Chloro-benquinone Modified on Graphene Oxide as Metal-free Catalyst: Strong Promotion of Hydroxyl Radical and Generation of Ultra-Small Graphene Oxide

Science.gov (United States)

Zhao, He; Wang, Juehua; Zhang, Di; Dai, Qin; Han, Qingzhen; Du, Penghui; Liu, Chenming; Xie, Yongbing; Zhang, Yi; Cao, Hongbin; Fan, Zhuangjun

2017-03-01

Carbon-based metal-free catalyst has attracted more and more attention. It is a big challenge to improve catalytic activity of metal-free catalyst for decomposition of H2O2 to produce hydroxyl radical (HO•). Here, we report chloro-benquinone (TCBQ) modified on graphene oxide (GO) as metal-free catalyst for strong promotion of HO•. By the incorporation of GO, the HO• production by H2O2 and TCBQ is significantly promoted. Based on density functional theory, TCBQ modified GO (GO-TCBQ) is more prone to be nucleophilic attacked by H2O2 to yield HO• via electron transfer acceleration. Furthermore, the generated HO• can cut GO nanosheets into uniform ultra-small graphene oxide (USGO) through the cleavage of epoxy and C-C bonds. Interestingly, the damaged GO and in situ formed GO fragments can further enhance decomposition of H2O2 to produce HO•. Different from other catalytic processes, the GO-TCBQ metal-free catalysis process can be enhanced by GO itself, producing more HO•, and uniform USGO also can be generated. Thus, the metal free catalysis will be considered a fabrication method for uniform USGO, and may be extended to other fields including detoxifying organic pollutants and the application as disinfectants.

Studies of Heterogenous Palladium and Related Catalysts for Aerobic Oxidation of Primary Alcohols

Science.gov (United States)

Ahmed, Maaz S.

alcohol solvent and the surface of the catalyst: (listed in order of strength) lone pair-surface (heterocyclic primary alcohols) > pi-surface (aryl primary alcohols) > van der Waals-surface (alkyl primary alcohols). These interactions were previously underappreciated in condensed phase heterogeneously catalyzed aerobic oxidations. Bi and Te serve as synergistic promoters that enhance both the rate and yield of the reactions relative to reactions employing Pd alone or Pd in combination with Bi or with Te as the sole promoter. We report X-ray absorption spectroscopic studies of the heterogenous catalyst. These methods show that the promoters undergo oxidation in preference to Pd, maintaining the Pd surface in the active metallic state and preventing inhibition by surface Pd-oxide formation. The data also suggest formation of a Pd-Te alloy phase that modifies the electronic properties of the Pd catalyst. Collectively, these results provide valuable insights into the synergistic benefits of multiple promoters in heterogeneous catalytic oxidation reactions.

Nanoparticular metal oxide/anatase catalysts

DEFF Research Database (Denmark)

2010-01-01

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

Cerium promoted Fischer-Tropsch catalysts

International Nuclear Information System (INIS)

Fiato, R.A.; Bar-Gadda, R.; Miseo, S.

1987-01-01

This patent describes a hydrocarbon synthesis catalyst composition comprising sintered combination metal oxides having the following components in the stated weight percentage of the catalyst composition: (a) about 5 to about 80 weight percent Fe oxide; (b) about 4 to about 20 weight percent Zn oxide; (c) about 10 to about 40 weight percent Ti and/or Mn oxide; (d) about 1 to about 5 weight percent K, Rb, and/or Cs oxide; and (e) about 1 to about 10 weight percent Ce oxide, such that where the catalyst contains Fe, the sintered combination comprises a series of Fe, Zn, and/or Ti and/or Mn spinels and oxides of K, Rb and/or Cs, dispersed in a Ce oxide matrix

Reducible oxide based catalysts

Science.gov (United States)

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

2010-04-06

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

Catalyst for Ammonia Oxidation

DEFF Research Database (Denmark)

2015-01-01

The present invention relates to a bimetallic catalyst for ammonia oxidation, a method for producing a bimetallic catalyst for ammonia oxidation and a method for tuning the catalytic activity of a transition metal. By depositing an overlayer of less catalytic active metal onto a more catalytic...

Studies on the promotion of nickel—alumina coprecipitated catalysts: III. Cerium oxide

NARCIS (Netherlands)

Lansink Rotgerink, H.G.J.; Slaa, J.C.; van Ommen, J.G.; Ross, J.R.H.

1988-01-01

Three series of cerium-promoted nickel—alumina catalysts with different nickel-to-aluminium ratios each containing different amounts of cerium have been prepared and characterized. The calcination and reduction behaviour were found not to be altered by the presence of cerium. Part of the promoter

Studies on the promotion of nickel—alumina coprecipitated catalysts: I. Titanium oxide

NARCIS (Netherlands)

Lansink Rotgerink, H.G.J.; Mercera, P.D.L.; van Ommen, J.G.; Ross, J.R.H.

1988-01-01

A series of TiO2-promoted nickel—alumina catalysts has been prepared and characterized. The promoter was added in various proportions to a calcined coprecipitated nickel—alumina material by adsorption of the acetylacetonate complex of titanium, followed by further calcination and reduction. The

Iron oxide/cassava starch-supported Ziegler-Natta catalysts for in situ ethylene polymerization.

Science.gov (United States)

Chancharoenrith, Sittikorn; Kamonsatikul, Choavarit; Namkajorn, Montree; Kiatisevi, Supavadee; Somsook, Ekasith

2015-03-06

Iron oxide nanoparticles were used as supporters for in situ polymerization to produce polymer nanocomposites with well-dispersed fillers in polymer matrix. Iron oxide could be sustained as colloidal solutions by cassava starch to produce a good dispersion of iron oxide in the matrix. New supports based on iron oxide/cassava starch or cassava starch for Ziegler-Natta catalysts were utilized as heterogeneous supporters for partially hydrolyzed triethylaluminum. Then, TiCl4 was immobilized on the supports as catalysts for polymerization of ethylene. High-density polyethylene (HDPE) composites were obtained by the synthesized catalysts. A good dispersion of iron oxide/cassava starch particles was observed in the synthesized polymer matrix promoting to good mechanical properties of HDPE. Copyright © 2014 Elsevier Ltd. All rights reserved.

Oxidation of methyl heterocyclic compounds on vanadium oxide catalysts

International Nuclear Information System (INIS)

Shimanskaya, M.V.; Lejtis, L.A.; Iovel', I.G.; Gol'dberg, Yu.Sh.; Skolmejstere, R.A.; Golender, L.O.

1985-01-01

Data on vapor-phase oxidation of methyl derivatives of thiophene, Δ 2 - thiazo line, pyridine, pyrazine and pyramidine on oxide vanadium-molybdenum catalysts to corresponding heterylaldehydes are generalized. The dependence of catalytic properties of oxide vanadium-molybdenum systems in oxidation reactions of methylheterocyclic compounds on V:Mo ratio in the catalyst is revealed. It is shown that heterocyclic compounds are coordinated by a heteroatom on Lewis centres of V-Mo-O-catalyst primarily with partially reduced vanadium ions

Influence of Reduction Promoters on Stability of Cobalt/g-Alumina Fischer-Tropsch Synthesis Catalysts

Directory of Open Access Journals (Sweden)

Gary Jacobs

2014-03-01

Full Text Available This focused review article underscores how metal reduction promoters can impact deactivation phenomena associated with cobalt Fischer-Tropsch synthesis catalysts. Promoters can exacerbate sintering if the additional cobalt metal clusters, formed as a result of the promoting effect, are in close proximity at the nanoscale to other cobalt particles on the surface. Recent efforts have shown that when promoters are used to facilitate the reduction of small crystallites with the aim of increasing surface Co0 site densities (e.g., in research catalysts, ultra-small crystallites (e.g., <2–4.4 nm formed are more susceptible to oxidation at high conversion relative to larger ones. The choice of promoter is important, as certain metals (e.g., Au that promote cobalt oxide reduction can separate from cobalt during oxidation-reduction (regeneration cycles. Finally, some elements have been identified to promote reduction but either poison the surface of Co0 (e.g., Cu, or produce excessive light gas selectivity (e.g., Cu and Pd, or Au at high loading. Computational studies indicate that certain promoters may inhibit polymeric C formation by hindering C-C coupling.

Ce - promoted catalyst from hydrotalcites for CO2 reforming of methane: calcination temperature effect

Directory of Open Access Journals (Sweden)

Carlos Enrique Daza

2012-01-01

Full Text Available Ce-promoted Ni-catalysts from hydrotalcites were obtained. The effect of calcination temperature on the chemical and physical properties of the catalysts was studied. Several techniques were used to determine the chemical and physical characteristics of oxides. The apparent activation energies of reduction were determined. Catalytic experiments at 48 L g-1h-1 without pre-reduction in CO2 reforming of methane were performed. The spinel-like phase in these oxides was only formed at 1000 ºC. The reduction of Ni2+ in the oxides was clearly affected by the calcination temperature which was correlated with catalytic performance. The catalyst calcined at 700 ºC showed the greatest activity.

Development of Vanadium Phosphaate Catalysts for Methanol Production by Selective Oxidation of Methane.

Energy Technology Data Exchange (ETDEWEB)

McCormick, R.L.

1997-10-01

This DOE sponsored study of methane partial oxidation was initiated at Amax Research and Development in Golden, CO in October of 1993. Shortly thereafter the management of Amax closed this R&D facility and the PI moved to the Colorado School of Mines. The project was begun again after contract transfer via a novation agreement. Experimental work began with testing of vandyl pyrophosphate (VPO), a well known alkane selective oxidation catalyst. It was found that VPO was not a selective catalyst for methane conversion yielding primarily CO. However, promotion of VPO with Fe, Cr, and other first row transition metals led to measurable yields for formaldehyde, as noted in the summary table. Catalyst characterization studies indicated that the role of promoters was to stabilize some of the vanadium in the V{sup 5+} oxidation state rather than the V{sup 4+} state formally expected for (VO){sub 2}P{sub 2}O{sub 7}.

Selective propene oxidation on mixed metal oxide catalysts

International Nuclear Information System (INIS)

James, David William

2002-01-01

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

Catalyst for Decomposition of Nitrogen Oxides

Science.gov (United States)

Schryer, David R. (Inventor); Jordan, Jeffrey D. (Inventor); Akyurtlu, Ates (Inventor); Akyurtlu, Jale (Inventor)

2015-01-01

This invention relates generally to a platinized tin oxide-based catalyst. It relates particularly to an improved platinized tin oxide-based catalyst able to decompose nitric oxide to nitrogen and oxygen without the necessity of a reducing gas.

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

Newly designed PdRuBi/N-Graphene catalysts with synergistic effects for enhanced ethylene glycol electro-oxidation

International Nuclear Information System (INIS)

Li, Tengfei; Huang, Yiyin; Ding, Kui; Wu, Peng; Abbas, Syed Comail; Ghausi, Muhammad Arsalan; Zhang, Teng; Wang, Yaobing

2016-01-01

Graphical abstract: We rationally design and synthesize a ternary PdRuBi/NG catalyst with significantly enhanced catalytic activity with synergetic effect of Ru and Bi towards ethylene glycol electro-oxidation. - Abstract: Palladium (Pd)-based catalysts are appealing electro-catalysts for alcohol oxidation reaction in fuel cell, but still not efficient as the complicated oxidation process and sluggish kinetic. Here we rationally design and synthesize a PdRuBi/NG tri-metallic catalyst with space synergetic effect for enhanced ethylene glycol electro-oxidation, in which both Ru and Bi in the catalyst are synergistic effective in promoting catalytic activity of Pd catalytic interlayer by electronic effect and surface modification mechanism respectively. It shows 4.2 times higher peak current density towards ethylene glycol electro-oxidation than commercial Pd/C catalyst, and the catalytic durability is also greatly improved.

Heteropoly acid promoted catalyst for SCR of NOx with ammonia

DEFF Research Database (Denmark)

2012-01-01

The present invention concerns the selective removal of nitrogen oxides (NOx) from gases. In particular, the invention concerns a process, a highly alkali metal resistant heteropoly acid promoted catalyst and the use of said catalyst for removal of NOx from exhaust or flue gases, said gases...... comprising alkali or earth alkali metals. Such gases comprise for example flue gases arising from the burning of biomass, combined biomass and fossil fuel, and from waste incineration units. The process comprises the selective catalytic reduction (SCR) of NOx, such as nitrogen dioxide (NO2) and nitrogen...

Selectivity and Activity of Iron Molybdate Catalysts in Oxidation of Methanol

Directory of Open Access Journals (Sweden)

Khalid Khazzal Hummadi

2009-06-01

Full Text Available The selectivity and activity of iron molybdate catalysts prepared by different methods are compared with those of a commercial catalyst in the oxidation of methanol to formaldehyde in a continuous tubular bed reactor at 200-350 oC (473-623 oK, 10 atm (1013 kPa, with a methanol-oxygen mixture fixed at 5.5% by volume methanol: air ratio. The iron(III molybdate catalyst prepared by co-precipitation and filtration had a selectivity towards formaldehyde in methanol oxidation comparable with a commercial catalyst; maximum selectivity (82.3% was obtained at 573oK when the conversion was 59.7%. Catalysts prepared by reacting iron (III and molybdate by kneading or precipitation followed by evaporation, omitting a filtration stage, were less active and less selective. The selectivity-activity relationships of these catalysts as a function of temperature were discussed in relation to the method of preparation, surface areas and composition. By combing this catalytic data with data from the patent literature we demonstrate a synergy between iron and molybdenum in regard to methanol oxidation to formaldehyde; the optimum composition corresponded to an iron mole fraction 0.2-0.3. The selectivity to formaldehyde was practically constant up to an iron mole fraction 0.3 and then decreased at higher iron concentrations. The iron component can be regarded as the activity promoter. The iron molybdate catalysts can thus be related to other two-component MoO3-based selective oxidation catalysts, e.g. bismuth and cobalt molybdates. The iron oxide functions as a relatively basic oxide abstracting, in the rate-controlling step, a proton from the methyl of a bound methoxy group of chemisorbed methanol. It was proposed that a crucial feature of the sought after iron(III molybdate catalyst is the presence of -O-Mo-O-Fe-O-Mo-O- groups as found in the compound Fe2(MoO43 and for Fe3+ well dispersed in MoO3 generally. At the higher iron(III concentrations the loss of

Quantifying the promotion of Cu catalysts by ZnO for methanol synthesis

DEFF Research Database (Denmark)

Kuld, Sebastian; Thorhauge, Max; Falsig, Hanne

2016-01-01

Promoter elements enhance the activity and selectivity of heterogeneous catalysts. Here, we show how methanol synthesis from synthesis gas over copper (Cu) nanoparticles is boosted by zinc oxide (ZnO) nanoparticles. By combining surface area titration, electron microscopy, activity measurement, d...

Oxidation catalysts on alkaline earth supports

Science.gov (United States)

Mohajeri, Nahid

2017-03-21

An oxidation catalyst includes a support including particles of an alkaline earth salt, and first particles including a palladium compound on the support. The oxidation catalyst can also include precious metal group (PMG) metal particles in addition to the first particles intermixed together on the support. A gas permeable polymer that provides a continuous phase can completely encapsulate the particles and the support. The oxidation catalyst may be used as a gas sensor, where the first particles are chemochromic particles.

Heterogeneous Metal Catalysts for Oxidation Reactions

Directory of Open Access Journals (Sweden)

Md. Eaqub Ali

2014-01-01

Full Text Available Oxidation reactions may be considered as the heart of chemical synthesis. However, the indiscriminate uses of harsh and corrosive chemicals in this endeavor are threating to the ecosystems, public health, and terrestrial, aquatic, and aerial flora and fauna. Heterogeneous catalysts with various supports are brought to the spotlight because of their excellent capabilities to accelerate the rate of chemical reactions with low cost. They also minimize the use of chemicals in industries and thus are friendly and green to the environment. However, heterogeneous oxidation catalysis are not comprehensively presented in literature. In this short review, we clearly depicted the current state of catalytic oxidation reactions in chemical industries with specific emphasis on heterogeneous catalysts. We outlined here both the synthesis and applications of important oxidation catalysts. We believe it would serve as a reference guide for the selection of oxidation catalysts for both industries and academics.

Alkaline Ionic Liquid Modified Pd/C Catalyst as an Efficient Catalyst for Oxidation of 5-Hydroxymethylfurfural

Directory of Open Access Journals (Sweden)

Zou Bin

2018-01-01

Full Text Available Conversion of HMF into FDCA was carried out by a simple and green process based on alkaline ionic liquid (IL modified Pd/C catalyst (Pd/C-OH−. Alkaline ionic liquids were chosen to optimize Pd/C catalyst for special hydrophilicity and hydrophobicity, redox stability, and unique dissolving abilities for polar compounds. The Pd/C-OH− catalyst was successfully prepared and characterized by SEM, XRD, TG, FT-IR, and CO2-TPD technologies. Loading of alkaline ionic liquid on the surface of Pd/C was 2.54 mmol·g−1. The catalyst showed excellent catalytic activity in the HMF oxidation after optimization of reaction temperature, reaction time, catalyst amount, and solvent. Supported alkaline ionic liquid (IL could be a substitute and promotion for homogeneous base (NaOH. Under optimal reaction conditions, high HMF conversion of 100% and FDCA yield of 82.39% were achieved over Pd/C-OH− catalyst in water at 373 K for 24 h.

Promoted V2O5/TiO2 catalysts for selective catalytic reduction of NO with NH3 at low temperatures

DEFF Research Database (Denmark)

Putluru, Siva Sankar Reddy; Schill, Leonhard; Godiksen, Anita

2016-01-01

characterized by N2 physisorption, XRPD, NH3-TPD, H2-TPR, Raman, FTIR and EPR spectroscopy to investigate the properties of the catalysts. XRPD, Raman and FTIR showed that promotion with 15 wt.% HPA does not cause V2O5 to be present in crystalline form, also at a loading of 5 wt.% V2O5. Hence, use of HPAs does......The influence of varying the V2O5 content (3–6 wt.%) was studied for the selective catalytic reduction (SCR) of nitrogen oxides by ammonia on heteropoly acid (HPA)- and tungsten oxide (WO3)-promoted V2O5/TiO2 catalysts. The SCR activity and alkali deactivation resistance of HPA-promoted V2O5/TiO2...... catalysts was found to be much higher than for WO3-promoted catalysts. By increasing the vanadium content from 3 to 5 wt.% the catalysts displayed a two fold increase in activity at 225 °C and retained their initial activity after alkali doping at a molar K/V ratio of 0.181. Furthermore, the catalysts were...

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

CSIR Research Space (South Africa)

Maphoru, MV

2014-01-01

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

On the mechanism of hydrogen-promoted gold-catalyzed CO oxidation

KAUST Repository

Quinet, Elodie

2009-12-10

The kinetics of CO oxidation, H2 oxidation and preferential CO oxidation (PrOx) over Au/Al2O3 catalysts have been investigated. The catalysts with the smallest particles (∼2 nm) are the most active for all three reactions. As previously observed, the presence of H2 greatly promotes CO oxidation, which becomes faster than CO-free H2 oxidation at low temperature. From these results and on the basis of previous works, we propose a complete PrOx mechanism. The reaction involves Au-OOH, Au-OH and Au-H intermediates, also involved in H2 oxidation, and benefits from the presence of low-coordination sites. © 2009 Elsevier Inc. All rights reserved.

On the mechanism of hydrogen-promoted gold-catalyzed CO oxidation

KAUST Repository

Quinet, Elodie; Piccolo, Laurent; Morfin, Franck; Avenier, Priscilla; Diehl, Fabrice; Caps, Valerie; Rousset, Jean Luc

2009-01-01

The kinetics of CO oxidation, H2 oxidation and preferential CO oxidation (PrOx) over Au/Al2O3 catalysts have been investigated. The catalysts with the smallest particles (∼2 nm) are the most active for all three reactions. As previously observed, the presence of H2 greatly promotes CO oxidation, which becomes faster than CO-free H2 oxidation at low temperature. From these results and on the basis of previous works, we propose a complete PrOx mechanism. The reaction involves Au-OOH, Au-OH and Au-H intermediates, also involved in H2 oxidation, and benefits from the presence of low-coordination sites. © 2009 Elsevier Inc. All rights reserved.

Plasma and catalyst for the oxidation of NOx

Science.gov (United States)

Jõgi, Indrek; Erme, Kalev; Levoll, Erik; Raud, Jüri; Stamate, Eugen

2018-03-01

Efficient exhaust gas cleaning from NO x (NO and NO2) by absorption and adsorption based methods requires the oxidation of NO. The application of non-thermal plasma is considered as a promising oxidation method but the oxidation of NO by direct plasma remains limited due to the back-reaction of NO2 to NO mediated by O radicals in plasma. Indirect NO oxidation by plasma produced ozone allows to circumvent the back-reaction and further oxidize NO2 to N2O5 but the slow reaction rate for the latter process limits the efficiency of this process. Present paper gives an overview of the role of metal-oxide catalysts in the improvement of oxidation efficiency for both direct and indirect plasma oxidation of NO x . The plasma produced active oxygen species (O, O3) were shown to play an important role in the reactions taking place on the catalyst surfaces while the exact mechanism and extent of the effect were different for direct and indirect oxidation. In the case of direct plasma oxidation, both short and long lifetime oxygen species could reach the catalyst and participate in the oxidation of NO to NO2. The back-reaction in the plasma phase remained still important factor and limited the effect of catalyst. In the case of indirect oxidation, only ozone could reach the catalyst surface and improve the oxidation of NO2 to N2O5. The effect of catalyst at different experimental conditions was quantitatively described with the aid of simple global chemical kinetic models derived for the NO x oxidation either by plasma or ozone. The models allowed to compare the effect of different catalysts and to analyze the limitations for the efficiency improvement by catalyst.

PILOT TESTING OF MERCURY OXIDATION CATALYSTS FOR UPSTREAM OF WET FGD SYSTEMS

International Nuclear Information System (INIS)

Gary M. Blythe

2002-01-01

The objective of this project is to demonstrate at pilot scale the use of solid honeycomb catalysts to promote the oxidation of elemental mercury in the flue gas from coal combustion. The project is being funded by the U.S. DOE National Energy Technology Laboratory under Cooperative Agreement DE-FC26-01NT41185. EPRI, Great River Energy (GRE), and City Public Service (CPS) of San Antonio are project co-funders. URS Group is the prime contractor. The mercury catalytic oxidation process under development uses catalyst materials applied to honeycomb substrates to promote the oxidation of elemental mercury in the flue gas from coal-fired power plants that have wet lime or limestone flue gas desulfurization (FGD) systems. Oxidized mercury is removed in the wet FGD absorbers and co-precipitates in a stable form with the byproducts from the FGD system. The co-precipitated mercury does not appear to adversely affect the disposal or reuse properties of the FGD byproduct. The current project will test previously identified, effective catalyst materials at a larger, pilot scale and in a commercial form, so as to provide engineering data for future full-scale designs. The pilot-scale tests will continue for up to 14 months at each of two sites to provide longer-term catalyst life data. This is the first full reporting period for the subject Cooperative Agreement. During this period, most of the project efforts were related to project initiation and planning. There is no significant technical progress to report for the current period

Isotope exchange in oxide-containing catalyst

Science.gov (United States)

Brown, Kenneth G. (Inventor); Upchurch, Billy T. (Inventor); Hess, Robert V. (Inventor); Miller, Irvin M. (Inventor); Schryer, David R. (Inventor); Sidney, Barry D. (Inventor); Wood, George M. (Inventor); Hoyt, Ronald F. (Inventor)

1989-01-01

A method of exchanging rare-isotope oxygen for common-isotope oxygen in the top several layers of an oxide-containing catalyst is disclosed. A sample of an oxide-containing catalyst is exposed to a flowing stream of reducing gas in an inert carrier gas at a temperature suitable for the removal of the reactive common-isotope oxygen atoms from the surface layer or layers of the catalyst without damaging the catalyst structure. The reduction temperature must be higher than any at which the catalyst will subsequently operate. Sufficient reducing gas is used to allow removal of all the reactive common-isotope oxygen atoms in the top several layers of the catalyst. The catalyst is then reoxidized with the desired rare-isotope oxygen in sufficient quantity to replace all of the common-isotope oxygen that was removed.

Novel metalloporphyrin catalysts for the oxidation of hydrocarbons

Energy Technology Data Exchange (ETDEWEB)

Showalter, M.C.; Nenoff, T.M.; Shelnutt, J.A.

1996-11-01

Work was done for developing biomimetic oxidation catalysts. Two classes of metalloporphyrin catalysts were studied. The first class of catalysts studied were a novel series of highly substituted metalloporphyrins, the fluorinated iron dodecaphenylporphyrins. These homogeneous metalloporphyrin catalysts were screened for activity as catalysts in the oxidation of hydrocarbons by dioxygen. Results are discussed with respect to catalyst structural features. The second type of catalysts studied were heterogeneous catalysts consisting of metalloporphyrins applied to inorganic supports. Preliminary catalytic testing results with these materials are presented.

OXIDATIVE-REFORMING OF METHANE AND PARTIAL OXIDATION OF METHANE REACTIONS OVER NiO/PrO2/ZrO2 CATALYSTS: EFFECT OF NICKEL CONTENT

Directory of Open Access Journals (Sweden)

Y. J. O. Asencios

Full Text Available Abstract In this work the behavior of NiO-PrO2-ZrO2 catalysts containing various nickel loadings was evaluated in the partial oxidation of methane and oxidative-reforming reactions of methane. The catalysts were characterized by X-Ray Diffraction Analysis (in situ-XRD, Temperature Programmed Reduction (H2-TPR, Scanning Electron Microscopy (SEM/EDX and Adsorption-Desorption of nitrogen (BET area. The reactions were carried out at 750 °C and 1 atm for 5 hours. The catalysts were studied with different nickel content: 0, 5, 10 and 15% (related to total weight of catalyst, wt%. In both reactions, the catalyst containing the mixture of the three oxides (NiO/PrO2/ZrO2 with 15% nickel (15NiPrZr catalyst showed the best activity for the conversion of the reactants into Syngas and showed high selectivity for H2 and CO. The results suggest that the promoter PrO2 and the Niº centers are in a good proportion in the catalyst with 15% Ni. Our results showed that low nickel concentrations in the catalyst led to high metallic dispersion; however, very low nickel concentrations did not favor the methane transformation into Syngas. The catalyst containing only NiO/ZrO2 in the mixture was not sufficient for the catalysis. The presence of the promoter PrO2 was very important for the catalysis of the POM.

Studies on the promotion of nickel—alumina coprecipitated catalysts: II. Lanthanum oxide

NARCIS (Netherlands)

Lansink Rotgerink, H.G.J.; Paalman, R.P.A.M.; van Ommen, J.G.; Ross, J.R.H.

1988-01-01

Two series of lanthanum promoted nickel—alumina catalysts have been prepared by coprecipitation of the metal nitrates, using potassium carbonate. The molar ratio between nickel and the sum of aluminium and lanthanum was kept constant at 2.5 or 9.0 within each series. The calcination and reduction of

Tin-antimony oxide oxidation catalysts

Energy Technology Data Exchange (ETDEWEB)

Berry, Frank J. [Open University, Department of Chemistry (United Kingdom)

1998-12-15

Tin-antimony oxide catalysts for the selective oxidation of hydrocarbons have been made by precipitation techniques. The dehydration of the amorphous dried precipitate by calcination at increasingly higher temperatures induces the crystallisation of a rutile-related tin dioxide-type phase and the segregation of antimony oxides which volatilise at elevated temperatures. The rutile-related tin dioxide-type phase contains antimony(V) in the bulk and antimony(III) in the surface. Specific catalytic activity for the oxidative dehydrogenation of butene to butadiene is associated with materials with large concentrations of antimony(III) in the surface.

Oxidative dehydrogenation of ethane on rare-earth oxide-based catalysts

Energy Technology Data Exchange (ETDEWEB)

Buyevskaya, O.; Baerns, M. [Institut fuer Angewandte Chemie Berlin-Adlershof e.V., Berlin (Germany)

1998-12-31

Results on the oxidative dehydrogenation of ethane on rare-earth oxide (REO) based catalysts (Na-P-Sm-O, Sm-Sr(Ca)-O, La-Sr-O and Nd-Sr-O) are described. Oxygen adsorption was found to be a key factor which determines the activity of this type of catalysts. Continuous flow experiments in the presence of catalysts which reveal strong oxygen adsorption showed that the reaction mixture is ignited resulting in an enhanced heat generation at the reactor inlet. The heat produced by the oxidative reactions was sufficient under the conditions chosen for the endothermic thermal pyrolysis which takes place preferentially in the gas phase. Ignition of the reaction mixture is an important catalyst function. Contrary to non-catalytic oxidative dehydrogenation, reaction temperatures above 700 C could be achieved without significant external heat input. Ethylene yields of up to 34-45% (S=66-73%) were obtained on REO-based catalysts under non-isothermal conditions (T{sub max}=810-865 C) at contact times in the order of 30 to 40 ms. (orig.)

Fischer-Tropsch diesel production over calcium-promoted Co/alumina catalyst: Effect of reaction conditions

Energy Technology Data Exchange (ETDEWEB)

A.R. de la Osa; A. De Lucas; A. Romero; J.L. Valverde; P. Sanchez [University of Castilla-La Mancha, Ciudad Real (Spain). Chemical Engineering Department

2011-05-15

The effects of reaction conditions on the Fischer-Tropsch activity and product distribution of an alkali-earth metal promoted cobalt based catalyst were studied. The influence of the promoter on the reducibility and cobalt particle size was studied by different techniques, including N{sub 2} adsorption, X-ray diffraction, temperature-programmed reduction, temperature-programmed desorption and acid-base titrations. Experiments were carried out on a bench-scale fixed bed reactor and catalysts were prepared by incipient wetness impregnation. It was observed that addition of a small amount of calcium oxide as a promoter (0.6 wt.%) improved the cobalt oxide reducibility and reduced the formation of cobalt-aluminate species. A positive correlation between basicity and particle size was observed. In terms of FTS results, CO conversion and C{sub 5}{sup +} selectivity were found to be enhanced by the addition of this promoter. It was important to note that the addition of calcium shifted the distribution to mainly C{sub 16}-C{sub 18} hydrocarbons fraction, which could be greatly considered for a diesel formulation. Furthermore, the variation of the reaction conditions seemed to influence product distribution in a lesser extent than unpromoted catalyst. Also, a displacement of hydrocarbon distribution to higher molecular weight with decreasing space velocity and temperature was observed. Moreover, the addition of calcium to the cobalt based catalyst was found to greatly maintain selectivity to C{sub 5}{sup +} for a wide range of H{sub 2}/CO molar ratios. 60 refs., 10 figs., 5 tabs.

A predictive tool for selective oxidation of hydrocarbons: optical basicity of catalysts

Energy Technology Data Exchange (ETDEWEB)

Moriceau, P.; Lebouteiller, A.; Bordes, E.; Courtine, P. [Universite de Technologie de Compiegne, 60 (France). Dept. de Genie Chimique

1998-12-31

Whatever the composition of the catalyst (promoted, supported, multicomponent, etc.) is, it is possible to calculate its electron donor capacity {Lambda}. However, one important question remains: How are the surface and the bulk values of {Lambda} related? Most oxidation catalysts exhibit either a layered structure as V{sub 2}O{sub 5}, and approximately {Lambda}{sub th}{proportional_to}{Lambda}{sub surf}, or a molecular structure as polyoxometallates, and no correction seems to be needed. Work is in progress on that point. Of great importance is also the actual oxidation and coordination states of cations at the stedy state: {Lambda}s have been calculated from the composition determined by XANES and XPS. Finally, the model is able to discriminate between `paraffins` and olefins as reactants. These calibration curves should help to find new catalysts. (orig.)

Selective liquid-phase oxidation of alcohols catalyzed by a silver-based catalyst promoted by the presence of ceria

DEFF Research Database (Denmark)

Beier, Matthias Josef; Hansen, Thomas Willum; Grunwaldt, Jan-Dierk

2009-01-01

simultaneously. When a high catalytic conversion (>30% over 2 h) was found the number of catalyst components was reduced in the following tests. Thereby, a collaborative effect between a physical mixture of ceria nanoparticles and silver-impregnated silica (10 wt.% Ag–SiO2) was found. The catalytic activity...... by in situ XAS experiments. Oxygen species incorporated in the silver lattice appear to be important for the catalytic oxidation of the alcohol for which a preliminary mechanism is presented. The application of the catalyst was extended to the oxidation of a wide range of primary and secondary alcohols....... Compared to palladium and gold catalysts, the new silver catalyst performed similarly or even superior in the presence of CeO2. In addition, the presence of ceria increased the catalytic activity of all investigated catalysts....

Bioinspired aerobic oxidation of secondary amines and nitrogen heterocycles with a bifunctional quinone catalyst.

Science.gov (United States)

Wendlandt, Alison E; Stahl, Shannon S

2014-01-08

Copper amine oxidases are a family of enzymes with quinone cofactors that oxidize primary amines to aldehydes. The native mechanism proceeds via an iminoquinone intermediate that promotes high selectivity for reactions with primary amines, thereby constraining the scope of potential biomimetic synthetic applications. Here we report a novel bioinspired quinone catalyst system consisting of 1,10-phenanthroline-5,6-dione/ZnI2 that bypasses these constraints via an abiological pathway involving a hemiaminal intermediate. Efficient aerobic dehydrogenation of non-native secondary amine substrates, including pharmaceutically relevant nitrogen heterocycles, is demonstrated. The ZnI2 cocatalyst activates the quinone toward amine oxidation and provides a source of iodide, which plays an important redox-mediator role to promote aerobic catalytic turnover. These findings provide a valuable foundation for broader development of aerobic oxidation reactions employing quinone-based catalysts.

Alkali promotion effect in Fischer-Tropsch cobalt-alumina catalyst

Energy Technology Data Exchange (ETDEWEB)

Eliseev, O.L.; Tsapkina, M.V.; Davydov, P.E.; Kazantsev, R.V. [Russian Academy of Sciences, Moscow (Russian Federation). N.D. Zelinsky Inst. of Organic Chemistry; Belousova, O.S.; Lapidus, A.L. [Gubkin Russian State Univ. of Oil and Gas, Moscow (Russian Federation)

2011-07-01

Promoting Co-alumina Fischer-Tropsch synthesis catalysts with alkali and alkaline-earth metals was studied. XRD, oxygen titration and CO chemisorption were used for the characterization of the catalysts. The best results in terms of catalyst selectivity and long-chain alkanes content in synthesized products were obtained with K-promoted catalyst. Catalytic performance strongly depends on K:Co atomic ratio as well as preparation procedure. Effect of K loading on selectivities is non-linear with extreme point at K:Co=0.01. Significant increase in C{sub 5+} selectivity of K-promoted catalyst may be explained as a result of strong CO adsorption on the catalyst surface, as was confirmed in CO chemisorption experiments. (orig.)

Water oxidation catalysts and methods of use thereof

Energy Technology Data Exchange (ETDEWEB)

Hill, Craig L.; Gueletii, Yurii V.; Musaev, Djamaladdin G.; Yin, Qiushi; Botar, Bogdan

2017-12-05

Homogeneous water oxidation catalysts (WOCs) for the oxidation of water to produce hydrogen ions and oxygen, and methods of making and using thereof are described herein. In a preferred embodiment, the WOC is a polyoxometalate WOC which is hydrolytically stable, oxidatively stable, and thermally stable. The WOC oxidized waters in the presence of an oxidant. The oxidant can be generated photochemically, using light, such as sunlight, or electrochemically using a positively biased electrode. The hydrogen ions are subsequently reduced to form hydrogen gas, for example, using a hydrogen evolution catalyst (HEC). The hydrogen gas can be used as a fuel in combustion reactions and/or in hydrogen fuel cells. The catalysts described herein exhibit higher turn over numbers, faster turn over frequencies, and/or higher oxygen yields than prior art catalysts.

Activity of molybdenum-containing oxide catalysts in the reaction of ethane oxidation

International Nuclear Information System (INIS)

Konovalov, V.I.; Ehpova, T.I.; Shchukin, V.P.; Averbukh, A.Ya.

1977-01-01

Investigation results concerning the catalytic activity of molybdenum-containing catalysts in ethane oxidation reaction are presented. It has been found that the greatest activity in the temperature range from 450 to 600 deg C is exhibited by cobalt-molybdenum catalyst; at 600 deg C bismuth-molybdenum catalyst is the most active. Nickel-molybdenum catalyst is selective and active with respect to ethylene. Iron- and manganese-molybdenum catalysts do not show high ethane oxidation rates and their selectivity is insignificant

Synthesis of a molecularly defined single-active site heterogeneous catalyst for selective oxidation of N-heterocycles.

Science.gov (United States)

Zhang, Yujing; Pang, Shaofeng; Wei, Zhihong; Jiao, Haijun; Dai, Xingchao; Wang, Hongli; Shi, Feng

2018-04-13

Generally, a homogeneous catalyst exhibits good activity and defined active sites but it is difficult to recycle. Meanwhile, a heterogeneous catalyst can easily be reused but its active site is difficult to reveal. It is interesting to bridge the gap between homogeneous and heterogeneous catalysis via controllable construction of a heterogeneous catalyst containing defined active sites. Here, we report that a molecularly defined, single-active site heterogeneous catalyst has been designed and prepared via the oxidative polymerization of maleimide derivatives. These polymaleimide derivatives can be active catalysts for the selective oxidation of heterocyclic compounds to quinoline and indole via the recycling of -C=O and -C-OH groups, which was confirmed by tracing the reaction with GC-MS using maleimide as the catalyst and by FT-IR analysis with polymaleimide as the catalyst. These results might promote the development of heterogeneous catalysts with molecularly defined single active sites exhibiting a comparable activity to homogeneous catalysts.

Chemical engineering design of CO oxidation catalysts

Science.gov (United States)

Herz, Richard K.

1987-01-01

How a chemical reaction engineer would approach the challenge of designing a CO oxidation catalyst for pulsed CO2 lasers is described. CO oxidation catalysts have a long history of application, of course, so it is instructive to first consider the special requirements of the laser application and then to compare them to the characteristics of existing processes which utilize CO oxidation catalysts. All CO2 laser applications require a CO oxidation catalyst with the following characteristics: (1) active at stoichiometric ratios of O2 and CO, (2) no inhibition by CO2 or other components of the laser environment, (3) releases no particulates during vibration or thermal cycling, and (4) long lifetime with a stable activity. In all applications, low consumption of power is desirable, a characteristic especially critical in aerospace applications and, thus, catalyst activity at low temperatures is highly desirable. High power lasers with high pulse repetition rates inherently require circulation of the gas mixture and this forced circulation is available for moving gas past the catalyst. Low repetition rate lasers, however, do not inherently require gas circulation, so a catalyst that did not require such circulation would be favorable from the standpoint of minimum power consumption. Lasers designed for atmospheric penetration of their infrared radiation utilize CO2 formed from rare isotopes of oxygen and this application has the additional constraint that normal abundance oxygen isotopes in the catalyst must not exchange with rare isotopes in the gas mixture.

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).

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 ...

Secondary promoters in alumina-supported nickel-molybdenum hydroprocessing catalysts

Energy Technology Data Exchange (ETDEWEB)

Lewis, J.M.

1992-01-01

Two secondary promoters, phosphorus and fluoride, have been investigated for their influences on the physicochemical properties of alumina-supported nickel-molybdenum hydroprocessing catalysts. Model compound reactions and infrared spectroscopy were used to probe the functionalities of the different catalysts, and the catalysts were tested in the hydroprocessing of a low-nitrogen and a high-nitrogen (quinoline-spiked) gas oil feed to assess the utility of the model compound reaction studies. Fluoride-promoted catalysts with high cumene hydrocracking activity and with comparable thiophene hydrodesulphurization (HDS) activity to Ni-Mo/Al[sub 2]O[sub 3] can be prepared by coimpregnation of the F, Ni and Mo additives. Fluoride promotes the hydrogenation (HYD) and HDS activity of Ni-Mo/Al[sub 2]O[sub 3] in the hydroprocessing (HYD) and HDS activity of Ni-Mo/Al[sub 2]O[sub 3] in the hydroprocessing of a low-nitrogen feed. Fluoride promotes the quinoline hydrodenitrogenation (HDN) activity of Ni-Mo/Al[sub 2]O[sub 3] catalysts. Impregnation of phosphorus prior to the metal additives results in catalysts which are more active in HDS. Phosphorus increases indirectly the Broensted acidity of the catalyst by increasing the activity of the MoS[sub 2]-associated acid sites. Phosphorus promotes the HDSW and HYD activities of Ni-Mo/Al[sub 2]O[sub 3] in the hydroprocessing of the low-N feed. A promotional effect of phosphorus is seen in quinoline HDN. P- and F-promoted Ni-MO/Al[sub 2]O[sub 3] catalysts are very active in quinoline HDN and maintain good activity in HDS and HYD of the high-N feed. Thiophene HDS was a good reaction for probing the activity of catalysts in the HDS of sterically-unhindered molecules, but an inaccurate probe for the HDS of hindered compounds.

Structure-activity relationships of carbon-supported platinum-bismuth and platinum-antimony oxidation catalysts

CSIR Research Space (South Africa)

Maphoru, MV

2017-04-01

Full Text Available Compositional and morphological studies on supported platinum are important for the improvement and expanded use of catalysts for oxidative coupling reactions. Nanocomposites consisting of 5% Pt supported on activated carbon and promoted with 5% Bi...

Aerobic Oxidation of Alcohols over Gold Catalysts: Role of Acid and Base

DEFF Research Database (Denmark)

Klitgaard, Søren Kegnæs; DeLa Riva, Andrew T.; Helveg, Stig

2008-01-01

Gold nanoparticles are deposited on potassium titanate nanowires and used as heterogeneous catalysts in the aerobic oxidation of benzyl alcohol in methanol to methyl benzoate at ambient conditions. The presence of a catalytic amount of base promotes the reaction and the formation of free benzoic...

Plasma and catalyst for the oxidation of NOx

DEFF Research Database (Denmark)

Jõgi, Indrek; Erme, Kalev; Levoll, Erik

2018-01-01

. In the case of indirect oxidation, only ozone could reach the catalyst surface and improve the oxidation of NO2 to N2O5. The effect of catalyst at different experimental conditions was quantitatively described with the aid of simple global chemical kinetic models derived for the NO x oxidation either...... by plasma or ozone. The models allowed to compare the effect of different catalysts and to analyze the limitations for the efficiency improvement by catalyst....... to NO mediated by O radicals in plasma. Indirect NO oxidation by plasma produced ozone allows to circumvent the back-reaction and further oxidize NO2 to N2O5 but the slow reaction rate for the latter process limits the efficiency of this process. Present paper gives an overview of the role of metal...

Rational design of Mg-Al mixed oxide-supported bimetallic catalysts for dry reforming of methane

Energy Technology Data Exchange (ETDEWEB)

Tsyganok, Andrey I. [Centre for Catalysis Research and Innovation, Department of Chemistry, University of Ottawa, D' Iorio Hall, 10 Marie Curie Street, Ottawa, Ont. (Canada); Inaba, Mieko [Natural Gas Technology Development Team, Teikoku Oil Co., 9-23-30 Kitakarasuyama, Setagaya-ku, Tokyo 157-0061 (Japan); Tsunoda, Tatsuo; Uchida, Kunio; Suzuki, Kunio; Hayakawa, Takashi [Institute for Materials and Chemical Process, National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba Central 5, 1-1-1 Higashi, Tsukuba 305-8565 (Japan); Takehira, Katsuomi [Department of Applied Chemistry, Faculty of Engineering, Hiroshima University, 1-4-1 Kagamiyama, Higashi-Hiroshima 739-8527 (Japan)

2005-09-18

A novel synthetic strategy for preparing bimetallic Ru-M (M=Cr, Fe, Co, Ni and Cu) catalysts, supported on Mg-Al mixed oxide, has been introduced. It was based on a 'memory effect', i.e. on the ability of Mg-Al mixed oxide to reconstruct a layered structure upon rehydration with an aqueous solution. By repeated calcinations-rehydration cycles, layered double hydroxide (LDH) precursors of catalysts containing two different metals were synthesized. Bimetallic catalysts were then generated (1) in situ from LDH under methane reforming reaction conditions and (2) from mixed metal oxides obtained by preliminary LDH calcination. Among all the LDH-derived catalysts, a Ru{sup 0.1%}-Ni{sup 5.0%}/MgAlO{sub x} sample revealed the highest activity and selectivity to syngas, a suitable durability and a low coking capacity. A promoting effect of ruthenium on catalytic function of supported nickel was demonstrated. Preliminary LDH calcination was shown to markedly affect the catalytic activity of the derived catalysts and especially their coking properties.

Plasma and catalyst for the oxidation of NOx

DEFF Research Database (Denmark)

Jögi, I.; Erme, K.; Levoll, E.

2017-01-01

The removal of NOx from the exhaust gases requires the oxidation of most abundant NO to NO2 or N2O5. The oxidation can be done by non-thermal plasma but the efficiency is limited due to the back-reaction of NO2 to NO by O radicals. Present contribution investigates the role of catalysts in the im......The removal of NOx from the exhaust gases requires the oxidation of most abundant NO to NO2 or N2O5. The oxidation can be done by non-thermal plasma but the efficiency is limited due to the back-reaction of NO2 to NO by O radicals. Present contribution investigates the role of catalysts...... in the improvement of oxidation efficiency based on the stationary and time-dependent studies of the NOx oxidation at different reactor configurations and experimental conditions. The plasma produced active oxygen species (O, O3) were shown to play an important role in the reactions taking place on the catalyst...... surfaces while the exact mechanism and extent of the effect depended on the reactor configuration. The effect of catalyst at different experimental conditions was quantitatively described with the aid of analytical lumped kinetic models derived for the NOx oxidation when the catalyst was directly...

Mechanism of 1, 1-d2 propene oxidation over oxide catalysts

International Nuclear Information System (INIS)

Portefaix, J.L.; Figueras, F.; Forissier, M.

1980-01-01

CD 2 CHCH 3 was oxidized over bismuth molybdate, tin-antimony mixed oxides and supported molybdenum and vanadium oxide catalysts. The deuterium retention is high ( > 90%) in the recovered propene. Percentage retentions of deuterium in the acrolein agree with literature data when bismuth molybdate is used as catalyst. On Sb-Sn-O and supported Mo and V oxides, no isotope effect is noticed for the abstraction of the second hydrogen from the olefin. The slow step of the reaction may therefore be different for the oxidation of propene on Bi-Mo-O and Sb-Sn-O. The ethanal produced by oxidation of CD 2 CHCH 3 contains only minor amounts of deuterium, whatever the catalyst used. It is suggested that partial oxidation of propene to acrolein and C-C bond rupture are parallel reactions which involve different intermediates. Possible mechanisms adapted from organic chemistry are presented to explain these findings. 4 tables

Sol-gel based oxidation catalyst and coating system using same

Science.gov (United States)

Watkins, Anthony N. (Inventor); Leighty, Bradley D. (Inventor); Oglesby, Donald M. (Inventor); Patry, JoAnne L. (Inventor); Schryer, Jacqueline L. (Inventor)

2010-01-01

An oxidation catalyst system is formed by particles of an oxidation catalyst dispersed in a porous sol-gel binder. The oxidation catalyst system can be applied by brush or spray painting while the sol-gel binder is in its sol state.

Samarium-modified vanadium phosphate catalyst for the selective oxidation of n-butane to maleic anhydride

International Nuclear Information System (INIS)

Wu, Hua-Yi; Wang, Hai-Bo; Liu, Xin-Hua; Li, Jian-Hui; Yang, Mei-Hua; Huang, Chuan-Jing; Weng, Wei-Zheng; Wan, Hui-Lin

2015-01-01

Graphical abstract: The addition of a small amount of Sm into VPO catalyst brought about great changes in its physicochemical properties such as surface area, surface morphology, phase composition and redox property, thus leading to a higher catalytic performance in the selective oxidation of n-butane to maleic anhydride, as compared to the undoped VPO catalyst. - Highlights: • The addition of Sm leads to great changes in the structure of VPO catalyst. • Sm improves performance of VPO for oxidation of n-butane to maleic anhydride. • Catalytic performance is closely related to structure of VPO catalyst. - Abstract: A series of samarium-modified vanadium phosphate catalysts were prepared and studied in selective oxidation of n-butane to maleic anhydride. The catalytic evaluation showed that Sm modification significantly increased the overall n-butane conversion and intrinsic activity. N 2 -adsorption, XRD, SEM, Raman, XPS, EPR and H 2 -TPR techniques were used to investigate the intrinsic difference among these catalysts. The results revealed that the addition of Sm to VPO catalyst can increase the surface area of the catalyst, lead to a significant change in catalyst morphology from plate-like structure into rosette-shape clusters, and largely promote the formation of (VO) 2 P 2 O 7 . All of these were related to the different catalytic performance of Sm-doped and undoped VPO catalysts. The roles of the different VOPO 4 phases and the influence of Sm were also described and discussed

Catalytic oxidation of volatile organic compounds (n-hexane, benzene, toluene, o-xylene promoted by cobalt catalysts supported on γ-Al2O3-CeO2

Directory of Open Access Journals (Sweden)

R. Balzer

2014-09-01

Full Text Available Cobalt catalysts supported on γ-alumina, ceria and γ-alumina-ceria, with 10 or 20%wt of cobalt load, prepared by the wet impregnation method and characterized by X-ray diffraction (XRD, scanning electron microscopy (SEM, field emission transmission electron microscopy (FETEM, N2 adsorption-desorption isotherms (BET/BJH methods, energy-dispersive X-ray spectroscopy (EDX, X-ray photoemission spectroscopy (XPS, O2-chemisorption and temperature programmed reduction (TPR were used to promote the oxidation of volatile organic compounds (n-hexane, benzene, toluene and o-xylene. For a range of low temperatures (50-350 °C, the activity of the catalysts with a higher cobalt load (20% wt was greater than that of the catalysts with a lower cobalt load (10% wt. The Co/γ-Al2O3-CeO2 catalytic systems presented the best performances. The results obtained in the characterization suggest that the higher catalytic activity of the Co20/γ-Al2O3-CeO2 catalyst may be attributed to the higher metal content and amount of oxygen vacancies, as well as the effects of the interaction between the cobalt and the alumina and cerium oxides.

Thermally oxidized aluminum as catalyst-support layer for vertically aligned single-walled carbon nanotube growth using ethanol

Energy Technology Data Exchange (ETDEWEB)

Azam, Mohd Asyadi, E-mail: asyadi@jaist.ac.jp [School of Materials Science, Japan Advanced Institute of Science and Technology (JAIST), 1-1 Asahidai, Nomi, Ishikawa 923-1292 (Japan); Fujiwara, Akihiko [Research and Utilization Division, Japan Synchrotron Radiation Research Institute (JASRI), 1-1-1, Kouto, Sayo-cho, Sayo, Hyogo 679-5198 (Japan); Shimoda, Tatsuya [School of Materials Science, Japan Advanced Institute of Science and Technology (JAIST), 1-1 Asahidai, Nomi, Ishikawa 923-1292 (Japan)

2011-11-01

Characteristics and role of Al oxide (Al-O) films used as catalyst-support layer for vertical growth of single-walled carbon nanotubes (SWCNTs) were studied. EB-deposited Al films (20 nm) were thermally oxidized at 400 deg. C (10 min, static air) to produce the most appropriate surface structure of Al-O. Al-O catalyst-support layers were characterized using various analytical measurements, i.e., atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), and spectroscopy ellipsometry (SE). The thermally oxidized Al-O has a highly roughened surface, and also has the most suitable surface chemical states compared to other type of Al-O support layers. We suggest that the surface of thermally oxidized Al-O characterized in this work enhanced Co catalyst activity to promote the vertically aligned SWCNT growth.

WATER-GAS SHIFT KINETICS OVER IRON OXIDE CATALYSTS AT MEMBRANE REACTOR CONDITIONS; A

International Nuclear Information System (INIS)

Carl R.F. Lund

2001-01-01

This report covers the second year of a project investigating water-gas shift catalysts for use in membrane reactors. It has been established that a simple iron high temperature shift catalyst becomes ineffective in a membrane reactor because the reaction rate is severely inhibited by the build-up of the product CO(sub 2). During the past year, an improved microkinetic model for water-gas shift over iron oxide was developed. Its principal advantage over prior models is that it displays the correct asymptotic behavior at all temperatures and pressures as the composition approaches equilibrium. This model has been used to explore whether it might be possible to improve the performance of iron high temperature shift catalysts under conditions of high CO(sub 2) partial pressure. The model predicts that weakening the surface oxygen bond strength by less than 5% should lead to higher catalytic activity as well as resistance to rate inhibition at higher CO(sub 2) partial pressures. Two promoted iron high temperature shift catalysts were studied. Ceria and copper were each studied as promoters since there were indications in the literature that they might weaken the surface oxygen bond strength. Ceria was found to be ineffective as a promoter, but preliminary results with copper promoted FeCr high temperature shift catalyst show it to be much more resistant to rate inhibition by high levels of CO(sub 2). Finally, the performance of sulfided CoMo/Al(sub 2)O(sub 3) catalysts under conditions of high CO(sub 2) partial pressure was simulated using an available microkinetic model for water-gas shift over this catalyst. The model suggests that this catalyst might be quite effective in a medium temperature water-gas shift membrane reactor, provided that the membrane was resistant to the H(sub 2)S that is required in the feed

Ionic Liquids in Selective Oxidation: Catalysts and Solvents.

Science.gov (United States)

Dai, Chengna; Zhang, Jie; Huang, Chongpin; Lei, Zhigang

2017-05-24

Selective oxidation has an important role in environmental and green chemistry (e.g., oxidative desulfurization of fuels and oxidative removal of mercury) as well as chemicals and intermediates chemistry to obtain high-value-added special products (e.g., organic sulfoxides and sulfones, aldehydes, ketones, carboxylic acids, epoxides, esters, and lactones). Due to their unique physical properties such as the nonvolatility, thermal stability, nonexplosion, high polarity, and temperature-dependent miscibility with water, ionic liquids (ILs) have attracted considerable attention as reaction solvents and media for selective oxidations and are considered as green alternatives to volatile organic solvents. Moreover, for easy separation and recyclable utilization, IL catalysts have attracted unprecedented attention as "biphasic catalyst" or "immobilized catalyst" by immobilizing metal- or nonmetal-containing ILs onto mineral or polymer supports to combine the unique properties of ILs (chemical and thermal stability, capacity for extraction of polar substrates and reaction products) with the extended surface of the supports. This review highlights the most recent outcomes on ILs in several important typical oxidation reactions. The contents are arranged in the series of oxidation of sulfides, oxidation of alcohols, epoxidation of alkenes, Baeyer-Villiger oxidation reaction, oxidation of alkanes, and oxidation of other compounds step by step involving ILs as solvents, catalysts, reagents, or their combinations.

Supramolecular water oxidation with rubda-based catalysts

KAUST Repository

Richmond, Craig J.

2014-11-05

Extremely slow and extremely fast new water oxidation catalysts based on the Rubda (bda = 2,2′-bipyri-dine-6,6′-dicarboxylate) systems are reported with turnover frequencies in the range of 1 and 900 cycless"1, respectively. Detailed analyses of the main factors involved in the water oxidation reaction have been carried out and are based on a combination of reactivity tests, electrochemical experiments, and DFT calculations. These analyses give a convergent interpretation that generates a solid understanding of the main factors involved in the water oxidation reaction, which in turn allows the design of catalysts with very low energy barriers in all the steps involved in the water oxidation catalytic cycle. We show that for this type of system p-stacking interactions are the key factors that influence reactivity and by adequately controlling them we can generate exceptionally fast water oxidation catalysts.

Study of propane partial oxidation on vanadium-containing catalysts

Energy Technology Data Exchange (ETDEWEB)

Komashko, G.A.; Khalamejda, S.V.; Zazhigalov, V.A. [AN Ukrainskoj SSR, Kiev (Ukraine). Inst. Fizicheskoj Khimii

1998-12-31

The present results indicate that maximum selectivity to acrylic acid can be reached over V-P-Zr-O catalysts. When the hydrocarbon concentration is 5.1 vol.% the selectivity is about 30% at quite high paraffin conversion. Conclusively, some explanations to the observed facts can be given. The V-P-O catalyst promotion with lanthanum by means of mechanochemical treatment is distinguished by the additive uniform spreading all over the matrix surface. Such twophase system is highly active in propane conversion (lanthanum oxide) and further oxidation of the desired products. The similar properties are attributed to V-P-Bi-La-O catalyst. Bismuth, tellurium and zirconium additives having clearly defined acidic properties provoke the surface acidity strengthening and make easier desorption of the acidic product (acrylic acid) from the surface lowering its further oxidation. Additionally, since bismuth and zirconium are able to form phosphates and, according to, to create space limitations for the paraffin molecule movement out of the active group boundaries, this can be one more support in favour of the selectivity increase. With this point of view very interesting results were obtained. It has been shown that the more limited the size of the vanadium unit, the higher the selectivity is. Monoclinic phase AV{sub 2}P{sub 2}O{sub 10} which consists in clusters of four vanadium atoms is sensibly more reactive than the orthorhombic phase consists in V{sub {infinity}} infinite chains. (orig.)

Catalytic wet air oxidation of chlorophenols over supported ruthenium catalysts

International Nuclear Information System (INIS)

Li Ning; Descorme, Claude; Besson, Michele

2007-01-01

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

Hydrous titanium oxide-supported catalysts

International Nuclear Information System (INIS)

Dosch, R.G.; Stohl, F.V.; Richardson, J.T.

1990-01-01

Catalysts were prepared on hydrous titanium oxide (HTO) supports by ion exchange of an active metal for Na + ions incorporated in the HTO support during preparation by reaction with the parent Ti alkoxide. Strong active metal-HTO interactions as a result of the ion exchange reaction can require significantly different conditions for activation as compared to catalysts prepared by more widely used incipient wetness methods. The latter catalysts typically involve conversion or while the HTO catalysts require the alteration of electrostatic bonds between the metal and support with subsequent alteration of the support itself. In this paper, the authors discuss the activation, via sulfidation or reduction, of catalysts consisting of Co, Mo, or Ni-Mo dispersed on HTO supports by ion exchange. Correlations between the activation process and the hydrogenation, hydrodeoxygenation, and hydrodesulfurization activities of the catalysts are presented

Nitrogen oxides storage catalysts containing cobalt

Science.gov (United States)

Lauterbach, Jochen; Snively, Christopher M.; Vijay, Rohit; Hendershot, Reed; Feist, Ben

2010-10-12

Nitrogen oxides (NO.sub.x) storage catalysts comprising cobalt and barium with a lean NO.sub.x storage ratio of 1.3 or greater. The NO.sub.x storage catalysts can be used to reduce NO.sub.x emissions from diesel or gas combustion engines by contacting the catalysts with the exhaust gas from the engines. The NO.sub.x storage catalysts can be one of the active components of a catalytic converter, which is used to treat exhaust gas from such engines.

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.

An improved method of preparation of nanoparticular metal oxide catalysts

DEFF Research Database (Denmark)

2014-01-01

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

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...

Metal Phosphate-Supported Pt Catalysts for CO Oxidation

Directory of Open Access Journals (Sweden)

Xiaoshuang Qian

2014-12-01

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

Synthesis of waste cooking oil based biodiesel via ferric-manganese promoted molybdenum oxide / zirconia nanoparticle solid acid catalyst: influence of ferric and manganese dopants.

Science.gov (United States)

Alhassan, Fatah H; Rashid, Umer; Taufiq-Yap, Yun Hin

2015-01-01

The utilization of ferric-manganese promoted molybdenum oxide/zirconia (Fe-Mn- MoO3/ZrO2) (FMMZ) solid acid catalyst for production of biodiesel was demonstrated. FMMZ is produced through impregnation reaction followed by calcination at 600°C for 3 h. The characterization of FMMZ had been done using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), thermal gravimetric analysis (TGA), temperature programmed desorption of NH3 (TPD-NH3), transmission electron microscopy(TEM) and Brunner-Emmett-Teller (BET) surface area measurement. The effect of waste cooking oil methyl esters (WCOME's) yield on the reactions variables such as reaction temperature, catalyst loading, molar ratio of methanol/oil and reusability were also assessed. The catalyst was used to convert the waste cooking oil into corresponding methyl esters (95.6%±0.15) within 5 h at 200℃ reaction temperature, 600 rpm stirring speed, 1:25 molar ratio of oil to alcohol and 4% w/w catalyst loading. The reported catalyst was successfully recycled in six connective experiments without loss in activity. Moreover, the fuel properties of WCOME's were also reported using ASTM D 6751 methods.

The kinetic and mechanistic aspects of the oxidative dehydrogenation of ethane over Li/Na/MgO catalysts

NARCIS (Netherlands)

Swaan, H.M.; Swaan, H.M.; Toebes, A.; Toebes, A.; van Ommen, J.G.; Seshan, Kulathuiyer; Ross, J.R.H.; Ross, J.R.H.

1992-01-01

Kinetic and mechanistic aspects of the oxidative dehydrogenation of ethane catalysed by Li/MgO and Li/Na/MgO have been investigated. Initial rate measurements at 600°C; revealed that the Li/MgO catalyst produced C2H4, CO2, CO and H2 by parallel reactions whereas the sodium-promoted catalyst produced

Bimetallic catalysts for continuous catalytic wet air oxidation of phenol.

Science.gov (United States)

Fortuny, A; Bengoa, C; Font, J; Fabregat, A

1999-01-29

Catalytic wet oxidation has proved to be effective at eliminating hazardous organic compounds, such as phenol, from waste waters. However, the lack of active long-life oxidation catalysts which can perform in aqueous phase is its main drawback. This study explores the ability of bimetallic supported catalysts to oxidize aqueous phenol solutions using air as oxidant. Combinations of 2% of CoO, Fe2O3, MnO or ZnO with 10% CuO were supported on gamma-alumina by pore filling, calcined and later tested. The oxidation was carried out in a packed bed reactor operating in trickle flow regime at 140 degrees C and 900 kPa of oxygen partial pressure. Lifetime tests were conducted for 8 days. The pH of the feed solution was also varied. The results show that all the catalysts tested undergo severe deactivation during the first 2 days of operation. Later, the catalysts present steady activity until the end of the test. The highest residual phenol conversion was obtained for the ZnO-CuO, which was significantly higher than that obtained with the 10% CuO catalyst used as reference. The catalyst deactivation is related to the dissolution of the metal oxides from the catalyst surface due to the acidic reaction conditions. Generally, the performance of the catalysts was better when the pH of the feed solution was increased.

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.

Mechanism-Based Design of Green Oxidation Catalysts

Energy Technology Data Exchange (ETDEWEB)

Rybak-Akimova, Elena [Tufts Univ., Medford, MA (United States)

2015-03-16

situation. Growing families of synthetic iron complexes that resemble active sites of metalloenzymes produce metal-based intermediates (rather than hydroxyl radicals) in reactions with oxygen donors. These complexes are very promising for selective oxygen and peroxide activation. In order to understand the mechanisms of metal-based small molecule activation, kinetically competent metal-oxygen intermediates must be identified. One of the grand challenges identified by the Department of Energy workshop "Catalysis for Energy" is understanding mechanisms and dynamics of catalyzed reactions. The research summarized herein focuses on detailed characterization of the formation and reactivity of various iron-peroxo- and iron-oxo intermediates that are involved in catalysis. Rates of rapid reactions were studied at low temperatures by a specialized technique termed cryogenic stopped-flow spectrophotometry. These measurements identified reaction conditions which favor the formation of catalytically competent oxidants. Chemical structures of reactive complexes was determined, and new, efficient catalysts for hydrocarbon oxidation were synthesized. Importantly, these catalysts are selective, they promote oxidation of hydrocarbons at a specific site. The catalysts are also efficient and robust, hundreds of cycles of substrate oxidation occur within minutes at room temperature. Furthermore, they enable utilization of environmentally friendly oxidants, such as hydrogen peroxide, which produces water as the only byproduct. Mechanistic insights uncovered the role of various acid-containing additives in catalytic oxidations. Proton delivery to the active catalytic sites facilitated oxidations, similarly to the catalytic pathways in metal-containing enzymes. Under certain conditions, two metals in one complex can act in concert, modeling the reactivity of a bacterial enzyme which converts methane into methanol. In related studies, a family of nickel complexes that react with carbon dioxide at

Remarkable promotion effect of trace sulfation on OMS-2 nanorod catalysts for the catalytic combustion of ethanol.

Science.gov (United States)

Zhang, Jie; Zhang, Changbin; He, Hong

2015-09-01

OMS-2 nanorod catalysts were synthesized by a hydrothermal redox reaction method using MnSO4 (OMS-2-SO4) and Mn(CH3COO)2 (OMS-2-AC) as precursors. SO4(2-)-doped OMS-2-AC catalysts with different SO4(2-) concentrations were prepared next by adding (NH4)2SO4 solution into OMS-2-AC samples to investigate the effect of the anion SO4(2-) on the OMS-2-AC catalyst. All catalysts were then tested for the catalytic oxidation of ethanol. The OMS-2-SO4 catalyst synthesized demonstrated much better activity than OMS-2-AC. The SO4(2-) doping greatly influenced the activity of the OMS-2-AC catalyst, with a dramatic promotion of activity for suitable concentration of SO4(2-) (SO4/catalyst=0.5% W/W). The samples were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), inductively coupled plasma optical emission spectroscopy (ICP-OES), NH3-TPD and H2-TPR techniques. The results showed that the presence of a suitable amount of SO4(2-) species in the OMS-2-AC catalyst could decrease the Mn-O bond strength and also enhance the lattice oxygen and acid site concentrations, which then effectively promoted the catalytic activity of OMS-2-AC toward ethanol oxidation. Thus it was confirmed that the better catalytic performance of OMS-2-SO4 compared to OMS-2-AC is due to the presence of some residual SO4(2-) species in OMS-2-SO4 samples. Copyright © 2015. Published by Elsevier B.V.

Mitigation of hydrogen by oxidation using nitrous oxide and noble metal catalysts

International Nuclear Information System (INIS)

Britton, M.D.

1995-01-01

This test studied the ability of a blend of nuclear-grade, noble-metal catalysts to catalyze a hydrogen/nitrous oxide reaction in an effort to mitigate a potential hydrogen (H 2 ) gas buildup in the Hanford Site Grout Disposal Facility. For gases having H 2 and a stoichiometric excess of either nitrous oxide or oxygen, the catalyst blend can effectively catalyze the H 2 oxidation reaction at a rate exceeding 380 μmoles of H 2 per hour per gram of catalyst (μmol/h/g) and leave the gas with less than a 0.15 residual H 2 Concentration. This holds true in gases with up to 2.25% water vapor and 0.1% methane. This should also hold true for gases with up to 0.1% carbon monoxide (CO) but only until the catalyst is exposed to enough CO to block the catalytic sites and stop the reaction. Gases with ammonia up to 1% may be slightly inhibited but can have reaction rates greater than 250 μmol/h/g with less than a 0.20% residual H 2 concentration. The mechanism for CO poisoning of the catalyst is the chemisorption of CO to the active catalyst sites. The CO sorption capacity (SC) of the catalyst is the total amount of CO that the catalyst will chemisorb. The average SC for virgin catalyst was determined to be 19.3 ± 2.0 μmoles of CO chemisorbed to each gram of catalyst (μmol/g). The average SC for catalyst regenerated with air was 17.3 ± 1.9 μmol/g

Chemical nature of catalysts of oxide nanoparticles in environment

Indian Academy of Sciences (India)

Carbon nanostructures (CNS) are often grown using oxide nanoparticles as catalyst in chemical vapour deposition and these oxides are not expected to survive as such during growth. In the present study, the catalysts of cobalt- and nickel oxide-based nanoparticles of sizes varying over a range have been reduced at 575 ...

Effect of catalysts on heterogeneous oxidation of coal

Energy Technology Data Exchange (ETDEWEB)

Glazkova, A P; Kazarova, Yu A; Suslov, A V

1978-01-01

Analyzes the effects of catalysts on the heterogeneous oxidation of coal in deflagration processes of stoichiometric mixtures. The following substances are studied as catalysts: alkali and alkaline-earth metals, and compounds of copper, lead, chromium, iron, and sulfur. In the first case the catalysts are used in the form of nitrates and the nitrate simultaneously plays the role of an oxidizer. In the second case the catalysts are added to stoichiometric mixtures of ammonium nitrate with carbon. It is shown that during carbon oxidation by nitrates the catalytic efficiency of the metals studied forms the following order: sodium > lead > potassium > barium > aluminium > calcium > magnesium > copper. The calculated and experimental parameters of combustion are given. The problem of dependence of combustion rate on combustion heat, the mechanism of the combustion reaction and the catalytic effects of the additives are discussed. Features of heterogeneous catalysis in the oxidation process of carbon by various oxidizers are analyzed. The investigations on the combustion process are important as the process takes place during explosion of coal dust in underground coal mines and during burning of coal in industrial furnaces. (34 refs.) (In Russian)

Coke formation on hydrodesulphurization catalysts. [Including effects of different promoters

Energy Technology Data Exchange (ETDEWEB)

Ternan, M.; Furimsky, E.; Parsons, B.I.

1979-02-01

The extent of coke formation was measured on a number of different hydrodesulfurization catalysts, primarily as a function of the catalyst chemical composition. Variations in the concentration of MoO/sub 3/ on the alumina, the type of catalyst promoter, the promoter/MoO/sub 3/ ratio, the presulfiding material and the reaction temperature were made. Increases in the reaction rate caused by either changes in the catalyst composition or by moderate changes in the reaction temperature were compared to the catalyst coke content. It was suggested that two types of coke were present on the catalyst, a reactive coke which is subsequently converted to reaction products and an unreactive coke which blocks catalytic sites.

Catalytic activity of oxide cerium-molybdenum-tellurium catalysts in oxidation ammonolysis

International Nuclear Information System (INIS)

Dzhordano, N.; Bart, D.; Madzhori, R.

1984-01-01

A commercial catalyst containing a mixture of Ce-, Mo-, Te oxides deposited on SiO 2 is shown to manifest a high efficiency in oxidative ammonolysis of propylene (C 3 - ) to acrylonitrile (AN). The dependence of the catalytic properties on the catalyst composition and reaction conditions is studied. It is established that three-component mixtures are more active and selective than the systems with a lesser number of components. Using the catalyst with the optimum ratio of constituent oxides in a microreactor at 440 deg enabled one to achieve initial selectivity in terms of AN equal to 82.5% at 97% conversion of C 3 - . Acrolein, acetonitrile, HCN and nitrogen oxides are the reaction by-products. A supposition is made that the reaction proceeds via the formation of π-compleXes on the centres of Te(4). Setective oxidation occurs on oxygen atoms bonded with the Mo(6) ions. Tellurium enhances the molybdenum reducibleness due to delocalization of electrons, whereas the cerium addition to the mixture of tellurium- and molybdenum oxides increases the rate of molybdenum reoxidation and thus enhances the catalytic system stability

Reactivation of a tin oxide-containing catalyst

Science.gov (United States)

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

1989-01-01

A method for the reactivation of a tin oxide-containing catalyst of a CO.sub.2 laser is provided. First, the catalyst is pretreated by a standard procedure. When the catalyst experiences diminished activity during usage, the heated zone surrounding the catalyst is raised to a temperature which is the operating temperature of the laser and 400.degree. C. for approximately one hour. The catalyst is exposed to the same laser gas mixture during this period. The temperature of the heated zone is then lowered to the operating temperature of the CO.sub.2 laser.

The Complete Oxidation of Ethanol at Low Temperature over a Novel Pd-Ce/γ-Al2O3-TiO2 Catalyst

International Nuclear Information System (INIS)

Wang, Yanping; Zhao, Jinshuang; Wang, Xiaoli; Li, Zhe; Liu, Pengfei

2013-01-01

Pd-Ce/γ-Al 2 O 3 -TiO 2 catalysts were prepared by combined sol.gel and impregnation methods. Transmission electron microscopy, X-ray diffraction, H 2 -temperature-programmed reduction, O 2 -temperature-programmed desorption, and ethanol oxidation experiments were conducted to determine the properties of the catalysts. Addition of an optimal amount of Ce improved the performance of the Pd/γ-Al 2 O 3 -TiO 2 catalyst in promoting the complete oxidation of ethanol. The catalyst with 1% Ce exhibited the highest activity, and catalyzed complete oxidation of ethanol at 175 .deg. C; its selectivity to CO 2 reached 87%. Characterization results show that addition of appropriate amount of Ce could enrich the PdO species, and weaken the Pd-O bonds, thus enhancing oxidation ability of the catalyst. Meanwhile, the introduction of CeO 2 could make PdO better dispersed on γ-Al 2 O 3 -TiO 2 , which is beneficial for the improvement of the catalytic oxidation activity

Catalytic Oxidation of Cyanogen Chloride over a Monolithic Oxidation Catalyst

National Research Council Canada - National Science Library

Campbell, Jeffrey

1997-01-01

The catalytic oxidation of cyanogen chloride was evaluated over a monolithic oxidation catalyst at temperatures between 200 and 300 deg C in air employing feed concentrations between 100 and 10,000 ppm...

The oxidation of copper catalysts during ethylene epoxidation.

Science.gov (United States)

Greiner, M T; Jones, T E; Johnson, B E; Rocha, T C R; Wang, Z J; Armbrüster, M; Willinger, M; Knop-Gericke, A; Schlögl, R

2015-10-14

The oxidation of copper catalysts during ethylene epoxidation was characterized using in situ photoemission spectroscopy and electron microscopy. Gas chromatography, proton-transfer reaction mass spectrometry and electron-ionization mass spectrometry were used to characterize the catalytic properties of the oxidized copper. We find that copper corrodes during epoxidation in a 1 : 1 mixture of oxygen and ethylene. The catalyst corrosion passes through several stages, beginning with the formation of an O-terminated surface, followed by the formation of Cu2O scale and eventually a CuO scale. The oxidized catalyst exhibits measurable activity for ethylene epoxidation, but with a low selectivity of 8/2500) Cu2O forms and eventually covers the surface.

Catalysts with Cu base supported in mixed oxides to generate H2: reformed of methanol in oxidant atmosphere

International Nuclear Information System (INIS)

Aguila M, M.M.; Perez H, R.; Rodriguez L, V.

2006-01-01

In this work, the characterization of Cu supported in CeO 2 -ZrO 2 , for to generate H 2 starting from the one reformed of methanol with water vapor and oxygen is presented. The sol-gel technique and classic impregnation for the obtaining of the supports and catalysts respectively were used. The materials were characterized by XRD, SEM, adsorption- desorption of N 2 and TPR. The catalytic materials presented crystalline phases associated with the zircon (tetragonal and monoclinic phase) and the ceria (cubic phase) depending on the CeO 2 /ZrO 2 relationship. The morphology of the catalysts was analyzed by SEM being observed semispheric particles for the rich materials in ZrO 2 and added planars in the rich materials in CeO 2 . The ceria addition to the zircon favors the specific area of the mixed oxides CeO 2 -ZrO 2 and it promotes the reducibility of the copper oxide at low temperatures. The rich catalysts in ceria also showed high activity in the methanol transformation and bigger selectivity toward the production of H 2 . This result is associated with the presence of copper species that decrease to low temperature present in the rich catalysts in ceria and that they are not present in the rich catalysts in zircon. (Author)

Selective Oxidations using Nanostructured Heterogeneous Catalysts

DEFF Research Database (Denmark)

Mielby, Jerrik Jørgen

and because they produce H2O as the only by-product. Chapter 1 gives a short introduction to basic concepts in heterogeneous catalysis and green chemistry. Furthermore, the chapter gives an overview of the most important strategies to synthesise functional nanostructured materials and highlights how detailed......The aim of this thesis is to investigate and develop new efficient methods to oxidise alcohols and amines using heterogeneous catalysts and either O2 or H2O2 as oxidants. From an economic and environmental point of view, these oxidants are ideal, because they are cheap and readily available...... understanding of size, shape and structure can help in the development of new and more efficient heterogeneous catalysts. The chapter is not intended to give a complete survey, but rather to introduce some of the recent developments in the synthesis of nanostructured heterogeneous catalysts. Finally...

Poly (p-phenylendiamine/TiO2) nanocomposite promoted Pt/C catalyst for methanol and ethanol electrooxidation in alkaline medium

International Nuclear Information System (INIS)

Rostami, Hussein; Rostami, Abbas Ali; Omrani, Abdollah

2016-01-01

In the present study, poly (p-phenylendiamine/titanium dioxide) (PpPDA/TiO 2 ) nanocomposites (NCs) were prepared by in situ polymerization of p-phenylenediamine monomer with of different TiO 2 loading. A facile method was developed to promote the electrocatalytic activity of commercial Pt/C catalyst by ultrasonically mixing Pt/C catalyst and PpPDA/TiO 2 NCs. The PpPDA/TiO 2 NC, Pt/C catalyst and composite catalyst of Pt/C + PpPDA/TiO 2 were characterized by scanning electron microscopy (SEM) and Fourier transform infrared (FTIR) spectroscopy. The surface morphology of Pt/C is significantly influenced by the presence of PpPDA/TiO 2 NC as confirmed by SEM observations. Cyclic voltammetry (CV) measurements showed that the PpPDA/TiO 2 NC leads to a significant improvement in the activity and stability of Pt/C for alcohol oxidation especially for ethanol oxidation in alkaline medium. For Pt/C + PpPDA/TiO 2 , the onset potentials shift to negative values by 30 and 160 mV compared to the onset potentials of Pt/C for methanol and ethanol oxidation, respectively. Chronoamperometry (CA) and electrochemical impedance spectroscopy (EIS) results also confirmed that this composite catalyst has superior catalytic performance towards ethanol oxidation compared to the pure Pt/C catalyst.

One-pot synthesis of reduced graphene oxide supported PtCuy catalysts with enhanced electro-catalytic activity for the methanol oxidation reaction

International Nuclear Information System (INIS)

Peng, Xinglan; Zhao, Yanchun; Chen, Duhong; Fan, Yanfang; Wang, Xiao; Wang, Weili; Tian, Jianniao

2014-01-01

The outstanding performance PtCu y (y = 1,2,3) alloy nanoparticles supported on reduced graphene oxide (rGO) have been synthesized by a facile, efficient, one-pot hydrothermal synthesis approach. The as-prepared PtCu y /rGO catalysts are comprehensively characterized by X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy. Cyclic voltammetry, CO-stripping voltammetry and chronoamperometry results reveal that the PtCu y /rGO catalysts have higher electro-catalytic activity, more negative onset oxidative potential, more excellent tolerance ability for CO poisoning and enhanced stability for the electro-oxidation of methanol compared to pure Pt/rGO. As far as the as-made PtCu y /rGO catalysts are concerned, the PtCu 2 /rGO exhibits the highest electro-catalytic activity. The mechanism of the promoting effect of Cu on Pt is explained based on the electronic modification effect. The nature of interfacial interactions between the Pt-Cu active metal phase and the rGO supporting materials is crucial to achieving high performance

Electrical conductivity of uranium-antimony oxide catalysts

International Nuclear Information System (INIS)

Golunski, S.E.; Nevell, T.G.; Hucknall, D.J.

1985-01-01

The relative ionic and electronic contributions to the electrical conductivity of a uranium-antimony oxide catalyst and of USbO 5 have been determined from measurements of a.c. and d.c. conductance. Under inert atmospheres (390 to 775 K) conduction in the catalyst (predominantly USb 3 O 10 together with small proportions of Sb 2 O 4 and USbO 5 ) is associated with both electronic and effectively charged atomic point defects. Only electronic conduction occurs in USbO 5 . Under oxygen (10 to 70 kPa, 493 to 682 K) both materials are n-type semiconductors at higher temperatures, but at lower temperatures semiconducting behaviour varies with the pressure of oxygen. Heating USbO 5 in oxygen induces an ionic contribution to conductivity. Ionic conduction in the catalyst is eliminated by heating in hydrogen or propene at 470 K but is restored by heating in oxygen. It is suggested that both charged oxygen vacancies and interstitial oxide ions are involved in interactions of gaseous components with uranium-antimony oxides. With alkenes, interstitial oxide ions give rise to the products of selective partial oxidation. (author)

Electrical conductivity of uranium-antimony oxide catalysts

Energy Technology Data Exchange (ETDEWEB)

Golunski, S.E.; Nevell, T.G. (Portsmouth Polytechnic (UK)); Hucknall, D.J. (Southampton Univ. (UK). Dept. of Chemistry)

1985-05-01

The relative ionic and electronic contributions to the electrical conductivity of a uranium-antimony oxide catalyst and of USbO/sub 5/ have been determined from measurements of a.c. and d.c. conductance. Under inert atmospheres (390 to 775 K) conduction in the catalyst (predominantly USb/sub 3/O/sub 10/ together with small proportions of Sb/sub 2/O/sub 4/ and USbO/sub 5/) is associated with both electronic and effectively charged atomic point defects. Only electronic conduction occurs in USbO/sub 5/. Under oxygen (10 to 70 kPa, 493 to 682 K) both materials are n-type semiconductors at higher temperatures, but at lower temperatures semiconducting behaviour varies with the pressure of oxygen. Heating USbO/sub 5/ in oxygen induces an ionic contribution to conductivity. Ionic conduction in the catalyst is eliminated by heating in hydrogen or propene at 470 K but is restored by heating in oxygen. It is suggested that both charged oxygen vacancies and interstitial oxide ions are involved in interactions of gaseous components with uranium-antimony oxides. With alkenes, interstitial oxide ions give rise to the products of selective partial oxidation.

Supramolecular water oxidation with Ru-bda-based catalysts.

Science.gov (United States)

Richmond, Craig J; Matheu, Roc; Poater, Albert; Falivene, Laura; Benet-Buchholz, Jordi; Sala, Xavier; Cavallo, Luigi; Llobet, Antoni

2014-12-22

Extremely slow and extremely fast new water oxidation catalysts based on the Ru-bda (bda=2,2'-bipyridine-6,6'-dicarboxylate) systems are reported with turnover frequencies in the range of 1 and 900 cycles s(-1) , respectively. Detailed analyses of the main factors involved in the water oxidation reaction have been carried out and are based on a combination of reactivity tests, electrochemical experiments, and DFT calculations. These analyses give a convergent interpretation that generates a solid understanding of the main factors involved in the water oxidation reaction, which in turn allows the design of catalysts with very low energy barriers in all the steps involved in the water oxidation catalytic cycle. We show that for this type of system π-stacking interactions are the key factors that influence reactivity and by adequately controlling them we can generate exceptionally fast water oxidation catalysts. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Soot oxidation over NOx storage catalysts. Activity and deactivation

International Nuclear Information System (INIS)

Krishna, K.; Makkee, M.

2006-01-01

Soot oxidation activity and deactivation of NO x storage and reduction (NSR) catalysts containing Pt, K, and Ba supported on Al 2 O 3 , are studied under a variety of reaction conditions. K-containing catalysts decrease soot oxidation temperature with O 2 alone and the presence of Pt further enhance the activity due to synergetic effect. The active species responsible for synergism on Pt/K-Al 2 O 3 are unstable and cannot be regenerated. Soot oxidation temperature decreases by about 150 o C with NO+O 2 exhaust feed gas and under lean conditions NSR system acts as catalysed soot filter (CSF). The reactions that are mainly responsible for decreasing soot oxidation temperature are: (1) soot oxidation with NO 2 followed by NO recycles to NO 2 , and (2) soot oxidation with O 2 assisted by NO 2 . Only a part of the stored NO x that is decomposed at high temperatures under lean conditions is found to be useful for soot oxidation. NO x storage capacity of NSR catalysts decreases upon ageing under soot oxidising conditions. This will lead to a decreased soot oxidation activity on stored nitrate decomposition. Pt/K-Al 2 O 3 catalyst is more active, but least stable compared with Pt/Ba-Al 2 O 3 . (author)

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

Single-site catalyst promoters accelerate metal-catalyzed nitroarene hydrogenation

KAUST Repository

Wang, Liang

2018-04-04

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

Single-site catalyst promoters accelerate metal-catalyzed nitroarene hydrogenation

KAUST Repository

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

2018-01-01

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

Mercury Oxidation over Selective Catalytic Reduction (SCR) Catalysts - Ph.d. thesis Karin Madsen

DEFF Research Database (Denmark)

Madsen, Karin

The vanadium-based SCR catalyst used for NOx-control promotes the oxidation of elemental mercury Hg0 to Hg2+ in flue gases from coal-fired power plants. Hg2+ is water soluble and can effectively be captured in a wet scrubber. This means that the combination of an SCR with a wet FGD can offer an e...

Synthesis of MoVTeNb Oxide Catalysts with Tunable Particle Dimensions

DEFF Research Database (Denmark)

Kolenko, Yury V.; Zhang, Wei; d'Alnoncourt, Raoul Naumann

2011-01-01

Reliable procedures for the controlled synthesis of phase-pure MoVTeNb mixed oxides with M1 structure (ICSD 55097) and tunable crystal dimensions were developed to study the structure sensitivity of the selective oxidation of propane to acrylic acid. A series of powdered M1 catalysts...... catalysts were studied in the selective oxidation of propane to acrylic acid, revealing that active sites appear on the entire M1 surface and illustrating the high sensitivity of catalyst performance on the catalyst synthesis method....

Oxidation catalysts and process for preparing same

International Nuclear Information System (INIS)

1980-01-01

Compounds particularly suitable as oxidation catalysis are described, comprising specified amounts of uranium, antimony and tin as oxides. Processes for making and using the catalysts are described. (U.K.)

Lanthanoid-free perovskite oxide catalyst for dehydrogenation of ethylbenzene working with redox mechanism

Science.gov (United States)

Watanabe, Ryo; Ikushima, Maiko; Mukawa, Kei; Sumomozawa, Fumitaka; Ogo, Shuhei; Sekine, Yasushi

2013-01-01

For the development of highly active and robust catalysts for dehydrogenation of ethylbenzene (EBDH) to produce styrene; an important monomer for polystyrene production, perovskite-type oxides were applied to the reaction. Controlling the mobility of lattice oxygen by changing the structure of Ba1 − xSrxFeyMn1 − yO3 − δ (0 ≤ x ≤ 1, 0.2 ≤ y ≤ 0.8), perovskite catalyst showed higher activity and stability on EBDH. The optimized Ba/Sr and Fe/Mn molar ratios were 0.4/0.6 and 0.6/0.4, respectively. Comparison of the dehydrogenation activity of Ba0.4Sr0.6Fe0.6Mn0.4O3 − δ catalyst with that of an industrial potassium promoted iron (Fe–K) catalyst revealed that the Ba0.4Sr0.6Fe0.6Mn0.4O3 − δ catalyst showed higher initial activity than the industrial Fe–K oxide catalyst. Additionally, the Ba0.4Sr0.6Fe0.6Mn0.4O3 − δ catalyst showed high activity and stability under severe conditions, even at temperatures as low as 783 K, or at the low steam/EB ratio of 2, while, the Fe–K catalyst showed low activity in such conditions. Comparing reduction profiles of the Ba0.4Sr0.6Fe0.6Mn0.4O3 − δ and the Fe–K catalysts in a H2O/H2 atmosphere, reduction was suppressed by the presence of H2O over the Ba0.4Sr0.6Fe0.6Mn0.4O3 − δ catalyst while the Fe–K catalyst was reduced. In other words, Ba0.4Sr0.6Fe0.6Mn0.4O3 − δ catalyst had higher potential for activating the steam than the Fe–K catalyst. The lattice oxygen in perovskite-structure was consumed by H2, subsequently the consumed lattice oxygen was regenerated by H2O. So the catalytic performance of Ba0.4Sr0.6Fe0.6Mn0.4O3 − δ was superior to that of Fe–K catalyst thanks to the high redox property of the Ba0.4Sr0.6Fe0.6Mn0.4O3 − δ perovskite oxide. PMID:24790949

Lanthanoid-free perovskite oxide catalyst for dehydrogenation of ethylbenzene working with redox mechanism

Directory of Open Access Journals (Sweden)

Ryo eWatanabe

2013-10-01

Full Text Available For the development of highly active and robust catalysts for dehydrogenation of ethylbenzene (EBDH to produce styrene; an important monomer for polystyrene production, perovskite-type oxides were applied to the reaction. Controlling the mobility of lattice oxygen by changing the structure of Ba1–xSrxFeyMn1–yO3–d(0 ≤ x≤ 1, 0.2 ≤ y≤ 0.8, perovskite catalyst showed higher activity and stability on EBDH. The optimized Ba/Sr and Fe/Mn molar ratios were 0.4/0.6 and 0.6/0.4, respectively. Comparison of the dehydrogenation activity of Ba0.4Sr0.6Fe0.6Mn0.4O3–d catalyst with that of an industrial potassium promoted iron (Fe–K catalyst revealed that the Ba0.4Sr0.6Fe0.6Mn0.4O3–d catalyst showed higher initial activity than the industrial Fe–K oxide catalyst. Additionally, the Ba0.4Sr0.6Fe0.6Mn0.4O3–d catalyst showed high activity and stability under severe conditions, even at temperatures as low as 783 K, or at the low steam/EB ratio of 2, while, the Fe–K catalyst showed low activity in such conditions. Comparing reduction profiles of the Ba0.4Sr0.6Fe0.6Mn0.4O3–d and the Fe–K catalysts in aH2O/H2 atmosphere, reduction was suppressed by the presence of H2O over the Ba0.4Sr0.6Fe0.6Mn0.4O3–d catalyst while the Fe–K catalyst was reduced. In other words, Ba0.4Sr0.6Fe0.6Mn0.4O3–d catalyst had higher potential for activating the steam than the Fe–K catalyst. The lattice oxygen in perovskite-structure was consumed by H2, subsequently the consumed lattice oxygen was regenerated by H2O. So the catalytic performance of Ba0.4Sr0.6Fe0.6Mn0.4O3–d was superior to that of Fe–K catalyst thanks to the high redox property of the Ba0.4Sr0.6Fe0.6Mn0.4O3–d perovskite oxide.

Lanthanoid-free perovskite oxide catalyst for dehydrogenation of ethylbenzene working with redox mechanism

Science.gov (United States)

Watanabe, Ryo; Ikushima, Maiko; Mukawa, Kei; Sumomozawa, Fumitaka; Ogo, Shuhei; Sekine, Yasushi

2013-10-01

For the development of highly active and robust catalysts for dehydrogenation of ethylbenzene (EBDH) to produce styrene; an important monomer for polystyrene production, perovskite-type oxides were applied to the reaction. Controlling the mobility of lattice oxygen by changing the structure of Ba1-xSrxFeyMn1-yO3-d(0 ≤ x≤ 1, 0.2 ≤ y≤ 0.8), perovskite catalyst showed higher activity and stability on EBDH. The optimized Ba/Sr and Fe/Mn molar ratios were 0.4/0.6 and 0.6/0.4, respectively. Comparison of the dehydrogenation activity of Ba0.4Sr0.6Fe0.6Mn0.4O3-d catalyst with that of an industrial potassium promoted iron (Fe-K) catalyst revealed that the Ba0.4Sr0.6Fe0.6Mn0.4O3-d catalyst showed higher initial activity than the industrial Fe-K oxide catalyst. Additionally, the Ba0.4Sr0.6Fe0.6Mn0.4O3-d catalyst showed high activity and stability under severe conditions, even at temperatures as low as 783 K, or at the low steam/EB ratio of 2, while, the Fe-K catalyst showed low activity in such conditions. Comparing reduction profiles of the Ba0.4Sr0.6Fe0.6Mn0.4O3-d and the Fe-K catalysts in aH2O/H2 atmosphere, reduction was suppressed by the presence of H2O over the Ba0.4Sr0.6Fe0.6Mn0.4O3-d catalyst while the Fe-K catalyst was reduced. In other words, Ba0.4Sr0.6Fe0.6Mn0.4O3-d catalyst had higher potential for activating the steam than the Fe-K catalyst. The lattice oxygen in perovskite-structure was consumed by H2, subsequently the consumed lattice oxygen was regenerated by H2O. So the catalytic performance of Ba0.4Sr0.6Fe0.6Mn0.4O3-d was superior to that of Fe-K catalyst thanks to the high redox property of the Ba0.4Sr0.6Fe0.6Mn0.4O3-d perovskite oxide.

Lanthanoid-free perovskite oxide catalyst for dehydrogenation of ethylbenzene working with redox mechanism.

Science.gov (United States)

Watanabe, Ryo; Ikushima, Maiko; Mukawa, Kei; Sumomozawa, Fumitaka; Ogo, Shuhei; Sekine, Yasushi

2013-01-01

For the development of highly active and robust catalysts for dehydrogenation of ethylbenzene (EBDH) to produce styrene; an important monomer for polystyrene production, perovskite-type oxides were applied to the reaction. Controlling the mobility of lattice oxygen by changing the structure of Ba1 - x SrxFe y Mn1 - y O3 - δ (0 ≤ x ≤ 1, 0.2 ≤ y ≤ 0.8), perovskite catalyst showed higher activity and stability on EBDH. The optimized Ba/Sr and Fe/Mn molar ratios were 0.4/0.6 and 0.6/0.4, respectively. Comparison of the dehydrogenation activity of Ba0.4Sr0.6Fe0.6Mn0.4O3 - δ catalyst with that of an industrial potassium promoted iron (Fe-K) catalyst revealed that the Ba0.4Sr0.6Fe0.6Mn0.4O3 - δ catalyst showed higher initial activity than the industrial Fe-K oxide catalyst. Additionally, the Ba0.4Sr0.6Fe0.6Mn0.4O3 - δ catalyst showed high activity and stability under severe conditions, even at temperatures as low as 783 K, or at the low steam/EB ratio of 2, while, the Fe-K catalyst showed low activity in such conditions. Comparing reduction profiles of the Ba0.4Sr0.6Fe0.6Mn0.4O3 - δ and the Fe-K catalysts in a H2O/H2 atmosphere, reduction was suppressed by the presence of H2O over the Ba0.4Sr0.6Fe0.6Mn0.4O3 - δ catalyst while the Fe-K catalyst was reduced. In other words, Ba0.4Sr0.6Fe0.6Mn0.4O3 - δ catalyst had higher potential for activating the steam than the Fe-K catalyst. The lattice oxygen in perovskite-structure was consumed by H2, subsequently the consumed lattice oxygen was regenerated by H2O. So the catalytic performance of Ba0.4Sr0.6Fe0.6Mn0.4O3 - δ was superior to that of Fe-K catalyst thanks to the high redox property of the Ba0.4Sr0.6Fe0.6Mn0.4O3 - δ perovskite oxide.

Nanosized spinel oxide catalysts for CO-oxidation prepared via CoMnMgAl quaternary hydrotalcite route

Energy Technology Data Exchange (ETDEWEB)

Mokhtar, M., E-mail: mmoustafa@kau.edu.s [Chemistry Department, Faculty of Science, King Abdulaziz University, 21589 Jeddah, P.O. Box 80203 (Saudi Arabia); Basahel, S.N.; Al-Angary, Y.O. [Chemistry Department, Faculty of Science, King Abdulaziz University, 21589 Jeddah, P.O. Box 80203 (Saudi Arabia)

2010-03-18

Catalytic activity of the Co-Mn-Mg-Al mixed oxide spinel catalysts was examined in CO oxidation by O{sub 2}. The prepared catalysts were characterized by chemical analysis (ICP), infrared spectroscopy (FTIR), thermal analysis (TG, DTG), powder X-ray diffraction (XRD), surface area measurements, and scanning electron microscopy (SEM).The calcined hydrotalcite-like precursor was composed of spinel-like Co-Mn-Mg-Al mixed oxide as the only XRD crystalline phases. The nanosized spinel oxide catalysts produced by calcination of hydrotalcites showed higher S{sub BET} than CoMn-hydrotalcite samples as calcination led to dehydroxylation and carbonate decomposition of anions in interlayer spaces. All the catalysts showed 100% CO conversion at high temperature even those calcined at 800 {sup o}C. A catalyst with Co/Mn = 4 and calcined at 500 {sup o}C showed 100% CO conversion at 160 {sup o}C. Moreover, this catalyst exhibited quite good durability without deactivation in 60 h stability test.

Catalytic wet air oxidation of aniline with nanocasted Mn-Ce-oxide catalyst.

Science.gov (United States)

Levi, R; Milman, M; Landau, M V; Brenner, A; Herskowitz, M

2008-07-15

The catalytic wet air oxidation of aqueous solution containing 1000 ppm aniline was conducted in a trickle-bed reactor packed with a novel nanocasted Mn-Ce-oxide catalyst (surface area of 300 m2/g) prepared using SBA-15 silica as a hard template. A range of liquid hourly space velocities (5-20 h(-1)) and temperatures (110-140 degrees C) at 10 bar of oxygen were tested. The experiments were conducted to provide the intrinsic performance of the catalysts. Complete aniline conversion, 90% TOC conversion, and 80% nitrogen mineralization were achieved at 140 degrees C and 5 h(-1). Blank experiments yielded relatively low homogeneous aniline (<35%) and negligible TOC conversions. Fast deactivation of the catalysts was experienced due to leaching caused by complexation with aniline. Acidification of the solution with HCI (molar HCI to aniline ratio of 1.2) was necessary to avoid colloidization and leaching of the nanoparticulate catalyst components. The catalyst displayed stable performance for over 200 h on stream.

Electrochemical promotion of catalytic reactions with Pt/C (or Pt/Ru/C)//PBI catalysts

DEFF Research Database (Denmark)

Petrushina, Irina; Bjerrum, Niels; Bandur, Viktor

2007-01-01

The paper is an overview of the results of the investigation on electrochemical promotion of three catalytic reactions: methane oxidation with oxygen, NO reduction with hydrogen at 135 degrees C and Fischer-Tropsch synthesis (FTS) at 170 degrees C in the [CH4/O-2(or NO/H-2 or CO/H-2)/Ar//Pt(or Pt....../Ru)//PBI(H3PO4)/H-2, Ar] fuel cell. It has been shown that the partial methane oxidation to C2H2 and the C-2 selectivity were electrochemically promoted by the negative catalyst polarization. This was also the case in NO reduction with hydrogen for low NO and H-2 partial pressures. In both cases the catalytic...... reactions have been promoted by the electrochemically produced hydrogen. It has been found that the NO reduction with hydrogen on the Pt/PBI strongly depends on NO and hydrogen partial pressures in the working gas mixture. At higher NO and H-2 partial pressures the catalysis is promoted...

Low-temperature conversion of ammonia to nitrogen in water with ozone over composite metal oxide catalyst.

Science.gov (United States)

Chen, Yunnen; Wu, Ye; Liu, Chen; Guo, Lin; Nie, Jinxia; Chen, Yu; Qiu, Tingsheng

2018-04-01

As one of the most important water pollutants, ammonia nitrogen emissions have increased year by year, which has attracted people's attention. Catalytic ozonation technology, which involves production of ·OH radical with strong oxidation ability, is widely used in the treatment of organic-containing wastewater. In this work, MgO-Co 3 O 4 composite metal oxide catalysts prepared with different fabrication conditions have been systematically evaluated and compared in the catalytic ozonation of ammonia (50mg/L) in water. In terms of high catalytic activity in ammonia decomposition and high selectivity for gaseous nitrogen, the catalyst with MgO-Co 3 O 4 molar ratio 8:2, calcined at 500°C for 3hr, was the best one among the catalysts we tested, with an ammonia nitrogen removal rate of 85.2% and gaseous nitrogen selectivity of 44.8%. In addition, the reaction mechanism of ozonation oxidative decomposition of ammonia nitrogen in water with the metal oxide catalysts was discussed. Moreover, the effect of coexisting anions on the degradation of ammonia was studied, finding that SO 4 2- and HCO 3 - could inhibit the catalytic activity while CO 3 2- and Br - could promote it. The presence of coexisting cations had very little effect on the catalytic ozonation of ammonia nitrogen. After five successive reuses, the catalyst remained stable in the catalytic ozonation of ammonia. Copyright © 2017. Published by Elsevier B.V.

Research advances in the catalysts for the selective oxidation of ethane to aldehydes

Institute of Scientific and Technical Information of China (English)

ZHANG Zhe; ZHAO Zhen; XU Chunming

2005-01-01

Selective oxidation of ethane to aldehydes is one of the most difficult processes in the catalysis researches of low alkanes. The development of selective oxidation of ethane to aldehydes (formaldehyde, acetaldehyde and acrolein) is discussed. The latest progress of the catalysts, including bulk or supported metal oxide catalysts, highly dispersed and isolated active sites catalysts, and the photo-catalytic ethane oxidation catalysts, partial oxidation of ethane in the gas phase, and the proposed reaction pathways from ethane to aldehydes are involved.

Ni–Ta–O mixed oxide catalysts for the low temperature oxidative dehydrogenation of ethane to ethylene

KAUST Repository

Zhu, Haibo

2015-09-01

The "wet" sol-gel and "dry" solid-state methods were used to prepare Ni-Ta-O mixed oxide catalysts. The resulting Ni-Ta oxides exhibit high activity and selectivity for the low temperature oxidative dehydrogenation of ethane to ethylene. The Ta/(Ni + Ta) atomic ratios (varying from 0 to 0.11 in "wet" sol-gel method, and from 0 to 0.20 in "dry" solid-state method) as well as the preparation methods used in the synthesis, play important roles in controlling catalyst structure, activity, selectivity and stability in the oxidative dehydrogenation of ethane. Electron microscopy characterizations (TEM, EELS mapping, and HAADF-STEM) clearly demonstrate that the Ta atoms are inserted into NiO crystal lattice, resulting in the formation of a new Ni-Ta oxide solid solution. More Ta atoms are found to be located at the lattice sites of crystal surface in sol-gel catalyst. While, a small amount of thin layer of Ta2O5 clusters are detected in solid-state catalyst. Further characterization by XRD, N2 adsorption, SEM, H2-TPR, XPS, and Raman techniques reveal different properties of these two Ni-Ta oxides. Due to the different properties of the Ni-Ta oxide catalysts prepared by two distinct approaches, they exhibit different catalytic behaviors in the ethane oxidative dehydrogenation reaction at low temperature. Thus, the catalytic performance of Ni-Ta-O mixed oxide catalysts can be systematically modified and tuned by selecting a suitable synthesis method, and then varying the Ta content. ©2015 Elsevier Inc. All rights reserved.

Radiation modification of vanadium catalyst for anthracene oxidation

International Nuclear Information System (INIS)

Norek, J.; Vymetal, J.; Mucka, V.; Pospisil, M.; Cabicar, J.

1985-01-01

Vanadium pentoxide on a suitable carrier is often used as catalyst for the oxidation of anthracene in the gaseous phase to 9,10-anthraquinone. The activity and selectivity of the catalyst may be affected by irradiation. The effects were studied of gamma radiation on the properties of the catalyst where the active system was a V 2 O 5 -KOH-K 2 SO 4 mixture on a Al 2 O 3 +SiO 2 carrier. The 60 Co radiation source had an activity of 185 TBq; the carrier of the catalyst was irradiated at a dose rate of 3.05, 1.98 and 0.084 kGy/h to a total dose of 10 kGy. Irradiation increased the selectivity of the catalyst such that in the oxidation temperature optimum of 300 to 400 degC the yield of 9,10-anthraquinone increased by 4.6 to 4.8 %mol. to roughly 90 %mol.; a significant reduction of the content of acid components (phthalanhydride) in the oxidation product also occurred. This effect remained unchanged for 5 months after irradiation. A reduction of selectivity was observed at lower dose rates only in the temperature range between 400 and 480 degC. (A.K.)

Selective hydrogenation of 4-isobutylacetophenone over a sodium-promoted Pd/C catalyst

International Nuclear Information System (INIS)

Cho, Hong-Baek; Lee, Bae Uk; Nakayama, Tadachika; Park, Yeung-Ho; Ryu, Chung-Han

2013-01-01

The effect of sodium promotion on the selective hydrogenation of 4-isobutylacetophenone, 4-IBAP, was investigated over a Pd/C catalyst. A precipitation and deposition method was used to prepare the catalyst, and sodium was promoted on the Pd/C catalyst via post-impregnation while varying the sodium content. The sodium-promoted Pd/C catalyst resulted in a significantly improved yield greater than 96% of the desired product, 1-(4-isobutylphenyl) ethanol (4-IBPE), compared with the non-patented literature results under a mild hydrogenation condition. A detailed hydrogenation network over the Pd/C catalyst was suggested. The reaction mechanism for the yield and selectivity enhancement of 4-IBPE induced-by the promoted Pd/C was elucidated in relation to the geometric and electronic effects of reactant molecules in the microporous support depending on the reaction steps

Oxidations of amines with molecular oxygen using bifunctional gold–titania catalysts

DEFF Research Database (Denmark)

Klitgaard, Søren Kegnæs; Egeblad, Kresten; Mentzel, Uffe Vie

2008-01-01

–titania catalysts can be employed to facilitate the oxidation of amines into amides with high selectivity. Furthermore, we report that pure titania is in fact itself a catalyst for the oxidation of amines with molecular oxygen under very mild conditions. We demonstrate that these new methodologies open up for two......Over the past decades it has become clear that supported gold nanoparticles are surprisingly active and selective catalysts for several green oxidation reactions of oxygen-containing hydrocarbons using molecular oxygen as the stoichiometric oxidant. We here report that bifunctional gold...

Oxidative dehydrogenation of ethylbenzene using nitrous oxide over vanadia-magnesia catalysts

NARCIS (Netherlands)

Shiju, N.R.; Anilkumar, M.; Gokhale, S.P.; Rao, B.S.; Satyanarayana, C.V.V.

2011-01-01

A series of V-Mg-O catalysts with different loadings of vanadia were prepared by the wet impregnation method and the effect of the local structure of these catalysts on the oxidative dehydrogenation of ethylbenzene with N2O was investigated. High styrene selectivity (97%) was obtained at 773 K. The

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

SnO2 promoted by alkali metal oxides for soot combustion: The effects of surface oxygen mobility and abundance on the activity

Science.gov (United States)

Rao, Cheng; Shen, Jiating; Wang, Fumin; Peng, Honggen; Xu, Xianglan; Zhan, Hangping; Fang, Xiuzhong; Liu, Jianjun; Liu, Wenming; Wang, Xiang

2018-03-01

In this study, SnO2-based catalysts promoted by different alkali metal oxides with a Sn/M (M = Li, Na, K, Cs) molar ratio of 9/1 have been prepared for soot combustion. In comparison with the un-modified SnO2 support, the activity of the modified catalysts has been evidently enhanced, following the sequence of CsSn1-9 > KSn1-9 > NaSn1-9 > LiSn1-9 > SnO2. As testified by Raman, H2-TPR, soot-TPR-MS, XPS and O2-TPD results, the incorporation of various alkali metal oxides can induce the formation of more abundant and mobile oxygen species on the surface of the catalysts. Moreover, quantified results have proved that the amount of the surface active oxygen species is nearly proportional to the activity of the catalysts. CsSn1-9, the catalyst promoted by cesium oxide, owns the largest amount of surface mobile oxygen species, thus having the highest activity among all the studied catalysts. It is concluded that the amount of surface active and mobile oxygen species is the major factor determining the activity of the catalysts for soot combustion.

Oxidation of elemental mercury by modified spent TiO2-based SCR-DeNOx catalysts in simulated coal-fired flue gas.

Science.gov (United States)

Zhao, Lingkui; Li, Caiting; Zhang, Xunan; Zeng, Guangming; Zhang, Jie; Xie, Yin'e

2016-01-01

In order to reduce the costs, the recycle of spent TiO2-based SCR-DeNOx catalysts were employed as a potential catalytic support material for elemental mercury (Hg(0)) oxidation in simulated coal-fired flue gas. The catalytic mechanism for simultaneous removal of Hg(0) and NO was also investigated. The catalysts were characterized by Brunauer-Emmett-Teller (BET), scanning electron microscope (SEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) method. Results indicated that spent TiO2-based SCR-DeNOx catalyst supported Ce-Mn mixed oxides catalyst (CeMn/SCR1) was highly active for Hg(0) oxidation at low temperatures. The Ce1.00Mn/SCR1 performed the best catalytic activities, and approximately 92.80% mercury oxidation efficiency was obtained at 150 °C. The inhibition effect of NH3 on Hg(0) oxidation was confirmed in that NH3 consumed the surface oxygen. Moreover, H2O inhibited Hg(0) oxidation while SO2 had a promotional effect with the aid of O2. The XPS results illustrated that the surface oxygen was responsible for Hg(0) oxidation and NO conversion. Besides, the Hg(0) oxidation and NO conversion were thought to be aided by synergistic effect between the manganese and cerium oxides.

Templating Routes to Supported Oxide Catalysts by Design

Energy Technology Data Exchange (ETDEWEB)

Notestein, Justin M. [Northwestern Univ., Evanston, IL (United States)

2016-09-08

The rational design and understanding of supported oxide catalysts requires at least three advancements, in order of increasing complexity: the ability to quantify the number and nature of active sites in a catalytic material, the ability to place external controls on the number and structure of these active sites, and the ability to assemble these active sites so as to carry out more complex functions in tandem. As part of an individual investigator research program that is integrated with the Northwestern University Institute for Catalysis in Energy Processes (ICEP) as of 2015, significant advances were achieved in these three areas. First, phosphonic acids were utilized in the quantitative assessment of the number of active and geometrically-available sites in MO_x-SiO₂ catalysts, including nanocrystalline composites, co-condensed materials, and grafted structures, for M=Ti, Zr, Hf, Nb, and Ta. That work built off progress in understanding supported Fe, Cu, and Co oxide catalysts from chelating and/or multinuclear precursors to maximize surface reactivity. Secondly, significant progress was made in the new area of using thin oxide overcoats containing ‘nanocavities’ from organic templates as a method to control the dispersion and thermal stability of subsequently deposited metal nanoparticles or other catalytic domains. Similar methods were used to control surface reactivity in SiO₂-Al₂O₃ acid catalysts and to control reactant selectivity in Al₂O₃-TiO₂ photocatalysts. Finally, knowledge gained from the first two areas has been combined to synthesize a tandem catalyst for hydrotreating reactions and an orthogonal tandem catalyst system where two subsequent reactions in a reaction network are independently controlled by light and heat. Overall, work carried out under this project significantly advanced the knowledge of synthesis-structure-function relationships in supported

High-throughput technology for novel SO2 oxidation catalysts

International Nuclear Information System (INIS)

Loskyll, Jonas; Stoewe, Klaus; Maier, Wilhelm F

2011-01-01

We review the state of the art and explain the need for better SO 2 oxidation catalysts for the production of sulfuric acid. A high-throughput technology has been developed for the study of potential catalysts in the oxidation of SO 2 to SO 3 . High-throughput methods are reviewed and the problems encountered with their adaptation to the corrosive conditions of SO 2 oxidation are described. We show that while emissivity-corrected infrared thermography (ecIRT) can be used for primary screening, it is prone to errors because of the large variations in the emissivity of the catalyst surface. UV-visible (UV-Vis) spectrometry was selected instead as a reliable analysis method of monitoring the SO 2 conversion. Installing plain sugar absorbents at reactor outlets proved valuable for the detection and quantitative removal of SO 3 from the product gas before the UV-Vis analysis. We also overview some elements used for prescreening and those remaining after the screening of the first catalyst generations. (topical review)

Highly selective oxidation of styrene to benzaldehyde over a tailor-made cobalt oxide encapsulated zeolite catalyst.

Science.gov (United States)

Liu, Jiangyong; Wang, Zihao; Jian, Panming; Jian, Ruiqi

2018-05-01

A tailor-made catalyst with cobalt oxide particles encapsulated into ZSM-5 zeolites (Co 3 O 4 @HZSM-5) was prepared via a hydrothermal method with the conventional impregnated Co 3 O 4 /SiO 2 catalyst as the precursor and Si source. Various characterization results show that the Co 3 O 4 @HZSM-5 catalyst has well-organized structure with Co 3 O 4 particles compatibly encapsulated in the zeolite crystals. The Co 3 O 4 @HZSM-5 catalyst was employed as an efficient catalyst for the selective oxidation of styrene to benzaldehyde with hydrogen peroxide as a green and economic oxidant. The effect of various reaction conditions including reaction time, reaction temperature, different kinds of solvents, styrene/H 2 O 2 molar ratio and catalyst dosage on the catalytic performance were systematically investigated. Under the optimized reaction condition, the yield of benzaldehyde can achieve 78.9% with 96.8% styrene conversion and 81.5% benzaldehyde selectivity. Such an excellent catalytic performance can be attributed to the synergistic effect between the confined reaction environment and the proper acidic property. In addition, the reaction mechanism with Co 3 O 4 @HZSM-5 as the catalyst for the selective oxidation of styrene to benzaldehyde was reasonably proposed. Copyright © 2018 Elsevier Inc. All rights reserved.

Oxidation of mercury across selective catalytic reduction catalysts in coal-fired power plants

Energy Technology Data Exchange (ETDEWEB)

Constance L. Senior [Reaction Engineering International, Salt Lake City, UT (United States)

2006-01-15

A kinetic model for predicting the amount of mercury (Hg) oxidation across selective catalytic reduction (SCR) systems in coal-fired power plants was developed and tested. The model incorporated the effects of diffusion within the porous SCR catalyst and the competition between ammonia and Hg for active sites on the catalyst. Laboratory data on Hg oxidation in simulated flue gas and slipstream data on Hg oxidation in flue gas from power plants were modeled. The model provided good fits to the data for eight different catalysts, both plate and monolith, across a temperature range of 280-420{sup o}C, with space velocities varying from 1900 to 5000 hr{sup -1}. Space velocity, temperature, hydrochloric acid content of the flue gas, ratio of ammonia to nitric oxide, and catalyst design all affected Hg oxidation across the SCR catalyst. The model can be used to predict the impact of coal properties, catalyst design, and operating conditions on Hg oxidation across SCRs. 20 refs., 9 figs., 2 tabs.

Oxidative desulfurization of benzothiophene and thiophene with WOx/ZrO2 catalysts: Effect of calcination temperature of catalysts

International Nuclear Information System (INIS)

Hasan, Zubair; Jeon, Jaewoo; Jhung, Sung Hwa

2012-01-01

Highlights: ► Oxidative desulfurization was studied with WO x /ZrO 2 calcined at different temp. ► The importance of the phases of zirconia and tungsten oxide was suggested. ► The catalyst was analyzed thoroughly with Raman and XRD techniques. ► The importance of electron density on S was confirmed with the kinetics of oxidation. - Abstract: Oxidative desulfurization (ODS) of model fuel containing benzothiophene (BT) or thiophene (Th) has been carried out with WO x /ZrO 2 catalyst, which was calcined at various temperatures. Based on the conversion of BT in the model fuel, it can be shown that the optimum calcination temperature of WO x /ZrO 2 catalyst is around 700 °C. The most active catalyst is composed of tetragonal zirconia (ZrO 2 ) with well dispersed polyoxotungstate species and it is necessary to minimize the contents of the crystalline WO 3 and monoclinic ZrO 2 for a high BT conversion. The oxidation rate was interpreted with the first-order kinetics, and it demonstrated the importance of electron density since the kinetic constant for BT was higher than that for Th even though the BT is larger than Th in size. A WO x /ZrO 2 catalyst, treated suitably, can be used as a reusable active catalyst in the ODS.

Oxidation Catalysts for Elemental Mercury in Flue Gases—A Review

Directory of Open Access Journals (Sweden)

Liliana Lazar

2012-02-01

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2007-08-01

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

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

International Nuclear Information System (INIS)

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

2007-01-01

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

Optimization of Cs Content in Co-Mn-Al Mixed Oxide as Catalyst for N2O Decomposition.

Czech Academy of Sciences Publication Activity Database

Chromčáková, Ž.; Obalová, L.; Kustrowski, P.; Drozdek, M.; Karásková, K.; Jirátová, Květa; Kovanda, F.

2015-01-01

Roč. 41, č. 12 (2015), s. 9319-9332 ISSN 0922-6168. [Pannonian Symposium on Catalysis /12./. Třešť, 16.09.2014-20.09.2014] R&D Projects: GA ČR GA14-13750S Institutional support: RVO:67985858 Keywords : nitrous oxide * mixed oxide catalysts * cesium promoter * layered double hydroxides Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 1.833, year: 2015

Oxidative desulfurization of synthetic diesel using supported catalysts. Part 3. Support effect on vanadium-based catalysts

Energy Technology Data Exchange (ETDEWEB)

Cedeno-Caero, Luis; Gomez-Bernal, Hilda; Fraustro-Cuevas, Adriana; Guerra-Gomez, Hector D.; Cuevas-Garcia, Rogelio [UNICAT, Facultad de Quimica, Universidad Nacional Autonoma de Mexico, Cd. Universitaria 04510, Mexico D.F. (Mexico)

2008-04-15

Oxidesulfurization (ODS) of benzothiophenic compounds prevailing in diesel was conducted with hydrogen peroxide in presence of various catalysts, using a model diesel and actual diesel fuel. ODS activities of dibenzothiophenes (DBTs) in hexadecane for a series of V{sub 2}O{sub 5} catalysts supported on alumina, titania, ceria, niobia and silica, were evaluated. Results show that the oxidation activity of DBTs depends on the support used. It was observed that the sulfone yield is not proportional to textural properties or V content. For all catalysts, ODS of benzothiophene (BT), dibenzothiophene (DBT), 4-methyl dibenzothiophene (4-MDBT) and 4,6-dimethyl dibenzothiophene (4,6-DMDBT) decreased in the following order: DBT > 4-MDBT > 4,6-DMDBT > BT. This trend does not depend on the catalyst used or the textural properties of the catalysts and supports. In presence of indole ODS activities diminish, except with catalysts supported on alumina-titania mixed oxide, whereas with V{sub 2}O{sub 5}/TiO{sub 2} catalyst the performance is the highest. ODS of Mexican diesel fuel was carried out in presence of this catalyst and S level was diminished in about 99%. (author)

Quasi-zero-dimensional cobalt-doped CeO2 dots on Pd catalysts for alcohol electro-oxidation with enhanced poisoning-tolerance.

Science.gov (United States)

Tan, Qiang; Zhu, Haiyan; Guo, Shengwu; Chen, Yuanzhen; Jiang, Tao; Shu, Chengyong; Chong, Shaokun; Hultman, Benjamin; Liu, Yongning; Wu, Gang

2017-08-31

Deactivation of an anode catalyst resulting from the poisoning of CO ad -like intermediates is one of the major problems for methanol and ethanol electro-oxidation reactions (MOR & EOR), and remains a grand challenge towards achieving high performance for direct alcohol fuel cells (DAFCs). Herein, we report a new approach for the preparation of ultrafine cobalt-doped CeO 2 dots (Co-CeO 2 , d = 3.6 nm), which can be an effective anti-poisoning promoter for Pd catalysts towards MOR and EOR in alkaline media. Compared to Pd/CeO 2 and pure Pd, the hybrid Pd/Co-CeO 2 nanocomposite catalyst exhibited a much enhanced activity and remarkable anti-poisoning ability for both MOR and EOR. The nanocomposite catalyst showed much higher mass activity (4×) than a state-of-the-art PtRu catalyst. The promotional mechanism was elucidated using extensive characterization and density-functional theory (DFT). A bifunctional effect of the Co-CeO 2 dots was discovered to be due to (i) an enhanced electronic interaction between Co-CeO 2 and Pd dots and (ii) the increased oxygen storage capacity of Co-CeO 2 dots to facilitate the oxidation of CO ad . Therefore, the Pd/Co-CeO 2 nanocomposite appears to be a promising catalyst for advanced DAFCs with low cost and high performance.

The acidic properties of mixed tin and antimony oxide catalysts

Energy Technology Data Exchange (ETDEWEB)

Irving, E.A.; Taylor, D.

1978-01-01

The acidic properties of mixed tin + antimony oxide catalysts were studied in the isomerization of 3,3-dimethyl-1-butene, cyclopropane, 1-butene, and cis-2-butene and the dehydration of isopropanol over the mixed oxides outgassed at room temperature and 698/sup 0/K. Only the zero-order portions of the reaction were used for calculations. With catalysts outgassed at room temperature, weakly acidic sites were present, and all the reactions probably occurred by a carbonium ion mechanism with Broensted acid sites as a source of protons. The rates increased with increasing antimony content to a maximum at approx. 50 at. % and then decreased with further increase in the antimony content. Outgassing of the catalysts at 698/sup 0/K increased the isomerization rate of 3,3-dimethyl-1-butene, but decreased those for cyclopropane and isopropanol due to poisoning by the propylene produced. For 1-butene and cis-2-butene and catalysts outgassed at 698/sup 0/K, only catalysts with less than 50Vertical Bar3< antimony were active. The catalysts were poisoned by treatment with bases or with sodium acetate. A proposed correlation between rates and acidity led to the conclusion that the catalyst composition corresponding to maximum acidity differs from that for maximum selective oxidation activity. Graphs and 10 references.

Bi-modified Pd/C catalyst via irreversible adsorption and its catalytic activity for ethanol oxidation in alkaline medium

International Nuclear Information System (INIS)

Cai, Jindi; Huang, Yiyin; Guo, Yonglang

2013-01-01

Highlights: • Pd-Bi/C catalysts were easily prepared by irreversible adsorption of Bi on Pd/C surface. • The adsorption of Bi increases the oxygen-containing species obviously on Pd-Bi/C surface. • Only a little amount of Bi on Pd-Bi/C can play a significant role in ethanol oxidation reaction (EOR). • Current density of EOR on Pd-Bi/C (20:1) is 2.4 times higher than that on Pd/C. • Anti-poisoning ability and durability of Pd-Bi/C (20:1) is greatly enhanced. -- Abstract: A facile approach to promote ethanol electro-oxidation on Pd-based catalysts is presented by the modification of Bi on Pd/C catalyst via irreversible adsorption. X-ray diffraction (XRD), transmission electron microscope (TEM) and X-ray photoelectron spectroscopy (XPS) measurements show that the modification of Bi has no significant effect on the Pd morphology and particle size distribution. Bi(III) and Pd(0) are the dominant forms in Pd-Bi/C catalyst. Electrochemical tests show that the modification of the appropriate amount of Bi on Pd/C catalyst can remarkably enhance activity toward ethanol oxidation reaction (EOR) up to about 2.4 times higher compared to Pd/C catalyst. The Pd-Bi/C (20:1) catalyst exhibits excellent stability and enhances CO tolerance. The enhanced electrochemical performance of Pd-Bi/C catalyst is attributed to the electronic effect and the bifunctional mechanism. The high exchange current density and the low apparent activation energy on Pd-Bi/C (20:1) catalyst reveal its faster kinetics and higher intrinsic activity compared to Pd/C catalyst

Studies of Deactivation of Methanol to Formaldehyde Selective Oxidation Catalyst

DEFF Research Database (Denmark)

Raun, Kristian Viegaard; Schumann, Max; Høj, Martin

This work presents a study of the deactivation behavior of Fe-Mo oxide catalyst during selective oxidation of methanol to formaldehyde in a period of 5 days. The structural changes in the catalyst have been investigated in situ for the initial 10 h by Raman spectroscopy, and the structure after 5...

Comparison of Preparation Methods of Copper Based PGMFree Diesel-Soot Oxidation Catalysts

Directory of Open Access Journals (Sweden)

R. Prasad

2011-05-01

Full Text Available CuO-CeO2 systems have been proposed as a promising catalyst for low temperature diesel-soot oxidation. CuO-CeO2 catalysts prepared by various methods were examined for air oxidation of the soot in a semi batch tubular flow reactor. The air oxidation of soot was carried out under tight contact with soot/catalyst ratio of 1/10. Air flow rate was 150 ml/min, soot-catalyst mixture was 110 mg, heating rate was 5 0C/min. Prepared catalysts were calcined at 500 0C and their stability was examined by further heating to 800 0C for 4 hours. It was found that the selectivity of all the catalysts was nearly 100% to CO2 production. It was observed that the activity and stability of the catalysts greatly influenced by the preparation methods. The strong interaction between CuO and CeO2 is closely related to the preparation route that plays a crucial role in the soot oxidation over the CuO-CeO2 catalysts. The ranking order of the preparation methods of the catalysts in the soot oxidation performance is as follows: sol-gel > urea nitrate combustion > Urea gelation method > thermal decomposition > co-precipitation. Copyright © 2011 BCREC UNDIP. All rights reserved.(Received: 27th June 2010, Revised: 7th August 2010; Accepted: 13rd October 2010[How to Cite: R. Prasad, V.R. Bella. (2011. Comparison of Preparation Methods of Copper Based PGMFree Diesel-Soot Oxidation Catalysts. Bulletin of Chemical Reaction Engineering and Catalysis, 6(1: 15-21. doi:10.9767/bcrec.6.1.822.15-21][How to Link / DOI: http://dx.doi.org/10.9767/bcrec.6.1.822.15-21 || or local: http://ejournal.undip.ac.id/index.php/bcrec/article/view/822 | View in 

Enhanced methanol electro-oxidation activity of Pt/MWCNTs electro-catalyst using manganese oxide deposited on MWCNTs

International Nuclear Information System (INIS)

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

2014-01-01

Highlights: • Promoting effects of manganese oxide (MnO x ) on methanol electro-oxidation over Pt/MWCNTs are studied. • 3.3 times higher activity and improved stability are observed on Pt/MnO x -MWCNTs in MOR. • Both hydrogen spill over and bi-functional mechanism are facilitated in presence of MnO x . • MnO x significantly enhances electrochemical active surface area and dispersion of Pt nanoparticles. • Proton conductivity of electrocatalyst layer is improved upon MnO x incorporation. - Abstract: Electro-oxidation of methanol on platinum nanoparticles supported on a nanocomposite of manganese oxide (MnO x ) and multi-wall carbon nanotubes (MWCNTs) is investigated. The morphology, structure, and chemical composition of the electro-catalysts are characterized by TEM, XRD, EDS, TGA, and H 2 -TPR. The electro-catalytic properties of electrodes are examined by cyclic voltammetry, CO-stripping, electrochemical impedance spectroscopy (EIS), and linear sweep voltammetry (LSV). Compared to Pt/MWCNTs, the Pt/MnO x -MWCNTs electro-catalyst exhibits about 3.3 times higher forward peak current density, during cyclic voltammetry, and 4.6 times higher exchange current density in methanol electro-oxidation reaction. In addition, deposition of manganese oxide onto MWCNTs dramatically increases the electrochemical active surface area from 29.7 for Pt/MWCNTs to 89.4 m 2 g −1 Pt for Pt/MnO x -MWCNTs. The results of long-term cyclic voltammetry show superior stability of Pt nanoparticles upon addition of manganese oxide to the support. Furthermore, the kinetics of formation of the chemisorbed OH groups improves upon manganese oxide incorporation. This leads to a lower onset potential of CO ads oxidation on Pt/MnO x -MWCNTs than on Pt/MWCNTs

Effect of drying method on properties of vanadium-molybdenum oxide catalysts

International Nuclear Information System (INIS)

Gorshkova, T.P.; Savchenko, L.A.; Tarasova, D.V.; Tret'yakov, Yu.D.; Olen'kova, I.P.; Nikoro, T.A.; Maksimov, N.G.

1981-01-01

Effect of drying method of molybdenum and vanadium salt solutions on physicochemical and catalytical properties of vanadium-molybdenum catalysts is studied. It is shown that the drying method of solutions determines the completeness of vanadium binding into oxide vanadium-molybdenum compounds and thus effects the activity and selectivity of catalysts in acrolein oxidation into acrylic acid. Besides the drying method determines the porous structure of catalysts [ru

Studies of Deactivation of Methanol to Formaldehyde Selective Oxidation Catalyst

DEFF Research Database (Denmark)

Raun, Kristian Viegaard; Schumann, Max; Høj, Martin

Formaldehyde (CH2O) may be synthesized industrially by selective oxidation of methanol over an iron-molybdate (Fe-Mo) oxide catalyst according to: CH3OH + ½O2 →CH2O + H2O. The reaction is normally carried out in a multitubular reactor with excess of air at 250-400 °C (yield = 90-95 %), known...... the activity of the catalyst [2]. Pure MoO3 in itself has low activity. Literature from the last decades agrees that the major reason for the deactivation is loss of molybdenum from the catalyst. Molybdenum forms volatile species with methanol, which can leave behind Mo poor zones. The catalyst is usually...

Hydrogen production by ethanol partial oxidation over nano-iron oxide catalysts produced by chemical vapour synthesis

Energy Technology Data Exchange (ETDEWEB)

Ahmed, Wael Ahmed Abou Taleb Sayed

2011-01-13

This work presents the experimental results of the synthesis of unsupported and supported SiC iron oxide nanoparticles and their catalytic activity towards ethanol partial oxidation. For comparison, further unsupported iron oxide phases were investigated towards the ethanol partial oxidation. These {gamma}-Fe{sub 2}O{sub 3} and {alpha}/{gamma}-Fe{sub 2}O{sub 3} phase catalysts were prepared by the CVS method using Fe(CO){sub 5} as precursor, supplied by another author. The {alpha}-Fe{sub 2}O{sub 3} and SiC nanoparticles were prepared by the CVS method using a home made hot wall reactor technique at atmospheric pressure. Ferrocene and tetramethylsilane were used as precursor for the production process. Process parameters of precursor evaporation temperature, precursor concentration, gas mixture velocity and gas mixture dilution were investigated and optimised to produce particle sizes in a range of 10 nm. For Fe{sub 2}O{sub 3}/SiC catalyst series production, a new hot wall reactor setup was used. The particles were produced by simultaneous thermal decomposition of ferrocene and tetramethylsilane in one reactor from both sides. The production parameters of inlet tube distance inside the reactor, precursor evaporation temperature and carrier gas flow were investigated to produce a series of samples with different iron oxide content. The prepared catalysts composition, physical and chemical properties were characterized by XRD, EDX, SEM, BET surface area, FTIR, XPS and dynamic light scattering (DLS) techniques. The catalytic activity for the ethanol gas-phase oxidation was investigated in a temperature range from 260 C to 290 C. The product distributions obtained over all catalysts were analysed with mass spectrometry analysis tool. The activity of bulk Fe{sub 2}O{sub 3} and SiC nanoparticles was compared with prepared nano-iron oxide phase catalysts. The reaction parameters, such as reaction temperature and O{sub 2}/ethanol ratio were investigated. The catalysts

Atomic origins of water-vapour-promoted alloy oxidation.

Science.gov (United States)

Luo, Langli; Su, Mao; Yan, Pengfei; Zou, Lianfeng; Schreiber, Daniel K; Baer, Donald R; Zhu, Zihua; Zhou, Guangwen; Wang, Yanting; Bruemmer, Stephen M; Xu, Zhijie; Wang, Chongmin

2018-05-07

The presence of water vapour, intentional or unavoidable, is crucial to many materials applications, such as in steam generators, turbine engines, fuel cells, catalysts and corrosion 1-4 . Phenomenologically, water vapour has been noted to accelerate oxidation of metals and alloys 5,6 . However, the atomistic mechanisms behind such oxidation remain elusive. Through direct in situ atomic-scale transmission electron microscopy observations and density functional theory calculations, we reveal that water-vapour-enhanced oxidation of a nickel-chromium alloy is associated with proton-dissolution-promoted formation, migration, and clustering of both cation and anion vacancies. Protons derived from water dissociation can occupy interstitial positions in the oxide lattice, consequently lowering vacancy formation energy and decreasing the diffusion barrier of both cations and anions, which leads to enhanced oxidation in moist environments at elevated temperatures. This work provides insights into water-vapour-enhanced alloy oxidation and has significant implications in other material and chemical processes involving water vapour, such as corrosion, heterogeneous catalysis and ionic conduction.

Regenerable cobalt oxide loaded magnetosphere catalyst from fly ash for mercury removal in coal combustion flue gas.

Science.gov (United States)

Yang, Jianping; Zhao, Yongchun; Zhang, Junying; Zheng, Chuguang

2014-12-16

To remove Hg(0) in coal combustion flue gas and eliminate secondary mercury pollution of the spent catalyst, a new regenerable magnetic catalyst based on cobalt oxide loaded magnetospheres from fly ash (Co-MF) was developed. The catalyst, with an optimal loading of 5.8% cobalt species, attained approximately 95% Hg(0) removal efficiency at 150 °C under simulated flue gas atmosphere. O2 could enhance the Hg(0) removal activity of magnetospheres catalyst via the Mars-Maessen mechanism. SO2 displayed an inhibitive effect on Hg(0) removal capacity. NO with lower concentration could promote the Hg(0) removal efficiency. However, when increasing the NO concentration to 300 ppm, a slightly inhibitive effect of NO was observed. In the presence of 10 ppm of HCl, greater than 95.5% Hg(0) removal efficiency was attained, which was attributed to the formation of active chlorine species on the surface. H2O presented a seriously inhibitive effect on Hg(0) removal efficiency. Repeated oxidation-regeneration cycles demonstrated that the spent Co-MF catalyst could be regenerated effectively via thermally treated at 400 °C for 2 h.

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

Energy Technology Data Exchange (ETDEWEB)

Larsson, Per-Olof

1999-05-01

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

Understanding the performance and mechanism of Mg-containing oxides as support catalysts in the thermal dry reforming of methane.

Science.gov (United States)

Khairudin, Nor Fazila; Sukri, Mohd Farid Fahmi; Khavarian, Mehrnoush; Mohamed, Abdul Rahman

2018-01-01

Dry reforming of methane (DRM) is one of the more promising methods for syngas (synthetic gas) production and co-utilization of methane and carbon dioxide, which are the main greenhouse gases. Magnesium is commonly applied in a Ni-based catalyst in DRM to improve catalyst performance and inhibit carbon deposition. The aim of this review is to gain better insight into recent developments on the use of Mg as a support or promoter for DRM catalysts. Its high basicity and high thermal stability make Mg suitable for introduction into the highly endothermic reaction of DRM. The introduction of Mg as a support or promoter for Ni-based catalysts allows for good metal dispersion on the catalyst surface, which consequently facilitates high catalytic activity and low catalyst deactivation. The mechanism of DRM and carbon formation and reduction are reviewed. This work further explores how different constraints, such as the synthesis method, metal loading, pretreatment, and operating conditions, influence the dry reforming reactions and product yields. In this review, different strategies for enhancing catalytic activity and the effect of metal dispersion on Mg-containing oxide catalysts are highlighted.

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

DEFF Research Database (Denmark)

Poreddy, Raju; Engelbrekt, Christian; Riisager, Anders

2015-01-01

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

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.

Biodiesel production using calcium manganese oxide as catalyst and different raw materials

International Nuclear Information System (INIS)

Dias, Joana Maia; Conceição Machado Alvim-Ferraz, Maria; Fonseca Almeida, Manuel; Méndez Díaz, José Diego; Sánchez Polo, Manuel; Rivera Utrilla, José

2013-01-01

Highlights: ► Biodiesel production using a calcium manganese oxide catalyst was studied. ► The active specie was Ca 0.9 Mn 0.1 O and its deactivation occurred by hydration. ► The studied catalyst presented lower activation temperature than CaO. ► Biodiesel production and quality using different raw materials is reported. ► Compared to the conventional process, biodiesel water content improved. - Abstract: The use of heterogeneous catalysts for biodiesel production aims to simplify the production process as well as to reduce purification costs and related environmental impacts. Calcium manganese oxide was recently identified by the authors as an interesting heterogeneous catalyst for biodiesel production from animal fat; however, the difference between this and other catalysts, the catalyst activation/deactivation mechanisms, its behaviour in the synthesis using different raw materials as well as the impacts of its use on product quality remained unclear. Therefore, the present work: (i) compared biodiesel production using calcium manganese oxide and other catalysts (CaO and NaOH); (ii) studied the reasons leading to activation/deactivation of the heterogeneous catalyst; (iii) analysed biodiesel heterogeneous synthesis using calcium manganese oxide and different raw materials (lard, waste frying oil and a mixture); and (iv) evaluated raw material and catalyst impact on the product quality. Considering the use of different catalysts, the results showed that, after 8 h of reaction, product purity was similar using the different catalysts, being 92.5 wt.% using both NaOH and calcium manganese oxide and 93.8 wt.% using CaO. The active species of the heterogeneous catalysts were CaO, in the case of calcinated calcium carbonate, and Ca 0.9 Mn 0.1 O, in the case of calcinated calcium manganese oxide. Because the deactivating species were different for both catalysts, the calcium manganese oxide required lower activation temperature, which should be an advantage

STUDY OF EPOXIDE DECYCLISATION OF CARYOPHYLENE OXIDE WITH SYNTHETIC ZEOLITE AS CATALYSTS

Directory of Open Access Journals (Sweden)

Winarto Haryadi

2010-06-01

Full Text Available The reaction of epoxide ring opening of caryophillene oxide has been done using zeolite H-Y, H-sodalit, and H-ZSM-5 as catalysts. The reactions were done in two types, there were in dioxane solvent at temperature of 110 oC and without solvent at temperature of 175 oC. The catalyst weight was 10 % from caryophillene oxide weight, and the time of reaction was four hours. The product of reaction was analyzed using GC, FTIR, and GC-MS. The reactions of caryophillene oxide in dioxane solvent with the three kinds of zeolites did not give any targeted product. Whereas, the reactions without solvent gave three main products, there was one compound with one group of secondary hidroxyl (secondary alcohol, and two compounds of ketone from caryophillene. The reaction product of caryophillene oxide obtained without using solvent with the three type of catalysts were then compared. Conversion of three main products produced by H-ZSM-5 catalyst, H-sodalit catalyst and H-Y catalyst were 82.11 %, 54.92 % and 38.53 % respectively. For that reason, the transformation of caryophillene oxide using H-ZSM-5 catalyst was considered to be the best selective product. The alcohol product was resulted from reaction between caryophillene oxide and Bronsted acid, and  the ketone products was resulted from the reaction with Lewis acid in zeolite.   Keywords: Epoxide ring opening, HY, H-sodalit and HZSM-5

Catalytic Oxidation of Propene over Pd Catalysts Supported on CeO2, TiO2, Al2O3 and M/Al2O3 Oxides (M = Ce, Ti, Fe, Mn

Directory of Open Access Journals (Sweden)

Sonia Gil

2015-04-01

Full Text Available In the following work, the catalytic behavior of Pd catalysts prepared using different oxides as support (Al2O3, CeO2 and TiO2 in the catalytic combustion of propene, in low concentration in excess of oxygen, to mimic the conditions of catalytic decomposition of a volatile organic compound of hydrocarbon-type is reported. In addition, the influence of different promoters (Ce, Ti, Fe and Mn when added to a Pd/Al2O3 catalyst was analyzed. Catalysts were prepared by the impregnation method and were characterized by ICP-OES, N2 adsorption, temperature-programmed reduction, temperature-programmed oxidation, X-ray diffraction, X-ray photoelectron spectroscopy and transmission electron microscopy. Catalyst prepared using CeO2 as the support was less easily reducible, due to the stabilization effect of CeO2 over the palladium oxides. Small PdO particles and, therefore, high Pd dispersion were observed for all of the catalysts, as confirmed by XRD and TEM. The addition of Ce to the Pd/Al2O3 catalysts increased the metal-support interaction and the formation of highly-dispersed Pd species. The addition of Ce and Fe improved the catalytic behavior of the Pd/Al2O3 catalyst; however, the addition of Mn and Ti decreased the catalytic activity in the propene oxidation. Pd/TiO2 showed the highest catalytic activity, probably due to the high capacity of this catalyst to reoxidize Pd into PdO, as has been found in the temperature-programmed oxidation (TPO experiments.

FY 2000 report on the promotion projects by Research Institute of Innovative Technology for the Earth. Proceedings of the international seminar (Reports presented to the international workshop for selective oxidation catalysts); 2000 nendo chikyu kankyo sangyo gijutsu kaihatsu suishin jigyo kokusai seminar jigyo shiryo. Sentaku sanka shokubai kokusai workshop hokokusho

Energy Technology Data Exchange (ETDEWEB)

NONE

2001-03-01

Described herein are the FY 2000 results of the international workshop for selective oxidation catalysts, promoted by RITE. The session of methane activation includes a comprehensive lecture on designs of selective alkane oxidation catalysts developed since the 1980s, describing the simplified catalyst design procedures and, at the same time, pointing out the vapor-phase reactions governing the overall reactions at high temperature. The session of alkane oxidation includes a lecture on oxidation of ethane into acrolein in the presence of a silica catalyst supporting isolated active sites, stressing necessity for controlling the vapor-phase reactions and importance of isolating the active sites. The session of crystalline materials includes a lecture on Ti-siting in Ti-containing molecular sieve and selective oxidation catalyst functions, concentrating discussion on oxidation with H{sub 2}O{sub 2} as the oxidant on TS-1. The session of engineering hybrid includes a lecture on catalytic partial oxidation of alkanes in millisecond reactors, describing that possibility of controlling the vapor-phase reactions in the presence of monolith, porous-plate catalysts in a reactor through which the reactant gases pass in a very short time, of the order of millisecond. (NEDO)

Relating FTS Catalyst Properties to Performance

Science.gov (United States)

Ma, Wenping; Ramana Rao Pendyala, Venkat; Gao, Pei; Jermwongratanachai, Thani; Jacobs, Gary; Davis, Burton H.

2016-01-01

During the reporting period June 23, 2011 to August 31, 2013, CAER researchers carried out research in two areas of fundamental importance to the topic of cobalt-based Fischer-Tropsch Synthesis (FTS): promoters and stability. The first area was research into possible substitute promoters that might be used to replace the expensive promoters (e.g., Pt, Re, and Ru) that are commonly used. To that end, three separate investigations were carried out. Due to the strong support interaction of ?-Al2O3 with cobalt, metal promoters are commonly added to commercial FTS catalysts to facilitate the reduction of cobalt oxides and thereby boost active surface cobalt metal sites. To date, the metal promoters examined have been those up to and including Group 11. Because two Group 11 promoters (i.e., Ag and Au) were identified to exhibit positive impacts on conversion, selectivity, or both, research was undertaken to explore metals in Groups 12 - 14. The three metals selected for this purpose were Cd, In, and Sn. At a higher loading of 25%Co on alumina, 1% addition of Cd, In, or Sn was found to-on average-facilitate reduction by promoting a heterogeneous distribution of cobalt consisting of larger lesser interacting cobalt clusters and smaller strongly interacting cobalt species. The lesser interacting species were identified in TPR profiles, where a sharp low temperature peak occurred for the reduction of larger, weakly interacting, CoO species. In XANES, the Cd, In, and Sn promoters were found to exist as oxides, whereas typical promoters (e.g., Re, Ru, Pt) were previously determined to exist in an metallic state in atomic coordination with cobalt. The larger cobalt clusters significantly decreased the active site density relative to the unpromoted 25%Co/Al2O3 catalyst. Decreasing the cobalt loading to 15%Co eliminated the large non-interacting species. The TPR peak for reduction of strongly interacting CoO in the Cd promoted catalyst occurred at a measurably lower temperature

Sulfidation of alumina-supported iron and iron-molybdenum oxide catalysts

NARCIS (Netherlands)

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

1990-01-01

The transition of alumina-supported iron and iron-molybdenum catalysts from the oxidic precursor to the sulfided catalysts was systematically studied by means of in-situ Mössbauer spectroscopy at room temperature. This enabled the adjudgement of various sulfidic phases in the sulfided catalysts. The

Application of a mixed metal oxide catalyst to a metallic substrate

Science.gov (United States)

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

2009-01-01

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

Catalytic oxidation of n-hexane promoted by Ce1−xCuxO2 catalysts prepared by one-step polymeric precursor method

International Nuclear Information System (INIS)

Araújo, Vinícius D.; Lima, Maurício M. de; Cantarero, Andrés; Bernardi, Maria I.B.; Bellido, Jorge D.A.; Assaf, Elisabete M.; Balzer, Rosana; Probst, Luiz F.D.; Fajardo, Humberto V.

2013-01-01

Ceria-supported copper catalysts (Ce 1−x Cu x O 2 , with x (mol) = 0, 0.01, 0.03, 0.05 and 0.10) were prepared in one step through the polymeric precursor method. The textural properties of the catalysts were investigated by X-ray diffraction (XRD), Rietveld refinement, N 2 -physisorption (BET surface area), electron paramagnetic resonance (EPR), UV–visible diffuse reflectance and photoluminescence spectroscopies and temperature-programmed reduction (TPR). In a previous study ceria-supported copper catalysts were found to be efficient in the preferential oxidation of CO. In this study, we extended the catalytic application of Ce 1−x Cu x O 2 systems to n-hexane oxidation and it was verified that the catalysts were highly efficient in the proposed reaction. The best performance (up to 95% conversion) was observed for the catalysts with low copper loads (Ce 0.97 Cu 0.03 O 2 and Ce 0.99 Cu 0.01 O 2 , respectively). The physicochemical characterizations revealed that these behaviors could be attributed to the copper species present in the catalysts and the interaction between CuO and CeO 2 , which vary according to the copper content. - Highlights: • Synthesis of CuO/CeO2 catalysts by the one-step polymeric precursor method. • 95% n-hexane conversion on Ce0.97Cu0.03O2 catalyst. • Redox properties play a key role in the catalytic performance

Uranium oxide catalysts: environmental applications for treatment of chlorinated organic waste from nuclear industry.

Science.gov (United States)

Lazareva, Svetlana; Ismagilov, Zinfer; Kuznetsov, Vadim; Shikina, Nadezhda; Kerzhentsev, Mikhail

2018-02-05

Huge amounts of nuclear waste, including depleted uranium, significantly contribute to the adverse environmental situation throughout the world. An approach to the effective use of uranium oxides in catalysts for the deep oxidation of chlorine-containing hydrocarbons is suggested. Investigation of the catalytic activity of the synthesized supported uranium oxide catalysts doped with Cr, Mn and Co transition metals in the chlorobenzene oxidation showed that these catalysts are comparable with conventional commercial ones. Physicochemical properties of the catalysts were studied by X-ray diffraction, temperature-programmed reduction with hydrogen (H 2 -TPR), and Fourier transform infrared spectroscopy. The higher activity of Mn- and Co-containing uranium oxide catalysts in the H 2 -TPR and oxidation of chlorobenzene in comparison with non-uranium catalysts may be related to the formation of a new disperse phase represented by uranates. The study of chlorobenzene adsorption revealed that the surface oxygen is involved in the catalytic process.

Perovskite catalysts for oxidative coupling

Science.gov (United States)

Campbell, Kenneth D.

1991-01-01

Perovskites of the structure A.sub.2 B.sub.2 C.sub.3 O.sub.10 are useful as catalysts for the oxidative coupling of lower alkane to heavier hydrocarbons. A is alkali metal; B is lanthanide or lanthanum, cerium, neodymium, samarium, praseodymium, gadolinium or dysprosium; and C is titanium.

Transformation of Unsaturated Fatty Acids/Esters to Corresponding Keto Fatty Acids/Esters by Aerobic Oxidation with Pd(II)/Lewis Acid Catalyst.

Science.gov (United States)

Senan, Ahmed M; Zhang, Sicheng; Zeng, Miao; Chen, Zhuqi; Yin, Guochuan

2017-08-16

Utilization of renewable biomass to partly replace the fossil resources in industrial applications has attracted attention due to the limited fossil feedstock with the increased environmental concerns. This work introduced a modified Wacker-type oxidation for transformation of unsaturated fatty acids/esters to the corresponding keto fatty acids/esters, in which Cu 2+ cation was replaced with common nonredox metal ions, that is, a novel Pd(II)/Lewis acid (LA) catalyst. It was found that adding nonredox metal ions can effectively promote Pd(II)-catalyzed oxidation of unsaturated fatty acids/esters to the corresponding keto fatty acids/esters, even much better than Cu 2+ , and the promotional effect is highly dependent on the Lewis acidity of added nonredox metal ions. The improved catalytic efficiency is attributed to the formation of heterobimetallic Pd(II)/LA species, and the oxidation mechanism of this Pd(II)/LA catalyst is also briefly discussed.

Role of CeO2 promoter in NiO/α-Al2O3 catalyst for dry reforming of methane

Science.gov (United States)

Loc, Luu Cam; Phuong, Phan Hong; Tri, Nguyen

2017-09-01

A series of Ni/α-Al2O3 (NiAl) catalysts promoted by CeO2 was prepared by co-impregnation methods with content of (NiO+CeO2) being in the range of 10-30 wt%. The NiO:CeO2 weight ratio was fluctuated at 1:1, 1:2 and 1:3. Several techniques, including X-ray powder diffraction (XRD), Hydrogen temperature-programmed reduction (H2-TPR), and transmission electron microscopy (TEM) were used to investigate catalysts' physico-chemical properties. The activity of these catalysts in dry reforming of CH4 was investigated at temperature range of 550-800 °C. The results revealed that the most suitable CeO2 promoted Ni catalyst contained 20 wt% of (NiO+CeO2) and NiO:CeO2 weight ratio of 1:2. The best catalytic performance of catalyst [20(1Ni2Ce)Al] due to a better reducibility resulted in a higher amount of free small particle NiO. At 700 °C and CH4:CO2 molar ratio of 1:1, the conversion of CH4 and CO2 on the most suitable CeO2 promoted Ni catalyst reached 86% and 67%, respectively; H2 and CO selectivity of 90% and H2:CO molar ratio of 1.15 were obtained. Being similar to MgO [1], promoter CeO2 could improve catalytic activity of Ni/α-Al2O3 catalyst at a lower range of temperature. Besides, both MgO and CeO2 had a great impact on improving coke resistance of Ni catalysts. At higher temperature, the role of CeO2 as well as MgO in preventing coke formation on catalyst was clarified by temperature-programmed oxidation (TPO) technique. Coke amount formed after 30-h TOS on 20(1Ni2Ce) catalyst was found to be 22.18 mgC/gcat, being less than on non-promoted catalyst (36.75 mgC/gcat), but more than on 20(1Ni2Mg)Al one (5.25 mgC/gcat).

Heteropoly acid promoted Cu and Fe catalysts for the selective catalytic reduction of NO with ammonia

DEFF Research Database (Denmark)

Putluru, Siva Sankar Reddy; Mossin, Susanne L.; Riisager, Anders

2011-01-01

Cu/TiO2, Fe/TiO2 and heteropoly acid promoted Cu/TiO2, Fe/TiO2 catalysts were prepared and characterized by N2 physisorption, XRPD, NH3-TPD, H2-TPR and EPR. The catalysts exhibited only crystalline TiO2 phases with the active metals and promoters in highly dispersed state. The acidic properties...... activity and acidity was lower for promoted catalysts than for unpromoted catalysts. In the heteropoly acid promoted catalysts the SCR active Cu and Fe metals were protected from potassium poisons by bonding of the potassium to the Brønsted acid centres. Thus heteropoly acid promoted catalysts might...... be suitable for biomass fired power plant SCR applications....

Facile preparation of a Pt/Prussian blue/graphene composite and its application as an enhanced catalyst for methanol oxidation

International Nuclear Information System (INIS)

Wang, Zonghua; Shi, Guoyu; Xia, Jianfei; Xia, Yanzhi; Zhang, Feifei; Xia, Lin; Song, Daimin; Liu, Jingquan; Li, Yanhui; Xia, Linhua; Brito, Manuel E.

2014-01-01

Graphical abstract: - Highlights: • Pt/Prussian blue/graphene catalyst was easily synthesized by the sequential electrodeposition method. • Prussian blue can promote the homogeneous growth of small Pt nanoparticles. • The as-made catalyst exhibited enhanced electro-catalytic performance for methanol oxidation. • The interplay of Prussian blue and Pt plays a significant role in reducing CO poisoning of the catalyst. - Abstract: Graphene nanosheets (GN) are modified by electrodeposition of Prussian blue (PB) followed by shape-regulated depositing of small Pt nanoparticles via the interaction between PB and PtCl 6 2− to form a novel catalyst Pt/PB/GN. The Pt/PB/GN composite exhibits significantly enhanced electrocatalytic activity with a mass activity of 445 mA mg −1 Pt (at 0.68 V vs. SCE) and high stability towards methanol oxidation. The high catalytic activity can be attributed to the unique porous architecture and peculiar electrical property of Prussian blue integrated with graphene layers which can not only well accommodate Pt nanoparticles but also provide multidimensional pathways to facilitate the mass and electron transport for methanol oxidation. This strategy can be readily extended to fabrication of other graphene-based hybrid supports for precious metal catalysts in fuel cell applications

Effect of Ca, Ce or K oxide addition on the activity of Ni/SiO{sub 2} catalysts for the methane decomposition reaction

Energy Technology Data Exchange (ETDEWEB)

Zapata, Beatriz; Torres-Garcia, Enelio [Instituto Mexicano del Petroleo, Programa de Procesos y Reactores, Eje C. 152, Mexico, D.F., C.P. 07730 (Mexico); Valenzuela, Miguel A.; Palacios, Jorge [Instituto Politecnico Nacional-ESIQIE, Lab. Catalisis y Materiales, Zacatenco, Mexico, D.F., C.P. 07738 (Mexico)

2010-11-15

To increase the activity and stability of Ni/SiO{sub 2} catalysts, a series of Ni-Ca, Ni-K and Ni-Ce promoted catalysts were prepared by successive impregnations. The textural properties, reducibility and catalytic performance in the methane decomposition reaction were investigated. The catalyst containing 30 wt.% Ni and 30 wt.% cerium oxide greatly increased the conversion of methane (90% of equilibrium value) and improved the stability, whereas the Ni-K and Ni-Ca were less active and stable than the Ni/SiO{sub 2} catalyst. The results suggest that Ce addition prevents the sintering of nickel particles during reduction process maintaining a random distribution between the silica and cerium oxide improving the distribution and migration of deposited carbon. (author)

Low-Temperature Oxidation of Dimethyl Ether to Polyoxymethylene Dimethyl Ethers over CNT-Supported Rhenium Catalyst

Directory of Open Access Journals (Sweden)

Qingde Zhang

2016-03-01

Full Text Available Due to its excellent conductivity, good thermal stability and large specific surface area, carbon nano-tubes (CNTs were selected as support to prepare a Re-based catalyst for dimethyl ether (DME direct oxidation to polyoxymethylene dimethyl ethers (DMMx. The catalyst performance was tested in a continuous flow type fixed-bed reactor. H3PW12O40 (PW12 was used to modify Re/CNTs to improve its activity and selectivity. The effects of PW12 content, reaction temperature, gas hourly space velocity (GHSV and reaction time on DME oxidation to DMMx were investigated. The results showed that modification of CNT-supported Re with 30% PW12 significantly increased the selectivity of DMM and DMM2 up to 59.0% from 6.6% with a DME conversion of 8.9%; besides that, there was no COx production observed in the reaction under the optimum conditions of 513 K and 1800 h−1. The techniques of XRD, BET, NH3-TPD, H2-TPR, XPS, TEM and SEM were used to characterize the structure, surface properties and morphology of the catalysts. The optimum amount of weak acid sites and redox sites promotes the synthesis of DMM and DMM2 from DME direct oxidation.

Low temperature incineration of mixed wastes using bulk metal oxide catalysts

International Nuclear Information System (INIS)

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

1996-01-01

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

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

KAUST Repository

Zhu, Haibo

2014-06-01

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

Influence of phosphorous addition on Bi3Mo2Fe1 oxide catalysts for the oxidative dehydrogenation of 1-butene

KAUST Repository

Park, Jung-Hyun

2016-01-22

Bi3Mo2Fe1Px oxide catalysts were prepared by a co-precipitation method and the influence of phosphorous content on the catalytic performance in the oxidative dehydrogenation of 1-butene was investigated. The addition of phosphorous up to 0.4mole ratio to Bi3Mo2Fe1 oxide catalyst led to an increase in the catalytic performance; however, a higher phosphorous content (above P=0.4) led to a decrease of conversion. Of the tested catalysts, Bi3Mo2Fe1P0.4 oxide catalyst exhibited the highest catalytic performance. Characterization results showed that the catalytic performance was related to the quantity of a π-allylic intermediate, facile desorption behavior of adsorbed intermediates and ability for re-oxidation of catalysts. © 2015 Korean Institute of Chemical Engineers, Seoul, Korea

Influence of phosphorous addition on Bi3Mo2Fe1 oxide catalysts for the oxidative dehydrogenation of 1-butene

KAUST Repository

Park, Jung-Hyun; Shin, Chae-Ho

2016-01-01

Bi3Mo2Fe1Px oxide catalysts were prepared by a co-precipitation method and the influence of phosphorous content on the catalytic performance in the oxidative dehydrogenation of 1-butene was investigated. The addition of phosphorous up to 0.4mole ratio to Bi3Mo2Fe1 oxide catalyst led to an increase in the catalytic performance; however, a higher phosphorous content (above P=0.4) led to a decrease of conversion. Of the tested catalysts, Bi3Mo2Fe1P0.4 oxide catalyst exhibited the highest catalytic performance. Characterization results showed that the catalytic performance was related to the quantity of a π-allylic intermediate, facile desorption behavior of adsorbed intermediates and ability for re-oxidation of catalysts. © 2015 Korean Institute of Chemical Engineers, Seoul, Korea

Bio-inspired Iron Catalysts for Hydrocarbon Oxidations

Energy Technology Data Exchange (ETDEWEB)

Que, Jr., Lawrence [Univ. of Minnesota, Minneapolis, MN (United States)

2016-03-22

Stereoselective oxidation of C–H and C=C bonds are catalyzed by nonheme iron enzymes. Inspired by these bioinorganic systems, our group has been exploring the use of nonheme iron complexes as catalysts for the oxidation of hydrocarbons using H2O2 as an environmentally friendly and atom-efficient oxidant in order to gain mechanistic insights into these novel transformations. In particular, we have focused on clarifying the nature of the high-valent iron oxidants likely to be involved in these transformations.

Impacts of acid gases on mercury oxidation across SCR catalyst

International Nuclear Information System (INIS)

Zhuang, Ye; Laumb, Jason; Liggett, Richard; Holmes, Mike; Pavlish, John

2007-01-01

A series of bench-scale experiments were completed to evaluate acid gases of HCl, SO 2 , and SO 3 on mercury oxidation across a commercial selective catalytic reduction (SCR) catalyst. The SCR catalyst was placed in a simulated flue gas stream containing O 2 , CO 2 , H 2 O, NO, NO 2 , and NH 3 , and N 2 . HCl, SO 2 , and SO 3 were added to the gas stream either separately or in combination to investigate their interactions with mercury over the SCR catalyst. The compositions of the simulated flue gas represent a medium-sulfur and low- to medium-chlorine coal that could represent either bituminous or subbituminous. The experimental data indicated that 5-50 ppm HCl in flue gas enhanced mercury oxidation within the SCR catalyst, possibly because of the reactive chlorine species formed through catalytic reactions. An addition of 5 ppm HCl in the simulated flue gas resulted in mercury oxidation of 45% across the SCR compared to only 4% mercury oxidation when 1 ppm HCl is in the flue gas. As HCl concentration increased to 50 ppm, 63% of Hg oxidation was reached. SO 2 and SO 3 showed a mitigating effect on mercury chlorination to some degree, depending on the concentrations of SO 2 and SO 3 , by competing against HCl for SCR adsorption sites. High levels of acid gases of HCl (50 ppm), SO 2 (2000 ppm), and SO 3 (50 ppm) in the flue gas deteriorate mercury adsorption on the SCR catalyst. (author)

Cobalt doped CuMnOx catalysts for the preferential oxidation of carbon monoxide

Science.gov (United States)

Dey, Subhashish; Dhal, Ganesh Chandra; Mohan, Devendra; Prasad, Ram; Gupta, Rajeev Nayan

2018-05-01

Carbon monoxide (CO) is a poisonous gas, recognized as a silent killer for the 21st century. It is produced from the partial oxidation of carbon containing compounds. The catalytic oxidation of CO receives a huge attention due to its applications in different fields. In the present work, hopcalite (CuMnOx) catalysts were synthesized using a co-precipitation method for CO oxidation purposes. Also, it was doped with the cobalt by varying concentration from 1 to 5wt%. It was observed that the addition of cobalt into the CuMnOx catalyst (by the deposition-precipitation method) improved the catalytic performance for the low-temperature CO oxidation. CuMnOx catalyst doped with 3wt% of cobalt exhibited most active performance and showed the highest activity than other cobalt concentrations. Different analytical tools (i.e. XRD, FTIR, BET, XPS and SEM-EDX) were used to characterize the as-synthesized catalysts. It was expected that the introduction of cobalt will introduce new active sites into the CuMnOx catalyst that are associated with the cobalt nano-particles. The order of calcination strategies based on the activity for cobalt doped CuMnOx catalysts was observed as: Reactive calcinations (RC) > flowing air > stagnant air. Therefore, RC (4.5% CO in air) route can be recommended for the synthesis of highly active catalysts. The catalytic activity of doped CuMnOx catalysts toward CO oxidation shows a correlation among average oxidation number of Mn and the position and the nature of the doped cobalt cation.

An oxidation-resistant indium tin oxide catalyst support for proton exchange membrane fuel cells

Energy Technology Data Exchange (ETDEWEB)

Chhina, H.; Campbell, S. [Ballard Power Systems Inc., 9000 Glenlyon Parkway, Burnaby, BC V5J 5J8 (Canada); Kesler, O. [Department of Mechanical Engineering, University of British Columbia, Vancouver, BC, V6T 1Z4 (Canada)

2006-10-27

The oxidation of carbon catalyst supports causes degradation in catalyst performance in proton exchange membrane fuel cells (PEMFCs). Indium tin oxide (ITO) is considered as a candidate for an alternative catalyst support. The electrochemical stability of ITO was studied by use of a rotating disk electrode (RDE). Oxidation cycles between +0.6 and +1.8V were applied to ITO supporting a Pt catalyst. Cyclic voltammograms (CVs) both before and after the oxidation cycles were obtained for Pt on ITO, Hispec 4000 (a commercially available catalyst), and 40wt.% Pt dispersed in-house on Vulcan XC-72R. Pt on ITO showed significantly better electrochemical stability, as determined by the relative change in electrochemically active surface area after cycling. Hydrogen desorption peaks in the CVs existed even after 100 cycles from 0.6 to 1.8V for Pt on ITO. On the other hand, most of the active surface area was lost after 100 cycles of the Hispec 4000 catalyst. The 40wt.% Pt on Vulcan made in-house also lost most of its active area after only 50 cycles. Pt on ITO was significantly more electrochemically stable than both Hispec 4000 and Pt on Vulcan XC-72R. In this study, it was found that the Pt on ITO had average crystallite sizes of 13nm for Pt and 38nm for ITO. Pt on ITO showed extremely high thermal stability, with only {approx}1wt.% loss of material for ITO versus {approx}57wt.% for Hispec 4000 on heating to 1000{sup o}C. The TEM data show Pt clusters dispersed on small crystalline ITO particles. The SEM data show octahedral shaped ITO particles supporting Pt. (author)

Ammonia synthesis over multi-promoted iron catalysts obtained by high-energy ball-milling

DEFF Research Database (Denmark)

Jacobsen, C.J.H.; Jiang, Jianzhong; Mørup, Steen

1999-01-01

The feasibility of producing ammonia synthesis catalysts from high-energy ball-milling of a simple mixture of the constituent oxides has been investigated. The effect of ball-milling the fused oxidic precursor of the industrial KM1 ammonia synthesis catalyst has also been studied. The results show...

Electron microscopic studies of natural gas oxidation catalyst – Effects of thermally accelerated aging on catalyst microstructure

DEFF Research Database (Denmark)

Honkanen, Mari; Hansen, Thomas Willum; Jiang, Hua

2017-01-01

Structural changes of PtPd nanoparticles in a natural gas oxidation catalyst were studied at elevated temperatures in air and low-oxygen conditions and in situ using environmental transmission electron microscopy (ETEM). The fresh catalyst shows

Carbon monoxide oxidation over three different states of copper: Development of a model metal oxide catalyst

Energy Technology Data Exchange (ETDEWEB)

Jernigan, Glenn Geoffrey [California Univ., Berkeley, CA (United States). Dept. of Chemistry

1994-10-01

Carbon monoxide oxidation was performed over the three different oxidation states of copper -- metallic (Cu), copper (I) oxide (Cu₂O), and copper (II) oxide (CuO) as a test case for developing a model metal oxide catalyst amenable to study by the methods of modern surface science and catalysis. Copper was deposited and oxidized on oxidized supports of aluminum, silicon, molybdenum, tantalum, stainless steel, and iron as well as on graphite. The catalytic activity was found to decrease with increasing oxidation state (Cu > Cu₂O > CuO) and the activation energy increased with increasing oxidation state (Cu, 9 kcal/mol < Cu₂O, 14 kcal/mol < CuO, 17 kcal/mol). Reaction mechanisms were determined for the different oxidation states. Lastly, NO reduction by CO was studied. A Cu and CuO catalyst were exposed to an equal mixture of CO and NO at 300--350 C to observe the production of N₂ and CO₂. At the end of each reaction, the catalyst was found to be Cu₂O. There is a need to study the kinetics of this reaction over the different oxidation states of copper.

Methanol Oxidation Using Ozone on Titania-Supported Vanadium Catalyst

Science.gov (United States)

Ozone-enhanced catalytic oxidation of methanol has been conducted at mild temperatures of 100 to 250NC using V2O5/TiO2 catalyst prepared by the sol-gel method. The catalyst was characterized using XRD, surface area measurements, and temperature-programmed desorption of methanol. ...

Catalytic Oxidation of Phenol over Zeolite Based Cu/Y-5 Catalyst: Part 1: Catalyst Preparation and Characterization

Directory of Open Access Journals (Sweden)

K. Maduna Valkaj

2015-01-01

Full Text Available The necessity to remove organic pollutants from the industrial wastewater streams has forced the development of new technologies that can produce better results in terms of pollutant removal and process efficiency in combination with low investment and operating costs. One of the new emerging processes with a potential to fulfil these demands is catalytic wet peroxide oxidation, commonly known as the CWPO process. The oxidative effect of the hydrogen peroxide is intensified by the addition of a heterogeneous catalyst that can reduce the operating conditions to atmospheric pressure and temperatures below 383 K. Zeolites, among others, are especially appealing as catalysts for selective oxidation processes due to their unique characteristics such as shape selectivity, thermal and chemical stability, and benign effect on nature and the living world. In this work, catalytic activity, selectivity and stability of Cu/Y-5 zeolite in phenol oxidation with hydrogen peroxide was examined. Catalyst samples were prepared by ion exchange method of the protonic form of commercial zeolite. The catalysts were characterized with powder X-ray diffraction (XRD, scanning electron microscopy (SEM, and AAS elemental analysis, while the adsorption techniques were used for the measurement of the specific surface area. The catalytic tests were carried out in a stainless steel Parr reactor in batch operation mode at the atmospheric pressure and in the temperature range from 323 to 353 K. The catalyst was prepared in powdered form and the mass fraction of the active metal component on the zeolite was 3.46 %. The initial concentration of phenol solution was equal to 0.01 mol dm−3 and the concentration of hydrogen peroxide ranged from 0.01 to 0.10 mol dm−3. The obtained experimental data was tested to a proposed kinetic model for phenol oxidation r = k1 cF cVP and hydrogen peroxide decomposition rHP = k2 cHP. The kinetic parameters were estimated using the Nelder

Selectivity and Activity of Iron Molybdate Catalysts in Oxidation of Methanol

OpenAIRE

Khalid Khazzal Hummadi; Karim H. Hassan; Phillip C.H. Mitchell

2009-01-01

The selectivity and activity of iron molybdate catalysts prepared by different methods are compared with those of a commercial catalyst in the oxidation of methanol to formaldehyde in a continuous tubular bed reactor at 200-350 oC (473-623 oK), 10 atm (1013 kPa), with a methanol-oxygen mixture fixed at 5.5% by volume methanol: air ratio. The iron(III) molybdate catalyst prepared by co-precipitation and filtration had a selectivity towards formaldehyde in methanol oxidation comparable with a c...

Rh promoted La0.75Sr0.25(Fe0.8Co0.2)1−xGaxO3-δ perovskite catalysts: Characterization and catalytic performance for methane partial oxidation to synthesis gas

International Nuclear Information System (INIS)

Palcheva, R.; Olsbye, U.; Palcut, M.; Rauwel, P.; Tyuliev, G.; Velinov, N.; Fjellvåg, H.H.

2015-01-01

Graphical abstract: - Highlights: • Perovskites type-oxide La 0.75 Sr 0.25 (Fe 0.8 Co 0.2 ) 1−x Ga x O 3-δ (x = 0.1, 0.25, 0.4) prepared by the sol–gel citrate method. • Bulk and surface analysis to determine catalysts composition evolution. • Anaerobic catalytic partial oxidation of methane to syngas at 600 °C in a pulse apparatus over Rh promoted perovskites. • The catalysts showed high stability and selectivity. - Abstract: Synthesis gas production via selective oxidation of methane at 600 °C in a pulse reaction over La 0.75 Sr 0.25 (Fe 0.8 Co 0.2 ) 1−x Ga x O 3-δ (x = 0.1, 0.25, 0.4) perovskite-supported rhodium catalysts, was investigated. The perovskite oxides were prepared by sol–gel citrate method and characterized by X-ray Diffraction (XRD), Moessbauer Spectroscopy (MS), Temperature Programmed Reduction (TPR-H 2 ), X-ray Photoelectron Spectroscopy (XPS) and High Resolution Transmission Electron Microscopy (HRTEM). According to XRD analysis, the synthesized samples were a single perovskite phase. The perovskite structure of Ga substituted samples remained stable after TPR-H 2 , as confirmed by XRD. Data of MS identified Fe 3+ ions in two distinctive coordination environments, and Fe 4+ ions. The Rh 2 O 3 thin overlayer was detected by the HRTEM for the Rh impregnated perovskite oxides. During the interaction of methane with oxidized perovskite-supported Rh (0.5 wt.%) catalysts, besides CO, H 2 , and surface carbon, CO 2 and H 2 O were formed. The Rh perovskite catalyst with x = 0.25 gallium exhibits the highest catalytic activity of 83% at 600 °C. The CO selectivity was affected by the reducibility of La 0.75 Sr 0.25 (Fe 0.8 Co 0.2 ) 1−x Ga x O 3-δ perovskite materials.

Atomic Scale Structure-Chemistry Relationships at Oxide Catalyst Surfaces and Interfaces

Science.gov (United States)

McBriarty, Martin E.

Oxide catalysts are integral to chemical production, fuel refining, and the removal of environmental pollutants. However, the atomic-scale phenomena which lead to the useful reactive properties of catalyst materials are not sufficiently understood. In this work, the tools of surface and interface science and electronic structure theory are applied to investigate the structure and chemical properties of catalytically active particles and ultrathin films supported on oxide single crystals. These studies focus on structure-property relationships in vanadium oxide, tungsten oxide, and mixed V-W oxides on the surfaces of alpha-Al2O3 and alpha-Fe2O 3 (0001)-oriented single crystal substrates, two materials with nearly identical crystal structures but drastically different chemical properties. In situ synchrotron X-ray standing wave (XSW) measurements are sensitive to changes in the atomic-scale geometry of single crystal model catalyst surfaces through chemical reaction cycles, while X-ray photoelectron spectroscopy (XPS) reveals corresponding chemical changes. Experimental results agree with theoretical calculations of surface structures, allowing for detailed electronic structure investigations and predictions of surface chemical phenomena. The surface configurations and oxidation states of V and W are found to depend on the coverage of each, and reversible structural shifts accompany chemical state changes through reduction-oxidation cycles. Substrate-dependent effects suggest how the choice of oxide support material may affect catalytic behavior. Additionally, the structure and chemistry of W deposited on alpha-Fe 2O3 nanopowders is studied using X-ray absorption fine structure (XAFS) measurements in an attempt to bridge single crystal surface studies with real catalysts. These investigations of catalytically active material surfaces can inform the rational design of new catalysts for more efficient and sustainable chemistry.

Lanthanum-promoted copper-based hydrotalcites derived mixed oxides for NO{sub x} adsorption, soot combustion and simultaneous NO{sub x}-soot removal

Energy Technology Data Exchange (ETDEWEB)

Wang, Zhongpeng [School of Resources and Environment, University of Jinan, 106 Jiwei Road, Jinan 250022 (China); Inorganic Chemistry Laboratory, University of Oxford, South Parks Road, Oxford OX1 3QR (United Kingdom); Yan, Xiaotong; Bi, Xinlin; Wang, Liguo [School of Resources and Environment, University of Jinan, 106 Jiwei Road, Jinan 250022 (China); Zhang, Zhaoliang, E-mail: chm_zhangzl@ujn.edu.cn [School of Resources and Environment, University of Jinan, 106 Jiwei Road, Jinan 250022 (China); Jiang, Zheng; Xiao, Tiancun [Inorganic Chemistry Laboratory, University of Oxford, South Parks Road, Oxford OX1 3QR (United Kingdom); Umar, Ahmad [Department of Chemistry, College of Science and Arts, Najran University, P.O. Box 1988, Najran 11001 (Saudi Arabia); Promising Centre for Sensors and Electronic Devices (PCSED), Najran University, P.O. Box 1988, Najran 11001 (Saudi Arabia); Wang, Qiang, E-mail: qiang.wang.ox@gmail.com [College of Environmental Science and Engineering, Beijing Forestry University, 35 Tsinghua East Road, Beijing 100083 (China)

2014-03-01

Graphical abstract: - Highlights: • The addition of La in Cu-based oxides increased the types of active oxygen. • NO{sub x} adsorption, soot oxidation and simultaneous NO{sub x}-soot removal were enhanced. • The possible catalytic mechanism was studied via in situ FTIR analysis. • Soot oxidation was promoted by the NO{sub 2} intermediate. - Abstract: La-promoted Cu-based hydrotalcites derived mixed oxides were prepared and their catalytic activities for NO{sub x} adsorption, soot oxidation, and simultaneous NO{sub x}-soot removal were investigated. The catalysts were characterized by XRD, DTG, BET, FTIR, H2-TPR, TPD and TPO techniques. The oxides catalysts exhibited mesoporous properties with specific surface area of 45–160 m{sup 2}/g. The incorporation of La and Cu decreased the amount of basic sites due to the large decrease in surface areas. Under O{sub 2} atmosphere, La incorporation is dominant for soot oxidation activity, while Cu favors high selectivity to CO{sub 2} formation. A synergetic effect between La and Cu for catalyzed soot oxidation lies in the improved redox property and suitable basicity. The presence of NO in O{sub 2} significantly promoted soot oxidation on the catalysts with the ignition temperature decreased to about 300 °C. In O{sub 2}/NO atmosphere, NO{sub 2} acts as an intermediate which oxidizes soot to CO{sub 2} at a lower temperature with itself reduced to NO or N{sub 2}, contributing to the high catalytic performance in simultaneous removal of NO{sub x} and soot.

Effects of K and Pt promoters on the performance of cobalt catalyst supported on CNTs

International Nuclear Information System (INIS)

Zabidi, Noor Asmawati Mohd; Ali, Sardar; Subbarao, Duvvuri

2014-01-01

This paper presents a comparative study on the effects of incorporation of potassium (K) and platinum (Pt) as promoters on the physicochemical properties of cobalt catalyst. The catalyst was prepared by a wet impregnation method on a CNTs support. Samples were characterized using transmission electron microscopy (TEM), H 2 -temperature-programmed reduction (TPR) and X-ray photoelectron spectroscopy (XPS) techniques. Fischer-Tropsch Synthesis (FTS) was carried out in a fixed-bed microreactor at 543 K and 1 atm, with H 2 /CO = 2v/v and space velocity, SV of 12 L/g.h for 5 hours. The K-promoted and Pt-promoted Co catalysts have different physicochemical properties and catalytic performances compared to that of the un-promoted Co catalyst. XPS analysis revealed that K and Pt promoters induced electronic modifications as exhibited by the shifts in the Co binding energies. Incorporation of 0.06 wt% K and 0.06 wt% Pt in Co/CNTs catalyst resulted in an increase in the CO conversion and C 5+ selectivity and a decrease in methane selectivity. Potassium was found to be a better promoter for Co/CNTs catalyst compared to platinum

Effects of K and Pt promoters on the performance of cobalt catalyst supported on CNTs

Energy Technology Data Exchange (ETDEWEB)

Zabidi, Noor Asmawati Mohd, E-mail: noorasmawati-mzabidi@petronas.com.my [Department of Fundamental and Applied Sciences, Universiti Teknologi PETRONAS, Bandar Seri Iskandar, 31750 Tronoh, Perak (Malaysia); Ali, Sardar, E-mail: alikhan-635@yahoo.com [Centralized Analytical Laboratory, Universiti Teknologi PETRONAS, Bandar Seri Iskandar, 31750 Tronoh, Perak (Malaysia); Subbarao, Duvvuri, E-mail: duvvuri-subbarao@petronas.com.my [Department of Chemical Engineering, Universiti Teknologi PETRONAS, Bandar Seri Iskandar, 31750 Tronoh, Perak (Malaysia)

2014-10-24

This paper presents a comparative study on the effects of incorporation of potassium (K) and platinum (Pt) as promoters on the physicochemical properties of cobalt catalyst. The catalyst was prepared by a wet impregnation method on a CNTs support. Samples were characterized using transmission electron microscopy (TEM), H{sub 2}-temperature-programmed reduction (TPR) and X-ray photoelectron spectroscopy (XPS) techniques. Fischer-Tropsch Synthesis (FTS) was carried out in a fixed-bed microreactor at 543 K and 1 atm, with H{sub 2}/CO = 2v/v and space velocity, SV of 12 L/g.h for 5 hours. The K-promoted and Pt-promoted Co catalysts have different physicochemical properties and catalytic performances compared to that of the un-promoted Co catalyst. XPS analysis revealed that K and Pt promoters induced electronic modifications as exhibited by the shifts in the Co binding energies. Incorporation of 0.06 wt% K and 0.06 wt% Pt in Co/CNTs catalyst resulted in an increase in the CO conversion and C{sub 5+} selectivity and a decrease in methane selectivity. Potassium was found to be a better promoter for Co/CNTs catalyst compared to platinum.

Niobium, catalyst repair kit

International Nuclear Information System (INIS)

Tanabe, K.

1991-01-01

This paper reports that niobium oxides, when small amounts are added to known catalysts, enhance catalytic activity and selectivity and prolong catalyst life. Moreover, niobium oxides exhibit a pronounced effect as supports of metal or metal oxide catalysts. Recently we found that the surface acidity of hydrated niobium pentoxide, niobic acid (Nb 2 O 5 · nH 2 O), corresponds to the acidity of 70% sulfuric acid and exhibits high catalytic activity, selectivity, and stability for acid-catalyzed reactions in which water molecules participate. Although there are few differences in electronegativity and ionic radius between niobium and its neighbors in the periodic table, it is interesting that the promoter effect, support effect, and acidic nature of niobium compounds are quite different from those of compounds of the surrounding elements. Here we review what's known of niobium compounds from the viewpoint of their pronounced catalytic behavior

Effect of thermal treatment conditions on properties of vanadium molybdenum oxide catalyst in acrolein oxidation reaction to acrylic acid

International Nuclear Information System (INIS)

Gorshkova, T.P.; Tarasova, D.V.; Olen'kova, I.P.; Andrushkevich, T.V.; Nikoro, T.A.

1984-01-01

The effect of thermal treatment conditions (temperature and gas medium) on properties of vanadium molybdenum oxide catalyst in acrolein oxidation reaction to acrylic acid is investigated. It is shown that active and selective catalysts are formed in the course of thermal decomposition of the drying product of ammonium metavanadate and paramolybdate under the conditions ensuring the vanadium ion reduction up to tetravalent state with conservation of molybdenum oxidation degree equal to 6. It is possible to realize it either by treatment of the catalyst calcinated in the air flow at 300 deg by the reaction mixture at the activation stage or by gas-reducer flow treatment at 280 deg. Thermal treatment in the reducing medium of the oxidized catalyst does not lead to complete regeneration of its properties

Ni catalysts with different promoters supported on zeolite for dry reforming of methane

KAUST Repository

Alotaibi, Raja; Alenazey, Feraih; Alotaibi, Faisal; Wei, Nini; Al-Fatesh, Ahmed; Fakeeha, Anis

2015-01-01

Dry reforming of methane (DRM) is considered a high endothermic reaction with operating temperatures between 700 and 1000 °C to achieve high equilibrium conversion of CH4 and CO2 to the syngas (H2 and CO). The conventional catalysts used for DRM are Ni-based catalysts. However, many of these catalysts suffer from the short longevity due to carbon deposition. This study aims to evaluate the effect of La and Ca as promoters for Ni-based catalysts supported on two different zeolite supports, ZL (A) (BET surface area = 925 m2/g, SiO2/Al2O3 mol ratio = 5.1), and ZL (B) (BET surface area = 730 m2/g, SiO2/Al2O3 mol ratio = 12), for DRM. The physicochemical properties of the prepared catalysts were characterized with XRD, BET, TEM and TGA. These catalysts were tested for DRM in a microtubular reactor at reaction conditions of 700 °C. The catalyst activity results show that the catalysts Ni/ZL (B) and Ca-Ni/ZL (B) give the highest methane conversion (60 %) with less time on stream stability compared with promoted Ni on ZL (A). In contrast, La-containing catalysts, La-Ni/ZL (B), show more time on stream stability with minimum carbon content for the spent catalyst indicating the enhancement of the promoters to the Ni/ZL (A) and (B), but with less catalytic activity performance in terms of methane and carbon dioxide conversions due to rapid catalyst deactivation.

Ni catalysts with different promoters supported on zeolite for dry reforming of methane

KAUST Repository

Alotaibi, Raja

2015-07-08

Dry reforming of methane (DRM) is considered a high endothermic reaction with operating temperatures between 700 and 1000 °C to achieve high equilibrium conversion of CH4 and CO2 to the syngas (H2 and CO). The conventional catalysts used for DRM are Ni-based catalysts. However, many of these catalysts suffer from the short longevity due to carbon deposition. This study aims to evaluate the effect of La and Ca as promoters for Ni-based catalysts supported on two different zeolite supports, ZL (A) (BET surface area = 925 m2/g, SiO2/Al2O3 mol ratio = 5.1), and ZL (B) (BET surface area = 730 m2/g, SiO2/Al2O3 mol ratio = 12), for DRM. The physicochemical properties of the prepared catalysts were characterized with XRD, BET, TEM and TGA. These catalysts were tested for DRM in a microtubular reactor at reaction conditions of 700 °C. The catalyst activity results show that the catalysts Ni/ZL (B) and Ca-Ni/ZL (B) give the highest methane conversion (60 %) with less time on stream stability compared with promoted Ni on ZL (A). In contrast, La-containing catalysts, La-Ni/ZL (B), show more time on stream stability with minimum carbon content for the spent catalyst indicating the enhancement of the promoters to the Ni/ZL (A) and (B), but with less catalytic activity performance in terms of methane and carbon dioxide conversions due to rapid catalyst deactivation.

Heterogeneous catalytic ozonation of ciprofloxacin in water with carbon nanotube supported manganese oxides as catalyst

Energy Technology Data Exchange (ETDEWEB)

Sui, Minghao, E-mail: suiminghao.sui@gmail.com [State Key Laboratory of Pollution Control and Resource Reuse, School of Environmental Science and Engineering, Tongji University, 1239 Siping Road, Shanghai 200092 (China); Xing, Sichu; Sheng, Li; Huang, Shuhang; Guo, Hongguang [State Key Laboratory of Pollution Control and Resource Reuse, School of Environmental Science and Engineering, Tongji University, 1239 Siping Road, Shanghai 200092 (China)

2012-08-15

Highlights: Black-Right-Pointing-Pointer Ciprofloxacin in water was degraded by heterogeneous catalytic ozonation. Black-Right-Pointing-Pointer MnOx were supported on MWCNTs to serve as catalyst for ozonation. Black-Right-Pointing-Pointer MnOx/MWCNT exhibited highly catalytic activity on ozonation of ciprofloxacin in water. Black-Right-Pointing-Pointer MnOx/MWCNT resulted in effective antibacterial activity inhibition on ciprofloxacin. Black-Right-Pointing-Pointer MnOx/MWCNT promoted the generation of hydroxyl radicals. - Abstract: Carbon nanotube-supported manganese oxides (MnOx/MWCNT) were used as catalysts to assist ozone in degrading ciprofloxacin in water. Manganese oxides were successfully loaded on multi-walled carbon nanotube surfaces by simply impregnating the carbon nanotube with permanganate solution. The catalytic activities of MnOx/MWCNT in ciprofloxacin ozonation, including degradation, mineralization effectiveness, and antibacterial activity change, were investigated. The presence of MnOx/MWCNT significantly elevated the degradation and mineralization efficiency of ozone on ciprofloxacin. The microbiological assay with a reference Escherichia coli strain indicated that ozonation with MnOx/MWCNT results in more effective antibacterial activity inhibition of ciprofloxacin than that in ozonation alone. The effects of catalyst dose, initial ciprofloxacin concentration, and initial pH conditions on ciprofloxacin ozonation with MnOx/MWCNT were surveyed. Electron spin resonance trapping was applied to assess the role of MnOx/MWCNT in generating hydroxyl radicals (HO{center_dot}) during ozonation. Stronger 5,5-dimethyl-1-pyrroline-N-oxide-OH signals were observed in the ozonation with MnOx/MWCNT compared with those in ozonation alone, indicating that MnOx/MWCNT promoted the generation of hydroxyl radicals. The degradation of ciprofloxacin was studied in drinking water and wastewater process samples to gauge the potential effects of water background matrix on

Catalytic dehydration of ethanol using transition metal oxide catalysts.

Science.gov (United States)

Zaki, T

2005-04-15

The aim of this work is to study catalytic ethanol dehydration using different prepared catalysts, which include Fe(2)O(3), Mn(2)O(3), and calcined physical mixtures of both ferric and manganese oxides with alumina and/or silica gel. The physicochemical properties of these catalysts were investigated via X-ray powder diffraction (XRD), acidity measurement, and nitrogen adsorption-desorption at -196 degrees C. The catalytic activities of such catalysts were tested through conversion of ethanol at 200-500 degrees C using a catalytic flow system operated under atmospheric pressure. The results obtained indicated that the dehydration reaction on the catalyst relies on surface acidity, whereas the ethylene production selectivity depends on the catalyst chemical constituents.

Comparison of direct and indirect plasma oxidation of NO combined with oxidation by catalyst

DEFF Research Database (Denmark)

Jogi, Indrek; Stamate, Eugen; Irimiea, Cornelia

2015-01-01

of the DBD reactor decreased the long-term efficiency of direct plasma oxidation. At the same time, the efficiency of indirect oxidation increased at elevated reactor temperatures. Additional experiments were carried out to investigate the improvement of indirect oxidation by the introduction of catalyst...

Selectivity in the oxidative dehydrogenation of butene on zinc-iron oxide catalyst

Energy Technology Data Exchange (ETDEWEB)

Kung, H.H.; Kundalkar, B.; Kung, M.C.; Cheng, W.H.

1980-02-21

Adsorption, temperature-programed desorption, and pulse reaction studies of cis-2-butene and butadiene on spinel zinc ferrite by previously described methods provided evidence that the selectivity for oxidative dehydrogenation of butenes increases when zinc is added to the iron oxide catalyst because selective oxidation and complete oxidation proceed on separate sites, as they do on pure iron; because the density of sites for selective oxidation is higher and the density of sites for complete combustion is lower than on pure iron oxide; and because the activity of the combustion sites is lower.

Synthesis of honeycomb-like mesoporous nitrogen-doped carbon nanospheres as Pt catalyst supports for methanol oxidation in alkaline media

Science.gov (United States)

Zhang, Yunmao; Liu, Yong; Liu, Weihua; Li, Xiying; Mao, Liqun

2017-06-01

This paper reports the convenient synthesis of honeycomb-like mesoporous nitrogen-doped carbon spheres (MNCS) using a self-assembly strategy that employs dopamine (DA) as a carbon and nitrogen precursor and a polystyrene-b-poly(ethylene oxide) (PS173-b-PEO170) diblock copolymer as a soft template. The MNCS have large BET surface areas of up to 554 m2 g-1 and high nitrogen contents of up to 6.9 wt%. The obtained MNCS are used as a support for Pt catalysts, which promote methanol oxidation in alkaline media. The MNCS-supported Pt (Pt/MNCS) catalyst has a larger electrochemically active surface area (ESA) (89.2 m2 g-1) than does a commercially available Vulcan XC-72R supported Pt/C catalyst. Compared to the Pt/C catalyst, Pt/MNCS displays a higher peak current density (1007 mA mg-1) and is more stable during methanol oxidation. These improvements are attributed to the honeycomb-like porous structure of the MNCS and the introduction of nitrogen to the carbon support. The MNCS effectively stabilize Pt nanoparticles and assuage the agglomeration of the nanoparticles, suggesting that MNCS are potential and promising application as electrocatalyst supports in alkaline direct methanol fuel cells.

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

International Nuclear Information System (INIS)

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

1985-01-01

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

Dehydrogenation of propane in the presence of carbon dioxide over chromium and gallium oxides catalysts

Energy Technology Data Exchange (ETDEWEB)

Lapidus, A.L.; Agafonov, Yu.A.; Gaidai, N.A.; Nekrasov, N.V.; Menshova, M.V.; Kunusova, R.M. [Russian Academy of Sciences, Moscow (Russian Federation). N.D. Zelinsky Inst. of Organic Chemistry

2011-07-01

Effective chromium and gallium oxides supported catalysts were prepared and tested in longduration experiments for propane dehydrogenation in the presence of CO{sub 2}. The optimal concentrations of active metals were found. It was shown that the activity, selectivity and stability of chromium oxides catalysts were higher than these parameters for gallium ones. Mechanism of propane oxidative dehydrogenation was studied over both catalysts using unstationary and spectroscopic methods. The employment of these methods allowed to establish the differences in process mechanism. It was shown that surface hydroxides took participation in propene formation over Cr-catalysts and hydrides - over Ga-ones. Propane and carbon dioxide participated in the reaction from the adsorbed state over both catalysts but they were differed by the adsorption capacity of the reaction components: CO2 was tied more firmly than C{sub 3}H{sub 6} over both catalysts, CO{sub 2} and C{sub 3}H{sub 6} were tied more strongly with Cr-catalysts than with Ga-ones. It was shown that CO{sub 2} took active participation in reverse watergas shift reaction and in oxidation of catalyst surface over chromium oxides catalysts. The main role of CO{sub 2} in propane dehydrogenation over gallium catalysts consisted in a decrease of coke formation. Step-schemes of propene and cracking products formation were proposed on the basis of literature and obtained data: via the redox mechanism over Cr-catalysts and through a heterolytic dissociation reaction pathway over Ga-ones. (orig.)

Iron-tellurium-selenium mixed oxide catalysts for the selective oxidation of propylene to acrolein

International Nuclear Information System (INIS)

Patel, B.M.; Price, G.L.

1990-01-01

This paper reports on iron-tellurium-selenium mixed oxide catalysts prepared by coprecipitation from aqueous solution investigated for the propylene to acrolein reaction in the temperature range 543-773 K. Infrared spectroscopy, electron dispersive X-ray analysis, X-ray diffraction, and isotopic tracer techniques have also been employed to characterize this catalytic system. Properties of the Fe-Te-Se mixed oxide catalysts have been compared with Fe-Te mixed oxides in an effort to deduce the functionality of Se. The selenium in the Fe-Te-Se-O catalyst has been found to be the hydrocarbon activating site. The activation energies for the acrolein and carbon dioxide formation are 71 and 54 kJ/mol, respectively. Reactions carried out with 18 O 2 have shown lattice oxygen to be primarily responsible for the formation of both acrolein and carbon dioxide. The initial and rate-determining step for acrolein formation is hydrogen abstraction as determined by an isotope effect associated with the C 3 D 6 reaction. No isotope effect is observed for carbon dioxide formation from C 3 D 6 suggesting that CO 2 is formed by parallel, not consecutive, oxidation of propylene

Oxidative desulfurization of benzothiophene and thiophene with WOx/ZrO2 catalysts: effect of calcination temperature of catalysts.

Science.gov (United States)

Hasan, Zubair; Jeon, Jaewoo; Jhung, Sung Hwa

2012-02-29

Oxidative desulfurization (ODS) of model fuel containing benzothiophene (BT) or thiophene (Th) has been carried out with WO(x)/ZrO2 catalyst, which was calcined at various temperatures. Based on the conversion of BT in the model fuel, it can be shown that the optimum calcination temperature of WOx/ZrO2 catalyst is around 700 °C. The most active catalyst is composed of tetragonal zirconia (ZrO2) with well dispersed polyoxotungstate species and it is necessary to minimize the contents of the crystalline WO3 and monoclinic ZrO2 for a high BT conversion. The oxidation rate was interpreted with the first-order kinetics, and it demonstrated the importance of electron density since the kinetic constant for BT was higher than that for Th even though the BT is larger than Th in size. A WOx/ZrO2 catalyst, treated suitably, can be used as a reusable active catalyst in the ODS. Copyright © 2012 Elsevier B.V. All rights reserved.

The thermal stability and catalytic performance of Ce-Zr promoted Rh-Pd/γ-Al2O3 automotive catalysts

International Nuclear Information System (INIS)

Wu Xiaodong; Xu Luhua; Weng Duan

2004-01-01

The noble metals (Rh, Pd) supported on alumina promoted with Ce-Zr mixed oxides were investigated as catalysts under diverse oxidants/reductants ratios of simulated automotive exhaust feed gas. Aging test was performed in air at 1000 deg. C for 20 h. Both fresh and aged catalysts, as well as alumina-supported Ce-Zr mixed powders, were characterized by means of X-ray diffraction (XRD), scanning electron microscope (SEM), Brunauer-Emmett-Teller (BET) and X-ray photoelectron spectroscopy (XPS). The results confirmed the oxygen storage capacity of Ce-Zr mixed oxides favored CO, C 3 H 8 and NO conversions in stationary versus dynamic stoichiometric operation. The accelerated aging of the systems produced inconspicuous effect on the phase structure, specific surface area and chemical state of these samples. Accordingly, the aged samples still showed low light-off temperature and broad λ-window, which suggested the relative low relevance of the thermal degradation on the overall catalytic performance of the system

Oxidation of 1-butene over uranium oxide (UO3)-antimony oxide (Sb2O3) catalysts

NARCIS (Netherlands)

Simons, T.; Houtman, P.N.; Schuit, G.C.A.

1971-01-01

The oxidative dehydrogenation of butene to butadiene over U-Sb catalysts was investigated. The presence of two compds., (UO2)Sb3O7 and Sb3U3O14, reported by Grasselli and Callahan (1969), was confirmed with (UO2)Sb3O7 being the actual catalyst. The reaction is first order in butene and zero order in

Oxidative desulfurization of benzothiophene and thiophene with WO{sub x}/ZrO{sub 2} catalysts: Effect of calcination temperature of catalysts

Energy Technology Data Exchange (ETDEWEB)

Hasan, Zubair; Jeon, Jaewoo [Department of Chemistry and Green-Nano Materials Research Center, Kyungpook National University, Daegu 702-701 (Korea, Republic of); Jhung, Sung Hwa, E-mail: sung@knu.ac.kr [Department of Chemistry and Green-Nano Materials Research Center, Kyungpook National University, Daegu 702-701 (Korea, Republic of)

2012-02-29

Highlights: Black-Right-Pointing-Pointer Oxidative desulfurization was studied with WO{sub x}/ZrO{sub 2} calcined at different temp. Black-Right-Pointing-Pointer The importance of the phases of zirconia and tungsten oxide was suggested. Black-Right-Pointing-Pointer The catalyst was analyzed thoroughly with Raman and XRD techniques. Black-Right-Pointing-Pointer The importance of electron density on S was confirmed with the kinetics of oxidation. - Abstract: Oxidative desulfurization (ODS) of model fuel containing benzothiophene (BT) or thiophene (Th) has been carried out with WO{sub x}/ZrO{sub 2} catalyst, which was calcined at various temperatures. Based on the conversion of BT in the model fuel, it can be shown that the optimum calcination temperature of WO{sub x}/ZrO{sub 2} catalyst is around 700 Degree-Sign C. The most active catalyst is composed of tetragonal zirconia (ZrO{sub 2}) with well dispersed polyoxotungstate species and it is necessary to minimize the contents of the crystalline WO{sub 3} and monoclinic ZrO{sub 2} for a high BT conversion. The oxidation rate was interpreted with the first-order kinetics, and it demonstrated the importance of electron density since the kinetic constant for BT was higher than that for Th even though the BT is larger than Th in size. A WO{sub x}/ZrO{sub 2} catalyst, treated suitably, can be used as a reusable active catalyst in the ODS.

Highly efficient bioinspired molecular Ru water oxidation catalysts with negatively charged backbone ligands.

Science.gov (United States)

Duan, Lele; Wang, Lei; Li, Fusheng; Li, Fei; Sun, Licheng

2015-07-21

The oxygen evolving complex (OEC) of the natural photosynthesis system II (PSII) oxidizes water to produce oxygen and reducing equivalents (protons and electrons). The oxygen released from PSII provides the oxygen source of our atmosphere; the reducing equivalents are used to reduce carbon dioxide to organic products, which support almost all organisms on the Earth planet. The first photosynthetic organisms able to split water were proposed to be cyanobacteria-like ones appearing ca. 2.5 billion years ago. Since then, nature has chosen a sustainable way by using solar energy to develop itself. Inspired by nature, human beings started to mimic the functions of the natural photosynthesis system and proposed the concept of artificial photosynthesis (AP) with the view to creating energy-sustainable societies and reducing the impact on the Earth environments. Water oxidation is a highly energy demanding reaction and essential to produce reducing equivalents for fuel production, and thereby effective water oxidation catalysts (WOCs) are required to catalyze water oxidation and reduce the energy loss. X-ray crystallographic studies on PSII have revealed that the OEC consists of a Mn4CaO5 cluster surrounded by oxygen rich ligands, such as oxyl, oxo, and carboxylate ligands. These negatively charged, oxygen rich ligands strongly stabilize the high valent states of the Mn cluster and play vital roles in effective water oxidation catalysis with low overpotential. This Account describes our endeavors to design effective Ru WOCs with low overpotential, large turnover number, and high turnover frequency by introducing negatively charged ligands, such as carboxylate. Negatively charged ligands stabilized the high valent states of Ru catalysts, as evidenced by the low oxidation potentials. Meanwhile, the oxygen production rates of our Ru catalysts were improved dramatically as well. Thanks to the strong electron donation ability of carboxylate containing ligands, a seven

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.

Potassium/calcium/nickel oxide catalysts for the oxidative coupling of methane

NARCIS (Netherlands)

Dooley, K.; Dooley, Kerry M.; Ross, J.R.H.; Ross, Julian R.H.

1992-01-01

A series of potassium/calcium/nickel oxides were tested for the oxidative coupling of methane (OCM) at 843–943 K and water addition to the feed at 0–66 mol-%. The K/Ni ratios varied from 0.0–0.6 and Ca/Ni from 0.0–11; catalysts with no nickel were also tested. At least 10% water in the feed and

Ozone Decomposition on the Surface of Metal Oxide Catalyst

Directory of Open Access Journals (Sweden)

Batakliev Todor Todorov

2014-12-01

Full Text Available The catalytic decomposition of ozone to molecular oxygen over catalytic mixture containing manganese, copper and nickel oxides was investigated in the present work. The catalytic activity was evaluated on the basis of the decomposition coefficient which is proportional to ozone decomposition rate, and it has been already used in other studies for catalytic activity estimation. The reaction was studied in the presence of thermally modified catalytic samples operating at different temperatures and ozone flow rates. The catalyst changes were followed by kinetic methods, surface measurements, temperature programmed reduction and IR-spectroscopy. The phase composition of the metal oxide catalyst was determined by X-ray diffraction. The catalyst mixture has shown high activity in ozone decomposition at wet and dry O3/O2 gas mixtures. The mechanism of catalytic ozone degradation was suggested.

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

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).

Calcium-based mixed oxide catalysts for methanolysis of Jatropha curcas oil to biodiesel

International Nuclear Information System (INIS)

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

2011-01-01

Calcium-based mixed oxides catalysts (CaMgO and CaZnO) have been investigated for the transesterification of Jatropha curcas oil (JCO) with methanol, in order to evaluate their potential as heterogeneous catalysts for biodiesel production. Both CaMgO and CaZnO catalysts were prepared by coprecipitation method of the corresponding mixed metal nitrate solution in the presence of a soluble carbonate salt at ∼ pH 8-9. The catalysts were characterized by X-ray diffraction (XRD), temperature programmed desorption of CO 2 (CO 2 -TPD), scanning electron microscopy (SEM) and N 2 adsorption (BET). The conversion of JCO by CaMgO and CaZnO were studied and compared with calcium oxide (CaO), magnesium oxide (MgO) and zinc oxide (ZnO) catalysts. Both CaMgO and CaZnO catalysts showed high activity as CaO and were easily separated from the product. CaMgO was found more active than CaZnO in the transesterification of JCO with methanol. Under the suitable transesterification conditions at 338 K (catalyst amount = 4 wt. %, methanol/oil molar ratio = 15, reaction time = 6 h), the JCO conversion of more than 80% can be achieved over CaMgO and CaZnO catalysts. Even though CaO gave the highest activity, the conversion of JCO decreased significantly after reused for forth run whereas the conversion was only slightly lowered for CaMgO and CaZnO after sixth run.

Bioinspired organocatalytic aerobic C-H oxidation of amines with an ortho-quinone catalyst.

Science.gov (United States)

Qin, Yan; Zhang, Long; Lv, Jian; Luo, Sanzhong; Cheng, Jin-Pei

2015-03-20

A simple bioinspired ortho-quinone catalyst for the aerobic oxidative dehydrogenation of amines to imines is reported. Without any metal cocatalysts, the identified optimal ortho-quinone catalyst enables the oxidations of α-branched primary amines and cyclic secondary amines. Mechanistic studies have disclosed the origins of different performances of ortho-quinone vs para-quinone in biomimetic amine oxidations.

Computationally Probing the Performance of Hybrid, Heterogeneous, and Homogeneous Iridium-Based Catalysts for Water Oxidation

Energy Technology Data Exchange (ETDEWEB)

García-Melchor, Max [SUNCAT Center for Interface Science and Catalysis, Department of Chemical Engineering, Stanford University, Stanford CA (United States); Vilella, Laia [Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology (BIST),Tarragona (Spain); Departament de Quimica, Universitat Autonoma de Barcelona, Barcelona (Spain); López, Núria [Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology (BIST), Tarragona (Spain); Vojvodic, Aleksandra [SUNCAT Center for Interface Science and Catalysis, SLAC National Accelerator Laboratory, Menlo Park CA (United States)

2016-04-29

An attractive strategy to improve the performance of water oxidation catalysts would be to anchor a homogeneous molecular catalyst on a heterogeneous solid surface to create a hybrid catalyst. The idea of this combined system is to take advantage of the individual properties of each of the two catalyst components. We use Density Functional Theory to determine the stability and activity of a model hybrid water oxidation catalyst consisting of a dimeric Ir complex attached on the IrO₂(110) surface through two oxygen atoms. We find that homogeneous catalysts can be bound to its matrix oxide without losing significant activity. Hence, designing hybrid systems that benefit from both the high tunability of activity of homogeneous catalysts and the stability of heterogeneous systems seems feasible.

Mechanochemical synthesis of graphene oxide-supported transition metal catalysts for the oxidation of isoeugenol to vanillin.

Science.gov (United States)

Franco, Ana; De, Sudipta; Balu, Alina M; Garcia, Araceli; Luque, Rafael

2017-01-01

Vanillin is one of the most commonly used natural products, which can also be produced from lignin-derived feedstocks. The chemical synthesis of vanillin is well-established in large-scale production from petrochemical-based starting materials. To overcome this problem, lignin-derived monomers (such as eugenol, isoeugenol, ferulic acid etc.) have been effectively used in the past few years. However, selective and efficient production of vanillin from these feedstocks still remains an issue to replace the existing process. In this work, new transition metal-based catalysts were proposed to investigate their efficiency in vanillin production. Reduced graphene oxide supported Fe and Co catalysts showed high conversion of isoeugenol under mild reaction conditions using H 2 O 2 as oxidizing agent. Fe catalysts were more selective as compared to Co catalysts, providing a 63% vanillin selectivity at 61% conversion in 2 h. The mechanochemical process was demonstrated as an effective approach to prepare supported metal catalysts that exhibited high activity for the production of vanillin from isoeugenol.

Supramolecular water oxidation with rubda-based catalysts

KAUST Repository

Richmond, Craig J.; Matheu, Roc; Poater, Albert; Falivene, Laura; Benet-Buchholz, Jordi; Sala, Xavier; Cavallo, Luigi; Llobet, Antoni A.

2014-01-01

Extremely slow and extremely fast new water oxidation catalysts based on the Rubda (bda = 2,2′-bipyri-dine-6,6′-dicarboxylate) systems are reported with turnover frequencies in the range of 1 and 900 cycless"1, respectively. Detailed analyses

Magnesium oxide prepared via metal-chitosan complexation method: Application as catalyst for transesterification of soybean oil and catalyst deactivation studies

Science.gov (United States)

Almerindo, Gizelle I.; Probst, Luiz F. D.; Campos, Carlos E. M.; de Almeida, Rusiene M.; Meneghetti, Simoni M. P.; Meneghetti, Mario R.; Clacens, Jean-Marc; Fajardo, Humberto V.

2011-10-01

A simple method to prepare magnesium oxide catalysts for biodiesel production by transesterification reaction of soybean oil with ethanol is proposed. The method was developed using a metal-chitosan complex. Compared to the commercial oxide, the proposed catalysts displayed higher surface area and basicity values, leading to higher yield in terms of fatty acid ethyl esters (biodiesel). The deactivation of the catalyst due to contact with CO2 and H2O present in the ambient air was verified. It was confirmed that the active catalytic site is a hydrogenocarbonate adsorption site.

Mo-V-Te-Nb oxides as catalysts for ethene production by oxidative dehydrogenation of ethane

Energy Technology Data Exchange (ETDEWEB)

Hartmann, D. [Technische Universitaet Muenchen, Garching (Germany). Dept. of Chemistry and Catalysis Research Center; Meiswinkel, A.; Thaller, C.; Bock, M.; Alvarado, L. [Linde AG, Pullach (Germany)

2013-11-01

The availability of ethane in shale gas, as well as the interest in valorising previously underutilized carbon feedstocks, makes the oxidative dehydrogenation (ODH) of ethane an attractive alternative to the industrially established processes for production of ethylene. Mo-V-Te-Nb mixed oxide has been chosen as catalyst for the ODH reaction in view of its outstanding ability to activate alkane molecules. Catalytic test results showed that this type of catalyst can selectively oxidize ethane to ethene at moderate temperatures (350-400 C) with minor production of CO{sub x}. The catalytic performance of Mo-V-Te-Nb mixed-oxide is mainly attributable to the crystalline phase 'M1'. Rietveld analysis of the X-Ray diffractograms allowed us to quantify the amount of MoVTeNb oxide that has crystallized as M1. In this way, it was possible to find a linear correlation of the reaction rate with the abundance of M1 in the solid. Therefore, it is clear that for improving the efficiency of MoVTeNb oxide in ODH, the amount of M1 in the catalyst should be maximized. With this purpose, several MoVTeNb oxides were subject to different thermal treatments prior to the catalytic test. Structural changes in the catalyst were monitored by in-situ XRD technique. Under oxidative atmosphere, it was observed a recrystallization of M2 and possibly, amorphous oxide, into M1 phase, leading to correspondingly more active and selective catalysts (selectivities above 95 % for ethane conversions up to 40 % under industrially relevant conditions). The active site of M1 involves V species, likely with redox properties enhanced by the proximity of Mo and Te species, while the function of the crystalline structure itself is to provide the spatial configuration that allows interaction between these species. However, ethene formation rate was observed to be independent of the V content of the samples. The vanadium species exposed at the surface were studied by LEIS and by IR spectroscopy of CO

Formation of nitrogen compounds from nitrogen-containing rings during oxidative regeneration of spent hydroprocessing catalysts

Energy Technology Data Exchange (ETDEWEB)

Furimsky, E.; Nielsen, M.; Jurasek, P. [CANMET, Ottawa, ON (Canada). Energy Research Laboratories

1995-05-01

Commercial CoMo and NiMo catalysts in an oxidic and sulfided form and a {gamma}-alumina were deposited with pyrrole, pyridine, and quinoline. The deposited catalysts and two spent hydroprocessing catalysts were pyrolyzed and oxidized under conditions typical of regeneration of hydroprocessing catalysts. The formation of NH{sub 3} and HCN, as well as selected cases of N{sub 2}O and NO, was monitored during the experiments. NH{sub 3} and HCN were formed during pyrolysis of pyrrole-deposited catalysts whereas only NH{sub 3} was formed during that of pyridine-and quinoline-deposited catalysts. For all deposited catalysts, both NH{sub 3} and HCN were formed during temperature programmed oxidation in 2% O{sub 2}. For spent catalysts, a small amount of N{sub 2}O was formed in 2 and 4% O{sub 2}. For pyrrole-deposited catalysts, large yields of N{sub 2}O were formed in 4% O{sub 2}. Under the same conditions, N{sub 2}O yields for pyridine- and quinoline-deposited catalysts were very small. 13 refs., 12 figs., 6 tabs.

Stepwise mechanism of oxidative ammonolysis of propane to acrylonitrile over gallium-antimony oxide catalysts

Energy Technology Data Exchange (ETDEWEB)

Osipova, Z.G.; Sokolovskii, V.D.

1979-03-01

The stepwise mechanism of oxidative ammonolysis of propane to acrylonitrile over gallium-antimony oxide catalysts GaSb/sub 19/O/sub x/, GaSb/sub 3/Ni/sub 1.5/0/sub x/, and GaSb/sub 2.5/Ni/sub 1.5/PW/sub 0//sub 0.25/O/sub x/ was studied at 450/sup 0/ and 550/sup 0/C by introducing alternating pulses of 0.5Vertical Bar3< propane/0.6Vertical Bar3< ammonia/helium (to reduce the steady-state catalytic surface) and 0.5Vertical Bar3< propane/0.6Vertical Bar3< ammonia/1.86Vertical Bar3< oxygen/helium mixtures into a fluidized-bed catalytic reactor. Over all the catalysts studied, the rates of acrylonitrile formation during the two types of pulses were very similar, but carbon dioxide was formed much faster during the reducing pulses, particularly at 450/sup 0/C. These findings suggested that acrylonitrile is formed by a stepwise redox mechanism involving consecutive interaction of propane and ammonia with the surface oxygen of the catalysts and oxidation of the reduced catalyst surface by gas-phase oxygen. The formation of carbon dioxide proceeds by both stepwise and associative mechanisms, the latter being more important at higher temperatures. The results are similar to published results for ammoxidation of propylene and olefins.

Structural analysis of nickel doped cerium oxide catalysts for fuel reforming in solid oxide fuel cells

Science.gov (United States)

Cavendish, Rio

As world energy demands increase, research into more efficient energy production methods has become imperative. Heterogeneous catalysis and nanoscience are used to promote chemical transformations important for energy production. These concepts are important in solid oxide fuel cells (SOFCs) which have attracted attention because of their potential to provide an efficient and environmentally favorable power generation system. The SOFC is also fuel-flexible with the ability to run directly on many fuels other than hydrogen. Internal fuel reforming directly in the anode of the SOFC would greatly reduce the cost and complexity of the device. Methane is the simplest hydrocarbon and a main component in natural gas, making it useful when testing catalysts on the laboratory scale. Nickel (Ni) and gadolinium (Gd) doped ceria (CeO 2) catalysts for potential use in the SOFC anode were synthesized with a spray drying method and tested for catalytic performance using partial oxidation of methane and steam reforming. The relationships between catalytic performance and structure were then investigated using X-ray diffraction, transmission electron microscopy, and environmental transmission electron microscopy. The possibility of solid solutions, segregated phases, and surface layers of Ni were explored. Results for a 10 at.% Ni in CeO2 catalyst reveal a poor catalytic behavior while a 20 at.% Ni in CeO2 catalyst is shown to have superior activity. The inclusion of both 10 at.% Gd and 10 at.% Ni in CeO2 enhances the catalytic performance. Analysis of the presence of Ni in all 3 samples reveals Ni heterogeneity and little evidence for extensive solid solution doping. Ni is found in small domains throughout CeO2 particles. In the 20 at.% Ni sample a segregated, catalytically active NiO phase is observed. Overall, it is found that significant interaction between Ni and CeO2 occurs that could affect the synthesis and functionality of the SOFC anode.

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

Science.gov (United States)

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

1990-01-01

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

Activity of Cu-activated carbon fiber catalyst in wet oxidation of ammonia solution.

Science.gov (United States)

Hung, Chang-Mao

2009-07-30

Aqueous solutions of 200-1000 mg/L of ammonia were oxidized in a trickle-bed reactor using Cu-activated carbon fiber (ACF) catalysts, which were prepared by incipient wet impregnation with aqueous solutions of copper nitrate that was deposited on ACF substrates. The results reveal that the conversion of ammonia by wet oxidation in the presence of Cu-ACF catalysts was a function of the metal loading weight ratio of the catalyst. The total conversion efficiency of ammonia was 95% during wet oxidation over the catalyst at 463 K at an oxygen partial pressure of 3.0 MPa. Moreover, the effect of the initial concentration of ammonia and the reaction temperature on the removal of ammonia from the effluent streams was also studied at a liquid space velocity of less than 3.0 h(-1).

Activity of Cu-activated carbon fiber catalyst in wet oxidation of ammonia solution

International Nuclear Information System (INIS)

Hung, Chang-Mao

2009-01-01

Aqueous solutions of 200-1000 mg/L of ammonia were oxidized in a trickle-bed reactor using Cu-activated carbon fiber (ACF) catalysts, which were prepared by incipient wet impregnation with aqueous solutions of copper nitrate that was deposited on ACF substrates. The results reveal that the conversion of ammonia by wet oxidation in the presence of Cu-ACF catalysts was a function of the metal loading weight ratio of the catalyst. The total conversion efficiency of ammonia was 95% during wet oxidation over the catalyst at 463 K at an oxygen partial pressure of 3.0 MPa. Moreover, the effect of the initial concentration of ammonia and the reaction temperature on the removal of ammonia from the effluent streams was also studied at a liquid space velocity of less than 3.0 h -1 .

Titania Supported Co-Mn-Al Oxide Catalysts in Total Oxidation of Ethanol

Czech Academy of Sciences Publication Activity Database

Ludvíková, Jana; Jirátová, Květa; Klempa, Jan; Böhmová, Vlasta; Obalová, L.

2012-01-01

Roč. 179, č. 1 (2012), s. 164-169 ISSN 0920-5861 R&D Projects: GA ČR GAP106/10/1762; GA ČR GD203/08/H032 Institutional research plan: CEZ:AV0Z40720504; CEZ:AV0Z30130516 Keywords : mixed oxide catalysts * voc oxidation * titania Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 2.980, year: 2012

Catalysts for synthetic liquid fuels

Energy Technology Data Exchange (ETDEWEB)

Bruce, L.A.; Turney, T.W.

1987-12-01

Fischer-Tropsch catalysts have been designed, characterized and tested for the selective production of hydrocarbons suitable as synthetic liquid transport fuels from synthesis gas (i.e., by the reduction of carbon monoxide with hydrogen). It was found that hydrocarbons in the middle distillate range, or suitable for conversion to that range, could be produced over several of the new catalyst systems. The various catalysts examined included: (1) synthetic cobalt clays, mainly cobalt chlorites; (2) cobalt hydrotalcites; (3) ruthenium metal supported on rare earth oxides of high surface area; and (4) a novel promoted cobalt catalyst. Active and selective catalysts have been obtained, in each category. With the exception of the clays, reproducibility of catalyst performance has been good. Catalysts in groups 2 and 4 have exhibited very high activity, with long lifetimes and easy regeneration.

Solid oxide fuel cells fueled with reducible oxides

Science.gov (United States)

Chuang, Steven S.; Fan, Liang Shih

2018-01-09

A direct-electrochemical-oxidation fuel cell for generating electrical energy includes a cathode provided with an electrochemical-reduction catalyst that promotes formation of oxygen ions from an oxygen-containing source at the cathode, a solid-state reduced metal, a solid-state anode provided with an electrochemical-oxidation catalyst that promotes direct electrochemical oxidation of the solid-state reduced metal in the presence of the oxygen ions to produce electrical energy, and an electrolyte disposed to transmit the oxygen ions from the cathode to the solid-state anode. A method of operating a solid oxide fuel cell includes providing a direct-electrochemical-oxidation fuel cell comprising a solid-state reduced metal, oxidizing the solid-state reduced metal in the presence of oxygen ions through direct-electrochemical-oxidation to obtain a solid-state reducible metal oxide, and reducing the solid-state reducible metal oxide to obtain the solid-state reduced metal.

Aluminum Oxide Formation On Fecral Catalyst Support By Electro-Chemical Coating

Directory of Open Access Journals (Sweden)

Yang H.S.

2015-06-01

Full Text Available FeCrAl is comprised essentially of Fe, Cr, Al and generally considered as metallic substrates for catalyst support because of its advantage in the high-temperature corrosion resistance, high mechanical strength, and ductility. Oxidation film and its adhesion on FeCrAl surface with aluminum are important for catalyst life. Therefore various appropriate surface treatments such as thermal oxidation, Sol, PVD, CVD has studied. In this research, PEO (plasma electrolytic oxidation process was applied to form the aluminum oxide on FeCrAl surface, and the formed oxide particle according to process conditions such as electric energy and oxidation time were investigated. Microstructure and aluminum oxide particle on FeCrAl surface after PEO process was observed by FE-SEM and EDS with element mapping analysis. The study presents possibility of aluminum oxide formation by electro-chemical coating process without any pretreatment of FeCrAl.

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

DEFF Research Database (Denmark)

Li, Hu; Kotni, Ramakrishna; Zhang, Qiuyun

2015-01-01

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

Synthesis of cerium oxide catalysts supported on MCM-41 molecular sieve

International Nuclear Information System (INIS)

Souza, E.L.S.; Barros, T.R.B.; Sousa, B.V. de

2016-01-01

Porous materials have been widely studied as catalysts and catalyst support. The MCM-41 structure is the one that has been most studied because of its application possibilities in chemical processes. This work aimed to obtain and characterize cerium oxide catalysts supported on MCM-41 molecular sieve. The molecular sieve was synthesized by the conventional method with the following molar composition: 1 SiO2: 0.30 CTABr: NH3 11: 144 H2O. Then, 25% w/w cerium was incorporated into the MCM-41 using the wet impregnation process and the material obtained was activated by calcination. From the XRD patterns was confirmed the structure of the molecular sieve, and were identified the cerium oxide phases in its structure. The textural catalysts characteristics were investigated by isotherms of N2 adsorption/desorption (BET method). (author)

The role of potassium as a promoter in iron catalysts for ammonia synthesis

NARCIS (Netherlands)

Altenburg, K.; Bosch, H.; van Ommen, J.G.; Gellings, P.J.

1980-01-01

Five ammonia synthesis catalysts, mainly differing in potassium content, were prepared from a commercial doubly promoted iron catalyst. The activities of these catalysts were measured at 350–450 °C and 5–200 atm. The experimental reaction rates were fitted to the modified Temkin rate equation.

Selective oxidation of propylene to acrolein by silica-supported bismuth molybdate catalysts

DEFF Research Database (Denmark)

Duc, Duc Truong; Ha, Hanh Nguyen; Fehrmann, Rasmus

2011-01-01

Silica-supported bismuth molybdate catalysts have been prepared by impregnation, structurally characterized and examined as improved catalysts for the selective oxidation of propylene to acrolein. Catalysts with a wide range of loadings (from 10 to 90 wt%) of beta bismuth molybdate (β-Bi2Mo2O9) w...

Strategies for catalyst development: possibilities of the ``rational approach`` illustrated with partial oxidation reactions

Energy Technology Data Exchange (ETDEWEB)

Weiss, W.; Schedel-Niedrig, T.; Schloegl, R. [Fritz-Haber-Institut der Max-Planck-Gesellschaft, Berlin (Germany). Abt. Oberflaechenphysik

1998-12-31

The paper discusses two petrochemical selective oxidation reactions namely the practised formation of styrene (STY) and the desired oxidative functionalisation of propane. The present knowledge about the mode of operation of oxide catalysts is critically considered. The dehydrogenation of ethylbenzene (EB) should be described by an oxidehydration with water acting as oxidant. The potential role of the coke formed during catalytic reaction as co-catalyst will be discussed. Selective oxidation is connected with the participation of lattice oxygen mechanism which transforms unselective gas phase oxygen into selective oxygen. The atomistic description of this process is still quite unclear as well as the electron structural properties of the activated oxygen atom. The Role of solid state acidity as compared to the role of lattice oxygen is much less well investigated modern multiphase-multielement oxide (MMO) catalysts. The rationale is that the significant efforts made to improve current MMO systems by chemical modifications can be very much more fruitful when in a first step the mode of action of a catalyst is clarified on the basis of suitable experiments. Such time-consuming experiments at the beginning of a campaign for catalyst improvement pay back their investment in later stages of the project when strategies of chemical development can be derived on grounds of understanding. (orig.)

IR-doped ruthenium oxide catalyst for oxygen evolution

Science.gov (United States)

Valdez, Thomas I. (Inventor); Narayanan, Sekharipuram R. (Inventor)

2012-01-01

A method for preparing a metal-doped ruthenium oxide material by heating a mixture of a doping metal and a source of ruthenium under an inert atmosphere. In some embodiments, the doping metal is in the form of iridium black or lead powder, and the source of ruthenium is a powdered ruthenium oxide. An iridium-doped or lead-doped ruthenium oxide material can perform as an oxygen evolution catalyst and can be fabricated into electrodes for electrolysis cells.

Electrocatalytic Water Oxidation by a Homogeneous Copper Catalyst Disfavors Single-Site Mechanisms.

Science.gov (United States)

Koepke, Sara J; Light, Kenneth M; VanNatta, Peter E; Wiley, Keaton M; Kieber-Emmons, Matthew T

2017-06-28

Deployment of solar fuels derived from water requires robust oxygen-evolving catalysts made from earth abundant materials. Copper has recently received much attention in this regard. Mechanistic parallels between Cu and single-site Ru/Ir/Mn water oxidation catalysts, including intermediacy of terminal Cu oxo/oxyl species, are prevalent in the literature; however, intermediacy of late transition metal oxo species would be remarkable given the high d-electron count would fill antibonding orbitals, making these species high in energy. This may suggest alternate pathways are at work in copper-based water oxidation. This report characterizes a dinuclear copper water oxidation catalyst, {[(L)Cu(II)] 2 -(μ-OH) 2 }(OTf) 2 (L = Me 2 TMPA = bis((6-methyl-2-pyridyl)methyl)(2-pyridylmethyl)amine) in which water oxidation proceeds with high Faradaic efficiency (>90%) and moderate rates (33 s -1 at ∼1 V overpotential, pH 12.5). A large kinetic isotope effect (k H /k D = 20) suggests proton coupled electron transfer in the initial oxidation as the rate-determining step. This species partially dissociates in aqueous solution at pH 12.5 to generate a mononuclear {[(L)Cu(II)(OH)]} + adduct (K eq = 0.0041). Calculations that reproduce the experimental findings reveal that oxidation of either the mononuclear or dinuclear species results in a common dinuclear intermediate, {[LCu(III)] 2 -(μ-O) 2 } 2+ , which avoids formation of terminal Cu(IV)═O/Cu(III)-O • intermediates. Calculations further reveal that both intermolecular water nucleophilic attack and redox isomerization of {[LCu(III)] 2 -(μ-O) 2 } 2+ are energetically accessible pathways for O-O bond formation. The consequences of these findings are discussed in relation to differences in water oxidation pathways between Cu catalysts and catalysts based on Ru, Ir, and Mn.

The role of promoters for Ni catalysts in low temperature (membrane) steam methane reforming

NARCIS (Netherlands)

Ligthart, D.A.J.M.; Pieterse, J.A.Z.; Hensen, E.J.M.

2011-01-01

In the search for active and stable Ni-based catalysts for steam methane reforming in membrane reactors, the effect of three different promoters La, B and Rh was compared. Promoted and unpromoted Ni catalysts were characterized by TEM, TPR and X-ray absorption spectroscopy. The average Ni particle

Modelling of the partial oxidation of {alpha}, {beta}-unsaturated aldehydes on Mo-V-oxides based catalysts

Energy Technology Data Exchange (ETDEWEB)

Boehnke, H.; Petzoldt, J.C.; Stein, B.; Weimer, C.; Gaube, J.W. [Technische Univ. Darmstadt (Germany). Inst. fuer Chemische Technologie

1998-12-31

A kinetic model based on the Mars-van Krevelen mechanism that allows to describe the microkinetics of the heterogeneously catalysed partial oxidation of {alpha}, {beta}-unsaturated aldehydes is presented. This conversion is represented by a network, composed of the oxidation of the {alpha}, {beta}-unsaturated aldehyde towards the {alpha}, {beta}-unsaturated carboxylic acid and the consecutive oxidation of the acid as well as the parallel reaction of the aldehyde to products of deeper oxidation. The reaction steps of aldehyde respectively acid oxidation and catalyst reoxidation have been investigated separately in transient experiments. The combination of steady state and transient experiments has led to an improved understanding of the interaction of the catalyst with the aldehyde and the carboxylic acids as well as to a support of the kinetic model assumptions. (orig.)

The Effect of Annealing Temperature on Nickel on Reduced Graphene Oxide Catalysts on Urea Electrooxidation

International Nuclear Information System (INIS)

Glass, Dean E.; Galvan, Vicente; Prakash, G.K. Surya

2017-01-01

Highlights: •Nickel was reduced on graphene oxide and annealed under argon from 300 to 700 °C. •Nickel was oxidized from the removal of oxygen groups on the graphene oxide. •Higher annealed catalysts displayed decreased urea electrooxidation currents. •Micro direct urea/hydrogen peroxide fuel cells were employed for the first time. •Ni/rGO catalysts displayed enhanced fuel cell performance than the bare nickel. -- Abstract: The annealing temperature effects on nickel on reduced graphene oxide (Ni/rGO) catalysts for urea electrooxidation were investigated. Nickel chloride was directly reduced in an aqueous solution of graphene oxide (GO) followed by annealing under argon at 300, 400, 500, 600, and 700 °C, respectively. X-ray Diffraction (XRD) patterns revealed an increase in the crystallite size of the nickel nanoparticles while the Raman spectra displayed an increase in the graphitic disorder of the reduced graphene oxide at higher annealing temperatures due to the removal of oxygen functional groups. The Ni/rGO catalysts annealed at higher temperatures displayed oxidized nickel surface characteristics from the Ni 2p X-ray Photoelectron Spectra (XPS) due to the oxidation of the nickel from the oxygen functional groups in the graphitic lattice. In the half-cell testing, the onset potential of urea electrooxidation decreased while the urea electrooxidation currents decreased as the annealing temperature was increased. The nickel catalyst annealed at 700 °C displayed a 31% decrease in peak power density while the catalyst annealed at 300 °C displayed a 13% increase compared with the unannealed Ni/rGO catalyst in the micro direct urea/hydrogen peroxide fuel cells tests.

Silver-promoted catalyst for removal of nitrogen oxides from emission of diesel engines

Energy Technology Data Exchange (ETDEWEB)

Masuda, K.; Tsujimura, K. [New ACE Institute Co., Ltd., Ibaraki (Japan); Shinoda, K.; Kato, T. [Mitsui Mining and Smelting Co., Ltd. Ageo, Saitama (Japan)

1996-02-29

Removal of NO{sub x} from diesel exhaust gas using C{sub 3}H{sub 6}, CH{sub 3}OH or (CH{sub 3}){sub 2}O as a reducing agent was investigated on Ag/Al{sub 2}O{sub 3}, Ag/ZSM-5 and Ag/mordenite catalysts over a wide range of temperatures. Among them, (CH{sub 3}){sub 2}O was found to be suitable for the elimination of NO{sub x} over Ag/mordenite catalyst at the relatively low temperature of 200C to 350C. CH{sub 3}OH was suitable over Ag/Al{sub 2}O{sub 3} catalyst from 350C to 450C while the Ag/mordenite catalyst using (CH{sub 3}){sub 2}O was superior to the Ag/Al{sub 2}O{sub 3} catalyst using CH{sub 3}OH with respect to the temperature range. The Ag/ZSM-5 catalyst had a poor elimination ability when compared with Ag/Al{sub 2}O{sub 3} and Ag/mordenite catalysts. The effects of Ag on mordenite and Al{sub 2}O{sub 3} were also investigated. It was found that Ag improved the removal of NO{sub x} in the higher range of temperatures with mordenite, while Ag improved the removal of NO{sub x} in the lower temperature range with Al{sub 2}O{sub 3}. It was concluded that Ag/mordenite catalyst using (CH{sub 3}){sub 2}O as a reducing agent has a good ability for NO{sub x} removal over a wide range of temperatures

Chlorination of antimony and its volatilization treatment of waste antimony-uranium composite oxide catalyst

International Nuclear Information System (INIS)

Sawada, K.; Enokida, Y.

2011-01-01

For the waste antimony-uranium composite oxide catalyst, the chlorination of antimony and its volatilization treatment were proposed, and evaluated using hydrogen chloride gas at 873-1173 K. During the treatment, the weight loss of the composite oxide sample, which resulted from the volatilization of antimony, was confirmed. An X-ray diffraction analysis showed that uranium oxide, U 3 O 8 , was formed during the reaction. After the treatment at 1173 K for 1 h, almost all the uranium contained in the waste catalyst was dissolved by a 3 M nitric acid solution at 353 K within 10 min, although that of the non-treated catalyst was less than 0.1%. It was found that the chlorination and volatilization treatment was effective to separate antimony from the composite oxide catalyst and change uranium into its removable form. (orig.)

Mechanochemical synthesis of graphene oxide-supported transition metal catalysts for the oxidation of isoeugenol to vanillin

Directory of Open Access Journals (Sweden)

Ana Franco

2017-07-01

Full Text Available Vanillin is one of the most commonly used natural products, which can also be produced from lignin-derived feedstocks. The chemical synthesis of vanillin is well-established in large-scale production from petrochemical-based starting materials. To overcome this problem, lignin-derived monomers (such as eugenol, isoeugenol, ferulic acid etc. have been effectively used in the past few years. However, selective and efficient production of vanillin from these feedstocks still remains an issue to replace the existing process. In this work, new transition metal-based catalysts were proposed to investigate their efficiency in vanillin production. Reduced graphene oxide supported Fe and Co catalysts showed high conversion of isoeugenol under mild reaction conditions using H2O2 as oxidizing agent. Fe catalysts were more selective as compared to Co catalysts, providing a 63% vanillin selectivity at 61% conversion in 2 h. The mechanochemical process was demonstrated as an effective approach to prepare supported metal catalysts that exhibited high activity for the production of vanillin from isoeugenol.

Ni–Ta–O mixed oxide catalysts for the low temperature oxidative dehydrogenation of ethane to ethylene

KAUST Repository

Zhu, Haibo; Rosenfeld, Devon C.; Anjum, Dalaver H.; Sangaru, Shiv; Saih, Youssef; Ould-Chikh, Samy; Basset, Jean-Marie

2015-01-01

The "wet" sol-gel and "dry" solid-state methods were used to prepare Ni-Ta-O mixed oxide catalysts. The resulting Ni-Ta oxides exhibit high activity and selectivity for the low temperature oxidative dehydrogenation of ethane to ethylene. The Ta

Activity of Cu-activated carbon fiber catalyst in wet oxidation of ammonia solution

Energy Technology Data Exchange (ETDEWEB)

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

2009-07-30

Aqueous solutions of 200-1000 mg/L of ammonia were oxidized in a trickle-bed reactor using Cu-activated carbon fiber (ACF) catalysts, which were prepared by incipient wet impregnation with aqueous solutions of copper nitrate that was deposited on ACF substrates. The results reveal that the conversion of ammonia by wet oxidation in the presence of Cu-ACF catalysts was a function of the metal loading weight ratio of the catalyst. The total conversion efficiency of ammonia was 95% during wet oxidation over the catalyst at 463 K at an oxygen partial pressure of 3.0 MPa. Moreover, the effect of the initial concentration of ammonia and the reaction temperature on the removal of ammonia from the effluent streams was also studied at a liquid space velocity of less than 3.0 h{sup -1}.

Highly Efficient Gas-Phase Oxidation of Renewable Furfural to Maleic Anhydride over Plate Vanadium Phosphorus Oxide Catalyst.

Science.gov (United States)

Li, Xiukai; Ko, Jogie; Zhang, Yugen

2018-02-09

Maleic anhydride (MAnh) and its acids are critical intermediates in chemical industry. The synthesis of maleic anhydride from renewable furfural is one of the most sought after processes in the field of sustainable chemistry. In this study, a plate vanadium phosphorus oxide (VPO) catalyst synthesized by a hydrothermal method with glucose as a green reducing agent catalyzes furfural oxidation to MAnh in the gas phase. The plate catalyst-denoted as VPO HT -has a preferentially exposed (200) crystal plane and exhibited dramatically enhanced activity, selectivity and stability as compared to conventional VPO catalysts and other state-of-the-art catalytic systems. At 360 °C reaction temperature with air as an oxidant, about 90 % yield of MAnh was obtained at 10 vol % of furfural in the feed, a furfural concentration value that is much higher than those (<2 vol %) reported for other catalytic systems. The catalyst showed good long-term stability and there was no decrease in activity or selectivity for MAnh during the time-on-stream of 25 h. The high efficiency and catalyst stability indicate the great potential of this system for the synthesis of maleic anhydride from renewable furfural. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

ZIF-67-derived hollow nanocages with layered double oxides shell as high-Efficiency catalysts for CO oxidation

Science.gov (United States)

Kong, Wenpeng; Li, Jing; Chen, Yao; Ren, Yuqing; Guo, Yonghua; Niu, Shengli; Yang, Yanzhao

2018-04-01

Constructing non-precious hybrid metal oxides with specific morphology as cost-effective and highly efficient catalysts is a promising way for the automotive exhaust purification. In this work, we report a facile strategy for the fabrication of a unique hollow Co-Ni layered double oxides (HLDO) nanocages by using zeolitic imidazole frameworks (ZIFs) as template. The synthesis of intermediate core-shell and hollow Co-Ni layered double hydroxides (HLDH) nanoflakes as well as the corresponding Co-Ni oxides products were successfully controlled, and the formation process was also explained. Among ZIF-67-derived oxides, HLDO exhibits excellent catalytic activities (complete conversion of CO into CO2 at 118 °C) and long-term stability for CO oxidation. The remarkable catalytic activities of HLDO can be attributed to high surface area (258 m2 g-1) inherited from the HLDH, which could provide more active sites for CO oxidation. In addition, active oxygen species indicated by the O 1 s XPS spectrum and improved synergistic effect between NiO and Co3O4 reflected by H2-TPR, further explain the enhanced performance of the HLDO catalysts. The presented strategy for controlled design and synthesis of hollow multicomponent metal oxides will provide prospects in developing highly effective catalysts.

Catalyst for reduction of nitrogen oxides

Science.gov (United States)

Ott, Kevin C.

2010-04-06

A Selective Catalytic Reduction (SCR) catalyst was prepared by slurry coating ZSM-5 zeolite onto a cordierite monolith, then subliming an iron salt onto the zeolite, calcining the monolith, and then dipping the monolith either into an aqueous solution of manganese nitrate and cerium nitrate and then calcining, or by similar treatment with separate solutions of manganese nitrate and cerium nitrate. The supported catalyst containing iron, manganese, and cerium showed 80 percent conversion at 113 degrees Celsius of a feed gas containing nitrogen oxides having 4 parts NO to one part NO.sub.2, about one equivalent ammonia, and excess oxygen; conversion improved to 94 percent at 147 degrees Celsius. N.sub.2O was not detected (detection limit: 0.6 percent N.sub.2O).

Effect of Au Precursor and Support on the Catalytic Activity of the Nano-Au-Catalysts for Propane Complete Oxidation

Directory of Open Access Journals (Sweden)

Arshid M. Ali

2015-01-01

Full Text Available Catalytic activity of nano-Au-catalyst(s for the complete propane oxidation was investigated. The results showed that the nature of both Au precursor and support strongly influences catalytic activity of the Au-catalyst(s for the propane oxidation. Oxidation state, size, and dispersion of Au nanoparticles in the Au-catalysts, surface area, crystallinity, phase structure, and redox property of the support are the key aspects for the complete propane oxidation. Among the studied Au-catalysts, the AuHAuCl4-Ce catalyst is found to be the most active catalyst.

Influence of Gold on Ce-Zr-Co Fluorite-Type Mixed Oxide Catalysts for Ethanol Steam Reforming

Directory of Open Access Journals (Sweden)

Véronique Pitchon

2012-02-01

Full Text Available The effect of gold presence on carbon monoxide oxidation and ethanol steam reforming catalytic behavior of two Ce-Zr-Co mixed oxides catalysts with a constant Co charge and different Ce/Zr ratios was investigated. The Ce-Zr-Co mixed oxides were obtained by the pseudo sol-gel like method, based on metallic propionates polymerization and thermal decomposition, whereas the gold-supported Ce-Zr-Co mixed oxides catalysts were prepared using the direct anionic exchange. The catalysts were characterized using XRD, TPR, and EDXS-TEM. The presence of Au in doped Ce-Zr-Co oxide catalyst decreases the temperature necessary to reduce the cobalt and the cerium loaded in the catalyst and favors a different reaction pathway, improving the acetaldehyde route by ethanol dehydrogenation, instead of the ethylene route by ethanol dehydration or methane re-adsorption, thus increasing the catalytic activity and selectivity into hydrogen.

Revisiting the electrochemical oxidation of ammonia on carbon-supported metal nanoparticle catalysts

International Nuclear Information System (INIS)

Li, Zhe-Fei; Wang, Yuxuan; Botte, Gerardine G.

2017-01-01

Highlights: • A procedure to pretreat electrocatalysts to study the ammonia oxidation is provided. • N ads and O/OH ads were identified as the major deactivation species that prevent ammonia oxidatoin. • The electrocatalytic activity, thermodynamics, and possible deactivation mechanisms for ammonia oxidation were elucidated. • The onset potential for ammonia oxidation is related to the hydrogen binding energy of the catalyst. • Ammonia electro-oxidation involves a complex decoupled electron and proton transfer process. - Abstract: The ammonia electro-oxidation reaction (AOR) has been studied due to its promising applications in ammonia electrolysis, wastewater remediation, direct ammonia fuel cells, and sensors. However, it is difficult to compare and analyze the reported electrocatalytic activity of AOR reliably, likely due to the variation in catalyst synthesis, electrode composition, electrode morphology, and testing protocol. In this paper, the electro-oxidation of ammonia on different carbon-supported precious metal nanoparticle catalysts was revisited. The effect of experimental conditions, electrochemical test parameters, electrocatalytic activity, thermodynamics, and possible deactivation mechanism of the catalysts were investigated. Pt/C catalyst possesses the highest electrocatalytic activity, while Ir/C and Rh/C show lower overpotential. The onset potential of the AOR is related to the hydrogen binding energy of the catalyst. N ads is one major cause of deactivation accompanied with the formation of surface O/OH ads at high potentials. The coulombic efficiency of N ads formation on Pt is about 1% initially and gradually decreases with reaction time. Increase in ammonia concentration leads to increase in current density, while increase in hydroxyl ions concentration can enhance the current density and reduce the overpotential simultaneously. The slopes of AOR onset potential and hydrogen adsorption/desorption potential of Pt/C as a function of p

Effects of p-substituents on electrochemical CO oxidation by Rh porphyrin-based catalysts.

Science.gov (United States)

Yamazaki, Shin-ichi; Yamada, Yusuke; Takeda, Sahori; Goto, Midori; Ioroi, Tsutomu; Siroma, Zyun; Yasuda, Kazuaki

2010-08-21

Electrochemical CO oxidation by several carbon-supported rhodium tetraphenylporphyrins with systematically varied meso-substituents was investigated. A quantitative analysis revealed that the p-substituents on the meso-phenyl groups significantly affected CO oxidation activity. The electrocatalytic reaction was characterized in detail based on the spectroscopic and X-ray structural results as well as electrochemical analyses. The difference in the activity among Rh porphyrins is discussed in terms of the properties of p-substituents along with a proposed reaction mechanism. Rhodium tetrakis(4-carboxyphenyl)porphyrin (Rh(TCPP)), which exhibited the highest activity among the porphyrins tested, oxidized CO at a high rate at much lower potentials (means that CO is electrochemically oxidized by this catalyst when a slight overpotential is applied during the operation of a proton exchange membrane fuel cell. This catalyst exhibited little H(2) oxidation activity, in contrast to Pt-based catalysts.

Aerobic oxidation of aldehydes under ambient conditions using supported gold nanoparticle catalysts

DEFF Research Database (Denmark)

Marsden, Charlotte Clare; Taarning, Esben; Hansen, David

2008-01-01

A new, green protocol for producing simple esters by selectively oxidizing an aldehyde dissolved in a primary alcohol has been established, utilising air as the oxidant and supported gold nanoparticles as catalyst. The oxidative esterifications proceed with excellent selectivities at ambient cond...... conditions; the reactions can be performed in an open flask and at room temperature. Benzaldehyde is even oxidised at a reasonable rate below -70 degrees C. Acrolein is oxidised to methyl acrylate in high yield using the same protocol.......A new, green protocol for producing simple esters by selectively oxidizing an aldehyde dissolved in a primary alcohol has been established, utilising air as the oxidant and supported gold nanoparticles as catalyst. The oxidative esterifications proceed with excellent selectivities at ambient...

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

Science.gov (United States)

Herz, Richard K.

1989-01-01

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

Characterization of electro-oxidation catalysts using scanning electrochemical and mass spectral methods

Science.gov (United States)

Jambunathan, Krishnakumar

Low temperature fuel cells have many potential benefits, including high efficiency, high energy density and environmental friendliness. However, logistically appealing fuels for this system, such as reformed hydrocarbons or alcohols, exhibit poor performance because of catalyst poisoning that occurs during oxidation at the anode. This research focuses on the analysis of several model fuels and catalyst materials to understand the impact of catalyst poisoning on reactivity. Two novel experimental tools were developed based upon the local measurement of catalyst performance using scanning, reactivity mapping probes. The Scanning Electrochemical Microscope (SECM) was used to directly measure the rate constant for hydrogen oxidation in the presence and absence of dissolved CO. The Scanning Differential Electrochemical Mass Spectrometer (SDEMS) was exploited to measure the partial and complete oxidation products of methanol and ethanol oxidation. The reactivity of Pt and Pt/Ru catalysts towards the hydrogen oxidation reaction in the absence and presence of adsorbed CO was elucidated using the SECM. Steady state rate constant measurements in the absence of CO showed that the rate of hydrogen oxidation reaction exceeded 1 cms-1 . Steady state rate constant measurements in the presence of CO indicated that the platinum surface is completely inactive due to adsorbed CO. Addition of as little as 6% Ru to the Pt electrode was found to significantly improve the activity of the electrode towards CO removal. SDEMS was used to study the electro-oxidation of methanol on Pt xRuy electrodes at different electrode potentials and temperatures. Screening measurements performed with the SDEMS showed that PtxRu y electrodes containing 6--40% Ru had the highest activity for methanol oxidation. Current efficiencies for CO2 were also calculated under different conditions. SDEMS was also used to study the electro-oxidation of ethanol on Pt xRuy electrodes. The reaction was found to occur

Promotion of Nb2O5 on the wustite-based iron catalyst for ammonia synthesis

International Nuclear Information System (INIS)

Han, Wenfeng; Huang, Shiliang; Cheng, Tianhong; Tang, Haodong; Li, Ying; Liu, Huazhang

2015-01-01

Highlights: • Niobium enhances the reduction of wustite-based ammonia synthesis catalyst significantly. • Nb 2 O 5 inhibits the segregation or formation of solid solutions on the catalyst surface. • Nb 2 O 5 doping enhances the growth rates of [2 1 1] and [2 0 0] planes rather than their amounts. - Abstract: Niobium was selected and investigated as a potential promoter for wustite-based catalyst (WBC) for ammonia synthesis. Experiments on reduction performance, activity test and H 2 -TGA, in situ XRD as well as XPS were carried out to obtain the promotion effect and mechanism involved. Niobium as a promoter was confirmed to enhance the reduction of WBC significantly. This behavior is highly desired for industry in terms of catalyst regeneration and lesser pretreatment time for fabrication regardless the unimproved catalytic performance for Nb 2 O 5 -doped wustite-based catalyst (Nb-WBC). Possible reasons for these phenomena are discussed. It is suggested that Nb 2 O 5 is not favorable for the segregation or formation of solid solutions on the catalyst surface, which are difficult to be reduced. However, it seems that niobium does not promote the growth of [2 1 1] plane, which is active for ammonia synthesis.

Development and Comparison of the Substrate Scope of Pd-Catalysts for the Aerobic Oxidation of Alcohols

Science.gov (United States)

Schultz, Mitchell J.; Hamilton, Steven S.; Jensen, David R.; Sigman, Matthew S.

2009-01-01

Three catalysts for aerobic oxidation of alcohols are discussed and the effectiveness of each is evaluated for allylic, benzylic, aliphatic, and functionalized alcohols. Additionally, chiral nonracemic substrates as well as chemoselective and diastereoselective oxidations are investigated. In this study, the most convenient system for the Pd-catalyzed aerobic oxidation of alcohols is Pd(OAc)2 in combination with triethylamine. This system functions effectively for the majority of alcohols tested and uses mild conditions (3 to 5 mol % of catalyst, room temperature). Pd(IiPr)(OAc)2(H2O) (1) also successfully oxidizes the majority of alcohols evaluated. This system has the advantage of significantly lowering catalyst loadings but requires higher temperatures (0.1 to 1 mol % of catalyst, 60 °C). A new catalyst is also disclosed, Pd(IiPr)(OPiv)2 (2). This catalyst operates under very mild conditions (1 mol %, room temperature, and air as the O2 source) but with a more limited substrate scope. PMID:15844968

The effect of promoters on the electronic structure of ruthenium catalysts supported on carbon

International Nuclear Information System (INIS)

Guraya, Monica; Sprenger, Susanne; Rarog-Pilecka, Wioletta; Szmigiel, Dariusz; Kowalczyk, Zbigniew; Muhler, Martin

2004-01-01

Alkali- and earth-alkali-promoted ruthenium catalysts supported on graphitized carbon were investigated by means of X-ray and ultraviolet photoelectron spectroscopy (XPS and UPS) in order to study the effect of promoters on the electronic structure of this metal-support system. Samples were measured as prepared and after thorough reduction in hydrogen. The C 1s spectra of reduced alkali-promoted catalysts showed a shift towards higher binding energies and an asymmetric broadening. Neither non-promoted nor Ba-promoted Ru/C samples exhibited such a behaviour after similar treatments. The most important feature in the UP spectra of the reduced alkali-promoted catalysts was the appearance of a well defined Fermi edge absent in the semimetal-like electronic structure of graphite. No significant effects appeared in the case of non-promoted or Ba-promoted catalysts. The increase in the density of occupied states at the Fermi energy indicates a shift of this level into the conduction band, due to a charge transfer from the promoter to the support. This interpretation also provides an explanation for the observed higher C 1s binding energy and asymmetric broadening, due to the off-set introduced in the binding energy scale and the increasing probability of inelastic excitations near the Fermi level. In addition to photoelectron spectroscopy, low energy ion scattering (ISS) was used to obtain information about the localisation of the promoters. Based on the mild sputtering effect during prolonged series of spectra, it was possible to conclude that potassium covers both the carbon support and the Ru metal particles

Hysteresis Phenomena in Sulfur Dioxide Oxidation over Supported Vanadium Catalysts

DEFF Research Database (Denmark)

Masters, Stephen G.; Eriksen, Kim Michael; Fehrmann, Rasmus

1997-01-01

Catalyst deactivation and hysteresis behavior in industrial SO2-oxidation catalysts have been studied in the temperature region 350-480 C by combined in situ EPR spectroscopy and catalytic activity measurements. The feed gas composition simulated sulfuric acid synthesis gas and wet/dry de......NOx'ed flue gas. The vanadium (IV) compound K4(VO)3(SO4)5 precipitated during all the investigated conditions hence causing catalyst deactivation. Hysteresis behavior of both the catalytic activity and the V(IV) content was observed during reheating....

Synthesis and Evaluation of Nanostructured Gold-Iron Oxide Catalysts for the Oxidative Dehydrogenation of Cyclohexane

Science.gov (United States)

Wu, Peng

Shape-controlled iron oxide and gold-iron oxide catalysts with a cubic inverse spinel structure were studied in this thesis for the oxidative dehydrogenation of cyclohexane. The structure of iron oxide and gold-iron oxide catalysts has no major impact on their oxidative dehydrogenation activity. However, the product selectivity is influenced. Both cyclohexene and benzene are formed on bare iron oxide nanoshapes, while benzene is the only dehydrogenation product in the presence of gold. The selectivity of benzene over CO2 depends strongly on the stability of the iron oxide support and the gold-support interaction. The highest benzene yield has been observed on gold-iron oxide octahedra. {111}-bound nanooctahedra are highly stable in reaction conditions at 300 °C, while {100}-bound nanocubes start to sinter above 250 °C. The highest benzene yield has been observed on gold-iron oxide nanooctahedra, which are likely to have gold atoms, and few-atom gold clusters strongly-bound on their surface. Cationic gold appears to be the active site for benzene formation. An all-organic method to prepare Au-FeOx nano-catalysts is needed due to the inconvenience of the half-organic, half-inorganic synthesis process discussed above. Several methods from the literature to prepare gold-iron oxide nanocomposites completely in organic solvents were reviewed and followed. FeOx Au synthesis procedures in literatures are initially designed for a Au content of over 70%. This approach was tried here to prepare composites with a much lower Au content (2-5 atom. %). Heat treatment is required to bond Au and FeOx NPs in the organic-phase syntheses. Au-FeOx-4 was obtained as a selective catalyst for the ODH of cyclohexane. A Audelta+ peak is observed in the UV-Vis spectrum of sample Au-FeOx-4. This different Au delta+ form may be cationic Au nano-clusters interacting with the FeOx support. It has been demonstrated that cationic gold is responsible for dehydrogenation behavior. Furthermore, the

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

Energy Technology Data Exchange (ETDEWEB)

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

2015-11-02

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

A mechanistic study on the oxidative coupling of methane over lithium doped magnesium oxide catalysts

NARCIS (Netherlands)

Geerts, J.W.M.H.; Kasteren, van J.M.N.; Wiele, van der K.; Imarisio, G.; Frias, M.; Berntgen, J.M.

1988-01-01

To elucidate the importance of various reaction steps in the oxidative convers ion of methane, experiments were carried out with three reaction products: ethane, ethylene and carbon monoxide. These products were studied seperately, in oxidation experiments with and without a catalyst. Moreover , the

Room temperature aerobic oxidation of amines by a nanocrystalline ruthenium oxide pyrochlore nafion composite catalyst.

Science.gov (United States)

Venkatesan, Shanmuganathan; Kumar, Annamalai Senthil; Lee, Jyh-Fu; Chan, Ting-Shan; Zen, Jyh-Myng

2012-05-14

The aerobic oxidation of primary amines to their respective nitriles has been carried out at room temperature using a highly reusable nanocrystalline ruthenium oxide pyrochlore Nafion composite catalyst (see figure). Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Selective Oxidation of Styrene to Benzaldehyde by Co-Ag Codoped ZnO Catalyst and H2O2 as Oxidant

Directory of Open Access Journals (Sweden)

Abderrazak Aberkouks

2018-01-01

Full Text Available Various ratio of Co-Ag supported on ZnO have been evaluated in the selective catalytic oxidation of styrene to benzaldehyde, using H2O2 as an oxidant. The catalysts were prepared by a sol-gel process and were characterized using XRD, FT-IR, TG-DTG, BET, and SEM/EDX. The performance of the prepared catalyst was investigated under different parameters such as solvent, temperature, substrate/oxidant molar ratios, reaction time, and doping percent. The Zn1−x−yAgxCoyO catalysts exhibit a good activity and a high selectivity towards benzaldehyde (95% with the formation of only 5% of acetophenone.

Influence of vanadium oxidation states on the performance of V-Mg-Al mixed-oxide catalysts for the oxidative dehydrogenation of propane

International Nuclear Information System (INIS)

Schacht, L.; Navarrete, J.; Schacht, P.; Ramirez, M. A.

2010-01-01

V-Mg-Al mixed-oxide catalysts for oxidative dehydrogenation of propane were prepared by thermal decomposition of Mg-Al-layered double hydroxides with vanadium interlayer doping. The obtained catalysts were tested for the oxidative dehydrogenation of propane, obtaining good results in catalytic activity (conversion 16.55 % and selectivity 99.97 %) Results indicated that catalytic performance of these materials depends on how vanadium is integrated in the layered structure, which is determined by the Mg/Al ratio. Vanadium interlayer doping modifies the oxidation state of vanadium and consequently catalytic properties. Surface properties were studied by X-ray photoelectron spectroscopic and diffuse reflectance, UV-visible spectroscopy, and temperature programmed reduction. The analyses provided information about the oxidation state, before and after the reaction. From these results, it is suggested that selectivity to propylene and catalytic activity depend mainly of vanadium oxidation state. (Author)

Influence of vanadium oxidation states on the performance of V-Mg-Al mixed-oxide catalysts for the oxidative dehydrogenation of propane

Energy Technology Data Exchange (ETDEWEB)

Schacht, L. [IPN, Escuela Superior de Fisica y Matematicas, Departamento de Ciencia de Materiales, Av. IPN s/n, Edificio 9, Col. Lindavista, 07738 Mexico D. F. (Mexico); Navarrete, J.; Schacht, P.; Ramirez, M. A., E-mail: pschacha@imp.m [Instituto Mexicano del Petroleo, Programa de Ingenieria Molecular, Eje Central Lazaro Cardenas No. 152, 07730 Mexico D. F. (Mexico)

2010-07-01

V-Mg-Al mixed-oxide catalysts for oxidative dehydrogenation of propane were prepared by thermal decomposition of Mg-Al-layered double hydroxides with vanadium interlayer doping. The obtained catalysts were tested for the oxidative dehydrogenation of propane, obtaining good results in catalytic activity (conversion 16.55 % and selectivity 99.97 %) Results indicated that catalytic performance of these materials depends on how vanadium is integrated in the layered structure, which is determined by the Mg/Al ratio. Vanadium interlayer doping modifies the oxidation state of vanadium and consequently catalytic properties. Surface properties were studied by X-ray photoelectron spectroscopic and diffuse reflectance, UV-visible spectroscopy, and temperature programmed reduction. The analyses provided information about the oxidation state, before and after the reaction. From these results, it is suggested that selectivity to propylene and catalytic activity depend mainly of vanadium oxidation state. (Author)

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.

Improved performance of Nb-doped vanadyl pyrophosphate, catalyst for n-butane oxidation to maleic anhydride

Energy Technology Data Exchange (ETDEWEB)

Pavarelli, G.; Caldarelli, A.; Cavani, F. [Bologna Univ. (Italy). Dipt. di Chimica Industriale ' Toso Montanari' ; Cortelli, C.; Luciani, S. [Polynt SpA, Scanzorosciate (Italy)

2013-11-01

We report here about an investigation on the role of Nb{sup 5+} when used as a promoter for vanadyl pyrophosphate, catalyst for the oxidation of n-butane to maleic anhydride. The effect of Nb was very complex, a function of both its amount and the reaction temperature used. The optimal catalytic behavior was shown for very low Nb contents, i.e., for a V/Nb atomic ratio as low as 150. The main role of Nb was that of accelerating the formation of a limited amount of {gamma}-VOPO{sub 4} on the surface of vanadyl pyrophosphate, by accelerating the oxidation of V{sup 4+} into V{sup 5+} under reaction conditions. (orig.)

Study of ternary-component bismuth molybdate catalysts by 18O2 tracer in the oxidation of propylene to acrolein

International Nuclear Information System (INIS)

Ueda, W.; Moro-oka, Y.; Ikawa, T.

1981-01-01

Participation of lattice oxide ions of ternary-component bismuth molybdate catalysts M-Bi-Mo-O (M = Ni, Co, Mg, Mn, Ca, Sr, Ba, and Pb) was investigated using the 18 O 2 tracer in the selective oxidation of propylene to acrolein. The participation of the lattice oxide ions in the oxidation is prominent on every catalyst but the extent of the participation varies significantly depending on the structure of the catalyst. Only lattice oxide ions in the bismuth molybdate phase are incorporated into the oxidized products on the catalysts (M = Ni, Co, Mg, and Mn) where M have smaller ionic radius than Bi 3+ ; catalyst particles are composed of a shell of bismuth molybdates and a core of MMoO 4 . On the other hand, whole oxide ions in the active particles are involved in the oxidation on catalysts having a scheelite-type structure (M = Ca, Sr, Ba, and Pb) where M has a comparable ionic radius to Bi 3+

New Catalysts for Direct Methanol Oxidation Fuel Cells

Energy Technology Data Exchange (ETDEWEB)

Adzic, Radoslav

1998-08-01

A new class of efficient electrocatalytic materials based on platinum - metal oxide systems has been synthetized and characterized by several techniques. Best activity was found with NiWO{sub 4}-, CoWO{sub 4}-, and RuO{sub 2}- sr¡pported platinum catalysts. A very similar activity at room temperature was observed with the electrodes prepared with the catalyst obtained from International Fuel Cells Inc. for the same Pt loading. Surprisingly, the two tungstates per se show a small activity for methanol oxidation without any Pt loading. Synthesis of NiWO{sub 4} and CoWO{sub 4} were carried out by solid-state reactions. FTIR spectroscopy shows that the tungstates contain a certain amount of physically adsorbed water even after heating samples at 200{degrees}C. A direct relationship between the activity for methanol oxidation and the amount of adsorbed water on those oxides has been found. The Ru(0001) single crystal shows a very small activity for CO adsorption and oxidation, in contrast to the behavior of polycrystalline Ru. In situ extended x-ray absorption fine structure spectroscopy (EXAFS) and x-ray absorption near edge spectroscopy (XANES) showed that the OH adsorption on Ru in the Pt-Ru alloy appears to be the limiting step in methanol oxidation. This does not occur for Pt-RuO{SUB 2} electrocatalyst, which explains its advantages over the Pt-Ru alloys. The IFCC electrocatalyst has the properties of the Pt-Ru alloy.

ENVIRONMENTAL TECHNOLOGY VERIFICATION, TEST REPORT OF MOBILE SOURCE EMISSIONS CONTROL DEVICES/CLEAN DIESEL TECHNOLOGIES FUEL BORNE CATALYST WITH CLEANAIR SYSTEM'S DIESEL OXIDATION CATALYST

Science.gov (United States)

The Environmental Technology Verification report discusses the technology and performance of the Fuel-Borne Catalyst with CleanAir System's Diesel Oxidation Catalyst manufactured by Clean Diesel Technologies, Inc. The technology is a fuel-borne catalyst used in ultra low sulfur d...

[Synergetic effects of silicon carbide and molecular sieve loaded catalyst on microwave assisted catalytic oxidation of toluene].

Science.gov (United States)

Wang, Xiao-Hui; Bo, Long-Li; Liu, Hai-Nan; Zhang, Hao; Sun, Jian-Yu; Yang, Li; Cai, Li-Dong

2013-06-01

Molecular sieve loaded catalyst was prepared by impregnation method, microwave-absorbing material silicon carbide and the catalyst were investigated for catalytic oxidation of toluene by microwave irradiation. Research work examined effects of silicon carbide and molecular sieve loading Cu-V catalyst's mixture ratio as well as mixed approach changes on degradation of toluene, and characteristics of catalyst were measured through scanning electron microscope, specific surface area test and X-ray diffraction analysis. The result showed that the fixed bed reactor had advantages of both thermal storage property and low-temperature catalytic oxidation when 20% silicon carbide was filled at the bottom of the reactor, and this could effectively improve the utilization of microwave energy as well as catalytic oxidation efficiency of toluene. Under microwave power of 75 W and 47 W, complete-combustion temperatures of molecular sieve loaded Cu-V catalyst and Cu-V-Ce catalyst to toluene were 325 degrees C and 160 degrees C, respectively. Characteristics of the catalysts showed that mixture of rare-earth element Ce increased the dispersion of active components in the surface of catalyst, micropore structure of catalyst effectively guaranteed high adsorption capacity for toluene, while amorphous phase of Cu and V oxides increased the activity of catalyst greatly.

Catalytic Activity and Deactivation of SO2 Oxidation Catalysts in Simulated Power Plant Flue Gases

DEFF Research Database (Denmark)

Masters, Stephen G.; Chrissanthopoulos, Asthanassios; Eriksen, Kim Michael

1997-01-01

The catalyst deactivation and the simultaneious formation of compounds in commercial SO2 oxidation catalysts have been studied by combined activity measurements and in situ EPR spectroscopy in the temperature range 350-480 C in wet and dry simulated power plant flue gas.......The catalyst deactivation and the simultaneious formation of compounds in commercial SO2 oxidation catalysts have been studied by combined activity measurements and in situ EPR spectroscopy in the temperature range 350-480 C in wet and dry simulated power plant flue gas....

A Highly Practical Copper(I)/TEMPO Catalyst System for Chemoselective Aerobic Oxidation of Primary Alcohols

Science.gov (United States)

Hoover, Jessica M.; Stahl, Shannon S.

2011-01-01

Aerobic oxidation reactions have been the focus of considerable attention, but their use in mainstream organic chemistry has been constrained by limitations in their synthetic scope and by practical factors, such as the use of pure O2 as the oxidant or complex catalyst synthesis. Here, we report a new (bpy)CuI/TEMPO catalyst system that enables efficient and selective aerobic oxidation of a broad range of primary alcohols, including allylic, benzylic and aliphatic derivatives, to the corresponding aldehydes using readily available reagents, at room temperature with ambient air as the oxidant. The catalyst system is compatible with a wide range of functional groups and the high selectivity for 1° alcohols enables selective oxidation of diols that lack protecting groups. PMID:21861488

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

International Nuclear Information System (INIS)

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

2015-01-01

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

Reactivation of a Tin-Oxide-Containing Catalyst

Science.gov (United States)

Hess, Robert; Sidney, Barry; Schryer, David; Miller, Irvin; Miller, George; Upchurch, Bill; Davis, Patricia; Brown, Kenneth

2010-01-01

The electrons in electric-discharge CO2 lasers cause dissociation of some CO2 into O2 and CO, and attach themselves to electronegative molecules such as O2, forming negative O2 ions, as well as larger negative ion clusters by collisions with CO or other molecules. The decrease in CO2 concentration due to dissociation into CO and O2 will reduce the average repetitively pulsed or continuous wave laser power, even if no disruptive negative ion instabilities occur. Accordingly, it is the primary object of this invention to extend the lifetime of a catalyst used to combine the CO and O2 products formed in a laser discharge. A promising low-temperature catalyst for combining CO and O2 is platinum on tin oxide (Pt/SnO2). First, the catalyst is pretreated by a standard procedure. The pretreatment is considered complete when no measurable quantity of CO2 is given off by the catalyst. After this standard pretreatment, the catalyst is ready for its low-temperature use in the sealed, high-energy, pulsed CO2 laser. However, after about 3,000 minutes of operation, the activity of the catalyst begins to slowly diminish. When the catalyst experiences diminished activity during exposure to the circulating gas stream inside or external to the laser, the heated zone surrounding the catalyst is raised to a temperature between 100 and 400 C. A temperature of 225 C was experimentally found to provide an adequate temperature for reactivation. During this period, the catalyst is still exposed to the circulating gas inside or external to the laser. This constant heating and exposing the catalyst to the laser gas mixture is maintained for an hour. After heating and exposing for an appropriate amount of time, the heated zone around the catalyst is allowed to return to the nominal operating temperature of the CO2 laser. This temperature normally resides in the range of 23 to 100 C. Catalyst activity can be measured as the percentage conversion of CO to CO2. In the specific embodiment

Perovskite Catalysts—A Special Issue on Versatile Oxide Catalysts

Directory of Open Access Journals (Sweden)

Yu-Chuan Lin

2014-08-01

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

Reduction and reoxidation of cobalt Fischer-Tropsch catalysts

Energy Technology Data Exchange (ETDEWEB)

Hilmen, Anne-Mette

1996-12-31

The Fischer-Tropsch synthesis involves the hydrogenation of carbon monoxide to produce mainly hydrocarbons, water and carbon dioxide, but also alcohols, aldehydes and acids are formed. The distribution of these products is determined by the choice of catalyst and synthesis conditions. This thesis studies the reduction and reoxidation of 17%Co/Al{sub 2}O{sub 3} and 17%Co-1%Re/Al{sub 2}O{sub 3} by means of several characterization techniques. The effect of small amounts of Re on the reduction properties of Al{sub 2}O{sub 3}-supported Co catalysts has been studied by temperature-programmed reduction (TPR). An intimate mixture of CoAl{sub 2}O{sub 3} and Re/Al{sub 2}O{sub 3} catalysts showed a promoting effect of Re similar to that for co impregnated CoRe/Al{sub 2}O{sub 3}. A loose mixture of Co/Al{sub 2}O{sub 3} + Re/Al{sub 2}O{sub 3} did not show any effect of Re on the reduction of Co. But a promoting effect was observed if the mixture had been pre-treated with Ar saturated with water before the TPR. It is suggested that Re promotes the reduction of Co oxide by hydrogen spillover. It is shown that a high temperature TPK peak at 1200K assigned to Co aluminate is mainly caused by the diffusion of Co ions during the TPR and not during calcination. The Co particle size measured by x-ray diffraction on oxidized catalysts decreased compared to the particle size on the calcined catalysts, while the dispersion measured by volumetric chemisorption decreased somewhat after the oxidation-reduction treatment. The role of water in the deactivation of Co/Al{sub 2}O{sub 3} and CoRe/Al{sub 2}O{sub 3} Fischer-Tropsch catalysts has been extensively studied. There were significant differences in the reducibility of the phases formed for the two catalysts during exposure to H{sub 2}O/He. 113 refs., 76 figs., 18 tabs.

Fundamental Studies of Butane Oxidation over Model-Supported Vanadium Oxide Catalysts: Molecular Structure-Reactivity Relationships

NARCIS (Netherlands)

Wachs, I.E.; Jehng, J.M.; Deo, G.; Weckhuysen, B.M.; Guliants, V.V.; Benziger, J.B.; Sundaresan, S.

1997-01-01

The oxidation of n-butane to maleic anhydride was investigated over a series of model-supported vanadia catalysts where the vanadia phase was present as a two-dimensional metal oxide overlayer on the different oxide supports (TiO2, ZrO2, CeO2, Nb2O5, Al2O3, and SiO2). No correlation was found

Hydrogen purification for fuel cells using gold catalysts promoted with copper; Purificacao de hidrogenio para celulas a combustivel utilizando catalisadores de ouro promovidos com cobre

Energy Technology Data Exchange (ETDEWEB)

Mozer, Thiago Simonato; Passos, Fabio Barboza [Universidade Federal Fluminense (UFF), Niteroi, RJ (Brazil). Dept. de Engenharia Quimica e de Petroleo. Lab. de Reatores, Cinetica e Catalise (RECAT)]. E-mail: mozer@vm.uff.br

2008-07-01

The selective CO oxidation in the presence of H2 was investigated on Au catalysts promoted with different amounts of Cu. Au catalysts were prepared by the deposition-precipitation method and exhibited a satisfactory activity at 50 deg C with adequate selectivity. The addition of Cu to Au/Al{sub 2}O{sub 3} catalysts caused an increase in the selectivity to CO oxidation due to an interaction between Au and Cu on the surface of the catalysts. However, this beneficial effect was limited to an optimal content of Cu. Through the temperature programmed reduction (TPR) and ultraviolet visible diffuse reflectance spectroscopy (UV-vis DRS) techniques, the formation of small bimetallic Au-Cu particles was verified. The best result was obtained with 2.5% Au-0.5% Cu/Al{sub 2}O{sub 3} catalyst, the CO conversion was higher than 95% and the selectivity was around 70% at 50 deg C. The catalysts showed stable catalytic activity during 24 hours time -on-stream. In the presence of H{sub 2}O and CO{sub 2}, a small decrease in the CO conversion was observed in the stability test, probably due to the deactivation caused by the CO{sub 2} presence. (author)

Catalytic oxidation of n-hexane promoted by Ce{sub 1−x}Cu{sub x}O{sub 2} catalysts prepared by one-step polymeric precursor method

Energy Technology Data Exchange (ETDEWEB)

Araújo, Vinícius D., E-mail: dantas@ursa.ifsc.usp.br [Instituto de Física, Universidade de São Paulo – USP, 13560-970 São Carlos, SP (Brazil); Lima, Maurício M. de [Instituto de Ciencia de los Materiales, Universidad de Valencia, E-46071 Valencia (Spain); Fundación General, Universitat de Valencia, Valencia (Spain); Cantarero, Andrés [Instituto de Ciencia de los Materiales, Universidad de Valencia, E-46071 Valencia (Spain); Bernardi, Maria I.B. [Instituto de Física, Universidade de São Paulo – USP, 13560-970 São Carlos, SP (Brazil); Bellido, Jorge D.A. [CAP-Engenharia Química, Universidade Federal de São João Del-Rei – UFSJ, São João Del-Rei, MG (Brazil); Assaf, Elisabete M. [Instituto de Química, Universidade de São Paulo – USP, 13560-970 São Carlos, SP (Brazil); Balzer, Rosana; Probst, Luiz F.D. [Departamento de Química, Universidade Federal de Santa Catarina – UFSC, 88040-900 Florianópolis, SC (Brazil); Fajardo, Humberto V. [Departamento de Química, Universidade Federal de Ouro Preto – UFOP, 35400-000 Ouro Preto, MG (Brazil)

2013-11-01

Ceria-supported copper catalysts (Ce{sub 1−x}Cu{sub x}O{sub 2}, with x (mol) = 0, 0.01, 0.03, 0.05 and 0.10) were prepared in one step through the polymeric precursor method. The textural properties of the catalysts were investigated by X-ray diffraction (XRD), Rietveld refinement, N{sub 2}-physisorption (BET surface area), electron paramagnetic resonance (EPR), UV–visible diffuse reflectance and photoluminescence spectroscopies and temperature-programmed reduction (TPR). In a previous study ceria-supported copper catalysts were found to be efficient in the preferential oxidation of CO. In this study, we extended the catalytic application of Ce{sub 1−x}Cu{sub x}O{sub 2} systems to n-hexane oxidation and it was verified that the catalysts were highly efficient in the proposed reaction. The best performance (up to 95% conversion) was observed for the catalysts with low copper loads (Ce{sub 0.97}Cu{sub 0.03}O{sub 2} and Ce{sub 0.99}Cu{sub 0.01}O{sub 2}, respectively). The physicochemical characterizations revealed that these behaviors could be attributed to the copper species present in the catalysts and the interaction between CuO and CeO{sub 2}, which vary according to the copper content. - Highlights: • Synthesis of CuO/CeO2 catalysts by the one-step polymeric precursor method. • 95% n-hexane conversion on Ce0.97Cu0.03O2 catalyst. • Redox properties play a key role in the catalytic performance.

Toluene decomposition performance and NOx by-product formation during a DBD-catalyst process.

Science.gov (United States)

Guo, Yufang; Liao, Xiaobin; Fu, Mingli; Huang, Haibao; Ye, Daiqi

2015-02-01

Characteristics of toluene decomposition and formation of nitrogen oxide (NOx) by-products were investigated in a dielectric barrier discharge (DBD) reactor with/without catalyst at room temperature and atmospheric pressure. Four kinds of metal oxides, i.e., manganese oxide (MnOx), iron oxide (FeOx), cobalt oxide (CoOx) and copper oxide (CuO), supported on Al2O3/nickel foam, were used as catalysts. It was found that introducing catalysts could improve toluene removal efficiency, promote decomposition of by-product ozone and enhance CO2 selectivity. In addition, NOx was suppressed with the decrease of specific energy density (SED) and the increase of humidity, gas flow rate and toluene concentration, or catalyst introduction. Among the four kinds of catalysts, the CuO catalyst showed the best performance in NOx suppression. The MnOx catalyst exhibited the lowest concentration of O3 and highest CO2 selectivity but the highest concentration of NOx. A possible pathway for NOx production in DBD was discussed. The contributions of oxygen active species and hydroxyl radicals are dominant in NOx suppression. Copyright © 2014. Published by Elsevier B.V.

Heterogeneous Catalysts for VOC Oxidation from Red Mud and Bagasse Ash Carbon

Science.gov (United States)

Pande, Gaurav

A range of VOC oxidation catalysts have been prepared in this study from agricultural and industrial waste as the starting point. The aim is to prepare catalysts with non-noble metal oxides as the active catalytic component (iron in red mud). The same active component was also supported on activated carbon obtained from unburned carbon in bagasse ash. Red mud which is an aluminum industry waste and rich in different phases of iron as oxide and hydroxide is used as the source for the catalytically active species. It is our aim to enhance the catalytic performance of red mud which though high in iron concentration has a low surface area and may not have the properties of an ideal catalyst by itself. In one of the attempts to enhance the catalytic performance, we have tried to leach red mud for which we have explored a range of leaching acids for effecting the leaching most efficiently and then precipitated the iron from the leachate as its hydroxide by precipitating with alkali solution followed by drying and calcination to give high surface area metal oxide material. Extensive surface characterization and VOC oxidation catalytic testing were performed for these solids. In a step to further enhance the catalytic activity towards oxidation, copper was introduced by taking another industrial waste from the copper tubing industry viz. the pickling acid. Copper has a more favourable redox potential making it catalytically more effective than iron. To make the mixed metal oxide, red mud leachate was mixed with the pickling acid in a pre-decided ratio before precipitating with alkali solution followed by drying and calcination as was done with the red mud leachate. The results from these experiments are encouraging. The temperature programmed reduction (TPR) of the solids show that the precipitate of red mud leachates show hydrogen uptake peak at a lower temperature than for just the calcined red mud. This could be due to the greatly enhanced surface area of the prepared

Oxidation of Catechol using Titanium Silicate (TS-1 Catalyst: Modeling and Optimization

Directory of Open Access Journals (Sweden)

Sonali Sengupta

2013-12-01

Full Text Available The oxidation of catechol was studied in an eco-friendly process with commercial titanium silicate-1 (TS-1 catalyst and hydrogen peroxide as oxidant in absence of all mass transfer effects. The process was opti-mized by Box-Behnken design in terms of three independent process variables such as reaction tempera-ture, moles of hydrogen peroxide per mole of catechol and catalyst amount whose optimum values of the process variables were found to be 60 °C, 13.2 and 1.24 g respectively for maximum conversion of 75.8 %. The effects of different process parameters such as mole ratio of hydrogen peroxide to catechol, catalyst par-ticle size, catalyst amount, temperature and reaction time were studied. A pseudo first order kinetic model was fitted with the experimental rate data. The apparent activation energy for the reaction was found to be 11.37 kJ/mole.  © 2013 BCREC UNDIP. All rights reservedReceived: 22nd April 2013; Revised: 25th October 2013; Accepted: 1st November 2013[How to Cite: Sengupta, S., Ghosal, D., Basu, J.K. (2013. Oxidation of Catechol using Titanium Silicate (TS-1 Catalyst: Modeling and Optimization. Bulletin of Chemical Reaction Engineering & Catalysis, 8 (2: 167-177. (doi:10.9767/bcrec.8.2.4759.167-177][Permalink/DOI: http://dx.doi.org/10.9767/bcrec.8.2.4759.167-177

Polyethers for biomedical applications. Polymerization of propylene oxide by organozinc/organotin catalysts

NARCIS (Netherlands)

Bots, Jan Gert; van der Does, L.; Bantjes, Adriaan; Broersma, Jaap

1987-01-01

The polymerization of propylene oxide to obtain a high-molecular-weight polymer with an atactic structure required for the application as artificial blood vessels was investigated using combinations of organozinc and organotin compounds as catalyst. The composition of the most active catalyst,

Simple Copper Catalysts for the Aerobic Oxidation of Amines: Selectivity Control by the Counterion.

Science.gov (United States)

Xu, Boran; Hartigan, Elizabeth M; Feula, Giancarlo; Huang, Zheng; Lumb, Jean-Philip; Arndtsen, Bruce A

2016-12-19

We describe the use of simple copper-salt catalysts in the selective aerobic oxidation of amines to nitriles or imines. These catalysts are marked by their exceptional efficiency, operate at ambient temperature and pressure, and allow the oxidation of amines without expensive ligands or additives. This study highlights the significant role counterions can play in controlling selectivity in catalytic aerobic oxidations. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Heterogeneous catalysis in the liquid-phase oxidation of olefins--3. The activity of supported vanadium-chromium binary oxide catalyst for the oxidation of cyclohexene

Energy Technology Data Exchange (ETDEWEB)

Takehira, K; Hayakawa, T; Ishikawa, T

1979-03-01

The activity of supported vanadium-chromium binary oxide catalyst for the oxidation of cyclohexene to 1-cyclohexenyl hydroperoxide, 2-cyclohexene-1-one, 2-cyclohexene-1-ol, and cyclohexene oxide was due to the interaction between the metal oxides and the carriers. The oxidation reaction was carried out in benzene at 60/sup 0/C for four hours with the binary oxide supported on (GAMMA)-alumina or silica; three series of catalysts were prepared by combining the vanadium and chromium oxide components with alumina hydrate or silica sol by a kneading method. The silica-supported catalysts had the greatest activity, the highest being the V/sub 2/O/sub 5//SiO/sub 2/ system, which lost its activity quickly during the reaction. This was followed in activity by the Cr/sub 2/O/sub 3//SiO/sub 2/ system, containing the chromium(V) species. The Cr/sub 2/O/sub 3//Al/sub 2/O/sub 3/ system also had high activity and the chromium(V) species. The vanadium and chromium metal ions are probably coordinated tetrahedrally on the support, and these complexes catalyze cyclohexene autoxidation by decomposing 1-cyclohexenyl hydroperoxide.

NO oxidation on Zeolite Supported Cu Catalysts: Formation and Reactivity of Surface Nitrates

Energy Technology Data Exchange (ETDEWEB)

Chen, Hai-Ying; Wei, Zhehao; Kollar, Marton; Gao, Feng; Wang, Yilin; Szanyi, Janos; Peden, Charles HF

2016-04-18

The comparative activities of a small-pore Cu-CHA and a large-pore Cu-BEA catalyst for the selective catalytic reduction (SCR) of NOx with NH3, and for the oxidation of NO to NO2 and the subsequent formation of surface nitrates were investigated. Although both catalysts are highly active in SCR reactions, they exhibit very low NO oxidation activity. Furthermore, Cu-CHA is even less active than Cu-BEA in catalyzing NO oxidation but is clearly more active for SCR reactions. Temperature-programed desorption (TPD) experiments following the adsorption of (NO2 + NO + O2) with different NO2:NO ratios reveal that the poor NO oxidation activity of the two catalysts is not due to the formation of stable surface nitrates. On the contrary, NO is found to reduce and decompose the surface nitrates on both catalysts. To monitor the reaction pathways, isotope exchange experiments were conducted by using 15NO to react with 14N-nitrate covered catalyst surfaces. The evolution of FTIR spectra during the isotope exchange process demonstrates that 14N-nitrates are simply displaced with no formation of 15N-nitrates on the Cu-CHA sample, which is clearly different from that observed on the Cu-BEA sample where formation of 15N-nitrates is apparent. The results suggest that the formal oxidation state of N during the NO oxidation on Cu-CHA mainly proceeds from its original +2 to a +3 oxidation state, whereas reaching a higher oxidation state for N, such as +4 or +5, is possible on Cu-BEA. The authors at PNNL gratefully acknowledge the US Department of Energy (DOE), Energy Efficiency and Renewable Energy, Vehicle Technologies Office for the support of this work. The research described in this paper was performed at the Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by the DOE’s Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory (PNNL). PNNL is operated for the US DOE by Battelle.

Hydroformylation of 1-Hexene over Rh/Nano-Oxide Catalysts

Directory of Open Access Journals (Sweden)

Sari Suvanto

2013-03-01

Full Text Available The effect of nanostructured supports on the activity of Rh catalysts was studied by comparing the catalytic performance of nano- and bulk-oxide supported Rh/ZnO, Rh/SiO2 and Rh/TiO2 systems in 1-hexene hydroformylation. The highest activity with 100% total conversion and 96% yield of aldehydes was obtained with the Rh/nano-ZnO catalyst. The Rh/nano-ZnO catalyst was found to be more stable and active than the corresponding rhodium catalyst supported on bulk ZnO. The favorable morphology of Rh/nano-ZnO particles led to an increased metal content and an increased number of weak acid sites compared to the bulk ZnO supported catalysts. Both these factors favored the improved catalytic performance. Improvements of catalytic properties were obtained also with the nano-SiO2 and nano-TiO2 supports in comparison with the bulk supports. All of the catalysts were characterized by scanning electron microscope (SEM, inductively coupled plasma mass spectrometry (ICP-MS, BET, powder X-ray diffraction (PXRD and NH3- temperature-programmed desorption (TPD.

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.

Kinetics of the reduction of uranium oxide catalysts

International Nuclear Information System (INIS)

Heynen, H.W.G.; Camp-van Berkel, M.M.; Bann, H.S. van der

1977-01-01

The reduction of uranium oxide and uranium oxide on alumina catalysts by ethylbenzene and by hydrogen has been studied in a thermobalance. Ethylbenzene mole fractions between 0.0026 and 0.052 and hydrogen mole fractions between 0.1 and 0.6 were applied at temperatures of 425--530 0 C. During the reduction the uranium oxides are converted into UO 2 . The rate of reduction of pure uranium oxide appears to be constant in the composition region UO/sub 2.6/-UO/sub 2.25/. The extent of this region is independent of the concentration of the reducing agents and of the reaction temperature. The constant rate is explained in terms of a constant oxygen pressure which is in equilibrium with the two solid phases, U 3 O/sub 8-x/ and U 4 O 9 . The reduction rate is first order in hydrogen and zero order in ethylbenzene with activation energies of 120 and 190 kJ mol -1 , respectively. Oxygen diffusion through the lattice is probably not rate limiting. The reduction behavior of uranium oxide on alumina is different from that of pure uranium oxide; the rate of reduction continuously decreases with increasing degree of reduction. An explanation for this behavior has been given by visualizing this catalyst as a set of isolated uranium oxide crystallites with a relative wide variation of diameters, in an alumina matrix. At the beginning of the reduction, carbon dioxide and water are the only reaction products. Thereafter, benzene is found as well and, finally, at U/O ratios below 2.25, styrene also appears in the reactor outlet

Preparation and Characterization of Promoted Fe-V/SiO2 Nanocatalysts for Oxidation of Alcohols

Directory of Open Access Journals (Sweden)

Hamid Reza Rafiee

2013-01-01

Full Text Available A series of SiO2 supported iron-vanadium catalysts were prepared using sol-gel and wetness impregnation methods. This research investigates the effects of V and Cu on the structure and morphology of Fe/SiO2 catalysts. The SiO2 supported catalyst with the highest specific surface area and pore volume was obtained when it is containing 40 wt.% Fe, 15 wt.% V, and 2 wt.% Cu. Characterization of prepared catalysts was carried out by powder X-ray diffraction (XRD, scanning electron microcopy (SEM, vibrating sample magnetometry (VSM, Fourier transform infrared (FT-IR spectrometry, temperature program reduction (TPR, N2 physisorption, and thermal analysis methods such as thermal gravimetric analysis (TGA and differential scanning calorimetry (DSC. The Fe-V/SiO2 catalyst promoted with 2 wt.% of Cu exhibited typical ferromagnetic behavior at room temperature with a saturation magnetization value of 11.44 emu/g. This character of catalyst indicated great potential for application in magnetic separation technologies. The prepared catalyst was found to act as an efficient recoverable nanocatalyst for oxidation reaction of alcohols to aldehydes and ketones in aqueous media under mild condition. Moreover, the catalyst was reused five times without significant degradation in catalytic activity and performance.

V{sub 2}O{sub 5}-ZrO{sub 2} catalysts for the oxidative dehydrogenation of propane - influence of the niobium oxide doping

Energy Technology Data Exchange (ETDEWEB)

Albrecht, S.; Hallmeier, K.H.; Wendt, G. [Leipzig Univ. (Germany). Fakultaet fuer Chemie und Mineralogie; Lippold, G. [Leipzig Univ. (Germany). Fakultaet fuer Physik und Geowissenschaften

1998-12-31

The oxidative dehydrogenation (ODH) of light alkanes is an alternative way for the production of olefins. A wide variety of catalytic systems has been investigated. Vanadium oxide based catalysts were described in the literature as effective catalysts for the ODH of propane. The catalytic activity and selectivity depend on the kind of support material, the kind of dopants and the formation of complex metal oxide phases. In recent papers it was claimed that both orthovanadate and/or pyrovanadate species are selective for the ODH of propane. Niobia based materials were investigated as catalysts for acidic and selective oxidation type reactions. In the ODH of propane niobia exhibited a high selectivity to propene but the conversion of propane was low. V{sub 2}O{sub 5}-Nb{sub 2}O{sub 5} catalysts proved to be catalytically active and selective and showed no formation of oxygenates. In the present study the influence of the niobia dopant of the catalytic properties of V{sub 2}O{sub 5}-ZrO{sub 2} catalysts in the ODH of propane was examined. The structural and textural properties of the catalysts were investigated using several methods. (orig.)

Catalytic wet air oxidation of 2-chlorophenol over sewage sludge-derived carbon-based catalysts

Energy Technology Data Exchange (ETDEWEB)

Tu, Yuting [Institut de recherches sur la catalyse et l’environnement de Lyon (IRCELYON), CNRS – Université Claude Bernard Lyon 1, 2 Avenue Albert Einstein, 69626 Villeurbanne Cedex (France); School of Environmental Science and Engineering, Sun Yat-Sen University, Guangzhou 510275 (China); Xiong, Ya; Tian, Shuanghong [School of Environmental Science and Engineering, Sun Yat-Sen University, Guangzhou 510275 (China); Guangdong Provincial Key Laboratory of Environmental Pollution Control and Remediation Technology, Guangzhou 510275 (China); Kong, Lingjun [School of Environmental Science and Engineering, Sun Yat-Sen University, Guangzhou 510275 (China); Descorme, Claude, E-mail: claude.descorme@ircelyon.univ-lyon1.fr [Institut de recherches sur la catalyse et l’environnement de Lyon (IRCELYON), CNRS – Université Claude Bernard Lyon 1, 2 Avenue Albert Einstein, 69626 Villeurbanne Cedex (France)

2014-07-15

Highlights: • A sewage sludge derived carbon-supported iron oxide catalyst (FeSC) was prepared. • FeSC exhibited high catalytic activity in the wet air oxidation of 2-chlorophenol. • A strong correlation was observed between the 2-CP conversion, the iron leaching and the pH. • Using an acetate buffer, the iron leaching was suppressed while keeping some catalytic activity. • A simplified reaction pathway was proposed for the CWAO of 2-CP over the FeSC catalyst. - Abstract: A sewage sludge derived carbon-supported iron oxide catalyst (FeSC) was prepared and used in the Catalytic Wet Air Oxidation (CWAO) of 2-chlorophenol (2-CP). The catalysts were characterized in terms of elemental composition, surface area, pH{sub PZC}, XRD and SEM. The performances of the FeSC catalyst in the CWAO of 2-CP was assessed in a batch reactor operated at 120 °C under 0.9 MPa oxygen partial pressure. Complete decomposition of 2-CP was achieved within 5 h and 90% Total Organic Carbon (TOC) was removed after 24 h of reaction. Quite a straight correlation was observed between the 2-CP conversion, the amount of iron leached in solution and the pH of the reaction mixture at a given reaction time, indicating a strong predominance of the homogeneous catalysis contribution. The iron leaching could be efficiently prevented when the pH of the solution was maintained at values higher than 4.5, while the catalytic activity was only slightly reduced. Upon four successive batch CWAO experiments, using the same FeSC catalyst recovered by filtration after pH adjustment, only a very minor catalyst deactivation was observed. Finally, based on all the identified intermediates, a simplified reaction pathway was proposed for the CWAO of 2-CP over the FeSC catalyst.

Role of the acid-base properties of gallium-antimony oxide catalyst in oxidative ammonolysis of propane to acrylonitrile (AN)

Energy Technology Data Exchange (ETDEWEB)

Osipova, Z.G.; Sokolovskii, V.D.

1979-07-01

The role of the acid-base properties of gallium-antimony oxide catalyst in oxidative ammonolysis of propane to acrylonitrile (AN) was studied in a differential flow reactor at 550/sup 0/C, with the reaction mixture containing 5 3< by vol propane, 6 3< ammonia, and 18.6Vertical Bar3< oxygen diluted in helium, over ebulliated beds of a 5Vertical Bar3< Ga/Sb or a 1:3:1.5:1 Ga/Sb/Ni/P catalysts, the basicity of which was varied by adding 5 mole Vertical Bar3< of an alkaline earth metal (added as the nitrate and calcined). Both the rate of propane conversion and that of AN formation increased with increasing concentration of the basic sites (determined by back titration with benzoic acid) on both types of the catalysts and linearly correlated with the amount of nitrous oxide desorbed from the catalysts after the reaction. The presence of ammonia in the reaction mixture increased the activity and selectivity of the catalysts and the concentration of the active basic sites. Apparently, the reaction rate is limited by proton abstraction from a propane molecule with the formation of a carbanion stabilized on alkaline-earth metal cations. The rate-determining proton abstraction occurs on nucleophile basic sites, formed by dissociative adsorption of ammonia to form species such as NH, NH/sub 2/, and HNO, which are then oxidized to N/sub 2/ and N/sub 2/O.

Nanocarbons as catalyst for selective oxidation of acrolein to acrylic acid

Energy Technology Data Exchange (ETDEWEB)

Frank, B.; Blume, R.; Rinaldi, A.; Trunschke, A.; Schloegl, R. [Fritz Haber Institute of the Max Planck Society, Berlin (Germany). Dept. of Inorganic Chemistry

2011-07-01

Selective oxidations are key steps of industrial oil and gas processing for the synthesis of high-value chemicals. Mixed metal oxides based on redox active V or Mo are frequently used for oxidative C-H bond activation. However, multiple processes require precious metals or suffer from low product selectivity demanding an ongoing search for cost-effective alternatives. Recently, the nanostructured carbon was reported to catalyze the metal-free selective alkane activation by oxidative dehydrogenation (ODH). Electron-rich surface carbonyls coordinate this reaction and mimic the active oxygen species in metal oxide catalysts. Here we show that the graphitic carbon, beyond ODH, has the potential to selectively mediate the insertion of an oxygen atom into an organic molecule, i.e., acrolein. Multi-step atom rearrangements considerably exceed the mechanistic complexity of hydrogen abstraction and were so far believed to be the exclusive domain of metal (oxide) catalysis. In the carbon catalyzed process, the nucleophilic oxygen atoms terminating the graphite (0001) surface abstract the formyl hydrogen and the activated aldehyde gets oxidized by epoxide-type mobile oxygen, thus the sp{sup 2} carbon acts as a bifunctional catalyst. Substantial similarities between the metal oxide- and carbon-catalyzed reactions could be identified. Our results shed light on a rarely known facet of applications of nanostructured carbon materials being decorated with diverse oxygen functionalities to coordinate complex catalytic processes. We could successfully transfer the results obtained from the graphite model to carbon nanotubes (CNTs) providing a higher surface area, defect density, and intrinsic activity, to substantially increase the reactivity per catalyst volume. Indeed, low dimensional nanostructured carbon is a highly flexible and robust material which can be modified in a multiple manner to optimize its properties with respect to the intended application. The exploration of

High activity PtRu/C catalysts synthesized by a modified impregnation method for methanol electro-oxidation

International Nuclear Information System (INIS)

Ma Liang; Liu Changpeng; Liao Jianhui; Lu Tianhong; Xing Wei; Zhang Jiujun

2009-01-01

A modified impregnation method was used to prepare highly dispersive carbon-supported PtRu catalyst (PtRu/C). Two modifications to the conventional impregnation method were performed: one was to precipitate the precursors ((NH 4 ) 2 PtCl 6 and Ru(OH) 3 ) on the carbon support before metal reduction; the other was to add a buffer into the synthetic solution to stabilize the pH. The prepared catalyst showed a much higher activity for methanol electro-oxidation than a catalyst prepared by the conventional impregnation method, even higher than that of current commercially available, state-of-the-art catalysts. The morphology of the prepared catalyst was characterized using TEM and XRD measurements to determine particle sizes, alloying degree, and lattice parameters. Electrochemical methods were also used to ascertain the electrochemical active surface area and the specific activity of the catalyst. Based on XPS measurements, the high activity of this catalyst was found to originate from both metallic Ru (Ru 0 ) and hydrous ruthenium oxides (RuO x H y ) species on the catalyst surface. However, RuO x H y was found to be more active than metallic Ru. In addition, the anhydrous ruthenium oxide (RuO 2 ) species on the catalyst surface was found to be less active.

Second-Order Biomimicry: In Situ Oxidative Self-Processing Converts Copper(I)/Diamine Precursor into a Highly Active Aerobic Oxidation Catalyst.

Science.gov (United States)

McCann, Scott D; Lumb, Jean-Philip; Arndtsen, Bruce A; Stahl, Shannon S

2017-04-26

A homogeneous Cu-based catalyst system consisting of [Cu(MeCN) 4 ]PF 6 , N , N '-di- tert -butylethylenediamine (DBED), and p -( N , N -dimethylamino)pyridine (DMAP) mediates efficient aerobic oxidation of alcohols. Mechanistic study of this reaction shows that the catalyst undergoes an in situ oxidative self-processing step, resulting in conversion of DBED into a nitroxyl that serves as an efficient cocatalyst for aerobic alcohol oxidation. Insights into this behavior are gained from kinetic studies, which reveal an induction period at the beginning of the reaction that correlates with the oxidative self-processing step, EPR spectroscopic analysis of the catalytic reaction mixture, which shows the buildup of the organic nitroxyl species during steady state turnover, and independent synthesis of oxygenated DBED derivatives, which are shown to serve as effective cocatalysts and eliminate the induction period in the reaction. The overall mechanism bears considerable resemblance to enzymatic reactivity. Most notable is the "oxygenase"-type self-processing step that mirrors generation of catalytic cofactors in enzymes via post-translational modification of amino acid side chains. This higher-order function within a synthetic catalyst system presents new opportunities for the discovery and development of biomimetic catalysts.

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

Energy Technology Data Exchange (ETDEWEB)

Laate, Leiv

2002-07-01

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

Influence of Catalyst Acid/Base Properties in Acrolein Production by Oxidative Coupling of Ethanol and Methanol.

Science.gov (United States)

Lilić, Aleksandra; Bennici, Simona; Devaux, Jean-François; Dubois, Jean-Luc; Auroux, Aline

2017-05-09

Oxidative coupling of methanol and ethanol represents a new route to produce acrolein. In this work, the overall reaction was decoupled in two steps, the oxidation and the aldolization, by using two consecutive reactors to investigate the role of the acid/base properties of silica-supported oxide catalysts. The oxidation of a mixture of methanol and ethanol to formaldehyde and acetaldehyde was performed over a FeMoO x catalyst, and then the product mixture was transferred without intermediate separation to a second reactor, in which the aldol condensation and dehydration to acrolein were performed over the supported oxides. The impact of the acid/base properties on the selectivity towards acrolein was investigated under oxidizing conditions for the first time. The acid/base properties of the catalysts were investigated by NH 3 -, SO 2 -, and methanol-adsorption microcalorimetry. A MgO/SiO 2 catalyst was the most active in acrolein production owing to an appropriate ratio of basic to acidic sites. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Supported catalyst systems and method of making biodiesel products using such catalysts

Science.gov (United States)

Kim, Manhoe; Yan, Shuli; Salley, Steven O.; Ng, K. Y. Simon

2015-10-20

A heterogeneous catalyst system, a method of preparing the catalyst system and a method of forming a biodiesel product via transesterification reactions using the catalyst system is disclosed. The catalyst system according to one aspect of the present disclosure represents a class of supported mixed metal oxides that include at least calcium oxide and another metal oxide deposited on a lanthanum oxide or cerium oxide support. Preferably, the catalysts include CaO--CeO.sub.2ZLa.sub.2O.sub.3 or CaO--La.sub.2O.sub.3/CeO.sub.2. Optionally, the catalyst may further include additional metal oxides, such as CaO--La.sub.2O.sub.3--GdOxZLa.sub.2O.sub.3.

Selective oxidation of methane to ethane and ethylene over various oxide catalysts

NARCIS (Netherlands)

Roos, J.A.; Bakker, A.G.; Bosch, H.; van Ommen, J.G.; Ross, J.R.H.

1987-01-01

Preliminary results are reported for the oxidative coupling of methane to give ethane/ethylene mixtures over a series of different catalyst formulations; the temperature range studied is 650–850°C. A comparison is made of the behaviour of lead/alumina and lithium/magnesia materials. It is found that

β-cyclodextrin functionalized on glass micro-particles: A green catalyst for selective oxidation of toluene to benzaldehyde

Energy Technology Data Exchange (ETDEWEB)

Tahir, M. Nazir, E-mail: tahir.muhammad_nazir@courrier.uqam.ca [Department of Chemistry and Bioscience, Aalborg University, Frederik Bajers Vej 7H, DK-9220, Aalborg East (Denmark); Department of Chemistry, University of Quebec at Montreal, QC, H3C 3P8 (Canada); Nielsen, Thorbjørn T.; Larsen, Kim L. [Department of Chemistry and Bioscience, Aalborg University, Frederik Bajers Vej 7H, DK-9220, Aalborg East (Denmark)

2016-12-15

Highlights: • Functionalization of βCD onto glass micro-particles (GMP-βCD). • Application of GMP-βCD as a green catalyst for the oxidation of toluene. • 82% yield at room temperature. • Repeated use of the catalyst for several cycles. - Abstract: Oxidation of toluene is considered an important process which often requires high temperatures and specific conditions along with heavy-metals based catalysts. In this study, we have developed a green catalyst by functionalizing beta-cyclodextrin onto glass micro-particle surfaces. All surfaces were characterized by X-ray photoelectron spectroscopy and applied to catalyze the selective oxidation of toluene into benzaldehyde (82% yield) at room temperature. The catalyst was stable and could be used repeatedly for several cycles without losing efficiency.

Role of ultrasonic irradiation on transesterification of palm oil using calcium oxide as a solid base catalyst

International Nuclear Information System (INIS)

Poosumas, Jutipong; Ngaosuwan, Kanokwan; Quitain, Armando T.; Assabumrungrat, Suttichai

2016-01-01

Highlights: • Transesterification of palm oil using a circulated continuous flow ultrasonic reactor. • Heterogeneous system using CaO as catalyst. • Effects of ultrasonic frequency and power, and catalyst reusability were considered. • A single high frequency and high intensity irradiation is favorable for heterogeneous system. - Abstract: Biodiesel production from transesterification of palm oil using a circulated continuous flow ultrasonic reactor was investigated. Transesterification was carried out at 60 °C, 1 atm and a methanol-to-oil molar ratio of 9:1. The highest reaction rate was achieved at the catalyst loading of 2 wt%, and biodiesel yield constantly increased until transesterification equilibrium (about 80%) was reached. A higher ultrasonic frequency (50 kHz) promoted the heterogeneously catalyzed transesterification of refined palm oil, because the three-phase system (packed solid catalyst, methanol and oil) required more spatial distribution by ultrasonic irradiation. Moreover, the highest ultrasonic power also provided highest transesterification rate and biodiesel yield due to cavitation activity enhancement. Reusability of calcium oxide catalysts was also investigated, and results showed that this can be reused to provide high biodiesel yield for at least three operations with slight decrease in the rate of reaction due to counter balance effect of organic compounds deposition on the catalyst surface. The results from this study can be a basis for scaling up of the process to industrial scale.

Enhanced oxidation of naphthalene using plasma activation of TiO2/diatomite catalyst.

Science.gov (United States)

Wu, Zuliang; Zhu, Zhoubin; Hao, Xiaodong; Zhou, Weili; Han, Jingyi; Tang, Xiujuan; Yao, Shuiliang; Zhang, Xuming

2018-04-05

Non-thermal plasma technology has great potential in reducing polycyclic aromatic hydrocarbons (PAHs) emission. But in plasma-alone process, various undesired by-products are produced, which causes secondary pollutions. Here, a dielectric barrier discharge (DBD) reactor has been developed for the oxidation of naphthalene over a TiO 2 /diatomite catalyst at low temperature. In comparison to plasma-alone process, the combination of plasma and TiO 2 /diatomite catalyst significantly enhanced naphthalene conversion (up to 40%) and CO x selectivity (up to 92%), and substantially reduced the formation of aerosol (up to 90%) and secondary volatile organic compounds (up to near 100%). The mechanistic study suggested that the presence of the TiO 2 /diatomite catalyst intensified the electron energy in the DBD. Meantime, the energized electrons generated in the discharge activated TiO 2 , while the presence of ozone enhanced the activity of the TiO 2 /diatomite catalyst. This plasma-catalyst interaction led to the synergetic effect resulting from the combination of plasma and TiO 2 /diatomite catalyst, consequently enhanced the oxidation of naphthalene. Importantly, we have demonstrated the effectiveness of plasma to activate the photocatalyst for the deep oxidation of PAH without external heating, which is potentially valuable in the development of cost-effective gas cleaning process for the removal of PAHs in vehicle applications during cold start conditions. Copyright © 2017 Elsevier B.V. All rights reserved.

Understanding of catalysis on early transition metal oxide-based catalysts through exploration of surface structure and chemistry during catalysis using in-situ approaches

Energy Technology Data Exchange (ETDEWEB)

Tao, Franklin [Univ. of Kansas, Lawrence, KS (United States). Dept. of Chemical and Petroleum Engineering. Dept. of Chemistry

2015-09-14

Two main categories of heterogeneous catalysts are metal and metal oxide which catalyze 80% chemical reactions at solid-gas and solid-liquid interfaces. Metal oxide catalysts are much more complicated than metal catalysts. The reason is that the cations of the metal atoms could exhibit a few different oxidation states on surface of the same catalyst particle such as Co₃O₄ or change of their oxidation states under different reactive environments. For a metal catalyst, there is only one oxidation state typically. In addition, surface of a metal oxide can be terminated with multiple surface functionalities including O atoms with different binding configurations and OH group. For metal, only metal atoms are exposed typically. Obviously, the complication of surface chemistry and structure of a metal oxide makes studies of surface of an oxide catalyst very challenging. Due to the complication of surface of a meal oxide, the electronic and geometric structures of surface of a metal oxide and the exposed species have received enormous attention since oxide catalysts catalyze at least 1/3 chemical reactions in chemical and energy industries. Understanding of catalytic reactions on early transition metal oxide-based catalysts is fundamentally intriguing and of great practical interest in energy- and environment-related catalysis. Exploration of surface chemistry of oxide-based catalysts at molecular level during catalysis has remained challenging though it is critical in deeply understanding catalysis on oxide-based catalysts and developing oxide-based catalysts with high activity and selectivity. Thus, the overall objective of this project is to explore surface chemistry and structure of early transition metal oxide-based catalysts through in-situ characterization of surface of catalysts, measurements of catalytic performances, and then build an intrinsic correlation of surface chemistry and structure with their catalytic performances in a few

Catalytic oxidation of albendazole using molybdenum supported on carbon nanotubes as catalyst

International Nuclear Information System (INIS)

Sun-Kou, Maria del Rosario; Vega Carrasco, Edgar R.; Picasso Escobar, Gino I.

2013-01-01

The catalytic oxidation reaction of the thioether group (-S-) in the structure to the drug albendazole (C 12 H 15 N 3 O 2 S) was studied in order to obtain a pharmacologically active molecule known as albendazole sulfoxide. With this purpose, three heterogeneous catalysts were prepared using molybdenum (Mo) as active phase and carbon nanotubes as a multiple-layer catalyst support. The incorporation of the active phase was performed by wet impregnation, with subsequent calcination for 4 hours at 400 o C. For the catalytic oxidation reaction was employed hydrogen peroxide-urea (H 2 NCONH 2 ·H 2 O 2 ) as oxidizing agent and methanol (CH 3 OH) as reaction medium. The textural and morphology characterization of carbon nanoparticles and catalysts was carried out by adsorption-desorption of N 2 (BET) and scanning electron microscopy (SEM). The identification and quantification of the reaction products were followed by Fourier transform infrared spectroscopy (FTIR) and high performance liquid chromatography (HPLC), respectively. With the yield, selectivity and conversion higher than 90% after 60 minutes of reaction, albendazole sulphoxide was obtained as major product of oxidation reaction. (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

Ir catalysts: Preventing CH3COOH formation in ethanol oxidation

Science.gov (United States)

Miao, Bei; Wu, Zhipeng; Xu, Han; Zhang, Minhua; Chen, Yifei; Wang, Lichang

2017-11-01

Current catalysts used for ethanol oxidation reaction (EOR) cannot effectively prevent CH3COOH formation, and thus become a major hindrance for direct ethanol fuel cell applications. We report an Ir catalyst that shows great promise for a complete EOR based on density functional theory calculations using PBE functional. The reaction barrier on Ir(1 0 0) was found to be 2.10 eV for CH3COOH formation, which is much higher than currently used Pd and Pt, and 0.57 eV for Csbnd C bond cleavage in CHCO species, which are comparable to Pd and Pt. The result suggests future directions for studying optimal complete EOR catalysts.

CO2 methanation on the catalyst of Ni/MCM-41 promoted with CeO2.

Science.gov (United States)

Wang, Xiaoliu; Zhu, Lingjun; Liu, Yincong; Wang, Shurong

2018-06-01

CO 2 as a raw feed combined with renewable hydrogen for the production of useful chemicals and alternative energy products is one of the solutions to environmental and energy problems. In this study, a series of Ni-xCeO 2 /MCM-41 catalysts with a nickel content of 20wt% were prepared through deposition precipitation method for CO 2 methanation. Different characterization methods, including BET, XRD, TEM, SEM, H 2 -TPR and H 2 -TPD were applied to help explore the influence mechanism of CeO 2 on Ni/MCM-41 in CO 2 methanation. It was found that all CeO 2 -promoted catalysts exhibited enhanced catalytic activity when compared to Ni/MCM-41. The catalyst modified with 20wt% CeO 2 showed the best catalytic performance, with CO 2 conversion and CH 4 selectivity of 85.6% and 99.8%, respectively, at the temperature of 380°C under atmospheric pressure. The synergetic effects among Ni 0 active sites, the promoter and the support, including nickel dispersion improvement and increased CO 2 adsorption sites due to the addition of CeO 2 , were considered as important factors for high reactivity of the promoted catalysts. The stability test showed that the promoted catalyst maintained its high reactivity after 30h. Copyright © 2017 Elsevier B.V. All rights reserved.

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

Oxidative desulfurization of diesel fuel using amphiphilic quaternary ammonium phosphomolybdate catalysts

Energy Technology Data Exchange (ETDEWEB)

Qiu, Jianghua; Wang, Guanghui; Zeng, Danlin; Tang, Yan [College of Chemical Engineering and Technology, Wuhan University of Science and Technology, Wuhan 430081 (China); Wang, Meng; Li, Yanjun [College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072 (China)

2009-12-15

Phosphomolybdic acid (HPMo) modified respectively with tetramethyl ammonium chloride (TMAC), dodecyl trimethyl ammonium chloride (DTAC) and hexadecyl trimethyl ammonium chloride (HTAC) as the catalysts were prepared and characterized by FT-IR, XRD and SEM. The catalysts were evaluated for the oxidative desulfurization of benzothiophene (BT), dibenzothiophene (DBT) and straight-run diesel using hydrogen peroxide as an oxidant. Results show that all of the catalysts keep the Keggin structures and are finely dispersed with mixing of quaternary ammonium salts. Hexadecyl chains are more favorable to wrap up DBT to the catalytic center and form stable emulsion system with higher conversion rates of DBT. The shorter dodecyl chains can wrap up BT more suitably and bring smaller steric hindrance, which display higher conversion rates of BT. The oxidative reactions fit apparent first-order kinetics, and the apparent activation energies of DBT are much lower than those of BT. The desulfurization rate of straight-run diesel can be up to 84.4% with the recovery rate of 98.1% catalyzed by [HPMo][HTAC]{sub 2} in 2 h. When increasing the extraction times, the desulfurization rates increase, but the recovery rates of diesel decrease significantly. (author)

Use of Graphite Oxide and Graphene Oxide as Catalysts in the Synthesis of Dipyrromethane and Calix[4]pyrrole

Directory of Open Access Journals (Sweden)

Sweta Mishra

2011-08-01

Full Text Available Graphite oxide and graphene oxides have been used as solid catalysts for the synthesis of 5,5-dialkyldipyrromethanes and calix[4]pyrroles in organic and aqueous solutions at room temperature.

Morphological Effect of Pd Catalyst on Ethanol Electro-Oxidation Reaction

Directory of Open Access Journals (Sweden)

Rosalba Fuentes Ramírez

2012-09-01

Full Text Available In the present study, three different structures with preferentially exposed crystal faces were supported on commercial carbon black by the polyol method (nanoparticles (NP/C, nanobars (NB/C and nanorods (NR/C. The electrocatalysts were characterized by XRD, TEM, TGA and cyclic voltammetry at three different ethanol concentrations. Considerable differences were found in terms of catalytic electroactivity. At all ethanol concentrations, the trend observed for the ethanol oxidation peak potential was preserved as follows: NB/C < NP/C< NR/C < commercial Pd/C. This result indicates that, from a thermodynamics point of view, the NB/C catalyst enclosed by Pd(100 facets presented the highest activity with respect to ethanol electro-oxidation among all of the catalysts studied.

Electrochemical study on the cationic promotion of the catalytic SO2 oxidation in pyrosulfate melts

DEFF Research Database (Denmark)

Petrushina, Irina; Bjerrum, Niels; Cappeln, Frederik Vilhelm

1998-01-01

The electrochemical behavior of the molten V2O5-M2S2O7 (M = K, Cs, or Na) system was studied using a gold working electrode at 440 degrees C in argon and air atmosphere. The aim of the present investigation was to find a possible correlation between the promoting effect of Cs+ and Na+ ions...... on the catalytic oxidation of SO2 in the V2O5-M2S2O7 system and the effect of these alkali cations on the electrochemical behavior of V2O5 in the alkali pyrosulfate melts It has been shown that Na+ ions had a promoting effect on the V(V) reversible arrow V(IV) electrochemical reaction. Sodium ions accelerate both...... in the catalytic SO, oxidation most likely is the oxidation of V(IV) to V(V) and the Na+ and Cs+ promoting effect is based on the acceleration of this stage. It has also been proposed that voltammetric measurements can be used for fast optimization of the composition of the vanadium catalyst (which...

Hydrogen purification for fuel cell by copper promoted gold catalysts; Purificacao de hidrogenio para pilha a combustivel utilizando catalisadores de ouro promovidos com cobre

Energy Technology Data Exchange (ETDEWEB)

Mozer, Thiago S.; Vieira, Carlos T.P.; Passos, Fabio B. [Universidade Federal Fluminense (UFF), Niteroi, RJ (Brazil); Dziuba, Dominika A. [Hochschule Mannheim (Germany)

2008-07-01

Copper promoted gold catalysts were studied for hydrogen purification through selective CO oxidation. The Cu acted as a selectivity promoter favoring the CO conversion and decreasing the H{sub 2} consumption. The deposition-precipitation method, used to prepare the samples generated small and well dispersed gold particles, as the UV-vis DRS spectra did not show the 'plasmon' band, which indicates that the samples are active for SELOX. The activity tests showed high CO conversion, the bimetallic 2,5%Au-0,5%Cu/Al{sub 2}O{sub 3} catalyst showed the best behavior in the tested condition, 95% of CO conversion and 75% of selectivity at 50 deg C. Increasing the O{sub 2} content in the feedstream the CO conversion also increased, although the selectivity decreased. (author)

Cyanide Containing Wastewater Treatment by Ozone Enhanced Catalytic Oxidation over Diatomite Catalysts

Directory of Open Access Journals (Sweden)

Lin Mingguo

2018-01-01

Full Text Available Cyanide containing wastewater that discharged from gold mining process creates environmental problems due to the toxicity of cyanide. As one of the promising advanced oxidation process, catalytic oxidation with ozone is considered to be effective on the purification of cyanide. Diatomite, a natural mineral, was used as catalyst in this study. The effect of O3 dosage, salinity, initial cyanide concentration and initial pH condition were investigated. It was observed that the removal rate of cyanide was much higher in the catalytic oxidation with ozone process than the one in zone alone process. Alkaline condition was especially favorable for cyanide in catalytic oxidation with ozone. The ozone and catalytic oxidation with ozone were simulated by pseudo-first-order kinetics model. The apparent first-order rate constant contribution of the diatomite catalyst was 0.0757 min-1, and the contribution percentage was 65.77%.

Rh promoted La{sub 0.75}Sr{sub 0.25}(Fe{sub 0.8}Co{sub 0.2}){sub 1−x}Ga{sub x}O{sub 3-δ} perovskite catalysts: Characterization and catalytic performance for methane partial oxidation to synthesis gas

Energy Technology Data Exchange (ETDEWEB)

Palcheva, R., E-mail: radost@ic.bas.bg [InGAP Centre for Research-based Innovation, SMN, University of Oslo, PO Box 1033, Blindern, Oslo 0315 Norway (Norway); Olsbye, U.; Palcut, M. [InGAP Centre for Research-based Innovation, SMN, University of Oslo, PO Box 1033, Blindern, Oslo 0315 Norway (Norway); Rauwel, P. [Department of Physics, SMN, University of Oslo, PO Box B 1048 Blindern, Oslo 0316 (Norway); Tyuliev, G.; Velinov, N. [Institute of Catalysis, Bulgarian Academy of Sciences, G. Bonchev Str., Bldg. 11, Sofia 1113 (Bulgaria); Fjellvåg, H.H. [InGAP Centre for Research-based Innovation, SMN, University of Oslo, PO Box 1033, Blindern, Oslo 0315 Norway (Norway)

2015-12-01

Graphical abstract: - Highlights: • Perovskites type-oxide La{sub 0.75}Sr{sub 0.25}(Fe{sub 0.8}Co{sub 0.2}){sub 1−x}Ga{sub x}O{sub 3-δ} (x = 0.1, 0.25, 0.4) prepared by the sol–gel citrate method. • Bulk and surface analysis to determine catalysts composition evolution. • Anaerobic catalytic partial oxidation of methane to syngas at 600 °C in a pulse apparatus over Rh promoted perovskites. • The catalysts showed high stability and selectivity. - Abstract: Synthesis gas production via selective oxidation of methane at 600 °C in a pulse reaction over La{sub 0.75}Sr{sub 0.25}(Fe{sub 0.8}Co{sub 0.2}){sub 1−x}Ga{sub x}O{sub 3-δ} (x = 0.1, 0.25, 0.4) perovskite-supported rhodium catalysts, was investigated. The perovskite oxides were prepared by sol–gel citrate method and characterized by X-ray Diffraction (XRD), Moessbauer Spectroscopy (MS), Temperature Programmed Reduction (TPR-H{sub 2}), X-ray Photoelectron Spectroscopy (XPS) and High Resolution Transmission Electron Microscopy (HRTEM). According to XRD analysis, the synthesized samples were a single perovskite phase. The perovskite structure of Ga substituted samples remained stable after TPR-H{sub 2}, as confirmed by XRD. Data of MS identified Fe{sup 3+} ions in two distinctive coordination environments, and Fe{sup 4+} ions. The Rh{sub 2}O{sub 3} thin overlayer was detected by the HRTEM for the Rh impregnated perovskite oxides. During the interaction of methane with oxidized perovskite-supported Rh (0.5 wt.%) catalysts, besides CO, H{sub 2}, and surface carbon, CO{sub 2} and H{sub 2}O were formed. The Rh perovskite catalyst with x = 0.25 gallium exhibits the highest catalytic activity of 83% at 600 °C. The CO selectivity was affected by the reducibility of La{sub 0.75}Sr{sub 0.25}(Fe{sub 0.8}Co{sub 0.2}){sub 1−x}Ga{sub x}O{sub 3-δ} perovskite materials.

Novel synthesis of manganese and vanadium mixed oxide (V2O5/OMS-2) as an efficient and selective catalyst for the oxidation of alcohols in liquid phase

International Nuclear Information System (INIS)

Mahdavi, Vahid; Soleimani, Shima

2014-01-01

Graphical abstract: Oxidation of various alcohols is studied in the liquid phase over new composite mixed oxide (V 2 O 5 /OMS-2) catalyst using tert-butyl hydroperoxide (TBHP). The activity of V 2 O 5 /OMS-2 samples was considerably increased with respect to OMS-2 catalyst and these samples are found to be suitable for the selective oxidation of alcohols. - Highlights: • V 2 O 5 /K-OMS-2 with different V/Mn molar ratios prepared by the impregnation method. • Oxidation of alcohols was studied in the liquid phase over V 2 O 5 /K-OMS-2 catalyst. • V 2 O 5 /K-OMS-2 catalyst had excellent activity for alcohol oxidation. • Benzyl alcohol oxidation using excess TBHP followed a pseudo-first order kinetic. • The selected catalyst was reused without significant loss of activity. - Abstract: This work reports the synthesis and characterization of mixed oxide vanadium–manganese V 2 O 5 /K-OMS-2 at various V/Mn molar ratios and prepared by the impregnation method. Characterization of these new composite materials was made by elemental analysis, BET, XRD, FT-IR, SEM and TEM techniques. Results of these analyses showed that vanadium impregnated samples contained mixed phases of cryptomelane and crystalline V 2 O 5 species. Oxidation of various alcohols was studied in the liquid phase over the V 2 O 5 /K-OMS-2 catalyst using tert-butyl hydroperoxide (TBHP) and H 2 O 2 as the oxidant. Activity of the V 2 O 5 /K-OMS-2 samples was increased considerably with respect to K-OMS-2 catalyst due to the interaction of manganese oxide and V 2 O 5 . The kinetic of benzyl alcohol oxidation using excess TBHP over V 2 O 5 /K-OMS-2 catalyst was investigated at different temperatures and a pseudo-first order reaction was determined with respect to benzyl alcohol. The effects of reaction time, oxidant/alcohol molar ratio, reaction temperature, solvents, catalyst recycling potential and leaching were investigated

Intrinsic Activity of MnOx-CeO2 Catalysts in Ethanol Oxidation

Directory of Open Access Journals (Sweden)

Dimitrios Delimaris

2017-11-01

Full Text Available MnOx-CeO2 mixed oxides are considered efficient oxidation catalysts superior to the corresponding single oxides. Although these oxides have been the subject of numerous studies, their fundamental performance indicators, such as turnover frequency (TOF or specific activity, are scarcely reported. The purpose of the present work is to investigate the effect of catalyst composition on the concentration of active sites and intrinsic activity in ethanol oxidation by the employment of temperature-programmed desorption and oxidation of isotopically-labelled ethanol, 12CH313CH2OH. The transformation pathways of preadsorbed ethanol in the absence of gaseous oxygen refer to dehydrogenation to acetaldehyde followed by its dissociation combined with oxidation by lattice oxygen. In the presence of gaseous oxygen, lattice oxygen is rapidly restored and the main products are acetaldehyde, CO2, and water. CO2 forms less easily on mixed oxides than on pure MnOx. The TOF of ethanol oxidation has been calculated assuming that the amount of adsorbed ethanol and CO2 produced during temperature-programmed oxidation (TPO is a reliable indicator of the concentration of the active sites.

o-Naphthoquinone-Catalyzed Aerobic Oxidation of Amines to (Ket)imines: A Modular Catalyst Approach.

Science.gov (United States)

Goriya, Yogesh; Kim, Hun Young; Oh, Kyungsoo

2016-10-07

A modular aerobic oxidation of amines to imines has been achieved using an ortho-naphthoquinone (o-NQ) catalyst. The cooperative catalyst system of o-NQ and Cu(OAc) 2 enabled the formation of homocoupled imines from benzylamines, while the presence of TFA helped the formation of cross-coupled imines in excellent yields. The current mild aerobic oxidation protocol could also be applied to the oxidation of secondary amines to imines or ketimines with the help of cocatalyst, Ag 2 CO 3 , with excellent yields.

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.

Physico-Chemical and Structural Properties of DeNOx and SO2 Oxidation Catalysts

DEFF Research Database (Denmark)

Masters, Stephen Grenville; Oehlers, Cord; Nielsen, Kurt

1996-01-01

Commercial catalysts for NOx removal and SO2 oxidation and their model systems have been investigated by spectroscopic, thermal, electrochemical and X-ray methods. Structural information on the vanadium complexes and compounds as well as physico-chemical properties for catalyst model systems have...

Heterogeneous biomimetic catalysis using iron porphyrin for cyclohexane oxidation promoted by chitosan

Energy Technology Data Exchange (ETDEWEB)

Huang, Guan, E-mail: huangg66@126.com; Liu, Yao; Cai, Jing Li; Chen, Xiang Feng; Zhao, Shu Kai; Guo, Yong An; Wei, Su Juan; Li, Xu

2017-04-30

Graphical abstract: A biomimetic catalyst of iron-tetrakis(4-sulfonatophenyl)porphyrin immobilized on powdered chitosan achieves efficient cyclohexane oxidation with high ketone and alcohol yields. - Highlights: • Fe (TPPS)/pd-CTS is an excellent catalyst for cyclohexane oxidation. • Amino ligation alters the electron cloud density around the iron cation. • Amino coordination likely reduces the activation energy of Fe (TPPS). • The catalyst achieved 22.9 mol% yields of cyclohexanone and cyclohexanol. - Abstract: This study investigates how ligands modulate metalloporphyrin activity with the goal of producing a practical biomimetic catalyst for use in the chemical industry. We immobilized iron porphyrinate [iron-tetrakis-(4-sulfonatophenyl)-porphyrin; Fe(III) (TPPS)] on powdered chitosan (pd-CTS) to form an immobilized catalyst Fe(III) (TPPS)/pd-CTS, which was characterized using modern spectroscopic techniques and used for catalytic oxidation of cyclohexane with O{sub 2}. Amino coordination to iron porphyrin in Fe(III) (TPPS)/pd-CTS altered the electron cloud density around the iron cation, probably by reducing the activation energy of Fe(III) (TPPS) and raising the reactivity of the iron ion catalytic center, thereby improving the catalytic efficiency. One milligram of Fe(III) (TPPS) catalyst can be reused three times for the oxidation reaction to yield an average of 22.9 mol% of cyclohexanone and cyclohexanol.

CO oxidation on PtSn nanoparticle catalysts occurs at the interface of Pt and Sn oxide domains formed under reaction conditions

KAUST Repository

Michalak, William D.

2014-04-01

The barrier to CO oxidation on Pt catalysts is the strongly bound adsorbed CO, which inhibits O2 adsorption and hinders CO2 formation. Using reaction studies and in situ X-ray spectroscopy with colloidally prepared, monodisperse ∼2 nm Pt and PtSn nanoparticle catalysts, we show that the addition of Sn to Pt provides distinctly different reaction sites and a more efficient reaction mechanism for CO oxidation compared to pure Pt catalysts. To probe the influence of Sn, we intentionally poisoned the Pt component of the nanoparticle catalysts using a CO-rich atmosphere. With a reaction environment comprised of 100 Torr CO and 40 Torr O2 and a temperature range between 200 and 300 C, Pt and PtSn catalysts exhibited activation barriers for CO2 formation of 133 kJ/mol and 35 kJ/mol, respectively. While pure Sn is readily oxidized and is not active for CO oxidation, the addition of Sn to Pt provides an active site for O2 adsorption that is important when Pt is covered with CO. Sn oxide was identified as the active Sn species under reaction conditions by in situ ambient pressure X-ray photoelectron spectroscopy measurements. While chemical signatures of Pt and Sn indicated intermixed metallic components under reducing conditions, Pt and Sn were found to reversibly separate into isolated domains of Pt and oxidic Sn on the nanoparticle surface under reaction conditions of 100 mTorr CO and 40 mTorr O2 between temperatures of 200-275 C. Under these conditions, PtSn catalysts exhibited apparent reaction orders in O2 for CO 2 production that were 0.5 and lower with increasing partial pressures. These reaction orders contrast the first-order dependence in O 2 known for pure Pt. The differences in activation barriers, non-first-order dependence in O2, and the presence of a partially oxidized Sn indicate that the enhanced activity is due to a reaction mechanism that occurs at a Pt/Sn oxide interface present at the nanoparticle surface. © 2014 Published by Elsevier Inc.

Power generation using spinel manganese-cobalt oxide as a cathode catalyst for microbial fuel cell applications.

Science.gov (United States)

Mahmoud, Mohamed; Gad-Allah, Tarek A; El-Khatib, K M; El-Gohary, Fatma

2011-11-01

This study focused on the use of spinel manganese-cobalt (Mn-Co) oxide, prepared by a solid state reaction, as a cathode catalyst to replace platinum in microbial fuel cells (MFCs) applications. Spinel Mn-Co oxides, with an Mn/Co atomic ratios of 0.5, 1, and 2, were prepared and examined in an air cathode MFCs which was fed with a molasses-laden synthetic wastewater and operated in batch mode. Among the three Mn-Co oxide cathodes and after 300 h of operation, the Mn-Co oxide catalyst with Mn/Co atomic ratio of 2 (MnCo-2) exhibited the highest power generation 113 mW/m2 at cell potential of 279 mV, which were lower than those for the Pt catalyst (148 mW/m2 and 325 mV, respectively). This study indicated that using spinel Mn-Co oxide to replace platinum as a cathodic catalyst enhances power generation, increases contaminant removal, and substantially reduces the cost of MFCs. Copyright © 2011 Elsevier Ltd. All rights reserved.

Removal of toluene by sequential adsorption-plasma oxidation: Mixed support and catalyst deactivation.

Science.gov (United States)

Qin, Caihong; Huang, Xuemin; Zhao, Junjie; Huang, Jiayu; Kang, Zhongli; Dang, Xiaoqing

2017-07-15

A sequential adsorption-plasma oxidation system was used to remove toluene from simulated dry air using γ-Al 2 O 3 , HZSM-5, a mixture of the two materials or their supported Mn-Ag catalyst as adsorbents under atmospheric pressure and room temperature. After 120min of plasma oxidation, γ-Al 2 O 3 had a better carbon balance (∼75%) than HZSM-5, but the CO 2 yield of γ-Al 2 O 3 was only ∼50%; and there was some desorption of toluene when γ-Al 2 O 3 was used. When a mixture of HZSM-5 and γ-Al 2 O 3 with a mass ratio of 1/2 was used, the carbon balance was up to 90% and 82% of this was CO 2 . The adsorption performance and electric discharge characteristics of the mixed supports were tested in order to rationalize this high CO x yield. After seven cycles of sequential adsorption-plasma oxidation, support and Mn-Ag catalyst deactivation occurred. The support and catalyst were characterized before and after deactivation by SEM, a BET method, XRD, XPS and GC-MS in order to probe the mechanism of their deactivation. 97.6% of the deactivated supports and 76% of the deactivated catalysts could be recovered by O 2 temperature-programmed oxidation. Copyright © 2017 Elsevier B.V. All rights reserved.

Change in activity of catalysts for the oxidation of tritium during a fire event

International Nuclear Information System (INIS)

Iwai, Yasunori; Sato, Katsumi; Yamanishi, Toshihiko

2012-01-01

Highlights: ► We experimentally demonstrated the influence of produced gases from burned low-halogen cable on the activity of catalysts for tritium oxidation. ► At 423 K, no considerable decrease in catalytic activity was observed. ► At 293 K, considerable increase in catalytic activity was initially observed due to the effect of produced hydrogen. Then the temporary decrease was observed due mainly to the effect of produced moisture, however the activity was gradually recovered. - Abstract: The catalytic performance should be maintained in any off normal events. Fire accident is the typical off normal event. In the fusion plant, typical combustibles are evaluated to be polymeric low-halogen cables. Produced gases from burned low-halogen cable may affect the activity of catalysts for the oxidation of tritium. We experimentally demonstrated the influence of produced gases from burned low-halogen cable on the activity of catalyst using tritium gas. Our evaluation showed that ethylene, methane and benzene were major produced gases. The activity of catalysts for the oxidation of tritium during a fire event was evaluated using a commercial hydrophilic Pt/Al 2 O 3 catalyst and a commercial hydrophobic Pt-catalyst. The temperature of catalytic reactor was selected to be 423 and 293 K. At 423 K, no considerable decrease in catalytic activity was observed for both catalysts even in the presence of produced gases from burned low-halogen cable. At 293 K, considerable increase in catalytic activity was initially observed for both catalysts due to the effect of produced hydrogen. Then the temporary decrease was observed, however the catalytic activity was gradually recovered to be the original activity. Consequently, the irreversible decrease in activity of the catalysts during a fire event was not observed.

Promotion of catalytic performance by adding W into Pt/ZrO{sub 2} catalyst for selective catalytic oxidation of ammonia

Energy Technology Data Exchange (ETDEWEB)

Sun, Mengmeng [Institute of New Energy and Low-Carbon Technology, Sichuan University, Chengdu 610064, Sichuan (China); Wang, Suning; Li, Yuanshan [College of Chemical Engineering, Sichuan University, Chengdu 610064, Sichuan (China); Xu, Haidi, E-mail: xuhaidi@scu.edu.cn [Institute of New Energy and Low-Carbon Technology, Sichuan University, Chengdu 610064, Sichuan (China); Chen, Yaoqiang, E-mail: nic7501@scu.edu.cn [Institute of New Energy and Low-Carbon Technology, Sichuan University, Chengdu 610064, Sichuan (China); College of Chemical Engineering, Sichuan University, Chengdu 610064, Sichuan (China)

2017-04-30

Highlights: • The tungsten species weaken platinum-oxygen bond strength. • Pt{sup 0} was the active species of ammonia oxidation reaction in the low temperature. • Some PtO species could convert to Pt [111] beside WO{sub 3} species. - Abstract: Pt-WO{sub 3}/ZrO{sub 2} catalyst was prepared by co-impregnation method to improve the ammonia oxidation performance of Pt/ZrO{sub 2}. Differences in textural, structural, surface chemical states, redox properties and acid properties, together with the catalytic performance of Pt/ZrO{sub 2} and Pt-WO{sub 3}/ZrO{sub 2} catalysts were investigated systematically. The results of H{sub 2}-TPR revealed that higher reduction ability was possessed by Pt-WO{sub 3}/ZrO{sub 2} than that of Pt/ZrO{sub 2} due to the influence of tungsten on platinum. The XPS results showed that electron transfer from tungsten to platinum species made higher electron density around platinum. The TEM results revealed that the active lattice plane Pt[111] was obtained by modification of W species. Consequently, Pt-WO{sub 3}/ZrO{sub 2} exhibited obviously better ammonia oxidation performance compared with Pt/ZrO{sub 2}, the light-off temperature of NH{sub 3} shifted from 284 °C to 249 °C, the activation energy decreased from 113.4 kJ mol{sup −1} to 96.2 kJ mol{sup −1}.

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

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...

Effects of manganese oxide and sulphate on the olefin selectivity of iron catalysts in the Fischer Tropsch reaction

NARCIS (Netherlands)

Dijk, van W.L.; Niemantsverdriet, J.W.; Kraan, van der A.M.; van der Baan, Hessel

1982-01-01

Although it has been claimed by various authors that the addition of manganese oxide, MnO, to an iron catalyst gives a marked increase in the olefin selectivity of iron catalysts, we have been unable to confirm these claims in Fischer Tropsch experiments at 513 K for an iron manganese oxide catalyst

Supported chromium-molybdenum and tungsten sulfide catalysts

International Nuclear Information System (INIS)

Chianelli, R.R.; Jacobson, A.J.; Young, A.R.

1988-01-01

This patent describes the process for preparing a supported hydroprocessing catalyst. The process comprising compositing a quantity of a particulate, porous catalyst support material comprising one or more refactory oxides with one or more catalyst precursor salts and heating the composite at elevated temperature of at least about 200/sup 0/C up to about 600/sup 0/, in the presence of a sulfur-bearing compound in an amount whereby sulfur in the form of the sulfur-bearing compound in an amount whereby sulfur in the form of the sulfur bearing compound is present in excess of that contained in the catalyst precursor and under oxygen-free conditions for a time sufficient to form the catalyst. The catalyst precursor salt contains a tetrathiometallate anion of Mo, W or mixture therof and a cation comprising trivalent chromium or a mixture of trivalent chromium with one or more divalent promoter metals selected from the group consisting of Fe, Ni, Co, Mn, Cu and a mixture thereof wherein the trivalent chromium and divalent promoter metals are chelated by at least one neutral, nitrogen-containing polydentate ligand, L

PdRu/C catalysts for ethanol oxidation in anion-exchange membrane direct ethanol fuel cells

Science.gov (United States)

Ma, Liang; He, Hui; Hsu, Andrew; Chen, Rongrong

2013-11-01

Carbon supported PdRu catalysts with various Pd:Ru atomic ratios were synthesized by impregnation method, and characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), electrochemical half-cell tests, and the anion-exchange membrane direct ethanol fuel cell (AEM-DEFC) tests. XRD results suggest that the PdRu metal exists on carbon support in an alloy form. TEM study shows that the bimetallic PdRu/C catalysts have slightly smaller average particle size than the single metal Pd/C catalyst. Lower onset potential and peak potential and much higher steady state current for ethanol oxidation in alkaline media were observed on the bimetallic catalysts (PdxRuy/C) than on the Pd/C, while the activity for ethanol oxidation on the pure Ru/C was not noticeable. By using Pd/C anode catalysts and MnO2 cathode catalysts, AEM-DEFCs free from the expensive Pt catalyst were assembled. The AEM DEFC using the bimetallic Pd3Ru/C anode catalyst showed a peak power density as high as 176 mW cm-2 at 80 °C, about 1.8 times higher than that using the single metal Pd/C catalyst. The role of Ru for enhancing the EOR activity of Pd/C catalysts is discussed.

Supported sub-nanometer Ta oxide clusters as model catalysts for the selective epoxidation of cyclooctene

KAUST Repository

Zwaschka, Gregor; Rondelli, Manuel; Krause, Maximilian; Rö tzer, Marian David; Hedhili, Mohamed N.; Heiz, Ulrich; Basset, Jean-Marie; Schweinberger, Florian; D'Elia, Valerio

2018-01-01

The preparation of organic ligands-free, isolated tantalum oxide atoms (Ta1) and small clusters (Tan>1) on flat silicate supports was accomplished by ultra-high vacuum (UHV) techniques followed by oxidation in air. The resulting surface complexes were thoroughly characterized and tested as supported catalysts for the epoxidation of cycloalkenes. The observed catalytic performance highlights the potential of the applied method for the production of active catalysts and the study of well-defined, ligand-free metal oxide moieties.

Supported sub-nanometer Ta oxide clusters as model catalysts for the selective epoxidation of cyclooctene

KAUST Repository

Zwaschka, Gregor

2018-01-22

The preparation of organic ligands-free, isolated tantalum oxide atoms (Ta1) and small clusters (Tan>1) on flat silicate supports was accomplished by ultra-high vacuum (UHV) techniques followed by oxidation in air. The resulting surface complexes were thoroughly characterized and tested as supported catalysts for the epoxidation of cycloalkenes. The observed catalytic performance highlights the potential of the applied method for the production of active catalysts and the study of well-defined, ligand-free metal oxide moieties.

Iron carbide on titania surface modified with group VA oxides as Fischer-Tropsch catalysts

International Nuclear Information System (INIS)

Wachs, I.E.; Fiato, R.A.; Chersich, C.C.

1986-01-01

A catalyst is described comprising iron carbide supported on a surface modified titania wherein the support comprises an oxide of a metal selected form the group consisting of niobium, vanadium, tantalum or mixture thereof supported on the titania wherein at least a portion of the supported oxide of niobium, vanandium, tantalum or mixture is in a non-crystalline form. The amount of the supported oxide ranges from about 0.5 to 25 weight percent metal oxide on the titania support based on the total support composition and the catalyst contains at least about 2 milligrams of iron, calculated as Fe/sub 2/O/sub 3/, per square meter of support surface

Uniform Pt Nanoparticles Incorporated into Reduced Graphene Oxides with MoO_3 as Advanced Anode Catalysts for Methanol Electro-oxidation

International Nuclear Information System (INIS)

Hao, Yanfei; Wang, Xudan; Zheng, Yuanyuan; Shen, Jianfeng; Yuan, Junhua; Wang, Ai-jun; Niu, Li; Huang, Shengtang

2016-01-01

Highlights: • Pt nanoparticles were uniformly deposited on graphene with MoO_3. Their size can be tuned by controlling MoO_3 loading. These Pt catalysts are high active on methanol oxidation. They also show high tolerance to CO poisoning. - Abstract: Pt nanoparticles (NPs) were uniformly deposited on the reduced graphene oxides (RGOs) by one-pot thermoreduction strategy with assist of MoO_3. MoO_3 can significantly reduce the size of Pt NPs on RGOs. These Pt NPs can be averaged to be 3.0 to 4.1 nm with MoO_3 loading from 27.4 to 8.8%. Without MoO_3, the size of Pt NPs can reach up to 15.2 nm. In addition, MoO_3 in Pt-MoO_3/RGO catalysts conducts a surface-confined reversible electron transfer. And the Pt-MoO_3/RGO catalysts show strong resistance to CO poisoning and high activity towards methanol oxidation reaction (MOR). Among these Pt-based catalysts, Pt-MoO_3/RGO catalysts with 16.5% MoO_3 loading possess a largest MOR current up to 610 mA mg"−"1 Pt with a smallest deteriorate rate of 0.000425 s"−"1 polarizing for 5000 s at 0.65 V. These results demonstrate commercial feasibility for Pt catalysts to reduce significantly the amount of precious metals Pt in parallel to maintain a high MOR activity and CO tolerance.

Crystalline structure and propylene oxidation in complex bismuth-molybdenum oxide catalysts

International Nuclear Information System (INIS)

Manaila, R.; Ionescu, N.I.; Caldararu, M.

1980-01-01

Complex Bi-Mo oxide catalysts supported on amorphous SiO 2 were prepared by coprecipitation and tested in the reaction of selective oxidation of propylene to acrolein. They consist of a mixture of molybdate phases and excess MoO 3 . The Fe 2 (MoO 4 ) 3 phase was found to have a high concentration of lattice defects, induced by a Mo excess. These defects could be related to the catalytic conversion and to the selectivity to total oxidation by varying the calcination temperature. Calcination above 500 0 C induced also the transition of the metastable modification β-NiMoO 4 to the stable form α, accompanied by a loss of conversion. A complex Bi molybdate with scheelitic structure was found to have a high selectivity to acrolein. (author)

Transesterification of Jatropha curcas crude oil to biodiesel on calcium lanthanum mixed oxide catalyst: Effect of stoichiometric composition

International Nuclear Information System (INIS)

Taufiq-Yap, Yun Hin; Teo, Siow Hwa; Rashid, Umer; Islam, Aminul; Hussien, Mohd Zobir; Lee, Keat Teong

2014-01-01

Highlights: • Biodiesel synthesis from Jatropha curcas oil catalyzed by CaO–La 2 O 3 mixed oxide. • Effects of Ca-to-La ratio, catalyst concentration, methanol/oil ratio and reaction temperature were optimized. • Biodiesel yield >85% was achieved at 65 °C temperature. • CaO–La 2 O 3 catalyst can be easy regenerated. - Abstract: Heterogeneous solid mixed oxide (CaO–La 2 O 3 ) catalysts with different molar ratios of calcium to lanthanum (Ca-to-La) were synthesized by co-precipitation method. The synthesized solid CaO–La 2 O 3 mixed metal oxide catalysts were utilized in transesterification of Jatropha curcus oil as feedstock to produce biodiesel. Under the optimized conditions at 65 °C, 4% catalyst dose with 24:1 MeOH to Jatropha oil molar ratio, the transesterification reaction exhibited 86.51% of biodiesel yield. The prepared catalysts were characterized using various techniques such as X-ray diffraction (XRD), nitrogen sorption with Brunauer–Emmer–Teller (BET) method, temperature-programmed desorption of CO 2 (CO 2 -TPD) and scanning electron microscopy (SEM). Influence of Ca-to-La atomic ratio in the mixed metal oxide catalyst, catalyst amount, methanol to oil molar ratio, reaction time, different oils on the fatty acid methyl ester (FAME) yield were appraised. Different catalyst regeneration procedures were also performed to investigate the reusability of the CaO–La 2 O 3 catalyst

W-containing oxide layers obtained on aluminum and titanium by PEO as catalysts in thiophene oxidation

Science.gov (United States)

Rudnev, V. S.; Lukiyanchuk, I. V.; Vasilyeva, M. S.; Morozova, V. P.; Zelikman, V. M.; Tarkhanova, I. G.

2017-11-01

W-containing oxide layers fabricated on titanium and aluminum alloys by Plasma electrolytic oxidation (PEO) have been tested in the reaction of the peroxide oxidation of thiophene. Samples with two types of coatings have been investigated. Coatings I contained tungsten oxide in the matrix and on the surface of amorphous silica-titania or silica-alumina layers, while coatings II comprised crystalline WO3 and/or Al2(WO4)3. Aluminum-supported catalyst containing a smallest amount of transition metals in the form of tungsten oxides and manganese oxides in low oxidation levels showed high activity and stability.

Dehydrogenation of Ethylbenzene with Carbon Dioxide as Soft Oxidant over Supported Vanadium-Antimony Oxide Catalyst

Energy Technology Data Exchange (ETDEWEB)

Hong, Do Young; Vislovskiy, Vladislav P.; Yoo, Jin S.; Chang, Jong San [Korea Research Institute of Chemical Technology, Daejeon (Korea, Republic of); Park, Sang Eon [Inha University, Incheon (Korea, Republic of); Park, Min Seok [Mongolia International University, Ulaanbaatar (Mongolia)

2005-11-15

This work presents that carbon dioxide, which is a main contributor to the global warming effect, could be utilized as a selective oxidant in the oxidative dehydrogenation of ethylbenzene. The dehydrogenation of ethylbenzene over alumina-supported vanadium-antimony oxide catalyst has been studied under different atmospheres such as inert nitrogen, steam, oxygen or carbon dioxide as diluent or oxidant. Among them, the addition of carbon dioxide gave the highest styrene yield (up to 82%) and styrene selectivity (up to 97%) along with stable activity. Carbon dioxide could play a beneficial role of a selective oxidant in the improvement of the catalytic behavior through the oxidative pathway.

Oxidation of methanol to formaldehyde over a series of Fe1-xAlx-V-oxide catalysts

DEFF Research Database (Denmark)

Häggblad, Robert; Wagner, Jakob Birkedal; Hansen, Staffan

2008-01-01

A series of triclinic Fe1−xAlxVO4 phases with 0x1 were prepared and used in the oxidation of methanol to formaldehyde. The activity measurements revealed that both the activity and especially the selectivity to formaldehyde increased with time of operation for at least 16 h, indicating...... restructuring of the catalysts. Characterisation of the catalysts with XRD, XANES, and electron microscopy after use in methanol oxidation showed that the stability of the bulk phases improved when Al was substituted for Fe in the structure. XRD and XANES of the used FeVO4 showed that it partly transformed...... in methanol oxidation revealed no significant change in the metal composition, in good agreement with the corresponding bulk values, except for a lower Fe value. Steady-state activity data showed a modest increase in specific activity with the Al content, whereas the selectivity to formaldehyde was about 90...

Solid source growth of Si oxide nanowires promoted by carbon nanotubes

Energy Technology Data Exchange (ETDEWEB)

Lu, Congxiang [CINTRA CNRS/NTU/THALES, Nanyang Technological University, Singapore 637553 (Singapore); Novitas, Nanoelectronics Centre of Excellence, School of Electrical and Electronic Engineering, Nanyang Technological University, Singapore 639798 (Singapore); Liu, Wen-wen; Wang, Xingli [Novitas, Nanoelectronics Centre of Excellence, School of Electrical and Electronic Engineering, Nanyang Technological University, Singapore 639798 (Singapore); Li, Xiaocheng [Laboratory of clean energy chemistry and materials, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, No. 18 Tianshui Middle Road, Lanzhou 730000 (China); Tan, Chong Wei [CINTRA CNRS/NTU/THALES, Nanyang Technological University, Singapore 637553 (Singapore); Novitas, Nanoelectronics Centre of Excellence, School of Electrical and Electronic Engineering, Nanyang Technological University, Singapore 639798 (Singapore); Tay, Beng Kang, E-mail: ebktay@ntu.edu.sg [CINTRA CNRS/NTU/THALES, Nanyang Technological University, Singapore 637553 (Singapore); Novitas, Nanoelectronics Centre of Excellence, School of Electrical and Electronic Engineering, Nanyang Technological University, Singapore 639798 (Singapore); Coquet, Philippe [CINTRA CNRS/NTU/THALES, Nanyang Technological University, Singapore 637553 (Singapore)

2014-09-30

Highlights: • An array of well aligned and uniform CNTs is successfully fabricated by PECVD. • SiONW growth utilizes Si substrate as the source, ruling out the usage of silane. • With CNT array on the substrate, SiONW growth is improved significantly. • CNTs help dispersion of the catalysts and diffusion of the Si atoms. - Abstract: We report a method to promote solid source growth of Si oxide nanowires (SiONWs) by using an array of vertically aligned carbon nanotubes (CNTs). It starts with the fabrication of CNT array by plasma enhanced chemical vapor deposition (PECVD) on Si wafers, followed by growth of SiONWs. Herein, CNTs serve as a scaffold, which helps the dispersion of catalysts for SiONWs and also provides space for hydrogen which boosts the diffusion of Si atoms and hence formation of SiONWs. As the result, a three dimensional (3D) hybrid network of densely packed SiONWs and CNTs can be produced rapidly.

Cobalt nanoparticles as recyclable catalyst for aerobic oxidation of alcohols in liquid phase

Energy Technology Data Exchange (ETDEWEB)

Mondal, Arijit; Mukherjee, Debkumar, E-mail: debkumarmukherjee@rediffmail.com [Ramsaday College, Department of Chemistry (India); Adhikary, Bibhutosh, E-mail: adhikarybibhu@yahoo.com [Indian Institute of Engineering, Sciences and Technology, Shibpur, Department of Chemistry (India); Ahmed, Md Azharuddin [University of Calcutta, Department of Physics (India)

2016-05-15

Cobalt nanoparticles prepared at room temperature from cobalt sulphate and tetrabutyl ammonium bromide as surfactant have been found to be effective oxidation catalysts. Palladium and platinum nanoparticles (average size 4–6 nm) can also be prepared from PdCl{sub 2} and K{sub 2}PtCl{sub 4}, respectively, using the same surfactant but require high temperature (~120 °C) and much longer preparation time. Agglomeration of nanoparticles prepared from metals like palladium and platinum in common solvents, however, restricts their use as catalysts. It is therefore our endeavour to find the right combination of catalyst and solvent that will be beneficial from industrial point of view. Magnetic property measurement of cobalt nanoclusters was made using SQUID to identify their reusability nature. Herein, we report the use of cobalt nanoparticles (average size 90–95 nm) in dichloromethane solvent as effective reusable catalysts for aerobic oxidation of a variety of alcohols.Graphical Abstract.

Chemical nature of catalysts of oxide nanoparticles in environment ...

Indian Academy of Sciences (India)

12

Chemical nature of catalysts of oxide nanoparticles in environment prevailing during growth of carbon nanostructures by CCVD. M. Jana*, A. Sil and S. Ray. †. Department of Metallurgical and Materials Engineering. Indian Institute of Technology Roorkee. Roorkee 247 667, India. Present address: *School of Materials ...

Hydroxylation of benzene to phenol over magnetic recyclable nanostructured CuFe mixed-oxide catalyst

CSIR Research Space (South Africa)

Makgwane, PR

2015-03-01

Full Text Available A highly active and magnetically recyclable nanostructured copper–iron oxide (CuFe) catalyst has been synthesized for hydroxylation of benzene to phenol under mild reaction conditions. The obtained catalytic results were correlated with the catalyst...

Heteropoly acid promoted V2O5/TiO2 catalysts for NO abatement with ammonia in alkali containing flue gases

DEFF Research Database (Denmark)

Putluru, Siva Sankar Reddy; Jensen, Anker Degn; Riisager, Anders

2011-01-01

V2O5/TiO2 and heteropoly acid promoted V2O5/TiO2 catalysts were prepared and characterized by N2 physisorption, XRPD and NH3-TPD. The influence of the calcination temperature from 400 to 700 1C on crystallinity and acidic properties was studied and compared with the activity for the selective...... catalytic reduction (SCR) of NO with ammonia. The SCR activity of heteropoly acid promoted catalysts was found to be much higher than for unpromoted catalysts. The stability of heteropoly acid promoted catalysts is dependent on calcination temperature and there is a gradual decrease in SCR activity...... and acidity with increase in calcination temperatures. Furthermore, the heteropoly acid promoted V2O5/TiO2 catalysts showed excellent alkali deactivation resistance and might therefore be alternative deNOx catalysts in biomass fired power plants....

Effect of Promoters in Co-Mn-Al Mixed Oxide Catalyst on N2O Decomposition

Czech Academy of Sciences Publication Activity Database

Karásková, K.; Obalová, L.; Jirátová, Květa; Kovanda, F.

2010-01-01

Roč. 160, č. 2 (2010), s. 480-487 ISSN 1385-8947 R&D Projects: GA ČR GA106/09/1664 Institutional research plan: CEZ:AV0Z40720504 Keywords : nitrous oxide * catalytic decomposition * promoter effect Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 3.074, year: 2010

Advances in Base-Free Oxidation of Bio-Based Compounds on Supported Gold Catalysts

Directory of Open Access Journals (Sweden)

Robert Wojcieszak

2017-11-01

Full Text Available The oxidation of bio-based molecules in general, and of carbohydrates and furanics in particular, is a highly attractive process. The catalytic conversion of renewable compounds is of high importance. Acids and other chemical intermediates issued from oxidation processes have many applications related, especially, to food and detergents, as well as to pharmaceutics, cosmetics, and the chemical industry. Until now, the oxidation of sugars, furfural, or 5-hydroxymethylfurfural has been mainly conducted through biochemical processes or with strong inorganic oxidants. The use of these processes very often presents many disadvantages, especially regarding products separation and selectivity control. Generally, the oxidation is performed in batch conditions using an appropriate catalyst and a basic aqueous solution (pH 7–9, while bubbling oxygen or air through the slurry. However, there is a renewed interest in working in base-free conditions to avoid the production of salts. Actually, this gives direct access to different acids or diacids without laborious product purification steps. This review focuses on processes applying gold-based catalysts, and on the catalytic properties of these systems in the base-free oxidation of important compounds: C5–C6 sugars, furfural, and 5-hydroxymethylfurfural. A better understanding of the chemical and physical properties of the catalysts and of the operating conditions applied in the oxidation reactions is essential. For this reason, in this review we put emphasis on these most impacting factors.

TECHNOLOGY DEVELOPMENT FOR IRON AND COBALT FISCHER-TROPSCH CATALYSTS

International Nuclear Information System (INIS)

Burtron H. Davis

1999-01-01

The impact of activation procedure on the phase composition of precipitated iron Fischer-Tropsch (FT) catalysts has been studied. Catalyst samples taken during activation and FT synthesis have been characterized by Moessbauer spectroscopy. Formation of iron carbide is necessary for high FT activity. Hydrogen activation of precipitated iron catalysts results in reduction to predominantly metallic iron and Fe(sub 3)O(sub 4). Metallic iron is not stable under FT 3 4 conditions and is rapidly converted to(epsilon)(prime)-Fe(sub 2.2)C. Activation with carbon monoxide or syngas 2.2 with low hydrogen partial pressure reduces catalysts to(chi)-Fe(sub 5)C(sub 2) and a small amount of 5 2 superparamagnetic carbide. Exposure to FT conditions partially oxidizes iron carbide to Fe(sub 3)O(sub 4); however, catalysts promoted with potassium or potassium and copper maintain a constant carbide content and activity after the initial oxidation. An unpromoted iron catalyst which was activated with carbon monoxide to produce 94%(chi)-Fe(sub 5)C(sub 2), deactivated rapidly as the carbide was oxidized to Fe(sub 3)O(sub 4). No difference in activity, stability or deactivation rate was found for(chi)-Fe(sub 5)C(sub 2) and(epsilon)(prime)-Fe(sub 2.2)C

TECHNOLOGY DEVELOPMENT FOR IRON AND COBALT FISCHER-TROPSCH CATALYSTS

Energy Technology Data Exchange (ETDEWEB)

Burtron H. Davis

1999-04-30

The impact of activation procedure on the phase composition of precipitated iron Fischer-Tropsch (FT) catalysts has been studied. Catalyst samples taken during activation and FT synthesis have been characterized by Moessbauer spectroscopy. Formation of iron carbide is necessary for high FT activity. Hydrogen activation of precipitated iron catalysts results in reduction to predominantly metallic iron and Fe{sub 3}O{sub 4}. Metallic iron is not stable under FT 3 4 conditions and is rapidly converted to {epsilon}{prime}-Fe{sub 2.2}C. Activation with carbon monoxide or syngas 2.2 with low hydrogen partial pressure reduces catalysts to {chi}-Fe{sub 5}C{sub 2} and a small amount of 5 2 superparamagnetic carbide. Exposure to FT conditions partially oxidizes iron carbide to Fe{sub 3}O{sub 4}; however, catalysts promoted with potassium or potassium and copper maintain a constant carbide content and activity after the initial oxidation. An unpromoted iron catalyst which was activated with carbon monoxide to produce 94% {chi}-Fe{sub 5}C{sub 2}, deactivated rapidly as the carbide was oxidized to Fe{sub 3}O{sub 4}. No difference in activity, stability or deactivation rate was found for {chi}-Fe{sub 5}C{sub 2} and {epsilon}{prime}-Fe{sub 2.2}C.

Study of the oxides nature effect of rare and rare earth elements on the aluminium-chromium catalyst properties

International Nuclear Information System (INIS)

Dadashev, B.A.; Abbasov, S.G.; Sarydzhanov, A.A.; AN Azerbajdzhanskoj SSR, Baku. Inst. Neftekhimicheskikh Protsessov)

1975-01-01

Adsorption studies have shown that oxides of rare and rare earth elements REE appreciably influence the structure of aluminium-chrome catalyst. Alkaline promotors, unlike REE, contribute to the formation of developed contact surface. Electrophysical investigations show that oxides of rare elements introduced into the catalyst increase its conductivity and activation energy. As for REE oxides, they decrease the conductivity and increase the activation energy. Catalysts with developed surface and high conductivity are also more active in the reaction of isopentane dehydration

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

Energy Technology Data Exchange (ETDEWEB)

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

2015-04-30

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

Influence of ionizing radiation on the catalytic properties of oxide catalysts tested by hydrogen peroxide decomposition

International Nuclear Information System (INIS)

Mucka, V.

1987-01-01

Results of a study of some physical and catalytic properties of different oxide catalysts as affected by ionizing radiation (γ, n, e - ) and tested by the decomposition of hydrogen peroxide in aqueous solution are presented in this paper. The oxidation state of the active component present on the catalyst surface was found to be one of the most sensitive properties to the ionizing radiation. Changes of this state induced by γ-irradiation were found to be positive in most cases; electron pre-irradiation of the oxides leads, as a rule, to negative effects and the effects of neutron irradiation may be positive or negative. On the other hand, changes in the catalytic activity of the oxides after γ-or electron-irradiation seem to be mostly negative and positive, respectively; the effects of fast neutrons seem to vary here. Neither quantitative or qualitative correlation was found between the radiation-induced changes in these two quantities. The results give evidence that ionizing radiation principally affects the surface concentration of the catalytic sites. Both the character and magnitude of the changes in surface oxidation abilities and in catalytic activities of the oxide catalysts seem to be dependent upon the actual state of the catalyst surface. (author)