Silica Supported Platinum Catalysts for Total Oxidation of the Polyaromatic Hydrocarbon Naphthalene: An Investigation of Metal Loading and Calcination Temperature

Directory of Open Access Journals (Sweden)

David R. Sellick

2015-04-01

Full Text Available A range of catalysts comprising of platinum supported on silica, prepared by an impregnation method, have been studied for the total oxidation of naphthalene, which is a representative Polycyclic Aromatic Hydrocarbon. The influence of platinum loading and calcination temperature on oxidation activity was evaluated. Increasing the platinum loading up to 2.5 wt.% increased the catalyst activity, whilst a 5.0 wt.% catalyst was slightly less active. The catalyst containing the optimum 2.5 wt.% loading was most active after calcination in air at 550 °C. Characterisation by carbon monoxide chemisorption and X-ray photoelectron spectroscopy showed that low platinum dispersion to form large platinum particles, in combination with platinum in metallic and oxidised states was important for high catalyst activity. Catalyst performance improved after initial use in repeat cycles, whilst there was slight deactivation after prolonged time-on-stream.

Investigation of altenative carbon materials for fuel-cell catalyst support

DEFF Research Database (Denmark)

Larsen, Mikkel Juul

In order to ensure high utilization of the catalyst material in a polymer electrolyte membrane fuel cell (PEMFC) it is usually fixed in the form of nanoparticles on a supporting material. The catalyst is platinum or a platinum alloy, and the commonly used support is carbon black (CB). Although...... structured carbon forms such as graphitized CBs, carbon nanotubes (CNTs), and carbon nanofibres (CNFs). This thesis concerns the investigation of an array of different materials which may prospec-tively replace the conventional materials used in the catalyst. The study comprised 13 carbon samples which...... nanotubes (GMWCNTs), and graphitized carbon nanofibre (CNF), while the Pt/C samples were platinized samples of some of the CNTs and CNFs (Pt/FWCNT, Pt/GMWCNT, and Pt/CNF, respectively) as well as two commercial Pt/CB reference catalysts. Comparative analyses have been performed in order to be able to assess...

Methanol Steam Reforming Promoted by Molten Salt-Modified Platinum on Alumina Catalysts

Science.gov (United States)

Kusche, Matthias; Agel, Friederike; Ní Bhriain, Nollaig; Kaftan, Andre; Laurin, Mathias; Libuda, Jörg; Wasserscheid, Peter

2014-01-01

We herein describe a straight forward procedure to increase the performance of platinum-on-alumina catalysts in methanol steam reforming by applying an alkali hydroxide coating according to the “solid catalyst with ionic liquid layer” (SCILL) approach. We demonstrate by diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and temperature-programmed desorption (TPD) studies that potassium doping plays an important role in the catalyst activation. Moreover, the hygroscopic nature and the basicity of the salt modification contribute to the considerable enhancement in catalytic performance. During reaction, a partly liquid film of alkali hydroxides/carbonates forms on the catalyst/alumina surface, thus significantly enhancing the availability of water at the catalytically active sites. Too high catalyst pore fillings with salt introduce a considerable mass transfer barrier into the system as indicated by kinetic studies. Thus, the optimum interplay between beneficial catalyst modification and detrimental mass transfer effects had to be identified and was found on the applied platinum-on-alumina catalyst at KOH loadings around 7.5 mass %. PMID:25124120

Highly active carbon supported Pd cathode catalysts for direct formic acid fuel cells

Energy Technology Data Exchange (ETDEWEB)

Mikolajczuk-Zychora, A., E-mail: amikolajczuk@ichf.edu.pl [Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw (Poland); Borodzinski, A.; Kedzierzawski, P.; Mierzwa, B. [Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw (Poland); Mazurkiewicz-Pawlicka, M. [Faculty of Materials Science and Engineering, Warsaw University of Technology, Wołoska 141, 02-507 Warsaw (Poland); Faculty of Chemical and Process Engineering, Warsaw University of Technology, Warynskiego 1, Warsaw (Poland); Stobinski, L. [Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw (Poland); Faculty of Chemical and Process Engineering, Warsaw University of Technology, Warynskiego 1, Warsaw (Poland); Ciecierska, E. [Faculty of Materials Science and Engineering, Warsaw University of Technology, Wołoska 141, 02-507 Warsaw (Poland); Zimoch, A.; Opałło, M. [Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw (Poland)

2016-12-01

Highlights: • Palladium catalyst used on the cathode DFAFC is comparable to commercial platinum catalyst. • The treatment of carbon supports in nitric acid(V) increases the electrochemically available metal surface area and the catalytic activity in oxygen reduction reaction of catalysts. - Abstract: One of the drawbacks of low-temperature fuel cells is high price of platinum-based catalysts used for the electroreduction of oxygen at the cathode of the fuel cell. The aim of this work is to develop the palladium catalyst that will replace commonly used platinum cathode catalysts. A series of palladium catalysts for oxygen reduction reaction (ORR) were prepared and tested on the cathode of Direct Formic Acid Fuel Cell (DFAFC). Palladium nanoparticles were deposited on the carbon black (Vulcan) and on multiwall carbon nanotubes (MWCNTs) surface by reduction of palladium(II) acetate dissolved in ethanol. Hydrazine was used as a reducing agent. The effect of functionalization of the carbon supports on the catalysts physicochemical properties and the ORR catalytic activity on the cathode of DFAFC was studied. The supports were functionalized by treatment in nitric acid for 4 h at 80 °C. The structure of the prepared catalysts has been characterized by thermogravimetric analysis (TGA), X-ray diffraction (XRD), transmission electron microscope (TEM) and cyclic voltammetry (CV). Hydrophilicity of the catalytic layers was determined by measuring contact angles of water droplets. The performance of the prepared catalysts has been compared with that of the commercial 20 wt.% Pt/C (Premetek) catalyst. The maximum power density obtained for the best palladium catalyst, deposited on the surface of functionalized carbon black, is the same as that for the commercial Pt/C (Premetek). Palladium is cheaper than platinum, therefore the developed cathode catalyst is promising for future applications.

Oxidative dehydrogenation of aqueous ethanol on a carbon supported platinum catalyst

NARCIS (Netherlands)

Tillaart, van den J.A.A.; Kuster, B.F.M.; Marin, G.B.M.M.

1994-01-01

The kinetics of the selective oxidative dehydrogenation of ethanol to ethanal over a platinum on graphite catalyst with oxygen in water was investigated in a three-phase continuous stirred tank reactor by variation of temp., pH and reactant concns. No effect of the pH on the disappearance rate of

Methanol oxidation at platinum electrodes in acid solution: comparison between model and real catalysts

Directory of Open Access Journals (Sweden)

A. V. TRIPKOVIC

2006-12-01

Full Text Available Methanol oxidation in acid solution was studied at platinum single crystals, Pt(hkl, as the model catalyst, and at nanostructural platinum supported on high surface area carbon, Pt/C, as the real catalyst. The linear extrapolation method was used to determine the beginning of hydroxyl anion adsorption. Structural sensitivity of the adsorption was proved and a correlation with the onset of the methanol oxidation current was established at all catalysts. Bisulfate and chloride anions were found to decrease the methanol oxidation rate, but probably did not influence the reaction parth. The specific activity for the reaction increased in the sequence Pt(110 < Pt/C < Pt(111, suggesting that the activity of the supported Pt catalyst can be correlated with the activities of the dominating crystal planes on its surface.

Reactions of neopentane and neohexane on platinum/Y-zeolite and platinum/silica catalysts

Energy Technology Data Exchange (ETDEWEB)

Foger, K.; Anderson, J.R.

1978-10-13

The hydrocracking/hydroisomerization reaction of 20:1 hydrogen/neopentane at 455-625/sup 0/K was studied on platinum-exchanged sodium, calcium, and lanthanum Y zeolites and Aerosil-supported platinum of 1-20 nm average platinum particle size, by analysis of the product distribution, ESCA, and temperature-programed desorption. The results suggested that the reaction occurs only on platinum and that it proceeds by two parallel pathways which have different activation energies and whose relative proportion depends on the particle size. One pathway is the conventionally accepted one on low-index crystallite facets; the other proceeds on single-surface platinum atoms of low coordination (corner or edge atoms) which become more abundant at lower crystallite size. In both cases, the adsorbed intermediate may undergo either isomerization or hydrogenolysis; the selectivity depends on the hydrogen partial pressure and the relative strength of adsorption of hydrogen and neopentane. Neohexane isomerization selectivity on the same catalysts is consistent with a carbonium ion mechanism on a dual-function catalyst.

Poisoning by carbon monoxide in the hydrogen exchange reaction between deuterium gas and water preadsorbed on a platinum--alumina catalyst

International Nuclear Information System (INIS)

Iida, I.; Tamaru, K.

1979-01-01

Poisoning by carbon monoxide in the exchange reaction between deuterium and the water preadsorbed on a platinum--alumina catalyst was studied, by measuring not only the rate of reaction but also its kinetic behavior and the adsorption of reactants on the catalyst surface. The shape of the poisoning curve is closely associated with the kinetic behavior and exhibited an abrupt change on freezing the adsorbed water below 273 0 K. When the rate is proportional to deuterium pressure and independent of the amount of water adsorbed, the exchange rate dropped sharply by carbon monoxide adsorbed of a few percent coverage without any marked changes in the amount and the rate of hydrogen adsorption on the platinum surface. However, at temperatures lower than 273 0 K and at higher deuterium pressures, the rate depends not on the deuterium pressure but on the amount of water adsorbed. The migration of hydrogen in or through the adsorbed water is seemingly sufficiently suppressed by freezing to control the overall reaction rate. In this case, a small amount of adsorption of carbon monoxide did not show any toxicity, but then a steep poisoning started accompanying a change in the kinetic behavior. It was accordingly demonstrated that the mechanism of the reaction may be better understood by studying poisoning and measuring adsorption, overall rate, and kinetic behavior

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)

Highly active carbon supported Pd cathode catalysts for direct formic acid fuel cells

Science.gov (United States)

Mikolajczuk-Zychora, A.; Borodzinski, A.; Kedzierzawski, P.; Mierzwa, B.; Mazurkiewicz-Pawlicka, M.; Stobinski, L.; Ciecierska, E.; Zimoch, A.; Opałło, M.

2016-12-01

One of the drawbacks of low-temperature fuel cells is high price of platinum-based catalysts used for the electroreduction of oxygen at the cathode of the fuel cell. The aim of this work is to develop the palladium catalyst that will replace commonly used platinum cathode catalysts. A series of palladium catalysts for oxygen reduction reaction (ORR) were prepared and tested on the cathode of Direct Formic Acid Fuel Cell (DFAFC). Palladium nanoparticles were deposited on the carbon black (Vulcan) and on multiwall carbon nanotubes (MWCNTs) surface by reduction of palladium(II) acetate dissolved in ethanol. Hydrazine was used as a reducing agent. The effect of functionalization of the carbon supports on the catalysts physicochemical properties and the ORR catalytic activity on the cathode of DFAFC was studied. The supports were functionalized by treatment in nitric acid for 4 h at 80 °C. The structure of the prepared catalysts has been characterized by thermogravimetric analysis (TGA), X-ray diffraction (XRD), transmission electron microscope (TEM) and cyclic voltammetry (CV). Hydrophilicity of the catalytic layers was determined by measuring contact angles of water droplets. The performance of the prepared catalysts has been compared with that of the commercial 20 wt.% Pt/C (Premetek) catalyst. The maximum power density obtained for the best palladium catalyst, deposited on the surface of functionalized carbon black, is the same as that for the commercial Pt/C (Premetek). Palladium is cheaper than platinum, therefore the developed cathode catalyst is promising for future applications.

Non-platinum nanocatalyst on porous nitrogen-doped carbon fabricated by cathodic vacuum arc plasma technique

Energy Technology Data Exchange (ETDEWEB)

Sirirak, Reungruthai [Material Science Research Center, Faculty of Science, Chiang Mai University, Chiang Mai 50200 (Thailand); Department of Chemistry and Center of Excellence for Innovation in Chemistry (PERCH-CIC), Faculty of Science, Chiang Mai University, Chiang Mai 50200 (Thailand); Sarakonsri, Thapanee, E-mail: tsarakonsri@gmail.com [Material Science Research Center, Faculty of Science, Chiang Mai University, Chiang Mai 50200 (Thailand); Department of Chemistry and Center of Excellence for Innovation in Chemistry (PERCH-CIC), Faculty of Science, Chiang Mai University, Chiang Mai 50200 (Thailand); Medhesuwakul, Min [Plasma & Beam Physics Research Facility, Department of Physics and Materials Science, Faculty of Science, Chiang Mai University, Chiang Mai 50200 (Thailand)

2015-11-30

Highlights: • High surface area porous coral-like nitrogen-doped carbon (NC) and non-platinum nanocatalysts were fabricated on proton exchange membrane using the cathodic vacuum arc plasma (CVAP) technique. • It is a one-step catalysts preparation directly on nafion proton exchange membrane. This CVAP technique is the first new method that was applied in a polymer electrolyte membrane fuel cells (PEMFCs) catalysts preparation. • Due to these excellent characteristics of nitrogen-doped carbon, it is expected to exhibit a good catalyst supporter for PEMFC. • In addition, the Fe–NC catalysts fabricated via this CVAP technique are sphere-like nanoparticle and well disperse on coral-like NC film, which particularity exhibits that these prepared catalysts ought to be a good oxygen reduction reaction (ORR) catalyst for PEMFC. • This approach can be extended to the synthesis of other non-platinum ORR catalyst for broad range applications in energy conversion. - Abstract: Polymer electrolyte membrane fuel cells (PEMFCs) convert chemical energy directly into electrical energy where catalysts composing of non-noble transition metals, nitrogen, and carbon compounds are the most promising materials to replace the expensive platinum catalysts for oxygen reduction reaction (ORR). In this research, cathodic vacuum arc plasma (CVAP) technique was used to fabricate porous nitrogen doped carbon (NC) and non-platinum catalyst on porous NC (Fe–NC) directly on ion exchange membrane for being used as an ORR catalyst at the cathode. The porous NC layer was fabricated on silicon wafer at 0.05 mTorr, 0.1 mTorr, 0.5 mTorr, 1 mTorr, and 5 mTorr of nitrogen gas inlet. The AFM, and SEM images are observed to be regularly big with quite high hillocks and thin NC layers; these results indicate that the optimum process pressure of nitrogen gas inlet is 5 mTorr for porous NC fabrication. The SEM–EDS detects Fe, N, and C elements in the prepared catalysts, and the XRD pattern reviews

Non-platinum nanocatalyst on porous nitrogen-doped carbon fabricated by cathodic vacuum arc plasma technique

International Nuclear Information System (INIS)

Sirirak, Reungruthai; Sarakonsri, Thapanee; Medhesuwakul, Min

2015-01-01

Highlights: • High surface area porous coral-like nitrogen-doped carbon (NC) and non-platinum nanocatalysts were fabricated on proton exchange membrane using the cathodic vacuum arc plasma (CVAP) technique. • It is a one-step catalysts preparation directly on nafion proton exchange membrane. This CVAP technique is the first new method that was applied in a polymer electrolyte membrane fuel cells (PEMFCs) catalysts preparation. • Due to these excellent characteristics of nitrogen-doped carbon, it is expected to exhibit a good catalyst supporter for PEMFC. • In addition, the Fe–NC catalysts fabricated via this CVAP technique are sphere-like nanoparticle and well disperse on coral-like NC film, which particularity exhibits that these prepared catalysts ought to be a good oxygen reduction reaction (ORR) catalyst for PEMFC. • This approach can be extended to the synthesis of other non-platinum ORR catalyst for broad range applications in energy conversion. - Abstract: Polymer electrolyte membrane fuel cells (PEMFCs) convert chemical energy directly into electrical energy where catalysts composing of non-noble transition metals, nitrogen, and carbon compounds are the most promising materials to replace the expensive platinum catalysts for oxygen reduction reaction (ORR). In this research, cathodic vacuum arc plasma (CVAP) technique was used to fabricate porous nitrogen doped carbon (NC) and non-platinum catalyst on porous NC (Fe–NC) directly on ion exchange membrane for being used as an ORR catalyst at the cathode. The porous NC layer was fabricated on silicon wafer at 0.05 mTorr, 0.1 mTorr, 0.5 mTorr, 1 mTorr, and 5 mTorr of nitrogen gas inlet. The AFM, and SEM images are observed to be regularly big with quite high hillocks and thin NC layers; these results indicate that the optimum process pressure of nitrogen gas inlet is 5 mTorr for porous NC fabrication. The SEM–EDS detects Fe, N, and C elements in the prepared catalysts, and the XRD pattern reviews

Performance of Platinum Nanoparticles / Multiwalled Carbon Nanotubes / Bacterial Cellulose Composite as Anode Catalyst for Proton Exchange Membrane Fuel Cells

Directory of Open Access Journals (Sweden)

Henry Fonda Aritonang

2017-05-01

Full Text Available Highly dispersed platinum (Pt nanoparticles / multiwalled carbon nanotubes (MWCNTs on bacterial cellulose (BC as anode catalysts for proton exchange membrane fuel cells (PEMFC were prepared with various precursors and their electro-catalytic activities towards hydrogen oxidation at 70 oC under non-humidified conditions. The composite was prepared by deposition of Pt nanoparticles and MWCNTs on BC gel by impregnation method using a water solution of metal precursors and MWCNTs followed by reducing reaction using a hydrogen gas. The composite was characterized by using TEM (transmission electron microscopy, EDS (energy dispersive spectroscopy, and XRD (X-ray diffractometry techniques. TEM images and XRD patterns both lead to the observation of spherical metallic Pt nanoparticles with mean diameter of 3-11 nm well impregnated into the BC fibrils. Preliminary tests on a single cell indicate that renewable BC is a good prospect to be explored as a membrane in fuel cell field. Copyright © 2017 BCREC Group. All rights reserved Received: 21st November 2016; Revised: 26th February 2017; Accepted: 27th February 2017 How to Cite: Aritonang, H.F., Kamu, V.S., Ciptati, C., Onggo, D., Radiman, C.L. (2017. Performance of Platinum Nanoparticles / Multiwalled Carbon Nanotubes / Bacterial Cellulose Composite as Anode Catalyst for Proton Exchange Membrane Fuel Cells. Bulletin of Chemical Reaction Engineering & Catalysis, 12 (2: 287-292 (doi:10.9767/bcrec.12.2.803.287-292 Permalink/DOI: http://dx.doi.org/10.9767/bcrec.12.2.803.287-292

Single-Atom Catalyst of Platinum Supported on Titanium Nitride for Selective Electrochemical Reactions.

Science.gov (United States)

Yang, Sungeun; Kim, Jiwhan; Tak, Young Joo; Soon, Aloysius; Lee, Hyunjoo

2016-02-05

As a catalyst, single-atom platinum may provide an ideal structure for platinum minimization. Herein, a single-atom catalyst of platinum supported on titanium nitride nanoparticles were successfully prepared with the aid of chlorine ligands. Unlike platinum nanoparticles, the single-atom active sites predominantly produced hydrogen peroxide in the electrochemical oxygen reduction with the highest mass activity reported so far. The electrocatalytic oxidation of small organic molecules, such as formic acid and methanol, also exhibited unique selectivity on the single-atom platinum catalyst. A lack of platinum ensemble sites changed the reaction pathway for the oxygen-reduction reaction toward a two-electron pathway and formic acid oxidation toward direct dehydrogenation, and also induced no activity for the methanol oxidation. This work demonstrates that single-atom platinum can be an efficient electrocatalyst with high mass activity and unique selectivity. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Rapid and Efficient Collection of Platinum from Karstedt's Catalyst Solution via Ligands-Exchange-Induced Assembly.

Science.gov (United States)

Yang, Gonghua; Wei, Yanlong; Huang, Zhenzhu; Hu, Jiwen; Liu, Guojun; Ou, Ming; Lin, Shudong; Tu, Yuanyuan

2018-02-21

Reported herein is a novel strategy for the rapid and efficient collection of platinum from Karstedt's catalyst solution. By taking advantage of a ligand-exchange reaction between alkynols and the 1,3-divinyltetramethyldisiloxane ligand (M Vi M Vi ) that coordinated with platinum (Pt(0)), the Karstedt's catalyst particles with a size of approximately 2.5 ± 0.7 nm could be reconstructed and assembled into larger particles with a size of 150 ± 35 nm due to the hydrogen bonding between the hydroxyl groups of the alkynol. In addition, because the silicone-soluble M Vi M Vi ligand of the Karstedt's catalyst was replaced by water-soluble alkynol ligands, the resultant large particles were readily dispersed in water, resulting in rapid, efficient, and complete collection of platinum from the Karstedt's catalyst solutions with platinum concentrations in the range from ∼20 000 to 0.05 ppm. Our current strategy not only was used for the rapid and efficient collection of platinum from the Karstedt's catalyst solutions, but it also enabled the precise evaluation of the platinum content in the Karstedt's catalysts, even if this platinum content was extremely low (i.e., 0.05 ppm). Moreover, these platinum specimens that were efficiently collected from the Karstedt's catalyst solutions could be directly used for the evaluation of platinum without the need for pretreatment processes, such as calcination and digestion with hydrofluoric acid, that were traditionally used prior to testing via inductively coupled plasma mass spectrometry in conventional methods.

Electrochemical behavior of platinum nanoparticles on a carbon xerogel support modified with a [(trifluoromethyl)-benzenesulfonyl]imide electrolyte.

Science.gov (United States)

Liu, Bing; Mei, Hua; DesMarteau, Darryl; Creager, Stephen E

2014-12-11

A monoprotic [(trifluoromethyl)benzenesulfonyl]imide (SI) superacid electrolyte was used to covalently modify a mesoporous carbon xerogel (CX) support via reaction of the corresponding trifluoromethyl aryl sulfonimide diazonium zwitterion with the carbon surface. Electrolyte attachment was demonstrated by elemental analysis, acid-base titration, and thermogravimetric analysis. The ion-exchange capacity of the fluoroalkyl-aryl-sulfonimide-grafted carbon xerogel (SI-CX) was ∼0.18 mequiv g(-1), as indicated by acid-base titration. Platinum nanoparticles were deposited onto the SI-grafted carbon xerogel samples by the impregnation and reduction method, and these materials were employed to fabricate polyelectrolyte membrane fuel-cell (PEMFC) electrodes by the decal transfer method. The SI-grafted carbon-xerogel-supported platinum (Pt/SI-CX) was characterized by X-ray diffraction and transmission electron microscopy to determine platinum nanoparticle size and distribution, and the findings are compared with CX-supported platinum catalyst without the grafted SI electrolyte (Pt/CX). Platinum nanoparticle sizes are consistently larger on Pt/SI-CX than on Pt/CX. The electrochemically active surface area (ESA) of platinum catalyst on the Pt/SI-CX and Pt/CX samples was measured with ex situ cyclic voltammetry (CV) using both hydrogen adsorption/desorption and carbon monoxide stripping methods and by in situ CV within membrane electrode assemblies (MEAs). The ESA values for Pt/SI-CX are consistently lower than those for Pt/CX. Some possible reasons for the behavior of samples with and without grafted SI layers and implications for the possible use of SI-grafted carbon layers in PEMFC devices are discussed.

Pretreatment of Platinum/Tin Oxide-Catalyst

Science.gov (United States)

Hess, Robert V.; Paulin, Patricia A.; Miller, Irvin M.; Schryer, David R.; Sidney, Barry D.; Wood, George M.; Upchurch, Billy T.; Brown, Kenneth G.

1987-01-01

Addition of CO to He pretreatment doubles catalytic activity. In sealed, high-energy, pulsed CO2 laser, CO and O2 form as decomposition products of CO2 in laser discharge zone. Products must be recombined, because oxygen concentration of more than few tenths of percent causes rapid deterioration of power, ending in unstable operation. Promising low-temperature catalyst for combining CO and O2 is platinum on tin oxide. New development increases activity of catalyst so less needed for recombination process.

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

Phase-field model for deposition process of platinum nanoparticles on carbon substrate

International Nuclear Information System (INIS)

Yamakawa, S; Hyodo, S; Okazaki-Maeda, K; Kohyama, M

2008-01-01

Platinum supported on a carbon carrier is widely used as a catalyst for polymer electrolyte membrane fuel cells. The catalytic activity is significantly affected by the size distribution and morphologies of the platinum particles. The objective of this study is to extend the phase-field approach to describe the formation process of platinum particles onto the substrate. The microstructural evolution of a nanoparticle was represented by the temporal evolution of the field variables related to the platinum concentration, long-range crystallographic ordering and phase transition. First-principles calculations were performed in order to estimate the interaction energies between several different types of platinum clusters and a graphene sheet. The platinum density profile concentrated over the substrate surface led to the formation of three-dimensional islands in accordance with the Volmer-Weber mode of growth. The size distributions of the platinum particles were sensitive to the heterogeneity of the substrate surface and to the competitive nucleation and growth processes

Characteristics improvement of hydrophobic polytetrafluoroethylene-platinum catalysts for tritium separation

International Nuclear Information System (INIS)

Popescu, I.; Ionita, Gh.; Dobrinescu, D.; Varlam, C.; Stefanescu, I.

2006-01-01

Full text: Based on the long experience of the authors in the preparation, testing and evaluation of the performances of hydrophobic catalysts and based on the reviewed references, this paper presents up-to-date R and D activities on the preparation methods and applications of the hydrophobic catalysts in tritium separation. The objectives of the paper are: how to improve the characteristics and performance of platinum hydrophobic catalysts; to assess and find a new procedure for the preparation of a new improved hydrophobic catalyst. From reviewed references one can conclude that platinum is the most active and efficient catalytic metal while the polytetrafluoroethylene is the best wet-proofing agent. A new improved hydrophobic Pt-catalyst has been proposed and its testing is now underway. The main steps and experimental conditions of preparation are thoroughly discussed. A new wet-proofing agent and new binders (titanium dioxide, cerium dioxide, zirconium dioxide) with a catalytic role are proposed and tested. The physico-structural parameters of the improved catalyst have been determined and are discussed in detail. The new proposal is a promising idea to improve the performance of conventional hydrophobic Pt-catalysts. (authors)

Sulfur tolerant zeolite supported platinum catalysts for aromatics hydrogenation

Energy Technology Data Exchange (ETDEWEB)

Bergem, Haakon

1997-12-31

The increased demand for transportation fuels at the expence of heavier fuel oil has forced the refinery industry to expand their conversion capacity with hydrotreating as one of the key processes. A shift towards more diesel powered vehicles along with tightening fuel regulations demanding cleaner fuels has lead to increasing interest in catalytic processes for the manufacturing of such environmentally acceptable fuels. This provides the motivation for this thesis. Its main objective was to study possible catalysts active for desulfurization, hydrogenation, and ring-opening of aromatics all in the presence of sulfur. A close examination of the physical properties and kinetical behaviour of the chosen catalysts has been performed. A high pressure reactor setup was designed and built for activity measurements. Zeolite supported platinum catalysts were prepared and both the metal and acid functions were characterized utilizing various experimental techniques. Hydrogenation of toluene was used as a model reaction and the effect of sulfur adsorption on the activity and kinetic behaviour of the catalysts was investigated. The catalyst samples showed hydrogenation activities comparable to a commercial Pt/Al2O3 catalyst. There were no clear differences in the effect of the various sulfur compounds studied. Platinum supported on zeolite Y gave considerably more sulfur tolerant catalysts compared to Al2O3 as support. 155 refs., 58 figs., 36 tabs.

Controllable deposition of platinum nanoparticles on single-wall carbon nanohorns as catalyst for direct methanol fuel cells.

Science.gov (United States)

Niu, Ben; Xu, Wei; Guo, Zhengduo; Zhou, Nengzhi; Liu, Yang; Shi, Zujin; Lian, Yongfu

2012-09-01

Uniform and well dispersed platinum nanoparticles were successfully deposited on single-walled carbon nanohorns with the assistance of 4,4-dipydine and ion liquids, respectively. In particular, the size of platinum nanoparticles could be controlled in a very narrow range (2.2 to 2.5 nm) when ion liquids were applied. The crystalline nature of these platinum nanoparticles was confirmed by high resolution transmission electron microscopy observation and X-ray power diffraction analysis, and two species of platinum Pt(0) and Pt(II) were detected by X-ray photoelectron spectroscopy. Electrochemical studies revealed that thus obtained nanocomposites had much better electrocatalytic activity for the methanol oxidation than those prepared with carbon nanotubes as supporter.

Development of Ultra-Low Platinum Alloy Cathode Catalysts for PEM Fuel Cells

Energy Technology Data Exchange (ETDEWEB)

Popov, Branko N. [Univ. of South Carolina, Columbia, SC (United States). Dept. of Chemical Engineering; Weidner, John [Univ. of South Carolina, Columbia, SC (United States)

2016-01-07

The goal of this project is to synthesize a low cost PEM fuel cell cathode catalyst and support with optimized average mass activity, stability of mass activity, initial high current density performance under H₂/air (power density), and catalyst and support stability able to meet 2017 DOE targets for electrocatalysts for transportation applications. Pt*/ACCS-2 catalyst was synthesized according to a novel methodology developed at USC through: (i) surface modification, (ii) metal catalyzed pyrolysis and (iii) chemical leaching to remove excess meal used to dope the support. Pt* stands for suppressed platinum catalyst synthesized with Co doped platinum. The procedure results in increasing carbon graphitization, inclusion of cobalt in the bulk and formation of non-metallic active sites on the carbon surface. Catalytic activity of the support shows an onset potential of 0.86 V for the oxygen reduction reaction (ORR) with well-defined kinetic and mass transfer regions and 2.5% H₂O₂ production. Pt*/ACCS-2 catalyst durability under 0.6-1.0 V potential cycling and support stability under 1.0-1.5 V potential cycling was evaluated. The results indicated excellent catalyst and support performance under simulated start-up/shut down operating conditions (1.0 – 1.5 V, 5000 cycles) which satisfy DOE 2017 catalyst and support durability and activity. The 30% Pt*/ACCS-2 catalyst showed high initial mass activity of 0.34 A/mg_PGM at 0.9 ViR-free and loss of mass activity of 45% after 30,000 cycles (0.6-1.0 V). The catalyst performance under H₂-air fuel cell operating conditions showed only 24 mV (iR-free) loss at 0.8 A/cm² with an ECSA loss of 42% after 30,000 cycles (0.6-1.0 V). The support stability under 1.0-1.5 V potential cycling showed mass activity loss of 50% and potential loss of 8 mV (iR-free) at 1.5 A/cm². The ECSA loss was 22% after 5,000 cycles. Furthermore, the Pt*/ACCS-2 catalyst showed an

Characterizing the structural degradation in a PEMFC cathode catalyst layer : carbon corrosion

Energy Technology Data Exchange (ETDEWEB)

Young, A.; Stumper, J. [Ballard Power Systems, Burnaby, BC (Canada); Gyenge, E. [British Columbia Univ., Vancouver, BC (Canada). Dept. of Chemical and Biological Engineering

2009-07-01

The structural degradation resulting from carbon corrosion of a cathode catalyst layer in a polymer electrolyte membrane fuel cell (PEMFC) was investigated in this study. In order to oxidize the catalyst carbon support, the PEMFC catalyst layer was subjected to a 30 hour accelerated stress test that cycled the cathode potential from 0.1 to 1.5 VRHE at 30 and 150 second intervals. The rate and amount of carbon loss was determined by measuring the carbon dioxide in the exhaust gas. The structural degradation of the catalyst layer was characterized and correlated to the PEMFC performance using cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), scanning electron microscopy (SEM) and polarization analyses. This analysis revealed a clear thinning of the cathode catalyst layer and gas diffusion layer carbon sub-layer, and a reduction in the effective platinum surface area due to the carbon support oxidation. The thinned cathode catalyst layer changed the water management, and increased the voltage loss associated with the oxygen mass transport and catalyst layer ohmic resistance. In order to further develop and verify this methodology for other degradation mechanisms, emphasis was placed on EIS measurements.

Adsorption and temperature-programmed desorption of hydrogen with dispersed platinum and platinum-gold catalysts

Energy Technology Data Exchange (ETDEWEB)

Anderson, J.R.; Foger, K.; Breakspere, R.J.

1979-05-01

Adsorption and temperature-programmed desorption of hydrogen with dispersed platinum and platinum-gold catalysts was studied with 0.9-3Vertical Bar3< platinum on silica gel, aerosil, sodium and lanthanum Y zeolites, and ..gamma..-alumina, and on aerosil-supported gold-platinum alloys containing 2, 10, 24, 33, and 85Vertical Bar3< gold. Surface enrichment with gold in the alloy systems, as derived from hydrogen adsorption data and predicted from surface enrichment theory and electron microscopic measurements of particle size, were in good agreement, which indicated that equilibrium was achieved by the thermal treatment (oxygen at 573/sup 0/K, hydrogen at 620/sup 0/K, repeated cycles) used. Hydrogen spillover to gold was observed at the higher hydrogen pressures tested on the alloys with high gold content, and to the zeolite supports. The temperature-programed desorption profiles were independent of gold content, which indicated that gold acts only as diluent, and that isolated surface platinum atoms become populated with hydrogen atoms either by hydrogen atom spillover from platinum ensembles to gold and from the gold to the isolated platinum, and/or by adsorption of a molecule directly on the isolated platinum and chemisorption of one H atom at an adjacent gold atom. The distribution of surface platinum ensembles was evaluated by a computer simulation method.

Formic acid oxidation at platinum-bismuth catalysts

Directory of Open Access Journals (Sweden)

Popović Ksenija Đ.

2015-01-01

Full Text Available The field of heterogeneous catalysis, specifically catalysis on bimetallic surfaces, has seen many advances over the past few decades. Bimetallic catalysts, which often show electronic and chemical properties that are distinct from those of their parent metals, offer the opportunity to obtain new catalysts with enhanced selectivity, activity, and stability. The oxidation of formic acid is of permanent interest as a model reaction for the mechanistic understanding of the electrooxidation of small organic molecules and because of its technical relevance for fuel cell applications. Platinum is one of the most commonly used catalysts for this reaction, despite the fact that it shows a few significant disadvantages: high cost and extreme susceptibility to poisoning by CO. To solve this problem, several approaches have been used, but generally, they all consist in the modification of platinum with a second element. Especially, bismuth has received significant attention as Pt modifier. According to the results presented in this survey dealing with the effects influencing the formic acid oxidation it was found that two types of Pt-Bi bimetallic catalysts (bulk and low loading deposits on GC showed superior catalytic activity in terms of the lower onset potential and oxidation current density, as well as exceptional stability compared to Pt. The findings in this report are important for the understanding of mechanism of formic acid electrooxidation on a bulk alloy and decorated surface, for the development of advanced anode catalysts for direct formic acid fuel cells, as well as for the synthesis of novel low-loading bimetallic catalysts. The use of bimetallic compounds as the anode catalysts is an effective solution to overcoming the problems of the formic acid oxidation current stability for long term applications. In the future, the tolerance of both CO poisoning and electrochemical leaching should be considered as the key factors in the development

Durability of Carbon Nanofiber (CNF) & Carbon Nanotube (CNT) as Catalyst Support for Proton Exchange Membrane Fuel Cells

DEFF Research Database (Denmark)

Andersen, Shuang Ma; Borghei, Maryam; Lund, Peter

2013-01-01

a standard polyol method were prepared and fabricated as cathodes of Membrane Electrode Assemblies (MEA) for PEMFC. Both the catalysts as such and the MEAs made out of them were evaluated regarding to thermal and electrochemical stability using traditional carbon black (Vulcan XC72) as a reference. Thermal...... gravimetric analysis (TGA), cyclic voltammetry (CV), polarization curve and impedance spectroscopy were applied on the samples under accelerated stress conditions. The carbon nano-materials demonstrated better stability as support for nano-sized platinum catalyst under PEMFC related operating conditions. Due...

Temperature-programmed reduction and cyclic voltammetry of Pt/carbon-fibre paper catalysts for methanol electrooxidation

International Nuclear Information System (INIS)

Attwood, P.A.; McNicol, B.D.; Short, R.T.

1981-01-01

Temperature-programmed reduction (TPR) and cyclic voltammetry (CV) studies of platinum catalysts supported on pyrographite-coated carbon-fibre paper, and prepared by either ion exchange or impregnation, clearly demonstrate the nature of the interactions between the platinum species and the support. After drying the above catalysts at 120 0 C, the ion-exchanged preparation exhibits the stronger interaction with the carbon support, as might be expected since a chemical interaction with carbon surface groups is known to occur in such catalysts. The presence of a fraction of bulk Pt(NH 3 ) 4 (OH) 2 impregnating salt in the impregnated catalyst has been detected using TPR. After air activation at 300 0 C, subambient reduction peaks were observed and the strength of binding of Pt in the ion-exchanged catalyst was reflected by its increased difficulty of reduction in comparison with that of the impregnated catalyst. The stoichiometry of reduction in ion-exchanged catalysts corresponds to Pt 2+ → Pt 0 in both dried and activated catalysts, with a small amount of Pt 4+ present in the latter. Upon activation the impregnated catalyst showed the presence of some Pt metal, which was thought to arise from the decomposition of the fraction of bulk Pt(NH 3 ) 4 (OH) 2 in the dried catalyst. Activation of ion-exchanged catalysts at temperatures higher than 300 0 C led to a progressive weakening of the Pt-support interaction and consequent smaller Pt surface areas. Activation at 500 0 C in air produced Pt metal exclusively and very low Pt surface areas. The strong interaction between Pt and the carbon support upon activation of the ion-exchanged catalyst at 300 0 C is thought to be the origin of the large metal surface area and the high catalytic activity for methanol electrooxidation found upon reduction

A Study of Iron-Nitrogen-Carbon Fuel Cell Catalysts: Chemistry - Nanostructure - Performance

Science.gov (United States)

Workman, Michael J., Jr.

focused ion beam tomography is modified and optimized for platinum-group metal free catalyst layers, facilitating direct observation of catalyst integration into catalyst layers. I present evidence supporting the hypothesis that atomically dispersed iron coordinated with nitrogen are the dominant active sites in these catalysts. Further, that the concentration of surface oxides in the carbon structure, which can be directly influenced by synthesis parameters, correlates with both the concentration of active sites in the material and with fuel cell performance. Catalyst performance is hindered by the addition of carbon nanotubes and by the presence of metallic iron. Evidence consistent with the catalytic active sites residing in the graphitic plane is also presented.

Structural consideration with respect to the thermal stability of a new platinum supported lanthanum-alumina catalyst

International Nuclear Information System (INIS)

Oudet, F.; Bordes, E.; Courtine, P.; Maxant, G.; Lambert, C.; Guerlet, J.P.

1987-01-01

The influence of lanthanum aluminate, LaAlO 3 , on the thermal stability of both alumina and platinum supported alumina catalysts is investigated. In the case of alumina, the stabilization is interpreted in terms of structural coherence between δ-Al 2 O 3 and a three-fold superstructure of LaAlO 3 . The addition of LaAlO 3 , is shown to increase both the dispersion and the resistance to sintering of the platinum supported alumina catalyst. Moreover, lanthanum hexa-aluminate (La-β-Al 2 O 3 ) is present in the platinum catalyst fired at 1150 0 C. These observations are assumed to result for the epitaxial relations between platinum and the lanthanum-alumina support. 23 refs.; 8 figs.; 2 tabs

Observation of ionomer in catalyst ink of polymer electrolyte fuel cell using cryogenic transmission electron microscopy

International Nuclear Information System (INIS)

Takahashi, Shinichi; Shimanuki, Junichi; Mashio, Tetsuya; Ohma, Atsushi; Tohma, Hajime; Ishihara, Ayumi; Ito, Yoshiko; Nishino, Yuri; Miyazawa, Atsuo

2017-01-01

Optimizing the catalyst layer structure is one of the key issues for improving performance despite lower platinum loading. The catalyst ink, consisting of platinum-loaded carbon particles and ionomer dispersed in an aqueous solvent, is a key factor for controlling the structure of the catalyst layer because the catalyst layer is prepared in a wet coating process. For that purpose, we visualized the nanostructure of the ionomer in the catalyst ink by cryogenic electron microscopy, especially cryogenic transmission electron microscopy (cryo-TEM). By cryo-TEM, it was revealed that ionomer molecules formed rod-like aggregates macro-homogeneously in the solvent, and a similar morphology was observed in a carbon-particle-containing solvent. In contrast, ionomer aggregates in the catalyst ink containing platinum nanoparticles loaded on carbon particles were denser in the vicinity of the platinum-loaded carbon particles. That can be attributed to strong interaction between platinum nanoparticles and sulfonic acid groups in the ionomer. It also implies that a good understanding of ionomer morphology in the catalyst ink can play an important role in controlling the catalyst layer microstructure for reducing platinum loading.

Influence of the Synthesis Method for Pt Catalysts Supported on Highly Mesoporous Carbon Xerogel and Vulcan Carbon Black on the Electro-Oxidation of Methanol

Directory of Open Access Journals (Sweden)

Cinthia Alegre

2015-03-01

Full Text Available Platinum catalysts supported on carbon xerogel and carbon black (Vulcan were synthesized with the aim of investigating the influence of the characteristics of the support on the electrochemical performance of the catalysts. Three synthesis methods were compared: an impregnation method with two different reducing agents, sodium borohydride and formic acid, and a microemulsion method, in order to study the effect of the synthesis method on the physico-chemical properties of the catalysts. X-ray diffraction and transmission electron microscopy were applied. Cyclic voltammetry and chronoamperometry were used for studying carbon monoxide and methanol oxidation. Catalysts supported on carbon xerogel presented higher catalytic activities towards CO and CH3OH oxidation than catalysts supported on Vulcan. The higher mesoporosity of carbon xerogel was responsible for the favored diffusion of reagents towards catalytic centers.

Gaseous exchange reaction of deuterium between hydrogen and water on hydrophobic catalyst supporting platinum

International Nuclear Information System (INIS)

Izawa, Hirozumi; Isomura, Shohei; Nakane, Ryohei.

1979-01-01

The deuterium exchange reaction between hydrogen and water in the gas phase where the fed hydrogen gas is saturated with water vapor is studied experimentally by use of the proper hydrophobic catalysts supporting platinum. It is found that the activities of those catalysts for this reaction system are very high compared with the other known ones for the systems in which gas and liquid should coexist on catalyst surfaces, and that the apparent catalytic activity becomes larger as the amount of platinum supported on a catalyst particle increases. By analyses of the data the following informations are obtained. The exchange reaction can be expressed by a first order reversible reaction kinetics. The pore diffusion in the catalyst particles has significant effect on the overall reaction mechanisms. (author)

Platinum-nickel alloy nanoparticles supported on carbon for 3-pentanone hydrogenation

Energy Technology Data Exchange (ETDEWEB)

Zhu, Lihua, E-mail: lihuazhu@stu.xmu.edu.cn [School of Metallurgy and Chemical Engineering, Jiangxi University of Science and Technology, Ganzhou 341000, Jiang Xi (China); Department of Chemical and Biochemical Engineering, National Engineering Laboratory for Green Productions of Alcohols-Ethers-Esters, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005 (China); Zheng, Tuo; Yu, Changlin [School of Metallurgy and Chemical Engineering, Jiangxi University of Science and Technology, Ganzhou 341000, Jiang Xi (China); Zheng, Jinbao [Department of Chemical and Biochemical Engineering, National Engineering Laboratory for Green Productions of Alcohols-Ethers-Esters, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005 (China); Tang, Zhenbiao [School of Metallurgy and Chemical Engineering, Jiangxi University of Science and Technology, Ganzhou 341000, Jiang Xi (China); Zhang, Nuowei [Department of Chemical and Biochemical Engineering, National Engineering Laboratory for Green Productions of Alcohols-Ethers-Esters, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005 (China); Shu, Qing [School of Metallurgy and Chemical Engineering, Jiangxi University of Science and Technology, Ganzhou 341000, Jiang Xi (China); Chen, Bing H., E-mail: chenbh@xmu.edu.cn [Department of Chemical and Biochemical Engineering, National Engineering Laboratory for Green Productions of Alcohols-Ethers-Esters, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005 (China)

2017-07-01

Highlights: • The PtNi/Ni(OH){sub 2}/C catalyst was successfully synthesized at room temperature. • PtNi alloy/C was obtained after PtNi/Ni(OH){sub 2}/C reduced in hydrogen at 300 °C. • Nanostructures of the PtNi catalysts were characterized by numerous techniques. • PtNi alloy/C exhibited high catalytic activity for 3-pentanone hydrogenation. - Abstract: In this work, we prepared the Ni/Ni(OH){sub 2}/C sample at room temperature by hydrazine hydrate reducing method. The galvanic replacement reaction method was applied to deposit platinum on the Ni/Ni(OH){sub 2} nanoparticles, to prepare the PtNi/Ni(OH){sub 2}/C catalyst. The catalyst of platinum-nickel alloy nanoparticles supported on carbon (signed as PtNi/C) was obtained by the thermal treatment of PtNi/Ni(OH){sub 2}/C in flowing hydrogen at 300 °C for 2 h. The size, nanostructure, surface properties, Pt and Ni chemical states of the PtNi/C catalyst were analyzed using powder X-ray diffraction (XRD), transmission electron microscope (TEM) and high resolution transmission electron microscope (HRTEM), high-angle annular dark-field scanning TEM (HAADF-STEM) and elemental energy dispersive X-ray spectroscopy (EDS) line scanning, X-ray photoelectron spectroscopy (XPS) and high-sensitivity low-energy ion scattering spectroscopy (HS-LEIS) techniques. The as-synthesized PtNi/C catalyst showed enhanced catalytic performance relative to the Ni/Ni(OH){sub 2}/C, Ni/C, Pt/C and PtNi/Ni(OH){sub 2}/C catalysts for 3-pentanone hydrogenation due to electron synergistic effect between Pt and Ni species in the PtNi/C catalyst. The PtNi/C catalyst also had exceling stability, with industrial application value.

Hydrogen Temperature-Programmed Desorption (H2 TPD) of Supported Platinum Catalysts.

NARCIS (Netherlands)

Koningsberger, D.C.; Miller, J.T.; Meyers, B.L.; Modica, F.S.; Lane, G.S.; Vaarkamp, M.

1993-01-01

Hydrogen temperature-programmed desorption (TPD) of supported platinum catalysts, Pt/KLTL, Pt/H-LTL, Pt/K-MAZ, Pt/H-MAZ, Pt/-Al2O3, and Pt/SiO2, was performed after hydrogen reduction at 300, 450, or 650°C. For all catalysts, reversible desorption of chemisorbed hydrogen occurred at approximately

Determination of surface coverage of catalysts : temperature programmed experiments on platinum and iridium sponge catalysts after low temperature ammonia oxidation

NARCIS (Netherlands)

van den Broek, A.C.M.; Grondelle, van J.; Santen, van R.A.

1999-01-01

The activity of iridium and platinum sponge catalysts was studied in the low temperature gas phase oxidation of ammonia with oxygen. Under the reaction conditions used, iridium was found to be more active and more selective to nitrogen than platinum. Furthermore it was established from activity

Power generation in microbial fuel cells using platinum group metal-free cathode catalyst: Effect of the catalyst loading on performance and costs.

Science.gov (United States)

Santoro, Carlo; Kodali, Mounika; Herrera, Sergio; Serov, Alexey; Ieropoulos, Ioannis; Atanassov, Plamen

2018-02-28

Platinum group metal-free (PGM-free) catalyst with different loadings was investigated in air breathing electrodes microbial fuel cells (MFCs). Firstly, the electrocatalytic activity towards oxygen reduction reaction (ORR) of the catalyst was investigated by rotating ring disk electrode (RRDE) setup with different catalyst loadings. The results showed that higher loading led to an increased in the half wave potential and the limiting current and to a further decrease in the peroxide production. The electrons transferred also slightly increased with the catalyst loading up to the value of ≈3.75. This variation probably indicates that the catalyst investigated follow a 2x2e - transfer mechanism. The catalyst was integrated within activated carbon pellet-like air-breathing cathode in eight different loadings varying between 0.1 mgcm -2 and 10 mgcm -2 . Performance were enhanced gradually with the increase in catalyst content. Power densities varied between 90 ± 9 μWcm -2 and 262 ± 4 μWcm -2 with catalyst loading of 0.1 mgcm -2 and 10 mgcm -2 respectively. Cost assessments related to the catalyst performance are presented. An increase in catalyst utilization led to an increase in power generated with a substantial increase in the whole costs. Also a decrease in performance due to cathode/catalyst deterioration over time led to a further increase in the costs.

Platinum-gold nanoclusters as catalyst for direct methanol fuel cells.

Science.gov (United States)

Giorgi, L; Giorgi, R; Gagliardi, S; Serra, E; Alvisi, M; Signore, M A; Piscopiello, E

2011-10-01

Nanosized platinum-gold alloys clusters have been deposited on gas diffusion electrode by sputter deposition. The deposits were characterized by FE-SEM, TEM and XPS in order to verify the formation of alloy nanoparticles and to study the influence of deposition technique on the nanomorphology. The deposition by sputtering process allowed a uniform distribution of metal particles on porous surface of carbon supports. Typical island growth mode was observed with the formation of a dispersed metal nanoclusters (mean size about 5 nm). Cyclic voltammetry was used to determine the electrochemical active surface and the electrocatalytic performance of the PtAu electrocatalysts for methanol oxidation reaction. The data were re-calculated in the form of mass specific activity (MSA). The sputter-catalyzed electrodes showed higher performance and stability compared to commercial catalysts.

Tungsten carbide/porous carbon composite as superior support for platinum catalyst toward methanol electro-oxidation

International Nuclear Information System (INIS)

Jiang, Liming; Fu, Honggang; Wang, Lei; Mu, Guang; Jiang, Baojiang; Zhou, Wei; Wang, Ruihong

2014-01-01

Graphical abstract: The WC nanoparticles are well dispersed in the carbon matrix. The size of WC nanoparticles is about 30 nm. It can be concluded that tungsten carbide and carbon composite was successfully prepared by the present synthesis conditions. - Highlights: • The WC/PC composite with high specific surface area was prepared by a simple way. • The Pt/WC/PC catalyst has superior performance toward methanol electro-oxidation. • The current density for methanol electro-oxidation is as high as 595.93 A g −1 Pt. • The Pt/WC/PC catalyst shows better durability and stronger CO electro-oxidation. • The performance of Pt/WC/PC is superior to the commercial Pt/C (JM) catalyst. - Abstract: Tungsten carbide/porous carbon (WC/PC) composites have been successfully synthesized through a surfactant assisted evaporation-induced-assembly method, followed by a thermal treatment process. In particular, WC/PC-35-1000 composite with tungsten content of 35% synthesized at the carbonized temperature of 1000 °C, exhibited a specific surface area (S BET ) of 457.92 m 2 g −1 . After loading Pt nanoparticles (NPs), the obtained Pt/WC/PC-35-1000 catalyst exhibits the highest unit mass electroactivity (595.93 A g −1 Pt) toward methanol electro-oxidation, which is about 2.6 times as that of the commercial Pt/C (JM) catalyst. Furthermore, the Pt/WC/PC-35-1000 catalyst displays much stronger resistance to CO poisoning and better durability toward methanol electrooxidation compared with the commercial Pt/C (JM) catalyst. The high electrocatalytic activity, strong poison-resistivity and good stability of Pt/WC/PC-35-1000 catalyst are attributed to the porous structures and high specific surface area of WC/PC support could facilitate the rapid mass transportation. Moreover, synergistic effect between WC and Pt NPs is favorable to the higher catalytic performance

A Simple Synthesis of an N-Doped Carbon ORR Catalyst: Hierarchical Micro/Meso/Macro Porosity and Graphitic Shells

NARCIS (Netherlands)

Eisenberg, D.; Stroek, W.; Geels, N.J.; Sandu, C.S.; Heller, A.; Yan, N.; Rothenberg, G.

2016-01-01

Replacing platinum as an oxygen reduction catalyst is an important scientific and technological challenge. Herein we report a simple synthesis of a complex carbon with very good oxygen reduction reaction (ORR) activity at pH 13. Pyrolysis of magnesium nitrilotriacetate yields a carbon with

Oxidation of 4-methoxy-1-naphthol on promoted platinum catalysts

CSIR Research Space (South Africa)

Maphoru, MV

2017-07-01

Full Text Available , July 2017, Volume 58, Issue 4, pp 441–447 Oxidation of 4-methoxy-1-naphthol on promoted platinum catalysts M. V. Maphoru J. Heveling S. Kesavan Pillai Abstract Oxidative coupling of naphthols is a useful method for the formation of new...

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

NARCIS (Netherlands)

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

2014-01-01

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

CATALYSTS NHI Thermochemical Systems FY 2009 Year-End Report

International Nuclear Information System (INIS)

Ginosar, Daniel M.

2009-01-01

Fiscal Year 2009 work in the Catalysts project focused on advanced catalysts for the decomposition of sulfuric acid, a reaction common to both the Sulfur-Iodine (S-I) cycle and the Hybrid Sulfur cycle. Prior years effort in this project has found that although platinum supported on titanium oxide will be an acceptable catalyst for sulfuric acid decomposition in the integrated laboratory scale (ILS) project, the material has short comings, including significant cost and high deactivation rates due to sintering and platinum evaporation. For pilot and larger scale systems, the catalyst stability needs to be improved significantly. In Fiscal Year 2008 it was found that at atmospheric pressure, deactivation rates of a 1 wt% platinum catalyst could be reduced by 300% by adding either 0.3 wt% iridium (Ir) or 0.3 wt% ruthenium (Ru) to the catalyst. In Fiscal Year 2009, work focused on examining the platinum group metal catalysts activity and stability at elevated pressures. In addition, simple and complex metal oxides are known to catalyze the sulfuric acid decomposition reaction. These metal oxides could offer activities comparable to platinum but at significantly reduced cost. Thus a second focus for Fiscal Year 2009 was to explore metal oxide catalysts for the sulfuric acid decomposition reaction. In Fiscal Year 2007 several commercial activated carbons had been identified for the HI decomposition reaction; a reaction specific to the S-I cycle. Those materials should be acceptable for the pilot scale project. The activated carbon catalysts have some disadvantages including low activity at the lower range of reactor operating temperature (350 to 400 C) and a propensity to generate carbon monoxide in the presence of water that could contaminate the hydrogen product, but due to limited funding, this area had low priority in Fiscal Year 2009. Fiscal Year 2009 catalyst work included five tasks: development, and testing of stabilized platinum based H2SO4 catalysts

EFFECT OF IMPREGNATION PROCEDURE OF Pt/γ-Al2O3 CATALYSTS UPON CATALYTIC OXIDATION OF CO

Directory of Open Access Journals (Sweden)

Triyono Triyono

2010-06-01

Full Text Available The oxidation of carbon monoxide by oxygen using two catalysts prepared by two different methods has been investigated. In the first method, catalyst prepared by immersing γ-Al2O3 into the hexa-chloroplatinic acid solution at 80oC for 4 h, resulted Pt/γ-Al2O3 catalyst having platinum highly dispersed on the support. While that of immersing γ-Al2O3 in the hexa-chloroplatinic acid solution at room temperature for 12 h, produced Pt/ γ-Al2O3 catalyst where platinum dispersion was much lower. Catalytic activity test showed that platinum well dispersed on the support enhanced the activity of oxidation of carbon monoxide. The platinum impregnated at room temperature resulted in the poor activity.   Keyword: Catalyst, CO Oxidation, Platinum.

Elaboration, physical and electrochemical characterizations of CO tolerant PEMFC anode materials. Study of platinum-molybdenum and platinum-tungsten alloys and composites; Elaborations et caracterisations electrochimiques et physiques de materiaux d'anode de PEMFC peu sensibles a l'empoisonnement par CO: etude d'alliages et de composites a base de platine-molybdene et de platine-tungstene

Energy Technology Data Exchange (ETDEWEB)

Peyrelade, E.

2005-06-15

PEMFC development is hindered by the CO poisoning ability of the anode platinum catalyst. It has been previously shown that the oxidation potential of carbon monoxide adsorbed on the platinum atoms can be lowered using specific Pt based catalysts, either metallic alloys or composites. The objective is then to realize a catalyst for which the CO oxidation is compatible with the working potential of a PEMFC anode. In our approach, to enhance the CO tolerance of platinum based catalyst supported on carbon, we studied platinum-tungsten and platinum-molybdenum alloys and platinum-metal oxide materials (Pt-WO{sub x} and Pt-MoO{sub x}). The platinum based alloys demonstrate a small effect of the second metal towards the oxidation of carbon monoxide. The platinum composites show a better tolerance to carbon monoxide. Electrochemical studies on both Pt-MoO{sub x} and Pt-WO{sub x} demonstrate the ability of the metal-oxides to promote the ability of Pt to oxidize CO at low potentials. However, chrono-amperometric tests reveal a bigger influence of the tungsten oxide. Complex chemistry reactions on the molybdenum oxide surface make it more difficult to observe. (author)

Tungsten carbide/porous carbon composite as superior support for platinum catalyst toward methanol electro-oxidation

Energy Technology Data Exchange (ETDEWEB)

Jiang, Liming [School of Chemical Engineering and Technology, Harbin Institute of Technology, Harbin 150001 (China); Fu, Honggang, E-mail: fuhg@vip.sina.com [School of Chemical Engineering and Technology, Harbin Institute of Technology, Harbin 150001 (China); Key Laboratory of Functional Inorganic Material Chemistry, Heilongjiang University, Harbin 150080 (China); Wang, Lei; Mu, Guang; Jiang, Baojiang; Zhou, Wei; Wang, Ruihong [Key Laboratory of Functional Inorganic Material Chemistry, Heilongjiang University, Harbin 150080 (China)

2014-01-01

Graphical abstract: The WC nanoparticles are well dispersed in the carbon matrix. The size of WC nanoparticles is about 30 nm. It can be concluded that tungsten carbide and carbon composite was successfully prepared by the present synthesis conditions. - Highlights: • The WC/PC composite with high specific surface area was prepared by a simple way. • The Pt/WC/PC catalyst has superior performance toward methanol electro-oxidation. • The current density for methanol electro-oxidation is as high as 595.93 A g{sup −1} Pt. • The Pt/WC/PC catalyst shows better durability and stronger CO electro-oxidation. • The performance of Pt/WC/PC is superior to the commercial Pt/C (JM) catalyst. - Abstract: Tungsten carbide/porous carbon (WC/PC) composites have been successfully synthesized through a surfactant assisted evaporation-induced-assembly method, followed by a thermal treatment process. In particular, WC/PC-35-1000 composite with tungsten content of 35% synthesized at the carbonized temperature of 1000 °C, exhibited a specific surface area (S{sub BET}) of 457.92 m{sup 2} g{sup −1}. After loading Pt nanoparticles (NPs), the obtained Pt/WC/PC-35-1000 catalyst exhibits the highest unit mass electroactivity (595.93 A g{sup −1} Pt) toward methanol electro-oxidation, which is about 2.6 times as that of the commercial Pt/C (JM) catalyst. Furthermore, the Pt/WC/PC-35-1000 catalyst displays much stronger resistance to CO poisoning and better durability toward methanol electrooxidation compared with the commercial Pt/C (JM) catalyst. The high electrocatalytic activity, strong poison-resistivity and good stability of Pt/WC/PC-35-1000 catalyst are attributed to the porous structures and high specific surface area of WC/PC support could facilitate the rapid mass transportation. Moreover, synergistic effect between WC and Pt NPs is favorable to the higher catalytic performance.

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...

Development of radioactive platinum group metal catalysts

International Nuclear Information System (INIS)

Chung, H.S.; Kim, Y.S.; Kim, Y.E.

1999-03-01

The fission product nuclides generated during the irradiation of reactor fuel include many useful elements, among them platinum group metals such as ruthenium, rhodium and palladium which are of great industrial importance, occur rarely in nature and are highly valuable. In this research, the authors reviewed various PGM recovery methods. Recovery of palladium from seven-component simulated waste solutions was conducted by selective precipitation method. The recovery yield was more than 99.5% and the purity of the product was more than 99%. Wet-proof catalyst was prepared with the recovered palladium. The specific surface area of the catalyst support was more than 400m 2 /g. The content of palladium impregnated on the support was 1 to 10 wt. %. Hydrogen isotope exchange efficiency of more than 93% to equilibrium with small amount of the catalyst was obtained. It was turned out possible to consider using such palladium or other very low active PGM materials in applications where its activity is unimportant as in nuclear industries. (author). 86 refs., 44 tabs., 88 figs

Development of radioactive platinum group metal catalysts

Energy Technology Data Exchange (ETDEWEB)

Chung, H.S.; Kim, Y.S.; Kim, Y.E. [and others

1999-03-01

The fission product nuclides generated during the irradiation of reactor fuel include many useful elements, among them platinum group metals such as ruthenium, rhodium and palladium which are of great industrial importance, occur rarely in nature and are highly valuable. In this research, the authors reviewed various PGM recovery methods. Recovery of palladium from seven-component simulated waste solutions was conducted by selective precipitation method. The recovery yield was more than 99.5% and the purity of the product was more than 99%. Wet-proof catalyst was prepared with the recovered palladium. The specific surface area of the catalyst support was more than 400m{sup 2}/g.The content of palladium impregnated on the support was 1 to 10 wt. %. Hydrogen isotope exchange efficiency of more than 93% to equilibrium with small amount of the catalyst was obtained. It was turned out possible to consider using such palladium or other very low active PGM materials in applications where its activity is unimportant as in nuclear industries. (author). 86 refs., 44 tabs., 88 figs.

Catalytic transformation of carbon dioxide and methane into syngas over ruthenium and platinum supported hydroxyapatites

International Nuclear Information System (INIS)

Rêgo De Vasconcelos, Bruna; Zhao, Lulu; Sharrock, Patrick; Nzihou, Ange; Pham Minh, Doan

2016-01-01

Highlights: • Formation of nanoparticles of Pt and Ru on hydroxyapatite surface support (HAP). • Pt catalyst more active and stable than Ru catalyst in dry reforming of methane (DRM). • Low carbon deposition on the surface of Pt catalyst after reaction. • Quantification of water as by-product of the reaction for the first time. • Good mass balance of the reaction. - Abstract: This work focused on the catalytic transformation of methane (CH 4 ) and carbon dioxide (CO 2 ) into syngas (mixture of CO and H 2 ). Ruthenium- and platinum-based catalysts were prepared using hydroxyapatite (HAP) as catalyst support. Different methods for metal deposition were used including incipient wetness impregnation (IWI), excess liquid phase impregnation (LIM), and cationic exchange (CEX). Metal particle size varied in large range from less than 1 nm to dozens nm. All catalysts were active at 400–700 °C but only Pt catalyst prepared by IWI method (Pt/HAP IWI) was found stable. The catalytic performance of Pt/HAP IWI could be comparable with the literature data on noble metal-based catalysts, prepared on metal oxide supports. For the first time, water was experimentally quantified as a by-product of the reaction. This helped to correctly buckle the mass balance of the process.

Catalytic transformation of carbon dioxide and methane into syngas over ruthenium and platinum supported hydroxyapatites

Energy Technology Data Exchange (ETDEWEB)

Rêgo De Vasconcelos, Bruna; Zhao, Lulu; Sharrock, Patrick; Nzihou, Ange; Pham Minh, Doan, E-mail: doan.phamminh@mines-albi.fr

2016-12-30

Highlights: • Formation of nanoparticles of Pt and Ru on hydroxyapatite surface support (HAP). • Pt catalyst more active and stable than Ru catalyst in dry reforming of methane (DRM). • Low carbon deposition on the surface of Pt catalyst after reaction. • Quantification of water as by-product of the reaction for the first time. • Good mass balance of the reaction. - Abstract: This work focused on the catalytic transformation of methane (CH{sub 4}) and carbon dioxide (CO{sub 2}) into syngas (mixture of CO and H{sub 2}). Ruthenium- and platinum-based catalysts were prepared using hydroxyapatite (HAP) as catalyst support. Different methods for metal deposition were used including incipient wetness impregnation (IWI), excess liquid phase impregnation (LIM), and cationic exchange (CEX). Metal particle size varied in large range from less than 1 nm to dozens nm. All catalysts were active at 400–700 °C but only Pt catalyst prepared by IWI method (Pt/HAP IWI) was found stable. The catalytic performance of Pt/HAP IWI could be comparable with the literature data on noble metal-based catalysts, prepared on metal oxide supports. For the first time, water was experimentally quantified as a by-product of the reaction. This helped to correctly buckle the mass balance of the process.

Separation of deuterium by H2/H2O reaction with hydrophobic platinum catalyst

International Nuclear Information System (INIS)

Kitamoto, A.; Takashima, Y.; Shimizu, M.

The separation performance of a trickle bed exchange column packed with a hydrophobic or waterproof catalyst is related to operating conditions such as hydrogen surface velocity, water flow rate, and temperature. The optimum carrier type and catalyst platinum content were determined. The continuous injection of roughly 10 3 ppm O 2 regenerates the catalyst effectively. The ratio of hydrophobic catalyst to hydrophilic packing is an important factor in increasing the exchange rate in deuterium extraction

Development of industrial hydrogenating catalyst on rhenium base

International Nuclear Information System (INIS)

Chistyakova, G.A.; Bat', I.I.; Rebrova, V.V.

1975-01-01

Processes for forming rhenium catalysts on carbon carrier and their catalytic properties in nitrobenzene (NB) reduction were studied. Application of an ammonia preparation to the carbon surface produced impregnated carbon saturated at room temperature with a water solution of the ammonia preparation, taken in a volume equal to the volumetric capacity of the carbon. With one impregnation, 2% rhenium was taken up. Catalysts containing more than 5% rhenium were obtained by impregnating the carbon with heating and use of more concentrated solutions. Catalysts made in this way and dried at 100 0 C had the composition Re 2 OH/carbon/. The most active catalysts were those reduced at 200-250 0 C; higher temperatures, up to 300-500 0 C, decreased the activity. Study of the catalytic properties of the rhenium catalysts in a liquid phase reduction of NB showed that the specific activity of rhenium depends only slightly on the content of the active component in the catalyst and is close to the specific activity of palladium and considerably exceeds that of nickel. Study of the effect of the NB concentration and hydrogen pressure on the activity and stability of the 5% rhenium catalyst indicated that with NB concentrations from 50 to 10% the process takes place at an essentially constant rate; the order of the reaction was close to zero with an apparent activation energy of about 7000 cal/mole. At pressures of 15-200 atm the yield with the 5% catalyst was proportional to the hydrogen pressure. A big advantage of the rhenium catalysts in the reduction of NB is their high selectivity. With a higher activity than palladium and nickel catalysts, 5% rhenium catalyst produces a high operating capacity in a wide range of contact charges, which has considerable significance for industrial use in contact apparatus of the column type. Comparison of the costs of rhenium catalysts and granular carbon carrier with those of nickel, platinum, and palladium showed that 5% rhenium catalyst can

Outstanding low temperature HC-SCR of NOx over platinum-group catalysts supported on mesoporous materials expecting diesel-auto emission regulation

International Nuclear Information System (INIS)

Komatsu, Tamikuni; Tomokuni, Keizou; Yamada, Issaku

2006-01-01

Outstanding low temperature HC-SCR of NOx over platinum-group catalysts supported on mesoporous materials, which does not rely on the conventional NOx-absorption-reduction-catalysts, is presented for the purpose of de-NOx of diesel-auto emissions. The established catalysts basically consist of mesoporous silica or metal-substituted mesoporous silicates for supports and platinum for active species, which is operated under lean- and rich-conditions. The new catalysts are very active at 150-200 o C and free from difficult problems of SOx-deactivation and hydrothermal ageing of the NOx-absorption-reduction catalyst. (author)

Ruthenium–Platinum Catalysts and Direct Methanol Fuel Cells (DMFC: A Review of Theoretical and Experimental Breakthroughs

Directory of Open Access Journals (Sweden)

Ana S. Moura

2017-02-01

Full Text Available The increasing miniaturization of devices creates the need for adequate power sources and direct methanol fuel cells (DMFC are a strong option in the various possibilities under current development. DMFC catalysts are mostly based on platinum, for its outperformance in three key areas (activity, selectivity and stability within methanol oxidation framework. However, platinum poisoning with products of methanol oxidation led to the use of alloys. Ruthenium–platinum alloys are preferred catalysts active phases for methanol oxidation from an industrial point of view and, indeed, ruthenium itself is a viable catalyst for this reaction. In addition, the route of methanol decomposition is crucial in the goal of producing H2 from water reaction with methanol. However, the reaction pathway remains elusive and new approaches, namely in computational methods, have been ensued to determine it. This article reviews the various recent theoretical approaches for determining the pathway of methanol decomposition, and systematizes their validation with experimental data, within methodological context.

Carbons and carbon supported catalysts in hydroprocessing

Energy Technology Data Exchange (ETDEWEB)

Furimsky, Edward

2009-07-01

This book is a comprehensive summary of recent research in the field and covers all areas of carbons and carbon materials. The potential application of carbon supports, particularly those of carbon black (CB) and activated carbon (AC) in hydroprocessing catalysis are covered. Novel carbon materials such as carbon fibers and carbon nano tubes (CNT) are also covered, including the more recent developments in the use of fullerenes in hydroprocessing applications. Although the primary focus of this book is on carbons and carbon supported catalysts, it also identifies the difference in the effect of carbon supports compared with the oxidic supports, particularly that of the Al{sub 2}O{sub 3}. The difference in catalyst activity and stability was estimated using both model compounds and real feeds under variable conditions. The conditions applied during the preparation of carbon supported catalysts are also comprehensively covered and include various methods of pretreatment of carbon supports to enhance catalyst performance. The model compounds results consistently show higher hydrodesulfurization and hydrodeoxygenation activities of carbon supported catalysts than that of the Al{sub 2}O{sub 3} supported catalysts. Also, the deactivation of the former catalysts by coke deposition was much less evident. Chapter 6.3.1.3 is on carbon-supported catalysts: coal-derived liquids.

Structure, activity, and stability of platinum alloys as catalysts for the oxygen reduction reaction

DEFF Research Database (Denmark)

Vej-Hansen, Ulrik Grønbjerg

In this thesis I present our work on theoretical modelling of platinum alloys as catalysts for the Oxygen Reduction Reaction (ORR). The losses associated with the kinetics of the ORR is the main bottleneck in low-temperature fuel cells for transport applications, and more active catalysts...... are essential for wide-spread use of this technology. platinum alloys have shown great promise as more active catalysts, which are still stable under reaction conditions. We have investigated these systems on multiple scales, using either Density Functional Theory (DFT) or Effective Medium Theory (EMT......), depending on the length and time scales involved. Using DFT, we show how diffusion barriers in transition metal alloys in the L12 structure depend on the alloying energy, supporting the assumption that an intrinsically more stable alloy is also more stable towards diffusion-related degradation...

Highly Durable Platinum Single-Atom Alloy Catalyst for Electrochemical Reactions

DEFF Research Database (Denmark)

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

2018-01-01

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

bis-Nitrile and bis-Dialkylcyanamide Platinum(II) Complexes as Efficient Catalysts for Hydrosilylation Cross-Linking of Siloxane Polymers.

Science.gov (United States)

Islamova, Regina M; Dobrynin, Mikhail V; Ivanov, Daniil M; Vlasov, Andrey V; Kaganova, Elena V; Grigoryan, Galina V; Kukushkin, Vadim Yu

2016-03-05

cis- and trans-Isomers of the platinum(II) nitrile complexes [PtCl2(NCR)2] (R = NMe2, N(C₅H10), Ph, CH2Ph) were examined as catalysts for hydrosilylation cross-linking of vinyl-terminated polydimethylsiloxane and trimethylsilyl-terminated poly(dimethylsiloxane-co-ethylhydrosiloxane) producing high quality silicone rubbers. Among the tested platinum species the cis-complexes are much more active catalysts than their trans-congeners and for all studied platinum complexes cis-[PtCl2(NCCH2Ph)2] exhibits the best catalytic activity (room temperature, c = 1.0 × 10(-4) mol/L, τpot-life 60 min, τcuring 6 h). Although cis-[PtCl₂(NCCH2Ph)2] is less active than the widely used Karstedt's catalyst, its application for the cross-linking can be performed not only at room temperature (c = 1.0 × 10(-4) mol/L), but also, more efficiently, at 80 °C (c = 1.0 × 10(-4)-1.0 × 10(-5) mol/L) and it prevents adherence of the formed silicone rubbers to equipment. The usage of the cis- and trans-[PtCl2(NCR)2] complexes as the hydrosilylation catalysts do not require any inhibitors and, moreover, the complexes and their mixtures with vinyl- and trimethylsilyl terminated polysiloxanes are shelf-stable in air. Tested catalysts do not form colloid platinum particles after the cross-linking.

Redeposition of electrochemically dissolved platinum as nanoparticles on carbon

DEFF Research Database (Denmark)

Norgaard, C. F.; Stamatin, S. N.; Skou, E. M.

2014-01-01

communication reports a simple chemical method for reprecipitating platinum as nanoparticles of reasonable particle size on a carbon substrate without intermediary separation and handling of solid platinum salt. After electrochemical dissolution, platinum was reprecipitated using a polyol based method. Platinum...

Design of Polymer-Coated Multi-Walled Carbon Nanotube/Carbon Black-based Fuel Cell Catalysts with High Durability and Performance Under Non-humidified Condition

International Nuclear Information System (INIS)

Yang, Zehui; Berber, Mohamed R.; Nakashima, Naotoshi

2015-01-01

To realize a high catalyst utilization, better fuel cell performance and durability as well as low production cost, an efficient design strategy of the catalyst layer that can improve both the oxygen accessibility and structure stability is highly required. Here, we describe the preparation of fuel cell electrocatalysts with an efficient fuel cell performance and better stability based on hybrids of multi-walled carbon nanotubes (MWNTs) and carbon black (CB) which were wrapped by a proton conducting polymer, poly[2,2′-(2,6-pyridine)-5,5′-bibenzimidazole], before deposition of the platinum (Pt) metal catalyst. The catalyst mass activity after feeding only 10%-MWNTs to CB increased by 1.5 and 2 times than those of the MWNTs-based- and CB-based catalysts, respectively. The results also demonstrated that 90 wt% of the MWNTs in the catalyst layer allows it to be replaced by CB without any significant change in its durability and performance under 120 °C and non-humidified condition

Influence of surface morphology on methanol oxidation at a glassy carbon-supported Pt catalyst

Directory of Open Access Journals (Sweden)

S. STEVANOVIC

2008-08-01

Full Text Available Platinum supported on glassy carbon (GC was used as a model system for studying the influence of the surface morphology of a Pt catalyst on methanol oxidation in alkaline and acidic solutions. Platinum was deposited by the potential step method on GC samples from H2SO4 + H2PtCl6 solution under the same conditions with loadings from 10 to 80 mg cm-2. AFM and STM images of the GC/Pt electrodes showed that the Pt was deposited in the form of 3D agglomerates composed of spherical particles. Longer deposition times resulted in increased growth of Pt forms and a decrease in the specific area of the Pt. The real surface area of Pt increased with loading but the changes were almost negligible at higher loadings. Nevertheless, both the specific and mass activity of platinum supported on glassy carbon for methanol oxidation in acidic and in alkaline solutions exhibit a volcanic dependence with respect to the platinum loading. The increase in the activity can be explained by the increasing the particle size with the loading and thus an increase in the contiguous Pt sites available for adsorption and decomposition of methanol. However, the decrease in the activity of the catalyst with further increase of loading and particle size after reaching the maximum is related to the decrease of active sites available for methanol adsorption and their accessibility as a result of more close proximity and pronounced coalescence of the Pt particles.

High performance platinum single atom electrocatalyst for oxygen reduction reaction

Science.gov (United States)

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

2017-07-01

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

Platinum group metal recovery and catalyst manufacturing process

Energy Technology Data Exchange (ETDEWEB)

Chung, H. S.; Kim, Y. S.; Yoo, J. H.; Lee, H. S.; Ahn, D. H.; Kim, K. R.; Lee, S. H.; Paek, S. W.; Kang, H. S.

1998-03-01

The fission product nuclides generated during the irradiation of reactor fuel include many useful elements, among them platinum group metal such as ruthenium, rhodium and palladium which are of great industrial importance, occur rarely in nature and are highly valuable. In this research, the authors reviewed various PGM recovery methods. Recovery of palladium from seven-component simulated waste solution was conducted by selective precipitation method. The recovery yield was more than 99.5% and the purity of the product was more than 99%. Wet-proof catalyst was prepared with the recovered palladium. The specific surface area of the catalyst support was more than 400 m{sup 2}/g. The content of palladium impregnated on the support was 10 wt.%. Hydrogen isotope exchange efficiency of 93 % to equilibrium with small amount of the catalyst was obtained. It was turned out possible to consider using such palladium or other very low active PGM materials in applications where its actively is unimportant as in nuclear industries. (author). 63 refs., 38 tabs., 36 figs.

UV-induced polymerization of size-controlled platinum/poly[styrene-divinylbenzene-tri(propylene glycol) diacrylate] hydrophobic catalyst beads in microfluidics

Energy Technology Data Exchange (ETDEWEB)

Wi, Jun; Li, Xiang; Song, Tong; Song, Zi Fan; Chang, Zhen Qi [School of Nuclear Science and Technology, University of Science and Technology of China, Hefei (China); Meng, Da Qiao [Si Chuan Institute of Materials and Technology, Jiang You (China)

2015-10-15

The catalytic exchange of hydrogen isotopes between hydrogen and water has been known to be a very useful process for the separation of tritium from tritiated water. For the process, a highly active hydrophobic catalyst is needed. This study provides an effective fabrication method of size-controlled platinum/poly[styrene-divinylbenzene-tri(propylene glycol) diacrylate] [Pt/poly(SDB-TPGDA)] hydrophobic catalyst beads with a narrow size distribution. Platinum nanoparticles were prepared by γ-ray-induced reduction in the aqueous phase first, and then uniformly dispersed in SDB-TPGDA comonomer after the hydrophobization of platinum nanoparticles with alkylamine stabilizers. The porous Pt/poly(SDB-TPGDA) hydrophobic catalyst beads were synthesized by the UV-initiated polymerization of the mixture droplets prepared in a capillary-based microfluidic system. The size of as-prepared catalyst beads can be controlled in the range of 200-1,000 μm by adjusting the flow rate of dispersed and continuous phases, as well as the viscosity of the continuous phase. Sorbitan monooleate and cyclohexanol were used as coporogens to control the porosities of the catalyst beads.

UV-induced polymerization of size-controlled platinum/poly[styrene-divinylbenzene-tri(propylene glycol) diacrylate] hydrophobic catalyst beads in microfluidics

International Nuclear Information System (INIS)

Wi, Jun; Li, Xiang; Song, Tong; Song, Zi Fan; Chang, Zhen Qi; Meng, Da Qiao

2015-01-01

The catalytic exchange of hydrogen isotopes between hydrogen and water has been known to be a very useful process for the separation of tritium from tritiated water. For the process, a highly active hydrophobic catalyst is needed. This study provides an effective fabrication method of size-controlled platinum/poly[styrene-divinylbenzene-tri(propylene glycol) diacrylate] [Pt/poly(SDB-TPGDA)] hydrophobic catalyst beads with a narrow size distribution. Platinum nanoparticles were prepared by γ-ray-induced reduction in the aqueous phase first, and then uniformly dispersed in SDB-TPGDA comonomer after the hydrophobization of platinum nanoparticles with alkylamine stabilizers. The porous Pt/poly(SDB-TPGDA) hydrophobic catalyst beads were synthesized by the UV-initiated polymerization of the mixture droplets prepared in a capillary-based microfluidic system. The size of as-prepared catalyst beads can be controlled in the range of 200-1,000 μm by adjusting the flow rate of dispersed and continuous phases, as well as the viscosity of the continuous phase. Sorbitan monooleate and cyclohexanol were used as coporogens to control the porosities of the catalyst beads

Catalytic wet oxidation of ammonia solution: Activity of the nanoscale platinum-palladium-rhodium composite oxide catalyst

International Nuclear Information System (INIS)

Hung, C.-M.

2009-01-01

Aqueous solutions of 400-1000 mg/L of ammonia were oxidized in a trickle-bed reactor (TBR) in this study of nanoscale platinum-palladium-rhodium composite oxide catalysts, which were prepared by the co-precipitation of H 2 PtCl 6 , Pd(NO 3 ) 3 and Rh(NO 3 ) 3 . Hardly any of the dissolved ammonia was removed by wet oxidation in the absence of any catalyst, whereas about 99% of the ammonia was reduced during wet oxidation over nanoscale platinum-palladium-rhodium composite oxide catalysts at 503 K in an oxygen partial pressure of 2.0 MPa. A synergistic effect exists in the nanoscale platinum-palladium-rhodium composite structure, which is the material with the highest ammonia reduction activity. The nanometer-sized particles were characterized by TEM, XRD and FTIR. The effect of the initial concentration and reaction temperature on the removal of ammonia from the effluent streams was also studied at a liquid hourly space velocity of under 9 h -1 in the wet catalytic processes

Catalytic wet oxidation of ammonia solution: Activity of the nanoscale platinum-palladium-rhodium composite oxide catalyst

Energy Technology Data Exchange (ETDEWEB)

Hung, C.-M. [Department of Industry Engineering and Management, Yung-Ta Institute of Technology and Commerce, 316 Chung-shan Road, Linlo, Pingtung 909, Taiwan (China)], E-mail: hungcm1031@gmail.com

2009-04-15

Aqueous solutions of 400-1000 mg/L of ammonia were oxidized in a trickle-bed reactor (TBR) in this study of nanoscale platinum-palladium-rhodium composite oxide catalysts, which were prepared by the co-precipitation of H{sub 2}PtCl{sub 6}, Pd(NO{sub 3}){sub 3} and Rh(NO{sub 3}){sub 3}. Hardly any of the dissolved ammonia was removed by wet oxidation in the absence of any catalyst, whereas about 99% of the ammonia was reduced during wet oxidation over nanoscale platinum-palladium-rhodium composite oxide catalysts at 503 K in an oxygen partial pressure of 2.0 MPa. A synergistic effect exists in the nanoscale platinum-palladium-rhodium composite structure, which is the material with the highest ammonia reduction activity. The nanometer-sized particles were characterized by TEM, XRD and FTIR. The effect of the initial concentration and reaction temperature on the removal of ammonia from the effluent streams was also studied at a liquid hourly space velocity of under 9 h{sup -1} in the wet catalytic processes.

Catalytic wet oxidation of ammonia solution: activity of the nanoscale platinum-palladium-rhodium composite oxide catalyst.

Science.gov (United States)

Hung, Chang-Mao

2009-04-15

Aqueous solutions of 400-1000 mg/L of ammonia were oxidized in a trickle-bed reactor (TBR) in this study of nanoscale platinum-palladium-rhodium composite oxide catalysts, which were prepared by the co-precipitation of H(2)PtCl(6), Pd(NO(3))(3) and Rh(NO(3))(3). Hardly any of the dissolved ammonia was removed by wet oxidation in the absence of any catalyst, whereas about 99% of the ammonia was reduced during wet oxidation over nanoscale platinum-palladium-rhodium composite oxide catalysts at 503 K in an oxygen partial pressure of 2.0 MPa. A synergistic effect exists in the nanoscale platinum-palladium-rhodium composite structure, which is the material with the highest ammonia reduction activity. The nanometer-sized particles were characterized by TEM, XRD and FTIR. The effect of the initial concentration and reaction temperature on the removal of ammonia from the effluent streams was also studied at a liquid hourly space velocity of under 9 h(-1) in the wet catalytic processes.

Hydrodeoxygenation of phenols as lignin models under acid-free conditions with carbon-supported platinum catalysts.

Science.gov (United States)

Ohta, Hidetoshi; Kobayashi, Hirokazu; Hara, Kenji; Fukuoka, Atsushi

2011-11-28

Carbon-supported Pt catalysts are highly active and reusable for the aqueous-phase hydrodeoxygenation of phenols as lignin models without adding any acids. It is suggested that Pt/carbon facilitates the hydrogenation of phenols and the hydrogenolysis of the resulting cyclohexanols.

Recycling of platinum group metals from the automotive catalysts; Reciclagem de metais do grupo da platina proveniente de catalisadores automotivos

Energy Technology Data Exchange (ETDEWEB)

Benevit, Mariana; Petter, Patricia Melo Halmenschlager; Veit, Hugo Marcelo, E-mail: patymhp@yahoo.com.br [Universidade Federal do Rio Grande do Sul (UFRGS), Porto Alegre, RS (Brazil). Faculdade de Engenharia. Departamento de Materiais

2014-07-01

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)

Co-deposition of Pt and ceria anode catalyst in supercritical carbon dioxide for direct methanol fuel cell applications

International Nuclear Information System (INIS)

You, Eunyoung; Guzmán-Blas, Rolando; Nicolau, Eduardo; Aulice Scibioh, M.; Karanikas, Christos F.; Watkins, James J.; Cabrera, Carlos R.

2012-01-01

Pt and mixed Pt-ceria catalysts were deposited onto gas diffusion layers using supercritical fluid deposition (SFD) to fabricate thin layer electrodes for direct methanol fuel cells. Dimethyl (1,5-cyclooctadiene) platinum (II) (CODPtMe 2 ) and tetrakis (2,2,6,6-tetramethyl 3,5-heptanedionato) cerium (IV) (Ce(tmhd) 4 ) were used as precursors. Hydrogen-assisted Pt deposition was performed in compressed carbon dioxide at 60 °C and 17.2 MPa to yield high purity Pt on carbon-black based gas diffusion layers. During the preparation of the mixed Pt-ceria catalyst, hydrogen reduction of CODPtMe 2 to yield Pt catalyzed the deposition of ceria from Ce(tmhd) 4 enabling co-deposition at 150 °C. The catalyst layers were characterized using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and scanning electron microscope-energy dispersive spectral (SEM-EDS) analyses. Their electrochemical performance toward methanol oxidation was examined in half cell mode using a three electrode assembly as well as in fuel cell mode. The thin layer electrodes formed via SFD exhibited higher performance in fuel cell operations compared to those prepared by the conventional brush-paint method. Furthermore, the Pt-ceria catalyst with an optimized composition exhibited greater methanol oxidation activity than pure platinum.

A new catalyst for heavy water production and its prospect

International Nuclear Information System (INIS)

Sato, Toshio; Ohkoshi, Sumio; Takahashi, Tomiki

1978-01-01

The heavy water production process utilizing isotope exchange reaction between liquid water and hydrogen is the most promising method. Study was made for developing highly active and long life catalyst practically applied for this process. As platinum is used as this catalyst, catalytic activities using varieties of Polapacs and Shodexes instead of active carbon as the carriers of platinum catalyst were investigated. It became clear that the catalytic activity using Pt/Shodex 104 (3 wt %) was 1000 times as high as the activity using Pt/active carbon (1 wt %). This method is considered to be reasonable enough economically. There are many problems which must be solved hereafter for its practical use, and the further studies are required regarding the following points; forming of catalyst, life of catalyst, mass production of catalyst, most appropriate counter flow reacting device of hydrophobic catalyst, pressure and temperature effects on reaction. (Kobatake, H.)

Catalysts for the production of hydrocarbons from carbon monoxide and water

Science.gov (United States)

Sapienza, R.S.; Slegeir, W.A.; Goldberg, R.I.

1985-11-06

A method of converting low H/sub 2//CO ratio syngas to carbonaceous products comprising reacting the syngas with water or steam at 200 to 350/sup 0/C in the presence of a metal catalyst supported on zinc oxide. Hydrocarbons are produced with a catalyst selected from cobalt, nickel or ruthenium and alcohols are produced with a catalyst selected from palladium, platinum, ruthenium or copper on the zinc oxide support. The ratio of the reactants are such that for alcohols and saturated hydrocarbons: (2n + 1) greater than or equal to x greater than or equal to O and for olefinic hydrocarbons: 2n greater than or equal to x greater than or equal to O where n is the number of carbon atoms in the product and x is the molar amount of water in the reaction mixture.

Reaction selectivity studies on nanolithographically-fabricated platinum model catalyst arrays

Energy Technology Data Exchange (ETDEWEB)

Grunes, Jeffrey Benjamin [Univ. of California, Berkeley, CA (United States)

2004-05-01

In an effort to understand the molecular ingredients of catalytic activity and selectivity toward the end of tuning a catalyst for 100% selectivity, advanced nanolithography techniques were developed and utilized to fabricate well-ordered two-dimensional model catalyst arrays of metal nanostructures on an oxide support for the investigation of reaction selectivity. In-situ and ex-situ surface science techniques were coupled with catalytic reaction data to characterize the molecular structure of the catalyst systems and gain insight into hydrocarbon conversion in heterogeneous catalysis. Through systematic variation of catalyst parameters (size, spacing, structure, and oxide support) and catalytic reaction conditions (hydrocarbon chain length, temperature, pressures, and gas composition), the data presented in this dissertation demonstrate the ability to direct a reaction by rationally adjusting, through precise control, the design of the catalyst system. Electron beam lithography (EBL) was employed to create platinum nanoparticles on an alumina (Al₂O₃) support. The Pt nanoparticle spacing (100-150-nm interparticle distance) was varied in these samples, and they were characterized using x-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), scanning electron microscopy (SEM), and atomic force microscopy (AFM), both before and after reactions. The TEM studies showed the 28-nm Pt nanoparticles with 100 and 150-nm interparticle spacing on alumina to be polycrystalline in nature, with crystalline sizes of 3-5 nm. The nanoparticle crystallites increased significantly after heat treatment. The nanoparticles were still mostly polycrystalline in nature, with 2-3 domains. The 28-nm Pt nanoparticles deposited on alumina were removed by the AFM tip in contact mode with a normal force of approximately 30 nN. After heat treatment at 500 C in vacuum for 3 hours, the AFM tip, even at 4000 nN, could not remove the platinum

Ionic Liquids as Solvents for Rhodium and Platinum Catalysts Used in Hydrosilylation Reaction

Directory of Open Access Journals (Sweden)

Witold Zielinski

2016-08-01

Full Text Available A group of imidazolium and pyridinium based ionic liquids has been synthetized, and their ability to dissolve and activate the catalysts used in hydrosilylation reaction of 1-octane and 1,1,1,3,5,5,5-heptamethyltrisiloxane was investigated. An organometallic catalyst as well as inorganic complexes of platinum and rhodium dissolved in ionic liquids were used, forming liquid solutions not miscible with the substrates or with the products of the reaction. The results show that application of such a simple biphasic catalytic system enables reuse of ionic liquid phase with catalysts in multiple reaction cycles reducing the costs and decreasing the amount of catalyst needed per mole of product.

Nanolithographic Fabrication and Heterogeneous Reaction Studies ofTwo-Dimensional Platinum Model Catalyst Systems

Energy Technology Data Exchange (ETDEWEB)

Contreras, Anthony Marshall [Univ. of California, Berkeley, CA (United States)

2006-05-20

In order to better understand the fundamental components that govern catalytic activity, two-dimensional model platinum nanocatalyst arrays have been designed and fabricated. These catalysts arrays are meant to model the interplay of the metal and support important to industrial heterogeneous catalytic reactions. Photolithography and sub-lithographic techniques such as electron beam lithography, size reduction lithography and nanoimprint lithography have been employed to create these platinum nanoarrays. Both in-situ and ex-situ surface science techniques and catalytic reaction measurements were used to correlate the structural parameters of the system to catalytic activity.

Carbon nanostructures as catalyst support for polymer electrolyte membrane fuel cells

Energy Technology Data Exchange (ETDEWEB)

Natarajan, S.K.; Hamelin, J. [Quebec Univ., Trois Rivieres, PQ (Canada). Inst. de recherche sur l' hydrogene

2008-07-01

This paper reported on a study that investigated potential alternatives to Vulcan XC-72 as a catalyst supports for polymer electrolyte membrane fuel cells (PEMFCs). These included carbon nanostructures (CNS) prepared by high energy ball milling of graphite and transition metal catalysts, followed by heat treatment. Among the key factors discussed were the graphitic content, high surface area, microporous structure, good electrical conductivity and the ability of the material to attach functional groups. Some graphic results supporting the usage of CNS as catalyst support for PEMFCs were presented. Upon chemical oxidation, surface functional groups such as carbonyl, carboxyl, and hydroxyl were populated on the surface of CNS. Nanosized platinum particles with particle size distribution between 3 nm and 5 nm were reduced on the functionalized sites of CNS in a colloidal medium. The paper also presented cyclic voltammograms, XPS, HRTEM and PSD results. 3 refs.

Electrocatalytic activity mapping of model fuel cell catalyst films using scanning electrochemical microscopy

International Nuclear Information System (INIS)

Nicholson, P.G.; Zhou, S.; Hinds, G.; Wain, A.J.; Turnbull, A.

2009-01-01

Scanning electrochemical microscopy has been employed to spatially map the electrocatalytic activity of model proton exchange membrane fuel cell (PEMFC) catalyst films towards the hydrogen oxidation reaction (the PEMFC anode reaction). The catalyst films were composed of platinum-loaded carbon nanoparticles, similar to those typically used in PEMFCs. The electrochemical characterisation was correlated with a detailed physical characterisation using dynamic light scattering, transmission electron microscopy and field-emission scanning electron microscopy. The nanoparticles were found to be reasonably mono-dispersed, with a tendency to agglomerate into porous bead-type structures when spun-cast. The number of carbon nanoparticles with little or no platinum was surprisingly higher than would be expected based on the platinum-carbon mass ratio. Furthermore, the platinum-rich carbon particles tended to agglomerate and the clusters formed were non-uniformly distributed. This morphology was reflected in a high degree of heterogeneity in the film activity towards the hydrogen oxidation reaction.

Metal Oxide-Supported Platinum Overlayers as Proton-Exchange Membrane Fuel Cell Cathodes

DEFF Research Database (Denmark)

Tripkovic, Vladimir; Abild-Pedersen, Frank; Studt, Felix

2012-01-01

We investigated the activity and stability of n=(1, 2, 3) platinum layers supported on a number of rutile metal oxides (MO2; M=Ti, Sn, Ta, Nb, Hf and Zr). A suitable oxide support can alleviate the problem of carbon corrosion and platinum dissolution in Pt/C catalysts. Moreover, it can increase t...

The role of support and promoter on the oxidation of sulfur dioxide using platinum based catalysts

DEFF Research Database (Denmark)

Koutsopoulos, Sotiris; Rasmussen, Søren Birk; Eriksen, Kim Michael

2006-01-01

The catalytic oxidation of SO2 to SO3 was studied over platinum based catalysts in the absence and the presence of dopants. The active metal was supported on silica gel or titania (anatase) by impregnation. The activities of the silica supported catalysts were found to follow the order PtRh/SiO2 ...

Pt/Al/sub 2/O/sub 3/- carbon nanocomposite as a catalyst for fuel cells

International Nuclear Information System (INIS)

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

2013-01-01

Catalysts comprising platinum nanoparticles (Pt NPs) on carbon support are used in fuel cells for the hydrogen and electricity production by electrochemical oxidation of methanol. However, the catalyst is not the best in terms of its performance. Considering role of the support as significant towards efficiency and durability of the catalyst, there is need for introducing novel support materials to replace carbon alone. Deposition of various metallic NPs on ceramic-carbon (hybrid) supports has been reported to improve thermal, mechanical, electrical and chemical properties of different types of catalyst. In search of better performing catalysts for proton exchange membrane fuel cells (PEMFCs), hybrid supports having different ceramic materials should be synthesized. In this regard Pt/Al/sub 2/O/sub 3/-Carbon (nanocomposites) have been synthesized and applied as promising catalysts in the PEMFCs; results obtained for the nanocomposites were compared with Pt/carbon and Pt/Al/sub 2/O/sub 3/. Vulcan carbon was purified and functionalized prior to use; presence of oxygen containing functional groups on carbon was established from the FTIR spectrum, Hybrid support (1:8 by weight ratio of ceramic and carbon) were already prepared in aqueous 2-propanol employing sonication method on to which Pt NPs (10% by weight in all the cases) were deposited by simple chemical reduction of PtCl/sub 4/ by NaBH/sub 4/ under controlled conditions. The catalysts were subjected to various characterization techniques like TGA (for thermal stability), EDX (for chemical composition), SEM (for surface morphology) and XRD (for cell-shape and -volume, material density and average crystalline size). Catalysts efficiencies for the methanol oxidation were investigated through cyclic voltammetery (CV) by comparing electrochemical surface area, peak current, exchange current density and rate constant in the acidic and basic media. Pt/Al/sub 2/O/sub 3/-carbon exhibited better catalytic efficiencies

Enhancement of micropore filling of water on carbon black by platinum loading

Energy Technology Data Exchange (ETDEWEB)

Miyajima, Naoya, E-mail: miyajima@yamanashi.ac.jp [Interdisciplinary Graduate School of Medicine and Engineering, 4-3-11 Takeda, Kofu, Yamanashi 400-8511 (Japan); Hatori, Hiroaki [Institute of Advanced Industrial Science and Technology (AIST), 16-1 Onogawa, Tsukuba, Ibaraki 305-8569 (Japan); Radovic, Ljubisa R. [Department of Energy and Geo-Environmental Engineering, The Pennsylvania State University, University Park, PA 16802 (United States); Yamada, Yoshio [Institute of Advanced Industrial Science and Technology (AIST), 16-1 Onogawa, Tsukuba, Ibaraki 305-8569 (Japan)

2010-10-15

Two kinds of typical carbons, carbon black and activated carbon fibers, were modified with platinum nanoparticles without changing their original pore structures. The surface properties of the modified carbons were investigated by measuring of water adsorption isotherms. Micropore filling of water was facilitated by the presence of platinum nanoparticles on the surface of the carbon black. On the other hand, such a filling effect was not observed in the case of the activated carbon fibers. A critical content and/or size of platinum nanoparticles could be required to promote efficiently the water adsorption.

Dye sensitized solar cell based on platinum decorated multiwall carbon nanotubes as catalytic layer on the counter electrode

International Nuclear Information System (INIS)

Mathew, Ambily; Rao, G. Mohan; Munichandraiah, N.

2011-01-01

Graphical abstract: I-V characteristics of the DSSCs with Pt CE and Pt/MWCNT CE measured at 100 mW/cm 2 . It shows relatively better performance with Pt/MWCNT counter electrodes. Highlights: → Synthesis of multiwalled carbon nanotubes by pyrolysis. → Synthesis of Pt/MWCNT composite by chemical reduction. → Fabrication DSSC using Pt/MWCNT as catalytic layer on the counter electrode. → Study of catalytic activity by Electrochemical Impedance Spectroscopy. -- Abstract: In this study we have employed multiwall carbon nanotubes (MWCNT), decorated with platinum as catalytic layer for the reduction of tri-iodide ions in dye sensitized solar cell (DSSC). MWCNTs have been prepared by a simple one step pyrolysis method using ferrocene as the catalyst and xylene as the carbon source. Platinum decorated MWCNTs have been prepared by chemical reduction method. The as prepared MWCNTs and Pt/MWCNTs have been characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). In combination with a dye adsorbed TiO 2 photoanode and an organic liquid electrolyte, Pt/MWCNT composite showed an enhanced short circuit current density of 16.12 mA/cm 2 leading to a cell efficiency of 6.50% which is comparable to that of Platinum.

Dye sensitized solar cell based on platinum decorated multiwall carbon nanotubes as catalytic layer on the counter electrode

Energy Technology Data Exchange (ETDEWEB)

Mathew, Ambily [Department of Instrumentation and Applied Physics, Indian Institute of Science, Bangalore 560012 India (India); Rao, G. Mohan, E-mail: gmrao@isu.iisc.ernet.in [Department of Instrumentation and Applied Physics, Indian Institute of Science, Bangalore 560012 India (India); Munichandraiah, N. [Department of Inorgonic and Physical Chemistry, Indian Institute of Science, Bangalore 560012 India (India)

2011-11-15

Graphical abstract: I-V characteristics of the DSSCs with Pt CE and Pt/MWCNT CE measured at 100 mW/cm{sup 2}. It shows relatively better performance with Pt/MWCNT counter electrodes. Highlights: {yields} Synthesis of multiwalled carbon nanotubes by pyrolysis. {yields} Synthesis of Pt/MWCNT composite by chemical reduction. {yields} Fabrication DSSC using Pt/MWCNT as catalytic layer on the counter electrode. {yields} Study of catalytic activity by Electrochemical Impedance Spectroscopy. -- Abstract: In this study we have employed multiwall carbon nanotubes (MWCNT), decorated with platinum as catalytic layer for the reduction of tri-iodide ions in dye sensitized solar cell (DSSC). MWCNTs have been prepared by a simple one step pyrolysis method using ferrocene as the catalyst and xylene as the carbon source. Platinum decorated MWCNTs have been prepared by chemical reduction method. The as prepared MWCNTs and Pt/MWCNTs have been characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). In combination with a dye adsorbed TiO{sub 2} photoanode and an organic liquid electrolyte, Pt/MWCNT composite showed an enhanced short circuit current density of 16.12 mA/cm{sup 2} leading to a cell efficiency of 6.50% which is comparable to that of Platinum.

In situ XAFS studies of the oxygen reduction reaction on carbon supported platinum and platinum nickel nano-scale alloys as cathode catalysts in fuel cells

Science.gov (United States)

Jia, Qingying

Platinum based bimetallic alloys have been investigated by conducting Pt L3 and Ni K edge in situ XAFS measurements on carbon supported Pt and PtNi(1:1) nanoscale catalysts under a wide range of operating potentials. We observed that (1) the Pt-Pt bond distance in PtNi alloys is shorter than that of Pt, and the bond distance between Pt and oxygen adsorbate is longer for PtNi. (2) Pt has a tendency to stay on the surface while Ni is mostly underneath the surface. (3) While a change in oxidation of pure Pt was clearly observed at different potentials, the Pt in the PtNi alloy remained nearly oxygen-free at all potentials, but an accompanying oxidation change of Ni was observed instead. (4) PtNi has higher open circuit voltage than Pt/C. These results indicate that the chemisorption energy between Pt and oxygen adsorbate is reduced in PtNi alloys, which prevents the poison of oxygen adsorbate and hence improves the reactivity. In addition, the strain and ligand effects in PtNi nanoparticle alloys were studied by FEW calculations using experimental data as a guide to understand the factors causing the reduction of chemisorptions energy of Pt. Our calculation indicates that Pt d-band is broader and lower in energy when the bond distance between Pt is shorter, resulting in weaker chemisorption energy between Pt and absorbed oxygen atom on top, and vice verse. Meanwhile, the investigation of ligand effect shows two trends in modifying Pt's properties within alloyed transition metals. The strain effect dominates in PtNi bimetallic system, corresponding to weaker chemisorptions energy and lower white intensity of Pt L3 edge, which is in consistent with our experimental results. The implications of these results afford a good guideline in understanding the reactivity enhancement mechanism and in the context of alloy catalysts design.

Role of bonding mechanisms during transfer hydrogenation reaction on heterogeneous catalysts of platinum nanoparticles supported on zinc oxide nanorods

Science.gov (United States)

Al-Alawi, Reem A.; Laxman, Karthik; Dastgir, Sarim; Dutta, Joydeep

2016-07-01

For supported heterogeneous catalysis, the interface between a metal nanoparticle and the support plays an important role. In this work the dependency of the catalytic efficiency on the bonding chemistry of platinum nanoparticles supported on zinc oxide (ZnO) nanorods is studied. Platinum nanoparticles were deposited on ZnO nanorods (ZnO NR) using thermal and photochemical processes and the effects on the size, distribution, density and chemical state of the metal nanoparticles upon the catalytic activities are presented. The obtained results indicate that the bonding at Pt-ZnO interface depends on the deposition scheme which can be utilized to modulate the surface chemistry and thus the activity of the supported catalysts. Additionally, uniform distribution of metal on the catalyst support was observed to be more important than the loading density. It is also found that oxidized platinum Pt(IV) (platinum hydroxide) provided a more suitable surface for enhancing the transfer hydrogenation reaction of cyclohexanone with isopropanol compared to zero valent platinum. Photochemically synthesized ZnO supported nanocatalysts were efficient and potentially viable for upscaling to industrial applications.

Electrochemical performance for the electro-oxidation of ethylene glycol on a carbon-supported platinum catalyst at intermediate temperature

International Nuclear Information System (INIS)

Kosaka, Fumihiko; Oshima, Yoshito; Otomo, Junichiro

2011-01-01

Highlights: → High oxidation current in ethylene glycol electro-oxidation at intermediate temperature. → High C-C bond dissociation ratio of ethylene glycol at intermediate temperature. → Low selectivity for CH 4 in ethylene glycol electro-oxidation. → High selectivity for CO 2 according to an increase in steam to carbon ratios. - Abstract: To determine the kinetic performance of the electro-oxidation of a polyalcohol operating at relatively high temperatures, direct electrochemical oxidation of ethylene glycol on a carbon supported platinum catalyst (Pt/C) was investigated at intermediate temperatures (235-255 o C) using a single cell fabricated with a proton-conducting solid electrolyte, CsH 2 PO 4 , which has high proton conductivity (>10 -2 S cm -1 ) in the intermediate temperature region. A high oxidation current density was observed, comparable to that for methanol electro-oxidation and also higher than that for ethanol electro-oxidation. The main products of ethylene glycol electro-oxidation were H 2 , CO 2 , CO and a small amount of CH 4 formation was also observed. On the other hand, the amounts of C 2 products such as acetaldehyde, acetic acid and glycolaldehyde were quite small and were lower by about two orders of magnitude than the gaseous reaction products. This clearly shows that C-C bond dissociation proceeds almost to completion at intermediate temperatures and the dissociation ratio reached a value above 95%. The present observations and kinetic analysis suggest the effective application of direct alcohol fuel cells operating at intermediate temperatures and indicate the possibility of total oxidation of alcohol fuels.

A Platinum Monolayer Core-Shell Catalyst with a Ternary Alloy Nanoparticle Core and Enhanced Stability for the Oxygen Reduction Reaction

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Haoxiong Nan

2015-01-01

Full Text Available We synthesize a platinum monolayer core-shell catalyst with a ternary alloy nanoparticle core of Pd, Ir, and Ni. A Pt monolayer is deposited on carbon-supported PdIrNi nanoparticles using an underpotential deposition method, in which a copper monolayer is applied to the ternary nanoparticles; this is followed by the galvanic displacement of Cu with Pt to generate a Pt monolayer on the surface of the core. The core-shell Pd1Ir1Ni2@Pt/C catalyst exhibits excellent oxygen reduction reaction activity, yielding a mass activity significantly higher than that of Pt monolayer catalysts containing PdIr or PdNi nanoparticles as cores and four times higher than that of a commercial Pt/C electrocatalyst. In 0.1 M HClO4, the half-wave potential reaches 0.91 V, about 30 mV higher than that of Pt/C. We verify the structure and composition of the carbon-supported PdIrNi nanoparticles using X-ray powder diffraction, X-ray photoelectron spectroscopy, thermogravimetry, transmission electron microscopy, and energy dispersive X-ray spectrometry, and we perform a stability test that confirms the excellent stability of our core-shell catalyst. We suggest that the porous structure resulting from the dissolution of Ni in the alloy nanoparticles may be the main reason for the catalyst’s enhanced performance.

Design criteria for stable Pt/C fuel cell catalysts

Directory of Open Access Journals (Sweden)

Josef C. Meier

2014-01-01

Full Text Available Platinum and Pt alloy nanoparticles supported on carbon are the state of the art electrocatalysts in proton exchange membrane fuel cells. To develop a better understanding on how material design can influence the degradation processes on the nanoscale, three specific Pt/C catalysts with different structural characteristics were investigated in depth: a conventional Pt/Vulcan catalyst with a particle size of 3–4 nm and two Pt@HGS catalysts with different particle size, 1–2 nm and 3–4 nm. Specifically, Pt@HGS corresponds to platinum nanoparticles incorporated and confined within the pore structure of the nanostructured carbon support, i.e., hollow graphitic spheres (HGS. All three materials are characterized by the same platinum loading, so that the differences in their performance can be correlated to the structural characteristics of each material. The comparison of the activity and stability behavior of the three catalysts, as obtained from thin film rotating disk electrode measurements and identical location electron microscopy, is also extended to commercial materials and used as a basis for a discussion of general fuel cell catalyst design principles. Namely, the effects of particle size, inter-particle distance, certain support characteristics and thermal treatment on the catalyst performance and in particular the catalyst stability are evaluated. Based on our results, a set of design criteria for more stable and active Pt/C and Pt-alloy/C materials is suggested.

Revealing the Dynamics of Platinum Nanoparticle Catalysts on Carbon in Oxygen and Water Using Environmental TEM

Energy Technology Data Exchange (ETDEWEB)

Luo, Langli [Environmental; Engelhard, Mark H. [Environmental; Shao, Yuyan [Environmental; Wang, Chongmin [Environmental

2017-10-02

Deactivation of supported metal nanoparticle catalysts, especially in relevant gas condition, is a critical challenge for many technological applications, including heterogeneous catalysis, electrocatalysis, fuel cells, biomedical imaging and drug delivery. It has been far more commonly realized that deactivation of catalysts stems from surface area loss due to particle coarsening, however, for which the mechanism remains largely unclear. Herein, we use aberration corrected environmental transmission electron microscopy, at atomic level, to in-situ observe the dynamics of Pt catalyst in fuel cell relevant gas conditions. Particles migration and coalescence is observed to be the dominant coarsening process. As compared with the case of H2O, O2 promotes Pt nanoparticle migration on carbon surface. Surprisingly, coating Pt/carbon with a nanofilm of electrolyte (Nafion ionomer) leads to a faster migration of Pt in H2O than in O2, a consequence of Nafion-carbon interface water “lubrication” effect. Atomically, the particles coalescence is featured by re-orientation of particles towards lattice matching, a process driven by orientation dependent van der Waals force. These results provide direct observations of dynamics of metal nanoparticles at critical surface/interface under relevant conditions and yield significant insights into the multi-phase interaction in related technological processes.

Electrochemical DNA biosensors based on platinum nanoparticles combined carbon nanotubes

International Nuclear Information System (INIS)

Zhu Ningning; Chang Zhu; He Pingang; Fang Yuzhi

2005-01-01

Platinum nanoparticles were used in combination with multi-walled carbon nanotubes (MWCNTs) for fabricating sensitivity-enhanced electrochemical DNA biosensor. Multi-walled carbon nanotubes and platinum nanoparticles were dispersed in Nafion, which were used to fabricate the modification of the glassy carbon electrode (GCE) surface. Oligonucleotides with amino groups at the 5' end were covalently linked onto carboxylic groups of MWCNTs on the electrode. The hybridization events were monitored by differential pulse voltammetry (DPV) measurement of the intercalated daunomycin. Due to the ability of carbon nanotubes to promote electron-transfer reactions, the high catalytic activities of platinum nanoparticles for chemical reactions, the sensitivity of presented electrochemical DNA biosensors was remarkably improved. The detection limit of the method for target DNA was 1.0 x 10 -11 mol l -1

Carbon-supported co-pyridine as non-platinum cathode catalyst for alkaline membrane fuel cells

International Nuclear Information System (INIS)

Qiao, Jinli; Xu, Li; Liu, Yuyu; Xu, Pan; Shi, Jingjing; Liu, Shiyao; Tian, Binglun

2013-01-01

Development of high-performance cost-effective electrocatalyts that can replace Pt catalyst have been a central theme in polymer electrolyte membrane fuel cells (PEMFCs) including direct methanol fuel cells (DMFCs). Here we show that carbon-supported pyridine–cobalt nanoparticles (CoPy/C) can generate a high catalytic activity toward the oxygen reduction reaction (ORR). The catalysts are synthesized using cobalt sulfate heptahydrate (CoSO 4 ·7H 2 O) and pyridine (Py) as the Co and N precursors via a solid state reaction by heat-treatment in an inert atmosphere at 800 °C. In particular, the ORR kinetics on these catalyst materials are evaluated using rotating disk electrode (RDE) technique in electrolytes of various KOH concentrations, ranging from 0.05 to 12 M. The Koutecky–Levich equation analyses indicate that the transferred electron number, n, per oxygen molecule on CoPy/C electrode depend on the low negative ovevrpotentials in low KOH concentrations, whereas in high KOH concentrations the values of n for oxygen reduction depend on the high negative overpotentials, and varies between 3.5 and 4.0. These catalysts exhibit the superior methanol tolerance to commercial 40%Pt/C catalyst, and the negative effect of high KOH concentration is much less for CoPy/C than for Pt/C, suggesting the promising utilization of CoPy/C as electrocatalysts for alkaline polymer electrolyte membrane fuel cells

Bio-inspired routes for synthesizing efficient nanoscale platinum electrocatalysts

Energy Technology Data Exchange (ETDEWEB)

Cha, Jennifer N. [Univ. of California, San Diego, CA (United States); Wang, Joseph [Univ. of California, San Diego, CA (United States)

2014-08-31

The overall objective of the proposed research is to use fundamental advances in bionanotechnology to design powerful platinum nanocrystal electrocatalysts for fuel cell applications. The new economically-viable, environmentally-friendly, bottom-up biochemical synthetic strategy will produce platinum nanocrystals with tailored size, shape and crystal orientation, hence leading to a maximum electrochemical reactivity. There are five specific aims to the proposed bio-inspired strategy for synthesizing efficient electrocatalytic platinum nanocrystals: (1) isolate peptides that both selectively bind particular crystal faces of platinum and promote the nucleation and growth of particular nanocrystal morphologies, (2) pattern nanoscale 2-dimensional arrays of platinum nucleating peptides from DNA scaffolds, (3) investigate the combined use of substrate patterned peptides and soluble peptides on nanocrystal morphology and growth (4) synthesize platinum crystals on planar and large-area carbon electrode supports, and (5) perform detailed characterization of the electrocatalytic behavior as a function of catalyst size, shape and morphology. Project Description and Impact: This bio-inspired collaborative research effort will address key challenges in designing powerful electrocatalysts for fuel cell applications by employing nucleic acid scaffolds in combination with peptides to perform specific, environmentally-friendly, simultaneous bottom-up biochemical synthesis and patterned assembly of highly uniform and efficient platinum nanocrystal catalysts. Bulk synthesis of nanoparticles usually produces a range of sizes, accessible catalytic sites, crystal morphologies, and orientations, all of which lead to inconsistent catalytic activities. In contrast, biological systems routinely demonstrate exquisite control over inorganic syntheses at neutral pH and ambient temperature and pressures. Because the orientation and arrangement of the templating biomolecules can be precisely

Dissolved oxygen removal in a column packed with catalyst

International Nuclear Information System (INIS)

Lee, Han Soo; Chung, Hong Suk; Cho, Young Hyun; Ahn, Do Hee; Kim, Eun Kee

1996-01-01

The dissolved oxygen removed by H 2 -O 2 reaction in column packed with various catalysts was examined. The catalysts employed were the prepared polymeric catalyst, platinum on activated carbon, and Lewatit OC-1045 which is available commercially. The column experiments with the prepared polymeric catalyst showed the dissolved oxygen reduced to 35 ppb which is below the limit in feel water of power plants. This implies the likely application of the prepared catalyst for practical use. The activated carbon required the pre-treatment for the removed of dissolved oxygen, since the surface of activated carbon contains much oxygen adsorbed initially. The Lewatit catalyst exposed the best performance, however, the aged one showed the gradual loss of catalytic activity due to degradation of resin catalyst. 14 refs., 6 figs., 2 tabs. (author)

Methanol-Tolerant Platinum-Palladium Catalyst Supported on Nitrogen-Doped Carbon Nanofiber for High Concentration Direct Methanol Fuel Cells.

Science.gov (United States)

Kim, Jiyoung; Jang, Jin-Sung; Peck, Dong-Hyun; Lee, Byungrok; Yoon, Seong-Ho; Jung, Doo-Hwan

2016-08-15

Pt-Pd catalyst supported on nitrogen-doped carbon nanofiber (N-CNF) was prepared and evaluated as a cathode electrode of the direct methanol fuel cell (DMFC). The N-CNF, which was directly synthesized by the catalytic chemical vapor deposition from acetonitrile at 640 °C, was verified as having a change of electrochemical surface properties such as oxygen reduction reaction (ORR) activities and the electrochemical double layer compared with common carbon black (CB). To attain the competitive oxygen reduction reaction activity with methanol tolerance, the Pt and Pd metals were supported on the CB or the N-CNF. The physical and electrochemical characteristics of the N-CNF-supported Pt-Pd catalyst were examined and compared with catalyst supported on the CB. In addition, DMFC single cells using these catalysts as the cathode electrode were applied to obtain I-V polarization curves and constant current operating performances with high-concentration methanol as the fuel. Pt-Pd catalysts had obvious ORR activity even in the presence of methanol. The higher power density was obtained at all the methanol concentrations when it applied to the membrane electrode assembly (MEA) of the DMFC. When the N-CNF is used as the catalyst support material, a better performance with high-concentration methanol is expected.

Methanol-Tolerant Platinum-Palladium Catalyst Supported on Nitrogen-Doped Carbon Nanofiber for High Concentration Direct Methanol Fuel Cells

Directory of Open Access Journals (Sweden)

Jiyoung Kim

2016-08-01

Full Text Available Pt-Pd catalyst supported on nitrogen-doped carbon nanofiber (N-CNF was prepared and evaluated as a cathode electrode of the direct methanol fuel cell (DMFC. The N-CNF, which was directly synthesized by the catalytic chemical vapor deposition from acetonitrile at 640 °C, was verified as having a change of electrochemical surface properties such as oxygen reduction reaction (ORR activities and the electrochemical double layer compared with common carbon black (CB. To attain the competitive oxygen reduction reaction activity with methanol tolerance, the Pt and Pd metals were supported on the CB or the N-CNF. The physical and electrochemical characteristics of the N-CNF–supported Pt-Pd catalyst were examined and compared with catalyst supported on the CB. In addition, DMFC single cells using these catalysts as the cathode electrode were applied to obtain I-V polarization curves and constant current operating performances with high-concentration methanol as the fuel. Pt-Pd catalysts had obvious ORR activity even in the presence of methanol. The higher power density was obtained at all the methanol concentrations when it applied to the membrane electrode assembly (MEA of the DMFC. When the N-CNF is used as the catalyst support material, a better performance with high-concentration methanol is expected.

Novel catalysts for isotopic exchange between hydrogen and liquid water

International Nuclear Information System (INIS)

Butler, J.P.; Rolston, J.H.; Stevens, W.H.

1978-01-01

Catalytic isotopic exchange between hydrogen and liquid water offers many inherent potential advantages for the separation of hydrogen isotopes which is of great importance in the Canadian nuclear program. Active catalysts for isotopic exchange between hydrogen and water vapor have long been available, but these catalysts are essentially inactive in the presence of liquid water. New, water-repellent platinum catalysts have been prepared by: (1) treating supported catalysts with silicone, (2) depositing platinum on inherently hydrophobic polymeric supports, and (3) treating platinized carbon with Teflon and bonding to a carrier. The activity of these catalysts for isotopic exchange between countercurrent streams of liquid water and hydrogen saturated with water vapor has been measured in a packed trickle bed integral reactor. The performance of these hydrophobic catalysts is compared with nonwetproofed catalysts. The mechanism of the overall exchange reaction is briefly discussed. 6 figures

Electrochemical performance for the electro-oxidation of ethylene glycol on a carbon-supported platinum catalyst at intermediate temperature

Energy Technology Data Exchange (ETDEWEB)

Kosaka, Fumihiko; Oshima, Yoshito [Department of Environment Systems, Graduate School of Frontier Sciences, University of Tokyo, 5-1-5 Kashiwanoha, Kashiwa, Chiba 277-8563 (Japan); Otomo, Junichiro, E-mail: otomo@k.u-tokyo.ac.jp [Department of Environment Systems, Graduate School of Frontier Sciences, University of Tokyo, 5-1-5 Kashiwanoha, Kashiwa, Chiba 277-8563 (Japan)

2011-11-30

Highlights: > High oxidation current in ethylene glycol electro-oxidation at intermediate temperature. > High C-C bond dissociation ratio of ethylene glycol at intermediate temperature. > Low selectivity for CH{sub 4} in ethylene glycol electro-oxidation. > High selectivity for CO{sub 2} according to an increase in steam to carbon ratios. - Abstract: To determine the kinetic performance of the electro-oxidation of a polyalcohol operating at relatively high temperatures, direct electrochemical oxidation of ethylene glycol on a carbon supported platinum catalyst (Pt/C) was investigated at intermediate temperatures (235-255 {sup o}C) using a single cell fabricated with a proton-conducting solid electrolyte, CsH{sub 2}PO{sub 4}, which has high proton conductivity (>10{sup -2} S cm{sup -1}) in the intermediate temperature region. A high oxidation current density was observed, comparable to that for methanol electro-oxidation and also higher than that for ethanol electro-oxidation. The main products of ethylene glycol electro-oxidation were H{sub 2}, CO{sub 2}, CO and a small amount of CH{sub 4} formation was also observed. On the other hand, the amounts of C{sub 2} products such as acetaldehyde, acetic acid and glycolaldehyde were quite small and were lower by about two orders of magnitude than the gaseous reaction products. This clearly shows that C-C bond dissociation proceeds almost to completion at intermediate temperatures and the dissociation ratio reached a value above 95%. The present observations and kinetic analysis suggest the effective application of direct alcohol fuel cells operating at intermediate temperatures and indicate the possibility of total oxidation of alcohol fuels.

Electro-oxidation of Ethanol on Carbon Supported PtSn and PtSnNi Catalysts

Directory of Open Access Journals (Sweden)

Nur Hidayati

2016-03-01

Full Text Available Even though platinum is known as an active electro-catalyst for ethanol oxidation at low temperatures (< 100 oC, choosing the electrode material for ethanol electro-oxidation is a crucial issue. It is due to its property which easily poisoned by a strong adsorbed species such as CO. PtSn-based electro-catalysts have been identified as better catalysts for ethanol electro-oxidation. The third material is supposed to improved binary catalysts performance. This work presents a study of the ethanol electro-oxidation on carbon supported Pt-Sn and Pt-Sn-Ni catalysts. These catalysts were prepared by alcohol reduction. Nano-particles with diameters between 2.5-5.0 nm were obtained. The peak of (220 crystalline face centred cubic (fcc Pt phase for PtSn and PtSnNi alloys was repositioned due to the presence of Sn and/or Ni in the alloy. Furthermore, the modification of Pt with Sn and SnNi improved ethanol and CO electro-oxidation. Copyright © 2016 BCREC GROUP. All rights reserved Received: 10th November 2015; Revised: 1st February 2016; Accepted: 1st February 2016 How to Cite: Hidayati, N., Scott, K. (2016. Electro-oxidation of Ethanol on Carbon Supported PtSn and PtSnNi Catalysts. Bulletin of Chemical Reaction Engineering & Catalysis, 11 (1: 10-20. (doi:10.9767/bcrec.11.1.394.10-20 Permalink/DOI: http://dx.doi.org/10.9767/bcrec.11.1.394.10-20

Growth of vertically aligned single-walled carbon nanotubes with metallic chirality through faceted FePt-Au catalysts

Science.gov (United States)

Ohashi, Toshiyuki; Iwama, Hiroki; Shima, Toshiyuki

2016-02-01

Direct synthesis of vertically aligned metallic single-walled carbon nanotubes (m-SWCNT forests) is a difficult challenge. We have successfully synthesized m-SWCNT forests using faceted iron platinum-gold catalysts epitaxially grown on a single crystalline magnesium oxide substrate. The metallic content of the forests estimated by Raman spectroscopy reaches 90%. From the standpoint of growth rate of the forests, the growth mechanism is probably based on the catalyst of solid state. It is suggested that preferential growth of m-SWCNTs is achieved when both factors are satisfied, namely, {111} dominant octahedral facet and ideal size (fine particles) of FePt particles.

Electrochemical and microstructural characterization of platinum supported on glassy carbon

Directory of Open Access Journals (Sweden)

Terzić Sanja

2007-01-01

Full Text Available The effect of the electrochemical oxidation of glassy carbon on the deposition of platinum particles and the electrocatalytic activity of platinum supported on oxidized glassy carbon were studied for methanol oxidation in H2SO4 solution. Platinum was potentiostatically deposited from H2SO4 + 6mM H2PtCl6 solution. Glassy carbon was anodically polarized in 1 M NaOH at 1.41 V (SCE for 35 and 95 s and in 0.5 M H2SO4 at 2V (SCE for 35; 95 s and 2.25 V for 35 and 95 s. Electrochemical treatment of the GC support leads to a better distribution of platinum on the substrate and has remarkable effect on the activity. The activity of the Pt/GCox electrode for methanol oxidation is larger than that of polycrystalline Pt and by more than one order of magnitude larger than that of a Pt/GC electrode. This increase in activity indicates the pronounced role of the organic residues of the GC support on the properties of Pt particles deposited on glassy carbon.

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.

De-oxygenation of CO2 by using Hydrogen, Carbon and Methane over Alumina-Supported Catalysts

Directory of Open Access Journals (Sweden)

R.Y. Raskar

2012-06-01

Full Text Available The de-oxygenation of CO2 was explored by using hydrogen, methane, carbon etc., over alumina supported catalysts. The alumina-supported ruthenium, rhodium, platinum, molybdenum, vanadium and magnesium catalysts were first reduced in hydrogen atmosphere and then used for the de-oxygenation of CO2. Furthermore, experimental variables for the de-oxygenation of CO2 were temperature (range 50 to 650 oC, H2/CO2 mole ratios (1.0 to 5, and catalyst loading (0.5 to 10 wt %. During the de-oxygenation of CO2 with H2 or CH4 or carbon, conversion of CO2, selectivity to CO and CH4 were estimated. Moreover, 25.4 % conversion of CO2 by hydrogen was observed over 1 wt% Pt/Al2O3 catalyst at 650 oC with 33.8 % selectivity to CH4. However, 8.1 to 13.9 % conversion of CO2 was observed over 1 wt% Pt/Al2O3 catalyst at 550 oC in the presence of both H2 and CH4. Moreover, 42.8 to 79.4 % CH4 was converted with 9 to 23.1 % selectivity to CO. It was observed that the de-oxygenation of CO2 by hydrogen, carbon and methane produced carbon, CO and CH4. © 2012 BCREC UNDIP. All rights reservedReceived: 6th February 2012; Revised: 23rd April 2012; Accepted: 24th April 2012[How to Cite: R. Y. Raskar, K. B. Kale, A. G. Gaikwad. (2011. De-oxygenation of CO2 by using Hydrogen, Carbon and Methane over Alumina-Supported Catalysts. Bulletin of Chemical Reaction Engineering & Catalysis, 7 (1: 59-69.  doi:10.9767/bcrec.7.1.1631.59-69][How to Link / DOI: http://dx.doi.org/10.9767/bcrec.7.1.1631.59-69 ] | View in 

Pt -based anode catalysts for direct ethanol fuel cells

International Nuclear Information System (INIS)

Hoyos, Bibian; Sanchez, Carlos; Gonzalez, Javier

2007-01-01

In this work it is studied the electro-catalytic behavior of pure platinum and platinum-based alloys with Ru, Sn, Ir, and Os supported on carbon to the ethanol electro-oxidation in aims to develop anodic catalysts for direct ethanol fuel cells, additionally, porous electrodes and membrane electrode assemblies were built for proton exchange membrane fuel cells in which the electrodes were tested. Catalysts characterization was made by cyclic voltammetry whereas the fuel cells behavior tests were made by current-potential polarization curves. in general, all alloys show a lower on-set reaction potential and a higher catalytic activity than pure platinum. However, in the high over potential zone, pure platinum has higher catalytic activity than the alloys. In agreement with these results, the alloys studied here could be useful in fuel cells operating on moderated and low current

ETEM observation of Pt/C electrode catalysts in a moisturized cathode atmosphere

International Nuclear Information System (INIS)

Yoshida, K; Zhang, X; Tanaka, N; Boyes, E D; Gai, P L

2014-01-01

There have been reports of challenges in designing platinum carbon (Pt/C) electrode catalysts for PEMFC. Pt/C electrode catalysts deactivate much faster on the cathode (in moisturized O 2 ) than on the anode (in H 2 ). To understand influences of moisture and oxygen on the deactivation of the Pt/C catalysts in proton-exchange-membrane fuel cells (PEMFCs), spherical-aberration-corrected environmental transmission electron microscopy (AC-ETEM) was applied with a high-speed CCD camera. Structural changes of the Pt/C electrode catalysts were dynamically recorded in moisturized nitrogen, oxygen and hydrogen. The mass spectrometry confirmed the moisture content (between 5 to 30 %) of nitrogen driving gas through a humidifier. Coalescence of platinum nanoparticles (D = 3.24 nm) was carefully evaluated in pure N 2 and moisturized N 2 atmosphere. The Pt/C showed considerable structural weakness in a moisturized N2 atmosphere. Comparable results obtained by AC-ETEM in different gas atmospheres also suggested ways to improve the oxygen reduction reaction (ORR). In this paper, the deactivation process due to moisture (hydroxylation) of carbon supports is discussed using for comparison the movement of platinum nanoparticles measured in moisturized nitrogen and pure nitrogen atmospheres

Catalysts for oxidation of mercury in flue gas

Science.gov (United States)

Granite, Evan J [Wexford, PA; Pennline, Henry W [Bethel Park, PA

2010-08-17

Two new classes of catalysts for the removal of heavy metal contaminants, especially mercury (Hg) from effluent gases. Both of these classes of catalysts are excellent absorbers of HCl and Cl.sub.2 present in effluent gases. This adsorption of oxidizing agents aids in the oxidation of heavy metal contaminants. The catalysts remove mercury by oxidizing the Hg into mercury (II) moieties. For one class of catalysts, the active component is selected from the group consisting of iridium (Ir) and iridum-platinum (Ir/Pt) alloys. The Ir and Ir/Pt alloy catalysts are especially corrosion resistant. For the other class of catalyst, the active component is partially combusted coal or "Thief" carbon impregnated with Cl.sub.2. Untreated Thief carbon catalyst can be self-activating in the presence of effluent gas streams. The Thief carbon catalyst is disposable by means of capture from the effluent gas stream in a particulate collection device (PCD).

Treatment of ammonia by catalytic wet oxidation process over platinum-rhodium bimetallic catalyst in a trickle-bed reactor: effect of pH.

Science.gov (United States)

Hung, Chang-Mao; Lin, Wei-Bang; Ho, Ching-Lin; Shen, Yun-Hwei; Hsia, Shao-Yi

2010-08-01

This work adopted aqueous solutions of ammonia for use in catalytic liquid-phase reduction in a trickle-bed reactor with a platinum-rhodium bimetallic catalyst, prepared by the co-precipitation of chloroplatinic acid (H2PtCl6) and rhodium nitrate [Rh(NO3)3]. The experimental results demonstrated that a minimal amount of ammonia was removed from the solution by wet oxidation in the absence of any catalyst, while approximately 97.0% of the ammonia was removed by wet oxidation over the platinum-rhodium bimetallic catalyst at 230 degrees C with an oxygen partial pressure of 2.0 MPa. The oxidation of ammonia has been studied as a function of pH, and the main reaction products were determined. A synergistic effect is manifest in the platinum-rhodium bimetallic structure, in which the material has the greatest capacity to reduce ammonia. The reaction pathway linked the oxidizing ammonia to nitric oxide, nitrogen, and water.

LDRD final report on synthesis of shape-and size-controlled platinum and platinum alloy nanostructures on carbon with improved durability.

Energy Technology Data Exchange (ETDEWEB)

Shelnutt, John Allen; Garcia, Robert M.; Song, Yujiang; Moreno, Andres M.; Stanis, Ronald J.

2008-10-01

This project is aimed to gain added durability by supporting ripening-resistant dendritic platinum and/or platinum-based alloy nanostructures on carbon. We have developed a new synthetic approach suitable for directly supporting dendritic nanostructures on VXC-72 carbon black (CB), single-walled carbon nanotubes (SWCNTs), and multi-walled carbon nanotubes (MWCNTs). The key of the synthesis is to creating a unique supporting/confining reaction environment by incorporating carbon within lipid bilayer relying on a hydrophobic-hydrophobic interaction. In order to realize size uniformity control over the supported dendritic nanostructures, a fast photocatalytic seeding method based on tin(IV) porphyrins (SnP) developed at Sandia was applied to the synthesis by using SnP-containing liposomes under tungsten light irradiation. For concept approval, one created dendritic platinum nanostructure supported on CB was fabricated into membrane electrode assemblies (MEAs) for durability examination via potential cycling. It appears that carbon supporting is essentially beneficial to an enhanced durability according to our preliminary results.

Tin-oxide-coated single-walled carbon nanotube bundles supporting platinum electrocatalysts for direct ethanol fuel cells

International Nuclear Information System (INIS)

Hsu, Ryan S; Higgins, Drew; Chen Zhongwei

2010-01-01

Novel tin-oxide (SnO 2 )-coated single-walled carbon nanotube (SWNT) bundles supporting platinum (Pt) electrocatalysts for ethanol oxidation were developed for direct ethanol fuel cells. SnO 2 -coated SWNT (SnO 2 -SWNT) bundles were synthesized by a simple chemical-solution route. SnO 2 -SWNT bundles supporting Pt (Pt/SnO 2 -SWNTs) electrocatalysts and SWNT-supported Pt (Pt/SWNT) electrocatalysts were prepared by an ethylene glycol reduction method. The catalysts were physically characterized using TGA, XRD and TEM and electrochemically evaluated through cyclic voltammetry experiments. The Pt/SnO 2 -SWNTs showed greatly enhanced electrocatalytic activity for ethanol oxidation in acid medium, compared to the Pt/SWNT. The optimal SnO 2 loading of Pt/SnO 2 -SWNT catalysts with respect to specific catalytic activity for ethanol oxidation was also investigated.

Tin-oxide-coated single-walled carbon nanotube bundles supporting platinum electrocatalysts for direct ethanol fuel cells.

Science.gov (United States)

Hsu, Ryan S; Higgins, Drew; Chen, Zhongwei

2010-04-23

Novel tin-oxide (SnO(2))-coated single-walled carbon nanotube (SWNT) bundles supporting platinum (Pt) electrocatalysts for ethanol oxidation were developed for direct ethanol fuel cells. SnO(2)-coated SWNT (SnO(2)-SWNT) bundles were synthesized by a simple chemical-solution route. SnO(2)-SWNT bundles supporting Pt (Pt/SnO(2)-SWNTs) electrocatalysts and SWNT-supported Pt (Pt/SWNT) electrocatalysts were prepared by an ethylene glycol reduction method. The catalysts were physically characterized using TGA, XRD and TEM and electrochemically evaluated through cyclic voltammetry experiments. The Pt/SnO(2)-SWNTs showed greatly enhanced electrocatalytic activity for ethanol oxidation in acid medium, compared to the Pt/SWNT. The optimal SnO(2) loading of Pt/SnO(2)-SWNT catalysts with respect to specific catalytic activity for ethanol oxidation was also investigated.

Studies on PEM fuel cell noble metal catalyst dissolution

DEFF Research Database (Denmark)

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

2011-01-01

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

Influence of plasma treatment of carbon blacks on electrochemical activity of Pt/carbon blacks catalysts for DMFCs

Science.gov (United States)

Kim, Seok; Cho, Mi-Hwa; Lee, Jae-Rock; Park, Soo-Jin

In this work, in order to improve the dispersion of platinum catalysts deposited on carbon materials, the effects of surface plasma treatment of carbon blacks (CBs) were investigated. The surface characteristics of the CBs were determined by fourier transformed-infrared (FT-IR), X-ray photoelectron spectroscopy (XPS), and Boehm's titration method. The electrochemical properties of the plasma-treated CBs-supported Pt (Pt/CBs) catalysts were analyzed by linear sweep voltammetry (LSV) experiments. From the results of FT-IR and acid-base values, N 2-plasma treatment of the CBs at 300 W intensity led to a formation of a free radical on the CBs. The peak intensity increased with increase of the treatment time, due to the formation of new basic functional groups (such as C-N, C dbnd N, -NH 3 +, -NH, and dbnd NH) by the free radical on the CBs. Accordingly, the basic values were enhanced by the basic functional groups. However, after a specific reaction time, N 2-plasma treatment could hardly influence on change of the surface functional groups of CBs, due to the disappearance of free radical. Consequently, it was found that optimal treatment time was 30 s for the best electro activity of Pt/CBs catalysts and the N 2-plasma treated Pt/CBs possessed the better electrochemical properties than the pristine Pt/CBs.

Spatio-temporal dynamics of oscillatory heterogeneous catalysis: CO oxidation on platinum

Science.gov (United States)

Yamamoto, S. Y.; Surko, C. M.; Maple, M. B.; Pina, R. K.

1995-06-01

Reaction-rate oscillations in the oxidation of carbon monoxide on the surface of platinum catalysts are studied in a continuous flow reactor at atmospheric pressure using infrared imaging. Small-amplitude temperature oscillations (0.2-8 K) result in approximately isothermal conditions, where changes in rate constants, for typical activation energies and temperatures, are small. The catalysts are in the form of platinum thin films on quartz substrates and provide highly repeatable oscillatory behavior. The platinum films are fabricated in the form of annular rings which provide a quasi-one-dimensional geometry in order to simplify comparison to theoretical models. Time-series measurements by means of thermocouples are used to characterize the oscillations. The infrared images show that most oscillations are spatially synchronized to within the 0.25 s time resolution of the experiment. The images also show that ``fine structure'' oscillations (i.e., small-amplitude, high frequency oscillations superimposed on larger-amplitude waveforms) are associated with spatially desynchronized patterns.

A Pd/C-CeO2 Anode Catalyst for High-Performance Platinum-Free Anion Exchange Membrane Fuel Cells.

Science.gov (United States)

Miller, Hamish A; Lavacchi, Alessandro; Vizza, Francesco; Marelli, Marcello; Di Benedetto, Francesco; D'Acapito, Francesco; Paska, Yair; Page, Miles; Dekel, Dario R

2016-05-10

One of the biggest obstacles to the dissemination of fuel cells is their cost, a large part of which is due to platinum (Pt) electrocatalysts. Complete removal of Pt is a difficult if not impossible task for proton exchange membrane fuel cells (PEM-FCs). The anion exchange membrane fuel cell (AEM-FC) has long been proposed as a solution as non-Pt metals may be employed. Despite this, few examples of Pt-free AEM-FCs have been demonstrated with modest power output. The main obstacle preventing the realization of a high power density Pt-free AEM-FC is sluggish hydrogen oxidation (HOR) kinetics of the anode catalyst. Here we describe a Pt-free AEM-FC that employs a mixed carbon-CeO2 supported palladium (Pd) anode catalyst that exhibits enhanced kinetics for the HOR. AEM-FC tests run on dry H2 and pure air show peak power densities of more than 500 mW cm(-2) . © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The platinum catalyst layer in polymer-electrolyte fuel cells[Dissertation 17127]; Die Platinkatalysatorschicht in Polymerelektrolyt-Brennstoffzellen. Beitraege zum Verstaendnis und zur Optimierung

Energy Technology Data Exchange (ETDEWEB)

Reiner, A.

2007-07-01

This illustrated, comprehensive dissertation by Dr. Andreas Reiner presents an in-depth analysis of polymer electrolyte fuel cells (PEFC) and in particular, their platinum catalyst layer. First of all, the thermodynamics and kinetics involved are reviewed, along with components, their efficiencies and the catalyst layer. The methods used, including scanning electron microscope, x-ray and Rutherford spectroscopy are discussed. The structure and composition of co-sputtered catalyst layers and their production are described. Electro-chemical activation and the electro-chemical properties of the layers are discussed. The second part of the dissertation deals with the principle of hydrogen under-potential deposition. This method provides information about the electrochemically active platinum surface fraction. The results of investigations made are presented and discussed.

Selective hydrogenation of halogenated arenes using porous manganese oxide (OMS-2) and platinum supported OMS-2 catalysts.

Science.gov (United States)

McManus, Iain J; Daly, Helen; Manyar, Haresh G; Taylor, S F Rebecca; Thompson, Jillian M; Hardacre, Christopher

2016-07-04

Porous manganese oxide (OMS-2) and platinum supported on OMS-2 catalysts have been shown to facilitate the hydrogenation of the nitro group in chloronitrobenzene to give chloroaniline with no dehalogenation. Complete conversion was obtained within 2 h at 25 °C and, although the rate of reaction increased with increasing temperature up to 100 °C, the selectivity to chloroaniline remained at 99.0%. Use of Pd/OMS-2 or Pt/Al2O3 resulted in significant dechlorination even at 25 °C and 2 bar hydrogen pressure giving a selectivity to chloroaniline of 34.5% and 77.8%, respectively, at complete conversion. This demonstrates the potential of using platinum group metal free catalysts for the selective hydrogenation of halogenated aromatics. Two pathways were observed for the analogous nitrobenzene hydrogenation depending on the catalyst used. The hydrogenation of nitrobenzene was found to follow a direct pathway to aniline and nitrosobenzene over Pd/OMS-2 in contrast to the OMS and Pt/OMS-2 catalysts which resulted in formation of nitrosobenzene, azoxybenzene and azobenzene/hydrazobenzene intermediates before complete conversion to aniline. These results indicate that for Pt/OMS-2 the hydrogenation proceeds predominantly over the support with the metal acting to dissociate hydrogen. In the case of Pd/OMS-2 both the hydrogenation and hydrogen adsorption occur on the metal sites.

Platinum recycling in the United States in 1998

Science.gov (United States)

Hilliard, Henry E.

2001-01-01

In the United States, catalytic converters are the major source of secondary platinum for recycling. Other sources of platinum scrap include reforming and chemical process catalysts. The glass industry is a small but significant source of platinum scrap. In North America, it has been estimated that in 1998 more than 20,000 kilograms per year of platinum-group metals from automobile catalysts were available for recycling. In 1998, an estimated 7,690 kilograms of platinum were recycled in the United States. U.S. recycling efficiency was calculated to have been 76 percent in 1998; the recycling rate was estimated at 16 percent.

Recovery of Platinum Group Metals from Spent Catalysts Using Iron Chloride Vapor Treatment

Science.gov (United States)

Taninouchi, Yu-ki; Okabe, Toru H.

2018-05-01

The recovery of platinum group metals (PGMs) from spent automobile catalysts is a difficult process because of their relatively low contents in the scrap. In this study, to improve the efficiency of the existing recycling techniques, a novel physical concentration method involving treatment with FeCl2 vapor has been examined. The reactions occurring between typical catalyst components and FeCl2 vapor are discussed from the thermodynamic point of view, and the validity of the proposed technique was experimentally verified. The obtained results indicate that the vapor treatment at around 1200 K (927 °C) can effectively alloy PGMs (Pt, Pd, and Rh) with Fe, resulting in the formation of a ferromagnetic alloy. It was also confirmed that cordierite and alumina (the major catalyst components) remained unreacted after the vapor treatment, while ceria species were converted into oxychlorides. The samples simulating the automobile catalyst were also subjected to magnetic separation after the treatment with FeCl2 vapor; as a result, PGMs were successfully extracted and concentrated in the form of a magnetic powder. Thus, the FeCl2 vapor treatment followed by magnetic separation can be utilized for recovering PGMs directly from spent catalysts as an effective pretreatment for the currently used recycling methods.

Carbon monoxide tolerant anodes for proton exchange membrane (PEM) fuel cells. 1. Catalyst development approach

Energy Technology Data Exchange (ETDEWEB)

Holleck, G L; Pasquariello, D M; Clauson, S L

1998-07-01

PEM fuel cells are highly attractive for distributed power and cogeneration systems. They are efficient and function virtually without noise or pollution. To be competitive PEM fuel cells must operate on fuel mixtures obtained by reforming of widely available natural gas or liquid hydrocarbons. Reformed fuel gas mixtures invariably contain CO, a strong poison for Pt. Therefore CO tolerant anode catalysts are essential for wide spread PEMFC introduction. It is the objective to develop effective CO tolerant fuel cell catalysts based on multi-component platinum-transition metal alloys. Towards this goal the authors have developed a novel approach for the synthesis and performance evaluation of multifunctional ternary alloy fuel cell catalysts. The alloys are prepared as well-defined thin films on standard TFE-bonded carbon substrates via a dc magnetron sputtering technique. The anodes are laminated to Nafion membranes and the electrochemical performance is measured in a representative fuel cell configuration with H{sub 2} and H{sub 2}/CO gas mixtures. The multi-target sputtering technique permits one to reproducibly synthesize true alloy films of controlled composition. The deposit morphology and electrode structure are determined by the standardized TFE bonded carbon substrate. The thin catalyst layer is concentrated at the electrode ionomer interface where it can be fully utilized in a representative fuel cell configuration. Thus, a true comparative fuel cell catalyst evaluation is possible. The effectiveness of this approach will be demonstrated with Pt, Pt-Ru and Pt-Ru-X catalyzed anodes.

Rapid in situ synthesis of spherical microflower Pt/C catalyst via spray-drying for high performance fuel cell application

Energy Technology Data Exchange (ETDEWEB)

Balgis, R.; Ogi, T.; Okuyama, K. [Department of Chemical Engineering, Graduate School of Engineering, Hiroshima University, Higashi Hiroshima, Hiroshima (Japan); Anilkumar, G.M.; Sago, S. [Research and Development Centre, Noritake Co., Ltd., Higashiyama, Miyoshi, Aichi (Japan)

2012-08-15

A facile route for the rapid in situ synthesis of platinum nanoparticles on spherical microflower carbon has been developed. An aqueous precursor slurry containing carbon black, polystyrene latex (PSL), polyvinyl alcohol, and platinum salt was spray-dried, followed by calcination to simultaneously reduce platinum salt and to decompose PSL particles. Prepared Pt/C catalyst showed high-performance electrocatalytic activity with excellent durability. The mass activity and specific activity values were 132.26 mA mg{sup -1} Pt and 207.62 {mu}A cm{sup -2} Pt, respectively. This work presents a future direction for the production of high-performance Pt/C catalyst in an industrial scale. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Electrochemical Deposition of Platinum and Palladium on Gold Nanoparticles Loaded Carbon Nanotube Support for Oxidation Reactions in Fuel Cell

Directory of Open Access Journals (Sweden)

Surin Saipanya

2014-01-01

Full Text Available Pt and Pd sequentially electrodeposited Au nanoparticles loaded carbon nanotube (Au-CNT was prepared for the electrocatalytic study of methanol, ethanol, and formic acid oxidations. All electrochemical measurements were carried out in a three-electrode cell. A platinum wire and Ag/AgCl were used as auxiliary and reference electrodes, respectively. Suspension of the Au-CNT, phosphate buffer, isopropanol, and Nafion was mixed and dropped on glassy carbon as a working electrode. By sequential deposition method, PdPtPt/Au-CNT, PtPdPd/Au-CNT, and PtPdPt/Au-CNT catalysts were prepared. Cyclic voltammograms (CVs of those catalysts in 1 M H2SO4 solution showed hydrogen adsorption and hydrogen desorption reactions. CV responses for those three catalysts in methanol, ethanol, and formic acid electrooxidations studied in 2 M CH3OH, CH3CH2OH, and HCOOH in 1 M H2SO4 show characteristic oxidation peaks. The oxidation peaks at anodic scan contribute to those organic substance oxidations while the peaks at cathodic scan are related with the reoxidation of the adsorbed carbonaceous species. Comparing all those three catalysts, it can be found that the PdPtPt/Au-CNT catalyst is good at methanol oxidation; the PtPdPt/Au-CNT effectively enhances ethanol oxidation while the PtPdPd/Au-CNT exceptionally catalyzes formic acid oxidation. Therefore, a different stoichiometry affects the electrochemical active surface area of the catalysts to achieve the catalytic oxidation reactions.

Mechanooptic Regulation of Photoconduction in Functionalized Carbon Nanotubes Decorated with Platinum

Directory of Open Access Journals (Sweden)

C. Mercado-Zúñiga

2014-01-01

Full Text Available The observation of photoconduction and nonlinear optical absorption on functionalized multiwall carbon nanotubes decorated with platinum is reported. The samples were prepared by a chemical vapor deposition method. The electrical conductivity of the carbon nanotubes seems to be decreased by the functionalization process; but this property is strongly enhanced after the incorporation of platinum particles. Nonresonant photoconductive experiments at 532 nm and 445 nm wavelengths allow us to detect a selective participation of the platinum to the photoelectrical response. A mechanooptic effect based on Fresnel reflection was obtained through a photoconductive modulation induced by the rotation of a silica substrate where the samples were deposited as a thin film. A two-photon absorption process was identified as the main physical mechanism responsible for the nonlinear optical absorption. We consider that important changes in the nonlinear photon interactions with carbon nanotubes can be related to the population losses derived from phonons and the detuning of the frequency originated by functionalization.

Electrocatalytic activity of carbon-supported catalysts for direct ethanol fuel cell applications

Energy Technology Data Exchange (ETDEWEB)

Rodriguez Varela, F.J. [CINVESTAV-Unidad Saltillo, Coahuila, (Mexico). Grupo de Investigacion en Energia; Savadogo, O. [Ecole Polytechnique de Montreal, Montreal, PQ (Canada). Laboratoire de nouveaux materiaux pour l' energie et l' electrochimie

2008-07-01

Proton exchange membrane fuel cells (PEMFCs) can be fueled with hydrogen, alcohols, hydrocarbons and acetals. Ethanol is an important fuel candidate because it can be electro-oxidized to carbon dioxide on platinum (Pt)-based electrocatalysts in a direct ethanol fuel cell (DEFC) at relatively low temperatures. This study investigated the electrocatalytic activity of some carbon-supported electrocatalysts towards the ethanol oxidation (EOR) and the oxygen reduction reaction (ORR) in the presence of ethanol. Compared to other anode catalysts such as Pt, PtRu and Pt oxide, anodes based on PtSn alloys have a higher catalytic activity for the EOR. When tested in a DEFC, the current density at 0.4V and 90 degrees C based on a PtSn/C anode and a Pt/C cathode was 2 times higher than that of a cell based on a PtRu/C-Pt/C membrane electrode assembly (MEA) configuration. In addition, cathode catalysts based on Ru/C had good catalytic activity for the ORR and exhibited high selectivity for this reaction in the presence of ethanol. The results showed that in the presence of 0.125, 0.25 or 0.5 M ethanol concentrations, a decrease in onset potential of about 60, 62 and 68 mV emerged, respectively. These values were about 10 times lower than those measured for some Pt-based cathode catalysts tested in this study in the presence of 0.125 M EtOH. 20 refs., 5 figs.

A Robust Fiber Bragg Grating Hydrogen Gas Sensor Using Platinum-Supported Silica Catalyst Film

OpenAIRE

Marina Kurohiji; Seiji Ichiriyama; Naoki Yamasaku; Shinji Okazaki; Naoya Kasai; Yusuke Maru; Tadahito Mizutani

2018-01-01

A robust fiber Bragg grating (FBG) hydrogen gas sensor for reliable multipoint-leakage monitoring has been developed. The sensing mechanism is based on shifts of center wavelength of the reflection spectra due to temperature change caused by catalytic combustion heat. The sensitive film which consists of platinum-supported silica (Pt/SiO2) catalyst film was obtained using sol-gel method. The precursor solution was composed of hexachloroplatinic acid and commercially available silica precursor...

Iron catalyst for preparation of polymethylene from synthesis gas and method for producing the catalyst

Science.gov (United States)

Sapienza, R.S.; Slegeir, W.A.

1990-05-15

This invention relates to a process for synthesizing hydrocarbons; more particularly, the invention relates to a process for synthesizing long-chain hydrocarbons known as polymethylene from carbon monoxide and hydrogen or from carbon monoxide and water or mixtures thereof in the presence of a catalyst comprising iron and platinum or palladium or mixtures thereof which may be supported on a solid material, preferably an inorganic refractory oxide. This process may be used to convert a carbon monoxide containing gas to a product which could substitute for high density polyethylene.

Catalyst for Carbon Monoxide Oxidation

Science.gov (United States)

Davis, Patricia; Brown, Kenneth; VanNorman, John; Brown, David; Upchurch, Billy; Schryer, David; Miller, Irvin

2010-01-01

In many applications, it is highly desirable to operate a CO2 laser in a sealed condition, for in an open system the laser requires a continuous flow of laser gas to remove the dissociation products that occur in the discharge zone of the laser, in order to maintain a stable power output. This adds to the operating cost of the laser, and in airborne or space applications, it also adds to the weight penalty of the laser. In a sealed CO2 laser, a small amount of CO2 gas is decomposed in the electrical discharge zone into corresponding quantities of CO and O2. As the laser continues to operate, the concentration of CO2 decreases, while the concentrations of CO and O2 correspondingly increase. The increasing concentration of O2 reduces laser power, because O2 scavenges electrons in the electrical discharge, thereby causing arcing in the electric discharge and a loss of the energetic electrons required to boost CO2 molecules to lasing energy levels. As a result, laser power decreases rapidly. The primary object of this invention is to provide a catalyst that, by composition of matter alone, contains chemisorbed water within and upon its structure. Such bound moisture renders the catalyst highly active and very long-lived, such that only a small quantity of it needs to be used with a CO2 laser under ambient operating conditions. This object is achieved by a catalyst that consists essentially of about 1 to 40 percent by weight of one or more platinum group metals (Pt, Pd, Rh, Ir, Ru, Os, Pt being preferred); about 1 to 90 percent by weight of one or more oxides of reducible metals having multiple valence states (such as Sn, Ti, Mn, Cu, and Ce, with SnO2 being preferred); and about 1 to 90 percent by weight of a compound that can bind water to its structure (such as silica gel, calcium chloride, magnesium sulfate, hydrated alumina, and magnesium perchlorate, with silica gel being preferred). Especially beneficial results are obtained when platinum is present in the

Optimization of the Pd-Fe-Mo Catalysts for Oxygen Reduction Reaction in Proton-Exchange Membrane Fuel Cells

International Nuclear Information System (INIS)

Lee, Yeayeon; Jang, Jeongseok; Lee, Jin Goo; Jeon, Ok Sung; Kim, Hyeong Su; Hwang, Ho Jung; Shul, Yong Gun

2016-01-01

Highlights: • Pd-Mo-Fe catalysts show high catalytic activity and stability for oxygen-reduction reactions in acid media. • The optimum compositions were 7.5:1.5:1.0 for Pd-Fe-Mo, and the optimum temperatures were 500 °C. • The Pd-Fe-Mo catalysts were successfully applied to the PEMFC cathode, showing ∼500 mA cm −1 at 0.6 V. • The lattice constant was strongly related to the activity and stability of the catalysts for oxygen-reduction reactions. - Abstract: Highly active and durable non-platinum catalysts for oxygen-reduction reaction (ORR) have been developed for energy conversion devices such as proton-exchange membrane fuel cells (PEMFCs). In this study, Pd-Fe-Mo catalyst is reported as a non-platinum catalyst for ORR. The atomic ratio and annealing temperatures are controlled on the catalysts to understand interplay between their physical and chemical properties and electrochemical activities. The Pd-Fe-Mo catalyst optimized with 7.5:1.5:1.0 of the atomic ratio and 500 °C of the annealing temperature shows 32.18 mA mg −1 PGM (PGM: platinum group metal) of the kinetic current density at 0.9 V for ORR, which is comparable to that of commercial Pt/C catalyst. The current density is degraded to 6.20 mA mg −1 PGM after 3000 cycling of cyclic voltammetry, but it is greatly enhanced value compared to other non-platinum catalysts. In actual application to PEMFCs, the 20% Pd-Fe-Mo catalyst supported on carbons exhibits a high performance of 506 mA cm −2 at 0.6 V. The results suggest that the Pd-Fe-Mo catalyst can be a good candidate for non-platinum ORR catalysts.

Investigating the effects of proton exchange membrane fuel cell conditions on carbon supported platinum electrocatalyst composition and performance

Energy Technology Data Exchange (ETDEWEB)

Patel, Anant; Artyushkova, Kateryna; Atanassov, Plamen; Colbow, Vesna; Dutta, Monica; Harvey, Davie; Wessel, Silvia

2011-12-01

Changes that carbon-supported platinum electrocatalysts undergo in a proton exchange membrane fuel cell environment were simulated by ex situ heat treatment of catalyst powder samples at 150 C and 100% relative humidity. In order to study modifications that are introduced to chemistry, morphology, and performance of electrocatalysts, XPS, HREELS and three-electrode rotating disk electrode experiments were performed. Before heat treatment, graphitic content varied by 20% among samples with different types of carbon supports, with distinct differences between bulk and surface compositions within each sample. Following the aging protocol, the bulk and surface chemistry of the samples were similar, with graphite content increasing or remaining constant and Pt-carbide decreasing for all samples. From the correlation of changes in chemical composition and losses in performance of the electrocatalysts, we conclude that relative distribution of Pt particles on graphitic and amorphous carbon is as important for electrocatalytic activity as the absolute amount of graphitic carbon present

Investigating the effects of proton exchange membrane fuel cell conditions on carbon supported platinum electrocatalyst composition and performance

Energy Technology Data Exchange (ETDEWEB)

A. Patel; K. Artyushkova; P. Atanassov; V. Colbow; M. Dutta; D. Harvey; S. Wessel

2012-04-30

Changes that carbon-supported platinum electrocatalysts undergo in a proton exchange membrane fuel cell environment were simulated by ex situ heat treatment of catalyst powder samples at 150 C and 100% relative humidity. In order to study modifications that are introduced to chemistry, morphology, and performance of electrocatalysts, XPS, HREELS and three-electrode rotating disk electrode experiments were performed. Before heat treatment, graphitic content varied by 20% among samples with different types of carbon supports, with distinct differences between bulk and surface compositions within each sample. Following the aging protocol, the bulk and surface chemistry of the samples were similar, with graphite content increasing or remaining constant and Pt-carbide decreasing for all samples. From the correlation of changes in chemical composition and losses in performance of the electrocatalysts, we conclude that relative distribution of Pt particles on graphitic and amorphous carbon is as important for electrocatalytic activity as the absolute amount of graphitic carbon present

SEM method for direct visual tracking of nanoscale morphological changes of platinum based electrocatalysts on fixed locations upon electrochemical or thermal treatments.

Science.gov (United States)

Zorko, Milena; Jozinović, Barbara; Bele, Marjan; Hodnik, Nejc; Gaberšček, Miran

2014-05-01

A general method for tracking morphological surface changes on a nanometer scale with scanning electron microscopy (SEM) is introduced. We exemplify the usefulness of the method by showing consecutive SEM images of an identical location before and after the electrochemical and thermal treatments of platinum-based nanoparticles deposited on a high surface area carbon. Observations reveal an insight into platinum based catalyst degradation occurring during potential cycling treatment. The presence of chloride clearly increases the rate of degradation. At these conditions the dominant degradation mechanism seems to be the platinum dissolution with some subsequent redeposition on the top of the catalyst film. By contrast, at the temperature of 60°C, under potentiostatic conditions some carbon corrosion and particle aggregation was observed. Temperature treatment simulating the annealing step of the synthesis reveals sintering of small platinum based composite aggregates into uniform spherical particles. The method provides a direct proof of induced surface phenomena occurring on a chosen location without the usual statistical uncertainty in usual, random SEM observations across relatively large surface areas. Copyright © 2014 Elsevier B.V. All rights reserved.

SEM method for direct visual tracking of nanoscale morphological changes of platinum based electrocatalysts on fixed locations upon electrochemical or thermal treatments

Energy Technology Data Exchange (ETDEWEB)

Zorko, Milena [National Institute of Chemistry, Hajdrihova 19, Ljubljana (Slovenia); Centre of Excellence for Low-Carbon Technologies, Hajdrihova 19, Ljubljana (Slovenia); Jozinović, Barbara [Centre of Excellence for Low-Carbon Technologies, Hajdrihova 19, Ljubljana (Slovenia); Bele, Marjan [National Institute of Chemistry, Hajdrihova 19, Ljubljana (Slovenia); Centre of Excellence for Low-Carbon Technologies, Hajdrihova 19, Ljubljana (Slovenia); Hodnik, Nejc, E-mail: nejc.hodnik@ki.si [National Institute of Chemistry, Hajdrihova 19, Ljubljana (Slovenia); Gaberšček, Miran [National Institute of Chemistry, Hajdrihova 19, Ljubljana (Slovenia); Centre of Excellence for Low-Carbon Technologies, Hajdrihova 19, Ljubljana (Slovenia)

2014-05-01

A general method for tracking morphological surface changes on a nanometer scale with scanning electron microscopy (SEM) is introduced. We exemplify the usefulness of the method by showing consecutive SEM images of an identical location before and after the electrochemical and thermal treatments of platinum-based nanoparticles deposited on a high surface area carbon. Observations reveal an insight into platinum based catalyst degradation occurring during potential cycling treatment. The presence of chloride clearly increases the rate of degradation. At these conditions the dominant degradation mechanism seems to be the platinum dissolution with some subsequent redeposition on the top of the catalyst film. By contrast, at the temperature of 60 °C, under potentiostatic conditions some carbon corrosion and particle aggregation was observed. Temperature treatment simulating the annealing step of the synthesis reveals sintering of small platinum based composite aggregates into uniform spherical particles. The method provides a direct proof of induced surface phenomena occurring on a chosen location without the usual statistical uncertainty in usual, random SEM observations across relatively large surface areas. - Highlights: • A new SEM method for observations of identical locations. • Nanoscale morphological consecutive changes on identical locations. • Electrochemical and thermal treatments on platinum based nanoparticles. • Potential cycling induces platinum dissolution with redeposition on top of the film. • At 1.4 V vs. RHE and 60 °C carbon corrosion and particle aggregation is observed.

Electrostatic layer-by-layer a of platinum-loaded multiwall carbon nanotube multilayer: A tunable catalyst film for anodic methanol oxidation

International Nuclear Information System (INIS)

Yuan Junhua; Wang Zhijuan; Zhang Yuanjian; Shen Yanfei; Han Dongxue; Zhang Qixian; Xu Xiaoyu; Niu Li

2008-01-01

A simple layer-by-layer (LBL) electrostatic adsorption technique was developed for deposition of films composed of alternating layers of positively charged poly(diallyldimethylammonium chloride) (PDDA) and negatively charged multiwall carbon nanotubes bearing platinum nanoparticles (Pt-CNTs). PDDA/Pt-CNT film structure and morphology up to six layers were characterized by scanning electron microscopy and ultraviolet-visible spectroscopy, showing the Pt-CNT layers to be porous and uniformly deposited within the multilayer films. Electrochemical properties of the PDDA/Pt-CNT films, as well as electrocatalytic activity toward methanol oxidation, were investigated with cyclic voltammetry. Significant activity toward anodic methanol oxidation was observed and is readily tunable through changing film thickness and/or platinum-nanoparticle loading. Overall, the observed properties of these PDDA/Pt-CNT multilayer films indicated unique potential for application in direct methanol fuel cell

Platinum(0-1,3-divinyl-1,1,3,3-tetramethyldisiloxane Complex as a Pt Source for Pt/SnO2 Catalyst

Directory of Open Access Journals (Sweden)

Agnieszka Martyla

2014-01-01

Full Text Available This paper presents new preparation method of Pt/SnO2, an important catalytic system. Besides of its application as a heterogenic industrial catalyst, it is also used as a catalyst in electrochemical processes, especially in fuel cells. Platinum is commonly used as an anode catalyst in low temperature fuel cells, fuelled with alcohols of low molecular weight such as methanol. Platinum(0-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex was used as a precursor of metallic phase. The aim of the research was to obtain a highly active in electrochemical system Pt/SnO2 catalyst with low metal load. Considering small size of Pt crystallites, it should result in high activity of Pt/SnO2 system. The presented method of SnO2 synthesis allows for obtaining support consisting of nanoparticles. The effect of the thermal treatment on activity of Pt/SnO2 gel was demonstrated. The system properties were investigated using TEM, FTIR (ATR, and XRD techniques to describe its thermal structural evolution. The results showed two electrocatalytical activity peaks for drying at a temperature of 430 K and above 650 K.

Atomic layer deposited highly dispersed platinum nanoparticles supported on non-functionalized multiwalled carbon nanotubes for the hydrogenation of xylose to xylitol

Science.gov (United States)

Liang, Xinhua; Jiang, Chengjun

2013-09-01

Highly dispersed platinum nanoparticles were deposited on gram quantities of non-functionalized multiwalled carbon nanotubes (MWCNTs) by atomic layer deposition (ALD) in a fluidized bed reactor at 300 °C. (Methylcyclopentadienyl) trimethylplatinum and oxygen were used as precursors. The results of TEM analysis showed that 1.3 nm Pt nanoparticles were highly dispersed on non-functionalized MWCNTs. The porous structures of MWCNTs did not change with the deposition of Pt nanoparticles. For comparison, the commercial 3 wt% Pt/C catalyst was also characterized. The ALD-prepared Pt/MWCNT was used for the hydrogenation of xylose to xylitol. The ALD-prepared Pt/MWCNT showed the best catalytic performance with 100 % conversion of xylose and 99.3 % selectivity to xylitol, compared to commercially available Pt/C, Ru/C, and Raney Ni catalysts. The stability of ALD produced Pt/MWCNT catalyst was higher than that of the commercial Pt/C, due to the presence of surface defects on the MWCNTs and the strong metal-support interaction for the ALD-prepared Pt/MWCNT catalyst.

Atomic layer deposited highly dispersed platinum nanoparticles supported on non-functionalized multiwalled carbon nanotubes for the hydrogenation of xylose to xylitol

Energy Technology Data Exchange (ETDEWEB)

Liang, Xinhua, E-mail: liangxin@mst.edu [Missouri University of Science and Technology, Department of Chemical and Biochemical Engineering (United States); Jiang, Chengjun [Zhejiang University of Science and Technology, Department of Chemical and Biological Engineering (China)

2013-09-15

Highly dispersed platinum nanoparticles were deposited on gram quantities of non-functionalized multiwalled carbon nanotubes (MWCNTs) by atomic layer deposition (ALD) in a fluidized bed reactor at 300 Degree-Sign C. (Methylcyclopentadienyl) trimethylplatinum and oxygen were used as precursors. The results of TEM analysis showed that {approx}1.3 nm Pt nanoparticles were highly dispersed on non-functionalized MWCNTs. The porous structures of MWCNTs did not change with the deposition of Pt nanoparticles. For comparison, the commercial 3 wt% Pt/C catalyst was also characterized. The ALD-prepared Pt/MWCNT was used for the hydrogenation of xylose to xylitol. The ALD-prepared Pt/MWCNT showed the best catalytic performance with 100 % conversion of xylose and 99.3 % selectivity to xylitol, compared to commercially available Pt/C, Ru/C, and Raney Ni catalysts. The stability of ALD produced Pt/MWCNT catalyst was higher than that of the commercial Pt/C, due to the presence of surface defects on the MWCNTs and the strong metal-support interaction for the ALD-prepared Pt/MWCNT catalyst.

Determination of platinum group metals by ICP-AES in environmental samples after preconcentration

International Nuclear Information System (INIS)

Vlasankova, R.; Sommer, L.

1999-01-01

Platinum group metal (PGM) may have toxic properties and their presence in the environment represent danger for human health. With the introduction of automobile catalytic converters containing PGM, the emission of these noble metals into atmosphere has increased. Platinum, palladium and rhodium are used in this catalytic converters to decrease toxic emissions of carbon monoxide, unburnt hydrocarbons and nitrogen oxides in vehicles exhaust gases. These catalysts are mobile sources of PGM into the environment. Thus, increased platinum concentrations have been found in various objects of environment because of the massive introduction of such catalytic converters are present. The preconcentration and separation of PGM and their determination by ICP-AES in environmental samples are described

Active carbon catalyst for heavy oil upgrading

Energy Technology Data Exchange (ETDEWEB)

Fukuyama, Hidetsugu; Terai, Satoshi [Technology Research Center, Toyo Engineering Corporation, 1818 Azafujimi, Togo, Mobara-shi, Chiba 297-00017 (Japan); Uchida, Masayuki [Business Planning and Exploring Department, Overseas Business Development and Marketing Division, Toyo Engineering Corporation, 2-8-1 Akanehama, Narashino-shi, Chiba 275-0024 (Japan); Cano, Jose L.; Ancheyta, Jorge [Maya Crude Treatment Project, Instituto Mexicano del Petroleo, Eje Central Lazaro Cardenas No. 152, Col. San Bartolo Atepehuacan, Mexico D.F. 07730 (Mexico)

2004-11-24

The active carbon (AC) catalyst was studied by hydrocracking of Middle Eastern vacuum residue (VR) for heavy oil upgrading. It was observed that the active carbon has the affinity to heavy hydrocarbon compounds and adsorption selectivity to asphaltenes, and exhibits better ability to restrict the coke formation during the hydrocracking reaction of VR. The mesopore of active carbon was thought to play an important role for effective conversion of heavy hydrocarbon compounds into lighter fractions restricting carbon formation. The performance of the AC catalyst was examined by continuous hydrocracking by CSTR for the removal of such impurities as sulfur and heavy metals (nickel and vanadium), which are mostly concentrated in the asphaltenes. The AC catalyst was confirmed to be very effective for the removal of heavy metals from Middle Eastern VR, Maya/Istmo VR and Maya VR. The extruded AC catalysts were produced by industrial manufacturing method. The application test of the extruded AC catalyst for ebullating-bed reactor as one of the commercially applicable reactors was carried out at the ebullating-bed pilot plant for 500h. The ebullition of the extruded AC catalyst was successfully traced and confirmed by existing {gamma}-ray density meter. The extruded AC catalyst showed stable performance with less sediment formation at an equivalent conversion by conventional alumina catalyst at commercial ebullating-bed unit. The degradation of the AC catalyst at the aging test was observed to be less than that of the conventional alumina catalyst. Thus, the AC catalyst was confirmed to be effective and suitable for upgrading of heavy oil, especially such heavy oils as Maya, which contains much heavy metals.

Carbon nanotube/platinum nanoparticle nanocomposites: preparation, characterization and application in electro oxidation of alcohols

International Nuclear Information System (INIS)

Kalinke, Adir H.; Zarbin, Aldo J. G.

2014-01-01

The synthesis and characterization of different platinum nanoparticle/ carbon nanotube nanocomposite samples are described along with the application of these nanocomposites as electrocatalysts for alcohol oxidation. Samples were prepared by a biphasic system in which platinum nanoparticles (Pt-NPs) are synthesized in situ in contact with a carbon nanotube (CNT) dispersion. Variables including platinum precursor/CNT ratio, previous chemical treatment of carbon nanotubes, and presence or absence of a capping agent were evaluated and correlated with the characteristic of the synthesized materials. Samples were characterized by Raman spectroscopy, X-ray diffraction, thermogravimetric analysis and transmission electron microscopy. Glassy carbon electrodes were modified by the nanocomposite samples and evaluated as electrocatalysts for alcohol oxidation. Current densities of 56.1 and 79.8/104.7 mA cm -2 were determined for the oxidation of methanol and ethanol, respectively. (author)

Bimetallic Catalysts and Platinum Surfaces Studied by X-ray Absorption Spectroscopy and Scanning Tunnelling Microscopy

Energy Technology Data Exchange (ETDEWEB)

Roenning, Magnus

2000-07-01

Bimetallic catalyst systems used in Fischer-Tropsch synthesis (Co-Re/Al{sub 2}O{sub 3}) and in the naphtha reforming process (Pt-Re/Al{sub 2}O{sub 3}) have been studied in situ using X-ray absorption spectroscopy (EXAFS). Additionally, the adsorption of ethene on platinum single crystal surfaces has been investigated using scanning tunnelling microscopy. In situ EXAFS at the cobalt K absorption edge have been carried out at 450{sup o}C on the hydrogen reduction of a rhenium-promoted Co{sub 3}O{sub 4}/Al{sub 2}O{sub 3} catalyst. Reductions carried out using 100% hydrogen and 5% hydrogen in helium gave different results. Whereas the reduction using dilute hydrogen leads to bulk-like metallic cobalt particles (hcp or fcc), reaction with pure hydrogen yields a more dispersed system with smaller cobalt metal particles (< 40 A). The results are rationalised in terms of different degrees of reoxidation of cobalt by the higher and lower concentrations of water generated during the reduction of cobalt oxide by 100% and 5% hydrogen, respectively. Additionally, in both reduction protocols a small fraction (3 -4 wt%) of the cobalt content is randomly dispersed over the tetrahedral vacancies of the alumina support. This dispersion occurs during reduction and not calcination. The cobalt in these sites cannot be reduced at 450 {sup o}C. The local environments about the rhenium atoms in Co-Re/{gamma}-A1{sub 2}O{sub 3} catalyst after different reduction periods have been studied by X-ray absorption spectroscopy. A bimetallic catalyst containing 4.6 wt% cobalt and 2 wt% rhenium has been compared with a corresponding monometallic sample with 2 wt% rhenium on the same support. The rhenium L{sub III} EXAFS analysis shows that bimetallic particles are formed after reduction at 450{sup o}C with the average particle size being 10-15 A. Rhenium is shown to be reduced at a later stage than cobalt. The fraction of cobalt atoms entering the support obstructs the access to the support for the

Catalyst Deactivation Simulation Through Carbon Deposition in Carbon Dioxide Reforming over Ni/CaO-Al2O3 Catalyst

Directory of Open Access Journals (Sweden)

Istadi Istadi

2011-11-01

Full Text Available Major problem in CO2 reforming of methane (CORM process is coke formation which is a carbonaceous residue that can physically cover active sites of a catalyst surface and leads to catalyst deactivation. A key to develop a more coke-resistant catalyst lies in a better understanding of the methane reforming mechanism at a molecular level. Therefore, this paper is aimed to simulate a micro-kinetic approach in order to calculate coking rate in CORM reaction. Rates of encapsulating and filamentous carbon formation are also included. The simulation results show that the studied catalyst has a high activity, and the rate of carbon formation is relatively low. This micro-kinetic modeling approach can be used as a tool to better understand the catalyst deactivation phenomena in reaction via carbon deposition. Copyright © 2011 BCREC UNDIP. All rights reserved.(Received: 10th May 2011; Revised: 16th August 2011; Accepted: 27th August 2011[How to Cite: I. Istadi, D.D. Anggoro, N.A.S. Amin, and D.H.W. Ling. (2011. Catalyst Deactivation Simulation Through Carbon Deposition in Carbon Dioxide Reforming over Ni/CaO-Al2O3 Catalyst. Bulletin of Chemical Reaction Engineering & Catalysis, 6 (2: 129-136. doi:10.9767/bcrec.6.2.1213.129-136][How to Link / DOI: http://dx.doi.org/10.9767/bcrec.6.2.1213.129-136 || or local:  http://ejournal.undip.ac.id/index.php/bcrec/article/view/1213 ] | View in  |  

Mass-produced multi-walled carbon nanotubes as catalyst supports for direct methanol fuel cells.

Science.gov (United States)

Jang, In Young; Park, Ki Chul; Jung, Yong Chae; Lee, Sun Hyung; Song, Sung Moo; Muramatsu, Hiroyuki; Kim, Yong Jung; Endo, Morinobu

2011-01-01

Commercially mass-produced multi-walled carbon nanotubes, i.e., VGNF (Showa Denko Co.), were applied to support materials for platinum-ruthenium (PtRu) nanoparticles as anode catalysts for direct methanol fuel cells. The original VGNFs are composed of high-crystalline graphitic shells, which hinder the favorable surface deposition of the PtRu nanoparticles that are formed via borohydride reduction. The chemical treatment of VGNFs with potassium hydroxide (KOH), however, enables highly dispersed and dense deposition of PtRu nanoparticles on the VGNF surface. This capability becomes more remarkable depending on the KOH amount. The electrochemical evaluation of the PtRu-deposited VGNF catalysts showed enhanced active surface areas and methanol oxidation, due to the high dispersion and dense deposition of the PtRu nanoparticles. The improvement of the surface deposition states of the PtRu nanoparticles was significantly due to the high surface area and mesorporous surface structure of the KOH-activated VGNFs.

Application of hydrophobic Pt catalysts in hydrogen isotopes separation from nuclear effluents

Energy Technology Data Exchange (ETDEWEB)

Ionita, G.; Popescu, I.; Stefanescu, I.; Retegan, T. [National Institute of Cryogenics and Isotopic Separation (Romania)

2003-09-01

According to reviewed references and to tests effected by authors the platinum/carbon/teflon is the most active and the most stable catalyst for removal of tritium from nuclear effluents by isotopic exchange between hydrogen and liquid water. To improve the performances of process it is recommended to use the catalyst as ordered or random mixed catalytic packing in a trickle bed reactor. (O.M.)

Two Catalysts for Selective Oxidation of Contaminant Gases

Science.gov (United States)

Wright, John D.

2011-01-01

Two catalysts for the selective oxidation of trace amounts of contaminant gases in air have been developed for use aboard the International Space Station. These catalysts might also be useful for reducing concentrations of fumes in terrestrial industrial facilities especially facilities that use halocarbons as solvents, refrigerant liquids, and foaming agents, as well as facilities that generate or utilize ammonia. The first catalyst is of the supported-precious-metal type. This catalyst is highly active for the oxidation of halocarbons, hydrocarbons, and oxygenates at low concentrations in air. This catalyst is more active for the oxidation of hydrocarbons and halocarbons than are competing catalysts developed in recent years. This catalyst completely converts these airborne contaminant gases to carbon dioxide, water, and mineral acids that can be easily removed from the air, and does not make any chlorine gas in the process. The catalyst is thermally stable and is not poisoned by chlorine or fluorine atoms produced on its surface during the destruction of a halocarbon. In addition, the catalyst can selectively oxidize ammonia to nitrogen at a temperature between 200 and 260 C, without making nitrogen oxides, which are toxic. The temperature of 260 C is higher than the operational temperature of any other precious-metal catalyst that can selectively oxidize ammonia. The purpose of the platinum in this catalyst is to oxidize hydrocarbons and to ensure that the oxidation of halocarbons goes to completion. However, the platinum exhibits little or no activity for initiating the destruction of halocarbons. Instead, the attack on the halocarbons is initiated by the support. The support also provides a high surface area for exposure of the platinum. Moreover, the support resists deactivation or destruction by halogens released during the destruction of halocarbons. The second catalyst is of the supported- metal-oxide type. This catalyst can selectively oxidize ammonia to

Hall Measurements on Carbon Nanotube Paper Modified With Electroless Deposited Platinum

Directory of Open Access Journals (Sweden)

Iwuoha Emmanuel

2009-01-01

Full Text Available Abstract Carbon nanotube paper, sometimes referred to as bucky paper, is a random arrangement of carbon nanotubes meshed into a single robust structure, which can be manipulated with relative ease. Multi-walled carbon nanotubes were used to make the nanotube paper, and were subsequently modified with platinum using an electroless deposition method based on substrate enhanced electroless deposition. This involves the use of a sacrificial metal substrate that undergoes electro-dissolution while the platinum metal deposits out of solution onto the nanotube paper via a galvanic displacement reaction. The samples were characterized using SEM/EDS, and Hall-effect measurements. The SEM/EDS analysis clearly revealed deposits of platinum (Pt distributed over the nanotube paper surface, and the qualitative elemental analysis revealed co-deposition of other elements from the metal substrates used. When stainless steel was used as sacrificial metal a large degree of Pt contamination with various other metals was observed. Whereas when pure sacrificial metals were used bimetallic Pt clusters resulted. The co-deposition of a bimetallic system upon carbon nanotubes was a function of the metal type and the time of exposure. Hall-effect measurements revealed some interesting fluctuations in sheet carrier density and the dominant carrier switched from N- to P-type when Pt was deposited onto the nanotube paper. Perspectives on the use of the nanotube paper as a replacement to traditional carbon cloth in water electrolysis systems are also discussed.

Non-carbon titanium cobalt nitride nanotubes supported platinum catalyst with high activity and durability for methanol oxidation reaction

Science.gov (United States)

Chen, Xiaoxiang; Li, Wuyi; Pan, Zhanchang; Xu, Yanbin; Liu, Gen; Hu, Guanghui; Wu, Shoukun; Li, Jinghong; Chen, Chun; Lin, Yingsheng

2018-05-01

Titanium cobalt nitride nanotubes (Ti0.95Co0.05N NTs) hybrid support, a novel robust non-carbon support material prepared by solvothermal and post-nitriding processes, is further decorated with Pt nanoparticles for the electrooxidation of methanol. The catalyst is characterized by X-ray diffraction (XRD), nitrogen adsorption/desorption, transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and electrochemical measurements. The morphology, structure and composition of the synthesized Ti0.95Co0.05N NTs suggest that the nanotube wall is porous and consists of homogeneous cohesively attached nitrides nanocube particles. Notable, Ti0.95Co0.05N NTs supported Pt catalyst exhibits significantly improved catalytic activity and durability for methanol electrooxidation compared with the conventional JM Pt/C catalyst. The experimental data indicate that enhanced catalytic activity and stability of Pt/Ti0.95Co0.05N NTs towards methanol electrooxidation might be mainly attributed to the tubular nanostructures and synergistic effect introduced by the Co doping. Both of them are playing an important role in improving the activity and durability of the Ti0.95Co0.05N NTs catalyst.

Less sensitive electrocatalysts towards carbon monoxide for PEMFC fed by hydrogen produced from reforming gas; Recherche de catalyseurs peu sensibles a la presence de monoxyde de carbone pour piles a combustible PEMFC alimentees en gaz de reformage

Energy Technology Data Exchange (ETDEWEB)

Boucher, A.C.

2002-11-15

The aim of this work was to prepare bimetallic catalysts based on platinum to elaborate anodes for fuel cells fed by hydrogen produced from reforming gas and containing thus some ppm of carbon monoxide. In order to avoid platinum poisoning, another metal, such as tin, was added. This leads to a more tolerant material to CO. A Pt-Sn catalyst supported on Vulcan XC-72 carbon was prepared by a chemical route, using a platinum carbonyl complex. This material was characterized by physical and chemical methods which indicate that it is formed by nano-structured Pt{sub 3}Sn particles. These particles have a narrow size distribution with a mean diameter of approximately 2 nm. Its activity towards CO, particularly under fuel cell conditions, was compared with a similar commercial E-TEK catalyst. This study shows that the catalyst prepared from the carbonyl precursor is less sensitive to CO than the commercial one. (author)

Determination of the potentiostatic stability of PEMFC electro catalysts at elevated temperatures

NARCIS (Netherlands)

Dam, V.A.T.; Jayasayee, K.; Bruijn, de F.A.

2009-01-01

The electrochemical stability of platinum on carbon catalyst (Hispec TM 4000, Johnson Matthey) has been investigated predominantly at constant potentials ranging from 0.95 to 1.25 V at elevated temperatures. By combining a quartz crystal microbalance (QCM) with electrochemical techniques, dynamic

Tethered catalysts for the hydration of carbon dioxide

Science.gov (United States)

Valdez, Carlos A; Satcher, Jr., Joe H; Aines, Roger D; Wong, Sergio E; Baker, Sarah E; Lightstone, Felice C; Stolaroff, Joshuah K

2014-11-04

A system is provided that substantially increases the efficiency of CO.sub.2 capture and removal by positioning a catalyst within an optimal distance from the air-liquid interface. The catalyst is positioned within the layer determined to be the highest concentration of carbon dioxide. A hydrophobic tether is attached to the catalyst and the hydrophobic tether modulates the position of the catalyst within the liquid layer containing the highest concentration of carbon dioxide.

Carbon a support for sulfide catalysts

NARCIS (Netherlands)

Vissers, J.P.R.; Lensing, T.J.; Mercx, F.P.M.; Beer, de V.H.J.; Prins, R.

1983-01-01

Two types of carbon materials, carbon black composite and carbon covered alumina, were studied for-their use as support for sulfide catalysts. The following parameters were varied: type of carbon black, carbon coverage of the alumina and carbon pretreatment. Pore size distributions were determined

CO Adsorption and Oxidation at the Catalyst-Water Interface: An Investigation by Attenuated Total Reflection Infrared Spectroscopy.

NARCIS (Netherlands)

Ebbesen, S.D.; Mojet, Barbara; Lefferts, Leonardus

2006-01-01

Adsorption of carbon monoxide and oxidation of preadsorbed carbon monoxide from gas and aqueous phases were studied on a platinum catalyst deposited on a ZnSe internal reflection element (IRE) using attenuated total reflection infrared (ATR-IR) spectroscopy. The results of this study convincingly

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.

Magnetic properties of carbon nanotubes with and without catalyst

Energy Technology Data Exchange (ETDEWEB)

Lipert, Kamil; Ritschel, Manfred; Leonhardt, Albrecht; Krupskaya, Yulia; Buechner, Bernd; Klingeler, Ruediger, E-mail: k.lipert@ifw-dresden.d [Leibniz Institute for Solid State and Materials Research (IFW) Dresden (Germany)

2010-01-01

In this paper we report on the magnetic properties of single- and multiwalled carbon nanotubes synthesized using different chemical vapour deposition methods and with variety of catalyst materials (ferromagnetic Fe, FeCo and diamagnetic Re). Different methods yield carbon nanotubes with different morphologies and different quantity of residual catalyst material. Catalyst particles are usually encapsulated in the nanotubes and influence the magnetic respond of the samples. Varying ferromagnetic properties depending on the shape, size and type of catalyst are discussed in detail. The data are compared with M(H) characteristics of carbon nanotubes without catalysts and with nonmagnetic rhenium, as a reference.

Isotopic exchange between deuterium and neohexane on supported platinum and palladium catalysts

International Nuclear Information System (INIS)

Eskinazi, V.

1979-01-01

The isotopic exchange reaction between neohexane and deuterium on supported Pt/SiO 2 and Pd/SiO 2 catalysts has been investigated in the temperature range 86.5 to 110 0 C. Rates of exchange were studied as functions of percentage of metal atoms exposed, the conditions of catalyst pretreatment, and the reaction temperature. The rates of exchange were not strongly dependent upon percentage exposed; however, the relative yields of d 1 through d 5 in the ethyl moiety or neohexane were dependent on the percentage metal atoms exposed. The Pt/SiO 2 catalysts were found to be more active for exchange than the Pd/SiO 2 catalysts by an order of magnitude. Both the turnover frequencies and the exchange pattern were observed to be influenced by the pretreatment of the catalyst. Maxima in the exchange pattern occurred at d 3 and d 5 in the case of Pt/SiO 2 and at d 5 only in the case of the Pd/SiO 2 catalysts. In order to account for the d 3 maximum observed for Pt catalysts, some extension of the Horiuti-Polanyi mechanism is required. Mechanisms by which the d 3 species might be formed are proposed and discussed. On Pd/SiO 2 catalysts exchange occurs preferentially in the ethyl substituent of the quaternary carbon atom rather than on the three methyl substituents of the quaternary carbon atom. Such preference is not observed on Pt/SiO 2 catalysts; in fact, in some cases, this preference is reversed. Whenever exchange occurs in the three methyl substituents, mostly the d 1 product is obtained. For Pt/SiO 2 catalysts, the exchange pattern appears to be influenced by steric effects, but the data suggest that factors other than steric effects are important on Pd

Pt/Ceria-based Catalysts for Small Alcohol Electrooxidation

Science.gov (United States)

Menendez-Mora, Christian L.

High emissions of fossil-based energy sources have led to scientists around the world to develop new alternatives for the future. In this sense, fuel cells are a remarkable and promising energy option with less environmental impact. The most used fuels for this technology are hydrogen and small chain alcohols, which can be oxidized to transform their chemical energy into electrical power. To do this, fuel cells need catalysts that will act as an active surface where the oxidation can take place. The problem with platinum catalysts is its possible CO poisoning with intermediates that are produced before the complete oxidation of alcohol to CO2. Different approaches have been taken to try to resolve this issue. In this case, cerium oxide (ceria) was selected as a co-catalyst to mitigate the effect of CO poisoning of platinum. Ceria is a compound that has the ability to work as an "oxygen tank" and can donate oxygen to carbon monoxide that is strongly adsorbed at platinum surface to produce CO2 (carbon dioxide), regenerating the Pt surface for further alcohol oxidation. Therefore, enhancing the current density as well as the power output of a fuel cell. First, an occlusion deposition technique was used to prepare platinum/ceria composite electrodes and tested them towards small chain alcohol oxidation such as methanol oxidation reaction in acidic and alkaline media. The preliminary results demonstrated that the Pt/ceria electrodes were more efficient towards methanol electrooxidation when compared to Pt electrodes. This enhancement was attributed to the presence of ceria. A second preparation method was selected for the synthesis of ceria/Pt catalysts. In this case, a hydrothermal method was used and the catalysis were studied for the effect of MeOH, EtOH and n-BuOH oxidation. The observed effect was that electrodes made of Pt/Pt:CeO2-x showed better catalytic effect than Pt/ceria and platinum electrodes. Moreover, a comparison between ceria nanorods versus

Cyclic voltammetric investigations of microstructured and platinum-covered glassy carbon electrodes in contact with a polymer electrolyte membrane

Energy Technology Data Exchange (ETDEWEB)

Scherer, G G; Veziridis, Z; Staub, M [Paul Scherrer Inst. (PSI), Villigen (Switzerland); Freimuth, H [Inst. fuer Mikrotechnik Mainz IMM, Mainz (Germany)

1997-06-01

Model gas diffusion electrodes were prepared by microstructuring glassy carbon surfaces with high aspect ratios and subsequent deposition of platinum. These electrodes were characterized by hydrogen under-potential deposition (H-upd) in contact with a polymer electrolyte membrane employing cyclic voltametry. H-upd was found on platinum areas not in direct contact to the solid electrolyte, as long as a continuous platinum-path existed. A carbon surface between platinum acts as barrier for H-upd. (author) 4 figs., 5 refs.

Hydrogenation of carbon monoxide over supported palladium catalysts

Energy Technology Data Exchange (ETDEWEB)

Fujimoto, K.; Hashimoto, H.; Kunugi, T.

1978-03-01

An alumina-supported 2% palladium catalyst had higher activity for carbon monoxide hydrogenation than a silica-supported 2% palladium catalyst, at 250/sup 0/-400/sup 0/C and 1 atm. The addition of lanthanum oxide or thorium oxide, but not of potassium oxide, to the silica-supported catalyst increased the conversion at 350/sup 0/C from 1.1% to 81.0% with a selectivity of 56.1% for methane, 1.4% for C/sub 2/ compounds, 0.1% for C/sub 3/ compounds, and 42.5% for carbon dioxide. Temperature-programed desorption of carbon monoxide in a hydrogen stream showed that of two desorption peaks observed for carbon monoxide, the one at higher temperature corresponded to the carbon monoxide species which hydrogenates to methane and that the area of this peak increased with increasing thorium content of the catalyst. Graphs, tables, and 12 references.

Platinum-TM (TM = Fe, Co) alloy nanoparticles dispersed nitrogen doped (reduced graphene oxide-multiwalled carbon nanotube) hybrid structure cathode electrocatalysts for high performance PEMFC applications.

Science.gov (United States)

Vinayan, B P; Ramaprabhu, S

2013-06-07

The efforts to push proton exchange membrane fuel cells (PEMFC) for commercial applications are being undertaken globally. In PEMFC, the sluggish kinetics of oxygen reduction reactions (ORR) at the cathode can be improved by the alloying of platinum with 3d-transition metals (TM = Fe, Co, etc.) and with nitrogen doping, and in the present work we have combined both of these aspects. We describe a facile method for the synthesis of a nitrogen doped (reduced graphene oxide (rGO)-multiwalled carbon nanotubes (MWNTs)) hybrid structure (N-(G-MWNTs)) by the uniform coating of a nitrogen containing polymer over the surface of the hybrid structure (positively surface charged rGO-negatively surface charged MWNTs) followed by the pyrolysis of these (rGO-MWNTs) hybrid structure-polymer composites. The N-(G-MWNTs) hybrid structure is used as a catalyst support for the dispersion of platinum (Pt), platinum-iron (Pt3Fe) and platinum-cobalt (Pt3Co) alloy nanoparticles. The PEMFC performances of Pt-TM alloy nanoparticle dispersed N-(G-MWNTs) hybrid structure electrocatalysts are 5.0 times higher than that of commercial Pt-C electrocatalysts along with very good stability under acidic environment conditions. This work demonstrates a considerable improvement in performance compared to existing cathode electrocatalysts being used in PEMFC and can be extended to the synthesis of metal, metal oxides or metal alloy nanoparticle decorated nitrogen doped carbon nanostructures for various electrochemical energy applications.

Development of Water Detritiation Process Using the Hydrophobic Platinum Catalyst

International Nuclear Information System (INIS)

Ahn, D.H.; Paek, S.; Choi, H.J.; Kim, K.R.; Chung, H.; Yim, S.P.; Lee, M.S.

2006-01-01

Radioactive emissions and occupational doses by tritium are mainly caused by tritiated water escaping from equipment in the nuclear industry. Improving the leak-tightness of equipment is effective in reducing emissions and internal dose but is not a long-term solution. Water detritiation was consider to be the most effective tritium control option since tritium is removed right from the source. The WTRF (Wolsong Tritium Removal Facility) is under construction now with the completion date of June, 2006 in Korea. It is designed to remove tritium from tritiated heavy water in each of the existing four Candu units at Wolsong site. We developed a hydrophobic platinum catalyst (Pt/SDBC catalyst) that would be used at the LPCE (Liquid Phase Catalytic Exchange) column in the WTRF. The catalytic rate constants of the newly developed catalyst for the deuterium exchange reaction between water vapor and hydrogen gas were measured in a recycle reactor. The catalytic rate constants of the Pt/SDBC catalyst decreased with reaction time and were much greater than that required, 2.0 x 10 -4 mol (D 2 )/s/g(pellet) in the design of the WTRF. Tritium removal efficiency of the WTRF, which is important for a safe and reliable operation of the facility, depends on the design and operating variables. A theoretical model based on the design and operating variables of the LPCE process was set up, and the equations between the parameters were derived. Numerical calculation result from a computer program shows steep increase of the detritiation factor of the LPCE process with respect to temperature increase and mild increase with respect to pressure decrease. The other parametric study shows that the calculated detritiation factors increase as the catalyst efficiency, number of theoretical stages of hydrophilic packing, the detritiation factor of cryogenic distillation system and the total number of sections increase. We also proceeded with the experiments for the hydrogen isotopic exchange

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.

Platinum assisted by carbon quantum dots for methanol electro-oxidation

Science.gov (United States)

Pan, Dan; Li, Xingwei; Zhang, Aofeng

2018-01-01

Various types of fuel cells as clean and portable power sources show a great attraction, especially direct methanol fuel cell (DMFC) having high energy density, low operating temperature and convenient fuel storage. However, the preparation of low-cost Pt-based catalysts with satisfactory catalytic performance still faces many challenges for its commercialization on large scale. Here, Pt catalysts assisted by carbon quantum dots (CQDs) are reported. The synergistic effect of carbon quantum dots and Pt metals is similar to a bi-component catalyst, such as PtRu. First, carbon quantum dots derived from Vulcan XC-72 carbon black are synthesized by mixed acid etching. Then, carbon black (Vulcan XC-72) is soaked in carbon quantum dots solution for several days to obtain carbon black modified by carbon quantum dots (XC-72-CQDs). Finally, Pt catalysts are supported on XC-72-CQDs (Pt/XC-72-CQDs) through a simple chemical reduction method. For methanol electro-oxidation reaction, the catalytic performance of Pt/XC-72-CQDs is compared with commercial PtRu/C (30% Pt + 15% Ru). Results show that a typical product (Pt/XC-72-CQDs5) exhibits a better catalytic activity than PtRu/C. In cyclic voltammetry test, the specific activity of Pt/XC-72-CQDs5 is 1.06 mA cm-2 Pt and 477.6 mA mg-1 Pt, while that of PtRu/C is 0.77 mA cm-2 Pt and 280.6 mA mg-1 Pt.

On the mobility of carbon-supported platinum nanoparticles towards unveiling cathode degradation in water electrolysis

Science.gov (United States)

Paciok, Paul; Schalenbach, Maximilian; Carmo, Marcelo; Stolten, Detlef

2017-10-01

This study investigates the influence of the hydrogen evolution reaction (HER) overpotential on the mobility of carbon-supported platinum particles. The migration of the platinum over the carbon support was analyzed by means of identical location transmission electron microscopy (IL-TEM). While at potentials of 0.1 and 0 V vs. reversible hydrogen electrode (RHE), no changes to the Pt/C material were observed. With a decrease of the overpotential to -0.1 V vs. RHE, an increase in the quantity of migrating platinum particles took place. At -0.2 V vs. RHE, a further rise in the particle migration was observed. The effect of the overpotential on the migration was explained by a higher hydrogen generation rate, the formation of a hydrogen monolayer on the platinum and the resulting changes of the platinum support distance. The mechanisms revealed in this study could describe a relevant source of degradation of PEM water electrolyzers.

Electrocatalytic properties of graphite nanofibers-supported platinum catalysts for direct methanol fuel cells.

Science.gov (United States)

Park, Soo-Jin; Park, Jeong-Min; Seo, Min-Kang

2009-09-01

Graphite nanofibers (GNFs) treated at various temperatures were used as carbon supports to improve the efficiency of PtRu catalysts. The electrochemical properties of the PtRu/GNFs catalysts were then investigated to evaluate their potential for application in DMFCs. The results indicated that the particle size and dispersibility of PtRu in the catalysts were changed by heat treatment, and the electrochemical activity of the catalysts was improved. Consequently, it was found that heat treatments could have an influence on the surface and structural properties of GNFs, resulting in enhancing an electrocatalytic activity of the catalysts for DMFCs.

Hydrogenation of hexene over platinum on alumina vs. platinum in a Na-Y zeolite

International Nuclear Information System (INIS)

Miner, R.S. Jr.; Ione, K.G.; Namba, S.; Turkevich, J.

1978-01-01

In order to study the efficacy of zeolites as supports, several platinum H--Y zeolites were prepared by ion exchanging an H--Y zeolite with Pt(NH 3 ) 4 Cl 2 and reducing these products with hydrazine hydrate (A, B, C). Another preparation was made by adsorbing 32-A platinum sol on the zeolite crystallites (D). These catalysts were studied for hydrogenation and isomerization of hexene-1, ethylene hydrogenation, hydrogen chemisorption, and poison titration. They were compared with monodisperse Pt (32 A diameter) on alumina. A marked difference was found between the behavior of hexene-1 with the platinum-in-zeolite and with the platinum-on-alumina

Effect of titania on the characteristics of a Tin-Platinum catalyst

Energy Technology Data Exchange (ETDEWEB)

Morales-Gil, P., E-mail: moralesp@imp.mx; Nava, N. [Instituto Mexicano del Petróleo (Mexico); Baggio-Saitovitch, E. [Centro Brasileiro de Pesquisas Físicas (Brazil)

2015-06-15

Pt-Sn bimetallic catalysts dispersed on alumina are commonly used for reforming and dehydrogenation reactions. In this research work, Pt and Sn were supported on titania. The resulting interactions between the components in the prepared samples, before and after treatment with hydrogen, were studied by Mössbauer spectroscopy, X-ray diffraction and Rietveld refinement. The results show the presence of Pt and SnO{sub 2} after calcinations. After the reduction process, metallic Pt, PtSn, and Pt{sub 3}Sn alloys were identified. The Rietveld refinement analysis shows that some Ti{sup 4+} atoms were replaced by Sn{sup 4+} atoms in the titania structure. Finally, the Mössbauer spectroscopy and X-ray diffraction results indicate that metallic platinum and SnO{sub 2} are encapsulated by a TiOx layer.

Catalyst design for carbon nanotube growth using atomistic modeling

International Nuclear Information System (INIS)

Pint, Cary L; Bozzolo, Guillermo; Hauge, Robert

2008-01-01

The formation and stability of bimetallic catalyst particles, in the framework of carbon nanotube growth, is studied using the Bozzolo-Ferrante-Smith (BFS) method for alloys. Monte Carlo-Metropolis simulations with the BFS method are utilized in order to predict and study equilibrium configurations for nanoscale catalyst particles which are directly relevant to the catalyst state prior to growth of carbon nanotubes. At the forefront of possible catalyst combinations is the popular Fe-Mo bimetallic catalyst, which we have recently studied experimentally. We explain our experimental results, which indicate that the growth observed is dependent on the order of co-catalyst deposition, in the straightforward interpretation of BFS strain and chemical energy contributions toward the formation of Fe-Mo catalyst prior to growth. We find that the competition between the formation of metastable inner Mo cores and clusters of surface-segregated Mo atoms in Fe-Mo catalyst particles influences catalyst formation, and we investigate the role of Mo concentration and catalyst particle size in this process. Finally, we apply the same modeling approach to other prominent bimetallic catalysts and suggest that this technique can be a powerful tool to understand and manipulate catalyst design for highly efficient carbon nanotube growth

Activity of platinum/carbon and palladium/carbon catalysts promoted by Ni2 P in direct ethanol fuel cells.

Science.gov (United States)

Li, Guoqiang; Feng, Ligang; Chang, Jinfa; Wickman, Björn; Grönbeck, Henrik; Liu, Changpeng; Xing, Wei

2014-12-01

Ethanol is an alternative fuel for direct alcohol fuel cells, in which the electrode materials are commonly based on Pt or Pd. Owing to the excellent promotion effect of Ni2 P that was found in methanol oxidation, we extended the catalyst system of Pt or Pd modified by Ni2 P in direct ethanol fuel cells. The Ni2 P-promoted catalysts were compared to commercial catalysts as well as to reference catalysts promoted with only Ni or only P. Among the studied catalysts, Pt/C and Pd/C modified by Ni2 P (30 wt %) showed both the highest activity and stability. Upon integration into the anode of a homemade direct ethanol fuel cell, the Pt-Ni2 P/C-30 % catalyst showed a maximum power density of 21 mW cm(-2) , which is approximately two times higher than that of a commercial Pt/C catalyst. The Pd-Ni2 P/C-30 % catalyst exhibited a maximum power density of 90 mW cm(-2) . This is approximately 1.5 times higher than that of a commercial Pd/C catalyst. The discharge stability on both two catalysts was also greatly improved over a 12 h discharge operation. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Preparation And Characterization Of Cr/Activated Carbon Catalyst From Palm Empty Fruit Bunch

Directory of Open Access Journals (Sweden)

Zainal Fanani

2016-02-01

Full Text Available Preparation and characterization of Cr/activated carbon catalyst from palm empty fruit bunch had been done. The research were to determine the effect of carbonization temperature towards adsorption of ammonia, iodine number, metilen blue number, and porosity of activated carbon and Cr/activated carbon catalyst. The determination of porosity include surface area, micropore volume and total pore volume. The results showed the best carbonization temperature activated carbon and Cr/activated carbon catalyst at 700°C. The adsorption ammonia of activated carbon and Cr/activated carbon catalyst as 6.379 mmol/g and 8.1624 mmol/g. The iodine number of activated carbon and Cr/activated carbon catalyst as 1520.16 mg/g and 1535.67 mg/g. The metilen blue number of activated carbon and Cr/activated carbon catalyst as 281.71 mg/g and 319.18 mg/g. The surface area of activated carbon and Cr/activated carbon catalyst as 1527.80 m2/g and 1652.58 m2/g. The micropore volume of activated carbon and Cr/activated carbon catalyst as 0.7460 cm3/g and 0.8670 cm3/g. The total pore volume of activated carbon and Cr/activated carbon catalyst as 0.8243 cm3/g and 0.8970 cm3/g.

pH-dependent release of trace elements including platinum group elements (PGEs) from gasoline and diesel catalysts

Science.gov (United States)

Sucha, Veronika; Mihaljevic, Martin; Ettler, Vojtech; Strnad, Ladislav

2014-05-01

The release of trace metals and platinum group elements (PGEs) from automobile exhaust catalysts represents a remarkable source of higly dispersed environmental contamination. Especially, PGEs have shown increasing research interest due to their possible bioaccessibility. In our research, we focused on leaching behaviour of trace metals from gasoline and diesel automobile catalysts. While catalysts for gasoline engines contain a mixture of Pt-Pd-Rh or Pd-Rh, catalysts for diesel engines are composed only of Pt. We used dust from two crushed gasoline and two crushed diesel catalysts (new and aged). The dust of gasoline catalysts contains significant concentrations of Pt (700 mg.kg-1), Pd (11 000 mg.kg-1) and Rh (700 mg.kg-1). And the dust of diesel catalysts are composed of Pt (3 900 mg.kg-1) and they contains negligible amounts of Pd dan Rh (leaching of trace metals from dust we used pH-stat leaching test according to the European standard CEN/TS 14997. The concentrations of cations: PGEs (Pt, Pd a Rh), K, Na, Ca, Mg, Al, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd, Pb, La and Ce were determined by inductively coupled plasma mass spectrometry (ICP-MS) and atomic absorption spectrometry (AAS), and anions: F-, Cl-, SO42- and NO3- by high-performance liquid chromatography. Although the dusts from catalysts were relatively stable to acid/base influence, the leaching of trace metals from catalysts showed a dependence on pH. Generally, the highest concentrations were released under acidic conditions. The leaching of PGEs was higher for Pt in diesel catalysts and for Pd and Rh in gasoline catalysts. The highest concentrations of Zn and Pb were observed in old catalysts. The rare earth metals were released more from gasoline catalysts. Catalysts particles represent health risk especially with respect to their PGEs contents.

Platinum metals in the environment

Energy Technology Data Exchange (ETDEWEB)

Zereini, Fathi [Frankfurt Univ. (Germany). Dept. of Environmental Analytical Chemistry; Wiseman, Clare L.S. (ed.) [Toronto Univ. (Canada). School of the Environment

2015-03-01

This book contains the five chapters with the following topics: 1. SOURCES OF PGE EMISSIONS ELEMENTS: Sources of Platinum Group Elements (PGE) in the Environment; Impact of Platinum Group Element Emissions from Mining and Production Activities. 2. ANALYTICAL METHODS FOR THE DETERMINATION OF PGE IN BIOLOGICAL AND ENVIRONMENTAL MATRICES: Appraisal of Biosorption for Recovery, Separation and Determination of Platinum, Palladium and Rhodium in Environmental Samples; On the Underestimated Factors Influencing the Accuracy of Determination of Pt and Pd by Electrothermal Atomic Absorption Spectrometry in Road Dust Samples; Application of Solid Sorbents for Enrichment and Separation of Platinum Metal Ions; Voltammetric Analysis of Platinum in Environmental Matrices; Speciation Analysis of Chloroplatinates; Analysis of Platinum Group Elements in Environmental Samples: A Review. 3. OCCURRENCE, CHEMICAL BEHAVIOR AND FATE OF PGE IN THE ENVIRONMENT: Brazilian PGE Research Data Survey on Urban and Roadside Soils; Platinum, Palladium and Rhodium in a Bavarian Roadside Soil; Increase of Platinum Group Element Concentrations in Soils and Airborne Dust During the Period of Vehicular Exhaust Catalysts Introduction; Platinum-Group Elements in Urban Fluvial Bed Sediments-Hawaii; Long-Term Monitoring of Palladium and Platinum Contents in Road Dust of the City of Munich, Germany; Characterization of PGEs and Other Elements in Road Dusts and Airborne Particles in Houston, Texas; Accumulation and Distribution of Pt and Pd in Roadside Dust, Soil and Vegetation in Bulgaria; Increase of the Environmental Pt Concentration in the Metropolitan Area of Mexico City Associated to the Use of Automobile Catalytic Converters; Solubility of Emitted Platinum Group Elements (Pt, Pd and Rh) in Airborne Particulate Matter (PM10) in the Presence of Organic Complexing Agents; The Influence of Anionic Species (Cl{sup -}, NO{sub 3}{sup -}, SO{sub 4}{sup 2-}) on the Transformation and Solubility of Platinum in

Electrochemical characterization of platinum nanoparticles stabilized by amines

International Nuclear Information System (INIS)

Ramirez-Meneses, E.; Dominguez-Crespo, M.A.; Montiel-Palma, V.; Chavez-Herrera, V.H.; Gomez, E.; Hernandez-Tapia, G.

2009-01-01

In this work we present the synthesis by Chaudret approach of Pt nanoparticles stabilized by primary amine (-NH 2 ) compounds. Their electrochemical performance as cathodes in low temperature polymer electrolite fuel cells on the oxygen reduction reaction (ORR) is also presented. Transmission electron microscopy (TEM) images of the samples show Pt nanostructures with particle size varying from 10 to 100 nm depending on the kind of the stabilizer used during the catalyst preparation. In some cases well-dispersed isolated platinum nanoparticles were observed. The activity of the dispersed catalysts (Pt/C) with respect to the ORR was investigated using steady state polarization measurements. The kinetic parameters showed that although no significant differences between the Tafel slopes of the Pt catalysts exist, transfer coefficients and exchange current densities show higher activities when the Pt nanoparticles were stabilized by tert-butylamine (TBA). The performance with respect to the ORR of the Pt/C catalyst on vulcan carbon substrate is active and comparable to that reported in the literature for state-of-art electrocatalysts.

Direct atomic-level insight into the active sites of a high-performance PGM-free ORR catalyst

Science.gov (United States)

Chung, Hoon T.; Cullen, David A.; Higgins, Drew; Sneed, Brian T.; Holby, Edward F.; More, Karren L.; Zelenay, Piotr

2017-08-01

Platinum group metal-free (PGM-free) metal-nitrogen-carbon catalysts have emerged as a promising alternative to their costly platinum (Pt)-based counterparts in polymer electrolyte fuel cells (PEFCs) but still face some major challenges, including (i) the identification of the most relevant catalytic site for the oxygen reduction reaction (ORR) and (ii) demonstration of competitive PEFC performance under automotive-application conditions in the hydrogen (H2)-air fuel cell. Herein, we demonstrate H2-air performance gains achieved with an iron-nitrogen-carbon catalyst synthesized with two nitrogen precursors that developed hierarchical porosity. Current densities recorded in the kinetic region of cathode operation, at fuel cell voltages greater than ~0.75 V, were the same as those obtained with a Pt cathode at a loading of 0.1 milligram of Pt per centimeter squared. The proposed catalytic active site, carbon-embedded nitrogen-coordinated iron (FeN4), was directly visualized with aberration-corrected scanning transmission electron microscopy, and the contributions of these active sites associated with specific lattice-level carbon structures were explored computationally.

Characterization of a surface modified carbon cryogel and a carbon supported Pt catalyst

Directory of Open Access Journals (Sweden)

BILJANA M. BABIĆ

2007-08-01

Full Text Available A carbon cryogel, synthesized by carbonization of a resorcinol/formaldehyde cryogel and oxidized in nitric acid, was used as catalyst support for Pt nano-particles. The Pt/C catalyst was prepared by a modified polyol synthesis method in an ethylene glycol (EG solution. Characterization by nitrogen adsorption showed that the carbon cryogel support and the Pt/C catalyst were mesoporous materials with high specific surface areas (SBET > 400 m2 g-1 and large mesoporous volumes. X-Ray diffraction of the catalyst demonstrated the successful reduction of the Pt precursor to metallic form. TEM Images of the Pt/C catalyst and Pt particle size distribution showed that the mean Pt particle size was about 3.3 nm. Cyclic voltammetry (CV experiments at various scan rates (from 2 to 200 mV s-1 were performed in 0.5 mol dm-3 HClO4 solution. The large capacitance of the oxidized carbon cryogel electrode, which arises from a combination of the double-layer capacitance and pseudocapacitance, associated with the participation of surface redox-type reactions was demonstrated. For the oxidized carbon cryogel, the total specific capacitance determined by 1/C vs. ν0.5 extrapolation method was found to be 386 F g-1. The hydrogen oxidation reaction at the investigated Pt/C catalyst proceeded as an electrochemically reversible, two-electron direct discharge reaction.

Catalyst Degradation in High Temperature Proton Exchange Membrane Fuel Cells Based on Acid Doped Polybenzimidazole Membranes

DEFF Research Database (Denmark)

Cleemann, Lars Nilausen; Buazar, F.; Li, Qingfeng

2013-01-01

and multi‐walled carbon nanotubes were used as supports for electrode catalysts and evaluated in accelerated durability tests under potential cycling at 150 °C. Measurements of open circuit voltage, area specific resistance and hydrogen permeation through the membrane were carried out, indicating little...... contribution of the membrane degradation to the performance losses during the potential cycling tests. As the major mechanism of the fuel cell performance degradation, the electrochemical active area of the cathodic catalysts showed a steady decrease in the cyclic voltammetric measurements, which was also......Degradation of carbon supported platinum catalysts is a major failure mode for the long term durability of high temperature proton exchange membrane fuel cells based on phosphoric acid doped polybenzimidazole membranes. With Vulcan carbon black as a reference, thermally treated carbon black...

Electronic states of carbon alloy catalysts and nitrogen substituent effects on catalytic activity

Science.gov (United States)

Hata, Tomoyuki; Ushiyama, Hiroshi; Yamashita, Koichi

2013-03-01

In recent years, Carbon Alloy Catalysts (CACs) are attracting attention as a candidate for non-platinum-based cathode catalysts in fuel cells. Oxygen reduction reactions at the cathode are divided into two elementary processes, electron transfer and oxygen adsorption. The electron transfer reaction is the rate-determining, and by comparison of energy levels, catalytic activity can be evaluated quantitatively. On the other hand, to begin with, adsorption mechanism is obscure. The purpose of this study is to understand the effect of nitrogen substitution and oxygen adsorption mechanism, by first-principle electronic structure calculations for nitrogen substituted models. To reproduce the elementary processes of oxygen adsorption, we assumed that the initial structures are formed based on the Pauling model, a CACs model and nitrogen substituted CACs models in which various points are replaced with nitrogen. When we try to focus only on the DOS peaks of oxygen, in some substituted model that has high adsorption activity, a characteristic partial occupancy state was found. We conclude that this state will affect the adsorption activity, and discuss on why partially occupied states appear with simplification by using an orbital correlation diagram.

Fabrication and Characterization of New Composite Tio2 Carbon Nanofiber Anodic Catalyst Support for Direct Methanol Fuel Cell via Electrospinning Method

Science.gov (United States)

Abdullah, N.; Kamarudin, S. K.; Shyuan, L. K.; Karim, N. A.

2017-12-01

Platinum (Pt) is the common catalyst used in a direct methanol fuel cell (DMFC). However, Pt can lead towards catalyst poisoning by carbonaceous species, thus reduces the performance of DMFC. Thus, this study focuses on the fabrication of a new composite TiO2 carbon nanofiber anodic catalyst support for direct methanol fuel cells (DMFCs) via electrospinning technique. The distance between the tip and the collector (DTC) and the flow rate were examined as influencing parameters in the electrospinning technique. To ensure that the best catalytic material is fabricated, the nanofiber underwent several characterizations and electrochemical tests, including FTIR, XRD, FESEM, TEM, and cyclic voltammetry. The results show that D18, fabricated with a flow rate of 0.1 mLhr-1 and DTC of 18 cm, is an ultrafine nanofiber with the smallest average diameter, 136.73 ± 39.56 nm. It presented the highest catalyst activity and electrochemical active surface area value as 274.72 mAmg-1 and 226.75m2 g-1 PtRu, respectively, compared with the other samples.

Manganese dioxide as a new cathode catalyst in microbial fuel cells

Science.gov (United States)

Li, Xiang; Hu, Boxun; Suib, Steven; Lei, Yu; Li, Baikun

This study focused on manganese oxides with a cryptomelane-type octahedral molecular sieve (OMS-2) structure to replace platinum as a cathode catalyst in microbial fuel cells (MFCs). Undoped (ud-OSM-2) and three catalysts doped with cobalt (Co-OMS-2), copper (Cu-OMS-2), and cerium (Ce-OMS-2) to enhance their catalytic performances were investigated. The novel OMS-2 cathodes were examined in granular activated carbon MFC (GACMFC) with sodium acetate as the anode reagent and oxygen in air as the cathode reagent. The results showed that after 400 h of operation, the Co-OMS-2 and Cu-OMS-2 exhibited good catalytic performance in an oxygen reduction reaction (ORR). The voltage of the Co-OMS-2 GACMFC was 217 mV, and the power density was 180 mW m -2. The voltage of the Cu-OMS-2 GACMFC was 214 mV and the power density was 165 mW m -2. The internal resistance (R in) of the OMS-2 GACMFCs (18 ± 1 Ω) was similar to that of the platinum GACMFCs (17 Ω). Furthermore, the degradation rates of organic substrates in the OMS-2 GACMFCs were twice those in the platinum GACMFCs, which enhance their wastewater treatment efficiencies. This study indicated that using OMS-2 manganese oxides to replace platinum as a cathodic catalyst enhances power generation, increases contaminant removal, and substantially reduces the cost of MFCs.

Manganese dioxide as a new cathode catalyst in microbial fuel cells

Energy Technology Data Exchange (ETDEWEB)

Li, Xiang; Li, Baikun [Department of Civil and Environmental Engineering, University of Connecticut, Storrs, CT 06269 (United States); Hu, Boxun [Institute of Materials Science, University of Connecticut, Storrs, CT 06269 (United States); Suib, Steven [Institute of Materials Science, University of Connecticut, Storrs, CT 06269 (United States); Department of Chemistry, University of Connecticut, Storrs, CT 06269 (United States); Department of Chemical and Biomolecular Engineering, University of Connecticut, Storrs, CT 06269 (United States); Lei, Yu. [Department of Chemical and Biomolecular Engineering, University of Connecticut, Storrs, CT 06269 (United States)

2010-05-01

This study focused on manganese oxides with a cryptomelane-type octahedral molecular sieve (OMS-2) structure to replace platinum as a cathode catalyst in microbial fuel cells (MFCs). Undoped (ud-OSM-2) and three catalysts doped with cobalt (Co-OMS-2), copper (Cu-OMS-2), and cerium (Ce-OMS-2) to enhance their catalytic performances were investigated. The novel OMS-2 cathodes were examined in granular activated carbon MFC (GACMFC) with sodium acetate as the anode reagent and oxygen in air as the cathode reagent. The results showed that after 400 h of operation, the Co-OMS-2 and Cu-OMS-2 exhibited good catalytic performance in an oxygen reduction reaction (ORR). The voltage of the Co-OMS-2 GACMFC was 217 mV, and the power density was 180 mW m{sup -2}. The voltage of the Cu-OMS-2 GACMFC was 214 mV and the power density was 165 mW m{sup -2}. The internal resistance (R{sub in}) of the OMS-2 GACMFCs (18 {+-} 1 {omega}) was similar to that of the platinum GACMFCs (17 {omega}). Furthermore, the degradation rates of organic substrates in the OMS-2 GACMFCs were twice those in the platinum GACMFCs, which enhance their wastewater treatment efficiencies. This study indicated that using OMS-2 manganese oxides to replace platinum as a cathodic catalyst enhances power generation, increases contaminant removal, and substantially reduces the cost of MFCs. (author)

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

International Nuclear Information System (INIS)

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

2010-01-01

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

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...

Oxygen Reduction Reaction Activity of Platinum Thin Films with Different Densities

Energy Technology Data Exchange (ETDEWEB)

Ergul, Busra; Begum, Mahbuba; Kariuki, Nancy; Myers, Deborah J.; Karabacak, Tansel

2017-08-24

Platinum thin films with different densities were grown on glassy carbon electrodes by high pressure sputtering deposition and evaluated as oxygen reduction reaction catalysts for polymer electrolyte fuel cells using cyclic voltammetry and rotating disk electrode techniques in aqueous perchloric acid electrolyte. The electrochemically active surface area, ORR mass activity (MA) and specific activity (SA) of the thin film electrodes were obtained. MA and SA were found to be higher for low-density films than for high-density film.

Recovery of platinum-group metals (PGMS from spent automotive catalysts: Part II: Automotive catalysts: Structures and principle of operation

Directory of Open Access Journals (Sweden)

Dimitrijević Mile D.

2015-01-01

Full Text Available Catalytic converters are incorporated into motor vehicle emission systems (passenger cars, trucks and other motor vehicles, as well as civil and agricultural machines, as of lately to reduce air pollution as well as to meet the emission standards. Their purpose is to convert toxic emissions generated by combustion of liquid fossil fuels into less harmful products. In catalytic converters, rhodium is used for the reduction of gasses, whereas platinum and palladium are used for the oxidation of gasses. This paper presents the structure and operating principle of automotive catalysts in view of the fact that cars are the most prevalent motor vehicles worldwide and due to the fact that the production of cars with gasoline and diesel engines will dominate until at least 2020.

New efficient catalyst for ammonia synthesis: barium-promoted cobalt on carbon

DEFF Research Database (Denmark)

Hagen, Stefan; Barfod, Rasmus; Fehrmann, Rasmus

2002-01-01

Barium-promoted cobalt catalysts supported on carbon exhibit higher ammonia activities at synthesis temperatures than the commercial, multipromoted iron catalyst and also a lower ammonia......Barium-promoted cobalt catalysts supported on carbon exhibit higher ammonia activities at synthesis temperatures than the commercial, multipromoted iron catalyst and also a lower ammonia...

Conical nano-structure arrays of Platinum cathode catalyst for enhanced cell performance in PEMFC (proton exchange membrane fuel cell)

International Nuclear Information System (INIS)

Khan, Aziz; Nath, Bhabesh Kumar; Chutia, Joyanti

2015-01-01

Conical nanostructure arrays of Pt (Platinum) as cathode catalyst are developed using a novel integrated plasma sputtering technique. The integration method involves successive deposition of Pt catalyst arrays one upon another maintaining a uniform time gap. Deposition by integrated approach results in the formation of dense arrays of Pt nanostructure as compared to continuous deposition. These high number density integrated arrays with low Pt loading of 0.10 mg cm −2 at the cathode provide enhanced performance compared to non-integrated cathode catalyst prepared by continuous deposition and standard commercial electrodes with Pt loadings of 1 mg cm −2 . The performance is compared on the basis of polarization curve measurements and the calculated power density values. PEM fuel cell with dual integrated cathode showed an improved power density of 0.90 W cm −2 , which is higher than continuously deposited cathode catalyst with maximum power density of 0.67 W cm −2 for the same Pt loading of 0.10 mg cm −2 . - Highlights: • Conical nanostructures with high number density are prepared by a novel integrated deposition technique. • Electrode with such catalyst shows maximum performance of 0.9 W cm −2 . • Integrated catalyst performs better than continuously prepared nanostructure catalyst.

A novel reusable platinum nanocatalyst

International Nuclear Information System (INIS)

Zhou Weiqiang; Wang Jing; Wang Chuanyi; Du Yukou; Xu Jingkun; Yang Ping

2010-01-01

Recyclability of noble metal catalysts is a challenging issue when dealing with their industrial applications. Smart pH-sensitive Pt nanoparticles were successfully prepared for the first time by using octa(N,N-diacetic acid phenylamine)silsesquioxane (OAPAS) as a macromolecular protective agent. As-prepared Pt nanoparticles can self-aggregate or redisperse by only changing the pH of the system solution. In the weak acidic or alkaline solution (pH > 4.0), the Pt nanoparticles dispersed homogenously; while in the acidic solution (pH = 2.5), they self-aggregated. The dynamic self-aggregation and redispersion processes of the Pt nanoparticles driven by pH changes were revealed by transmission electron microscopy measurements. Electrocatalytic experiments proved that the platinum nanoparticles as a recyclable catalyst showed excellent activity for the hydrogenation of aldehyde after runs of five times. Such platinum nanoparticles are thereby anticipated to have great potential functioning as 'smart' catalysts for industrial applications.

Development of Sulfur and Carbon Tolerant Reforming Alloy Catalysts Aided Fundamental Atomistic Insights

Energy Technology Data Exchange (ETDEWEB)

Suljo Linic

2008-12-31

Current hydrocarbon reforming catalysts suffer from rapid carbon and sulfur poisoning. Even though there is a tremendous incentive to develop more efficient catalysts, these materials are currently formulated using inefficient trial and error experimental approaches. We have utilized a hybrid experimental/theoretical approach, combining quantum Density Functional Theory (DFT) calculations and various state-of-the-art experimental tools, to formulate carbon tolerant reforming catalysts. We have employed DFT calculations to develop molecular insights into the elementary chemical transformations that lead to carbon poisoning of Ni catalysts. Based on the obtained molecular insights, we have identified, using DFT quantum calculation, various Ni alloy catalysts as potential carbon tolerant reforming catalysts. The alloy catalysts were synthesized and tested in steam reforming and partial oxidation of methane, propane, and isooctane. We demonstrated that the alloy catalysts are much more carbon-tolerant than monometallic Ni catalysts under nearly stoichiometric steam-to-carbon ratios. Under these conditions, monometallic Ni is rapidly poisoned by sp2 carbon deposits. The research approach is distinguished by two characteristics: (a) knowledge-based, bottomup approach, compared to the traditional trial and error approach, allows for a more efficient and systematic discovery of improved catalysts. (b) the focus is on exploring alloy materials which have been largely unexplored as potential reforming catalysts.

Platinum Catalysts Supported on Ce, Zr, Pr - Oxides in Catalytic Wet Air Oxidation of Acetic Acid

Czech Academy of Sciences Publication Activity Database

Mikulová, Jana; Rossignol, S.; Barbier Jr., J.; Duprez, D.; Kappenstein, C.

2007-01-01

Roč. 146, č. 3 (2007), s. 1248-1253 ISSN 0304-3894 Institutional research plan: CEZ:AV0Z40720504 Keywords : platinum * cerium oxide * carbonate species Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.337, year: 2007

Interfacial charge distributions in carbon-supported palladium catalysts

DEFF Research Database (Denmark)

Rao, Radhika G.; Blume, Raoul; Hansen, Thomas Willum

2017-01-01

Controlling the charge transfer between a semiconducting catalyst carrier and the supported transition metal active phase represents an elite strategy for fine turning the electronic structure of the catalytic centers, hence their activity and selectivity. These phenomena have been theoretically...... and experimentally elucidated for oxide supports but remain poorly understood for carbons due to their complex nanoscale structure. Here, we combine advanced spectroscopy and microscopy on model Pd/C samples to decouple the electronic and surface chemistry effects on catalytic performance. Our investigations reveal...... treatments can be used to tune the interfacial charge distribution, hereby providing a strategy to rationally design carbon-supported catalysts.Control over charge transfer in carbon-supported metal nanoparticles is essential for designing new catalysts. Here, the authors show that thermal treatments...

Platinum catalysts recovery of the proton exchange membrane fuel cell; Recuperacao de catalisadores de platina da celula a combustibel de membrana polimerica trocadora de protons

Energy Technology Data Exchange (ETDEWEB)

Fukurozaki, S.H.; Seo, E.S.M. [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil). Centro de Ciencia e Tecnologia de Materiais. Lab. de Processamento de Residuos

2006-07-01

Currently, platinum is the most feasible catalyst for the Proton Exchange Membrane Fuel Cells - PEMFC. Along with platinum's significant importance in this energy system are the high cost of this noble metal and its detrimental effects on the environment. Therefore, recycling this material seems as an alternative to decrease its impacts on the environment and, at the same time, to provide a reduction of the system's costs. A search was conducted for literature and studies about platinum recycling methods. However, only two techniques of platinum recovery, which are still in development, were found. In face of this situation, a recovery method of platinum from deactivated Membrane Electrode Assembly - MEA's was developed, with attention to aspects related to the environment and the necessary requirements for its primary recycling. The results found showed a high recovery ratio and a possibility to reintroduce this metal into the production cycle. (author)

Nitrogen-doped carbon-supported cobalt-iron oxygen reduction catalyst

Science.gov (United States)

Zelenay, Piotr; Wu, Gang

2014-04-29

A Fe--Co hybrid catalyst for oxygen reaction reduction was prepared by a two part process. The first part involves reacting an ethyleneamine with a cobalt-containing precursor to form a cobalt-containing complex, combining the cobalt-containing complex with an electroconductive carbon supporting material, heating the cobalt-containing complex and carbon supporting material under conditions suitable to convert the cobalt-containing complex and carbon supporting material into a cobalt-containing catalyst support. The second part of the process involves polymerizing an aniline in the presence of said cobalt-containing catalyst support and an iron-containing compound under conditions suitable to form a supported, cobalt-containing, iron-bound polyaniline species, and subjecting said supported, cobalt-containing, iron bound polyaniline species to conditions suitable for producing a Fe--Co hybrid catalyst.

An efficient and pH-universal ruthenium-based catalyst for the hydrogen evolution reaction

Science.gov (United States)

Mahmood, Javeed; Li, Feng; Jung, Sun-Min; Okyay, Mahmut Sait; Ahmad, Ishfaq; Kim, Seok-Jin; Park, Noejung; Jeong, Hu Young; Baek, Jong-Beom

2017-05-01

The hydrogen evolution reaction (HER) is a crucial step in electrochemical water splitting and demands an efficient, durable and cheap catalyst if it is to succeed in real applications. For an energy-efficient HER, a catalyst must be able to trigger proton reduction with minimal overpotential and have fast kinetics. The most efficient catalysts in acidic media are platinum-based, as the strength of the Pt-H bond is associated with the fastest reaction rate for the HER. The use of platinum, however, raises issues linked to cost and stability in non-acidic media. Recently, non-precious-metal-based catalysts have been reported, but these are susceptible to acid corrosion and are typically much inferior to Pt-based catalysts, exhibiting higher overpotentials and lower stability. As a cheaper alternative to platinum, ruthenium possesses a similar bond strength with hydrogen (˜65 kcal mol-1), but has never been studied as a viable alternative for a HER catalyst. Here, we report a Ru-based catalyst for the HER that can operate both in acidic and alkaline media. Our catalyst is made of Ru nanoparticles dispersed within a nitrogenated holey two-dimensional carbon structure (Ru@C2N). The Ru@C2N electrocatalyst exhibits high turnover frequencies at 25 mV (0.67 H2 s-1 in 0.5 M H2SO4 solution; 0.75 H2 s-1 in 1.0 M KOH solution) and small overpotentials at 10 mA cm-2 (13.5 mV in 0.5 M H2SO4 solution; 17.0 mV in 1.0 M KOH solution) as well as superior stability in both acidic and alkaline media. These performances are comparable to, or even better than, the Pt/C catalyst for the HER.

Thief carbon catalyst for oxidation of mercury in effluent stream

Science.gov (United States)

Granite, Evan J [Wexford, PA; Pennline, Henry W [Bethel Park, PA

2011-12-06

A catalyst for the oxidation of heavy metal contaminants, especially mercury (Hg), in an effluent stream is presented. The catalyst facilitates removal of mercury through the oxidation of elemental Hg into mercury (II) moieties. The active component of the catalyst is partially combusted coal, or "Thief" carbon, which can be pre-treated with a halogen. An untreated Thief carbon catalyst can be self-promoting in the presence of an effluent gas streams entrained with a halogen.

Carbonized tantalum catalysts for catalytic chemical vapor deposition of silicon films

Energy Technology Data Exchange (ETDEWEB)

Cheng Shimin [State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023 (China); Dalian National Laboratory for Clean Energy, Dalian 116023 (China); Graduate University of Chinese Academy of Sciences, Beijing 100049 (China); Gao Huiping; Ren Tong; Ying Pinliang [State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023 (China); Dalian National Laboratory for Clean Energy, Dalian 116023 (China); Li Can, E-mail: canli@dicp.ac.cn [State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023 (China); Dalian National Laboratory for Clean Energy, Dalian 116023 (China)

2012-06-01

Catalytic chemical vapor deposition (Cat-CVD) has been demonstrated as a promising way to prepare device-quality silicon films. However, catalyst ageing due to Si contamination is an urgency to be solved for the practical application of the technique. In this study, the effect of carbonization of tantalum catalyst on its structure and performance was investigated. The carbonized Ta catalyst has a TaC surface layer which is preserved over the temperature range between 1450 and 1750 Degree-Sign C and no Si contamination occurs on the catalyst after long-term use. Si film prepared using the carbonized Ta catalyst has a similar crystal structure to that prepared by uncarbonized Ta catalyst. Formation of the TaC surface layer can alleviate the ageing problem of the catalyst, which shows great potential as a stable catalyst for Cat-CVD of Si films. - Highlights: Black-Right-Pointing-Pointer Si films prepared by catalytic chemical vapor deposition. Black-Right-Pointing-Pointer Carbonized Ta with a TaC surface layer used as catalyst. Black-Right-Pointing-Pointer TaC surface structure preserved after long-term use in a wide temperature range. Black-Right-Pointing-Pointer Help to solve the ageing problem of metal catalysts. Black-Right-Pointing-Pointer Si film obtained has a similar crystal structure to that prepared by Ta catalyst.

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.

Catalysts for Efficient Production of Carbon Nanotubes

Science.gov (United States)

Sun, Ted X.; Dong, Yi

2009-01-01

Several metal alloys have shown promise as improved catalysts for catalytic thermal decomposition of hydrocarbon gases to produce carbon nanotubes (CNTs). Heretofore almost every experiment on the production of carbon nanotubes by this method has involved the use of iron, nickel, or cobalt as the catalyst. However, the catalytic-conversion efficiencies of these metals have been observed to be limited. The identification of better catalysts is part of a continuing program to develop means of mass production of high-quality carbon nanotubes at costs lower than those achieved thus far (as much as $100/g for purified multi-wall CNTs or $1,000/g for single-wall CNTs in year 2002). The main effort thus far in this program has been the design and implementation of a process tailored specifically for high-throughput screening of alloys for catalyzing the growth of CNTs. The process includes an integral combination of (1) formulation of libraries of catalysts, (2) synthesis of CNTs from decomposition of ethylene on powders of the alloys in a pyrolytic chemical-vapor-decomposition reactor, and (3) scanning- electron-microscope screening of the CNTs thus synthesized to evaluate the catalytic efficiencies of the alloys. Information gained in this process is put into a database and analyzed to identify promising alloy compositions, which are to be subjected to further evaluation in a subsequent round of testing. Some of these alloys have been found to catalyze the formation of carbon nano tubes from ethylene at temperatures as low as 350 to 400 C. In contrast, the temperatures typically required for prior catalysts range from 550 to 750 C.

Fine platinum nanoparticles supported on a porous ceramic membrane as efficient catalysts for the removal of benzene.

Science.gov (United States)

Liu, Hui; Li, Chengyin; Ren, Xiaoyong; Liu, Kaiqi; Yang, Jun

2017-11-29

It would be desirable to remove volatile organic compounds (VOCs) while we eliminate the dusts using silicon carbide (SiC)-based porous ceramics from the hot gases. Aiming at functionalizing SiC-based porous ceramics with catalytic capability, we herein report a facile strategy to integrate high efficient catalysts into the porous SiC substrates for the VOC removal. We demonstrate an aqueous salt method for uniformly distributing fine platinum (Pt) particles on the alumina (Al 2 O 3 ) layers, which are pre-coated on the SiC substrates as supports for VOC catalysts. We confirm that at a Pt mass loading as low as 0.176% and a weight hourly space velocity of 6000 mL g -1 h -1 , the as-prepared Pt/SiC@Al 2 O 3 catalysts can convert 90% benzene at a temperature of ca. 215 °C. The results suggest a promising way to design ceramics-based bi-functional materials for simultaneously eliminating dusts and harmful VOCs from various hot gases.

To alloy or not to alloy? Cr modified Pt/C cathode catalysts for PEM fuel cells.

Science.gov (United States)

Wells, Peter P; Qian, Yangdong; King, Colin R; Wiltshire, Richard J K; Crabb, Eleanor M; Smart, Lesley E; Thompsett, David; Russell, Andrea E

2008-01-01

The cathode electrocatalysts for proton exchange membrane (PEM) fuel cells are commonly platinum and platinum based alloy nanoparticles dispersed on a carbon support. Control over the particle size and composition has, historically, been attained empirically, making systematic studies of the effects of various structural parameters difficult. The controlled surface modification methodology used in this work has enabled the controlled modification of carbon supported Pt nanoparticles by Cr so as to yield nanoalloy particles with defined compositions. Subsequent heat treatment in 5% H2 in N2 resulted in the formation of a distinct Pt3Cr alloy phase which was either restricted to the surface of the particles or present throughout the bulk of the particle structure. Measurement of the oxygen reduction activity of the catalysts was accomplished using the rotating thin film electrode method and the activities obtained were related to the structure of the nanoalloy catalyst particles, largely determined using Cr K edge and Pt L3 edge XAS.

Development of styrene divinyl benzene catalyst in isotopic exchange reaction of water and hydrogen

International Nuclear Information System (INIS)

Morishita, Teizo; Noda, Shigeyuki; Tan, Tsutomu; Noguchi, Hiroshi

1982-01-01

Styrene divinyl benzene copolymer (SDBC) is hydrophobic, and porous with large specific surface area. Utilizing these properties, the SDBC was used for the carrier of catalyst in water-hydrogen exchange reaction process, and the hydrophobic platinum catalyst with very high performance was able to be developed. However, the SDBC is usually fine particles smaller than 1 mm, and is not suitable as the filling catalyst for exchange reaction towers. Therefore, in this study, using only platinum as a catalyst metal, the improvement of the property of carriers was emphatically examined, and platinum bearing was proved with an optical or electron microscope. As the result, it was found that the SDBC catalyst showed high activity practically usable as the hydrophobic catalyst for heavy water or tritium exchange reaction. The characteristics of SDBC are explained. The manufacturing processes of the catalyst by making SDBC carriers with fine particles and letting them bear platinum are described. The results of the trial manufacture of spherical, extrusion-formed and honeycomb carrier catalysts are reported. Platinum must be dispersed over the large specific surface area of SDBC carriers. (Kako, I.)

Core-shell rhodium sulfide catalyst for hydrogen evolution reaction / hydrogen oxidation reaction in hydrogen-bromine reversible fuel cell

Science.gov (United States)

Li, Yuanchao; Nguyen, Trung Van

2018-04-01

Synthesis and characterization of high electrochemical active surface area (ECSA) core-shell RhxSy catalysts for hydrogen evolution oxidation (HER)/hydrogen oxidation reaction (HOR) in H2-Br2 fuel cell are discussed. Catalysts with RhxSy as shell and different percentages (5%, 10%, and 20%) of platinum on carbon as core materials are synthesized. Cyclic voltammetry is used to evaluate the Pt-equivalent mass specific ECSA and durability of these catalysts. Transmission electron microscopy (TEM), X-ray Photoelectron spectroscopy (XPS) and Energy-dispersive X-ray spectroscopy (EDX) techniques are utilized to characterize the bulk and surface compositions and to confirm the core-shell structure of the catalysts, respectively. Cycling test and polarization curve measurements in the H2-Br2 fuel cell are used to assess the catalyst stability and performance in a fuel cell. The results show that the catalysts with core-shell structure have higher mass specific ECSA (50 m2 gm-Rh-1) compared to a commercial catalyst (RhxSy/C catalyst from BASF, 6.9 m2 gm-Rh-1). It also shows better HOR/HER performance in the fuel cell. Compared to the platinum catalyst, the core-shell catalysts show more stable performance in the fuel cell cycling test.

Activity targets for nanostructured platinum-group-metal-free catalysts in hydroxide exchange membrane fuel cells

Science.gov (United States)

Setzler, Brian P.; Zhuang, Zhongbin; Wittkopf, Jarrid A.; Yan, Yushan

2016-12-01

Fuel cells are the zero-emission automotive power source that best preserves the advantages of gasoline automobiles: low upfront cost, long driving range and fast refuelling. To make fuel-cell cars a reality, the US Department of Energy has set a fuel cell system cost target of US$30 kW-1 in the long-term, which equates to US$2,400 per vehicle, excluding several major powertrain components (in comparison, a basic, but complete, internal combustion engine system costs approximately US$3,000). To date, most research for automotive applications has focused on proton exchange membrane fuel cells (PEMFCs), because these systems have demonstrated the highest power density. Recently, however, an alternative technology, hydroxide exchange membrane fuel cells (HEMFCs), has gained significant attention, because of the possibility to use stable platinum-group-metal-free catalysts, with inherent, long-term cost advantages. In this Perspective, we discuss the cost profile of PEMFCs and the advantages offered by HEMFCs. In particular, we discuss catalyst development needs for HEMFCs and set catalyst activity targets to achieve performance parity with state-of-the-art automotive PEMFCs. Meeting these targets requires careful optimization of nanostructures to pack high surface areas into a small volume, while maintaining high area-specific activity and favourable pore-transport properties.

Nitrogen-doped carbon nanotubes as a metal catalyst support

CSIR Research Space (South Africa)

Mabena, LF

2011-05-01

Full Text Available ., which are among the most commonly used heterogeneous catalyst supports (Mart??nez-Me?ndez et al. 2006). Catalyst activity depends on the particle size and appropriate dis- tance between each particle. These catalysts deposited on a support... supported Pt electrodes. Appl Catal B Environ 80:286?295 Maldonado S, Morin S, Stevenson KJ (2006) Structure, composition, and chemical reactivity of carbon nanotubes by selective nitrogen doping. Carbon 44:1429?1437 Mart??nez-Me?ndez S, Henr??quez Y...

Power generation using an activated carbon fiber felt cathode in an upflow microbial fuel cell

KAUST Repository

Deng, Qian

2010-02-01

An activated carbon fiber felt (ACFF) cathode lacking metal catalysts is used in an upflow microbial fuel cell (UMFC). The maximum power density with the ACFF cathode is 315 mW m-2, compared to lower values with cathodes made of plain carbon paper (67 mW m-2), carbon felt (77 mW m-2), or platinum-coated carbon paper (124 mW m-2, 0.2 mg-Pt cm-2). The addition of platinum to the ACFF cathode (0.2 mg-Pt cm-2) increases the maximum power density to 391 mW m-2. Power production is further increased to 784 mW m-2 by increasing the cathode surface area and shaping it into a tubular form. With ACFF cutting into granules, the maximum power is 481 mW m-2 (0.5 cm granules), and 667 mW m-2 (1.0 cm granules). These results show that ACFF cathodes lacking metal catalysts can be used to substantially increase power production in UMFC compared to traditional materials lacking a precious metal catalyst. © 2009 Elsevier B.V.

Proton Exchange Membrane Fuel Cell With Enhanced Durability Using Fluorinated Carbon As Electrocatalyst

Directory of Open Access Journals (Sweden)

Ahmad Yasser

2017-01-01

Full Text Available This study evaluates the fluorination of a carbon aerogel and its effects on the durability of the resulting electrocatalyst for Proton Exchange Membrane Fuel Cell (PEMFC. Fluorine has been introduced before or after platinum deposition. The different electrocatalysts are physico-chemically and electrochemically characterized, and the results discussed by comparison with commercial Pt/XC72 from E-Tek. The results demonstrate that the level of fluorination of the carbon aerogel can be controlled. The fluorination modifies the texture of the carbons by increasing the pore size and decreasing the specific surface area, but the textures remain appropriate for PEMFC applications. Two fluorination sites are observed, leading to both high covalent C-F bond and weakened ones, the quantity of which depends on whether the treatment is done before or after platinum deposition. The order of the different treatments is very important. The presence of platinum contributes to the fluorination mechanism, but leads to amorphous platinum rather inactive towards the Oxygen Reduction Reaction. Finally, a better durability was demonstrated for the fluorinated then platinized catalyst compared both to the same but not fluorinated catalyst and to the reference commercial material (based on the loss of the electrochemical real surface area after accelerated stress tests.

Platinum supported on titanium-ruthenium oxide is a remarkably stable electrocatayst for hydrogen fuel cell vehicles.

Science.gov (United States)

Parrondo, Javier; Han, Taehee; Niangar, Ellazar; Wang, Chunmei; Dale, Nilesh; Adjemian, Kev; Ramani, Vijay

2014-01-07

We report a unique and highly stable electrocatalyst-platinum (Pt) supported on titanium-ruthenium oxide (TRO)-for hydrogen fuel cell vehicles. The Pt/TRO electrocatalyst was exposed to stringent accelerated test protocols designed to induce degradation and failure mechanisms identical to those seen during extended normal operation of a fuel cell automobile-namely, support corrosion during vehicle startup and shutdown, and platinum dissolution during vehicle acceleration and deceleration. These experiments were performed both ex situ (on supports and catalysts deposited onto a glassy carbon rotating disk electrode) and in situ (in a membrane electrode assembly). The Pt/TRO was compared against a state-of-the-art benchmark catalyst-Pt supported on high surface-area carbon (Pt/HSAC). In ex situ tests, Pt/TRO lost only 18% of its initial oxygen reduction reaction mass activity and 3% of its oxygen reduction reaction-specific activity, whereas the corresponding losses for Pt/HSAC were 52% and 22%. In in situ-accelerated degradation tests performed on membrane electrode assemblies, the loss in cell voltage at 1 A · cm(-2) at 100% RH was a negligible 15 mV for Pt/TRO, whereas the loss was too high to permit operation at 1 A · cm(-2) for Pt/HSAC. We clearly show that electrocatalyst support corrosion induced during fuel cell startup and shutdown is a far more potent failure mode than platinum dissolution during fuel cell operation. Hence, we posit that the need for a highly stable support (such as TRO) is paramount. Finally, we demonstrate that the corrosion of carbon present in the gas diffusion layer of the fuel cell is only of minor concern.

Growth mechanism of graphene on platinum: Surface catalysis and carbon segregation

International Nuclear Information System (INIS)

Sun, Jie; Lindvall, Niclas; Yurgens, August; Nam, Youngwoo; Cole, Matthew T.; Teo, Kenneth B. K.; Woo Park, Yung

2014-01-01

A model of the graphene growth mechanism of chemical vapor deposition on platinum is proposed and verified by experiments. Surface catalysis and carbon segregation occur, respectively, at high and low temperatures in the process, representing the so-called balance and segregation regimes. Catalysis leads to self-limiting formation of large area monolayer graphene, whereas segregation results in multilayers, which evidently “grow from below.” By controlling kinetic factors, dominantly monolayer graphene whose high quality has been confirmed by quantum Hall measurement can be deposited on platinum with hydrogen-rich environment, quench cooling, tiny but continuous methane flow and about 1000 °C growth temperature

The exchange reaction between deuterium and water vapour on platinum deposited over a hydrophobic support

International Nuclear Information System (INIS)

Itsuo, Iida; Junko, Kato; Kenzi, Tamuru

1977-01-01

Isotope exchange reaction between deuterium gas and water vapour at room temperature and below on platinum deposited on hydrophobic supports such as polytetrafluoroethylene (PTFE) or Porapak Q (copolymer of styrene and divinylbenzene) was studied and the results were compared with those of the exchange reaction on platinum over hydrophilic support such as alumina. It was demonstrated that the exchange reaction at temperatures below the boiling point of water is markedly retarded by the multilayer adsorption of water over the platinum catalyst deposited on hydrophilic support, whereas the platinum catalyst on hydrophobic support exhibited a high catalytic activity, being not retarded by the water, forming no multilayer of adsorbed water over platinum surface. Therefore in the case of the hydrogen isotope exchange reaction on platinum over hydrophobic support, the chemical exchange rate can be measured even under a saturated vapour pressure of water. The surface area of platinum was estimated by hydrogen chemisorption and hydrogen titration and specific activities of the catalyst were calculated at both room temperature and freezing point of water, which revealed that the specific rate of this reaction does not differ so much over various supports. (orig.) [de

Catalyst layers for PEMFC manufactured by flexography printing process: performances and structure

Energy Technology Data Exchange (ETDEWEB)

Bois, C.; Blayo, A.; Chaussy, D. [Laboratory of Pulp and Paper Science and Graphic Arts (LGP2) (UMR 5518 CNRS-CTP-INPG), Grenoble Institute of Technology (INP Grenoble - PAGORA), St Martin d' Heres (France); Vincent, R.; Mercier, A.G.; Nayoze, C. [Commissariat a l' Energie Atomique et aux Energies Alternatives (CEA)/DRT/LITEN, Laboratoire des Composants Piles a Combustible, Electrolyse et Modelisation (LCPEM), Grenoble (France)

2012-04-15

This article focuses on the potential of a classic printing process, flexography, for manufacturing proton exchange membrane fuel cells (PEMFCs). Gas diffusion electrodes (GDEs) are produced by deposition of a water-based catalyst ink on a gas diffusion layer (GDL). The affinity between the ink and the GDL is quantified. Thus, the strong hydrophobic character of the GDL and the poor printability of the ink are demonstrated. However, the permeability of the GDL allows developing a multilayer protocol. The deposition by superimposition of ink layers allows control of the platinum amount and to obtain catalyst layers with a similar density of platinum nanoparticles to coated samples. At similar platinum loading, flexography and coating made catalyst layers offer similar performances, which confirm the relevance of flexography in catalyst layer manufacturing. Structural characterization shows that manufacturing protocol and process has an influence on catalyst layer microstructure. However, catalyst layer cracking and aggregation are increased with the catalyst layer thickness, diminishing the charge and gas diffusion into the catalyst layer resulting in performance degradation. Consequently, a catalyst layer with 0.46 mgPt cm{sup -2} reaches similar performances to catalyst layers with 1.77 and 2.01 times less platinum loading. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Synthesis of carbon nanotubes by CCVD of natural gas using hydrotreating catalysts

Directory of Open Access Journals (Sweden)

Ahmed E. Awadallah

2012-12-01

Full Text Available Carbon nanotubes have been successfully synthesized using the catalytic chemical vapor deposition (CCVD technique over typical refining hydrotreating catalysts (hydrodesulfurization and hydrodenitrogenation containing Ni–Mo and Co–Mo supported on Al2O3 catalysts at 700°C in a fixed bed horizontal reactor using natural gas as a carbon source. The catalysts and the as-grown CNTs were characterized by transmission electron microscopy, HRTEM, X-ray diffraction patterns, EDX and TGA–DTG. The obtained data clarified that the Ni–Mo catalyst gives higher yield, higher purity and selectivity for CNTs compared to Co–Mo catalyst. XRD, TEM and TGA reveal also that the Ni–Mo catalyst produces mostly CNTs with different diameters whereas the Co–Mo catalyst produces largely amorphous carbon.

Mild in situ growth of platinum nanoparticles on multiwalled carbon nanotube-poly (vinyl alcohol) hydrogel electrode for glucose electrochemical oxidation

Energy Technology Data Exchange (ETDEWEB)

Liu, Shumin; Zheng, Yudong, E-mail: zhengyudong@mater.ustb.edu.cn; Qiao, Kun [University of Science and Technology Beijing, School of Material Science and Engineering (China); Su, Lei [University of Science and Technology Beijing, School of Chemistry and Biological Engineering (China); Sanghera, Amendeep; Song, Wenhui [University College London, UCL Centre for Nanotechnology & Regenerative Medicine, Division of Surgery and Interventional Science (United Kingdom); Yue, Lina; Sun, Yi [University of Science and Technology Beijing, School of Material Science and Engineering (China)

2015-12-15

This investigation describes an effective strategy to fabricate an electrochemically active hybrid hydrogel made from platinum nanoparticles that are highly dense, uniformly dispersed, and tightly embedded throughout the conducting hydrogel network for the electrochemical oxidation of glucose. A suspension of multiwalled carbon nanotubes and polyvinyl alcohol aqueous was coated on glassy carbon electrode by electrophoretic deposition and then physically crosslinked to form a three-dimensional porous conductive hydrogel network by a process of freezing and thawing. The network offered 3D interconnected mass-transport channels (around 200 nm) and confined nanotemplates for in situ growth of uniform platinum nanoparticles via the moderate reduction agent, ascorbic acid. The resulting hybrid hydrogel electrode membrane demonstrates an effective method for loading platinum nanoparticles on multiwalled carbon nanotubes by the electrostatic adsorption between multiwalled carbon nanotubes and platinum ions within porous hydrogel network. The average diameter of platinum nanoparticles is 37 ± 14 nm, which is less than the particle size by only using the moderate reduction agent. The hybrid hydrogel electrode membrane-coated glassy carbon electrode showed excellent electrocatalytic activity and good long-term stability toward glucose electrochemical oxidation. The glucose oxidation current exhibited a linear relationship with the concentration of glucose in the presence of chloride ions, promising for potential applications of implantable biofuel cells, biosensors, and electronic devices.

Phosphoric acid fuel cell platinum use study

Science.gov (United States)

Lundblad, H. L.

1983-05-01

The U.S. Department of Energy is promoting the private development of phosphoric acid fuel cell (PAFC) power plants for terrestrial applications. Current PAFC technology utilizes platinum as catalysts in the power electrodes. The possible repercussions that the platinum demand of PAFC power plant commercialization will have on the worldwide supply and price of platinum from the outset of commercialization to the year 2000 are investigated. The platinum demand of PAFC commercialization is estimated by developing forecasts of platinum use per unit of generating capacity and penetration of PAFC power plants into the electric generation market. The ability of the platinum supply market to meet future demands is gauged by assessing the size of platinum reserves and the capability of platinum producers to extract, refine and market sufficient quantities of these reserves. The size and timing of platinum price shifts induced by the added demand of PAFC commercialization are investigated by several analytical methods. Estimates of these price shifts are then used to calculate the subsequent effects on PAFC power plant capital costs.

Reduction of Furfural to Furfuryl Alcohol in Liquid Phase over a Biochar-Supported Platinum Catalyst

Directory of Open Access Journals (Sweden)

Ariadna Fuente-Hernández

2017-02-01

Full Text Available In this work, the liquid phase hydrogenation of furfural has been studied using a biochar-supported platinum catalyst in a batch reactor. Reactions were performed between 170 °C and 320 °C, using 3 wt % and 5 wt % of Pt supported on a maple-based biochar under hydrogen pressure varying from 500 psi to 1500 psi for reaction times between 1 h and 6 h in various solvents. Under all reactive conditions, furfural conversion was significant, whilst under specific conditions furfuryl alcohol (FA was obtained in most cases as the main product showing a selectivity around 80%. Other products as methylfuran (MF, furan, and trace of tetrahydrofuran (THF were detected. Results showed that the most efficient reaction conditions involved a 3% Pt load on biochar and operations for 2 h at 210 °C and 1500 psi using toluene as solvent. When used repetitively, the catalyst showed deactivation although only a slight variation in selectivity toward FA at the optimal experimental conditions was observed.

Renewable hydrogen: carbon formation on Ni and Ru catalysts during ethanol steam-reforming

DEFF Research Database (Denmark)

Rass-Hansen, Jeppe; Christensen, Christina Hviid; Sehested, J.

2007-01-01

for the production of hydrogen is investigated, along with quantitative and qualitative determinations of carbon formation on the catalysts by TPO and TEM experiments. A Ru/ MgAl2O4 catalyst, a Ni/MgAl2O4 catalyst as well as Ag-and K-promoted Ni/ MgAl2O4 catalysts were studied. The operating temperature was between...... addition was a rapid deactivation of the catalyst due to an enhanced gum carbon formation on the Ni crystals. Contrary to this, the effect of K addition was a prolonged resistance against carbon formation and therefore against deactivation. The Ru catalyst operates better than all the Ni catalysts...

Influence of platinum group metal-free catalyst synthesis on microbial fuel cell performance

Science.gov (United States)

Santoro, Carlo; Rojas-Carbonell, Santiago; Awais, Roxanne; Gokhale, Rohan; Kodali, Mounika; Serov, Alexey; Artyushkova, Kateryna; Atanassov, Plamen

2018-01-01

Platinum group metal-free (PGM-free) ORR catalysts from the Fe-N-C family were synthesized using sacrificial support method (SSM) technique. Six experimental steps were used during the synthesis: 1) mixing the precursor, the metal salt, and the silica template; 2) first pyrolysis in hydrogen rich atmosphere; 3) ball milling; 4) etching the silica template using harsh acids environment; 5) the second pyrolysis in ammonia rich atmosphere; 6) final ball milling. Three independent batches were fabricated following the same procedure. The effect of each synthetic parameters on the surface chemistry and the electrocatalytic performance in neutral media was studied. Rotating ring disk electrode (RRDE) experiment showed an increase in half wave potential and limiting current after the pyrolysis steps. The additional improvement was observed after etching and performing the second pyrolysis. A similar trend was seen in microbial fuel cells (MFCs), in which the power output increased from 167 ± 2 μW cm-2 to 214 ± 5 μW cm-2. X-ray Photoelectron Spectroscopy (XPS) was used to evaluate surface chemistry of catalysts obtained after each synthetic step. The changes in chemical composition were directly correlated with the improvements in performance. We report outstanding reproducibility in both composition and performance among the three different batches.

Sulfidation of carbon-supported iron oxide catalysts

NARCIS (Netherlands)

Ramselaar, W.L.T.M.; Hadders, R.H.; Gerkema, E.; Beer, de V.H.J.; Oers, van E.M.; Kraan, van der A.M.

1989-01-01

The sulfidation of carbon-supported iron oxide catalysts was studied by means of in-situ Mössbauer spectroscopy at temperatures down to 4.2 K. The catalysts were dried in two different ways and then sulfided in a flow of 10% H2S in H2 at temperatures between 293 and 773 K. Thiophene

Modeling chemisorption kinetics of carbon monoxide on polycrystalline platinum

Energy Technology Data Exchange (ETDEWEB)

Donnelly, R.G.; Modell, M.; Baddour, R.F.

1978-04-01

Seven distinct desorption surface states of carbon monoxide on polycrystalline platinum were detected by deconvoluting temperature-programed desorption spectra of 4-100% carbon monoxide monolayer coverage. The adstates had fixed activation energies of desorption (22.5-32.6 kcal/mole) over the entire coverage range. Rates of formation and populations were derived. The chemisorption was modeled by a Hinshelwood-type expression which allowed for site creation and suggested that adsorbed molecules are sufficiently mobile during desorption heating to fill ordered states of minimum energy and that chemisorption into these states is noncompetitive and determined by the surface. Spectra, diagrams, graphs, tables, and 49 references.

Carbon coated (carbonous) catalyst in ebullated bed reactor for production of oxygenated chemicals from syngas/CO2

International Nuclear Information System (INIS)

Peizheng Zhou

2002-01-01

This report summarizes the work completed under DOE's Support of Advanced Fuel Research program, Contract No. DE-FG26-99FT40681. The contract period was October 2000 through September 2002. This R and D program investigated the modification of the mechanical strength of catalyst extrudates using Hydrocarbon Technologies, Inc. (HTI) carbon-coated catalyst technology so that the ebullated bed technology can be utilized to produce valuable oxygenated chemicals from syngas/CO 2 efficiently and economically. Exothermic chemical reactions benefit from the temperature control and freedom from catalyst fouling provided by the ebullated bed reactor technology. The carbon-coated extrudates prepared using these procedures had sufficient attrition resistance and surface area for use in ebullated bed operation. The low cost of carbon coating makes the carbon-coated catalysts highly competitive in the market of catalyst extrudates

Physicochemical investigations of carbon nanofiber supported Cu/ZrO2 catalyst

International Nuclear Information System (INIS)

Din, Israf Ud; Shaharun, Maizatul S.; Subbarao, Duvvuri; Naeem, A.

2014-01-01

Zirconia-promoted copper/carbon nanofiber catalysts (Cu‐ZrO 2 /CNF) were prepared by the sequential deposition precipitation method. The Herringbone type of carbon nanofiber GNF-100 (Graphite nanofiber) was used as a catalyst support. Carbon nanofiber was oxidized to (CNF-O) with 5% and 65 % concentration of nitric acid (HNO 3 ). The CNF activated with 5% HNO 3 produced higher surface area which is 155 m 2 /g. The catalyst was characterized by X-ray Diffraction (XRD), Fourier Transform Infra-Red (FTIR) and N 2 adsorption-desorption. The results showed that increase of HNO 3 concentration reduced the surface area and porosity of the catalyst

Hydrogenation of o-cresol on platinum catalyst: Catalytic experiments and first-principles calculations

Energy Technology Data Exchange (ETDEWEB)

Li, Yaping [Department of Physics and Engineering Physics, The University of Tulsa, Tulsa, OK 74104 (United States); Liu, Zhimin [School of Chemical, Biological and Materials Engineering, University of Oklahoma, Norman, OK 73019 (United States); Xue, Wenhua [Department of Physics and Engineering Physics, The University of Tulsa, Tulsa, OK 74104 (United States); Crossley, Steven P.; Jentoft, Friederike C. [School of Chemical, Biological and Materials Engineering, University of Oklahoma, Norman, OK 73019 (United States); Wang, Sanwu, E-mail: sanwu-wang@utulsa.edu [Department of Physics and Engineering Physics, The University of Tulsa, Tulsa, OK 74104 (United States)

2017-01-30

Highlights: • Hydrogenation of o-cresol over Pt results in formation of two products. • Dissociation of hydrogen from the −OH group involves a low activation energy. • Following hydrogenation of the aromatic ring forms 2-methyl-cyclohexanone. • Further hydrogenation produces the final product, 2-methyl-cyclohexanol. - Abstract: Catalytic experiments were performed for the hydrogenation of o-cresol in n-dodecane over a platinum catalyst. Batch reactions analyzed with an in-situ ATR IR probe suggest that the hydrogenation results in the formation of the final product, 2-methyl-cyclohexanol, with 2-methyl-cyclohexanone as the intermediate product. Ab initio density-functional theory was employed to investigate the atomic-scale mechanism of o-cresol hydrogenation on the Pt(111) surface. The formation of 2-methyl-cyclohexanone was found to involve two steps. The first step is a hydrogen abstraction, that is, the H atom in the hydroxyl group migrates to the Pt surface. The second step is hydrogenation, that is, the pre-existing H atoms on Pt react with the carbon atoms in the aromatic ring. On the other hand, 2-methyl-cyclohexanonol may be produced through two paths, with activation energies slightly greater than that for the formation of 2-methyl-cyclohexanone. One path involves direct hydrogenation of the aromatic ring. Another path involves three steps, with the partial hydrogenation of the ring as the first step, hydrogen abstraction of the −OH group as the second, and hydrogenation of remaining C atoms and the O atom the last.

TiO2-anatase modified by carbon as the photo catalyst under visible light

International Nuclear Information System (INIS)

Morawski, A.W.; Janus, M.; Tryba, B.; Kalucki, K.; Tryba, B.; Inagaki, M.

2006-01-01

The photo-catalytic oxidation of phenol in water under a visible light over anatase-type titanium dioxide (Tytanpol A11, Poland), modified by carbon deposited via n-hexane carbonization, was investigated. The catalysts, which had small (0-0.2 mass%) and high (0.69-0.85 mass%) contents of carbon showed a little lower catalytic photo-activity than pristine TiO 2 . However, the catalyst with high content of carbon (0.85 mass%) gave almost 14-times lower turbidity in the phenol solution after the photo-catalyst sedimentation. These two factors depend on the carbon content and have an influence on the 'practical efficiency' of the catalysts. The 'practical efficiency' of the catalyst under visible light, calculated from these two factors, was therefore 14-times higher for the catalyst containing 0.85 mass% carbon (whereas for UV radiation, it was found to be lower - 0.2 mass% -; this is the result of a previous work). The surface modification of the catalyst with 0.85% carbon seemed to be stable under visible light. The deposition of carbon on TiO 2 by carbonization of n-hexane was supposed to lead to obtain the catalyst, which could be easily used in a water-treatment system under visible light. (authors)

Controlled synthesis of the tricontinuous mesoporous material IBN-9 and its carbon and platinum derivatives

KAUST Repository

Zhao, Yunfeng; Zhang, Daliang; Zhao, Lan; Wang, Guangchao; Zhu, Yihan; Cairns, Amy; Sun, Junliang; Zou, Xiaodong; Han, Yu

2011-01-01

materials (e.g., carbon and platinum) via a "hard- templating" synthesis route. The obtained carbon material possesses large surface area (∼1900 m2/g), high pore volume (1.56 cm 3/g), and remarkable gas adsorption capability at both cryogenic temperatures

Corrosion Studies of Platinum Nano-Particles for Fuel Cells

DEFF Research Database (Denmark)

Shim, Signe Sarah

The main focus of the present thesis is on corrosion and prevention of corrosion of platinum particles supported on carbon. This is important for instance in connection with start up and shutdown of fuel cells. The degradation mechanism of platinum particles supported on carbon has been character......The main focus of the present thesis is on corrosion and prevention of corrosion of platinum particles supported on carbon. This is important for instance in connection with start up and shutdown of fuel cells. The degradation mechanism of platinum particles supported on carbon has been...... characterized during oxygen reduction reaction (ORR) condition using identical location (IL) transmission electron microscopy (TEM). A TEM grid was used as the working electrode in an electrochemical setup allowing a direct correlation between the electrochemical response and the TEM analysis. The main results...... thirds and one monolayer of gold on platinum supported on carbon were synthesized by an inverse micelle method. The results obtained appear independent of the gold coverage. It has been shown that the electrochemical active surface areas of the platinum and platinum gold particles synthesized...

Infinite dilution partial molar volumes of platinum(II) 2,4-pentanedionate in supercritical carbon dioxide.

Science.gov (United States)

Kong, Chang Yi; Siratori, Tomoya; Funazukuri, Toshitaka; Wang, Guosheng

2014-10-03

The effects of temperature and density on retention of platinum(II) 2,4-pentanedionate in supercritical fluid chromatography were investigated at temperatures of 308.15-343.15K and pressure range from 8 to 40MPa by the chromatographic impulse response method with curve fitting. The retention factors were utilized to derive the infinite dilution partial molar volumes of platinum(II) 2,4-pentanedionate in supercritical carbon dioxide. The determined partial molar volumes were small and positive at high pressures but exhibited very large and negative values in the highly compressible near critical region of carbon dioxide. Copyright © 2014 Elsevier B.V. All rights reserved.

Synthesis and characterization of ternary Pt-Ni-M/C (M=Cu, Fe, Ce, Mo, W) nano-catalysts for low temperature fuel cells

International Nuclear Information System (INIS)

Ahmed, Riaz; Jamil, Rabia; Ansari, Muhammad Shahid

2014-01-01

Ternary metal catalysts were synthesized by impregnation method. The mixture of metal solutions was reduced slowly under inert atmosphere and the reduced metals were deposited on the Vulcan Carbon(VC). Tungsten, molybdenum, cerium, iron and copper were added to specified amounts of platinum and nickel. Addition of nickel generally improves catalytic activity of platinum. The XRD of the catalysts was done and the crystallite size and other parameters were calculated. Crystallite sizes were in the range of 5 to 16 nm. Electrochemical surface areas of the catalysts were determined by cyclic voltammetry (CV) in acidic media and are compared. Electro oxidation of methanol on the catalysts was done and peak potential, peak current, mass activity of the catalysts were calculated and are compared. These parameters were determined in acidic and basic media. It was found that mass activity increased significantly in basic media. Rate constants for the electro oxidation of methanol were also calculated in acidic and basic media and are compared and discussed. Rate constants were generally higher in basic media. Ternary catalysts showed improved catalytic activity than the binary catalyst. Nano alloying improved the catalytic activity and stability of the ternary catalysts

Carbon formation on nickel and nickel-copper alloy catalysts

Energy Technology Data Exchange (ETDEWEB)

Alstrup, I.; Soerensen, O.; Rostrup-Nielsen, J.R. [Haldor Topsoe Research Labs., Lyngby (Denmark); Tavares, M.T.; Bernardo, C.A.

1998-05-01

Equilibrium, kinetic and morphological studies of carbon formation in CH{sub 4} + H{sub 2}, CO, and CO + H{sub 2} gases on silica supported nickel and nickel-copper catalysts are reviewed. The equilibrium deviates in all cases from graphite equilibrium and more so in CO + CO{sub 2} than in CH{sub 4} + H{sub 2}. A kinetic model based on information from surface science results with chemisorption of CH{sub 4} and possibly also the first dehydrogenation step as rate controlling describes carbon formation on nickel catalyst in CH{sub 4} + H{sub 2} well. The kinetics of carbon formation in CO and CO + H{sub 2} gases are in agreement with CO disproportionation as rate determining step. The presence of hydrogen influences strongly the chemisorption of CO. Carbon filaments are formed when hydrogen is present in the gas while encapsulating carbon dominates in pure CO. Small amounts of Cu alloying promotes while larger amounts (Cu : Ni {>=} 0.1) inhibits carbon formation and changes the morphology of the filaments (``octopus`` carbon formation). Adsorption induced nickel segregation changes the kinetics of the alloy catalysts at high carbon activities. Modifications suggested in some very recent papers on the basis of new results are also briefly discussed. (orig.) 31 refs.

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.

Nitrogen controlled iron catalyst phase during carbon nanotube growth

Energy Technology Data Exchange (ETDEWEB)

Bayer, Bernhard C., E-mail: bernhard.bayer@univie.ac.at [Department of Engineering, University of Cambridge, Cambridge CB3 0FA (United Kingdom); Faculty of Physics, University of Vienna, A-1090 Vienna (Austria); Baehtz, Carsten [Institute of Ion Beam Physics and Materials Research, Helmholtz-Zentrum Dresden-Rossendorf, D-01314 Dresden (Germany); Kidambi, Piran R.; Weatherup, Robert S.; Caneva, Sabina; Cabrero-Vilatela, Andrea; Hofmann, Stephan [Department of Engineering, University of Cambridge, Cambridge CB3 0FA (United Kingdom); Mangler, Clemens; Kotakoski, Jani; Meyer, Jannik C. [Faculty of Physics, University of Vienna, A-1090 Vienna (Austria); Goddard, Caroline J. L. [Department of Materials Science and Metallurgy, University of Cambridge, Cambridge CB3 0FS (United Kingdom)

2014-10-06

Close control over the active catalyst phase and hence carbon nanotube structure remains challenging in catalytic chemical vapor deposition since multiple competing active catalyst phases typically co-exist under realistic synthesis conditions. Here, using in-situ X-ray diffractometry, we show that the phase of supported iron catalyst particles can be reliably controlled via the addition of NH{sub 3} during nanotube synthesis. Unlike polydisperse catalyst phase mixtures during H{sub 2} diluted nanotube growth, nitrogen addition controllably leads to phase-pure γ-Fe during pre-treatment and to phase-pure Fe{sub 3}C during growth. We rationalize these findings in the context of ternary Fe-C-N phase diagram calculations and, thus, highlight the use of pre-treatment- and add-gases as a key parameter towards controlled carbon nanotube growth.

Preparation of Pt-SDB hydrophobic catalyst used in H2-H2O isotope exchange reaction

International Nuclear Information System (INIS)

Li Junhua; Kang Yi; Ruan Hao; Dou Qincheng; Han Yande; Hu Shilin

2001-01-01

The preparation of Pt-SDB hydrophobic catalyst is studied, in which platinum as active metal and polystyrene divinylbenzene (SDB) as the carrier. Hydrogen isotope exchange reaction is carried out with Pt-SDB catalyst in counter-current in the trickle bed. The effect of preparing condition on the activity of catalyst is discussed. The results show that the excellent catalyst is obtained by reduced at the temperature of 200 degree C over 8 hours. Hydrophobic catalyst is high activity and stability as the amount of platinum content is 3%, the platinum can reach the economic use with the content of (1-2)%

Development of Sulfur and Carbon Tolerant Reforming Alloy Catalysts Aided by Fundamental Atomistics Insights

Energy Technology Data Exchange (ETDEWEB)

Suljo Linic

2006-08-31

Current hydrocarbon reforming catalysts suffer from rapid carbon and sulfur poisoning. Even though there is a tremendous incentive to develop more efficient catalysts, these materials are currently formulated using inefficient trial and error experimental approaches. We have utilized a novel hybrid experimental/theoretical approach, combining quantum Density Functional Theory (DFT) calculations and various state-of-the-art experimental tools, to formulate carbon tolerant reforming catalysts. We have employed DFT calculations to develop molecular insights into the elementary chemical transformations that lead to carbon poisoning of Ni catalysts. Based on the obtained molecular insights, we have identified, using DFT quantum calculation, Sn/Ni alloy as a potential carbon tolerant reforming catalyst. Sn/Ni alloy was synthesized and tested in steam reforming of methane, propane, and isooctane. We demonstrated that the alloy catalyst is carbon-tolerant under nearly stoichiometric steam-to-carbon ratios. Under these conditions, monometallic Ni is rapidly poisoned by sp2 carbon deposits. The research approach is distinguished by a few characteristics: (a) Knowledge-based, bottom-up approach, compared to the traditional trial and error approach, allows for a more efficient and systematic discovery of improved catalysts. (b) The focus is on exploring alloy materials which have been largely unexplored as potential reforming catalysts.

Characterization of Pt/Sn catalyst for the electrochemical oxidation of methanol

Energy Technology Data Exchange (ETDEWEB)

Andrew, M.R.; Drury, J.S.; McNicol, B.D.; Pinnington, C.; Short, R.T.

1976-03-01

Pt/Sn electrodeposited catalysts have been prepared, characterized and tested for the electro-oxidation of methanol. Catalyst activities were measured in 3 M H/sub 2/SO/sub 4/ electrolyte between ambient temperature and 95/sup 0/C. Enhancement in specific activity by a factor of about 50 was found over electrodeposited platinum black. This behavior is in contrast to that of alloys of platinum and tin which were found to have very low activities compared with platinum catalysts and to be readily corroded in H/sub 2/SO/sub 4/ electrolyte. ESCA (electron spectroscopy for chemical analysis) studies and Moessbauer spectroscopy showed the majority of the tin in the deposit to be present in an oxidized form. A small amount (approximately 17%) was present as a dilute alloy of tin in platinum. Surface area measurements and X-ray powder diffraction indicated that the increase in activity over platinum black was not attributable to smaller platinum particle size. It seems that the combination of platinum and tin results in a decrease in the poisoning effect by strongly adsorbed organic residues. Whether this arises from the operation of a cyclic Sn(II)/Sn(IV) redox system or from modification of the platinum surface remains unresolved.

A review of carbon-based and non-carbon-based catalyst supports for the selective catalytic reduction of nitric oxide.

Science.gov (United States)

Anthonysamy, Shahreen Binti Izwan; Afandi, Syahidah Binti; Khavarian, Mehrnoush; Mohamed, Abdul Rahman Bin

2018-01-01

Various types of carbon-based and non-carbon-based catalyst supports for nitric oxide (NO) removal through selective catalytic reduction (SCR) with ammonia are examined in this review. A number of carbon-based materials, such as carbon nanotubes (CNTs), activated carbon (AC), and graphene (GR) and non-carbon-based materials, such as Zeolite Socony Mobil-5 (ZSM-5), TiO 2 , and Al 2 O 3 supported materials, were identified as the most up-to-date and recently used catalysts for the removal of NO gas. The main focus of this review is the study of catalyst preparation methods, as this is highly correlated to the behaviour of NO removal. The general mechanisms involved in the system, the Langmuir-Hinshelwood or Eley-Riedeal mechanism, are also discussed. Characterisation analysis affecting the surface and chemical structure of the catalyst is also detailed in this work. Finally, a few major conclusions are drawn and future directions for work on the advancement of the SCR-NH 3 catalyst are suggested.

Biodiesel production from Silybum marianum L. seed oil with high FFA content using sulfonated carbon catalyst for esterification and base catalyst for transesterification

International Nuclear Information System (INIS)

Fadhil, Abdelrahman B.; Aziz, Akram M.; Al-Tamer, Marwa H.

2016-01-01

Highlights: • PET was converted to activated carbon and then sulfonated to prepare carbon acid catalyst. • Carbon acid catalyst was used for esterification of high acid value Silybum marianum L. seed oil. • Biodiesel was obtained with 96.98% efficiency. - Abstract: In this research work, waste of polyethylene terephthalate (PET) was converted into activated carbon and the latter was used in the preparation of a carbon acid catalyst. Waste of PET was converted into activated carbon via carbonization and steam activation, then the activated carbon was sulfonated using fuming sulfuric acid in order to produce the carbon acid catalyst. The prepared carbon acid catalyst was tested for esterification of high acid value non-edible oil, Silybum marianum L. seed oil (SMSO) via optimized protocol. Amount of the carbon acid catalyst, methanol to oil molar ratio, temperature and time were the experimental variables optimized. Esterification of SMSO with methanol using the prepared carbon acid catalyst reduced its parent acid value (20.0 mg KOH/g) to the acceptable limits for base-catalyzed transesterification (<2.0 mg KOH/g) using 6.0% w/w of the catalyst, 15:1 methanol to oil molar ratio, 68 °C reaction temperature and 180 min of reaction. The performance of the catalyst was reduced gradually during its recycling and reached to 60.0% at the 5th cycle. Kinetics of esterification of SMSO using the prepared carbon acid catalyst followed pseudo first order kinetics, and the activation energy was found to be 70.98 kJ/mol. The esterified oil was converted to biodiesel through optimized base-catalyzed transesterification with methanol. Biodiesel with (96.98% yield and purity of 96.69% w/w) yield was obtained using 0.80% KOH w/w, 6:1 methanol to oil molar ratio, 60 °C reaction temperature, 75 min of reaction and 600 rpm rate of stirring. The biodiesel properties were within the recommended biodiesel standards as prescribed by ASTM D 6751 and EN 14214. Transesterification of

Inhibition of ammonia poisoning by addition of platinum to Ru/α-Al2 O3 for preferential CO oxidation in fuel cells.

Science.gov (United States)

Sato, Katsutoshi; Yagi, Sho; Zaitsu, Shuhei; Kitayama, Godai; Kayada, Yuto; Teramura, Kentaro; Takita, Yusaku; Nagaoka, Katsutoshi

2014-12-01

In polymer electrolyte fuel cell (PEFC) systems, small amounts of ammonia (NH3 ) present in the reformate gas deactivate the supported ruthenium catalysts used for preferential oxidation (PROX) of carbon monoxide (CO). In this study, we investigated how the addition of a small amount of platinum to a Ru/α-Al2 O3 catalyst (Pt/Ru=1:9 w/w) affected the catalyst's PROX activity in both the absence and the presence of NH3 (130 ppm) under conditions mimicking the reformate conditions during steam reforming of natural gas. The activity of undoped Ru/α-Al2 O3 decreased sharply upon addition of NH3 , whereas Pt/Ru/α-Al2 O3 exhibited excellent PROX activity even in the presence of NH3 . Ruthenium K-edge X-ray absorption near-edge structure (XANES) spectra indicated that in the presence of NH3 , some of the ruthenium in the undoped catalyst was oxidized in the presence of NH3 , whereas ruthenium oxidation was not observed with Pt/Ru/α-Al2 O3 . These results suggest that ruthenium oxidation is retarded by the platinum, so that the catalyst shows high activity even in the presence of NH3 . © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Catalyst for hydrocarbon conversion

International Nuclear Information System (INIS)

Duhaut, P.; Miquel, J.

1975-01-01

A description is given for a catalyst and process for hydrocarbon conversions, e.g., reforming. The catalyst contains an alumina carrier, platinum, iridium, at least one metal selected from uranium, vanadium, and gallium, and optionally halogen in the form of metal halide of one of the aforesaid components. (U.S.)

Formation of carbonato and hydroxo complexes in the reaction of platinum anticancer drugs with carbonate.

Science.gov (United States)

Di Pasqua, Anthony J; Centerwall, Corey R; Kerwood, Deborah J; Dabrowiak, James C

2009-02-02

The second-generation Pt(II) anticancer drug carboplatin is here shown to react with carbonate, which is present in blood, interstitial fluid, cytosol, and culture medium, to produce platinum-carbonato and -hydroxo complexes. Using [(1)H-(15)N] HSQC NMR and (15)N-labeled carboplatin, we observe that cis-[Pt(CBDCA-O)(OH)(NH(3))(2)](-), cis-[Pt(OH)(2)(NH(3))(2)], cis-[Pt(CO(3))(OH)(NH(3))(2)](-), and what may be cis-[Pt(CO(3))(NH(3))(2)] are produced when 1 is allowed to react in 23.8 mM carbonate buffer. When (15)N-labeled carboplatin is allowed to react in 0.5 M carbonate buffer, these platinum species, as well as other hydroxo and carbonato species, some of which may be dinuclear complexes, are produced. Furthermore, we show that the carbonato species cis-[Pt(CO(3))(OH)(NH(3))(2)](-) is also produced when cisplatin is allowed to react in carbonate buffer. The study outlines the conditions under which carboplatin and cisplatin form carbonato and aqua/hydroxo species in carbonate media.

Dimethyl carbonate synthesis via transesterification of propylene carbonate with methanol by ceria-zinc catalysts: Role of catalyst support and reaction parameters

Energy Technology Data Exchange (ETDEWEB)

Kumar, Praveen; Srivastava, Vimal Chandra; Mishra, Indra Mani [Indian Institute of Technology Roorkee, Roorkee 247667, Uttarakhand (India)

2015-09-15

Ceria and zinc oxide catalyst were impregnated onto various oxide supports, namely Al{sub 2}O{sub 3}, TiO{sub 2} and SiO{sub 2}, individually by deposition-coprecipitation method. The synthesized catalysts (CZA, CZS and CZT having supports Al{sub 2}O{sub 3}, TiO{sub 2} and SiO{sub 2}, respectively) were characterized by X-ray diffraction (XRD), NH{sub 3}- and CO{sub 2}-temperature programmed desorption (TPD) and N2 adsorption. These catalysts were used for synthesis of dimethyl carbonate (DMC) from methanol and propylene carbonate in a batch reactor. CZS was found to have larger average grain size as compared to CZA and CZT. Composite oxides (catalysts) were found to contain individual phases of ZnO, CeO{sub 2} and some spinel forms of Zn, Ce along with their supports. CZS having highest basicity and surface area showed better catalytic activity as compared to CZA and CZT. Effect of reaction temperature and methanol/PC molar ratio on DMC yield was studied and a reaction mechanism has been discussed. Maximum DMC yield of 77% was observed with CZS catalyst at 170 .deg. C with methanol/PC molar ratio of 10.

The deuterium-exchange reaction between water and hydrogen with the thin-film hydrophobic catalyst

International Nuclear Information System (INIS)

Yamashita, Hisao; Mizumoto, Mamoru; Matsuda, Shimpei

1985-01-01

The deuterium-exchange reaction between water and hydrogen with a hydrophobic catalyst was studied. The hydrophobic catalyst was composed of platinum as an active component and porous poly(tetrafluoroethylene) (PTFE) as a support. The PTFE support was in two forms, i.e., (a) a pellet and (b) a thin-film with the thickness of 50 μm. The primary purpose of the thin film hydrophobic catalyst was to reduce the platinum usage in the reactor. The activity of the catalyst was measured in a trickle bed reactor at atmospheric pressure and temperature of 20 ∼ 70 deg C. It has been found that the employment of the thin-film catalyst reduced the platinum usage to 1/5 of the reactor in the case of using a conventional catalyst. Platinum particles on the thin-film catalyst work efficiently because the reactants were easily diffused to the active sites. It has also been found that the isotopic exchange rate with the thin-film catalyst increased with the increase in the ratio of liquid/gas and increased with the rise of the reaction temperature. It was found from an endurance test that the activity of the thin-film catalyst decreased gradually due to the condensation of water vapor in the catalyst, but was regenarated by heating the catalyst to remove the condensed water. (author)

Process for Making a Noble Metal on Tin Oxide Catalyst

Science.gov (United States)

Davis, Patricia; Miller, Irvin; Upchurch, Billy

2010-01-01

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

The electrochemical behavior of cobalt phthalocyanine/platinum as methanol-resistant oxygen-reduction electrocatalysts for DMFC

Energy Technology Data Exchange (ETDEWEB)

Lu, Yuhao; Reddy, Ramana G. [Department of Metallurgical and Materials Engineering, The University of Alabama, P.O. Box 870202, Tuscaloosa, AL 35487 (United States)

2007-02-01

The electrochemical behavior of cobalt phthalocyanine/platinum as methanol-resistant oxygen-reduction electrocatalyst for DMFC was investigated. Platinum was chemically deposited on the carbon-supported cobalt phthalocyanine (CoPc), and then it was heat-treated in high purity nitrogen at 300 C, 635 C and 980 C. In order to evaluate the electrocatalytic behavior of CoPc-Pt/C, the PtCo/C and Pt/C as reference catalysts were employed. TGA, XRD, EDAX, XPS and electrochemical experiments were used to study the thermal stability, crystal structure, physical characterization and electrochemical behavior of these catalysts. These catalysts exhibited similar electrocatalytic activity for oxygen reaction in 0.5 M H{sub 2}SO{sub 4} solution. In methanol tolerance experiments, Pt/C, PtCo/C and CoPc-Pt/C heated at 980 C were active for the methanol oxidation reaction (MOR). The presence of Co did not improve resistance to methanol poisoning. However, the CoPc-Pt/C after 300 C or 635 C heat-treatment demonstrated significant inactivity for MOR, hence they have a good ability to resist methanol poisoning. The current study indicated that the macrocyclic structure of phthalocyanine is the most important factor to improve the methanol tolerance of CoPc-Pt/C as the oxygen-reduction reaction (ORR) electrocatalyst. The CoPc-Pt based catalyst should be a good alternation for oxygen electro-reduction reaction in DMFC. (author)

Pulsed laser dewetting of nickel catalyst for carbon nanofiber growth

International Nuclear Information System (INIS)

Guan, Y F; Pearce, R C; Simpson, M L; Rack, P D; Melechko, A V; Hensley, D K

2008-01-01

We present a pulsed laser dewetting technique that produces single nickel catalyst particles from lithographically patterned disks for subsequent carbon nanofiber growth through plasma enhanced chemical vapor deposition. Unlike the case for standard heat treated Ni catalyst disks, for which multiple nickel particles and consequently multiple carbon nanofibers (CNFs) are observed, single vertically aligned CNFs could be obtained from the laser dewetted catalyst. Different laser dewetting parameters were tested in this study, such as the laser energy density and the laser processing time measured by the total number of laser pulses. Various nickel disk radii and thicknesses were attempted and the resultant number of carbon nanofibers was found to be a function of the initial disk dimension and the number of laser pulses

In situ FTIRS study of ethanol electro-oxidation on anode catalysts in direct ethanol fuel cells

Energy Technology Data Exchange (ETDEWEB)

Wang, Q.; Sun, G.; Jiang, L.; Zhu, M.; Yan, S.; Wang, G.; Xin, Q. [Chinese Academy of Sciences, Dalian (China). Dalian Inst. of Chemical Physics; Chen, Q.; Li, J.; Jiang, Y.; Sun, S. [Xiamen Univ., Xiamen (China). State Key Lab. for Physical Chemistry of Solid Surfaces

2006-07-01

The low activation of ethanol oxidation at lower temperatures is an obstacle to the development of cost-effective direct ethanol fuel cells (DEFCs). This study used a modified polyol method to prepare carbon-supported platinum (Pt) based catalysts. Carbon supported Pt-based catalysts were fabricated by a modified polyol method and characterized through transmission electron spectroscopy (TEM) and X-ray diffraction (XRD). Results of the study showed that the particles in the Pt/C and PtRu/C and PtSn/C catalysts were distributed on the carbon support uniformly. Diffraction peaks of the Pt shifted positively in the PtRu/C catalysts and negatively in the PtSn/C catalysts. In situ Fourier Transform Infra-red spectroscopy (FTIR) was used to investigate the adsorption and oxidation process of ethanol on the catalysts. Results showed that the electrocatalytic activity of ethanol oxidation on the materials was enhanced. Linear bonded carbon monoxide (CO) was the most strongly absorbed species, and the main products produced by the catalysts were carbon dioxide (CO{sub 2}), acetaldehyde, and acetic acid. Results showed that the PtRu/C catalyst broke the C-C bond more easily than the Pt/C and PtSn/C compounds. However, the results of a linear sweep voltammogram analysis showed that ethanol oxidation of the PtSn/C was enhanced. Bands observed on the compound indicated the formation of acetic acid and acetaldehyde. It was concluded that the enhancement of PtSn/C for ethanol oxidation was due to the formation of acetic acid and acetaldehyde at lower potentials. 4 refs., 1 fig.

Application of sodium carbonate prevents sulphur poisoning of catalysts in automated total mercury analysis

Science.gov (United States)

McLagan, David S.; Huang, Haiyong; Lei, Ying D.; Wania, Frank; Mitchell, Carl P. J.

2017-07-01

Analysis of high sulphur-containing samples for total mercury content using automated thermal decomposition, amalgamation, and atomic absorption spectroscopy instruments (USEPA Method 7473) leads to rapid and costly SO2 poisoning of catalysts. In an effort to overcome this issue, we tested whether the addition of powdered sodium carbonate (Na2CO3) to the catalyst and/or directly on top of sample material increases throughput of sulphur-impregnated (8-15 wt%) activated carbon samples per catalyst tube. Adding 5 g of Na2CO3 to the catalyst alone only marginally increases the functional lifetime of the catalyst (31 ± 4 g of activated carbon analyzed per catalyst tube) in relation to unaltered catalyst of the AMA254 total mercury analyzer (17 ± 4 g of activated carbon). Adding ≈ 0.2 g of Na2CO3 to samples substantially increases (81 ± 17 g of activated carbon) catalyst life over the unaltered catalyst. The greatest improvement is achieved by adding Na2CO3 to both catalyst and samples (200 ± 70 g of activated carbon), which significantly increases catalyst performance over all other treatments and enables an order of magnitude greater sample throughput than the unaltered samples and catalyst. It is likely that Na2CO3 efficiently sequesters SO2, even at high furnace temperatures to produce Na2SO4 and CO2, largely negating the poisonous impact of SO2 on the catalyst material. Increased corrosion of nickel sampling boats resulting from this methodological variation is easily resolved by substituting quartz boats. Overall, this variation enables an efficient and significantly more affordable means of employing automated atomic absorption spectrometry instruments for total mercury analysis of high-sulphur matrices.

Physicochemical investigations of carbon nanofiber supported Cu/ZrO{sub 2} catalyst

Energy Technology Data Exchange (ETDEWEB)

Din, Israf Ud, E-mail: drisraf@yahoo.com, E-mail: maizats@petronas.com.my; Shaharun, Maizatul S., E-mail: drisraf@yahoo.com, E-mail: maizats@petronas.com.my [Department of Fundamental and Applied Sciences, Universiti Teknologi PETRONAS (Malaysia); Subbarao, Duvvuri, E-mail: duvvuri-subbarao@petronas.com.my [Department of Chemical Engineering, Universiti Teknologi PETRONAS (Malaysia); Naeem, A., E-mail: naeeem64@yahoo.com [National Centre of Excellence in Physical Chemistry, University of Peshawar (Pakistan)

2014-10-24

Zirconia-promoted copper/carbon nanofiber catalysts (Cu‐ZrO{sub 2}/CNF) were prepared by the sequential deposition precipitation method. The Herringbone type of carbon nanofiber GNF-100 (Graphite nanofiber) was used as a catalyst support. Carbon nanofiber was oxidized to (CNF-O) with 5% and 65 % concentration of nitric acid (HNO{sub 3}). The CNF activated with 5% HNO{sub 3} produced higher surface area which is 155 m{sup 2}/g. The catalyst was characterized by X-ray Diffraction (XRD), Fourier Transform Infra-Red (FTIR) and N{sub 2} adsorption-desorption. The results showed that increase of HNO{sub 3} concentration reduced the surface area and porosity of the catalyst.

Highly Active, Carbon-supported, PdSn Nano-core, Partially ...

African Journals Online (AJOL)

Carbon-supported, Pt partially covered, PdSn alloy nanoparticles (Pt-PdSn/C) were synthesized via a metathetical reaction of PdSn alloy nanoparticles, and a platinum precursor. The electrochemical activity was evaluated by methanol oxidation. The Pt-PdSn/C catalysts were characterized by transmission electron ...

An investigation into carbon nanostructured materials as catalyst support in proton exchange membrane fuel cells

DEFF Research Database (Denmark)

Veltzé, Sune

acid treatment on the Vapour Grown Carbon Fibers™ manufactured by Showa Denko K. K. From these fibres, twelve platinised samples were investigated, of which one was platinised by a platinum phtalocyanine impregnation method, two were platinised by the polyol method and the remaining by the Bönnemann......Polymer electrolyte fuel cells (PEFCs) are among the key research areas concerning clean cost-effective energy. Carbon nano fibres (CNF), single walled carbon nano tubes (SWCNT), multi walled carbon nano tubes (MWCNT) and other related materials are among the possible successors to standard carbon...... black support materials for low platinum containing electrocatalyst. This is partly due to their high electronic conductivity. Partly due to their high surface area needed for the dispersion of nanoparticulate metal-clusters. In addition carbon nano-structures (CNF, SWCNT, MWCNT etc.) are more durable...

Hydrogen isotope separation in hydrophobic catalysts between hydrogen and liquid water

Energy Technology Data Exchange (ETDEWEB)

Ye, Linsen, E-mail: yls2005@mail.ustc.edu.cn [China Academy of Engineering Physics, Mianyang 621900 (China); Luo, Deli [Science and Technology on Surface Physics and Chemistry Laboratory, Jiangyou 621907 (China); Tang, Tao; Yang, Wan; Yang, Yong [China Academy of Engineering Physics, Mianyang 621900 (China)

2015-11-15

Hydrogen isotope catalytic exchange between hydrogen and liquid water is a very effective process for deuterium-depleted potable water production and heavy water detritiation. To improve the characteristics of hydrophobic catalysts for this type of reaction, foamed and cellular structures of hydrophobic carbon-supported platinum catalysts were successfully prepared. Separation of deuterium or tritium from liquid water was carried out by liquid-phase catalytic exchange. At a gas–liquid ratio of 1.53 and exchange temperature of 70 °C, the theoretical plate height of the hydrophobic catalyst (HETP = 34.2 cm) was slightly lower than previously reported values. Changing the concentration of the exchange column outlet water yielded nonlinear changes in the height of the packing layer. Configurations of deuterium-depleted potable water and detritiation of heavy water provide references for practical applications.

Application of aromatization catalyst in synthesis of carbon nanotubes

Indian Academy of Sciences (India)

In a typical chemical vapour deposition (CVD) process for synthesizing carbon nanotubes (CNTs), it was found that the aromatization catalysts could promote effectively the formation of CNT. The essence of this phenomenon was attributed to the fact that the aromatization catalyst can accelerate the ...

Enhanced catalytic activity of nanoscale platinum islands loaded ...

Indian Academy of Sciences (India)

2016-08-26

Aug 26, 2016 ... In the present study, different catalysts (∼ 10 nm thick) including metals, noble metals and metal oxides, were loaded in dotted island form over SnO2 thin film for LPG gas detection. A comparison of various catalysts indicated that the presence of platinum dotted islands over SnO2 thin film deposited by r.f. ...

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...

Sustainable production of acetaldehyde from lactic acid over the carbon catalysts

Energy Technology Data Exchange (ETDEWEB)

Tang, Congming; Peng, Jiansheng; Li, Xinli; Zhai, Zhanjie; Gao, Hejun; Liao, Yunwen [China West Normal University, Nanchong (China); Bai, Wei; Jiang, Ning [Chengdu Institute of Organic Chemistry, Chinese Academy of Sciences, Chengdu (China)

2016-01-15

The synthesis of acetaldehyde from lactic acid over the carbon material catalysts was investigated. The carbon materials were characterized by scanning electron microscopy for morphologic features, by X-ray diffraction for crystal phases, by Fourier transform infrared spectroscopy for functional group structures, by N2 sorption for specific surface area and by ammonia temperature-programed desorption for acidity, respectively. Among the tested carbon catalysts, mesoporous carbon displayed the most excellent catalytic performance. By acidity analysis, the medium acidity is a crucial factor for catalytic performance: more medium acidity favored the formation of acetaldehyde from lactic acid. To verify, we compared the catalytic performance of fresh activated carbon with that of the activated carbon treated by nitric acid. Similarly, the modified activated carbon also displayed better activity due to a drastic increase of medium acidity amount. However, in contrast to fresh carbon nanotube, the treated sample displayed worse activity due to decrease of medium acidity amount. The effect of reaction temperature and time on stream on the catalytic performance was also investigated. Under the optimal reaction conditions, 100% lactic acid conversion and 91.6% acetaldehyde selectivity were achieved over the mesoporous carbon catalyst.

Deactivation by carbon of iron catalysts for indirect liquefaction

Energy Technology Data Exchange (ETDEWEB)

Bartholomew, C.H.

1990-10-11

This report describes recent progress in a fundamental, three-year investigation of carbon formation and its effects on the activity and selectivity of promoted iron catalysts for Fischer-Tropsch (FT) synthesis, the objectives of which are: determine rates and mechanisms of carbon deactivation of unsupported Fe and Fe/K catalysts during CO hydrogenation over a range of CO concentrations, CO:H{sub 2} ratios, and temperatures; model the rates of deactivation of the same catalysts in fixed-bed reactors. During the thirteenth quarter design of software for a computer-automated reactor system to be used in the kinetic and deactivation studies was continued. Further progress was made toward the completion of the control language, control routines, and software for operating this system. Progress was also made on the testing of the system hardware and software. H{sub 2} chemisorption capacities and activity selectivity data were also measured for three iron catalysts promoted with 1% alumina. 47 refs., 8 figs., 1 tab.

Carbon determination in uranium and its compounds

International Nuclear Information System (INIS)

Silva Queiroz, C.A. da; Abrao, A.

1982-01-01

Carbon content in uranium and its compounds, especially ceramic grade UO 2 , must be controlled rigorously. A method for the determination of carbon with the aid of commercial equipment which uses platinum as a catalyst for the oxidation of CO, and infrared cells for CO 2 measurement is described. The detection limit is 5μg C/g U and the determination range is 0.0005 to 5% C/U. The method is being used routinely to control the carbon content in nuclear fuel materials. (Author) [pt

Oxygen-reducing catalyst layer

Science.gov (United States)

O'Brien, Dennis P [Maplewood, MN; Schmoeckel, Alison K [Stillwater, MN; Vernstrom, George D [Cottage Grove, MN; Atanasoski, Radoslav [Edina, MN; Wood, Thomas E [Stillwater, MN; Yang, Ruizhi [Halifax, CA; Easton, E Bradley [Halifax, CA; Dahn, Jeffrey R [Hubley, CA; O'Neill, David G [Lake Elmo, MN

2011-03-22

An oxygen-reducing catalyst layer, and a method of making the oxygen-reducing catalyst layer, where the oxygen-reducing catalyst layer includes a catalytic material film disposed on a substrate with the use of physical vapor deposition and thermal treatment. The catalytic material film includes a transition metal that is substantially free of platinum. At least one of the physical vapor deposition and the thermal treatment is performed in a processing environment comprising a nitrogen-containing gas.

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

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.

Graphitic Carbon Nitride as a Catalyst Support in Fuel Cells and Electrolyzers

International Nuclear Information System (INIS)

Mansor, Noramalina; Miller, Thomas S.; Dedigama, Ishanka; Jorge, Ana Belen; Jia, Jingjing; Brázdová, Veronika; Mattevi, Cecilia; Gibbs, Chris; Hodgson, David; Shearing, Paul R.; Howard, Christopher A.; Corà, Furio; Shaffer, Milo; Brett, Daniel J.L.

2016-01-01

Highlights: • Graphitic carbon nitride (gCN) describes many materials with different structures. • gCNs can exhibit excellent mechanical, chemical and thermal resistance. • A major obstacle for pure gCN catalyst supports is limited electronic conductivity. • Composite/Hybrid gCN structures show excellent performance as catalyst supports. • gCNs have great potential for use in fuel calls and water electrolyzers. - Abstract: Electrochemical power sources, such as polymer electrolyte membrane fuel cells (PEMFCs), require the use of precious metal catalysts which are deposited as nanoparticles onto supports in order to minimize their mass loading and therefore cost. State-of-the-art/commercial supports are based on forms of carbon black. However, carbon supports present disadvantages including corrosion in the operating fuel cell environment and loss of catalyst activity. Here we review recent work examining the potential of different varieties of graphitic carbon nitride (gCN) as catalyst supports, highlighting their likely benefits, as well as the challenges associated with their implementation. The performance of gCN and hybrid gCN-carbon materials as PEMFC electrodes is discussed, as well as their potential for use in alkaline systems and water electrolyzers. We illustrate the discussion with examples taken from our own recent studies.

Nanostructured TiOx as a catalyst support material for proton exchange membrane fuel cells

Science.gov (United States)

Phillips, Richard S.

Recent interest in the development of new catalyst support materials for proton exchange membrane fuel cells (PEMFCs) has stimulated research into the viability of TiO2-based support structures. Specifically, substoichiometric TiO2 (TiOx) has been reported to exhibit a combination of high conductivity, stability, and corrosion resistance. These properties make TiOx-based support materials a promising prospect when considering the inferior corrosion resistance of traditional carbon-based supports. This document presents an investigation into the formation of conductive and stable TiOx thin films employing atomic layer deposition (ALD) and a post deposition oxygen reducing anneal (PDORA). Techniques for manufacturing TiOx-based catalyst support nanostructures by means of ALD in conjunction with carbon black (CB), anodic aluminum oxide (AAO) and silicon nanowires (SiNWs) will also be presented. The composition and thickness of resulting TiOx thin films was determined with the aid of Auger electron spectroscopy (AES), Rutherford backscattering spectrometry (RBS), X-ray photoelectron spectroscopy (XPS), energy-dispersive X-ray spectroscopy (EDS), and scanning electron microscopy (SEM). Film crystal structure was determined with X-ray diffraction (XRD) analysis. Film conductivity was calculated using four-point probe (4-PP) and film thickness measurement data. Resulting thin films show a significant decrease of oxygen in ALD TiOx films corresponding with a great increase in conductivity following the PDORA. The effectiveness of the PDORA was also found to be highly dependent on ALD process parameters. TiOx-based nanostructures were coated with platinum using one of three Pt deposition techniques. First, liquid phase deposition (LPD), which was performed at room temperature, provided equal access to catalyst support material surfaces which were suspended in solution. Second, plasma enhanced atomic layer deposition (PEALD), which was performed at 450°C, provided good Pt

Bimetallic catalysts for HI decomposition in the iodine-sulfur thermochemical cycle

International Nuclear Information System (INIS)

Wang Laijun; Hu Songzhi; Xu Lufei; Li Daocai; Han Qi; Chen Songzhe; Zhang Ping; Xu Jingming

2014-01-01

Among the different kinds of thermochemical water-splitting cycles, the iodine-sulfur (IS) cycle has attracted more and more interest because it is one of the promising candidates for economical and massive hydrogen production. However, there still exist some science and technical problems to be solved before industrialization of the IS process. One such problem is the catalytic decomposition of hydrogen iodide. Although the active carbon supported platinum has been verified to present the excellent performance for HI decomposition, it is very expensive and easy to agglomerate under the harsh condition. In order to decrease the cost and increase the stability of the catalysts for HI decomposition, a series of bimetallic catalysts were prepared and studied at INET. This paper summarized our present research advances on the bimetallic catalysts (Pt-Pd, Pd-Ir and Pt-Ir) for HI decomposition. In the course of the study, the physical properties, structure, and morphology of the catalysts were characterized by specific surface area, X-ray diffractometer; and transmission electron microscopy, respectively. The catalytic activity for HI decomposition was investigated in a fixed bed reactor under atmospheric pressure. The results show that due to the higher activity and better stability, the active carbon supported bimetallic catalyst is more potential candidate than mono metallic Pt catalyst for HI decomposition in the IS thermochemical cycle. (author)

TiO2 and Al2O3 promoted Pt/C nanocomposites as low temperature fuel cell catalysts for electro oxidation of methanol in acidic media

International Nuclear Information System (INIS)

Naeem, Rabia; Ahmed, Riaz; Ansari, Muhammad Shahid

2014-01-01

Carbon corrosion and platinum dissolution are the two major catalyst layer degradation problems in polymer electrolyte membrane fuel cells (PEMFC). Ceramic addition can reduce the corrosion of carbon and increase the stability of catalysts. Pt/TiO 2 , Pt/TiO 2 -C, Pt/Al 2 O 3 and Pt/Al 2 O 3 -C catalysts were synthesized and characterized. Electrochemical surface area of Pt/TiO 2 -C and Pt/Al 2 O 3 -C nanocomposite catalysts was much higher than the Pt/TiO 2 and Pt/Al 2 O 3 catalysts. Peak current, specific activity and mass activity of the catalysts was also determined by cyclic voltammetry and were much higher for the carbon nanocomposites. Exchange current densities were determined from Tafel plots. Heterogeneous rates of reaction of electro oxidation of methanol were determined for all the catalysts and were substantially higher for titania catalysts as compared to alumina added catalysts. Mass activity of Pt/TiO 2 -C was much higher than mass activity of Pt/Al 2 O 3 -C. Stability studies showed that addition of ceramics have increased the catalytic activity and durability of the catalysts considerably

Analysis of proton exchange membrane fuel cell catalyst layers for reduction of platinum loading at Nissan

International Nuclear Information System (INIS)

Ohma, Atsushi; Mashio, Tetsuya; Sato, Kazuyuki; Iden, Hiroshi; Ono, Yoshitaka; Sakai, Kei; Akizuki, Ken; Takaichi, Satoshi; Shinohara, Kazuhiko

2011-01-01

The biggest issue that must be addressed in promoting widespread use of fuel cell vehicles (FCVs) is to reduce the cost of the fuel cell system. Especially, it is of vital importance to reduce platinum (Pt) loading of catalyst layers (CLs) in the membrane electrode assembly (MEA) of a proton exchange membrane fuel cell (PEMFC). In order to lower the Pt loading of the MEA, mass transport of reactants related to the performance in high current density should be enhanced significantly as well as kinetics of the catalyst, which can result in the better Pt utilization and effectiveness. In this study, we summarized our analytical approach and methods for reduction of Pt loading in CLs. Microstructure, mass transport properties of the reactants, and their relation in CLs were elucidated by applying experimental analyses and computational methods. A simple CL model for I–V performance prediction was then established, where experimentally elucidated parameters of the microstructure and the properties in CLs were taken into account. Finally, we revealed the impact of lowering the Pt loading on the transport properties, polarization, and the I–V performance.

Phosphorus poisoning of molybdenum sulfide hydrodesulfurization catalysts supported on carbon and alumina

NARCIS (Netherlands)

Bouwens, S.M.A.M.; Vissers, J.P.R.; Beer, de V.H.J.; Prins, R.

1988-01-01

Phosphorus-containing Mo sulfide catalysts supported on ¿-Al2O3 and activated carbon were evaluated for their thiophene HDS activities. Phosphorus was added as phosphoric acid to the carrier material prior to the molybdenum component. The thiophene HDS activity of the carbon-supported catalysts was

Synthesis and Characterization of Carbon nanofibers on Co and Cu Catalysts by Chemical Vapor Deposition

International Nuclear Information System (INIS)

Park, Eunsil; Kim, Jongwon; Lee, Changseop

2014-01-01

This study reports on the synthesis of carbon nanofibers via chemical vapor deposition using Co and Cu as catalysts. In order to investigate the suitability of their catalytic activity for the growth of nanofibers, we prepared catalysts for the synthesis of carbon nanofibers with Cobalt nitrate and Copper nitrate, and found the optimum concentration of each respective catalyst. Then we made them react with Aluminum nitrate and Ammonium Molybdate to form precipitates. The precipitates were dried at a temperature of 110 .deg. C in order to be prepared into catalyst powder. The catalyst was sparsely and thinly spread on a quartz tube boat to grow carbon nanofibers via thermal chemical vapor deposition. The characteristics of the synthesized carbon nanofibers were analyzed through SEM, EDS, XRD, Raman, XPS, and TG/DTA, and the specific surface area was measured via BET. Consequently, the characteristics of the synthesized carbon nanofibers were greatly influenced by the concentration ratio of metal catalysts. In particular, uniform carbon nanofibers of 27 nm in diameter grew when the concentration ratio of Co and Cu was 6:4 at 700 .deg. C of calcination temperature; carbon nanofibers synthesized under such conditions showed the best crystallizability, compared to carbon nanofibers synthesized with metal catalysts under different concentration ratios, and revealed 1.26 high amorphicity as well as 292 m 2 g -1 high specific surface area

Catalyst deposition for the preparation of carbon nanotubes

DEFF Research Database (Denmark)

2013-01-01

patterned surface is configured to ensure that no more than a single island of catalyst is formed on each plateau, so that a sub sequent growth of carbon nanotubes from the deposited islands result in that no more than a single carbon nanotube is grown from each plateau....

Fuel cell testing of Pt–Ru catalysts supported on differently prepared and pretreated carbon nanotubes

International Nuclear Information System (INIS)

Tokarz, Wojciech; Lota, Grzegorz; Frackowiak, Elzbieta; Czerwiński, Andrzej; Piela, Piotr

2013-01-01

Proton-exchange membrane fuel cell (PEMFC) testing of Pt–Ru catalysts supported on differently prepared multiwall carbon nanotube (MCNT) supports was performed to elucidate the influence of the different supports on the operating characteristics of the catalysts under real direct methanol fuel cell (DMFC) anode and H 2 -PEMFC anode conditions. The MCNTs were either thin, entangled or thick, disentangled. Pretreatment of the MCNTs was also done and it was either high-temperature KOH etching or annealing (graphitization). The performance of the catalysts was compared against the performance of a commercial Pt–Ru catalyst supported on a high-surface-area carbon black. Among the different MCNT supports, the graphitized, entangled support offered the best performance in all tests, which was equal to the performance of the commercial catalyst, despite the MCNT catalyst layer was ca. 2.2 times thicker than the carbon black catalyst layer. Even for an MCNT catalyst layer, which was almost 7 times thicker than the carbon black catalyst layer, the transport limitations were not prohibitive. This confirmed the expected potential of nanotube supports for providing superior reactant transport properties of the PEMFC catalyst layers

Catalyst retention in continuous flow with supercritical carbon dioxide

NARCIS (Netherlands)

Stouten, S.C.; Noel, T.; Wang, Q.; Hessel, V.

2014-01-01

This review discusses the retention of organometallic catalysts in continuous flow processes utilizing supercritical carbon dioxide. Due to its innovative properties, supercritical carbon dioxide offers interesting possibilities for process intensification. As a result of safety and cost

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

Dearomatization of jet fuel on irradiated platinum-supported catalyst

International Nuclear Information System (INIS)

Mucka, V.; Ostrihonova, A.; Kopernicky, I.; Mikula, O.

1983-01-01

The effect of ionizing radiation ( 60 Co #betta#-rays) on Pt-supported catalyst used for the dearomatization of jet fuel with distillation in the range 395 to 534 K has been studied. Pre-irradiation of the catalyst with doses in the range 10 2 to 5 x 10 4 Gy leads to the partial catalyst activation. Irradiation of the catalyst enhances its resistance to catalyst poisons, particularly to sulphur-compounds, and this is probably the reason for its catalytic activity being approx. 60 to 100% greater than that of un-irradiated catalyst. Optimum conditions for dearomatization on the irradiated catalyst were found and, by means of a rotary three-factorial experiment, it was shown that these lie at lower temperatures and lower pressures than those for un-irradiated catalyst. (author)

Carbon nanotube forests growth using catalysts from atomic layer deposition

Energy Technology Data Exchange (ETDEWEB)

Chen, Bingan; Zhang, Can; Esconjauregui, Santiago; Xie, Rongsi; Zhong, Guofang; Robertson, John [Department of Engineering, University of Cambridge, Cambridge CB3 0FA (United Kingdom); Bhardwaj, Sunil [Istituto Officina dei Materiali-CNR Laboratorio TASC, s.s. 14, km 163.4, I-34012 Trieste (Italy); Sincrotone Trieste S.C.p.A., s.s. 14, km 163.4, I-34149 Trieste (Italy); Cepek, Cinzia [Istituto Officina dei Materiali-CNR Laboratorio TASC, s.s. 14, km 163.4, I-34012 Trieste (Italy)

2014-04-14

We have grown carbon nanotubes using Fe and Ni catalyst films deposited by atomic layer deposition. Both metals lead to catalytically active nanoparticles for growing vertically aligned nanotube forests or carbon fibres, depending on the growth conditions and whether the substrate is alumina or silica. The resulting nanotubes have narrow diameter and wall number distributions that are as narrow as those grown from sputtered catalysts. The state of the catalyst is studied by in-situ and ex-situ X-ray photoemission spectroscopy. We demonstrate multi-directional nanotube growth on a porous alumina foam coated with Fe prepared by atomic layer deposition. This deposition technique can be useful for nanotube applications in microelectronics, filter technology, and energy storage.

Synthesis of carbon nanotubes and nanotube forests on copper catalyst

International Nuclear Information System (INIS)

Kruszka, Bartosz; Terzyk, Artur P; Wiśniewski, Marek; Gauden, Piotr A; Szybowicz, Mirosław

2014-01-01

The growth of carbon nanotubes on bulk copper is studied. We show for the first time, that super growth chemical vapor deposition method can be successfully applied for preparation of nanotubes on copper catalyst, and the presence of hydrogen is necessary. Next, different methods of copper surface activation are studied, to improve catalyst efficiency. Among them, applied for the first time for copper catalyst in nanotubes synthesis, sulfuric acid activation is the most promising. Among tested samples the surface modified for 10 min is the most active, causing the growth of vertically aligned carbon nanotube forests. Obtained results have potential importance in application of nanotubes and copper in electronic chips and nanodevices. (paper)

A facile approach towards increasing the nitrogen-content in nitrogen-doped carbon nanotubes via halogenated catalysts

International Nuclear Information System (INIS)

Ombaka, L.M.; Ndungu, P.G.; Omondi, B.; McGettrick, J.D.; Davies, M.L.; Nyamori, V.O.

2016-01-01

Nitrogen-doped carbon nanotubes (N-CNTs) have been synthesized at 850 °C via a CVD deposition technique by use of three ferrocenyl derivative catalysts, i.e. para-CN, -CF_3 and -Cl substituted-phenyl rings. The synthesized catalysts have been characterized by NMR, IR, HR-MS and XRD. The XRD analysis of the para-CF_3 catalyst indicates that steric factors influence the X-ray structure of 1,1′-ferrocenylphenyldiacrylonitriles. Acetonitrile or pyridine was used as carbon and nitrogen sources to yield mixtures of N-CNTs and carbon spheres (CS). The N-CNTs obtained from the para-CF_3 catalysts, in pyridine, have the highest nitrogen-doping level, show a helical morphology and are less thermally stable compared with those synthesized by use of the para-CN and -Cl as catalyst. This suggests that fluorine heteroatoms enhance nitrogen-doping in N-CNTs and formation of helical-N-CNTs (H-N-CNTs). The para-CF_3 and para-Cl catalysts in acetonitrile yielded iron-filled N-CNTs, indicating that halogens promote encapsulation of iron into the cavity of N-CNT. The use of acetonitrile, as carbon and nitrogen source, with the para-CN and -Cl as catalysts also yielded a mixture of N-CNTs and carbon nanofibres (CNFs), with less abundance of CNFs in the products obtained using para-Cl catalysts. However, para-CF_3 catalyst in acetonitrile gave N-CNTs as the only shaped carbon nanomaterials. - Graphical abstract: Graphical abstract showing the synthesis of N-CNTs using halogenated-ferrocenyl derivatives as catalyst with pyridine or acetonitrile as nitrogen and carbon sources via the chemical vapour deposition technique. - Highlights: • N-CNTs were synthesized from halogenated ferrocenyl catalysts. • Halogenated catalysts promote nitrogen-doping and pyridinic nitrogen in N-CNTs. • Halogenated catalysts facilitate iron filling of N-CNTs.

Composite catalyst for carbon monoxide and hydrocarbon oxidation

Science.gov (United States)

Liu, Wei; Flytzani-Stephanopoulos, Maria

1996-01-01

A method and composition for the complete oxidation of carbon monoxide and/or hydrocarbon compounds. The method involves reacting the carbon monoxide and/or hydrocarbons with an oxidizing agent in the presence of a metal oxide composite catalyst. The catalyst is prepared by combining fluorite-type oxygen ion conductors with active transition metals. The fluorite oxide, selected from the group consisting of cerium oxide, zirconium oxide, thorium oxide, hafnium oxide, and uranium oxide, and may be doped by alkaline earth and rare earth oxides. The transition metals, selected from the group consisting of molybdnum, copper, cobalt, maganese, nickel, and silver, are used as additives. The atomic ratio of transition metal to fluorite oxide is less than one.

Effect of the platinum content on the microstructure and micropore size distribution of Pt/alumina-pillared clays.

Science.gov (United States)

Barrera-Vargas, M; Valencia-Rios, J; Vicente, M A; Korili, S A; Gil, A

2005-12-15

The aim of this work is to study the effect of the platinum content (0-1.8 wt % Pt) on the microstructure of an alumina-pillared clay. For this purpose, the nitrogen physisorption data at -196 degrees C, the micropore size distributions of the supported platinum catalysts, and the hydrogen chemisorption results at 30 degrees C have been analyzed and compared. The preparation of the catalysts has modified the textural properties of the Al-pillared clay support, giving rise to a loss of surface area and micropore volume. After reduction at 420 degrees C, the presence of dispersed metallic platinum with mean crystallite size in the 22-55 A range has been found by hydrogen adsorption. Comparison of all results reveals that the platinum species block the micropore entrances by steric hindrance to nitrogen access as the platinum content increases.

Magnetic Carbon Supported Palladium Nanoparticles: An Efficient and Sustainable Catalyst for Hydrogenation Reactions

Science.gov (United States)

Magnetic carbon supported Pd catalyst has been synthesized via in situ generation of nanoferrites and incorporation of carbon from renewable cellulose via calcination; the catalyst can be used for the hydrogenation of alkenes and reduction of aryl nitro compounds.

Surface treated carbon catalysts produced from waste tires for fatty acids to biofuel conversion

Science.gov (United States)

Hood, Zachary D.; Adhikari, Shiba P.; Wright, Marcus W.; Lachgar, Abdessadek; Li, Yunchao; Naskar, Amit K.; Paranthaman, Mariappan Parans

2018-02-06

A method of making solid acid catalysts includes the step of sulfonating waste tire pieces in a first sulfonation step. The sulfonated waste tire pieces are pyrolyzed to produce carbon composite pieces having a pore size less than 10 nm. The carbon composite pieces are then ground to produce carbon composite powders having a size less than 50 .mu.m. The carbon composite particles are sulfonated in a second sulfonation step to produce sulfonated solid acid catalysts. A method of making biofuels and solid acid catalysts are also disclosed.

Pyrolysis-catalysis of waste plastic using a nickel-stainless-steel mesh catalyst for high-value carbon products.

Science.gov (United States)

Zhang, Yeshui; Nahil, Mohamad A; Wu, Chunfei; Williams, Paul T

2017-11-01

A stainless-steel mesh loaded with nickel catalyst was produced and used for the pyrolysis-catalysis of waste high-density polyethylene with the aim of producing high-value carbon products, including carbon nanotubes (CNTs). The catalysis temperature and plastic-to-catalyst ratio were investigated to determine the influence on the formation of different types of carbon deposited on the nickel-stainless-steel mesh catalyst. Increasing temperature from 700 to 900°C resulted in an increase in the carbon deposited on the nickel-loaded stainless-steel mesh catalyst from 32.5 to 38.0 wt%. The increase in sample-to-catalyst ratio reduced the amount of carbon deposited on the mesh catalyst in terms of g carbon g -1 plastic. The carbons were found to be largely composed of filamentous carbons, with negligible disordered (amorphous) carbons. Transmission electron microscopy analysis of the filamentous carbons revealed them to be composed of a large proportion (estimated at ∼40%) multi-walled carbon nanotubes (MWCNTs). The optimum process conditions for CNT production, in terms of yield and graphitic nature, determined by Raman spectroscopy, was catalysis temperature of 800°C and plastic-to-catalyst ratio of 1:2, where a mass of 334 mg of filamentous/MWCNTs g -1 plastic was produced.

Electroreduction of oxygen on carbon-supported gold catalysts

International Nuclear Information System (INIS)

Erikson, Heiki; Juermann, Gea; Sarapuu, Ave; Potter, Robert J.; Tammeveski, Kaido

2009-01-01

The electrochemical reduction of oxygen was studied on Au/C catalysts (20 and 30 wt%) in 0.5 M H 2 SO 4 and 0.1 M KOH solutions using the rotating disk electrode (RDE) method. The thickness of the Au/C-Nafion layers was varied between 1.5 and 10 μm. The specific activity of Au was independent of catalyst loading in both solutions, indicating that the transport of reactants through the catalyst layer does not limit the process of oxygen reduction under these conditions. The mass activity of 20 wt% Au/C catalysts was higher due to smaller particle size. The number of electrons involved in the reaction and the Tafel slopes were found; the values of these parameters are similar to that of bulk polycrystalline gold and indicate that the mechanism of O 2 reduction is not affected by carbon support or the catalyst configuration.

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.

Evaluation of the isotope separation rate of deuterium exchange reaction between H2 and H2O with platinum catalyst

International Nuclear Information System (INIS)

Kitamoto, Asashi; Takashima, Yoichi; Shimizu, Masami.

1983-01-01

The high performance catalysts of hydrophobic carrier with fully dispersed platinum were used to measure the isotope separation performance of hydrogen by the chemical exchange method. The continuous injection of oxygen on the order of 10 3 ppm was effective in regenerating catalyst activity and in maintaining high performance for a long time. The separation performance in a trickle bed column should be evaluated by using two parameters, ksub(g) and ksub(l). These two parameters were unified to the overall transfer coefficient ksub(fg), which may be sufficient in the estimation of overall performance or the design of a separation plant by the chemical exchange method. When one wants to increase the transfer rate in a chemical exchange column, the improvement of ksub(l) rather than ksub(g) may be more effective in increasing the overall transfer rate (its coefficient is expressed by ksub(fg) in this paper). (author)

Platinum incorporation in the Na Y zeolite through impregnation method, and characterization by XRD, FTIR and nitrogen adsorption

International Nuclear Information System (INIS)

Araujo, A.S.; Sousa, B.V.; Andrade, A.C.C.; Rodrigues, M.G.F.; Rangel, M.C.

2007-01-01

Supported metal catalysts are widely used in petroleum refining, chemical and petroleum industries. These catalysts are important in ammonia synthesis, conversion of hydrocarbons with water vapor to synthesis gas, reforming, hydrocracking, ... Platinum has long been used in cracking, hydrogenation and dehydrogenation processes. The aim of this project is the Na Y zeolitic sample preparation through impregnation for incipient humidity, with 0,5% concentration of platinum, aiming its use as a catalyst in the steam reforming reaction. The characterization techniques used were: X Rays Diffraction (XRD), Fourier Transform Infrared spectroscopy (FTIR) and Nitrogen Adsorption (BET Method). From the obtained results through the techniques mentioned previously it is possible to evidence that the platinum impregnation process did not change the Na Y zeolite structure. Through the superficial specific area (BET) it was possible to observe that the platinum impregnation process caused a decrease in the specific area due to the reduction to the accessibility to the micropores of the zeolitic structure. (author)

Biogenic platinum and palladium nanoparticles as new catalysts for the removal of pharmaceutical compounds.

Science.gov (United States)

Martins, Mónica; Mourato, Cláudia; Sanches, Sandra; Noronha, João Paulo; Crespo, M T Barreto; Pereira, Inês A C

2017-01-01

Pharmaceutical products (PhP) are one of the most alarming emergent pollutants in the environment. Therefore, it is of extreme importance to investigate efficient PhP removal processes. Biologic synthesis of platinum nanoparticles (Bio-Pt) has been reported, but their catalytic activity was never investigated. In this work, we explored the potential of cell-supported platinum (Bio-Pt) and palladium (Bio-Pd) nanoparticles synthesized with Desulfovibrio vulgaris as biocatalysts for removal of four PhP: ciprofloxacin, sulfamethoxazole, ibuprofen and 17β-estradiol. The catalytic activity of the biological nanoparticles was compared with the PhP removal efficiency of D. vulgaris whole-cells. In contrast with Bio-Pd, Bio-Pt has a high catalytic activity in PhP removal, with 94, 85 and 70% removal of 17β-estradiol, sulfamethoxazole and ciprofloxacin, respectively. In addition, the estrogenic activity of 17β-estradiol was strongly reduced after the reaction with Bio-Pt, showing that this biocatalyst produces less toxic effluents. Bio-Pt or Bio-Pd did not act on ibuprofen, but this could be completely removed by D. vulgaris whole-cells, demonstrating that sulfate-reducing bacteria are among the microorganisms capable of biotransformation of ibuprofen in anaerobic environments. This study demonstrates for the first time that Bio-Pt has a high catalytic activity, and is a promising catalyst to be used in water treatment processes for the removal of antibiotics and endocrine disrupting compounds, the most problematic PhP. Copyright © 2016 Elsevier Ltd. All rights reserved.

KOH-activated multi-walled carbon nanotubes as platinum supports for oxygen reduction reaction

Science.gov (United States)

He, Chaoxiong; Song, Shuqin; Liu, Jinchao; Maragou, Vasiliki; Tsiakaras, Panagiotis

In the present investigation, multi-walled carbon nanotubes (MWCNTs) thermally treated by KOH were adopted as the platinum supporting material for the oxygen reduction reaction electrocatalysts. FTIR and Raman spectra were used to investigate the surface state of MWCNTs treated by KOH at different temperatures (700, 800, and 900 °C) and showed MWCNTs can be successfully functionalized. The structural properties of KOH-activated MWCNTs supported Pt were determined by X-ray diffraction (XRD) and transmission electron microscopy (TEM), and their electrochemical performance was evaluated by the aid of cyclic voltammetry (CV) and rotating disk electrode (RDE) voltammetry. According to the experimental findings of the present work, the surrface of MWCNTs can be successfully functionalized with oxygen-containing groups after activation by KOH, favoring the good dispersion of Pt nanoparticles with narrow size distribution. The as-prepared Pt catalysts supported on KOH treated MWCNTs at higher temperature, possess higher electrochemical surface area and exhibit desirable activity towards oxygen reduction reaction (ORR). More precisely, it has been found that the electrochemical active area of Pt/MWCNTs-900 is approximately two times higher than that of Pt/MWCNTs. It can be concluded that KOH activation is an effective way to decorate MWCNTs' surface with oxygen-containing groups and bigger surface area, which makes them more suitable as electrocatalyst support materials.

One-step electrochemically-codeposited polyaniline-platinum for dye-sensitized solar cell applications

Energy Technology Data Exchange (ETDEWEB)

Thiangkaew, Anongnad; Keothongkham, Khamsone; Maiaugree, Wasan; Jarernboon, Wirat [Khon Kaen University, Khon Kaen (Thailand); Kamwanna, Teerasak; Pimanpang, Samuk; Amornkitbamrung, Vittaya [Khon Kaen University, Khon Kaen (Thailand); Nanotec-KKU Center of Excellence on Advanced Nanomaterials for Energy Production and Storage, Khon Kaen (Thailand)

2014-05-15

Platinum, polyaniline and composite polyaniline-platinum films were coated on conductive glass by using electrochemical deposition. They were then used as dye-sensitized solar cell counter electrodes. The efficiencies of platinum, polyaniline and composite polyaniline-platinum cells were 2.47, 4.47 and 6.62%, respectively. The improvement of composite polyaniline-platinum solar cell efficiency over pure polyaniline and platinum cells is because of an increase in the film's catalytic activity and a decrease in charge-transfer resistance between its counter electrode and electrolyte, as observed by using cyclic voltammogram and electrochemical impedance spectroscopy measurements, respectively. Co-deposition of polyaniline and Pt catalysts was confirmed by the presence of Pt and N peaks in the X-ray photoelectron spectroscopy spectrum.

Nitrogen-doped hierarchical lamellar porous carbon synthesized from the fish scale as support material for platinum nanoparticle electrocatalyst toward the oxygen reduction reaction.

Science.gov (United States)

Liu, Haijing; Cao, Yinliang; Wang, Feng; Huang, Yaqin

2014-01-22

Novel hierarchical lamellar porous carbon (HLPC) with high BET specific surface area of 2730 m(2) g(-1) and doped by nitrogen atoms has been synthesized from the fish scale without any post-synthesis treatment, and applied to support the platinum (Pt) nanoparticle (NP) catalysts (Pt/HLPC). The Pt NPs could be highly dispersed on the porous surface of HLPC with a narrow size distribution centered at ca. 2.0 nm. The results of the electrochemical analysis reveal that the electrochemical active surface area (ECSA) of Pt/HLPC is larger than the Pt NP electrocatalyst supported on the carbon black (Pt/Vulcan XC-72). Compared with the Pt/Vulcan XC-72, the Pt/HLPC exhibits larger current density, lower overpotential, and enhanced catalytic activity toward the oxygen reduction reaction (ORR) through the direct four-electron pathway. The improved catalytic activity is mainly attributed to the high BET specific surface area, hierarchical porous structures and the nitrogen-doped surface property of HLPC, indicating the superiority of HLPC as a promising support material for the ORR electrocatalysts.

Novel type of carbon-supported catalysts. I.Preparation and characterization

NARCIS (Netherlands)

van Doorn, J.; Staugaard, P.; Moulijn, J.A.; Beer, de V.H.J.

1989-01-01

The exposure of CoO/Al2O3 catalysts to carbon monoxide leads, after reduction to cobalt metal, to the formation of filamentary carbon in addition to a less reactive form of deposited carbon. The filament diameters were determined by scanning electron microscopy. The carbon content was determined by

The effect of alkaline doped catalysts on the CVD synthesis of carbon nanotubes

DEFF Research Database (Denmark)

Nemeth, Krisztian; Nemeth, Zoltan; Fejes, Dora

2011-01-01

The aim of this work was to develop new doped catalysts for chemical vapour deposition (CVD) synthesis in order to increase the quantity and quality of carbon nanotubes (CNTs). Doping compounds such as CsBr, CsCl, KBr and KCl were used to reach higher carbon deposit and carbon yield. The amount o...... of the dopant alkali compounds varied from 1 to 5%. As prepared CNTs were characterized by transmission electron microscopy (TEM), X‐ray diffraction (XRD) and Raman microscopy. Results revealed that both carbon yield and deposit could be increased over doped catalysts.......The aim of this work was to develop new doped catalysts for chemical vapour deposition (CVD) synthesis in order to increase the quantity and quality of carbon nanotubes (CNTs). Doping compounds such as CsBr, CsCl, KBr and KCl were used to reach higher carbon deposit and carbon yield. The amount...

Carbon catalysts for electrochemical hydrogen peroxide production in acidic media

DEFF Research Database (Denmark)

Čolić, Viktor; Yang, Sungeun; Révay, Zsolt

2018-01-01

Hydrogen peroxide is a commodity chemical, as it is an environmentally friendly oxidant. The electrochemical production of H2O2 from oxygen and water by the reduction of oxygen is of great interest, as it would allow the decentralized, on-site, production of pure H2O2. The ability to run...... the reaction in an acidic electrolyte with high performance is particularly important, as it would allow the use of polymer solid electrolytes and the production of pH-neutral hydrogen peroxide. Carbon catalysts, which are cheap, abundant, durable and can be highly selective show promise as potential catalysts...... for such systems. In this work, we examine the electrocatalytic performance and properties of seven commercially available carbon materials for H2O2 production by oxygen electroreduction. We show that the faradaic efficiencies for the reaction lie in a wide range of 18-82% for different carbon catalysts. In order...

Functionalized Natural Carbon-Supported Nanoparticles as Excellent Catalysts for Hydrocarbon Production.

Science.gov (United States)

Sun, Jian; Guo, Lisheng; Ma, Qingxiang; Gao, Xinhua; Yamane, Noriyuki; Xu, Hengyong; Tsubaki, Noritatsu

2017-02-01

We report a one-pot and eco-friendly synthesis of carbon-supported cobalt nanoparticles, achieved by carbonization of waste biomass (rice bran) with a cobalt source. The functionalized biomass provides carbon microspheres as excellent catalyst support, forming a unique interface between hydrophobic and hydrophilic groups. The latter, involving hydroxyl and amino groups, can catch much more active cobalt nanoparticles on surface for Fischer-Tropsch synthesis than chemical carbon. The loading amount of cobalt on the final catalyst is much higher than that prepared with a chemical carbon source, such as glucose. The proposed concept of using a functionalized natural carbon source shows great potential compared with conventional carbon sources, and will be meaningful for other fields concerning carbon support, such as heterogeneous catalysis or electrochemical fields. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

A Comparative Study of Carbon Nanotubes Synthesized from Co/Zn/Al and Fe/Ni/Al Catalyst

Directory of Open Access Journals (Sweden)

Ezekiel Dixon Dikio

2011-01-01

Full Text Available The catalyst systems Fe/Ni/Al and Co/Zn/Al were synthesized and used in the synthesis of carbon nanotubes. The carbon nanotubes produced were characterized by Field Emission Scanning Electron Microscope (FE-SEM, Energy Dispersive x-ray Spectroscopy (EDS, Raman spectroscopy, Thermogravimetric Analysis (TGA and Transmission Electron Microscope (TEM. A comparison of the morphological profile of the carbon nanotubes produced from these catalysts indicates the catalyst system Fe/Ni/Al to have produced higher quality carbon nanotubes than the catalyst system Co/Zn/Al.

Oxygen reduction at platinum nanoparticles supported on carbon cryogel in alkaline solution

Directory of Open Access Journals (Sweden)

N. R. ELEZOVIC

2007-07-01

Full Text Available The oxygen reduction reaction was investigated in 0.1 M NaOH solution, on a porous coated electrode formed of Pt particles supported on carbon cryogel. The Pt/C catalyst was characterized by the X-ray diffraction (XRD, transmission electron microscopy (TEM and cyclic voltammetry techniques. The results demonstrated a successful reduction of Pt to metallic form and homogenous Pt particle size distribution with a mean particle size of about 2.7 nm. The ORR kinetics was investigated by linear sweep polarization at a rotating disc electrode. The results showed the existence of two E – log j regions, usually referred to polycrystalline Pt in acid and alkaline solution. At low current densities (lcd, the Tafel slope was found to be close to –2.3RT/F, while at high current densities (hcd it was found to be close to –2×2.3RT/F. It is proposed that the main path in the ORR mechanism on Pt particles was the direct four-electron process, with the transfer of the first electron as the rate determining step. If the activities are expressed through the specific current densities, a small enhancement of the catalytic activity for Pt/C was observed compared to that of polycrystalline Pt. The effect of the Pt particle size on the electrocatalysis of oxygen reduction was ascribed to the predominant (111 facets of the platinum crystallites.

Controlled surface segregation leads to efficient coke-resistant nickel/platinum bimetallic catalysts for the dry reforming of methane

KAUST Repository

Li, Lidong; Zhou, Lu; Ould-Chikh, Samy; Anjum, Dalaver; Kanoun, Mohammed; Scaranto, Jessica; Hedhili, Mohamed Nejib; Khalid, Syed; Laveille, Paco; D'Souza, Lawrence; Clo, Alain M.; Basset, Jean-Marie

2015-01-01

Surface composition and structure are of vital importance for heterogeneous catalysts, especially for bimetallic catalysts, which often vary as a function of reaction conditions (known as surface segregation). The preparation of bimetallic catalysts with controlled metal surface composition and structure is very challenging. In this study, we synthesize a series of Ni/Pt bimetallic catalysts with controlled metal surface composition and structure using a method derived from surface organometallic chemistry. The evolution of the surface composition and structure of the obtained bimetallic catalysts under simulated reaction conditions is investigated by various techniques, which include CO-probe IR spectroscopy, high-angle annular dark-field scanning transmission electron microscopy, energy-dispersive X-ray spectroscopy, extended X-ray absorption fine structure analysis, X-ray absorption near-edge structure analysis, XRD, and X-ray photoelectron spectroscopy. It is demonstrated that the structure of the bimetallic catalyst is evolved from Pt monolayer island-modified Ni nanoparticles to core-shell bimetallic nanoparticles composed of a Ni-rich core and a Ni/Pt alloy shell upon thermal treatment. These catalysts are active for the dry reforming of methane, and their catalytic activities, stabilities, and carbon formation vary with their surface composition and structure. The reform of reforming: A series of alumina-supported Ni/Pt bimetallic nanoparticles (NPs) with controlled surface composition and structure are prepared. Remarkable surface segregation for these bimetallic NPs is observed upon thermal treatment. These bimetallic NPs are active catalysts for CO2 reforming of CH4, and their catalytic activities, stabilities, and carbon formation vary with their surface composition and structure.

Controlled surface segregation leads to efficient coke-resistant nickel/platinum bimetallic catalysts for the dry reforming of methane

KAUST Repository

Li, Lidong

2015-02-03

Surface composition and structure are of vital importance for heterogeneous catalysts, especially for bimetallic catalysts, which often vary as a function of reaction conditions (known as surface segregation). The preparation of bimetallic catalysts with controlled metal surface composition and structure is very challenging. In this study, we synthesize a series of Ni/Pt bimetallic catalysts with controlled metal surface composition and structure using a method derived from surface organometallic chemistry. The evolution of the surface composition and structure of the obtained bimetallic catalysts under simulated reaction conditions is investigated by various techniques, which include CO-probe IR spectroscopy, high-angle annular dark-field scanning transmission electron microscopy, energy-dispersive X-ray spectroscopy, extended X-ray absorption fine structure analysis, X-ray absorption near-edge structure analysis, XRD, and X-ray photoelectron spectroscopy. It is demonstrated that the structure of the bimetallic catalyst is evolved from Pt monolayer island-modified Ni nanoparticles to core-shell bimetallic nanoparticles composed of a Ni-rich core and a Ni/Pt alloy shell upon thermal treatment. These catalysts are active for the dry reforming of methane, and their catalytic activities, stabilities, and carbon formation vary with their surface composition and structure. The reform of reforming: A series of alumina-supported Ni/Pt bimetallic nanoparticles (NPs) with controlled surface composition and structure are prepared. Remarkable surface segregation for these bimetallic NPs is observed upon thermal treatment. These bimetallic NPs are active catalysts for CO2 reforming of CH4, and their catalytic activities, stabilities, and carbon formation vary with their surface composition and structure.

Sea urchin-like mesoporous carbon material grown with carbon nanotubes as a cathode catalyst support for fuel cells

Energy Technology Data Exchange (ETDEWEB)

Kuo, Ping-Lin; Hsu, Chun-Han; Li, Wan-Ting; Jhan, Jing-Yi; Chen, Wei-Fu [Department of Chemical Engineering, National Cheng Kung University, Tainan 70101 (China)

2010-12-15

A sea urchin-like carbon (UC) material with high surface area (416 m{sup 2} g{sup -1}), adequate electrical conductivity (59.6 S cm{sup -1}) and good chemical stability was prepared by growing carbon nanotubes onto mesoporous carbon hollow spheres. A uniform dispersion of Pt nanoparticles was then anchored on the UC, where the Pt nanoparticles were prepared using benzylamine as the stabilizer. For this Pt loaded carbon, cyclic voltammogram measurements showed an exceptionally high electrochemically active surface area (EAS) (114.8 m{sup 2} g{sup -1}) compared to the commonly used commercial E-TEK catalyst (65.2 m{sup 2} g{sup -1}). The durability test demonstrates that the carbon used as a support exhibited minor loss in EAS of Pt. Compared to the E-TEK (20 wt%) cathode catalyst, this Pt loaded UC catalyst has greatly enhanced catalytic activity toward the oxygen reduction reaction, less cathode flooding and considerably improved performance, resulting in an enhancement of ca. 37% in power density compared with that of E-TEK. Based on the results obtained, the UC is an excellent support for Pt nanoparticles used as cathode catalysts in proton exchange membrane fuel cells. (author)

The kinetics of steam-carbon dioxide conversion, rational ways and production catalysts of process gas

International Nuclear Information System (INIS)

Khamroev, F.B.

2016-01-01

The purpose of the present work is to study the kinetics of steam-carbon dioxide conversion, rational ways and production catalysts of process gas. The experimental equation of steam-carbon methane conversion, heat stability increasing and catalyst efficiency, decreasing of hydrodynamical resistance of catalyst layer were determined.

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

Platinum nanocube catalysts for methanol and ethanol electrooxidation

Energy Technology Data Exchange (ETDEWEB)

Han, Sang-Beom; Song, You-Jung; Lee, Jong-Min; Kim, Jy-Yeon; Park, Kyung-Won [Department of Chemical and Environmental Engineering, Soongsil University, Seoul 156-743 (Korea)

2008-07-15

We prepared Pt nanocube catalyst with about 3.6 nm in size by a polyol process in the presence of PVP as a stabilizer and Fe ion as a kinetic controller. The crystal structure of Pt nanocube with {l_brace}1 0 0{r_brace} faces was confirmed by field-emission transmission electron microscopy. In a cyclic voltammogram, we found that the Pt nanocube catalyst showed relatively high ratio of the forward anodic peak current to the reverse anodic peak current resulting in less accumulation of residues on the catalyst. The Pt nanocube catalyst with the edge of stepped {l_brace}1 0 0{r_brace} faces was preferable to breakage of CH{sub 3}OH and CH{sub 3}CH{sub 2}OH compared to polycrystalline Pt nanocatalyst. In an electrochemical measurement for methanol and ethanol electrooxidation, the Pt nanocube catalyst showed an excellent catalytic activity, i.e., lower onset potential and higher current density, compared to the polycrystalline Pt nanocatalyst. (author)

Homogeneous deuterium exchange using rhenium and platinum chloride catalysts

International Nuclear Information System (INIS)

Fawdry, R.M.

1979-01-01

Previous studies of homogeneous hydrogen isotope exchange are mostly confined to one catalyst, the tetrachloroplatinite salt. Recent reports have indicated that chloride salts of iridium and rhodium may also be homogeneous exchange catalysts similar to the tetrachloroplatinite, but with much lower activities. Exchange by these homogeneous catalysts is frequently accompanied by metal precipitation with the termination of homogeneous exchange, particularly in the case of alkane exchange. The studies presented in this thesis describe two different approaches to overcome this limitation of homogeneous hydrogen isotope exchange catalysts. The first approach was to improve the stability of an existing homogeneous catalyst and the second was to develop a new homogeneous exchange catalyst which is free of the instability limitation

Effect of catalyst preparation on the yield of carbon nanotube growth

International Nuclear Information System (INIS)

Escobar, Mariano; Rubiolo, Gerardo; Candal, Roberto; Goyanes, Silvia

2009-01-01

Multi-wall carbon nanotubes (MWCNTs) were synthesized by catalytic chemical vapor deposition (CVD) on catalytic iron nanoparticles dispersed in a silica matrix, prepared by sol gel method. In this contribution, variation of gelation condition on catalyst structure and its influence on the yield of carbon nanotubes growth was studied. The precursor utilized were tetraethyl-orthosilicate and iron nitrate. The sols were dried at two different temperatures in air (25 or 80 deg. C) and then treated at 450 deg. C for 10 h. The xerogels were introduced into the chamber and reduced in a hydrogen/nitrogen (10%v/v) atmosphere at 600 deg. C. MWCNTs were formed by deposition of carbon atoms from decomposition of acetylene at 700 deg. C. The system gelled at RT shows a yield of 100% respect to initial catalyst mass whereas the yield of that gelled at 80 deg. C was lower than 10%. Different crystalline phases are observed for both catalysts in each step of the process. Moreover, TPR analysis shows that iron oxide can be efficiently reduced to metallic iron only in the system gelled at room temperature. Carbon nanotubes display a diameter of about 25-40 nm and several micron lengths. The growth mechanism of MWCNTs is base growth mode for both catalysts.

Effect of catalyst preparation on the yield of carbon nanotube growth

Energy Technology Data Exchange (ETDEWEB)

Escobar, Mariano, E-mail: mescobar@df.uba.a [Dep. Quimica Inorganica, Analitica y Quimica Fisica, FCEyN, UBA, Ciudad Universitaria (1428), Bs As (Argentina); LP and MC, Dep. Fisica, FCEyN, UBA (Argentina); Rubiolo, Gerardo [Unidad de Actividad Materiales, CNEA, Av Gral Paz 1499, San Martin (1650), Bs As (Argentina); Consejo Nacional de Investigaciones Cientificas y Tecnicas (CONICET) (Argentina); Candal, Roberto [Consejo Nacional de Investigaciones Cientificas y Tecnicas (CONICET) (Argentina); Instituto de Fisico-quimica de Materiales, Ambiente y Energia (INQUIMAE), CONICET - UBA (Argentina); Goyanes, Silvia [LP and MC, Dep. Fisica, FCEyN, UBA (Argentina); Consejo Nacional de Investigaciones Cientificas y Tecnicas (CONICET) (Argentina)

2009-10-01

Multi-wall carbon nanotubes (MWCNTs) were synthesized by catalytic chemical vapor deposition (CVD) on catalytic iron nanoparticles dispersed in a silica matrix, prepared by sol gel method. In this contribution, variation of gelation condition on catalyst structure and its influence on the yield of carbon nanotubes growth was studied. The precursor utilized were tetraethyl-orthosilicate and iron nitrate. The sols were dried at two different temperatures in air (25 or 80 deg. C) and then treated at 450 deg. C for 10 h. The xerogels were introduced into the chamber and reduced in a hydrogen/nitrogen (10%v/v) atmosphere at 600 deg. C. MWCNTs were formed by deposition of carbon atoms from decomposition of acetylene at 700 deg. C. The system gelled at RT shows a yield of 100% respect to initial catalyst mass whereas the yield of that gelled at 80 deg. C was lower than 10%. Different crystalline phases are observed for both catalysts in each step of the process. Moreover, TPR analysis shows that iron oxide can be efficiently reduced to metallic iron only in the system gelled at room temperature. Carbon nanotubes display a diameter of about 25-40 nm and several micron lengths. The growth mechanism of MWCNTs is base growth mode for both catalysts.

Features of the kinetics of heterogeneous reactions with phase transformations on catalyst surfaces

Energy Technology Data Exchange (ETDEWEB)

Berman, A D; Krylov, O V

1978-01-01

This paper presents a review of 41 bibliographic references to experiments on the adsorption of various gases (e.g., carbon monoxide, formic acid, ammonia, and oxygen) on metals (e.g., nickel, molybdenum, and platinum) and oxides covers observations of two-dimensional phases during adsorption; the kinetics of adsorption and catalysis associated with two-dimensional phase transitions; and several approximate models for describing the kinetics of heterogeneous catalysis which account for two-dimensional phase transformations on catalyst surfaces.

Magnetism for understanding catalyst analysis of purified carbon nanotubes

Energy Technology Data Exchange (ETDEWEB)

Bellouard, Christine; Mercier, Guillaume; Cahen, Sébastien; Ghanbaja, Jaafar; Medjahdi, Ghouti [Institut Jean Lamour, CNRS-Université de Lorraine, BP 70239, 54506 Vandoeuvre-lès-Nancy (France); Gleize, Jérôme [Laboratoire de Chimie Physique-Approche Multi-échelle de Milieux Complexes-Université de Lorraine, 1 Bd Arago, 57078 Metz (France); Lamura, Gianrico [CNR-SPIN – Dipartimento di Fisica, via Dodecaneso 33, 16146 Genova (Italy); Hérold, Claire [Institut Jean Lamour, CNRS-Université de Lorraine, BP 70239, 54506 Vandoeuvre-lès-Nancy (France); Vigolo, Brigitte, E-mail: Brigitte.Vigolo@univ-lorraine.fr [Institut Jean Lamour, CNRS-Université de Lorraine, BP 70239, 54506 Vandoeuvre-lès-Nancy (France)

2016-08-01

The precise quantification of catalyst residues in purified carbon nanotubes is often a major issue in view of any fundamental and/or applicative studies. More importantly, since the best CNTs are successfully grown with magnetic catalysts, their quantification becomes strictly necessary to better understand intrinsic properties of CNT. For these reasons, we have deeply analyzed the catalyst content remained in nickel–yttrium arc-discharge single walled carbon nanotubes purified by both a chlorine-gas phase and a standard acid-based treatment. The study focuses on Ni analysis which has been investigated by transmission electron microscopy, X-ray diffraction, thermogravimetry analysis, and magnetic measurements. In the case of the acid-based treatment, all quantifications result in a decrease of the nanocrystallized Ni by a factor of two. In the case of the halogen gas treatment, analysis and quantification of Ni content is less straightforward: a huge difference appears between X-ray diffraction and thermogravimetry results. Thanks to magnetic measurements, this disagreement is explained by the presence of Ni{sup 2+} ions, belonging to NiCl{sub 2} formed during the Cl-based purification process. In particular, NiCl{sub 2} compound appears under different magnetic/crystalline phases: paramagnetic or diamagnetic, or well intercalated in between carbon sheets with an ordered magnetic phase at low temperature. - Highlights: • Cl-gas treatment of Ni catalyst of carbon nanotubes leads to NiCl{sub 2} residue. • Magnetic measurements show the transformation of Ni{sup 0} in Ni{sup 2+}through a purification process. • High temperature Cl treatment removes 75% of metallic impurities. • Cl-purification yields to an amount of metal of 1.5% in arc-discharge CNT samples.

Anti-bacteria activity of carbon nanotubes grown on trimetallic catalyst

Science.gov (United States)

Ibrahim, S. O.; Abdulkareem, A. S.; Isah, K. U.; Ahmadu, U.; Bankole, M. T.; Kariim, I.

2018-06-01

Trimetallic catalyst was prepared using wet impregnation method to produce carbon nanotubes (CNTs) through the method of catalytic chemical vapor deposition (CCVD). Characterization of the developed catalyst and CNTs were carried out using thermogravimetric analysis (TGA), x-ray diffraction (XRD), specific surface area Brunauer-Emmett-Teller (BET), Fourier-transform infrared spectroscopy (FTIR), high-resolution scanning electron microscopy (HRSEM)/energy dispersive x-ray spectroscopy (EDS) and high-resolution transmission electron microscopy (HRTEM)/selected area electron diffraction (SAED). The BET and TGA analysis indicated that the catalyst has a high surface area and is thermally stable. The FTIR of the developed catalyst shows notable functional group with presence of unbound water. The HRSEM of the catalyst revealed agglomerated, homogeneous and porous particles while the HRSEM/HRTEM of the produced CNTs gave the formation of long strand of multiwalled carbon nanotubes (MWCNTs), and homogeneous crystalline fringe like structure with irregular diameter. EDS revealed the dominance of carbon in the elemental composition. XRD/SAED patterns of the catalyst suggest high dispersion of the metallic particles in the catalyst mixture while that of the CNTs confirmed that the produced MWCNTs were highly graphitized and crystalline in nature with little structural defects. The anti-bacteria activity of the produced MWCNTs on Klebsiella pneumoneae, Escherichia coli, and Pseudomonas aeruginosa was also carried out. It was observed that the produced MWCNTs have an inhibitory property on bacteria; Escherichia coli and Klebsiella pneumoneae from zero day ( and ) through to twelfth day (Nil count) respectively. It has no effect on Pseudomonas aeruginosa with too numerous to count at zero-sixth day, but a breakdown in its growth at ninth-twelfth day (). This study implied that MWCNTs with varying diameter and well-ordered nano-structure can be produced from catalyst via CCVD

Activated Carbon, Carbon Nanofiber and Carbon Nanotube Supported Molybdenum Carbide Catalysts for the Hydrodeoxygenation of Guaiacol

Directory of Open Access Journals (Sweden)

Eduardo Santillan-Jimenez

2015-03-01

Full Text Available Molybdenum carbide was supported on three types of carbon support—activated carbon; multi-walled carbon nanotubes; and carbon nanofibers—using ammonium molybdate and molybdic acid as Mo precursors. The use of activated carbon as support afforded an X-ray amorphous Mo phase, whereas crystalline molybdenum carbide phases were obtained on carbon nanofibers and, in some cases, on carbon nanotubes. When the resulting catalysts were tested in the hydrodeoxygenation (HDO of guaiacol in dodecane, catechol and phenol were obtained as the main products, although in some instances significant amounts of cyclohexane were produced. The observation of catechol in all reaction mixtures suggests that guaiacol was converted into phenol via sequential demethylation and HDO, although the simultaneous occurrence of a direct demethoxylation pathway cannot be discounted. Catalysts based on carbon nanofibers generally afforded the highest yields of phenol; notably, the only crystalline phase detected in these samples was Mo2C or Mo2C-ζ, suggesting that crystalline Mo2C is particularly selective to phenol. At 350 °C, carbon nanofiber supported Mo2C afforded near quantitative guaiacol conversion, the selectivity to phenol approaching 50%. When guaiacol HDO was performed in the presence of acetic acid and furfural, guaiacol conversion decreased, although the selectivity to both catechol and phenol was increased.

Nickel catalysts for internal reforming in molten carbonate fuel cells

NARCIS (Netherlands)

Berger, R.J.; Berger, R.J.; Doesburg, E.B.M.; Doesburg, E.B.M.; van Ommen, J.G.; Ross, J.R.H.; Ross, J.R.H.

1996-01-01

Natural gas may be used instead of hydrogen as fuel for the molten carbonate fuel cell (MCFC) by steam reforming the natural gas inside the MCFC, using a nickel catalyst (internal reforming). The severe conditions inside the MCFC, however, require that the catalyst has a very high stability. In

Beneficial effects of rhodium and tin oxide on carbon supported platinum catalysts for ethanol electrooxidation

Science.gov (United States)

Soares, Layciane A.; Morais, Claudia; Napporn, Teko W.; Kokoh, K. Boniface; Olivi, Paulo

2016-05-01

This work investigates ethanol electrooxidation on Pt/C, PtxRhy/C, Pt-SnO2/C, and PtxRhy-SnO2/C catalysts synthesized by the Pechini and microwave-assisted polyol methods. The catalysts are characterized by energy dispersive X-ray analysis (EDX), transmission electron microscopy (TEM), and X-ray diffraction (XRD) techniques. The electrochemical properties of these electrode materials are examined by cyclic voltammetry and chronoamperometry experiments in acid medium. The products obtained during ethanol electrolysis are identified by high performance liquid chromatography (HPLC). The adsorbed intermediates are evaluated by an in situ reflectance Infrared Spectroscopy technique combined with cyclic voltammetry. Catalysts performance in a direct ethanol fuel cell (DEFC) is also assessed. The electrical performance of the electrocatalysts in a single DEFC at 80 °C decreases in the following order Pt70Rh30SnO2 > Pt80Rh20SnO2 > Pt60Rh40SnO2 ∼ PtSnO2 > PtxRhy ∼ Pt, showing that the presence of SnO2 enhances the ability of Pt to catalyze ethanol electrooxidation.

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

International Nuclear Information System (INIS)

Elgart, M.F.

1976-01-01

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

Properties and application of noble metal catalysts for heterogeneous catalytic hydrogenations

Energy Technology Data Exchange (ETDEWEB)

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

1976-07-01

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

Fe catalysts for methane decomposition to produce hydrogen and carbon nano materials

KAUST Repository

Zhou, Lu; Enakonda, Linga Reddy; Harb, Moussab; Saih, Youssef; Aguilar Tapia, Antonio; Ould-Chikh, Samy; Hazemann, Jean-louis; Li, Jun; Wei, Nini; Gary, Daniel; Del-Gallo, Pascal; Basset, Jean-Marie

2017-01-01

Conducting catalytic methane decomposition over Fe catalysts is a green and economic route to produce H2 without CO/CO2 contamination. Fused 65wt% and impregnated 20wt% Fe catalysts were synthesized with different additives to investigate their activity, whereas showing Fe-Al2O3 combination as the best catalyst. Al2O3 is speculated to expose more Fe00 for the selective deposition of carbon nano tubes (CNTs). A fused Fe (65wt%)-Al2O3 sample was further investigated by means of H2-TPR, in-situ XRD, HRTEM and XAS to conclude 750°C is the optimized temperature for H2 pre-reduction and reaction to obtain a high activity. Based on density functional theory (DFT) study, a reaction mechanism over Fe catalysts was proposed to explain the formation of graphite from unstable supersaturated iron carbides decomposition. A carbon deposition model was further proposed which explains the formation of different carbon nano materials.

Fe catalysts for methane decomposition to produce hydrogen and carbon nano materials

KAUST Repository

Zhou, Lu

2017-02-21

Conducting catalytic methane decomposition over Fe catalysts is a green and economic route to produce H2 without CO/CO2 contamination. Fused 65wt% and impregnated 20wt% Fe catalysts were synthesized with different additives to investigate their activity, whereas showing Fe-Al2O3 combination as the best catalyst. Al2O3 is speculated to expose more Fe00 for the selective deposition of carbon nano tubes (CNTs). A fused Fe (65wt%)-Al2O3 sample was further investigated by means of H2-TPR, in-situ XRD, HRTEM and XAS to conclude 750°C is the optimized temperature for H2 pre-reduction and reaction to obtain a high activity. Based on density functional theory (DFT) study, a reaction mechanism over Fe catalysts was proposed to explain the formation of graphite from unstable supersaturated iron carbides decomposition. A carbon deposition model was further proposed which explains the formation of different carbon nano materials.

Adsorption of CO on Ru and Pt blacks and catalysts and the possibility of its utilization for the determination of the ruthenium-free surface

Czech Academy of Sciences Publication Activity Database

Paseka, Ivo

2007-01-01

Roč. 11, č. 1 (2007), s. 52-58 ISSN 1432-8488 R&D Projects: GA ČR(CZ) GA104/03/0409 Institutional research plan: CEZ:AV0Z40320502 Keywords : hydrogen/ carbon monoxide adsorption * platinum/ruthenium catalysts * specific surface Subject RIV: CA - Inorganic Chemistry Impact factor: 1.535, year: 2007

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.

Synthesis of 2D Nitrogen-Doped Mesoporous Carbon Catalyst for Oxygen Reduction Reaction

Directory of Open Access Journals (Sweden)

Zhipeng Yu

2017-02-01

Full Text Available 2D nitrogen-doped mesoporous carbon (NMC is synthesized by using a mesoporous silica film as hard template, which is then investigated as a non-precious metal catalyst for the oxygen reduction reaction (ORR. The effect of the synthesis conditions on the silica template and carbon is extensively investigated. In this work, we employ dual templates—viz. graphene oxide and triblock copolymer F127—to control the textural features of a 2D silica film. The silica is then used as a template to direct the synthesis of a 2D nitrogen-doped mesoporous carbon. The resultant nitrogen-doped mesoporous carbon is characterized by transmission electron microscopy (TEM, nitrogen ad/desorption isotherms, X-ray photoelectron spectroscopy (XPS, cyclic voltammetry (CV, and rotating disk electrode measurements (RDE. The electrochemical test reveals that the obtained 2D-film carbon catalyst yields a highly electrochemically active surface area and superior electrocatalytic activity for the ORR compared to the 3D-particle. The superior activity can be firstly attributed to the difference in the specific surface area of the two catalysts. More importantly, the 2D-film morphology makes more active sites accessible to the reactive species, resulting in a much higher utilization efficiency and consequently better activity. Finally, it is noted that all the carbon catalysts exhibit a higher ORR activity than a commercial Pt catalyst, and are promising for use in fuel cells.

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.

Platinum-modified cobalt nanosheets supported on three-dimensional carbon sponge as a high-performance catalyst for hydrogen peroxide electroreduction

International Nuclear Information System (INIS)

Ye, Ke; Zhang, Dongming; Zhang, Hongyu; Cheng, Kui; Wang, Guiling; Cao, Dianxue

2015-01-01

Graphical abstract: - Highlights: • The Pt-Co NS@carbon sponge electrode shows unique nanosheet structure on the three-dimensional (3D) porous network skeleton with a large surface area. • The Pt-Co NS@carbon sponge electrode achieves a reduction current density of −1.38 A cm"−"2 mg"−"1 in 3.0 mol L"−"1 KOH and 1.5 mol L"−"1 H_2O_2 at −0.50 V (vs. Ag/AgCl) • The Pt-Co NS@carbon sponge electrode exhibits a desirable stability for the H_2O_2 electroreduction. - Abstract: Pt-modified Co nanosheet@carbon sponge (Pt-Co NS@carbon sponge) electrode is synthesized via a facile sponge carbonization method coupled with a direct Co electrodeposition and Pt chemical-deposition. The obtained electrodes are characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX) and transmission electron microscopy (TEM). The catalytic performances of H_2O_2 electroreduction in alkaline medium are investigated by cyclic voltammetry (CV), chronoamperometry (CA) and electrochemical impedance spectroscopy (EIS). The Pt-Co NS@carbon sponge electrode exhibits unique nanosheet structure on the three-dimensional (3D) porous network skeleton with a large surface area and displays excellent catalytic performance. The Pt-Co NS@carbon sponge electrode achieves a reduction current density of −1.38 A cm"−"2 mg"−"1 in 3.0 mol L"−"1 KOH and 1.5 mol L"−"1 H_2O_2 at −0.50 V (vs. Ag/AgCl) accompanied with a desirable stability, which is significantly higher than the catalytic activity of H_2O_2 electroreduction achieved previously with precious metals as catalysts. The impressive electrocatalytic performance is largely attributed to the superior 3D open structure and high electronic conductivity, which ensures the full utilization of Pt surfaces and makes the electrode have higher electrochemical activity. Original Pt-Co NS@carbon sponge electordes have a great potential for the

Activated carbon from orange peels as supercapacitor electrode and catalyst support for oxygen reduction reaction in proton exchange membrane fuel cell

Directory of Open Access Journals (Sweden)

M. Dhelipan

2017-05-01

Full Text Available Activated carbon is synthesized using orange peel as precursor through chemical activation using H3PO4 and its ability as electrocatalyst support for ORR reaction is examined. The prepared material was subjected to various structural, compositional, morphological and electrochemical studies. For ORR activity, the platinum loaded on activated carbon (Pt/OP-AC was investigated by cyclic voltammograms (CVs recorded in N2 and O2 saturated 0.1 M aqueous HClO4. For supercapacitor performance, three electrode systems was tested in aqueous H2SO4 for feasibility determination and showed electrochemical double layer capacitance (EDLC behaviour which is expected for activated carbon like materials. Electrochemical surface area (ECSA of the activated carbon from orange peel is measured using CV. The physical properties of the prepared carbon are studied using SEM (scanning electron microscope, XRD (X-ray diffraction, Fourier transform infrared (FT-IR spectroscopy and Raman spectroscopy. The AC derived from orange peels delivered a high specific capacitance of 275 F g−1 at 10 mV s-1 scan rate. Hence, this study suggested that orange peels may be considered not only as a potential alternative source for synthesizing carbon supported catalyst for fuel cell application but also highlight the production of low-cost carbon for further applications like supercapacitors.

Stability of Porous Platinum Nanoparticles: Combined In Situ TEM and Theoretical Study

DEFF Research Database (Denmark)

Chang, Shery L. Y.; Barnard, Amanda S.; Dwyer, Christian

2012-01-01

Porous platinum nanoparticles provide a route for the development of catalysts that use less platinum without sacrificing catalytic performance. Here, we examine porous platinum nanoparticles using a combination of in situ transmission electron microscopy and calculations based on a first-principles......-parametrized thermodynamic model. Our experimental observations show that the initially irregular morphologies of the as-sythesized porous nanoparticles undergo changes at high temperatures to morphologies having faceted external surfaces with voids present in the interior of the particles. The increasing size of stable...

thesis of high-purity carbon nanotubes over alumina and silica supported bimetallic catalysts

Directory of Open Access Journals (Sweden)

Sanja Ratković

2009-10-01

Full Text Available Carbon nanotubes (CNTs were synthesized by a catalytic chemical vapor deposition method (CCVD of ethylene over alumina and silica supported bimetallic catalysts based on Fe, Co and Ni. The catalysts were prepared by a precipitation method, calcined at 600 °C and in situ reduced in hydrogen flow at 700 °C. The CNTs growth was carried out by a flow the mixture of C2H4 and nitrogen over the catalyst powder in a horizontal oven. The structure and morphology of as-synthesized CNTs were characterized using SEM. The as-synthesized nanotubes were purified by acid and basic treatments in order to remove impurities such as amorphous carbon, graphite nanoparticles and metal catalysts. XRD and DTA/TG analyses showed that the amounts of by-products in the purified CNTs samples were reduced significantly. According to the observed results, ethylene is an active carbon source for growing high-density CNTs with high yield but more on alumina-supported catalysts than on their silica- supported counterparts. The last might be explained by SMSI formed in the case of alumina-supported catalysts, resulting in higher active phase dispersion.

A study of Rh xS y/C and RuSe x/C as methanol-tolerant oxygen reduction catalysts for mixed-reactant fuel cell applications

International Nuclear Information System (INIS)

Papageorgopoulos, Dimitrios C.; Liu, Fang; Conrad, Olaf

2007-01-01

For efficient operation, mixed-reactant fuel cells utilise highly selective anode and cathode electrocatalysts. While platinum and its alloys are the most widely used ORR electrocatalysts in conventional DMFCs, they suffer from both their very high activity for methanol oxidation and their inherent cost. Platinum-free precious metal chalcogenides have been suggested as alternatives with comparable oxygen reduction activity in the presence of methanol. Of these, commercially available carbon supported rhodium sulphide and developmental ruthenium selenium were electrochemically tested and assessed for their potential as selective ORR cathode catalysts. Both materials exhibited oxygen reduction activity approaching that of platinum, albeit at potentials 150 and 80 mV more negative. The three materials' ability to maintain their oxygen reduction activity in the presence of methanol ranks ruthenium selenium > rhodium sulphide >> platinum

Preparation of SnO{sub 2}-CNTs supported Pt catalysts and their electrocatalytic properties for ethanol oxidation

Energy Technology Data Exchange (ETDEWEB)

Pang, H.L.; Lu, J.P. [State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082 (China); Chen, J.H. [State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082 (China)], E-mail: chenjinhua@hnu.cn; Huang, C.T.; Liu, B.; Zhang, X.H. [State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082 (China)

2009-03-30

SnO{sub 2}-carbon nanotubes (CNTs) composites were prepared by sol-gel method, and characterized by scanning electron microscopy and X-ray diffraction. Due to high stability in diluted acidic solution, SnO{sub 2}-CNTs composites were selected as the catalyst support and second catalyst for ethanol electrooxidation. The electrocatalytic properties of the SnO{sub 2}-CNTs supported platinum (Pt) catalyst (Pt/SnO{sub 2}-CNTs) for ethanol oxidation have been investigated by typical electrochemical methods. Under the same mass loading of Pt, the Pt/SnO{sub 2}-CNTs catalyst shows higher electrocatalytic activity and better long-term cycle stability than Pt/SnO{sub 2} catalyst. Additionally, the effect of the mass ratio of CNTs to SnO{sub 2} on the electrocatalytic activity of the electrode for ethanol oxidation was investigated, and the optimum mass ratio of CNTs to SnO{sub 2} in the Pt/SnO{sub 2}-CNTs catalyst is 1/6.3.

Direct Olefination of Alcohols with Sulfones by Using Heterogeneous Platinum Catalysts.

Science.gov (United States)

Siddiki, S M A Hakim; Touchy, Abeda Sultana; Kon, Kenichi; Shimizu, Ken-Ichi

2016-04-18

Carbon-supported Pt nanoparticles (Pt/C) were found to be effective heterogeneous catalysts for the direct Julia olefination of alcohols in the presence of sulfones and KOtBu under oxidant-free conditions. Primary alcohols, including aryl, aliphatic, allyl, and heterocyclic alcohols, underwent olefination with dimethyl sulfone and aryl alkyl sulfones to give terminal and internal olefins, respectively. Secondary alcohols underwent methylenation with dimethyl sulfone. Under 2.5 bar H2, the same reaction system was effective for the transformation of alcohol OH groups to alkyl groups. Structural and mechanistic studies of the terminal olefination system suggested that Pt(0) sites on the Pt metal particles are responsible for the rate-limiting dehydrogenation of alcohols and that KOtBu may deprotonate the sulfone reagent. The Pt/C catalyst was reusable after the olefination, and this method showed a higher turnover number (TON) and a wider substrate scope than previously reported methods, which demonstrates the high catalytic efficiency of the present method. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Single-wall carbon nanotube chemical attachment at platinum electrodes

International Nuclear Information System (INIS)

Rosario-Castro, Belinda I.; Contes-de-Jesus, Enid J.; Lebron-Colon, Marisabel; Meador, Michael A.; Scibioh, M. Aulice; Cabrera, Carlos R.

2010-01-01

Self-assembled monolayer (SAM) techniques were used to adsorb 4-aminothiophenol (4-ATP) on platinum electrodes in order to obtain an amino-terminated SAM as the base for the chemical attachment of single-wall carbon nanotubes (SWCNTs). A physico-chemical, morphological and electrochemical characterizations of SWCNTs attached onto the modified Pt electrodes was done by using reflection-absorption infrared spectroscopy (RAIR), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, scanning electron microscopy (SEM), atomic force microscopy (AFM), and cyclic voltammetry (CV) techniques. The SWNTs/4-ATP/Pt surface had regions of small, medium, and large thickness of carbon nanotubes with heights of 100-200 nm, 700 nm to 1.5 μm, and 1.0-3.0 μm, respectively. Cyclic voltammetries (CVs) in sulfuric acid demonstrated that attachment of SWNTs on 4-ATP/Pt is markedly stable, even after 30 potential cycles. CV in ruthenium hexamine was similar to bare Pt electrodes, suggesting that SWNTs assembly is similar to a closely packed microelectrode array.

Carbon aerogel electrodes for direct energy conversion

Science.gov (United States)

Mayer, Steven T.; Kaschmitter, James L.; Pekala, Richard W.

1997-01-01

A direct energy conversion device, such as a fuel cell, using carbon aerogel electrodes, wherein the carbon aerogel is loaded with a noble catalyst, such as platinum or rhodium and soaked with phosphoric acid, for example. A separator is located between the electrodes, which are placed in a cylinder having plate current collectors positioned adjacent the electrodes and connected to a power supply, and a pair of gas manifolds, containing hydrogen and oxygen positioned adjacent the current collectors. Due to the high surface area and excellent electrical conductivity of carbon aerogels, the problems relative to high polarization resistance of carbon composite electrodes conventionally used in fuel cells are overcome.

Coatings of Different Carbon Nanotubes on Platinum Electrodes for Neuronal Devices: Preparation, Cytocompatibility and Interaction with Spiral Ganglion Cells.

Science.gov (United States)

Burblies, Niklas; Schulze, Jennifer; Schwarz, Hans-Christoph; Kranz, Katharina; Motz, Damian; Vogt, Carla; Lenarz, Thomas; Warnecke, Athanasia; Behrens, Peter

2016-01-01

Cochlear and deep brain implants are prominent examples for neuronal prostheses with clinical relevance. Current research focuses on the improvement of the long-term functionality and the size reduction of neural interface electrodes. A promising approach is the application of carbon nanotubes (CNTs), either as pure electrodes but especially as coating material for electrodes. The interaction of CNTs with neuronal cells has shown promising results in various studies, but these appear to depend on the specific type of neurons as well as on the kind of nanotubes. To evaluate a potential application of carbon nanotube coatings for cochlear electrodes, it is necessary to investigate the cytocompatibility of carbon nanotube coatings on platinum for the specific type of neuron in the inner ear, namely spiral ganglion neurons. In this study we have combined the chemical processing of as-delivered CNTs, the fabrication of coatings on platinum, and the characterization of the electrical properties of the coatings as well as a general cytocompatibility testing and the first cell culture investigations of CNTs with spiral ganglion neurons. By applying a modification process to three different as-received CNTs via a reflux treatment with nitric acid, long-term stable aqueous CNT dispersions free of dispersing agents were obtained. These were used to coat platinum substrates by an automated spray-coating process. These coatings enhance the electrical properties of platinum electrodes, decreasing the impedance values and raising the capacitances. Cell culture investigations of the different CNT coatings on platinum with NIH3T3 fibroblasts attest an overall good cytocompatibility of these coatings. For spiral ganglion neurons, this can also be observed but a desired positive effect of the CNTs on the neurons is absent. Furthermore, we found that the well-established DAPI staining assay does not function on the coatings prepared from single-wall nanotubes.

Tuning the structure of platinum particles on ceria in situ for enhancing the catalytic performance of exhaust gas catalysts

International Nuclear Information System (INIS)

Gaenzler, Andreas M.; Casapu, Maria; Grunwaldt, Jan-Dierk; Vernoux, Philippe; Loridant, Stephane; Cadete Santos Aires, Francisco J.; Epicier, Thierry; Betz, Benjamin; Hoyer, Ruediger

2017-01-01

A dynamic structural behavior of Pt nanoparticles on the ceria surface under reducing/oxidizing conditions was found at moderate temperatures (<500 C) and exploited to enhance the catalytic activity of Pt/CeO 2 -based exhaust gas catalysts. Redispersion of platinum in an oxidizing atmosphere already occurred at 400 C. A protocol with reducing pulses at 250-400 C was applied in a subsequent step for controlled Pt-particle formation. Operando X-ray absorption spectroscopy unraveled the different extent of reduction and sintering of Pt particles: The choice of the reductant allowed the tuning of the reduction degree/particle size and thus the catalytic activity (CO>H 2 >C 3 H 6 ). This dynamic nature of Pt on ceria at such low temperatures (250-500 C) was additionally confirmed by in situ environmental transmission electron microscopy. A general concept is proposed to adjust the noble metal dispersion (size, structure), for example, during operation of an exhaust gas catalyst. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

Tuning the structure of platinum particles on ceria in situ for enhancing the catalytic performance of exhaust gas catalysts

Energy Technology Data Exchange (ETDEWEB)

Gaenzler, Andreas M.; Casapu, Maria; Grunwaldt, Jan-Dierk [Institute for Chemical Technology and Polymer Chemistry (ITCP), Karlsruhe Institute of Technology (KIT), Karlsruhe (Germany); Vernoux, Philippe; Loridant, Stephane; Cadete Santos Aires, Francisco J. [Institut de Recherches sur la Catalyse et l' Environnement de Lyon, UMR 5256, CNRS, Universite Claude Bernard Lyon 1, Universite de Lyon, Villeurbanne (France); Epicier, Thierry [Materiaux, Ingenierie et Science, UMR 5510, CNRS, INSA de Lyon, Universite de Lyon, Villeurbanne (France); Betz, Benjamin [Umicore AG and Co. KG, Hanau (Germany); Ernst-Berl Institut, Technische Universitaet Darmstadt (Germany); Hoyer, Ruediger [Umicore AG and Co. KG, Hanau (Germany)

2017-10-09

A dynamic structural behavior of Pt nanoparticles on the ceria surface under reducing/oxidizing conditions was found at moderate temperatures (<500 C) and exploited to enhance the catalytic activity of Pt/CeO{sub 2}-based exhaust gas catalysts. Redispersion of platinum in an oxidizing atmosphere already occurred at 400 C. A protocol with reducing pulses at 250-400 C was applied in a subsequent step for controlled Pt-particle formation. Operando X-ray absorption spectroscopy unraveled the different extent of reduction and sintering of Pt particles: The choice of the reductant allowed the tuning of the reduction degree/particle size and thus the catalytic activity (CO>H{sub 2}>C{sub 3}H{sub 6}). This dynamic nature of Pt on ceria at such low temperatures (250-500 C) was additionally confirmed by in situ environmental transmission electron microscopy. A general concept is proposed to adjust the noble metal dispersion (size, structure), for example, during operation of an exhaust gas catalyst. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

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

Energy Technology Data Exchange (ETDEWEB)

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

2010-07-01

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

Growth of carbon nanocone arrays on a metal catalyst: The effect of carbon flux ionization

International Nuclear Information System (INIS)

Levchenko, I.; Khachan, J.; Vladimirov, S. V.; Ostrikov, K.

2008-01-01

The growth of carbon nanocone arrays on metal catalyst particles by deposition from a low-temperature plasma is studied by multiscale Monte Carlo/surface diffusion numerical simulation. It is demonstrated that the variation in the degree of ionization of the carbon flux provides an effective control of the growth kinetics of the carbon nanocones, and leads to the formation of more uniform arrays of nanostructures. In the case of zero degree of ionization (neutral gas process), a width of the distribution of nanocone heights reaches 360 nm with the nanocone mean height of 150 nm. When the carbon flux of 75% ionization is used, the width of the distribution of nanocone heights decreases to 100 nm, i.e., by a factor of 3.6. A higher degree of ionization leads to a better uniformity of the metal catalyst saturation and the nanocone growth, thus contributing to the formation of more height-uniform arrays of carbon nanostructures.

High platinum utilization in ultra-low Pt loaded PEM fuel cell cathodes prepared by electrospraying

Energy Technology Data Exchange (ETDEWEB)

Martin, S.; Garcia-Ybarra, P.L.; Castillo, J.L. [Dept. Fisica Matematica y de Fluidos, Facultad de Ciencias, UNED, Senda del Rey 9, 28040 Madrid (Spain)

2010-10-15

Cathode electrodes for proton exchange membrane fuel cells (PEMFCs) with ultra-low platinum loadings as low as 0.012 mg{sub Pt}cm{sup -2} have been prepared by the electrospray method. The electrosprayed layers have nanostructured fractal morphologies with dendrites formed by clusters (about 100 nm diameter) of a few single catalyst particles rendering a large exposure surface of the catalyst. Optimization of the control parameters affecting this morphology has allowed us to overcome the state of the art for efficient electrodes prepared by electrospraying. Thus, using these cathodes in membrane electrode assemblies (MEAs), a high platinum utilization in the range 8-10 kW g{sup -1} was obtained for the fuel cell operating at 40 C and atmospheric pressure. Moreover, a platinum utilization of 20 kW g{sup -1} was attained under more suitable operating conditions (70 C and 3.4 bar over-pressure). These results substantially improve the performances achieved previously with other low platinum loading electrodes prepared by electrospraying. (author)

Phosphorylated mesoporous carbon as effective catalyst for the selective fructose dehydration to HMF

Energy Technology Data Exchange (ETDEWEB)

Villa, Alberto [Universita di Milano, Italy; Schiavoni, Marco [University of Milan and INFN, Milano, Italy; Fulvio, Pasquale F [ORNL; Mahurin, Shannon Mark [ORNL; Dai, Sheng [ORNL; Mayes, Richard T [ORNL; Veith, Gabriel M [ORNL; Prati, Laura [Universita di Milano, Italy

2013-01-01

Phosphorylated mesoporous carbons (PMCs) have been synthesized using an already reported one pot methodology. These materials have been applied as acidic catalysts in the dehydration of fructose to hydroxymethylfurfural (HMF). PMCs showed better selectivity to HMF compared to sulfonated carbon catalyst (SC) despite lower activity. The concentration of P-O groups correlates to the activity/selectivity of the catalysts; the higher the P-O concentration the higher the activity. However, the higher the P-O content the lower the selectivity to HMF. Indeed a lower concentration of the P-O groups (and even the acidic groups) minimized the degradation of HMF to levulinic acid and the formation of by-products, such as humines. Stability tests showed that these systems deactivate due to the formation of humines, water insoluble by-products derived from the dehydration of fructose, blocking the active site of the catalyst. Increasing the amount of P-O groups, higher amount of humines are formed; therefore carbons containing lower amount of phosphorylated groups, such as P/N-0.25, are less prone to deactivation. Keywords: Phosphorylated mesoporous carbons; fructose dehydration; HMF

Carbon/H-ZSM-5 composites as supports for bi-functional Fischer-Tropsch synthesis catalysts

NARCIS (Netherlands)

Valero-Romero, M.J.; Sartipi, S.; Sun, X.; Rodríguez-Mirasol, J.; Cordero, T.; Kapteijn, F.; Gascon, J.

2016-01-01

Mesoporous H-ZSM-5–carbon composites, prepared via tetrapropylammonium hydroxide (TPAOH) post treatment of H-ZSM-5 followed by deposition of pyrolytic carbon, have been used as the support for the preparation of Co-based Fischer–Tropsch catalysts. The resulting catalysts display an improved

The Edison lamp: O-15 carbon monoxide production in the target

International Nuclear Information System (INIS)

Votaw, J.R.; Satter, M.R.; Sunderland, J.J.; Martin, C.C.; Nickles, R.J.

1986-01-01

A target has been developed for the on line production of C 15 O in order to maximize the available activity for PET studies. The target features an internal carbon filament which is heated to perform the conversion from 15 O-O 2 to either C 15 O or C 15 O 2 . After the initial success of a bare carbon filament, the experiment was repeated using a platinum plated filament in the hope that the platinum would act as a catalyst allowing the conversion reaction to C 15 O to take place at reduced temperatures. Results indicate that the Pt did not alter the conversion, but did greatly increase the temperature to which the filament could be heated and it also increased the filament lifetime. (author)

Carbon and Mo transformations during the synthesis of mesoporous Mo2C/carbon catalysts by carbothermal hydrogen reduction

Science.gov (United States)

Wang, Haiyan; Liu, Shida; Liu, Bing; Montes, Vicente; Hill, Josephine M.; Smith, Kevin J.

2018-02-01

The synthesis of mesoporous Mo2C/carbon catalysts by carbothermal hydrogen reduction is reported. Petroleum coke (petcoke) was activated with KOH at 800 °C to obtain high surface area microporous activated petcoke (APC; 2000 m2/g). The APC was wet impregnated with ammonium heptamolybdate (AHM: 10 wt% Mo), dried and reduced in H2 at temperatures from 400 to 800 °C, to yield Mo2C/APC catalysts. Increased reduction temperature increased the Mo2C yield and the mesoporous volume of the Mo2C/APC. At a reduction temperature of 750 °C the mesopore volume of the catalyst doubled compared to the APC support and accounted for 37% of the total pore volume. Maintaining the final CHR temperature for 90 min further increased the Mo2C yield and mesoporosity of the catalyst. The role of Mo2C in the catalytic hydrogenation of the APC and mesopore generation is demonstrated. The activity of the Mo2C/carbon catalysts in the hydrodeoxygenation of 4-methyl phenol increased with increased CHR temperature and catalyst mesoporosity.

Flame synthesis of carbon nano onions using liquefied petroleum gas without catalyst

International Nuclear Information System (INIS)

Dhand, Vivek; Prasad, J. Sarada; Rao, M. Venkateswara; Bharadwaj, S.; Anjaneyulu, Y.; Jain, Pawan Kumar

2013-01-01

Densely agglomerated, high specific surface area carbon nano onions with diameter of 30–40 nm have been synthesized. Liquefied petroleum gas and air mixtures produced carbon nano onions in diffusion flames without catalyst. The optimized oxidant to fuel ratio which produces carbon nano onions has been found to be 0.1 slpm/slpm. The experiment yielded 70% pure carbon nano onions with a rate of 5 g/h. X-ray diffraction, high-resolution electron microscopy and Raman spectrum reveal the densely packed sp 2 hybridized carbon with (002) semi-crystalline hexagonal graphite reflection. The carbon nano onions are thermally stable up to 600 °C. - Highlights: ►Flame synthesized carbon nano onions with 30–40 nm diameters. ►LPG/air, diffusion type flame used in absence of catalyst to produce nano onions. ►Carbon nano onion production rate is 5 g/hr and with 70% purity.

Synthesis and properties of platinum on multiwall carbon nanotube modified by chitosan

Science.gov (United States)

Fikriyyah, A. K.; Chaldun, E. R.; Indriyati

2018-03-01

Platinum nanoparticles on multiwall carbon nanotubes (Pt/MWCNT) play an important role in fuel cell to convert the chemical energy from a fuel into electricity. In this study, Pt/MWCNT electrocatalysts were prepared by chemical reduction of the metal salts in chitosan as the support. Firstly, commercial MWCNTs were functionalized by oxidative process using a mixture of nitric acid and sulfuric acid. Then, functionalized MWCNTs were mixed with chitosan-acetic acid solution to conduct grafting reaction with NH2 groups in chitosan by solution polymerization method. Platinum nanoparticles were loaded onto the surface of the MWCNTs after hexachloroplatinic acid was reduced by sodium hydroxide solution. The result showed that Pt was attached on MWCNT based on analysis from EDS, XRD, and UV Vis Spectroscopy. UV Vis analysis indicates the plasmon absorbance band of Pt nanoparticles in Pt/MWCNT, while XRD analysis confirmed the size of Pt particle in nanometer. This elucidates the potential procedure to synthesize Pt/MWCNT using chitosan.

Hydroisomerization of n-dodecane over Pt/Al-MCM-48 catalysts.

Science.gov (United States)

Yun, Soyoung; Park, Young-Kwon; Jeong, Soon-Yong; Han, Jeongsik; Jeon, Jong-Ki

2014-04-01

The objective of this study is to evaluate the catalytic potential of Pt/Al-MCM-48 catalysts in hydroisomerization of n-dodecane. The effects of the Si/Al ratio and platinum loading on the acid characteristics of Al-MCM-48 and the catalytic performance in n-dodecane hydroisomerization were analyzed. The catalysts were characterized by X-ray diffraction, nitrogen adsorption, infrared spectroscopy of pyridine adsorption, and temperature programmed desorption of ammonia. The number of weak strength acid sites on Al-MCM-48 increased with 0.5 wt% platinum loading. The weak strength acid sites of Pt/Al-MCM-48 catalysts were ascribed to Lewis acid sites, which can be confirmed by NH3-TPD and FTIR spectra of pyridine adsorption. Iso-dodecane can be produced with high selectivity in n-dodecane hydrosisomerization over Pt/Al-MCM-48 catalysts. This is attributed to the mild acidic properties of Pt/Al-MCM-48 catalysts.

Preparation of Monodispersed Fe-Mo Nanoparticles as the Catalyst for CVD Synthesis of Carbon Nanotubes

National Research Council Canada - National Science Library

Li, Yan; Liu, Jie; Wang, Yongqian; Wang, Zhong L

2001-01-01

...particles were systematically studied. The prepared nanoparticles were used as catalysts for single-walled carbon nanotube growth and the results indicate that there is an upper limit for the size of the catalyst particles to nucleate singlewalled carbon nanotubes.

Growth of uniform thin-walled carbon nanotubes with spin-coated Fe catalyst and the correlation between the pre-growth catalyst size and the nanotube diameter

International Nuclear Information System (INIS)

Seah, Choon-Ming; Chai, Siang-Piao; Ichikawa, Satoshi; Mohamed, Abdul Rahman

2013-01-01

Single-walled carbon nanotubes (CNTs) and double-walled CNTs with a selectivity of 93 % were obtained by means of the novel homemade iron catalysts which were spin coated on silicon wafer. The average diameters of the iron particles prepared from the colloidal solutions containing 30, 40, 50, 60, and 70 mmol/L of iron nitrate were 8.2, 5.1, 20.8, 32.2, and 34.7 nm, respectively, and growing thin-walled CNTs with the average diameters of 4.1, 2.2, 9.2, 11.1, and 18.1 nm, respectively. The diameters of the CNTs were correlated with the geometric sizes of the pre-growth catalyst particles. Thin-walled CNTs were found to have a catalyst mean diameter-to-CNT average diameter ratio of 2.31. Iron carbide was formed after the growth of CNTs, and it is believed that during the growth of CNTs, carbon source decomposed and deposited on the surface of catalyst, followed by the diffusion of surface carbon into the iron catalyst particles, resulting in carbon supersaturation state before the growth of CNTs.

Solar-Driven Hydrogen Peroxide Production Using Polymer-Supported Carbon Dots as Heterogeneous Catalyst

Science.gov (United States)

Gogoi, Satyabrat; Karak, Niranjan

2017-10-01

Safe, sustainable, and green production of hydrogen peroxide is an exciting proposition due to the role of hydrogen peroxide as a green oxidant and energy carrier for fuel cells. The current work reports the development of carbon dot-impregnated waterborne hyperbranched polyurethane as a heterogeneous photo-catalyst for solar-driven production of hydrogen peroxide. The results reveal that the carbon dots possess a suitable band-gap of 2.98 eV, which facilitates effective splitting of both water and ethanol under solar irradiation. Inclusion of the carbon dots within the eco-friendly polymeric material ensures their catalytic activity and also provides a facile route for easy catalyst separation, especially from a solubilizing medium. The overall process was performed in accordance with the principles of green chemistry using bio-based precursors and aqueous medium. This work highlights the potential of carbon dots as an effective photo-catalyst.

Behavior of oxidized platinum nanoparticles on an aligned carbon nanotube forest

Energy Technology Data Exchange (ETDEWEB)

Matsuda, Keita, E-mail: matsuda.keita@c.mbox.nagoya-u.ac.jp; Norimatsu, Wataru [Department of Applied Chemistry, Nagoya University, Nagoya 464-8603 (Japan); Arai, Shigeo; Kusunoki, Michiko [Institute of Materials and Systems for Sustainability, Nagoya University, Nagoya 464-8603 (Japan)

2016-10-14

We observed and analyzed the behavior of platinum nanoparticles (PtNPs) supported on aligned-carbon nanotubes (CNTs) at high temperatures by X-ray photoelectron spectroscopy and high-resolution transmission electron microscope observations. We found that the PtNPs moved toward the inner-side along each CNT on which they were deposited. The mechanism of this behavior is related to the redox reaction of Pt with the carbon atoms in the CNT. We also performed in-situ observation of this process at a high temperature using an environmental transmission electron microscope under an oxygen atmosphere. We found that the PtNPs penetrated down into a high-density aligned CNT forest along the tube axis and that the PtNPs changed their shape to fit the structure of the CNTs during their movement.

The Use of C-MnO2 as Hybrid Precursor Support for a Pt/C-MnxO1+x Catalyst with Enhanced Activity for the Methanol Oxidation Reaction (MOR

Directory of Open Access Journals (Sweden)

Alessandro H.A. Monteverde Videla

2015-07-01

Full Text Available Platinum (Pt nanoparticles are deposited on a hybrid support (C-MnO2 according to a polyol method. The home-made catalyst, resulted as Pt/C-MnxO1+x, is compared with two different commercial platinum based materials (Pt/C and PtRu/C. The synthesized catalyst is characterized by means of FESEM, XRD, ICP-MS, XPS and μRS analyses. MnO2 is synthesized and deposited over a commercial grade of carbon (Vulcan XC72 by facile reduction of potassium permanganate in acidic solution. Pt nanoparticles are synthesized on the hybrid support by a polyol thermal assisted method (microwave irradiation, followed by an annealing at 600 °C. The obtained catalyst displays a support constituted by a mixture of manganese oxides (Mn2O3 and Mn3O4 with a Pt loading of 19 wt. %. The electro-catalytic activity towards MOR is assessed by RDE in acid conditions (0.5 M H2SO4, evaluating the ability to oxidize methanol in 1 M concentration. The synthesized Pt/C-MnxO1+x catalyst shows good activity as well as good stability compared to the commercial Pt/C based catalyst.

The role of Ni in sulfided carbon-supported Ni-Mo hydrodesulfurization catalysts

NARCIS (Netherlands)

Bouwens, S.M.A.M.; Barthe-Zahir, N.; Beer, de V.H.J.; Prins, R.

1991-01-01

The thiophene hydrodesulfurization activities of Ni and Ni---Mo sulfide catalysts supported on activated carbon were measured at atmospheric pressure and the catalyst structures were studied by means of X-ray photoelectron spectroscopy, dynamic oxygen chemisorption, and chemical sulfur analysis. The

Engineering catalytic activity via ion beam bombardment of catalyst supports for vertically aligned carbon nanotube growth

Science.gov (United States)

Islam, A. E.; Nikolaev, P.; Amama, P. B.; Zakharov, D.; Sargent, G.; Saber, S.; Huffman, D.; Erford, M.; Semiatin, S. L.; Stach, E. A.; Maruyama, B.

2015-09-01

Carbon nanotube growth depends on the catalytic activity of metal nanoparticles on alumina or silica supports. The control on catalytic activity is generally achieved by variations in water concentration, carbon feed, and sample placement on a few types of alumina or silica catalyst supports obtained via thin film deposition. We have recently expanded the choice of catalyst supports by engineering inactive substrates like c-cut sapphire via ion beam bombardment. The deterministic control on the structure and chemistry of catalyst supports obtained by tuning the degree of beam-induced damage have enabled better regulation of the activity of Fe catalysts only in the ion beam bombarded areas and hence enabled controllable super growth of carbon nanotubes. A wide range of surface characterization techniques were used to monitor the catalytically active surface engineered via ion beam bombardment. The proposed method offers a versatile way to control carbon nanotube growth in patterned areas and also enhances the current understanding of the growth process. With the right choice of water concentration, carbon feed and sample placement, engineered catalyst supports may extend the carbon nanotube growth yield to a level that is even higher than the ones reported here, and thus offers promising applications of carbon nanotubes in electronics, heat exchanger, and energy storage.

Process intensification by combination of activated carbon supported catalysts and alternative energy sources

OpenAIRE

Calvino Casilda, Vanesa; Pérez-Mayoral, E.

2014-01-01

[EN] Activated carbons are well known for their catalytic properties and for being used as a catalyst support in heterogeneous catalysis. Activated carbons possess most of the desired properties of a catalyst support; inertness towards unwanted reactions, stability under regeneration and reaction conditions, suitable mechanical properties, tunable surface area, porosity, and the possibility of being manufactured in different size and shape. On the other hand, the in...

Flame synthesis of carbon nano onions using liquefied petroleum gas without catalyst

Energy Technology Data Exchange (ETDEWEB)

Dhand, Vivek, E-mail: vivekdhand2012@gmail.com [Centre for Knowledge Management of Nanoscience and Technology, 12-5-32/8, Vijayapuri Colony, Tarnaka, Secunderabad-500 017, A.P (India); Prasad, J. Sarada; Rao, M. Venkateswara [Centre for Environment, Institute of Science and Technology, Jawaharlal Nehru Technological University, Kukatpally, Hyderabad 500 085 (India); Bharadwaj, S. [Department of Physics, CVR College of Engineering and Osmania University, Hyderabad 501510, A.P (India); Anjaneyulu, Y. [TLGVRC, Jackson State University, JSU Box 18739, Jackson, MS 39217-0939 (United States); Jain, Pawan Kumar [International Advanced Research Centre for Powder Metallurgy and New Materials (ARCI), Balapur PO, Hyderabad 500005, Andhra Pradesh (India)

2013-03-01

Densely agglomerated, high specific surface area carbon nano onions with diameter of 30-40 nm have been synthesized. Liquefied petroleum gas and air mixtures produced carbon nano onions in diffusion flames without catalyst. The optimized oxidant to fuel ratio which produces carbon nano onions has been found to be 0.1 slpm/slpm. The experiment yielded 70% pure carbon nano onions with a rate of 5 g/h. X-ray diffraction, high-resolution electron microscopy and Raman spectrum reveal the densely packed sp{sup 2} hybridized carbon with (002) semi-crystalline hexagonal graphite reflection. The carbon nano onions are thermally stable up to 600 Degree-Sign C. - Highlights: Black-Right-Pointing-Pointer Flame synthesized carbon nano onions with 30-40 nm diameters. Black-Right-Pointing-Pointer LPG/air, diffusion type flame used in absence of catalyst to produce nano onions. Black-Right-Pointing-Pointer Carbon nano onion production rate is 5 g/hr and with 70% purity.

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.

Electrochemical removal of hexavalent chromium from wastewater using Platinum-Iron/Iron-carbon nanotubes and bipolar Electrodes

Directory of Open Access Journals (Sweden)

Hoshyar Hossini

2015-01-01

Full Text Available Background: In recent decades, electrocoagulation (EC has engrossed much attention as an environmental-friendly and effectiveness process. In addition, the EC process is a potential suitable way for treatment of wastewater with concern to costs and environment. The object of this study was electrochemical evaluation of chromium removal from industrial wastewater using Platinum and carbon nanotubes electrodes. Materials and Methods: The effect of key variables including pH (3–9, hexavalent chromium concentration (50–300 mg/l, supporting electrolyte (NaCl, KCl, Na2CO3 and KNO3 and its dosage, Oxidation-Reduction variations, sludge generation rate and current density (2–20 mA/cm2 was determined. Results: Based on experimental data, optimum conditions were determined in 20, 120 min, pH 3, NaCl 0.5% and 100 mg/L initial concentration of chromium. Conclusions: Removal of hexavalent chromium from the wastewater could be successfully performanced using Platinum-Iron/Iron-carbon nanotubes and bipolar Electrodes.

Enhanced activity and durability of platinum anode catalyst by the modification of cobalt phosphide for direct methanol fuel cells

International Nuclear Information System (INIS)

Li, Xiang; Wang, Hongjuan; Yu, Hao; Liu, Ziwu; Wang, Haihui; Peng, Feng

2015-01-01

Graphical abstract: A novel Pt/CoP/CNTs electrocatalyst with has been designed and prepared, which exhibits high activity and stability for methanol oxidation reaction. - Highlights: • Pt-cobalt phosphide catalyst supported on carbon nanotubes (Pt/CoP/CNTs) is designed. • Pt/CoP/CNTs exhibit high activity and stability for methanol oxidation reaction(MOR). • The effect of CoP content on electrocatalytic performances for MOR is studied. • CoP decreases the Pt particle size and increases the electrochemical surface areas. • The interaction between Pt and CoP is evidenced by X-ray photoelectron spectroscopy. - Abstract: In this study, carbon nanotubes (CNTs) supported Pt-cobalt phosphide (CoP) electrocatalyst (Pt/CoP/CNTs) is designed and prepared for methanol oxidation (MOR) for the first time. The modification of CoP decreases the Pt particle size significantly and increases the electrochemical surface areas due to the interaction between Pt and CoP, which is evidenced by transmission electron microscopy, X-ray diffraction and X-ray photoelectron spectroscopy. Among all these catalysts, Pt/4%CoP/CNTs catalyst exhibits the best MOR activity of 1600 mA mg −1 Pt , which is six times that of Pt/CNTs. Moreover, this catalyst also exhibits the higher onset current density and steady current density than the other Pt-based catalysts. The work provides a promising method to develop the highly active and stable Pt-based catalyst for direct methanol fuel cells.

A phototactic micromotor based on platinum nanoparticle decorated carbon nitride.

Science.gov (United States)

Ye, Zhenrong; Sun, Yunyu; Zhang, Hui; Song, Bo; Dong, Bin

2017-11-30

In this paper, we report a unique phototactic (both positive and negative) micromotor based on platinum nanoparticle decorated carbon nitride. The phototaxis relies on the self-diffusiophoretic mechanism and different surface modifications. The micromotor reported in the current study does not require the addition of any external fuels and shows versatile motion behaviour, i.e. start, stop, directional and programmable motion, which is controlled by light. In addition, since the actuation of the precipitated micromotors at the bottom of a solution using light results in the opacity changes from transparent to translucent, we anticipate that the current micromotor may have potential application in the field of smart windows.

Recent progress in solution plasma-synthesized-carbon-supported catalysts for energy conversion systems

Science.gov (United States)

Lun Li, Oi; Lee, Hoonseung; Ishizaki, Takahiro

2018-01-01

Carbon-based materials have been widely utilized as the electrode materials in energy conversion and storage technologies, such as fuel cells and metal-air batteries. In these systems, the oxygen reduction reaction is an important step that determines the overall performance. A novel synthesis route, named the solution plasma process, has been recently utilized to synthesize various types of metal-based and heteroatom-doped carbon catalysts. In this review, we summarize cutting-edge technologies involving the synthesis and modeling of carbon-supported catalysts synthesized via solution plasma process, followed by current progress on the electrocatalytic performance of these catalysts. This review provides the fundamental and state-of-the-art performance of solution-plasma-synthesized electrode materials, as well as the remaining scientific and technological challenges for this process.

Novel synthesis of highly durable and active Pt catalyst encapsulated in nitrogen containing carbon for polymer electrolyte membrane fuel cell

Science.gov (United States)

Lee, Hyunjoon; Sung, Yung-Eun; Choi, Insoo; Lim, Taeho; Kwon, Oh Joong

2017-09-01

Novel synthesis of a Pt catalyst encapsulated in a N-containing carbon layer for use in a polymer electrolyte membrane fuel cell is described in this study. A Pt-aniline complex, formed by mixing Pt precursor and aniline monomer, was used as the source of Pt, C, and N. Heat treatment of the Pt-aniline complex with carbon black yielded 5 nm Pt nanoparticles encapsulated by a N-containing carbon layer originating from aniline carbonization. The synthesized Pt catalyst exhibited higher mass specific activity to oxygen reduction reaction than that shown by conventional Pt/C catalyst because pyridinic N with graphitic carbon in the carbon layer provided active sites for oxygen reduction reaction in addition to those provided by Pt. In single cell testing, initial performance of the synthesized catalyst was limited because the thick catalyst layer increased resistance related to mass transfer. However, it was observed that the carbon layer successfully prevented Pt nanoparticles from growing via agglomeration and Ostwald ripening under fuel cell operation, thereby improving durability. Furthermore, a mass specific performance of the synthesized catalyst higher than that of a conventional Pt/C catalyst was achieved by modifying the synthesized catalyst's layer thickness.

Synthesis of Carbon Nano tubes Using Anadara Granosa Shells as Catalyst Support

International Nuclear Information System (INIS)

Mohd Zobir Hussein; Mohd Zobir Hussein; Salwani Asyikin Zakarya; Siti Halimah Sarijo

2011-01-01

The synthesis of carbon nano tubes (CNTs) by chemical vapor deposition (CVD) method using natural calcite prepared from Anadara granosa shells (CS), as metal catalyst support was studied. Hexane and iron were used as carbon precursor and catalyst, respectively. The as synthesised CNTs was characterized using XRD, TEM and FESEM. From the XRD patterns the CNTs peak can be seen more incisive after purification process and from the FESEM micrographs the CNTs can be seen as a bunch of rope-like structures. (author)

Hydrogenation of carbon monoxide on WO/sub 3/-Supported ruthenium catalysts

Energy Technology Data Exchange (ETDEWEB)

Yoshinari, Tomohiro; Suganuma, Fujio; Sera, Chikara

1988-01-01

In this study, a WO/sub 3/-supported catalyst was prepared to conduct hydrogenation of CO for examining the product distribution and composition of hydrocarbons, using a gamma-alumina-supported catalyst for comparison. These catalysts were used under pressure to conduct a distributive reaction and the desorbing behavior of CO or H/sub 2/ at elevated temperature was measured to examine the influence of the type of carrier or the method of preparation on the activity and the distribution of products formed. The WO/sub 3/-supported catalyst gave a carbon chain length distribution that did not comply with the rule of Schulz-Flory, giving a composition richer in the isomers. Carbon number distribution is affected by Ru-dispersion, and the selectivity of isomers depends on the acidity of the carrier. Formed products distribution of the WO/sub 3/-supported reaction is attributable to the secondary reaction, which relates to the acidic point of the carrier, of the primary product formed on the metal. (7 figs, 4 tabs, 18 refs)

Carbon Nanofiber Supported Transition-Metal Carbide Catalysts for the Hydrodeoxygenation of Guaiacol

NARCIS (Netherlands)

Jongerius, A.; Gosselink, R.W.; Dijkstra, J.; Bitter, J.H.; Bruijnincx, P.C.A.; Weckhuysen, B.M.

2013-01-01

Hydrodeoxygenation (HDO) studies over carbon nanofiber-supported (CNF) W2C and Mo2C catalysts were performed on guaiacol, a prototypical substrate to evaluate the potential of a catalyst for valorization of depolymerized lignin streams. Typical reactions were executed at 55 bar hydrogen pressure

Synergistic effect of Brønsted acid and platinum on purification of automobile exhaust gases.

Science.gov (United States)

Fu, Wei; Li, Xin-Hao; Bao, Hong-Liang; Wang, Kai-Xue; Wei, Xiao; Cai, Yi-Yu; Chen, Jie-Sheng

2013-01-01

The catalytic purification of automobile exhaust gases (CO, NOx and hydrocarbons) is one of the most practiced conversion processes used to lower the emissions and to reduce the air pollution. Nevertheless, the good performance of exhaust gas purification catalysts often requires the high consumption of noble metals such as platinum. Here we report that the Brønsted acid sites on the external surface of a microporous silicoaluminophosphate (SAPO) act as a promoter for exhaust gas purification, effectively cutting the loading amount of platinum in the catalyst without sacrifice of performance. It is revealed that in the Pt-loaded SAPO-CHA catalyst, there exists a remarkable synergistic effect between the Brønsted acid sites and the Pt nanoparticles, the former helping to adsorb and activate the hydrocarbon molecules for NO reduction during the catalytic process. The thermal stability of SAPO-CHA also makes the composite catalyst stable and reusable without activity decay.

Synergistic effect of Brønsted acid and platinum on purification of automobile exhaust gases

Science.gov (United States)

Fu, Wei; Li, Xin-Hao; Bao, Hong-Liang; Wang, Kai-Xue; Wei, Xiao; Cai, Yi-Yu; Chen, Jie-Sheng

2013-01-01

The catalytic purification of automobile exhaust gases (CO, NOx and hydrocarbons) is one of the most practiced conversion processes used to lower the emissions and to reduce the air pollution. Nevertheless, the good performance of exhaust gas purification catalysts often requires the high consumption of noble metals such as platinum. Here we report that the Brønsted acid sites on the external surface of a microporous silicoaluminophosphate (SAPO) act as a promoter for exhaust gas purification, effectively cutting the loading amount of platinum in the catalyst without sacrifice of performance. It is revealed that in the Pt-loaded SAPO-CHA catalyst, there exists a remarkable synergistic effect between the Brønsted acid sites and the Pt nanoparticles, the former helping to adsorb and activate the hydrocarbon molecules for NO reduction during the catalytic process. The thermal stability of SAPO-CHA also makes the composite catalyst stable and reusable without activity decay. PMID:23907148

Pt/XC-72 catalysts coated with nitrogen-doped carbon (Pt/XC-72@C–N) for methanol electro-oxidation

Energy Technology Data Exchange (ETDEWEB)

Cao, Jun; Chu, Yuanyuan; Tan, Xiaoyao, E-mail: cestanxy@aliyun.com

2014-03-01

Pt/XC-72 catalysts coated with N-doped carbon (denoted as Pt/XC-72@C–N) for the electro-oxidation of methanol are prepared through a combined microwave-assisted polyol with in-situ carbonization of N-doped carbon coating process using polyvinylpyrrolidone (PVP), 1-vinyl-3-ethylimidazolium nitrate (VEIN) or 1-ethyl-3-methylimidazolium dicyanamide (EMID) ionic liquid as the N-doped carbon precursor. X-ray diffraction, energy dispersive of X-ray, transmission electron microscopy, X-ray photoelectron spectroscopy, cyclic voltammograms and accelerated aging test techniques are applied to characterize the structure and the electro-catalytic activity of the catalysts. The results show that the Pt particles with the average size of around 2.5 nm are highly dispersed in face-centered cubic crystal structure in the carbon support. The structure of the N-doped carbon coating precursor has considerable influence on the electro-catalytic performance of the catalysts. The resultant catalyst with EMID ionic liquid as the N-doped carbon source exhibits 115.9 m{sup 2} g{sup −1}Pt electrochemical surface area (ESA) and 0.66 A mg{sup −1}Pt catalytic activity towards the electro-oxidation of methanol, which are 1.37 times the ESA and 1.35 times the catalytic activity of the PVP-derived catalyst, and 2.02 times the electrochemical surface area and 1.94 times the catalytic activity of the VEIN-derived catalyst. The appropriate amount of the EMID ionic liquid used in the catalyst synthesis process is around 10 uL for 100 mg XC-72 support so as to obtain the highest electro-catalytic activity. - Highlights: • N-doped carbon coated Pt/C catalyst is prepared for methanol electro-oxidation. • Pt/XC-72@C–N exhibits excellent electrocatalytic activity over uncoated catalysts. • Ionic liquid with anionic cyano groups is most suitable as N-doped carbon precursor. • The appropriate amount of ionic liquid for coating is around 10 μL for 100 mg carbon.

Platinum supported on titanium–ruthenium oxide is a remarkably stable electrocatayst for hydrogen fuel cell vehicles

Science.gov (United States)

Parrondo, Javier; Han, Taehee; Niangar, Ellazar; Wang, Chunmei; Dale, Nilesh; Adjemian, Kev; Ramani, Vijay

2014-01-01

We report a unique and highly stable electrocatalyst—platinum (Pt) supported on titanium–ruthenium oxide (TRO)—for hydrogen fuel cell vehicles. The Pt/TRO electrocatalyst was exposed to stringent accelerated test protocols designed to induce degradation and failure mechanisms identical to those seen during extended normal operation of a fuel cell automobile—namely, support corrosion during vehicle startup and shutdown, and platinum dissolution during vehicle acceleration and deceleration. These experiments were performed both ex situ (on supports and catalysts deposited onto a glassy carbon rotating disk electrode) and in situ (in a membrane electrode assembly). The Pt/TRO was compared against a state-of-the-art benchmark catalyst—Pt supported on high surface-area carbon (Pt/HSAC). In ex situ tests, Pt/TRO lost only 18% of its initial oxygen reduction reaction mass activity and 3% of its oxygen reduction reaction-specific activity, whereas the corresponding losses for Pt/HSAC were 52% and 22%. In in situ-accelerated degradation tests performed on membrane electrode assemblies, the loss in cell voltage at 1 A · cm−2 at 100% RH was a negligible 15 mV for Pt/TRO, whereas the loss was too high to permit operation at 1 A · cm−2 for Pt/HSAC. We clearly show that electrocatalyst support corrosion induced during fuel cell startup and shutdown is a far more potent failure mode than platinum dissolution during fuel cell operation. Hence, we posit that the need for a highly stable support (such as TRO) is paramount. Finally, we demonstrate that the corrosion of carbon present in the gas diffusion layer of the fuel cell is only of minor concern. PMID:24367118

Electrochemical titration of hydrogen adsorbed on supported platinum catalysts

Czech Academy of Sciences Publication Activity Database

Paseka, Ivo

2007-01-01

Roč. 329, - (2007), s. 161-163 ISSN 0926-860X R&D Projects: GA ČR GA104/03/0409 Institutional research plan: CEZ:AV0Z40320502 Keywords : platinum * hydrogen adsorption * specific surface area Subject RIV: CA - Inorganic Chemistry Impact factor: 3.166, year: 2007

Platinum-Niobium(V Oxide/Carbon Nanocomposites Prepared By Microwave Synthesis For Ethanol Oxidation

Directory of Open Access Journals (Sweden)

Virginija KEPENIENĖ

2016-05-01

Full Text Available In the present work, Pt nanoparticles were deposited by means of microwave synthesis on the primary carbon supported Nb2O5 composite which was prepared in two different ways: (A by dispersion of Nb2O5 and carbon with the mass ratio equal to 1:1 in a 2-propanol solution by ultrasonication for 30 min. with further desiccation of the mixture and (B by heating the Nb2O5/C composite obtained according to the procedure (A at 500 °C for 2 h. The transmission electron microscopy was used to determine the shape and the size of catalyst particles. X-ray diffraction and inductively coupled plasma optical emission spectroscopy were employed to characterize the structure and composition of the synthesized catalysts. The electrocatalytic activity of the synthesized catalysts towards the oxidation of ethanol in an alkaline medium was investigated by means of cyclic voltammetry.DOI: http://dx.doi.org/10.5755/j01.ms.22.2.8609

Oxidation catalyst

Science.gov (United States)

Ceyer, Sylvia T.; Lahr, David L.

2010-11-09

The present invention generally relates to catalyst systems and methods for oxidation of carbon monoxide. The invention involves catalyst compositions which may be advantageously altered by, for example, modification of the catalyst surface to enhance catalyst performance. Catalyst systems of the present invention may be capable of performing the oxidation of carbon monoxide at relatively lower temperatures (e.g., 200 K and below) and at relatively higher reaction rates than known catalysts. Additionally, catalyst systems disclosed herein may be substantially lower in cost than current commercial catalysts. Such catalyst systems may be useful in, for example, catalytic converters, fuel cells, sensors, and the like.

High Performance Fe- and N- Doped Carbon Catalyst with Graphene Structure for Oxygen Reduction

Science.gov (United States)

Peng, Hongliang; Mo, Zaiyong; Liao, Shijun; Liang, Huagen; Yang, Lijun; Luo, Fan; Song, Huiyu; Zhong, Yiliang; Zhang, Bingqing

2013-05-01

Proton exchange membrane fuel cells are promising candidates for a clean and efficient energy conversion in the future, the development of carbon based inexpensive non-precious metal ORR catalyst has becoming one of the most attractive topics in fuel cell field. Herein we report a Fe- and N- doped carbon catalyst Fe-PANI/C-Mela with graphene structure and the surface area up to 702 m2 g-1. In 0.1 M HClO4 electrolyte, the ORR onset potential for the catalyst is high up to 0.98 V, and the half-wave potential is only 60 mV less than that of the Pt/C catalyst (Loadings: 51 μg Pt cm-2). The catalyst shows high stability after 10,000 cyclic voltammetry cycles. A membrane electrode assembly made with the catalyst as a cathode is tested in a H2-air single cell, the maximum power density reached ~0.33 W cm2 at 0.47 V.

Iodometric determination of platinum(4) using amperometry

International Nuclear Information System (INIS)

Zakharov, V.A.; Gavva, N.F.; Songina, O.A.

1976-01-01

The possibility of iodometric determination of platinum (4) by amperometric titration has been investigated. Titration has been conducted at zero potential of platinum reference electrode. Voltampere curves and absorption spectra of the solutions have been recorded to elucidate the nature of platinum (4) interaction with iodide-ion. It has been established that in the case of small excess of iodide complex [PtI 6 ] 2- is formed. When there is a considerable excess of KI, platinum (4) is reduced to Pt(2) with the formation of [PtI 4 ] 2 - and liberation of free iodine. Optimal for iodometric titration of Pt(4) is the use of acetate ot phosphate background solution with pH 6-8 with respect to 1M KI which is attained by adding 3 g of solid KI to 20 ml of the solution being titrated. Under these conditions the limit of platinum detection is 0.5 mkg/ml. Determination of Pt (4) is not hindered by the presence of 200-fold amounts of Cr(6), V(5), and Ni(2) as well as by 20-10-fold amounts of As(5), Sb(5), Se(4), Te(4), Rh(3), and Ir(3), Determination is hindered by the presence of Pd(2), Fe(3), Ir(4), and Cu(2) which, however, can easily be overcome. The possibility has been shown of using the developed technique for analysis of platinum catalysts and alloys

Functionalization of multi-walled carbon nanotubes with iron phthalocyanine via a liquid chemical reaction for oxygen reduction in alkaline media

Science.gov (United States)

Yan, Xiaomei; Xu, Xiao; Liu, Qin; Guo, Jia; Kang, Longtian; Yao, Jiannian

2018-06-01

Iron single-atom catalyst in form of iron-nitrogen-carbon structure possesses the excellent catalytic activity in various chemical reactions. However, exploring a sustainable and stable single-atom metal catalyst still faces a great challenge due to low yield and complicated synthesis. Here, we report a functional multi-wall carbon nanotubes modified with iron phthalocyanine molecules via a liquid chemical reaction and realize the performance of similar single-atom catalysis for oxygen reduction reaction. A serial of characterizations strongly imply the structure change of iron phthalocyanine molecule and its close recombination with multi-wall carbon nanotubes, which are in favor of ORR catalysis. Compared to commercial platinum-carbon catalyst, composites exhibit superior activity for oxygen reduction reaction with higher half-wave potential (0.86 V), lower Tafel slope (38 mV dec-1), higher limiting current density and excellent electrochemical stability. The corresponding Zinc-air battery also presents higher maximum power density and discharge stability. Therefore, these findings provide a facile route to synthesize a highly efficient non-precious metal carbon-based catalyst.

Upgrading of glycerol from biodiesel synthesis with dimethyl carbonate on reusable Sr–Al mixed oxide catalysts

International Nuclear Information System (INIS)

Algoufi, Y.T.; Akpan, U.G.; Kabir, G.; Asif, M.; Hameed, B.H.

2017-01-01

Highlights: • Catalytic transesterification with dimethyl carbonate (DMC) converts glycerol into glycerol carbonate (GLC). • DMC and Sr_x–Al catalysts affect the reaction mechanisms that convert glycerol into GLC. • The morphology and textural structure of Sr_x–Al catalysts perpetuate catalytic activity. • The atomic ratio of Sr/Al has a unique effect on Sr–Al catalytic activity. • Sr_0_._5–Al catalyst exhibits limited leaching after five reaction cycles. - Abstract: The high demand for renewable energy has led to the upsurge of methanol-assisted biodiesel synthesis. Therefore, glycerol as a byproduct entered the waste stream given the oversupply of biodiesel to the market. The dimethyl carbonate (DMC)-assisted transesterification of glycerol on a catalyst has been a popular approach for converting glycerol into valuable glycerol carbonate (GLC). The synthesis of GLC from the DMC-assisted transesterification of glycerol on mixed oxide catalysts (Sr_x–Al) with different Sr/Al ratios was examined in this study. A glycerol conversion of 99.4% and a GLC yield of 100% were achieved in a catalyst with Sr/Al = 0.5 (Sr_0_._5–Al). Both values are higher than those in catalysts synthesized with Sr/Al = 0.25 and 0.75. The Sr_0_._5–Al catalyst withstood five transesterification reaction cycles without a serious deactivation induced by the leaching of active SrO. Therefore, the Sr_0_._5–Al catalyst is suitable for consecutive uses in the DMC-assisted transesterification of glycerol with DMC into GLC.

Sequential Electrodeposition of Platinum-Ruthenium at Boron-Doped Diamond Electrodes for Methanol Oxidation

Directory of Open Access Journals (Sweden)

Ileana González-González

2011-01-01

Full Text Available Sequential electrodeposition of Pt and Ru on boron-doped diamond (BDD films, in 0.5 M H2SO4 by cyclic voltammetry, has been prepared. The potential cycling, in the aqueous solutions of the respective metals, was between 0.00 and 1.00 V versus Ag/AgCl. The catalyst composites, Pt and PtRu, deposited on BDD film substrates, were tested for methanol oxidation. The modified diamond surfaces were also characterized by scanning electron microscopy-X-ray fluorescence-energy dispersive spectroscopy, X-ray photoelectron spectroscopy, and Auger electron spectroscopy. The scanning Auger electron spectroscopy mapping showed the ruthenium signal only in areas where platinum was electrodeposited. Ruthenium does not deposit on the oxidized diamond surface of the boron-doped diamond. Particles with 5–10% of ruthenium with respect to platinum exhibited better performance for methanol oxidation in terms of methanol oxidation peak current and chronoamperometric current stability. The electrogenerated •OH radicals on BDD may interact with Pt surface, participating in the methanol oxidation as shown in oxidation current and the shift in the peak position. The conductive diamond surface is a good candidate as the support for the platinum electrocatalyst, because it ensures catalytic activity, which compares with the used carbon, and higher stability under severe anodic and cathodic conditions.

Engineering Platinum Alloy Electrocatalysts in Nanoscale for PEMFC Application

Energy Technology Data Exchange (ETDEWEB)

He, Ting [Idaho National Laboratory

2016-03-01

Fuel cells are expected to be a key next-generation energy source used for vehicles and homes, offering high energy conversion efficiency and minimal pollutant emissions. However, due to large overpotentials on anode and cathode, the efficiency is still much lower than theoretically predicted. During the past decades, considerable efforts have been made to investigate synergy effect of platinum alloyed with base metals. But, engineering the alloy particles in nanoscale has been a challenge. Most important challenges in developing nanostructured materials are the abilities to control size, monodispersity, microcomposition, and even morphology or self-assembly capability, so called Nanomaterials-by-Design, which requires interdisciplinary collaborations among computational modeling, chemical synthesis, nanoscale characterization as well as manufacturing processing. Electrocatalysts, particularly fuel cell catalysts, are dramatically different from heterogeneous catalysts because the surface area in micropores cannot be electrochemically controlled on the same time scale as more transport accessible surfaces. Therefore, electrocatalytic architectures need minimal microporous surface area while maximizing surfaces accessible through mesopores or macropores, and to "pin" the most active, highest performance physicochemical state of the materials even when exposed to thermodynamic forces, which would otherwise drive restructuring, crystallization, or densification of the nanoscale materials. In this presentation, results of engineering nanoscale platinum alloy particles down to 2 ~ 4 nm will be discussed. Based on nature of alloyed base metals, various synthesis technologies have been studied and developed to achieve capabilities of controlling particle size and particle microcomposition, namely, core-shell synthesis, microemulsion technique, thermal decomposition process, surface organometallic chemical method, etc. The results show that by careful engineering the

Fabrication of Fischer-Tropsch Catalysts by Deposition of Iron Nanocrystals on Carbon Nanotubes

NARCIS (Netherlands)

Casavola, Marianna; Hermannsdoerfer, Justus; de Jonge, Niels; Dugulan, A. Iulian; de Jong, Krijn P.

2015-01-01

The fabrication of supported catalysts consisting of colloidal iron oxide nanocrystals with tunable size, geometry, and loadinghomogeneously dispersed on carbon nanotube (CNT) supportsis described herein. The catalyst synthesis is performed in a two-step approach. First, colloidal iron and iron

PT AND PT/NI "NEEDLE" ELETROCATALYSTS ON CARBON NANOTUBES WITH HIGH ACTIVITY FOR THE ORR

Energy Technology Data Exchange (ETDEWEB)

Colon-Mercado, H.

2011-11-10