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.

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.

Niobium-based catalysts prepared by reactive radio-frequency magnetron sputtering and arc plasma methods as non-noble metal cathode catalysts for polymer electrolyte fuel cells

International Nuclear Information System (INIS)

Ohnishi, Ryohji; Katayama, Masao; Takanabe, Kazuhiro; Kubota, Jun; Domen, Kazunari

2010-01-01

Two vacuum methods, reactive radio-frequency (RF) magnetron sputtering and arc plasma deposition, were used to prepare niobium-based catalysts for an oxygen reduction reaction (ORR) as non-noble metal cathodes for polymer electrode fuel cells (PEFCs). Thin films with various N and O contents, denoted as NbO x and Nb-O-N, were prepared on glassy carbon plates by RF magnetron sputtering with controlled partial pressures of oxygen and nitrogen. Electrochemical measurements indicated that the introduction of the nitrogen species into the thin film resulted in improved ORR activity compared to the oxide-only film. Using an arc plasma method, niobium was deposited on highly oriented pyrolytic graphite (HOPG) substrates, and the sub-nanoscale surface morphology of the deposited particles was investigated using scanning tunneling microscopy (STM). To prepare practical cathode catalysts, niobium was deposited on carbon black (CB) powders by arc plasma method. STM and transmission electron microscopy observations of samples on HOPG and CB indicated that the prepared catalysts were highly dispersed at the atomic level. The onset potential of oxygen reduction on Nb-O-N/CB was 0.86 V vs. a reversible hydrogen electrode, and the apparent current density was drastically improved by the introduction of nitrogen.

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 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

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

A general approach to mesoporous metal oxide microspheres loaded with noble metal nanoparticles

KAUST Repository

Jin, Zhao; Xiao, Manda; Bao, Zhihong; Wang, Peng; Wang, Jianfang

2012-01-01

Catalytic microspheres: A general approach is demonstrated for the facile preparation of mesoporous metal oxide microspheres loaded with noble metal nanoparticles (see TEM image in the picture). Among 18 oxide/noble metal catalysts, TiO 2/0.1 mol Pd microspheres showed the highest turnover frequency in NaBH 4 reduction of 4-nitrophenol (see picture). Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A general approach to mesoporous metal oxide microspheres loaded with noble metal nanoparticles

KAUST Repository

Jin, Zhao

2012-04-26

Catalytic microspheres: A general approach is demonstrated for the facile preparation of mesoporous metal oxide microspheres loaded with noble metal nanoparticles (see TEM image in the picture). Among 18 oxide/noble metal catalysts, TiO 2/0.1 mol Pd microspheres showed the highest turnover frequency in NaBH 4 reduction of 4-nitrophenol (see picture). Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Hemoglobin-carbon nanotube derived noble-metal-free Fe5C2-based catalyst for highly efficient oxygen reduction reaction

Science.gov (United States)

Vij, Varun; Tiwari, Jitendra N.; Lee, Wang-Geun; Yoon, Taeseung; Kim, Kwang S.

2016-02-01

High performance non-precious cathodic catalysts for oxygen reduction reaction (ORR) are vital for the development of energy materials and devices. Here, we report an noble metal free, Fe5C2 nanoparticles-studded sp2 carbon supported mesoporous material (CNTHb-700) as cathodic catalyst for ORR, which was prepared by pyrolizing the hybrid adduct of single walled carbon nanotubes (CNT) and lyophilized hemoglobin (Hb) at 700 °C. The catalyst shows onset potentials of 0.92 V in 0.1 M HClO4 and in 0.1 M KOH which are as good as commercial Pt/C catalyst, giving very high current density of 6.34 and 6.69 mA cm-2 at 0.55 V vs. reversible hydrogen electrode (RHE), respectively. This catalyst has been confirmed to follow 4-electron mechanism for ORR and shows high electrochemical stability in both acidic and basic media. Catalyst CNTHb-700 possesses much higher tolerance towards methanol than the commercial Pt/C catalyst. Highly efficient catalytic properties of CNTHb-700 could lead to fundamental understanding of utilization of biomolecules in ORR and materialization of proton exchange membrane fuel cells for clean energy production.

Exotic species with explicit noble metal-noble gas-noble metal linkages.

Science.gov (United States)

Moreno, Norberto; Restrepo, Albeiro; Hadad, C Z

2018-02-14

We present a study of the isoelectronic Pt 2 Ng 2 F 4 and [Au 2 Ng 2 F 4 ] 2+ species with noble gas atoms (Ng = Kr, Xe, Rn) acting as links bridging the two noble metal atoms. The stability of the species is investigated using several thermodynamic, kinetic and reactivity indicators. The results are compared against [AuXe 4 ] 2+ , which is thermodynamically unstable in the gas phase but is stabilized in the solid state to the point that it has been experimentally detected as [AuXe 4 ](Sb 2 F 11 ) 2 (S. Seidel and K. Seppelt, Science, 2000, 290, 117-118). Our results indicate that improving upon [AuXe 4 ] 2+ , these exotic combinations between the a priori non-reactive noble metals and noble gases lead to metastable species, and, therefore, they have the possibility of existing in the solid state under adequate conditions. Our calculations include accurate energies and geometries at both the CCSD/SDDALL and MP2/SDDALL levels. We offer a detailed description of the nature of the bonding interactions using orbital and density-based analyses. The computational evidence suggests partially covalent and ionic interactions as the stabilization factors.

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

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.

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.

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...

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

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...

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

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.

Recycling of spent noble metal catalysts with emphasis on pyrometallurgical processing

Energy Technology Data Exchange (ETDEWEB)

Hagelueken, C. [Degussa Huels AG, Hanau (Germany)

1999-09-01

Precious metal catalysts for catalytic Naphta Reforming, Isomerization, Hydrogenation and other chemical and petrochemical processes are valuable assets for oil refineries and chemical companies. At the end of the service life of a reactor load of catalyst, the efficient and reliable recovery of the precious metals contained in the catalyst is of paramount importance. More than 150 years of technological advances at Degussa-Huels have resulted in refining methods for all kinds of precious metal containing materials which guarantee an optimum technical yield of the precious metals included. The refining of catalysts today is one of the important activities in the precious metals business unit. In the state-of-the-art precious metal refinery at Hanau in the centre of Germany, a wide variety of processes for the recovery of all precious metals is offered. These processes include accurate preparation, sampling and analysis as well as both wet-chemical and pyrometallurgical recovery techniques. Special emphasis in this presentation is laid on the advantages of pyrometallurgical processes for certain kinds of catalysts. To avoid any risks during transport, sampling and treatment of the spent catalyst, all parties involved in the recycling chain strictly have to follow the relevant safety regulations. Under its commitment to 'Responsible Care' standard procedures have been developed which include pre-shipment samples, safety data sheets/questionnaires and inspection of spent catalysts. These measures not only support a safe and environmentally sound catalyst recycling but also enable to determine the most suitable and economic recovery process - for the benefit of the customer. (orig.)

Screening of Catalysts for Hydrodeoxygenation of Phenol as Model Compound for Bio-oil

DEFF Research Database (Denmark)

Mortensen, Peter Mølgaard; Grunwaldt, Jan-Dierk; Jensen, Peter Arendt

2013-01-01

Four groups of catalysts have been tested for hydrodeoxygenation (HDO) of phenol as a model compound of bio-oil, including: oxide catalysts, methanol synthesis catalysts, reduced noble metal catalysts, and reduced non-noble metal catalysts. In total 23 different catalysts were tested at 100 bar H2...... and 275 °C in a batch reactor. The experiments showed that none of the tested oxides and methanol synthesis catalysts had any significant activity for phenol HDO at the given conditions, which were linked to their inability to hydrogenate the phenol. HDO of phenol over reduced metal catalysts could...... on a carbon support, but more active than the carbon supported noble metal catalysts when supported on ZrO2. This observation indicates that the nickel based catalysts require a metal oxide as carrier on which the activation of the phenol for the hydrogenation can take place through heterolytic dissociation...

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.

Reducible oxide based catalysts

Science.gov (United States)

Thompson, Levi T.; Kim, Chang Hwan; Bej, Shyamal K.

2010-04-06

A catalyst is disclosed herein. The catalyst includes a reducible oxide support and at least one noble metal fixed on the reducible oxide support. The noble metal(s) is loaded on the support at a substantially constant temperature and pH.

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

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.

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...

Production of Jet Fuel-Range Hydrocarbons from Hydrodeoxygenation of Lignin over Super Lewis Acid Combined with Metal Catalysts.

Science.gov (United States)

Wang, Hongliang; Wang, Huamin; Kuhn, Eric; Tucker, Melvin P; Yang, Bin

2018-01-10

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/Al 2 O 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 deoxygenation reactions catalyzed by super Lewis acids. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

The effect of noble metals on catalytic methanation reaction over supported Mn/Ni oxide based catalysts

Directory of Open Access Journals (Sweden)

Wan Azelee Wan Abu Bakar

2015-09-01

Full Text Available Carbon dioxide (CO2 in sour natural gas can be removed using green technology via catalytic methanation reaction by converting CO2 to methane (CH4 gas. Using waste to wealth concept, production of CH4 would increase as well as creating environmental friendly approach for the purification of natural gas. In this research, a series of alumina supported manganese–nickel oxide based catalysts doped with noble metals such as ruthenium and palladium were prepared by wetness impregnation method. The prepared catalysts were run catalytic screening process using in-house built micro reactor coupled with Fourier Transform Infra Red (FTIR spectroscopy to study the percentage CO2 conversion and CH4 formation analyzed by GC. Ru/Mn/Ni(5:35:60/Al2O3 calcined at 1000 °C was found to be the potential catalyst which gave 99.74% of CO2 conversion and 72.36% of CH4 formation at 400 °C reaction temperature. XRD diffractogram illustrated that the supported catalyst was in polycrystalline with some amorphous state at 1000 °C calcination temperature with the presence of NiO as active site. According to FESEM micrographs, both fresh and used catalysts displayed spherical shape with small particle sizes in agglomerated and aggregated mixture. Nitrogen Adsorption analysis revealed that both catalysts were in mesoporous structures with BET surface area in the range of 46–60 m2/g. All the impurities have been removed at 1000 °C calcination temperature as presented by FTIR, TGA–DTA and EDX data.

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.

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.

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.

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

Recovery and use of fission product noble metals

International Nuclear Information System (INIS)

Jensen, G.A.; Rohmann, C.A.; Perrigo, L.D.

1980-06-01

Noble metals in fission products are of strategic value. Market prices for noble metals are rising more rapidly than recovery costs. A promising concept has been developed for recovery of noble metals from fission product waste. Although the assessment was made only for the three noble metal fission products (Rh, Pd, Ru), there are other fission products and actinides which have potential value

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)

Noble-Metal Chalcogenide Nanotubes

Directory of Open Access Journals (Sweden)

Nourdine Zibouche

2014-10-01

Full Text Available We explore the stability and the electronic properties of hypothetical noble-metal chalcogenide nanotubes PtS2, PtSe2, PdS2 and PdSe2 by means of density functional theory calculations. Our findings show that the strain energy decreases inverse quadratically with the tube diameter, as is typical for other nanotubes. Moreover, the strain energy is independent of the tube chirality and converges towards the same value for large diameters. The band-structure calculations show that all noble-metal chalcogenide nanotubes are indirect band gap semiconductors. The corresponding band gaps increase with the nanotube diameter rapidly approaching the respective pristine 2D monolayer limit.

Graphene layer encapsulated metal nanoparticles as a new type of non-precious metal catalysts for oxygen reduction

DEFF Research Database (Denmark)

Hu, Yang; Zhong, Lijie; Jensen, Jens Oluf

2016-01-01

Cheap and efficient non-precious metal catalysts for oxygen reduction have been a focus of research in the field of low-temperature fuel cells. This review is devoted to a brief summary of the recent work on a new type of catalysts, i.e., the graphene layer encapsulated metal nanoparticles....... The discussion is focused on the synthesis, structure, mechanism, performance, and further research....

Inert anode containing base metal and noble metal useful for the electrolytic production of aluminum

Science.gov (United States)

Ray, Siba P.; Liu, Xinghua

2000-01-01

An inert anode for production of metals such as aluminum is disclosed. The inert anode comprises a base metal selected from Cu and Ag, and at least one noble metal selected from Ag, Pd, Pt, Au, Rh, Ru, Ir and Os. The inert anode may optionally be formed of sintered particles having interior portions containing more base metal than noble metal and exterior portions containing more noble metal than base metal. In a preferred embodiment, the base metal comprises Cu, and the noble metal comprises Ag, Pd or a combination thereof.

Improving performance of catalysts for water electrolysis

DEFF Research Database (Denmark)

Frydendal, Rasmus

This Ph.D. thesis presents work on non-noble metal oxide catalysts for the oxygen evolution reaction, OER. This reaction is currently a bottleneck in electrolyzer technologies, which are promising for energy storage purposes. In particular, Polymer Electrolyte Membrane, PEM, cells are attractive...

SISGR-Fundamental Experimental and Theoretical Studies on a Novel Family of Oxide Catalyst Supports for Water Electrolysis

Energy Technology Data Exchange (ETDEWEB)

Kumta, Prashant [University of Pittsburgh

2014-10-03

Identification and development of non-noble metal based electro-catalysts or electro-catalysts with significant reduction of expensive noble metal contents (E.g. IrO2, Pt) with comparable electrochemical performance as the standard noble metal/metal oxide for proton exchange membrane (PEM) based water electrolysis would constitute a major breakthrough in the generation of hydrogen by water electrolysis. Accomplishing such a system would not only result reduction of the overall capital costs of PEM based water electrolyzers, but also help attain the targeted hydrogen production cost [< $ 3.0 / gallon gasoline equivalent (gge)] comparable to conventional liquid fuels. In line with these goals, it was demonstrated that fluorine doped IrO2 thin films and nanostructured high surface area powders display remarkably higher electrochemical activity, and comparable durability as pure IrO2 electro-catalyst for the oxygen evolution reaction (OER) in PEM based water electrolysis. Furthermore, corrosion resistant SnO2 and NbO2 support has been doped with F and coupled with IrO2 or RuO2 for use as an OER electro-catalyst. A solid solution of SnO2:F or NbO2:F with only 20 - 30 mol.% IrO2 or RuO2 yielding a rutile structure in the form of thin films and bulk nanoparticles displays similar electrochemical activity and stability as pure IrO2/RuO2. This would lead to more than 70 mol.% reduction in the noble metal oxide content. Novel nanostructured ternary (Ir,Sn,Nb)O2 thin films of different compositions FUNDAMENTAL STUDY OF NANOSTRUCTURED ELECTRO-CATALYSTS WITH REDUCED NOBLE METAL CONTENT FOR PEM BASED WATER ELECTROLYSIS 4 have also been studied. It has been shown that (Ir0.40Sn0.30Nb0.30)O2 shows similar electrochemical activity and enhanced chemical robustness as compared to pure IrO2. F doping of the ternary (Ir,Sn,Nb)O2 catalyst helps in further decreasing the noble metal oxide content of the catalyst. As a result, these reduced noble metal oxide catalyst systems would

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.

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.

Excellent photocatalytic hydrogen production over CdS nanorods via using noble metal-free copper molybdenum sulfide (Cu{sub 2}MoS{sub 4}) nanosheets as co-catalysts

Energy Technology Data Exchange (ETDEWEB)

Hong, Sangyeob; Kumar, D. Praveen; Reddy, D. Amaranatha; Choi, Jiha; Kim, Tae Kyu, E-mail: tkkim@pusan.ac.kr

2017-02-28

Highlights: • Developed Cu{sub 2}MoS{sub 4} nanosheets as co-catalysts. • Cu{sub 2}MoS{sub 4} as active replacements for precious noble metal. • Controlled charge recombination for use in photocatalytic H{sub 2} evolution. • Obtained superior rate of H{sub 2} production by using Cu{sub 2}MoS{sub 4} loaded CdS nanorods. - Abstract: Charge carrier recombination and durability issues are major problems in photocatalytic hydrogen (H{sub 2}) evolution processes. Thus, there is a very important necessitate to extend an efficient photocatalyst to control charge-carrier dynamics in the photocatalytic system. We have developed copper molybdenum sulfide (Cu{sub 2}MoS{sub 4}) nanosheets as co-catalysts with CdS nanorods for controlling charge carriers without recombination for use in photocatalytic H{sub 2} evolution under simulated solar light irradiation. Effective control and utilization of charge carriers are possible by loading Cu{sub 2}MoS{sub 4} nanosheets onto the CdS nanorods. The loading compensates for the restrictions of CdS, and stimulated synergistic effects, such as efficient photoexcited charge separation, lead to an improvement in photostability because of the layered structure of the Cu{sub 2}MoS{sub 4}nanosheets. These layered Cu{sub 2}MoS{sub 4} nanosheets have emerged as novel and active replacements for precious noble metal co-catalysts in photocatalytic H{sub 2} production by water splitting. We have obtained superior H{sub 2} production rates by using Cu{sub 2}MoS{sub 4} loaded CdS nanorods. The physicochemical properties of the composites are analyzed by diverse characterization techniques.

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.

Recent Scientific Progress on Developing Supported Ni Catalysts for Dry (CO2 Reforming of Methane

Directory of Open Access Journals (Sweden)

Hyun Ook Seo

2018-03-01

Full Text Available Two major green house gases (CO2 and CH4 can be converted into useful synthetic gas (H2 and CO during dry reforming of methane (DRM reaction, and a lot of scientific efforts has been made to develop efficient catalysts for dry reforming of methane (DRM. Noble metal-based catalysts can effectively assist DRM reaction, however they are not economically viable. Alternatively, non-noble based catalysts have been studied so far, and supported Ni catalysts have been considered as a promising candidate for DRM catalyst. Main drawback of Ni catalysts is its catalytic instability under operating conditions of DRM (>700 °C. Recently, it has been demonstrated that the appropriate choice of metal-oxide supports can address this issue since the chemical and physical of metal-oxide supports can prevent coke formation and stabilize the small Ni nanoparticles under harsh conditions of DRM operation. This mini-review covers the recent scientific findings on the development of supported Ni catalysts for DRM reaction, including the synthetic methods of supported Ni nanoparticles with high sintering resistance.

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

Size Controlled Synthesis of Transition Metal Nanoparticles for Catalytic Applications

KAUST Repository

Esparza, Angel

2011-07-07

Catalysis offers cleaner and more efficient chemical reactions for environmental scientists. More than 90% of industrial processes are performed with a catalyst involved, however research it is still required to improve the catalyst materials. The purpose of this work is to contribute with the development of catalysts synthesis with two different approaches. First, the precise size control of non-noble metals nanoparticles. Second, a new one-pot synthesis method based on a microemulsion system was developed to synthesize size-controlled metal nanoparticles in oxide supports. The one-pot method represents a simple approach to synthesize both support and immobilized nanometer-sized non-noble metal nanoparticles in the same reaction system. Narrow size distribution nickel, cobalt, iron and cobalt-nickel nanoparticles were obtained. High metal dispersions are attainable regardless the metal or support used in the synthesis. Thus, the methodology is adaptable and robust. The sizecontrolled supported metal nanoparticles offer the opportunity to study size effects and metal-support interactions on different catalytic reactions with different sets of metals and supports.

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.)

Activity Tests of Macro-Meso Porous Catalysts over Metal Foam Plate for Steam Reforming of Bio-Ethanol.

Science.gov (United States)

Park, No-Kuk; Jeong, Yong Han; Kang, Misook; Lee, Tae Jin

2018-09-01

The catalytic activity of a macro-mesoporous catalyst coated on a metal foam plate in the reforming of bio-ethanol to synthesis gas was investigated. The catalysts were prepared by coating a support with a noble metal and transition metal. The catalytic activity for the production of synthetic gas by the reforming of bio-ethanol was compared according to the support material, reaction temperature, and steam/carbon ratio. The catalysts coated on the metal foams were prepared using a template method, in which macro-pores and meso-pores were formed by mixing polymer beads. In particular, the thermodynamic equilibrium composition of bio-ethanol reforming with the reaction temperature and steam/carbon ratio to produce synthetic gas was examined using the HSC (Enthalpy-Entropy-Heat capacity) chemistry program in this study. The composition of hydrogen and carbon monoxide in the reformate gas produced by steam reforming over the Rh/Ni-Ce-Zr/Al2O3-based pellet type catalysts and metal foam catalysts that had been coated with the Rh/Al-Ce-Zr-based catalysts was investigated by experimental activity tests. The activity of the metal foam catalyst was higher than that of the pellet type catalyst.

Recovery of noble metals from fission products

International Nuclear Information System (INIS)

Jenson, G.A.; Platt, A.M.; Mellinger, G.B.; Bjorklund, W.J.

1982-11-01

Scoping studies were started in 1979 to develop a cost-effective, waste-management-compatible process to extract noble metals from fission products. The process, involving the reaction with glassmelting chemicals, a metal oxide (PbO), and a reducing agent (charcoal), was demonstrated for recovering noble metals from simulated high-level waste oxides. The process has now been demonstrated on a laboratory scale (100 g) using irradiated fuels. Recoveries in the recovered lead averaged 80% for Pd, 60% for Rh, and 14% Ru. The resulting glass product was homogeneous in appearance, and the chemical durability was comparable to other waste oxides

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)

Highly Active Non-PGM Catalysts Prepared from Metal Organic Frameworks

Directory of Open Access Journals (Sweden)

Heather M. Barkholtz

2015-06-01

Full Text Available Finding inexpensive alternatives to platinum group metals (PGMs is essential for reducing the cost of proton exchange membrane fuel cells (PEMFCs. Numerous materials have been investigated as potential replacements of Pt, of which the transition metal and nitrogen-doped carbon composites (TM/Nx/C prepared from iron doped zeolitic imidazolate frameworks (ZIFs are among the most active ones in catalyzing the oxygen reduction reaction based on recent studies. In this report, we demonstrate that the catalytic activity of ZIF-based TM/Nx/C composites can be substantially improved through optimization of synthesis and post-treatment processing conditions. Ultimately, oxygen reduction reaction (ORR electrocatalytic activity must be demonstrated in membrane-electrode assemblies (MEAs of fuel cells. The process of preparing MEAs using ZIF-based non-PGM electrocatalysts involves many additional factors which may influence the overall catalytic activity at the fuel cell level. Evaluation of parameters such as catalyst loading and perfluorosulfonic acid ionomer to catalyst ratio were optimized. Our overall efforts to optimize both the catalyst and MEA construction process have yielded impressive ORR activity when tested in a fuel cell system.

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.

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.

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.

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.

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.

Selective Conversion of Lignin-Derivable 4-Alkylguaiacols to 4-Alkylcyclohexanols over Noble and Non-Noble-Metal Catalysts

Energy Technology Data Exchange (ETDEWEB)

Schutyser, Wouter; Van den Bossche, Gil; Raaffels, Anton; Van den Bosch, Sander; Koelewijn, Steven-Friso; Renders, Tom; Sels, Bert F.

2016-10-03

Recent lignin-first catalytic lignocellulosic biorefineries produce large quantities of two potential platform chemicals, 4-n-propylguaiacol (PG) and 4-n-propylsyringol. Because conversion into 4-n-propylcyclohexanol (PCol), a precursor for novel polymer building blocks, presents a promising valorization route, reductive demethoxylation of PG was examined here in the liquid-phase over three commercial hydrogenation catalysts, viz. 5 wt % Ru/C, 5 wt % Pd/C and 65 wt % Ni/SiO2-Al2O3, at elevated temperatures ranging from 200 to 300 degrees C under hydrogen atmosphere. Kinetic profiles suggest two parallel conversion pathways: Pathway I involves PG hydrogenation to 4-n-propyl-2-methoxycyclohexanol (PMCol), followed by its demethoxylation to PCol, whereas Pathway II constitutes PG hydrodemethoxylation to 4-n-propylphenol (PPh), followed by its hydrogenation into PCol. The slowest step in the catalytic formation of PCol is the reductive methoxy removal from PMCol. Moreover, under the applied reaction conditions, PCol may react further into hydrocarbons. The following criteria are therefore essential to reach a high PCol yield: (i) catalytic pathway II is preferred as this route does not involve stable intermediates; (ii) reactivity of PMCol should be higher than that of PCol, and (iii) the overall carbon balance should be high. Both the catalyst type and the reaction conditions have a substantial impact on the PCol yield. Only the commercial Ni catalyst meets the three criteria, provided the reaction is performed at 250 degrees C in hexadecane. Additional advantages of this solvent choice are a high boiling point (low operational pressure in closed reactor systems), high solubility of PG and derived products, high thermal, reductive stability, and easy derivability from fatty biomass feedstock. This Ni catalyst also showed an excellent stability in recycling runs and is capable of converting highly concentrated (up to 20 wt %) PG in hexadecane. Ru and Pd on carbon

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.

Modeling of carbon monoxide oxidation kinetics over NASA carbon dioxide laser catalysts

Science.gov (United States)

Herz, Richard K.

1989-01-01

The recombination of CO and O2 formed by the dissociation of CO2 in a sealed CO2 laser discharge zone is examined. Conventional base-metal-oxide catalysts and conventional noble-metal catalysts are not effective in recombining the low O2/CO ratio at the low temperatures used by the lasers. The use of Pt/SnO2 as the noble-metal reducible-oxide (NMRO), or other related materials from Group VIIIA and IB and SnO2 interact synergistically to produce a catalytic activity that is substantially higher than either componet separately. The Pt/SnO2 and Pd/SnO2 were reported to have significant reaction rates at temperatures as low as -27 C, conditions under which conventional catalysts are inactive. The gas temperature range of lasers is 0 + or - 40 C. There are three general ways in which the NMRO composite materials can interact synergistically: one component altering the properties of another component; the two components each providing independent catalytic functions in a complex reaction mechanism; and the formation of catalytic sites through the combination of two components at the atomic level. All three of these interactions may be important in low temperature CO oxidation over NMRO catalysts. The effect of the noble metal on the oxide is discussed first, followed by the effect of the oxide on the noble metal, the interaction of the noble metal and oxide to form catalytic sites, and the possible ways in which the CO oxidation reaction is catalyzed by the NMRO materials.

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.

Structural and plasmonic properties of noble metal doped ZnO nanomaterials

Science.gov (United States)

Pathak, Trilok K.; Swart, H. C.; Kroon, R. E.

2018-04-01

Noble metal doped ZnO has been synthesized by the combustion method and the effect of different metals (Ag, Au, Pd) on the structural, morphological, optical, photoluminescence and localized surface plasmon resonance (LSPR) properties has been investigated. X-ray diffraction analysis revealed that the ZnO had a hexagonal wurtzite structure and the crystallite sizes were affected by the doping. The formation of noble metal nanoparticles (NPs) was investigated using transmission electron microscopy and diffuse reflectance spectra. The LSPR of the metallic NPs was predicted using Mie theory calculations. The absorption spectra were calculated using the Kubelka-Munk function and the optical bandgap varied from 3.06 to 3.18 eV for the different doping materials. The experimental results suggest that the origin of enhanced emission was due to direct interaction between the laser photons and the noble material NPs which in turn leads to photoemission transfer of electrons from the noble metals NPs to the conduction band of ZnO.

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.

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.

Employment of an ion implantation technique for catalyst coating on various substrates

International Nuclear Information System (INIS)

Bannikov, M.G.; Chattha, J.A.; Zlobin, V.N.; Vasilve, I.P.; Cherkasov, J.A.; Gawrilenko, P.N.

2001-01-01

Catalysts are widely used in the chemical industry as well as in the production of vehicle catalytic converters. Precious metals are employed increasingly as catalytic materials. Traditional methods of coating, such as impregnation, are thought to reduce the porosity and specific area of catalyst thus reducing the catalytic efficiency. Apart from that, impregnation technology leads to the high expense of precious metals. To reduce the content of noble metals in catalysts the ion implantation method of coating has been investigated. Several samples of catalysts on various substrates were prepared by ion implantation technique and tested. New catalysts have shown high nitric oxides (NO/sub x/) and carbon monoxide (CO) conversion efficiency, with the content of noble metals reduced substantially. Experiment has also shown that specific area of substrates coated by an ion implantation had not decreased. Schematic of an ion implanter and experimental results are provided. (author)

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

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)

Characterization of three-way automotive catalysts

Energy Technology Data Exchange (ETDEWEB)

Kenik, E.A.; More, K.L. [Oak Ridge National Lab., TN (United States); LaBarge, W. [Delphi Automotive Systems, Flint, MI (United States)] [and others

1997-04-01

The CRADA between Delphi Automotive Systems (Delphi; formerly General Motors - AC Delco, Systems) and Lockheed Martin Energy Research (LMER) on automotive catalysts was completed at the end of FY96, after a ten month, no-cost extension. The CRADA was aimed at improved performance and lifetime of noble metal based three-way-catalysts (TWC), which are the primary catalytic system for automotive emission control systems. While these TWC can meet the currently required emission standards, higher than optimum noble metal loadings are often required to meet lifetime requirements. In addition, more stringent emission standards will be imposed in the near future, demanding improved performance and service life from these catalysts. Understanding the changes of TWC conversion efficiency with ageing is a critical need in improving these catalysts. Initially in a fresh catalyst, the active material is often distributed on a very fine scale, approaching single atoms or small atomic clusters. As such, a wide range of analytical techniques have been employed to provide high spatial resolution characterization of the evolving state of the catalytic material.

Excellent photocatalytic hydrogen production over CdS nanorods via using noble metal-free copper molybdenum sulfide (Cu2MoS4) nanosheets as co-catalysts

Science.gov (United States)

Hong, Sangyeob; Kumar, D. Praveen; Reddy, D. Amaranatha; Choi, Jiha; Kim, Tae Kyu

2017-02-01

Charge carrier recombination and durability issues are major problems in photocatalytic hydrogen (H2) evolution processes. Thus, there is a very important necessitate to extend an efficient photocatalyst to control charge-carrier dynamics in the photocatalytic system. We have developed copper molybdenum sulfide (Cu2MoS4) nanosheets as co-catalysts with CdS nanorods for controlling charge carriers without recombination for use in photocatalytic H2 evolution under simulated solar light irradiation. Effective control and utilization of charge carriers are possible by loading Cu2MoS4 nanosheets onto the CdS nanorods. The loading compensates for the restrictions of CdS, and stimulated synergistic effects, such as efficient photoexcited charge separation, lead to an improvement in photostability because of the layered structure of the Cu2MoS4nanosheets. These layered Cu2MoS4 nanosheets have emerged as novel and active replacements for precious noble metal co-catalysts in photocatalytic H2 production by water splitting. We have obtained superior H2 production rates by using Cu2MoS4 loaded CdS nanorods. The physicochemical properties of the composites are analyzed by diverse characterization techniques.

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.

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)

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

Platinum Group Metal-free Catalysts for Hydrogen Evolution Reaction in Microbial Electrolysis Cells.

Science.gov (United States)

Yuan, Heyang; He, Zhen

2017-07-01

Hydrogen gas is a green energy carrier with great environmental benefits. Microbial electrolysis cells (MECs) can convert low-grade organic matter to hydrogen gas with low energy consumption and have gained a growing interest in the past decade. Cathode catalysts for the hydrogen evolution reaction (HER) present a major challenge for the development and future applications of MECs. An ideal cathode catalyst should be catalytically active, simple to synthesize, durable in a complex environment, and cost-effective. A variety of noble-metal free catalysts have been developed and investigated for HER in MECs, including Nickel and its alloys, MoS 2 , carbon-based catalysts and biocatalysts. MECs in turn can serve as a research platform to study the durability of the HER catalysts. This personal account has reviewed, analyzed, and discussed those catalysts with an emphasis on synthesis and modification, system performance and potential for practical applications. It is expected to provide insights into the development of HER catalysts towards MEC applications. © 2017 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hierarchical hybrid of Ni{sub 3}N/N-doped reduced graphene oxide nanocomposite as a noble metal free catalyst for oxygen reduction reaction

Energy Technology Data Exchange (ETDEWEB)

Zhao, Qi; Li, Yingjun; Li, Yetong [College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021 (China); Huang, Keke [State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun 130012 (China); Wang, Qin, E-mail: qinwang@imu.edu.cn [College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021 (China); Inner Mongolia Key Lab. of Nanoscience and Nanotechnology, Inner Mongolia University, Hohhot 010021 (China); Zhang, Jun, E-mail: cejzhang@imu.edu.cn [College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021 (China); Inner Mongolia Key Lab. of Nanoscience and Nanotechnology, Inner Mongolia University, Hohhot 010021 (China)

2017-04-01

Highlights: • Hybrid of Ni{sub 3}N/N-RGO catalysts are synthesized by using a two-step method. • The catalysts manifest superior catalytic activity towards the ORR. • High activities are attributed to enhanced electron density and synergistic effects. - Abstract: Novel nickel nitride (Ni{sub 3}N) nanoparticles supported on nitrogen-doped reduced graphene oxide nanosheets (N-RGOs) are synthesized via a facile strategy including hydrothermal and subsequent calcination methods, in which the reduced graphene oxide nanosheets (RGOs) are simultaneously doped with nitrogen species. By varying the content of the RGOs, a series of Ni{sub 3}N/N-RGO nanocomposites are obtained. The Ni{sub 3}N/N-RGO-30% hybrid nanocomposite exhibits superior catalytic activity towards oxygen reduction reaction (ORR) under alkaline condition (0.1 M KOH). Furthermore, this hybrid catalyst also demonstrates high tolerance to methanol poisoning. The RGO containing rich N confers the nanocomposite with large specific surface area and high electronic conduction ability, which can enhance the catalytic efficiency of Ni{sub 3}N nanoparticles. The enhanced catalytic activity can be attributed to the synergistic effect between Ni{sub 3}N and nitrogen doped reduced graphene oxide. In addition, the sufficient contact between Ni{sub 3}N nanoparticles and the N-RGO nanosheets simultaneously promotes good nanoparticle dispersion and provides a consecutive activity sites to accelerate electron transport continuously, which further enhance the ORR performance. The Ni{sub 3}N/N-RGO may be further an ideal candidate as efficient and inexpensive noble metal-free ORR electrocatalyst in fuel cells.

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.

Down-conversion phosphors as noble-metal-free co-catalyst in ZnO for efficient visible light photocatalysis

Energy Technology Data Exchange (ETDEWEB)

Chu, Haipeng [Institute of Coordination Bond Metrology and Engineering, College of Materials Science and Engineering, China Jiliang University, Hangzhou 310018 (China); Liu, Xinjuan, E-mail: lxj669635@126.com [Institute of Coordination Bond Metrology and Engineering, College of Materials Science and Engineering, China Jiliang University, Hangzhou 310018 (China); Liu, Jiaqing [Engineering Research Center for Nanophotonics & Advanced Instrument, Ministry of Education, Department of Physics, East China Normal University, Shanghai 200062 (China); Lei, Wenyan [Institute of Coordination Bond Metrology and Engineering, College of Materials Science and Engineering, China Jiliang University, Hangzhou 310018 (China); Li, Jinliang [Engineering Research Center for Nanophotonics & Advanced Instrument, Ministry of Education, Department of Physics, East China Normal University, Shanghai 200062 (China); Wu, Tianyang [Institute of Coordination Bond Metrology and Engineering, College of Materials Science and Engineering, China Jiliang University, Hangzhou 310018 (China); Li, Ping [Shanghai Nanotechnology Promotion Center, Shanghai 200237 (China); Li, Huili; Pan, Likun [Engineering Research Center for Nanophotonics & Advanced Instrument, Ministry of Education, Department of Physics, East China Normal University, Shanghai 200062 (China)

2017-01-01

Graphical abstract: ZnO-Lu{sub 3}(Al,Si){sub 5}(O,N){sub 12}:Ce{sup 3+} hybrid photocatalysts were synthesized via a fast microwave-assisted approach for visible light photocatalytic degradation of organic pollutions with a high degradation rate of 91%. - Highlights: • ZnO-Lu{sub 3}(Al,Si){sub 5}(O,N){sub 12}:Ce{sup 3+} were synthesized via a facile microwave-assisted method. • Lu{sub 3}(Al,Si){sub 5}(O,N){sub 12}:Ce{sup 3+} acts as co-catalyst to facilitates the self-sensitized degradation of MB. • ZnO-Lu{sub 3}(Al,Si){sub 5}(O,N){sub 12}:Ce{sup 3+} exhibited enhanced visible light photocatalytic activity. • A high MB degradation rate of 91% was achieved under visible light irradiation. - Abstract: Exploring novel visible light responsive photocatalysts is one of greatly significant issues from the viewpoint of using solar energy. Here we report the yellow-orange emitting α-Si{sub 3}N{sub 4}-doped Lu{sub 3}Al{sub 5}O{sub 12}:Ce{sup 3+} (Lu{sub 3}Al{sub 5-x}Si{sub x}O{sub 12-x}N{sub x}:Ce{sup 3+}) phosphors as a noble-metal-free co-catalyst for enhanced visible light photocatalytic activity of ZnO. The results show that ZnO-Lu{sub 3}Al{sub 5-x}Si{sub x}O{sub 12-x}N{sub x}:Ce{sup 3+} hybrid photocatalysts using a fast microwave-assisted approach exhibits a 91% methylene blue (MB) degradation under visible light irradiation at 240 min, which evidence the synergistic effect of ZnO and Lu{sub 3}Al{sub 5-x}Si{sub x}O{sub 12-x}N{sub x}:Ce{sup 3+} that suppress the rate of charge recombination and increase the self-sensitized degradation of MB. ZnO-down conversion phosphors can be envisaged as potential candidate in environmental engineering and solar energy applications.

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

Energy Technology Data Exchange (ETDEWEB)

Wang, Yujia; Shen, Yueyue; Qiu, Yunfei; Zhang, Ting; Liao, Yang; Zhao, Shilin; Ma, Jun, E-mail: 1044208419@qq.com; Mao, Hui, E-mail: rejoice222@163.com [Sichuan Normal University, College of Chemistry and Materials Science (China)

2016-10-15

Noble metal nanoparticles are promising candidates to replace conventional bulk counterparts owing to their high activity and selectivity. To enable catalyst recovery, noble metal nanoparticles are often supported onto solid matrices to prepare heterogeneous catalyst. Although recycle of noble metal nanoparticles is realized by heterogenization, a loss of activity is usually encountered. In the present investigation, Pt nanoparticles with tunable particle size (1.85–2.80 nm) were facilely prepared by using polyphenols as amphiphilic stabilizers. The as-prepared Pt nanoparticles colloid solution could be used as highly active catalyst in aqueous–organic biphasic catalysis. The phenolic hydroxyls of polyphenols could constrain Pt nanoparticles in aqueous phase, and simultaneously, the aromatic scaffold of polyphenols ensured effective interactions between substrates and Pt nanoparticles. As a consequence, the obtained polyphenols-stabilized Pt nanoparticles exhibited high activity and cycling stability in biphasic hydrogenation of a series of unsaturated compounds. Compared with conventional heterogeneous Pt-C and Pt-Al{sub 2}O{sub 3} catalysts, polyphenols-stabilized Pt nanoparticles showed obvious advantage both in activity and cycling stability.

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

International Nuclear Information System (INIS)

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

2016-01-01

Noble metal nanoparticles are promising candidates to replace conventional bulk counterparts owing to their high activity and selectivity. To enable catalyst recovery, noble metal nanoparticles are often supported onto solid matrices to prepare heterogeneous catalyst. Although recycle of noble metal nanoparticles is realized by heterogenization, a loss of activity is usually encountered. In the present investigation, Pt nanoparticles with tunable particle size (1.85–2.80 nm) were facilely prepared by using polyphenols as amphiphilic stabilizers. The as-prepared Pt nanoparticles colloid solution could be used as highly active catalyst in aqueous–organic biphasic catalysis. The phenolic hydroxyls of polyphenols could constrain Pt nanoparticles in aqueous phase, and simultaneously, the aromatic scaffold of polyphenols ensured effective interactions between substrates and Pt nanoparticles. As a consequence, the obtained polyphenols-stabilized Pt nanoparticles exhibited high activity and cycling stability in biphasic hydrogenation of a series of unsaturated compounds. Compared with conventional heterogeneous Pt-C and Pt-Al 2 O 3 catalysts, polyphenols-stabilized Pt nanoparticles showed obvious advantage both in activity and cycling stability.

Sinter-Resistant Platinum Catalyst Supported by Metal-Organic Framework

Energy Technology Data Exchange (ETDEWEB)

Kim, In Soo [Materials Science Division, Argonne National Lab, 9700 S Cass Ave. Argonne IL 60439 USA; Nanophotonics Center, Korea Institute of Science and Technology, Seoul 02792 South Korea; Li, Zhanyong [Department of Chemistry, Northwestern University, 2145 Sheridan Rd. Evanston IL 60208 USA; Zheng, Jian [Institute for Integrated Catalysis, Pacific Northwest National Lab, P.O. Box 999 Richland WA 99352 USA; Platero-Prats, Ana E. [X-ray Science Division, Argonne National Lab, 9700 S Cass Ave. Argonne IL 60439 USA; Mavrandonakis, Andreas [Department of Chemistry, University of Minnesota, 207 Pleasant St. SE Minneapolis MN 55455 USA; Pellizzeri, Steven [Chemical and Biomolecular Engineering, Clemson University, 205 Earle Hall Clemson SC 29634 USA; Ferrandon, Magali [Chemical Sciences and Engineering Division, Argonne National Lab, 9700 S. Cass Ave. Argonne IL 60439 USA; Vjunov, Aleksei [Institute for Integrated Catalysis, Pacific Northwest National Lab, P.O. Box 999 Richland WA 99352 USA; Gallington, Leighanne C. [X-ray Science Division, Argonne National Lab, 9700 S Cass Ave. Argonne IL 60439 USA; Webber, Thomas E. [Department of Chemistry, University of Minnesota, 207 Pleasant St. SE Minneapolis MN 55455 USA; Vermeulen, Nicolaas A. [Department of Chemistry, Northwestern University, 2145 Sheridan Rd. Evanston IL 60208 USA; Penn, R. Lee [Department of Chemistry, University of Minnesota, 207 Pleasant St. SE Minneapolis MN 55455 USA; Getman, Rachel B. [Chemical and Biomolecular Engineering, Clemson University, 205 Earle Hall Clemson SC 29634 USA; Cramer, Christopher J. [Department of Chemistry, University of Minnesota, 207 Pleasant St. SE Minneapolis MN 55455 USA; Chapman, Karena W. [X-ray Science Division, Argonne National Lab, 9700 S Cass Ave. Argonne IL 60439 USA; Camaioni, Donald M. [Institute for Integrated Catalysis, Pacific Northwest National Lab, P.O. Box 999 Richland WA 99352 USA; Fulton, John L. [Institute for Integrated Catalysis, Pacific Northwest National Lab, P.O. Box 999 Richland WA 99352 USA; Lercher, Johannes A. [Institute for Integrated Catalysis, Pacific Northwest National Lab, P.O. Box 999 Richland WA 99352 USA; Department of Chemistry and Catalysis Research Institute, Technische Universität München, Lichtenbergstrasse 4 85748 Garching Germany; Farha, Omar K. [Department of Chemistry, Northwestern University, 2145 Sheridan Rd. Evanston IL 60208 USA; Hupp, Joseph T. [Materials Science Division, Argonne National Lab, 9700 S Cass Ave. Argonne IL 60439 USA; Department of Chemistry, Northwestern University, 2145 Sheridan Rd. Evanston IL 60208 USA; Martinson, Alex B. F. [Materials Science Division, Argonne National Lab, 9700 S Cass Ave. Argonne IL 60439 USA

2018-01-02

Installed on the zirconia nodes of a metal-organic framework (MOF) NU-1000 via targeted vapor-phase synthesis. The catalytic Pt clusters, site-isolated by organic linkers, are shown to exhibit high catalytic activity for ethylene hydrogenation while exhibiting resistance to sintering up to 200 degrees C. In situ IR spectroscopy reveals the presence of both single atoms and few-atom clusters that depend upon synthesis conditions. Operando X-ray absorption spectroscopy and Xray pair distribution analyses reveal unique changes in chemical bonding environment and cluster size stability while on stream. Density functional theory calculations elucidate a favorable reaction pathway for ethylene hydrogenation with the novel catalyst. These results provide evidence that atomic layer deposition (ALD) in MOFs is a versatile approach to the rational synthesis of size-selected clusters, including noble metals, on a high surface area support.

Metal nanostructures for non-enzymatic glucose sensing

International Nuclear Information System (INIS)

Tee, Si Yin; Teng, Choon Peng; Ye, Enyi

2017-01-01

This review covers the recent development of metal nanostructures in electrochemical non-enzymatic glucose sensing. It highlights a variety of nanostructured materials including noble metals, other transition metals, bimetallic systems, and their hybrid with carbon-based nanomaterials. Particularly, attention is devoted to numerous approaches that have been implemented for improving the sensors performance by tailoring size, shape, composition, effective surface area, adsorption capability and electron-transfer properties. The correlation of the metal nanostructures to the glucose sensing performance is addressed with respect to the linear concentration range, sensitivity and detection limit. In overall, this review provides important clues from the recent scientific achievements of glucose sensor nanomaterials which will be essentially useful in designing better and more effective electrocatalysts for future electrochemical sensing industry. - Highlights: • Overview of recent development of metal nanostructures in electrochemical non-enzymatic glucose sensing. • Special attention is focussed on noble metals, other transition metals, bimetallic systems, and their hybrid with carbon-based nanomaterials. • Merits and limitations of various metal nanostructures in electrochemical non-enzymatic glucose sensing. • Strategies to improve the glucose sensing performance of metal nanostructures as electrocatalysts.

Monodisperse Platinum and Rhodium Nanoparticles as Model Heterogeneous Catalysts

Energy Technology Data Exchange (ETDEWEB)

Grass, Michael Edward [Univ. of California, Berkeley, CA (United States)

2008-09-01

Model heterogeneous catalysts have been synthesized and studied to better understand how the surface structure of noble metal nanoparticles affects catalytic performance. In this project, monodisperse rhodium and platinum nanoparticles of controlled size and shape have been synthesized by solution phase polyol reduction, stabilized by polyvinylpyrrolidone (PVP). Model catalysts have been developed using these nanoparticles by two methods: synthesis of mesoporous silica (SBA-15) in the presence of nanoparticles (nanoparticle encapsulation, NE) to form a composite of metal nanoparticles supported on SBA-15 and by deposition of the particles onto a silicon wafer using Langmuir-Blodgett (LB) monolayer deposition. The particle shapes were analyzed by transmission electron microscopy (TEM) and high resolution TEM (HRTEM) and the sizes were determined by TEM, X-ray diffraction (XRD), and in the case of NE samples, room temperature H₂ and CO adsorption isotherms. Catalytic studies were carried out in homebuilt gas-phase reactors. For the nanoparticles supported on SBA-15, the catalysts are in powder form and were studied using the homebuilt systems as plug-flow reactors. In the case of nanoparticles deposited on silicon wafers, the same systems were operated as batch reactors. This dissertation has focused on the synthesis, characterization, and reaction studies of model noble metal heterogeneous catalysts. Careful control of particle size and shape has been accomplished though solution phase synthesis of Pt and Rh nanoparticles in order to elucidate further structure-reactivity relationships in noble metal catalysis.

Engineering Single-Atom Cobalt Catalysts toward Improved Electrocatalysis.

Science.gov (United States)

Wan, Gang; Yu, Pengfei; Chen, Hangrong; Wen, Jianguo; Sun, Cheng-Jun; Zhou, Hua; Zhang, Nian; Li, Qianru; Zhao, Wanpeng; Xie, Bing; Li, Tao; Shi, Jianlin

2018-04-01

The development of cost-effective catalysts to replace noble metal is attracting increasing interests in many fields of catalysis and energy, and intensive efforts are focused on the integration of transition-metal sites in carbon as noble-metal-free candidates. Recently, the discovery of single-atom dispersed catalyst (SAC) provides a new frontier in heterogeneous catalysis. However, the electrocatalytic application of SAC is still subject to several theoretical and experimental limitations. Further advances depend on a better design of SAC through optimizing its interaction with adsorbates during catalysis. Here, distinctive from previous studies, favorable 3d electronic occupation and enhanced metal-adsorbates interactions in single-atom centers via the construction of nonplanar coordination is achieved, which is confirmed by advanced X-ray spectroscopic and electrochemical studies. The as-designed atomically dispersed cobalt sites within nonplanar coordination show significantly improved catalytic activity and selectivity toward the oxygen reduction reaction, approaching the benchmark Pt-based catalysts. More importantly, the illustration of the active sites in SAC indicates metal-natured catalytic sites and a media-dependent catalytic pathway. Achieving structural and electronic engineering on SAC that promotes its catalytic performances provides a paradigm to bridge the gap between single-atom catalysts design and electrocatalytic applications. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.)

Oxidation behaviour of noble-metal inclusions in used UO2 nuclear fuel

International Nuclear Information System (INIS)

McEachern, R.

1997-07-01

The literature on the chemistry of the noble-metal (Mo-Rh-Ru-Pd-Tc) inclusions found in used nuclear fuel has been reviewed. The Mo-Ru-Pd phase diagram is reasonably well understood, and the pseudoternary Mo-(Tc+Ru)-Rh+Pd) system can be used to qualitatively understand the phase chemistry of the noble-metal inclusions. The kinetics of the oxidation reaction are not particularly well understood, but they are of limited applicability to understanding the properties of used fuel. In contrast, it is important to determine the thermodynamic activity of molybdenum in noble-metal inclusions, so that analysis of their molybdenum content can be used as a probe of the local oxygen potential of the used fuel. (author)

Support effects on adsorption and catalytic activation of O2 in single atom iron catalysts with graphene-based substrates.

Science.gov (United States)

Gao, Zheng-Yang; Yang, Wei-Jie; Ding, Xun-Lei; Lv, Gang; Yan, Wei-Ping

2018-03-07

The adsorption and catalytic activation of O 2 on single atom iron catalysts with graphene-based substrates were investigated systematically by density functional theory calculation. It is found that the support effects of graphene-based substrates have a significant influence on the stability of the single atom catalysts, the adsorption configuration, the electron transfer mechanism, the adsorption energy and the energy barrier. The differences in the stable adsorption configuration of O 2 on single atom iron catalysts with different graphene-based substrates can be well understood by the symmetrical matching principle based on frontier molecular orbital analysis. There are two different mechanisms of electron transfer, in which the Fe atom acts as the electron donor in single vacancy graphene-based substrates while the Fe atom mainly acts as the bridge for electron transfer in double vacancy graphene-based substrates. The Fermi softness and work function are good descriptors of the adsorption energy and they can well reveal the relationship between electronic structure and adsorption energy. This single atom iron catalyst with single vacancy graphene modified by three nitrogen atoms is a promising non-noble metal single atom catalyst in the adsorption and catalytic oxidation of O 2 . Furthermore, the findings can lay the foundation for the further study of graphene-based support effects and provide a guideline for the development and design of new non-noble-metal single atom catalysts.

Design of sintering-stable heterogeneous catalysts

DEFF Research Database (Denmark)

Gallas-Hulin, Agata

One of the major issues in the use of metal nanoparticles in heterogeneous catalysis is sintering. Sintering occurs at elevated temperatures because of increased mobility of nanoparticles, leading to their agglomeration and, as a consequence, to the deactivation of the catalyst. It is an emerging...... problem especially for the noble metals-based catalysis. These metals being expensive and scarce, it is worth developing catalyst systems which preserve their activity over time. Encapsulation of nanoparticles inside zeolites is one of the ways to prevent sintering. Entrapment of nanoparticles inside...

Ni-Based Catalysts for Low Temperature Methane Steam Reforming: Recent Results on Ni-Au and Comparison with Other Bi-Metallic Systems

Directory of Open Access Journals (Sweden)

Anna M. Venezia

2013-06-01

Full Text Available Steam reforming of light hydrocarbons provides a promising method for hydrogen production. Ni-based catalysts are so far the best and the most commonly used catalysts for steam reforming because of their acceptably high activity and significantly lower cost in comparison with alternative precious metal-based catalysts. However, nickel catalysts are susceptible to deactivation from the deposition of carbon, even when operating at steam-to-carbon ratios predicted to be thermodynamically outside of the carbon-forming regime. Reactivity and deactivation by carbon formation can be tuned by modifying Ni surfaces with a second metal, such as Au through alloy formation. In the present review, we summarize the very recent progress in the design, synthesis, and characterization of supported bimetallic Ni-based catalysts for steam reforming. The progress in the modification of Ni with noble metals (such as Au and Ag is discussed in terms of preparation, characterization and pretreatment methods. Moreover, the comparison with the effects of other metals (such as Sn, Cu, Co, Mo, Fe, Gd and B is addressed. The differences of catalytic activity, thermal stability and carbon species between bimetallic and monometallic Ni-based catalysts are also briefly shown.

Catalytic reduction of NOx in gasoline engine exhaust over copper- and nickel-exchanged X-zeolite catalysts

International Nuclear Information System (INIS)

Bhattacharyya, S.; Das, R.K.

2001-01-01

Catalytic removal of NO x in engine exhaust gases can be accomplished by non-selective reduction, selective reduction and decomposition. Noble metals are extensively used for non-selective reduction of NO x and up to 90% of engine NO x emissions can be reduced in a stoichiometric exhaust. This requirement of having the stoichiometric fuel-air ratio acts against efficiency improvement of engines. Selective NO x reduction in the presence of different reductants such as, NH 3 , urea or hydrocarbons, requires close control of the amount of reductant being injected which otherwise may be emitted as a pollutant. Catalytic decomposition is the best option for NO x removal. Nevertheless, catalysts which are durable, economic and active for NO x reduction at normal engine exhaust temperature ranges are still being investigated. Three catalysts based on X-zeolite have been developed by exchanging the Na+ ion with copper, nickel and copper-nickel metal ions and applied to the exhaust of a stationary gasoline engine to explore their potential for catalytic reduction of NO x under a wide range of engine and exhaust conditions. Some encouraging results have been obtained. The catalyst Cu-X exhibits much better NO x reduction performance at any temperature in comparison to Cu-Ni-X and Ni-X; while Cu-Ni-X catalyst exhibits slightly better performance than Ni-X catalyst. Maximum NO x efficiency achieved with Cu-X catalyst is 59.2% at a space velocity (sv) of 31 000 h -1 ; while for Cu-Ni-X and Ni-X catalysts the equivalent numbers are 60.4% and 56% respectively at a sv of 22 000 h -1 . Unlike noble metals, the doped X-zeolite catalysts exhibit significant NO x reduction capability for a wide range of air/fuel ratio and with a slower rate of decline as well with increase in air/fuel ratio. (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)

CuCo2O4 nanoplate film as a low-cost, highly active and durable catalyst towards the hydrolytic dehydrogenation of ammonia borane for hydrogen production

Science.gov (United States)

Liu, Quanbing; Zhang, Shengjie; Liao, Jinyun; Feng, Kejun; Zheng, Yuying; Pollet, Bruno G.; Li, Hao

2017-07-01

Catalytic dehydrogenation of ammonia borane is one of the most promising routes for the production of clean hydrogen as it is seen as a highly efficient and safe method. However, its large-scale industrial application is either limited by the high cost of the catalyst (usually a noble metal based catalyst) or by the low activity and poor reusability (usually a non-noble metal catalyst). In this study, we have successfully prepared three low-cost CuCo2O4 nanocatalysts, namely: (i) Ti supported CuCo2O4 film made of CuCo2O4 nanoplates, (ii) Ti supported CuCo2O4 film made of CuCo2O4 nanosheets, and (iii) unsupported CuCo2O4 nanoparticles. Among the three catalysts used for the hydrolytic dehydrogeneration of ammonia borane, the CuCo2O4 nanoplate film exhibits the highest catalytic activity with a turnover frequency (TOF) of ∼44.0 molhydrogen min-1 molcat-1. This is one of the largest TOF value for noble-metal-free catalysts ever reported in the literature. Moreover, the CuCo2O4 nanoplate film almost keeps its original catalytic activity after eight cycles, indicative of its high stability and good reusability. Owing to its advantages, the CuCo2O4 nanoplate film can be a promising catalyst for the hydrolytic dehydrogenation of ammonia borane, which may find important applications in the field of hydrogen energy.

Nanoparticular metal oxide/anatase catalysts

DEFF Research Database (Denmark)

2010-01-01

The present invention concerns a method of preparation of nanoparticular metal oxide catalysts having a narrow particle size distribution. In particular, the invention concerns preparation of nanoparticular metal oxide catalyst precursors comprising combustible crystallization seeds upon which...... the catalyst metai oxide is co-precipitated with the carrier metal oxide, which crystallization seeds are removed by combustion in a final calcining step. The present invention also concerns processes wherein the nanoparticular metal oxide catalysts of the invention are used, such as SCR (deNOx) reactions...

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

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.

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

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

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.

Carbon Nanofibers as Catalyst Support for Noble Metals

NARCIS (Netherlands)

Toebes, M.L.

2004-01-01

In the quest for new and well-defined support materials for heterogeneous catalysts we explored the potential of carbon nanofibers (CNF). CNF belongs to the by now extensive family of synthetic graphite-like carbon materials with advantageous and tunable physico-chemical properties. Aim of the work

Development of Coke-tolerant Transition Metal Catalysts for Dry Reforming of Methane

KAUST Repository

Al-Sabban, Bedour E.

2016-11-07

Dry reforming of methane (DRM) is an attractive and promising process for the conversion of methane and carbon dioxide which are the most abundant carbon sources into valuable syngas. The produced syngas, which is a mixture of hydrogen and carbon monoxide, can be used as intermediates in the manufacture of numerous chemicals. To achieve high conversion, DRM reaction is operated at high temperatures (700-900 °C) that can cause major drawbacks of catalyst deactivation by carbon deposition, metal sintering or metal oxidation. Therefore, the primary goal is to develop a metal based catalyst for DRM that can completely suppress carbon formation by designing the catalyst composition. The strategy of this work was to synthesize Ni-based catalysts all of which prepared by homogeneous deposition precipitation method (HDP) to produce nanoparticles with narrow size distribution. In addition, control the reactivity of the metal by finely tuning the bimetallic composition and the reaction conditions in terms of reaction temperature and pressure. The highly endothermic dry reforming of methane proceeds via CH4 decomposition to leave surface carbon species, followed by removal of C with CO2-derived species to give CO. Tuning the reactivity of the active metal towards these reactions during DRM allows in principle the catalyst surface to remain active and clean without carbon deposition for a long-term. The initial attempt was to improve the resistance of Ni catalyst towards carbon deposition, therefore, a series of 5 wt.% bimetallic Ni9Pt1 were supported on various metal oxides (Al2O3, CeO2, and ZrO2). The addition of small amount of noble metal improved the stability of the catalyst compared to their monometallic Ni and Pt catalysts, but still high amount of carbon (> 0.1 wt.%) was formed after 24 h of the reaction. The obtained results showed that the catalytic performance, particle size and amount of deposited carbon depends on the nature of support. Among the tested

Noble metal alloys for metal-ceramic restorations.

Science.gov (United States)

Anusavice, K J

1985-10-01

A review of the comparative characteristics and properties of noble metal alloys used for metal-ceramic restorations has been presented. Selection of an alloy for one's practice should be based on long-term clinical data, physical properties, esthetic potential, and laboratory data on metal-ceramic bond strength and thermal compatibility with commercial dental porcelains. Although gold-based alloys, such as the Au-Pt-Pd, Au-Pd-Ag, and Au-Pd classes, may appear to be costly compared with the palladium-based alloys, they have clearly established their clinical integrity and acceptability over an extended period of time. Other than the relatively low sag resistance of the high gold-low silver content alloys and the potential thermal incompatibility with some commercial porcelain products, few clinical failures have been observed. The palladium-based alloys are less costly than the gold-based alloys. Palladium-silver alloys require extra precautions to minimize porcelain discoloration. Palladium-copper and palladium-cobalt alloys may also cause porcelain discoloration, as copper and cobalt are used as colorants in glasses. The palladium-cobalt alloys are least susceptible to high-temperature creep compared with all classes of noble metals. Nevertheless, insufficient clinical data exist to advocate the general use of the palladium-copper and palladium-cobalt alloys at the present time. One should base the selection and use of these alloys in part on their ability to meet the requirements of the ADA Acceptance Program. A list of acceptable or provisionally acceptable alloys is available from the American Dental Association and is published annually in the Journal of the American Dental Association. Dentists have the legal and ethical responsibility for selection of alloys used for cast restorations. This responsibility should not be delegated to the dental laboratory technician. It is advisable to discuss the criteria for selection of an alloy with the technician and the

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

Noble metal behavior during melting of simulated high-level nuclear waste glass feeds

International Nuclear Information System (INIS)

Anderson, L.D.; Dennis, T.; Elliott, M.L.; Hrma, P.

1994-01-01

Noble metals and their oxides can settle in waste glass melters and cause electrical shorting. Simulate waste feeds from Hanford, Savannah River, and Kernforschungszentrum Karlsruhe were heat treated for 1 hour in a gradient furnace at temperatures ranging from approximately 600 degrees C to 1000 degrees C and examined by electron microscopy to determine shapes, sizes, and distribution of noble metal particles as a function of temperature. Individual noble metal particles and agglomerates of rhodium (Rh), ruthenium (RuO 2 ), and palladium (Pd), as well as their alloys, were seen. The majority of particles and agglomerates were generally less than 10 μm; however, large agglomerations (up to 1 mm) were found in the German feed. 5 refs., 6 figs., 2 tabs

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.

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.

Sinter-Resistant Platinum Catalyst Supported by Metal-Organic Framework.

Science.gov (United States)

Kim, In Soo; Li, Zhanyong; Zheng, Jian; Platero-Prats, Ana E; Mavrandonakis, Andreas; Pellizzeri, Steven; Ferrandon, Magali; Vjunov, Aleksei; Gallington, Leighanne C; Webber, Thomas E; Vermeulen, Nicolaas A; Penn, R Lee; Getman, Rachel B; Cramer, Christopher J; Chapman, Karena W; Camaioni, Donald M; Fulton, John L; Lercher, Johannes A; Farha, Omar K; Hupp, Joseph T; Martinson, Alex B F

2018-01-22

Single atoms and few-atom clusters of platinum are uniformly installed on the zirconia nodes of a metal-organic framework (MOF) NU-1000 via targeted vapor-phase synthesis. The catalytic Pt clusters, site-isolated by organic linkers, are shown to exhibit high catalytic activity for ethylene hydrogenation while exhibiting resistance to sintering up to 200 °C. In situ IR spectroscopy reveals the presence of both single atoms and few-atom clusters that depend upon synthesis conditions. Operando X-ray absorption spectroscopy and X-ray pair distribution analyses reveal unique changes in chemical bonding environment and cluster size stability while on stream. Density functional theory calculations elucidate a favorable reaction pathway for ethylene hydrogenation with the novel catalyst. These results provide evidence that atomic layer deposition (ALD) in MOFs is a versatile approach to the rational synthesis of size-selected clusters, including noble metals, on a high surface area support. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Noble Metal Decoration and Presulfation on TiO2: Increased Photocatalytic Activity and Efficient Esterification of n-Butanol with Citric Acid

Directory of Open Access Journals (Sweden)

Yu Niu

2016-01-01

Full Text Available TiO2 has been widely used as a key catalyst in photocatalytic reactions; it also shows good catalytic activity for esterification reactions. Different sulfated M-TiO2 nanoparticles (M = Ag, Au, Rh, and Pt were prepared by photodeposition and ultrasonic methods. The results show that the noble metal nanoparticles, which were loaded onto a TiO2 surface, slightly affected the crystal phase and particle size of TiO2. Among all the catalysts, SO42-/Au-TiO2 exhibited the best catalytic activity in the esterification reaction for the synthesis of citric acid n-butyl acetate and in the decomposition of methyl orange, as confirmed by a high conversion rate of up to 98.2% and 100% degradation rate, respectively. This can be attributed to an increase in the Lewis acidity of the catalyst and increased separation efficiency of electron-hole pairs. This superior catalyst has great potential applications in esterification reactions and wastewater treatments.

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

Catalyst design for clean and efficient fuels

DEFF Research Database (Denmark)

Šaric, Manuel

cobalt promoted MoS2 catalyst. Reactivity of a series of model molecules, found in oil prior to desulfurization, is studied on cobalt promoted MoS2. Such an approach has the potential to explain the underlying processes involved in the removal of sulfur at each specific site of the catalyst. The goal...... is to identify which sites are active towards specific molecules and in getting insight to what the ideal catalyst should look like in terms of morphology. Dimethyl carbonate is an environmentally benign compound that can be used as a solvent and precursor in chemical synthesis or as a fuel and fuel additive...... processes currently used. It is found that noble metals can be used as electrocatalysts for the synthesis of dimethyl carbonate, significantly lowering the potential when using copper instead of gold. Besides being active, copper was found to be selective towards dimethyl carbonate. A non-selective catalyst...

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)

Synthesis and characterization of platinum supported on alumina doped with cerium catalyst

International Nuclear Information System (INIS)

Yusof Abdullah; Abd Fatah Awang Mat; Mohd Ali Sufi; Sarimah Mahat; Razali Kassim; Nurhaslinda Abdullah.

1996-03-01

The synthesis and characterization of gamma-alumina doped with cerium as platinum support for the automobile exhaust catalyst are described. Platinum/alumina/ceria catalyst were prepared by impregnation of hexachloroplatinic acid and sintered at 500 degree Celsius to obtain metal dispersions of 1.0 wt%. Catalyst distribution inside the powder and the effects of the addition of cerium to alumina were analyzed by the scanning electron microscopy (SEM) and x-ray fluorescence spectroscopy (XRF). The results showed that the alumina - supported catalysts contained well dispersion of the noble metal

Nature of the metal-support interface in supported metal catalysts: results from x-ray absorption spectroscopy

NARCIS (Netherlands)

Koningsberger, D.C.; Gates, B.C.

1992-01-01

X-ray absorption spectra characterizing the metal-support interface in supported metal complexes and supported metal catalysts are summarized and evaluated with 29 refs. Mononuclear transition metal complexes on non-reducible metal oxide supports are bonded with metal-oxygen bonds of .apprx.2.15

Controllable synthesis of Co3O4 nanocrystals as efficient catalysts for oxygen reduction reaction

Science.gov (United States)

Li, Baoying; Zhang, Yihe; Du, Ruifeng; Liu, Lei; Yu, Xuelian

2018-03-01

The electrochemical oxygen reduction reaction (ORR) has received great attention due to its importance in fuel cells and metal-air batteries. Here, we present a simple approach to prepare non-noble metal catalyst-Co3O4 nanocrystals (NCs). The particle size and shape were simply controlled by different types and concentrations of metal precursor. Furthermore, different sizes and shapes of Co3O4 NCs are explored as electrocatalysts for ORR, and it has been observed that particles with a similar shape, and smaller particle size led to greater catalytic current densities because of the greater surface area. For particles with a comparable size, the shape or crystalline structure governed the activity of the electrocatalytic reactions. Most importantly, the 9 nm-Co3O4 were demonstrated to act as low-cost catalysts for the ORR with a similar performance to that of Pt catalysts.

Microwave assisted green synthesis and characterizations of noble metal nanoparticles and their roles as catalysts in organic reduction reactions and anticancer agent

Science.gov (United States)

Francis, Sijo; Koshy, Ebey P.; Mathew, Beena

2018-04-01

Nanomaterials are interesting chemicals that uncover the explorations and expectations of decades. The report suggests environmentally benevolent and easy route for the synthesis of noble metal nanoparticles. Personnel, laboratory and ecological benefits of the synthesized nanoparticles are demonstrated herein. The aqueous extract from the leaves of Litchi chinensis Sonn is performed as the alternative reducing agent. The microwave activated silver and gold nanoparticles have spherical geometries with crystalline essence. X-ray diffraction technique witnessed the face centered cubic lattice for the nano silver and gold particles that preferentially oriented towards the (111) plane. The reduction of nitro anilines is performed to elucidate the heterogeneous catalytic power of the nanoparticles. The nano catalyst is a potential candidate to meet the challenges raised from organic pollutant dye that cause environmental contamination. The chemical stability, low-cost factor and plant based origin of the new nanoparticles are admired. The multitudes of health hazards especially human carcinoma can be effectively inhibited by the silver and gold nanoparticles. The leaf extract, silver and gold nanoparticles showed IC50 values 66.56 ± 0.80, 23.55 ± 0.43 and 20.38 ± 0.41 μg ml‑1 respectively against the human lung adenocarcinoma cell lines A549 determined using the MTT dye conversion assay.

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.

Noble metal behavior during melting of simulated high-level nuclear waste glass feeds

International Nuclear Information System (INIS)

Anderson, L.D.; Dennis, T.; Elliott, M.L.; Hrma, P.

1993-04-01

Noble metals and their oxides can settle in waste glass melters and cause electrical shorting. Simulated waste feeds from Hanford, Savannah River, and Germany were heat treated for 1 hour in a gradient furnace at temperatures ranging from approximately 600 degrees C--1000 degrees C and examined by electron microscopy to determine shapes, sizes, and distribution of noble metal particles as a function of temperature. Individual noble metal particles and agglomerates of rhodium (Rh), ruthenium (RuO 2 ), and palladium (Pd), as well as their alloys, were seen. the majority of particles and agglomerates were generally less than 10 microns; however, large agglomerations (up to 1 mm) were found in the German feed. Detailed particle distribution and characterization was performed for a Hanford waste to provide input to computer modeling of particle settling in the melter

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.

Rare earth metals for automotive exhaust catalysts

International Nuclear Information System (INIS)

Shinjoh, Hirohumi

2006-01-01

The usage of rare earth metals for automotive exhaust catalysts is demonstrated in this paper. Rare earth metals have been widely used in automotive catalysts. In particular, three-way catalysts require the use of ceria compounds as oxygen storage materials, and lanthana as both a stabilizer of alumina and a promoter. The application for diesel catalysts is also illustrated. Effects of inclusion of rare earth metals in automotive catalysts are discussed

Transition-Metal-Controlled Inorganic Ligand-Supported Non-Precious Metal Catalysts for the Aerobic Oxidation of Amines to Imines.

Science.gov (United States)

Yu, Han; Zhai, Yongyan; Dai, Guoyong; Ru, Shi; Han, Sheng; Wei, Yongge

2017-10-09

Most state-of-art transition-metal catalysts usually require organic ligands, which are essential for controlling the reactivity and selectivity of reactions catalyzed by transition metals. However, organic ligands often suffer from severe problems including cost, toxicity, air/moisture sensitivity, and being commercially unavailable. Herein, we show a simple, mild, and efficient aerobic oxidation procedure of amines using inorganic ligand-supported non-precious metal catalysts 1, (NH 4 ) n [MMo 6 O 18 (OH) 6 ] (M=Cu 2+ ; Fe 3+ ; Co 3+ ; Ni 2+ ; Zn 2+ , n=3 or 4), synthesized by a simple one-step method in water at 100 °C, demonstrating that the catalytic activity and selectivity can be significantly improved by changing the central metal atom. In the presence of these catalysts, the catalytic oxidation of primary and secondary amines, as well as the coupling of alcohols and amines, can smoothly proceed to afford various imines with O 2 (1 atm) as the sole oxidant. In particular, the catalysts 1 have transition-metal ion core, and the planar arrangement of the six Mo VI centers at their highest oxidation states around the central heterometal can greatly enhance the Lewis acidity of catalytically active sites, and also enable the electrons in the center to delocalize onto the six edge-sharing MO 6 units, in the same way as ligands in traditional organometallic complexes. The versatility of this methodology maybe opens a path to catalytic oxidation through inorganic ligand-coordinated metal catalysis. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

NiMn layered double hydroxide nanosheets/NiCo2O4 nanowires with surface rich high valence state metal oxide as an efficient electrocatalyst for oxygen evolution reaction

Science.gov (United States)

Yang, Liting; Chen, Lin; Yang, Dawen; Yu, Xu; Xue, Huaiguo; Feng, Ligang

2018-07-01

High valence transition metal oxide is significant for anode catalyst of proton membrane water electrolysis technique. Herein, we demonstrate NiMn layered double hydroxide nanosheets/NiCo2O4 nanowires hierarchical nanocomposite catalyst with surface rich high valence metal oxide as an efficient catalyst for oxygen evolution reaction. A low overpotential of 310 mV is needed to drive a 10 mA cm-2 with a Tafel slope of 99 mV dec-1, and a remarkable stability during 8 h is demonstrated in a chronoamperometry test. Theoretical calculation displays the change in the rate-determining step on the nanocomposite electrode in comparison to NiCo2O4 nanowires alone. It is found high valence Ni and Mn oxide in the catalyst system can efficiently facilitate the charge transport across the electrode/electrolyte interface. The enhanced electrical conductivity, more accessible active sites and synergistic effects between NiMn layered double hydroxide nanosheets and NiCo2O4 nanowires can account for the excellent oxygen evolution reaction. The catalytic performance is comparable to most of the best non-noble catalysts and IrO2 noble catalyst, indicating the promising applications in water-splitting technology. It is an important step in the development of hierarchical nanocomposites by surface valence state tuning as an alternative to noble metals for oxygen evolution reaction.

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

Synthesis of Hydrophilic Sulfur-Containing Adsorbents for Noble Metals Having Thiocarbonyl Group Based on a Methacrylate Bearing Dithiocarbonate Moieties

Directory of Open Access Journals (Sweden)

Haruki Kinemuchi

2018-01-01

Full Text Available Novel hydrophilic sulfur-containing adsorbents for noble metals were prepared by the radical terpolymerization of a methacrylate bearing dithiocarbonate moieties (DTCMMA, hydrophilic monomers, and a cross-linker. The resulting adsorbents efficiently and selectively adsorbed noble metals (Au, Ag, and Pd from various multielement aqueous solutions at room temperature owing to the thiocarbonyl group having high affinity toward noble metals. The metal adsorption by the adsorbents was proceeded by simple mixing followed by filtration. The noble metal selectivity of the adsorbent obtained from DTCMMA and N-isopropylacrylamide was higher than that of the adsorbent obtained from DTCMMA and N,N-dimethylacrylamide due to the lower nonspecific adsorption.

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

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

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

Studies on PEM Fuel Cell Noble Metal Catalyst Dissolution

DEFF Research Database (Denmark)

Ma, Shuang; Skou, Eivind Morten

Incredibly vast advance has been achieved in fuel cell technology regarding to catalyst efficiency, improvement of electrolyte conductivity and optimization of cell system. With breathtakingly accelerating progress, Proton Exchange Membrane Fuel Cells (PEMFC) is the most promising and most widely...

Catalytic reduction of NO{sub x} in gasoline engine exhaust over copper- and nickel-exchanged X-zeolite catalysts

Energy Technology Data Exchange (ETDEWEB)

Bhattacharyya, S. [Indian Inst. of Technology, Kharagpur (India). Dept. of Mechanical Engineering; Das, R.K. [Indian School of Mines, Dhanbad (India). Dept. of Engineering and Mining Machinery

2001-10-11

Catalytic removal of NO{sub x} in engine exhaust gases can be accomplished by non-selective reduction, selective reduction and decomposition. Noble metals are extensively used for non-selective reduction of NO{sub x} and up to 90% of engine NO{sub x} emissions can be reduced in a stoichiometric exhaust. This requirement of having the stoichiometric fuel-air ratio acts against efficiency improvement of engines. Selective NO{sub x} reduction in the presence of different reductants such as, NH{sub 3}, urea or hydrocarbons, requires close control of the amount of reductant being injected which otherwise may be emitted as a pollutant. Catalytic decomposition is the best option for NO{sub x} removal. Nevertheless, catalysts which are durable, economic and active for NO{sub x} reduction at normal engine exhaust temperature ranges are still being investigated. Three catalysts based on X-zeolite have been developed by exchanging the Na+ ion with copper, nickel and copper-nickel metal ions and applied to the exhaust of a stationary gasoline engine to explore their potential for catalytic reduction of NO{sub x} under a wide range of engine and exhaust conditions. Some encouraging results have been obtained. The catalyst Cu-X exhibits much better NO{sub x} reduction performance at any temperature in comparison to Cu-Ni-X and Ni-X; while Cu-Ni-X catalyst exhibits slightly better performance than Ni-X catalyst. Maximum NO{sub x} efficiency achieved with Cu-X catalyst is 59.2% at a space velocity (sv) of 31 000 h{sup -1}; while for Cu-Ni-X and Ni-X catalysts the equivalent numbers are 60.4% and 56% respectively at a sv of 22 000 h{sup -1}. Unlike noble metals, the doped X-zeolite catalysts exhibit significant NO{sub x} reduction capability for a wide range of air/fuel ratio and with a slower rate of decline as well with increase in air/fuel ratio. (author)

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

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

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)

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

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.

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

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.

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.

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)

Bi-metallic catalysts, methods of making, and uses thereof

KAUST Repository

Basset, Jean-Marie

2017-01-19

Provided herein are bi-metallic catalysts, methods of making, and uses thereof. In some embodiments, the bi-metallic catalyst contains two different metal catalysts that can be used in hydrocarbon metathesis reactions, in some embodiments, the methods of making the bi-metallic catalysts can include two steps utilizing a surface organometallic chemistry approach in which the two different metal catalysts are sequentially grafted onto a support.

Bi-metallic catalysts, methods of making, and uses thereof

KAUST Repository

Basset, Jean-Marie; Samantaray, Manoja K.; Dey, Raju; Abou-Hamad, Edy; Kavitake, Santosh

2017-01-01

Provided herein are bi-metallic catalysts, methods of making, and uses thereof. In some embodiments, the bi-metallic catalyst contains two different metal catalysts that can be used in hydrocarbon metathesis reactions, in some embodiments, the methods of making the bi-metallic catalysts can include two steps utilizing a surface organometallic chemistry approach in which the two different metal catalysts are sequentially grafted onto a support.

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.

Catalyst of a metal heteropoly acid salt that is insoluble in a polar solvent on a non-metallic porous support and method of making

Science.gov (United States)

Wang, Yong [Richland, WA; Peden, Charles H. F. [West Richland, WA; Choi, Saemin [Richland, WA

2002-10-29

The present invention includes a catalyst having (a) a non-metallic support having a plurality of pores; (b) a metal heteropoly acid salt that is insoluble in a polar solvent on the non-metallic support; wherein at least a portion of the metal heteropoly acid salt is dispersed within said plurality of pores. The present invention also includes a method of depositing a metal heteropoly acid salt that is insoluble in a polar solvent onto a non-metallic support having a plurality of pores. The method has the steps of: (a) obtaining a first solution containing a first precursor of a metal salt cation; (b) obtaining a second solution containing a second precursor of a heteropoly acid anion in a solvent having a limited dissolution potential for said first precursor; (c) impregnating the non-metallic support with the first precursor forming a first precursor deposit within the plurality of pores, forming a first precursor impregnated support; (d) heating said first precursor impregnated support forming a bonded first precursor impregnated support; (e) impregnating the second precursor that reacts with the precursor deposit and forms the metal heteropoly acid salt.

DOE Award No. DE-FC36-03GO13108 NOVEL NON-PRECIOUS METAL CATALYSTS FOR PEMFC: CATALYST SELECTION THROUGH MOLECULAR MODELING AND DURABILITY STUDIES Final Report (September 2003 – October 2008)

Energy Technology Data Exchange (ETDEWEB)

Branko N. Popov

2009-02-20

The objective of this project is to develop novel non-precious metal electrocatalysts for oxygen reduction reaction (ORR), and demonstrate the potential of the catalysts to perform at least as good as conventional Pt catalysts currently in use in polymer electrolyte membrane fuel cell (PEMFC) with a cost at least 50 % less than a target of 0.2 g (Pt loading)/peak kW and with durability > 2,000 h operation with less than 10 % power degradation. A novel nitrogen-modified carbon-based catalyst was obtained by modifying carbon black with nitrogen-containing organic precursor in the absence of transition metal precursor. The catalyst shows the onset potential of approximately 0.76 V (NHE) for ORR and the amount of H2O2 of approximately 3% at 0.5 V (NHE). Furthermore, a carbon composite catalyst was achieved through the high-temperature pyrolysis of the precursors of transition metal (Co and Fe) and nitrogen supported on the nitrogen-modified carbon-based catalyst, followed by chemical post-treatment. This catalyst showed an onset potential for ORR as high as 0.87 V (NHE), and generated less than 1 % of H2O2. The PEM fuel cell exhibited a current density of 2.3 A cm-2 at 0.2 V for a catalyst loading of 6.0 mg cm-2. No significant performance degradation was observed for 480 h continuous operation. The characterization studies indicated that the metal-nitrogen chelate complexes decompose at the temperatures above 800 oC. During the pyrolysis, the transition metals facilitate the incorporation of pyridinic and graphitic nitrogen groups into the carbon matrix, and the carbon surface modified with nitrogen is active for ORR. In order to elucidate the role of transition metal precursor played in the formation of active sites in the non-precious metal catalysts, a novel ruthenium-based chelate (RuNx) catalyst was synthesized by using RuCl3 and propylene diammine as the Ru and N precursors, respectively, followed by high-temperature pyrolysis. This catalyst exhibited comparable

DOE Award No. DE-FC36-03GO13108 NOVEL NON-PRECIOUS METAL CATALYSTS FOR PEMFC: CATALYST SELECTION THROUGH MOLECULAR MODELING AND DURABILITY STUDIES Final Report (September 2003 – October 2008)

Energy Technology Data Exchange (ETDEWEB)

Branko N. Popov

2009-03-03

The objective of this project is to develop novel non-precious metal electrocatalysts for oxygen reduction reaction (ORR), and demonstrate the potential of the catalysts to perform at least as good as conventional Pt catalysts currently in use in polymer electrolyte membrane fuel cell (PEMFC) with a cost at least 50 % less than a target of 0.2 g (Pt loading)/peak kW and with durability > 2,000 h operation with less than 10 % power degradation. A novel nitrogen-modified carbon-based catalyst was obtained by modifying carbon black with nitrogen-containing organic precursor in the absence of transition metal precursor. The catalyst shows the onset potential of approximately 0.76 V (NHE) for ORR and the amount of H2O2 of approximately 3% at 0.5 V (NHE). Furthermore, a carbon composite catalyst was achieved through the high-temperature pyrolysis of the precursors of transition metal (Co and Fe) and nitrogen supported on the nitrogen-modified carbon-based catalyst, followed by chemical post-treatment. This catalyst showed an onset potential for ORR as high as 0.87 V (NHE), and generated less than 1 % of H2O2. The PEM fuel cell exhibited a current density of 2.3 A cm-2 at 0.2 V for a catalyst loading of 6.0 mg cm-2. No significant performance degradation was observed for 480 h continuous operation. The characterization studies indicated that the metal-nitrogen chelate complexes decompose at the temperatures above 800 oC. During the pyrolysis, the transition metals facilitate the incorporation of pyridinic and graphitic nitrogen groups into the carbon matrix, and the carbon surface modified with nitrogen is active for ORR. In order to elucidate the role of transition metal precursor played in the formation of active sites in the non-precious metal catalysts, a novel ruthenium-based chelate (RuNx) catalyst was synthesized by using RuCl3 and propylene diammine as the Ru and N precursors, respectively, followed by high-temperature pyrolysis. This catalyst exhibited comparable

Catalytic activity of mono and bimetallic Zn/Cu/MWCNTs catalysts for the thermocatalyzed conversion of methane to hydrogen

Energy Technology Data Exchange (ETDEWEB)

Erdelyi, B. [Department of Physical Chemistry, Faculty of Science, P.J. Šafárik University, Moyzesova 11, 041 54 Košice (Slovakia); Institute of Physics, Faculty of Science, P.J. Šafárik University, Park Angelium 9, 040 01 Košice (Slovakia); Oriňak, A., E-mail: andrej.orinak@upjs.sk [Department of Physical Chemistry, Faculty of Science, P.J. Šafárik University, Moyzesova 11, 041 54 Košice (Slovakia); Oriňaková, R. [Department of Physical Chemistry, Faculty of Science, P.J. Šafárik University, Moyzesova 11, 041 54 Košice (Slovakia); Lorinčík, J. [Research Center Rez, Hlavní 130, 250 68 Husinec-Řež (Czech Republic); Jerigová, M. [Department of Physical Chemistry, Comenius University, Mlynská dolina 842 15 Bratislava 4 (Slovakia); Velič, D. [Department of Physical Chemistry, Comenius University, Mlynská dolina 842 15 Bratislava 4 (Slovakia); International Laser Centre, Ilkovičová 3, 841 01 Bratislava (Slovakia); Mičušík, M. [Polymer institute, Slovak Academy of Sciences, Dubravská cesta 9, 84541 Bratislava (Slovakia); and others

2017-02-28

Highlights: • Zn/Cu/MWCNTs catalyst with good activity. • Methane conversion to hydrogen with high effectivity. • ZnO/Cu responsible for catalytic activity. - Abstract: Mono and bimetallic multiwalled carbon nanotubes (MWCNTs) fortified with Cu and Zn metal particles were studied to improve the efficiency of the thermocatalytic conversion of methane to hydrogen. The surface of the catalyst and the dispersion of the metal particles were studied by scanning electron microscopy (SEM), secondary ion mass spectrometry (SIMS) and with energy-dispersive X-ray spectroscopy (EDS). It was confirmed that the metal particles were successfully dispersed on the MWCNT surface and XPS analysis showed that the Zn was oxidised to ZnO at high temperatures. The conversion of methane to hydrogen during the catalytic pyrolysis was studied by pyrolysis gas chromatography using different amounts of catalyst. The best yields of hydrogen were obtained using pyrolysis conditions of 900 °C and 1.2 mg of Zn/Cu/MWCNT catalyst for 1.5 mL of methane.The initial conversion of methane to hydrogen obtained with Zn/Cu/MWCNTs was 49%, which represent a good conversion rate of methane to hydrogen for a non-noble metal catalyst.

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

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.)

Effect of Ce on performance and physicochemical properties of Pt-containing automotive emission control catalysts

International Nuclear Information System (INIS)

Nunan, J.G.; Silver, R.G.; Bradley, S.A.

1992-01-01

Present-day automotive emission control catalysts contain noble metals such as Pt, Pd and Rh all on an alumina support with a variety of promoters. Ce is one of the most important promoters. In this paper, the interaction between Pt and Ce is studied using TPR and STEM on a variety of catalysts. The degree of Pt/Ce interaction is increased by decreasing CeO 2 crystallite size, and to a lesser extent by increasing CeO 2 loading. Direct Pt/Ce interaction leads to a synergistic reduction of both Pt and surface Ce. This reduction qualitatively correlates with catalyst performance after activation in a reducing gas. It is proposed that this synergistic reduction of Pt and Ce is associated with observed improvements in catalyst performance using a non-oscillating exhaust gas

Supported rhodium catalysts for ammonia-borane hydrolysis. Dependence of the catalytic activity on the highest occupied state of the single rhodium atoms

Energy Technology Data Exchange (ETDEWEB)

Wang, Liangbing; Li, Hongliang; Zhang, Wenbo; Zhao, Xiao; Qiu, Jianxiang; Li, Aowen; Zheng, Xusheng; Zeng, Jie [Hefei National Lab. for Physical Sciences at the Microscale, Key Lab. of Strongly-Coupled Quantum Matter Physics, Chinese Academy of Sciences, Hefei, Anhui(China); Department of Chemical Physics, University of Science and Technology of China, Hefei, Anhui (China); Hu, Zhenpeng [School of Physics, Nankai University, Tianjin (China); Si, Rui [Shanghai Synchrotron Radiation Facility, Shanghai Institute of Applied Physics, Chinese Academy of Sciences (China)

2017-04-18

Supported metal nanocrystals have exhibited remarkable catalytic performance in hydrogen generation reactions, which is influenced and even determined by their supports. Accordingly, it is of fundamental importance to determine the direct relationship between catalytic performance and metal-support interactions. Herein, we provide a quantitative profile for exploring metal-support interactions by considering the highest occupied state in single-atom catalysts. The catalyst studied consisted of isolated Rh atoms dispersed on the surface of VO{sub 2} nanorods. It was observed that the activation energy of ammonia-borane hydrolysis changed when the substrate underwent a phase transition. Mechanistic studies indicate that the catalytic performance depended directly on the highest occupied state of the single Rh atoms, which was determined by the band structure of the substrates. Other metal catalysts, even with non-noble metals, that exhibited significant catalytic activity towards NH{sub 3}BH{sub 3} hydrolysis were rationally designed by adjusting their highest occupied states. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

Polyoxometalate electrocatalysts based on earth-abundant metals for efficient water oxidation in acidic media

Science.gov (United States)

Blasco-Ahicart, Marta; Soriano-López, Joaquín; Carbó, Jorge J.; Poblet, Josep M.; Galan-Mascaros, J. R.

2018-01-01

Water splitting is a promising approach to the efficient and cost-effective production of renewable fuels, but water oxidation remains a bottleneck in its technological development because it largely relies on noble-metal catalysts. Although inexpensive transition-metal oxides are competitive water oxidation catalysts in alkaline media, they cannot compete with noble metals in acidic media, in which hydrogen production is easier and faster. Here, we report a water oxidation catalyst based on earth-abundant metals that performs well in acidic conditions. Specifically, we report the enhanced catalytic activity of insoluble salts of polyoxometalates with caesium or barium counter-cations for oxygen evolution. In particular, the barium salt of a cobalt-phosphotungstate polyanion outperforms the state-of-the-art IrO2 catalyst even at pH < 1, with an overpotential of 189 mV at 1 mA cm-2. In addition, we find that a carbon-paste conducting support with a hydrocarbon binder can improve the stability of metal-oxide catalysts in acidic media by providing a hydrophobic environment.

N, S co-doped carbon spheres with highly dispersed CoO as non-precious metal catalyst for oxygen reduction reaction

Science.gov (United States)

Chen, Linlin; Guo, Xingpeng; Zhang, Guoan

2017-08-01

It is still a great challenge in preparing non-precious metal catalysts with high activity and long-term stability to substitute for precious metal catalysts for oxygen reduction reaction (ORR) in fuel cells. Herein, we report a novel and facile catalyst-N, S co-doped carbon spheres with highly dispersed CoO (CoO@NS-CSs), where biomass glucose spheres act as carbon precursor and H2S, NH3 derived from the decomposition of thiourea not only provide N, S sources but also can etch carbon spheres to produce nanoporous structure. CoO@NS-CSs catalyst exhibits excellent ORR activity with a high onset potential of 0.946 V vs. RHE (reversible hydrogen electrode) and a half-wave potential of 0.821 V vs. RHE through a four-electron pathway in alkaline solution, which is comparable to commercial Pt/C catalyst (onset potential: 0.926 V vs. RHE, half-wave potential: 0.827 V vs. RHE). Furthermore, both the long-term stability and methanol-tolerance of CoO@NS-CSs catalyst are superior to those of commercial Pt/C catalyst. The excellent ORR performance of CoO@NS-CSs catalyst can be attributed to its micro-mesopore structure, high specific surface area (667 m2 g-1), and highly dispersed CoO. This work manifests that the obtained CoO@NS-CSs catalyst is promising to be applied to fuel cells.

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

Lattice Boltzmann Pore-Scale Investigation of Coupled Physical-electrochemical Processes in C/Pt and Non-Precious Metal Cathode Catalyst Layers in Proton Exchange Membrane Fuel Cells

International Nuclear Information System (INIS)

Chen, Li; Wu, Gang; Holby, Edward F; Zelenay, Piotr; Tao, Wen-Quan; Kang, Qinjun

2015-01-01

Highlights: • Nanoscale structures of catalyst layer are reconstructed. • Pore-scale simulation is performed to predict macroscopic transport properties. • Reactive transport in catalyst layer with non-precious metal and Pt catalysts is studied. • Mesopores rather than micropores are required to enhance mass transport. - Abstract: High-resolution porous structures of catalyst layers (CLs) including non-precious metal catalysts (NPMCs) or Pt for proton exchange membrane fuel cells are reconstructed using the quartet structure generation set. The nanoscale structures are analyzed in terms of pore size distribution, specific surface area, and phase connectivity. Pore-scale simulation methods based on the lattice Boltzmann method are developed to predict the macroscopic transport properties in CLs. The non-uniform distribution of ionomer in CL generates more tortuous pathways for reactant transport, greatly reducing the effective diffusivity. The tortuosity of CLs is much higher than that adopted by the Bruggeman equation. Knudsen diffusion plays a significant role in oxygen diffusion and significantly reduces the effective diffusivity. Reactive transport inside the CLs is also investigated. Although the reactive surface area of the non-precious metal catalyst (NPMC) CL is much higher than that of the Pt CL, the oxygen reaction rate is lower in the NPMC CL due to the much lower reaction rate coefficient. Although pores of a few nanometers in size can increase the number of reactive sites in NPMC CLs, they contribute little to enhance the mass transport. Mesopores, which are a few tens of nanometers or larger in size, are shown to be required in order to increase the mass transport rate

Nickel oxide and carbon nanotube composite (NiO/CNT) as a novel cathode non-precious metal catalyst in microbial fuel cells.

Science.gov (United States)

Huang, Jianjian; Zhu, Nengwu; Yang, Tingting; Zhang, Taiping; Wu, Pingxiao; Dang, Zhi

2015-10-15

Comparing with the precious metal catalysts, non-precious metal catalysts were preferred to use in microbial fuel cells (MFCs) due to the low cost and high oxygen reduction reaction (ORR) efficiency. In this study, the transmission electron microscope and X-ray diffraction as well as Raman investigation revealed that the prepared nanoscale NiO was attached on the surface of CNT. Cyclic voltammogram and rotating ring-disk electrode tests showed that the NiO/CNT composite catalyst had an apparent oxygen reduction peak and 3.5 electron transfer pathway was acquired under oxygen atmosphere. The catalyst performance was highly dependent on the percentage of NiO in the CNT nanocomposites. When 77% NiO/CNT nano-sized composite was applied as cathode catalyst in membrane free single-chamber air cathode MFC, a maximum power density of 670 mW/m(2) and 0.772 V of OCV was obtained. Moreover, the MFC with pure NiO (control) could not achieve more than 0.1 V. All findings suggested that NiO/CNT could be a potential cathode catalyst for ORR in MFCs. Copyright © 2015 Elsevier B.V. All rights reserved.

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.

Non-Fermi Liquids as Highly Active Oxygen Evolution Reaction Catalysts.

Science.gov (United States)

Hirai, Shigeto; Yagi, Shunsuke; Chen, Wei-Tin; Chou, Fang-Cheng; Okazaki, Noriyasu; Ohno, Tomoya; Suzuki, Hisao; Matsuda, Takeshi

2017-10-01

The oxygen evolution reaction (OER) plays a key role in emerging energy conversion technologies such as rechargeable metal-air batteries, and direct solar water splitting. Herein, a remarkably low overpotential of ≈150 mV at 10 mA cm -2 disk in alkaline solutions using one of the non-Fermi liquids, Hg 2 Ru 2 O 7 , is reported. Hg 2 Ru 2 O 7 displays a rapid increase in current density and excellent durability as an OER catalyst. This outstanding catalytic performance is realized through the coexistence of localized d-bands with the metallic state that is unique to non-Fermi liquids. The findings indicate that non-Fermi liquids could greatly improve the design of highly active OER catalysts.

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.)

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)

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)

Facile solid-state synthesis of highly dispersed Cu nanospheres anchored on coal-based activated carbons as an efficient heterogeneous catalyst for the reduction of 4-nitrophenol

Science.gov (United States)

Wang, Shan; Gao, Shasha; Tang, Yakun; Wang, Lei; Jia, Dianzeng; Liu, Lang

2018-04-01

Coal-based activated carbons (AC) were acted as the support, Cu/AC catalysts were synthesized by a facile solid-state reaction combined with subsequent heat treatment. In Cu/AC composites, highly dispersed Cu nanospheres were anchored on AC. The catalytic activity for 4-nitrophenol (4-NP) was investigated, the effects of activation temperature and copper loading on the catalytic performance were studied. The catalysts exhibited very high catalytic activity and moderate chemical stability due to the unique characteristics of the particle-assembled nanostructures, the high surface area and the porous structure of coal-based AC and the good dispersion of metal particles. Design and preparation of non-noble metal composite catalysts provide a new direction for improving the added value of coal.

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)

Low temperature incineration of mixed wastes using bulk metal oxide catalysts

International Nuclear Information System (INIS)

Gordon, M.J.; Gaur, S.; Kelkar, S.; Baldwin, R.M.

1996-01-01

Volume reduction of low-level mixed wastes from former nuclear weapons facilities is a significant environmental problem. Processing of these materials presents unique scientific and engineering problems due to the presence of minute quantities of radionuclides which must be contained and concentrated for later safe disposal. Low-temperature catalytic incineration is one option that has been utilized at the Rocky Flats facility for this purpose. This paper presents results of research regarding evaluation of bulk metal oxides as catalysts for low-temperature incineration of carbonaceous residues which are typical by-products of fluidized bed combustion of mixed wastes under oxygen-lean conditions. A series of 14 metal oxides were screened in a thermogravimetric analyzer, using on-line mass spectrometry for speciation of reaction product gases. Catalyst evaluation criteria focused on the thermal-redox activity of the metals using both carbon black and PVC char as surrogate waste materials. Results indicated that metal oxides which were P-type semiconductor materials were suitable as catalysts for this application. Oxides of cobalt, molybdenum, vanadium, and manganese were found to be particularly stable and active catalysts under conditions specific to this process (T<650C, low oxygen partial pressures). Bench-scale evaluation of these metal oxides with respect to stability to chlorine (HCl) attack was carried out at 550C using a TG/MS system. Cobalt oxide was found to be resistant to metal loss in a HCl/He gaseous environment while metal loss from Mo, Mn, and V-based catalysts was moderate to severe. XRD and SEM/EDX analysis of spent Co catalysts indicated the formation of non-stoichiometric cobalt chlorides. Regeneration of chlorinated cobalt was found to successfully restore the low-temperature combustion activity to that of the fresh metal oxide

Non-Precious Bimetallic Catalysts for Selective Dehydrogenation of an Organic Chemical Hydride System

KAUST Repository

Shaikh Ali, Anaam

2015-07-06

Methylcyclohexane (MCH)-Toluene (TOL) chemical hydride cycles as a hydrogen carrier system is successful with the selective dehydrogenation reaction of MCH to TOL, which has been achieved only using precious Pt-based catalysts. Herein, we report improved selectivity using non-precious metal nickel-based bimetallic catalysts, where the second metal occupies the unselective step sites.

One-step flame synthesis of an active Pt/TiO2 catalyst for SO2 oxidation

DEFF Research Database (Denmark)

Johannessen, Tue; Koutsopoulos, Sotiris

2002-01-01

Flame synthesis as a route for production of composite metal oxides has been employed for the one-step synthesis of a supported noble metal catalyst, i.e. a Pt/TiO2 catalyst, by simultaneous combustion of Ti-isopropoxide and platinum acetylacetonate in a quench-cooled flame reactor. The average...... size of the platinum particles supported on aggregated nano-particles of TiO2 is approximately 2 nm. The high SO2-oxidation activity of the catalyst proves that platinum is not hidden in the titania matrix. The flame-produced catalyst showed catalytic activity similar to samples prepared by wet...

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.

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...

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.

Molybdenum-containing acidic catalysts to convert cellulosic biomass to glycolic acid

KAUST Repository

Han, Yu

2014-09-30

Embodiments of the present invention include methods and compositions related to catabolic conversion of cellulosic biomass to glycolic acid using molybdenum-containing acidic catalysts. The invention includes the use of heteropoly and isopoly acids and salts as the molybdenum-containing multi-functional catalysts for biomass conversion. In embodiments of the invention, the reactions employ successive hydrolysis, retro-aldol fragmentation, and selective oxidation in a noble metal-free system.

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)

Tantalum oxide-based compounds as new non-noble cathodes for polymer electrolyte fuel cell

International Nuclear Information System (INIS)

Ishihara, Akimitsu; Tamura, Motoko; Matsuzawa, Koichi; Mitsushima, Shigenori; Ota, Ken-ichiro

2010-01-01

Tantalum oxide-based compounds were examined as new non-noble cathodes for polymer electrolyte fuel cell. Tantalum carbonitride powder was partially oxidized under a trace amount of oxygen gas at 900 o C for 4 or 8 h. Onset potential for oxygen reduction reaction (ORR) of the specimen heat-treated for 8 h was 0.94 V vs. reversible hydrogen electrode in 0.1 mol dm -3 sulfuric acid at 30 o C. The partial oxidation of tantalum carboniride was effective to enhance the catalytic activity for the ORR. The partially oxidized specimen with highest catalytic activity had ca. 5.25 eV of ionization potential, indicating that there was most suitable strength of the interaction of oxygen and tantalum on the catalyst surface.

Synthesis of self-supported non-precious metal catalysts for oxygen reduction reaction with preserved nanostructures from the polyaniline nanofiber precursor

DEFF Research Database (Denmark)

Hu, Yang; Zhao, Xiao; Huang, Yunjie

2013-01-01

Non-precious metal catalysts (NPMCs) for the oxygen reduction reaction (ORR) are an active subject of recent research on proton exchange membrane fuel cells. In this study, we report a new approach to preparation of self-supported and nano-structured NPMCs using pre-prepared polyaniline (PANI...

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

Single-site catalyst promoters accelerate metal-catalyzed nitroarene hydrogenation

KAUST Repository

Wang, Liang

2018-04-04

Atomically dispersed supported metal catalysts are drawing wide attention because of the opportunities they offer for new catalytic properties combined with efficient use of the metals. We extend this class of materials to catalysts that incorporate atomically dispersed metal atoms as promoters. The catalysts are used for the challenging nitroarene hydrogenation and found to have both high activity and selectivity. The promoters are single-site Sn on TiO2 supports that incorporate metal nanoparticle catalysts. Represented as M/Sn-TiO2 (M = Au, Ru, Pt, Ni), these catalysts decidedly outperform the unpromoted supported metals, even for hydrogenation of nitroarenes substituted with various reducible groups. The high activity and selectivity of these catalysts result from the creation of oxygen vacancies on the TiO2 surface by single-site Sn, which leads to efficient, selective activation of the nitro group coupled with a reaction involving hydrogen atoms activated on metal nanoparticles.

Single-site catalyst promoters accelerate metal-catalyzed nitroarene hydrogenation

KAUST Repository

Wang, Liang; Guan, Erjia; Zhang, Jian; Yang, Junhao; Zhu, Yihan; Han, Yu; Yang, Ming; Cen, Cheng; Fu, Gang; Gates, Bruce C.; Xiao, Feng-Shou

2018-01-01

Atomically dispersed supported metal catalysts are drawing wide attention because of the opportunities they offer for new catalytic properties combined with efficient use of the metals. We extend this class of materials to catalysts that incorporate atomically dispersed metal atoms as promoters. The catalysts are used for the challenging nitroarene hydrogenation and found to have both high activity and selectivity. The promoters are single-site Sn on TiO2 supports that incorporate metal nanoparticle catalysts. Represented as M/Sn-TiO2 (M = Au, Ru, Pt, Ni), these catalysts decidedly outperform the unpromoted supported metals, even for hydrogenation of nitroarenes substituted with various reducible groups. The high activity and selectivity of these catalysts result from the creation of oxygen vacancies on the TiO2 surface by single-site Sn, which leads to efficient, selective activation of the nitro group coupled with a reaction involving hydrogen atoms activated on metal nanoparticles.

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...

Perovskite Catalysts—A Special Issue on Versatile Oxide Catalysts

Directory of Open Access Journals (Sweden)

Yu-Chuan Lin

2014-08-01

Full Text Available Perovskite-type catalysts have been prominent oxide catalysts for many years due to attributes such as flexibility in choosing cations, significant thermal stability, and the unique nature of lattice oxygen. Nearly 90% metallic elements of the Periodic Table can be stabilized in perovskite’s crystalline framework [1]. Moreover, by following the Goldschmidt rule [2], the A- and/or B-site elements can be partially substituted, making perovskites extremely flexible in catalyst design. One successful example is the commercialization of noble metal-incorporated perovskites (e.g., LaFe0.57Co0.38Pd0.05O3 for automotive emission control used by Daihatsu Motor Co. Ltd. [3]. Thus, growing interest in, and application of perovskites in the fields of material sciences, heterogeneous catalysis, and energy storage have prompted this Special Issue on perovskite catalysts. [...

CuNi NPs supported on MIL-101 as highly active catalysts for the hydrolysis of ammonia borane

Science.gov (United States)

Gao, Doudou; Zhang, Yuhong; Zhou, Liqun; Yang, Kunzhou

2018-01-01

The catalysts containing Cu, Ni bi-metallic nanoparticles were successfully synthesized by in-situ reduction of Cu2+ and Ni2+ salts into the highly porous and hydrothermally stable metal-organic framework MIL-101 via a simple liquid impregnation method. When the total amount of loading metal is 3 × 10-4 mol, Cu2Ni1@MIL-101 catalyst shows higher catalytic activity comparing to CuxNiy@MIL-101 with different molar ratio of Cu and Ni (x, y = 0, 0.5, 1.5, 2, 2.5, 3). Cu2Ni1@MIL-101 catalyst has the highest catalytic activity comparing to mono-metallic Cu and Ni counterparts and pure bi-metallic CuNi nanoparticles in hydrolytic dehydrogeneration of ammonia borane (AB) at room temperature. Additionally, in the hydrolysis reaction, the Cu2Ni1@MIL- 101 catalyst possesses excellent catalytic performances, which exhibit highly catalytic activity with turn over frequency (TOF) value of 20.9 mol H2 min-1 Cu mol-1 and a very low activation energy value of 32.2 kJ mol-1. The excellent catalytic activity has been successfully achieved thanks to the strong bi-metallic synergistic effects, uniform distribution of nanoparticles and the bi-functional effects between CuNi nanoparticles and the host of MIL-101. Moreover, the catalyst also displays satisfied durable stability after five cycles for the hydrolytically releasing H2 from AB. The non-noble metal catalysts have broad prospects for commercial applications in the field of hydrogen-stored materials due to the low prices and excellent catalytic activity.

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)

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.

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

Dissolution of Metal Supported Spent Auto Catalysts in Acids

Directory of Open Access Journals (Sweden)

Fornalczyk A.

2016-03-01

Full Text Available Metal supported auto catalysts, have been used in sports and racing cars initially, but nowadays their application systematically increases. In Metal Substrate (supported Converters (MSC, catalytic functions are performed by the Platinum Group Metals (PGM: Pt, Pd, Rh, similarly to the catalysts on ceramic carriers. The contents of these metals make that spent catalytic converters are valuable source of precious metals. All over the world there are many methods for the metals recovery from the ceramic carriers, however, the issue of platinum recovery from metal supported catalysts has not been studied sufficiently yet. The paper presents preliminary results of dissolution of spent automotive catalyst on a metal carrier by means of acids: H2SO4, HCl, HNO3, H3PO4. The main assumption of the research was the dissolution of base metals (Fe, Cr, Al from metallic carrier of catalyst, avoiding dissolution of PGMs. Dissolution was the most effective when concentrated hydrochloric acid, and 2M sulfuric acid (VI was used. It was observed that the dust, remaining after leaching, contained platinum in the level of 0.8% and 0.7%, respectively.

Catalytic wet air oxidation of chlorophenols over supported ruthenium catalysts

International Nuclear Information System (INIS)

Li Ning; Descorme, Claude; Besson, Michele

2007-01-01

A series of noble metal (Pt, Pd, Ru) loaded zirconia catalysts were evaluated in the catalytic wet air oxidation (CWAO) of mono-chlorophenols (2-CP, 3-CP, 4-CP) under relatively mild reaction conditions. Among the investigated noble metals, Ru appeared to be the best to promote the CWAO of CPs as far as incipient-wetness impregnation was used to prepare all the catalysts. The position of the chlorine substitution on the aromatic ring was also shown to have a significant effect on the CP reactivity in the CWAO over 3 wt.% Ru/ZrO 2 . 2-CP was relatively easier to degradate compared to 3-CP and 4-CP. One reason could be the higher adsorption of 2-CP on the catalyst surface. Further investigations suggested that 3 wt.% Ru/ZrO 2 is a very efficient catalyst in the CWAO of 2-CP as far as high 2-CP conversion and TOC abatement could still be reached at even lower temperature (393 K) and lower total pressure (3 MPa). Additionally, the conversion of 2-CP was demonstrated to increase with the initial pH of the 2-CP solution. The dechlorination reaction is promoted at higher pH. In all cases, the adsorption of the reactants and the reaction intermediates was shown to play a major role. All parameters that would control the molecule speciation in solution or the catalyst surface properties would have a key effect

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)

Heterogeneous hydrogenation of unsaturated compounds with catalyst P-2-Ni with turnover numbers up to 90,000

Energy Technology Data Exchange (ETDEWEB)

Strohmeier, W; Pfoehler, M; Steigerwald, H [Wuerzburg Univ. (Germany, F.R.). Inst. fuer Physikalische Chemie

1977-12-01

Unsaturated compounds are very rapidly hydrogenated with nickel-boride catalyst P-2-Ni without solvent under mild conditions (70-85/sup 0/C and 10 bar). Turnover numbers UZ up to 90,000 and space-time-yields of 7.440 mmol product per l and 1 mgA Nickel in one hour with a mean catalyst activity a = 124 were observed. This hydrogenation catalyst has a power, which is in the same magnitude of very active noble metal catalysts.

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.

Fundamentals of Hydrocarbon Upgrading to Liquid Fuels and Commodity Chemicals over Catalytic Metallic Nanoparticles

Science.gov (United States)

Chen, Tao

Promising new technologies for biomass conversion into fuels and chemical feedstocks rely on the production of bio-oils, which need to be upgraded in order to remove oxygen-containing hydrocarbons and water. A high oxygen concentration makes bio-oils acidic and corrosive, unstable during storage, and less energetically valuable per unit weight than petroleum-derived hydrocarbons. Although there are efficient processes for the production of bio-oils, there are no efficient technologies for their upgrading. Current technologies utilize traditional petroleum refining catalysts, which are not optimized for biomass processing. New upgrading technologies are, therefore, urgently needed for development of sustainable energy resources. Development of such new technologies, however, is severely hindered by a lack of fundamental understanding of how oxygen and oxygen-containing hydrocarbons derived from biomass interact with promising noble-metal catalysts. In this study, kinetic reaction measurements, catalyst characterization and quantum chemical calculations using density functional theory were combined for determining adsorption modes and reaction mechanisms of hydrocarbons in the presence of oxygen on surfaces of catalytic noble-metal nanoparticles. The results were used for developing improved catalyst formulations and optimization of reaction conditions. The addition of molybdenum to platinum catalysts was shown to improve catalytic activity, stability, and selectivity in hydrodeoxygenation of acetic acid, which served as a model biomass compound. The fundamental results that describe interactions of oxygen and hydrocarbons with noble-metal catalysts were extended to other reactions and fields of study: evaluation of the reaction mechanism for hydrogen peroxide decomposition, development of improved hydrogenation catalysts and determination of adsorption modes of a spectroscopic probe molecule.

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.

Catalysts for petroleum desulfurization

Energy Technology Data Exchange (ETDEWEB)

Mueller, A.; Diemann, E.; Baumann, F.W.

1988-01-01

In order to obtain marketable products from low-quality oils, efficient hydrogenation processes are required for removing sulfur (hydrodesulfurization, HDS), nitrogen (hydrodenitrification, HDN), and oxygen (hydrodeoxygenation, HDO), which would poison the noble metal catalysts of the downstream petrochemical processes. Hydrogenation will produce low-sulfur, low-nitrogen fuels and thus contribute to the reduction of SO/sub 2/ and NO/sub x/ emissions which is long overdue from the ecological point of view (forest decline, acidification of surface bodies of water, etc.).

Gasification of carbon deposits on catalysts and metal surfaces

Energy Technology Data Exchange (ETDEWEB)

Figueiredo, J L

1986-10-01

'Coke' deposited on catalysts and reactor surfaces includes a variety of carbons of different structures and origins, their reactivities being conveniently assessed by Temperature Programmed Reaction (TPR). The gasification of carbon deposits obtained in the laboratory under well controlled conditions, and the regeneration of coked catalysts from petroleum refining processes are reviewed and discussed. Filamentary carbon deposits, containing dispersed metal particles, behave as supported metal catalysts during gasification, and show high reactivities. Pyrolytic and acid catalysis carbons are less reactive on their own, as the gasification is not catalysed; however, metal components of the catalyst or metal impurities deposited on the surface may enhance gasification. 26 refs., 8 figs., 2 tabs.

Metal-free carbon materials-catalyzed sulfate radical-based advanced oxidation processes: A review on heterogeneous catalysts and applications.

Science.gov (United States)

Zhao, Qingxia; Mao, Qiming; Zhou, Yaoyu; Wei, Jianhong; Liu, Xiaocheng; Yang, Junying; Luo, Lin; Zhang, Jiachao; Chen, Hong; Chen, Hongbo; Tang, Lin

2017-12-01

In recent years, advanced oxidation processes (AOPs), especially sulfate radical based AOPs have been widely used in various fields of wastewater treatment due to their capability and adaptability in decontamination. Recently, metal-free carbon materials catalysts in sulfate radical production has been more and more concerned because these materials have been demonstrated to be promising alternatives to conventional metal-based catalysts, but the review of metal-free catalysts is rare. The present review outlines the current state of knowledge on the generation of sulfate radical using metal-free catalysts including carbon nanotubes, graphene, mesoporous carbon, activated carbon, activated carbon fiber, nanodiamond. The mechanism such as the radical pathway and non-radical pathway, and factors influencing of the activation of sulfate radical was also be revealed. Knowledge gaps and research needs have been identified, which include the perspectives on challenges related to metal-free catalyst, heterogeneous metal-free catalyst/persulfate systems and their potential in practical environmental remediation. Copyright © 2017 Elsevier Ltd. All rights reserved.

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...

Recycling of platinum group metals from the automotive catalysts

International Nuclear Information System (INIS)

Benevit, Mariana; Petter, Patricia Melo Halmenschlager; Veit, Hugo Marcelo

2014-01-01

Currently it is very important to use alternative sources of raw material for obtaining metals, avoiding the traditional mining. This work aims to characterize and evaluate the recoverability of platinum group metals present in automotive catalysts. Thus, the catalysts were divided into two groups: the first was catalysts used in 1.0 cars and the second was catalyst used in 2.0 cars. DRX and FRX techniques and chemical analysis performed by ICP/OES was used to characterized these materials. The results showed that there is a significant amount of platinum group elements in catalyst waste, which can be separated and reused. In the next step, hydro and pyrometallurgical routes, for metals extraction from catalyst waste, will be studied. (author)

Study on the poisoning effect-of non-vanadium catalysts by potassium

Science.gov (United States)

Zeng, Huanmu; Liu, Ying; Yu, Xiaowei; Lin, Yasi

2018-02-01

The poisoning effect of catalyst by alkali metals is one of the problems in the selective catalytic reduction (SCR) of NO by NH3. Serious deactivation by alkali poisoning have been proved to take place in the commercial vanadium catalyst. Recently, non-vanadium catalysts such as copper oxides, manganese oxides, chromium oxides and cerium oxides have attracted special attentions in SCR application. However, their tolerance in the presence of alkali metals is still doubtful. In this paper, copper oxides, manganese oxides, chromium oxides and cerium oxides supported on TiO2 nanoparticle was prepared by impregnating method. Potassium nitrate was chosen as the precursor of poisoner. Catalytic activities of these catalysts were evaluated before and after the addition of potassium. Some characterization methods including X-ray diffraction and temperature programmed desorption was utilized to reveal the main reason of alkali deactivation.

Single-Step Electrophoretic Deposition of Non-noble Metal Catalyst Layer with Low Onset Voltage for Ethanol Electro-oxidation.

Science.gov (United States)

Ahmadi Daryakenari, Ahmad; Hosseini, Davood; Ho, Ya-Lun; Saito, Takumi; Apostoluk, Aleksandra; Müller, Christoph R; Delaunay, Jean-Jacques

2016-06-29

A single-step electrophoretic deposition (EPD) process is used to fabricate catalyst layers which consist of nickel oxide nanoparticles attached on the surface of nanographitic flakes. Magnesium ions present in the colloid charge positively the flake's surface as they attach on it and are also used to bind nanographitic flakes together. The fabricated catalyst layers showed a very low onset voltage (-0.2 V vs Ag/AgCl) in the electro-oxidation of ethanol. To clarify the occurring catalytic mechanism, we performed annealing treatment to produce samples having a different electrochemical behavior with a large onset voltage. Temperature dependence measurements of the layer conductivity pointed toward a charge transport mechanism based on hopping for the nonannealed layers, while the drift transport is observed in the annealed layers. The hopping charge transport is responsible for the appearance of the low onset voltage in ethanol electro-oxidation.

Oxidative coupling of 1-naphthols over noble and base metal catalysts

CSIR Research Space (South Africa)

Maphoru, MV

2014-01-01

Full Text Available Bismuth-promoted platinum catalysts were tested for the oxidative coupling of 2- and 4-substituted 1-naphthols at different temperatures and ambient pressure. The principal final products are the 3,3'-substituted 1,1'-binaphthalenylidene-4,4'-diones...

The synthesis of nanostructured, phase pure catalysts by hydrodynamic cavitation

Energy Technology Data Exchange (ETDEWEB)

Moser, W.R.; Sunstrom, J.E.; Marshik-Geurts, B.J. [Worcester Polytechnic Institute, Worcester, MA (United States)

1995-12-01

A new process for the synthesis of advanced catalytic materials based on performing the synthesis under hydrodynamic cavitation conditions has been discovered. This continuous process for catalyst synthesis resulted in the formation of both supported and unsupported catalysts. The advantage of the process over classical methods of synthesis is that it permits the formation of a wide variety of nanostructured catalysts in exceptionally high phase purities. The synthesis of platinum and palladium catalysts supported on alumina and other supports resulted in high dispersions of the noble metals. The synthesis of alpha, beta- and gamma-bismuth molybdates resulted in catalysts having superior phase purities as compared to several other classical methods of synthesis. The beta-bismuth molybdate was synthesized directly onto Cabosil. These studies showed that the particle size of the active component could be varied from a few manometers to much larger grains. The process enabled the synthesis of other complex metal oxides like perovskites as pure phases. The process uses a commercially available Microfluidizer.

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.

Mechanistic Investigation of the Reduction of NOx over Pt- and Rh-Based LNT Catalysts

Directory of Open Access Journals (Sweden)

Lukasz Kubiak

2016-03-01

Full Text Available The influence of the noble metals (Pt vs. Rh on the NOx storage reduction performances of lean NOx trap catalysts is here investigated by transient micro-reactor flow experiments. The study indicates a different behavior during the storage in that the Rh-based catalyst showed higher storage capacity at high temperature as compared to the Pt-containing sample, while the opposite is seen at low temperatures. It is suggested that the higher storage capacity of the Rh-containing sample at high temperature is related to the higher dispersion of Rh as compared to Pt, while the lower storage capacity of Rh-Ba/Al2O3 at low temperature is related to its poor oxidizing properties. The noble metals also affect the catalyst behavior upon reduction of the stored NOx, by decreasing the threshold temperature for the reduction of the stored NOx. The Pt-based catalyst promotes the reduction of the adsorbed NOx at lower temperatures if compared to the Rh-containing sample, due to its superior reducibility. However, Rh-based material shows higher reactivity in the NH3 decomposition significantly enhancing N2 selectivity. Moreover, formation of small amounts of N2O is observed on both Pt- and Rh-based catalyst samples only during the reduction of highly reactive NOx stored at 150 °C, where NOx is likely in the form of nitrites.

Enhanced performance and durability of low catalyst loading PEM water electrolyser based on a short-side chain perfluorosulfonic ionomer

International Nuclear Information System (INIS)

Siracusano, Stefania; Baglio, Vincenzo; Van Dijk, Nicholas; Merlo, Luca; Aricò, Antonino Salvatore

2017-01-01

Graphical abstract: Tripling current density (>3 A·cm"−"2) with respect to the state of the art of commercial PEM electrolyser can be achieved also in the presence of a significant reduction, about 4-fold, of the total noble metal loading (0.5 mg·cm"−"2) while achieving high efficiency (>80%) and proper durability. - Highlights: • Current density >3 A·cm"−"2 is achieved in electrolysis cells with efficiency >80%. • A 4-fold reduction of noble metal loading is demonstrated in electrolysis cells. • Degradation rate <5 μV/h is achieved in a 1000 h durability test at 1 A·cm"−"2. • Degradation associated to a change in Lewis acidity characteristics is observed. - Abstract: Water electrolysis supplied by renewable energy is the foremost technology for producing “green” hydrogen for fuel cell vehicles. In addition, the ability to rapidly follow an intermittent load makes electrolysis an ideal solution for grid-balancing caused by differences in supply and demand for energy generation and consumption. Membrane-electrode assemblies (MEAs) designed for polymer electrolyte membrane (PEM) water electrolysis, based on a novel short-side chain (SSC) perfluorosulfonic acid (PFSA) membrane, Aquivion®, with various cathode and anode noble metal loadings, were investigated in terms of both performance and durability. Utilizing a nanosized Ir_0_._7Ru_0_._3O_x solid solution anode catalyst and a supported Pt/C cathode catalyst, in combination with the Aquivion® membrane, gave excellent electrolysis performances exceeding 3.2 A·cm"−"2 at 1.8 V terminal cell voltage (∼80% efficiency) at 90 °C in the presence of a total catalyst loading of 1.6 mg⋅cm"−"2. A very small loss of efficiency, corresponding to 30 mV voltage increase, was recorded at 3 A⋅cm"−"2 using a total noble metal catalyst loading of less than 0.5 mg·cm"−"2 (compared to the industry standard of 2 mg·cm"−"2). Steady-state durability tests, carried out for 1000 h at 1 A�

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

Combinatorial discovery of new methanol-tolerant non-noble metal cathode electrocatalysts for direct methanol fuel cells.

Science.gov (United States)

Yu, Jong-Sung; Kim, Min-Sik; Kim, Jung Ho

2010-12-14

Combinatorial synthesis and screening were used to identify methanol-tolerant non-platinum cathode electrocatalysts for use in direct methanol fuel cells (DMFCs). Oxygen reduction consumes protons at the surface of DMFC cathode catalysts. In combinatorial screening, this pH change allows one to differentiate active catalysts using fluorescent acid-base indicators. Combinatorial libraries of carbon-supported catalyst compositions containing Ru, Mo, W, Sn, and Se were screened. Ternary and quaternary compositions containing Ru, Sn, Mo, Se were more active than the "standard" Alonso-Vante catalyst, Ru(3)Mo(0.08)Se(2), when tested in liquid-feed DMFCs. Physical characterization of the most active catalysts by powder X-ray diffraction, gas adsorption, and X-ray photoelectron spectroscopy revealed that the predominant crystalline phase was hexagonal close-packed (hcp) ruthenium, and showed a surface mostly covered with oxide. The best new catalyst, Ru(7.0)Sn(1.0)Se(1.0), was significantly more active than Ru(3)Se(2)Mo(0.08), even though the latter contained smaller particles.

Superior mercury-free catalysts for acetylene hydrochlorination to VCM. Achieving high productivities and long catalyst life-time

Energy Technology Data Exchange (ETDEWEB)

Liebens, A.T.; Piccinini, M. [Solvay S.A., Bruxelles (Belgium)

2013-11-01

New mercury-free catalytic systems based on the use of ionic liquids (IL) and noble metals (e.g. Pd, Au) have been evaluated for the hydrochlorination reaction of acetylene to produce Vinyl Chloride Monomer (VCM). Two different approaches have been investigated: gas-liquid homogeneous catalytic systems in the presence of molten IL/Metal and heterogeneous gas-solid ones using solid materials. For the latter case, very positive results have been obtained using SILP-type catalysts (SILP: Supported Ionic Liquid Phase) where IL/Metal were deposited onto a solid mesoporous support. Remarkably, both systems display very high Space Time Yield (STY) and breakthrough life-time stability. No deactivation is observed even after 500 h on stream indicating the strong advantages of these new materials compared to most investigated Au/C supported systems. The development of heterogeneous catalysts was preferred as the scale-up of gas-liquid technology implies important CAPEX investments to convert current plants from gas-solid to gas-liquid equipment. (orig.)

Microwave-Assisted Conversion of Levulinic Acid to γ-Valerolactone Using Low-Loaded Supported Iron Oxide Nanoparticles on Porous Silicates

Directory of Open Access Journals (Sweden)

Alfonso Yepez

2015-09-01

Full Text Available The microwave-assisted conversion of levulinic acid (LA has been studied using low-loaded supported Fe-based catalysts on porous silicates. A very simple, productive, and highly reproducible continuous flow method has been used for the homogeneous deposition of metal oxide nanoparticles on the silicate supports. Formic acid was used as a hydrogen donating agent for the hydrogenation of LA to effectively replace high pressure H2 mostly reported for LA conversion. Moderate LA conversion was achieved in the case of non-noble metal-based iron oxide catalysts, with a significant potential for further improvements to compete with noble metal-based catalysts.

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)

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

Oxidation Catalysts for Elemental Mercury in Flue Gases—A Review

Directory of Open Access Journals (Sweden)

Liliana Lazar

2012-02-01

Full Text Available The removal of mercury from flue gases in scrubbers is greatly facilitated if the mercury is present as water-soluble oxidized species. Therefore, increased mercury oxidation upstream of scrubber devices will improve overall mercury removal. For this purpose heterogeneous catalysts have recently attracted a great deal of interest. Selective catalytic reduction (SCR, noble metal and transition metal oxide based catalysts have been investigated at both the laboratory and plant scale with this objective. A review article published in 2006 covers the progress in the elemental mercury (Hgel catalytic oxidation area. This paper brings the review in this area up to date. To this end, 110 papers including several reports and patents are reviewed. For each type of catalyst the possible mechanisms as well as the effect of flue gas components on activity and stability are examined. Advantages and main problems are analyzed. The possible future directions of catalyst development in this environmental research area are outlined.

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

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

Catalytic properties of graphene–metal nanoparticle hybrid prepared using an aromatic amino acid as the reducing agent

International Nuclear Information System (INIS)

Adhikari, Bimalendu; Banerjee, Arindam

2013-01-01

An easy and single step process of making reduced graphene oxide nanosheet from graphene oxide (GO) in water medium has been demonstrated by using a naturally occurring non-proteinaceous amino acid (2,4-dihydroxy phenyl alanine, Dopa) as a new reducing agent and stabilizing agent. This amino acid has also been used to reduce the noble metal salt (AuCl 3 /AgNO 3 ) to produce the corresponding noble metal nanoparticles (MNP) without using any external reducing and stabilizing agents. So, this amino acid has been used to reduce simultaneously GO to RGO and noble metal salts to produce corresponding MNP to form RGO–MNP nanohybrid system in a single step in water medium and also in absence of any external toxic reducing and stabilizing agents. Different techniques UV–Visible absorption spectroscopy, X-ray diffraction, transmission electron microscopy, atomic force microscopy and others have been used to characterize the reduction of GO to RGO, metal salts to produce corresponding MNPs and the formation of RGO–MNP nanohybrid systems. Moreover, this metal nanoparticle containing RGO–MNP nanohybrid system acts as a potential catalyst for the reduction of aromatic nitro to aromatic amino group. - Graphical abstract: This study demonstrates an easy, single step and eco-friendly method to make RGO and Au/AgNP simultaneously from respective precursors to form a RGO–Au/AgNP nanohybrid system using an aromatic amino acid (2,4-dihydroxy phenyl alanine, Dopa) as a new reducing agent as well as stabilizing agent in water medium. Highlights: ► Synthesis of reduced graphene oxide (RGO) nanosheet using an amino acid. ► The amino acid (Dopa) can reduce noble metal salt (Au 3+ /Ag + ) to metal nanoparticle (MNP). ► Single step and eco-friendly synthesis of RGO-MNP nanohybrid using Dopa. ► Characterization of RGO, MNP and RGO–MNP nanohybrid. ► RGO-MNP nanohybrid acts as a catalyst for the reduction of aromatic nitro

Metal Phosphate-Supported Pt Catalysts for CO Oxidation

Directory of Open Access Journals (Sweden)

Xiaoshuang Qian

2014-12-01

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

Metal nanoparticles as a conductive catalyst

Science.gov (United States)

Coker, Eric N [Albuquerque, NM

2010-08-03

A metal nanocluster composite material for use as a conductive catalyst. The metal nanocluster composite material has metal nanoclusters on a carbon substrate formed within a porous zeolitic material, forming stable metal nanoclusters with a size distribution between 0.6-10 nm and, more particularly, nanoclusters with a size distribution in a range as low as 0.6-0.9 nm.

Stability of Transition-metal Carbides in Liquid Phase Reactions Relevant for Biomass-Based Conversion

NARCIS (Netherlands)

Souza Macêdo, L.; Stellwagen, D.R.; Teixeira da Silva, V.; Bitter, J.H.

2015-01-01

Transition-metal carbides have been employed for biobased conversions aiming to replace the rare noble metals. However, when reactions are in liquid phase, many authors have observed catalyst deactivation. The main routes of deactivation in liquid phase biobased conversions are coke deposition,

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

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

Automotive catalyst strategies for future emission systems

International Nuclear Information System (INIS)

Williamson, W.B.; Summers, J.C.; Scaparo, J.A.

1992-01-01

This paper reports that while significant advances in Pt/Rh three-way catalyst (TWC) formulations have been accomplished, the use of Pd-containing catalysts for three-way emission control are of interest for overall noble metal cost reduction, lower Rh usage, and potential durability improvements. Applications of Pd are demonstrated for replacement of Pt in conventional Pt/Rh TWC systems, for use in Pd-only three-way catalysts and for lowering methanol and formaldehyde emissions at close-coupled locations on a methanol-fueled vehicle. The individual contributions of Pt, Pd and Rh for aged three-way performance indicate significant advantages of using Pd over Pt. A comparison of vehicle system control strategies illustrates that higher system temperatures significantly lower HC emissions, while air/fuel control strategies are most critical in lowering NO x emissions

Electrochemical dopamine sensor based on P-doped graphene: Highly active metal-free catalyst and metal catalyst support.

Science.gov (United States)

Chu, Ke; Wang, Fan; Zhao, Xiao-Lin; Wang, Xin-Wei; Tian, Ye

2017-12-01

Heteroatom doping is an effective strategy to enhance the catalytic activity of graphene and its hybrid materials. Despite a growing interest of P-doped graphene (P-G) in energy storage/generation applications, P-G has rarely been investigated for electrochemical sensing. Herein, we reported the employment of P-G as both metal-free catalyst and metal catalyst support for electrochemical detection of dopamine (DA). As a metal-free catalyst, P-G exhibited prominent DA sensing performances due to the important role of P doping in improving the electrocatalytic activity of graphene toward DA oxidation. Furthermore, P-G could be an efficient supporting material for loading Au nanoparticles, and resulting Au/P-G hybrid showed a dramatically enhanced electrocatalytic activity and extraordinary sensing performances with a wide linear range of 0.1-180μM and a low detection limit of 0.002μM. All these results demonstrated that P-G might be a very promising electrode material for electrochemical sensor applications. Copyright © 2017 Elsevier B.V. All rights reserved.

Metal porphyrin intercalated reduced graphene oxide nanocomposite utilized for electrocatalytic oxygen reduction

Directory of Open Access Journals (Sweden)

Mingyan Wang

2017-07-01

Full Text Available In this paper, we report a simple and facile self-assembly method to successfully fabricate cationic metal porphyrin –MtTMPyP (Mt= Cobalt (II, Manganese (III, or Iron (III; TMPyP = 5, 10, 15, 20-tetrakis (N-methylpyridinium-4-yl porphyrin intercalated into the layer of graphene oxide (GO by the cooperative effects of electrostatic and π–π stacking interaction between positively charged metal porphyrin and negatively charged GO sheets. Followed by reduction with hydrazine vapor, a series of novel 2D MtTMPyP/rGOn were fabricated. The as-prepared 2D hybrids were fully characterized and tested as non-noble metal catalysts for oxygen reduction reaction (ORR in an alkaline medium. The MtTMPyP/rGOn hybrids, especially CoTMPyP/rGO5, demonstrated an improved electrocatalytic activity for ORR and a number of exchanged electrons close to 4-electron reaction, increased stability and excellent tolerance to methanol, showing a potential alternative catalyst for ORR in fuel cells and air batteries. Keywords: Metal porphyrin, Reduced graphene oxide, Intercalation, Oxygen reduction reaction, Catalyst

Hydrodeoxygenation of mono- and dimeric lignin model compounds on noble metal catalysts

NARCIS (Netherlands)

Guvenatam, Burcu; Kursun, Osman; Heeres, Hero; Pidko, Evgeny A.; Hensen, Emiel J. M.

2014-01-01

The influence of reaction conditions (temperature, acidity) on the catalytic performance of supported Pt, Pd and Ru catalysts for the aqueous phase hydrodeoxygenation (HDO) of lignin model compounds was systematically investigated. Phenol conversion proceeds via hydrogenation of the aromatic ring

Antipollution processing of a used refining catalyst and metal recovery

Energy Technology Data Exchange (ETDEWEB)

Trinh Dinh Chan; Llido, E.

1992-04-30

The used catalyst, containing metals such as vanadium, nickel and iron, is unloaded from the plant and is first processed by stripping; it is then calcined in critical conditions, and the catalyst metals are leached with a sodium hydroxide or sodium carbonate aqueous solution. The antipollution process can be applied to oil fraction hydroconversion or hydroprocessing catalysts.

Carbide-forming groups IVB-VIB metals: a new territory in the periodic table for CVD growth of graphene.

Science.gov (United States)

Zou, Zhiyu; Fu, Lei; Song, Xiuju; Zhang, Yanfeng; Liu, Zhongfan

2014-07-09

Early transition metals, especially groups IVB-VIB metals, can form stable carbides, which are known to exhibit excellent "noble-metal-like" catalytic activities. We demonstrate herein the applications of groups IVB-VIB metals in graphene growth using atmospheric pressure chemical vapor deposition technique. Similar to the extensively studied Cu, Ni, and noble metals, these transition-metal foils facilitate the catalytic growth of single- to few-layer graphene. The most attractive advantage over the existing catalysts is their perfect control of layer thickness and uniformity with highly flexible experimental conditions by in situ converting the dissolved carbons into stable carbides to fully suppress the upward segregation/precipitation effect. The growth performance of graphene on these transition metals can be well explained by the periodic physicochemical properties of elements. Our work has disclosed a new territory of catalysts in the periodic table for graphene growth and is expected to trigger more interest in graphene research.

Synthesis, Characterizations, and Applications of Metal-Ions Incorporated High Quality MCM-41 Catalysts

International Nuclear Information System (INIS)

Lim, Steven S.; Haller, Gary L.

2013-01-01

Various metal ions (transition and base metals) incorporated MCM-41 catalysts can be synthesized using colloidal and soluble silica with non-sodium involved process. Transition metal ion-typically V 5+ , Co 2+ , and Ni 2+ -incorporated MCM-41 catalysts were synthesized by isomorphous substitution of Si ions in the framework. Each incorporated metal ion created a single species in the silica framework, single-site solid catalyst, showing a substantial stability in reduction and catalytic activity. Radius of pore curvature effect was investigated with Co-MCM-41 by temperature programmed reduction (TPR). The size of metallic Co clusters, sub-nanometer, could be controlled by a proper reduction treatment of Co-MCM-41 having different pore size and the initial pH adjustment of the Co-MCM-41 synthesis solution. These small metallic clusters showed a high stability under a harsh reaction condition without serious migration, resulting from a direct anchoring of small metallic clusters to the partially or unreduced metal ions on the surface. After a complete reduction, partial occlusion of the metallic cluster surface by amorphous silica stabilized the particles against aggregations. As a probe reaction of particle size sensitivity, carbon single wall nanotubes (SWNT) were synthesized using Co-MCM-41. A metallic cluster stability test was performed by CO methanation using Co- and Ni-MCM-41. Methanol and methane partial oxidations were carried out with V-MCM-41, and the radius of pore curvature effect on the catalytic activity was investigated

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.

Heteroatom-Doped Carbon Materials for Electrocatalysis.

Science.gov (United States)

Asefa, Tewodros; Huang, Xiaoxi

2017-08-10

Fuel cells, water electrolyzers, and metal-air batteries are important energy systems that have started to play some roles in our renewable energy landscapes. However, despite much research works carried out on them, they have not yet found large-scale applications, mainly due to the unavailability of sustainable catalysts that can catalyze the reactions employed in them. Currently, noble metal-based materials are the ones that are commonly used as catalysts in most commercial fuel cells, electrolyzers, and metal-air batteries. Hence, there has been considerable research efforts worldwide to find alternative noble metal-free and metal-free catalysts composed of inexpensive, earth-abundant elements for use in the catalytic reactions employed in these energy systems. In this concept paper, a brief introduction on catalysis in renewable energy systems, followed by the recent efforts to develop sustainable, heteroatom-doped carbon and non-noble metal-based electrocatalysts, the challenges to unravel their structure-catalytic activity relationships, and the authors' perspectives on these topics and materials, are discussed. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Recent Development of Catalysts for Removal of Volatile Organic Compounds in Flue Gas by Combustion: A Review

Directory of Open Access Journals (Sweden)

Marco Tomatis

2016-01-01

Full Text Available Volatile organic compounds (VOCs emitted from anthropogenic sources pose direct and indirect hazards to both atmospheric environment and human health due to their contribution to the formation of photochemical smog and potential toxicity including carcinogenicity. Therefore, to abate VOCs emission, the catalytic oxidation process has been extensively studied in laboratories and widely applied in various industries. This report is mainly focused on the benzene, toluene, ethylbenzene, and xylene (BTEX with additional discussion about chlorinated VOCs. This review covers the recent developments in catalytic combustion of VOCs over noble metal catalysts, nonnoble metal catalysts, perovskite catalysts, spinel catalysts, and dual functional adsorbent-catalysts. In addition, the effects of supports, coke formation, and water effects have also been discussed. To develop efficient and cost-effective catalysts for VOCs removal, further research in catalytic oxidation might need to be carried out to strengthen the understanding of catalytic mechanisms involved.

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....

Production of perovskite catalysts on ceramic monoliths with nanoparticles for dual fuel system automobiles

International Nuclear Information System (INIS)

Khanfekr, A.; Arzani, K.; Nemati, A.; Hosseini, M.

2009-01-01

(Lanthanum, Cerium)(Iron, Manganese, Cobalt, Palladium)(Oxygen) 3 ,-Perovskite catalyst was prepared by the citrate route and deposited on ceramic monoliths via dip coating procedure. The catalyst was applied on a car with X U 7 motors and the amount of emission was monitored with vehicle emission test systems in Sapco company. The results were compared with the imported catalyst with noble metals such as Palladium, Platinum and Rhodium by Iran Khodro company based on the Euro III standards. The catalysts were characterized by specific surface area measurements, scanning electron microscopy, X-ray diffraction, line scan and map. In the results, obtained in the home made sample, the amount of carbon monoxide, nitrogen oxides and hydrocarbons were lower than imported catalyst with Iran Khodro company with nobel metals. The illustration shows nano particles size on coat. The microstructure evaluation showed that the improved properties can be related to the existence of nano particles on coating

Palladium Loaded on Magnetic Nanoparticles as Efficient and Recyclable Catalyst for the Suzuki- Miyaura Reaction

Directory of Open Access Journals (Sweden)

H. Khojasteh

2015-07-01

Full Text Available Palladium is the best metal catalyst for Suzuki cross coupling reaction for synthesize of unsymmetrical biaryl compounds. But its high cost limits its application in wide scale. Using of nanoscale particles as active catalytic cites is a good approach for reducing needed noble metal. By loading precious nanoparticles on magnetic nanocores as a support, recycling and reusing of catalyst will be possible. Magnetic nanoparticles have super paramagnetic feature and applying an external magnetic field can collect the supported catalyst from reaction milieu simply. In this work new palladium catalyst immobilized on modified magnetic nanoparticles containing NNO donor atoms were synthesized. Then the catalyst characterized by FT-IR spectroscopy, thermogravimetric analysis, X-ray diffraction and ICP. Prepared catalyst showed high activity in the Suzuki– Miyaura cross-coupling reaction of phenylboronic acid with aryl halides. Activity, Pd loading, reusability and Pd leaching of catalyst were studied. Results showed that the supported catalyst has the advantage to be completely recoverable with the simple application of an external magnetic field.

Pt/SnO2-based CO-oxidation catalysts for long-life closed-cycle CO2 lasers

Science.gov (United States)

Schryer, David R.; Upchurch, Billy T.; Hess, Robert V.; Wood, George M.; Sidney, Barry D.; Miller, Irvin M.; Brown, Kenneth G.; Vannorman, John D.; Schryer, Jacqueline; Brown, David R.

1990-01-01

Noble-metal/tin-oxide based catalysts such as Pt/SnO2 have been shown to be good catalysts for the efficient oxidation of CO at or near room temperature. These catalysts require a reductive pretreatment and traces of hydrogen or water to exhibit their full activity. Addition of Palladium enhances the activity of these catalysts with about 15 to 20 percent Pt, 4 percent Pd, and the balance SnO2 being an optimum composition. Unfortunately, these catalysts presently exhibit significant decay due in part to CO2 retention, probably as a bicarbonate. Research on minimizing the decay in activity of these catalysts is currently in progress. A proposed mechanism of CO oxidation on Pt/SnO2-based catalysts has been developed and is discussed.

An improved method of preparation of nanoparticular metal oxide catalysts

DEFF Research Database (Denmark)

2014-01-01

The present invention concerns an improved method of preparation of nanoparticular vanadium oxide/anatase titania catalysts having a narrow particle size distribution. In particular, the invention concerns preparation of nanoparticular vanadium oxide/anatase titania catalyst precursors comprising...... combustible crystallization seeds upon which the catalyst metal oxide is coprecipitated with the carrier metal oxide, which crystallization seeds are removed by combustion in a final calcining step....

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.

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

Study of (La, Ce)(Pd, Mn, Fe, Co) O3-Perovskite catalysts characterization with nanoparticles produced by compressor and vacuum until 20/000 km and comparison with imported catalyst of Iran Khodro

International Nuclear Information System (INIS)

Khanfekr, A.; Arzani, K.; Nemati, A.; Hossaini, M.

2009-01-01

(La,Ce)(Pd,Mn,Fe,Co)O 3 - Perovskite catalyst was prepared by the citrate route and deposited on ceramic monoliths via dip coating procedure by compressor and vacuum method. The catalyst was applied on Rd car with XU7 motors model and the amount of emission was monitored with vehicle emission test systems in Sapco Company after 10000 and 20/000 Km. The results indicate low emission in catalyst with vacuum method and were compared with the imported catalyst with noble metals such as Palladium, Platinum and Rhodium by Iran Khodro Company b ased on the Euro III standards . The catalysts were characterized by specific surface area measurements, scanning electron microscopy, X-ray diffraction, line scan and map. In the results indicated in the home made sample, the amount of carbon monoxide, nitrogen oxides and hydrocarbons were lower than imported catalyst with Iran Khodro company with nobel metals. The illustration shows Nano Particles size on coat. The microstructure evaluation showed that the improved properties can he related to the existence of nano particles on coating.

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.

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.

Molecular metal catalysts on supports: organometallic chemistry meets surface science.

Science.gov (United States)

Serna, Pedro; Gates, Bruce C

2014-08-19

Recent advances in the synthesis and characterization of small, essentially molecular metal complexes and metal clusters on support surfaces have brought new insights to catalysis and point the way to systematic catalyst design. We summarize recent work unraveling effects of key design variables of site-isolated catalysts: the metal, metal nuclearity, support, and other ligands on the metals, also considering catalysts with separate, complementary functions on supports. The catalysts were synthesized with the goal of structural simplicity and uniformity to facilitate incisive characterization. Thus, they are essentially molecular species bonded to porous supports chosen for their high degree of uniformity; the supports are crystalline aluminosilicates (zeolites) and MgO. The catalytic species are synthesized in reactions of organometallic precursors with the support surfaces; the precursors include M(L)2(acetylacetonate)1-2, with M = Ru, Rh, Ir, or Au and the ligands L = C2H4, CO, or CH3. Os3(CO)12 and Ir4(CO)12 are used as precursors of supported metal clusters, and some such catalysts are made by ship-in-a-bottle syntheses to trap the clusters in zeolite cages. The simplicity and uniformity of the supported catalysts facilitate precise structure determinations, even in reactive atmospheres and during catalysis. The methods of characterizing catalysts in reactive atmospheres include infrared (IR), extended X-ray absorption fine structure (EXAFS), X-ray absorption near edge structure (XANES), and nuclear magnetic resonance (NMR) spectroscopies, and complementary methods include density functional theory and atomic-resolution aberration-corrected scanning transmission electron microscopy for imaging of individual metal atoms. IR, NMR, XANES, and microscopy data demonstrate the high degrees of uniformity of well-prepared supported species. The characterizations determine the compositions of surface metal complexes and clusters, including the ligands and the metal

Metal leaching from refinery waste hydroprocessing catalyst.

Science.gov (United States)

Marafi, Meena; Rana, Mohan S

2018-05-18

The present study aims to develop an eco-friendly methodology for the recovery of nickel (Ni), molybdenum (Mo), and vanadium (V) from the refinery waste spent hydroprocessing catalyst. The proposed process has two stages: the first stage is to separate alumina, while the second stage involves the separation of metal compounds. The effectiveness of leaching agents, such as NH 4 OH, (NH 4 ) 2 CO 3 , and (NH 4 ) 2 S 2 O 8 , for the extraction of Mo, V, Ni, and Al from the refinery spent catalyst has been reported as a function of reagent concentration (0.5 to 2.0 molar), leaching time (1 to 6 h), and temperature (35 to 60°C). The optimal leaching conditions were achieved to obtain the maximum recovery of Mo, Ni, and V metals. The effect of the mixture of multi-ammonium salts on the metal extraction was also studied, which showed an adverse effect for Ni and V, while marginal improvement was observed for Mo leaching. The ammonium salts can form soluble metal complexes, in which stability or solubility depends on the nature of ammonium salt and the reaction conditions. The extracted metals and support can be reused to synthesize a fresh hydroprocessing catalyst. The process will reduce the refinery waste and recover the expensive metals. Therefore, the process is not only important from an environmental point of view but also vital from an economic perspective.

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

Non-PGM cell catalysts

Energy Technology Data Exchange (ETDEWEB)

Colon-Mercado, H. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Elvington, M. [Savannah River Consulting, Aiken, SC (United States); Ganesan, P. [Savannah River Consulting, Aiken, SC (United States)

2017-09-27

A unique approach has been developed to probe the non-PGM catalyst active site for the Oxygen Reduction Reaction (ORR) for PEMFCs. Iron based functionalities have been engineered into a variety of catalysts to evaluate their impact on activity for the ORR. A series of high surface area catalysts were synthesized and the impact of the chemical structure on the electrochemical and electrocatalytic properties was investigated. Elemental and surface analyses of the prepared catalysts reveal the incorporation of iron in a targeted and controlled manner. A high surface area framework catalyst was prepared that shows exceptional activity, comparable to state-of-the-art materials. The results of this research project provided critical seed data for the newly awarded ElectroCat project, which focuses on rationally designed framework catalysts for the oxygen reduction reaction.

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

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.

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)

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)

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)

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.

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.

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.

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.

The recent development of efficient Earth-abundant transition-metal nanocatalysts.

Science.gov (United States)

Wang, Dong; Astruc, Didier

2017-02-06

Whereas noble metal compounds have long been central in catalysis, Earth-abundant metal-based catalysts have in the same time remained undeveloped. Yet the efficacy of Earth-abundant metal catalysts was already shown at the very beginning of the 20th century with the Fe-catalyzed Haber-Bosch process of ammonia synthesis and later in the Fischer-Tropsch reaction. Nanoscience has revolutionized the world of catalysis since it was observed that very small Au nanoparticles (NPs) and other noble metal NPs are extraordinarily efficient. Therefore the development of Earth-abundant metals NPs is more recent, but it has appeared necessary due to their "greenness". This review highlights catalysis by NPs of Earth-abundant transition metals that include Mn, Fe, Co, Ni, Cu, early transition metals (Ti, V, Cr, Zr, Nb and W) and their nanocomposites with emphasis on basic principles and literature reported during the last 5 years. A very large spectrum of catalytic reactions has been successfully disclosed, and catalysis has been examined for each metal starting with zero-valent metal NPs followed by oxides and other nanocomposites. The last section highlights the catalytic activities of bi- and trimetallic NPs. Indeed this later family is very promising and simultaneously benefits from increased stability, efficiency and selectivity, compared to monometallic NPs, due to synergistic substrate activation.

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.

Allotropic Carbon Nanoforms as Advanced Metal-Free Catalysts or as Supports

Directory of Open Access Journals (Sweden)

Hermenegildo Garcia

2014-01-01

Full Text Available This perspective paper summarizes the use of three nanostructured carbon allotropes as metal-free catalysts (“carbocatalysts” or as supports of metal nanoparticles. After an introductory section commenting the interest of developing metal-free catalysts and main features of carbon nanoforms, the main body of this paper is focused on exemplifying the opportunities that carbon nanotubes, graphene, and diamond nanoparticles offer to develop advanced catalysts having active sites based on carbon in the absence of transition metals or as large area supports with special morphology and unique properties. The final section provides my personal view on future developments in this field.

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.

Polymer Catalysts Imprinted with Metal Ions as Biomimics of Metalloenzymes

Directory of Open Access Journals (Sweden)

Joanna Czulak

2013-01-01

Full Text Available This work presents the preparation and properties of molecularly imprinted polymers (MIPs with catalytic centers that mimic the active sites of metalloenzymes. The MIP synthesis was based on suspension polymerization of functional monomers (4-vinylpyridine and acrylonitrile with trimethylolpropane trimethacrylate as a crosslinker in the presence of transition metal ions and 4-methoxybenzyl alcohol as a template. Four metal ions have been chosen for imprinting from among the microelements that are the most essential in the native enzymes: Cu2+, Co2+, Mn2+, and Zn2+. To prepare catalysts, the required loading of metal ions was obtained during sorption process. The catalysts imprinted with Cu2+, Co2+, and Zn2+ were successfully used for hydroquinone oxidation in the presence of hydrogen peroxide. The Mn2+-imprinted catalyst showed no activity due to the insufficient metal loading. Cu2+ MIP showed the highest efficiency. In case of Cu- and Co-MIP catalysts, their activity was additionally increased by the use of surface imprinting technique.

Solid, double-metal cyanide catalysts for synthesis of ...

Indian Academy of Sciences (India)

Sci. Vol. 126, No. 2, March 2014, pp. 499–509. c Indian Academy of Sciences. Solid, double-metal cyanide catalysts for ... drimers, HPs have a highly branched structural design ... geneous catalysts and corrosion of the reactor lin- ... Carbon dioxide is a greenhouse gas. .... polymer product was reprecipitated from the liquid.

Dispersed metal cluster catalysts by design. Synthesis, characterization, structure, and performance

Energy Technology Data Exchange (ETDEWEB)

Arslan, Ilke [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Dixon, David A. [Univ. of Alabama, Tuscaloosa, AL (United States); Gates, Bruce C. [Univ. of California, Davis, CA (United States); Katz, Alexander [Univ. of California, Berkeley, CA (United States)

2015-09-30

To understand the class of metal cluster catalysts better and to lay a foundation for the prediction of properties leading to improved catalysts, we have synthesized metal catalysts with well-defined structures and varied the cluster structures and compositions systematically—including the ligands bonded to the metals. These ligands include supports and bulky organics that are being tuned to control both the electron transfer to or from the metal and the accessibility of reactants to influence catalytic properties. We have developed novel syntheses to prepare these well-defined catalysts with atomic-scale control the environment by choice and placement of ligands and applied state-of-the art spectroscopic, microscopic, and computational methods to determine their structures, reactivities, and catalytic properties. The ligands range from nearly flat MgO surfaces to enveloping zeolites to bulky calixarenes to provide controlled coverages of the metal clusters, while also enforcing unprecedented degrees of coordinative unsaturation at the metal site—thereby facilitating bonding and catalysis events at exposed metal atoms. With this wide range of ligand properties and our arsenal of characterization tools, we worked to achieve a deep, fundamental understanding of how to synthesize robust supported and ligand-modified metal clusters with controlled catalytic properties, thereby bridging the gap between active site structure and function in unsupported and supported metal catalysts. We used methods of organometallic and inorganic chemistry combined with surface chemistry for the precise synthesis of metal clusters and nanoparticles, characterizing them at various stages of preparation and under various conditions (including catalytic reaction conditions) and determining their structures and reactivities and how their catalytic properties depend on their compositions and structures. Key characterization methods included IR, NMR, and EXAFS spectroscopies to identify

First-row transition metal hydrogenation and hydrosilylation catalysts

Science.gov (United States)

Trovitch, Ryan J.; Mukhopadhyay, Tufan K.; Pal, Raja; Levin, Hagit Ben-Daat; Porter, Tyler M.; Ghosh, Chandrani

2017-07-18

Transition metal compounds, and specifically transition metal compounds having a tetradentate and/or pentadentate supporting ligand are described, together with methods for the preparation thereof and the use of such compounds as hydrogenation and/or hydrosilylation catalysts.

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.

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

New catalysts for coal processing: Metal carbides and nitrides

Energy Technology Data Exchange (ETDEWEB)

S. Ted Oyama; David F. Cox

1999-12-03

The subject of this research project was to investigate the catalytic properties of a new class of materials, transition metal carbides and nitrides, for treatment of coal liquid and petroleum feedstocks. The main objectives were: (1) preparation of catalysts in unsupported and supported form; (2) characterization of the materials; (3) evaluation of their catalytic properties in HDS and HDN; (4) measurement of the surface properties; and (5) observation of adsorbed species. All of the objectives were substantially carried out and the results will be described in detail below. The catalysts were transition metal carbides and nitrides spanning Groups 4--6 in the Periodic Table. They were chosen for study because initial work had shown they were promising materials for hydrotreating. The basic strategy was first to prepare the materials in unsupported form to identify the most promising catalyst, and then to synthesize a supported form of the material. Already work had been carried out on the synthesis of the Group VI compounds Mo{sub 2}C, Mo{sub 2}N, and WC, and new methods were developed for the Group V compounds VC and NbC. All the catalysts were then evaluated in a hydrotreating test at realistic conditions. It was found that the most active catalyst was Mo{sub 2}C, and further investigations of the material were carried out in supported form. A new technique was employed for the study of the bulk and surface properties of the catalysts, near edge x-ray absorption spectroscopy (NEXAFS), that fingerprinted the electronic structure of the materials. Finally, two new research direction were explored. Bimetallic alloys formed between two transition metals were prepared, resulting in catalysts having even higher activity than Mo{sub 2}C. The performance of the catalysts in hydrodechloration was also investigated.

COATING OF POLYMERIC SUBSTRATE CATALYSTS ON METALLIC SURFACES

Directory of Open Access Journals (Sweden)

H. HOSSEINI

2010-12-01

Full Text Available This article presents results of a study on coating of a polymeric substrate ca-talyst on metallic surface. Stability of coating on metallic surfaces is a proper specification. Sol-gel technology was used to synthesize adhesion promoters of polysilane compounds that act as a mediator. The intermediate layer was coated by synthesized sulfonated polystyrene-divinylbenzene as a catalyst for production of MTBE in catalytic distillation process. Swelling of catalyst and its separation from the metal surface was improved by i increasing the quantity of divinylbenzene in the resin’s production process and ii applying adhesion pro¬moters based on the sol-gel process. The rate of ethyl silicate hydrolysis was intensified by increasing the concentration of utilized acid while the conden¬sation polymerization was enhanced in the presence of OH–. Sol was formed at pH 2, while the pH should be 8 for the formation of gel. By setting the ratio of the initial concentrations of water to ethyl silicate to 8, the gel formation time was minimized.

Application of Metal Catalysts for High Selectivity of Glycerol Conversion to Alcohols

Science.gov (United States)

2010-11-01

The objective of this project is to determine the applicability of metal-based catalysts and optimize the process conditions for thermochemically producing primary alcohols. Metal catalysts were evaluated for their selectivities for producing alcohol...

Highly stable noble-metal nanoparticles in tetraalkylphosphonium ionic liquids for in situ catalysis.

Science.gov (United States)

Banerjee, Abhinandan; Theron, Robin; Scott, Robert W J

2012-01-09

Gold and palladium nanoparticles were prepared by lithium borohydride reduction of the metal salt precursors in tetraalkylphosphonium halide ionic liquids in the absence of any organic solvents or external nanoparticle stabilizers. These colloidal suspensions remained stable and showed no nanoparticle agglomeration over many months. A combination of electrostatic interactions between the coordinatively unsaturated metal nanoparticle surface and the ionic-liquid anions, bolstered by steric protection offered by the bulky alkylated phosphonium cations, is likely to be the reason behind such stabilization. The halide anion strongly absorbs to the nanoparticle surface, leading to exceptional nanoparticle stability in halide ionic liquids; other tetraalkylphosphonium ionic liquids with non-coordinating anions, such as tosylate and hexafluorophosphate, show considerably lower affinities towards the stabilization of nanoparticles. Palladium nanoparticles stabilized in the tetraalkylphosphonium halide ionic liquid were stable, efficient, and recyclable catalysts for a variety of hydrogenation reactions at ambient pressures with sustained activity. Aerial oxidation of the metal nanoparticles occurred over time and was readily reversed by re-reduction of oxidized metal salts. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Development of biomimetic catalytic oxidation methods and non-salt methods using transition metal-based acid and base ambiphilic catalysts

Science.gov (United States)

MURAHASHI, Shun-Ichi

2011-01-01

This review focuses on the development of ruthenium and flavin catalysts for environmentally benign oxidation reactions based on mimicking the functions of cytochrome P-450 and flavoenzymes, and low valent transition-metal catalysts that replace conventional acids and bases. Several new concepts and new types of catalytic reactions based on these concepts are described. PMID:21558760

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

Science.gov (United States)

Zhao, Chunjiang; Wu, Huarui

2018-03-01

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

Selective hydrodeoxygenation of cyclic vicinal diols to cyclic alcohols over tungsten oxide-palladium catalysts.

Science.gov (United States)

Amada, Yasushi; Ota, Nobuhiko; Tamura, Masazumi; Nakagawa, Yoshinao; Tomishige, Keiichi

2014-08-01

Hydrodeoxygenation of cyclic vicinal diols such as 1,4-anhydroerythritol was conducted over catalysts containing both a noble metal and a group 5-7 transition-metal oxide. The combination of Pd and WOx allowed the removal of one of the two OH groups selectively. 3-Hydroxytetrahydrofuran was obtained from 1,4-anhydroerythritol in 72 and 74% yield over WOx -Pd/C and WOx -Pd/ZrO2 , respectively. The WOx -Pd/ZrO2 catalyst was reusable without significant loss of activity if the catalyst was calcined as a method of regeneration. Characterization of WOx -Pd/C with temperature-programmed reduction, X-ray diffraction, and transmission electron microscopy/energy-dispersive X-ray spectroscopy suggested that Pd metal particles approximately 9 nm in size were formed on amorphous tungsten oxide particles. A reaction mechanism was proposed on the basis of kinetics, reaction results with tungsten oxides under an atmosphere of Ar, and density functional theory calculations. A tetravalent tungsten center (W(IV) ) was formed by reduction of WO3 with the Pd catalyst and H2 , and this center served as the reductant for partial hydrodeoxygenation. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Fundamental Studies of the Reforming of Oxygenated Compounds over Supported Metal Catalysts

Energy Technology Data Exchange (ETDEWEB)

Dumesic, James A. [Univ. of Wisconsin, Madison, WI (United States)

2016-01-04

The main objective of our research has been to elucidate fundamental concepts associated with controlling the activity, selectivity, and stability of bifunctional, metal-based heterogeneous catalysts for tandem reactions, such as liquid-phase conversion of oxygenated hydrocarbons derived from biomass. We have shown that bimetallic catalysts that combine a highly-reducible metal (e.g., platinum) with an oxygen-containing metal promoter (e.g., molybdenum) are promising materials for conversion of oxygenated hydrocarbons because of their high activity for selective cleavage for carbon-oxygen bonds. We have developed methods to stabilize metal nanoparticles against leaching and sintering under liquid-phase reaction conditions by using atomic layer deposition (ALD) to apply oxide overcoat layers. We have used controlled surface reactions to produce bimetallic catalysts with controlled particle size and controlled composition, with an important application being the selective conversion of biomass-derived molecules. The synthesis of catalysts by traditional methods may produce a wide distribution of metal particle sizes and compositions; and thus, results from spectroscopic and reactions kinetics measurements have contributions from a distribution of active sites, making it difficult to assess how the size and composition of the metal particles affect the nature of the surface, the active sites, and the catalytic behavior. Thus, we have developed methods to synthesize bimetallic nanoparticles with controlled particle size and controlled composition to achieve an effective link between characterization and reactivity, and between theory and experiment. We have also used ALD to modify supported metal catalysts by addition of promoters with atomic-level precision, to produce new bifunctional sites for selective catalytic transformations. We have used a variety of techniques to characterize the metal nanoparticles in our catalysts, including scanning transmission electron

Chemoselective single-site Earth-abundant metal catalysts at metal–organic framework nodes

Energy Technology Data Exchange (ETDEWEB)

Manna, Kuntal; Ji, Pengfei; Lin, Zekai; Greene, Francis X.; Urban, Ania; Thacker, Nathan C.; Lin, Wenbin (UC)

2016-08-30

Earth-abundant metal catalysts are critically needed for sustainable chemical synthesis. Here we report a simple, cheap and effective strategy of producing novel earth-abundant metal catalysts at metal–organic framework (MOF) nodes for broad-scope organic transformations. The straightforward metalation of MOF secondary building units (SBUs) with cobalt and iron salts affords highly active and reusable single-site solid catalysts for a range of organic reactions, including chemoselective borylation, silylation and amination of benzylic C–H bonds, as well as hydrogenation and hydroboration of alkenes and ketones. Our structural, spectroscopic and kinetic studies suggest that chemoselective organic transformations occur on site-isolated, electron-deficient and coordinatively unsaturated metal centres at the SBUs via σ-bond metathesis pathways and as a result of the steric environment around the catalytic site. MOFs thus provide a novel platform for the development of highly active and affordable base metal catalysts for the sustainable synthesis of fine chemicals.

Development of biomimetic catalytic oxidation methods and non-salt methods using transition metal-based acid and base ambiphilic catalysts.

Science.gov (United States)

Murahashi, Shun-Ichi

2011-01-01

This review focuses on the development of ruthenium and flavin catalysts for environmentally benign oxidation reactions based on mimicking the functions of cytochrome P-450 and flavoenzymes, and low valent transition-metal catalysts that replace conventional acids and bases. Several new concepts and new types of catalytic reactions based on these concepts are described. (Communicated by Ryoji Noyori, M.J.A.).

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

Chemoselective Oxidation of Bio-Glycerol with Nano-Sized Metal Catalysts

DEFF Research Database (Denmark)

Li, Hu; Kotni, Ramakrishna; Zhang, Qiuyun

2015-01-01

to selectively oxidize glycerol and yield products with good selectivity is the use of nano-sized metal particles as heterogeneous catalysts. In this short review, recent developments in chemoselective oxidation of glycerol to specific products over nano-sized metal catalysts are described. Attention is drawn...... to various reaction parameters such as the type of the support, the size of the metal particles, and the acid/base properties of the reaction medium which were illustrated to largely influence the activity of the nanocatalyst and selectivity to the target product. - See more at: http...

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

Effect of Phosphine Doping and the Surface Metal State of Ni on the Catalytic Performance of Ni/Al2O3 Catalyst

Directory of Open Access Journals (Sweden)

Xiaoru Li

2015-04-01

Full Text Available Ni-based catalysts as replacement for noble metal catalysts are of particular interest in the catalytic conversion of biomass due to their cheap and satisfactory catalytic activity. The Ni/SiO2 catalyst has been studied for the hydrogenolysis of glycerol, and doping with phosphorus (P found to improve the catalytic performance significantly because of the formation of Ni2P alloys. However, in the present work we disclose a different catalytic phenomenon for the P-doped Ni/Al2O3 catalyst. We found that doping with P has a significant effect on the state of the active Ni species, and thus improves the selectivity to 1,2-propanediol (1,2-PDO significantly in the hydrogenolysis of glycerol, although Ni-P alloys were not observed in our catalytic system. The structure and selectivity correlations were determined from the experimental data, combining the results of X-ray diffraction (XRD, X-ray photoelectron spectroscopy (XPS, hydrogen temperature-programmed reduction (H2-TPR and ammonia temperature-programmed desorption (NH3-TPD. The presence of NiO species, formed from P-doped Ni/Al2O3 catalyst, was shown to benefit the formation of 1,2-PDO. This was supported by the results of the Ni/Al2O3 catalyst containing NiO species with incomplete reduction. Furthermore, the role the NiO species played in the reaction and the potential reaction mechanism over the P-doped Ni/Al2O3 catalyst is discussed. The new findings in the present work open a new vision for Ni catalysis and will benefit researchers in designing Ni-based catalysts.

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.

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.

Efficient Hydrogenolysis of Guaiacol over Highly Dispersed Ni/MCM-41 Catalyst Combined with HZSM-5

Directory of Open Access Journals (Sweden)

Songbai Qiu

2016-09-01

Full Text Available A series of MCM-41 supported Ni catalysts with high metal dispersion was successfully synthesized by simple co-impregnation using proper ethylene glycol (EG. The acquired Ni-based catalysts performed the outstanding hydrogenolysis activity of guaiacol. The effects of the synthesis parameters including drying temperature, calcination temperature, and metal loading on the physical properties of NiO nanoparticles were investigated through the use of X-ray diffraction (XRD. The drying temperature was found to significantly influence the particle sizes of NiO supported on MCM-41, but the calcination temperature and metal loading had less influence. Interestingly, the small particle size (≤3.3 nm and the high dispersion of NiO particles were also obtained for co-impregnation on the mixed support (MCM-41:HZSM-5 = 1:1, similar to that on the single MCM-41 support, leading to excellent hydrogenation activity at low temperature. The guaiacol conversion could reach 97.9% at 150 °C, and the catalytic activity was comparative with that of noble metal catalysts. The hydrodeoxygenation (HDO performance was also promoted by the introduction of acidic HZSM-5 zeolite and an 84.1% yield of cyclohexane at 240 °C was achieved. These findings demonstrate potential applications for the future in promoting and improving industrial catalyst performance.

Highly efficient transition metal and nitrogen co-doped carbide-derived carbon electrocatalysts for anion exchange membrane fuel cells

Science.gov (United States)

Ratso, Sander; Kruusenberg, Ivar; Käärik, Maike; Kook, Mati; Puust, Laurits; Saar, Rando; Leis, Jaan; Tammeveski, Kaido

2018-01-01

The search for an efficient electrocatalyst for oxygen reduction reaction (ORR) to replace platinum in fuel cell cathode materials is one of the hottest topics in electrocatalysis. Among the many non-noble metal catalysts, metal/nitrogen/carbon composites made by pyrolysis of cheap materials are the most promising with control over the porosity and final structure of the catalyst a crucial point. In this work we show a method of producing a highly active ORR catalyst in alkaline media with a controllable porous structure using titanium carbide derived carbon as a base structure and dicyandiamide along with FeCl3 or CoCl2 as the dopants. The resulting transition metal-nitrogen co-doped carbide derived carbon (M/N/CDC) catalyst is highly efficient for ORR electrocatalysis with the activity in 0.1 M KOH approaching that of commercial 46.1 wt.% Pt/C. The catalyst materials are also investigated by scanning electron microscopy, Raman spectroscopy and X-ray photoelectron spectroscopy to characterise the changes in morphology and composition causing the raise in electrochemical activity. MEA performance of M/N/CDC cathode materials in H2/O2 alkaline membrane fuel cell is tested with the highest power density reached being 80 mW cm-2 compared to 90 mW cm-2 for Pt/C.

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...

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)

Process for the regeneration of metallic catalysts

Science.gov (United States)

Katzer, James R.; Windawi, Hassan

1981-01-01

A method for the regeneration of metallic hydrogenation catalysts from the class consisting of Ni, Rh, Pd, Ir, Pt and Ru poisoned with sulfur, with or without accompanying carbon deposition, comprising subjecting the catalyst to exposure to oxygen gas in a concentration of about 1-10 ppm. intermixed with an inert gas of the group consisting of He, A, Xe, Kr, N.sub.2 and air substantially free of oxygen to an extent such that the total oxygen molecule throughout is in the range of about 10 to 20 times that of the hydrogen sulfide molecular exposure producing the catalyst poisoning while maintaining the temperature in the range of about 300.degree. to 500.degree. C.

Rejuvenation of residual oil hydrotreating catalysts by leaching of foulant metals. Modelling of the metal leaching process

Energy Technology Data Exchange (ETDEWEB)

Marafi, M.; Kam, E.K.T.; Stanislaus, A.; Absi-Halabi, M. [Petroleum Technology Department, Petroleum, Petrochemicals and Materials Division, Kuwait Institute for Scientific Research, Safat (Kuwait)

1996-11-19

Increasing emphasis has been paid in recent years on the development of processes for the rejuvenation of spent residual oil hydroprocessing catalysts, which are deactivated by deposition of metals (e.g. vanadium) and coke. As part of a research program on this subject, we have investigated selective removal of the major metal foulant from the spent catalyst by chemical leaching. In the present paper, we report the development of a model for foulant metals leaching from the spent catalyst. The leaching process is considered to involve two consecutive operations: (1) removal of metal foulants along the main mass transfer channels connected to the narrow pores until the pore structure begins to develop and (2) removal of metal foulants from the pore structure. Both kinetic and mass transfer aspects were considered in the model development, and a good agreement was noticed between experimental and simulated results

Cross-Linked CoMoO4/rGO Nanosheets as Oxygen Reduction Catalyst

Directory of Open Access Journals (Sweden)

Jiaqi Fu

2017-12-01

Full Text Available Development of inexpensive and robust electrocatalysts towards oxygen reduction reaction (ORR is crucial for the cost-affordable manufacturing of metal-air batteries and fuel cells. Here we show that cross-linked CoMoO4 nanosheets and reduced graphene oxide (CoMoO4/rGO can be integrated in a hybrid material under one-pot hydrothermal conditions, yielding a composite material with promising catalytic activity for oxygen reduction reaction (ORR. Cyclic voltammetry (CV and linear sweep voltammetry (LSV were used to investigate the efficiency of the fabricated CoMoO4/rGO catalyst towards ORR in alkaline conditions. The CoMoO4/rGO composite revealed the main reduction peak and onset potential centered at 0.78 and 0.89 V (vs. RHE, respectively. This study shows that the CoMoO4/rGO composite is a highly promising catalyst for the ORR under alkaline conditions, and potential noble metal replacement cathode in fuel cells and metal-air batteries.

Efficient selective catalytic reduction of NO by novel carbon-doped metal catalysts made from electroplating sludge.

Science.gov (United States)

Zhang, Jia; Zhang, Jingyi; Xu, Yunfeng; Su, Huimin; Li, Xiaoman; Zhou, Ji Zhi; Qian, Guangren; Li, Li; Xu, Zhi Ping

2014-10-07

Electroplating sludges, once regarded as industrial wastes, are precious resources of various transition metals. This research has thus investigated the recycling of an electroplating sludge as a novel carbon-doped metal (Fe, Ni, Mg, Cu, and Zn) catalyst, which was different from a traditional carbon-supported metal catalyst, for effective NO selective catalytic reduction (SCR). This catalyst removed >99.7% NO at a temperature as low as 300 °C. It also removed NO steadily (>99%) with a maximum specific accumulative reduced amount (MSARA) of 3.4 mmol/g. Gas species analyses showed that NO removal was accompanied by evolving N2 and CO2. Moreover, in a wide temperature window, the sludge catalyst showed a higher CO2 selectivity (>99%) than an activated carbon-supported metal catalyst. Structure characterizations revealed that carbon-doped metal was transformed to metal oxide in the sludge catalyst after the catalytic test, with most carbon (2.33 wt %) being consumed. These observations suggest that NO removal over the sludge catalyst is a typical SCR where metals/metal oxides act as the catalytic center and carbon as the reducing reagent. Therefore, our report probably provides an opportunity for high value-added utilizations of heavy-metal wastes in mitigating atmospheric pollutions.

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)

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.

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

High-Throughput Screening of Heterogeneous Catalysts for the Conversion of Furfural to Bio-Based Fuel Components

Directory of Open Access Journals (Sweden)

Roberto Pizzi

2015-12-01

Full Text Available The one-pot catalytic reductive etherification of furfural to 2-methoxymethylfuran (furfuryl methyl ether, FME, a valuable bio-based chemical or fuel, is reported. A large number of commercially available hydrogenation heterogeneous catalysts based on nickel, copper, cobalt, iridium, palladium and platinum catalysts on various support were evaluated by a high-throughput screening approach. The reaction was carried out in liquid phase with a 10% w/w furfural in methanol solution at 50 bar of hydrogen. Among all the samples tested, carbon-supported noble metal catalysts were found to be the most promising in terms of productivity and selectivity. In particular, palladium on charcoal catalysts show high selectivity (up to 77% to FME. Significant amounts of furfuryl alcohol (FA and 2-methylfuran (2-MF are observed as the major by-products.

Copper oxide as efficient catalyst for oxidative dehydrogenation of alcohols with air

DEFF Research Database (Denmark)

Poreddy, Raju; Engelbrekt, Christian; Riisager, Anders

2015-01-01

The oxidative dehydrogenation of alcohols to carbonyl compounds was studied using CuO nanoparticle catalysts prepared by solution synthesis in buffered media. CuO nanoparticles synthesized in N-cyclohexyl- 3-aminopropanesulfonic acid buffer showed high catalytic activity for the oxidation...... of benzylic, alicyclic and unsaturated alcohols to their corresponding carbonyl compounds with excellent selectivities. The observed trend in activity for conversion of substituted alcohols suggested a β-H elimination step to be involved, thus enabling a possible reaction mechanism for oxidative...... dehydrogenation of benzyl alcohols to be proposed. The use of CuO as an inexpensive and efficient heterogeneous catalyst under aerobic conditions provides a new noble metal-free and green reaction protocol for carbonyl compound synthesis....

Turbostratic carbon supported palladium as an efficient catalyst for reductive purification of water from trichloroethylene

Directory of Open Access Journals (Sweden)

Emil Kowalewski

2017-12-01

Full Text Available This work investigates the catalytic properties of turbostratic carbon supported Pd catalyst in hydrodechlorination of trichloroethylene (TCE HDC in aqueous phase. 1.57 wt% Pd/C was thoroughly characterized by BET, TPHD, CO chemisorption, PXRD, STEM, XPS and used as the catalyst in removal of trichloroethylene from drinking water in batch and continuous-flow reactors. The studies showed that catalytic performance of Pd/C depended on the hydrophobicity and textural properties of carbon support, which influenced noble metal dispersion and increased catalyst tolerance against deactivation by chlorination. Palladium in the form of uniformly dispersed small (~3.5 nm nanoparticles was found to be very active and stable in purification of water from TCE both in batch and continuous-flow operation.

THE THEORY OF DEVELOPMENT OF SUPPORTED METAL-COMPLEX CATALYSTS

Directory of Open Access Journals (Sweden)

T. L. Rakitskaya

2015-06-01

Full Text Available Some results of the investigations for the purpose of development of supported metal-complex catalysts for phosphine and carbon monoxide oxidation as well as for ozone decomposition are summarized. The activity of such catalysts has been found to depend not only on a nature of a central atom and ligands but also on a nature of supports. The theoretical model explaining mechanisms of surface complex formation taking into account the influence of physicochemical and structural-adsorption properties of the supports (SiO2, Al2O3, carbon materials, zeolites, dispersed silicas, lamellar aluminosilicates, etc. has been proposed. For quantitative description of the support effect, such a thermodynamic parameter as the adsorbed water activity assignable with the help of water vapor adsorption isotherms has been introduced. Successive stability constants of the surface metal complexes have been calculated by the kinetic method and, hence, compositions and partial catalytic activity of the latter have been determined. Taking into account the competitive adsorption of metal ions on the supports, some schemes of formation of surface bimetallic complexes have been suggested. The compositions of the supported metal-complex catalysts have been optimized to meet requirements of their use in respirators and plants for air purification from foregoing gaseous toxicants.

Selective catalytic oxidation of NO as a process stage in NOx separation from power plant and production systems off-gases. Catalyst development and reaction kinetics. Final report. Die selektive katalytische Oxidation des NO als Prozess-Stufe bei der Stickoxidabscheidung aus Abgasen von Kraftwerken und Produktionsanlagen. Katalysatorentwicklung und Reaktionskinetik. Abschlussbericht

Energy Technology Data Exchange (ETDEWEB)

Emig, G.; Seifert, J.

1989-06-01

The research project was to investigate the heterogeneously catalyzed oxidation of NO in flue gas using 1. metal oxide catalysts (commonly on a MnO{sub 2} basis), 2. ZSM5 zeolites (pentasil), and 3. noble metal catalysts. Apart from the reaction kinetics, also the activity and resistance to typical catalyst poisons (SO{sub 2}, HCl, HF, heavy metals) were investigated. A fully automatic, computer-controlled experimental apparatus was developed which apart from the analysis of reaction products permitted also dynamic experiments with time constants in the seconds range and experiments with cyclic variation of concentration, temperature, and time of residue. (RB).

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.

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)

EXAFS characterization of supported metal catalysts in chemically dynamic environments

International Nuclear Information System (INIS)

Robota, H.J.

1991-01-01

Characterization of catalysts focuses on the identification of an active site responsible for accelerating desirable chemical reactions. The identification, characterization, and selective modification of such sites is fundamental to the development of structure-function relationships. Unfortunately, this goal is far from realized in nearly all catalysts, and particularly in catalysts comprised of small supported metal particles. X-ray absorption spectroscopy (XAS) has had a dramatic effect on our understanding of supported metal particles in their resting state. However, the performance of a catalyst can not be assessed from such simple resting state measurements. Among the factors which influence catalyst performance are the exact catalyst composition, including the support and any modifiers; particle size; catalyst finishing and pretreatment conditions; pressure, composition, and temperature of the operating environment; time. Gaining an understanding of how the structure of a catalytic site can change with such an array of variables requires that we begin to develop measurement methods which are effective under chemically dynamic conditions. Ideally, it should be possible to obtain a full X-ray absorption spectrum of each element thought to have a causal relationship with observed catalyst properties. From these spectra, we can optimally extract only a relatively limited amount of information which we must then piece together with information derived from other characterization methods and intuition to arrive at a hypothetical structure of the operating catalyst. Information about crystallinity, homogeneity, and general disorder can be obtained from the Debye-Waller factor. Finally, through analogy with known compounds, the electronic structure of the active atoms can be inferred from near edge absorption features

One-dimensional manganese-cobalt oxide nanofibres as bi-functional cathode catalysts for rechargeable metal-air batteries

OpenAIRE

Jung, Kyu-Nam; Hwang, Soo Min; Park, Min-Sik; Kim, Ki Jae; Kim, Jae-Geun; Dou, Shi Xue; Kim, Jung Ho; Lee, Jong-Won

2015-01-01

Rechargeable metal-air batteries are considered a promising energy storage solution owing to their high theoretical energy density. The major obstacles to realising this technology include the slow kinetics of oxygen reduction and evolution on the cathode (air electrode) upon battery discharging and charging, respectively. Here, we report non-precious metal oxide catalysts based on spinel-type manganese-cobalt oxide nanofibres fabricated by an electrospinning technique. The spinel oxide nanof...

Development of super thin foil metal supported catalyst; Chousuhaku metal tantai shokubai no kaihatsu

Energy Technology Data Exchange (ETDEWEB)

Sanji, F; Takada, T [Toyota Motor Corp., Aichi (Japan)

1997-10-01

In order to improve warm-up performance, high heat resistance and long life durability of catalysts, the reduction of the metal support heat capacity has been focused. The effects of both reducing foil thickness and lowering cell density on low heat capacity have been investigated. As a result of engine bench and vehicle test, it was apparent that the reduction of foil thickness has greater effects. Newly developed 30 {mu} m foil thickness metal supported catalyst has quicker warm-up performance, and its structural durability up to 950degC is confirmed. 3 refs., 11 figs., 1 tab.

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)

Transesterification of jatropha oil with methanol over Mg–Zn mixed metal oxide catalysts

International Nuclear Information System (INIS)

Lee, H.V.; Taufiq-Yap, Y.H.; Hussein, M.Z.; Yunus, R.

2013-01-01

A design was developed for the transesterification reaction of non-edible Jatropha Curcas oil using a heterogeneous catalysis system to replace the use of a homogeneous catalytic reaction. Investigations were conducted on solid MgO–ZnO mixed metal oxide catalyst bases with different atomic ratios of magnesium to zinc (Mg/Zn). These catalysts were characterized by BET (Brunauer–Emmer–Teller) surface area analysis, X-ray Diffraction (XRD), and Scanning Electron Microscopy (SEM) with Energy Dispersive X-ray Spectroscopy (EDS), and the alkalinity of the catalysts was studied by Temperature Programmed Desorption of carbon dioxide (TPD-CO 2 ). The physicochemical properties of the MgO–ZnO binary system were superior to those of the individual bulk oxides of MgO and ZnO. In addition, the formation of a binary system between MgO and ZnO established an effective method for transesterification processes. In this study, the effects of stoichiometric composition and surface characteristics on the transesterification activity of MgO–ZnO were investigated. The catalysts exhibited high catalytic activity (∼80%) with reliable reusability for biodiesel production. -- Highlights: ► Transesterification reaction of non-edible jatropha oil using solid base catalyst. ► MgO–ZnO binary system showed superior effect than the individual MgO and ZnO. ► More than 80% of FAME yield was achieved under mild condition. ► MgO–ZnO catalyst showed reliable reusability throughout 5 runs. ► Fuel properties of prepared biodiesel were complying with the biodiesel standards.

New antipollution processing of a used refining catalyst and complete recovery of the catalyst metallic components

Energy Technology Data Exchange (ETDEWEB)

Trinh Dinh Chan; Llido, E.

1992-05-15

The used refining catalyst, containing metals such as vanadium, nickel and iron, is first processed by stripping; it is then calcined in critical conditions and heat processed in the presence of a melted alkaline base; the resulting solid matter is then water processed. The antipollution process can be applied to oil fraction hydroconversion or hydroprocessing catalysts.

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

Controlled metal nitrate decomposition for the preparation of supported metal Catalysts

NARCIS (Netherlands)

Wolters, M.

2010-01-01

High surface area supported metal (oxide) catalysts are essential for the production of fuels, chemicals, pharmaceuticals and the abatement of environmental pollution. Impregnation of high surface area supports, often silica or alumina, followed by drying, calcination and reduction is one of the

Pt-based Bi-metallic Monolith Catalysts for Partial Upgrading of Microalgae Oil

Energy Technology Data Exchange (ETDEWEB)

Lawal, Adeniyi [Stevens Inst. of Technology, Hoboken, NJ (United States); Manganaro, James [Anasyn LLC, Princeton, NJ (United States); Goodall, Brian [Valicor Renewables LLC, Dexter, MI (United States); Farrauto, Robert [Columbia Univ., New York, NY (United States)

2015-03-24

Valicor’s proprietary wet extraction process in conjunction with thermochemical pre-treatment was performed on algal biomass from two different algae strains, Nannochloropsis Salina (N.S.) and Chlorella to produce algae oils. Polar lipids such as phospholipids were hydrolyzed, and metals and metalloids, known catalyst poisons, were separated into the aqueous phase, creating an attractive “pre-refined” oil for hydrodeoxygenation (HDO) upgrading by Stevens. Oil content and oil extraction efficiency of approximately 30 and 90% respectively were achieved. At Stevens, we formulated a Pt-based bi-metallic catalyst which was demonstrated to be effective in the hydro-treating of the algae oils to produce ‘green’ diesel. The bi-metallic catalyst was wash-coated on a monolith, and in conjunction with a high throughput high pressure (pilot plant) reactor system, was used in hydrotreating algae oils from N.S. and Chlorella. Mixtures of these algae oils and refinery light atmospheric gas oil (LAGO) supplied by our petroleum refiner partner, Marathon Petroleum Corporation, were co-processed in the pilot plant reactor system using the Pt-based bi-metallic monolith catalyst. A 26 wt% N.S. algae oil/74 wt % LAGO mixture hydrotreated in the reactor system was subjected to the ASTM D975 Diesel Fuel Specification Test and it met all the important requirements, including a cetane index of 50.5. An elemental oxygen analysis performed by an independent and reputable lab reported an oxygen content of trace to none found. The successful co-processing of a mixture of algae oil and LAGO will enable integration of algae oil as a refinery feedstock which is one of the goals of DOE-BETO. We have presented experimental data that show that our precious metal-based catalysts consume less hydrogen than the conventional hydrotreating catalyst NiMo Precious metal catalysts favor the hydrodecarbonylation/hydrodecarboxylation route of HDO over the dehydration route preferred by base metal

Design of Embedded Metal Catalysts via Reverser Micro-Emulsion System: a Way to Suppress Catalyst Deactivation by Metal Sintering

KAUST Repository

AlMana, Noor

2016-06-19

The development of highly selective and active, long-lasting, robust, low-cost and environmentally benign catalytic materials is the greatest challenge in the area of catalysis study. In this context, core-shell structures where the active sites are embedded inside the protecting shell have attracted a lot of researchers working in the field of catalysis owing to their enhanced physical and chemical properties suppress catalyst deactivation. Also, a new active site generated at the interface between the core and shell may increases the activity and efficiency of the catalyst in catalytic reactions especially for oxide shells that exhibit redox properties such as TiO2 and CeO2. Moreover, coating oxide layer over metal nanoparticles (NPs) can be designed to provide porosity (micropore/mesopore) that gives selectivity of the various reactants by the different gas diffusion rates. In this thesis, we will discuss the concept of catalyst stabilization against metal sintering by a core-shell system. In particular we will study the mechanistic of forming core-shell particles and the key parameters that can influence the properties and morphology of the Pt metal particle core and SiO2 shell (Pt@SiO2) using the reverse micro-emulsion method. The Pt@SiO2 core-shell catalysts were investigated for low-temperature CO oxidation reaction. The study was further extended to other catalytic applications by varying the composition of the core as well as the chemical nature of the shell material. The Pt NPs were embedded within another oxide matrix such as ZrO2 and TiO2 for CO oxidation reaction. These materials were studied in details to identify the factors governing the coating of the oxide around the metal NPs. Next, a more challenging system, namely, bimetallic Ni9Pt NPs embedded in TiO2 and ZrO2 matrix were investigated for dry reforming of methane reaction at high temperatures. The challenges of designing Ni9Pt@oxide core-shell structure with TiO2 and ZrO2 and their tolerance

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.

Biopropionic acid production via molybdenumcatalyzed deoxygenation of lactic acid

NARCIS (Netherlands)

Korstanje, T.J.; Kleijn, H.; Jastrzebski, J.T.B.H.; Klein Gebbink, R.J.M.

2013-01-01

As the search for non-fossil based building blocks for the chemical industry increases, new methods for the deoxygenation of biomass-derived substrates are required. Here we present the deoxygenation of lactic acid to propionic acid, using a catalyst based on the non-noble and abundant metal

Cobalt oxide-based catalysts deposited by cold plasma for proton exchange membrane fuel cells

Energy Technology Data Exchange (ETDEWEB)

Kazimierski, P.; Jozwiak, L.; Sielski, J.; Tyczkowski, J., E-mail: jacek.tyczkowski@p.lodz.pl

2015-11-02

In proton exchange membrane fuel cells (PEMFC), both the anodic hydrogen oxidation reaction and the cathodic oxygen reduction reaction (ORR) require appropriate catalysts. So far, platinum-based catalysts are still the best option for this purpose. However, because these catalysts are too expensive for making commercially viable fuel cells, extensive research over the past decade has focused on developing noble metal-free alternative catalysts. In this paper, an approach based on cobalt oxide films fabricated by plasma-enhanced metal-organic chemical vapor deposition is presented. Such a material can be used to prepare catalysts for ORR in PEMFC. The films containing CoO{sub X} were deposited on a carbon paper thereby forming the electrode. Morphology and atomic composition of the films were investigated by scanning electron microscopy and energy-dispersive X-ray spectroscopy, respectively. The possibility of their application as the electro-catalyst for ORR in PEMFC was investigated and the electro-catalytic activities were evaluated by the electrochemical measurements and single cell tests. It was found that the fuel cell with Pt as the anode catalyst and CoO{sub X} deposit as the cathode catalyst was characterized by the open circuit voltage of 635 mV, Tafel slope of approx. 130 mV/dec and the maximum power density of 5.3 W/m{sup 2}. - Highlights: • Cobalt oxide catalyst for proton exchange membrane fuel cells was plasma deposited. • The catalyst exhibits activity for the oxygen reduction reaction. • Morphology and atomic composition of the catalyst were determined.

Oxygen-assisted conversion of propane over metal and metal oxide catalysts

Energy Technology Data Exchange (ETDEWEB)

Laate, Leiv

2002-07-01

An experimental set-up has been build and applied in activity/selectivity studies of the oxygen-assisted conversion of propane over metals and metal oxide catalysts. The apparatus has been used in order to achieve an improved understanding of the reactions between alkanes/alkenes and oxygen. Processes that have been studied arc the oxidative dehydrogenation of propane over a VMgO catalyst and the selective combustion of hydrogen in the presence of hydrocarbons over Pt-based catalysts and metal oxide catalysts. From the experiments, the following conclusions are drawn: A study of the oxidative dehydrogenation of propane over a vanadium-magnesium-oxide catalyst confirmed that the main problem with this system is the lack of selectivity due to complete combustion. Selectivity to propene up to about 60% was obtained at 10% conversion at 500{sup o}C, but the selectivity decreased with increasing conversion. No oxygenates were detected, the only by- products were CO and CO{sub 2}. The selectivity to propene is a strong function of the conversion of propane. The reaction rate of propane was found to be 1.0 {+-} 0.1 order in propane and 0.07 {+-} 0.02 order in oxygen. The kinetic results are in agreement with a Mars van Krevelen mechanism with the activation of the hydrocarbons as the slow step. The rate of propene oxidation to CO{sub 2} was studied and found to be significantly higher than that of propane. Another possible process involves the simultaneous equilibrium dehydrogenation of alkanes to alkenes and combustion of the hydrogen formed to shift the equilibrium dehydrogenation reaction further to the product alkenes. A study of the selective combustion of hydrogen in the presence of propane/propene was found to be possible under certain reaction conditions over some metal oxide catalysts. In{sub 2}O{sub 3}/SiO{sub 2}, unsupported Bi{sub 2}O{sub 3} and ZSM-5 show the ability to combust hydrogen in a gas mixture with propane and oxygen with good selectivity. Bi{sub 2

Evaluation of mechanical properties in metal wire mesh supported selective catalytic reduction (SCR) catalyst structures

Science.gov (United States)

Rajath, S.; Siddaraju, C.; Nandakishora, Y.; Roy, Sukumar

2018-04-01

The objective of this research is to evaluate certain specific mechanical properties of certain stainless steel wire mesh supported Selective catalytic reduction catalysts structures wherein the physical properties of the metal wire mesh and also its surface treatments played vital role thereby influencing the mechanical properties. As the adhesion between the stainless steel wire mesh and the catalyst material determines the bond strength and the erosion resistance of catalyst structures, surface modifications of the metal- wire mesh structure in order to facilitate the interface bonding is therefore very important to realize enhanced level of mechanical properties. One way to enhance such adhesion properties, the stainless steel wire mesh is treated with the various acids, i.e., chromic acid, phosphoric acid including certain mineral acids and combination of all those in various molar ratios that could generate surface active groups on metal surface that promotes good interface structure between the metal- wire mesh and metal oxide-based catalyst material and then the stainless steel wire mesh is dipped in the glass powder slurry containing some amount of organic binder. As a result of which the said catalyst material adheres to the metal-wire mesh surface more effectively that improves the erosion profile of supported catalysts structure including bond strength.

Highly aligned vertical GaN nanowires using submonolayer metal catalysts

Science.gov (United States)

Wang, George T [Albuquerque, NM; Li, Qiming [Albuquerque, NM; Creighton, J Randall [Albuquerque, NM

2010-06-29

A method for forming vertically oriented, crystallographically aligned nanowires (nanocolumns) using monolayer or submonolayer quantities of metal atoms to form uniformly sized metal islands that serve as catalysts for MOCVD growth of Group III nitride nanowires.

Synthesis, characterization and electrochemical studies of Pt- W/C catalyst for polymer electrolyte membrane fuel cells

International Nuclear Information System (INIS)

Ahmed, R.; Shahid, S.; Ansari, M. S.

2013-01-01

Pt-W/C catalyst was synthesized by slow reduction of platinum and tungsten solutions in the desired ratio with subsequent deposition on the Vulcan carbon already added to the solution. Crystallite size of catalyst was about 9 nm and its density, cell volume, d-spacing and lattice parameter were also calculated. EDX analysis of the catalyst was also done. Electrochemical surface area of the catalyst was determined by cyclic voltammetry (CV). CV of the catalyst was done both in acidic and basic media to find out the peak potential, peak current, specific activity and mass activity of the catalyst. Peak potential versus scan rate plots showed that the electro oxidation of methanol is an irreversible process. Tafel equation was used to plot polarization curves to find out the exchange current density. Higher values of exchange current indicate better catalysts. Specific activities of the catalyst were determined in acidic and basic media and it was found that the specific activity in basic media increased substantially as compared to acidic media. The specific activity in acidic media was 83 mA/mg pt whereas in basic media it was 137mA/mg pt which is a substantial increase. Heterogeneous rate constant in acidic media was 6.15 * 10-6 cm/ s and in basic media it was 4.92 * 10-5 cm/s which is much higher in basic media. In this binary catalyst addition of tungsten has increased the catalytic activity but it is non-noble metal thus will decrease the cost. Stability studies of the catalyst were done upto fifty cycles both in acidic and basic media and was found quite stable in both the media. (author)

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.

Metal Nanoparticle Catalysts for Carbon Nanotube Growth

Science.gov (United States)

Pierce, Benjamin F.

2003-01-01

Work this summer involved and new and unique process for producing the metal nanoparticle catalysts needed for carbon nanotube (CNT) growth. There are many applications attributed to CNT's, and their properties have deemed them to be a hot spot in research today. Many groups have demonstrated the versatility in CNT's by exploring a wide spectrum of roles that these nanotubes are able to fill. A short list of such promising applications are: nanoscaled electronic circuitry, storage media, chemical sensors, microscope enhancement, and coating reinforcement. Different methods have been used to grow these CNT's. Some examples are laser ablation, flame synthesis, or furnace synthesis. Every single approach requires the presence of a metal catalyst (Fe, Co, and Ni are among the best) that is small enough to produce a CNT. Herein lies the uniqueness of this work. Microemulsions (containing inverse micelles) were used to generate these metal particles for subsequent CNT growth. The goal of this summer work was basically to accomplish as much preliminary work as possible. I strived to pinpoint which variable (experimental process, metal product, substrate, method of application, CVD conditions, etc.) was the determining factor in the results. The resulting SEM images were sufficient for the appropriate comparisons to be made. The future work of this project consists of the optimization of the more promising experimental procedures and further exploration onto what exactly dictated the results.

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.

Noble metal abundances in komatiite suites from Alexo, Ontario and Gorgona Island, Colombia

Science.gov (United States)

Brügmann, G. E.; Arndt, N. T.; Hofmann, A. W.; Tobschall, H. J.

1987-08-01

The distribution of the chalcophile and siderophile metals Cu, Ni, Au, Pd, Ir, Os and Ru in an Archaean komatiite flow from Alexo, Ontario and in a Phanerozoic komatiitic suite of Gorgona Island, Colombia, provides new information about the geochemical behaviour of these elements. Copper, Au and Pd behave as incompatible elements during the crystallization of these ultramafic magmas. In contrast, Ni, Ir, Os and Ru concentrations systematically decrease with decreasing MgO contents, a pattern characteristic of compatible elements. These trends are most probably controlled by olivine crystallization, which implies that Ir, Os and Ru are compatible in olivine. Calculated partition coefficients for Ir, Os and Ru between olivine and the melt are about 1.8. Compared to primitive mantle, parental komatiitic liquids are enriched in (incompatible) Cu, Au and Pd and depleted in (compatible) Ir, Os and Ru. Within both Archaean and Phanerozoic komatiites, noble metal ratios such as Au/Pd, Ir/Os, Os/Ru and Ru/Ir and ratios of lithophile and siderophile elements such as Ti/Pd, Ti/Au are constant and similar to primitive mantle values. This implies that Au and Pd are moderately incompatible elements and that there has been no significant fractionation of siderophile and lithophile elements since the Archaean. Platinum-group element abundances of normal MORB are highly variable and always much lower than in komatiites, because MORB magma is saturated with sulfur and a variable but minor amount of sulfide segregated during mantle melting or during the ascent of magma to the surface. Sulfide deposits associated with komatiites display similar chalcophile element patterns to those of komatiites. Noble metal ratios such as Pd/Ir, Au/Ir, Pd/Os and Pd/Ru can be used to determine the composition of the host komatiite at the time of sulfide segregation.

C-H functionalization: thoroughly tuning ligands at a metal ion, a chemist can greatly enhance catalyst's activity and selectivity.

Science.gov (United States)

Shul'pin, Georgiy B

2013-09-28

This brief essay consists of a few "exciting stories" devoted to relations within a metal-complex catalyst between a metal ion and a coordinated ligand. When, as in the case of a human couple, the rapport of the partners is cordial and a love cements these relations, a chemist finds an ideal married couple, in other words he obtains a catalyst of choice which allows him to functionalize C-H bonds very efficiently and selectively. Examples of such lucky marriages in the catalytic world of ions and ligands are discussed here. Activity of the catalyst is characterized by turnover number (TON) or turnover frequency (TOF) as well as by yield of a target product. Introducing a chelating N,N- or N,O-ligand to the catalyst molecule (this can be an iron or manganese derivative) sharply enhances its activity. However, the activity of vanadium derivatives (with additionally added to the solution pyrazinecarboxylic acid, PCA) as well as of various osmium complexes does not dramatically depend on the nature of ligands surrounding metal ions. Complexes of these metals are very efficient catalysts in oxidations with H2O2. Osmium derivatives are record-holders exhibiting extremely high TONs whereas vanadium complexes are on the second position. Finally, elegant examples of alkane functionalization on the ions of non-transition metals (aluminium, gallium etc.) are described when one ligand within the metal complex (namely, hydroperoxyl ligand HOO(-)) helps other ligand of this complex (H2O2 molecule coordinated to the metal) to disintegrate into two species, generating very reactive hydroxyl radical. Hydrogen peroxide molecule, even ligated to the metal ion, is perfectly stable without the assistance of the neighboring HOO(-) ligand. This ligand can be easily oxidized donating an electron to its partner ligand (H2O2). In an analogous case, when the central ion in the catalyst is a transition metal, this ion changing its oxidation state can donate an electron to the coordinated H2O2

Design of Highly Selective Platinum Nanoparticle Catalysts for the Aerobic Oxidation of KA-Oil using Continuous-Flow Chemistry.

Science.gov (United States)

Gill, Arran M; Hinde, Christopher S; Leary, Rowan K; Potter, Matthew E; Jouve, Andrea; Wells, Peter P; Midgley, Paul A; Thomas, John M; Raja, Robert

2016-03-08

Highly active and selective aerobic oxidation of KA-oil to cyclohexanone (precursor for adipic acid and ɛ-caprolactam) has been achieved in high yields using continuous-flow chemistry by utilizing uncapped noble-metal (Au, Pt & Pd) nanoparticle catalysts. These are prepared using a one-step in situ methodology, within three-dimensional porous molecular architectures, to afford robust heterogeneous catalysts. Detailed spectroscopic characterization of the nature of the active sites at the molecular level, coupled with aberration-corrected scanning transmission electron microscopy, reveals that the synthetic methodology and associated activation procedures play a vital role in regulating the morphology, shape and size of the metal nanoparticles. These active centers have a profound influence on the activation of molecular oxygen for selective catalytic oxidations. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Precious metal assay analysis of fresh reforming catalyst by x-ray fluorescence spectrometry

International Nuclear Information System (INIS)

McElroy, F.C.; Mulhall, J.M.

1991-01-01

This paper reports that precious metal analysis of fresh reforming catalysts are typically performed by both the catalyst manufacturer and buyer to arrive at a financial settlement on the quantity of metal in each lot of commercial catalyst. Traditional assay methods involve a variety of fire assay or wet chemical acid digestion schemes coupled with gravimetric, colorimetic, or titrimetric measurement for precious metals. Methods must have sufficient precision and accuracy to afford interlaboratory agreement of within one half of one percent relative between the catalyst supplier and purchaser. To meet this requirement many laboratories rely on classical methods. Unfortunately these proceeders are labor intensive and time consuming. X-ray fluorescence has the inherent instrument precision to achieve typical intralaboratory precision of 0.5% RSD on a wide variety of elements and numerous sample types. We have developed an X-ray fluorescence method for the assay quality analysis of fresh reforming catalyst containing platinum, rhenium, and iridium. This method was applied to numerous samples over the past five years

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)

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.

Metal recovery from spent refinery catalysts by means of biotechnological strategies

International Nuclear Information System (INIS)

Beolchini, F.; Fonti, V.; Ferella, F.; Veglio, F.

2010-01-01

A bioleaching study aimed at recovering metals from hazardous spent hydroprocessing catalysts was carried out. The exhaust catalyst was rich in nickel (4.5 mg/g), vanadium (9.4 mg/g) and molybdenum (4.4 mg/g). Involved microorganisms were iron/sulphur oxidizing bacteria. Investigated factors were elemental sulphur addition, ferrous iron addition and actions contrasting a possible metal toxicity (either adding powdered activated charcoal or simulating a cross current process by means of periodical filtration). Ferrous iron resulted to be essential for metal extraction: nickel and vanadium extraction yields were 83% and 90%, respectively, while about 50% with no iron. The observed values for molybdenum extraction yields were not as high as Ni and V ones (the highest values were around 30-40%). The investigated actions aimed at contrasting a possible metal toxicity resulted not to be effective; in contrast, sequential filtration of the liquor leach had a significant negative effect on metals extraction. Nickel and vanadium dissolution kinetics resulted to be significantly faster than molybdenum dissolution ones. Furthermore, a simple first order kinetic model was successfully fitted to experimental data. All the observed results supported the important role of the indirect mechanism in bioleaching of LC-Finer catalysts.

Metal recovery from spent refinery catalysts by means of biotechnological strategies

Energy Technology Data Exchange (ETDEWEB)

Beolchini, F., E-mail: f.beolchini@univpm.it [Department of Marine Sciences, Polytechnic University of Marche, Via Brecce Bianche, 60131 Ancona (Italy); Fonti, V. [Department of Marine Sciences, Polytechnic University of Marche, Via Brecce Bianche, 60131 Ancona (Italy); Ferella, F.; Veglio, F. [Department of Chemistry, Chemical Engineering and Materials, University of L' Aquila, Monteluco di Roio, 67040 L' Aquila (Italy)

2010-06-15

A bioleaching study aimed at recovering metals from hazardous spent hydroprocessing catalysts was carried out. The exhaust catalyst was rich in nickel (4.5 mg/g), vanadium (9.4 mg/g) and molybdenum (4.4 mg/g). Involved microorganisms were iron/sulphur oxidizing bacteria. Investigated factors were elemental sulphur addition, ferrous iron addition and actions contrasting a possible metal toxicity (either adding powdered activated charcoal or simulating a cross current process by means of periodical filtration). Ferrous iron resulted to be essential for metal extraction: nickel and vanadium extraction yields were 83% and 90%, respectively, while about 50% with no iron. The observed values for molybdenum extraction yields were not as high as Ni and V ones (the highest values were around 30-40%). The investigated actions aimed at contrasting a possible metal toxicity resulted not to be effective; in contrast, sequential filtration of the liquor leach had a significant negative effect on metals extraction. Nickel and vanadium dissolution kinetics resulted to be significantly faster than molybdenum dissolution ones. Furthermore, a simple first order kinetic model was successfully fitted to experimental data. All the observed results supported the important role of the indirect mechanism in bioleaching of LC-Finer catalysts.

Kinetics on NiZn Bimetallic Catalysts for Hydrogen Evolution via Selective Dehydrogenation of Methylcyclohexane to Toluene

KAUST Repository

Shaikh Ali, Anaam

2017-01-18

Liquid organic chemical hydrides are effective hydrogen storage media for easy and safe transport. The chemical couple of methylcyclohexane (MCH) and toluene (TOL) has been considered one of the feasible cycles for a hydrogen carrier, but the selective dehydrogenation of MCH to TOL has been reported using only Pt-based noble metal catalysts. This study reports MCH dehydrogenation to TOL using supported NiZn as a selective, non-noble-metal catalyst. A combined experimental and computational study was conducted to provide insight into the site requirements and reaction mechanism for MCH dehydrogenation to TOL, which were compared with those for cyclohexane (CH) dehydrogenation to benzene (BZ). The kinetic measurements carried out at 300-360°C showed an almost zero order with respect to MCH pressure in the high-pressure region (≥10 kPa) and nearly a positive half order with respective to H pressure (≤40 kPa). These kinetic data for the dehydrogenation reaction paradoxically indicate that hydrogenation of a strongly chemisorbed intermediate originating from TOL is the rate-determining step. Density functional theory (DFT) calculation confirms that the dehydrogenated TOL species at the aliphatic (methyl) position group (CHCH) were strongly adsorbed on the surface, which must be hydrogenated to desorb as TOL. This hydrogen-assisted desorption mechanism explains the essential role of excess H present in the feed in maintaining the activity of the metallic surface for hydrogenation. The rate of the CH to BZ reaction was less sensitive to H pressure than that of MCH to TOL, which can be explained by the absence of a methyl group in the structure, which in turn reduces the binding energy of the adsorbed species. DFT suggests that the improved TOL selectivity by adding Zn to Ni was due to Zn atoms preferentially occupying low-coordination sites on the surface (the corner and edge sites), which are likely the unselective sites responsible for the C-C dissociation of the

Kinetics on NiZn Bimetallic Catalysts for Hydrogen Evolution via Selective Dehydrogenation of Methylcyclohexane to Toluene

KAUST Repository

Shaikh Ali, Anaam; Jedidi, Abdesslem; Anjum, Dalaver H.; Cavallo, Luigi; Takanabe, Kazuhiro

2017-01-01

Liquid organic chemical hydrides are effective hydrogen storage media for easy and safe transport. The chemical couple of methylcyclohexane (MCH) and toluene (TOL) has been considered one of the feasible cycles for a hydrogen carrier, but the selective dehydrogenation of MCH to TOL has been reported using only Pt-based noble metal catalysts. This study reports MCH dehydrogenation to TOL using supported NiZn as a selective, non-noble-metal catalyst. A combined experimental and computational study was conducted to provide insight into the site requirements and reaction mechanism for MCH dehydrogenation to TOL, which were compared with those for cyclohexane (CH) dehydrogenation to benzene (BZ). The kinetic measurements carried out at 300-360°C showed an almost zero order with respect to MCH pressure in the high-pressure region (≥10 kPa) and nearly a positive half order with respective to H pressure (≤40 kPa). These kinetic data for the dehydrogenation reaction paradoxically indicate that hydrogenation of a strongly chemisorbed intermediate originating from TOL is the rate-determining step. Density functional theory (DFT) calculation confirms that the dehydrogenated TOL species at the aliphatic (methyl) position group (CHCH) were strongly adsorbed on the surface, which must be hydrogenated to desorb as TOL. This hydrogen-assisted desorption mechanism explains the essential role of excess H present in the feed in maintaining the activity of the metallic surface for hydrogenation. The rate of the CH to BZ reaction was less sensitive to H pressure than that of MCH to TOL, which can be explained by the absence of a methyl group in the structure, which in turn reduces the binding energy of the adsorbed species. DFT suggests that the improved TOL selectivity by adding Zn to Ni was due to Zn atoms preferentially occupying low-coordination sites on the surface (the corner and edge sites), which are likely the unselective sites responsible for the C-C dissociation of the

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

Energy Technology Data Exchange (ETDEWEB)

Reismann, Maximilian

2009-12-08

of the described procedure is the lack of superposition of the changes in the recorded spectra by spectral contributions of shape and size of the nanoparticle. This simplifies the interpretation of the recorded spectra considerably. An essential requirement for the application of noble-metal nanoparticles in medical technology consist of their tunability into the near-infrared spectral region. In this spectral region, the human tissue is more transparent to light irradiation than in the visible region, which allows for using light irradiation to affect nanoparticles in vivo. Elongated gold nanoparticles (nanorods) are promising candidates for this task as their resonance frequency can be tuned over a wide spectral region by varying their size and their aspect ratio. Damping of the plasmon oscillation is an important physical origin for this dependency on shape and size. In this thesis, a contribution of the plasmon damping is investigated that is caused by electronic-scattering of the oscillating conduction electrons at the nanoparticle surface. For this investigation, light-scattering spectra of single gold nanorods are recorded in a systematic approach. The large enhancement of optical fields at the surface of nanoparticles can be used to excite non linear optical phenomena, for example Raman scattering. In this thesis, the construction of a setup is presented that aims at using this enhancement effect for the detection of Raman-scattering signals. This setup is tested, and the ability to enhance the detection of Raman signals is compared to different nanostructured samples. (orig.)

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.

Nanoporous Au: an unsupported pure gold catalyst?

Energy Technology Data Exchange (ETDEWEB)

Wittstock, A; Neumann, B; Schaefer, A; Dumbuya, K; Kuebel, C; Biener, M; Zielasek, V; Steinrueck, H; Gottfried, M; Biener, J; Hamza, A; B?umer, M

2008-09-04

The unique properties of gold especially in low temperature CO oxidation have been ascribed to a combination of various effects. In particular, particle sizes below a few nm and specific particle-support interactions have been shown to play important roles. On the contrary, recent reports revealed that monolithic nanoporous gold (npAu) prepared by leaching a less noble metal, such as Ag, out of the corresponding alloy can also exhibit remarkably high catalytic activity for CO oxidation, even though no support is present. Therefore, it was claimed to be a pure and unsupported gold catalyst. We investigated npAu with respect to its morphology, surface composition and catalytic properties. In particular, we studied the reaction kinetics for low temperature CO oxidation in detail taking mass transport limitation due to the porous structure of the material into account. Our results reveal that Ag, even if removed almost completely from the bulk, segregates to the surface resulting in surface concentrations of up to 10 at%. Our data suggest that this Ag plays a significant role in activation of molecular oxygen. Therefore, npAu should be considered as a bimetallic catalyst rather than a pure Au catalyst.

Metal Fluorides, Metal Chlorides and Halogenated Metal Oxides as Lewis Acidic Heterogeneous Catalysts. Providing Some Context for Nanostructured Metal Fluorides.

Science.gov (United States)

Lennon, David; Winfield, John M

2017-01-28

Aspects of the chemistry of selected metal fluorides, which are pertinent to their real or potential use as Lewis acidic, heterogeneous catalysts, are reviewed. Particular attention is paid to β-aluminum trifluoride, aluminum chlorofluoride and aluminas γ and η, whose surfaces become partially fluorinated or chlorinated, through pre-treatment with halogenating reagents or during a catalytic reaction. In these cases, direct comparisons with nanostructured metal fluorides are possible. In the second part of the review, attention is directed to iron(III) and copper(II) metal chlorides, whose Lewis acidity and potential redox function have had important catalytic implications in large-scale chlorohydrocarbons chemistry. Recent work, which highlights the complexity of reactions that can occur in the presence of supported copper(II) chloride as an oxychlorination catalyst, is featured. Although direct comparisons with nanostructured fluorides are not currently possible, the work could be relevant to possible future catalytic developments in nanostructured materials.

Monodisperse metal nanoparticle catalysts on silica mesoporous supports: synthesis, characterizations, and catalytic reactions

Energy Technology Data Exchange (ETDEWEB)

Somorjai, G.A.

2009-09-14

The design of high performance catalyst achieving near 100% product selectivity at maximum activity is one of the most important goals in the modern catalytic science research. To this end, the preparation of model catalysts whose catalytic performances can be predicted in a systematic and rational manner is of significant importance, which thereby allows understanding of the molecular ingredients affecting the catalytic performances. We have designed novel 3-dimensional (3D) high surface area model catalysts by the integration of colloidal metal nanoparticles and mesoporous silica supports. Monodisperse colloidal metal NPs with controllable size and shape were synthesized using dendrimers, polymers, or surfactants as the surface stabilizers. The size of Pt, and Rh nanoparticles can be varied from sub 1 nm to 15 nm, while the shape of Pt can be controlled to cube, cuboctahedron, and octahedron. The 3D model catalysts were generated by the incorporation of metal nanoparticles into the pores of mesoporous silica supports via two methods: capillary inclusion (CI) and nanoparticle encapsulation (NE). The former method relies on the sonication-induced inclusion of metal nanoparticles into the pores of mesoporous silica, whereas the latter is performed by the encapsulation of metal nanoparticles during the hydrothermal synthesis of mesoporous silica. The 3D model catalysts were comprehensively characterized by a variety of physical and chemical methods. These catalysts were found to show structure sensitivity in hydrocarbon conversion reactions. The Pt NPs supported on mesoporous SBA-15 silica (Pt/SBA-15) displayed significant particle size sensitivity in ethane hydrogenolysis over the size range of 1-7 nm. The Pt/SBA-15 catalysts also exhibited particle size dependent product selectivity in cyclohexene hydrogenation, crotonaldehyde hydrogenation, and pyrrole hydrogenation. The Rh loaded SBA-15 silica catalyst showed structure sensitivity in CO oxidation reaction. In

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

Metal oxides modified NiO catalysts for oxidative dehydrogenation of ethane to ethylene

KAUST Repository

Zhu, Haibo

2014-06-01

The sol-gel method was applied to the synthesis of Zr, Ti, Mo, W, and V modified NiO based catalysts for the ethane oxidative dehydrogenation reaction. The synthesized catalysts were characterized by XRD, N2 adsorption, SEM and TPR techniques. The results showed that the doping metals could be highly dispersed into NiO domains without the formation of large amount of other bulk metal oxide. The modified NiO materials have small particle size, larger surface area, and higher reduction temperature in contrast to pure NiO. The introduction of group IV, V and VI transition metals into NiO decreases the catalytic activity in ethane ODH. However, the ethylene selectivity is enhanced with the highest level for the Ni-W-O and Ni-Ti-O catalysts. As a result, these two catalysts show improved efficiency of ethylene production in the ethane ODH reaction. © 2014 Elsevier B.V. All rights reserved.

Comparative study of metal and non-metal ion implantation in polymers: Optical and electrical properties

International Nuclear Information System (INIS)

Resta, V.; Quarta, G.; Farella, I.; Maruccio, L.; Cola, A.; Calcagnile, L.

2014-01-01

The implantation of 1 MeV metal ( 63 Cu + , 107 Ag + , 197 Au + ) and non-metal ( 4 He + , 12 C + ) ions in a polycarbonate (PC) matrix has been studied in order to evaluate the role of ion species in the modification of optical and electrical properties of the polymer. When the ion fluence is above ∼1 × 10 13 ions cm −2 , the threshold for latent tracks overlapping is overcome and π-bonded carbon clusters grow and aggregate forming a network of conjugated C=C bonds. For fluences around 1 × 10 17 ions cm −2 , the aggregation phenomena induce the formation of amorphous carbon and/or graphite like structures. At the same time, nucleation of metal nanoparticles (NPs) from implanted species can take place when the supersaturation threshold is overcome. The optical absorption of the samples increases in the visible range and the optical band gap redshifts from 3.40 eV up to 0.70 eV mostly due to the carbonization process and the formation of C 0x clusters and cluster aggregates. Specific structures in the extinction spectra are observed when metal ions are selected in contrast to the non-metal ion implanted PC, thus revealing the possible presence of noble metal based NPs interstitial to the C 0x cluster network. The corresponding electrical resistance decreases much more when metal ions are implanted with at least a factor of 2 orders of magnitude difference than the non-metal ions based samples. An absolute value of ∼10 7 Ω/sq has been measured for implantation with metals at doses higher than 5 × 10 16 ions cm −2 , being 10 17 Ω/sq the corresponding sheet resistance for pristine PC

Comparative study of metal and non-metal ion implantation in polymers: Optical and electrical properties

Energy Technology Data Exchange (ETDEWEB)

Resta, V., E-mail: vincenzo.resta@le.infn.it [Department of Engineering for Innovation, University of Salento, Via Monteroni, Lecce I-73100 (Italy); Quarta, G. [Department of Engineering for Innovation, University of Salento, Via Monteroni, Lecce I-73100 (Italy); Farella, I. [Institute for Microelectronics and Microsystems – Unit of Lecce, National Council of Research (IMM/CNR), Lecce I-73100 (Italy); Maruccio, L. [Department of Engineering for Innovation, University of Salento, Via Monteroni, Lecce I-73100 (Italy); Cola, A. [Institute for Microelectronics and Microsystems – Unit of Lecce, National Council of Research (IMM/CNR), Lecce I-73100 (Italy); Calcagnile, L. [Department of Engineering for Innovation, University of Salento, Via Monteroni, Lecce I-73100 (Italy)

2014-07-15

The implantation of 1 MeV metal ({sup 63}Cu{sup +}, {sup 107}Ag{sup +}, {sup 197}Au{sup +}) and non-metal ({sup 4}He{sup +}, {sup 12}C{sup +}) ions in a polycarbonate (PC) matrix has been studied in order to evaluate the role of ion species in the modification of optical and electrical properties of the polymer. When the ion fluence is above ∼1 × 10{sup 13} ions cm{sup −2}, the threshold for latent tracks overlapping is overcome and π-bonded carbon clusters grow and aggregate forming a network of conjugated C=C bonds. For fluences around 1 × 10{sup 17} ions cm{sup −2}, the aggregation phenomena induce the formation of amorphous carbon and/or graphite like structures. At the same time, nucleation of metal nanoparticles (NPs) from implanted species can take place when the supersaturation threshold is overcome. The optical absorption of the samples increases in the visible range and the optical band gap redshifts from 3.40 eV up to 0.70 eV mostly due to the carbonization process and the formation of C{sub 0x} clusters and cluster aggregates. Specific structures in the extinction spectra are observed when metal ions are selected in contrast to the non-metal ion implanted PC, thus revealing the possible presence of noble metal based NPs interstitial to the C{sub 0x} cluster network. The corresponding electrical resistance decreases much more when metal ions are implanted with at least a factor of 2 orders of magnitude difference than the non-metal ions based samples. An absolute value of ∼10{sup 7} Ω/sq has been measured for implantation with metals at doses higher than 5 × 10{sup 16} ions cm{sup −2}, being 10{sup 17} Ω/sq the corresponding sheet resistance for pristine PC.

Highly Dense Isolated Metal Atom Catalytic Sites

DEFF Research Database (Denmark)

Chen, Yaxin; Kasama, Takeshi; Huang, Zhiwei

2015-01-01

-ray diffraction. A combination of electron microscopy images with X-ray absorption spectra demonstrated that the silver atoms were anchored on five-fold oxygen-terminated cavities on the surface of the support to form highly dense isolated metal active sites, leading to excellent reactivity in catalytic oxidation......Atomically dispersed noble-metal catalysts with highly dense active sites are promising materials with which to maximise metal efficiency and to enhance catalytic performance; however, their fabrication remains challenging because metal atoms are prone to sintering, especially at a high metal...... loading. A dynamic process of formation of isolated metal atom catalytic sites on the surface of the support, which was achieved starting from silver nanoparticles by using a thermal surface-mediated diffusion method, was observed directly by using in situ electron microscopy and in situ synchrotron X...

Single-atom catalysts for CO2 electroreduction with significant activity and selectivity improvements.

Science.gov (United States)

Back, Seoin; Lim, Juhyung; Kim, Na-Young; Kim, Yong-Hyun; Jung, Yousung

2017-02-01

A single-atom catalyst (SAC) has an electronic structure that is very different from its bulk counterparts, and has shown an unexpectedly high specific activity with a significant reduction in noble metal usage for CO oxidation, fuel cell and hydrogen evolution applications, although physical origins of such performance enhancements are still poorly understood. Herein, by means of density functional theory (DFT) calculations, we for the first time investigate the great potential of single atom catalysts for CO 2 electroreduction applications. In particular, we study a single transition metal atom anchored on defective graphene with single or double vacancies, denoted M@sv-Gr or M@dv-Gr, where M = Ag, Au, Co, Cu, Fe, Ir, Ni, Os, Pd, Pt, Rh or Ru, as a CO 2 reduction catalyst. Many SACs are indeed shown to be highly selective for the CO 2 reduction reaction over a competitive H 2 evolution reaction due to favorable adsorption of carboxyl (*COOH) or formate (*OCHO) over hydrogen (*H) on the catalysts. On the basis of free energy profiles, we identified several promising candidate materials for different products; Ni@dv-Gr (limiting potential U L = -0.41 V) and Pt@dv-Gr (-0.27 V) for CH 3 OH production, and Os@dv-Gr (-0.52 V) and Ru@dv-Gr (-0.52 V) for CH 4 production. In particular, the Pt@dv-Gr catalyst shows remarkable reduction in the limiting potential for CH 3 OH production compared to any existing catalysts, synthesized or predicted. To understand the origin of the activity enhancement of SACs, we find that the lack of an atomic ensemble for adsorbate binding and the unique electronic structure of the single atom catalysts as well as orbital interaction play an important role, contributing to binding energies of SACs that deviate considerably from the conventional scaling relation of bulk transition metals.

Synthesis of Single-Walled Carbon Nanotubes: Effects of Active Metals, Catalyst Supports, and Metal Loading Percentage

Directory of Open Access Journals (Sweden)

Wei-Wen Liu

2013-01-01

Full Text Available The effects of active metals, catalyst supports, and metal loading percentage on the formation of single-walled carbon nanotubes (SWNTs were studied. In particular, iron, cobalt, and nickel were investigated for SWNTs synthesis. Iron was found to grow better-quality SWNTs compared to cobalt and nickel. To study the effect of catalyst supports, magnesium oxide, silicon oxide, and aluminium oxide were chosen for iron. Among the studied supports, MgO was identified to be a suitable support for iron as it produced SWNTs with better graphitisation determined by Raman analysis. Increasing the iron loading decreased the quality of SWNTs due to extensive agglomeration of the iron particles. Thus, lower metal loading percentage is preferred to grow better-quality SWNTs with uniform diameters.

Synthesis, characterization and electrochemical studies of Pt-W/C catalyst for polymer electrolyte membrane fuel cells

International Nuclear Information System (INIS)

Ahmed, Riaz; Shahid, Saliha; Ansari, Muhammad Shahid

2014-01-01

Pt-W/C catalyst was synthesized by slow reduction of platinum and tungsten solutions in the desired ratio with subsequent deposition on the Vulcan carbon already added to the solution. Crystallite size of catalyst was about 9 nm and its density, cell volume, d-spacing and lattice parameter were also calculated. EDX analysis of the catalyst was also done. Electrochemical surface area of the catalyst was determined by cyclic voltammetry (CV). CV of the catalyst was done both in acidic and basic media to find out the peak potential, peak current, specific activity and mass activity of the catalyst. Peak potential versus scan rate plots showed that the electro oxidation of methanol is an irreversible process. Tafel equation was used to plot polarization curves to find out the exchange current density. Higher values of exchange current indicate better catalysts. Specific activities of the catalyst were determined in acidic and basic media and it was found that the specific activity in basic media increased substantially as compared to acidic media. The specific activity in acidic media was 83 mA/mg pt whereas in basic media it was 137mA/mg pt which is a substantial increase. Heterogeneous rate constant in acidic media was 6.15 x 10 −6 cm/ s and in basic media it was 4.92 x 10 −5 cm/s which is much higher in basic media. In this binary catalyst addition of tungsten has increased the catalytic activity but it is non-noble metal thus will decrease the cost. Stability studies of the catalyst were done upto fifty cycles both in acidic and basic media and was found quite stable in both the media

Mesoporous metal catalysts formed by ultrasound

Energy Technology Data Exchange (ETDEWEB)

Schaeferhans, Jana; Pazos Perez, Nicolas; Andreeva, Daria [Physikalische Chemie II, Universitaet Bayreuth (Germany)

2010-07-01

We study the ultrasound-driven formation of mesoporous metal sponges. The collapse of acoustic cavitations leads to very high temperatures and pressures on very short scales. Therefore, structures may be formed and quenched far from equilibrium. Mechanism of metal modification by ultrasound is complex and involves a variety of aspects. We propose that modification of metal particles and formation of mesoporous inner structures can be achieved due to thermal etching of metals by ultrasound stimulated high speed jets of liquid. Simultaneously, oxidation of metal surfaces by free radicals produced in water during cavitation stabilizes developed metal structures. Duration and intensity of the ultrasonication treatment is able to control the structure and morphology of metal sponges. We expect that this approach to the formation of nanoscale composite sponges is universal and opens perspective for a whole new class of catalytic materials that can be prepared in a one-step process. The developed method makes it possible to control the sponge morphology and can be used for formation of modern types of catalysts. For example, the sonication technique allows to combine the fabrication of mesoporous support and distribution of metal (Cu, Pd, Au, Pt etc.) nanoparticles in its pores into a single step.

Surface/structure functionalization of copper-based catalysts by metal-support and/or metal–metal interactions

Energy Technology Data Exchange (ETDEWEB)

Konsolakis, Michalis, E-mail: mkonsol@science.tuc.gr [School of Production Engineering and Management, Technical University of Crete, GR-73100 Chania, Crete (Greece); Ioakeimidis, Zisis [Department of Mechanical Engineering, University of Western Macedonia, Bakola and Sialvera, GR-50100 Kozani (Greece)

2014-11-30

Highlights: • The surface chemistry of Cu-based catalysts is adjusted by metal-support or metal–metal interactions. • Three series of catalysts, i.e., Cu/REOs, Cu/Ce{sub 1−x}Sm{sub x}O{sub δ} and Cu–Co/CeO{sub 2} were prepared. • The local structure of Cu sites is remarkably affected by support or active phase modification. • Useful insights toward the fundamental understanding of Cu-catalyzed reactions are provided. - Abstract: Cu-based catalysts have recently attracted great attention both in catalysis and electro-catalysis fields due to their excellent catalytic performance and low cost. Given that their performance is determined, to a great extent, by Cu sites local environment, considerable efforts have been devoted on the strategic modifications of the electronic and structural properties of Cu sites. In this regard, the feasibility of tuning the local structure of Cu entities by means of metal-support or metal–metal interactions is investigated. More specifically, the physicochemical properties of Cu entities are modified by employing: (i) different oxides (CeO{sub 2}, La{sub 2}O{sub 3}, Sm{sub 2}O{sub 3}), or (ii) ceria-based mixed oxides (Ce{sub 1−x}Sm{sub x}O{sub δ}) as supporting carriers, and (iii) a second metal (Cobalt) adjacent to Cu (bimetallic Cu–Co/CeO{sub 2}). A characterization study, involving BET, XRD, TPR, and XPS, reveal that significant modifications on structural, redox and electronic properties of Cu sites can be induced by adopting either different oxide carriers or bimetallic complexes. Fundamental insights into the tuning of Cu local environment by metal-support or metal–metal interactions are provided, paving the way for real-life industrial applications.

Effect of temperature in hydrocracking of light cycle oil on a noble metal-supported catalyst for fuel production

Energy Technology Data Exchange (ETDEWEB)

Gutierrez, A.; Arandes, J.M.; Castano, P.; Olazar, M.; Bilbao, J. [Universidad del Pais Vasco (UPV-EHU), Departamento de Ingenieria Quimica, Bilbao (Spain); Barona, A. [Universidad del Pais Vasco (UPV-EHU), Escuela de Ingenieria, Departamento de Ingenieria Quimica y Medio Ambiente, Alda, Urkijo s/n, Bilbao (Spain)

2012-04-15

The effect of temperature has been studied in hydrocracking of light cycle oil (LCO), byproduct of fluidized catalytic cracking (FCC) units on a bifunctional catalyst (Pt-Pd/HY zeolite). The increase in both temperature and H{sub 2} partial pressure have an important attenuating effect on catalyst deactivation, given that they decrease sulfur equilibrium adsorption and enhance hydrocracking of coke precursors. Therefore, the catalyst maintains significant hydrodesulfurization and hydrocracking activity. As the temperature is increased, hydrocracking conversion and naphtha selectivity increase, although there is no significant dearomatization of the medium distillate fraction in the range of the studied experimental conditions. 400 C is the more suitable temperature for obtaining a high yield of naphtha with a high content of i-paraffins. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

A theoretical study on the mechanism of hydrogen evolution on non-precious partially oxidized nickel-based heterostructures for fuel cells.

Science.gov (United States)

Pan, Xinju; Zhou, Gang

2018-03-28

It is desirable, yet challenging, to utilize non-precious metals instead of noble-metals as efficient catalysts in the renewable energy manufacturing industry. Using first principles calculations, we study the structural characteristics of partially oxidized nickel-based nanoheterostructures (NiO/Ni NHSs), and the interfacial effects on hydrogen evolution. The origin of the enhanced hydrogen evolution performance is discussed at the microscopic level. This study identifies two types of active sites of the exposed Ni surface available for the hydrogen evolution reaction (HER). One is the hcp-hollow sites near the perimeter boundary that exhibit a more excellent HER performance than platinum (Pt), and the other the second nearest neighbor fcc-hollow sites away from the boundary that exhibit a similar performance to Pt. The interfacial effects result from the competitive charge transfer between NiO and Ni surfaces in NHSs, and enhance the reactivity of NiO/Ni NHSs by shifting the d-states of surface atoms down in energy. The illumination of the mechanism would be helpful for the design of more efficient and cheap transition metal-based catalysts.

Catalytic incineration of CO and VOC emissions over supported metal oxide catalysts

Energy Technology Data Exchange (ETDEWEB)

Larsson, Per-Olof

1999-05-01

Catalytic incineration is one of the methods to reduce the emissions of CO and VOCs. Low operation temperature and low catalyst cost are essential parameters for catalytic incinerators. Pt/Al{sub 2}O{sub 3} catalysts are frequently used today, but the cheaper metal oxide catalysts can be very competitive if comparable overall activity is obtained. This thesis concerns how it is possible to decrease the operation temperature for supported metal oxide catalysts by using different supports, active metal oxides and additives. In the thesis it is demonstrated that different copper oxide based catalysts have the best activity and durability for complete oxidation among several tested metal oxide catalysts. CuO{sub x} supported on TiO{sub 2} and Al{sub 2}O{sub 3} showed increased activity with the CuO{sub x} loading up to the threshold coverage for formation of crystalline CuO particles, which is 12 {mu}mol/m{sup 2} on TiO{sub 2} and 6 {mu}mol/m{sup 2} on Al{sub 2}O{sub 3}. Up to the threshold coverage for CuO formation, well dispersed copper oxide species were formed on TiO{sub 2}, and a dispersed copper aluminate surface phase was formed on Al{sub 2}O{sub 3}. Durability tests showed accelerated sintering of TiO{sub 2} by copper, but stabilisation was possible by modification of the TiO{sub 2} with CeO{sub x} before the deposition of CuO{sub x}. The stabilisation was obtained by formation of a Ce-O-Ti surface phase. Addition of CeO{sub x} also enhanced the activity of the copper oxide species thanks to favourable interaction between the active copper oxide species and the CeO{sub x} on the support, which could be seen as increased reducibility in TPR experiments. The increased activity and reducibility was also observed for CuO{sub x} supported on ceria modified Al{sub 2}O{sub 3}. In this regard it was shown that CuO{sub x} deposited on CeO{sub 2}(001) surfaces was substantially more active for CO oxidation than copper oxide deposited on CeO{sub 2}(111) Surfaces. This

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

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.

Spray pyrolysis synthesis of γ-Al_2O_3 supported metal and metal phosphide catalysts and their activity in the hydrodeoxygenation of a bio-oil model compound

International Nuclear Information System (INIS)

Ly, Hoang Vu; Im, Kyungmin; Go, Youngchae; Galiwango, Emmanuel; Kim, Seung-Soo; Kim, Jinsoo; Choi, Jae Hyung; Woo, Hee Chul

2016-01-01

Highlights: • Spherical γ-Al_2O_3 supported metal and metal phosphide catalysts were synthesized by spray pyrolysis method. • Hydrodeoxygenation (HDO) of 2-furyl methyl ketone (FMK) was conducted using metal/metal phosphide catalysts. • FMK was converted into 2-allyl furan and methyl cyclohexane. • The highest FMK conversion of 83% was achieved over 10 wt% Ni/γ-Al_2O_3 catalysts at reaction temperature of 400 °C. - Abstract: In this study, spherical γ-Al_2O_3 supported metal and metal phosphide (Ni, Co, Ni_2P and CoP) catalysts were successfully prepared by combining sol-gel and spray pyrolysis methods. First boehmite sol was prepared based on the Yoldas process and then the corresponding metal salts were added to the sol at the desired concentration, followed by spray pyrolysis of the mixed solution. As the well-mixed solution was transformed to spherical γ-Al_2O_3 supported metal and metal phosphide catalysts during spray pyrolysis process, the metal species were uniformly distributed in the mesoporous γ-Al_2O_3 supports. The product catalysts were investigated under different conditions for hydrodeoxygenation of bio-oil model compound, 2-furyl methyl ketone (FMK), which is the main component of the bio-oil product from pyrolysis of Saccharina japonica. Among the investigated catalysts, the 10 wt% Ni/γ-Al_2O_3 catalyst after calcination at 800 °C showed the highest FMK conversion of 83.02% at the reaction temperature of 400 °C. The gas and liquid products were analyzed by gas chromatography (GC) with TCD/FID detectors and GC–MS, respectively, to determine the product compositions.

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.

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

A review of metal recovery from spent petroleum catalysts and ash.

Science.gov (United States)

Akcil, Ata; Vegliò, Francesco; Ferella, Francesco; Okudan, Mediha Demet; Tuncuk, Aysenur

2015-11-01

With the increase in environmental awareness, the disposal of any form of hazardous waste has become a great concern for the industrial sector. Spent catalysts contribute to a significant amount of the solid waste generated by the petrochemical and petroleum refining industry. Hydro-cracking and hydrodesulfurization (HDS) catalysts are extensively used in the petroleum refining and petrochemical industries. The catalysts used in the refining processes lose their effectiveness over time. When the activity of catalysts decline below the acceptable level, they are usually regenerated and reused but regeneration is not possible every time. Recycling of some industrial waste containing base metals (such as V, Ni, Co, Mo) is estimated as an economical opportunity in the exploitation of these wastes. Alkali roasted catalysts can be leached in water to get the Mo and V in solution (in which temperature plays an important role during leaching). Several techniques are possible to separate the different metals, among those selective precipitation and solvent extraction are the most used. Pyrometallurgical treatment and bio-hydrometallurgical leaching were also proposed in the scientific literature but up to now they did not have any industrial application. An overview on patented and commercial processes was also presented. Copyright © 2015 Elsevier Ltd. All rights reserved.

Selective propene oxidation on mixed metal oxide catalysts

International Nuclear Information System (INIS)

James, David William

2002-01-01

Selective catalytic oxidation processes represent a large segment of the modern chemical industry and a major application of these is the selective partial oxidation of propene to produce acrolein. Mixed metal oxide catalysts are particularly effective in promoting this reaction, and the two primary candidates for the industrial process are based on iron antimonate and bismuth molybdate. Some debate exists in the literature regarding the operation of these materials and the roles of their catalytic components. In particular, iron antimonate catalysts containing excess antimony are known to be highly selective towards acrolein, and a variety of proposals for the enhanced selectivity of such materials have been given. The aim of this work was to provide a direct comparison between the behaviour of bismuth molybdate and iron antimonate catalysts, with additional emphasis being placed on the component single oxide phases of the latter. Studies were also extended to other antimonate-based catalysts, including cobalt antimonate and vanadium antimonate. Reactivity measurements were made using a continuous flow microreactor, which was used in conjunction with a variety of characterisation techniques to determine relationships between the catalytic behaviour and the properties of the materials. The ratio of Fe/Sb in the iron antimonate catalyst affects the reactivity of the system under steady state conditions, with additional iron beyond the stoichiometric value being detrimental to the acrolein selectivity, while extra antimony provides a means of enhancing the selectivity by decreasing acrolein combustion. Studies on the single antimony oxides of iron antimonate have shown a similarity between the reactivity of 'Sb 2 O 5 ' and FeSbO 4 , and a significant difference between these and the Sb 2 O 3 and Sb 2 O 4 phases, implying that the mixed oxide catalyst has a surface mainly comprised of Sb 5+ . The lack of reactivity of Sb 2 O 4 implies a similarity of the surface with

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)

Electrodes synthesized from carbon nanostructures coated with a smooth and conformal metal adlayer

Science.gov (United States)