Catalytic modification of cellulose and hemicellulose - Sugarefine

Energy Technology Data Exchange (ETDEWEB)

Repo, T. [Helsinki Univ. (Finland),Laboratory of Inorganic Chemistry], email: timo.repo@helsinki.fi

2012-07-01

The main goal of the project is to develop catalytic methods for the modification of lignocellulose-based saccharides in the biorefineries. The products of these reactions could be used for example as biofuel components, raw materials for the chemical industry, solvents and precursors for biopolymers. The catalyst development aims at creating efficient, selective and green catalytic methods for profitable use in biorefineries. The project is divided in three work packages: In WP1 (Catalytic dehydration of cellulose) the aim is at developing non-toxic, efficient methods for the catalytic dehydration of cellulose the target molecule being here 5-hydroxymethylfurfural (5-HMF). 5-HMF is an interesting platform chemical for the production of fuel additives, solvents and polymers. In WP2 (Catalytic reduction), the objective of the catalytic reduction studies is to produce commercially interesting monofunctional chemicals, such as 1-butanol or 2-methyltetrahydrofuran (2-MeTHF). In WP3 (Catalytic oxidation), the research focuses on developing a green and efficient oxidation method for producing acids. Whereas acetic and formic acids are bulk chemicals, diacids such as glucaric and xylaric acids are valuable specialty chemicals for detergent, polymer and food production.

Catalytic asymmetric epoxidation of alpha,beta-unsaturated amides: efficient synthesis of beta-aryl alpha-hydroxy amides using a one-pot tandem catalytic asymmetric epoxidation-Pd-catalyzed epoxide opening process.

Science.gov (United States)

Nemoto, Tetsuhiro; Kakei, Hiroyuki; Gnanadesikan, Vijay; Tosaki, Shin-Ya; Ohshima, Takashi; Shibasaki, Masakatsu

2002-12-11

The catalytic asymmetric epoxidation of alpha,beta-unsaturated amides using Sm-BINOL-Ph3As=O complex was succeeded. Using 5-10 mol % of the asymmetric catalyst, a variety of amides were epoxidized efficiently, yielding the corresponding alpha,beta-epoxy amides in up to 99% yield and in more than 99% ee. Moreover, the novel one-pot tandem process, one-pot tandem catalytic asymmetric epoxidation-Pd-catalyzed epoxide opening process, was developed. This method was successfully utilized for the efficient synthesis of beta-aryl alpha-hydroxy amides, including beta-aryllactyl-leucine methyl esters. Interestingly, it was found that beneficial modifications on the Pd catalyst were achieved by the constituents of the first epoxidation, producing a more suitable catalyst for the Pd-catalyzed epoxide opening reaction in terms of chemoselectivity.

Highly Efficient Catalytic Cyclic Carbonate Formation by Pyridyl Salicylimines.

Science.gov (United States)

Subramanian, Saravanan; Park, Joonho; Byun, Jeehye; Jung, Yousung; Yavuz, Cafer T

2018-03-21

Cyclic carbonates as industrial commodities offer a viable nonredox carbon dioxide fixation, and suitable heterogeneous catalysts are vital for their widespread implementation. Here, we report a highly efficient heterogeneous catalyst for CO 2 addition to epoxides based on a newly identified active catalytic pocket consisting of pyridine, imine, and phenol moieties. The polymeric, metal-free catalyst derived from this active site converts less-reactive styrene oxide under atmospheric pressure in quantitative yield and selectivity to the corresponding carbonate. The catalyst does not need additives, solvents, metals, or co-catalysts, can be reused at least 10 cycles without the loss of activity, and scaled up easily to a kilogram scale. Density functional theory calculations reveal that the nucleophilicity of pyridine base gets stronger due to the conjugated imines and H-bonding from phenol accelerates the reaction forward by stabilizing the intermediate.

In situ formed catalytically active ruthenium nanocatalyst in room temperature dehydrogenation/dehydrocoupling of ammonia-borane from Ru(cod)(cot) precatalyst.

Science.gov (United States)

Zahmakiran, Mehmet; Ayvalı, Tuğçe; Philippot, Karine

2012-03-20

The development of simply prepared and effective catalytic materials for dehydrocoupling/dehydrogenation of ammonia-borane (AB; NH(3)BH(3)) under mild conditions remains a challenge in the field of hydrogen economy and material science. Reported herein is the discovery of in situ generated ruthenium nanocatalyst as a new catalytic system for this important reaction. They are formed in situ during the dehydrogenation of AB in THF at 25 °C in the absence of any stabilizing agent starting with homogeneous Ru(cod)(cot) precatalyst (cod = 1,5-η(2)-cyclooctadiene; cot = 1,3,5-η(3)-cyclooctatriene). The preliminary characterization of the reaction solutions and the products was done by using ICP-OES, ATR-IR, TEM, XPS, ZC-TEM, GC, EA, and (11)B, (15)N, and (1)H NMR, which reveal that ruthenium nanocatalyst is generated in situ during the dehydrogenation of AB from homogeneous Ru(cod)(cot) precatalyst and B-N polymers formed at the initial stage of the catalytic reaction take part in the stabilization of this ruthenium nanocatalyst. Moreover, following the recently updated approach (Bayram, E.; et al. J. Am. Chem. Soc.2011, 133, 18889) by performing Hg(0), CS(2) poisoning experiments, nanofiltration, time-dependent TEM analyses, and kinetic investigation of active catalyst formation to distinguish single metal or in the present case subnanometer Ru(n) cluster-based catalysis from polymetallic Ru(0)(n) nanoparticle catalysis reveals that in situ formed Ru(n) clusters (not Ru(0)(n) nanoparticles) are kinetically dominant catalytically active species in our catalytic system. The resulting ruthenium catalyst provides 120 total turnovers over 5 h with an initial turnover frequency (TOF) value of 35 h(-1) at room temperature with the generation of more than 1.0 equiv H(2) at the complete conversion of AB to polyaminoborane (PAB; [NH(2)BH(2)](n)) and polyborazylene (PB; [NHBH](n)) units.

Crystal structures of wild-type Trichoderma reesei Cel7A catalytic domain in open and closed states

Energy Technology Data Exchange (ETDEWEB)

Bodenheimer, Annette M. [Molecular and Structural Biochemistry Department, North Carolina State University, Raleigh NC USA; Neutron Sciences Directorate, Oak Ridge National Laboratory, TN USA; Meilleur, Flora [Molecular and Structural Biochemistry Department, North Carolina State University, Raleigh NC USA; Neutron Sciences Directorate, Oak Ridge National Laboratory, TN USA

2016-11-07

Trichoderma reesei Cel7A efficiently hydrolyses cellulose. We report here the crystallographic structures of the wild-type TrCel7A catalytic domain (CD) in an open state and, for the first time, in a closed state. Molecular dynamics (MD) simulations indicate that the loops along the CD tunnel move in concerted motions. Together, the crystallographic and MD data suggest that the CD cycles between the tense and relaxed forms that are characteristic of work producing enzymes. Analysis of the interactions formed by R251 provides a structural rationale for the concurrent decrease in product inhibition and catalytic efficiency measured for product-binding site mutants.

Catalytic process for tritium exchange reaction

International Nuclear Information System (INIS)

Hansoo Lee; Kang, H.S.; Paek, S.W.; Hongsuk Chung; Yang Geun Chung; Sook Kyung Lee

2001-01-01

The catalytic activities for a hydrogen isotope exchange were measured through the reaction of a vapor and gas mixture. The catalytic activity showed to be comparable with the published data. Since the gas velocity is relatively low, the deactivation was not found clearly during the 5-hour experiment. Hydrogen isotope transfer experiments were also conducted through the liquid phase catalytic exchange reaction column that consisted of a catalytic bed and a hydrophilic bed. The efficiencies of both the catalytic and hydrophilic beds were higher than 0.9, implying that the column performance was excellent. (author)

Improved catalytic efficiency, thermophilicity, anti-salt and detergent tolerance of keratinase KerSMD by partially truncation of PPC domain.

Science.gov (United States)

Fang, Zhen; Zhang, Juan; Du, Guocheng; Chen, Jian

2016-06-14

The keratinase from Stenotrophomonas maltophilia (KerSMD) is known for its high activity and pH stability in keratin degradation. However, catalytic efficiency and detergent tolerability need to be improved in order to be used for industrial application. In this work, we obtained several keratinase variants with enhanced catalytic efficiency, thermophilicity, and anti-salt and detergent tolerability by partially truncating the PPC domain of KerSMD. The variants all showed improved catalytic efficiency to synthetic substrate AAPF, with the V355 variant having the highest kcat /Km value of 143.6 s(-1) mM(-1). The truncation of keratinase had little effect on alkaline stability but obviously decreased collagenase activity, developing its potential application in leather treatment. The variants V380, V370, and V355 were thermophilic, with a 1.7-fold enhancement of keratinlytic activity at 60 °C when compared to the wild type. The entire truncation of PPC domain obtained the variant V355 with improved tolerance to alkalinity, salt, chaotropic agents, and detergents. The V355 variant showed more than a 40% improvement in activity under 15% (w/v) NaCl or 4% (w/v) SDS solution, showing excellent stability under harsh washing and unhairing conditions. Our work investigated how protein engineering affects the function of PPC domain of KerSMD.

Lysosome-controlled efficient ROS overproduction against cancer cells with a high pH-responsive catalytic nanosystem

Science.gov (United States)

Fu, Jingke; Shao, Yiran; Wang, Liyao; Zhu, Yingchun

2015-04-01

Excess reactive oxygen species (ROS) have been proved to damage cancer cells efficiently. ROS overproduction is thus greatly desirable for cancer therapy. To date, ROS production is generally uncontrollable and outside cells, which always bring severe side-effects in the vasculature. Since most ROS share a very short half-life and primarily react close to their site of formation, it would be more efficient if excess ROS are controllably produced inside cancer cells. Herein, we report an efficient lysosome-controlled ROS overproduction via a pH-responsive catalytic nanosystem (FeOx-MSNs), which catalyze the decomposition of H2O2 to produce considerable ROS selectively inside the acidic lysosomes (pH 5.0) of cancer cells. After a further incorporation of ROS-sensitive TMB into the nanosystem (FeOx-MSNs-TMB), both a distinct cell labeling and an efficient death of breast carcinoma cells are obtained. This lysosome-controlled efficient ROS overproduction suggests promising applications in cancer treatments.Excess reactive oxygen species (ROS) have been proved to damage cancer cells efficiently. ROS overproduction is thus greatly desirable for cancer therapy. To date, ROS production is generally uncontrollable and outside cells, which always bring severe side-effects in the vasculature. Since most ROS share a very short half-life and primarily react close to their site of formation, it would be more efficient if excess ROS are controllably produced inside cancer cells. Herein, we report an efficient lysosome-controlled ROS overproduction via a pH-responsive catalytic nanosystem (FeOx-MSNs), which catalyze the decomposition of H2O2 to produce considerable ROS selectively inside the acidic lysosomes (pH 5.0) of cancer cells. After a further incorporation of ROS-sensitive TMB into the nanosystem (FeOx-MSNs-TMB), both a distinct cell labeling and an efficient death of breast carcinoma cells are obtained. This lysosome-controlled efficient ROS overproduction suggests

Steam reformer with catalytic combustor

Science.gov (United States)

Voecks, Gerald E. (Inventor)

1990-01-01

A steam reformer is disclosed having an annular steam reforming catalyst bed formed by concentric cylinders and having a catalytic combustor located at the center of the innermost cylinder. Fuel is fed into the interior of the catalytic combustor and air is directed at the top of the combustor, creating a catalytic reaction which provides sufficient heat so as to maintain the catalytic reaction in the steam reforming catalyst bed. Alternatively, air is fed into the interior of the catalytic combustor and a fuel mixture is directed at the top. The catalytic combustor provides enhanced radiant and convective heat transfer to the reformer catalyst bed.

Significant Improvement of Catalytic Efficiencies in Ionic Liquids

International Nuclear Information System (INIS)

Song, Choong Eui; Yoon, Mi Young; Choi, Doo Seong

2005-01-01

The use of ionic liquids as reaction media can confer many advantages upon catalytic reactions over reactions in organic solvents. In ionic liquids, catalysts having polar or ionic character can easily be immobilized without additional structural modification and thus the ionic solutions containing the catalyst can easily be separated from the reagents and reaction products, and then, be reused. More interestingly, switching from an organic solvent to an ionic liquid often results in a significant improvement in catalytic performance (e.g., rate acceleration, (enantio)selectivity improvement and an increase in catalyst stability). In this review, some recent interesting results which can nicely demonstrate these positive 'ionic liquid effect' on catalysis are discussed

Supercritical CO{sub 2} mediated synthesis and catalytic activity of graphene/Pd nanocomposites

Energy Technology Data Exchange (ETDEWEB)

Tang, Lulu [School of Chemical Engineering, Yeungnam University, Gyeongsan, Gyeoungbuk 712-749 (Korea, Republic of); Nguyen, Van Hoa [School of Chemical Engineering, Yeungnam University, Gyeongsan, Gyeoungbuk 712-749 (Korea, Republic of); Department of Chemistry, Nha Trang University, 2 Nguyen Dinh Chieu, Nha Trang (Viet Nam); Shim, Jae-Jin, E-mail: jjshim@yu.ac.kr [School of Chemical Engineering, Yeungnam University, Gyeongsan, Gyeoungbuk 712-749 (Korea, Republic of)

2015-11-15

Highlights: • RGO/Pd composite was efficiently prepared via a facile method in supercritical CO{sub 2}. • Graphene sheets were coated uniformly with Pd nanoparticles with a size of ∼8 nm. • Composites exhibited excellent catalytic activity in the Suzuki reaction even after 10 cycles. - Abstract: Graphene sheets were decorated with palladium nanoparticles using a facile and efficient method in supercritical CO{sub 2}. The nanoparticles were formed on the graphene sheets by the simple hydrogen reduction of palladium(II) hexafluoroacetylacetonate precursor in supercritical CO{sub 2}. The product was characterized by X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, and X-ray photoelectron spectroscopy. Highly dispersed nanoparticles with various sizes and shapes adhered well to the graphene sheets. The composites showed high catalytic activities for the Suzuki reaction under aqueous and aerobic conditions within 5 min. The effects of the different Pd precursor loadings on the catalytic activities of the composites were also examined.

Highly efficient conversion of terpenoid biomass to jet-fuel range cycloalkanes in a biphasic tandem catalytic process

Energy Technology Data Exchange (ETDEWEB)

Yang, Xiaokun [Univ. of Nevada, Reno, NV (United States); Li, Teng [Washington State Univ., Pullman, WA (United States); Tang, Kan [Washington State Univ., Pullman, WA (United States); Zhou, Xinpei [Univ. of Nevada, Reno, NV (United States); Lu, Mi [Univ. of Nevada, Reno, NV (United States); Ounkham, Whalmany L. [Univ. of Nevada, Reno, NV (United States); Spain, Stephen M. [Univ. of Nevada, Reno, NV (United States); Frost, Brian J. [Univ. of Nevada, Reno, NV (United States); Lin, Hongfei [Washington State Univ., Pullman, WA (United States)

2017-06-12

The demand for bio-jet fuels to reduce carbon emissions is increasing substantially in the aviation sector, while the scarcity of high-density jet fuel components limits the use of bio-jet fuels in high-performance aircrafts compared with conventional jet fuels. In this paper, we report a novel biphasic tandem catalytic process (biTCP) for synthesizing cycloalkanes from renewable terpenoid biomass, such as 1,8-cineole. Multistep tandem reactions, including C–O ring opening by hydrolysis, dehydration, and hydrogenation, were carried out in the “one-pot” biTCP. 1,8-Cineole was efficiently converted to p-menthane at high yields (>99%) in the biTCP under mild reaction conditions. Finally, the catalytic reaction mechanism is discussed.

Upgrading of bio-oil to boiler fuel by catalytic hydrotreatment and esterification in an efficient process

International Nuclear Information System (INIS)

Zhang, Xinghua; Chen, Lungang; Kong, Wei; Wang, Tiejun; Zhang, Qi; Long, Jinxing; Xu, Ying; Ma, Longlong

2015-01-01

Bio-oil can't be directly used as fuel due to its deteriorate properties. Here, an efficient catalytic upgrading process for the bio-oil, including esterification, hydrogenation, hydrodeoxygenation and depolymerization, is proposed with multifunctional catalyst Ni/SiO 2 –ZrO 2 and biomass-derived solvent ethanol. Results showed that esters, alcohols, phenolics, and cyclo-ketones were the main components in the upgraded bio-oil while aldehydes were removed completely via catalytic hydrogenation and acids were removed by catalytic esterification with supercritical ethanol. The pH value of upgraded bio-oil rose drastically from 2.38 to 5.24, and the high heating value increased to 24.4 MJ kg −1 . Comparison characterization on the upgraded and crude bio-oil using FT-IR, GPC (Gel permeation chromatography) and 13 C NMR (Nuclear Magnetic Resonance) demonstrated that lignin-derived oligomers contained in crude bio-oil were further depolymerized over Ni/SiO 2 –ZrO 2 catalyst. The improved properties suggest that the upgraded bio-oil is more suitable to be used as boiler fuel. Furthermore, the loss of carbon is negligible because formation of coke is suppressed during the upgrading process. - Highlights: • Acid can be converted via catalytic esterification in supercritical ethanol. • Aldehydes can be removed completely during the upgrading process. • Lignin-derived oligomers were further depolymerized during the upgrading process. • Formation of coke is effectively inhibited during the upgrading process

Experimental demonstration of the reverse flow catalytic membrane reactor concept for energy efficient syngas production. Part 2: Model development

NARCIS (Netherlands)

Smit, J.; Bekink, G.J.; Sint Annaland, van M.; Kuipers, J.A.M.

2007-01-01

In this contribution the technical feasibility of the reverse flow catalytic membrane reactor (RFCMR) concept with porous membranes for energy efficient syngas production is investigated. In earlier work an experimental proof of principle was already provided [Smit, J., Bekink, G.J., van Sint

Heterogeneous catalytic materials solid state chemistry, surface chemistry and catalytic behaviour

CERN Document Server

Busca, Guido

2014-01-01

Heterogeneous Catalytic Materials discusses experimental methods and the latest developments in three areas of research: heterogeneous catalysis; surface chemistry; and the chemistry of catalysts. Catalytic materials are those solids that allow the chemical reaction to occur efficiently and cost-effectively. This book provides you with all necessary information to synthesize, characterize, and relate the properties of a catalyst to its behavior, enabling you to select the appropriate catalyst for the process and reactor system. Oxides (used both as catalysts and as supports for cata

Comparison of Efficiencies and Mechanisms of Catalytic Ozonation of Recalcitrant Petroleum Refinery Wastewater by Ce, Mg, and Ce-Mg Oxides Loaded Al2O3

Directory of Open Access Journals (Sweden)

Chunmao Chen

2017-02-01

Full Text Available The use of catalytic ozonation processes (COPs for the advanced treatment of recalcitrant petroleum refinery wastewater (RPRW is rapidly expanding. In this study, magnesium (Mg, cerium (Ce, and Mg-Ce oxide-loaded alumina (Al2O3 were developed as cost efficient catalysts for ozonation treatment of RPRW, having performance metrics that meet new discharge standards. Interactions between the metal oxides and the Al2O3 support influence the catalytic properties, as well as the efficiency and mechanism. Mg-Ce/Al2O3 (Mg-Ce/Al2O3-COP reduced the chemical oxygen demand by 4.7%, 4.1%, 6.0%, and 17.5% relative to Mg/Al2O3-COP, Ce/Al2O3-COP, Al2O3-COP, and single ozonation, respectively. The loaded composite metal oxides significantly increased the hydroxyl radical-mediated oxidation. Surface hydroxyl groups (–OHs are the dominant catalytic active sites on Al2O3. These active surface –OHs along with the deposited metal oxides (Mg2+ and/or Ce4+ increased the catalytic activity. The Mg-Ce/Al2O3 catalyst can be economically produced, has high efficiency, and is stable under acidic and alkaline conditions.

High-efficiency plasma catalytic removal of dilute benzene from air

International Nuclear Information System (INIS)

Fan, Hong-Yu; Shi, Chuan; Li, Xiao-Song; Zhao, De-Zhi; Xu, Yong; Zhu, Ai-Min

2009-01-01

Achieving complete oxidation, good humidity tolerance and low energy cost is the key issue that needs to be addressed in plasma catalytic volatile organic compounds removal from air. For this purpose, Ag/HZSM-5 catalyst-packed dielectric barrier discharge using a cycled system composed of a storage stage and a discharge stage was studied. For dilute benzene removal from simulated air, Ag/HZSM-5 catalysts exhibit not only preferential adsorption of benzene in humid air at the storage stage but also almost complete oxidation of adsorbed benzene at the discharge stage. Five 'storage-discharge' cycles were examined, which suggests that Ag/HZSM-5 catalysts are very stable during the cycled 'storage-discharge' (CSD) plasma catalytic process. High oxidation rate of absorbed benzene as well as low energy cost can be achieved at a moderate discharge power. In an example of the CSD plasma catalytic remedy of simulated air containing 4.7 ppm benzene with 50% RH and 600 ml min -1 flow rate, the energy cost was as low as 3.7 x 10 -3 kWh m -3 air. This extremely low energy cost to remove low-concentration pollutants from air undoubtedly makes the environmental applications of the plasma catalytic technique practical.

Highly efficient catalytic reductive degradation of various organic ...

Indian Academy of Sciences (India)

aDepartment of Applied Sciences (Chemical Science Division), GUIST, Gauhati University, ... Highly improved catalytic reductive degradation of different organic dyes, in the ... was prepared by a facile co-precipitation method using ultra-high dilute aqueous solutions. ...... face chemical-modification for engineering the intrin-.

SS-mPEG chemical modification of recombinant phospholipase C for enhanced thermal stability and catalytic efficiency.

Science.gov (United States)

Fang, Xian; Wang, Xueting; Li, Guiling; Zeng, Jun; Li, Jian; Liu, Jingwen

2018-05-01

PEGylation is one of the most promising and extensively studied strategies for improving the properties of proteins as well as enzymic physical and thermal stability. Phospholipase C, hydrolyzing the phospholipids offers tremendous applications in diverse fields. However, the poor thermal stability and higher cost of production have restricted its industrial application. This study focused on improving the stabilization of recombinant PLC by chemical modification with methoxypolyethylene glycol-Succinimidyl Succinate (SS-mPEG, MW 5000). PLC gene from isolate Bacillus cereus HSL3 was fused with SUMO, a novel small ubiquitin-related modifier expression vector and over expressed in Escherichia coli. The soluble fraction of SUMO-PLC reached 80% of the total recombinant protein. The enzyme exhibited maximum catalytic activity at 80 °C and was relatively thermostable at 40-70 °C. It showed extensive substrate specificity pattern and marked activity toward phosphatidylcholine, which made it a typical non-specific PLC for industrial purpose. SS-mPEG-PLC complex exhibited an enhanced thermal stability at 70-80 °C and the catalytic efficiency (K cat /K m ) had increased by 3.03 folds compared with free PLC. CD spectrum of SS-mPEG-PLC indicated a possible enzyme aggregation after chemical modification, which contributed to the higher thermostability of SS-mPEG-PLC. The increase of antiparallel β sheets in secondary structure also made it more stable than parallel β sheets. The presence of SS-mPEG chains on the enzyme molecule surface somewhat changed the binding rate of the substrates, leading to a significant improvement in catalytic efficiency. This study provided an insight into the addition of SS-mPEG for enhancing the industrial applications of phospholipase C at higher temperature. Copyright © 2018 Elsevier B.V. All rights reserved.

Efficiency of Different Nitrogen Forms in Buckwheat (Fagopyrum esculentum Moench

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Burhan Kara

2016-06-01

Full Text Available The research was carried out with aim to determination the efficient of nitrogen forms (ammonium sulfate, ammonium nitrate and urea on nitrogen use efficient for buckwheat in Isparta during 2014 and 2015 years. All the examined characteristics were determined higher values in applied nitrogen forms according to non-nitrogen parcel. In compared to nitrogen forms, the highest grain yield (1456 and 1325 kg ha-1, biological yield (4873 and 4512 kg ha-1, 1000 grain weight (24.9 and 24.8 g, agronomic efficient (24.96% and 24.25%, recycling efficient (0.24% and 0.22% and utilization efficient (0.25% and 0.18% were obtained from ammonium sulfate, the highest protein content (11.37% and 12.44% and agro-physiological efficient (0.27% and 0.24% from ammonium nitrate in both years. Among the nitrogen forms weren’t significant differently in physiological efficient in both years, recycling and utilization efficient in the first year. The mineral nutrient content varied according to nitrogen forms. Generally, ammonium sulfate was positive effect to yield and some quality parameters.

Multi-Walled Carbon Nanotube-Assisted Electrodeposition of Silver Dendrite Coating as a Catalytic Film

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Li Fu

2017-12-01

Full Text Available A multi-walled carbon nanotube (MWCNT-coated indium tin oxide (ITO slide was used as a platform for the growth of a silver dendrite (Ag-D film using cyclic voltammetry. The particular dendritic nanostructures were formed by the diffusion-limited-aggregation model due to the potential difference between the MWCNTs and the ITO surface. The Ag-D-coated ITO film was then used for the catalytic degradation of methyl orange (MO and methylene blue (MB under static aqueous conditions. The network structure of the Ag-D allows the efficient diffusion of MO and MB, and consequently enhances the catalytic performance. Since the thin film is much easier to use for the post-treatment of powder catalysts, the proposed method shows great potential in many catalytic applications.

Testing the Weak Form Efficiency of Karachi Stock Exchange

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Muhammad Arshad Haroon

2012-12-01

Full Text Available In an efficient market, share prices reflect all available information. The study of efficient market hypothesis helps to take right decisions related to investments. In this research,weak form efficiency has been tested of Karachi Stock Exchange—KSE covering the period of 2nd November 1991 to 2nd November 2011. Descriptive statistics indicated the absence of weak form efficiency while results of non-parametric tests, showed consistency as well. We employed non-parametric tests were KS Goodness-of-Fit test,run test and autocorrelation test to find out serial independency of the data. Results prove that KSE is not weak-form-efficient. This happens because KSE is an emerging market and there, it has been observed that information take time to be processed. Thus it can besaid that technical analysis may be applied to gain abnormal returns.

Small Molecules that Enhance the Catalytic Efficiency of HLA-DM

International Nuclear Information System (INIS)

Nicholson, M.; Moradi, B.; Seth, N.; Xing, X.; Cuny, G.; Stein, R.; Wucherpfenning, K.

2006-01-01

HLA-DM (DM) plays a critical role in Ag presentation to CD4 T cells by catalyzing the exchange of peptides bound to MHC class II molecules. Large lateral surfaces involved in the DM:HLA-DR (DR) interaction have been defined, but the mechanism of catalysis is not understood. In this study, we describe four small molecules that accelerate DM-catalyzed peptide exchange. Mechanistic studies demonstrate that these small molecules substantially enhance the catalytic efficiency of DM, indicating that they make the transition state of the DM:DR/peptide complex energetically more favorable. These compounds fall into two functional classes: two compounds are active only in the presence of DM, and binding data for one show a direct interaction with DM. The remaining two compounds have partial activity in the absence of DM, suggesting that they may act at the interface between DM and DR/peptide. A hydrophobic ridge in the DMβ1 domain was implicated in the catalysis of peptide exchange because the activity of three of these enhancers was substantially reduced by point mutations in this area

Catalytic Ozonation of Phenolic Wastewater: Identification and Toxicity of Intermediates

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Mahdi Farzadkia

2014-01-01

Full Text Available A new strategy in catalytic ozonation removal method for degradation and detoxification of phenol from industrial wastewater was investigated. Magnetic carbon nanocomposite, as a novel catalyst, was synthesized and then used in the catalytic ozonation process (COP and the effects of operational conditions such as initial pH, reaction time, and initial concentration of phenol on the degradation efficiency and the toxicity assay have been investigated. The results showed that the highest catalytic potential was achieved at optimal neutral pH and the removal efficiency of phenol and COD is 98.5% and 69.8%, respectively. First-order modeling demonstrated that the reactions were dependent on the initial concentration of phenol, with kinetic constants varying from 0.038 min−1  ([phenol]o = 1500 mg/L to 1.273 min−1 ([phenol]o = 50 mg/L. Bioassay analysis showed that phenol was highly toxic to Daphnia magna (LC50 96 h=5.6 mg/L. Comparison of toxicity units (TU of row wastewater (36.01 and the treated effluent showed that TU value, after slightly increasing in the first steps of ozonation for construction of more toxic intermediates, severely reduced at the end of reaction (2.23. Thus, COP was able to effectively remove the toxicity of intermediates which were formed during the chemical oxidation of phenolic wastewaters.

Experimental demonstration of the reverse flow catalytic membrane reactor concept for energy efficient syngas production. Part 1: Influence of operating conditions

NARCIS (Netherlands)

Smit, J.; Bekink, G.J.; Sint Annaland, van M.; Kuipers, J.A.M.

2007-01-01

In this contribution the technical feasibility of the reverse flow catalytic membrane reactor (RFCMR) concept with porous membranes for energy efficient syngas production is investigated. In earlier work an experimental proof of principle was already provided [Smit, J., Bekink, G.J., van Sint

Progress in catalytic naphtha reforming process: A review

International Nuclear Information System (INIS)

Rahimpour, Mohammad Reza; Jafari, Mitra; Iranshahi, Davood

2013-01-01

Catalytic naphtha reforming process is a vital process for refineries due to the production of high-octane components, which is intensely demanded in our modern life. The significance of this industrial process induced researchers to investigate different aspects of catalytic naphtha reforming process intensively. Some of the investigators try to improve this process by representing more effective catalysts, while others try to elucidate its kinetic and deactivation mechanisms and design more efficient reactor setups. The amount of these established papers is so much that may confuse some of the researchers who want to find collective information about catalytic naphtha reforming process. In the present paper, the published studies from 1949 until now are categorized into three main groups including finding suitable catalyst, revealing appropriate kinetic and deactivation model, and suggesting efficient reactor configuration and mode of operation. These studies are reviewed separately, and a suitable reference is provided for those who want to have access to generalized information about catalytic naphtha reforming process. Finally, various suggestions for revamping the catalytic naphtha reforming process have been proposed as a guideline for further investigations

Improving the reversibility of thermal denaturation and catalytic efficiency of Bacillus licheniformis α-amylase through stabilizing a long loop in domain B.

Directory of Open Access Journals (Sweden)

Zhu Li

Full Text Available The reversibility of thermal denaturation and catalytic efficiency of Bacillus licheniformis α-amylase were improved through site-directed mutagenesis. By using multiple sequence alignment and PoPMuSiC algorithm, Ser187 and Asn188, which located within a long loop in Domain B of Bacillus licheniformis α-amylase, were selected for mutation. In addition, Ala269, which is adjacent to Ser187 and Asn188, was also investigated. Seven mutants carrying the mutations S187D, N188T, N188S, A269K, A269K/S187D, S187D/N188T, and A269K/S187D/N188T were generated and characterized. The most thermostable mutant, A269K/S187D/N188T, exhibited a 9-fold improvement in half-life at 95°C and pH 5.5, compared with that of the wild-type enzyme. Mutant A269K/S187D/N188T also exhibited improved catalytic efficiency. The catalytic efficiency of mutant A269K/S187D/N188T reached 5.87×103±0.17 g·L-1·s-1 at pH 5.5, which is 1.84-fold larger than the corresponding value determined for the wild-type enzyme. Furthermore, the structure analysis showed that immobilization of the loop containing Ser187 and Asn188 plays a significant role in developing the properties of Bacillus licheniformis α-amylase.

Improving the reversibility of thermal denaturation and catalytic efficiency of Bacillus licheniformis α-amylase through stabilizing a long loop in domain B.

Science.gov (United States)

Li, Zhu; Duan, Xuguo; Chen, Sheng; Wu, Jing

2017-01-01

The reversibility of thermal denaturation and catalytic efficiency of Bacillus licheniformis α-amylase were improved through site-directed mutagenesis. By using multiple sequence alignment and PoPMuSiC algorithm, Ser187 and Asn188, which located within a long loop in Domain B of Bacillus licheniformis α-amylase, were selected for mutation. In addition, Ala269, which is adjacent to Ser187 and Asn188, was also investigated. Seven mutants carrying the mutations S187D, N188T, N188S, A269K, A269K/S187D, S187D/N188T, and A269K/S187D/N188T were generated and characterized. The most thermostable mutant, A269K/S187D/N188T, exhibited a 9-fold improvement in half-life at 95°C and pH 5.5, compared with that of the wild-type enzyme. Mutant A269K/S187D/N188T also exhibited improved catalytic efficiency. The catalytic efficiency of mutant A269K/S187D/N188T reached 5.87×103±0.17 g·L-1·s-1 at pH 5.5, which is 1.84-fold larger than the corresponding value determined for the wild-type enzyme. Furthermore, the structure analysis showed that immobilization of the loop containing Ser187 and Asn188 plays a significant role in developing the properties of Bacillus licheniformis α-amylase.

Characterization of catalytic efficiency parameters of brain cholinesterases in tropical fish.

Science.gov (United States)

de Assis, Caio Rodrigo Dias; Linhares, Amanda Guedes; Oliveira, Vagne Melo; França, Renata Cristina Penha; Santos, Juliana Ferreira; Marcuschi, Marina; Carvalho, Elba Verônica Matoso Maciel; Bezerra, Ranilson Souza; Carvalho, Luiz Bezerra

2014-12-01

Brain cholinesterases from four fish (Arapaima gigas, Colossoma macropomum, Rachycentron canadum and Oreochromis niloticus) were characterized using specific substrates and selective inhibitors. Parameters of catalytic efficiency such as activation energy (AE), k(cat) and k(cat)/k(m) as well as rate enhancements produced by these enzymes were estimated by a method using crude extracts described here. Despite the BChE-like activity, specific substrate kinetic analysis pointed to the existence of only acetylcholinesterase (AChE) in brain of the species studied. Selective inhibition suggests that C. macropomum brain AChE presents atypical activity regarding its behavior in the presence of selective inhibitors. AE data showed that the enzymes increased the rate of reactions up to 10(12) in relation to the uncatalyzed reactions. Zymograms showed the presence of AChE isoforms with molecular weights ranging from 202 to 299 kDa. Values of k(cat) and k(cat)/k(m) were similar to those found in the literature.

Method of fabricating a catalytic structure

Science.gov (United States)

Rollins, Harry W [Idaho Falls, ID; Petkovic, Lucia M [Idaho Falls, ID; Ginosar, Daniel M [Idaho Falls, ID

2009-09-22

A precursor to a catalytic structure comprising zinc oxide and copper oxide. The zinc oxide has a sheet-like morphology or a spherical morphology and the copper oxide comprises particles of copper oxide. The copper oxide is reduced to copper, producing the catalytic structure. The catalytic structure is fabricated by a hydrothermal process. A reaction mixture comprising a zinc salt, a copper salt, a hydroxyl ion source, and a structure-directing agent is formed. The reaction mixture is heated under confined volume conditions to produce the precursor. The copper oxide in the precursor is reduced to copper. A method of hydrogenating a carbon oxide using the catalytic structure is also disclosed, as is a system that includes the catalytic structure.

Efficient fully controlled up-to-date equipment for catalytic treatment of waste gases

International Nuclear Information System (INIS)

Dvorak, Radek; Stulir, Roman; Cagas, Pavel

2007-01-01

This paper describes research and development of a new unit for catalytic destruction of waste gases polluted mainly by volatile organic compounds (VOC), halogenated organic compounds (HOC) or carbon monoxide. Novel equipment has considerable advantages compared with commonly used arrangement (combustion chamber (catalytic reactor)-pipeline-heat exchanger). It is very compact and light and has the combustion chamber, catalytic reactor and heat exchanger integrated into one unit. Maximum utilizing heat losses in the combustion chamber and catalytic reactor is achieved. During the development of this unit experience from tests of previously developed equipment used for thermal treatment of waste gases was used, as well as from experimental studies of catalytic disposal of various VOC carried out in the newly built experimental unit. During the development calculation methods were created allowing design modifications of this unit for real industrial applications. The newly developed unit can be used in various branches of industry such as paint shops, refining plants, sewage treatment plants, food processing industry, pharmaceutical industry, but also in companies processing and transporting crude-oil or natural gas, etc

Catalytic aerobic oxidation of bio-renewable chemicals

DEFF Research Database (Denmark)

Gorbanev, Yury

, EDS, XRF and other methods. Supported gold and ruthenium hydroxide catalyst systems were explored for the aerobic oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDA), a potential polymer building block for the plastic industry, or its dimethyl ester (FDMC). High product......-free conditions. Moreover, a detailed study on the performance and stability of the ruthenium hydroxide catalysts on magnesium-containing supports under reaction conditions was conducted. The aerobic oxidation of HMF to form another value-added chemical, 2,5-diformylfuran (DFF), was also investigated......Ox deposited on various metal oxides. Furthermore, this thesis presents the results of the catalytic aerobic oxidative degradation of higher alcohols over supported ruthenium hydroxide catalysts. A very efficient oxidative cleavage of vic-diols to form respective acids was also shown under examined conditions...

Optimized bacterial expression and purification of the c-Src catalytic domain for solution NMR studies

International Nuclear Information System (INIS)

Piserchio, Andrea; Ghose, Ranajeet; Cowburn, David

2009-01-01

Progression of a host of human cancers is associated with elevated levels of expression and catalytic activity of the Src family of tyrosine kinases (SFKs), making them key therapeutic targets. Even with the availability of multiple crystal structures of active and inactive forms of the SFK catalytic domain (CD), a complete understanding of its catalytic regulation is unavailable. Also unavailable are atomic or near-atomic resolution information about their interactions, often weak or transient, with regulating phosphatases and downstream targets. Solution NMR, the biophysical method best suited to tackle this problem, was previously hindered by difficulties in bacterial expression and purification of sufficient quantities of soluble, properly folded protein for economically viable labeling with NMR-active isotopes. Through a choice of optimal constructs, co-expression with chaperones and optimization of the purification protocol, we have achieved the ability to bacterially produce large quantities of the isotopically-labeled CD of c-Src, the prototypical SFK, and of its activating Tyr-phosphorylated form. All constructs produce excellent spectra allowing solution NMR studies of this family in an efficient manner

Enhanced catalytic behavior of Ni alloys in steam methane reforming

Science.gov (United States)

Yoon, Yeongpil; Kim, Hanmi; Lee, Jaichan

2017-08-01

The dissociation process of methane on Ni and Ni alloys are investigated by density functional theory (DFT) in terms of catalytic efficiency and carbon deposition. Examining the dissociation to CH3, CH2, CH, C, and H is not sufficient to properly predict the catalytic efficiency and carbon deposition, and further investigation of the CO gas-evolving reaction is required to completely understand methane dissociation in steam. The location of alloying element in Ni alloy needed be addressed from the results of ab-inito molecular dynamics (MD). The reaction pathway of methane dissociation associated with CO gas evolution is traced by performing first-principles calculations of the adsorption and activation energies of each dissociation step. During the dissociation process, two alternative reaction steps producing adsorbed C and H or adsorbed CO are critically important in determining coking inhibition as well as H2 gas evolution (i.e., the catalytic efficiency). The theoretical calculations presented here suggest that alloying Ni with Ru is an effective way to reduce carbon deposition and enhance the catalytic efficiency of H2 fueling in solid oxide fuel cells (SOFCs).

A new approach to inertise the containments during catalytic removal of hydrogen

International Nuclear Information System (INIS)

Chakraborty, A.K.; Markandeya, S.G.

1994-01-01

Use of catalytic recombiners for the removal of hydrogen during a severe accident has been recommended by the German Reactor Safety Commission (RSK) due to numerous successful demonstrations of their performances. At the early stages of the accident, a huge quantity of hydrogen is expected to be released in some compartments requiring supplementary measures to ensure that the excess hydrogen concentration wouldn't pose a threat of deflagration /1/. In this presentation a new idea based on catalytic removal of hydrogen with simultaneous passive inertisation of the atmosphere is proposed for large dry containments particularly for those compartments where high H 2 -concentrations are expected. During the catalytic oxidation of hydrogen, the large exothermic heat of reaction causes strong heating of the catalytic plates as well as a continuous energy input in the containment. This can be limited if this large heat energy is efficiently used for heating some chemical compounds to release inert gases such as steam and/or CO 2 by dissociation at moderate temperatures. Such compounds can be arranged in the form of thin slabs in good thermal contact with the catalytic plates. Several such compounds have been identified which are capable of releasing steam and CO 2 equivalent to about 40 - 75% of their mass. Preliminary calculations have been carded out to demonstrate the effectiveness of the proposed concept for the case of two such selected chemicals placed adjacent to the catalytic plate type recombiners. The calculations performed show promising results. (author)

The proteolytic system of pineapple stems revisited: Purification and characterization of multiple catalytically active forms.

Science.gov (United States)

Matagne, André; Bolle, Laetitia; El Mahyaoui, Rachida; Baeyens-Volant, Danielle; Azarkan, Mohamed

2017-06-01

Crude pineapple proteases extract (aka stem bromelain; EC 3.4.22.4) is an important proteolytic mixture that contains enzymes belonging to the cysteine proteases of the papain family. Numerous studies have been reported aiming at the fractionation and characterization of the many molecular species present in the extract, but more efforts are still required to obtain sufficient quantities of the various purified protease forms for detailed physicochemical, enzymatic and structural characterization. In this work, we describe an efficient strategy towards the purification of at least eight enzymatic forms. Thus, following rapid fractionation on a SP-Sepharose FF column, two sub-populations with proteolytic activity were obtained: the unbound (termed acidic) and bound (termed basic) bromelain fractions. Following reversible modification with monomethoxypolyethylene glycol (mPEG), both fractions were further separated on Q-Sepharose FF and SP-Sepharose FF, respectively. This procedure yielded highly purified molecular species, all titrating ca. 1 mol of thiol group per mole of enzyme, with distinct biochemical properties. N-terminal sequencing allowed identifying at least eight forms with proteolytic activity. The basic fraction contained previously identified species, i.e. basic bromelain forms 1 and 2, ananain forms 1 and 2, and comosain (MEROPS identifier: C01.027). Furthermore, a new proteolytic species, showing similarities with basic bomelain forms 1 and 2, was discovered and termed bromelain form 3. The two remaining species were found in the acidic bromelain fraction and were arbitrarily named acidic bromelain forms 1 and 2. Both, acidic bromelain forms 1, 2 and basic bromelain forms 1, 2 and 3 are glycosylated, while ananain forms 1 and 2, and comosain are not. The eight protease forms display different amidase activities against the various substrates tested, namely small synthetic chromogenic compounds (DL-BAPNA and Boc-Ala-Ala-Gly-pNA), fluorogenic compounds

Tunable preparation of ruthenium nanoparticles with superior size-dependent catalytic hydrogenation properties

Energy Technology Data Exchange (ETDEWEB)

Zhao, Yuan; Luo, Yaodong; Yang, Xuan; Yang, Yaxin; Song, Qijun, E-mail: qsong@jiangnan.edu.cn

2017-06-15

Highlights: • A facile and efficient strategy is firstly developed for the synthesis of Ru NPs. • Ru NPs are stable and uniform with the controllable sizes from 2.6 to 51.5 nm. • Ru NPs exhibit size-dependent and superior catalytic hydrogenation activity. - Abstract: Ruthenium (Ru) featured with an unusual catalytic behavior is of great significance in several heterogeneous and electro-catalytic reactions. The preparation of tractable Ru nanocatalysts and the building of highly active catalytic system at ambient temperature remains a grand challenge. Herein, a facile strategy is developed for the controllable preparation of Ru nanoparticles (NPs) with the sizes ranging from 2.6 to 51.5 nm. Ru NPs show superior size-dependent catalytic performance with the best kinetic rate constant as high as −1.52 min{sup −1}, which could far surpass the other traditional noble metals. Ru NPs exert exceedingly efficient low-temperature catalytic activity and good recyclability in the catalytic reduction of nitroaromatic compounds (NACs) and azo dyes. The developed catalytic system provides a distinguishing insight for the artificial preparation of Ru NPs with desired sizes, and allows for the development of rational design rules for exploring catalysts with superior catalytic performances, potentially broadening the applications of metallic NP-enabled catalytic analysis.

Catalytic immunoglobulin gene delivery in a mouse model of Alzheimer's disease: prophylactic and therapeutic applications.

Science.gov (United States)

Kou, Jinghong; Yang, Junling; Lim, Jeong-Eun; Pattanayak, Abhinandan; Song, Min; Planque, Stephanie; Paul, Sudhir; Fukuchi, Ken-Ichiro

2015-02-01

Accumulation of amyloid beta-peptide (Aβ) in the brain is hypothesized to be a causal event leading to dementia in Alzheimer's disease (AD). Aβ vaccination removes Aβ deposits from the brain. Aβ immunotherapy, however, may cause T cell- and/or Fc-receptor-mediated brain inflammation and relocate parenchymal Aβ deposits to blood vessels leading to cerebral hemorrhages. Because catalytic antibodies do not form stable immune complexes and Aβ fragments produced by catalytic antibodies are less likely to form aggregates, Aβ-specific catalytic antibodies may have safer therapeutic profiles than reversibly-binding anti-Aβ antibodies. Additionally, catalytic antibodies may remove Aβ more efficiently than binding antibodies because a single catalytic antibody can hydrolyze thousands of Aβ molecules. We previously isolated Aβ-specific catalytic antibody, IgVL5D3, with strong Aβ-hydrolyzing activity. Here, we evaluated the prophylactic and therapeutic efficacy of brain-targeted IgVL5D3 gene delivery via recombinant adeno-associated virus serotype 9 (rAAV9) in an AD mouse model. One single injection of rAAV9-IgVL5D3 into the right ventricle of AD model mice yielded widespread, high expression of IgVL5D3 in the unilateral hemisphere. IgVL5D3 expression was readily detectable in the contralateral hemisphere but to a much lesser extent. IgVL5D3 expression was also confirmed in the cerebrospinal fluid. Prophylactic and therapeutic injection of rAAV9-IgVL5D3 reduced Aβ load in the ipsilateral hippocampus of AD model mice. No evidence of hemorrhages, increased vascular amyloid deposits, increased proinflammatory cytokines, or infiltrating T-cells in the brains was found in the experimental animals. AAV9-mediated anti-Aβ catalytic antibody brain delivery can be prophylactic and therapeutic options for AD.

Catalytic efficiency of natural and synthetic compounds used as laccase-mediators in oxidising veratryl alcohol and a kraft lignin, estimated by electrochemical analysis

International Nuclear Information System (INIS)

Gonzalez Arzola, K.; Arevalo, M.C.; Falcon, M.A.

2009-01-01

The electrochemical properties of eighteen natural and synthetic compounds commonly used to expand the oxidative capacity of laccases were evaluated in an aqueous buffered medium using cyclic voltammetry. This clarifies which compounds fulfil the requisites to be considered as redox mediators or enhancers. Cyclic voltammetry was also applied as a rapid way to assess the catalytic efficiency (CE) of those compounds which oxidise a non-phenolic lignin model (veratryl alcohol, VA) and a kraft lignin (KL). With the exception of gallic acid and catechol, all assayed compounds were capable of oxidising VA with varying CE. However, only some of them were able to oxidise KL. Although the oxidised forms of HBT and acetovanillone were not electrochemically stable, their reduced forms were quickly regenerated in the presence of VA. They thus act as chemical catalysts. Importantly, HBT and HPI did not attack the KL via the same mechanism as in VA oxidation. Electrochemical evidence suggests that violuric acid oxidises both substrates by an electron transfer mechanism, unlike the other N-OH compounds HBT and HPI. Acetovanillone was found to be efficient in oxidising VA and KL, even better than the synthetic mediators TEMPO, violuric acid or ABTS. Most of the compounds produced a generalised increase in the oxidative charge of KL, probably attributed to chain reactions arising between the phenolic and non-phenolic components of this complex molecule

Catalytic efficiency of natural and synthetic compounds used as laccase-mediators in oxidising veratryl alcohol and a kraft lignin, estimated by electrochemical analysis

Energy Technology Data Exchange (ETDEWEB)

Gonzalez Arzola, K. [Department of Microbiology and Cell Biology, Faculty of Pharmacy, University of La Laguna, 38206 La Laguna, Tenerife (Spain); Arevalo, M.C. [Department of Physical Chemistry, Faculty of Chemistry, University of La Laguna, 38206 La Laguna, Tenerife (Spain)], E-mail: carevalo@ull.es; Falcon, M.A. [Department of Microbiology and Cell Biology, Faculty of Pharmacy, University of La Laguna, 38206 La Laguna, Tenerife (Spain)], E-mail: mafalcon@ull.es

2009-03-30

The electrochemical properties of eighteen natural and synthetic compounds commonly used to expand the oxidative capacity of laccases were evaluated in an aqueous buffered medium using cyclic voltammetry. This clarifies which compounds fulfil the requisites to be considered as redox mediators or enhancers. Cyclic voltammetry was also applied as a rapid way to assess the catalytic efficiency (CE) of those compounds which oxidise a non-phenolic lignin model (veratryl alcohol, VA) and a kraft lignin (KL). With the exception of gallic acid and catechol, all assayed compounds were capable of oxidising VA with varying CE. However, only some of them were able to oxidise KL. Although the oxidised forms of HBT and acetovanillone were not electrochemically stable, their reduced forms were quickly regenerated in the presence of VA. They thus act as chemical catalysts. Importantly, HBT and HPI did not attack the KL via the same mechanism as in VA oxidation. Electrochemical evidence suggests that violuric acid oxidises both substrates by an electron transfer mechanism, unlike the other N-OH compounds HBT and HPI. Acetovanillone was found to be efficient in oxidising VA and KL, even better than the synthetic mediators TEMPO, violuric acid or ABTS. Most of the compounds produced a generalised increase in the oxidative charge of KL, probably attributed to chain reactions arising between the phenolic and non-phenolic components of this complex molecule.

PARAMETRIC EVALUATION OF VOC CONVERSION VIA CATALYTIC INCINERATION

Directory of Open Access Journals (Sweden)

Kaskantzis Neto G.

1997-01-01

Full Text Available Abstract - A pilot-scale catalytic incineration system was used to investigate the effectiveness of catalytic incineration as a means of reducing volatile organic compound (VOC air pollutants. The objectives of the study were: 1 to investigate the effects of operating and design variables on the reduction efficiency of VOCs; and 2 to evaluate reduction efficiencies for specific compounds in different chemical classes. The study results verified that the following factors affect the catalyst performance: inlet temperature, space velocity, compound type, and compound inlet concentration. Tests showed that reduction efficiencies exceeding 98% were possible, given sufficiently high inlet gas temperatures for the following classes of compounds: alcohols, acetates, ketones, hydrocarbons, and aromatics

Chemically-modified cellulose paper as a microstructured catalytic reactor.

Science.gov (United States)

Koga, Hirotaka; Kitaoka, Takuya; Isogai, Akira

2015-01-15

We discuss the successful use of chemically-modified cellulose paper as a microstructured catalytic reactor for the production of useful chemicals. The chemical modification of cellulose paper was achieved using a silane-coupling technique. Amine-modified paper was directly used as a base catalyst for the Knoevenagel condensation reaction. Methacrylate-modified paper was used for the immobilization of lipase and then in nonaqueous transesterification processes. These catalytic paper materials offer high reaction efficiencies and have excellent practical properties. We suggest that the paper-specific interconnected microstructure with pulp fiber networks provides fast mixing of the reactants and efficient transport of the reactants to the catalytically-active sites. This concept is expected to be a promising route to green and sustainable chemistry.

Chemically-Modified Cellulose Paper as a Microstructured Catalytic Reactor

Directory of Open Access Journals (Sweden)

Hirotaka Koga

2015-01-01

Full Text Available We discuss the successful use of chemically-modified cellulose paper as a microstructured catalytic reactor for the production of useful chemicals. The chemical modification of cellulose paper was achieved using a silane-coupling technique. Amine-modified paper was directly used as a base catalyst for the Knoevenagel condensation reaction. Methacrylate-modified paper was used for the immobilization of lipase and then in nonaqueous transesterification processes. These catalytic paper materials offer high reaction efficiencies and have excellent practical properties. We suggest that the paper-specific interconnected microstructure with pulp fiber networks provides fast mixing of the reactants and efficient transport of the reactants to the catalytically-active sites. This concept is expected to be a promising route to green and sustainable chemistry.

Catalytic cleavage activities of 10–23 DNAzyme analogs functionalized with an amino group in its catalytic core

Directory of Open Access Journals (Sweden)

Qi Wang

2012-02-01

Full Text Available Functionalization of the catalytic loop of 10–23 DNAzyme with an amino group was performed by incorporation of 7-(3-aminopropyl-8-aza-7-deaza-2′-deoxyadenosine in different single positions. Among the nine modified positions in the catalytic loop, A9 is the unique position with positive contribution by such modification. These results indicated that more efficient deoxyribozymes remain to be explored by introduction of exogenous functional groups in an appropriate position in the catalytic loop of 10–23 DNAzyme, such as the combination of 7-functional group substituted 8-aza-7-deaza-2′-deoxyadenosine analogs and A9 position.

Catalytic Combustion of Gasified Waste

Energy Technology Data Exchange (ETDEWEB)

Kusar, Henrik

2003-09-01

This thesis concerns catalytic combustion for gas turbine application using a low heating-value (LHV) gas, derived from gasified waste. The main research in catalytic combustion focuses on methane as fuel, but an increasing interest is directed towards catalytic combustion of LHV fuels. This thesis shows that it is possible to catalytically combust a LHV gas and to oxidize fuel-bound nitrogen (NH{sub 3}) directly into N{sub 2} without forming NO{sub x} The first part of the thesis gives a background to the system. It defines waste, shortly describes gasification and more thoroughly catalytic combustion. The second part of the present thesis, paper I, concerns the development and testing of potential catalysts for catalytic combustion of LHV gases. The objective of this work was to investigate the possibility to use a stable metal oxide instead of noble metals as ignition catalyst and at the same time reduce the formation of NO{sub x} In paper II pilot-scale tests were carried out to prove the potential of catalytic combustion using real gasified waste and to compare with the results obtained in laboratory scale using a synthetic gas simulating gasified waste. In paper III, selective catalytic oxidation for decreasing the NO{sub x} formation from fuel-bound nitrogen was examined using two different approaches: fuel-lean and fuel-rich conditions. Finally, the last part of the thesis deals with deactivation of catalysts. The various deactivation processes which may affect high-temperature catalytic combustion are reviewed in paper IV. In paper V the poisoning effect of low amounts of sulfur was studied; various metal oxides as well as supported palladium and platinum catalysts were used as catalysts for combustion of a synthetic gas. In conclusion, with the results obtained in this thesis it would be possible to compose a working catalytic system for gas turbine application using a LHV gas.

Catalytic Kinetic Resolution of Biaryl Compounds.

Science.gov (United States)

Ma, Gaoyuan; Sibi, Mukund P

2015-08-10

Biaryl compounds with axial chirality are very common in synthetic chemistry, especially in catalysis. Axially chiral biaryls are important due to their biological activities and extensive applications in asymmetric catalysis. Thus the development of efficient enantioselective methods for their synthesis has attracted considerable attention. This Minireview discusses the progress made in catalytic kinetic resolution of biaryl compounds and chronicles significant advances made recently in catalytic kinetic resolution of biaryl scaffolds. © 2015 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim.

Catalytic conversion of ethanol on H-Y zeolite

Directory of Open Access Journals (Sweden)

Čegar Nedeljko

2005-01-01

Full Text Available The catalytic activity of the H-form of synthetic zeolite NaY was examined in this study. The catalytic activity was determined according to the rate of ethanol conversion in a gas phase in the static system. In the conversion of ethanol on synthetic NaY zeolite at 585, 595, and 610 K, on which the reaction develops at an optimal rate, ethene and diethyl ether are evolved in approximately the same quantity. After transforming the NaY zeolite into the H-form, its catalytic activity was extremely increases so, the reaction develops at a significantly lower temperature with a very large increase in the reaction rate. The distribution of the products also changes, so that at lower temperatures diethyl ether is elvolved in most cases, and the development of ethene is favored at higher ones, and after a certain period of time there is almost complete conversion of ethanol into ethene. The increase in catalytic activity, as well as the change of selectivity of conversion of ethanol on the H-form of zeolite, is the result of removing Na+ cations in the NaY zeolite, so that more acidic catalyst is obtained which contains a number of acidic catalytically active centers, as well as a more powerful one compared to the original NaY zeolite.

Catalytic Stereoinversion of L-Alanine to Deuterated D-Alanine.

Science.gov (United States)

Moozeh, Kimia; So, Soon Mog; Chin, Jik

2015-08-03

A combination of an achiral pyridoxal analogue and a chiral base has been developed for catalytic deuteration of L-alanine with inversion of stereochemistry to give deuterated D-alanine under mild conditions (neutral pD and 25 °C) without the use of any protecting groups. This system can also be used for catalytic deuteration of D-alanine with retention of stereochemistry to give deuterated D-alanine. Thus a racemic mixture of alanine can be catalytically deuterated to give an enantiomeric excess of deuterated D-alanine. While catalytic deracemization of alanine is forbidden by the second law of thermodynamics, this system can be used for catalytic deracemization of alanine with deuteration. Such green and biomimetic approach to catalytic stereocontrol provides insights into efficient amino acid transformations. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Including lateral interactions into microkinetic models of catalytic reactions

DEFF Research Database (Denmark)

Hellman, Anders; Honkala, Johanna Karoliina

2007-01-01

In many catalytic reactions lateral interactions between adsorbates are believed to have a strong influence on the reaction rates. We apply a microkinetic model to explore the effect of lateral interactions and how to efficiently take them into account in a simple catalytic reaction. Three differ...... different approximations are investigated: site, mean-field, and quasichemical approximations. The obtained results are compared to accurate Monte Carlo numbers. In the end, we apply the approximations to a real catalytic reaction, namely, ammonia synthesis....

Catalytic exhaust control

Energy Technology Data Exchange (ETDEWEB)

Heinemann, H

1973-09-01

Recent achievements and problems in the development of exhaust control devices in the USA are reviewed. To meet the 1976 emission standards, catalytic systems for the oxidation of carbon monoxide and hydrocarbons and for the reduction of nitrogen oxides to nitrogen and water are needed. While oxidizing catalysts using platinum, palladium, copper, vanadium, and chromium appplied on alumina or ceramic materials are more or less effective in emission control, there are no catalytic devices for the reduction of nitrogen oxides with the required useful life of 25,000 to 50,000 miles as yet available. In the case of platinum catalysts on monolithic supports, the operating temperature of 650 to 750/sup 0/C as required for the oxidation process may cause inactivation of the catalysts and fusion of the support material. The oxidation of CO and hydrocarbons is inhibited by high concentrations of CO, nitric oxide, and hydrocarbons. The use of catalytic converters requires the use of lead-free or low-lead gasoline. The nitrogen oxides conversion efficiency is considerably influenced by the oxygen-to-CO ratio of the exhaust gas, which makes limitation of this ratio necessary.

Towards Prebiotic Catalytic Amyloids Using High Throughput Screening.

Directory of Open Access Journals (Sweden)

Michael P Friedmann

Full Text Available Enzymes are capable of directing complex stereospecific transformations and of accelerating reaction rates many orders of magnitude. As even the simplest known enzymes comprise thousands of atoms, the question arises as to how such exquisite catalysts evolved. A logical predecessor would be shorter peptides, but they lack the defined structure and size that are apparently necessary for enzyme functions. However, some very short peptides are able to assemble into amyloids, thereby forming a well-defined tertiary structure called the cross-β-sheet, which bestows unique properties upon the peptides. We have hypothesized that amyloids could have been the catalytically active precursor to modern enzymes. To test this hypothesis, we designed an amyloid peptide library that could be screened for catalytic activity. Our approach, amenable to high-throughput methodologies, allowed us to find several peptides and peptide mixtures that form amyloids with esterase activity. These results indicate that amyloids, with their stability in a wide range of conditions and their potential as catalysts with low sequence specificity, would indeed be fitting precursors to modern enzymes. Furthermore, our approach can be efficiently expanded upon in library size, screening conditions, and target activity to yield novel amyloid catalysts with potential applications in aqueous-organic mixtures, at high temperature and in other extreme conditions that could be advantageous for industrial applications.

Testing weak form efficiency on the capital markets in Serbia

Directory of Open Access Journals (Sweden)

Kršikapa-Rašajski Jovana

2016-01-01

Full Text Available Weak-form efficient market hypothesis assumes that participants on the financial markets are not able to achieve above-average returns based on historical prices. In order to establish the presence of a weak-form market efficiency in the Serbian market, the analysis incorporates daily data of the two most prominent indices on the Belgrade Stock Exchange, BELEX 15 and BELEX LINE, since their inception until 31 December 2014. Results obtained by the analysis and testing indicate that the capital market in Serbia can not be considered sufficiently efficient, more precisely it indicates that postulates assumed by the weak-form market efficiency are not fully met. Taking into account that the capital market in Serbia is still underdeveloped, primarily because of the small volumes, turnover and types of securities which are traded on the market, as well as the fact that it is not sufficiently regulated and transparent, lack of investors is noticeable. Consequently, analysis presented in this paper indicates a weak sustainability of the efficient market hypothesis in Serbia.

Testing the Weak Form Efficiency in Pakistan’s Equity, Badla and Money Markets

OpenAIRE

Rashid, Abdul; Husain, Fazal

2009-01-01

The paper test the weak form market efficient hypothesis for Pakistan’s equity, badla and money markets with an aim to investigate which one of them is most efficient in the weak form sense. The analysis provides evidence, under the assumption of heteroscedasticity, that the KSE is weak-form efficient over the full-length sample period. Nevertheless, the analysis reports that over the same period the other two markets viz. badla and money are not weak form efficient. The badla market was effi...

Enhanced propylene production in FCC by novel catalytic materials

Energy Technology Data Exchange (ETDEWEB)

Kelkar, C.P.; Harris, D.; Xu, M.; Fu, J. [BASF Catalyst LLC, Iselin, NJ (United States)

2007-07-01

Fluid catalytic cracking is expected to increasingly supply the additional incremental requirements for propylene. The most efficient route to increase propylene yield from an FCC unit is through the use of medium pore zeolites such as ZSM-5. ZSM-5 zeolite cracks near linear olefins in the gasoline range to LPG olefins such as propylene and butylenes. This paper will describe catalytic approaches to increase gasoline range olefins and the chemistry of ZSM-5 to crack those olefins. The paper will also describe novel catalytic materials designed to increase propylene. (orig.)

A non-acid-assisted and non-hydroxyl-radical-related catalytic ozonation with ceria supported copper oxide in efficient oxalate degradation in water

KAUST Repository

Zhang, Tao

2012-06-01

Oxalate is usually used as a refractory model compound that cannot be effectively removed by ozone and hydroxyl radical oxidation in water. In this study, we found that ceria supported CuO significantly improved oxalate degradation in reaction with ozone. The optimum CuO loading amount was 12%. The molar ratio of oxalate removed/ozone consumption reached 0.84. The catalytic ozonation was most effective in a neutral pH range (6.7-7.9) and became ineffective when the water solution was acidic or alkaline. Moreover, bicarbonate, a ubiquitous hydroxyl radical scavenger in natural waters, significantly improved the catalytic degradation of oxalate. Therefore, the degradation relies on neither hydroxyl radical oxidation nor acid assistance, two pathways usually proposed for catalytic ozonation. These special characters of the catalyst make it suitable to be potentially used for practical degradation of refractory hydrophilic organic matter and compounds in water and wastewater. With in situ characterization, the new surface Cu(II) formed from ozone oxidation of the trace Cu(I) of the catalyst was found to be an active site in coordination with oxalate forming multi-dentate surface complex. It is proposed that the complex can be further oxidized by molecular ozone and then decomposes through intra-molecular electron transfer. The ceria support enhanced the activity of the surface Cu(I)/Cu(II) in this process. © 2012 Elsevier B.V.

Green and facile synthesis of fibrous Ag/cotton composites and their catalytic properties for 4-nitrophenol reduction

Science.gov (United States)

Li, Ziyu; Jia, Zhigang; Ni, Tao; Li, Shengbiao

2017-12-01

Natural cotton, featuring abundant oxygen-containing functional groups, has been utilized as a reductant to synthesize Ag nanoparticles on its surface. Through the facile and environment-friendly reduction process, the fibrous Ag/cotton composite (FAC) was conveniently synthesized. Various characterization techniques including XRD, XPS, TEM, SEM, EDS and FT-IR had been utilized to study the material microstructure and surface properties. The resulting FAC exhibited favorable activity on the catalytic reduction of 4-nitrophenol with high reaction rate. Moreover, the fibrous Ag/cotton composites were capable to form a desirable catalytic mat for catalyzing and simultaneous product separation. Reactants passing through the mat could be catalytically transformed to product, which is of great significance for water treatment. Such catalyst (FAC) was thus expected to have the potential as a highly efficient, cost-effective and eco-friendly catalyst for industrial applications. More importantly, this newly developed synthetic methodology could serve as a general tool to design and synthesize other metal/biomass composites catalysts for a wider range of catalytic applications.

Catalytic Conversion of Biofuels

DEFF Research Database (Denmark)

Jørgensen, Betina

This thesis describes the catalytic conversion of bioethanol into higher value chemicals. The motivation has been the unavoidable coming depletion of the fossil resources. The thesis is focused on two ways of utilising ethanol; the steam reforming of ethanol to form hydrogen and the partial oxida...

Application of BiFeO3-based on nickel foam composites with a highly efficient catalytic activity and easily recyclable in Fenton-like process under microwave irradiation

Science.gov (United States)

Li, Shuo; Zhang, Guangshan; Zheng, Heshan; Zheng, Yongjie; Wang, Peng

2018-05-01

In this study, BiFeO3 (BFO) powders decorated on nickel foam (NF) with a high catalytic activity are prepared via a one-step microwave-assisted hydrothermal method. The factors that influence the degradation of bisphenol A (BPA) with BFO/NFs as catalysts are optimized to improve the catalytic activity in a microwave-enhanced Fenton-like process. BFO/NF exhibit a superior catalytic activity with a high BPA removal ratio (98.4%) and TOC removal ratio (69.5%) within 5 min. Results indicate that NF significantly affect the improvement of the catalytic activity of BFO because it served as a source of hydroxyl radicals (•OH) during degradation. The amount of •OH generated by BFO/NF is approximately 1.65-fold higher than that by pure BFO. After six reaction cycles, the stability and reusability of •OH remain high. These findings provide new insights into the synthesis of composites on heterogeneous catalysts with high efficiency and easy recyclability for water treatment applications.

Investigation of combustion and thermodynamic performance of a lean burn catalytic combustion gas turbine system

International Nuclear Information System (INIS)

Yin Juan; Weng Yiwu

2011-01-01

The goals of this research were to investigate the combustion and thermodynamic performance of a lean burn catalytic combustion gas turbine. The characteristics of lean burn catalytic combustion were investigated by utilising 1D heterogeneous plug flow model which was validated by experiments. The effects of operating parameters on catalytic combustion were numerically analysed. The system models were built in ASPEN Plus and three independent design variables, i.e. compressor pressure ratio (PR), regenerator effectiveness (RE) and turbine inlet temperature (TIT) were selected to analyse the thermodynamic performance of the thermal cycle. The main results show that: simulations from 1D heterogeneous plug flow model can capture the trend of catalytic combustion and describe the behavior of the catalytic monolith in detail. Inlet temperature is the most significant parameter that impacts operation of the catalytic combustor. When TIT and RE are constant, the increase of PR results in lowering the inlet temperature of the catalytic combustor, which results in decreasing methane conversion. The peak thermal efficiency and the optimal PR at a constant TIT increase with the increase of TIT; and at the constant PR, the thermal efficiency increases with the increase of TIT. However, with lower TIT conditions, the optimal PR and the peak efficiency at a constant TIT of the LBCCGT cycle are relative low to that of the conventional cycle. When TIT and PR are constant, the decrease of RE may result in lower methane conversion. The influences of RE on the methane conversion and the thermal efficiency are more significant at higher PRs. The higher thermal efficiency for the lower RE is achieved at lower PR.

MECHANISMS OF THE COMPLEX FORMATION BY d-METALS ON POROUS SUPPORTS AND THE CATALYTIC ACTIVITY OF THE FORMED COMPLEXES IN REDOX REACTIONS

Directory of Open Access Journals (Sweden)

T. L. Rakitskaya

2015-11-01

Full Text Available The catalytic activity of supported complexes of d metals in redox reactions with participation of gaseous toxicants, PH3, CO, O3, and SO2, depends on their composition. Owing to the variety of physicochemical and structural-adsorption properties of available supports, their influence on complex formation processes, the composition and catalytic activity of metal complexes anchored on them varies over a wide range. The metal complex formation on sup-ports with weak ion-exchanging properties is similar to that in aqueous solutions. In this case, the support role mainly adds up to the ability to reduce the activity of water adsorbed on them. The interaction between a metal complex and a support surface occurs through adsorbed water molecules. Such supports can also affect complex formation processes owing to protolytic reactions on account of acidic properties of sorbents used as supports. The catalytic activity of metal complexes supported on polyphase natural sorbents considerably depends on their phase relationship. In the case of supports with the nonsimple structure and pronounced ion-exchanging properties, for instance, zeolites and laminar silicates, it is necessary to take into account the variety of places where metal ions can be located. Such location places determine distinctions in the coordination environment of the metal ions and the strength of their bonding with surface adsorption sites and, therefore, the catalytic activity of surface complexes formed by theses metal ions. Because of the energy surface inhomogeneity, it is important to determine a relationship between the strength of a metal complex bonding with a support surface and its catalytic activity. For example, bimetallic complexes are catalytically active in the reactions of oxidation of the above gaseous toxicants. In particular, in the case of carbon monoxide oxidation, the most catalytic activity is shown by palladium-copper complexes in which copper(II is strongly

Aerobic, catalytic oxidation of alcohols in ionic liquids

Directory of Open Access Journals (Sweden)

Souza Roberto F. de

2006-01-01

Full Text Available An efficient and simple catalytic system based on RuCl3 dissolved in ionic liquids has been developed for the oxidation of alcohols into aldehydes and ketones under mild conditions. A new fluorinated ionic liquid, 1-n-butyl-3-methylimidazolium pentadecafluorooctanoate, was synthesized and demonstrated better performance that the other ionic liquids employed. Moreover this catalytic system utilizes molecular oxygen as an oxidizing agent, producing water as the only by-product.

OPERATING SPECIFICATIONS OF CATALYTIC CLEANING OF GAS FROM BIOMASS GASIFICATION

Directory of Open Access Journals (Sweden)

Martin Lisý

2015-12-01

Full Text Available The paper focuses on the theoretical description of the cleaning of syngas from biomass and waste gasification using catalytic methods, and on the verification of the theory through experiments. The main obstruction to using syngas from fluid gasification of organic matter is the presence of various high-boiling point hydrocarbons (i.e., tar in the gas. The elimination of tar from the gas is a key factor in subsequent use of the gas in other technologies for cogeneration of electrical energy and heat. The application of a natural or artificial catalyst for catalytic destruction of tar is one of the methods of secondary elimination of tar from syngas. In our experiments, we used a natural catalyst (dolomite or calcium magnesium carbonate from Horní Lánov with great mechanical and catalytic properties, suitable for our purposes. The advantages of natural catalysts in contrast to artificial catalysts include their availability, low purchase prices and higher resilience to the so-called catalyst poison. Natural calcium catalysts may also capture undesired compounds of sulphure and chlorine. Our paper presents a theoretical description and analysis of catalytic destruction of tar into combustible gas components, and of the impact of dolomite calcination on its efficiency. The efficiency of the technology is verified in laboratories. The facility used for verification was a 150 kW pilot gasification unit with a laboratory catalytic filter. The efficiency of tar elimination reached 99.5%, the tar concentration complied with limits for use of the gas in combustion engines, and the tar content reached approximately 35 mg/mn3. The results of the measurements conducted in laboratories helped us design a pilot technology for catalytic gas cleaning.

THE WEAK FORM OF INFORMATIONAL EFFICIENCY: CASE OF TUNISIAN BANKING SECTOR

Directory of Open Access Journals (Sweden)

Fatma SIALA GUERMEZI

2016-02-01

Full Text Available This paper investigates the weak form of market efficiency hypothesis over eleven Tunisian banks listed on the Tunisian Stock Exchange during the period July 2012 to June 2013. GARCH (1, 1 and its extension EGARCH (1,1 are developed in order to describe the sign and size of financial volatility asymmetry. The results indicate that the Tunisian stock market, in particular the banking sector would not show characteristics of market efficiency. Some of the bank securities asymmetrically reacted to good and bad news. The presence of the leverage effect would imply that negative innovation (news has a greater impact on volatility than a positive innovation (news. This implies that this sector is not efficient under the weak form of the hypothesis. The implication of rejecting the weak form of efficiency for investors is that they can better predict stock price movements and abnormal earnings.

Microwave catalytic NOx and SO{sub 2} removal using FeCu/zeolite as catalyst

Energy Technology Data Exchange (ETDEWEB)

Z.S. Wei; G.H. Zeng; Z.R. Xie; C.Y. Ma; X.H. Liu; J.L. Sun; L.H. Liu [Sun Yat-sen University, Guangzhou (China). School of Environmental Science and Engineering

2011-04-15

Non-thermal plasma technology is a promising process for flue gas treatment. Microwave catalytic NOx and SO{sub 2} removal simultaneously has been investigated using FeCu/zeolite as catalyst. The experimental results showed that a microwave reactor with FeCu/zeolite only could be used to microwave catalytic oxidative 91.7% NOx to nitrates and 79.6% SO{sub 2} to sulfate; the reaction efficiencies of microwave catalytic reduction of NOx and SO{sub 2} in a microwave reactor with FeCu/zeolite and ammonium bicarbonate (NH{sub 4}HCO{sub 3}) as a reducing agent could be up to 95.8% and 93.4% respectively. Microwave irradiation accentuates catalytic reduction of SO{sub 2} and NOx treatment, and microwave addition can increases SO{sub 2} removal efficiency from 14.5% to 18.7%, and NOx removal efficiency from 13.4% to 18.7%, separately. FeCu/zeolite catalyst was characterized by X-ray diffraction (XRD), X-ray photoelectron spectrum analysis (XPS), scanning electron microscopy (SEM) and the Brunauer Emmett Teller (BET) method. Microwave catalytic NOx and SO{sub 2} removal follows Langmuir-Hinshelwood (L-H) kinetics. 25 refs., 7 figs., 1 tab.

Mutant form C115H of Clostridium sporogenes methionine γ-lyase efficiently cleaves S-Alk(en)yl-l-cysteine sulfoxides to antibacterial thiosulfinates.

Science.gov (United States)

Kulikova, Vitalia V; Anufrieva, Natalya V; Revtovich, Svetlana V; Chernov, Alexander S; Telegin, Georgii B; Morozova, Elena A; Demidkina, Tatyana V

2016-10-01

Pyridoxal 5'-phosphate-dependent methionine γ-lyase (MGL) catalyzes the β-elimination reaction of S-alk(en)yl-l-cysteine sulfoxides to thiosulfinates, which possess antimicrobial activity. Partial inactivation of the enzyme in the course of the reaction occurs due to oxidation of active site cysteine 115 conserved in bacterial MGLs. In this work, the C115H mutant form of Clostridium sporogenes MGL was prepared and the steady-state kinetic parameters of the enzyme were determined. The substitution results in an increase in the catalytic efficiency of the mutant form towards S-substituted l-cysteine sulfoxides compared to the wild type enzyme. We used a sulfoxide/enzyme system to generate antibacterial activity in situ. Two-component systems composed of the mutant enzyme and three S-substituted l-cysteine sulfoxides were demonstrated to be effective against Gram-positive and Gram-negative bacteria and three clinical isolates from mice. © 2016 IUBMB Life, 68(10):830-835, 2016. © 2016 International Union of Biochemistry and Molecular Biology.

Preparation and photo-catalytic activities of FeOOH/ZnO/MMT composite

Energy Technology Data Exchange (ETDEWEB)

Zhou, Yao, E-mail: zy19830808@163.com [College of Environment and Safety Engineering, Qingdao University of Science and Technology, Qingdao 266042 (China); Liu, Fusheng; Yu, Shitao [College of Chemical Engineering, Qingdao University of Science and Technology, Qingdao 266042 (China)

2015-11-15

Highlights: • The montmorillonite was used as the carrier for the synthesis of FeOOH nano-material and FeOOH/ZnO nano-material. • TEM was used to study the structure of the two nano-materials with the composite structure of goethite and wurtzite. • TEM was used to demonstrate FeOOH/ZnO nano-material can formed with the appropriate interface: wurtzite-(1 0 1)/(1 1 1)-goethite. • There were some coupling effect between FeOOH and ZnO, which can improve the photo-catalytic activities of FeOOH. • According to FTIR and TOC, PCP was degraded to aromatic ketone compounds and then to H{sub 2}O, CO{sub 2}, HCl. - Abstract: Montmorillonite (MMT) was used as the carrier for synthesis of FeOOH and FeOOH/ZnO nano-material. FeOOH and FeOOH/ZnO were synthesized by the aqueous solutions of Fe(NO{sub 3}){sub 3}–HNO{sub 3} and Zn(NO{sub 3}){sub 2}–NaOH/Fe(NO{sub 3}){sub 3}–HNO{sub 3} with the carrier of montmorillonite respectively. Transmission electron-microscopy (TEM) and X-ray diffraction (XRD) were used to study the morphology form and structure of the nano-materials. TEM was also used to demonstrate that FeOOH/ZnO can be formed with the appropriate interface. According to UV–vis absorption spectra, FeOOH/ZnO has a better response to visible light than FeOOH and ZnO, which indicates there is some coupling effect between FeOOH and ZnO. Pentachlorophenol (PCP) was used as a representative organic pollutant to evaluate the photo-catalytic efficiency of the FeOOH/ZnO and FeOOH catalysts in visible light (λ > 400 nm). The photo-catalytic efficiency of FeOOH/ZnO/MMT is better than FeOOH/MMT. According to FTIR, changes of pH and TOC, the degradation mechanism was also discussed. PCP was degraded to aromatic ketone and chloro-hydrocarbon compounds and then to H{sub 2}O, CO{sub 2} and HCl.

Processing and structural characterization of porous reforming catalytic films

International Nuclear Information System (INIS)

Hou Xianghui; Williams, Jey; Choy, Kwang-Leong

2006-01-01

Nickel-based catalysts are often used to reform methanol into hydrogen. The preparation and installation of these catalysts are costly and laborious. As an alternative, directly applying catalytic films onto the separator components can improve the manufacturing efficiency. This paper reports the successful deposition of adherent porous NiO-Al 2 O 3 -based catalytic films with well-controlled stoichiometry, using a single-step Aerosol Assisted Chemical Vapour Deposition (AACVD) method. The microstructure, composition and crystalline phase of the as-deposited catalytic films are characterized using a combination of X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and Fourier Transform Infrared (FTIR) Spectrometer. The results have demonstrated the capability of AACVD to produce porous NiO-Al 2 O 3 -based catalytic films

Oxygen Reduction Reaction for Generating H2 O2 through a Piezo-Catalytic Process over Bismuth Oxychloride.

Science.gov (United States)

Shao, Dengkui; Zhang, Ling; Sun, Songmei; Wang, Wenzhong

2018-02-09

Oxygen reduction reaction (ORR) for generating H 2 O 2 through green pathways have gained much attention in recent years. Herein, we introduce a piezo-catalytic approach to obtain H 2 O 2 over bismuth oxychloride (BiOCl) through an ORR pathway. The piezoelectric response of BiOCl was directly characterized by piezoresponse force microscopy (PFM). The BiOCl exhibits efficient catalytic performance for generating H 2 O 2 (28 μmol h -1 ) only from O 2 and H 2 O, which is above the average level of H 2 O 2 produced by solar-to-chemical processes. A piezo-catalytic mechanism was proposed: with ultrasonic waves, an alternating electric field will be generated over BiOCl, which can drive charge carriers (electrons) to interact with O 2 and H 2 O, then to form H 2 O 2 . © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Efficient implicit FEM simulation of sheet metal forming

NARCIS (Netherlands)

van den Boogaard, Antonius H.; Meinders, Vincent T.; Huetink, Han

2003-01-01

For the simulation of industrial sheet forming processes, the time discretisation is one of the important factors that determine the accuracy and efficiency of the algorithm. For relatively small models, the implicit time integration method is preferred, because of its inherent equilibrium check.

4. Seminar on efficient metal forming and machining: papers

International Nuclear Information System (INIS)

1982-01-01

The 4th seminar on efficient metal forming and machining was held at the CSIR conference centre in Pretoria on 16 November 1982. This conference basically discussed the forming, fabrication and machining of metals which included the different methods used as well as new developments on tools manufacturing and their applications. The topics that were discussed cover subjects such as the creep feed grinding, thermal properties of coating materials and their effect on the efficiency of coated cutting tools, economic rough and finish milling, the design and application of high speed steel cutting tools, aluminium extrusion, the manufacturing and finishing of extrusion dies, broaching techniques, cold forming in the fastener industry, finishing methods for spiral, bevel and hypoid gears, laser cutting, press tool design, and productivity in the forging industry. Another topic that were discussed, is the current status of diamond and cubic boron nitride composites, their synthesis and roll in the production of a new range of ultra hard ceramic-type materials

Biopolymer coated gold nanocrystals prepared using the green chemistry approach and their shape-dependent catalytic and surface-enhanced Raman scattering properties.

Science.gov (United States)

Chou, Chih-Wei; Hsieh, Hui-Hsuan; Hseu, You-Cheng; Chen, Ko-Shao; Wang, Gou-Jen; Chang, Hsien-Chang; Pan, Yong-Li; Wei, Yi-Syuan; Chang, Ko Hsin; Harn, Yeu-Wei

2013-07-21

This study deals with the preparation of multi-shaped nanoscale gold crystals under synthetically simple, green, and efficient conditions using a seed-mediated growth approach in the presence of hyaluronic acid (HA). These highly biocompatible multi-shaped gold nanocrystals were examined to evaluate their catalytic and surface enhanced Raman scattering (SERS) properties. The results show that the size and shape of the nanocrystals are mainly correlated to the amount of seed, seed size, HA concentration, and reaction temperature. Gold seeds accelerate the reduction of the gold precursor to form gold nanocrystals using HA. The HA serves as a reducing agent and a growth template for the reduction of Au(III) and nanocrystal stabilization. The multi-shaped gold nanocrystals showed superior catalytic properties and higher SERS performance. The simple, green approach efficiently controls the nanocrystals and creates many opportunities for future applications.

Catalytic asymmetric synthesis of the alkaloid (+)-myrtine

NARCIS (Netherlands)

Pizzuti, Maria Gabriefla; Minnaard, Adriaan J.; Feringa, Ben L.

2008-01-01

A new protocol for the asymmetric synthesis of trans-2,6-disubstituted-4-piperidones has been developed using a catalytic enantioselective conjugate addition reaction in combination with a diastereoselective lithiation-substitution sequence; an efficient synthesis of (+)-myrtine has been achieved

A comparative evaluation on the emission characteristics of ceramic and metallic catalytic converter in internal combustion engine

Science.gov (United States)

Leman, A. M.; Jajuli, Afiqah; Rahman, Fakhrurrazi; Feriyanto, Dafit; Zakaria, Supaat

2017-09-01

Enforcement of a stricter regulation on exhaust emission by many countries has led to utilization of catalytic converter to reduce the harmful pollutant emission. Ceramic and metallic catalytic converters are the most common type of catalytic converter used. The purpose of this study is to evaluate the performance of the ceramic and metallic catalytic converter on its conversion efficiency using experimental measurement. Both catalysts were placed on a modified exhaust system equipped with a Mitshubishi 4G93 single cylinder petrol engine that was tested on an eddy current dynamometer under steady state conditions for several engine speeds. The experimental results show that the metallic catalytic converter reduced a higher percentage of CO up to 98.6% reduction emissions while ceramic catalytic converter had a better reduction efficiency of HC up to 85.4% and 87.2% reduction of NOx.

A QM/MM study of the catalytic mechanism of nicotinamidase.

Science.gov (United States)

Sheng, Xiang; Liu, Yongjun

2014-02-28

Nicotinamidase (Pnc1) is a member of Zn-dependent amidohydrolases that hydrolyzes nicotinamide (NAM) to nicotinic acid (NA), which is a key step in the salvage pathway of NAD(+) biosynthesis. In this paper, the catalytic mechanism of Pnc1 has been investigated by using a combined quantum-mechanical/molecular-mechanical (QM/MM) approach based on the recently obtained crystal structure of Pnc1. The reaction pathway, the detail of each elementary step, the energetics of the whole catalytic cycle, and the roles of key residues and Zn-binding site are illuminated. Our calculation results indicate that the catalytic water molecule comes from the bulk solvent, which is then deprotonated by residue D8. D8 functions as a proton transfer station between C167 and NAM, while the activated C167 serves as the nucleophile. The residue K122 only plays a role in stabilizing intermediates and transition states. The oxyanion hole formed by the amide backbone nitrogen atoms of A163 and C167 has the function to stabilize the hydroxyl anion of nicotinamide. The Zn-binding site rather than a single Zn(2+) ion acts as a Lewis acid to influence the reaction. Two elementary steps, the activation of C167 in the deamination process and the decomposition of catalytic water in the hydrolysis process, correspond to the large energy barriers of 25.7 and 28.1 kcal mol(-1), respectively, meaning that both of them contribute a lot to the overall reaction barrier. Our results may provide useful information for the design of novel and efficient Pnc1 inhibitors and related biocatalytic applications.

Silica Sulphuric Acid as an Efficient Catalyst for the Catalytic and ...

African Journals Online (AJOL)

NJD

presence of a catalytic amount of silica sulphuric acid under micellar media in moderate to good yields. KEYWORDS. Sodium ... Production of aromatic nitro compounds is an important industrial process and involves the unsolved problems of ... V7 and Re9) and titanium and chromium silicates.10 Some of the procedures ...

Catalytic pleat filter bags for combined particulate separation and nitrogen oxides removal from flue gas streams

International Nuclear Information System (INIS)

Park, Young Ok; Choi, Ho Kyung

2010-01-01

The development of a high temperature catalytically active pleated filter bag with hybrid filter equipment for the combined removal of particles and nitrogen oxides from flue gas streams is presented. A special catalyst load in stainless steel mesh cartridge with a high temperature pleated filter bag followed by optimized catalytic activation was developed to reach the required nitrogen oxides levels and to maintain the higher collection efficiencies. The catalytic properties of the developed high temperature filter bags with hybrid filter equipment were studied and demonstrated in a pilot scale test rig and a demonstration plant using commercial scale of high temperature catalytic pleated filter bags. The performance of the catalytic pleated filter bags were tested under different operating conditions, such as filtration velocity and operating temperature. Moreover, the cleaning efficiency and residual pressure drop of the catalyst loaded cartridges in pleated filter bags were tested. As result of theses studies, the optimum operating conditions for the catalytic pleated filter bags are determined. (author)

Testing the Weak-Form Market Efficiency of the Euronext Wheat

Directory of Open Access Journals (Sweden)

Mihai Cristian Dinică

2015-03-01

Full Text Available Using a trading system based on various simple moving average crossings, the paper examines the weak-form market efficiency of the wheat traded at the Euronext exchange. After optimizing over the sample period, the best strategy is selected and then applied over the out-of-sample period. The profitability of this strategy is then compared with the simple buy and hold strategy. The methodology is then repeated for different sub-samples in order to check the results’ robustness. The results show that the weak-form market efficiency hypothesis cannot be rejected for the wheat case.

ABOUT FORMS, EFFICIENCY AND ASSESSMENT OF ENVIRONMENTAL MANAGEMENT

Directory of Open Access Journals (Sweden)

H. Bachev

2015-03-01

Full Text Available We suggest a holistic framework for analyzing, assessment and improvement of environmental management using “agrariansector” as an example. It incorporates an interdisciplinary approach (Economics, Organization, Law, Sociology, Ecology, Technology, Behavioral and Political Sciences and includes: specification of managerial actors, needs and spectrum of governing modes (institutional environment; private, collective, market, public modes at different level of decision-making (individual, farm, eco-system, local, regional, national, transnational, global; specification of critical socio-economic, natural, technological, behavioral etc. factors of managerial choice, and feasible spectrum of managerial forms; defining and assessing comparative and absolute efficiency of eco-management forms and system; improvement of forms of public intervention in eco-management.

Effect of process parameters and injector position on the efficiency of NOx reduction by selective non catalytic reduction technique

International Nuclear Information System (INIS)

Hamid, A.; Mehmood, M.A.; Irfan, N.; Javed, M.T.; Waheed, K.

2009-01-01

An experimental investigation has been performed to study the effect of atomizer pressure dilution of the reducing reagent and the injector position on the efficiency or the NOx reduction by a selective non-catalytic reduction technique using urea as a reducing agent. Experiments were performed with a flow reactor in which flue gas was generated by the combustion of methane in air at stoichiometric amount of oxygen and the desired levels of initial NOx (400-450 ppm) were achieved by doping the flame with ammonia. The work was directed to investigate the effect of atomizer pressure, dilution of urea reagent and the injector position. The atomizer pressure was varied from 1 to 3bar and 20-25% increase in efficiency was observed by decreasing the pressure. Effect of dilution of urea solution was investigated by varying the strength of the solution from the 8 to 32% and 40-45% increase in the efficiency was observed. Effects of injector position was investigated by injecting the urea solution both in co current and counter current direction of the flue gases and 20-25% increase in the efficiency was observed in counter current direction. (author)

Synthesis of E- and Z-trisubstituted alkenes by catalytic cross-metathesis

Science.gov (United States)

Nguyen, Thach T.; Koh, Ming Joo; Mann, Tyler J.; Schrock, Richard R.; Hoveyda, Amir H.

2017-12-01

Catalytic cross-metathesis is a central transformation in chemistry, yet corresponding methods for the stereoselective generation of acyclic trisubstituted alkenes in either the E or the Z isomeric forms are not known. The key problems are a lack of chemoselectivity—namely, the preponderance of side reactions involving only the less hindered starting alkene, resulting in homo-metathesis by-products—and the formation of short-lived methylidene complexes. By contrast, in catalytic cross-coupling, substrates are more distinct and homocoupling is less of a problem. Here we show that through cross-metathesis reactions involving E- or Z-trisubstituted alkenes, which are easily prepared from commercially available starting materials by cross-coupling reactions, many desirable and otherwise difficult-to-access linear E- or Z-trisubstituted alkenes can be synthesized efficiently and in exceptional stereoisomeric purity (up to 98 per cent E or 95 per cent Z). The utility of the strategy is demonstrated by the concise stereoselective syntheses of biologically active compounds, such as the antifungal indiacen B and the anti-inflammatory coibacin D.

Millisecond dynamics in glutaredoxin during catalytic turnover is dependent on substrate binding and absent in the resting states

DEFF Research Database (Denmark)

Jensen, Kristine Steen; Winther, Jakob R; Teilum, Kaare

2011-01-01

to the glutathione exchange rate was observed for 23 residues. Binding of reduced glutathione resulted in competitive inhibition of the reduced enzyme having kinetics similar to that of the reaction. This observation couples the motions observed during catalysis directly to substrate binding. Backbone motions......Conformational dynamics is important for enzyme function. Which motions of enzymes determine catalytic efficiency and whether the same motions are important for all enzymes, however, are not well understood. Here we address conformational dynamics in glutaredoxin during catalytic turnover...... with a combination of NMR magnetization transfer, R(2) relaxation dispersion, and ligand titration experiments. Glutaredoxins catalyze a glutathione exchange reaction, forming a stable glutathinoylated enzyme intermediate. The equilibrium between the reduced state and the glutathionylated state was biochemically...

Energy Efficient Microlith-Based Catalytic Reactor and Recuperator for Air Quality Control Applications

Science.gov (United States)

Vilekar, Saurabh A.; Hawley, Kyle; Junaedi, Christian; Crowder, Bruce; Prada, Julian; Mastanduno, Richard; Perry, Jay L.; Kayatin, Matthew J.

2017-01-01

Precision Combustion, Inc. (PCI) and NASA’s Marshall Space Flight Center (MSFC) have been developing, characterizing, and optimizing high temperature catalytic oxidizers (HTCO) based on PCI’s patented Microlith technology to meet the requirements of future extended human spaceflight explorations. Previous efforts focused on integrating PCI’s HTCO unit with a compact, simple recuperative heat exchanger to reduce the overall system size and weight. Significant improvement was demonstrated over traditional approaches of integrating the HTCO with an external recuperative heat exchanger. While the critical target performance metrics were achieved, the thermal effectiveness of PCI’s recuperator remained a potential area of improvement to further reduce the energy requirements of the integrated system. Using the same material combinations and an improved recuperator design, the redesigned prototype has experimentally demonstrated 20 – 30% reduction (flow dependent) in steady state power consumption compared to the earlier prototype without compromising the destruction efficiency of methane and volatile organic compounds (VOCs). Moreover, design modifications and improvements allow our redesigned prototype to be more easily manufactured compared to traditional brazed plate-fin recuperator designs. The redesigned prototype was delivered to MSFC for validation testing. Here, we report and discuss the performance of the improved prototype HTCO unit with a high efficiency recuperative heat exchanger based on testing at PCI and MSFC. The device is expected to provide a reliable and robust means of disposing of trace levels of methane and VOCs by oxidizing them into carbon dioxide and water in order to maintain clean air in enclosed spaces, such as crewed spacecraft cabins.

On the study of catalytic membrane reactor for water detritiation: Modeling approach

Energy Technology Data Exchange (ETDEWEB)

Liger, Karine, E-mail: karine.liger@cea.fr [CEA, DEN, DTN/SMTA/LIPC Cadarache, Saint Paul-lez-Durance F-13108 (France); Mascarade, Jérémy [CEA, DEN, DTN/SMTA/LIPC Cadarache, Saint Paul-lez-Durance F-13108 (France); Joulia, Xavier; Meyer, Xuan-Mi [Université de Toulouse, INPT, UPS, Laboratoire de Génie Chimique, 4, Allée Emile Monso, Toulouse F-31030 (France); CNRS, Laboratoire de Génie Chimique, Toulouse F-31030 (France); Troulay, Michèle; Perrais, Christophe [CEA, DEN, DTN/SMTA/LIPC Cadarache, Saint Paul-lez-Durance F-13108 (France)

2016-11-01

Highlights: • Experimental results for the conversion of tritiated water (using deuterium as a simulant of tritium) by means of a catalytic membrane reactor in view of tritium recovery. • Phenomenological 2D model to represent catalytic membrane reactor behavior including the determination of the compositions of gaseous effluents. • Good agreement between the simulation results and experimental measurements performed on the dedicated facility. • Explanation of the unexpected behavior of the catalytic membrane reactor by the modeling results and in particular the gas composition estimation. - Abstract: In the framework of tritium recovery from tritiated water, efficiency of packed bed membrane reactors have been successfully demonstrated. Thanks to protium isotope swamping, tritium bonded water can be recovered under the valuable Q{sub 2} form (Q = H, D or T) by means of isotope exchange reactions occurring on catalyst surface. The use of permselective Pd-based membrane allows withdrawal of reactions products all along the reactor, and thus limits reverse reaction rate to the benefit of the direct one (shift effect). The reactions kinetics, which are still little known or unknown, are generally assumed to be largely greater than the permeation ones so that thermodynamic equilibriums of isotope exchange reactions are generally assumed. This paper proposes a new phenomenological 2D model to represent catalytic membrane reactor behavior with the determination of gas effluents compositions. A good agreement was obtained between the simulation results and experimental measurements performed on a dedicated facility. Furthermore, the gas composition estimation permits to interpret unexpected behavior of the catalytic membrane reactor. In the next future, further sensitivity analysis will be performed to determine the limits of the model and a kinetics study will be conducted to assess the thermodynamic equilibrium of reactions.

On the study of catalytic membrane reactor for water detritiation: Modeling approach

International Nuclear Information System (INIS)

Liger, Karine; Mascarade, Jérémy; Joulia, Xavier; Meyer, Xuan-Mi; Troulay, Michèle; Perrais, Christophe

2016-01-01

Highlights: • Experimental results for the conversion of tritiated water (using deuterium as a simulant of tritium) by means of a catalytic membrane reactor in view of tritium recovery. • Phenomenological 2D model to represent catalytic membrane reactor behavior including the determination of the compositions of gaseous effluents. • Good agreement between the simulation results and experimental measurements performed on the dedicated facility. • Explanation of the unexpected behavior of the catalytic membrane reactor by the modeling results and in particular the gas composition estimation. - Abstract: In the framework of tritium recovery from tritiated water, efficiency of packed bed membrane reactors have been successfully demonstrated. Thanks to protium isotope swamping, tritium bonded water can be recovered under the valuable Q_2 form (Q = H, D or T) by means of isotope exchange reactions occurring on catalyst surface. The use of permselective Pd-based membrane allows withdrawal of reactions products all along the reactor, and thus limits reverse reaction rate to the benefit of the direct one (shift effect). The reactions kinetics, which are still little known or unknown, are generally assumed to be largely greater than the permeation ones so that thermodynamic equilibriums of isotope exchange reactions are generally assumed. This paper proposes a new phenomenological 2D model to represent catalytic membrane reactor behavior with the determination of gas effluents compositions. A good agreement was obtained between the simulation results and experimental measurements performed on a dedicated facility. Furthermore, the gas composition estimation permits to interpret unexpected behavior of the catalytic membrane reactor. In the next future, further sensitivity analysis will be performed to determine the limits of the model and a kinetics study will be conducted to assess the thermodynamic equilibrium of reactions.

Facile synthesis of polypyrrole functionalized nickel foam with catalytic activity comparable to Pt for the poly-generation of hydrogen and electricity

Science.gov (United States)

Tang, Tiantian; Li, Kan; Shen, Zhemin; Sun, Tonghua; Wang, Yalin; Jia, Jinping

2016-01-01

Polypyrrole functionalized nickel foam is facilely prepared through the potentiostatic electrodeposition. The PPy-functionalized Ni foam functions as a hydrogen-evolution cathode in a rotating disk photocatalytic fuel cell, in which hydrogen energy and electric power are generated by consuming organic wastes. The PPy-functionalized Ni foam cathode exhibits stable catalytic activities after thirteen continuous runs. Compared with net or plate structure, the Ni foam with a unique three-dimensional reticulate structure is conducive to the electrodeposition of PPy. Compared with Pt-group electrode, PPy-coated Ni foam shows a satisfactory catalytic performance for the H2 evolution. The combination of PPy and Ni forms a synergistic effect for the rapid trapping and removal of proton from solution and the catalytic reduction of proton to hydrogen. The PPy-functionalized Ni foam could be applied in photocatalytic and photoelectrochemical generation of H2. In all, we report a low cost, high efficient and earth abundant PPy-functionalized Ni foam with a satisfactory catalytic activities comparable to Pt for the practical application of poly-generation of hydrogen and electricity.

Orion EFT-1 Catalytic Tile Experiment Overview and Flight Measurements

Science.gov (United States)

Salazar, Giovanni; Amar, Adam; Hyatt, Andrew; Rezin, Marc D.

2016-01-01

This paper describes the design and results of a surface catalysis flight experiment flown on the Orion Multipurpose Crew Vehicle during Exploration Flight Test 1 (EFT1). Similar to previous Space Shuttle catalytic tile experiments, the present test consisted of a highly catalytic coating applied to an instrumented TPS tile. However, the present catalytic tile experiment contained significantly more instrumentation in order to better resolve the heating overshoot caused by the change in surface catalytic efficiency at the interface between two distinct materials. In addition to collecting data with unprecedented spatial resolution of the "overshoot" phenomenon, the experiment was also designed to prove if such a catalytic overshoot would be seen in turbulent flow in high enthalpy regimes. A detailed discussion of the results obtained during EFT1 is presented, as well as the challenges associated with data interpretation of this experiment. Results of material testing carried out in support of this flight experiment are also shown. Finally, an inverse heat conduction technique is employed to reconstruct the flight environments at locations upstream and along the catalytic coating. The data and analysis presented in this work will greatly contribute to our understanding of the catalytic "overshoot" phenomenon, and have a significant impact on the design of future spacecraft.

Drastic reduction in the surface recombination velocity of crystalline silicon passivated with catalytic chemical vapor deposited SiNx films by introducing phosphorous catalytic-doped layer

International Nuclear Information System (INIS)

Thi, Trinh Cham; Koyama, Koichi; Ohdaira, Keisuke; Matsumura, Hideki

2014-01-01

We improve the passivation property of n-type crystalline silicon (c-Si) surface passivated with a catalytic chemical vapor deposited (Cat-CVD) Si nitride (SiN x ) film by inserting a phosphorous (P)-doped layer formed by exposing c-Si surface to P radicals generated by the catalytic cracking of PH 3 molecules (Cat-doping). An extremely low surface recombination velocity (SRV) of 2 cm/s can be achieved for 2.5 Ω cm n-type (100) floating-zone Si wafers passivated with SiN x /P Cat-doped layers, both prepared in Cat-CVD systems. Compared with the case of only SiN x passivated layers, SRV decreases from 5 cm/s to 2 cm/s. The decrease in SRV is the result of field effect created by activated P atoms (donors) in a shallow P Cat-doped layer. Annealing process plays an important role in improving the passivation quality of SiN x films. The outstanding results obtained imply that SiN x /P Cat-doped layers can be used as promising passivation layers in high-efficiency n-type c-Si solar cells.

Electrochemical catalytic treatment of phenol wastewater

International Nuclear Information System (INIS)

Ma Hongzhu; Zhang Xinhai; Ma Qingliang; Wang Bo

2009-01-01

The slurry bed catalytic treatment of contaminated water appears to be a promising alternative for the oxidation of aqueous organic pollutants. In this paper, the electrochemical oxidation of phenol in synthetic wastewater catalyzed by ferric sulfate and potassium permanganate adsorbed onto active bentonite in slurry bed electrolytic reactor with graphite electrode has been investigated. In order to determine the optimum operating condition, the orthogonal experiments were devised and the results revealed that the system of ferric sulfate, potassium permanganate and active bentonite showed a high catalytic efficiency on the process of electrochemical oxidation phenol in initial pH 5. When the initial concentration of phenol was 0.52 g/L (the initial COD 1214 mg/L), up to 99% chemical oxygen demand (COD) removal was obtained in 40 min. According to the experimental results, a possible mechanism of catalytic degradation of phenol was proposed. Environmental estimation was also done and the results showed that the treated wastewater have little impact on plant growth and could totally be applied to irrigation.

Electrochemical catalytic treatment of phenol wastewater

Energy Technology Data Exchange (ETDEWEB)

Ma Hongzhu, E-mail: hzmachem@snnu.edu.cn [Institute of Energy Chemistry, School of Chemistry and Materials Science, Shaanxi Normal University, Xi' an 710062 (China); Zhang Xinhai [Institute of Energy Chemistry, School of Chemistry and Materials Science, Shaanxi Normal University, Xi' an 710062 (China); Ma Qingliang [Department of Applied Physics, College of Sciences, Taiyuan University of Technology, 030024 Taiyuan (China); Wang Bo [Institute of Energy Chemistry, School of Chemistry and Materials Science, Shaanxi Normal University, Xi' an 710062 (China)

2009-06-15

The slurry bed catalytic treatment of contaminated water appears to be a promising alternative for the oxidation of aqueous organic pollutants. In this paper, the electrochemical oxidation of phenol in synthetic wastewater catalyzed by ferric sulfate and potassium permanganate adsorbed onto active bentonite in slurry bed electrolytic reactor with graphite electrode has been investigated. In order to determine the optimum operating condition, the orthogonal experiments were devised and the results revealed that the system of ferric sulfate, potassium permanganate and active bentonite showed a high catalytic efficiency on the process of electrochemical oxidation phenol in initial pH 5. When the initial concentration of phenol was 0.52 g/L (the initial COD 1214 mg/L), up to 99% chemical oxygen demand (COD) removal was obtained in 40 min. According to the experimental results, a possible mechanism of catalytic degradation of phenol was proposed. Environmental estimation was also done and the results showed that the treated wastewater have little impact on plant growth and could totally be applied to irrigation.

Identification of a third form of NaK-ATPase catalytic subunit in rat brain by photoaffinity labeling

International Nuclear Information System (INIS)

Lowndes, J.M.; Millan, N.M.; Ruoho, A.E.; Hokin-Neaverson, M.

1987-01-01

Using photoaffinity labeling, they have found a form of the NaK-ATPase catalytic subunit, α(-), in the rat brain that is distinct from the α and α(+) forms. Strong radiolabeling of α(-) was obtained with [ 125 I]azido-iodophenethylamido-succinyl-cymarin (AISC). AISC is a new cardiotonic steroid photolabel which they have synthesized and characterized chemically and biochemically. This compound labels α(-) better than the photolabels that they have previously reported. SDS-PAGE (5%) of photolabeled rat brain microsomes showed that α(-) migrated with faster mobility than the dog kidney α subunit. The α(-) appears to have different specificity for different cardiotonic steroids than either α(+) or α. The radiolabeling of rat brain α(+) and dog kidney α with [ 125 I]AISC was protectable by ouabain; in contrast, 1 mM ouabain did not reduce the [ 125 I]AISC-labeling of α(-), although the labeling was protected with 200 μM cymarin or AISC. The results indicate that the α(-) form of the NaK-ATPase in rat brain binds cymarin and its derivative but has little affinity for ouabain. It is possible that α(-) may be the translation product of the rat brain α(III) mRNA which has recently been described

Directed modification of L-LcLDH1, an L-lactate dehydrogenase from Lactobacillus casei, to improve its specific activity and catalytic efficiency towards phenylpyruvic acid.

Science.gov (United States)

Li, Jian-Fang; Li, Xue-Qing; Liu, Yan; Yuan, Feng-Jiao; Zhang, Ting; Wu, Min-Chen; Zhang, Ji-Ru

2018-05-22

To improve the specific activity and catalytic efficiency of L-LcLDH1, an NADH-dependent allosteric L-lactate dehydrogenase from L. casei, towards phenylpyruvic acid (PPA), its directed modification was conducted based on the semi-rational design. The three variant genes, Lcldh1 Q88R , Lcldh1 I229A and Lcldh1 T235G , were constructed by whole-plasmid PCR as designed theoretically, and expressed in E. coli BL21(DE3), respectively. The purified mutant, L-LcLDH1 Q88R or L-LcLDH1 I229A , displayed the specific activity of 451.5 or 512.4 U/mg towards PPA, by which the asymmetric reduction of PPA afforded L-phenyllactic acid (PLA) with an enantiomeric excess (ee p ) more than 99%. Their catalytic efficiencies (k cat /K m ) without D-fructose-1,6-diphosphate (D-FDP) were 4.8- and 5.2-fold that of L-LcLDH1. Additionally, the k cat /K m values of L-LcLDH1 Q88R and L-LcLDH1 I229A with D-FDP were 168.4- and 8.5-fold higher than those of the same enzymes without D-FDP, respectively. The analysis of catalytic mechanisms by molecular docking (MD) simulation indicated that substituting I229 in L-LcLDH1 with Ala enlarges the space of substrate-binding pocket, and that the replacement of Q88 with Arg makes the inlet of pocket larger than that of L-LcLDH1. Copyright © 2018 Elsevier B.V. All rights reserved.

Nanocrystalline Mn-Mo-Ce Oxide Anode Doped Rare Earth Ce and Its Selective Electro-catalytic Performance

Directory of Open Access Journals (Sweden)

SHI Yan-hua

2017-09-01

Full Text Available The anode oxide of nanocrystalline Mn-Mo-Ce was prepared by anode electro-deposition technology, and its nanostructure and selective electro-catalytic performance were investigated using the SEM, EDS, XRD, HRTEM, electrochemical technology and oxygen evolution efficiency testing. Furthermore, the selective electro-catalytic mechanism of oxygen evolution and chlorine depression was discussed. The results show that the mesh-like nanostructure Mn-Mo-Ce oxide anode with little cerium doped is obtained, and the oxygen evolution efficiency for the anode in the seawater is 99.51%, which means a high efficiency for the selective electro-catalytic for the oxygen evolution. Due to the structural characteristics of γ-MnO2, the OH- ion is preferentially absorbed, while Cl- absorption is depressed. OH- accomplishes the oxygen evolution process during the valence transition electrocatalysis of Mn4+/Mn3+, completing the selective electro-catalysis process. Ce doping greatly increases the reaction activity, and promotes the absorption and discharge; the rising interplanar spacing between active (100 crystalline plane promotes OH- motion and the escape of newborn O2, so that the selective electro-catalytic property with high efficient oxygen evolution and chlorine depression is achieved from the nano morphology effect.

THE FORM OF THE COOKING VESSEL AND THE ENERGETIC EFFICIENCY OF COOKING

Directory of Open Access Journals (Sweden)

PAUL KRÄMER

2009-09-01

Full Text Available The present paper examines the contribution of the form of the cooking vessel to the heat transfer efficiency of the stove/pot system. A rounded (convex pot bottom increases the surface available for heat transfer and, hence, heat transfer efficiency. We suggest that combustion-efficient stoves combined with rounded-bottom vessels compare favourably to the same stoves in combination with flat-bottom stoves. Clay pots with a rounded bottom correspond to African traditions. Nowadays metal pots with rounded bottoms are locally produced in some areas. Implications of pot forms for the outcome of Water Boiling Tests are also discussed.

Catalytic reduction of organic dyes at gold nanoparticles impregnated silica materials: influence of functional groups and surfactants

International Nuclear Information System (INIS)

Azad, Uday Pratap; Ganesan, Vellaichamy; Pal, Manas

2011-01-01

Gold nanoparticles (Au NPs) in three different silica based sol–gel matrixes with and without surfactants are prepared. They are characterized by UV–vis absorbance and transmission electron microscopic (TEM) studies. The size and shape of Au NPs varied with the organo-functional group present in the sol–gel matrix. In the presence of mercaptopropyl functionalized organo-silica, large sized (200–280 nm) spherical Au NPs are formed whereas in the presence of aminopropyl functionalized organo-silica small sized (5–15 nm) Au NPs are formed inside the tube like organo-silica. Further, it is found that Au NPs act as efficient catalyst for the reduction of organic dyes. The catalytic rate constant is evaluated from the decrease in absorbance of the dye molecules. Presence of cationic or anionic surfactants greatly influences the catalytic reaction. The other factors like hydrophobicity of the organic dyes, complex formation of the dyes with anionic surfactants, repulsion between dyes and cationic surfactant, adsorption of dyes on the Au NPs also play important role on the reaction rate.

Catalytic reduction of organic dyes at gold nanoparticles impregnated silica materials: influence of functional groups and surfactants

Energy Technology Data Exchange (ETDEWEB)

Azad, Uday Pratap; Ganesan, Vellaichamy, E-mail: velganesh@yahoo.com; Pal, Manas [Banaras Hindu University, Department of Chemistry, Faculty of Science (India)

2011-09-15

Gold nanoparticles (Au NPs) in three different silica based sol-gel matrixes with and without surfactants are prepared. They are characterized by UV-vis absorbance and transmission electron microscopic (TEM) studies. The size and shape of Au NPs varied with the organo-functional group present in the sol-gel matrix. In the presence of mercaptopropyl functionalized organo-silica, large sized (200-280 nm) spherical Au NPs are formed whereas in the presence of aminopropyl functionalized organo-silica small sized (5-15 nm) Au NPs are formed inside the tube like organo-silica. Further, it is found that Au NPs act as efficient catalyst for the reduction of organic dyes. The catalytic rate constant is evaluated from the decrease in absorbance of the dye molecules. Presence of cationic or anionic surfactants greatly influences the catalytic reaction. The other factors like hydrophobicity of the organic dyes, complex formation of the dyes with anionic surfactants, repulsion between dyes and cationic surfactant, adsorption of dyes on the Au NPs also play important role on the reaction rate.

Catalytic Oxidation of Allylic Alcohols to Methyl Esters

DEFF Research Database (Denmark)

Gallas-Hulin, Agata; Kotni, Rama Krishna; Nielsen, Martin

2017-01-01

Aerobic oxidation of allylic alcohols to methyl esters using gold nanoparticles supported on different metal oxide carriers has been performed successfully under mild conditions (room temperature, 0.1 MPa O2) without significant loss of catalytic activity. The effects of different reaction...... parameters are studied to find the suitable reaction conditions. All catalysts are characterised by XRD, XRF and TEM. Among these catalysts, Au/TiO2 showed the most efficient catalytic activity towards the selective oxidation of allylic alcohols to the corresponding esters. Moreover, the same Au/TiO2...... to synthesize methyl esters from allylic alcohols....

A Temperature Window for the Synthesis of Single-Walled Carbon Nanotubes by Catalytic Chemical Vapor Deposition of CH4over Mo2-Fe10/MgO Catalyst

Directory of Open Access Journals (Sweden)

Yu Ouyang

2009-01-01

Full Text Available Abstract A temperature window for the synthesis of single-walled carbon nanotubes by catalytic chemical vapor deposition of CH4over Mo2-Fe10/MgO catalyst has been studied by Raman spectroscopy. The results showed that when the temperature is lower than 750 °C, there were few SWCNTs formed, and when the temperature is higher than 950 °C, mass amorphous carbons were formed in the SWCNTs bundles due to the self-decomposition of CH4. The temperature window of SWCNTs efficient growth is between 800 and 950 °C, and the optimum growth temperature is about 900 °C. These results were supported by transmission electron microscope images of samples formed under different temperatures. The temperature window is important for large-scale production of SWCNTs by catalytic chemical vapor deposition method.

Chemistry - Toward efficient hydrogen production at surfaces

DEFF Research Database (Denmark)

Nørskov, Jens Kehlet; Christensen, Claus H.

2006-01-01

Calculations are providing a molecular picture of hydrogen production on catalytic surfaces and within enzymes, knowledge that may guide the design of new, more efficient catalysts for the hydrogen economy.......Calculations are providing a molecular picture of hydrogen production on catalytic surfaces and within enzymes, knowledge that may guide the design of new, more efficient catalysts for the hydrogen economy....

Functional tuning of the catalytic residue pKa in a de novo designed esterase.

Science.gov (United States)

Hiebler, Katharina; Lengyel, Zsófia; Castañeda, Carlos A; Makhlynets, Olga V

2017-09-01

AlleyCatE is a de novo designed esterase that can be allosterically regulated by calcium ions. This artificial enzyme has been shown to hydrolyze p-nitrophenyl acetate (pNPA) and 4-nitrophenyl-(2-phenyl)-propanoate (pNPP) with high catalytic efficiency. AlleyCatE was created by introducing a single-histidine residue (His 144 ) into a hydrophobic pocket of calmodulin. In this work, we explore the determinants of catalytic properties of AlleyCatE. We obtained the pK a value of the catalytic histidine using experimental measurements by NMR and pH rate profile and compared these values to those predicted from electrostatics pK a calculations (from both empirical and continuum electrostatics calculations). Surprisingly, the pK a value of the catalytic histidine inside the hydrophobic pocket of calmodulin is elevated as compared to the model compound pK a value of this residue in water. We determined that a short-range favorable interaction with Glu 127 contributes to the elevated pK a of His 144 . We have rationally modulated local electrostatic potential in AlleyCatE to decrease the pK a of its active nucleophile, His 144 , by 0.7 units. As a direct result of the decrease in the His 144 pK a value, catalytic efficiency of the enzyme increased by 45% at pH 6. This work shows that a series of simple NMR experiments that can be performed using low field spectrometers, combined with straightforward computational analysis, provide rapid and accurate guidance to rationally improve catalytic efficiency of histidine-promoted catalysis. Proteins 2017; 85:1656-1665. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

Catalytic Ammonia Decomposition over High-Performance Ru/Graphene Nanocomposites for Efficient COx-Free Hydrogen Production

Directory of Open Access Journals (Sweden)

Gang Li

2017-01-01

Full Text Available Highly-dispersed Ru nanoparticles were grown on graphene nanosheets by simultaneously reducing graphene oxide and Ru ions using ethylene glycol (EG, and the resultant Ru/graphene nanocomposites were applied as a catalyst to ammonia decomposition for COx-free hydrogen production. Tuning the microstructures of Ru/graphene nanocomposites was easily accomplished in terms of Ru particle size, morphology, and loading by adjusting the preparation conditions. This was the key to excellent catalytic activity, because ammonia decomposition over Ru catalysts is structure-sensitive. Our results demonstrated that Ru/graphene prepared using water as a co-solvent greatly enhanced the catalytic performance for ammonia decomposition, due to the significantly improved nano architectures of the composites. The long-term stability of Ru/graphene catalysts was evaluated for COx-free hydrogen production from ammonia at high temperatures, and the structural evolution of the catalysts was investigated during the catalytic reactions. Although there were no obvious changes in the catalytic activities at 450 °C over a duration of 80 h, an aggregation of the Ru nanoparticles was still observed in the nanocomposites, which was ascribed mainly to a sintering effect. However, the performance of the Ru/graphene catalyst was decreased gradually at 500 °C within 20 h, which was ascribed mainly to both the effect of the methanation of the graphene nanosheet under a H2 atmosphere and to enhanced sintering under high temperatures.

Computational Efficient Upscaling Methodology for Predicting Thermal Conductivity of Nuclear Waste forms

International Nuclear Information System (INIS)

Li, Dongsheng; Sun, Xin; Khaleel, Mohammad A.

2011-01-01

This study evaluated different upscaling methods to predict thermal conductivity in loaded nuclear waste form, a heterogeneous material system. The efficiency and accuracy of these methods were compared. Thermal conductivity in loaded nuclear waste form is an important property specific to scientific researchers, in waste form Integrated performance and safety code (IPSC). The effective thermal conductivity obtained from microstructure information and local thermal conductivity of different components is critical in predicting the life and performance of waste form during storage. How the heat generated during storage is directly related to thermal conductivity, which in turn determining the mechanical deformation behavior, corrosion resistance and aging performance. Several methods, including the Taylor model, Sachs model, self-consistent model, and statistical upscaling models were developed and implemented. Due to the absence of experimental data, prediction results from finite element method (FEM) were used as reference to determine the accuracy of different upscaling models. Micrographs from different loading of nuclear waste were used in the prediction of thermal conductivity. Prediction results demonstrated that in term of efficiency, boundary models (Taylor and Sachs model) are better than self consistent model, statistical upscaling method and FEM. Balancing the computation resource and accuracy, statistical upscaling is a computational efficient method in predicting effective thermal conductivity for nuclear waste form.

Multiple functionalities of Ni nanoparticles embedded in carboxymethyl guar gum polymer: catalytic activity and superparamagnetism

International Nuclear Information System (INIS)

Sardar, Debasmita; Sengupta, Manideepa; Bordoloi, Ankur; Ahmed, Md. A.; Neogi, S.K.; Bandyopadhyay, Sudipta; Jain, Ruchi; Gopinath, Chinnakonda S.; Bala, Tanushree

2017-01-01

Highlights: • Ni nanoparticles were synthesized in polymer to form Ni-Polymer composite. • Ni nanoparticles retain their superparamagnetism in the composite. • Ni-Polymer composites showed catalytic activity. - Abstract: Composites comprising of metallic nanoparticles in polymer matrices have allured significant importance due to multifunctionalities. Here a simple protocol has been described to embed Ni nanoparticles in carboxymethyl guar gum (CMGG) polymer. The composite formation helps in the stabilization of Ni nanoparticles which are otherwise prone towards aerial oxidation. Further the nanoparticles retain their superparamagnetic nature and catalytic capacity. Ni-Polymer composite catalyses the reduction of 4-Nitrophenol to 4-Aminophenol very efficiently in presence of NaBH_4, attaining a complete conversion under some experimental conditions. Ni-Polymer composite is well characterized using UV–vis spectroscopy, FTIR, XPS, powder XRD, TGA, SEM and TEM. A detailed magnetic measurement using superconducting quantum interference device-vibrating sample magnetometer (SQUID-VSM) reveals superparamagnetic behaviour of the composite.

Multiple functionalities of Ni nanoparticles embedded in carboxymethyl guar gum polymer: catalytic activity and superparamagnetism

Energy Technology Data Exchange (ETDEWEB)

Sardar, Debasmita [Department of Chemistry, University of Calcutta, 92 A.P.C. Road, Kolkata 700009 (India); Sengupta, Manideepa; Bordoloi, Ankur [Nano Catalysis, Catalytic Conversion and Process Division, CSIR—Indian Institute of Petroleum (IIP), Mohkampur, Dehradun 248005 (India); Ahmed, Md. A.; Neogi, S.K.; Bandyopadhyay, Sudipta [Department of Physics, University of Calcutta, 92 A.P.C. Road, Kolkata 700009 (India); Jain, Ruchi; Gopinath, Chinnakonda S. [Catalysis Division and Center of Excellence on Surface Science, CSIR—National Chemical Laboratory, Dr. Homi Bhabha Road, Pune 411 008 (India); Bala, Tanushree, E-mail: tanushreebala@gmail.com [Department of Chemistry, University of Calcutta, 92 A.P.C. Road, Kolkata 700009 (India)

2017-05-31

Highlights: • Ni nanoparticles were synthesized in polymer to form Ni-Polymer composite. • Ni nanoparticles retain their superparamagnetism in the composite. • Ni-Polymer composites showed catalytic activity. - Abstract: Composites comprising of metallic nanoparticles in polymer matrices have allured significant importance due to multifunctionalities. Here a simple protocol has been described to embed Ni nanoparticles in carboxymethyl guar gum (CMGG) polymer. The composite formation helps in the stabilization of Ni nanoparticles which are otherwise prone towards aerial oxidation. Further the nanoparticles retain their superparamagnetic nature and catalytic capacity. Ni-Polymer composite catalyses the reduction of 4-Nitrophenol to 4-Aminophenol very efficiently in presence of NaBH{sub 4}, attaining a complete conversion under some experimental conditions. Ni-Polymer composite is well characterized using UV–vis spectroscopy, FTIR, XPS, powder XRD, TGA, SEM and TEM. A detailed magnetic measurement using superconducting quantum interference device-vibrating sample magnetometer (SQUID-VSM) reveals superparamagnetic behaviour of the composite.

Solvent-free Oxidation of Alcohols and Mild Catalytic Deprotection of ...

African Journals Online (AJOL)

tetrabromobenzene- 1,3-disulphonamide (TBBDA) can be used for solvent-free oxidation of primary and secondary alcohols to the corresponding carbonyl compounds without over-oxidation, and efficient catalytic deprotection of various silyl ...

Green technology for conversion of renewable hydrocarbon based on plasma-catalytic approach

Science.gov (United States)

Fedirchyk, Igor; Nedybaliuk, Oleg; Chernyak, Valeriy; Demchina, Valentina

2016-09-01

The ability to convert renewable biomass into fuels and chemicals is one of the most important steps on our path to green technology and sustainable development. However, the complex composition of biomass poses a major problem for established conversion technologies. The high temperature of thermochemical biomass conversion often leads to the appearance of undesirable byproducts and waste. The catalytic conversion has reduced yield and feedstock range. Plasma-catalytic reforming technology opens a new path for biomass conversion by replacing feedstock-specific catalysts with free radicals generated in the plasma. We studied the plasma-catalytic conversion of several renewable hydrocarbons using the air plasma created by rotating gliding discharge. We found that plasma-catalytic hydrocarbon conversion can be conducted at significantly lower temperatures (500 K) than during the thermochemical ( 1000 K) and catalytic (800 K) conversion. By using gas chromatography, we determined conversion products and found that conversion efficiency of plasma-catalytic conversion reaches over 85%. We used obtained data to determine the energy yield of hydrogen in case of plasma-catalytic reforming of ethanol and compared it with other plasma-based hydrogen-generating systems.

Preparation and characterization of LTA-type zeolite framework dispersed ruthenium nanoparticles and their catalytic application in the hydrolytic dehydrogenation of ammonia–borane for efficient hydrogen generation

International Nuclear Information System (INIS)

Zahmakiran, Mehmet

2012-01-01

Highlights: ► Ru(0)NPs-ZK-4 were prepared and characterized by advanced analytical techniques. ► They achieve the hydrolysis of ammonia-borane with TOF = 5410 h −1 and TTO = 36700. ► They maintain 85% of their activity even at the fifth catalytic run. - Abstract: The safe and efficient hydrogen storage and production are major obstacles to use hydrogen as an energy carrier. Therefore, significant efforts have been focused on the development of new materials for the chemical hydrogen storage and production. Of particular importance, ammonia–borane (NH 3 BH 3 ) is emerging as one of the most promising solid hydrogen carrier due to its high gravimetric hydrogen storage capacity (19.6 wt.%) and low molecular weight (30.8 g/mol). ammonia–borane can release hydrogen gas upon catalytic hydrolysis under mild conditions. Herein, the discovery of a new catalytic material, ruthenium nanoparticles stabilized by ZK-4 zeolite framework, for this important reaction has been reported. This new catalyst system was prepared by borohydride reduction of ruthenium(III)-exchanged ZK-4 zeolite in water at room temperature. The characterization of the resulting material by advanced analytical tools shows the formation of ZK-4 zeolite dispersed ruthenium nanoparticles (2.9 ± 0.9 nm). The catalytic performance of the resulting supported ruthenium nanoparticles depending on activity, lifetime and reusability was demonstrated in the hydrolytic dehydrogenation of ammonia–borane. They were found to be highly active (initial TOF = 5410 h −1 ), long-lived (TTO = 36,700) and reusable catalyst (retaining of >85% of initial activity in the 5th reuse) in this important catalytic reaction at room temperature under air.

Catalytic production of metal carbonyls from metal oxides

Science.gov (United States)

Sapienza, Richard S.; Slegeir, William A.; Foran, Michael T.

1984-01-01

This invention relates to the formation of metal carbonyls from metal oxides and specially the formation of molybdenum carbonyl and iron carbonyl from their respective oxides. Copper is used here in admixed form or used in chemically combined form as copper molybdate. The copper/metal oxide combination or combined copper is utilized with a solvent, such as toluene and subjected to carbon monoxide pressure of 25 atmospheres or greater at about 150.degree.-260.degree. C. The reducing metal copper is employed in catalytic concentrations or combined concentrations as CuMoO.sub.4 and both hydrogen and water present serve as promoters. It has been found that the yields by this process have been salutary and that additionally the catalytic metal may be reused in the process to good effect.

NOx Selective Catalytic Reduction (SCR) on Self-Supported V-W-doped TiO2 Nanofibers

DEFF Research Database (Denmark)

Marani, Debora; Silva, Rafael Hubert; Dankeaw, Apiwat

2017-01-01

Electrospun V–W–TiO2 catalysts, resulting in a solid solution of V and W in the anatase phase, are prepared as nonwoven nanofibers for NOx selective catalytic reduction (SCR). Preliminary catalytic characterization indicates their superior NOx conversion efficiency to the-state-of-the-art materia...

The evolution of catalytic function

Science.gov (United States)

Maurel, Marie-Christine; Ricard, Jacques

2006-03-01

It is very likely that the main driving force of enzyme evolution is the requirement to improve catalytic and regulatory efficiency which results from the intrinsic performance as well as from the spatial and functional organization of enzymes in living cells. Kinetic co-operativity may occur in simple monomeric proteins if they display “slow” conformational transitions, at the cost of catalytic efficiency. Oligomeric enzymes on the other hand can be both efficient and co-operative. We speculate that the main reason for the emergence of co-operative oligomeric enzymes is the need for catalysts that are both cooperative and efficient. As it is not useful for an enzyme to respond to a change of substrate concentration in a complex kinetic way, the emergence of symmetry has its probable origin in a requirement for “functional simplicity”. In a living cell, enzyme are associated with other macromolecules and membranes. The fine tuning of their activity may also be reached through mutations of the microenvironment. Our hypothesis is that these mutations are related to the vectorial transport of molecules, to achieve the hysteresis loops of enzyme reactions generated by the coupling of reaction and diffusion, through the co-operativity brought about by electric interactions between a charged substrate and a membrane, and last but not least, through oscillations. As the physical origins of these effects are very simple and do not require complex molecular devices, it is very likely that the functional advantage generated by the spatial and functional organization of enzyme molecules within the cell have appeared in prebiotic catalysis or very early during the primeval stages of biological evolution. We shall began this paper by presenting the nature of the probable earliest catalysts in the RNA world.

Computer-aided modeling framework – a generic modeling template for catalytic membrane fixed bed reactors

DEFF Research Database (Denmark)

Fedorova, Marina; Sin, Gürkan; Gani, Rafiqul

2013-01-01

and users to generate and test models systematically, efficiently and reliably. In this way, development of products and processes can be faster, cheaper and very efficient. In this contribution, as part of the framework a generic modeling template for the systematic derivation of problem specific catalytic...... membrane fixed bed models is developed. The application of the modeling template is highlighted with a case study related to the modeling of a catalytic membrane reactor coupling dehydrogenation of ethylbenzene with hydrogenation of nitrobenzene....

VUV photo-oxidation of gaseous benzene combined with ozone-assisted catalytic oxidation: Effect on transition metal catalyst

International Nuclear Information System (INIS)

Huang, Haibao; Lu, Haoxian; Zhan, Yujie; Liu, Gaoyuan; Feng, Qiuyu; Huang, Huiling; Wu, Muyan; Ye, Xinguo

2017-01-01

Graphical abstract: Mn nanoparticles are highly dispersed on ZSM-5 and most efficient in benzene degradation in the VUV-OZCO process. - Highlights: • Vacuum UV irradiation is well combined with O_3 catalytic oxidation. • O_3 byproducts was used to enhance catalytic oxidation of VOCs. • Mn/ZSM-5 achieved the best catalytic activity for benzene degradation. - Abstract: Volatile organic compounds (VOCs) cause the major air pollution concern. In this study, a series of ZSM-5 supported transition metals were prepared by impregnation method. They were combined with vacuum UV (VUV) photo-oxidation in a continuous-flow packed-bed reactor and used for the degradation of benzene, a typical toxic VOCs. Compared with VUV photo-oxidation alone, the introduction of catalysts can greatly enhance benzene oxidation under the help of O_3, the by-products from VUV irradiation, via ozone-assisted catalytic oxidation (OZCO). The catalytic activity of transition metals towards benzene oxidation followed the order: Mn > Co > Cu > Ni > Fe. Mn achieved the best catalytic activity due to the strongest capability for O_3 catalytic decomposition and utilization. Benzene and O_3 removal efficiency reached as high as 97% and 100% after 360 min, respectively. O_3 was catalytically decomposed, generating highly reactive oxidants such as ·OH and ·O for benzene oxidation.

VUV photo-oxidation of gaseous benzene combined with ozone-assisted catalytic oxidation: Effect on transition metal catalyst

Energy Technology Data Exchange (ETDEWEB)

Huang, Haibao, E-mail: seabao8@gmail.com [School of Environmental Science and Engineering, Sun Yat-Sen University (China); Guangdong Provincial Key Laboratory of Environmental Pollution Control and Remediation Technology (Sun Yat-sen University) (China); Lu, Haoxian; Zhan, Yujie; Liu, Gaoyuan; Feng, Qiuyu; Huang, Huiling; Wu, Muyan; Ye, Xinguo [School of Environmental Science and Engineering, Sun Yat-Sen University (China)

2017-01-01

Graphical abstract: Mn nanoparticles are highly dispersed on ZSM-5 and most efficient in benzene degradation in the VUV-OZCO process. - Highlights: • Vacuum UV irradiation is well combined with O{sub 3} catalytic oxidation. • O{sub 3} byproducts was used to enhance catalytic oxidation of VOCs. • Mn/ZSM-5 achieved the best catalytic activity for benzene degradation. - Abstract: Volatile organic compounds (VOCs) cause the major air pollution concern. In this study, a series of ZSM-5 supported transition metals were prepared by impregnation method. They were combined with vacuum UV (VUV) photo-oxidation in a continuous-flow packed-bed reactor and used for the degradation of benzene, a typical toxic VOCs. Compared with VUV photo-oxidation alone, the introduction of catalysts can greatly enhance benzene oxidation under the help of O{sub 3}, the by-products from VUV irradiation, via ozone-assisted catalytic oxidation (OZCO). The catalytic activity of transition metals towards benzene oxidation followed the order: Mn > Co > Cu > Ni > Fe. Mn achieved the best catalytic activity due to the strongest capability for O{sub 3} catalytic decomposition and utilization. Benzene and O{sub 3} removal efficiency reached as high as 97% and 100% after 360 min, respectively. O{sub 3} was catalytically decomposed, generating highly reactive oxidants such as ·OH and ·O for benzene oxidation.

Photolytic AND Catalytic Destruction of Organic Waste Water Pollutants

Science.gov (United States)

Torosyan, V. F.; Torosyan, E. S.; Kryuchkova, S. O.; Gromov, V. E.

2017-01-01

The system: water supply source - potable and industrial water - wastewater - sewage treatment - water supply source is necessary for water supply and efficient utilization of water resources. Up-to-date technologies of waste water biological treatment require for special microorganisms, which are technologically complex and expensive but unable to solve all the problems. Application of photolytic and catalytically-oxidizing destruction is quite promising. However, the most reagents are strong oxidizers in catalytic oxidation of organic substances and can initiate toxic substance generation. Methodic and scientific approaches to assess bread making industry influence on the environment have been developed in this paper in order to support forecasting and taking technological decisions concerning reduction of this influence. Destructive methods have been tested: ultra violet irradiation and catalytic oxidation for extraction of organic compounds from waste water by natural reagents.

Cross-catalytic peptide nucleic acid (PNA) replication based on templated ligation

DEFF Research Database (Denmark)

Singhal, Abhishek; Nielsen, Peter E

2014-01-01

We report the first PNA self-replicating system based on template directed cross-catalytic ligation, a process analogous to biological replication. Using two template PNAs and four pentameric precursor PNAs, all four possible carbodiimide assisted amide ligation products were detected...... precursors. Cross-catalytic product formation followed product inhibited kinetics, but approximately two replication rounds were observed. Analogous but less efficient replication was found for a similar tetrameric system. These results demonstrate that simpler nucleobase replication systems than natural...

Catalytic conversion of light alkanes

Energy Technology Data Exchange (ETDEWEB)

Lyons, J.E.

1992-06-30

The second Quarterly Report of 1992 on the Catalytic Conversion of Light Alkanes reviews the work done between April 1, 1992 and June 31, 1992 on the Cooperative Agreement. The mission of this work is to devise a new catalyst which can be used in a simple economic process to convert the light alkanes in natural gas to oxygenate products that can either be used as clean-burning, high octane liquid fuels, as fuel components or as precursors to liquid hydrocarbon uwspomdon fuel. During the past quarter we have continued to design, prepare, characterize and test novel catalysts for the mild selective reaction of light hydrocarbons with air or oxygen to produce alcohols directly. These catalysts are designed to form active metal oxo (MO) species and to be uniquely active for the homolytic cleavage of the carbon-hydrogen bonds in light alkanes producing intermediates which can form alcohols. We continue to investigate three molecular environments for the active catalytic species that we are trying to generate: electron-deficient macrocycles (PHASE I), polyoxometallates (PHASE II), and regular oxidic lattices including zeolites and related structures as well as other molecular surface structures having metal oxo groups (PHASE I).

Formalization of hydrocarbon conversion scheme of catalytic cracking for mathematical model development

Science.gov (United States)

Nazarova, G.; Ivashkina, E.; Ivanchina, E.; Kiseleva, S.; Stebeneva, V.

2015-11-01

The issue of improving the energy and resource efficiency of advanced petroleum processing can be solved by the development of adequate mathematical model based on physical and chemical regularities of process reactions with a high predictive potential in the advanced petroleum refining. In this work, the development of formalized hydrocarbon conversion scheme of catalytic cracking was performed using thermodynamic parameters of reaction defined by the Density Functional Theory. The list of reaction was compiled according to the results of feedstock structural-group composition definition, which was done by the n-d-m-method, the Hazelvuda method, qualitative composition of feedstock defined by gas chromatography-mass spectrometry and individual composition of catalytic cracking gasoline fraction. Formalized hydrocarbon conversion scheme of catalytic cracking will become the basis for the development of the catalytic cracking kinetic model.

Transition state analogue imprinted polymers as artificial amidases for amino acid p-nitroanilides: morphological effects of polymer network on catalytic efficiency.

Science.gov (United States)

Mathew, Divya; Thomas, Benny; Devaky, K S

2017-11-13

The morphology of the polymer network - porous/less porous - plays predominant role in the amidase activities of the polymer catalysts in the hydrolytic reactions of amino acid p-nitroanilides. Polymers with the imprints of stable phosphonate analogue of the intermediate of hydrolytic reactions were synthesized as enzyme mimics. Molecular imprinting was carried out in thermodynamically stable porogen dimethyl sulphoxide and unstable porogen chloroform, to investigate the morphological effects of polymers on catalytic amidolysis. It was found that the medium of polymerization has vital influence in the amidase activities of the enzyme mimics. The morphological studies of the polymer catalysts were carried out by scanning electron microscopy and Bruner-Emmett-Teller analysis. The morphology of the polymer catalysts and their amidase activities are found to be dependent on the composition of reaction medium. The polymer catalyst prepared in dimethyl sulphoxide is observed to be efficient in 1:9 acetonitrile (ACN)-Tris HCl buffer and that prepared in chloroform is noticed to be stereo specifically and shape-selectively effective in 9:1 ACN-Tris HCl buffer. The solvent memory effect in catalytic amidolysis was investigated using the polymer prepared in acetonitrile.

Malbranchea cinnamomea: A thermophilic fungal source of catalytically efficient lignocellulolytic glycosyl hydrolases and metal dependent enzymes.

Science.gov (United States)

Mahajan, Chhavi; Basotra, Neha; Singh, Surender; Di Falco, Marcos; Tsang, Adrian; Chadha, B S

2016-01-01

This study reports thermophilic fungus Malbranchea cinnamomea as an important source of lignocellulolytic enzymes. The secretome analysis using LC-MS/MS orbitrap showed that fungus produced a spectrum of glycosyl hydrolases (cellulase/hemicellulase), polysaccharide lyases (PL) and carbohydrate esterases (CE) in addition to cellobiose dehydrogenase (CDH) indicating the presence of functional classical and oxidative cellulolytic mechanisms. The protein fractions in the secretome resolved by ion exchange chromatography were analyzed for ability to hydrolyze alkali treated carrot grass (ATCG) in the presence of Mn(2+)/Cu(2+). This strategy in tandem with peptide mass fingerprinting led to identification of metal dependent protein hydrolases with no apparent hydrolytic activity, however, showed 5.7 folds higher saccharification in presence of Mn(2+). Furthermore, adding different protein fractions to commercial cellulase (Novozymes: Cellic CTec2) resulted in enhanced hydrolysis of ATCG ranging between 1.57 and 3.43 folds indicating the enzymes from M. cinnamomea as catalytically efficient. Copyright © 2015 Elsevier Ltd. All rights reserved.

Complementary structure sensitive and insensitive catalytic relationships

NARCIS (Netherlands)

Santen, van R.A.

2009-01-01

The burgeoning field of nanoscience has stimulated an intense interest in properties that depend on particle size. For transition metal particles, one important property that depends on size is catalytic reactivity, in which bonds are broken or formed on the surface of the particles. Decreased

Pulsed laser synthesis in liquid of efficient visible-light-active ZnO/rGO nanocomposites for improved photo-catalytic activity

Science.gov (United States)

Moqbel, Redhwan A.; Gondal, Mohammed A.; Qahtan, Talal F.; Dastageer, Mohamed A.

2018-03-01

In this work the synthesis of visible light active zinc oxide/reduced graphene oxide (ZnO/rGO) nanocomposite by laser induced fragmentation of particulates in liquid, its morphological/optical characterizations, and its application in the process of photo-catalytic degradation of toxic Rhodamine B (RhB) dye under visible radiation were studied. It is observed from the optical and morphological characterization that the anchoring of ZnO on the rGO sheets in ZnO/rGO nanocomposite considerably reduced the aggregation of ZnO (increased surface area), reduced the recombination of photo-induced charge carriers, promoted more adsorption of reactants on the catalytic surface and also enhanced and extended the light absorption in the visible spectral region. With all these improved characteristics of ZnO/rGO nanocomposite, it was found that this material as a photo-catalyst yielded an RhB degradation efficiency of 86%, as compared to the 40% degradation with pure ZnO NPs under the same experimental conditions. In the ZnO/rGO nanocomposite, rGO functions as an electron acceptor to promote charge separation, an aggregation inhibitor to enhance the active surface area, a co-catalyst, a good dye adsorber and also as a supporting matrix for ZnO.

Pyrrolic-N-doped graphene oxide/Fe2O3 mesocrystal nanocomposite: Efficient charge transfer and enhanced photo-Fenton catalytic activity

Science.gov (United States)

Liu, Bing; Tian, Lihong; Wang, Ran; Yang, Jinfeng; Guan, Rong; Chen, Xiaobo

2017-11-01

Though α-Fe2O3 has attracted much attention in photocatalytic or Fenton-catalytic degradation of organic contaminants, its performance is still unsatisfactory due to fast recombination of electrons and holes in photocatalytic process and the difficult conversion of Fe(II) and Fe(III) in Fenton reaction. Herein, a pyrrolic N-doped graphene oxide/Fe2O3 mesocrystal (NG-Fe2O3) nanocomposite with good distribution is synthesized by a simple solvothermal method and adjusting the oxygen-containing groups on graphene oxide. The morphology of NG-Fe2O3 contributes to a relatively large BET surface area and an intimate contact between NG and Fe2O3. These two important factors along with the excellent electro-conductivity of pyrrolic-N doped GO result in the efficient separation of electron-hole pairs and fast conversion of Fe(II)and Fe(III) in photo-Fenton synergistic reaction. Thus, a remarkably improved photo-Fenton catalytic activity of NG-Fe2O3 is obtained. The degrading rate on methyl blue increases by 1.5 times and the conversion rate of glyphosate increases by 2.3 times under visible light irradiation, compared to pristine α-Fe2O3 mesocrystals.

Catalytic Efficiency of Basidiomycete Laccases: Redox Potential versus Substrate-Binding Pocket Structure

Directory of Open Access Journals (Sweden)

Olga A. Glazunova

2018-04-01

Full Text Available Laccases are copper-containing oxidases that catalyze a one-electron abstraction from various phenolic and non-phenolic compounds with concomitant reduction of molecular oxygen to water. It is well-known that laccases from various sources have different substrate specificities, but it is not completely clear what exactly provides these differences. The purpose of this work was to study the features of the substrate specificity of four laccases from basidiomycete fungi Trametes hirsuta, Coriolopsis caperata, Antrodiella faginea, and Steccherinum murashkinskyi, which have different redox potentials of the T1 copper center and a different structure of substrate-binding pockets. Enzyme activity toward 20 monophenolic substances and 4 phenolic dyes was measured spectrophotometrically. The kinetic parameters of oxidation of four lignans and lignan-like substrates were determined by monitoring of the oxygen consumption. For the oxidation of the high redox potential (>700 mV monophenolic substrates and almost all large substrates, such as phenolic dyes and lignans, the redox potential difference between the enzyme and the substrate (ΔE played the defining role. For the low redox potential monophenolic substrates, ΔE did not directly influence the laccase activity. Also, in the special cases, the structure of the large substrates, such as dyes and lignans, as well as some structural features of the laccases (flexibility of the substrate-binding pocket loops and some amino acid residues in the key positions affected the resulting catalytic efficiency.

Low and medium heating value coal gas catalytic combustor characterization

Science.gov (United States)

Schwab, J. A.

1982-01-01

Catalytic combustion with both low and medium heating value coal gases obtained from an operating gasifier was demonstrated. A practical operating range for efficient operation was determined, and also to identify potential problem areas were identified for consideration during stationary gas turbine engine design. The test rig consists of fuel injectors, a fuel-air premixing section, a catalytic reactor with thermocouple instrumentation and a single point, water cooled sample probe. The test rig included inlet and outlet transition pieces and was designed for installation into an existing test loop.

Testing the Week Form Efficiency of Pakistani Stock Market (2000-2010

Directory of Open Access Journals (Sweden)

Abdul Haque

2011-01-01

Full Text Available This empirical paper tests out the weak form efficiency of Pakistani stock market by examining the weekly index over the period . Return series has a leptokurtic and negatively skewed distribution, which is away from normal distribution as reflected by significant Jarque-Bera statistic. Estimated results of ADF (1979, PP (1988 and KPSS (1992 tests, Ljung-Box Q-Statistic of autocorrelations and runs test of randomness reject the Random Walk Hypothesis (RWH for the returns series. Moreover the results of variance ratio test (Lo and MacKinlay (1988 also reject the RWH and prove the robustness of other estimated results. The rejection of RWH reveals that the Pakistani stock prices are not Weak Form Efficient.

Indium triflate in 1-isobutyl-3-methylimidazolium dihydrogenphosphate: an efficient and green catalytic system for Friedel-Crafts acylation

DEFF Research Database (Denmark)

Tran, Phuong Hoang; Hoang, Huy Manh; Chau, Duy-Khiem Nguyen

2015-01-01

Indium triflate in the ionic liquid, 1-isobutyl-3-methylimidazolium dihydrogen phosphate ([i-BMIM]H2PO4), was found to show enhanced catalytic activity in the Friedel–Crafts acylation of various aromatic compounds with acid anhydrides. The catalytic system was easily recovered and reused without...

The Performance of Chrome-Coated Copper as Metallic Catalytic Converter to Reduce Exhaust Gas Emissions from Spark-Ignition Engine

Science.gov (United States)

Warju; Harto, S. P.; Soenarto

2018-01-01

One of the automotive technologies to reduce exhaust gas emissions from the spark-ignition engine (SIE) is by using a catalytic converter. The aims of this research are firstly to conduct a metallic catalytic converter, secondly to find out to what extend chrome-coated copper plate (Cu+Cr) as a catalyst is efficient. To measure the concentration of carbon monoxide (CO) and hydrocarbon (HC) on the frame there are two conditions required. First is when the standard condition, and second is when Cu+Cr metallic catalytic converter is applied using exhaust gas analyzer. Exhaust gas emissions from SIE are measured by using SNI 19-7118.1-2005. The testing of CO and HC emissions were conducted with variable speed to find the trend of exhaust gas emissions from idle speed to high speed. This experiment results in the fact that the use of Cu+Cr metallic catalytic converter can reduce the production of CO and HC of a four-stroke gasoline engine. The reduction of CO and HC emission are 95,35% and 79,28%. Using active metal catalyst in form of metallic catalytic converter, it is gained an optimum effective surface of a catalyst which finally is able to decrease the amount of CO and HC emission significantly in every spinning happened in the engine. Finally, this technology can be applied to the spark ignition engine both car and motorcycle to support blue sky program in Indonesia.

Catalytic stereoselective synthesis of highly substituted indanones via tandem Nazarov cyclization and electrophilic fluorination trapping.

Science.gov (United States)

Nie, Jing; Zhu, Hong-Wei; Cui, Han-Feng; Hua, Ming-Qing; Ma, Jun-An

2007-08-02

A new catalytic stereoselective tandem transformation via Nazarov cyclization/electrophilic fluorination has been accomplished. This sequence is efficiently catalyzed by a Cu(II) complex to afford fluorine-containing 1-indanone derivatives with two new stereocenters with high diastereoselectivity (trans/cis up to 49/1). Three examples of catalytic enantioselective tandem transformation are presented.

A catalytic distillation process for light gas oil hydrodesulfurization

Energy Technology Data Exchange (ETDEWEB)

Vargas-Villamil, F.D.; Marroquin, J.O.; Paz, C. de la; Rodriguez, E. [Prog. de Matematicas Aplicadas y Computacion, Prog. de Tratamiento de Crudo Maya, Instituto Mexicano del Petroleo, Mexico City, DF (Mexico)

2004-07-01

A light gas oil hydrodesulfurization process via catalytic distillation is developed and compared to a conventional process. By integrating the separation and reaction into a single unit, the catalytic distillation may produce a diesel with low concentration of sulfur compounds at a lower cost than the traditional reaction/separation process. The process proposed in this work is compared to an optimised conventional hydrodesulfurization unit which represents fairly well a plant that belongs to the National System of Refineries. During the optimisation of the conventional process, a compromise is established among the production of diesel and naphtha and the operating costs. The results show that the light gas oil hydrodesulfurization via catalytic distillation is as or more efficient than the conventional process. However, the removal of the sulfur compounds is carried out under less rigorous conditions. This design reduces the fix and operational costs. (author)

Catalytic decomposition of gaseous 1,2-dichlorobenzene over CuOx/TiO₂ and CuOx/TiO₂-CNTs catalysts: Mechanism and PCDD/Fs formation.

Science.gov (United States)

Wang, Qiu-lin; Huang, Qun-xing; Wu, Hui-fan; Lu, Sheng-yong; Wu, Hai-long; Li, Xiao-dong; Yan, Jian-hua

2016-02-01

Gaseous 1,2-dichlorobenzene (1,2-DCBz) was catalytically decomposed in a fixed-bed catalytic reactor using composite copper-based titanium oxide (CuOx/TiO2) catalysts with different copper ratios. Carbon nanotubes (CNTs) were introduced to produce novel CuOx/TiO2-CNTs catalysts by the sol-gel method. The catalytic performances of CuOx/TiO2 and CuOx/TiO2-CNTs on 1,2-DCBz oxidative destruction under different temperatures (150-350 °C) were experimentally examined and the correlation between catalyst structure and catalytic activity was characterized and the role of oxygen in catalytic reaction was discussed. Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) generation during 1,2-DCBz catalytic oxidation by CuOx/TiO2-CNTs composite catalyst was also examined. Results indicate that the 1,2-DCBz destruction/removal efficiencies of CuOx (4 wt%)/TiO2 catalyst at 150 °C and 350 °C with a GHSV of 3400 h(-1) are 59% and 94% respectively and low-temperature (150 °C) catalytic activity of CuOx/TiO2 on 1,2-DCBz oxidation can be improved from 59 to 77% when CNTs are introduced. Furthermore, oxygen either in catalyst or from reaction atmosphere is indispensible in reaction. The former is offered to activate and oxidize the 1,2-DCBz adsorbed on catalyst, thus can be generally consumed during reaction and the oxygen content in catalyst is observed lost from 39.9 to 35.0 wt% after reacting under inert atmosphere; the latter may replenish the vacancy in catalyst created by the consumed oxygen thus extends the catalyst life and raises the destruction/removal efficiency. The introduction of CNTs also increases the Cu(2+)/Cu(+) ratio, chemisorbed oxygen concentration and surface lattice oxygen binding energy which are closely related with catalytic activity. PCDD/Fs is confirmed to be formed when 1,2-DCBz catalytically oxidized by CuOx/TiO2-CNTs composite catalyst with sufficient oxygen (21%), proper temperature (350 °C) and high concentration of 1,2-DCBz feed (120 ppm

Heterogeneous Photo catalytic Degradation of Hazardous Waste in Aqueous Suspension

International Nuclear Information System (INIS)

Sadek, S.A.; Ebraheem, S.; Friesen, K.J.

1999-01-01

The photo catalytic degradation of hazardous waste like chlorinated paraffin compound (1,12-Dichlorodoecane Ded) was investigated in different aquatic media using GC-MSD. The direct photolysis of Ded in HPLC water was considered to be negligible (k = 0.0020+-0.0007h - 1 ) . An acceleration of the photodegradation rate was occurred in presence of different TiO 2 catalyst systems. Molecular oxygen was found to play a vital role in the degradation process. Anatase TiO 2 was proved to be the most efficient one (k=0.7670+-0.0876h -1 ), while the rate constant of the rutile TiO 2 was calculated to be 0.2780+-0.0342h -1 . Improvement of photo catalytic efficiency of rutile TiO 2 was achieved by addition of Fe +2 giving a rate constant =0.6710+-0.0786h -1

Degradation of paracetamol by catalytic wet air oxidation and sequential adsorption – Catalytic wet air oxidation on activated carbons

International Nuclear Information System (INIS)

Quesada-Peñate, I.; Julcour-Lebigue, C.; Jáuregui-Haza, U.J.; Wilhelm, A.M.; Delmas, H.

2012-01-01

Highlights: ► Three activated carbons (AC) compared as adsorbents and oxidation catalysts. ► Similar evolution for catalytic and adsorptive properties of AC over reuses. ► Acidic and mesoporous AC to be preferred, despite lower initial efficiency. ► Oxidative degradation of paracetamol improves biodegradability. ► Convenient hybrid adsorption–regenerative oxidation process for continuous treatment. - Abstract: The concern about the fate of pharmaceutical products has raised owing to the increasing contamination of rivers, lakes and groundwater. The aim of this paper is to evaluate two different processes for paracetamol removal. The catalytic wet air oxidation (CWAO) of paracetamol on activated carbon was investigated both as a water treatment technique using an autoclave reactor and as a regenerative treatment of the carbon after adsorption in a sequential fixed bed process. Three activated carbons (ACs) from different source materials were used as catalysts: two microporous basic ACs (S23 and C1) and a meso- and micro-porous acidic one (L27). During the first CWAO experiment the adsorption capacity and catalytic performance of fresh S23 and C1 were higher than those of fresh L27 despite its higher surface area. This situation changed after AC reuse, as finally L27 gave the best results after five CWAO cycles. Respirometry tests with activated sludge revealed that in the studied conditions the use of CWAO enhanced the aerobic biodegradability of the effluent. In the ADOX process L27 also showed better oxidation performances and regeneration efficiency. This different ageing was examined through AC physico-chemical properties.

Atomistic structure of cobalt-phosphate nanoparticles for catalytic water oxidation.

Science.gov (United States)

Hu, Xiao Liang; Piccinin, Simone; Laio, Alessandro; Fabris, Stefano

2012-12-21

Solar-driven water splitting is a key photochemical reaction that underpins the feasible and sustainable production of solar fuels. An amorphous cobalt-phosphate catalyst (Co-Pi) based on earth-abundant elements has been recently reported to efficiently promote water oxidation to protons and dioxygen, a main bottleneck for the overall process. The structure of this material remains largely unknown. We here exploit ab initio and classical atomistic simulations combined with metadynamics to build a realistic and statistically meaningful model of Co-Pi nanoparticles. We demonstrate the emergence and stability of molecular-size ordered crystallites in nanoparticles initially formed by a disordered Co-O network and phosphate groups. The stable crystallites consist of bis-oxo-bridged Co centers that assemble into layered structures (edge-sharing CoO(6) octahedra) as well as in corner- and face-sharing cubane units. These layered and cubane motifs coexist in the crystallites, which always incorporate disordered phosphate groups at the edges. Our computational nanoparticles, although limited in size to ~1 nm, can contain more than one crystallite and incorporate up to 18 Co centers in the cubane/layered structures. The crystallites are structurally stable up to high temperatures. We simulate the extended X-ray absorption fine structure (EXAFS) of our nanoparticles. Those containing several complete and incomplete cubane motifs-which are believed to be essential for the catalytic activity-display a very good agreement with the experimental EXAFS spectra of Co-Pi grains. We propose that the crystallites in our nanoparticles are reliable structural models of the Co-Pi catalyst surface. They will be useful to reveal the origin of the catalytic efficiency of these novel water-oxidation catalysts.

Fluid catalytic cracking : Feedstocks and reaction mechanism

NARCIS (Netherlands)

Dupain, X.

2006-01-01

The Fluid Catalytic Cracking (FCC) process is one of the key units in a modern refinery. Traditionally, its design is primarily aimed for the production of gasoline from heavy oil fractions, but as co-products also diesel blends and valuable gasses (e.g. propene and butenes) are formed in

Flame assisted synthesis of catalytic ceramic membranes

DEFF Research Database (Denmark)

Johansen, Johnny; Mosleh, Majid; Johannessen, Tue

2004-01-01

technology it is possible to make supported catalysts, composite metal oxides, catalytically active surfaces, and porous ceramic membranes. Membrane layers can be formed by using a porous substrate tube (or surface) as a nano-particle filter. The aerosol gas from the flame is led through a porous substrate...

Catalytic applications of bio-inspired nanomaterials

Science.gov (United States)

Pacardo, Dennis Kien Balaong

The biomimetic synthesis of Pd nanoparticles was presented using the Pd4 peptide, TSNAVHPTLRHL, isolated from combinatorial phage display library. Using this approach, nearly monodisperse and spherical Pd nanoparticles were generated with an average diameter of 1.9 +/- 0.4 nm. The peptide-based nanocatalyst were employed in the Stille coupling reaction under energy-efficient and environmentally friendly reaction conditions of aqueous solvent, room temperature and very low catalyst loading. To this end, the Pd nanocatalyst generated high turnover frequency (TOF) value and quantitative yields using ≥ 0.005 mol% Pd as well as catalytic activities with different aryl halides containing electron-withdrawing and electron-donating groups. The Pd4-capped Pd nanoparticles followed the atom-leaching mechanism and were found to be selective with respect to substrate identity. On the other hand, the naturally-occurring R5 peptide (SSKKSGSYSGSKGSKRRIL) was employed in the synthesis of biotemplated Pd nanomaterials which showed morphological changes as a function of Pd:peptide ratio. TOF analysis for hydrogenation of olefinic alcohols showed similar catalytic activity regardless of nanomorphology. Determination of catalytic properties of these bio-inspired nanomaterials are important as they serve as model system for alternative green catalyst with applications in industrially important transformations.

Vapor-Driven Propulsion of Catalytic Micromotors

Science.gov (United States)

Dong, Renfeng; Li, Jinxing; Rozen, Isaac; Ezhilan, Barath; Xu, Tailin; Christianson, Caleb; Gao, Wei; Saintillan, David; Ren, Biye; Wang, Joseph

2015-08-01

Chemically-powered micromotors offer exciting opportunities in diverse fields, including therapeutic delivery, environmental remediation, and nanoscale manufacturing. However, these nanovehicles require direct addition of high concentration of chemical fuel to the motor solution for their propulsion. We report the efficient vapor-powered propulsion of catalytic micromotors without direct addition of fuel to the micromotor solution. Diffusion of hydrazine vapor from the surrounding atmosphere into the sample solution is instead used to trigger rapid movement of iridium-gold Janus microsphere motors. Such operation creates a new type of remotely-triggered and powered catalytic micro/nanomotors that are responsive to their surrounding environment. This new propulsion mechanism is accompanied by unique phenomena, such as the distinct off-on response to the presence of fuel in the surrounding atmosphere, and spatio-temporal dependence of the motor speed borne out of the concentration gradient evolution within the motor solution. The relationship between the motor speed and the variables affecting the fuel concentration distribution is examined using a theoretical model for hydrazine transport, which is in turn used to explain the observed phenomena. The vapor-powered catalytic micro/nanomotors offer new opportunities in gas sensing, threat detection, and environmental monitoring, and open the door for a new class of environmentally-triggered micromotors.

Free-standing hierarchical α-MnO2@CuO membrane for catalytic filtration degradation of organic pollutants.

Science.gov (United States)

Luo, Xinsheng; Liang, Heng; Qu, Fangshu; Ding, An; Cheng, Xiaoxiang; Tang, Chuyang Y; Li, Guibai

2018-06-01

Catalytic membrane, due to its compact reactor assembling, high catalytic performance as well as low energy consumption, has proved to be more attractive for wastewater treatment. In this work, a free-standing α-MnO 2 @CuO membrane with hierarchical nanostructures was prepared and evaluated as the catalytic membrane to generate radicals from peroxymonosulfate (PMS) for the oxidative degradation of organic dyes in aqueous solution. Benefiting from the high mass transport efficiency and the hierarchical nanostructures, a superior catalytic activity of the membrane was observed for organic dyes degradation. As a typical organic dye, more than 99% of methylene blue (MB) was degraded within 0.23 s using dead-end filtration cell. The effects of flow rate, PMS concentration and buffer solution on MB degradation were further investigated. Besides MB, the catalytic membrane also showed excellent performance for the removal of other dyes, such as congo red, methyl orange, rhodamine B, acid chrome blue K and malachite green. Moreover, the mechanism study indicated that OH and SO 4 - generated from the interaction between PMS and Mn/Cu species with different oxidation states mainly accounted for the dyes degradation. The catalytic filtration process using α-MnO 2 @CuO catalytic membrane could provide a novel method for wastewater purification with high efficiency and low energy consumption. Copyright © 2018 Elsevier Ltd. All rights reserved.

Methods of using structures including catalytic materials disposed within porous zeolite materials to synthesize hydrocarbons

Science.gov (United States)

Rollins, Harry W [Idaho Falls, ID; Petkovic, Lucia M [Idaho Falls, ID; Ginosar, Daniel M [Idaho Falls, ID

2011-02-01

Catalytic structures include a catalytic material disposed within a zeolite material. The catalytic material may be capable of catalyzing a formation of methanol from carbon monoxide and/or carbon dioxide, and the zeolite material may be capable of catalyzing a formation of hydrocarbon molecules from methanol. The catalytic material may include copper and zinc oxide. The zeolite material may include a first plurality of pores substantially defined by a crystal structure of the zeolite material and a second plurality of pores dispersed throughout the zeolite material. Systems for synthesizing hydrocarbon molecules also include catalytic structures. Methods for synthesizing hydrocarbon molecules include contacting hydrogen and at least one of carbon monoxide and carbon dioxide with such catalytic structures. Catalytic structures are fabricated by forming a zeolite material at least partially around a template structure, removing the template structure, and introducing a catalytic material into the zeolite material.

Degradation of paracetamol by catalytic wet air oxidation and sequential adsorption - Catalytic wet air oxidation on activated carbons

Energy Technology Data Exchange (ETDEWEB)

Quesada-Penate, I. [Universite de Toulouse, INPT, UPS, Laboratoire de Genie Chimique, 4, Allee Emile Monso, F-31432 Toulouse (France); CNRS, Laboratoire de Genie Chimique, F-31432 Toulouse (France); Julcour-Lebigue, C., E-mail: carine.julcour@ensiacet.fr [Universite de Toulouse, INPT, UPS, Laboratoire de Genie Chimique, 4, Allee Emile Monso, F-31432 Toulouse (France); CNRS, Laboratoire de Genie Chimique, F-31432 Toulouse (France); Jauregui-Haza, U. J. [Instituto Superior de Tecnologias y Ciencias Aplicadas, Ave. Salvador Allende y Luaces, Habana (Cuba); Wilhelm, A. M.; Delmas, H. [Universite de Toulouse, INPT, UPS, Laboratoire de Genie Chimique, 4, Allee Emile Monso, F-31432 Toulouse (France); CNRS, Laboratoire de Genie Chimique, F-31432 Toulouse (France)

2012-06-30

Highlights: Black-Right-Pointing-Pointer Three activated carbons (AC) compared as adsorbents and oxidation catalysts. Black-Right-Pointing-Pointer Similar evolution for catalytic and adsorptive properties of AC over reuses. Black-Right-Pointing-Pointer Acidic and mesoporous AC to be preferred, despite lower initial efficiency. Black-Right-Pointing-Pointer Oxidative degradation of paracetamol improves biodegradability. Black-Right-Pointing-Pointer Convenient hybrid adsorption-regenerative oxidation process for continuous treatment. - Abstract: The concern about the fate of pharmaceutical products has raised owing to the increasing contamination of rivers, lakes and groundwater. The aim of this paper is to evaluate two different processes for paracetamol removal. The catalytic wet air oxidation (CWAO) of paracetamol on activated carbon was investigated both as a water treatment technique using an autoclave reactor and as a regenerative treatment of the carbon after adsorption in a sequential fixed bed process. Three activated carbons (ACs) from different source materials were used as catalysts: two microporous basic ACs (S23 and C1) and a meso- and micro-porous acidic one (L27). During the first CWAO experiment the adsorption capacity and catalytic performance of fresh S23 and C1 were higher than those of fresh L27 despite its higher surface area. This situation changed after AC reuse, as finally L27 gave the best results after five CWAO cycles. Respirometry tests with activated sludge revealed that in the studied conditions the use of CWAO enhanced the aerobic biodegradability of the effluent. In the ADOX process L27 also showed better oxidation performances and regeneration efficiency. This different ageing was examined through AC physico-chemical properties.

X-ray structures of the Pseudomonas cichorii D-tagatose 3-epimerase mutant form C66S recognizing deoxy sugars as substrates.

Science.gov (United States)

Yoshida, Hiromi; Yoshihara, Akihide; Ishii, Tomohiko; Izumori, Ken; Kamitori, Shigehiro

2016-12-01

Pseudomonas cichorii D-tagatose 3-epimerase (PcDTE), which has a broad substrate specificity, efficiently catalyzes the epimerization of not only D-tagatose to D-sorbose but also D-fructose to D-psicose (D-allulose) and also recognizes the deoxy sugars as substrates. In an attempt to elucidate the substrate recognition and catalytic reaction mechanisms of PcDTE for deoxy sugars, the X-ray structures of the PcDTE mutant form with the replacement of Cys66 by Ser (PcDTE_C66S) in complexes with deoxy sugars were determined. These X-ray structures showed that substrate recognition by the enzyme at the 1-, 2-, and 3-positions is responsible for enzymatic activity and that substrate-enzyme interactions at the 4-, 5-, and 6-positions are not essential for the catalytic reaction of the enzyme leading to the broad substrate specificity of PcDTE. They also showed that the epimerization site of 1-deoxy 3-keto D-galactitol is shifted from C3 to C4 and that 1-deoxy sugars may bind to the catalytic site in the inhibitor-binding mode. The hydrophobic groove that acts as an accessible surface for substrate binding is formed through the dimerization of PcDTE. In PcDTE_C66S/deoxy sugar complex structures, bound ligand molecules in both the linear and ring forms were detected in the hydrophobic groove, while bound ligand molecules in the catalytic site were in the linear form. This result suggests that the sugar-ring opening of a substrate may occur in the hydrophobic groove and also that the narrow channel of the passageway to the catalytic site allows a substrate in the linear form to pass through.

An application of almost marginal conditional stochastic dominance (AMCSD) on forming efficient portfolios

Science.gov (United States)

Slamet, Isnandar; Mardiana Putri Carissa, Siska; Pratiwi, Hasih

2017-10-01

Investors always seek an efficient portfolio which is a portfolio that has a maximum return on specific risk or minimal risk on specific return. Almost marginal conditional stochastic dominance (AMCSD) criteria can be used to form the efficient portfolio. The aim of this research is to apply the AMCSD criteria to form an efficient portfolio of bank shares listed in the LQ-45. This criteria is used when there are areas that do not meet the criteria of marginal conditional stochastic dominance (MCSD). On the other words, this criteria can be derived from quotient of areas that violate the MCSD criteria with the area that violate and not violate the MCSD criteria. Based on the data bank stocks listed on LQ-45, it can be stated that there are 38 efficient portfolios of 420 portfolios where each portfolio comprises of 4 stocks and 315 efficient portfolios of 1710 portfolios with each of portfolio has 3 stocks.

[Studies on photo-electron-chemical catalytic degradation of the malachite green].

Science.gov (United States)

Li, Ming-yu; Diao, Zeng-hui; Song, Lin; Wang, Xin-le; Zhang, Yuan-ming

2010-07-01

A novel two-compartment photo-electro-chemical catalytic reactor was designed. The TiO2/Ti thin film electrode thermally formed was used as photo-anode, and graphite as cathode and a saturated calomel electrode (SCE) as the reference electrode in the reactor. The anode compartment and cathode compartment were connected with the ionic exchange membrane in this reactor. Effects of initial pH, initial concentration of malachite green and connective modes between the anode compartment and cathode compartment on the decolorization efficiency of malachite green were investigated. The degradation dynamics of malachite green was studied. Based on the change of UV-visible light spectrum, the degradation process of malachite green was discussed. The experimental results showed that, during the time of 120 min, the decolouring ratio of the malachite green was 97.7% when initial concentration of malachite green is 30 mg x L(-1) and initial pH is 3.0. The catalytic degradation of malachite green was a pseudo-first order reaction. In the degradation process of malachite green the azo bond cleavage and the conjugated system of malachite green were attacked by hydroxyl radical. Simultaneity, the aromatic ring was oxidized. Finally, malachite green was degraded into other small molecular compounds.

Short hydrogen bonds in the catalytic mechanism of serine proteases

Directory of Open Access Journals (Sweden)

VLADIMIR LESKOVAC

2008-04-01

Full Text Available The survey of crystallographic data from the Protein Data Bank for 37 structures of trypsin and other serine proteases at a resolution of 0.78–1.28 Å revealed the presence of hydrogen bonds in the active site of the enzymes, which are formed between the catalytic histidine and aspartate residues and are on average 2.7 Å long. This is the typical bond length for normal hydrogen bonds. The geometric properties of the hydrogen bonds in the active site indicate that the H atom is not centered between the heteroatoms of the catalytic histidine and aspartate residues in the active site. Taken together, these findings exclude the possibility that short “low-barrier” hydrogen bonds are formed in the ground state structure of the active sites examined in this work. Some time ago, it was suggested by Cleland that the “low-barrier hydrogen bond” hypothesis is operative in the catalytic mechanism of serine proteases, and requires the presence of short hydrogen bonds around 2.4 Å long in the active site, with the H atom centered between the catalytic heteroatoms. The conclusions drawn from this work do not exclude the validity of the “low-barrier hydrogen bond” hypothesis at all, but they merely do not support it in this particular case, with this particular class of enzymes.

Catalytic properties of lanthanide amide, imide and nitride formed by thermal degradation of liquid ammonia solutions of Eu and Yb metal

International Nuclear Information System (INIS)

Imamura, H.; Mizuno, K.; Ohishi, K.; Suda, E.; Kanda, K.; Sakata, Y.; Tsuchiya, S.

1998-01-01

The catalytic properties of lanthanide amide, imide and nitride prepared by the use of liquid ammonia solutions of lanthanide metals (Ln=Eu and Yb) were studied for catalytic hydrogenation. The reaction of Eu or Yb metal solutions in liquid ammonia with silica yielded SiO 2 -grafted lanthanide amide in the divalent state. The divalent amide showed catalytic activity for the selective hydrogenation of dienes and benzene. It was found that partial hydrogenation of benzene occurred with a very high selectivity for cyclohexene. Amides of calcium, strontium and barium were examined similarly in connection with catalytic studies on divalent amides. Imide and nitride, into which the lanthanide (Ln/AC) deposited by impregnation of active carbon (AC) with liquid ammonia solutions of lanthanide metals were converted thermally, were studied catalytically. It was concluded that imide or imide-like species generated during the thermal degradation of lanthanide amide to nitride were very active in the hydrogenation of ethene. Lanthanide nitride was virtually inactive, but the nitride highly dispersed on active carbon was activated when subjected to evacuation treatment above about 1000 K. (orig.)

A PEG/copper(i) halide cluster as an eco-friendly catalytic system for C-N bond formation.

Science.gov (United States)

Li, Cheng-An; Ji, Wei; Qu, Jian; Jing, Su; Gao, Fei; Zhu, Dun-Ru

2018-05-22

The catalytic activities of eight copper(i) halide clusters assembled from copper(i) halide and ferrocenyltelluroethers, 1-8, were investigated in C-N formation under various conditions. A catalytic procedure using poly(ethylene glycol) (PEG-400) as a greener alternative organic solvent has been developed. The PEG-400/5 system can achieve 99% targeted yield with a mild reaction temperature and short reaction time. After the isolation of the products by extraction with diethyl ether, this PEG-400/cluster system could be easily recycled. Spectroscopic studies elucidate a stepwise mechanism: firstly, proton-coupled electron transfer (PCET) involving the transfer of an electron from Cu+ and a proton from imidazole results in the formation of a labile penta-coordinated Cu2+ and aryl radical; the following effective electron transfer from the ferrocene unit reduces Cu2+ and forms the target product; finally, the ferrocenium unit is reduced by the I- anion. The merits of this eco-friendly synthesis are the efficient utilization of reagents and easy recyclability.

Structured materials for catalytic and sensing applications

Science.gov (United States)

Hokenek, Selma

The optical and chemical properties of the materials used in catalytic and sensing applications directly determine the characteristics of the resultant catalyst or sensor. It is well known that a catalyst needs to have high activity, selectivity, and stability to be viable in an industrial setting. The hydrogenation activity of palladium catalysts is known to be excellent, but the industrial applications are limited by the cost of obtaining catalyst in amounts large enough to make their use economical. As a result, alloying palladium with a cheaper, more widely available metal while maintaining the high catalytic activity seen in monometallic catalysts is, therefore, an attractive option. Similarly, the optical properties of nanoscale materials used for sensing must be attuned to their application. By adjusting the shape and composition of nanoparticles used in such applications, very fine changes can be made to the frequency of light that they absorb most efficiently. The design, synthesis, and characterization of (i) size controlled monometallic palladium nanoparticles for catalytic applications, (ii) nickel-palladium bimetallic nanoparticles and (iii) silver-palladium nanoparticles with applications in drug detection and biosensing through surface plasmon resonance, respectively, will be discussed. The composition, size, and shape of the nanoparticles formed were controlled through the use of wet chemistry techniques. After synthesis, the nanoparticles were analyzed using physical and chemical characterization techniques such as X-Ray Diffraction (XRD), Transmission Electron Microscopy (TEM), and Scanning Transmission Electron Microscopy- Energy-Dispersive Spectrometry (STEM-EDX). The Pd and Ni-Pd nanoparticles were then supported on silica for catalytic testing using mass spectrometry. The optical properties of the Ag-Pd nanoparticles in suspension were further investigated using ultraviolet-visible spectrometry (UV-Vis). Monometallic palladium particles have

Engineered disulfide bonds increase active-site local stability and reduce catalytic activity of a cold-adapted alkaline phosphatase.

Science.gov (United States)

Asgeirsson, Bjarni; Adalbjörnsson, Björn Vidar; Gylfason, Gudjón Andri

2007-06-01

Alkaline phosphatase is an extracellular enzyme that is membrane-bound in eukaryotes but resides in the periplasmic space of bacteria. It normally carries four cysteine residues that form two disulfide bonds, for instance in the APs of Escherichia coli and vertebrates. An AP variant from a Vibrio sp. has only one cysteine residue. This cysteine is second next to the nucleophilic serine in the active site. We have individually modified seven residues to cysteine that are on two loops predicted to be within a 5 A radius. Four of them formed a disulfide bond to the endogenous cysteine. Thermal stability was monitored by circular dichroism and activity measurements. Global stability was similar to the wild-type enzyme. However, a significant increase in heat-stability was observed for the disulfide-containing variants using activity as a measure, together with a large reduction in catalytic rates (k(cat)) and a general decrease in Km values. The results suggest that a high degree of mobility near the active site and in the helix carrying the endogenous cysteine is essential for full catalytic efficiency in the cold-adapted AP.

Robust Approach to Verifying the Weak Form of the Efficient Market Hypothesis

Science.gov (United States)

Střelec, Luboš

2011-09-01

The weak form of the efficient markets hypothesis states that prices incorporate only past information about the asset. An implication of this form of the efficient markets hypothesis is that one cannot detect mispriced assets and consistently outperform the market through technical analysis of past prices. One of possible formulations of the efficient market hypothesis used for weak form tests is that share prices follow a random walk. It means that returns are realizations of IID sequence of random variables. Consequently, for verifying the weak form of the efficient market hypothesis, we can use distribution tests, among others, i.e. some tests of normality and/or some graphical methods. Many procedures for testing the normality of univariate samples have been proposed in the literature [7]. Today the most popular omnibus test of normality for a general use is the Shapiro-Wilk test. The Jarque-Bera test is the most widely adopted omnibus test of normality in econometrics and related fields. In particular, the Jarque-Bera test (i.e. test based on the classical measures of skewness and kurtosis) is frequently used when one is more concerned about heavy-tailed alternatives. As these measures are based on moments of the data, this test has a zero breakdown value [2]. In other words, a single outlier can make the test worthless. The reason so many classical procedures are nonrobust to outliers is that the parameters of the model are expressed in terms of moments, and their classical estimators are expressed in terms of sample moments, which are very sensitive to outliers. Another approach to robustness is to concentrate on the parameters of interest suggested by the problem under this study. Consequently, novel robust testing procedures of testing normality are presented in this paper to overcome shortcomings of classical normality tests in the field of financial data, which are typical with occurrence of remote data points and additional types of deviations from

Oxidative cracking of n-hexane: a catalytic pathway to olefins

NARCIS (Netherlands)

Boyadjian, C.A.

2010-01-01

Steam cracking, the major, current existing route for light olefin production, is the most energy consuming process in the chemical industry. The need for an energy efficient processes, urged substantial research work for the development of new catalytic technologies for light olefin production.

Photo catalytic Degradation of Organic Dye by Sol-Gel-Derived Gallium-Doped Anatase Titanium Oxide Nanoparticles for Environmental Remediation

International Nuclear Information System (INIS)

Arghya, N.B.; Sang, W.J.; Bong-Ki, M.

2012-01-01

Photo catalytic degradation of toxic organic chemicals is considered to be the most efficient green method for surface water treatment. We have reported the sol-gel synthesis of Gadoped anatase TiO 2 nanoparticles and the photo catalytic oxidation of organic dye into nontoxic inorganic products under UV irradiation. Photodegradation experiments show very good photo catalytic activity of Ga-doped TiO 2 nanoparticles with almost 90% degradation efficiency within 3 hrs of UV irradiation, which is faster than the undoped samples. Doping levels created within the bandgap of TiO 2 act as trapping centers to suppress the photo generated electron-hole recombination for proper and timely utilization of charge carriers for the generation of strong oxidizing radicals to degrade the organic dye. Photo catalytic degradation is found to follow the pseudo-first-order kinetics with the apparent 1 st-order rate constant around 1.3 x 10 -2 min -1 . The cost-effective, sol-gel-derived TiO 2 : Ga nanoparticles can be used efficiently for light-assisted oxidation of toxic organic molecules in the surface water for environmental remediation.

Market Returns and Weak-Form Efficiency: the case of the Ghana Stock Exchange

OpenAIRE

Frimpong, Joseph Magnus; Oteng-Abayie, Eric Fosu

2007-01-01

This paper examines the weak-form efficient market hypothesis (EMH) in the case of the Ghana Stock Exchange (GSE) an emerging market. Daily returns from the Databank Stock Index (DSI) over a 5-year period 1999-2004 were used for the exercise. Random walk (RW) and GARCH(1,1) models are used as the basis for our analysis. The GSE DSI returns series exhibit volatility clustering, an indication of inefficiency on the GSE. The weak-form efficient market (random walk) hypothesis was rejected for t...

Construction and in vivo assembly of a catalytically proficient and hyperthermostable de novo enzyme.

Science.gov (United States)

Watkins, Daniel W; Jenkins, Jonathan M X; Grayson, Katie J; Wood, Nicola; Steventon, Jack W; Le Vay, Kristian K; Goodwin, Matthew I; Mullen, Anna S; Bailey, Henry J; Crump, Matthew P; MacMillan, Fraser; Mulholland, Adrian J; Cameron, Gus; Sessions, Richard B; Mann, Stephen; Anderson, J L Ross

2017-08-25

Although catalytic mechanisms in natural enzymes are well understood, achieving the diverse palette of reaction chemistries in re-engineered native proteins has proved challenging. Wholesale modification of natural enzymes is potentially compromised by their intrinsic complexity, which often obscures the underlying principles governing biocatalytic efficiency. The maquette approach can circumvent this complexity by combining a robust de novo designed chassis with a design process that avoids atomistic mimicry of natural proteins. Here, we apply this method to the construction of a highly efficient, promiscuous, and thermostable artificial enzyme that catalyzes a diverse array of substrate oxidations coupled to the reduction of H 2 O 2 . The maquette exhibits kinetics that match and even surpass those of certain natural peroxidases, retains its activity at elevated temperature and in the presence of organic solvents, and provides a simple platform for interrogating catalytic intermediates common to natural heme-containing enzymes.Catalytic mechanisms of enzymes are well understood, but achieving diverse reaction chemistries in re-engineered proteins can be difficult. Here the authors show a highly efficient and thermostable artificial enzyme that catalyzes a diverse array of substrate oxidations coupled to the reduction of H 2 O 2 .

Synthesis of ternary oxide for efficient photo catalytic conversion of CO2

Science.gov (United States)

Wan, Lijuan

2018-01-01

Zn2GeO4 Nan rods were prepared by solution phase route. The morphology and structure of the as-prepared products were characterized by scanning electron microscopy (SEM) and Bruner-Emmett-Teller (BET) surface area measurements. The results revealed that Zn2GeO4 Nan rods with higher surface area have higher photo catalytic activity in photo reduction of CO2 than Zn2GeO4 prepared through solid-state reaction.

Deuterohemin-Peptide Enzyme Mimic-Embedded Metal-Organic Frameworks through Biomimetic Mineralization with Efficient ATRP Catalytic Activity.

Science.gov (United States)

Jiang, Wei; Wang, Xinghuo; Chen, Jiawen; Liu, Ying; Han, Haobo; Ding, Yi; Li, Quanshun; Tang, Jun

2017-08-16

An enzyme mimic harboring iron porphyrin (DhHP-6) embedded in zeolite imidazolate framework-8 (ZIF-8) was constructed through a biomimetic mineralization approach to obtain composite DhHP-6@ZIF-8. The composite was then used as a catalyst in the atom transfer radical polymerization (ATRP) of poly(ethylene glycol) methyl ether methacrylate (PEGMA 500 ) in which poly(PEGMA 500 ) could be synthesized with monomer conversion of 76.1% and M n of 45 900 g/mol, stronger than that obtained when using free DhHP-6 as a catalyst. More importantly, it could efficiently overcome the drawbacks of free DhHP-6 and achieve the easy separation of DhHP-6 from the catalytic system and the elimination of iron residues in the synthesized polymer. In addition, it exhibited an enhanced recyclability with monomer conversion of 75.7% after five cycles and favorable stability during the ATRP reaction with mimic-ZIF-8 composite developed through biomimetic mineralization can be potentially used as an effective catalyst for preparing well-defined polymers with biomedical applications.

Enantioselective catalytic fluorinative aza-semipinacol rearrangement.

Science.gov (United States)

Romanov-Michailidis, Fedor; Pupier, Marion; Besnard, Céline; Bürgi, Thomas; Alexakis, Alexandre

2014-10-03

An efficient and highly stereoselective fluorinative aza-semipinacol rearrangement is described. The catalytic reaction requires use of Selectfluor in combination with the chiral, enantiopure phosphate anion derived from acid L3. Under optimized conditions, cyclopropylamines A were transformed into β-fluoro cyclobutylimines B in good yields and high levels of diastereo- and enantiocontrol. Furthermore, the optically active cyclobutylimines were reduced diastereoselectively with L-Selectride in the corresponding fluorinated amines C, compounds of significant interest in the pharmacological industry.

Synthesis of MoO3 nanoparticles for azo dye degradation by catalytic ozonation

International Nuclear Information System (INIS)

Manivel, Arumugam; Lee, Gang-Juan; Chen, Chin-Yi; Chen, Jing-Heng; Ma, Shih-Hsin; Horng, Tzzy-Leng; Wu, Jerry J.

2015-01-01

Highlights: • Synthesis of one-dimensional MoO 3 nanostructures using hydrothermal, microwave, and sonochemical methods. • Sonochemical synthesized MoO 3 presents the best efficiency for the dye removal by catalytic ozonation. • Efficient environmental remediation process. - Abstract: One-dimensional molybdenum trioxide nanostructures were prepared in three different approaches, including thermal, microwave, and sonochemical methods. The physicochemical properties of the obtained MoO 3 nanoparticles were investigated by diffused reflectance spectroscopy, X-ray diffraction analysis, field emission scanning electron microscopy, high resolution transmission electron microscopy, and Brunauer–Emmett–Teller surface area analysis. Among the methods as investigated, sonochemical synthesis gave well-dispersed fine MoO 3 nanoparticles compared with the other approaches. All the synthesized MoO 3 nanostructures were examined for the catalytic ozonation to degrade azo dye in aqueous environment. Different performances were obtained for the catalyst prepared in different methods and the catalytic efficiencies were found to be the order of sonochemical, microwave, and then thermal methods. The sonochemical MoO 3 catalyst allowed the total dye removal within 20 min and its good performance was justified according to their higher surface area with higher number of active sites that provide effective dye interaction for better degradation

Fundamental study of manganese dioxide for catalytic recombustion of exhaust gas of motor car

Energy Technology Data Exchange (ETDEWEB)

Shimoyamada, T

1974-01-01

The catalytic activities of five manganese dioxide preparations were tested in a pulse reactor to assess their carbon monoxide-oxidizing capability in relation to the catalytic afterburning of automobile exhaust gases. Catalysts prepared from manganese sulfate showed diminished catalytic activity as a result of sulfate poisoning. Higher oxidation activity was obtained with a catalyst prepared by precipitating the permanganate salt in acidic solution. Two forms of carbon monoxide adsorption were demonstrated, each with a characteristic activation energy and reaction temperature.

Simulation on Toxic Gases in Vehicle Exhaust Equipped with Modified Catalytic Converter : A Review

Directory of Open Access Journals (Sweden)

Leman A.M.

2016-01-01

Full Text Available Air pollution and global warming is a major issue nowadays. One of the main contributors to be the emission of harmful gases produced by vehicle exhausts lines. The harmful gases like NOx, CO, unburned HC and particulate matter increases the global warming, so catalytic converter plays a vital role in reducing harmful gases. Catalytic converters are used on most vehicles on the road today. This research deals with the gas emission flow in the catalytic converter involving the heat transfer, velocity flow, back pressure and others chemical reaction in the modified catalytic converter by using FeCrAl as a substrate that is treated using the ultrasonic bath and electroplating techniques. The objective of this study is to obtain a quantitative description of the gas emission in the catalytic converter system of automobile exhaust gas using ANSYS Software. The description of the gas emission in the catalytic converter system of automobile exhaust gas using ANSYS Software was simulated in this research in order to provide better efficiency and ease the reusability of the catalytic converter by comparing experimental data with software analysing data. The result will be expected to demonstrate a good approximation of gas emission in the modified catalytic converter simulation data compared to experimental data in order to verify the effectiveness of modified catalytic converter. Therefore studies on simulation of flow through the modified catalytic converter are very important to increase the accuracy of the obtained emission result.

Low concentration volatile organic pollutants removal in combined adsorber-desorber-catalytic reactor system

Directory of Open Access Journals (Sweden)

Arsenijević Zorana

2008-01-01

Full Text Available The removal of volatile organic compounds (VOCs from numerous emission sources is of crucial importance due to more rigorous demands on air quality. Different technologies can be used to treat the VOCs from effluent gases: absorption, physical adsorption, open flame combustion, thermal and catalytic incineration. Their appropriateness for the specific process depends on several factors such as efficiency, energy consumption, secondary pollution, capital investments etc. The distinctive features of the catalytic combustion are high efficiency and selectivity toward be­nign products, low energy consumption and absence of secondary polluti­on. The supported noble catalysts are widely used for catalytic incineration due to their low ignition temperatures and high thermal and chemical stability. In our combined system adsorption and desorption are applied in the spouted bed with draft tube (SBDT unit. The annular zone, loaded with sorbent, was divided in adsorption and desorption section. Draft tube enabled sorbent recirculation between sections. Combustion of desorbed gases to CO2 and water vapor are realized in additive catalytic reactor. This integrated device provided low concentrations VOCs removal with reduced energy consumption. Experiments were conducted on a pilot unit of 220 m3/h nominal capacity. The sorbent was activated carbon, type K81/B - Trayal Corporation, Krusevac. A sphere shaped commercial Pt/Al2O3 catalyst with "egg-shell" macro-distribution was used for the investigation of xylene deep oxidation. Within this paper the investigations of removal of xylene vapors, a typical pollutant in production of liquid pesticides, in combined adsorber/desorber/catalytic reactor system is presented.

Testing the weak-form efficiency of the WTI crude oil futures market

Science.gov (United States)

Jiang, Zhi-Qiang; Xie, Wen-Jie; Zhou, Wei-Xing

2014-07-01

The weak-form efficiency of energy futures markets has long been studied and empirical evidence suggests controversial conclusions. In this work, nonparametric methods are adopted to estimate the Hurst indexes of the WTI crude oil futures prices (1983-2012) and a strict statistical test in the spirit of bootstrapping is put forward to verify the weak-form market efficiency hypothesis. The results show that the crude oil futures market is efficient when the whole period is considered. When the whole series is divided into three sub-series separated by the outbreaks of the Gulf War and the Iraq War, it is found that the Gulf War reduced the efficiency of the market. If the sample is split into two sub-series based on the signing date of the North American Free Trade Agreement, the market is found to be inefficient in the sub-periods during which the Gulf War broke out. The same analysis on short-time series in moving windows shows that the market is inefficient only when some turbulent events occur, such as the oil price crash in 1985, the Gulf war, and the oil price crash in 2008.

Carbon nanotube aerogel-CoS2 hybrid catalytic counter electrodes for enhanced photovoltaic performance dye-sensitized solar cells.

Science.gov (United States)

Liu, Tao; Mai, Xianmin; Chen, Haijun; Ren, Jing; Liu, Zheting; Li, Yingxiang; Gao, Lina; Wang, Ning; Zhang, Jiaoxia; He, Hongcai; Guo, Zhanhu

2018-03-01

The carbon nanotube aerogel (CNA) with an ultra-low density, three-dimensional network nanostructure, superior electronic conductivity and large surface area is being widely employed as a catalytic electrode and catalytic support. Impressively, dye-sensitized solar cells (DSSCs) assembled with a CNA counter electrode (CE) achieved a maximum power conversion efficiency (PCE) of 8.28%, which exceeded that of the conventional platinum (Pt)-based DSSC (7.20%) under the same conditions. Furthermore, highly dispersed CoS 2 nanoparticles endowed with excellent intrinsic catalytic activity were hydrothermally incorporated to form a CNA-supported CoS 2 (CNA-CoS 2 ) CE, which was due to the large number of catalytically active sites and sufficient connections between CoS 2 and the CNA. The electrocatalytic ability and stability were systematically evaluated by cyclic voltammetry (CV), electrochemical impedance spectra (EIS) and Tafel polarization, which confirmed that the resultant CNA-CoS 2 hybrid CE exhibited a remarkably higher electrocatalytic activity toward I 3 - reduction, and faster ion diffusion and electron transfer than the pure CNA CE. Such cost-effective DSSCs assembled with an optimized CNA-CoS 2 CE yielded an enhanced PCE of 8.92%, comparable to that of the cell fabricated with the CNA-Pt hybrid CE reported in our published literature (9.04%). These results indicate that the CNA-CoS 2 CE can be considered as a promising candidate for Pt-free CEs used in low-cost and high-performance DSSCs.

Characterization of nicotinamidases: steady state kinetic parameters, classwide inhibition by nicotinaldehydes, and catalytic mechanism.

Science.gov (United States)

French, Jarrod B; Cen, Yana; Vrablik, Tracy L; Xu, Ping; Allen, Eleanor; Hanna-Rose, Wendy; Sauve, Anthony A

2010-12-14

Nicotinamidases are metabolic enzymes that hydrolyze nicotinamide to nicotinic acid. These enzymes are widely distributed across biology, with examples found encoded in the genomes of Mycobacteria, Archaea, Eubacteria, Protozoa, yeast, and invertebrates, but there are none found in mammals. Although recent structural work has improved our understanding of these enzymes, their catalytic mechanism is still not well understood. Recent data show that nicotinamidases are required for the growth and virulence of several pathogenic microbes. The enzymes of Saccharomyces cerevisiae, Drosophila melanogaster, and Caenorhabditis elegans regulate life span in their respective organisms, consistent with proposed roles in the regulation of NAD(+) metabolism and organismal aging. In this work, the steady state kinetic parameters of nicotinamidase enzymes from C. elegans, Sa. cerevisiae, Streptococcus pneumoniae (a pathogen responsible for human pneumonia), Borrelia burgdorferi (the pathogen that causes Lyme disease), and Plasmodium falciparum (responsible for most human malaria) are reported. Nicotinamidases are generally efficient catalysts with steady state k(cat) values typically exceeding 1 s(-1). The K(m) values for nicotinamide are low and in the range of 2 -110 μM. Nicotinaldehyde was determined to be a potent competitive inhibitor of these enzymes, binding in the low micromolar to low nanomolar range for all nicotinamidases tested. A variety of nicotinaldehyde derivatives were synthesized and evaluated as inhibitors in kinetic assays. Inhibitions are consistent with reaction of the universally conserved catalytic Cys on each enzyme with the aldehyde carbonyl carbon to form a thiohemiacetal complex that is stabilized by a conserved oxyanion hole. The S. pneumoniae nicotinamidase can catalyze exchange of (18)O into the carboxy oxygens of nicotinic acid with H(2)(18)O. The collected data, along with kinetic analysis of several mutants, allowed us to propose a catalytic

Carbon nanotube growth from catalytic nano-clusters formed by hot-ion-implantation into the SiO{sub 2}/Si interface

Energy Technology Data Exchange (ETDEWEB)

Hoshino, Yasushi, E-mail: yhoshino@kanagawa-u.ac.jp [Department of Information Sciences, Kanagawa University, 2946 Tsuchiya, Hiratsuka, Kanagawa 259-1293 (Japan); Arima, Hiroki; Yokoyama, Ai; Saito, Yasunao; Nakata, Jyoji [Department of Information Sciences, Kanagawa University, 2946 Tsuchiya, Hiratsuka, Kanagawa 259-1293 (Japan)

2012-07-01

We have studied growth of chirality-controlled carbon nanotubes (CNTs) from hot-implantation-formed catalytic nano-clusters in a thermally grown SiO{sub 2}/Si substrate. This procedure has the advantage of high controllability of the diameter and the number of clusters by optimizing the conditions of the ion implantation. In the present study, Co{sup +} ions with ion dose of 8 Multiplication-Sign 10{sup 16} cm{sup -2} are implanted in the vicinity of the SiO{sub 2}/Si interface at 300 Degree-Sign C temperature. The implanted Co atoms located in the SiO{sub 2} layer has an amorphous-like structure with a cluster diameter of several nm. In contrast, implanted Co atoms in the Si substrate are found to take a cobalt silicide structure, confirmed by the high-resolution image of transmission electron microscope. CNTs are grown by microwave-plasma-enhanced chemical vapor deposition. We have confirmed a large amount of vertically-aligned multi-walled CNTs from the Co nano-clusters formed by the hot-ion-implantation near the SiO{sub 2}/Si interface.

Production of hydrogen from bio-ethanol in catalytic membrane reactor

International Nuclear Information System (INIS)

Gernot, E.; Aupretre, F.; Deschamps, A.; Etievant, C.; Epron, F.; Marecot, P.; Duprez, D.

2006-01-01

Production of hydrogen from renewable energy sources offers a great potential for CO 2 emission reduction, responsible for global warming. Among renewable energies, liquid biofuels are very convenient hydrogen carriers for decentralized applications such as micro-cogeneration and transports. Ethanol, produced from sugar plants and cereals, allows a reduction of more than 60% of CO 2 emissions in comparison to gasoline. BIOSTAR is an R and D project, co-funded by the French Agency for Environment and Energy Management (ADEME) which aims at developing an efficient source of hydrogen from bio-ethanol, suitable for proton exchange membrane fuel cell systems. The objectives are to obtain, through catalytic process at medium temperature range, an efficient conversion of bio-ethanol into pure hydrogen directly usable for PEMFC. CETH has developed a catalytic membrane reformer (CMR), based on a patented technology, integrating a steam reforming catalyst as well as a combustion catalyst. Both catalysts have been developed and optimized for membrane reactor in partnership with the University of Poitiers. The composite metallic membrane developed by CETH allows hydrogen extraction near the hydrogen production sites, which enhances both efficiency and compactness. (authors)

Catalytic applications of immobilized ionic liquids for synthesis of cyclic carbonates from carbon dioxide and epoxides

International Nuclear Information System (INIS)

Kim, Dong-Woo; Roshan, Roshith; Tharun, Jose; Cherian, Amal; Park, Dae-Won

2013-01-01

The catalytic applicability of ionic liquids immobilized on various support materials such as silica, polystyrene and biopolymers in the cycloaddition of carbon dioxide with epoxides is reviewed in this work. Comparisons of the catalytic efficiency of these various catalysts have been done from the aspect of turnover number and reusability. The studies revealed that ionic liquids or support materials possessing hydrogen bonding capable groups exhibited enhanced catalytic activity towards cyclic carbonate synthesis. Moreover, the increased quest towards environmentally benign materials has renewed the search for biocompatible materials as support for ionic liquids

Iron Phthalocyanine as New Efficient Catalyst for Catalytic Transfer Hydrogenation of Simple Aldehydes and Ketones

Czech Academy of Sciences Publication Activity Database

Bata, P.; Notheisz, F.; Klusoň, Petr; Zsigmond, A.

2015-01-01

Roč. 29, JAN 2015 (2015), s. 45-49 ISSN 0268-2605 Institutional support: RVO:67985858 Keywords : heterogenized complexes * catalytic transfer hydrogenation * reusable catalyst Subject RIV: CC - Organic Chemistry Impact factor: 2.452, year: 2015

Catalytic destruction of tar in biomass derived producer gas

International Nuclear Information System (INIS)

Zhang Ruiqin; Brown, Robert C.; Suby, Andrew; Cummer, Keith

2004-01-01

The purpose of this study is to investigate catalytic destruction of tar formed during gasification of biomass, with the goal of improving the quality of the producer gas. This work focuses on nickel based catalysts treated with alkali in an effort to promote steam gasification of the coke that deposits on catalyst surfaces. A tar conversion system consisting of a guard bed and catalytic reactor was designed to treat the producer gas from an air blown, fluidized bed biomass gasifier. The guard bed used dolomite to crack the heavy tars. The catalytic reactor was used to evaluate three commercial steam reforming catalysts. These were the ICI46-1 catalyst from Imperial Chemical Industry and Z409 and RZ409 catalysts from Qilu Petrochemical Corp. in China. A 0.5-3 l/min slipstream from a 5 tpd biomass gasifier was used to test the tar conversion system. Gas and tar were sampled before and after the tar conversion system to evaluate the effectiveness of the system. Changes in gas composition as functions of catalytic bed temperature, space velocity and steam/TOC (total organic carbon) ratio are presented. Structural changes in the catalysts during the tests are also described

Foliage efficiency of forest-forming species in the climatic gradients of Eurasia

Directory of Open Access Journals (Sweden)

V. A. Usoltsev

2017-08-01

Full Text Available The paperis of the scientific area of biogeography and devoted to a new aspect in the study of biological productivity of forest ecosystems on a geographical basis, expressed indirectly by climate parameters, namely, the foliage efficiency that until now is not investigated at the global level. Foliage efficiency is the ratio of net primary production (NPP to foliage biomass and is expressed in relative units. Some features of change of foliage efficiency of vicarious forest-forming species in Eurasian transcontinental gradients are showed for the first time using the voluminous factual material. The set of published biomass and NPP data (t/ha obtained in a number of 2192 plots is compiled. Using multiple regression analysis technique, the statistically significant changes in foliage efficiency values according to two transcontinental gradients, namely by zonal belts and continentality of climate, are stated for each forest-forming species. The species-specificity of age dynamics of stem volume and foliage efficiency is shown. It is monotonically decreased almost for all tree species in the following order: spruce and fir, pine, birch, oak, larch and aspen-poplar. When climate continentality increasing, foliage efficiency values of mature forests is dropping, most intensively in pines, less intensive in deciduous forests and virtually no changes in spruce-fir communities. In zonal gradient from the northern temperate to the subequatorial belt, foliage efficiency of deciduous species decreases, but it of the evergreen spruce and pine increases in the same direction. One of the possible causes of these opposite zonal trends of foliage efficiency in evergreen and deciduous species consists in different conditions of physiological processes in the year cycle, in particular, in year-round assimilates accumulation in the first and seasonal one in the second.

Degradation of the ammonia wastewater in aqueous medium with ozone in combination with mesoporous TiO2 catalytic

Science.gov (United States)

Liu, Zhiwu; Qiu, Jianping; Zheng, Chaocan; Li, Liqing

2017-03-01

TiO2 mesoporous nanomaterials are now widely used in catalytic ozone technology. In this paper, the market P25 as precursor hydrothermal method to prepare TiO2 mesoporous materials, ozone catalyst material characterization by transmission electron microscopy, surface area analyzers, and X-ray diffraction technique and found that nanotubes, nanosheets, nanorods through characterization results, nano-particles of different morphology and anatase and rutile proportion of the ozone catalytic material can be controlled by the calcination temperature and the temperature of hot water to give, and with the hot water temperature and calcination temperature, the catalyst becomes small aperture size larger catalyst crystalline phase from anatase to rutile gradually shift. Catalytic materials have been prepared by the Joint ozone degradation of ammonia wastewater to evaluate mesoporous TiO2 nanomaterials ozone catalytic performance, the results showed that: ammonia wastewater removal efficiency of various catalytic materials relatively separate ozone and markets P25 effects are significantly improved, and TiO2 nanotubes cooperate with ozone degradation ammonia wastewater highest efficiency, in addition, rutile TiO2 catalysts, the more the better the performance of their ozone catalysis.

Catalytic nanoporous membranes

Science.gov (United States)

Pellin, Michael J; Hryn, John N; Elam, Jeffrey W

2013-08-27

A nanoporous catalytic membrane which displays several unique features Including pores which can go through the entire thickness of the membrane. The membrane has a higher catalytic and product selectivity than conventional catalysts. Anodic aluminum oxide (AAO) membranes serve as the catalyst substrate. This substrate is then subjected to Atomic Layer Deposition (ALD), which allows the controlled narrowing of the pores from 40 nm to 10 nm in the substrate by deposition of a preparatory material. Subsequent deposition of a catalytic layer on the inner surfaces of the pores reduces pore sizes to less than 10 nm and allows for a higher degree of reaction selectivity. The small pore sizes allow control over which molecules enter the pores, and the flow-through feature can allow for partial oxidation of reactant species as opposed to complete oxidation. A nanoporous separation membrane, produced by ALD is also provided for use in gaseous and liquid separations. The membrane has a high flow rate of material with 100% selectivity. Also provided is a method for producing a catalytic membrane having flow-through pores and discreet catalytic clusters adhering to the inside surfaces of the pores.

Solid strong base K-Pt/NaY zeolite nano-catalytic system for completed elimination of formaldehyde at room temperature

Science.gov (United States)

Song, Shaoqing; Wu, Xi; Lu, Changhai; Wen, Meicheng; Le, Zhanggao; Jiang, Shujuan

2018-06-01

Solid strong base nano-catalytic system of K-modification NaY zeolite supported 0.08% Pt (K-Pt/NaY) were constructed for eliminating HCHO at room temperature. In the catalytic process, activation energy over K-Pt/NaY nano-catalytic system was greatly decreased along with the enhanced reaction rate. Characterization and catalytic tests revealed the surface electron structure of K-Pt/NaY was improved, as reflected by the enhanced HCHO adsorption capability, high sbnd OH concentration, and low-temperature reducibility. Therefore, the optimal K-Pt/NaY showed high catalytic efficiency and strong H2O tolerance for HCHO elimination by directly promoting the reaction between active sbnd OH and formate species. These results may suggest a new way for probing the advanced solid strong base nano-catalytic system for the catalytic elimination of indoor HCHO.

Effect of High-Pressure Treatment on Catalytic and Physicochemical Properties of Pepsin.

Science.gov (United States)

Wang, Jianan; Bai, Tenghui; Ma, Yaping; Ma, Hanjun

2017-10-11

For a long time, high-pressure treatment has been used to destroy the compact structures of natural proteins in order to promote subsequent enzymatic hydrolysis. However, there are few reports evaluating the feasibility of directly improving the catalytic capability of proteases by using high-pressure treatments. In this study, the effects of high-pressure treatment on the catalytic capacity and structure of pepsin were investigated, and the relationship between its catalytic properties and changes in its physicochemical properties was explored. It was found that high-pressure treatment could lead to changes of the sulfhydryl group/disulfide bond content, hydrophobicity, hydrodynamic radius, intrinsic viscosity, and subunit composition of pepsin, and the conformational change of pepsin resulted in improvement to its enzymatic activity and hydrolysis efficiency, which had an obvious relationship with the high-pressure treatment conditions.

Catalytic Ketone Hydrodeoxygenation Mediated by Highly Electrophilic Phosphonium Cations.

Science.gov (United States)

Mehta, Meera; Holthausen, Michael H; Mallov, Ian; Pérez, Manuel; Qu, Zheng-Wang; Grimme, Stefan; Stephan, Douglas W

2015-07-06

Ketones are efficiently deoxygenated in the presence of silane using highly electrophilic phosphonium cation (EPC) salts as catalysts, thus affording the corresponding alkane and siloxane. The influence of distinct substitution patterns on the catalytic effectiveness of several EPCs was evaluated. The deoxygenation mechanism was probed by DFT methods. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Catalytic reduction of hexaminecobalt(III) by pitch-based spherical activated carbon (PBSAC)

Energy Technology Data Exchange (ETDEWEB)

Chen, Yu; Mao, Yan-Peng; Zhu, Hai-Song; Cheng, Jing-Yi; Long, Xiang-Li; Yuan, Wei-Kang [State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Shanghai (China)

2010-07-15

The wet ammonia (NH{sub 3}) desulfurization process can be retrofitted to remove nitric oxide (NO) and sulfur dioxide (SO{sub 2}) simultaneously by adding soluble cobalt(II) salt into the aqueous ammonia solution. Activated carbon is used as a catalyst to regenerate hexaminecobalt(II), Co(NH{sub 3}){sub 6}{sup 2+}, so that NO removal efficiency can be maintained at a high level for a long time. In this study, the catalytic performance of pitch-based spherical activated carbon (PBSAC) in the simultaneous removal of NO and SO{sub 2} with this wet ammonia scrubbing process has been studied systematically. Experiments have been performed in a batch stirred cell to test the catalytic characteristics of PBSAC in the catalytic reduction of hexaminecobalt(III), Co(NH{sub 3}){sub 6}{sup 3+}. The experimental results show that PBSAC is a much better catalyst in the catalytic reduction of Co(NH{sub 3}){sub 6}{sup 3+} than palm shell activated carbon (PSAC). The Co(NH{sub 3}){sub 6}{sup 3+} reduction reaction rate increases with PBSAC when the PBSAC dose is below 7.5 g/L. The Co(NH{sub 3}){sub 6}{sup 3+} reduction rate increases with its initial concentration. Best Co(NH{sub 3}){sub 6}{sup 3+} conversion is gained at a pH range of 2.0-6.0. A high temperature is favorable to such reaction. The intrinsic activation energy of 51.00 kJ/mol for the Co(NH{sub 3}){sub 6}{sup 3+} reduction catalyzed by PBSAC has been obtained. The experiments manifest that the simultaneous elimination of NO and SO{sub 2} by the hexaminecobalt solution coupled with catalytic regeneration of hexaminecobalt(II) can maintain a NO removal efficiency of 90% for a long time. (Abstract Copyright [2010], Wiley Periodicals, Inc.)

Catalytic molecularly imprinted polymer membranes: development of the biomimetic sensor for phenols detection.

Science.gov (United States)

Sergeyeva, T A; Slinchenko, O A; Gorbach, L A; Matyushov, V F; Brovko, O O; Piletsky, S A; Sergeeva, L M; Elska, G V

2010-02-05

Portable biomimetic sensor devices for the express control of phenols content in water were developed. The synthetic binding sites mimicking active site of the enzyme tyrosinase were formed in the structure of free-standing molecularly imprinted polymer membranes. Molecularly imprinted polymer membranes with the catalytic activity were obtained by co-polymerization of the complex Cu(II)-catechol-urocanic acid ethyl ester with (tri)ethyleneglycoldimethacrylate, and oligourethaneacrylate. Addition of the elastic component oligourethaneacrylate provided formation of the highly cross-linked polymer with the catalytic activity in a form of thin, flexible, and mechanically stable membrane. High accessibility of the artificial catalytic sites for the interaction with the analyzed phenol molecules was achieved due to addition of linear polymer (polyethyleneglycol Mw 20,000) to the initial monomer mixture before the polymerization. As a result, typical semi-interpenetrating polymer networks (semi-IPNs) were formed. The cross-linked component of the semi-IPN was represented by the highly cross-linked catalytic molecularly imprinted polymer, while the linear one was represented by polyethyleneglycol Mw 20,000. Extraction of the linear polymer from the fully formed semi-IPN resulted in formation of large pores in the membranes' structure. Concentration of phenols in the analyzed samples was detected using universal portable device oxymeter with the oxygen electrode in a close contact with the catalytic molecularly imprinted polymer membrane as a transducer. The detection limit of phenols detection using the developed sensor system based on polymers-biomimics with the optimized composition comprised 0.063 mM, while the linear range of the sensor comprised 0.063-1 mM. The working characteristics of the portable sensor devices were investigated. Storage stability of sensor systems at room temperature comprised 12 months (87%). As compared to traditional methods of phenols

Method for producing bio-fuel that integrates heat from carbon-carbon bond-forming reactions to drive biomass gasification reactions

Science.gov (United States)

Cortright, Randy D [Madison, WI; Dumesic, James A [Verona, WI

2011-01-18

A low-temperature catalytic process for converting biomass (preferably glycerol recovered from the fabrication of bio-diesel) to synthesis gas (i.e., H.sub.2/CO gas mixture) in an endothermic gasification reaction is described. The synthesis gas is used in exothermic carbon-carbon bond-forming reactions, such as Fischer-Tropsch, methanol, or dimethylether syntheses. The heat from the exothermic carbon-carbon bond-forming reaction is integrated with the endothermic gasification reaction, thus providing an energy-efficient route for producing fuels and chemicals from renewable biomass resources.

CATALYTIC PROPERTIES AND ACIDITY OF MODIFIED MCM-41 ...

African Journals Online (AJOL)

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obtain H-form catalysts, samples were heated to remove the NH3 gas. Catalytic tests .... Chem. Soc. Ethiop. 2006, 20(1). 102. 0. 50. 100. 150. 200. 250. 300. 350. 400. 450. 0. 0.2 ..... Zhao, X.S.; Lu, G.Q.; Millar, G.J.; Li, X.S. Catal. Lett. 1996, 38 ...

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

Science.gov (United States)

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

2014-10-07

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

Removal of elemental mercury by TiO₂doped with WO₃ and V₂O₅ for their photo- and thermo-catalytic removal mechanisms.

Science.gov (United States)

Shen, Huazhen; Ie, Iau-Ren; Yuan, Chung-Shin; Hung, Chung-Hsuang; Chen, Wei-Hsiang

2016-03-01

The catalytic removal of Hg(0) was investigated to ascertain whether the catalysts could simultaneously possess both thermo- and photo-catalytic reactivity. The immobilized V2O5/TiO2 and WO3/TiO2 catalysts were synthesized by sol-gel method and then coated on the surface of glass beads for catalytic removal of Hg(0). They were also characterized by SEM, BET, XRD, UV-visible, and XPS analysis, and their catalytic reactivity was tested under 100-160 °C under the near-UV irradiation. The results indicated that V2O5/TiO2 solely possessed the thermo-catalytic reactivity while WO3/TiO2 only had photo-catalytic reactivity. Although the synthesis catalytic reactivity has not been found for these catalysts up to date, but compared with TiO2, the removal efficiencies of Hg(0) at 140 and 160 °C were enhanced; particularly, the efficiency was improved from 20 % at 160 °C by TiO2 to nearly 90 % by WO3/TiO2 under the same operating conditions. The effects of doping amount of V2O5 and WO3 were also investigated, and the results showed that 10 % V2O5 and 5 % WO3/TiO2 were the best immobilized catalysts for thermo- and photo-catalytic reactivity, respectively. The effect of different influent concentrations of Hg(0) was demonstrated that the highest concentration of Hg(0) led to the best removal efficiencies for V2O5/TiO2 and WO3/TiO2 at 140 and 160 °C, because high Hg(0) concentration increased the mass transfer rate of Hg(0) toward the surface of catalysts and drove the reaction to proceed. At last, the effect of single gas component on the removal of Hg(0) was also investigated.

Treatment of Row Leachate Using Catalytic Wet Oxidation Processes in Combination Hydrogen Peroxide, A Case Study of Isfahan Composting Factory Leachate

Directory of Open Access Journals (Sweden)

Behrouz Karimi

2013-08-01

Full Text Available Treatment of toxic organic compounds is one of the major applications of the Wet Air Oxidation (WAO processes. The process can be defined  as the oxidation of substances, either in the form of solutions or suspensions, with the use of an oxidant (oxygen or air at elevated pressure and temperature. The aim of this paper was to study of Catalytic Wet Oxidation (CWAO with hydrogen peroxide to improve removal efficiency of organic matter and ammonia mainly produced in Isfahan composting factory leachate. The experiment was carried out by adding 1.5 Lit pretreated leachate sample to 3 Lit autoclave reactor. Four parameters are considered: pressure (8–12 bar; temperature (100–300 °C; retention time (30–90 min; H2O2 (1–5 mL/L.The highest removal efficiencies of COD and BOD were achieved at 300°C; approximately 44% and 48% were destroyed, respectively. On the other hand, highest ammonium removal efficiency was achieved at 100 °C in which approximately 63.8% was removed. The efficiency of aqueous phase oxidation can be largely improved by the use of H2O2 as catalyst. Therefore, catalytic wet oxidation would provide an environmentally attractive option for control of organic and toxic wastes problems. Temperature was found to be the most important control variable of the wet oxidation process of leachate.

Solar photo catalytic treatment of simulated dyestuff effluents

Energy Technology Data Exchange (ETDEWEB)

Kositzi, M.; Antoniadis, A.; Poulios, I.; Kiridies, I.; Malato, S.

2003-07-01

The photo catalytic organic content reduction of two selected synthetic wastewater from the textile dyeing industry, by the use heterogeneous and homogeneous photo catalytic methods under solar irradiation, has been studied at a pilot plant scale at the Plataforma Solar de Almeria. the effect of two different TiO{sub 2} modifications with oxidants such as H{sub 2}O{sub 2} and Na{sub 2}S{sub 2}O{sub 8}, on the decolorisation and the organic content reduction (DOC) of the wastewater was examined. the TiO{sub 2}/H{sub 2}O{sub 2} system seems to be more efficient in comparison to the synergetic action which appears when using persulfate and TiO{sub 2} in these specific wastewaters. By an accumulation energy of 50 KJ L''-1 the synergetic effect of TiO{sub 2} P-25 with H{sub 2}O{sub 2} and Na{sub 2}S{sub 2}O{sub 8} leads to a 70% and 57% DOC reduction, respectively, in the case of cotton synthetic wastewater, while the decolorisation was almost complete. The photo catalytic decolorisation, as well as the DOC reduction in the case of naylon simulated wastewater is a slower process and by an accumulation energy of 50 KJ L''-1 leads to 54% mineralization in both cases. The Photo-Fenton process in both cases was more efficient for this type of wastewater in comparison to the TiO{sub 2}/oxidant system. An accumulation of energy of 50 KJ L''-1 leads to 90% reduction of the organic content. (Author) 13 refs.

Weak Form Efficiency of the Insurance Industry: Empirical Evidence from Nigeria

Directory of Open Access Journals (Sweden)

Emenike Kalu Onwukwe

2018-02-01

Full Text Available This paper evaluated the insurance sector of Nigeria Stock Exchange (NSE for evidence weak-form efficiency using daily returns from January 2009 to February 2016. The study employs descriptive analysis, non-parametric runs test and autocorrelation function as well as Ljung-Box Q statistics in conducting the evaluation. Descriptive statistics of the insurance sector return series showed negative skewness and leptokurtic distribution. Estimates from the Jarque-Bera normality test showed that the insurance sector returns did not follow normal distribution. Results of the runs test reject null hypothesis of randomness in the return series of the insurance sector in the period studied. Furthermore, the autocorrelation functions and the Ljung-Box Q tests provide evidence of serial correlation in the stock returns of the insurance sector. Overall results from the study suggested that the insurance sector of NSE is not weak-form efficient. Consequently, technical analysis on the insurance sector of the NSE may not be fruitless.

Weak-form Efficiency of the Insurance Industry: Empirical Evidence from Nigeria

Directory of Open Access Journals (Sweden)

Emenike Kalu Onwukwe

2018-02-01

Full Text Available This paper evaluates the insurance sector of Nigeria Stock Exchange (NSE for evidence weak-form efficiency using daily returns from January 2009 to February 2016. The study employs descriptive analysis, non-parametric runs test and autocorrelation function as well as Ljung-Box Q statistics in conducting the evaluation. Descriptive statistics of the insurance sector return series show negative skewness and leptokurtic distribution. Estimates from the Jarque-Bera normality test show that the insurance sector returns do not follow a normal distribution. Results of the runs test reject the null hypothesis of randomness in the return series of the insurance sector in the period studied. Furthermore, the autocorrelation functions and the Ljung-Box Q tests provide evidence of serial correlation in the stock returns of the insurance sector. Overall results from the study suggest that the insurance sector of NSE is not weak-form efficient. Consequently, technical analysis on the insurance sector of the NSE may not be fruitless.

Reaction Current Phenomenon in Bifunctional Catalytic Metal-Semiconductor Nanostructures

Science.gov (United States)

Hashemian, Mohammad Amin

Energy transfer processes accompany every elementary step of catalytic chemical processes on material surface including molecular adsorption and dissociation on atoms, interactions between intermediates, and desorption of reaction products from the catalyst surface. Therefore, detailed understanding of these processes on the molecular level is of great fundamental and practical interest in energy-related applications of nanomaterials. Two main mechanisms of energy transfer from adsorbed particles to a surface are known: (i) adiabatic via excitation of quantized lattice vibrations (phonons) and (ii) non-adiabatic via electronic excitations (electron/hole pairs). Electronic excitations play a key role in nanocatalysis, and it was recently shown that they can be efficiently detected and studied using Schottky-type catalytic nanostructures in the form of measureable electrical currents (chemicurrents) in an external electrical circuit. These nanostructures typically contain an electrically continuous nanocathode layers made of a catalytic metal deposited on a semiconductor substrate. The goal of this research is to study the direct observations of hot electron currents (chemicurrents) in catalytic Schottky structures, using a continuous mesh-like Pt nanofilm grown onto a mesoporous TiO2 substrate. Such devices showed qualitatively different and more diverse signal properties, compared to the earlier devices using smooth substrates, which could only be explained on the basis of bifunctionality. In particular, it was necessary to suggest that different stages of the reaction are occurring on both phases of the catalytic structure. Analysis of the signal behavior also led to discovery of a formerly unknown (very slow) mode of the oxyhydrogen reaction on the Pt/TiO2(por) system occurring at room temperature. This slow mode was producing surprisingly large stationary chemicurrents in the range 10--50 microA/cm2. Results of the chemicurrent measurements for the bifunctional

AMP-forming acetyl-CoA synthetases in Archaea show unexpected diversity in substrate utilization

Science.gov (United States)

Ingram-Smith, Cheryl; Smith, Kerry S.

2007-01-01

Adenosine monophosphate (AMP)-forming acetyl-CoA synthetase (ACS; acetate:CoA ligase (AMP-forming), EC 6.2.1.1) is a key enzyme for conversion of acetate to acetyl-CoA, an essential intermediate at the junction of anabolic and catabolic pathways. Phylogenetic analysis of putative short and medium chain acyl-CoA synthetase sequences indicates that the ACSs form a distinct clade from other acyl-CoA synthetases. Within this clade, the archaeal ACSs are not monophyletic and fall into three groups composed of both bacterial and archaeal sequences. Kinetic analysis of two archaeal enzymes, an ACS from Methanothermobacter thermautotrophicus (designated as MT-ACS1) and an ACS from Archaeoglobus fulgidus (designated as AF-ACS2), revealed that these enzymes have very different properties. MT-ACS1 has nearly 11-fold higher affinity and 14-fold higher catalytic efficiency with acetate than with propionate, a property shared by most ACSs. However, AF-ACS2 has only 2.3-fold higher affinity and catalytic efficiency with acetate than with propionate. This enzyme has an affinity for propionate that is almost identical to that of MT-ACS1 for acetate and nearly tenfold higher than the affinity of MT-ACS1 for propionate. Furthermore, MT-ACS1 is limited to acetate and propionate as acyl substrates, whereas AF-ACS2 can also utilize longer straight and branched chain acyl substrates. Phylogenetic analysis, sequence alignment and structural modeling suggest a molecular basis for the altered substrate preference and expanded substrate range of AF-ACS2 versus MT-ACS1. PMID:17350930

AMP-forming acetyl-CoA synthetases in Archaea show unexpected diversity in substrate utilization

Directory of Open Access Journals (Sweden)

Cheryl Ingram-Smith

2006-01-01

Full Text Available Adenosine monophosphate (AMP-forming acetyl-CoA synthetase (ACS; acetate:CoA ligase (AMP-forming, EC 6.2.1.1 is a key enzyme for conversion of acetate to acetyl-CoA, an essential intermediate at the junction of anabolic and catabolic pathways. Phylogenetic analysis of putative short and medium chain acyl-CoA synthetase sequences indicates that the ACSs form a distinct clade from other acyl-CoA synthetases. Within this clade, the archaeal ACSs are not monophyletic and fall into three groups composed of both bacterial and archaeal sequences. Kinetic analysis of two archaeal enzymes, an ACS from Methanothermobacter thermautotrophicus (designated as MT-ACS1 and an ACS from Archaeoglobus fulgidus (designated as AF-ACS2, revealed that these enzymes have very different properties. MT-ACS1 has nearly 11-fold higher affinity and 14-fold higher catalytic efficiency with acetate than with propionate, a property shared by most ACSs. However, AF-ACS2 has only 2.3-fold higher affinity and catalytic efficiency with acetate than with propionate. This enzyme has an affinity for propionate that is almost identical to that of MT-ACS1 for acetate and nearly tenfold higher than the affinity of MT-ACS1 for propionate. Furthermore, MT-ACS1 is limited to acetate and propionate as acyl substrates, whereas AF-ACS2 can also utilize longer straight and branched chain acyl substrates. Phylogenetic analysis, sequence alignment and structural modeling suggest a molecular basis for the altered substrate preference and expanded substrate range of AF-ACS2 versus MT-ACS1.

Heterogeneous kinetic modeling of the catalytic conversion of cycloparaffins

Science.gov (United States)

Al-Sabawi, Mustafa N.

The limited availability of high value light hydrocarbon feedstocks along with the rise in crude prices has resulted in the international recognition of the vast potential of Canada's oil sands. With the recent expansion of Canadian bitumen production come, however, many technical challenges, one of which is the significant presence of aromatics and cycloparaffins in bitumen-derived feedstocks. In addition to their negative environmental impact, aromatics limit fluid catalytic cracking (FCC) feedstock conversion, decrease the yield and quality of valuable products such as gasoline and middle distillates, increase levels of polyaromatic hydrocarbons prone to form coke on the catalyst, and ultimately compromise the FCC unit performance. Although cycloparaffins do not have such negative impacts, they are precursors of aromatics as they frequently undergo hydrogen transfer reactions. However, cycloparaffin cracking chemistry involves other competing reactions that are complex and need much investigation. This dissertation provides insights and understanding of the fundamentals of the catalytic cracking of cycloparaffins using carefully selected model compounds such as methylcyclohexane (MCH) and decalin. Thermal and catalytic cracking of these cycloparaffins on FCC-type catalysts are carried out using the CREC Riser Simulator under operating conditions similar to those of the industrial FCC units in terms of temperature, reaction time, reactant partial pressure and catalyst-to-hydrocarbon ratio. The crystallite size of the supported zeolites is varied between 0.4 and 0.9 microns, with both activity and selectivity being monitored. Catalytic conversions ranged between 4 to 16 wt% for MCH and between 8 to 27 wt% for decalin. Reaction pathways of cycloparaffins are determined, and these include ring-opening, protolytic cracking, isomerization, hydrogen transfer and transalkylation. The yields and selectivities of over 60 and 140 products, formed during MCH and decalin

Characterization of Nicotinamidases: Steady-State Kinetic Parameters, Class-wide Inhibition by Nicotinaldehydes and Catalytic Mechanism†

Science.gov (United States)

French, Jarrod B.; Cen, Yana; Vrablik, Tracy L.; Xu, Ping; Allen, Eleanor; Hanna-Rose, Wendy; Sauve, Anthony A.

2010-01-01

Nicotinamidases are metabolic enzymes that hydrolyze nicotinamide to nicotinic acid. These enzymes are widely distributed across biology, with examples found encoded in the genomes of Mycobacteria, Archaea, Eubacteria, Protozoa, yeast and invertebrates but there are none found in mammals. Although recent structural work has improved understanding of these enzymes, their catalytic mechanism is still not well understood. Recent data shows that nicotinamidases are required for growth and virulence of several pathogenic microbes. The enzymes of Saccharomyces cerevisiae, Drosophila melanogaster and Caenorhabditis elegans regulate lifespan in their respective organisms, consistent with proposed roles in the regulation of NAD+ metabolism and organismal aging. In this manuscript, the steady state kinetic parameters of nicotinamidase enzymes from C. elegans, S. cerevisiae, Streptococcus pneumoniae (a pathogen responsible for human pneumonia), Borrelia burgdorferi (the pathogen that causes Lyme Disease) and Plasmodium falciparum (responsible for most human malaria) are reported. Nicotinamidases are generally efficient catalysts with steady state kcat values typically exceeding 1 s−1. The Km values for nicotinamide are low and are in the range from 2 – 110 µM. Nicotinaldehyde was determined to be a potent competitive inhibitor of these enzymes, binding in the low µM to low nM range for all nicotinamidases tested. A variety of nicotinaldehyde derivatives were synthesized and evaluated as inhibitors in kinetic assays. Inhibitions are consistent with reaction of the universally conserved catalytic Cys on each enzyme with the aldehyde carbonyl carbon to form a thiohemiacetal complex which is stabilized by a conserved oxyanion hole. The S. pneumoniae nicotinamidase can catalyse exchange of 18O into the carboxy oxygens of nicotinic acid with 18O-water. The collected data, along with kinetic analysis of several mutants, allowed us to propose a catalytic mechanism that explains

Outstanding catalytic activity of ultra-pure platinum nanoparticles.

Science.gov (United States)

Januszewska, Aneta; Dercz, Grzegorz; Piwowar, Justyna; Jurczakowski, Rafal; Lewera, Adam

2013-12-09

Small (4 nm) nanoparticles with a narrow size distribution, exceptional surface purity, and increased surface order, which exhibits itself as an increased presence of basal crystallographic planes, can be obtained without the use of any surfactant. These nanoparticles can be used in many applications in an as-received state and are threefold more active towards a model catalytic reaction (oxidation of ethylene glycol). Furthermore, the superior properties of this material are interesting not only due to the increase in their intrinsic catalytic activity, but also due to the exceptional surface purity itself. The nanoparticles can be used directly (i.e., as-received, without any cleaning steps) in biomedical applications (i.e., as more efficient drug carriers due to an increased number of adsorption sites) and in energy-harvesting/data-storage devices. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Coral-like CeO{sub 2}/NiO nanocomposites with efficient enzyme-mimetic activity for biosensing application

Energy Technology Data Exchange (ETDEWEB)

Mu, Jianshuai; Zhao, Xin; Li, Jie [College of Chemistry, Key Laboratory of Inorganic-Organic Hybrid Functional Material Chemistry, Ministry of Education, Tianjin Key Laboratory of Structure and Performance for Functional Molecules, Tianjin Normal University, Tianjin 300387 (China); Yang, En-Cui, E-mail: encui_yang@163.com [College of Chemistry, Key Laboratory of Inorganic-Organic Hybrid Functional Material Chemistry, Ministry of Education, Tianjin Key Laboratory of Structure and Performance for Functional Molecules, Tianjin Normal University, Tianjin 300387 (China); Zhao, Xiao-Jun, E-mail: xiaojun_zhao15@163.com [College of Chemistry, Key Laboratory of Inorganic-Organic Hybrid Functional Material Chemistry, Ministry of Education, Tianjin Key Laboratory of Structure and Performance for Functional Molecules, Tianjin Normal University, Tianjin 300387 (China); Collaborative Innovation Center of Chemical Science and Engineering, Tianjin 300071 (China)

2017-05-01

Development of nanomaterials-based enzymatic mimics has gained considerable attention in recent years, because of their low cost, high stability and efficiently catalytic ability. Here, CeO{sub 2} was successfully incorporated into the coral-like NiO nanostructures assembled by nanoflakes with high surface area, forming the coral-like CeO{sub 2}/NiO nanocomposites. The morphology and composition of CeO{sub 2}/NiO nanocomposites were characterized by XRD, SEM, element mapping and XPS. The results of characterization showed that cerium was highly dispersed in the coral-like NiO nanostructures. The peroxidase-like activity of CeO{sub 2}/NiO nanocomposites was investigated, and they exhibited enhanced peroxidase-like activity in comparison to that of pure NiO or CeO{sub 2}. The catalytic activity was dependent on the cerium content, and the optimal content was 2.5%. The enhanced catalytic activity of CeO{sub 2}/NiO nanocomposites arised from their high ability of electron transfer because of cerium incorporation. The catalytic performance of CeO{sub 2}/NiO nanocomposites was evaluated by steady-state kinetic, which showed that the CeO{sub 2}/NiO nanocomposites exhibited higher affinity for the substrates and similar catalytic efficiency compared with natural peroxidase. Based on the efficient peroxidase-like activity, CeO{sub 2}/NiO was used for H{sub 2}O{sub 2} determination. The constructed colorimetric H{sub 2}O{sub 2} sensor had fast response for only 5 min, a wide linear range from 0.05 to 40 mM and a low detection limit with 0.88 μM. The CeO{sub 2}/NiO nanocomposites were expected to have potential applications in clinical diagnosis and biotechnology as enzymatic mimics. - Highlights: • Coral-like CeO{sub 2}/NiO nanocomposites with different Ce content were synthesized. • CeO{sub 2} was highly dispersed in the NiO matrixes with high surface area. • CeO{sub 2}/NiO nanocomposites exhibited efficient peroxidase-like activity. • A colorimetric H{sub 2}O

Oxyfuel combustion using a catalytic ceramic membrane reactor

Energy Technology Data Exchange (ETDEWEB)

Tan, Xiaoyao; Li, K. [Department of Chemical Engineering, Imperial College London, University of London, South Kensington, London SW7 2AZ (United Kingdom); Thursfield, A.; Metcalfe, I.S. [School of Chemical Engineering and Advanced Materials, Newcastle University, Newcastle upon Tyne, NE1 7RU (United Kingdom)

2008-02-29

Membrane catalytic combustion (MCC) is an environmentally friendly technique for heat and power generation from methane. This work demonstrates the performances of a MCC perovskite hollow fibre membrane reactor for the catalytic combustion of methane. The ionic-electronic La{sub 0.6}Sr{sub 0.4}Co{sub 0.2}Fe{sub 0.8}O{sub 3-{alpha}} (LSCF6428) mixed conductor, in the form of an oxygen-permeable hollow fibre membrane, has been prepared successfully by means of a phase-inversion spinning/sintering technique. For this process polyethersulfone (PESf) was used as a binder, N-methyl-2-pyrrollidone (NMP) as solvent and polyvinylpyrrolidone (PVP, K16-18) as an additive. With the prepared LSCF6428 hollow fibre membranes packed with catalyst, hollow fibre membrane reactors (HFMRs) have been assembled to perform the catalytic combustion of methane. A simple mathematical model that combines the local oxygen permeation rate with approximate catalytic reaction kinetics has been developed and can be used to predict the performance of the HFMRs for methane combustion. The effects of operating temperature and methane and air feed flow rates on the performance of the HFMR have been investigated both experimentally and theoretically. Both the methane conversion and oxygen permeation rate can be improved by means of coating platinum on the air side of the hollow fibre membranes. (author)

Evaluation of the conversion efficiency of ceramic and metallic three way catalytic converters

International Nuclear Information System (INIS)

Santos, H.; Costa, M.

2008-01-01

Ceramic and metallic three way catalytic converters have been compared to assess the influence of the substrate geometrical and physical parameters on the exhaust gas conversions for several vehicle operating conditions. Both catalysts were placed on a vehicle equipped with a 2.8 l DOHC V6 spark ignition engine that was tested on a chassis dynamometer under steady state conditions for several engine speeds and loads. The data obtained include exhaust gas species concentrations and temperature taken both upstream and downstream of the catalytic converter, as well as temperatures in various locations within the substrate of the catalysts. The experimental data revealed that: (i) at low space velocities, the ceramic substrate presents better conversions, particularly for HC and CO, as compared to the metallic substrate, possibly because of its lower thermal conductivity which facilitates local ignition; (ii) at high space velocities, the metallic substrate presents better conversions, as compared to the ceramic substrate, mainly because of its larger geometric surface area and lower transverse Peclet number; and (iii) in general, the HC conversion for small space velocities is kinetically controlled while for high space velocities it is mass transfer limited; both limitations are less pronounced for the CO conversion and insignificant for the NO x conversion

In situ synthesis and catalytic application of reduced graphene oxide supported cobalt nanowires

Science.gov (United States)

Xu, Zhiqiang; Long, Qin; Deng, Yi; Liao, Li

2018-05-01

Controlled synthesis of magnetic nanocomposite with outstanding catalytic performances is a promising strategy in catalyst industry. We proposed a novel concept for fabrication of reduced graphene oxide-supported cobalt nanowires (RGO/Co-NWs) nanocomposite as high-efficient magnetic catalyst. Unlike the majority of experiments necessitating harsh synthesis conditions such as high-pressure, high-temperature and expensive template, here the RGO/Co-NWs were successfully prepared in aqueous solution under mild conditions with the assistance of external magnetic field. The synthetic process was facile and external magnetic force was adopted to induce the unidirectional self-assembly of cobalt crystals on graphene oxide to form RGO/Co-NWs. The possible formation mechanism laid on the fact that the dipole magnetic moments of the nanoparticles were aligned along the magnetic induction lines with the external magnetic field direction resulting in the formation of nanowires elongating in the direction of the magnetization axis. Simultaneously, a series of controlled reactions were conducted to illuminate the effect of graphene oxide, external magnetic field and PVP on the morphology and size of RGO/Co-NWs in the present approach. More importantly, the nanocomposite exhibited a high catalytic performance towards ammonia borane. Hence the novel nanocomposite holds a great potential for technological applications such as catalyst industry.

Plasma-catalytic reforming of ethanol: influence of air activation rate and reforming temperature

International Nuclear Information System (INIS)

Nedybaliuk, O.A.; Chernyak, V.Ya.; Fedirchuk, I.I.; Demchina, V.P.; Bortyshevsky, V.A.; Korzh, R.V.

2016-01-01

This paper presents the study of the influence that air activation rate and reforming temperature have on the gaseous products composition and conversion efficiency during the plasma-catalytic reforming of ethanol. The analysis of product composition showed that the conversion efficiency of ethanol has a maximum in the studied range of reforming temperatures. Researched system provided high reforming efficiency and high hydrogen energy yield at the lower temperatures than traditional conversion technologies

Nano-Fe 3 O 4 /O 2 : Green, Magnetic and Reusable Catalytic ...

African Journals Online (AJOL)

, efficient, heterogeneous and reusable catalytic system for the synthesis of benzimidazoles via the reactions of o-phenylenediamine (1 eq) with aryl aldehydes (1 eq) in excellentyields (85–97 %) and short reaction times (30–100 min) with a ...

Natural Variants of the KPC-2 Carbapenemase have Evolved Increased Catalytic Efficiency for Ceftazidime Hydrolysis at the Cost of Enzyme Stability.

Directory of Open Access Journals (Sweden)

Shrenik C Mehta

2015-06-01

Full Text Available The spread of β-lactamases that hydrolyze penicillins, cephalosporins and carbapenems among Gram-negative bacteria has limited options for treating bacterial infections. Initially, Klebsiella pneumoniae carbapenemase-2 (KPC-2 emerged as a widespread carbapenem hydrolyzing β-lactamase that also hydrolyzes penicillins and cephalosporins but not cephamycins and ceftazidime. In recent years, single and double amino acid substitution variants of KPC-2 have emerged among clinical isolates that show increased resistance to ceftazidime. Because it confers multi-drug resistance, KPC β-lactamase is a threat to public health. In this study, the evolution of KPC-2 function was determined in nine clinically isolated variants by examining the effects of the substitutions on enzyme kinetic parameters, protein stability and antibiotic resistance profile. The results indicate that the amino acid substitutions associated with KPC-2 natural variants lead to increased catalytic efficiency for ceftazidime hydrolysis and a consequent increase in ceftazidime resistance. Single substitutions lead to modest increases in catalytic activity while the double mutants exhibit significantly increased ceftazidime hydrolysis and resistance levels. The P104R, V240G and H274Y substitutions in single and double mutant combinations lead to the largest increases in ceftazidime hydrolysis and resistance. Molecular modeling suggests that the P104R and H274Y mutations could facilitate ceftazidime hydrolysis through increased hydrogen bonding interactions with the substrate while the V240G substitution may enhance backbone flexibility so that larger substrates might be accommodated in the active site. Additionally, we observed a strong correlation between gain of catalytic function for ceftazidime hydrolysis and loss of enzyme stability, which is in agreement with the 'stability-function tradeoff' phenomenon. The high Tm of KPC-2 (66.5°C provides an evolutionary advantage as

Catalytic Reforming of Oxygenates: State of the Art and Future Prospects.

Science.gov (United States)

Li, Di; Li, Xinyu; Gong, Jinlong

2016-10-12

This Review describes recent advances in the design, synthesis, reactivity, selectivity, structural, and electronic properties of the catalysts for reforming of a variety of oxygenates (e.g., from simple monoalcohols to higher polyols, then to sugars, phenols, and finally complicated mixtures like bio-oil). A comprehensive exploration of the structure-activity relationship in catalytic reforming of oxygenates is carried out, assisted by state-of-the-art characterization techniques and computational tools. Critical emphasis has been given on the mechanisms of these heterogeneous-catalyzed reactions and especially on the nature of the active catalytic sites and reaction pathways. Similarities and differences (reaction mechanisms, design and synthesis of catalysts, as well as catalytic systems) in the reforming process of these oxygenates will also be discussed. A critical overview is then provided regarding the challenges and opportunities for research in this area with a focus on the roles that systems of heterogeneous catalysis, reaction engineering, and materials science can play in the near future. This Review aims to present insights into the intrinsic mechanism involved in catalytic reforming and provides guidance to the development of novel catalysts and processes for the efficient utilization of oxygenates for energy and environmental purposes.

Development of catalytic microreactors by plasma processes: application to wastewater treatment

NARCIS (Netherlands)

Da Silva, B.T.

2015-01-01

A key aspect in overcoming the energy and environmental challenges is to improve the efficiency of existing and new processes. Nowadays, almost all major chemicals are produced by catalytic processes. However, a better understanding of the reaction pathways and kinetics is needed. In the field of

Non-thermal plasmas for non-catalytic and catalytic VOC abatement

International Nuclear Information System (INIS)

Vandenbroucke, Arne M.; Morent, Rino; De Geyter, Nathalie; Leys, Christophe

2011-01-01

Highlights: → We review the current status of catalytic and non-catalytic VOC abatement based on a vast number of research papers. → The underlying mechanisms of plasma-catalysis for VOC abatement are discussed. → Critical process parameters that determine the influent are discussed and compared. - Abstract: This paper reviews recent achievements and the current status of non-thermal plasma (NTP) technology for the abatement of volatile organic compounds (VOCs). Many reactor configurations have been developed to generate a NTP at atmospheric pressure. Therefore in this review article, the principles of generating NTPs are outlined. Further on, this paper is divided in two equally important parts: plasma-alone and plasma-catalytic systems. Combination of NTP with heterogeneous catalysis has attracted increased attention in order to overcome the weaknesses of plasma-alone systems. An overview is given of the present understanding of the mechanisms involved in plasma-catalytic processes. In both parts (plasma-alone systems and plasma-catalysis), literature on the abatement of VOCs is reviewed in close detail. Special attention is given to the influence of critical process parameters on the removal process.

(Gold core) at (ceria shell) nanostructures for plasmon-enhanced catalytic reactions under visible light

KAUST Repository

Wang, Jianfang; Li, Benxia; Gu, Ting; Ming, Tian; Wang, Junxin; Wang, Peng; Yu, Jimmy C.

2014-01-01

Driving catalytic reactions with sunlight is an excellent example of sustainable chemistry. A prerequisite of solar-driven catalytic reactions is the development of photocatalysts with high solar-harvesting efficiencies and catalytic activities. Herein, we describe a general approach for uniformly coating ceria on monometallic and bimetallic nanocrystals through heterogeneous nucleation and growth. The method allows for control of the shape, size, and type of the metal core as well as the thickness of the ceria shell. The plasmon shifts of the Au@CeO2 nanostructures resulting from the switching between Ce(IV) and Ce(III) are observed. The selective oxidation of benzyl alcohol to benzaldehyde, one of the fundamental reactions for organic synthesis, performed under both broad-band and monochromatic light, demonstrates the visible-light-driven catalytic activity and reveals the synergistic effect on the enhanced catalysis of the Au@CeO2 nanostructures. © 2014 American Chemical Society.

(Gold core) at (ceria shell) nanostructures for plasmon-enhanced catalytic reactions under visible light

KAUST Repository

Wang, Jianfang

2014-08-26

Driving catalytic reactions with sunlight is an excellent example of sustainable chemistry. A prerequisite of solar-driven catalytic reactions is the development of photocatalysts with high solar-harvesting efficiencies and catalytic activities. Herein, we describe a general approach for uniformly coating ceria on monometallic and bimetallic nanocrystals through heterogeneous nucleation and growth. The method allows for control of the shape, size, and type of the metal core as well as the thickness of the ceria shell. The plasmon shifts of the Au@CeO2 nanostructures resulting from the switching between Ce(IV) and Ce(III) are observed. The selective oxidation of benzyl alcohol to benzaldehyde, one of the fundamental reactions for organic synthesis, performed under both broad-band and monochromatic light, demonstrates the visible-light-driven catalytic activity and reveals the synergistic effect on the enhanced catalysis of the Au@CeO2 nanostructures. © 2014 American Chemical Society.

The development of catalytic nucleophilic additions of terminal alkynes in water.

Science.gov (United States)

Li, Chao-Jun

2010-04-20

One of the major research endeavors in synthetic chemistry over the past two decades is the exploration of synthetic methods that work under ambient atmosphere with benign solvents, that maximize atom utilization, and that directly transform natural resources, such as renewable biomass, from their native states into useful chemical products, thus avoiding the need for protecting groups. The nucleophilic addition of terminal alkynes to various unsaturated electrophiles is a classical (textbook) reaction in organic chemistry, allowing the formation of a C-C bond while simultaneously introducing the alkyne functionality. A prerequisite of this classical reaction is the stoichiometric generation of highly reactive metal acetylides. Over the past decade, our laboratory and others have been exploring an alternative, the catalytic and direct nucleophilic addition of terminal alkynes to unsaturated electrophiles in water. We found that various terminal alkynes can react efficiently with a wide range of such electrophiles in water (or organic solvent) in the presence of simple and readily available catalysts, such as copper, silver, gold, iron, palladium, and others. In this Account, we describe the development of these synthetic methods, focusing primarily on results from our laboratory. Our studies include the following: (i) catalytic reaction of terminal alkynes with acid chloride, (ii) catalytic addition of terminal alkynes to aldehydes and ketones, (iii) catalytic addition of alkynes to C=N bonds, and (iv) catalytic conjugate additions. Most importantly, these reactions can tolerate various functional groups and, in many cases, perform better in water than in organic solvents, clearly defying classical reactivities predicated on the relative acidities of water, alcohols, and terminal alkynes. We further discuss multicomponent and enantioselective reactions that were developed. These methods provide an alternative to the traditional requirement of separate steps in

Efficient catalytic system for the direct transformation of lignocellulosic biomass to furfural and 5-hydroxymethylfurfural.

Science.gov (United States)

Zhang, Luxin; Xi, Guoyun; Zhang, Jiaxin; Yu, Hongbing; Wang, Xiaochang

2017-01-01

A feasible approach was developed for the co-production of 5-hydroxymethylfurfural (5-HMF) and furfural from corncob via a new porous polytriphenylamine-SO 3 H (SPTPA) solid acid catalyst in lactone solvents. XRD, SEM, XPS, N 2 adsorption-desorption, elemental analysis, TG-DTA, acid-base titration and FTIR spectroscopy techniques were used to characterize the catalyst. This study demonstrates and optimizes the catalytic performance of SPTPA and solvent selection. SPTPA was found to exhibit superior catalytic ability in γ-valerolactone (GVL). Under the optimum reaction conditions, simultaneously encouraging yields of furfural (73.9%) and 5-HMF (32.3%) were achieved at 448K. The main advantages of this process include reasonable yields of both 5-HMF and furfural in the same reaction system, practical simplicity for the raw biomass utilization, and the use of a safe and environmentally benign solvent. Copyright © 2016 Elsevier Ltd. All rights reserved.

Selective catalytic oxidation of ammonia

Energy Technology Data Exchange (ETDEWEB)

Leppaelahti, J; Koljonen, T [VTT Energy, Espoo (Finland)

1997-12-31

In the combustion of fossil fuels, the principal source of nitrogen oxides is nitrogen bound in the fuel structure. In gasification, a large part of fuel nitrogen forms NH{sub 3}, which may form nitrogen oxides during gas combustion. If NH{sub 3} and other nitrogen species could be removed from hot gas, the NO emission could be considerably reduced. However, relatively little attention has been paid to finding new means of removing nitrogen compounds from the hot gasification gas. The possibility of selectively oxidizing NH{sub 3} to N{sub 2} in the hot gasification has been studied at VTT Energy. The largest NH{sub 3} reductions have been achieved by catalytic oxidation on aluminium oxides. (author) (4 refs.)

Selective catalytic oxidation of ammonia

Energy Technology Data Exchange (ETDEWEB)

Leppaelahti, J.; Koljonen, T. [VTT Energy, Espoo (Finland)

1996-12-31

In the combustion of fossil fuels, the principal source of nitrogen oxides is nitrogen bound in the fuel structure. In gasification, a large part of fuel nitrogen forms NH{sub 3}, which may form nitrogen oxides during gas combustion. If NH{sub 3} and other nitrogen species could be removed from hot gas, the NO emission could be considerably reduced. However, relatively little attention has been paid to finding new means of removing nitrogen compounds from the hot gasification gas. The possibility of selectively oxidizing NH{sub 3} to N{sub 2} in the hot gasification has been studied at VTT Energy. The largest NH{sub 3} reductions have been achieved by catalytic oxidation on aluminium oxides. (author) (4 refs.)

Catalytic distillation process

Science.gov (United States)

Smith, L.A. Jr.

1982-06-22

A method is described for conducting chemical reactions and fractionation of the reaction mixture comprising feeding reactants to a distillation column reactor into a feed zone and concurrently contacting the reactants with a fixed bed catalytic packing to concurrently carry out the reaction and fractionate the reaction mixture. For example, a method for preparing methyl tertiary butyl ether in high purity from a mixed feed stream of isobutene and normal butene comprising feeding the mixed feed stream to a distillation column reactor into a feed zone at the lower end of a distillation reaction zone, and methanol into the upper end of said distillation reaction zone, which is packed with a properly supported cationic ion exchange resin, contacting the C[sub 4] feed and methanol with the catalytic distillation packing to react methanol and isobutene, and concurrently fractionating the ether from the column below the catalytic zone and removing normal butene overhead above the catalytic zone.

Catalytic biofilms on structured packing for the production of glycolic acid.

Science.gov (United States)

Li, Xuan Zhong; Hauer, Bernhard; Rosche, Bettina

2013-02-01

While structured packing modules are known to be efficient for surface wetting and gas-liquid exchange in abiotic surface catalysis, this model study explores structured packing as a growth surface for catalytic biofilms. Microbial biofilms have been proposed as self-immobilized and self-regenerating catalysts for the production of chemicals. A concern is that the complex and dynamic nature of biofilms may cause fluctuations in their catalytic performance over time or may affect process reproducibility. An aerated continuous trickle-bed biofilm reactor system was designed with a 3 L structured packing, liquid recycling and pH control. Pseudomonas diminuta established a biofilm on the stainless steel structured packing with a specific surface area of 500 m2 m-3 and catalyzed the oxidation of ethylene glycol to glycolic acid for over two months of continuous operation. A steady-state productivity of up to 1.6 gl-1h-1 was achieved at a dilution rate of 0.33 h-1. Process reproducibility between three independent runs was excellent, despite process interruptions and activity variations in cultures grown from biofilm effluent cells. The results demonstrate the robustness of a catalytic biofilm on structured packing, despite its dynamic nature. Implementation is recommended for whole-cell processes that require efficient gas-liquid exchange, catalyst retention for continuous operation, or improved catalyst stability.

Modeling and Re-Engineering of Azotobacter vinelandii Alginate Lyase to Enhance Its Catalytic Efficiency for Accelerating Biofilm Degradation.

Science.gov (United States)

Jang, Chul Ho; Piao, Yu Lan; Huang, Xiaoqin; Yoon, Eun Jeong; Park, So Hee; Lee, Kyoung; Zhan, Chang-Guo; Cho, Hoon

2016-01-01

Alginate is known to prevent elimination of Pseudomonas aeruginosa biofilms. Alginate lyase (AlgL) might therefore facilitate treatment of Pseudomonas aeruginosa-infected cystic fibrosis patients. However, the catalytic activity of wild-type AlgL is not sufficiently high. Therefore, molecular modeling and site-directed mutagenesis of AlgL might assist in enzyme engineering for therapeutic development. AlgL, isolated from Azotobacter vinelandii, catalyzes depolymerization of alginate via a β-elimination reaction. AlgL was modeled based on the crystal structure template of Sphingomonas AlgL species A1-III. Based on this computational analysis, AlgL was subjected to site-directed mutagenesis to improve its catalytic activity. The kcat/Km of the K194E mutant showed a nearly 5-fold increase against the acetylated alginate substrate, as compared to the wild-type. Double and triple mutants (K194E/K245D, K245D/K319A, K194E/K245D/E312D, and K194E/K245D/K319A) were also prepared. The most potent mutant was observed to be K194E/K245D/K319A, which has a 10-fold improved kcat value (against acetylated alginate) compared to the wild-type enzyme. The antibiofilm effect of both AlgL forms was identified in combination with piperacillin/tazobactam (PT) and the disruption effect was significantly higher in mutant AlgL combined with PT than wild-type AlgL. However, for both the wild-type and K194E/K245D/K319A mutant, the use of the AlgL enzyme alone did not show significant antibiofilm effect.

Modeling and Re-Engineering of Azotobacter vinelandii Alginate Lyase to Enhance Its Catalytic Efficiency for Accelerating Biofilm Degradation.

Directory of Open Access Journals (Sweden)

Chul Ho Jang

Full Text Available Alginate is known to prevent elimination of Pseudomonas aeruginosa biofilms. Alginate lyase (AlgL might therefore facilitate treatment of Pseudomonas aeruginosa-infected cystic fibrosis patients. However, the catalytic activity of wild-type AlgL is not sufficiently high. Therefore, molecular modeling and site-directed mutagenesis of AlgL might assist in enzyme engineering for therapeutic development. AlgL, isolated from Azotobacter vinelandii, catalyzes depolymerization of alginate via a β-elimination reaction. AlgL was modeled based on the crystal structure template of Sphingomonas AlgL species A1-III. Based on this computational analysis, AlgL was subjected to site-directed mutagenesis to improve its catalytic activity. The kcat/Km of the K194E mutant showed a nearly 5-fold increase against the acetylated alginate substrate, as compared to the wild-type. Double and triple mutants (K194E/K245D, K245D/K319A, K194E/K245D/E312D, and K194E/K245D/K319A were also prepared. The most potent mutant was observed to be K194E/K245D/K319A, which has a 10-fold improved kcat value (against acetylated alginate compared to the wild-type enzyme. The antibiofilm effect of both AlgL forms was identified in combination with piperacillin/tazobactam (PT and the disruption effect was significantly higher in mutant AlgL combined with PT than wild-type AlgL. However, for both the wild-type and K194E/K245D/K319A mutant, the use of the AlgL enzyme alone did not show significant antibiofilm effect.

Advanced treatment of biologically pretreated coal chemical industry wastewater using the catalytic ozonation process combined with a gas-liquid-solid internal circulating fluidized bed reactor.

Science.gov (United States)

Li, Zhipeng; Liu, Feng; You, Hong; Ding, Yi; Yao, Jie; Jin, Chao

2018-04-01

This paper investigated the performance of the combined system of catalytic ozonation and the gas-liquid-solid internal circulating fluidized bed reactor for the advanced treatment of biologically pretreated coal chemical industry wastewater (CCIW). The results indicated that with ozonation alone for 60min, the removal efficiency of chemical oxygen demand (COD) could reach 34%. The introduction of activated carbon, pumice, γ-Al 2 O 3 carriers improved the removal performance of COD, and the removal efficiency was increased by 8.6%, 4.2%, 2%, respectively. Supported with Mn, the catalytic performance of activated carbon and γ-Al 2 O 3 were improved significantly with COD removal efficiencies of 46.5% and 41.3%, respectively; however, the promotion effect of pumice supported with Mn was insignificant. Activated carbon supported with Mn had the best catalytic performance. The catalytic ozonation combined system of MnO X /activated carbon could keep ozone concentration at a lower level in the liquid phase, and promote the transfer of ozone from the gas phase to the liquid phase to improve ozonation efficiency.

Influence and efficiency of catalytic stripper in organic carbon removal from laboratory generated soot aerosols

Science.gov (United States)

A catalytic stripper (CS) is a device used to remove the semi-volatile, typically organic carbon, fraction by passing raw or diluted exhaust over an oxidation catalyst heated to 300˚C. The oxidation catalyst used in this study is a commercially available diesel oxidation ca...

FORMING OF THE SUSTAINABLE SUPPLY CHAINS BASED ON INCREASING OF THEIR INTEGRATED ENERGY EFFICIENCY

Directory of Open Access Journals (Sweden)

SHVETS V. J.

2016-03-01

Full Text Available Purpose. Key challenges and barriers of mining machinery enterprises in the context of forming sustainable supply chains in the mining industry are specified. Methodology. The algorithm of forming the industrial relations, which are carried out by the enterprises of mining machinery in order to increase the sustainable development of a mining industry, is offered. Conclusions.. Modern supply chains are confronted with dynamic trends and developments that are hard to predict. In order to respond to these changes and remain competitive advantage, companies should be able to identify and understand new sustainability issues in their branches. It is established that in the conditions of globalization of the market and the general orientation of Ukraine’s economy to the European principles of development, for mining machinery enterprises a proof of the commitment and observance of requirements of energy efficiency, i.e. energy saving, energy safety and social energy responsibility are very important. Supply channels should increase not only energy efficiency, economic and production stability of the company, but also strengthen the stability of all participants in the production chain, as well as other stakeholders (business partners, customers, investors, local communities, etc.. Originality. The interrelation of an indicator of energy efficiency in forming sustainable supply chain in a mining industry is established. Practical value. Using the principles of sustainable development in the forming of value chains will improve energy efficiency of industry in general; provide a competitive advantage to entry into the global production chains in terms of European integration of Ukraine.

Fuel Flexible, Low Emission Catalytic Combustor for Opportunity Fuel Applications

Energy Technology Data Exchange (ETDEWEB)

Eteman, Shahrokh

2013-06-30

Limited fuel resources, increasing energy demand and stringent emission regulations are drivers to evaluate process off-gases or process waste streams as fuels for power generation. Often these process waste streams have low energy content and/or highly reactive components. Operability of low energy content fuels in gas turbines leads to issues such as unstable and incomplete combustion. On the other hand, fuels containing higher-order hydrocarbons lead to flashback and auto-ignition issues. Due to above reasons, these fuels cannot be used directly without modifications or efficiency penalties in gas turbine engines. To enable the use of these wide variety of fuels in gas turbine engines a rich catalytic lean burn (RCL®) combustion system was developed and tested in a subscale high pressure (10 atm.) rig. The RCL® injector provided stability and extended turndown to low Btu fuels due to catalytic pre-reaction. Previous work has shown promise with fuels such as blast furnace gas (BFG) with LHV of 85 Btu/ft3 successfully combusted. This program extends on this work by further modifying the combustor to achieve greater catalytic stability enhancement. Fuels containing low energy content such as weak natural gas with a Lower Heating Value (LHV) of 6.5 MJ/m3 (180 Btu/ft3 to natural gas fuels containing higher hydrocarbon (e.g ethane) with LHV of 37.6 MJ/m3 (1010 Btu/ft3) were demonstrated with improved combustion stability; an extended turndown (defined as the difference between catalytic and non-catalytic lean blow out) of greater than 250oF was achieved with CO and NOx emissions lower than 5 ppm corrected to 15% O2. In addition, for highly reactive fuels the catalytic region preferentially pre-reacted the higher order hydrocarbons with no events of flashback or auto-ignition allowing a stable and safe operation with low NOx and CO emissions.

Exciplex-Forming Co-Host-Based Red Phosphorescent Organic Light-Emitting Diodes with Long Operational Stability and High Efficiency.

Science.gov (United States)

Lee, Jeong-Hwan; Shin, Hyun; Kim, Jae-Min; Kim, Kwon-Hyeon; Kim, Jang-Joo

2017-02-01

The use of exciplex forming cohosts and phosphors incredibly boosts the efficiency of organic light-emitting diodes (OLEDs) by providing a barrier-free charge injection into an emitting layer and a broad recombination zone. However, most of the efficient OLEDs based on the exciplex forming cohosts has suffered from the short operational lifetime. Here, we demonstrated phosphorescent OLEDs (PhOLEDs) having both high efficiency and long lifetime by using a new exciplex forming cohost composed of N,N'-diphenyl-N,N'-bis(1,1'-biphenyl)-4,4'-diamine (NPB) and (1,3,5-triazine-2,4,6-triyl)tris(benzene-3,1-diyl))tris(diphenylphosphine oxide) (PO-T2T). The red-emitting PhOLEDs using the exciplex forming cohost achieved a maximum external quantum efficiency (EQE) of 34.1% and power efficiency of 62.2 lm W 1- with low operating voltages and low efficiency roll-offs. More importantly, the device demonstrated a long lifetime around 2249 h from 1000 cd m -2 to 900 cd m -2 (LT 90 ) under a continuous flow of constant current. The efficiencies of the devices are the highest for red OLEDs with an LT 90 > 1000 h.

Uniformity index measurement technology using thermocouples to improve performance in urea-selective catalytic reduction systems

Science.gov (United States)

Park, Sangki; Oh, Jungmo

2018-05-01

The current commonly used nitrogen oxides (NOx) emission reduction techniques employ hydrocarbons (HCs), urea solutions, and exhaust gas emissions as the reductants. Two of the primary denitrification NOx (DeNOx) catalyst systems are the HC-lean NOx trap (HC-LNT) catalyst and urea-selective catalytic reduction (urea-SCR) catalyst. The secondary injection method depends on the type of injector, injection pressure, atomization, and spraying technique. In addition, the catalyst reaction efficiency is directly affected by the distribution of injectors; hence, the uniformity index (UI) of the reductant is very important and is the basis for system optimization. The UI of the reductant is an indicator of the NOx conversion efficiency (NCE), and good UI values can reduce the need for a catalyst. Therefore, improving the UI can reduce the cost of producing a catalytic converter, which are expensive due to the high prices of the precious metals contained therein. Accordingly, measurement of the UI is an important process in the development of catalytic systems. Two of the commonly used methods for measuring the reductant UI are (i) measuring the exhaust emissions at many points located upstream/downstream of the catalytic converter and (ii) acquisition of a reductant distribution image on a section of the exhaust pipe upstream of the catalytic converter. The purpose of this study is to develop a system and measurement algorithms to measure the exothermic response distribution in the exhaust gas as the reductant passes through the catalytic converter of the SCR catalyst system using a set of thermocouples downstream of the SCR catalyst. The system is used to measure the reductant UI, which is applied in real-time to the actual SCR system, and the results are compared for various types of mixtures for various engine operating conditions and mixer types in terms of NCE.

Zinc oxide nanostructures and its nano-compounds for efficient visible light photo-catalytic processes

Science.gov (United States)

Adam, Rania E.; Alnoor, Hatim; Elhag, Sami; Nur, Omer; Willander, Magnus

2017-02-01

Zinc oxide (ZnO) in its nanostructure form is a promising material for visible light emission/absorption and utilization in different energy efficient photocatalytic processes. We will first present our recent results on the effect of varying the molar ratio of the synthesis nutrients on visible light emission. Further we will use the optimized conditions from the molar ration experiments to vary the synthesis processing parameters like stirring time etc. and the effect of all these parameters in order to optimize the efficiency and control the emission spectrum are investigated using different complementary techniques. Cathodoluminescence (CL) is combined with photoluminescence (PL) and electroluminescence (EL) as the techniques to investigate and optimizes visible light emission from ZnO/GaN light emitting diodes. We will then show and discuss our recent finding of the use of high quality ZnO nanoparticles (NPs) for efficient photo-degradation of toxic dyes using the visible spectra, namely with a wavelength up to 800 nm. In the end, we show how ZnO nanorods (NRs) are used as the first template to be transferred to bismuth zinc vanadate (BiZn2VO6). The BiZn2VO6 is then used to demonstrate efficient and cost effective hydrogen production through photoelectrochemical water splitting using solar radiation.

Catalytic bioreactors and methods of using same

Science.gov (United States)

Worden, Robert Mark; Liu, Yangmu Chloe

2017-07-25

Various embodiments provide a bioreactor for producing a bioproduct comprising one or more catalytically active zones located in a housing and adapted to keep two incompatible gaseous reactants separated when in a gas phase, wherein each of the one or more catalytically active zones may comprise a catalytic component retainer and a catalytic component retained within and/or thereon. Each of the catalytically active zones may additionally or alternatively comprise a liquid medium located on either side of the catalytic component retainer. Catalytic component may include a microbial cell culture located within and/or on the catalytic component retainer, a suspended catalytic component suspended in the liquid medium, or a combination thereof. Methods of using various embodiments of the bioreactor to produce a bioproduct, such as isobutanol, are also provided.

Selenium utilization in thioredoxin and catalytic advantage provided by selenocysteine

International Nuclear Information System (INIS)

Kim, Moon-Jung; Lee, Byung Cheon; Hwang, Kwang Yeon; Gladyshev, Vadim N.; Kim, Hwa-Young

2015-01-01

Thioredoxin (Trx) is a major thiol-disulfide reductase that plays a role in many biological processes, including DNA replication and redox signaling. Although selenocysteine (Sec)-containing Trxs have been identified in certain bacteria, their enzymatic properties have not been characterized. In this study, we expressed a selenoprotein Trx from Treponema denticola, an oral spirochete, in Escherichia coli and characterized this selenoenzyme and its natural cysteine (Cys) homologue using E. coli Trx1 as a positive control. 75 Se metabolic labeling and mutation analyses showed that the SECIS (Sec insertion sequence) of T. denticola selenoprotein Trx is functional in the E. coli Sec insertion system with specific selenium incorporation into the Sec residue. The selenoprotein Trx exhibited approximately 10-fold higher catalytic activity than the Sec-to-Cys version and natural Cys homologue and E. coli Trx1, suggesting that Sec confers higher catalytic activity on this thiol-disulfide reductase. Kinetic analysis also showed that the selenoprotein Trx had a 30-fold higher K m than Cys-containing homologues, suggesting that this selenoenzyme is adapted to work efficiently with high concentrations of substrate. Collectively, the results of this study support the hypothesis that selenium utilization in oxidoreductase systems is primarily due to the catalytic advantage provided by the rare amino acid, Sec. - Highlights: • The first characterization of a selenoprotein Trx is presented. • The selenoenzyme Trx exhibits 10-fold higher catalytic activity than Cys homologues. • Se utilization in Trx is primarily due to the catalytic advantage provided by Sec residue

Selenium utilization in thioredoxin and catalytic advantage provided by selenocysteine

Energy Technology Data Exchange (ETDEWEB)

Kim, Moon-Jung [Department of Biochemistry and Molecular Biology, Yeungnam University College of Medicine, Daegu 705-717 (Korea, Republic of); Lee, Byung Cheon [Division of Genetics, Department of Medicine, Brigham and Women' s Hospital, Harvard Medical School, Boston, MA 02115 (United States); Division of Biotechnology, College of Life Sciences & Biotechnology, Korea University, Seoul 136-701 (Korea, Republic of); Hwang, Kwang Yeon [Division of Biotechnology, College of Life Sciences & Biotechnology, Korea University, Seoul 136-701 (Korea, Republic of); Gladyshev, Vadim N. [Division of Genetics, Department of Medicine, Brigham and Women' s Hospital, Harvard Medical School, Boston, MA 02115 (United States); Kim, Hwa-Young, E-mail: hykim@ynu.ac.kr [Department of Biochemistry and Molecular Biology, Yeungnam University College of Medicine, Daegu 705-717 (Korea, Republic of)

2015-06-12

Thioredoxin (Trx) is a major thiol-disulfide reductase that plays a role in many biological processes, including DNA replication and redox signaling. Although selenocysteine (Sec)-containing Trxs have been identified in certain bacteria, their enzymatic properties have not been characterized. In this study, we expressed a selenoprotein Trx from Treponema denticola, an oral spirochete, in Escherichia coli and characterized this selenoenzyme and its natural cysteine (Cys) homologue using E. coli Trx1 as a positive control. {sup 75}Se metabolic labeling and mutation analyses showed that the SECIS (Sec insertion sequence) of T. denticola selenoprotein Trx is functional in the E. coli Sec insertion system with specific selenium incorporation into the Sec residue. The selenoprotein Trx exhibited approximately 10-fold higher catalytic activity than the Sec-to-Cys version and natural Cys homologue and E. coli Trx1, suggesting that Sec confers higher catalytic activity on this thiol-disulfide reductase. Kinetic analysis also showed that the selenoprotein Trx had a 30-fold higher K{sub m} than Cys-containing homologues, suggesting that this selenoenzyme is adapted to work efficiently with high concentrations of substrate. Collectively, the results of this study support the hypothesis that selenium utilization in oxidoreductase systems is primarily due to the catalytic advantage provided by the rare amino acid, Sec. - Highlights: • The first characterization of a selenoprotein Trx is presented. • The selenoenzyme Trx exhibits 10-fold higher catalytic activity than Cys homologues. • Se utilization in Trx is primarily due to the catalytic advantage provided by Sec residue.

Development of a catalytically assisted combustor for a gas turbine

Energy Technology Data Exchange (ETDEWEB)

Ozawa, Yasushi; Fujii, Tomoharu; Sato, Mikio [Central Research Institute of Electric Power Industry, 2-6-1 Nagasaka, Yokosuka, Kanagawa 240-01 (Japan); Kanazawa, Takaaki; Inoue, Hitoshi [Kansai Electric Power Company, Inc., 3-11-20 Nakoji, Amagasaki, Hyoho 661 (Japan)

1999-01-01

A catalytically assisted low NO{sub x} combustor has been developed which has the advantage of catalyst durability. This combustor is composed of a burner section and a premixed combustion section behind the burner section. The burner system consists of six catalytic combustor segments and six premixing nozzles, which are arranged alternately and in parallel. Fuel flow rate for the catalysts and the premixing nozzles are controlled independently. The catalytic combustion temperature is maintained under 1000C, additional premixed gas is injected from the premixing nozzles into the catalytic combustion gas, and lean premixed combustion at 1300C is carried out in the premixed combustion section. This system was designed to avoid catalytic deactivation at high temperature and thermal or mechanical shock fracture of the honeycomb monolith. In order to maintain the catalyst temperature under 1000C, the combustion characteristics of catalysts at high pressure were investigated using a bench scale reactor and an improved catalyst was selected for the combustor test. A combustor for a 20MW class multi-can type gas turbine was designed and tested under high pressure conditions using LNG fuel. Measurements of NO{sub x}, CO and unburned hydrocarbon were made and other measurements were made to evaluate combustor performance under various combustion temperatures and pressures. As a result of the tests, it was proved that NO{sub x} emission was lower than 10ppm converted at 16% O{sub 2}, combustion efficiency was almost 100% at 1300C of combustor outlet temperature and 13.5ata of combustor inlet pressure

Electro-catalytic oxidation of reactive Orange 107 using cerium doped oxides of Nd3+ nanoparticle

International Nuclear Information System (INIS)

Rajkumar, K.; Muthukumar, M.; Mangalaraja, R.V.

2011-01-01

A new rare earth doped cerium oxide powder was used as a catalyst to investigate the removal of colour and TOC from simulated wastewater of Reactive Orange 107. The electro oxidation process was carried out in the reactor in presence of an electrolyte NaCl. Graphite electrode was used as anode and cathode and electrolysis were carried out at a current density of 34.96 mAcm -2 with a catalyst concentration of 0.05g L -1 . In order to find the efficiency of nanocatalyst, experiments were also conducted without catalyst. From the experiment, it was found that complete colour removal was achieved on electrocatalytic oxidation as well as electro oxidation. When comparing the above processes, catalytic oxidation shows more efficient than electro oxidation. With respect to the degradation of the dye, catalytic oxidation shows more TOC removal than the oxidation taken place without catalyst. It infers that even though the electro-catalytic oxidation process achieves complete decolouration but it does not achieve complete mineralisation. The FTIR and GCMS studies confirmed the formation of by-products. (author)

Catalytic Reforming: Methodology and Process Development for a Constant Optimisation and Performance Enhancement

Directory of Open Access Journals (Sweden)

Avenier Priscilla

2016-05-01

Full Text Available Catalytic reforming process has been used to produce high octane gasoline since the 1940s. It would appear to be an old process that is well established and for which nothing new could be done. It is however not the case and constant improvements are proposed at IFP Energies nouvelles. With a global R&D approach using new concepts and forefront methodology, IFPEN is able to: propose a patented new reactor concept, increasing capacity; ensure efficiency and safety of mechanical design for reactor using modelization of the structure; develop new catalysts to increase process performance due to a high comprehension of catalytic mechanism by using, an experimental and innovative analytical approach (119Sn Mössbauer and X-ray absorption spectroscopies and also a Density Functional Theory (DFT calculations; have efficient, reliable and adapted pilots to validate catalyst performance.

Gold Decorated Graphene for Rapid Dye Reduction and Efficient Electro Catalytic Oxidation of Ethanol

Science.gov (United States)

Siddhardha, R. S.; Kumar v, Lakshman; Kaniyoor, A.; Podila, R.; Kumar, V. S.; Venkataramaniah, K.; Ramaprabhu, S.; Rao, A.; Ramamurthy, S. S.; Clemson University Team; Sri Sathya Sai Institute of Higher Learning Team; IITMadras Team

2013-03-01

A well known disadvantage in fabrication of metal-graphene composite is the use of surfactants that strongly adsorb on the surface and reduce the performance of the catalyst. Here, we demonstrate a novel one pot synthesis of gold nanoparticles (AuNPs) by laser ablation of gold strip and simultaneous decoration of these on functionalized graphene derivatives. Not only the impregnation of AuNPs was linker free, but also the synthesis by itself was surfactant free. This resulted in in-situ decoration of pristine AuNPs on functionalized graphene derivatives. These materials were well characterized and tested for catalytic applications pertaining to dye reduction and electrooxidation. The catalytic reduction rates are 1.4 x 102 and 9.4x102 times faster for Rhodamine B and Methylene Blue dyes respectively, compared to earlier reports. The enhanced rate involves synergistic interplay of electronic relay between AuNPs and the dye, also charge transfer between the graphene system and dye. In addition, the onset potential for ethanol oxidation was found to be more negative ~ 100 mV, an indication of its promising application in direct ethanol fuel cells.

GC of catalytic reactions products involved in the promising fuel synthesis

Energy Technology Data Exchange (ETDEWEB)

Zheivot, V.; Sazonova, N. [Russian Academy of Sciences, Novosibirsk (Russian Federation). Boreskov Inst. of Catalysis

2012-09-15

Catalytic reactions involved in the synthesis of the promising kinds of novel fuel and products formed in these reactions were systematized according to the resulting fuel type. Generalization of the retention of the substances comprising these products is presented. Chromatograms exhibiting their separation on chromatographic materials with the surface of different chemical properties are summarized. We propose procedures for gas-chromatographic analysis of the catalytic reactions products formed in the synthesis of hydrogen, methanol, dimethyl ether and hydrocarbons as a new generation of fuel alternative to petroleum and coal. For partial oxidation of methane into synthesis gas, on-line determination of the components obtained in the reaction was carried out by gas chromatography and gas analyzer based on different physicochemical methods (IR spectroscopy and electrochemical methods). Similarity of the results obtained using these methods is demonstrated. (orig.)

Development of advanced mesostructured catalytic coatings on different substrates for fine chemical synthesis

NARCIS (Netherlands)

Protasova, L.N.

2011-01-01

Catalytic microstructured reactors are becoming widely recognized for their unique properties, such as high surface–to–volume ratios, isothermal conditions due to high heat transfer rates, enhanced safety, and potential applications in chemistry and in chemical industry. The efficient use of

Spectrophotometric evaluation of surface morphology dependent catalytic activity of biosynthesized silver and gold nanoparticles using UV–vis spectra: A comparative kinetic study

Energy Technology Data Exchange (ETDEWEB)

Ankamwar, Balaprasad, E-mail: bankamwar@yahoo.com [Bio-inspired Materials Research Laboratory, Department of Chemistry, Savitribai Phule Pune University, Ganeshkhind, Pune 411007 (India); Kamble, Vaishali; Sur, Ujjal Kumar [Bio-inspired Materials Research Laboratory, Department of Chemistry, Savitribai Phule Pune University, Ganeshkhind, Pune 411007 (India); Santra, Chittaranjan [Department of Chemistry, Netaji Nagar Day College, Regent Park, Kolkata 700092 (India)

2016-03-15

Graphical abstract: - Highlights: • The biosynthesized silver nanoparticles were stable for 6 months and used as effective SERS active substrate. • They are effective catalyst in the chemical reduction of 4-nitrophenol to 4-aminophenol. • Comparative catalytic efficiency of both silver and gold nanoparticles was studied spectrophotometrically. • Our results demonstrate surface morphology dependent catalytic activity of both nanoparticles. - Abstract: The development of eco-friendly and cost-effective synthetic protocol for the preparation of nanomaterials, especially metal nanoparticles is an emerging area of research in nanotechnology. These metal nanoparticles, especially silver can play a crucial role in various catalytic reactions. The biosynthesized silver nanoparticles described here was very stable up to 6 months and can be further exploited as an effective catalyst in the chemical reduction of 4-nitrophenol to 4-aminophenol. The silver nanoparticles were utilized as an efficient surface-enhanced Raman scattering (SERS) active substrate using Rhodamine 6G as Raman probe molecule. We have also carried out systematic comparative studies on the catalytic efficiency of both silver and gold nanoparticles using UV–vis spectra to monitor the above reaction spectrophotometrically. We find that the reaction follows pseudo-first order kinetics and the catalytic activity can be explained by a simple model based on Langmuir–Hinshelwood mechanism for heterogeneous catalysis. We also find that silver nanoparticles are more efficient as a catalyst compare to gold nanoparticles in the reduction of 4-nitrophenol to 4-aminophenol, which can be explained by the morphology of the nanoparticles as determined by transmission electron microscopy.

Spectrophotometric evaluation of surface morphology dependent catalytic activity of biosynthesized silver and gold nanoparticles using UV–vis spectra: A comparative kinetic study

International Nuclear Information System (INIS)

Ankamwar, Balaprasad; Kamble, Vaishali; Sur, Ujjal Kumar; Santra, Chittaranjan

2016-01-01

Graphical abstract: - Highlights: • The biosynthesized silver nanoparticles were stable for 6 months and used as effective SERS active substrate. • They are effective catalyst in the chemical reduction of 4-nitrophenol to 4-aminophenol. • Comparative catalytic efficiency of both silver and gold nanoparticles was studied spectrophotometrically. • Our results demonstrate surface morphology dependent catalytic activity of both nanoparticles. - Abstract: The development of eco-friendly and cost-effective synthetic protocol for the preparation of nanomaterials, especially metal nanoparticles is an emerging area of research in nanotechnology. These metal nanoparticles, especially silver can play a crucial role in various catalytic reactions. The biosynthesized silver nanoparticles described here was very stable up to 6 months and can be further exploited as an effective catalyst in the chemical reduction of 4-nitrophenol to 4-aminophenol. The silver nanoparticles were utilized as an efficient surface-enhanced Raman scattering (SERS) active substrate using Rhodamine 6G as Raman probe molecule. We have also carried out systematic comparative studies on the catalytic efficiency of both silver and gold nanoparticles using UV–vis spectra to monitor the above reaction spectrophotometrically. We find that the reaction follows pseudo-first order kinetics and the catalytic activity can be explained by a simple model based on Langmuir–Hinshelwood mechanism for heterogeneous catalysis. We also find that silver nanoparticles are more efficient as a catalyst compare to gold nanoparticles in the reduction of 4-nitrophenol to 4-aminophenol, which can be explained by the morphology of the nanoparticles as determined by transmission electron microscopy.

An efficient RuCl3·H2O/I2 catalytic system: A facile access to 3-aroylimidazo[1,2-a]pyridines from 2-aminopyridines and chalcones

Directory of Open Access Journals (Sweden)

P.V. Sri Ramya

2018-01-01

Full Text Available A simple and efficient protocol has been demonstrated for the preparation of densely functionalized 3-aroylimidazo[1,2-a]pyridines from 2-aminopyridines and chalcones using RuCl3·H2O/I2 catalytic system. The advantages, such as low catalyst loading, broad substrate scope with respect to substitutions on aminopyridines as well as chalcones, stability of heterocycles such as thiophene under the reaction conditions, operationally simple procedure and higher yields makes this approach remarkable for synthetic applications.

Removal of nitrogen compounds from gasification gas by selective catalytic or non-catalytic oxidation; Typpiyhdisteiden poisto kaasutuskaasusta selektiivisellae katalyyttisellae ja ei-katalyyttisellae hapetuksella

Energy Technology Data Exchange (ETDEWEB)

Leppaelahti, J.; Koljonen, T. [VTT Energy, Espoo (Finland)

1996-12-01

In gasification reactive nitrogenous compounds are formed from fuel nitrogen, which may form nitrogen oxides in gas combustion. In fluidized bed gasification the most important nitrogenous compound is ammonia (NH{sub 3}). If ammonia could be decomposed to N{sub 2} already before combustion, the emissions if nitrogen oxides could be reduced significantly. One way of increasing the decomposition rate of NH{sub 3} could be the addition of suitable reactants to the gas, which would react with NH{sub 3} and produce N{sub 2}. The aim of this research is to create basic information, which can be used to develop a new method for removal of nitrogen compounds from gasification gas. The reactions of nitrogen compounds and added reactants are studied in reductive atmosphere in order to find conditions, in which nitrogen compounds can be oxidized selectively to N{sub 2}. The project consists of following subtasks: (1) Selective non-catalytic oxidation (SNCO): Reactions of nitrogen compounds and oxidizers in the gas phase, (2) Selective catalytic oxidation (SCO): Reactions of nitrogen compounds and oxidizers on catalytically active surfaces, (3) Kinetic modelling of experimental results in co-operation with the Combustion Chemistry Research Group of Aabo Akademi University. The most important finding has been that NH{sub 3} can be made to react selectively with the oxidizers even in the presence of large amounts of CO and H{sub 2}. Aluminium oxides were found to be the most effective materials promoting selectivity. (author)

Contributions to the theory of catalytic titrations-III Neutralization catalytic titrations.

Science.gov (United States)

Gaál, F F; Abramović, B F

1985-07-01

Neutralization catalytic titrations of weak monoprotic adds and bases with both volumetric and coulometric addition of the titrant (strong base/acid) have been simulated by taking into account the equilibrium concentration of the catalyst during the titration. The influence of several factors on the shape of the simulated catalytic titration curve has been investigated and is discussed.

Investigation of hybrid plasma-catalytic removal of acetone over CuO/γ-Al2O3 catalysts using response surface method.

Science.gov (United States)

Zhu, Xinbo; Tu, Xin; Mei, Danhua; Zheng, Chenghang; Zhou, Jinsong; Gao, Xiang; Luo, Zhongyang; Ni, Mingjiang; Cen, Kefa

2016-07-01

In this work, plasma-catalytic removal of low concentrations of acetone over CuO/γ-Al2O3 catalysts was carried out in a cylindrical dielectric barrier discharge (DBD) reactor. The combination of plasma and the CuO/γ-Al2O3 catalysts significantly enhanced the removal efficiency of acetone compared to the plasma process using the pure γ-Al2O3 support, with the 5.0 wt% CuO/γ-Al2O3 catalyst exhibiting the best acetone removal efficiency of 67.9%. Catalyst characterization was carried out to understand the effect the catalyst properties had on the activity of the CuO/γ-Al2O3 catalysts in the plasma-catalytic reaction. The results indicated that the formation of surface oxygen species on the surface of the catalysts was crucial for the oxidation of acetone in the plasma-catalytic reaction. The effects that various operating parameters (discharge power, flow rate and initial concentration of acetone) and the interactions between these parameters had on the performance of the plasma-catalytic removal of acetone over the 5.0 wt% CuO/γ-Al2O3 catalyst were investigated using central composite design (CCD). The significance of the independent variables and their interactions were evaluated by means of the Analysis of Variance (ANOVA). The results showed that the gas flow rate was the most significant factor affecting the removal efficiency of acetone, whilst the initial concentration of acetone played the most important role in determining the energy efficiency of the plasma-catalytic process. Copyright © 2016 Elsevier Ltd. All rights reserved.

Effects of metal ions on the catalytic degradation of dicofol by cellulase.

Science.gov (United States)

Zhai, Zihan; Yang, Ting; Zhang, Boya; Zhang, Jianbo

2015-07-01

A new technique whereby cellulase immobilized on aminated silica was applied to catalyze the degradation of dicofol, an organochlorine pesticide. In order to evaluate the performance of free and immobilized cellulase, experiments were carried out to measure the degradation efficiency. The Michaelis constant, Km, of the reaction catalyzed by immobilized cellulase was 9.16 mg/L, and the maximum reaction rate, Vmax, was 0.40 mg/L/min, while that of free cellulase was Km=8.18 mg/L, and Vmax=0.79 mg/L/min, respectively. The kinetic constants of catalytic degradation were calculated to estimate substrate affinity. Considering that metal ions may affect enzyme activity, the effects of different metal ions on the catalytic degradation efficiency were explored. The results showed that the substrate affinity decreased after immobilization. Monovalent metal ions had no effect on the reaction, while divalent metal ions had either positive or inhibitory effects, including activation by Mn2+, reversible competition with Cd2+, and irreversible inhibition by Pb2+. Ca2+ promoted the catalytic degradation of dicofol at low concentrations, but inhibited it at high concentrations. Compared with free cellulase, immobilized cellulase was affected less by metal ions. This work provided a basis for further studies on the co-occurrence of endocrine-disrupting chemicals and heavy metal ions in the environment. Copyright © 2015. Published by Elsevier B.V.

VUV photo-oxidation of gaseous benzene combined with ozone-assisted catalytic oxidation: Effect on transition metal catalyst

Science.gov (United States)

Huang, Haibao; Lu, Haoxian; Zhan, Yujie; Liu, Gaoyuan; Feng, Qiuyu; Huang, Huiling; Wu, Muyan; Ye, Xinguo

2017-01-01

Volatile organic compounds (VOCs) cause the major air pollution concern. In this study, a series of ZSM-5 supported transition metals were prepared by impregnation method. They were combined with vacuum UV (VUV) photo-oxidation in a continuous-flow packed-bed reactor and used for the degradation of benzene, a typical toxic VOCs. Compared with VUV photo-oxidation alone, the introduction of catalysts can greatly enhance benzene oxidation under the help of O3, the by-products from VUV irradiation, via ozone-assisted catalytic oxidation (OZCO). The catalytic activity of transition metals towards benzene oxidation followed the order: Mn > Co > Cu > Ni > Fe. Mn achieved the best catalytic activity due to the strongest capability for O3 catalytic decomposition and utilization. Benzene and O3 removal efficiency reached as high as 97% and 100% after 360 min, respectively. O3 was catalytically decomposed, generating highly reactive oxidants such as rad OH and rad O for benzene oxidation.

Distinct structural and catalytic roles for Zap70 in formation of the immunological synapse in CTL

Science.gov (United States)

Jenkins, Misty R; Stinchcombe, Jane C; Au-Yeung, Byron B; Asano, Yukako; Ritter, Alex T; Weiss, Arthur; Griffiths, Gillian M

2014-01-01

T cell receptor (TCR) activation leads to a dramatic reorganisation of both membranes and receptors as the immunological synapse forms. Using a genetic model to rapidly inhibit Zap70 catalytic activity we examined synapse formation between cytotoxic T lymphocytes and their targets. In the absence of Zap70 catalytic activity Vav-1 activation occurs and synapse formation is arrested at a stage with actin and integrin rich interdigitations forming the interface between the two cells. The membranes at the synapse are unable to flatten to provide extended contact, and Lck does not cluster to form the central supramolecular activation cluster (cSMAC). Centrosome polarisation is initiated but aborts before reaching the synapse and the granules do not polarise. Our findings reveal distinct roles for Zap70 as a structural protein regulating integrin-mediated control of actin vs its catalytic activity that regulates TCR-mediated control of actin and membrane remodelling during formation of the immunological synapse. DOI: http://dx.doi.org/10.7554/eLife.01310.001 PMID:24596147

The catalytic function of cytochrome P450 is entwined with its membrane-bound nature [version 1; referees: 4 approved

Directory of Open Access Journals (Sweden)

Carlo Barnaba

2017-05-01

Full Text Available Cytochrome P450, a family of monooxygenase enzymes, is organized as a catalytic metabolon, which requires enzymatic partners as well as environmental factors that tune its complex dynamic. P450 and its reducing counterparts—cytochrome P450-reductase and cytochrome b5—are membrane-bound proteins located in the cytosolic side of the endoplasmic reticulum. They are believed to dynamically associate to form functional complexes. Increasing experimental evidence signifies the role(s played by both protein-protein and protein-lipid interactions in P450 catalytic function and efficiency. However, the biophysical challenges posed by their membrane-bound nature have severely limited high-resolution understanding of the molecular interfaces of these interactions. In this article, we provide an overview of the current knowledge on cytochrome P450, highlighting the environmental factors that are entwined with its metabolic function. Recent advances in structural biophysics are also discussed, setting up the bases for a new paradigm in the study of this important class of membrane-bound enzymes.

Exciplex-Forming Cohost for High Efficiency and High Stability Phosphorescent Organic Light-Emitting Diodes.

Science.gov (United States)

Shih, Chun-Jen; Lee, Chih-Chien; Chen, Ying-Hao; Biring, Sajal; Kumar, Gautham; Yeh, Tzu-Hung; Sen, Somaditya; Liu, Shun-Wei; Wong, Ken-Tsung

2018-01-17

An exciplex forming cohost system is employed to achieve a highly efficient organic light-emitting diode (OLED) with good electroluminescent lifetime. The exciplex is formed at the interfacial contact of a conventional star-shaped carbazole hole-transporting material, 4,4',4″-tris(N-carbazolyl)-triphenylamine (TCTA), and a triazine electron-transporting material, 2,4,6-tris[3-(1H-pyrazol-1-yl)phenyl]-1,3,5-triazine (3P-T2T). The excellent combination of TCTA and 3P-T2T is applied as the cohost of a common green phosphorescent emitter with almost zero energy loss. When Ir(ppy) 2 (acac) is dispersed in such exciplex cohost system, OLED device with maximum external quantum efficiency of 29.6%, the ultrahigh power efficiency of 147.3 lm/W, and current efficiency of 107 cd/A were successfully achieved. More importantly, the OLED device showed a low-efficiency roll-off and an operational lifetime (τ 80 ) of ∼1020 min with the initial brightness of 2000 cd/m 2 , which is 56 times longer than the reference device. The significant difference of device stability was attributed to the degradation of exciplex system for energy transfer process, which was investigated by the photoluminescence aging measurement at room temperature and 100 K, respectively.

Coupling catalytic hydrolysis and oxidation on Mn/TiO2-Al2O3 for HCN removal

Science.gov (United States)

Wang, Langlang; Wang, Xueqian; Cheng, Jinhuan; Ning, Ping; Lin, Yilong

2018-05-01

The manganese-modified titania-alumina (Mn/TiO2-Al2O3) catalyst synthesized by sol-gol method was used to remove hydrogen cyanide (HCN) from simulated flue gas. Further, effects of the mass ratios of Ti/Al, Mn loading, calcination temperature, and relative humidity on HCN conversion efficiency and catalytic activity were systematically investigated. The results indicated that the Mn/TiO2-Al2O3 catalyst exhibited significantly enhanced HCN removal efficiency, and the maximum yield of N2 increased to 68.02% without the participation of water vapor. When water vapor was added into the flue gas, the yield of N2 decreased and the formation of NOx was also inhibited. The XRD and XPS results indicated that Mn was mainly present in the form of Mn2+, Mn3+, and Mn4+ on the surface of catalyst and chemisorbed oxygen played a major role in the HCN catalytic oxidation process. The results of DSC-TGA analysis and H2-TPR indicated that the catalyst also exhibited a good thermal and chemical stability. NH3-TPD and CO2-TPD indicated that the surface of the catalyst mainly contained acidic sites. During the reaction, part of NH3 was adsorbed by Brönsted and Lewis acid sites. NH3 adsorbed on Lewis acid sites participated in NH3-SCR, which reduced the amount of NOx produced and resulted in a high N2 yield.

Computational and Physical Analysis of Catalytic Compounds

Science.gov (United States)

Wu, Richard; Sohn, Jung Jae; Kyung, Richard

2015-03-01

Nanoparticles exhibit unique physical and chemical properties depending on their geometrical properties. For this reason, synthesis of nanoparticles with controlled shape and size is important to use their unique properties. Catalyst supports are usually made of high-surface-area porous oxides or carbon nanomaterials. These support materials stabilize metal catalysts against sintering at high reaction temperatures. Many studies have demonstrated large enhancements of catalytic behavior due to the role of the oxide-metal interface. In this paper, the catalyzing ability of supported nano metal oxides, such as silicon oxide and titanium oxide compounds as catalysts have been analyzed using computational chemistry method. Computational programs such as Gamess and Chemcraft has been used in an effort to compute the efficiencies of catalytic compounds, and bonding energy changes during the optimization convergence. The result illustrates how the metal oxides stabilize and the steps that it takes. The graph of the energy computation step(N) versus energy(kcal/mol) curve shows that the energy of the titania converges faster at the 7th iteration calculation, whereas the silica converges at the 9th iteration calculation.

Endotoxin Removal from Water Using Heterogenus Catalytic Ozonation by Bone Char

Directory of Open Access Journals (Sweden)

Abas Rezaee

2011-10-01

Full Text Available The endotoxin is one of pollutants with lipopolysaccharide structure which release from gram negative bacteria and cyanobacters. The aim of this study was removal of endotoxin from water using catalytic ozonation by bone char. The endotoxin for experiments have extracted from Escherichia coli bacterium cell wall by Stefan and Jan method. Chromogenic limulus ambusite lysate method in 405-410 nm wave length was used for analysing of endotoxin. The ozone have analysed by potassium iodine method. Results: Results of the research shown endotoxin removal rates using heterogenous catalytic ozonation were 6.0 Eu/ml.min and 0.5 Eu/ml.min for grey bone char and white bone char, respectively. The efficency of the process was found eighty percent. Primary concentration of basic compounds had no effect on endotoxin removal rate. Therefore, endotoxin removal kinetic of reaction is a zero order reaction. This study revealed that ozonation process using bone char is more efficient than other proposed methods such as ozonation or chlorination and can be used successfully for endotoxin removal from water as a efficient method.

Catalytic reactor for low-Btu fuels

Science.gov (United States)

Smith, Lance; Etemad, Shahrokh; Karim, Hasan; Pfefferle, William C.

2009-04-21

An improved catalytic reactor includes a housing having a plate positioned therein defining a first zone and a second zone, and a plurality of conduits fabricated from a heat conducting material and adapted for conducting a fluid therethrough. The conduits are positioned within the housing such that the conduit exterior surfaces and the housing interior surface within the second zone define a first flow path while the conduit interior surfaces define a second flow path through the second zone and not in fluid communication with the first flow path. The conduit exits define a second flow path exit, the conduit exits and the first flow path exit being proximately located and interspersed. The conduits define at least one expanded section that contacts adjacent conduits thereby spacing the conduits within the second zone and forming first flow path exit flow orifices having an aggregate exit area greater than a defined percent of the housing exit plane area. Lastly, at least a portion of the first flow path defines a catalytically active surface.

Catalytic distillation structure

Science.gov (United States)

Smith, L.A. Jr.

1984-04-17

Catalytic distillation structure is described for use in reaction distillation columns, and provides reaction sites and distillation structure consisting of a catalyst component and a resilient component intimately associated therewith. The resilient component has at least about 70 volume % open space and is present with the catalyst component in an amount such that the catalytic distillation structure consists of at least 10 volume % open space. 10 figs.

Removal of ethylene from air stream by adsorption and plasma-catalytic oxidation using silver-based bimetallic catalysts supported on zeolite.

Science.gov (United States)

Trinh, Quang Hung; Lee, Sang Baek; Mok, Young Sun

2015-03-21

Dynamic adsorption of ethylene on 13X zeolite-supported Ag and Ag-M(x)O(y) (M: Co, Cu, Mn, and Fe), and plasma-catalytic oxidation of the adsorbed ethylene were investigated. The experimental results showed that the incorporation of Ag into zeolite afforded a marked enhancement in the adsorptivity for ethylene. The addition of transition metal oxides was found to have a positive influence on the ethylene adsorption, except Fe(x)O(y). The presence of the additional metal oxides, however, appeared to somewhat interrupt the diffusion of ozone into the zeolite micro-pores, leading to a decrease in the plasma-catalytic oxidation efficiency of the ethylene adsorbed there. Among the second additional metal oxides, Fe(x)O(y) was able to reduce the emission of ozone during the plasma-catalytic oxidation stage while keeping a high effectiveness for the oxidative removal of the adsorbed ethylene. The periodical treatment consisting of adsorption followed by plasma-catalytic oxidation may be a promising energy-efficient ethylene abatement method. Copyright © 2014 Elsevier B.V. All rights reserved.

The catalytic cycle of nitrous oxide reductase - The enzyme that catalyzes the last step of denitrification.

Science.gov (United States)

Carreira, Cíntia; Pauleta, Sofia R; Moura, Isabel

2017-12-01

The reduction of the potent greenhouse gas nitrous oxide requires a catalyst to overcome the large activation energy barrier of this reaction. Its biological decomposition to the inert dinitrogen can be accomplished by denitrifiers through nitrous oxide reductase, the enzyme that catalyzes the last step of the denitrification, a pathway of the biogeochemical nitrogen cycle. Nitrous oxide reductase is a multicopper enzyme containing a mixed valence CuA center that can accept electrons from small electron shuttle proteins, triggering electron flow to the catalytic sulfide-bridged tetranuclear copper "CuZ center". This enzyme has been isolated with its catalytic center in two forms, CuZ*(4Cu1S) and CuZ(4Cu2S), proven to be spectroscopic and structurally different. In the last decades, it has been a challenge to characterize the properties of this complex enzyme, due to the different oxidation states observed for each of its centers and the heterogeneity of its preparations. The substrate binding site in those two "CuZ center" forms and which is the active form of the enzyme is still a matter of debate. However, in the last years the application of different spectroscopies, together with theoretical calculations have been useful in answering these questions and in identifying intermediate species of the catalytic cycle. An overview of the spectroscopic, kinetics and structural properties of the two forms of the catalytic "CuZ center" is given here, together with the current knowledge on nitrous oxide reduction mechanism by nitrous oxide reductase and its intermediate species. Copyright © 2017 Elsevier Inc. All rights reserved.

Fuel cell research: Towards efficient energy

CSIR Research Space (South Africa)

Rohwer, MB

2008-11-01

Full Text Available fuel cells by optimising the loading of catalyst (being expensive noble metals) and ionomer; 2) Improving conventional acidic direct alcohol fuel cells by developing more efficient catalysts and by investigating other fuels than methanol; 3... these components add significantly to the overall cost of a PEMFC. 1 We focused our research activities on: 1) The effect of the loading of catalytic ink on cell performance; 2) The effect of the ionomer content in the catalytic ink; 3) Testing...

Exploration of alternate catalytic mechanisms and optimization strategies for retroaldolase design.

Science.gov (United States)

Bjelic, Sinisa; Kipnis, Yakov; Wang, Ling; Pianowski, Zbigniew; Vorobiev, Sergey; Su, Min; Seetharaman, Jayaraman; Xiao, Rong; Kornhaber, Gregory; Hunt, John F; Tong, Liang; Hilvert, Donald; Baker, David

2014-01-09

Designed retroaldolases have utilized a nucleophilic lysine to promote carbon-carbon bond cleavage of β-hydroxy-ketones via a covalent Schiff base intermediate. Previous computational designs have incorporated a water molecule to facilitate formation and breakdown of the carbinolamine intermediate to give the Schiff base and to function as a general acid/base. Here we investigate an alternative active-site design in which the catalytic water molecule was replaced by the side chain of a glutamic acid. Five out of seven designs expressed solubly and exhibited catalytic efficiencies similar to previously designed retroaldolases for the conversion of 4-hydroxy-4-(6-methoxy-2-naphthyl)-2-butanone to 6-methoxy-2-naphthaldehyde and acetone. After one round of site-directed saturation mutagenesis, improved variants of the two best designs, RA114 and RA117, exhibited among the highest kcat (>10(-3)s(-1)) and kcat/KM (11-25M(-1)s(-1)) values observed for retroaldolase designs prior to comprehensive directed evolution. In both cases, the >10(5)-fold rate accelerations that were achieved are within 1-3 orders of magnitude of the rate enhancements reported for the best catalysts for related reactions, including catalytic antibodies (kcat/kuncat=10(6) to 10(8)) and an extensively evolved computational design (kcat/kuncat>10(7)). The catalytic sites, revealed by X-ray structures of optimized versions of the two active designs, are in close agreement with the design models except for the catalytic lysine in RA114. We further improved the variants by computational remodeling of the loops and yeast display selection for reactivity of the catalytic lysine with a diketone probe, obtaining an additional order of magnitude enhancement in activity with both approaches. © 2013.

Catalytic site identification—a web server to identify catalytic site structural matches throughout PDB

Science.gov (United States)

Kirshner, Daniel A.; Nilmeier, Jerome P.; Lightstone, Felice C.

2013-01-01

The catalytic site identification web server provides the innovative capability to find structural matches to a user-specified catalytic site among all Protein Data Bank proteins rapidly (in less than a minute). The server also can examine a user-specified protein structure or model to identify structural matches to a library of catalytic sites. Finally, the server provides a database of pre-calculated matches between all Protein Data Bank proteins and the library of catalytic sites. The database has been used to derive a set of hypothesized novel enzymatic function annotations. In all cases, matches and putative binding sites (protein structure and surfaces) can be visualized interactively online. The website can be accessed at http://catsid.llnl.gov. PMID:23680785

Weak Form Efficiency of the Nigerian Stock Market: An Empirical Analysis (1984 – 2009

Directory of Open Access Journals (Sweden)

Pyemo Afego

2012-01-01

Full Text Available This paper examines the weak-form of the efficient markets hypothesis for the Nigerian Stock Exchange (NSE by testing for random walks in the monthly index returns over the period 1984-2009. The results of the non-parametric runs test show that index returns on the NSE display a predictable component, thus suggesting that traders can earn superior returns by employing trading rules. Statistically significant deviations from randomness are also suggestive of sub-optimal allocation of investment capital within the economy. The findings, in general, contradict the weak-form of the efficient markets hypothesis, and a range of policy strategies for improving the allocative capacity and quality of the information environment of the NSE are discussed.

Plasma-assisted catalytic ionization using porous nickel plate

International Nuclear Information System (INIS)

Oohara, W.; Maeda, T.; Higuchi, T.

2011-01-01

Hydrogen atomic pair ions, i.e., H + and H - ions, are produced by plasma-assisted catalytic ionization using a porous nickel plate. Positive ions in a hydrogen plasma generated by dc arc discharge are irradiated to the porous plate, and pair ions are produced from the back of the irradiation plane. It becomes clear that the production quantity of pair ions mainly depends on the irradiation current of positive ions and the irradiation energy affects the production efficiency of H - ions.

Endogenous Catalytic Generation of O2 Bubbles for In Situ Ultrasound-Guided High Intensity Focused Ultrasound Ablation.

Science.gov (United States)

Liu, Tianzhi; Zhang, Nan; Wang, Zhigang; Wu, Meiying; Chen, Yu; Ma, Ming; Chen, Hangrong; Shi, Jianlin

2017-09-26

High intensity focused ultrasound (HIFU) surgery generally suffers from poor precision and low efficiency in clinical application, especially for cancer therapy. Herein, a multiscale hybrid catalytic nanoreactor (catalase@MONs, abbreviated as C@M) has been developed as a tumor-sensitive contrast and synergistic agent (C&SA) for ultrasound-guided HIFU cancer surgery, by integrating dendritic-structured mesoporous organosilica nanoparticles (MONs) and catalase immobilized in the large open pore channels of MONs. Such a hybrid nanoreactor exhibited sensitive catalytic activity toward H 2 O 2 , facilitating the continuous O 2 gas generation in a relatively mild manner even if incubated with 10 μM H 2 O 2 , which finally led to enhanced ablation in the tissue-mimicking PAA gel model after HIFU exposure mainly resulting from intensified cavitation effect. The C@M nanoparticles could be accumulated within the H 2 O 2 -enriched tumor region through enhanced permeability and retention effect, enabling durable contrast enhancement of ultrasound imaging, and highly efficient tumor ablation under relatively low power of HIFU exposure in vivo. Very different from the traditional perfluorocarbon-based C&SA, such an on-demand catalytic nanoreactor could realize the accurate positioning of tumor without HIFU prestimulation and efficient HIFU ablation with a much safer power output, which is highly desired in clinical HIFU application.

Synthesis and visible-light-induced catalytic activity of Ag{sub 2}S-coupled TiO{sub 2} nanoparticles and nanowires

Energy Technology Data Exchange (ETDEWEB)

Xie Yi; Heo, Sung Hwan; Kim, Yong Nam; Yoo, Seung Hwa; Cho, Sung Oh, E-mail: socho@kaist.ac.kr [Department of Nuclear and Quantum Engineering, Korea Advanced Institute of Science and Technology (KAIST), 373-1 Guseong, Yuseong, Daejeon 305-701 (Korea, Republic of)

2010-01-08

We present the synthesis and visible-light-induced catalytic activity of Ag{sub 2}S-coupled TiO{sub 2} nanoparticles (NPs) and TiO{sub 2} nanowires (NWs). Through a simple wet chemical process from a mixture of peroxo titanic acid (PTA) solution, thiourea and AgAc, a composite of Ag{sub 2}S NPs and TiO{sub 2} NPs with sizes of less than 7 nm was formed. When the NP composite was further treated with NaOH solution followed by annealing at ambient conditions, a new nanocomposite material comprising Ag{sub 2}S NPs on TiO{sub 2} NWs was created. Due to the coupling with such a low bandgap material as Ag{sub 2}S, the TiO{sub 2} nanocomposites could have a visible-light absorption capability much higher than that of pure TiO{sub 2}. As a result, the synthesized Ag{sub 2}S/TiO{sub 2} nanocomposites exhibited much higher catalytic efficiency for the decomposition of methyl orange than commercial TiO{sub 2} (Degussa P25, Germany) under visible light.

Polymer and Membrane Design for Low Temperature Catalytic Reactions

KAUST Repository

Villalobos, Luis Francisco; Xie, Yihui; Nunes, Suzana Pereira; Peinemann, Klaus-Viktor

2016-01-01

Catalytically active asymmetric membranes have been developed with high loadings of palladium nanoparticles located solely in the membrane's ultrathin skin layer. The manufacturing of these membranes requires polymers with functional groups, which can form insoluble complexes with palladium ions. Three polymers have been synthesized for this purpose and a complexation/nonsolvent induced phase separation followed by a palladium reduction step is carried out to prepare such membranes. Parameters to optimize the skin layer thickness and porosity, the palladium loading in this layer, and the palladium nanoparticles size are determined. The catalytic activity of the membranes is verified with the reduction of a nitro-compound and with a liquid phase Suzuki-Miyaura coupling reaction. Very low reaction times are observed. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Polymer and Membrane Design for Low Temperature Catalytic Reactions

KAUST Repository

Villalobos, Luis Francisco

2016-02-29

Catalytically active asymmetric membranes have been developed with high loadings of palladium nanoparticles located solely in the membrane\\'s ultrathin skin layer. The manufacturing of these membranes requires polymers with functional groups, which can form insoluble complexes with palladium ions. Three polymers have been synthesized for this purpose and a complexation/nonsolvent induced phase separation followed by a palladium reduction step is carried out to prepare such membranes. Parameters to optimize the skin layer thickness and porosity, the palladium loading in this layer, and the palladium nanoparticles size are determined. The catalytic activity of the membranes is verified with the reduction of a nitro-compound and with a liquid phase Suzuki-Miyaura coupling reaction. Very low reaction times are observed. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Novel dextran derivatives with unconventional structure formed in an efficient one-pot reaction.

Science.gov (United States)

Hotzel, Konrad; Heinze, Thomas

2016-11-03

An efficient one-pot synthesis of new dextran derivatives is described. The functional groups of β-alanine, i.e., the carboxyl- and amine group, are converted independently in one-step by iminium chloride to form products with a single substituent. The dextran N-[(dimethylamino)methylene]-β-alanine ester is formed selectively. The structure of the resulting polymers is unambiguously determined by means of NMR- and FTIR-spectroscopy and elemental analysis. Copyright © 2016 Elsevier Ltd. All rights reserved.

Preparation, Characterization and Catalytic Activity of Nickel Molybdate (NiMoO4 Nanoparticles

Directory of Open Access Journals (Sweden)

Hicham Oudghiri-Hassani

2018-01-01

Full Text Available Nickel molybdate (NiMoO4 nanoparticles were synthesized via calcination of an oxalate complex in static air at 500 °C. The oxalate complex was analyzed by thermal gravimetric analysis (TGA and Fourier transform infrared spectroscopy (FTIR. The as-synthesized nickel molybdate was characterized by Brunauer–Emmett–Teller technique (BET, X-ray diffraction (XRD, and transmission electron microscopy (TEM and its catalytic efficiency was tested in the reduction reaction of the three-nitrophenol isomers. The nickel molybdate displays a very high activity in the catalytic reduction of the nitro functional group to an amino. The reduction progress was controlled using Ultraviolet-Visible (UV-Vis absorption.

Catalytic Ozonation by Iron Coated Pumice for the Degradation of Natural Organic Matters

Directory of Open Access Journals (Sweden)

Alper Alver

2018-05-01

Full Text Available The use of iron-coated pumice (ICP in heterogeneous catalytic ozonation significantly enhanced the removal efficiency of natural organic matters (NOMs in water, due to the synergistic effect of hybrid processes when compared to sole ozonation and adsorption. Multiple characterization analyses (BET, TEM, XRD, DLS, FT-IR, and pHPZC were employed for a systematic investigation of the catalyst surface properties. This analysis indicated that the ICP crystal structure was α-FeOOH, the surface hydroxyl group of ICP was significantly increased after coating, the particle size of ICP was about 200–250 nm, the BET surface area of ICP was about 10.56 m2 g−1, the pHPZC value of ICP was about 7.13, and that enhancement by iron loading was observed in the FT-IR spectra. The contribution of surface adsorption, hydroxyl radicals, and sole ozonation to catalytic ozonation was determined as 21.29%, 66.22%, and 12.49%, respectively. The reaction kinetic analysis with tert-Butyl alcohol (TBA was used as a radical scavenger, confirming that surface ferrous iron loading promoted the role of the hydroxyl radicals. The phosphate was used as an inorganic probe, and significantly inhibited the removal efficiency of catalytic NOM ozonation. This is an indication that the reactions which occur are more dominant in the solution phase.

Carbohydrates as efficient catalysts for the hydration of α-amino nitriles.

Science.gov (United States)

Chitale, Sampada; Derasp, Joshua S; Hussain, Bashir; Tanveer, Kashif; Beauchemin, André M

2016-11-01

Directed hydration of α-amino nitriles was achieved under mild conditions using simple carbohydrates as catalysts exploiting temporary intramolecularity. A broadly applicable procedure using both formaldehyde and NaOH as catalysts efficiently hydrated a variety of primary and secondary susbtrates, and allowed the hydration of enantiopure substrates to proceed without racemization. This work also provides a rare comparison of the catalytic activity of carbohydrates, and shows that the simple aldehydes at the basis of chemical evolution are efficient organocatalysts mimicking the function of hydratase enzymes. Optimal catalytic efficiency was observed with destabilized aldehydes, and with difficult substrates only simple carbohydrates such as formaldehyde and glycolaldehyde proved reliable.

Effects of electric current upon catalytic steam reforming of biomass gasification tar model compounds to syngas

International Nuclear Information System (INIS)

Tao, Jun; Lu, Qiang; Dong, Changqing; Du, Xiaoze; Dahlquist, Erik

2015-01-01

Highlights: • ECR technique was proposed to convert biomass gasification tar model compounds. • Electric current enhanced the reforming efficiency remarkably. • The highest toluene conversion reached 99.9%. • Ni–CeO 2 /γ-Al 2 O 3 exhibited good stability during the ECR performance. - Abstract: Electrochemical catalytic reforming (ECR) technique, known as electric current enhanced catalytic reforming technique, was proposed to convert the biomass gasification tar into syngas. In this study, Ni–CeO 2 /γ-Al 2 O 3 catalyst was prepared, and toluene was employed as the major feedstock for ECR experiments using a fixed-bed lab-scale setup where thermal electrons could be generated and provided to the catalyst. Several factors, including the electric current intensity, reaction temperature and steam/carbon (S/C) ratio, were investigated to reveal their effects on the conversion of toluene as well as the composition of the gas products. Moreover, toluene, two other tar model compounds (benzene and 1-methylnaphthalene) and real tar (tar-containing wastewater) were subjected to the long period catalytic stability tests. All the used catalysts were analyzed to determine their carbon contents. The results indicated that the presence of electric current enhanced the catalytic performance remarkably. The toluene conversion reached 99.9% under the electric current of 4 A, catalytic temperature of 800 °C and S/C ratio of 3. Stable conversion performances of benzene, 1-methylnaphthalene and tar-containing wastewater were also observed in the ECR process. H 2 and CO were the major gas products, while CO 2 and CH 4 were the minor ones. Due to the promising capability, the ECR technique deserves further investigation and application for efficient tar conversion

Effect of support on the catalytic activity of manganese oxide catalyts for toluene combustion

International Nuclear Information System (INIS)

Pozan, Gulin Selda

2012-01-01

Highlights: ► α-Al 2 O 3 , obtained from Bohmite, as a support for enhancing of the activity. ► The support material for catalytic oxidation. ► The manganese state and oxygen species effect on the catalytic combustion reaction. - Abstract: The aim of this work was to study combustion of toluene (1000 ppm) over MnO 2 modified with different supports. α-Al 2 O 3 and γ-Al 2 O 3 obtained from Boehmite, γ-Al 2 O 3 (commercial), SiO 2 , TiO 2 and ZrO 2 were used as commercial support materials. In view of potential interest of this process, the influence of support material on the catalytic performance was discussed. The deposition of 9.5MnO 2 was performed by impregnation over support. The catalysts were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), temperature programmed reduction and oxidation (TPR/TPO) and thermogravimetric analysis (TGA). The catalytic tests were carried out at atmospheric pressure in a fixed-bed flow reactor. 9.5MnO 2 /α-Al 2 O 3 (B) (synthesized from Boehmite) catalyst exhibits the highest catalytic activity, over which the toluene conversion was up to 90% at a temperature of 289 °C. Considering all the characterization and reaction data reported in this study, it was concluded that the manganese state and oxygen species played an important role in the catalytic activity.

Diesel Engine Emission Reduction Using Catalytic Nanoparticles: An Experimental Investigation

Directory of Open Access Journals (Sweden)

Ajin C. Sajeevan

2013-01-01

Full Text Available Cerium oxide being a rare earth metal with dual valance state existence has exceptional catalytic activity due to its oxygen buffering capability, especially in the nanosized form. Hence when used as an additive in the diesel fuel it leads to simultaneous reduction and oxidation of nitrogen dioxide and hydrocarbon emissions, respectively, from diesel engine. The present work investigates the effect of cerium oxide nanoparticles on performance and emissions of diesel engine. Cerium oxide nanoparticles were synthesized by chemical method and techniques such as TEM, EDS, and XRD have been used for the characterization. Cerium oxide was mixed in diesel by means of standard ultrasonic shaker to obtain stable suspension, in a two-step process. The influence of nanoparticles on various physicochemical properties of diesel fuel has also been investigated through extensive experimentation by means of ASTM standard testing methods. Load test was done in the diesel engine to investigate the effect of nanoparticles on the efficiency and the emissions from the engine. Comparisons of fuel properties with and without additives are also presented.

Silver nanowires as catalytic cathodes for stabilizing lithium-oxygen batteries

Science.gov (United States)

Kwak, Won-Jin; Jung, Hun-Gi; Lee, Seon-Hwa; Park, Jin-Bum; Aurbach, Doron; Sun, Yang-Kook

2016-04-01

Silver nanowires have been investigated as a catalytic cathode material for lithium-oxygen batteries. Their high aspect ratio contributes to the formation of a corn-shaped layer structure of the poorly crystalline lithium peroxide (Li2O2) nanoparticles produced by oxygen reduction in poly-ether based electrolyte solutions. The nanowire morphology seems to provide the necessary large contact area and facile electron supply for a very effective oxygen reduction reaction. The unique morphology and structure of the Li2O2 deposits and the catalytic nature of the silver nano-wires promote decomposition of Li2O2 at low potentials (below 3.4 V) upon the oxygen evolution. This situation avoids decomposition of the solution species and oxidation of the electrodes during the anodic (charge) reactions, leading to high electrical efficiently of lithium-oxygen batteries.

Biodiesel production through non-catalytic supercritical transesterification: current state and perspectives

OpenAIRE

Silva, C. da; Oliveira, J. Vladimir

2014-01-01

The inconveniences of the conventional method for biodiesel production by alkaline catalysis suggests research towards alternative methods, with the non-catalytic transesterification using an alcohol at supercritical conditions proposed as a promising technique for biodiesel production. The so-called supercritical method (SCM) has powerful advantages over conventional techniques, such as fast reaction rates, feedstock flexibility, production efficiency and environmentally friendly benefits. H...

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

Science.gov (United States)

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

2017-10-05

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

Substitutions in conserved regions preceding and within the linker affect activity and flexibility of tRNase ZL, the long form of tRNase Z.

Directory of Open Access Journals (Sweden)

Makenzie Saoura

Full Text Available The enzyme tRNase Z, a member of the metallo-β-lactamase family, endonucleolytically removes 3' trailers from precursor tRNAs, preparing them for CCA addition and aminoacylation. The short form of tRNase Z, tRNase ZS, functions as a homodimer and is found in all prokaryotes and some eukaryotes. The long form, tRNase ZL, related to tRNase ZS through tandem duplication and found only in eukaryotes, possesses ~2,000-fold greater catalytic efficiency than tRNase ZS. tRNase ZL consists of related but diverged amino and carboxy domains connected by a flexible linker (also referred to as a flexible tether and functions as a monomer. The amino domain retains the flexible arm responsible for substrate recognition and binding while the carboxy domain retains the active site. The linker region was explored by Ala-scanning through two conserved regions of D. melanogaster tRNase Z: NdomTprox, located at the carboxy end of the amino domain proximal to the linker, and Tflex, a flexible site in the linker. Periodic substitutions in a hydrophobic patch (F329 and L332 at the carboxy end of NdomTprox show 2,700 and 670-fold impairment relative to wild type, respectively, accompanied by reduced linker flexibility at N-T inside the Ndom- linker boundary. The Ala substitution for N378 in the Tflex region has 10-fold higher catalytic efficiency than wild type and locally decreased flexibility, while the Ala substitution at R382 reduces catalytic efficiency ~50-fold. These changes in pre-tRNA processing kinetics and protein flexibility are interpreted in light of a recent crystal structure for S. cerevisiae tRNase Z, suggesting transmission of local changes in hydrophobicity into the skeleton of the amino domain.

Kinetic study of the catalytic pyrolysis of elephant grass using Ti-MCM-41

Energy Technology Data Exchange (ETDEWEB)

Fontes, Maria do Socorro Braga; Melo, Dulce Maria de Araujo; Rodrigues, Glicelia, E-mail: socorro.fontes@yahoo.com.br [Universidade Federal do Rio Grande do Norte (UFRN), Natal, RN (Brazil); Barros, Joana Maria de Farias [Universidade Federal de Campina Grande (UFCG), Cuite, PB (Brazil). Dept. de Quimica; Braga, Renata Martins [Universidade Federal da Paraiba (UFPB/CEAR/DEER), Joao Pessoa, PB (Brazil). Centro de Energias Alternativas e Renovaveis. Dept. de Engenharia de Energia Renovaveis

2014-08-15

This work aimed to study the kinetics of thermal and catalytic pyrolysis using Ti-MCM-41 as catalyst in order to assess the catalytic pyrolysis efficiency compared to thermal pyrolysis of elephant grass. Ti-MCM-41 molecular sieve was synthesized by hydrothermal method from hydrogel with the following molar composition: 1.00 CTMABr: 4.00 SiO{sub 2}:X TiO{sub 2}: 1 + X Na{sub 2}O: 200.00 H{sub 2}O, which structure template used was cetyltrimethylammonium bromide (CTMABr). The materials synthesized were characterized by X-ray diffraction, IR spectroscopy, thermogravimetric analysis and specific area by the BET method, for subsequent application in the biomass pyrolysis process. The kinetic models proposed by Vyazovkin and Flynn-Wall were used to determine the apparent activation energy involved in the thermal and catalytic pyrolysis of elephant grass and the results showed that the catalyst used was effective in reducing the apparent activation energy involved in the thermal decomposition of elephant grass. (author)

Selective Catalytic Synthesis Using the Combination of Carbon Dioxide and Hydrogen: Catalytic Chess at the Interface of Energy and Chemistry.

Science.gov (United States)

Klankermayer, Jürgen; Wesselbaum, Sebastian; Beydoun, Kassem; Leitner, Walter

2016-06-20

The present Review highlights the challenges and opportunities when using the combination CO2 /H2 as a C1 synthon in catalytic reactions and processes. The transformations are classified according to the reduction level and the bond-forming processes, covering the value chain from high volume basic chemicals to complex molecules, including biologically active substances. Whereas some of these concepts can facilitate the transition of the energy system by harvesting renewable energy into chemical products, others provide options to reduce the environmental impact of chemical production already in today's petrochemical-based industry. Interdisciplinary fundamental research from chemists and chemical engineers can make important contributions to sustainable development at the interface of the energetic and chemical value chain. The present Review invites the reader to enjoy this exciting area of "catalytic chess" and maybe even to start playing some games in her or his laboratory. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Kinetics and Thermodynamics of DNA Processing by Wild Type DNA-Glycosylase Endo III and Its Catalytically Inactive Mutant Forms

Directory of Open Access Journals (Sweden)

Olga A. Kladova

2018-03-01

Full Text Available Endonuclease III (Endo III or Nth is one of the key enzymes responsible for initiating the base excision repair of oxidized or reduced pyrimidine bases in DNA. In this study, a thermodynamic analysis of structural rearrangements of the specific and nonspecific DNA-duplexes during their interaction with Endo III is performed based on stopped-flow kinetic data. 1,3-diaza-2-oxophenoxazine (tCO, a fluorescent analog of the natural nucleobase cytosine, is used to record multistep DNA binding and lesion recognition within a temperature range (5–37 °C. Standard Gibbs energy, enthalpy, and entropy of the specific steps are derived from kinetic data using Van’t Hoff plots. The data suggest that enthalpy-driven exothermic 5,6-dihydrouracil (DHU recognition and desolvation-accompanied entropy-driven adjustment of the enzyme–substrate complex into a catalytically active state play equally important parts in the overall process. The roles of catalytically significant amino acids Lys120 and Asp138 in the DNA lesion recognition and catalysis are identified. Lys120 participates not only in the catalytic steps but also in the processes of local duplex distortion, whereas substitution Asp138Ala leads to a complete loss of the ability of Endo III to distort a DNA double chain during enzyme–DNA complex formation.

Catalytic pyrolysis of recalcitrant, insoluble humin byproducts from C6 sugar biorefineries

NARCIS (Netherlands)

Agarwal, Shilpa; van Es, Daan; Heeres, Hero Jan

Humins are solid by-products formed during the acid-catalysed conversions of C-6 sugars to platform chemicals like hydroxymethylfurfural and levulinic acid. We here report an experimental study on the liquefaction/depolymerisation of humins using catalytic pyrolysis. Synthetic humins (SH) and crude

Selective catalytic reduction of NO{sub x} by olefins

Energy Technology Data Exchange (ETDEWEB)

Radtke, F

1997-12-31

The removal of nitrogen oxides from the exhaust of lean-burn gasoline fuelled and diesel-fuelled engines, operating under net oxidizing conditions, has recently attracted considerable attention. In this work, three different catalytic systems (Al{sub 2}O{sub 3}, Cu/Al{sub 2}O{sub 3} and Cu/ZSM-5) are investigated for their suitability as catalysts for the selective reduction of nitrogen oxides by hydrocarbons in excess oxygen. Special emphasis is given to the formation of potentially harmful byproducts such as hydrogen cyanide (HCN), cyanic acid (HNCO), ammonia (NH{sub 3}) and nitrous oxide (N{sub 2}O). The effect of reaction temperature, nitrogen oxide (NO, NO{sub 2}), hydrocarbon (ethene, propene) and water on activity and the formation of byproducts is investigated. In situ FTIR spectroscopy and temperature-programmed surface reactions (TPSR) of absorbed species in different atmospheres were used to investigate the nature and reactivity of adsorbates formed under reaction conditions. The catalytic activity was strongly influenced by the presence of water in the feed. The effects of the other parameters were suppressed and the performance generally decreased, except when propene was used for the reduction of NO{sub x} over Cu/ZSM-5. Over Cu/ZSM-5 clearly higher conversion was obtained, when ethene was used as reducing agent, while there was no significant difference when starting from NO or NO{sub 2}. In contrast, with {gamma}-Al{sub 2}O{sub 3} NO{sub 2} was reduced more efficiently than NO with both reductants. The impregnation of {gamma}-Al{sub 2}O{sub 3} with copper led to an extensive loss of this performance. For dry feeds and with increasing CuO loading, the catalysts reached maximum activity at lower temperature and the maximum yield of nitrogen slightly decreased. (author) figs., tabs., refs.

New self-assembled material based on Ru nanoparticles and 4-sulfocalix[4]arene as an efficient and recyclable catalyst for reduction of brilliant yellow azo dye in water: a new model catalytic reaction

Energy Technology Data Exchange (ETDEWEB)

Rambabu, Darsi; Pradeep, Chullikkattil P.; Dhir, Abhimanew, E-mail: abhimanew@iitmandi.ac.in [Indian Institute of Technology (India)

2016-12-15

New self-assembled material (Ru@SC) with ruthenium nanoparticles (Ru NPs) and 4-sulfocalix[4]arene (SC) is synthesized in water at room temperature. Ru@SC is characterized by thermal gravimetric analysis, FT-IR, powder x-ray diffraction, TEM and SEM analysis. The size of Ru nanoparticles in the self-assembly is approximately 5 nm. The self-assembled material Ru@SC shows an efficient catalytic reduction of toxic ‘brilliant yellow’ (BY) azo dye. The reduced amine products were successfully separated and confirmed by single-crystal XRD, NMR and UV-Vis spectroscopy. Ru@SC showed a better catalytic activity in comparison with commercial catalysts Ru/C (ruthenium on charcoal 5 %) and Pd/C (palladium on charcoal 5 and 10 %). The catalyst also showed a promising recyclability and heterogeneous nature as a catalyst for reduction of ‘BY’ azo dye.

Analysis of Catalytic Material Effect on the Photovoltaic Properties of Monolithic Dye-sensitized Solar Cells

Directory of Open Access Journals (Sweden)

Natalita Maulani Nursam

2017-12-01

Full Text Available Dye-sensitized solar cells (DSSC are widely developed due to their attractive appearance and simple fabrication processes. One of the challenges that arise in the DSSC fabrication involves high material cost associated with the cost of conductive substrate. DSSC with monolithic configuration was then developed on the basis of this motivation. In this contribution, titanium dioxide-based monolithic type DSSCs were fabricated on a single fluorine-doped transparent oxide coated glass using porous ZrO2 as spacer. Herein, the catalytic material for the counter-electrode was varied using carbon composite and platinum in order to analyze their effect on the solar cell efficiency. Four-point probe measurement revealed that the carbon composite exhibited slightly higher conductivity with a sheet resistance of 9.8 Ω/sq and 10.9 Ω/sq for carbon and platinum, respectively. Likewise, the photoconversion efficiency of the monolithic cells with carbon counter-electrode almost doubled the efficiency of the cells with platinum counter-electrode. Our results demonstrate that carbon could outperform the performance of platinum as catalytic material in monolithic DSSC.

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

Energy Technology Data Exchange (ETDEWEB)

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

2016-05-15

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

Comparative Study of Catalytic Oxidation of Ethanol to Acetaldehyde Using Fe(III Dispersed on Sb2O5 Grafted on SiO2 and on Untreated SiO2 Surfaces

Directory of Open Access Journals (Sweden)

Benvenutti Edilson V.

1998-01-01

Full Text Available Fe(III was supported on Sb(V oxide grafted on the silica gel surface and directly on the silica gel surface using ion-exchange and impregnation processes producing Fe/Sb/SiO2 and Fe/SiO2, respectively. The catalytic conversion of ethanol to acetaldehyde was much more efficient using Fe/Sb/SiO2 than Fe/SiO2 as catalyst. This higher efficiency of the former catalyst takes into account two aspects: a the new phase FeSbO4 formed when Fe/Sb/SiO2 is heat treated and, b it is higher dispersion on the matrix.

Evaluation of SI engine exhaust gas emissions upstream and downstream of the catalytic converter

International Nuclear Information System (INIS)

Silva, C.M.; Costa, M.; Farias, T.L.; Santos, H.

2006-01-01

The conversion efficiency of a catalytic converter, mounted on a vehicle equipped with a 2.8 l spark ignition engine, was evaluated under steady state operating conditions. The inlet and outlet chemical species concentration, temperature and air fuel ratio (A/F) were measured as a function of the brake mean effective pressure (BMEP) and engine speed (rpm). Oil temperature, coolant temperature, brake power and spark advance were also monitored. In parallel, a mathematical model for the catalytic converter has been developed. The main inputs of the model are the temperature, flow rate, chemical species mass flow and local A/F ratio as measured at the catalyst inlet section. The main conclusions are: (i) the exhaust gas and substrate wall temperatures at the catalyst outlet increase with BMEP and rpm; (ii) the HC conversion efficiency increases with the value of BMEP up to a maximum beyond which it decreases; (iii) the CO conversion efficiencies typically increase with BMEP; (iv) the NO x conversion efficiency remains nearly constant regardless of BMEP and rpm; (v) except for idle, the NO x conversion efficiency is typically the highest, followed in turn by the CO and HC conversion efficiencies; (vi) conversion efficiencies are lower for idle conditions, which can be a problem under traffic conditions where idle is a common situation; (vii) regardless of rpm and load, for the same flow rate the conversion efficiency is about the same; (viii) the model predictions slightly over estimate the exhaust gas temperature data at the catalyst outlet section with the observed differences decreasing with BMEP and engine speed; (ix) in general, the model predictions of the conversion efficiencies are satisfactory

Pretreated Landfill Gas Conversion Process via a Catalytic Membrane Reactor for Renewable Combined Fuel Cell-Power Generation

Directory of Open Access Journals (Sweden)

Zoe Ziaka

2013-01-01

Full Text Available A new landfill gas-based reforming catalytic processing system for the conversion of gaseous hydrocarbons, such as incoming methane to hydrogen and carbon oxide mixtures, is described and analyzed. The exit synthesis gas (syn-gas is fed to power effectively high-temperature fuel cells such as SOFC types for combined efficient electricity generation. The current research work is also referred on the description and design aspects of permreactors (permeable reformers carrying the same type of landfill gas-reforming reactions. Membrane reactors is a new technology that can be applied efficiently in such systems. Membrane reactors seem to perform better than the nonmembrane traditional reactors. The aim of this research includes turnkey system and process development for the landfill-based power generation and fuel cell industries. Also, a discussion of the efficient utilization of landfill and waste type resources for combined green-type/renewable power generation with increased processing capacity and efficiency via fuel cell systems is taking place. Moreover, pollution reduction is an additional design consideration in the current catalytic processors fuel cell cycles.

Fractional Multistage Hydrothermal Liquefaction of Biomass and Catalytic Conversion into Hydrocarbons

Energy Technology Data Exchange (ETDEWEB)

Cortright, Randy [Virent, Inc., Madison, WI (United States); Rozmiarek, Robert [Virent, Inc., Madison, WI (United States); Dally, Brice [Virent, Inc., Madison, WI (United States); Holland, Chris [Virent, Inc., Madison, WI (United States)

2017-08-31

The objective of this project was to develop an improved multistage process for the hydrothermal liquefaction (HTL) of biomass to serve as a new front-end, deconstruction process ideally suited to feed Virent’s well-proven catalytic technology, which is already being scaled up. This process produced water soluble, partially de-oxygenated intermediates that are ideally suited for catalytic finishing to fungible distillate hydrocarbons. Through this project, Virent, with its partners, demonstrated the conversion of pine wood chips to drop-in hydrocarbon distillate fuels using a multi-stage fractional conversion system that is integrated with Virent’s BioForming® process. The majority of work was in the liquefaction task and included temperature scoping, solvent optimization, and separations.

Biofunctionalized conductive polymers enable efficient CO2 electroreduction

Science.gov (United States)

Coskun, Halime; Aljabour, Abdalaziz; De Luna, Phil; Farka, Dominik; Greunz, Theresia; Stifter, David; Kus, Mahmut; Zheng, Xueli; Liu, Min; Hassel, Achim W.; Schöfberger, Wolfgang; Sargent, Edward H.; Sariciftci, Niyazi Serdar; Stadler, Philipp

2017-01-01

Selective electrocatalysts are urgently needed for carbon dioxide (CO2) reduction to replace fossil fuels with renewable fuels, thereby closing the carbon cycle. To date, noble metals have achieved the best performance in energy yield and faradaic efficiency and have recently reached impressive electrical-to-chemical power conversion efficiencies. However, the scarcity of precious metals makes the search for scalable, metal-free, CO2 reduction reaction (CO2RR) catalysts all the more important. We report an all-organic, that is, metal-free, electrocatalyst that achieves impressive performance comparable to that of best-in-class Ag electrocatalysts. We hypothesized that polydopamine—a conjugated polymer whose structure incorporates hydrogen-bonded motifs found in enzymes—could offer the combination of efficient electrical conduction, together with rendered active catalytic sites, and potentially thereby enable CO2RR. Only by developing a vapor-phase polymerization of polydopamine were we able to combine the needed excellent conductivity with thin film–based processing. We achieve catalytic performance with geometric current densities of 18 mA cm−2 at 0.21 V overpotential (−0.86 V versus normal hydrogen electrode) for the electrosynthesis of C1 species (carbon monoxide and formate) with continuous 16-hour operation at >80% faradaic efficiency. Our catalyst exhibits lower overpotentials than state-of-the-art formate-selective metal electrocatalysts (for example, 0.5 V for Ag at 18 mA cm−1). The results confirm the value of exploiting hydrogen-bonded sequences as effective catalytic centers for renewable and cost-efficient industrial CO2RR applications. PMID:28798958

Progress in controlling the size, composition and nanostructure of supported gold-palladium nanoparticles for catalytic applications

NARCIS (Netherlands)

Paalanen, P.P.|info:eu-repo/dai/nl/370602013; Weckhuysen, B.M.|info:eu-repo/dai/nl/285484397; Sankar, M.

2013-01-01

This review article gives an overview of the recent developments in the synthesis strategies of supported goldbased bimetallic nanoparticle catalysts. The catalytic efficiency of these supported bimetallic nanoparticles, similar to monometallic nanoparticles, depends on their structural

Cycloaddition of CO 2 to challenging N -tosyl aziridines using a halogen-free niobium complex: Catalytic activity and mechanistic insights

KAUST Repository

Arayachukiat, Sunatda

2017-11-06

An efficient and facile approach to the regioselective synthesis of N-tosyloxazolidinones from the corresponding N-tosylaziridines and CO2 was developed using dual catalytic systems involving an early transition metal coordination compound as a Lewis acid and a nucleophilic cocatalyst. Among the screened Lewis acids, halogen-free niobium pentaethoxide (Nb(OEt)5) displayed the best catalytic activity when used in the presence of tetrabutylammonium iodide (TBAI). Systematic DFT calculations, supported by catalytic experiments, demonstrate that CO2 insertion is the rate determining step for this process and it is highly dependent on the steric hindrance at the niobium center.

Cycloaddition of CO 2 to challenging N -tosyl aziridines using a halogen-free niobium complex: Catalytic activity and mechanistic insights

KAUST Repository

Arayachukiat, Sunatda; Yingcharoen, Prapussorn; Vummaleti, Sai V. C.; Cavallo, Luigi; Poater, Albert; D’ Elia, Valerio

2017-01-01

An efficient and facile approach to the regioselective synthesis of N-tosyloxazolidinones from the corresponding N-tosylaziridines and CO2 was developed using dual catalytic systems involving an early transition metal coordination compound as a Lewis acid and a nucleophilic cocatalyst. Among the screened Lewis acids, halogen-free niobium pentaethoxide (Nb(OEt)5) displayed the best catalytic activity when used in the presence of tetrabutylammonium iodide (TBAI). Systematic DFT calculations, supported by catalytic experiments, demonstrate that CO2 insertion is the rate determining step for this process and it is highly dependent on the steric hindrance at the niobium center.

Efficient Diethylzinc/Gallic Acid and Diethylzinc/Gallic Acid Ester Catalytic Systems for the Ring-Opening Polymerization of rac-Lactide

Directory of Open Access Journals (Sweden)

Karolina Żółtowska

2015-12-01

Full Text Available Polylactide (PLA represents one of the most promising biomedical polymers due to its biodegradability, bioresorbability and good biocompatibility. This work highlights the synthesis and characterization of PLAs using novel diethylzinc/gallic acid (ZnEt2/GAc and diethylzinc/propyl gallate (ZnEt2/PGAc catalytic systems that are safe for human body. The results of the ring-opening polymerization (ROP of rac-lactide (rac-LA in the presence of zinc-based catalytic systems have shown that, depending on the reaction conditions, “predominantly isotactic”, disyndiotactic or atactic PLA can be obtained. Therefore, the controlled and stereoselective ROP of rac-LA is discussed in detail in this paper.

Cationic Phospholipids Forming Cubic Phases: Lipoplex Structure and Transfection Efficiency

Energy Technology Data Exchange (ETDEWEB)

Koynova, Rumiana; Wang, Li; MacDonald, Robert C. (NWU)

2008-10-29

The transfection activity and the phase behavior of two novel cationic O-alkyl-phosphatidylcholines, 1,2-dioleoyl-sn-glycero-3-hexylphosphocholine (C6-DOPC) and 1,2-dierucoyl-sn-glycero-3-ethylphosphocholine (di22:1-EPC), have been examined with the aim of more completely understanding the mechanism of lipid-mediated DNA delivery. Both lipids form cubic phases: C6-DOPC in the entire temperature range from -10 to 90 C, while di22:1-EPC exhibits an irreversible lamellar-cubic transition between 50 and 70 C on heating. The lipoplexes formed by C6-DOPC arrange into hexagonal phase, while the lipoplexes of di22:1-EPC are lamellar. Both lipids exhibit lower transfection activity than the lamellar-forming 1,2-dioleoyl-sn-glycero-3-ethylphosphocholine (EDOPC). Thus, for the studied cationic phospholipid-DNA systems, the lipoplex phase state is a factor that does not seem to correlate with transfection activity. The parameter that exhibits better correlation with the transfection activity within the present data set is the phase state of the lipid dispersion prior to the addition of DNA. Thus, the lamellar lipid dispersion (EDOPC) produces more efficient lipoplexes than the dispersion with coexisting lamellar and cubic aggregates (diC22:1-EPC), which is even more efficient than the purely cubic dispersions (C6-DOPC; diC22:1-EPC after heating). It could be inferred from these data and from previous research that cubic phase lipid aggregates are unlikely to be beneficial to transfection. The lack of correlation between the phase state of lipoplexes and their transfection activity observed within the present data set does not mean that lipid phase state is generally unimportant for lipofection: a viewpoint now emerging from our previous studies is that the critical factor in lipid-mediated transfection is the structural evolution of lipoplexes within the cell, upon interacting and mixing with cellular lipids.

Cationic phospholipids forming cubic phases: lipoplex structure and transfection efficiency.

Science.gov (United States)

Koynova, Rumiana; Wang, Li; Macdonald, Robert C

2008-01-01

The transfection activity and the phase behavior of two novel cationic O-alkyl-phosphatidylcholines, 1,2-dioleoyl- sn-glycero-3-hexylphosphocholine (C6-DOPC) and 1,2-dierucoyl- sn-glycero-3-ethylphosphocholine (di22:1-EPC), have been examined with the aim of more completely understanding the mechanism of lipid-mediated DNA delivery. Both lipids form cubic phases: C6-DOPC in the entire temperature range from -10 to 90 degrees C, while di22:1-EPC exhibits an irreversible lamellar-cubic transition between 50 and 70 degrees C on heating. The lipoplexes formed by C6-DOPC arrange into hexagonal phase, while the lipoplexes of di22:1-EPC are lamellar. Both lipids exhibit lower transfection activity than the lamellar-forming 1,2-dioleoyl- sn-glycero-3-ethylphosphocholine (EDOPC). Thus, for the studied cationic phospholipid-DNA systems, the lipoplex phase state is a factor that does not seem to correlate with transfection activity. The parameter that exhibits better correlation with the transfection activity within the present data set is the phase state of the lipid dispersion prior to the addition of DNA. Thus, the lamellar lipid dispersion (EDOPC) produces more efficient lipoplexes than the dispersion with coexisting lamellar and cubic aggregates (diC22:1-EPC), which is even more efficient than the purely cubic dispersions (C6-DOPC; diC22:1-EPC after heating). It could be inferred from these data and from previous research that cubic phase lipid aggregates are unlikely to be beneficial to transfection. The lack of correlation between the phase state of lipoplexes and their transfection activity observed within the present data set does not mean that lipid phase state is generally unimportant for lipofection: a viewpoint now emerging from our previous studies is that the critical factor in lipid-mediated transfection is the structural evolution of lipoplexes within the cell, upon interacting and mixing with cellular lipids.

Energy Efficient Catalytic Activation of Hydrogen peroxide for Green Chemical Processes: Final Report

Energy Technology Data Exchange (ETDEWEB)

Collins, Terrence J.; Horwitz, Colin

2004-11-12

A new, highly energy efficient approach for using catalytic oxidation chemistry in multiple fields of technology has been pursued. The new catalysts, called TAML® activators, catalyze the reactions of hydrogen peroxide and other oxidants for the exceptionally rapid decontamination of noninfectious simulants (B. atrophaeus) of anthrax spores, for the energy efficient decontamination of thiophosphate pesticides, for the facile, low temperature removal of color and organochlorines from pulp and paper mill effluent, for the bleaching of dyes from textile mill effluents, and for the removal of recalcitrant dibenzothiophene compounds from diesel and gasoline fuels. Highlights include the following: 1) A 7-log kill of Bacillus atrophaeus spores has been achieved unambiguously in water under ambient conditions within 15 minutes. 2) The rapid total degradation under ambient conditions of four thiophosphate pesticides and phosphonate degradation intermediates has been achieved on treatment with TAML/peroxide, opening up potential applications of the decontamination system for phosphonate structured chemical warfare agents, for inexpensive, easy to perform degradation of stored and aged pesticide stocks (especially in Africa and Asia), for remediation of polluted sites and water bodies, and for the destruction of chemical warfare agent stockpiles. 3) A mill trial conducted in a Pennsylvanian bleached kraft pulp mill has established that TAML catalyst injected into an alkaline peroxide bleach tower can significantly lower color from the effluent stream promising a new, more cost effective, energy-saving approach for color remediation adding further evidence of the value and diverse engineering capacity of the approach to other field trials conducted on effluent streams as they exit the bleach plant. 4) Dibenzothiophenes (DBTs), including 4,6-dimethyldibenzothiophene, the most recalcitrant sulfur compounds in diesel and gasoline, can be completely removed from model gasoline

Catalytic briquettes from low-rank coal for NO reduction

Energy Technology Data Exchange (ETDEWEB)

A. Boyano; M.E. Galvez; R. Moliner; M.J. Lazaro [Instituto de Carboquimica, CSIC, Zaragoza (Spain)

2007-07-01

The briquetting is one of the most ancient and widespread techniques of coal agglomeration which is nowadays becoming useless for combustion home applications. However, the social increasing interest in environmental protection opens new applications to this technique, especially in developed countries. In this work, a series of catalytic briquettes were prepared from low-rank Spanish coal and commercial pitch by means of a pressure agglomeration method. After that, they were cured in air and doped by equilibrium impregnation with vanadium compounds. Preparation conditions (especially those of activation and oxidizing process) were changed to study their effects on catalytic behaviour. Catalytic briquettes showed a relative high NO conversion at low temperatures in all cases, however, a strong relation between the preparation process and the reached NO conversion was observed. Preparation procedure has an effect not only on the NO reduction efficiency but also on the mechanical strength of the briquettes as a consequence of the structural and chemical changes carried out during the activation and oxidation procedures. Generally speaking mechanical resistance is enhanced by an optimal porous volume and the creation of new carboxyl groups on surface. Just on the contrary, NO reduction is promoted by high microporous structures and higher amounts of surface oxygen groups. Both facts force to find an optimum point in the preparation produce which will depend on the application. 24 refs., 4 figs., 3 tabs.

Preparation of Pd-Diimine@SBA-15 and Its Catalytic Performance for the Suzuki Coupling Reaction

Directory of Open Access Journals (Sweden)

Jiahuan Yu

2016-11-01

Full Text Available A highly efficient and stable Pd-diimine@SBA-15 catalyst was successfully prepared by immobilizing Pd onto diimine-functionalized mesoporous silica SBA-15. With the help of diimine functional groups grafted onto the SBA-15, Pd could be anchored on a support with high dispersion. Pd-diimine@SBA-15 catalyst exhibited excellent catalytic performance for the Suzuki coupling reaction of electronically diverse aryl halides and phenylboronic acid under mild conditions with an ultralow amount of Pd (0.05 mol % Pd. When the catalyst amount was increased, it could catalyze the coupling reaction of chlorinated aromatics with phenylboronic acid. Compared with the catalytic performances of Pd/SBA-15 and Pd-diimine@SiO2 catalysts, the Pd-diimine@SBA-15 catalyst exhibited higher hydrothermal stability and could be repeatedly used four times without a significant decrease of its catalytic activity.

Catalytic Enantioselective Alkylation of β-Keto Esters with Xanthydrol in the Presence of Chiral Palladium Complex

Energy Technology Data Exchange (ETDEWEB)

Kim, Kyu Yeon; Kim, Dae Young [Soonchunhyang Univ., Asan (Korea, Republic of)

2016-01-15

Our research interest has been directed toward the development of synthetic methods for the enantioselective construction of stereogenic carbon centers. Recently, we explored the catalytic enantioselective functionalization of active methines in the presence of chiral palladium(II) complexes. In conclusion, we have accomplished the efficient catalytic enantioselective alkylation of β-keto esters 1 with xanthydrol 2 with high yields and excellent enantioselectivity (up to 98% ee). It should be noted that this alkyaltion reaction proceeds well using air- and moisture-stable chiral palladium com- plexes with low loading (1 mol%)

Fabrication of Sesame Sticks-like Silver Nanoparticles/Polystyrene Hybridnanotubes and Their Catalytic Effects.

Science.gov (United States)

Peng, Fang; Wang, Qi; Shi, Rongjia; Wang, Zeyi; You, Xin; Liu, Yuhong; Wang, Fenghe; Gao, Jay; Mao, Chun

2016-12-21

A novel and efficient catalyst is one of the goals in the material field, and the involvement of nanoscience and technology has brought new vigor to the development of catalyst. This research aimed to develop a simple two-step route to fabricate Fe 3 O 4 @PS/PDA-Ag hybridnanotubes with size-controllable and highly dispersed silver nanoparticles (NPs). First, Fe 3 O 4 @PS nanotubes of a sound mechanical property were prepared using polystyrene (PS)/toluene solution containing highly dispersed oleic acid modified Fe 3 O 4 particles in a commercial AAO template. Next, the facile technique was used to form in situ silver NPs on the surface of magnetic PS (Fe 3 O 4 @PS) nanotubes through dopamine coating. The catalytic effects of the prepared Fe 3 O 4 @PS/PDA-Ag hybridnanotubes with highly dispersed AgNPs were characterized using a range of analytical methods, including transmission electron microscopy, thermogravimetric analysis, UV-Visible spectroscopy, and X-ray diffraction. It was found that such prepared Fe 3 O 4 @PS/PDA-Ag hybridnanotubes had a large specific surface area. They possessed excellent activities in catalyzing the reduction of 4-nitrophenol (4-NP) by NaBH 4 in the aqueous phase. Furthermore, they were readily separated from fluid and retrieved by an external magnet. Their catalyst activity and recyclability demonstrated that this approach we proposed had the potential to become a new idea and route for catalytic platform.

Large-Scale Analysis Exploring Evolution of Catalytic Machineries and Mechanisms in Enzyme Superfamilies.

Science.gov (United States)

Furnham, Nicholas; Dawson, Natalie L; Rahman, Syed A; Thornton, Janet M; Orengo, Christine A

2016-01-29

Enzymes, as biological catalysts, form the basis of all forms of life. How these proteins have evolved their functions remains a fundamental question in biology. Over 100 years of detailed biochemistry studies, combined with the large volumes of sequence and protein structural data now available, means that we are able to perform large-scale analyses to address this question. Using a range of computational tools and resources, we have compiled information on all experimentally annotated changes in enzyme function within 379 structurally defined protein domain superfamilies, linking the changes observed in functions during evolution to changes in reaction chemistry. Many superfamilies show changes in function at some level, although one function often dominates one superfamily. We use quantitative measures of changes in reaction chemistry to reveal the various types of chemical changes occurring during evolution and to exemplify these by detailed examples. Additionally, we use structural information of the enzymes active site to examine how different superfamilies have changed their catalytic machinery during evolution. Some superfamilies have changed the reactions they perform without changing catalytic machinery. In others, large changes of enzyme function, in terms of both overall chemistry and substrate specificity, have been brought about by significant changes in catalytic machinery. Interestingly, in some superfamilies, relatives perform similar functions but with different catalytic machineries. This analysis highlights characteristics of functional evolution across a wide range of superfamilies, providing insights that will be useful in predicting the function of uncharacterised sequences and the design of new synthetic enzymes. Copyright © 2015 The Authors. Published by Elsevier Ltd.. All rights reserved.

Spatial decoupling of light absorption and catalytic activity of Ni-Mo-loaded high-aspect-ratio silicon microwire photocathodes

Science.gov (United States)

Vijselaar, Wouter; Westerik, Pieter; Veerbeek, Janneke; Tiggelaar, Roald M.; Berenschot, Erwin; Tas, Niels R.; Gardeniers, Han; Huskens, Jurriaan

2018-03-01

A solar-driven photoelectrochemical cell provides a promising approach to enable the large-scale conversion and storage of solar energy, but requires the use of Earth-abundant materials. Earth-abundant catalysts for the hydrogen evolution reaction, for example nickel-molybdenum (Ni-Mo), are generally opaque and require high mass loading to obtain high catalytic activity, which in turn leads to parasitic light absorption for the underlying photoabsorber (for example silicon), thus limiting production of hydrogen. Here, we show the fabrication of a highly efficient photocathode by spatially and functionally decoupling light absorption and catalytic activity. Varying the fraction of catalyst coverage over the microwires, and the pitch between the microwires, makes it possible to deconvolute the contributions of catalytic activity and light absorption to the overall device performance. This approach provided a silicon microwire photocathode that exhibited a near-ideal short-circuit photocurrent density of 35.5 mA cm-2, a photovoltage of 495 mV and a fill factor of 62% under AM 1.5G illumination, resulting in an ideal regenerative cell efficiency of 10.8%.

Lamellar zirconium phosphates to host metals for catalytic purposes.

Science.gov (United States)

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

2018-02-27

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

Radiolytic Synthesis of Pt-Ru Catalysts Based on Functional Polymer-Grafted MWNT and Their Catalytic Efficiency for CO and MeOH

Directory of Open Access Journals (Sweden)

Dae-Soo Yang

2011-01-01

Full Text Available Pt-Ru catalysts based on functional polymer-grafted MWNT (Pt-Ru@FP-MWNT were prepared by radiolytic deposition of Pt-Ru nanoparticles on functional polymer-grafted multiwalled carbon nanotube (FP-MWNT. Three different types of functional polymers, poly(acrylic acid (PAAc, poly(methacrylic acid (PMAc, and poly(vinylphenyl boronic acid (PVPBAc, were grafted on the MWNT surface by radiation-induced graft polymerization (RIGP. Then, Pt-Ru nanoparticles were deposited onto the FP-MWNT supports by the reduction of metal ions using γ-irradiation to obtain Pt-Ru@FP-MWNT catalysts. The Pt-Ru@FP-MWNT catalysts were then characterized by XRD, XPS, TEM ,and elemental analysis. The catalytic efficiency of Pt-Ru@FP-MWNT catalyst was examined for CO stripping and MeOH oxidation for use in a direct methanol fuel cell (DMFC. The Pt-Ru@PVPBAc-MWNT catalyst shows enhanced activity for electro-oxidation of CO and MeOH oxidation over that of the commercial E-TEK catalyst.

Catalytic Upgrading of Thermochemical Intermediates to Hydrocarbons: Conversion of Lignocellulosic Feedstocks to Aromatic Fuels and High Value Chemicals

Energy Technology Data Exchange (ETDEWEB)

Cortright, Randy [Virent, Inc., Madison, WI (United States); Rozmiarek, Bob [Virent, Inc., Madison, WI (United States); Van Straten, Matt [Virent, Inc., Madison, WI (United States)

2017-11-28

The principal objective of this project was to develop a fully integrated catalytic process that efficiently converts lignocellulosic feedstocks (e.g. bagasse, corn stover, and loblolly pine) into aromatic-rich fuels and chemicals. Virent led this effort with key feedstock support from Iowa State University. Within this project, Virent leveraged knowledge of catalytic processing of sugars and biomass to investigate two liquefaction technologies (Reductive Catalytic Liquefaction (USA Patent No. 9,212,320, 2015) and Solvolysis (USA Patent No. 9,157,030, 2015) (USA Patent No. 9,157,031, 2015)) that take advantage of proprietary catalysts at temperatures less than 300°C in the presence of unique solvent molecules generated in-situ within the liquefaction processes.

Catalytic oxidative pyrolysis of spent organic ion exchange resins from nuclear power plants

International Nuclear Information System (INIS)

Sathi Sasidharan, N.; Deshingkar, D.S.; Wattal, P.K.; Shirsat, A.N.; Bharadwaj, S.R.

2005-08-01

The spent IX resins from nuclear power reactors are highly active solid wastes generated during operations of nuclear reactors. Catalytic oxidative pyrolysis of these resins can lead to high volume reduction of these wastes. Low temperature pyrolysis of transition metal ion loaded IX resins in presence of nitrogen was carried out in order to optimize catalyst composition to achieve maximum weight reduction. Thermo gravimetric analysis of the pyrolysis residues was carried out in presence of air in order to compare the oxidative characteristics of transition metal oxide catalysts. Copper along with iron, chromium and nickel present in the spent IX resins gave the most efficient catalyst combination for catalytic and oxidative pyrolysis of the residues. During low temperature catalytic pyrolysis, 137 Cesium volatility was estimated to be around 0.01% from cationic resins and around 0.1% from anionic resins. During oxidative pyrolysis at 700 degC, nearly 10 to 40% of 137 Cesium was found to be released to off gases depending upon type of resin and catalyst loaded on to it. The oxidation of pyrolytic residues at 700 degC gave weight reduction of 15% for cationic resins and 93% for anionic resins. Catalytic oxidative pyrolysis is attractive for reducing weight and volume of spent cationic resins from PHWRs and VVERs. (author)

Regulation of catalytic behaviour of hydrolases through interactions with functionalized carbon-based nanomaterials

International Nuclear Information System (INIS)

Pavlidis, Ioannis V.; Vorhaben, Torge; Gournis, Dimitrios; Papadopoulos, George K.; Bornscheuer, Uwe T.; Stamatis, Haralambos

2012-01-01

The interaction of enzymes with carbon-based nanomaterials (CBNs) is crucial for the function of biomolecules and therefore for the design and development of effective nanobiocatalytic systems. In this study, the effect of functionalized CBNs, such as graphene oxide (GO) and multi-wall carbon nanotubes (CNTs), on the catalytic behaviour of various hydrolases of biotechnological interest was monitored and the interactions between CBNs and proteins were investigated. The enzyme–nanomaterial interactions significantly affect the catalytic behaviour of enzymes, resulting in an increase up to 60 % of the catalytic efficiency of lipases and a decrease up to 30 % of the esterase. Moreover, the use of CNTs and GO derivatives, especially those that are amine-functionalized, led to increased thermal stability of most the hydrolases tested. Fluorescence and circular dichroism studies indicated that the altered catalytic behaviour of enzymes in the presence of CBNs arises from specific enzyme–nanomaterial interactions, which can lead to significant conformational changes. In the case of lipases, the conformational changes led to a more active and rigid structure, while in the case of esterases this led to destabilization and unfolding. Kinetic and spectroscopic studies indicated that the extent of the interactions between CBNs and hydrolases can be mainly controlled by the functionalization of nanomaterials than by their geometry.

Regulation of catalytic behaviour of hydrolases through interactions with functionalized carbon-based nanomaterials

Energy Technology Data Exchange (ETDEWEB)

Pavlidis, Ioannis V. [University of Ioannina, Laboratory of Biotechnology, Department of Biological Applications and Technologies (Greece); Vorhaben, Torge [Institute of Biochemistry, Greifswald University, Department of Biotechnology and Enzyme Catalysis (Germany); Gournis, Dimitrios [University of Ioannina, Department of Materials Science and Engineering (Greece); Papadopoulos, George K. [Epirus Institute of Technology, Laboratory of Biochemistry and Biophysics, Faculty of Agricultural Technology (Greece); Bornscheuer, Uwe T. [Institute of Biochemistry, Greifswald University, Department of Biotechnology and Enzyme Catalysis (Germany); Stamatis, Haralambos, E-mail: hstamati@cc.uoi.gr [University of Ioannina, Laboratory of Biotechnology, Department of Biological Applications and Technologies (Greece)

2012-05-15

The interaction of enzymes with carbon-based nanomaterials (CBNs) is crucial for the function of biomolecules and therefore for the design and development of effective nanobiocatalytic systems. In this study, the effect of functionalized CBNs, such as graphene oxide (GO) and multi-wall carbon nanotubes (CNTs), on the catalytic behaviour of various hydrolases of biotechnological interest was monitored and the interactions between CBNs and proteins were investigated. The enzyme-nanomaterial interactions significantly affect the catalytic behaviour of enzymes, resulting in an increase up to 60 % of the catalytic efficiency of lipases and a decrease up to 30 % of the esterase. Moreover, the use of CNTs and GO derivatives, especially those that are amine-functionalized, led to increased thermal stability of most the hydrolases tested. Fluorescence and circular dichroism studies indicated that the altered catalytic behaviour of enzymes in the presence of CBNs arises from specific enzyme-nanomaterial interactions, which can lead to significant conformational changes. In the case of lipases, the conformational changes led to a more active and rigid structure, while in the case of esterases this led to destabilization and unfolding. Kinetic and spectroscopic studies indicated that the extent of the interactions between CBNs and hydrolases can be mainly controlled by the functionalization of nanomaterials than by their geometry.

Catalytic ozonation of ammonia using biomass char and wood fly ash.

Science.gov (United States)

Kastner, James R; Miller, Joby; Kolar, Praveen; Das, K C

2009-05-01

Catalytic ozonation of gaseous ammonia was investigated at room temperature using wood fly ash (WFA) and biomass char as catalysts. WFA gave the best results, removing ammonia (11 ppmv NH(3), 45% conversion) at 23 degrees C at a residence time of 0.34 s, using 5 g of catalyst or ash at the lowest ozone concentration (62 ppmv). Assuming pseudo zero order kinetics in ozone, a power rate law of -r(NH3) = 7.2 x 10(-8) C(NH3)(0.25) (r, mol g(-1)s(-1), C(NH3)molL(-1)) was determined at 510 ppmv O(3) and 23 degrees C for WFA. Water vapor approximately doubled the oxidation rate using WFA and catalytic ozonation activity was not measured for the char without humidifying the air stream. Overall oxidation rates using the crude catalysts were lower than commercial catalysts, but the catalytic ozonation process operated at significantly lower temperatures (23 vs. 300 degrees C). Nitric oxide was not detected and the percentage of NO(2) formed from NH(3) oxidation ranged from 0.3% to 3% (v/v), with WFA resulting in the lowest NO(2) level (at low O(3) levels). However, we could not verify that N(2)O was not formed, so further research is needed to determine if N(2) is the primary end-product. Additional research is required to develop techniques to enhance the oxidation activity and industrial application of the crude, but potentially inexpensive catalysts.

Detection of Intracellular Reduced (Catalytically Active) SHP-1 and Analyses of Catalytically Inactive SHP-1 after Oxidation by Pervanadate or H2O2.

Science.gov (United States)

Choi, Seeyoung; Love, Paul E

2018-01-05

Oxidative inactivation of cysteine-dependent Protein Tyrosine Phosphatases (PTPs) by cellular reactive oxygen species (ROS) plays a critical role in regulating signal transduction in multiple cell types. The phosphatase activity of most PTPs depends upon a 'signature' cysteine residue within the catalytic domain that is maintained in the de-protonated state at physiological pH rendering it susceptible to ROS-mediated oxidation. Direct and indirect techniques for detection of PTP oxidation have been developed (Karisch and Neel, 2013). To detect catalytically active PTPs, cell lysates are treated with iodoacetyl-polyethylene glycol-biotin (IAP-biotin), which irreversibly binds to reduced (S - ) cysteine thiols. Irreversible oxidation of SHP-1 after treatment of cells with pervanadate or H 2 O 2 is detected with antibodies specific for the sulfonic acid (SO 3 H) form of the conserved active site cysteine of PTPs. In this protocol, we describe a method for the detection of the reduced (S - ; active) or irreversibly oxidized (SO 3 H; inactive) form of the hematopoietic PTP SHP-1 in thymocytes, although this method is applicable to any cysteine-dependent PTP in any cell type.

Combined photolysis and catalytic ozonation of dimethyl phthalate in a high-gravity rotating packed bed

Energy Technology Data Exchange (ETDEWEB)

Chang, C.-C. [Graduate Institute of Environmental Engineering, National Taiwan University, Taipei 106, Taiwan (China); Chiu, C.-Y. [Department of Cosmetic Science and Application, Lan-Yang Institute of Technology, I-Lan 261, Taiwan (China); Chang, C.-Y. [Graduate Institute of Environmental Engineering, National Taiwan University, Taipei 106, Taiwan (China)], E-mail: cychang3@ntu.edu.tw; Chang, C.-F. [Department of Environmental Science and Engineering, Tunghai University, Taichung 407, Taiwan (China); Chen, Y.-H. [Department of Chemical and Material Engineering, National Kaohsiung University of Applied Science, Kaohsiung City 807, Taiwan (China); Ji, D.-R.; Yu, Y.-H.; Chiang, P.-C. [Graduate Institute of Environmental Engineering, National Taiwan University, Taipei 106, Taiwan (China)

2009-01-15

In this study, a high-gravity rotating packed bed (HGRPB) was used as a catalytic ozonation reactor to decompose dimethyl phthalate (DMP), an endocrine disrupting chemical commonly encountered. The HGRPB is an effective gas-liquid mixing equipment which can enhance the ozone mass transfer coefficient. Platinum-containing catalyst (Pt/-Al{sub 2}O{sub 3}) of Dash 220N and ultra violet (UV) lamp were combined in the high-gravity ozonation (HG-OZ) system to enhance the self-decomposition of molecular ozone in liquid to form highly reactive radical species. Different combinations of HG-OZ with Dash 220N and UV for the degradation of DMP were tested. These include HG-OZ, HG catalytic OZ (HG-Pt-OZ), HG photolysis OZ (HG-UV-OZ) and HG-UV-Pt-OZ. The result indicated that all the above four ozonation processes result in significant decomposition of DMP and mineralization of total organic carbon (TOC) at the applied ozone dosage per volume of liquid sample of 1.2 g L{sup -1}. The UV and Pt/{gamma}-Al{sub 2}O{sub 3} combined in HG-OZ can enhance the TOC mineralization efficiency ({eta}{sub TOC}) to 56% (via HG-UV-OZ) and 57% (via HG-Pt-OZ), respectively, while only 45% with ozone only. The process of HG-UV-Pt-OZ offers the highest {eta}{sub TOC} of about 68%.

Photo catalytic degradation of nitrobenzene using nanocrystalline TiO2 photo catalyst doped with Zn ions

International Nuclear Information System (INIS)

Reynoso S, E. A.; Perez S, S.; Reyes C, A. P.; Castro R, C. L.; Felix N, R. M.; Lin H, S. W.; Paraguay D, F.; Alonso N, G.

2013-01-01

Photo catalysis is a method widely used in the degradation of organic pollutants of the environment. The development of new materials is very important to improve the photo catalytic properties and to find new applications for TiO 2 as a photo catalyst. In this article we reported the synthesis of a photo catalyst based on TiO 2 doped with Zn 2+ ions highly efficient in the degradation of nitrobenzene. The results of photo catalytic activity experiments showed that the Zn 2+ doped TiO 2 is more active that un-doped TiO 2 catalyst with an efficiency of 99% for the nitrobenzene degradation at 120 min with an apparent rate constant of 35 x 10 -3 min -1 . For the characterization of photo catalyst X-ray diffraction, transmission electron microscopy and Raman spectroscopy were used. (Author)

Biorecovery of gold as nanoparticles and its catalytic activities for p-nitrophenol degradation.

Science.gov (United States)

Zhu, Nengwu; Cao, Yanlan; Shi, Chaohong; Wu, Pingxiao; Ma, Haiqin

2016-04-01

Recovery of gold from aqueous solution using simple and economical methodologies is highly desirable. In this work, recovery of gold as gold nanoparticles (AuNPs) by Shewanella haliotis with sodium lactate as electron donor was explored. The results showed that the process was affected by the concentration of biomass, sodium lactate, and initial gold ions as well as pH value. Specifically, the presence of sodium lactate determines the formation of nanoparticles, biomass, and AuCl4 (-) concentration mainly affected the size and dispersity of the products, reaction pH greatly affected the recovery efficiency, and morphology of the products in the recovery process. Under appropriate conditions (5.25 g/L biomass, 40 mM sodium lactate, 0.5 mM AuCl4 (-), and pH of 5), the recovery efficiency was almost 99 %, and the recovered AuNPs were mainly spherical with size range of 10-30 nm (~85 %). Meanwhile, Fourier transforms infrared spectroscopy and X-ray photoelectron spectroscopy demonstrated that carboxyl and amine groups might play an important role in the process. In addition, the catalytic activity of the AuNPs recovered under various conditions was testified by analyzing the reduction rate of p-nitrophenol by borohydride. The biorecovered AuNPs exhibited interesting size and shape-dependent catalytic activity, of which the spherical particle with smaller size showed the highest catalytic reduction activity with rate constant of 0.665 min(-1).

Investigating the effect of gas flow rate, inlet ozone concentration and relative humidity on the efficacy of catalytic ozonation process in the removal of xylene from waste airstream

Directory of Open Access Journals (Sweden)

H.R. MokaramI

2010-10-01

Full Text Available Background and aimsThe catalytic ozonation is an efficient process for the degradation of volatile organic compounds from contaminated air stream. This study was aimed at investigating the efficacy of catalytic ozonation process in removal of xylene from the polluted air stream andthe influence of retention time (gas flow rate, inlet ozone dose and relative humidity on this performanceMethodsthe catalytic ozonation of xylene was conducted using a bench scale set-up consisted of a syringe pump,an air pump, an ozone generator, and a glass reactor packed with activated carbon. Several experimental run was defined to investigate the influence of the selectedoperational variables.ResultsThe results indicated that the efficiency of catalytic ozonation was greater than that of single adsorption in removal of xylene under similar inlet concentration and relative humidity. We found a significant catalytic effect for activated carbon when used in combination with ozonation process, leading to improvement of xylene removal percentage. In addition, the elimination capacity of the system improved with the increase of inlet ozone dose as well as gas flow rate. The relative humidity showed a positive effect of the xylene removal at the range of 5 to 50%, while the higher humidity (more than 50% resulted in reduction of the performance.ConclusionThe findings of the present work revealed that the catalytic ozonation process can be an efficient technique for treating the air streams containing industrial concentrations of xylene. Furthermore, there is a practical potential to retrofit the present adsorption systems intothe catalytic ozonation simply by coupling them with the ozonation system. the catalytic ozonation of xylene was conducted using a bench scale set-up consisted of a syringe pump,an air pump, an ozone generator, and a glass reactor packed with activated carbon. Several experimental run was defined to investigate the influence of the selected

Kinetic and catalytic performance of a BI-porous composite material in catalytic cracking and isomerisation reactions

KAUST Repository

Al-Khattaf, S.

2012-01-10

Catalytic behaviour of pure zeolite ZSM-5 and a bi-porous composite material (BCM) were investigated in transformation of m-xylene, while zeolite HY and the bi-porous composite were used in the cracking of 1,3,5-triisopropylbenzene (TIPB). The micro/mesoporous material was used to understand the effect of the presence of mesopores on these reactions. Various characterisation techniques, that is, XRD, SEM, TGA, FT-IR and nitrogen sorption measurements were applied for complete characterisation of the catalysts. Catalytic tests using CREC riser simulator showed that the micro/mesoporous composite catalyst exhibited higher catalytic activity as compared with the conventional microporous ZSM-5 and HY zeolite for transformation of m-xylene and for the catalytic cracking of TIPB, respectively. The outstanding catalytic reactivity of m-xylene and TIPB molecules were mainly attributed to the easier access of active sites provided by the mesopores. Apparent activation energies for the disappearance of m-xylene and TIPB over all catalysts were found to decrease in the order: EBCM>EZSM-5 and EBCM>EHY, respectively. © 2012 Canadian Society for Chemical Engineering.

The effect of Ce ion substituted OMS-2 nanostructure in catalytic activity for benzene oxidation

Science.gov (United States)

Hou, Jingtao; Li, Yuanzhi; Mao, Mingyang; Zhao, Xiujian; Yue, Yuanzheng

2014-11-01

The nanostructure of Ce doped OMS-2 plays a very important role in its catalytic property. We demonstrate by density functional theory (DFT) calculations that the unique nanostructure of the Ce ion substituted OMS-2 with Mn vacancy in the framework is beneficial for the improvement of catalytic activity, while the nanostructure of the Ce ion substituted OMS-2 without defects are detrimental to the catalytic activity. We establish a novel and facile strategy of synthesizing these unique Ce ion substituted OMS-2 nanostructure with Mn vacancies in the framework by hydrothermal redox reaction between Ce(NO3)3 and KMnO4 with KMnO4/Ce(NO3)3 at a molar ratio of 3 : 1 at 120 °C. Compared to pure OMS-2, the produced catalyst of Ce ion substituted OMS-2 ultrathin nanorods exhibits an enormous enhancement in the catalytic activity for benzene oxidation, which is evidenced by a significant decrease (ΔT50 = 100 °C, ΔT90 = 129 °C) in the reaction temperature of T50 and T90 (corresponding to the benzene conversion = 50% and 90%), which is considerably more efficient than the expensive supported noble metal catalyst (Pt/Al2O3). We combine both theoretical and experimental evidence to provide a new physical insight into the significant effect due to the defects induced by the Ce ion substitution on the catalytic activity of OMS-2. The formation of unique Ce ion substituted OMS-2 nanostructure with Mn vacancies in the framework leads to a significant enhancement of the lattice oxygen activity, thus tremendously increasing the catalytic activity.The nanostructure of Ce doped OMS-2 plays a very important role in its catalytic property. We demonstrate by density functional theory (DFT) calculations that the unique nanostructure of the Ce ion substituted OMS-2 with Mn vacancy in the framework is beneficial for the improvement of catalytic activity, while the nanostructure of the Ce ion substituted OMS-2 without defects are detrimental to the catalytic activity. We establish a novel

Engineered Humicola insolens cutinase for efficient cellulose acetate deacetylation.

Science.gov (United States)

Shirke, Abhijit N; Butterfoss, Glenn L; Saikia, Rakhi; Basu, Aditya; de Maria, Leonardo; Svendsen, Allan; Gross, Richard A

2017-08-01

Cutinases comprise a family of esterases with broad hydrolytic activity for chain and pendant ester groups. This work aimed to identify and improve an efficient cutinase for cellulose acetate (CA) deacetylation. The development of a mild method for CA fiber surface deacetylation will result in improved surface hydrophilicity and reactivity while, when combined with cellulases, a route to the full recycling of CA to acetate and glucose. In this study, the comparative CA deacetylation activity of four homologous wild-type (wt) fungal cutinases from Aspergillus oryzae (AoC), Thiellavia terrestris (TtC), Fusarium solani (FsC), and Humicola insolens (HiC) was determined by analysis of CA deacetylation kinetics. wt-HiC had the highest catalytic efficiency (≈32 [cm 2 L -1 ] -1 h -1 ). Comparison of wt-cutinase catalytic constants revealed that differences in catalytic efficiency are primarily due to corresponding variations in corresponding substrate binding constants. Docking studies with model tetrameric substrates also revealed structural origins for differential substrate binding amongst these cutinases. Comparative docking studies of HiC point mutations led to the identification of two important rationales for engineering cutinases for CA deacetylation: (i) create a tight but not too closed binding groove, (ii) allow for hydrogen bonding in the extended region around the active site. Rationally designed HiC with amino acid substitutions I36S, predicted to hydrogen bond to CA, combined with F70A, predicted to remove steric constraints, showed a two-fold improvement in catalytic efficiency. Continued cutinase optimization guided by a detailed understanding of structure-activity relationships, as demonstrated here, will be an important tool to developing practical cutinases for commercial green chemistry technologies. Copyright © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Degradation of paracetamol by catalytic wet air oxidation and sequential adsorption - Catalytic wet air oxidation on activated carbons.

Science.gov (United States)

Quesada-Peñate, I; Julcour-Lebigue, C; Jáuregui-Haza, U J; Wilhelm, A M; Delmas, H

2012-06-30

The concern about the fate of pharmaceutical products has raised owing to the increasing contamination of rivers, lakes and groundwater. The aim of this paper is to evaluate two different processes for paracetamol removal. The catalytic wet air oxidation (CWAO) of paracetamol on activated carbon was investigated both as a water treatment technique using an autoclave reactor and as a regenerative treatment of the carbon after adsorption in a sequential fixed bed process. Three activated carbons (ACs) from different source materials were used as catalysts: two microporous basic ACs (S23 and C1) and a meso- and micro-porous acidic one (L27). During the first CWAO experiment the adsorption capacity and catalytic performance of fresh S23 and C1 were higher than those of fresh L27 despite its higher surface area. This situation changed after AC reuse, as finally L27 gave the best results after five CWAO cycles. Respirometry tests with activated sludge revealed that in the studied conditions the use of CWAO enhanced the aerobic biodegradability of the effluent. In the ADOX process L27 also showed better oxidation performances and regeneration efficiency. This different ageing was examined through AC physico-chemical properties. Copyright © 2012 Elsevier B.V. All rights reserved.

Catalytic Enantioselective Synthesis of Naturally Occurring Butenolides via Hetero-Allylic Alkylation and Ring Closing Metathesis

NARCIS (Netherlands)

Mao, Bin; Geurts, Koen; Fañanás-Mastral, Martín; Zijl, Anthoni W. van; Fletcher, Stephen P.; Minnaard, Adriaan J.; Feringa, Bernard

2011-01-01

An efficient catalytic asymmetric synthesis of chiral γ-butenolides was developed based on the hetero-allylic asymmetric alkylation (h-AAA) in combination with ring closing metathesis (RCM). The synthetic potential of the h-AAA-RCM protocol was illustrated with the facile synthesis of (-)-whiskey

Global financial crisis and weak-form efficiency of Islamic sectoral stock markets: An MF-DFA analysis

Science.gov (United States)

Mensi, Walid; Tiwari, Aviral Kumar; Yoon, Seong-Min

2017-04-01

This paper estimates the weak-form efficiency of Islamic stock markets using 10 sectoral stock indices (basic materials, consumer services, consumer goods, energy, financials, health care, industrials, technology, telecommunication, and utilities). The results based on the multifractal detrended fluctuation analysis (MF-DFA) approach show time-varying efficiency for the sectoral stock markets. Moreover, we find that they tend to show high efficiency in the long term but moderate efficiency in the short term, and that these markets become less efficient after the onset of the global financial crisis. These results have several significant implications in terms of asset allocation for investors dealing with Islamic markets.

Processing of mixed waste via quantum-catalytic extraction processing (Q-CEP trademark), a case study

International Nuclear Information System (INIS)

Evans, L.; Richards, T.; McGowan, B.

1996-01-01

Catalytic Extraction Processing (CEP) as developed by Molten Metal Technology (MMT), Inc. employs the use of a refractory-lined, steel-shell reactor vessel and an inductively-heated metal bath. When molten, the metal bath can process gaseous, liquid, and solid wastes and recycle their constituents into commercially valuable products. Quantum-Catalytic Extraction Processing, or Q-CEP, is the application of CEP technology to radioactive and mixed wastes. The Q-CEP technology can take wastes in various physical forms (gas, liquid, slurry, sludge, or grindable solid) and inject them into the molten metal bath of iron, nickel, or copper. The bath acts as both a catalyst and solvent and breaks the compounds of the waste feed into their original constituent elements. The flexibility and robustness of the Q-CEP process are attributed to the open-quote singular close-quote dissolved elemental intermediate through which reactions proceed. open-quotes Singular close-quote refers to the fact that the catalytic and salvation effects of the liquid metal ensure that the constituents of the feed are only found in the liquid metal as dissolved elements (e.g. dissolved carbon). As a result, Q-CEP feed conversion is independent of the complexity of the molecular structure of the feed molecule. Destruction and Removal Efficiencies (DREs) exceeding 99.9999% (six nines) are typical in CEP regardless of the complexity of feed materials. Q-CEP is not a combustion technology. Unlike incineration where wastes are volume reduced and residuals buried, Q-CEP allows for the formation of commercially valuable products. Chemical reactions are performed in a highly reducing environment which results in extremely low concentrations of free oxygen, preventing the formation of furans, dioxins, or other products of incomplete combustion

Investigations for the implementation of catalytic recombiners in large dry containments in Germany

International Nuclear Information System (INIS)

Rohde, J.; Tiltmann, M.; Froehmel, T.

1997-01-01

During the past few years, several concepts of mitigation have been developed and tested to limit the hydrogen concentrations in the containment atmosphere during the course of a severe accident. Extensive efforts have been given, especially in Germany and Canada, to investigate the use of catalytic recombiners. Based on the outcome of these research efforts in Germany it was recommended by the Reactor Safety Commission (RSK) in June 1994 to implement a hydrogen mitigation system, based on catalytic recombiners in large dry containments of PWR plants. Investigations are carried out at GRS, sponsored by the German Ministry of Environment, Nature Conservation and Nuclear Safety (BMU), to develop basic requirements for the implementation of a catalytic recombiner system in large dry containments. Severe accidents scenarios were calculated with the system code MELCOR to determine the mass- and energy release rates from the primary system into the containment, necessary to prepare the input data for the containment code calculations. A detailed nodalisation of the containment system of a German PWR plant (Konvoi-type) was developed for the code RA-LOC MOD4 to investigate the effectiveness of a catalytic recombiner system which consists of 53 of such devices, being distributed in the complex room arrangement. The effectiveness of such a system is demonstrated by comparing a representative severe accident sequence without and with the catalytic recombination of hydrogen. The results showed, that only in some limited areas in the containment combustible gas mixtures were formed for a limited time span and that at the end of the first day after the onset of the accident the catalytic reaction is limited due to oxygen depletion. The work is still in progress while additional severe accident sequences have to be analyzed to develop some generic guidelines for the implementation of a catalytic recombiner system in large dry containments. (author)

Efficient oxidation of alcohols to carbonyl compounds with molecular oxygen catalyzed by N-hydroxyphthalimide combined with a Co species

Science.gov (United States)

Iwahama; Yoshino; Keitoku; Sakaguchi; Ishii

2000-10-06

Highly efficient catalytic oxidation of alcohols with molecular oxygen by N-hydroxyphthalimide (NHPI) combined with a Co species was developed. The oxidation of 2-octanol in the presence of catalytic amounts of NHPI and Co(OAc)2 under atmospheric dioxygen in AcOEt at 70 degrees C gave 2-octanone in 93% yield. The oxidation was significantly enhanced by adding a small amount of benzoic acid to proceed smoothly even at room temperature. Primary alcohols were oxidized by NHPI in the absence of any metal catalyst to form the corresponding carboxylic acids in good yields. In the oxidation of terminal vic-diols such as 1,2-butanediol, carbon-carbon bond cleavage was induced to give one carbon less carboxylic acids such as propionic acid, while internal vic-diols were selectively oxidized to 1,2-diketones.

Internal Dynamics and Ionization States of the Macrophage Migration Inhibitory Factor: Comparison Between Wild-Type and Mutant Forms

International Nuclear Information System (INIS)

Soares, T A.; Lins, R D.; Straatsma, TP; Briggs, J M.

2002-01-01

The macrophage migration inhibitory factor (MIF) is a cytokine which shares a common structural architecture and catalytic strategy with three isomerases: 4-oxalocrotonate tautomerase, 5-carboxymethyl-2-hydroxymuconate isomerase and D-dopachrome tautomerase. A highly conserved N-terminal proline acts as a base/acid during the proton transfer reaction catalyzed by these enzymes. Such unusual catalytic strategy appears to be possible only due to the N-terminal proline pKa be shifted to 5.0-6.0 units. Mutations of this residue result in a significant decrease of the catalytic activity of MIF. Two hypotheses have been proposed to explain the catalytic inefficiency of MIF: the lower basicity of primary amines with regard to secondary ones and the increased flexibility resulting from the replacement of a proline by residues like glycine. To investigate that, we have performed molecular dynamics simulations of MIF-wt and its mutant P1G as well as calculated the protonation properties of sever al mutant forms. It has been found that the N-terminal glycine does not show larger fluctuations compared to proline, but the former residue is more exposed to the solvent throughout the simulations. The apparent pKa of these residues displays very little change (as expected from the structural rigidity of MIF) and is not significantly affected by the surrounding ionizable residues. Instead, the hydrophobic character of the active site seems to be the main factor in determining the pKa of the N-terminal residue and the catalytic efficiency of MIF

Catalytic growth of ZnO nanostructures by r.f. magnetron sputtering

Directory of Open Access Journals (Sweden)

Arroyo-Hernández María

2011-01-01

Full Text Available Abstract The catalytic effect of gold seed particles deposited on a substrate prior to zinc oxide (ZnO thin film growth by magnetron sputtering was investigated. For this purpose, selected ultra thin gold layers, with thicknesses close to the percolation threshold, are deposited by thermal evaporation in ultra high vacuum (UHV conditions and subsequently annealed to form gold nanodroplets. The ZnO structures are subsequently deposited by r.f. magnetron sputtering in a UHV chamber, and possible morphological differences between the ZnO grown on top of the substrate and on the gold are investigated. The results indicate a moderate catalytic effect for a deposited gold underlayer of 4 nm, quite close to the gold thin film percolation thickness.

Testing Weak Form Market Efficiency for Emerging Economies: A Nonlinear Approach

OpenAIRE

Omay, Nazli C.; Karadagli, Ece C.

2010-01-01

In this paper, we address weak form stock market efficiency of Emerging Economies, by testing whether the price series of these markets contain unit root. Nonlinear behavior of stock prices is well documented in the literature, and thus linear unit root tests may not be appropriate in this case. For this purpose, we employ the nonlinear unit root test procedure recently developed by Kapetanios et al. (2003) and nonlinear panel unit root test Ucar and Omay (2009) that has a better power than s...

Engineering reactors for catalytic reactions

Indian Academy of Sciences (India)

Extensive studies have been conducted to establish sound basis for design and engineering of reactors for practising such catalytic reactions and for realizing improvements in reactor performance. In this article, application of recent (and not so recent) developments in engineering reactors for catalytic reactions is ...

Effect of Ni-Co Ternary Molten Salt Catalysts on Coal Catalytic Pyrolysis Process

Science.gov (United States)

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.

Catalytic strategy used by the myosin motor to hydrolyze ATP.

Science.gov (United States)

Kiani, Farooq Ahmad; Fischer, Stefan

2014-07-22

Myosin is a molecular motor responsible for biological motions such as muscle contraction and intracellular cargo transport, for which it hydrolyzes adenosine 5'-triphosphate (ATP). Early steps of the mechanism by which myosin catalyzes ATP hydrolysis have been investigated, but still missing are the structure of the final ADP·inorganic phosphate (Pi) product and the complete pathway leading to it. Here, a comprehensive description of the catalytic strategy of myosin is formulated, based on combined quantum-classical molecular mechanics calculations. A full exploration of catalytic pathways was performed and a final product structure was found that is consistent with all experiments. Molecular movies of the relevant pathways show the different reorganizations of the H-bond network that lead to the final product, whose γ-phosphate is not in the previously reported HPγO4(2-) state, but in the H2PγO4(-) state. The simulations reveal that the catalytic strategy of myosin employs a three-pronged tactic: (i) Stabilization of the γ-phosphate of ATP in a dissociated metaphosphate (PγO3(-)) state. (ii) Polarization of the attacking water molecule, to abstract a proton from that water. (iii) Formation of multiple proton wires in the active site, for efficient transfer of the abstracted proton to various product precursors. The specific role played in this strategy by each of the three loops enclosing ATP is identified unambiguously. It explains how the precise timing of the ATPase activation during the force generating cycle is achieved in myosin. The catalytic strategy described here for myosin is likely to be very similar in most nucleotide hydrolyzing enzymes.

Investigation of the degradation mechanism of catalytic wires during oxidation of ammonia process

International Nuclear Information System (INIS)

Pura, Jarosław; Wieciński, Piotr; Kwaśniak, Piotr; Zwolińska, Marta; Garbacz, Halina; Zdunek, Joanna; Laskowski, Zbigniew; Gierej, Maciej

2016-01-01

Highlights: • Degradation mechanisms of precious metal catalytic gauzes is proposed. • Significant change of gauzes morphology and chemical composition was observed. • Samples were analyzed using SEM, EDS and micro-XCT techniques. - Abstract: The most common catalysts for the ammonia oxidation process are 80 μm diameter platinum-rhodium wires knitted or woven into the form of a gauze. In an aggressive environment and under extreme conditions (temperature 800–900 °C, intensive gas flow, high pressure) precious elements are drained from the surface of the wires. Part of this separated material quickly decomposes on the surface in the form of characteristic “cauliflower-shape protrusions”. The rest of the platinum is captured by palladium-nickel catalytic-capture gauzes located beneath. In our investigation we focused on the effects of the degradation of gauzes from one industrial catalytic system. The aim of the study was to compare the degree and the mechanism of degradation of gauzes from a different part of the reactor. The study covered PtRh7 catalytic and PdNi5 catalytic-capture gauzes. X-ray computer microtomography investigation revealed that despite strong differences in morphology, each Pt-Rh wire has a similar specific surface area. This indicates that the oxidation process and morphological changes of the wires occur in a self-regulating balance, resulting in the value of the specific surface area of the catalyst. Microtomography analysis of Pd-Ni wires revealed strong redevelopment of the wires’ surface, which is related to the platinum capture phenomenon. Scanning electron microscope observations also revealed the nanostructure in the cauliflower-shape protrusions and large grains in the wires’ preserved cores. The high temperature in the reactor and the long-term nature of the process do not favor the occurrence of the nanostructure in this type of material. Further and detailed analysis of this phenomena will provide a better

Investigation of the degradation mechanism of catalytic wires during oxidation of ammonia process

Energy Technology Data Exchange (ETDEWEB)

Pura, Jarosław, E-mail: jaroslawpura@gmail.com [Faculty of Material Science and Engineering, Warsaw University of Technology, Wołoska 141, 02-507 Warsaw (Poland); Wieciński, Piotr; Kwaśniak, Piotr; Zwolińska, Marta; Garbacz, Halina; Zdunek, Joanna [Faculty of Material Science and Engineering, Warsaw University of Technology, Wołoska 141, 02-507 Warsaw (Poland); Laskowski, Zbigniew; Gierej, Maciej [Precious Metal Mint, Weteranów 95, 05-250 Radzymin (Poland)

2016-12-01

Highlights: • Degradation mechanisms of precious metal catalytic gauzes is proposed. • Significant change of gauzes morphology and chemical composition was observed. • Samples were analyzed using SEM, EDS and micro-XCT techniques. - Abstract: The most common catalysts for the ammonia oxidation process are 80 μm diameter platinum-rhodium wires knitted or woven into the form of a gauze. In an aggressive environment and under extreme conditions (temperature 800–900 °C, intensive gas flow, high pressure) precious elements are drained from the surface of the wires. Part of this separated material quickly decomposes on the surface in the form of characteristic “cauliflower-shape protrusions”. The rest of the platinum is captured by palladium-nickel catalytic-capture gauzes located beneath. In our investigation we focused on the effects of the degradation of gauzes from one industrial catalytic system. The aim of the study was to compare the degree and the mechanism of degradation of gauzes from a different part of the reactor. The study covered PtRh7 catalytic and PdNi5 catalytic-capture gauzes. X-ray computer microtomography investigation revealed that despite strong differences in morphology, each Pt-Rh wire has a similar specific surface area. This indicates that the oxidation process and morphological changes of the wires occur in a self-regulating balance, resulting in the value of the specific surface area of the catalyst. Microtomography analysis of Pd-Ni wires revealed strong redevelopment of the wires’ surface, which is related to the platinum capture phenomenon. Scanning electron microscope observations also revealed the nanostructure in the cauliflower-shape protrusions and large grains in the wires’ preserved cores. The high temperature in the reactor and the long-term nature of the process do not favor the occurrence of the nanostructure in this type of material. Further and detailed analysis of this phenomena will provide a better

TEMPO functionalized C60 fullerene deposited on gold surface for catalytic oxidation of selected alcohols

International Nuclear Information System (INIS)

Piotrowski, Piotr; Pawłowska, Joanna; Sadło, Jarosław Grzegorz; Bilewicz, Renata; Kaim, Andrzej

2017-01-01

C 60 TEMPO 10 catalytic system linked to a microspherical gold support through a covalent S-Au bond was developed. The C 60 TEMPO 10 @Au composite catalyst had a particle size of 0.5–0.8 μm and was covered with the fullerenes derivative of 2.3 nm diameter bearing ten nitroxyl groups; the organic film showed up to 50 nm thickness. The catalytic composite allowed for the oxidation under mild conditions of various primary and secondary alcohols to the corresponding aldehyde and ketone analogues with efficiencies as high as 79–98%, thus giving values typical for homogeneous catalysis, while retaining at the same time all the advantages of heterogeneous catalysis, e.g., easy separation by filtration from the reaction mixture. The catalytic activity of the resulting system was studied by means of high pressure liquid chromatography. A redox mechanism was proposed for the process. In the catalytic cycle of the oxidation process, the TEMPO moiety was continuously regenerated in situ with an applied primary oxidant, for example, O 2 /Fe 3+ system. The new intermediate composite components and the final catalyst were characterized by various spectroscopic methods and thermogravimetry.

Catalytic Upgrading of Biomass-Derived Furfuryl Alcohol to Butyl Levulinate Biofuel over Common Metal Salts

Directory of Open Access Journals (Sweden)

Lincai Peng

2016-09-01

Full Text Available Levulinate ester has been identified as a promising renewable fuel additive and platform chemical. Here, the use of a wide range of common metal salts as acid catalysts for catalytic upgrading of biomass-derived furfuryl alcohol to butyl levulinate was explored by conventional heating. Both alkali and alkaline earth metal chlorides did not lead effectively to the conversion of furfuryl alcohol, while several transition metal chlorides (CrCl3, FeCl3, and CuCl2 and AlCl3 exhibited catalytic activity for the synthesis of butyl levulinate. For their sulfates (Cr(III, Fe(III, Cu(II, and Al(III, the catalytic activity was low. The reaction performance was correlated with the Brønsted acidity of the reaction system derived from the hydrolysis/alcoholysis of cations, but was more dependent on the Lewis acidity from the metal salts. Among these investigated metal salts, CuCl2 was found to be uniquely effective, leading to the conversion of furfuryl alcohol to butyl levulinate with an optimized yield of 95%. Moreover, CuCl2 could be recovered efficiently from the resulting reaction mixture and remained with almost unchanged catalytic activity in multiple recycling runs.

Fe-Mn bi-metallic oxides loaded on granular activated carbon to enhance dye removal by catalytic ozonation.

Science.gov (United States)

Tang, Shoufeng; Yuan, Deling; Zhang, Qi; Liu, Yameng; Zhang, Qi; Liu, Zhengquan; Huang, Haiming

2016-09-01

A Fe-Mn bi-metallic oxide supported on granular activated carbon (Fe-Mn GAC) has been fabricated by an impregnation-desiccation method and tested in the catalytic ozonation of methyl orange (MO) degradation and mineralization. X-ray diffraction, scanning electron microscopy, and Fourier transform infrared spectroscopy characterizations revealed that Fe-Mn oxides were successfully loaded and uniformly distributed on the GAC, and nitrogen adsorption isotherms showed that the supported GAC retained a large surface area and a high pore volume compared with the pristine GAC. The catalytic activity was systematically assessed by monitoring the MO removal efficiencies at different operational parameters, such as catalyst dosage, initial solution pH, and ozone flow rate. The Fe-Mn GAC exhibited better catalytic activity relative to ozone alone and GAC alone, improving the TOC removal by 24.5 and 11.5 % and COD removal by 13.6 and 7.3 %, respectively. The reusability of the hybrid was examined over five consecutive cyclic treatments. The Fe-Mn GAC catalytic activity was only a slight loss in the cycles, showing good stability. The addition of Na2CO3 as hydroxyl radicals (•OH) scavengers proved that the catalytic ozonation mechanism was the enhanced generation of •OH by the Fe-Mn GAC. The above results render the Fe-Mn GAC an industrially promising candidate for catalytic ozonation of dye contaminant removal.

SNCR technology for NO sub x reduction in the cement industry. [Selective non-catalytic reduction

Energy Technology Data Exchange (ETDEWEB)

Kupper, D; Brentrup, L [Krupp Polysius AG, Beckum (Germany)

1992-03-01

This article discusses the selective non-catalytic (SNCR) process for reducing nitrogen oxides in exhaust gases from cement plants. Topics covered include operating experience, injection of additives, selection of the additive, operating costs, reduction efficiency of SNCR, capital expenditure, secondary emissions and cycles of ammonium. (UK).

Investigating the Synthesis, Structure, and Catalytic Properties of Versatile Gold-Based Nanocatalvsts

Science.gov (United States)

Pretzer, Lori A.

Transition metal nanomaterials are used to catalyze many chemical reactions, including those key to environmental, medicinal, and petrochemical fields. Improving their catalytic properties and lifetime would have significant economic and environmental rewards. Potentially expedient options to make such advancements are to alter the shape, size, or composition of transition metal nanocatalysts. This work investigates the relationships between structure and catalytic properties of synthesized Au, Pd-on-Au, and Au-enzyme model transition metal nanocatalysts. Au and Pd-on-Au nanomaterials were studied due to their wide-spread application and structure-dependent electronic and geometric properties. The goal of this thesis is to contribute design procedures and synthesis methods that enable the preparation of more efficient transition metal nanocatalysts. The influence of the size and composition of Pd-on-Au nanoparticles (NPs) was systematically investigated and each was found to affect the catalyst's surface structure and catalytic properties. The catalytic hydrodechlorination of trichloroethene and reduction of 4-nitrophenol by Pd-on-Au nanoparticles were investigated as these reactions are useful for environmental and pharmaceutical synthesis applications, respectively. Structural characterization revealed that the dispersion and oxidation state of surface Pd atoms are controlled by the Au particle size and concentration of Pd. These structural changes are correlated with observed Pd-on-Au NP activities for both probe reactions, providing new insight into the structure-activity relationships of bimetallic nanocatalysts. Using the structure-dependent electronic properties of Au NPs, a new type of light-triggered biocatalyst was prepared and used to remotely control a model biochemical reaction. This biocatalyst consists of a model thermophilic glucokinase enzyme covalently attached to the surface of Au nanorods. The rod-like shape of the Au nanoparticles made the

Pyroelectrically Induced Pyro-Electro-Chemical Catalytic Activity of BaTiO3 Nanofibers under Room-Temperature Cold–Hot Cycle Excitations

Directory of Open Access Journals (Sweden)

Yuntao Xia

2017-04-01

Full Text Available A pyro-electro-chemical catalytic dye decomposition using lead-free BaTiO3 nanofibers was realized under room-temperature cold–hot cycle excitation (30–47 °C with a high Rhodamine B (RhB decomposition efficiency ~99%, which should be ascribed to the product of pyro-electric effect and electrochemical redox reaction. Furthermore, the existence of intermediate product of hydroxyl radical in pyro-electro-chemical catalytic process was also observed. There is no significant decrease in pyro-electro-chemical catalysis activity after being recycled five times. The pyro-electrically induced pyro-electro-chemical catalysis provides a high-efficient, reusable and environmentally friendly technology to remove organic pollutants from water.

Catalytic combustion in gas stoves - Phase II

Energy Technology Data Exchange (ETDEWEB)

Hjelm, Anna-Karin [CATATOR AB, Lund (Sweden)

2003-06-01

Several independent studies show that gas stoves to some degree contribute to the indoor emissions of NO{sub x} especially in situations were the ventilation flow is poor. The peak-NO{sub x} concentrations can reach several hundred ppb but the integral concentration seldom exceeds about 20 - 50 ppb, which corresponds to an indoor-outdoor ratio of about 1 - 2.5. Epidemiological studies indicate increasing problems with respiratory symptoms in sensitive people at concentrations as low as 15 ppb of NO{sub 2}. Consequently, the NO{sub x}-concentration in homes where gas stoves are used is high enough to cause health effects. However, in situations where the ventilation flow is high (utilisation of ventilation hoods) the NO{sub x}-emissions are not likely to cause any health problems. This study has been aimed at investigating the possibilities to reduce the NO{sub x} emissions from gas stoves by replacing the conventional flame combustion with catalytic combustion. The investigation is requested by Swedish Gas Center, and is a following-up work of an earlier conducted feasibility study presented in April-2002. The present investigation reports on the possibility to use cheap and simple retro-fit catalytic design suggestions for traditional gas stoves. Experiments have been conducted with both natural and town gas, and parameters such as emissions of NO{sub x}, CO and unburned fuel gas and thermal efficiency, etc, have been examined and are discussed. The results show that it is possible to reduce the NO{sub x} emissions up to 80% by a simple retro-fit installation, without decreasing the thermal efficiency of the cooking plate. The measured source strengths correspond to indoor NO{sub x} concentrations that are below or equal to the average outdoor concentration, implying that no additional detrimental health effects are probable. The drawback of the suggested installations is that the concentration of CO and in some cases also CH{sub 4} are increased in the flue gases

Substrate-Directed Catalytic Selective Chemical Reactions.

Science.gov (United States)

Sawano, Takahiro; Yamamoto, Hisashi

2018-05-04

The development of highly efficient reactions at only the desired position is one of the most important subjects in organic chemistry. Most of the reactions in current organic chemistry are reagent- or catalyst-controlled reactions, and the regio- and stereoselectivity of the reactions are determined by the inherent nature of the reagent or catalyst. In sharp contrast, substrate-directed reaction determines the selectivity of the reactions by the functional group on the substrate and can strictly distinguish sterically and electronically similar multiple reaction sites in the substrate. In this Perspective, three topics of substrate-directed reaction are mainly reviewed: (1) directing group-assisted epoxidation of alkenes, (2) ring-opening reactions of epoxides by various nucleophiles, and (3) catalytic peptide synthesis. Our newly developed synthetic methods with new ligands including hydroxamic acid derived ligands realized not only highly efficient reactions but also pinpointed reactions at the expected position, demonstrating the substrate-directed reaction as a powerful method to achieve the desired regio- and stereoselective functionalization of molecules from different viewpoints of reagent- or catalyst-controlled reactions.

Catalytic conversion of alcohols to hydrocarbons with low benzene content

Energy Technology Data Exchange (ETDEWEB)

Narula, Chaitanya K.; Davison, Brian H.; Keller, Martin

2016-03-08

A method for converting an alcohol to a hydrocarbon fraction having a lowered benzene content, the method comprising: converting said alcohol to a hydrocarbon fraction by contacting said alcohol, under conditions suitable for converting said alcohol to said hydrocarbon fraction, with a metal-loaded zeolite catalyst catalytically active for converting said alcohol to said hydrocarbon fraction, and contacting said hydrocarbon fraction with a benzene alkylation catalyst, under conditions suitable for alkylating benzene, to form alkylated benzene product in said hydrocarbon fraction. Also described is a catalyst composition useful in the method, comprising a mixture of (i) a metal-loaded zeolite catalyst catalytically active for converting said alcohol to said hydrocarbon, and (ii) a benzene alkylation catalyst, in which (i) and (ii) may be in a mixed or separated state. A reactor for housing the catalyst and conducting the reaction is also described.

Catalytic conversion of alcohols to hydrocarbons with low benzene content

Energy Technology Data Exchange (ETDEWEB)

Narula, Chaitanya K.; Davison, Brian H.; Keller, Martin

2016-09-06

A method for converting an alcohol to a hydrocarbon fraction having a lowered benzene content, the method comprising: converting said alcohol to a hydrocarbon fraction by contacting said alcohol, under conditions suitable for converting said alcohol to said hydrocarbon fraction, with a metal-loaded zeolite catalyst catalytically active for converting said alcohol to said hydrocarbon fraction, and contacting said hydrocarbon fraction with a benzene alkylation catalyst, under conditions suitable for alkylating benzene, to form alkylated benzene product in said hydrocarbon fraction. Also described is a catalyst composition useful in the method, comprising a mixture of (i) a metal-loaded zeolite catalyst catalytically active for converting said alcohol to said hydrocarbon, and (ii) a benzene alkylation catalyst, in which (i) and (ii) may be in a mixed or separated state. A reactor for housing the catalyst and conducting the reaction is also described.

Direct catalytic asymmetric aldol-Tishchenko reaction.

Science.gov (United States)

Gnanadesikan, Vijay; Horiuchi, Yoshihiro; Ohshima, Takashi; Shibasaki, Masakatsu

2004-06-30

A direct catalytic asymmetric aldol reaction of propionate equivalent was achieved via the aldol-Tishchenko reaction. Coupling an irreversible Tishchenko reaction to a reversible aldol reaction overcame the retro-aldol reaction problem and thereby afforded the products in high enantio and diastereoselectivity using 10 mol % of the asymmetric catalyst. A variety of ketones and aldehydes, including propyl and butyl ketones, were coupled efficiently, yielding the corresponding aldol-Tishchenko products in up to 96% yield and 95% ee. Diastereoselectivity was generally below the detection limit of 1H NMR (>98:2). Preliminary studies performed to clarify the mechanism revealed that the aldol products were racemic with no diastereoselectivity. On the other hand, the Tishchenko products were obtained in a highly enantiocontrolled manner.

Activation of Al–Cu–Fe quasicrystalline surface: fabrication of a fine nanocomposite layer with high catalytic performance

Directory of Open Access Journals (Sweden)

Satoshi Kameoka

2014-01-01

Full Text Available A fine layered nanocomposite with a total thickness of about 200 nm was formed on the surface of an Al63Cu25Fe12 quasicrystal (QC. The nanocomposite was found to exhibit high catalytic performance for steam reforming of methanol. The nanocomposite was formed by a self-assembly process, by leaching the Al–Cu–Fe QC using a 5 wt% Na2CO3 aqueous solution followed by calcination in air at 873 K. The quasiperiodic nature of the QC played an important role in the formation of such a structure. Its high catalytic activity originated from the presence of highly dispersed copper and iron species, which also suppressed the sintering of nanoparticles.

Optimization of the catalytic converter internal flow by using 3D-CFD; Sanjigen nagare kaiseki ni yoru shokubai converter nai nagare no saitekika

Energy Technology Data Exchange (ETDEWEB)

Toi, M; Sugiura, S [Toyota Motor Corp., Tokyo (Japan)

1997-10-01

By using computational fluid dynamics and statistical quality control method, we investigated the contribution of front and rear catalytic converter cone shape for the pressure loss and the partial flow, also led the optimal terms and the predictional formulations efficiently. According to this, we can investigate the optimal position of the catalytic converter from the planning. 8 figs., 6 tabs.

Advanced purification of petroleum refinery wastewater by catalytic vacuum distillation.

Science.gov (United States)

Yan, Long; Ma, Hongzhu; Wang, Bo; Mao, Wei; Chen, Yashao

2010-06-15

In our work, a new process, catalytic vacuum distillation (CVD) was utilized for purification of petroleum refinery wastewater that was characteristic of high chemical oxygen demand (COD) and salinity. Moreover, various common promoters, like FeCl(3), kaolin, H(2)SO(4) and NaOH were investigated to improve the purification efficiency of CVD. Here, the purification efficiency was estimated by COD testing, electrolytic conductivity, UV-vis spectrum, gas chromatography-mass spectrometry (GC-MS) and pH value. The results showed that NaOH promoted CVD displayed higher efficiency in purification of refinery wastewater than other systems, where the pellucid effluents with low salinity and high COD removal efficiency (99%) were obtained after treatment, and the corresponding pH values of effluents varied from 7 to 9. Furthermore, environment estimation was also tested and the results showed that the effluent had no influence on plant growth. Thus, based on satisfied removal efficiency of COD and salinity achieved simultaneously, NaOH promoted CVD process is an effective approach to purify petroleum refinery wastewater. Copyright 2010 Elsevier B.V. All rights reserved.

Synthesis, spectroscopic characterization and catalytic oxidation ...

Indian Academy of Sciences (India)

were characterized by infrared, electronic, electron paramagnetic resonance ... The catalytic oxidation property of ruthenium(III) complexes were also ... cies at room temperature. ..... aldehyde part of Schiff base ligands, catalytic activ- ity of new ...

Size control and catalytic activity of bio-supported palladium nanoparticles.

Science.gov (United States)

Søbjerg, Lina Sveidal; Lindhardt, Anders T; Skrydstrup, Troels; Finster, Kai; Meyer, Rikke Louise

2011-07-01

The development of nanoparticles has greatly improved the catalytic properties of metals due to the higher surface to volume ratio of smaller particles. The production of nanoparticles is most commonly based on abiotic processes, but in the search for alternative protocols, bacterial cells have been identified as excellent scaffolds of nanoparticle nucleation, and bacteria have been successfully employed to recover and regenerate platinum group metals from industrial waste. We report on the formation of bio-supported palladium (Pd) nanoparticles on the surface of two bacterial species with distinctly different surfaces: the gram positive Staphylococcus sciuri and the gram negative Cupriavidus necator. We investigated how the type of bacterium and the amount of biomass affected the size and catalytic properties of the nanoparticles formed. By increasing the biomass:Pd ratio, we could produce bio-supported Pd nanoparticles smaller than 10nm in diameter, whereas lower biomass:Pd ratios resulted in particles ranging from few to hundreds of nm. The bio-supported Pd nanoparticle catalytic properties were investigated towards the Suzuki-Miyaura cross coupling reaction and hydrogenation reactions. Surprisingly, the smallest nanoparticles obtained at the highest biomass:Pd ratio showed no reactivity towards the test reactions. The lack of reactivity appears to be caused by thiol groups, which poison the catalyst by binding strongly to Pd. Different treatments intended to liberate particles from the biomass, such as burning or rinsing in acetone, did not re-establish their catalytic activity. Sulphur-free biomaterials should therefore be explored as more suitable scaffolds for Pd(0) nanoparticle formation. Copyright © 2011 Elsevier B.V. All rights reserved.

The Arabidopsis thaliana proteome harbors undiscovered multi-domain molecules with functional guanylyl cyclase catalytic centers

KAUST Repository

Wong, Aloysius Tze; Gehring, Christoph A

2013-01-01

plants, guanylyl cyclases (GCs), enzymes that generate cGMP from guanosine-5'-triphosphate (GTP) have remained elusive until recently. GC search motifs constructed from the alignment of known GCs catalytic centers form vertebrates and lower eukaryotes

Efficient Catalytic Conversion of Ethanol to 1-Butanol via the Guerbet Reaction over Copper- and Nickel-Doped Porous

NARCIS (Netherlands)

Sun, Zhuohua; Vasconcelos, Anais Couto; Bottari, Giovanni; Stuart, Marc C. A.; Bonura, Giuseppe; Cannilla, Catia; Frusteri, Francesco; Barta, Katalin

The direct conversion of ethanol to higher value 1-butanol is a catalytic transformation of great interest in light of the expected wide availability of bioethanol originating from the fermentation of renewable resources. In this contribution we describe several novel compositions of porous metal

Recent developments in research on catalytic reaction networks

Directory of Open Access Journals (Sweden)

Roberto Serra

2013-09-01

Full Text Available Over the last years, analyses performed on a stochastic model of catalytic reaction networks have provided some indications about the reasons why wet-lab experiments hardly ever comply with the phase transition typically predicted by theoretical models with regard to the emergence of collectively self-replicating sets of molecule (also defined as autocatalytic sets, ACSs, a phenomenon that is often observed in nature and that is supposed to have played a major role in the emergence of the primitive forms of life. The model at issue has allowed to reveal that the emerging ACSs are characterized by a general dynamical fragility, which might explain the difficulty to observe them in lab experiments. In this work, the main results of the various analyses are reviewed, with particular regard to the factors able to affect the generic properties of catalytic reactions network, for what concerns, not only the probability of ACSs to be observed, but also the overall activity of the system, in terms of production of new species, reactions and matter.

Catalytic synthesis of enantiopure mixed diacylglycerols - synthesis of a major M. tuberculosis phospholipid and platelet activating factor

NARCIS (Netherlands)

Fodran, Peter; Minnaard, Adriaan J.

2013-01-01

An efficient catalytic one-pot synthesis of TBDMS-protected diacylglycerols has been developed, starting from enantiopure glycidol. Subsequent migration-free deprotection leads to stereo- and regiochemically pure diacylglycerols. This novel strategy has been applied to the synthesis of a major

Catalytic Wittig and aza-Wittig reactions

Directory of Open Access Journals (Sweden)

Zhiqi Lao

2016-11-01

Full Text Available This review surveys the literature regarding the development of catalytic versions of the Wittig and aza-Wittig reactions. The first section summarizes how arsenic and tellurium-based catalytic Wittig-type reaction systems were developed first due to the relatively easy reduction of the oxides involved. This is followed by a presentation of the current state of the art regarding phosphine-catalyzed Wittig reactions. The second section covers the field of related catalytic aza-Wittig reactions that are catalyzed by both phosphine oxides and phosphines.

Adsorbent catalytic nanoparticles and methods of using the same

Energy Technology Data Exchange (ETDEWEB)

Slowing, Igor Ivan; Kandel, Kapil

2017-01-31

The present invention provides an adsorbent catalytic nanoparticle including a mesoporous silica nanoparticle having at least one adsorbent functional group bound thereto. The adsorbent catalytic nanoparticle also includes at least one catalytic material. In various embodiments, the present invention provides methods of using and making the adsorbent catalytic nanoparticles. In some examples, the adsorbent catalytic nanoparticles can be used to selectively remove fatty acids from feedstocks for biodiesel, and to hydrotreat the separated fatty acids.

Catalytic combustion of gasified waste - Experimental part. Final report

Energy Technology Data Exchange (ETDEWEB)

Jaeraas, Sven; Kusar, Henrik [Royal Institute of Technology, Stockholm (Sweden). Chemical Engineering and Technology

2003-08-01

This final report covers the work that has been performed within the project P 10547-2, 'Catalytic combustion of gasified waste - system analysis ORWARE'. This project is part of the research programme 'Energy from Waste' financed by the Swedish National Energy Administration. The project has been carried out at the division of Industrial Ecology and at the division of Chemical Technology at Royal Inst. of Technology. The aim of the project has been to study the potentials for catalytic combustion of gasified waste. The supposed end user of the technique is a smaller community in Sweden with 15,000-20,000 inhabitants. The project contains of two sub projects: an experimental part carried out at Chemical Technology and a system analysis carried out at Industrial Ecology. This report covers the experimental part of the project carried out at Chemical Technology. The aim for the experimental part has been to develop and test catalysts with long life-time and a high performance, to reduce the thermal-NO{sub x} below 5 ppm and to significantly reduce NO{sub x} formed from fuel-bound nitrogen. Different experimental studies have been carried out within the project: a set-up of catalytic materials have been tested over a synthetic mixture of the gasified waste, the influence of sulfur present in the gas stream, NO{sub x} formation from fuel bound nitrogen, kinetic studies of CO and H{sub 2} with and without the presence of water and the effects of adding a co-metal to palladium catalysts Furthermore a novel annular reactor design has been used to carry out experiments for kinetic measurements. Real gasification tests of waste pellets directly coupled to catalytic combustion have successfully been performed. The results obtained from the experiments, both the catalytic combustion and from the gasification, have been possible to use in the system analysis. The aim of the system analysis of catalytic combustion of gasified waste takes into consideration

Occurrence of dead core in catalytic particles containing immobilized enzymes: analysis for the Michaelis-Menten kinetics and assessment of numerical methods.

Science.gov (United States)

Pereira, Félix Monteiro; Oliveira, Samuel Conceição

2016-11-01

In this article, the occurrence of dead core in catalytic particles containing immobilized enzymes is analyzed for the Michaelis-Menten kinetics. An assessment of numerical methods is performed to solve the boundary value problem generated by the mathematical modeling of diffusion and reaction processes under steady state and isothermal conditions. Two classes of numerical methods were employed: shooting and collocation. The shooting method used the ode function from Scilab software. The collocation methods included: that implemented by the bvode function of Scilab, the orthogonal collocation, and the orthogonal collocation on finite elements. The methods were validated for simplified forms of the Michaelis-Menten equation (zero-order and first-order kinetics), for which analytical solutions are available. Among the methods covered in this article, the orthogonal collocation on finite elements proved to be the most robust and efficient method to solve the boundary value problem concerning Michaelis-Menten kinetics. For this enzyme kinetics, it was found that the dead core can occur when verified certain conditions of diffusion-reaction within the catalytic particle. The application of the concepts and methods presented in this study will allow for a more generalized analysis and more accurate designs of heterogeneous enzymatic reactors.

Dimerization interface of 3-hydroxyacyl-CoA dehydrogenase tunes the formation of its catalytic intermediate.

Directory of Open Access Journals (Sweden)

Yingzhi Xu

Full Text Available 3-Hydroxyacyl-CoA dehydrogenase (HAD, EC 1.1.1.35 is a homodimeric enzyme localized in the mitochondrial matrix, which catalyzes the third step in fatty acid β-oxidation. The crystal structures of human HAD and subsequent complexes with cofactor/substrate enabled better understanding of HAD catalytic mechanism. However, numerous human diseases were found related to mutations at HAD dimerization interface that is away from the catalytic pocket. The role of HAD dimerization in its catalytic activity needs to be elucidated. Here, we solved the crystal structure of Caenorhabditis elegans HAD (cHAD that is highly conserved to human HAD. Even though the cHAD mutants (R204A, Y209A and R204A/Y209A with attenuated interactions on the dimerization interface still maintain a dimerization form, their enzymatic activities significantly decrease compared to that of the wild type. Such reduced activities are in consistency with the reduced ratios of the catalytic intermediate formation. Further molecular dynamics simulations results reveal that the alteration of the dimerization interface will increase the fluctuation of a distal region (a.a. 60-80 that plays an important role in the substrate binding. The increased fluctuation decreases the stability of the catalytic intermediate formation, and therefore the enzymatic activity is attenuated. Our study reveals the molecular mechanism about the essential role of the HAD dimerization interface in its catalytic activity via allosteric effects.

Catalytic pyrolysis of hydrocarbons

Energy Technology Data Exchange (ETDEWEB)

Vail' eva, N A; Buyanov, R A

1979-01-01

Catalytic pyrolysis of petroleum fractions (undecane) was performed with the object of clarifying such questions as the mechanism of action of the catalyst, the concepts of activity and selectivity of the catalyst, the role of transport processes, the temperature ranges and limitations of the catalytic process, the effect of the catalyst on secondary processes, and others. Catalysts such as quartz, MgO, Al/sub 2/O/sub 3/, were used. Analysis of the experimental findings and the fact that the distribution of products is independent of the nature of the surface, demonstrate that the pyrolysis of hydrocarbons in the presence of catalysts is based on the heterogeneous-homogeneous radical-chain mechanism of action, and that the role of the catalysts reduces to increasing the concentration of free radicals. The concept of selectivity cannot be applied to catalysts here, since they do not affect the mechanism of the unfolding of the process of pyrolysis and their role consists solely in initiating the process. In catalytic pyrolysis the concepts of kinetic and diffusive domains of unfolding of the catalytic reaction do not apply, and only the outer surface of the catalyst is engaged, whereas the inner surface merely promotes deletorious secondary processes reducing the selectivity of the process and the activity of the catalyst. 6 references, 2 figures.

Performance simulations of catalytic converters during the Federal Test Procedure

Energy Technology Data Exchange (ETDEWEB)

Shen, H.; Shamim, T.; Sengupta, S.; Son, S.; Adamczyk, A.A.

1999-07-01

A numerical study is carried out to predict the tailpipe emissions and emission conversion efficiencies of unburned hydrocarbon, nitrogen oxide and carbon monoxide flowing through a catalytic converter during the Federal Test Procedure (FTP). The model considers the effect of heat transfer in the catalytic converter, coupled with catalyst chemical kinetics, including an oxygen storage mechanism. The resulting governing equations based on the conservation of mass and energy are solved by a tridiagonal matrix algorithm (TDMA) with a successive line under relaxation method. The numerical scheme for this non-linear problem is found to have good convergence efficiency. The simulation for the complete FTP cycle is accomplished in less than fifteen minutes on a desktop personal computer. A 13-step reaction mechanism plus a nine-step O{sub 2} storage mechanism is used to simulate the chemical kinetics. The energy equations include the heat loss due to conduction and convection plus the energy liberated by chemical reactions. The effect of radiation is assumed to be negligible and is not considered. The results of the numerical model for both the instantaneous and accumulated emissions are found to be in good agreement with experimental measurements. The conversion efficiencies of HC, CO and NO as predicted by the model are found to be within 5% of those dynamic measurements, and calculated results of accumulated HC, CO and NO{sub x} are in fair agreement with experimental measurements. The transient measurements are also used to check the robustness of the numerical model. The model is found to be robust and hence can simulate various operating conditions of engine output to the converter.

Volatilisation and catalytic effects of alkali and alkaline earth metallic species during the pyrolysis and gasification of Victorian brown coal. Part IV. Catalytic effects of NaCl and ion-exchangeable Na in coal on char reactivity

Energy Technology Data Exchange (ETDEWEB)

Dimple Mody Quyn; Hongwei Wu; Jun-ichiro Hayashi; Chun-Zhu Li, [Monash University, Monash, Vic. (Australia). CRC for Clean Power from Lignite, Department of Chemical Engineering

2003-03-01

The purpose of this study is to investigate the catalytic effects of Na as NaCl or as sodium carboxylates ( COONa) in Victorian brown coal on the char reactivity. A Na-exchanged coal and a set of NaCl-loaded coal samples prepared from a Loy Yang brown coal were pyrolysed in a fluidised-bed/fixed-bed reactor and in a thermogravimetric analyser (TGA). The reactivities of the chars were measured in air at 400{sup o}C using the TGA. The experimental data indicate that the Na in coal as NaCl and as sodium carboxylates ( COONa) had very different catalytic effects on the char reactivity. It is the chemical form and dispersion of Na in char, not in coal, that govern the catalytic effects of Na. For the Na-form (Na-exchanged) coal, the char reactivity increased with increasing pyrolysis temperature from 500 to 700{sup o}C and then decreased with pyrolysis temperature from 700 to 900{sup o}C. The increase in reactivity with pyrolysis temperature (500 700{sup o}C) is mainly due to the changes in the relative distribution of Na in the char matrix and on the pore surface. For the NaCl-loaded coals, when Cl was released during pyrolysis or gasification, the Na originally present in coal as NaCl showed good catalytic effects for the char gasification. Otherwise, Cl would combine with Na in the char to form NaCl during gasification, preventing Na from becoming an active catalyst. Controlling the pyrolysis conditions to favour the release of Cl can be a promising way to transform NaCl in coal into an active catalyst for char gasification. 38 refs., 5 figs.

Design and Experimentation with Sandwich Microstructure for Catalytic Combustion-Type Gas Sensors

Directory of Open Access Journals (Sweden)

Jun-Tao Gu

2014-03-01

Full Text Available The traditional handmade catalytic combustion gas sensor has some problems such as a pairing difficulty, poor consistency, high power consumption, and not being interchangeable. To address these issues, integrated double catalytic combustion of alcohol gas sensor was designed and manufactured using silicon micro-electro-mechanical systems (MEMS technology. The temperature field of the sensor is analyzed using the ANSYS finite element analysis method. In this work, the silicon oxide-PECVD-oxidation technique is used to manufacture a SiO2-Si3N2-SiO2 microstructure carrier with a sandwich structure, while wet etching silicon is used to form a beam structure to reduce the heat consumption. Thin-film technology is adopted to manufacture the platinum-film sensitive resistance. Nano Al2O3-ZrO-ThO is coated to format the sensor carrier, and the sensitive unit is dipped in a Pt-Pd catalyst solution to form the catalytic sensitive bridge arm. Meanwhile the uncoated catalyst carrier is considered as the reference unit, realizing an integrated chip based on a micro double bridge and forming sensors. The lines of the Pt thin-film resistance have been observed with an electronic microscope. The compensation of the sensitive material carriers and compensation materials have been analyzed using an energy spectrum. The results show that the alcohol sensor can detect a volume fraction between 0 and 4,500 × 10−6 and has good linear output characteristic. The temperature ranges from −20 to +40 °C. The humidity ranges from 30% to 85% RH. The zero output of the sensor is less than ±2.0% FS. The power consumption is ≤0.2 W, and both the response and recovery time are approximately 20 s.

Study of the technology of the plasma nanostructuring of silicon to form highly efficient emission structures

Energy Technology Data Exchange (ETDEWEB)

Galperin, V. A.; Kitsyuk, E. P. [“Technological Center” Research-and-Production Company (Russian Federation); Pavlov, A. A. [Russian Academy of Sciences, Institute of Nanotechnologies in Microelectronics (Russian Federation); Shamanaev, A. A., E-mail: artemiy.shamanaev@tcen.ru [“Technological Center” Research-and-Production Company (Russian Federation)

2015-12-15

New methods for silicon nanostructuring and the possibility of raising the aspect ratios of the structures being formed are considered. It is shown that the technology developed relates to self-formation methods and is an efficient tool for improving the quality of field-emission cathodes based on carbon nanotubes (CNTs) by increasing the Si–CNT contact area and raising the efficiency of the heat sink.

Preparation of magnetic imprinted graphene oxide composite for catalytic degradation of Congo red under dark ambient conditions.

Science.gov (United States)

Yang, Xiaochao; You, Xiaoxiao; Zhang, Bin; Guo, Chuigen; Yu, Chaosheng

2017-10-01

Magnetic imprinted N-doped P25/Fe 3 O 4 -graphene oxide (MIGNT) was prepared with methyl orange as the dummy template and pyrrole as functional monomer for catalytic degradation of Congo red (CR). Hummers method and the hydrothermal method were used to synthesize Fe 3 O 4 -GO and N-doped P25, respectively. The results of adsorption and degradation experiments showed that the adsorption capacity and catalytic degradation ability of the imprinted composite for CR were obviously higher than those of a non-imprinted one. Moreover, the effect factors on degradation efficiency of CR, such as the initial concentration of CR, catalysis time, pH of the solution and temperature, were investigated. The MIGNT was characterized by X-ray diffraction, Fourier transform infrared spectroscopy, transmission electron microscopy, a physical property measurement system and a thermal gravimetric analyzer. The degradation products of CR were detected with high performance liquid chromatography and a mass spectrometer. The MIGNT was a brand-new imprinted composite and had high degradation efficiency for CR under dark ambient conditions. The MIGNT could be recycled conveniently, due to its magnetic property, and could be used as an effective, environmentally friendly and low-cost catalytic degradation material for the treatment of water contaminated by CR.

QM/MM simulations identify the determinants of catalytic activity differences between type II dehydroquinase enzymes.

Science.gov (United States)

Lence, Emilio; van der Kamp, Marc W; González-Bello, Concepción; Mulholland, Adrian J

2018-05-16

Type II dehydroquinase enzymes (DHQ2), recognized targets for antibiotic drug discovery, show significantly different activities dependent on the species: DHQ2 from Mycobacterium tuberculosis (MtDHQ2) and Helicobacter pylori (HpDHQ2) show a 50-fold difference in catalytic efficiency. Revealing the determinants of this activity difference is important for our understanding of biological catalysis and further offers the potential to contribute to tailoring specificity in drug design. Molecular dynamics simulations using a quantum mechanics/molecular mechanics potential, with correlated ab initio single point corrections, identify and quantify the subtle determinants of the experimentally observed difference in efficiency. The rate-determining step involves the formation of an enolate intermediate: more efficient stabilization of the enolate and transition state of the key step in MtDHQ2, mainly by the essential residues Tyr24 and Arg19, makes it more efficient than HpDHQ2. Further, a water molecule, which is absent in MtDHQ2 but involved in generation of the catalytic Tyr22 tyrosinate in HpDHQ2, was found to destabilize both the transition state and the enolate intermediate. The quantification of the contribution of key residues and water molecules in the rate-determining step of the mechanism also leads to improved understanding of higher potencies and specificity of known inhibitors, which should aid ongoing inhibitor design.

Aziridine- and Azetidine-Pd Catalytic Combinations. Synthesis and Evaluation of the Ligand Ring Size Impact on Suzuki-Miyaura Reaction Issues

Directory of Open Access Journals (Sweden)

Hamza Boufroura

2017-01-01

Full Text Available The synthesis of new vicinal diamines based on aziridine and azetidine cores as well as the comparison of their catalytic activities as ligand in the Suzuki-Miyaura coupling reaction are described in this communication. The synthesis of three- and four-membered ring heterocycles substituted by a methylamine pendant arm is detailed from the parent nitrile derivatives. Complexation to palladium under various conditions has been examined affording vicinal diamines or amine-imidate complexes. The efficiency of four new catalytic systems is compared in the preparation of variously substituted biaryls. Aziridine- and azetidine-based catalytic systems allowed Suzuki-Miyaura reactions from aryl halides including chlorides with catalytic loadings until 0.001% at temperatures ranging from 100 °C to r.t. The evolution of the Pd-metallacycle ring strain moving from azetidine to aziridine in combination with a methylamine or an imidate pendant arm impacted the Suzuki-Miyaura reaction issue.

On the nanostructuring and catalytic promotion of intermediate temperature solid oxide fuel cell (IT-SOFC) cathodes

Science.gov (United States)

Serra, José M.; Buchkremer, Hans-Peter

Solid oxide fuel cells (SOFCs) are highly efficient energy converters for both stationary and mobile purposes. However, their market introduction still demands the reduction of manufacture costs and one possible way to reach this goal is the decrease of the operating temperatures, which entails the improvement of the cathode electrocatalytic properties. An ideal cathode material may have mixed ionic and electronic conductivity as well as proper catalytic properties. Nanostructuring and catalytic promotion of mixed conducting perovskites (e.g. La 0.58Sr 0.4Fe 0.8Co 0.2O 3- δ) seem to be promising approaches to overcoming cathode polarization problems and are briefly illustrated here. The preparation of nanostructured cathodes with relatively high surface area and enough thermal stability enables to improve the oxygen exchange rate and therefore the overall SOFC performance. A similar effect was obtained by catalytic promoting the perovskite surface, allowing decoupling the catalytic and ionic-transport properties in the cathode design. Noble metal incorporation may improve the reversibility of the reduction cycles involved in the oxygen reduction. Under the cathode oxidizing conditions, Pd seems to be partially dissolved in the perovskite structure and as a result very well dispersed.

Catalytic cracking models developed for predictive control purposes

Directory of Open Access Journals (Sweden)

Dag Ljungqvist

1993-04-01

Full Text Available The paper deals with state-space modeling issues in the context of model-predictive control, with application to catalytic cracking. Emphasis is placed on model establishment, verification and online adjustment. Both the Fluid Catalytic Cracking (FCC and the Residual Catalytic Cracking (RCC units are discussed. Catalytic cracking units involve complex interactive processes which are difficult to operate and control in an economically optimal way. The strong nonlinearities of the FCC process mean that the control calculation should be based on a nonlinear model with the relevant constraints included. However, the model can be simple compared to the complexity of the catalytic cracking plant. Model validity is ensured by a robust online model adjustment strategy. Model-predictive control schemes based on linear convolution models have been successfully applied to the supervisory dynamic control of catalytic cracking units, and the control can be further improved by the SSPC scheme.

Performance of new generation TWC catalytic systems working under different conditions in order to reduce the emission of a global warming gas: N{sub 2}O

Energy Technology Data Exchange (ETDEWEB)

Mac-Beath, I.; Castillo, S.; Camposeco, R.; Moran-Pineda, M. [Instituto Mexicano del Petroleo, Mexico, D.F. (Mexico). Programa de Ingenieria Molecular

2010-07-01

In this work, three-way catalytic systems (TWC-K, TWC-M and TWC-P) were prepared and tested experimentally in order to analyze N{sub 2}O emissions. Various types and quantities of precious metals (Pt-Pd-Rh), and different mixed oxides (CexBayLazMgwO{sub 2}-Al{sub 2}O{sub 3}) to prepare the supports were used. The catalytic tests were carried out by using common exhaust gases from a gasoline engine under different oxidizing conditions. The TWC catalytic compositions were based on catalytic converters used in retrofitting programs in the Metropolitan Area in Mexico City. Fresh and aged TWC catalytic samples were tested; in both conditions, the catalytic compositions were characterized by BET, TEM-EDS and XRD in order to analyze the efficiency of the catalytic behavior. Due to the fact that the 4{sup th} TWC generation (Pd-Only TWC) has Pd as main active metal, the tested TWC catalytic samples were synthesized by having Pd in a higher proportion with regard to Pt and Rh used as complements with some differences in support composition. (orig.)

A non-catalytic N-terminal domain negatively influences the nucleotide exchange activity of translation elongation factor 1Bα.

Science.gov (United States)

Trosiuk, Tetiana V; Shalak, Vyacheslav F; Szczepanowski, Roman H; Negrutskii, Boris S; El'skaya, Anna V

2016-02-01

Eukaryotic translation elongation factor 1Bα (eEF1Bα) is a functional homolog of the bacterial factor EF-Ts, and is a component of the macromolecular eEF1B complex. eEF1Bα functions as a catalyst of guanine nucleotide exchange on translation elongation factor 1A (eEF1A). The C-terminal domain of eEF1Bα is necessary and sufficient for its catalytic activity, whereas the N-terminal domain interacts with eukaryotic translation elongation factor 1Bγ (eEF1Bγ) to form a tight complex. However, eEF1Bγ has been shown to enhance the catalytic activity of eEF1Bα attributed to the C-terminal domain of eEF1Bα. This suggests that the N-terminal domain of eEF1Bα may in some way influence the guanine nucleotide exchange process. We have shown that full-length recombinant eEF1Bα and its truncated forms are non-globular proteins with elongated shapes. Truncation of the N-terminal domain of eEF1Bα, which is dispensable for catalytic activity, resulted in acceleration of the rate of guanine nucleotide exchange on eEF1A compared to full-length eEF1Bα. A similar effect on the catalytic activity of eEF1Bα was observed after its interaction with eEF1Bγ. We suggest that the non-catalytic N-terminal domain of eEF1Bα may interfere with eEF1A binding to the C-terminal catalytic domain, resulting in a decrease in the overall rate of the guanine nucleotide exchange reaction. Formation of a tight complex between the eEF1Bγ and eEF1Bα N-terminal domains abolishes this inhibitory effect. © 2015 FEBS.

Effect of inlet cone pipe angle in catalytic converter

Science.gov (United States)

Amira Zainal, Nurul; Farhain Azmi, Ezzatul; Arifin Samad, Mohd

2018-03-01

The catalytic converter shows significant consequence to improve the performance of the vehicle start from it launched into production. Nowadays, the geometric design of the catalytic converter has become critical to avoid the behavior of backpressure in the exhaust system. The backpressure essentially reduced the performance of vehicles and increased the fuel consumption gradually. Consequently, this study aims to design various models of catalytic converter and optimize the volume of fluid flow inside the catalytic converter by changing the inlet cone pipe angles. Three different geometry angles of the inlet cone pipe of the catalytic converter were assessed. The model is simulated in Solidworks software to determine the optimum geometric design of the catalytic converter. The result showed that by decreasing the divergence angle of inlet cone pipe will upsurge the performance of the catalytic converter.

Pd-MnO2 nanoparticles/TiO2 nanotube arrays (NTAs) photo-electrodes photo-catalytic properties and their ability of degrading Rhodamine B under visible light.

Science.gov (United States)

Thabit, Mohamed; Liu, Huiling; Zhang, Jian; Wang, Bing

2017-10-01

Pd-MnO 2 /TiO 2 nanotube arrays (NTAs) photo-electrodes were successfully fabricated via anodization and electro deposition subsequently; the obtained Pd-MnO 2 /TiO 2 NTAs photo electrodes were analyzed by scanning electron microscopy (SEM), X-ray diffraction (XRD) and characterized accordingly. Moreover, the light harvesting and absorption properties were investigated via ultraviolet-visible diffuse reflectance spectrum (DRS); photo degradation efficiency was investigated via analyzing the photo catalytic degradation of Rhodamine B under visible illumination (xenon light). The performed analyses illustrated that Pd-MnO 2 codoped particles were successfully deposited onto the surface of the TiO 2 nanotube arrays; DRS results showed significant improvement in visible light absorption which was between 400 and 700nm. Finally, the photo catalytic degradation efficiency results of the designated organic pollutant (Rhodamine B) illustrated a superior photocatalytic (PC) efficiency of approximately 95% compared to the bare TiO 2 NTAs, which only exhibited a photo catalytic degradation efficiency of approximately 61%, thus it indicated the significant enhancement of the light absorption properties of fabricated photo electrodes and their yield of OH radicals. Copyright © 2017. Published by Elsevier B.V.

Photo catalytic degradation of nitrobenzene using nanocrystalline TiO{sub 2} photo catalyst doped with Zn ions

Energy Technology Data Exchange (ETDEWEB)

Reynoso S, E. A.; Perez S, S.; Reyes C, A. P.; Castro R, C. L.; Felix N, R. M.; Lin H, S. W. [Instituto Tecnologico de Tijuana, Centro de Graduados e Investigacion, Apdo. Postal 1166, 22000 Tijuana, Baja California (Mexico); Paraguay D, F. [Centro de Investigacion en Materiales Avanzados, Apdo. Postal 311109, Chihuahua (Mexico); Alonso N, G. [UNAM, Centro de Nanociencias y Nanotecnologia, Carretera Tijuana-Ensenada Km 107, Apdo. Postal 356, 22800 Ensenada, Baja California (Mexico)

2013-07-01

Photo catalysis is a method widely used in the degradation of organic pollutants of the environment. The development of new materials is very important to improve the photo catalytic properties and to find new applications for TiO{sub 2} as a photo catalyst. In this article we reported the synthesis of a photo catalyst based on TiO{sub 2} doped with Zn{sup 2+} ions highly efficient in the degradation of nitrobenzene. The results of photo catalytic activity experiments showed that the Zn{sup 2+} doped TiO{sub 2} is more active that un-doped TiO{sub 2} catalyst with an efficiency of 99% for the nitrobenzene degradation at 120 min with an apparent rate constant of 35 x 10{sup -3} min{sup -1}. For the characterization of photo catalyst X-ray diffraction, transmission electron microscopy and Raman spectroscopy were used. (Author)

Catalytic burners in larger boiler appliances

Energy Technology Data Exchange (ETDEWEB)

Silversand, Fredrik; Persson, Mikael (Catator AB, Lund (Sweden))

2009-02-15

This project focuses on the scale up of a Catator's catalytic burner technology to enable retrofit installation in existing boilers and the design of new innovative combinations of catalytic burners and boilers. Different design approaches are discussed and evaluated in the report and suggestions are made concerning scale-up. Preliminary test data, extracted from a large boiler installation are discussed together with an accurate analysis of technical possibilities following an optimization of the boiler design to benefit from the advantages of catalytic combustion. The experimental work was conducted in close collaboration with ICI Caldaie (ICI), located in Verona, Italy. ICI is a leading European boiler manufacturer in the effect segment ranging from about 20 kWt to several MWt. The study shows that it is possibly to scale up the burner technology and to maintain low emissions. The boilers used in the study were designed around conventional combustion and were consequently not optimized for implementation of catalytic burners. From previous experiences it stands clear that the furnace volume can be dramatically decreased when applying catalytic combustion. In flame combustion, this volume is normally dimensioned to avoid flame impingement on cold surfaces and to facilitate completion of the gas-phase reactions. The emissions of nitrogen oxides can be reduced by decreasing the residence time in the furnace. Even with the over-dimensioned furnace used in this study, we easily reached emission values close to 35 mg/kWh. The emissions of carbon monoxide and unburned hydrocarbons were negligible (less than 5 ppmv). It is possible to decrease the emissions of nitrogen oxides further by designing the furnace/boiler around the catalytic burner, as suggested in the report. Simultaneously, the size of the boiler installation can be reduced greatly, which also will result in material savings, i.e. the production cost can be reduced. It is suggested to optimize the

Pyroelectrically Induced Pyro-Electro-Chemical Catalytic Activity of BaTiO3 Nanofibers under Room-Temperature Cold–Hot Cycle Excitations

OpenAIRE

Yuntao Xia; Yanmin Jia; Weiqi Qian; Xiaoli Xu; Zheng Wu; Zichen Han; Yuanting Hong; Huilin You; Muhammad Ismail; Ge Bai; Liwei Wang

2017-01-01

A pyro-electro-chemical catalytic dye decomposition using lead-free BaTiO3 nanofibers was realized under room-temperature cold–hot cycle excitation (30–47 °C) with a high Rhodamine B (RhB) decomposition efficiency ~99%, which should be ascribed to the product of pyro-electric effect and electrochemical redox reaction. Furthermore, the existence of intermediate product of hydroxyl radical in pyro-electro-chemical catalytic process was also observed. There is no significant decrease in pyro-ele...

Chemiluminescence analyzer of NOx as a high-throughput screening tool in selective catalytic reduction of NO

International Nuclear Information System (INIS)

Oh, Kwang Seok; Woo, Seong Ihl

2011-01-01

A chemiluminescence-based analyzer of NO x gas species has been applied for high-throughput screening of a library of catalytic materials. The applicability of the commercial NO x analyzer as a rapid screening tool was evaluated using selective catalytic reduction of NO gas. A library of 60 binary alloys composed of Pt and Co, Zr, La, Ce, Fe or W on Al 2 O 3 substrate was tested for the efficiency of NO x removal using a home-built 64-channel parallel and sequential tubular reactor. The NO x concentrations measured by the NO x analyzer agreed well with the results obtained using micro gas chromatography for a reference catalyst consisting of 1 wt% Pt on γ-Al 2 O 3 . Most alloys showed high efficiency at 275 °C, which is typical of Pt-based catalysts for selective catalytic reduction of NO. The screening with NO x analyzer allowed to select Pt-Ce (X) (X=1–3) and Pt–Fe (2) as the optimal catalysts for NO x removal: 73% NO x conversion was achieved with the Pt–Fe (2) alloy, which was much better than the results for the reference catalyst and the other library alloys. This study demonstrates a sequential high-throughput method of practical evaluation of catalysts for the selective reduction of NO.

Concentric catalytic combustor

Science.gov (United States)

Bruck, Gerald J [Oviedo, FL; Laster, Walter R [Oviedo, FL

2009-03-24

A catalytic combustor (28) includes a tubular pressure boundary element (90) having a longitudinal flow axis (e.g., 56) separating a first portion (94) of a first fluid flow (e.g., 24) from a second portion (95) of the first fluid flow. The pressure boundary element includes a wall (96) having a plurality of separate longitudinally oriented flow paths (98) annularly disposed within the wall and conducting respective portions (100, 101) of a second fluid flow (e.g., 26) therethrough. A catalytic material (32) is disposed on a surface (e.g., 102, 103) of the pressure boundary element exposed to at least one of the first and second portions of the first fluid flow.

Thermodynamic characteristics of a low concentration methane catalytic combustion gas turbine

International Nuclear Information System (INIS)

Yin, Juan; Su, Shi; Yu, Xin Xiang; Weng, Yiwu

2010-01-01

Low concentration methane, emitted from coal mines, landfill, animal waste, etc. into the atmosphere, is not only a greenhouse gas, but also a waste energy source if not utilised. Methane is 23 times more potent than CO 2 in terms of trapping heat in the atmosphere over a timeframe of 100 years. This paper studies a novel lean burn catalytic combustion gas turbine, which can be powered with about 1% methane (volume) in air. When this technology is successfully developed, it can be used not only to mitigate the methane for greenhouse gas reduction, but also to utilise such methane as a clean energy source. This paper presents our study results on the thermodynamic characteristics of this new lean burn catalytic combustion gas turbine system by conducting thermal performance analysis of the turbine cycle. The thermodynamic data including thermal efficiencies and exergy loss of main components of the turbine system are presented under different pressure ratios, turbine inlet temperatures and methane concentrations.

Effect of support on the catalytic activity of manganese oxide catalyts for toluene combustion.

Science.gov (United States)

Pozan, Gulin Selda

2012-06-30

The aim of this work was to study combustion of toluene (1000ppm) over MnO(2) modified with different supports. α-Al(2)O(3) and γ-Al(2)O(3) obtained from Boehmite, γ-Al(2)O(3) (commercial), SiO(2), TiO(2) and ZrO(2) were used as commercial support materials. In view of potential interest of this process, the influence of support material on the catalytic performance was discussed. The deposition of 9.5MnO(2) was performed by impregnation over support. The catalysts were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), temperature programmed reduction and oxidation (TPR/TPO) and thermogravimetric analysis (TGA). The catalytic tests were carried out at atmospheric pressure in a fixed-bed flow reactor. 9.5MnO(2)/α-Al(2)O(3)(B) (synthesized from Boehmite) catalyst exhibits the highest catalytic activity, over which the toluene conversion was up to 90% at a temperature of 289°C. Considering all the characterization and reaction data reported in this study, it was concluded that the manganese state and oxygen species played an important role in the catalytic activity. Copyright © 2012 Elsevier B.V. All rights reserved.

Efficient hydrogen evolution catalysis using ternary pyrite-type cobalt phosphosulphide

KAUST Repository

Cabán-Acevedo, Miguel

2015-09-14

The scalable and sustainable production of hydrogen fuel through water splitting demands efficient and robust Earth-abundant catalysts for the hydrogen evolution reaction (HER). Building on promising metal compounds with high HER catalytic activity, such as pyrite structure cobalt disulphide (CoS 2), and substituting non-metal elements to tune the hydrogen adsorption free energy could lead to further improvements in catalytic activity. Here we present a combined theoretical and experimental study to establish ternary pyrite-type cobalt phosphosulphide (CoPS) as a high-performance Earth-abundant catalyst for electrochemical and photoelectrochemical hydrogen production. Nanostructured CoPS electrodes achieved a geometrical catalytic current density of 10 mA cm at overpotentials as low as 48mV, with outstanding long-term operational stability. Integrated photocathodes of CoPS on n -p-p silicon micropyramids achieved photocurrents up to 35 mA cm at 0 V versus the reversible hydrogen electrode (RHE), onset photovoltages as high as 450 mV versus RHE, and the most efficient solar-driven hydrogen generation from Earth-abundant systems.

Novel catalytic micromotor of porous zeolitic imidazolate framework-67 for precise drug delivery.

Science.gov (United States)

Wang, Linlin; Zhu, Hongli; Shi, Ying; Ge, You; Feng, Xiaomiao; Liu, Ruiqing; Li, Yi; Ma, Yanwen; Wang, Lianhui

2018-06-07

Micromotors hold promise as drug carriers for targeted drug delivery owing to the characteristics of self-propulsion and directional navigation. However, several defects still exist, including high cost, short movement life, low drug loading and slow release rate. Herein, a novel catalytic micromotor based on porous zeolitic imidazolate framework-67 (ZIF-67) synthesized by a greatly simplified wet chemical method assisted with ultrasonication is described as an efficient anticancer drug carrier. These porous micromotors display effective autonomous motion in hydrogen peroxide and long durable movement life of up to 90 min. Moreover, the multifunctional micromotor ZIF-67/Fe3O4/DOX exhibits excellent performance in precise drug delivery under external magnetic field with high drug loading capacity of fluorescent anticancer drug DOX up to 682 μg mg-1 owing to its porous nature, high surface area and rapid drug release based on dual stimulus of catalytic reaction and solvent effects. Therefore, these porous ZIF-67-based catalytic micromotors combine the domains of metal-organic frameworks (MOFs) and micomotors, thus developing potential resources for micromotors and holding great potential as label-free and precisely controlled high-quality candidates of drug delivery systems for biomedical applications.

Soluble organic nanotubes for catalytic systems

Science.gov (United States)

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

2016-03-01

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.

Soluble organic nanotubes for catalytic systems.

Science.gov (United States)

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.

Predicting CYP2C19 Catalytic Parameters for Enantioselective Oxidations Using Artificial Neural Networks and a Chirality Code

Science.gov (United States)

Hartman, Jessica H.; Cothren, Steven D.; Park, Sun-Ha; Yun, Chul-Ho; Darsey, Jerry A.; Miller, Grover P.

2013-01-01

Cytochromes P450 (CYP for isoforms) play a central role in biological processes especially metabolism of chiral molecules; thus, development of computational methods to predict parameters for chiral reactions is important for advancing this field. In this study, we identified the most optimal artificial neural networks using conformation-independent chirality codes to predict CYP2C19 catalytic parameters for enantioselective reactions. Optimization of the neural networks required identifying the most suitable representation of structure among a diverse array of training substrates, normalizing distribution of the corresponding catalytic parameters (kcat, Km, and kcat/Km), and determining the best topology for networks to make predictions. Among different structural descriptors, the use of partial atomic charges according to the CHelpG scheme and inclusion of hydrogens yielded the most optimal artificial neural networks. Their training also required resolution of poorly distributed output catalytic parameters using a Box-Cox transformation. End point leave-one-out cross correlations of the best neural networks revealed that predictions for individual catalytic parameters (kcat and Km) were more consistent with experimental values than those for catalytic efficiency (kcat/Km). Lastly, neural networks predicted correctly enantioselectivity and comparable catalytic parameters measured in this study for previously uncharacterized CYP2C19 substrates, R- and S-propranolol. Taken together, these seminal computational studies for CYP2C19 are the first to predict all catalytic parameters for enantioselective reactions using artificial neural networks and thus provide a foundation for expanding the prediction of cytochrome P450 reactions to chiral drugs, pollutants, and other biologically active compounds. PMID:23673224

Catalytic residues Lys197 and Arg199 of Bacillus subtilis phosphoribosyl diphosphate synthase. Alanine-scanning mutagenesis of the flexible catalytic loop

DEFF Research Database (Denmark)

Hove-Jensen, Bjarne; Bentsen, Ann-Kristin K; Harlow, Kenneth W

2005-01-01

Eleven of the codons specifying the amino acids of the flexible catalytic loop [KRRPRPNVAEVM(197-208)] of Bacillus subtilis phosphoribosyl diphosphate synthase have been changed individually to specify alanine. The resulting variant enzyme forms, as well as the wildtype enzyme, were produced...... in an Escherichia coli strain lacking endogenous phosphoribosyl diphosphate synthase activity and purified to near homogeneity. The B. subtilis phosphoribosyl diphosphate synthase mutant variants K197A and R199A were studied in detail. The physical properties of the two enzymes were similar to those of the wildtype...

Catalytic Palladium Film Deposited by Scalable Low-Temperature Aqueous Combustion.

Science.gov (United States)

Voskanyan, Albert A; Li, Chi-Ying Vanessa; Chan, Kwong-Yu

2017-09-27

This article describes a novel method for depositing a dense, high quality palladium thin film via a one-step aqueous combustion process which can be easily scaled up. Film deposition of Pd from aqueous solutions by conventional chemical or electrochemical methods is inhibited by hydrogen embrittlement, thus resulting in a brittle palladium film. The method outlined in this work allows a direct aqueous solution deposition of a mirror-bright, durable Pd film on substrates including glass and glassy carbon. This simple procedure has many advantages including a very high deposition rate (>10 cm 2 min -1 ) and a relatively low deposition temperature (250 °C), which makes it suitable for large-scale industrial applications. Although preparation of various high-quality oxide films has been successfully accomplished via solution combustion synthesis (SCS) before, this article presents the first report on direct SCS production of a metallic film. The mechanism of Pd film formation is discussed with the identification of a complex formed between palladium nitrate and glycine at low temperature. The catalytic properties and stability of films are successfully tested in alcohol electrooxidation and electrochemical oxygen reduction reaction. It was observed that combustion deposited Pd film on a glassy carbon electrode showed excellent catalytic activity in ethanol oxidation without using any binder or additive. We also report for the first time the concept of a reusable "catalytic flask" as illustrated by the Suzuki-Miyaura cross-coupling reaction. The Pd film uniformly covers the inner walls of the flask and eliminates the catalyst separation step. We believe the innovative concept of a reusable catalytic flask is very promising and has the required features to become a commercial product in the future.

Catalytic models developed through social work

DEFF Research Database (Denmark)

Jensen, Mogens

2015-01-01

of adolescents placed in out-of-home care and is characterised using three situated cases as empirical data. Afterwards the concept of catalytic processes is briefly presented and then applied in an analysis of pedagogical treatment in the three cases. The result is a different conceptualisation of the social......The article develops the concept of catalytic processes in relation to social work with adolescents in an attempt to both reach a more nuanced understanding of social work and at the same time to develop the concept of catalytic processes in psychology. The social work is pedagogical treatment...

The DNA topoisomerase II catalytic inhibitor merbarone is genotoxic and induces endoreduplication

International Nuclear Information System (INIS)

Pastor, Nuria; Domínguez, Inmaculada; Orta, Manuel Luís; Campanella, Claudia; Mateos, Santiago; Cortés, Felipe

2012-01-01

In the last years a number of reports have shown that the so-called topoisomerase II (topo II) catalytic inhibitors are able to induce DNA and chromosome damage, an unexpected result taking into account that they do not stabilize topo II-DNA cleavable complexes, a feature of topo II poisons such as etoposide and amsacrine. Merbarone inhibits the catalytic activity of topo II by blocking DNA cleavage by the enzyme. While it was first reported that merbarone does not induce genotoxic effects in mammalian cells, this has been challenged by reports showing that the topo II inhibitor induces efficiently chromosome and DNA damage, and the question as to a possible behavior as a topo II poison has been put forward. Given these contradictory results, and the as yet incomplete knowledge of the molecular mechanism of action of merbarone, in the present study we have tried to further characterize the mechanism of action of merbarone on cell proliferation, cell cycle, as well as chromosome and DNA damage in cultured CHO cells. Merbarone was cytotoxic as well as genotoxic, inhibited topo II catalytic activity, and induced endoreduplication. We have also shown that merbarone-induced DNA damage depends upon ongoing DNA synthesis. Supporting this, inhibition of DNA synthesis causes reduction of DNA damage and increased cell survival.

[Mechanism of catalytic ozonation for the degradation of paracetamol by activated carbon].

Science.gov (United States)

Wang, Jia-Yu; Dai, Qi-Zhou; Yu, Jie; Yan, Yi-Zhou; Chen, Jian-Meng

2013-04-01

The degradation of paracetamol (APAP) in aqueous solution was studied with ozonation integrated with activated carbon (AC). The synergistic effect of ozonation/AC process was explored by comparing the degradation efficiency of APAP in three processes (ozonation alone, activated carbon alone and ozonation integrated with activated carbon). The operational parameters that affected the reaction rate were carefully optimized. Based on the intermediates detected, the possible pathway for catalytic degradation was discussed and the reaction mechanism was also investigated. The results showed that the TOC removal reached 55.11% at 60 min in the AC/O3 system, and was significantly better than the sum of ozonation alone (20.22%) and activated carbon alone (27.39%), showing the great synergistic effect. And the BOD5/COD ratio increased from 0.086 (before reaction) to 0.543 (after reaction), indicating that the biodegradability was also greatly improved. The effects of the initial concentration of APAP, pH value, ozone dosage and AC dosage on the variation of reaction rate were carefully discussed. The catalytic reaction mechanism was different at different pH values: the organic pollutions were removed by adsorption and direct ozone oxidation at acidic pH, and mainly by catalytic ozonation at alkaline pH.

Catalytic ozonation of pentachlorophenol in aqueous solutions using granular activated carbon

Science.gov (United States)

Asgari, Ghorban; Samiee, Fateme; Ahmadian, Mohammad; Poormohammadi, Ali; solimanzadeh, Bahman

2017-03-01

The efficiency of granular activated carbon (GAC) was investigated in this study as a catalyst for the elimination of pentachlorophenol (PCP) from contaminated streams in a laboratory-scale semi-batch reactor. The influence of important parameters including solution pH (2-10), radical scavenger (tert-butanol, 0.04 mol/L), catalyst dosage (0.416-8.33 g/L), initial PCP concentration (100-1000 mg/L) and ozone flow rate (2.3-12 mg/min) was examined on the efficiency of the catalytic ozonation process (COP) in degradation and mineralization of PCP in aqueous solution. The experimental results showed that catalytic ozonation with GAC was most effective at pH of 8 with ozone flow rate of 12 mg/min and a GAC dosage of 2 g. Compared to the sole ozonation process (SOP), the removal levels of PCP and COP were, 98, and 79 %, respectively. The degradation rate of kinetics was also investigated. The results showed that using a GAC catalyst in the ozonation of PCP produced an 8.33-fold increase in rate kinetic compared to the SOP under optimum conditions. Tert-butanol alcohol (TBA) was used as a radical scavenger. The results demonstrated that COP was affected less by TBA than by SOP. These findings suggested that GAC acts as a suitable catalyst in COP to remove refractory pollutants from aqueous solution.

Detailed modelling of processes inside a catalytic recombiner for hydrogen removal

International Nuclear Information System (INIS)

Heitsch, M.

1999-01-01

Under accidental conditions, considerable amounts of hydrogen may be released into the containment. Catalytic reacting surfaces in recombiners are a reliable method to recombine this hydrogen and other burnable gases like carbon monoxide from the atmosphere in a passive way. Many experiments have been carried out to study the main phenomena occurring inside recombiners, like the efficiency of hydrogen removal, the start-up conditions, poisoning, oxygen starvation, steam and water impact, and others. In addition, the global behavior of a given recombiner device in a larger environment has been investigated in order to demonstrate the effectiveness and to facilitate the derivation of simplified models for long term, severe accident analyses. These long-term severe accident models are complemented by detailed investigations to understand the interaction of chemistry and flow inside a recombiner box. This helps to provide the dependencies of non-measurable variables (e.g. the reaction rate distribution), of local surface temperatures etc. to make long-term or system models more reliable. It also offers possibilities for increasing the chemical efficiency by optimising the geometric design properly. Computational Fluid Dynamics (CFD) codes are available for use as development tools to include the specifics of catalytic surface reactors. The present paper describes the use of the code system CFX [1] for creating a recombiner model. Some model predictions are compared to existing test data. (author)

An efficient closed-form solution for acoustic emission source location in three-dimensional structures

Directory of Open Access Journals (Sweden)

Xibing Li

2014-02-01

Full Text Available This paper presents an efficient closed-form solution (ECS for acoustic emission(AE source location in three-dimensional structures using time difference of arrival (TDOA measurements from N receivers, N ≥ 6. The nonlinear location equations of TDOA are simplified to linear equations. The unique analytical solution of AE sources for unknown velocity system is obtained by solving the linear equations. The proposed ECS method successfully solved the problems of location errors resulting from measured deviations of velocity as well as the existence and multiplicity of solutions induced by calculations of square roots in existed close-form methods.

On the functional form of an efficiency index

DEFF Research Database (Denmark)

Hougaard, Jens Leth; Keiding, Hans

1998-01-01

An input efficiency index gives a numeric assessment of the degree to which a given input combination falls short of being efficient in producing a fixed amount of output. This paper presents a system of axioms which characterise a certain family of efficiency indices containing the well-known Fa...

Catalytically favorable surface patterns in Pt-Au nanoclusters

KAUST Repository

Mokkath, Junais Habeeb

2013-01-01

Motivated by recent experimental demonstrations of novel PtAu nanoparticles with highly enhanced catalytic properties, we present a systematic theoretical study that explores principal catalytic indicators as a function of the particle size and composition. We find that Pt electronic states in the vicinity of the Fermi level combined with a modified electron distribution in the nanoparticle due to Pt-to-Au charge transfer are the origin of the outstanding catalytic properties. From our model we deduce the catalytically favorable surface patterns that induce ensemble and ligand effects. © The Royal Society of Chemistry 2013.

Synthesis and Investigation the Catalytic Behavior of Cr2O3 Nanoparticles

Directory of Open Access Journals (Sweden)

R. Karimian

2013-03-01

Full Text Available The use of an inorganic phase in water-in-oil (w/o microemulsion has recently received considerable attention for preparing metal oxide nanoparticles. This is a technique, which allows preparation of ultrafine metal oxide nanoparticles within the size range 40 to 80 nm. Preparation of nano chromium (III oxide studied investigated in the inverse microemulsion system. Therefore the nucleation of metal particles proceeds in the water capsules of the microemulsion. the main advantage of this method is easily controllable conditions with using low cost chromium source is merit to be considered for scaling up by industrial researchers. Besides we mainly focus on the catalytic property nano chromium (III oxide. Oxidation of aromatic aldehyde/alcohol to the corresponding carboxylic acids can be performed highly efficiently in the presence of a catalytic amount of nano chromium (III oxide in THF as solvent under mild conditions.

Research progress on catalytic denitrification technology in chemical industry

Science.gov (United States)

Jin, Yezhi

2017-12-01

In recent years, due to the rising emission of NOx annually, attention has been aroused widely by people on more and more severe environmental problems. This paper first discusses applying NOx removal and control technologies and relating chemical principles. Of many technologies, selective reduction reaction (SCR) is the most widely used. Catalysts, the concentration of NOx at the entrance of SCR catalytic reactor, reaction temperature, NH3/NOx mole ratio and NH3 slip rate analyzed later contributes to the removal efficiency of NOx. Finally, the processing and configuration of SCR de-NOx system are briefly introduced.

Evaluation of catalytic combustion of actual coal-derived gas

Science.gov (United States)

Blanton, J. C.; Shisler, R. A.

1982-01-01

The combustion characteristics of a Pt-Pl catalytic reactor burning coal-derived, low-Btu gas were investigated. A large matrix of test conditions was explored involving variations in fuel/air inlet temperature and velocity, reactor pressure, and combustor exit temperature. Other data recorded included fuel gas composition, reactor temperatures, and exhaust emissions. Operating experience with the reactor was satisfactory. Combustion efficiencies were quite high (over 95 percent) over most of the operating range. Emissions of NOx were quite high (up to 500 ppm V and greater), owing to the high ammonia content of the fuel gas.

Fabrication of highly electro catalytic active layer of multi walled carbon nanotube/enzyme for Pt-free dye sensitized solar cells

Energy Technology Data Exchange (ETDEWEB)

Arbab, Alvira Ayoub, E-mail: alvira_arbab@yahoo.com [Department of Organic and Nano Engineering, Hanyang University, Seoul 133-791 (Korea, Republic of); Sun, Kyung Chul, E-mail: hytec@hanyang.ac.kr [Department of Fuel cells and hydrogen technology, Hanyang University, Seoul 133-791 (Korea, Republic of); Sahito, Iftikhar Ali, E-mail: iftikhar.sahito@faculty.muet.edu.pk [Department of Organic and Nano Engineering, Hanyang University, Seoul 133-791 (Korea, Republic of); Qadir, Muhammad Bilal, E-mail: bilal_ntu81@hotmail.com [Department of Organic and Nano Engineering, Hanyang University, Seoul 133-791 (Korea, Republic of); Jeong, Sung Hoon, E-mail: shjeong@hanyang.ac.kr [Department of Organic and Nano Engineering, Hanyang University, Seoul 133-791 (Korea, Republic of)

2015-09-15

Graphical abstract: - Highlights: • We prepared three different types of enzyme dispersed multiwall carbon nanotube (E-MWCNT) layer for application in Pt-free dye sensitized solar cell (DSSCs). • E-MWCNT catalysts exhibited an extremely good electro-catalytic activity (ECA), compared with the conventional catalyst, when synthesized with lipase enzyme. • E-MWCNT as counter electrode exhibits a high power conversion efficiency (PCE) of 7.5%, which can be compared to 8% efficiency of Pt catalyst. - Abstract: Highly dispersed conductive suspensions of multi walled carbon nanotubes (MWCNT) can have intrinsic electrical and electrochemical characteristics, which make them useful candidate for platinum (Pt)-free, dye sensitized solar cells (DSSCs). High energy conversion efficiency of 7.52% is demonstrated in DSSCs, based on enzyme dispersed MWCNT (E-MWCNT) layer deposited on fluorine doped tin oxide (FTO) glass. The E-MWCNT layer shows a pivotal role as platform to reduce large amount of iodide species via electro catalytically active layer, fabricated by facile tape casting under air drying technique. The E-MWCNT layer with large surface area, high mechanical adhesion, and good interconnectivity is derived from an appropriate enzyme dispersion, which provides not only enhanced interaction sites for the electrolyte/counter electrode interface but also improved electron transport mechanism. The surface morphology and structural characterization were investigated using field emission-scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), x-ray photoelectron spectroscopy (XPS), Raman spectroscopy and electronic microscopy techniques. Electro catalytic activity (ECA) and electrochemical properties of E-MWCNT counter electrode (CE) were investigated using cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS) measurements. The high power conversion efficiency (PCE) of E-MWCNT CE is associated with the low charge transfer

Fabrication of highly electro catalytic active layer of multi walled carbon nanotube/enzyme for Pt-free dye sensitized solar cells

International Nuclear Information System (INIS)

Arbab, Alvira Ayoub; Sun, Kyung Chul; Sahito, Iftikhar Ali; Qadir, Muhammad Bilal; Jeong, Sung Hoon

2015-01-01

Graphical abstract: - Highlights: • We prepared three different types of enzyme dispersed multiwall carbon nanotube (E-MWCNT) layer for application in Pt-free dye sensitized solar cell (DSSCs). • E-MWCNT catalysts exhibited an extremely good electro-catalytic activity (ECA), compared with the conventional catalyst, when synthesized with lipase enzyme. • E-MWCNT as counter electrode exhibits a high power conversion efficiency (PCE) of 7.5%, which can be compared to 8% efficiency of Pt catalyst. - Abstract: Highly dispersed conductive suspensions of multi walled carbon nanotubes (MWCNT) can have intrinsic electrical and electrochemical characteristics, which make them useful candidate for platinum (Pt)-free, dye sensitized solar cells (DSSCs). High energy conversion efficiency of 7.52% is demonstrated in DSSCs, based on enzyme dispersed MWCNT (E-MWCNT) layer deposited on fluorine doped tin oxide (FTO) glass. The E-MWCNT layer shows a pivotal role as platform to reduce large amount of iodide species via electro catalytically active layer, fabricated by facile tape casting under air drying technique. The E-MWCNT layer with large surface area, high mechanical adhesion, and good interconnectivity is derived from an appropriate enzyme dispersion, which provides not only enhanced interaction sites for the electrolyte/counter electrode interface but also improved electron transport mechanism. The surface morphology and structural characterization were investigated using field emission-scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), x-ray photoelectron spectroscopy (XPS), Raman spectroscopy and electronic microscopy techniques. Electro catalytic activity (ECA) and electrochemical properties of E-MWCNT counter electrode (CE) were investigated using cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS) measurements. The high power conversion efficiency (PCE) of E-MWCNT CE is associated with the low charge transfer

Structural Insight into the Critical Role of the N-Terminal Region in the Catalytic Activity of Dual-Specificity Phosphatase 26.

Directory of Open Access Journals (Sweden)

Eun-Young Won

Full Text Available Human dual-specificity phosphatase 26 (DUSP26 is a novel target for anticancer therapy because its dephosphorylation of the p53 tumor suppressor regulates the apoptosis of cancer cells. DUSP26 inhibition results in neuroblastoma cell cytotoxicity through p53-mediated apoptosis. Despite the previous structural studies of DUSP26 catalytic domain (residues 61-211, DUSP26-C, the high-resolution structure of its catalytically active form has not been resolved. In this study, we determined the crystal structure of a catalytically active form of DUSP26 (residues 39-211, DUSP26-N with an additional N-terminal region at 2.0 Å resolution. Unlike the C-terminal domain-swapped dimeric structure of DUSP26-C, the DUSP26-N (C152S monomer adopts a fold-back conformation of the C-terminal α8-helix and has an additional α1-helix in the N-terminal region. Consistent with the canonically active conformation of its protein tyrosine phosphate-binding loop (PTP loop observed in the structure, the phosphatase assay results demonstrated that DUSP26-N has significantly higher catalytic activity than DUSP26-C. Furthermore, size exclusion chromatography-multiangle laser scattering (SEC-MALS measurements showed that DUSP26-N (C152S exists as a monomer in solution. Notably, the crystal structure of DUSP26-N (C152S revealed that the N-terminal region of DUSP26-N (C152S serves a scaffolding role by positioning the surrounding α7-α8 loop for interaction with the PTP-loop through formation of an extensive hydrogen bond network, which seems to be critical in making the PTP-loop conformation competent for phosphatase activity. Our study provides the first high-resolution structure of a catalytically active form of DUSP26, which will contribute to the structure-based rational design of novel DUSP26-targeting anticancer therapeutics.

Turning goals into results: the power of catalytic mechanisms.

Science.gov (United States)

Collins, J

1999-01-01

Most executives have a big, hairy, audacious goal. They write vision statements, formalize procedures, and develop complicated incentive programs--all in pursuit of that goal. In other words, with the best of intentions, they install layers of stultifying bureaucracy. But it doesn't have to be that way. In this article, Jim Collins introduces the catalytic mechanism, a simple yet powerful managerial tool that helps translate lofty aspirations into concrete reality. Catalytic mechanisms are the crucial link between objectives and performance; they are a galvanizing, nonbureaucratic means to turn one into the other. What's the difference between catalytic mechanisms and most traditional managerial controls? Catalytic mechanisms share five characteristics. First, they produce desired results in unpredictable ways. Second, they distribute power for the benefit of the overall system, often to the discomfort of those who traditionally hold power. Third, catalytic mechanisms have teeth. Fourth, they eject "viruses"--those people who don't share the company's core values. Finally, they produce an ongoing effect. Catalytic mechanisms are just as effective for reaching individual goals as they are for corporate ones. To illustrate how catalytic mechanisms work, the author draws on examples of individuals and organizations that have relied on such mechanisms to achieve their goals. The same catalytic mechanism that works in one organization, however, will not necessarily work in another. Catalytic mechanisms must be tailored to specific goals and situations. To help readers get started, the author offers some general principles that support the process of building catalytic mechanisms effectively.

The N domain of somatic angiotensin-converting enzyme negatively regulates ectodomain shedding and catalytic activity

OpenAIRE

Woodman, Zenda L.; Schwager, Sylva L. U.; Redelinghuys, Pierre; Carmona, Adriana K.; Ehlers, Mario R. W.; Sturrock, Edward D.

2005-01-01

sACE (somatic angiotensin-converting enzyme) consists of two homologous, N and C domains, whereas the testis isoenzyme [tACE (testis ACE)] consists of a single C domain. Both isoenzymes are shed from the cell surface by a sheddase activity, although sACE is shed much less efficiently than tACE. We hypothesize that the N domain of sACE plays a regulatory role, by occluding a recognition motif on the C domain required for ectodomain shedding and by influencing the catalytic efficiency. To test ...

Atomically Precise Metal Nanoclusters for Catalytic Application

Energy Technology Data Exchange (ETDEWEB)

Jin, Rongchao [Carnegie Mellon Univ., Pittsburgh, PA (United States)

2016-11-18

The central goal of this project is to explore the catalytic application of atomically precise gold nanoclusters. By solving the total structures of ligand-protected nanoclusters, we aim to correlate the catalytic properties of metal nanoclusters with their atomic/electronic structures. Such correlation unravel some fundamental aspects of nanocatalysis, such as the nature of particle size effect, origin of catalytic selectivity, particle-support interactions, the identification of catalytically active centers, etc. The well-defined nanocluster catalysts mediate the knowledge gap between single crystal model catalysts and real-world conventional nanocatalysts. These nanoclusters also hold great promise in catalyzing certain types of reactions with extraordinarily high selectivity. These aims are in line with the overall goals of the catalytic science and technology of DOE and advance the BES mission “to support fundamental research to understand, predict, and ultimately control matter and energy at the level of electrons, atoms, and molecules”. Our group has successfully prepared different sized, robust gold nanoclusters protected by thiolates, such as Au₂₅(SR)₁₈, Au₂₈(SR)₂₀, Au₃₈(SR)₂₄, Au₉₉(SR)₄₂, Au₁₄₄(SR)₆₀, etc. Some of these nanoclusters have been crystallographically characterized through X-ray crystallography. These ultrasmall nanoclusters (< 2 nm diameter) exhibit discrete electronic structures due to quantum size effect, as opposed to quasicontinuous band structure of conventional metal nanoparticles or bulk metals. The available atomic structures (metal core plus surface ligands) of nanoclusters serve as the basis for structure-property correlations. We have investigated the unique catalytic properties of nanoclusters (i.e. not observed in conventional nanogold catalysts) and revealed the structure-selectivity relationships. Highlights of our

Critical Role of Interdomain Interactions in the Conformational Change and Catalytic Mechanism of Endoplasmic Reticulum Aminopeptidase 1.

Science.gov (United States)

Stamogiannos, Athanasios; Maben, Zachary; Papakyriakou, Athanasios; Mpakali, Anastasia; Kokkala, Paraskevi; Georgiadis, Dimitris; Stern, Lawrence J; Stratikos, Efstratios

2017-03-14

Endoplasmic reticulum aminopeptidase 1 (ERAP1) is an intracellular enzyme that is important for the generation of antigenic epitopes and major histocompatibility class I-restricted adaptive immune responses. ERAP1 processes a vast variety of different peptides but still shows length and sequence selectivity, although the mechanism behind these properties is poorly understood. X-ray crystallographic analysis has revealed that ERAP1 can assume at least two distinct conformations in which C-terminal domain IV is either proximal or distal to active site domain II. To improve our understanding of the role of this conformational change in the catalytic mechanism of ERAP1, we used site-directed mutagenesis to perturb key salt bridges between domains II and IV. Enzymatic analysis revealed that these mutations, although located away from the catalytic site, greatly reduce the catalytic efficiency and change the allosteric kinetic behavior. The variants were more efficiently activated by small peptides and bound a competitive inhibitor with weaker affinity and faster dissociation kinetics. Molecular dynamics analysis suggested that the mutations affect the conformational distribution of ERAP1, reducing the population of closed states. Small-angle X-ray scattering indicated that both the wild type and the ERAP1 variants are predominantly in an open conformational state in solution. Overall, our findings suggest that electrostatic interactions between domains II and IV in ERAP1 are crucial for driving a conformational change that regulates the structural integrity of the catalytic site. The extent of domain opening in ERAP1 probably underlies its specialization for antigenic peptide precursors and should be taken into account in inhibitor development efforts.

Ni0 encapsulated in N-doped carbon nanotubes for catalytic reduction of highly toxic hexavalent chromium

Science.gov (United States)

Yao, Yunjin; Zhang, Jie; Chen, Hao; Yu, Maojing; Gao, Mengxue; Hu, Yi; Wang, Shaobin

2018-05-01

N-doped carbon nanotubes encapsulating Ni0 nanoparticles (Ni@N-C) were fabricated via thermal reduction of dicyandiamide and NiCl2·6H2O, and used to remove CrVI in polluted water. The resultant products present an excellent catalytic activity for CrVI reduction using formic acid under relatively mild conditions. The CrVI reduction efficiency of Ni@N-C was significantly affected by the preparation conditions including the mass of nickel salt and synthesis temperatures. The impacts of several reaction parameters, such as initial concentrations of CrVI and formic acid, solution pH and temperatures, as well as inorganic anions in solution on CrVI reduction efficiency were also evaluated in view of scalable industrial applications. Owing to the synergistic effects amongst tubes-coated Ni0, doped nitrogen, oxygen containing groups, and the configuration of carbon nanotubes, Ni@N-C catalysts exhibit excellent catalytic activity and recyclable capability for CrVI reduction. Carbon shell can efficiently protect inner Ni0 core and N species from corrosion and subsequent leaching, while Ni0 endows the Ni@N-C catalysts with ferromagnetism, so that the composites can be easily separated via a permanent magnet. This study opens up an avenue for design of N-doped carbon nanotubes encapsulating Ni0 nanoparticles with high CrVI removal efficiency and magnetic recyclability as low-cost catalysts for industrial applications.

In situ catalytic growth of large-area multilayered graphene/MoS2 heterostructures

Science.gov (United States)

Fu, Wei; Du, Fei-Hu; Su, Juan; Li, Xin-Hao; Wei, Xiao; Ye, Tian-Nan; Wang, Kai-Xue; Chen, Jie-Sheng

2014-04-01

Stacking various two-dimensional atomic crystals on top of each other is a feasible approach to create unique multilayered heterostructures with desired properties. Herein for the first time, we present a controlled preparation of large-area graphene/MoS2 heterostructures via a simple heating procedure on Mo-oleate complex coated sodium sulfate under N2 atmosphere. Through a direct in situ catalytic reaction, graphene layer has been uniformly grown on the MoS2 film formed by the reaction of Mo species with S pecies, which is from the carbothermal reduction of sodium sulfate. Due to the excellent graphene ``painting'' on MoS2 atomic layers, the significantly shortened lithium ion diffusion distance and the markedly enhanced electronic conductivity, these multilayered graphene/MoS2 heterostructures exhibit high specific capacity, unprecedented rate performance and outstanding cycling stability, especially at a high current density, when used as an anode material for lithium batteries. This work provides a simple but efficient route for the controlled fabrication of large-area multilayered graphene/metal sulfide heterostructures with promising applications in battery manufacture, electronics or catalysis.

Catalytic Conversion of Cellulose to Levulinic Acid by Metal Chlorides

Directory of Open Access Journals (Sweden)

Beixiao Zhang

2010-08-01

Full Text Available The catalytic performance of various metal chlorides in the conversion of cellulose to levulinic acid in liquid water at high temperatures was investigated. The effects of reaction parameters on the yield of levulinic acid were also explored. The results showed that alkali and alkaline earth metal chlorides were not effective in conversion of cellulose, while transition metal chlorides, especially CrCl3, FeCl3 and CuCl2 and a group IIIA metal chloride (AlCl3, exhibited high catalytic activity. The catalytic performance was correlated with the acidity of the reaction system due to the addition of the metal chlorides, but more dependent on the type of metal chloride. Among those metal chlorides, chromium chloride was found to be exceptionally effective for the conversion of cellulose to levulinic acid, affording an optimum yield of 67 mol % after a reaction time of 180 min, at 200 °C, with a catalyst dosage of 0.02 M and substrate concentration of 50 wt %. Chromium metal, most of which was present in its oxide form in the solid sample and only a small part in solution as Cr3+ ion, can be easily separated from the resulting product mixture and recycled. Finally, a plausible reaction scheme for the chromium chloride catalyzed conversion of cellulose in water was proposed.

High electro-catalytic activities of glucose oxidase embedded one-dimensional ZnO nanostructures

International Nuclear Information System (INIS)

Sarkar, Nirmal K; Bhattacharyya, Swapan K

2013-01-01

One-dimensional ZnO nanorods and nanowires are separately synthesized on Zn substrate by simple hydrothermal processes at low temperatures. Electro-catalytic responses of glucose oxidase/ZnO/Zn electrodes using these two synthesized nanostructures of ZnO are reported and compared with others available in literature. It is apparent the Michaelis–Menten constant, K M app , for the present ZnO nanowire, having a greater aspect ratio, is found to be the lowest when compared with others. This sensor shows lower oxidation peak potential with a long detection range of 6.6 μM–380 mM and the highest sensitivity of ∼35.1 μA cm −2 mM −1 , among the reported values in the literature. Enzyme catalytic efficiency and turnover numbers are also found to be remarkably high. (paper)

Kinetic Parameters of Non-Isothermal Thermogravimetric Non-Catalytic and Catalytic Pyrolysis of Empty Fruit Bunch with Alumina by Kissinger and Ozawa Methods

Science.gov (United States)

Rahayu Mohamed, Alina; Li, Nurfahani; Sohaimi, Khairunissa Syairah Ahmad; Izzati Iberahim, Nur; Munirah Rohaizad, Nor; Hamzah, Rosniza

2018-03-01

The non-isothermal thermogravimetric non-catalytic and catalytic empty fruit bunch (EFB) pyrolysis with alumina were performed at different heating rates of 10, 15, 20, 25, 30 and 40 K/min under nitrogen atmosphere at a flow rate of 100 ml/min under dynamic conditions from 301 K to 1273 K. The activation energy were calculated based on Kissinger and Ozawa methods. Both reactions followed first order reactions. By Kissinger method, the activation energy and Ln A values for non-catalytic and catalytic EFB pyrolysis with alumina were 188.69 kJ mol-1 and 201.67 kJ/mol respectively. By Ozawa method, the activation energy values for non-catalytic and catalytic EFB pyrolysis with alumina were 189.13 kJ/mol and 201.44 kJ/mol respectively. The presence of catalyst increased the activation energy values for EFB pyrolysis as calculated by Kissinger and Ozawa methods.

Examination of bacterial inhibition using a catalytic DNA.

Directory of Open Access Journals (Sweden)

Long Qu

Full Text Available Determination of accurate dosage of existing antibiotics and discovery of new antimicrobials or probiotics entail simple but effective methods that can conveniently track bacteria growth and inhibition. Here we explore the application of a previously reported fluorogenic E. coli-specific DNAzyme (catalytic DNA, RFD-EC1, as a molecular probe for monitoring bacterial inhibition exerted by antibiotics and for studying bacterial competition as a result of cohabitation. Because the DNAzyme method provides a convenient way to monitor the growth of E. coli, it is capable of determining the minimal inhibitory concentration (MIC of antibiotics much faster than the conventional optical density (OD method. In addition, since the target for RFD-EC1 is an extracellular protein molecule from E. coli, RFD-EC1 is able to identify pore-forming antibiotics or compounds that can cause membrane leakage. Finally, RFD-EC1 can be used to analyse the competition of cohabitating bacteria, specifically the inhibition of growth of E. coli by Bacillus subtilis. The current work represents the first exploration of a catalytic DNA for microbiological applications and showcases the utility of bacteria-sensing fluorogenic DNAzymes as simple molecular probes to facilitate antibiotic and probiotic research.

Catalytic properties and biomedical applications of cerium oxide nanoparticles

KAUST Repository

Walkey, Carl D.; Das, Soumen C.; Seal, Sudipta; Erlichman, Joseph S.; Heckman, Karin L.; Ghibelli, Lina; Traversa, Enrico; McGinnis, James F.; Self, William Thomas

2014-01-01

Cerium oxide nanoparticles (nanoceria) have shown promise as catalytic antioxidants in the test tube, cell culture models and animal models of disease. However given the reactivity that is well established at the surface of these nanoparticles, the biological utilization of nanoceria as a therapeutic still poses many challenges. Moreover the form that these particles take in a biological environment, such as the changes that can occur due to a protein corona, are not well established. This review aims to summarize the existing literature on biological use of nanoceria, and to raise questions about what further study is needed to apply this interesting catalytic material to biomedical applications. These questions include: 1) How does preparation, exposure dose, route and experimental model influence the reported effects of nanoceria in animal studies? 2) What are the considerations to develop nanoceria as a therapeutic agent in regards to these parameters? 3) What biological targets of reactive oxygen species (ROS) and reactive nitrogen species (RNS) are relevant to this targeting, and how do these properties also influence the safety of these nanomaterials?

Catalytic properties and biomedical applications of cerium oxide nanoparticles

KAUST Repository

Walkey, Carl D.

2014-11-10

Cerium oxide nanoparticles (nanoceria) have shown promise as catalytic antioxidants in the test tube, cell culture models and animal models of disease. However given the reactivity that is well established at the surface of these nanoparticles, the biological utilization of nanoceria as a therapeutic still poses many challenges. Moreover the form that these particles take in a biological environment, such as the changes that can occur due to a protein corona, are not well established. This review aims to summarize the existing literature on biological use of nanoceria, and to raise questions about what further study is needed to apply this interesting catalytic material to biomedical applications. These questions include: 1) How does preparation, exposure dose, route and experimental model influence the reported effects of nanoceria in animal studies? 2) What are the considerations to develop nanoceria as a therapeutic agent in regards to these parameters? 3) What biological targets of reactive oxygen species (ROS) and reactive nitrogen species (RNS) are relevant to this targeting, and how do these properties also influence the safety of these nanomaterials?

Enhanced photo-catalytic activity of ordered mesoporous indium oxide nanocrystals in the conversion of CO2 into methanol.

Science.gov (United States)

Gondal, M A; Dastageer, M A; Oloore, L E; Baig, U; Rashid, S G

2017-07-03

Ordered mesoporous indium oxide nanocrystal (m-In 2 O 3 ) was synthesized by nanocasting technique, in which highly ordered mesoporous silca (SBA-15) was used as structural matrix. X-ray diffraction (XRD), Field Emission Scanning Electron Microscopy (FESEM) Brunauer-Emmett-Teller (BET) and Barrett-Joyner-Halanda (BJH) studies were carried out on m-In 2 O 3 and the results revealed that this material has a highly ordered mesoporous surface with reduced grain size, increased surface area and surface volume compared to the non porous indium oxide. The diffuse reluctance spectrum exhibited substantially improved light absorption efficiency in m-In 2 O 3 compared to normal indium oxide, however, no considerable change in the band gap energies of these materials was observed. When m-In 2 O 3 was used as a photo-catalyst in the photo-catalytic process of converting carbon dioxide (CO 2 ) into methanol under the pulsed laser radiation of 266-nm wavelengths, an enhanced photo-catalytic activity with the quantum efficiency of 4.5% and conversion efficiency of 46.3% were observed. It was found that the methanol production yield in this chemical process is as high as 485 µlg -1 h -1 after 150 min of irradiation, which is substantially higher than the yields reported in the literature. It is quite clear from the results that the introduction of mesoporosity in indium oxide, and the consequent enhancement of positive attributes required for a photo-catalyst, transformed photo-catalytically weak indium oxide into an effective photo-catalyst for the conversion of CO 2 into methanol.

A Review on Catalytic Membranes Production and Applications

Directory of Open Access Journals (Sweden)

Heba Abdallah

2017-05-01

Full Text Available The development of the chemical industry regarding reducing the production cost and obtaining a high-quality product with low environmental impact became the essential requirements of the world in these days. The catalytic membrane is considered as one of the new alternative solutions of catalysts problems in the industries, where the reaction and separation can be amalgamated in one unit. The catalytic membrane has numerous advantages such as breaking the thermodynamic equilibrium limitation, increasing conversion rate, reducing the recycle and separation costs. But the limitation or most disadvantages of catalytic membranes related to the high capital costs for fabrication or the fact that manufacturing process is still under development. This review article summarizes the most recent advances and research activities related to preparation, characterization, and applications of catalytic membranes. In this article, various types of catalytic membranes are displayed with different applications and explained the positive impacts of using catalytic membranes in various reactions. Copyright © 2017 BCREC Group. All rights reserved. Received: 1st April 2016; Revised: 14th February 2017; Accepted: 22nd February 2017 How to Cite: Abdallah, H. (2017. A Review on Catalytic Membranes Production and Applications. Bulletin of Chemical Reaction Engineering & Catalysis, 12 (2: 136-156 (doi:10.9767/bcrec.12.2.462.136-156 Permalink/DOI: http://dx.doi.org/10.9767/bcrec.12.2.462.136-156

TEMPO functionalized C{sub 60} fullerene deposited on gold surface for catalytic oxidation of selected alcohols

Energy Technology Data Exchange (ETDEWEB)

Piotrowski, Piotr; Pawłowska, Joanna [University of Warsaw, Department of Chemistry (Poland); Sadło, Jarosław Grzegorz [Institute of Nuclear Chemistry and Technology (Poland); Bilewicz, Renata; Kaim, Andrzej, E-mail: akaim@chem.uw.edu.pl [University of Warsaw, Department of Chemistry (Poland)

2017-05-15

C{sub 60}TEMPO{sub 10} catalytic system linked to a microspherical gold support through a covalent S-Au bond was developed. The C{sub 60}TEMPO{sub 10}@Au composite catalyst had a particle size of 0.5–0.8 μm and was covered with the fullerenes derivative of 2.3 nm diameter bearing ten nitroxyl groups; the organic film showed up to 50 nm thickness. The catalytic composite allowed for the oxidation under mild conditions of various primary and secondary alcohols to the corresponding aldehyde and ketone analogues with efficiencies as high as 79–98%, thus giving values typical for homogeneous catalysis, while retaining at the same time all the advantages of heterogeneous catalysis, e.g., easy separation by filtration from the reaction mixture. The catalytic activity of the resulting system was studied by means of high pressure liquid chromatography. A redox mechanism was proposed for the process. In the catalytic cycle of the oxidation process, the TEMPO moiety was continuously regenerated in situ with an applied primary oxidant, for example, O{sub 2}/Fe{sup 3+} system. The new intermediate composite components and the final catalyst were characterized by various spectroscopic methods and thermogravimetry.

Fabrication of palladium nanoparticles immobilized on an amine-functionalized ceramic membrane support using a nanoparticulate colloidal impregnation method with enhanced catalytic properties

Energy Technology Data Exchange (ETDEWEB)

Du, Yan; Chen, Rizhi [Nanjing Tech University, Nanjing (China)

2015-09-15

An efficient and reusable catalyst was developed by depositing palladium nanoparticles on an amine-functionalized ceramic membrane support using a nanoparticulate colloidal impregnation method. The as-prepared Pdloaded ceramic membrane support was characterized by XRD, SEM, EDS, TEM, XPS, ICP, and its catalytic properties were investigated in the liquid-phase p-nitrophenol hydrogenation. A comparative study was also made with the palladium nanoparticles deposited on an amine-functionalized ceramic membrane support by an impregnation-reduction method. The palladium nanoparticles could be homogeneously immobilized on the ceramic membrane support surface, and exhibited excellent catalytic performance in the p-nitrophenol hydrogenation. The catalytic activity of the Pdloaded ceramic membrane support prepared by the nanoparticulate colloidal impregnation method increased by 16.6% compared to that of impregnation-reduction method. In the nanoparticulate colloidal impregnation method, palladium nanoparticles were presynthesized, higher loading of Pd(0) could be obtained, resulting in better catalytic activity. The as-prepared Pd-loaded ceramic membrane support could be easily reused for several cycles without appreciable degradation of catalytic activity.

Efficient C-O and C-N bond forming cross-coupling reactions catalyzed by core-shell structured Cu/Cu2O nanowires

KAUST Repository

Elshewy, Ahmed M.

2013-12-01

Oxygen and Nitrogen containing compounds are of utmost importance due to their interesting and diverse biological activities. The construction of the C-O and C–N bonds is of significance as it opens avenues for the introduction of ether and amine linkages in organic molecules. Despite significant advancements in this field, the construction of C-O and C–N bonds is still a major challenge for organic chemists, due to the involvement of harsh reaction conditions or the use of expensive catalysts or ligands in many cases. Thus, it is a challenge to develop alternative, milder, cheaper and more reproducible methodologies for the construction of these types of bonds. Herein, we introduce a new efficient ligand free catalytic system for C-O and C-N bond formation reactions.

Co and Fe-catalysts supported on sepiolite: effects of preparation conditions on their catalytic behaviors in high temperature gas flow treatment of dye.

Science.gov (United States)

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.

Catalytic reduction of 4-nitrophenol using gold nanoparticles biosynthesized by cell-free extracts of Aspergillus sp. WL-Au

Energy Technology Data Exchange (ETDEWEB)

Shen, Wenli; Qu, Yuanyuan, E-mail: qyy@dlut.edu.cn; Pei, Xiaofang; Li, Shuzhen; You, Shengnan; Wang, Jingwei; Zhang, Zhaojing; Zhou, Jiti

2017-01-05

Highlights: • A green process for AuNPs synthesis was achieved by fungus Aspergillus. • Uniform spherical AuNPs with well dispersity and stability were biosynthesized. • The biogenic AuNPs possessed remarkable catalytic activities for 4-NP reduction. - Abstract: A facile one-pot eco-friendly process for synthesis of gold nanoparticles (AuNPs) with high catalytic activity was achieved using cell-free extracts of Aspergillus sp. WL-Au as reducing, capping and stabilizing agents. The surface plasmon resonance band of UV–vis spectrum at 532 nm confirmed the presence of AuNPs. Transmission electron microscopy images showed that quite uniform spherical AuNPs were synthesized and the average size of nanoparticles increased from 4 nm to 29 nm with reaction time. X-ray diffraction analysis verified the formation of nano-crystalline gold particles. Fourier transform infrared spectra showed the presence of functional groups on the surface of biosynthesized AuNPs, such as O−H, N−H, C=O, C−H, C−OH and C−O−C groups, which increased the stability of AuNPs. The biogenic AuNPs could serve as a highly efficient catalyst for 4-nitrophenol reduction. The reaction rate constant was linearly correlated with the concentration of AuNPs, which increased from 0.59 min{sup −1} to 1.51 min{sup −1} with the amount of AuNPs increasing form 1.46 × 10{sup −6} to 17.47 × 10{sup −6} mmol. Moreover, the as-synthesized AuNPs exhibited a remarkable normalized catalytic activity (4.04 × 10{sup 5} min{sup −1} mol{sup −1}), which was much higher than that observed for AuNPs synthesized by other biological and conventional chemical methods.

Catalytic reduction of 4-nitrophenol using gold nanoparticles biosynthesized by cell-free extracts of Aspergillus sp. WL-Au

International Nuclear Information System (INIS)

Shen, Wenli; Qu, Yuanyuan; Pei, Xiaofang; Li, Shuzhen; You, Shengnan; Wang, Jingwei; Zhang, Zhaojing; Zhou, Jiti

2017-01-01

Highlights: • A green process for AuNPs synthesis was achieved by fungus Aspergillus. • Uniform spherical AuNPs with well dispersity and stability were biosynthesized. • The biogenic AuNPs possessed remarkable catalytic activities for 4-NP reduction. - Abstract: A facile one-pot eco-friendly process for synthesis of gold nanoparticles (AuNPs) with high catalytic activity was achieved using cell-free extracts of Aspergillus sp. WL-Au as reducing, capping and stabilizing agents. The surface plasmon resonance band of UV–vis spectrum at 532 nm confirmed the presence of AuNPs. Transmission electron microscopy images showed that quite uniform spherical AuNPs were synthesized and the average size of nanoparticles increased from 4 nm to 29 nm with reaction time. X-ray diffraction analysis verified the formation of nano-crystalline gold particles. Fourier transform infrared spectra showed the presence of functional groups on the surface of biosynthesized AuNPs, such as O−H, N−H, C=O, C−H, C−OH and C−O−C groups, which increased the stability of AuNPs. The biogenic AuNPs could serve as a highly efficient catalyst for 4-nitrophenol reduction. The reaction rate constant was linearly correlated with the concentration of AuNPs, which increased from 0.59 min −1 to 1.51 min −1 with the amount of AuNPs increasing form 1.46 × 10 −6 to 17.47 × 10 −6 mmol. Moreover, the as-synthesized AuNPs exhibited a remarkable normalized catalytic activity (4.04 × 10 5 min −1 mol −1 ), which was much higher than that observed for AuNPs synthesized by other biological and conventional chemical methods.

Synthesis of New Chiral Ligands Based on Thiophene Derivatives for Use in Catalytic Asymmetric Oxidation of Sulfides

International Nuclear Information System (INIS)

Jeong, Yong Chul; Ahn, Dae Jun; Lee, Woo Sun; Lee, Seung Han; Ahn, Kwang Hyun

2011-01-01

We discovered that the vanadium complexes of new Schiff base ligands and prepared from thiophene derivatives efficiently catalyze the asymmetric oxidation of sulfides by hydrogen peroxide to provide sulfoxides with enantioselectivities up to 79% ee and in yields up to 89%. Notably, Schiff base showed better or similar enantioselectivity than the well-studied Schiff base. These results suggest possible applications of Schiff bases derived from and in other catalytic asymmetric reactions. Chiral sulfoxides are important functional groups for various applications. For example, the biological activities of sulfoxide containing drugs such as omeprazole are strongly related to the chirality of the sulfoxide group; for this reason, esomeprazole, the enantiomerically pure form of omeprazole, was later developed. There are several chiral sulfoxide based drugs that have been introduced by the pharmaceutical industry including armodafinil, aprikalim, oxisurane, and ustiloxin. Chiral sulfoxides have also been utilized as chiral auxiliaries in asymmetric syntheses of chiral intermediates

Studies of Catalytic Model Systems

DEFF Research Database (Denmark)

Holse, Christian

The overall topic of this thesis is within the field of catalysis, were model systems of different complexity have been studied utilizing a multipurpose Ultra High Vacuum chamber (UHV). The thesis falls in two different parts. First a simple model system in the form of a ruthenium single crystal...... of the Cu/ZnO nanoparticles is highly relevant to industrial methanol synthesis for which the direct interaction of Cu and ZnO nanocrystals synergistically boost the catalytic activity. The dynamical behavior of the nanoparticles under reducing and oxidizing environments were studied by means of ex situ X......-ray Photoelectron Electron Spectroscopy (XPS) and in situ Transmission Electron Microscopy (TEM). The surface composition of the nanoparticles changes reversibly as the nanoparticles exposed to cycles of high-pressure oxidation and reduction (200 mbar). Furthermore, the presence of metallic Zn is observed by XPS...

A conserved mechanism of autoinhibition for the AMPK kinase domain: ATP-binding site and catalytic loop refolding as a means of regulation

International Nuclear Information System (INIS)

Littler, Dene R.; Walker, John R.; Davis, Tara; Wybenga-Groot, Leanne E.; Finerty, Patrick J. Jr; Newman, Elena; Mackenzie, Farell; Dhe-Paganon, Sirano

2010-01-01

A 1.9 Å resolution crystal structure of the isolated kinase domain from the α2 subunit of human AMPK, the first from a multicellular organism, is presented. The AMP-activated protein kinase (AMPK) is a highly conserved trimeric protein complex that is responsible for energy homeostasis in eukaryotic cells. Here, a 1.9 Å resolution crystal structure of the isolated kinase domain from the α2 subunit of human AMPK, the first from a multicellular organism, is presented. This human form adopts a catalytically inactive state with distorted ATP-binding and substrate-binding sites. The ATP site is affected by changes in the base of the activation loop, which has moved into an inhibited DFG-out conformation. The substrate-binding site is disturbed by changes within the AMPKα2 catalytic loop that further distort the enzyme from a catalytically active form. Similar structural rearrangements have been observed in a yeast AMPK homologue in response to the binding of its auto-inhibitory domain; restructuring of the kinase catalytic loop is therefore a conserved feature of the AMPK protein family and is likely to represent an inhibitory mechanism that is utilized during function

On the Structural Context and Identification of Enzyme Catalytic Residues

Directory of Open Access Journals (Sweden)

Yu-Tung Chien

2013-01-01

Full Text Available Enzymes play important roles in most of the biological processes. Although only a small fraction of residues are directly involved in catalytic reactions, these catalytic residues are the most crucial parts in enzymes. The study of the fundamental and unique features of catalytic residues benefits the understanding of enzyme functions and catalytic mechanisms. In this work, we analyze the structural context of catalytic residues based on theoretical and experimental structure flexibility. The results show that catalytic residues have distinct structural features and context. Their neighboring residues, whether sequence or structure neighbors within specific range, are usually structurally more rigid than those of noncatalytic residues. The structural context feature is combined with support vector machine to identify catalytic residues from enzyme structure. The prediction results are better or comparable to those of recent structure-based prediction methods.

Effect of citrate on Aspergillus niger phytase adsorption and catalytic activity in soil

Science.gov (United States)

Mezeli, Malika; Menezes-Blackburn, Daniel; Zhang, Hao; Giles, Courtney; George, Timothy; Shand, Charlie; Lumsdon, David; Cooper, Patricia; Wendler, Renate; Brown, Lawrie; Stutter, Marc; Blackwell, Martin; Darch, Tegan; Wearing, Catherine; Haygarth, Philip

2015-04-01

Current developments in cropping systems that promote mobilisation of phytate in agricultural soils, by exploiting plant-root exudation of phytase and organic acids, offer potential for developments in sustainable phosphorus use. However, phytase adsorption to soil particles and phytate complexion has been shown to inhibit phytate dephosphorylation, thereby inhibiting plant P uptake, increasing the risk of this pool contributing to diffuse pollution and reducing the potential benefits of biotechnologies and management strategies aimed to utilise this abundant reserve of 'legacy' phosphorus. Citrate has been seen to increase phytase catalytic efficiency towards complexed forms of phytate, but the mechanisms by which citrate promotes phytase remains poorly understood. In this study, we evaluated phytase (from Aspergillus niger) inactivation, and change in catalytic properties upon addition to soil and the effect citrate had on adsorption of phytase and hydrolysis towards free, precipitated and adsorbed phytate. A Langmuir model was fitted to phytase adsorption isotherms showing a maximum adsorption of 0.23 nKat g-1 (19 mg protein g-1) and affinity constant of 435 nKat gˉ1 (8.5 mg protein g-1 ), demonstrating that phytase from A.niger showed a relatively low affinity for our test soil (Tayport). Phytases were partially inhibited upon adsorption and the specific activity was of 40.44 nKat mgˉ1 protein for the free enzyme and 25.35 nKat mgˉ1 protein when immobilised. The kinetics of adsorption detailed that most of the adsorption occurred within the first 20 min upon addition to soil. Citrate had no effect on the rate or total amount of phytase adsorption or loss of activity, within the studied citrate concentrations (0-4mM). Free phytases in soil solution and phytase immobilised on soil particles showed optimum activity (>80%) at pH 4.5-5.5. Immobilised phytase showed greater loss of activity at pH levels over 5.5 and lower activities at the secondary peak at pH 2

Catalytic ozonation not relying on hydroxyl radical oxidation: A selective and competitive reaction process related to metal-carboxylate complexes

KAUST Repository

Zhang, Tao

2014-01-01

Catalytic ozonation following non-hydroxyl radical pathway is an important technique not only to degrade refractory carboxylic-containing organic compounds/matter but also to avoid catalyst deactivation caused by metal-carboxylate complexation. It is unknown whether this process is effective for all carboxylates or selective to special molecule structures. In this work, the selectivity was confirmed using O3/(CuO/CeO2) and six distinct ozone-resistant probe carboxylates (i.e., acetate, citrate, malonate, oxalate, pyruvate and succinate). Among these probe compounds, pyruvate, oxalate, and citrate were readily degraded following the rate order of oxalate>citrate>pyruvate, while the degradation of acetate, malonate, and succinate was not promoted. The selectivity was independent on carboxylate group number of the probe compounds and solution pH. Competitive degradation was observed for carboxylate mixtures following the preference order of citrate, oxalate, and finally pyruvate. The competitive degradation was ascribed to competitive adsorption on the catalyst surface. It was revealed that the catalytically degradable compounds formed bidentate chelating or bridging complexes with surface copper sites of the catalyst, i.e., the active sites. The catalytically undegradable carboxylates formed monodentate complexes with surface copper sites or just electrostatically adsorbed on the catalyst surface. The selectivity, relying on the structure of surface metal-carboxylate complex, should be considered in the design of catalytic ozonation process. © 2013 Elsevier B.V.

Catalytic activity of Au nanoparticles

DEFF Research Database (Denmark)

Larsen, Britt Hvolbæk; Janssens, Ton V.W.; Clausen, Bjerne

2007-01-01

Au is usually viewed as an inert metal, but surprisingly it has been found that Au nanoparticles less than 3–5 nm in diameter are catalytically active for several chemical reactions. We discuss the origin of this effect, focusing on the way in which the chemical activity of Au may change with par......Au is usually viewed as an inert metal, but surprisingly it has been found that Au nanoparticles less than 3–5 nm in diameter are catalytically active for several chemical reactions. We discuss the origin of this effect, focusing on the way in which the chemical activity of Au may change...... with particle size. We find that the fraction of low-coordinated Au atoms scales approximately with the catalytic activity, suggesting that atoms on the corners and edges of Au nanoparticles are the active sites. This effect is explained using density functional calculations....

Hydrogen production from palm kernel shell via integrated catalytic adsorption (ICA) steam gasification

International Nuclear Information System (INIS)

Khan, Zakir; Yusup, Suzana; Ahmad, Murni Melati; Chin, Bridgid Lai Fui

2014-01-01

Highlights: • The paper presents integrated catalytic adsorption (ICA) steam gasification for H 2 yield. • Effects of adsorbent to biomass, biomass particle size and fluidization velocity on H 2 yield are examined. • The present study produces higher H 2 yield as compared to that obtained in literatures. • The ICA provides enhancement of H 2 yield as compared to independent catalytic and CO 2 adsorption gasification systems. - Abstract: The present study investigates the integrated catalytic adsorption (ICA) steam gasification of palm kernel shell for hydrogen production in a pilot scale atmospheric fluidized bed gasifier. The biomass steam gasification is performed in the presence of an adsorbent and a catalyst in the system. The effect of adsorbent to biomass (A/B) ratio (0.5–1.5 wt/wt), fluidization velocity (0.15–0.26 m/s) and biomass particle size (0.355–2.0 mm) are studied at temperature of 675 °C, steam to biomass (S/B) ratio of 2.0 (wt/wt) and biomass to catalyst ratio of 0.1 (wt/wt). Hydrogen composition and yield, total gas yield, and lower product gas heating values (LHV gas ) increases with increasing A/B ratio, while particle size has no significant effect on hydrogen composition and yield, total gas and char yield, gasification and carbon conversion efficiency. However, gas heating values increased with increasing biomass particle size which is due to presence of high methane content in product gas. Meanwhile, medium fluidization velocity of 0.21 m/s favoured hydrogen composition and yield. The results showed that the maximum hydrogen composition and yield of 84.62 vol% and 91.11 g H 2 /kg biomass are observed at A/B ratio of 1.5, S/B ratio of 2.0, catalyst to biomass ratio of 0.1 and temperature of 675 °C. The product gas heating values are observed in the range of 10.92–17.02 MJ/N m 3 . Gasification and carbon conversion efficiency are observed in the range of 25.66–42.95% and 20.61–41.95%, respectively. These lower

Structural Evidence of a Major Conformational Change Triggered by Substrate Binding in DapE Enzymes: Impact on the Catalytic Mechanism.

Science.gov (United States)

Nocek, Boguslaw; Reidl, Cory; Starus, Anna; Heath, Tahirah; Bienvenue, David; Osipiuk, Jerzy; Jedrzejczak, Robert; Joachimiak, Andrzej; Becker, Daniel P; Holz, Richard C

2018-02-06

The X-ray crystal structure of the dapE-encoded N-succinyl-l,l-diaminopimelic acid desuccinylase from Haemophilus influenzae (HiDapE) bound by the products of hydrolysis, succinic acid and l,l-DAP, was determined at 1.95 Å. Surprisingly, the structure bound to the products revealed that HiDapE undergoes a significant conformational change in which the catalytic domain rotates ∼50° and shifts ∼10.1 Å (as measured at the position of the Zn atoms) relative to the dimerization domain. This heretofore unobserved closed conformation revealed significant movements within the catalytic domain compared to that of wild-type HiDapE, which results in effectively closing off access to the dinuclear Zn(II) active site with the succinate carboxylate moiety bridging the dinculear Zn(II) cluster in a μ-1,3 fashion forming a bis(μ-carboxylato)dizinc(II) core with a Zn-Zn distance of 3.8 Å. Surprisingly, His194.B, which is located on the dimerization domain of the opposing chain ∼10.1 Å from the dinuclear Zn(II) active site, forms a hydrogen bond (2.9 Å) with the oxygen atom of succinic acid bound to Zn2, forming an oxyanion hole. As the closed structure forms upon substrate binding, the movement of His194.B by more than ∼10 Å is critical, based on site-directed mutagenesis data, for activation of the scissile carbonyl carbon of the substrate for nucleophilic attack by a hydroxide nucleophile. Employing the HiDapE product-bound structure as the starting point, a reverse engineering approach called product-based transition-state modeling provided structural models for each major catalytic step. These data provide insight into the catalytic reaction mechanism and also the future design of new, potent inhibitors of DapE enzymes.

Reactivity and Catalytic Activity of Hydrogen Atom Chemisorbed Silver Clusters.

Science.gov (United States)

Manzoor, Dar; Pal, Sourav

2015-06-18

Metal clusters of silver have attracted recent interest of researchers as a result of their potential in different catalytic applications and low cost. However, due to the completely filled d orbital and very high first ionization potential of the silver atom, the silver-based catalysts interact very weakly with the reacting molecules. In the current work, density functional theory calculations were carried out to investigate the effect of hydrogen atom chemisorption on the reactivity and catalytic properties of inert silver clusters. Our results affirm that the hydrogen atom chemisorption leads to enhancement in the binding energy of the adsorbed O2 molecule on the inert silver clusters. The increase in the binding energy is also characterized by the decrease in the Ag-O and increase in the O-O bond lengths in the case of the AgnH silver clusters. Pertinent to the increase in the O-O bond length, a significant red shift in the O-O stretching frequency is also noted in the case of the AgnH silver clusters. Moreover, the hydrogen atom chemisorbed silver clusters show low reaction barriers and high heat of formation of the final products for the environmentally important CO oxidation reaction as compared to the parent catalytically inactive clusters. The obtained results were compared with those of the corresponding gold and hydrogen atom chemisorbed gold clusters obtained at the same level of theory. It is expected the current computational study will provide key insights for future advances in the design of efficient nanosilver-based catalysts through the adsorption of a small atom or a ligand.

Cu/Cu{sub 2}O/CuO loaded on the carbon layer derived from novel precursors with amazing catalytic performance

Energy Technology Data Exchange (ETDEWEB)

Zhao, Xiaoli, E-mail: zhaoxiaoli_zxl@126.com [State Key Laboratory of Environmental Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012 (China); Tan, Yixin [State Key Laboratory of Environmental Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012 (China); State Key Laboratory of Environmental Chemistry and Ecotoxicology, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085 (China); Wu, Fengchang, E-mail: wu_fengchang@126.com [State Key Laboratory of Environmental Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012 (China); Niu, Hongyun [State Key Laboratory of Environmental Chemistry and Ecotoxicology, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085 (China); Tang, Zhi [State Key Laboratory of Environmental Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012 (China); Cai, Yaqi [State Key Laboratory of Environmental Chemistry and Ecotoxicology, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085 (China); Giesy, John P. [State Key Laboratory of Environmental Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012 (China); Department of Veterinary Biomedical Sciences and Toxicology Centre, University of Saskatchewan, Saskatoon, Saskatchewan (Canada)

2016-11-15

A simple, novel method for synthesis of Cu/Cu{sub 2}O/CuO on surfaces of carbon (Cu/Cu{sub 2}O/CuO@C) as a non-noble-metal catalyst for reduction of organic compounds is presented. Compared with noble metals, Cu/Cu{sub 2}O/CuO@C particles are more efficient and less expensive. Characterization of the Cu/Cu{sub 2}O/CuO@C composites by high-resolution transmission electron microscope (HRTEM), x-ray diffraction (XRD), infrared spectroscopy and Raman analysis, revealed that it was composed of graphitized carbon with numerous nanoparticles (100 nm in diameter) of Cu/CuO/Cu{sub 2}O that were uniformly distributed on internal and external surfaces of the carbon support. Gallic acid (GA) has been used as both organic ligand and carbon precursor with metal organic frameworks (MOFs) as the sacrificial template and metal oxide precursor in this green synthesis. The material combined the advantages of MOFs and Cu-containing materials, the porous structure provided a large contact area and channels for the pollutions, which results in more rapid catalytic degradation of pollutants and leads to greater efficiency of catalysis. The material gave excellent catalytic performance for organic dyes and phenols. In this study, Cu/Cu{sub 2}O/CuO@C was used as catalytic to reduce 4-NP, which has been usually adopted as a model reaction to check the catalytic ability. Catalytic experiment results show that 4-NP was degraded approximately 3 min by use of 0.04 mg of catalyst and the conversion of pollutants can reach more than 99%. The catalyst exhibited little change in efficacy after being utilized five times. Rates of degradation of dyes, such as Methylene blue (MB) and Rhodamine B (RhB) and phenolic compounds such as O-Nitrophenol (O-NP) and 2-Nitroaniline (2-NA) were all similar. - Highlights: • We present an effective catalyst for reductive degradation of organic dyes and phenols in water. • Compared with noble metals, Cu/Cu{sub 2}O/CuO@C particles are more efficient and less

Engineering Metallic Nanoparticles for Enhancing and Probing Catalytic Reactions.

Science.gov (United States)

Collins, Gillian; Holmes, Justin D

2016-07-01

Recent developments in tailoring the structural and chemical properties of colloidal metal nanoparticles (NPs) have led to significant enhancements in catalyst performance. Controllable colloidal synthesis has also allowed tailor-made NPs to serve as mechanistic probes for catalytic processes. The innovative use of colloidal NPs to gain fundamental insights into catalytic function will be highlighted across a variety of catalytic and electrocatalytic applications. The engineering of future heterogenous catalysts is also moving beyond size, shape and composition considerations. Advancements in understanding structure-property relationships have enabled incorporation of complex features such as tuning surface strain to influence the behavior of catalytic NPs. Exploiting plasmonic properties and altering colloidal surface chemistry through functionalization are also emerging as important areas for rational design of catalytic NPs. This news article will highlight the key developments and challenges to the future design of catalytic NPs. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Catalytic combustion in small wood burning appliances

Energy Technology Data Exchange (ETDEWEB)

Oravainen, H [VTT Energy, Jyvaeskylae (Finland)

1997-12-31

There is over a million hand fired small heating appliances in Finland where about 5,4 million cubic meters of wood fuel is used. Combustion in such heating appliances is a batch-type process. In early stages of combustion when volatiles are burned, the formation of carbon monoxide (CO) and other combustible gases are difficult to avoid when using fuels that have high volatile matter content. Harmful emissions are formed mostly after each fuel adding but also during char burnout period. When the CO-content in flue gases is, say over 0.5 %, also other harmful emissions will be formed. Methane (CH{sub 4}) and other hydrocarbons are released and the amount of polycyclic aromatic hydrocarbons (PAH)-compounds can be remarkable. Some PAH-compounds are very carcinogenic. It has been estimated that in Finland even more than 90 % of hydrocarbon and PAH emissions are due to small scale wood combustion. Emissions from transportation is excluded from these figures. That is why wood combustion has a net effect on greenhouse gas phenomena. For example carbon monoxide emissions from small scale wood combustion are two fold compared to that of energy production in power plants. Methane emission is of the same order as emission from transportation and seven fold compared with those of energy production. Emissions from small heating appliances can be reduced by developing the combustion techniques, but also by using other means, for example catalytic converters. In certain stages of the batch combustion, temperature is not high enough, gas mixing is not good enough and residence time is too short for complete combustion. When placed to a suitable place inside a heating appliance, a catalytic converter can oxidize unburned gases in the flue gas into compounds that are not harmful to the environment. (3 refs.)

Catalytic combustion in small wood burning appliances

Energy Technology Data Exchange (ETDEWEB)

Oravainen, H. [VTT Energy, Jyvaeskylae (Finland)

1996-12-31

There is over a million hand fired small heating appliances in Finland where about 5,4 million cubic meters of wood fuel is used. Combustion in such heating appliances is a batch-type process. In early stages of combustion when volatiles are burned, the formation of carbon monoxide (CO) and other combustible gases are difficult to avoid when using fuels that have high volatile matter content. Harmful emissions are formed mostly after each fuel adding but also during char burnout period. When the CO-content in flue gases is, say over 0.5 %, also other harmful emissions will be formed. Methane (CH{sub 4}) and other hydrocarbons are released and the amount of polycyclic aromatic hydrocarbons (PAH)-compounds can be remarkable. Some PAH-compounds are very carcinogenic. It has been estimated that in Finland even more than 90 % of hydrocarbon and PAH emissions are due to small scale wood combustion. Emissions from transportation is excluded from these figures. That is why wood combustion has a net effect on greenhouse gas phenomena. For example carbon monoxide emissions from small scale wood combustion are two fold compared to that of energy production in power plants. Methane emission is of the same order as emission from transportation and seven fold compared with those of energy production. Emissions from small heating appliances can be reduced by developing the combustion techniques, but also by using other means, for example catalytic converters. In certain stages of the batch combustion, temperature is not high enough, gas mixing is not good enough and residence time is too short for complete combustion. When placed to a suitable place inside a heating appliance, a catalytic converter can oxidize unburned gases in the flue gas into compounds that are not harmful to the environment. (3 refs.)

Catalytic combustion for the elimination of methane, BTEX and other VOC : IV

International Nuclear Information System (INIS)

Hayes, R.E.; Wanke, S.E.

2008-01-01

Options for volatile organic compound combustion include homogeneous combustion (flaring) or catalytic combustion involving a flameless combustion process that uses a solid catalyst to promote the combustion reaction. This presentation discussed relative reactivity testing for volatile organic compounds (VOCs) over commercial catalysts. Several commercial pad catalysts were tested, as well as other powders. The relative reactivity of methane as well as benzene, toluene, ethylbenzene, and xylene (BTEX) were investigated. The purpose of the project was to evaluate combustion of concentrated methane streams that contained BTEX compounds; evaluate catalytic combustion using a counter diffusive radiant heater; develop mathematical models for the reactor to enhance design and understanding; improve the catalyst for BTEX combustion; and target application-dehydrator units. Topics that were addressed in the presentation included methane and benzene conversion; catalytic radiant heaters; small industrial and commercial units; measured temperature distribution; fuel slippage, methane conversion; the effect of water and hydrocarbons; the effect of water-liquid injection; and water addition as vapour. Several observations were offered, including that high percentages of injected liquid water can reduce reactor operating temperature; combustion of BTEX remained highly efficient, however liquid injection could also cause temperature reductions and ultimately the reactor would extinguish; and pre-heating the feed can eliminate the temperature drop and pad wetness problem. It was concluded that BTEX compounds are reactive, and the technology appears promising. 19 figs

Catalytic combustion for the elimination of methane, BTEX and other VOC : IV

Energy Technology Data Exchange (ETDEWEB)

Hayes, R.E.; Wanke, S.E. [Alberta Univ., Edmonton, AB (Canada). Dept. of Chemical and Materials Engineering

2008-07-01

Options for volatile organic compound combustion include homogeneous combustion (flaring) or catalytic combustion involving a flameless combustion process that uses a solid catalyst to promote the combustion reaction. This presentation discussed relative reactivity testing for volatile organic compounds (VOCs) over commercial catalysts. Several commercial pad catalysts were tested, as well as other powders. The relative reactivity of methane as well as benzene, toluene, ethylbenzene, and xylene (BTEX) were investigated. The purpose of the project was to evaluate combustion of concentrated methane streams that contained BTEX compounds; evaluate catalytic combustion using a counter diffusive radiant heater; develop mathematical models for the reactor to enhance design and understanding; improve the catalyst for BTEX combustion; and target application-dehydrator units. Topics that were addressed in the presentation included methane and benzene conversion; catalytic radiant heaters; small industrial and commercial units; measured temperature distribution; fuel slippage, methane conversion; the effect of water and hydrocarbons; the effect of water-liquid injection; and water addition as vapour. Several observations were offered, including that high percentages of injected liquid water can reduce reactor operating temperature; combustion of BTEX remained highly efficient, however liquid injection could also cause temperature reductions and ultimately the reactor would extinguish; and pre-heating the feed can eliminate the temperature drop and pad wetness problem. It was concluded that BTEX compounds are reactive, and the technology appears promising. 19 figs.

Membrane Guanylate Cyclase catalytic Subdomain: Structure and Linkage with Calcium Sensors and Bicarbonate

Directory of Open Access Journals (Sweden)

Sarangan Ravichandran

2017-06-01

Full Text Available Membrane guanylate cyclase (MGC is a ubiquitous multi-switching cyclic GMP generating signaling machine linked with countless physiological processes. In mammals it is encoded by seven distinct homologous genes. It is a single transmembrane spanning multi-modular protein; composed of integrated blocks and existing in homo-dimeric form. Its core catalytic domain (CCD module is a common transduction center where all incoming signals are translated into the production of cyclic GMP, a cellular signal second messenger. Crystal structure of the MGC’s CCD does not exist and its precise identity is ill-defined. Here, we define it at a sub-molecular level for the phototransduction-linked MGC, the rod outer segment guanylate cyclase type 1, ROS-GC1. (1 The CCD is a conserved 145-residue structural unit, represented by the segment V820-P964. (2 It exists as a homo-dimer and contains seven conserved catalytic elements (CEs wedged into seven conserved motifs. (3 It also contains a conserved 21-residue neurocalcin δ-modulated structural domain, V836-L857. (4 Site-directed mutagenesis documents that each of the seven CEs governs the cyclase’s catalytic activity. (5 In contrast to the soluble and the bacterium MGC which use Mn2+-GTP substrate for catalysis, MGC CCD uses the natural Mg2+-GTP substrate. (6 Strikingly, the MGC CCD requires anchoring by the Transmembrane Domain (TMD to exhibit its major (∼92% catalytic activity; in isolated form the activity is only marginal. This feature is not linked with any unique sequence of the TMD; there is minimal conservation in TMD. Finally, (7 the seven CEs control each of four phototransduction pathways- -two Ca2+-sensor GCAPs-, one Ca2+-sensor, S100B-, and one bicarbonate-modulated. The findings disclose that the CCD of ROS-GC1 has built-in regulatory elements that control its signal translational activity. Due to conservation of these regulatory elements, it is proposed that these elements also control the

Cyanogel-derived N-doped C nanosheets immobilizing Pd-P nanoparticles: One-pot synthesis and enhanced hydrogenation catalytic performance

Energy Technology Data Exchange (ETDEWEB)

Zhang, Hao; Yan, Xiaohong; Huang, Yundi; Zhang, Mengru; Tang, Yawen; Sun, Dongmei; Xu, Lin, E-mail: njuxulin@gmail.com; Wei, Shaohua, E-mail: weishaohua@njnu.edu.cn

2017-02-28

Highlights: • Cyanogel-bridged approach was developed for the synthesis of Pd-P@N-Cnanosheets. • Pd-P@N-C nanosheets exhibit high activity and stability for reduction of 4-NP. • Compositional and structural advantages account for the high catalytic activity. • The feasible synthesis could be extendable to other carbon-based nanohybrids. - Abstract: For Pd-based nanocatalysts, stabilization of Pd nanoparticles on carbon support could not only effectively avoid particle aggregation and maintain catalytic stability during catalytic processes, but also facilitate enhancing the catalytic activity due to the synergy between Pd nanoparticles and carbon support. Furthermore, the incorporation of non-metal of phosphorus (P) into Pd could effectively modulate the electronic structure of Pd and thus help to boost the catalytic properties. However, one-pot synthesis of such nanohybrids remains a great challenge due to the distinct physiochemical properties of Pd, P and C components. Herein, we demonstrate a one-pot and scalable synthesis of highly dispersed PdP alloy nanoparticle-immobilized on N-doped graphitic carbon nanosheets (abbreviated as Pd-P@N-C nanosheets) by using inorganic-organic hybrid cyanogel as a reaction precursor. In virtue of both compositional and structural advantages, the as-synthesized Pd-P@N-C nanosheets manifest a superior catalytic activity and stability toward the hydrogenation of 4-nitrophenol (4-NP). We believe that the present work will provide a feasible and versatile strategy for the development of efficient catalysts for environmental remediation and can also be extendable to other carbon-based nanohybrids with desirable functionalities.

Catalytic Conversion of Carbohydrates to Initial Platform Chemicals: Chemistry and Sustainability.

Science.gov (United States)

Mika, László T; Cséfalvay, Edit; Németh, Áron

2018-01-24

The replacement of fossil resources that currently provide more than 90% of our energy needs and feedstocks of the chemical industry in combination with reduced emission of carbon dioxide is one of the most pressing challenges of mankind. Biomass as a globally available resource has been proposed as an alternative feedstock for production of basic building blocks, which could partially or even fully replace the currently utilized fossil-based ones in well-established chemical processes. The destruction of lignocellulosic feed followed by oxygen removal from its cellulose and hemicellulose content by catalytic processes results in the formation of initial platform chemicals (IPCs). However, their sustainable production strongly depends on the availability of resources, their efficient or even industrially viable conversion processes, and replenishment time of feedstocks. Herein, we overview recent advances and developments in catalytic transformations of the carbohydrate content of lignocellulosic biomass to IPCs (i.e., ethanol, 3-hydroxypropionic acid, isoprene, succinic and levulinic acids, furfural, and 5-hydroxymethylfurfural). The mechanistic aspects, development of new catalysts, different efficiency indicators (yield and selectivity), and conversion conditions of their production are presented and compared. The potential biochemical production routes utilizing recently engineered microorganisms are reviewed, as well. The sustainability metrics that could be applied to the chemical industry (individual set of sustainability indicators, composite indices methods, material and energy flow analysis-based metrics, and ethanol equivalents) are also overviewed as well as an outlook is provided to highlight challenges and opportunities associated with this huge research area.

MAP: an iterative experimental design methodology for the optimization of catalytic search space structure modeling.

Science.gov (United States)

Baumes, Laurent A

2006-01-01

One of the main problems in high-throughput research for materials is still the design of experiments. At early stages of discovery programs, purely exploratory methodologies coupled with fast screening tools should be employed. This should lead to opportunities to find unexpected catalytic results and identify the "groups" of catalyst outputs, providing well-defined boundaries for future optimizations. However, very few new papers deal with strategies that guide exploratory studies. Mostly, traditional designs, homogeneous covering, or simple random samplings are exploited. Typical catalytic output distributions exhibit unbalanced datasets for which an efficient learning is hardly carried out, and interesting but rare classes are usually unrecognized. Here is suggested a new iterative algorithm for the characterization of the search space structure, working independently of learning processes. It enhances recognition rates by transferring catalysts to be screened from "performance-stable" space zones to "unsteady" ones which necessitate more experiments to be well-modeled. The evaluation of new algorithm attempts through benchmarks is compulsory due to the lack of past proofs about their efficiency. The method is detailed and thoroughly tested with mathematical functions exhibiting different levels of complexity. The strategy is not only empirically evaluated, the effect or efficiency of sampling on future Machine Learning performances is also quantified. The minimum sample size required by the algorithm for being statistically discriminated from simple random sampling is investigated.

Destruction of organochlorated compounds and CFCs by catalytic hydrodechloration; Destruccion de compuestos organoclorados y CFCs mediante hidrodecloracion catalitica

Energy Technology Data Exchange (ETDEWEB)

Ordonez Garcia, S.; Sastre Andres, H.; Diez Sanz, F. V.

1998-12-01

The destruction of organohalogenated compounds ( for example chlorinated solvents, PCBs and CFCs) is a very serious environmental problems. Catalytic hydrodechlorination has shown to be potentially efficient method for the destruction of these compounds. In this technique the halogenated compound reacts with hydrogen, tielding a non-chlorinated compound (environmentally harmless) and hydrogen-chloride. In this article, different set-ups and catalysts employed in the catalytic hydrogechlorination were described. Finally, some applications of this technique to the treatment of industrial effluents, such as the destruction of chlorinated solvents (as trichloroethylene o tetrachloromethane), conversion of CFCs into HCFCs, destruction of PCBs and treatment of water polluted with chlorinated pesticides. (Author) 28 refs.

Efficient free-form surface representation with application in orthodontics

Science.gov (United States)

Yamany, Sameh M.; El-Bialy, Ahmed M.

1999-03-01

Orthodontics is the branch of dentistry concerned with the study of growth of the craniofacial complex. The detection and correction of malocclusion and other dental abnormalities is one of the most important and critical phases of orthodontic diagnosis. This paper introduces a system that can assist in automatic orthodontics diagnosis. The system can be used to classify skeletal and dental malocclusion from a limited number of measurements. This system is not intended to deal with several cases but is aimed at cases more likely to be encountered in epidemiological studies. Prior to the measurement of the orthodontics parameters, the position of the teeth in the jaw model must be detected. A new free-form surface representation is adopted for the efficient and accurate segmentation and separation of teeth from a scanned jaw model. THe new representation encodes the curvature and surface normal information into a 2D image. Image segmentation tools are then sued to extract structures of high/low curvature. By iteratively removing these structures, individual teeth surfaces are obtained.

Hydrocarbon conversion with an attenuated superactive multimetallic catalytic composite

International Nuclear Information System (INIS)

Antos, G.J.

1981-01-01

Hydrocarbons are converted by contacting them at hydrocarbon conversion conditions with a novel attenuated superactive multimetallic catalytic composite comprising a combination of a catalytically effective amount of a pyrolyzed rhenium carbonyl component with a porous carrier material containing a uniform dispersion of catalytically effective amounts of a platinum group component, which is maintained in the elemental metallic state during the incorporation and pyrolysis of the rhenium carbonyl component, and of an iron component. In a highly preferred embodiment, this novel catalytic composite also contains a catalytically effective amount of a halogen component. The platinum group component, pyrolyzed rhenium carbonyl component, iron component and optional halogen component are preferably present in the multimetallic catalytic composite in amounts, calculated on an elemental basis, corresponding to about 0.01 to about 2 wt. % platinum group metal, about 0.01 to about 5 wt. % rhenium, about 0.005 to about 4 wt. % iron and about 0.1 to about 5 wt. % halogen. A key feature associated with the preparation of the subject catalytic composite is reaction of a rhenium carbonyl complex with a porous carrier material containing a uniform dispersion of an iron component and of a platinum group component maintained in the elemental state, whereby the interaction of the rhenium moiety with the platinum group moiety is maximized due to the platinophilic (i.e., platinum-seeking) propensities of the carbon monoxide ligands associated with the rhenium reagent. A specific example of the type of hydrocarbon conversion process disclosed herein is a process for the catalytic reforming of a low octane gasoline fraction wherein the gasoline fraction and a hydrogen stream are contacted with the attenuated superactive multimetallic catalytic composite at reforming conditions

Selenoglutathione Diselenide: Unique Redox Reactions in the GPx-Like Catalytic Cycle and Repairing of Disulfide Bonds in Scrambled Protein.

Science.gov (United States)

Shimodaira, Shingo; Asano, Yuki; Arai, Kenta; Iwaoka, Michio

2017-10-24

Selenoglutathione (GSeH) is a selenium analogue of naturally abundant glutathione (GSH). In this study, this water-soluble small tripeptide was synthesized in a high yield (up to 98%) as an oxidized diselenide form, i.e., GSeSeG (1), by liquid-phase peptide synthesis (LPPS). Obtained 1 was applied to the investigation of the glutathione peroxidase (GPx)-like catalytic cycle. The important intermediates, i.e., GSe - and GSeSG, besides GSeO 2 H were characterized by 77 Se NMR spectroscopy. Thiol exchange of GSeSG with various thiols, such as cysteine and dithiothreitol, was found to promote the conversion to GSe - significantly. In addition, disproportionation of GSeSR to 1 and RSSR, which would be initiated by heterolytic cleavage of the Se-S bond and catalyzed by the generated selenolate, was observed. On the basis of these redox behaviors, it was proposed that the heterolytic cleavage of the Se-S bond can be facilitated by the interaction between the Se atom and an amino or aromatic group, which is present at the GPx active site. On the other hand, when a catalytic amount of 1 was reacted with scrambled 4S species of RNase A in the presence of NADPH and glutathione reductase, native protein was efficiently regenerated, suggesting a potential use of 1 to repair misfolded proteins through reduction of the non-native SS bonds.

Catalytic treatment

Energy Technology Data Exchange (ETDEWEB)

Bindley, W T.R.

1931-04-18

An apparatus is described for the catalytic treatment of liquids, semi-liquids, and gases comprising a vessel into which the liquid, semi-liquid, or gas to be treated is introduced through a common inlet to a chamber within the vessel whence it passes to contact with a catalyst through radially arranged channels or passages to a common outlet chamber.

Research of Hydrogen Preparation with Catalytic Steam-Carbon Reaction Driven by Photo-Thermochemistry Process

Directory of Open Access Journals (Sweden)

Xiaoqing Zhang

2013-01-01

Full Text Available An experiment of hydrogen preparation from steam-carbon reaction catalyzed by K2CO3 was carried out at 700°C, which was driven by the solar reaction system simulated with Xenon lamp. It can be found that the rate of reaction with catalyst is 10 times more than that without catalyst. However, for the catalytic reaction, there is no obvious change for the rate of hydrogen generation with catalyst content range from 10% to 20%. Besides, the conversion efficiency of solar energy to chemical energy is more than 13.1% over that by photovoltaic-electrolysis route. An analysis to the mechanism of catalytic steam-carbon reaction with K2CO3 is given, and an explanation to the nonbalanced [H2]/[CO + 2CO2] is presented, which is a phenomenon usually observed in experiment.

Tuning Catalytic Performance through a Single or Sequential Post-Synthesis Reaction(s) in a Gas Phase

Energy Technology Data Exchange (ETDEWEB)

Shan, Junjun [Department; Department; Zhang, Shiran [Department; Department; Choksi, Tej [Department; Nguyen, Luan [Department; Department; Bonifacio, Cecile S. [Department; Li, Yuanyuan [Department; Zhu, Wei [Department; Department; College; Tang, Yu [Department; Department; Zhang, Yawen [College; Yang, Judith C. [Department; Greeley, Jeffrey [Department; Frenkel, Anatoly I. [Department; Tao, Franklin [Department; Department

2016-12-05

Catalytic performance of a bimetallic catalyst is determined by geometric structure and electronic state of the surface or even the near-surface region of the catalyst. Here we report that single and sequential postsynthesis reactions of an as-synthesized bimetallic nanoparticle catalyst in one or more gas phases can tailor surface chemistry and structure of the catalyst in a gas phase, by which catalytic performance of this bimetallic catalyst can be tuned. Pt–Cu regular nanocube (Pt–Cu RNC) and concave nanocube (Pt–Cu CNC) are chosen as models of bimetallic catalysts. Surface chemistry and catalyst structure under different reaction conditions and during catalysis were explored in gas phase of one or two reactants with ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) and extended X-ray absorption fine structure (EXAFS) spectroscopy. The newly formed surface structures of Pt–Cu RNC and Pt–Cu CNC catalysts strongly depend on the reactive gas(es) used in the postsynthesis reaction(s). A reaction of Pt–Cu RNC-as synthesized with H2 at 200 °C generates a near-surface alloy consisting of a Pt skin layer, a Cu-rich subsurface, and a Pt-rich deep layer. This near-surface alloy of Pt–Cu RNC-as synthesized-H2 exhibits a much higher catalytic activity in CO oxidation in terms of a low activation barrier of 39 ± 4 kJ/mol in contrast to 128 ± 7 kJ/mol of Pt–Cu RNC-as synthesized. Here the significant decrease of activation barrier demonstrates a method to tune catalytic performances of as-synthesized bimetallic catalysts. A further reaction of Pt–Cu RNC-as synthesized-H2 with CO forms a Pt–Cu alloy surface, which exhibits quite different catalytic performance in CO oxidation. It suggests the capability of generating a different surface by using another gas. The capability of tuning surface chemistry and structure of bimetallic catalysts was also demonstrated in restructuring of Pt–Cu CNC-as synthesized.

Smoke emissions from a catalytic wood stove

International Nuclear Information System (INIS)

Cowburn, D.A.; Stephens, N.P.J.

1994-01-01

The work reported here was concerned with testing a catalytic wood burning stove (roomheater) following the most applicable UK procedures. The identical stove has also been tested in several other nations to their individual procedures. The results will be submitted to the International Energy Agency (IEA) such that appropriate comparisons can be made. The results comprised: burning rate; an indicative appliance efficiency; heat output; carbon dioxide emissions; carbon monoxide emissions; and smoke emissions. These results were determined with the appliance at three nominal burning rates (high, medium and low). Comparing the results with those obtained in other countries indicates good agreement except when the appliance was operated at low burning rates, under which conditions the UK results indicate significantly worse smoke emissions than those measured by other researchers. (author)

Low temperature catalytic combustion of natural gas - hydrogen - air mixtures

Energy Technology Data Exchange (ETDEWEB)

Newson, E; Roth, F von; Hottinger, P; Truong, T B [Paul Scherrer Inst. (PSI), Villigen (Switzerland)

1999-08-01

The low temperature catalytic combustion of natural gas - air mixtures would allow the development of no-NO{sub x} burners for heating and power applications. Using commercially available catalysts, the room temperature ignition of methane-propane-air mixtures has been shown in laboratory reactors with combustion efficiencies over 95% and maximum temperatures less than 700{sup o}C. After a 500 hour stability test, severe deactivation of both methane and propane oxidation functions was observed. In cooperation with industrial partners, scaleup to 3 kW is being investigated together with startup dynamics and catalyst stability. (author) 3 figs., 3 refs.

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

Energy Technology Data Exchange (ETDEWEB)

Larsson, Per-Olof

1999-05-01

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

Structural basis and catalytic mechanism for the dual functional endo-beta-N-acetylglucosaminidase A.

Directory of Open Access Journals (Sweden)

Jie Yin

Full Text Available Endo-beta-N-acetylglucosaminidases (ENGases are dual specificity enzymes with an ability to catalyze hydrolysis and transglycosylation reactions. Recently, these enzymes have become the focus of intense research because of their potential for synthesis of glycopeptides. We have determined the 3D structures of an ENGase from Arthrobacter protophormiae (Endo-A in 3 forms, one in native form, one in complex with Man(3GlcNAc-thiazoline and another in complex with GlcNAc-Asn. The carbohydrate moiety sits above the TIM-barrel in a cleft region surrounded by aromatic residues. The conserved essential catalytic residues - E173, N171 and Y205 are within hydrogen bonding distance of the substrate. W216 and W244 regulate access to the active site during transglycosylation by serving as "gate-keepers". Interestingly, Y299F mutation resulted in a 3 fold increase in the transglycosylation activity. The structure provides insights into the catalytic mechanism of GH85 family of glycoside hydrolases at molecular level and could assist rational engineering of ENGases.

A conceptual design of catalytic gasification fuel cell hybrid power plant with oxygen transfer membrane

Science.gov (United States)

Shi, Wangying; Han, Minfang

2017-09-01

A hybrid power generation system integrating catalytic gasification, solid oxide fuel cell (SOFC), oxygen transfer membrane (OTM) and gas turbine (GT) is established and system energy analysis is performed. In this work, the catalytic gasifier uses steam, recycled anode off-gas and pure oxygen from OTM system to gasify coal, and heated by hot cathode off-gas at the same time. A zero-dimension SOFC model is applied and verified by fitting experimental data. Thermodynamic analysis is performed to investigate the integrated system performance, and system sensitivities on anode off-gas back flow ratio, SOFC fuel utilization, temperature and pressure are discussed. Main conclusions are as follows: (1) System overall electricity efficiency reaches 60.7%(HHV) while the gasifier operates at 700 °C and SOFC at 850 °C with system pressure at 3.04 bar; (2) oxygen enriched combustion simplify the carbon-dioxide capture process, which derives CO2 of 99.2% purity, but results in a penalty of 6.7% on system electricity efficiency; (3) with SOFC fuel utilization or temperature increasing, the power output of SOFC increases while GT power output decreases, and increasing system pressure can improve both the performance of SOFC and GT.

[Degradation of m-Cresol with Fe-MCM-41 in Catalytic Ozonation].

Science.gov (United States)

Sun, Wen-jing; Wang, Ya-min; Wei, Huang-zhao; Wang, Sen; Li, Xu-ning; Li, Jing-mei; Sun, Cheng-lin; An, Lu-yang

2015-04-01

Fe-MCM-41 was first used for the treatment of m-cresol in catalytic ozonation. The effect of the percentage of Fe dopping mass, catalyst dosage and the natural concentration of substrate on m-cresol conversion and TOC removal were studied. The structural property of Fe-MCM-41 was characterized by X-ray diffraction, temperature-programmed reduction, Mössbauer spectra and BET of catalysts. The results showed that Fe dopping mass had a great effect on the catalytic activity of Fe-MCM-41 in catalytic ozonation and the optimal percentage of dopping mass was 4.4% (wt). The results showed that with Fe dopping mass increase, the degree of crystallinity became weaker, the crystal surface distance reduced, as well as the specific surface area, pore volume and aperture. γ-Fe2O3 was the only form staying on the surface of MCM-41, and the catalyst had good ferromagnetism and stability. Ozonation played a role of both direct oxidation and indirect oxidation in the reaction, approximately the same ratio. Under the experimental condition of the natural pH of model wastewater,using 4.4% (wt) Fe-MCM-41 as catalyst, natural concentration of m-cresol 500 mg x L(-1), catalyst dosage 0.1 g x L(-1) and reaction time 30 min, m-cresol conversion and TOC removal were 100% and 26.8%, respectively.

Isotopic tracer studies to evaluate relative efficiency of different forms of P for growing rice on different soil types

Energy Technology Data Exchange (ETDEWEB)

Dash, R N; Mohanty, S K; Patnaik, S [Central Rice Research Inst., Cuttack (India)

1977-12-01

The relative efficiency of different forms of P in relation to their time of application for growing rice on different soil types has been studied by using /sup 32/P tagged mono-, di-, and tri-calcium phosphate, ammonium nitrate phosphate containing all the P in the citrate-soluble form and potassium meta-phosphate. P-deficient acid laterite soil from Burdwan, red loam soil from Peramanpur and calcareous black soil from Hyderabad were used in the study. The different P forms were found to be compatible in the acid, red and laterite soils when the phosphorus forms were primed to moist acid soils 2 weeks prior to flooding. On application at flooding, fertilizers containing citrate-soluble phosphate were found to be less effective as compared to those containing water-soluble phosphate. In the calcareous black soil, however, the fertilizers, containing insoluble or citrate-soluble phosphates were not as efficient as the water-soluble forms, possibly because of lack of dissolution process. Potassium meta-phosphate was found to be effective in all the soil types whether applied at flooding or primed to the moist soil.

Synthesis of Rh/Macro-Porous Alumina Over Micro-Channel Plate and Its Catalytic Activity Tests for Diesel Reforming.

Science.gov (United States)

Seong, Yeon Baek; Kim, Yong Sul; Park, No-Kuk; Lee, Tae Jin

2015-11-01

Macro-porous Al2O3 as the catalytic support material was synthesized using colloidal polystyrene spheres over a micro-channel plate. The colloidal polystyrene spheres were used as a template for the production of an ordered macro porous material using an alumina nitrate solution as the precursor for Al2O3. The close-packed colloidal crystal array template method was applied to the formulation of ordered macro-porous Al2O3 used as a catalytic support material over a micro-channel plate. The solvent in the mixture solution, which also contained the colloidal polystyrene solution, aluminum nitrate solution and the precursor of the catalytic active materials (Rh), was evaporated in a vacuum oven at 50 degrees C. The ordered polystyrene spheres and aluminum salt of the solid state were deposited over a micro channel plate, and macro-porous Al2O3 was formed after calcination at 600 degrees C to remove the polystyrene spheres. The catalytic activity of the Rh/macro-porous alumina supported over the micro-channel plate was tested for diesel reforming.

Studies Relevent to Catalytic Activation Co & other small Molecules

Energy Technology Data Exchange (ETDEWEB)

Ford, Peter C

2005-02-22

Detailed annual and triannual reports describing the progress accomplished during the tenure of this grant were filed with the Program Manager for Catalysis at the Office of Basic Energy Sciences. To avoid unnecessary duplication, the present report will provide a brief overview of the research areas that were sponsored by this grant and list the resulting publications and theses based on this DOE supported research. The scientific personnel participating in (and trained by) this grant's research are also listed. Research carried out under this DOE grant was largely concerned with the mechanisms of the homogeneous catalytic and photocatalytic activation of small molecules such as carbon monoxide, dihydrogen and various hydrocarbons. Much of the more recent effort has focused on the dynamics and mechanisms of reactions relevant to substrate carbonylations by homogeneous organometallic catalysts. A wide range of modern investigative techniques were employed, including quantitative fast reaction methodologies such as time-resolved optical (TRO) and time-resolved infrared (TRIR) spectroscopy and stopped flow kinetics. Although somewhat diverse, this research falls within the scope of the long-term objective of applying quantitative techniques to elucidate the dynamics and understand the principles of mechanisms relevant to the selective and efficient catalytic conversions of fundamental feedstocks to higher value materials.

Catalytic conversion of corncob and corncob pretreatment hydrolysate to furfural in a biphasic system with addition of sodium chloride.

Science.gov (United States)

Qing, Qing; Guo, Qi; Zhou, Linlin; Wan, Yilun; Xu, Youqing; Ji, Huilong; Gao, Xiaohang; Zhang, Yue

2017-02-01

Catalytic conversion of corncob pretreatment hydrolysate and raw corncob into furfural in a modified biphasic system by SO 4 2- /SnO 2 - MMT solid catalyst has been developed. The influence of the organic solvent type, organic to water phase ratio, sodium chloride concentration, reaction temperature and time on the furfural production were comparatively evaluated. The results showed that furfural yields of 81.7% and 66.1% were achieved at 190°C for 15mins and 190°C for 20mins, respectively, for corncob pretreatment hydrolysate and raw corncob by this solid catalyst. The solid catalyst used in this study exhibited good stability and high efficiency applied in the modified biphasic system in addition to excellent recyclability. The proposed catalytic system displayed high performance for catalytic conversion of lignocellulosic biomass into important platform chemicals and has great potential in industrial application. Copyright © 2016 Elsevier Ltd. All rights reserved.

Nature of active centers of catalytic system of VOCl/sub 3/ - Al(C/sub 2/H/sub 5/)/sub 2/Cl

Energy Technology Data Exchange (ETDEWEB)

Dubnikova, I L; Meshkova, I N [AN SSSR, Moscow. Inst. Khimicheskoj Fiziki

1977-05-01

To investigate the nature of the active sites of the catalyst VOCl/sub 3/-Al(C/sub 2/H/sub 5/)/sub 2/Cl during olefine polymerization, the following factors have been studied: composition and catalytic activity of homogeneous and heterogeneous components of the system, valent state of vanadium entering into the composition of the catalytic sites, effect of an organoaluminium component on the catalytic activity of the system, and the properties of the polymeric products being formed. It has been shown that the catalytic sites of the system VOCl/sub 3/-Al(C/sub 4/H/sub 5/)/sub 2/Cl are located, predominantly, in the heterogeneus phase of the catalyst. A conclusion has been made that heterogeneous catalytic sites are bimetal complexes of alkyl derivatives of vanadium trichloride and aluminuim alkylchlorides and that polycentral mechanism of catalysis of olefine polymerization in the presence of VOCl/sub 3/-Al(C/sub 2/H/sub 5/)/sub 2/Cl is caused by two types of active vanadium-aluminium complexes differing in the nature of an organoaluminium component.

Expression, purification and preliminary crystallographic studies on the catalytic region of the nonreceptor tyrosine kinase Fes

International Nuclear Information System (INIS)

Gnemmi, Ilaria; Scotti, Claudia; Cappelletti, Donata; Canonico, Pier Luigi; Condorelli, Fabrizio; Rosano, Camillo

2006-01-01

The catalytic domain of human Fes tyrosine kinase has been cloned, expressed, purified and crystallized. The proto-oncogene tyrosine protein kinase c-fps/fes encodes a structurally unique protein (Fes) of the nonreceptor protein-tyrosine kinase (PTK) family. Its expression has been demonstrated in myeloid haematopoietic cells, vascular endothelial cells and in neurons. In human-derived and murine-derived cell lines, the activated form of this kinase can induce cellular transformation; moreover, it has been shown that Fes is involved in the regulation of cell–cell and cell–matrix interactions mediated by adherens junctions and focal adhesions. The N-terminus of Fes contains the FCH (Fps/Fes/Fer/CIP4 homology) domain, which is unique to the Fes/Fer kinase family. It is followed by three coiled-coil domains and an SH2 (Src-homology 2) domain. The catalytic region (Fes-CR) is located at the C-terminus of the protein. The successful expression, purification and crystallization of the catalytic part of Fes (Fes-CR) are described

Stability and Catalytic Kinetics of Horseradish Peroxidase Confined in Nanoporous SBA-15

DEFF Research Database (Denmark)

Ikemoto, Hediki; Chi, Qijin; Ulstrup, Jens

2010-01-01

We have synthesized nanoporous silica, SBA-15 in the 1 m size range with the pore diameter of 7.6 nm. The redox enzyme horseradish peroxidase (HRP) was entrapped in the pores to form nanostructured hybrid materials. The catalytic activity of free and immobilized enzyme was first compared at room...... likely due to different hydrogen bonding of water and increased hydration strength of the protein inside the nanopores....

Rice Cellulose SynthaseA8 Plant-Conserved Region Is a Coiled-Coil at the Catalytic Core Entrance