highly effective catalyst: Topics by Science.gov

Sample records for highly effective catalyst

Effect of Electric Discharge on Properties of Nano-Particulate Catalyst for Plasma-Catalysis.

PubMed

Lee, Chung Jun; Kim, Jip; Kim, Taegyu

2016-02-01

Heterogeneous catalytic processes have been used to produce hydrogen from hydrocarbons. However, high reforming temperature caused serious catalyst deteriorations and low energy efficiency. Recently, a plasma-catalyst hybrid process was used to reduce the reforming temperature and to improve the stability and durability of reforming catalysts. Effect of electric discharges on properties of nanoparticulate catalysts for plasma-catalysis was investigated in the present study. Catalyst-bed porosity was varied by packing catalyst beads with the different size in a reactor. Discharge power and onset voltage of the plasma were measured as the catalyst-bed porosity was varied. The effect of discharge voltage, frequency and voltage waveforms such as the sine, pulse and square was investigated. We found that the optimal porosity of the catalyst-bed exists to maximize the electric discharge. At a low porosity, the electric discharge was unstable to be sustained because the space between catalysts got narrow nearly close to the sheath region. On the other hand, at a high porosity, the electric discharge became weak because the plasma was not sufficient to interact with the surface of catalysts. The discharge power increased as the discharge voltage and frequency increased. The square waveform was more efficient than the sine and pulse one. At a high porosity, however, the effect of the voltage waveform was not considerable because the space between catalysts was too large for plasma to interact with the surface of catalysts.
Effect of Oxide Coating on Performance of Copper-Zinc Oxide-Based Catalyst for Methanol Synthesis via Hydrogenation of Carbon Dioxide.

PubMed

Umegaki, Tetsuo; Kojima, Yoshiyuki; Omata, Kohji

2015-11-16

The effect of oxide coating on the activity of a copper-zinc oxide-based catalyst for methanol synthesis via the hydrogenation of carbon dioxide was investigated. A commercial catalyst was coated with various oxides by a sol-gel method. The influence of the types of promoters used in the sol-gel reaction was investigated. Temperature-programmed reduction-thermogravimetric analysis revealed that the reduction peak assigned to the copper species in the oxide-coated catalysts prepared using ammonia shifts to lower temperatures than that of the pristine catalyst; in contrast, the reduction peak shifts to higher temperatures for the catalysts prepared using L(+)-arginine. These observations indicated that the copper species were weakly bonded with the oxide and were easily reduced by using ammonia. The catalysts prepared using ammonia show higher CO₂ conversion than the catalysts prepared using L(+)-arginine. Among the catalysts prepared using ammonia, the silica-coated catalyst displayed a high activity at high temperatures, while the zirconia-coated catalyst and titania-coated catalyst had high activity at low temperatures. At high temperature the conversion over the silica-coated catalyst does not significantly change with reaction temperature, while the conversion over the zirconia-coated catalyst and titania-coated catalyst decreases with reaction time. From the results of FTIR, the durability depends on hydrophilicity of the oxides.
Effect of Oxide Coating on Performance of Copper-Zinc Oxide-Based Catalyst for Methanol Synthesis via Hydrogenation of Carbon Dioxide

PubMed Central

Umegaki, Tetsuo; Kojima, Yoshiyuki; Omata, Kohji

2015-01-01

The effect of oxide coating on the activity of a copper-zinc oxide–based catalyst for methanol synthesis via the hydrogenation of carbon dioxide was investigated. A commercial catalyst was coated with various oxides by a sol-gel method. The influence of the types of promoters used in the sol-gel reaction was investigated. Temperature-programmed reduction-thermogravimetric analysis revealed that the reduction peak assigned to the copper species in the oxide-coated catalysts prepared using ammonia shifts to lower temperatures than that of the pristine catalyst; in contrast, the reduction peak shifts to higher temperatures for the catalysts prepared using L(+)-arginine. These observations indicated that the copper species were weakly bonded with the oxide and were easily reduced by using ammonia. The catalysts prepared using ammonia show higher CO2 conversion than the catalysts prepared using L(+)-arginine. Among the catalysts prepared using ammonia, the silica-coated catalyst displayed a high activity at high temperatures, while the zirconia-coated catalyst and titania-coated catalyst had high activity at low temperatures. At high temperature the conversion over the silica-coated catalyst does not significantly change with reaction temperature, while the conversion over the zirconia-coated catalyst and titania-coated catalyst decreases with reaction time. From the results of FTIR, the durability depends on hydrophilicity of the oxides. PMID:28793674
Reducing fischer-tropsch catalyst attrition losses in high agitation reaction systems

DOEpatents

Singleton, Alan H.; Oukaci, Rachid; Goodwin, James G.

2001-01-01

A method for reducing catalyst attrition losses in hydrocarbon synthesis processes conducted in high agitation reaction systems; a method of producing an attrition-resistant catalyst; a catalyst produced by such method; a method of producing an attrition-resistant catalyst support; and a catalyst support produced by such method. The inventive method of reducing catalyst attrition losses comprises the step of reacting a synthesis gas in a high agitation reaction system in the presence of a catalyst. In one aspect, the catalyst preferably comprises a .gamma.-alumina support including an amount of titanium effective for increasing the attrition resistance of the catalyst. In another aspect, the catalyst preferably comprises a .gamma.-alumina support which has been treated, after calcination, with an acidic, aqueous solution. The acidic aqueous solution preferably has a pH of not more than about 5. In another aspect, the catalyst preferably comprises cobalt on a .gamma.-alumina support wherein the cobalt has been applied to the .gamma.-alumina support by totally aqueous, incipient wetness-type impregnation. In another aspect, the catalyst preferably comprises cobalt on a .gamma.-alumina support with an amount of a lanthana promoter effective for increasing the attrition resistance of the catalyst. In another aspect, the catalyst preferably comprises a .gamma.-alumina support produced from boehmite having a crystallite size, in the 021 plane, in the range of from about 30 to about 55 .ANG.ngstrons. In another aspect, the inventive method of producing an attrition-resistant catalyst comprises the step of treating a .gamma.-alumina support, after calcination of and before adding catalytic material to the support, with an acidic solution effective for increasing the attrition resistance of the catalyst. In another aspect, the inventive method of producing an attrition-resistant catalyst support comprises the step of treating calcined .gamma.-alumina with an acidic, aqueous solution effective for increasing the attrition resistance of the .gamma.-alumina.
Effective rate constants for nanostructured heterogeneous catalysts

NASA Astrophysics Data System (ADS)

Hendy, Shaun; Gaston, Nicola; Zhang, Philip; Lund, Nat

2012-02-01

There is currently a high level of interest in the use of nanostructured materials for catalysis. For instance, gold, which is largely inert in the bulk, can exhibit strong catalytic activity when in nanoparticle form. With precious metal catalysts such as Pt and Pd in high demand, the use of these materials in nanoparticle form can also substantially reduce costs by exposure of more surface area for the same volume of material. When reactants are plentiful, the effective activity of a nanoparticulate catalyst will increase roughly with its surface area. However, under diffusion-limited conditions, the reactant must diffuse to active sites on the catalyst, so a high surface area and a high density of active sites may bring diminishing returns if reactant is consumed faster than it arrives. Here we apply a mathematical homogenisation approach to derive simple expressions for the effective reactivity of a nanostructured catalyst under diffusion limited conditions that relate the intrinsic rate constants of the surfaces presented by the catalyst to an effective rate constant. When highly active catalytic sites, such as step edges or other defects are present, we show that distinct limiting cases emerge depending on the degree of overlap of the reactant depletion zone about each site. In gases, the size of this depletion zone is approximately the mean free path, so the effective reactivity will depend on the structure of the catalyst on that scale. We discuss implications for the optimal design of nanoparticle catalysts.
Rapid Catalyst Screening by a Continuous-Flow Microreactor Interfaced with Ultra High Pressure Liquid Chromatography

PubMed Central

Fang, Hui; Xiao, Qing; Wu, Fanghui; Floreancig, Paul E.; Weber, Stephen G.

2010-01-01

A high-throughput screening system for homogeneous catalyst discovery has been developed by integrating a continuous-flow capillary-based microreactor with ultra-high pressure liquid chromatography (UHPLC) for fast online analysis. Reactions are conducted in distinct and stable zones in a flow stream that allows for time and temperature regulation. UHPLC detection at high temperature allows high throughput online determination of substrate, product, and byproduct concentrations. We evaluated the efficacies of a series of soluble acid catalysts for an intramolecular Friedel-Crafts addition into an acyliminium ion intermediate within one day and with minimal material investment. The effects of catalyst loading, reaction time, and reaction temperature were also screened. This system exhibited high reproducibility for high-throughput catalyst screening and allowed several acid catalysts for the reaction to be identified. Major side products from the reactions were determined through off-line mass spectrometric detection. Er(OTf)3, the catalyst that showed optimal efficiency in the screening, was shown to be effective at promoting the cyclization reaction on a preparative scale. PMID:20666502
Boron and oxygen-codoped porous carbon as efficient oxygen reduction catalysts

NASA Astrophysics Data System (ADS)

Lei, Zhidan; Chen, Hongbiao; Yang, Mei; Yang, Duanguang; Li, Huaming

2017-12-01

A low-cost boron- and oxygen-codoped porous carbon electrocatalyst towards oxygen reduction reaction (ORR) has been fabricated by a facile one-step pyrolysis approach, while a boron- and oxygen-rich polymer network was used as precursor. The boron- and oxygen-codoped carbon catalyst with high ORR electrocatalytic activity is comparable to that of Pt/C and is superior to that of catalysts doped solely with boron atoms or with oxygen atoms. Furthermore, the optimized boron- and oxygen-codoped carbon catalyst possesses excellent methanol tolerance and long-term durability in alkaline media. The high electrocatalytic activity of the dual-doped carbon catalysts can be attributed to the synergistic effects of high surface area, predominant mesostructure, abundant active oxygen-containing groups, and effective boron doping. The present results show that this boron- and oxygen-codoping strategy could be as a promising way for the preparation of highly efficient ORR catalysts.
Final Technical Report for GO15052 Intematix: Combinatorial Synthesis and High Throughput Screening of Effective Catalysts for Chemical Hydrides

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

Melman, Jonathan

The objectives of this project are: to discover cost-effective catalysts for release of hydrogen from chemical hydrogen storage systems; and to discover cost-effective catalysts for the regeneration of spent chemical hydrogen storage materials.
An Overview of Recent Development in Composite Catalysts from Porous Materials for Various Reactions and Processes

PubMed Central

Xie, Zaiku; Liu, Zhicheng; Wang, Yangdong; Yang, Qihua; Xu, Longya; Ding, Weiping

2010-01-01

Catalysts are important to the chemical industry and environmental remediation due to their effective conversion of one chemical into another. Among them, composite catalysts have attracted continuous attention during the past decades. Nowadays, composite catalysts are being used more and more to meet the practical catalytic performance requirements in the chemical industry of high activity, high selectivity and good stability. In this paper, we reviewed our recent work on development of composite catalysts, mainly focusing on the composite catalysts obtained from porous materials such as zeolites, mesoporous materials, carbon nanotubes (CNT), etc. Six types of porous composite catalysts are discussed, including amorphous oxide modified zeolite composite catalysts, zeolite composites prepared by co-crystallization or overgrowth, hierarchical porous catalysts, host-guest porous composites, inorganic and organic mesoporous composite catalysts, and polymer/CNT composite catalysts. PMID:20559508
Evaluation of the Effect of Water Vapor On the Performance of NASA's NMRO Catalysts for Carbon Monoxide Oxidation

NASA Technical Reports Server (NTRS)

Akyurtlu, Ates; Akyurtlu, Jale F.; Ammons, Vaughnery; Battle, Taikelia; Gay, Amy; Bray, Kyle; Washington, Boe; Schryer, David (Technical Monitor); Jordan, Jeff (Technical Monitor)

2002-01-01

The Noble Metal Reducible Oxide (NMRO) catalysts for the low temperature oxidation of carbon monoxide were developed by NASA for the reoxidation of carbon monoxide which forms by the dissociation of carbon dioxide during the operation of sealed carbon dioxide lasers. The NMRO catalyst, which consists of a noble metal in conjunction with a reducible metal oxide, was evaluated under conditions that will be encountered in a CO2 laser operation, namely temperatures in the range 298 to 373 K and no significant reaction gas components other than CO, CO2 and O2. The NMRO catalysts may have significant potential for spin-off applications such as the prevention of carbon monoxide build-up in closed spaces as in space vehicle cabins or submarines, and the elimination of the cold start-up problem of automobile exhaust catalysts. The most significant difference in the conditions of these possible future applications is the high moisture content of the gases to be processed. Lack of understanding of the effects of water vapor and high temperature on catalyst activity and operation for extended periods are currently the main stumbling blocks for the transfer of this NASA technology to be used for commercial purposes. In the original proposal the following objectives were stated: To obtain experimental data on the adsorption, desorption and reaction characteristics of CO and CO2 the catalysts under high moisture conditions; to collect evidence on the presence of carbonate and hydroxyl surface species and their involvement in the CO oxidation mechanism; and to model the reaction system using a Monte-Carlo simulation to gain insight on the various steps involved. After the work has commenced the NASA technical monitor Mr. David Scheyer informed us that there was increased interest in the possible use of the NMRO catalysts as automobile exhaust catalysts and therefore NASA wanted to know whether the catalysts can operate at high temperatures as well as with high moisture gases. At that meeting it was decided that investigation of the high temperature performance of the NMRO catalysts should be given priority and replace the Monte-Carlo simulation objective. As a result, the modified objectives of the investigation were taken as the investigation of the high-temperature activity of the NMRO catalysts, and the effect of water vapor on the performance of these catalysts.
Regeneration and reuse of iron catalyst for Fenton-like reactions.

PubMed

Cao, Guo-min; Sheng, Mei; Niu, Wen-feng; Fei, Yu-lei; Li, Dong

2009-12-30

Fenton and Fenton-like reactions employed for oxidative treatment of a typical industrial wastewater generate a large amount of ferric hydroxide sludge which has to be properly disposed at a high cost. This paper presents a simple and cost-effective method for recovering the iron catalyst from the iron hydroxide sludge for oxidative treatment of industrial wastewaters. The sludge was dewatered, dried and baked at 350-400 degrees C for 20-30 min; the residual solids were dissolved in sulfuric acid to form the reusable catalyst for Fenton and Fenton-like reactions. The recovered catalyst was highly effective for the oxidative pretreatment of a fine chemical wastewater to improve its biodegradability; the resulting COD removal and BOD(5)/COD ratio of the treated stream remained nearly unchanged during the time period when the regenerated catalyst was reused six times. The simple and effective catalyst regeneration method will make Fenton and Fenton-like oxidation a more cost-effective wastewater treatment alternative.
Cumulative effect of transition metals on nitrogen and fluorine co-doped graphite nanofibers: an efficient and highly durable non-precious metal catalyst for the oxygen reduction reaction.

PubMed

Peera, S Gouse; Arunchander, A; Sahu, A K

2016-08-14

Nitrogen and fluorine co-doped graphite nanofibers (N/F-GNF) and their cumulative effect with Fe and Co have been developed as an alternative non-precious metal catalyst for efficient oxygen reduction reaction (ORR) in acidic media. The synergistic effect between the doped hetero atoms and the co-ordinated Fe and Co towards ORR activity and durability of the catalyst is deeply investigated. A high ORR onset potential comparable with commercial Pt/C catalyst is observed with the Fe-Co/NF-GNF catalyst, which indicates that this catalyst is a potential alternative to Pt/C. A fivefold increase in mass activity is achieved by the Fe-Co/NF-GNF catalyst compared to the simple N/F-GNF catalyst, which endorses the significant role of transition metal atoms in enhancing ORR activity. The advanced Fe-Co/NF-GNF catalyst also exhibits complete tolerance to CH3OH and CO. The Fe-Co/NF-GNF catalyst also exhibits excellent durability towards the ORR with only a 10 mV negative shift in its half wave potential after a 10 000 repeated potential cycling test, whereas in the case of a commercial Pt/C catalyst there was an ∼110 mV negative shift under similar environmental conditions. More stringent corrosive test cycles were also performed by maintaining the cell as high as 1.4 V with a later decrease to 0.6 V vs. RHE for 300 cycles, which showed the excellent durability of the Fe-Co/NF-GNF catalyst in comparison with the Pt/C catalyst. XPS analysis of the Fe-Co/NF-GNF catalyst presents the ORR active chemical states of N (pyridinic-N and graphitic-N) and F (semi-ionic-F) and the co-ordinated sites of Fe and Co species with the dopants. The excellent performance and durability of the Fe-Co/NF-GNF catalyst is due to the synergistic effect between the hetero atoms dopants (N and F) and strong co-ordinating bonds of M-N-C, which protect the graphene layers around the metallic species and greatly mitigates the leaching of Co and Fe during the long term cycling test. The high activity and long term durability of the Fe-Co/NF-GNF catalyst make it a promising ORR electrocatalyst for the fuel cell cathode reaction.
Nanocarbon/oxide composite catalysts for bifunctional oxygen reduction and evolution in reversible alkaline fuel cells: A mini review

NASA Astrophysics Data System (ADS)

Chen, Mengjie; Wang, Lei; Yang, Haipeng; Zhao, Shuai; Xu, Hui; Wu, Gang

2018-01-01

A reversible fuel cell (RFC), which integrates a fuel cell with an electrolyzer, is similar to a rechargeable battery. This technology lies on high-performance bifunctional catalysts for the oxygen reduction reaction (ORR) in the fuel cell mode and the oxygen evolution reaction (OER) in the electrolyzer mode. Current catalysts are platinum group metals (PGM) such as Pt and Ir, which are expensive and scarce. Therefore, it is highly desirable to develop PGM-free catalysts for large-scale application of RFCs. In this mini review, we discussed the most promising nanocarbon/oxide composite catalysts for ORR/OER bifunctional catalysis in alkaline media, which is mainly based on our recent progress. Starting with the effectiveness of selected oxides and nanocarbons in terms of their activity and stability, we outlined synthetic methods and the resulting structures and morphologies of catalysts to provide a correlation between synthesis, structure, and property. A special emphasis is put on understanding of the possible synergistic effect between oxide and nanocarbon for enhanced performance. Finally, a few nanocomposite catalysts are discussed as typical examples to elucidate the rules of designing highly active and durable bifunctional catalysts for RFC applications.
Titanium Dioxide as a Catalyst Support in Heterogeneous Catalysis

PubMed Central

Bagheri, Samira; Muhd Julkapli, Nurhidayatullaili; Bee Abd Hamid, Sharifah

2014-01-01

The lack of stability is a challenge for most heterogeneous catalysts. During operations, the agglomeration of particles may block the active sites of the catalyst, which is believed to contribute to its instability. Recently, titanium oxide (TiO2) was introduced as an alternative support material for heterogeneous catalyst due to the effect of its high surface area stabilizing the catalysts in its mesoporous structure. TiO2 supported metal catalysts have attracted interest due to TiO2 nanoparticles high activity for various reduction and oxidation reactions at low pressures and temperatures. Furthermore, TiO2 was found to be a good metal oxide catalyst support due to the strong metal support interaction, chemical stability, and acid-base property. The aforementioned properties make heterogeneous TiO2 supported catalysts show a high potential in photocatalyst-related applications, electrodes for wet solar cells, synthesis of fine chemicals, and others. This review focuses on TiO2 as a support material for heterogeneous catalysts and its potential applications. PMID:25383380
Nanocrystalline Iron-Ore-Based Catalysts for Fischer-Tropsch Synthesis.

PubMed

Yong, Seok; Park, Ji Chan; Lee, Ho-Tae; Yang, Jung-Il; Hong, SungJun; Jung, Heon; Chun, Dong Hyun

2016-02-01

Nanocrystalline iron ore particles were fabricated by a wet-milling process using an Ultra Apex Mill, after which they were used as raw materials of iron-based catalysts for low-temperature Fischer-Tropsch synthesis (FTS) below 280 degrees C, which usually requires catalysts with a high surface area, a large pore volume, and a small crystallite size. The wet-milling process using the Ultra Apex Mill effectively destroyed the initial crystallite structure of the natural iron ores of several tens to hundreds of nanometers in size, resulting in the generation of nanocrystalline iron ore particles with a high surface area and a large pore volume. The iron-ore-based catalysts prepared from the nanocrystalline iron ore particles effectively catalyzed the low-temperature FTS, displaying a high CO conversion (about 90%) and good C5+ hydrocarbon productivity (about 0.22 g/g(cat)(-h)). This demonstrates the feasibility of using the iron-ore-based catalysts as inexpensive and disposable catalysts for the low-temperature FTS.
Development of highly active and stable hybrid cathode catalyst for PEMFCs

NASA Astrophysics Data System (ADS)

Jung, Won Suk

Polymer electrolyte membrane fuel cells (PEMFCs) are attractive power sources of the future for a variety of applications including portable electronics, stationary power, and automobile application. However, sluggish cathode kinetics, high Pt cost, and durability issues inhibit the commercialization of PEMFCs. To overcome these drawbacks, research has been focused on alloying Pt with transition metals since alloy catalysts show significantly improved catalytic properties like high activity, selectivity, and durability. However, Pt-alloy catalysts synthesized using the conventional impregnation method exhibit uneven particle size and poor particle distribution resulting in poor performance and/or durability in PEMFCs. In this dissertation, a novel catalyst synthesis methodology is developed and compared with catalysts prepared using impregnation method and commercial catalysts. Two approaches are investigated for the catalyst development. The catalyst durability was studied under U. S. DRIVE Fuel Cell Tech Team suggested protocols. In the first approach, the carbon composite catalyst (CCC) having active sites for oxygen reduction reaction (ORR) is employed as a support for the synthesis of Pt/CCC catalyst. The structural and electrochemical properties of Pt/CCC catalyst are investigated using high-resolution transmission electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy, while RDE and fuel cell testing are carried out to study the electrochemical properties. The synergistic effect of CCC and Pt is confirmed by the observed high activity towards ORR for the Pt/CCC catalyst. The second approach is the synthesis of Co-doped hybrid cathode catalysts (Co-doped Pt/CCC) by diffusing the Co metal present within the CCC support into the Pt nanoparticles during heat-treatment. The optimized Co-doped Pt/CCC catalyst performed better than the commercial catalysts and the catalyst prepared using the impregnation method in PEMFCs and showed high stability under 30,000 potential cycles between 0.6 and 1.0 V. To further increase the stability of the catalyst at high potential cycles (1.0-1.5 V), high temperature treatment is used to obtain graphitized carbon having optimum BET surface area. The novel catalyst synthesis procedure developed in this study was successfully applied for the synthesis of Co-doped Pt catalysts supported on the graphitized carbon which showed high activity and enhanced stability at high potentials.
The effects of the catalytic converter and fuel sulfur level on motor vehicle particulate matter emissions: light duty diesel vehicles.

PubMed

Maricq, M Matti; Chase, Richard E; Xu, Ning; Laing, Paul M

2002-01-15

Wind tunnel measurements and direct tailpipe particulate matter (PM) sampling are utilized to examine how the combination of oxidation catalyst and fuel sulfur content affects the nature and quantity of PM emissions from the exhaust of a light duty diesel truck. When low sulfur fuel (4 ppm) is used, or when high sulfur (350 ppm)fuel is employed without an active catalyst present, a single log-normal distribution of exhaust particles is observed with a number mean diameter in the range of 70-83 nm. In the absence of the oxidation catalyst, the high sulfur level has at most a modest effect on particle emissions (<50%) and a minor effect on particle size (<5%). In combination with the active oxidation catalyst tested, high sulfur fuel can lead to a second, nanoparticle, mode, which appears at approximately 20 nm during high speed operation (70 mph), but is not present at low speed (40 mph). A thermodenuder significantly reduces the nanoparticle mode when set to temperatures above approximately 200 degrees C, suggesting that these particles are semivolatile in nature. Because they are observed only when the catalyst is present and the sulfur level is high, this mode likely originates from the nucleation of sulfates formed over the catalyst, although the composition may also include hydrocarbons.
Method of depositing a catalyst on a fuel cell electrode

DOEpatents

Dearnaley, Geoffrey; Arps, James H.

2000-01-01

Fuel cell electrodes comprising a minimal load of catalyst having maximum catalytic activity and a method of forming such fuel cell electrodes. The method comprises vaporizing a catalyst, preferably platinum, in a vacuum to form a catalyst vapor. A catalytically effective amount of the catalyst vapor is deposited onto a carbon catalyst support on the fuel cell electrode. The electrode preferably is carbon cloth. The method reduces the amount of catalyst needed for a high performance fuel cell electrode to about 0.3 mg/cm.sup.2 or less.
Studies of potassium-promoted nickel catalysts for methane steam reforming: Effect of surface potassium location

NASA Astrophysics Data System (ADS)

Borowiecki, Tadeusz; Denis, Andrzej; Rawski, Michał; Gołębiowski, Andrzej; Stołecki, Kazimierz; Dmytrzyk, Jaromir; Kotarba, Andrzej

2014-05-01

The effect of potassium addition to the Ni/Al2O3 steam reforming catalyst has been investigated on several model systems, including K/Al2O3 with various amounts of alkali promoters (1-4 wt% of K2O), a model catalyst 90%NiO-10%Al2O3 promoted with potassium and a commercial catalyst. The potassium surface state and stability were investigated by means of the Species Resolved Thermal Alkali Desorption method (SR-TAD). The activity of the catalysts in the steam reforming of methane and their coking-resistance were also evaluated. The results reveal that the beneficial effect of potassium addition is strongly related to its location in the catalysts. The catalyst surface should be promoted with potassium in order to obtain high coking-resistant catalysts. Moreover, the catalyst preparation procedure should ensure a direct interaction of potassium with the Al2O3 support surface. Due to the low stability of potassium on θ-Al2O3 this phase is undesirable during the preparation of a stable steam reforming catalyst.
Quantifying ligand effects in high-oxidation-state metal catalysis

NASA Astrophysics Data System (ADS)

Billow, Brennan S.; McDaniel, Tanner J.; Odom, Aaron L.

2017-09-01

Catalysis by high-valent metals such as titanium(IV) impacts our lives daily through reactions like olefin polymerization. In any catalysis, optimization involves a careful choice of not just the metal but also the ancillary ligands. Because these choices dramatically impact the electronic structure of the system and, in turn, catalyst performance, new tools for catalyst development are needed. Understanding ancillary ligand effects is arguably one of the most critical aspects of catalyst optimization and, while parameters for phosphines have been used for decades with low-valent systems, a comparable system does not exist for high-valent metals. A new electronic parameter for ligand donation, derived from experiments on a high-valent chromium species, is now available. Here, we show that the new parameters enable quantitative determination of ancillary ligand effects on catalysis rate and, in some cases, even provide mechanistic information. Analysing reactions in this way can be used to design better catalyst architectures and paves the way for the use of such parameters in a host of high-valent processes.

Graphene-derived Fe/Co-N-C catalyst in direct methanol fuel cells: Effects of the methanol concentration and ionomer content on cell performance

NASA Astrophysics Data System (ADS)

Park, Jong Cheol; Choi, Chang Hyuck

2017-08-01

Non-precious metal catalysts (typically Fe(Co)-N-C catalysts) have been widely investigated for use as cost-effective cathode materials in low temperature fuel cells. Despite the high oxygen reduction activity and methanol-tolerance of graphene-based Fe(Co)-N-C catalysts in an acidic medium, their use in direct methanol fuel cells (DMFCs) has not yet been successfully implemented, and only a few studies have investigated this topic. Herein, we synthesized a nano-sized graphene-derived Fe/Co-N-C catalyst by physical ball-milling and a subsequent chemical modification of the graphene oxide. Twelve membrane-electrode-assemblies are fabricated with various cathode compositions to determine the effects of the methanol concentration, ionomer (i.e. Nafion) content, and catalyst loading on the DMFC performance. The results show that a graphene-based catalyst is capable of tolerating a highly-concentrated methanol feed up to 10.0 M. The optimized electrode composition has an ionomer content and catalyst loading of 66.7 wt% and 5.0 mg cm-2, respectively. The highest maximum power density is ca. 32 mW cm-2 with a relatively low PtRu content (2 mgPtRu cm-2). This study overcomes the drawbacks of conventional graphene-based electrodes using a nano-sized graphene-based catalyst and further shows the feasibility of their potential applications in DMFC systems.
Enhancement of biodiesel production from marine alga, Scenedesmus sp. through in situ transesterification process associated with acidic catalyst.

PubMed

Kim, Ga Vin; Choi, Woonyong; Kang, Dohyung; Lee, Shinyoung; Lee, Hyeonyong

2014-01-01

The aim of this study was to increase the yield of biodiesel produced by Scenedesmus sp. through in situ transesterification by optimizing various process parameters. Based on the orthogonal matrix analysis for the acidic catalyst, the effects of the factors decreased in the order of reaction temperature (47.5%) > solvent quantity (26.7%) > reaction time (17.5%) > catalyst amount (8.3%). Based on a Taguchi analysis, the effects of the factors decreased in the order of solvent ratio (34.36%) > catalyst (28.62%) > time (19.72%) > temperature (17.32%). The overall biodiesel production appeared to be better using NaOH as an alkaline catalyst rather than using H2SO4 in an acidic process, at 55.07 ± 2.18% (based on lipid weight) versus 48.41 ± 0.21%. However, in considering the purified biodiesel, it was found that the acidic catalyst was approximately 2.5 times more efficient than the alkaline catalyst under the following optimal conditions: temperature of 70 °C (level 2), reaction time of 10 hrs (level 2), catalyst amount of 5% (level 3), and biomass to solvent ratio of 1 : 15 (level 2), respectively. These results clearly demonstrated that the acidic solvent, which combined oil extraction with in situ transesterification, was an effective catalyst for the production of high-quantity, high-quality biodiesel from a Scenedesmus sp.
Enhancement of Biodiesel Production from Marine Alga, Scenedesmus sp. through In Situ Transesterification Process Associated with Acidic Catalyst

PubMed Central

Kim, Ga Vin; Choi, WoonYong; Kang, DoHyung; Lee, ShinYoung; Lee, HyeonYong

2014-01-01

The aim of this study was to increase the yield of biodiesel produced by Scenedesmus sp. through in situ transesterification by optimizing various process parameters. Based on the orthogonal matrix analysis for the acidic catalyst, the effects of the factors decreased in the order of reaction temperature (47.5%) > solvent quantity (26.7%) > reaction time (17.5%) > catalyst amount (8.3%). Based on a Taguchi analysis, the effects of the factors decreased in the order of solvent ratio (34.36%) > catalyst (28.62%) > time (19.72%) > temperature (17.32%). The overall biodiesel production appeared to be better using NaOH as an alkaline catalyst rather than using H2SO4 in an acidic process, at 55.07 ± 2.18% (based on lipid weight) versus 48.41 ± 0.21%. However, in considering the purified biodiesel, it was found that the acidic catalyst was approximately 2.5 times more efficient than the alkaline catalyst under the following optimal conditions: temperature of 70°C (level 2), reaction time of 10 hrs (level 2), catalyst amount of 5% (level 3), and biomass to solvent ratio of 1 : 15 (level 2), respectively. These results clearly demonstrated that the acidic solvent, which combined oil extraction with in situ transesterification, was an effective catalyst for the production of high-quantity, high-quality biodiesel from a Scenedesmus sp. PMID:24689039
[Synergetic effects of silicon carbide and molecular sieve loaded catalyst on microwave assisted catalytic oxidation of toluene].

PubMed

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.
Preparation of a magnetic N-Fe/AC catalyst for aqueous pharmaceutical treatment in heterogeneous sonication system.

PubMed

Zhang, Nan; Zhao, He; Zhang, Guangming; Chong, Shan; Liu, Yucan; Sun, Liyan; Chang, Huazhen; Huang, Ting

2017-02-01

High efficiency and facile separation are desirable for catalysts used in water treatment. In this study, a magnetic catalyst (nitrogen doped iron/activated carbon) was prepared and used for pharmaceutical wastewater treatment. The catalyst was characterized using BET, SEM, XRD, VSM and XPS. Results showed that iron and nitrogen were successfully loaded and doped, magnetic Fe 2 N was formed, large amount of active surface oxygen and Fe(II) were detected, and the catalyst could be easily separated from water. Diclofenac was then degraded using the catalyst in ultrasound system. The catalyst showed high catalytic activity with 95% diclofenac removal. Analysis showed that ·OH attack of diclofenac was a main pathway, and then ·OH generation mechanism was clarified. The effects of catalyst dosage, sonication time, ultrasonic density, initial pH, and inorganic anions on diclofenac degradation were studied. Sulfate anion enhanced the degradation of diclofenac. Mechanism in the catalytic ultrasonic process was analyzed and reactions were clarified. Large quantity of oxidants was generated on the catalyst surface, including ·OH, O 2 - , O - and HO 2 ·, which degraded diclofenac efficiently. In the solution and interior of cavitation bubbles, ·OH and "hot spot" effects contributed to the degradation of diclofenac. Reuse of the catalyst was further investigated to enhance its economy, and the catalyst maintained activity after seven uses. Copyright © 2016 Elsevier Ltd. All rights reserved.
Highly efficient and robust molecular ruthenium catalysts for water oxidation.

PubMed

Duan, Lele; Araujo, Carlos Moyses; Ahlquist, Mårten S G; Sun, Licheng

2012-09-25

Water oxidation catalysts are essential components of light-driven water splitting systems, which could convert water to H(2) driven by solar radiation (H(2)O + hν → 1/2O(2) + H(2)). The oxidation of water (H(2)O → 1/2O(2) + 2H(+) + 2e(-)) provides protons and electrons for the production of dihydrogen (2H(+) + 2e(-) → H(2)), a clean-burning and high-capacity energy carrier. One of the obstacles now is the lack of effective and robust water oxidation catalysts. Aiming at developing robust molecular Ru-bda (H(2)bda = 2,2'-bipyridine-6,6'-dicarboxylic acid) water oxidation catalysts, we carried out density functional theory studies, correlated the robustness of catalysts against hydration with the highest occupied molecular orbital levels of a set of ligands, and successfully directed the synthesis of robust Ru-bda water oxidation catalysts. A series of mononuclear ruthenium complexes [Ru(bda)L(2)] (L = pyridazine, pyrimidine, and phthalazine) were subsequently synthesized and shown to effectively catalyze Ce(IV)-driven [Ce(IV) = Ce(NH(4))(2)(NO(3))(6)] water oxidation with high oxygen production rates up to 286 s(-1) and high turnover numbers up to 55,400.
In situ characterization of catalysts and membranes in a microchannel under high-temperature water gas shift reaction conditions

NASA Astrophysics Data System (ADS)

Cavusoglu, G.; Dallmann, F.; Lichtenberg, H.; Goldbach, A.; Dittmeyer, R.; Grunwaldt, J.-D.

2016-05-01

Microreactor technology with high heat transfer in combination with stable catalysts is a very attractive approach for reactions involving major heat effects such as methane steam reforming and to some extent, also the high temperature water gas shift (WGS) reaction. For this study Rh/ceria catalysts and an ultrathin hydrogen selective membrane were characterized in situ in a microreactor specially designed for x-ray absorption spectroscopic measurements under WGS conditions. The results of these experiments can serve as a basis for further development of the catalysts and membranes.
Zinc-assisted hydrodeoxygenation of biomass-derived 5-hydroxymethylfurfural to 2,5-dimethylfuran.

PubMed

Saha, Basudeb; Bohn, Christine M; Abu-Omar, Mahdi M

2014-11-01

2,5-Dimethylfuran (DMF), a promising cellulosic biofuel candidate from biomass derived intermediates, has received significant attention because of its low oxygen content, high energy density, and high octane value. A bimetallic catalyst combination containing a Lewis-acidic Zn(II) and Pd/C components is effective for 5-hydroxymethylfurfural (HMF) hydrodeoxygenation (HDO) to DMF with high conversion (99%) and selectivity (85% DMF). Control experiments for evaluating the roles of zinc and palladium revealed that ZnCl2 alone did not catalyze the reaction, whereas Pd/C produced 60% less DMF than the combination of both metals. The presence of Lewis acidic component (Zn) was also found to be beneficial for HMF HDO with Ru/C catalyst, but the synergistic effect between the two metal components is more pronounced for the Pd/Zn system than the Ru/Zn. A comparative analysis of the Pd/Zn/C catalyst to previously reported catalytic systems show that the Pd/Zn system containing at least four times less precious metal than the reported catalysts gives comparable or better DMF yields. The catalyst shows excellent recyclability up to 4 cycles, followed by a deactivation, which could be due to coke formation on the catalyst surface. The effectiveness of this combined bimetallic catalyst has also been tested for one-pot conversion of fructose to DMF. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
NiO-PTA supported on ZIF-8 as a highly effective catalyst for hydrocracking of Jatropha oil

PubMed Central

Liu, Jing; He, Jing; Wang, Luying; Li, Rong; Chen, Pan; Rao, Xin; Deng, Lihong; Rong, Long; Lei, Jiandu

2016-01-01

Nickel oxide (NiO) and phosphotungstic acid (PTA) supported on a ZIF-8 (NiO-PTA/ZIF-8) catalyst was first synthesized and it showed high activity and good selectivity for the hydrocracking of Jatropha oil. The catalyst was characterized by SEM, SEM-EDS, TEM, N2 adsorption, FT-IR, XRD and XPS. Compared with the NiO-PTA/Al2O3 catalyst, the selectivity of C15-C18 hydrocarbon increased over 36%, and catalytic efficiency increased 10 times over the NiO-PTA/ZIF-8 catalyst. The prepared NiO-PTA/ZIF-8 catalyst was stable for a reaction time of 104 h and the kinetic behavior was also analyzed. This catalyst was found to bypass the presulfurization process, showing promise as an alternative to sulfided catalysts for green diesel production. PMID:27020579
Nannochloropsis algae pyrolysis with ceria-based catalysts for production of high-quality bio-oils.

PubMed

Aysu, Tevfik; Sanna, Aimaro

2015-10-01

Pyrolysis of Nannochloropsis was carried out in a fixed-bed reactor with newly prepared ceria based catalysts. The effects of pyrolysis parameters such as temperature and catalysts on product yields were investigated. The amount of bio-char, bio-oil and gas products, as well as the compositions of the resulting bio-oils was determined. The results showed that both temperature and catalyst had significant effects on conversion of Nannochloropsis into solid, liquid and gas products. The highest bio-oil yield (23.28 wt%) and deoxygenation effect was obtained in the presence of Ni-Ce/Al2O3 as catalyst at 500°C. Ni-Ce/Al2O3 was able to retain 59% of the alga starting energy in the bio-oil, compared to only 41% in absence of catalyst. Lower content of acids and oxygen in the bio-oil, higher aliphatics (62%), combined with HHV show promise for production of high-quality bio-oil from Nannochloropsis via Ni-Ce/Al2O3 catalytic pyrolysis. Copyright © 2015 Elsevier Ltd. All rights reserved.
Ordered micro/macro porous K-OMS-2/SiO2 nanocatalysts: Facile synthesis, low cost and high catalytic activity for diesel soot combustion

PubMed Central

Yu, Xuehua; Zhao, Zhen; Wei, Yuechang; Liu, Jian

2017-01-01

A series of novel oxide catalysts, which contain three-dimensionally ordered macroporous (3DOM) and microporous structure, were firstly designed and successfully synthesized by simple method. In the as-prepared catalysts, 3DOM SiO2 is used as support and microporous K-OMS-2 oxide nanoparticles are supported on the wall of SiO2. 3DOM K-OMS-2/SiO2 oxide catalysts were firstly used in soot particle oxidation reaction and they show very high catalytic activities. The high activities of K-OMS-2/SiO2 oxide catalysts can be assigned to three possible reasons: macroporous effect of 3DOM structure for improving contact between soot and catalyst, microporous effect of K-OMS-2 for adsorption of small gas molecules and interaction of K and Mn for activation of gas molecules. The catalytic activities of catalysts are comparable to or even higher than noble metal catalyst in the medium and high temperature range. For example, the T50 of K-OMS-2/SiO2-50, 328 °C, is much lower than those of Pt/Al2O3 and 3DOM Au/LaFeO3, 464 and 356 °C,respectively. Moreover, catalysts exhibited high catalytic stability. It is attributed to that the K+ ions are introduced into the microporous structure of OMS-2 and stabilized in the catalytic reaction. Meanwhile, the K+ ions play an important role in templating and stabilizing the tunneled framework of OMS-2. PMID:28443610
Oxygenates vs. synthesis gas

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

Kamil Klier; Richard G. Herman; Alessandra Beretta

1999-04-01

Methanol synthesis from H{sub 2}/CO has been carried out at 7.6 MPa over zirconia-supported copper catalysts. Catalysts with nominal compositions of 10/90 mol% and 30/70 mol% Cu/ZrO{sub 2} were used in this study. Additionally, a 3 mol% cesium-doped 10/90 catalyst was prepared to study the effect of doping with heavy alkali, and this promoter greatly increased the methanol productivity. The effects of CO{sub 2} addition, water injection, reaction temperature, and H{sub 2}/C0 ratio have been investigated. Both CO{sub 2} addition to the synthesis gas and cesium doping of the catalyst promoted methanol synthesis, while inhibiting the synthesis of dimethyl ether.more » Injection of water, however, was found to slightly suppress methanol and dimethyl ether formation while being converted to CO{sub 2} via the water gas shift reaction over these catalysts. There was no clear correlation between copper surface area and catalyst activity. Surface analysis of the tested samples revealed that copper tended to migrate and enrich the catalyst surface. The concept of employing a double-bed reactor with a pronounced temperature gradient to enhance higher alcohol synthesis was explored, and it was found that utilization of a Cs-promoted Cu/ZnO/Cr{sub 2}O{sub 3} catalyst as a first lower temperature bed and a Cs-promoted ZnO/Cr{sub 2}O{sub 3} catalyst as a second high-temperature bed significantly promoted the productivity of 2-methyl-1-propanol (isobutanol) from H{sub 2}/CO synthesis gas mixtures. While the conversion of CO to C{sub 2+} oxygenates over the double-bed configuration was comparable to that observed over the single Cu-based catalyst, major changes in the product distribution occurred by the coupling to the zinc chromite catalyst; that is, the productivity of the C{sub 1}-C{sub 3} alcohols decreased dramatically, and 2-methyl branched alcohols were selectively formed. The desirable methanol/2-methyl oxygenate molar ratios close to 1 were obtained in the present double-bed system that provides the feedstock for the synthesis of high octane and high cetane ethers, where the isobutanol productivity was as high as 139 g/kg cat/hr. Higher alcohol synthesis has been investigated over a Cs/Cu/ZnO/Cr{sub 2}O{sub 3} catalyst at temperatures higher (up to 703K) than those previously utilized, and no sintering of the catalyst was observed during the short-term testing. However, the higher reaction temperatures led to lower CO conversion levels and lower yield of alcohols, especially of methanol, because of equilibrium limitations. With the double catalyst bed configuration, the effect of pressure in the range of 7.6--12.4 MPa on catalyst activity and selectivity was studied. The upper bed was composed of the copper-based catalyst at 598K, and the lower bed consisted of a copper-free Cs-ZnO/Cr{sub 2}O{sub 3} catalyst at a high temperature of 678K. High pressure was found to increase CO conversion to oxygenated products, although the increase in isobutanol productivity did not keep pace with that of methanol. It was also shown that the Cs/Cu/ZnO/Cr{sub 2}O{sub 3} catalyst could be utilized to advantage as the second-bed catalyst at 613--643K instead of the previously used copper-free Cs-ZnO/ Cr{sub 2}O{sub 3} catalyst at higher temperature, With double Cs/Cu/ZnO/Cr{sub 2}O{sub 3} catalysts, high space time yields of up to 202 g/kg cat/hr, with high selectivity to isobutanol, were achieved.« less
Hydrodeoxygenation of water-insoluble bio-oil to alkanes using a highly dispersed Pd-Mo catalyst.

PubMed

Duan, Haohong; Dong, Juncai; Gu, Xianrui; Peng, Yung-Kang; Chen, Wenxing; Issariyakul, Titipong; Myers, William K; Li, Meng-Jung; Yi, Ni; Kilpatrick, Alexander F R; Wang, Yu; Zheng, Xusheng; Ji, Shufang; Wang, Qian; Feng, Junting; Chen, Dongliang; Li, Yadong; Buffet, Jean-Charles; Liu, Haichao; Tsang, Shik Chi Edman; O'Hare, Dermot

2017-09-19

Bio-oil, produced by the destructive distillation of cheap and renewable lignocellulosic biomass, contains high energy density oligomers in the water-insoluble fraction that can be utilized for diesel and valuable fine chemicals productions. Here, we show an efficient hydrodeoxygenation catalyst that combines highly dispersed palladium and ultrafine molybdenum phosphate nanoparticles on silica. Using phenol as a model substrate this catalyst is 100% effective and 97.5% selective for hydrodeoxygenation to cyclohexane under mild conditions in a batch reaction; this catalyst also demonstrates regeneration ability in long-term continuous flow tests. Detailed investigations into the nature of the catalyst show that it combines hydrogenation activity of Pd and high density of both Brønsted and Lewis acid sites; we believe these are key features for efficient catalytic hydrodeoxygenation behavior. Using a wood and bark-derived feedstock, this catalyst performs hydrodeoxygenation of lignin, cellulose, and hemicellulose-derived oligomers into liquid alkanes with high efficiency and yield.Bio-oil is a potential major source of renewable fuels and chemicals. Here, the authors report a palladium-molybdenum mixed catalyst for the selective hydrodeoxygenation of water-insoluble bio-oil to mixtures of alkanes with high carbon yield.
Nanocrystalline Hierarchical ZSM-5: An Efficient Catalyst for the Alkylation of Phenol with Cyclohexene.

PubMed

Radhika, N P; Selvin, Rosilda; Kakkar, Rita; Roselin, L Selva

2018-08-01

In this paper, authors report the synthesis of nanocrystalline hierarchical zeolite ZSM-5 and its application as a heterogeneous catalyst in the alkylation of phenol with cyclohexene. The catalyst was synthesized by vacuum-concentration coupled hydrothermal technique in the presence of two templates. This synthetic route could successfully introduce pores of higher hierarchy in the zeolite ZSM-5 structure. Hierarchical ZSM-5 could catalyse effectively the industrially important reaction of cyclohexene with phenol. We ascribe the high efficiency of the catalyst to its conducive structural features such as nanoscale size, high surface area, presence of hierarchy of pores and existence of Lewis sites along with Brønsted acid sites. The effect of various reaction parameters like duration, catalyst amount, reactant mole ratio and temperature were assessed. Under optimum reaction conditions, the catalyst showed up to 65% selectivity towards the major product, cyclohexyl phenyl ether. There was no discernible decline in percent conversion or selectivity even when the catalyst was re-used for up to four runs. Kinetic studies were done through regression analysis and a mechanistic route based on LHHW model was suggested.
Catalytic fast pyrolysis of durian rind using silica-alumina catalyst: Effects of pyrolysis parameters.

PubMed

Tan, Y L; Abdullah, A Z; Hameed, B H

2018-05-18

Silica-alumina catalyst was prepared and used in the catalytic fast pyrolysis of durian rind in a drop-type two-stage reactor. The effects of catalytic temperature (400 °C-600 °C) and catalyst-to-durian rind ratio (1:30-3:30) were evaluated. Bio-oil yield was increased with increased catalytic temperature due to considerable dehydration process, but it was reduced with high catalyst loading due to the overcracking of organics into light gases. Silica-alumina catalyst possessed good selectivity and the products changed according to the temperature. The major components in bio-oil were hydrocarbons, furan derivatives, and aromatic compounds at 400 °C, 500 °C, and 600 °C, respectively. The hydrogen and carbon contents of bio-oil were reduced with high catalyst loading due to the overcracking of organics, and the deoxygenation process became unfavorable. The silica-alumina catalyst worked well in catalytic fast pyrolysis of durian rind, and the condition may be adjusted based on the desired products. Copyright © 2018 Elsevier Ltd. All rights reserved.
Low-temperature growth of nitrogen-doped carbon nanofibers by acetonitrile catalytic CVD using Ni-based catalysts

NASA Astrophysics Data System (ADS)

Iwasaki, Tomohiro; Makino, Yuri; Fukukawa, Makoto; Nakamura, Hideya; Watano, Satoru

2016-11-01

To synthesize nitrogen-doped carbon nanofibers (N-CNFs) at high growth rates and low temperatures less than 673 K, nickel species (metallic nickel and nickel oxide) supported on alumina particles were used as the catalysts for an acetonitrile catalytic chemical vapor deposition (CVD) process. The nickel:alumina mass ratio in the catalysts was fixed at 0.05:1. The catalyst precursors were prepared from various nickel salts (nitrate, chloride, sulfate, acetate, and lactate) and then calcined at 1073 K for 1 h in oxidative (air), reductive (hydrogen-containing argon), or inert (pure argon) atmospheres to activate the nickel-based catalysts. The effects of precursors and calcination atmosphere on the catalyst activity at low temperatures were studied. We found that the catalysts derived from nickel nitrate had relatively small crystallite sizes of nickel species and provided N-CNFs at high growth rates of 57 ± 4 g-CNF/g-Ni/h at 673 K in the CVD process using 10 vol% hydrogen-containing argon as the carrier gas of acetonitrile vapor, which were approximately 4 times larger than that of a conventional CVD process. The obtained results reveal that nitrate ions in the catalyst precursor and hydrogen in the carrier gas can contribute effectively to the activation of catalysts in low-temperature CVD. The fiber diameter and nitrogen content of N-CNFs synthesized at high growth rates were several tens of nanometers and 3.5 ± 0.3 at.%, respectively. Our catalysts and CVD process may lead to cost reductions in the production of N-CNFs.
Silica nanosphere-supported palladium(II) furfural complex as a highly efficient and recyclable catalyst for oxidative amination of aldehydes.

PubMed

Sharma, R K; Sharma, Shivani

2014-01-21

The present work reports the fabrication of a novel and highly efficient silica nanospheres-based palladium catalyst (SiO2@APTES@Pd-FFR) via immobilization of a palladium complex onto silica nanospheres functionalized with 3-aminopropyltriethoxysilane (APTES), and its catalytic application for the oxidative amination of aldehydes to yield commercially important amides. The structure of the nano-catalyst was confirmed by Solid-state (13)C CPMAS and (29)Si CPMAS NMR spectroscopy, Brunauer-Emmett-Teller (BET) surface area analysis, Fourier transform infrared spectroscopy (FT-IR), Energy dispersive X-ray fluorescence spectroscopy (ED-XRF), Atomic absorption spectroscopy (AAS), Transmission electron microscopy (TEM) and elemental analysis. The nano-catalyst was found to be highly effective for the oxidative amination of aldehydes using hydrogen peroxide as an environmentally benign oxidant to give amides. The effect of various reaction parameters such as temperature, amount of catalyst, reaction time, type of solvent, oxidant used, substrate to oxidant ratio etc. have been demonstrated to achieve high catalytic efficacy. Moreover, this nanostructured catalyst could be recovered with simplicity and reused for several cycles without any significant loss in its catalytic activity. In addition, the stability of the reused nano-catalyst was proved by FT-IR and HRTEM techniques. It is worth noting that the features of mild reaction conditions, simple work-up procedure, high product yield, no use of toxic organic solvents, high turn-over frequency (TOF), and easy recovery and reusability of the present quasi-homogeneous nano-catalyst make this protocol an attractive alternative to the existing catalytic methods for the oxidative amination of aldehydes to furnish industrially important amides.
Co-Liquefaction of Elbistan Lignite with Manure Biomass; Part 1. Effect of Catalyst Concentration

NASA Astrophysics Data System (ADS)

Koyunoglu, Cemil; Karaca, Hüseyin

2017-12-01

The hydrogenation of coal by molecular hydrogen has not been appreciable unless a catalyst has been used, especially at temperatures below 500 °C. Conversion under these conditions is essentially the result of the pyrolysis of coal, although hydrogen increases the yield of conversion due to the stabilization of radicals and other reactive species. Curtis and his co-workers has shown that highly effective and accessible catalyst are required to achieve high levels of oil production from the coprocessing of coal and heavy residua. In their work, powdered hydrotreating catalyst at high loadings an oil-soluble metal salts of organic acids as catalyst precursors achieved the highest levels of activity for coal conversion and oil production. Red mud which is iron-based catalysed has been used in several co-processing studies. It was used as an inexpensive sulphur sink for the H2S evolved to convert Fe into pyrrohotite during coal liquefaction. In this study, Elbistan Lignite (EL) processed with manure using red mud as a catalyst with the range of concentration from 3% to 12%. The main point of using red mud catalyst is to enhance oil products yield of coal liquefaction, which deals with its catalytic activity. On the other hand, red mud acts on EL liquefaction with manure as a catalyst and represents an environmental option to produce lower sulphur content oil products as well.
Understanding the performance and mechanism of Mg-containing oxides as support catalysts in the thermal dry reforming of methane.

PubMed

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

PubMed Central

Khairudin, Nor Fazila; Sukri, Mohd Farid Fahmi; Khavarian, Mehrnoush

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. PMID:29719767

Highly efficient organosolv fractionation of cornstalk into cellulose and lignin in organic acids.

PubMed

Shui, Tao; Feng, Shanghuan; Yuan, Zhongshun; Kuboki, Takashi; Xu, Chunbao Charles

2016-10-01

In this study, effects of fractionation solvents, catalysts, temperatures and residence time on yields, purity and chemical composition of the products were investigated at the solid/solvent ratio of 1:5 (g/g). It was revealed that mixture of acetic acid/formic acid/water at the ratio of 3:6:1 (v/v/v) resulted in crude cellulose and lignin products of relatively high purity. The use of HCl catalyst contributed to a high crude cellulose yield, while H2SO4 showed an adverse effect on cellulose yield. However, both of these acidic catalysts contributed to much lower hemicellulose contents in the resulted crude cellulose products compared with those obtained without a catalyst. Fractionation at 90°C for 180min in mixed solvents of acetic acid/formic acid/water (3:6:1, v/v/v) with or without catalyst produced crude cellulose with very low residual lignin contents (<4%). Copyright © 2016. Published by Elsevier Ltd.
TiO2 Nanotube-Carbon (TNT-C) as Support for Pt-based Catalyst for High Methanol Oxidation Reaction in Direct Methanol Fuel Cell.

PubMed

Abdullah, M; Kamarudin, S K; Shyuan, L K

2016-12-01

In this study, TiO 2 nanotubes (TNTs) were synthesized via a hydrothermal method using highly concentrated NaOH solutions varying from 6 to 12 M at 180 °C for 48 h. The effects of the NaOH concentration and the TNT crystal structure on the performance for methanol oxidation were investigated to determine the best catalyst support for Pt-based catalysts. The results showed that TNTs produced with 10 M NaOH exhibited a length and a diameter of 550 and 70 nm, respectively; these TNTs showed the best nanotube structure and were further used as catalyst supports for a Pt-based catalyst in a direct methanol fuel cell. The synthesized TNT and Pt-based catalysts were analysed by FESEM, TEM, BET, EDX, XRD and FTIR. The electrochemical performance of the catalysts was investigated using cyclic voltammetry (CV) and chronoamperometric (CA) analysis to further understand the methanol oxidation in the direct methanol fuel cell (DMFC). Finally, the result proves that Pt-Ru/TNT-C catalyst shows high performance in methanol oxidation as the highest current density achieved at 3.3 mA/cm 2 (normalised by electrochemically active surface area) and high catalyst tolerance towards poisoning species was established.
In situ Generated Ruthenium Catalyst Systems Bearing Diverse N-Heterocyclic Carbene Precursors for Atom-Economic Amide Synthesis from Alcohols and Amines.

PubMed

Cheng, Hua; Xiong, Mao-Qian; Cheng, Chuan-Xiang; Wang, Hua-Jing; Lu, Qiang; Liu, Hong-Fu; Yao, Fu-Bin; Chen, Cheng; Verpoort, Francis

2018-02-16

The transition-metal-catalyzed direct synthesis of amides from alcohols and amines is herein demonstrated as a highly environmentally benign and atom-economic process. Among various catalyst systems, in situ generated N-heterocyclic carbene (NHC)-based ruthenium (Ru) halide catalyst systems have been proven to be active for this transformation. However, these existing catalyst systems usually require an additional ligand to achieve satisfactory results. In this work, through extensive screening of a diverse variety of NHC precursors, we discovered an active in situ catalyst system for efficient amide synthesis without any additional ligand. Notably, this catalyst system was found to be insensitive to the electronic effects of the substrates, and various electron-deficient substrates, which were not highly reactive with our previous catalyst systems, could be employed to afford the corresponding amides efficiently. Furthermore, mechanistic investigations were performed to provide a rationale for the high activity of the optimized catalyst system. NMR-scale reactions indicated that the rapid formation of a Ru hydride intermediate (signal at δ=-7.8 ppm in the 1 H NMR spectrum) after the addition of the alcohol substrate should be pivotal in establishing the high catalyst activity. Besides, HRMS analysis provided possible structures of the in situ generated catalyst system. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
Heterometallic metal-organic framework-templated synthesis of porous Co3O4/ZnO nanocage catalysts for the carbonylation of glycerol

NASA Astrophysics Data System (ADS)

Lü, Yinyun; Jiang, Yating; Zhou, Qi; Li, Yunmei; Chen, Luning; Kuang, Qin; Xie, Zhaoxiong; Zheng, Lansun

2017-12-01

The efficient synthesis of glycerol carbonate (GLC) has recently received great attention due to its significance in reducing excess glycerol in biodiesel production as well as its promising applications in several industrial fields. However, the achievement of high conversion and high selectivity of GLC from glycerol in heterogeneous catalytic processes remains a challenge due to the absence of high-performance solid catalysts. Herein, highly porous nanocage catalysts composed of well-mixed Co3O4 and ZnO nanocrystals were successfully fabricated via a facile heterometallic metal-organic framework (MOF)-templated synthetic route. Benefiting from a high porosity and the synergistic effect between Co3O4 and ZnO, the as-prepared composite catalysts exhibited a significantly enhanced production efficiency of GLC in the carbonylation reaction of glycerol with urea compared to the single-component counterparts. The yield of GLC over the Co50Zn50-350 catalyst reached 85.2%, with 93.3% conversion and near 91% GLC selectivity, and this catalytic performance was superior to that over most heterogeneous catalysts. More importantly, the proposed templated synthetic strategy of heterometallic MOFs facilitates the regulation of catalyst composition and surface structure and can therefore be potentially extended in the tailoring of other metal oxide composite catalysts.
Novel nano-semiconductor film layer supported nano-Pd Complex Nanostructured Catalyst Pd/Ⓕ-MeOx/AC for High Efficient Selective Hydrogenation of Phenol to Cyclohexanone.

PubMed

Si, Jiaqi; Ouyang, Wenbing; Zhang, Yanji; Xu, Wentao; Zhou, Jicheng

2017-04-28

Supported metal as a type of heterogeneous catalysts are the most widely used in industrial processes. High dispersion of the metal particles of supported catalyst is a key factor in determining the performance of such catalysts. Here we report a novel catalyst Pd/Ⓕ-MeO x /AC with complex nanostructured, Pd nanoparticles supported on the platelike nano-semiconductor film/activated carbon, prepared by the photocatalytic reduction method, which exhibited high efficient catalytic performance for selective hydrogenation of phenol to cyclohexanone. Conversion of phenol achieved up to more than 99% with a lower mole ratio (0.5%) of active components Pd and phenol within 2 h at 70 °C. The synergistic effect of metal nanoparticles and nano-semiconductors support layer and the greatly increasing of contact interface of nano-metal-semiconductors may be responsible for the high efficiency. This work provides a clear demonstration that complex nanostructured catalysts with nano-metal and nano-semiconductor film layer supported on high specific surface AC can yield enhanced catalytic activity and can afford promising approach for developing new supported catalyst.
Thermally stable single-atom platinum-on-ceria catalysts via atom trapping

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

Jones, John; Xiong, Haifeng; DelaRiva, Andrew

2016-07-08

Catalysts based on single atoms of scarce precious metals can lead to more efficient use through enhanced reactivity and selectivity. However, single atoms on catalyst supports can be mobile and aggregate into nanoparticles when heated at elevated temperatures. High temperatures are detrimental to catalyst performance unless these mobile atoms can be trapped. We used ceria powders having similar surface areas but different exposed surface facets. When mixed with a platinum/ aluminum oxide catalyst and aged in air at 800°C, the platinum transferred to the ceria and was trapped. Polyhedral ceria and nanorods were more effective than ceria cubes at anchoringmore » the platinum. Performing synthesis at high temperatures ensures that only the most stable binding sites are occupied, yielding a sinter-resistant, atomically dispersed catalyst.« less
DOE Office of Scientific and Technical Information (OSTI.GOV)

Not Available

Twelve catalyst test runs were made; ten of these runs used catalysts that contained cobalt as the metal component, while the remaining two runs used catalysts that contained iron as the metal component. Five of the ten cobalt catalyst test runs were made with the catalysts containing one of two different shape selective components (UCC-101 and UCC-108) at two different metal component: shape selective component ratios (1:1 and 3:14). The remaining five cobalt catalyst test runs were made with the catalysts containing different additives incorporated into the cobalt. The five cobalt catalyst test runs using catalysts with different additives showedmore » that these additives had pronounced effects on the catalysts' activity, selectivity, and stability. The most outstanding effect was realized with the additive used in the Run 9 catalyst. This additive greatly improved the stability of the catalyst. While having the same initial activity of an additive-free catalyst, its deactivation rate was only one fourth of that of the additive-free catalyst. Futhermore, this additive improved the quality of the hydrocarbon product, which had a high, stable yield of olefins, and, unlike the product of any other cobalt/UCC-101 catalyst, was free of suspended wax. This lack of suspended wax resulted in jet fuel and diesel oil fractions that had substantially lower pour points than did the fractions produced from an additive-free catalyst.« less
Ambient temperature NO oxidation over Cr-based amorphous mixed oxide catalysts: effects from the second oxide components

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

Wang, Aiyong; Lin, Bo; Zhang, Hanlei

2017-01-01

Three series of Cr-based mixed oxides (Cr-Co, Cr-Fe, and Cr-Ni oxides) with high specific surface areas and amorphous textures were synthesized using a novel sol-gel method. These mixed oxides, in comparison to their pure metal oxide (CrOx, Co3O4, FeOx and NiO) counterparts, display enhanced performance for catalytic oxidation of low-concentration NO at room temperature. The best performing catalysts achieve 100% NO conversion for ~30 h of operation at a high space velocity of 45,000 ml g-1 h-1. The amorphous structure was found to be critical for these catalysts to maintain high activity and durability. Control of Cr/M (M=Co, Fe andmore » Ni) molar ratio, nitrate precursor decomposition temperature and catalyst calcination temperature was key to the synthesis of these highly active catalysts.« less
Development of inexpensive metal macrocyclic complexes for use in fuel cells

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

Doddapaneni, N.; Ingersoll, D.; Kosek, J.A.

Several metal macrocyclic complexes were synthesized for use as catalysts in fuel cells. An initial evaluation of their ability to catalyze the fuel cell reactions were completed. Based on this initial evaluation, one metal macrocyclic catalyst was selected and long-term stability testing in a fuel cell was initiated. The fuel cell employing this catalyst was operated continuously for one year with little signs of catalyst degradation. The effect of synthetic reformates on the performance of the catalyst in the fuel cell environment also demonstrated high tolerance of this catalyst for common contaminants and poisons.
Hydrogen production via reforming of biogas over nanostructured Ni/Y catalyst: Effect of ultrasound irradiation and Ni-content on catalyst properties and performance

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

Sharifi, Mahdi; Reactor and Catalysis Research Center; Haghighi, Mohammad, E-mail: haghighi@sut.ac.ir

2014-12-15

Highlights: • Synthesis of nanostructured Ni/Y catalyst by sonochemical and impregnation methods. • Enhancement of size distribution and active phase dispersion by employing sonochemical method. • Evaluation of biogas reforming over Ni/Y catalyst with different Ni-loadings. • Preparation of highly active and stable catalyst with low Ni content for biogas reforming. • Getting H{sub 2}/CO very close to equilibrium ratio by employing sonochemical method. - Abstract: The effect of ultrasound irradiation and various Ni-loadings on dispersion of active phase over zeolite Y were evaluated in biogas reforming for hydrogen production. X-ray diffraction, field emission scanning electron microscopy, energy dispersive X-ray,more » Brunauer–Emmett–Teller, Fourier transform infrared analysis and TEM analysis were employed to observe the characteristics of nanostructured catalysts. The characterizations implied that utilization of ultrasound irradiation enhanced catalyst physicochemical properties including high dispersion of Ni on support, smallest particles size and high catalyst surface area. The reforming reactions were carried out at GHSV = 24 l/g.h, P = 1 atm, CH{sub 4}/CO{sub 2} = 1 and temperature range of 550–850 °C. Activity test displayed that ultrasound irradiated Ni(5 wt.%)/Y had the best performance and the activity remained stable during 600 min. Furthermore, the proposed reaction mechanism showed that there are three major reaction channels in biogas reforming.« less
Effects of copper-precursors on the catalytic activity of Cu/graphene catalysts for the selective catalytic oxidation of ammonia

NASA Astrophysics Data System (ADS)

Li, Jingying; Tang, Xiaolong; Yi, Honghong; Yu, Qingjun; Gao, Fengyu; Zhang, Runcao; Li, Chenlu; Chu, Chao

2017-08-01

Different copper-precursors were used to prepare Cu/graphene catalysts by an impregnation method. XRD, Raman spectra, TEM, BET, XPS, H2-TPR, NH3-TPD, DRIFTS and catalytic activity test were used to characterize and study the effect of precursors on the catalytic activity of Cu/graphene catalysts for NH3-SCO reaction. The large specific surface area of Cu/graphene catalysts and high dispersion of the metal particles on the graphene caused the well catalytic activity of NH3-SCO reaction. Compared to Cu/GE(AC), Cu/GE(N) showed better catalytic performance, and the complete NH3 removal efficiency was obtained at 250 °C with N2 selectivity of 85%. The copper-precursors had influence on the distribution of surface Cu species and further affected the catalytic activity of Cu/GE catalysts. The more amount of surface Cu species and highly dispersed CuO particles on the graphene surface formed by using copper nitrate as precursor could significantly improve the reducibility of catalysts and enhance NH3 adsorption, thereby improving the catalytic activity of Cu/graphene catalyst.
High-performance oxygen reduction catalysts in both alkaline and acidic fuel cells based on pre-treating carbon material and iron precursor

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

Song, Ping; Barkholtz, Heather M.; Wang, Ying

We demonstrate a new and simple method for pre-treating the carbon material and iron precursor to prepare oxygen reduction reaction (ORR) catalysts, which can produce super-high performance and stability in alkaline solution, with high performance in acid solution. This strategy using cheap materials is simply controllable. Moreover, it has achieved smaller uniform nanoparticles to exhibit high stability, and the synergetic effect of Fe and N offered much higher performance in ORR than commercial Pt/C, with high maximum power density in alkaline and acid fuel cell test. So it can make this kind of catalysts be the most promising alternatives ofmore » Pt-based catalysts with best performance/price.« less
Hexagonal boron nitride catalyst in a fixed-bed reactor for exothermic propane oxidation dehydrogenation

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

Tian, Jinshu; Lin, Jinhan; Xu, Mingliang

Hexagonal boron nitride (h-BN) with high thermal conductivity is potentially an effective catalyst for highly exothermic propane oxidative dehydrogenation (ODH) reaction. Here, we report our experimental and theoretic studies of such a catalyst for propane ODH in a fixed-bed reactor. Based on the computational fluid dynamics calculation (CFD) results, the catalyst bed temperature increases by less than 1°C in the h-BN catalyst bed which is much smaller than that (8°C) in the VO x/γ-Al 2O 3 catalyst bed at a similar propane conversion (25%) using a micro-tubular reactor with a diameter of 6 mm. Even in an industrially relevant reactormore » with an inner diameter of 60 mm, a uniform temperature profile can still be maintained using the h-BN catalyst bed due to its excellent thermal conductivity as opposed to a temperature gradient of 47°C in the VO x/γ-Al 2O 3 catalyst bed. The results reported here provide useful information for potential application of h-BN catalyst in propane ODH.« less
Active site formation mechanism of carbon-based oxygen reduction catalysts derived from a hyperbranched iron phthalocyanine polymer.

PubMed

Hiraike, Yusuke; Saito, Makoto; Niwa, Hideharu; Kobayashi, Masaki; Harada, Yoshihisa; Oshima, Masaharu; Kim, Jaehong; Nabae, Yuta; Kakimoto, Masa-Aki

2015-01-01

Carbon-based cathode catalysts derived from a hyperbranched iron phthalocyanine polymer (HB-FePc) were characterized, and their active-site formation mechanism was studied by synchrotron-based spectroscopy. The properties of the HB-FePc catalyst are compared with those of a catalyst with high oxygen reduction reaction (ORR) activity synthesized from a mixture of iron phthalocyanine and phenolic resin (FePc/PhRs). Electrochemical measurements demonstrate that the HB-FePc catalyst does not lose its ORR activity up to 900°C, whereas that of the FePc/PhRs catalyst decreases above 700°C. Hard X-ray photoemission spectra reveal that the HB-FePc catalysts retain more nitrogen components than the FePc/PhRs catalysts between pyrolysis temperatures of 600°C and 800°C. This is because the linked structure of the HB-FePc precursor has high thermostability against nitrogen desorption. Consequently, effective doping of active nitrogen species into the sp (2) carbon network of the HB-FePc catalysts may occur up to 900°C.
Hexagonal boron nitride catalyst in a fixed-bed reactor for exothermic propane oxidation dehydrogenation

DOE PAGES

Tian, Jinshu; Lin, Jinhan; Xu, Mingliang; ...

2018-04-17

Hexagonal boron nitride (h-BN) with high thermal conductivity is potentially an effective catalyst for highly exothermic propane oxidative dehydrogenation (ODH) reaction. Here, we report our experimental and theoretic studies of such a catalyst for propane ODH in a fixed-bed reactor. Based on the computational fluid dynamics calculation (CFD) results, the catalyst bed temperature increases by less than 1°C in the h-BN catalyst bed which is much smaller than that (8°C) in the VO x/γ-Al 2O 3 catalyst bed at a similar propane conversion (25%) using a micro-tubular reactor with a diameter of 6 mm. Even in an industrially relevant reactormore » with an inner diameter of 60 mm, a uniform temperature profile can still be maintained using the h-BN catalyst bed due to its excellent thermal conductivity as opposed to a temperature gradient of 47°C in the VO x/γ-Al 2O 3 catalyst bed. The results reported here provide useful information for potential application of h-BN catalyst in propane ODH.« less
Fe-porphyrin-based metal–organic framework films as high-surface concentration, heterogeneous catalysts for electrochemical reduction of CO 2

DOE PAGES

Hod, Idan; Sampson, Matthew D.; Deria, Pravas; ...

2015-09-18

Realization of heterogeneous electrochemical CO 2-to-fuel conversion via molecular catalysis under high-flux conditions requires the assembly of large quantities of reactant-accessible catalysts on conductive surfaces. As a proof of principle, we demonstrate that electrophoretic deposition of thin films of an appropriately chosen metal–organic framework (MOF) material is an effective method for immobilizing the needed quantity of catalyst. For electrocatalytic CO 2 reduction, we used a material that contains functionalized Fe-porphyrins as catalytically competent, redox-conductive linkers. The approach yields a high effective surface coverage of electrochemically addressable catalytic sites (~10 15 sites/cm 2). The chemical products of the reduction, obtained withmore » ~100% Faradaic efficiency, are mixtures of CO and H 2. The results validate the strategy of using MOF chemistry to obtain porous, electrode-immobilized, networks of molecular catalysts having competency for energy-relevant electrochemical reactions.« less
The effect of precipitants on Ni-Al2O3 catalysts prepared by a co-precipitation method for internal reforming in molten carbonate fuel cells

PubMed Central

Jung, You-Shick; Yoon, Wang-Lai; Seo, Yong-Seog; Rhee, Young-Woo

2012-01-01

Ni-Al2O3 catalysts are prepared via the co-precipitation method using various precipitants: urea, Na2CO3, NaOH, K2CO3, KOH and NH4OH. The effects of the precipitants on the physicochemical properties and catalytic activities of the Ni-Al2O3 catalysts are investigated. The Ni50-urea catalyst displays the largest specific surface area and the highest pore volume. This catalyst also exhibits the highest Ni dispersion and the largest Ni surface area. Ni50-urea catalyst prepared with urea as precipitant and Ni50-K2CO3 catalyst prepared with K2CO3 as precipitant exhibit high pore volumes and good catalytic activities for methane steam reforming. The Ni50-urea catalyst exhibits the best physicochemical properties and shows good catalytic activity and a strong resistance to electrolyte contamination. PMID:22962548
Methanol oxidation reaction on core-shell structured Ruthenium-Palladium nanoparticles: Relationship between structure and electrochemical behavior

NASA Astrophysics Data System (ADS)

Kübler, Markus; Jurzinsky, Tilman; Ziegenbalg, Dirk; Cremers, Carsten

2018-01-01

In this work the relationship between structural composition and electrochemical characteristics of Palladium(Pd)-Ruthenium(Ru) nanoparticles during alkaline methanol oxidation reaction is investigated. The comparative study of a standard alloyed and a precisely Ru-core-Pd-shell structured catalyst allows for a distinct investigation of the electronic effect and the bifunctional mechanism. Core-shell catalysts benefit from a strong electronic effect and an efficient Pd utilization. It is found that core-shell nanoparticles are highly active towards methanol oxidation reaction for potentials ≥0.6 V, whereas alloyed catalysts show higher current outputs in the lower potential range. However, differential electrochemical mass spectrometry (DEMS) experiments reveal that the methanol oxidation reaction on core-shell structured catalysts proceeds via the incomplete oxidation pathway yielding formaldehyde, formic acid or methyl formate. Contrary, the alloyed catalyst benefits from the Ru atoms at its surface. Those are found to be responsible for high methanol oxidation activity at lower potentials as well as for complete oxidation of CH3OH to CO2 via the bifunctional mechanism. Based on these findings a new Ru-core-Pd-shell-Ru-terrace catalyst was synthesized, which combines the advantages of the core-shell structure and the alloy. This novel catalyst shows high methanol electrooxidation activity as well as excellent selectivity for the complete oxidation pathway.
Ordered mesoporous porphyrinic carbons with very high electrocatalytic activity for the oxygen reduction reaction

PubMed Central

Cheon, Jae Yeong; Kim, Taeyoung; Choi, YongMan; Jeong, Hu Young; Kim, Min Gyu; Sa, Young Jin; Kim, Jaesik; Lee, Zonghoon; Yang, Tae-Hyun; Kwon, Kyungjung; Terasaki, Osamu; Park, Gu-Gon; Adzic, Radoslav R.; Joo, Sang Hoon

2013-01-01

The high cost of the platinum-based cathode catalysts for the oxygen reduction reaction (ORR) has impeded the widespread application of polymer electrolyte fuel cells. We report on a new family of non-precious metal catalysts based on ordered mesoporous porphyrinic carbons (M-OMPC; M = Fe, Co, or FeCo) with high surface areas and tunable pore structures, which were prepared by nanocasting mesoporous silica templates with metalloporphyrin precursors. The FeCo-OMPC catalyst exhibited an excellent ORR activity in an acidic medium, higher than other non-precious metal catalysts. It showed higher kinetic current at 0.9 V than Pt/C catalysts, as well as superior long-term durability and MeOH-tolerance. Density functional theory calculations in combination with extended X-ray absorption fine structure analysis revealed a weakening of the interaction between oxygen atom and FeCo-OMPC compared to Pt/C. This effect and high surface area of FeCo-OMPC appear responsible for its significantly high ORR activity. PMID:24056308
Ce-Sn binary oxide catalyst for the selective catalytic reduction of NOx by NH3

NASA Astrophysics Data System (ADS)

Liu, Zhiming; Feng, Xu; Zhou, Zizheng; Feng, Yongjun; Li, Junhua

2018-01-01

Ce-Sn binary oxide catalysts prepared by the hydrothermal method have been investigated for the selective catalytic reduction (SCR) of NOx with NH3. Compared with pure CeO2 and SnO2, Ce-Sn binary oxide catalyst showed significantly higher NH3-SCR activity. Moreover, Ce-Sn catalyst showed high resistance against H2O and SO2. The high catalytic performance of Ce-Sn binary oxide is attributed to the synergetic effect between Ce and Sn species, which not only enhances the redox property of the catalyst but also increases the Lewis acidity, thus promoting the adsorption and activation of NH3 species, which contributes to improving the NH3-SCR performance.

Elucidation of reaction mechanism for m -cresol hydrodeoxygenation over Fe based catalysts: A kinetic study

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

Hong, Yongchun; Wang, Yong

Fe based catalysts are promising for hydrodeoxygenation (HDO) of lignin derived phenolics due to their high selectivity for aromatics. In this work, the reaction mechanism of m-cresol HDO on Fe catalysts and the kinetic consequence with Pd addition were elucidated by examining the effect of H2, H2O and m-cresol pressures on toluene formation rate on Fe and PdFe catalysts. A direct CO bond cleavage mechanism is proposed for HDO catalysis on both Fe and PdFe catalysts, while Pd provides a facilitated reaction pathway at the PdFe interface and therefore promotes the catalysis on Fe without changing the high selectivity towardsmore » aromatics.« less
CuCr2O4@rGO Nanocomposites as High-Performance Cathode Catalyst for Rechargeable Lithium-Oxygen Batteries

NASA Astrophysics Data System (ADS)

Liu, Jiandi; Zhao, Yanyan; Li, Xin; Wang, Chunge; Zeng, Yaping; Yue, Guanghui; Chen, Qiang

2018-06-01

Rechargeable lithium-oxygen batteries have been considered as a promising energy storage technology because of their ultra-high theoretical energy densities which are comparable to gasoline. In order to improve the electrochemical properties of lithium-oxygen batteries (LOBs), especially the cycling performance, a high-efficiency cathode catalyst is the most important component. Hence, we aim to demonstrate that CuCr2O4@rGO (CCO@rGO) nanocomposites, which are synthesized using a facile hydrothermal method and followed by a series of calcination processes, are an effective cathode catalyst. The obtained CCO@rGO nanocomposites which served as the cathode catalyst of the LOBs exhibited an outstanding cycling performance for over 100 cycles with a fixed capacity of 1000 mAh g-1 at a current density of 200 mA g-1. The enhanced properties were attributed to the synergistic effect between the high catalytic efficiency of the spinel-structured CCO nanoparticles, the high specific surface area, and high conductivity of the rGO.[Figure not available: see fulltext.
Gold-supported cerium-doped NiO x catalysts for water oxidation

DOE PAGES

Ng, Jia Wei Desmond; García-Melchor, Max; Bajdich, Michal; ...

2016-04-29

Here, the development of high-performance catalysts for the oxygen-evolution reaction (OER) is paramount for cost-effective conversion of renewable electricity to fuels and chemicals. Here we report the significant enhancement of the OER activity of electrodeposited NiO x films resulting from the combined effects of using cerium as a dopant and gold as a metal support. This NiCeO x–Au catalyst delivers high OER activity in alkaline media, and is among the most active OER electrocatalysts yet reported. On the basis of experimental observations and theoretical modelling, we ascribe the activity to a combination of electronic, geometric and support effects, where highlymore » active under-coordinated sites at the oxide support interface are modified by the local chemical binding environment and by doping the host Ni oxide with Ce. The NiCeO x–Au catalyst is further demonstrated in a device context by pairing it with a nickel–molybdenum hydrogen evolution catalyst in a water electrolyser, which delivers 50 mA consistently at 1.5 V over 24 h of continuous operation.« less
Highly efficient and robust molecular ruthenium catalysts for water oxidation

PubMed Central

Duan, Lele; Araujo, Carlos Moyses; Ahlquist, Mårten S.G.; Sun, Licheng

2012-01-01

Water oxidation catalysts are essential components of light-driven water splitting systems, which could convert water to H2 driven by solar radiation (H2O + hν → 1/2O2 + H2). The oxidation of water (H2O → 1/2O2 + 2H+ + 2e-) provides protons and electrons for the production of dihydrogen (2H+ + 2e- → H2), a clean-burning and high-capacity energy carrier. One of the obstacles now is the lack of effective and robust water oxidation catalysts. Aiming at developing robust molecular Ru-bda (H2bda = 2,2′-bipyridine-6,6′-dicarboxylic acid) water oxidation catalysts, we carried out density functional theory studies, correlated the robustness of catalysts against hydration with the highest occupied molecular orbital levels of a set of ligands, and successfully directed the synthesis of robust Ru-bda water oxidation catalysts. A series of mononuclear ruthenium complexes [Ru(bda)L2] (L = pyridazine, pyrimidine, and phthalazine) were subsequently synthesized and shown to effectively catalyze CeIV-driven [CeIV = Ce(NH4)2(NO3)6] water oxidation with high oxygen production rates up to 286 s-1 and high turnover numbers up to 55,400. PMID:22753518
An optimization study of PtSn/C catalysts applied to direct ethanol fuel cell: Effect of the preparation method on the electrocatalytic activity of the catalysts

NASA Astrophysics Data System (ADS)

Almeida, T. S.; Palma, L. M.; Leonello, P. H.; Morais, C.; Kokoh, K. B.; De Andrade, A. R.

2012-10-01

The aim of this work was to perform a systematic study of the parameters that can influence the composition, morphology, and catalytic activity of PtSn/C nanoparticles and compare two different methods of nanocatalyst preparation, namely microwave-assisted heating (MW) and thermal decomposition of polymeric precursors (DPP). An investigation of the effects of the reducing and stabilizing agents on the catalytic activity and morphology of Pt75Sn25/C catalysts prepared by microwave-assisted heating was undertaken for optimization purposes. The effect of short-chain alcohols such as ethanol, ethylene glycol, and propylene glycol as reducing agents was evaluated, and the use of sodium acetate and citric acid as stabilizing agents for the MW procedure was examined. Catalysts obtained from propylene glycol displayed higher catalytic activity compared with catalysts prepared in ethylene glycol. Introduction of sodium acetate enhanced the catalytic activity, but this beneficial effect was observed until a critical acetate concentration was reached. Optimization of the MW synthesis allowed for the preparation of highly dispersed catalysts with average sizes lying between 2.0 and 5.0 nm. Comparison of the best catalyst prepared by MW with a catalyst of similar composition prepared by the polymeric precursors method showed that the catalytic activity of the material can be improved when a proper condition for catalyst preparation is achieved.
Relationship between surface property and catalytic application of amorphous NiP/Hβ catalyst for n-hexane isomerization

NASA Astrophysics Data System (ADS)

Chen, Jinshe; Duan, Zunbin; Song, Zhaoyang; Zhu, Lijun; Zhou, Yulu; Xiang, Yuzhi; Xia, Daohong

2017-12-01

The amorphous NiP nanoparticles were synthesized and a novel amorphous NiP/Hβ catalyst was prepared successfully further. Due to the superior surface property of amorphous NiP/Hβ catalyst, it exhibited good catalytic application for n-hexane isomerization. The catalytic activity of amorphous NiP/Hβ catalyst was close to that of the prepared Pt/Hβ sample, and better than that of commercial catalyst and crystalline Ni2P/Hβ catalyst. What's more, the amorphous NiP/Hβ catalyst shows high resistance to different sulfur compounds and water on account of its unique surface property. The effect of loading amounts on surface property and catalytic performance was investigated, and the structure-function relationship among them was studied ulteriorly. The results demonstrate that loading amounts have effect on textural property and surface acid property, which further affect the catalytic performance. The 10 wt.% NiP/Hβ sample has appropriate pore structure and acid property with uniformly dispersed NiP nanoparticles on surface, which is helpful for providing suitable synergistic effect. The effects of reaction conditions on surface reactions and the mechanism for n-hexane isomerization were investigated further. Based on these results, the amorphous NiP/Hβ catalyst with superior surface property probably pavesa way to overcome the drawbacks of traditional noble metal catalyst, which shows good catalytic application prospects.
An efficient molybdenum disulfide/cobalt diselenide hybrid catalyst for electrochemical hydrogen generation

PubMed Central

Gao, Min-Rui; Liang, Jin-Xia; Zheng, Ya-Rong; Xu, Yun-Fei; Jiang, Jun; Gao, Qiang; Li, Jun; Yu, Shu-Hong

2015-01-01

The electroreduction of water for sustainable hydrogen production is a critical component of several developing clean-energy technologies, such as water splitting and fuel cells. However, finding a cheap and efficient alternative catalyst to replace currently used platinum-based catalysts is still a prerequisite for the commercialization of these technologies. Here we report a robust and highly active catalyst for hydrogen evolution reaction that is constructed by in situ growth of molybdenum disulfide on the surface of cobalt diselenide. In acidic media, the molybdenum disulfide/cobalt diselenide catalyst exhibits fast hydrogen evolution kinetics with onset potential of −11 mV and Tafel slope of 36 mV per decade, which is the best among the non-noble metal hydrogen evolution catalysts and even approaches to the commercial platinum/carbon catalyst. The high hydrogen evolution activity of molybdenum disulfide/cobalt diselenide hybrid is likely due to the electrocatalytic synergistic effects between hydrogen evolution-active molybdenum disulfide and cobalt diselenide materials and the much increased catalytic sites. PMID:25585911
A delafossite-based copper catalyst for sustainable Cl2 production by HCl oxidation.

PubMed

Mondelli, Cecilia; Amrute, Amol P; Schmidt, Timm; Pérez-Ramírez, Javier

2011-07-07

A copper catalyst based on a delafossite precursor (CuAlO(2)) displays high activity and extraordinary lifetime in the gas-phase oxidation of HCl to Cl(2), representing a cost-effective alternative to RuO(2)-based catalysts for chlorine recycling. This journal is © The Royal Society of Chemistry 2011
Instruments for Characterizing Carbon and Sulfur-Resistant Core-Shell Redox Catalysts for Combined Hydrocarbon Reforming and Water-Splitting

DTIC Science & Technology

2015-11-22

SECURITY CLASSIFICATION OF: This project aims to investigate a novel core-shell redox catalyst for combined methane partial oxidation and water...Properly designed redox catalyst are shown to be highly effective for syngas production (from methane ) and water-splitting. The resulting syngas has a...27709-2211 redox catalyst, methane partial oxidation, water-splitting REPORT DOCUMENTATION PAGE 11. SPONSOR/MONITOR’S REPORT NUMBER(S) 10. SPONSOR
High Throughput Spectroscopic Catalyst Screening via Surface Plasmon Spectroscopy

DTIC Science & Technology

2014-05-10

this spectroscopic method can distinguish different catalysts . We also find we can directly investigate the role of different support materials. (ii...dispersed onto glass or within various oxide matrices (e.g. ZnO, silica , titania) as long as they do not scatter light. II. Preparation of Catalyst ...effectively, while gold on silica does not function as a catalyst . • Hydrogen does not dissociate on gold nanoaprticles on TiO2 in N2:H2 mixtures
Fe2P as a novel efficient catalyst promoter in Pd/C system for formic acid electro-oxidation in fuel cells reaction

NASA Astrophysics Data System (ADS)

Wang, Fulong; Xue, Huaiguo; Tian, Zhiqun; Xing, Wei; Feng, Ligang

2018-01-01

Developing catalyst promoter for Pd/C catalyst is significant for the catalytic ability improvement in energy transfer related electrochemical reactions. Herein, we demonstrate Fe2P as an efficient catalyst promoter in Pd/C catalyst system for formic acid electro-oxidation in fuel cells reactions. Adding Fe2P in the Pd/C catalyst system greatly increases the performances for formic acid oxidation by 3-4 times; the CO stripping technique displays two kinds of active sites formation in the Pd-Fe2P/C catalyst system coming from the interaction of Pd, Fe2P and Pd oxide species and both are more efficient for formic acid and CO-species electrooxidation. The smaller charge transfer resistance and Tafel slope for formic acid oxidation indicate the improvements in kinetics by Fe2P in the Pd-Fe2P/C system. The nanostructured hybrid units of Pd, Fe2P and carbon are evidently visible in the high resolution microscopy images and XPS technique confirmes the electronic effect in the catalyst system. The promotion effect of Fe2P in the catalyst system arising from the structure, composition and electronic effect changes is discussed with the help from multiple physical and electrochemical techniques. It is concluded that Fe2P as a significant catalyst promoter will have potential application in energy transfer related electrochemical reactions.
Highly Effective Pt-Based Water-Gas Shift Catalysts by Surface Modification with Alkali Hydroxide Salts

DOE PAGES

Kusche, Matthias; Bustillo, Karen; Agel, Friederike; ...

2015-01-29

Here, we describe an economical and convenient method to improve the performance of Pt/alumina catalysts for the water–gas shift reaction through surface modification of the catalysts with alkali hydroxides according to the solid catalyst with ionic liquid layer approach. The results are in agreement with our findings reported earlier for methanol steam reforming. This report indicates that alkali doping of the catalyst plays an important role in the observed catalyst activation. In addition, the basic and hygroscopic nature of the salt coating contributes to a significant improvement in the performance of the catalyst. During the reaction, a partly liquid filmmore » of alkali hydroxide forms on the alumina surface, which increases the availability of H 2O at the catalytically active sites. Kinetic studies reveal a negligible effect of the KOH coating on the rate dependence of CO and H 2O partial pressures. In conclusion, TEM studies indicate an agglomeration of the active Pt clusters during catalyst preparation; restructuring of Pt nanoparticles occurs under reaction conditions, which leads to a highly active and stable system over 240h time on stream. Excessive pore fillings with KOH introduce a mass transfer barrier as indicated in a volcano-shaped curve of activity versus salt loading. The optimum KOH loading was found to be 7.5wt%.« less
Electrochemical treatment of aqueous solutions of organic pollutants by electro-Fenton with natural heterogeneous catalysts under pressure using Ti/IrO2-Ta2O5 or BDD anodes.

PubMed

Ltaïef, Aziza Hadj; Sabatino, Simona; Proietto, Federica; Ammar, Salah; Gadri, Abdellatif; Galia, Alessandro; Scialdone, Onofrio

2018-07-01

The treatment of toxic organic pollutants by electro-Fenton (EF) presents some drawbacks such as the necessity to work at low pH and the low solubility of oxygen in water contacted with air or oxygen at room pressure that results often in slow and relatively low abatements. Here, the coupled adoption of natural heterogeneous catalysts and of relatively high pressure was proposed in order to improve the performances of EF for the treatment of organic pollutants. Caffeic acid (CA) and 3-chlorophenol were used as model resistant organic pollutants. EF process was performed using both conventional homogeneous FeSO 4 and natural heterogeneous catalysts (pyrite, chalcopyrite, Fe 2 O 3 and Fe 3 O 4 ) as iron catalysts and oxygen at various pressures in the absence or in the presence of BDD anode. The effect of the nature of the catalyst, the oxygen pressure, the current density and the catalyst load was widely investigated in order to optimize the process. It was shown that the coupled utilization of a natural heterogeneous catalyst such as chalcopyrite and a relatively high pressure allows to obtain the total removal of CA and a high removal of the TOC (about 75%) in short times (2 h) with relatively high current efficiencies using an Iridium based anode. In the case of 3-chlorophenol, the utilization of a BDD anode was necessary to achieve a high removal of the pollutant and the TOC. It was shown that the removal of 3-chlorophenol can be effectively performed in different water bodies and with different initial concentrations of 3-chlorophenol. Copyright © 2018 Elsevier Ltd. All rights reserved.
Highly Selective TiN-Supported Highly Dispersed Pt Catalyst: Ultra Active toward Hydrogen Oxidation and Inactive toward Oxygen Reduction.

PubMed

Luo, Junming; Tang, Haibo; Tian, Xinlong; Hou, Sanying; Li, Xiuhua; Du, Li; Liao, Shijun

2018-01-31

The severe dissolution of the cathode catalyst, caused by an undesired oxygen reduction reaction at the anode during startup and shutdown, is a fatal challenge to practical applications of polymer electrolyte membrane fuel cells. To address this important issue, according to the distinct structure-sensitivity between the σ-type bond in H 2 and the π-type bond in O 2 , we design a HD-Pt/TiN material by highly dispersing Pt on the TiN surface to inhibit the unwanted oxygen reduction reaction. The highly dispersed Pt/TiN catalyst exhibits excellent selectivity toward hydrogen oxidation and oxygen reduction reactions. With a Pt loading of 0.88 wt %, our catalyst shows excellent hydrogen oxidation reaction activity, close to that of commercial 20 wt % Pt/C catalyst, and much lower oxygen reduction reaction activity than the commercial 20 wt % Pt/C catalyst. The lack of well-ordered Pt facets is responsible for the excellent selectivity of the HD-Pt/TiN materials toward hydrogen oxidation and oxygen reduction reactions. Our work provides a new and cost-effective solution to design selective catalysts toward hydrogen oxidation and oxygen reduction reactions, making the strategy of using oxygen-tolerant anode catalyst to improve the stability of polymer electrolyte membrane fuel cells during startup and shutdown more affordable and practical.
Pretreatment of CO oxidation catalysts

NASA Technical Reports Server (NTRS)

Vannorman, John D.

1988-01-01

CO oxidation catalysts with high activity in the range of 25 C to 100 C are important for long-life, closed-cycle operation of pulsed carbon dioxide 2 lasers. A reductive pretreatment with either CO or H sub 2 was shown to significantly enhance the activity of a commerically-available platinum on tin (IV) oxide (Pt/SnO2) catalyst relative to an oxidative or inert pretreatment or no pretreatment. Pretreatment at temperatures of 175 C and above caused an initial dip in observed CO or O sub 2 loss or CO sub 2 formation in a test gas mixture of 1 percent CO and 0.5 percent O sub 2 in a He gas matrix before a steady-state yield was obtained. This dip was found to be caused by dehydration of the surface of the catalyst and was readily eliminated by humidifying the catalyst or the test gas mixture. It was also found that too much moisture resulted in a lower overall yield of CO sub 2. Under similar conditions, it is hypothesized that the effect of the humidification is to increase the concentration of OH groups on the surface of the catalyst. The effect of having high concentration of CO sub 2 in the test gas mixture upon the loss of CO and O sub 2 as well as the effect of periods of relaxation of the catalyst under non-test gas conditions was studied. The purpose of these studies was to gain an insight into the mechanism of CO oxidation on this type of catalyst.
Allylic aminations with hindered secondary amine nucleophiles catalyzed by heterobimetallic Pd-Ti complexes.

PubMed

Walker, Whitney K; Anderson, Diana L; Stokes, Ryjul W; Smith, Stacey J; Michaelis, David J

2015-02-06

Phosphinoamide-scaffolded heterobimetallic palladium-titanium complexes are highly effective catalysts for allylic aminations of allylic chlorides with hindered secondary amine nucleophiles. Three titanium-containing ligands are shown to assemble active catalysts in situ and enable catalysis at room temperature. A variety of sterically bulky secondary amines are efficiently allylated in high yields with as little as 1 mol % palladium catalyst. Piperidine and pyrrolidine products are also efficiently generated via intramolecular aminations with hindered amine nucleophiles.
Visible light-induced degradation of acetone over SO42-/MoOx/MgF2 catalysts.

PubMed

He, Yiming; Sheng, Tianlu; Wu, Ying; Chen, Jianshan; Fu, Ruibiao; Hu, Shengming; Wu, Xintao

2009-08-30

A visible light active photodegration catalyst was prepared by doping MoO(3) into MgF(2) matrix. The addition of SO(4)(2-) into MoO(x)/MgF(2) could improve the catalytic activity greatly and an acetone conversion of 96.1% under visible light was obtained on the SO(4)(2-)/5%MoO(x)/MgF(2) (SMM) catalyst. By BET, XRD, Raman, FT-IR, XPS, UV-vis technology the specific area, structure and photoadsorption ability of the catalysts were characterized. The high photocatlaytic activity of the SMM catalyst is attributed to its large specific area, the high dispersal of MoO(3) domains in MgF(2) and the inhibiting effect of MgF(2) matrix on the electron-hole pair recombination.
Electroless plating of Ni-B film as a binder-free highly efficient electrocatalyst for hydrazine oxidation

NASA Astrophysics Data System (ADS)

Wen, Xiao-Ping; Dai, Hong-Bin; Wu, Lin-Song; Wang, Ping

2017-07-01

Hydrazine is a promising energy carrier for fuel cells owing to its combined advantages of high theoretical cell voltage, high-power density, and no greenhouse gas emission. By using an electroless plating process, we have prepared a robust Ni-B film grown on Ni foam that is highly effective for hydrazine electrooxidation in alkaline media. The effects of reaction temperature, concentrations of hydrous hydrazine and sodium hydroxide in the fuel solution on performance of hydrazine electrooxidation reaction are investigated. The mechanistic reason for the property advantage of as-prepared Ni-B/Ni foam catalyst over the relevant catalysts is discussed based on careful kinetics studies and characterization. The facile synthesis of Ni-based catalyst with high activity and good stability is of clear significance for the development of hydrous hydrazine as a viable energy carrier.
DOE Office of Scientific and Technical Information (OSTI.GOV)

Winter, Lea R.; Gomez, Elaine; Yan, Binhang

CO 2 hydrogenation over Fe-modified Ni/CeO 2 catalysts was investigated in a batch reactor using time-resolved in situ FTIR spectroscopy. Low loading of Ni/CeO 2 was associated with high selectivity to CO over CH 4, while higher Ni loading improved CO 2 hydrogenation activity with a reduced CO selectivity. X-ray absorption near-edge structure (XANES) analysis revealed Ni to be metallic for all catalysts including the CO-selective low loading 0.5% Ni catalyst, suggesting that the selectivity trend is due to structural rather than oxidation state effects. The loading amount of 1.5% Ni was selected for co-impregnation with Fe, based on themore » significant shift in product selectivity towards CH 4 for that loading amount, in order to shift the selectivity towards CO while maintaining high activity. Temperature programmed reduction (TPR) results indicated bimetallic interactions between Ni and Fe, and XANES analysis showed that about 70% of Fe in the bimetallic catalysts was oxidized. The Ni-Fe catalysts demonstrated improved selectivity towards CO without significantly compromising activity, coupling the high activity of Ni catalysts and the high CO selectivity of Fe. The general trends in Ni loading and bimetallic modification should guide efforts to develop non-precious metal catalysts for the selective production of CO by CO 2 hydrogenation.« less
Heterogeneous catalytic process for alcohol fuels from syngas

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

Minahan, D.M.; Nagaki, D.A.

1995-12-31

This project is focused on the discovery and evaluation of novel heterogeneous catalyst for the production of oxygenated fuel enhancers from synthesis gas. Catalysts have been studied and optimized for the production of methanol and isobutanol mixtures which may be used for the downstream synthesis of MTBE or related oxygenates. Higher alcohols synthesis (HAS) from syngas was studied; the alcohols that are produced in this process may be used for the downstream synthesis of MTBE or related oxygenates. This work has resulted in the discovery of a catalyst system that is highly selective for isobutanol compared with the prior art.more » The catalysts operate at high temperature (400{degrees}C), and consist of a spinel oxide support (general formula AB{sub 2}O{sub 4}, where A=M{sup 2+} and B = M{sup 3+}), promoted with various other elements. These catalysts operate by what is believed to be an aldol condensation mechanism, giving a product mix of mainly methanol and isobutanol. In this study, the effect of product feed/recycle (methanol, ethanol. n-propanol, isopropanol, carbon dioxide and water) on the performance of 10-DAN-55 (spinel oxide based catalyst) at 400{degrees}C, 1000 psi, GHSV = 12,000 and syngas (H{sub 2}/CO) ratio = 1:2 (alcohol addition) and 1:1 (carbon dioxide and water addition) was studied. The effect of operation at high temperatures and pressures on the performance of an improved catalyst formulation was also examined.« less

Need for optimizing catalyst loading for achieving affordable microbial fuel cells.

PubMed

Singh, Inderjeet; Chandra, Amreesh

2013-08-01

Microbial fuel cell (MFC) technology is a promising technology for electricity production together with simultaneous water treatment. Catalysts play an important role in deciding the MFC performance. In most reports, effect of catalyst - both type and quantity is not optimized. In this paper, synthesis of nanorods of MnO2-catalyst particles for application in Pt-free MFCs is reported. The effect of catalyst loading i.e., weight ratio, with respect to conducting element and binder has been optimized by employing large number of combinations. Using simple theoretical model, it is shown that too high (or low) concentration of catalysts result in loss of MFC performance. The operation of MFC has been investigated using domestic wastewater as source of bio-waste for obtaining real world situation. Maximum power density of ∼61 mW/m(2) was obtained when weight ratio of catalyst and conducting species was 1:1. Suitable reasons are given to explain the outcomes. Copyright © 2013 Elsevier Ltd. All rights reserved.
Nitrogen-doped graphene catalysts: High energy wet ball milling synthesis and characterizations of functional groups and particle size variation with time and speed

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

Zhuang, Shiqiang; Nunna, Bharath Babu; Boscoboinik, Jorge Anibal

Nitrogen-doped graphene (N-G) catalyst emerges as one of the promising non-platinum group metal (non-PGM) catalysts with the advantages of low cost, high oxygen reduction reaction (ORR) activity, stability, and selectivity to replace expensive PGM catalysts in electrochemical systems. This research investigated nanoscale high energy wet (NHEW) ball milling for the synthesis of N-G catalysts to make conventional problems such as sintering or localized overheating issues negligible. The successful synthesis of N-G catalysts with comparable catalytic performance to 10 wt% Pt/C by using this method has been published. This paper focuses on understanding the effect of grinding speed and grinding timemore » on the particle size and chemical state of N-G catalysts through the physical and chemical characterization. The research result shows that (1) the final particle size, nitrogen doping percentage, and nitrogen bonding composition of synthesized N-G catalysts are predictable and controllable by adjusting the grinding time, the grinding speed, and other relative experimental parameters; (2) the final particle size of N-G catalysts could be estimated from the derived relation between the cracking energy density and the particle size of ground material in the NHEW ball milling process with specified experimental parameters; and (3) the chemical composition of N-G catalysts synthesized by NHEW ball milling is controllable by adjusting the grinding time and grinding speed.« less
Nitrogen-doped graphene catalysts: High energy wet ball milling synthesis and characterizations of functional groups and particle size variation with time and speed

DOE PAGES

Zhuang, Shiqiang; Nunna, Bharath Babu; Boscoboinik, Jorge Anibal; ...

2017-07-26

Nitrogen-doped graphene (N-G) catalyst emerges as one of the promising non-platinum group metal (non-PGM) catalysts with the advantages of low cost, high oxygen reduction reaction (ORR) activity, stability, and selectivity to replace expensive PGM catalysts in electrochemical systems. This research investigated nanoscale high energy wet (NHEW) ball milling for the synthesis of N-G catalysts to make conventional problems such as sintering or localized overheating issues negligible. The successful synthesis of N-G catalysts with comparable catalytic performance to 10 wt% Pt/C by using this method has been published. This paper focuses on understanding the effect of grinding speed and grinding timemore » on the particle size and chemical state of N-G catalysts through the physical and chemical characterization. The research result shows that (1) the final particle size, nitrogen doping percentage, and nitrogen bonding composition of synthesized N-G catalysts are predictable and controllable by adjusting the grinding time, the grinding speed, and other relative experimental parameters; (2) the final particle size of N-G catalysts could be estimated from the derived relation between the cracking energy density and the particle size of ground material in the NHEW ball milling process with specified experimental parameters; and (3) the chemical composition of N-G catalysts synthesized by NHEW ball milling is controllable by adjusting the grinding time and grinding speed.« less
The effect of H2O and pretreatment on the activity of a Pt/SnO2 catalyst

NASA Technical Reports Server (NTRS)

Vannorman, John D.; Brown, Kenneth G.; Schryer, Jacqueline; Schryer, David R.; Upchurch, Billy T.; Sidney, Barry D.

1990-01-01

CO oxidation catalysts with high activity at 25 C to 100 C are important for long-life, closed-cycle operation of pulsed CO2 lasers. A reductive pretreatment with either CO or H2 has been shown to significantly enhance the activity of a commercially available platinum on tin (IV) oxide (Pt/SnO2) catalyst relative to an oxidative or inert pretreatment or no pretreatment. Pretreatment at temperatures of 175 C and above causes an initial dip in the observed CO2 yield before the steady-state yield is attained. This dip has been found to be caused by dehydration of the catalyst during pretreatment and is readily eliminated by humidifying the catalyst or the reaction gas mixture. It is hypothesized that the effect of humidification is to increase the concentration of OH groups on the catalyst surface which play a role in the reaction mechanism.
The effects of pretreatment conditions on a Pt/SnO2 catalyst for the oxidation of CO in CO2 lasers

NASA Technical Reports Server (NTRS)

Schryer, David R.; Vannorman, John D.; Brown, Kenneth G.; Schryer, Jacqueline

1989-01-01

CO oxidation catalysts with high activity at 25 to 100 C are important for long life, closed cycle operation of pulsed CO2 lasers. A reductive pretreatment with either CO or H2 was shown to significantly enhance the activity of a commercially available platinum on tin (IV) oxide (Pt/SnO2) catalyst relative to an oxidative or inert pretreatment of no pretreatment. Pretreatment at temperatures of 175 C and above causes an initial dip in the observed CO2 yield before the steady state yield is attained. This dip was found to be caused by dehydration of the catalyst during pretreatment and is readily eliminated by humidifying the catalyst or the reaction gas mixture. It is hypothesized that the effect of humidification is to increase the concentration of OH groups on the catalyst surface which play a role in the reaction mechanism.
a Novel Catalyst for Reductive Dechlorination of Chlorobenzene in Subcritical Water:. Bifunctional Fe/ZrO2

NASA Astrophysics Data System (ADS)

Wei, Guang-Tao; Wei, Chao-Hai; He, Feng-Mei; Wu, Chao-Fei

Bifunctional Fe/ZrO2 was prepared by mechanical mixing method, and its bifunctional effect on reductive dechlorination of chlorobenzene in subcritical water was studied. Dechlorination efficiency increased with increasing iron content in catalyst and catalyst amount. Dechlorination efficiency slowed when the iron content in catalyst reached 30%; bifunctional catalyst of Fe/ZrO2 was more efficient in dechlorination of chlorobenzene than Fe alone. Catalyst of Fe (30%)/ZrO2 was characterized by means of X-ray diffraction (XRD), H2 temperature programmed desorption (H2-TPD), and N2 adsorption. The possible mechanism of dechlorination in subcritical water by this bifunctional catalyst was proposed. H+ produced in the water dissociation formed the highly reactive spillover hydrogen on the surface of catalyst, and then reacted with chlorobenzene adsorbed on the catalyst surface by ZrO2 to form benzene and chloride ions.
Synthesis of high-quality diesel with furfural and 2-methylfuran from hemicellulose.

PubMed

Li, Guangyi; Li, Ning; Wang, Zhiqiang; Li, Changzhi; Wang, Aiqin; Wang, Xiaodong; Cong, Yu; Zhang, Tao

2012-10-01

Hydroxyalkylation-alkylation (HAA) coupled with hydrodeoxygenation is a promising route for the synthesis of renewable high-quality diesel or jet fuel. In this work, a series of solid-acid catalysts were firstly used for HAA between lignocellulose-derived furan and carbonyl compounds. Among the investigated catalysts, Nafion-212 resin demonstrated the highest activity and stability. Owing to the high activity of the reactants and the advantage in industrial integration, the HAA of 2-methylfuran (2-MF) and furfural can be considered as a prospective route in future applications. Catalyst loading, reaction temperature, and time had evident effects on the HAA of 2-MF and furfural over Nafion-212 resin. Finally, the HAA product of 2-MF and furfural was hydrogenated over a Pd/C catalyst and hydrodeoxygenated over Pt-loaded solid-acid catalysts. Pt/zirconium phosphate (Pt/ZrP) was found to be the best catalyst for hydrodeoxygenation. Over the 4 % Pt/ZrP catalyst, a 94 % carbon yield of diesel and 75 % carbon yield of C15 hydrocarbons (with 6-butylundecane as the major component) was achieved. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Hydroisomerization of n-hexadecane: remarkable selectivity of mesoporous silica post-synthetically modified with aluminum

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

Sabyrov, Kairat; Musselwhite, Nathan; Melaet, Gérôme

As the impact of acids on catalytically driven chemical transformations is tremendous, fundamental understanding of catalytically relevant factors is essential for the design of more efficient solid acid catalysts. In this work, we employed a post-synthetic doping method to synthesize a highly selective hydroisomerization catalyst and to demonstrate the effect of acid strength and density, catalyst microstructure, and platinum nanoparticle size on the reaction rate and selectivity. Aluminum doped mesoporous silica catalyzed gas-phase n-hexadecane isomerization with remarkably high selectivity to monobranched isomers (~95%), producing a substantially higher amount of isomers than traditional zeolite catalysts. Mildly acidic sites generated by post-syntheticmore » aluminum grafting were found to be the main reason for its high selectivity. The flexibility of the post-synthetic doping method enabled us to systematically explore the effect of the acid site density on the reaction rate and selectivity, which has been extremely difficult to achieve with zeolite catalysts. We found that a higher density of Brønsted acid sites leads to higher cracking of n-hexadecane presumably due to an increased surface residence time. Furthermore, regardless of pore size and microstructure, hydroisomerization turnover frequency linearly increased as a function of Brønsted acid site density. In addition to strength and density of acid sites, platinum nanoparticle size affected catalytic activity and selectivity. The smallest platinum nanoparticles produced the most effective bifunctional catalyst presumably because of higher percolation into aluminum doped mesoporous silica, generating more 'intimate' metallic and acidic sites. Finally, the aluminum doped silica catalyst was shown to retain its remarkable selectivity towards isomers even at increased reaction conversions.« less
Hydroisomerization of n-hexadecane: remarkable selectivity of mesoporous silica post-synthetically modified with aluminum

DOE PAGES

Sabyrov, Kairat; Musselwhite, Nathan; Melaet, Gérôme; ...

2017-01-01

As the impact of acids on catalytically driven chemical transformations is tremendous, fundamental understanding of catalytically relevant factors is essential for the design of more efficient solid acid catalysts. In this work, we employed a post-synthetic doping method to synthesize a highly selective hydroisomerization catalyst and to demonstrate the effect of acid strength and density, catalyst microstructure, and platinum nanoparticle size on the reaction rate and selectivity. Aluminum doped mesoporous silica catalyzed gas-phase n-hexadecane isomerization with remarkably high selectivity to monobranched isomers (~95%), producing a substantially higher amount of isomers than traditional zeolite catalysts. Mildly acidic sites generated by post-syntheticmore » aluminum grafting were found to be the main reason for its high selectivity. The flexibility of the post-synthetic doping method enabled us to systematically explore the effect of the acid site density on the reaction rate and selectivity, which has been extremely difficult to achieve with zeolite catalysts. We found that a higher density of Brønsted acid sites leads to higher cracking of n-hexadecane presumably due to an increased surface residence time. Furthermore, regardless of pore size and microstructure, hydroisomerization turnover frequency linearly increased as a function of Brønsted acid site density. In addition to strength and density of acid sites, platinum nanoparticle size affected catalytic activity and selectivity. The smallest platinum nanoparticles produced the most effective bifunctional catalyst presumably because of higher percolation into aluminum doped mesoporous silica, generating more 'intimate' metallic and acidic sites. Finally, the aluminum doped silica catalyst was shown to retain its remarkable selectivity towards isomers even at increased reaction conversions.« less
Development of attrition resistant iron-based Fischer-Tropsch catalysts

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

NONE

2000-09-20

The Fischer-Tropsch (F-T) reaction provides a way of converting coal-derived synthesis gas (CO+H{sub 2}) to liquid fuels. Since the reaction is highly exothermic, one of the major problems in control of the reaction is heat removal. Recent work has shown that the use of slurry bubble column reactors (SBCRs) can largely solve this problem. The use of iron-based catalysts is attractive not only due to their low cost and ready availability, but also due to their high water-gas shift activity which makes it possible to use these catalysts with low H{sub 2}/CO ratios. However, a serious problem with use ofmore » Fe catalysts in a SBCR is their tendency to undergo attrition. This can cause fouling/plugging of downstream filters and equipment, makes the separation of catalyst from the oil/wax product very difficult if not impossible, and results a steady loss of catalyst from the reactor. The objective of this research is to develop robust iron-based Fischer-Tropsch catalysts that have suitable activity, selectivity and stability to be used in the slurry bubble column reactor. Specifically we aim to develop to: (1) improve the performance and preparation procedure of the high activity, high attrition resistant, high alpha iron-based catalysts synthesized at Hampton University (2) seek improvements in the catalyst performance through variations in process conditions, pretreatment procedures and/or modifications in catalyst preparation steps and (3) investigate the performance in a slurry reactor. The effort during the reporting period has been devoted to effects of pretreating procedures, using H{sub 2}, CO and syngas (H{sub 2}/CO = 0.67) as reductants, on the performance (activity, selectivity and stability with time) of a precipitated iron catalyst (100Fe/5Cu/4.2K/10SiO{sub 2} on a mass basis ) during F-T synthesis were studied in a fixed-bed reactor.« less
Picolinamide-Based Iridium Catalysts for Dehydrogenation of Formic Acid in Water: Effect of Amide N Substituent on Activity and Stability

DOE PAGES

Kanega, Ryoichi; Onishi, Naoya; Wang, Lin; ...

2018-03-01

To develop highly efficient catalysts for dehydrogenation of formic acid in water, we investigated in this paper several Cp*Ir catalysts with various amide ligands. The catalyst with an N-phenylpicolinamide ligand exhibited a TOF of 118 000 h -1 at 60 °C. A constant rate (TOF>35 000 h -1) was maintained for six hours, and a TON of 1 000 000 was achieved at 50 °C.
Picolinamide-Based Iridium Catalysts for Dehydrogenation of Formic Acid in Water: Effect of Amide N Substituent on Activity and Stability

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

Kanega, Ryoichi; Onishi, Naoya; Wang, Lin

To develop highly efficient catalysts for dehydrogenation of formic acid in water, we investigated in this paper several Cp*Ir catalysts with various amide ligands. The catalyst with an N-phenylpicolinamide ligand exhibited a TOF of 118 000 h -1 at 60 °C. A constant rate (TOF>35 000 h -1) was maintained for six hours, and a TON of 1 000 000 was achieved at 50 °C.
Synthesis and Characterization of Polyethylene/Starch Nanocomposites: A Spherical Starch-Supported Catalyst and In Situ Ethylene Polymerization.

PubMed

Zhanga, Hao; Xi, Shixia; Wang, Shuwei; Liu, Jingsheng; Yoon, Keun-Byoung; Lee, Dong-Ho; Zhang, Hexin; Zhang, Xuequan

2017-01-01

In the present article, a novel spherical starch-supported vanadium (V)-based Ziegler-Natta catalyst was synthesized. The active centers of the obtained catalyst well dispersed in the starch through the SEM-EDX analysis. The effects of reaction conditions on ethylene polymerization were studied. The synthesized catalyst exhibited high activity toward ethylene polymerization in the presence of ethylaluminium sesquichloride (EASC) cocatalyst. Interestingly, the fiber shape PE was obtained directly during the polymerization process.
Facile solid-state synthesis of highly dispersed Cu nanospheres anchored on coal-based activated carbons as an efficient heterogeneous catalyst for the reduction of 4-nitrophenol

NASA Astrophysics Data System (ADS)

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

2018-04-01

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

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

Linehan, J.C.; Matson, D.W.; Darab, J.G.

1994-09-01

The use of coal as a source of transportation fuel is currently economically unfavorable due to an abundant world petroleum supply and the relatively high cost of coal liquefaction. Consequently, a reduction in the cost of coal liquefaction, for example by using less and/or less costly catalysts or lower liquefaction temperatures, must be accomplished if coal is to play an significant role as a source of liquid feedstock for the petrochemical industry. The authors and others have investigated the applicability of using inexpensive iron-based catalysts in place of more costly and environmentally hazardous metal catalysts for direct coal liquefaction. Iron-basedmore » catalysts can be effective in liquefying coal and in promoting carbon-carbon bond cleavage in model compounds. The authors have been involved in an ongoing effort to develop and optimize iron-based powders for use in coal liquefaction and related petrochemical applications. Research efforts in this area have been directed at three general areas. The authors have explored ways to optimize the effectiveness of catalyst precursor species through use of nanocrystalline materials and/or finely divided powders. In this effort, the authors have developed two new nanophase material production techniques, Modified Reverse Micelle (MRM) and the Rapid Thermal Decomposition of precursors in Solution (RTDS). A second effort has been aimed at optimizing the effectiveness of catalysts by variations in other factors. To this, the authors have investigated the effect that the crystalline phase has on the capacity of iron-based oxide and oxyhydroxide powders to be effectively converted to an active catalyst phase under liquefaction conditions. And finally, the authors have developed methods to produce active catalyst precursor powders in quantities sufficient for pilot-scale testing. Major results in these three areas are summarized.« less
DEVELOPMENT OF ATTRITION RESISTANT IRON-BASED FISCHER-TROPSCH CATALYSTS

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

Adeyinka A. Adeyiga

2001-09-01

The Fischer-Tropsch (F-T) reaction provides a way of converting coal-derived synthesis gas (CO+H{sub 2}) to liquid fuels. Since the reaction is highly exothermic, one of the major problems in control of the reaction is heat removal. Recent work has shown that the use of slurry bubble column reactors (SBCRs) can largely solve this problem. The use of iron-based catalysts is attractive not only due to their low cost and ready availability, but also due to their high water-gas shift activity which makes it possible to use these catalysts with low H{sub 2}/CO ratios. However, a serious problem with use ofmore » Fe catalysts in a SBCR is their tendency to undergo attrition. This can cause fouling/plugging of downstream filters and equipment, makes the separation of catalyst from the oil/wax product very difficult if not impossible, and results in a steady loss of catalyst from the reactor. Recently, fundamental understanding of physical attrition is being addressed by incorporating suitable binders into the catalyst recipe. This has resulted in the preparation of a spray dried Fe-based catalyst having aps of 70 mm with high attrition resistance. This Fe-based attrition resistant, active and selective catalyst gave 95% CO conversion through 125 hours of testing in a fixed-bed at 270 C, 1.48 MPa, H{sub 2}/CO=0.67 and 2.0 NL/g-cat/h with C{sub 5}{sup +} selectivity of >78% and methane selectivity of <5%. However, further development of the catalyst is needed to address the chemical attrition due to phase changes that any Fe-catalyst goes through potentially causing internal stresses within the particle and resulting in weakening, spalling or cracking. The objective of this research is to develop robust iron-based Fischer-Tropsch catalysts that have suitable activity, selectivity and stability to be used in the slurry bubble column reactor. Specifically we aim to develop to: (i) improve the performance and preparation procedure of the high activity, high attrition resistant, high alpha iron-based catalysts synthesized at Hampton University, (ii) seek improvements in the catalyst performance through variations in process conditions, pretreatment procedures and/or modifications in catalyst preparation steps and (iii) investigate the performance in a slurry reactor. The effort during the reporting period has been devoted to attrition study of the iron-based catalysts. Precipitated silica appeared to decrease attrition resistance of spray-dried iron FT catalysts. It was found that the catalyst with precipitated silica content at around 12wt% showed the lowest attrition resistance. The results of net change in volume moment and catalyst morphology showed supporting evidences to the attrition results. Catalysts with low attrition resistance generated more fines loss, had higher net change in volume moment and showed more breakage of particles. BET surface area and pore volume of this catalyst series fluctuated; therefore no conclusion can be drawn from the data obtained. However, catalyst with no precipitated silica showed the lowest in BET surface area and pore volume, as expected. Addition of precipitated silica to the catalysts had no effect to the phase changes of iron that could have significant influence to catalyst attrition. The presence of precipitated silica is needed for enhancing catalyst surface area; however, the amount of silica added should be compromising with attrition resistance of catalysts.« less
Direct production of biodiesel from high-acid value Jatropha oil with solid acid catalyst derived from lignin

PubMed Central

2011-01-01

Background Solid acid catalyst was prepared from Kraft lignin by chemical activation with phosphoric acid, pyrolysis and sulfuric acid. This catalyst had high acid density as characterized by scanning electron microscope (SEM), energy-dispersive x-ray spectrometry (EDX) and Brunauer, Emmett, and Teller (BET) method analyses. It was further used to catalyze the esterification of oleic acid and one-step conversion of non-pretreated Jatropha oil to biodiesel. The effects of catalyst loading, reaction temperature and oil-to-methanol molar ratio, on the catalytic activity of the esterification were investigated. Results The highest catalytic activity was achieved with a 96.1% esterification rate, and the catalyst can be reused three times with little deactivation under optimized conditions. Biodiesel production from Jatropha oil was studied under such conditions. It was found that 96.3% biodiesel yield from non-pretreated Jatropha oil with high-acid value (12.7 mg KOH/g) could be achieved. Conclusions The catalyst can be easily separated for reuse. This single-step process could be a potential route for biodiesel production from high-acid value oil by simplifying the procedure and reducing costs. PMID:22145867
Soluble organic nanotubes for catalytic systems.

PubMed

Xiong, Linfeng; Yang, Kunran; Zhang, Hui; Liao, Xiaojuan; Huang, Kun

2016-03-18

In this paper, we report a novel method for constructing a soluble organic nanotube supported catalyst system based on single-molecule templating of core–shell bottlebrush copolymers. Various organic or metal catalysts, such as sodium prop-2-yne-1-sulfonate (SPS), 1-(2-(prop-2-yn-1-yloxy)ethyl)-1H-imidazole (PEI) and Pd(OAc)2 were anchored onto the tube walls to functionalize the organic nanotubes via copper-catalyzed azide-alkyne cycloaddition (CuAAC) reaction. Depending on the 'confined effect' and the accessible cavity microenvironments of tubular structures, the organic nanotube catalysts showed high catalytic efficiency and site-isolation features. We believe that the soluble organic nanotubes will be very useful for the development of high performance catalyst systems due to their high stability of support, facile functionalization and attractive textural properties.
Asymmetric Volcano Trend in Oxygen Reduction Activity of Pt and Non-Pt Catalysts: In Situ Identification of the Site-Blocking Effect.

PubMed

Li, Jingkun; Alsudairi, Amell; Ma, Zi-Feng; Mukerjee, Sanjeev; Jia, Qingying

2017-02-01

Proper understanding of the major limitations of current catalysts for oxygen reduction reaction (ORR) is essential for further advancement. Herein by studying representative Pt and non-Pt ORR catalysts with a wide range of redox potential (E redox ) via combined electrochemical, theoretical, and in situ spectroscopic methods, we demonstrate that the role of the site-blocking effect in limiting the ORR varies drastically depending on the E redox of active sites; and the intrinsic activity of active sites with low E redox have been markedly underestimated owing to the overlook of this effect. Accordingly, we establish a general asymmetric volcano trend in the ORR activity: the ORR of the catalysts on the overly high E redox side of the volcano is limited by the intrinsic activity; whereas the ORR of the catalysts on the low E redox side is limited by either the site-blocking effect and/or intrinsic activity depending on the E redox .
The synthesis of Cu/Fe/Fe3O4 catalyst through the aqueous solution ball milling method assisted by high-frequency electromagnetic field

NASA Astrophysics Data System (ADS)

Yingzhe, Zhang; Yuxing, He; Qingdong, Qin; Fuchun, Wang; Wankun, Wang; Yongmei, Luo

2018-06-01

In this paper, nano-magnetic Cu/Fe/Fe3O4 catalyst was prepared by a new aqueous solution ball milling method assisted by high-frequency electromagnetic field at room temperature. The products were characterized by means of X-ray diffraction (XRD), high-resolution transmission electron microscope (HRTEM), selected area electron diffraction (SAED), and vibrating sample magnetometer (VSM). Microwave induced catalytic degradation of methylene blue (MB) was carried out in the presence of Cu/Fe/Fe3O4. The concentration of methylene blue was determined by UV-Vis spectrophotometry. The solid catalyst showed high catalytic activity of degrade MB and considerable saturation magnetization, lower remanence and coercivity. It indicate that the catalyst can be effectively separated for reuse by simply applying an external magnetic field and it can greatly promote their potential industrial application to eliminate organic pollutants from waste-water. Finally, we found that it is the non-thermal effect of microwave that activated the catalytic activity of Cu/Fe/Fe3O4 to degrade MB.

Robust Mesoporous CoMo/γ-Al2O3 Catalysts from Cyclodextrin-Based Supramolecular Assemblies for Hydrothermal Processing of Microalgae: Effect of the Preparation Method.

PubMed

Bleta, Rudina; Schiavo, Benedetto; Corsaro, Natale; Costa, Paula; Giaconia, Alberto; Interrante, Leonardo; Monflier, Eric; Pipitone, Giuseppe; Ponchel, Anne; Sau, Salvatore; Scialdone, Onofrio; Tilloy, Sébastien; Galia, Alessandro

2018-04-18

Hydrothermal liquefaction (HTL) is a promising technology for the production of biocrude oil from microalgae. Although this catalyst-free technology is efficient under high-temperature and high-pressure conditions, the biocrude yield and quality can be further improved by using heterogeneous catalysts. The design of robust catalysts that preserve their performance under hydrothermal conditions will be therefore very important in the development of biorefinery technologies. In this work, we describe two different synthetic routes (i.e., impregnation and cyclodextrin-assisted one-pot colloidal approach), for the preparation in aqueous phase of six high surface area CoMo/γ-Al 2 O 3 catalysts. Catalytic tests performed on the HTL of Nannochloropsis gaditana microalga indicate that solids prepared by the one-pot colloidal approach show higher hydrothermal stability and enhanced biocrude yield with respect to the catalyst-free test. The positive effect of the substitution of the block copolymer Tetronic T90R4 for Pluronic F127 in the preparation procedure was evidenced by diffuse reflectance UV-visible spectroscopy, X-ray diffraction, N 2 -adsorption-desorption, and H 2 -temperature-programmed reduction measurements and confirmed by the higher quality of the obtained biocrude, which exhibited lower oxygen content and higher-energy recovery equal to 62.5% of the initial biomass.
Identification of carbon-encapsulated iron nanoparticles as active species in non-precious metal oxygen reduction catalysts

PubMed Central

Varnell, Jason A.; Tse, Edmund C. M.; Schulz, Charles E.; Fister, Tim T.; Haasch, Richard T.; Timoshenko, Janis; Frenkel, Anatoly I.; Gewirth, Andrew A.

2016-01-01

The widespread use of fuel cells is currently limited by the lack of efficient and cost-effective catalysts for the oxygen reduction reaction. Iron-based non-precious metal catalysts exhibit promising activity and stability, as an alternative to state-of-the-art platinum catalysts. However, the identity of the active species in non-precious metal catalysts remains elusive, impeding the development of new catalysts. Here we demonstrate the reversible deactivation and reactivation of an iron-based non-precious metal oxygen reduction catalyst achieved using high-temperature gas-phase chlorine and hydrogen treatments. In addition, we observe a decrease in catalyst heterogeneity following treatment with chlorine and hydrogen, using Mössbauer and X-ray absorption spectroscopy. Our study reveals that protected sites adjacent to iron nanoparticles are responsible for the observed activity and stability of the catalyst. These findings may allow for the design and synthesis of enhanced non-precious metal oxygen reduction catalysts with a higher density of active sites. PMID:27538720
Evolution of a Fourth Generation Catalyst for the Amination and Thioetherification of Aryl Halides

PubMed Central

Hartwig, John F.

2010-01-01

Conspectus Synthetic methods to form the carbon-nitrogen bonds in aromatic amines are fundamental enough to be considered part of introductory organic courses. Arylamines are important because they are common precursors to or substructures within active pharmaceutical ingredients and herbicides produced on ton scales, as well as conducting polymers and layers of organic light-emitting diodes produced on small scale. For many years, this class of compound was prepared from classical methods, such as nitration, reduction and reductive alkylation, copper-mediated chemistry at high temperatures, addition to benzyne intermediates, or direct nucleophilic substitution on particularly electron-poor aromatic or heteroaromatic halides. During the past decade, these methods to form aromatic amines have been largely supplanted by palladium-catalyzed coupling reactions of amines with aryl halides. The scope and efficiency of the palladium-catalyzed processes has gradually improved with successive generations of catalysts to the point of being useful for the synthesis of both milligrams and kilograms of product. This Account describes the conceptual basis and utility of our latest, “fourth-generation” catalyst for the coupling of amines and related reagents with aryl halides. The introductory sections of this account describe the progression of catalyst development from the first-generation to current systems and the motivation for selection of the components of the fourth-generation catalyst. This progression began with catalysts containing palladium and sterically hindered monodentate aromatic phosphines used initially for coupling of tin amides with haloarenes in the first work on C-N coupling. A second generation of catalysts was then developed based on the combination of palladium and aromatic bisphosphines. These systems were then followed by third-generation systems catalysts on the combination of palladium and a sterically hindered alkylmonophosphine or N-heterocyclic carbene. During the past five years, we have studied a fourth-generation catalyst for these reactions containing ligands that combine the chelating properties of the second-generation systems with the steric hindrance and strong electron donation of the third-generation systems. This combination has created a catalyst that couples aryl chlorides, bromides and iodides with primary amines, N-H imines, and hydrazones in high yield, with broad scope, high functional group tolerance, nearly perfect selectivity for monoarylation, and the lowest levels of palladium that have been used for C-N coupling. This catalyst is based on palladium and a sterically hindered version of the Josiphos family of ligands that possesses a ferrocenyl-1-ethylbackbone, a hindered di-tert-butylphosphino group, and a hindered dicyclohexylphosphino group. This latest generation of catalyst not only improves the coupling of primary amines and related nucleophiles, but it has dramatically improved the coupling of thiols with haloarenes to form C-S bonds. This catalyst system couples both aliphatic and aromatic thiols with chloroarenes with much greater scope, functional group tolerance, and turnover numbers than had been observed previously. The effects of structural features of the Josiphos ligand on catalyst activity have been revealed by examining the reactivity of catalysts generated from ligands lacking one or more of the structural elements of the most active catalyst. These modified ligands lack the relative stereochemistry of the ferrocenyl-1-ethyl backbone, the strong electron donation of the dialkylphosphino groups, the steric demands of the alkylphosphine groups, or the stability of the ferrocenyl unit. This set of studies showed that each one of these structural features contributed to the high reactivity and selectivity of the catalyst containing the hindered, bidentate Josiphos ligand. Finally, a series of studies on the effect of electronic properties on the rates of reductive elimination have recently distinguished between the effect of the properties of the M-N σ-bond and the nitrogen electron pair on the rate of reductive elimination. These studies have shown that the effect of substituents attached to the metal-bound nitrogen or carbon atoms on the rate of reductive elimination are similar. Because the amido ligands contain an electron pair, while the alkyl ligands do not, we have concluded that the major electronic effect is transmitted through the σ-bond. In other words, we have concluded that the electronic effect on the metal-nitrogen σ bond dominates an electronic effect on the nitrogen electron pair. PMID:18681463
Palladium-tin catalysts for the direct synthesis of H 2O 2 with high selectivity

DOE PAGES

Freakley, Simon J.; He, Qian; Harrhy, Jonathan H.; ...

2016-02-25

The direct synthesis of hydrogen peroxide (H 2O 2 ) from H 2 and O 2 represents a potentially atom-efficient alternative to the current industrial indirect process. We show that the addition of tin to palladium catalysts coupled with an appropriate heat treatment cycle switches off the sequential hydrogenation and decomposition reactions, enabling selectivities of >95% toward H 2O 2 . This effect arises from a tin oxide surface layer that encapsulates small Pd-rich particles while leaving larger Pd-Sn alloy particles exposed. In conclusion, we show that this effect is a general feature for oxide-supported Pd catalysts containing an appropriatemore » second metal oxide component, and we set out the design principles for producing high-selectivity Pd-based catalysts for direct H 2O 2 production that do not contain gold.« less
Effect of Pt and Fe catalysts in the transformation of carbon black into carbon nanotubes

NASA Astrophysics Data System (ADS)

Asokan, Vijayshankar; Myrseth, Velaug; Kosinski, Pawel

2015-06-01

In this research carbon nanotubes and carbon nano onion-like structures were synthesized from carbon black using metal catalysts at 400 °C and 700 °C. Platinum and iron-group metals were used as catalysts for the transformation of CB into graphitized nanocarbon and the effect of both metals was compared. The synthesized products were characterized using X-ray diffraction (XRD), transmission electron microscope (TEM), high resolution transmission electron microscope (HRTEM) and Raman spectroscopy. The characterization shows that this process is very efficient in the synthesis of high quality graphitized products from amorphous carbon black, even though the process temperature was relatively low in comparison with previous studies. Distinguished graphitic walls of the newly formed carbon nanostructures were clearly visible in the HRTEM images. Possible growth difference related to the type of catalyst used is briefly explained with the basis of electron vacancies in d-orbitals of metals.
NASA - Johnson Space Center's New Capabilities for Air Purification

NASA Technical Reports Server (NTRS)

Graf, John

2015-01-01

NASA has some unique and challenging air purification problems that cannot be adequately met with COTS technology: 1) ammonia removal from air, 2) hydrazine removal from air, 3) CO conversion to CO2 in low temperature, high humidity environments. NASA has sponsored the development of new sorbents and new catalysts. These new sorbents and catalysts work better than COTS technology for our application. If attendees have a need for an effective ammonia sorbent, an effective hydrazine sorbent, or an effective CO conversion catalyst, we should learn to see if NASA sponsored technology development can help.
Selective oxidation of carbon monoxide in fuel processor gas

NASA Astrophysics Data System (ADS)

Manasilp, Akkarat

The trace amount of CO present in the hydrogen-rich stream coming from fuel reformers poisons the platinum anode electrode of proton exchange membrane (PEM) fuel cells and reduces the power output. Removal of low levels of CO present in the reformed gas must take place before the gas enters the fuel cell. The tolerable level of CO is around 10 ppm. We investigated the performance of single step sol-gel prepared Pt/alumina catalyst and Pt supported on sol gel made alumina. The effect of water vapor, carbon dioxide, CO and oxygen concentrations, temperature, and Pt loading on the activity and selectivity are presented. Our results showed that a 2%Pt/alumina sol-gel catalyst can selectively oxide CO down to a few ppm with constant selectivity and high space velocity. Water vapor in the feed increases the activity of catalysts dramatically and in the absence of water vapor, CO2 in the feed stream decreases the activity of the catalysts significantly. We also found that the presence of potassium as an electron donor did not improve the performance of Pt/alumina catalyst to the selective CO oxidation. For Pt supported on sol gel made alumina, we found that the combination of CO2 and H2O in the gas feed has a strong effect on selective CO oxidation over Pt/Al2O3. It could be a positive or negative effect depending upon Pt loading in the catalyst. With high Pt loading, the CO2 effect tends to dominate the H2O effect resulting in the decrease in CO conversion. Moreover, the presence of CeO2 as an oxygen storage compound promotes the performance of Pt supported on alumina at low temperature ˜90°C when Pt loading was 5%. Amongst the examined catalysts, the 5%Pt/15%CeO2/Al 2O3 catalyst showed the highest selectivity, with high CO conversion at a low temperature ˜90°C. The beneficial effect of the addition of CeO2 is most likely due to spillover of O2 from CeO2 to Pt at the Pt sites at the interface of Pt and CeO 2.
Carbon nanotube-supported Au-Pd alloy with cooperative effect of metal nanoparticles and organic ketone/quinone groups as a highly efficient catalyst for aerobic oxidation of amines.

PubMed

Deng, Weiping; Chen, Jiashu; Kang, Jincan; Zhang, Qinghong; Wang, Ye

2016-05-21

Functionalised carbon nanotube (CNT)-supported Au-Pd alloy nanoparticles were highly efficient catalysts for the aerobic oxidation of amines. We achieved the highest turnover frequencies (>1000 h(-1)) for the oxidative homocoupling of benzylamine and the oxidative dehydrogenation of dibenzylamine. We discovered a cooperative effect between Au-Pd nanoparticles and ketone/quinone groups on CNTs.
Performance of (CoPC)n catalyst in active lithium-thionyl chloride cells

NASA Technical Reports Server (NTRS)

Shah, Pinakin M.

1990-01-01

An experimental study was conducted with anode limited D size cells to characterize the performance of an active lithium-thionyl chloride (Li/SOCl2) system using the polymeric cobalt phthalocyanine, (CoPC)n, catalyst in carbon cathodes. The author describes the results of this experiment with respect to initial voltage delays, operating voltages, and capacities. The effectiveness of the preconditioning methods evolved to alleviate passivation effects on storage are also discussed. The results clearly demonstrated the superior high rate capability of cells with the catalyst. The catalyst did not adversely impact the performance of cells after active storage for up to 6 months, while retaining its beneficial influences.
Selective Hydrogenation of Furfural to Furfuryl Alcohol in the Presence of a Recyclable Cobalt/SBA-15 Catalyst.

PubMed

Audemar, Maïté; Ciotonea, Carmen; De Oliveira Vigier, Karine; Royer, Sébastien; Ungureanu, Adrian; Dragoi, Brindusa; Dumitriu, Emil; Jérôme, François

2015-06-08

The hydrogenation of furfural to furfuryl alcohol was performed in the presence of a Co/SBA-15 catalyst. High selectivity (96 %) at a conversion higher than 95 % is reported over this catalytic system. As the conversion of furfural to furfuryl alcohol occurs over metallic Co sites, the effect of reduction temperature, H2 pressure, and reaction temperature were studied. Optimum reaction conditions were: 150 °C, 1.5 h, 2.0 MPa of H2 . The catalyst was recyclable, and furfuryl alcohol was recovered with a purity higher than 90 %. The effect of the solvent concentration was also studied. With a minimum of 50 wt % of solvent, the selectivity to furfuryl alcohol and the conversion of furfural remained high (both over 80 %). Likewise, the activity of the catalyst is maintained even in pure furfural, which confirms the real potential of the proposed catalytic system. This catalyst was also used in the hydrogenation of levulinic acid to produce γ-valerolactone selectively. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Nanoscale Catalysts for NMR Signal Enhancement by Reversible Exchange

PubMed Central

2015-01-01

Two types of nanoscale catalysts were created to explore NMR signal enhancement via reversible exchange (SABRE) at the interface between heterogeneous and homogeneous conditions. Nanoparticle and polymer comb variants were synthesized by covalently tethering Ir-based organometallic catalysts to support materials composed of TiO2/PMAA (poly(methacrylic acid)) and PVP (polyvinylpyridine), respectively, and characterized by AAS, NMR, and DLS. Following parahydrogen (pH2) gas delivery to mixtures containing one type of “nano-SABRE” catalyst particle, a target substrate, and ethanol, up to ∼(−)40-fold and ∼(−)7-fold 1H NMR signal enhancements were observed for pyridine substrates using the nanoparticle and polymer comb catalysts, respectively, following transfer to high field (9.4 T). These enhancements appear to result from intact particles and not from any catalyst molecules leaching from their supports; unlike the case with homogeneous SABRE catalysts, high-field (in situ) SABRE effects were generally not observed with the nanoscale catalysts. The potential for separation and reuse of such catalyst particles is also demonstrated. Taken together, these results support the potential utility of rational design at molecular, mesoscopic, and macroscopic/engineering levels for improving SABRE and HET-SABRE (heterogeneous-SABRE) for applications varying from fundamental studies of catalysis to biomedical imaging. PMID:26185545
Quasi-zero-dimensional cobalt-doped CeO2 dots on Pd catalysts for alcohol electro-oxidation with enhanced poisoning-tolerance.

PubMed

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.
Investigation of heterogeneous asymmetric dihydroxylation over OsO{sub 4}-(QN){sub 2}PHAL catalysts of functionalized bimodal mesoporous silica with ionic liquid

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

Qiu, Shenjie; Sun, Jihong, E-mail: jhsun@bjut.edu.cn; Li, Yuzhen

2011-08-15

Highlights: {yields} Functionalized bimodal mesoporous silica with MTMSPIm{sup +}Cl{sup -}. {yields} Mesoporous catalyst immobilized with OsO{sub 4}-(QN){sub 2}PHAL. {yields} Catalysts for asymmetric dihydroxylation reaction with high yield and enatioselectivity. {yields} Recyclable catalysts. -- Abstract: A novel synthesis of the functionalized bimodal mesoporous silica with ionic liquid (FBMMs) was performed. After grafting 1-methyl-3-(trimethoxysilyl)propylimidazolium chloride onto the surface of bimodal mesoporous silicas, 1,4-bis(9-O-quininyl)phthalazine ((QN){sub 2}-PHAL) and K{sub 2}Os(OH){sub 4}.2H{sub 2}O were immobilized onto the modified FBMMs by adsorption or ionic exchange methods, and then, the asymmetric dihydroxylation reaction was carried out by using solid catalysts. Techniques such as X-ray diffraction, Fourier Transformmore » Infrared spectroscopy, N{sub 2} adsorption and desorption were employed to characterize their structure and properties. The results showed that the mesoporous ordering degree of bimodal mesoporous silica decreased after functionalization and immobilization of OsO{sub 4}-(QN){sub 2}PHAL. Being very effective in asymmetric dihydroxylation with high yield and enantioselectivity, the prepared heterogeneous solid catalyst could be recycled for five times with little loss of enantioselectivity, with comparison of those results obtained in homophase system. Moreover, the effect of Osmium catalyst on asymmetric dihydroxylation was investigated.« less
Ultrasound accelerated Claisen Schmidt condensation: A green route to chalcones

NASA Astrophysics Data System (ADS)

Calvino, V.; Picallo, M.; López-Peinado, A. J.; Martín-Aranda, R. M.; Durán-Valle, C. J.

2006-06-01

Chalcones have been synthesized under sonochemical irradiation by Claisen-Schmidt condensation between benzaldehyde and acetophenone. Two basic activated carbons (Na and Cs-Norit) have been used as catalysts. The effect of the ultrasound activation has been studied. A substantial enhancing effect in the yield was observed when the carbon catalyst was activated under ultrasonic waves. This "green" method (combination of alkaline-doped carbon catalyst and ultrasound waves) has been applied to the synthesis of several chalcones with antibacterial properties achieving, in all cases, excellent activities and selectivities. A comparative study under non-sonic activation has showed that the yields are lower in silent conditions, indicating that the sonication exerts a positive effect on the activity of the catalyst. Cs-doped carbon is presented as the optimum catalyst, giving excellent activity for this type of condensation. Cs-Norit carbon catalyst can compete with the traditional NaOH/EtOH when the reaction is carried out under ultrasounds. The role of solvent in this reaction was studied with ethanol. High conversion was obtained in absence of solvent. The carbons were characterized by thermal analysis, nitrogen adsorption and X-ray photoelectron spectroscopy.
Nitrogen-doped microporous carbon: An efficient oxygen reduction catalyst for Zn-air batteries

NASA Astrophysics Data System (ADS)

Zhang, Li-Yuan; Wang, Meng-Ran; Lai, Yan-Qing; Li, Xiao-Yan

2017-08-01

N-doped microporous carbon as an exceptional metal-free catalyst from waste biomass (banana peel as representative) was obtained via fast catalysis carbonization, followed by N-doping modification. The method achieves a relatively high C conversion efficiency of ∼41.9%. The final carbon materials are doped by N (∼3 at.%) and possess high surface area (∼1097 m2 g-1) and abundant micropores. Compared to commercial Pt/C materials, the as-prepared carbon catalyst exhibits a comparable electrocatalytic activity and much better stability. Furthermore, the metal-free catalyst loaded Zn-air battery possesses higher discharge voltage and power density as compared with that of commercial Pt/C. This novel technique can also be readily applied to produce metal-free carbon catalysts from other typical waste biomass (e.g., orange peel, leaves) as the carbon sources. The method can be developed as a potentially general and effective industrial route to transform waste biomass into high value-added microporous carbon with superior functionalities.
CuNi NPs supported on MIL-101 as highly active catalysts for the hydrolysis of ammonia borane

NASA Astrophysics Data System (ADS)

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

2018-01-01

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

DOE PAGES

Winter, Lea R.; Gomez, Elaine; Yan, Binhang; ...

2017-10-16

CO 2 hydrogenation over Fe-modified Ni/CeO 2 catalysts was investigated in a batch reactor using time-resolved in situ FTIR spectroscopy. Low loading of Ni/CeO 2 was associated with high selectivity to CO over CH 4, while higher Ni loading improved CO 2 hydrogenation activity with a reduced CO selectivity. X-ray absorption near-edge structure (XANES) analysis revealed Ni to be metallic for all catalysts including the CO-selective low loading 0.5% Ni catalyst, suggesting that the selectivity trend is due to structural rather than oxidation state effects. The loading amount of 1.5% Ni was selected for co-impregnation with Fe, based on themore » significant shift in product selectivity towards CH 4 for that loading amount, in order to shift the selectivity towards CO while maintaining high activity. Temperature programmed reduction (TPR) results indicated bimetallic interactions between Ni and Fe, and XANES analysis showed that about 70% of Fe in the bimetallic catalysts was oxidized. The Ni-Fe catalysts demonstrated improved selectivity towards CO without significantly compromising activity, coupling the high activity of Ni catalysts and the high CO selectivity of Fe. The general trends in Ni loading and bimetallic modification should guide efforts to develop non-precious metal catalysts for the selective production of CO by CO 2 hydrogenation.« less
Durability of Pt-Co Alloy Polymer Electrolyte Fuel Cell Cathode Catalysts under Accelerated Stress Tests

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

Papadias, D. D.; Ahluwalia, R. K.; Kariuki, N.

The durability of Pt-Co alloy cathode catalysts supported on high surface area carbon is investigated by subjecting them to accelerated stress tests (ASTs). The catalysts had different initial Co contents and nanoparticle morphologies: a “spongy” porous morphology for the high-Co (H) content catalyst, and a fully alloyed crystalline morphology for the medium-Co (M) and low-Co (L) content catalysts. The specific activity of the catalysts depends on their initial Co content, morphology and nanoparticle size, and remained higher than 1000 μA/cm 2-Pt after 27–50% Co loss. The H-catalyst electrode showed the smallest kinetic overpotentials (η c s) due to higher initialmore » Pt loading than the other two electrodes, but it had the fastest increase in ηcs with AST cycling due to lower Co retention; the L-catalyst electrode showed higher η c s due to a lower initial Pt loading, but had a smaller increase in η c s with aging due to higher Co retention; the M-catalyst electrode showed a similar increase in η c s with aging, but this increase was due to the combined effects of Co dissolution and electrochemically active surface area (ECSA) loss. In conclusion, the modeled increase in mass transfer overpotentials with aging correlates with the initial Pt loading, ECSA loss and the initial catalyst morphology« less
Durability of Pt-Co Alloy Polymer Electrolyte Fuel Cell Cathode Catalysts under Accelerated Stress Tests

DOE PAGES

Papadias, D. D.; Ahluwalia, R. K.; Kariuki, N.; ...

2018-03-17

The durability of Pt-Co alloy cathode catalysts supported on high surface area carbon is investigated by subjecting them to accelerated stress tests (ASTs). The catalysts had different initial Co contents and nanoparticle morphologies: a “spongy” porous morphology for the high-Co (H) content catalyst, and a fully alloyed crystalline morphology for the medium-Co (M) and low-Co (L) content catalysts. The specific activity of the catalysts depends on their initial Co content, morphology and nanoparticle size, and remained higher than 1000 μA/cm 2-Pt after 27–50% Co loss. The H-catalyst electrode showed the smallest kinetic overpotentials (η c s) due to higher initialmore » Pt loading than the other two electrodes, but it had the fastest increase in ηcs with AST cycling due to lower Co retention; the L-catalyst electrode showed higher η c s due to a lower initial Pt loading, but had a smaller increase in η c s with aging due to higher Co retention; the M-catalyst electrode showed a similar increase in η c s with aging, but this increase was due to the combined effects of Co dissolution and electrochemically active surface area (ECSA) loss. In conclusion, the modeled increase in mass transfer overpotentials with aging correlates with the initial Pt loading, ECSA loss and the initial catalyst morphology« less
Improved Oxygen Reduction Activity and Durability of Dealloyed PtCo x Catalysts for Proton Exchange Membrane Fuel Cells: Strain, Ligand, and Particle Size Effects.

PubMed

Jia, Qingying; Caldwell, Keegan; Strickland, Kara; Ziegelbauer, Joseph M; Liu, Zhongyi; Yu, Zhiqiang; Ramaker, David E; Mukerjee, Sanjeev

2015-01-02

The development of active and durable catalysts with reduced platinum content is essential for fuel cell commercialization. Herein we report that the dealloyed PtCo/HSC and PtCo 3 /HSC nanoparticle (NP) catalysts exhibit the same levels of enhancement in oxygen reduction activity (~4-fold) and durability over pure Pt/C NPs. Surprisingly, ex situ high-angle annular dark field scanning transmission electron microscopy (HAADF STEM) shows that the bulk morphologies of the two catalysts are distinctly different: D-PtCo/HSC catalyst is dominated by NPs with solid Pt shells surrounding a single ordered PtCo core; however, the D-PtCo 3 /HSC catalyst is dominated by NPs with porous Pt shells surrounding multiple disordered PtCo cores with local concentration of Co. In situ X-ray absorption spectroscopy (XAS) reveals that these two catalysts possess similar Pt-Pt and Pt-Co bond distances and Pt coordination numbers (CNs), despite their dissimilar morphologies. The similar activity of the two catalysts is thus ascribed to their comparable strain, ligand, and particle size effects. Ex situ XAS performed on D-PtCo 3 /HSC under different voltage cycling stage shows that the continuous dissolution of Co leaves behind the NPs with a Pt-like structure after 30k cycles. The attenuated strain and/or ligand effects caused by Co dissolution are presumably counterbalanced by the particle size effects with particle growth, which likely accounts for the constant specific activity of the catalysts along with voltage cycling.

Improved Oxygen Reduction Activity and Durability of Dealloyed PtCo x Catalysts for Proton Exchange Membrane Fuel Cells: Strain, Ligand, and Particle Size Effects

DOE PAGES

Jia, Qingying; Caldwell, Keegan; Strickland, Kara; ...

2014-11-19

The development of active and durable catalysts with reduced platinum content is essential for fuel cell commercialization. Here in this paper, we report that the dealloyed PtCo/HSC and PtCo 3/HSC nanoparticle (NP) catalysts exhibit the same levels of enhancement in oxygen reduction activity (~4-fold) and durability over pure Pt/C NPs. Surprisingly, ex situ high-angle annular dark field scanning transmission electron microscopy (HAADF STEM) shows that the bulk morphologies of the two catalysts are distinctly different: D-PtCo/HSC catalyst is dominated by NPs with solid Pt shells surrounding a single ordered PtCo core; however, the D-PtCo 3/HSC catalyst is dominated by NPsmore » with porous Pt shells surrounding multiple disordered PtCo cores with local concentration of Co. In situ X-ray absorption spectroscopy (XAS) reveals that these two catalysts possess similar Pt–Pt and Pt–Co bond distances and Pt coordination numbers (CNs), despite their dissimilar morphologies. The similar activity of the two catalysts is thus ascribed to their comparable strain, ligand, and particle size effects. Ex situ XAS performed on D-PtCo 3/HSC under different voltage cycling stage shows that the continuous dissolution of Co leaves behind the NPs with a Pt-like structure after 30k cycles. The attenuated strain and/or ligand effects caused by Co dissolution are presumably counterbalanced by the particle size effects with particle growth, which likely accounts for the constant specific activity of the catalysts along with voltage cycling.« less
Spectroscopic insights into the nature of active sites in iron–nitrogen–carbon electrocatalysts for oxygen reduction in acid

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

Jia, Qingying; Ramaswamy, Nagappan; Tylus, Urszula

Developing efficient and inexpensive catalysts for the sluggish oxygen reduction reaction (ORR) constitutes one of the grand challenges in the fabrication of commercially viable fuel cell devices and metal–air batteries for future energy applications. Despite recent achievements in designing advanced Pt-based and Pt-free catalysts, current progress primarily involves an empirical approach of trial-and-error combination of precursors and synthesis conditions, which limits further progress. Rational design of catalyst materials requires proper understanding of the mechanistic origin of the ORR and the underlying surface properties under operating conditions that govern catalytic activity. Herein, several different groups of iron-based catalysts synthesized via differentmore » methods and/or precursors were systematically studied by combining multiple spectroscopic techniques under ex situ and in situ conditions in an effort to obtain a comprehensive understanding of the synthesis-products correlations, nature of active sites, and the reaction mechanisms. These catalysts include original macrocycles, macrocycle-pyrolyzed catalysts, and Fe-N–C catalysts synthesized from individual Fe, N, and C precursors including polymer-based catalysts, metal organic framework (MOF)-based catalysts, and sacrificial support method (SSM)-based catalysts. The latter group of catalysts is most promising as not only they exhibit exceptional ORR activity and/or durability, but also the final products are controllable. We show that the high activity observed for most pyrolyzed Fe-based catalysts can mainly be attributed to a single active site: non-planar Fe–N 4 moiety embedded in distorted carbon matrix characterized by a high potential for the Fe 2+/3+ redox transition in acidic electrolyte/environment. The high intrinsic ORR activity, or turnover frequency (TOF), of this site is shown to be accounted for by redox catalysis mechanism that highlights the dominant role of the site-blocking effect. Moreover, a highly active MOF-based catalyst without Fe–N moieties was developed, and the active sites were identified as nitrogen-doped carbon fibers with embedded iron particles that are not directly involved in the oxygen reduction pathway. The high ORR activity and durability of catalysts involving this second site, as demonstrated in fuel cell, are attributed to the high density of active sites and the elimination or reduction of Fenton-type processes. The latter are initiated by hydrogen peroxide but are known to be accelerated by iron ions exposed to the surface, resulting in the formation of damaging free-radicals.« less
Highly Stable and Active Catalyst for Sabatier Reactions

NASA Technical Reports Server (NTRS)

Hu, Jianli; Brooks, Kriston P.

2012-01-01

Highly active Ru/TiO2 catalysts for Sabatier reaction have been developed. The catalysts have shown to be stable under repeated shutting down/startup conditions. When the Ru/TiO2 catalyst is coated on the engineered substrate Fe-CrAlY felt, activity enhancement is more than doubled when compared with an identically prepared engineered catalyst made from commercial Degussa catalyst. Also, bimetallic Ru-Rh/TiO2 catalysts show high activity at high throughput.
A surfactant free preparation of ultradispersed surface-clean Pt catalyst with highly stable electrocatalytic performance

NASA Astrophysics Data System (ADS)

Tao, Lu; Zhao, Yueping; Zhao, Yufeng; Huang, Shifei; Yang, Yunxia; Tong, Qi; Gao, Faming

2018-02-01

High efficiency platinum-based catalyst demands the ultrafine size and well dispersion of Pt nanoparticles (NPs), with clean surface and strong interactions between the supports. In this work, we demonstrate a simple strategy for the preparation of ultra-dispersed surface-clean Pt catalyst with high stability, in which the Pt nanoparticles (NPs) with 1.8 ± 0.6 nm in size are anchored tightly on a 3D hierarchical porous graphitized carbon (3D-HPG) through galvanic replacement reaction. The as-obtained catalyst can undergo 2000 voltage cycles with negligible activity decay and no apparent structure and size changes for MOR during the durability test, and its mass activity for ORR only reduce 18.3% after 5000 cycles. The excellent performance is attributed to strong anchoring effect between carbon support and Pt nanoparticles.
Highly active carbon supported Pd cathode catalysts for direct formic acid fuel cells

NASA Astrophysics Data System (ADS)

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

2016-12-01

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

PubMed

Jayakumar, Sanjeevi; Li, He; Chen, Jian; Yang, Qihua

2018-01-24

The development of solid catalysts containing multiple active sites that work cooperatively is very attractive for biomimetic catalysis. Herein, we report the synthesis of bifunctional catalysts by supporting cationic porphyrin-based polymers on carbon nanotubes (CNTs) using the direct reaction of 5,10,15,20-tetrakis(4-pyridyl)porphyrin zinc(II), di(1H-imidazol-1-yl)methane, and 1,4-bis(bromomethyl)benzene in the presence of CNTs. The bifunctional catalysts could efficiently catalyze the cycloaddition reaction of epoxides and CO 2 under solvent-free conditions with porphyrin zinc(II) as the Lewis acid site and a bromine anion as a nucleophilic agent working in a cooperative way. Furthermore, a relative amount of porphyrin zinc(II) and quaternary ammonium bromide could be facilely adjusted for facilitating cooperative behavior. The bifunctional catalyst with a TOF up to 2602 h -1 is much more active than the corresponding homogeneous counterpart and is one of the most active heterogeneous catalysts ever reported under cocatalyst-free conditions. The high activity is mainly attributed to the enhanced cooperation effect of the bifunctional catalyst. With a wide substrate scope, the bifunctional catalyst could be stably recycled. This work demonstrates a new approach for the generation of a cooperative activation effect for solid catalysts.
Development of a reaction cell for in-situ/operando studies of surface of a catalyst under a reaction condition and during catalysis.

PubMed

Nguyen, Luan; Tao, Franklin Feng

2016-06-01

Tracking surface chemistry of a catalyst during catalysis is significant for fundamental understanding of catalytic performance of the catalyst since it allows for establishing an intrinsic correlation between surface chemistry of a catalyst at its working status and its corresponding catalytic performance. Ambient pressure X-ray photoelectron spectroscopy can be used for in-situ studies of surfaces of different materials or devices in a gas. To simulate the gaseous environment of a catalyst in a fixed-bed a flowing gaseous environment of reactants around the catalyst is necessary. Here, we report the development of a new flowing reaction cell for simulating in-situ study of a catalyst surface under a reaction condition in gas of one reactant or during catalysis in a mixture of reactants of a catalytic reaction. The homemade reaction cell is installed in a high vacuum (HV) or ultrahigh vacuum (UHV) environment of a chamber. The flowing gas in the reaction cell is separated from the HV or UHV environment through well sealings at three interfaces between the reaction cell and X-ray window, sample door and aperture of front cone of an energy analyzer. Catalyst in the cell is heated through infrared laser beam introduced through a fiber optics interfaced with the reaction cell through a homemade feedthrough. The highly localized heating on the sample holder and Au-passivated internal surface of the reaction cell effectively minimizes any unwanted reactions potentially catalyzed by the reaction cell. The incorporated laser heating allows a fast heating and a high thermal stability of the sample at a high temperature. With this cell, a catalyst at 800 °C in a flowing gas can be tracked readily.
Characteristics of a commercially aged Ni-Mo/Al2O3 hydrotreating catalyst: component distribution, nature of coke and effects of regeneration

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

Bogdanor, J.M.

1984-01-01

Information concerning the morphology and behavior of active components on commercially aged catalyst, the effects of regeneration conditions on activity, and insights into the nature of coke and contaminant metal deposits could lead to improved catalysts and operating conditions , yielding significant economic returns. Spent Ni-Mo/Al2O3 hydrotreating catalyst from a commercial hydrotreater was examined using TGA, SEM, STEM, XPS, and a microreactor. Information concerning intraparticle distributions of active components, characteristics of the coke and metal deposits, and catalytic activity for fresh, spent and regenerated catalyst was used to draw general conclusions concerning hydrotreating catalyst deactivation. It was found that catalyticmore » activity was reduced and the nature of the hydrogenation function was altered due to bulk migration and agglomeration of molybdenum. This process was found to be accelerated by high-temperature regeneration. Results also indicated that iron deposits might catalyze formation of coke. Tentative generalizations and suggestions on improved reactor operation are presented.« less
ZIF-67-derived hollow nanocages with layered double oxides shell as high-Efficiency catalysts for CO oxidation

NASA Astrophysics Data System (ADS)

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.
Leaching behavior of lanthanum, nickel and iron from spent catalyst using inorganic acids

NASA Astrophysics Data System (ADS)

Astuti, W.; Prilitasari, N. M.; Iskandar, Y.; Bratakusuma, D.; Petrus, H. T. B. M.

2018-01-01

Highly technological applications of rare earth metals (REs) and scarcity of supply have become an incentive torecover the REs from various resources, which include high grade and low grade ores, as well as recycledwaste materials. Spent hydrocracking catalyst contain lanthanum and a variety of valuable metals such as nickel and iron. This study investigated the recovery of lanthanum, nickel and iron from spent hydrocracking catalyst by leaching using various inorganic acid (sulfuric acid, hydrochloric acid, and nitric acid). The effect of acid concentration, type of acid and leaching temperature was conducted to study the leaching behavior of each valuable metal from spent-catalyst. It has been shown that it is possible to recover more than 90% of lanthanum, however the leaching efficiency of nickel and iron in this process was very low. It can be concluded that the leaching process is selective for lanthanum recovery from hydrocracking spent-catalyst.
Achieving significantly enhanced visible-light photocatalytic efficiency using a polyelectrolyte: the composites of exfoliated titania nanosheets, graphene, and poly(diallyl-dimethyl-ammonium chloride)

NASA Astrophysics Data System (ADS)

Zhang, Qian; An, Qi; Luan, Xinglong; Huang, Hongwei; Li, Xiaowei; Meng, Zilin; Tong, Wangshu; Chen, Xiaodong; Chu, Paul K.; Zhang, Yihe

2015-08-01

A high-performance visible-light-active photocatalyst is prepared using the polyelectrolyte/exfoliated titania nanosheet/graphene oxide (GO) precursor by flocculation followed by calcination. The polyelectrolyte poly(diallyl-dimethyl-ammonium chloride) serves not only as an effective binder to precipitate GO and titania nanosheets, but also boosts the overall performance of the catalyst significantly. Unlike most titania nanosheet-based catalysts reported in the literature, the composite absorbs light in the UV-Vis-NIR range. Its decomposition rate of methylene blue is 98% under visible light. This novel strategy of using a polymer to enhance the catalytic performance of titania nanosheet-based catalysts affords immense potential in designing and fabricating next-generation photocatalysts with high efficiency.A high-performance visible-light-active photocatalyst is prepared using the polyelectrolyte/exfoliated titania nanosheet/graphene oxide (GO) precursor by flocculation followed by calcination. The polyelectrolyte poly(diallyl-dimethyl-ammonium chloride) serves not only as an effective binder to precipitate GO and titania nanosheets, but also boosts the overall performance of the catalyst significantly. Unlike most titania nanosheet-based catalysts reported in the literature, the composite absorbs light in the UV-Vis-NIR range. Its decomposition rate of methylene blue is 98% under visible light. This novel strategy of using a polymer to enhance the catalytic performance of titania nanosheet-based catalysts affords immense potential in designing and fabricating next-generation photocatalysts with high efficiency. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr03256c
Highly efficient bioinspired molecular Ru water oxidation catalysts with negatively charged backbone ligands.

PubMed

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-coordinate Ru(IV) species was isolated as a reaction intermediate, shedding light on the reaction mechanisms of Ru-catalyzed water oxidation chemistry. Auxiliary ligands have dramatic effects on the water oxidation catalysis in terms of the reactivity and the reaction mechanism. For instance, Ru-bda (H2bda = 2,2'-bipyridine-6,6'-dicarboxylic acid) water oxidation catalysts catalyze Ce(IV)-driven water oxidation extremely fast via the radical coupling of two Ru(V)═O species, while Ru-pda (H2pda = 1,10-phenanthroline-2,9-dicarboxylic acid) water oxidation catalysts catalyze the same reaction slowly via water nucleophilic attack on a Ru(V)═O species. With a number of active Ru catalysts in hands, light driven water oxidation was accomplished using catalysts with low catalytic onset potentials. The structures of molecular catalysts could be readily tailored to introduce additional functional groups, which favors the fabrication of state-of-the-art Ru-based water oxidation devices, such as electrochemical water oxidation anodes and photo-electrochemical anodes. The development of efficient water oxidation catalysts has led to a step forward in the sustainable energy system.
Intensification of biodiesel production from soybean oil and waste cooking oil in the presence of heterogeneous catalyst using high speed homogenizer.

PubMed

Joshi, Saurabh; Gogate, Parag R; Moreira, Paulo F; Giudici, Reinaldo

2017-11-01

In the present work, high speed homogenizer has been used for the intensification of biodiesel synthesis from soybean oil and waste cooking oil (WCO) used as a sustainable feedstock. High acid value waste cooking oil (27mg of KOH/g of oil) was first esterified with methanol using sulphuric acid as catalyst in two stages to bring the acid value to desired value of 1.5mg of KOH/g of oil. Transesterification of soybean oil (directly due to lower acid value) and esterified waste cooking oil was performed in the presence of heterogeneous catalyst (CaO) for the production of biodiesel. Various experiments were performed for understanding the effect of operating parameters viz. molar ratio, catalyst loading, reaction temperature and speed of rotation of the homogenizer. For soybean oil, the maximum biodiesel yield as 84% was obtained with catalyst loading of 3wt% and molar ratio of oil to methanol of 1:10 at 50°C with 12,000rpm as the speed of rotation in 30min. Similarly biodiesel yield of 88% was obtained from waste cooking oil under identical operating conditions except for the catalyst loading which was 1wt%. Significant increase in the rate of biodiesel production with yields from soybean oil as 84% (in 30min) and from WCO as 88% (30min) was established due to the use of high speed homogenizer as compared to the conventional stirring method (requiring 2-3h for obtaining similar biodiesel yield). The observed intensification was attributed to the turbulence caused at microscale and generation of fine emulsions due to the cavitational effects. Overall it can be concluded from this study that high speed homogenizer can be used as an alternate cavitating device to efficiently produce biodiesel in the presence of heterogeneous catalysts. Copyright © 2017 Elsevier B.V. All rights reserved.
PILOT-SCALE STUDY OF THE EFFECT OF SELECTIVE CATALYTIC REDUCTION CATALYST ON MERCURY SPECIATION IN ILLINOIS AND POWDER RIVER BASIN COAL COMBUSTION FLUE GASES

EPA Science Inventory

A study was conducted to investigate the effect of selective catalytic reduction (SCR) catalyst on mercury (Hg) speciation in bituminous and subbituminous coal combustion flue gases. Three different Illinois Basin bituminous coals (from high to low sulfur and chlorine) and one Po...
Electrochemical Catalyst-Support Effects and Their Stabilizing Role for IrOx Nanoparticle Catalysts during the Oxygen Evolution Reaction.

PubMed

Oh, Hyung-Suk; Nong, Hong Nhan; Reier, Tobias; Bergmann, Arno; Gliech, Manuel; Ferreira de Araújo, Jorge; Willinger, Elena; Schlögl, Robert; Teschner, Detre; Strasser, Peter

2016-09-28

Redox-active support materials can help reduce the noble-metal loading of a solid chemical catalyst while offering electronic catalyst-support interactions beneficial for catalyst durability. This is well known in heterogeneous gas-phase catalysis but much less discussed for electrocatalysis at electrified liquid-solid interfaces. Here, we demonstrate experimental evidence for electronic catalyst-support interactions in electrochemical environments and study their role and contribution to the corrosion stability of catalyst/support couples. Electrochemically oxidized Ir oxide nanoparticles, supported on high surface area carbons and oxides, were selected as model catalyst/support systems for the electrocatalytic oxygen evolution reaction (OER). First, the electronic, chemical, and structural state of the catalyst/support couple was compared using XANES, EXAFS, TEM, and depth-resolved XPS. While carbon-supported oxidized Ir particle showed exclusively the redox state (+4), the Ir/IrOx/ATO system exhibited evidence of metal/metal-oxide support interactions (MMOSI) that stabilized the metal particles on antimony-doped tin oxide (ATO) in sustained lower Ir oxidation states (Ir(3.2+)). At the same time, the growth of higher valent Ir oxide layers that compromise catalyst stability was suppressed. Then the electrochemical stability and the charge-transfer kinetics of the electrocatalysts were evaluated under constant current and constant potential conditions, where the analysis of the metal dissolution confirmed that the ATO support mitigates Ir(z+) dissolution thanks to a stronger MMOSI effect. Our findings raise the possibility that MMOSI effects in electrochemistry-largely neglected in the past-may be more important for a detailed understanding of the durability of oxide-supported nanoparticle OER catalysts than previously thought.
Sodium citrate assisted facile synthesis of AuPd alloy networks for ethanol electrooxidation with high activity and durability

NASA Astrophysics Data System (ADS)

Zhai, Yanling; Zhu, Zhijun; Lu, Xiaolin; Zhou, H. Susan

2016-10-01

The direct ethanol fuel cell is an emerging energy conversion device for which palladium is considered as the one of the most effective components for anode catalyst, however, its widespread application has been still limited by the activity and durability of the anode catalyst. In this work, AuPd alloy networks (NWs) are synthesized using H2PdCl4 and HAuCl4 as precursors reduced by NaBH4 in the presence of sodium citrate (SC). The results reveal that SC plays significant role in network structure, resulting in the enhanced electrocatalytic activity of the catalyst. This self-supported AuPd NWs catalyst exhibits much higher electrochemical catalytic activity than commercial Pd/C catalyst toward ethanol electrooxidation in alkaline solution. Significantly, AuPd NWs catalyst shows extremely high durability at the beginning of the chronoamperometry test, and as high as 49% of the mass current density (1.41 A/mgPd) remains after 4000 s current-time test at -0.3 V (vs. Ag/AgCl) in N2-saturated KOH-ethanol solution. This strategy provides a facile method for the preparation of alloy networks with high electrochemical activity, and can be potentially expanded to a variety of electrochemical applications.
Effect of Ni-Co Ternary Molten Salt Catalysts on Coal Catalytic Pyrolysis Process

NASA Astrophysics Data System (ADS)

Cui, Xin; Qi, Cong; Li, Liang; Li, Yimin; Li, Song

2017-08-01

In order to facilitate efficient and clean utilization of coal, a series of Ni-Co ternary molten salt crystals are explored and the catalytic pyrolysis mechanism of Datong coal is investigated. The reaction mechanisms of coal are achieved by thermal gravimetric analyzer (TGA), and a reactive kinetic model is constructed. The microcosmic structure and macerals are observed by scanning electron microscope (SEM). The catalytic effects of ternary molten salt crystals at different stages of pyrolysis are analyzed. The experimental results show that Ni-Co ternary molten salt catalysts have the capability to bring down activation energy required by pyrolytic reactions at its initial phase. Also, the catalysts exert a preferable catalytic action on macromolecular structure decomposition and free radical polycondensation reactions. Furthermore, the high-temperature condensation polymerization is driven to decompose further with a faster reaction rate by the additions of Ni-Co ternary molten salt crystal catalysts. According to pyrolysis kinetic research, the addition of catalysts can effectively decrease the activation energy needed in each phase of pyrolysis reaction.
The effect of activated carbon support surface modification on characteristics of carbon nanospheres prepared by deposition precipitation of Fe-catalyst

NASA Astrophysics Data System (ADS)

Kristianto, H.; Arie, A. A.; Susanti, R. F.; Halim, M.; Lee, J. K.

2016-11-01

In this study the effect of activated carbon support modification to synthesis of CNSs was observed. Modification of activated carbon was done by using nitric acid. The effect of modification was analyzed from its FTIR spectra. The Fe catalysts were deposited on to the support by using urea deposition precipitation method at various initial catalysts concentration. CNSs was synthesized by utilizing cooking palm oil as renewable carbon source, and pyrolized at 700°C for 1 hour under nitrogen atmosphere. The products obtained then analyzed using SEM-EDS, TEM, XRD, and Raman spectroscopy. The modification of activated carbon support had increased the oxygen functional group. This increase resulted on increase of metal catalysts deposited on activated carbon surface. Peak of C (100) was observed, while ID/IG of samples were obtained around 0.9, which is commonly obtained for CNSs. High catalysts loading on modified activated carbon support caused decomposition of CNSs and formation carbon onion.
Ru-assisted synthesis of Pd/Ru nanodendrites with high activity for ethanol electrooxidation

NASA Astrophysics Data System (ADS)

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

2015-07-01

Due to the specific physical and chemical properties of a highly branched noble metal, the controllable synthesis has attracted much attention. This article reports the synthesis of Pd/Ru nanodendrites by a facile method using an oil bath in the presence of polyvinyl pyrrolidone, potassium bromide and ascorbic acid. The morphology, structure, and composition of the as-prepared catalysts were characterized by means of X-ray diffraction, X-ray photoelectron spectroscopy and transmission electron microscopy. In the electrochemical measurement, the as-prepared Pd7/Ru1 bimetallic nanodendrites provide a large electrochemically active surface area and exhibit high peak current density in the forward scan toward ethanol electrooxidation, which is nearly four times higher than those of a pure Pd catalyst. The as-prepared Pd7/Ru1 catalysts also exhibit significantly enhanced cycling stability toward ethanol oxidation in alkaline medium, which are mainly ascribed to the synergetic effect between Pd and Ru. This indicates that the Pd7/Ru1 catalysts should have great potential applications in direct ethanol fuel cells.Due to the specific physical and chemical properties of a highly branched noble metal, the controllable synthesis has attracted much attention. This article reports the synthesis of Pd/Ru nanodendrites by a facile method using an oil bath in the presence of polyvinyl pyrrolidone, potassium bromide and ascorbic acid. The morphology, structure, and composition of the as-prepared catalysts were characterized by means of X-ray diffraction, X-ray photoelectron spectroscopy and transmission electron microscopy. In the electrochemical measurement, the as-prepared Pd7/Ru1 bimetallic nanodendrites provide a large electrochemically active surface area and exhibit high peak current density in the forward scan toward ethanol electrooxidation, which is nearly four times higher than those of a pure Pd catalyst. The as-prepared Pd7/Ru1 catalysts also exhibit significantly enhanced cycling stability toward ethanol oxidation in alkaline medium, which are mainly ascribed to the synergetic effect between Pd and Ru. This indicates that the Pd7/Ru1 catalysts should have great potential applications in direct ethanol fuel cells. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr02713f
Acidic Mesoporous Zeolite ZSM-5 Supported Cu Catalyst with Good Catalytic Performance in the Hydroxysulfurization of Styrenes with Disulfides.

PubMed

Hu, Jun; Zhu, Chaojie; Xia, Feifei; Fang, Zhongxue; Yang, Fengli; Weng, Jushi; Yao, Pengfei; Zheng, Chunzhi; Dong, Hai; Fu, Wenqian

2017-12-19

Development of highly active heterogeneous catalysts is an effective strategy for modern organic synthesis chemistry. In this work, acidic mesoporous zeolite ZSM-5 (HZSM-5-M), acidic-free mesoporous zeolite TS-1 (TS-1-M), and basic ETS-10 zeolite supported metal Cu catalysts were prepared to investigate their catalytic performances in the hydroxysulfurization of styrenes with diaryl disulfides. The effect of pore size and acidities of the supports, as well as the Cu species electronic properties of the catalysts on reaction activity were investigated. The results show that Cu⁺ and Cu 2+ binded on HZSM-5-M show the highest activity and product selectivity for the desired β -hydroxysulfides compounds.

Acidic Mesoporous Zeolite ZSM-5 Supported Cu Catalyst with Good Catalytic Performance in the Hydroxysulfurization of Styrenes with Disulfides

PubMed Central

Hu, Jun; Zhu, Chaojie; Xia, Feifei; Fang, Zhongxue; Yang, Fengli; Weng, Jushi; Yao, Pengfei; Zheng, Chunzhi; Dong, Hai; Fu, Wenqian

2017-01-01

Development of highly active heterogeneous catalysts is an effective strategy for modern organic synthesis chemistry. In this work, acidic mesoporous zeolite ZSM-5 (HZSM-5-M), acidic-free mesoporous zeolite TS-1 (TS-1-M), and basic ETS-10 zeolite supported metal Cu catalysts were prepared to investigate their catalytic performances in the hydroxysulfurization of styrenes with diaryl disulfides. The effect of pore size and acidities of the supports, as well as the Cu species electronic properties of the catalysts on reaction activity were investigated. The results show that Cu+ and Cu2+ binded on HZSM-5-M show the highest activity and product selectivity for the desired β-hydroxysulfides compounds. PMID:29257075
CO-oxidation catalysts: Low-temperature CO oxidation over Noble-Metal Reducible Oxide (NMRO) catalysts

NASA Technical Reports Server (NTRS)

Herz, Richard K.

1990-01-01

Oxidation of CO to CO2 is an important reaction technologically and environmentally and a complex and interesting reaction scientifically. In most cases, the reaction is carried out in order to remove CO as an environmental hazard. A major application of heterogeneous catalysts is catalytic oxidation of CO in the exhaust of combustion devices. The reaction over catalysts in exhaust gas is fast and often mass-transfer-limited since exhaust gases are hot and O2/CO ratios are high. The main challenges to catalyst designers are to control thermal sintering and chemical poisoning of the active materials. The effect of the noble metal on the oxide is discussed, followed by the effect of the oxide on the noble metal, the interaction of the noble metal and oxide to form unique catalytic sites, and the possible ways in which the CO oxidation reaction is catalyzed by the NMRO materials.
External Catalyst Breakup Phenomena

DTIC Science & Technology

1976-06-01

catalyst particle can cause high internal pressures which result in particle destruction. Analytical results suggest rhat erosion effects from solid...mechanisms. * Pressure Forces. High G loadings and bed pressure drops should be avoided. Bed pre-loads should be kept at a minimum value. Thruster...5.2.7.1 Failure Theories ............................ 243 5.2.7.2 Maximum Tension Stress Criterion ............ 244 5.2.7.3 Distortion Energy Approach
Hydro-isomerization of n-hexane on bi-functional catalyst: Effect of total and hydrogen partial pressures

NASA Astrophysics Data System (ADS)

Thoa, Dao Thi Kim; Loc, Luu Cam

2017-09-01

The effect of both total pressure and hydrogen partial pressure during n-hexane hydro-isomerization over platinum impregnated on HZSM-5 was studied. n-Hexane hydro-isomerization was conducted at atmospheric pressure and 0.7 MPa to observe the influence of total pressure. In order to see the effect of hydrogen partial pressure, the reaction was taken place at different partial pressure of hydrogen varied from 307 hPa to 718 hPa by dilution with nitrogen to keep the total pressure at 0.1 MPa. Physico-chemical characteristics of catalyst were determined by the methods of nitrogen physi-sorption BET, SEM, XRD, TEM, NH3-TPD, TPR, and Hydrogen Pulse Chemi-sorption. Activity of catalyst in the hydro-isomerization of n-hexane was studied in a micro-flow reactor in the temperature range of 225-325 °C; the molar ratio H2/ hydrocarbon: 5.92, concentration of n-hexane: 9.2 mol.%, GHSV 2698 h-1. The obtained catalyst expressed high acid density, good reducing property, high metal dispersion, and good balance between metallic and acidic sites. It is excellent contact for n-hexane hydro-isomerization. At 250 °C, n-hexane conversion and selectivity were as high as 59-76 % and 85-99 %, respectively. It was found that catalytic activity was promoted either by total pressure or hydrogen partial pressure. At total pressure of 0.7 MPa while hydrogen partial pressure of 718 hPa, catalyst produced 63 RON liquid product containing friendly environmental iso-paraffins which is superior blending stock for green gasoline. Hydrogen did not only preserve catalyst actives by depressing hydrocracking and removing coke precursors but also facilitated hydride transfer step in the bi-functional bi-molecular mechanism.
Non-Noble Metal Oxide Catalysts for Methane Catalytic Combustion: Sonochemical Synthesis and Characterisation

PubMed Central

Jędrzejczyk, Roman J.; Dziedzicka, Anna; Kuterasiński, Łukasz; Sitarz, Maciej

2017-01-01

The aim of this study was to obtain nanocrystalline mixed metal-oxide–ZrO2 catalysts via a sonochemically-induced preparation method. The effect of a stabiliser’s addition on the catalyst parameters was investigated by several characterisation methods including X-ray Diffraction (XRD), nitrogen adsorption, X-ray fluorescence (XRF), scanning electron microscopy (SEM) equipped with energy dispersive X-ray spectrometer (EDS), transmission electron microscopy (TEM) and µRaman. The sonochemical preparation method allowed us to manufacture the catalysts with uniformly dispersed metal-oxide nanoparticles at the support surface. The catalytic activity was tested in a methane combustion reaction. The activity of the catalysts prepared by the sonochemical method was higher than that of the reference catalysts prepared by the incipient wetness method without ultrasonic irradiation. The cobalt and chromium mixed zirconia catalysts revealed their high activities, which are comparable with those presented in the literature. PMID:28686190
Calcium Oxide Derived from Waste Shells of Mussel, Cockle, and Scallop as the Heterogeneous Catalyst for Biodiesel Production

PubMed Central

Chaiyut, Nattawut; Worawanitchaphong, Phatsakon

2013-01-01

The waste shell was utilized as a bioresource of calcium oxide (CaO) in catalyzing a transesterification to produce biodiesel (methyl ester). The economic and environmen-friendly catalysts were prepared by a calcination method at 700–1,000°C for 4 h. The heterogeneous catalysts were characterized by X-ray diffraction (XRD), X-ray fluorescence (XRF), scanning electron microscopy (SEM), and the Brunauer-Emmett-Teller (BET) method. The effects of reaction variables such as reaction time, reaction temperature, methanol/oil molar ratio, and catalyst loading on the yield of biodiesel were investigated. Reusability of waste shell catalyst was also examined. The results indicated that the CaO catalysts derived from waste shell showed good reusability and had high potential to be used as biodiesel production catalysts in transesterification of palm oil with methanol. PMID:24453854
Turning Biodiesel Waste Glycerol into 1,3-Propanediol: Catalytic Performance of Sulphuric acid-Activated Montmorillonite Supported Platinum Catalysts in Glycerol Hydrogenolysis.

PubMed

Samudrala, Shanthi Priya; Kandasamy, Shalini; Bhattacharya, Sankar

2018-05-10

Direct C-O hydrogenolysis of bioglycerine to produce 1,3-propanediol selectively is a vital technology that can expand the scope of biodiesel industry and green chemical production from biomass. Herein we report sulphuric acid-activated montmorillonite clay supported platinum nanoparticles as highly effective solid acid catalysts for the selective production of 1,3-propanediol from glycerol. The catalytic performances of the catalysts were investigated in the hydrogenolysis of glycerol with a fixed bed reactor under ambient pressure. The results were found promising and showed that the activation of montmorillonite by sulphuric acid incorporated Brønsted acidity in the catalyst and significantly improved the selectivity to 1,3-propanediol. The catalytic performance of different platinum loaded catalysts was examined and 2 wt% Pt/S-MMT catalyst presented superior activity among others validating 62% 1,3-propanediol selectivity at 94% glycerol conversion. The catalytic activity of 2Pt/S-MMT was systematically investigated under varying reaction parameters including reaction temperature, hydrogen flow rate, glycerol concentration, weight hourly space velocity, and contact time to derive the optimum conditions for the reaction. The catalyst stability, reusability and structure-activity correlation were also elucidated. The high performance of the catalyst could be ascribed to well disperse Pt nanoparticles immobilized on acid-activated montmorillonite, wider pore-structure and appropriate acid sites of the catalyst.
Synthesis of High-Quality Biodiesel Using Feedstock and Catalyst Derived from Fish Wastes.

PubMed

Madhu, Devarapaga; Arora, Rajan; Sahani, Shalini; Singh, Veena; Sharma, Yogesh Chandra

2017-03-15

A low-cost and high-purity calcium oxide (CaO) was prepared from waste crab shells, which were extracted from the dead crabs, was used as an efficient solid base catalyst in the synthesis of biodiesel. Raw fish oil was extracted from waste parts of fish through mechanical expeller followed by solvent extraction. Physical as well as chemical properties of raw fish oil were studied, and its free fatty acid composition was analyzed with GC-MS. Stable and high-purity CaO was obtained when the material was calcined at 800 °C for 4 h. Prepared catalyst was characterized by XRD, FT-IR, and TGA/DTA. The surface structure of the catalyst was analyzed with SEM, and elemental composition was determined by EDX spectra. Esterification followed by transesterification reactions were conducted for the synthesis of biodiesel. The effect of cosolvent on biodiesel yield was studied in each experiment using different solvents such as toluene, diethyl ether, hexane, tetrahydrofuran, and acetone. High-quality and pure biodiesel was synthesized and characterized by 1 H NMR and FT-IR. Biodiesel yield was affected by parameters such as reaction temperature, reaction time, molar ratio (methanol:oil), and catalyst loading. Properties of synthesized biodiesel such as density, kinematic viscosity, and cloud point were determined according to ASTM standards. Reusability of prepared CaO catalyst was checked, and the catalyst was found to be stable up to five runs without significant loss of catalytic activity.
Catalytic activity of CuOn-La2O3/gamma-Al2O3 for microwave assisted ClO2 catalytic oxidation of phenol wastewater.

PubMed

Bi, Xiaoyi; Wang, Peng; Jiang, Hong

2008-06-15

In order to develop a catalyst with high activity and stability for microwave assisted ClO2 catalytic oxidation, we prepared CuOn-La2O3/gamma-Al2O3 by impregnation-deposition method, and determined its properties using BET, XRF, XPS and chemical analysis techniques. The test results show that, better thermal ability of gamma-Al2O3 and high loading of Cu in the catalyst can be achieved by adding La2O3. The microwave assisted ClO2 catalytic oxidation process with CuOn-La2O3/gamma-Al2O3 used as catalyst was also investigated, and the results show that the catalyst has an excellent catalytic activity in treating synthetic wastewater containing 100 mg/L phenol, and 91.66% of phenol and 50.35% of total organic carbon (TOC) can be removed under the optimum process conditions. Compared with no catalyst process, CuOn-La2O3/gamma-Al2O3 can effectively degrade contaminants in short reaction time and with low oxidant dosage, extensive pH range. The comparison of phenol removal efficiency in the different process indicates that microwave irradiation and catalyst work together to oxidize phenol effectively. It can therefore be concluded from results and discussion that CuOn-La2O3/gamma-Al2O3 is a suitable catalyst in microwave assisted ClO2 catalytic oxidation process.
UV Light-Assisted Synthesis of Highly Efficient Pd-Based Catalyst over NiO for Hydrogenation of o-Chloronitrobenzene

PubMed Central

Jiang, Weidong; Xu, Bin; Fan, Guangyin; Zhang, Kaiming; Xiang, Zhen; Liu, Xiaoqiang

2018-01-01

Supported Pd-based catalyst over active nickel oxide (NiO) was repared using the impregnation method companying with UV-light irradiation. Moreover, the catalytic performance of the obtained Pd-based catalysts was evaluated towards the hydrogenation of o-chloronitrobenzene (o-CNB). Observations indicate that the as-prepared UV-irradiated Pd/NiO catalyst with a mole fraction 0.2% (0.2%Pd/NiO) has higher activity and selectivity in the o-CNB hydrogenation. Especially, UV-light irradiation played a positive role in the improvement of catalytic activity of 0.2%Pd/NiO catalyst, exhibiting an excess 11-fold activity superiority in contrast with non-UV-irradiated 0.2%Pd/NiO catalyst. In addition, it was investigated that effects of varied factors (i.e., reaction time, temperature, o-CNB/Pd ratio, Pd loading, hydrogen pressure) on the selective hydrogenation of ο-CNB catalyzed by UV-irradiated 0.2%Pd/NiO catalyst. Under the reaction conditions of 60 °C, 0.5 h, 1 MPa H2 pressure, 100% conversion of o-CNB, and 81.1% o-CAN selectivity were obtained, even at high molar ratio (8000:1) of o-CNB to Pd. PMID:29662004
UV Light-Assisted Synthesis of Highly Efficient Pd-Based Catalyst over NiO for Hydrogenation of o-Chloronitrobenzene.

PubMed

Jiang, Weidong; Xu, Bin; Fan, Guangyin; Zhang, Kaiming; Xiang, Zhen; Liu, Xiaoqiang

2018-04-14

Supported Pd-based catalyst over active nickel oxide (NiO) was repared using the impregnation method companying with UV-light irradiation. Moreover, the catalytic performance of the obtained Pd-based catalysts was evaluated towards the hydrogenation of o -chloronitrobenzene ( o -CNB). Observations indicate that the as-prepared UV-irradiated Pd/NiO catalyst with a mole fraction 0.2% (0.2%Pd/NiO) has higher activity and selectivity in the o -CNB hydrogenation. Especially, UV-light irradiation played a positive role in the improvement of catalytic activity of 0.2%Pd/NiO catalyst, exhibiting an excess 11-fold activity superiority in contrast with non-UV-irradiated 0.2%Pd/NiO catalyst. In addition, it was investigated that effects of varied factors (i.e., reaction time, temperature, o -CNB/Pd ratio, Pd loading, hydrogen pressure) on the selective hydrogenation of ο -CNB catalyzed by UV-irradiated 0.2%Pd/NiO catalyst. Under the reaction conditions of 60 °C, 0.5 h, 1 MPa H₂ pressure, 100% conversion of o -CNB, and 81.1% o -CAN selectivity were obtained, even at high molar ratio (8000:1) of o -CNB to Pd.
Anti-bacteria activity of carbon nanotubes grown on trimetallic catalyst

NASA Astrophysics Data System (ADS)

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

2018-06-01

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

NASA Astrophysics Data System (ADS)

Huang, Binbin; Wang, Yan; Zhan, Shuzhong; Ye, Jianshan

2017-02-01

Schiff base metal complexes have been applied in many fields, especially, a potential homogeneous catalyst for water splitting. However, the high overpotential, time consumed synthesis process and complicated working condition largely limit their application. In the present work, a one-step approach to fabricate Schiff base cobalt complex modified electrode is developed. Microrod clusters (MRC) and rough spherical particles (RSP) can be obtained on the ITO electrode through different electrochemical deposition condition. Both of the MRC and RSP present favorable activity for oxygen evolution reaction (OER) compared to the commercial Co3O4, taking an overpotential of 650 mV and 450 mV to drive appreciable catalytic current respectively. The highly active and stable RSP shows a Tafel plot of 84 mV dec-1 and negligible decrease of the current density for 12 h bulk electrolysis. The synthesis strategy of effective and stable catalyst in this work provide a simple method to fabricate heterogeneous OER catalyst with Schiff base metal complex.
Picolinamide-Based Iridium Catalysts for Dehydrogenation of Formic Acid in Water: Effect of Amide N Substituent on Activity and Stability.

PubMed

Kanega, Ryoichi; Onishi, Naoya; Wang, Lin; Murata, Kazuhisa; Muckerman, James T; Fujita, Etsuko; Himeda, Yuichiro

2018-03-01

To develop highly efficient catalysts for dehydrogenation of formic acid in water, we investigated several Cp*Ir catalysts with various amide ligands. The catalyst with an N-phenylpicolinamide ligand exhibited a TOF of 118 000 h -1 at 60 °C. A constant rate (TOF>35 000 h -1 ) was maintained for six hours, and a TON of 1 000 000 was achieved at 50 °C. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
Heterogeneous electro-Fenton catalyst for 1-butylpyridinium chloride degradation.

PubMed

Meijide, Jessica; Pazos, Marta; Sanromán, Maria Ángeles

2017-10-15

The application of the electro-Fenton process for organic compound mineralisation has been widely reported over the past years. However, operational problems related to the use of soluble iron salt as a homogeneous catalyst involve the development of novel catalysts that are able to operate in a wide pH range. For this purpose, polyvinyl alcohol-alginate beads, containing goethite as iron, were synthesised and evaluated as heterogeneous electro-Fenton catalyst for 1-butylpyridinium chloride mineralisation. The influence of catalyst dosage and pH solution on ionic liquid degradation was analysed, achieving almost total oxidation after 60 min under optimal conditions (2 g/L catalyst concentration and pH 3). The results showed good catalyst stability and reusability, although its effectiveness decreases slightly after three successive cycles. Furthermore, a plausible mineralisation pathway was proposed based on the oxidation byproducts determined by chromatographic techniques. Finally, the Microtox® test revealed notable detoxification after treatment which demonstrates high catalyst ability for pyridinium-based ionic liquid degradation by the electro-Fenton process.
Methanol Steam Reforming Promoted by Molten Salt-Modified Platinum on Alumina Catalysts

PubMed Central

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

2014-01-01

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

NASA Astrophysics Data System (ADS)

Baricci, Andrea; Casalegno, Andrea

2016-09-01

Limiting current density of oxygen reduction reaction in polymer electrolyte fuel cells is determined by several mass transport resistances that lower the concentration of oxygen on the catalyst active site. Among them, diffusion across porous media plays a significant role. Despite the extensive experimental activity documented in PEMFC literature, only few efforts have been dedicated to the measurement of the effective transport properties in porous layers. In the present work, a methodology for ex situ measurement of the effective diffusion coefficient and Knudsen radius of porous layers for polymer electrolyte fuel cells (gas diffusion layer, micro porous layer and catalyst layer) is described and applied to high temperature polymer fuel cells State of Art materials. Regression of the measured quantities by means of a quasi 2D physical model is performed to quantify the Knudsen effect, which is reported to account, respectively, for 30% and 50% of the mass transport resistance in micro porous layer and catalyst layer. On the other side, the model reveals that pressure gradient consequent to permeation in porous layers of high temperature polymer fuel cells has a negligible effect on oxygen concentration in relevant operating conditions.
Synthesis of subnanometer-diameter vertically aligned single-walled carbon nanotubes with copper-anchored cobalt catalysts

NASA Astrophysics Data System (ADS)

Cui, Kehang; Kumamoto, Akihito; Xiang, Rong; An, Hua; Wang, Benjamin; Inoue, Taiki; Chiashi, Shohei; Ikuhara, Yuichi; Maruyama, Shigeo

2016-01-01

We synthesize vertically aligned single-walled carbon nanotubes (VA-SWNTs) with subnanometer diameters on quartz (and SiO2/Si) substrates by alcohol CVD using Cu-anchored Co catalysts. The uniform VA-SWNTs with a nanotube diameter of 1 nm are synthesized at a CVD temperature of 800 °C and have a thickness of several tens of μm. The diameter of SWNTs was reduced to 0.75 nm at 650 °C with the G/D ratio maintained above 24. Scanning transmission electron microscopy energy-dispersive X-ray spectroscopy (EDS-STEM) and high angle annular dark field (HAADF-STEM) imaging of the Co/Cu bimetallic catalyst system showed that Co catalysts were captured and anchored by adjacent Cu nanoparticles, and thus were prevented from coalescing into a larger size, which contributed to the small diameter of SWNTs. The correlation between the catalyst size and the SWNT diameter was experimentally clarified. The subnanometer-diameter and high-quality SWNTs are expected to pave the way to replace silicon for next-generation optoelectronic and photovoltaic devices.We synthesize vertically aligned single-walled carbon nanotubes (VA-SWNTs) with subnanometer diameters on quartz (and SiO2/Si) substrates by alcohol CVD using Cu-anchored Co catalysts. The uniform VA-SWNTs with a nanotube diameter of 1 nm are synthesized at a CVD temperature of 800 °C and have a thickness of several tens of μm. The diameter of SWNTs was reduced to 0.75 nm at 650 °C with the G/D ratio maintained above 24. Scanning transmission electron microscopy energy-dispersive X-ray spectroscopy (EDS-STEM) and high angle annular dark field (HAADF-STEM) imaging of the Co/Cu bimetallic catalyst system showed that Co catalysts were captured and anchored by adjacent Cu nanoparticles, and thus were prevented from coalescing into a larger size, which contributed to the small diameter of SWNTs. The correlation between the catalyst size and the SWNT diameter was experimentally clarified. The subnanometer-diameter and high-quality SWNTs are expected to pave the way to replace silicon for next-generation optoelectronic and photovoltaic devices. Electronic supplementary information (ESI) available: Comparison between the Co monometallic catalyst system and the Co/Mo bimetallic catalyst system, the effect of CVD temperature on the G/D ratio, the effect of ethanol partial pressure on the morphology, diameter and quality of SWNT films, and Raman spectra of the Si/SiO2 substrate. See DOI: 10.1039/c5nr06007a
Highly efficient Cu-decorated iron oxide nanocatalyst for low pressure CO 2 conversion

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

Halder, Avik; Kilianová, Martina; Yang, Bing

We report a nanoparticulate iron oxide based catalyst for CO2 conversion with high efficiency at low pressures and on the effect of the presence of copper on the catalyst's restructuring and its catalytic performance. In situ X-ray scattering reveals the restructuring of the catalyst at the nanometer scale. In situ X-ray absorption near edge structure (XANES) shows the evolution of the composition and oxidation state of the iron and copper components under reaction conditions along with the promotional effect of copper on the chemical transformation of the iron component. X-ray diffraction (XRD), XANES and Raman spectroscopy proved that the startingmore » nano catalyst is composed of iron oxides differing in chemical nature (alpha-Fe2O3, Fe3O4, FeO(OH)) and dimensionality, while the catalyst after CO2 conversion was identified as a mixture of alpha-Fe, Fe3C, and traces of Fe5C2. The significant increase of the rate CO2 is turned over in the presence of copper nanoparticles indicates that Cu nanoparticles activate hydrogen, which after spilling over to the neighbouring iron sites, facilitate a more efficient conversion of carbon dioxide.« less
High-effective approach from amino acid esters to chiral amino alcohols over Cu/ZnO/Al2O3 catalyst and its catalytic reaction mechanism

NASA Astrophysics Data System (ADS)

Zhang, Shuangshuang; Yu, Jun; Li, Huiying; Mao, Dongsen; Lu, Guanzhong

2016-09-01

Developing the high-efficient and green synthetic method for chiral amino alcohols is an intriguing target. We have developed the Mg2+-doped Cu/ZnO/Al2O3 catalyst for hydrogenation of L-phenylalanine methyl ester to chiral L-phenylalaninol without racemization. The effect of different L-phenylalanine esters on this title reaction was studied, verifying that Cu/ZnO/Al2O3 is an excellent catalyst for the hydrogenation of amino acid esters to chiral amino alcohols. DFT calculation was used to study the adsorption of substrate on the catalyst, and showed that the substrate adsorbs on the surface active sites mainly by amino group (-NH2) absorbed on Al2O3, and carbonyl (C=O) and alkoxy (RO-) group oxygen absorbed on the boundary of Cu and Al2O3. This catalytic hydrogenation undergoes the formation of a hemiacetal intermediate and the cleavage of the C-O bond (rate-determining step) by reacting with dissociated H to obtain amino aldehyde and methanol ad-species. The former is further hydrogenated to amino alcohols, and the latter desorbs from the catalyst surface.

High-effective approach from amino acid esters to chiral amino alcohols over Cu/ZnO/Al2O3 catalyst and its catalytic reaction mechanism

PubMed Central

Zhang, Shuangshuang; Yu, Jun; Li, Huiying; Mao, Dongsen; Lu, Guanzhong

2016-01-01

Developing the high-efficient and green synthetic method for chiral amino alcohols is an intriguing target. We have developed the Mg2+-doped Cu/ZnO/Al2O3 catalyst for hydrogenation of L-phenylalanine methyl ester to chiral L-phenylalaninol without racemization. The effect of different L-phenylalanine esters on this title reaction was studied, verifying that Cu/ZnO/Al2O3 is an excellent catalyst for the hydrogenation of amino acid esters to chiral amino alcohols. DFT calculation was used to study the adsorption of substrate on the catalyst, and showed that the substrate adsorbs on the surface active sites mainly by amino group (-NH2) absorbed on Al2O3, and carbonyl (C=O) and alkoxy (RO-) group oxygen absorbed on the boundary of Cu and Al2O3. This catalytic hydrogenation undergoes the formation of a hemiacetal intermediate and the cleavage of the C–O bond (rate-determining step) by reacting with dissociated H to obtain amino aldehyde and methanol ad-species. The former is further hydrogenated to amino alcohols, and the latter desorbs from the catalyst surface. PMID:27619990
The Effect of Copper Addition on the Activity and Stability of Iron-Based CO₂ Hydrogenation Catalysts.

PubMed

Bradley, Matthew J; Ananth, Ramagopal; Willauer, Heather D; Baldwin, Jeffrey W; Hardy, Dennis R; Williams, Frederick W

2017-09-20

Iron-based CO₂ catalysts have shown promise as a viable route to the production of olefins from CO₂ and H₂ gas. However, these catalysts can suffer from low conversion and high methane selectivity, as well as being particularly vulnerable to water produced during the reaction. In an effort to improve both the activity and durability of iron-based catalysts on an alumina support, copper (10-30%) has been added to the catalyst matrix. In this paper, the effects of copper addition on the catalyst activity and morphology are examined. The addition of 10% copper significantly increases the CO₂ conversion, and decreases methane and carbon monoxide selectivity, without significantly altering the crystallinity and structure of the catalyst itself. The FeCu/K catalysts form an inverse spinel crystal phase that is independent of copper content and a metallic phase that increases in abundance with copper loading (>10% Cu). At higher loadings, copper separates from the iron oxide phase and produces metallic copper as shown by SEM-EDS. An addition of copper appears to increase the rate of the Fischer-Tropsch reaction step, as shown by modeling of the chemical kinetics and the inter- and intra-particle transport of mass and energy.
Highly selective oxidation of styrene to benzaldehyde over a tailor-made cobalt oxide encapsulated zeolite catalyst.

PubMed

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.
Preparation of a novel carbon-based solid acid from cassava stillage residue and its use for the esterification of free fatty acids in waste cooking oil.

PubMed

Wang, Lingtao; Dong, Xiuqin; Jiang, Haoxi; Li, Guiming; Zhang, Minhua

2014-04-01

A novel carbon-based solid acid catalyst was prepared by the sulfonation of incompletely carbonized cassava stillage residue (CSR) with concentrated sulfuric acid, and employed to catalyze the esterification of methanol and free fatty acids (FFAs) in waste cooking oil (WCO). The effects of the carbonization and the sulfonation temperatures on the pore structure, acid density and catalytic activity of the CSR-derived catalysts were systematically investigated. Low temperature carbonization and high temperature sulfonation can cause the collapse of the carbon framework, while high temperature carbonization is not conducive to the attachment of SO3H groups on the surface. The catalyst showed high catalytic activity for esterification, and the acid value for WCO is reduced to below 2mg KOH/g after reaction. The activity of catalyst can be well maintained after five cycles. CSR can be considered a promising raw material for the production of a new eco-friendly solid acid catalyst. Copyright © 2014 Elsevier Ltd. All rights reserved.
Novel application of thermally expanded graphite as the support of catalysts for direct synthesis of DMC from CH3OH and CO2.

PubMed

Bian, J; Xiao, M; Wang, S J; Lu, Y X; Meng, Y Z

2009-06-01

Novel Cu-Ni bimetallic catalysts supported on thermally expanded graphite (TEG) were prepared as an example to show the particular characteristics of TEG as a carbon support material. The structures of TEG and the synthesized Cu-Ni/TEG catalysts were characterized using BET, FTIR, TG, SEM, TEM, XRD and TPR techniques. The catalytic activities of the prepared catalysts were investigated by performing micro-reaction in the direct synthesis of dimethyl carbonate (DMC) from CH3OH and CO2. The experimental results indicated that the prepared Cu-Ni/TEG catalysts exhibited highly catalytic activity. Under the optimal catalytic conditions at 100 degrees C and under 1.2 MPa, the highest conversion of CH3OH of 4.97% and high selectivity of DMC of 89.3% can be achieved. The highly catalytic activity of Cu-Ni/TEG in DMC synthesis can be attributed to the synergetic effects of metal Cu, Ni and Cu-Ni alloy in the activation of CH3OH and CO2 and the particular characteristics of TEG as a carbon support material.
Nitrogen-doped graphdiyne as a metal-free catalyst for high-performance oxygen reduction reactions

NASA Astrophysics Data System (ADS)

Liu, Rongji; Liu, Huibiao; Li, Yuliang; Yi, Yuanping; Shang, Xinke; Zhang, Shuangshuang; Yu, Xuelian; Zhang, Suojiang; Cao, Hongbin; Zhang, Guangjin

2014-09-01

Fuel cells and metal-air batteries will only become widely available in everyday life when the expensive platinum-based electrocatalysts used for the oxygen reduction reactions are replaced by other efficient, low-cost and stable catalysts. We report here the use of nitrogen-doped graphdiyne as a metal-free electrode with a comparable electrocatalytic activity to commercial Pt/C catalysts for the oxygen reduction reaction in alkaline fuel cells. Nitrogen-doped graphdiyne has a better stability and increased tolerance to the cross-over effect than conventional Pt/C catalysts.Fuel cells and metal-air batteries will only become widely available in everyday life when the expensive platinum-based electrocatalysts used for the oxygen reduction reactions are replaced by other efficient, low-cost and stable catalysts. We report here the use of nitrogen-doped graphdiyne as a metal-free electrode with a comparable electrocatalytic activity to commercial Pt/C catalysts for the oxygen reduction reaction in alkaline fuel cells. Nitrogen-doped graphdiyne has a better stability and increased tolerance to the cross-over effect than conventional Pt/C catalysts. Electronic supplementary information (ESI) available: Detailed RDE and RRDE experiments, additional tables and figures. See DOI: 10.1039/c4nr03185g
Membrane catalyst layer for fuel cells

DOEpatents

Wilson, Mahlon S.

1993-01-01

A gas reaction fuel cell incorporates a thin catalyst layer between a solid polymer electrolyte (SPE) membrane and a porous electrode backing. The catalyst layer is preferably less than about 10 .mu.m in thickness with a carbon supported platinum catalyst loading less than about 0.35 mgPt/cm.sup.2. The film is formed as an ink that is spread and cured on a film release blank. The cured film is then transferred to the SPE membrane and hot pressed into the surface to form a catalyst layer having a controlled thickness and catalyst distribution. Alternatively, the catalyst layer is formed by applying a Na.sup.+ form of a perfluorosulfonate ionomer directly to the membrane, drying the film at a high temperature, and then converting the film back to the protonated form of the ionomer. The layer has adequate gas permeability so that cell performance is not affected and has a density and particle distribution effective to optimize proton access to the catalyst and electronic continuity for electron flow from the half-cell reaction occurring at the catalyst.
Gold Nanoparticles on Polymer-Wrapped Carbon Nanotubes: An Efficient and Selective Catalyst for the Electroreduction of CO2.

PubMed

Jhong, Huei-Ru Molly; Tornow, Claire E; Kim, Chaerin; Verma, Sumit; Oberst, Justin L; Anderson, Paul S; Gewirth, Andrew A; Fujigaya, Tsuyohiko; Nakashima, Naotoshi; Kenis, Paul J A

2017-11-17

Multiple approaches will be needed to reduce the atmospheric CO 2 levels, which have been linked to the undesirable effects of global climate change. The electroreduction of CO 2 driven by renewable energy is one approach to reduce CO 2 emissions while producing chemical building blocks, but current electrocatalysts exhibit low activity and selectivity. Here, we report the structural and electrochemical characterization of a promising catalyst for the electroreduction of CO 2 to CO: Au nanoparticles supported on polymer-wrapped multiwall carbon nanotubes. This catalyst exhibits high selectivity for CO over H 2 : 80-92 % CO, as well as high activity: partial current density for CO as high as 160 mA cm -2 . The observed high activity, originating from a high electrochemically active surface area (23 m 2 g -1 Au), in combination with the low loading (0.17 mg cm -2 ) of the highly dispersed Au nanoparticles underscores the promise of this catalyst for efficient electroreduction of CO 2 . © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
DOE Office of Scientific and Technical Information (OSTI.GOV)

Nguyen, Luan; Tao, Franklin, E-mail: franklin.tao.2011@gmail.com; Department of Chemical and Petroleum Engineering, University of Kansas, Lawrence, Kansas 66045

Tracking surface chemistry of a catalyst during catalysis is significant for fundamental understanding of catalytic performance of the catalyst since it allows for establishing an intrinsic correlation between surface chemistry of a catalyst at its working status and its corresponding catalytic performance. Ambient pressure X-ray photoelectron spectroscopy can be used for in-situ studies of surfaces of different materials or devices in a gas. To simulate the gaseous environment of a catalyst in a fixed-bed a flowing gaseous environment of reactants around the catalyst is necessary. Here, we report the development of a new flowing reaction cell for simulating in-situ studymore » of a catalyst surface under a reaction condition in gas of one reactant or during catalysis in a mixture of reactants of a catalytic reaction. The homemade reaction cell is installed in a high vacuum (HV) or ultrahigh vacuum (UHV) environment of a chamber. The flowing gas in the reaction cell is separated from the HV or UHV environment through well sealings at three interfaces between the reaction cell and X-ray window, sample door and aperture of front cone of an energy analyzer. Catalyst in the cell is heated through infrared laser beam introduced through a fiber optics interfaced with the reaction cell through a homemade feedthrough. The highly localized heating on the sample holder and Au-passivated internal surface of the reaction cell effectively minimizes any unwanted reactions potentially catalyzed by the reaction cell. The incorporated laser heating allows a fast heating and a high thermal stability of the sample at a high temperature. With this cell, a catalyst at 800 °C in a flowing gas can be tracked readily.« less
Hydrogen production by steam reforming of liquefied natural gas over a nickel catalyst supported on mesoporous alumina xerogel

NASA Astrophysics Data System (ADS)

Seo, Jeong Gil; Youn, Min Hye; Cho, Kyung Min; Park, Sunyoung; Song, In Kyu

Mesoporous alumina xerogel (A-SG) is prepared by a sol-gel method for use as a support for a nickel catalyst. The Ni/A-SG catalyst is then prepared by an impregnation method, and is applied to hydrogen production by steam reforming of liquefied natural gas (LNG). The effect of the mesoporous alumina xerogel support on the catalytic performance of Ni/A-SG catalyst is investigated. For the purpose of comparison, a nickel catalyst supported on commercial alumina (A-C) is also prepared by an impregnation method (Ni/A-C). Both the hydroxyl-rich surface and the electron-deficient sites of the A-SG support enhance the dispersion of the nickel species on the support during the calcination step. The formation of the surface nickel aluminate phase in the Ni/A-SG catalyst remarkably increases the reducibility and stability of the catalyst. Furthermore, the high-surface area and the well-developed mesoporosity of the Ni/A-SG catalyst enhance the gasification of surface hydrocarbons that are adsorbed in the reaction. In the steam reforming of LNG, the Ni/A-SG catalyst exhibits a better catalytic performance than the Ni/A-C catalyst in terms of LNG conversion and hydrogen production. Moreover, the Ni/A-SG catalyst shows strong resistance toward catalyst deactivation.
Influence of lanthanum on the surface structure and CO hydrogenation activity of supported cobalt catalysts

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

Ledford, J.S.; Houalla, M.; Proctor, A.

1989-09-07

X-ray photoelectron spectroscopy (ESCA or XPS), X-ray diffraction (XRD), Raman spectroscopy, H{sub 2} chemisorption, and gravimetric analysis have been used to characterize three series of La/Al{sub 3}O{sub 3} and CoLa/Al{sub 2}O{sub 3} catalysts. CoLa/Al{sub 2}O{sub 3} catalysts were prepared by two methods: impregnation of La first followed by Co (designated CoLay) and impregnation of Co first followed by La (designated LayCo). The information obtained from surface and bulk characterization has been compared with CO hydrogenation activity and selectivity of the supported Co/Al{sub 2}O{sub 3} catalysts. For CoLay catalysts with low La loadings (La/Al atomic ratio {le} 0.026), the presence ofmore » La had little effect on the structure or CO hydrogenation activity. However, the selectivity to higher hydrocarbons and olefinic products increased with increasing La content. For CoLay catalysts with higher La loadings, Co{sub 3}O{sub 4} is suppressed in favor of an amorphous dispersed La-Co mixed oxide. ESCA and H{sub 2} chemisorption indicated higher dispersion of the metallic cobalt phase for high La loadings. The turnover frequency (TOF) for CO hydrogenation decreased dramatically for high La loadings. This has been correlated to the decrease in the amount of Co{sub 3}O{sub 4} present in the La-rich catalysts. Catalysts prepared by reverse impregnation (LayCo) showed little evidence of La-Co interaction. No significant variation in reducibility or cobalt metal dispersion was observed. Lanthanum addition had little effect on the TOF for CO hydrogenation or the selectivity to olefinic products and higher hydrocarbons.« less
Sub-nanometer surface chemistry and orbital hybridization in lanthanum-doped ceria nano-catalysts revealed by 3D electron microscopy.

PubMed

Collins, Sean M; Fernandez-Garcia, Susana; Calvino, José J; Midgley, Paul A

2017-07-14

Surface chemical composition, electronic structure, and bonding characteristics determine catalytic activity but are not resolved for individual catalyst particles by conventional spectroscopy. In particular, the nano-scale three-dimensional distribution of aliovalent lanthanide dopants in ceria catalysts and their effect on the surface electronic structure remains unclear. Here, we reveal the surface segregation of dopant cations and oxygen vacancies and observe bonding changes in lanthanum-doped ceria catalyst particle aggregates with sub-nanometer precision using a new model-based spectroscopic tomography approach. These findings refine our understanding of the spatially varying electronic structure and bonding in ceria-based nanoparticle aggregates with aliovalent cation concentrations and identify new strategies for advancing high efficiency doped ceria nano-catalysts.
Towards Highly Performing and Stable PtNi Catalysts in Polymer Electrolyte Fuel Cells for Automotive Application

PubMed Central

Zignani, Sabrina C.; Baglio, Vincenzo; Sebastián, David; Saccà, Ada; Gatto, Irene; Aricò, Antonino S.

2017-01-01

In order to help the introduction on the automotive market of polymer electrolyte fuel cells (PEFCs), it is mandatory to develop highly performing and stable catalysts. The main objective of this work is to investigate PtNi/C catalysts in a PEFC under low relative humidity and pressure conditions, more representative of automotive applications. Carbon supported PtNi nanoparticles were prepared by reduction of metal precursors with formic acid and successive thermal and leaching treatments. The effect of the chemical composition, structure and surface characteristics of the synthesized samples on their electrochemical behavior was investigated. The catalyst characterized by a larger Pt content (Pt3Ni2/C) presented the highest catalytic activity (lower potential losses in the activation region) among the synthesized bimetallic PtNi catalysts and the commercial Pt/C, used as the reference material, after testing at high temperature (95 °C) and low humidification (50%) conditions for automotive applications, showing a cell potential (ohmic drop-free) of 0.82 V at 500 mA·cm−2. In order to assess the electro-catalysts stability, accelerated degradation tests were carried out by cycling the cell potential between 0.6 V and 1.2 V. By comparing the electrochemical and physico-chemical parameters at the beginning of life (BoL) and end of life (EoL), it was demonstrated that the Pt1Ni1/C catalyst was the most stable among the catalyst series, with only a 2% loss of voltage at 200 mA·cm−2 and 12.5% at 950 mA·cm−2. However, further improvements are needed to produce durable catalysts. PMID:28772677
Hydrogen production by steam reforming of liquefied natural gas (LNG) over nickel catalysts supported on cationic surfactant-templated mesoporous aluminas

NASA Astrophysics Data System (ADS)

Seo, Jeong Gil; Youn, Min Hye; Park, Sunyoung; Jung, Ji Chul; Kim, Pil; Chung, Jin Suk; Song, In Kyu

Two types of mesoporous γ-aluminas (denoted as A-A and A-S) are prepared by a hydrothermal method under different basic conditions using cationic surfactant (cetyltrimethylammonium bromide, CTAB) as a templating agent. A-A and A-S are synthesized in a medium of ammonia solution and sodium hydroxide solution, respectively. Ni/γ-Al 2O 3 catalysts (Ni/A-A and Ni/A-S) are then prepared by an impregnation method, and are applied to hydrogen production by steam reforming of liquefied natural gas (LNG). The effect of a mesoporous γ-Al 2O 3 support on the catalytic performance of Ni/γ-Al 2O 3 is investigated. The identity of basic solution strongly affects the physical properties of the A-A and A-S supports. The high surface-area of the mesoporous γ-aluminas and the strong metal-support interaction of supported catalysts greatly enhance the dispersion of nickel species on the catalyst surface. The well-developed mesopores of the Ni/A-A and Ni/A-S catalysts prohibit the polymerization of carbon species on the catalyst surface during the reaction. In the steam reforming of LNG, both Ni/A-A and Ni/A-S catalysts give better catalytic performance than the nickel catalyst supported on commercial γ-Al 2O 3 (Ni/A-C). In addition, the Ni/A-A catalyst is superior to the Ni/A-S catalyst. The relatively strong metal-support interaction of Ni/A-A catalyst effectively suppresses the sintering of metallic nickel and the carbon deposition in the steam reforming of LNG. The large pores of the Ni/A-A catalyst also play an important role in enhancing internal mass transfer during the reaction.
Platinum single-atom and cluster catalysis of the hydrogen evolution reaction

NASA Astrophysics Data System (ADS)

Cheng, Niancai; Stambula, Samantha; Wang, Da; Banis, Mohammad Norouzi; Liu, Jian; Riese, Adam; Xiao, Biwei; Li, Ruying; Sham, Tsun-Kong; Liu, Li-Min; Botton, Gianluigi A.; Sun, Xueliang

2016-11-01

Platinum-based catalysts have been considered the most effective electrocatalysts for the hydrogen evolution reaction in water splitting. However, platinum utilization in these electrocatalysts is extremely low, as the active sites are only located on the surface of the catalyst particles. Downsizing catalyst nanoparticles to single atoms is highly desirable to maximize their efficiency by utilizing nearly all platinum atoms. Here we report on a practical synthesis method to produce isolated single platinum atoms and clusters using the atomic layer deposition technique. The single platinum atom catalysts are investigated for the hydrogen evolution reaction, where they exhibit significantly enhanced catalytic activity (up to 37 times) and high stability in comparison with the state-of-the-art commercial platinum/carbon catalysts. The X-ray absorption fine structure and density functional theory analyses indicate that the partially unoccupied density of states of the platinum atoms' 5d orbitals on the nitrogen-doped graphene are responsible for the excellent performance.
Chemoselective single-site Earth-abundant metal catalysts at metal–organic framework nodes

PubMed Central

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

2016-01-01

Earth-abundant metal catalysts are critically needed for sustainable chemical synthesis. Here we report a simple, cheap and effective strategy of producing novel earth-abundant metal catalysts at metal–organic framework (MOF) nodes for broad-scope organic transformations. The straightforward metalation of MOF secondary building units (SBUs) with cobalt and iron salts affords highly active and reusable single-site solid catalysts for a range of organic reactions, including chemoselective borylation, silylation and amination of benzylic C–H bonds, as well as hydrogenation and hydroboration of alkenes and ketones. Our structural, spectroscopic and kinetic studies suggest that chemoselective organic transformations occur on site-isolated, electron-deficient and coordinatively unsaturated metal centres at the SBUs via σ-bond metathesis pathways and as a result of the steric environment around the catalytic site. MOFs thus provide a novel platform for the development of highly active and affordable base metal catalysts for the sustainable synthesis of fine chemicals. PMID:27574182
Chemoselective single-site Earth-abundant metal catalysts at metal–organic framework nodes

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

Manna, Kuntal; Ji, Pengfei; Lin, Zekai

2016-08-30

Earth-abundant metal catalysts are critically needed for sustainable chemical synthesis. Here we report a simple, cheap and effective strategy of producing novel earth-abundant metal catalysts at metal–organic framework (MOF) nodes for broad-scope organic transformations. The straightforward metalation of MOF secondary building units (SBUs) with cobalt and iron salts affords highly active and reusable single-site solid catalysts for a range of organic reactions, including chemoselective borylation, silylation and amination of benzylic C–H bonds, as well as hydrogenation and hydroboration of alkenes and ketones. Our structural, spectroscopic and kinetic studies suggest that chemoselective organic transformations occur on site-isolated, electron-deficient and coordinatively unsaturatedmore » metal centres at the SBUs via σ-bond metathesis pathways and as a result of the steric environment around the catalytic site. MOFs thus provide a novel platform for the development of highly active and affordable base metal catalysts for the sustainable synthesis of fine chemicals.« less
Deoxygenation of glycolaldehyde and furfural on Mo2C/Mo(100)

NASA Astrophysics Data System (ADS)

McManus, Jesse R.; Vohs, John M.

2014-12-01

The desire to produce fuels and chemicals in an energy conscious, environmentally sympathetic approach has motivated considerable research on the use of cellulosic biomass feedstocks. One of the major challenges facing the utilization of biomass is finding effective catalysts for the efficient and selective removal of oxygen from the highly-oxygenated, biomass-derived platform molecules. Herein, a study of the reaction pathways for the biomass-derived platform molecule furfural and biomass-derived sugar model compound glycolaldehyde provides insight into the mechanisms of hydrodeoxygenation (HDO) on a model molybdenum carbide catalyst, Mo2C/Mo(100). Using temperature programmed desorption (TPD) and high resolution electron energy loss spectroscopy (HREELS), it was found that the Mo2C/Mo(100) catalyst was active for selective deoxygenation of the aldehyde carbonyl by facilitating adsorption of the aldehyde in an η2(C,O) bonding configuration. Furthermore, the catalyst showed no appreciable activity for furanic ring hydrogenation, highlighting the promise of relatively inexpensive Mo2C catalysts for selective HDO chemistry.
Platinum single-atom and cluster catalysis of the hydrogen evolution reaction

PubMed Central

Cheng, Niancai; Stambula, Samantha; Wang, Da; Banis, Mohammad Norouzi; Liu, Jian; Riese, Adam; Xiao, Biwei; Li, Ruying; Sham, Tsun-Kong; Liu, Li-Min; Botton, Gianluigi A.; Sun, Xueliang

2016-01-01

Platinum-based catalysts have been considered the most effective electrocatalysts for the hydrogen evolution reaction in water splitting. However, platinum utilization in these electrocatalysts is extremely low, as the active sites are only located on the surface of the catalyst particles. Downsizing catalyst nanoparticles to single atoms is highly desirable to maximize their efficiency by utilizing nearly all platinum atoms. Here we report on a practical synthesis method to produce isolated single platinum atoms and clusters using the atomic layer deposition technique. The single platinum atom catalysts are investigated for the hydrogen evolution reaction, where they exhibit significantly enhanced catalytic activity (up to 37 times) and high stability in comparison with the state-of-the-art commercial platinum/carbon catalysts. The X-ray absorption fine structure and density functional theory analyses indicate that the partially unoccupied density of states of the platinum atoms' 5d orbitals on the nitrogen-doped graphene are responsible for the excellent performance. PMID:27901129
High Performance Heteroatoms Quaternary-doped Carbon Catalysts Derived from Shewanella Bacteria for Oxygen Reduction.

PubMed

Guo, Zhaoyan; Ren, Guangyuan; Jiang, Congcong; Lu, Xianyong; Zhu, Ying; Jiang, Lei; Dai, Liming

2015-11-25

A novel heteroatoms (N, P, S and Fe) quaternary-doped carbon (HQDC-X, X refers to the pyrolysis temperature) can be fabricated by directly pyrolyzing a gram-negative bacteria, S. oneidensis MR-1 as precursors at 800 °C, 900 °C and 1000 °C under argon atmosphere. These HQDC-X catalysts maintain the cylindrical shape of bacteria after pyrolysis under high temperatures, while heteroatoms including N, P, S and Fe distribute homogeneously on the carbon frameworks. As a result, HQDC-X catalysts exhibit excellent electrocatalytic activity for ORR via a dominant four-electron oxygen reduction pathway in alkaline medium, which is comparable with that of commercial Pt/C. More importantly, HQDC-X catalysts show better tolerance for methanol crossover and CO poisoning effects, long-term durability than commercial Pt/C, which could be promising alternatives to costly Pt-based electrocatalysts for ORR. The method may provide a promising avenue to develop cheap ORR catalysts from inexpensive, scalable and biological recursors.

Perovskite-nitrogen-doped carbon nanotube composite as bifunctional catalysts for rechargeable lithium-air batteries.

PubMed

Park, Hey Woong; Lee, Dong Un; Park, Moon Gyu; Ahmed, Raihan; Seo, Min Ho; Nazar, Linda F; Chen, Zhongwei

2015-03-01

Developing an effective bifunctional catalyst is a significant issue, as rechargeable metal-air batteries are very attractive for future energy systems. In this study, a facile one-pot process is introduced to prepare an advanced bifunctional catalyst (op-LN) incorporating nitrogen-doped carbon nanotubes (NCNTs) into perovskite La0.5 Sr0.5 Co0.8 Fe0.2 O3 nanoparticles (LSCF-NPs). Confirmed by half-cell testing, op-LN exhibits synergistic effects of LSCF-NP and NCNT with excellent bifunctionality for both the oxygen reduction reaction and the oxygen evolution reaction. Furthermore, op-LN exhibits comparable performances in these reactions to Pt/C and Ir/C, respectively, which highlights its potential for use as a commercially viable bifunctional catalyst. Moreover, the results obtained by testing op-LN in a practical Li-air battery demonstrate improved and complementary charge/discharge performance compared to those of LSCF-NP and NCNT, and this confirms that simply prepared op-LN is a promising candidate as a highly effective bifunctional catalyst for rechargeable metal-air batteries. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Design of Pd/PANI/Pd sandwich-structured nanotube array catalysts with special shape effects and synergistic effects for ethanol electrooxidation.

PubMed

Wang, An-Liang; Xu, Han; Feng, Jin-Xian; Ding, Liang-Xin; Tong, Ye-Xiang; Li, Gao-Ren

2013-07-24

Low cost, high activity, and long-term durability are the main requirements for commercializing fuel cell electrocatalysts. Despite tremendous efforts, developing non-Pt anode electrocatalysts with high activity and long-term durability at low cost remains a significant technical challenge. Here we report a new type of hybrid Pd/PANI/Pd sandwich-structured nanotube array (SNTA) to exploit shape effects and synergistic effects of Pd-PANI composites for the oxidation of small organic molecules for direct alcohol fuel cells. These synthesized Pd/PANI/Pd SNTAs exhibit significantly improved electrocatalytic activity and durability compared with Pd NTAs and commercial Pd/C catalysts. The unique SNTAs provide fast transport and short diffusion paths for electroactive species and high utilization rate of catalysts. Besides the merits of nanotube arrays, the improved electrocatalytic activity and durability are especially attributed to the special Pd/PANI/Pd sandwich-like nanostructures, which results in electron delocalization between Pd d orbitals and PANI π-conjugated ligands and in electron transfer from Pd to PANI.
Palladium-metalated porous organic polymers as recyclable catalysts for chemoselective decarbonylation of aldehydes.

PubMed

Li, Wen-Hao; Li, Cun-Yao; Li, Yan; Tang, Hai-Tao; Wang, Heng-Shan; Pan, Ying-Ming; Ding, Yun-Jie

2018-06-07

A novel palladium nanoparticle (NP)-metalated porous organic ligand (Pd NPs/POL-xantphos) has been prepared for the chemoselective decarbonylation of aldehydes. This heterogenous catalyst not only has excellent catalytic activity and chemoselectivity, but also holds high activity after 10 runs of reuse. The effective usage of this method is demonstrated through the synthesis of biofuels such as furfuryl alcohol (FFA) via the highly chemoselective decarbonylation of biomass-derived 5-hydroxy-methylfurfural (HMF) with a TON up to 1540. More importantly, 9-fluorenone could be obtained in one step through the decarbonylation of 2-bromobenzaldehyde by using this heterogeneous catalyst.
Catalysts for cleaner combustion of coal, wood and briquettes sulfur dioxide reduction options for low emission sources

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

Smith, P.V.

1995-12-31

Coal fired, low emission sources are a major factor in the air quality problems facing eastern European cities. These sources include: stoker-fired boilers which feed district heating systems and also meet local industrial steam demand, hand-fired boilers which provide heat for one building or a small group of buildings, and masonary tile stoves which heat individual rooms. Global Environmental Systems is marketing through Global Environmental Systems of Polane, Inc. catalysts to improve the combustion of coal, wood or fuel oils in these combustion systems. PCCL-II Combustion Catalysts promotes more complete combustion, reduces or eliminates slag formations, soot, corrosion and somemore » air pollution emissions and is especially effective on high sulfur-high vanadium residual oils. Glo-Klen is a semi-dry powder continuous acting catalyst that is injected directly into the furnace of boilers by operating personnel. It is a multi-purpose catalyst that is a furnace combustion catalyst that saves fuel by increasing combustion efficiency, a cleaner of heat transfer surfaces that saves additional fuel by increasing the absorption of heat, a corrosion-inhibiting catalyst that reduces costly corrosion damage and an air pollution reducing catalyst that reduces air pollution type stack emissions. The reduction of sulfur dioxides from coal or oil-fired boilers of the hand fired stoker design and larger, can be controlled by the induction of the Glo-Klen combustion catalyst and either hydrated lime or pulverized limestone.« less
Investigation on the light alkanes aromatization over Zn and Ga modified HZSM-5 catalysts in the presence of methane

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

Li, Qingyin; Zhang, Fengqi; Jarvis, Jack

The catalytic co-aromatization of methane and paraffin-rich raffinate oil was investigated along with hexane, heptane and octane as its model compounds over zinc and gallium modified ZSM-5 zeolite catalysts. The benzene, toluene and xylene (BTX) components derived from light alkane aromatization were highly promoted with the assistance of methane. The co-existence of Zn and Ga metal species has a positive effect on the formation of BTX components, whereas the individual metal loaded catalyst resulted in the production of heavy aromatics, suggesting that zinc and gallium have a synergistic effect on the formation of BTX under the methane environment. When concernedmore » with gaseous analysis, the introduced methane might interact with smaller intermediates and then transform into larger hydrocarbons. From the DRIFT observation, it was witnessed that the interaction between light alkane and methane occurred on the surface of the charged Zn-Ga/ZSM-5 catalyst. According to the comprehensive catalyst characterizations, the excellent catalytic performance may be closely associated with greatly dispersed metal species on the zeolite support, improved microporous characteristic, moderate Bronsted and increased Lewis acidic sites during the paraffin-rich liquid feedstock aromatization under methane environment. This research provides a promising pathway for the highly effective and profitable utilization of petrochemical resources and natural gas.« less
Investigation on the light alkanes aromatization over Zn and Ga modified HZSM-5 catalysts in the presence of methane

DOE PAGES

Li, Qingyin; Zhang, Fengqi; Jarvis, Jack; ...

2018-03-16

The catalytic co-aromatization of methane and paraffin-rich raffinate oil was investigated along with hexane, heptane and octane as its model compounds over zinc and gallium modified ZSM-5 zeolite catalysts. The benzene, toluene and xylene (BTX) components derived from light alkane aromatization were highly promoted with the assistance of methane. The co-existence of Zn and Ga metal species has a positive effect on the formation of BTX components, whereas the individual metal loaded catalyst resulted in the production of heavy aromatics, suggesting that zinc and gallium have a synergistic effect on the formation of BTX under the methane environment. When concernedmore » with gaseous analysis, the introduced methane might interact with smaller intermediates and then transform into larger hydrocarbons. From the DRIFT observation, it was witnessed that the interaction between light alkane and methane occurred on the surface of the charged Zn-Ga/ZSM-5 catalyst. According to the comprehensive catalyst characterizations, the excellent catalytic performance may be closely associated with greatly dispersed metal species on the zeolite support, improved microporous characteristic, moderate Bronsted and increased Lewis acidic sites during the paraffin-rich liquid feedstock aromatization under methane environment. This research provides a promising pathway for the highly effective and profitable utilization of petrochemical resources and natural gas.« less
Effect of Particle Size and Operating Conditions on Pt 3Co PEMFC Cathode Catalyst Durability

DOE PAGES

Gummalla, Mallika; Ball, Sarah; Condit, David; ...

2015-05-29

The initial performance and decay trends of polymer electrolyte membrane fuel cells (PEMFC) cathodes with Pt 3Co catalysts of three mean particle sizes (4.9 nm, 8.1 nm, and 14.8 nm) with identical Pt loadings are compared. Even though the cathode based on 4.9 nm catalyst exhibited the highest initial electrochemical surface area (ECA) and mass activity, the cathode based on 8.1 nm catalyst showed better initial performance at high currents. Owing to the low mass activity of the large particles, the initial performance of the 14.8 nm Pt3Co-based electrode was the lowest. The performance decay rate of the electrodes withmore » the smallest Pt 3Co particle size was the highest and that of the largest Pt 3Co particle size was lowest. Interestingly, with increasing number of decay cycles (0.6 to 1.0 V, 50 mV/s), the relative improvement in performance of the cathode based on 8.1 nm Pt 3Co over the 4.9 nm Pt 3Co increased, owing to better stability of the 8.1 nm catalyst. The electron microprobe analysis (EMPA) of the decayed membrane-electrode assembly (MEA) showed that the amount of Co in the membrane was lower for the larger particles, and the platinum loss into the membrane also decreased with increasing particle size. This suggests that the higher initial performance at high currents with 8.1 nm Pt 3Co could be due to lower contamination of the ionomer in the electrode. Furthermore, lower loss of Co from the catalyst with increased particle size could be one of the factors contributing to the stability of ECA and mass activity of electrodes with larger cathode catalyst particles. To delineate the impact of particle size and alloy effects, these results are compared with prior work from our research group on size effects of pure platinum catalysts. The impact of PEMFC operating conditions, including upper potential, relative humidity, and temperature on the alloy catalyst decay trends, along with the EMPA analysis of the decayed MEAs, are reported.« less
Innovative Clean Coal Technology (ICCT). Demonstration of Selective Catalytic Reduction (SCR) technology for the control of nitrogen oxide (NO{sub x}) emissions from high-sulfur coal-fired boilers: Volume 1. Final report

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

NONE

1996-10-01

The objective of this project is to demonstrate and evaluate commercially available Selective Catalytic Reduction (SCR) catalysts from U.S., Japanese and European catalyst suppliers on a high-sulfur U.S. coal-fired boiler. SCR is a post-combustion nitrogen oxide (NO.) control technology that involves injecting ammonia into the flue gas generated from coal combustion in an electric utility boiler. The flue gas containing ammonia is then passed through a reactor that contains a specialized catalyst. In the presence of the catalyst, the ammonia reacts with NO. to convert it to nitrogen and water vapor. Although SCR is widely practiced in Japan and Europemore » on gas-, oil-, and low-sulfur coal- fired boilers, there are several technical uncertainties associated with applying SCR to U.S. coals. These uncertainties include: 1) potential catalyst deactivation due to poisoning by trace metal species present in U.S. coals that are not present in other fuels. 2) performance of the technology and effects on the balance-of- plant equipment in the presence of high amounts of SO{sub 2} and SO{sub 3}. 3) performance of a wide variety of SCR catalyst compositions, geometries and methods of manufacturer under typical high-sulfur coal-fired utility operating conditions. These uncertainties were explored by operating nine small-scale SCR reactors and simultaneously exposing different SCR catalysts to flue gas derived from the combustion of high sulfur U.S. coal. In addition, the test facility operating experience provided a basis for an economic study investigating the implementation of SCR technology.« less
Demonstration of Selective Catalytic Reduction (SCR) technology for the control of nitrogen oxide (NO sub x ) emissions from high-sulfur coal-fired boilers: Innovative Clean Coal Technology (ICCT)

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

Not Available

1992-05-01

The objective of this project is to demonstrate and evaluate commercially available Selective Catalytic Reduction (SCR) catalysts from US, Japanese and European catalyst suppliers on a high-sulfur US coal-fired boiler. SCR is a post-combustion nitrogen oxide (NO{sub x}) control technology that involves injecting ammonia into the flue gas generated from coal combustion in an electric utility boiler. The flue gas containing ammonia is then passed through a reactor that contains a specialized catalyst. In the presence of the catalyst, the amonia reacts with NO{sub x} to convert it to nitrogen and water vapor. Although SCR is widely practiced in Japanmore » and Europe, there are numerous technical uncertainties associated with applying SCR to US coals. These uncertainties include: (1) potential catalyst deactivation due to poisoning by trace metal species present in US coals that are not present in other fuels. (2) performance of the technology and effects on the balance-of-plant equipment in the presence of high amounts of SO, and SO{sub 3}. (3) performance of a wide variety of SCR catalyst compositions, geometries and methods of manufacture under typical high-sulfur coal-fired utility operating conditions. These uncertainties will be explored by constructing a series of small-scale SCR reactors and simultaneously exposing different SCR catalysts to flue gas derived from the combustion of high sulfur US coal. The demonstration will be performed at Gulf Power Company's Plant Crist Unit No. 5 (75 MW capacity) near Pensacola, Florida. The project will be funded by the US Department of Energy (DOE), Southern Company Services, Inc. (SCS on behalf of the entire Southern electric system), and the Electric Power Research Institute.« less
Tungsten carbide/porous carbon composite as superior support for platinum catalyst toward methanol electro-oxidation

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

Jiang, Liming; Fu, Honggang, E-mail: fuhg@vip.sina.com; Key Laboratory of Functional Inorganic Material Chemistry, Heilongjiang University, Harbin 150080

2014-01-01

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

PubMed

Marzo, Leyre; Luis-Barrera, Javier; Mas-Ballesté, Rubén; Ruano, José Luis García; Alemán, José

2016-11-07

A highly diastereoselective synthesis of trisubstituted Z- or E-enals, which are important intermediates in organic synthesis, as well as being present in natural products, is described using different alkynals and nucleophiles as starting materials. Diastereocontrol is mainly governed by the appropriate catalyst. Therefore, those reactions controlled by steric effects, such as the Jørgensen-Hayashi's catalyst, give access to E isomers, and those catalysts that facilitate hydrogen bonding, such as tetrazol-pyrrolidine Ley's catalyst, allow the synthesis of Z isomers. A stereochemical model based on DFT calculations is proposed. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
Multisource Synergistic Electrocatalytic Oxidation Effect of Strongly Coupled PdM (M = Sn, Pb)/N-doped Graphene Nanocomposite on Small Organic Molecules

PubMed Central

Wu, Peng; Huang, Yiyin; Kang, Longtian; Wu, Maoxiang; Wang, Yaobing

2015-01-01

A series of palladium-based catalysts of metal alloying (Sn, Pb) and/or (N-doped) graphene support with regular enhanced electrocatalytic activity were investigated. The peak current density (118.05 mA cm−2) of PdSn/NG is higher than the sum current density (45.63 + 47.59 mA cm−2) of Pd/NG and PdSn/G. It reveals a synergistic electrocatalytic oxidation effect in PdSn/N-doped graphene Nanocomposite. Extend experiments show this multisource synergetic catalytic effect of metal alloying and N-doped graphene support in one catalyst on small organic molecule (methanol, ethanol and Ethylene glycol) oxidation is universal in PdM(M = Sn, Pb)/NG catalysts. Further, The high dispersion of small nanoparticles, the altered electron structure and Pd(0)/Pd(II) ratio of Pd in catalysts induced by strong coupled the metal alloying and N-doped graphene are responsible for the multisource synergistic catalytic effect in PdM(M = Sn, Pb) /NG catalysts. Finally, the catalytic durability and stability are also greatly improved. PMID:26434949
Preparation and Characterization of NiMo/Al2O3Catalyst for Hydrocracking Processing

NASA Astrophysics Data System (ADS)

Widiyadi, Aditya; Guspiani, Gema Adil; Riady, Jeffry; Andreanto, Rikky; Chaiunnisa, Safina Dea; Widayat

2018-02-01

Hydrocracking is a chemical process used in petroleum refineries for converting high boiling hydrocarbons in petroleum crude oils to more valuable lower boiling products such as gasoline, kerosene, and diesel oil that operate at high temperature and pressure. Catalyst was used in hydrocracking to reduce temperature and pressure. Hydrocracking catalyst are composed of active components and support. Alumina is widely used in hydrocracking process as catalyst support due to its high surface area, high thermal stability, and low prices. The objective of this research was preparated NiMo/Al2O3 catalyst that used as hydrocracking catalyst. Catalyst was synthesized by wetness impregnation method and simple heating method with various kind of Al2O3. The physicochemical properties of catalyst were investigated by X-ray diffraction (XRD) to determine type of crystal and scanning electron microscopy (SEM) to determine morphology of the catalyst. The NiMo/Al2O3 catalyst prepared by aluminium potassium sulfate dodecahydrate exhibited the highest crystallinity of 90.23% and it is clear that MoO3 and NiO crystallites are highly dispersed on the NiMo/Al2O3 catalyst which indicates as the best catalyst. The catalytic activity in hydrocracking process was successfully examined to convert fatty acid into hydrocarbon.
NO[sub x] reduction by sulfur tolerant coronal-catalytic apparatus and method

DOEpatents

Mathur, V.K.; Breault, R.W.; McLarnon, C.R.; Medros, F.G.

1992-09-15

This invention presents an NO[sub x] environment effective reduction apparatus comprising a sulfur tolerant coronal-catalyst such as high dielectric coronal-catalysts like glass wool, ceramic-glass wool or zirconium glass wool and method of use. In one embodiment the invention comprises an NO[sub x] reduction apparatus of sulfur tolerant coronal-catalyst adapted and configured for hypercritical presentation to an NO[sub x] bearing gas stream at a minimum of at least about 75 watts/cubic meter. 7 figs.
NO.sub.x reduction by sulfur tolerant coronal-catalytic apparatus and method

DOEpatents

Mathur, Virendra K.; Breault, Ronald W.; McLarnon, Christopher R.; Medros, Frank G.

1993-01-01

This invention presents an NO.sub.x environment effective reduction apparatus comprising a sulfur tolerant coronal-catalyst such as high dielectric coronal-catalysts like glass wool, ceramic-glass wool or zirconium glass wool and method of use. In one embodiment the invention comprises an NO.sub.x reduction apparatus of sulfur tolerant coronal-catalyst adapted and configured for hypercritical presentation to an NO.sub.x bearing gas stream at a minimum of at least about 75 watts/cubic meter.
NO.sub.x reduction by sulfur tolerant coronal-catalytic apparatus and method

DOEpatents

Mathur, Virendra K.; Breault, Ronald W.; McLarnon, Christopher R.; Medros, Frank G.

1992-01-01

This invention presents an NO.sub.x environment effective reduction apparatus comprising a sulfur tolerant coronal-catalyst such as high dielectric coronal-catalysts like glass wool, ceramic-glass wool or zirconium glass wool and method of use. In one embodiment the invention comprises an NO.sub.x reduction apparatus of sulfur tolerant coronal-catalyst adapted and configured for hypercritical presentation to an NO.sub.x bearing gas stream at a minimum of at least about 75 watts/cubic meter.
NOx reduction by sulfur tolerant coronal-catalytic apparatus and method

DOEpatents

Mathur, V.K.; Breault, R.W.; McLarnon, C.R.; Medros, F.G.

1993-08-31

This invention presents an NO[sub x] environment effective reduction apparatus comprising a sulfur tolerant coronal-catalyst such as high dielectric coronal-catalysts like glass wool, ceramic-glass wool or zirconium glass wool and method of use. In one embodiment the invention comprises an NO[sub x] reduction apparatus of sulfur tolerant coronal-catalyst adapted and configured for hypercritical presentation to an NO[sub x] bearing gas stream at a minimum of at least about 75 watts/cubic meter.
Unusual catalysts from molasses: synthesis, properties and application in obtaining biofuels from algae.

PubMed

Samorì, Chiara; Torri, Cristian; Fabbri, Daniele; Falini, Giuseppe; Faraloni, Cecilia; Galletti, Paola; Spera, Silvia; Tagliavini, Emilio; Torzillo, Giuseppe

2012-08-01

Acid catalysts were prepared by sulfonation of carbon materials obtained from the pyrolysis of sugar beet molasses, a cheap, viscous byproduct in the processing of sugar beets into sugar. Conditions for the pyrolysis of molasses (temperature and time) influenced catalyst performance; the best combination came from pyrolysis at low temperature (420 °C) for a relatively long time (8-15 h), which ensured better stability of the final material. The most effective molasses catalyst was highly active in the esterification of fatty acids with methanol (100 % yield after 3 h) and more active than common solid acidic catalysts in the transesterification of vegetable oils with 25-75 wt % of acid content (55-96 % yield after 8 h). A tandem process using a solid acid molasses catalyst and potassium hydroxide in methanol was developed to de-acidificate and transesterificate algal oils from Chlamydomonas reinhardtii, Nannochloropsis gaditana, and Phaeodactylum tricornutum, which contain high amounts of free fatty acids. The amount of catalyst required for the de-acidification step was influenced by the chemical composition of the algal oil, thus operational conditions were determined not only in relation to free fatty acids content in the oil, but according to the composition of the lipid extract of each algal species. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
ATTRITION RESISTANT IRON-BASED FISCHER-TROPSCH CATALYSTS

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

JAMES G. GOODWIN, JR.; JAMES J. SPIVEY; K. JOTHIMURUGESAN

1998-09-17

The Fischer-Tropsch (F-T) reaction provides a way of converting coal-derived synthesis gas (CO+H{sub 2}) to liquid fuels. Since the reaction is highly exothermic, one of the major problems in control of the reaction is heat removal. Recent work has shown that the use of slurry bubble column reactors (SBCRs) can largely solve this problem. Iron-based (Fe) catalysts are preferred catalysts for F-T when using low CO/H{sub 2} ratio synthesis gases derived from modern coal gasifiers. This is because in addition to reasonable F-T activity, the F-T catalysts also possess high water gas shift (WGS) activity. However, a serious problem withmore » the use of Fe catalysts in a SBCR is their tendency to undergo attrition. This can cause fouling/plugging of downstream filters and equipment, making the separation of catalyst from the oil/wax product very difficult if not impossible, and results in a steady loss of catalyst from the reactor. The objectives of this research are to develop a better understanding of the parameters affecting attrition resistance of Fe F-T catalysts suitable for use in SBCRs and to incorporate this understanding into the design of novel Fe catalysts having superior attrition resistance. Catalyst preparations will be based on the use of spray drying and will be scalable using commercially available equipment. The research will employ among other measurements, attrition testing and F-T synthesis, including long duration slurry reactor runs in order to ascertain the degree of success of the various preparations. The goal is to develop an Fe catalyst which can be used in a SBCR having only an internal filter for separation of the catalyst from the liquid product, without sacrificing F-T activity and selectivity. The effect of silica addition via coprecipitation and as a binder to a doubly promoted Fischer-Tropsch synthesis iron catalyst (100 Fe/5 Cu/4.2 K) was studied. The catalysts were prepared by coprecipitation, followed by binder addition and drying in a 1 m diameter, 2 m tall spray dryer. The binder silica content was varied from 0 to 20 wt %. A catalyst with 12 wt % binder silica was found to have the highest attrition resistance. F-T reaction studies over 100 hours in a fixed-bed reactor showed that this catalyst maintained around 95 % CO conversion with a methane selectivity of less than 7 wt % and a C{sub 5}{sup +} selectivity of greater than 73 wt %. The effect of adding precipitated silica from 0 to 20 parts by weight to this catalyst (containing 12 wt % binder silica) was also studied. Addition of precipitated silica was found to be detrimental to attrition resistance and resulted in increased methane and reduced wax formation.« less
Graphitic Carbon Nitride Supported Catalysts for Polymer Electrolyte Fuel Cells

PubMed Central

2014-01-01

Graphitic carbon nitrides are investigated for developing highly durable Pt electrocatalyst supports for polymer electrolyte fuel cells (PEFCs). Three different graphitic carbon nitride materials were synthesized with the aim to address the effect of crystallinity, porosity, and composition on the catalyst support properties: polymeric carbon nitride (gCNM), poly(triazine) imide carbon nitride (PTI/Li+Cl–), and boron-doped graphitic carbon nitride (B-gCNM). Following accelerated corrosion testing, all graphitic carbon nitride materials are found to be more electrochemically stable compared to conventional carbon black (Vulcan XC-72R) with B-gCNM support showing the best stability. For the supported catalysts, Pt/PTI-Li+Cl– catalyst exhibits better durability with only 19% electrochemical surface area (ECSA) loss versus 36% for Pt/Vulcan after 2000 scans. Superior methanol oxidation activity is observed for all graphitic carbon nitride supported Pt catalysts on the basis of the catalyst ECSA. PMID:24748912

Biodiesel production from used cooking oil by two-step heterogeneous catalyzed process.

PubMed

Srilatha, K; Prabhavathi Devi, B L A; Lingaiah, N; Prasad, R B N; Sai Prasad, P S

2012-09-01

The present study demonstrates the production of biodiesel from used cooking oil containing high free fatty acid by a two-step heterogeneously catalyzed process. The free fatty acids were first esterified with methanol using a 25 wt.% TPA/Nb(2)O(5) catalyst followed by transesterification of the oil with methanol over ZnO/Na-Y zeolite catalyst. The catalysts were characterized by XRD, FT-IR, BET surface area and CO(2)-TPD. In the case of transesterification the effect of reaction parameters, such as catalyst concentration, methanol to oil molar ratio and reaction temperature, on the yield of ester were investigated. The catalyst with 20 wt.% ZnO loading on Na-Y exhibited the highest activity among the others. Both the solid acid and base catalysts were found to be reusable for several times indicating their efficacy in the two-step process. Copyright © 2012 Elsevier Ltd. All rights reserved.
Process for magnetic beneficiating petroleum cracking catalyst

DOEpatents

Doctor, R.D.

1993-10-05

A process is described for beneficiating a particulate zeolite petroleum cracking catalyst having metal values in excess of 1000 ppm nickel equivalents. The particulate catalyst is passed through a magnetic field in the range of from about 2 Tesla to about 5 Tesla generated by a superconducting quadrupole open-gradient magnetic system for a time sufficient to effect separation of said catalyst into a plurality of zones having different nickel equivalent concentrations. A first zone has nickel equivalents of about 6,000 ppm and greater, a second zone has nickel equivalents in the range of from about 2000 ppm to about 6000 ppm, and a third zone has nickel equivalents of about 2000 ppm and less. The zones of catalyst are separated and the second zone material is recycled to a fluidized bed of zeolite petroleum cracking catalyst. The low nickel equivalent zone is treated while the high nickel equivalent zone is discarded. 1 figures.
Process for magnetic beneficiating petroleum cracking catalyst

DOEpatents

Doctor, Richard D.

1993-01-01

A process for beneficiating a particulate zeolite petroleum cracking catalyst having metal values in excess of 1000 ppm nickel equivalents. The particulate catalyst is passed through a magnetic field in the range of from about 2 Tesla to about 5 Tesla generated by a superconducting quadrupole open-gradient magnetic system for a time sufficient to effect separation of said catalyst into a plurality of zones having different nickel equivalent concentrations. A first zone has nickel equivalents of about 6,000 ppm and greater, a second zone has nickel equivalents in the range of from about 2000 ppm to about 6000 ppm, and a third zone has nickel equivalents of about 2000 ppm and less. The zones of catalyst are separated and the second zone material is recycled to a fluidized bed of zeolite petroleum cracking catalyst. The low nickel equivalent zone is treated while the high nickel equivalent zone is discarded.
Methods and catalysts for making biodiesel from the transesterification and esterification of unrefined oils

DOEpatents

Yan, Shuli [Detroit, MI; Salley, Steven O [Grosse Pointe Park, MI; Ng, K Y. Simon [West Bloomfield, MI

2012-04-24

A method of forming a biodiesel product and a heterogeneous catalyst system used to form said product that has a high tolerance for the presence of water and free fatty acids (FFA) in the oil feedstock is disclosed. This catalyst system may simultaneously catalyze both the esterification of FAA and the transesterification of triglycerides present in the oil feedstock. The catalyst system according to one aspect of the present disclosure represents a class of zinc and lanthanum oxide heterogeneous catalysts that include different ratios of zinc oxide to lanthanum oxides (Zn:La ratio) ranging from about 10:0 to 0:10. The Zn:La ratio in the catalyst is believed to have an effect on the number and reactivity of Lewis acid and base sites, as well as the transesterification of glycerides, the esterification of fatty acids, and the hydrolysis of glycerides and biodiesel.
Hydroisomerization of n-dodecane over Pt/Al-MCM-48 catalysts.

PubMed

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

2014-04-01

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

NASA Technical Reports Server (NTRS)

Cassell, Alan M.; Verma, Sunita; Delzeit, Lance; Meyyappan, M.; Han, Jie

2000-01-01

Libraries of liquid-phase catalyst precursor solutions were printed onto iridium-coated silicon substrates and evaluated for their effectiveness in catalyzing the growth of multi-walled carbon nanotubes (MWNTs) by chemical vapor deposition (CVD). The catalyst precursor solutions were composed of inorganic salts and a removable tri-block copolymer (EO)20(PO)70(EO)20 (EO = ethylene oxide, PO = propylene oxide) structure-directing agent (SDA), dissolved in ethanol/methanol mixtures. Sample libraries were quickly assayed using scanning electron microscopy after CVD growth to identify active catalysts and CVD conditions. Composition libraries and focus libraries were then constructed around the active spots identified in the discovery libraries to understand how catalyst precursor composition affects the yield, density, and quality of the nanotubes. Successful implementation of combinatorial optimization methods in the development of highly active, carbon nanotube catalysts is demonstrated, as well as the identification of catalyst formulations that lead to varying densities and shapes of aligned nanotube towers.
Hydrogenation of biofuels with formic acid over a palladium-based ternary catalyst with two types of active sites.

PubMed

Wang, Liang; Zhang, Bingsen; Meng, Xiangju; Su, Dang Sheng; Xiao, Feng-Shou

2014-06-01

A composite catalyst including palladium nanoparticles on titania (TiO2) and on nitrogen-modified porous carbon (Pd/TiO2@N-C) is synthesized from palladium salts, tetrabutyl titanate, and chitosan. N2 sorption isotherms show that the catalyst has a high BET surface area (229 m(2) g(-1)) and large porosity. XPS and TEM characterization of the catalyst shows that palladium species with different chemical states are well dispersed across the TiO2 and nitrogen-modified porous carbon, respectively. The Pd/TiO2@N-C catalyst is very active and shows excellent stability towards hydrogenation of vanillin to 2-methoxy-4-methylphenol using formic acid as hydrogen source. This activity can be attributed to a synergistic effect between the Pd/TiO2 (a catalyst for dehydrogenation of formic acid) and Pd/N-C (a catalyst for hydrogenation of vanillin) sites. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Conversion of corn stalk into furfural using a novel heterogeneous strong acid catalyst in γ-valerolactone.

PubMed

Xu, Zhiping; Li, Wenzhi; Du, Zhijie; Wu, Hao; Jameel, Hasan; Chang, Hou-Min; Ma, Longlong

2015-12-01

A novel solid acid catalyst was prepared by the copolymerization of p-toluenesulfonic acid and paraformaldehyde and then characterized by FT-IR, TG/DTG, HRTEM and N2-BET. Furfural was successfully produced by the dehydration of xylose and xylan using the novel catalyst in γ-valerolactone. This investigation focused on effects of various reaction conditions including solvent, acid catalyst, reaction temperature, residence time, water concentration, xylose loading and catalyst dosage on the dehydration of xylose to furfural. It was found that the solid catalyst displayed extremely high activity for furfural production. 80.4% furfural yield with 98.8% xylose conversion was achieved at 170°C for 10 min. The catalyst could be recycled at least five times without significant loss of activity. Furthermore, 83.5% furfural yield and 19.5% HMF yield were obtained from raw corn stalk under more severe conditions (190°C for 100 min). Copyright © 2015 Elsevier Ltd. All rights reserved.
NiFe (Oxy) Hydroxides Derived from NiFe Disulfides as an Efficient Oxygen Evolution Catalyst for Rechargeable Zn-Air Batteries: The Effect of Surface S Residues.

PubMed

Wang, Tanyuan; Nam, Gyutae; Jin, Yue; Wang, Xingyu; Ren, Pengju; Kim, Min Gyu; Liang, Jiashun; Wen, Xiaodong; Jang, Haeseong; Han, Jiantao; Huang, Yunhui; Li, Qing; Cho, Jaephil

2018-05-21

A facile H 2 O 2 oxidation treatment to tune the properties of metal disulfides for oxygen evolution reaction (OER) activity enhancement is introduced. With this method, the degree of oxidation can be readily controlled and the effect of surface S residues in the resulted metal (oxy)hydroxides for the OER is revealed for the first time. The developed NiFe (oxy)hydroxide catalyst with residual S demonstrates an extraordinarily low OER overpotential of 190 mV at the current density of 10 mA cm -2 after coupling with carbon nanotubes, and outstanding performance in Zn-air battery tests. Theoretical calculation suggests that the surface S residues can significantly reduce the adsorption free energy difference between O* and OH* intermediates on the Fe sites, which should account for the high OER activity of NiFe (oxy)hydroxide catalysts. This work provides significant insight regarding the effect of surface heteroatom residues in OER electrocatalysis and offers a new strategy to design high-performance and cost-efficient OER catalysts. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Sodium-promoted Pd/TiO2 for catalytic oxidation of formaldehyde at ambient temperature.

PubMed

Zhang, Changbin; Li, Yaobin; Wang, Yafei; He, Hong

2014-05-20

Catalytic oxidation of formaldehyde (HCHO) to CO2 at ambient conditions is of great interest for indoor HCHO purification. Here, we report that sodium-doped Pd/TiO2 is a highly effective catalyst for the catalytic oxidation of HCHO at room temperature. It was observed that Na doping has a dramatic promotion effect on the Pd/TiO2 catalyst and that nearly 100% HCHO conversion could be achieved over the 2Na-Pd/TiO2 catalyst at a GHSV of 95000 h(-1) and HCHO inlet concentration of 140 ppm at 25 °C. The mechanism of the Na-promotion effect was investigated by using Brunauer-Emmett-Teller (BET), X-ray diffraction (XRD), CO chemisorption, Temperature-programmed reduction by H2 (H2-TPR), X-ray photoelectron spectroscopy (XPS) and temperature-programmed desorption of O2 (O2-TPD) methods. The results showed that Na species addition can induce and further stabilize a negatively charged and well-dispersed Pd species, which then facilitates the activation of H2O and chemisorbed oxygen, therefore resulting in the high performance of the 2Na-Pd/TiO2 catalyst for the ambient HCHO destruction.
High Performance and Cost-Effective Direct Methanol Fuel Cells: Fe-N-C Methanol-Tolerant Oxygen Reduction Reaction Catalysts.

PubMed

Sebastián, David; Serov, Alexey; Artyushkova, Kateryna; Gordon, Jonathan; Atanassov, Plamen; Aricò, Antonino S; Baglio, Vincenzo

2016-08-09

Direct methanol fuel cells (DMFCs) offer great advantages for the supply of power with high efficiency and large energy density. The search for a cost-effective, active, stable and methanol-tolerant catalyst for the oxygen reduction reaction (ORR) is still a great challenge. In this work, platinum group metal-free (PGM-free) catalysts based on Fe-N-C are investigated in acidic medium. Post-treatment of the catalyst improves the ORR activity compared with previously published PGM-free formulations and shows an excellent tolerance to the presence of methanol. The feasibility for application in DMFC under a wide range of operating conditions is demonstrated, with a maximum power density of approximately 50 mW cm(-2) and a negligible methanol crossover effect on the performance. A review of the most recent PGM-free cathode formulations for DMFC indicates that this formulation leads to the highest performance at a low membrane-electrode assembly (MEA) cost. Moreover, a 100 h durability test in DMFC shows suitable applicability, with a similar performance-time behavior compared to common MEAs based on Pt cathodes. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Efficient and stable MoS2 catalyst integrated on Si photocathodes by photoreduction and post-annealing for water splitting

NASA Astrophysics Data System (ADS)

Zhou, Jungui; Dai, Song; Dong, Wen; Su, Xiaodong; Fang, Liang; Zheng, Fengang; Wang, Xiongdong; Shen, Mingrong

2016-05-01

MoS2 has been studied as an efficient and cheap hydrogen evolution reaction (HER) catalyst; however, its effective integration with a photocathode remains a challenge. Here, crystalline MoS2 catalyst was deposited on top of a ˜2 nm Al2O3 protected n+p-Si photocathode using a simple photoreduction method following a post-annealing. The amount of MoS2 is optimized for HER of the photocathode, balanced between its catalytic effect and light absorption. High efficiency with 0.35 V onset potential vs. reversible hydrogen electrode and 34.5 mA/cm2 saturated photocurrent and high stability after 2 min ultrasonication or under 40 h continuous HER were observed. Such properties are much superior to the corresponding photocathodes coated by the traditional electrodeposited amorphous MoS2. Furthermore, the MoS2 layer is also an effective support for Pt nanoparticles with considerable reduction in the Pt amount while keeping the photoelectrochemical reactivity. This study indicates that the cheap-made MoS2 can be an efficient and stable HER catalyst for the Si photocathode.
High Coke-Resistance Pt/Mg1-xNixO Catalyst for Dry Reforming of Methane

PubMed Central

Al-Doghachi, Faris A. J.; Islam, Aminul; Zainal, Zulkarnain; Saiman, Mohd Izham; Embong, Zaidi; Taufiq-Yap, Yun Hin

2016-01-01

A highly active and stable nano structured Pt/Mg1-xNixO catalysts was developed by a simple co-precipitation method. The obtained Pt/Mg1-xNixO catalyst exhibited cubic structure nanocatalyst with a size of 50–80 nm and realized CH4 and CO2 conversions as high as 98% at 900°C with excellent stability in the dry reforming of methane. The characterization of catalyst was performed using various kinds of analytical techniques including XRD, BET, XRF, TPR-H2, TGA, TEM, FESEM, FT-IR, and XPS analyses. Characterization of spent catalyst further confirms that Pt/Mg1-xNixO catalyst has high coke-resistance for dry reforming. Thus, the catalyst demonstrated in this study, offers a promising catalyst for resolving the dilemma between dispersion and reducibility of supported metal, as well as activity and stability during high temperature reactions. PMID:26745623
Development of HAN-based Liquid Propellant Thruster

NASA Astrophysics Data System (ADS)

Hisatsune, K.; Izumi, J.; Tsutaya, H.; Furukawa, K.

2004-10-01

Many of propellants that are applied to the conventional spacecraft propulsion system are toxic propellants. Because of its toxicity, considering the environmental pollution or safety on handling, it will be necessary to apply the "green" propellant to the spacecraft propulsion system. The purpose of this study is to apply HAN based liquid propellant (LP1846) to mono propellant thruster. Compared to the hydrazine that is used in conventional mono propellant thruster, HAN based propellant is not only lower toxic but also can obtain higher specific impulse. Moreover, HAN based propellant can be decomposed by the catalyst. It means there are the possibility of applying to the mono propellant thruster that can leads to the high reliability of the propulsion system.[1],[2] However, there are two technical subjects, to apply HAN based propellant to the mono propellant thruster. One is the high combustion temperature. The catalyst will be damaged under high temperature condition. The other is the low catalytic activity. It is the serious problem on application of HAN based propellant to the mono propellant thruster that is used for attitude control of spacecraft. To improve the catalytic activity of HAN based propellant, it is necessary to screen the best catalyst for HAN based propellant. The adsorption analysis is conducted by Monte Carlo Simulation to screen the catalyst metal for HAN and TEAN. The result of analysis shows the Iridium is the best catalyst metal for HAN and TEAN. Iridium is the catalyst metal that is used at conventional mono propellant thruster catalyst Shell405. Then, to confirm the result of analysis, the reaction test about catalyst is conducted. The result of this test is the same as the result of adsorption analysis. That means the adsorption analysis is effective in screening the catalyst metal. At the evaluating test, the various types of carrier of catalyst are also compared to Shell 405 to improve catalytic activity. The test result shows the inorganic porous media is superior to Shell405 in catalytic activity. Next, the catalyst life with HAN based propellant (LP1846) is evaluated. The Shell405 and inorganic porous media catalyst are compared at the life test. The test result shows the inorganic porous media catalyst is superior to Shell405 in catalyst life. In this paper, the detail of the result of adsorption analysis and evaluating test are reported.
DOE Office of Scientific and Technical Information (OSTI.GOV)

Not Available

The five iron catalysts reported were all promoted with potassium. The most promising results were obtained with the catalyst containing UCC-111 (Appendix B, Run 10225-3). In earlier studies UCC-111 alone had been found to be a poor Task 1 catalyst for oligomerizing propylene. Physically combined with potassium-promoted iron, however, it proved surprisingly effective as a syngas catalyst in Task 2. It produced straight-chain olefinic hydrocarbons, as a normal Fischer-Tropsch catalyst does, but unlike the normal Fischer-Tropsch catalyst, it may also have isomerized the carbon-carbon double bond. Transfer of the double bond from the usual Position 1, typical for Fischer-Tropsch products,more » to an interior position, should not only lower the pour point of the liquid product, but it should raise its octane number as well. Four of the six cobalt catalysts reported this quarter were promoted with either thorium or thorium and potassium. All six were synthesized by the precipitate-slurry method, with either LZ-105-6, LZ-Y-82, UCC-101 or UCC-107 as the Molecular Sieve component. The test results for most of these catalysts indicate that cobalt is more effective than iron in producing a high yield of motor fuels. This increase in motor fuel yield was due primarily to a higher yield of diesel oil, with the gasoline yield remaining approximately the same as for the iron catalysts. This increased diesel oil yield, as well as an increased methane yield, was balanced against a decreased C/sub 2/-C/sub 4/ yield. The yields of the heavy fractions for both metal catalysts remained relatively low.« less
Cobalt nanoparticles encapsulated in nitrogen-rich carbon nanotubes as efficient catalysts for organic pollutants degradation via sulfite activation.

PubMed

Wu, Deming; Ye, Peng; Wang, Manye; Wei, Yi; Li, Xiaoxia; Xu, Aihua

2018-06-15

The activation of sulfite by heterogeneous catalysts displays a great potential in the development of new sulfate radials based technologies for wastewater treatment. Herein, cobalt nanoparticles embedded in N-doped carbon nanotubes (Co@NC) were prepared by a simple pyrolysis method. Due to the synergistic effects of the cobalt nanoparticles and N-doped carbon nanotubes, the Co@NC catalyst intrinsically shows an outstanding efficiency, excellent reusability and high stability in the catalytic oxidation of methyl orange (MO) in the presence of sulfite and dioxygen. The structure and efficiency of the catalyst was significantly affected by the content of cobalt and pyrolysis temperature. Several quenching experiments and electron paramagnetic resonance were carried out to investigate the catalytic mechanism. It is found that hydroxyl and sulfate radicals worked together to degrade MO in the system. The formation and decomposition of peroxymonosulfate may be an important route of these reactive radicals production. The effect of different anions, bicarbonate concentration, initial solution pH and dye types on the performance of the catalyst was also studied. This study can open a new approach for design and preparation of encapsulated cobalt in carbon materials as effective catalysts for pollutants degradation via sulfite activation. Copyright © 2018 Elsevier B.V. All rights reserved.
Methanol steam reforming promoted by molten salt-modified platinum on alumina catalysts.

PubMed

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

2014-09-01

We herein describe a straight forward procedure to increase the performance of platinum-on-alumina catalysts in methanol steam reforming by applying an alkali hydroxide coating according to the "solid catalyst with ionic liquid layer" (SCILL) approach. We demonstrate by diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and temperature-programmed desorption (TPD) studies that potassium doping plays an important role in the catalyst activation. Moreover, the hygroscopic nature and the basicity of the salt modification contribute to the considerable enhancement in catalytic performance. During reaction, a partly liquid film of alkali hydroxides/carbonates forms on the catalyst/alumina surface, thus significantly enhancing the availability of water at the catalytically active sites. Too high catalyst pore fillings with salt introduce a considerable mass transfer barrier into the system as indicated by kinetic studies. Thus, the optimum interplay between beneficial catalyst modification and detrimental mass transfer effects had to be identified and was found on the applied platinum-on-alumina catalyst at KOH loadings around 7.5 mass%. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Hydrogen generation from catalytic hydrolysis of alkaline sodium borohydride solution using attapulgite clay-supported Co-B catalyst

NASA Astrophysics Data System (ADS)

Tian, Hongjing; Guo, Qingjie; Xu, Dongyan

An attapulgite clay-supported cobalt-boride (Co-B) catalyst used in portable fuel cell fields is prepared in this paper by impregnation-chemical reduction method. The cost of attapulgite clay is much lower compared with some other inert carriers, such as activated carbon and carbon nanotube. Its microstructure and catalytic activity are analyzed in this paper. The effects of NaOH concentration, NaBH 4 concentration, reacting temperature, catalyst loadings and recycle times on the performance of the catalysts in hydrogen production from alkaline NaBH 4 solutions are investigated. Furthermore, characteristics of these catalysts are carried out in SEM, XRD and TEM analysis. The high catalytic activity of the catalyst indicates that it is a promising and practical catalyst. Activation energy of hydrogen generation using such catalysts is estimated to be 56.32 kJ mol -1. In the cycle test, from the 1st cycle to the 9th cycle, the average hydrogen generation rate decreases gradually from 1.27 l min -1 g -1 Co-B to 0.87 l min -1 g -1 Co-B.
The production of high efficiency Ziegler-Natta catalyst with dual active sites nature using cyclohexyl chloride as promoter with super activity and produced superior polyethylene with controllable molecular weight distribution.

PubMed

Seifali Abbas-Abadi, Mehrdad

2017-01-01

In the previous studies, the several halocarbons (HC) were tested as promoters for a Ti-based Ziegler-Natta (ZN) catalyst at different polymerization conditions. The Results showed that chloro cyclohexane has the best operation in catalyst activity, polymer particle size growth, hydrogen responsibility and wax reduction too. For the first time in this study, the effect of Al/Ti ratio on the optimum HC/Ti ratio has been considered and the results showed that the optimum HC/Ti ratio depends on the Al/Ti ratio directly. In the optimum HC/Ti ratio, the catalyst activity and hydrogen responsibility ratio of the catalyst increase up to 125 and 55% respectively. The acceptable growth of polymer powder up to 46%, lower flow rate ratio (FRR) up to 19% and decrease of wax amount up to 12%, completed the promotion results. Furthermore, in the next part of this study and as key note, a little dose of halocarbon was used in the catalyst preparation to produce the special catalysts with dual active sites. In the catalyst preparation, the concentration of each active sites depends on the halocarbon amount and it can control the molecular weight distribution of the produced polyethylene; because each active sites have different response to hydrogen. The halocarbon based catalysts showed the remarkable effect on the catalyst activity, the molecular weight and especially molecular weight distribution (MWD). The flow rate ratio and MWD could be increased up to 77 and 88% respectively as the main result of halocarbon addition during the catalyst preparation.
The production of high efficiency Ziegler–Natta catalyst with dual active sites nature using cyclohexyl chloride as promoter with super activity and produced superior polyethylene with controllable molecular weight distribution

PubMed Central

Seifali Abbas-Abadi, Mehrdad

2017-01-01

Abstract In the previous studies, the several halocarbons (HC) were tested as promoters for a Ti-based Ziegler–Natta (ZN) catalyst at different polymerization conditions. The Results showed that chloro cyclohexane has the best operation in catalyst activity, polymer particle size growth, hydrogen responsibility and wax reduction too. For the first time in this study, the effect of Al/Ti ratio on the optimum HC/Ti ratio has been considered and the results showed that the optimum HC/Ti ratio depends on the Al/Ti ratio directly. In the optimum HC/Ti ratio, the catalyst activity and hydrogen responsibility ratio of the catalyst increase up to 125 and 55% respectively. The acceptable growth of polymer powder up to 46%, lower flow rate ratio (FRR) up to 19% and decrease of wax amount up to 12%, completed the promotion results. Furthermore, in the next part of this study and as key note, a little dose of halocarbon was used in the catalyst preparation to produce the special catalysts with dual active sites. In the catalyst preparation, the concentration of each active sites depends on the halocarbon amount and it can control the molecular weight distribution of the produced polyethylene; because each active sites have different response to hydrogen. The halocarbon based catalysts showed the remarkable effect on the catalyst activity, the molecular weight and especially molecular weight distribution (MWD). The flow rate ratio and MWD could be increased up to 77 and 88% respectively as the main result of halocarbon addition during the catalyst preparation. PMID:29491824

Towards the Rational Design of Nanoparticle Catalysts

NASA Astrophysics Data System (ADS)

Dash, Priyabrat

This research is focused on development of routes towards the rational design of nanoparticle catalysts. Primarily, it is focused on two main projects; (1) the use of imidazolium-based ionic liquids (ILs) as greener media for the design of quasi-homogeneous nanoparticle catalysts and (2) the rational design of heterogeneous-supported nanoparticle catalysts from structured nanoparticle precursors. Each project has different studies associated with the main objective of the design of nanoparticle catalysts. In the first project, imidazolium-based ionic liquids have been used for the synthesis of nanoparticle catalysts. In particular, studies on recyclability, reuse, mode-of-stability, and long-term stability of these ionic-liquid supported nanoparticle catalysts have been done; all of which are important factors in determining the overall "greenness" of such synthetic routes. Three papers have been published/submitted for this project. In the first publication, highly stable polymer-stabilized Au, Pd and bimetallic Au-Pd nanoparticle catalysts have been synthesized in imidazolium-based 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM]PF6) ionic liquid (Journal of Molecular Catalysis A: Chemical, 2008, 286, 114). The resulting nanoparticles were found to be effective and selective quasi-homogeneous catalysts towards a wide-range of hydrogenation reactions and the catalyst solution was reused for further catalytic reactions with minimal loss in activity. The synthesis of very pure and clean ILs has allowed a platform to study the effects of impurities in the imidazolium ILs on nanoparticle stability. In a later study, a new mode of stabilization was postulated where the presence of low amounts of 1-methylimidazole has substantial effects on the resulting stability of Au and Pd-Au nanoparticles in these ILs (Chemical Communications, 2009, 812). In further continuation of this study, a comparative study involving four stabilization protocols for nanoparticle stabilization in BMIMPF6 IL is described, and have shown that nanoparticle stability and catalytic activity of nanoparticles is dependent on the overall stability of the nanoparticles towards aggregation (manuscript submitted). The second major project is focused on synthesizing structurally well-defined supported catalysts by incorporating the nanoparticle precursors (both alloy and core shell) into oxide frameworks (TiO2 and Al2O 3), and examining their structure-property relationships and catalytic activity. a full article has been published on this project (Journal of Physical Chemistry C, 2009, 113, 12719) in which a route to rationally design supported catalysts from structured nanoparticle precursors with precise control over size, composition, and internal structure of the nanoparticles has been shown. In a continuation of this methodology for the synthesis of heterogeneous catalysts, efforts were carried out to apply the same methodology in imidazolium-based ILs as a one-pot media for the synthesis of supported-nanoparticle heterogeneous catalysts via the trapping of pre-synthesized nanoparticles into porous inorganic oxide materials. Nanoparticle catalysts in highly porous titania supports were synthesized using this methodology (manuscript to be submitted).
Pore structure modification of diatomite as sulfuric acid catalyst support by high energy electron beam irradiation and hydrothermal treatment

NASA Astrophysics Data System (ADS)

Li, Chong; Zhang, Guilong; Wang, Min; Chen, Jianfeng; Cai, Dongqing; Wu, Zhengyan

2014-08-01

High energy electron beam (HEEB) irradiation and hydrothermal treatment (HT), were applied in order to remove the impurities and enlarge the pore size of diatomite, making diatomite more suitable to be a catalyst support. The results demonstrated that, through thermal, charge, impact and etching effects, HEEB irradiation could make the impurities in the pores of diatomite loose and remove some of them. Then HT could remove rest of them from the pores and contribute significantly to the modification of the pore size distribution of diatomite due to thermal expansion, water swelling and thermolysis effects. Moreover, the pore structure modification improved the properties (BET (Brunauer-Emmett-Teller) specific surface area, bulk density and pore volume) of diatomite and the catalytic efficiency of the catalyst prepared from the treated diatomite.
High performance, high durability non-precious metal fuel cell catalysts

DOEpatents

Wood, Thomas E.; Atanasoski, Radoslav; Schmoeckel, Alison K.

2016-03-15

This invention relates to non-precious metal fuel cell cathode catalysts, fuel cells that contain these catalysts, and methods of making the same. The fuel cell cathode catalysts are highly nitrogenated carbon materials that can contain a transition metal. The highly nitrogenated carbon materials can be supported on a nanoparticle substrate.
Mechanistically Driven Development of Iridium Catalysts for Asymmetric Allylic Substitution

PubMed Central

Hartwig, John F.; Stanley, Levi M.

2010-01-01

Conspectus Enantioselective allylic substitution reactions comprise some of the most versatile methods for preparing enantiomerically enriched materials. These reactions form products that contain multiple functionalities by creating carbon–nitrogen, carbon–oxygen, carbon–carbon, and carbon–sulfur bonds. For many years, the development of catalysts for allylic substitution focused on palladium complexes. However, studies of complexes of other metals have revealed selectivities that often complement those of palladium systems. Most striking is the observation that reactions with unsymmetrical allylic electrophiles that typically occur with palladium catalysts at the less hindered site of an allylic electrophile occur at the more hindered site with catalysts based on other metals. In this Account, we describe an iridium precursor and a phosphoramidite ligand that catalyze reactions with a particularly broad scope of nucleophiles. The active form of this iridium catalyst is not generated by the simple binding of the phosphoramidite ligand to the metal precursor. Instead, the initial phosphoramidite and iridium precursor react in the presence of base to form a metallacyclic species that is the active catalyst. This species is generated either in situ or separately in isolated form by reactions with added base. The identification of the structure of the active catalyst led to the development of simplified catalysts as well as the most active form of the catalyst now available, which is stabilized by a loosely bound ethylene. Most recently, this structure was used to prepare intermediates containing allyl ligands, the structures of which provide a model for the enantioselectivities discussed here. Initial studies from our laboratory on the scope of iridium-catalyzed allylic substitution showed that reactions of primary and secondary amines, including alkylamines, benzylamines, and allylamines, and reactions of phenoxides and alkoxides occurred in high yields, with high branched-to-linear ratios and high enantioselectivities. Parallel mechanistic studies had revealed the metallacyclic structure of the active catalyst, and subsequent experiments with the purposefully formed metallacycle increased the reaction scope dramatically. Aromatic amines, azoles, ammonia, and amides and carbamates as ammonia equivalents all reacted with high selectivities and yields. Moreover, weakly basic enolates (such as silyl enol ethers) and enolate equivalents (such as enamines) also reacted, and other research groups have used this catalyst to conduct reactions of stabilized carbon nucleophiles in the absence of additional base. One hallmark of the reactions catalyzed by this iridium system is the invariably high enantioselectivity, which reflects a high stereoselectivity for formation of the allyl intermediate. Enantioselectivity typically exceeds 95%, regioselectivity for formation of branched over linear products is usually near 20:1, and yields generally exceed 75% and are often greater than 90%. Thus, the development of iridium catalysts for enantioselective allylic substitution shows how studies of reaction mechanism can lead to a particularly active and a remarkably general system for an enantioselective process. In this case, a readily accessible catalyst effects allylic substitution, with high enantioselectivity and regioselectivity complementary to that of the venerable palladium systems. PMID:20873839
An investigation into the effects of different existing states of aluminum isopropoxide on copper-based catalysts for direct synthesis of dimethyl ether from syngas

NASA Astrophysics Data System (ADS)

Sun, Kai; Wang, Peng; Bian, Zhongkai; Huang, Wei

2018-01-01

Aluminum isopropoxide (AIP) is a vital raw material to produce high surface area alumina catalyst, which is used for catalytic applications, such as hydrocracking, Fischer-Tropsch and STD (syngas to dimethyl ether) reactions. However, the different existing states have an effect on hydrolysis and condensation in the process of precursor preparation. The Cu/Zn/Al slurry catalysts were prepared by aluminum isopropoxide, which were liquid state, crystalline state and solid state, utilizing a complete liquid phase preparation technology. In the dimethyl ether (DME) synthesis reaction, the aluminum resource of crystalline state was prepared for slurry catalyst, which presented high CO conversion and DME selectivity of 54.32% and 69.74%, respectively. Characterization results indicated that different forms of AIP have the variant coordination numbers of Al-O and polymerization degrees, and the catalyst prepared by crystalline state consists amount of tetra-coordinated Al and few hexa-coordinated Al, which can exert different hydrolysis and condensation process compared with other aluminum sources, and finally it contributes to the strong interaction between active site copper species and Zn/Al species, confirming more Cu+ is responsible for the synthesis of DME in the slurry reactor.
Effect of different promoter precursors in a model Ru-Cs/graphite system on the catalytic selectivity for Fischer-Tropsch reaction

NASA Astrophysics Data System (ADS)

Eslava, José L.; Iglesias-Juez, Ana; Fernández-García, Marcos; Guerrero-Ruiz, Antonio; Rodríguez-Ramos, Inmaculada

2018-07-01

The effect of using two different promoter precursors on the Fischer-Tropsch synthesis was studied over cesium promoted ruthenium catalysts supported on a high surface area graphite support. In this work we reveal significant modifications in the selectivity values for Fischer-Tropsch reaction depending on the Cs promoter precursor (CsCl vs CsNO3). Specifically the bimetallic catalyst (4Ru-4Cs), prepared from nitrates both for metal and promoter precursors, showed a high selectivity to CO2 during reaction. By modifying the cesium precursor, it was possible to inhibit the water gas shift reaction, decreasing significantly the selectivity to CO2. In order to understand the chemical origin of these modifications a careful characterization of the materials was performed including: X-ray absorption near edge spectroscopy, transmission electron microscopy measurements, temperature programmed reduction studies, determination of the CO uptakes on the catalysts and the evolution of the CO adsorption heats as a function of surface coverages. It was found that upon reduction and under reaction atmosphere the promoter in the ex-nitrate catalyst appears as Cs2O which is considered responsible of the CO2 production, while in the catalysts prepared with Cs chloride the promoter remains as CsCl suffering a slight partial reduction.
Catalytic hydroprocessing of coal-derived gasification residues to fuel blending stocks: effect of reaction variables and catalyst on hydrodeoxygenation (HDO), hydrodenitrogenation (HDN), and hydrodesulfurization (HDS)

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

Dieter Leckel

2006-10-15

Gas liquors, tar oils, and tar products resulting from the coal gasification of a high-temperature Fischer-Tropsch plant can be successfully refined to fuel blending components by the use of severe hydroprocessing conditions. High operating temperatures and pressures combined with low space velocities ensure the deep hydrogenation of refractory oxygen, sulfur, and nitrogen compounds. Hydrodeoxygenation, particularly the removal of phenolic components, hydrodesulfurization, and hydrodenitrogenation were obtained at greater than 99% levels using the NiMo and NiW on {gamma}-Al{sub 2}O{sub 3} catalysts. Maximum deoxygenation activity was achieved using the NiMo/{gamma}-Al{sub 2}O{sub 3} catalyst having a maximum pore size distribution in the rangemore » of 110-220{angstrom}. The NiMo/{gamma}-Al{sub 2}O{sub 3} catalyst, which also has a relatively high proportion of smaller pore sizes (35-60 {angstrom}), displays lower hydrogenation activity. 30 refs., 1 fig. 8 tabs.« less
Nanosheet Supported Single-Metal Atom Bifunctional Catalyst for Overall Water Splitting.

PubMed

Ling, Chongyi; Shi, Li; Ouyang, Yixin; Zeng, Xiao Cheng; Wang, Jinlan

2017-08-09

Nanosheet supported single-atom catalysts (SACs) can make full use of metal atoms and yet entail high selectivity and activity, and bifunctional catalysts can enable higher performance while lowering the cost than two separate unifunctional catalysts. Supported single-atom bifunctional catalysts are therefore of great economic interest and scientific importance. Here, on the basis of first-principles computations, we report a design of the first single-atom bifunctional eletrocatalyst, namely, isolated nickel atom supported on β 12 boron monolayer (Ni 1 /β 12 -BM), to achieve overall water splitting. This nanosheet supported SAC exhibits remarkable electrocatalytic performance with the computed overpotential for oxygen/hydrogen evolution reaction being just 0.40/0.06 V. The ab initio molecular dynamics simulation shows that the SAC can survive up to 800 K elevated temperature, while enacting a high energy barrier of 1.68 eV to prevent isolated Ni atoms from clustering. A viable experimental route for the synthesis of Ni 1 /β 12 -BM SAC is demonstrated from computer simulation. The desired nanosheet supported single-atom bifunctional catalysts not only show great potential for achieving overall water splitting but also offer cost-effective opportunities for advancing clean energy technology.
Evaluation of Alkylamine Modified Pt Nanoparticles as Oxygen Reduction Reaction Electrocatalyst for Fuel Cells via Electrochemical Impedance Spectroscopy.

PubMed

Joshi, Prerna; Okada, Toshihiko; Miyabayashi, Keiko; Miyake, Mikio

2018-05-15

Organically (octyl amine, OA) surface modified electrocatalyst (OA-Pt/CB) was studied for its oxygen reduction reaction (ORR) activity via dc methods and its charge and mass transfer properties were studied via electrochemical impedance spectroscopy (EIS). Comparison with a commercial catalyst (TEC10V30E) with similar Pt content was also carried out. In EIS, both the catalysts showed a single time-constant with an emerging high-frequency semicircle of very small diameter which was fitted using suitable equivalent circuits. The organically modified catalyst showed lower charge-transfer resistance and hence, low polarization resistance in high potential region as compared to the commercial catalyst. The dominance of kinetic processes was observed at 0.925-1.000 V, whereas domination of diffusion based processes was observed at lower potential region for the organic catalyst. No effect due to the presence of carbon was observed in the EIS spectra. Using the hydrodynamic method, higher current penetration depth was obtained for the organically modified catalyst at 1600 rpm. Exchange current density and Tafel slopes for both the electrocatalysts were calculated from the polarization resistance obtained from EIS which was in correlation with the results obtained from dc methods.
Process for degrading hypochlorite and sodium hypochlorite

DOEpatents

Huxtable, William P.; Griffith, William L.; Compere, Alicia L.

1990-01-01

A process for degrading hypochlorite waste and lithium hypochlorite solutions uses a cobalt oxide/molybdenum oxide catalyst formed from about 1-10 w/w % cobalt oxide and 1-15 w/w % molybdenum oxide disposed on a suitable substrate. The major advantage of the catalyst lies in its high degree of effectiveness and its very low cost.
Highly active Pt/MoC and Pt/TiC catalysts for the low-temperature water-gas shift reaction: Effects of the carbide metal/carbon ratio on the catalyst performance

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

Rodriguez, José A.; Ramírez, Pedro J.; Gutierrez, Ramón A.

We present that Pt/MoC and Pt/TiC(001) are excellent catalysts for the low-temperature water-gas shift (WGS, CO + H 2O → H 2 + CO 2) reaction. They exhibit high-activity, stability and selectivity. The highest catalytic activities are seen for small coverages of Pt on the carbide substrates. Synergistic effects at the metal-carbide interface produce an enhancement in chemical activity with respect to pure Pt, MoC and TiC. A clear correlation is found between the ability of the Pt/MoC and Pt/TiC(001) surfaces to partially dissociate water and their catalytic activity for the WGS reaction. Finally, an overall comparison of the resultsmore » for Pt/MoC and Pt/Mo 2C(001) indicates that the metal/carbon ratio in the carbide support can have a strong influence in the stability and selectivity of WGS catalysts and is a parameter that must be taken into consideration when designing these systems.« less
Dry reforming of methane on a highly-active Ni-CeO 2 catalyst: Effects of metal-support interactions on C–H bond breaking

DOE PAGES

Liu, Zongyuan; Grinter, David C.; Lustemberg, Pablo G.; ...

2016-05-04

Ni-CeO 2 is a highly efficient, stable and non-expensive catalyst for methane dry reforming at relative low temperatures (700 K). The active phase of the catalyst consists of small nanoparticles of nickel dispersed on partially reduced ceria. Experiments of ambient pressure XPS indicate that methane dissociates on Ni/CeO 2 at temperatures as low as 300 K, generating CH x and CO x species on the surface of the catalyst. Strong metal–support interactions activate Ni for the dissociation of methane. The results of density-functional calculations show a drop in the effective barrier for methane activation from 0.9 eV on Ni(111) tomore » only 0.15 eV on Ni/CeO 2–x(111). At 700 K, under methane dry reforming conditions, no signals for adsorbed CH x or C species are detected in the C1s XPS region. As a result, the reforming of methane proceeds in a clean and efficient way.« less
Highly active Pt/MoC and Pt/TiC catalysts for the low-temperature water-gas shift reaction: Effects of the carbide metal/carbon ratio on the catalyst performance

DOE PAGES

Rodriguez, José A.; Ramírez, Pedro J.; Gutierrez, Ramón A.

2016-09-20

We present that Pt/MoC and Pt/TiC(001) are excellent catalysts for the low-temperature water-gas shift (WGS, CO + H 2O → H 2 + CO 2) reaction. They exhibit high-activity, stability and selectivity. The highest catalytic activities are seen for small coverages of Pt on the carbide substrates. Synergistic effects at the metal-carbide interface produce an enhancement in chemical activity with respect to pure Pt, MoC and TiC. A clear correlation is found between the ability of the Pt/MoC and Pt/TiC(001) surfaces to partially dissociate water and their catalytic activity for the WGS reaction. Finally, an overall comparison of the resultsmore » for Pt/MoC and Pt/Mo 2C(001) indicates that the metal/carbon ratio in the carbide support can have a strong influence in the stability and selectivity of WGS catalysts and is a parameter that must be taken into consideration when designing these systems.« less
Hierarchical Mesoporous NiO/MnO2@PANI Core-Shell Microspheres, Highly Efficient and Stable Bifunctional Electrocatalysts for Oxygen Evolution and Reduction Reactions.

PubMed

He, Junkai; Wang, Mingchao; Wang, Wenbo; Miao, Ran; Zhong, Wei; Chen, Sheng-Yu; Poges, Shannon; Jafari, Tahereh; Song, Wenqiao; Liu, Jiachen; Suib, Steven L

2017-12-13

We report on the new facile synthesis of mesoporous NiO/MnO 2 in one step by modifying inverse micelle templated UCT (University of Connecticut) methods. The catalyst shows excellent electrocatalytic activity and stability for both the oxygen evolution reaction (OER) and the oxygen reduction reaction (ORR) in alkaline media after further coating with polyaniline (PANI). For electrochemical performance, the optimized catalyst exhibits a potential gap, ΔE, of 0.75 V to achieve a current of 10 mA cm -2 for the OER and -3 mA cm -2 for the ORR in 0.1 M KOH solution. Extensive characterization methods were applied to investigate the structure-property of the catalyst for correlations with activity (e.g., XRD, BET, SEM, HRTEM, FIB-TEM, XPS, TGA, and Raman). The high electrocatalytic activity of the catalyst closely relates to the good electrical conductivity of PANI, accessible mesoporous structure, high surface area, as well as the synergistic effect of the specific core-shell structure. This work opens a new avenue for the rational design of core-shell structure catalysts for energy conversion and storage applications.
CeO2-CuO/Cu2O/Cu monolithic catalysts with three-kind morphologies Cu2O layers for preferential CO oxidation

NASA Astrophysics Data System (ADS)

Jing, Guojuan; Zhang, Xuejiao; Zhang, Aiai; Li, Meng; Zeng, Shanghong; Xu, Changjin; Su, Haiquan

2018-03-01

The supports of copper slices with three-kind morphologies Cu2O layers were prepared by the hydrothermal method. The Cu2O layers are rod-like structure, three-dimensional reticular and porous morphology as well as flower-like morphology, respectively. The CeO2-CuO/Cu2O/Cu monolithic catalysts present porous and network structure or foam morphology after loading CeO2 and CuO. Cu and Ce elements are uniformly dispersed onto the support surface. It is found that the monolithic catalyst with flower-like Cu2O layer displays better low-temperature activity because of highly-dispersed CuO and high Olatt concentration. The monolithic catalysts with rod-like or reticular-morphology Cu2O layers present high-temperature activity due to larger CuO crystallite sizes and good synergistic effect at copper-ceria interfacial sites. The as-prepared CeO2-CuO/Cu2O/Cu monolithic catalysts show good performance in the CO-PROX reaction. The generation of Cu2O layers with three-kind morphologies is beneficial to the loading and dispersion of copper oxides and ceria.
Atomic Scale Analysis of the Enhanced Electro- and Photo-Catalytic Activity in High-Index Faceted Porous NiO Nanowires

NASA Astrophysics Data System (ADS)

Shen, Meng; Han, Ali; Wang, Xijun; Ro, Yun Goo; Kargar, Alireza; Lin, Yue; Guo, Hua; Du, Pingwu; Jiang, Jun; Zhang, Jingyu; Dayeh, Shadi A.; Xiang, Bin

2015-02-01

Catalysts play a significant role in clean renewable hydrogen fuel generation through water splitting reaction as the surface of most semiconductors proper for water splitting has poor performance for hydrogen gas evolution. The catalytic performance strongly depends on the atomic arrangement at the surface, which necessitates the correlation of the surface structure to the catalytic activity in well-controlled catalyst surfaces. Herein, we report a novel catalytic performance of simple-synthesized porous NiO nanowires (NWs) as catalyst/co-catalyst for the hydrogen evolution reaction (HER). The correlation of catalytic activity and atomic/surface structure is investigated by detailed high resolution transmission electron microscopy (HRTEM) exhibiting a strong dependence of NiO NW photo- and electrocatalytic HER performance on the density of exposed high-index-facet (HIF) atoms, which corroborates with theoretical calculations. Significantly, the optimized porous NiO NWs offer long-term electrocatalytic stability of over one day and 45 times higher photocatalytic hydrogen production compared to commercial NiO nanoparticles. Our results open new perspectives in the search for the development of structurally stable and chemically active semiconductor-based catalysts for cost-effective and efficient hydrogen fuel production at large scale.
Highly tunable porous organic polymer (POP) supports for metallocene-based ethylene polymerization

NASA Astrophysics Data System (ADS)

Wang, Xiong; Li, Zhenyou; Han, Xiaoyu; Han, Zhengang; Bai, Yongxiao

2017-10-01

Porous organic Polymers (POPs) can not only exhibit high specific surface area and pore volume, but also tunable pore size distribution. Herein, copolymers of 2-hydroxyethylmethylacrylate (HEMA) and divinylbenzene (DVB) with specific pore structure were synthesized via a dispersion polymerization strategy, and then immobilized metallocene catalysts with well-defined pore structure were obtained on the produced POP supports. The nitrogen sorption and Gel permeation chromatography (GPC) results demonstrate that the pore structure of the immobilized metallocene catalyst is highly dependent on the pore structure of the POPs, and the pore structure of metallocene catalysts or the POPs has a significant influence on the molecular chain growth of the produced polyethylene. By tuning the distribution of the active species scattered in the micro- and the narrow meso-pore range (roughly ≤4 nm), the chain growth of the polyolefin can be tailored effectively during the polymerization process, although differential scanning calorimetry (DSC) and temperature rising elution fractionation (TREF) results show that the chemical composition distributions (CCDs) of produced PE from the POPs-supported metallocene catalysts are not determined by polymerization activity or molecule chain length, but mainly by the active site species scattered in the supported catalysts. Scanning electron micrograph (SEM) shows that the produced polyethylene has highly porous fabric which consists of nanofiber and spherical beads of micron dimension.
Effect of EtOH/MgCl(2) molar ratios on the catalytic properties of MgCl(2)-SiO(2)/TiCl(4) Ziegler-Natta catalyst for ethylene polymerization.

PubMed

Patthamasang, Supanan; Jongsomjit, Bunjerd; Praserthdam, Piyasan

2011-09-29

MgCl(2)-SiO(2)/TiCl(4) Ziegler-Natta catalysts for ethylene polymerization were prepared by impregnation of MgCl(2) on SiO(2) in heptane and further treatment with TiCl(4). MgCl(2)·nEtOH adduct solutions were prepared with various EtOH/MgCl(2) molar ratios for preparation of the MgCl(2)-supported and MgCl(2)-SiO(2)-supported catalysts in order to investigate the effect on polymerization performance of both catalyst systems. The catalytic activities for ethylene polymerization decreased markedly with increased molar ratios of [EtOH]/[MgCl(2)] for the MgCl(2)-supported catalysts, while for the bi-supported catalysts, the activities only decreased slightly. The MgCl(2)-SiO(2)-supported catalyst had relatively constant activity, independent of the [EtOH]/[MgCl(2)] ratio. The lower [EtOH]/[MgCl(2)] in MgCl(2)-supported catalyst exhibited better catalytic activity. However, for the MgCl(2)-SiO(2)-supported catalyst, MgCl(2) can agglomerate on the SiO(2) surface at low [EtOH]/[MgCl(2)] thus not being not suitable for TiCl(4) loading. It was found that the optimized [EtOH]/[MgCl(2)] value for preparation of bi-supported catalysts having high activity and good spherical morphology with little agglomerated MgCl(2) was 7. Morphological studies indicated that MgCl(2)-SiO(2)-supported catalysts have good morphology with spherical shapes that retain the morphology of SiO(2). The BET measurement revealed that pore size is the key parameter dictating polymerization activity. The TGA profiles of the bi-supported catalyst also confirmed that it was more stable than the mono-supported catalyst, especially in the ethanol removal region.
ATTRITION RESISTANT IRON-BASED FISCHER-TROPSCH CATALYSTS

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

James G. Goodwin, Jr.; James J. Spivey; K. Jothimurugesan

1999-03-29

The Fischer-Tropsch (F-T) reaction provides a way of converting coal-derived synthesis gas (CO+H{sub 2}) to liquid fuels. Since the reaction is highly exothermic, one of the major problems in control of the reaction is heat removal. Recent work has shown that the use of slurry bubble column reactors (SBCRs) can largely solve this problem. Iron-based (Fe) catalysts are preferred catalysts for F-T when using low CO/H2 ratio synthesis gases derived from modern coal gasifiers. This is because in addition to reasonable F-T activity, the F-T catalysts also possess high water gas shift (WGS) activity. However, a serious problem with themore » use of Fe catalysts in a SBCR is their tendency to undergo attrition. This can cause fouling/plugging of downstream filters and equipment, making the separation of catalyst from the oil/wax product very difficult if not impossible, and results in a steady loss of catalyst from the reactor. The objectives of this research are to develop a better understanding of the parameters affecting attrition resistance of Fe F-T catalysts suitable for use in SBCRs and to incorporate this understanding into the design of novel Fe catalysts having superior attrition resistance. Catalyst preparations will be based on the use of spray drying and will be scalable using commercially available equipment. The research will employ among other measurements, attrition testing and F-T synthesis, including long duration slurry reactor runs in order to ascertain the degree of success of the various preparations. The goal is to develop an Fe catalyst which can be used in a SBCR having only an internal filter for separation of the catalyst from the liquid product, without sacrificing F-T activity and selectivity. The effect of silica addition via coprecipitation and as a binder to a doubly promoted Fischer-Tropsch synthesis iron catalyst (100 Fe/5 Cu/4.2 K) was studied. The catalysts were prepared by coprecipitation, followed by binder addition and drying in a 1 m diameter, 2 m tall spray dryer. The binder silica content was varied from 0 to 20 wt %. A catalyst with 12 wt % binder silica was found to have the highest attrition resistance. F-T reaction studies over 100 hours in a fixed-bed reactor showed that this catalyst maintained around 95 % CO conversion with a methane selectivity of less than 7 wt % and a C5 + selectivity of greater than 73 wt %. The effect of adding precipitated silica from 0 to 20 parts by weight to this catalyst (containing 12 wt % binder silica) was also studied. Addition of precipitated silica was found to be detrimental to attrition resistance and resulted in increased methane and reduced wax formation. An HPR series of proprietary catalysts was prepared to further improve the attrition resistance. Based on the experience gained, a proprietary HPR-43 catalyst has been successfully spray dried in 500 g quantity. This catalyst showed 95 % CO conversion over 125 h and had less than 4 % methane selectivity. Its attrition resistance was one of the highest among the catalyst tested.« less
NiMn layered double hydroxide nanosheets/NiCo2O4 nanowires with surface rich high valence state metal oxide as an efficient electrocatalyst for oxygen evolution reaction

NASA Astrophysics Data System (ADS)

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

2018-07-01

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

The enhancement of CuO modified V2O5-WO3/TiO2 based SCR catalyst for Hg° oxidation in simulated flue gas

NASA Astrophysics Data System (ADS)

Chen, Chuanmin; Jia, Wenbo; Liu, Songtao; Cao, Yue

2018-04-01

CuO modified V2O5-WO3/TiO2 based SCR catalysts prepared by improved impregnation method were investigated to evaluate the catalytic activity for elemental mercury (Hg°) oxidation in simulated flue gas at 150-400 °C. Nitrogen adsorption, X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) were used to characterize the catalysts. It was found that V0.8WTi-Cu3 catalyst exhibited the superior Hg° oxidation activity and wide operating temperature window at the gas hourly space velocity (GHSV) of 3 × 105 h-1. The BET and XRD results showed that CuO was well loaded and highly dispersed on the catalysts surface. The XPS results suggested that the addition of CuO generated abundant chemisorbed oxygen, which was due to the synergistic effect between CuO and V2O5. The existence of the redox cycle of V4+ + Cu2+ ↔ V5+ + Cu+ in V0.8WTi-Cu3 catalyst enhanced Hg° oxidation activity. The effects of flue gas components (O2, NO, SO2 and H2O) on Hg° oxidation over V0.8WTi-Cu3 catalyst were also explored. Moreover, the co-presence of NO and NH3 remarkably inhibited Hg° oxidation, which was due to the competitive adsorption and reduction effect of NH3 at SCR condition. Fortunately, this inhibiting effect was gradually scavenged with the decrease of GHSV. The mechanism of Hg° oxidation was also investigated.
Low-temperature conversion of ammonia to nitrogen in water with ozone over composite metal oxide catalyst.

PubMed

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.
Synthesis of Highly Active Sub-Nanometer Pt@Rh Core-Shell Nanocatalyst via a Photochemical Route: Porous Titania Nanoplates as a Superior Photoactive Support.

PubMed

Zhan, Wen-Wen; Zhu, Qi-Long; Dang, Song; Liu, Zheng; Kitta, Mitsunori; Suenaga, Kazutomo; Zheng, Lan-Sun; Xu, Qiang

2017-04-01

Sub-nanometer Pt@Rh nanoparticles highly dispersed on MIL-125-derived porous TiO 2 nanoplates are successfully prepared for the first time by a photochemical route, where the porous TiO 2 nanoplates with a relatively high specific surface area play a dual role as both effective photoreductant and catalyst support. The resulting Pt@Rh/p-TiO 2 can be utilized as a highly active catalyst. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Cobalt-embedded carbon nanofiber derived from a coordination polymer as a highly efficient heterogeneous catalyst for activating oxone in water.

PubMed

Lin, Kun-Yi Andrew; Tong, Wai-Chi; Du, Yunchen

2018-03-01

Carbon fiber (CF) supported cobalt nanoparticles (NPs) are promising catalysts for activating Oxone because carbon is non-metal and earth-abundant, and CF-based catalysts exhibit a high aspect ratio, which affords more accessible and dense catalytic sites. Nevertheless, most of CF-supported catalysts are fabricated by post-synthetic methods, which involve complicated preparations. More importantly, metallic NPs are attached to the outer surface of CF rather than embedded within CF. However, there is still a great demand for developing Co-bearing carbon fibers for Oxone activation via simple and effective methods. Thus, this study proposes to develop a cobalt NP-embedded carbon nanofiber (CCNF) by a simple hydrothermal reaction of Co and nitrilotriacetic acid (NA), followed by one-step carbonization. Owing to the coordinative structure of CoNA, the derivative CCNF exhibits a fibrous carbon matrix embedded with evenly distributed and densely packed Co 3 O 4 and magnetic Co 0 nanoparticles. The fibrous structure, magnetism and embedded Co NPs enable CCNF to be a promising catalyst for Oxone activation. As degradation of Rhodamine B (RhB) is selected as a model reaction, CCNF not only rapidly activates Oxone to fully degrade RhB but also shows a much higher catalytic activity than the most common Oxone activator, Co 3 O 4 . CCNF also exhibits the lowest activation energy than any reported catalysts for Oxone activation to degrade RhB. In addition, CCNF could be re-used to activate Oxone for RhB degradation. These results indicate that CCNF is a conveniently prepared and highly effective fibrous Co/C hybrid material for activating Oxone to oxidize contaminants in water. Copyright © 2017. Published by Elsevier Ltd.
Z-Selective Metathesis Homocoupling of 1,3-Dienes by Molybdenum and Tungsten Monoaryloxide Pyrrolide (MAP) Complexes

PubMed Central

Townsend, Erik M.; Schrock, Richard R.; Hoveyda, Amir H.

2012-01-01

Molybdenum or tungsten MAP complexes that contain OHIPT as the aryloxide (hexaisopropylterphenoxide) are effective catalysts for homocoupling of simple (E)-1,3-dienes to give (E,Z,E)-trienes in high yield and with high Z selectivities. A vinylalkylidene MAP species was shown to have the expected syn structure in an X-ray study. MAP catalysts that contain OHMT (hexamethylterphenoxide) are relatively inefficient. PMID:22734508
Plastic catalytic pyrolysis to fuels as tertiary polymer recycling method: effect of process conditions.

PubMed

Gulab, Hussain; Jan, Muhammad Rasul; Shah, Jasmin; Manos, George

2010-01-01

This paper presents results regarding the effect of various process conditions on the performance of a zeolite catalyst in pyrolysis of high density polyethylene. The results show that polymer catalytic degradation can be operated at relatively low catalyst content reducing the cost of a potential industrial process. As the polymer to catalyst mass ratio increases, the system becomes less active, but high temperatures compensate for this activity loss resulting in high conversion values at usual batch times and even higher yields of liquid products due to less overcracking. The results also show that high flow rate of carrier gas causes evaporation of liquid products falsifying results, as it was obvious from liquid yield results at different reaction times as well as the corresponding boiling point distributions. Furthermore, results are presented regarding temperature effects on liquid selectivity. Similar values resulted from different final reactor temperatures, which are attributed to the batch operation of the experimental equipment. Since polymer and catalyst both undergo the same temperature profile, which is the same up to a specific time independent of the final temperature. Obviously, this common temperature step determines the selectivity to specific products. However, selectivity to specific products is affected by the temperature, as shown in the corresponding boiling point distributions, with higher temperatures showing an increased selectivity to middle boiling point components (C(8)-C(9)) and lower temperatures increased selectivity to heavy components (C(14)-C(18)).
A novel nano-Ni/SiO2 catalyst for hydrogen production from steam reforming of ethanol.

PubMed

Wu, Chunfei; Williams, Paul T

2010-08-01

Catalytic steam reforming of ethanol has been regarded as a promising way to produce hydrogen. However, catalytic deactivation is a key problem in the process. In this paper, a novel nano-Ni/SiO2 catalyst was prepared by a simple sol-gel method and compared to catalysts prepared by an impregnation method in relation to the steam reforming ethanol process. Good Ni dispersion and high BET surface areas (>700 m2 g(-1)) were obtained for sol-gel catalysts, whereas only 1 m2 g(-1) surface area was obtained for the Ni/SiO2 impregnation catalyst. The results of catalytic steam reforming of ethanol showed that about twice of the hydrogen production was produced with the Ni/SiO2 catalyst prepared by sol-gel (around 0.2 g h(-1)) compared with that prepared by impregnation (around 0.1 g h(-1)). The analysis of the used catalysts showed that 10Ni/SiO2-B and 20Ni/SiO2-B presented the highest stability, while other catalysts were fragmented into small pieces after the reforming process, especially the catalysts prepared by impregnation. A novel catalyst has been produced that has been shown to be effective in the production of hydrogen from the steam reforming of ethanol.
The Dependence of CNT Aerogel Synthesis on Sulfur-driven Catalyst Nucleation Processes and a Critical Catalyst Particle Mass Concentration.

PubMed

Hoecker, Christian; Smail, Fiona; Pick, Martin; Weller, Lee; Boies, Adam M

2017-11-06

The floating catalyst chemical vapor deposition (FC-CVD) process permits macro-scale assembly of nanoscale materials, enabling continuous production of carbon nanotube (CNT) aerogels. Despite the intensive research in the field, fundamental uncertainties remain regarding how catalyst particle dynamics within the system influence the CNT aerogel formation, thus limiting effective scale-up. While aerogel formation in FC-CVD reactors requires a catalyst (typically iron, Fe) and a promotor (typically sulfur, S), their synergistic roles are not fully understood. This paper presents a paradigm shift in the understanding of the role of S in the process with new experimental studies identifying that S lowers the nucleation barrier of the catalyst nanoparticles. Furthermore, CNT aerogel formation requires a critical threshold of Fe x C y > 160 mg/m 3 , but is surprisingly independent of the initial catalyst diameter or number concentration. The robustness of the critical catalyst mass concentration principle is proved further by producing CNTs using alternative catalyst systems; Fe nanoparticles from a plasma spark generator and cobaltocene and nickelocene precursors. This finding provides evidence that low-cost and high throughput CNT aerogel routes may be achieved by decoupled and enhanced catalyst production and control, opening up new possibilities for large-scale CNT synthesis.
Low energy electron catalyst: the electronic origin of catalytic strategies.

PubMed

Davis, Daly; Sajeev, Y

2016-10-12

Using a low energy electron (LEE) as a catalyst, the electronic origin of the catalytic strategies corresponding to substrate selectivity, reaction specificity and reaction rate enhancement is investigated for a reversible unimolecular elementary reaction. An electronic energy complementarity between the catalyst and the substrate molecule is the origin of substrate selectivity and reaction specificity. The electronic energy complementarity is induced by tuning the electronic energy of the catalyst. The energy complementarity maximizes the binding forces between the catalyst and the molecule. Consequently, a new electronically metastable high-energy reactant state and a corresponding new low barrier reaction path are resonantly created for a specific reaction of the substrate through the formation of a catalyst-substrate transient adduct. The LEE catalysis also reveals a fundamental structure-energy correspondence in the formation of the catalyst-substrate transient adduct. Since the energy complementarities corresponding to the substrate molecules of the forward and the backward steps of the reversible reactions are not the same due to their structural differences, the LEE catalyst exhibits a unique one-way catalytic strategy, i.e., the LEE catalyst favors the reversible reaction more effectively in one direction. A characteristic stronger binding of the catalyst to the transition state of the reaction than in the initial reactant state and the final product state is the molecular origin of barrier lowering.
Highly selective hydrogenation of furfural to furfuryl alcohol over Pt nanoparticles supported on g-C3N4 nanosheets catalysts in water.

PubMed

Chen, Xiufang; Zhang, Ligang; Zhang, Bo; Guo, Xingcui; Mu, Xindong

2016-06-22

Graphitic carbon nitride nanosheets were investigated for developing effective Pt catalyst supports for selective hydrogenation of furfural to furfuryl alcohol in water. The nanosheets with an average thickness of about 3 nm were synthesized by a simple and green method through thermal oxidation etching of bulk g-C3N4 in air. Combined with the unique feature of nitrogen richness and locally conjugated structure, the g-C3N4 nanosheets with a high surface area of 142 m(2) g(-1) were demonstrated to be an excellent supports for loading small-size Pt nanoparticles. Superior furfural hydrogenation activity in water with complete conversion of furfural and high selectivity of furfuryl alcohol (>99%) was observed for g-C3N4 nanosheets supported Pt catalysts. The large specific surface area, uniform dispersion of Pt nanoparticles and the stronger furfural adsorption ability of nanosheets contributed to the considerable catalytic performance. The reusability tests showed that the novel Pt catalyst could maintain high activity and stability in the furfural hydrogenation reaction.
Highly selective hydrogenation of furfural to furfuryl alcohol over Pt nanoparticles supported on g-C3N4 nanosheets catalysts in water

NASA Astrophysics Data System (ADS)

Chen, Xiufang; Zhang, Ligang; Zhang, Bo; Guo, Xingcui; Mu, Xindong

2016-06-01

Graphitic carbon nitride nanosheets were investigated for developing effective Pt catalyst supports for selective hydrogenation of furfural to furfuryl alcohol in water. The nanosheets with an average thickness of about 3 nm were synthesized by a simple and green method through thermal oxidation etching of bulk g-C3N4 in air. Combined with the unique feature of nitrogen richness and locally conjugated structure, the g-C3N4 nanosheets with a high surface area of 142 m2 g-1 were demonstrated to be an excellent supports for loading small-size Pt nanoparticles. Superior furfural hydrogenation activity in water with complete conversion of furfural and high selectivity of furfuryl alcohol (>99%) was observed for g-C3N4 nanosheets supported Pt catalysts. The large specific surface area, uniform dispersion of Pt nanoparticles and the stronger furfural adsorption ability of nanosheets contributed to the considerable catalytic performance. The reusability tests showed that the novel Pt catalyst could maintain high activity and stability in the furfural hydrogenation reaction.
Highly selective hydrogenation of furfural to furfuryl alcohol over Pt nanoparticles supported on g-C3N4 nanosheets catalysts in water

PubMed Central

Chen, Xiufang; Zhang, Ligang; Zhang, Bo; Guo, Xingcui; Mu, Xindong

2016-01-01

Graphitic carbon nitride nanosheets were investigated for developing effective Pt catalyst supports for selective hydrogenation of furfural to furfuryl alcohol in water. The nanosheets with an average thickness of about 3 nm were synthesized by a simple and green method through thermal oxidation etching of bulk g-C3N4 in air. Combined with the unique feature of nitrogen richness and locally conjugated structure, the g-C3N4 nanosheets with a high surface area of 142 m2 g−1 were demonstrated to be an excellent supports for loading small-size Pt nanoparticles. Superior furfural hydrogenation activity in water with complete conversion of furfural and high selectivity of furfuryl alcohol (>99%) was observed for g-C3N4 nanosheets supported Pt catalysts. The large specific surface area, uniform dispersion of Pt nanoparticles and the stronger furfural adsorption ability of nanosheets contributed to the considerable catalytic performance. The reusability tests showed that the novel Pt catalyst could maintain high activity and stability in the furfural hydrogenation reaction. PMID:27328834
Effect of the Mn oxidation state and lattice oxygen in Mn-based TiO2 catalysts on the low-temperature selective catalytic reduction of NO by NH3.

PubMed

Lee, Sang Moon; Park, Kwang Hee; Kim, Sung Su; Kwon, Dong Wook; Hong, Sung Chang

2012-09-01

TiO2-supported manganese oxide catalysts formed using different calcination temperatures were prepared by using the wet-impregnation method and were investigated for their activity in the low-temperature selective catalytic reduction (SCR) of NO by NH3 with respect to the Mn valence and lattice oxygen behavior. The surface and bulk properties of these catalysts were examined using Brunauer-Emmett-Teller (BET) surface area, X-ray diffraction (XRD), temperature-programmed reduction (TPR), and temperature-programmed desorption (TPD). Catalysts prepared using lower calcination temperatures, which contained Mn4+ displayed high SCR activity at low temperatures and possessed several acid sites and active oxygen. The TPD analysis determined that the Brönsted and Lewis acid sites in the Mn/TiO2 catalysts were important for the low-temperature SCR at 80-160 and 200-350 degrees C, respectively. In addition, the available lattice oxygen was important for attaining high NO to NO2 oxidation at low temperatures. Recently, various Mn catalysts have been evaluated as SCR catalysts. However, there have been no studies on the relationship of adsorption and desorption properties and behavior of lattice oxygen according to the valence state for manganese oxides (MnO(x)). Therefore, in this study, the catalysts were prepared by the wet-impregnation method at different calcination temperatures in order to show the difference of manganese oxidation state. These catalysts were then characterized using various physicochemical techniques, including BET, XRD, TPR, and TPD, to understand the structure, oxidation state, redox properties, and adsorption and desorption properties of the Mn/TiO2 catalysts.
Magnetic diatomite(Kieselguhr)/Fe2O3/TiO2 composite as an efficient photo-Fenton system for dye degradation

NASA Astrophysics Data System (ADS)

Barbosa, Isaltino A.; Zanatta, Lucas D.; Espimpolo, Daniela M.; da Silva, Douglas L.; Nascimento, Leandro F.; Zanardi, Fabrício B.; de Sousa Filho, Paulo C.; Serra, Osvaldo A.; Iamamoto, Yassuko

2017-10-01

We explored the potential use of diatomite/Fe2O3/TiO2 composites as catalysts for heterogeneous photo-Fenton degradation of methylene blue under neutral pH. Such system consists in magnetic solids synthesized by co-precipitation with Fe2+/Fe3+ in the presence of diatomite, followed by impregnation of TiO2. The results showed that the optimal amount of the catalyst was 2.0 g L-1, since aggregation phenomena become significant above this concentration, which decreases the photodegradation activity. The catalyst is highly efficient in the degradation of methylene blue and shows an easy recovery by an external magnetic field. This allows for an effective catalyst reuse without significant loss of activity in catalytic cycles, which is a highly interesting prospect for recyclable dye degradation systems.
DOE Office of Scientific and Technical Information (OSTI.GOV)

Fang, Howard L.; Wang, Jerry C.; Yu, Robert C.

Sulfur poisoning from engine fuel and lube is one of the most recognizable degradation mechanisms of a NOx adsorber catalyst system for diesel emission reduction. Even with the availability of 15 ppm sulfur diesel fuel, NOx adsorber will be deactivated without an effective sulfur management. Two general pathways are currently being explored for sulfur management: (1) the use of a disposable SOx trap that can be replaced or rejuvenated offline periodically, and (2) the use of diesel fuel injection in the exhaust and high temperature de-sulfation approach to remove the sulfur poisons to recover the NOx trapping efficiency. The majormore » concern of the de-sulfation process is the many prolonged high temperature rich cycles that catalyst will encounter during its useful life. It is shown that NOx adsorber catalyst suffers some loss of its trapping capacity upon high temperature lean-rich exposure. With the use of a disposable SOx trap to remove large portion of the sulfur poisons from the exhaust, the NOx adsorber catalyst can be protected and the numbers of de-sulfation events can be greatly reduced. Spectroscopic techniques, such as DRIFTS and Raman, have been used to monitor the underlying chemical reactions during NOx trapping/ regeneration and de-sulfation periods, and provide a fundamental understanding of NOx storage capacity and catalyst degradation mechanism using model catalysts. This paper examines the sulfur effect on two model NOx adsorber catalysts. The chemistry of SOx/base metal oxides and the sulfation product pathways and their corresponding spectroscopic data are discussed. SAE Paper SAE-2003-01-3245 {copyright} 2003 SAE International. This paper is published on this website with permission from SAE International. As a user of this website, you are permitted to view this paper on-line, download this pdf file and print one copy of this paper at no cost for your use only. The downloaded pdf file and printout of this SAE paper may not be copied, distributed or forwarded to others or for the use of others.« less
Functionalized carbon dot adorned coconut shell char derived green catalysts for the rapid synthesis of amidoalkyl naphthols.

PubMed

Narayanan, Divya P; Cherikallinmel, Sudha Kochiyil; Sankaran, Sugunan; Narayanan, Binitha N

2018-06-15

A one pot synthesis of carbon dot incorporated porous coconut shell char derived sulphonated catalyst is reported here for the first time and is effectively used in the multicomponent synthesis of amidoalkyl naphthol. Macroporous nature of the char is revealed from scanning electron microscopic (SEM) analysis, whereas the dispersion of carbon dots (CDs) on the porous coconut shell char is confirmed from the high resolution transmission electron microscopic (HRTEM) analysis. Fluorescence emission spectrum further confirmed the presence of CDs in the catalyst. Fourier-transform infrared (FTIR) spectral analysis of the materials indicated that sulphonation occurred both to the CD and to the porous char. X-ray photo electron spectroscopic (XPS) analysis of the most active catalyst confirmed the presence of both sulphonic acid and carboxylic acid groups in the catalyst. The coconut shell char derived materials prepared by varying the amount of H 2 SO 4 are successfully utilized as efficient alternative green catalysts for the multicomponent reaction, where excellent activity in amidoalkyl naphthol synthesis is obtained within short periods under solvent free reaction conditions. A maximum yield of 98% is obtained in the synthesis of N-[Phenyl-(2-hydroxy-naphthalen-1-yl)-methyl]-benzamide, the representative amidoalkyl naphthol, with the best catalyst within 3 min of reaction. The catalyst is highly active for the reactions carried out with varieties of aldehydes and amides with a product yield in the range of 88-98%. The best catalyst system retained more than 90% of its initial activity even upto 6 th repeated run. Copyright © 2018 Elsevier Inc. All rights reserved.
Recent progress in asymmetric bifunctional catalysis using multimetallic systems.

PubMed

Shibasaki, Masakatsu; Kanai, Motomu; Matsunaga, Shigeki; Kumagai, Naoya

2009-08-18

The concept of bifunctional catalysis, wherein both partners of a bimolecular reaction are simultaneously activated, is very powerful for designing efficient asymmetric catalysts. Catalytic asymmetric processes are indispensable for producing enantiomerically enriched compounds in modern organic synthesis, providing more economical and environmentally benign results than methods requiring stoichiometric amounts of chiral reagents. Extensive efforts in this field have produced many asymmetric catalysts, and now a number of reactions can be rendered asymmetric. We have focused on the development of asymmetric catalysts that exhibit high activity, selectivity, and broad substrate generality under mild reaction conditions. Asymmetric catalysts based on the concept of bifunctional catalysis have emerged as a particularly effective class, enabling simultaneous activation of multiple reaction components. Compared with conventional catalysts, bifunctional catalysts generally exhibit enhanced catalytic activity and higher levels of stereodifferentiation under milder reaction conditions, attracting much attention as next-generation catalysts for prospective practical applications. In this Account, we describe recent advances in enantioselective catalysis with bifunctional catalysts. Since our identification of heterobimetallic rare earth-alkali metal-BINOL (REMB) complexes, we have developed various types of bifunctional multimetallic catalysts. The REMB catalytic system is effective for catalytic asymmetric Corey-Chaykovsky epoxidation and cyclopropanation. A dinucleating Schiff base has emerged as a suitable multidentate ligand for bimetallic catalysts, promoting catalytic syn-selective nitro-Mannich, anti-selective nitroaldol, and Mannich-type reactions. The sugar-based ligand GluCAPO provides a suitable platform for polymetallic catalysts; structural elucidation revealed that their higher order polymetallic structures are a determining factor for their function in the catalytic asymmetric Strecker reaction. Rational design identified a related ligand, FujiCAPO, which exhibits superior performance in catalytic asymmetric conjugate addition of cyanide to enones and a catalytic asymmetric Diels-Alder-type reaction. The combination of an amide-based ligand with a rare earth metal constitutes a unique catalytic system: the ligand-metal association is in equilibrium because of structural flexibility. These catalytic systems are effective for asymmetric amination of highly coordinative substrate as well as for Mannich-type reaction of alpha-cyanoketones, in which hydrogen bonding cooperatively contributes to substrate activation and stereodifferentiation. Most of the reactions described here generate stereogenic tetrasubstituted carbons or quaternary carbons, noteworthy accomplishments even with modern synthetic methods. Several reactions have been incorporated into the asymmetric synthesis of therapeutics (or their candidate molecules) such as Tamiflu, AS-3201 (ranirestat), GRL-06579A, and ritodrine, illustrating the usefulness of bifunctional asymmetric catalysis.
Enhanced activity and stability of La-doped CeO2 monolithic catalysts for lean-oxygen methane combustion.

PubMed

Zhu, Wenjun; Jin, Jianhui; Chen, Xiao; Li, Chuang; Wang, Tonghua; Tsang, Chi-Wing; Liang, Changhai

2018-02-01

Effective utilization of coal bed methane is very significant for energy utilization and environment protection. Catalytic combustion of methane is a promising way to eliminate trace amounts of oxygen in the coal bed methane and the key to this technology is the development of high-efficiency catalysts. Herein, we report a series of Ce 1-x La x O 2-δ (x = 0-0.8) monolithic catalysts for the catalytic combustion of methane, which are prepared by citric acid method. The structural characterization shows that the substitution of La enhance the oxygen vacancy concentration and reducibility of the supports and promote the migration of the surface oxygen, as a result improve the catalytic activity of CeO 2 . M-Ce 0.8 La 0.2 O 2-δ (monolithic catalyst, Ce 0.8 La 0.2 O 2-δ coated on cordierite honeycomb) exhibits outstanding activity for methane combustion, and the temperature for 10 and 90% methane conversion are 495 and 580 °C, respectively. Additionally, Ce 0.8 La 0.2 O 2-δ monolithic catalyst presents excellent stability at high temperature. These Ce 1-x La x O 2-δ monolithic materials with a small amount of La incorporation therefore show promises as highly efficient solid solution catalysts for lean-oxygen methane combustion. Graphical abstract ᅟ.
MicroChannel Reactors for ISRU Applications Using Nanofabricated Catalysts

NASA Astrophysics Data System (ADS)

Carranza, Susana; Makel, Darby B.; Vander Wal, Randall L.; Berger, Gordon M.; Pushkarev, Vladimir V.

2006-01-01

With the new direction of NASA to emphasize the exploration of the Moon, Mars and beyond, quick development and demonstration of efficient systems for In-Situ Resources Utilization (ISRU) is more critical and timely than ever before. Affordable planning and execution of prolonged manned space missions depend upon the utilization of local resources and the waste products which are formed in manned spacecraft and surface bases. This paper presents current development of miniaturized chemical processing systems that combine microchannel reactor design with nanofabricated catalysts. Carbon nanotubes (CNT) are used to produce a nanostructure within microchannel reactors, as support for catalysts. By virtue of their nanoscale dimensions, nanotubes geometrically restrict the catalyst particle size that can be supported upon the tube walls. By confining catalyst particles to sizes smaller than the CNT diameter, a more uniform catalyst particle size distribution may be maintained. The high dispersion permitted by the vast surface area of the nanoscale material serves to retain the integrity of the catalyst by reducing sintering or coalescence. Additionally, catalytic efficiency increases with decreasing catalyst particle size (reflecting higher surface area per unit mass) while chemical reactivity frequently is enhanced at the nanoscale. Particularly significant is the catalyst exposure. Rather than being confined within a porous material or deposited upon a 2-d surface, the catalyst is fully exposed to the reactant gases by virtue of the nanofabricated support structure. The combination of microchannel technology with nanofabricated catalysts provides a synergistic effect, enhancing both technologies with the potential to produce much more efficient systems than either technology alone. The development of highly efficient microchannel reactors will be applicable to multiple ISRU programs. By selection of proper nanofabricated catalysts, the microchannel reactors can be designed for the processes that generate the most benefit for each mission, from early demonstration missions to long term settlements.
Morphological effects on the selectivity of intramolecular versus intermolecular catalytic reaction on Au nanoparticles.

PubMed

Wang, Dan; Sun, Yuanmiao; Sun, Yinghui; Huang, Jing; Liang, Zhiqiang; Li, Shuzhou; Jiang, Lin

2017-06-14

It is hard for metal nanoparticle catalysts to control the selectivity of a catalytic reaction in a simple process. In this work, we obtain active Au nanoparticle catalysts with high selectivity for the hydrogenation reaction of aromatic nitro compounds, by simply employing spine-like Au nanoparticles. The density functional theory (DFT) calculations further elucidate that the morphological effect on thermal selectivity control is an internal key parameter to modulate the nitro hydrogenation process on the surface of Au spines. These results show that controlled morphological effects may play an important role in catalysis reactions of noble metal NPs with high selectivity.

Distribution of free radicals and intermediates during the photodegradation of polychlorinated biphenyls strongly affected by cosolvents and TiO₂ catalyst.

PubMed

Zhu, Xiangdong; Wang, Yujun; Qin, Wenxiu; Zhang, Shicheng; Zhou, Dongmei

2016-02-01

Polychlorinated biphenyls (PCBs) pose potential ecological risk because of their high toxicity and carcinogenicity. Photodegradation, which is an important process for the removal of PCBs, is greatly influenced by the cosolvent and catalyst. Hence, it is important to explore their effects on the photodegradation behavior of PCBs. In this study, 2,4,4'-trichlorobiphenyl (PCB28) was selected as a model compound, and the effects of two typical cosolvents, namely acetone and ethanol, and TiO2 catalyst on the distributions of free radicals and intermediates were investigated. Interestingly, the TiO2 catalyst did not promote PCB28 photodegradation. Moreover, the free radical distribution was greatly influenced in the presence of the TiO2 catalyst, while was only slightly affected in its absence by the cosolvent kinds. The main photodegradation pathways are proposed on the basis of the distribution of detected intermediates, which were significantly regulated by both the cosolvent and TiO2 catalyst. The results provide novel insights into the photodegradation of PCBs and may have important implications for choosing cosolvent in desorbing soil PCBs and consequently enhancing PCBs degradation. Copyright © 2015 Elsevier Ltd. All rights reserved.
Catalytic Oxidation of Hydroquinone in Aqueous Solution over Bimetallic PdCo Catalyst Supported on Carbon: Effect of Interferents and Electrochemical Measurement.

PubMed

Ye, Weichun; Shi, Xuezhao; Zhang, Yane; Hong, Chenghui; Wang, Chunming; Budzianowski, Wojciech M; Xue, Desheng

2016-02-10

Palladium-cobalt alloy nanoparticles were synthesized and dispersed on carbon black support, aiming to have a less expensive catalyst. Catalytic behaviors of PdCo/C catalyst for the oxidation of hydroquinone (HQ) with H2O2 in aqueous solution were evaluated using high-performance liquid chromatography (HPLC). The results revealed that PdCo/C catalyst had better catalytic activity than an equal amount of commercial Pd/C and Co/C catalysts because of the d-band hybridization between Pd and Co. The effects of pH value, solvent, and various interferents including inorganic and organic compounds on the efficiency of HQ oxidation were further investigated. Furthermore, on the basis of mixed potential theory, comprehensive electrochemical measurements such as the open-circuit potential-time (OCP-t) technique and Tafel plot were efficient to assess the catalytic activity of the catalyst, and the results obtained were consistent with those of HPLC measurements. The efficient HQ oxidation was closely associated with the catalytic activity of PdCo nanoparticles because they accelerated the electron-transfer process and facilitated the generation of OH radicals.
Microwave-assisted Extraction of Rare Earth Elements from Petroleum Refining Catalysts and Ambient Fine Aerosols Prior to Inductively Coupled Plasma - Mass Spectrometry

NASA Technical Reports Server (NTRS)

Mittlefehldt, David W.; Kulkarni, Pranav; Chellam, Shankar

2006-01-01

In the absence of a certified reference material, a robust microwave-assisted acid digestion procedure followed by inductively coupled plasma - mass spectrometry (ICP-MS) was developed to quantify rare earth elements (REEs) in fluidized-bed catalytic cracking (FCC) catalysts and atmospheric fine particulate matter (PM2.5). High temperature (200 C), high pressure (200 psig), acid digestion (HNO3, HF, and H3BO3) with 20 minute dwell time effectively solubilized REEs from six fresh catalysts, a spent catalyst, and PM2.5. This method was also employed to measure 27 non-REEs including Na, Mg, Al, Si, K, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, As, Se, Rb, Sr, Zr, Mo, Cd, Cs, Ba, Pb, and U. Complete extraction of several REEs (Y, La, Ce, Pr, Nd, Tb, Dy, and Er) required HF indicating that they were closely associated with the aluminosilicate structure of the zeolite FCC catalysts. Internal standardization using 115In quantitatively corrected non-spectral interferences in the catalyst digestate matrix. Inter-laboratory comparison using ICP-optical emission spectroscopy (ICP-OES) and instrumental neutron activation analysis (INAA) demonstrated the applicability of the newly developed analytical method for accurate analysis of REEs in FCC catalysts. The method developed for FCC catalysts was also successfully implemented to measure trace to ultra-trace concentrations of La, Ce, Pr, Nd, Sm, Gd, Eu, and Dy in ambient PM2.5 in an industrial area of Houston, TX.
Bifunctional catalysts for upgrading of biomass-derived oxygenates: A review

DOE PAGES

Robinson, Allison M.; Hensley, Jesse E.; Medlin, J. Will

2016-06-21

Deoxygenation is an important reaction in the conversion of biomass-derived oxygenates to fuels and chemicals. A key route for biomass refining involves the production of pyrolysis oil through rapid heating of the raw biomass feedstock. Pyrolysis oil as produced is highly oxygenated, so the feasibility of this approach depends in large part on the ability to selectively deoxygenate pyrolysis oil components to create a stream of high-value finished products. Identification of catalytic materials that are active and selective for deoxygenation of pyrolysis oil components has therefore represented a major research area. One catalyst is rarely capable of performing the differentmore » types of elementary reaction steps required to deoxygenate biomass-derived compounds. For this reason, considerable attention has been placed on bifunctional catalysts, where two different active materials are used to provide catalytic sites for diverse reaction steps. Here, we review recent trends in the development of catalysts, with a focus on catalysts for which a bifunctional effect has been proposed. We summarize recent studies of hydrodeoxygenation (HDO) of pyrolysis oil and model compounds for a range of materials, including supported metal and bimetallic catalysts as well as transition-metal oxides, sulfides, carbides, nitrides, and phosphides. Particular emphasis is placed on how catalyst structure can be related to performance via molecular-level mechanisms. Finally, these studies demonstrate the importance of catalyst bifunctionality, with each class of materials requiring hydrogenation and C-O scission sites to perform HDO at reasonable rates.« less
Evaluation of the Optimum Composition of Low-Temperature Fuel Cell Electrocatalysts for Methanol Oxidation by Combinatorial Screening.

PubMed

Antolini, Ermete

2017-02-13

Combinatorial chemistry and high-throughput screening represent an innovative and rapid tool to prepare and evaluate a large number of new materials, saving time and expense for research and development. Considering that the activity and selectivity of catalysts depend on complex kinetic phenomena, making their development largely empirical in practice, they are prime candidates for combinatorial discovery and optimization. This review presents an overview of recent results of combinatorial screening of low-temperature fuel cell electrocatalysts for methanol oxidation. Optimum catalyst compositions obtained by combinatorial screening were compared with those of bulk catalysts, and the effect of the library geometry on the screening of catalyst composition is highlighted.
DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhu, Yuanyuan; Sushko, Peter V.; Melzer, Daniel

A novel pathway of increasing the surface density of catalytically active oxygen radical sites on a MoVTeNb oxide (M1 phase) catalyst during alkane oxidative dehydrogenation is reported. The novel sites form when a fraction of Te4+ is reduced and emitted from the M1 crystals under catalytic operating conditions, without compromising structural integrity of the catalyst framework. Density functional theory calculations show this Te reduction induces multiple inter-related electron transfers, and the associated cooperative effects lead to the formation of O- radicals. The in situ observations identify complex dynamic changes in the catalyst on an atomistic level, highlighting a new waymore » to tailor structure and dynamics for highly active catalysts.« less
Particle size and support effects in electrocatalysis.

PubMed

Hayden, Brian E

2013-08-20

Researchers increasingly recognize that, as with standard supported heterogeneous catalysts, the activity and selectivity of supported metal electrocatalysts are influenced by particle size, particle structure, and catalyst support. Studies using model supported heterogeneous catalysts have provided information about these effects. Similarly, model electrochemical studies on supported metal electrocatalysts can provide insight into the factors determining catalytic activity. High-throughput methods for catalyst synthesis and screening can determine systematic trends in activity as a function of support and particle size with excellent statistical certainty. In this Account, we describe several such studies investigating methods for dispersing precious metals on both carbon and oxide supports, with particular emphasis on the prospects for the development of low-temperature fuel-cell electrocatalysts. One key finding is a decrease in catalytic activity with decreasing particle size independent of the support for both oxygen reduction and CO oxidation on supported gold and platinum. For these reactions, there appears to be an intrinsic particle size effect that results in a loss of activity at particle sizes below 2-3 nm. A titania support, however, also increases activity of gold particles in the electrooxidation of CO and in the reduction of oxygen, with an optimum at 3 nm particle size. This optimum may represent the superposition of competing effects: a titania-induced enhanced activity versus deactivation at small particle sizes. The titania support shows catalytic activity at potentials where carbon-supported and bulk-gold surfaces are normally oxidized and CO electrooxidation is poisoned. On the other hand, platinum on amorphous titania shows a different effect: the oxidation reduction reaction is strongly poisoned in the same particle size range. We correlated the influence of the titania support with titania-induced changes in the surface redox behavior of the platinum particles. For both supported gold and platinum particles in electrocatalysis, we observe parallels to the effects of particle size and support in the equivalent heterogeneous catalysts. Studies of model supported-metal electrocatalysts, performs efficiently using high throughput synthetic and screening methodologies, will lead to a better understanding of the mechanisms responsible for support and particle size effects in electrocatalysis, and will drive the development of more effective and robust catalysts in the future.
Surface hydrophobicity and acidity effect on alumina catalyst in catalytic methanol dehydration reaction

PubMed Central

Osman, Ahmed I; Thompson, Jillian; Halawy, Samih A; Mohamed, Mohamed A

2017-01-01

Abstract BACKGROUND Methanol to dimethyl ether (MTD) is considered one of the main routes for the production of clean bio‐fuel. The effect of copper loading on the catalytic performance of different phases of alumina that formed by calcination at two different temperatures was examined for the dehydration of methanol to dimethyl ether (DME). RESULTS A range of Cu loadings of (1, 2, 4, 6, 10 and 15% Cu wt/wt) on Al2O3 calcined at 350 and 550 °C were prepared and characterized by TGA, XRD, BET, NH3‐TPD, TEM, H2‐TPR, SEM, EDX, XPS and DRIFT‐Pyridine techniques. The prepared catalysts were used in a fixed bed reactor under reaction conditions in which the temperature ranged from 180–300 °C with weight hourly space velocity (WHSV) = 12.1 h‐1. It was observed that all catalysts calcined at 550 °C (γ‐Al2O3 support phase) exhibited higher activity than those calcined at 350 °C (γ‐AlOOH), and this is due to the phase support change. Furthermore, the optimum Cu loading was found to be 6% Cu/γ‐Al2O3 with this catalyst also showing a high degree of stability under steady state conditions and this is attributed to the enhancement in surface acidity and hydrophobicity. CONCLUSION The addition of copper to the support improved the catalyst properties and activity. For all the copper modified catalysts, the optimum catalyst with high degree of activity and stability was 6% copper loaded on gamma alumina. © 2017 The Authors. Journal of Chemical Technology & Biotechnology published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry. PMID:29200585
Highly dispersed catalysts for coal liquefaction. Quarterly report No. 9, August 23, 1993--November 22, 1993

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

Hirschon, A.S.; Wilson, R.B.

We analyzed two sets of liquefaction experiments, one involved the liquefaction of Black Thunder Coal with the corresponding recycle vehicle, and the second set of liquefaction runs involved the liquefaction of Argonne North Dakota Lignite. We compared coal conversions of Black Thunder coal and recycle solvent using Fe(CO){sub 5} and carbon monoxide/hydrogen atmospheres and a MolyVanL molybdenum catalyst under a hydrogen atmosphere. We also continued our investigation of the effect of water on the conversions. We found that addition of water seemed to decrease the amount of oils; we determined the effect of water with the recycle solvent alone, (nomore » coal added) under similar conditions, and again produced a decrease in oil yields. FIMS analyses of the hexane and toluene soluble fractions seem to indicate that in the experiment when water was added, a considerable amount of light material remained behind in the toluene layer, suggesting that somehow the addition of water decreased the amount of extracted material, perhaps by increasing the amount of polarity of the product. When the conversion was conducted with the MolyVanL molybdenum catalyst a good quality product in terms of lower viscosity was produced; however, conversions to THF soluble material was not increased. We believe the molybdenum catalyst hydrogenated the recycle vehicle rather than effectively converted the coal. In order to eliminate the effect of solvent we have often conducted experiments in an inert solvent with Argonne coals. We conducted several coal conversions experiments using an Argonne North Dakota lignite. We compared several dispersed Fe catalysts and in addition, a nickel catalyst. We investigated nickel as a catalyst since we believe this metal may be more effective in decarboxylating low rank coals. Consistent with this premise we found that the nickel catalyst gave the highest conversions.« less
Synergistic effect of Brønsted acid and platinum on purification of automobile exhaust gases

PubMed Central

Fu, Wei; Li, Xin-Hao; Bao, Hong-Liang; Wang, Kai-Xue; Wei, Xiao; Cai, Yi-Yu; Chen, Jie-Sheng

2013-01-01

The catalytic purification of automobile exhaust gases (CO, NOx and hydrocarbons) is one of the most practiced conversion processes used to lower the emissions and to reduce the air pollution. Nevertheless, the good performance of exhaust gas purification catalysts often requires the high consumption of noble metals such as platinum. Here we report that the Brønsted acid sites on the external surface of a microporous silicoaluminophosphate (SAPO) act as a promoter for exhaust gas purification, effectively cutting the loading amount of platinum in the catalyst without sacrifice of performance. It is revealed that in the Pt-loaded SAPO-CHA catalyst, there exists a remarkable synergistic effect between the Brønsted acid sites and the Pt nanoparticles, the former helping to adsorb and activate the hydrocarbon molecules for NO reduction during the catalytic process. The thermal stability of SAPO-CHA also makes the composite catalyst stable and reusable without activity decay. PMID:23907148
Synergistic effect of Brønsted acid and platinum on purification of automobile exhaust gases.

PubMed

Fu, Wei; Li, Xin-Hao; Bao, Hong-Liang; Wang, Kai-Xue; Wei, Xiao; Cai, Yi-Yu; Chen, Jie-Sheng

2013-01-01

The catalytic purification of automobile exhaust gases (CO, NOx and hydrocarbons) is one of the most practiced conversion processes used to lower the emissions and to reduce the air pollution. Nevertheless, the good performance of exhaust gas purification catalysts often requires the high consumption of noble metals such as platinum. Here we report that the Brønsted acid sites on the external surface of a microporous silicoaluminophosphate (SAPO) act as a promoter for exhaust gas purification, effectively cutting the loading amount of platinum in the catalyst without sacrifice of performance. It is revealed that in the Pt-loaded SAPO-CHA catalyst, there exists a remarkable synergistic effect between the Brønsted acid sites and the Pt nanoparticles, the former helping to adsorb and activate the hydrocarbon molecules for NO reduction during the catalytic process. The thermal stability of SAPO-CHA also makes the composite catalyst stable and reusable without activity decay.
Controlled growth of vertically aligned carbon nanotubes on metal substrates

NASA Astrophysics Data System (ADS)

Gao, Zhaoli

Carbon nanotube (CNT) is a fascinating material with extraordinary electrical thermal and mechanical properties. Growing vertically aligned CNT (VACNT) arrays on metal substrates is an important step in bringing CNT into practical applications such as thermal interface materials (TIMs) and microelectrodes. However, the growth process is challenging due to the difficulties in preventing catalyst diffusion and controlling catalyst dewetting on metal substrates with physical surface heterogeneity. In this work, the catalyst diffusion mechanism and catalyst dewetting theory were studied for the controlled growth of VACNTs on metal substrates. The diffusion time of the catalyst, the diffusion coefficients for the catalyst in the substrate materials and the number density of catalyst nanoparticles after dewetting are identified as the key parameters, based on which three strategies are developed. Firstly, a fast-heating catalyst pretreatment strategy was used, aiming at preserving the amount of catalyst prior to CNT growth by reducing the catalyst diffusion time. The catalyst lifetime is extended from half an hour to one hour on a patterned Al thin film and a VACNT height of 106 mum, about twenty fold of that reported in the literature, was attained. Secondly, a diffusion barrier layer strategy is employed for a reduction of catalyst diffusion into the substrate materials. Enhancement of VACNT growth on Cu substrates was achieved by adopting a conformal Al2O 3 diffusion barrier layer fabricated by a specially designed atomic layer deposition (ALD) system. Lastly, a novel catalyst glancing angle deposition (GLAD) strategy is performed to manipulate the morphology of a relatively thick catalyst on metal substrates with physical surface heterogeneity, aiming to obtain uniform and dense catalyst nanoparticles after dewetting in the pretreatment process for enhanced VACNT growth. We are able to control the VACNT growth conditions on metal substrates in terms of their distribution, heights and alignments. Catalyst loss is controlled by the catalyst diffusion time and catalyst diffusion coefficients. A shorter catalyst diffusion time and smaller diffusion coefficient enhance VACNT growth on metals due to reduced catalyst loss during the pretreatment process. The dewetting behaviors of the thin film catalysts are influenced by the physical surface heterogeneity of the substrates which leads to non-uniform growth of VACNTs. The GLAD process facilitates the deposition of a relatively thick catalyst layer for the creation of dense and uniform catalyst nanoparticles. Applications of VACNT-metal structures in TIMs and microelectrodes are demonstrated. The VACNT-TIMs fabricated on Al alloy substrates have a typical thermal contact resistivity of 17.1 mm2˙K/W and their effective application in high-brightness LED thermal management was demonstrated. Electrochemical characterization was carried out on VACNT microelectrodes for the development of high resolution retinal prostheses and a satisfactory electrochemical property was again demonstrated.
Manipulating the Rate-Limiting Step in Water Oxidation Catalysis by Ruthenium Bipyridine–Dicarboxylate Complexes

DOE PAGES

Shaffer, David W.; Xie, Yan; Szalda, David J.; ...

2016-11-01

In order to gain a deeper mechanistic understanding of water oxidation by [(bda)Ru(L) 2] catalysts (bdaH 2 = [2,2'-bipyridine]-6,6'-dicarboxylic acid; L = pyridine-type ligand), a series of modified catalysts with one and two trifluoromethyl groups in the 4 position of the bda 2– ligand was synthesized and studied using stopped-flow kinetics. The additional $-$CF 3 groups increased the oxidation potentials for the catalysts and enhanced the rate of electrocatalytic water oxidation at low pH. Stopped-flow measurements of cerium(IV)-driven water oxidation at pH 1 revealed two distinct kinetic regimes depending on catalyst concentration. At relatively high catalyst concentration (ca. ≥10 –4more » M), the rate-determining step (RDS) was a proton-coupled oxidation of the catalyst by cerium(IV) with direct kinetic isotope effects (KIE > 1). At low catalyst concentration (ca. ≤10 –6 M), the RDS was a bimolecular step with k H/k D ≈ 0.8. The results support a catalytic mechanism involving coupling of two catalyst molecules. The rate constants for both RDSs were determined for all six catalysts studied. The presence of $-$CF 3 groups had inverse effects on the two steps, with the oxidation step being fastest for the unsubstituted complexes and the bimolecular step being faster for the most electron-deficient complexes. Finally, though the axial ligands studied here did not significantly affect the oxidation potentials of the catalysts, the nature of the ligand was found to be important not only in the bimolecular step but also in facilitating electron transfer from the metal center to the sacrificial oxidant.« less
The Effect of PtRuIr Nanoparticle Crystallinity in Electrocatalytic Methanol Oxidation

PubMed Central

Ma, Yanjiao; Wang, Rongfang; Wang, Hui; Liao, Shijun; Key, Julian; Linkov, Vladimir; Ji, Shan

2013-01-01

Two structural forms of a ternary alloy PtRuIr/C catalyst, one amorphous and one highly crystalline, were synthesized and compared to determine the effect of their respective structures on their activity and stability as anodic catalysts in methanol oxidation. Characterization techniques included TEM, XRD, and EDX. Electrochemical analysis using a glassy carbon disk electrode for cyclic voltammogram and chronoamperometry were tested in a solution of 0.5 mol L−1 CH3OH and 0.5 mol L−1 H2SO4. Amorphous PtRuIr/C catalyst was found to have a larger electrochemical surface area, while the crystalline PtRuIr/C catalyst had both a higher activity in methanol oxidation and increased CO poisoning rate. Crystallinity of the active alloy nanoparticles has a big impact on both methanol oxidation activity and in the CO poisoning rate. PMID:28809233
3D CNT macrostructure synthesis catalyzed by MgFe2O4 nanoparticles-A study of surface area and spinel inversion influence

NASA Astrophysics Data System (ADS)

Zampiva, Rúbia Young Sun; Kaufmann Junior, Claudir Gabriel; Pinto, Juliano Schorne; Panta, Priscila Chaves; Alves, Annelise Kopp; Bergmann, Carlos Pérez

2017-11-01

The MgFe2O4 spinel exhibits remarkable magnetic properties that open up numerous applications in biomedicine, the environment and catalysis. MgFe2O4 nanoparticles are excellent catalyst for carbon nanotube (CNT) production. In this work, we proposed to use MgFe2O4 nanopowder as a catalyst in the production of 3D macroscopic structures based on CNTs. The creation of these nanoengineered 3D architectures remains one of the most important challenges in nanotechnology. These systems have high potential as supercapacitors, catalytic electrodes, artificial muscles and in environmental applications. 3D macrostructures are formed due to an elevated density of CNTs. The quantity and quality of the CNTs are directly related to the catalyst properties. A heat treatment study was performed to produce the most effective catalyst. Factors such as superficial area, spinel inversion, crystallite size, degree of agglomeration and its correlation with van der Waals forces were examined. As result, the ideal catalyst properties for CNT production were determined and high-density 3D CNT macrostructures were produced successfully.
Selective preparation of zeolite X and A from flyash and its use as catalyst for biodiesel production.

PubMed

Volli, Vikranth; Purkait, M K

2015-10-30

This work discusses the utilization of flyash for synthesis of heterogeneous catalyst for transesterification. Different types of zeolites were synthesized from alkali fusion followed by hydrothermal treatment of coal flyash as source material. The synthesis conditions were optimized to obtain highly crystalline zeolite based on degree of crystallinity and cation exchange capacity (CEC). The effect of CEC, acid treatment, Si/Al ratio and calcination temperature (800, 900 and 1000 °C) on zeolite formation was also studied. Pure, single phase and highly crystalline zeolite was obtained at flyash/NaOH ratio (1:1.2), fusion temperature (550 °C), fusion time (1 h), hydrothermal temperature (110 °C) and hydrothermal time (12h). The synthesized zeolite was ion-exchanged with potassium and was used as catalyst for transesterification of mustard oil to obtain a maximum conversion of 84.6% with 5 wt% catalyst concentration, 12:1 methanol to oil molar ratio, reaction time of 7 h at 65 °C. The catalyst was reused for 3 times with marginal reduction in activity. Copyright © 2015 Elsevier B.V. All rights reserved.
A Tandem Catalyst with Multiple Metal Oxide Interfaces Produced by Atomic Layer Deposition.

PubMed

Ge, Huibin; Zhang, Bin; Gu, Xiaomin; Liang, Haojie; Yang, Huimin; Gao, Zhe; Wang, Jianguo; Qin, Yong

2016-06-13

Ideal heterogeneous tandem catalysts necessitate the rational design and integration of collaborative active sites. Herein, we report on the synthesis of a new tandem catalyst with multiple metal-oxide interfaces based on a tube-in-tube nanostructure using template-assisted atomic layer deposition, in which Ni nanoparticles are supported on the outer surface of the inner Al2 O3 nanotube (Ni/Al2 O3 interface) and Pt nanoparticles are attached to the inner surface of the outer TiO2 nanotube (Pt/TiO2 interface). The tandem catalyst shows remarkably high catalytic efficiency in nitrobenzene hydrogenation over Pt/TiO2 interface with hydrogen formed in situ by the decomposition of hydrazine hydrate over Ni/Al2 O3 interface. This can be ascribed to the synergy effect of the two interfaces and the confined nanospace favoring the instant transfer of intermediates. The tube-in-tube tandem catalyst with multiple metal-oxide interfaces represents a new concept for the design of highly efficient and multifunctional nanocatalysts. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Editors' Choice—Electrochemically Active Surface Area Measurement of Aged Pt Alloy Catalysts in PEM Fuel Cells by CO Stripping

DOE PAGES

Garrick, Taylor R.; Moylan, Thomas E.; Carpenter, Michael K.; ...

2016-12-13

The use of hydrogen adsorption/desorption (HAD) is a convenient method to measure the Pt surface area of a catalyst. However, it was shown that electrochemical charges measured by this technique can underestimate the Pt surface area by up to a factor of two for small Pt nanoparticles or Pt alloy nanoparticles. Electrooxidation of CO, so-called CO stripping, has been shown to be more accurate. Yet measurements of CO stripping in MEAs are scarce, especially on high activity alloy catalysts. In this study we investigated CO stripping and the ratio between Pt surface areas measured by CO and by HAD onmore » several Pt and Pt alloy catalysts. The effects on these measurements of temperature and catalyst aging by voltage cycling are discussed.« less
Editors' Choice—Electrochemically Active Surface Area Measurement of Aged Pt Alloy Catalysts in PEM Fuel Cells by CO Stripping

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

Garrick, Taylor R.; Moylan, Thomas E.; Carpenter, Michael K.

The use of hydrogen adsorption/desorption (HAD) is a convenient method to measure the Pt surface area of a catalyst. However, it was shown that electrochemical charges measured by this technique can underestimate the Pt surface area by up to a factor of two for small Pt nanoparticles or Pt alloy nanoparticles. Electrooxidation of CO, so-called CO stripping, has been shown to be more accurate. Yet measurements of CO stripping in MEAs are scarce, especially on high activity alloy catalysts. In this study we investigated CO stripping and the ratio between Pt surface areas measured by CO and by HAD onmore » several Pt and Pt alloy catalysts. The effects on these measurements of temperature and catalyst aging by voltage cycling are discussed.« less
Studies on Nano-Engineered TiO2 Photo Catalyst for Effective Degradation of Dye

NASA Astrophysics Data System (ADS)

Sowmya, S. R.; Madhu, G. M.; Hashir, Mohammed

2018-02-01

All Heterogeneous photo catalysis employing efficient photo-catalyst is the advanced dye degradation technology for the purification of textile effluent. The present work focuses on Congo red dye degradation employing synthesized Ag doped TiO2 nanoparticles as photocatalyst which is characterized using SEM, XRD and FTIR. Studies are conducted to study the effect of various parameters such as initial dye concentration, catalyst loading and pH of solution. Ag Doped TiO2 photocatalyst improve the efficacy of TiO2 by reducing high band gap and electron hole recombination of TiO2. The reaction kinetics is analyzed and the process is found to follow pseudo first order kinetics.

Diethyl Ether Production during Catalytic Dehydration of Ethanol over Ru- and Pt- modified H-beta Zeolite Catalysts.

PubMed

Kamsuwan, Tanutporn; Praserthdam, Piyasan; Jongsomjit, Bunjerd

2017-01-01

In the present study, the catalytic dehydration of ethanol over H-beta zeolite (HBZ) catalyst with ruthenium (Ru-HBZ) and platinum (Pt-HBZ) modification was investigated. Upon the reaction temperature between 200 and 400°C, it revealed that ethanol conversion and ethylene selectivity increased with increasing temperature for both Ru and Pt modification. At lower temperature (200 to 250°C), diethyl ether (DEE) was the major product. It was found that Ru and Pt modification on HBZ catalyst can result in increased DEE yield at low reaction temperature due to increased ethanol conversion without a significant change in DEE selectivity. By comparing the DEE yield of all catalysts in this study, the Ru-HBZ catalyst apparently exhibited the highest DEE yield (ca. 47%) at 250°C. However, at temperature from 350 to 400°C, the effect of Ru and Pt was less pronounced on ethylene yield. With various characterization techniques, the effects of Ru and Pt modification on HBZ catalyst were elucidated. It revealed that Ru and Pt were present in the highly dispersed forms and well distributed in the catalyst granules. It appeared that the weak acid sites measured by NH 3 temperature-programmed desorption technique also decreased with Ru and Pt promotion. Thus, the increased DEE yields with the Ru and Pt modification can be attributed to the presence of optimal weak acid sites leading to increased intrinsic activity of the catalysts. It can be concluded that the modification of Ru and Pt on HBZ catalyst can improve the DEE yields by ca. 10%.
Method of preparing meso-haloalkylporphyrins

DOEpatents

Wijesekera, Tilak; Lyons, James E.; Ellis, Jr., Paul E.; Bhinde, Manoj V.

1998-01-01

Transition metal complexes of meso-haloalkylporphyrins, wherein the haloalkyl groups contain 2 to 8 carbon atoms have been found to be highly effective catalysts for oxidation of alkanes and for the decomposition of hydroperoxides. Also disclosed is a process for the preparation of meso-halocarbyl-porphyrins which comprises contacting a halocarbyl dipyrromethane with a halocarbyl-substituted aldehyde in the presence of an acid granular solid catalyst. Also disclosed is a process for the preparation of meso-halocarbyl-porphyrins which comprises contacting a halocarbyl dipyrromethane with a halocarbyl-substituted aldehyde in the presence of an acid granular solic catalyst.
Nitrogen-Coordinated Single Cobalt Atom Catalysts for Oxygen Reduction in Proton Exchange Membrane Fuel Cells

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

Wang, Xiao Xia; Cullen, David A.; Pan, Yung-Tin

Due to the Fenton reaction, the presence of Fe and peroxide in electrodes generates free radicals causing serious degradation of the organic ionomer and the membrane. Pt-free and Fe-free cathode catalysts therefore are urgently needed for durable and inexpensive proton exchange membrane fuel cells (PEMFCs). In this paper, a high-performance nitrogen-coordinated single Co atom catalyst is derived from Co-doped metal-organic frameworks (MOFs) through a one-step thermal activation. Aberration-corrected electron microscopy combined with X-ray absorption spectroscopy virtually verifies the CoN 4 coordination at an atomic level in the catalysts. Through investigating effects of Co doping contents and thermal activation temperature, anmore » atomically Co site dispersed catalyst with optimal chemical and structural properties has achieved respectable activity and stability for the oxygen reduction reaction (ORR) in challenging acidic media (e.g., half-wave potential of 0.80 V vs reversible hydrogen electrode (RHE). The performance is comparable to Fe-based catalysts and 60 mV lower than Pt/C -60 μg Pt cm -2). Fuel cell tests confirm that catalyst activity and stability can translate to high-performance cathodes in PEMFCs. Finally, the remarkably enhanced ORR performance is attributed to the presence of well-dispersed CoN 4 active sites embedded in 3D porous MOF-derived carbon particles, omitting any inactive Co aggregates.« less
Nitrogen-Coordinated Single Cobalt Atom Catalysts for Oxygen Reduction in Proton Exchange Membrane Fuel Cells

DOE PAGES

Wang, Xiao Xia; Cullen, David A.; Pan, Yung-Tin; ...

2018-01-24

Due to the Fenton reaction, the presence of Fe and peroxide in electrodes generates free radicals causing serious degradation of the organic ionomer and the membrane. Pt-free and Fe-free cathode catalysts therefore are urgently needed for durable and inexpensive proton exchange membrane fuel cells (PEMFCs). In this paper, a high-performance nitrogen-coordinated single Co atom catalyst is derived from Co-doped metal-organic frameworks (MOFs) through a one-step thermal activation. Aberration-corrected electron microscopy combined with X-ray absorption spectroscopy virtually verifies the CoN 4 coordination at an atomic level in the catalysts. Through investigating effects of Co doping contents and thermal activation temperature, anmore » atomically Co site dispersed catalyst with optimal chemical and structural properties has achieved respectable activity and stability for the oxygen reduction reaction (ORR) in challenging acidic media (e.g., half-wave potential of 0.80 V vs reversible hydrogen electrode (RHE). The performance is comparable to Fe-based catalysts and 60 mV lower than Pt/C -60 μg Pt cm -2). Fuel cell tests confirm that catalyst activity and stability can translate to high-performance cathodes in PEMFCs. Finally, the remarkably enhanced ORR performance is attributed to the presence of well-dispersed CoN 4 active sites embedded in 3D porous MOF-derived carbon particles, omitting any inactive Co aggregates.« less
Synthesis of TiO2-CNT hybrid nanocatalyst and its application in direct oxidation of H2S to S

NASA Astrophysics Data System (ADS)

Daraee, Maryam; Baniadam, Majid; Rashidi, Alimorad; Maghrebi, Morteza

2018-07-01

In this study, a TiO2-CNT hybrid catalyst has been synthesized and its catalytic activity in the oxidation of H2S to S has been investigated and compared with those of TiO2 nanoparticles and pyrolyzed TiO2-CNT hybrid (P-TiO2-CNT). The optimum catalyst amount was determined using central composite design (CCD) method. Catalysts were characterized by various analytical techniques. The H2S conversion, sulfur selectivity and yield at the optimal temperature of 200 °C and O2/H2S ratio of 0.5 were 98.3, 99.5 and 97%, respectively. TiO2-CNT16% catalyst has a higher surface area than TiO2 nanoparticles and P-TiO2-CNT. In addition, the former catalyst gives a high conversion of H2S and sulfur selectivity at 200 °C and O2/H2S ratio of 0.5 compared with the latter two catalysts. The superior conversion (over 10%) of TiO2-CNT16% hybrid compared to TiO2 nanoparticles can be attributed to the synergistic effects of TiO2 and CNT, the reduced band gap of TiO2-CNT16% hybrid and high specific surface area of the catalyst.
Lean NO x reduction over Ag/alumina catalysts via ethanol-SCR using ethanol/gasoline blends

DOE PAGES

Gunnarsson, Fredrik; Pihl, Josh A.; Toops, Todd J.; ...

2016-09-04

This paper focuses on the activity for lean NO x reduction over sol-gel synthesized silver alumina (Ag/Al 2O 3) catalysts, with and without platinum doping, using ethanol (EtOH), EtOH/C 3H 6 and EtOH/gasoline blends as reducing agents. The effect of ethanol concentration, both by varying the hydrocarbon-to-NO x ratio and by alternating the gasoline concentration in the EtOH/gasoline mixture, is investigated. High activity for NO x reduction is demonstrated for powder catalysts for EtOH and EtOH/C 3H 6 as well as for monolith coated catalysts (EtOH and EtOH/gasoline). The results show that pure Ag/Al 2O 3 catalysts display higher NOmore » x reduction and lower light-off temperature as compared to the platinum doped samples. The 4 wt.% Ag/Al 2O 3 catalyst displays 100% reduction in the range 340–425 °C, with up to 37% selectivity towards NH 3. These results are also supported by DRIFTS (Diffuse reflection infrared Fourier transform spectroscopy) experiments. Finally, the high ammonia formation could, in combination with an NH 3-SCR catalyst, be utilized to construct a NO x reduction system with lower fuel penalty cf. stand alone HC-SCR. In addition, it would result in an overall decrease in CO 2 emissions.« less
Nitrogen-Coordinated Single Cobalt Atom Catalysts for Oxygen Reduction in Proton Exchange Membrane Fuel Cells.

PubMed

Wang, Xiao Xia; Cullen, David A; Pan, Yung-Tin; Hwang, Sooyeon; Wang, Maoyu; Feng, Zhenxing; Wang, Jingyun; Engelhard, Mark H; Zhang, Hanguang; He, Yanghua; Shao, Yuyan; Su, Dong; More, Karren L; Spendelow, Jacob S; Wu, Gang

2018-03-01

Due to the Fenton reaction, the presence of Fe and peroxide in electrodes generates free radicals causing serious degradation of the organic ionomer and the membrane. Pt-free and Fe-free cathode catalysts therefore are urgently needed for durable and inexpensive proton exchange membrane fuel cells (PEMFCs). Herein, a high-performance nitrogen-coordinated single Co atom catalyst is derived from Co-doped metal-organic frameworks (MOFs) through a one-step thermal activation. Aberration-corrected electron microscopy combined with X-ray absorption spectroscopy virtually verifies the CoN 4 coordination at an atomic level in the catalysts. Through investigating effects of Co doping contents and thermal activation temperature, an atomically Co site dispersed catalyst with optimal chemical and structural properties has achieved respectable activity and stability for the oxygen reduction reaction (ORR) in challenging acidic media (e.g., half-wave potential of 0.80 V vs reversible hydrogen electrode (RHE). The performance is comparable to Fe-based catalysts and 60 mV lower than Pt/C -60 μg Pt cm -2 ). Fuel cell tests confirm that catalyst activity and stability can translate to high-performance cathodes in PEMFCs. The remarkably enhanced ORR performance is attributed to the presence of well-dispersed CoN 4 active sites embedded in 3D porous MOF-derived carbon particles, omitting any inactive Co aggregates. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Co- and defect-rich carbon nanofiber films as a highly efficient electrocatalyst for oxygen reduction

NASA Astrophysics Data System (ADS)

Kim, Il To; Song, Myeong Jun; Shin, Seoyoon; Shin, Moo Whan

2018-03-01

Many efforts are continuously devoted to developing high-efficiency, low-cost, and highly scalable oxygen reduction reaction (ORR) electrocatalysts to replace precious metal catalysts. Herein, we successfully synthesize Co- and defect-rich carbon nanofibers (CNFs) using an efficient heat treatment approach involving the pyrolysis of electrospun fibers at 370 °C under air. The heat treatment process produces Co-decorated CNFs with a high Co mass ratio, enriched pyridinic N, Co-pyridinic Nx clusters, and defect-rich carbon structures. The synergistic effects from composition and structural changes in the designed material increase the number of catalytically active sites for the ORR in an alkaline solution. The prepared Co- and defect-rich CNFs exhibit excellent ORR activities with a high ORR onset potential (0.954 V vs. RHE), a large reduction current density (4.426 mA cm-2 at 0.40 V), and a nearly four-electron pathway. The catalyst also exhibits a better long-term durability than commercial Pt/C catalysts. This study provides a novel hybrid material as an efficient ORR catalyst and important insight into the design strategy for CNF-based hybrid materials as electrochemical electrodes.
Effect of polymer binders in anode catalyst layer on performance of alkaline direct ethanol fuel cells

NASA Astrophysics Data System (ADS)

Li, Y. S.; Zhao, T. S.; Liang, Z. X.

In preparing low-temperature fuel cell electrodes, a polymer binder is essential to bind discrete catalyst particles to form a porous catalyst layer that simultaneously facilitates the transfer of ions, electrons, and reactants/products. For two types of polymer binder, namely, an A3-an anion conducting ionomer and a PTFE-a neutral polymer, an investigation is made of the effect of the content of each binder in the anode catalyst layer on the performance of an alkaline direct ethanol fuel cell (DEFC) with an anion-exchange membrane and non-platinum (non-Pt) catalysts. Experiments are performed by feeding either ethanol (C 2H 5OH) solution or ethanol-potassium hydroxide (C 2H 5OH-KOH) solution. The experimental results for the case of feeding C 2H 5OH solution without added KOH indicate that the cell performance varies with the A3 ionomer content in the anode catalyst layer, and a content of 10 wt.% exhibits the best performance. When feeding C 2H 5OH-KOH solution, the results show that: (i) in the region of low current density, the best performance is achieved for a membrane electrode assembly without any binder in the anode catalyst layer; (ii) in the region of high current density, the performance is improved with incorporation of PTFE binder in the anode catalyst layer; (iii) the PTFE binder yields better performance than does the A3 binder.
Platinum and palladium nano-structured catalysts for polymer electrolyte fuel cells and direct methanol fuel cells.

PubMed

Long, Nguyen Viet; Thi, Cao Minh; Yong, Yang; Nogami, Masayuki; Ohtaki, Michitaka

2013-07-01

In this review, we present the synthesis and characterization of Pt, Pd, Pt based bimetallic and multi-metallic nanoparticles with mixture, alloy and core-shell structure for nano-catalysis, energy conversion, and fuel cells. Here, Pt and Pd nanoparticles with modified nanostructures can be controllably synthesized via chemistry and physics for their uses as electro-catalysts. The cheap base metal catalysts can be studied in the relationship of crystal structure, size, morphology, shape, and composition for new catalysts with low cost. Thus, Pt based alloy and core-shell catalysts can be prepared with the thin Pt and Pt-Pd shell, which are proposed in low and high temperature proton exchange membrane fuel cells (PEMFCs), and direct methanol fuel cells (DMFCs). We also present the survey of the preparation of Pt and Pd based catalysts for the better catalytic activity, high durability, and stability. The structural transformations, quantum-size effects, and characterization of Pt and Pd based catalysts in the size ranges of 30 nm (1-30 nm) are presented in electro-catalysis. In the size range of 10 nm (1-10 nm), the pure Pt catalyst shows very large surface area for electro-catalysis. To achieve homogeneous size distribution, the shaped synthesis of the polyhedral Pt nanoparticles is presented. The new concept of shaping specific shapes and morphologies in the entire nano-scale from nano to micro, such as polyhedral, cube, octahedra, tetrahedra, bar, rod, and others of the nanoparticles is proposed, especially for noble and cheap metals. The uniform Pt based nanosystems of surface structure, internal structure, shape, and morphology in the nanosized ranges are very crucial to next fuel cells. Finally, the modifications of Pt and Pd based catalysts of alloy, core-shell, and mixture structures lead to find high catalytic activity, durability, and stability for nano-catalysis, energy conversion, fuel cells, especially the next large-scale commercialization of next PEMFCs, and DMFCs.
Review of the state-of-the-art of exhaust particulate filter technology in internal combustion engines.

PubMed

Guan, Bin; Zhan, Reggie; Lin, He; Huang, Zhen

2015-05-01

The increasingly stringent emission regulations, such as US 2010, Tier 2 Bin 5 and beyond, off-road Tier 4 final, and Euro V/5 for particulate matter (PM) reduction applications, will mandate the use of the diesel particulate filters (DPFs) technology, which is proven to be the only way that can effectively control the particulate emissions. This paper covers a comprehensive overview of the state-of-the-art DPF technologies, including the advanced filter substrate materials, the novel catalyst formulations, the highly sophisticated regeneration control strategies, the DPF uncontrolled regenerations and their control methodologies, the DPF soot loading prediction, and the soot sensor for the PM on-board diagnostics (OBD) legislations. Furthermore, the progress of the highly optimized hybrid approaches, which involves the integration of diesel oxidation catalyst (DOC) + (DPF, NOx reduction catalyst), the selective catalytic reduction (SCR) catalyst coated on DPF, as well as DPF in the high-pressure exhaust gas recirculation (EGR) loop systems, is well discussed. Besides, the impacts of the quality of fuel and lubricant on the DPF performance and the maintenance and retrofit of DPF are fully elaborated. Meanwhile, the high efficiency gasoline particulate filter (GPF) technology is being required to effectively reduce the PM and particulate number (PN) emissions from the gasoline direct injection (GDI) engines to comply with the future increasingly stricter emissions regulations. Copyright © 2015 Elsevier Ltd. All rights reserved.
Oxidative desulfurization of benzothiophene and thiophene with WOx/ZrO2 catalysts: effect of calcination temperature of catalysts.

PubMed

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

Nata, Iryanti Fatyasari, E-mail: yanti_tkunlam@yahoo.com; Irawan, Chairul; Mardina, Primata

Highly sulfonated carbonaceous spheres with diameter of 100–500 nm can be generated by hydrothermal carbonization of glucose in the presence of hydroxyethylsulfonic acid and acrylic acid at 180 °C for 4 h. The acidity of the prepared carbonaceous sphere C4-SO{sub 3}H can reach 2.10 mmol/g. It was used as a solid acid catalyst for the hydrolysis of cornstarch. Total reducing sugar (TRS) concentration of 19.91 mg/mL could be obtained by hydrolyzing 20 mg/mL cornstarch at 150 °C for 6 h using C4-SO{sub 3}H as solid acid catalyst. The solid acid catalyst demonstrated good stability that only 9% decrease in TRSmore » concentration was observed after five repeat uses. The as-prepared carbon-based solid acid catalyst can be an environmentally benign replacement for homogeneous catalyst. - Highlights: • Carbon solid acid was successfully prepared by one-step hydrothermal carbonization. • The acrylic acid as monomer was effectively reduce the diameter size of particle. • The solid acid catalyst show good catalytic performance of starch hydrolysis. • The solid acid catalyst is not significantly deteriorated after repeated use.« less
Pt based PEMFC catalysts prepared from colloidal particle suspensions--a toolbox for model studies.

PubMed

Speder, Jozsef; Altmann, Lena; Roefzaad, Melanie; Bäumer, Marcus; Kirkensgaard, Jacob J K; Mortensen, Kell; Arenz, Matthias

2013-03-14

A colloidal synthesis approach is presented that allows systematic studies of the properties of supported proton exchange membrane fuel cell (PEMFC) catalysts. The applied synthesis route is based on the preparation of monodisperse nanoparticles in the absence of strong binding organic stabilizing agents. No temperature post-treatment of the catalyst is required rendering the synthesis route ideally suitable for comparative studies. We report work concerning a series of catalysts based on the same colloidal Pt nanoparticle (NP) suspension, but with different high surface area (HSA) carbon supports. It is shown that for the prepared catalysts the carbon support has no catalytic co-function, but carbon pre-treatment leads to enhanced sticking of the Pt NPs on the support. An unwanted side effect, however, is NP agglomeration during synthesis. By contrast, enhanced NP sticking without agglomeration can be accomplished by the addition of an ionomer to the NP suspension. The catalytic activity of the prepared catalysts for the oxygen reduction reaction is comparable to industrial catalysts and no influence of the particle size is found in the range of 2-5 nm.
2D and 3D imaging of the gas phase close to an operating model catalyst by planar laser induced fluorescence

NASA Astrophysics Data System (ADS)

Blomberg, Sara; Zhou, Jianfeng; Gustafson, Johan; Zetterberg, Johan; Lundgren, Edvin

2016-11-01

In recent years, efforts have been made in catalysis related surface science studies to explore the possibilities to perform experiments at conditions closer to those of a technical catalyst, in particular at increased pressures. Techniques such as high pressure scanning tunneling/atomic force microscopy (HPSTM/AFM), near ambient pressure x-ray photoemission spectroscopy (NAPXPS), surface x-ray diffraction (SXRD) and polarization-modulation infrared reflection absorption spectroscopy (PM-IRAS) at semi-realistic conditions have been used to study the surface structure of model catalysts under reaction conditions, combined with simultaneous mass spectrometry (MS). These studies have provided an increased understanding of the surface dynamics and the structure of the active phase of surfaces and nano particles as a reaction occurs, providing novel information on the structure/activity relationship. However, the surface structure detected during the reaction is sensitive to the composition of the gas phase close to the catalyst surface. Therefore, the catalytic activity of the sample itself will act as a gas-source or gas-sink, and will affect the surface structure, which in turn may complicate the assignment of the active phase. For this reason, we have applied planar laser induced fluorescence (PLIF) to the gas phase in the vicinity of an active model catalysts. Our measurements demonstrate that the gas composition differs significantly close to the catalyst and at the position of the MS, which indeed should have a profound effect on the surface structure. However, PLIF applied to catalytic reactions presents several beneficial properties in addition to investigate the effect of the catalyst on the effective gas composition close to the model catalyst. The high spatial and temporal resolution of PLIF provides a unique tool to visualize the on-set of catalytic reactions and to compare different model catalysts in the same reactive environment. The technique can be applied to a large number of molecules thanks to the technical development of lasers and detectors over the last decades, and is a complementary and visual alternative to traditional MS to be used in environments difficult to asses with MS. In this article we will review general considerations when performing PLIF experiments, our experimental set-up for PLIF and discuss relevant examples of PLIF applied to catalysis.
Investigating the effects of alkali metal Na addition on catalytic activity of HZSM-5 for methyl mercaptan elimination

NASA Astrophysics Data System (ADS)

Yu, Jie; He, Dedong; Chen, Dingkai; Liu, Jiangping; Lu, Jichang; Liu, Feng; Liu, Pan; Zhao, Yutong; Xu, Zhizhi; Luo, Yongming

2017-10-01

Na-modified HZSM-5 catalysts with different Na loading amounts were prepared by incipient-wetness impregnation method and their catalytic activities for methyl mercaptan catalytic elimination were analyzed. XRD, N2 adsorption-desorption, NH3-TPD, CO2-TPD and FT-IR measurements were carried out to investigate the effects of modification of alkali metal Na on the physicochemical properties of the HZSM-5 zeolite catalyst. Research results illustrated that the introduction of alkali metal Na can improve catalytic activity for CH3SH catalytic elimination. CH3SH can be almost completely converted over 3%-Na/HZSM-5 at 450 °C compared to pure HZSM-5 at 600 °C based on our experimental results and the results from previous research. The improved catalytic activity could be attributed to the regulated acid-base properties of the HZSM-5 catalysts by doping with alkali metal Na. High alkali concentration treatment, however, may destroy the framework structure of the catalyst sample, thus causing the poor stability performance of the obtained catalyst.
High-Flux, High Performance H2O2 Catalyst Bed for ISTAR

NASA Technical Reports Server (NTRS)

Ponzo, J.

2005-01-01

On NASA's ISTAR RBCC program packaging and performance requirements exceeded traditional H2O2 catalyst bed capabilities. Aerojet refined a high performance, monolithic 90% H202 catalyst bed previously developed and demonstrated. This approach to catalyst bed design and fabrication was an enabling technology to the ISTAR tri-fluid engine. The catalyst bed demonstrated 55 starts at throughputs greater than 0.60 lbm/s/sq in for a duration of over 900 seconds in a physical envelope approximately 114 of traditional designs. The catalyst bed uses photoetched plates of metal bonded into a single piece monolithic structure. The precise control of the geometry and complete mixing results in repeatable, quick starting, high performing catalyst bed. Three different beds were designed and tested, with the best performing bed used for tri-fluid engine testing.
Synthesis and Characterization of AlCl3 Impregnated Molybdenum Oxide as Heterogeneous Nano-Catalyst for the Friedel-Crafts Acylation Reaction in Ambient Condition.

PubMed

Jadhav, Arvind H; Chinnappan, Amutha; Hiremath, Vishwanath; Seo, Jeong Gil

2015-10-01

Aluminum trichloride (AlCl3) impregnated molybdenum oxide heterogeneous nano-catalyst was prepared by using simple impregnation method. The prepared heterogeneous catalyst was characterized by powder X-ray diffraction, FT-IR spectroscopy, solid-state NMR spectroscopy, SEM imaging, and EDX mapping. The catalytic activity of this protocol was evaluated as heterogeneous catalyst for the Friedel-Crafts acylation reaction at room temperature. The impregnated MoO4(AlCl2)2 catalyst showed tremendous catalytic activity in Friedel-Crafts acylation reaction under solvent-free and mild reaction condition. As a result, 84.0% yield of acyl product with 100% consumption of reactants in 18 h reaction time at room temperature was achieved. The effects of different solvents system with MoO4(AlCl2)2 catalyst in acylation reaction was also investigated. By using optimized reaction condition various acylated derivatives were prepared. In addition, the catalyst was separated by simple filtration process after the reaction and reused several times. Therefore, heterogeneous MoO4(AlCl2)2 catalyst was found environmentally benign catalyst, very convenient, high yielding, and clean method for the Friedel-Crafts acylation reaction under solvent-free and ambient reaction condition.
microcrystals as an efficient heterogeneous Fenton-like catalyst in degradation of rhodamine 6G

NASA Astrophysics Data System (ADS)

Li, Zhan Jun; Ali, Ghafar; Kim, Hyun Jin; Yoo, Seong Ho; Cho, Sung Oh

2014-05-01

We present a novel heterogeneous Fenton-like catalyst of LiFePO4 (LFP). LFP has been widely used as an electrode material of a lithium ion battery, but we observed that commercial LFP (LFP-C) could act as a good Fenton-like catalyst to decompose rhodamine 6G. The catalytic activity of LFP-C microparticles was much higher than a popular catalyst, magnetite nanoparticles. Furthermore, we found that the catalytic activity of LFP-C could be further increased by increasing the specific surface area. The reaction rate constant of the hydrothermally synthesized LFP microcrystals (LFP-H) is at least 18 times higher than that of magnetite nanoparticles even though the particle size of LFP is far larger than magnetite nanoparticles. The LFP catalysts also exhibited a good recycling behavior and high stability under an oxidizing environment. The effects of the experimental parameters such as the concentration of the catalysts, pH, and the concentration of hydrogen peroxide on the catalytic activity of LFP were also analyzed.
Iron doped fibrous-structured silica nanospheres as efficient catalyst for catalytic ozonation of sulfamethazine.

PubMed

Bai, Zhiyong; Wang, Jianlong; Yang, Qi

2018-04-01

Sulfonamide antibiotics are ubiquitous pollutants in aquatic environments due to their large production and extensive application. In this paper, the iron doped fibrous-structured silica (KCC-1) nanospheres (Fe-KCC-1) was prepared, characterized, and applied as a catalyst for catalytic ozonation of sulfamethazine (SMT). The effects of ozone dosage, catalyst dosage, and initial concentration of SMT were examined. The experimental results showed that Fe-KCC-1 had large surface area (464.56 m2 g -1 ) and iron particles were well dispersed on the catalyst. The catalyst had high catalytic performance especially for the mineralization of SMT, with mineralization ratio of about 40% in a wide pH range. With addition of Fe-KCC-1, the ozone utilization increased nearly two times than single ozonation. The enhancement of SMT degradation was mainly due to the surface reaction, and the increased mineralization of SMT was due to radical mechanism. Fe-KCC-1 was an efficient catalyst for SMT degradation in catalytic ozonation system.

Exploring green catalysts for production of biofuels and value added chemicals for renewable and sustainable energy future

NASA Astrophysics Data System (ADS)

Budhi, Sridhar

Porous silica have attracted significant attention in the past few decades due to their unique textural properties. They were extensively investigated for applications in catalysis, separation, environmental remediation and drug delivery. We have investigated the porous metal incorporated silica in the synthetic as well as catalytic perspectives. The synthesis of metal incorporated mesoporous silica via co-condensation such as SBA-15, KIT-5 are still challenging as it involves acidic synthetic route. Synthesis in high acidity conditions affects the incorporation of metal in silica due to high dissolution of metal precursors and breaking of metal oxygen and silica bond. The research presented here demonstrates an efficient way to incorporate metals by addition of diammonium hydrogen phosphate along with metal precursor during the synthesis. The incorporation efficiency has increased 2-3 times with this approach. Catalytic studies were performed to support our hypothesis. Such synthesized molybdenum incorporated mesoporous silica were investigated as catalyst for fast pyrolysis. When molydenum incorporated in silica was used as catalyst for fast pyrolysis of pine, it selectively produced furans (furan, methylfuran and dimethylfuran). Furans are considered value-added chemicals and can be used as a blendstock for diesel/jet grade fuel. The catalyst was very stable to harsh pyrolysis conditions and had a longer life before deactivation when compared with traditional zeolites. Further, this catalyst did not produce aromatic hydrocarbons in significant yields unlike zeolites. The origin of the furans was determined to be biopolymer cellulose and the selectivity for furans are attributed to low catalyst acidity. The effect of silica to alumina ratio (SAR) of beta-zeolite was investigated ranging to elucidate the relationship between the of number of acid sites on product speciation and catalyst deactivation on catalysts supplied by Johnson Matthey. The catalyst with low SAR (more acid sites) produced predominantly aromatic hydrocarbons and olefins with no detectable oxygen containing species. In contrary, the catalyst with high SAR (fewer acid sites) produced a suite of oxygenated products such as furans, phenols and cresols. The coke deposited on each catalyst and the yield of aromatic hydrocarbons were in direct proportion to the number of acid sites. When catalysts were active, the biomass selectivity towards hydrocarbons and amount of coke were constant regardless of SAR.
Bioleaching of metals from spent refinery petroleum catalyst using moderately thermophilic bacteria: effect of particle size.

PubMed

Srichandan, Haragobinda; Singh, Sradhanjali; Pathak, Ashish; Kim, Dong-Jin; Lee, Seoung-Won; Heyes, Graeme

2014-01-01

The present work investigated the leaching potential of moderately thermophilic bacteria in the recovery of metals from spent petroleum catalyst of varying particle sizes. The batch bioleaching experiments were conducted by employing a mixed consortium of moderate thermophilic bacteria at 45°C and by using five different particle sizes (from 45 to >2000 μm) of acetone-washed spent catalyst. The elemental mapping by FESEM confirmed the presence of Al, Ni, V and Mo along with sulfur in the spent catalyst. During bioleaching, Ni (92-97%) and V (81-91%) were leached in higher concentrations, whereas leaching yields of Al (23-38%) were found to be lowest in all particle sizes investigated. Decreasing the particle size from >2000 μm to 45-106 μm caused an increase in leaching yields of metals during initial hours. However, the final metals leaching yields were almost independent of particle sizes of catalyst. Leaching kinetics was observed to follow the diffusion-controlled model showing the linearity more close than the chemical control. The results of the present study suggested that bioleaching using moderate thermophilic bacteria was highly effective in removing the metals from spent catalyst. Moreover, bioleaching can be conducted using spent catalyst of higher particle size (>2000 μm), thus saving the grinding cost and making process attractive for larger scale application.
Cobalt-Catalyzed C(sp(2))-H Borylation: Mechanistic Insights Inspire Catalyst Design.

PubMed

Obligacion, Jennifer V; Semproni, Scott P; Pappas, Iraklis; Chirik, Paul J

2016-08-24

A comprehensive study into the mechanism of bis(phosphino)pyridine (PNP) cobalt-catalyzed C-H borylation of 2,6-lutidine using B2Pin2 (Pin = pinacolate) has been conducted. The experimentally observed rate law, deuterium kinetic isotope effects, and identification of the catalyst resting state support turnover limiting C-H activation from a fully characterized cobalt(I) boryl intermediate. Monitoring the catalytic reaction as a function of time revealed that borylation of the 4-position of the pincer in the cobalt catalyst was faster than arene borylation. Cyclic voltammetry established the electron withdrawing influence of 4-BPin, which slows the rate of C-H oxidative addition and hence overall catalytic turnover. This mechanistic insight inspired the next generation of 4-substituted PNP cobalt catalysts with electron donating and sterically blocking methyl and pyrrolidinyl substituents that exhibited increased activity for the C-H borylation of unactivated arenes. The rationally designed catalysts promote effective turnover with stoichiometric quantities of arene substrate and B2Pin2. Kinetic studies on the improved catalyst, 4-(H)2BPin, established a change in turnover limiting step from C-H oxidative addition to C-B reductive elimination. The iridium congener of the optimized cobalt catalyst, 6-(H)2BPin, was prepared and crystallographically characterized and proved inactive for C-H borylation, a result of the high kinetic barrier for reductive elimination from octahedral Ir(III) complexes.
Enhancement of Glycerol Steam Reforming Activity and Thermal Stability by Incorporating CeO2 and TiO2 in Ni- and Co-MCM-41 Catalysts

NASA Astrophysics Data System (ADS)

Dade, William N.

Hydrogen (H2) has many applications in industry with current focus shifted to production of hydrocarbon fuels and valuable oxygenates using the Fischer-Tropsch technology and direct use in proton exchange membrane fuel cell (PEMFC). Hydrogen is generally produced via steam reforming of natural gas or alcohols like methanol and ethanol. Glycerol, a by-product of biodiesel production process, is currently considered to be one of the most attractive sources of sustainable H2 due to its high H/C ratio and bio-based origin. Ni and Co based catalysts have been reported to be active in glycerol steam reforming (GSR); however, deactivation of the catalysts by carbon deposition and sintering under GSR operating conditions is a major challenge. In this study, a series of catalysts containing Ni and Co nanoparticles incorporated in CeO2 and TiO2 modified high surface area MCM-41 have been synthesized using one-pot method. The catalysts are tested for GSR (at H2O/Glycerol mole ratio of 12 and GHSV of 2200 h-1) to study the effect of support modification and reaction temperature (450 - 700 °C) on the product selectivity and long term stability. GSR results revealed that all the catalysts performed significantly well exhibiting over 85% glycerol conversion at 650 °C except Ni catalysts that showed better low temperature activities. Deactivation studies of the catalysts conducted at 650 °C indicated that the Ni-TiO2-MCM-41 and Ni-CeO 2-MCM-41 were resistant to deactivation with ˜100% glycerol conversion for 40 h. In contrast, Co-TiO2-MCM-41 perform poorly as the catalyst rapidly deactivated after 12 h to yield ˜20% glycerol conversion after 40 h. The WAXRD and TGA-DSC analyses of spent catalysts showed a significant amount of coke deposition that might explain catalysts deactivation. The flattening shape of the original BET type IV isotherm with drastic reduction of catalyst surface area can also be responsible for observed drop in catalysts activities.
Spherical α-MnO₂ Supported on N-KB as Efficient Electrocatalyst for Oxygen Reduction in Al-Air Battery.

PubMed

Chen, Kui; Wang, Mei; Li, Guangli; He, Quanguo; Liu, Jun; Li, Fuzhi

2018-04-13

Traditional noble metal platinum (Pt) is regarded as a bifunctional oxygen catalyst due to its highly catalytic efficiency, but its commercial availability and application is often restricted by high cost. Herein, a cheap and effective catalyst mixed with α-MnO₂ and nitrogen-doped Ketjenblack (N-KB) (denoted as MnO₂-SM150-0.5) is examined as a potential electrocatalyst in oxygen reduction reactions (ORR) and oxygen evolution reactions (OER). This α-MnO₂ is prepared by redox reaction between K₂S₂O₈ and MnSO₄ in acid conditions with a facile hydrothermal process (named the SM method). As a result, MnO₂-SM150-0.5 exhibits a good catalytic performance for ORR in alkaline solution, and this result is comparable to a Pt/C catalyst. Moreover, this catalyst also shows superior durability and methanol tolerance compared with a Pt/C catalyst. It also displays a discharge voltage (~1.28 V) at a discharge density of 50 mA cm -2 in homemade Al-air batteries that is higher than commercial 20% Pt/C (~1.19 V). The superior electrocatalytic performance of MnO₂-SM150-0.5 could be attributed to its higher Mn 3+ /Mn 4+ ratio and the synergistic effect between MnO₂ and the nitrogen-doped KB. This study provides a novel strategy for the preparation of an MnO₂-based composite electrocatalyst.
DOE Office of Scientific and Technical Information (OSTI.GOV)

Gunnarsson, Fredrik; Pihl, Josh A.; Toops, Todd J.

This paper focuses on the activity for lean NO x reduction over sol-gel synthesized silver alumina (Ag/Al 2O 3) catalysts, with and without platinum doping, using ethanol (EtOH), EtOH/C 3H 6 and EtOH/gasoline blends as reducing agents. The effect of ethanol concentration, both by varying the hydrocarbon-to-NO x ratio and by alternating the gasoline concentration in the EtOH/gasoline mixture, is investigated. High activity for NO x reduction is demonstrated for powder catalysts for EtOH and EtOH/C 3H 6 as well as for monolith coated catalysts (EtOH and EtOH/gasoline). The results show that pure Ag/Al 2O 3 catalysts display higher NOmore » x reduction and lower light-off temperature as compared to the platinum doped samples. The 4 wt.% Ag/Al 2O 3 catalyst displays 100% reduction in the range 340–425 °C, with up to 37% selectivity towards NH 3. These results are also supported by DRIFTS (Diffuse reflection infrared Fourier transform spectroscopy) experiments. Finally, the high ammonia formation could, in combination with an NH 3-SCR catalyst, be utilized to construct a NO x reduction system with lower fuel penalty cf. stand alone HC-SCR. In addition, it would result in an overall decrease in CO 2 emissions.« less
Enhancement of the electrooxidation of ethanol on Pt-Sn-P/C catalysts prepared by chemical deposition process

NASA Astrophysics Data System (ADS)

Xue, Xinzhong; Ge, Junjie; Tian, Tian; Liu, Changpeng; Xing, Wei; Lu, Tianhong

In this paper, five Pt 3Sn 1/C catalysts have been prepared using three different methods. It was found that phosphorus deposited on the surface of carbon with Pt and Sn when sodium hypophosphite was used as reducing agent by optimization of synthetic conditions such as pH in the synthetic solution and temperature. The deposition of phosphorus should be effective on the size reduction and markedly reduces PtSn nanoparticle size, and raise electrochemical active surface (EAS) area of catalyst and improve the catalytic performance. TEM images show PtSnP nanoparticles are highly dispersed on the carbon surface with average diameters of 2 nm. The optimum composition is Pt 3Sn 1P 2/C (note PtSn/C-3) catalyst in my work. With this composition, it shows very high activity for the electrooxidation of ethanol and exhibit enhanced performance compared with other two Pt 3Sn 1/C catalysts that prepared using ethylene glycol reduction method (note PtSn/C-EG) and borohydride reduction method (note PtSn/-B). The maximum power densities of direct ethanol fuel cell (DEFC) were 61 mW cm -2 that is 150 and 170% higher than that of the PtSn/C-EG and PtSn/C-B catalyst.
Demonstration of Selective Catalytic Reduction (SCR) technology for the control of nitrogen oxide (NO{sub x}) emissions from high-sulfur coal-fired boilers: Innovative Clean Coal Technology (ICCT). Quarterly report No. 7, January--March 1992

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

Not Available

1992-05-01

The objective of this project is to demonstrate and evaluate commercially available Selective Catalytic Reduction (SCR) catalysts from US, Japanese and European catalyst suppliers on a high-sulfur US coal-fired boiler. SCR is a post-combustion nitrogen oxide (NO{sub x}) control technology that involves injecting ammonia into the flue gas generated from coal combustion in an electric utility boiler. The flue gas containing ammonia is then passed through a reactor that contains a specialized catalyst. In the presence of the catalyst, the amonia reacts with NO{sub x} to convert it to nitrogen and water vapor. Although SCR is widely practiced in Japanmore » and Europe, there are numerous technical uncertainties associated with applying SCR to US coals. These uncertainties include: (1) potential catalyst deactivation due to poisoning by trace metal species present in US coals that are not present in other fuels. (2) performance of the technology and effects on the balance-of-plant equipment in the presence of high amounts of SO, and SO{sub 3}. (3) performance of a wide variety of SCR catalyst compositions, geometries and methods of manufacture under typical high-sulfur coal-fired utility operating conditions. These uncertainties will be explored by constructing a series of small-scale SCR reactors and simultaneously exposing different SCR catalysts to flue gas derived from the combustion of high sulfur US coal. The demonstration will be performed at Gulf Power Company`s Plant Crist Unit No. 5 (75 MW capacity) near Pensacola, Florida. The project will be funded by the US Department of Energy (DOE), Southern Company Services, Inc. (SCS on behalf of the entire Southern electric system), and the Electric Power Research Institute.« less
High-performance bimetallic alloy catalyst using Ni and N co-doped composite carbon for the oxygen electro-reduction.

PubMed

Jung, Won Suk

2018-03-15

In this study, a novel synthesis method for the bimetallic alloy catalyst is reported, which is subsequently used as an oxygen reduction catalyst in polymer electrolyte membrane fuel cells (PEMFCs). The support prepared from the Ni-chelate complex shows a mesoporous structure with a specific surface area of ca. 400 m 2  g -1 indicating the suitable support for PEMFC applications. Ethylenediamine is converted to the nitrogen and carbon layers to protect the Ni particles which will diffuse into the Pt lattice at 800 °C. The PtNi/NCC catalyst with PtNi cores and Pt-rich shells is successfully formed when acid-treated as evidenced by line scan profiles. The catalyst particles thus synthesized are well-dispersed on the N-doped carbon support, while the average particle size is ca. 3 nm. In the PEMFC test, the maximum power density of the PtNi/NCC catalyst shows approximately 25% higher than that of the commercial Pt/C catalyst. The mass activity of the PtNi/NCC catalyst showed approximately 3-fold higher than that of the commercial Pt/C catalyst. The mass activity strongly depends on the ratio of Pt to Ni since the strain effect can be strong for catalysts due to the mismatch of lattice parameters of the Ni and Pt. Copyright © 2017 Elsevier Inc. All rights reserved.
Understanding low temperature oxidation activity of nanoarray-based monolithic catalysts: from performance observation to structural and chemical insights

DOE PAGES

Du, Shoucheng; Tang, Wenxiang; Guo, Yanbing; ...

2016-12-30

Monolithic catalysts have been widely used in automotive, chemical, and energy relevant industries. Nano-array based monolithic catalysts have been developed, demonstrating high catalyst utilization efficiency and good thermal/mechanical robustness. Compared with the conventional wash-coat based monolithic catalysts, they have shown advances in precise and optimum microstructure control and feasibility in correlating materials structure with properties. Recently, the nano-array based monolithic catalysts have been studied for low temperature oxidation of automotive engine exhaust and exhibited interesting and promising catalytic activities. Here, this review focuses on discussing the key catalyst structural parameters that affect the catalytic performance from the following aspects, (1)more » geometric shape and crystal planes, (2) guest atom doping and defects, (3) array size and size-assisted active species loading, and (4) the synergy effect of metal oxide in composite nano-arrays. Prior to the discussion, an overview of the current status of synthesis and development of the nano-array based monolithic catalysts is introduced. The performance of these materials in low temperature simulated engine exhaust oxidation is also demonstrated. Finally, we hope this review will elucidate the science and chemistry behind the good oxidation performance of the nanoarray- based monolithic catalysts, and serve as a timely and useful research guide for rational design and further improvement of the nano-array based monolithic catalysts for automobile emission control.« less
Understanding low temperature oxidation activity of nanoarray-based monolithic catalysts: from performance observation to structural and chemical insights

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

Du, Shoucheng; Tang, Wenxiang; Guo, Yanbing

Monolithic catalysts have been widely used in automotive, chemical, and energy relevant industries. Nano-array based monolithic catalysts have been developed, demonstrating high catalyst utilization efficiency and good thermal/mechanical robustness. Compared with the conventional wash-coat based monolithic catalysts, they have shown advances in precise and optimum microstructure control and feasibility in correlating materials structure with properties. Recently, the nano-array based monolithic catalysts have been studied for low temperature oxidation of automotive engine exhaust and exhibited interesting and promising catalytic activities. Here, this review focuses on discussing the key catalyst structural parameters that affect the catalytic performance from the following aspects, (1)more » geometric shape and crystal planes, (2) guest atom doping and defects, (3) array size and size-assisted active species loading, and (4) the synergy effect of metal oxide in composite nano-arrays. Prior to the discussion, an overview of the current status of synthesis and development of the nano-array based monolithic catalysts is introduced. The performance of these materials in low temperature simulated engine exhaust oxidation is also demonstrated. Finally, we hope this review will elucidate the science and chemistry behind the good oxidation performance of the nanoarray- based monolithic catalysts, and serve as a timely and useful research guide for rational design and further improvement of the nano-array based monolithic catalysts for automobile emission control.« less
Synthesis, characterization, and catalytic activity in Suzuki coupling and catalase-like reactions of new chitosan supported Pd catalyst.

PubMed

Baran, Talat; Inanan, Tülden; Menteş, Ayfer

2016-07-10

The aim of this study is to analyze the synthesis of a new chitosan supported Pd catalyst and examination of its catalytic activity in: Pd catalyst was synthesized using chitosan as a biomaterial and characterized with FTIR, TG/DTG, XRD, (1)H NMR, (13)C NMR, SEM-EDAX, ICP-OES, Uv-vis spectroscopies, and magnetic moment, along with molar conductivity analysis. Biomaterial supported Pd catalyst indicated high activity and long life time as well as excellent turnover number (TON) and turnover frequency (TOF) values in Suzuki reaction. Biomaterial supported Pd catalyst catalyzed H2O2 decomposition reaction with considerable high activity using comparatively small loading catalyst (10mg). Redox potential of biomaterial supported Pd catalyst was still high without negligible loss (13% decrease) after 10 cycles in reusability tests. As a consequence, eco-friendly biomaterial supported Pd catalyst has superior properties such as high thermal stability, long life time, easy removal from reaction mixture and durability to air, moisture and high temperature. Copyright © 2016 Elsevier Ltd. All rights reserved.
Molybdenum carbides, active and in situ regenerable catalysts in hydroprocessing of fast pyrolysis bio-oil

DOE PAGES

Choi, Jae -Soon; Zacher, Alan; Wang, Huamin; ...

2016-05-19

This paper describes properties of molybdenum carbides as a potential catalyst for fast pyrolysis bio-oil hydroprocessing. Currently, high catalyst cost, short catalyst lifetime, and lack of effective regeneration methods are hampering the development of this otherwise attractive renewable hydrocarbon technology. A series of metal-doped bulk Mo carbides were synthesized, characterized, and evaluated in sequential low-temperature stabilization and high-temperature deoxygenation of a pine-derived bio-oil. During a typical 60 h run, Mo carbides were capable of upgrading raw bio-oil to a level suitable for direct insertion into the current hydrocarbon infrastructure with residual oxygen content and total acid number of upgraded oilsmore » below 2 wt % and 0.01 mg KOH g –1, respectively. The performance was shown to be sensitive to the type of metal dopant, Ni-doped Mo carbides outperforming Co-, Cu-, or Ca-doped counterparts; a higher Ni loading led to a superior catalytic performance. No bulk oxidation or other significant structural changes were observed. Besides the structural robustness, another attractive property of Mo carbides was in situ regenerability. The effectiveness of regeneration was demonstrated by successfully carrying out four consecutive 60 h runs with a reductive decoking between two adjacent runs. These results strongly suggest that Mo carbides are a good catalyst candidate which could lead to a significant cost reduction in hydroprocessing bio-oils. Furthermore, we highlight areas for future research which will be needed to further understand carbide structure–function relationships and help design practical bio-oil upgrading catalysts based on Mo carbides.« less
Remarkable support effect on the reactivity of Pt/In2O3/MOx catalysts for methanol steam reforming

NASA Astrophysics Data System (ADS)

Liu, Xin; Men, Yong; Wang, Jinguo; He, Rong; Wang, Yuanqiang

2017-10-01

Effects of supports over Pt/In2O3/MOx catalysts with extremely low loading of Pt (1 wt%) and In2O3 loadings (3 wt%) are investigated for the hydrogen production of methanol steam reforming (MSR) in the temperature range of 250-400 °C. Under practical conditions without the pre-reduction, the 1Pt/3In2O3/CeO2 catalyst shows the highly efficient catalytic performance, achieving almost complete methanol conversion (98.7%) and very low CO selectivity of 2.6% at 325 °C. The supported Pt/In2O3 catalysts are characterized by means of Brunauer-Emmett-Teller (BET) surface area, X-ray diffraction (XRD), high-resolution transmission microscopy (HRTEM), temperature programmed reduction with hydrogen (H2-TPR), CO pulse chemisorption, temperature programmed desorption of methanol and water (CH3OH-TPD and H2O-TPD). These demonstrate that the nature of catalyst support of Pt/In2O3/MOx plays crucial roles in the Pt dispersion associated by the strong interaction among Pt, In2O3 and supporting materials and the surface redox properties at low temperature, and thus affects their capability to activate the reactants and determines the catalytic activity of methanol steam reforming. The superior 1Pt/3In2O3/CeO2 catalyst, exhibiting a remarkable reactivity and stability for 32 h on stream, demonstrates its potential for efficient hydrogen production of methanol steam reforming in mobile and de-centralized H2-fueled PEMFC systems.
Molybdenum carbides, active and in situ regenerable catalysts in hydroprocessing of fast pyrolysis bio-oil

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

Choi, Jae -Soon; Zacher, Alan; Wang, Huamin

This paper describes properties of molybdenum carbides as a potential catalyst for fast pyrolysis bio-oil hydroprocessing. Currently, high catalyst cost, short catalyst lifetime, and lack of effective regeneration methods are hampering the development of this otherwise attractive renewable hydrocarbon technology. A series of metal-doped bulk Mo carbides were synthesized, characterized, and evaluated in sequential low-temperature stabilization and high-temperature deoxygenation of a pine-derived bio-oil. During a typical 60 h run, Mo carbides were capable of upgrading raw bio-oil to a level suitable for direct insertion into the current hydrocarbon infrastructure with residual oxygen content and total acid number of upgraded oilsmore » below 2 wt % and 0.01 mg KOH g –1, respectively. The performance was shown to be sensitive to the type of metal dopant, Ni-doped Mo carbides outperforming Co-, Cu-, or Ca-doped counterparts; a higher Ni loading led to a superior catalytic performance. No bulk oxidation or other significant structural changes were observed. Besides the structural robustness, another attractive property of Mo carbides was in situ regenerability. The effectiveness of regeneration was demonstrated by successfully carrying out four consecutive 60 h runs with a reductive decoking between two adjacent runs. These results strongly suggest that Mo carbides are a good catalyst candidate which could lead to a significant cost reduction in hydroprocessing bio-oils. Furthermore, we highlight areas for future research which will be needed to further understand carbide structure–function relationships and help design practical bio-oil upgrading catalysts based on Mo carbides.« less
Carbon deposition in the Bosch process with ruthenium and ruthenium-iron alloy catalysts. M.S. Thesis. Final Report, Jan. 1981 - Jul. 1982

NASA Technical Reports Server (NTRS)

Manning, M. P.; Reid, R. C.; Sophonpanich, C.

1982-01-01

The effectiveness of ruthenium and the alloys 50Ru50Fe and 33Ru67Fe as alternatives to iron, nickel, and cobalt catalysts in recovering oxygen from metabolic carbon dioxide was investigated. Carbon deposition boundaries over the unsupported alloys are reported. Experiments were also carried out over 50Ru50Fe and 97Ru3Fe3 catalysts supported on gamma-alumina to determine their performance in the synthesis of low molecular weight olefins. High production of ethylene and propylene would be beneficial for an improvement of an overall Bosch process, as a gas phase containing high olefin content would enhance carbon deposition in a Bosch reactor.
Combustion of chlorinated VOC on nanostructured chromia aerogel as catalyst and catalyst support.

PubMed

Rotter, H; Landau, M V; Herskowitz, M

2005-09-01

The chromia-based catalysts have been reported to combine the high activity and resistance to deactivation in oxidative removal of chlorinated VOC. However, their activity is limited by the low amount of chromia that can be deposited on supports maintaining the optimal state of surface species and high surface area. The pure nanostructured chromia was used as a catalytically active support for noble metals and transition-metal oxide oxidation catalysts. High efficiency of Pt-promoted CrOOH aerogel with surface area of 500 m2*g(-1) was demonstrated in full combustion of 1,2-dichloroethane (DCE) and chlorobenzene (CB). At gas hour space velocity (GHSV) of 46 000 h(-1), the total conversion to CO2/H2O/HCl was achieved at 330 degrees C (DCE) and 380 degrees C (CB). The combustion rate constants measured at standard conditions with 0.5% Pt/CrOOH catalyst were 1 or 2 orders of magnitude higher than measured with 15%Cr2O3/Al2O3 or 0.5%Pt/Al2O3, respectively. The effects of Pt, Au, Mn, and Ce additives on the performance of CrOOH aerogel in combustion of chlorinated VOC were analyzed related to the materials structure.
Metal-Free Cataluminescence Gas Sensor for Hydrogen Sulfide Based on Its Catalytic Oxidation on Silicon Carbide Nanocages.

PubMed

Wu, Liqian; Zhang, Lichun; Sun, Mingxia; Liu, Rui; Yu, Lingzhu; Lv, Yi

2017-12-19

Cataluminescence- (CTL-) based sensors are among the most attractive and effective tools for gas sensing, owing to their efficient selectivity, high sensitivity, and rapidity. As the sensing materials of CTL-based sensors, metal-based catalysts easily bring about high costs and environmental pollution of heavy metals. More importantly, the long-term stability of metal-based catalysts is usually rather poor. Metal-free catalysts have unique advantages such as environmental friendliness, low costs, and long-term stability, making them promising materials for CTL-based sensors. Herein, we report the fabrication of a CTL sensor based on a metal-free catalyst. F-doped cage-like SiC was synthesized by wet chemical etching. The as-prepared products showed a rapid, stable, highly selective, and sensitive cataluminescent response to H 2 S. The stability of the sensor was demonstrated to be fairly good for at least 15 days. After CTL tests, F-doped cage-like SiC retained its original morphology, structure, and chemical composition. In addition, to the best of our knowledge, this is the first report of a metal-free CTL sensor. Metal-free catalysts are environmentally friendly and low in cost and exhibit long-term stability, which could open a new avenue of CTL sensing.
Green diesel production via catalytic hydrogenation/decarboxylation of triglycerides and fatty acids of vegetable oil and brown grease

NASA Astrophysics Data System (ADS)

Sari, Elvan

Increase in the petroleum prices, projected increases in the world's energy demand and environmental awareness have shifted the research interest to the alternative fuel technologies. In particular, green diesel, vegetable oil/animal fat/waste oil and grease derived hydrocarbons in diesel boiling range, has become an attractive alternative to biodiesel---a mixture of fatty acid methyl esters, particularly due to its superior fuel properties that are similar to petroleum diesel. Hence, green diesel can be used as a drop-in fuel in the current diesel engines. The current technology for production of green diesel-hydrodeoxygenation of triglycerides and fatty acids over conventional hydrotreating catalysts suffers from fast catalyst deactivation in the absence of hydrogen combined with high temperatures and high fatty acid content in the feedstock. Additionally, excess hydrogen requirement for hydrodeoxygenation technique leads to high production costs. This thesis proposes a new technology-selective decarboxylation of brown grease, which is a mixture of fats and oils collected from waste water trap and rich in fatty acids, over a supported noble metal catalyst that overcomes the green diesel production challenges. In contrast to other feedstocks used for liquid biofuel production, brown grease is inexpensive and non-food competing feedstock, therefore the process finds solution to waste management issues, reduces the renewable fuel production cost and does not add to the global food shortage problems. Special catalyst formulations were developed to have a high activity and stability in the absence of hydrogen in the fatty acid decarboxylation process. The study shows how catalyst innovations can lead to a new technology that overcomes the process challenges. First, the effect of reaction parameters on the activity and the selectivity of brown grease decarboxylation with minimum hydrogen consumption over an activated carbon supported palladium catalyst were investigated. A 90% conversion of brown grease in a semi-batch mode was obtained in 7 hours. In contrast, in a batch reaction the conversion was roughly 40% in the same reaction time. However, by pre-treating the "as received" brown grease with H 2, the conversion in a batch reactor was increased 1.4--fold; and when the H2 to BG ratio was increased to 3/1 (mol/mol), the conversion was further improved. Therefore, such a two-step processing with selective hydrogenation prior to the decarboxylation of BG improves the product selectivity. The commercial 5% Pd/C catalyst was highly active for the decarboxylation of brown grease to green diesel at 300 °C and 1.5 MPa. Second, a class of Pd catalyst supported on a silica-activated carbon nanocomposite for free fatty acid decarboxylation was developed, and displayed excellent activity and operation stability selectively for the green diesel hydrocarbons formation in the absence of hydrogen under mild reaction conditions. The decarboxylation activities of different amount of silica containing catalysts were investigated in a batch reactor under inert gas. Among them, the formulation with the fewer oxygen surface groups (Pd/Si--C--4) was the most active catalyst for the decarboxylation of an unsaturated fatty acid. The high activity of the Pd/Si--C--4 catalyst is attributed to its accessible and well-distributed metallic Pd nanoparticles inside hybrid mesopores as well as to its low acidity, weak surface interactions and inertness. Thus, Pd supported on carbon modified with silica may be regarded as a prospective decarboxylation catalyst for the removal of oxygen from vegetable oil/animal fat without the need of additional hydrogen. Third, in order to design a suitable catalyst for conversion of brown grease to green diesel, a systematic study of the model compounds--oleic acid was conducted on various catalysts in super-critical water to understand the reaction pathways in the absence of hydrogen. A Si--C support was more effective than activated carbon itself for both decarboxylation of oleic acid and hydrogenation of alkenes. In an additional effort to reduce Pd amount in the catalyst, Pd2Co/C catalysts with various Pd content were prepared and the catalytic activity study showed that 0.5 wt% Pd2Co/C catalyst performs even better than a 5 wt% Pd/C catalyst. Pd and Co alloys were very well dispersed and formed fine clusters, which led to a higher active metal surface area and hence favored the decarboxylation of oleic acid. This study showed that an alloy of Pd on carbon with a significantly low Pd content is much more active and selective to diesel hydrocarbons production from an unsaturated fatty acid in super-critical water and may be regarded as a prospective feasible decarboxylation catalyst for the removal of oxygen from vegetable oil/animal fat without the need of additional hydrogen.
Catalytic Decarboxylation of Fatty Acids to Aviation Fuels over Nickel Supported on Activated Carbon

PubMed Central

Wu, Jianghua; Shi, Juanjuan; Fu, Jie; Leidl, Jamie A.; Hou, Zhaoyin; Lu, Xiuyang

2016-01-01

Decarboxylation of fatty acids over non-noble metal catalysts without added hydrogen was studied. Ni/C catalysts were prepared and exhibited excellent activity and maintenance for decarboxylation. Thereafter, the effects of nickel loading, catalyst loading, temperature, and carbon number on the decarboxylation of fatty acids were investigated. The results indicate that the products of cracking increased with high nickel loading or catalyst loading. Temperature significantly impacted the conversion of stearic acid but did not influence the selectivity. The fatty acids with large carbon numbers tend to be cracked in this reaction system. Stearic acid can be completely converted at 370 °C for 5 h, and the selectivity to heptadecane was around 80%. PMID:27292280

Attrition Resistant Iron-Based Catalysts For F-T SBCRs

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

Adeyinka A. Adeyiga

2006-01-31

The Fischer-Tropsch (F-T) reaction provides a way of converting coal-derived synthesis gas (CO+ H{sub 2}) to liquid fuels. Since the reaction is highly exothermic, one of the major problems in control of the reaction is heat removal. Recent work has shown that the use of slurry bubble column reactors (SBCRs) can largely solve this problem. The use of iron-(FE) based catalysts is attractive not only due to their low cost and ready availability, but also due to their high water-gas shift activity which makes it possible to use these catalysts with low H{sub 2}/CO ratios. However, a serious problem withmore » the use of Fe catalysts in a SBCR is their tendency to undergo attrition. This can cause fouling/plugging of downstream filters and equipment; makes the separation of catalyst from the oil/wax product very difficult, if not impossible; and results in a steady loss of catalyst from the reactor. Under a previous Department of Energy (DOE)/University Research Grant (UCR) grant, Hampton University reported, for the first time, the development of demonstrably attrition-resistant Fe F-T synthesis catalysts having good activity, selectivity, and attrition resistance. These catalysts were prepared by spray drying Fe catalysts with potassium (K), copper (Cu), and silica (SiO{sub 2}) as promoters. SiO{sub 2} was also used as a binder for spray drying. These catalysts were tested for activity and selectivity in a laboratory-scale fixed-bed reactor. Fundamental understanding of attrition is being addressed by incorporating suitable binders into the catalyst recipe. This has resulted in the preparation of a spray dried HPR-43 catalyst having average particle size (aps) of 70 {micro}m with high attrition resistance. This HPR-43 attrition resistant, active and selective catalyst gave 95% CO conversion through 125 hours of testing in a fixed-bed at 270 C, 1.48 MPa, H{sub 2}/CO=0.67 and 2.0 NL/g-cat/h with C{sub 5+} selectivity of >78% and methane selectivity of less than 5% at an {alpha} of 0.9. Research is proposed to enable further development and optimization of these catalysts by (1) better understanding the role and interrelationship of various catalyst composition and preparation parameters on attrition resistance, activity, and selectivity of these catalysts, (2) the presence of sulfide ions on a precipitated iron catalyst, and (3) the effect of water on sulfided iron F-T catalysts for its activity, selectivity, and attrition. Catalyst preparations will be based on spray drying. The research employed, among other measurements, attrition testing and F-T synthesis at high pressure. Catalyst activity and selectivity is evaluated using a small fixed-bed reactor and a continuous stirred tank reactor (CSTR). The catalysts were prepared by co-precipitation, followed by binder addition and spray drying at 250 C in a 1-m-diameter, 2-m-tall spray dryer. The binder silica content was varied from 0 to 20 wt%. The results show that the use of small amounts of precipitated SiO{sub 2} alone in spray-dried Fe catalysts can result in good attrition resistance. All catalysts investigated with SiO2 wt% {le} 12 produced fines less than 10 wt% during the jet cup attrition test, making them suitable for long-term use in a slurry bubble column reactor. Thus, concentration rather than the type of SiO{sub 2} incorporated into catalyst has a more critical impact on catalyst attrition resistance of spray-dried Fe catalysts. Lower amounts of SiO{sub 2} added to a catalyst give higher particle densities and therefore higher attrition resistances. In order to produce a suitable SBCR catalyst, however, the amount of SiO{sub 2} added has to be optimized to provide adequate surface area, particle density, and attrition resistance. Two of the catalysts with precipitated and binder silica were tested in Texas A&M University's CSTR (Autoclave Engineers). The two catalysts were also tested at The Center for Applied Energy Research in Lexington, Kentucky of the University of Kentucky. Spray-dried catalysts with compositions 100 Fe/5 Cu/4.2 K/11 (P) SiO{sub 2} and 100 Fe/5 Cu/4.2 K/1.1 (B) SiO{sub 2} have excellent selectivity characteristics (low methane and high C{sub 5+} yields), but their productivity and stability (deactivation rate) need to be improved. Mechanical integrity (attrition strength) of these two catalysts was markedly dependent upon their morphological features. The attrition strength of the catalyst made out of largely spherical particles (1.1 (B) SiO{sub 2}) was considerably higher than that of the catalyst consisting of irregularly shaped particles (11 (P) SiO{sub 2}).« less
Reactor for tracking catalyst nanoparticles in liquid at high temperature under a high-pressure gas phase with X-ray absorption spectroscopy.

PubMed

Nguyen, Luan; Tao, Franklin Feng

2018-02-01

Structure of catalyst nanoparticles dispersed in liquid phase at high temperature under gas phase of reactant(s) at higher pressure (≥5 bars) is important for fundamental understanding of catalytic reactions performed on these catalyst nanoparticles. Most structural characterizations of a catalyst performing catalysis in liquid at high temperature under gas phase at high pressure were performed in an ex situ condition in terms of characterizations before or after catalysis since, from technical point of view, access to the catalyst nanoparticles during catalysis in liquid phase at high temperature under high pressure reactant gas is challenging. Here we designed a reactor which allows us to perform structural characterization using X-ray absorption spectroscopy including X-ray absorption near edge structure spectroscopy and extended X-ray absorption fine structure spectroscopy to study catalyst nanoparticles under harsh catalysis conditions in terms of liquid up to 350 °C under gas phase with a pressure up to 50 bars. This reactor remains nanoparticles of a catalyst homogeneously dispersed in liquid during catalysis and X-ray absorption spectroscopy characterization.
Catalytic oxidative desulfurization of liquid hydrocarbon fuels using air

NASA Astrophysics Data System (ADS)

Sundararaman, Ramanathan

Conventional approaches to oxidative desulfurization of liquid hydrocarbons involve use of high-purity, expensive water soluble peroxide for oxidation of sulfur compounds followed by post-treatment for removal of oxidized sulfones by extraction. Both are associated with higher cost due to handling, storage of oxidants and yield loss with extraction and water separation, making the whole process more expensive. This thesis explores an oxidative desulfurization process using air as an oxidant followed by catalytic decomposition of sulfones thereby eliminating the aforementioned issues. Oxidation of sulfur compounds was realized by a two step process in which peroxides were first generated in-situ by catalytic air oxidation, followed by catalytic oxidation of S compounds using the peroxides generated in-situ completing the two step approach. By this technique it was feasible to oxidize over 90% of sulfur compounds present in real jet (520 ppmw S) and diesel (41 ppmw S) fuels. Screening of bulk and supported CuO based catalysts for peroxide generation using model aromatic compound representing diesel fuel showed that bulk CuO catalyst was more effective in producing peroxides with high yield and selectivity. Testing of three real diesel fuels obtained from different sources for air oxidation over bulk CuO catalyst showed different level of effectiveness for generating peroxides in-situ which was consistent with air oxidation of representative model aromatic compounds. Peroxides generated in-situ was then used as an oxidant to oxidize sulfur compounds present in the fuel over MoO3/SiO2 catalyst. 81% selectivity of peroxides for oxidation of sulfur compounds was observed on MoO3/SiO2 catalyst at 40 °C and under similar conditions MoO3/Al2O3 gave only 41% selectivity. This difference in selectivity might be related to the difference in the nature of active sites of MoO3 on SiO2 and Al2O 3 supports as suggested by H2-TPR and XRD analyses. Testing of supported and bulk MgO catalysts for decomposition of sulfones showed that these catalysts are effective in decomposing oxidized sulfur compounds such as dibenzothiophene sulfone and 3-methyl benzothiophene sulfone to biphenyl and isopropyl benzene respectively and SO2. Study of catalyst structure-activity relationship revealed that in the range of 40--140 nm of MgO, crystallite size plays a critical role on activity of the catalyst for sulfone decomposition. In testing other alkali oxides, it was demonstrated that CaO was effective as a reagent in decomposing oxidized sulfur compounds in a crude oil at a much lower temperature than used for MgO based catalyst. Preliminary data on potential regeneration scheme of spent CaO is also discussed.
Influence of physicochemical treatments on iron-based spent catalyst for catalytic oxidation of toluene.

PubMed

Kim, Sang Chai; Shim, Wang Geun

2008-06-15

The catalytic oxidation of toluene was studied over an iron-based spent and regenerated catalysts. Air, hydrogen, or four different acid solutions (oxalic acid (C2H2O4), citric acid (C6H8O7), acetic acid (CH3COOH), and nitric acid (HNO3)) were employed to regenerate the spent catalyst. The properties of pretreated spent catalyst were characterized by the Brunauer Emmett Teller (BET), inductively coupled plasma (ICP), temperature programmed reduction (TPR), and X-ray diffraction (XRD) analyses. The air pretreatment significantly enhanced the catalytic activity of the spent catalyst in the pretreatment temperature range of 200-400 degrees C, but its catalytic activity diminished at the pretreatment temperature of 600 degrees C. The catalytic activity sequence with respect to the air pretreatment temperatures was 400 degrees C>200 degrees C>parent>600 degrees C. The TPR results indicated that the catalytic activity was correlated with both the oxygen mobility and the amount of available oxygen on the catalyst. In contrast, the hydrogen pretreatment had a negative effect on the catalytic activity, and toluene conversion decreased with increasing pretreatment temperatures (200-600 degrees C). The XRD and TPR results confirmed the formation of metallic iron which had a negative effect on the catalytic activity with increasing pretreatment temperature. The acid pretreatment improved the catalytic activity of the spent catalyst. The catalytic activity sequence with respect to different acids pretreatment was found to be oxalic acid>citric acid>acetic acid>or=nitric acid>parent. The TPR results of acid pretreated samples showed an increased amount of available oxygen which gave a positive effect on the catalytic activity. Accordingly, air or acid pretreatments were more promising methods of regenerating the iron-based spent catalyst. In particular, the oxalic acid pretreatment was found to be most effective in the formation of FeC2O4 species which contributed highly to the catalytic combustion of toluene.
Target-directed catalytic metallodrugs

PubMed Central

Joyner, J.C.; Cowan, J.A.

2013-01-01

Most drugs function by binding reversibly to specific biological targets, and therapeutic effects generally require saturation of these targets. One means of decreasing required drug concentrations is incorporation of reactive metal centers that elicit irreversible modification of targets. A common approach has been the design of artificial proteases/nucleases containing metal centers capable of hydrolyzing targeted proteins or nucleic acids. However, these hydrolytic catalysts typically provide relatively low rate constants for target inactivation. Recently, various catalysts were synthesized that use oxidative mechanisms to selectively cleave/inactivate therapeutic targets, including HIV RRE RNA or angiotensin converting enzyme (ACE). These oxidative mechanisms, which typically involve reactive oxygen species (ROS), provide access to comparatively high rate constants for target inactivation. Target-binding affinity, co-reactant selectivity, reduction potential, coordination unsaturation, ROS products (metal-associated vs metal-dissociated; hydroxyl vs superoxide), and multiple-turnover redox chemistry were studied for each catalyst, and these parameters were related to the efficiency, selectivity, and mechanism(s) of inactivation/cleavage of the corresponding target for each catalyst. Important factors for future oxidative catalyst development are 1) positioning of catalyst reduction potential and redox reactivity to match the physiological environment of use, 2) maintenance of catalyst stability by use of chelates with either high denticity or other means of stabilization, such as the square planar geometric stabilization of Ni- and Cu-ATCUN complexes, 3) optimal rate of inactivation of targets relative to the rate of generation of diffusible ROS, 4) targeting and linker domains that afford better control of catalyst orientation, and 5) general bio-availability and drug delivery requirements. PMID:23828584
Ru-assisted synthesis of Pd/Ru nanodendrites with high activity for ethanol electrooxidation.

PubMed

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

2015-08-07

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

PubMed

Wu, Chang-Hsun; Lin, Jyun-Ting; Lin, Kun-Yi Andrew

2018-05-01

Direct carbonization of cobalt complexes represents as a convenient approach to prepare magnetic carbon/cobalt nanocomposites (MCCNs) as heterogeneous environmental catalysts. However, most of MCCNs derived from consist of sheet-like carbon matrices with very sparse cobaltic nanoparticles (NPs), making them exhibit relatively low catalytic activities, porosity and magnetism. In this study, dipicolinic acid (DPA) is selected to prepare a 3-dimensional cobalt coordination polymer (CoDPA). MCCN derived from CoDPA can consist of a porous carbon matrix embedded with highly-dense Co 0 and Co 3 O 4 NPs. This magnetic Co 0 /Co 3 O 4 NP-anchored carbon composite (MCNC) appears as a promising heterogeneous catalyst for oxidative and reductive environmental catalytic reactions. As peroxymonosulfate (PMS) activation is selected as a model catalytic oxidative reaction, MCNC exhibits a much higher catalytic activity than Co 3 O 4 , a benchmark catalyst for PMS activation. The reductive catalytic activity of MCNC is demonstrated through 4-nitrophenol (4-NP) reduction in the presence of NaBH 4 . MCNC could rapidly react with NaBH 4 to generate H 2 for hydrogenation of 4-NP to 4-aminophenol (4-AP). In comparison with other precious metallic catalysts, MCNC also shows a relatively high catalytic activity. These results indicate that MCNC is a conveniently prepared and highly effective and stable carbon-supported cobaltic heterogeneous catalyst for versatile environmental catalytic applications. Copyright © 2018 Elsevier Inc. All rights reserved.
Nafion induced surface confinement of oxygen in carbon-supported oxygen reduction catalysts

DOE PAGES

Chlistunoff, Jerzy; Sansinena, Jose -Maria

2016-11-17

We studied the surface confinement of oxygen inside layers of Nafion self-assembled on carbon-supported oxygen reduction reaction (ORR) catalysts. It is demonstrated that oxygen accumulates in the hydrophobic component of the polymer remaining in contact with the carbon surface. Furthermore, the amount of surface confined oxygen increases with the degree of carbon surface graphitization, which promotes the self-assembly of the polymer. Planar macrocyclic ORR catalysts possessing a delocalized system of π electrons such as Co and Fe porphyrins and phthalocyanines have virtually no effect on the surface confinement of oxygen, in accordance with their structural similarity to graphitic carbon surfacesmore » where they adsorb. Platinum particles in carbon-supported ORR catalysts with high metal contents (20%) disrupt the self-assembly of Nafion and virtually eliminate the oxygen confinement, but the phenomenon is still observed for low Pt loading (4.8%) catalysts.« less
Nafion induced surface confinement of oxygen in carbon-supported oxygen reduction catalysts

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

Chlistunoff, Jerzy; Sansinena, Jose -Maria

We studied the surface confinement of oxygen inside layers of Nafion self-assembled on carbon-supported oxygen reduction reaction (ORR) catalysts. It is demonstrated that oxygen accumulates in the hydrophobic component of the polymer remaining in contact with the carbon surface. Furthermore, the amount of surface confined oxygen increases with the degree of carbon surface graphitization, which promotes the self-assembly of the polymer. Planar macrocyclic ORR catalysts possessing a delocalized system of π electrons such as Co and Fe porphyrins and phthalocyanines have virtually no effect on the surface confinement of oxygen, in accordance with their structural similarity to graphitic carbon surfacesmore » where they adsorb. Platinum particles in carbon-supported ORR catalysts with high metal contents (20%) disrupt the self-assembly of Nafion and virtually eliminate the oxygen confinement, but the phenomenon is still observed for low Pt loading (4.8%) catalysts.« less
Synthesis of 5'-O-DMT-2'-O-TBS Mononucleosides Using an Organic Catalyst.

PubMed

Lee, Sunggi; Blaisdell, Thomas P; Kasaplar, Pinar; Sun, Xixi; Tan, Kian L

2014-06-24

This unit describes a highly effective method to produce 5'-O-DMT-2'-O-TBS mononucleosides selectively using a small organic catalyst. This methodology avoids the tedious protection/deprotection strategy necessary to differentiate the 2'- and 3'-hydroxyl groups in a ribonucleoside. The catalyst was synthesized in two steps, starting from the condensation of valinol and cyclopentyl aldehyde, followed by anionic addition of N-methylimidazole. Ring closure of the amino alcohol with N,N-dimethylformamide dimethyl acetal in methanol furnishes the catalyst. All four 2'-O-TBS protected mono-nucleosides, U, A(Bz), G(Ib), and C(Ac), were produced in a single step using 10 to 20 mol% of the catalyst at room temperature with excellent yields and selectivity. Further transformation to phosphoramidite demonstrates the utility of this protocol in the preparation of monomers useful for automated synthesis of RNA. Copyright © 2014 John Wiley & Sons, Inc.
N, S co-doped carbon spheres with highly dispersed CoO as non-precious metal catalyst for oxygen reduction reaction

NASA Astrophysics Data System (ADS)

Chen, Linlin; Guo, Xingpeng; Zhang, Guoan

2017-08-01

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

PubMed

Wi, Rinbok; Imran, Muhammad; Lee, Kyoung G; Yoon, Sun Hong; Cho, Bong Gyoo; Kim, Do Hyun

2011-07-01

Zinc oxide (ZnO) and cerium oxide (CeO2) nanoparticles were deposited on the surface of preformed silica spheres with diameters ranging from 60 to 750 nm. Ultrasonic irradiation was employed to promote the deposition of the metal oxide nanoparticles on the surface of silica. Silica-supported zinc oxide or cerium oxide was used as a catalyst in the glycolysis of polyethylene terephthalate, one of the key processes in the depolymerization of polyethylene terephthalate. The effect of the support size on the catalytic activity was studied in terms of monomer yield, and the monomer concentration was analyzed via high-performance liquid chromatography (HPLC). The morphologies and surface properties of the catalysts were characterized using a scanning electron microscope, a transmission electron microscope, and a BET surface area analyzer, while the monomer was characterized via HPLC and nuclear-magnetic-resonance spectroscopy. Both the zinc oxide and cerium oxide deposited on a smaller support showed better distribution and less aggregation. The high specific surface area of the smaller support catalysts provided a large number of active sites. The highest monomer yield was obtained with a catalyst of 60-nm silica support.
Heterojunction-Assisted Co3 S4 @Co3 O4 Core-Shell Octahedrons for Supercapacitors and Both Oxygen and Carbon Dioxide Reduction Reactions.

PubMed

Yan, Yibo; Li, Kaixin; Chen, Xiaoping; Yang, Yanhui; Lee, Jong-Min

2017-12-01

Expedition of electron transfer efficiency and optimization of surface reactant adsorption products desorption processes are two main challenges for developing non-noble catalysts in the oxygen reduction reaction (ORR) and CO 2 reduction reaction (CRR). A heterojunction prototype on Co 3 S 4 @Co 3 O 4 core-shell octahedron structure is established via hydrothermal lattice anion exchange protocol to implement the electroreduction of oxygen and carbon dioxide with high performance. The synergistic bifunctional catalyst consists of p-type Co 3 O 4 core and n-type Co 3 S 4 shell, which afford high surface electron density along with high capacitance without sacrificing mechanical robustness. A four electron ORR process, identical to the Pt catalyzed ORR, is validated using the core-shell octahedron catalyst. The synergistic interaction between cobalt sulfide and cobalt oxide bicatalyst reduces the activation energy to convert CO 2 into adsorbed intermediates and hereby enables CRR to run at a low overpotential, with formate as the highly selective main product at a high faraday efficiency of 85.3%. The remarkable performance can be ascribed to the synergistic coupling effect of the structured co-catalysts; heterojunction structure expedites the electron transfer efficiency and optimizes surface reactant adsorption product desorption processes, which also provide theoretical and pragmatic guideline for catalyst development and mechanism explorations. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Encapsulated heterogeneous base catalysts onto SBA-15 nanoporous material as highly active catalysts in the transesterification of sunflower oil to biodiesel

NASA Astrophysics Data System (ADS)

Albayati, Talib M.; Doyle, Aidan M.

2015-02-01

Alkali metals and their hydroxides, Na, NaOH, Li, and LiOH, were encapsulated onto SBA-15 nanoporous material as highly active catalysts for the production of biodiesel fuel from sunflower oil. The incipient wetness impregnation method was adopted for the prepared catalysts. The characterization properties of the catalysts and unmodified SBA-15 were determined using X-ray diffraction, scanning electron microscopy, EDAX, nitrogen adsorption-desorption porosimetry (Brunauer-Emmett-Teller), Fourier-transform infrared spectroscopy, and transmission electron microscopy. Transesterification was conducted in a batch reactor at atmospheric pressure and 65 °C. The catalysts were highly active with yields of fatty acid methyl ester (FAME) in the range 96-99 %. Na/SBA-15 catalyst was reused for seven consecutive cycles under the same reaction conditions; the yield to FAME on the final cycle was 96 %. This study shows that the alkali metals and their hydroxides supported on SBA-15-based catalyst are excellent catalysts for the biodiesel reaction.
Application of a mixed metal oxide catalyst to a metallic substrate

NASA Technical Reports Server (NTRS)

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.
Combustion behaviors and kinetics of sewage sludge blended with pulverized coal: With and without catalysts.

PubMed

Wang, Zhiqiang; Hong, Chen; Xing, Yi; Li, Yifei; Feng, Lihui; Jia, Mengmeng

2018-04-01

The combustion behaviors of sewage sludge (SS), pulverized coal (PC), and their blends were studied using a thermogravimetric analyzer. The effect of the mass ratio of SS to PC on the co-combustion characteristics was analyzed. The experiments showed that the ignition performance of the blends improved significantly as the mass percentage of SS increased, but its combustion intensity decreased. The burnout temperature (T b ) and comprehensive combustibility index (S) of the blends were almost unchanged when the mass percentage of SS was less than 10%. However, a high mass percentage of SS (>10%) resulted in a great increase in T b and a notable decrease in S. Subsequently, the effects of different catalysts (CaO, CeO 2 , MnO 2 , and Fe 2 O 3 ) on the combustion characteristics and activation energy of the SS/PC blend were investigated. The four catalysts promoted the release and combustion of volatile matters in the blended fuels and shifted their combustion profiles to a low temperature. In addition, their peak separating tendencies were obvious at 350-550 C, resulting in high peak widths. All the catalysts improved combustion activity of the blended fuel and accelerated fixed carbon combustion, which decreased the ignition temperature and burnout temperature of the fuels. CeO 2 had the best catalytic effects in terms of the comprehensive combustion performance and activation energy, followed closely by Fe 2 O 3 . However, the rare-earth compounds are expensive to be applied in the catalytic combustion process of SS/PC blend at present. Based on both catalytic effects and economy, Fe 2 O 3 was potentially an optimal option for catalytic combustion among the tested catalysts. Copyright © 2018 Elsevier Ltd. All rights reserved.
Ultrasound assisted transesterification of waste cooking oil using heterogeneous solid catalyst.

PubMed

Pukale, Dipak D; Maddikeri, Ganesh L; Gogate, Parag R; Pandit, Aniruddha B; Pratap, Amit P

2015-01-01

Transesterification based biodiesel production from waste cooking oil in the presence of heterogeneous solid catalyst has been investigated in the present work. The effect of different operating parameters such as type of catalyst, catalyst concentration, oil to methanol molar ratio and the reaction temperature on the progress of the reaction was studied. Some studies related to catalyst reusability have also been performed. The important physicochemical properties of the synthesized biodiesel have also been investigated. The results showed that tri-potassium phosphate exhibits high catalytic activity for the transesterification of waste cooking oil. Under the optimal conditions, viz. catalyst concentration of 3wt% K3PO4, oil to methanol molar ratio of 1:6 and temperature of 50°C, 92.0% of biodiesel yield was obtained in 90min of reaction time. Higher yield was obtained in the presence of ultrasound as compared to conventional approach under otherwise similar conditions, which can be attributed to the cavitational effects. Kinetic studies have been carried out to determine the rate constant at different operating temperatures. It was observed that the kinetic rate constant increased with an increase in the temperature and the activation energy was found to be 64.241kJ/mol. Copyright © 2014 Elsevier B.V. All rights reserved.
Thiolate-bridged dinuclear ruthenium and iron complexes as robust and efficient catalysts toward oxidation of molecular dihydrogen in protic solvents.

PubMed

Yuki, Masahiro; Sakata, Ken; Hirao, Yoshifumi; Nonoyama, Nobuaki; Nakajima, Kazunari; Nishibayashi, Yoshiaki

2015-04-01

Thiolate-bridged dinuclear ruthenium and iron complexes are found to work as efficient catalysts toward oxidation of molecular dihydrogen in protic solvents such as water and methanol under ambient reaction conditions. Heterolytic cleavage of the coordinated molecular dihydrogen at the dinuclear complexes and the sequential oxidation of the produced hydride complexes are involved as key steps to promote the present catalytic reaction. The catalytic activity of the dinuclear complexes toward the chemical oxidation of molecular dihydrogen achieves up to 10000 TON (turnover number), and electrooxidation of molecular dihydrogen proceeds quite rapidly. The result of the density functional theory (DFT) calculation on the reaction pathway indicates that a synergistic effect between the two ruthenium atoms plays an important role to realize the catalytic oxidation of molecular dihydrogen efficiently. The present dinuclear ruthenium complex is found to work as an efficient organometallic anode catalyst for the fuel cell. It is noteworthy that the present dinuclear complex worked not only as an effective catalyst toward chemical and electrochemical oxidation of molecular dihydrogen but also as a good anode catalyst for the fuel cell. We consider that the result described in this paper provides useful and valuable information to develop highly efficient and low-cost transition metal complexes as anode catalysts in the fuel cell.
Robust and Porous β-Diketiminate-Functionalized Metal–Organic Frameworks for Earth-Abundant-Metal-Catalyzed C–H Amination and Hydrogenation

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

Thacker, Nathan C.; Lin, Zekai; Zhang, Teng

We have designed a strategy for postsynthesis installation of the β-diketiminate (NacNac) functionality in a metal–organic framework (MOF) of UiO-topology. Metalation of the NacNac-MOF (I) with earth-abundant metal salts afforded the desired MOF-supported NacNac-M complexes (M = Fe, Cu, and Co) with coordination environments established by detailed EXAFS studies. The NacNac-Fe-MOF catalyst, I•Fe(Me), efficiently catalyzed the challenging intramolecular sp 3 C–H amination of a series of alkyl azides to afford α-substituted pyrrolidines. The NacNac-Cu-MOF catalyst, I•Cu(THF), was effective in promoting the intermolecular sp 3 C–H amination of cyclohexene using unprotected anilines to provide access to secondary amines in excellent selectivity.more » Finally, the NacNac-Co-MOF catalyst, I•Co(H), was used to catalyze alkene hydrogenation with turnover numbers (TONs) as high as 700 000. All of the NacNac-M-MOF catalysts were more effective than their analogous homogeneous catalysts and could be recycled and reused without a noticeable decrease in yield. The NacNac-MOFs thus provide a novel platform for engineering recyclable earth-abundant-element-based single-site solid catalysts for many important organic transformations.« less
Monopropellant engine investigation for space shuttle reaction control system, volume 1

NASA Technical Reports Server (NTRS)

1975-01-01

The results are presented of an investigation to determine the capability of a monopropellant hydrazine thruster to meet the requirements specified for the space shuttle reaction control system (RCS). Of those requirements, the major concern was whether the 100,000 seconds life could be achieved at thrust levels within the specified range. Although burn times in excess of 200,000 seconds have been demonstrated at low thrust levels, the corresponding total impulse values have been substantially lower than that required for the space shuttle RCS. Two other areas of concern, involving the catalyst, were: (1) the effects of the relatively high vehicle vibration levels on catalyst attrition and (2) the effect of exposure of the catalyst to air during atmospheric reentry of the vehicle.

Highly dispersed metal catalyst

DOEpatents

Xiao, Xin; West, William L.; Rhodes, William D.

2016-11-08

A supported catalyst having an atomic level single atom structure is provided such that substantially all the catalyst is available for catalytic function. A process of forming a single atom catalyst unto a porous catalyst support is also provided.
DOE Office of Scientific and Technical Information (OSTI.GOV)

Sun, Junming; Baylon, Rebecca A.; Liu, Changjun

The effects of surface acidity on the cascade ethanol-to-isobutene conversion were studied using ZnxZryOz catalysts. The ethanol-to-isobutene reaction was found to be limited by the secondary reaction of the key intermediate, acetone, namely the acetone-to-isobutene reaction. Although the catalysts with coexisting Brønsted acidity could catalyze the rate-limiting acetone-to-isobutene reaction, the presence of Brønsted acidity is also detrimental. First, secondary isobutene isomerization is favored, producing a mixture of butene isomers. Second, undesired polymerization and coke formation prevail, leading to rapid catalyst deactivation. Most importantly, both steady-state and kinetic reaction studies as well as FTIR analysis of adsorbed acetone-d6 and D2O unambiguouslymore » showed that a highly active and selective nature of balanced Lewis acid-base pairs was masked by the coexisting Brønsted acidity in the aldolization and self-deoxygenation of acetone to isobutene. As a result, ZnxZryOz catalysts with only Lewis acid-base pairs were discovered, on which nearly a theoretical selectivity to isobutene (~88.9%) was successfully achieved, which has never been reported before. Moreover, the absence of Brønsted acidity in such ZnxZryOz catalysts also eliminates the side isobutene isomerization and undesired polymerization/coke reactions, resulting in the production of high purity isobutene with significantly improved catalyst stability (< 2% activity loss after 200 h time-on-stream). This work not only demonstrates a balanced Lewis acid-base pair for the highly active and selective cascade ethanol-to-isobutene reaction, but also sheds light on the rational design of selective and robust acid-base catalyst for C-C coupling via aldolization reaction.« less
CoMoS2/rGO/C3N4 ternary heterojunctions catalysts with high photocatalytic activity and stability for hydrogen evolution under visible light irradiation

NASA Astrophysics Data System (ADS)

Xu, Xuejun; Si, Zhichun; Liu, Liping; Wang, Zehao; Chen, Ze; Ran, Rui; He, Yonghong; Weng, Duan

2018-03-01

Noble metal free MoS2/g-C3N4 catalyst has attracted intense attentions for visible light photocatalytic hydrogen evolution as a result of its earth abundance, low cost and unique heterojunctions stacked with two dimensional sheets. However, the low charge separation efficiency resulted from the poor conductivity of g-C3N4 and MoS2, and lack of abundant active sites from coordinative unsaturated atoms in MoS2, restricts the photocatalytic hydrogen evolution activity and stability enhancement of MoS2/C3N4 composite catalysts. Herein, CoMoS2/rGO/g-C3N4 catalysts with ternary heterojunctions are prepared by facile solvothermal method, which exhibit high visible light photocatalytic activity and stability for hydrogen evolution. The optimal hydrogen evolution rate of CoMoS2/rGO/g-C3N4 catalysts is 684 μmol g-1 h-1 when the content of CoMoS2 is 2% and the content of rGO is 0.5%. The stability of CoMoS2/rGO/C3N4 catalysts just decrease about 3% after 4 cycling runs for 16 h. The good catalytic performances of catalysts are attributed to the synergistic effect among the g-C3N4 nanosheets, rGO nanosheets and CoMoS2 nanosheets. The high conductivity of rGO nanosheets enhances the electron-hole separation and charge transfer, and Co doping increases the active sites for hydrogen evolution due to the increase of unsaturated atoms in CoMoS2 nanosheets.
The degradation of wheat straw lignin

NASA Astrophysics Data System (ADS)

Liang, Jiaqi

2017-03-01

Lignin is a kind of formed by polymerization of aromatic alcohol, prices are lower and sources of renewable resources. Using lignin as raw material, through the push to resolve together preparation phenolic high value-added fine chemicals alkanes and aromatic hydrocarbons, such as the high grade biofuels, can partly replace fossil fuels as raw material to the production process, biomass resources is an important part of the comprehensive utilization of effective components. In lignin push solve clustering method, catalytic hydrogenolysis can directly to the lignin into liquid fuels, low oxygen content in the use of biofuels shows great potential. In this paper, through the optimization of the reaction time, reaction temperature, catalyst type and solvent type, dosage of catalyst, etc factors, determines the alcoholysis - hydrogen solution two-step degradation of lignin, the optimal process conditions: lignin alcoholysis under 50% methanol and NaOH catalyst in the solution, the lignin in methanol solution and 50% hydrogen solution under the Pd/C catalyst. In this process, the degradation of lignin yield can reach 42%.
Cross-linked lysozyme crystal templated synthesis of Au nanoparticles as high-performance recyclable catalysts.

PubMed

Liang, Miao; Wang, Libing; Liu, Xia; Qi, Wei; Su, Rongxin; Huang, Renliang; Yu, Yanjun; He, Zhimin

2013-06-21

Bio-nanomaterials fabricated using a bioinspired templating technique represent a novel class of composite materials with diverse applications in biomedical, electronic devices, drug delivery, and catalysis. In this study, Au nanoparticles (NPs) are synthesized within the solvent channels of cross-linked lysozyme crystals (CLLCs) in situ without the introduction of extra chemical reagents or physical treatments. The as-prepared AuNPs-in-protein crystal hybrid materials are characterized by light microscopy, transmission electron microscopy, x-ray diffraction, and Fourier-transform infrared spectroscopy analyses. Small AuNPs with narrow size distribution reveal the restriction effects of the porous structure in the lysozyme crystals. These composite materials are proven to be active heterogeneous catalysts for the reduction of 4-nitrophenol to 4-aminophenol. These catalysts can be easily recovered and reused at least 20 times because of the physical stability and macro-dimension of CLLCs. This work is the first to use CLLCs as a solid biotemplate for the preparation of recyclable high-performance catalysts.
Cross-linked lysozyme crystal templated synthesis of Au nanoparticles as high-performance recyclable catalysts

NASA Astrophysics Data System (ADS)

Liang, Miao; Wang, Libing; Liu, Xia; Qi, Wei; Su, Rongxin; Huang, Renliang; Yu, Yanjun; He, Zhimin

2013-06-01

Bio-nanomaterials fabricated using a bioinspired templating technique represent a novel class of composite materials with diverse applications in biomedical, electronic devices, drug delivery, and catalysis. In this study, Au nanoparticles (NPs) are synthesized within the solvent channels of cross-linked lysozyme crystals (CLLCs) in situ without the introduction of extra chemical reagents or physical treatments. The as-prepared AuNPs-in-protein crystal hybrid materials are characterized by light microscopy, transmission electron microscopy, x-ray diffraction, and Fourier-transform infrared spectroscopy analyses. Small AuNPs with narrow size distribution reveal the restriction effects of the porous structure in the lysozyme crystals. These composite materials are proven to be active heterogeneous catalysts for the reduction of 4-nitrophenol to 4-aminophenol. These catalysts can be easily recovered and reused at least 20 times because of the physical stability and macro-dimension of CLLCs. This work is the first to use CLLCs as a solid biotemplate for the preparation of recyclable high-performance catalysts.
Recent progress in the development of solid catalysts for biomass conversion into high value-added chemicals

PubMed Central

Hara, Michikazu; Nakajima, Kiyotaka; Kamata, Keigo

2015-01-01

In recent decades, the substitution of non-renewable fossil resources by renewable biomass as a sustainable feedstock has been extensively investigated for the manufacture of high value-added products such as biofuels, commodity chemicals, and new bio-based materials such as bioplastics. Numerous solid catalyst systems for the effective conversion of biomass feedstocks into value-added chemicals and fuels have been developed. Solid catalysts are classified into four main groups with respect to their structures and substrate activation properties: (a) micro- and mesoporous materials, (b) metal oxides, (c) supported metal catalysts, and (d) sulfonated polymers. This review article focuses on the activation of substrates and/or reagents on the basis of groups (a)–(d), and the corresponding reaction mechanisms. In addition, recent progress in chemocatalytic processes for the production of five industrially important products (5-hydroxymethylfurfural, lactic acid, glyceraldehyde, 1,3-dihydroxyacetone, and furan-2,5-dicarboxylic acid) as bio-based plastic monomers and their intermediates is comprehensively summarized. PMID:27877800
Surface Characterization of Mesoporous CoOx/SBA-15 Catalyst upon 1,2-Dichloropropane Oxidation.

PubMed

Finocchio, Elisabetta; Gonzalez-Prior, Jonatan; Gutierrez-Ortiz, Jose Ignacio; Lopez-Fonseca, Ruben; Busca, Guido; de Rivas, Beatriz

2018-05-29

The active combustion catalyst that is based on 30 wt % cobalt oxide on mesoporous SBA-15 has been tested in 1,2-dichloropropane oxidation and is characterized by means of FT-IR (Fourier transform infrared spectroscopy) and ammonia-TPD (temperature-programmed desorption). In this work, we report the spectroscopic evidence for the role of surface acidity in chloroalkane conversion. Both Lewis acidity and weakly acidic silanol groups from SBA support are involved in the adsorption and initial conversion steps. Moreover, total oxidation reaction results in the formation of new Bronsted acidic sites, which are likely associated with the generation of HCl at high temperature and its adsorption at the catalyst surface. Highly dispersed Co oxide on the mesoporous support and Co-chloride or oxychloride particles, together with the presence of several families of acidic sites originated from the conditioning effect of reaction products may explain the good activity of this catalyst in the oxidation of Chlorinated Volatile Organic Compounds.
Recent progress in the development of solid catalysts for biomass conversion into high value-added chemicals.

PubMed

Hara, Michikazu; Nakajima, Kiyotaka; Kamata, Keigo

2015-06-01

In recent decades, the substitution of non-renewable fossil resources by renewable biomass as a sustainable feedstock has been extensively investigated for the manufacture of high value-added products such as biofuels, commodity chemicals, and new bio-based materials such as bioplastics. Numerous solid catalyst systems for the effective conversion of biomass feedstocks into value-added chemicals and fuels have been developed. Solid catalysts are classified into four main groups with respect to their structures and substrate activation properties: (a) micro- and mesoporous materials, (b) metal oxides, (c) supported metal catalysts, and (d) sulfonated polymers. This review article focuses on the activation of substrates and/or reagents on the basis of groups (a)-(d), and the corresponding reaction mechanisms. In addition, recent progress in chemocatalytic processes for the production of five industrially important products (5-hydroxymethylfurfural, lactic acid, glyceraldehyde, 1,3-dihydroxyacetone, and furan-2,5-dicarboxylic acid) as bio-based plastic monomers and their intermediates is comprehensively summarized.
Recent progress in the development of solid catalysts for biomass conversion into high value-added chemicals

NASA Astrophysics Data System (ADS)

Hara, Michikazu; Nakajima, Kiyotaka; Kamata, Keigo

2015-06-01

In recent decades, the substitution of non-renewable fossil resources by renewable biomass as a sustainable feedstock has been extensively investigated for the manufacture of high value-added products such as biofuels, commodity chemicals, and new bio-based materials such as bioplastics. Numerous solid catalyst systems for the effective conversion of biomass feedstocks into value-added chemicals and fuels have been developed. Solid catalysts are classified into four main groups with respect to their structures and substrate activation properties: (a) micro- and mesoporous materials, (b) metal oxides, (c) supported metal catalysts, and (d) sulfonated polymers. This review article focuses on the activation of substrates and/or reagents on the basis of groups (a)-(d), and the corresponding reaction mechanisms. In addition, recent progress in chemocatalytic processes for the production of five industrially important products (5-hydroxymethylfurfural, lactic acid, glyceraldehyde, 1,3-dihydroxyacetone, and furan-2,5-dicarboxylic acid) as bio-based plastic monomers and their intermediates is comprehensively summarized.
Re-examination of the Pt Particle Size Effect on the Oxygen Reduction Reaction for Ultrathin Uniform Pt/C Catalyst Layers without Influence from Nafion

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

Shinozaki, Kazuma; Morimoto, Yu; Pivovar, Bryan S.

The platinum 'particle size effect' on the oxygen reduction reaction (ORR) has been re-evaluated using commercial Pt/C catalysts (2-10 nm Pt particle) and polycrystalline Pt (poly-Pt) in 0.1 M HClO4 with a rotating disk electrode method. Nafion-free catalyst layers were employed to obtain specific activities (SA) that were not perturbed (suppressed) by sulfonate anion adsorption/blocking. By using ultrathin uniform catalyst layers, O2 diffusion limitation was minimized as confirmed from the high SAs of our supported catalysts that were comparable to unsupported sputtered Pt having controlled sizes. The specific activity (SA) steeply increased for the particle sizes in the range -2-10more » nm (0.8-1.8 mA/cm2Pt at 0.9 V vs. RHE) and plateaued over -10 nm to 2.7 mA/cm2Pt for bulk poly-Pt. On the basis of the activity trend for the range of particle sizes studied, it appears that the effect of carbon support on activity is negligible. The experimental results and the concomitant profile of SA vs. particle size was found to be in an agreement to a truncated octahedral particle model that assumes active terrace sites.« less
Interfaces in Heterogeneous Catalysts: Advancing Mechanistic Understanding through Atomic-Scale Measurements.

PubMed

Gao, Wenpei; Hood, Zachary D; Chi, Miaofang

2017-04-18

Developing novel catalysts with high efficiency and selectivity is critical for enabling future clean energy conversion technologies. Interfaces in catalyst systems have long been considered the most critical factor in controlling catalytic reaction mechanisms. Interfaces include not only the catalyst surface but also interfaces within catalyst particles and those formed by constructing heterogeneous catalysts. The atomic and electronic structures of catalytic surfaces govern the kinetics of binding and release of reactant molecules from surface atoms. Interfaces within catalysts are introduced to enhance the intrinsic activity and stability of the catalyst by tuning the surface atomic and chemical structures. Examples include interfaces between the core and shell, twin or domain boundaries, or phase boundaries within single catalyst particles. In supported catalyst nanoparticles (NPs), the interface between the metallic NP and support serves as a critical tuning factor for enhancing catalytic activity. Surface electronic structure can be indirectly tuned and catalytically active sites can be increased through the use of supporting oxides. Tuning interfaces in catalyst systems has been identified as an important strategy in the design of novel catalysts. However, the governing principle of how interfaces contribute to catalyst behavior, especially in terms of interactions with intermediates and their stability during electrochemical operation, are largely unknown. This is mainly due to the evolving nature of such interfaces. Small changes in the structural and chemical configuration of these interfaces may result in altering the catalytic performance. These interfacial arrangements evolve continuously during synthesis, processing, use, and even static operation. A technique that can probe the local atomic and electronic interfacial structures with high precision while monitoring the dynamic interfacial behavior in situ is essential for elucidating the role of interfaces and providing deeper insight for fine-tuning and optimizing catalyst properties. Scanning transmission electron microscopy (STEM) has long been a primary characterization technique used for studying nanomaterials because of its exceptional imaging resolution and simultaneous chemical analysis. Over the past decade, advances in STEM, that is, the commercialization of both aberration correctors and monochromators, have significantly improved the spatial and energy resolution. Imaging atomic structures with subangstrom resolution and identifying chemical species with single-atom sensitivity are now routine for STEM. These advancements have greatly benefitted catalytic research. For example, the roles of lattice strain and surface elemental distribution and their effect on catalytic stability and reactivity have been well documented in bimetallic catalysts. In addition, three-dimensional atomic structures revealed by STEM tomography have been integrated in theoretical modeling for predictive catalyst NP design. Recent developments in stable electronic and mechanical devices have opened opportunities to monitor the evolution of catalysts in operando under synthesis and reaction conditions; high-speed direct electron detectors have achieved sub-millisecond time resolutions and allow for rapid structural and chemical changes to be captured. Investigations of catalysts using these latest microscopy techniques have provided new insights into atomic-level catalytic mechanisms. Further integration of new microscopy methods is expected to provide multidimensional descriptions of interfaces under relevant synthesis and reaction conditions. In this Account, we discuss recent insights on understanding catalyst activity, selectivity, and stability using advanced STEM techniques, with an emphasis on how critical interfaces dictate the performance of precious metal-based heterogeneous catalysts. The role of extended interfacial structures, including those between core and shell, between separate phases and twinned grains, between the catalyst surface and gas, and between metal and support are discussed. We also provide an outlook on how emerging electron microscopy techniques, such as vibrational spectroscopy and electron ptychography, will impact future catalysis research.
High-temperature catalyst for catalytic combustion and decomposition

NASA Technical Reports Server (NTRS)

Mays, Jeffrey A. (Inventor); Lohner, Kevin A. (Inventor); Sevener, Kathleen M. (Inventor); Jensen, Jeff J. (Inventor)

2005-01-01

A robust, high temperature mixed metal oxide catalyst for propellant composition, including high concentration hydrogen peroxide, and catalytic combustion, including methane air mixtures. The uses include target, space, and on-orbit propulsion systems and low-emission terrestrial power and gas generation. The catalyst system requires no special preheat apparatus or special sequencing to meet start-up requirements, enabling a fast overall response time. Start-up transients of less than 1 second have been demonstrated with catalyst bed and propellant temperatures as low as 50 degrees Fahrenheit. The catalyst system has consistently demonstrated high decomposition effeciency, extremely low decomposition roughness, and long operating life on multiple test particles.
A systematic study on photocatalysis of antipyrine: Catalyst characterization, parameter optimization, reaction mechanism a toxicity evolution to plankton.

PubMed

Gong, Han; Chu, Wei; Chen, Meijuan; Wang, Qinxing

2017-04-01

The toxicity of antipyrine (AP) in the photodegradation using UV/CoFe 2 O 4 /TiO 2 was investigated by analyzing the characteristic of the catalyst, the effect of parameters (light source wavelength, catalyst dose, pH and initial AP concentration), the reaction mechanism (the organic intermediates, TOC reduction and inorganic ions release) and the newly proposed low-dosage-high-effective radical reaction approach. The catalyst shows the optimal removal efficiency under the conditions of wavelength at 350 nm, the catalyst dose at 0.5 g/L, and pH value at 5.5. Ten organic intermediates were identified, and five of them were newly reported in AP treatment process. Hydroxylation, demethylation and the cleavage of the pentacyclic ring were included in the decomposition pathways. The ring opening was certified by the 45% TOC reduction and 60% ammonia release during the process. The parent compound AP and its degradation products show positive effects on the growth of the algae. However, acute toxicity of AP was detected on brine shrimps Artemia salina. The toxicity was eliminated gradually with the decomposition of AP and the generation of the byproducts. The results indicate that the photocatalysis process is effective in AP removal, TOC reduction and toxicity elimination. Copyright © 2017 Elsevier Ltd. All rights reserved.
Visible-Light-Responsive Catalysts Using Quantum Dot-Modified TiO2 for Air and Water Purification

NASA Technical Reports Server (NTRS)

Coutts, Janelle L.; Hintze, Paul E.; Clausen, Christian; Richards, Jeffrey Todd

2014-01-01

Photocatalysis, the oxidation or reduction of contaminants by light-activated catalysts, utilizing titanium dioxide (TiO2) as the catalytic substrate has been widely studied for trace contaminant control in both air and water applications. The interest in this process is due primarily to its low energy consumption and capacity for catalyst regeneration. Titanium dioxide requires ultraviolet light for activation due to its relatively large band gap energy of 3.2 eV. Traditionally, Hg-vapor fluorescent light sources are used in PCO reactors; however, the use of mercury precludes the use of this PCO technology in a spaceflight environment due to concerns over crew Hg exposure. The development of a visible-light responsive (VLR) TiO2-based catalyst would eliminate the concerns over mercury contamination. Further, VLR development would allow for the use of ambient visible solar radiation or highly efficient LEDs, both of which would make PCO approaches more efficient, flexible, economical, and safe. Though VLR catalyst development has been an active area of research for the past two decades, there are few commercially available VLR catalysts. Those VLR catalysts that are commercially available do not have adequate catalytic activity, in the visible region, to make them competitive with those operating under UV irradiation. This study was initiated to develop more effective VLR catalysts through a novel method in which quantum dots (QD) consisting of narrow band gap semiconductors (e.g., CdS, CdSe, PbS, ZnSe, etc.) are coupled to TiO2 via two preparation methods: 1) photodeposition and 2) mechanical alloying using a high-speed ball mill. A library of catalysts was developed and screened for gas and aqueous phase applications using ethanol and 4-chlorophenol as the target contaminants, respectively. Both target compounds are well studied in photocatalytic systems and served as model contaminants for this research. Synthesized catalysts were compared in terms of preparation method, nature of the quantum dots, and dosage of quantum dots.
Facile and Low-cost Synthesis of Mesoporous Ti-Mo Bi-metal Oxide Catalysts for Biodiesel Production from Esterification of Free Fatty Acids in Jatropha curcas Crude Oil.

PubMed

Zhang, Qiuyun; Li, Hu; Yang, Song

2018-05-01

Mesoporous Ti-Mo bi-metal oxides with various titanium-molybdenum ratios were successfully fabricated via a facile approach by using stearic acid as a low-cost template agent. thermal gravity (TG) /differential scanning calorimetry (DSC) analysis, X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, nitrogen adsorption-desorption isotherm, NH 3 temperature-programmed desorption (NH 3 -TPD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) measurements indicated these materials possessing mesoporous structure, sufficient pore size and high acid intensity. The catalytic performance of prepared catalysts was evaluated by esterification of free fatty acids in Jatropha curcas crude oil (JCCO) with methanol. The effects of various parameters on FFA conversion were investigated. The esterification conversion of 87.8% was achieved under the condition of 180°C, 2 h, methanol to JCCO molar ratio of 20:1 and 3.0 wt.% catalyst (relative to the weight of JCCO). The mesoporous catalysts were found to exhibit high activities toward the simultaneous esterification and transesterification of JCCO. Furthermore, the catalyst could be recovered with a good reusability.
CO2 hydrogenation to methanol on supported Au catalysts under moderate reaction conditions: support and particle size effects.

PubMed

Hartadi, Yeusy; Widmann, Daniel; Behm, R Jürgen

2015-02-01

The potential of metal oxide supported Au catalysts for the formation of methanol from CO2 and H2 under conditions favorable for decentralized and local conversion, which could be concepts for chemical energy storage, was investigated. Significant differences in the catalytic activity and selectivity of Au/Al2 O3 , Au/TiO2 , AuZnO, and Au/ZrO2 catalysts for methanol formation under moderate reaction conditions at a pressure of 5 bar and temperatures between 220 and 240 °C demonstrate pronounced support effects. A high selectivity (>50 %) for methanol formation was obtained only for Au/ZnO. Furthermore, measurements on Au/ZnO samples with different Au particle sizes reveal distinct Au particle size effects: although the activity increases strongly with the decreasing particle size, the selectivity decreases. The consequences of these findings for the reaction mechanism and for the potential of Au/ZnO catalysts for chemical energy storage and a "green" methanol technology are discussed. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Efficient selective catalytic reduction of NO by novel carbon-doped metal catalysts made from electroplating sludge.

PubMed

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

2014-10-07

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

PubMed

Millán, María; Zamora, Héctor; Rodrigo, Manuel A; Lobato, Justo

2017-02-22

PtCo alloy catalysts for high temperature PEMFCs (protonic exchange membrane fuel cells) were synthesized on a novel noncarbonaceous support (SiCTiC) using the impregnation method with NaBH 4 as the reducing agent at different synthesis temperatures to evaluate the effect of this variable on their physicochemical and electrochemical properties. The catalysts were characterized by inductively coupled plasma optical emission spectrometry, scanning electron microscopy-energy dispersive X-ray spectroscopy, X-ray diffraction, transmission electron microscope-energy dispersive X-ray,and temperature-programmed reduction. In addition, the electrochemical characterization (i.e., cyclic voltammetry, oxygen reduction reaction, and chronoamperometry) was carried out with a rotating disk electrode. For the cyclic voltammetry investigation, 400 cycles were performed in hot phosphoric acid and a half-cell to evaluate the stability of the synthesized catalysts. The catalyst synthesized on SiCTiC exhibited excellent durability compared to the catalyst synthesized on a Vulcan support. In addition, all synthesized catalysts exhibited better catalytic activity than that of the PtCo/C catalysts. The best results were observed for the catalyst synthesized at 80 °C due to its shorter Pt-Pt nearest-neighbor and higher alloy degree. Finally, a preliminary stability test was conducted in an HT-PEMFC, and promising results in terms of stability and performance were observed.
Hydrogen production by aqueous phase reforming of light oxygenated hydrocarbons

NASA Astrophysics Data System (ADS)

Shabaker, John William

Aqueous phase reforming (APR) of renewable oxygenated hydrocarbons (e.g., methanol, ethylene glycol, glycerol, sorbitol, glucose) is a promising new technology for the catalytic production of high-purity hydrogen for fuel cells and chemical processing. Supported Pt catalysts are effective catalysts for stable and rapid H2 production at temperatures near 500 K (H 2 turnover frequencies near 10 min-1). Inexpensive Raney Ni-based catalysts have been developed using a combination of fundamental and high-throughput studies that have similar catalytic properties as Pt-based materials. Promotion of Raney Ni with Sn by controlled surface reaction of organometallic tin compounds is necessary to control formation of thermodynamically-favorable alkane byproducts. Detailed characterization by Mossbauer spectroscopy, electron microscopy, adsorption studies, and x-ray photoelectron spectroscopy (XPS/ESCA) has shown that NiSn alloys are formed during heat treatment, and may be responsible for enhanced stability and selectivity for hydrogen production. Detailed kinetic studies led to the development of a kinetic mechanism for the APR reaction on Pt and NiSn catalysts, in which the oxygenate decomposes through C--H and O--H cleavage, followed by C--C cleavage and water gas shift of the CO intermediate. The rate limiting step on Pt surfaces is the initial dehydrogenation, while C--C cleavage appears rate limiting over NiSn catalysts. Tin promotion of Raney Ni catalysts suppresses C--O bond scission reactions that lead to alkane formation without inhibiting fast C--C and C--H cleavage steps that are necessary for high rates of reforming. A window of operating temperature, pressure, and reactor residence time has been identified for use of the inexpensive NiSn catalysts as a Pt substitute. Concentrated feed stocks and aggressive pretreatments have been found to counteract catalyst deactivation by sintering in the hydrothermal APR environment and allow stable, long-term production of H2 over Raney-NiSn materials.

Steam Reforming of Ethylene Glycol over MgAl₂O₄ Supported Rh, Ni, and Co Catalysts

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

Mei, Donghai; Lebarbier, Vanessa M.; Xing, Rong

Steam reforming of ethylene glycol (EG) over MgAl₂O₄ supported metal (15 wt.% Ni, 5 wt.% Rh, and 15 wt.% Co) catalysts were investigated using combined experimental and theoretical methods. Compared to highly active Rh and Ni catalysts with 100% conversion, the steam reforming activity of EG over the Co catalyst is comparatively lower with only 42% conversion under the same reaction conditions (500°C, 1 atm, 119,000 h⁻¹, S/C=3.3 mol). However, CH₄ selectivity over the Co catalyst is remarkably lower. For example, by varying the gas hour space velocity (GHSV) such that complete conversion is achieved for all the catalysts, CH₄more » selectivity for the Co catalyst is only 8%, which is much lower than the equilibrium CH₄ selectivity of ~ 24% obtained for both the Rh and Ni catalysts. Further studies show that varying H₂O concentration over the Co catalyst has a negligible effect on activity, thus indicating zero-order dependence on H₂O. These experimental results suggest that the supported Co catalyst is a promising EG steam reforming catalyst for high hydrogen production. To gain mechanistic insight for rationalizing the lower CH₃ selectivity observed for the Co catalyst, the initial decomposition reaction steps of ethylene glycol via C-O, O-H, C-H, and C-C bond scissions on the Rh(111), Ni(111) and Co(0001) surfaces were investigated using density functional theory (DFT) calculations. Despite the fact that the bond scission sequence in the EG decomposition on the three metal surfaces varies, which leads to different reaction intermediates, the lower CH₄ selectivity over the Co catalyst, as compared to the Rh and Ni catalysts, is primarily due to the higher barrier for CH₄ formation. The higher S/C ratio enhances the Co catalyst stability, which can be elucidated by the facile water dissociation and an alternative reaction path to remove the CH species as a coking precursor via the HCOH formation. This work was financially supported by the United States Department of Energy (DOE)’s Bioenergy Technologies Office (BETO) and performed at the Pacific Northwest National Laboratory (PNNL). PNNL is a multi-program national laboratory operated for DOE by Battelle Memorial Institute. Computing time and advanced catalyst characterization use was granted by a user proposal at the William R. Wiley Environmental Molecular Sciences Laboratory (EMSL). EMSL is a national scientific user facility sponsored by the Department of Energy’s Office of Biological and Environmental Research and located at PNNL.« less
Visible-light photo-Fenton oxidation of phenol with rGO-α-FeOOH supported on Al-doped mesoporous silica (MCM-41) at neutral pH: Performance and optimization of the catalyst.

PubMed

Wang, Ying; Liang, Mingxing; Fang, Jiasheng; Fu, Jun; Chen, Xiaochun

2017-09-01

In this study, α-FeOOH on reduced graphene oxide (rGO-α-FeOOH) supported on an Al-doped MCM-41 catalyst (RFAM) was optimized for the visible-light photo-Fenton oxidation of phenol at neutral pH. The stability of the catalysts, effect of bubbling aeration, and degradation intermediates were investigated. Results indicated that RFAM with a large Brunauer-Emmett-Teller (BET) area and mesoporous structure displayed excellent catalytic activity for the visible-light-driven (VLD) photo-Fenton process. Phenol degradation was well described by a pseudo-first-order reaction kinetics model. Raman analysis demonstrated that an rGO-α-FeOOH (RF) composite is formed during the ferrous-ion-induced self-assembly process. Al-MCM-41 could uniformly disperse RF nanosheets and promote the mobility and diffusion of matter. The activity of the main catalyst α-FeOOH was enhanced after the incorporation of rGO nanosheets. The α-FeOOH crystal in RFAM showed catalytic activity superior to those of Fe 3 O 4 and Fe 2 O 3 . The RFAM catalyst, with an optimal GO-Fe 2+ mass ratio of 2.33, exhibited a larger BET area, pore size, and pore volume, and thus exhibited high performance and energy utilization efficiency in the VLD photo-Fenton reaction with remarkable stability. Bubbling N 2 inhibited catalytic performance, while bubbling O 2 or air only slightly accelerated the phenol degradation. Visible light played an important role in accelerating the formation of reactive oxygen species (·OH) for the highly efficient phenol degradation. Analysis of degradation intermediates indicated a high phenol mineralization level and the formation of low-molecular-weight organic acids. This work would be helpful in providing an insight into a new type of catalyst assembly and a possible route to a promising heterogeneous catalyst applicable in the visible light photo-Fenton process for effective wastewater remediation at neutral pH. Copyright © 2017. Published by Elsevier Ltd.
[Catalytic combustion of soot on combined oxide catalysts].

PubMed

He, Xu-wen; Yu, Jun-jie; Kang, Shou-fang; Hao, Zheng-ping; Hu, Chun

2005-01-01

Combined oxide catalysts are prepared for catalytic combustion of soot and regeneration from diesel emissions. Thermo-gravimetric analysis(TGA) and temperature programmed oxidation(TPO)are used to evaluate the activity of catalysts under the influence of composition,atomic ration, H2O, calcinations temperature and mass ration between catalysts and soot. Results show that Cu-Mo-O had high activity among double metal oxide catalysts. Among multicomponent metal oxide catalysts, Cu-K-Mo-O had high activity when atomic ratio Cu: K: Mo = 1:1:2 and mass ration between catalysts and soot equals 5: 1. Under this condition, soot ignition temperature of Cu-K-Mo-O catalyst was 327 degrees C. H2O addition and calcinations temperature had little influence on it,which is one kind of compatible catalyst for soot control and catalytic regeneration from diesel emissions.
Study on Endurance and Performance of Impregnated Ruthenium Catalyst for Thruster System.

PubMed

Kim, Jincheol; Kim, Taegyu

2018-02-01

Performance and endurance of the Ru catalyst were studied for nitrous oxide monopropellant thruster system. The thermal decomposition of N2O requires a considerably high temperature, which make it difficult to be utilized as a thruster propellant, while the propellant decomposition temperature can be reduced by using the catalyst through the decomposition reaction with the propellant. However, the catalyst used for the thruster was frequently exposed to high temperature and high-pressure environment. Therefore, the state change of the catalyst according to the thruster operation was analyzed. Characterization of catalyst used in the operation condition of the thruster was performed using FE-SEM and EDS. As a result, performance degradation was occurred due to the volatilization of Ru catalyst and reduction of the specific surface area according to the phase change of Al2O3.
Cooperative catalysis for the direct hydrodeoxygenation of vegetable oils into diesel-range alkanes over Pd/NbOPO4.

PubMed

Xia, Qineng; Zhuang, Xiaojing; Li, Molly Meng-Jung; Peng, Yung-Kang; Liu, Guoliang; Wu, Tai-Sing; Soo, Yun-Liang; Gong, Xue-Qing; Wang, Yanqin; Tsang, Shik Chi Edman

2016-04-14

Near quantitative carbon yields of diesel-range alkanes were achieved from the hydrodeoxygenation of triglycerides over Pd/NbOPO4 under mild conditions with no catalyst deactivation: catalyst characterization and theoretical calculations suggest that the high hydrodeoxygenation activity originated from the synergistic effect of Pd and strong Lewis acidity on the unique structure of NbOPO4.
Selective hydrogenation of amides to alcohols in water solvent over a heterogeneous CeO2-supported Ru catalyst.

PubMed

Tamura, Masazumi; Ishikawa, Susumu; Betchaku, Mii; Nakagawa, Yoshinao; Tomishige, Keiichi

2018-06-20

CeO2-supported Ru (Ru/CeO2) worked as an effective and reusable heterogeneous catalyst for the selective dissociation of the C-N bond in amides, particularly primary amides, with H2 in water solvent at low reaction temperature of 333 K, and high yields of the corresponding alcohols were obtained from primary amides.
Study on the NO removal efficiency of the lignite pyrolysis coke catalyst by selective catalytic oxidation method

PubMed Central

Wen, Xin; Ma, Zhenhua; Zhang, Lei; Sha, Xiangling; He, Huibin; Zeng, Tianyou; Wang, Yusu; Chen, Jihao

2017-01-01

Selective catalytic oxidation (SCO) method is commonly used in wet denitration technology; NO after the catalytic oxidation can be removed with SO2 together by wet method. Among the SCO denitration catalysts, pyrolysis coke is favored by the advantages of low cost and high catalytic activity. In this paper, SCO method combined with pyrolysis coke catalyst was used to remove NO from flue gas. The effects of different SCO operating conditions and different pyrolysis coke catalyst made under different process conditions were studied. Besides, the specific surface area of the catalyst and functional groups were analyzed with surface area analyzer and Beohm titration. The results are: (1) The optimum operating conditions of SCO is as follows: the reaction temperature is 150°C and the oxygen content is 6%. (2) The optimum pyrolysis coke catalyst preparation processes are as follows: the pyrolysis final temperature is 750°C, and the heating rate is 44°C / min. (3) The characterization analysis can be obtained: In the denitration reaction, the basic functional groups and the phenolic hydroxyl groups of the catalyst play a major role while the specific surface area not. PMID:28793346
Catalytic oxidation of low-concentration CO at ambient temperature over supported Pd-Cu catalysts.

PubMed

Wang, Fagen; Zhang, Haojie; He, Dannong

2014-01-01

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

NASA Astrophysics Data System (ADS)

Husin, H.; Asnawi, T. M.; Firdaus, A.; Husaini, H.; Ibrahim, I.; Hasfita, F.

2018-05-01

Solid nanocatalyst derived from oil-palm empty fruit bunches (OP-EFB) fiber was successfully synthesized and its application for biodiesel production was investigated. The OPEFB was treated by burning, milling and heating methods to generate ashes in a nanoparticle size. The nanoparticle palm-bunch ash was characterized by scanning electron microscopy (SEM) and x-ray diffraction (XRD). The effects of the calcination temperature and catalyst amounts for transesterification reactions were investigated. XRD analysis of palm bunch ash exhibited that the highest composition of peaks characteristic were potassium oxide (K2O). SEM analysis showed that the nano palm bunch ash have a particle size ranging of 150-400 nm. The highest conversion of palm-oil to biodiesel reach to 97.90% was observed by using of palm bunch ash nanocatalyst which heated at 600°C, 3 h reaction time and 1% catalyst amount. Reusability of palm bunch ash catalysts was also examined. It was found that of its high active sites, reusable solid catalyst was obtained by just heating of palm bunch ash. It has a capability to reduce not only the amount of catalyst consumption but also reduce the reaction time of transesterification process.
TiO2@TDI@DMAPA: an amine-modified nanoparticle, tailored to act as an economic basic heterogeneous nanocatalyst

NASA Astrophysics Data System (ADS)

Esfahanian, Farzane; Amoozadeh, Ali; Bitaraf, Mehrnoosh

2018-06-01

This study has represented an easy and inexpensive method for the synthesis of a new basic nanocatalyst. In this regard, 3-dimethylaminopropylamine (DMAPA), an economic, industrial, and readily obtainable basic compound, has been grafted onto nano-titania particles by the use of 2,4-toluene diisocyanate (TDI) as a bi-functional, inexpensive, and highly reactive linker. The prepared catalyst has been characterized using the spectroscopic FT-IR method, XRD, FE-SEM, EDX, and back titration. Furthermore, it was identified as an effective catalyst in the preparation of DHPM derivatives and pyranopyrazoles which results in high purity and high yields of products. Response surface methodology (RSM) based on a central composite design (CCD) was employed to reach the optimal conditions. The catalyst can be readily separated and recycled up to six times. [Figure not available: see fulltext.
Promoting Ethylene Selectivity from CO2 Electroreduction on CuO Supported onto CO2 Capture Materials.

PubMed

Yang, Hui-Juan; Yang, Hong; Hong, Yu-Hao; Zhang, Peng-Yang; Wang, Tao; Chen, Li-Na; Zhang, Feng-Yang; Wu, Qi-Hui; Tian, Na; Zhou, Zhi-You; Sun, Shi-Gang

2018-03-09

Cu is a unique catalyst for CO 2 electroreduction, since it can catalyze CO 2 reduction to a series of hydrocarbons, alcohols, and carboxylic acids. Nevertheless, such Cu catalysts suffer from poor selectivity. High pressure of CO 2 is considered to facilitate the activity and selectivity of CO 2 reduction. Herein, a new strategy is presented for CO 2 reduction with improved C 2 H 4 selectivity on a Cu catalyst by using CO 2 capture materials as the support at ambient pressure. N-doped carbon (N x C) was synthesized through high-temperature carbonization of melamine and l-lysine. We observed that the CO 2 uptake capacity of N x C depends on both the microporous area and the content of pyridinic N species, which can be controlled by the carbonization temperature (600-800 °C). The as-prepared CuO/N x C catalysts exhibit a considerably higher C 2 H 4 faradaic efficiency (36 %) than CuO supported on XC-72 carbon black (19 %), or unsupported CuO (20 %). Moreover, there is a good linear relationship between the C 2 H 4 faradaic efficiency and CO 2 uptake capacity of the supports for CuO. The local high CO 2 concentration near Cu catalysts, created by CO 2 capture materials, was proposed to increase the coverage of CO intermediate, which is favorable for the coupling of two CO units in the formation of C 2 H 4 . This study demonstrates that pairing Cu catalysts with CO 2 capture supports is a promising approach for designing highly effective CO 2 reduction electrocatalysts. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
Free-standing ternary NiWP film for efficient water oxidation reaction

NASA Astrophysics Data System (ADS)

Yang, Yunpeng; Zhou, Kuo; Ma, Lili; Liang, Yanqin; Yang, Xianjin; Cui, Zhenduo; Zhu, Shengli; Li, Zhaoyang

2018-03-01

High-efficient catalysts for oxygen evolution reaction (OER) is of great concern in improving energy efficiency for water splitting. Here we report a high-performance OER electrocatalyst of nickel-tungsten-phosphorus (NiWP) film prepared by template method. This free-standing ternary electrocatalyst exhibits a remarkable electrocatalytic activity of OER in alkaline medium due to the synergetic effect among these elements and the good electrical conductivity. The reported NiWP composite catalyst has an overpotential of as low as 0.4 V (vs. RHE) at 30 mA cm-2, better than that of the commercial RuO2 catalyst. Moreover, a small charge transfer resistance of 4.06 Ω and a Tafel slope of 68 mV dec-1 demonstrate the outstanding catalytic activity.
Selective One-Pot Production of High-Grade Diesel-Range Alkanes from Furfural and 2-Methylfuran over Pd/NbOPO4.

PubMed

Xia, Qineng; Xia, Yinjiang; Xi, Jinxu; Liu, Xiaohui; Zhang, Yongguang; Guo, Yong; Wang, Yanqin

2017-02-22

A one-pot method for the selective production of high-grade diesel-range alkanes from biomass-derived furfural and 2-methylfuran (2-MF) was developed by combining the hydroxyalkylation/alkylation (HAA) condensation of furfural with 2-MF and the subsequent hydrodeoxygenation (HDO) over a multifunctional Pd/NbOPO 4 catalyst. The effects of various reaction conditions as well as a variety of solid-acid catalysts and metal-loaded NbOPO 4 catalysts were systematically investigated to optimize the reaction conditions for both reactions. Under the optimal reaction conditions up to 89.1 % total yield of diesel-range alkanes was obtained from furfural and 2-MF by this one-pot method. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
DEHYDROGENATION CATALYST FOR PRODUCTION OF MTBE

EPA Science Inventory

The objectives of this project were to better understand the effect of different catalyst preparation parameters, the effect of different catalyst treatment parameters, and the mechanism of deactivation. Accordingly, catalysts were made using various preparation methods and with...
Biofuel Production from Jatropha Bio-Oil Derived Fast Pyrolysis: Effect and Mechanism of CoMoS Supported on Al2O3

NASA Astrophysics Data System (ADS)

Rodseanglung, T.; Ratana, T.; Phongaksorn, M.; Tungkamani, S.

2018-03-01

The aims of this research was to understand the CoMo/Al2O3 sulfide catalyst effect to remove oxygen-containing and nitrogen-containing molecules from Jatropha bio-oil derived fast pyrolysis converted to biofuels via hydrotreating process. The activity and selectivity of CoMo/γ-Al2O3 sulfided catalysts in hydrodeoxygenation (HDO) of Jatropha bio-oil derived fast pyrolysis was evaluated in a Parr batch reactor under 50 bar of H2 atmosphere for 2 h at 300 320 and 340 °C. It appeared that the CoMo/Al2O3 sulfide catalyst have high performance in activity for promoting the fatty acid, fatty ester, fatty amide and fatty nitrile compounds were converted to paraffin/olefin (Diesel range), this could be the CUS site on supported Al2O3 catalyst. The difference in selectivity products allowed us to propose a reaction scheme.
Development of Metal-impregnated Single Walled Carbon Nanotubes for Toxic Gas Contaminant Control in Advanced Life Support Systems

NASA Technical Reports Server (NTRS)

Pisharody, Suresh A.; Fisher, John W.; Wignarajah, K.

2002-01-01

The success of physico-chemical waste processing and resource recovery technologies for life support application depends partly on the ability of gas clean-up systems to efficiently remove trace contaminants generated during the process with minimal use of expendables. Carbon nanotubes promise superior performance over conventional approaches to gas clean-up due to their ability to direct the selective uptake of gaseous species based on their controlled pore size, high surface area, ordered chemical structure that allows functionalization and their effectiveness also as catalyst support materials for toxic gas conversion. We present results and findings from a preliminary study on the effectiveness of metal impregnated single walled nanotubes as catalyst/catalyst support materials for toxic gas contaminate control. The study included the purification of single walled nanotubes, the catalyst impregnation of the purified nanotubes, the experimental characterization of the surface properties of purified single walled nanotubes and the characterization of physisorption and chemisorption of uptake molecules.
Controlling Catalyst Bulk Reservoir Effects for Monolayer Hexagonal Boron Nitride CVD.

PubMed

Caneva, Sabina; Weatherup, Robert S; Bayer, Bernhard C; Blume, Raoul; Cabrero-Vilatela, Andrea; Braeuninger-Weimer, Philipp; Martin, Marie-Blandine; Wang, Ruizhi; Baehtz, Carsten; Schloegl, Robert; Meyer, Jannik C; Hofmann, Stephan

2016-02-10

Highly controlled Fe-catalyzed growth of monolayer hexagonal boron nitride (h-BN) films is demonstrated by the dissolution of nitrogen into the catalyst bulk via NH3 exposure prior to the actual growth step. This "pre-filling" of the catalyst bulk reservoir allows us to control and limit the uptake of B and N species during borazine exposure and thereby to control the incubation time and h-BN growth kinetics while also limiting the contribution of uncontrolled precipitation-driven h-BN growth during cooling. Using in situ X-ray diffraction and in situ X-ray photoelectron spectroscopy combined with systematic growth calibrations, we develop an understanding and framework for engineering the catalyst bulk reservoir to optimize the growth process, which is also relevant to other 2D materials and their heterostructures.
Synthesis, characterization and application of a nano-manganese-catalyst as an efficient solid catalyst for solvent free selective oxidation of ethylbenzene, cyclohexene, and benzylalcohol

NASA Astrophysics Data System (ADS)

Habibi, Davood; Faraji, Ali Reza

2013-07-01

The object of this study is to synthesize the heterogeneous Mn-nano-catalyst (MNC) which has been covalently anchored on a modified nanoscaleSiO2/Al2O3, and characterized by FT-IR, UV-Vis, CHN elemental analysis, EDS, TEM, and EDX. The method is efficient for the highly selective oxidation of ethylbenzene, cyclohexene, and benzylalcohol without the need to any solvents, using tert-butyl hydroperoxide (TBHP) as an oxidant. Oxidation of ethylbenzene, cyclohexene, and benzylalcohol gave acetophenone, 2-cyclohexene-1-one and benzaldehyde, respectively, as major products. Reaction conditions have been optimized by considering the effect of various factors such as reaction time, amounts of substrates and oxidant, Mn-nano-catalyst and application of various solvents.
Ultra-high-performance core–shell structured Ru@Pt/C catalyst prepared by a facile pulse electrochemical deposition method

DOE PAGES

Chen, Dan; Li, Yuexia; Liao, Shijun; ...

2015-08-03

Core–shell structured catalysts, made by placing either a monolayer or a thin layer of a noble metal on relatively cheap core-metal nanoparticles, are fascinating and promising fuel cell catalysts due to their high utilization of noble metals. Here, we report our development of a core–shell structured catalyst, Ru@Pt/C, generated by a novel and facile pulse electrochemical deposition (PED) approach. We demonstrate that compared with a commercial Pt/C catalyst, this novel catalyst achieves over four times higher mass activity towards the anodic oxidation of methanol, and 3.6 times higher mass activity towards the cathodic reduction of oxygen. Importantly, we find thatmore » the intrinsic activity of Pt in this Ru@Pt/C catalyst is doubled due to the formation of the core–shell structure. The catalyst also shows superior stability: even after 2000 scans, it still retains up to 90% of the peak current. As a result, our findings demonstrate that this novel PED approach is a promising method for preparing high-performance core–shell catalysts for fuel cell applications.« less
Highly efficient molybdenum-based catalysts for enantioselective alkene metathesis

PubMed Central

Malcolmson, Steven J.; Meek, Simon J.; Sattely, Elizabeth S.; Schrock, Richard R.; Hoveyda, Amir H.

2009-01-01

Discovery of efficient catalysts is one of the most compelling objectives of modern chemistry. Chiral catalysts are in particularly high demand, as they facilitate synthesis of enantiomerically enriched small molecules that are critical to developments in medicine, biology and materials science1. Especially noteworthy are catalysts that promote—with otherwise inaccessible efficiency and selectivity levels—reactions demonstrated to be of great utility in chemical synthesis. Here we report a class of chiral catalysts that initiate alkene metathesis1 with very high efficiency and enantioselectivity. Such attributes arise from structural fluxionality of the chiral catalysts and the central role that enhanced electronic factors have in the catalytic cycle. The new catalysts have a stereogenic metal centre and carry only monodentate ligands; the molybdenum-based complexes are prepared stereoselectively by a ligand exchange process involving an enantiomerically pure aryloxide, a class of ligands scarcely used in enantioselective catalysis2,3. We demonstrate the application of the new catalysts in an enantioselective synthesis of the Aspidosperma alkaloid, quebrachamine, through an alkene metathesis reaction that cannot be promoted by any of the previously reported chiral catalysts. PMID:19011612

Advantages of MgAlOx over gamma-Al2O3 as a support material for potassium-based high temperature lean NOx traps

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

Luo, Jinyong; Gao, Feng; Karim, Ayman M.

MgAlOx mixed oxides were employed as supports for potassium-based lean NOx traps (LNTs) targeted for high temperature applications. Effects of support compositions, K/Pt loadings, thermal aging and catalyst regeneration on NOx storage capacity were systematically investigated. The catalysts were characterized by XRD, NOx-TPD, TEM, STEM-HAADF and in-situ XAFS. The results indicate that MgAlOx mixed oxides have significant advantages over conventional gamma-Al2O3-supports for LNT catalysts, in terms of high temperature NOx trapping capacity and thermal stability. First, as a basic support, MgAlOx stabilizes stored nitrates (in the form of KNO3) to much higher temperatures than mildly acidic gamma-Al2O3. Second, MgAlOx minimizesmore » Pt sintering during thermal aging, which is not possible for gamma-Al2O3 supports. Notably, combined XRD, in-situ XAFS and STEM-HAADF results indicate that Pt species in the thermally aged Pt/MgAlOx samples are finely dispersed in the oxide matrix as isolated atoms. This strong metal-support interaction stabilizes Pt and minimizes the extent of sintering. However, such strong interactions result in Pt oxidation via coordination with the support so that NO oxidation activity can be adversely affected after aging which, in turn, decreases NOx trapping ability for these catalysts. Interestingly, a high-temperature reduction treatment regenerates essentially full NOx trapping performance. In fact, regenerated Pt/K/MgAlOx catalyst exhibits much better NOx trapping performance than fresh Pt/K/Al2O3 LNTs over the entire temperature range investigated here. In addition to thermal aging, Pt/K loading effects were systemically studied over the fresh samples. The results indicate that NOx trapping is kinetically limited at low temperatures, while thermodynamically limited at high temperatures. A simple conceptual model was developed to explain the Pt and K loading effects on NOx storage. An optimized K loading, which allows balancing between the stability of nitrates and exposed Pt surface, gives the best NOx trapping capability.« less
Choice of precipitant and calcination temperature of precursor for synthesis of NiCo2O4 for control of CO-CH4 emissions from CNG vehicles.

PubMed

Trivedi, Suverna; Prasad, Ram

2018-03-01

Compressed natural gas (CNG) is most appropriate an alternative of conventional fuel for automobiles. However, emissions of carbon-monoxide and methane from such vehicles adversely affect human health and environment. Consequently, to abate emissions from CNG vehicles, development of highly efficient and inexpensive catalysts is necessary. Thus, the present work attempts to scan the effects of precipitants (Na 2 CO 3 , KOH and urea) for nickel cobaltite (NiCo 2 O 4 ) catalysts prepared by co-precipitation from nitrate solutions and calcined in a lean CO-air mixture at 400°C. The catalysts were used for oxidation of a mixture of CO and CH 4 (1:1). The catalysts were characterized by X-ray diffractometer, Brunauer-Emmett-Teller surface-area, X-ray photoelectron spectroscopy; temperature programmed reduction and Scanning electron microscopy coupled with Energy-Dispersive X-Ray Spectroscopy. The Na 2 CO 3 was adjudged as the best precipitant for production of catalyst, which completely oxidized CO-CH 4 mixture at the lowest temperature (T 100 =350°C). Whereas, for catalyst prepared using urea, T 100 =362°C. On the other hand the conversion of CO-CH 4 mixture over the catalyst synthesized by KOH limited to 97% even beyond 400°C. Further, the effect of higher calcination temperatures of 500 and 600°C was examined for the best catalyst. The total oxidation of the mixture was attained at higher temperatures of 375 and 410°C over catalysts calcined at 500 and 600°C respectively. Thus, the best precipitant established was Na 2 CO 3 and the optimum calcination temperature of 400°C was found to synthesize the NiCo 2 O 4 catalyst for the best performance in CO-CH 4 oxidation. Copyright © 2017. Published by Elsevier B.V.
Design and assembly of a catalyst bed gas generator for the catalytic decomposition of high concentration hydrogen peroxide propellants and the catalytic combustion of hydrocarbon/air mixtures

NASA Technical Reports Server (NTRS)

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

2004-01-01

A method for designing and assembling a high performance catalyst bed gas generator for use in decomposing propellants, particularly hydrogen peroxide propellants, for use in target, space, and on-orbit propulsion systems and low-emission terrestrial power and gas generation. The gas generator utilizes a sectioned catalyst bed system, and incorporates a robust, high temperature mixed metal oxide catalyst. The gas generator requires no special preheat apparatus or special sequencing to meet start-up requirements, enabling a fast overall response time. The high performance catalyst bed gas generator system has consistently demonstrated high decomposition efficiency, extremely low decomposition roughness, and long operating life on multiple test articles.
CO2 methanation on the catalyst of Ni/MCM-41 promoted with CeO2.

PubMed

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.
Fe3-xCuxO4 as highly active heterogeneous Fenton-like catalysts toward elemental mercury removal.

PubMed

Zhou, Changsong; Sun, Lushi; Zhang, Anchao; Wu, Xiaofeng; Ma, Chuan; Su, Sheng; Hu, Song; Xiang, Jun

2015-04-01

A series of novel spinel Fe3-xCuxO4 (0
Ambient-temperature NO oxidation over amorphous CrOx-ZrO 2 mixed oxide catalysts: Significant promoting effect of ZrO 2

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

Wang, Aiyong; Guo, Yanglong; Gao, Feng

2017-03-01

Three series of Cr-based mixed oxides (Cr-Co, Cr-Fe, and Cr-Ni oxides) with high specific surface areas and amorphous textures are synthesized using a novel sol-gel method. These mixed oxides, in comparison to their pure metal oxide (CrOx, Co3O4, FeOx and NiO) counterparts, display enhanced performance for catalytic oxidation of low-concentration NO at room temperature. Over best performing catalysts, 100% NO conversion can be maintained up to 30 h of operation at a high space velocity of 45,000 ml g-1 h-1. The amorphous structure is found to be critical for these catalysts to maintain high activity and durability. Cr/M (M=Co, Femore » and Ni) molar ratio, nitrate precursor decomposition temperature and catalyst calcination temperature are important criteria for the synthesis of the highly active catalysts. This work was supported by National Basic Research Program of China (2013CB933200), National Natural Science Foundation of China (21577035, 21577034), Commission of Science and Technology of Shanghai Municipality (15DZ1205305) and 111 Project (B08021). Aiyong Wang gratefully acknowledges the China Scholarship Council for the Joint-Training Scholarship Program with the Pacific Northwest National Laboratory (PNNL). PNNL is operated for the U.S. Department of Energy (DOE) by Battelle. FG and CHFP are supported by the U.S. DOE/Office of Energy Efficiency and Renewable Energy, Vehicle Technologies Office.« less
Flexible 3D Fe@VO2 core-shell mesh: A highly efficient and easy-recycling catalyst for the removal of organic dyes.

PubMed

Li, Jing; Wang, Ruoqi; Su, Zhen; Zhang, Dandan; Li, Heping; Yan, Youwei

2018-10-01

Nowadays, it is extremely urgent to search for efficient and effective catalysts for water purification due to the severe worldwide water-contamination crises. Here, 3D Fe@VO 2 core-shell mesh, a highly efficient catalyst toward removal of organic dyes with excellent recycling ability in the dark is designed and developed for the first time. This novel core-shell structure is actually 304 stainless steel mesh coated by VO 2 , fabricated by an electrophoretic deposition method. In such a core-shell structure, Fe as the core allows much easier separation from the water, endowing the catalyst with a flexible property for easy recycling, while VO 2 as the shell is highly efficient in degradation of organic dyes with the addition of H 2 O 2 . More intriguingly, the 3D Fe@VO 2 core-shell mesh exhibits favorable performance across a wide pH range. The 3D Fe@VO 2 core-shell mesh can decompose organic dyes both in a light-free condition and under visible irradiation. The possible catalytic oxidation mechanism of Fe@VO 2 /H 2 O 2 system is also proposed in this work. Considering its facile fabrication, remarkable catalytic efficiency across a wide pH range, and easy recycling characteristic, the 3D Fe@VO 2 core-shell mesh is a newly developed high-performance catalyst for addressing the universal water crises. Copyright © 2018 Elsevier B.V. All rights reserved.
Hydrophobic and hydrophilic nanosheet catalysts with high catalytic activity and recycling stability through control of the outermost ligand

NASA Astrophysics Data System (ADS)

Ko, Younji; Kim, Donghee; Kwon, Cheong Hoon; Cho, Jinhan

2018-04-01

In this study, we introduce hydrophobic and hydrophilic graphene oxide nanosheet (GON) catalysts prepared by consecutive ligand replacement of hydrophobically stabilized magnetic and catalytic nanoparticles (NPs); it exhibits high catalytic activity, fast magnetic response, and good dispersion in both nonpolar and aqueous media, allowing high loading amount of magnetic and catalytic NPs onto GON sheets. More specifically, these GON catalysts showed a high product yield of 66-99% and notable recyclability (93% of the initial product yield after 10 reaction cycles) in a Suzuki-Miyaura reaction in nonpolar media, outperforming the performance of the conventional hydrophilic GON catalysts. Additional coating of a hydrophilic layer onto GON catalysts also showed the notable performance (product yield ∼99%) in catalytic reactions performed in aqueous media. Given that ligand-controlled catalytic NPs adsorbed onto 2D nanosheets can be used as hydrophobic and hydrophilic stabilizers as well as catalysts, our approach can provide a tool for developing and designing 2D-nanosheet catalysts with high performance in nonpolar and polar media.
Impact of support calcination and competitive adsorbate in Fe/Mo-Al2O3 catalyst for synthesis of carbon nanotubes by V-flame

NASA Astrophysics Data System (ADS)

Sun, Ya-Ping; Sun, Bao-Min; Zhai, Gang; Guo, Yong-Hong; Jia, Xiao-Wei; Kang, Zhi-Zhong

2018-05-01

Carbon nanotubes (CNTs) were synthesized via carbon monoxide decomposition with aid of various Fe/Mo-Al2O3 catalysts by V-type flame method. The influences of support calcination and competitive adsorbates on the morphology and properties of CNTs were studied. SEM, HRTEM, TPO and Raman spectroscopy were applied to investigate the morphology and microstructure of CNT products. XRD, H2-TPR were employed to characterize catalysts. The obtained results indicate that calcinated support can increase production and promote the formation of CNTs with small diameter. Utilizing citric acid as a competitive adsorbate is successful in improving the quality of CNTs. Besides, the addition of citric acid and calcinated support in catalyst enhances the catalytic growth activity. The obtained CNTs have a diameter around 4–6 nm within a narrow diameter distribution range. Raman spectrum analysis also illustrates that highly graphitized CNTs are produced on the catalyst with calcinated support and citric acid. These results suggest that support calcination and competitive adsorbate have pronounced effect on the average diameter, diameter distribution, and graphitization of CNTs, which provides a simple and effective way to tune the properties of CNTs.
Towards Stable CuZnAl Slurry Catalysts for the Synthesis of Ethanol from Syngas

NASA Astrophysics Data System (ADS)

Dong, Weibing; Gao, Zhihua; Zhang, Qian; Huang, Wei

2018-07-01

A stable CuZnAl slurry catalyst for the synthesis of ethanol from syngas has been developed by adjusting the heat treatment conditions of the complete liquid-phase method. The activity evaluation results showed that the CuZnAl catalyst, when heat-treated under a high pressure and temperature, was a stable catalyst for the synthesis of ethanol. The selectivity of ethanol using the CuZnAl slurry catalyst, which was heat-treated at 553 K under 4.0 MPa, increased continuously with time and was stable at approximately 26.00% after 144 h. The characterization results indicated that the CuZnAl slurry catalyst heat-treated under high pressure conditions could facilitate the formation of a more perfect structure with a larger specific surface area. The prepared catalyst contained a balance of strong and weak acid sites, an appropriate form of Cu2O and a high Cu/Zn atomic ratio at the catalyst surface, providing its stability in ethanol synthesis from syngas.
Highly Reactive, General and Long-Lived Catalysts for Palladium-Catalyzed Amination of Heteroaryl and Aryl Chlorides, Bromides and Iodides: Scope and Structure-Activity Relationships

PubMed Central

Shen, Qilong; Ogata, Tokutaro; Hartwig, John F.

2010-01-01

We describe a systematic study of the scope and relationship between ligand structure and activity for a highly efficient and selective class of catalysts for the amination of heteroaryl and aryl chlorides, bromides and iodides containing sterically hindered chelating alkylphosphines. In the presence of this catalyst, aryl and heteroaryl chlorides, bromides and iodides react with many primary amines in high yields with part-per-million quantities of palladium precursor and ligand. Many reactions of primary amines with both heteroaryl and aryl chlorides, bromides and iodides occur to completion with 0.0005-0.05 mol % catalysts. A comparison of the reactivity of this catalyst for coupling of primary amines at these loadings is made with catalysts generated from hindered monophosphines and carbenes, and these data illustrate the benefits of chelation. Thus, these complexes constitute a fourth-generation catalyst for the amination of aryl halides, whose activity complements catalysts based on monophosphines and carbenes. PMID:18444639
Catalytic Oxidation of Chlorobenzene over MnxCe1-xO2/HZSM-5 Catalysts: A Study with Practical Implications.

PubMed

Weng, Xiaole; Sun, Pengfei; Long, Yu; Meng, Qingjie; Wu, Zhongbiao

2017-07-18

Industrial-use catalysts usually encounter severe deactivation after long-term operation for catalytic oxidation of chlorinate volatile organic compounds (CVOCs), which becomes a "bottleneck" for large-scale application of catalytic combustion technology. In this work, typical acidic solid-supported catalysts of Mn x Ce 1-x O 2 /HZSM-5 were investigated for the catalytic oxidation of chlorobenzene (CB). The activation energy (E a ), Brønsted and Lewis acidities, CB adsorption and activation behaviors, long-term stabilities, and surficial accumulation compounds (after aging) were studied using a range of analytical techniques, including XPS, H 2 -TPR, pyridine-IR, DRIFT, and O 2 -TP-Ms. Experimental results revealed that the Brønsted/Lewis (B/L) ratio of Mn x Ce 1-x O 2 /HZSM-5 catalysts could be adjusted by ion exchange of H• (in HZSM-5) with Mn n+ (where the exchange with Ce 4+ did not distinctly affect the acidity); the long-term aged catalysts could accumulate ca. 14 organic compounds at surface, including highly toxic tetrachloromethane, trichloroethylene, tetrachloroethylene, o-dichlorobenzene, etc.; high humid operational environment could ensure a stable performance for Mn x Ce 1-x O 2 /HZSM-5 catalysts; this was due to the effective removal of Cl• and coke accumulations by H 2 O washing, and the distinct increase of Lewis acidity by the interaction of H 2 O with HZSM-5. This work gives an in-depth view into the CB oxidation over acidic solid-supported catalysts and could provide practical guidelines for the rational design of reliable catalysts for industrial applications.
Uniform Pt/Pd Bimetallic Nanocrystals Demonstrate Platinum Effect on Palladium Methane Combustion Activity and Stability

DOE PAGES

Goodman, Emmett D.; Dai, Sheng; Yang, An-Chih; ...

2017-05-18

Bimetallic catalytic materials are in widespread use for numerous reactions, as the properties of a monometallic catalyst are often improved upon addition of a second metal. In studies with bimetallic catalysts, it remains challenging to establish clear structure–property relationships using traditional impregnation techniques, due to the presence of multiple coexisting active phases of different sizes, shapes, and compositions. Here, a convenient approach to prepare small and uniform Pt/Pd bimetallic nanocrystals with tailorable composition is demonstrated, despite the metals being immiscible in the bulk. By depositing this set of controlled nanocrystals onto a high-surface-area alumina support, we systematically investigate the effectmore » of adding platinum to palladium catalysts for methane combustion. At low temperatures and in the absence of steam, all bimetallic catalysts show activity nearly identical with that of Pt/Al 2O 3, with much lower rates in comparison to that of the Pd/Al 2O 3 sample. BUt, unlike Pd/Al 2O 3, which experiences severe low-temperature steam poisoning, all Pt/Pd bimetallic catalysts maintain combustion activity on exposure to excess steam. These features are due to the influence of Pt on the Pd oxidation state, which prevents the formation of a bulk-type PdO phase. Despite lower initial combustion rates, hydrothermal aging of the Pd-rich bimetallic catalyst induces segregation of a PdO phase in close contact to a Pd/Pt alloy phase, forming more active and highly stable sites for methane combustion. Altogether, this work unambiguously clarifies the activity and stability attributes of Pt/Pd phases which often coexist in traditionally synthesized bimetallic catalysts and demonstrates how well-controlled bimetallic catalysts elucidate structure–property relationships.« less
Uniform Pt/Pd Bimetallic Nanocrystals Demonstrate Platinum Effect on Palladium Methane Combustion Activity and Stability

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

Goodman, Emmett D.; Dai, Sheng; Yang, An-Chih

Bimetallic catalytic materials are in widespread use for numerous reactions, as the properties of a monometallic catalyst are often improved upon addition of a second metal. In studies with bimetallic catalysts, it remains challenging to establish clear structure–property relationships using traditional impregnation techniques, due to the presence of multiple coexisting active phases of different sizes, shapes, and compositions. Here, a convenient approach to prepare small and uniform Pt/Pd bimetallic nanocrystals with tailorable composition is demonstrated, despite the metals being immiscible in the bulk. By depositing this set of controlled nanocrystals onto a high-surface-area alumina support, we systematically investigate the effectmore » of adding platinum to palladium catalysts for methane combustion. At low temperatures and in the absence of steam, all bimetallic catalysts show activity nearly identical with that of Pt/Al 2O 3, with much lower rates in comparison to that of the Pd/Al 2O 3 sample. BUt, unlike Pd/Al 2O 3, which experiences severe low-temperature steam poisoning, all Pt/Pd bimetallic catalysts maintain combustion activity on exposure to excess steam. These features are due to the influence of Pt on the Pd oxidation state, which prevents the formation of a bulk-type PdO phase. Despite lower initial combustion rates, hydrothermal aging of the Pd-rich bimetallic catalyst induces segregation of a PdO phase in close contact to a Pd/Pt alloy phase, forming more active and highly stable sites for methane combustion. Altogether, this work unambiguously clarifies the activity and stability attributes of Pt/Pd phases which often coexist in traditionally synthesized bimetallic catalysts and demonstrates how well-controlled bimetallic catalysts elucidate structure–property relationships.« less
A new V-doped Bi2(O,S)3 oxysulfide catalyst for highly efficient catalytic reduction of 2-nitroaniline and organic dyes.

PubMed

Abay, Angaw Kelemework; Kuo, Dong-Hau; Chen, Xiaoyun; Saragih, Albert Daniel

2017-12-01

A new type of convenient, and environmentally friendly, Vanadium (V)-doped Bi 2 (O,S) 3 oxysulfide catalyst with different V contents was successfully synthesized via a simple and facile method. The obtained V-doped Bi 2 (O,S) 3 solid solution catalysts were fully characterized by conventional methods. The catalytic performance of the samples was tested by using the reduction of 2-nitroaniline (2-NA) in aqueous solution. The reduction/decolorization of methylene blue (MB) and rhodamine B (RhB) was also chosen to evaluate the universality of catalysts. It was observed that the introduction of V can improve the catalytic performance, and 20%V-Bi 2 (O,S) 3 was found to be the optimal V doping concentration for the reduction of 2-NA, MB, and RhB dyes. For comparative purposes, a related V-free Bi 2 (O, S) 3 oxysulfide material was synthesized and tested as the catalyst. The superior activity of V-doped Bi 2 (O,S) 3 over pure Bi 2 (O,S) 3 was ascribed mainly to an increase in active sites of the material and also due to the presence of synergistic effects. The presence of V 5+ as found from XPS analysis may interact with Bi atoms and enhancing the catalytic activity of the sample. In the catalytic reduction of 2-NA, MB and RhB, the obtained V-doped Bi 2 (O,S) 3 oxysulfide catalyst exhibited excellent catalytic activity as compared with other reported catalysts. Furthermore this highly efficient, low-cost and easily reusable V-doped Bi 2 (O,S) 3 catalyst is anticipated to be of great potential in catalysis in the future. Copyright © 2017 Elsevier Ltd. All rights reserved.
Optimizing C–C Coupling on Oxide-Derived Copper Catalysts for Electrochemical CO 2 Reduction

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

Lum, Yanwei; Yue, Binbin; Lobaccaro, Peter

Here, copper electrodes, prepared by reduction of oxidized metallic copper, have been reported to exhibit higher activity for the electrochemical reduction of CO 2 and better selectivity toward C 2 and C 3 (C 2+) products than metallic copper that has not been preoxidized. We report here an investigation of the effects of four different preparations of oxide-derived electrocatalysts on their activity and selectivity for CO 2 reduction, with particular attention given to the selectivity to C 2+ products. All catalysts were tested for CO 2 reduction in 0.1 M KHCO 3 and 0.1 M CsHCO 3 at applied voltagesmore » in the range from –0.7 to –1.0 V vs RHE. The best performing oxide-derived catalysts show up to ~70% selectivity to C 2+ products and only ~3% selectivity to C 1 products at –1.0 V vs RHE when CsHCO 3 is used as the electrolyte. In contrast, the selectivity to C 2+ products decreases to ~56% for the same catalysts tested in KHCO 3. By studying all catalysts under identical conditions, the key factors affecting product selectivity could be discerned. These efforts reveal that the surface area of the oxide-derived layer is a critical parameter affecting selectivity. A high selectivity to C 2+ products is attained at an overpotential of –1 V vs RHE by operating at a current density sufficiently high to achieve a moderately high pH near the catalyst surface but not so high as to cause a significant reduction in the local concentration of CO 2. On the basis of recent theoretical studies, a high pH suppresses the formation of C 1 relative to C 2+ products. At the same time, however, a high local CO 2 concentration is necessary for the formation of C 2+ products.« less
Optimizing C–C Coupling on Oxide-Derived Copper Catalysts for Electrochemical CO 2 Reduction

DOE PAGES

Lum, Yanwei; Yue, Binbin; Lobaccaro, Peter; ...

2017-07-06

Here, copper electrodes, prepared by reduction of oxidized metallic copper, have been reported to exhibit higher activity for the electrochemical reduction of CO 2 and better selectivity toward C 2 and C 3 (C 2+) products than metallic copper that has not been preoxidized. We report here an investigation of the effects of four different preparations of oxide-derived electrocatalysts on their activity and selectivity for CO 2 reduction, with particular attention given to the selectivity to C 2+ products. All catalysts were tested for CO 2 reduction in 0.1 M KHCO 3 and 0.1 M CsHCO 3 at applied voltagesmore » in the range from –0.7 to –1.0 V vs RHE. The best performing oxide-derived catalysts show up to ~70% selectivity to C 2+ products and only ~3% selectivity to C 1 products at –1.0 V vs RHE when CsHCO 3 is used as the electrolyte. In contrast, the selectivity to C 2+ products decreases to ~56% for the same catalysts tested in KHCO 3. By studying all catalysts under identical conditions, the key factors affecting product selectivity could be discerned. These efforts reveal that the surface area of the oxide-derived layer is a critical parameter affecting selectivity. A high selectivity to C 2+ products is attained at an overpotential of –1 V vs RHE by operating at a current density sufficiently high to achieve a moderately high pH near the catalyst surface but not so high as to cause a significant reduction in the local concentration of CO 2. On the basis of recent theoretical studies, a high pH suppresses the formation of C 1 relative to C 2+ products. At the same time, however, a high local CO 2 concentration is necessary for the formation of C 2+ products.« less
Linking morphology with activity through the lifetime of pretreated PtNi nanostructured thin film catalysts

DOE PAGES

Cullen, David A.; Lopez-Haro, Miguel; Bayle-Guillemaud, Pascale; ...

2015-04-10

In this study, the nanoscale morphology of highly active Pt 3Ni 7 nanostructured thin film fuel cell catalysts is linked with catalyst surface area and activity following catalyst pretreatments, conditioning and potential cycling. The significant role of fuel cell conditioning on the structure and composition of these extended surface catalysts is demonstrated by high resolution imaging, elemental mapping and tomography. The dissolution of Ni during fuel cell conditioning leads to highly complex, porous structures which were visualized in 3D by electron tomography. Quantification of the rendered surfaces following catalyst pretreatment, conditioning, and cycling shows the important role pore structure playsmore » in surface area, activity, and durability.« less
LiFePO4 microcrystals as an efficient heterogeneous Fenton-like catalyst in degradation of rhodamine 6G.

PubMed

Li, Zhan Jun; Ali, Ghafar; Kim, Hyun Jin; Yoo, Seong Ho; Cho, Sung Oh

2014-01-01

We present a novel heterogeneous Fenton-like catalyst of LiFePO4 (LFP). LFP has been widely used as an electrode material of a lithium ion battery, but we observed that commercial LFP (LFP-C) could act as a good Fenton-like catalyst to decompose rhodamine 6G. The catalytic activity of LFP-C microparticles was much higher than a popular catalyst, magnetite nanoparticles. Furthermore, we found that the catalytic activity of LFP-C could be further increased by increasing the specific surface area. The reaction rate constant of the hydrothermally synthesized LFP microcrystals (LFP-H) is at least 18 times higher than that of magnetite nanoparticles even though the particle size of LFP is far larger than magnetite nanoparticles. The LFP catalysts also exhibited a good recycling behavior and high stability under an oxidizing environment. The effects of the experimental parameters such as the concentration of the catalysts, pH, and the concentration of hydrogen peroxide on the catalytic activity of LFP were also analyzed.
Integrating Semiconducting Catalyst of ReS2 Nanosheets into P-silicon Photocathode toward Enhanced Solar Water Reduction.

PubMed

Zhao, Heng; Dai, Zhengyi; Xu, Xiaoyong; Pan, Jing; Hu, Jingguo

2018-06-22

Loading the electro-catalysts at the semiconductor-electrolyte interface is one of promising strategies to develop photoelectrochemical (PEC) water splitting cells. However, the assembly of compatible and synergistic heterojunction between the semiconductor and the selected catalyst remains challenging. Here, we report a hierarchical p-Si/ReS2 heterojunction photocathode fabricated through uniform growth vertically standing ReS2 nanosheets (NSs) on planar p-Si substrate for solar-driven hydrogen evolution reaction (HER). The laden ReS2 NSs not only serve as a high-activity HER catalyst but also render a suitable electronic band coupled with p-Si into a Ⅱ-type heterojunction, which facilitates the photo-induced charge production, separation and utilization. As a result, the assembled p-Si/ReS2 photocathode exhibits a 23-fold-increased photocurrent density at 0 VRHE and a 35-fold-enhanced photoconversion efﬁciency compared to pure p-Si counterpart. The bifunctional ReS2 as catalyst and semiconductor enables multi effects in improving light harvesting, charge separation and catalytic kinetics, highlighting the potential of semiconducting catalysts integrated into solar water splitting devices.

High performance and durability of order-structured cathode catalyst layer based on TiO2@PANI core-shell nanowire arrays

NASA Astrophysics Data System (ADS)

Chen, Ming; Wang, Meng; Yang, Zhaoyi; Wang, Xindong

2017-06-01

In this paper, an order-structured cathode catalyst layer consisting of Pt-TiO2@PANI core-shell nanowire arrays that in situ grown on commercial gas diffusion layer (GDL) are prepared and applied to membrane electrode assembly (MEA) of proton exchange membrane fuel cell (PEMFC). In order to prepare the TiO2@PANI core-shell nanowire arrays with suitable porosity and prominent conductivity, the morphologies of the TiO2 nanoarray and electrochemical polymerization process of aniline are schematically investigated. The MEA with order-structured cathode catalyst layer is assembled in the single cell to evaluate the electrochemical performance and durability of PEMFC. As a result, the PEMFC with order-structured cathode catalyst layer shows higher peak power density (773.54 mW cm-2) than conventional PEMFC (699.30 mW cm-2). Electrochemically active surface area (ECSA) and charge transfer impedance (Rct) are measured before and after accelerated degradation test (ADT), and the corresponding experimental results indicate the novel cathode structure exhibits a better stability with respect to conventional cathode. The enhanced electrochemical performance and durability toward PEMFC can be ascribed to the order-structured cathode nanoarray structure with high specific surface area increases the utilization of catalyst and reduces the tortuosity of transport pathways, and the synergistic effect between TiO2@PANI support and Pt nanoparticles promotes the high efficiency of electrochemical reaction and improves the stability of catalyst. This research provides a facile and controllable method to prepare order-structured membrane electrode with lower Pt loading for PEMFC in the future.
Current advances in precious metal core-shell catalyst design.

PubMed

Wang, Xiaohong; He, Beibei; Hu, Zhiyu; Zeng, Zhigang; Han, Sheng

2014-08-01

Precious metal nanoparticles are commonly used as the main active components of various catalysts. Given their high cost, limited quantity, and easy loss of catalytic activity under severe conditions, precious metals should be used in catalysts at low volumes and be protected from damaging environments. Accordingly, reducing the amount of precious metals without compromising their catalytic performance is difficult, particularly under challenging conditions. As multifunctional materials, core-shell nanoparticles are highly important owing to their wide range of applications in chemistry, physics, biology, and environmental areas. Compared with their single-component counterparts and other composites, core-shell nanoparticles offer a new active interface and a potential synergistic effect between the core and shell, making these materials highly attractive in catalytic application. On one hand, when a precious metal is used as the shell material, the catalytic activity can be greatly improved because of the increased surface area and the closed interfacial interaction between the core and the shell. On the other hand, when a precious metal is applied as the core material, the catalytic stability can be remarkably improved because of the protection conferred by the shell material. Therefore, a reasonable design of the core-shell catalyst for target applications must be developed. We summarize the latest advances in the fabrications, properties, and applications of core-shell nanoparticles in this paper. The current research trends of these core-shell catalysts are also highlighted.
DOE Award No. DE-FC36-03GO13108 NOVEL NON-PRECIOUS METAL CATALYSTS FOR PEMFC: CATALYST SELECTION THROUGH MOLECULAR MODELING AND DURABILITY STUDIES Final Report (September 2003 – October 2008)

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

Branko N. Popov

2009-03-03

The objective of this project is to develop novel non-precious metal electrocatalysts for oxygen reduction reaction (ORR), and demonstrate the potential of the catalysts to perform at least as good as conventional Pt catalysts currently in use in polymer electrolyte membrane fuel cell (PEMFC) with a cost at least 50 % less than a target of 0.2 g (Pt loading)/peak kW and with durability > 2,000 h operation with less than 10 % power degradation. A novel nitrogen-modified carbon-based catalyst was obtained by modifying carbon black with nitrogen-containing organic precursor in the absence of transition metal precursor. The catalyst showsmore » the onset potential of approximately 0.76 V (NHE) for ORR and the amount of H2O2 of approximately 3% at 0.5 V (NHE). Furthermore, a carbon composite catalyst was achieved through the high-temperature pyrolysis of the precursors of transition metal (Co and Fe) and nitrogen supported on the nitrogen-modified carbon-based catalyst, followed by chemical post-treatment. This catalyst showed an onset potential for ORR as high as 0.87 V (NHE), and generated less than 1 % of H2O2. The PEM fuel cell exhibited a current density of 2.3 A cm-2 at 0.2 V for a catalyst loading of 6.0 mg cm-2. No significant performance degradation was observed for 480 h continuous operation. The characterization studies indicated that the metal-nitrogen chelate complexes decompose at the temperatures above 800 oC. During the pyrolysis, the transition metals facilitate the incorporation of pyridinic and graphitic nitrogen groups into the carbon matrix, and the carbon surface modified with nitrogen is active for ORR. In order to elucidate the role of transition metal precursor played in the formation of active sites in the non-precious metal catalysts, a novel ruthenium-based chelate (RuNx) catalyst was synthesized by using RuCl3 and propylene diammine as the Ru and N precursors, respectively, followed by high-temperature pyrolysis. This catalyst exhibited comparable catalytic activity and selectivity for ORR as the Pt catalyst. A theoretical analysis is made of the four-electron reduction reaction of oxygen to water over the mixed anion and cation (202) surface of pentlandite structure Co9Se8, one of several selenide phases. Reversible potentials for forming adsorbed reaction intermediates in acid are predicted using adsorption energies calculated with the Vienna ab initio simulation program (VASP) and the known bulk solution values together in a linear Gibbs energy relationship. The effect of hydrophobic and structural properties of a single/dual-layer cathode gas diffusion layer on mass transport in PEM fuel cells was studied using an analytical expression. The simulations indicated that liquid water transport at the cathode is controlled by the fraction of hydrophilic surface and the average pore diameter in the cathode gas diffusion layer. The optimized hydrophobicity and pore geometry in a dual-layer cathode GDL leads to an effective water management, and enhances the oxygen diffusion kinetics.« less
DOE Award No. DE-FC36-03GO13108 NOVEL NON-PRECIOUS METAL CATALYSTS FOR PEMFC: CATALYST SELECTION THROUGH MOLECULAR MODELING AND DURABILITY STUDIES Final Report (September 2003 – October 2008)

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

Branko N. Popov

2009-02-20

The objective of this project is to develop novel non-precious metal electrocatalysts for oxygen reduction reaction (ORR), and demonstrate the potential of the catalysts to perform at least as good as conventional Pt catalysts currently in use in polymer electrolyte membrane fuel cell (PEMFC) with a cost at least 50 % less than a target of 0.2 g (Pt loading)/peak kW and with durability > 2,000 h operation with less than 10 % power degradation. A novel nitrogen-modified carbon-based catalyst was obtained by modifying carbon black with nitrogen-containing organic precursor in the absence of transition metal precursor. The catalyst showsmore » the onset potential of approximately 0.76 V (NHE) for ORR and the amount of H2O2 of approximately 3% at 0.5 V (NHE). Furthermore, a carbon composite catalyst was achieved through the high-temperature pyrolysis of the precursors of transition metal (Co and Fe) and nitrogen supported on the nitrogen-modified carbon-based catalyst, followed by chemical post-treatment. This catalyst showed an onset potential for ORR as high as 0.87 V (NHE), and generated less than 1 % of H2O2. The PEM fuel cell exhibited a current density of 2.3 A cm-2 at 0.2 V for a catalyst loading of 6.0 mg cm-2. No significant performance degradation was observed for 480 h continuous operation. The characterization studies indicated that the metal-nitrogen chelate complexes decompose at the temperatures above 800 oC. During the pyrolysis, the transition metals facilitate the incorporation of pyridinic and graphitic nitrogen groups into the carbon matrix, and the carbon surface modified with nitrogen is active for ORR. In order to elucidate the role of transition metal precursor played in the formation of active sites in the non-precious metal catalysts, a novel ruthenium-based chelate (RuNx) catalyst was synthesized by using RuCl3 and propylene diammine as the Ru and N precursors, respectively, followed by high-temperature pyrolysis. This catalyst exhibited comparable catalytic activity and selectivity for ORR as the Pt catalyst. A theoretical analysis is made of the four-electron reduction reaction of oxygen to water over the mixed anion and cation (202) surface of pentlandite structure Co9Se8, one of several selenide phases. Reversible potentials for forming adsorbed reaction intermediates in acid are predicted using adsorption energies calculated with the Vienna ab initio simulation program (VASP) and the known bulk solution values together in a linear Gibbs energy relationship. The effect of hydrophobic and structural properties of a single/dual-layer cathode gas diffusion layer on mass transport in PEM fuel cells was studied using an analytical expression. The simulations indicated that liquid water transport at the cathode is controlled by the fraction of hydrophilic surface and the average pore diameter in the cathode gas diffusion layer. The optimized hydrophobicity and pore geometry in a dual-layer cathode GDL leads to an effective water management, and enhances the oxygen diffusion kinetics.« less
Co and Fe-catalysts supported on sepiolite: effects of preparation conditions on their catalytic behaviors in high temperature gas flow treatment of dye.

PubMed

Lin, Xiangfeng; Fang, Jian; Chen, Menglin; Huang, Zhi; Su, Chengyuan

2016-08-01

An efficient adsorbent/catalyst Co and Fe-catalysts loaded on sepiolite (Co-Fe/sepiolite) was successfully prepared for high temperature gas flow catalytic reaction by a simple impregnation method. The impact of preparation conditions (such as pH value of impregnation solution, impregnation time, calcination temperature, and time) on catalytic activity was studied. We found that the catalytic activity of Co-Fe/sepiolite was strongly influenced by all the investigated parameters. The regeneration efficiency (RE) was used to evaluate the catalytic activity. The RE is more noticeable at pH 5.0 of impregnation solution, impregnation time 18 h, calcination temperature 650 °C, and calcination time 3 h. This Co-Fe/sepiolite has great adsorption capacity in absorbing dye. It is used for an adsorbent to adsorb dye from wastewater solution under dynamic adsorption and saturated with dye, then regenerated with high temperature gas flow for adsorption/oxidation cycles. The Co-Fe/sepiolite acts as a catalyst to degrade the dye during regeneration under high temperature gas flow. Hence, the Co-Fe/sepiolite is not only an adsorbent but also a catalyst. The Co-Fe/sepiolite is more stable than sepiolite when applied in the treatment of plant's wastewater. The Co-Fe/sepiolite can be reused in adsorption-regeneration cycle. The results indicate the usability of the proposed combined process, dye adsorption on Co-Fe/sepiolite followed by the catalytic oxidation in high temperature gas flow.
Platinum/Tin Oxide/Silica Gel Catalyst Oxidizes CO

NASA Technical Reports Server (NTRS)

Upchurch, Billy T.; Davis, Patricia P.; Schryer, David R.; Miller, Irvin M.; Brown, David; Van Norman, John D.; Brown, Kenneth G.

1991-01-01

Heterogeneous catalyst of platinum, tin oxide, and silica gel combines small concentrations of laser dissociation products, CO and O2, to form CO22 during long times at ambient temperature. Developed as means to prevent accumulation of these products in sealed CO2 lasers. Effective at ambient operating temperatures and installs directly in laser envelope. Formulated to have very high surface area and to chemisorb controlled quantities of moisture: chemisorbed water contained within and upon its structure, makes it highly active and very longlived so only small quantity needed for long times.
Reactivity and Characterization of Solid State Hydrodesulfurization Catalysts.

NASA Astrophysics Data System (ADS)

Lindner, James Henry

1990-01-01

The identification of the phase responsible for hydrodesulfurization (HDS) activity has been the subject of extensive research. In this study, model solid state catalysts prepared from elemental starting materials were synthesized, characterized, and then used to desulfurize thiophene at temperatures ranging from 200-400 ^circC and a pressure of one atmosphere. The results of this work indicate that an increased HDS activity can be correlated with the presence of a poorly crystalline molybdenum sulfide-like phase detected by XRD, HREM, or AEM. The formation of this sulfur-deficient, non-stoichiometric phase could be accomplished by either removing sulfur directly from the catalyst synthesis mixture to yield a non-stoichiometric MoS_{ rm 2-x} moiety, or by introducing a transition metal promoter such as Fe, Co, Ni, or Cu into the system. The promoter atoms induced structural changes in the molybdenum sulfide edge planes by effectively scavenging sulfur during catalyst synthesis to form promoter sulfide species, which enhanced the formation of a non-stoichiometric, highly active molybdenum sulfide. This morphological effect was the primary function of the promoter in this system. All model catalysts displayed similar structure in the (0002) basal plane of MoS_2; however, only the catalytically active samples showed a high concentration of defects and disorder in the (1010), (1011), and (1012) edge planes. The HREM images obtained from these edge planes and their correlation with HDS activity dramatically illustrated the importance of the often-discussed edge plane structure of MoS_2 and its significance on HDS catalysis. Normalization of the HDS activities for the solid state models and a commercial catalyst with O_2 or CO chemisorption uptakes suggested that a similarity may exist between the catalytically active sites of these materials. In-situ XPS revealed that increasing promoter atom concentrations resulted in a more complete reduction of the promoter atom; but this shift to lower binding energies could not necessarily be correlated with activity. However, it was observed that the more active catalysts all exhibited the ability to dissociate H_2 and remove oxygen from their surface. This H_2 spillover or activation may also influence catalyst performance.
Properties of gasification-derived char and its utilization for catalytic tar reforming

NASA Astrophysics Data System (ADS)

Qian, Kezhen

Char is a low-value byproduct of biomass gasification and pyrolysis with many potential applications, such as soil amendment and the synthesis of activated carbon. The overall goal of the proposed research was to develop novel methods to use char derived from gasification for high-value applications in syngas conditioning. The first objective was to investigate effects of gasification condition and feedstock on properties of char derived from fluidized bed gasification. Results show that the surface areas of most of the char were 1--10 m 2/g and increased as the equivalence ratio increased. Char moisture and fixed carbon contents decreased while ash content increased as equivalence ratio increased. The next objective was to study the properties of sorghum and red cedar char derived from downdraft gasifier. Red cedar char contained more aliphatic carbon and o-alkyl carbon than sorghum char. Char derived from downdraft gasification had higher heating values and lower ash contents than char derived from fluidized bed gasification. The gasification reactivity of red cedar char was higher than that of sorghum char. Then, red cedar char based catalysts were developed with different preparation method to reform toluene and naphthalene as model tars. The catalyst prepared with nickel nitrate was found to be better than that with nickel acetate. The nickel particle size of catalyst impregnated with nickel nitrate was smaller than that of catalyst impregnated with nickel acetate. The particle size of catalyst impregnated with nickel acetate decreased by hydrazine reduction. The catalyst impregnated with nickel nitrate had the highest toluene removal efficiency, which was 70%--100% at 600--800 °C. The presence of naphthalene in tar reduced the catalyst efficiency. The toluene conversion was 36--99% and the naphthalene conversion was 37%--93% at 700--900 °C. Finally, effects of atmosphere and pressure on catalytic reforming of lignin-derived tars over the developed catalyst were investigated. An increase in reaction temperature led to an increase in removal of most tar components except naphthalene. High pressure promoted the catalytic conditioning of lignin tar. Hydrogen promoted the conversion of lignin into non-condensable gas.
Hemoglobin-carbon nanotube derived noble-metal-free Fe5C2-based catalyst for highly efficient oxygen reduction reaction

NASA Astrophysics Data System (ADS)

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

2016-02-01

High performance non-precious cathodic catalysts for oxygen reduction reaction (ORR) are vital for the development of energy materials and devices. Here, we report an noble metal free, Fe5C2 nanoparticles-studded sp2 carbon supported mesoporous material (CNTHb-700) as cathodic catalyst for ORR, which was prepared by pyrolizing the hybrid adduct of single walled carbon nanotubes (CNT) and lyophilized hemoglobin (Hb) at 700 °C. The catalyst shows onset potentials of 0.92 V in 0.1 M HClO4 and in 0.1 M KOH which are as good as commercial Pt/C catalyst, giving very high current density of 6.34 and 6.69 mA cm-2 at 0.55 V vs. reversible hydrogen electrode (RHE), respectively. This catalyst has been confirmed to follow 4-electron mechanism for ORR and shows high electrochemical stability in both acidic and basic media. Catalyst CNTHb-700 possesses much higher tolerance towards methanol than the commercial Pt/C catalyst. Highly efficient catalytic properties of CNTHb-700 could lead to fundamental understanding of utilization of biomolecules in ORR and materialization of proton exchange membrane fuel cells for clean energy production.
Carbon nanotubes-modified graphitic carbon nitride photocatalysts with synergistic effect of nickel(II) sulfide and molybdenum(II) disulfide co-catalysts for more efficient H2 evolution.

PubMed

Zhang, Yun-Xiao; Li, Kui; Yu, Yu-Xiang; Zhang, Wei-De

2018-09-15

This work reports effective photocatalysts which are composed of carbon nitride (CN), carbon nanotubes (CNTs), MoS 2 and NiS, for hydrogen evolution aiming at energy crises and environmental pollutions. The morphologies and optical properties of the photocatalysts were carefully characterized and their photocatalytic performance towards water reduction was studied afterwards. MoS 2 and NiS exhibit a significant synergistic effect working as co-catalysts. Compared to MoS 2 /CN nanohybrid, carbon nanotubes and NiS improved the absorption of visible light and the separation of charge carriers effectively. NiS-MoS 2 /CNTs/CN catalyst exhibits high performance for H 2 evolution and the optimized rate is 309.9 μmol·h -1 ·g -1 with no noble metals under visible light irradiation. The study demonstrates a non-noble metal photocatalyst system for effective generation of hydrogen with low cost. Copyright © 2018 Elsevier Inc. All rights reserved.
Rationally Designed Hierarchically Structured Tungsten Nitride and Nitrogen-Rich Graphene-Like Carbon Nanocomposite as Efficient Hydrogen Evolution Electrocatalyst.

PubMed

Zhu, Yanping; Chen, Gao; Zhong, Yijun; Zhou, Wei; Shao, Zongping

2018-02-01

Practical application of hydrogen production from water splitting relies strongly on the development of low-cost and high-performance electrocatalysts for hydrogen evolution reaction (HER). The previous researches mainly focused on transition metal nitrides as HER catalysts due to their electrical conductivity and corrosion stability under acidic electrolyte, while tungsten nitrides have reported poorer activity for HER. Here the activity of tungsten nitride is optimized through rational design of a tungsten nitride-carbon composite. More specifically, tungsten nitride (WN x ) coupled with nitrogen-rich porous graphene-like carbon is prepared through a low-cost ion-exchange/molten-salt strategy. Benefiting from the nanostructured WN x , the highly porous structure and rich nitrogen dopant (9.5 at%) of the carbon phase with high percentage of pyridinic-N (54.3%), and more importantly, their synergistic effect, the composite catalyst displays remarkably high catalytic activity while maintaining good stability. This work highlights a powerful way to design more efficient metal-carbon composites catalysts for HER.
Raman studies of nanocomposites catalysts: temperature and pressure effects of CeAl, CeMn and NiAl oxides

NASA Astrophysics Data System (ADS)

da Silva, Antonio N.; Neto, Antonio B. S.; Oliveira, Alcemira C.; Junior, Manoel C.; Junior, Jose A. L.; Freire, Paulo T. C.; Filho, Josué M.; Oliveira, Alcineia C.; Lang, Rossano

2018-06-01

High temperature and pressure effects on the physicochemical properties of binary oxides catalysts were investigated. The nanocomposites catalysts comprising of CeAl, CeMn and NiAl were characterized through various physicochemical techniques. A study of the temperature and pressure induced phenomena monitored by Raman spectroscopy was proposed and discussed. Spectral modifications of the Raman modes belonging to the CeMn suggest structural changes in the solid due to the MnO2 phase oxidation with increasing temperature. The thermal expansion and lattice anharmonicity effects were observed on CeMn due to lack of stability of the lattice vacancies. The CeAl and NiAl composites presented crystallographic stability at low temperatures however, undertake a phase transformation of NiO/Al2O3 into NiAl2O4, mostly without any deformation in its structure with increasing the temperature. It was also inferred that the binary oxides are more stables in comparison with monoxides. Detailed pressure-dependent Raman measurements of the T2g phonon mode of CeMn and NiAl revealed that the pressure contributes to modify bonds length and reduces the particles sizes of the solids. On the contrary, high pressure on CeAl sample improved the stability with addition of Al2O3 in the CeO2 lattice. The results then suggest a good stability of CeAl and NiAl composite catalysts at high pressure and low temperature and show how to prospect of tuning the catalysis for surface reactions entirely through in situ spectroscopic investigations means.
Pd-Catalyzed Aerobic Oxidative Biaryl Coupling: Non-Redox Cocatalysis by Cu(OTf)2 and Discovery of Fe(OTf)3 as a Highly Effective Cocatalyst.

PubMed

Wang, Dian; Stahl, Shannon S

2017-04-26

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

Xing, Rong; Dagle, Vanessa Lebarbier; Flake, Matthew

In this study we examine feasibility for steam reforming the mixed oxygenate aqueous fraction derived from mildly hydrotreated fast pyrolysis bio-oils. Catalysts selective towards hydrogen formation and resistant to carbon formation utilizing feeds with relatively low steam-to-carbon (S/C) ratios are desired. Rh (5 wt%), Pt (5 wt%), Ru (5 wt%), Ir (5 wt%), Ni (15 wt%), and Co (15 wt%) metals supported on MgAl 2O 4 were evaluated for catalytic performance at 500°C and 1 atm using a complex feed mixture comprising of acids, polyols, cycloalkanes, and phenolic compounds. The Rh catalyst was found to be the most active andmore » resistant to carbon formation. The Ni and Co catalysts were found to be more active than the other noble metal catalysts investigated (Pt, Ru, and Ir). However, Ni was found to form significantly more carbon (coke) on the catalyst surface. Furthermore, Co was found to be the most selective towards H 2 formation. Evaluating the effect of temperature on stability for the Rh catalyst we found that catalyst stability was best when operated at 500°C as compared to the higher temperatures investigated (700, 800°C). When operating at 700°C significantly more graphitic formation was observed on the spent catalyst surface. Operating at 800°C resulted in reactor plugging as a result of thermal decomposition of the reactants. Thus, a concept analogous to the petroleum industries’ use of a pre-reformer, operated at approximately 500°C for steam reforming of the heavier naphtha components, followed by a high temperature methane reforming operated in the 600-850°C temperature range, could be applied in the case of steam reforming biomass derived oxygenates. Moreover, stability evaluations were performed over the Rh, Ni, and Co catalysts at 500°C and 1 atm, under similar initial conversions, reveal the Co catalyst to be the most stable and selective towards H 2 production. Conversion and selectivity to CH 4 over Co remained relatively stable at approximately 80% and 1.2%, respectively. By contrast, the Rh and Ni catalysts CH 4 selectivity’s were approximately 7-8%. Thus suggesting that a Co type catalyst may be more suitable for the steam reforming of biomass derived oxygenates as compared to the more conventional Ni and Rh type steam reforming catalysts. However, deposition of carbon on the surface was observed. High resolution TEM on the spent catalysts revealed the formation of graphitic carbon on the Rh catalyst, and filamentous carbon formation was observed on both the Ni and Co catalysts, albeit less pronounced on Co. Thus there is certainly opportunity for improvement in Co catalyst design and/or with process optimization.« less
Pd-catalysts for DFAFC prepared by magnetron sputtering

NASA Astrophysics Data System (ADS)

Bieloshapka, I.; Jiricek, P.; Vorokhta, M.; Tomsik, E.; Rednyk, A.; Perekrestov, R.; Jurek, K.; Ukraintsev, E.; Hruska, K.; Romanyuk, O.; Lesiak, B.

2017-10-01

Samples of a palladium catalyst for direct formic acid fuel cell (DFAFC) applications were prepared on the Elat® carbon cloth by magnetron sputtering. The quantity of Pd was equal to 3.6, 120 and 720 μg/cm2. The samples were tested in a fuel cell for electro-oxidation of formic acid, and were characterized by atomic force microscopy (AFM), scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). The XPS measurements revealed a high contribution of PdCx phase formed at the Pd/Elat® surface interface, with carbon concentration in PdCx from x = 9.9-14.6 at.%, resulting from the C substrate and CO residual gases. Oxygen groups, e.g. hydroxyl (-OH), carbonyl (Cdbnd O) and carboxyl (COOH), resulted from the synthesis conditions due to the presence of residual gases, electro-oxidation during the reaction and oxidation in the atmosphere. Because of the formation of CO and CO2 on the catalysts during the reaction, or because of poisoning by impurities containing the -CH3 group, together with the risk of Pd losses due to dissolution in formic acid, there was a negative effect of catalyst degradation on the active area surface. The effect of different loadings of Pd layers led to increasing catalyst efficiency. Current-voltage curves showed that different amounts of catalyst did not increase the DFAFC power to a great extent. One reason for this was the catalyst structure formed on the carbon cloth. AFM and SEM measurements showed a layer-by-layer growth with no significant variations in morphology. The results for electric power recalculated for the Pd loading per 1 mg of catalyst layers in comparison to carbon substrates decorated by Pd nanoparticles showed that there is potential for applying anodes for formic acid fuel cells prepared by magnetron sputtering.
Visible light driven mineralization of spiramycin over photostructured N-doped TiO2 on up conversion phosphors.

PubMed

Sacco, Olga; Vaiano, Vincenzo; Sannino, Diana; Ciambelli, Paolo

2017-04-01

A novel visible light-active photocatalyst formulation (NdT/OP) was obtained by supporting N-doped TiO 2 (NdT) particles on up-conversion luminescent organic phosphors (OP). The photocatalytic activity of such catalysts was evaluated for the mineralization process of spiramycin in aqueous solution. The effect of NdT loading in the range 15-60wt.% on bulk and surface characteristics of NdT/OP catalysts was investigated by several chemico-physical characterization techniques. The photocatalytic performance of NdT/OP catalysts in the removal of spyramicin from aqueous solution was assessed through photocatalytic tests under visible light irradiation. Total organic carbon (TOC) of aqueous solution, and CO and CO 2 gas concentrations evolved during the photodegradation were analyzed. A dramatic enhancement of photocatalytic activity of the photostructured visible active NdT/OP catalysts, compared to NdT catalyst, was observed. Only CO 2 was detected in gas-phase during visible light irradiation, proving that the photocatalytic process is effective in the mineralization of spiramycin, reaching very high values of TOC removal. The photocatalyst NdT/OP at 30wt.% of NdT loading showed the highest photocatalytic activity (58% of TOC removed after 180min irradiation against only 31% removal after 300min of irradiation of NdT). We attribute this enhanced activity to the high effectiveness in the utilization of visible light through improved light harvesting and exploiting. OP particles act as "photoactive support", able to be excited by the external visible light irradiation, and reissue luminescence of wavelength suitable to promote NdT photomineralization activity. Copyright © 2016. Published by Elsevier B.V.
Porous bimetallic PdNi catalyst with high electrocatalytic activity for ethanol electrooxidation.

PubMed

Feng, Yue; Bin, Duan; Yan, Bo; Du, Yukou; Majima, Tetsuro; Zhou, Weiqiang

2017-05-01

Porous bimetallic PdNi catalysts were fabricated by a novel method, namely, reduction of Pd and Ni oxides prepared via calcining the complex chelate of PdNi-dimethylglyoxime (PdNi-dmg). The morphology and composition of the as-prepared PdNi were investigated by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD). Furthermore, the electrochemical properties of PdNi catalysts towards ethanol electrooxidation were also studied by electrochemical impedance spectrometry (EIS), cyclic voltammetry (CV) and chronoamperometry (CA) measurement. In comparison with porous Pd and commercial Pd/C catalysts, porous structural PdNi catalysts showed higher electrocatalytic activity and durability for ethanol electrooxidation, which may be ascribed to Pd and Ni property, large electroactive surface area and high electron transfer property. The Ni exist in the catalyst in the form of the nickel hydroxides (Ni(OH) 2 and NiOOH) which have a high electron and proton conductivity enhances the catalytic activity of the catalysts. All results highlight the great potential application of the calcination-reduction method for synthesizing high active porous PdNi catalysts in direct ethanol fuel cells. Copyright © 2017 Elsevier Inc. All rights reserved.
Effects of Activated Carbon Surface Property on Structure and Activity of Ru/AC Catalysts

NASA Astrophysics Data System (ADS)

Xu, S. K.; Li, L. M.; Guo, N. N.

2018-05-01

The activated carbon (AC) was modified by supercritical (SC) methanol, HNO3 oxidation, or HNO3 oxidation plus SC methanol, respectively. Then, the original and the modified AC were used as supports for Ru/AC catalysts prepared via the impregnation method. The results showed that the SC methanol modification decreased the content of surface acidic groups of AC. While HNO3 oxidation displayed the opposite behavior. Furthermore, the dispersion of ruthenium and the activity of catalysts were highly dependent on the content of surface acidic groups, and the SC methanol modified sample exhibited the highest activity for hydrogenation of glucose.
Develop high activity, low cost non-PGM fuel cell electrocatalyst and stable supports

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

Colon-Mercado, H. R.; Elvington, M. C.; Garcia-Diaz, B. L.

2016-09-28

A unique approach has been developed to probe the non-PGM catalyst active site for the Oxygen Reduction Reaction (ORR) for PEMFC. Iron based functionalities have been engineered into Metallic Organic Framework (MOF) catalysts to evaluate their impact on activity for the ORR. A series of FePhen@MOF catalysts have been synthesized with varying [Fe] to investigate the effect on electrochemical and electrocatalytic properties. The magnitude of the Fe II/III redox couple and the electrochemical surface area are analyzed to determine if there is a correlation between [Fe] and the ORR onset potential and/or the relative number of active sites.
Bosch Reactor Development for High Percentage Oxygen Recovery from Carbon Dioxide

NASA Technical Reports Server (NTRS)

Howard, David; Abney, Morgan

2015-01-01

This next Generation Life Support Project entails the development and demonstration of Bosch reaction technologies to improve oxygen recovery from metabolically generated oxygen and/or space environments. A primary focus was placed on alternate carbon formation reactor concepts to improve useful catalyst life for space vehicle applications, and make use of in situ catalyst resources for non-terrestrial surface missions. Current state-of-the-art oxygen recovery systems onboard the International Space Station are able to effectively recover approximately 45 percent of the oxygen consumed by humans and exhausted in the form of carbon dioxide (CO2). Excess CO2 is vented overboard and the oxygen contained in the molecules is lost. For long-duration missions beyond the reaches of Earth for resupply, it will be necessary to recover greater amounts of constituents such as oxygen that are necessary for sustaining life. Bosch technologies theoretically recover 100 percent of the oxygen from CO2, producing pure carbon as the sole waste product. Challenges with this technology revolve around the carbon product fouling catalyst materials, drastically limiting catalyst life. This project successfully demonstrated techniques to extend catalyst surface area exposure times to improve catalyst life for vehicle applications, and demonstrated the use of Martian and lunar regolith as viable catalyst Bosch Reactor Development for High Percentage Oxygen Recovery From Carbon Dioxide materials for surface missions. The Bosch process generates carbon nanotube formation within the regolith, which has been shown to improve mechanical properties of building materials. Production of bricks from post reaction regolith for building and radiation shielding applications were also explored.

High-performance oxygen reduction and evolution carbon catalysis: From mechanistic studies to device integration

DOE PAGES

To, John W. F.; Ng, Jia Wei Desmond; Siahrostami, Samira; ...

2016-11-30

The development of high-performance and low-cost oxygen reduction and evolution catalysts that can be easily integrated into existing devices is crucial for the wide deployment of energy storage systems that utilize O 2-H 2O chemistries, such as regenerative fuel cells and metal-air batteries. Herein, we report an NH 3-activated N-doped hierarchical carbon (NHC) catalyst synthesized via a scalable route, and demonstrate its device integration. The NHC catalyst exhibited good performance for both the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER), as demonstrated by means of electrochemical studies and evaluation when integrated into the oxygen electrode of amore » regenerative fuel cell. The activities observed for both the ORR and the OER were comparable to those achieved by state-of-the-art Pt and Ir catalysts in alkaline environments. We have further identified the critical role of carbon defects as active sites for electrochemical activity through density functional theory calculations and high-resolution TEM visualization. As a result, this work highlights the potential of NHC to replace commercial precious metals in regenerative fuel cells and possibly metal-air batteries for cost-effective storage of intermittent renewable energy.« less
High-performance oxygen reduction and evolution carbon catalysis: From mechanistic studies to device integration

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

To, John W. F.; Ng, Jia Wei Desmond; Siahrostami, Samira

The development of high-performance and low-cost oxygen reduction and evolution catalysts that can be easily integrated into existing devices is crucial for the wide deployment of energy storage systems that utilize O 2-H 2O chemistries, such as regenerative fuel cells and metal-air batteries. Herein, we report an NH 3-activated N-doped hierarchical carbon (NHC) catalyst synthesized via a scalable route, and demonstrate its device integration. The NHC catalyst exhibited good performance for both the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER), as demonstrated by means of electrochemical studies and evaluation when integrated into the oxygen electrode of amore » regenerative fuel cell. The activities observed for both the ORR and the OER were comparable to those achieved by state-of-the-art Pt and Ir catalysts in alkaline environments. We have further identified the critical role of carbon defects as active sites for electrochemical activity through density functional theory calculations and high-resolution TEM visualization. As a result, this work highlights the potential of NHC to replace commercial precious metals in regenerative fuel cells and possibly metal-air batteries for cost-effective storage of intermittent renewable energy.« less
Mechanistic Effects of Water on the Fe-Catalyzed Hydrodeoxygenation of Phenol. The Role of Brønsted Acid Sites

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

Hensley, Alyssa J. R.; Wang, Yong; Mei, Donghai

A mechanistic understanding of the roles of water is essential for developing highly active and selective catalysts for hydrodeoxygenation (HDO) reactions since water is ubiquitous in such reaction systems. Here, we present a study for phenol HDO on Fe catalysts using density functional theory which examines the effect of water on three elementary pathways for phenol HDO using an explicit solvation model. The presence of water is found to significantly decrease activation barriers required by hydrogenation reactions via two pathways. First, the proton transfer in the hydrogen bonding network of the liquid water phase is nearly barrierless, which significantly promotesmore » the direct through space tautomerization of phenol. Second, due to the high degree of oxophilicity on Fe, liquid water molecules are found to be easily dissociated into surface hydroxyl groups that can act as Brønsted acid sites. These sites dramatically promote hydrogenation reactions on the Fe surface. As a result, the hydrogen assisted dehydroxylation becomes the dominant phenol HDO pathway. This work provides new fundamental insights into aqueous phase HDO of biomass-derived oxygenates over Fe-based catalysts; e.g., the activity of Fe-based catalysts can be optimized by tuning the surface coverage of Brønsted acid sites via surface doping.« less
Selective hydrogenation of citral over supported Pt catalysts: insight into support effects

NASA Astrophysics Data System (ADS)

Wang, Xiaofeng; Hu, Weiming; Deng, Baolin; Liang, Xinhua

2017-04-01

Highly dispersed platinum (Pt) nanoparticles (NPs) were deposited on various substrates by atomic layer deposition (ALD) in a fluidized bed reactor at 300 °C. The substrates included multi-walled carbon nanotubes (MWCNTs), silica gel (SiO2), commercial γ-Al2O3, and ALD-prepared porous Al2O3 particles (ALD-Al2O3). The results of TEM analysis showed that 1.3 nm Pt NPs were highly dispersed on all different supports. All catalysts were used for the reaction of selective hydrogenation of citral to unsaturated alcohols (UA), geraniol, and nerol. Both the structure and acidity of supports affected the activity and selectivity of Pt catalysts. Pt/SiO2 showed the highest activity due to the strong acidity of SiO2 and the conversion of citral reached 82% after 12 h with a selectivity of 58% of UA. Pt/MWCNTs showed the highest selectivity of UA, which reached 65% with a conversion of 38% due to its unique structure and electronic effect. The cycling experiments indicated that Pt/MWCNTs and Pt/ALD-Al2O3 catalysts were more stable than Pt/SiO2, as a result of the different interactions between the Pt NPs and the supports.
Solution Structures of Highly Active Molecular Ir Water-Oxidation Catalysts from Density Functional Theory Combined with High-Energy X-ray Scattering and EXAFS Spectroscopy.

PubMed

Yang, Ke R; Matula, Adam J; Kwon, Gihan; Hong, Jiyun; Sheehan, Stafford W; Thomsen, Julianne M; Brudvig, Gary W; Crabtree, Robert H; Tiede, David M; Chen, Lin X; Batista, Victor S

2016-05-04

The solution structures of highly active Ir water-oxidation catalysts are elucidated by combining density functional theory, high-energy X-ray scattering (HEXS), and extended X-ray absorption fine structure (EXAFS) spectroscopy. We find that the catalysts are Ir dimers with mono-μ-O cores and terminal anionic ligands, generated in situ through partial oxidation of a common catalyst precursor. The proposed structures are supported by (1)H and (17)O NMR, EPR, resonance Raman and UV-vis spectra, electrophoresis, etc. Our findings are particularly valuable to understand the mechanism of water oxidation by highly reactive Ir catalysts. Importantly, our DFT-EXAFS-HEXS methodology provides a new in situ technique for characterization of active species in catalytic systems.
Hollow spheres of iron carbide nanoparticles encased in graphitic layers as oxygen reduction catalysts.

PubMed

Hu, Yang; Jensen, Jens Oluf; Zhang, Wei; Cleemann, Lars N; Xing, Wei; Bjerrum, Niels J; Li, Qingfeng

2014-04-01

Nonprecious metal catalysts for the oxygen reduction reaction are the ultimate materials and the foremost subject for low-temperature fuel cells. A novel type of catalysts prepared by high-pressure pyrolysis is reported. The catalyst is featured by hollow spherical morphologies consisting of uniform iron carbide (Fe3 C) nanoparticles encased by graphitic layers, with little surface nitrogen or metallic functionalities. In acidic media the outer graphitic layers stabilize the carbide nanoparticles without depriving them of their catalytic activity towards the oxygen reduction reaction (ORR). As a result the catalyst is highly active and stable in both acid and alkaline electrolytes. The synthetic approach, the carbide-based catalyst, the structure of the catalysts, and the proposed mechanism open new avenues for the development of ORR catalysts. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Autothermal reforming catalyst having perovskite structure

DOEpatents

Krumpel, Michael [Naperville, IL; Liu, Di-Jia [Naperville, IL

2009-03-24

The invention addressed two critical issues in fuel processing for fuel cell application, i.e. catalyst cost and operating stability. The existing state-of-the-art fuel reforming catalyst uses Rh and platinum supported over refractory oxide which add significant cost to the fuel cell system. Supported metals agglomerate under elevated temperature during reforming and decrease the catalyst activity. The catalyst is a perovskite oxide or a Ruddlesden-Popper type oxide containing rare-earth elements, catalytically active firs row transition metal elements, and stabilizing elements, such that the catalyst is a single phase in high temperature oxidizing conditions and maintains a primarily perovskite or Ruddlesden-Popper structure under high temperature reducing conditions. The catalyst can also contain alkaline earth dopants, which enhance the catalytic activity of the catalyst, but do not compromise the stability of the perovskite structure.
Stability of High-Performance Pt-Based Catalysts for Oxygen Reduction Reactions.

PubMed

Lin, Rui; Cai, Xin; Zeng, Hao; Yu, Zhuoping

2018-04-01

Due to their environmental sustainability and high efficiency, proton-exchange-membrane fuel cells (PEMFCs) are expected to be an essential type of energy source for electric vehicles, energy generation, and the space industry in the coming decades. Here, the recent developments regarding shape-controlled nanostructure catalysts are reviewed, with a focus on the stability of high-performance Pt-based catalysts and related mechanisms. The catalysts, which possess great activity, are still far from meeting the requirements of their applications, due to stability issues, especially in membrane electrode assemblies (MEAs). Thus, solutions toward the comprehensive performance of Pt-based catalysts are discussed here. The research trends and related theories that can promote the application of Pt-based catalysts are also provided. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Hydrogen production from methane using oxygen-permeable ceramic membranes

NASA Astrophysics Data System (ADS)

Faraji, Sedigheh

Non-porous ceramic membranes with mixed ionic and electronic conductivity have received significant interest in membrane reactor systems for the conversion of methane and higher hydrocarbons to higher value products like hydrogen. However, hydrogen generation by this method has not yet been commercialized and suffers from low membrane stability, low membrane oxygen flux, high membrane fabrication costs, and high reaction temperature requirements. In this dissertation, hydrogen production from methane on two different types of ceramic membranes (dense SFC and BSCF) has been investigated. The focus of this research was on the effects of different parameters to improve hydrogen production in a membrane reactor. These parameters included operating temperature, type of catalyst, membrane material, membrane thickness, membrane preparation pH, and feed ratio. The role of the membrane in the conversion of methane and the interaction with a Pt/CeZrO2 catalyst has been studied. Pulse studies of reactants and products over physical mixtures of crushed membrane material and catalyst have clearly demonstrated that a synergy exists between the membrane and the catalyst under reaction conditions. The degree of catalyst/membrane interaction strongly impacts the conversion of methane and the catalyst performance. During thermogravimetric analysis, the onset temperature of oxygen release for BSCF was observed to be lower than that for SFC while the amount of oxygen release was significantly greater. Pulse injections of CO2 over crushed membranes at 800°C have shown more CO2 dissociation on the BSCF membrane than the SFC membrane, resulting in higher CO formation on the BSCF membrane. Similar to the CO2 pulses, when CO was injected on the samples at 800°C, CO2 production was higher on BSCF than SFC. It was found that hydrogen consumption on BSCF particles is 24 times higher than that on SFC particles. Furthermore, Raman spectroscopy and temperature programmed desorption studies of CO and CO2 showed a higher CO and CO2 adsorption (for temperatures ranging from room temperature to 600°C) on BSCF compared to the SFC membrane. CO2 reforming reactions on BSCF and SFC dense membranes in a membrane reactor showed higher methane conversion and H2/CO ratio on BSCF than SFC in the presence of the Pt/CeZrO2 catalyst. This high conversion and H2/CO ratio could be ascribed to higher CO, CO2, and H2 adsorption on BSCF than SFC, resulting in higher steam and CO2 reforming on the BSCF. The Pt-Ni/CeZrO2 catalyst exhibits promising performance for hydrogen production. Platinum enhances the reducibility of Ni/Al2O 3 and Ni/CeZrO2 catalysts resulting in improved catalysts for H2 production at moderate temperatures. TPR and Raman studies show an alloy formation in the Pt-Ni/Al2O3 catalyst. Further work is required to study the interaction between Pt and Ni in the bimetallic Pt-Ni/CeZrO2 and Pt-Ni/Al2O3 catalysts. Although the Pt-Ni/Al2O3 catalyst shows high methane conversion in the presence of the BSCF membrane at 800°C, the activity of this catalyst is low at 600°C. Pt-Ni/CeZrO2 bimetallic catalyst demonstrates superior performance compared to Pt-Ni/Al2O3 catalyst at 600°C. The thinner BSCF membrane (2.2 mm) demonstrates a higher methane conversion and H2:CO ratio than the thicker BSCF membrane (2.6 mm) because membrane oxygen flux is inversely proportional to thickness. Varying the pH of the precursor solution during membrane preparation has no significant effect on the oxygen flux or the reaction. The CH 4:CO2 feed ratio significantly affects the hydrogen production over the BSCF membrane. Altering the CH4:CO2 ratio has a direct impact on the oxygen flux, which in turn can influence the reaction pathway. These studies suggest that the Pt-Ni/CeZrO2 catalyst might be suitable for low-temperature hydrocarbon conversion reactions over thin BSCF ceramic membranes. Most importantly, the BSCF membrane can reduce the apparent activation energy of the CO2 reforming reaction by changing the reaction pathway to include more steam reforming.
Nano-Array Integrated Structured Catalysts: A New Paradigm upon Conventional Wash-Coated Monolithic Catalysts?

DOE PAGES

Weng, Junfei; Lu, Xingxu; Gao, Pu-Xian

2017-08-28

The monolithic catalyst, namely the structured catalyst, is one of the important categories of catalysts used in various fields, especially in catalytic exhaust after-treatment. Despite its successful application in conventional wash-coated catalysts in both mobile and stationary catalytic converters, washcoat-based technologies are facing multi-fold challenges, including: (1) high Pt-group metals (PGM) material loading being required, driving the market prices; (2) less-than ideal distribution of washcoats in typically square-shaped channels associated with pressure drop sacrifice; and (3) far from clear correlations between macroscopic washcoat structures and their catalytic performance. To tackle these challenges, the well-defined nanostructure array (nano-array)-integrated structured catalysts whichmore » we invented and developed recently have been proven to be a promising class of cost-effective and efficient devices that may complement or substitute wash-coated catalysts. This new type of structured catalysts is composed of honeycomb-structured monoliths, whose channel surfaces are grown in situ with a nano-array forest made of traditional binary transition metal oxide support such as Al 2O 3, CeO 2, Co 3O 4, MnO 2, TiO 2, and ZnO, or newer support materials including perovskite-type ABO3 structures, for example LaMnO 3, LaCoO 3, LaNiO, and LaFeO 3. The integration strategy parts from the traditional washcoat technique. Instead, an in situ nanomaterial assembly method is utilized, such as a hydro (solva-) thermal synthesis approach, in order to create sound structure robustness, and increase ease and complex-shaped substrate adaptability. Specifically, the critical fabrication procedures for nano-array structured catalysts include deposition of seeding layer, in situ growth of nano-array, and loading of catalytic materials. The generic methodology utilization in both the magnetic stirring batch process and continuous flow reactor synthesis offers the nano-array catalysts with great potential to be scaled up readily and cost-effectively. The tunability of the structure and catalytic performance could be achieved through morphology and geometry adjustment and guest atoms and defect manipulation, as well as composite nano-array catalyst manufacture. Excellent stabilities under various conditions were also present compared to conventional wash-coated catalysts.« less
Nano-Array Integrated Structured Catalysts: A New Paradigm upon Conventional Wash-Coated Monolithic Catalysts?

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

Weng, Junfei; Lu, Xingxu; Gao, Pu-Xian

The monolithic catalyst, namely the structured catalyst, is one of the important categories of catalysts used in various fields, especially in catalytic exhaust after-treatment. Despite its successful application in conventional wash-coated catalysts in both mobile and stationary catalytic converters, washcoat-based technologies are facing multi-fold challenges, including: (1) high Pt-group metals (PGM) material loading being required, driving the market prices; (2) less-than ideal distribution of washcoats in typically square-shaped channels associated with pressure drop sacrifice; and (3) far from clear correlations between macroscopic washcoat structures and their catalytic performance. To tackle these challenges, the well-defined nanostructure array (nano-array)-integrated structured catalysts whichmore » we invented and developed recently have been proven to be a promising class of cost-effective and efficient devices that may complement or substitute wash-coated catalysts. This new type of structured catalysts is composed of honeycomb-structured monoliths, whose channel surfaces are grown in situ with a nano-array forest made of traditional binary transition metal oxide support such as Al 2O 3, CeO 2, Co 3O 4, MnO 2, TiO 2, and ZnO, or newer support materials including perovskite-type ABO3 structures, for example LaMnO 3, LaCoO 3, LaNiO, and LaFeO 3. The integration strategy parts from the traditional washcoat technique. Instead, an in situ nanomaterial assembly method is utilized, such as a hydro (solva-) thermal synthesis approach, in order to create sound structure robustness, and increase ease and complex-shaped substrate adaptability. Specifically, the critical fabrication procedures for nano-array structured catalysts include deposition of seeding layer, in situ growth of nano-array, and loading of catalytic materials. The generic methodology utilization in both the magnetic stirring batch process and continuous flow reactor synthesis offers the nano-array catalysts with great potential to be scaled up readily and cost-effectively. The tunability of the structure and catalytic performance could be achieved through morphology and geometry adjustment and guest atoms and defect manipulation, as well as composite nano-array catalyst manufacture. Excellent stabilities under various conditions were also present compared to conventional wash-coated catalysts.« less
High Electrocatalytic Hydrogen Evolution Activity of an Anomalous Ruthenium Catalyst.

PubMed

Zheng, Yao; Jiao, Yan; Zhu, Yihan; Li, Lu Hua; Han, Yu; Chen, Ying; Jaroniec, Mietek; Qiao, Shi-Zhang

2016-12-14

Hydrogen evolution reaction (HER) is a critical process due to its fundamental role in electrocatalysis. Practically, the development of high-performance electrocatalysts for HER in alkaline media is of great importance for the conversion of renewable energy to hydrogen fuel via photoelectrochemical water splitting. However, both mechanistic exploration and materials development for HER under alkaline conditions are very limited. Precious Pt metal, which still serves as the state-of-the-art catalyst for HER, is unable to guarantee a sustainable hydrogen supply. Here we report an anomalously structured Ru catalyst that shows 2.5 times higher hydrogen generation rate than Pt and is among the most active HER electrocatalysts yet reported in alkaline solutions. The identification of new face-centered cubic crystallographic structure of Ru nanoparticles was investigated by high-resolution transmission electron microscopy imaging, and its formation mechanism was revealed by spectroscopic characterization and theoretical analysis. For the first time, it is found that the Ru nanocatalyst showed a pronounced effect of the crystal structure on the electrocatalytic activity tested under different conditions. The combination of electrochemical reaction rate measurements and density functional theory computation shows that the high activity of anomalous Ru catalyst in alkaline solution originates from its suitable adsorption energies to some key reaction intermediates and reaction kinetics in the HER process.
Co3O4 nanorod-supported Pt with enhanced performance for catalytic HCHO oxidation at room temperature

NASA Astrophysics Data System (ADS)

Yan, Zhaoxiong; Xu, Zhihua; Cheng, Bei; Jiang, Chuanjia

2017-05-01

Formaldehyde (HCHO) removal from air at room (ambient) temperature by effective catalysts is of significance for improving indoor air quality, and catalysts with high efficiency and good recyclability are highly desirable. In this study, platinum (Pt) supported on nanorod-shaped Co3O4 (Pt/Co3O4) was prepared by calcination of microwave-assisted synthesized Co3O4 precursor followed by NaBH4-reduction of Pt precursor. The as-prepared Co3O4 exhibited a morphology of nanorods with lengths of 400-700 nm and diameters of approximately 40-50 nm, which were self-assembled by nanoparticles. The Pt/Co3O4 catalyst exhibited a superior catalytic performance for HCHO oxidation at room temperature compared to Pt supported on commercial Co3O4 (Pt/Co3O4-c) and Pt supported on commercial TiO2 (Pt/TiO2), which is mainly due to the high oxygen mobility resulting from its distinct nanorod morphology, strong metal-support interaction between Pt and Co3O4, and the intrinsic redox nature of the Co3O4 support. This study provides new insights into the fabrication of high-performance catalysts for indoor air purification.
In-situ upgrading of biomass pyrolysis vapors: catalyst screening on a fixed bed reactor.

PubMed

Stefanidis, S D; Kalogiannis, K G; Iliopoulou, E F; Lappas, A A; Pilavachi, P A

2011-09-01

In-situ catalytic upgrading of biomass fast pyrolysis vapors was performed in a fixed bed bench-scale reactor at 500°C, for catalyst screening purposes. The catalytic materials tested include a commercial equilibrium FCC catalyst (E-cat), various commercial ZSM-5 formulations, magnesium oxide and alumina materials with varying specific surface areas, nickel monoxide, zirconia/titania, tetragonal zirconia, titania and silica alumina. The bio-oil was characterized measuring its water content, the carbon-hydrogen-oxygen (by difference) content and the chemical composition of its organic fraction. Each catalytic material displayed different catalytic effects. High surface area alumina catalysts displayed the highest selectivity towards hydrocarbons, yielding however low organic liquid products. Zirconia/titania exhibited good selectivity towards desired compounds, yielding higher organic liquid product than the alumina catalysts. The ZSM-5 formulation with the highest surface area displayed the most balanced performance having a moderate selectivity towards hydrocarbons, reducing undesirable compounds and producing organic liquid products at acceptable yields. Copyright © 2011 Elsevier Ltd. All rights reserved.
Discovery of true electrochemical reactions for ultrahigh catalyst mass activity in water splitting

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

Mo, Jingke; Kang, Zhenye; Retterer, Scott T.

Better understanding of true electrochemical reaction behaviors in electrochemical energy devices has long been desired. It has been assumed so far that the reactions occur across the entire catalyst layer (CL), which is designed and fabricated uniformly with catalysts, conductors of protons and electrons, and pathways for reactants and products. By introducing a state-of-the-art characterization system, a thin, highly tunable liquid/gas diffusion layer (LGDL), and an innovative design of electrochemical proton exchange membrane electrolyzer cells (PEMECs), the electrochemical reactions on both microspatial and microtemporal scales are revealed for the first time. Surprisingly, reactions occur only on the CL adjacent tomore » good electrical conductors. On the basis of these findings, new CL fabrications on the novel LGDLs exhibit more than 50 times higher mass activity than conventional catalyst-coated membranes in PEMECs. In conclusion, this discovery presents an opportunity to enhance the multiphase interfacial effects, maximizing the use of the catalysts and significantly reducing the cost of these devices.« less
Discovery of true electrochemical reactions for ultrahigh catalyst mass activity in water splitting

PubMed Central

Mo, Jingke; Kang, Zhenye; Retterer, Scott T.; Cullen, David A.; Toops, Todd J.; Green, Johney B.; Mench, Matthew M.; Zhang, Feng-Yuan

2016-01-01

Better understanding of true electrochemical reaction behaviors in electrochemical energy devices has long been desired. It has been assumed so far that the reactions occur across the entire catalyst layer (CL), which is designed and fabricated uniformly with catalysts, conductors of protons and electrons, and pathways for reactants and products. By introducing a state-of-the-art characterization system, a thin, highly tunable liquid/gas diffusion layer (LGDL), and an innovative design of electrochemical proton exchange membrane electrolyzer cells (PEMECs), the electrochemical reactions on both microspatial and microtemporal scales are revealed for the first time. Surprisingly, reactions occur only on the CL adjacent to good electrical conductors. On the basis of these findings, new CL fabrications on the novel LGDLs exhibit more than 50 times higher mass activity than conventional catalyst-coated membranes in PEMECs. This discovery presents an opportunity to enhance the multiphase interfacial effects, maximizing the use of the catalysts and significantly reducing the cost of these devices. PMID:28138516
Assessment of the Pozzolanic Activity of a Spent Catalyst by Conductivity Measurement of Aqueous Suspensions with Calcium Hydroxide

PubMed Central

Velázquez, Sergio; Monzó, José M.; Borrachero, María V.; Payá, Jordi

2014-01-01

The pozzolanic activity of the spent catalyst produced by fluid catalytic cracking (FCC) has been studied by various methods in recent years. However, no quick and easy method has been reported for this activity based on the associated studies. In this work, the pozzolanic activity of a spent catalyst was investigated by measuring its electrical conductivity in aqueous suspensions of pozzolan/calcium hydroxide. The behavior of the FCC catalyst residue was compared to that of reactive and inert materials of similar chemical compositions. Further, the influence of temperature on the suspension was studied, and also, a new method was proposed in which the pozzolan/calcium hydroxide ratio was varied (with the initial presence of solid Ca(OH)2 in the system). It was concluded that the method is effective, fast and simple for evaluating the high reactivity of the catalyst. Therefore, this method is an alternative for the evaluation of the reactivity of pozzolanic materials. PMID:28788583
Discovery of true electrochemical reactions for ultrahigh catalyst mass activity in water splitting

DOE PAGES

Mo, Jingke; Kang, Zhenye; Retterer, Scott T.; ...

2016-11-18

Better understanding of true electrochemical reaction behaviors in electrochemical energy devices has long been desired. It has been assumed so far that the reactions occur across the entire catalyst layer (CL), which is designed and fabricated uniformly with catalysts, conductors of protons and electrons, and pathways for reactants and products. By introducing a state-of-the-art characterization system, a thin, highly tunable liquid/gas diffusion layer (LGDL), and an innovative design of electrochemical proton exchange membrane electrolyzer cells (PEMECs), the electrochemical reactions on both microspatial and microtemporal scales are revealed for the first time. Surprisingly, reactions occur only on the CL adjacent tomore » good electrical conductors. On the basis of these findings, new CL fabrications on the novel LGDLs exhibit more than 50 times higher mass activity than conventional catalyst-coated membranes in PEMECs. In conclusion, this discovery presents an opportunity to enhance the multiphase interfacial effects, maximizing the use of the catalysts and significantly reducing the cost of these devices.« less
SBA-15/hydrotalcite nanocomposite as an efficient support for the immobilization of heteropolyacid: A triply-hybrid catalyst for the synthesis of 2-amino-4H-pyrans in water

NASA Astrophysics Data System (ADS)

Sadjadi, Samahe; Heravi, Majid M.; Zadsirjan, Vahideh; Farzaneh, Vahid

2017-12-01

To circumvent the high solubility and low surface area of heteropolyacid and in attempt to develop a bi-functional heterogeneous catalyst for promoting organic transformations, heteropolyacid was embedded in functionalized SBA-15 and subsequently hybridized with layered double hydroxide. The catalyst could be considered as a bi-functional catalyst with both acidic and basic properties. The acidic properties emerged from the SBA-15 and heteropolyacid component while layered double hydroxide render the catalyst basic. The catalyst was characterized by using SEM/EDX, FT-IR, XRD, ICP-AES, BET and elemental mapping analysis. The catalytic activity of the catalyst was studied for promoting one-pot three-component condensation of aromatic aldehydes, malononitrile or ethyl cyanoacetate and C-H activated acidic molecules in aqueous media for the synthesis of 2-amino-4H-pyran derivatives. The catalyst exhibited high catalytic activity, which was superior to the previously reported ones. Moreover, the reusability of the catalyst was excellent and the leaching of heteropolyacid was dramatically suppressed. High yields, short reaction times, eco-friendly conditions, simplicity of the procedure, reusability of the catalyst and broad substrate scope are the merits of this protocol.
Chemical Processing in High-Pressure Aqueous Environments. 9. Process Development for Catalytic Gasification of Algae Feedstocks

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

Elliott, Douglas C.; Hart, Todd R.; Neuenschwander, Gary G.

Through the use of a metal catalyst, gasification of wet algae slurries can be accomplished with high levels of carbon conversion to gas at relatively low temperature (350 C). In a pressurized-water environment (20 MPa), near-total conversion of the organic structure of the algae to gases has been achieved in the presence of a supported ruthenium metal catalyst. The process is essentially steam reforming, as there is no added oxidizer or reagent other than water. In addition, the gas produced is a medium-heating value gas due to the synthesis of high levels of methane, as dictated by thermodynamic equilibrium. Asmore » opposed to earlier work, biomass trace components were removed by processing steps so that they did not cause processing difficulties in the fixed catalyst bed tubular reactor system. As a result, the algae feedstocks, even those with high ash contents, were much more reliably processed. High conversions were obtained even with high slurry concentrations. Consistent catalyst operation in these short-term tests suggested good stability and minimal poisoning effects. High methane content in the product gas was noted with significant carbon dioxide captured in the aqueous byproduct in combination with alkali constituents and the ammonia byproduct derived from proteins in the algae. High conversion of algae to gas products was found with low levels of byproduct water contamination and low to moderate loss of carbon in the mineral separation step.« less

A modified preparation procedure for carbon nanotube-confined Nd/Na heterobimetallic catalyst for anti-selective catalytic asymmetric nitroaldol reactions.

PubMed

Sureshkumar, Devarajulu; Hashimoto, Kazuki; Kumagai, Naoya; Shibasaki, Masakatsu

2013-11-15

A recyclable asymmetric metal-based catalyst is a rare entity among the vast collection of asymmetric catalysts developed so far. Recently we found that the combination of a self-assembling metal-based asymmetric catalyst and multiwalled carbon nanotubes (MWNTs) produced a highly active and recyclable catalyst in which the catalytically active metal complex was dispersed in the MWNT network. Herein we describe an improved preparation procedure and full details of a Nd/Na heterobimetallic complex confined in MWNTs. Facilitated self-assembly of the catalyst with MWNTs avoided the sacrificial use of excess chiral ligand for the formation of the heterobimetallic complex, improving the loading ratio of the catalyst components. Eighty-five percent of the catalyst components were incorporated onto MWNTs to produce the confined catalyst, which was a highly efficient and recyclable catalyst for the anti-selective asymmetric nitroaldol reaction. The requisite precautions for the catalyst preparation to elicit reproducible catalytic performance are summarized. Superior catalytic profiles over the prototype catalyst without MWNTs were revealed in the synthesis of optically active 1,2-nitroalkanols, which are key intermediates for the synthesis of therapeutics.
Application of sodium carbonate prevents sulphur poisoning of catalysts in automated total mercury analysis

NASA Astrophysics Data System (ADS)

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

2017-07-01

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

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

Xin, Le; Yang, Fan; Xie, Jian

2017-01-01

This work demonstrates that functionalizing annealed-Pt/Ketjen black EC300j (a-Pt/KB) and dealloyed-PtNi/Ketjen black EC300j (d-PtNi/KB) catalysts using p-phenyl sulfonic acid can effectively enhance performance in the membrane electrode assemblies (MEAs) of proton exchange membrane fuel cells (PEMFCs). The functionalization increased the size of both Pt and PtNi catalyst particles and resulted in the further leaching of Ni from the PtNi catalyst while promoting the formation of nanoporous PtNi nanoparticles. The size of the SO3H-Pt/KB and SO3H-PtNi/KB carbon-based aggregates decreased dramatically, leading to the formation of catalyst layers with narrower pore size distributions.MEA tests highlighted the benefits of the surface functionalization, inmore » which the cells with SO3H-Pt/KB and SO3H-PtNi/KB cathode catalysts showed superior high current density performance under reduced RH conditions, in comparison with cells containing annealed Pt/KB (a-Pt/KB) and de-alloyed PtNi/KB (d-PtNi/KB) catalysts. The performance improvement was particularly evident when using reactant gases with low relative humidity, indicating that the hydrophilic functional groups on the carbon improved the water retention in the cathode catalyst layer. These results show a new avenue for enhancing catalyst performance for the next generation of catalytic materials for PEMFCs.« less
Magnetically Recoverable Pd/Fe 3O 4 Core-Shell Nanowire Clusters with Increased Hydrogenation Activity

DOE PAGES

Watt, John; Kotula, Paul G.; Huber, Dale L.

2017-02-06

Core-shell nanostructures are promising candidates for the next generation of catalysts due to synergistic effects which can arise from having two active species in close contact, leading to increased activity. Likewise, catalysts displaying added functionality, such as a magnetic response, can increase their scientific and industrial potential. Here, we synthesize Pd/Fe 3O 4 core-shell nanowire clusters and apply them as hydrogenation catalysts for an industrially important hydrogenation reaction; the conversion of acetophenone to 1-phenylethanol. During synthesis, the palladium nanowires self-assemble into clusters which act as a high surface area framework for the growth of a magnetic iron oxide shell. Wemore » demonstrate excellent catalytic activity due to the presence of palladium while the strong magnetic properties provided by the iron oxide shell enable facile catalyst recovery.« less
Isoelectronic Manganese and Iron Hydrogenation/Dehydrogenation Catalysts: Similarities and Divergences.

PubMed

Gorgas, Nikolaus; Kirchner, Karl

2018-06-19

Sustainable processes that utilize nontoxic, readily available, and inexpensive starting materials for organic synthesis constitute a major objective in modern chemical research. In this context, it is highly important to perform reactions under catalytic conditions and to replace precious metal catalysts by earth-abundant nonprecious metal catalysts. In particular, iron and manganese are promising candidates, as these are among the most abundant metals in the earth's crust, are inexpensive, and exhibit a low environmental impact. As far as chemical processes are concerned, hydrogenations and acceptorless alcohol dehydrogenation (AAD), sometimes in conjunction with hydrogen autotransfer reactions, are becoming important areas of research. While the first is a very important synthetic process representing a highly atom-efficient and clean methodology, AAD is an oxidant-free, environmentally benign reaction where carbonyl compounds together with dihydrogen as a valuable product and/or reactant (autotransfer) and water are formed. Carbonyl compounds, typically generated in situ, can be converted into other useful organic materials such as amines, imines, or heterocycles. In 2016 several groups, including ours, discovered for the first time the potential of hydride biscarbonyl Mn(I) complexes bearing strongly bound PNP pincer ligands or related tridentate ligands as highly effective and versatile catalysts for hydrogenation, transfer hydrogenation, and dehydrogenation reactions. These complexes are isoelectronic analogues of the respective hydride monocarbonyl Fe(II) PNP compounds and display similar reactivities but also quite divergent behavior depending on the coligands. Moreover, manganese compounds show improved long-term stability and high robustness toward harsh reaction conditions. In light of these recent achievements, this Account contrasts Mn(I) and Fe(II) PNP pincer catalysts, highlighting specific features that are connected to particular structural and electronic properties. It also addresses opportunities and restrictions in their catalytic applications. Apart from classical hydrogenations, it also covers the most recent developments of these catalysts for AAD resulting in the synthesis of complex organic molecules such as heterocycles via multicomponent reactions. The ambivalent hydrogen-based redox chemistry provides access to a variety of synthetically valuable reductive and oxidative coupling reactions. Hence, these catalysts cover a broad scope of catalytic applications and exhibit activities and productivities that are becoming competitive with those of well-established precious metal catalysts. The knowledge about the nature and characteristics of active Mn(I)- and Fe(II)-based systems paves the way for conceptually and mechanistically well-founded research, which might lead to further developments and the discovery of novel catalysts extending the current scope and limitations of reactivity. It underlines that base metal catalysts are beginning to challenge precious metal catalysts and contributes to the further advancement of waste-free sustainable base metal catalysis.
Enhanced activity and stability of copper oxide/γ-alumina catalyst in catalytic wet-air oxidation: Critical roles of cerium incorporation

NASA Astrophysics Data System (ADS)

Zhang, Yongli; Zhou, Yanbo; Peng, Chao; Shi, Junjun; Wang, Qingyu; He, Lingfeng; Shi, Liang

2018-04-01

By successive impregnation method, the Ce-modified Cu-O/γ-Al2O3 catalyst was prepared and characterized using nitrogen adsorption-desorption, scanning electron microscopy energy dispersive X-ray analysis (SEM-EDS), high-resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Raman, and H2-Temperature programming reduction (H2-TPR). In catalytic wet-air oxidation (CWAO) process for the printing and dyeing wastewater (PDW), the effects of Ce addition on performance, mechanism and kinetics of the catalyst were investigated. The Ce addition increases the Brunauer-Emmett-Teller (BET) surface area and pore volume of the catalyst and makes the active components uniformly distributed on the catalyst surface. Formation of a stable CuAl2O4 solid solution by anchoring Cu onto the γ-Al2O3 crystal lattice leads to a significant decrease in metal leaching of the Ce-modified catalyst. The proportion of lattice oxygen in the catalyst substantially increases and the apparent activation energy of Cu-O/γ-Al2O3 catalyst decreases owing to Ce addition. Therefore, the catalytic activity and stability of the Ce-modified catalyst are considerably improved. The scavengers experiments identify the active species existed in the CWAO reaction system, with the order of reactivity: h+ > O2•- > H2O2 > HO•. This novel Cu-Ce-O/γ-Al2O3 catalyst has great potential in applications for treatment of concentrated organic wastewater due to its superior catalytic activity and improved stability.
Dosimetric properties of new formulation of PRESAGE® with tin organometal catalyst: Development of sensitivity and stability to megavoltage energy.

PubMed

Khezerloo, Davood; Nedaie, Hassan Ali; Takavar, Abbas; Zirak, Alireza; Farhood, Bagher; Banaee, Nooshin; Alidokht, Eisa

2018-01-01

Tin-base catalyst is one of the widely used organometallic catalysts in polyurethane technology. The purpose of this study was to evaluate the effect of tin organometallic catalyst in the radiation response and radiological properties of a new formula of PRESAGE ® . In the study, two types of PRESAGE were fabricated. A very little amount of dibutyltindillaurate (DBTDL) (0.07% weight) was used as a catalyst in the fabrication of new PRESAGE (i.e., PRESAGE with catalyst), which components were: 93.93% weight polyurethane, 5% weight tetrachloride, and 1% weight leucomalachite green (LMG). For PRESAGE without catalyst, 94% weight polyurethane, 4% weight tetrachloride, and 2% weight LMG were used. Radiochromic response and postirradiation stability of PRESAGEs were determined. Also, radiological characteristics of PRESAGEs, such as mass density, electron density, mass attenuation coefficient, and mass stopping power in different photon energies were assessed and compared with water. The absorption peak of new PRESAGE compared to PRESAGE without catalyst was observed without change. Sensitivity of new PRESAGE was higher than PRESAGE without catalyst and its stability after the first 1 h was relatively constant. Also, Mass attenuation coefficient of new PRESAGE in energy ranges <0.1 MeV was 10% more than water, whereas the maximum difference of mass stopping power was only 3%. Tin organometallic catalyst in very low concentration can be used in fabrication of radiochromic polymer gel to achieve high sensitivity and stability as well as good radiological properties in the megavoltage photon beam.
Adsorption and bio-sorption of nickel ions and reuse for 2-chlorophenol catalytic ozonation oxidation degradation from water.

PubMed

Ma, Wei; Zong, Panpan; Cheng, Zihong; Wang, Baodong; Sun, Qi

2014-02-15

This work explored the preparation of an effective and low-cost catalyst and investigated its catalytic capacity for 2-chlorophenol ozonation oxidation degradation in wastewater by using an ozone oxidation batch reactor. The catalyst was directly prepared by the reuse of fly ash and sawdust after saturated adsorption of nickel ions from wastewater, which was proposed as an efficient and economic approach. The obtained catalyst was characterized by TGA, BET, FTIR, XRD, and SEM, the results showed that fly ash as the basic framework has high specific surface area and the addition of sawdust as the porogen agent could improve the pore structure of the catalyst. The adsorption of nickel ions by fly ash and sawdust from aqueous solution was also investigated in this study. The results obtained from the experiments indicated that adsorption of nickel ions by fly ash and biomass sawdust could be well described by Langmuir isotherm model and pseudo second order kinetic model. The catalytic performance of catalyst was studied in terms of the effect of time, liquid-solid ratio and pH on 2-chlorophenol ozonation degradation. It was found that the catalyst could effectively improve the ozonation reaction rate at pH=7 with a 2:1 liquid-solid ratio. The kinetic study demonstrated that the reaction followed the first order model, and the rate constant increased 267% (0.03-0.1 min(-1)) of 2-chlorophenol ozonation degradation with 5 mmol/L concentration at pH=7.0 compared with ozonation alone. Copyright © 2013 Elsevier B.V. All rights reserved.
Easy solid-phase synthesis of pH-insensitive heterogeneous CNTs/FeS Fenton-like catalyst for the removal of antibiotics from aqueous solution.

PubMed

Ma, Jie; Yang, Mingxuan; Yu, Fei; Chen, Junhong

2015-04-15

We report a facile solid method to synthesize efficient carbon-based Fenton-like catalyst (CNTs/FeS) using as-prepared carbon nanotubes (APCNTs), which makes full use of the iron nanoparticles in APCNTs without needless purification. Furthermore, the CNTs/FeS was characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), thermogravimetric (TG) and other analysis techniques, and then the CNTs/FeS was used as a Fenton-like catalyst for removing ciprofloxacin from aqueous solution. Response Surface Methodology (RSM) was applied to find the effect of the reaction parameter and the optimum operating condition. Results shows the catalytic reaction had better suitability than previous studies in a wide range of pH values (pH 3-8) and the Fenton-like catalyst CNTs/FeS exhibits good catalytic activity for removing of antibiotic, which be attributed to the synergistic effect of adsorption-advanced oxidation and significantly improves efficiency of advanced oxidation. More importantly, the CNTs/FeS catalyst exhibit good regeneration performance and retains a high catalytic capacity (>75%) even after four reaction cycles. The catalytic mechanism were also studied further, the removal mechanism of ciprofloxacin by a CNTs/FeS heterogeneous Fenton-like process primarily involves three removal pathways occurring simultaneously: (a) adsorption removal by CNTs, (b) Fenton-like degradation catalyzed by FeS, (c) catalytic degradation by CNTs catalyst. And these actions also have synergistic effects for ciprofloxacin removal. Copyright © 2014 Elsevier Inc. All rights reserved.
Catalyst system comprising a first catalyst system tethered to a supported catalyst

DOEpatents

Angelici, Robert J.; Gao, Hanrong

1998-08-04

The present invention provides new catalyst formats which comprise a supported catalyst tethered to a second and different catalyst by a suitable tethering ligand. A preferred system comprises a heterogeneous supported metal catalyst tethered to a homogeneous catalyst. This combination of homogeneous and heterogeneous catalysts has a sufficient lifetime and unusually high catalytic activity in arene hydrogenations, and potentially many other reactions as well, including, but not limited to hydroformylation, hydrosilation, olefin oxidation, isomerization, hydrocyanation, olefin metathesis, olefin polymerization, carbonylation, enantioselective catalysis and photoduplication. These catalysts are easily separated from the products, and can be reused repeatedly, making these systems very economical.
Catalyst system comprising a first catalyst system tethered to a supported catalyst

DOEpatents

Angelici, R.J.; Gao, H.

1998-08-04

The present invention provides new catalyst formats which comprise a supported catalyst tethered to a second and different catalyst by a suitable tethering ligand. A preferred system comprises a heterogeneous supported metal catalyst tethered to a homogeneous catalyst. This combination of homogeneous and heterogeneous catalysts has a sufficient lifetime and unusually high catalytic activity in arene hydrogenations, and potentially many other reactions as well, including, but not limited to hydroformylation, hydrosilication, olefin oxidation, isomerization, hydrocyanidation, olefin metathesis, olefin polymerization, carbonylation, enantioselective catalysis and photoduplication. These catalysts are easily separated from the products, and can be reused repeatedly, making these systems very economical. 2 figs.
CeO2 nanocubes-graphene oxide as durable and highly active catalyst support for proton exchange membrane fuel cell

PubMed Central

Lei, M.; Wang, Z. B.; Li, J. S.; Tang, H. L.; Liu, W. J.; Wang, Y. G.

2014-01-01

Rapid degradation of cell performance still remains a significant challenge for proton exchange membrane fuel cell (PEMFC). In this work, we develop novel CeO2 nanocubes-graphene oxide nanocomposites as durable and highly active catalyst support for proton exchange membrane fuel cell. We show that the use of CeO2 as the radical scavenger in the catalysts remarkably improves the durability of the catalyst. The catalytic activity retention of Pt-graphene oxide-8 wt.% CeO2 nanocomposites reaches as high as 69% after 5000 CV-cycles at a high voltage range of 0.8–1.23 V, in contrast to 19% for that of the Pt-graphene oxide composites. The excellent durability of the Pt-CeO2 nanocubes-graphene oxide catalyst is attributed to the free radical scavenging activity of CeO2, which significantly slows down the chemical degradation of Nafion binder in catalytic layers, and then alleviates the decay of Pt catalysts, resulting in the excellent cycle life of Pt-CeO2-graphene oxide nanocomposite catalysts. Additionally, the performance of single cell assembled with Nafion 211 membrane and Pt-CeO2-graphene oxide catalysts with different CeO2 contents in the cathode as well as the Pt-C catalysts in the anode are also recorded and discussed in this study. PMID:25491655
CeO2 nanocubes-graphene oxide as durable and highly active catalyst support for proton exchange membrane fuel cell.

PubMed

Lei, M; Wang, Z B; Li, J S; Tang, H L; Liu, W J; Wang, Y G

2014-12-10

Rapid degradation of cell performance still remains a significant challenge for proton exchange membrane fuel cell (PEMFC). In this work, we develop novel CeO2 nanocubes-graphene oxide nanocomposites as durable and highly active catalyst support for proton exchange membrane fuel cell. We show that the use of CeO2 as the radical scavenger in the catalysts remarkably improves the durability of the catalyst. The catalytic activity retention of Pt-graphene oxide-8 wt.% CeO2 nanocomposites reaches as high as 69% after 5000 CV-cycles at a high voltage range of 0.8-1.23 V, in contrast to 19% for that of the Pt-graphene oxide composites. The excellent durability of the Pt-CeO2 nanocubes-graphene oxide catalyst is attributed to the free radical scavenging activity of CeO2, which significantly slows down the chemical degradation of Nafion binder in catalytic layers, and then alleviates the decay of Pt catalysts, resulting in the excellent cycle life of Pt-CeO2-graphene oxide nanocomposite catalysts. Additionally, the performance of single cell assembled with Nafion 211 membrane and Pt-CeO2-graphene oxide catalysts with different CeO2 contents in the cathode as well as the Pt-C catalysts in the anode are also recorded and discussed in this study.
CeO2 nanocubes-graphene oxide as durable and highly active catalyst support for proton exchange membrane fuel cell

NASA Astrophysics Data System (ADS)

Lei, M.; Wang, Z. B.; Li, J. S.; Tang, H. L.; Liu, W. J.; Wang, Y. G.

2014-12-01

Rapid degradation of cell performance still remains a significant challenge for proton exchange membrane fuel cell (PEMFC). In this work, we develop novel CeO2 nanocubes-graphene oxide nanocomposites as durable and highly active catalyst support for proton exchange membrane fuel cell. We show that the use of CeO2 as the radical scavenger in the catalysts remarkably improves the durability of the catalyst. The catalytic activity retention of Pt-graphene oxide-8 wt.% CeO2 nanocomposites reaches as high as 69% after 5000 CV-cycles at a high voltage range of 0.8-1.23 V, in contrast to 19% for that of the Pt-graphene oxide composites. The excellent durability of the Pt-CeO2 nanocubes-graphene oxide catalyst is attributed to the free radical scavenging activity of CeO2, which significantly slows down the chemical degradation of Nafion binder in catalytic layers, and then alleviates the decay of Pt catalysts, resulting in the excellent cycle life of Pt-CeO2-graphene oxide nanocomposite catalysts. Additionally, the performance of single cell assembled with Nafion 211 membrane and Pt-CeO2-graphene oxide catalysts with different CeO2 contents in the cathode as well as the Pt-C catalysts in the anode are also recorded and discussed in this study.
Co-production of hydrogen and carbon nanotubes on nickel foam via methane catalytic decomposition

NASA Astrophysics Data System (ADS)

Ping, Dan; Wang, Chaoxian; Dong, Xinfa; Dong, Yingchao

2016-04-01

The co-production of COx-free hydrogen and carbon nanotubes (CNTs) was achieved on 3-dimensional (3D) macroporous nickel foam (NF) via methane catalytic decomposition (MCD) over nano-Ni catalysts using chemical vapor deposition (CVD) technique. By a simple coating of a NiO-Al2O3 binary mixture sol followed by a drying-calcination-reduction treatment, NF supported composite catalysts (denoted as NiyAlOx/NF) with Al2O3 transition-layer incorporated with well-dispersed nano-Ni catalysts were successfully prepared. The effects of Ni loading, calcination temperature and reaction temperature on the performance for simultaneous production of COx-free hydrogen and CNTs were investigated in detail. Catalysts before and after MCD were characterized by XRD, TPR, SEM, TEM, TG and Raman spectroscopy technology. Results show that increasing Ni loading, lowering calcination temperature and optimizing MCD reaction temperature resulted in high production efficiency of COx-free H2 and carbon, but broader diameter distribution of CNTs. Through detailed parameter optimization, the catalyst with a Ni/Al molar ratio of 0.1, calcination temperature of 550 °C and MCD temperature of 650 °C was favorable to simultaneously produce COx-free hydrogen with a growth rate as high as 10.3% and CNTs with uniform size on NF.
Advancing Fenton and photo-Fenton water treatment through the catalyst design.

PubMed

Vorontsov, Alexander V

2018-04-20

The review is devoted to modern Fenton, photo-Fenton, as well as Fenton-like and photo-Fenton-like reactions with participation of iron species in liquid phase and as heterogeneous catalysts. Mechanisms of these reactions were considered that include hydroxyl radical and oxoferryl species as the reactive intermediates. The barriers in the way of application of these reactions to wastewater treatment were discussed. The following fundamental problems need further research efforts: inclusion of more mechanism steps and quantum calculations of all rate constants lacking in the literature, checking the outer sphere electron transfer contribution, determination of the causes for the key changes in the homogeneous Fenton reaction mechanism with a change in the reagents concentration. The key advances for Fenton reactions implementation for the water treatment are related to tremendous hydrodynamical effects on the catalytic activity, design of ligands for high rate and completeness of mineralization in short time, and design of highly active heterogeneous catalysts. While both homogeneous and heterogeneous Fenton and photo-Fenton systems are open for further improvements, heterogeneous photo-Fenton systems are most promising for practical applications because of the inherent higher catalyst stability. Modern methods of quantum chemistry are expected to play a continuously increasing role in development of such catalysts. Copyright © 2018 Elsevier B.V. All rights reserved.
Performance enhancement of iron-chromium redox flow batteries by employing interdigitated flow fields

NASA Astrophysics Data System (ADS)

Zeng, Y. K.; Zhou, X. L.; Zeng, L.; Yan, X. H.; Zhao, T. S.

2016-09-01

The catalyst for the negative electrode of iron-chromium redox flow batteries (ICRFBs) is commonly prepared by adding a small amount of Bi3+ ions in the electrolyte and synchronously electrodepositing metallic particles onto the electrode surface at the beginning of charge process. Achieving a uniform catalyst distribution in the porous electrode, which is closely related to the flow field design, is critically important to improve the ICRFB performance. In this work, the effects of flow field designs on catalyst electrodeposition and battery performance are investigated. It is found that compared to the serpentine flow field (SFF) design, the interdigitated flow field (IFF) forces the electrolyte through the porous electrode between the neighboring channels and enhances species transport during the processes of both the catalyst electrodeposition and iron/chromium redox reactions, thus enabling a more uniform catalyst distribution and higher mass transport limitation. It is further demonstrated that the energy efficiency of the ICRFB with the IFF reaches 80.7% at a high current density (320 mA cm-2), which is 8.2% higher than that of the ICRFB with the SFF. With such a high performance and intrinsically low-cost active materials, the ICRFB with the IFF offers a great promise for large-scale energy storage.
Highly Durable Supportless Pt Hollow Spheres Designed for Enhanced Oxygen Transport in Cathode Catalyst Layers of Proton Exchange Membrane Fuel Cells.

PubMed

Dogan, Didem C; Cho, Seonghun; Hwang, Sun-Mi; Kim, Young-Min; Guim, Hwanuk; Yang, Tae-Hyun; Park, Seok-Hee; Park, Gu-Gon; Yim, Sung-Dae

2016-10-10

Supportless Pt catalysts have several advantages over conventional carbon-supported Pt catalysts in that they are not susceptible to carbon corrosion. However, the need for high Pt loadings in membrane electrode assemblies (MEAs) to achieve state-of-the-art fuel cell performance has limited their application in proton exchange membrane fuel cells. Herein, we report a new approach to the design of a supportless Pt catalyst in terms of catalyst layer architecture, which is crucial for fuel cell performance as it affects water management and oxygen transport in the catalyst layers. Large Pt hollow spheres (PtHSs) 100 nm in size were designed and prepared using a carbon template method. Despite their large size, the unique structure of the PtHSs, which are composed of a thin-layered shell of Pt nanoparticles (ca. 7 nm thick), exhibited a high surface area comparable to that of commercial Pt black (PtB). The PtHS structure also exhibited twice the durability of PtB after 2000 potential cycles (0-1.3 V, 50 mV/s). A MEA fabricated with PtHSs showed significant improvement in fuel cell performance compared to PtB-based MEAs at high current densities (>800 mA/cm 2 ). This was mainly due to the 2.7 times lower mass transport resistance in the PtHS-based catalyst layers compared to that in PtB, owing to the formation of macropores between the PtHSs and high porosity (90%) in the PtHS catalyst layers. The present study demonstrates a successful example of catalyst design in terms of catalyst layer architecture, which may be applied to a real fuel cell system.
Catalysts and process for liquid hydrocarbon fuel production

DOEpatents

White, Mark G; Liu, Shetian

2014-12-09

The present invention provides a novel process and system in which a mixture of carbon monoxide and hydrogen synthesis gas, or syngas, is converted into hydrocarbon mixtures composed of high quality gasoline components, aromatic compounds, and lower molecular weight gaseous olefins in one reactor or step. The invention utilizes a novel molybdenum-zeolite catalyst in high pressure hydrogen for conversion, as well as a novel rhenium-zeolite catalyst in place of the molybdenum-zeolite catalyst, and provides for use of the novel catalysts in the process and system of the invention.
Pt and PtRu catalyst bilayers increase efficiencies for ethanol oxidation in proton exchange membrane electrolysis and fuel cells

NASA Astrophysics Data System (ADS)

Altarawneh, Rakan M.; Pickup, Peter G.

2017-10-01

Polarization curves, product distributions, and reaction stoichiometries have been measured for the oxidation of ethanol at anodes consisting of Pt and PtRu bilayers and a homogeneous mixture of the two catalysts. These anode structures all show synergies between the two catalysts that can be attributed to the oxidation of acetaldehyde produced at the PtRu catalyst by the Pt catalyst. The use of a PtRu layer over a Pt layer produces the strongest effect, with higher currents than a Pt on PtRu bilayer, mixed layer, or either catalyst alone, except for Pt at high potentials. Reaction stoichiometries (average number of electrons transferred per ethanol molecule) were closer to the values for Pt alone for both of the bilayer configurations but much lower for PtRu and mixed anodes. Although Pt alone would provide the highest overall fuel cell efficiency at low power densities, the PtRu on Pt bilayer would provide higher power densities without a significant loss of efficiency. The origin of the synergy between the Pt and PtRu catalysts was elucidated by separation of the total current into the individual components for generation of carbon dioxide and the acetaldehyde and acetic acid byproducts.

Investigation of Mixed Oxide Catalysts for NO Oxidation

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

Szanyi, Janos; Karim, Ayman M.; Pederson, Larry R.

2014-12-09

The oxidation of engine-generated NO to NO2 is an important step in the reduction of NOx in lean engine exhaust because NO2 is required for the performance of the LNT technology [2], and it enhances the activities of ammonia selective catalytic reduction (SCR) catalysts [1]. In particular, for SCR catalysts an NO:NO2 ratio of 1:1 is most effective for NOx reduction, whereas for LNT catalysts, NO must be oxidized to NO2 before adsorption on the storage components. However, NO2 typically constitutes less than 10% of NOx in lean exhaust, so catalytic oxidation of NO is essential. Platinum has been foundmore » to be especially active for NO oxidation, and is widely used in DOC and LNT catalysts. However, because of the high cost and poor thermal durability of Pt-based catalysts, there is substantial interest in the development of alternatives. The objective of this project, in collaboration with partner General Motors, is to develop mixed metal oxide catalysts for NO oxidation, enabling lower precious metal usage in emission control systems. [1] M. Koebel, G. Madia, and M. Elsener, Catalysis Today 73, 239 (2002). [2] C. H. Kim, G. S. Qi, K. Dahlberg, and W. Li, Science 327, 1624 (2010).« less
Lignin Depolymerization with Nitrate-Intercalated Hydrotalcite Catalysts

DOE PAGES

Kruger, Jacob S.; Cleveland, Nicholas S.; Zhang, Shuting; ...

2016-01-13

Hydrotalcites (HTCs) exhibit multiple adjustable parameters to tune catalytic activity, including interlayer anion composition, metal hydroxide layer composition, and catalyst preparation methods. Here in this paper, we report the influence of several of these parameters on β-O-4 bond scission in a lignin model dimer, 2-phenoxy-1-phenethanol (PE), to yield phenol and acetophenone. We find that the presence of both basic and NO 3– anions in the interlayer increases the catalyst activity by 2–3-fold. In contrast, other anions or transition metals do not enhance catalytic activity in comparison to blank HTC. The catalyst is not active for C–C bond cleavage on ligninmore » model dimers and has no effect on dimers without an α-OH group. Most importantly, the catalyst is highly active in the depolymerization of two process-relevant lignin substrates, producing a significant amount of low-molecular-weight aromatic species. The catalyst can be recycled until the NO 3– anions are depleted, after which the activity can be restored by replenishing the NO 3– reservoir and regenerating the hydrated HTC structure. These results demonstrate a route to selective lignin depolymerization in a heterogeneous system with an inexpensive, earth-abundant, commercially relevant, and easily regenerated catalyst.« less
Mechanism of Copper(I)/TEMPO-Catalyzed Aerobic Alcohol Oxidation

PubMed Central

Hoover, Jessica M.; Ryland, Bradford L.; Stahl, Shannon S.

2013-01-01

Homogeneous Cu/TEMPO catalyst systems (TEMPO = 2,2,6,6-tetramethylpiperidine-N-oxyl) have emerged as some of the most versatile and practical catalysts for aerobic alcohol oxidation. Recently, we disclosed a (bpy)CuI/TEMPO/NMI catalyst system (NMI = N-methylimidazole) that exhibits fast rates and high selectivities, even with unactivated aliphatic alcohols. Here, we present a mechanistic investigation of this catalyst system, in which we compare the reactivity of benzylic and aliphatic alcohols. This work includes analysis of catalytic rates by gas-uptake and in situ IR kinetic methods and characterization of the catalyst speciation during the reaction by EPR and UV–visible spectroscopic methods. The data support a two-stage catalytic mechanism consisting of (1) “catalyst oxidation” in which CuI and TEMPO–H are oxidized by O2 via a binuclear Cu2O2 intermediate and (2) “substrate oxidation” mediated by CuII and the nitroxyl radical of TEMPO via a CuII-alkoxide intermediate. Catalytic rate laws, kinetic isotope effects, and spectroscopic data show that reactions of benzylic and aliphatic alcohols have different turnover-limiting steps. Catalyst oxidation by O2 is turnover limiting with benzylic alcohols, while numerous steps contribute to the turnover rate in the oxidation of aliphatic alcohols. PMID:23317450
Effect of carbon supports on RhRe bifunctional catalysts for selective hydrogenolysis of tetrahydropyran-2-methanol

DOE PAGES

Karanjkar, Pranav U.; Burt, Samuel P.; Chen, Xiaoli; ...

2016-09-12

Tetrahydropyran-2-methanol undergoes selective C–O–C hydrogenolysis to produce 1,6-hexanediol using a bifunctional RhRe (reducible metal with an oxophilic promoter) catalyst supported on Vulcan XC-72 carbon (VXC) with >90% selectivity. This RhRe/VXC catalyst is stable over 40 h of reaction in a continuous flow fixed bed reactor. The hydrogenolysis activity of RhRe/VXC is two orders-of-magnitude higher than that of RhRe supported on Norit Darco 12X40 activated carbon (NDC). STEM–EDS analysis reveals that, compared to the RhRe/VXC catalyst, the Re and Rh component metals are segregated on the surface of the low activity RhRe/NDC catalyst, suggesting that Rh and Re in close proximitymore » (“bimetallic” particles) are required for an active hydrogenolysis catalyst. Differences in metal distribution on the carbon surfaces are, in turn, linked to the properties of the carbons: NDC has both a higher surface area and surface oxygen content. Thus, the low areal density of Rh and Re precursors on the high area NDC and/or interactions of the precursors with its O functional groups may interfere with the formation of the bimetallic species required for an active catalyst.« less
The effect of electrospun nanofibers alignment on the synthesis of one-dimensional silicon carbide nanostructure

NASA Astrophysics Data System (ADS)

Hooshyar, Ali; Kokabi, Mehrdad

2018-01-01

One-dimensional silicon carbide (1D SiC) nanostructure has shown unusual properties such as extremely high strength, good flexibility, fracture toughness, wide band gap ( 3.2eV), large breakdown electric field strength (>2 MV cm-1, 10 times that of silicon), and inverse Hall-Petch effect. Because of these advantages, 1D SiC nanomaterial has gained extensive attention on the wide range of applications in microelectronics, optoelectronics, nanocomposites, and catalyst supports. Many methods have been used for the synthesis of 1D SiC nanostructures such as chemical vapor deposition, carbon nanotube-confined reaction, laser ablation, high-frequency induction heating, and arc discharge. However, these methods have also some shortcomings such as using catalyst, high-cost, low yield, irregular geometry and impurity. In this work, electrospinning was used to prepare aligned PVA/SiO2 composite nanofibers and the effect of fiber alignment on the production efficiency and quality of 1D SiC nanostructure was investigated. For this purpose, aligned electrospun nanofibers, as the desirable precursor, were put in a tube furnace and heated up to 1250°C under a controlled program in an inert atmosphere. Finally, the grown 1D SiC nanostructure product was characterized using SEM, XRD, and FTIR. The results confirmed the successful synthesis of pure crystalline1D β-SiC nanostructure with high yield, more regular, and metal catalyst-free.
Carbon-Supported Pd and PdFe Alloy Catalysts for Direct Methanol Fuel Cell Cathodes.

PubMed

Rivera Gavidia, Luis M; Sebastián, David; Pastor, Elena; Aricò, Antonino S; Baglio, Vincenzo

2017-05-25

Direct methanol fuel cells (DMFCs) are electrochemical devices that efficiently produce electricity and are characterized by a large flexibility for portable applications and high energy density. Methanol crossover is one of the main obstacles for DMFC commercialization, forcing the search for highly electro-active and methanol tolerant cathodes. In the present work, carbon-supported Pd and PdFe catalysts were synthesized using a sodium borohydride reduction method and physico-chemically characterized using transmission electron microscopy (TEM) and X-ray techniques such as photoelectron spectroscopy (XPS), diffraction (XRD) and energy dispersive spectroscopy (EDX). The catalysts were investigated as DMFC cathodes operating at different methanol concentrations (up to 10 M) and temperatures (60 °C and 90 °C). The cell based on PdFe/C cathode presented the best performance, achieving a maximum power density of 37.5 mW·cm -2 at 90 °C with 10 M methanol, higher than supported Pd and Pt commercial catalysts, demonstrating that Fe addition yields structural changes to Pd crystal lattice that reduce the crossover effects in DMFC operation.
Carbon-Supported Pd and PdFe Alloy Catalysts for Direct Methanol Fuel Cell Cathodes

PubMed Central

Rivera Gavidia, Luis M.; Sebastián, David; Pastor, Elena; Aricò, Antonino S.; Baglio, Vincenzo

2017-01-01

Direct methanol fuel cells (DMFCs) are electrochemical devices that efficiently produce electricity and are characterized by a large flexibility for portable applications and high energy density. Methanol crossover is one of the main obstacles for DMFC commercialization, forcing the search for highly electro-active and methanol tolerant cathodes. In the present work, carbon-supported Pd and PdFe catalysts were synthesized using a sodium borohydride reduction method and physico-chemically characterized using transmission electron microscopy (TEM) and X-ray techniques such as photoelectron spectroscopy (XPS), diffraction (XRD) and energy dispersive spectroscopy (EDX). The catalysts were investigated as DMFC cathodes operating at different methanol concentrations (up to 10 M) and temperatures (60 °C and 90 °C). The cell based on PdFe/C cathode presented the best performance, achieving a maximum power density of 37.5 mW·cm−2 at 90 °C with 10 M methanol, higher than supported Pd and Pt commercial catalysts, demonstrating that Fe addition yields structural changes to Pd crystal lattice that reduce the crossover effects in DMFC operation. PMID:28772937
Self-Supported Mesostructured Pt-Based Bimetallic Nanospheres Containing an Intermetallic Phase as Ultrastable Oxygen Reduction Electrocatalysts.

PubMed

Kim, Ho Young; Cho, Seonghun; Sa, Young Jin; Hwang, Sun-Mi; Park, Gu-Gon; Shin, Tae Joo; Jeong, Hu Young; Yim, Sung-Dae; Joo, Sang Hoon

2016-10-01

Developing highly active and stable cathode catalysts is of pivotal importance for proton exchange membrane fuel cells (PEMFCs). While carbon-supported nanostructured Pt-based catalysts have so far been the most active cathode catalysts, their durability and single-cell performance are yet to be improved. Herein, self-supported mesostructured Pt-based bimetallic (Meso-PtM; M = Ni, Fe, Co, Cu) nanospheres containing an intermetallic phase are reported, which can combine the beneficial effects of transition metals (M), an intermetallic phase, a 3D interconnected framework, and a mesoporous structure. Meso-PtM nanospheres show enhanced oxygen reduction reaction (ORR) activity, compared to Pt black and Pt/C catalysts. Notably, Meso-PtNi containing an intermetallic phase exhibits ultrahigh stability, showing enhanced ORR activity even after 50 000 potential cycles, whereas Pt black and Pt/C undergo dramatic degradation. Importantly, Meso-PtNi with an intermetallic phase also demonstrated superior activity and durability when used in a PEMFC single-cell, with record-high initial mass and specific activities. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Novel windows for "solar commodities": a device for CO2 reduction using plasmonic catalyst activation.

PubMed

Navarrete, Alexander; Muñoz, Sergio; Sanz-Moral, Luis M; Brandner, Juergen J; Pfeifer, Peter; Martín, Ángel; Dittmeyer, Roland; Cocero, María J

2015-01-01

A novel plasmonic reactor concept is proposed and tested to work as a visible energy harvesting device while allowing reactions to transform CO2 to be carried out. Particularly the reverse water gas shift (RWGS) reaction has been tested as a means to introduce renewable energy into the economy. The development of the new reactor concept involved the synthesis of a new composite capable of plasmonic activation with light, the development of an impregnation method to create a single catalyst reactor entity, and finally the assembly of a reaction system to test the reaction. The composite developed was based on a Cu/ZnO catalyst dispersed into transparent aerogels. This allows efficient light transmission and a high surface area for the catalyst. An effective yet simple impregnation method was developed that allowed introduction of the composites into glass microchannels. The activation of the reaction was made using LEDs that covered all the sides of the reactor allowing a high power delivery. The results of the reaction show a stable process capable of low temperature transformations.
Recent developments of nano-structured materials as the catalysts for oxygen reduction reaction

NASA Astrophysics Data System (ADS)

Kang, SungYeon; Kim, HuiJung; Chung, Yong-Ho

2018-04-01

Developments of high efficient materials for electrocatalyst are significant topics of numerous researches since a few decades. Recent global interests related with energy conversion and storage lead to the expansion of efforts to find cost-effective catalysts that can substitute conventional catalytic materials. Especially, in the field of fuel cell, novel materials for oxygen reduction reaction (ORR) have been noticed to overcome disadvantages of conventional platinum-based catalysts. Various approaching methods have been attempted to achieve low cost and high electrochemical activity comparable with Pt-based catalysts, including reducing Pt consumption by the formation of hybrid materials, Pt-based alloys, and not-Pt metal or carbon based materials. To enhance catalytic performance and stability, numerous methods such as structural modifications and complex formations with other functional materials are proposed, and they are basically based on well-defined and well-ordered catalytic active sites by exquisite control at nanoscale. In this review, we highlight the development of nano-structured catalytic materials for ORR based on recent findings, and discuss about an outlook for the direction of future researches.
Rational Design of Zirconium-doped Titania Photocatalysts with Synergistic Brønsted Acidity and Photoactivity.

PubMed

Ma, Runyuan; Wang, Liang; Zhang, Bingsen; Yi, Xianfeng; Zheng, Anmin; Deng, Feng; Yan, Xuhua; Pan, Shuxiang; Wei, Xiao; Wang, Kai-Xue; Su, Dang Sheng; Xiao, Feng-Shou

2016-10-06

The preparation of photocatalysts with high activities under visible-light illumination is challenging. We report the rational design and construction of a zirconium-doped anatase catalyst (S-Zr-TiO 2 ) with Brønsted acidity and photoactivity as an efficient catalyst for the degradation of phenol under visible light. Electron microscopy images demonstrate that the zirconium sites are uniformly distributed on the sub-10 nm anatase crystals. UV-visible spectrometry indicates that the S-Zr-TiO 2 is a visible-light-responsive catalyst with narrower band gap than conventional anatase. Pyridine-adsorption infrared and acetone-adsorption 13 C NMR spectra confirm the presence of Brønsted acidic sites on the S-Zr-TiO 2 sample. Interestingly, the S-Zr-TiO 2 catalyst exhibits high catalytic activity in the degradation of phenol under visible-light illumination, owing to a synergistic effect of the Brønsted acidity and photoactivity. Importantly, the S-Zr-TiO 2 shows good recyclability. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
A highly selective and stable ZnO-ZrO2 solid solution catalyst for CO2 hydrogenation to methanol

PubMed Central

Wang, Jijie; Li, Guanna; Li, Zelong; Tang, Chizhou; Feng, Zhaochi; An, Hongyu; Liu, Hailong; Liu, Taifeng; Li, Can

2017-01-01

Although methanol synthesis via CO hydrogenation has been industrialized, CO2 hydrogenation to methanol still confronts great obstacles of low methanol selectivity and poor stability, particularly for supported metal catalysts under industrial conditions. We report a binary metal oxide, ZnO-ZrO2 solid solution catalyst, which can achieve methanol selectivity of up to 86 to 91% with CO2 single-pass conversion of more than 10% under reaction conditions of 5.0 MPa, 24,000 ml/(g hour), H2/CO2 = 3:1 to 4:1, 320° to 315°C. Experimental and theoretical results indicate that the synergetic effect between Zn and Zr sites results in the excellent performance. The ZnO-ZrO2 solid solution catalyst shows high stability for at least 500 hours on stream and is also resistant to sintering at higher temperatures. Moreover, no deactivation is observed in the presence of 50 ppm SO2 or H2S in the reaction stream. PMID:28989964
Morphological effect of BiVO4 catalysts on degradation of aqueous paracetamol under visible light irradiation.

PubMed

Hu, Changying; Xu, Jie; Zhu, Yaqi; Chen, Acong; Bian, Zhaoyong; Wang, Hui

2016-09-01

Morphological effect of bismuth vanadate (BiVO4) on visible light-driven catalytic degradation of aqueous paracetamol was carefully investigated using four monoclinic BiVO4 catalysts. The catalysts with different morphologies were controllably prepared by a hydrothermal method without any additions. The prepared catalysts were fully characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and UV-Vis diffuse reflectance spectroscopy (DRS). Under the visible light irradiation, these catalysts with different morphology were investigated to degrade aqueous paracetamol contaminant. The degradation effects were evaluated based on the catalyst morphology, solution pH, initial paracetamol concentration, and catalyst dosage. Cube-like BiVO4 powders exhibited excellent photocatalytic performance. The optimal photocatalytic performance of the cube-like BiVO4 in degrading paracetamol was achieved.
Small-sized and contacting Pt-WC nanostructures on graphene as highly efficient anode catalysts for direct methanol fuel cells.

PubMed

Wang, Ruihong; Xie, Ying; Shi, Keying; Wang, Jianqiang; Tian, Chungui; Shen, Peikang; Fu, Honggang

2012-06-11

The synergistic effect between Pt and WC is beneficial for methanol electro-oxidation, and makes Pt-WC catalyst a promising anode candidate for the direct methanol fuel cell. This paper reports on the design and synthesis of small-sized and contacting Pt-WC nanostructures on graphene that bring the synergistic effect into full play. Firstly, DFT calculations show the existence of a strong covalent interaction between WC and graphene, which suggests great potential for anchoring WC on graphene with formation of small-sized, well-dispersed WC particles. The calculations also reveal that, when Pt attaches to the pre-existing WC/graphene hybrid, Pt particles preferentially grow on WC rather than graphene. Our experiments confirmed that highly disperse WC nanoparticles (ca. 5 nm) can indeed be anchored on graphene. Also, Pt particles 2-3 nm in size are well dispersed on WC/graphene hybrid and preferentially grow on WC grains, forming contacting Pt-WC nanostructures. These results are consistent with the theoretical findings. X-ray absorption fine structure spectroscopy further confirms the intimate contact between Pt and WC, and demonstrates that the presence of WC can facilitate the crystallinity of Pt particles. This new Pt-WC/graphene catalyst exhibits a high catalytic efficiency toward methanol oxidation, with a mass activity 1.98 and 4.52 times those of commercial PtRu/C and Pt/C catalysts, respectively. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Oxidation catalysts comprising metal exchanged hexaaluminate wherein the metal is Sr, Pd, La, and/or Mn

DOEpatents

Wickham, David [Boulder, CO; Cook, Ronald [Lakewood, CO

2008-10-28

The present invention provides metal-exchanged hexaaluminate catalysts that exhibit good catalytic activity and/or stability at high temperatures for extended periods with retention of activity as combustion catalysts, and more generally as oxidation catalysts, that make them eminently suitable for use in methane combustion, particularly for use in natural gas fired gas turbines. The hexaaluminate catalysts of this invention are of particular interest for methane combustion processes for minimization of the generation of undesired levels (less than about 10 ppm) of NOx species. Metal exchanged hexaaluminate oxidation catalysts are also useful for oxidation of volatile organic compounds (VOC), particularly hydrocarbons. Metal exchanged hexaaluminate oxidation catalysts are further useful for partial oxidation, particularly at high temperatures, of reduced species, particularly hydrocarbons (alkanes and alkenes).
Novel schemes for production of biodiesel and value-added co-products from microalgal oil using heterogeneous catalysts

NASA Astrophysics Data System (ADS)

Dong, Tao

Microalgae are promising sources of biofuels primarily because of their higher potential productivity compared to terrestrial biofuel crops. However, the production of liquid fuels from microalgae suffers from a lack of viable methods of extraction, conversion and fractionation of various components of the algal biomass. In this dissertation study, a rapid method was developed to accurately evaluate the biodiesel potential of microalgae biomass. The major advantage of this method is in situ fatty acid methyl ester (FAME) preparation directly from wet fresh microalgal and yeast biomass, without prior solvent extraction or dehydration. FAMEs were prepared by a sequential alkaline hydrolysis and acidic esterification process. This method can be used even with high amount of water in the biomass and is applicable to a vast range of microalgae and yeast species. A two-step in situ process was also investigated in this study to obtain a high FAME yield from microalgae biomass that had high free fatty acids (FFA) content. This process has the potential to reduce the production cost of microalgae-derived FAME and be more environmental compatible due to the higher FAME yield with reduced catalyst consumption. A cost-effective bio-char based catalyst was tested for the two-step biodiesel production. The results indicated that the bio-char catalyst was superior to commercial Amberly-15. A scalable chlorophyll remove process was also developed as a part of the system. The research resulted in a practical and cost-effective approach for producing biodiesel from crude microalgal oil. An integrated approach was explored in the fourth part of the study to produce biodiesel and fractionate high-value polyunsaturated fatty acid (PUFA). Zeolites were employed as the catalyst for selective esterification of fatty acids according to their chain length and degree of saturation. Low-value short chain FFA could be largely converted into FAME, while PUFA would remain unreacted due to steric hindrance. Both a high quality biodiesel and high-value PUFA could be obtained by employing this novel approach.
High Performance Fe- and N- Doped Carbon Catalyst with Graphene Structure for Oxygen Reduction

NASA Astrophysics Data System (ADS)

Peng, Hongliang; Mo, Zaiyong; Liao, Shijun; Liang, Huagen; Yang, Lijun; Luo, Fan; Song, Huiyu; Zhong, Yiliang; Zhang, Bingqing

2013-05-01

Proton exchange membrane fuel cells are promising candidates for a clean and efficient energy conversion in the future, the development of carbon based inexpensive non-precious metal ORR catalyst has becoming one of the most attractive topics in fuel cell field. Herein we report a Fe- and N- doped carbon catalyst Fe-PANI/C-Mela with graphene structure and the surface area up to 702 m2 g-1. In 0.1 M HClO4 electrolyte, the ORR onset potential for the catalyst is high up to 0.98 V, and the half-wave potential is only 60 mV less than that of the Pt/C catalyst (Loadings: 51 μg Pt cm-2). The catalyst shows high stability after 10,000 cyclic voltammetry cycles. A membrane electrode assembly made with the catalyst as a cathode is tested in a H2-air single cell, the maximum power density reached ~0.33 W cm2 at 0.47 V.
Simple-Cubic Carbon Frameworks with Atomically Dispersed Iron Dopants toward High-Efficiency Oxygen Reduction.

PubMed

Wang, Biwei; Wang, Xinxia; Zou, Jinxiang; Yan, Yancui; Xie, Songhai; Hu, Guangzhi; Li, Yanguang; Dong, Angang

2017-03-08

Iron and nitrogen codoped carbons (Fe-N-C) have attracted increasingly greater attention as electrocatalysts for oxygen reduction reaction (ORR). Although challenging, the synthesis of Fe-N-C catalysts with highly dispersed and fully exposed active sites is of critical importance for improving the ORR activity. Here, we report a new type of graphitic Fe-N-C catalysts featuring numerous Fe single atoms anchored on a three-dimensional simple-cubic carbon framework. The Fe-N-C catalyst, derived from self-assembled Fe 3 O 4 nanocube superlattices, was prepared by in situ ligand carbonization followed by acid etching and ammonia activation. Benefiting from its homogeneously dispersed and fully accessible active sites, highly graphitic nature, and enhanced mass transport, our Fe-N-C catalyst outperformed Pt/C and many previously reported Fe-N-C catalysts for ORR. Furthermore, when used for constructing the cathode for zinc-air batteries, our Fe-N-C catalyst exhibited current and power densities comparable to those of the state-of-the-art Pt/C catalyst.
A molecular catalyst for water oxidation that binds to metal oxide surfaces

PubMed Central

Sheehan, Stafford W.; Thomsen, Julianne M.; Hintermair, Ulrich; Crabtree, Robert H.; Brudvig, Gary W.; Schmuttenmaer, Charles A.

2015-01-01

Molecular catalysts are known for their high activity and tunability, but their solubility and limited stability often restrict their use in practical applications. Here we describe how a molecular iridium catalyst for water oxidation directly and robustly binds to oxide surfaces without the need for any external stimulus or additional linking groups. On conductive electrode surfaces, this heterogenized molecular catalyst oxidizes water with low overpotential, high turnover frequency and minimal degradation. Spectroscopic and electrochemical studies show that it does not decompose into iridium oxide, thus preserving its molecular identity, and that it is capable of sustaining high activity towards water oxidation with stability comparable to state-of-the-art bulk metal oxide catalysts. PMID:25757425
Magnetic nanoparticle supported phosphotungstic acid: An efficient catalyst for the synthesis of xanthene derivatives

NASA Astrophysics Data System (ADS)

Patel, Nipun; Katheriya, Deepak; Dadhania, Harsh; Dadhania, Abhishek

2018-05-01

Magnetic nanoparticle supported phosphotungstic acid (Fe3O4@SiO2-HPW) was applied as a highly efficient catalyst for the synthesis of 14H-dibenzoxanthene derivatives via condensation reaction of 2-naphthol and aryl aldehydes. The catalyst was found highly efficient for the synthesis of xanthene derivatives under solvent free condition. The catalyst showed high activity and stability during the reaction and provided excellent yield of the corresponding products in short reaction time. All the synthesized compounds were characterized through FT-IR, 1H-NMR and 13C-NMR spectroscopic techniques. Furthermore, the catalyst is magnetically recoverable and can be reused several times without significant loss of its catalytic activity.

Researching the Possibility of Creating Highly Effective Catalysts for the Thermochemical Heat Regeneration and Hydrocarbon Reforming

DTIC Science & Technology

2006-11-01

PHYSICAL PROPERTIES OF THE PLASMA SPRAYING PROCESS The sprayed -on material is formed by gradual deposition of separate discretely solidifying with great... deposition processes and their ecological purity. Essentially, the method of ion-plasma spraying is evaporation of a metal (or alloy ) atoms from the...29 5.1 PHYSICAL PROPERTIES OF THE PLASMA SPRAYING PROCESS ...................34 6. CATALYST SUPPORTERS FOR THE 1ST STAGE OF
Nitrogen-doped graphene/CoNi alloy encased within bamboo-like carbon nanotube hybrids as cathode catalysts in microbial fuel cells

NASA Astrophysics Data System (ADS)

Hou, Yang; Yuan, Heyang; Wen, Zhenhai; Cui, Shumao; Guo, Xiaoru; He, Zhen; Chen, Junhong

2016-03-01

Cost-effective catalysts are of key importance to the successful deployment of microbial fuel cells (MFCs) for electricity generation from organic wastes. Herein, a novel catalyst prepared by one-step synthesis strategy is reported. The catalyst features N-doped bamboo-like carbon nanotube (BCNT) in which CoNi-alloy is encapsulated at the end and/or the middle section of the tube with many graphene layers inside inner cavities of BCNT (N-G@CoNi/BCNT). The prepared N-G@CoNi/BCNT exhibits a high oxygen reduction reaction (ORR) activity with an early onset potential of 0.06 V vs. Ag/AgCl and a comparable exchange current density to that of commercial Pt/C. The excellent catalytic activity is further evidenced by a high electron transfer number of 3.63. When being applied in MFCs, the N-G@CoNi/BCNT yields an average current density of 6.7 A m-2, slightly lower than that of Pt/C but with a less mass transfer potential loss. The cost of the N-G@CoNi/BCNT for constructing a 1-m2 cathode electrode is 200 times lower than that of Pt/C. With such a competitive price and excellent electrocatalytic-activity resulting from its unique morphology, CoNi-alloy/nitrogen dopants, considerable specific surface area, and carbon-coated alloy/graphene hybridization, the present catalyst is a promising candidate for ORR catalysts in MFCs for energy recovery from wastes.
Fast Optimization of LiMgMnOx/La2O3 Catalysts for the Oxidative Coupling of Methane.

PubMed

Li, Zhinian; He, Lei; Wang, Shenliang; Yi, Wuzhong; Zou, Shihui; Xiao, Liping; Fan, Jie

2017-01-09

The development of efficient catalyst for oxidative coupling of methane (OCM) reaction represents a grand challenge in direct conversion of methane into other useful products. Here, we reported that a newly developed combinatorial approach can be used for ultrafast optimization of La 2 O 3 -based multicomponent metal oxide catalysts in OCM reaction. This new approach integrated inkjet printing assisted synthesis (IJP-A) with multidimensional group testing strategy (m-GT) tactfully takes the place of conventionally high-throughput synthesis-and-screen experiment. Just within a week, 2048 formulated LiMgMnO x -La 2 O 3 catalysts in a 64·8·8·8·8 = 262 144 compositional space were fabricated by IJP-A in a four-round synthesis-and-screen process, and an optimized formulation has been successfully identified through only 4·8 = 32 times of tests via m-GT screening strategy. The screening process identifies the most promising ternary composition region is Li 0-0.48 Mg 0-6.54 Mn 0-0.62 -La 100 O x with an external C 2 yield of 10.87% at 700 °C. The yield of C 2 is two times as high as the pure nano-La 2 O 3 . The good performance of the optimized catalyst formulation has been validated by the manual preparation, which further prove the effectiveness of the new combinatorial methodology in fast discovery of heterogeneous catalyst.
Method of treating intermetallic alloy hydrogenation/oxidation catalysts for improved impurity poisoning resistance, regeneration and increased activity

DOEpatents

Wright, Randy B.

1992-01-01

Alternate, successive high temperature oxidation and reduction treatments, in either order, of intermetallic alloy hydrogenation and intermetallic alloy oxidation catalysts unexpectedly improves the impurity poisoning resistance, regeneration capacity and/or activity of the catalysts. The particular alloy, and the final high temperature treatment given alloy (oxidation or reduction) will be chosen to correspond to the function of the catalyst (oxidation or hydrogenation).
Silica-supported, single-site titanium catalysts for olefin epoxidation. A molecular precursor strategy for control of catalyst structure.

PubMed

Jarupatrakorn, Jonggol; Don Tilley, T

2002-07-17

A molecular precursor approach involving simple grafting procedures was used to produce site-isolated titanium-supported epoxidation catalysts of high activity and selectivity. The tris(tert-butoxy)siloxy titanium complexes Ti[OSi(O(t)Bu)(3)](4) (TiSi4), ((i)PrO)Ti[OSi(O(t)Bu)(3)](3) (TiSi3), and ((t)BuO)(3)TiOSi(O(t)Bu)(3) (TiSi) react with the hydroxyl groups of amorphous Aerosil, mesoporous MCM-41, and SBA-15 via loss of HO(t)Bu and/or HOSi(O(t)Bu)(3) and introduction of titanium species onto the silica surface. Powder X-ray diffraction, nitrogen adsorption/desorption, infrared, and diffuse reflectance ultraviolet spectroscopies were used to investigate the structures and chemical natures of the surface-bound titanium species. The titanium species exist mainly in isolated, tetrahedral coordination environments. Increasing the number of siloxide ligands in the molecular precursor decreases the amount of titanium that can be introduced this way, but also enhances the catalytic activity and selectivity for the epoxidation of cyclohexene with cumene hydroperoxide as oxidant. In addition, the high surface area mesoporous silicas (MCM-41 and SBA-15) are more effective than amorphous silica as supports for these catalysts. Supporting TiSi3 on the SBA-15 affords highly active cyclohexene epoxidation catalysts (0.25-1.77 wt % Ti loading) that provide turnover frequencies (TOFs) of 500-1500 h(-1) after 1 h (TOFs are reduced by about half after calcination). These results demonstrate that oxygen-rich siloxide complexes of titanium are useful as precursors to supported epoxidation catalysts.
Electrocatalytic Water Oxidation by a Homogeneous Copper Catalyst Disfavors Single-Site Mechanisms.

PubMed

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.
Molybdenum Carbides, Active and In Situ Regenerable Catalysts in Hydroprocessing of Fast Pyrolysis Bio-Oil

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

Choi, Jae-Soon; Zacher, Alan H.; Wang, Huamin

We assessed molybdenum carbides as a potential catalyst for fast pyrolysis bio-oil hydroprocessing. Currently, high catalyst cost, short catalyst lifetime, and lack of effective regeneration methods are hampering the development of this otherwise attractive renewable hydrocarbon technology. A series of metal-doped bulk Mo carbides were synthesized, characterized and evaluated in sequential low-temperature stabilization and high-temperature deoxygenation of a pine-derived bio-oil. During a typical 60-h run, Mo carbides were capable of upgrading raw bio-oil to a level suitable for direct insertion into the current hydrocarbon infrastructure with residual oxygen content and total acid number of upgraded oils below 2 wt% andmore » 0.01 mg KOH g-1, respectively. The performance was shown to be sensitive to the type of metal dopant, Ni-doped Mo carbides outperforming Co-, Cu-, or Ca-doped counterparts; a higher Ni loading led to a superior catalytic performance. No bulk oxidation or other significant structural changes were observed. Besides the structural robustness, another attractive property of Mo carbides was in situ regenerability. The effectiveness of regeneration was demonstrated by successfully carrying out four consecutive 60-h runs with a reductive decoking between two adjacent runs. These results strongly suggest that Mo carbides are promising catalytic materials which could lead to a significant cost reduction in hydroprocessing bio-oils. This paper highlights areas for future research which will be needed to further understand carbide structure-function relationships and help design practical bio-oil upgrading catalysts based on Mo carbides.« less
Systematic Identification of Promoters for Methane Oxidation Catalysts Using Size- and Composition-Controlled Pd-Based Bimetallic Nanocrystals.

PubMed

Willis, Joshua J; Goodman, Emmett D; Wu, Liheng; Riscoe, Andrew R; Martins, Pedro; Tassone, Christopher J; Cargnello, Matteo

2017-08-30

Promoters enhance the performance of catalytic active phases by increasing rates, stability, and/or selectivity. The process of identifying promoters is in most cases empirical and relies on testing a broad range of catalysts prepared with the random deposition of active and promoter phases, typically with no fine control over their localization. This issue is particularly relevant in supported bimetallic systems, where two metals are codeposited onto high-surface area materials. We here report the use of colloidal bimetallic nanocrystals to produce catalysts where the active and promoter phases are colocalized to a fine extent. This strategy enables a systematic approach to study the promotional effects of several transition metals on palladium catalysts for methane oxidation. In order to achieve these goals, we demonstrate a single synthetic protocol to obtain uniform palladium-based bimetallic nanocrystals (PdM, M = V, Mn, Fe, Co, Ni, Zn, Sn, and potentially extendable to other metal combinations) with a wide variety of compositions and sizes based on high-temperature thermal decomposition of readily available precursors. Once the nanocrystals are supported onto oxide materials, thermal treatments in air cause segregation of the base metal oxide phase in close proximity to the Pd phase. We demonstrate that some metals (Fe, Co, and Sn) inhibit the sintering of the active Pd metal phase, while others (Ni and Zn) increase its intrinsic activity compared to a monometallic Pd catalyst. This procedure can be generalized to systematically investigate the promotional effects of metal and metal oxide phases for a variety of active metal-promoter combinations and catalytic reactions.
Design and application of sporopollenin microcapsule supported palladium catalyst: Remarkably high turnover frequency and reusability in catalysis of biaryls.

PubMed

Baran, Talat; Sargin, Idris; Kaya, Murat; Menteş, Ayfer; Ceter, Talip

2017-01-15

Bio-based catalyst support materials with high thermal and structural stability are desired for catalysts systems requiring harsh conditions. In this study, a thermally stable palladium catalyst (up to 440°C) was designed from sporopollenin, which occurs naturally in the outer exine layer of pollens and is widely acknowledged as chemically very stable and inert biological material. Catalyst design procedure included (1) extraction of sporopollenin microcapsules from Betula pendula pollens (∼25μm), (2) amino-functionalisation of the microcapsules, (3) Schiff base modification and (4) preparation of Pd(II) catalyst. The catalytic activity of the sporopollenin microcapsule supported palladium catalyst was tested in catalysis of biaryls by following a fast, simple and green microwave-assisted method. We recorded outstanding turnover number (TON: 40,000) and frequency (TOF: 400,000) for the catalyst in Suzuki coupling reactions. The catalyst proved to be reusable at least in eight cycles. The catalyst can be suggested for different catalyst systems due to its thermal and structural durability, reusability, inertness to air and its eco-friendly nature. Copyright © 2016 Elsevier Inc. All rights reserved.
High hydrogen desorption properties of Mg-based nanocomposite at moderate temperatures: The effects of multiple catalysts in situ formed by adding nickel sulfides/graphene

NASA Astrophysics Data System (ADS)

Xie, Xiubo; Chen, Ming; Liu, Peng; Shang, Jiaxiang; Liu, Tong

2017-12-01

Nickel sulfides decorated reduced graphene oxide (rGO) has been produced by co-reducing Ni2+ and graphene oxide (GO), and is subsequently ball milled with Mg nanoparticles (NPs) produced by hydrogen plasma metal reaction (HPMR). The nickel sulfides of about 800 nm completely in situ change to MgS, Mg2Ni and Ni multiple catalysts after first hydrogenation/dehydrogenation process at 673 K. The Mg-5wt%NiS/rGO nanocomposite shows the highest hydrogen desorption kinetics and capacity properties, and the catalytic effect order of the additives is NiS/rGO, NiS and rGO. At 573 K, the Mg-NiS/rGO nanocomposite can quickly desorb 3.7 wt% H2 in 10 min and 4.5 wt% H2 in 60 min. The apparent hydrogen absorption and desorption activation energies of the Mg-5wt%NiS/rGO nanocomposite are decreased to 44.47 and 63.02 kJ mol-1, smaller than those of the Mg-5wt%rGO and Mg-5wt%NiS samples. The best hydrogen desorption properties of the Mg-5wt%NiS/rGO nanocomposite can be explained by the synergistic catalytic effects of the highly dispersed MgS, Mg2Ni and Ni catalysts on the rGO sheets, and the more nucleation sites between the catalysts, rGO sheets and Mg matrix.
Application of surface modified nano ferrite nickel in catalytic reaction (epoxidation of alkenes) and investigation on its antibacterial and antifungal activities.

PubMed

Golkhatmi, Faezeh Mahdinejad; Bahramian, Bahram; Mamarabadi, Mojtaba

2017-09-01

Newly, magnetic nanoparticles have extensively been used as alternative catalyst supports, in the view of their high surface area which results in high catalyst loading capacity, high dispersion, low toxicity, environmental preservation, distinguished stability, and suitable catalyst reusing. In the present study, the magnetite nanoparticles, NiFe 2 O 4 @Ag and NiFe 2 O 4 @Mo, were synthesized and characterized. The antimicrobial activities and catalytic properties of synthesized nanoparticles were tested afterwards. For synthetizing the nanoparticle NiFe 2 O 4 @Ag, silver ions were loaded onto the surface of the modified NiFe 2 O 4 and reduced to silver crystal by adding NaBH 4 . The antibacterial effects of NiFe 2 O 4 @Ag were examined against two species of soil and plant related bacteria named Bacillus subtilis (gram positive) and Pseudomonas syringae (gram negative), respectively. The antifungal activity of this nanoparticle was evaluated against two species of plant pathogenic fungi called Alternaria solani and Fusarium oxysporum. Biological results indicated that the synthesized material has shown an excellent antibacterial and antifungal activity against all examined bacteria and fungi so that, their growth were completely inhibited 24h after treatment with NiFe 2 O 4 @Ag. For the synthesis of a heterogeneous catalyst NiFe 2 O 4 @Mo, complex Mo(CO) 6 was loaded onto the surface of the modified NiFe 2 O 4 nanoparticle. This catalyst was found as an efficient catalyst for epoxidation of cis-cyclooctene and a wide variety of alkenes, including aromatic and aliphatic terminal ones using tert-butyl hydroperoxide as oxidant. This new heterogenized catalyst could easily be recovered by using a magnetic separator and reused four consecutive and loss only 13% of its catalytic activity. Copyright © 2017 Elsevier B.V. All rights reserved.
Methane combustion reactivity during the metal→metallic oxide transformation of Pd-Pt catalysts: Effect of oxygen pressure

NASA Astrophysics Data System (ADS)

Qi, Wenjie; Ran, Jingyu; Zhang, Zhien; Niu, Juntian; Zhang, Peng; Fu, Lijuan; Hu, Bo; Li, Qilai

2018-03-01

Density functional theory combined with kinetic models were used to probe different kinetics consequences by which methane activation on different oxygen chemical potential surfaces as oxygen pressure increased. The metallic oxide → metal transformation temperature of Pd-Pt catalysts increased with the increase of the Pd content or/and O2 pressure. The methane conversion rate on Pt catalyst increased and then decreased to a constant value when increasing the O2 pressure, and Pd catalyst showed a poor activity performance in the case of low O2 pressure. Moreover, its activity increased as the oxygen chemical potential for O2 pressure increased in the range of 2.5-10 KPa. For metal clusters, the Csbnd H bond and Odbnd O bond activation steps occurred predominantly on *-* site pairs. The methane conversion rate was determined by O2 pressure because the adsorbed O atoms were rapidly consumed by other adsorbed species in this kinetic regime. As the O2 pressure increased, the metallic active sites for methane activation were decreased and there was no longer lack of adsorbed O atoms, resulting in the decrease of the methane conversion rate. Furthermore, when the metallic surfaces were completely covered by adsorbed oxygen atoms at higher oxygen chemical potentials, Pt catalyst showed a poor activity due to a high Csbnd H bond activation barrier on O*sbnd O*. In the case of high O2 pressure, Pd atoms preferred to segregate to the active surface of Pd-Pt catalysts, leading to the formation of PdO surfaces. The increase of Pd segregation promoted a subsequent increase in active sites and methane conversion rate. The PdO was much more active than metallic and O* saturated surfaces for methane activation, inferred from the theory and experimental study. Pd-rich bimetallic catalyst (75% molar Pd) showed a dual high methane combustion activity on O2-poor and O2-rich conditions.
Role of flue gas components in mercury oxidation over TiO2 supported MnOx-CeO2 mixed-oxide at low temperature.

PubMed

Li, Hailong; Wu, Chang-Yu; Li, Ying; Li, Liqing; Zhao, Yongchun; Zhang, Junying

2012-12-01

MnO(x)-CeO(2) mixed-oxide supported on TiO(2) (Mn-Ce/Ti) was synthesized by an ultrasound-assisted impregnation method and employed to oxidize elemental mercury (Hg(0)) at 200°C in simulated coal combustion flue gas. Over 90% of Hg(0) oxidation was achieved on the Mn-Ce/Ti catalyst at 200°C under simulated flue gas representing those from burning low-rank coals with a high gas hourly space velocity of 60,000 h(-1). Gas-phase O(2) regenerated the lattice oxygen and replenished the chemisorbed oxygen, which facilitated Hg(0) oxidation. HCl was the most effective flue gas component responsible for Hg(0) oxidation. 10 ppm HCl plus 4% O(2) resulted in 100% Hg(0) oxidation under the experimental conditions. SO(2) competed with Hg(0) for active sites, thus deactivating the catalyst's capability in oxidizing Hg(0). NO covered the active sites and consumed surface oxygen active for Hg(0) oxidation, hence limiting Hg(0) oxidation. Water vapor showed prohibitive effect on Hg(0) oxidation due to its competition with HCl and Hg(0) for active adsorption sites. This study provides information about the promotional or inhibitory effects of individual flue gas components on Hg(0) oxidation over a highly effective Mn-Ce/Ti catalyst. Such knowledge is of fundamental importance for industrial applications of the Mn-Ce/Ti catalyst in coal-fired power plants. Copyright © 2012 Elsevier B.V. All rights reserved.
Synthesis of Metal-organic Frameworks Based on Zr4+ and Benzene 1,3,5-Tricarboxylate Linker as Heterogeneous Catalyst in the Esterification Reaction of Palmitic Acid

NASA Astrophysics Data System (ADS)

Larasati, I.; Winarni, D.; Putri, F. R.; Hanif, Q. A.; Lestari, W. W.

2017-07-01

The conversion of the biomass into biodiesels via catalytic esterification and trans-esterification became an interesting topic due to the depletion of fossil-based energy. Homogenous catalysts such as HCl, H2SO4 and NaOH commonly used as catalyst, however, the use of this kind of catalyst causes more problems, such as the difficulties on the separation from the product and the pollution effect on the environment. Heterogeneous catalysts, such as Metal-Organic Frameworks (MOFs) give an alternative promising way to substitute these limitations due to their strong catalytic site, porosity, high specific surface area, and easy-separation and reusable properties. Herein, we reported the synthesis of MOFs based on zirconium(IV) and H3BTC linker (H3BTC = benzene-1,3,5-tricarboxylic acid) by solvothermal and reflux method. Solvothermal reaction at 120 °C was found to be the optimum method, that was indicated by most crystalline product compared to the simulated pattern in XRD analysis. The formation of the framework was characterized by FTIR analysis, which showed a significant shift from 1722 cm-1 to 1620 cm-1. The synthesized Zr(IV)-BTC was thermally stable up to 322°C as shown by TG/DTA analysis. This high thermal stability was related to the high oxidation state of Zr(IV), which give a significant covalent character to the Zr-O bond.
The effect of titanium nickel nitride decorated carbon nanotubes-reduced graphene oxide hybrid support for methanol oxidation

NASA Astrophysics Data System (ADS)

Liu, Gen; Pan, Zhanchang; Li, Wuyi; Yu, Ke; Xia, Guowei; Zhao, Qixiang; Shi, Shikun; Hu, Guanghui; Xiao, Chumin; Wei, Zhigang

2017-07-01

Titanium nickel nitride (TiNiN) decorated three-dimensional (3D) carbon nanotubes-reduced graphene oxide (CNT-rGO), a fancy 3D platinum (Pt)-based catalyst hybrid support, is prepared by a solvothermal process followed by a nitriding process, which is tested as anodic catalyst support for the methanol oxidation reaction (MOR). The structure, morphology and composition of the synthesized TiNiN/CNT-rGO exhibits a uniform particle dispersion with high purity and interpenetrating 3D network structure. Notably, Pt/TiNiN/CNT-rGO catalyst exhibits significantly improved catalytic activity and durability for methanol oxidation in comparison with Pt/CNT-rGO and conventional Pt/C (JM). The outstanding electrochemical performance was attributed to structure and properties. That is, the 3D CNT-rGO provided a fast transport network for charge-transfer and mass-transfer as well as TiNiN NPs with good synergistic effect and the strong electronic coupling between different domains in TiNiN/CNT-rGO, thus the catalytic activity of the novel catalyst is greatly improved. These results evidences 3D TiNiN/CNT-rGO as a promising catalyst support for a wide range of applications in fuel cells.
Two Catalysts for Selective Oxidation of Contaminant Gases

NASA Technical Reports Server (NTRS)

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 nitrogen at temperatures up to 400 C, without producing nitrogen oxides. This catalyst converts ammonia completely to nitrogen, even when the concentration of ammonia is very low. No other catalyst is known to oxidize ammonia selectively at such a high temperature and low concentration. Both the metal oxide and the support contribute to the activity and selectivity of this catalyst.
Effects of acid catalyst type on structural, morphological, and optoelectrical properties of spin-coated TiO2 thin film

NASA Astrophysics Data System (ADS)

Golobostanfard, Mohammad Reza; Abdizadeh, Hossein

2013-03-01

The effects of different acid catalysts of nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, boric acid, acetic acid, and citric acid on structural, morphological, and optoelectrical properties of nanocrystalline spin-coated TiO2 thin films synthesized via alkoxide sol-gel route were investigated. It was found that only the sols with HNO3 and HCl are suitable for film preparation. The X-ray diffractometry and Raman analysis showed that crystalline phases could be controlled by the type of acid catalyst. Although the H2SO4 sol shows good stability, it causes extremely different morphology to form due to its different sol nature and high contact angle. Fourier transformed infrared spectra confirmed the presence of acid anion species in all samples even after calcination. Furthermore, it was inferred from UV-visable absorption spectra that although the band gap and thickness of the films are independent of acid catalyst type, the refractive index and porosity of the films are strongly affected by the type of acids.
Hollow PdCo alloy nanospheres with mesoporous shells as high-performance catalysts for methanol oxidation.

PubMed

Sheng, Guoqing; Chen, Jiahui; Ye, Huangqing; Hu, Zhixiong; Fu, Xian-Zhu; Sun, Rong; Huang, Weixin; Wong, Ching-Ping

2018-07-15

Monodisperse hollow mesoporous PdCo alloy nanospheres are prepared via a simple galvanic replacement reaction. The as-prepared PdCo hollow nanospheres have small diameter, such as Pd 78 Co 22 nanospheres of diameter about 25 nm and mesoporous shells about 4-5 nm. The Pd 78 Co 22 hollow mesoporous nanospheres possess the largest electrochemical active surface areas (ECSA, 53.91 m 2  g -1 ), mass activity (1488 mA mg -1 ) and specific activity (2.76 mA cm -2 ) towards to methanol oxidation relative to the Pd 68 Co 32 , Pd 92 Co 8 hollow mesoporous nanospheres and commercial Pd/C catalysts. Moreover, the activity of Pd 78 Co 22 after long-term stability tests is still the best and even better than those of fresh Pd 68 Co 32 and commercial Pd/C catalysts. The PdCo catalysts not only effectively reduce the Pd usage by forming hollow structure, but also fully realize the Pd-Co alloying effects for enhancing the methanol oxidation catalytic performance. Copyright © 2018 Elsevier Inc. All rights reserved.
Metallic nanocatalysts for electrochemical CO2 reduction in aqueous solutions.

PubMed

Wang, Yuanxing; Niu, Cailing; Wang, Dunwei

2018-05-16

How to effectively and efficiently reduce carbon dioxide (CO 2 ) to value-added chemicals represent a frontier in catalysis research. Due to the high activation energy needs and the endothermic nature of CO 2 reduction, the reactions are difficult to carry out. When H 2 O is present, hydrogen evolution reactions (HER) often compete favorably with CO 2 reduction reactions. For these reactions, catalysts are of critical importance to CO 2 reduction. In this article, we review the various metal nanocatalysts for electrochemical CO 2 reduction (ECR) reactions. In recognition of the importance of H 2 O to CO 2 reduction, we focus our discussions on systems in aqueous solutions. Nanostructured metal catalysts are chosen for the discussions because they represent the most effective catalysts for ECR. After a brief introduction of the fundamental principles of ECR, we devote the rest of the article on the discussions of various types of nanostructured metallic catalysts, which are categorized by their compositions and working mechanisms. Lastly, strategies for improving reaction efficiency and selectivity are discussed. Copyright © 2018 Elsevier Inc. All rights reserved.
Subnanometer and nanometer catalysts, method for preparing size-selected catalysts

DOEpatents

Vajda, Stefan , Pellin, Michael J.; Elam, Jeffrey W [Elmhurst, IL; Marshall, Christopher L [Naperville, IL; Winans, Randall A [Downers Grove, IL; Meiwes-Broer, Karl-Heinz [Roggentin, GR

2012-04-03

Highly uniform cluster based nanocatalysts supported on technologically relevant supports were synthesized for reactions of top industrial relevance. The Pt-cluster based catalysts outperformed the very best reported ODHP catalyst in both activity (by up to two orders of magnitude higher turn-over frequencies) and in selectivity. The results clearly demonstrate that highly dispersed ultra-small Pt clusters precisely localized on high-surface area supports can lead to affordable new catalysts for highly efficient and economic propene production, including considerably simplified separation of the final product. The combined GISAXS-mass spectrometry provides an excellent tool to monitor the evolution of size and shape of nanocatalyst at action under realistic conditions. Also provided are sub-nanometer gold and sub-nanometer to few nm size-selected silver catalysts which possess size dependent tunable catalytic properties in the epoxidation of alkenes. Invented size-selected cluster deposition provides a unique tool to tune material properties by atom-by-atom fashion, which can be stabilized by protective overcoats.

Some links on this page may take you to non-federal websites. Their policies may differ from this site.