heiko; Madler, Lutz; Strobel, Reto

conditions influence the resulting noble metal particles size in those systems [1]. For every specific application the particle size and the metal/metal oxide interaction affect the performance of these nano-composite materials [2]. Recently, aerosol processes have been successfully used to produce platinum...

Engineering noble metal nanomaterials for environmental applications

Science.gov (United States)

Li, Jingguo; Zhao, Tingting; Chen, Tiankai; Liu, Yanbiao; Ong, Choon Nam; Xie, Jianping

2015-04-01

Besides being valuable assets in our daily lives, noble metals (namely, gold, silver, and platinum) also feature many intriguing physical and chemical properties when their sizes are reduced to the nano- or even subnano-scale; such assets may significantly increase the values of the noble metals as functional materials for tackling important societal issues related to human health and the environment. Among which, designing/engineering of noble metal nanomaterials (NMNs) to address challenging issues in the environment has attracted recent interest in the community. In general, the use of NMNs for environmental applications is highly dependent on the physical and chemical properties of NMNs. Such properties can be readily controlled by tailoring the attributes of NMNs, including their size, shape, composition, and surface. In this feature article, we discuss recent progress in the rational design and engineering of NMNs with particular focus on their applications in the field of environmental sensing and catalysis. The development of functional NMNs for environmental applications is highly interdisciplinary, which requires concerted efforts from the communities of materials science, chemistry, engineering, and environmental science.

Engineering noble metal nanomaterials for environmental applications.

Science.gov (United States)

Li, Jingguo; Zhao, Tingting; Chen, Tiankai; Liu, Yanbiao; Ong, Choon Nam; Xie, Jianping

2015-05-07

Besides being valuable assets in our daily lives, noble metals (namely, gold, silver, and platinum) also feature many intriguing physical and chemical properties when their sizes are reduced to the nano- or even subnano-scale; such assets may significantly increase the values of the noble metals as functional materials for tackling important societal issues related to human health and the environment. Among which, designing/engineering of noble metal nanomaterials (NMNs) to address challenging issues in the environment has attracted recent interest in the community. In general, the use of NMNs for environmental applications is highly dependent on the physical and chemical properties of NMNs. Such properties can be readily controlled by tailoring the attributes of NMNs, including their size, shape, composition, and surface. In this feature article, we discuss recent progress in the rational design and engineering of NMNs with particular focus on their applications in the field of environmental sensing and catalysis. The development of functional NMNs for environmental applications is highly interdisciplinary, which requires concerted efforts from the communities of materials science, chemistry, engineering, and environmental science.

Comparison of the tensile bond strength of high-noble, noble, and base metal alloys bonded to enamel.

Science.gov (United States)

Sen, D; Nayir, E; Pamuk, S

2000-11-01

Although the bond strengths of various resin composite luting materials have been reported in the literature, the evaluation of these systems with various cast alloys of different compositions has not been completely clarified. To evaluate the tensile bond strength of sandblasted high-noble, noble, and base metal alloys bonded to etched enamel by 2 different bonding agents of different chemical composition: Panavia-Ex (BIS-GMA) and Super-Bond (4-META acrylic). Flat enamel surfaces were prepared on buccal surfaces of 60 extracted noncarious human incisors. Teeth were divided into 3 groups of 20 each. Twenty circular disks of 5 mm diameter were prepared for casting for each group. Group I was cast with a high-noble, group II with a noble, and group III with a base metal alloy. The surfaces of the disks were sandblasted with 250 microm Al(2)O(3). Ten disks of each group were bonded to exposed enamel surfaces with Super-Bond and 10 disks with Panavia-Ex as recommended by the manufacturer. The tensile bond strength was measured with an Instron universal testing machine with a crosshead speed of 0.5 mm/min until failure occurred. Two-way ANOVA was used to evaluate the results. The differences in bond strengths of Super-Bond and Panavia-Ex with different alloys were not significant. The highest bond strengths were obtained in base metal alloys, followed by noble and high-noble alloys. These results were significant. Panavia-Ex and Super-Bond exhibited comparable tensile bond strengths. For both luting agents, the highest bond strengths were achieved with base metal alloys and the lowest with high-noble alloys.

The role of van der Waals interactions in the adsorption of noble gases on metal surfaces

Energy Technology Data Exchange (ETDEWEB)

Chen, De-Li; Al-Saidi, W A; Johnson, J Karl

2012-10-03

Adsorption of noble gases on metal surfaces is determined by weak interactions. We applied two versions of the nonlocal van der Waals density functional (vdW-DF) to compute adsorption energies of Ar, Kr, and Xe on Pt(111), Pd(111), Cu(111), and Cu(110) metal surfaces. We have compared our results with data obtained using other density functional approaches, including the semiempirical vdW corrected DFT-D2. The vdW-DF results show considerable improvements in the description of adsorption energies and equilibrium distances over other DFTbased methods, giving good agreement with experiments. We have also calculated perpendicular vibrational energies for noble gases on the metal surfaces using vdWDF data and found excellent agreement with available experimental results. Our vdW-DF calculations show that adsorption of noble gases on low-coordination sites is energetically favored over high-coordination sites, but only by a few meV. Analysis of the 2-dimensional potential energy surface shows that the high-coordination sites are local maxima on the 2-dimensional potential energy surface and therefore unlikely to be observed in experiments, which provides an explanation of the experimental observations. The DFT-D2 approach with the standard parameterization was found to overestimate the dispersion interactions, and to give the wrong adsorption site preference for four of the nine systems we studied.

Ab initio theory of noble gas atoms in bcc transition metals.

Science.gov (United States)

Jiang, Chao; Zhang, Yongfeng; Gao, Yipeng; Gan, Jian

2018-06-18

Systematic ab initio calculations based on density functional theory have been performed to gain fundamental understanding of the interactions between noble gas atoms (He, Ne, Ar and Kr) and bcc transition metals in groups 5B (V, Nb and Ta), 6B (Cr, Mo and W) and 8B (Fe). Our charge density analysis indicates that the strong polarization of nearest-neighbor metal atoms by noble gas interstitials is the electronic origin of their high formation energies. Such polarization becomes more significant with an increasing gas atom size and interstitial charge density in the host bcc metal, which explains the similar trend followed by the unrelaxed formation energies of noble gas interstitials. Upon allowing for local relaxation, nearby metal atoms move farther away from gas interstitials in order to decrease polarization, albeit at the expense of increasing the elastic strain energy. Such atomic relaxation is found to play an important role in governing both the energetics and site preference of noble gas atoms in bcc metals. Our most notable finding is that the fully relaxed formation energies of noble gas interstitials are strongly correlated with the elastic shear modulus of the bcc metal, and the physical origin of this unexpected correlation has been elucidated by our theoretical analysis based on the effective-medium theory. The kinetic behavior of noble gas atoms and their interaction with pre-existing vacancies in bcc transition metals have also been discussed in this work.

Structure determination of chitosan-stabilized Pt and Pd based bimetallic nanoparticles by X-ray photoelectron spectroscopy and transmission electron microscopy

International Nuclear Information System (INIS)

Wu, Lihua; Shafii, Salimah; Nordin, Mohd Ridzuan; Liew, Kong Yong; Li, Jinlin

2012-01-01

Chitosan (CTS)-stabilized bimetallic nanoparticles were prepared at room temperature (rt.) in aqueous solution. Palladium (Pd) and platinum (Pt) were selected as the first metals while iron (Fe) and nickel (Ni) functioned as the second metals. In order to obtain the noble metal core-transition metal shell structures, bimetallic nanoparticles were prepared in a two-step process: the preparation of mono noble metallic (Pd or Pt) nanoparticles and the deposition of transition metals (Fe or Ni) on the surface of the monometallic nanoparticles. The structures of the nanoparticles were studied using X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). The XPS results show that Pd and Pt exist mainly in zero valences. The presence of Fe and Ni in the bimetallic nanoparticles affects the binding energy of Pd and Pt. Moreover, the studies of O 1s spectra indicate the presence of Fe or Ni shells. The analyses of TEM micrographs give the particle size and size distributions while the high-resolution TEM (HRTEM) micrographs show the existence of noble metal core lattices. The results confirm the formation of noble metal core-transition metal shell structures. -- Highlights: ► Chitosan-stabilized bimetallic nanoparticles were prepared at room temperature in aqueous solution. ► The presence of Fe or Ni shells was proven by XPS study. ► The existence of noble metal cores covered by amorphous shells was indicated by TEM study. ► The formation of noble metal core-transition metal shell structures was confirmed.

Metal-organic frameworks for adsorption and separation of noble gases

Energy Technology Data Exchange (ETDEWEB)

Allendorf, Mark D.; Greathouse, Jeffery A.; Staiger, Chad

2017-05-30

A method including exposing a gas mixture comprising a noble gas to a metal organic framework (MOF), including an organic electron donor and an adsorbent bed operable to adsorb a noble gas from a mixture of gases, the adsorbent bed including a metal organic framework (MOF) including an organic electron donor.

Synthesis and characterization of fluorescence-labelled silica core-shell and noble metal-decorated ceria nanoparticles

Directory of Open Access Journals (Sweden)

Rudolf Herrmann

2014-12-01

Full Text Available The present review article covers work done in the cluster NPBIOMEM in the DFG priority programme SPP 1313 and focuses on synthesis and characterization of fluorescent silica and ceria nanoparticles. Synthetic methods for labelling of silica and polyorganosiloxane/silica core–shell nanoparticles with perylenediimide derivatives are described, as well as the modification of the shell with thiol groups. Photometric methods for the determination of the number of thiol groups and an estimate for the number of fluorescent molecules per nanoparticles, including a scattering correction, have been developed. Ceria nanoparticles decorated with noble metals (Pt, Pd, Rh are models for the decomposition products of automobile catalytic converters which appear in the exhaust gases and finally interact with biological systems including humans. The control of the degree of agglomeration of small ceria nanoparticles is the basis for their synthesis. Almost monodisperse agglomerates (40 ± 4–260 ± 40 nm diameter can be prepared and decorated with noble metal nanoparticles (2–5 nm diameter. Fluorescence labelling with ATTO 647N gave the model particles which are now under biophysical investigation.

The behavior and effects of the noble metals in the DWPF melter system

International Nuclear Information System (INIS)

Hutson, N.D.; Smith, M.E.

1992-01-01

Fission-product noble metals have caused severe operating problems in numerous worldwide waste vitrification facilities. These dense, highly conductive noble metals have tended to accumulate on the floor of joule-heated glass melters causing electrical distortions which have, in some occurrences, rendered the melter inoperable. A pilot scale vitrification research facility at the U.S. Department of Energy's Savannah River Laboratory has been operated for more than a year with simulated feed streams containing noble metals. In this paper the behavior of these noble metals in the melter system and final glass product and their effects on the scaled DWPF-type melter are discussed

Biomimetic synthesis of noble metal nanocrystals

Science.gov (United States)

Chiu, Chin-Yi

At the nanometer scale, the physical and chemical properties of materials heavily depend on their sizes and shapes. This fact has triggered considerable efforts in developing controllable nanomaterial synthesis. The controlled growth of colloidal nanocrystal is a kinetic process, in which high-energy facets grow faster and then vanish, leading to a nanocrystal enclosed by low-energy facets. Identifying a surfactant that can selectively bind to a particular crystal facet and thus lower its surface energy, is critical and challenging in shape controlled synthesis of nanocrystals. Biomolecules exhibiting exquisite molecular recognition properties can be exploited to precisely engineer nanostructured materials. In the first part of my thesis, we employed the phage display technique to select a specific multifunctional peptide sequence which can bind on Pd surface and mediate Pd crystal nucleation and growth, achieving size controlled synthesis of Pd nanocrystals in aqueous solution. We further demonstrated a rational biomimetic approach to the predictable synthesis of nanocrystals enclosed by a particular facet in the case of Pt. Specifically, Pt {100} and Pt {111} facet-specific peptides were identified and used to synthesize Pt nanocubes and Pt nano-tetrahedrons, respectively. The mechanistic studies of Pt {111} facet-specific peptide had led us to study the facet-selective adsorption of aromatic molecules on noble metal surfaces. The discoveries had achieved the development of design strategies to select facet-selective molecules which can synthesize nanocrystals with expected shapes in both Pt and Pd system. At last, we exploited Pt facet-specific peptides and controlled the molecular interaction to produce one- and three- dimensional nanostructures composed of anisotropic nanoparticles in synthetic conditions without supramolecular pre-organization, demonstrating the full potential of biomolecules in mediating material formation process. My research on biomimetic

Contributions to the determination of the noble metals gold, iridium, palladium, platinum, rhodium and application to environmentally relevant samples

International Nuclear Information System (INIS)

Zischka, M.

1998-11-01

The concentrations of noble metals in the environment are still very low (low ng/g and sub ng/g range), although they are emitted to an increasing extent as components of catalytic exhaust emission converters into the environment. The determination of these elements can be error prone even when the determinations are carried out by use of highly sensitive methods in combination with high performance sample preparation techniques. Accurate data with smallest possible measurement uncertainties are a prerequisite for the interpretation of the distribution of noble metals in the environment and their possible toxicological effects. Difficulties related to the determination of the noble metals could be the incomplete recovery after sample preparation, sample digestion and interferences arising in subsequent instrumental determination methods. For this reason two different sample decomposition methods in combination with powerful instrumental techniques are checked for suitability for the determination of the noble metals in environmentally relevant samples. Digestion methods under evaluation are the NiS fire assay and the leaching with aqua regia in closed vessels under high pressure and high temperature. The NiS fire assay provides pre-concentration of the noble-metals and matrix separation of most of the remaining matrix elements. Disadvantages of this method are the need for experienced analysts, the awkward handling and the time-consuming procedure. On the other hand leaching with aqua regia under high pressure at high temperatures is easy to handle and not time-consuming with the crucial disadvantage that neither a pre-concentration of the noble metals nor a matrix separation can be achieved. Investigated instrumental techniques are the ICP-AES (inductively coupled plasma atomic emission spectrometry) with an axially arranged plasma either with a cross-flow or with an ultrasonic nebulizer, the quadrupole ICP-MS (inductively coupled plasma mass spectrometry) and the

Polymer-noble metal nanocomposites: Review

CSIR Research Space (South Africa)

Folarin, OM

2011-09-01

Full Text Available because of their multi-functionality, ease of process-ability, potential for large-scale manufacturing, significantly lighter than metals, ease of synthesis when compared to the oxide/noble metal multi-layers (Gass et al., 2006; Lee et al., 2003.... their easy aggregation arising from their high surface free energy (Lee et al., 2006). In the design of nanocomposites, one must consider the properties of the polymer matrix as well as the stability of the nanoparticles and more importantly...

On the methodology of radiochemical neutron activation analysis of noble metals

International Nuclear Information System (INIS)

Chai, C.F.; Ma, S.L.; Mao, X.Y.; Liao, K.N.; Liu, W.C.

1986-01-01

Two different radiochemical procedures were developed: chelate ion resin exchange and amine solvent extraction. Two kinds of new Chinese chelate resins (NANKAI-3926 and BEI-5) and a new long-chain primary amine N 1923 were compared with Srafion NMRR and the tertiary amine N 235 in absorption performance of noble metals, respectively. Influences of various experimental conditions, e.g. sample digestion, acidity, equilibrium time, as well as elution of noble metals, on analytical sensitivity and chemical yield were discussed. Combining with neutron activation, the radiochemical separation procedures developed were used to determine the noble metal contents in the geological samples from Permina/Triassic boundary in South China. (author)

Green synthesis of noble nanometals (Au, Pt, Pd) using glycerol under microwave irradiation conditions

Science.gov (United States)

A newer application of glycerol in the field of nanomaterials synthesis has been developed from both the economic and environmental points of view. Glycerol can act as a reducing agent for the fabrication of noble nanometals, such as Au, Pt, and Pd, under microwave irradiation. T...

Techniques for the quantitative analysis of fission-product noble metals

International Nuclear Information System (INIS)

Lautensleger, A.W.; Hara, F.T.

1982-08-01

Analytical procedures for the determination of ruthenium, rhodium, and palladium in precursor waste, solvent metal, and final glass waste forms have been developed. Two procedures for the analysis of noble metals in the calcine and glass waste forms are described in this report. The first is a fast and simple technique that combines inductively coupled argon plasma atomic emission spectrometry (ICP) and x-ray fluorescence techniques and can only be used on nonradioactive materials. The second procedure is based on a noble metal separation step, followed by an analysis using ICP. This second method is more complicated than the first, but it will work on radioactive materials. Also described is a procedure for the ICP analysis of noble metals in the solvent metal matrix. The only solvent metal addressed in this procedure is lead, but with minor changes the procedure could be applied to any of the solvent metals being considered in the Pacific Northwest Laboratory (PNL) extraction process. A brief explanation of atomic spectroscopy and the ICP analytical process, as well as of certain aspects of ICP performance (interelement spectral line interferences and certain matrix effects) is given

The prevalent synthesis of one-dimensional noble metal nanostructures based on sulfonated polyaniline at room temperature

International Nuclear Information System (INIS)

Xia Youyi

2011-01-01

We describe a prevalent method of synthesizing one-dimensional (1D) noble metal nanostructures (silver nanobelts and palladium nanowires) by treatment of corresponding noble metal ions only in the presence of the conductive sulfonated polyaniline without using any other reducing agents or energies. The results show that the sulfonated polyaniline provides the dual reductant and “soft template” roles to promoting noble metal ions to form shape-controlled 1D noble metal nanostructures in high yield. The employed approach may also shed some light on the preparation of other noble metal nanostructure by using conductive polymer.

Behavior of shut-down dose rate of recirculation piping of BWR under noble metal application

International Nuclear Information System (INIS)

Fuse, Motomasa; Nagase, Makoto; Aizawa, Motohiro; Wada, Yoichi; Ishida, Kazushige; Hosokawa, Hideyuki; Hettiarachchi, Samson; Weber, Christoph

2014-01-01

The cause of shut-down dose rate change of the recirculation piping observed in KKM (Kern Kraftwerk Mühleberg) after application of noble metal injection method is analyzed. The plant experienced the sharp decrease of piping dose rate in the cycle just after the application of noble metal(classic NobleChem TM ) and re-buildup of radioactivity in the subsequent several cycles. After the application of online noble metal injection (online NobleChem TM ), gradual decrease of dose rate has been observed. The presence of a certain amount of noble metal on the iron rich oxide film promotes the dissolution of the oxide under hydrogen addition, resulting in a decrease of deposited noble metal on the oxide film surface as well as of radioactive species in the film. Under the condition of lower amount of noble metal on the surface oxides, the oxidant species, especially hydrogen peroxide, slightly increases facilitating the re-growth of iron rich oxides along with re-buildup of radioactivity. After the application of online noble metal injection during each cycle, gradual dissolution of iron rich oxides and gradual decrease of radioactivity in the oxides proceed to decrease the piping dose rate. In the radioactivity decreasing phase, the presence of zinc is considered to assist the suppression of radioactivity buildup in the oxide film. From the analysis, treating piping surface with platinum after chemical decontamination process is expected to work well for suppression of the piping dose rate. (author)

Rational design of binder-free noble metal/metal oxide arrays with nanocauliflower structure for wide linear range nonenzymatic glucose detection

KAUST Repository

Li, Zhenzhen; Xin, Yanmei; Zhang, Zhonghai; Wu, Hongjun; Wang, Peng

2015-01-01

One-dimensional nanocomposites of metal-oxide and noble metal were expected to present superior performance for nonenzymatic glucose detection due to its good conductivity and high catalytic activity inherited from noble metal and metal oxide

The Simple, Effective Synthesis of Highly Dispersed Pd/C and CoPd/C Heterogeneous Catalysts via Charge-Enhanced Dry Impregnation

Directory of Open Access Journals (Sweden)

Lawrence D’Souza

2016-05-01

Full Text Available Pd/C and CoPd/C heterogeneous catalysts have been synthesized by adopting Charge Enhanced Dry Impregnation (CEDI. The particles size distribution, their high metal surface-to-bulk ratios, and synthesis feasibility are unmatchable to any known noble metal bimetallic heterogeneous catalyst preparation techniques. Next generation Fuel Cells and Fischer-Tropsch catalytic processes economy will be benefited from the proposed methodology.

Pd surface functionalization of 3D electroformed Ni and Ni-Mo alloy metallic nanofoams for hydrogen production

Science.gov (United States)

Petica, A.; Brincoveanu, O.; Golgovici, F.; Manea, A. C.; Enachescu, M.; Anicai, L.

2018-03-01

The paper presents some experimental results regarding the functionalization of 3D electroformed Ni and Ni-Mo alloy nanofoams with Pd nanoclusters, as potential cathodic materials suitable for HER during seawater electrolysis. The electrodeposition from aqueous electrolytes containing NiCl2 and NH4Cl has been applied to prepare the 3D Ni nanofoams. Ni-Mo alloys have been electrodeposited involving aqueous ammonium citrate type electrolytes. Pd surface functionalization has been performed using both electroless and electrochemical procedures. Pd content varied in the range of 0.5 – 8 wt.%, depending on the applied procedure and the operation conditions. The use of a porous structure associated with alloying element (i.e. Mo) and Pd surface functionalization facilitated enhanced performances from HER view point in seawater electrolyte (lower Tafel slopes). The determined Tafel slope values ranged from 123 to 105 mV.dec-1, suggesting the Volmer step as rate determining step. The improvement of the HER catalytic activity may be ascribed to a synergistic effect between the high real active area of the 3D electroformed metallic substrate, Ni alloying with a left transition metal and surface modification using Pd noble metal.

Ethanol electrooxidation on Pt/C and Pd/C catalysts promoted with oxide

Energy Technology Data Exchange (ETDEWEB)

Xu, Changwei [Department of Chemistry and Institute of Nanochemistry, Jinan University, Guangzhou 510632 (China); State Key Laboratory of Optoelectronic Materials and Technologies, School of Physics and Engineering, Sun Yat-Sen University, Guangzhou 510275 (China); Shen, Pei kang [State Key Laboratory of Optoelectronic Materials and Technologies, School of Physics and Engineering, Sun Yat-Sen University, Guangzhou 510275 (China); Liu, Yingliang [Department of Chemistry and Institute of Nanochemistry, Jinan University, Guangzhou 510632 (China)

2007-02-10

This research aims to investigate Pd-based catalysts as a replacement for Pt-based catalysts for ethanol electrooxidation in alkaline media. The results show that Pd/C has a higher catalytic activity and better steady-state behaviour for ethanol oxidation than that of Pt/C. The effect of the addition of CeO{sub 2} and NiO to the Pt/C and Pd/C electrocatalysts on ethanol oxidation is also studied in alkaline media. The electrocatalysts with a weight ratio of noble metal (Pt, Pd) to CeO{sub 2} of 2:1 and a noble metal to NiO ration 6:1 show the highest catalytic activity for ethanol oxidation. The oxide promoted Pt/C and Pd/C electrocatalysts show a higher activity than the commercial E-TEK PtRu/C electrocatalyst for ethanol oxidation in alkaline media. (author)

Near transferable phenomenological n-body potentials for noble metals.

Science.gov (United States)

Pontikis, Vassilis; Baldinozzi, Gianguido; Luneville, Laurence; Simeone, David

2017-09-06

We present a semi-empirical model of cohesion in noble metals with suitable parameters reproducing a selected set of experimental properties of perfect and defective lattices in noble metals. It consists of two short-range, n-body terms accounting respectively for attractive and repulsive interactions, the former deriving from the second moment approximation of the tight-binding scheme and the latter from the gas approximation of the kinetic energy of electrons. The stability of the face centred cubic versus the hexagonal compact stacking is obtained via a long-range, pairwise function of customary use with ionic pseudo-potentials. Lattice dynamics, molecular statics, molecular dynamics and nudged elastic band calculations show that, unlike previous potentials, this cohesion model reproduces and predicts quite accurately thermodynamic properties in noble metals. In particular, computed surface energies, largely underestimated by existing empirical cohesion models, compare favourably with measured values, whereas predicted unstable stacking-fault energy profiles fit almost perfectly ab initio evaluations from the literature. All together the results suggest that this semi-empirical model is nearly transferable.

Properties and application of noble metal catalysts for heterogeneous catalytic hydrogenations

Energy Technology Data Exchange (ETDEWEB)

Horn, G; Frohning, C D; Cornils, B [Ruhrchemie A.G., Oberhausen (Germany, F.R.)

1976-07-01

The special properties of the six platinum group elements - ruthenium, rhodium, palladium, osmium, iridium, platinum - make them useful as active metals for catalytic reactions. Especially valuable is their property of favouring a single reaction even when the possibility of a number of parallel reactions exists under certain reaction conditions. This selectivity of the noble metal catalyst may be directed or enhanced through appropriate choise of the metal, the reaction conditions, the duration of the reaction, the amount of hydrogen etc. Even the physical state of the catalyst - supported or unsupported - is of influence when using noble metal catalysts as described in this report.

The predicted effectiveness of noble metal treatment at the Chinshan boiling water reactor

International Nuclear Information System (INIS)

Yeh Tsungkuang; Chu Fang; Chang Ching; Huang Chiashen

2000-01-01

The technique of noble metal treatment (NMT) available in a form of noble metal cooling (NMC) or noble metal chemical addition (NMCA), was introduced to enhance effectiveness of hydrogen water chemistry. Since it is technically difficult to gain access to an entire primary heat transport circuit (PHTC) of a BWR and monitor variation on electrochemical corrosion potential (ECP), a question whether the NMC technology is indeed effective for lowering the ECP of every location in a BWR is not still well understood at the moment. Then, computer modeling is so far the best tool to help investigate effectiveness of the NMT along PHCT of the BWR. Here was discussed on how the computer model was calibrated by using measured chemistry data obtained from No. 2 unit (BWR) in the Kuosheng Plant. The effect of noble metal treatment coupled with hydrogen water chemistry has been quantitatively molded, on a base of two different sets of ECD enhancement data. It was predicted that No. 1 unit in the Chinshan could be protected by noble metal treatment with lower [H 2 ] FW . In the case of competitive enhancing factors for the ECDs of oxygen reduction, hydrogen peroxide reduction, and hydrogen oxidation reactions, HWC had always to be present for noble metal treatment to be effective for protecting a reactor. Otherwise, according to a model calculation based upon the results from Kim's work, the ECP might instead be increased due to the enhanced reduction reaction rate of oxygen and hydrogen peroxide, especially in the near core regions. (G.K.)

An effective hydrothermal route for the synthesis of multiple PDDA-protected noble-metal nanostructures.

Science.gov (United States)

Chen, Hongjun; Wang, Yuling; Dong, Shaojun

2007-12-10

In this article, we demonstrate an effective hydrothermal route for the synthesis of multiple PDDA-protected (PDDA = poly(diallyl dimethylammonium) chloride) noble-metal (including silver, platinum, palladium, and gold) nanostructures in the absence of any seeds and surfactants, in which PDDA, an ordinary and water-soluble polyelectrolyte, acts as both a reducing and a stabilizing agent. Under optimal experimental conditions, Ag nanocubes, Pt and Pd nanopolyhedrons, and Au nanoplates can be obtained, which were characterized by transmission electron microscopy , scanning electron microscopy, energy-dispersive spectroscopy, and X-ray diffraction. More importantly, the nanostructures synthesized show potential applications in surface-enhanced Raman scattering and electrocatalysis, in which Ag nanocubes and Pt nanopolyhedrons were chosen as the examples, respectively.

Role of noble metal nanoparticles in DNA base damage and catalysis: a radiation chemical investigation

International Nuclear Information System (INIS)

Sharma, Geeta K.

2011-01-01

In the emerging field of nanoscience and nanotechnology, tremendous focus has been made by researcher to explore the applications of nanomaterials for human welfare by converting the findings into technology. Some of the examples have been the use of nanoparticles in the field of opto-electronic, fuel cells, medicine and catalysis. These wide applications and significance lies in the fact that nanoparticles possess unique physical and chemical properties very different from their bulk precursors. Numerous methods for the synthesis of noble nanoparticles with tunable shape and size have been reported in literature. The goal of our group is to use different methods of synthesis of noble metal nanoparticles (Au, Ag, Pt and Pd) and test their protective/damaging role towards DNA base damage induced by ionizing radiation (Au and Ag) and to test the catalytic activity of nanoparticles (Pt and Pd) in certain known organic synthesis/electron transfer reactions. Using radiation chemical techniques such as pulse radiolysis and steady state radiolysis complemented by the product analysis using HPLC/LC-MS, a detailed mechanism for the formation of transient species, kinetics leading to the formation of stable end products is studied in the DNA base damage induced by ionizing radiation in presence and absence of Au and Ag nanoparticles. Unraveling the complex interaction between catalysts and reactants under operando conditions is a key step towards gaining fundamental insight in catalysis. The catalytic activity of Pt and Pd nanoparticles in electron transfer and Suzuki coupling reactions has been determined. Investigations are currently underway to gain insight into the interaction between catalysts and reactants using time resolved spectroscopic measurements. These studies will be detailed during the presentation. (author)

One parameter model potential for noble metals

International Nuclear Information System (INIS)

Idrees, M.; Khwaja, F.A.; Razmi, M.S.K.

1981-08-01

A phenomenological one parameter model potential which includes s-d hybridization and core-core exchange contributions is proposed for noble metals. A number of interesting properties like liquid metal resistivities, band gaps, thermoelectric powers and ion-ion interaction potentials are calculated for Cu, Ag and Au. The results obtained are in better agreement with experiment than the ones predicted by the other model potentials in the literature. (author)

New technique for the determination of trace noble metal content in geological and process materials

Energy Technology Data Exchange (ETDEWEB)

Mitkin, V.N. E-mail: mit@che.nsk.su; Zayakina, S.B.; Anoshin, G.N

2003-02-03

A new two-step sample preparation technique is proposed for the instrumental determination of trace quantities of noble metals (NM) in refractory geological and process materials. The decomposition procedure is based on the oxidizing fluorination of samples with subsequent sulfatization (OFS) of the sample melt or cake. Fluorination of samples is accomplished using a mixture of KHF{sub 2}+KBrF{sub 4} or KHF{sub 2}+BrF{sub 3} depending on the ratio of sample mass to oxidizing mixture. Both cakes and melts can result using this procedure. Sulfatization of resulting fluorides is completed using concentrated sulfuric acid heated to 550 deg. C. Validation studies using certified geostandard reference materials (GSO VP-2, ZH-3, Matte RTP, HO-1, SARM-7) have shown that the proposed method is fast, convenient and most often produces non-hygroscopic homogeneous residues suitable for analysis by atomic absorption spectrometry (AAS) and atomic emission spectrometry (AES). Results obtained for NM concentrations in reference materials agreed with certified concentration ranges and results obtained using other methods of analysis. The OFS procedure combined with direct current plasma d.c. plasma AES achieved the following limits of detection (LOD) for the noble metals: Ag, Au, Pd, 1-2x10{sup -6}; Pt, 5x10{sup -6}; and Ru, Rh, Ir, Os, 1-3x10{sup -7} wt.%. Using graphite furnace AAS (GFAAS) combined extraction pre-concentration the following LODs for NMs were achieved: Pt, Ru, 1x10{sup -6}; Pd, Rh, 1x10{sup -7}; and Au, Ag, 1-2x10{sup -8} wt.%. The relative standard deviation for NM determinations (S{sub r}) was dependent on NM concentration and sample type, but commonly was in the range of 3-15% for d.c. plasma AES and 5-30% for GFAAS.

Methanol and ethanol electrooxidation on Pt and Pd supported on carbon microspheres in alkaline media

Energy Technology Data Exchange (ETDEWEB)

Xu, Changwei; Cheng, Liqiang; Liu, Yingliang [Department of Chemistry and Institute of Nanochemistry, Jinan University, Guangzhou 510632 (China); Shen, Peikang [State Key Laboratory of Optoelectronic Materials and Technologies, School of Physics and Engineering, Sun Yat-Sen University, Guangzhou 510275 (China)

2007-05-15

Noble metal (Pt, Pd) electrocatalysts supported on carbon microspheres (CMS) are used for methanol and ethanol oxidation in alkaline media. The results show that noble metal electrocatalysts supported on carbon microspheres give better performance than that supported on carbon black. It is well known that palladium is not a good electrocatalyst for methanol oxidation, but it shows excellently higher activity and better steady-state electrolysis than Pt for ethanol electrooxidation in alkaline media. The results show a synergistic effect by the interaction between Pd and carbon microspheres. The Pd supported on carbon microspheres in this paper possesses excellent electrocatalytic properties and may be of great potential in direct ethanol fuel cells. (author)

Process for Making a Noble Metal on Tin Oxide Catalyst

Science.gov (United States)

Davis, Patricia; Miller, Irvin; Upchurch, Billy

2010-01-01

To produce a noble metal-on-metal oxide catalyst on an inert, high-surface-area support material (that functions as a catalyst at approximately room temperature using chloride-free reagents), for use in a carbon dioxide laser, requires two steps: First, a commercially available, inert, high-surface-area support material (silica spheres) is coated with a thin layer of metal oxide, a monolayer equivalent. Very beneficial results have been obtained using nitric acid as an oxidizing agent because it leaves no residue. It is also helpful if the spheres are first deaerated by boiling in water to allow the entire surface to be coated. A metal, such as tin, is then dissolved in the oxidizing agent/support material mixture to yield, in the case of tin, metastannic acid. Although tin has proven especially beneficial for use in a closed-cycle CO2 laser, in general any metal with two valence states, such as most transition metals and antimony, may be used. The metastannic acid will be adsorbed onto the high-surface-area spheres, coating them. Any excess oxidizing agent is then evaporated, and the resulting metastannic acid-coated spheres are dried and calcined, whereby the metastannic acid becomes tin(IV) oxide. The second step is accomplished by preparing an aqueous mixture of the tin(IV) oxide-coated spheres, and a soluble, chloride-free salt of at least one catalyst metal. The catalyst metal may be selected from the group consisting of platinum, palladium, ruthenium, gold, and rhodium, or other platinum group metals. Extremely beneficial results have been obtained using chloride-free salts of platinum, palladium, or a combination thereof, such as tetraammineplatinum (II) hydroxide ([Pt(NH3)4] (OH)2), or tetraammine palladium nitrate ([Pd(NH3)4](NO3)2).

The efficacy of noble metal alloy urinary catheters in reducing catheter-associated urinary tract infection

Directory of Open Access Journals (Sweden)

Alanood Ahmed Aljohi

2016-01-01

Results: A 90% relative risk reduction in the rate of CAUTI was observed with the noble metal alloy catheter compared to the standard catheter (10 vs. 1 cases, P = 0.006. When considering both catheter-associated asymptomatic bacteriuria and CAUTI, the relative risk reduction was 83% (12 vs. 2 cases, P = 0.005. In addition to CAUTI, the risk of acquiring secondary bacteremia was lower (100% for the patients using noble metal alloy catheters (3 cases in the standard group vs. 0 case in the noble metal alloy catheter group, P = 0.24. No adverse events related to any of the used catheters were recorded. Conclusion: Results from this study revealed that noble metal alloy catheters are safe to use and significantly reduce CAUTI rate in ICU patients after 3 days of use.

Solid polymer electrolyte composite membrane comprising a porous support and a solid polymer electrolyte including a dispersed reduced noble metal or noble metal oxide

Science.gov (United States)

Liu, Han; Mittelsteadt, Cortney K; Norman, Timothy J; Griffith, Arthur E; LaConti, Anthony B

2015-02-24

A solid polymer electrolyte composite membrane and method of manufacturing the same. According to one embodiment, the composite membrane comprises a thin, rigid, dimensionally-stable, non-electrically-conducting support, the support having a plurality of cylindrical, straight-through pores extending perpendicularly between opposing top and bottom surfaces of the support. The pores are unevenly distributed, with some or no pores located along the periphery and more pores located centrally. The pores are completely filled with a solid polymer electrolyte, the solid polymer electrolyte including a dispersed reduced noble metal or noble metal oxide. The solid polymer electrolyte may also be deposited over the top and/or bottom surfaces of the support.

Development of Non-Noble Metal Ni-Based Catalysts for Dehydrogenation of Methylcyclohexane

KAUST Repository

Shaikh Ali, Anaam

2016-01-01

to TOL has only been achieved using the noble Pt-based catalysts. The aim of this study is to develop non-noble, cost-effective metal catalysts that can show excellent catalytic performance, mainly maintaining high TOL selectivity achievable by Pt based

Grains of Nonferrous and Noble Metals in Iron-Manganese Formations and Igneous Rocks of Submarine Elevations of the Sea of Japan

Science.gov (United States)

Kolesnik, O. N.; Astakhova, N. V.

2018-01-01

Iron-manganese formations and igneous rocks of submarine elevations in the Sea of Japan contain overlapping mineral phases (grains) with quite identical morphology, localization, and chemical composition. Most of the grains conform to oxides, intermetallic compounds, native elements, sulfides, and sulfates in terms of the set of nonferrous, noble, and certain other metals (Cu, Zn, Sn, Pb, Ni, Mo, Ag, Pd, and Pt). The main conclusion that postvolcanic hydrothermal fluids are the key sources of metals is based upon a comparison of the data of electron microprobe analysis of iron-manganese formations and igneous rocks dredged at the same submarine elevations in the Sea of Japan.

Noble metal catalyzed aqueous phase hydrogenation and hydrodeoxygenation of lignin-derived pyrolysis oil and related model compounds.

Science.gov (United States)

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.

The preparation of primary standard solutions for each of the noble metals

International Nuclear Information System (INIS)

Mallett, R.C.; Wall, G.J.; Jones, E.A.; Royal, S.J.

1977-01-01

A revised method for the preparation of primary standard solutions for each of the noble metals is described. It is now recommended that standard noble-metal solutions should be made from the pure metals and not from salts as previously described. Metals should have a certified purity of 99,95 per cent or better, and the purity should be confirmed by analysis, the techniques of emission spectography or spark-source mass spectrography being used. After the metals have been dissolved, the solutions are made up to volume and the metal content of the standard solutions is checked. For most instrumental techniques for which the standards are intended, the check analysis should be within 0,3 per cent of the certified value

Preparation and Heat-Treatment of DWPF Simulants With and Without Co-Precipitated Noble Metals

International Nuclear Information System (INIS)

Koopman, David C.:Eibling, Russel E

2005-01-01

The Savannah River National Laboratory is in the process of investigating factors suspected of impacting catalytic hydrogen generation in the Chemical Process Cell of the Defense Waste Processing Facility, DWPF. Noble metal catalyzed hydrogen generation in simulation work constrains the allowable acid addition operating window in DWPF. This constraint potentially impacts washing strategies during sludge batch preparation. It can also influence decisions related to the addition of secondary waste streams to a sludge batch. Noble metals have historically been added as trim chemicals to process simulations. The present study investigated the potential conservatism that might be present from adding the catalytic species as trim chemicals to the final sludge simulant versus co-precipitating the noble metals into the insoluble sludge solids matrix. Parallel preparations of two sludge simulants targeting the composition of Sludge Batch 3 were performed in order to evaluate the impact of the form of noble metals. Identical steps were used except that one simulant had dissolved palladium, rhodium, and ruthenium present during the precipitation of the insoluble solids. Noble metals were trimmed into the other stimulant prior to process tests. Portions of both sludge simulants were held at 97 C for about eight hours to qualitatively simulate the effects of long term storage on particle morphology and speciation. The simulants were used as feeds for Sludge Receipt and Adjustment Tank, SRAT, process simulations. The following conclusions were drawn from the simulant preparation work: (1) The first preparation of a waste slurry simulant with co-precipitated noble metals was successful, based on the data obtained. It appears that 99+% of the noble metals were retained in the simulant. (2) Better control of carbonate, hydroxide, and post-wash trim chemical additions is needed before the new method of simulant preparation will be as reproducible as the old method. (3) The two new

Lamellar zirconium phosphates to host metals for catalytic purposes.

Science.gov (United States)

Ballesteros-Plata, Daniel; Infantes-Molina, Antonia; Rodríguez-Aguado, Elena; Braos-García, Pilar; Rodríguez-Castellón, Enrique

2018-02-27

In the present study a porous lamellar zirconium phosphate heterostructure (PPH) formed from zirconium(iv) phosphate expanded with silica galleries (P/Zr molar ratio equal to 2 and (Si + Zr)/P equal to 3) was prepared to host noble metals. Textural and structural characterization of PPH-noble metal materials was carried out in order to elucidate the location and dispersion of the metallic particles and the properties of the resulting material to be used in catalytic processes. In the present paper, their activity in the catalytic hydrodeoxygenation (HDO) reaction of dibenzofuran (DBF) was evaluated. X-ray diffraction (XRD), solid state nuclear magnetic resonance (NMR) and X-ray photoelectron spectroscopy (XPS) evidenced that the structure of the pillared zirconium phosphate material was not modified by the incorporation of Pt and Pd. Moreover, transmission electron microscopy (TEM) showed a different dispersion of the noble metal. The acidity of the resulting PPH-noble metal materials also changed, although in all cases the acidity was of weak nature, and the incorporation of noble metals affected Brønsted acid sites as observed from 31 P NMR spectra. In general, the textural, structural and acidic properties of the resulting materials suggest that PPH can be considered a good candidate to be used as a catalytic support. Thus, the catalytic results of the PPH-noble metal samples indicated that the Pd sample showed a stable behavior probably ascribed to a high dispersion of the active phase. However, the Pt sample suffered from fast deactivation. The selectivity to the reaction products was strongly dependent on the noble metal employed.

Electrospun Polymer Nanofibers Decorated with Noble Metal Nanoparticles for Chemical Sensing.

Science.gov (United States)

Chen, Chen; Tang, Yongan; Vlahovic, Branislav; Yan, Fei

2017-12-01

The integration of different noble metal nanostructures, which exhibit desirable plasmonic and/or electrocatalytic properties, with electrospun polymer nanofibers, which display unique mechanical and thermodynamic properties, yields novel hybrid nanoscale systems of synergistic properties and functions. This review summarizes recent advances on how to incorporate noble metal nanoparticles into electrospun polymer nanofibers and illustrates how such integration paves the way towards chemical sensing applications with improved sensitivity, stability, flexibility, compatibility, and selectivity. It is expected that further development of this field will eventually make a wide impact on many areas of research.

The Behavior and Effects of the Noble Metals in the DWPF Melter System

International Nuclear Information System (INIS)

Smith, M.E.; Bickford, D.F.

1997-01-01

Governments worldwide have committed to stabilization of high-level nuclear waste (HLW) by vitrification to a durable glass form for permanent disposal. All of these nuclear wastes contain the fission-product noble metals: ruthenium, rhodium, and palladium. SRS wastes also contain natural silver from iodine scrubbers. Closely associated with the noble metals are the fission products selenium and tellurium which are chemical analogs of sulfur and which combine with noble metals to influence their behavior and properties. Experience has shown that these melt insoluble metals and their compounds tend to settle to the floor of Joule-heated ceramic melters. In fact, almost all of the major research and production facilities have experienced some operational problem which can be associated with the presence of dense accumulations of these relatively conductive metals and/or their compounds. In most cases, these deposits have led to a loss of production capability, in some cases, to the point that melter operation could not continue. HLW nuclear waste vitrification facilities in the United States are the Department of Energy's Defense Waste Processing Facility (DWPF) at the Savannah River Site, the planned Hanford Waste Vitrification Plant (HWVP) at the Hanford Site and the operating West Valley Demonstration Project (WVDP) at West Valley, NY. The Integrated DWPF Melter System (IDMS) is a vitrification test facility at the Savannah River Technology Center (SRTC). It was designed and constructed to provide an engineering-scale representation of the DWPF melter and its associated feed preparation and off-gas treatment systems. An extensive noble metals testing program was begun in 1990. The objectives of this task were to explore the effects of the noble metals on the DWPF melter feed preparation and waste vitrification processes. This report focuses on the vitrification portion of the test program

Facile preparation of ZIF-8@Pd-CSS sandwich-type microspheres via in situ growth of ZIF-8 shells over Pd-loaded colloidal carbon spheres with aggregation-resistant and leach-proof properties for the Pd nanoparticles

Energy Technology Data Exchange (ETDEWEB)

Zhang, Tong; Lin, Lu [State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology, Dalian, 116024 (China); Zhang, Xiongfu, E-mail: xfzhang@dlut.edu.cn [State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology, Dalian, 116024 (China); Liu, Haiou; Yan, Xinjuan [State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology, Dalian, 116024 (China); Liu, Zhang; Yeung, King Lun [Department of Chemical and Biomolecular Engineering, Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong SAR (China)

2015-10-01

Graphical abstract: - Highlights: • Uniform-sized colloidal carbon spheres were synthesized from low-cost glucose. • Pd nanoparticles were loaded onto the carbon spheres via self-reduction method. • A layer of ZIF-8 shell was in situ grown over the Pd-loaded carbon spheres. • The ZIF-8@Pd-CCS showed leach-proof and aggregation-resistant properties of Pd. - Abstract: Aiming to enhance the stability of noble metal nanoparticles that are anchored on the surface of colloidal carbon spheres (CCSs), we designed and prepared a new kind of sandwich-structured ZIF-8@Pd-CCS microsphere. Typically, uniform CCSs were first synthesized by the aromatization and carbonization of glucose under hydrothermal conditions. Subsequently, noble metal nanoparticles, herein Pd nanoparticles, were attached to the surface of CCSs via self-reduction route, followed by in situ assembly of a thin layer of ZIF-8 over the Pd nanoparticles to form the sandwich-type ZIF-8@Pd-CCS microspheres. X-ray diffraction (XRD) patterns and Fourier transform infrared spectroscopy (FTIR) spectra confirmed the presence of crystalline ZIF-8, while TEM analysis revealed that the ZIF-8 shells were closely bound to the Pd-loaded CCSs. The shell thickness could be tuned by varying the ZIF-8 assembly cycles. Further, liquid-phase hydrogenation of 1-hexene as the probe reaction was carried out over the ZIF-8@Pd-CCS microspheres and results showed that the prepared microspheres exhibited excellent agglomeration-resistant and leach-proof properties for the Pd nanoparticles, thus leading to the good reusability of the ZIF-8@Pd-CCS microspheres.

Modeling impurity-assisted chain creation in noble-metal break junctions

International Nuclear Information System (INIS)

Di Napoli, S; Thiess, A; Blügel, S; Mokrousov, Y

2012-01-01

In this work we present the generalization of the model for chain formation in break junctions, introduced by Thiess et al (2008 Nano Lett. 8 2144), to zigzag transition-metal chains with s and p impurities. We apply this extended model to study the producibility trends for noble-metal chains with impurities, often present in break junction experiments, namely, Cu, Ag and Au chains with H, C, O and N adatoms. Providing the material-specific parameters for our model from systematic full-potential linearized augmented plane-wave first-principles calculations, we find that the presence of such impurities crucially affects the binding properties of the noble-metal chains. We reveal that both the impurity-induced bond strengthening and the formation of zigzag bonds can lead to a significantly enhanced probability for chain formation in break junctions. (paper)

Rational design of binder-free noble metal/metal oxide arrays with nanocauliflower structure for wide linear range nonenzymatic glucose detection

KAUST Repository

Li, Zhenzhen

2015-06-12

One-dimensional nanocomposites of metal-oxide and noble metal were expected to present superior performance for nonenzymatic glucose detection due to its good conductivity and high catalytic activity inherited from noble metal and metal oxide respectively. As a proof of concept, we synthesized gold and copper oxide (Au/CuO) composite with unique one-dimensional nanocauliflowers structure. Due to the nature of the synthesis method, no any foreign binder was needed in keeping either Au or CuO in place. To the best of our knowledge, this is the first attempt in combining metal oxide and noble metal in a binder-free style for fabricating nonenzymatic glucose sensor. The Au/CuO nanocauliflowers with large electrochemical active surface and high electrolyte contact area would promise a wide linear range and high sensitive detection of glucose with good stability and reproducibility due to its good electrical conductivity of Au and high electrocatalytic activity of CuO.

Monometallic Pd and Pt and Bimetallic Pd-Pt/Al2O3-TiO2 for the HDS of DBT: Effect of the Pd and Pt Incorporation Method

Directory of Open Access Journals (Sweden)

Reynaldo Martínez Guerrero

2014-01-01

Full Text Available The effect of the preparation method of monometallic Pd and Pt and bimetallic Pd-Pt/Al2O3-TiO2 catalysts on the hydrodesulfurization (HDS of dibenzothiophene (DBT was investigated in this study. The synthesis was accomplished using three methods: (A impregnation, (B metal organic chemical vapor deposition (MOCVD, and (C impregnation-MOCVD. The bimetallic Pd-Pt catalyst prepared by the impregnation-MOCVD method was most active for the HDS of DBT compared to those prepared by the single impregnation or MOCVD method due to the synergetic effect between both noble metals. The greater selectivity toward biphenyl indicated that this bimetallic Pd-Pt catalyst preferentially removes sulfur via the direct desulfurization mechanism. However, the bimetallic Pd-Pt catalyst prepared using the single MOCVD method did not produce any cyclohexylbenzene, which is most likely associated with the hydrogenation/dehydrogenation sites.

Nanoparticles of noble metals in the supergene zone

Science.gov (United States)

Zhmodik, S. M.; Kalinin, Yu. A.; Roslyakov, N. A.; Mironov, A. G.; Mikhlin, Yu. L.; Belyanin, D. K.; Nemirovskaya, N. A.; Spiridonov, A. M.; Nesterenko, G. V.; Airiyants, E. V.; Moroz, T. N.; Bul'bak, T. A.

2012-04-01

Formation of noble metal nanoparticles is related to various geological processes in the supergene zone. Dispersed mineral phases appear during weathering of rocks with active participation of microorganisms, formation of soil, in aqueous medium and atmosphere. Invisible gold and other noble metals are incorporated into oxides, hydroxides, and sulfides, as well as in dispersed organic and inorganic carbonic matter. Sulfide minerals that occur in bedrocks and ores unaltered by exogenic processes and in cementation zone are among the main concentrators of noble metal nanoparticles. The ability of gold particles to disaggregate is well-known and creates problems in technological and analytical practice. When Au and PGE nanoparticles and clusters occur, these problems are augmented because of their unusual reactions and physicochemical properties. The studied gold, magnetite, titanomagnetite and pyrite microspherules from cementation zone and clay minerals of laterites in Republic of Guinea widen the knowledge of their abundance and inferred formation conditions, in particular, in the contemporary supergene zone. Morphology and composition of micrometer-sized Au mineral spherules were studied with SEM and laser microprobe. The newly formed segregations of secondary gold on the surface of its residual grains were also an object of investigation. The character of such overgrowths is the most indicative for nanoparticles. The newly formed Au particles provide evidence for redistribution of ultradispersed gold during weathering. There are serious prerequisites to state that microorganisms substantially control unusual nano-sized microspherical morphology of gold particles in the supergene zone. This is supported by experiments indicating active absorption of gold by microorganisms and direct evidence for participation of Ralstonia metallidurans bacteria in the formation of peculiar corroded bacteriomorphic surface of gold grains. In addition, the areas enriched in carbon

Wire gauze and cordierite supported noble metal catalysts for passive autocatalytic recombiner

International Nuclear Information System (INIS)

Sanap, Kiran K.; Varma, S.; Waghmode, S.B.; Bharadwaj, S.R.

2015-01-01

Highlights: • Synthesis by electroless deposition method and chemical reduction route. • Particle size of 0.1–0.5 μm & 3.5–5 nm for Pt–Pd/Wg & Pt–Pd/Cord catalysts. • Active for H_2 and O_2 reaction with initial H_2 concentration of 1.5 to 7% in air. • Active in presence of different contaminants like CO_2, CH_4, CO & relative humidity. • Enhanced resistance of Pt–Pd/Cord catalyst towards the poisoning of CO. - Abstract: Hydrogen released in nuclear reactor containment under severe accident scenario poses a threat to containment and hence needs to be regulated by catalytic recombination. Mixed noble metal catalysts with platinum–palladium supported on stainless steel wire gauze and cordierite support have been developed for this purpose. The developed catalysts have been found to be highly efficient for removal of hydrogen concentration in the range of 1.5 to 7.0% v/v in air. Though both the catalysts exhibit similar kinetics for lower hydrogen concentration, cordierite supported catalysts exhibits better kinetic rate at higher hydrogen concentration. The performances of these catalysts in presence of various probable catalytic poison like carbon monoxide and catalytic inhibitors like moisture, carbon dioxide, and hydrocarbons provide data for use of these catalysts under the actual scenario. Compared to stainless steel wire gauze supported catalyst, the cordierite based catalyst are found to exhibit enhanced resistance towards carbon monoxide and limited temperature rise for safer application at higher hydrogen concentrations.

The Role of Noble Metal Addition Methods on BWR Shut Down Dose Rates

International Nuclear Information System (INIS)

Cowan, Robert L.; Garcia Susan, E.

2012-09-01

Noble metal addition technology was developed for the BWR as a means of establishing low electrochemical corrosion potentials (ECP) on structural materials to mitigate intergranular stress corrosion cracking (IGSCC). When the reactor water molar ratio of H 2 / (O 2 +H 2 O 2 ) is > 2 on noble metal treated surfaces, the resulting ECP is near -500 mV (SHE), well into the mitigation range. This ratio can be achieved in most areas of the reactor with feedwater hydrogen additions in the range of 0.2 mg/kg, a condition that does not increase the radiation level in the main steam, a side effect of conventional hydrogen water chemistry (HWC). The resulting low ECP on the surface of stainless steel piping and components results in a change in form of the stable corrosion film to a spinel structure. Since it is the 60 Co incorporated into the corrosion film that is the primary source term of shutdown dose rates in BWRs, the structure and composition of the film can have a large influence in the resulting dose rates. The results of the first generation of noble metal technology, noble metal chemical addition (NMCA), showed that the reactor water ratio of 60 Co (s)/Zn (s) was a key parameter in determining shut down dose rate values. This paper will review that history and provide mechanistic understanding of how initial post NMCA dose rates are established and change with time. On-line noble metal chemical addition (OLNC) is the second generation of noble metal technology. The method utilizes the on-line injection of dilute Na 2 Pt (OH) 6 into the feedwater over a period of approximately 10 days. The first application of OLNC occurred at a European reactor in July of 2005 and to date over 20 BWRs have applied the technology, with many more applications scheduled. It is expected that OLNC will become the de facto standard because it eliminates 60 hours of outage application time and it addresses the crack flanking concerns that can arise under certain conditions. Because both

Noble metal catalyzed hydrogen generation from formic acid in nitrite-containing simulated nuclear waste media

International Nuclear Information System (INIS)

King, R.B.; Bhattacharyya, N.K.; Wiemers, K.D.

1994-08-01

Simulants for the Hanford Waste Vitrification Plant (HWVP) feed containing the major non-radioactive components Al, Cd, Fe, Mn, Nd, Ni, Si, Zr, Na, CO 3 2- , NO 3 -, and NO 2 - were used as media to evaluate the stability of formic acid towards hydrogen evolution by the reaction HCO 2 H → H 2 + CO 2 catalyzed by the noble metals Ru, Rh, and/or Pd found in significant quantities in uranium fission products. Small scale experiments using 40-50 mL of feed simulant in closed glass reactors (250-550 mL total volume) at 80-100 degree C were used to study the effect of nitrite and nitrate ion on the catalytic activities of the noble metals for formic acid decomposition. Reactions were monitored using gas chromatography to analyze the CO 2 , H 2 , NO, and N 2 O in the gas phase as a function of time. Rhodium, which was introduced as soluble RhCl 3 ·3H 2 O, was found to be the most active catalyst for hydrogen generation from formic acid above ∼80 degree C in the presence of nitrite ion in accord with earlier observations. The inherent homogeneous nature of the nitrite-promoted Rh-catalyzed formic acid decomposition is suggested by the approximate pseudo first-order dependence of the hydrogen production rate on Rh concentration. Titration of the typical feed simulants containing carbonate and nitrite with formic acid in the presence of rhodium at the reaction temperature (∼90 degree C) indicates that the nitrite-promoted Rh-catalyzed decomposition of formic acid occurs only after formic acid has reacted with all of the carbonate and nitrite present to form CO 2 and NO/N 2 O, respectively. The catalytic activities of Ru and Pd towards hydrogen generation from formic acid are quite different than those of Rh in that they are inhibited rather than promoted by the presence of nitrite ion

Non-noble metal based electro-catalyst compositions for proton exchange membrane based water electrolysis and methods of making

Science.gov (United States)

Kumta, Prashant N.; Kadakia, Karan Sandeep; Datta, Moni Kanchan; Velikokhatnyi, Oleg

2017-02-07

The invention provides electro-catalyst compositions for an anode electrode of a proton exchange membrane-based water electrolysis system. The compositions include a noble metal component selected from the group consisting of iridium oxide, ruthenium oxide, rhenium oxide and mixtures thereof, and a non-noble metal component selected from the group consisting of tantalum oxide, tin oxide, niobium oxide, titanium oxide, tungsten oxide, molybdenum oxide, yttrium oxide, scandium oxide, cooper oxide, zirconium oxide, nickel oxide and mixtures thereof. Further, the non-noble metal component can include a dopant. The dopant can be at least one element selected from Groups III, V, VI and VII of the Periodic Table. The compositions can be prepared using a surfactant approach or a sol gel approach. Further, the compositions are prepared using noble metal and non-noble metal precursors. Furthermore, a thin film containing the compositions can be deposited onto a substrate to form the anode electrode.

The role of noble metals in electric melting of nuclear waste glass

International Nuclear Information System (INIS)

Roth, G.; Weisenburger, S.

1990-01-01

Electrical melting of nuclear waste glass in ceramic melters applies Joule heating, with the molten glass acting as the conductive medium. The local energy release inside the melt relieves from the restriction of external heat addition, allowing to scale up the melter to industrial units. Certainly, that principle makes the melter operation susceptible for changes of the electrical properties of the glass melt. Hence, the melt properties are required to be locally uniform and constant with time. Temporary fluctuations in the feed composition, however, are usually attenuated by the high retention times being in the order of a day and more. More essential for the melter operation are segregation effects occurring systematically. This behaviour can be observed in the case of the so-called noble metal elements Ruthenium, Palladium and Rhodium, belonging to the Platinum metal group. The subject of this paper is to describe the behaviour of the noble metals in electric melting and the problems they can contribute to. The discussion is based on detailed knowledge gained from PAMELA's LEWC processing and from large-scale vitrification of commercial-like waste simulate at INE/KfK. Finally, ways are indicated to solve the noble metal problem technically

Graphene–Noble Metal Nano-Composites and Applications for Hydrogen Sensors

Directory of Open Access Journals (Sweden)

Sukumar Basu

2017-10-01

Full Text Available Graphene based nano-composites are relatively new materials with excellent mechanical, electrical, electronic and chemical properties for applications in the fields of electrical and electronic devices, mechanical appliances and chemical gadgets. For all these applications, the structural features associated with chemical bonding that involve other components at the interface need in-depth investigation. Metals, polymers, inorganic fibers and other components improve the properties of graphene when they form a kind of composite structure in the nano-dimensions. Intensive investigations have been carried out globally in this area of research and development. In this article, some salient features of graphene–noble metal interactions and composite formation which improve hydrogen gas sensing properties—like higher and fast response, quick recovery, cross sensitivity, repeatability and long term stability of the sensor devices—are presented. Mostly noble metals are effective for enhancing the sensing performance of the graphene–metal hybrid sensors, due to their superior catalytic activities. The experimental evidence for atomic bonding between metal nano-structures and graphene has been reported in the literature and it is theoretically verified by density functional theory (DFT. Multilayer graphene influences gas sensing performance via intercalation of metal and non-metal atoms through atomic bonding.

Neutron activation analysis for noble metals in matte leach residues

International Nuclear Information System (INIS)

Hart, R.J.

1978-01-01

The development of the neutron activation analysis technique as a method for rapid and precise determinations of platinum group metals in matte leach residues depends on obtaining a method for effecting complete and homogeneous sample dilution. A simple method for solid dilution of metal samples is outlined in this study, which provided a basis for the accurate determination of all the noble metals by the Neutron Activation Analysis technique

Deposition and characterization of noble metal onto surfaces of 304l stainless steel

International Nuclear Information System (INIS)

Contreras R, A.; Arganis J, C. R.; Aguilar T, J. A.; Medina A, A. L.

2010-10-01

Noble metal chemical addition (NMCA) plus hydrogen water chemistry is an industry-wide accepted approach for potential intergranular stress corrosion cracking mitigation of BWR internals components. NMCA is a method of applying noble metal onto BWR internals surfaces using reactor water as the transport medium that causes the deposition of noble metal from the liquid onto surfaces. In this work different platinum concentration solutions were deposited onto pre-oxidized surfaces of 304l steel at 180 C during 48 hr in an autoclave. In order to simulate the zinc water conditions, deposits of Zn and Pt-Zn were also carried out. The solutions used to obtain the deposits were: sodium hexahydroxyplatinate (IV), zinc nitrate hydrate and zinc oxide. The deposits obtained were characterized by scanning electron microscopy and X-ray diffraction. Finally, the electrochemical corrosion potential of pre-oxidized samples with Pt deposit were obtained and compared with the electrochemical corrosion potential of only pre-oxidized samples. (Author)

Biomimetic Synthesis of Gelatin Polypeptide-Assisted Noble-Metal Nanoparticles and Their Interaction Study

Science.gov (United States)

Liu, Ying; Liu, Xiaoheng; Wang, Xin

2011-12-01

Herein, the generation of gold, silver, and silver-gold (Ag-Au) bimetallic nanoparticles was carried out in collagen (gelatin) solution. It first showed that the major ingredient in gelatin polypeptide, glutamic acid, acted as reducing agent to biomimetically synthesize noble metal nanoparticles at 80°C. The size of nanoparticles can be controlled not only by the mass ratio of gelatin to gold ion but also by pH of gelatin solution. Interaction between noble-metal nanoparticles and polypeptide has been investigated by TEM, UV-visible, fluorescence spectroscopy, and HNMR. This study testified that the degradation of gelatin protein could not alter the morphology of nanoparticles, but it made nanoparticles aggregated clusters array (opposing three-dimensional α-helix folding structure) into isolated nanoparticles stabilized by gelatin residues. This is a promising merit of gelatin to apply in the synthesis of nanoparticles. Therefore, gelatin protein is an excellent template for biomimetic synthesis of noble metal/bimetallic nanoparticle growth to form nanometer-sized device.

TiO2 structures doped with noble metals and/or graphene oxide to improve the photocatalytic degradation of dichloroacetic acid.

Science.gov (United States)

Ribao, Paula; Rivero, Maria J; Ortiz, Inmaculada

2017-05-01

Noble metals have been used to improve the photocatalytic activity of TiO 2 . Noble metal nanoparticles prevent charge recombination, facilitating electron transport due to the equilibration of the Fermi levels. Furthermore, noble metal nanoparticles show an absorption band in the visible region due to a high localized surface plasmon resonance (LSPR) effect, which contributes to additional electron movements. Moreover, systems based on graphene, titanium dioxide, and noble metals have been used, considering that graphene sheets can carry charges, thereby reducing electron-hole recombination, and can be used as substrates of atomic thickness. In this work, TiO 2 -based nanocomposites were prepared by blending TiO 2 with noble metals (Pt and Ag) and/or graphene oxide (GO). The nanocomposites were mainly characterized via transmission electron microscopy (TEM), X-ray diffraction (XRD), Fourier transformed infrared (FTIR), Raman spectroscopy, and photocurrent analysis. Here, the photocatalytic performance of the composites was analyzed via oxidizing dichloroacetic acid (DCA) model solutions. The influence of the noble metal load on the composite and the ability of the graphene sheets to improve the photocatalytic activity were studied, and the composites doped with different noble metals were compared. The results indicated that the platinum structures show the best photocatalytic degradation, and, although the presence of graphene oxide in the composites is supposed to enhance their photocatalytic performance, graphene oxide does not always improve the photocatalytic process. Graphical abstract It is a schematic diagram. Where NM is Noble Metal and LSPR means Localized Surface Plasmon Resonance.

Optical Properties and Immunoassay Applications of Noble Metal Nanoparticles

International Nuclear Information System (INIS)

Zhu, S.; Zhou, W.

2010-01-01

Noble metal, especially gold (Au) and silver (Ag) nanoparticles exhibit unique and tunable optical properties on account of their surface plasmon resonance (SPR). In this paper, we mainly discussed the theory background of the enhanced optical properties of noble metal nanoparticles. Mie theory, transfer matrix method, discrete dipole approximation (DDA) method, and finite-difference time domain (FDTD) method applied brute-force computational methods for different nanoparticles optical properties. Some important nanostructure fabrication technologies such as nanosphere lithography (NSL) and focused ion beam (FIB) are also introduced in this paper. Moreover, these fabricated nanostructures are used in the plasmonic sensing fields. The binding signal between the antibody and antigen, amyloid-derived diffusible ligands (ADDLs)-potential Alzheimer's disease (AD) biomarkers, and staphylococcal enterotoxin B (SEB) in nano-Moore per liter (nM) concentration level are detected by our designed nanobiosensor. They have many potential applications in the biosensor, environment protection, food security, and medicine safety for health, and so forth, fields.

Optical Properties and Immunoassay Applications of Noble Metal Nanoparticles

Directory of Open Access Journals (Sweden)

Shaoli Zhu

2010-01-01

Full Text Available Noble metal, especially gold (Au and silver (Ag nanoparticles exhibit unique and tunable optical properties on account of their surface plasmon resonance (SPR. In this paper, we mainly discussed the theory background of the enhanced optical properties of noble metal nanoparticles. Mie theory, transfer matrix method, discrete dipole approximation (DDA method, and finite-difference time domain (FDTD method applied brute-force computational methods for different nanoparticles optical properties. Some important nanostructure fabrication technologies such as nanosphere lithography (NSL and focused ion beam (FIB are also introduced in this paper. Moreover, these fabricated nanostructures are used in the plasmonic sensing fields. The binding signal between the antibody and antigen, amyloid-derived diffusible ligands (ADDLs-potential Alzheimer's disease (AD biomarkers, and staphylococcal enterotixn B (SEB in nano-Moore per liter (nM concentration level are detected by our designed nanobiosensor. They have many potential applications in the biosensor, environment protection, food security, and medicine safety for health, and so forth, fields.

Non-noble metal fuel cell catalysts

CERN Document Server

Chen, Zhongwei; Zhang, Jiujun

2014-01-01

Written and edited by a group of top scientists and engineers in the field of fuel cell catalysts from both industry and academia, this book provides a complete overview of this hot topic. It covers the synthesis, characterization, activity validation and modeling of different non-noble metal and metalfree electrocatalysts for the reduction of oxygen, as well as their integration into acid or alkaline polymer exchange membrane (PEM) fuel cells and their performance validation, while also discussing those factors that will drive fuel cell commercialization. With its well-structured app

ALTERNATIVE MATERIALS TO PD MEMBRANES FOR HYDROGEN PURIFICATION

Energy Technology Data Exchange (ETDEWEB)

Korinko, P; T. Adams

2008-09-12

Development of advanced hydrogen separation membranes in support of hydrogen production processes such as coal gasification and as front end gas purifiers for fuel cell based system is paramount to the successful implementation of a national hydrogen economy. Current generation metallic hydrogen separation membranes are based on Pd-alloys. Although the technology has proven successful, at issue is the high cost of palladium. Evaluation of non-noble metal based dense metallic separation membranes is currently receiving national and international attention. The focal point of the reported work was to evaluate two different classes of materials for potential replacement of conventional Pd-alloy purification/diffuser membranes. Crystalline V-Ni-Ti and Amorphous Fe- and Co-based metallic glass alloys have been evaluated using gaseous hydrogen permeation testing techniques.

Solvent extraction of noble metals by formazans

International Nuclear Information System (INIS)

Grote, M.; Hueppe, U.; Kettrup, A.

1984-01-01

The extraction properties of ion-pairs composed of quaternary ammonium cations and a sulphonated formazan were compared with those of an unsulphonated formazan, for various solvent media. In dichloromethane the combined system behaves as a 'coloured anion-exchanger', with displacement of the sulphonated formazan, whereas in toluene Pd(II) and Ag(I) are extracted as the metal formazan chelates from aqueous medium. The rates of extraction are remarkably higher than with the simple extractants. Because of the higher stability only the simple chelating extraction systems afford satisfactory separation of Pd(II) from excess of Pt(IV) and of Ag(I) from Cu(II). The extracted metals can be stripped and the extractant regenerated. (author)

Characterisation and radiolysis of modified lithium orthosilicate pebbles with noble metal impurities

DEFF Research Database (Denmark)

Tamulevičius, Sigitas; Zariņš, A.; Valtenbergs, O.

2017-01-01

Modified lithium orthosilicate (Li4SiO4) pebbles with additions of titanium dioxide (TiO2) are suggested as an alternative tritium breeding ceramic for the European solid breeder test blanket module. The noble metals – platinum (Pt), gold (Au) and rhodium (Rh), can be introduced into the modified...... Li4SiO4 pebbles during the melt-based process, due to the corrosion of Pt-Rh and Pt-Au alloy crucible components. In this study, the surface microstructure, chemical and phase composition of the modified Li4SiO4 pebbles with different contents of the noble metals was analysed. The influence...

Flameless atomic absorption determination of noble metals after extraction by mixture of di-2-ethylhexyldithiophosphoric acid and n-octylaniline

International Nuclear Information System (INIS)

Yukhin, Yu.M.; Udalova, T.A.; Tsimbalist, V.G.; AN SSSR, Novosibirsk. Inst. Geologii i Geofiziki)

1985-01-01

A possibility of using the mixture of di-2-ethylhexyl dithiophosphoric acid (D2EHDTPA) and p-octylaniline (OA) (extractants of acid and basic character) for extraction atomic absorption determination of noble metals is studied. The mixture of D2EHDTPA with OA is shown to extract noble metals from hydrochloric acid solutions with distribution factors > 10 3 . An extraction atomic absorption method for determination of noble metals in copperbearing materials is suggested. The minimum determined contents of noble metals at the initial sample equal to 100 for gold, silver, platinum, palladium, rhodium and ruthenium make up (g/t) 0.0005, 0.0001, 0.015, 0.005, 0.002 and 0.015 respectively. Relative standard deviation constitutes Ssub(r)<0.2

Effect of noble metals on the corrosion of AISI 316L stainless steel in nitric acid

International Nuclear Information System (INIS)

Robin, R.; Andreoletti, G.; Fauvet, P.; Terlain, A.

2004-01-01

In the spent fuel treatment, the solutions of fission products contain dissolution fines, in particular platinoids. These solutions are stored into AISI 316L stainless steel tanks, and the contact of noble metallic particles such as platinoids with austenitic stainless steels may induce a shift of the steel corrosion potential towards the trans-passive domain by galvanic coupling. In that case, the steel may be polarized up to a potential value above the range of passive domain, that induces an increase of the corrosion current. The galvanic corrosion of AISI 316L stainless steel in contact with different platinoids has been investigated by electrochemical and gravimetric techniques. Two types of tests were conducted in 1 mol/L nitric acid media at 80 deg C: (1) polarization curves and (2) immersion tests with either platinoid powders (Ru, Rh, Pd) or true insoluble dissolution fines (radioactive laboratory test). The results of the study have shown that even if galvanic coupling enhances the corrosion rate by about a factor 10 in these conditions, the corrosion behavior of AISI 316L remains low (a corrosion rate below 6 μm/year, few small intergranular indentations). No specific effect of irradiation and of elements contained in radioactive fines (other than Ru, Rh and Pd) was observed on corrosion behavior. A platinoids-ranking has also been established according to their coupling potential: Ru > Pd > Rh. (authors)

Defense by-products production and utilization program: noble metal recovery screening experiments

International Nuclear Information System (INIS)

Hazelton, R.F.; Jensen, G.A.; Raney, P.J.

1986-03-01

Isotopes of the platinum metals (rutheium, rhodium, and palladium) are produced during uranium fuel fission in nuclear reactors. The strategic values of these noble metals warrant considering their recovery from spent fuel should the spent fuel be processed after reactor discharge. A program to evaluate methods for ruthenium, rhodium, and palladium recovery from spent fuel reprocessing liquids was conducted at Pacific Northwest Laboratory (PNL). The purpose of the work reported in this docuent was to evaluate several recovery processes revealed in the patent and technical literature. Beaker-scale screening tests were initiated for three potential recovery processes: precipitation during sugar denitration of nitric acid reprocessing solutions after plutonium-uranium solvent extraction, adsorption using nobe metal selective chelates on active carbon, and reduction forming solid noble metal deposits on an amine-borane reductive resin. Simulated reprocessing plant solutions representing typical nitric acid liquids from defense (PUREX) or commercial fuel reprocessing facilities were formulated and used for evaluation of the three processes. 9 refs., 3 figs., 9 tabs

Modification of titanium electrodes by a noble metal deposit

Energy Technology Data Exchange (ETDEWEB)

Devilliers, D.; Mahe, E. [Pierre et Marie Curie Univ., Paris (France). Laboratoire LI2C, UMR CNRS

2008-07-01

Titanium is commonly used as a substrate for dimensionally stable anodes (DSAs) because it is corrosion-resistant in acid media and because a passive titanium oxide (TiO2) film can be formed on the surface. This paper reported on a study in which titanium substrates were first covered by anodization with a TiO2 layer. The electrochemical properties of the Ti/TiO2 electrodes were investigated. The modification of the substrates by cathodic electrodeposition of a noble metal was described. The reactivity of the Ti/TiO2/Pt structures were illustrated by impedance spectroscopy experiments. The impedance studies performed with Ti/ TiO2 electrodes in the presence of a redox couple in solution (Fe3+/Fe2+ system in sulphuric acid) showed that the electronic transfer is very slow. It was concluded that the deposition of a noble metal coating on Ti/TiO2 substrates leads to modified titanium electrodes that exhibit electrocatalytic behaviour versus specific electrochemical reactions. 1 ref., 3 figs.

Development of supported noble metal catalyst for U(VI) to U(IV) reduction

International Nuclear Information System (INIS)

Tyagi, Deepak; Varma, Salil; Bhattacharyya, K.; Tripathi, A.K.; Bharadwaj, S.R.; Jain, V.K.; Sahu, Avinash; Vincent, Tessy; Jagatap, B.N.; Wattal, P.K.

2015-01-01

Uranium-plutonium separation is an essential step in the PUREX process employed in spent nuclear fuel reprocessing. This partitioning in the PUREX process is achieved by selective reduction of Pu(IV) to Pu(III) using uranous nitrate as reductant and hydrazine as stabilizer. Currently in our Indian reprocessing plants, the requirement of uranous nitrate is met by electrolytic reduction of uranyl nitrate. This process, however, suffers from a major drawback of incomplete reduction with a maximum conversion of ~ 60%. Catalytic reduction of U(VI) to U(IV) is being considered as one of the promising alternatives to the electro-reduction process due to fast kinetics and near total conversion. Various catalysts involving noble metals like platinum (Adams catalyst, Pt/Al 2 O 3 , Pt/SiO 2 etc.) have been reported for the reduction. Sustained activity and stability of the catalyst under harsh reaction conditions are still the issues that need to be resolved. We present here the results on zirconia supported noble metal catalyst that is developed in BARC for reduction of uranyl nitrate to uranous nitrate. Supported noble metal catalysts with varying metal loadings (0.5 - 2 wt%) were prepared via support precipitation and noble metal impregnation. The green catalysts were reduced either by chemical reduction using hydrazine hydrate or by heating in hydrogen flow or combination of both the steps. These catalysts were characterized by various techniques such as, XRD, SEM, TEM, N 2 adsorption and H 2 chemisorption. Performance of these catalysts was evaluated for U(VI) to U(IV) reduction with uranyl nitrate feed using hydrazine as reductant. The results with the most active catalyst are named as 'BARC-CAT', which was developed in our lab. (author)

Autoradiographic techniques to determine noble metal distribution in automotive catalyst substrates

International Nuclear Information System (INIS)

Lange, W.H.

1976-01-01

The distribution of noble metals in the ceramic substrates of automotive catalytic converter systems is important to the functional characteristics of the systems. A radiotracer technique involving microtomy of bead substrate samples and autoradiography using the resultant thin sections was developed to produce detailed images of the metal distributions. The method is particularly valuable to determine the distribution of one metal in the presence of another to aid in the development of more efficient systems

Noble metals in cretaceous/tertiary sediments from El Kef

International Nuclear Information System (INIS)

Kuslys, M.; Kraehenbuehl, U.

1983-01-01

Sediments from El Kef, Tunisia, were analysed by RNAA for Au, Ir and Os. All three elements show a 10-20 fold enrichment at the Cretaceous/Tertiary boundary. This enrichment must be the result of the addition of material with a high concentration of noble metals. It is plausible that this exotic material has an extra-terrestrial origin. (orig.)

Noble metals in Cretaceous/Tertiary sediments from El Kef

International Nuclear Information System (INIS)

Kuslys, M.; Kraehenbuehl, U.

1983-01-01

Sediments from El Kef, Tunisia, were analysed by RNAA for Au, Ir and Os. All three elements show a 10-20 fold enrichment at the Cretaceous/Tertiary boundary. This enrichment must be the result of the addition of material with a high concentration of noble metals. It is plausible that this exotic material has an extraterrestrial origin. (orig.)

Interaction between Nafion ionomer and noble metal catalyst for PEMFCs

DEFF Research Database (Denmark)

Andersen, Shuang Ma

The implement of polymer impregnation in electrode structure (catalyst layer) decreasing the noble metal catalyst loading by a factor of ten , , is one of the essential mile stones in the evolution of Proton Exchange Membrane Fuel Cells’ development among the application of catalyst support and e...

Dispersion forces and small-angle neutron scattering from liquid noble metals

International Nuclear Information System (INIS)

March, N.H.

1988-01-01

Maggs and Ashcroft [Phys. Rev. letts., 59,113 (1987)] have re-opened the question of the analogy between the cohesion of a molecular crystal, in which dispersion forces play a major role, and that in a metal crystal with polarizable ion cores. It is pointed out that small-angle neutron scattering from liquid noble metals could be used to test their predictions. (author)

Transparent and conductive electrodes by large-scale nano-structuring of noble metal thin-films

DEFF Research Database (Denmark)

Linnet, Jes; Runge Walther, Anders; Wolff, Christian

2018-01-01

grid, and nano-wire thin-films. The indium and carbon films do not match the chemical stability nor the electrical performance of the noble metals, and many metal films are not uniform in material distribution leading to significant surface roughness and randomized transmission haze. We demonstrate...... solution-processed masks for physical vapor-deposited metal electrodes consisting of hexagonally ordered aperture arrays with scalable aperture-size and spacing in an otherwise homogeneous noble metal thin-film that may exhibit better electrical performance than carbon nanotube-based thin-films...... for equivalent optical transparency. The fabricated electrodes are characterized optically and electrically by measuring transmittance and sheet resistance. The presented methods yield large-scale reproducible results. Experimentally realized thin-films with very low sheet resistance, Rsh = 2.01 ± 0.14 Ω...

Recovery of high-purity metallic Pd from Pd(II)-sorbed biosorbents by incineration.

Science.gov (United States)

Won, Sung Wook; Lim, Areum; Yun, Yeoung-Sang

2013-06-01

This work reports a direct way to recover metallic palladium with high purity from Pd(II)-sorbed polyethylenimine-modified Corynebacterium glutamicum biosorbent using a combined method of biosorption and incineration. This study is focused on the incineration part which affects the purity of recovered Pd. The incineration temperature and the amount of Pd loaded on the biosorbent were considered as major factors in the incineration process, and their effects were examined. The results showed that both factors significantly affected the enhancement of the recovery efficiency and purity of the recovered Pd. SEM-EDX and XRD analyses were used to confirm that Pd phase existed in the ash. As a result, the recovered Pd was changed from PdO to zero-valent Pd as the incineration temperature was increased from 600 to 900°C. Almost 100% pure metallic Pd was recovered with recovery efficiency above 99.0% under the conditions of 900°C and 136.9 mg/g. Copyright © 2013 Elsevier Ltd. All rights reserved.

Tuning the Morphology of Li2O2 by Noble and 3d metals: A Planar Model Electrode Study for Li-O2 Battery.

Science.gov (United States)

Yang, Yao; Liu, Wei; Wu, Nian; Wang, Xiaochen; Zhang, Tao; Chen, Linfeng; Zeng, Rui; Wang, Yingming; Lu, Juntao; Fu, Lei; Xiao, Li; Zhuang, Lin

2017-06-14

In this work, a planar model electrode method has been used to investigate the structure-activity relationship of multiple noble and 3d metal catalysts for the cathode reaction of Li-O 2 battery. The result shows that the battery performance (discharge/charge overpotential) strongly depends not only on the type of catalysts but also on the morphology of the discharge product (Li 2 O 2 ). Specifically, according to electrochemical characterization and scanning electron microscopy (SEM) observation, noble metals (Pd, Pt, Ru, Ir, and Au) show excellent battery performance (smaller discharge/charge overpotential), with wormlike Li 2 O 2 particles with size less than 200 nm on their surfaces. On the other hand, 3d metals (Fe, Co, Ni, and Mn) offered poor battery performance (larger discharge/charge overpotential), with much larger Li 2 O 2 particles (1 μm to a few microns) on their surfaces after discharging. Further research shows that a "volcano plot" is found by correlating the discharging/charging plateau voltage with the adsorption energy of LiO 2 on different metals. The metals with better battery performance and worm-like-shaped Li 2 O 2 are closer to the top of the "volcano", indicating adsorption energy of LiO 2 is one of the key characters for the catalyst to reach a good performance for the oxygen electrode of Li-O 2 battery, and it has a strong influence on the morphology of the discharge product on the electrode surface.

Electrical resistivity of noble-metal alloys: Roles of pseudopotential refinements

International Nuclear Information System (INIS)

Mujibar Rahman, S.M.

1983-08-01

The electrical resistivity of liquid noble-metal alloys i.e. CuAu and AgAu is calculated as a function of concentration. The calculations employ transition-metal-pseudopotentials that include nonlocal effects, hybridization and corrections due to orthogonalization hole and use the hard-sphere structure factors; the optimal values of the hard-sphere diameters are being determined by variational calculations. The calculated resistivities are comparable to the experimental values and to the available theoretical results. (author)

Photoemission studies of zinc-noble metal alloys: Zn--Cu, Zn--Ag, and Zn--Au films on Ru(001)

International Nuclear Information System (INIS)

Rodriguez, J.A.; Hrbek, J.

1993-01-01

Zn and the noble metals alloy when coadsorbed on Ru(001). The properties of Zn--Cu, Zn--Ag, and Zn--Au alloys have been studied using core- and valence-level photoemission and temperature programmed desorption. Alloy formation induces only small shifts (-0.2 to -0.3 eV) in the position of the Zn 2p, 3s, and 3d levels. In contrast, the core and valence levels of the noble metals show large shifts toward higher binding energy. For small amounts of Cu, Ag, and Au dissolved in Zn multilayers, the shifts in the core levels of the nobel metals follow the sequence: Cu(2p 3/2 ), 0.8 eV∼Ag(3d 5/2 ), 0.8 eV 7/2 ), 1.4 eV. The magnitude of the shift increases as the Pauling electronegativity of the noble metal increases. However, the sign of the shifts for the Cu(2p 3/2 ), Ag(3d 5/2 ), or Au(4f 7/2 ) levels is not directly determined by the direction of charge transfer within the corresponding Zn-noble metal bond

Transparent and conductive electrodes by large-scale nanostructuring of noble metal thin-films

DEFF Research Database (Denmark)

Linnet, Jes; Runge Walther, Anders; Wolff, Christian

grid, and nano-wire thin-films [1]. The indium and carbon films do not match the chemical stability nor the electrical performance of the noble metals, and many metal films are not uniform in material distribution leading to significant surface roughness and randomized transmission haze. We demonstrate...

Separation of the noble metals ruthenium and palladium from nitric acid solution of the nuclear fuel reprocessing containing complexing agents

International Nuclear Information System (INIS)

Ghafourian, H.

1989-06-01

Two extraction chromatographic techniques have been developed. N'N diethylthiourea (DETU), which forms complexes with ruthenium that can be retained on an AG50W-X2 ion exchanger, has proved to be a suitable reagent. The structures of these complexes were elucidated by electrophoresis, ion exchange and IR spectroscopy. Under the same conditions Pd forms an insoluble DETU-complex of the formula [Pd(DETU) 4 ] 2+ , which allows the separation of this metal quantitatively. With regard to the application of the developed technique for recovery of the mentioned noble metals from dissolver residues of the nuclear fuel reprocessing, comparative studies were carried out for accompanying fission product nuclides and actinides such as Mo, Tc, Zr, Ce, U and Pu. It was found out that no complex between diethylthiourea and the fission products zirconium, molybdenum and cerium and the actinides uranium, plutonium and americium were formed. Technetium, which was originally present as pertechnetate, is reduced to Tc(IV) and retained on the cation exchanger together with ruthenium. Ruthenium was eluted with 6 M HNO 3 . The efficiency of the developed process has been demonstrated with simulated solutions. The achieved decontamination factors ranged from 10 2 to 10 6 depending on the nuclide. (orig./RB) [de

Performance evaluation of a biodiesel fuelled transportation engine retrofitted with a non-noble metal catalysed diesel oxidation catalyst for controlling unregulated emissions.

Science.gov (United States)

Shukla, Pravesh Chandra; Gupta, Tarun; Agarwal, Avinash Kumar

2018-02-15

In present study, engine exhaust was sampled for measurement and analysis of unregulated emissions from a four cylinder transportation diesel engine using a state-of-the-art FTIR (Fourier transform infrared spectroscopy) emission analyzer. Test fuels used were Karanja biodiesel blend (B20) and baseline mineral diesel. Real-time emission measurements were performed for raw exhaust as well as exhaust sampled downstream of the two in-house prepared non-noble metal based diesel oxidation catalysts (DOCs) and a baseline commercial DOC based on noble metals. Two prepared non-noble metal based DOCs were based on Co-Ce mixed oxide and Lanthanum based perovskite catalysts. Perovskite based DOC performed superior compared to Co-Ce mixed oxide catalyst based DOC. Commercial noble metal based DOC was found to be the most effective in reducing unregulated hydrocarbon emissions in the engine exhaust, followed by the two in-house prepared non-noble metal based DOCs. Copyright © 2017 Elsevier B.V. All rights reserved.

Noble metals-compatible melter features development Phase 1: Establishing functional and design criteria and design concepts

International Nuclear Information System (INIS)

Elmore, M.R.; Siemens, D.H.; Chapman, C.C.

1996-03-01

Premature failures have occurred in melters at Japan's Tokai Mockup Facility and at the Federal Republic of Germany (FRG) PAMELA plant during processing of feeds with high levels of noble metals. Melter failure was due to the accumulation of an electrically conductive, noble metals-containing precipitates in the glass, that then resulted in short circuiting of the electrodes. A comparison was made of the anticipated Hanford Waste Vitrification Plant (HWVP) feed with the feeds processed in the FRG and Japanese melters. The evaluation showed that comparable levels of noble metals and other potential precipitate-forming components (e.g. Cr/Fe/Ni-spinels) exist in the HWVP feed. As a result, the HWVP project made a decision to modify the present reference melter design to include features to prevent the precipitation and accumulation or otherwise accommodate precipitated phases on a routine basis without loss of production capacity

Spectrochemical determination of impurities and noble metal traces in carnallite

International Nuclear Information System (INIS)

Goldbart, Z.; Carmi, U.; Harrel, A.

1978-02-01

A spectrochemical method was developed for the determination of impurities and noble metal traces in carnallite by DC arc excitation. The investigated sample is brought to a standard form of potassium-magnesium sulphate mixed with graphite. Detection limits of 1-10 ppm were determined for 27 elements; the dynamical detection range is 1-400 ppm

Nano-structured noble metal catalysts based on hexametallate architecture for the reforming of hydrocarbon fuels

Science.gov (United States)

Gardner, Todd H.

2015-09-15

Nano-structured noble metal catalysts based on hexametallate lattices, of a spinel block type, and which are resistant to carbon deposition and metal sulfide formation are provided. The catalysts are designed for the reforming of hydrocarbon fuels to synthesis gas. The hexametallate lattices are doped with noble metals (Au, Pt, Rh, Ru) which are atomically dispersed as isolated sites throughout the lattice and take the place of hexametallate metal ions such as Cr, Ga, In, and/or Nb. Mirror cations in the crystal lattice are selected from alkali metals, alkaline earth metals, and the lanthanide metals, so as to reduce the acidity of the catalyst crystal lattice and enhance the desorption of carbon deposit forming moieties such as aromatics. The catalysts can be used at temperatures as high as 1000.degree. C. and pressures up to 30 atmospheres. A method for producing these catalysts and applications of their use also is provided.

Oxidation of ethoxylated fatty alcohols to alkylpolyglycol carboxylic acids using noble metals as catalysts

Directory of Open Access Journals (Sweden)

Sagredos, Angelos

2009-09-01

Full Text Available The conversion of ethoxylated fatty alcohols to the corresponding carboxylic acids through dehydrogenation/ oxidation using noble-metal catalysts has been studied. Ethoxylated primary aliphatic alcohols, ethoxylated random secondary aliphatic alcohols and ethoxylated alkylphenols have been converted to the corresponding acids in the presence of a base. The noble metal catalysts Palladium and Platinum were used without significant degradation of the ethoxyl chain in yields that exceeded 90%. On the other hand, the catalysts Rhodium and Ruthenium gave yields of about 80% and 60% respectively.La conversión de alcoholes grasos etoxilados a los correspondientes ácidos carboxílicos por deshidrogenación/ oxidación con metales nobles como catalizador ha sido estudiada. Alcoholes primarios alifáticos etoxilados, alcoholes alifáticos secundarios etoxilados al azar y alquilfenoles etoxilados han sido convertidos a los correspondientes ácidos en presencia de base. Los catalizadores paladio y platino fueron usados sin degradación significativa de las cadenas etoxiladas con un rendimiento que excedió del 90%. Por otra parte catalizadores de rodio y rutenio produjeron rendimientos del 80 y 60%, respectivamente.

Application of noble metals on line in Cofrentes NPP and operation experience; Aplicacion de metales nobles en linea en C.N. Cofrentes y experiencia de operacion

Energy Technology Data Exchange (ETDEWEB)

Sanchez Zapata, J. D.

2015-07-01

Cofrentes NPP implemented in 2010 the Noble Metal Chemistry as a mitigation technique for the Primary System materials protection against IGSCC. the paper describes briefly the technology fundamentals, the implementation of the specific project, the initial application and the operating experience along the last 3 cycles of the plant. (Author)

Concentration of noble metals by sublimation during the analysis of massive samples

International Nuclear Information System (INIS)

Chuburkov, Yu.T.; Zhujkov, B.L.; Gehrbish, Sh.; Al'pert, L.K.; Chan Zuj Ty

1990-01-01

The possibility of concentrating noble metals from terrestrial samples of various composition by chemical sublimation in an air stream at a temperature of 1000-1200 deg C was examined. It was found that the chemical yields of Au, Pt, Ir, Ru, Os and Re for all the samples increased by introducing solid additives of FeCl 2 , TiO 2 and Nb 2 O 5 . The concentration technique provides the possibility of determining some noble metals in massive samples (up to 50 g) with widely ranging element contents. By using gamma and neutron activation on a microtron, the detection limits of 3x10 -2 ppm for Pt and Ir and 4x10 -3 ppm for Au were achieved. In the case of X-ray fluorescence analysis, the detection limit for these elements was 0.4 ppm

Noble Metal Arsenides and Gold Inclusions in Northwest Africa 8186

Science.gov (United States)

Srinivasan, P.; McCubbin, F. M.; Rahman, Z.; Keller, L. P.; Agee, C. B.

2016-01-01

CK carbonaceous chondrites are a highly thermally altered group of carbonaceous chondrites, experiencing temperatures ranging between approximately 576-867 degrees Centigrade. Additionally, the mineralogy of the CK chondrites record the highest overall oxygen fugacity of all chondrites, above the fayalite-magnetite-quartz (FMQ) buffer. Me-tallic Fe-Ni is extremely rare in CK chondrites, but magnetite and Fe,Ni sulfides are commonly observed. Noble metal-rich inclusions have previously been found in some magnetite and sulfide grains. These arsenides, tellurides, and sulfides, which contain varying amounts of Pt, Ru, Os, Te, As, Ir, and S, are thought to form either by condensation from a solar gas, or by exsolution during metamorphism on the chondritic parent body. Northwest Africa (NWA) 8186 is a highly metamorphosed CK chondrite. This meteorite is predominately composed of NiO-rich forsteritic olivine (Fo65), with lesser amounts of plagioclase (An52), augite (Fs11Wo49), magnetite (with exsolved titanomagnetite, hercynite, and titanohematite), monosulfide solid solution (with exsolved pentlandite), and the phosphate minerals Cl-apatite and merrillite. This meteorite contains coarse-grained, homogeneous silicates, and has 120-degree triple junctions between mineral phases, which indicates a high degree of thermal metamorphism. The presence of NiO-rich olivine, oxides phases all bearing Fe3 plus, and the absence of metal, are consistent with an oxygen fugacity above the FMQ buffer. We also observed noble metal-rich phases within sulfide grains in NWA 8186, which are the primary focus of the present study.

Enriching Silver Nanocrystals with a Second Noble Metal.

Science.gov (United States)

Wu, Yiren; Sun, Xiaojun; Yang, Yin; Li, Jumei; Zhang, Yun; Qin, Dong

2017-07-18

Noble-metal nanocrystals have received considerable interests owing to their fascinating properties and promising applications in areas including plasmonics, catalysis, sensing, imaging, and medicine. As demonstrated by ample examples, the performance of nanocrystals in these and related applications can be augmented by switching from monometallic to bimetallic systems. The inclusion of a second metal can enhance the properties and greatly expand the application landscape by bringing in new capabilities. Seeded growth offers a powerful route to bimetallic nanocrystals. This approach is built upon the concept that preformed nanocrystals with uniform, well-controlled size, shape, and structure can serve as seeds to template and direct the deposition of metal atoms. Seeded growth is, however, limited by galvanic replacement when the deposited metal is less reactive than the seed. The involvement of galvanic replacement not only makes it difficult to control the outcome of seeded growth but also causes degradation to some properties. We have successfully addressed this issue by reducing the salt precursor(s) into atoms with essentially no galvanic replacement. In the absence of self-nucleation, the atoms are preferentially deposited onto the seeds to generate bimetallic nanocrystals with controlled structures. In this Account, we use Ag nanocubes as an example to demonstrate the fabrication of Ag@M and Ag@Ag-M (M = Au, Pd, or Pt) nanocubes with a core-frame or core-shell structure by controlling the deposition of M atoms. A typical synthesis involves the titration of M n+ (a precursor to M) ions into an aqueous suspension containing Ag nanocubes, ascorbic acid, and poly(vinylpyrrolidone) under ambient conditions. In one approach, aqueous sodium hydroxide is introduced to increase the initial pH of the reaction system. At pH = 11.9, ascorbic acid is dominated by ascorbate monoanion, a much stronger reductant, to suppress the galvanic replacement between M n+ and Ag. In

Heterogeneous nanocomposites composed of silver sulfide and hollow structured Pd nanoparticles with enhanced catalytic activity toward formic acid oxidation

International Nuclear Information System (INIS)

Chen, Dong; Cui, Penglei; Liu, Hui; Yang, Jun

2015-01-01

Highlights: • Core–shell Ag-Ag/Pd nanoparticles with an Ag core and an Ag/Pd alloy shell are prepared via galvanic replacement reaction. • Heterogeneous Ag2S-hollow Pd nanocomposites are fabricated by converting the Ag component into Ag2S using element sulfur. • The heterogeneous Ag2S-hollow Pd nanocomposites display enhanced activity for formic acid oxidation due to electronic coupling effect. • The methodology may find applications to produce the semiconductor-metal nanocomposites with interesting architectures and tailored functionalities. - Abstract: Nanocomposites consisting semiconductor and noble metal domains are of great interest for their synergistic effect-based enhanced properties in a given application. Herein, we demonstrate a facile approach for the synthesis of heterogeneous nanocomposites consisting of silver sulfide (Ag 2 S) and hollow structured Pd nanoparticles (hPd). It begins with the preparation of core–shell nanoparticles with an Ag core and an alloy Ag/Pd shell in an organic solvent via galvanic replacement reaction (GRR) between Ag seed particles pre-synthesized and Pd 2+ ion precursors. The Ag component is then removed from the core and shell regions of core–shell Ag-Ag/Pd nanoparticles, and converted into Ag 2 S by elemental sulfur (S). The Ag 2 S forms the semiconductor domain in the nanocomposite and shares the solid-state interface with the resultant hollow structured Pd nanoparticle. As demonstrated, the Ag 2 S-hPd nanocomposites exhibit superior catalytic activity and durability for formic acid oxidation, compared to the pure Pd nanoparticles prepared by oleylamine reduction of Pd ion precursors and commercial Pd/C catalyst, due to the electronic coupling between semiconductor and noble metal domains in the nanocomposites. In addition, the structural transformation from core–shell to heterogeneous nanocomposites may provide new opportunities to design and fabricate hybrid nanostructures with interesting

Transparent and conductive electrodes by large-scale nano-structuring of noble metal thin-films

DEFF Research Database (Denmark)

Linnet, Jes; Runge Walther, Anders; Wolff, Christian

2018-01-01

grid, and nano-wire thin-films. The indium and carbon films do not match the chemical stability nor the electrical performance of the noble metals, and many metal films are not uniform in material distribution leading to significant surface roughness and randomized transmission haze. We demonstrate...

Bioactivity of noble metal nanoparticles decorated with biopolymers and their application in drug delivery.

Science.gov (United States)

Rai, Mahendra; Ingle, Avinash P; Gupta, Indarchand; Brandelli, Adriano

2015-12-30

The unique properties of nanomaterials can be applied to solve different problems including new ways of drug delivery. Noble metal nanoparticles are most promising because they have been used for medicinal purposes since ancient time. It is evident from the past studies that the metallic nanoparticles are much more effective against various microorganisms when compared to their conventional counterparts. However, decoration of such nanoparticles with biomaterials add more advantages to their antimicrobial activity. Decoration of metal nanoparticles with biopolymers is a quite new area of research. Studies performed hitherto shown that nanoparticles of noble metals like silver, gold and platinum demonstrated better antibacterial, antifungal and antiviral activities when conjugated with biopolymers. The development of such technology has potential to develop materials that are more effective in the field of health science. Considering the importance and uniqueness of this concept, the present review aims to discuss the use of biopolymer-decorated metal nanoparticles for combating various diseases caused by microbial pathogens. Moreover, the nanotoxicity aspect has also been discussed. Copyright © 2015 Elsevier B.V. All rights reserved.

3D-macroporous chitosan-based scaffolds with in situ formed Pd and Pt nanoparticles for nitrophenol reduction.

Science.gov (United States)

Berillo, Dmitriy; Cundy, Andrew

2018-07-15

3D-macroporous chitosan-based scaffolds (cryogels) were produced via growth of metal-polymer coordinated complexes and electrostatic interactions between oppositely charged groups of chitosan and metal ions under subzero temperatures. A mechanism of reduction of noble metal complexes inside the cryogel walls by glutaraldehyde is proposed, which produces discrete and dispersed noble metal nanoparticles. 3D-macroporous scaffolds prepared under different conditions were characterised using TGA, FTIR, nitrogen adsorption, SEM, EDX and TEM, and the distribution of platinum nanoparticles (PtNPs) and palladium nanoparticles (PdNPs) in the material assessed. The catalytic activity of the in situ synthesised PdNPs, at 2.6, 12.5 and 21.0 μg total mass, respectively, was studied utilising a model system of 4-nitrophenol reduction. The kinetics of the reaction under different conditions (temperature, concentration of catalyst) were examined, and a decrease of catalytic activity was not observed over 17 treatment cycles. Increasing the temperature of the catalytic reaction from 10 to 22 and 35 °C by PdNPs supported within the cryogel increased the kinetic rate by 44 and 126%, respectively. Turnover number and turnover frequency of the PdNPs catalysts at room temperature were in the range 0.20-0.53 h -1 . The conversion degree of 4-nitrophenol at room temperature reached 98.9% (21.0 μg PdNPs). Significantly less mass of palladium nanoparticles (by 30-40 times) was needed compared to published data to obtain comparable rates of reduction of 4-nitrophenol. Copyright © 2018 Elsevier Ltd. All rights reserved.

Spectrophotometric methods for determining noble metals

International Nuclear Information System (INIS)

Gur'eva, R.F.; Savvin, S.B.

2002-01-01

The main trends of the development of spectrophotometric methods for determining noble metals (NMs) including ruthenium are considered. One of these trends is the synthesis and study of new, highly sensitive and selective organic reagents for determining NMs in solutions and solid phase. Another trend is the search for and developing of new methodological approaches (techniques) and color reactions, including those that involve modified and immobilized reagents. The third trend includes the improvement of equipment and automation. It is shown that the present-day spectrophotometry can provide the determination of NMs in samples with concentrations from several to 10 -4 % (photometry and differential photometry) and down to 10 -7 % (test and sorption-spectroscopic methods based on photometry and diffuse-reflectance spectroscopy, including the use of chromaticity functions) [ru

Noble Metal Catalysts Supported on Nanofibrous Polymeric Membranes for Environmental Applications

Czech Academy of Sciences Publication Activity Database

Soukup, Karel; Topka, Pavel; Hejtmánek, Vladimír; Petráš, D.; Valeš, V.; Šolcová, Olga

2014-01-01

Roč. 236, NOV 1 (2014), s. 3-11 ISSN 0920-5861 R&D Projects: GA ČR GPP106/11/P459; GA ČR GP13-24186P Institutional support: RVO:67985858 Keywords : electrospinning * noble metals * catalytic oxidation * volatile organic compoundas Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 3.893, year: 2014

Ni/CeO{sub 2}-Al{sub 2}O{sub 3} catalysts promoted with noble metals for the hydrogen production by ethanol vapor reforming; Catalisadores de Ni/CeO{sub 2}-Al{sub 2}O{sub 3} promovidos com metais nobres para a producao de hidrogenio por reforma a vapor de etanol

Energy Technology Data Exchange (ETDEWEB)

Profeti, Luciene P.R.; Ticianelli, Edson Antonio; Assaf, Elisabete Moreira [Universidade de Sao Paulo (IQSC/USP), Sao Carlos, SP (Brazil). Inst. de Quimica]. E-mail: eassaf@iqsc.usp.br

2008-07-01

The catalytic activity of Ni/CeO{sub 2}-Al{sub 2}O{sub 3} catalysts modified with noble metals (Ru, Ir, Pt and Pd) was investigated in the steam reforming of ethanol. The catalysts were characterized by energy dispersive spectroscopy, X-ray diffraction, UV-Vis diffuse reflectance spectroscopy and H{sub 2} temperature-programmed reduction-X-ray absorption fine structure (XANES). The results showed that the formation of inactive nickel aluminate was avoided due to the presence of a CeO{sub 2} dispersed on the alumina. The promoting effect of noble metals included a decrease of the reduction temperatures of NiO species interacting with the support due to the hydrogen spillover effect, leading to an increase of the reducibilities of the promoted catalysts The better catalytic performance for the ethanol steam reforming was obtained for the NiPd/CeAl catalyst, which presented an effluent gaseous mixture with the highest H{sub 2} yield. (author)

Brazing of Cu with Pd-based metallic glass filler

Energy Technology Data Exchange (ETDEWEB)

Terajima, Takeshi [Joining and Welding Research Institute, Osaka University, 11-1 Mihogaoka, Ibaraki, Osaka 567-0047 (Japan)], E-mail: terajima@jwri.osaka-u.ac.jp; Nakata, Kazuhiro [Joining and Welding Research Institute, Osaka University, 11-1 Mihogaoka, Ibaraki, Osaka 567-0047 (Japan); Matsumoto, Yuji [Materials and Structures Laboratory, Tokyo Institute of Technology (Japan); Zhang, Wei; Kimura, Hisamichi; Inoue, Akihisa [Institute for Materials Research, Tohoku University (Japan)

2008-02-25

Metallic glass has several unique properties, including high mechanical strength, small solidification shrinkage, small elastic modulus and supercooling state, all of which are well suited as a residual stress buffer for metal and ceramic joining. In the present preliminary study, we demonstrated brazing of Cu rods with Pd{sub 40}Cu{sub 30}Ni{sub 10}P{sub 20} metallic glass filler. The brazing was carried out at 873 K for 1 min in a vacuum atmosphere (1 x 10{sup -3} Pa), and then the specimens were quenched at the rate of 30 K/s by blowing He. The metallic glass brazing of Cu using Pd{sub 40}Cu{sub 30}Ni{sub 10}P{sub 20} filler was successful, with the exception that several voids remained in the filler. According to micro-focused X-ray diffraction, no diffraction patterns were observed at both the center of the Pd{sub 40}Cu{sub 30}Ni{sub 10}P{sub 20} filler and the Cu/Pd{sub 40}Cu{sub 30}Ni{sub 10}P{sub 20} interface. The result showed that the Cu specimens were joined with Pd{sub 40}Cu{sub 30}Ni{sub 10}P{sub 20} filler in the glassy state. The tensile fracture strength of the brazed specimens ranged from 20 to 250 MPa. The crack extension from the voids in the Pd{sub 40}Cu{sub 30}Ni{sub 10}P{sub 20} filler may have caused the results to be uneven and very low compared to the strength of Pd-based bulk metallic glass.

Liquid state properties of certain noble and transition metals

International Nuclear Information System (INIS)

Bhuiyan, G.M.; Rahman, A.; Khaleque, M.A.; Rashid, R.I.M.A.; Mujibur Rahman, S.M.

1998-07-01

Certain structural, thermodynamic and atomic transport properties of a number of liquid noble and transition metals are reported. The underlying theory combines together a simple form of the N-body potential and the thermodynamically self-consistent variational modified hypernetted chain (VMHNC) theory of liquid. The static structure factors calculated by using the VMHNC resemble the hard sphere (HS) values. Consequently the HS model is used to calculate the thermodynamic properties viz. specific heat, entropy, isothermal compressibility and atomic transport properties. (author)

High-pressure phase transition of alkali metal-transition metal deuteride Li2PdD2

Science.gov (United States)

Yao, Yansun; Stavrou, Elissaios; Goncharov, Alexander F.; Majumdar, Arnab; Wang, Hui; Prakapenka, Vitali B.; Epshteyn, Albert; Purdy, Andrew P.

2017-06-01

A combined theoretical and experimental study of lithium palladium deuteride (Li2PdD2) subjected to pressures up to 50 GPa reveals one structural phase transition near 10 GPa, detected by synchrotron powder x-ray diffraction, and metadynamics simulations. The ambient-pressure tetragonal phase of Li2PdD2 transforms into a monoclinic C2/m phase that is distinct from all known structures of alkali metal-transition metal hydrides/deuterides. The structure of the high-pressure phase was characterized using ab initio computational techniques and from refinement of the powder x-ray diffraction data. In the high-pressure phase, the PdD2 complexes lose molecular integrity and are fused to extended [PdD2]∞ chains. The discovered phase transition and new structure are relevant to the possible hydrogen storage application of Li2PdD2 and alkali metal-transition metal hydrides in general.

Fabrication and magnetic-induced aggregation of Fe3O4–noble metal composites for superior SERS performances

International Nuclear Information System (INIS)

Gan, Zibao; Zhao, Aiwu; Zhang, Maofeng; Wang, Dapeng; Guo, Hongyan; Tao, Wenyu; Gao, Qian; Mao, Ranran; Liu, Erhu

2013-01-01

Fe 3 O 4 –noble metal composites were obtained by combining Au, Ag nanoparticles (NPs) with 3-aminopropyltrimethoxysilane-functionalized Fe 3 O 4 NPs. UV–Visible absorption spectroscopy demonstrates the obtained Fe 3 O 4 –noble metal composites inherit the typical surface plasmon resonance bands of Au, Ag at 533 and 453 nm, respectively. Magnetic measurements also indicated that the superparamagnetic Fe 3 O 4 –noble metal composites have excellent magnetic response behavior. A magnetic-induced idea was introduced to change their aggregated states and take full advantage of their surface-enhanced Raman scattering (SERS) performances. Under the induction of an external magnetic field, the bifunctional Fe 3 O 4 –noble metal aggregates exhibit the unique superiority in SERS detection of Rhodamine 6G (R6G), compared with the naturally dispersed Au, Ag NPs. Especially, the detection limit of the Fe 3 O 4 –Ag aggregates for R6G is as low as 10 −14  M, and the calculated EF reaches up to 1.2 × 10 6 , which meets the requirements for trace detection of analytes. Furthermore, the superiority could be extended to sensitive detection of other organic molecules, such as 4-mercaptopyridine. This work provides a new insight for active adjustment of the aggregated states of SERS substrates and the optimization of SERS performances

Microstructure and corrosion of Pd-modified Ti alloys produced by powder metallurgy

International Nuclear Information System (INIS)

Ashworth, M.A.; Davenport, A.J.; Ward, R.M.; Hamilton, H.G.C.

2010-01-01

A method for the fabrication of titanium alloy parts with enhanced corrosion resistance by a powder metallurgy route is presented in this paper. Commercial purity titanium powders modified with Pd have been hot isostatically pressed (HIPped) and the microstructure and distribution of the noble metal characterised by optical and scanning electron microscopy. The electrochemistry of the HIPped alloy has been assessed and the effect of powder size fraction evaluated. Results show that the phase composition and electrochemistry of the HIPped Pd-modified alloy is equivalent to that of wrought grade 7 Ti.

Classical and quantum effects in noble metal and graphene plasmonics

DEFF Research Database (Denmark)

Mortensen, N. Asger

2015-01-01

Plasmonics — the interaction of light with free electrons in metals — is commonly understood within classical electrodynamics using local-response constitutive laws (such as Ohm's law). However, the tight localization of plasmons to small volumes is revealing intriguing new physics such as noncla......Plasmonics — the interaction of light with free electrons in metals — is commonly understood within classical electrodynamics using local-response constitutive laws (such as Ohm's law). However, the tight localization of plasmons to small volumes is revealing intriguing new physics...... such as nonclassical electrodynamics with a nonlocal response of the plasmons. Nonlocal effects are being explored both theoretically and experimentally in different charge-conducting material systems with examples ranging from sub-10 nanometer noble metal particles to one-atom thin disks of doped graphene....

Synthesis, fabrication, and spectroscopy of nano-scale photonic noble metal materials

Science.gov (United States)

Egusa, Shunji

Nanometer is an interesting scale for physicists, chemists, and materials scientists, in a sense that it lies between the macroscopic and the atomic scales. In this regime, materials exhibit distinct physical and chemical properties that are clearly different from those of atoms or macroscopic bulk. This thesis is concerned about both physics and chemistry of noble metal nano-structures. Novel chemical syntheses and physical fabrications of various noble metal nano-structures, and the development of spectroscopic techniques for nano-structures are presented. Scanning microscopy/spectroscopy techniques inherently perturbs the true optical responses of the nano-structures. However, by using scanning tunneling microscope (STM) tip as the nanometer-confined excitation source of surface plasmons in the samples, and subsequently collecting the signals in the Fourier space, it is shown that the tip-perturbed part of the signals can be deconvoluted. As a result, the collected signal in this approach is the pure response of the sample. Coherent light is employed to study the optical response of nano-structures, in order to avoid complication from tip-perturbation as discussed above. White-light super-continuum excites the nano-structure, the monolayer of Au nanoparticles self-assembled on silicon nitride membrane substrates. The coherent excitation reveals asymmetric surface plasmon resonance in the nano-structures. One of the most important issues in nano-scale science is to gain control over the shape, size, and assembly of nanoparticles. A novel method is developed to chemically synthesize ligand-passivated atomic noble metal clusters in solution phase. The method, named thermal decomposition method, enables facile yet robust synthesis of fluorescent atomic clusters. Thus synthesized atomic clusters are very stable, and show behaviors of quantum dots. A novel and versatile approach for creation of nanoparticle arrays is developed. This method is different from the

Physical properties of Pd and Al transition metals and Pd-Al binary metal alloy investigated by using molecular dynamics simulation

International Nuclear Information System (INIS)

Coruh, A.; Uludogan, M.; Tomak, M.; Cagin, T.

2002-01-01

In this study, physical properties, such as Pair Distribution Function g(r), Structure Factor S(k)''1'',''4, Diffusion Coefficient D''2''.''4, Intermediate Scattering function S(k,t)''3'',''4 and Dynamical Structure Factor S(k,w)''3'',''4 of some transition metals and metal alloys are investigated by using molecular dynamics simulation method. The simulation is specified for Pd, Al transition metals and Pd-Al binary metal alloys in the liquid form for different concentrations and at various temperatures by using Quantum Sutton-Chen (Q-SC) inter atomic potential. Intermediate scattering function and dynamical structure factor are calculated for various values of wave vector k. Results are in good agreement with published data''1'',''3'',''4

Study of sorption of platinum metals, gold and silver by phosphonium hydroxide antonite

International Nuclear Information System (INIS)

Khudaybergenov, U.; Tajibaev, D.; Yuldasheva, K.T.

2002-01-01

The aim of the work was to study and to use a phosphonium hydroxide anionite for concentrating of trace amounts of platinum metals, gold and silver from the mixed solutions composed of copper, nickel, cobalt, iron and zinc. The experiments were done using radionuclides of determined and interfered elements. Conditions for sorption concentrating of the noble metals by phosphonium hydroxide were determined by the selectivity of the phosphonium hydroxide to the noble metals from acid solutions. A noble metal sorption degree was observed from the experiments to be rather high at the acid concentration level of 0.1-0.5 M. At higher than 0.5 M acid concentration sorption activity decreased. With increase of chlorine acid-concentration sorption of palladium was observed to considerably decrease, while iridium sorption was increased. The latter fact can be caused by lowering of hydration of iridium ions. A considerable decrease of capability of the noble metal sorption from nitric acid solutions was observed. It is possible that HNO 3 anions are strongly bound with the anionite functional group. Thus, nitric acid reduces sorption of the noble metals in the following order: Ir>Ru>Pd>Pt>Os, and it does not have effect on the sorption activity of Au and Ag. Increase of H 2 SO 4 concentration in the solution has slightly reduced noble metal sorption activity. Copper, nickel, iron and other metals accompanying the noble metals, at concentration ratio of 1:1000 have resulted in decrease of sorption activity of the noble metals, although sorption of iridium was increased in the presence of copper, silver and nickel. We suggest that copper, silver and nickel have formed the complex functional compounds, which can probably undergo an anion exchange

Screening metal-organic frameworks for selective noble gas adsorption in air: effect of pore size and framework topology.

Science.gov (United States)

Parkes, Marie V; Staiger, Chad L; Perry, John J; Allendorf, Mark D; Greathouse, Jeffery A

2013-06-21

The adsorption of noble gases and nitrogen by sixteen metal-organic frameworks (MOFs) was investigated using grand canonical Monte Carlo simulation. The MOFs were chosen to represent a variety of net topologies, pore dimensions, and metal centers. Three commercially available MOFs (HKUST-1, AlMIL-53, and ZIF-8) and PCN-14 were also included for comparison. Experimental adsorption isotherms, obtained from volumetric and gravimetric methods, were used to compare krypton, argon, and nitrogen uptake with the simulation results. Simulated trends in gas adsorption and predicted selectivities among the commercially available MOFs are in good agreement with experiment. In the low pressure regime, the expected trend of increasing adsorption with increasing noble gas polarizabilty is seen. For each noble gas, low pressure adsorption correlates with several MOF properties, including free volume, topology, and metal center. Additionally, a strong correlation exists between the Henry's constant and the isosteric heat of adsorption for all gases and MOFs considered. Finally, we note that the simulated and experimental gas selectivities demonstrated by this small set of MOFs show improved performance compared to similar values reported for zeolites.

Experimental study on the surface characteristics of Pd-based bulk metallic glass

Energy Technology Data Exchange (ETDEWEB)

Zhang, Xiang; Sun, Bingli [School of Mechanics and Engineering Science, Zhengzhou University, Zhengzhou 450001 (China); National Center for International Joint Research of Micro-nano Molding Technology, Zhengzhou University, Zhengzhou 450001 (China); Key Laboratory for Micro Molding Technology of Henan Province, Zhengzhou University, Zhengzhou, 450001 (China); Zhao, Na [National Center for International Joint Research of Micro-nano Molding Technology, Zhengzhou University, Zhengzhou 450001 (China); Key Laboratory for Micro Molding Technology of Henan Province, Zhengzhou University, Zhengzhou, 450001 (China); National Engineering Research Center for Advanced Polymer Processing Technology, Zhengzhou University, Zhengzhou 450002 (China); Li, Qian, E-mail: qianli@zzu.edu.cn [School of Mechanics and Engineering Science, Zhengzhou University, Zhengzhou 450001 (China); National Center for International Joint Research of Micro-nano Molding Technology, Zhengzhou University, Zhengzhou 450001 (China); Key Laboratory for Micro Molding Technology of Henan Province, Zhengzhou University, Zhengzhou, 450001 (China); National Engineering Research Center for Advanced Polymer Processing Technology, Zhengzhou University, Zhengzhou 450002 (China); Hou, Jianhua; Feng, Weina [School of Mechanics and Engineering Science, Zhengzhou University, Zhengzhou 450001 (China); National Center for International Joint Research of Micro-nano Molding Technology, Zhengzhou University, Zhengzhou 450001 (China); Key Laboratory for Micro Molding Technology of Henan Province, Zhengzhou University, Zhengzhou, 450001 (China)

2014-12-01

Highlights: • Wetting behavior of four polymer melts on Pd-based bulk metallic glass was investigated. • From results, in general, the contact angle of polymer on Pd-based BMG decreases with temperature increasing. • We find a critical temperature for each polymer, above this temperature, contact angle on Pd-based BMG does not decrease with temperature increasing. • Surface free energy of Pd-based BMG was estimated by Owens–Wendt method. - Abstract: The metallic glass has many unique and desirable physical and chemical characteristics for their long-range disordered atomic structure, among them the interfacial properties of the metallic glasses are crucial for their applications and manufacturing. In this work, the contact wetting angles between the polymer melts and Pd{sub 40}Cu{sub 30}Ni{sub 10}P{sub 20} bulk metallic glass (Pd-BMG) with four kinds of roughness were analyzed. Experiments show the order of four polymers wettability on Pd-BMG was PP > HDPE > COC > PC. The surface free energy of Pd-BMG was estimated by Owens–Wendt method using the contact angles of three testing liquids. Neumann method was also used to further evidence the surface free energy of Pd-BMG comparing with PTFE, mold steels NAK80 and LKM2343ESR. The results provide theoretical and technical supports for the fabrication of metallic glass micro mold and the parameter optimization of polymer micro injection molding.

Reaction pathways of biomass-derived oxygenates on noble metal surfaces

Science.gov (United States)

McManus, Jesse R.

As the global demand for energy continues to rise, the environmental concerns associated with increased fossil fuel consumption have motivated the use of biomass as an alternative, carbon-renewable energy feedstock. Controlling reactive chemistry of the sugars that comprise biomass through the use of catalysis becomes essential in effectively producing green fuels and value-added chemicals. Recent work on biomass conversion catalysts have demonstrated the efficacy of noble metal catalyst systems for the reforming of biomass to hydrogen fuel, and the hydrodeoxygenation of biomass-derived compounds to value-added chemicals. In particular, Pt and Pd surfaces have shown considerable promise as reforming catalysts in preliminary aqueous phase reforming studies. It becomes important to understand the mechanisms by which these molecules react on the catalyst surfaces in order to determine structure-activity relationships and bond scission energetics as to provide a framework for engineering more active and selective catalysts. Fundamental surface science techniques provide the tools to do this; however, work in this field has been so far limited to simple model molecules like ethanol and ethylene glycol. Herein, temperature programmed desorption and high resolution electron energy loss spectroscopy are utilized in an ultra-high vacuum surface science study of the biomass-derived sugar glucose on Pt and Pd single crystal catalysts. Overall, it was determined that the aldehyde function of a ring-open glucose molecule plays an integral part in the initial bonding and reforming reaction pathway, pointing to the use of aldoses glycolaldehyde and glyceraldehyde as the most appropriate model compounds for future studies. Furthermore, the addition of adatom Zn to a Pt(111) surface was found to significantly decrease the C-H and C-C bond scission activity in aldehyde containing compounds, resulting in a preferred deoxygenation pathway in opposition to the decarbonylation pathway

Noble Metal Nanoparticles Applications in Cancer

Directory of Open Access Journals (Sweden)

João Conde

2012-01-01

Full Text Available Nanotechnology has prompted new and improved materials for biomedical applications with particular emphasis in therapy and diagnostics. Special interest has been directed at providing enhanced molecular therapeutics for cancer, where conventional approaches do not effectively differentiate between cancerous and normal cells; that is, they lack specificity. This normally causes systemic toxicity and severe and adverse side effects with concomitant loss of quality of life. Because of their small size, nanoparticles can readily interact with biomolecules both at surface and inside cells, yielding better signals and target specificity for diagnostics and therapeutics. This way, a variety of nanoparticles with the possibility of diversified modification with biomolecules have been investigated for biomedical applications including their use in highly sensitive imaging assays, thermal ablation, and radiotherapy enhancement as well as drug and gene delivery and silencing. Here, we review the available noble metal nanoparticles for cancer therapy, with particular focus on those already being translated into clinical settings.

Noble metal (NM) behavior during simulated HLLW vitrification in induction melter with cold crucible

International Nuclear Information System (INIS)

Demin, A.V.; Matyunin, Y.I.; Fedorova, M.I.

1995-01-01

The investigation of noble metal (Ru, Rh, Pd) properties in, glass melts are connected with their specific behaviors during HLLW vitrification. Ruthenium, rhodium and palladium volatilities and heterogeneous platinoid phases forming on melts are investigated in reasonable details conformably to Joule's heating ceramic melters. The vitrification conditions in melters with induction heating of melts are differ from the vitrification ones in ceramic melters on some numbers of parameters (the availability of significant temperature gradients and convection flows in melts, short time of molten mass updating in melter and probability of definite interaction between high-frequency field and melt inhomogeneities). The results of simulated HLLW solidification modelling of the vitrification process in induction melter with cold crucible to produce phosphate and boron-silicate materials are presented. The properties of received glasses and behavior of platinoids are shown to have analogies and distinctions in comparison with compounds, synthesized in ceramic melter. The structures of dispersed particles of NM heterogeneous phases forming in glass melts prepared in induction melter with cold crucible are identified. The results of investigations show, that the marked distinctions between two processes can influence (in definite degree) as on property of synthesized materials, as on behavior of platinoid during vitrifications

Applications of UV/Vis Spectroscopy in Characterization and Catalytic Activity of Noble Metal Nanoparticles Fabricated in Responsive Polymer Microgels: A Review.

Science.gov (United States)

Begum, Robina; Farooqi, Zahoor H; Naseem, Khalida; Ali, Faisal; Batool, Madeeha; Xiao, Jianliang; Irfan, Ahmad

2018-11-02

Noble metal nanoparticles loaded smart polymer microgels have gained much attention due to fascinating combination of their properties in a single system. These hybrid systems have been extensively used in biomedicines, photonics, and catalysis. Hybrid microgels are characterized by using various techniques but UV/Vis spectroscopy is an easily available technique for characterization of noble metal nanoparticles loaded microgels. This technique is widely used for determination of size and shape of metal nanoparticles. The tuning of optical properties of noble metal nanoparticles under various stimuli can be studied using UV/Vis spectroscopic method. Time course UV/Vis spectroscopy can also be used to monitor the kinetics of swelling and deswelling of microgels and hybrid microgels. Growth of metal nanoparticles in polymeric network or growth of polymeric network around metal nanoparticle core can be studied by using UV/Vis spectroscopy. This technique can also be used for investigation of various applications of hybrid materials in catalysis, photonics, and sensing. This tutorial review describes the uses of UV/Vis spectroscopy in characterization and catalytic applications of responsive hybrid microgels with respect to recent research progress in this area.

Investigation of noble metal deposition behaviour in boiling water reactors. The NORA project

International Nuclear Information System (INIS)

Ritter, Stefan; Karastoyanov, Vasil; Abolhassani-Dadras, Sousan; Guenther-Leopold, Ines; Kivel, Niko

2010-01-01

NobleChem trademark is a technology developed by General Electric to reduce stress corrosion cracking (SCC) in reactor internals and recirculation pipes of boiling water reactors (BWRs) while preventing the negative side effects of classic hydrogen water chemistry. Noble metals (Pt, Rh) acting as electrocatalysts for the recombination of O 2 and H 2 O 2 with H 2 to H 2 O and thus reducing the corrosion potential more efficiently are injected into the feedwater during reactor shutdown (classic method) or on-line during power operation. They are claimed to deposit as very fine metallic particles on all water-wetted surfaces, including the most critical regions inside existing cracks, and to stay electrocatalytic over long periods of time. The effectiveness of this technology in plants still remains to be demonstrated. Based on highly credible laboratory experiments down to the sub-μg . kg -1 Pt concentration range, SCC mitigation may be expected, provided that a stoichiometric excess of H 2 and a sufficient surface coverage with very fine Pt particles exist simultaneously at the critical locations [1]. Very little is known about the deposition and (re-)distribution behaviour of the Pt in the reactor. For the validation of this technique the research project NORA (noble metal deposition behaviour in BWRs) has been started at the Paul Scherrer Institute (PSI) with two main objectives: (i) to gain phenomenological insights and a better basic understanding of the Pt distribution and deposition behaviour in BWRs; (ii) to develop and qualify a non-destructive technique to characterise the size and distribution of the Pt particles and the local concentration of Pt on reactor components. This paper presents the objectives of the project, the planned work and a brief description of the status of the project. (orig.)

Tailoring the supercapacitive performances of noble metal oxides, porous carbons and their composites

Directory of Open Access Journals (Sweden)

Panić Vladimir V.

2013-01-01

Full Text Available Porous electrochemical supercapacitive materials, as an important type of new-generation energy storage devices, require a detailed analysis and knowledge of their capacitive performances upon different charging/discharging regimes. The investigation of the responses to dynamic perturbations of typical representatives, noble metal oxides, carbonaceous materials and RuO2-impregnated carbon blacks, by electrochemical impedance spectroscopy (EIS is presented. This presentation follows a brief description of supercapacitive behavior and origin of pseudocapacitive response of noble metal oxides. For all investigated materials, the electrical charging/discharging equivalent of the EIS response was found to obey the transmission line model envisaged as so-called „resistor/capacitor (RC ladder“. The ladder features are correlated to material physicochemical properties, its composition and the composition of the electrolyte. Fitting of the EIS data of different supercapacitive materials to appropriate RC ladders enables the in-depth profiling of the capacitance and pore resistance of their porous thin-layers and finally the complete revelation of capacitive energy storage issues. [Projekat Ministarstva nauke Republike Srbije, br. 172060

Marginal discrepancy of noble metal-ceramic fixed dental prosthesis frameworks fabricated by conventional and digital technologies.

Science.gov (United States)

Afify, Ahmed; Haney, Stephan; Verrett, Ronald; Mansueto, Michael; Cray, James; Johnson, Russell

2018-02-01

Studies evaluating the marginal adaptation of available computer-aided design and computer-aided manufacturing (CAD-CAM) noble alloys for metal-ceramic prostheses are lacking. The purpose of this in vitro study was to evaluate the vertical marginal adaptation of cast, milled, and direct metal laser sintered (DMLS) noble metal-ceramic 3-unit fixed partial denture (FDP) frameworks before and after fit adjustments. Two typodont teeth were prepared for metal-ceramic FDP abutments. An acrylic resin pattern of the prepared teeth was fabricated and cast in nickel-chromium (Ni-Cr) alloy. Each specimen group (cast, milled, DMLS) was composed of 12 casts made from 12 impressions (n=12). A single design for the FDP substructure was created on a laboratory scanner and used for designing the specimens in the 3 groups. Each specimen was fitted to its corresponding cast by using up to 5 adjustment cycles, and marginal discrepancies were measured on the master Ni-Cr model before and after laboratory fit adjustments. The milled and DMLS groups had smaller marginal discrepancy measurements than those of the cast group (PDMLS and cast groups (F=30.643, P<.001). Metal-ceramic noble alloy frameworks fabricated by using a CAD-CAM workflow had significantly smaller marginal discrepancies compared with those with a traditional cast workflow, with the milled group demonstrating the best marginal fit among the 3 test groups. Manual refining significantly enhanced the marginal fit of all groups. All 3 groups demonstrated marginal discrepancies within the range of clinical acceptability. Copyright © 2017 Editorial Council for the Journal of Prosthetic Dentistry. Published by Elsevier Inc. All rights reserved.

Exploring methods for compositional and particle size analysis of noble metal nanoparticles in Daphnia manga

NARCIS (Netherlands)

Krystek, P.W.; Brandsma, S.H.; Leonards, P.E.G.; de Boer, J.

2016-01-01

The identification and quantification of the bioaccumulation of noble metal engineered nanoparticles (ENPs) by aquatic organisms is of great relevance to understand the exposure and potential toxicity mechanisms of nanoscale materials. Four analytical scenarios were investigated in relation to

Determination of noble metals in geological materials by radiochemical neutron-activation analysis

International Nuclear Information System (INIS)

Ahmad, I.; Ahmad, S.; Morris, D.F.C.

1977-01-01

A method for the determination of platinum, palladium, gold and iridium in geological materials following activation with thermal neutrons is described. Radionuclides formed from the elements are separated by a scheme based largely on liquid-liquid extractions. The procedure has been applied to the analysis of US Geological Survey standard rocks and to studies of the distribution of the noble metals in lateritic nickel ores. (author)

Ru-assisted synthesis of Pd/Ru nanodendrites with high activity for ethanol electrooxidation

Science.gov (United States)

Zhang, Ke; Bin, Duan; Yang, Beibei; Wang, Caiqin; Ren, Fangfang; Du, Yukou

2015-07-01

Due to the specific physical and chemical properties of a highly branched noble metal, the controllable synthesis has attracted much attention. This article reports the synthesis of Pd/Ru nanodendrites by a facile method using an oil bath in the presence of polyvinyl pyrrolidone, potassium bromide and ascorbic acid. The morphology, structure, and composition of the as-prepared catalysts were characterized by means of X-ray diffraction, X-ray photoelectron spectroscopy and transmission electron microscopy. In the electrochemical measurement, the as-prepared Pd7/Ru1 bimetallic nanodendrites provide a large electrochemically active surface area and exhibit high peak current density in the forward scan toward ethanol electrooxidation, which is nearly four times higher than those of a pure Pd catalyst. The as-prepared Pd7/Ru1 catalysts also exhibit significantly enhanced cycling stability toward ethanol oxidation in alkaline medium, which are mainly ascribed to the synergetic effect between Pd and Ru. This indicates that the Pd7/Ru1 catalysts should have great potential applications in direct ethanol fuel cells.Due to the specific physical and chemical properties of a highly branched noble metal, the controllable synthesis has attracted much attention. This article reports the synthesis of Pd/Ru nanodendrites by a facile method using an oil bath in the presence of polyvinyl pyrrolidone, potassium bromide and ascorbic acid. The morphology, structure, and composition of the as-prepared catalysts were characterized by means of X-ray diffraction, X-ray photoelectron spectroscopy and transmission electron microscopy. In the electrochemical measurement, the as-prepared Pd7/Ru1 bimetallic nanodendrites provide a large electrochemically active surface area and exhibit high peak current density in the forward scan toward ethanol electrooxidation, which is nearly four times higher than those of a pure Pd catalyst. The as-prepared Pd7/Ru1 catalysts also exhibit significantly

Novel Metal Nanomaterials and Their Catalytic Applications

Directory of Open Access Journals (Sweden)

Jiaqing Wang

2015-09-01

Full Text Available In the rapidly developing areas of nanotechnology, nano-scale materials as heterogeneous catalysts in the synthesis of organic molecules have gotten more and more attention. In this review, we will summarize the synthesis of several new types of noble metal nanostructures (FePt@Cu nanowires, Pt@Fe2O3 nanowires and bimetallic Pt@Ir nanocomplexes; Pt-Au heterostructures, Au-Pt bimetallic nanocomplexes and Pt/Pd bimetallic nanodendrites; Au nanowires, CuO@Ag nanowires and a series of Pd nanocatalysts and their new catalytic applications in our group, to establish heterogeneous catalytic system in “green” environments. Further study shows that these materials have a higher catalytic activity and selectivity than previously reported nanocrystal catalysts in organic reactions, or show a superior electro-catalytic activity for the oxidation of methanol. The whole process might have a great impact to resolve the energy crisis and the environmental crisis that were caused by traditional chemical engineering. Furthermore, we hope that this article will provide a reference point for the noble metal nanomaterials’ development that leads to new opportunities in nanocatalysis.

Update on the use of dissolved oxygen addition to monitor the effectiveness of noble metal applications in external manifolds

International Nuclear Information System (INIS)

Varela, J.A.; Huie, H.H.; Seeman, R.A.; Bourne, C.M.; Odell, A.D.

2014-01-01

Electrochemical corrosion potential (ECP) measurements in a Mitigation Monitoring System (MMS) ECP manifold have historically been a primary indicator of the effectiveness of an On-Line NobleChem™ (OLNC) application, with the MMS ECP intended to measure the catalytic effect of noble metal deposited on the ECP manifold surface. In some plants ECP measurements made on untreated surfaces prior to an OLNC application were significantly lower than what would be expected for stainless steel under reactor bulk chemistry conditions. This is due to the consumption and depletion of bulk liquid dissolved oxygen (DO) in the lines supplying reactor water to these external ECP measurement locations. This phenomenon degrades the ability to use these external manifolds to confirm noble metal deposition. Previous papers have described how the injection of an oxygen-rich stream to the MMS supply stream (DO Addition) can be used to re-establish the capability of external ECP measurements to monitor the catalytic behavior of platinum deposited during an OLNC injection. This paper will provide an update of how this method is being successfully used in operating BWRs to monitor OLNC injections. The paper will outline the overall approach used to characterize the catalytic behavior of external ECP manifolds before and after the noble metal application and present plant data collected during DO Additions performed under various conditions. (author)

Thermodynamics of Pore Filling Metal Clusters in Metal Organic Frameworks: Pd in UiO-66

DEFF Research Database (Denmark)

Vilhelmsen, Lasse; Sholl, David S.

2012-01-01

Metal organic frameworks (MOFs) have experimentally been demonstrated to be capable of supporting isolated transition-metal clusters, but the stability of these clusters with respect to aggregation is unclear. In this letter we use a genetic algorithm together with density functional theory...... calculations to predict the structure of Pd clusters in UiO-66. The cluster sizes examined are far larger than those in any previous modeling studies of metal clusters in MOFs and allow us to test the hypothesis that the physically separated cavities in UiO-66 could stabilize isolated Pd clusters. Our...... calculations show that Pd clusters in UiO-66 are, at best, metastable and will aggregate into connected pore filling structures at equilibrium....

Some remarks on the use of the effective medium approximation for the resistivity calculations in liquid noble metals

International Nuclear Information System (INIS)

Gorecki, J.

1982-09-01

The application of the effective medium approximation (EMA) to the muffin-tin model of liquid metal is considered. The triple correlation function is included in the expression for electrical resistivity. Good agreement with experimental data can be expected for liquid noble metals. (author)

The effect of dielectric constants on noble metal/semiconductor SERS enhancement: FDTD simulation and experiment validation of Ag/Ge and Ag/Si substrates.

Science.gov (United States)

Wang, Tao; Zhang, Zhaoshun; Liao, Fan; Cai, Qian; Li, Yanqing; Lee, Shuit-Tong; Shao, Mingwang

2014-02-11

The finite-difference time-domain (FDTD) method was employed to simulate the electric field distribution for noble metal (Au or Ag)/semiconductor (Ge or Si) substrates. The simulation showed that noble metal/Ge had stronger SERS enhancement than noble metal/Si, which was mainly attributed to the different dielectric constants of semiconductors. In order to verify the simulation, Ag nanoparticles with the diameter of ca. 40 nm were grown on Ge or Si wafer (Ag/Ge or Ag/Si) and employed as surface-enhanced Raman scattering substrates to detect analytes in solution. The experiment demonstrated that both the two substrates exhibited excellent performance in the low concentration detection of Rhodamine 6G. Besides, the enhancement factor (1.3 × 10(9)) and relative standard deviation values (less than 11%) of Ag/Ge substrate were both better than those of Ag/Si (2.9 × 10(7) and less than 15%, respectively), which was consistent with the FDTD simulation. Moreover, Ag nanoparticles were grown in-situ on Ge substrate, which kept the nanoparticles from aggregation in the detection. To data, Ag/Ge substrates showed the best performance for their sensitivity and uniformity among the noble metal/semiconductor ones.

Optical and structural properties of noble-metal nanoparticles; Optische und strukturelle Eigenschaften von Edelmetallnanopartikeln

Energy Technology Data Exchange (ETDEWEB)

Dahmen, C

2006-06-23

Noble-metal nanoparticles exhibit rich optical behavior, such as resonant light scattering and absorption and non-linear signal enhancement. This makes them attractive for a multitude of physical, chemical, and biophysical applications. For instance, recent biomedical experiments demonstrate the suitability of noble-metal nanoparticles for selective photothermal apoptosis by heat transport by laser irradiation. The applications of nanoparticles largely exploit that plasmons, i. e. collective oscillations of the conduction electrons, can be optically excited in these nanoparticles. In optical spectroscopy, these are seen as pronounced resonances. In the first part of this work, model calculations are employed to elucidate how radiation damping in noble-metal nanoparticles, i. e. the transformation of plasmons into photons, depends on particle size, particle shape, and on electromagnetic coupling between individual particles. Exact electrodynamic calculations are carried out for individual spheroidal particles and for pairs of spherical particles. These calculations for spheroidal particles demonstrate for the first time that radiative plasmon decay is determined by both the particle volume and the particle shape. Model calculations for pairs of large spherical particles reveal that the electromagnetic fields radiated by the particles mediate electromagnetic coupling at interparticle distances in the micrometer range. This coupling can lead to immense modulations of the plasmonic linewidth. The question whether this coupling is sufficiently strong to mediate extended, propagating, plasmon modes in nanoparticle arrays is addressed next. Detailed analysis reveals that this is not the case; instead, for the particle spacings regarded here, a non-resonant, purely diffractive coupling is observed, which is identified by steplike signatures in reflection spectra of the particle arrays. In the second part of this work, structural and optical properties of noble-metal

Fabrication and magnetic-induced aggregation of Fe{sub 3}O{sub 4}–noble metal composites for superior SERS performances

Energy Technology Data Exchange (ETDEWEB)

Gan, Zibao; Zhao, Aiwu, E-mail: awzhao@iim.ac.cn; Zhang, Maofeng; Wang, Dapeng; Guo, Hongyan; Tao, Wenyu; Gao, Qian; Mao, Ranran; Liu, Erhu [Chinese Academy of Sciences, Institute of Intelligent Machines (China)

2013-11-15

Fe{sub 3}O{sub 4}–noble metal composites were obtained by combining Au, Ag nanoparticles (NPs) with 3-aminopropyltrimethoxysilane-functionalized Fe{sub 3}O{sub 4} NPs. UV–Visible absorption spectroscopy demonstrates the obtained Fe{sub 3}O{sub 4}–noble metal composites inherit the typical surface plasmon resonance bands of Au, Ag at 533 and 453 nm, respectively. Magnetic measurements also indicated that the superparamagnetic Fe{sub 3}O{sub 4}–noble metal composites have excellent magnetic response behavior. A magnetic-induced idea was introduced to change their aggregated states and take full advantage of their surface-enhanced Raman scattering (SERS) performances. Under the induction of an external magnetic field, the bifunctional Fe{sub 3}O{sub 4}–noble metal aggregates exhibit the unique superiority in SERS detection of Rhodamine 6G (R6G), compared with the naturally dispersed Au, Ag NPs. Especially, the detection limit of the Fe{sub 3}O{sub 4}–Ag aggregates for R6G is as low as 10{sup −14} M, and the calculated EF reaches up to 1.2 × 10{sup 6}, which meets the requirements for trace detection of analytes. Furthermore, the superiority could be extended to sensitive detection of other organic molecules, such as 4-mercaptopyridine. This work provides a new insight for active adjustment of the aggregated states of SERS substrates and the optimization of SERS performances.

Non-noble metal graphene oxide-copper (II) ions hybrid electrodes for electrocatalytic hydrogen evolution reaction

KAUST Repository

Muralikrishna, S.; Ravishankar, T.N.; Ramakrishnappa, T.; Nagaraju, Doddahalli H.; Krishna Pai, Ranjith

2015-01-01

Non-noble metal and inexpensive graphene oxide-copper (II) ions (GO-Cu2+) hybrid catalysts have been explored for the hydrogen evolution reaction (HER). We were able to tune the binding abilities of GO toward the Cu2+ ions and hence their catalytic

Thiacalix[4]arene derivatives as extractants for metal ions in aqueous solutions: Application to the selective facilitated transport of Ag(I)

Energy Technology Data Exchange (ETDEWEB)

Zaghbani, Asma [Laboratoire Eau et Technologies Membranaires, CERTE, BP 273, 8020 Soliman (Tunisia); Fontas, Claudia [Department of Chemistry, University of Girona, 17071 Girona (Spain)], E-mail: claudia.fontas@udg.edu; Hidalgo, Manuela [Department of Chemistry, University of Girona, 17071 Girona (Spain); Tayeb, Rafik; Dhahbi, Mahmoud [Laboratoire Eau et Technologies Membranaires, CERTE, BP 273, 8020 Soliman (Tunisia); Vocanson, Francis; Lamartine, Roger [Universite de Lyon, Lyon, F-69003 (France); Universite Lyon 1, Villeurbanne, F-69622 (France); CNRS, UMR 5246, ICBMS, equipe CSAp, 43 boulevard du 11 novembre 1918, Villeurbanne, F-69622 (France); Seta, Patrick [Institut Europeen des Membranes, UMR CNRS 5635, 1919 route de Mende, 34293 Montpellier (France)

2008-07-01

The complexation abilities of different thiacalix[4]arene derivatives towards some rare earth metal ions, metallic pollutants, and noble metals have been investigated in liquid-liquid experiments. Thiacalix[4]arene dissolved in chloroform effectively extracts Pd(II) (in acidic chloride media) and also Ag(I), Cd(II), Sm(III) and Ce(III), all buffered at pH 6 or 8. The modification of this compound to form an amide derivative results in an effective extraction of noble metals, ranked according to Au(III) > Pd(II) > Pt(IV) > Ag(I). Moreover, a supported liquid membrane system for silver transport has been developed based on thiacalix[4]arene dissolved in NPOE, and parameters affecting its efficiency have been investigated, such as the stripping composition and the pH of the feed solution. Finally, the selectivity of the membrane system has been evaluated by using as feed sources mixtures of silver and other metal ion000.

Simulated optical properties of noble metallic nanopolyhedra with different shapes and structures

Science.gov (United States)

Zhang, An-Qi; Qian, Dong-Jin; Chen, Meng

2013-11-01

The optical properties of nanostructured architectures are highly sensitive to their compositions, structures, dimensions, geometries and embedding mediums. Nanopolyhedra, including homogeneous metal nanoparticles and core-shell structures, have unique optical properties. In the beginning of this study, Discrete Dipole Approximation (DDA) method has been introduced. Then the simulated extinction spectra of single-component metal nanoparticles and Au@Ag polyhedra were calculated using both Mie and DDA methods. The influence of morphology and components on the optical response is discussed and well-supported by previously published experimental results. It is observed that the Localized Surface Plasmon Resonance peaks are mainly decided by sharp vertexes and symmetry of noble metallic polyhedra, as well as the structure of the Au@Ag core-shell nanoparticles.

Enzyme-Free Electrochemical Glucose Sensors Prepared by Dealloying Pd-Ni-P Metallic Glasses

Directory of Open Access Journals (Sweden)

Yuqiao Zeng

2014-01-01

Full Text Available We report the formation of enzyme-free electrochemical glucose sensors by electrochemical dealloying palladium-containing Pd-Ni-P metallic glasses. When metallic glasses with different Pd contents are used as the dealloying precursor alloys, palladium-based nanoporous metals with different ligament and pore sizes can be obtained. The chemical compositions of the nanoporous metals also vary according to the different precursor compositions. All the as-obtained nanoporous metals exhibit electrochemical catalytic activity towards the oxidation of d-glucose, indicating that the nanoporous metals prepared by dealloying the Pd-Ni-P metallic glasses are promising materials for enzyme-free electrochemical glucose sensor.

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

Science.gov (United States)

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.

Effect of Ni and noble metals (Ru, Pd and Pt) on performance of bifunctional MoP/SiO2 for hydroconversion of methyl laurate

Science.gov (United States)

Nie, Ziyang; Zhang, Zhena; Chen, Jixiang

2017-10-01

SiO2 supported bifunctional MoP catalysts modified with different metal promoters (Ni, Ru, Pd, Pt), where Mo/Ni and Mo/M(M = Ru, Pd and Pt) atomic ratios was respectively 10 and 40, were prepared by TPR method from the phosphate precursors. It was found that the introduction of metal promoters facilitated the reduction of phosphate precursor and enhanced the dispersion of MoP. However, the MoP catalyst acidity was scarcely influenced by the small amount of metal promoters. In the hydroconversion of methyl laurate, the promoters enhanced the MoP catalyst activity for conversion of methyl laurate and hydrogenation of alkenes (intermediate), but reduced isomerization ability. Among the promoters, Ru was an optimum to decrease selectivity to alkenes while maintain high selectivity to iso-alkanes, and Mo40RuP showed better stability than MoP. At 380 °C and 3.0 MPa, the conversion of methyl laurate, the total selectivity to C11 and C12 hydrocarbons and the selectivity to iso-alkanes maintained at 100%, ∼94% and ∼30% on Mo40RuP during 102 h, respectively. The good stability of Mo40RuP is ascribed to that the presence of Ru prevented the sintering of MoP particles and suppressed carbon deposition.

Bare and protected sputtered-noble-metal films for surface-enhanced Raman spectroscopy

Science.gov (United States)

Talaga, David; Bonhommeau, Sébastien

2014-11-01

Sputtered silver and gold films with different surface morphologies have been prepared and coated with a benzenethiol self-assembled monolayer. Rough noble metal films showed strong Raman features assigned to adsorbed benzenethiol molecules upon irradiation over a wide energy range in the visible spectrum, which disclosed the occurrence of a significant surface-enhanced Raman scattering with maximal enhancement factors as high as 6 × 106. In addition, the adsorption of ethanethiol onto silver surfaces hinders their corrosion over days while preserving mostly intact enhancement properties of naked silver. This study may be applied to develop stable and efficient metalized probes for tip-enhanced Raman spectroscopy.

Highly selective electrodeposition of sub-10 nm crystalline noble metallic nanorods inside vertically aligned multiwall carbon nanotubes

Science.gov (United States)

Wang, Xuyang; Wang, Ranran; Wu, Qiang; Zhang, Xiaohua; Yang, Zhaohui; Guo, Jun; Chen, Muzi; Tang, Minghua; Cheng, Yajun; Chu, Haibin

2016-07-01

In this paper crystalline noble metallic nanorods including Au and Ag with sub-10 nm diameter, are encapsulated within prealigned and open-ended multiwall carbon nanotubes (MWCNTs) through an electrodeposition method. As the external surface of CNTs has been insulated by the epoxy the CNT channel becomes the only path for the mass transport as well as the nanoreactor for the metal deposition. Highly crystallized Au and Ag2O nanorods parallel to the radial direction of CNTs are confirmed by high-resolution transmission electron microscopy, energy dispersive x-ray spectroscopy and x-ray powder diffraction spectroscopy. The Ag2O nanorods are formed by air oxidation on the Ag metals and show a single crystalline structure with (111) planes. The Au nanorods exhibit a complex crystalline structure including twin-crystal and lattice dislocation with (111) and (200) planes. These crystalline noble metallic nanostructures may have important applications for nanocatalysts for fuel cells as well as nanoelectronic and nanophotonic devices. This method is deemed to benefit the precise deposition of other crystalline nanostructures inside CNTs with a small diameter.

Ni supported CdIn2S4 spongy-like spheres: a noble metal free high-performance sunlight driven photocatalyst for hydrogen production.

Science.gov (United States)

Vu, Manh-Hiep; Nguyen, Chinh-Chien; Sakar, M; Do, Trong-On

2017-11-08

Nickel supported CdIn 2 S 4 (Ni-CIS) spongy-like spheres have been developed using alcoholysis followed by a sulfidation process. The formation of nanocrystalline-single phase CdIn 2 S 4 was confirmed using X-ray diffraction studies. Electron microscopy images showed that the spongy-like spheres are composed of CdIn 2 S 4 nanoparticles with average sizes of around 25 nm. X-ray photoelectron spectra indicated the presence of elements with their respective stable oxidation states that led to the formation of single phase CdIn 2 S 4 with enhanced structural integrity and chemical composition. The absorption spectra indicated the visible light activity of the material and the band gap energy is deduced to be 2.23 eV. The photocatalytic efficiency of the synthesized Ni-CIS in relation to its ability to produce hydrogen under solar light irradiation is estimated to be 1060 μmol g -1 h -1 , which is around 5.5 and 3.6 fold higher than that of Pt-CIS (180 μmol g -1 h -1 ) and Pd-CIS (290 μmol g -1 h -1 ), respectively, as obtained in this study. Accordingly, the mechanism of the observed efficiency of the Ni-CIS nanoparticles is also proposed. The recyclability test showed consistent hydrogen evolution efficiency over 3 cycles (9 h), which essentially revealed the excellent photo- and chemical-stability of the photocatalyst. The strategy to utilize non-noble metals such as Ni, rather than noble-metals, as a co-catalyst opens up a new possibility to develop low cost and high-performance sunlight-driven photocatalysts as achieved in this study.

Investigation of the noble metal deposition behaviour in boiling water reactors - the NORA project

International Nuclear Information System (INIS)

Ritter, S.; Karastoyanov, V.; Abolhassani-Dadras, S.; Guenther-Leopold, I.; Kivel, N.

2010-01-01

NobleChem™ is a technology developed by General Electric to reduce stress corrosion cracking (SCC) in reactor internals and recirculation pipes of boiling water reactors (BWRs) while preventing the negative side effects of classical hydrogen water chemistry. Noble metals (Pt, Rh) acting as electrocatalysts for the recombination of O 2 and H 2 O 2 with H 2 to H 2 O and thus reducing the corrosion potential more efficiently are injected into the feed water during reactor shut-down (classical method) or on-line during power operation. They are claimed to deposit as very fine metallic particles on all water-wetted surfaces including the most critical regions inside existing cracks and to stay electrocatalytic over long periods of time. The effectiveness of this technology in plants remains still to be demonstrated. Based on highly credible laboratory experiments down to the sub-ppb Pt concentration range, SCC mitigation may be expected, provided that a stoichiometric excess of H 2 and a sufficient surface coverage with very fine Pt particles exist simultaneously at the critical locations. Very little is known about the deposition and (re-)distribution behaviour of the Pt in the reactor. For the validation of this technique the research project NORA (noble metal deposition behaviour in BWRs) has been started at PSI with two main objectives: (i) to gain phenomenological insights and a better basic understanding of the Pt distribution and deposition behaviour in BWRs; (ii) to develop and qualify a non-destructive technique to characterise the size and distribution of the Pt particles and its local concentration on reactor components. This paper presents the objectives of the project, the planned work and a brief description of the status of the project. (author)

Corrosion resistance of amorphous and crystalline Pd40Ni40P20 alloys in aqueous solutions

DEFF Research Database (Denmark)

Wu, Y.F.; Chiang, Wen-Chi; Chu, J.

2006-01-01

The corrosion behaviors of amorphous and crystalline Pd40Ni40P20 alloys in various aqueous solutions are reported in this paper. The corrosion resistance of crystalline (annealed) Pd40Ni40P20 is better than that of amorphous Pd40Ni40P20 in various corrosive solutions, due to crystalline Pd40Ni40P20...... and mainly consists of inert Pd5P2, NI3P, Ni2Pd2P and noble Pd phases. These inert and noble properties result in a higher corrosion resistance in crystalline Pd40Ni40P20....

Nanostructure analysis of friction welded Pd-Ni-P/Pd-Cu-Ni-P metallic glass interface

International Nuclear Information System (INIS)

Ohkubo, T.; Shoji, S.; Kawamura, Y.; Hono, K.

2005-01-01

Friction welded Pd 40 Ni 40 P 20 /Pd 40 Cu 30 Ni 10 P 20 metallic glass interface has been characterized by energy filtering transmission electron microscopy. The interface is fully amorphous with a gradual compositional change of Cu and Ni in the range of 30 nm. By annealing above T g , the interdiffusion of Cu and Ni progressed in the supercooled liquid region, and the crystallization occurred from the Pd 40 Ni 40 P 20 glass

Geological structure and prospects of noble metal ore mineralization of the Khayrkhan gabbroid massif (Western Mongolia)

Science.gov (United States)

Kurumshieva, K. R.; Gertner, I. F.; Tishin, P. A.

2017-12-01

An analysis of the distribution of noble metals in zones of sulfide mineralization makes it possible to justify the isolation of four ore-bearing horizons with a specific geochemical zonation. A rise in the gold content relative to palladium and platinum is observed from the bottom upwards along the section of the stratified series of gabbroids. The study of the mineral phases of sulphides and the noble minerals itself indicates the evolution of hydrothermal solutions, which determines the different activity and mobility of the fluid (mercury, tellurium, sulfur) and ore (copper, nickel, iron, platinum, gold and silver) components.

In Situ Studies of Surface Mobility on Noble Metal Model Catalysts Using STM and XPS at Ambient Pressure

Energy Technology Data Exchange (ETDEWEB)

Butcher, Derek Robert [Univ. of California, Berkeley, CA (United States)

2010-06-01

are present on the Pt(100) hex reconstructed phase, but not the (100)-(1x1) surface. The increase in ethylene pressure caused the adsorbate interactions to dominate the crystal morphology and imposed a surface layer structure that matched the ethylidyne binding geometry. The STM results also showed that the surface was reversibly deformed during imaging due to increases in Pt mobility at high pressure. The size dependence on the activity and surface chemistry of Rh nanoparticles was studied using AP-XPS. The activity was found to increase with particle size. The XPS spectra show that in reaction conditions the particle surface has an oxide layer which is chemically distinct from the surface structure formed by heating in oxygen alone. This surface oxide which is stabilized in the catalytically active CO oxidation conditions was found to be more prevalent on the smaller nanoparticles. The reaction-induced surface segregation behavior of bimetallic noble metal nanoparticles was observed with APXPS. Monodisperse 15 nm RhPd and PdPt nanoparticles were synthesized with well controlled Rh/Pd and Pd/Pt compositions. In-situ XPS studies showed that at 300 C in the presence of an oxidizing environment (100 mTorr NO or O₂) the surface concentration of the more easily oxidized element (Rh in RhPd and Pd in PdPt) was increased. Switching the gas environment to more reducing conditions (100 mTorr NO and 100 mTorr CO) caused the surface enrichment of the element with the lowest surface energy in its metallic state. Using in-situ characterization, the redox chemistry and the surface composition of bimetallic nanoparticle samples were monitored in reactive conditions. The particle surfaces were shown to reversibly restructure in response to the gas environment at high temperature. The oxidation behavior of the Pt(110) surface was studied using surface sensitive in-situ characterization by APXPS and STM. In the presence of 500 mTorr O₂ and temperatures between 25

Shape-controlled synthesis of Pd polyhedron supported on polyethyleneimine-reduced graphene oxide for enhancing the efficiency of hydrogen evolution reaction

Science.gov (United States)

Li, Jing; Zhou, Panpan; Li, Feng; Ma, Jianxin; Liu, Yang; Zhang, Xueyao; Huo, Hongfei; Jin, Jun; Ma, Jiantai

2016-01-01

The catalytic activity of noble-metal nanoparticles (NPs) often has closely connection with their sizes and geometric shape. In the work, polyhedral NPs of palladium (Pd) with controlled sizes, shapes, and different proportions of {100} to {111} facets on the surface were prepared by a seed-mediated approach. Electrochemical experiment demonstrates that the catalytic performance of the Pd nanocubes (NCs) enclosed by {100} facets is more active than Pd octahedrons enclosed by {111} facets for the hydrogen evolution reaction (HER), which is consistent with density functional theory (DFT) calculation results. Meanwhile, with the assistance of a polyethyleneimine-reduced graphene oxide (PEI-rGO) support, the examined Pd cube/PEI-rGO50:1 (10 wt. %) electrocatalyst presents outstanding HER activity comparable with that of commercial Pt/C catalyst. This correlation between the HER catalytic activity and surface structure will contribute to the reasonable design of Pd catalysts for HER with high efficiency and low metal loading.

The determination, by x-ray-fluorescence spectrometry, of noble and base metals in matte-leach residues

International Nuclear Information System (INIS)

Austen, C.E.

1977-01-01

An accurate and precise method is described for the determination of noble and base metals in matte-leach residues. Preparation of the samples essentially involves fusion with sodium peroxide in a zirconium crucible and leaching with hydrochloric and nitric acids. Matrix correction and calibration are achieved by use of the single-standard calibration method with reference solutions prepared from pure metals or from compounds of the element to be determined

Conversion of ion-exchange resins, catalysts and sludges to glass with optional noble metal recovery using the GMODS process

International Nuclear Information System (INIS)

Forsberg, C.W.; Beahm, E.C.

1996-01-01

Chemical processing and cleanup of waste streams (air and water) typically result in products, clean air, clean water, and concentrated hazardous residues (ion exchange resins, catalysts, sludges, etc.). Typically, these streams contain significant quantities of complex organics. For disposal, it is desirable to destroy the organics and immobilize any heavy metals or radioactive components into stable waste forms. If there are noble metals in the residues, it is desirable to recover these for reuse. The Glass Material Oxidation and Dissolution System (GMODS) is a new process that directly converts radioactive and hazardous chemical wastes to borosilicate glass. GMODS oxidizes organics with the residue converted to glass; converts metals, ceramics, and amorphous solids to glass; converts halides (eg chlorides) to borosilicate glass and a secondary sodium halide stream; and recovers noble metals. GMODS has been demonstrated on a small laboratory scale (hundreds of grams), and the equipment needed for larger masses has been identified

An investigation of the mimetic enzyme activity of two-dimensional Pd-based nanostructures

Science.gov (United States)

Wei, Jingping; Chen, Xiaolan; Shi, Saige; Mo, Shiguang; Zheng, Nanfeng

2015-11-01

In this work, we investigated the mimetic enzyme activity of two-dimensional (2D) Pd-based nanostructures (e.g. Pd nanosheets, Pd@Au and Pd@Pt nanoplates) and found that they possess intrinsic peroxidase-, oxidase- and catalase-like activities. These nanostructures were able to activate hydrogen peroxide or dissolved oxygen for catalyzing the oxidation of organic substrates, and decompose hydrogen peroxide to generate oxygen. More systematic investigations revealed that the peroxidase-like activities of these Pd-based nanomaterials were highly structure- and composition-dependent. Among them, Pd@Pt nanoplates displayed the highest peroxidase-like activity. Based on these findings, Pd-based nanostructures were applied for the colorimetric detection of H2O2 and glucose, and also the electro-catalytic reduction of H2O2. This work offers a promising prospect for the application of 2D noble metal nanostructures in biocatalysis.In this work, we investigated the mimetic enzyme activity of two-dimensional (2D) Pd-based nanostructures (e.g. Pd nanosheets, Pd@Au and Pd@Pt nanoplates) and found that they possess intrinsic peroxidase-, oxidase- and catalase-like activities. These nanostructures were able to activate hydrogen peroxide or dissolved oxygen for catalyzing the oxidation of organic substrates, and decompose hydrogen peroxide to generate oxygen. More systematic investigations revealed that the peroxidase-like activities of these Pd-based nanomaterials were highly structure- and composition-dependent. Among them, Pd@Pt nanoplates displayed the highest peroxidase-like activity. Based on these findings, Pd-based nanostructures were applied for the colorimetric detection of H2O2 and glucose, and also the electro-catalytic reduction of H2O2. This work offers a promising prospect for the application of 2D noble metal nanostructures in biocatalysis. Electronic supplementary information (ESI) available: TEM images, EDX and dispersion stability of Pd-based nanomaterials

Ultra-low Pt decorated PdFe Alloy Nanoparticles for Formic Acid Electro-oxidation

International Nuclear Information System (INIS)

Zhou, Yawei; Du, Chunyu; Han, Guokang; Gao, Yunzhi; Yin, Geping

2016-01-01

Highlights: • A cost-efficient way is used to prepare transition-noble metal alloy nanoparticles. • The Pd 50 Fe 50 /C catalyst shows excellent activity for formic acid oxidation (FAO). • Much activity enhancement of FAO is acquired by ultra-low Pt decorated Pd 50 Fe 50 . • A synergistic mechanism between Pt clusters and PdFe is proposed during the FAO. - Abstract: Palladium (Pd), has demonstrated promising electro-catalytic activity for formic acid oxidation, but suffers from extremely low abundance. Recently alloying with a transition metal has been considered as an effective approach to reducing the loading of Pd and enhancing the activity of Pd-based catalysts simultaneously. Herein, carbon supported PdFe nanoparticles (NPs) are synthesized at room temperature by using sodium borohydride as reducing agent and potassium ferrocyanide as Fe precursor. The Pd 50 Fe 50 alloy sample annealed at 900 °C for 1 h shows the best catalytic activity among Pd x Fe 1-x (x = 0.2, 0.4, 0.5, 0.6, and 0.8) towards formic acid oxidation. To further improve both catalytic activity and stability, the ultra-low Pt (0.09 wt %) decorated Pd 50 Fe 50 NPs (PtPd/PdFe) are prepared via the galvanic replacement reaction. Compared with Pd 50 Fe 50 /C, the PtPd/PdFe/C Exhibits 1.52 times higher catalytic activity and lower onset potential (−0.12 V). The significant enhancements of formic acid oxidation can be attributed to the accelerated dehydrogenation reaction of formic acid by Pt atomic clusters. Moreover, the PtPd/PdFe/C also demonstrates better tolerance to poisons during formic acid oxidation.

Effects of metal composition and ratio on peptide-templated multimetallic PdPt nanomaterials

International Nuclear Information System (INIS)

Merrill, Nicholas A.; Nitka, Tadeusz T.; McKee, Erik M.; Merino, Kyle C.; Drummy, Lawrence F.

2017-01-01

It can be difficult to simultaneously control the size, composition, and morphology of metal nanomaterials under benign aqueous conditions. For this, bioinspired approaches have become increasingly popular due to their ability to stabilize a wide array of metal catalysts under ambient conditions. In this regard, we used the R5 peptide as a three-dimensional template for formation of PdPt bimetallic nanomaterials. Monometallic Pd and Pt nanomaterials have been shown to be highly reactive toward a variety of catalytic processes, but by forming bimetallic species, increased catalytic activity may be realized. The optimal metal-to-metal ratio was determined by varying the Pd:Pt ratio to obtain the largest increase in catalytic activity. To better understand the morphology and the local atomic structure of the materials, the bimetallic PdPt nanomaterials were extensively studied by transmission electron microscopy, extended X-ray absorption fine structure spectroscopy, X-ray photoelectron spectroscopy, and pair distribution function analysis. The resulting PdPt materials were determined to form multicomponent nanostructures where the Pt component demonstrated varying degrees of oxidation based upon the Pd:Pt ratio. To test the catalytic reactivity of the materials, olefin hydrogenation was conducted, which indicated a slight catalytic enhancement for the multicomponent materials. Finally, these results suggest a strong correlation between the metal ratio and the stabilizing biotemplate in controlling the final materials morphology, composition, and the interactions between the two metal species.

Effects of Metal Composition and Ratio on Peptide-Templated Multimetallic PdPt Nanomaterials

Energy Technology Data Exchange (ETDEWEB)

Merrill, Nicholas A.; Nitka, Tadeusz T.; McKee, Erik M.; Merino, Kyle C.; Drummy, Lawrence F.; Lee, Sungsik; Reinhart, Benjamin; Ren, Yang; Munro, Catherine J.; Pylypenko, Svitlana; Frenkel, Anatoly I.; Bedford, Nicholas M.; Knecht, Marc R.

2017-02-22

It can be difficult to simultaneously control the size, composition, and morphology of metal nanomaterials under benign aqueous conditions. For this, bio-inspired approaches have become increasing popular due to their ability to stabilize a wide array of metal catalysts under ambient conditions. In this regard, we used the R5 peptide as a 3D template for the formation of PdPt bimetallic nanomaterials. Monometallic Pd and Pt nanomaterials have been shown to be highly reactive towards a variety of catalytic processes, but by forming bimetallic species, increased catalytic activity may be realized. The optimal metal-to-metal ratio was determined by varying the Pd:Pt ratio to obtain the largest increase in catalytic activity. To better understand the morphology and the local atomic structure of the materials, the bimetallic PdPt nanomaterials were extensively studied using transmission electron microscopy, extended X-ray absorption fine structure spectroscopy, X-ray photoelectron spectroscopy, and pair distribution function analysis. The resulting PdPt materials were determined to form multicomponent nanostructures where the Pt component demonstrated varying degrees of oxidation based upon the Pd:Pt ratio. To test the catalytic reactivity of the materials, olefin hydrogenation was conducted which indicated a slight catalytic enhancement for the multicomponent materials. These results suggest a strong correlation between the metal ratio and the stabilizing biotemplate in controlling the final materials morphology, composition, and the interactions between the two metal species.

Structure and Mobility of Metal Clusters in MOFs: Au, Pd, and AuPd Clusters in MOF-74

DEFF Research Database (Denmark)

Vilhelmsen, Lasse; Walton, Krista S.; Sholl, David S.

2012-01-01

is just as important for nanocluster adsorption as open Zn or Mg metal sites. Using the large number of clusters generated by the GA, we developed a systematic method for predicting the mobility of adsorbed clusters. Through the investigation of diffusion paths a relationship between the cluster......Understanding the adsorption and mobility of metal–organic framework (MOF)-supported metal nanoclusters is critical to the development of these catalytic materials. We present the first theoretical investigation of Au-, Pd-, and AuPd-supported clusters in a MOF, namely MOF-74. We combine density...... functional theory (DFT) calculations with a genetic algorithm (GA) to reliably predict the structure of the adsorbed clusters. This approach allows comparison of hundreds of adsorbed configurations for each cluster. From the investigation of Au8, Pd8, and Au4Pd4 we find that the organic part of the MOF...

Wigner Distribution Functions as a Tool for Studying Gas Phase Alkali Metal Plus Noble Gas Collisions

Science.gov (United States)

2014-03-27

WIGNER DISTRIBUTION FUNCTIONS AS A TOOL FOR STUDYING GAS PHASE ALKALI METAL PLUS NOBLE GAS COLLISIONS THESIS Keith A. Wyman, Second Lieutenant, USAF...the U.S. Government and is not subject to copyright protection in the United States. AFIT-ENP-14-M-39 WIGNER DISTRIBUTION FUNCTIONS AS A TOOL FOR...APPROVED FOR PUBLIC RELEASE; DISTRIBUTION UNLIMITED AFIT-ENP-14-M-39 WIGNER DISTRIBUTION FUNCTIONS AS A TOOL FOR STUDYING GAS PHASE ALKALI METAL PLUS

Crystal phase-based epitaxial growth of hybrid noble metal nanostructures on 4H/fcc Au nanowires

Science.gov (United States)

Lu, Qipeng; Wang, An-Liang; Gong, Yue; Hao, Wei; Cheng, Hongfei; Chen, Junze; Li, Bing; Yang, Nailiang; Niu, Wenxin; Wang, Jie; Yu, Yifu; Zhang, Xiao; Chen, Ye; Fan, Zhanxi; Wu, Xue-Jun; Chen, Jinping; Luo, Jun; Li, Shuzhou; Gu, Lin; Zhang, Hua

2018-03-01

Crystal-phase engineering offers opportunities for the rational design and synthesis of noble metal nanomaterials with unusual crystal phases that normally do not exist in bulk materials. However, it remains a challenge to use these materials as seeds to construct heterometallic nanostructures with desired crystal phases and morphologies for promising applications such as catalysis. Here, we report a strategy for the synthesis of binary and ternary hybrid noble metal nanostructures. Our synthesized crystal-phase heterostructured 4H/fcc Au nanowires enable the epitaxial growth of Ru nanorods on the 4H phase and fcc-twin boundary in Au nanowires, resulting in hybrid Au-Ru nanowires. Moreover, the method can be extended to the epitaxial growth of Rh, Ru-Rh and Ru-Pt nanorods on the 4H/fcc Au nanowires to form unique hybrid nanowires. Importantly, the Au-Ru hybrid nanowires with tunable compositions exhibit excellent electrocatalytic performance towards the hydrogen evolution reaction in alkaline media.

[Studies on high temperature oxidation of noble metal alloys for dental use. (III) On high temperature oxidation resistance of noble metal alloys by adding small amounts of alloying elements. (author's transl)].

Science.gov (United States)

Ohno, H

1976-11-01

The previous report pointed out the undesirable effects of high temperature oxidation on the casting. The influence of small separate additions of Zn, Mg, Si, Be and Al on the high temperature oxidation of the noble metal alloys was examined. These alloying elements were chosen because their oxide have a high electrical resistivity and they have much higher affinity for oxygen than Cu. The casting were oxidized at 700 degrees C for 1 hour in air. The results obtained were as follows: 1. The Cu oxides are not observed on the as-cast surface of noble metal alloys containing small amounts of Zn, Mg, Si, Be, and Al. The castings have gold- or silver-colored surface. 2. After heating of the unpolished and polished castings, the additions of Si, Be and Al are effective in preventing oxidation of Cu in the 18 carats gold alloys. Especially the golden surface is obtained by adding Be and Al. But there is no oxidation-resistance on the polished castings in the alloys containing Zn and Mg. 3. The zinc oxide film formed on the as-cast specimen is effective in preventing of oxidation Cu in 18 carats gold alloys. 4. It seems that the addition of Al is most available in dental application.

Facile synthesis of PdAgTe nanowires with superior electrocatalytic activity

Science.gov (United States)

Hong, Wei; Wang, Jin; Wang, Erkang

2014-12-01

In this work, ultrathin Te nanowires (NWs) with high-aspect-ratio are prepared by a simple hydrothermal method. By using Te NWs as the sacrificial template, we demonstrate a facile and efficient method for the synthesis of PdAgTe NWs with high-quality through the partly galvanic replacement between Te NWs and the corresponding noble metal salts precursors in an aqueous solution. The compositions of PdAgTe NWs can be tuned by simply altering the concentration of the precursors. After cyclic voltammetry treatment, multi-component PdAgTe NW with a highly active and stable surface can be obtained. The structure and composition of the as-prepared nanomaterials are analyzed by transmission electron microscope, X-ray diffraction, energy dispersive X-ray spectroscopy, inductively coupled plasma-mass spectroscopy and X-ray photoelectron spectroscopy. Electrochemical catalytic measurement results prove that the as synthesized PdAgTe NWs present superior catalytic activity toward ethanol electrooxidation in alkaline solution than the commercial Pd/C catalyst, which making them can be used as effective catalysts for the direct ethanol fuel cells.

Synthesis of Pd and Rh metal nanoparticles in the interlayer space of organically modified montmorillonite

International Nuclear Information System (INIS)

Patel, Hasmukh A.; Bajaj, Hari C.; Jasra, Raksh Vir

2008-01-01

This study reports the synthesis of palladium and rhodium metal nanoparticles supported on montmorillonite (MMT) and partially organically modified MMT (POMM) using tetraamine palladium and hexaamine rhodium complex as precursor for palladium and rhodium respectively. The synthesized nanoparticles were characterized by powder X-ray diffraction PXRD and TEM. The PXRD study shows characteristic crystallographic planes for Pd and Rh metal and confirm the formation of metal nanoparticles in MMT and POMM. The TEM images reveal the effect of organic modification of MMT on decreasing particle size of Pd and Rh metal. The Pd and Rh metal nanoparticles are agglomerated in pristine MMT while nanoparticles are well dispersed in POMM. ICP-AES analysis was carried out to estimate quantitative amount of Pd and Rh metal in MMT and POMM

Three-dimensional noble-metal nanostructure: A new kind of substrate for sensitive, uniform, and reproducible surface-enhanced Raman scattering

International Nuclear Information System (INIS)

Tian Cui-Feng; You Hong-Jun; Fang Ji-Xiang

2014-01-01

Surface-enhanced Raman spectroscopy (SERS) is a powerful vibrational spectroscopy technique for highly sensitive structural detection of low concentration analyte. The SERS activities largely depend on the topography of the substrate. In this review, we summarize the recent progress in SERS substrate, especially focusing on the three-dimensional (3D) noble-metal substrate with hierarchical nanostructure. Firstly, we introduce the background and general mechanism of 3D hierarchical SERS nanostructures. Then, a systematic overview on the fabrication, growth mechanism, and SERS property of various noble-metal substrates with 3D hierarchical nanostructures is presented. Finally, the applications of 3D hierarchical nanostructures as SERS substrates in many fields are discussed. (invited review — international conference on nanoscience and technology, china 2013)

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

Science.gov (United States)

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.

Mechanism of NO Photocatalytic Oxidationon g-C3N4 Was Changed by Pd-QDs Modification

Directory of Open Access Journals (Sweden)

Yuhan Li

2015-12-01

Full Text Available Quantum dot (QD sensitization can increase the light absorption and electronic transmission of photocatalysts. However, limited studies have been conducted on the photocatalytic activity of photocatalysts after modification by noble metal QDs. In this study, we developed a simple method for fabricating Pd-QD-modified g-C3N4. Results showed that the modification of Pd-QDs can improve the NO photocatalytic oxidation activity of g-C3N4. Moreover, Pd-QD modification changed the NO oxidation mechanism from the synergistic action of h+ and O2− to the single action of ·OH. We found that the main reason for the mechanism change was that Pd-QD modification changed the molecular oxygen activation pathway from single-electron reduction to two-electron reduction. This study can not only develop a novel strategy for modifying Pd-QDs on the surface of photocatalysts, but also provides insight into the relationship between Pd-QD modification and the NO photocatalytic oxidation activity of semiconductor photocatalysts.

A Phenomenological Study on the Synergistic Role of Precious Metals in the Steam Reforming of Logistic Fuels on Bimetal-Supported Catalysts

Directory of Open Access Journals (Sweden)

Abdul-Majeed Azad

2011-01-01

Full Text Available Fuel processors are required to convert sulfur-laden logistic fuels into hydrogen-rich reformate and deliver to the fuel cell stack with little or no sulfur. Since sulfur poisons and deactivates the reforming catalyst, robust sulfur-tolerant catalysts ought to be developed. In this paper, the development, characterization and evaluation of a series of reforming catalysts containing two noble metals (with total metal loading not exceeding 1 weight percent supported on nanoscale ceria for the steam-reforming of kerosene is reported. Due to inherent synergy, a bimetallic catalyst is superior to its monometallic analog, for the same level of loading. The choice of noble metal combination in the bimetallic formulations plays a vital and meaningful role in their performance. Presence of ruthenium and/or rhodium in formulations containing palladium showed improved sulfur tolerance and significant enhancement in their catalytic activity and stability. Rhodium was responsible for higher hydrogen yields in the logistic fuel reformate. Duration of steady hydrogen production was higher in the case of RhPd (75 h than for RuPd (68 h; hydrogen generation was stable over the longest period (88 h with RuRh containing no Pd. A mechanistic correlation between the characteristic role of precious metals in the presence of each other is discussed.

A fast response hydrogen sensor with Pd metallic grating onto a fiber's end-face

Science.gov (United States)

Yan, Haitao; Zhao, Xiaoyan; Zhang, Chao; Li, Qiu-Ze; Cao, Jingxiao; Han, Dao-Fu; Hao, Hui; Wang, Ming

2016-01-01

We demonstrated an integrated hydrogen sensor with Pd metallic grating fabricated on a fiber end-face. The grating consists of three thin metal layers in stacks, Au, WO3 and Pd. The WO3 is used as a waveguide layer between the Pd and Au layer. The Pd layer is etched by using a focused ion beam (FIB) method, forming a Pd metallic grating with period of 450 nm. The sensor is experimentally exposed to hydrogen gas environment. Changing the concentration from 0% to 4% which is the low explosive limit (LEL), the resonant wavelength measured from the reflection experienced 28.10 nm spectral changes in the visible range. The results demonstrated that the sensor is sensitive for hydrogen detection and it has fast response and low temperature effect.

Automated ion-exchange system for the radiochemical separation of the noble metals

International Nuclear Information System (INIS)

Parry, S.J.

1980-01-01

Ion-exchange separation is particularly suitable for mechanisation and automated ion exchange has been applied to the activation analysis of biological and environmental samples. In this work a system has been designed for experimental studies, which can be adapted for different modes of operation. The equipment is based on a large-volume sampler for the automatic presentation of 500 ml of liquid to a sampling probe. The sample is delivered to the ion-exchange column by means of a peristaltic pump. The purpose of this work was to automate a procedure for separating the noble metals from irradiated geological samples, for neutron-activation analysis. The process of digesting the rock sample is carried out manually in 30 min and is not suited to unattended operation. The volume of the resulting liquid sample may be 100 ml and so the manual separation step may take as long as 1.25 h per sample. The reason for automating this part of the procedure is to reduce the separation time for a group of five samples and consequently to improve the sensitivity of the analysis for radionuclides with short half-lives. This paper describes the automatic ion-exchange system and the ways in which it can be used. The mode of operation for the separation of the noble metals is given in detail. The reproducibility of the system has been assessed by repeated measurements on a standard reference matte. (author)

Surface Functionalization of g-C 3 N 4 : Molecular-Level Design of Noble-Metal-Free Hydrogen Evolution Photocatalysts

KAUST Repository

Chen, Yin; Lin, Bin; Yu, Weili; Yang, Yong; Bashir, Shahid M.; Wang, Hong; Takanabe, Kazuhiro; Idriss, Hicham; Basset, Jean-Marie

2015-01-01

A stable noble-metal-free hydrogen evolution photocatalyst based on graphite carbon nitride (g-C3N4) was developed by a molecular-level design strategy. Surface functionalization was successfully conducted to introduce a single nickel active site

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

DEFF Research Database (Denmark)

Andersen, O. Krogh

1970-01-01

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

Noble metal-free RGO/TiO2 composite nanofiber with enhanced photocatalytic H2-production performance

Science.gov (United States)

Xu, Difa; Li, Lingling; He, Rongan; Qi, Lifang; Zhang, Liuyang; Cheng, Bei

2018-03-01

1D reduced graphene oxide (RGO)/TiO2 nanocomposite fibers were fabricated by a facile two-step method. These samples demonstrated high photocatalytic H2-production activity from methanol aqueous solution, even without the aid of noble metal. When the ratio of RGO is 0.25 wt%, the highest H2-production rate was achieved. It increased by 10 fold than bare TiO2, reaching 149 μmol h-1 g-1 with quantum efficiency (QE) of 0.75%. The reasons were as follows. Firstly, the RGO nanosheets acted as electron acceptors. Secondly, some shallow trap states at the surface or interface of TiO2 were created by the reduction of GO during calcination. Thirdly, the redox potential position of graphene/graphene- was suitable. Fourthly, RGO could efficiently promote the separation of photogenerated electron-hole pairs and significantly enhance the photocatalytic H2-production activity. This interpretation was corroborated by transient photocurrent response. The aforementioned marvelous results provided a probable solution to replace noble metals (such as Pt) by graphene as an effective cocatalyst.

Production of mono- and bimetallic nanoparticles of noble metals by pyrolysis of organic extracts on silicon dioxide

International Nuclear Information System (INIS)

Serga, V; Kulikova, L; Cvetkov, A; Krumina, A; Kodols, M; Chornaja, S; Dubencovs, K; Sproge, E

2013-01-01

In the present work the influence of the tri-n-octylammonium (Oct 3 NH + ) salt anion (PtCl 6 2- , PdCl 4 2- , AuCl 4 − ) nature on the phase composition and mean size of crystallites of the extract pyrolysis products on the SiO 2 nanopowder has been studied. The XRD phase analysis of the composites (metal loading 2.4 wt.%) made under the same conditions, at the pyrolysis of Pt- and Au-containing extracts has shown the formation of nanoparticles of Pt (d Pt = 15 nm) and Au (d Au = 33 nm), respectively. The end-product of the pyrolysis of the Pd-containing extract has an admixture phase of PdO along with the main metal phase (d Pd = 21 nm). At the preparation of bimetallic particles (Pt-Pd, Pt-Au, Pd-Au) on the SiO 2 nanopowder it has been found that the nanoparticles of the PtPd alloy, Pt and Au or Pd and Au nanoparticles are the products of the thermal decomposition of two-component mixtures of extracts. The investigation of catalytic properties of the produced composites in the reaction of glycerol oxidation by molecular oxygen in alkaline aqueous solutions has shown that all bimetallic composites exhibit catalytic activity in contrast to monometallic ones

Development of guidelines on the application of noble metals to BWRs

International Nuclear Information System (INIS)

Wood, C.J.; Cowan, R.L.

2002-01-01

Water Chemistry plays a critical role in determining the economics of BWR (boiling water reactor) operation. The chemistry controls the probability of repairs due to stress corrosion cracking of piping and internals, the operating and shutdown dose rates (and thus personnel exposure), radiation waste generation and fuel corrosion performance. Simultaneously addressing the adverse effects from these phenomena requires a delicate balance of chemistry variables. Earlier papers have reviewed the technologies that have evolved to provide this balance including specific impurity limits, hydrogen water chemistry, and isotopically depleted zinc injection. This paper addresses the experience with the latest technology, noble metal chemical addition (NMCA). (authors)

Development of guidelines on the application of noble metals to BWRs

Energy Technology Data Exchange (ETDEWEB)

Wood, C.J. [EPRI, Palo Alto, CA (United States); Cowan, R.L

2002-07-01

Water Chemistry plays a critical role in determining the economics of BWR (boiling water reactor) operation. The chemistry controls the probability of repairs due to stress corrosion cracking of piping and internals, the operating and shutdown dose rates (and thus personnel exposure), radiation waste generation and fuel corrosion performance. Simultaneously addressing the adverse effects from these phenomena requires a delicate balance of chemistry variables. Earlier papers have reviewed the technologies that have evolved to provide this balance including specific impurity limits, hydrogen water chemistry, and isotopically depleted zinc injection. This paper addresses the experience with the latest technology, noble metal chemical addition (NMCA). (authors)

Noble metal emissions. Final presentation, Hanover, October 17/18, 1996; Edelmetall - Emissionen. Abschlusspraesentation, Hannover, 17. und 18. Oktober 1996. Kurzfassung der Vortraege

Energy Technology Data Exchange (ETDEWEB)

Pohl, D [comp.

1998-12-31

The discussion concerning noble metal emissions, in particular platinum emissions, and their environmental effects, started with the introduction of catalytical cleaning of gasoline engine exhaust. The Research Association for Noble Metal Emissions (Forschungsverbund Edelmetallemissionen) ws founded for the purpose of investigating problems concerning the types and volumes of noble metal emissions as well as their toxicological and allergological potential. In order to make valid statements on physiological and toxicological effects, it was necessary to identify the chemical forms of platinum and to develop powerful methods of analysis. Investigations of platinum concentrations in environmental samples suggest a 10 percent bioavailability. [Deutsch] Mit der Einfuehrung der katalytischen Abgasreinigung von Ottomotoren begann gleichzeitig die Diskussion ueber moegliche Emissionen von Edelmetallen, insbesondere von Platin, sowie ueber ihre eventuell moeglichen negativen Wirkungen in der Umwelt. Zur Erforschung der Fragestellungen zur Art und Menge der emittierten Platinmetalle, ihrer Aufnahme und dem Uebergang in den Nahrungskreislauf, sowie zu ihrem toxikologischen und allergologischen Potential wurde der Forschungsverbund ``Edelmetallemissionen`` gegruendet. Um Aussagen ueber physiologische und toxikologische Einfluesse zu machen, war es notwendig, die chemischen Erscheinungsformen des Platins zu identifizieren und nachweisstarke Analysenmethoden zu entwickeln. Untersuchungen zu Platinkonzentrationen in Umweltproben deuten auf eine Bioverfuegbarkeit von ca. 10 % hin. (ABI)

Noble metal emissions. Final presentation, Hanover, October 17/18, 1996; Edelmetall - Emissionen. Abschlusspraesentation, Hannover, 17. und 18. Oktober 1996. Kurzfassung der Vortraege

Energy Technology Data Exchange (ETDEWEB)

Pohl, D. [comp.

1997-12-31

The discussion concerning noble metal emissions, in particular platinum emissions, and their environmental effects, started with the introduction of catalytical cleaning of gasoline engine exhaust. The Research Association for Noble Metal Emissions (Forschungsverbund Edelmetallemissionen) ws founded for the purpose of investigating problems concerning the types and volumes of noble metal emissions as well as their toxicological and allergological potential. In order to make valid statements on physiological and toxicological effects, it was necessary to identify the chemical forms of platinum and to develop powerful methods of analysis. Investigations of platinum concentrations in environmental samples suggest a 10 percent bioavailability. [Deutsch] Mit der Einfuehrung der katalytischen Abgasreinigung von Ottomotoren begann gleichzeitig die Diskussion ueber moegliche Emissionen von Edelmetallen, insbesondere von Platin, sowie ueber ihre eventuell moeglichen negativen Wirkungen in der Umwelt. Zur Erforschung der Fragestellungen zur Art und Menge der emittierten Platinmetalle, ihrer Aufnahme und dem Uebergang in den Nahrungskreislauf, sowie zu ihrem toxikologischen und allergologischen Potential wurde der Forschungsverbund ``Edelmetallemissionen`` gegruendet. Um Aussagen ueber physiologische und toxikologische Einfluesse zu machen, war es notwendig, die chemischen Erscheinungsformen des Platins zu identifizieren und nachweisstarke Analysenmethoden zu entwickeln. Untersuchungen zu Platinkonzentrationen in Umweltproben deuten auf eine Bioverfuegbarkeit von ca. 10 % hin. (ABI)

Catalytic activity of polypyrrole nanotubes decorated with noble-metal nanoparticles and their conversion to carbonized analogues

Czech Academy of Sciences Publication Activity Database

Sapurina, Irina; Stejskal, Jaroslav; Šeděnková, Ivana; Trchová, Miroslava; Kovářová, Jana; Hromádková, Jiřina; Kopecká, J.; Cieslar, M.; Abu El-Nasr, A.; Ayad, M. M.

2016-01-01

Roč. 214, April (2016), s. 14-22 ISSN 0379-6779 R&D Projects: GA ČR(CZ) GA13-00270S; GA MŠk(CZ) LH14199; GA MŠk(CZ) LO1507 Institutional support: RVO:61389013 Keywords : conducting polymer * polypyrrole nanotubes * noble metals Subject RIV: CD - Macromolecular Chemistry Impact factor: 2.435, year: 2016

Interaction of noble-metal fission products with pyrolytic silicon carbide

International Nuclear Information System (INIS)

Lauf, R.J.; Braski, D.N.

1982-01-01

Fuel particles for the High-Temperature Gas-Cooled Reactor (HTGR) contain layers of pyrolytic carbon and silicon carbide, which act as a miniature pressure vessel and form the primary fission product barrier. Of the many fission products formed during irradiation, the noble metals are of particular interest because they interact significantly with the SiC layer and their concentrations are somewhat higher in the low-enriched uranium fuels currently under consideration. To study fission product-SiC interactions, particles of UO 2 or UC 2 are doped with fission product elements before coating and are then held in a thermal gradient up to several thousand hours. Examination of the SiC coatings by TEM-AEM after annealing shows that silver behaves differently from the palladium group

Development of Non-Noble Metal Ni-Based Catalysts for Dehydrogenation of Methylcyclohexane

KAUST Repository

Al-ShaikhAli, Anaam H.

2016-11-30

Liquid organic chemical hydride is a promising candidate for hydrogen storage and transport. Methylcyclohexane (MCH) to toluene (TOL) cycle has been considered as one of the feasible hydrogen carrier systems, but selective dehydrogenation of MCH to TOL has only been achieved using the noble Pt-based catalysts. The aim of this study is to develop non-noble, cost-effective metal catalysts that can show excellent catalytic performance, mainly maintaining high TOL selectivity achievable by Pt based catalysts. Mono-metallic Ni based catalyst is a well-known dehydrogenation catalyst, but the major drawback with Ni is its hydrogenolysis activity to cleave C-C bonds, which leads to inferior selectivity towards dehydrogenation of MCH to TOL. This study elucidate addition of the second metal to Ni based catalyst to improve the TOL selectivity. Herein, ubiquitous bi-metallic nanoparticles catalysts were investigated including (Ni–M, M: Ag, Zn, Sn or In) based catalysts. Among the catalysts investigated, the high TOL selectivity (> 99%) at low conversions was achieved effectively using the supported NiZn catalyst under flow of excess H2. In this work, a combined study of experimental and computational approaches was conducted to determine the main role of Zn over Ni based catalyst in promoting the TOL selectivity. A kinetic study using mono- and bimetallic Ni based catalysts was conducted to elucidate reaction mechanism and site requirement for MCH dehydrogenation reaction. The impact of different reaction conditions (feed compositions, temperature, space velocity and stability) and catalyst properties were evaluated. This study elucidates a distinctive mechanism of MCH dehydrogenation to TOL reaction over the Ni-based catalysts. Distinctive from Pt catalyst, a nearly positive half order with respect to H2 pressure was obtained for mono- and bi-metallic Ni based catalysts. This kinetic data was consistent with rate determining step as (somewhat paradoxically) hydrogenation

The growth of noble metals in (112-bar0)-oriented hexagonal close-packed nano-films by epitaxy on Nb(001)

International Nuclear Information System (INIS)

Hueger, E.; Osuch, K.

2005-01-01

The morphology and crystal structure of noble metal nano-films deposited on oxygen contaminated and oxygen-free Nb(001) surfaces have been studied with angle-resolved ultraviolet photoelectron spectroscopy, X-ray photo-electron diffraction, and reflection high energy electron diffraction. In the both cases a deposited noble metal film aligns its direction with the [110] direction of the Nb(001) surface. But, while a noble metal grows on an oxygen contaminated Nb(001) surface with the hexagonal close-packed (hcp) (111) planes parallel to the surface (i.e. in the (111)-oriented face centred cubic phase (fcc)), on a non-contaminated Nb(001) it grows with its hcp planes perpendicular to the surface. The latter happens because in the initial stages of the epitaxy the first two monolayers (MLs) of the noble metal grow pseudomorphically on a contamination-free Nb(001). The pseudomorphic layer is strongly extended parallel to the Nb(001) surface in comparison to its natural fcc (001) plane. As a consequence of the atomic volume conservation principle the out-of-plane lattice of the pseudomorphic layer is contracted. Thus, its body centred tetragonal (110) planes, which stay perpendicular to the surface, contract into denser-packed planes, i.e. in hcp ones. In the direction perpendicular to the surface, where the substrate does not have a direct influence on the film, the pseudomorphic layer relaxes into its natural close-packed phase, i.e. into hcp atomic planes. These planes appear as soon as the third pseudomorphic ML begins to grow. The stacking axis of the planes lies in the (100) surface of Nb and is locked by it. The fact that thick nano-films of Cu (up to 50 MLs), Ag and Au (up to 100 MLs) grow in the (112-bar0)-oriented hcp phase can be attributed to a much better fit of the hcp than of fcc stacking sequence to the four-fold symmetry of the Nb(001) surface

Hydrogen storage in Pd nanocrystals covered with a metal-organic framework

Science.gov (United States)

Li, Guangqin; Kobayashi, Hirokazu; Taylor, Jared M.; Ikeda, Ryuichi; Kubota, Yoshiki; Kato, Kenichi; Takata, Masaki; Yamamoto, Tomokazu; Toh, Shoichi; Matsumura, Syo; Kitagawa, Hiroshi

2014-08-01

Hydrogen is an essential component in many industrial processes. As a result of the recent increase in the development of shale gas, steam reforming of shale gas has received considerable attention as a major source of H2, and the more efficient use of hydrogen is strongly demanded. Palladium is well known as a hydrogen-storage metal and an effective catalyst for reactions related to hydrogen in a variety of industrial processes. Here, we present remarkably enhanced capacity and speed of hydrogen storage in Pd nanocrystals covered with the metal-organic framework (MOF) HKUST-1 (copper(II) 1,3,5-benzenetricarboxylate). The Pd nanocrystals covered with the MOF have twice the storage capacity of the bare Pd nanocrystals. The significantly enhanced hydrogen storage capacity was confirmed by hydrogen pressure-composition isotherms and solid-state deuterium nuclear magnetic resonance measurements. The speed of hydrogen absorption in the Pd nanocrystals is also enhanced by the MOF coating.

Analysis of noble metal on automotive exhaust catalysts by radioisotope-induce x-ray fluorescence

International Nuclear Information System (INIS)

Elgart, M.F.

1976-01-01

A technique was developed for the in-situ analysis of noble metals deposited on monolithic automotive exhaust catalysts. This technique is based on radioisotope-induced x-ray fluorescence, and provides a detailed picture of the distribution of palladium and platinum on catalyst samples. The experimental results for the cross section of a monolithic exhaust catalyst, analyzed in increments of 0.2 cm 3 , are compared with analyses for palladium and platinum obtained by instrumental neutron activation analysis

Examining changes in cellular communication in neuroendocrine cells after noble metal nanoparticle exposure.

Science.gov (United States)

Love, Sara A; Liu, Zhen; Haynes, Christy L

2012-07-07

As nanoparticles enjoy increasingly widespread use in commercial applications, the potential for unintentional exposure has become much more likely during any given day. Researchers in the field of nanotoxicity are working to determine the physicochemical nanoparticle properties that lead to toxicity in an effort to establish safe design rules. This work explores the effects of noble metal nanoparticle exposure in murine chromaffin cells, focusing on examining the effects of size and surface functionality (coating) in silver and gold, respectively. Carbon-fibre microelectrode amperometry was utilized to examine the effect of exposure on exocytosis function, at the single cell level, and provided new insights into the compromised functions of cells. Silver nanoparticles of varied size, between 15 and 60 nm diameter, were exposed to cells and found to alter the release kinetics of exocytosis for those cells exposed to the smallest examined size. Effects of gold were examined after modification with two commonly used 'bio-friendly' polymers, either heparin or poly (ethylene glycol), and gold nanoparticles were found to induce altered cellular adhesion or the number of chemical messenger molecules released, respectively. These results support the body of work suggesting that noble metal nanoparticles perturb exocytosis, typically altering the number of molecules and kinetics of release, and supports a direct disruption of the vesicle matrix by the nanoparticle. Overall, it is clear that various nanoparticle physicochemical properties, including size and surface coating, do modulate changes in cellular communication via exocytosis.

Studies on PEM fuel cell noble metal catalyst dissolution

DEFF Research Database (Denmark)

Andersen, S. M.; Grahl-Madsen, L.; Skou, E. M.

2011-01-01

A combination of electrochemical, spectroscopic and gravimetric methods was carried out on Proton Exchange Membrane (PEM) fuel cell electrodes with the focus on platinum and ruthenium catalysts dissolution, and the membrane degradation. In cyclic voltammetry (CV) experiments, the noble metals were...... found to dissolve in 1 M sulfuric acid solution and the dissolution increased exponentially with the upper potential limit (UPL) between 0.6 and 1.6 vs. RHE. 2-20% of the Pt (depending on the catalyst type) was found to be dissolved during the experiments. Under the same conditions, 30-100% of the Ru...... (depending on the catalyst type) was found to be dissolved. The faster dissolution of ruthenium compared to platinum in the alloy type catalysts was also confirmed by X-ray diffraction measurements. The dissolution of the carbon supported catalyst was found one order of magnitude higher than the unsupported...

Efficient recovery of gold and other noble metals from electronic and other scraps

Energy Technology Data Exchange (ETDEWEB)

Baba, Hidetoshi

1987-01-01

Pure gold is extracted from crude gold by the solvent extraction method in the recovery and refining process for Noble metals recovered from electronic and other scraps. This solvent extraction method is advantageous in that it facilitates rapid processing, thereby reducing the interest burden of gold staying too long in the unit. Therefore, the method is also used in the refining of platinum and palladium. Technological innovation has created more complex and diversified types of scraps, and efforts are being made to accommodate ourselves to such a trend.

Leaching characteristics of the metal waste form from the electrometallurgical treatment process: Product consistency testing

International Nuclear Information System (INIS)

Johnson, S. G.; Keiser, D. D.; Frank, S. M.; DiSanto, T.; Noy, M.

1999-01-01

Argonne National Laboratory is developing an electrometallurgical treatment for spent fuel from the experimental breeder reactor II. A product of this treatment process is a metal waste form that incorporates the stainless steel cladding hulls, zirconium from the fuel and the fission products that are noble to the process, i.e., Tc, Ru, Nb, Pd, Rh, Ag. The nominal composition of this waste form is stainless steel/15 wt% zirconium/1--4 wt% noble metal fission products/1--2 wt % U. Leaching results are presented from several tests and sample types: (1) 2 week monolithic immersion tests on actual metal waste forms produced from irradiated cladding hulls, (2) long term (>2 years) pulsed flow tests on samples containing technetium and uranium and (3) crushed sample immersion tests on cold simulated metal waste form samples. The test results will be compared and their relevance for waste form product consistency testing discussed

Journal of Chemical Sciences | Indian Academy of Sciences

Indian Academy of Sciences (India)

While adsorption of CO on noble metals ions is well-known, adsorption of CO on noble metal ions has not been studied because creating exclusive ionic sites has been difficult. Using first-principles density functional theory (DFT) we have shown that CO gets adsorbed on the noble metal Pt2+, Pd2+, Cu2+ ionic sites in the ...

Experimental and computational approaches to evaluate the environmental mitigation effect in narrow spaces by noble metal chemical addition (NMCA)

International Nuclear Information System (INIS)

Shimizu, Ryosuke; Ota, Nobuyuki; Nagase, Makoto; Aizawa, Motohiro; Ishida, Kazushige; Wada, Yoichi

2014-01-01

The environmental mitigation effect of NMCA in a narrow space was evaluated by experimental and computational approaches. In the experiment at 8 MPa and 553K, T-tube whose branched line had a narrow space was prepared, and the Zr electrodes were set in the branched line at certain intervals, which were 1, 3, 5, 7, 9, 11, 15 and 29 cm from the opening section of the branched line. Electrochemical corrosion potential (ECP) at the tip of the branched narrow space varied in response to the water chemistry in the main line which was at right angle with the branched line. Computational fluid dynamics (CFD) analysis reproduced the experimental results. It was also confirmed by CFD analysis that the ingress of water from the main line into the narrow space was accelerated by cavity flow and thermal convection. By CFD analysis in a thermal sleeve of actual plant condition, which had a narrow space, the concentration of dissolved oxygen at a tip of the thermal sleeve reached at 250 ppb within 300 sec, which was the same concentration of the main line. Noble metal deposition on the surface of the thermal sleeve was evaluated by mass transfer model. Noble metal deposition was the largest near the opening section of the branched line, and gradually decreased toward the tip section. In light of the consumption of dissolved oxygen in the branched line, noble metal deposition in the thermal sleeve was sufficient to reduce the ECP. It was expected that NMCA could mitigate the corrosion environment in the thermal sleeve. (author)

Electronic structure of transition metal dichalcogenides PdTe2 and Cu0.05PdTe2 superconductors obtained by angle-resolved photoemission spectroscopy

International Nuclear Information System (INIS)

Liu Yan; Zhao Jian-Zhou; Yu Li; Hu Cheng; Liu De-Fa; Peng Ying-Ying; Xie Zhuo-Jin; He Jun-Feng; Chen Chao-Yu; Feng Ya; Yi He-Mian; Liu Xu; Zhao Lin; He Shao-Long; Liu Guo-Dong; Dong Xiao-Li; Zhang Jun; Lin Cheng-Tian; Chen Chuang-Tian; Xu Zu-Yan

2015-01-01

The layered transition metal chalcogenides have been a fertile land in solid state physics for many decades. Various MX 2 -type transition metal dichalcogenides, such as WTe 2 , IrTe 2 , and MoS 2 , have triggered great attention recently, either for the discovery of novel phenomena or some extreme or exotic physical properties, or for their potential applications. PdTe 2 is a superconductor in the class of transition metal dichalcogenides, and superconductivity is enhanced in its Cu-intercalated form, Cu 0.05 PdTe 2 . It is important to study the electronic structures of PdTe 2 and its intercalated form in order to explore for new phenomena and physical properties and understand the related superconductivity enhancement mechanism. Here we report systematic high resolution angle-resolved photoemission (ARPES) studies on PdTe 2 and Cu 0.05 PdTe 2 single crystals, combined with the band structure calculations. We present in detail for the first time the complex multi-band Fermi surface topology and densely-arranged band structure of these compounds. By carefully examining the electronic structures of the two systems, we find that Cu-intercalation in PdTe 2 results in electron-doping, which causes the band structure to shift downwards by nearly 16 meV in Cu 0.05 PdTe 2 . Our results lay a foundation for further exploration and investigation on PdTe 2 and related superconductors. (rapid communication)

A facile one-pot solvothermal method for synthesis of magnetically recoverable Pd-Fe3O4 hybrid nanocatalysts for the Mizoroki-Heck reaction

Science.gov (United States)

Zhen, Fangchen; Ran, Maofei; Chu, Wei; Jiang, Chengfa; Sun, Wenjing

2018-03-01

Pd-Fe3O4 hybrid nanostructures were prepared using a simple one-pot hydrothermal method. The prepared materials were characterized by Fourier transform-infrared spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, transmission electron microscopy, inductively coupled plasma, N2 adsorption-desorption, and vibrating sample magnetometry. This self-assembled nanosystem acted as an efficient magnetically recyclable noble metal-based multi-functional nanocatalyst. It showed excellent catalytic activity and stability for the Heck reaction of iodobenzene and styrene under mild conditions. The methods used to prepare the Pd-Fe3O4 catalysts were simple and low-cost, which will be useful for the large-scale development and application of a magnetically recoverable Pd catalyst.

Noble metal-catalyzed homogeneous and heterogeneous processes in treating simulated nuclear waste media with formic acid

International Nuclear Information System (INIS)

King, R.B.; Bhattacharyya, N.K.; Smith, H.D.

1995-09-01

Simulants for the Hanford Waste Vitrification Plant feed containing the major non-radioactive components Al, Cd, Fe, Mn, Nd, Ni, Si, Zr, Na, CO 3 2 -, NO 3 -, and NO 2 - were used to study reactions of formic acid at 90 degrees C catalyzed by the noble metals Ru, Rh, and/or Pd found in significant quantities in uranium fission products. Such reactions were monitored using gas chromatography to analyze the CO 2 , H 2 , NO, and N 2 O in the gas phase and a microammonia electrode to analyze the NH 4 +/NH 3 in the liquid phase as a function of time. The following reactions have been studied in these systems since they are undesirable side reactions in nuclear waste processing: (1) Decomposition of formic acid to CO 2 + H 2 is undesirable because of the potential fire and explosion hazard of H 2 . Rhodium, which was introduced as soluble RhCl 3 -3H 2 O, was found to be the most active catalyst for H 2 generation from formic acid above ∼ 80 degrees C in the presence of nitrite ion. The H 2 production rate has an approximate pseudo first-order dependence on the Rh concentration, (2) Generation of NH 3 from the formic acid reduction of nitrate and/or nitrite is undesirable because of a possible explosion hazard from NH 4 NO 3 accumulation in a waste processing plant off-gas system. The Rh-catalyzed reduction of nitrogen-oxygen compounds to ammonia by formic acid was found to exhibit the following features: (a) Nitrate rather than nitrite is the principal source of NH 3 . (b) Ammonia production occurs at the expense of hydrogen production. (c) Supported rhodium metal catalysts are more active than rhodium in any other form, suggesting that ammonia production involves heterogeneous rather than homogeneous catalysis

Synthesis of PdO/MCM-41 nanocomposites using trans-[PdCl2(PEt3)2] as the source of metal

International Nuclear Information System (INIS)

Hernandez-Pineda, Jessica; Rio, Jose Manuel del; Carreto, Enrique; Terres, Eduardo; Montoya, J. Asencion; Zuniga-Gonzalez, Maria de Jesus; Morgado, Jorge

2009-01-01

Three PdO/MCM-41 nanocomposites containing PdO species that are dispersed on an MCM-41 support have been prepared using trans-[PdCl 2 (PEt 3 ) 2 ] as the source of metal. Thermal gravimetric analysis of the decomposition of this complex in air reveals a remarkable mass loss of all nonmetallic elements centered at 300 deg. C. The materials were characterized with X-ray powder diffraction (XRPD), nitrogen sorption and TEM, which showed that the PdO nanoparticles were present inside the pores of MCM-41. XRPD analysis confirms formation of PdO (palladinite) nanocrystals, as the sole crystalline phase present in the nanocomposites.

The effect of noble metal additives on the optimum operating temperature of SnO2 gas sensors

Science.gov (United States)

Mohammad-Yousefi, S.; Rahbarpour, S.; Ghafoorifard, H.

2017-12-01

The effect of Pd and Au additives on gas sensing properties of SnO2 was investigated. SnO2 pallets were fabricated and sintered at 900 °C for 90 minutes. Several nanometer layers of Pd and Au were deposited on separate SnO2 pallets and were intentionally dispersed into the SnO2 pallets by long heat treatment (400 °C for 1 Day). All metal loaded samples showed significant enhancement in response level and optimum operating temperature compare to pure SnO2 gas sensors. The amount of enhancement was strongly dependent on the material and the thickness of deposited metal layer. Studying butanol response showed that increasing the thickness of metal causes the response level to increase. Further thickness increase caused contrary effect and decreased the performance of sensors. Best results were achieved at 10 nm-thick Au and 7 nm-thick Pd. Generally, Pd-SnO2 samples demonstrated better performance than Au-SnO2 ones, however, Au-SnO2 samples were proved to be good candidate to sense reducing gases with lower hydrogen atoms in their formula. Given experimental results were also good evidence of chemical activity of gold and simply confirms the relation between chemical activity and gold particle size. Results were qualitatively described by gas diffusion theory and surface reactions take place on metal particles.The first section in your paper

Influence of the noble metals (Pd, Au, Ag) in the thermoluminescent signal induced by radiation in the ZrO{sub 2}; Influencia de los metales nobles (Pd, Au, Ag) en la senal termoluminiscente inducida por la radiacion en la ZrO{sub 2}

Energy Technology Data Exchange (ETDEWEB)

Villa S, G

2006-07-01

When increasing the use of the ionizing and non ionizing radiations (for example, gamma and ultraviolet radiation) in different areas of the science and technology, there is necessary to apply more accurate safety measures and to avoid over-exposures that could put in risk the life of workers that manipulate radiation sources, patient that are exposed to this under some medical treatment, as well as materials that undergo intentionally to radiation. Also, the UV radiation that arrives to the earth can cause some damages, to the one to weaken the protector layer of ozone the UV radiation increases that arrives to the earth surface being able to affect the alive beings and the materials. By this so much the development of new materials able to take a census of in a more accurate way, fields of gamma and UV radiation is becoming necessary. In this sense, this work presents the obtained results when quantifying radiation fields, through the analysis in the thermoluminescent behavior (TL) induced by the gamma and UV radiation in the zirconium dioxide synthesized by the sol gel method and doped with nanoparticles of Pd, Au and Ag. It is necessary to mention that in reported works in this respect its mention that the zircon has good thermoluminescent sensitivity induced by these radiation types, however it has shown high thermoluminescent instability that is translated in an important lost of the information after the irradiation. For that through the incorporation of the metallic nanoparticles it was intended to stabilize the TL behavior of zircon. The results showed that the doped zircon has a high sensitivity to the gamma and UV radiation. These also show that the ionizing and non ionizing radiation induce a thermoluminescent curve consisting of two TL peaks with maxima located around 65 C and 145 C and that the intensity is increased with the dose, following a lineal behavior in certain interval of dose exposure that is influenced by the presence of the nanoparticles

Green Synthesis of Ag and Pd Nanospheres, Nanowires, and Nanorods Using Vitamin B2: Catalytic Polymerisation of Aniline and Pyrrole

Directory of Open Access Journals (Sweden)

Mallikarjuna N. Nadagouda

2008-01-01

Full Text Available For the first time, we report green chemistry approach using vitamin B2 in the synthesis of silver (Ag and palladium (Pd, nanospheres, nanowires, and nanorods at room temperature without using any harmful reducing agents, such as sodium borohydride (NaBH4 or hydroxylamine hydrochloride and any special capping or dispersing agent. Vitamin B2 was used as reducing agent as well as capping agent due to its high-water solubility, biodegradability, and low-toxicity compared with other reducing agents. The average particle size of nanoprticle was found to be Ag (average size 6.1±0.1 nm and Pd (average size 4.1±0.1 nm nanoparticles in ethylene glycol and Ag (average size 5.9±0.1 nm, and average size 6.1±0.1 nanoparticles in acetic acid and NMP, respectively. The formation of noble multiple shape nanostructures and their self assembly were dependent on the solvent employed for the preparation. When water was used as solvent media, Ag and Pd nanoparticles started to self-assemble into rod-like structures and in isopropanol Ag and Pd nanoparticles yielded wire-like structures with a thickness in the range of 10 to 20 nm and several hundred microns in length. In acetone and acetonitrile medium, the Ag and Pd nanoparticles are self-assembled into a regular pattern making nanorod structures with thicknesses ranging from 100 to 200 nm and lengths of a few microns. The so-synthesized nanostructures were characterized using scanning electron microscopy (SEM, transmission electron microscopy (TEM, energy dispersive X-ray (EDX analysis, and UV spectroscopy. The ensuing Ag and Pd nanoparticles catalyzed the reactions of aniline and pyrrole to generate polyaniline and polypyrrole nanofibers and may find various technological and biological applications. This single-step greener approach is general and can be extended to other noble metals and transition metal oxides.

Fatigue and corrosion of a Pd-based bulk metallic glass in various environments

Energy Technology Data Exchange (ETDEWEB)

Watanabe, L.Y. [East Los Angeles College, Monterey Park, CA 91754 (United States); Roberts, S.N. [Keck Laboratory of Materials Science, California Institute of Technology, Pasadena, CA 91125 (United States); Baca, N. [Department of Chemistry and Biochemistry, California State University Northridge, Northridge, CA 91330 (United States); Wiest, A. [Naval Surface Warfare Center, Norco, CA (United States); Garrett, S.J. [Department of Chemistry and Biochemistry, California State University Northridge, Northridge, CA 91330 (United States); Conner, R.D., E-mail: rdconner@csun.edu [Department of Manufacturing Systems Engineering and Management, California State University Northridge, 18111 Nordhoff St., Mail Code 8295, Northridge, CA 91330 (United States)

2013-10-15

Bulk metallic glasses (BMGs) possess attractive properties for biomedical applications, including high strength, hardness and corrosion resistance, and low elastic modulus. In this study, we conduct rotating beam fatigue tests on Pd{sub 43}Ni{sub 10}Cu{sub 27}P{sub 20} bulk metallic glass in air and Eagle's medium (EM) and measure the corrosive resistance of the alloy by submersion in acidic and basic electrolytes. Fatigue results are compared to those of commonly used biometals in EM. Rotating beam fatigue tests conducted in air and in Eagle's medium show no deterioration in fatigue properties in this potentially corrosive environment out to 10{sup 7} cycles. A specimen size effect is revealed when comparing fatigue results to those of a similar alloy of larger minimum dimensions. Corrosion tests show that the alloy is not affected by highly basic (NaOH) or saline (NaCl) solutions, nor in EM, and is affected by chlorinated acidic solutions (HCl) to a lesser extent than other commonly used biometals. Corrosion in HCl initiates with selective leaching of late transition metals, followed by dissolution of Pd. - Highlights: • Fatigue limit of 600 MPa with no deterioration when exposed to Eagle's medium. • Fatigue shows sample size effect. • Pd-based BMG is unaffected by saline or strong basic solutions. • Pd-based BMG is substantially more resistant to chlorinated acids than CoCrMo, 316 L Stainless, or Ti6Al4V alloys. • Corrosion shows selective leaching of late transition metals, followed by Pd and P.

Formation of hydroxyapatite on Ti-coated Ti-Zr-Cu-Pd bulk metallic glass

International Nuclear Information System (INIS)

Qin, F.X.; Wang, X.M.; Wada, T.; Xie, G.Q.; Asami, K.; Inoue, A.

2009-01-01

In this research, Ti coating was conducted on Ti 40 Zr 10 Cu 36 Pd 14 bulk metallic glass (BMG) in order to increase the formation rate of hydroxyapatite layer. The formation behavior of bone-like hydroxyapatite on Ti-coated and uncoated Ti 40 Zr 10 Cu 36 Pd 14 bulk metallic glasses (BMGs) was studied. The surface morphology of Ti-coated and uncoated Ti 40 Zr 10 Cu 36 Pd 14 BMG was investigated by scanning electron microscopy and energy dispersive X-ray spectroscopy. The results revealed that the alkali pretreatment in 5 M NaOH solution at 60degC for 24 h had a beneficial effect on the formation of porous sodium titanate on Ti-coated Ti 40 Zr 10 Cu 36 Pd 14 BMG. A bone-like hydroxyapatite layer was able to form on the alkali-treated Ti-coated Ti 40 Zr 10 Cu 36 Pd 14 BMG after a short-time immersion in simulated body fluid (SBF). On the contrary, hydroxyapatite formation was not observed on the uncoated Ti 40 Zr 10 Cu 36 Pd 14 BMG after the same chemical treatments. (author)

Dithiocarbamate Self-Assembled Monolayers as Efficient Surface Modifiers for Low Work Function Noble Metals

Energy Technology Data Exchange (ETDEWEB)

Meyer, Dominik; Schäfer, Tobias; Schulz, Philip; Jung, Sebastian; Rittich, Julia; Mokros, Daniel; Segger, Ingolf; Maercks, Franziska; Effertz, Christian; Mazzarello, Riccardo; Wuttig, Matthias

2016-09-06

Tuning the work function of the electrode is one of the crucial steps to improve charge extraction in organic electronic devices. Here, we show that N,N-dialkyl dithiocarbamates (DTC) can be effectively employed to produce low work function noble metal electrodes. Work functions between 3.1 and 3.5 eV are observed for all metals investigated (Cu, Ag, and Au). Ultraviolet photoemission spectroscopy (UPS) reveals a maximum decrease in work function by 2.1 eV as compared to the bare metal surface. Electronic structure calculations elucidate how the complex interplay between intrinsic dipoles and dipoles induced by bond formation generates such large work function shifts. Subsequently, we quantify the improvement in contact resistance of organic thin film transistor devices with DTC coated source and drain electrodes. These findings demonstrate that DTC molecules can be employed as universal surface modifiers to produce stable electrodes for electron injection in high performance hybrid organic optoelectronics.

TiN nanoparticles on CNT-graphene hybrid support as noble-metal-free counter electrode for quantum-dot-sensitized solar cells.

Science.gov (United States)

Youn, Duck Hyun; Seol, Minsu; Kim, Jae Young; Jang, Ji-Wook; Choi, Youngwoo; Yong, Kijung; Lee, Jae Sung

2013-02-01

The development of an efficient noble-metal-free counter electrode is crucial for possible applications of quantum-dot-sensitized solar cells (QDSSCs). Herein, we present TiN nanoparticles on a carbon nanotube (CNT)-graphene hybrid support as a noble-metal-free counter electrode for QDSSCs employing a polysulfide electrolyte. The resulting TiN/CNT-graphene possesses an extremely high surface roughness, a good metal-support interaction, and less aggregation relative to unsupported TiN; it also has superior solar power conversion efficiency (4.13 %) when applying a metal mask, which is much higher than that of the state-of-the-art Au electrode (3.35 %). Based on electrochemical impedance spectroscopy measurements, the enhancement is ascribed to a synergistic effect between TiN nanoparticles and the CNT-graphene hybrid, the roles of which are to provide active sites for the reduction of polysulfide ions and electron pathways to TiN nanoparticles, respectively. The combination of graphene and CNTs leads to a favorable morphology that prevents stacking of graphene or bundling of CNTs, which maximizes the contact of the support with TiN nanoparticles and improves electron-transfer capability relative to either carbon material alone. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Science.gov (United States)

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.

Solvent and stabilizer free growth of Ag and Pd nanoparticles using metallic salts/cyclotriphosphazenes mixtures

Energy Technology Data Exchange (ETDEWEB)

Díaz Valenzuela, C. [Departamento de Química, Facultad de Química, Universidad de Chile, La Palmeras 3425, Nuñoa, Casilla 653, Santiago de Chile (Chile); Valenzuela, M.L., E-mail: mlvalenzuela@unab.cl [Universidad Andres Bello, Departamento de Ciencias Química, Facultad de Ciencias Exactas, Av. Republica 275, Santiago (Chile); Caceres, S.; Diaz, R. [Departamento de Química, Facultad de Química, Universidad de Chile, La Palmeras 3425, Nuñoa, Casilla 653, Santiago de Chile (Chile); O' Dwyer, C. [Applied Nanoscience Group, Department of Chemistry, University College Cork, Cork (Ireland); Micro and Nanoelectronics Centre, Tyndall National Institute, Lee Maltings, Cork (Ireland)

2013-12-16

Cyclotriphosphazene is used as a sacrificial solid-state template to synthesize a range of Ag and Pd nanoparticles with diverse geometries by thermal treatment using MLn/N{sub 3}P{sub 3}(O{sub 2}C{sub 12}H{sub 8}){sub 3} mixtures. The Pd and Ag nanoparticles are synthesized by solid-state pyrolysis of AgPPh{sub 3}[CF{sub 3}SO{sub 3}]/N{sub 3}P{sub 3}(O{sub 2}C{sub 12}H{sub 8}){sub 3} and PdCl{sub 2}/N{sub 3}P{sub 3}(O{sub 2}C{sub 12}H{sub 8}){sub 3} mixtures with molar relationships of 1:1, 1:5 and 1:10 respectively, in air and at 800 °C. The morphology of the as-prepared nanoparticles is found to depend on the molar ratio of the precursor mixture, the preparation method and of the nature of the metal. Ag and Pd, microcrystals were thermally grown on Si from the respective 1:1 precursors while that metal foams were grown from 1:5 ratios precursors on SiO{sub 2} wafers. High resolution transmission electron microscopy investigations reveal in most cases small crystals of Pd. HRSTEM measurements indicate that the formation of the Pd and Ag nanoparticles occurs through a phase demixing and dewetting mechanism. This approach has potential to be a useful and facile method to prepare metallic nanoparticles without requiring solutions or surfactants for application in electronic, catalytic and sensor materials and devices. - Highlights: • Pyrolysis MLn/N{sub 3}P{sub 3}(O{sub 2}C{sub 12}H{sub 8}){sub 3} mixtures under air, give Pd and Ag nanoparticles. • AgPPh{sub 3}[CF{sub 3}SO{sub 3}] and PdCl{sub 2} in molar ratios 1:1 and 1:5 were used. • Metal foams were obtained from 1:5 ratios when deposited on SiO{sub 2.} • Using crucible supporting in 1:1 metal/trimer <2 nm Pd nanoparticles were obtained. • The probable mechanism involves a dewetting, nucleation and ripening crystallization.

Characterization of the electrochemical behavior of coating by steel welding 308l and in presence of noble metals deposits; Caracterizacion del comportamiento electroquimico de recubrimiento por soldadura de acero 308L y en presencia de depositos de metales nobles

Energy Technology Data Exchange (ETDEWEB)

Piedras, P.; Arganis J, C. R., E-mail: pedro.piedras@hotmail.es [ININ, Carretera Mexico-Toluca s/n, 52750 Ocoyoacac, Estado de Mexico (Mexico)

2014-10-15

In this work the oxide deposits and noble metals deposit were characterized (Ag and Pt) on a coating of stainless steel 308l that were deposited by the shield metal arc welding (SMAW) on steel A36 by means of scanning electron microscopy, energy-dispersive X-ray spectroscopy and X-ray diffraction. The extrapolation of Tafel technique was also used to obtain the corrosion potential (Ec) for the pre-rusty steel and for the samples with deposits of Pt and Ag under conditions of hydrogen water chemistry (HWC), demonstrating that this parameter diminishes with the presence of this deposits. (Author)

Development of new generation of perovskite based noble metal/semiconductor photocatalysts for visible-light-driven hydrogen production

Science.gov (United States)

Shen, Peichuan

described in this dissertation. Noble metal nanoparticles have been proved to be effective co-catalysts due to their unique physical and chemical properties. Au and Pt nanoparticles with different sizes were synthesized and deposited on CdS. Sub-nanometer Au and Pt were found to be promising co-catalysts for photocatalytic hydrogen production reaction. Specifically, sub-nm Au and sub-nm Pt nanoparticles were found to enhance the photocatalytic activity in hydrogen production of CdS by 35 and 15 times respectively. Other noble metal co-catalysts, such as Ru, Pd and Rh were also deposited on CdS and their photocatalytic activities were investigated. Additionally, a novel chamber for photocatalytic reactions was developed as a part of this dissertation. The reaction chamber has several unique features allowing different reactions and measurements. The reactor was proved to be suitable for future projects in photocatalysis such as photocatalytic CO2 conversion into hydrocarbons.

Effects of noble-metal ion implantation on corrosion inhibition and charge injection capability of surgical Ti and Ti-6Al-4V

International Nuclear Information System (INIS)

Lee, I.S.

1989-01-01

Studies are described involving effects of noble-metal ion implantation on corrosion inhibition and charge injection capabilities of surgical Ti and Ti-6Al-4V. With surgical alloys, harmful biological responses are principally due to the type and quantity of metal ions released by the corrosion process. One approach to improve long-term biological performance involves surface modifications to significantly reduce degradation rates. With regard to surface-modifications, one of the most effective methods is through ion implantation. Results are presented for ion-implanted Au, Rh, and Ir. For the static in vitro corrosion properties, the noble-metal ion implanted Ti-6Al-4V and commercially-pure (CP) Ti were investigated in non-passivating acid and passivating saline solutions. It was postulated that during the early stages of corrosion (or during a corrosion pretreatment) the implanted noble-metal would enrich at the surface and significantly reduce subsequent corrosion rates. The observed behavior for the Ir and Rh implanted materials appeared to follow the postulated mechanism, with both initial and time-dependent improvements in corrosion resistance. However, the Au implanted material yielded early benefits, but the enhanced corrosion resistance deteriorated with time. X-ray photoelectron spectroscopy (XPS) analysis indicated that the implanted Au atoms remained as pure metallic Au, while the Ir and Rh atoms were in some oxide state, which gave the good adhesion of the Ir or Rh enriched surface to the Ti substrate. For a stimulating neural electrode, the charge density should be as large as possible to provide adequate stimulation of the nervous system while allowing for miniaturization of the electrode. Activated Ir has been known as having the highest charge injection capability of any material known

Characterisation and behaviour of Ti/TiO2/noble metal anodes

International Nuclear Information System (INIS)

Gueneau de Mussy, Jean-Paul; Macpherson, Julie V.; Delplancke, Jean-Luc

2003-01-01

The morphology, composition and the electrical and electrochemical behaviour of the anodic microporous layer, prepared by the galvanostatic anodisation of Ti after sparking, followed by galvanostatic deposition of Pt or Ir have been investigated. These electrodes are proposed to function as dimensionally stable anodes (DSAs). For Ti/TiO 2 /Pt electrodes, Pt is deposited within some of the micropores of the oxide film. In contrast, for Ti/TiO 2 /Ir, the metal is deposited preferentially on the top surface. This difference is thought to result from the position of the metal deposition potential with respect to the flat band potential of n-TiO 2 . Optical imaging of both types of DSA suggests that only a few sites on the surface are responsible for electron exchange at the DSA-electrolyte interface. C-AFM measurements of Ti/TiO 2 /Pt samples subjected to long-term anodic polarisation, suggest that the Ti-noble metal contact is progressively insulated by thickening of the TiO 2 barrier layer, promoting passivation of the DSA. For Ir coated anodes, catalytic activity is directly related to the presence of Ir and to the stability of the catalytic oxide layer. Under Cu electrowinning conditions, the electrochemically formed hydrated Ir oxide was found to be catalytically less stable, than the iridium oxide film subjected to a heat treatment

Radiolytic model of Cofrentes NPP using the BWRVIA: analysis of the effectiveness of mitigation in localizations of the vessel with noble metal application on-line; Modelo Radiolitico de C.N. Cofrentes utilizando el BWRVIA: analisis de la efectividad de mitigacion en localizaciones de la vasija con aplicacion de metales nobles on-line

Energy Technology Data Exchange (ETDEWEB)

Sanchez Zapata, J. D.; Martin-Serrano, C.

2013-03-01

Chemistry is one of the principal factors that takes part in IGSCC materials susceptibility. BWR industry has been applying different mitigation techniques against IGSCC: hydrogen injection and noble metals. Mitigation effectiveness is checked by studying chemical parameters: ECP (for hydrogen injection) and Molar Ratio (for noble metal application). There is a software from EPRI called BWRVIA that allows to modelize radiolysis influence in parameters variation and obtain them at different points in the vessel. Recently, this kind of studies have become very relevant within BWR industry because it is the previous step to implement BWRVIP-62-A guidelines in order to get longer inspection intervals at vessel location where mitigation effectiveness is justified, with the cost savings for plants that this means. (Author)

Investigation of Supported Pd-Based Electrocatalysts for the Oxygen Reduction Reaction: Performance, Durability and Methanol Tolerance

Directory of Open Access Journals (Sweden)

Carmelo Lo Vecchio

2015-11-01

Full Text Available Next generation cathode catalysts for direct methanol fuel cells (DMFCs must have high catalytic activity for the oxygen reduction reaction (ORR, a lower cost than benchmark Pt catalysts, and high stability and high tolerance to permeated methanol. In this study, palladium catalysts supported on titanium suboxides (Pd/TinO2n–1 were prepared by the sulphite complex route. The aim was to improve methanol tolerance and lower the cost associated with the noble metal while enhancing the stability through the use of titanium-based support; 30% Pd/Ketjenblack (Pd/KB and 30% Pd/Vulcan (Pd/Vul were also synthesized for comparison, using the same methodology. The catalysts were ex-situ characterized by physico-chemical analysis and investigated for the ORR to evaluate their activity, stability, and methanol tolerance properties. The Pd/KB catalyst showed the highest activity towards the ORR in perchloric acid solution. All Pd-based catalysts showed suitable tolerance to methanol poisoning, leading to higher ORR activity than a benchmark Pt/C catalyst in the presence of low methanol concentration. Among them, the Pd/TinO2n–1 catalyst showed a very promising stability compared to carbon-supported Pd samples in an accelerated degradation test of 1000 potential cycles. These results indicate good perspectives for the application of Pd/TinO2n–1 catalysts in DMFC cathodes.

Noble metal nanoparticle-functionalized ZnO nanoflowers for photocatalytic degradation of RhB dye and electrochemical sensing of hydrogen peroxide

International Nuclear Information System (INIS)

Hussain, Muhammad; Sun, Hongyu; Karim, Shafqat; Nisar, Amjad; Khan, Maaz; Ul Haq, Anwar; Iqbal, Munawar; Ahmad, Mashkoor

2016-01-01

Flower-like hierarchical Zinc oxide nanostructures synthesized by co-precipitation method have been hydrothermally functionalized with 8 nm Au NPs and 15 nm Ag nanoparticles. The photocatalytic and electrochemical performance of these structures are investigated. XPS studies show that the composite exhibits a strong interaction between noble metal nanoparticles (NPs) and Zinc oxide nanoflowers. The PL spectra exhibit UV emission arising due to near band edge transition and show that the reduced PL intensities of Au–ZnO and Ag–ZnO composites are responsible for improved photocatalytic activity arising due to increase in defects. Moreover, the presence of Au NPs on ZnO surface remarkably enhances photocatalytic activity as compared to Ag–ZnO and pure ZnO due to the higher catalytic activity and stability of Au NPs. On the other hand, Ag–ZnO-modified glassy carbon electrode shows good amperometric response to hydrogen peroxide (H_2O_2), with linear range from 1 to 20 µM, and detection limit of 2.5 µM (S/N = 3). The sensor shows high and reproducible sensitivity of 50.8 μA cm"−"2 μM"−"1 with a fast response less than 3 s and good stability as compared to pure ZnO and Au–ZnO-based sensors. All these results show that noble metal NPs-functionalized ZnO base nanocomposites exhibit great prospects for developing efficient non-enzymatic biosensor and environmental remediators.Graphical abstractZnO nanoflowers functionalized with noble metal nanoparticles enhance photocatalytic degradation of RhB dye and electrochemical sensing of hydrogen peroxide.

Noble metal nanoparticle-functionalized ZnO nanoflowers for photocatalytic degradation of RhB dye and electrochemical sensing of hydrogen peroxide

Energy Technology Data Exchange (ETDEWEB)

Hussain, Muhammad [PINSTECH, Nanomaterials Research Group, Physics Division (Pakistan); Sun, Hongyu [Tsinghua University, Laboratory of Advanced Materials and The State Key Laboratory of New Ceramics and Fine Processing, Department of Materials Science and Engineering Beijing, National Center for Electron Microscopy (China); Karim, Shafqat; Nisar, Amjad; Khan, Maaz [PINSTECH, Nanomaterials Research Group, Physics Division (Pakistan); Ul Haq, Anwar [PINSTECH, Non-destructive testing Group (Pakistan); Iqbal, Munawar [University of the Punjab, Centre for High Energy Physics (Pakistan); Ahmad, Mashkoor, E-mail: mashkoorahmad2003@yahoo.com [PINSTECH, Nanomaterials Research Group, Physics Division (Pakistan)

2016-04-15

Flower-like hierarchical Zinc oxide nanostructures synthesized by co-precipitation method have been hydrothermally functionalized with 8 nm Au NPs and 15 nm Ag nanoparticles. The photocatalytic and electrochemical performance of these structures are investigated. XPS studies show that the composite exhibits a strong interaction between noble metal nanoparticles (NPs) and Zinc oxide nanoflowers. The PL spectra exhibit UV emission arising due to near band edge transition and show that the reduced PL intensities of Au–ZnO and Ag–ZnO composites are responsible for improved photocatalytic activity arising due to increase in defects. Moreover, the presence of Au NPs on ZnO surface remarkably enhances photocatalytic activity as compared to Ag–ZnO and pure ZnO due to the higher catalytic activity and stability of Au NPs. On the other hand, Ag–ZnO-modified glassy carbon electrode shows good amperometric response to hydrogen peroxide (H{sub 2}O{sub 2}), with linear range from 1 to 20 µM, and detection limit of 2.5 µM (S/N = 3). The sensor shows high and reproducible sensitivity of 50.8 μA cm{sup −2} μM{sup −1} with a fast response less than 3 s and good stability as compared to pure ZnO and Au–ZnO-based sensors. All these results show that noble metal NPs-functionalized ZnO base nanocomposites exhibit great prospects for developing efficient non-enzymatic biosensor and environmental remediators.Graphical abstractZnO nanoflowers functionalized with noble metal nanoparticles enhance photocatalytic degradation of RhB dye and electrochemical sensing of hydrogen peroxide.

Study of the interface stability of the metal (Mo, Ni, Pd/HfO2/AlN/InGaAs MOS devices

Directory of Open Access Journals (Sweden)

Huy Binh Do

2017-08-01

Full Text Available The degeneration of the metal/HfO2 interfaces for Mo, Ni, and Pd gate metals was studied in this paper. An unstable PdOx interfacial layer formed at the Pd/HfO2 interface, inducing the oxygen segregation for the Pd/HfO2/InGaAs metal oxide capacitor (MOSCAP. The low dissociation energy for the Pd-O bond was the reason for oxygen segregation. The PdOx layer contains O2− and OH− ions which are mobile during thermal annealing and electrical stress test. The phenomenon was not observed for the (Mo, Ni/HfO2/InGaAs MOSCAPs. The results provide the guidance for choosing the proper metal electrode for the InGaAs based MOSFET.

Ion-beam-mixing in metal-metal systems and metal-silicon systems

International Nuclear Information System (INIS)

Hung, L.

1984-01-01

The influence of energetic ion bombardment on the composition and structure of thin film materials and utilization of ion-beam-mixing techniques to modify interfacial reactions are reported in this thesis. The phase formation in metals by using ion mixing techniques has been studied. Upon ion irradiation of Al/Pt, Al/Pd and Al/Ni thin films, only the simplest intermetallic compounds of PdAl and NiAl were formed in crystalline structure, while the amorphous phase has been observed over a large range of composition. Ion mixing of Au/Cu bilayers resulted in the formation of substitutional solid solutions with no trace of ordered compounds. The formation of the ordered compound CuAu was achieved either by irradiation of bilayers with Ar ions at elevated substrate temperature or by irradiation of the mixed layers with He ions at relatively low temperature. In the Au/Al system several crystal compounds existed in the as-deposited samples. These phases remained crystalline or transformed into other equilibrium compounds upon ion irradiation. The results suggest that the phase formation by ion mixing is dependent on the high quench rate in the collision cascade region and the atomic mobility at the irradiation temperature. The argument can be applied to silicide forming systems. With near-noble metals, the mixed atoms are mobile and form metallurgically distinct phases. With refractory metals, amorphous phases are formed due to lack of atomic mobility

A simple alkali-metal and noble gas ion source for SIMS equipments with mass separation of the primary ions

International Nuclear Information System (INIS)

Duesterhoeft, H.; Pippig, R.

1986-01-01

An alkali-metal ion source working without a store of alkali-metals is described. The alkali-metal ions are produced by evaporation of alkali salts and ionization in a low-voltage arc discharge stabilized with a noble gas plasma or in the case of small alkali-metal ion currents on the base of the well known thermic ionization at a hot tungsten wire. The source is very simple in construction and produces a stable ion current of 0.3 μA for more than 100 h. It is possible to change the ion species in a short time. This source is applicable to all SIMS equipments using mass separation for primary ions. (author)

Hydrogen production during processing of radioactive sludge containing noble metals

International Nuclear Information System (INIS)

Ha, B.C.; Ferrara, D.M.; Bibler, N.E.

1992-01-01

Hydrogen was produced when radioactive sludge from Savannah River Site radioactive waste containing noble metals was reacted with formic acid. This will occur in a process tank in the Defense Waste Facility at SRS when waste is vitrified. Radioactive sludges from four tanks were tested in a lab-scale apparatus. Maximum hydrogen generation rates varied from 5 x10 -7 g H 2 /hr/g of sludge from the least reactive sludge (from Waste Tank 51) to 2 x10 -4 g H 2 /hr/g of sludge from the most reactive sludge (from Waste Tank 11). The time required for the hydrogen generation to reach a maximum varied from 4.1 to 25 hours. In addition to hydrogen, carbon dioxide and nitrous oxide were produced and the pH of the reaction slurry increased. In all cases, the carbon dioxide and nitrous oxide were generated before the hydrogen. The results are in agreement with large-scale studies using simulated sludges

Titanium-Niobium Oxides as Non-Noble Metal Cathodes for Polymer Electrolyte Fuel Cells

Directory of Open Access Journals (Sweden)

Akimitsu Ishihara

2015-07-01

Full Text Available In order to develop noble-metal- and carbon-free cathodes, titanium-niobium oxides were prepared as active materials for oxide-based cathodes and the factors affecting the oxygen reduction reaction (ORR activity were evaluated. The high concentration sol-gel method was employed to prepare the precursor. Heat treatment in Ar containing 4% H2 at 700–900 °C was effective for conferring ORR activity to the oxide. Notably, the onset potential for the ORR of the catalyst prepared at 700 °C was approximately 1.0 V vs. RHE, resulting in high quality active sites for the ORR. X-ray (diffraction and photoelectron spectroscopic analyses and ionization potential measurements suggested that localized electronic energy levels were produced via heat treatment under reductive atmosphere. Adsorption of oxygen molecules on the oxide may be governed by the localized electronic energy levels produced by the valence changes induced by substitutional metal ions and/or oxygen vacancies.

Platinum and palladium alloys suitable as fuel cell electrodes

DEFF Research Database (Denmark)

2014-01-01

The present invention concerns electrode catalysts used in fuel cells, such as proton exchange membrane (PEM) fuel cells. The invention is related to the reduction of the noble metal content and the improvement of the catalytic efficiency by low level substitution of the noble metal to provide new...... and innovative catalyst compositions in fuel cell electrodes. The novel electrode catalysts of the invention comprise a noble metal selected from Pt and Pd alloyed with an alkaline earth metal....

Platinum and palladium alloys suitable as fuel cell electrodes

DEFF Research Database (Denmark)

2014-01-01

The present invention concerns electrode catalysts used in fuel cells, such as proton exchange membrane (PEM) fuel cells. The invention is related to the reduction of the noble metal content and the improvement of the catalytic5 efficiency by low level substitution of the noble metal to provide new...... and innovative catalyst compositions in fuel cell electrodes. The novel electrode catalysts of the invention comprise a noble metal selected from Pt and Pd alloyed with a lanthanide metal....

Synergistic effects of semiconductor substrate and noble metal nano-particles on SERS effect both theoretical and experimental aspects

Science.gov (United States)

Yang, Chen; Liang, Pei; Tang, Lisha; Zhou, Yongfeng; Cao, Yanting; Wu, Yanxiong; Zhang, De; Dong, Qianmin; Huang, Jie; He, Peng

2018-04-01

As a means of chemical identification and analysis, Surface enhanced Raman spectroscopy (SERS), with the advantages of high sensitivity and selectivity, non-destructive, high repeatability and in situ detection etc., has important significance in the field of composition detection, environmental science, biological medicine etc. Physical model of coupling effect between different semiconductor substrates and noble metal particles were investigated by using 3D-FDTD method. Mechanism and the effects of excitation wavelength, particle spacing and semiconductor substrate types on the SERS effect were discussed. The results showed that the optimal excitation wavelengths of three noble metals of Ag, Au, Cu, were located at 510, 600 and 630 nm, respectively; SERS effect of Ag, Au, Cu increases with the decreasing of the inter distance of particles, while the distance of the NPs reaches the critical value of 3 nm, the strength of SERS effect will be greatly enhanced. For the four different types of substrate of Ge, Si, SiO2 (glass) and Al2O3, the SERS effect of Ag on SiO2 > Ge > Al2O3 > Si. For Au and Cu nanoparticles, the SERS effect of them on oxide substrate is stronger than that on non-oxide substrate. In order to verify FDTD simulations, taking silver nanoparticles as an example, and silver nanoparticles prepared by chemical method were spinning coating on the four different substrates with R6G as probe molecules. The results show that the experimental results are consistent with FDTD theoretical simulations, and the SERS enhancement effect of Ag-SiO2 substrate is best. The results of this study have important theoretical significance to explain the variations of SERS enhancement on different noble metals, which is also an important guide for the preparation of SERS substrates, especially for the microfluidics. The better Raman effect can be realized by choosing proper substrate type, particle spacing and excitation wavelength, result in expanding the depth and width

Structural changes of noble metal catalysts during ignition and extinction of the partial oxidation of methane studied by advanced QEXAFS techniques

DEFF Research Database (Denmark)

Grunwaldt, Jan-Dierk; Beier, M.; Kimmerle, B.

2009-01-01

The dynamics of the ignition and extinction of the catalytic partial oxidation (CPO) of methane to hydrogen and carbon monoxide over Pt-Rh/Al2O3 and Pt/Al2O3 were studied in the subsecond timescale using quick-EXAFS with a novel cam-driven X-ray monochromator employing Si(111) and Si(311) crystals...... to discuss the potential and limitation of this technique in catalysis and related areas. With respect to the noble metal catalysed partial oxidation of methane, several interesting observations were made: structural changes during ignition were-independent of the chosen reaction conditions......-significantly faster than during the extinction of the reaction. The dynamic behavior of the catalysts was dependent on the flow conditions and the respective noble metal component(s). Higher reaction gas flow led to a faster ignition process. While the ignition over Pt-Rh/Al2O3 occurred at lower temperature than over...

Bimetallic Nanocatalysts in Mesoporous Silica for Hydrogen Production from Coal-Derived Fuels

Energy Technology Data Exchange (ETDEWEB)

Kuila, Debasish [North Carolina Agricultural & Technical State Univ., Greensboro, NC (United States); Ilias, Shamsuddin [North Carolina Agricultural & Technical State Univ., Greensboro, NC (United States)

2013-02-13

In steam reforming reactions (SRRs) of alkanes and alcohols to produce H₂, noble metals such as platinum (Pt) and palladium (Pd) are extensively used as catalyst. These metals are expensive; so, to reduce noble-metal loading, bi-metallic nanocatalysts containing non-noble metals in MCM-41 (Mobil Composition of Material No. 41, a mesoporous material) as a support material with high-surface area were synthesized using one-pot hydrothermal procedure with a surfactant such as cetyltrimethylammonium bromide (CTAB) as a template. Bi-metallic nanocatalysts of Pd-Ni and Pd-Co with varying metal loadings in MCM-41 were characterized by x-ray diffraction (XRD), N₂ adsorption, and Transmission electron microscopy (TEM) techniques. The BET surface area of MCM-41 (~1000 m²/g) containing metal nanoparticles decreases with the increase in metal loading. The FTIR studies confirm strong interaction between Si-O-M (M = Pd, Ni, Co) units and successful inclusion of metal into the mesoporous silica matrix. The catalyst activities were examined in steam reforming of methanol (SRM) reactions to produce hydrogen. Reference tests using catalysts containing individual metals (Pd, Ni and Co) were also performed to investigate the effect of the bimetallic system on the catalytic behavior in the SRM reactions. The bimetallic system remarkably improves the hydrogen selectivity, methanol conversion and stability of the catalyst. The results are consistent with a synergistic behavior for the Pd-Ni-bimetallic system. The performance, durability and thermal stability of the Pd-Ni/MCM-41 and Pd-Co/MCM-41 suggest that these materials may be promising catalysts for hydrogen production from biofuels. A part of this work for synthesis and characterization of Pd-Ni-MCM-41 and its activity for SRM reactions has been published (“Development of Mesoporous Silica Encapsulated Pd-Ni Nanocatalyst for Hydrogen Production” in “Production and Purification of Ultraclean

Separation of 103Pd from metal Rhodium by dry distillation

International Nuclear Information System (INIS)

Szuecs, Z.; Takacs, S.

2009-01-01

Complete text of publication follows. Introduction. The use of Auger emitters as potential radiopharmaceuticals is increasingly investigated. One such radionuclide of interest is 103m Rh. This can be produced from 103 Ru or from 103 Pd in an in vivo generator. It has been proven on theoretical considerations that use of 103 Pd/ 103m Rh in vivo generator will be successful in delivering 103 mRh to a target site when complexed to a tumor selective carrier. 103 Pd is widely used in internal radiotherapy with one of the production routes via the irradiation of Rh by protons in a cyclotron. The charged particle production of 103 Pd is the only way for no-carrier -added production of this radionuclide, which is required for use in nuclear medicine. However, the widely used separation technique to get 103 Pd from the target material (as well as recovery of the Rh) by wet chemistry is a very complicated, labour intensive and expensive procedure, resulting in low yields of 103 Pd and high amounts of radioactive waste. An alternative more efficient separation and production technology can be developed based on differential evaporation. The principle is the following: The produced 103 Pd 'contaminating' new element within the crystal structure of the Rh target can be forced to diffuse out from the deformed crystal lattice by heating up the target. In this process the 103 Pd accumulates on the surface of the target from where it can be evaporated. A prerequisite for this process is that the target metal (Rh) has a different partial pressure than the evaporated metal (Pd). The thick target yield is 6MBq/μ Ah and the activities of potential contaminating radioisotopes produced by side reaction are negligible, if the energy of the irradiating beam will be chosen precisely. The natural abundance of 116 Cd is 7,5%, it means that the price of the enriched material is reasonable. A potential cyclotron facility with α-beam was found at JINR, Dubna, Russia where the radiochemical

Improved ethanol electrooxidation performance by shortening Pd–Ni active site distance in Pd–Ni–P nanocatalysts

Science.gov (United States)

Chen, Lin; Lu, Lilin; Zhu, Hengli; Chen, Yueguang; Huang, Yu; Li, Yadong; Wang, Leyu

2017-01-01

Incorporating oxophilic metals into noble metal-based catalysts represents an emerging strategy to improve the catalytic performance of electrocatalysts in fuel cells. However, effects of the distance between the noble metal and oxophilic metal active sites on the catalytic performance have rarely been investigated. Herein, we report on ultrasmall (∼5 nm) Pd–Ni–P ternary nanoparticles for ethanol electrooxidation. The activity is improved up to 4.95 A per mgPd, which is 6.88 times higher than commercial Pd/C (0.72 A per mgPd), by shortening the distance between Pd and Ni active sites, achieved through shape transformation from Pd/Ni–P heterodimers into Pd–Ni–P nanoparticles and tuning the Ni/Pd atomic ratio to 1:1. Density functional theory calculations reveal that the improved activity and stability stems from the promoted production of free OH radicals (on Ni active sites) which facilitate the oxidative removal of carbonaceous poison and combination with CH3CO radicals on adjacent Pd active sites. PMID:28071650

Influence of the noble metals (Pd, Au, Ag) in the thermoluminescent signal induced by radiation in the ZrO2

International Nuclear Information System (INIS)

Villa S, G.

2006-01-01

When increasing the use of the ionizing and non ionizing radiations (for example, gamma and ultraviolet radiation) in different areas of the science and technology, there is necessary to apply more accurate safety measures and to avoid over-exposures that could put in risk the life of workers that manipulate radiation sources, patient that are exposed to this under some medical treatment, as well as materials that undergo intentionally to radiation. Also, the UV radiation that arrives to the earth can cause some damages, to the one to weaken the protector layer of ozone the UV radiation increases that arrives to the earth surface being able to affect the alive beings and the materials. By this so much the development of new materials able to take a census of in a more accurate way, fields of gamma and UV radiation is becoming necessary. In this sense, this work presents the obtained results when quantifying radiation fields, through the analysis in the thermoluminescent behavior (TL) induced by the gamma and UV radiation in the zirconium dioxide synthesized by the sol gel method and doped with nanoparticles of Pd, Au and Ag. It is necessary to mention that in reported works in this respect its mention that the zircon has good thermoluminescent sensitivity induced by these radiation types, however it has shown high thermoluminescent instability that is translated in an important lost of the information after the irradiation. For that through the incorporation of the metallic nanoparticles it was intended to stabilize the TL behavior of zircon. The results showed that the doped zircon has a high sensitivity to the gamma and UV radiation. These also show that the ionizing and non ionizing radiation induce a thermoluminescent curve consisting of two TL peaks with maxima located around 65 C and 145 C and that the intensity is increased with the dose, following a lineal behavior in certain interval of dose exposure that is influenced by the presence of the nanoparticles

Radiolytic model of Cofrentes NPP using the BWRVIA: analysis of the effectiveness of mitigation in localizations of the vessel with noble metal application on-line

International Nuclear Information System (INIS)

Sanchez Zapata, J. D.; Martin-Serrano, C.

2013-01-01

Chemistry is one of the principal factors that takes part in IGSCC materials susceptibility. BWR industry has been applying different mitigation techniques against IGSCC: hydrogen injection and noble metals. Mitigation effectiveness is checked by studying chemical parameters: ECP (for hydrogen injection) and Molar Ratio (for noble metal application). There is a software from EPRI called BWRVIA that allows to modelize radiolysis influence in parameters variation and obtain them at different points in the vessel. Recently, this kind of studies have become very relevant within BWR industry because it is the previous step to implement BWRVIP-62-A guidelines in order to get longer inspection intervals at vessel location where mitigation effectiveness is justified, with the cost savings for plants that this means. (Author)

Tunable reactivity of supported single metal atoms by impurity engineering of the MgO(001) support.

Science.gov (United States)

Pašti, Igor A; Johansson, Börje; Skorodumova, Natalia V

2018-02-28

Development of novel materials may often require a rational use of high price components, like noble metals, in combination with the possibility to tune their properties in a desirable way. Here we present a theoretical DFT study of Au and Pd single atoms supported by doped MgO(001). By introducing B, C and N impurities into the MgO(001) surface, the interaction between the surface and the supported metal adatoms can be adjusted. Impurity atoms act as strong binding sites for Au and Pd adatoms and can help to produce highly dispersed metal particles. The reactivity of metal atoms supported by doped MgO(001), as probed by CO, is altered compared to their counterparts on pristine MgO(001). We find that Pd atoms on doped MgO(001) are less reactive than on perfect MgO(001). In contrast, Au adatoms bind CO much more strongly when placed on doped MgO(001). In the case of Au on N-doped MgO(001) we find that charge redistribution between the metal atom and impurity takes place even when not in direct contact, which enhances the interaction of Au with CO. The presented results suggest possible ways for optimizing the reactivity of oxide supported metal catalysts through impurity engineering.

Understanding the superior photocatalytic activity of noble metals modified titania under UV and visible light irradiation.

Science.gov (United States)

Bumajdad, Ali; Madkour, Metwally

2014-04-28

Although TiO2 is one of the most efficient photocatalysts, with the highest stability and the lowest cost, there are drawbacks that hinder its practical applications like its wide band gap and high recombination rate of the charge carriers. Consequently, many efforts were directed toward enhancing the photocatalytic activity of TiO2 and extending its response to the visible region. To head off these attempts, modification of TiO2 with noble metal nanoparticles (NMNPs) received considerable attention due to their role in accelerating the transfer of photoexcited electrons from TiO2 and also due to the surface plasmon resonance which induces the photocatalytic activity of TiO2 under visible light irradiation. This insightful perspective is devoted to the vital role of TiO2 photocatalysis and its drawbacks that urged researchers to find solutions such as modification with NMNPs. In a coherent context, we discussed here the characteristics which qualify NMNPs to possess a great enhancement effect for TiO2 photocatalysis. Also we tried to understand the reasons behind this effect by means of photoluminescence (PL) and electron paramagnetic resonance (EPR) spectra, and Density Functional Theory (DFT) calculations. Then the mechanism of action of NMNPs upon deposition on TiO2 is presented. Finally we introduced a survey of the behaviour of these noble metal NPs on TiO2 based on the particle size and the loading amount.

Efficient hydrogenation of biomass-derived furfural and levulinic acid on the facilely synthesized noble-metal-free Cu–Cr catalyst

International Nuclear Information System (INIS)

Yan, Kai; Chen, Aicheng

2013-01-01

Biomass-derived platform intermediate furfural and levulinic acid were efficiently hydrogenated to the value-added furfuryl alcohol and promising biofuel γ-valerolactone, respectively, using a noble-metal-free Cu–Cr catalyst, which was facilely and successfully synthesized by a modified co-precipitation method using the cheap metal nitrates. In the first hydrogenation of furfural, 95% yield of furfuryl alcohol was highly selectively produced at 99% conversion of furfural under the mild conditions. For the hydrogenation of levulinic acid, 90% yield of γ-valerolactone was highly selectively produced at 97.8% conversion. Besides, the physical properties of the resulting Cu–Cr catalysts were studied by XRD (X-ray diffraction), EDX (Energy-dispersive X-ray), TEM (Transmission electron microscopy) and XPS (X-ray photoelectron spectroscopy) to reveal their influence on the catalytic performance. Subsequently, different reaction parameters were studied and it was found that Cu 2+ /Cr 3+ ratios (0.5, 1 and 2), reaction temperature (120–220 °C) and hydrogen pressure (35–70 bar) presented important influence on the catalytic activities. In the end, the stability of the Cu–Cr catalysts was also studied. - Highlights: • A noble-metal-free Cu–Cr catalyst was successfully synthesized using metal nitrates. • Cu–Cr catalysts were highly selective hydrogenation of biomass-derived furfural to FA. • Cu–Cr catalysts were efficient for hydrogenation of biomass-derived LA to biofuel GVL. • The physical properties of the resulting Cu–Cr catalysts were systematically studied. • Reaction parameters and stability in the hydrogenation of furfural were studied in details

Noble metals can have different effects on photocatalysis over metal-organic frameworks (MOFs): a case study on M/NH₂-MIL-125(Ti) (M=Pt and Au).

Science.gov (United States)

Sun, Dengrong; Liu, Wenjun; Fu, Yanghe; Fang, Zhenxing; Sun, Fangxiang; Fu, Xianzhi; Zhang, Yongfan; Li, Zhaohui

2014-04-14

M-doped NH2-MIL-125(Ti) (M=Pt and Au) were prepared by using the wetness impregnation method followed by a treatment with H2 flow. The resultant samples were characterized by powder X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), X-ray absorption fine structure (XAFS) analyses, N2-sorption BET surface area, and UV/Vis diffuse reflectance spectroscopy (DRS). The photocatalytic reaction carried out in saturated CO2 with triethanolamine (TEOA) as sacrificial agent under visible-light irradiations showed that the noble metal-doping on NH2-MIL-125(Ti) promoted the photocatalytic hydrogen evolution. Unlike that over pure NH2-MIL-125(Ti), in which only formate was produced, both hydrogen and formate were formed over Pt- and Au-loaded NH2-MIL-125(Ti). However, Pt and Au have different effects on the photocatalytic performance for formate production. Compared with pure NH2-MIL-125(Ti), Pt/NH2-MIL-125(Ti) showed an enhanced activity for photocatalytic formate formation, whereas Au has a negative effect on this reaction. To elucidate the origin of the different photocatalytic performance, electron spin resonance (ESR) analyses and density functional theory (DFT) calculations were carried out over M/NH2-MIL-125(Ti).The photocatalytic mechanisms over M/NH2-MIL-125(Ti) (M=Pt and Au) were proposed. For the first time, the hydrogen spillover from the noble metal Pt to the framework of NH2-MIL-125(Ti) and its promoting effect on the photocatalytic CO2 reduction is revealed. The elucidation of the mechanism on the photocatalysis over M/NH2-MIL-125(Ti) can provide some guidance in the development of new photocatalysts based on MOF materials. This study also demonstrates the potential of using noble metal-doped MOFs in photocatalytic reactions involving hydrogen as a reactant, like hydrogenation reactions. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrical conductivity dependence of thin metallic films of Au and Pd as a top electrode in capacitor applications

International Nuclear Information System (INIS)

Nazarpour, S.; Langenberg, E.; Jambois, O.; Ferrater, C.; Garcia-Cuenca, M.V.; Polo, M.C.; Varela, M.

2009-01-01

Electrical conductivity dependence of thin metallic films of Au and Pd over the different perovskites was investigated. It is found from electrical properties that crystallographic growth orientation of Au and Pd thin layers attained from X-ray diffraction results indicate the slop of current (I)-voltage (V) plots. Besides, surface morphology and topography was considered using Field Emission Scanning Electron Microscopy and Atomic Force Microscopy, respectively. Obtained results showed the Stranski-Krastanov growth of the Pd and Au. Indeed, diminishing of the root-mean-square roughness of Pd/BiMnO 3 /SrTiO 3 following by Au deposition should be concerned due to growth of Au onto the crack-like parts of the substrate. These crack-like parts appeared due to parasitic phases of the Bi-Mn-O system mainly Mn 3 O 4 (l 0 l) and Mn 3 O 4 (0 0 4 l). The different response in the electrical properties of heterostructures suggests that electrical conductance of the Au and Pd thin metallic films have the crystallographic orientation dependence. Furthermore, polycrystallinity of the thin metallic films are desired in electrode applications due to increase the conductivity of the metallic layers.

Characterization of the electrochemical behavior of coating by steel welding 308l and in presence of noble metals deposits

International Nuclear Information System (INIS)

Piedras, P.; Arganis J, C. R.

2014-10-01

In this work the oxide deposits and noble metals deposit were characterized (Ag and Pt) on a coating of stainless steel 308l that were deposited by the shield metal arc welding (SMAW) on steel A36 by means of scanning electron microscopy, energy-dispersive X-ray spectroscopy and X-ray diffraction. The extrapolation of Tafel technique was also used to obtain the corrosion potential (Ec) for the pre-rusty steel and for the samples with deposits of Pt and Ag under conditions of hydrogen water chemistry (HWC), demonstrating that this parameter diminishes with the presence of this deposits. (Author)

Intermetallic nickel silicide nanocatalyst-A non-noble metal-based general hydrogenation catalyst.

Science.gov (United States)

Ryabchuk, Pavel; Agostini, Giovanni; Pohl, Marga-Martina; Lund, Henrik; Agapova, Anastasiya; Junge, Henrik; Junge, Kathrin; Beller, Matthias

2018-06-01

Hydrogenation reactions are essential processes in the chemical industry, giving access to a variety of valuable compounds including fine chemicals, agrochemicals, and pharmachemicals. On an industrial scale, hydrogenations are typically performed with precious metal catalysts or with base metal catalysts, such as Raney nickel, which requires special handling due to its pyrophoric nature. We report a stable and highly active intermetallic nickel silicide catalyst that can be used for hydrogenations of a wide range of unsaturated compounds. The catalyst is prepared via a straightforward procedure using SiO 2 as the silicon atom source. The process involves thermal reduction of Si-O bonds in the presence of Ni nanoparticles at temperatures below 1000°C. The presence of silicon as a secondary component in the nickel metal lattice plays the key role in its properties and is of crucial importance for improved catalytic activity. This novel catalyst allows for efficient reduction of nitroarenes, carbonyls, nitriles, N-containing heterocycles, and unsaturated carbon-carbon bonds. Moreover, the reported catalyst can be used for oxidation reactions in the presence of molecular oxygen and is capable of promoting acceptorless dehydrogenation of unsaturated N-containing heterocycles, opening avenues for H 2 storage in organic compounds. The generality of the nickel silicide catalyst is demonstrated in the hydrogenation of over a hundred of structurally diverse unsaturated compounds. The wide application scope and high catalytic activity of this novel catalyst make it a nice alternative to known general hydrogenation catalysts, such as Raney nickel and noble metal-based catalysts.

Interactions of noble metal nanoparticles with their environment; Wechselwirkungen von Edelmetallnanopartikeln mit ihrer Umgebung

Energy Technology Data Exchange (ETDEWEB)

Reismann, Maximilian

2009-12-08

Upon irradiating noble metal nanoparticles with light, unique optical phenomena can occur, such as resonantly enhanced light-scattering and light-absorption, or a tremendous enhancement of the exciting optical field close to the surface of the nanoparticles. These phenomena rely on the excitations of collective oscillations of the conduction electrons within a nanoparticle. The optical properties of a nanoparticle are determined by the resonance frequency of these so-called plasmon oscillations. This resonance frequency and the light-scattering spectrum of a nanoparticle depend (among other effects) on the dielectric environment of the particle. Due to this effect, noble metal nanoparticles can be applied for local optical sensing of chemical substances. The large light-absorption properties of a nanoparticle also enable the usage of light-irradiation to deposit heat in the nanoparticle in a selective and highly localized manner. Therefore, a local temperature increase can be induced in the nanoparticle and its immediate environment. This temperature increase could be used to trigger chemical or biological reactions, or it could be used for a selective hyperthermia of biological material. These and further possible applications rely on the detection or the systematic excitation of interactions between the noble metal nanoparticle and its environment. These interactions are the central subject of this thesis. Particular attention is paid to photothermal interactions. An interesting question is to what extend a nanoparticle-supported, photothermally-induced temperature rise can be applied to trigger a biomolecular reaction in a spatially confined volume. By carefully adjusting the photothermal treatment, one aims at affecting the molecules without damaging their chemical functionality. The photothermal interaction is addressed in two projects: First, networks built up by gold nanoparticles are investigated. In these networks, double-stranded DNA-molecules are used to

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

Science.gov (United States)

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.

Synthesis of noble metal nanoparticles and their superstructures; Darstellung von Edelmetallnanopartikeln und deren Ueberstrukturen

Energy Technology Data Exchange (ETDEWEB)

Bigall, Nadja-Carola

2009-08-18

A modified synthesis procedure for citrate-stabilized gold nanoparticles in aqueous solution is transferred under application of equal concentrations to the systems silver, platinum, and palladium. The nanoparticles are analyzed by means of absorption spectroscopy and electron microscopy. Ordered superstructures of the noble-metal nanoparticles can be synthesized by infiltration of templates of block-copolymer films with aqueous nanoparticle solution. In dependence on the pre-treatment of the polymer films either two-dimensional periodical arrangements with a periodicity of less than 30 nm or fingerprint-like arrangements with a groove distance in the same order of magnitude. By removal of the polymer one- respectively two-dimensional arrangements of platinum nanowires respectively nanoparticles on a silicon waver arise.

Magnetic domains and frustration in metallic CePdAl

Energy Technology Data Exchange (ETDEWEB)

Lucas, Stefan; Huesges, Zita; Huang, Chien-Lung; Stockert, Oliver [Max Planck Institute CPfS, Dresden (Germany); Fritsch, Veronika; Sakai, Akito [EP 6, Electronic Correlations and Magnetism, University of Augsburg (Germany); Grube, Kai; Taubenheim, Christian; Loehneysen, Hilbert von [Karlsruhe Institute of Technology (Germany)

2016-07-01

Magnetic frustration is an exciting topic in condensed matter physics, since it can lead to new ground states of materials, e.g. a spin liquid or spin glass state. Effects of magnetic frustration have been investigated intensively for insulating materials. However, the existence of magnetic frustration in metallic systems is still under debate. CePdAl is a metallic Kondo system, where geometric magnetic frustration arises from the formation of Ce ions on a distorted Kagome lattice. Neutron scattering experiments revealed, that only two thirds of the magnetic Ce moments order antiferromagnetically below T{sub N}=2.7 K, whereas the other third remains mainly disordered. Thermodynamic as well as neutron scattering measurements are presented to verify the existence of partial magnetic frustration in CePdAl. Recently neutron diffraction experiments under magnetic fields applied along two orthogonal directions in the magnetically hard basal plane were performed. They show opposite effects on the magnetic intensity of a selected magnetic domain depending on the field direction with respect to the propagation vector. If this is only an effect of different domain population or also due to a change in magnetic frustration shall be discussed.

Synthesis and characterization of ZnO nanostructures on noble-metal coated substrates

Energy Technology Data Exchange (ETDEWEB)

Dikovska, A.Og. [Institute of Electronics, Bulgarian Academy of Sciences, 72 Tsarigradsko Chaussee, Sofia 1784 (Bulgaria); Atanasova, G.B. [Institute of General and Inorganic Chemistry, Bulgarian Academy of Sciences, Acad. G. Bonchev str., bl. 11, 1113 Sofia (Bulgaria); Avdeev, G.V. [Rostislaw Kaischew Institute of Physical Chemistry, Bulgarian Academy of Sciences, Acad. G. Bonchev str., bl. 11, 1113 Sofia (Bulgaria); Nedyalkov, N.N. [Institute of Electronics, Bulgarian Academy of Sciences, 72 Tsarigradsko Chaussee, Sofia 1784 (Bulgaria)

2016-06-30

Highlights: • ZnO nanostructures were fabricated on Au–Ag alloy coated silicon substrates by applying pulsed laser deposition. • Morphology of the ZnO nanostructures was related to the Au–Ag alloy content in the catalyst layer. • Increasing the Ag content in Au–Ag catalyst layer changes the morphology of the ZnO nanostructures from nanorods to nanobelts. - Abstract: In this work, ZnO nanostructures were fabricated on noble-metal (Au, Ag and Au–Ag alloys) coated silicon substrates by applying pulsed laser deposition. The samples were prepared at a substrate temperature of 550 °C, an oxygen pressure of 5 Pa, and a laser fluence of 2 J cm{sup −2} – process parameters usually used for deposition of smooth and dense thin films. The metal layer's role is substantial for the preparation of nanostructures. Heating of the substrate changed the morphology of the metal layer and, subsequently, nanoparticles were formed. The use of different metal particles resulted in different morphologies and properties of the ZnO nanostructures synthesized. The morphology of the ZnO nanostructures was related to the Au–Ag alloy's content of the catalyst layer. It was found that the morphology of the ZnO nanostructures evolved from nanorods to nanobelts as the ratio of Au/Ag in the alloy catalyst was varied. The use of a small quantity of Ag in the Au–Ag catalyst (Au{sub 3}Ag) layer resulted predominantly in the deposition of ZnO nanorods. A higher Ag content in the catalyst alloy (AuAg{sub 2}) layer resulted in the growth of a dense structure of ZnO nanobelts.

Electronic structure of Pd42.5Ni7.5Cu30P20, an excellent bulk metallic glass former: Comparison to the Pd40Ni40P20 reference glass

International Nuclear Information System (INIS)

Hosokawa, S.; Sato, H.; Happo, N.; Mimura, K.; Tezuka, Y.; Ichitsubo, T.; Matsubara, E.; Nishiyama, N.

2007-01-01

In-house photoemission and inverse-photoemission spectra (PES and IPES) were measured on Pd 42.5 Ni 7.5 Cu 30 P 20 and Pd 40 Ni 40 P 20 bulk metallic glasses in order to clarify the origin of excellent glass-forming ability from the viewpoint of electronic structure. Minima are observed for both the metallic glasses at a slightly higher energy than the Fermi level. Incident photon-energy dependent PES spectra were obtained using synchrotron radiation and the Pd 4d partial density of states (DOS) was estimated from the PES data. Soft X-ray emission spectra were also measured near the Ni and Cu 2p 3/2 absorption edges to evaluate, respectively, the Ni and Cu 3d partial DOS in the valence band. The Pd 4d and the Ni and Cu 3d partials in the conduction band were obtained from X-ray absorption spectra around the Pd 3p 3/2 and Ni and Cu 2p 3/2 absorption edges, respectively. It was found that the Pd 4d partial DOS near the Fermi energy largely decreases and becomes localized by replacing the Ni atoms with the Cu atoms, which may be closely related to the excellent glass-forming ability of the Pd 42.5 Ni 7.5 Cu 30 P 20 bulk metallic glass due to a selective formation of Pd-P covalent bonds

Neutron activation determination of noble metals in samples of terrestrial and cosmic origin using microfire assay concentration

International Nuclear Information System (INIS)

Kolesov, G.M.; Sapozhnikov, D.Yu.

1995-01-01

The effects of various factors (composition of mixture, relationship between the mass of mixture and sample, value of the Ni:S ratio, fusion time, and temperature) on the conditions of the fire assay concentration of the noble metals with nickel sulfide were investigated, and a method proposed for their quantitative separation from different geological matrices with a neutron activation determination for up to 10 -1 -10 -3 ppb. The proposed method is used to analyse geological samples, i.e. ores, stones, iron meteorites, chromites, soil and lunar rocks. (author)

The role of fission products (noble metal particles) in spent fuel corrosion process in a failed container

Energy Technology Data Exchange (ETDEWEB)

Wu, L., E-mail: lwu59@uwo.ca [Univ. of Western Ontario, Dept. of Chemistry, London, Ontario (Canada); Shoesmith, D.W. [Univ. of Western Ontario, Dept. of Chemistry, London, Ontario (Canada); Univ. of Western Ontario, Surface Science Western, London, Ontario (Canada)

2013-07-01

The corrosion/dissolution of simulated spent fuel has been studied electrochemically. Fission products within the UO{sub 2} matrix are found to have significant effect on the anodic dissolution behaviour of the fuel. It is observed that H{sub 2}O{sub 2}oxidation is accelerated on the surfaces of doped noble metal (ε) particles existing in the fuel matrix. It is concluded that H{sub 2}O{sub 2} decomposition rather than UO{sub 2} corrosion should be the dominant reaction under high H{sub 2}O{sub 2} concentrations. (author)

Tailoring of the PS surface with low energy ions: Relevance to growth and adhesion of noble metals

International Nuclear Information System (INIS)

Zaporojtchenko, V.; Zekonyte, J.; Wille, S.; Schuermann, U.; Faupel, F.

2005-01-01

Ion-polymer interaction induces different phenomena in the near surface layer of polymers, and promotes its adhesion to metals. Using XPS, TEM and AFM, polystyrene surface was examined after 1 keV ion-beam treatments with oxygen, nitrogen and argon ions in the ion fluence range from 10 12 to 10 16 cm -2 to clarify the following points: chemical reaction after treatment in vacuum and after exposure to air, identification of adsorption-relevant species for metal atoms, formation of cross-links in the outermost polymer layer. The early stages of metal-polymer interface formation during metallization play a crucial role in the metal-polymer adhesion. Therefore, the influence of the ion fluence and ion chemistry on the condensation of noble metals, film growth and peel strength were measured. The peel strength showed a maximum at a certain fluence depending on ion chemistry. For example, the surface treatment with very low fluence of oxygen ions improved the adhesion between copper and polystyrene by two orders of magnitude without significantly increasing the surface roughness measured with AFM. The locus of failure changed at the same time from interfacial failure for untreated polymer surfaces to cohesive failure in the polymer for modified surfaces. A multilayer model of the metal-polymer interface after ion treatment is suggested

Preparation and characterization of metallic supported thin Pd-Ag membranes for hydrogen separation

OpenAIRE

Fernandez, Ekain; Medrano, Jose Antonio; Melendez, Jon; Parco, Maria; Viviente, J.L.; van Sint Annaland, Martin; Gallucci, Fausto; Pacheco Tanaka, David A.

2015-01-01

This paper reports the preparation and characterization of thin-film (4-5 µm thick) Pd-Ag metallic supported membranes for high temperature applications. Various thin film membranes have been prepared by depositing a ceramic interdiffusion barrier layer prior to the simultaneous Pd-Ag electroless plating deposition. Two deposition techniques for ceramic layers (made of zirconia and alumina) have been evaluated: atmospheric plasma spraying and dip coating of a powder suspension. Initially, the...

Characterization and H2-O2 reactivity of noble nano-metal tailored single wall nano-carbons

International Nuclear Information System (INIS)

K Kaneko; T Itoh; E Bekyarova; H Kanoh; S Utsumi; H Tanaka; M Yudasaka; S Iijima; S Iijima

2005-01-01

Full text of publication follows: Single wall carbon nano-tube (SWNT) and single wall carbon nano-horn (SWNH) have nano-spaces in their particles and the nano-spaces become open by oxidation. In particular, SWNH forms a unique colloidal structure which has micropores and meso-pores between the SWNH particles. Although non-treated SWNH colloids have quasi-one dimensional nano-pores [1], oxidized SWNH colloids have both of interstitial and internal nano-pores [2-5]. SWNH colloids show excellent supercritical methane storage ability [6], molecular sieving effect [7], and unique hydrogen adsorption characteristic [8]. Selective adsorptivity of SWNH colloids for H 2 and D 2 due to uncertainty principle of those molecules was shown [9-10]. As SWNH has no metallic impurities, we can study the effect of tailoring of metallic nano-particles on the surface activities of SWNH [11]. We tailored Pd or Pt nano-particles on SWNH and SWNH oxidized at 823 K (ox-SWNH) using poly[(2-oxo-pyrrolidine-1-yl)ethylene]. The oxidation of SWNH donates nano-scale windows to the single wall. The tailored metal amount was determined by TG analysis. TEM showed uniform dispersion of nano-metal particles of 2-3 nm in the diameter on SWNH. The nitrogen adsorption amount of SWNH oxidized decreases by tailoring, indicating that nano-particles are attached to the nano-scale windows. The electronic states of tailored metals were characterized by X-ray photoelectron spectroscopy. The surface activities of Pd tailored SWNH and ox-SWNH were examined for the reaction of hydrogen and oxygen near room temperature. The catalytic reactivities of Pd tailored SWNH and ox-SWNH were 4 times greater than that of Pd-dispersed activated carbon. The temperature dependence of the surface activity will be discussed with the relevance to the tube porosity. References [1] T. Ohba et al, J. Phys. Chem. In press. [2] S. Utsumi et al, J. Phys. Chem. In press. [3] C.- Min Yang, et al. Adv. Mater. In press. [4]C.M. Yang, J

Self-regenerative function of the intelligent automotive catalyst

International Nuclear Information System (INIS)

Tanaka, Hirohisa; Nishihata, Yasuo

2007-01-01

Intelligent catalyst, in which noble metals are used as an active part of automotive catalyst, has been considered for keeping up their sufficient activity. The noble metals have a function of cleaning up the exhaust gas as well as that of self-regeneration. In 2002, a Pd system has been put to practical use, and continuously Rh and Pt systems have been commercialized. Now the catalyst has been used in more than three million vehicles. In this report, the atomic level mechanism of the catalyst and its self-regeneration function getting from analyses using synchrotron radiation are introduced. By the analysis using the Spring-8, the mechanism of keeping the active state of the Pd Perovskite Oxide without degradation was identified. The DXAFS (Dispersive X-ray Absorption Fine Structure) analysis in the ESRF (European Synchrotron Radiation Facility) made clear the self-regeneration mechanism of the Pd Perovskite Oxide. This knowledge could lead to the practical development of the Rh and Pt systems. The catalyst technology is counted on balancing resources of the noble metal and environmental sustainability. (A.H.)

First principles study on the interfacial properties of NM/graphdiyne (NM = Pd, Pt, Rh and Ir): The implications for NM growing

Energy Technology Data Exchange (ETDEWEB)

Lu, Zhansheng; Li, Shuo; Lv, Peng [College of Physics and Electronic Engineering, Henan Normal University, Xinxiang 453007 (China); He, Chaozheng, E-mail: hecz2013@nynu.edu.cn [College of Physics and Electronic Engineering, Nanyang Normal University, Nanyang 473061 (China); Ma, Dongwei [School of Physics, Anyang Normal University, Anyang 455000 (China); Yang, Zongxian, E-mail: yzx@henannu.edu.cn [College of Physics and Electronic Engineering, Henan Normal University, Xinxiang 453007 (China); Collaborative Innovation Center of Nano Functional Materials and Applications, Kaifeng (China)

2016-01-01

Graphical abstract: - Highlights: • The NM adatoms belong to embedded adsorption in 18C-hexagon of GDY. • The Rh and Ir/GDY can be applied to single metal catalysts or sensors. • A simple linear relationship between E{sub e-ads} and E{sub b} is presented. • The linear relationship can be used in the noble metal modified GDY. - Abstract: Based on the dispersion-corrected density functional calculations (DFT-D), we systematically studied the adsorption of noble metals (NM), Pd, Pt, Rh and Ir, on graphdiyne (GDY). We present a systematic study on the geometry, embedded adsorption energy and electronic structure of four different adatoms adsorbed on the GDY. The strong interaction between the NM adatoms and the GDY substrate is found with the NM embedded in the 18C-hexagon of the GDY. We investigated the mobility of the NM adatoms on the GDY, and found that the mobility barrier energy increases along with the increasing of the embedded adsorption energy. We present the NM adatoms growth of high concentrations on the GDY. Upon the analysis of the electronic structure and the frontier molecular orbitals, Rh and Ir adatoms of low concentrations (about 1.37 at%) on the GDY have the potential to be applied as single metal catalysts or gas molecule sensors.

Effect of electric arc, gas oxygen torch and induction melting techniques on the marginal accuracy of cast base-metal and noble metal-ceramic crowns.

Science.gov (United States)

Gómez-Cogolludo, Pablo; Castillo-Oyagüe, Raquel; Lynch, Christopher D; Suárez-García, María-Jesús

2013-09-01

The aim of this study was to identify the most appropriate alloy composition and melting technique by evaluating the marginal accuracy of cast metal-ceramic crowns. Seventy standardised stainless-steel abutments were prepared to receive metal-ceramic crowns and were randomly divided into four alloy groups: Group 1: palladium-gold (Pd-Au), Group 2: nickel-chromium-titanium (Ni-Cr-Ti), Group 3: nickel-chromium (Ni-Cr) and Group 4: titanium (Ti). Groups 1, 2 and 3 were in turn subdivided to be melted and cast using: (a) gas oxygen torch and centrifugal casting machine (TC) or (b) induction and centrifugal casting machine (IC). Group 4 was melted and cast using electric arc and vacuum/pressure machine (EV). All of the metal-ceramic crowns were luted with glass-ionomer cement. The marginal fit was measured under an optical microscope before and after cementation using image analysis software. All data was subjected to two-way analysis of variance (ANOVA). Duncan's multiple range test was run for post-hoc comparisons. The Student's t-test was used to investigate the influence of cementation (α=0.05). Uncemented Pd-Au/TC samples achieved the best marginal adaptation, while the worst fit corresponded to the luted Ti/EV crowns. Pd-Au/TC, Ni-Cr and Ti restorations demonstrated significantly increased misfit after cementation. The Ni-Cr-Ti alloy was the most predictable in terms of differences in misfit when either torch or induction was applied before or after cementation. Cemented titanium crowns exceeded the clinically acceptable limit of 120μm. The combination of alloy composition, melting technique, casting method and luting process influences the vertical seal of cast metal-ceramic crowns. An accurate use of the gas oxygen torch may overcome the results attained with the induction system concerning the marginal adaptation of fixed dental prostheses. Copyright © 2013 Elsevier Ltd. All rights reserved.

Hot-Electron Intraband Luminescence from Single Hot Spots in Noble-Metal Nanoparticle Films

Science.gov (United States)

Haug, Tobias; Klemm, Philippe; Bange, Sebastian; Lupton, John M.

2015-08-01

Disordered noble-metal nanoparticle films exhibit highly localized and stable nonlinear light emission from subdiffraction regions upon illumination by near-infrared femtosecond pulses. Such hot spot emission spans a continuum in the visible and near-infrared spectral range. Strong plasmonic enhancement of light-matter interaction and the resulting complexity of experimental observations have prevented the development of a universal understanding of the origin of light emission. Here, we study the dependence of emission spectra on excitation irradiance and provide the most direct evidence yet that the continuum emission observed from both silver and gold nanoparticle aggregate surfaces is caused by recombination of hot electrons within the conduction band. The electron gas in the emitting particles, which is effectively decoupled from the lattice temperature for the duration of emission, reaches temperatures of several thousand Kelvin and acts as a subdiffraction incandescent light source on subpicosecond time scales.

Synthesis of ultrathin face-centered-cubic Au@Pt and Au@Pd core-shell nanoplates from hexagonal-close-packed Au square sheets

KAUST Repository

Fan, Zhanxi; Zhu, Yihan; Huang, Xiao; Han, Yu; Wang, Qingxiao; Liu, Qing; Huang, Ying; Gan, Chee Lip; Zhang, Hua

2015-01-01

@Pd rhombic nanoplates, respectively. We believe that these findings will shed new light on the synthesis of novel noble bimetallic nanostructures. Phase change: Ultrathin Au@Pt and Au@Pd core-shell nanoplates were prepared from Au square sheets. A phase

A systematic chemical separation for thermal neutron activation analysis of seven noble metals in rock

International Nuclear Information System (INIS)

Ayabe, Muneo

1980-01-01

A method for the systematic activation analysis of seven noble metals - ruthenium, silver, rhenium, osmium, iridium, platinum and gold - in rocks were developed and examined with radiotracers and irradiated rock samples. After the fusion of the irradiated rock sample with sodium hydroxide and sodium peroxide, 10% sodium sulfide solution is added and rhenium is extracted with pyridine-benzene mixture from 6N sodium hydroxide solution. From the hydroxide-sulfide precipitate fraction, ruthenium and osmium are distilled as tetroxides, silver is precipitated as chloride, gold is extracted with ethyl acetate, and iridium and platinum are extracted with diantipyrylmethane. Each fraction is purified and subjected to the γ-ray spectrometry. Chemical yields for the elements are more than 60%. Determination limits are given for the seven elements. (author)

Electrochemistry of conductive polymers 39. Contacts between conducting polymers and noble metal nanoparticles studied by current-sensing atomic force microscopy.

Science.gov (United States)

Cho, Shin Hyo; Park, Su-Moon

2006-12-28

Electrical properties of contacts formed between conducting polymers and noble metal nanoparticles have been examined using current-sensing atomic force microscopy (CS-AFM). Contacts formed between electrochemically prepared pi-conjugated polymer films such as polypyrrole (PPy), poly(3-methylthiophene) (P3MeT), as well as poly(3,4-ethylenedioxythiophene) (PEDOT) and noble metal nanoparticles including platinum (Pt), gold (Au), and silver (Ag) have been examined. The Pt nanoparticles were electrochemically deposited on a pre-coated PPy film surface by reducing a platinum precursor (PtCl62-) at a constant potential. Both current and scanning electron microscopic images of the film showed the presence of Pt islands. The Au and Ag nanoparticles were dispersed on the P3MeT and PEDOT film surfaces simply by dipping the polymer films into colloid solutions containing Au or Ag particles for specified periods (5 to approximately 10 min). The deposition of Au or Ag particles resulted from either their physical adsorption or chemical bonding between particles and the polymer surface depending on the polymer. When compared with PPy, P3MeT and PEDOT showed a stronger binding to Au or Ag nanoparticles when dipped in their colloidal solutions for the same period. This indicates that Au and Ag particles are predominantly linked with the sulfur atoms via chemical bonding. Of the two, PEDOT was more conductive at the sites where the particles are connected to the polymer. It appears that PEDOT has better aligned sulfur atoms on the surface and is strongly bonded to Au and Ag nanoparticles due to their strong affinity to gold and silver. The current-voltage curves obtained at the metal islands demonstrate that the contacts between these metal islands and polymers are ohmic.

Non-enzymatic electrochemical immunoassay using noble metal nanoparticles: a review

International Nuclear Information System (INIS)

Tang, Juan; Tang, Dianping

2015-01-01

Electrochemical immunodetection has attracted considerable attention due to its high sensitivity, low cost and simplicity. Large efforts have recently made in order to design ultrasensitive assays. Noble metal nanoparticles (NM-NPs) offer advantages such as high conductivity and large surface-to-volume ratio. NM-NPs therefore are excellent candidates for developing electrochemical platforms for immunodetection and as signal tags. The use of biofunctionalized NM-NPs often results in amplified recognition via stronger loading of signal tags, and also in enhanced signal. This review (with 87 references) gives an overview on the current state in the use of NM-NPs in Non-enzymatic electrochemical immunosensing. We discuss the application of NM-NPs as electrode matrices and as electroactive labels (either as a carrier or as electrocatalytic labels), and compare the materials (mainly nanoparticles of gold, platinum, or of bimetallic materials) in terms of performance (for example by increasing sensitivity via label amplification or via high densities of capture molecules). A conclusion covers current challenges and gives an outlook. Rather than being exhaustive, the review focuses on representative examples that illustrate novel concepts and promising applications. NM-NPs based immunosensing opens a series of concepts for basic research and offers new tools for determination of trace amounts of protein-related analytes in environment and clinical applications. (author)

Radiolytic model of CN Cofrentes using BWRVIA: analysis of the effectiveness of mitigation in locations of the vessel with application of noble metal son-line; Modelo radiolitico de C. N: Cofrentes utilizando el BWRVIA: analisis de la efectividad de mitigacion en localizaciones de la vasija con aplicacion de metales nobles on-line

Energy Technology Data Exchange (ETDEWEB)

Martin-Serrano Ledesma, C.; Sanchez Zapata, J. D.

2012-07-01

The effectiveness of mitigation is found from two chemical parameters: electrochemical potential (pm-a hydrogen injection) and Molar Ratio (for the application of noble metals). EPRI code exists, the BWRVIA (BWR Vessel Internals Application,) which enables setting model the impact radiolysis of water, the balance of liquid-vapor phase and recirculation have on the chemical variation of these parameters.

Platinum and Palladium Alloys Suitable as Fuel Cell Electrodes

DEFF Research Database (Denmark)

2011-01-01

The present invention concerns electrode catalysts used in fuel cells, such as proton exchange membrane (PEM) fuel cells. The invention is related to the reduction of the noble metal content and the improvement of the catalytic efficiency by low level substitution of the noble metal to provide new...... and innovative catalyst compositions in fuel cell electrodes. The novel electrode catalysts of the invention comprise a noble metal selected from Pt, Pd and mixtures thereof alloyed with a further element selected from Sc, Y and La as well as any mixtures thereof, wherein said alloy is supported on a conductive...

Toward hybrid Au nanorods @ M (Au, Ag, Pd and Pt) core-shell heterostructures for ultrasensitive SERS probes

Science.gov (United States)

Xie, Xiaobin; Gao, Guanhui; Kang, Shendong; Lei, Yanhua; Pan, Zhengyin; Shibayama, Tamaki; Cai, Lintao

2017-06-01

Being able to precisely control the morphologies of noble metallic nanostructures is of essential significance for promoting the surface-enhanced Raman scattering (SERS) effect. Herein, we demonstrate an overgrowth strategy for synthesizing Au @ M (M = Au, Ag, Pd, Pt) core-shell heterogeneous nanocrystals with an orientated structural evolution and highly improved properties by using Au nanorods as seeds. With the same reaction condition system applied, we obtain four well-designed heterostructures with diverse shapes, including Au concave nanocuboids (Au CNs), Au @ Ag crystalizing face central cube nanopeanuts, Au @ Pd porous nanocuboids and Au @ Pt nanotrepangs. Subsequently, the exact overgrowth mechanism of the above heterostructural building blocks is further analysed via the systematic optimiziation of a series of fabrications. Remarkably, the well-defined Au CNs and Au @ Ag nanopeanuts both exhibit highly promoted SERS activity. We expect to be able to supply a facile strategy for the fabrication of multimetallic heterogeneous nanostructures, exploring the high SERS effect and catalytic activities.

Pd/NbOPO₄ multifunctional catalyst for the direct production of liquid alkanes from aldol adducts of furans.

Science.gov (United States)

Xia, Qi-Neng; Cuan, Qian; Liu, Xiao-Hui; Gong, Xue-Qing; Lu, Guan-Zhong; Wang, Yan-Qin

2014-09-08

Great efforts have been made to convert renewable biomass into transportation fuels. Herein, we report the novel properties of NbO(x)-based catalysts in the hydrodeoxygenation of furan-derived adducts to liquid alkanes. Excellent activity and stability were observed with almost no decrease in octane yield (>90% throughout) in a 256 h time-on-stream test. Experimental and theoretical studies showed that NbO(x) species play the key role in C-O bond cleavage. As a multifunctional catalyst, Pd/NbOPO4 plays three roles in the conversion of aldol adducts into alkanes: 1) The noble metal (in this case Pd) is the active center for hydrogenation; 2) NbO(x) species help to cleave the C-O bond, especially of the tetrahydrofuran ring; and 3) a niobium-based solid acid catalyzes the dehydration, thus enabling the quantitative conversion of furan-derived adducts into alkanes under mild conditions. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Radiological analysis by the addition of hydrogen and noble metals in the reactors of the Laguna Verde central

International Nuclear Information System (INIS)

Padilla C, I.

2006-01-01

During the operation of the nuclear power stations there are metals that are subject to condition and agents that cause that these they present indications of intergranular corrosion and for their importance they are subject to a continuous surveillance to assure their integrity. During the time of operation, for the level of indications, it can be necessary the substitution of these. The internal components of the vessel and particularly those of the structure of the reactor core are exposed during the operation to a neutron flow that causes that these they are activated and, in consequence, before an eventual repair it will be necessary to face high radiation levels. At the moment a technique that controls exists and it reduces the growth rate of the indications in the metals and it increases its useful life: the addition of hydrogen. The addition of hydrogen it is an ALARA measure from long term when protecting the internals of the vessel that requires to establish radiological controls in the stage of their application to avoid unnecessary dose to the personnel. The addition of hydrogen to the primary system has as objective to reduce the growth of indications taken place by intergranular corrosion in metals of the reactor core and this is achieved when the electrochemical thresholds are reached. Hydrogen to interacting with the metal surfaces it generates reductive reactions causing in consequence an increment in the concentration of soluble cobalt in the coolant one and an increment in the nitrogen concentration. To reduce the magnitude of the radiological impact that in some NC reach up to factors 10, its are injected to the system noble metals as the rhodium and the platinum, to reduce the concentration of hydrogen to the system and to be below the threshold electrochemical potential necessary to protect the internals of the reactor vessel. The external and internal operational experience generated on this protection technique to the internals of the vessel

Non-noble metal Cu-loaded TiO2 for enhanced photocatalytic H2 production.

Science.gov (United States)

Foo, Wei Jian; Zhang, Chun; Ho, Ghim Wei

2013-01-21

Here we have demonstrated the preparation of high-quality, monodispersed and tunable phases of Cu nanoparticles. Structural and chemical composition studies depict the evolution of Cu-Cu(2)O-CuO nanoparticles at various process stages. The loading of Cu and Cu oxide nanoparticles on TiO(2) catalyst has enhanced the photocatalytic H(2) production. Comparatively, H(2) treatment produces well-dispersed Cu nanoparticles with thin oxide shells that show the highest H(2) production amongst the samples. The relatively higher photocatalytic performance is deemed to result from reduced structural defects, higher surface area and dispersivity as well as favorable charge transfer, which inhibits recombination. The Cu nanoparticles are shown to be a promising alternative to noble metal-loaded TiO(2) catalyst systems due to their low cost and high performance in photocatalytic applications.

Ab initio study of the trapping of polonium on noble metals

Science.gov (United States)

Rijpstra, Kim; Van Yperen-De Deyne, Andy; Maugeri, Emilio Andrea; Neuhausen, Jörg; Waroquier, Michel; Van Speybroeck, Veronique; Cottenier, Stefaan

2016-04-01

In the future MYRRHA reactor, lead bismuth eutectic (LBE) will be used both as coolant and as spallation target. Due to the high neutron flux a small fraction of the bismuth will transmute to radiotoxic 210Po. Part of this radiotoxic element will evaporate into the gas above the coolant. Extracting it from the gas phase is necessary to ensure a safe handling of the reactor. An issue in the development of suitable filters is the lack of accurate knowledge on the chemical interaction between a candidate filter material and either elemental polonium or polonium containing molecules. Experimental work on this topic is complicated by the high radiotoxicity of polonium. Therefore, we present in this paper a first-principles study on the adsorption of polonium on noble metals as filter materials. The adsorption of monoatomic Po is considered on the candidate filter materials palladium, platinum, silver and gold. The case of the gold filter is looked upon in more detail by examining how bismuth pollution affects its capability to capture polonium and by studying the adsorption of the heavy diatomic molecules Po2, PoBi and PoPb on this gold filter.

Ab initio study of the trapping of polonium on noble metals

Energy Technology Data Exchange (ETDEWEB)

Rijpstra, Kim; Van Yperen-De Deyne, Andy [Center for Molecular Modeling (CMM), Ghent University, Technologiepark 903, 9052 Ghent (Belgium); Maugeri, Emilio Andrea; Neuhausen, Jörg [Laboratory for Radiochemistry, Paul Scherrer Institute (PSI), 5232 Villigen (Switzerland); Waroquier, Michel; Van Speybroeck, Veronique [Center for Molecular Modeling (CMM), Ghent University, Technologiepark 903, 9052 Ghent (Belgium); Cottenier, Stefaan, E-mail: stefaan.cottenier@ugent.be [Center for Molecular Modeling (CMM), Ghent University, Technologiepark 903, 9052 Ghent (Belgium); Department of Materials Science and Engineering, Ghent University, Technologiepark 903, 9052 Ghent (Belgium)

2016-04-15

In the future MYRRHA reactor, lead bismuth eutectic (LBE) will be used both as coolant and as spallation target. Due to the high neutron flux a small fraction of the bismuth will transmute to radiotoxic {sup 210}Po. Part of this radiotoxic element will evaporate into the gas above the coolant. Extracting it from the gas phase is necessary to ensure a safe handling of the reactor. An issue in the development of suitable filters is the lack of accurate knowledge on the chemical interaction between a candidate filter material and either elemental polonium or polonium containing molecules. Experimental work on this topic is complicated by the high radiotoxicity of polonium. Therefore, we present in this paper a first-principles study on the adsorption of polonium on noble metals as filter materials. The adsorption of monoatomic Po is considered on the candidate filter materials palladium, platinum, silver and gold. The case of the gold filter is looked upon in more detail by examining how bismuth pollution affects its capability to capture polonium and by studying the adsorption of the heavy diatomic molecules Po{sub 2}, PoBi and PoPb on this gold filter.

Study of Thermodynamics of Liquid Noble-Metals Alloys Through a Pseudopotential Theory

International Nuclear Information System (INIS)

Vora, Aditya M.

2010-01-01

The Gibbs-Bogoliubov (GB) inequality is applied to investigate the thermodynamic properties of some equiatomic noble metal alloys in liquid phase such as Au-Cu, Ag-Cu, and Ag-Au using well recognized pseudopotential formalism. For description of the structure, well known Percus-Yevick (PY) hard sphere model is used as a reference system. By applying a variation method the best hard core diameters have been found which correspond to minimum free energy. With this procedure the thermodynamic properties such as entropy and heat of mixing have been computed. The influence of local field correction function viz; Hartree (H), Taylor (T), Ichimaru-Utsumi (IU), Farid et al. (F), and Sarkar et al. (S) is also investigated. The computed results of the excess entropy compares favourably in the case of liquid alloys while the agreement with experiment is poor in the case of heats of mixing. This may be due to the sensitivity of the heats of mixing with the potential parameters and the dielectric function. (condensed matter: electronic structure, electrical, magnetic, and optical properties)

Effect of an in-plane ligand on the electronic structures of bromo-bridged nano-wire Ni-Pd mixed-metal complexes, [Ni(1-x)Pd(x)(bn)2Br]Br2 (bn = 2S,3S-diaminobutane).

Science.gov (United States)

Sasaki, Mari; Wu, Hashen; Kawakami, Daisuke; Takaishi, Shinya; Kajiwara, Takashi; Miyasaka, Hitoshi; Breedlove, Brian K; Yamashita, Masahiro; Kishida, Hideo; Matsuzaki, Hiroyuki; Okamoto, Hiroshi; Tanaka, Hisaaki; Kuroda, Shinichi

2009-08-03

Single crystals of quasi-one-dimensional bromo-bridged Ni-Pd mixed-metal complexes with 2S,3S-diaminobutane (bn) as an in-plane ligand, [Ni(1-x)Pd(x)(bn)(2)Br]Br(2), were obtained by using an electrochemical oxidation method involving mixed methanol/2-propanol (1:1) solutions containing different ratios of [Ni(II)(bn)(2)]Br(2) and [Pd(II)(bn)(2)]Br(2). To investigate the competition between the electron-correlation of the Ni(III) states, or Mott-Hubbard states (MH), and the electron-phonon interaction of the Pd(II)-Pd(IV) mixed valence states, or charge-density-wave states (CDW), in the Ni-Pd mixed-metal compounds, X-ray structure analyses, X-ray oscillation photograph, and Raman, IR, ESR, and single-crystal reflectance spectra were analyzed. In addition, the local electronic structures of Ni-Pd mixed-metal single crystals were directly investigated by using scanning tunneling microscopy (STM) at room temperature and ambient pressure. The oxidation states of [Ni(1-x)Pd(x)(bn)(2)Br]Br(2) changed from a M(II)-M(IV) mixed valence state to a M(III) MH state at a critical mixing ratio (x(c)) of approximately 0.8, which is lower than that of [Ni(1-x)Pd(x)(chxn)(2)Br]Br(2) (chxn = 1R,2R-diaminocyclohexane) (x(c) approximately 0.9) reported previously. The lower value of x(c) for [Ni(1-x)Pd(x)(bn)(2)Br]Br(2) can be explained by the difference in their CDW dimensionalities because the three-dimensional CDW ordering in [Pd(bn)(2)Br]Br(2) observed by using X-ray diffuse scattering stabilizes the Pd(II)-Pd(IV) mixed valence state more than two-dimensional CDW ordering in [Pd(chxn)(2)Br]Br(2) does, which has been reported previously.

Three dimensional nano-assemblies of noble metal nanoparticle-infinite coordination polymers as specific oxidase mimetics for degradation of methylene blue without adding any cosubstrate.

Science.gov (United States)

Wang, Lihua; Zeng, Yi; Shen, Aiguo; Zhou, Xiaodong; Hu, Jiming

2015-02-07

Novel three-dimensional (3D) nano-assemblies of noble metal nanoparticle (NP)-infinite coordination polymers (ICPs) are conveniently fabricated through the infiltration of HAuCl4 into hollow Au@Ag@ICPs core-shell nanostructures and its replacement reaction with Au@Ag NPs. The present 3D nano-assemblies exhibit highly efficient and specific intrinsic oxidase-like activity even without adding any cosubstrate.

The Role of Mg(OH)2 in the So-Called "Base-Free" Oxidation of Glycerol with AuPd Catalysts.

Science.gov (United States)

Fu, Jile; He, Qian; Miedziak, Peter J; Brett, Gemma L; Huang, Xiaoyang; Pattisson, Samuel; Douthwaite, Mark; Hutchings, Graham J

2018-02-16

Mg(OH) 2 - and Mg(OH) 2 -containing materials can provide excellent performance as supports for AuPd nanoparticles for the oxidation of glycerol in the absence of base, which is considered to be a result of additional basic sites on the surface of the support. However, its influence on the reaction solution is not generally discussed. In this paper, we examine the relationship between the basic Mg(OH) 2 support and AuPd nanoparticles in detail using four types of catalyst. For these reactions, the physical interaction between Mg(OH) 2 and AuPd was adjusted. It was found that the activity of the AuPd nanoparticles increased with the amount of Mg(OH) 2 added under base-free conditions, regardless of its interaction with the noble metals. In order to investigate how Mg(OH) 2 affected the glycerol oxidation, detailed information about the performance of AuPd/Mg(OH) 2 , physically mixed (AuPd/C+Mg(OH) 2 ) and (AuPd/C+NaHCO 3 ) was obtained and compared. Furthermore, NaOH and Mg(OH) 2 were added during the reaction using AuPd/C. All these results indicate that the distinctive and outstanding performance of Mg(OH) 2 supported catalysts in base-free condition is in fact directly related to its ability to affect the pH during the reaction and as such, assists with the initial activation of the primary alcohol, which is considered to be the rate determining step in the reaction. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Substrate-Based Noble-Metal Nanomaterials: Shape Engineering and Applications

Science.gov (United States)

Hajfathalian, Maryam

Nanostructures have potential for use in state-of-the-art applications such as sensing, imaging, therapeutics, drug delivery, and electronics. The ability to fabricate and engineer these nanoscale materials is essential for the continued development of such devices. Because the morphological features of nanomaterials play a key role in determining chemical and physical properties, there is great interest in developing and improving methods capable of controlling their size, shape, and composition. While noble nanoparticles have opened the door to promising applications in fields such as imaging, cancer targeting, photothermal treatment, drug delivery, catalysis and sensing, the synthetic processes required to form these nanoparticles on surfaces are not well-developed. Herein is a detailed account on efforts for adapting established solution-based seed-mediated synthetic protocols to structure in a substrate-based platform. These syntheses start by (i) defining heteroepitaxially oriented nanostructured seeds at site-specific locations using lithographic or directed-assembly techniques, and then (ii) transforming the seeds using either a solution or vapor phase processing route to activate kinetically- or thermodynamically-driven growth modes, to arrive at nanocrystals with complex and useful geometries. The first series of investigations highlight synthesis-routes based on heterogeneous nucleation, where templates serve as nucleation sites for metal atoms arriving in the vapor phase. In the first research direction, the vapor-phase heterogeneous nucleation of Ag on Au was carried out at high temperatures, where the Ag vapor was sourced from a sublimating foil onto adjacent Au templates. This process transformed both the composition and morphology of the initial Au Wulff-shaped nanocrystals to a homogeneous AuAg nanoprism. In the second case, the vapor-phase heterogeneous nucleation of Cu atoms on Au nanocrystal templates was investigated by placing a Cu foil next

Crystallization of Pd40CU30Ni10P20 bulk metallic glass with and without pressure

DEFF Research Database (Denmark)

Yang, B.; Jiang, Jianzhong; Zhuang, Yanxin

2007-01-01

The glass-transition behavior of Pd40Cu30Ni10P20 bulk metallic glass was investigated by differential scanning calorimetry (DSC) and X-ray powder diffraction (XRD). The effect of pressure on the crystallization behavior of Pd40Cu30Ni10P20 bulk glass was studied by in situ high-pressure and high...

Redox potential monitoring as a method to control unwanted noble metal-catalyzed hydrogen generation from formic acid treatment of simulated nuclear waste media

International Nuclear Information System (INIS)

King, R.B.; Bhattacharyya, N.K.

1998-01-01

Simulants for the Hanford Waste Vitrification Plant feed containing the major nonradioactive components Al, Cd, Fe, Mn, Nd, Ni, Si, Zr, Na, CO 3 2- , NO 3 - , and NO 2 - were used to study redox potential changes in reactions of formic acid at 90 C catalyzed by the noble metals Ru, Rh, and/or Pd found in significant quantities in uranium fission products. Such reactions were monitored using gas chromatography to analyze the CO 2 , H 2 , NO, and N 2 O in the gas phase and a redox electrode to follow redox potential changes as a function of time. In the initial phase of formic acid addition to nitrite-containing feed simulants, the redox potential of the reaction mixture rises typically to +400 mV relative to the Al/AgCl electrode because of the generation of the moderately strongly oxidizing nitrous acid. No H 2 production occurs at this stage of the reaction as long as free nitrous acid is present. After all of the nitrous acid has been destroyed by reduction to N 2 O and NO and disproportionation to NO/NO 3 - , the redox potential of the reaction mixture becomes more negative than the Ag/AgCl electrode. The experiments outlined in this paper suggest the feasibility of controlling the production of H 2 by limiting the amount of formic acid used and monitoring the redox potential during formic acid treatment

Experimental Challenges in Studying Hydrogen Absorption in Ultrasmall Metal Nanoparticles

International Nuclear Information System (INIS)

Zlotea, Claudia; Oumellal, Yassine; Provost, Karine; Ghimbeu, Camelia Matei

2016-01-01

Recent advances on synthesis, characterization, and hydrogen absorption properties of ultrasmall metal nanoparticles (defined here as objects with average size ≤3 nm) are briefly reviewed in the first part of this work. The experimental challenges encountered in performing accurate measurements of hydrogen absorption in Mg- and noble metal-based ultrasmall nanoparticles are addressed. The second part of this work reports original results obtained for ultrasmall bulk-immiscible Pd–Rh nanoparticles. Carbon-supported Pd–Rh nanoalloys in the whole binary chemical composition range have been successfully prepared by liquid impregnation method followed by reduction at 300°C. EXAFS investigations suggested that the local structure of these nanoalloys is partially segregated into Rh-rich core and Pd-rich surface coexisting within the same nanoparticles. Downsizing to ultrasmall dimensions completely suppresses the hydride formation in Pd-rich nanoalloys at ambient conditions, contrary to bulk and larger nanosized (5–6 nm) counterparts. The ultrasmall Pd 90 Rh 10 nanoalloy can absorb hydrogen-forming solid solutions under these conditions, as suggested by in situ X-ray diffraction (XRD). Apart from this composition, common laboratory techniques, such as in situ XRD, DSC, and PCI, failed to clarify the hydrogen interaction mechanism: either adsorption on developed surfaces or both adsorption and absorption with formation of solid solutions. Concluding insights were brought by in situ EXAFS experiments at synchrotron: ultrasmall Pd 75 Rh 25 and Pd 50 Rh 50 nanoalloys absorb hydrogen-forming solid solutions at ambient conditions. Moreover, the hydrogen solubility in these solid solutions is higher with increasing Pd content, and this trend can be understood in terms of hydrogen preferential occupation in the Pd-rich regions, as suggested by in situ EXAFS. The Rh-rich nanoalloys (Pd 25 Rh 75 and Pd 10 Rh 90 ) only adsorb hydrogen on the developed surface of ultrasmall

Noble Gases

Science.gov (United States)

Podosek, F. A.

2003-12-01

The noble gases are the group of elements - helium, neon, argon, krypton, xenon - in the rightmost column of the periodic table of the elements, those which have "filled" outermost shells of electrons (two for helium, eight for the others). This configuration of electrons results in a neutral atom that has relatively low electron affinity and relatively high ionization energy. In consequence, in most natural circumstances these elements do not form chemical compounds, whence they are called "noble." Similarly, much more so than other elements in most circumstances, they partition strongly into a gas phase (as monatomic gas), so that they are called the "noble gases" (also, "inert gases"). (It should be noted, of course, that there is a sixth noble gas, radon, but all isotopes of radon are radioactive, with maximum half-life a few days, so that radon occurs in nature only because of recent production in the U-Th decay chains. The factors that govern the distribution of radon isotopes are thus quite different from those for the five gases cited. There are interesting stories about radon, but they are very different from those about the first five noble gases, and are thus outside the scope of this chapter.)In the nuclear fires in which the elements are forged, the creation and destruction of a given nuclear species depends on its nuclear properties, not on whether it will have a filled outermost shell when things cool off and nuclei begin to gather electrons. The numerology of nuclear physics is different from that of chemistry, so that in the cosmos at large there is nothing systematically special about the abundances of the noble gases as compared to other elements. We live in a very nonrepresentative part of the cosmos, however. As is discussed elsewhere in this volume, the outstanding generalization about the geo-/cosmochemistry of the terrestrial planets is that at some point thermodynamic conditions dictated phase separation of solids from gases, and that the

Scattering of low energy noble gas ions from a metal surface

International Nuclear Information System (INIS)

Luitjens, S.B.

1980-01-01

Reflection of low energy (0.1-10 keV) noble gas ions can be used to analyse a solid surface. To study charge exchange processes, the ion fractions of neon and of argon, scattered from a Cu(100) surface, have been determined. (Auth.)

TLC-SERS Plates with a Built-In SERS Layer Consisting of Cap-Shaped Noble Metal Nanoparticles Intended for Environmental Monitoring and Food Safety Assurance

Directory of Open Access Journals (Sweden)

H. Takei

2015-01-01

Full Text Available We report on a thin layer chromatograph (TLC with a built-in surface enhanced Raman scattering (SERS layer for in-situ identification of chemical species separated by TLC. Our goal is to monitor mixture samples or diluted target molecules suspended in a host material, as happens often in environmental monitoring or detection of food additives. We demonstrate that the TLC-SERS can separate mixture samples and provide in-situ SERS spectra. One sample investigated was a mixture consisting of equal portions of Raman-active chemical species, rhodamine 6 G (R6G, crystal violet (CV, and 1,2-di(4-pyridylethylene (BPE. The three components could be separated and their SERS spectra were obtained from different locations. Another sample was skim milk with a trace amount of melamine. Without development, no characteristic peaks were observed, but after development, a peak was observed at 694 cm−1. Unlike previous TLC-SERS whereby noble metal nanoparticles are added after development of a sample, having a built-in SERS layer greatly facilitates analysis as well as maintaining high uniformity of noble metal nanoparticles.

Measuring the spin polarization of alkali-metal atoms using nuclear magnetic resonance frequency shifts of noble gases

Directory of Open Access Journals (Sweden)

X. H. Liu

2015-10-01

Full Text Available We report a novel method of measuring the spin polarization of alkali-metal atoms by detecting the NMR frequency shifts of noble gases. We calculated the profile of 87Rb D1 line absorption cross sections. We then measured the absorption profile of the sample cell, from which we calculated the 87Rb number densities at different temperatures. Then we measured the frequency shifts resulted from the spin polarization of the 87Rb atoms and calculated its polarization degrees at different temperatures. The behavior of frequency shifts versus temperature in experiment was consistent with theoretical calculation, which may be used as compensative signal for the NMRG closed-loop control system.

Toward control of the metal-organic interfacial electronic structure in molecular electronics: a first-principles study on self-assembled monolayers of pi-conjugated molecules on noble metals.

Science.gov (United States)

Heimel, Georg; Romaner, Lorenz; Zojer, Egbert; Brédas, Jean-Luc

2007-04-01

Self-assembled monolayers (SAMs) of organic molecules provide an important tool to tune the work function of electrodes in plastic electronics and significantly improve device performance. Also, the energetic alignment of the frontier molecular orbitals in the SAM with the Fermi energy of a metal electrode dominates charge transport in single-molecule devices. On the basis of first-principles calculations on SAMs of pi-conjugated molecules on noble metals, we provide a detailed description of the mechanisms that give rise to and intrinsically link these interfacial phenomena at the atomic level. The docking chemistry on the metal side of the SAM determines the level alignment, while chemical modifications on the far side provide an additional, independent handle to modify the substrate work function; both aspects can be tuned over several eV. The comprehensive picture established in this work provides valuable guidelines for controlling charge-carrier injection in organic electronics and current-voltage characteristics in single-molecule devices.

Noble metal nanoparticle-functionalized ZnO nanoflowers for photocatalytic degradation of RhB dye and electrochemical sensing of hydrogen peroxide

DEFF Research Database (Denmark)

Hussain, Muhammad; Sun, Hongyu; Karim, Shafqat

2016-01-01

Flower-like hierarchical Zinc oxide nanostructures synthesized by co-precipitation method have been hydrothermally functionalized with 8 nm Au NPs and 15 nm Ag nanoparticles. The photocatalytic and electrochemical performance of these structures are investigated. XPS studies show that the composite...... exhibits a strong interaction between noble metal nanoparticles (NPs) and Zinc oxide nanoflowers. The PL spectra exhibit UV emission arising due to near band edge transition and show that the reduced PL intensities of Au–ZnO and Ag–ZnO composites are responsible for improved photocatalytic activity arising...

Enhancing the biofuel upgrade performance for Pd nanoparticles via increasing the support hydrophilicity of metal-organic frameworks.

Science.gov (United States)

Sun, Qi; Chen, Meng; Aguila, Briana; Nguyen, Nicholas; Ma, Shengqian

2017-09-08

In this work, the influence of the hydrophilic/hydrophobic nature of metal-organic framework (MOF) materials on the catalytic performance of supported Pd nanoparticles for biofuel upgrade was studied. We show that the introduction of hydrophilic groups on a MOF can greatly enhance the performance of the resultant catalyst. Specifically, Pd nanoparticles supported on MIL-101-SO 3 Na with superhydrophilicity (Pd/MIL-101-SO 3 Na) far outperforms pristine MIL-101 and the benchmark catalyst Pd/C in the hydrodeoxygenation reaction of vanillin, a model component of pyrolysis oil derived from the lignin fraction. This is attributed to a favorable mode of adsorption of the highly water soluble reactants on the more hydrophilic support in the vicinity of the catalytically active Pd nanoparticles, thereby promoting their transformation.

NO reduction by CO over noble-metal catalysts under cycled feedstreams

International Nuclear Information System (INIS)

Muraki, H.; Fujitani, Y.

1986-01-01

The reduction of NO with CO was studied over α-Al/sub 2/O/sub 3/-supported Pt, Pd, Rh, Ru, and Ir catalysts. The activities were measured by using cycled feeds and steady noncycled feed. The activity sequence of the catalysts tested was Rh > Ru > Ir > Pd > Pt. The activities of Pt and Pd catalysts were increased under the cycled feed. The periodic operation effect on the Pt catalyst was more predominant than that on the Pd catalyst. The order of periodic operation effect corresponded to the order of their susceptibility to CO self-poisoning

Hydrazine reduction of metal ions to porous submicro-structures of Ag, Pd, Cu, Ni, and Bi

Energy Technology Data Exchange (ETDEWEB)

Wang Yue; Shi Yongfang; Chen Yubiao [State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002 (China); Wu Liming, E-mail: liming_wu@fjirsm.ac.cn [State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002 (China)

2012-07-15

Porous submicro-structures of Ag, Pd, Cu, Ni, and Bi with high surface area have been prepared by the reduction of hydrazine in glycerol-ethanol solution at room temperature or 120-180 Degree-Sign C. Phase purity, morphology, and specific surface area have been characterized. The reactions probably undergo three different mechanisms: simple reduction for Ag and Pd, coordination-then-reduction for Cu and Ni, and hydrolysis-then-reduction for Bi. The reductant hydrazine also plays an important role to the formation of the porous submicro-structure. The reaction temperature influences the size of the constituent particles and the overall architecture of the submicro-structure so as to influence the surface area value. The as-prepared porous metals have shown the second largest surface area ever reported, which are smaller than those made by the reduction of NaBH{sub 4}, but larger than those made by hard or soft template methods. - Graphical abstract: Porous submicro-structures of Ag, Pd, Cu, Ni, and Bi with high surface area have been prepared by the reduction of hydrazine in the glycerol-ethanol solution at room temperature or 120-180 Degree-Sign C. The reactions undergo different mechanisms: simple reduction for Ag and Pd, coordination-then-reduction for Cu and Ni, and hydrolysis-then-reduction for Bi. Highlights: Black-Right-Pointing-Pointer Syntheses of porous Ag, Pd, Cu, Ni, and Bi with high surface area. Black-Right-Pointing-Pointer Ag and Pd undergo simple reduction. Black-Right-Pointing-Pointer Cu and Ni undergo coordination-then-reduction. Black-Right-Pointing-Pointer Bi undergoes hydrolysis-then-reduction. Black-Right-Pointing-Pointer The as-prepared metals have shown the second largest surface area ever reported.

Metodologia para o crescimento de esferas monocristalinas de metais nobres A methodology for the growing of single crystal spheres of noble metals

Directory of Open Access Journals (Sweden)

Luiz H. Dall'Antonia

1999-09-01

Full Text Available This paper describes in detail a technique employed to grow quasi-spherical single crystals of noble metals for electrochemical applications, using platinum as an example. The metal beads were formed by melting the extremity of a wire in an oxygen / butane flame. X-ray techniques were used to check the crystallization and to determine the orientation of the crystals. Treatment with a pure hydrogen flame followed by a cooling procedure in a hydrogen / argon atmosphere were used for conditioning the well-defined platinum single crystal surfaces. Finally, electrochemical characterization of the Pt(111, Pt(110 and Pt(100 surfaces was done in diluted sulfuric acid solution in the hydrogen adsorption / desorption potential region.

Jingle-bell-shaped ferrite hollow sphere with a noble metal core: Simple synthesis and their magnetic and antibacterial properties

International Nuclear Information System (INIS)

Li Siheng; Wang Enbo; Tian Chungui; Mao Baodong; Kang Zhenhui; Li Qiuyu; Sun Guoying

2008-01-01

In this paper, a simple strategy is developed for rational fabrication of a class of jingle-bell-shaped hollow structured nanomaterials marked as Ag(MFe 2 O 4 ) (M=Ni, Co, Mg, Zn), consisting of ferrite hollow shells and metal nanoparticle cores, using highly uniform colloidal Ag(C) microspheres as template. The final composites were obtained by direct adsorption of metal cations Fe 3+ and M 2+ on the surface of the Ag(C) spheres followed by calcination process to remove the middle carbon shell and transform the metal ions into pure phase ferrites. The as-prepared composites were characterized by X-ray photoelectron spectroscopy (XPS), energy-dispersive X-ray analysis (EDX), X-ray powder diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), UV-vis spectroscopy and SQUID magnetometer. The results showed that the composites possess the magnetic property of the ferrite shell and the optical together with antibacterial property of the Ag core. - Graphical abstract: MFe 2 O 4 (M=Ni, Co, Mg, Zn) hollow spheres with a noble metal nanoparticle core were successfully prepared by using colloidal metal(C) core-shell spheres as templates with no need of surface modification. The shell thickness and magnetic properties of the ferrite hollow spheres could be controlled by varying the synthetic parameters

Fast microwave-assisted solvothermal synthesis of metal nanoparticles (Pd, Ni, Sn) supported on sulfonated MWCNTs: Pd-based bimetallic catalysts for ethanol oxidation in alkaline medium

CSIR Research Space (South Africa)

Ramulifho, T

2012-01-01

Full Text Available The preparation of metal nanoparticles (Pd, Ni, Sn) supported on sulfonated multi-walled carbon nanotubes (SF-MWCNTs) using a very rapid microwave-assisted solvothermal strategy has been described. Electrocatalytic behaviour of the SF...

Synthesis, Characterization and Spectral Studies of Noble Heterobinuclear Complexes of Transition Metal Ions and their Biological Activity

Directory of Open Access Journals (Sweden)

Netra Pal Singh

2011-01-01

Full Text Available Some noble heterobinuclear complexes of transition metal ions with bis(salicylaldehydemalonyl-dihydrazone in the presence of 5-nitroindazole Cu(II / Ni(II- chloride of the type [ML1M‘L2Cl2] or [ML1FeL2Cl2]Cl, where M = Ni(II, Cu(II and M' = Mn(II, Co(II, have been prepared. All the complexes have been characterized by IR, UV vis and EPR spectroscopy, elemental analysis, magnetic moment and molar conductance measurement. Spectral studies and magnetic moment measurement in DMF suggest the covalent nature of the complexes, except the [ML1FeL2Cl2]Cl complex which is 1:1 electrolyte. An octahedral geometry is proposed for M‘ and square planer for M for the heterobinuclear complexes. The low value of magnetic moment and overlapping EPR signals are due to spin crossover since both of the metals have unpaired electrons with same molecular symmetry. The lowering of the magnetic moment has been discussed. The biological activity (antifungal and antibacterial of the represented compounds has been studied.

Pressure effect on crystallization temperature in Zr70Pd30 metallic glass

DEFF Research Database (Denmark)

Jiang, Jianzhong; Jeppesen, S; Saida, J.

2004-01-01

The pressure effect on amorphous-to-quasicrystalline-to-intermetallic phase transformations in a Zr70Pd30 metallic glass has been investigated by in situ x-ray diffraction measurements using synchrotron radiation. It is found that the glass crystallizes in two steps: (1) amorphous...... temperature for the formation of quasicrystals has been further discussed with the nucleation theory. ©2004 American Institute of Physics....

Surface Functionalization of g-C 3 N 4 : Molecular-Level Design of Noble-Metal-Free Hydrogen Evolution Photocatalysts

KAUST Repository

Chen, Yin

2015-06-12

A stable noble-metal-free hydrogen evolution photocatalyst based on graphite carbon nitride (g-C3N4) was developed by a molecular-level design strategy. Surface functionalization was successfully conducted to introduce a single nickel active site onto the surface of the semiconducting g-C3N4. This catalyst family (with less than 0.1 wt% of Ni) has been found to produce hydrogen with a rate near to the value obtained by using 3 wt% platinum as co-catalyst. This new catalyst also exhibits very good stability under hydrogen evolution conditions, without any evidence of deactivation after 24h. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Size-dependent effects in supported highly dispersed Fe2O3 catalysts, doped with Pt and Pd

International Nuclear Information System (INIS)

Cherkezova-Zheleva, Zara; Shopska, Maya; Mitov, Ivan; Kadinov, Georgi

2010-01-01

Series of Fe and Fe–Me (Me = Pt or Pd) catalyst supported on γ-Al 2 O 3 , TiO 2 (anatase) or diatomite were prepared by the incipient wetness impregnation method. The metal loading was 8 wt.% Fe and 0.7 wt.% noble metal. The preparation and pretreatment conditions of all studied samples were kept to be the same. X-ray diffraction, Moessbauer spectroscopy, X-ray photoelectron spectroscopy and temperature-programmed reduction are used for characterization of the supports and the samples at different steps during their treatment and catalytic tests. The catalytic activity of the samples was tested in the reaction of total benzene oxidation. The physicochemical and catalytic properties of the obtained materials are compared with respect of the different chemical composition, dispersion of used carriers and of the supported phases. Samples with the same composition prepared by mechanical mixing are studied as catalysts for comparison and for clearing up the presence of size-dependent effect, also.

Vibration-accelerated activation of flow units in a Pd-based bulk metallic glass

Energy Technology Data Exchange (ETDEWEB)

Li, Ning, E-mail: hslining@mail.hust.edu.cn [School of Materials Science and Engineering, and State Key Laboratory of Material Processing and Die & Mould Technology, Huazhong University of Science and Technology, Wuhan 430074 (China); Liu, Ze [Department of Engineering Mechanics, School of Civil Engineering, Wuhan University, Wuhan 430072 (China); Wang, Xinyun [School of Materials Science and Engineering, and State Key Laboratory of Material Processing and Die & Mould Technology, Huazhong University of Science and Technology, Wuhan 430074 (China); Zhang, Meng [Institute of Advanced Wear & Corrosion Resistant and Functional Materials, Jinan University, Guangzhou 510632 (China)

2017-04-24

Controlled activation of flow units and in-situ characterization of mechanical properties in metallic glasses are facing challenges thus far. Here, vibrational loading is introduced through nanoscale dynamic mechanical analysis technique to probe vibration-accelerated atomic level flow that plays a crucial role in the mechanical behavior of metallic glasses. The intriguing finding is that high vibrational frequency induces deep indentation depth, prominent pop-in events on load–depth curves and low storage modulus, exhibiting a vibration-facilitated activation of flow units in Pd{sub 40}Cu{sub 30}Ni{sub 10}P{sub 20} metallic glass. Theoretical analysis revealed that vibration-moderated activation time-scale accelerate the activation of flow units and responsible for the above scenario.

Glycerol electro-oxidation in alkaline medium using Pd/C and PdSn/C electrocatalysts prepared by electron beam irradiation

International Nuclear Information System (INIS)

Geraldes, Adriana Napoleao; Silva, Dionisio Fortunato da; Pino, Eddy Segura; Spinace, Estevan Vitorio; Oliveira Neto, Almir; Linardi, Marcelo; Santos, Mauro Coelhos dos

2013-01-01

Carbon-supported metal nanoparticles were prepared for fuel cell applications by radiation-induced reduction of metal ions precursors. Pd/C and PdSn/C electrocatalysts (Pd:Sn atomic ratio 90:10), prepared by using electron beam irradiation, were tested for glycerol electro-oxidation in single alkaline direct glycerol fuel cell (ADGFC). EDX analysis showed that the Pd:Sn atomic ratio is very similar to the nominal one. X-ray diffractograms of PdSn/C electrocatalyst showed the presence of Pd (fcc) phase. Cyclic voltammetry (CV) indicated that Pd/C and PdSn/C electrocatalysts have good activity for glycerol electro-oxidation, at room temperature. Experiments with single ADGFC were carried out from 60 to 90 deg C, using Pd/C and PdSn/C electrocatalysts and glycerol 2.0 mol.L -1 , as fuel. The best performance was obtained at 85 deg C, for both electrocatalysts. The Pd/C and PdSn/C electrocatalysts showed similar performance (34 mW cm -2 ), at 85 deg C. (author)

Noble Gases in Lakes and Ground Waters

OpenAIRE

Kipfer, Rolf; Aeschbach-Hertig, Werner; Peeters, Frank; Stute, Marvin

2002-01-01

In contrast to most other fields of noble gas geochemistry that mostly regard atmospheric noble gases as 'contamination,' air-derived noble gases make up the far largest and hence most important contribution to the noble gas abundance in meteoric waters, such as lakes and ground waters. Atmospheric noble gases enter the meteoric water cycle by gas partitioning during air / water exchange with the atmosphere. In lakes and oceans noble gases are exchanged with the free atmosphere at the surface...

Application of a mixed metal oxide catalyst to a metallic substrate

Science.gov (United States)

Sevener, Kathleen M. (Inventor); Lohner, Kevin A. (Inventor); Mays, Jeffrey A. (Inventor); Wisner, Daniel L. (Inventor)

2009-01-01

A method for applying a mixed metal oxide catalyst to a metallic substrate for the creation of a robust, high temperature catalyst system for use in decomposing propellants, particularly hydrogen peroxide propellants, for use in propulsion systems. The method begins by forming a prepared substrate material consisting of a metallic inner substrate and a bound layer of a noble metal intermediate. Alternatively, a bound ceramic coating, or frit, may be introduced between the metallic inner substrate and noble metal intermediate when the metallic substrate is oxidation resistant. A high-activity catalyst slurry is applied to the surface of the prepared substrate and dried to remove the organic solvent. The catalyst layer is then heat treated to bind the catalyst layer to the surface. The bound catalyst layer is then activated using an activation treatment and calcinations to form the high-activity catalyst system.

Carbon nanotubes and other nanostructures as support material for nanoparticulate noble-metal catalysts in fuel cells

DEFF Research Database (Denmark)

Veltzé, Sune; Larsen, Mikkel Juul; Elina, Yli-Rantala

or platinum-alloy catalysts in the electrodes are required. To maximize the utilization of the noble metal it is frequently deposited as nanoparticles (1–5 nm) on a stabilizing support of carbon black. Carbon black provides good anchoring of the catalyst particles, but is prone to severe destructive oxidation...... at high electrical potentials encountered occasionally in fuel cells. Other nanostructures of carbon are being investigated as alternatives to carbon black as they have several beneficial properties. Multi-walled carbon nanotubes (MW-CNT) are an example of one type of these promising materials. Like...... of the fuel-cell electrodes. However, the low concentration of structural defects also poses challenges with regard to anchoring of the catalyst particles on the CNT surface. Thus, activation treatments introducing surface functional groups may be necessary. Also, the surface properties are responsible...

Ag Isotopic Evolution of the Mantle During Accretion: New Constraints from Pd and Ag Metal-Silicate Partitioning

Science.gov (United States)

Righter, K.; Schonbachler, M.

2018-01-01

Decay of (sup 107) Pd to (sup 107) Ag has a half-life of 6.5 times 10 (sup 6) mega-annums. Because these elements are siderophile but also volatile, they offer potential constraints on the timing of core formation as well as volatile addition. Initial modelling has shown that the Ag isotopic composition of the bulk silicate Earth (BSE) can be explained if accretion occurs with late volatile addition. These arguments were tested for sensitivity for pre-cursor Pd/Ag contents, and for a fixed Pd/Ag ratio of the BSE of 0.1. New Ag and Pd partitioning data has allowed a better understanding of the partitioning behavior of Pd and Ag during core formation. The effects of S, C and Si, and the effect of high temperature and pressure has been evaluated. We can now calculate D(Ag) and D(Pd) over the wide range of PT conditions and variable metallic liquid compositions that are known during accretion. We then use this new partitioning information to revisit the Ag isotopic composition of the BSE during accretion.

Noble metal extraction and sorption concentrating

International Nuclear Information System (INIS)

Petrukhin, O.M.; Malofeeva, G.I.

1985-01-01

Works performed in the USSR Academy of Sciences GEOCHI laboratory of extraction methods and devoted to selectivity problems of extraction and sorption methods of platinum metal, cadmium and indium concentrating in analytical chemistry are discussed. On choosing complexino. reagent main attention is paid to the selectivity variation based on different stability of metal complexes. Platinum metals are extracted in the form of ion associates when usinq hard, mainly oxyqen-containing, extractants. Coordination-solvated metal complexes are extracted white usinq extractants containing sulfur, trivalent phosphorus and aromatic nitroqen as donor anions. Selectivity is maximum for sulfur- and nitroren-containinq extractants and sorbents. In case of the group extraction of platinum metals sorption is preferable and in case of selective extraction of individual metals, especially, in case of need of relative concentratinq extraction is preferable

Non-noble metal graphene oxide-copper (II) ions hybrid electrodes for electrocatalytic hydrogen evolution reaction

KAUST Repository

Muralikrishna, S.

2015-08-25

Non-noble metal and inexpensive graphene oxide-copper (II) ions (GO-Cu2+) hybrid catalysts have been explored for the hydrogen evolution reaction (HER). We were able to tune the binding abilities of GO toward the Cu2+ ions and hence their catalytic properties by altering the pH. We have utilized the oxygen functional moieties such as carboxylate, epoxide, and hydroxyl groups on the edge and basal planes of the GO for binding the Cu2+ ions through dative bonds. The GO-Cu2+ hybrid materials were characterized by cyclic voltammetry in sodium acetate buffer solution. The morphology of the hybrid GO-Cu2+ was characterized by atomic force microscopy. The GO-Cu2+ hybrid electrodes show good electrocatalytic activity for HER with low overpotential in acidic solution. The Tafel slope for the GO-Cu2+ hybrid electrode implies that the primary discharge step is the rate determining step and HER proceed with Volmer step. © 2015 American Institute of Chemical Engineers Environ Prog.

Metal Carbides for Biomass Valorization

Directory of Open Access Journals (Sweden)

Carine E. Chan-Thaw

2018-02-01

Full Text Available Transition metal carbides have been utilized as an alternative catalyst to expensive noble metals for the conversion of biomass. Tungsten and molybdenum carbides have been shown to be effective catalysts for hydrogenation, hydrodeoxygenation and isomerization reactions. The satisfactory activities of these metal carbides and their low costs, compared with noble metals, make them appealing alternatives and worthy of further investigation. In this review, we succinctly describe common synthesis techniques, including temperature-programmed reaction and carbothermal hydrogen reduction, utilized to prepare metal carbides used for biomass transformation. Attention will be focused, successively, on the application of transition metal carbide catalysts in the transformation of first-generation (oils and second-generation (lignocellulose biomass to biofuels and fine chemicals.

An Amorphous Noble-Metal-Free Electrocatalyst that Enables Nitrogen Fixation under Ambient Conditions.

Science.gov (United States)

Lv, Chade; Yan, Chunshuang; Chen, Gang; Ding, Yu; Sun, Jingxue; Zhou, Yansong; Yu, Guihua

2018-02-23

N 2 fixation by the electrocatalytic nitrogen reduction reaction (NRR) under ambient conditions is regarded as a potential approach to achieve NH 3 production, which still heavily relies on the Haber-Bosch process at the cost of huge energy and massive production of CO 2 . A noble-metal-free Bi 4 V 2 O 11 /CeO 2 hybrid with an amorphous phase (BVC-A) is used as the cathode for electrocatalytic NRR. The amorphous Bi 4 V 2 O 11 contains significant defects, which play a role as active sites. The CeO 2 not only serves as a trigger to induce the amorphous structure, but also establishes band alignment with Bi 4 V 2 O 11 for rapid interfacial charge transfer. Remarkably, BVC-A shows outstanding electrocatalytic NRR performance with high average yield (NH 3 : 23.21 μg h -1  mg -1 cat. , Faradaic efficiency: 10.16 %) under ambient conditions, which is superior to the Bi 4 V 2 O 11 /CeO 2 hybrid with crystalline phase (BVC-C) counterpart. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Surface modification-a novel way of attaching cocatalysts on CdS semiconductors for photocatalytic hydrogen evolution

KAUST Repository

Yu, Weili

2014-08-22

Noble metals as cocatalysts for hydrogen evolution are widely investigated for semiconductor photocatalytic water splitting. In this paper, we present a novel way to attach not only noble metals, but also transitional metals onto CdS nanocrystals as cocatalysts for hydrogen evolution. The hydrogen evolution performances for each metal were compared and result shows that Pd attached CdS gives the highest hydrogen evolution rate of 250 μmol/h. The amounts of metal ions attached on the surface were measured by inductively coupled plasma optical emission spectrometry (ICP-OES). This work confirms that surface modification is a promising way of attaching cocatalysts onto semiconductor photocatalysts.

Surface modification-a novel way of attaching cocatalysts on CdS semiconductors for photocatalytic hydrogen evolution

KAUST Repository

Yu, Weili; Isimjan, Tayirjan; Lin, Bin; Takanabe, Kazuhiro

2014-01-01

Noble metals as cocatalysts for hydrogen evolution are widely investigated for semiconductor photocatalytic water splitting. In this paper, we present a novel way to attach not only noble metals, but also transitional metals onto CdS nanocrystals as cocatalysts for hydrogen evolution. The hydrogen evolution performances for each metal were compared and result shows that Pd attached CdS gives the highest hydrogen evolution rate of 250 μmol/h. The amounts of metal ions attached on the surface were measured by inductively coupled plasma optical emission spectrometry (ICP-OES). This work confirms that surface modification is a promising way of attaching cocatalysts onto semiconductor photocatalysts.

Size-dependent effects in supported highly dispersed Fe{sub 2}O{sub 3} catalysts, doped with Pt and Pd

Energy Technology Data Exchange (ETDEWEB)

Cherkezova-Zheleva, Zara; Shopska, Maya, E-mail: shopska@ic.bas.bg; Mitov, Ivan; Kadinov, Georgi [Bulgarian Academy of Sciences, Institute of Catalysis (Bulgaria)

2010-06-15

Series of Fe and Fe-Me (Me = Pt or Pd) catalyst supported on {gamma}-Al{sub 2}O{sub 3}, TiO{sub 2} (anatase) or diatomite were prepared by the incipient wetness impregnation method. The metal loading was 8 wt.% Fe and 0.7 wt.% noble metal. The preparation and pretreatment conditions of all studied samples were kept to be the same. X-ray diffraction, Moessbauer spectroscopy, X-ray photoelectron spectroscopy and temperature-programmed reduction are used for characterization of the supports and the samples at different steps during their treatment and catalytic tests. The catalytic activity of the samples was tested in the reaction of total benzene oxidation. The physicochemical and catalytic properties of the obtained materials are compared with respect of the different chemical composition, dispersion of used carriers and of the supported phases. Samples with the same composition prepared by mechanical mixing are studied as catalysts for comparison and for clearing up the presence of size-dependent effect, also.

Lipid solubility of the platinum group metals Pt, Pd and Rh in dependence on the presence of complexing agents

International Nuclear Information System (INIS)

Zimmermann, Sonja; Menzel, Christoph M.; Stueben, Doris; Taraschewski, Horst; Sures, Bernd

2003-01-01

All complexing agents had a significant influence on octanol solubility of PGM. - Investigations on the bioaccumulation of the platinum group metals (PGM) Pt, Pd and Rh in aquatic organisms are of growing interest in environmental research due to the increasing emission of these metals by motor vehicles with catalytic converters. Until now, nothing is known about the possible influence of complexing agents on the bioaccumulation capacity of these precious metals. According to the partition coefficient between 1-octanol and water (P OW ) as a measure of bioaccumulation, in this study a simple shaking method was performed in order to investigate the effects of different complexing agents (L-methionine, thio urea, EDTA, humic substances, bile compounds) on the octanol solubility of the PGM. The results demonstrated a significant influence of all agents used. L-Methionine and thio urea decreased the lipid solubility. In contrast, the presence of EDTA, humic substances and especially bile caused a higher transfer of metals in the octanol phase. For most complexing agents tested, the transfer of Pd to the lipid phase was significantly higher compared with Rh and Pt, except for bile acid where the highest octanol solubility was found for Pt. Recent experimental results on PGM accumulation in zebra mussels confirm a high bioaccumulation of Pd which could be predicted from the lipid solubility

Lipid solubility of the platinum group metals Pt, Pd and Rh in dependence on the presence of complexing agents

Energy Technology Data Exchange (ETDEWEB)

Zimmermann, Sonja; Menzel, Christoph M.; Stueben, Doris; Taraschewski, Horst; Sures, Bernd

2003-07-01

All complexing agents had a significant influence on octanol solubility of PGM. - Investigations on the bioaccumulation of the platinum group metals (PGM) Pt, Pd and Rh in aquatic organisms are of growing interest in environmental research due to the increasing emission of these metals by motor vehicles with catalytic converters. Until now, nothing is known about the possible influence of complexing agents on the bioaccumulation capacity of these precious metals. According to the partition coefficient between 1-octanol and water (P{sub OW}) as a measure of bioaccumulation, in this study a simple shaking method was performed in order to investigate the effects of different complexing agents (L-methionine, thio urea, EDTA, humic substances, bile compounds) on the octanol solubility of the PGM. The results demonstrated a significant influence of all agents used. L-Methionine and thio urea decreased the lipid solubility. In contrast, the presence of EDTA, humic substances and especially bile caused a higher transfer of metals in the octanol phase. For most complexing agents tested, the transfer of Pd to the lipid phase was significantly higher compared with Rh and Pt, except for bile acid where the highest octanol solubility was found for Pt. Recent experimental results on PGM accumulation in zebra mussels confirm a high bioaccumulation of Pd which could be predicted from the lipid solubility.

Noble gases in common rocks and their bearing on noble gas occurrences in the hydrological cycle

International Nuclear Information System (INIS)

Mazor, E.

1978-10-01

The comparison of the noble gases contents in different rocks and in thermal and cold water sources in the French Massif Central was aimed to define the amounts and nature of noble gases contributed by country rocks as opposed to atmospheric noble gases brought in by recharged water. No difference in the noble gas contents was found between waters coming in igneous rocks to those issuing in sedimentary rocks. In both, significant variations in the contents of atmospheric and radiogenic noble gases were found. Radiogenic helium has been found to reveal a positive correlation to the contents of atmospheric Ne, Ar, Kr. This indicates water recharge into the deep part of the systems, mixing with radiogenic He and Ar flushed from igneous and sedimentary rocks and subsequent partial gas loss. Loss of gas is evident from the observed low noble gas contents. These losses have been accompanied by a reversed retention pattern of Ne, Ar, Xc. This reversed retention pattern cannot be an artifact of sampling as well as cannot result by partial steam loss. A similar interpretation for the observed noble gas depletions that agrees with the fact that the observed fractionation patterns are not ''normal'' is given by deuterium and oxygen-18. The stable isotope data seem to exclude partial steam losses

Effects of composition and microstructure of Pd-Cu-Si metallic glassy alloy thin films on hydrogen absorbing properties

International Nuclear Information System (INIS)

Kajita, Susumu; Kohara, Shinji; Onodera, Yohei; Fukunaga, Toshiharu; Matsubara, Eiichiro

2011-01-01

Thin films of Pd-Cu-Si metallic glassy alloys for a hydrogen sensor were fabricated by a sputtering method. In order to find out the effect of the composition and the microstructure of them on the hydrogen absorbing property (the H 2 response), the structural parameters based on the short-range order (SRO) were measured. Additionally, the change of the structural parameters with hydrogen absorption was measured, and the correlations of the change with the H 2 response and the hydrogen induced linear expansion coefficient (LEC) were examined. The H 2 response decreased with increases in Si content and the structural parameters. These results can be explained by the positive effects of Si content and the structural parameters on the formation of a trigonal prism which is a structural unit of Pd-based amorphous alloys, and by the negative effect of the trigonal prism on absorbing hydrogen. From the observation of the elongation of the Pd-Pd atomic distance with absorbing hydrogen, H atoms are supposed to occupy the space between Pd atoms. The amount of the change in the Pd-Pd atomic distance showed the positive correlations with the H 2 response and the LEC. (author)

Magnetism in ordered metallic perovskite compound GdPd3BxC1-x

International Nuclear Information System (INIS)

Pandey, Abhishek; Mazumdar, Chandan; Ranganathan, R.; Dattagupta, S.

2009-01-01

We report results of dc-magnetization, ac-susceptibility and magnetoresistance measurements on crystalline metallic-perovskite compounds GdPd 3 B x C 1-x (x=0.25, 0.50, 0.75 and 1.00) and the parent cubic compound GdPd 3 . The interest in these materials stems from the observation of negative temperature coefficient of resistance and negative thermal expansion in some of the members of this series. In the present study, we show that by substitution of non-magnetic elements, boron and carbon, the nature of the magnetic interaction can be varied from dominating ferromagnetic to antiferromagnetic and finally to a canted magnetic structure without altering the crystal symmetry of the compounds. The variation of magnetic interaction by modifying the lattice parameter resembles Ruderman-Kittel-Kasuya-Yosida (RKKY) oscillations.

Promotion Effect of Alkali Metal Hydroxides on Polymer-Stabilized Pd Nanoparticles for Selective Hydrogenation of C–C Triple Bonds in Alkynols

OpenAIRE

Nikoshvili, Linda Zh.; Bykov, Alexey V.; Khudyakova, Tatiana E.; Lagrange, Thomas; Héroguel, Florent; Luterbacher, Jeremy S.; Matveeva, Valentina G.; Sulman, Esther M.; Dyson, Paul J.; Kiwi-Minsker, Lioubov

2017-01-01

Postimpregnation of Pd nanoparticles (NPs) stabilized within hyper-cross-linked polystyrene with sodium or potassium hydroxides of optimal concentration was found to significantly increase the catalytic activity for the partial hydrogenation of the C–C triple bond in 2-methyl-3-butyn-2-ol at ambient hydrogen pressure. The alkali metal hydroxide accelerates the transformation of the residual Pd(II) salt into Pd(0) NPs and diminishes the reaction induction period. In addition, the selectivity t...

Na+/K+-ATPase: Activity and inhibition

Science.gov (United States)

Čolović, M.; Krstić, D.; Krinulović, K.; Momić, T.; Savić, J.; Vujačić, A.; Vasić, V.

2009-09-01

The aim of the study was to give an overview of the mechanism of inhibition of Na+/K+-ATPase activity induced by some specific and non specific inhibitors. For this purpose, the effects of some ouabain like compounds (digoxin, gitoxin), noble metals complexes ([PtCl2DMSO2], [AuCl4]-, [PdCl4]2-, [PdCl(dien)]+, [PdCl(Me4dien)]+), transition metal ions (Cu2+, Zn2+, Fe2+, Co2+), and heavy metal ions (Hg2+, Pb2+, Cd2+) on the activity of Na+/K+-ATPase from rat synaptic plasma membranes (SPM), porcine cerebral cortex and human erythrocytes were discussed.

Positron scattering from noble gases future prospects

Energy Technology Data Exchange (ETDEWEB)

Jones, A C L; Caradonna, P; Makochekanwa, C; Slaughter, D S; Sullivan, J P; Buckman, S J [Centre for Antimatter-Matter Studies, Research School of Physics and Engineering, Australian National University, Canberra, ACT (Australia); Mitroy, J, E-mail: acj107@rsphysse.anu.edu.a [Faculty of Education Health and Science, Charles Darwin University, NT (Australia)

2009-11-01

Recent results for positron scattering from noble gases over an energy range from 0.5 to 60eV are presented. Measurements include the grand total ({sigma}{sub GT}), Ps formation ({sigma}{sub Ps}) and Grand total - Ps formation (({sigma}{sub GT}-P{sub s}) cross sections. Some preliminary DCS results will also be presented. Work on a formulation of modified effective range theory (MERT) is being undertaken to determine the value of the scattering length which may be useful for identifying a bound state. Plans for experiments on metal atoms will be outlined.

Raman spectroscopy of DNA-metal complexes. I. Interactions and conformational effects of the divalent cations: Mg, Ca, Sr, Ba, Mn, Co, Ni, Cu, Pd, and Cd

OpenAIRE

Duguid, J.; Bloomfield, V.A.; Benevides, J.; Thomas Jr, G.J.

1993-01-01

Interactions of divalent metal cations (Mg2+, Ca2+, Ba2+, Sr2+, Mn2+, Co2+, Ni2+, Cu2+, Pd2+, and Cd2+) with DNA have been investigated by laser Raman spectroscopy. Both genomic calf-thymus DNA (> 23 kilobase pairs) and mononucleosomal fragments (160 base pairs) were employed as targets of metal interaction in solutions containing 5 weight-% DNA and metal:phosphate molar ratios of 0.6:1. Raman difference spectra reveal that transition metal cations (Mn2+, Co2+, Ni2+, Cu2+, Pd2+, and Cd2+) ind...

Expeditious synthesis of noble metal nanoparticles using Vitamin B12 under microwave irradiation

Science.gov (United States)

A greener synthesis protocol for noble nanometals is developed using vitamin B12 as a reducing and capping agent in conjunction with the use of microwaves. Successful assembly of nanoparticles or microparticles with varied shapes and sizes have been demonstrated. The synthesized ...

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

Science.gov (United States)

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.

Noble metal catalysts in the production of biofuels

Energy Technology Data Exchange (ETDEWEB)

Gutierrez, A.

2013-11-01

The energy demand is increasing in the world together with the need to ensure energy security and the desire to decrease greenhouse gas emissions. While several renewable alternatives are available for the production of electricity, e.g. solar energy, wind power, and hydrogen, biomass is the only renewable source that can meet the demand for carbon-based liquid fuels and chemicals. The technology applied in the conversion of biomass depends on the type and complexity of the biomass, and the desired fuel. Hydrogen and hydrogen-rich mixtures (synthesis gas) are promising energy sources as they are more efficient and cleaner than existing fuels, especially when they are used in fuel cells. Hydrotreatment is a catalytic process that can be used in the conversion of biomass or biomass-derived liquids into fuels. In autothermal reforming (ATR), catalysts are used in the production of hydrogen-rich mixtures from conventional fuels or bio-fuels. The different nature of biomass and biomass-derived liquids and mineral oil makes the use of catalysts developed for the petroleum industry challenging. This requires the improvement of available catalysts and the development of new ones. To overcome the limitations of conventional hydrotreatment and ATR catalysts, zirconia-supported mono- and bimetallic rhodium, palladium, and platinum catalysts were developed and tested in the upgrading of model compounds for wood-based pyrolysis oil and in the production of hydrogen, using model compounds for gasoline and diesel. Catalysts were also tested in the ATR of ethanol. For comparative purposes commercial catalysts were tested and the results obtained with model compounds were compared with those obtained with real feedstocks (hydrotreatmet tests with wood-based pyrolysis oil and ATR tests with NExBTL renewable diesel). Noble metal catalysts were active and selective in the hydrotreatment of guaiacol used as the model compound for the lignin fraction of wood-based pyrolysis oil and wood

Phenomenological understanding of dewetting and embedding of noble metal nanoparticles in thin films induced by ion irradiation

Energy Technology Data Exchange (ETDEWEB)

Prakash, Jai, E-mail: jai.gupta1983@gmail.com [Department of Chemistry, MMH College (Ch. Charan Singh University Meerut), Ghaiziabad 201001 (India); Chemical Physics of Materials, Université Libre de Bruxelles, Campus de la Plaine, CP 243, B-1050 Bruxelles (Belgium); Tripathi, A. [Inter University Accelerator Centre, Aruna Asif Ali Marg, New Delhi 110067 (India); Gautam, Sanjeev; Chae, K.H.; Song, Jonghan [Advanced Analysis Center, Korea Institute of Science and Technology, Seoul 136–791 (Korea, Republic of); Rigato, V. [INFN Laboratori Nazionali di Legnaro, Via Romea. 4, 35020 Legnaro, Padova (Italy); Tripathi, Jalaj [Department of Chemistry, MMH College (Ch. Charan Singh University Meerut), Ghaiziabad 201001 (India); Asokan, K. [Inter University Accelerator Centre, Aruna Asif Ali Marg, New Delhi 110067 (India)

2014-10-15

The present experimental work provides the phenomenological approach to understand the dewetting in thin noble metal films with subsequent formation of nanoparticles (NPs) and embedding of NPs induced by ion irradiation. Au/polyethyleneterepthlate (PET) bilayers were irradiated with 150 keV Ar ions at varying fluences and were studied using scanning electron microscopy (SEM) and cross-sectional transmission electron microscopy (X-TEM). Thin Au film begins to dewet from the substrate after irradiation and subsequent irradiation results in spherical nanoparticles on the surface that at a fluence of 5 × 10{sup 16} ions/cm{sup 2} become embedded into the substrate. In addition to dewetting in thin films, synthesis and embedding of metal NPs by ion irradiation, the present article explores fundamental thermodynamic principles that govern these events systematically under the effect of irradiation. The results are explained on the basis of ion induced sputtering, thermal spike inducing local melting and of thermodynamic driving forces by minimization of the system free energy where contributions of surface and interfacial energies are considered with subsequent ion induced viscous flow in substrate. - Highlights: • Phenomenological interpretation of dewetting and embedding of metal NPs in thin film. • Exploring fundamental thermodynamic principles under influence of ion irradiation. • Ion induced surface/interface microstructural changes using SEM/X-TEM. • Ion induced sputtering, thermal spike induced local melting. • Thermodynamic driving forces relate to surface and interfacial energies.

Structural Stability and Performance of Noble Metal-Free SnO2-Based Gas Sensors

Directory of Open Access Journals (Sweden)

Antonio Tricoli

2012-05-01

Full Text Available The structural stability of pure SnO2 nanoparticles and highly sensitive SnO2-SiO2 nanocomposites (0–15 SiO2 wt% has been investigated for conditions relevant to their utilization as chemoresistive gas sensors. Thermal stabilization by SiO2 co-synthesis has been investigated at up to 600 °C determining regimes of crystal size stability as a function of SiO2-content. For operation up to 400 °C, thermally stable crystal sizes of ca. 24 and 11 nm were identified for SnO2 nanoparticles and 1.4 wt% SnO2-SiO2 nanocomposites, respectively. The effect of crystal growth during operation (TO = 320 °C on the sensor response to ethanol has been reported, revealing possible long-term destabilization mechanisms. In particular, crystal growth and sintering-neck formation were discussed with respect to their potential to change the sensor response and calibration. Furthermore, the effect of SiO2 cosynthesis on the cross-sensitivity to humidity of these noble metal-free SnO2-based gas sensors was assessed.

Leaching of gold, silver and accompanying metals from circuit boards (PCBs waste

Directory of Open Access Journals (Sweden)

Jana Ficeriová

2011-12-01

Full Text Available Au-Ag noble metal wastes represent a wide range of waste types and forms, with various accompanying metallic elements.The presented leaching strategy for Au-Ag contained in circuit boards (PCBs aims at gaining gold and silver in the metallic form.Application of the proposed ammonium thiosulphate leaching process for the treatment of the above mentioned Au-Ag containing wastesrepresents a practical, economic and at the same time an ecological solution. The ammonium thiosulphate based leaching of gold and silverfrom PCBs waste, using crushing as a pretreatment, was investigated. It was possible to achieve 98 % gold and 93 % silver recovery within48 hours of ammonium thiosulphate leaching. This type of leaching is a better leaching procedure for recovery of gold and silver from PCBwaste than the classical toxic cyanide leaching. 84 % Cu, 82 % Fe, 77 % Al, 76 % Zn, 70 % Ni, 90 % Pd, 88 % Pb and 83 % Sn recovery ofthe accompanying metals was achieved, using sulphuric acid with hydrogen peroxide, sodium chloride and aqua regia. A four steps leachingprocess gave a very satisfactory yield and a more rapid kinetics for all observed metals solubilization than other technologies.

Synthesis of Ultra-Small Platinum, Palladium and Gold Nanoparticles by Shewanella loihica PV-4 Electrochemically Active Biofilm and Their Enhanced Catalytic Activities

KAUST Repository

Ahmed, Elaf

2018-02-21

Ultra-small nanoparticles (USNPs) of noble metals have a great potential in a variety of applications due to their high surface areas and high reactivity. This works employed electrochemically active biofilms (EABs) composed of a single bacterium strain of Shewanella loihica PV-4 and successfully synthesized USNPs of noble metal Au, Pd, and Pt. The synthesized USNPs had a size range between 2 and 7 nm and exhibited excellent catalytic performance in dye decomposition. The results of this work shine lights on the use of EABs in nanoparticle synthesis.

Metal-dielectric-CNT nanowires for surface-enhanced Raman spectroscopy

Science.gov (United States)

Bond, Tiziana C.; Altun, Ali; Park, Hyung Gyu

2017-10-03

A sensor with a substrate includes nanowires extending vertically from the substrate, a hafnia coating on the nanowires that provides hafnia coated nanowires, and a noble metal coating on the hafnia coated nanowires. The top of the hafnia and noble metal coated nanowires bent onto one another to create a canopy forest structure. There are numerous randomly arranged holes that let through scattered light. The many points of contact, hot spots, amplify signals. The methods include the steps of providing a Raman spectroscopy substrate, introducing nano crystals to the Raman spectroscopy substrate, growing a forest of nanowires from the nano crystals on the Raman spectroscopy substrate, coating the nanowires with hafnia providing hafnia coated nanowires, and coating the hafnia coated nanowires with a noble metal or other metal.

Geochemical behaviour of palladium in soils and Pd/PdO model substances in the presence of the organic complexing agents L-methionine and citric acid.

Science.gov (United States)

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

Noble gas magnetic resonator

Science.gov (United States)

Walker, Thad Gilbert; Lancor, Brian Robert; Wyllie, Robert

2014-04-15

Precise measurements of a precessional rate of noble gas in a magnetic field is obtained by constraining the time averaged direction of the spins of a stimulating alkali gas to lie in a plane transverse to the magnetic field. In this way, the magnetic field of the alkali gas does not provide a net contribution to the precessional rate of the noble gas.

The use of masking agents in the determination, by hydride generation and atomic-absorption spectrophotometry, of arsenic, antimony, selenium, tellurium, and bismuth in the presence of noble metals

International Nuclear Information System (INIS)

Kellerman, S.P.

1982-01-01

The effectiveness of thiosemicarbazide, tellurium, and potassium iodide as masking agents to eliminate interferences was assessed. Thiosemicarbazide was found to be effective in eliminating or reducing the interferences on arsenic, antimony, and bismuth, and tellurium reduced the interferences on selenium. The interferences on tellurium could not be eliminated. Arsenic, antimony, selenium, and bismuth were determined in metal sulphide concentrates that were spiked with the noble metals (defined here as gold plus all the platinum-group metals except osmium). The relative standard deviations for arsenic, antimony, bismuth, and selenium were 0,061, 0,017, 0,029, and 0,145 respectively. The values obtained for all the analytes agreed favourably with the preferred values for two in-house reference samples. The laboratory method is detailed in an appendix

Nanostructured Ti-Zr-Pd-Si-(Nb) bulk metallic composites: Novel biocompatible materials with superior mechanical strength and elastic recovery.

Science.gov (United States)

Hynowska, A; Blanquer, A; Pellicer, E; Fornell, J; Suriñach, S; Baró, M D; Gebert, A; Calin, M; Eckert, J; Nogués, C; Ibáñez, E; Barrios, L; Sort, J

2015-11-01

The microstructure, mechanical behaviour, and biocompatibility (cell culture, morphology, and cell adhesion) of nanostructured Ti45 Zr15 Pd35- x Si5 Nbx with x = 0, 5 (at. %) alloys, synthesized by arc melting and subsequent Cu mould suction casting, in the form of rods with 3 mm in diameter, are investigated. Both Ti-Zr-Pd-Si-(Nb) materials show a multi-phase (composite-like) microstructure. The main phase is cubic β-Ti phase (Im3m) but hexagonal α-Ti (P63/mmc), cubic TiPd (Pm3m), cubic PdZr (Fm3m), and hexagonal (Ti, Zr)5 Si3 (P63/mmc) phases are also present. Nanoindentation experiments show that the Ti45 Zr15 Pd30 Si5 Nb5 sample exhibits lower Young's modulus than Ti45 Zr15 Pd35 Si5 . Conversely, Ti45 Zr15 Pd35 Si5 is mechanically harder. Actually, both alloys exhibit larger values of hardness when compared with commercial Ti-40Nb, (HTi-Zr-Pd-Si ≈ 14 GPa, HTi-Zr-Pd-Si-Nb ≈ 10 GPa and HTi-40Nb ≈ 2.7 GPa). Concerning the biological behaviour, preliminary results of cell viability performed on several Ti-Zr-Pd-Si-(Nb) discs indicate that the number of live cells is superior to 94% in both cases. The studied Ti-Zr-Pd-Si-(Nb) bulk metallic system is thus interesting for biomedical applications because of the outstanding mechanical properties (relatively low Young's modulus combined with large hardness), together with the excellent biocompatibility. © 2014 Wiley Periodicals, Inc.

Noble gases solubility in water

International Nuclear Information System (INIS)

Crovetto, Rosa; Fernandez Prini, Roberto.

1980-07-01

The available experimental data of solubility of noble gases in water for temperatures smaller than 330 0 C have been critically surveyed. Due to the unique structure of the solvent, the solubility of noble gases in water decreases with temperature passing through a temperature of minimum solubility which is different for each gas, and then increases at higher temperatures. As aresult of the analysis of the experimental data and of the features of the solute-solvent interaction, a generalized equation is proposed which enables thecalculation of Henry's coefficient at different temperatures for all noble gases. (author) [es

Evidence of polymorphous amorphous-to-quasicrystalline phase transformation in Zr66.7Pd33.3 metallic glass

DEFF Research Database (Denmark)

Jiang, Jianzhong; Saksl, K.; Saida, J.

2002-01-01

The amorphous-to-quasicrystalline phase transformation and the pressure effect on the transformation in a Zr66.7Pd33.3 metallic glass have been investigated by in situ x-ray diffraction measurements using synchrotron radiation. It is found that the transformation is a polymorphous reaction...

Theoretical studies of the work functions of Pd-based bimetallic surfaces

International Nuclear Information System (INIS)

Ding, Zhao-Bin; Wu, Feng; Wang, Yue-Chao; Jiang, Hong

2015-01-01

Work functions of Pd-based bimetallic surfaces, including mainly M/Pd(111), Pd/M, and Pd/M/Pd(111) (M = 4d transition metals, Cu, Au, and Pt), are studied using density functional theory. We find that the work function of these bimetallic surfaces is significantly different from that of parent metals. Careful analysis based on Bader charges and electron density difference indicates that the variation of the work function in bimetallic surfaces can be mainly attributed to two factors: (1) charge transfer between the two different metals as a result of their different intrinsic electronegativity, and (2) the charge redistribution induced by chemical bonding between the top two layers. The first factor can be related to the contact potential, i.e., the work function difference between two metals in direct contact, and the second factor can be well characterized by the change in the charge spilling out into vacuum. We also find that the variation in the work functions of Pd/M/Pd(111) surfaces correlates very well with the variation of the d-band center of the surface Pd atom. The findings in this work can be used to provide general guidelines to design new bimetallic surfaces with desired electronic properties

Efficient Catalytic Reduction of Hexavalent Chromium With Pd-decorated Carbon Nanotubes

Energy Technology Data Exchange (ETDEWEB)

Kim, Ji Dang; Choi, Hyun Chul [Chonnam National University, Gwangju (Korea, Republic of)

2016-05-15

Heavy metal pollution is currently a serious environmental issue. Chromium (Cr) and chromium compounds are commonly found in wastewater discharged by various industries such as wood preservation, leather tanning, electroplating, metal finishing, and the production of chemicals. Pd nanoparticles can easily be introduced into CNTs by performing DCC-activated amidation. Our TEM and XRD results indicate that well-dispersed metallic Pd nanoparticles are anchored on the surface of the amidated CNTs. The XPS results suggest that the Pd content of the sample is approximately 9.8 atomic %. In comparison with the commercial Pd catalyst, the prepared Pd-CNTs were demonstrated to exhibit good catalytic activity in the reduction of 4-NP by NaBH4. Moreover, the Pd-CNT catalyst can easily be separated by performing a simple filtration and reused over at least 10 cycles. This Pd-CNT catalyst is therefore believed to have significant potential for use as a reusable catalyst in the reduction of Cr(Vi)

Formation of Mixed-Ligand Complexes of Pd2+ with Nucleoside 5'-Monophosphates and Some Metal-Ion-Binding Nucleoside Surrogates

Directory of Open Access Journals (Sweden)

Oleg Golubev

2014-10-01

Full Text Available Formation of mixed-ligand Pd2+ complexes between canonical nucleoside 5'-monophosphates and five metal-ion-binding nucleoside analogs has been studied by 1H-NMR spectroscopy to test the ability of these nucleoside surrogates to discriminate between unmodified nucleobases by Pd2+-mediated base pairing. The nucleoside analogs studied included 2,6-bis(3,5-dimethylpyrazol-1-yl-, 2,6-bis(1-methylhydrazinyl- and 6-(3,5-dimethylpyrazol-1-yl-substituted 9-(β-d-ribofuranosylpurines 1–3, and 2,4-bis(3,5-dimethylpyrazol-1-yl- and 2,4-bis(1-methylhydrazinyl-substituted 5-(β-d-ribofuranosyl-pyrimidines 4–5. Among these, the purine derivatives 1-3 bound Pd2+ much more tightly than the pyrimidine derivatives 4, 5 despite apparently similar structures of the potential coordination sites. Compounds 1 and 2 formed markedly stable mixed-ligand Pd2+ complexes with UMP and GMP, UMP binding favored by 1 and GMP by 2. With 3, formation of mixed-ligand complexes was retarded by binding of two molecules of 3 to Pd2+.

Fe2Ni2N nanosheet array: an efficient non-noble-metal electrocatalyst for non-enzymatic glucose sensing

Science.gov (United States)

You, Chao; Dai, Rui; Cao, Xiaoqin; Ji, Yuyao; Qu, Fengli; Liu, Zhiang; Du, Gu; Asiri, Abdullah M.; Xiong, Xiaoli; Sun, Xuping; Huang, Ke

2017-09-01

It is very important to develop enhanced electrochemical sensing platforms for molecular detection and non-noble-metal nanoarray architecture, as electrochemical catalyst electrodes have attracted great attention due to their large specific surface area and easy accessibility to target molecules. In this paper, we demonstrate that an Fe2Ni2N nanosheet array grown on Ti mesh (Fe2Ni2N NS/TM) shows high electrocatalytic activity toward glucose electrooxidation in alkaline medium. As an electrochemical glucose sensor, such an Fe2Ni2N NS/TM catalyst electrode demonstrates superior sensing performance with a short response time of less than 5 s, a wide linear range of 0.05 μM-1.5 mM, a low detection limit of 0.038 μM (S/N = 3), a high sensitivity of 6250 μA mM-1 cm-2, as well as high selectivity and long-term stability.

Direct Activation Of Methane

KAUST Repository

Basset, Jean-Marie; Sun, Miao; Caps, Valerie; Pelletier, Jeremie; Abou-Hamad, Edy

2013-01-01

Heteropolyacids (HPAs) can activate methane at ambient temperature (e.g., 20.degree. C.) and atmospheric pressure, and transform methane to acetic acid, in the absence of any noble metal such as Pd). The HPAs can be, for example, those with Keggin

Alloying behaviour of electroplated Ag film with its underlying Pd/Ti film stack for low resistivity interconnect metallization

International Nuclear Information System (INIS)

Ezawa, Hirokazu; Miyata, Masahiro; Tatsumi, Kohei

2014-01-01

Highlights: • Alloying behavior of Ag/Pd/Ti film stack was studied by annealing at 400-800 °C. • The Ag film resistivity decreased with increasing annealing temperature. • Formation of the Pd-Ti intermetallics was found to be dominant over Ag-Pd alloying. • The excess Ti was consumed to form Ti oxides, which inhibited Ti alloying with Ag. -- Abstract: In this paper, viability of electroplated Ag film into device application was studied. Alloying behavior of the Ag film with its underlying Pd(50 nm)/Ti(100 nm) film stack was investigated with respect to heat treatment at different temperatures from 400 °C to 800 °C in an argon ambient. After annealing at 400 °C, the electrical resistivity of the Ag film increased due to Pd alloying with Ag. Formation of Pd–Ti intermetallic phases became dominant over Ag–Pd alloying with increasing annealing temperature, leading to the resistivity decrease of the Ag film. The resistivity of the 800 °C annealed Ag film approached that of its as-plated Ag film. The excess Ti atoms which were not consumed to form the intermetallic phases with the Pd atoms migrated to the Ag film surface to form Ti oxides along the Ag grain boundaries on the topmost film surface. The Ag/Pd/Ti film stack has been confirmed to maintain the resistivity of the Ag film at as-plated low levels after high temperature annealing. This paper also discusses process integration issues to enable the Ag metallization process for future scaled and three dimensionally chip stacked devices

Mineralogía y comportamiento geoquímico del oro en los macizos lherzoliticos Betico-Rifeños (España y Marruecos

Directory of Open Access Journals (Sweden)

Leblanc, M.

1991-12-01

Full Text Available The Lherzolite massifs from the Serranía de Ronda and Beni Bousera are pieces of the upper mantle emplaced in the continental crust. Before their crustal emplacement, the Lherzolite suffered several partial melting events, giving rise to depleted peridotites (harzburgites and dunites as well as to pyroxenites and magmatic Cr, Cr-Ni and (Fe-Ni-Cu sulfide ores. The average Au content are strongly concentrated in the mineralizations, especially in the Cr-Ni ores, in contrast with the usual behaviour of the noble metals in magmatic ores related to mafic-ultramafic rocks. Au, Pt and Pd are concentrated in the Ni arsenides where most of the former elements are hidden in solid solution in the niccolite. The alteration of niccolite produces the exsolution of native Au and alloys of Au-Cu and Au-Cu-Ag. In most (Fe-Ni-Cu sulfide ores, the Au content is very low. However, the bodies with the highest Cu/Ni ratio and with hydrothermally altered wall rocks are enriched in Au. The geochemical behaviour of noble metals suggests that the parental partial melts of the «ore magma» were generated from a depleted mantle source and originally, they were S- and As-undersaturated and enriched in noble metals. During ore formation, As played an important role as collector of Au (as well as of Pt and Pd; therefore, the earlier As saturation of the liquids and the subsequent crystallization of the Ni arsenides produced Au-, Pt- and Pd-depleted (Fe-Ni-Cu sulfide ores.Los macizos lherzolíticos de la Serranía de Ronda y de Beni Bousera representan porciones del Manto superior, emplazadas en la Corteza continental tras haber sufrido varios episodios de fusión parcial. Dichos macizos contienen gran variedad de rocas: lherzolitas, harzburgitas, dunitas, piroxenitas, y mineralizaciones magmáticas de Cr, de Cr-Ni, y de sulfuros de Fe-Ni-Cu. Los contenidos medios en Au en los distintos tipos de rocas indican un comportamiento de elemento incompatible durante los

Study of metal specific interaction, F-LUMO and VL shift to understand interface of CuPc thin films and noble metal surfaces

Energy Technology Data Exchange (ETDEWEB)

Sinha, Sumona; Mukherjee, M., E-mail: manabendra.mukherjee@saha.ac.in

2015-10-30

Graphical abstract: - Highlights: • F-LUMO, a hybridized state near E{sub F} confirms partial charge transfer. • Non-significant role of partial charge transfer in VL shift over push back effect. • Pyrrole sites affected for partial charge transfer from Cu and Ag substrates. • Negligible effect on pyrrole cites for Pt and Au substrates. - Abstract: The performances of organic electronic devices are significantly associated with their energy level alignment at organic semiconductor/metal–electrode interfaces. The electronic character of an organic semiconducting molecular over-layer on a metal surface can vary from semiconducting to metallic, depending on the nature of the molecular orbitals with respect to the Fermi level of the electrode. The general tendency of extrapolating established models for single crystal substrates to ‘real’ device substrates is highly misleading. Hence, the importance of metal specific interaction, former lowest unoccupied molecular orbital (F-LUMO) and vacuum level (VL) shift have been investigated as a function of thickness of the deposited films by means of photoelectron spectroscopy (XPS and UPS) to understand the interface between CuPc and Cu, Ag, Pt and Au foils sequentially. The XPS data provides the signature of affectability of pyrrole sites of CuPc molecules for partial charge transfer from Cu and Ag substrates while a negligible effect on pyrrole cites resulted for Pt and Au substrates. Furthermore, the appearance of F-LUMO, a hybridized state close to the Fermi level gives confirmatory information about partial charge transfer. Contrary to the general belief that vacuum level shift caused by charge transfer can partially or totally cancel that for push back effect, our observation indicates that the partial charge transfer does not play significant role in the shift of vacuum level. The entire thickness dependent electronic energy level alignment of CuPc films on all noble metal substrates is explained in terms

Study of metal specific interaction, F-LUMO and VL shift to understand interface of CuPc thin films and noble metal surfaces

International Nuclear Information System (INIS)

Sinha, Sumona; Mukherjee, M.

2015-01-01

Graphical abstract: - Highlights: • F-LUMO, a hybridized state near E_F confirms partial charge transfer. • Non-significant role of partial charge transfer in VL shift over push back effect. • Pyrrole sites affected for partial charge transfer from Cu and Ag substrates. • Negligible effect on pyrrole cites for Pt and Au substrates. - Abstract: The performances of organic electronic devices are significantly associated with their energy level alignment at organic semiconductor/metal–electrode interfaces. The electronic character of an organic semiconducting molecular over-layer on a metal surface can vary from semiconducting to metallic, depending on the nature of the molecular orbitals with respect to the Fermi level of the electrode. The general tendency of extrapolating established models for single crystal substrates to ‘real’ device substrates is highly misleading. Hence, the importance of metal specific interaction, former lowest unoccupied molecular orbital (F-LUMO) and vacuum level (VL) shift have been investigated as a function of thickness of the deposited films by means of photoelectron spectroscopy (XPS and UPS) to understand the interface between CuPc and Cu, Ag, Pt and Au foils sequentially. The XPS data provides the signature of affectability of pyrrole sites of CuPc molecules for partial charge transfer from Cu and Ag substrates while a negligible effect on pyrrole cites resulted for Pt and Au substrates. Furthermore, the appearance of F-LUMO, a hybridized state close to the Fermi level gives confirmatory information about partial charge transfer. Contrary to the general belief that vacuum level shift caused by charge transfer can partially or totally cancel that for push back effect, our observation indicates that the partial charge transfer does not play significant role in the shift of vacuum level. The entire thickness dependent electronic energy level alignment of CuPc films on all noble metal substrates is explained in terms of a

Surface modification of g-C3N4 by hydrazine: Simple way for noble-metal free hydrogen evolution catalysts

KAUST Repository

Chen, Yin

2015-11-02

The graphitic carbon nitride (g-C3N4) usually is thought to be an inert material and it’s difficult to have the surface terminated NH2 groups functionalized. By modifying the g-C3N4 surface with hydrazine, the diazanyl group was successfully introduced onto the g-C3N4 surface, which allows the introduction with many other function groups. Here we illustrated that by reaction of surface hydrazine group modified g-C3N4 with CS2 under basic condition, a water electrolysis active group C(=S)SNi can be implanted on the g-C3N4 surface, and leads to a noble metal free hydrogen evolution catalyst. This catalyst has 40% hydrogen evolution efficiency compare to the 3 wt% Pt photo precipitated g-C3N4, with only less than 0.2 wt% nickel.

Surface modification of g-C3N4 by hydrazine: Simple way for noble-metal free hydrogen evolution catalysts

KAUST Repository

Chen, Yin; Lin, Bin; Wang, Hong; Yang, Yong; Zhu, Haibo; Yu, Weili; Basset, Jean-Marie

2015-01-01

The graphitic carbon nitride (g-C3N4) usually is thought to be an inert material and it’s difficult to have the surface terminated NH2 groups functionalized. By modifying the g-C3N4 surface with hydrazine, the diazanyl group was successfully introduced onto the g-C3N4 surface, which allows the introduction with many other function groups. Here we illustrated that by reaction of surface hydrazine group modified g-C3N4 with CS2 under basic condition, a water electrolysis active group C(=S)SNi can be implanted on the g-C3N4 surface, and leads to a noble metal free hydrogen evolution catalyst. This catalyst has 40% hydrogen evolution efficiency compare to the 3 wt% Pt photo precipitated g-C3N4, with only less than 0.2 wt% nickel.

Process Intensification of Alkynol Semihydrogenation in a Tube Reactor Coated with a Pd/ZnO Catalyst

Directory of Open Access Journals (Sweden)

Nikolay Cherkasov

2017-11-01

Full Text Available Semihydrogenation of 2-methyl-3-butyn-2-ol (MBY was studied in a 5 m tube reactor wall-coated with a 5 wt% Pd/ZnO catalyst. The system allowed for the excellent selectivity towards the intermediate alkene of 97.8 ± 0.2% at an ambient H2 pressure and a MBY conversion below 90%. The maximum alkene yield reached 94.6% under solvent-free conditions and 96.0% in a 30 vol % MBY aqueous solution. The reactor stability was studied for 80 h on stream with a deactivation rate of only 0.07% per hour. Such a low deactivation rate provides a continuous operation of one month with only a two-fold decrease in catalyst activity and a metal leaching below 1 parts per billion (ppb. The excellent turn-over numbers (TON of above 105 illustrates a very efficient utilisation of the noble metal inside catalyst-coated tube reactors. When compared to batch operation at 70 °C, the reaction rate in flow reactor can be increased by eight times at a higher reaction temperature, keeping the same product decomposition of about 1% in both cases.

Pd/PdO functionalization of SnO{sub 2} nanowires and ZnO nanotetrapods

Energy Technology Data Exchange (ETDEWEB)

De Zorzi, C.; Rossetto, G. [ICIS-CNR, Padova (Italy); Calestani, D.; Zha, M.Z.; Zappettini, A.; Lazzarini, L.; Villani, M.; Zanotti, L. [IMEM-CNR, Parma (Italy); El Habra, N. [ICIS-CNR, Padova (Italy); Dipt. Scienze Chimiche, Universita di Padova (Italy)

2011-08-15

Tin oxide (SnO{sub 2}) and zinc oxide (ZnO) nanostructures are widely studied because of their peculiar physical and chemical properties and the large number of possible application fields. Surface functionalization of these materials is a very important topic because it is a powerful tool for modifying or tuning their properties, in order to better match the device requests. For example, palladium/palladium oxide (Pd/PdO) nanoparticles are often used to enhance selectivity of chemoresistive gas sensing properties of metal-oxide nanostructures. SnO{sub 2} nanowires and ZnO nanotetrapods have been grown on large areas by a combination of metal evaporation and controlled oxidation, while a MOCVD (Metal Organic Chemical Vapor Deposition) process has been chosen in order to deposit Pd/PdO nanoparticles on the surface of the obtained oxide nanostructures. Samples morphology, structure and composition have been studied by means of SEM and TEM microscopy, EDS microanalysis and X-Ray diffraction. The different results, obtained as a function of the synthesis and annealing parameters, are discussed focusing the attention to the experimental conditions that allowed the authors to obtain an optimal ''spotted'' coverage of oxide nanostructures, which is often required for gas sensing application. (copyright 2011 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

Highly active Pd-In/mesoporous alumina catalyst for nitrate reduction.

Science.gov (United States)

Gao, Zhenwei; Zhang, Yonggang; Li, Deyi; Werth, Charles J; Zhang, Yalei; Zhou, Xuefei

2015-04-09

The catalytic reduction of nitrate is a promising technology for groundwater purification because it transforms nitrate into nitrogen and water. Recent studies have mainly focused on new catalysts with higher activities for the reduction of nitrate. Consequently, metal nanoparticles supported on mesoporous metal oxides have become a major research direction. However, the complex surface chemistry and porous structures of mesoporous metal oxides lead to a non-uniform distribution of metal nanoparticles, thereby resulting in a low catalytic efficiency. In this paper, a method for synthesizing the sustainable nitrate reduction catalyst Pd-In/Al2O3 with a dimensional structure is introduced. The TEM results indicated that Pd and In nanoparticles could efficiently disperse into the mesopores of the alumina. At room temperature in CO2-buffered water and under continuous H2 as the electron donor, the synthesized material (4.9 wt% Pd) was the most active at a Pd-In ratio of 4, with a first-order rate constant (k(obs) = 0.241 L min(-1) g(cata)(-1)) that was 1.3× higher than that of conventional Pd-In/Al2O3 (5 wt% Pd; 0.19 L min(-1) g(cata)(-1)). The Pd-In/mesoporous alumina is a promising catalyst for improving the catalytic reduction of nitrate. Copyright © 2015 Elsevier B.V. All rights reserved.

Synthesis of Ultra-Small Platinum, Palladium and Gold Nanoparticles by Shewanella loihica PV-4 Electrochemically Active Biofilm and Their Enhanced Catalytic Activities

KAUST Repository

Ahmed, Elaf; Kalathil, Shafeer; Shi, Le; Alharbi, Ohoud; Li, Renyuan; Zaouri, Noor A.; Wang, Peng

2018-01-01

strain of Shewanella loihica PV-4 and successfully synthesized USNPs of noble metal Au, Pd, and Pt. The synthesized USNPs had a size range between 2 and 7 nm and exhibited excellent catalytic performance in dye decomposition. The results of this work

A palladium-doped ceria@carbon core-sheath nanowire network: a promising catalyst support for alcohol electrooxidation reactions

Science.gov (United States)

Tan, Qiang; Du, Chunyu; Sun, Yongrong; Du, Lei; Yin, Geping; Gao, Yunzhi

2015-08-01

A novel palladium-doped ceria and carbon core-sheath nanowire network (Pd-CeO2@C CSNWN) is synthesized by a template-free and surfactant-free solvothermal process, followed by high temperature carbonization. This hierarchical network serves as a new class of catalyst support to enhance the activity and durability of noble metal catalysts for alcohol oxidation reactions. Its supported Pd nanoparticles, Pd/(Pd-CeO2@C CSNWN), exhibit >9 fold increase in activity toward the ethanol oxidation over the state-of-the-art Pd/C catalyst, which is the highest among the reported Pd systems. Moreover, stability tests show a virtually unchanged activity after 1000 cycles. The high activity is mainly attributed to the superior oxygen-species releasing capability of Pd-doped CeO2 nanowires by accelerating the removal of the poisoning intermediate. The unique interconnected one-dimensional core-sheath structure is revealed to facilitate immobilization of the metal catalysts, leading to the improved durability. This core-sheath nanowire network opens up a new strategy for catalyst performance optimization for next-generation fuel cells.A novel palladium-doped ceria and carbon core-sheath nanowire network (Pd-CeO2@C CSNWN) is synthesized by a template-free and surfactant-free solvothermal process, followed by high temperature carbonization. This hierarchical network serves as a new class of catalyst support to enhance the activity and durability of noble metal catalysts for alcohol oxidation reactions. Its supported Pd nanoparticles, Pd/(Pd-CeO2@C CSNWN), exhibit >9 fold increase in activity toward the ethanol oxidation over the state-of-the-art Pd/C catalyst, which is the highest among the reported Pd systems. Moreover, stability tests show a virtually unchanged activity after 1000 cycles. The high activity is mainly attributed to the superior oxygen-species releasing capability of Pd-doped CeO2 nanowires by accelerating the removal of the poisoning intermediate. The unique

Metal-semiconductor transition at a comparable resistivity level and positive magnetoresistance in Mn3Mn1-x Pd x N thin films

Science.gov (United States)

Xu, T.; Ji, G. P.; Cao, Z. X.; Ji, A. L.

2018-02-01

Thin films of antiperovskite Mn3Mn1-x Pd x N with x up to 0.36 were grown by reactive magnetron co-sputtering method. All the deposits exhibit a [1 0 0] preferential orientation, with the lattice constant slightly enlarged in samples with ever more Pd atoms partially substituting the MnI atoms in Mn3MnN matrix. The replacement of MnI atoms in antiperovskite structure by Pd atoms, besides reducing the saturation magnetization, also invokes a metal-semiconductor transition which occurs remarkably at a comparable resistivity level. Moreover, a positive magnetoresistance was observed in samples of a high Pd content. These tunable electrical and magnetic properties of ternary antiperovskite compounds might promise some ingenious applications in electronic industry.

Investigating unexpected magnetism of mesoporous silica-supported Pd and PdO nanoparticles

KAUST Repository

Song, Hyon Min

2015-01-13

The synthesis and magnetic behavior of matrix-supported Pd and PdO nanoparticles (NPs) are described. Mesoporous silica with hexagonal columnal packing is selected as a template, and the impregnation method with thermal annealing is used to obtain supported Pd and PdO NPs. The heating rate and the annealing conditions determine the particle size and the phase of the NPs, with a fast heating rate of 30 °C/min producing the largest supported Pd NPs. Unusual magnetic behaviors are observed. (1) Contrary to the general belief that smaller Pd NPs or cluster size particles have higher magnetization, matrix-supported Pd NPs in this study maintain the highest magnetization with room temperature ferromagnetism when the size is the largest. (2) Twin boundaries along with stacking faults are more pronounced in these large Pd NPs and are believed to be the reason for this high magnetization. Similarly, supported PdO NPs were prepared under air conditions with different heating rates. Their phase is tetragonal (P42/mmc) with cell parameters of a = 3.050 Å and c = 5.344 Å, which are slightly larger than in the bulk phase (a = 3.03 Å, c = 5.33 Å). Faster heating rate of 30 °C/min also produces larger particles and larger magnetic hysteresis loop, although magnetization is smaller and few twin boundaries are observed compared to the supported metallic Pd NPs.

Method and electrochemical cell for synthesis and treatment of metal monolayer electrocatalysts metal, carbon, and oxide nanoparticles ion batch, or in continuous fashion

Science.gov (United States)

Adzic, Radoslav; Zhang, Junliang; Sasaki, Kotaro

2015-04-28

An apparatus and method for synthesis and treatment of electrocatalyst particles in batch or continuous fashion is provided. In one embodiment, the apparatus comprises a sonication bath and a two-compartment chamber submerged in the sonication bath. The upper and lower compartments are separated by a microporous material surface. The upper compartment comprises a cover and a working electrode (WE) connected to a Pt foil contact, with the foil contact connected to the microporous material. The upper chamber further comprises reference counter electrodes. The lower compartment comprises an electrochemical cell containing a solution of metal ions. In one embodiment, the method for synthesis of electrocatalysts comprises introducing a plurality of particles into the apparatus and applying sonication and an electrical potential to the microporous material connected to the WE. After the non-noble metal ions are deposited onto the particles, the non-noble metal ions are displaced by noble-metal ions by galvanic displacement.

Potential Energy Curves and Associated Line Shape of Alkali-Metal and Noble-Gas Interactions

Science.gov (United States)

2014-10-20

work. The ab initio calculations for M + Ng molecular combina- tions are reported and discussed in Chapter 3. Chapter 4 discusses both pedagogical ...mass of the noble-gas atom decreases. These barriers at R = rb are accompanied by shallow wells at R = rmin2 and, together with the shallow wells

Engineering Metal Nanostructure for SERS Application

Directory of Open Access Journals (Sweden)

Yanqin Cao

2013-01-01

Full Text Available Surface-enhanced Raman scattering (SERS has attracted great attention due to its remarkable enhancement and excellent selectivity in the detection of various molecules. Noble metal nanomaterials have usually been employed for producing substrates that can be used in SERS because of their unique local plasma resonance. As the SERS enhancement of signals depends on parameters such as size, shape, morphology, arrangement, and dielectric environment of the nanostructure, there have been a number of studies on tunable nanofabrication and synthesis of noble metals. In this work, we will illustrate progress in engineering metallic nanostructures with various morphologies using versatile methods. We also discuss their SERS applications in different fields and the challenges.

Plasma-chemical production of metal-polypyrrole-catalysts for the reduction of oxygen in fuel cells. Precious-metal-free catalysts for fuel cells.; Plasmachemische Erzeugung von Metall-Polypyrrol-Katalysatoren fuer die Sauerstoffreduktion in Brennstoffzellen. Edelmetallfreie Katalysatoren fuer Brennstoffzellen

Energy Technology Data Exchange (ETDEWEB)

Walter, Christian

2013-07-01

This thesis is about the production of non noble metal catalysts for the oxygen reduction reaction in fuel cells. Therefore, a novel dual plasma process is developed, constructed and the so-produced films are analysed by various electrochemical (CV, RDE and RRDE) and structural methods (SEM, EDX, IR, XPS, conductivity, XRD, NEXAFS, EXAFS and TEM). It is shown, that by doing this, non noble metal catalysts could be produced without the need of a high temperature treatment. Furthermore, the catalytic activity obtained is superior to that of chemically produced metal-polypyrrole films.

Adlayer Core-Level Shifts of Random Metal Overlayers on Transition-Metal Substrates

DEFF Research Database (Denmark)

Ganduglia-Pirovano, M. V.; Kudrnovský, J.; Scheffler, M.

1997-01-01

and the screening effects induced by the core hole, and study the influence of the alloy composition for a number of noble metal-transition metal systems. Our analysis clearly indicates the importance of final-state screening effects for the interpretation of measured core-level shifts. Calculated deviations from...

Session 6: Catalytic hydro-dehalogenation of halon 1211 (CBrClF{sub 2}) over carbon supported Pd-Fe, Pd-Co and Pd-Ni bimetallic catalysts

Energy Technology Data Exchange (ETDEWEB)

Hai, Yu; Kennedy, E.M.; Md Azhar, Uddin; Dlugogorski, B.Z. [Newcastle Univ., Process Safety and Environment Protection Group, School of Engineering, Callaghan, NSW (Australia)

2004-07-01

In the current study, we present the result of our investigation on the hydro-dehalogenation of halon 1211 with hydrogen over carbon supported Pd-Fe, Pd-Co and Pd-Ni bimetallic catalysts. In addition to dissociatively adsorbing hydrogen, Fe, Co and Ni themselves can facilitate cleavage of C-halogen bonds. The effect of the interaction of a second metal (Fe, Co and Ni) with Pd on the conversion of halon 1211 and selectivity to CH{sub 2}F{sub 2} for the catalytic hydro-dehalogenation of halon 1211 is discussed. Activated carbon is chosen as support in order to minimize the interaction of support with the metals. The obtained experimental results show that the introduction of Fe, Co and Ni to Pd catalysts has a significant influence on the catalytic hydro-dehalogenation of halon 1211, especially with respect to the selectivity to CH{sub 2}F{sub 2}. The presence of Fe increases the amount of halon 1211 adsorbed on the surface of catalysts and enhances the cleavage of C-halogen bonds in halon 1211, resulting in a higher halon 1211 conversion level and selectivity to hydrocarbons. Higher selectivity to CHBrF{sub 2} is ascribed to the secondary reaction: CF{sub 2} + HBr {yields} CHBrF{sub 2}. (authors)

GREEN SYNTHESIS OF SILVER AND PALLADIUM NANOPARTICLES AT ROOM TEMPERATURE USING COFFEE AND TEA EXTRACT

Science.gov (United States)

An extremely simple green approach that generates bulk quantities of nanocrystals of noble metals such as silver (Ag) and palladium (Pd) using coffee and tea extract at room temperature is described. The single-pot method uses no surfactant, capping agent, and/or template. The ob...

Muonium formation in noble gases and noble gas mixtures

International Nuclear Information System (INIS)

Stambaugh, R.D.; Casperson, D.E.; Crane, T.W.; Hughes, V.W.; Kaspar, H.F.; Souder, P.; Thompson, P.A.; Orth, H.; zu Putlitz, G.; Denison, A.B.

1974-01-01

An experiment is reported to study the behavior of positive muons stopped in He, Ne, and Xe in order to provide a more complete understanding of muonium formation in the noble gases. Free muon and muonium precession are plotted. (U.S.)

Impact of humic substances on the aqueous solubility, uptake and bioaccumulation of platinum, palladium and rhodium in exposure studies with Dreissena polymorpha

International Nuclear Information System (INIS)

Sures, Bernd; Zimmermann, Sonja

2007-01-01

Zebra mussels (Dreissena polymorpha) were exposed to different types of water containing PGE salts (PtCl 4 , PdSO 4 , RhCl 3 ) to investigate the influence of humic substances on the aqueous solubility, uptake and bioaccumulation of noble metals. The results showed a time dependent decrease of the aqueous PGE concentrations in tank water for all groups. This could mainly be related to non-biological processes. The aqueous solubility of Pd and Rh was higher in humic water compared with non-chlorinated tap water, whereas Pt showed opposing results. Highest metal uptake rates and highest bioaccumulation plateaus were found for Pd, followed by Pt and Rh. Pd uptake and bioaccumulation was significantly hampered by humic substances, whose presence appear to increase Pt uptake and bioaccumulation. No clear trend emerged for Rh. Differences in effects of humic matter among the PGE may be explained by formation of metal complexes with different fractions of humic substances. - Precious metal accumulation in Dreissena polymorpha is affected by humic substances

Density functional calculations on 13-atom Pd12M (M = Sc—Ni) bimetallic clusters

International Nuclear Information System (INIS)

Tang Chun-Mei; Chen Sheng-Wei; Zhu Wei-Hua; Tao Cheng-Jun; Zhang Ai-Mei; Gong Jiang-Feng; Zou Hua; Liu Ming-Yi; Zhu Feng

2012-01-01

The geometric structures, electronic and magnetic properties of the 3d transition metal doped clusters Pd 12 M (M = Sc—Ni) are studied using the semi-core pseudopots density functional theory. The groundstate geometric structure of the Pd 12 M cluster is probably of pseudoicosahedron. The I h -Pd 12 M cluster has the most thermodynamic stability in five different symmetric isomers. The energy gap shows that Pd 12 M cluster is partly metallic. Both the absolutely predominant metal bond and very weak covalent bond might exist in the Pd 12 M cluster. The magnetic moment of Pd 12 M varies from 0 to 5 μ B , implying that it has a potential application in new nanomaterials with tunable magnetic properties

Understanding Catalytic Activity Trends for NO Decomposition and CO Oxidation using Density Functional Theory and Microkinetic Modeling

DEFF Research Database (Denmark)

Falsig, Hanne

-metal surfaces by combining a database of adsorption energies on stepped metal surfaces with known Brønsted–Evans–Polanyi (BEP) relations for the activation barriers of dissociation of diatomic molecules over stepped transition- and noble-metal surfaces. The potential energy diagram directly points to why Pd......The main aim of this thesis is to understand the catalytic activity of transition metals and noble metals for the direct decomposition of NO and the oxidation of CO. The formation of NOx from combustion of fossil and renewable fuels continues to be a dominant environmental issue. We take one step...... towards rationalizing trends in catalytic activity of transition metal catalysts for NO decomposition by combining microkinetic modelling with density functional theory calculations. We establish the full potential energy diagram for the direct NO decomposition reaction over stepped transition...

Mitigation of hydrogen by oxidation using nitrous oxide and noble metal catalysts

International Nuclear Information System (INIS)

Britton, M.D.

1995-01-01

This test studied the ability of a blend of nuclear-grade, noble-metal catalysts to catalyze a hydrogen/nitrous oxide reaction in an effort to mitigate a potential hydrogen (H 2 ) gas buildup in the Hanford Site Grout Disposal Facility. For gases having H 2 and a stoichiometric excess of either nitrous oxide or oxygen, the catalyst blend can effectively catalyze the H 2 oxidation reaction at a rate exceeding 380 μmoles of H 2 per hour per gram of catalyst (μmol/h/g) and leave the gas with less than a 0.15 residual H 2 Concentration. This holds true in gases with up to 2.25% water vapor and 0.1% methane. This should also hold true for gases with up to 0.1% carbon monoxide (CO) but only until the catalyst is exposed to enough CO to block the catalytic sites and stop the reaction. Gases with ammonia up to 1% may be slightly inhibited but can have reaction rates greater than 250 μmol/h/g with less than a 0.20% residual H 2 concentration. The mechanism for CO poisoning of the catalyst is the chemisorption of CO to the active catalyst sites. The CO sorption capacity (SC) of the catalyst is the total amount of CO that the catalyst will chemisorb. The average SC for virgin catalyst was determined to be 19.3 ± 2.0 μmoles of CO chemisorbed to each gram of catalyst (μmol/g). The average SC for catalyst regenerated with air was 17.3 ± 1.9 μmol/g

Development of an inter-atomic potential for the Pd-H binary system.

Energy Technology Data Exchange (ETDEWEB)

Zimmerman, Jonathan A.; Hoyt, Jeffrey John (McMaster University, Hamilton, Ontario, Canada); Leonard, Francois Leonard; Griffin, Joshua D.; Zhou, Xiao Wang

2007-09-01

Ongoing research at Sandia National Laboratories has been in the area of developing models and simulation methods that can be used to uncover and illuminate the material defects created during He bubble growth in aging bulk metal tritides. Previous efforts have used molecular dynamics calculations to examine the physical mechanisms by which growing He bubbles in a Pd metal lattice create material defects. However, these efforts focused only on the growth of He bubbles in pure Pd and not on bubble growth in the material of interest, palladium tritide (PdT), or its non-radioactive isotope palladium hydride (PdH). The reason for this is that existing inter-atomic potentials do not adequately describe the thermodynamics of the Pd-H system, which includes a miscibility gap that leads to phase separation of the dilute (alpha) and concentrated (beta) alloys of H in Pd at room temperature. This document will report the results of research to either find or develop inter-atomic potentials for the Pd-H and Pd-T systems, including our efforts to use experimental data and density functional theory calculations to create an inter-atomic potential for this unique metal alloy system.

Initial Evaluation of Processing Methods for an Epsilon Metal Waste Form

International Nuclear Information System (INIS)

Crum, Jarrod V.; Strachan, Denis M.; Zumhoff, Mac R.

2012-01-01

During irradiation of nuclear fuel in a reactor, the five metals, Mo, Pd, Rh, Ru, and Tc, migrate to the fuel grain boundaries and form small metal particles of an alloy known as epsilon metal ((var e psilon)-metal). When the fuel is dissolved in a reprocessing plant, these metal particles remain behind with a residue - the undissolved solids (UDS). Some of these same metals that comprise this alloy that have not formed the alloy are dissolved into the aqueous stream. These metals limit the waste loading for a borosilicate glass that is being developed for the reprocessing wastes. Epsilon metal is being developed as a waste form for the noble metals from a number of waste streams in the aqueous reprocessing of used nuclear fuel (UNF) - (1) the (var e psilon)-metal from the UDS, (2) soluble Tc (ion-exchanged), and (3) soluble noble metals (TRUEX raffinate). Separate immobilization of these metals has benefits other than allowing an increase in the glass waste loading. These materials are quite resistant to dissolution (corrosion) as evidenced by the fact that they survive the chemically aggressive conditions in the fuel dissolver. Remnants of (var e psilon)-metal particles have survived in the geologically natural reactors found in Gabon, Africa, indicating that they have sufficient durability to survive for ∼ 2.5 billion years in a reducing geologic environment. Additionally, the (var e psilon)-metal can be made without additives and incorporate sufficient foreign material (oxides) that are also present in the UDS. Although (var e psilon)-metal is found in fuel and Gabon as small particles (∼10 (micro)m in diameter) and has survived intact, an ideal waste form is one in which the surface area is minimized. Therefore, the main effort in developing (var e psilon)-metal as a waste form is to develop a process to consolidate the particles into a monolith. Individually, these metals have high melting points (2617 C for Mo to 1552 C for Pd) and the alloy is expected

Magnetism and transport studies in off-stoichiometric metallic perovskite compounds GdPd{sub 3}B{sub x} (x=0.25, 0.50 and 0.75)

Energy Technology Data Exchange (ETDEWEB)

Pandey, Abhishek, E-mail: abhishek.phy@gmail.co [S. N. Bose National Centre for Basic Sciences, Block-JD, Sector-III, Salt Lake, Kolkata 700098 (India); Experimental Condensed Matter Physics Division, Saha Institute of Nuclear Physics, 1/AF, Bidhannagar, Kolkata 700064 (India); Mazumdar, Chandan, E-mail: chandan.mazumdar@saha.ac.i [Experimental Condensed Matter Physics Division, Saha Institute of Nuclear Physics, 1/AF, Bidhannagar, Kolkata 700064 (India); Ranganathan, R. [Experimental Condensed Matter Physics Division, Saha Institute of Nuclear Physics, 1/AF, Bidhannagar, Kolkata 700064 (India)

2010-12-15

We report the magnetic and transport properties of the off-stoichiometric metallic perovskite like compounds GdPd{sub 3}B{sub x} (x=0.25, 0.50 and 0.75). Our results show that doping with boron in the lattice of parent binary-compound GdPd{sub 3} leads to lattice expansion. Which in turn manifests in contrasting magnetic and transport behaviors of the doped compounds in comparison with the undoped GdPd{sub 3}. An attempt has been made to compare and correlate the results of magnetic and transport measurements of GdPd{sub 3}B{sub x} with that of stoichiometric compositions GdPd{sub 3}B{sub x}C{sub 1-x}. The comparative study of GdPd{sub 3}B{sub x} and GdPd{sub 3}B{sub x}C{sub 1-x} confirms that there is a strong correlations between the structural, magnetic and transport properties of these compounds.

Noble-metal-free NiO@Ni-ZnO/reduced graphene oxide/CdS heterostructure for efficient photocatalytic hydrogen generation

Science.gov (United States)

Chen, Fayun; Zhang, Laijun; Wang, Xuewen; Zhang, Rongbin

2017-11-01

Noble-metal-free semiconductor materials are widely used for photocatalytic hydrogen generation because of their low cost. ZnO-based heterostructures with synergistic effects exhibit an effective photocatalytic activity. In this work, NiO@Ni-ZnO/reduced graphene oxide (rGO)/CdS heterostructures are synthesized by a multi-step method. rGO nanosheets and CdS nanoparticles were introduced into the heterostructures via a redox reaction and light-assisted growth, respectively. A novel Ni-induced electrochemical growth method was developed to prepare ZnO rods from Zn powder. NiO@Ni-ZnO/rGO/CdS heterostructures with a wide visible-light absorption range exhibited highly photocatalytic hydrogen generation rates under UV-vis and visible light irradiation. The enhanced photocatalytic activity is attributed to the Ni nanoparticles that act as cocatalysts for capturing photoexcited electrons and the improved synergistic effect between ZnO and CdS due to the rGO nanosheets acting as photoexcited carrier transport channels.

Ion implantation - a useful tool for the preparation of new materials

International Nuclear Information System (INIS)

Buckel, W.

1975-01-01

The following experimental results on ion implantation in superconductors are discussed: 1) Implantation of paramagnetic manganese ions into the superconductors Sn, Pb, Hg lowers the transition temperature. 2) Sn implanted with Mn exhibits the Kondo effect, a minimum in the resistivity versus temperature immediately above Tsub(c). 3) Pd may become superconducting, when charged with H at ratios H/Pd > 0.8. Tsub(c) first increases with concentration and then drops again. The increase in Tsub(c) is still larger for Pd-noble metal alloys charged with H(D). (WBU) [de

Electrodes synthesized from carbon nanostructures coated with a smooth and conformal metal adlayer

Science.gov (United States)

Adzic, Radoslav; Harris, Alexander

2014-04-15

High-surface-area carbon nanostructures coated with a smooth and conformal submonolayer-to-multilayer thin metal films and their method of manufacture are described. The preferred manufacturing process involves the initial oxidation of the carbon nanostructures followed by a surface preparation process involving immersion in a solution with the desired pH to create negative surface dipoles. The nanostructures are subsequently immersed in an alkaline solution containing a suitable quantity of non-noble metal ions which adsorb at surface reaction sites. The metal ions are then reduced via chemical or electrical means. The nanostructures are exposed to a solution containing a salt of one or more noble metals which replace adsorbed non-noble surface metal atoms by galvanic displacement. The process can be controlled and repeated to obtain a desired film coverage. The resulting coated nanostructures may be used, for example, as high-performance electrodes in supercapacitors, batteries, or other electric storage devices.

Design of Pd-Based Bimetallic Catalysts for ORR: A DFT Calculation Study

Directory of Open Access Journals (Sweden)

Lihui Ou

2015-01-01

Full Text Available Developing Pd-lean catalysts for oxygen reduction reaction (ORR is the key for large-scale application of proton exchange membrane fuel cells (PEMFCs. In the present paper, we have proposed a multiple-descriptor strategy for designing efficient and durable ORR Pd-based alloy catalysts. We demonstrated that an ideal Pd-based bimetallic alloy catalyst for ORR should possess simultaneously negative alloy formation energy, negative surface segregation energy of Pd, and a lower oxygen binding ability than pure Pt. By performing detailed DFT calculations on the thermodynamics, surface chemistry and electronic properties of Pd-M alloys, Pd-V, Pd-Fe, Pd-Zn, Pd-Nb, and Pd-Ta, are identified theoretically to have stable Pd segregated surface and improved ORR activity. Factors affecting these properties are analyzed. The alloy formation energy of Pd with transition metals M can be mainly determined by their electron interaction. This may be the origin of the negative alloy formation energy for Pd-M alloys. The surface segregation energy of Pd is primarily determined by the surface energy and the atomic radius of M. The metals M which have smaller atomic radius and higher surface energy would tend to favor the surface segregation of Pd in corresponding Pd-M alloys.

Improved recovery of trace amounts of gold (III), palladium (II) and platinum (IV) from large amounts of associated base metals using anion-exchange resins

Energy Technology Data Exchange (ETDEWEB)

Matsubara, I. [Lab. of Chemistry, Tokyo Women' s Medical Univ. (Japan); Takeda, Y.; Ishida, K. [Lab. of Chemistry, Nippon Medical School, Kawasaki-shi, Kanagawa-ken (Japan)

2000-02-01

The adsorption and desorption behaviors of gold (III), palladium (II) and platinum (IV) were surveyed in column chromatographic systems consisting of one of the conventional anion-exchange resins of large ion-exchange capacity and dilute thiourea solutions. The noble metals were strongly adsorbed on the anion-exchange resins from dilute hydrochloric acid, while most base metals did not show any marked adsorbability. These facts made it possible to separate the noble metals from a large quantity of base metals such as Ag (I), Al (III), Co (II), Cu (II), Fe (III), Mn (II), Ni (II), Pb (II), and Zn (II). Although it used to be very difficult to desorb the noble metals from the resins used, the difficulty was easily overcome by use of dilute thiourea solutions as an eluant. In the present study, as little as 1.00 {mu}g of the respective noble metals was quantitatively separated and recovered from as much as ca. 10 mg of a number of metals on a small column by elution with a small amount of dilute thiourea solution. The present systems should be applicable to the separation, concentration and recovery of traces of the noble metals from a number of base metals coexisting in a more extended range of amounts and ratios. (orig.)

Seed-mediated co-reduction in a large lattice mismatch system: synthesis of Pd-Cu nanostructures.

Science.gov (United States)

Kunz, Meredith R; McClain, Sophia M; Chen, Dennis P; Koczkur, Kallum M; Weiner, Rebecca G; Skrabalak, Sara E

2017-06-08

Metal nanoparticles (NPs) are of interest for applications in catalysis, electronics, chemical sensing, and more. Their utility is dictated by their composition and physical parameters such as particle size, particle shape, and overall architecture (e.g., hollow vs. solid). Interestingly, the addition of a second metal to create bimetallic NPs adds multifunctionality, with new emergent properties common. However, synthesizing structurally defined bimetallic NPs remains a great challenge. One synthetic pathway to architecturally controlled bimetallic NPs is seed-mediated co-reduction (SMCR) in which two metal precursors are simultaneously co-reduced to deposit metal onto shape-controlled metal seeds, which direct the overgrowth. Previously demonstrated in a Au-Pd system, here SMCR is applied to a system with a larger lattice mismatch between the depositing metals: Pd and Cu (7% mismatch for Pd-Cu vs. 4% for Au-Pd). Through manipulation of precursor reduction kinetics, the morphology and bimetallic distribution of the resultant NPs can be tuned to achieve eight-branched Pd-Cu heterostructures with Cu localized at the tips of the Pd nanocubes as well as branched Pd-Cu alloyed nanostructures and polyhedra. Significantly, the symmetry of the seeds can be transferred to the final nanostructures. This study expands our understanding of SMCR as a route to structurally defined bimetallic nanostructures and the synthesis of multicomponent nanomaterials more generally.

Noble Gas signatures of Enhanced Oil Recovery

Science.gov (United States)

Barry, P. H.; Kulongoski, J. T.; Tyne, R. L.; Hillegonds, D.; Byrne, D. J.; Landon, M. K.; Ballentine, C. J.

2017-12-01

Noble gases are powerful tracers of fluids from various oil and gas production activities in hydrocarbon reservoirs and nearby groundwater. Non-radiogenic noble gases are introduced into undisturbed oil and natural gas reservoirs through exchange with formation waters [1-3]. Reservoirs with extensive hydraulic fracturing, injection for enhanced oil recovery (EOR), and/or waste disposal also show evidence for a component of noble gases introduced from air [4]. Isotopic and elemental ratios of noble gases can be used to 1) assess the migration history of the injected and formation fluids, and 2) determine the extent of exchange between multiphase fluids in different reservoirs. We present noble gas isotope and abundance data from casing, separator and injectate gases of the Lost Hills and Fruitvale oil fields in the San Joaquin basin, California. Samples were collected as part of the California State Water Resource Control Board's Oil and Gas Regional Groundwater Monitoring Program. Lost Hills (n=7) and Fruitvale (n=2) gases are geochemically distinct and duplicate samples are highly reproducible. Lost Hills casing gas samples were collected from areas where EOR and hydraulic fracturing has occurred in the past several years, and from areas where EOR is absent. The Fruitvale samples were collected from a re-injection port. All samples are radiogenic in their He isotopes, typical of a crustal environment, and show enrichments in heavy noble gases, resulting from preferential adsorption on sediments. Fruitvale samples reflect air-like surface conditions, with higher air-derived noble gas concentrations. Lost Hills gases show a gradation from pristine crustal signatures - indicative of closed-system exchange with formation fluids - to strongly air-contaminated signatures in the EOR region. Pristine samples can be used to determine the extent of hydrocarbon exchange with fluids, whereas samples with excess air can be used to quantify the extent of EOR. Determining noble

Noble magnetic barriers in the ASDEX UG tokamak

Science.gov (United States)

Ali, Halima; Punjabi, Alkesh; Vazquez, Justin

2010-02-01

The second-order perturbation method of creating invariant tori inside chaos in Hamiltonian systems (Ali, H.; Punjabi, A. Plasma Phys. Contr. F. 2007, 49, 1565-1582) is applied to the axially symmetric divertor experiment upgrade (ASDEX UG) tokamak to build noble irrational magnetic barriers inside chaos created by resonant magnetic perturbations (m, n)=(3, 2)+(4, 3), with m and n the poloidal and toroidal mode numbers of the Fourier expansion of the magnetic perturbation. The radial dependence of the Fourier modes is ignored. The modes are considered to be locked and have the same amplitude δ. A symplectic mathematical mapping in magnetic coordinates is used to integrate magnetic field line trajectories in the ASDEX UG. Tori with noble irrational rotational transform are the last ones to be destroyed by perturbation in Hamiltonian systems. For this reason, noble irrational magnetic barriers are built inside chaos, and the strongest noble irrational barrier is identified. Three candidate locations for the strongest noble barrier in ASDEX UG are selected. All three candidate locations are chosen to be roughly midway between the resonant rational surfaces ψ32 and ψ43. ψ is the magnetic coordinate of the flux surface. The three candidate surfaces are the noble irrational surfaces close to the surface with q value that is a mediant of q=3/2 and 4/3, q value of the physical midpoint of the two resonant surfaces, and the q value of the surface where the islands of the two perturbing modes just overlap. These q values of the candidate surfaces are denoted by q MED, q MID, and q OVERLAP. The strongest noble barrier close to q MED has the continued fraction representation (CFR) [1;2,2,1∞] and exists for δ≤2.6599×10-4; the strongest noble barrier close to q MID has CFR [1;2,2,2,1∞] and exists for δ≤4.6311×10-4; and the strongest noble barrier close to q OVERLAP has CFR [1;2,2,6,2,1∞] and exists for δ≤1.367770×10-4. From these results, the strongest

A fast cost-assessment method for boiler equipment made of noble materials

International Nuclear Information System (INIS)

Perreard, J.C.

1994-01-01

The method is aimed at assessing equipment costs for preliminary technical-economic studies or succinct project evaluation. Advantages and disadvantages of nobles metals such as nickel, tantalum, titanium, zirconium ... are reviewed. The economic evaluation method is based on a combination of parametric techniques and statistical results, and allows for the assessment of the various cost components as a function of mass, design and manufacturing complexity in the context of industrial specific operating constraints. 3 figs., 6 tabs., 2 refs

Measurement of benzenethiol adsorption to nanostructured Pt, Pd, and PtPd films using Raman spectroelectrochemistry.

Science.gov (United States)

Pomfret, Michael B; Pietron, Jeremy J; Owrutsky, Jeffrey C

2010-05-04

Raman spectroscopy and electrochemical methods were used to study the behavior of the model adsorbate benzenethiol (BT) on nanostructured Pt, Pd, and PtPd electrodes as a function of applied potential. Benzenethiol adsorbs out of ethanolic solutions as the corresponding thiolate, and voltammetric stripping data reveal that BT is oxidatively removed from all of the nanostructured metals upon repeated oxidative and reductive cycling. Oxidative stripping potentials for BT increase in the order Pt oxidizing potentials via cleavage of the Pt-S bond. In contrast, on nanoscale Pd and PtPd, BT is irreversibly lost due to cleavage of BT C-S bonds at oxidizing potentials, which leaves adsorbed sulfur oxides on Pd and PtPd films and effects the desulfurization of BT. While Pd and PtPd films are less sulfur-resistant than Pt films, palladium oxides, which form at higher potentials than Pt oxides, oxidatively desulfurize BT. In situ spectroelectrochemical Raman spectroscopy provides real-time, chemically specific information that complements the cyclic voltammetric data. The combination of these techniques affords a powerful and convenient method for guiding the development of sulfur-tolerant PEMFC catalysts.

Theoretical study of noble gases diffraction from Ru(0001) using van der Waals DFT-based potentials

International Nuclear Information System (INIS)

Del Cueto, M; Muzas, A S; Martín, F; Díaz, C

2015-01-01

This study aims to analyze the role of van der Waals forces in the diffraction process of noble gases from a metal surface. We made use of different vdW implementations to rationalize the effect of dispersion forces on the corrugation of the system, the resulting scattering patterns and on the eventual diffraction results. (paper)

Preparation technology of 103Pd-110Agm composite alloy membranes

International Nuclear Information System (INIS)

Liu Zhuo; Chen Daming; Jin Xiaohai; Li Zhongyong; Guo Feihu; Qin Hongbin

2012-01-01

The preparation of 103 Pd- 110 Ag m alloy membranes was the basis for the production of 103 Pd- 125 I composite sources. Taking 103 Pd and 110 Ag m as trace elements, the method of non-electrolytical plating was chosen to prepare the alloy membrane. A γ-detector and electron microscope (SEM) were used for quantitative and qualitative analysis, respectively. The pre-treatment of the support before the preparation of Palladium-silver composite membranes was discussed in detail. It was found that when the concentration of PdCl 2 was between 0.5 and 2.0 mmol/L the result was good. The effects of various factors were investigated, including the proportion of Pd and Ag, the concentrations of the total metal, ammonium hydroxide hydrazine and ethylenediaminetetraacetic acid, temperature, the time, and the rotation speed. By improving the reaction conditions the alloy membrane with metallic luster was obtained. Besides, the presence of Pd and Ag was observed in the alloy membranes by qualitative analysis. (authors)

Realization of Copper Melting Point for Thermocouple Calibrations

Directory of Open Access Journals (Sweden)

Y. A. ABDELAZIZ

2011-08-01

Full Text Available Although the temperature stability and uncertainty of the freezing plateau is better than that of the melting plateau in most of the thermometry fixed points, but realization of melting plateaus are easier than that of freezing plateaus for metal fixed points. It will be convenient if the melting points can be used instead of the freezing points in calibration of standard noble metal thermocouples because of easier realization and longer plateau duration of melting plateaus. In this work a comparison between the melting and freezing points of copper (Cu was carried out using standard noble metal thermocouples. Platinum - platinum 10 % rhodium (type S, platinum – 30 % rhodium / platinum 6 % rhodium (type B and platinum - palladium (Pt/Pd thermocouples are used in this study. Uncertainty budget analysis of the melting points and freezing points is presented. The experimental results show that it is possible to replace the freezing point with the melting point of copper cell in the calibration of standard noble metal thermocouples in secondary-level laboratories if the optimal methods of realization of melting points are used.

Formation of noble metal nanocrystals in the presence of biomolecules

Science.gov (United States)

Burt, Justin Lockheart

One of the most promising, yet least studied routes for producing biocompatible nanostructures involves synthesis in the presence of biomolecules. I hypothesized that globular proteins could provide a suitable framework to regulate the formation of noble metal nanocrystals. As proof of concept, I designed two novel synthesis protocols utilizing bovine serum albumin (BSA) protein to regulate the formation of gold nanocrystals. In the first case, the standard protocol for polyol reduction was modified by replacing ethylene glycol with glycerin, replacing synthetic polymers with BSA as protecting agent, and decreasing the reaction temperature. In the second case, the Brust-Schiffrin two-phase reduction was modified by replacing alkylthiols with BSA as protecting agent, which facilitated a strictly aqueous phase synthesis. Due to superior product yield and rapid reduction at room temperature, the aqueous protocol became the foundation for subsequent studies. I extended this approach to produce well-dispersed ˜2nm silver, gold, and platinum nanocrystals. Having demonstrated the feasibility of BSA-functionalized nanocrystals, some potential uses were explored. BSA-functionalized silver nanocrystals were employed in a broader study on the interaction of silver nanocrystals with HIV. BSA-functionalized gold nanocrystals were utilized for in vivo dosage of a contrast enhancing agent to bacteria. BSA-functionalized platinum nanocrystals were studied as hydrogenation catalysts. Since many intriguing uses for protein-functionalized nanocrystals involve incorporation into biosystems, I sought to enhance biocompatibility by using ascorbic acid as reducing agent. Initial experiments revealed elongated and branched nanocrystals. Such structures were not observed in previous synthesis protocols with BSA, so I hypothesized ascorbic acid was driving their formation. To test my assertion, I reduced ionic gold in an aqueous solution of ascorbic acid, thereby discovering a new method

The thermal stability and catalytic performance of Ce-Zr promoted Rh-Pd/γ-Al2O3 automotive catalysts

International Nuclear Information System (INIS)

Wu Xiaodong; Xu Luhua; Weng Duan

2004-01-01

The noble metals (Rh, Pd) supported on alumina promoted with Ce-Zr mixed oxides were investigated as catalysts under diverse oxidants/reductants ratios of simulated automotive exhaust feed gas. Aging test was performed in air at 1000 deg. C for 20 h. Both fresh and aged catalysts, as well as alumina-supported Ce-Zr mixed powders, were characterized by means of X-ray diffraction (XRD), scanning electron microscope (SEM), Brunauer-Emmett-Teller (BET) and X-ray photoelectron spectroscopy (XPS). The results confirmed the oxygen storage capacity of Ce-Zr mixed oxides favored CO, C 3 H 8 and NO conversions in stationary versus dynamic stoichiometric operation. The accelerated aging of the systems produced inconspicuous effect on the phase structure, specific surface area and chemical state of these samples. Accordingly, the aged samples still showed low light-off temperature and broad λ-window, which suggested the relative low relevance of the thermal degradation on the overall catalytic performance of the system

Enhancing Cooperativity in Bifunctional Acid–Pd Catalysts with Carboxylic Acid-Functionalized Organic Monolayers

Energy Technology Data Exchange (ETDEWEB)

Coan, Patrick D. [Department of Chemical and Biological Engineering, University of Colorado—Boulder, Boulder, Colorado 80309, United States; Ellis, Lucas D. [Department of Chemical and Biological Engineering, University of Colorado—Boulder, Boulder, Colorado 80309, United States; Griffin, Michael B. [National Bioenergy Center, National Renewable Energy Laboratory, Golden, Colorado 80401, United States; Schwartz, Daniel K. [Department of Chemical and Biological Engineering, University of Colorado—Boulder, Boulder, Colorado 80309, United States; Medlin, J. Will [Department of Chemical and Biological Engineering, University of Colorado—Boulder, Boulder, Colorado 80309, United States

2018-03-01

Cooperative catalysts containing a combination of noble metal hydrogenation sites and Bronsted acid sites are critical for many reactions, including the deoxygenation (DO) of biomass-derived oxygenates in the upgrading of pyrolysis oil. One route toward the design of cooperative catalysts is to tether two different catalytically active functions so that they are in close proximity while avoiding undesirable interactions that can block active sites. Here, we deposited carboxylic acid (CA)-functionalized organophosphonate monolayers onto Al2O3-supported Pd nanoparticle catalysts to prepare bifunctional catalysts containing both Bronsted acid and metal sites. Modification with phosphonic acids (PAs) improved activity and selectivity for gas-phase DO reactions, but the degree of improvement was highly sensitive to both the presence and positioning of the CA group, suggesting a significant contribution from both the PA and CA sites. Short spacer lengths of 1-2 methylene groups between the phosphonate head and CA tail were found to yield the best DO rates and selectivities, whereas longer chains performed similarly to self-assembled monolayers having alkyl tails. Results from a combination of density functional theory and Fourier transform infrared spectroscopy suggested that the enhanced catalyst performance on the optimally positioned CAs was due to the generation of strong acid sites on the Al2O3 support adjacent to the metal. Furthermore, the high activity of these sites was found to result from a hydrogen-bonded cyclic structure involving cooperativity between the phosphonate head group and CA tail function. More broadly, these results indicate that functional groups tethered to supports via organic ligands can influence catalytic chemistry on metal nanoparticles.

Magnetism in ordered metallic perovskite compound GdPd{sub 3}B{sub x}C{sub 1-x}

Energy Technology Data Exchange (ETDEWEB)

Pandey, Abhishek [S.N. Bose National Centre for Basic Sciences, Block-JD, Sector-III, Salt Lake, Kolkata 700098 (India); Experimental Condensed Matter Physics Division, Saha Institute of Nuclear Physics, 1/AF, Bidhannagar, Kolkata 700064 (India)], E-mail: abhishek.phy@gmail.com; Mazumdar, Chandan [Experimental Condensed Matter Physics Division, Saha Institute of Nuclear Physics, 1/AF, Bidhannagar, Kolkata 700064 (India)], E-mail: chandan.mazumdar@saha.ac.in; Ranganathan, R. [Experimental Condensed Matter Physics Division, Saha Institute of Nuclear Physics, 1/AF, Bidhannagar, Kolkata 700064 (India); Dattagupta, S. [Indian Institute of Science Education and Research, Block-HC, Sector-III, Salt Lake, Kolkata 700106 (India)

2009-08-15

We report results of dc-magnetization, ac-susceptibility and magnetoresistance measurements on crystalline metallic-perovskite compounds GdPd{sub 3}B{sub x}C{sub 1-x} (x=0.25, 0.50, 0.75 and 1.00) and the parent cubic compound GdPd{sub 3}. The interest in these materials stems from the observation of negative temperature coefficient of resistance and negative thermal expansion in some of the members of this series. In the present study, we show that by substitution of non-magnetic elements, boron and carbon, the nature of the magnetic interaction can be varied from dominating ferromagnetic to antiferromagnetic and finally to a canted magnetic structure without altering the crystal symmetry of the compounds. The variation of magnetic interaction by modifying the lattice parameter resembles Ruderman-Kittel-Kasuya-Yosida (RKKY) oscillations.

77 FR 70159 - Marble River, LLC v. Noble Clinton Windpark I, LLC, Noble Ellenburg Windpark, LLC, Noble...

Science.gov (United States)

2012-11-23

... DEPARTMENT OF ENERGY Federal Energy Regulatory Commission [Docket No. EL13-20-000] Marble River... Commission's (Commission) Rules of Practice and Procedure, Marble River, LLC (Marble River or Complainant.... (NYISO or Respondent), alleging that Noble failed to pay Marble River for headroom created by common...

Boosting catalytic activity of metal nanoparticles for 4-nitrophenol reduction: Modification of metal naoparticles with poly(diallyldimethylammonium chloride)

Energy Technology Data Exchange (ETDEWEB)

You, Jyun-Guo; Shanmugam, Chandirasekar [Department of Chemistry, National Sun Yat-sen University, Taiwan (China); Liu, Yao-Wen; Yu, Cheng-Ju [Department of Applied Physics and Chemistry, University of Taipei, Taiwan (China); Tseng, Wei-Lung, E-mail: tsengwl@mail.nsysu.edu.tw [Department of Chemistry, National Sun Yat-sen University, Taiwan (China); School of Pharmacy, College of Pharmacy, Kaohsiung Medical University, Taiwan (China); Center for Nanoscience and Nanotechnology, National Sun Yat-sen University, Taiwan (China)

2017-02-15

Highlights: • The choice of capping ligand determines catalytic activity of metal nanocatalysts. • PDDA-capped metal nanoparticles electrostatically interact with 4-NP and BH4{sup −}. • PDDA-capped metal nanoparticles have good recyclability and large scalability. • PDDA-capped Pd nanoparticles show the highest rate constant and activity parameter. - Abstract: Most of the previously reported studies have focused on the change in the size, morphology, and composition of metal nanocatalysts for improving their catalytic activity. Herein, we report poly(diallyldimethylammonium chloride) [PDDA]-stabilized nanoparticles (NPs) of platinum (Pt) and palladium (Pd) as highly active and efficient catalysts for hydrogenation of 4-nitrophenol (4-NP) in the presence of NaBH4. PDDA-stabilized Pt and Pd NPs possessed similar particle size and same facet with citrate-capped Pt and Pd NPs, making this study to investigate the inter-relationship between catalytic activity and surface ligand without the consideration of the effects of particle size and facet. Compared to citrate-capped Pt and Pd NPs, PDDA-stabilized Pt and Pd NPs exhibited excellent pH and salt stability. PDDA could serve as an electron acceptor for metal NPs to produce the net positive charges on the metal surface, which provide strong electrostatic attraction with negatively charged nitrophenolate and borohydride ions. The activity parameter and rate constant of PDDA-stabilized metal NPs were higher than those of citrate-capped metal NPs. Compared to the previously reported Pd nanomaterials for the catalysis of NaBH4-mediated reduction of 4-NP, PDDA-stabilized Pd NPs exhibited the extremely high activity parameter (195 s{sup −1} g{sup −1}) and provided excellent scalability and reusability.

Conditioning matrices from high level waste resulting from pyrochemical processing in fluorine salt

International Nuclear Information System (INIS)

Grandjean, Agnes; Advocat, Thierry; Bousquet, Nicolas; Jegou, Christophe

2007-01-01

Separating the actinides from the fission products through reductive extraction by aluminium in a LiF/AlF 3 medium is a process investigated for pyrometallurgical reprocessing of spent fuel. The process involves separation by reductive salt-metal extraction. After dissolving the fuel or the transmutation target in a salt bath, the noble metal fission products are first extracted by contacting them with a slightly reducing metal. After extracting the metal fission products, then the actinides are selectively separated from the remaining fission products. In this hypothesis, all the unrecoverable fission products would be conditioned as fluorides. Therefore, this process will generate first a metallic waste containing the 'reducible' fission products (Pd, Mo, Ru, Rh, Tc, etc.) and a fluorine waste containing alkali-metal, alkaline-earth and rare earth fission products. Immobilization of these wastes in classical borosilicate glasses is not feasible due to the very low solubility of noble metals, and of fluoride in these hosts. Alternative candidates have therefore been developed including silicate glass/ceramic system for fluoride fission products and metallic ones for noble metal fission products. These waste-forms were evaluated for their confinement properties like homogeneity, waste loading, volatility during the elaboration process, chemical durability, etc. using appropriate techniques. (authors)

MIS gas sensors based on porous silicon with Pd and WO{sub 3}/Pd electrodes

Energy Technology Data Exchange (ETDEWEB)

Solntsev, V.S. [Institute of Semiconductor Physics, National Academy of Science of Ukraine, 03028, Kiev (Ukraine); Gorbanyuk, T.I., E-mail: tatyanagor@mail.r [Institute of Semiconductor Physics, National Academy of Science of Ukraine, 03028, Kiev (Ukraine); Litovchenko, V.G.; Evtukh, A.A. [Institute of Semiconductor Physics, National Academy of Science of Ukraine, 03028, Kiev (Ukraine)

2009-09-30

Pd and WO{sub 3}/Pd gate metal-oxide-semiconductor (MIS) gas sensitive structures based on porous silicon layers are studied by the high frequency C(V) method. The chemical compositions of composite WO{sub 3}/Pd electrodes are characterized by secondary-ion mass spectrometry (SIMS). The atomic force microscopy (AFM) was used for morphologic studies of WO{sub 3}/Pd films. As shown in the experiments, WO{sub 3}/Pd structures are more sensitive and selective to the adsorption of hydrogen sulphide compared to Pd gate. The analyses of kinetic characteristics allow us to determine the response and characteristic times for these structures. The response time of MIS-structures with thin composite WO{sub 3}/Pd electrodes (the thickness of Pd is about 50 nm with WO{sub 3} clusters on its surface) is slower compared to the structures with Pd electrodes. Slower sensor responses of WO{sub 3}-based gas sensors may be associated with different mechanism of gas sensitivity of given structures. The enhanced sensitivity and selectivity to H{sub 2}S action of WO{sub 3}/Pd MIS-structures can also be explained by the chemical reaction that occurs at the catalytic active surface of gate electrodes. The possible mechanisms of enhanced sensitivity and selectivity to H{sub 2}S adsorption of MIS gas sensors with WO{sub 3}/Pd composite gate electrodes compared to pure Pd have been analyzed.

Generation and oxidation of aerosol deposited PdAg nanoparticles

Science.gov (United States)

Blomberg, S.; Gustafson, J.; Martin, N. M.; Messing, M. E.; Deppert, K.; Liu, Z.; Chang, R.; Fernandes, V. R.; Borg, A.; Grönbeck, H.; Lundgren, E.

2013-10-01

PdAg nanoparticles with a diameter of 10 nm have been generated by an aerosol particle method, and supported on a silica substrate. By using a combination of X-ray Energy Dispersive Spectroscopy and X-ray Photoelectron Spectroscopy it is shown that the size distribution of the particles is narrow and that the two metals form an alloy with a mixture of 75% Pd and 25% Ag. Under oxidizing conditions, Pd is found to segregate to the surface and a thin PdO like oxide is formed similar to the surface oxide previously reported on extended PdAg and pure Pd surfaces.

A GREENER SYNTHESIS OF CORE (FE, CU)-SHELL (AU, PT, PD AND AG) NANOCRYSTALS USING AQUEOUS VITAMIN C

Science.gov (United States)

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...

Production of Jet Fuel-Range Hydrocarbons from Hydrodeoxygenation of Lignin over Super Lewis Acid Combined with Metal Catalysts

International Nuclear Information System (INIS)

Wang, Hongliang; Wang, Huamin; Kuhn, Eric; Tucker, Melvin P.; Yang, Bin

2017-01-01

Super Lewis acids containing the triflate anion [e.g., Hf(OTf) 4 , Ln(OTf) 3 , In(OTf) 3 , Al(OTf) 3 ] and noble metal catalysts (e.g., Ru/C, Ru/Al2O 3 ) formed efficient catalytic systems to generate saturated hydrocarbons from lignin in high yields. In such catalytic systems, the metal triflates mediated rapid ether bond cleavage through selective bonding to etheric oxygens while the noble metal catalyzed subsequent hydrodeoxygenation (HDO) reactions. Near theoretical yields of hydrocarbons were produced from lignin model compounds by the combined catalysis of Hf(OTf)4 and ruthenium-based catalysts. When a technical lignin derived from a pilot-scale biorefinery was used, more than 30 wt % of the hydrocarbons produced with this catalytic system were cyclohexane and alkylcyclohexanes in the jet fuel range. Super Lewis acids are postulated to strongly interact with lignin substrates by protonating hydroxyl groups and ether linkages, forming intermediate species that enhance hydrogenation catalysis by supported noble metal catalysts. Meanwhile, the hydrogenation of aromatic rings by the noble metal catalysts can promote oxygenation reactions catalyzed by super Lewis acids.

Production of Jet Fuel-Range Hydrocarbons from Hydrodeoxygenation of Lignin over Super Lewis Acid Combined with Metal Catalysts

Energy Technology Data Exchange (ETDEWEB)

Wang, Hongliang [Department of Biological Systems Engineering, Washington State University, Richland WA 99354 USA; Current address: Center of Biomass Engineering/College of Agronomy and Biotechnology, China Agricultural University, Beijing 100193 PR China; Wang, Huamin [Pacific Northwest National Laboratory, 902 Battelle Boulevard Richland WA 99354 USA; Kuhn, Eric [National Bioenergy Center, National Renewable Energy Laboratory, 15013 Denver West Parkway Golden CO 80401 USA; Tucker, Melvin P. [National Bioenergy Center, National Renewable Energy Laboratory, 15013 Denver West Parkway Golden CO 80401 USA; Yang, Bin [Department of Biological Systems Engineering, Washington State University, Richland WA 99354 USA

2017-11-14

Super Lewis acids containing the triflate anion (e.g. Hf(OTf)4, Ln(OTf)3, Al(OTf)3) and noble metal catalysts (e.g. Ru/C, Ru/Al2O3) formed efficient catalytic systems to generate saturated hydrocarbons from lignin in high yields. In such catalytic systems, the metal triflates mediated rapid ether bond cleavage via selective bonding to etheric oxygens while the noble metal catalysed subsequent hydrodeoxygenation (HDO) reactions. Near theoretical yields of hydrocarbons were produced from lignin model compounds by the combined catalysis of Hf(OTf)4 and ruthenium-based catalysts. When a technical lignin derived from a pilot-scale biorefinery was used, more than 30 wt% of the hydrocarbons produced with this catalytic system were cyclohexane and alkylcyclohexanes in the jet fuel range. Super Lewis acids are postulated to strongly interact with lignin substrates via protonating hydroxyls and ether linkages, forming intermediate species that enhance hydrogenation catalysis by supported noble metal catalysts. Meanwhile, the hydrogenation of aromatic rings by the noble metal catalysts can promote oxygenation reactions catalysed by super Lewis acids.