WorldWideScience

Sample records for solution catalytically active

  1. 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.

  2. Catalytic Activity of Urchin-like Ni nanoparticles Prepared by Solvothermal Method for Hydrogen Evolution Reaction in Alkaline Solution

    International Nuclear Information System (INIS)

    Abbas, Syed Asad; Iqbal, Muhammad Ibrahim; Kim, Seong-Hoon; Jung, Kwang-Deog

    2017-01-01

    Highlights: • Urchin-like Ni is prepared in solvothermal reaction. • Urchin-like Ni is formed via Ni(OH) 2 aggregates in ethanol and oleylamine. • Exchange current density of urchin-like Ni is 0.191 mA cm −2 . • Urchin-like Ni exceeds the catalytic performance of commercial Pt/C in HER. - Abstract: Ni nanoparticles with different morphologies were synthesized for hydrogen evolution reaction (HER) in alkaline solution. Here, Ni(acac) 2 was converted into Ni metal nanoparticles in solvothermal reactions with simple alcohols and oleylamine (OAm). The morphology of the resulting Ni nanoparticles was dependent mainly on the OAm/Ni molar ratio in alcohol solvent. Aggregates of spherical Ni nanoparticles (NiEt-OAm1) were observed at the OAm/Ni molar ratio of 1.0, whereas two echinoid Ni nanoparticles (NiEt-OAm4 and NiEt-OAm6) could be prepared in ethanol at the OAm/Ni molar ratios of 4.0 and 6.0. Ni(OH) 2 formed in ethanol during a reaction time of 5 h was then reduced into echinoid Ni nanoparticles after 8 h. Echinoid Ni nanoparticles were formed by atomic addition on the tops of the multipod Ni particles formed via Ni(OH) 2 /NiO aggregates. Webbed feet-like particles (NiIPA-OAm4) with plate edges were also observed in isopropanol under the same reaction conditions. The catalytic activities of the prepared Ni nanoparticles for the hydrogen evolution reaction were evaluated in alkaline solution. The NiEt-OAm4 with urchin-like morphology was much more active than the NiIPA-OAm4 with webbed feet-like morphology. The exchange current density of Ni catalysts was increased with increasing the OAm/Ni molar ratio. The NiEt-OAm6 exhibited an exchange current of 0.191 mA cm −2 and the NiEt-OAm4 exceeded electrocatalytic performance of a commercial Pt catalysts (40% Pt on Vulcan XC 72) in a stability test for 100 kiloseconds at −1.5 V (vs. Hg/HgO) in 1.0 M NaOH due to its high stability.

  3. Heterogeneous catalytic degradation of polyacrylamide solution | Hu ...

    African Journals Online (AJOL)

    Modified with trace metal elements, the catalytic activity of Fe2O3/Al2O3 could be changed greatly. Among various trace metal elements, Fe2O3/Al2O3 catalysts modified with Co and Cu showed great increase on catalytic activity. International Journal of Engineering, Science and Technology, Vol. 2, No. 7, 2010, pp. 110- ...

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

    International Nuclear Information System (INIS)

    Hung, C.-M.

    2009-01-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2009-04-15

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

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

    Science.gov (United States)

    Hung, Chang-Mao

    2009-04-15

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

  7. 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....

  8. Base Catalytic Approach: A Promising Technique for the Activation of Biochar for Equilibrium Sorption Studies of Copper, Cu(II Ions in Single Solute System

    Directory of Open Access Journals (Sweden)

    Sharifah Bee Abdul Hamid

    2014-04-01

    Full Text Available This study examines the feasibility of catalytically pretreated biochar derived from the dried exocarp or fruit peel of mangostene with Group I alkali metal hydroxide (KOH. The pretreated char was activated in the presence of carbon dioxide gas flow at high temperature to upgrade its physiochemical properties for the removal of copper, Cu(II cations in single solute system. The effect of three independent variables, including temperature, agitation time and concentration, on sorption performance were carried out. Reaction kinetics parameters were determined by using linear regression analysis of the pseudo first, pseudo second, Elovich and intra-particle diffusion models. The regression co-efficient, R2 values were best for the pseudo second order kinetic model for all the concentration ranges under investigation. This implied that Cu(II cations were adsorbed mainly by chemical interactions with the surface active sites of the activated biochar. Langmuir, Freundlich and Temkin isotherm models were used to interpret the equilibrium data at different temperature. Thermodynamic studies revealed that the sorption process was spontaneous and endothermic. The surface area of the activated sample was 367.10 m2/g, whereas before base activation, it was only 1.22 m2/g. The results elucidated that the base pretreatment was efficient enough to yield porous carbon with an enlarged surface area, which can successfully eliminate Cu(II cations from waste water.

  9. Removal of ammonia solutions used in catalytic wet oxidation processes.

    Science.gov (United States)

    Hung, Chang Mao; Lou, Jie Chung; Lin, Chia Hua

    2003-08-01

    Ammonia (NH(3)) is an important product used in the chemical industry, and is common place in industrial wastewater. Industrial wastewater containing ammonia is generally either toxic or has concentrations or temperatures such that direct biological treatment is unfeasible. This investigation used aqueous solutions containing more of ammonia for catalytic liquid-phase oxidation in a trickle-bed reactor (TBR) based on Cu/La/Ce composite catalysts, prepared by co-precipitation of Cu(NO(3))(2), La(NO(3))(2), and Ce(NO(3))(3) at 7:2:1 molar concentrations. The experimental results indicated that the ammonia conversion of the wet oxidation in the presence of the Cu/La/Ce composite catalysts was determined by the Cu/La/Ce catalyst. Minimal ammonia was removed from the solution by the wet oxidation in the absence of any catalyst, while approximately 91% ammonia removal was achieved by wet oxidation over the Cu/La/Ce catalyst at 230 degrees C with oxygen partial pressure of 2.0 MPa. Furthermore, the effluent streams were conducted at a liquid hourly space velocity of under 9 h(-1) in the wet catalytic processes, and a reaction pathway was found linking the oxidizing ammonia to nitric oxide, nitrogen and water. The solution contained by-products, including nitrates and nitrites. Nitrite selectivity was minimized and ammonia removal maximized when the feed ammonia solution had a pH of around 12.0.

  10. Microwave-induced carbon nanotubes catalytic degradation of organic pollutants in aqueous solution

    International Nuclear Information System (INIS)

    Chen, Jing; Xue, Shuang; Song, Youtao; Shen, Manli; Zhang, Zhaohong; Yuan, Tianxin; Tian, Fangyuan; Dionysiou, Dionysios D.

    2016-01-01

    Highlights: • Microwave-induced CNTs-based catalytic degradation technology is developed. • Microwave catalytic activities of CNTs with different diameters are compared. • Organic pollutants with different structure can be degraded in MW/CNTs system. • The 10–20 nm CNTs shows the higher catalytic activity under MW irradiation. - Abstract: In this study, a new catalytic degradation technology using microwave induced carbon nanotubes (MW/CNTs) was proposed and applied in the treatment of organic pollutants in aqueous solution. The catalytic activity of three CNTs of 10–20 nm, 20–40 nm, and 40–60 nm diameters were compared. The results showed that organic pollutants such as methyl orange (MO), methyl parathion (MP), sodium dodecyl benzene sulfonate (SDBS), bisphenol A (BPA), and methylene blue (MB) in aqueous solution could be degraded effectively and rapidly in MW/CNTs system. CNTs with diameter of 10–20 nm exhibited the highest catalytic activity of the three CNTs under MW irradiation. Further, complete degradation was obtained using 10–20 nm CNTs within 7.0 min irradiation when 25 mL MO solution (25 mg/L), 1.2 g/L catalyst dose, 450 W, 2450 MHz, and pH = 6.0 were applied. The rate constants (k) for the degradation of SDBS, MB, MP, MO and BPA using 10–20 nm CNTs/MW system were 0.726, 0.679, 0.463, 0.334 and 0.168 min"−"1, respectively. Therefore, this technology may have potential application for the treatment of targeted organic pollutants in wastewaters.

  11. Microwave-induced carbon nanotubes catalytic degradation of organic pollutants in aqueous solution

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Jing; Xue, Shuang; Song, Youtao; Shen, Manli [School of Environment Science, Liaoning University, Shenyang 110036 (China); Zhang, Zhaohong, E-mail: lnuhjhx@163.com [School of Environment Science, Liaoning University, Shenyang 110036 (China); Yuan, Tianxin; Tian, Fangyuan [School of Environment Science, Liaoning University, Shenyang 110036 (China); Dionysiou, Dionysios D., E-mail: dionysios.d.dionysiou@uc.edu [Environmental Engineering and Science Program, University of Cincinnati, Cincinnati, OH 45221-0012 (United States)

    2016-06-05

    Highlights: • Microwave-induced CNTs-based catalytic degradation technology is developed. • Microwave catalytic activities of CNTs with different diameters are compared. • Organic pollutants with different structure can be degraded in MW/CNTs system. • The 10–20 nm CNTs shows the higher catalytic activity under MW irradiation. - Abstract: In this study, a new catalytic degradation technology using microwave induced carbon nanotubes (MW/CNTs) was proposed and applied in the treatment of organic pollutants in aqueous solution. The catalytic activity of three CNTs of 10–20 nm, 20–40 nm, and 40–60 nm diameters were compared. The results showed that organic pollutants such as methyl orange (MO), methyl parathion (MP), sodium dodecyl benzene sulfonate (SDBS), bisphenol A (BPA), and methylene blue (MB) in aqueous solution could be degraded effectively and rapidly in MW/CNTs system. CNTs with diameter of 10–20 nm exhibited the highest catalytic activity of the three CNTs under MW irradiation. Further, complete degradation was obtained using 10–20 nm CNTs within 7.0 min irradiation when 25 mL MO solution (25 mg/L), 1.2 g/L catalyst dose, 450 W, 2450 MHz, and pH = 6.0 were applied. The rate constants (k) for the degradation of SDBS, MB, MP, MO and BPA using 10–20 nm CNTs/MW system were 0.726, 0.679, 0.463, 0.334 and 0.168 min{sup −1}, respectively. Therefore, this technology may have potential application for the treatment of targeted organic pollutants in wastewaters.

  12. Method to produce catalytically active nanocomposite coatings

    Science.gov (United States)

    Erdemir, Ali; Eryilmaz, Osman Levent; Urgen, Mustafa; Kazmanli, Kursat

    2016-02-09

    A nanocomposite coating and method of making and using the coating. The nanocomposite coating is disposed on a base material, such as a metal or ceramic; and the nanocomposite consists essentially of a matrix of an alloy selected from the group of Cu, Ni, Pd, Pt and Re which are catalytically active for cracking of carbon bonds in oils and greases and a grain structure selected from the group of borides, carbides and nitrides.

  13. Method to produce catalytically active nanocomposite coatings

    Energy Technology Data Exchange (ETDEWEB)

    Erdemir, Ali; Eryilmaz, Osman Levent; Urgen, Mustafa; Kazmanli, Kursat

    2017-12-19

    A nanocomposite coating and method of making and using the coating. The nanocomposite coating is disposed on a base material, such as a metal or ceramic; and the nanocomposite consists essentially of a matrix of an alloy selected from the group of Cu, Ni, Pd, Pt and Re which are catalytically active for cracking of carbon bonds in oils and greases and a grain structure selected from the group of borides, carbides and nitrides.

  14. A study of the catalytic role of a gold electrode in the electrochemical activation of four macrolide antibiotics in sodium bicarbonate solution

    Directory of Open Access Journals (Sweden)

    Milka L. Avramov Ivić

    2010-07-01

    Full Text Available Using the cyclic voltammetry, it has been shown that hydrogen evolution at a gold electrode is necessary in the electrochemical activation of azithromycin dihydrate and erythromycin A. After four hours of the potential holding at –1.2 V vs. SCE, the pH of the electrolyte has been changed from 8.40 to 8.96; from 8.40 to 8.77 in the presence of erythromycin A, and from 8.40 to 9.18 in the presence of azithromycin, indicating the reaction of the hydrogen species with antibiotics. This effect has been confirmed by using the phenolphthalein indicator and by analysing colours of the solutions by UV-Vis, as well as by FTIR spectroscopy. Under the identical experimental conditions at the gold electrode, in contrast to azithromycin dihydrate and erythromycin A, roxithromycin and midecamycin electroactivity promotion has been obtained during the first forward sweep starting from the area of a double layer region.

  15. Highly Selective Synthesis of Catalytically Active Monodisperse Rhodium Nanocubes

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Y.; Grass, M.E.; Kuhn, J.N.; Tao, F.; Habas, S.E.; Huang, W.; Yang, P.; Somorjai, G.A.

    2009-02-21

    Synthesis of monodisperse and shape-controlled colloidal inorganic nanocrystals (NCs) is of increasing scientific interest and technological significance. Recently, shape control of Pt, Pd, Ag, Au, and Rh NCs has been obtained by tuning growth kinetics in various solution-phase approaches, including modified polyol methods, seeded growth by polyol reduction, thermolysis of organometallics, and micelle techniques. Control of reduction kinetics of the noble metal precursors and regulation of the relative growth rates of low-index planes (i.e. {l_brace}100{r_brace} and {l_brace}111{r_brace}) via selective adsorption of selected chemical species are two keys for achieving shape modification of noble metal NCs. One application for noble metal NCs of well-defined shape is in understanding how NC faceting (determines which crystallographic planes are exposed) affects catalytic performance. Rh NCs are used in many catalytic reactions, including hydrogenation, hydroformylation, hydrocarbonylation, and combustion reactions. Shape manipulation of Rh NCs may be important in understanding how faceting on the nanoscale affects catalytic properties, but such control is challenging and there are fewer reports on the shape control of Rh NCs compared to other noble metals. Xia and coworkers obtained Rh multipods exhibiting interesting surface plasmonic properties by a polyol approach. The Somorjai and Tilley groups synthesized crystalline Rh multipods, cubes, horns and cuboctahedra, via polyol seeded growth. Son and colleagues prepared catalytically active monodisperse oleylamine-capped tetrahedral Rh NCs for the hydrogenation of arenes via an organometallic route. More recently, the Somorjai group synthesized sizetunable monodisperse Rh NCs using a one-step polyol technique. In this Communication, we report the highly selective synthesis of catalytically active, monodisperse Rh nanocubes of < 10 nm by a seedless polyol method. In this approach, Br{sup -} ions from trimethyl

  16. Thermal activation of catalytic microjets in blood samples using microfluidic chips.

    Science.gov (United States)

    Soler, Lluís; Martínez-Cisneros, Cynthia; Swiersy, Anka; Sánchez, Samuel; Schmidt, Oliver G

    2013-11-21

    We demonstrate that catalytic microjet engines can out-swim high complex media composed of red blood cells and serum. Despite the challenge presented by the high viscosity of the solution at room temperature, the catalytic microjets can be activated at physiological temperature and, consequently, self-propel in diluted solutions of blood samples. We prove that these microjets self-propel in 10× diluted blood samples using microfluidic chips.

  17. Thermal activation of catalytic microjets in blood samples using microfluidic chips†

    Science.gov (United States)

    Soler, Lluís; Martínez-Cisneros, Cynthia; Swiersy, Anka; Sánchez, Samuel; Schmidt, Oliver G.

    2014-01-01

    We demonstrate that catalytic microjet engines can out-swim high complex media composed of red blood cells and serum. Despite the challenge presented by the high viscosity of the solution at room temperature, the catalytic microjets can be activated at physiological temperature and, consequently, self-propel in diluted solutions of blood samples. We prove that these microjets self-propel in 10× diluted blood samples using microfluidic chips. PMID:24089195

  18. 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

  19. Catalytic Sorption of (Chloro)Benzene and Napthalene in Aqueous Solutions by Granular Activated Carbon Supported Bimetallic Iron and Palladium Nanoparticles

    Science.gov (United States)

    Adsorption of benzene, chlorobenzene, and naphthalene on commercially available granular activated carbon (GAC) and bimetallic nanoparticle (Fe/Pd) loaded GAC was investigated for the potential use in active capping of contaminated sediments. Freundlich and Langmuir linearizatio...

  20. Effect of pH value and delayed-action time on catalytic activity of tartrate niobium(5) complexes

    International Nuclear Information System (INIS)

    Alekseeva, I.I.; Chernysheva, L.M.; Bobkova, M.V.; Solomonov, V.A.

    1987-01-01

    Results of thermokinetic study of catalytic activity of niobium (5) tartrate solutions in the oxidation of ascorbic acid with hydrogen peroxide are presented. Addition of tartrate-ions to a concentration of 1x10 -2 M and higher in niobium (5) diluted solution enhances the catalytic activity of Nb(5). Alkaline tartrate solutions of niobium (5) may be used as standard solutions in determination of niobium microquantities by kinetic method

  1. Microwave Catalytic Oxidation of Hydrocarbons in Aqueous Solutions

    National Research Council Canada - National Science Library

    Cha, Chang

    2003-01-01

    .... A sufficient amount of experimental work has been completed evaluating the performance of the microwave catalytic oxidation process and determining the effect of different operating parameters...

  2. Additive Manufacturing of Catalytically Active Living Materials.

    Science.gov (United States)

    Saha, Abhijit; Johnston, Trevor G; Shafranek, Ryan T; Goodman, Cassandra J; Zalatan, Jesse G; Storti, Duane W; Ganter, Mark A; Nelson, Alshakim

    2018-04-25

    Living materials, which are composites of living cells residing in a polymeric matrix, are designed to utilize the innate functionalities of the cells to address a broad range of applications such as fermentation and biosensing. Herein, we demonstrate the additive manufacturing of catalytically active living materials (AMCALM) for continuous fermentation. A multi-stimuli-responsive yeast-laden hydrogel ink, based on F127-dimethacrylate, was developed and printed using a direct-write 3D printer. The reversible stimuli-responsive behaviors of the polymer hydrogel inks to temperature and pressure are critical, as they enabled the facile incorporation of yeast cells and subsequent fabrication of 3D lattice constructs. Subsequent photo-cross-linking of the printed polymer hydrogel afforded a robust elastic material. These yeast-laden living materials were metabolically active in the fermentation of glucose into ethanol for 2 weeks in a continuous batch process without significant reduction in efficiency (∼90% yield of ethanol). This cell immobilization platform may potentially be applicable toward other genetically modified yeast strains to produce other high-value chemicals in a continuous biofermentation process.

  3. Enhanced catalytic performance of Pd catalyst for formic acid electrooxidation in ionic liquid aqueous solution

    Science.gov (United States)

    Feng, Yuan-Yuan; Yin, Qian-Ying; Lu, Guo-Ping; Yang, Hai-Fang; Zhu, Xiao; Kong, De-Sheng; You, Jin-Mao

    2014-12-01

    A protic ionic liquid (IL), n-butylammonium nitrate (N4NO3), is prepared and employed as the electrolyte for formic acid electrooxidation reaction (FAOR) on Pd catalysts. The oxidation peak potential of FAOR in the IL solution shows about a 200 mV negative shift as compared with those in traditional H2SO4/HClO4 electrolytes, suggesting that FAOR can be more easily carried out on Pd catalysts in IL media. The catalytic properties of Pd toward FAOR are not only dependent on the concentration of IL, as a consequence of the varied electronic conductivity of the IL solution, but also on the high potential limit of the cyclic voltammograms. When the Pd catalyst is cycled up to 1.0 V (vs. SCE), which induces a significant oxidation of Pd, it shows ca. 4.0 times higher activity than that not subjected to the Pd oxidation (up to 0.6 V). The Pd oxides, which are more easily formed in IL solution than in traditional H2SO4/HClO4 electrolytes, may play a crucial role in increasing the catalytic activities of Pd toward FAOR. Our work would shed new light on the mechanism of FAOR and highlight the potential applications of IL as green and environment-friendly electrolytes in fuel cells and other technologies.

  4. Surface composition of carburized tungsten trioxide and its catalytic activity

    International Nuclear Information System (INIS)

    Nakazawa, M.; Okamoto, H.

    1985-01-01

    The surface composition and electronic structure of carburized tungsten trioxide are investigated using x-ray photoelectron spectroscopy (XPS). The relationship between the surface composition and the catalytic activity for methanol electro-oxidation is clarified. The tungsten carbide concentration in the surface layer increases with the carburization time. The formation of tungsten carbide enhances the catalytic activity. On the other hand, the presence of free carbon or tungsten trioxide in the surface layer reduces the activity remarkably. It is also shown that, the higher the electronic density of states near the Fermi level, the higher the catalytic activity

  5. Characterization of microstructure and catalytic of cerium oxide obtained by colloidal solution

    International Nuclear Information System (INIS)

    Senisse, C.A.L.; Bergmann, C.P.; Alves, A.K.

    2012-01-01

    This study investigated to obtain particles of cerium oxide, for use as catalysts for the combustion of methane using the technique of through polymeric colloidal solution. Obtaining the colloidal system is based on hydrolysis of salts such as cerium acetylacetonate, cerium nitrate in the presence of additives such as polyvinylbutyral (PVB), polyvinylpyrrolidone (PVP) and polyvinyl acetate (PVA), at concentrations of 5, 10 and 15% in aqueous or alcoholic medium. These solutions containing ions of interest were subjected to a heat treatment at 650° C for 30 minutes, with heating rate of 2 ° C/ min. After heat treatment, the fibers were characterized according to their morphology, surface area, crystallinity, weight loss and catalytic activity. Samples obtained from cerium acetylacetonate were more reactive than the cerium nitrate to the combustion of methane, as showed greater conversions and higher temperatures reached during the process, which is of utmost importance since the combustion catalytic methane is used for generating thermal energy. After the reaction with methane, the samples underwent significant change in surface area, probably due to the intensity of combustion reactions of the nitrate and the generation of heat involved in this reaction, which gave rise to coarse particles. During the combustion process using the obtained from particles of cerium acetylacetonate, there was the release of large quantities of nitrogen compared to the results of assays with the particles obtained with cerium nitrate. (author)

  6. 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.

  7. Synthesis, structure characterization and catalytic activity of nickel tungstate nanoparticles

    International Nuclear Information System (INIS)

    Pourmortazavi, Seied Mahdi; Rahimi-Nasrabadi, Mehdi; Khalilian-Shalamzari, Morteza; Zahedi, Mir Mahdi; Hajimirsadeghi, Seiedeh Somayyeh; Omrani, Ismail

    2012-01-01

    Graphical abstract: NiWO 4 nanoparticles were prepared via precipitation technique. Experimental parameters of procedure were optimized statistically. Highlights: ► NiWO 4 spherical nanoparticles were synthesized via direct precipitation method. ► Taguchi robust design was used for optimization of synthesis reaction parameters. ► Composition and structural properties of NiWO 4 nanoparticles were characterized. ► EDAX, XRD, SEM, FT-IR, UV–vis and photoluminescence techniques were employed. ► Catalytic activity of the product in a cyclo-addition reaction was investigated. - Abstract: Taguchi robust design was applied to optimize experimental parameters for controllable, simple and fast synthesis of nickel tungstate nanoparticles. NiWO 4 nanoparticles were synthesized by precipitation reaction involving addition of nickel ion solution to the tungstate aqueous reagent and then formation of nickel tungstate nucleolus which are insoluble in aqueous media. Effects of various parameters such as nickel and tungstate concentrations, flow rate of reagent addition and reactor temperature on diameter of synthesized nickel tungstate nanoparticles were investigated experimentally by the aid of orthogonal array design. The results for analysis of variance (ANOVA) showed that particle size of nickel tungstate can be effectively tuned by controlling significant variables involving nickel and tungstate concentrations and flow rate; while, temperature of the reactor has a no considerable effect on the size of NiWO 4 particles. The ANOVA results proposed the optimum conditions for synthesis of nickel tungstate nanoparticles via this technique. Also, under optimum condition nanoparticles of NiWO 4 were prepared and their structure and chemical composition were characterized by means of EDAX, XRD, SEM, FT-IR spectroscopy, UV–vis spectroscopy, and photoluminescence. Finally, catalytic activity of the nanoparticles in a cycloaddition reaction was examined.

  8. Synthesis, structure characterization and catalytic activity of nickel tungstate nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Pourmortazavi, Seied Mahdi, E-mail: pourmortazavi@yahoo.com [Faculty of Material and Manufacturing Technologies, Malek Ashtar University of Technology, Tehran (Iran, Islamic Republic of); Rahimi-Nasrabadi, Mehdi, E-mail: rahiminasrabadi@gmail.com [Department of Chemistry, Imam Hossein University, Tehran (Iran, Islamic Republic of); Khalilian-Shalamzari, Morteza [Department of Chemistry, Imam Hossein University, Tehran (Iran, Islamic Republic of); Zahedi, Mir Mahdi; Hajimirsadeghi, Seiedeh Somayyeh [Islamic Azad University, Varamin Pishva Branch, Varamin (Iran, Islamic Republic of); Omrani, Ismail [Department of Chemistry, Imam Hossein University, Tehran (Iran, Islamic Republic of)

    2012-12-15

    Graphical abstract: NiWO{sub 4} nanoparticles were prepared via precipitation technique. Experimental parameters of procedure were optimized statistically. Highlights: Black-Right-Pointing-Pointer NiWO{sub 4} spherical nanoparticles were synthesized via direct precipitation method. Black-Right-Pointing-Pointer Taguchi robust design was used for optimization of synthesis reaction parameters. Black-Right-Pointing-Pointer Composition and structural properties of NiWO{sub 4} nanoparticles were characterized. Black-Right-Pointing-Pointer EDAX, XRD, SEM, FT-IR, UV-vis and photoluminescence techniques were employed. Black-Right-Pointing-Pointer Catalytic activity of the product in a cyclo-addition reaction was investigated. - Abstract: Taguchi robust design was applied to optimize experimental parameters for controllable, simple and fast synthesis of nickel tungstate nanoparticles. NiWO{sub 4} nanoparticles were synthesized by precipitation reaction involving addition of nickel ion solution to the tungstate aqueous reagent and then formation of nickel tungstate nucleolus which are insoluble in aqueous media. Effects of various parameters such as nickel and tungstate concentrations, flow rate of reagent addition and reactor temperature on diameter of synthesized nickel tungstate nanoparticles were investigated experimentally by the aid of orthogonal array design. The results for analysis of variance (ANOVA) showed that particle size of nickel tungstate can be effectively tuned by controlling significant variables involving nickel and tungstate concentrations and flow rate; while, temperature of the reactor has a no considerable effect on the size of NiWO{sub 4} particles. The ANOVA results proposed the optimum conditions for synthesis of nickel tungstate nanoparticles via this technique. Also, under optimum condition nanoparticles of NiWO{sub 4} were prepared and their structure and chemical composition were characterized by means of EDAX, XRD, SEM, FT-IR spectroscopy, UV

  9. 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.

  10. Catalytic Growth of Macroscopic Carbon Nanofibers Bodies with Activated Carbon

    Science.gov (United States)

    Abdullah, N.; Rinaldi, A.; Muhammad, I. S.; Hamid, S. B. Abd.; Su, D. S.; Schlogl, R.

    2009-06-01

    Carbon-carbon composite of activated carbon and carbon nanofibers have been synthesized by growing Carbon nanofiber (CNF) on Palm shell-based Activated carbon (AC) with Ni catalyst. The composites are in an agglomerated shape due to the entanglement of the defective CNF between the AC particles forming a macroscopic body. The macroscopic size will allow the composite to be used as a stabile catalyst support and liquid adsorbent. The preparation of CNT/AC nanocarbon was initiated by pre-treating the activated carbon with nitric acid, followed by impregnation of 1 wt% loading of nickel (II) nitrate solutions in acetone. The catalyst precursor was calcined and reduced at 300° C for an hour in each step. The catalytic growth of nanocarbon in C2H4/H2 was carried out at temperature of 550° C for 2 hrs with different rotating angle in the fluidization system. SEM and N2 isotherms show the level of agglomeration which is a function of growth density and fluidization of the system. The effect of fluidization by rotating the reactor during growth with different speed give a significant impact on the agglomeration of the final CNF/AC composite and thus the amount of CNFs produced. The macrostructure body produced in this work of CNF/AC composite will have advantages in the adsorbent and catalyst support application, due to the mechanical and chemical properties of the material.

  11. Study on the correlation between the surface active species of Pd/cordierite monolithic catalyst and its catalytic activity

    International Nuclear Information System (INIS)

    Liao, Hengcheng; Zuo, Peiyuan; Liu, Miaomiao

    2016-01-01

    Two Pd-loading routes and three Pd-precursor matters were adopted to prepare Pd/(Ce,Y)O_2/γ-Al_2O_3/cordierite monolithic catalyst. The surface active species on the catalyst were characterized by XPS, and its catalytic activity for methane combustion was tested, and the dynamics of the catalytic combustion reaction was also discussed. Pd-loading route and Pd-precursor mass have a significant influence on the catalytic activity and surface active species. The sol dipping method is more advanced than the aqueous solution impregnating method. PN-sol catalyst, by sol dipping combined with Pd(NO_3)_2-precursor, has the best catalytic activity. The physical reason is the unique active Pd phase coexisting with active PdO phase on the surface, and thus the Pd3d_5_/_2 binding energy of surface species and apparent activation energy of combustion reaction are considerably decreased. The catalytic activity index, Pd3d_5_/_2 binding energy and apparent activation energy are highly tied each other with exponential relations.

  12. Catalytic and physical properties of γ-irradiated catalase in dilute solution

    International Nuclear Information System (INIS)

    Gasyna, Z.; Bachman, S.

    1974-01-01

    The catalytic and physical properties of irradiated beef liver catalase have been studied. Modification of the enzyme by γ-rays brings about its reducibility by dithionite. The decrease of the catalytic activity is found to correspond to the decrease in the content of nonreducible catalase. Microaggregates of catalase molecules induced by irradiation have been fractionated. The results lead to the conclusion that aggregates are composed of active and modified catalase monomers. (author)

  13. Trends in the Catalytic CO Oxidation Activity of Nanoparticles

    DEFF Research Database (Denmark)

    Nørskov, Jens Kehlet; Falsig, Hanne; Larsen, Britt Hvolbæk

    2008-01-01

    Going for gold: Density functional calculations show how gold nanoparticles are more active catalysts for CO oxidation than other metal nanoparticles. The high catalytic activity of nanosized gold clusters at low temperature is found to be related to the ability of low-coordinate metal atoms...

  14. Mechanisms of catalytic activity in heavily coated hydrocracking catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Millan, M.; Adell, C.; Hinojosa, C.; Herod, A.A.; Kandiyoti, R. [University of London Imperial College Science Technology & Medicine, London (United Kingdom). Dept. of Chemical Engineering

    2008-01-15

    Catalyst deactivation by coke deposition has a direct impact on the economic viability of heavy hydrocarbon upgrading processes, such as coal liquefaction and oil residue hydroprocessing. Coke deposition is responsible for rapid loss of catalytic activity and it mostly takes place in the early stages of hydrocracking. The effect of carbonaceous deposition on the catalytic activity of a chromium pillared montmorillonite has been studied in the present work. Its catalytic activity in hydrocracking a coal extract was evaluated based on the boiling point distributions of feed and products obtained by thermogravimetric analysis (TGA), and their characterisation by size exclusion chromatography (SEC) and UV-Fluorescence spectroscopy (UV-F). A large deposition on the catalyst was observed after two successive 2-hour long runs in which the catalyst recovered from the first run was reused in the second. The pillared clay retained its activity even though it showed high carbon loading, a large drop in surface area and complete apparent pore blockage. Some observations may contribute to explain this persistent catalytic activity. First, there is evidence suggesting the dynamic nature of the carbonaceous deposits, which continuously exchange material with the liquid, allowing catalytic activity to continue. Secondly, Scanning Electron Microscopy (SEM) on the used Cr montmorillonite has shown preferential deposition on some regions of the catalyst, which leaves a fraction of the surface relatively exposed. Finally, evidence from SEM coupled to X-ray microanalysis also suggest that deposits are thinner in areas where the active phase of the catalyst is present in higher concentrations. Hydrogenation on the active sites would make the deposits more soluble in the liquid cleaning of surrounding area from deposits.

  15. Synthesis, structure characterization and catalytic activity of nickel tungstate nanoparticles

    Science.gov (United States)

    Pourmortazavi, Seied Mahdi; Rahimi-Nasrabadi, Mehdi; Khalilian-Shalamzari, Morteza; Zahedi, Mir Mahdi; Hajimirsadeghi, Seiedeh Somayyeh; Omrani, Ismail

    2012-12-01

    Taguchi robust design was applied to optimize experimental parameters for controllable, simple and fast synthesis of nickel tungstate nanoparticles. NiWO4 nanoparticles were synthesized by precipitation reaction involving addition of nickel ion solution to the tungstate aqueous reagent and then formation of nickel tungstate nucleolus which are insoluble in aqueous media. Effects of various parameters such as nickel and tungstate concentrations, flow rate of reagent addition and reactor temperature on diameter of synthesized nickel tungstate nanoparticles were investigated experimentally by the aid of orthogonal array design. The results for analysis of variance (ANOVA) showed that particle size of nickel tungstate can be effectively tuned by controlling significant variables involving nickel and tungstate concentrations and flow rate; while, temperature of the reactor has a no considerable effect on the size of NiWO4 particles. The ANOVA results proposed the optimum conditions for synthesis of nickel tungstate nanoparticles via this technique. Also, under optimum condition nanoparticles of NiWO4 were prepared and their structure and chemical composition were characterized by means of EDAX, XRD, SEM, FT-IR spectroscopy, UV-vis spectroscopy, and photoluminescence. Finally, catalytic activity of the nanoparticles in a cycloaddition reaction was examined.

  16. Sorting catalytically active polymersome nanoreactors by flow cytometry

    NARCIS (Netherlands)

    Nallani, M.; Woestenenk, R.; de Hoog, H.P.M.; van Dongen, S.F.M.; Boezeman, J.; Cornelissen, J.J.L.M.; Nolte, R.J.M.; van Hest, J.C.M.

    2009-01-01

    A strategy that involves a versatile one-step preparation procedure of enzyme filled porous and stable polymeric catalytically active nanoreactors (polymersomes) by flow cytometry was reported. A 1:1 mixture of the polymerase dispersions was analyzed in a Coulter Epics Elite Flow Cytometer, while

  17. Catalytic Activity Control via Crossover between Two Different Microstructures

    KAUST Repository

    Zhou, Yuheng

    2017-09-08

    Metal nanocatalysts hold great promise for a wide range of heterogeneous catalytic reactions, while the optimization strategy of catalytic activity is largely restricted by particle size or shape control. Here, we demonstrate that a reversible microstructural control through the crossover between multiply-twinned nanoparticle (MTP) and single crystal (SC) can be readily achieved by solvent post-treatment on gold nanoparticles (AuNPs). Polar solvents (e.g. water, methanol) direct the transformation from MTP to SC accompanied by the disappearance of twinning and stacking faults. A reverse transformation from SC to MTP is achieved in non-polar solvent (e.g. toluene) mixed with thiol ligands. The transformation between two different microstructures is directly observed by in-situ TEM and leads to a drastic modulation of catalytic activity towards the gas-phase selective oxidation of alcohols. There is a quasi-linear relationship between TOFs and MTP concentrations. Based on the combined experimental and theoretical investigations of alcohol chemisorption on these nanocatalysts, we propose that the exposure of {211}-like microfacets associated with twin boundaries and stack faults accounts for the strong chemisorption of alcohol molecules on MTP AuNPs and thus the exceptionally high catalytic activity.

  18. 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.)

  19. Catalytic Ethanol Dehydration over Different Acid-activated Montmorillonite Clays.

    Science.gov (United States)

    Krutpijit, Chadaporn; Jongsomjit, Bunjerd

    2016-01-01

    In the present study, the catalytic dehydration of ethanol to obtain ethylene over montmorillonite clays (MMT) with mineral acid activation including H2SO4 (SA-MMT), HCl (HA-MMT) and HNO3 (NA-MMT) was investigated at temperature range of 200 to 400°C. It revealed that HA-MMT exhibited the highest catalytic activity. Ethanol conversion and ethylene selectivity were found to increase with increased reaction temperature. At 400°C, the HA-MMT yielded 82% of ethanol conversion having 78% of ethylene yield. At lower temperature (i.e. 200 to 300°C), diethyl ether (DEE) was a major product. The highest activity obtained from HA-MMT can be attributed to an increase of weak acid sites and acid density by the activation of MMT with HCl. It can be also proven by various characterization techniques that in most case, the main structure of MMT did not alter by acid activation (excepted for NA-MMT). Upon the stability test for 72 h during the reaction, the MMT and HA-MMT showed only slight deactivation due to carbon deposition. Hence, the acid activation of MMT by HCl is promising to enhance the catalytic dehydration of ethanol.

  20. 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.)

  1. Natural clinoptilolite exchanged with iron: characterization and catalytic activity in nitrogen monoxide reduction

    Directory of Open Access Journals (Sweden)

    Daria Tito-Ferro

    2016-12-01

    Full Text Available The aim of this work was to characterize the natural clinoptilolite from Tasajeras deposit, Cuba, modified by hydrothermal ion-exchange with solutions of iron (II sulfate and iron (III nitrate in acid medium. Besides this, its catalytic activity to reduce nitrogen monoxide with carbon monoxide/propene in the presence of oxygen was evaluated. The characterization was performed by Mössbauer and UV-Vis diffuse reflectance spectroscopies and adsorption measurements. The obtained results lead to conclude that in exchanged samples, incorporated divalent and trivalent irons are found in octahedral coordination. Both irons should be mainly in cationic extra-framework positions inside clinoptilolite channels as charge compensating cations, and also as iron oxy-hydroxides resulting from limited hydrolysis of these cations. The iron (III exchanged samples has a larger amount of iron oxy-hydroxides agglomerates. The iron (II exchanged samples have additionally iron (II sulfate adsorbed. The catalytic activity in the nitrogen monoxide reduction is higher in the exchanged zeolites than starting. Among all samples, those exchanged of iron (II has the higher catalytic activity. This lead to outline that, main catalytically active centers are associated with divalent iron.

  2. 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.

  3. Study of the catalytic activity of supported technetium catalysts

    International Nuclear Information System (INIS)

    Spitsyn, V.I.; Mikhailenko, I.E.; Pokorovskaya, O.V.

    1985-01-01

    The radioactive d metal 43 Tc 99 has catalytic properties in the synthesis of ammonia. For the purpose of reducing the quantity of the radioactive metal and of increasing the specific surface, the active component was applied to BaTiO 3 and gamma-Al 2 O 3 supports. This paper uses charcoal as a support and a table presents the catalytic activity of the samples during the synthesis of ammonia. X-ray diffractometric investigation of the catalysts was carried out with the use of Cu K /SUB alpha/ radiation. It is shown that the catalysts. The values of the specific rate constants of technetium in the catalysts. The values of the specific rate constants remain practically constant for all the catalyst samples studied, attesting to the absence of a specific metal-support interaction during the synthesis of ammonia

  4. Catalytic activity of zeolite-containing catalysts in cumene cracking

    Energy Technology Data Exchange (ETDEWEB)

    Koval' chuk, L V; Takhtarova, G N; Topchieva, K V [Moskovskij Gosudarstvennyj Univ. (USSR). Kafedra Fizicheskoj Khimii

    1977-01-01

    The catalytic properties are studied of decationized forms (Ca and La) of zeolite-containing catalysts in relation to the nature of the cation and the degree of exchange in the cumene cracking reaction. It has been established that the increase in the activity of Ca-decationized catalysts occurs at a degree of exchange from 22 to 40% and at a ratio of the cation and decationized areas from 0.4 to 1. For La-decationized catalysts the activity increases at a degree of exchange up to 60% and at a ratio between the cation and decationized areas exceeding 1.

  5. Catalytic activity of lanthanum oxide for the reduction of cyclohexanone

    International Nuclear Information System (INIS)

    Sugunan, S.; Sherly, K.B.

    1994-01-01

    Lanthanum oxides, La 2 O 3 has been found to be an effective catalyst for the liquid phase reduction of cyclohexanone. The catalytic activities of La 2 O 3 activated at 300, 500 and 800 degC and its mixed oxides with alumina for the reduction of cylcohexanone with 2-propanol have been determined and the data parallel that of the electron donating properties of the catalysts. The electron donating properties of the catalysts have been determined from the adsorption of electron acceptors of different electron affinities on the surface of these oxides. (author). 15 refs., 2 figs., 1 tab

  6. Optical manipulation and catalytic activity enhanced by surface plasmon effect

    Science.gov (United States)

    Zou, Ningmu; Min, Jiang; Jiao, Wenxiang; Wang, Guanghui

    2017-02-01

    For optical manipulation, a nano-optical conveyor belt consisting of an array of gold plasmonic non-concentric nano-rings (PNNRs) is demonstrated for the realization of trapping and unidirectional transportation of nanoparticles by polarization rotation of excitation beam. These hot spots of an asymmetric plasmonic nanostructure are polarization dependent, therefore, one can use the incident polarization state to manipulate the trapped targets. Trapped particles could be transferred between adjacent PNNRs in a given direction just by rotating the polarization of incident beam due to unbalanced potential. The angular dependent distribution of electric field around PNNR has been solved using the three- dimensional finite-difference time-domain (FDTD) technique. For optical enhanced catalytic activity, the spectral properties of dimers of Au nanorod-Au nanorod nanostructures under the excitation of 532nm photons have been investigated. With a super-resolution catalytic mapping technique, we identified the existence of "hot spot" in terms of catalytic reactivity at the gap region within the twined plasmonic nanostructure. Also, FDTD calculation has revealed an intrinsic correlation between hot electron transfer.

  7. Halide-Enhanced Catalytic Activity of Palladium Nanoparticles Comes at the Expense of Catalyst Recovery

    Directory of Open Access Journals (Sweden)

    Azzedine Bouleghlimat

    2017-09-01

    Full Text Available In this communication, we present studies of the oxidative homocoupling of arylboronic acids catalyzed by immobilised palladium nanoparticles in aqueous solution. This reaction is of significant interest because it shares a key transmetallation step with the well-known Suzuki-Miyaura cross-coupling reaction. Additives can have significant effects on catalysis, both in terms of reaction mechanism and recovery of catalytic species, and our aim was to study the effect of added halides on catalytic efficiency and catalyst recovery. Using kinetic studies, we have shown that added halides (added as NaCl and NaBr can increase the catalytic activity of the palladium nanoparticles more than 10-fold, allowing reactions to be completed in less than half a day at 30 °C. However, this increased activity comes at the expense of catalyst recovery. The results are in agreement with a reaction mechanism in which, under conditions involving high concentrations of chloride or bromide, palladium leaching plays an important role. Considering the evidence for analogous reactions occurring on the surface of palladium nanoparticles under different reaction conditions, we conclude that additives can exert a significant effect on the mechanism of reactions catalyzed by nanoparticles, including switching from a surface reaction to a solution reaction. The possibility of this switch in mechanism may also be the cause for the disagreement on this topic in the literature.

  8. DNA-Catalytically Active Gold Nanoparticle Conjugates-Based Colorimetric Multidimensional Sensor Array for Protein Discrimination.

    Science.gov (United States)

    Wei, Xiangcong; Chen, Zhengbo; Tan, Lulu; Lou, Tianhong; Zhao, Yan

    2017-01-03

    A series of single-strand oligonucleotides functionalized catalytically active gold nanoparticle (AuNPs) as nonspecific receptors have been designed to build a protein sensing array. We take advantage of the correlation between the catalytic activity and the exposed surface area of AuNPs, i.e., DNA-proteins interactions mask the surface area of AuNPs, leading to poor catalytic performance of AuNPs. As the number of DNA-bound proteins increases, the surfaces of AuNPs become more masked; thus, the time of 4- nitrophenol/NaBH 4 reaction for color change (yellow → colorless) of the solution increases. Taking advantage of three nonspecific SH-labeled DNA sequences (A15, C15, and T15) as array sensing elements and the color-change time (CCT) of the solution as signal readout, colorimetric response patterns can be obtained on the array and identified via linear discriminant analysis (LDA). Eleven proteins have been completely distinguished with 100% accuracy with the naked eye at the 30 nM level. Remarkably, two similar proteins (bovine serum albumin and human serum albumin), two different proteins (bovine serum albumin and concanavalin) at the same concentration, and the mixtures of the two proteins with different molar ratios have been discriminated with 100%. The practicability of this sensor array is further validated by high accuracy (100%) identification of 11 proteins in human serum samples.

  9. 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.

  10. Intramolecular Crosstalk between Catalytic Activities of Receptor Kinases

    KAUST Repository

    Kwezi, Lusisizwe

    2018-01-22

    Signal modulation is important for the growth and development of plants and this process is mediated by a number of factors including physiological growth regulators and their associated signal transduction pathways. Protein kinases play a central role in signaling, including those involving pathogen response mechanisms. We previously demonstrated an active guanylate cyclase (GC) catalytic center in the brassinosteroid insensitive receptor (AtBRI1) within an active intracellular kinase domain resulting in dual enzymatic activity. Here we propose a novel type of receptor architecture that is characterized by a functional GC catalytic center nested in the cytosolic kinase domain enabling intramolecular crosstalk. This may be through a cGMP-AtBRI1 complex forming that may induce a negative feedback mechanism leading to desensitisation of the receptor, regulated through the cGMP production pathway. We further argue that the comparatively low but highly localized cGMP generated by the GC in response to a ligand is sufficient to modulate the kinase activity. This type of receptor therefore provides a molecular switch that directly and/or indirectly affects ligand dependent phosphorylation of downstream signaling cascades and suggests that subsequent signal transduction and modulation works in conjunction with the kinase in downstream signaling.

  11. Intramolecular Crosstalk between Catalytic Activities of Receptor Kinases

    KAUST Repository

    Kwezi, Lusisizwe; Wheeler, Janet I; Marondedze, Claudius; Gehring, Christoph A; Irving, Helen R

    2018-01-01

    Signal modulation is important for the growth and development of plants and this process is mediated by a number of factors including physiological growth regulators and their associated signal transduction pathways. Protein kinases play a central role in signaling, including those involving pathogen response mechanisms. We previously demonstrated an active guanylate cyclase (GC) catalytic center in the brassinosteroid insensitive receptor (AtBRI1) within an active intracellular kinase domain resulting in dual enzymatic activity. Here we propose a novel type of receptor architecture that is characterized by a functional GC catalytic center nested in the cytosolic kinase domain enabling intramolecular crosstalk. This may be through a cGMP-AtBRI1 complex forming that may induce a negative feedback mechanism leading to desensitisation of the receptor, regulated through the cGMP production pathway. We further argue that the comparatively low but highly localized cGMP generated by the GC in response to a ligand is sufficient to modulate the kinase activity. This type of receptor therefore provides a molecular switch that directly and/or indirectly affects ligand dependent phosphorylation of downstream signaling cascades and suggests that subsequent signal transduction and modulation works in conjunction with the kinase in downstream signaling.

  12. Combustion synthesis and catalytic activity of LaCoO{sub 3} for HMX thermal decomposition

    Energy Technology Data Exchange (ETDEWEB)

    Wei, Zhi-Xian; Chi, Ying-Nan [Department of Chemistry, Institute for Chemical Physics, Beijing Institute of Technology (China); Hu, Chang-Wen [State Key Laboratory of Explosion Science, Technology Beijing Institute of Technology, Beijing (China); Liu, Hai-Yan [Department of Chemistry, Science Institute, North China University, Taiyuan, Shanxi (China)

    2009-10-15

    Perovskite-type LaCoO{sub 3} was prepared by stearic acid solution combustion method and characterized by XRD, DSC-TG, and XPS techniques. The catalytic activities of LaCoO{sub 3} for HMX (octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine) thermal decomposition were investigated. The as-prepared LaCoO{sub 3} shows higher activity than the calcined one. This could be due to higher concentration of surface-adsorbed oxygen and hydroxyl species as well as higher BET surface area of the as-prepared LaCoO{sub 3}. (Abstract Copyright [2009], Wiley Periodicals, Inc.)

  13. [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.

  14. Growth of catalytically active nanostructures in the nonequilibrium epitaxy regime

    International Nuclear Information System (INIS)

    Gorshkov, V.M.; Kuzmenko, V.V.

    2015-01-01

    The dynamics of metal atom deposition on a flat metal substrate in the diffusion mode has been studied. Conditions for growing up the periodic structures with a developed surface morphology are found. The applicability of the results obtained to the manufacture of catalysts is analyzed. In particular, when platinum atoms are deposited on a gold substrate, which is expedient by cost reasons, a system of nanopyramids confined by (111) facets can be formed under special conditions. This structure possesses an ultrahigh catalytic activity and is promising for applications in chemical industry

  15. Structure and catalytic activity of regenerated spent hydrotreating catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Kim, C.S.; Massoth, F.E.; Furimsky, E. (Utah University, Salt Lake City, UT (USA). Dept. of Fuels Engineering)

    1992-11-01

    Two spent catalysts, obtained from different hydrodemetallation operations, were regenerated by two different treatments, viz. 2% (V/V) O[sub 2]/N[sub 2] and air. One spent catalyst (B), contained 3 wt% V and 15 wt% C, while the other (H) contained 10 wt% V, 14 wt% C and 8 wt% Fe. After regeneration in the O[sub 2]/N[sub 2] stream, catalyst B showed essentially complete recovery of its original surface area, whereas catalyst H showed only 70% recovery. Both catalysts showed substantial losses in surface area by the air treatment. Catalytic activity tests on the regenerated catalysts for hydrodesulfurization of thiophene and for hydrogenation of 1-hexene showed low recovery of activities, even for the regenerated catalyst in which the surface area had been completely recovered. X-ray diffraction analyses of the spent-regenerated catalysts revealed substantial changes in catalyst structure. Surface area and catalytic activity results were qualitatively explained by these catalyst structural changes. 17 refs., 1 fig., 3 tabs.

  16. Block copolymer hollow fiber membranes with catalytic activity and pH-response

    KAUST Repository

    Hilke, Roland

    2013-08-14

    We fabricated block copolymer hollow fiber membranes with self-assembled, shell-side, uniform pore structures. The fibers in these membranes combined pores able to respond to pH and acting as chemical gates that opened above pH 4, and catalytic activity, achieved by the incorporation of gold nanoparticles. We used a dry/wet spinning process to produce the asymmetric hollow fibers and determined the conditions under which the hollow fibers were optimized to create the desired pore morphology and the necessary mechanical stability. To induce ordered micelle assembly in the doped solution, we identified an ideal solvent mixture as confirmed by small-angle X-ray scattering. We then reduced p-nitrophenol with a gold-loaded fiber to confirm the catalytic performance of the membranes. © 2013 American Chemical Society.

  17. Block copolymer hollow fiber membranes with catalytic activity and pH-response

    KAUST Repository

    Hilke, Roland; Neelakanda, Pradeep; Madhavan, Poornima; Vainio, Ulla; Behzad, Ali Reza; Sougrat, Rachid; Nunes, Suzana Pereira; Peinemann, Klaus-Viktor

    2013-01-01

    We fabricated block copolymer hollow fiber membranes with self-assembled, shell-side, uniform pore structures. The fibers in these membranes combined pores able to respond to pH and acting as chemical gates that opened above pH 4, and catalytic activity, achieved by the incorporation of gold nanoparticles. We used a dry/wet spinning process to produce the asymmetric hollow fibers and determined the conditions under which the hollow fibers were optimized to create the desired pore morphology and the necessary mechanical stability. To induce ordered micelle assembly in the doped solution, we identified an ideal solvent mixture as confirmed by small-angle X-ray scattering. We then reduced p-nitrophenol with a gold-loaded fiber to confirm the catalytic performance of the membranes. © 2013 American Chemical Society.

  18. TET2 Regulates Mast Cell Differentiation and Proliferation through Catalytic and Non-catalytic Activities

    Directory of Open Access Journals (Sweden)

    Sara Montagner

    2016-05-01

    Full Text Available Summary: Dioxygenases of the TET family impact genome functions by converting 5-methylcytosine (5mC in DNA to 5-hydroxymethylcytosine (5hmC. Here, we identified TET2 as a crucial regulator of mast cell differentiation and proliferation. In the absence of TET2, mast cells showed disrupted gene expression and altered genome-wide 5hmC deposition, especially at enhancers and in the proximity of downregulated genes. Impaired differentiation of Tet2-ablated cells could be relieved or further exacerbated by modulating the activity of other TET family members, and mechanistically it could be linked to the dysregulated expression of C/EBP family transcription factors. Conversely, the marked increase in proliferation induced by the loss of TET2 could be rescued exclusively by re-expression of wild-type or catalytically inactive TET2. Our data indicate that, in the absence of TET2, mast cell differentiation is under the control of compensatory mechanisms mediated by other TET family members, while proliferation is strictly dependent on TET2 expression. : The impact of TET enzymes on gene expression and cell function is incompletely understood. Montagner et al. investigate the TET-mediated regulation of mast cell differentiation and function, uncover transcriptional pathways regulated by TET2, and identify both enzymatic activity-dependent and -independent functions of TET2. Keywords: differentiation, DNA hydroxymethylation, epigenetics, mast cells, proliferation, TET

  19. Removal of radionuclides from partitioning waste solutions by adsorption and catalytic oxidation methods

    Energy Technology Data Exchange (ETDEWEB)

    Yamagishi, Isao; Yamaguchi, Isoo [Japan Atomic Energy Research Inst., Tokai, Ibaraki (Japan). Tokai Research Establishment; Kubota, Masumitsu [Research Organization for Information Science and Technology (RIST), Tokai, Ibaraki (Japan)

    2000-09-01

    Adsorption of radionuclides with inorganic ion exchangers and catalytic oxidation of a complexant were studied for the decontamination of waste solutions generated in past partitioning tests with high-level liquid waste. Granulated ferrocyanide and titanic acid were used for adsorption of Cs and Sr, respectively, from an alkaline solution resulting from direct neutralization of an acidic waste solution. Both Na and Ba inhibited adsorption of Sr but Na did not that of Cs. These exchangers adsorbed Cs and Sr at low concentration with distribution coefficients of more than 10{sup 4}ml/g from 2M Na solution of pH11. Overall decontamination factors (DFs) of Cs and total {beta} nuclides exceeded 10{sup 5} and 10{sup 3}, respectively, at the neutralization-adsorption step of actual waste solutions free from a complexant. The DF of total {alpha} nuclides was less than 10{sup 3} for a waste solution containing diethylenetriaminepentaacetic acid (DTPA). DTPA was rapidly oxidized by nitric acid in the presence of a platinum catalyst, and radionuclides were removed as precipitates by neutralization of the resultant solution. The DF of {alpha} nuclides increased to 8x10{sup 4} by addition of the oxidation step. The DFs of Sb and Co were quite low through the adsorption step. A synthesized Ti-base exchanger (PTC) could remove Sb with the DF of more than 4x10{sup 3}. (author)

  20. A New Property of Conjugated Polymer PFP: Catalytic Degradation of Methylene Blue Aqueous Solution

    Institute of Scientific and Technical Information of China (English)

    2005-01-01

    A new property of conjugated polymer poly(furancarbinol-co-phenol)(PFP) was studied.The target copolymer was used as a catalyst after proper heating treatment. And dye methylene blue (MB) could be fully degraded and largely mineralized on PFP, under natural light or even in dark, in a few minutes. Furthermore, the catalytic activity could be preserved after several runs and the catalyst was readily separated. The effect of calcination temperature was also observed.

  1. Design parameters for measurements of local catalytic activity on surfaces

    DEFF Research Database (Denmark)

    Johansson, Martin; Johannessen, Tue; Jørgensen, Jan Hoffmann

    2006-01-01

    Computational fluid dynamics in combination with experiments is used to characterize a gas sampling device for measurements of the local catalytic activity on surfaces. The device basically consists of a quartz capillary mounted concentrically inside an aluminum tube. Reactant gas is blown toward......, the limits of the range in reaction rate, which can be Studied are estimated. (c) 2005 Elsevier B.V. All rights reserved.......Computational fluid dynamics in combination with experiments is used to characterize a gas sampling device for measurements of the local catalytic activity on surfaces. The device basically consists of a quartz capillary mounted concentrically inside an aluminum tube. Reactant gas is blown toward...... limit for the lateral resolution of the measurement, and that a flow rate of the order of 240 (ml/min)(n) is sufficient to achieve this resolution. The sensitivity is reasonable also with high flow rates, due to the presence of a pocket of stagnant gas under the tip of the capillary. Furthermore...

  2. Direct instrumental identification of catalytically active surface sites

    Science.gov (United States)

    Pfisterer, Jonas H. K.; Liang, Yunchang; Schneider, Oliver; Bandarenka, Aliaksandr S.

    2017-09-01

    The activity of heterogeneous catalysts—which are involved in some 80 per cent of processes in the chemical and energy industries—is determined by the electronic structure of specific surface sites that offer optimal binding of reaction intermediates. Directly identifying and monitoring these sites during a reaction should therefore provide insight that might aid the targeted development of heterogeneous catalysts and electrocatalysts (those that participate in electrochemical reactions) for practical applications. The invention of the scanning tunnelling microscope (STM) and the electrochemical STM promised to deliver such imaging capabilities, and both have indeed contributed greatly to our atomistic understanding of heterogeneous catalysis. But although the STM has been used to probe and initiate surface reactions, and has even enabled local measurements of reactivity in some systems, it is not generally thought to be suited to the direct identification of catalytically active surface sites under reaction conditions. Here we demonstrate, however, that common STMs can readily map the catalytic activity of surfaces with high spatial resolution: we show that by monitoring relative changes in the tunnelling current noise, active sites can be distinguished in an almost quantitative fashion according to their ability to catalyse the hydrogen-evolution reaction or the oxygen-reduction reaction. These data allow us to evaluate directly the importance and relative contribution to overall catalyst activity of different defects and sites at the boundaries between two materials. With its ability to deliver such information and its ready applicability to different systems, we anticipate that our method will aid the rational design of heterogeneous catalysts.

  3. 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.

  4. Synthesis of monodisperse palladium nanocubes and their catalytic activity for methanol electrooxidation

    International Nuclear Information System (INIS)

    Hao, Ding; Xue-Zhao, Shi; Cheng-Min, Shen; Chao, Hui; Zhi-Chuan, Xu; Chen, Li; Yuan, Tian; Deng-Ke, Wang; Hong-Jun, Gao

    2010-01-01

    The single crystalline palladium nanocubes with an average size of 7 nm were prepared in the presence of poly (vinyl pyrrolidone) (PVP) and KBr using the polyol method. The as-prepared Pd nanocubes were highly uniform in both size and shape. The ordered packing structures including monolayer and multilayer can be fabricated via the rate-controlled evaporation of solution solvent. The electrochemical catalytic activity of these Pd nanocubes towards methanol oxidation was found to be higher than that of spherical Pd nanoparticles of similar size. (condensed matter: structure, thermal and mechanical properties)

  5. Synthesis of monodisperse palladium nanocubes and their catalytic activity for methanol electrooxidation

    Science.gov (United States)

    Ding, Hao; Shi, Xue-Zhao; Shen, Cheng-Min; Hui, Chao; Xu, Zhi-Chuan; Li, Chen; Tian, Yuan; Wang, Deng-Ke; Gao, Hong-Jun

    2010-10-01

    The single crystalline palladium nanocubes with an average size of 7 nm were prepared in the presence of poly (vinyl pyrrolidone) (PVP) and KBr using the polyol method. The as-prepared Pd nanocubes were highly uniform in both size and shape. The ordered packing structures including monolayer and multilayer can be fabricated via the rate-controlled evaporation of solution solvent. The electrochemical catalytic activity of these Pd nanocubes towards methanol oxidation was found to be higher than that of spherical Pd nanoparticles of similar size.

  6. THE INFLUENCE OF THIOSEMICARBAZONE 2,3-DIHYDROXYBENZALDEHYDE ON CATALYTIC CURRENTS IN THE SYSTEM MOLYBDENUM (VI – POTASSIUM CHLORATE IN ACID SULFATE SOLUTIONS

    Directory of Open Access Journals (Sweden)

    Ludmila Chiriac

    2011-06-01

    Full Text Available The polarographic catalytic current in acid solutions of Mo(VI, thiosemicarbazone 2,3-dihydroxybenzaldehyde (TSC 2,3-DHBA and chlorate ions has been investigated. The scheme of reactions, taking place in the solutions and on the electrode, has been proposed. The increase of the catalytic current is explained by the formation of an active intermediate complex [Mo(V×TSC 2,3-DHBA (ClO-3]. The rate constant of this complex formation K = 2.56 × 106 mol-1×dm3×s-1, the activation energy Ea = 15.9 kcal×mol-1 and the reaction activation entropy ∆Sa¹ = -23.5 e.u. have been calculated.

  7. Reduced graphene oxide supported platinum nanocubes composites: one-pot hydrothermal synthesis and enhanced catalytic activity

    International Nuclear Information System (INIS)

    Li, Fumin; Gao, Xueqing; Xue, Qi; Li, Shuni; Chen, Yu; Lee, Jong-Min

    2015-01-01

    Reduced graphene oxide (rGO) supported platinum nanocubes (Pt-NCs) composites (Pt-NCs/rGO) were synthesized successfully by a water-based co-chemical reduction method, in which polyallylamine hydrochloride acted as a multi-functional molecule for the functionalization of graphene oxide, anchorage of Pt II precursor, and control of Pt crystal facets. The morphology, structure, composition, and catalytic property of Pt-NCs/rGO composites were characterized in detail by various spectroscopic techniques. Transmission electron microscopy images showed well-defined Pt-NCs with an average size of 9 nm uniformly distributed on the rGO surface. The as-prepared Pt-NCs/rGO composites had excellent colloidal stability in the aqueous solution, and exhibited superior catalytic activity towards the hydrogenation reduction of nitro groups compared to commercial Pt black. The improved catalytic activity originated from the abundant exposed Pt{100} facets of Pt-NCs, excellent dispersion of Pt-NCs on the rGO surface, and synergistic effect between Pt-NCs and rGO. (paper)

  8. 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.

  9. Triblock copolymer-mediated synthesis of catalytically active gold nanostructures

    Science.gov (United States)

    Santos, Douglas C.; de Souza, Viviane C.; Vasconcelos, Diego A.; Andrade, George R. S.; Gimenez, Iara F.; Teixeira, Zaine

    2018-04-01

    The design of nanostructures based on poly(ethylene oxide)-poly(propylene)-poly(ethylene oxide) (PEO-PPO-PEO) and metal nanoparticles is becoming an important research topic due to their multiple functionalities in different fields, including nanomedicine and catalysis. In this work, water-soluble gold nanoparticles have been prepared through a green aqueous synthesis method using Pluronic F127 as both reducing and stabilizing agents. The size dependence (varying from 2 to 70 nm) and stability of gold nanoparticles were systematically studied by varying some parameters of synthesis, which were the polymer concentration, temperature, and exposure to UV-A light, being monitored by UV-Vis spectroscopy and TEM. Also, an elaborated study regarding to the kinetic of formation (nucleation and growth) was presented. Finally, the as-prepared Pluronic-capped gold nanoparticles have shown excellent catalytic activity towards the reduction of 4-nitrophenol to 4-aminophenol with sodium borohydride, in which a higher catalytic performance was exhibited when compared with gold nanoparticles prepared by classical reduction method using sodium citrate. [Figure not available: see fulltext.

  10. Catalytic oxidation of NO to NO2 on activated carbon

    International Nuclear Information System (INIS)

    Zhancheng Guo; Yusheng Xie

    2001-01-01

    Catalytic oxidation of NO to NO 2 over activated carbons PAN-ACF, pitch-ACF and coconut-AC at room temperature (30 o C) were studied to develop a method based on oxidative removal of NO from flue gases. For a dry gas, under the conditions of a gas space flow rate 1500 h -1 in the presence of oxygen of 2-20% in volume concentration, the activated coconut carbon with a surface area 1200 m 2 /g converted about 81-94% of NO with increasing oxygen concentration, the pitch based activated carbon fiber with a surface area 1000 m 2 /g about 44-75%, and the polyacrylonitrile-based activated carbon fiber with a surface area 1810 m 2 /g about 25-68%. The order of activity of the activated carbons was PAN-ACF c P NO P O2 β (F/W), where β is 0.042, 0.16, 0.31 for the coconut-AC, the pitch-ACF and the PAN-ACF respectively, and k c is 0.94 at 30 o C. (author)

  11. Catalytic activity trends of CO oxidation – A DFT study

    DEFF Research Database (Denmark)

    Jiang, Tao

    theoretical study of CO oxidation with experimental studies. The latter shows promoted catalytic activity when gold particle size decreases to 5 nm. Oxidizing CO by N2O was found to involve a CO␣O transition state, with atomic O adsorbed on the gold B5 sites and CO on the corners. On the other hand, CO...... and experiment were found to be the same. The experiment findings are in good agreement with our theoretical calculations. The second part of the thesis focuses on improving the convergence property of Quasi-Newton algorithm. The eigenvalues of the Hessian matrix of 54 atoms bulk Cu model are calculated......, and the sizes of eigenvalues follow power-law distribution. It is found that the anharmonicity of the weak modes lead to poor Newton step and poor Hessian update in BFGS type Quasi-Newton algorithm, which slow down the geometry optimization. Line search that fulfills Wolff conditions is then applied to improve...

  12. Mesoporous templated silicas: stability, pore size engineering and catalytic activation

    International Nuclear Information System (INIS)

    Vansant, Etienne

    2003-01-01

    The Laboratory of Adsorption and Catalysis has focused its research activities on the synthesis and activation of new porous materials. In the past few years, we have succeeded in developing easy and reproducible pathways to synthesize a huge variety of mesoporous crystalline materials. Points of interest in the synthesis of Mesoporous Templated Silicas are (i) stabilization of the structure, to withstand hydrothermal, thermal and mechanical pressure, (ii) pore size engineering to systematically control the pore size, pore volume and the ratio micro/mesopores and (iii) ease and reproducibility of the synthesis procedure, applying green principles, such as template recuperation. By carefully adapting the synthesis conditions and composition of the synthesis gel, using surfactants (long chain quaternary ammonium ions) and co-templates (long chain amines, alcohols or alkanes), the pore size of the obtained materials can be controlled from 1.5 to 7.0 nm, retaining the very narrow pore size distribution. Alternatively, materials with combined micro- and mesoporosity can be synthesized, using neutral surfactants (triblock copolymers). Hereby, the optimization of the SBA-15 and SBA-16 synthesis is being done in order to create mesoporous materials with microporous walls. The second research line is the controlled activation of MTS materials, by grafting or incorporation of catalytic active centers. We have developed for this purpose the Molecular Designed Dispersion method, which uses metal diketonate complexes as precursors. It is shown that in all cases the dispersion of the metal oxides on the surface is much better compared to the conventional grafting techniques. We have studied and published activation with V, Ti, Mo, Fe, Al and Cr species on different MTS materials. The structure and location of the active metal ion is the subject of an extensive spectroscopic investigation, using FT-IR, FT-Raman, UV-Vis DR coupled with selective chemisorption experiments and

  13. Preparation of silver nanoparticles/polydopamine functionalized polyacrylonitrile fiber paper and its catalytic activity for the reduction 4-nitrophenol

    Energy Technology Data Exchange (ETDEWEB)

    Lu, Shixiang, E-mail: shixianglu@bit.edu.cn [School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 100081 (China); Univ. Lille, CNRS, Centrale Lille, ISEN, Univ. Valenciennes, UMR 8520 – IEMN, Lille F-59000 (France); Yu, Jianying; Cheng, Yuanyuan [School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 100081 (China); Wang, Qian; Barras, Alexandre [Univ. Lille, CNRS, Centrale Lille, ISEN, Univ. Valenciennes, UMR 8520 – IEMN, Lille F-59000 (France); Xu, Wenguo [School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 100081 (China); Szunerits, Sabine [Univ. Lille, CNRS, Centrale Lille, ISEN, Univ. Valenciennes, UMR 8520 – IEMN, Lille F-59000 (France); Cornu, David [Institut Européen des Membranes, UMR 5635, Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), CNRS, Université Montpellier 2, 276 rue de la Galéra, Montpellier 34000 (France); Boukherroub, Rabah, E-mail: rabah.boukherroub@iemn.univ-lille1.fr [Univ. Lille, CNRS, Centrale Lille, ISEN, Univ. Valenciennes, UMR 8520 – IEMN, Lille F-59000 (France)

    2017-07-31

    Graphical abstract: Illustration of the preparation of Ag nanoparticles coated paper and its catalytic application for 4-nitrophenol reduction into the corresponding 4-aminophenol. - Highlights: • Polyacrylonitrile paper was functionalized with polydopamine and Ag nanoparticles. • Polydopamine coating layer played both reductive and adhesive roles. • The composite material displayed good catalytic activity for 4-nitrophenol reduction. • The process was environmentally benign and facile. - Abstract: The study reports on the preparation of polyacrylonitrile fiber paper (PANFP) functionalized with polydopamine (PD) and silver nanoparticles (Ag NPs), named as Ag NPs/PD/PANFP. The composite material was obtained via a simple two-step chemical process. First, a thin polydopamine layer was coated onto the PANFP surface through immersion into an alkaline dopamine (pH 8.5) aqueous solution at room temperature. The reductive properties of polydopamine were further exploited for the deposition of Ag NPs. The morphology and chemical composition of the composite material were characterized using scanning electron microscopy (SEM), X-ray diffraction pattern (XRD) and X-ray photoelectron spectroscopy (XPS). The catalytic activity of the nanocomposite was evaluated for the reduction of 4-nitrophenol using sodium borohydride (NaBH{sub 4}) at room temperature. The Ag NPs/PD/PANFP displayed good catalytic performance with a full reduction of 4-nitrophenol into the corresponding 4-aminophenol within 30 min. Moreover, the composite material exhibited a good stability up to 4 cycles without a significant loss of its catalytic activity.

  14. 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

  15. Effect of dose and dose rate of gamma radiation on catalytic activity of catalase

    International Nuclear Information System (INIS)

    Vaclav Cuba; Tereza Pavelkova; Viliam Mucka

    2010-01-01

    Catalytic activity of gamma irradiated catalase from bovine liver was studied for hydrogen peroxide decomposition at constant temperature and pressure. The measurement was performed at temperatures 27, 32, 37, 42 and 47 deg C. Solutions containing 1 and 0.01 g dm -3 of catalase in phosphate buffer were used for the study. Repeatability of both sample preparation and kinetics measurement was experimentally verified. Rate constants of the reaction were determined for all temperatures and the activation energy was evaluated from Arrhenius plot. Gamma irradiation was performed using 60 Co radionuclide source Gammacell 220 at two different dose rates 5.5 and 70 Gy h -1 , with doses ranging from 10 to 1000 Gy. The observed reaction of irradiated and non-irradiated catalase with hydrogen peroxide is of the first order. Irradiation significantly decreases catalytic activity of catalase, but the activation energy does not depend markedly on the dose. The effect of irradiation is more significant at higher dose rate. (author)

  16. Synthesis of Co/N-HNTs composites and investigation on its catalytic activity for H2 generation

    International Nuclear Information System (INIS)

    Zhao, Dongcui; Cheng, Zhilin; Nan, Zhaodong

    2016-01-01

    Co/N-HNTs composites were synthesized via a one-pot solvothermal method, where amine functional halloysite nanotubes (N-HNTs) were used as support materials. Effects of sulfosuccinate sodium salt (AOT), an anionic surfactant, on morphology and dispersibility of Co particles anchored at the N-HNTs were studied. The dispersibility of the Co particles was promoted with the increase of the AOT concentration. The as-obtained composite was used as a catalyst to generate H 2 gas by hydrolysis of NaBH 4 solution. The catalytic activity of the composite was significantly enhanced than the pure Co and Co/graphene composite at the same experimental conditions reported by our laboratory, and the catalyst was conveniently separated from the solution by a magnet. The catalytic activity was enhanced when the dispersibility of the Co particles was improved at the surface of the N-HNTs and the Co content contained in the composite was lowed. At the same time, the Co particles anchored at the inner surface of the N-HNTs resulted in higher catalytic activity, where the Co particles may bond with nitrogen atoms. The activation energy for the hydrolysis of NaBH 4 was calculated to be about 15.42 kJ mol −1 . The catalyst can be continuously used for four times with about the same catalytic activity. - Highlights: • Co/N-HNTs composites are synthesized. • The dispersibility and morphology of the Co particles anchored at the N-HNTs are modified by AOT. • The composite shows higher catalytic activity for production H 2 gas.

  17. Synthesis of Co/N-HNTs composites and investigation on its catalytic activity for H{sub 2} generation

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, Dongcui; Cheng, Zhilin; Nan, Zhaodong, E-mail: zdnan@yzu.edu.cn

    2016-11-01

    Co/N-HNTs composites were synthesized via a one-pot solvothermal method, where amine functional halloysite nanotubes (N-HNTs) were used as support materials. Effects of sulfosuccinate sodium salt (AOT), an anionic surfactant, on morphology and dispersibility of Co particles anchored at the N-HNTs were studied. The dispersibility of the Co particles was promoted with the increase of the AOT concentration. The as-obtained composite was used as a catalyst to generate H{sub 2} gas by hydrolysis of NaBH{sub 4} solution. The catalytic activity of the composite was significantly enhanced than the pure Co and Co/graphene composite at the same experimental conditions reported by our laboratory, and the catalyst was conveniently separated from the solution by a magnet. The catalytic activity was enhanced when the dispersibility of the Co particles was improved at the surface of the N-HNTs and the Co content contained in the composite was lowed. At the same time, the Co particles anchored at the inner surface of the N-HNTs resulted in higher catalytic activity, where the Co particles may bond with nitrogen atoms. The activation energy for the hydrolysis of NaBH{sub 4} was calculated to be about 15.42 kJ mol{sup −1}. The catalyst can be continuously used for four times with about the same catalytic activity. - Highlights: • Co/N-HNTs composites are synthesized. • The dispersibility and morphology of the Co particles anchored at the N-HNTs are modified by AOT. • The composite shows higher catalytic activity for production H{sub 2} gas.

  18. Synthesis and catalytic activity of polysaccharide templated nanocrystalline sulfated zirconia

    Energy Technology Data Exchange (ETDEWEB)

    Sherly, K. B.; Rakesh, K. [Mahatma Gandhi University Regional Research Center in Chemistry, Department of Chemistry, Mar Athanasius College, Kothamangalam-686666, Kerala (India)

    2014-01-28

    Nanoscaled materials are of great interest due to their unique enhanced optical, electrical and magnetic properties. Sulfate-promoted zirconia has been shown to exhibit super acidic behavior and high activity for acid catalyzed reactions. Nanocrystalline zirconia was prepared in the presence of polysaccharide template by interaction between ZrOCl{sub 2}⋅8H{sub 2}O and chitosan template. The interaction was carried out in aqueous phase, followed by the removal of templates by calcination at optimum temperature and sulfation. The structural and textural features were characterized by powder XRD, TG, SEM and TEM. XRD patterns showed the peaks of the diffractogram were in agreement with the theoretical data of zirconia with the catalytically active tetragonal phase and average crystalline size of the particles was found to be 9 nm, which was confirmed by TEM. TPD using ammonia as probe, FTIR and BET surface area analysis were used for analyzing surface features like acidity and porosity. The BET surface area analysis showed the sample had moderately high surface area. FTIR was used to find the type species attached to the surface of zirconia. UV-DRS found the band gap of the zirconia was found to be 2.8 eV. The benzylation of o-xylene was carried out batchwise in atmospheric pressure and 433K temperature using sulfated zirconia as catalyst.

  19. Pair Interaction of Catalytical Sphere Dimers in Chemically Active Media

    Directory of Open Access Journals (Sweden)

    Jing-Min Shi

    2018-01-01

    Full Text Available We study the pair dynamics of two self-propelled sphere dimers in the chemically active medium in which a cubic autocatalytic chemical reaction takes place. Concentration gradient around the dimer, created by reactions occurring on the catalytic sphere surface and responsible for the self-propulsion, is greatly influenced by the chemical activities of the environment. Consequently, the pair dynamics of two dimers mediated by the concentration field are affected. In the particle-based mesoscopic simulation, we combine molecular dynamics (MD for potential interactions and reactive multiparticle collision dynamics (RMPC for solvent flow and bulk reactions. Our results indicate three different configurations between a pair of dimers after the collision, i.e., two possible scenarios of bound dimer pairs and one unbound dimer pair. A phase diagram is sketched as a function of the rate coefficients of the environment reactions. Since the pair interactions are the basic elements of larger scale systems, we believe the results may shed light on the understanding of the collective dynamics.

  20. Palladium-pyridyl catalytic films: a highly active and recyclable catalyst for hydrogenation of styrene under mild conditions.

    Science.gov (United States)

    Gao, Shuiying; Li, Weijin; Cao, Rong

    2015-03-01

    Palladium-pyridyl catalytic films, (PdCl2/bpy)n, were created by alternating immersions of a substrate in PdCl2 and bpy (bpy=4, 4'-bipyridyl) solutions. The as-prepared (PdCl2/bpy)10 catalyst demonstrated a remarkable catalytic activity toward hydrogenation of styrene under mild conditions and the turnover frequency (TOF) is as high as 6944h(-1). Pd(II) ions of (PdCl2/bpy)n films are in situ reduced to Pd nanoparticles (NPs) during the hydrogenation of styrene process, which results in the catalytic activity of the films. The results of X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) further demonstrate that Pd(II) ions of (PdCl2/bpy)n films were gradually converted to Pd(0) states. The catalytic activity is related to bilayer numbers and the activity increases with the number of bilayers below 10 bilayers. The solid substrates coated with (PdCl2/bpy)n multilayer catalysts were easily removed from the reaction mixture without separation filtration. Moreover, (PdCl2/bpy)n catalysts were reused for 10 consecutive reactions without loss of activity. The present (PdCl2/bpy)n heterogeneous catalysts have the advantages of easy separation and good recyclability. Copyright © 2014 Elsevier Inc. All rights reserved.

  1. 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).

  2. Catalytic activity of catalysts for steam reforming reaction. Contract research

    Energy Technology Data Exchange (ETDEWEB)

    Ohashi, Hirofumi; Inagaki, Yoshiyuki [Japan Atomic Energy Research Inst., Oarai, Ibaraki (Japan). Oarai Research Establishment

    2003-05-01

    Japan Atomic Energy Research Institute has been developing a hydrogen production system by means of steam reforming of methane (chemical reation: CH{sub 4} + H{sub 2}O = CO + 3H{sub 2}) coupling with High Temperature Engineering Test Reactor (HTTR) to demonstrate effectiveness of high-temperature nuclear heat utilization. Prior to construction of HTTR hydrogen production system, a mock-up test facility with a full-scale reaction tube was constructed to investigate transient behavior of the hydrogen production system an establish system controllability. In order to predict transient behavior and hydrogen productivity of the hydrogen production system, it is important to estimate the reaction characteristics under the same temperature and pressure conditions as those of HTTR hydrogen production system. For the purpose of investigate an apparent activation energy of catalysts, catalytic activity test using small apparatus was carried out under the condition of methane flow rate from 1.18 x 10{sup -3} to 3.19 x 10{sup -3} mol/s, temperature from 500 to 900degC, pressure from 1.1 to 4.1MPa, and mol ratio of steam to methane from 2.5 to 3.5. It was confirmed that apparent activation energies of two kinds of Ni catalysts which are to be used in the mock-up test were 51.7 and 57.4kJ/mol, respectively, and reaction rate constants were propositional to the value from P{sup -0.15} to P{sup -0.33}. (author)

  3. Plasma-activated core-shell gold nanoparticle films with enhanced catalytic properties

    Energy Technology Data Exchange (ETDEWEB)

    Llorca, Jordi, E-mail: jordi.llorca@upc.edu; Casanovas, Albert; Dominguez, Montserrat; Casanova, Ignasi [Universitat Politecnica de Catalunya, Institut de Tecniques Energetiques (Spain); Angurell, Inmaculada; Seco, Miquel; Rossell, Oriol [Universitat de Barcelona, Departament de Quimica Inorganica (Spain)

    2008-03-15

    Catalytically active gold nanoparticle films have been prepared from core-shell nanoparticles by plasma-activation and characterized by high-resolution transmission electron microscopy, atomic force microscopy, and X-ray photoelectron spectroscopy. Methane can be selectively oxidized into formic acid with an O{sub 2}-H{sub 2} mixture in a catalytic wall reactor functionalized with plasma-activated gold nanoparticle films containing well-defined Au particles of about 3.5 nm in diameter. No catalytic activity was recorded over gold nanoparticle films prepared by thermal decomposition of core-shell nanoparticles due to particle agglomeration.

  4. Plasma-activated core-shell gold nanoparticle films with enhanced catalytic properties

    International Nuclear Information System (INIS)

    Llorca, Jordi; Casanovas, Albert; Dominguez, Montserrat; Casanova, Ignasi; Angurell, Inmaculada; Seco, Miquel; Rossell, Oriol

    2008-01-01

    Catalytically active gold nanoparticle films have been prepared from core-shell nanoparticles by plasma-activation and characterized by high-resolution transmission electron microscopy, atomic force microscopy, and X-ray photoelectron spectroscopy. Methane can be selectively oxidized into formic acid with an O 2 -H 2 mixture in a catalytic wall reactor functionalized with plasma-activated gold nanoparticle films containing well-defined Au particles of about 3.5 nm in diameter. No catalytic activity was recorded over gold nanoparticle films prepared by thermal decomposition of core-shell nanoparticles due to particle agglomeration

  5. A general method for tritium labelling of benzimidazole carbamates by catalytic exchange in dioxane solutions

    Energy Technology Data Exchange (ETDEWEB)

    Lacey, E [Commonwealth Scientific and Industrial Research Organization, Glebe, NSW (Australia). Div. of Animal Health, McMaster Lab.; Dawson, M [Sydney Univ. (Australia). Dept. of Pharmacy; Long, M A; Than, C [New South Wales Univ., Kensington (Australia). School of Chemistry

    1989-12-01

    Benzimidazole carbamates (BZCs) act as inhibitors of the tubulin-microtubule equilibria in eukaryotic organisms. Recently drug resistance to this class of compounds in helminth parasites has been shown to be due to a reduced ability of resistant tubulin to bind BZCs. In order to quantitate the nature of the tubulin-BZC interaction a general method for the specific tritium labelling of BZCs has been developed. The BZCs: mebendazole, oxfendazole, parbendazole, oxibendazole, albendazole and fenbendazole were labelled by catalytic exchange using palladium on calcium carbonate in pure dioxane at 60{sup 0}C under tritium gas. The position of label incorporation for tritiated albendazole was determined by tritium-NMR as the 4-position of benzimadazole nucleus. The yields for individual BZCs varied from 8 to 68% for a range of specific activity of 0.44 to 13.4 Ci/mmole. (author).

  6. A general method for tritium labelling of benzimidazole carbamates by catalytic exchange in dioxane solutions

    International Nuclear Information System (INIS)

    Lacey, E.; Dawson, M.; Long, M.A.; Than, C.

    1989-01-01

    Benzimidazole carbamates (BZCs) act as inhibitors of the tubulin-microtubule equilibria in eukaryotic organisms. Recently drug resistance to this class of compounds in helminth parasites has been shown to be due to a reduced ability of resistant tubulin to bind BZCs. In order to quantitate the nature of the tubulin-BZC interaction a general method for the specific tritium labelling of BZCs has been developed. The BZCs: mebendazole, oxfendazole, parbendazole, oxibendazole, albendazole and fenbendazole were labelled by catalytic exchange using palladium on calcium carbonate in pure dioxane at 60 0 C under tritium gas. The position of label incorporation for tritiated albendazole was determined by tritium-NMR as the 4-position of benzimadazole nucleus. The yields for individual BZCs varied from 8 to 68% for a range of specific activity of 0.44 to 13.4 Ci/mmole. (author)

  7. Pressure Drop and Catalytic Dehydrogenation of NaBH{sub 4} Solution Across Pin Fin Structures in a Microchannel Reactor

    Energy Technology Data Exchange (ETDEWEB)

    Jung, Ki Moon [Korea Institute of Industrial Technology, Cheonan (Korea, Republic of); Choi, Seok Hyun [Key Valve Technologies Ltd., Siheung (Korea, Republic of); Lee, Hee Joon [Kookmin Univ., Seoul (Korea, Republic of)

    2017-06-15

    Dehydrogenation from the hydrolysis of a sodium borohydride (NaBH{sub 4}) solution has been of interest owing to its high theoretical hydrogen storage capacity (10.8 wt.%) and potentially safe operation. An experimental study has been performed on the catalytic reaction rate and pressure drop of a NaBH4 solution over both a single microchannel with a hydraulic diameter of 300 μm and a staggered array of micro pin fins in the microchannel with hydraulic diameter of 50 μm. The catalytic reaction rates and pressure drops were obtained under Reynolds numbers from 1 to 60 and solution concentrations from 5 to 20 wt.%. Moreover, reacting flows were visualized using a high-speed camera with a macro zoom lens. As a result, both the amount of hydrogenation and pressure drop are 2.45 times and 1.5 times larger in a pin fin microchannel array than in a single microchannel, respectively.

  8. Room-temperature solution synthesis of Ag nanoparticle functionalized molybdenum oxide nanowires and their catalytic applications

    International Nuclear Information System (INIS)

    Dong Wenjun; Huang Huandi; Zhu Yanjun; Li Xiaoyun; Wang Xuebin; Li Chaorong; Chen Benyong; Wang Ge; Shi Zhan

    2012-01-01

    A simple chemical solution route for the synthesis of large-scale high-quality Ag nanoparticle functionalized molybdenum oxide nanowire at room temperature has been developed. In the synthesis, the protonated amine was intercalated into the molybdenum bronze layers to reduce the electrostatic force of the lamellar structures, and then the Ag nanoparticle functionalized long nanowires could be easily induced by a redox reaction between a molybdenum oxide–amine intermediate and Ag + at room temperature. The intercalation lamellar structures improved the nucleation and growth of the Ag nanoparticles, with the result that uniform Ag nanoparticles occurred on the surface of the MoO 3 nanowire. In this way Ag nanoparticles with average sizes of around 6 nm, and high-purity nanowires with mean diameter of around 50 nm and with typical lengths of several tens to hundreds of micrometers were produced. The heteronanostructured nanowires were intricately and inseparably connected to each other with hydrogen bonds and/or bridge oxygen atoms and packed together, forming a paper-like porous network film. The Ag–MoO 3 nanowire film performs a promoted catalytic property for the epoxidation of cis-cyclooctene, and the heteronanostructured nanowire film sensor shows excellent sensing performance to hydrogen and oxygen at room temperature. (paper)

  9. Room-temperature solution synthesis of Ag nanoparticle functionalized molybdenum oxide nanowires and their catalytic applications.

    Science.gov (United States)

    Dong, Wenjun; Huang, Huandi; Zhu, Yanjun; Li, Xiaoyun; Wang, Xuebin; Li, Chaorong; Chen, Benyong; Wang, Ge; Shi, Zhan

    2012-10-26

    A simple chemical solution route for the synthesis of large-scale high-quality Ag nanoparticle functionalized molybdenum oxide nanowire at room temperature has been developed. In the synthesis, the protonated amine was intercalated into the molybdenum bronze layers to reduce the electrostatic force of the lamellar structures, and then the Ag nanoparticle functionalized long nanowires could be easily induced by a redox reaction between a molybdenum oxide-amine intermediate and Ag(+) at room temperature. The intercalation lamellar structures improved the nucleation and growth of the Ag nanoparticles, with the result that uniform Ag nanoparticles occurred on the surface of the MoO(3) nanowire. In this way Ag nanoparticles with average sizes of around 6 nm, and high-purity nanowires with mean diameter of around 50 nm and with typical lengths of several tens to hundreds of micrometers were produced. The heteronanostructured nanowires were intricately and inseparably connected to each other with hydrogen bonds and/or bridge oxygen atoms and packed together, forming a paper-like porous network film. The Ag-MoO(3) nanowire film performs a promoted catalytic property for the epoxidation of cis-cyclooctene, and the heteronanostructured nanowire film sensor shows excellent sensing performance to hydrogen and oxygen at room temperature.

  10. Pt@Ag and Pd@Ag core/shell nanoparticles for catalytic degradation of Congo red in aqueous solution

    Science.gov (United States)

    Salem, Mohamed A.; Bakr, Eman A.; El-Attar, Heba G.

    2018-01-01

    Platinum/silver (Pt@Ag) and palladium/silver (Pd@Ag) core/shell NPs have been synthesized in two steps reaction using the citrate method. The progress of nanoparticle formation was followed by the UV/Vis spectroscopy. Transmission electron microscopy revealed spherical shaped core/shell nanoparticles with average particle diameter 32.17 nm for Pt@Ag and 8.8 nm for Pd@Ag. The core/shell NPs were further characterized by FT-IR and XRD. Reductive degradation of the Congo red dye was chosen to demonstrate the excellent catalytic activity of these core/shell nanostructures. The nanocatalysts act as electron mediators for the transfer of electrons from the reducing agent (NaBH4) to the dye molecules. Effect of reaction parameters such as nanocatalyst dose, dye and NaBH4 concentrations on the dye degradation was investigated. A comparison between the catalytic activities of both nanocatalysts was made to realize which of them the best in catalytic performance. Pd@Ag was the higher in catalytic activity over Pt@Ag. Such greater activity is originated from the smaller particle size and larger surface area. Pd@Ag nanocatalyst was catalytically stable through four subsequent reaction runs under the utilized reaction conditions. These findings can thus be considered as possible economical alternative for environmental safety against water pollution by dyes.

  11. Retro-binding thrombin active site inhibitors: identification of an orally active inhibitor of thrombin catalytic activity.

    Science.gov (United States)

    Iwanowicz, Edwin J; Kimball, S David; Lin, James; Lau, Wan; Han, W-C; Wang, Tammy C; Roberts, Daniel G M; Schumacher, W A; Ogletree, Martin L; Seiler, Steven M

    2002-11-04

    A series of retro-binding inhibitors of human alpha-thrombin was prepared to elucidate structure-activity relationships (SAR) and optimize in vivo performance. Compounds 9 and 11, orally active inhibitors of thrombin catalytic activity, were identified to be efficacious in a thrombin-induced lethality model in mice.

  12. Correction: Towards the rationalization of catalytic activity values by means of local hyper-softness on the catalytic site: a criticism about the use of net electric charges.

    Science.gov (United States)

    Martínez-Araya, Jorge Ignacio; Grand, André; Glossman-Mitnik, Daniel

    2016-01-28

    Correction for 'Towards the rationalization of catalytic activity values by means of local hyper-softness on the catalytic site: a criticism about the use of net electric charges' by Jorge Ignacio Martínez-Araya et al., Phys. Chem. Chem. Phys., 2015, DOI: 10.1039/c5cp03822g.

  13. Energetic basis of catalytic activity of layered nanophase calcium manganese oxides for water oxidation.

    Science.gov (United States)

    Birkner, Nancy; Nayeri, Sara; Pashaei, Babak; Najafpour, Mohammad Mahdi; Casey, William H; Navrotsky, Alexandra

    2013-05-28

    Previous measurements show that calcium manganese oxide nanoparticles are better water oxidation catalysts than binary manganese oxides (Mn3O4, Mn2O3, and MnO2). The probable reasons for such enhancement involve a combination of factors: The calcium manganese oxide materials have a layered structure with considerable thermodynamic stability and a high surface area, their low surface energy suggests relatively loose binding of H2O on the internal and external surfaces, and they possess mixed-valent manganese with internal oxidation enthalpy independent of the Mn(3+)/Mn(4+) ratio and much smaller in magnitude than the Mn2O3-MnO2 couple. These factors enhance catalytic ability by providing easy access for solutes and water to active sites and facile electron transfer between manganese in different oxidation states.

  14. Study of the catalytic activity of ceramic nano fibers in the methane combustion

    International Nuclear Information System (INIS)

    Reolon, R.P.; Berutti, F.A.; Alves, A.K.; Bergmann, C.P.

    2009-01-01

    In this work titanium oxide fibers, doped with cerium and copper, were synthesized using the electro spinning process. Titanium propoxide was used as a precursor in the electro spinning synthesis. The obtained fibers were heat treated after receive a spray with an alcoholic solution of cerium acetate and copper nitrate. The non-tissue material obtained was characterized by X-ray diffraction to determine the phase and crystallite size, X-ray photoelectron spectroscopy (XPS), BET method to determine the surface and SEM to analyze the microstructure of the fibers. The catalytic activity was evaluated by methane and air combustion under different temperatures. The amount of combustion gases such as NO x , C x H y , CO e CO 2 , were analyzed. (author)

  15. 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.

  16. 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.

  17. Catalysis by Glomerella cingulata cutinase requires conformational cycling between the active and inactive states of its catalytic triad.

    Science.gov (United States)

    Nyon, Mun Peak; Rice, David W; Berrisford, John M; Hounslow, Andrea M; Moir, Arthur J G; Huang, Huazhang; Nathan, Sheila; Mahadi, Nor Muhammad; Bakar, Farah Diba Abu; Craven, C Jeremy

    2009-01-09

    Cutinase belongs to a group of enzymes that catalyze the hydrolysis of esters and triglycerides. Structural studies on the enzyme from Fusarium solani have revealed the presence of a classic catalytic triad that has been implicated in the enzyme's mechanism. We have solved the crystal structure of Glomerella cingulata cutinase in the absence and in the presence of the inhibitors E600 (diethyl p-nitrophenyl phosphate) and PETFP (3-phenethylthio-1,1,1-trifluoropropan-2-one) to resolutions between 2.6 and 1.9 A. Analysis of these structures reveals that the catalytic triad (Ser136, Asp191, and His204) adopts an unusual configuration with the putative essential histidine His204 swung out of the active site into a position where it is unable to participate in catalysis, with the imidazole ring 11 A away from its expected position. Solution-state NMR experiments are consistent with the disrupted configuration of the triad observed crystallographically. H204N, a site-directed mutant, was shown to be catalytically inactive, confirming the importance of this residue in the enzyme mechanism. These findings suggest that, during its catalytic cycle, cutinase undergoes a significant conformational rearrangement converting the loop bearing the histidine from an inactive conformation, in which the histidine of the triad is solvent exposed, to an active conformation, in which the triad assumes a classic configuration.

  18. Synthesis, characterization and study of catalytic activity of Silver ...

    Indian Academy of Sciences (India)

    The XRD results revealed that all the samples show wurtzite hexagonal phase of ZnO. .... (Zn(Ac)2.2H2O) was used as zinc oxide source. ... The catalytic experiments ... were filtered out from the catalyst and then oxidation ..... As shown in table 5, the best results were obtained when acetonitrile was used as the sol- vent.

  19. Very Low Rate Constants of Bimolecular CO Adsorption on Anionic Gold Clusters: Implications for Catalytic Activity

    Czech Academy of Sciences Publication Activity Database

    Balteanu, I.; Balaj, O. P.; Fox, B. S.; Beyer, M. K.; Bastl, Zdeněk; Bondybey, V. E.

    2003-01-01

    Roč. 5, - (2003), s. 1213-1218 ISSN 1463-9076 Institutional research plan: CEZ:AV0Z4040901 Keywords : bimolecular * adsorption * catalytic activity Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.959, year: 2003

  20. Catalytic Intermolecular Cross-Couplings of Azides and LUMO-Activated Unsaturated Acyl Azoliums

    KAUST Repository

    Li, Wenjun; Ajitha, Manjaly John; Lang, Ming; Huang, Kuo-Wei; Wang, Jian

    2017-01-01

    An example for the catalytic synthesis of densely functionalized 1,2,3-triazoles through a LUMO activation mode has been developed. The protocol is enabled by intermolecular cross coupling reactions of azides with in situ-generated alpha

  1. 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.

  2. Catalytic activity of metal borides in the reaction of decomposition

    International Nuclear Information System (INIS)

    Labodi, I.; Korablev, L.I.; Tavadyan, L.A.; Blyumberg, Eh.A.

    1982-01-01

    Catalytic effect of CoB, MoB 2 , ZrB 2 and NbB 2 , prepared by the method of self-propagating high-temperature synthesis, on decomposition of tertiary butyl hydroperoxide has been studied. A technigue of determination of action mechanism of heterogeneous catalysts in liquid-phase process is suggested. It is established that CoB in contrast to other metal borides catalyzes only hydroperoxide decomposition into radicals

  3. Catalytic purification of waste gases containing VOC mixtures with Ce/Zr solid solutions

    International Nuclear Information System (INIS)

    Gutierrez-Ortiz, Jose I.; De Rivas, Beatriz; Lopez-Fonseca, Ruben; Gonzalez-Velasco, Juan R.

    2006-01-01

    This study has been undertaken to investigate the efficiency of ceria, zirconia, and Ce x Zr 1-x O 2 mixed oxides as catalysts for the vapour-phase destruction in air of single model VOCs (n-hexane, 1,2-dichloroethane and trichloroethylene) and non-chlorinated VOC/chlorinated VOC binary mixtures. Considering all catalyst compositions examined for the individual destruction of these compounds, activity for complete oxidation decreased in the following order: n-hexane 0.5 Zr 0.5 O 2 and Ce 0.15 Zr 0.85 O 2 ) were different than that with the best performance for n-hexane oxidation (CeO 2 ). Concerning chlorinated VOCs conversion, it was observed that notable improvements in catalyst activity of CeO 2 could be achieved through structural doping with Zr ions. Mixed oxides exhibited promoted redox and acid properties, which resulted catalytically relevant for the oxidation of 1,2-dichloroethane and trichloroethylene. In contrast, the combustion of n-hexane was essentially controlled by surface oxygen species, which were more abundant on CeO 2 . Attainment of high n-hexane conversions with CeO 2 was also attributed in part to the hydrophobicity of the support and the reduced interaction with carbon dioxide. Significant 'mixture effects' on both activity and selectivity were noticed when a given chlorinated feed was decomposed in the presence of n-hexane. On one hand, each VOC decreased the reactivity of the other relative to that of the pure compound resulting in higher operating temperatures to achieve adequate destruction. Competitive adsorption played an important role in the reciprocal inhibition effects detected with all catalysts. On the other hand, the selectivity to HCl was noticeably enhanced when n-hexane was co-fed, probably due to the increased presence of water generated as an oxidation product. (author)

  4. Influence of peracetic acid modification on the physicochemical properties of activated carbon and its performance in the ozone-catalytic oxidation of gaseous benzene

    Science.gov (United States)

    Fang, Ruimei; Huang, Haibao; Huang, Wenjun; Ji, Jian; Feng, Qiuyu; Shu, Yajie; Zhan, Yujie; Liu, Gaoyuan; Xie, Ruijie

    2017-10-01

    Coal based activated carbon (AC) was pretreated by peracetic acid solution and used for supporting Mn catalyst towards oxidation of gaseous benzene by catalytic ozonation. The as-obtained activated carbon was characterized by XPS, BET, SEM, and TG technologies. It indicates that peracetic acid solution modification not only raised the quantity of chemisorbed oxygen or water, and hydroxyl group on activated carbon material surface, but also increased the specific surface area and benzene adsorption capacity of activated carbon. Benzene could be completely removed in 300 min and CO2 selectivity reached to 61.9% over Mn/AC-modified catalyst. A possible catalytic ozonation mechanism of activated carbon which was treated by peracetic acid solution supported Mn catalyst for oxidation of benzene was proposed.

  5. 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.

  6. 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.

  7. The Catalytic Activity of Modified Zeolite Lanthanum on the Catalytic Cracking of Al-Duara Atmospheric Distillation Residue

    Directory of Open Access Journals (Sweden)

    Karim Khalifa Esgair

    2016-03-01

    Full Text Available Atmospheric residue fluid catalytic cracking was selected as a probe reaction to test the catalytic performance of modified NaY zeolites and prepared NaY zeolites. Modified NaY zeolites have been synthesized by simple ion exchange methods. Three samples of modified zeolite Y have been obtained by replacing the sodium ions in the original sample with lanthanum and the weight percent added are 0.28, 0.53, and 1.02 respectively. The effects of addition of lanthanum to zeolite Y in different weight percent on the cracking catalysts were investigated using an experimental laboratory plant scale of fluidized bed reactor. The experiments have been performed with weight hourly space velocity (WHSV range of 6 to 24 h-1, and the range of temperature from 450 to 510 oC. The activity of the catalyst with 1.02 wt% lanthanum has been shown to be much greater than that of the sample parent NaY. Also it was observed that the addition of the lanthanum causes an increase in the thermal stability of the zeolite.

  8. Preparation, Characterization, and Catalytic Activity of MoCo/USY Catalyst on Hydrodeoxygenation Reaction of Anisole

    Science.gov (United States)

    Nugrahaningtyas, K. D.; Suharbiansah, R. S. R.; Rahmawati, F.

    2018-03-01

    This research aims to prepare, characterize, and study the catalytic activity of Molybdenum (Mo) and Cobalt (Co) metal with supporting material Ultra Stable Y-Zeolite (USY), to produce catalysts with activity in hydrotreatment reaction and in order to eliminate impurities compounds that containing unwanted groups heteroatoms. The bimetallic catalysts MoCo/USY were prepared by wet impregnation method with weight variation of Co metal 0%, 2%, 4%, 6%, 8%, and Mo metal 8% (w/w), respectively. Activation method of the catalyst included calcination, oxidation, reduction and the crystallinity was characterized using X-ray diffraction (XRD), the acidity of the catalyst was analyzed using Fourier Transform Infrared Spectroscopy (FT-IR) and gravimetry method, minerals present in the catalyst was analyzed using X-Ray Fluorescence (XRF), and surface of the catalyst was analyzed using Surface Area Analyzer (SAA). Catalytic activity test (benzene yield product) of MoCo/USY on hydrodeoxigenation reaction of anisole aimed to determine the effect of Mo-Co/USY for catalytic activity in the reaction hydrodeoxigenation (HDO) anisole. Based on characterization and test of catalytic activity, it is known that catalytic of MoCo/USY 2% (catalyst B) shows best activities with acidity of 10.209 mmol/g, specific area of catalyst of 426.295 m2/g, pore average of 14.135 Å, total pore volume 0.318 cc/g, and total yield of HDO products 6.06%.

  9. Preliminary X-ray crystallographic studies of BthTX-II, a myotoxic Asp49-phospholipase A2 with low catalytic activity from Bothrops jararacussu venom

    International Nuclear Information System (INIS)

    Corrêa, L. C.; Marchi-Salvador, D. P.; Cintra, A. C. O.; Soares, A. M.; Fontes, M. R. M.

    2006-01-01

    A myotoxic Asp49-PLA 2 with low catalytic activity from B. jararacussu (BthTX-II) was crystallized in the monoclinic crystal system; a complete X-ray diffraction data set was collected and a molecular-replacement solution was obtained. The oligomeric structure of BthTX-II resembles those of the Asp49-PLA 2 PrTX-III and all bothropic Lys49-PLA 2 s. For the first time, a complete X-ray diffraction data set has been collected from a myotoxic Asp49-phospholipase A 2 (Asp49-PLA 2 ) with low catalytic activity (BthTX-II from Bothrops jararacussu venom) and a molecular-replacement solution has been obtained with a dimer in the asymmetric unit. The quaternary structure of BthTX-II resembles the myotoxin Asp49-PLA 2 PrTX-III (piratoxin III from B. pirajai venom) and all non-catalytic and myotoxic dimeric Lys49-PLA 2 s. In contrast, the oligomeric structure of BthTX-II is different from the highly catalytic and non-myotoxic BthA-I (acidic PLA 2 from B. jararacussu). Thus, comparison between these structures should add insight into the catalytic and myotoxic activities of bothropic PLA 2 s

  10. Biomimetic synthesis of silver nanoparticles and evaluation of their catalytic activity towards degradation of methyl orange

    Science.gov (United States)

    Manjari Mishra, Pravat; Bihari Pani, Khirod

    2017-11-01

    This paper described the significant effect of process variables like reductant concentrations, substrate concentration, reaction pH and reaction temperature on the size, morphology and yield of the silver nanoparticles (AgNPs) synthesized using aqueous leaf extract of a medicinal plant Momordica charantia (Bitter guard). By means of UV-vis spectroscopy, XRD analysis, TEM analysis and Fluorescence analysis, it is observed that the reaction solution containing 10-3 M of AgNO3 of pH 5.3  +  10 ml of aqueous leaf extract at normal room temperature, was optimum for synthesis of stable, polydisperse, predominantly spherical AgNPs with average size of 12.15 nm. FT-IR and TEM studies confirmed the stability of AgNPs was due to the capping of phytoconstituents present in the leaf extract. The aqueous solution of leaf extract containing AgNPs showed remarkable catalytic activity towards degradation of methyl orange (MO) in aqueous medium.

  11. Catalytic purification of waste gases containing VOC mixtures with Ce/Zr solid solutions

    Energy Technology Data Exchange (ETDEWEB)

    Gutierrez-Ortiz, Jose I.; De Rivas, Beatriz; Lopez-Fonseca, Ruben; Gonzalez-Velasco, Juan R. [Chemical Technologies for Environmental Sustainability Group, Department of Chemical Engineering, Faculty of Science and Technology, Universidad del Pais Vasco/EHU, P.O. Box 644, E-48080 Bilbao (Spain)

    2006-06-06

    This study has been undertaken to investigate the efficiency of ceria, zirconia, and Ce{sub x}Zr{sub 1-x}O{sub 2} mixed oxides as catalysts for the vapour-phase destruction in air of single model VOCs (n-hexane, 1,2-dichloroethane and trichloroethylene) and non-chlorinated VOC/chlorinated VOC binary mixtures. Considering all catalyst compositions examined for the individual destruction of these compounds, activity for complete oxidation decreased in the following order: n-hexane<1,2-dichloroethaneactivity of CeO{sub 2} could be achieved through structural doping with Zr ions. Mixed oxides exhibited promoted redox and acid properties, which resulted catalytically relevant for the oxidation of 1,2-dichloroethane and trichloroethylene. In contrast, the combustion of n-hexane was essentially controlled by surface oxygen species, which were more abundant on CeO{sub 2}. Attainment of high n-hexane conversions with CeO{sub 2} was also attributed in part to the hydrophobicity of the support and the reduced interaction with carbon dioxide. Significant 'mixture effects' on both activity and selectivity were noticed when a given chlorinated feed was decomposed in the presence of n-hexane. On one hand, each VOC decreased the reactivity of the other relative to that of the pure compound resulting in higher operating temperatures to achieve adequate destruction. Competitive adsorption played an important role in the reciprocal inhibition effects detected with all catalysts. On the other hand, the selectivity to HCl was noticeably enhanced when n-hexane was co-fed, probably due to the increased presence of water generated as an

  12. Catalytic activity of bed materials from industrial CFB boilers for the decomposition of N2O

    International Nuclear Information System (INIS)

    Barisic, V.; Klingstedt, F.; Kilpinen, P.; Hupa, M.; Naydenov, A.; Stefanov, P.

    2005-01-01

    The correlation between the catalytic activity towards N 2 O decomposition and fuel type was studied for the bed materials sampled from the bottom bed of two industrial CFB boilers, a 12MW th and a 550MW th , burning biomass fuels and wastes, alone or as a mixture. It was found that the elemental composition of the surface of the bed material particles changed according to the composition of the ash from the parent fuel. The measured catalytic activity of the bed material samples increased with the amount of the catalytically active oxides (CaO, MgO, Fe 2 O 3 , Al 2 O 3 ). In the case of limestone addition, the activity of the bed material was influenced by both the elemental composition of the fuel, and the ratio between lime and sulfated lime

  13. A spectroscopic and catalytic investigation of active phase-support interactions

    Energy Technology Data Exchange (ETDEWEB)

    Haller, G.L.

    1991-01-01

    Active catalytic phases (metal, mixed metals, oxide or mixed oxides) interacting with oxide support on which the active phase is dispersed can affect the percentage exposed, the morphology of supported particles, the degree of reducibility of cations, etc., in a variety of ways. Our objective is to characterize the physical chemistry of the active phase-oxide support by spectroscopic methods and to correlate this structure with catalytic function. The three systems discussed in this progress report are Ag/TiO{sub 2}, Ru-Cu/SiO{sub 2} and SiO{sub 2}/Al{sub 2}O{sub 3}. 24 refs., 3 figs., 2 tabs.

  14. 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.

  15. Activity coefficients of solutes in binary solvents

    International Nuclear Information System (INIS)

    Gokcen, N.A.

    1982-01-01

    The activity coefficients in dilute ternary systems are discussed in detail by using the Margules equations. Analyses of some relevant data at high temperatures show that the sparingly dissolved solutes in binary solvents follow complex behavior even when the binary solvents are very nearly ideal. It is shown that the activity data on the solute or the binary system cannot permit computation of the remaining activities except for the regular solutions. It is also shown that a fourth-order equation is usually adequate in expressing the activity coefficient of a solute in binary solvents at high temperatures. When the activity data for a binary solvent are difficult to obtain in a certain range of composition, the activity data for a sparingly dissolved solute can be used to supplement determination of the binary activities

  16. 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

  17. Green synthesis of Silver and Gold Nanoparticles for Enhanced catalytic and bactericidal activity

    Science.gov (United States)

    Naraginti, S.; Tiwari, N.; Sivakumar, A.

    2017-11-01

    A rapid one step green synthetic method using kiwi fruit extract was employed for preparation of silver and gold nanoparticles. The synthesized nanoparticles were successfully used as green catalysts for the reduction of 4-nitrophenol (4-NP) and methylene blue (MB). They also exhibited excellent antimicrobial activity against clinically isolated Pseudomonas aeruginosa (P.aeruginosa) and Staphylococcus aureus (S.aureus). It was noticed that with increase in concentration of the aqueous silver and gold solutions, particle size of the Ag and Au NPS showed increase as evidenced from UV-Visible spectroscopy and TEM micrograph. The method employed for the synthesis required only a few minutes for more than 90% formation of nanoparticles when the temperature was raised to 80°C. It was also noticed that the catalytic activity of nanoparticles depends upon the size of the particles. These nanoparticles were observed to be crystalline from the clear lattice fringes in the transmission electron microscopic (TEM) images, bright circular spots in the selected area electron diffraction (SAED) pattern and peaks in the X-ray diffraction (XRD) pattern. The Fourier-transform infrared (FTIR) spectrum indicated the presence of different functional groups in the biomolecule capping the nanoparticles.

  18. Catalytic activity of metallic nanoisland coatings. The influence of size effects on the recombination properties

    International Nuclear Information System (INIS)

    Tomilina, O A; Berzhansky, V N; Shaposhnikov, A N; Tomilin, S V

    2016-01-01

    The results of investigations of the quantum-size effects influence on selective properties of heterogeneous nanocatalysts are presents. As etalon exothermic reaction was used the reaction of atomic hydrogen recombination. The nanostructured Pd and Pt films on Teflon substrate were used as a samples of heterogeneous nanocatalysts. It was shown that for nanoparticles with various sizes the catalytic activity has the periodic dependence. It has been found that for certain sizes of nanoparticles their catalytic activity is less than that of Teflon substrate. (paper)

  19. Ni-Pt nanoparticles growing on metal organic frameworks (MIL-96) with enhanced catalytic activity for hydrogen generation from hydrazine at room temperature.

    Science.gov (United States)

    Wen, Lan; Du, Xiaoqiong; Su, Jun; Luo, Wei; Cai, Ping; Cheng, Gongzhen

    2015-04-07

    Well-dispersed bimetallic Ni-Pt nanoparticles (NPs) with different compositions have been successfully grown on the MIL-96 by a simple liquid impregnation method using NaBH4 as the reducing agent. Powder X-ray diffraction, transmission electron microscopy, energy-dispersive X-ray spectroscopy, N2 adsorption-desorption, and inductively coupled plasma-atomic emission spectroscopy measurements were employed to characterize the NiPt/MIL-96. Catalytic activity of NiPt/MIL-96 catalysts was tested in the hydrogen generation from the aqueous alkaline solution of hydrazine at room temperature. These catalysts are composition dependent on their catalytic activity, while Ni64Pt36/MIL-96 exhibits the highest catalytic activity among all the catalysts tested, with a turnover frequency value of 114.3 h(-1) and 100% hydrogen selectivity. This excellent catalytic performance might be due to the synergistic effect of the MIL-96 support and NiPt NPs, while NiPt NPs supported on other conventional supports, such as SiO2, carbon black, γ-Al2O3, poly(N-vinyl-2-pyrrolidone) (PVP), and the physical mixture of NiPt and MIL-96, all of them exhibit inferior catalytic activity compared to that of NiPt/MIL-96.

  20. Cytochrome oxidase assembly does not require catalytically active cytochrome C.

    Science.gov (United States)

    Barrientos, Antoni; Pierre, Danielle; Lee, Johnson; Tzagoloff, Alexander

    2003-03-14

    Cytochrome c oxidase (COX), the terminal enzyme of the mitochondrial respiratory chain, catalyzes the transfer of electrons from reduced cytochrome c to molecular oxygen. COX assembly requires the coming together of nuclear- and mitochondrial-encoded subunits and the assistance of a large number of nuclear gene products acting at different stages of maturation of the enzyme. In Saccharomyces cerevisiae, expression of cytochrome c, encoded by CYC1 and CYC7, is required not only for electron transfer but also for COX assembly through a still unknown mechanism. We have attempted to distinguish between a functional and structural requirement of cytochrome c in COX assembly. A cyc1/cyc7 double null mutant strain was transformed with the cyc1-166 mutant gene (Schweingruber, M. E., Stewart, J. W., and Sherman, F. (1979) J. Biol. Chem. 254, 4132-4143) that expresses stable but catalytically inactive iso-1-cytochrome c. The COX content of the cyc1/cyc7 double mutant strain harboring non-functional iso-1-cytochrome c has been characterized spectrally, functionally, and immunochemically. The results of these studies demonstrate that cytochrome c plays a structural rather than functional role in assembly of cytochrome c oxidase. In addition to its requirement for COX assembly, cytochrome c also affects turnover of the enzyme. Mutants containing wild type apocytochrome c in mitochondria lack COX, suggesting that only the folded and mature protein is able to promote COX assembly.

  1. Synthesis, Characterization, and Catalytic Activity of Pd(II Salen-Functionalized Mesoporous Silica

    Directory of Open Access Journals (Sweden)

    Rotcharin Sawisai

    2017-01-01

    Full Text Available Salen ligand synthesized from 2-hydroxybenzaldehyde and 2-hydroxy-1-naphthaldehyde was used as a palladium chelating ligand for the immobilization of the catalytic site. Mesoporous silica supported palladium catalysts were prepared by immobilizing Pd(OAc2 onto a mesoporous silica gel through the coordination of the imine-functionalized mesoporous silica gel. The prepared catalysts were characterized by X-ray diffraction (XRD, scanning electron microscopy (SEM, energy dispersive X-ray (EDX, inductivity couple plasma (ICP, nitrogen adsorption-desorption, and Fourier transform infrared (FT-IR spectroscopy. The solid catalysts showed higher activity for the hydroamination of C-(tetra-O-acetyl-β-D-galactopyranosylallene with aromatic amines compared with the corresponding homogenous catalyst. The heterogeneous catalytic system can be easily recovered by simple filtration and reused for up to five cycles with no significant loss of catalytic activity.

  2. New potential nonsteroidal anti-inflammatory drugs with antileukotrienic effects: influence on model proteins with catalytic activity.

    Science.gov (United States)

    Netopilová, Miloslava; Drsata, Jaroslav; Beránek, Martin; Palicka, Vladimír

    2002-01-01

    Unspecific and side effects caused by interaction with proteins belong to common problems of many structures synthesized as potential medicaments. Possible in vitro interactions with proteins of a group of phenylsulfonyl benzoic acid derivatives (VUFB 19363, 19369, 19370, 19371, and 19760) as new potential anti-inflammatory compounds with anti-leukotrienic activities were studied in the present work. Three purified enzymes were used as model proteins with catalytic activities: Pig heart aspartate aminotransferase (AST, EC 2.6.1.1), alanine aminotransferase (ALT, EC 2.6.1.2), and glutamate decarboxylase (GAD, EC 4.1.1.15) from E. coli. Catalytic activities during incubation of individual compounds (6 x 10(-5) M solution to 5 x 10(-2) M suspension) at 37 degrees C with enzymes served as criteria of stability and function of the proteins. No immediate influence of any compound studied on enzyme activities was found. Aminotransferase activities were not affected even during incubation up to 20 d. In the case of GAD, the compounds VUFB 19369, 19370, 19371, and 19760 had stabilizing influence on GAD activity during incubation at enzyme concentrations of 11.25 and 5.62 mg prot/l. The lack of an immediate effect of compounds and the stability of enzymes during incubation them are favorable and support the prospective of the compounds as potential drugs.

  3. Solution structure of the parvulin-type PPIase domain of Staphylococcus aureus PrsA – Implications for the catalytic mechanism of parvulins

    Directory of Open Access Journals (Sweden)

    Koskela Harri

    2009-03-01

    Full Text Available Abstract Background Staphylococcus aureus is a Gram-positive pathogenic bacterium causing many kinds of infections from mild respiratory tract infections to life-threatening states as sepsis. Recent emergence of S. aureus strains resistant to numerous antibiotics has created a need for new antimicrobial agents and novel drug targets. S. aureus PrsA is a membrane associated extra-cytoplasmic lipoprotein which contains a parvulin-type peptidyl-prolyl cis-trans isomerase domain. PrsA is known to act as an essential folding factor for secreted proteins in Gram-positive bacteria and thus it is a potential target for antimicrobial drugs against S. aureus. Results We have solved a high-resolution solution structure of the parvulin-type peptidyl-prolyl cis-trans isomerase domain of S. aureus PrsA (PrsA-PPIase. The results of substrate peptide titrations pinpoint the active site and demonstrate the substrate preference of the enzyme. With detailed NMR spectroscopic investigation of the orientation and tautomeric state of the active site histidines we are able to give further insight into the structure of the catalytic site. NMR relaxation analysis gives information on the dynamic behaviour of PrsA-PPIase. Conclusion Detailed structural description of the S. aureus PrsA-PPIase lays the foundation for structure-based design of enzyme inhibitors. The structure resembles hPin1-type parvulins both structurally and regarding substrate preference. Even though a wealth of structural data is available on parvulins, the catalytic mechanism has yet to be resolved. The structure of S. aureus PrsA-PPIase and our findings on the role of the conserved active site histidines help in designing further experiments to solve the detailed catalytic mechanism.

  4. Reaction mechanisms of CO2 activation and catalytic reduction

    International Nuclear Information System (INIS)

    Wolff, Niklas von

    2016-01-01

    The use of CO 2 as a C1 chemical feedstock for the fine chemical industry is interesting both economically and ecologically, as CO 2 is non-toxic, abundant and cheap. Nevertheless, transformations of CO 2 into value-added products is hampered by its high thermodynamic stability and its inertness toward reduction. In order to design new catalysts able to overcome this kinetic challenge, a profound understanding of the reaction mechanisms at play in CO 2 reduction is needed. Using novel N/Si+ frustrated Lewis pairs (FLPs), the influence of CO 2 adducts and different hydro-borane reducing agents on the reaction mechanism in the catalytic hydroboration of CO 2 were investigated, both by DFT calculations and experiments. In a second step, the reaction mechanism of a novel reaction for the creation of C-C bonds from CO 2 and pyridyl-silanes (C 5 H 4 N-SiMe 3 ) was analyzed by DFT calculations. It was shown that CO 2 plays a double role in this transformation, acting both as a catalyst and a C1-building block. The fine understanding of this transformation then led to the development of a novel approach for the synthesis of sulfones and sulfonamides. Starting from SO 2 and aromatic silanes/amine silanes, these products were obtained in a single step under metal-free conditions. Noteworthy, sulfones and sulfonamides are common motifs in organic chemistry and found in a variety of highly important drugs. Finally, this concept was extended to aromatic halides as coupling partners, and it was thus shown for the first time that a sulfonylative Hiyama reaction is a possible approach to the synthesis of sulfones. (author) [fr

  5. Towards the rationalization of catalytic activity values by means of local hyper-softness on the catalytic site: a criticism about the use of net electric charges.

    Science.gov (United States)

    Ignacio Martínez-Araya, Jorge; Grand, André; Glossman-Mitnik, Daniel

    2015-11-28

    By means of the Spin-Polarized Conceptual Density Functional Theory (SP-CDFT), three 2,6-bis(imino)pyridine catalysts based on iron(II), used for polymerization of ethylene, were studied. The catalysts differed by the substituent group, bearing either -H, -NO2 or -OCH3. To date, catalytic activity, a purely experimental parameter measuring the mass of polyethylene produced per millimole of iron per time and pressure unit at a fixed temperature, has not been explained in terms of local hyper-softness. The latter is a purely theoretical parameter designed for quantifying electronic effects; it is measured using the metal atom responsible for the coordination process with the monomer (ethylene). Because steric effects are not relevant in these kinds of catalysts and only electronic effects drive the catalytic process, an interesting link is found between catalytic activity and the local hyper-softness condensed on the iron atom by means of four functionals (B3LYP, BP86, B97D, and VSXC). This work demonstrates that the use of local hyper-softness, predicted by the SP-CDFT, is a suitable parameter for explaining order relationships among catalytic activity values, thus quantifying the electronic influence of the substituent group inducing this difference; the use of only net electric charges does not lead to clear conclusions. This finding can aid in estimating catalytic activities leading to a more rational design of new catalysts via computational chemistry.

  6. Baicalin and scutellarin are proteasome inhibitors that specifically target chymotrypsin-like catalytic activity.

    Science.gov (United States)

    Wu, Yi-Xin; Sato, Eiji; Kimura, Wataru; Miura, Naoyuki

    2013-09-01

    Baicalin and scutellarin are the major active principal flavonoids extracted from the Chinese herbal medicines Scutellaria baicalensis and Erigeron breviscapus (Vant.) Hand-Mazz. It has recently been reported that baicalin and scutellarin have antitumor activity. However, the mechanisms of action are unknown. We previously reported that some flavonoids have a specific role in the inhibition of the activity of proteasome subunits and induced apoptosis in tumor cells. To further investigate these pharmacological effects, we examined the inhibitory activity of baicalin and scutellarin on the extracted proteasomes from mice and cancer cells. Using fluorogenic substrates for proteasome catalytic subunits, we found that baicalin and scutellarin specifically inhibited chymotrypsin-like activity but did not inhibit trypsin-like and peptidyl-glutamyl peptide hydrolyzing activities. These data suggested that baicalin and scutellarin specifically inhibit chymotrypsin-like catalytic activity in the proteasome. Copyright © 2012 John Wiley & Sons, Ltd.

  7. 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.

  8. Evolution behavior of catalytically activated replication—decline in a coagulation process

    International Nuclear Information System (INIS)

    Gao Yan; Wang Hai-Feng; Zhang Ji-Dong; Yang Xia; Sun Mao-Zhu; Lin Zhen-Quan

    2013-01-01

    We propose a catalytically activated replication—decline model of three species, in which two aggregates of the same species can coagulate themselves, an A aggregate of any size can replicate itself with the help of B aggregates, and the decline of A aggregate occurs under the catalysis of C aggregates. By means of mean-field rate equations, we derive the asymptotic solutions of the aggregate size distribution a k (t) of species A, which is found to depend strongly on the competition among three mechanisms: the self-coagulation of species A, the replication of species A catalyzed by species B, and the decline of species A catalyzed by species C. When the self-coagulation of species A dominates the system, the aggregate size distribution a k (t) satisfies the conventional scaling form. When the catalyzed replication process dominates the system, a k (t) takes the generalized scaling form. When the catalyzed decline process dominates the system, a k (t) approaches the modified scaling form. (condensed matter: structural, mechanical, and thermal properties)

  9. Biosynthesis of gold nanoparticles using Capsicum annuum var. grossum pulp extract and its catalytic activity

    Science.gov (United States)

    Yuan, Chun-Gang; Huo, Can; Yu, Shuixin; Gui, Bing

    2017-01-01

    Biological synthesis approach has been regarded as a green, eco-friendly and cost effective method for nanoparticles preparation without any toxic solvents and hazardous bi-products during the process. This present study reported a facile and rapid biosynthesis method for gold nanoparticles (GNPs) from Capsicum annuum var. grossum pulp extract in a single-pot process. The aqueous pulp extract was used as biotic reducing agent for gold nanoparticle growing. Various shapes (triangle, hexagonal, and quasi-spherical shapes) were observed within range of 6-37 nm. The UV-Vis spectra showed surface plasmon resonance (SPR) peak for the formed GNPs at 560 nm after 10 min incubation at room temperature. The possible influences of extract amount, gold ion concentration, incubation time, reaction temperature and solution pH were evaluated to obtain the optimized synthesis conditions. The effects of the experimental factors on NPs synthesis process were also discussed. The produced gold nanoparticles were characterized by transform electron microscopy (TEM), X-ray diffraction (XRD), energy dispersive X-ray (EDS) and Fourier Transform infrared spectroscopy (FTIR). The results demonstrated that the as-obtained GNPs were well dispersed and stable with good catalytic activity. Biomolecules in the aqueous extract were responsible for the capping and stabilization of GNPs.

  10. High catalytic activity of ultrafine nanoporous palladium for electro-oxidation of methanol, ethanol, and formic acid

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Xiaoguang; Wang, Weimin; Qi, Zhen; Zhao, Changchun; Ji, Hong; Zhang, Zhonghua [Key Laboratory for Liquid-Solid Structural Evolution and Processing of Materials (MOE), School of Materials Science and Engineering, Shandong University, Jingshi Road 73, Jinan 250061 (China)

    2009-10-15

    Nanoporous palladium (NPPd) with ultrafine ligament size of 3-6 nm was fabricated by dealloying of an Al-Pd alloy in an alkaline solution. Electrochemical measurements indicate that NPPd exhibits significantly high electrochemical active specific surface area (23 m{sup 2} g{sup -1}), and high catalytic activity for electro-oxidation of methanol, ethanol, and formic acid. Mass activities can reach 149, 148, 262 mA mg{sup -1} for the oxidation of methanol, ethanol and formic acid, respectively. Moreover, superior steady-state activities can be observed for all the electro-oxidation processes. NPPd will be a promising candidate for the anode catalyst for direct alcohol or formic acid fuel cells. (author)

  11. Catalytic Intermolecular Cross-Couplings of Azides and LUMO-Activated Unsaturated Acyl Azoliums

    KAUST Repository

    Li, Wenjun

    2017-02-15

    An example for the catalytic synthesis of densely functionalized 1,2,3-triazoles through a LUMO activation mode has been developed. The protocol is enabled by intermolecular cross coupling reactions of azides with in situ-generated alpha,beta-unsaturated acyl azoliums. High yields and broad scope as well as the investigation of reaction mechanism are reported.

  12. Time dependent growth of vertically aligned carbon nanotube forest using a laser activated catalytical CVD method

    NARCIS (Netherlands)

    Haluska, M.; Bellouard, Y.J.; Dietzel, A.H.

    2008-01-01

    We report the growth of vertically aligned single-wall and multi-wall carbon nanotube forest using a Laser Activated - Catalytic Chemical Vapor Deposition process. The experiments were performed in a cold-wall reactor filled with an ethylene-hydrogen-argon gas mixture in a 5:2:8 ratio at ambient

  13. Aligned carbon nanotube with electro-catalytic activity for oxygen reduction reaction

    Science.gov (United States)

    Liu, Di-Jia; Yang, Junbing; Wang, Xiaoping

    2010-08-03

    A catalyst for an electro-chemical oxygen reduction reaction (ORR) of a bundle of longitudinally aligned carbon nanotubes having a catalytically active transition metal incorporated longitudinally in said nanotubes. A method of making an electro-chemical catalyst for an oxygen reduction reaction (ORR) having a bundle of longitudinally aligned carbon nanotubes with a catalytically active transition metal incorporated throughout the nanotubes, where a substrate is in a first reaction zone, and a combination selected from one or more of a hydrocarbon and an organometallic compound containing an catalytically active transition metal and a nitrogen containing compound and an inert gas and a reducing gas is introduced into the first reaction zone which is maintained at a first reaction temperature for a time sufficient to vaporize material therein. The vaporized material is then introduced to a second reaction zone maintained at a second reaction temperature for a time sufficient to grow longitudinally aligned carbon nanotubes over the substrate with a catalytically active transition metal incorporated throughout the nanotubes.

  14. Pi-activated alcohols: an emerging class of alkylating agents for catalytic Friedel-Crafts reactions.

    Science.gov (United States)

    Bandini, Marco; Tragni, Michele

    2009-04-21

    The direct functionalization of aromatic compounds, via Friedel-Crafts alkylation reactions with alcohols, is one of the cornerstones in organic chemistry. The present emerging area deals with the recent advances in the use of pi-activated alcohols in the catalytic and stereoselective construction of benzylic stereocenters.

  15. Catalytic activity of metall-like carbides in carbon oxide oxidation reaction

    International Nuclear Information System (INIS)

    Kharlamov, A.I.; Kosolapova, T.Ya.; Rafal, A.N.; Kirillova, N.V.

    1980-01-01

    Kinetics of carbon oxide oxidation upon carbides of hafnium, niobium, tantalum, molybdenum, zirconium and chromium is studied. Probable mechanism of the catalysts action is suggested. The established character of the change of the carbide catalytic activity is explained by the change of d-electron contribution to the metal-metal interaction

  16. A highly sensitive technique for detecting catalytically active nanoparticles against a background of general workplace aerosols

    International Nuclear Information System (INIS)

    Neubauer, N; Weis, F; Seipenbusch, M; Kasper, G; Binder, A

    2011-01-01

    A new measurement technique was studied using catalysis to specifically detect airborne nanoparticles in presence of background particles in the workplace air. Catalytically active nanoparticles produced by spark discharge were used as aerosol catalysts. According to these particles suitable catalytic test reactions were chosen and investigated by two different approaches: catalysis on airborne nanoparticles and catalysis on deposited nanoparticles. The results indicate that catalysis is applicable for the specific measurement of nanoparticles in the workplace air. Catalysis on airborne particles is suitable for the specific detection of very active nanoparticles, e.g. platinum or nickel, at high concentrations of about 10 7 /cm 3 . The approach of catalysis on deposited particles is better suited for nanoparticle aerosols at low concentrations, for slow catalytic reactions or less active nanoparticles like iron oxide (Fe 2 O 3 ). On the basis of the experimental results detection limits in the range of μg or even ng were calculated which assure the good potential of catalysis for the specific detection of nanoparticles in the workplace air based on their catalytic activity.

  17. The activity of catalytic systems based on zero-valent nickel complexes in propene dimerization

    Energy Technology Data Exchange (ETDEWEB)

    Shmidt, F.K.; Mironova, L.V.; Proidakov, A.G.; Kalabin, G.A.; Ratovskii, G.V.; Dmitrieva, T.V.

    1978-01-01

    Catalytic systems consisting of Ni(PPh/sub 3/) or Ni(P(OEt)/sub 3/)/sub 4/, Lewis acids BF/sub 3/ or BF/sub 3/.OEt/sub 2/, and Broensted acids HF, H/sub 2/SO/sub 4/, EtOH, or H/sub 2/O (even in trace amounts), but not HCl, showed high catalytic activities (i.e., hexene yields of 1200-1600 g-mole per g-atom Ni per hour) with 67-84% methylpentenes. In the absence of Lewis acids, the catalytic activity decreased and linear hexenes were favored (up to 65%). The activity of the systems containing no Broensted additives (i.e., when the solvents were thoroughly dehydrated and evacuated) was very low (50 g-mole hexene per g-atom Ni per hour). Proton, phosphorus-31, and fluorine-19 NMR studies identified nickel hydride complexes (NHC) with PF(OEt)/sub 2/ ligands in the Ni(P(OC/sub 2/H/sub 5/)/sub 3/)/sub 4// BF/sub 3/(OC/sub 2/H/sub 5/)/sub 2//C/sub 2/H/sub 5/OH system, and a UV spectroscopic study showed that the catalytic activity was proportional to the concentration of NHC in the system. Tables, spectra, and 16 references.

  18. Catalytic Activity of a Bifunctional Catalyst for Hydrotreatment of Jatropha curcas L. Seed Oil

    Directory of Open Access Journals (Sweden)

    J. García-Dávila

    2018-01-01

    Full Text Available The hydrotreating process of vegetable oils (HPVO involves the transformation of vegetable oil triglycerides into straight chain alkanes, which are carried out by deoxygenation reactions, generating multiple hydrocarbon compounds, cuts similar to heavy vacuum oil. The HPVO is applied to Jatropha curcas oil on USY zeolite supported with gamma alumina and platinum deposition on the catalytic as hydrogenation component. The acid of additional activity of the supports allows the development of catalytic routes that the intervention of catalytic centers of different nature reaches the desired product. The products of the hydrotreating reaction with Jatropha curcas seed oil triglycerides were identified by Fourier transform infrared spectroscopy and by mass spectroscopy to identify and analyze the generated intermediate and final hydrocarbon compounds.

  19. Direct Hysteresis Heating of Catalytically Active Ni–Co Nanoparticles as Steam Reforming Catalyst

    DEFF Research Database (Denmark)

    Mortensen, Peter Mølgaard; Engbæk, Jakob Soland; Vendelbo, Søren Bastholm

    2017-01-01

    We demonstrated a proof-of-concept catalytic steam reforming flow reactor system heated only by supported magnetic nickel–cobalt nanoparticles in an oscillating magnetic field. The heat transfer was facilitated by the hysteresis heating in the nickel–cobalt nanoparticles alone. This produced...... a sufficient power input to equilibrate the reaction at above 780 °C with more than 98% conversion of methane. The high conversion of methane indicated that Co-rich nanoparticles with a high Curie temperature provide sufficient heat to enable the endothermic reaction, with the catalytic activity facilitated...... by the Ni content in the nanoparticles. The magnetic hysteresis losses obtained from temperature-dependent hysteresis measurements were found to correlate well with the heat generation in the system. The direct heating of the catalytic system provides a fast heat transfer and thereby overcomes the heat...

  20. Modulation of catalytic activity in multi-domain protein tyrosine phosphatases.

    Directory of Open Access Journals (Sweden)

    Lalima L Madan

    Full Text Available Signaling mechanisms involving protein tyrosine phosphatases govern several cellular and developmental processes. These enzymes are regulated by several mechanisms which include variation in the catalytic turnover rate based on redox stimuli, subcellular localization or protein-protein interactions. In the case of Receptor Protein Tyrosine Phosphatases (RPTPs containing two PTP domains, phosphatase activity is localized in their membrane-proximal (D1 domains, while the membrane-distal (D2 domain is believed to play a modulatory role. Here we report our analysis of the influence of the D2 domain on the catalytic activity and substrate specificity of the D1 domain using two Drosophila melanogaster RPTPs as a model system. Biochemical studies reveal contrasting roles for the D2 domain of Drosophila Leukocyte antigen Related (DLAR and Protein Tyrosine Phosphatase on Drosophila chromosome band 99A (PTP99A. While D2 lowers the catalytic activity of the D1 domain in DLAR, the D2 domain of PTP99A leads to an increase in the catalytic activity of its D1 domain. Substrate specificity, on the other hand, is cumulative, whereby the individual specificities of the D1 and D2 domains contribute to the substrate specificity of these two-domain enzymes. Molecular dynamics simulations on structural models of DLAR and PTP99A reveal a conformational rationale for the experimental observations. These studies reveal that concerted structural changes mediate inter-domain communication resulting in either inhibitory or activating effects of the membrane distal PTP domain on the catalytic activity of the membrane proximal PTP domain.

  1. Structural insights into the loss of catalytic competence in pectate lyase activity at low pH

    DEFF Research Database (Denmark)

    Ali, Salyha; Søndergaard, Chresten Rauff; Teixeira, Susana

    2015-01-01

    at the active centre (+1 subsite), they withdraw electrons acidifying the C5 proton facilitating its abstraction by the catalytic arginine. Here we show that activity is lost at low pH because protonation of aspartates results in the loss of the two catalytic calcium-ions causing a profound failure to correctly...

  2. Mn-Ce-V-WOx/TiO2 SCR Catalysts: Catalytic Activity, Stability and Interaction among Catalytic Oxides

    Directory of Open Access Journals (Sweden)

    Xuteng Zhao

    2018-02-01

    Full Text Available A series of Mn-Ce-V-WOx/TiO2 composite oxide catalysts with different molar ratios (active components/TiO2 = 0.1, 0.2, 0.3, 0.6 have been prepared by wet impregnation method and tested in selective catalytic reduction (SCR of NO by NH3 in a wide temperature range. These catalysts were also characterized by X-ray diffraction (XRD, Transmission Electron Microscope (TEM, in situ Fourier Transform infrared spectroscopy (in situ FTIR, H2-Temperature programmed reduction (H2-TPR and X-ray photoelectron spectroscopy (XPS. The results show the catalyst with a molar ratio of active components/TiO2 = 0.2 exhibits highest NO conversion value between 150 °C to 400 °C and good resistance to H2O and SO2 at 250 °C with a gas hourly space velocity (GHSV value of 40,000 h−1. Different oxides are well dispersed and interact with each other. NH3 and NO are strongly adsorbed on the catalyst surface and the adsorption of the reactant gas leads to a redox cycle with the valence state change among the surface oxides. The adsorption of SO2 on Mn4+ and Ce4+ results in good H2O and SO2 resistance of the catalyst, but the effect of Mn and Ce are more than superior water and sulfur resistance. The diversity of valence states of the four active components and their high oxidation-reduction performance are the main reasons for the high NO conversion in this system.

  3. Effects of Mn- and K-addition on catalytic activity of calcium oxide for methane activation

    International Nuclear Information System (INIS)

    Park, Jong Sik; Kong, Jang Il; Lee, Sung Han; Jun, Jong Ho

    1998-01-01

    Pure CaO, Mn-doped CaO, Mn/CaO, and K/CaO catalysts were prepared and tested as catalysts for the oxidative coupling of methane in the temperature range of 600 to 800 .deg. C to investigate the effects of Mn- and K-addition on the catalytic activity of calcium oxide. To characterize the catalysts, X-ray powder diffraction (XRD), XPS, SEM, DSC, and TG analyses were performed. The catalytic reaction was carried out in a single-pass flow reactor using on-line gas chromatography system. Normalized reaction conditions were generally p(CH 4 )/p(O 2 )=250 Torr/50 Torr, total feed flow rate=30 mL/min, and 1 atm of total pressure with He being used as diluent gas. Among the catalysts tested, 6.3 mol% Mn-doped CaO catalyst showed the best C 2 yield of 8.0% with a selectivity of 43.2% at 775 .deg. C. The C 2 selectivity increased on lightly doped CaO catalysts, while decreased on heavily doped CaO((Mn)>6.3 mol%)catalysts. 6 wt.% Mn/CaO and 6 wt.% K/CaO catalysts showed the C 2 selectivities of 13.2% and 30.9%, respectively, for the reaction. Electrical conductivities of CaO and Mn-doped CaO were measured in the temperature range of 500 to 1000 .deg. C at Po2's of 10 -3 to 10 -1 atm. The electrical conductivity was decreased with Mn-doping and increased with increasing Po 2 in the range of 10 -3 to 10 -1 atm, indicating the specimens to be p-type semiconductors. It was suggested that the interstitial oxygen ions formed near the surface can activate methane and the formation of interstitial oxygen ions was discussed on the basis of solid-state chemistry

  4. Designer Ligands. Part 13. Synthesis and Catalytic Activity of ...

    African Journals Online (AJOL)

    Copper(I), copper(II), cobalt(II) and zinc(II) complexes of a macrocyclic, multidentate Schiff-base ligand have been prepared and, with the exception of the zinc(II) complex, have been shown to exhibit biomimetic catecholase activity. Keywords: Copper(II);Cobalt(II); Zinc(II); Biomimetic complexes; Catecholase activity

  5. Activating basal-plane catalytic activity of two-dimensional MoS2 monolayer with remote hydrogen plasma

    KAUST Repository

    Cheng, Chia-Chin; Lu, Ang-Yu; Tseng, Chien-Chih; Yang, Xiulin; Hedhili, Mohamed N.; Chen, Min-Cheng; Wei, Kung-Hwa; Li, Lain-Jong

    2016-01-01

    that account for a small percentage of the surface area, rather than the basal planes, of MoS2 monolayer have been confirmed as their active catalytic sites. As a result, extensive efforts have been developing in activating the basal planes of MoS2

  6. Catalytic Synthesis and Antifungal Activity of New Polychlorinated Natural Terpenes

    Directory of Open Access Journals (Sweden)

    Hana Ighachane

    2017-01-01

    Full Text Available Various unsaturated natural terpenes were selectively converted to the corresponding polychlorinated products in good yields using iron acetylacetonate in combination with nucleophilic cocatalyst. The synthesized compounds were evaluated for their in vitro antifungal activity. The antifungal bioassays showed that 2c and 2d possessed significant antifungal activity against Fusarium oxysporum f. sp. albedinis (Foa, Fusarium oxysporum f. sp. canariensis (Foc, and Verticillium dahliae (Vd.

  7. Synthesis, Characterization and Catalytic Activity of Cu/Cu2O Nanoparticles Prepared in Aqueous Medium

    Directory of Open Access Journals (Sweden)

    Sayed M. Badawy

    2015-07-01

    Full Text Available Copper/Copper oxide (Cu/Cu2O nanoparticles were synthesized by modified chemical reduction method in an aqueous medium using hydrazine as reducing agent and copper sulfate pentahydrate as precursor. The Cu/Cu2O nanoparticles were characterized by X-ray Diffraction (XRD, Energy Dispersive X-ray Fluorescence (EDXRF, Scanning Electron Microscope (SEM, and Transmission Electron Microscope (TEM. The analysis revealed the pattern of face-centered cubic (fcc crystal structure of copper Cu metal and cubic cuprites structure for Cu2O. The SEM result showed monodispersed and agglomerated particles with two micron sizes of about 180 nm and 800 nm, respectively. The TEM result showed few single crystal particles of face-centered cubic structures with average particle size about 11-14 nm. The catalytic activity of Cu/Cu2O nanoparticles for the decomposition of hydrogen peroxide was investigated and compared with manganese oxide MnO2. The results showed that the second-order equation provides the best correlation for the catalytic decomposition of H2O2 on Cu/Cu2O. The catalytic activity of hydrogen peroxide by Cu/Cu2O is less than the catalytic activity of MnO2 due to the presence of copper metal Cu with cuprous oxide Cu2O. © 2015 BCREC UNDIP. All rights reservedReceived: 6th January 2015; Revised: 14th March 2015; Accepted: 15th March 2015How to Cite: Badawy, S.M., El-Khashab, R.A., Nayl, A.A. (2015. Synthesis, Characterization and Catalytic Activity of Cu/Cu2O Nanoparticles Prepared in Aqueous Medium. Bulletin of Chemical Reaction Engineering & Catalysis, 10 (2: 169-174. (doi:10.9767/bcrec.10.2.7984.169-174 Permalink/DOI: http://dx.doi.org/10.9767/bcrec.10.2.7984.169-174  

  8. Investigation of the Origin of Catalytic Activity in Oxide-Supported Nanoparticle Gold

    Energy Technology Data Exchange (ETDEWEB)

    Harrison, Ian [Univ. of Virginia, Charlottesville, VA (United States)

    2017-05-26

    Since Haruta’s discovery in 1987 of the surprising catalytic activity of supported Au nanoparticles, we have seen a very large number of experimental and theoretical efforts to explain this activity and to fully understand the nature of the behavior of the responsible active sites. In 2011, we discovered that a dual catalytic site at the perimeter of ~3nm diameter Au particles supported on TiO2 is responsible for oxidative catalytic activity. O2 molecules bind with Au atoms and Ti4+ ions in the TiO2 support and the weakened O-O bond dissociates at low temperatures, proceeding to produce O atoms which act as oxidizing agents for the test molecule, CO. The papers supported by DOE have built on this finding and have been concerned with two aspects of the behavior of Au/TiO2 catalysts: (1). Mechanistic behavior of dual catalytic sites in the oxidation of organic molecules such as ethylene and acetic acid; (2). Studies of the electronic properties of the TiO2 (110) single crystal in relation to its participation in charge transfer at the occupied dual catalytic site. A total of 20 papers have been produced through DOE support of this work. The papers combine IR spectroscopic investigations of Au/TiO2 catalysts with surface science on the TiO2(110) and TiO2 nanoparticle surfaces with modern density functional modeling. The primary goals of the work were to investigate the behavior of the dual Au/Ti4+ site for the partial oxidation of alcohols to acids, the hydrogenation of aldehydes and ketones to alcohols, and the condensation of oxygenate intermediates- all processes related to the utilization of biomass in the production of useful chemical energy sources.

  9. 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

  10. Polystyrene-Supported Acyclic Diaminocarbene Palladium Complexes in Sonogashira Cross-Coupling: Stability vs. Catalytic Activity

    Directory of Open Access Journals (Sweden)

    Vladimir N. Mikhaylov

    2018-04-01

    Full Text Available Two types of immobilized on the amino-functionalized polystyrene-supported acyclic diaminocarbene palladium complexes (ADC-PdII are investigated under Sonogashira cross-coupling conditions. Depending on substituents in the diaminocarbene fragment immobilized ADC-PdII, systems are found to have different catalytic activity and stability regarding Pd-leaching. PdII-diaminocarbenes possessing protons at both nitrogen atoms smoothly decompose into Pd0-containing species providing a catalytic “cocktail system” with high activity and ability to reuse within nine runs. Polymer-supported palladium (II complex bearing NBn–Ccarbene–NH-moiety exhibits greater stability while noticeably lower activity under Sonogashira cross-coupling. Four molecular ADC-PdII complexes are also synthesized and investigated with the aim of confirming proposed base-promoted pathway of ADC-PdII conversion through carbodiimide into an active Pd0 forms.

  11. Reactive oxygen species inhibit catalytic activity of peptidylarginine deiminase

    DEFF Research Database (Denmark)

    Damgaard, Dres; Bjørn, Mads Emil; Jensen, Peter Østrup

    2017-01-01

    on calcium and reducing conditions. However, reactive oxygen species (ROS) have been shown to induce citrullination of histones in granulocytes. Here we examine the ability of H2O2 and leukocyte-derived ROS to regulate PAD activity using citrullination of fibrinogen as read-out. H2O2 at concentrations above...... from stimulated leukocytes was unaffected by exogenously added H2O2 at concentrations up to 1000 µM. The role of ROS in regulating PAD activity may play an important part in preventing hypercitrullination of proteins....

  12. Eco-friendly synthesis of silver nanoparticles using green algae (Caulerpa serrulata): reaction optimization, catalytic and antibacterial activities.

    Science.gov (United States)

    Aboelfetoh, Eman F; El-Shenody, Rania A; Ghobara, Mohamed M

    2017-07-01

    Stable colloidal silver nanoparticles (AgNPs) were synthesized using Caulerpa serrulata (green marine algae) aqueous extract as an efficient reducing and stabilizing agent. This method is considered to be a sustainable alternate to the more complicated chemical procedures. To achieve the optimization synthesis of AgNPs, several effects such as extract concentration, contact time, pH values, and temperature were examined. The synthesized AgNPs were characterized by UV-Vis spectroscopy, FT-IR, XRD, and HR-TEM. The synthesized AgNPs showed an intense surface plasmon resonance band at 412 nm at the optimal conditions (20% (v/v) extract and 95 °C). TEM reveal that higher extract concentration and higher temperature leading to the formation of spherical AgNPs with an average particle size of 10 ± 2 nm. The synthesized AgNPs showed excellent catalytic reduction activity of Congo red (CR) dye from aqueous solutions. The degradation percentage of CR with AgNPs accelerated by increasing either NaBH 4 concentration or catalytic dosage. The AgNPs synthesized at higher temperature (e.g., 10Ag-95) exhibited the highest catalytic activity. The reaction kinetics was found to be pseudo first order with respect to the dye concentration. Moreover, the AgNPs displayed antibacterial activity at lower concentration against Staphylococcus aureus, Pseudomonas aeruginosa, Shigella sp., Salmonella typhi, and Escherichia coli and may be a good alternative therapeutic approach. The outcomes of the current study confirmed that the synthesized AgNPs had an awesome guarantee for application in catalysis and wastewater treatment.

  13. Catalytic activation of molecular hydrogen in alkyne hydrogenation reactions by lanthanide metal vapor reaction products

    International Nuclear Information System (INIS)

    Evans, W.J.; Bloom, I.; Engerer, S.C.

    1983-01-01

    A rotary metal vapor was used in the synthesis of Lu, Er, Nd, Sm, Yb, and La alkyne, diene, and phosphine complexes. A typical catalytic hydrogenation experiment is described. The lanthanide metal vapor product is dissolved in tetrahydrofuran or toluene and placed in a pressure reaction vessel 3-hexyne (or another substrate) is added, the chamber attached to a high vacuum line, cooled to -196 0 C, evacuated, warmed to ambient temperature and hydrogen is added. The solution is stirred magnetically while the pressure in monitored. The reaction products were analyzed by gas chromatography. Rates and products of various systems are listed. This preliminary survey indicates that catalytic reaction chemistry is available to these metals in a wide range of coordination environments. Attempts to characterize these compounds are hampered by their paramagnetic nature and their tendency to polymerize

  14. Peroxidase-like catalytic activities of ionic metalloporphyrins ...

    Indian Academy of Sciences (India)

    Unknown

    the various PS-MTPPS was seen to be Co>Mn>Fe, with CoTPPS showing efficiency ... obtained, by simple ion exchange method in aqueous conditions to get ... The relative activities of the PS-MTPPS resins were then evaluated by comparing.

  15. Trends in Catalytic Activity for SOFC Anode materials

    DEFF Research Database (Denmark)

    Rossmeisl, Jan; Bessler, W. G.

    2008-01-01

    that oxygen spillover, where adsorbed oxygen is a key intermediate, is the dominant reaction pathway under the conditions used in the experiments. In this way the activity is linked directly to the microscopic binding affinities of reaction intermediates, providing a new understanding of the anode reaction...

  16. Comparative catalytic activity of PET track-etched membranes with embedded silver and gold nanotubes

    Science.gov (United States)

    Mashentseva, Anastassiya; Borgekov, Daryn; Kislitsin, Sergey; Zdorovets, Maxim; Migunova, Anastassiya

    2015-12-01

    Irradiated by heavy ions nanoporous polyethylene terephthalate track-etched membranes (PET TeMs) after +15Kr84 ions bombardment (1.75 MeV/nucl with the ion fluency of 1 × 109 cm-2) and sequential etching was applied in this research as a template for development of composites with catalytically enriched properties. A highly ordered silver and gold nanotubes arrays were embedded in 100 nm pores of PET TeMs via electroless deposition technique at 4 °C during 1 h. All "as-prepared" composites were examined for catalytic activity using reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) by sodium borohydride as a common reaction to test metallic nanostructures catalysts. The effect of temperature on the catalytic activity was investigated in range of 292-313 K and activation energy were calculated. Kapp of Ag/PET composites linearly increase with an increase of the temperature thus normal Arrhenius behavior have been seen and the activation energy was calculated to be 42.13 kJ/mol. Au/PET composites exhibit not only more powerful catalytic activity but also non-linear dependence of rate constant from temperature. Kapp increased with increasing temperature throughout the 292-308 K temperature range; the reaction had an activation energy 65.32 kJ/mol. In range 311-313 K rate constant dramatically decreased and the apparent activation energy at this temperature rang was -91.44 kJ/mol due some structural changes, i.e. agglomeration of Au nanoparticles on the surface of composite.

  17. Stability and phase transfer of catalytically active platinum nanoparticle suspensions

    International Nuclear Information System (INIS)

    Sriram, Indira; Curtin, Alexandra E.; Chiaramonti, Ann N.; Cuchiaro, J. Hunter; Weidner, Andrew R.; Tingley, Tegan M.; Greenlee, Lauren F.; Jeerage, Kavita M.

    2015-01-01

    In this work, we present a robust synthesis protocol for platinum nanoparticles that yields a monomodal dispersion of particles that are approximately 100 nm in diameter. We determine that these particles are actually agglomerates of much smaller particles, creating a “raspberry” morphology. We demonstrate that these agglomerates are stable at room temperature for at least 8 weeks by dynamic light scattering. Furthermore, we demonstrate consistent electrocatalytic activity for methanol oxidation. Finally, we quantitatively explore the relationship between dispersion solvent and particle agglomeration; specifically, particles are found to agglomerate abruptly as solvent polarity decreases

  18. Stability and phase transfer of catalytically active platinum nanoparticle suspensions

    Energy Technology Data Exchange (ETDEWEB)

    Sriram, Indira; Curtin, Alexandra E.; Chiaramonti, Ann N.; Cuchiaro, J. Hunter; Weidner, Andrew R.; Tingley, Tegan M.; Greenlee, Lauren F.; Jeerage, Kavita M., E-mail: jeerage@boulder.nist.gov [National Instrument of Standards and Technology, Applied Chemicals and Materials Division (United States)

    2015-05-15

    In this work, we present a robust synthesis protocol for platinum nanoparticles that yields a monomodal dispersion of particles that are approximately 100 nm in diameter. We determine that these particles are actually agglomerates of much smaller particles, creating a “raspberry” morphology. We demonstrate that these agglomerates are stable at room temperature for at least 8 weeks by dynamic light scattering. Furthermore, we demonstrate consistent electrocatalytic activity for methanol oxidation. Finally, we quantitatively explore the relationship between dispersion solvent and particle agglomeration; specifically, particles are found to agglomerate abruptly as solvent polarity decreases.

  19. A Short Review on the Catalytic Activity of Hydrotalcite-Derived Materials for Dry Reforming of Methane

    Directory of Open Access Journals (Sweden)

    Radosław Dębek

    2017-01-01

    Full Text Available Nickel-containing hydrotalcite-derived materials have been recently proposed as promising materials for methane dry reforming (DRM. Based on a literature review and on the experience of the authors, this review focuses on presenting past and recent achievements on increasing activity and stability of hydrotalcite-based materials for DRM. The use of different NiMgAl and NiAl hydrotalcite (HT precursors, various methods for nickel introduction into HT structure, calcination conditions and promoters are discussed. HT-derived materials containing nickel generally exhibit high activity in DRM; however, the problem of preventing catalyst deactivation by coking, especially below 700 °C, is still an open question. The proposed solutions in the literature include: catalyst regeneration either in oxygen atmosphere or via hydrogasification; or application of various promoters, such as Zr, Ce or La, which was proven to enhance catalytic stability.

  20. Highly Oriented Growth of Catalytically Active Zeolite ZSM-5 Films with a Broad Range of Si/Al Ratios

    NARCIS (Netherlands)

    Fu, Donglong|info:eu-repo/dai/nl/412516918; Schmidt, Joel E.|info:eu-repo/dai/nl/413333736; Ristanovic, Zoran|info:eu-repo/dai/nl/328233005; Chowdhury, Abhishek Dutta|info:eu-repo/dai/nl/412438003; Meirer, Florian; Weckhuysen, Bert M.|info:eu-repo/dai/nl/285484397

    2017-01-01

    Highly b-oriented zeolite ZSM-5 films are critical for applications in catalysis and separations and may serve as models to study diffusion and catalytic properties in single zeolite channels. However, the introduction of catalytically active Al3+ usually disrupts the orientation of zeolite films.

  1. Nanodiamond-Gold Nanocomposites with the Peroxidase-Like Oxidative Catalytic Activity.

    Science.gov (United States)

    Kim, Min-Chul; Lee, Dukhee; Jeong, Seong Hoon; Lee, Sang-Yup; Kang, Eunah

    2016-12-21

    Novel nanodiamond-gold nanocomposites (NDAus) are prepared, and their oxidative catalytic activity is examined. Gold nanoparticles are deposited on carboxylated nanodiamonds (NDs) by in situ chemical reduction of gold precursor ions to produce NDAus, which exhibit catalytic activity for the oxidation of o-phenylenediamine in the presence of hydrogen peroxide similarly to a peroxidase. This remarkable catalytic activity is exhibited only by the gold nanoparticle-decorated NDs and is not observed for either Au nanoparticles or NDs separately. Kinetic oxidative catalysis studies show that NDAus exhibit a ping-pong mechanism with an activation energy of 93.3 kJ mol -1 , with the oxidation reaction rate being proportional to the substrate concentration. NDAus retain considerable activity even after several instances of reuse and are compatible with a natural enzyme, allowing the detection of xanthine using cascade catalysis. Association with gold nanoparticles makes NDs a good carbonic catalyst due to charge transfer at the metal-carbon interface and facilitated substrate adsorption. The results of this study suggest that diverse carbonic catalysts can be obtained by interfacial incorporation of various metal/inorganic substances.

  2. Redox competition mode of scanning electrochemical microscopy (RC-SECM) for visualisation of local catalytic activity.

    Science.gov (United States)

    Eckhard, Kathrin; Chen, Xingxing; Turcu, Florin; Schuhmann, Wolfgang

    2006-12-07

    In order to locally analyse catalytic activity on modified surfaces a transient redox competition mode of scanning electrochemical microscopy (SECM) has been developed. In a bi-potentiostatic experiment the SECM tip competes with the sample for the very same analyte. This leads to a current decrease at the SECM tip, if it is positioned in close proximity to an active catalyst site on the surface. Specifically, local catalytic activity of a Pt-catalyst modified sample with respect to the catalytic reduction of molecular oxygen was investigated. At higher local catalytic activity the local 02 partial pressure within the gap between accurately positioned SECM tip and sample is depleted, leading to a noticeable tip current decrease over active sites. A flexible software module has been implemented into the SECM to adapt the competition conditions by proper definition of tip and sample potentials. A potential pulse profile enables the localised electrochemically induced generation of molecular oxygen prior to the competition detection. The current decay curves are recorded over the entire duration of the applied reduction pulse. Hence, a time resolved processing of the acquired current values provides movies of the local oxygen concentration against x,y-position. The SECM redox competition mode was verified with a macroscopic Pt-disk electrode as a test sample to demonstrate the feasibility of the approach. Moreover, highly dispersed electro-deposited spots of gold and platinum on glassy carbon were visualised using the redox competition mode of SECM. Catalyst spots of different nature as well as activity inhomogeneities within one spot caused by local variations in Pt-loading were visualised successfully.

  3. Preparation of amino-functionalized regenerated cellulose membranes with high catalytic activity.

    Science.gov (United States)

    Wang, Wei; Bai, Qian; Liang, Tao; Bai, Huiyu; Liu, Xiaoya

    2017-09-01

    The modification of regenerated cellulose (RC) membranes was carried out by using silane coupling agents presenting primary and secondary amino-groups. The grafting of the amino groups onto the modified cellulose molecule was confirmed by X-ray photoelectron spectroscopies and 13 C nuclear magnetic resonance spectroscopic analyses. The crystallinity of the cellulose membranes (CM) decreased after chemical modification as indicated by the X-ray diffraction results. Moreover, a denser structure was observed at the surface and cross section of the modified membranes by SEM images. The contact angle measurements showed that the silane coupling treatment enhanced the hydrophobicity of the obtained materials. Then the catalytic properties of two types of modified membranes were studied in a batch process by evaluating their catalytic performance in a Knoevenagel condensation. The results indicated that the cellulose membrane grafted with many secondary amines exhibited a better catalytic activity compared to the one grafted only by primary amines. In addition, the compact structure of the modified membranes permitted their application in a pervaporation catalytic membrane reactor. Therefore, functional CM that prepared in this paper represented a promising material in the field of industrial catalysis. Copyright © 2017 Elsevier B.V. All rights reserved.

  4. Catalytic oxidation of dibromomethane over Ti-modified Co3O4 catalysts: Structure, activity and mechanism.

    Science.gov (United States)

    Mei, Jian; Huang, Wenjun; Qu, Zan; Hu, Xiaofang; Yan, Naiqiang

    2017-11-01

    Ti-modified Co 3 O 4 catalysts with various Co/Ti ratios were synthesized using the co-precipitation method and were used in catalytic oxidation of dibromomethane (CH 2 Br 2 ), which was selected as the model molecule for brominated volatile organic compounds (BVOCs). Addition of Ti distorted the crystal structure and led to the formation of a Co-O-Ti solid solution. Co 4 Ti 1 (Co/Ti molar ratio was 4) achieved higher catalytic activity with a T 90 (the temperature needed for 90% conversion) of approximately 245°C for CH 2 Br 2 oxidation and higher selectivity to CO 2 at a low temperature than the other investigated catalysts. In addition, Co 4 Ti 1 was stable for at least 30h at 500ppm CH 2 Br 2 , 0 or 2vol% H 2 O, 0 or 500ppm p-xylene (PX), and 10% O 2 at a gas hourly space velocity of 60,000h -1 . The final products were CO x , Br 2 , and HBr, without the formation of other Br-containing organic byproducts. The high catalytic activity was attributed to the high Co 3+ /Co 2+ ratio and high surface acidity. Additionally, the synergistic effect of Co and Ti made it superior for CH 2 Br 2 oxidation. Furthermore, based on the analysis of products and in situ DRIFTs studies, a receivable reaction mechanism for CH 2 Br 2 oxidation over Ti-modified Co 3 O 4 catalysts was proposed. Copyright © 2017 Elsevier Inc. All rights reserved.

  5. Preparation and Characterization of Cu loaded TiO2 Nano tube Arrays and their Photo catalytic Activity

    International Nuclear Information System (INIS)

    Syazwani Mohd Zaki; Sreekantan, Srimala

    2011-01-01

    This paper described the preparation of Cu loaded TiO 2 nano tube arrays. Firstly, TiO 2 nano tube arrays were formed by anodization. Afterwards, the formed nano tube arrays were incorporated with Cu by wet impregnation method. The soaking time and concentration were varied to obtain an optimum set of parameter for Cu incorporation in TiO 2 nano tubes. After anodization, all samples were annealed at 400 degree Celsius for 4 hours to obtain anatase phase. The nano tube arrays were characterized by field emission scanning electron microscopy (FESEM), x-ray diffraction (XRD) and x-ray photoelectron spectra (XPS). An average diameter 63.02 nm and length 12.15 μm were obtained for TiO 2 nano tubes. The photo catalytic activity of these nano tubes were investigated with methyl orange (MO) and the TiO 2 nano tube prepared in 0.01 M of Cu (NO 3 ) 2 solution within 3 hours demonstrates the highest photo catalytic activity with 83.6 % degradation of methyl orange. (author)

  6. Catalytic activity of pyrite for coal liquefaction reaction; Tennen pyrite no shokubai seino ni kansuru kento

    Energy Technology Data Exchange (ETDEWEB)

    Hirano, K.; Kozu, M.; Okada, T.; Kobayashi, M. [Nippon Coal Oil Co. Ltd., Tokyo (Japan)

    1996-10-28

    Since natural pyrite is easy to obtain and cheap as coal liquefaction catalyst, it is to be used for the 150 t/d scale NEDOL process bituminous coal liquefaction pilot plant. NEDO and NCOL have investigated the improvement of catalytic activity of pulverized natural pyrite for enhancing performance and economy of the NEDOL process. In this study, coal liquefaction tests were conducted using natural pyrite catalyst pulverized by dry-type bowl mill under nitrogen atmosphere. Mechanism of catalytic reaction of the natural pyrite was discussed from relations between properties of the catalyst and liquefaction product. The natural pyrite provided an activity to transfer gaseous hydrogen into the liquefaction product. It was considered that pulverized pyrite promotes the hydrogenation reaction of asphaltene because pulverization increases its contact rate with reactant and the amount of active points on its surface. It was inferred that catalytic activity of pyrite is affected greatly by the chemical state of Fe and S on its surface. 3 refs., 4 figs., 1 tab.

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

    Science.gov (United States)

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

    2015-09-01

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

  8. Gold Incorporated Mesoporous Silica Thin Film Model Surface as a Robust SERS and Catalytically Active Substrate

    Directory of Open Access Journals (Sweden)

    Anandakumari Chandrasekharan Sunil Sekhar

    2016-05-01

    Full Text Available Ultra-small gold nanoparticles incorporated in mesoporous silica thin films with accessible pore channels perpendicular to the substrate are prepared by a modified sol-gel method. The simple and easy spin coating technique is applied here to make homogeneous thin films. The surface characterization using FESEM shows crack-free films with a perpendicular pore arrangement. The applicability of these thin films as catalysts as well as a robust SERS active substrate for model catalysis study is tested. Compared to bare silica film our gold incorporated silica, GSM-23F gave an enhancement factor of 103 for RhB with a laser source 633 nm. The reduction reaction of p-nitrophenol with sodium borohydride from our thin films shows a decrease in peak intensity corresponding to –NO2 group as time proceeds, confirming the catalytic activity. Such model surfaces can potentially bridge the material gap between a real catalytic system and surface science studies.

  9. Twinning in fcc lattice creates low-coordinated catalytically active sites in porous gold

    Energy Technology Data Exchange (ETDEWEB)

    Krajčí, Marian [Institute of Physics, Slovak Academy of Sciences, Dúbravská cesta 9, SK-84511 Bratislava (Slovakia); Kameoka, Satoshi; Tsai, An-Pang [Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, Sendai 980-8577 (Japan)

    2016-08-28

    We describe a new mechanism for creation of catalytically active sites in porous gold. Samples of porous gold prepared by de-alloying Al{sub 2}Au exhibit a clear correlation between the catalytic reactivity towards CO oxidation and structural defects in the fcc lattice of Au. We have found that on the stepped (211) surfaces quite common twin boundary defects in the bulk structure of porous gold can form long close-packed rows of atoms with the coordination number CN = 6. DFT calculations confirm that on these low-coordinated Au sites dioxygen chemisorbs and CO oxidation can proceed via the Langmuir–Hinshelwood mechanism with the activation energy of 37 kJ/mol or via the CO–OO intermediate with the energy barrier of 19 kJ/mol. The existence of the twins in porous gold is stabilized by the surface energy.

  10. Multifaceted catalytic hydrogenation of amides via diverse activation of a sterically confined bipyridine-ruthenium framework.

    Science.gov (United States)

    Miura, Takashi; Naruto, Masayuki; Toda, Katsuaki; Shimomura, Taiki; Saito, Susumu

    2017-05-16

    Amides are ubiquitous and abundant in nature and our society, but are very stable and reluctant to salt-free, catalytic chemical transformations. Through the activation of a "sterically confined bipyridine-ruthenium (Ru) framework (molecularly well-designed site to confine adsorbed H 2 in)" of a precatalyst, catalytic hydrogenation of formamides through polyamide is achieved under a wide range of reaction conditions. Both C=O bond and C-N bond cleavage of a lactam became also possible using a single precatalyst. That is, catalyst diversity is induced by activation and stepwise multiple hydrogenation of a single precatalyst when the conditions are varied. The versatile catalysts have different structures and different resting states for multifaceted amide hydrogenation, but the common structure produced upon reaction with H 2 , which catalyzes hydrogenation, seems to be "H-Ru-N-H."

  11. Integrating nanotubes into microsystems with electron beam lithography and in situ catalytically activated growth

    DEFF Research Database (Denmark)

    Gjerde, Kjetil; Fornés-Mora, Marc; Kjelstrup-Hansen, Jakob

    2006-01-01

    Integration of freestanding wire-like structures such as multi walled carbon nanotubes (MWCNT) into microsystems has many potential applications. Devices such as AFM tips or improved electrodes for conductivity measurements are obvious candidates. Catalytically activated growth opens up the possi......Integration of freestanding wire-like structures such as multi walled carbon nanotubes (MWCNT) into microsystems has many potential applications. Devices such as AFM tips or improved electrodes for conductivity measurements are obvious candidates. Catalytically activated growth opens up...... the possibility of waferscale fabrication of such devices. We combine conventional microfabrication techniques with state of the art electron beam lithography (EBL) to precisely position catalyst nanoparticles with sub 100 nm diameter into the microsystems. In particular, we have explored two main approaches...

  12. Synthesis and characterization of tantalum organometallic complexes. Catalytic activity for olefins

    International Nuclear Information System (INIS)

    Baley, A.S.

    1990-11-01

    Synthesis of monoaryloxy (alcoxy) neopentyl compounds is investigated. The tantalum-oxygen bond is formed by two parallel ways from TaCl 5 or TaR 2 Cl 3 with R = neopentyl and the tantalum carbon bond from a neopentyl derivative of the main series. Some compounds were isolated and characterized by NMR, elemental analysis and sometimes X-ray structure, some others are characterized in solution only. Catalytic effect is tested by ethylene dimerization and olefin polymerization. Reactivity of tantalum aryloxy neopentyl in respect to complexing and chelating ligands is studied for preparation of neopentylidene complexes

  13. 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

  14. 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.

  15. Investigation into catalytic activity of chelates of transition elements with azomethine in connection with their bacteriostatic action

    Energy Technology Data Exchange (ETDEWEB)

    Aptekar' , M D; Gordeev, Yu M [Voroshilovgradskij Mashinostroitel' nyj Inst. (USSR)

    1975-07-01

    By gas-volumimetric methods catalytic activity of VKS Co(2), Ni(2), Cu(2), Zn(2) and Cd(2) on the o-oxyarylazometine basis in the hydroperoxide decomposition and ascorbic acid oxidation reactions was studied. Dependence of catalytic activity of VKS on nature of central atom, aldehyde and amine fragments structure of ligands, complex stability was determined. It was shown that some similarity exist between catalytic activity of studied VKS and their bacteriostatic influence on E.coli,Staph. aureus,B.subtilis.

  16. 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.

  17. Probing the electrostatics of active site microenvironments along the catalytic cycle for Escherichia coli dihydrofolate reductase.

    Science.gov (United States)

    Liu, C Tony; Layfield, Joshua P; Stewart, Robert J; French, Jarrod B; Hanoian, Philip; Asbury, John B; Hammes-Schiffer, Sharon; Benkovic, Stephen J

    2014-07-23

    Electrostatic interactions play an important role in enzyme catalysis by guiding ligand binding and facilitating chemical reactions. These electrostatic interactions are modulated by conformational changes occurring over the catalytic cycle. Herein, the changes in active site electrostatic microenvironments are examined for all enzyme complexes along the catalytic cycle of Escherichia coli dihydrofolate reductase (ecDHFR) by incorporation of thiocyanate probes at two site-specific locations in the active site. The electrostatics and degree of hydration of the microenvironments surrounding the probes are investigated with spectroscopic techniques and mixed quantum mechanical/molecular mechanical (QM/MM) calculations. Changes in the electrostatic microenvironments along the catalytic environment lead to different nitrile (CN) vibrational stretching frequencies and (13)C NMR chemical shifts. These environmental changes arise from protein conformational rearrangements during catalysis. The QM/MM calculations reproduce the experimentally measured vibrational frequency shifts of the thiocyanate probes across the catalyzed hydride transfer step, which spans the closed and occluded conformations of the enzyme. Analysis of the molecular dynamics trajectories provides insight into the conformational changes occurring between these two states and the resulting changes in classical electrostatics and specific hydrogen-bonding interactions. The electric fields along the CN axes of the probes are decomposed into contributions from specific residues, ligands, and solvent molecules that make up the microenvironments around the probes. Moreover, calculation of the electric field along the hydride donor-acceptor axis, along with decomposition of this field into specific contributions, indicates that the cofactor and substrate, as well as the enzyme, impose a substantial electric field that facilitates hydride transfer. Overall, experimental and theoretical data provide evidence for

  18. Selectivity of an Active Natural Zeolite in Catalytic Conversion Process of Bangkirai, Kruing and Kamper Woods Biofuel to Gasoline Fraction

    Directory of Open Access Journals (Sweden)

    Wega Trisunaryanti

    2010-06-01

    Full Text Available The selectivity of an active natural zeolite (ZAAH in catalytic conversion process of Bangkirai, Kruing and Kamper woods biofuels has been studied. The ZAAH catalyst was prepared from a natural zeolite (ZA treated with acids solution (1% HF and 6M HCI and hydrothermal then calcined at 500 °C and oxidized at 400 °C under nitrogen and oxygen gas stream, respectively. Characterizations of the catalysts including Si/Al ratio and acidity were determined by atomic adsorption spectroscopy (AAS and ammonia gas adsorption method, respectively. The conversion process was carried out in a flow reactor system at 400 °C, under N2 stream (20 mL/min. The biofuel was vaporized from the pyrolysis zone to the catalytic reactor. A liquid product was covered and analyzed by gas chromatograph (GC and that connected with mass spectroscopy (GC-MS. The characterization results showed that the Si/AI ratio and acidity of the ZAAH were higher than that of the ZA catalyst. The GC-MS data showed that the highest product selectivity was 2,4-dimethyl heptane and 1,2-dimethyl benzene. The total product selectivity using the ZAAH catalyst (bangkirai = 68.10%; kruing = 54.76%; kamper = 50.72% was higher than that of the ZA catalyst (bangkirai = 39.24%; kruing = 44.38%; kamper = 46.11%.

  19. Preparation of H3-labelled methyl ethers of saturated fatty acids by heterogeneous catalytic isotope exchange in solution with gaseous tritium

    International Nuclear Information System (INIS)

    Shevchenko, V.P.; Myasoedov, N.F.

    1980-01-01

    A simple method of preparing 3 H-labelled methyl ethers of saturated fatty acids in the dioxane solution using the method of isotopic heterogenous catalytic exchange with gaseous tritium, is suggested. 3 H-labelled natural fatty acids (C 12 -C 18 ) are prepared by alkaline hydrolysis [ru

  20. 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.

  1. Catalytic activity of supported silver and potassium salts of tungstophosphoric acid in dehydration of ethanol

    International Nuclear Information System (INIS)

    Haber, J.; Matachowski, L.; Pamin, K.; Napruszewska, B.

    2002-01-01

    Potassium and silver salts of tungstophosphoric acid (HPW) have been supported on silica. Two series of potassium and silver salts of tungstophosphoric acid K x H 3-x PW 12 O 40 and Ag x H 3-x PW 12 O 40 where x = 1;2;3 supported on silica were prepared using incipient wetness method. In a typical synthesis, the heteropolyacid which after deposition on silica was washed with water to remove the part of heteropolyacid not bound to the support was reacted with silver or potassium salt. The vapor-phase dehydration of ethanol was employed as a test reaction. All the catalytic tests were carried out in a conventional flow type reactor, under atmospheric pressure, in the temperature range 125-500 o C. The results of these studies were used to explain the differences between the catalytic activities of heteropolysalts of potassium and silver supported on silica. (author)

  2. 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.

  3. Silver nanoparticles containing hybrid polymer microgels with tunable surface plasmon resonance and catalytic activity

    Energy Technology Data Exchange (ETDEWEB)

    Ajmal, Muhammad; Siddiq, Mohammad [Quaid-I-Azam University, Islamabad (Pakistan); Farooqi, Zahoor Hussain [University of the Punjab, Lahore (Pakistan)

    2013-11-15

    Multi-responsive poly(N-isopropylacrylamide-methacrylic acid-acrylamide) [P(NIPAM-MAA-AAm)] copolymer microgel was prepared by free radical emulsion polymerization. Silver nanoparticles were fabricated inside the microgel network by in-situ reduction of silver nitrate. Swelling and deswelling behavior of the pure microgels was studied under various conditions of pH and temperature using dynamic light scattering. A red shift was observed in surface plasmon resonance wavelength of Ag nanoparticles with pH induced swelling of hybrid microgel. The catalytic activity of the hybrid system was investigated by monitoring the reduction of p-nitrophenol under different conditions of temperature and amount of catalysts. For this catalytic reaction a time delay of 8 to 10min was observed at room temperature, which was reduced to 2 min at high temperature due to swelling of microgels, which facilitated diffusion of reactants to catalyst surface and increased rate of reaction.

  4. Catalytic Activity of Silicon Nanowires Decorated with Gold and Copper Nanoparticles Deposited by Pulsed Laser Ablation

    Directory of Open Access Journals (Sweden)

    Michele Casiello

    2018-01-01

    Full Text Available Silicon nanowires (SiNWs decorated by pulsed laser ablation with gold or copper nanoparticles (labeled as AuNPs@SiNWs and CuNPs@SiNWs were investigated for their catalytic properties. Results demonstrated high catalytic performances in the Caryl–N couplings and subsequent carbonylations for gold and copper catalysts, respectively, that have no precedents in the literature. The excellent activity, attested by the very high turn over number (TON values, was due both to the uniform coverage along the NW length and to the absence of the chemical shell surrounding the metal nanoparticles (MeNPs. A high recyclability was also observed and can be ascribed to the strong covalent interaction at the Me–Si interface by virtue of metal “silicides” formation.

  5. 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.

  6. Synthesis, characterization and catalytic activity toward methanol oxidation of electrocatalyst Pt4+-NH2-MCM-41

    International Nuclear Information System (INIS)

    Zheng Huajun; Chen Zuo; Wang Limin; Ma Chun’an

    2012-01-01

    Highlights: ► It was first confirmed that the Pt 4+ exhibited a good electro-catalytic property for methanol oxidation. ► The Pt 4+ perfectly distributed on a mesoporous molecular sieve matrix synthesis by a facile method. ► The good performance of catalyst resistance to poisoning because of a homogeneous distribution of Pt 4+ and large specific surface area. - Abstract: Mesoporous material with functional group (Pt 4+ -NH 2 -MCM-41) was prepared by grafting aminopropyl group and adsorbing platinum ions on the surface of the commercial molecular sieve (MCM-41). The characterization carried out by X-ray photoelectron spectroscopy, X-ray diffraction, and N 2 adsorption–desorption measurement pointed out that Pt was adsorbed on the NH 2 -MCM-41 surface as the oxidation state (Pt 4+ ) and the surface area of Pt 4+ -NH 2 -MCM-41 was up to 564 m 2 /g. Transmission electron microscopy and elemental mapping indicated a homogeneous distribution of Pt 4+ throughout all surface of the mesoporous materials. Electro-catalytic properties of methanol oxidation on the Pt 4+ -NH 2 -MCM-41 electrode were investigated with electrochemical methods. The results showed that the Pt 4+ -NH 2 -MCM-41 electrode exhibited catalytic activity in the methanol electro-oxidation with the apparent activation energy being 49.29 kJ/mol, and the control step of methanol electro-oxidation was the mass transfer process. It is first proved that platinum ions had good electro-catalytic property for methanol oxidation and provided a new idea for developing electrode materials in future.

  7. Surface Characteristics and Catalytic Activity of Copper Deposited Porous Silicon Powder

    Directory of Open Access Journals (Sweden)

    Muhammad Yusri Abdul Halim

    2014-12-01

    Full Text Available Porous structured silicon or porous silicon (PS powder was prepared by chemical etching of silicon powder in an etchant solution of HF: HNO3: H2O (1:3:5 v/v. An immersion time of 4 min was sufficient for depositing Cu metal from an aqueous solution of CuSO4 in the presence of HF. Scanning electron microscopy (SEM analysis revealed that the Cu particles aggregated upon an increase in metal content from 3.3 wt% to 9.8 wt%. H2-temperature programmed reduction (H2-TPR profiles reveal that re-oxidation of the Cu particles occurs after deposition. Furthermore, the profiles denote the existence of various sizes of Cu metal on the PS. The Cu-PS powders show excellent catalytic reduction on the p-nitrophenol regardless of the Cu loadings.

  8. Electrosynthesis and catalytic activity of polymer-nickel particles composite electrode materials

    International Nuclear Information System (INIS)

    Melki, Tahar; Zouaoui, Ahmed; Bendemagh, Barkahoum; Oliveira, Ione M.F. de; Oliveira, Gilver F. de; Lepretre, Jean-Claude; Bucher, Christophe; Mou tet, Jean-Claude

    2009-01-01

    Nickel-polymer composite electrode materials have been synthesized using various strategies, all comprising the electrochemical reduction of nickel(II) cations or complexes, incorporated by either ion-exchange or complexation into various poly(pyrrole-carboxylate) thin films coated by oxidative electropolymerization onto carbon electrodes. The electrocatalytic activity and the stability of the different composites have been then evaluated in the course of the electrocatalytic hydrogenation of ketones and enones in aqueous electrolytes. The best results were obtained using nickel-polymer composites synthesized by electroreduction of nickel(II) ions complexed into polycarboxylate films, which are characterized by a high catalytic activity and a good operational stability. (author)

  9. Electrosynthesis and catalytic activity of polymer-nickel particles composite electrode materials

    Energy Technology Data Exchange (ETDEWEB)

    Melki, Tahar; Zouaoui, Ahmed; Bendemagh, Barkahoum [Universite Ferhat Abbas, Setif (Algeria). Faculte des Sciences de l' Ingenieur. Dept. du Tronc Commun; Oliveira, Ione M.F. de; Oliveira, Gilver F. de [Universidade Federal de Minas Gerais (UFMG), Belo Horizonte, MG (Brazil). Dept. de Quimica; Lepretre, Jean-Claude [UMR-5631 CNRS-INPG-UJF, St. Martin d' Heres Cedex (France). Lab. d' Electrochimie et de Physicochimie des Materiaux et Interfaces; Bucher, Christophe; Mou tet, Jean-Claude [Universite Joseph Fourier Grenoble 1 (France). Dept. de Chimie Moleculaire], e-mail: Jean-Claude.Moutet@ujf-grenoble.fr

    2009-07-01

    Nickel-polymer composite electrode materials have been synthesized using various strategies, all comprising the electrochemical reduction of nickel(II) cations or complexes, incorporated by either ion-exchange or complexation into various poly(pyrrole-carboxylate) thin films coated by oxidative electropolymerization onto carbon electrodes. The electrocatalytic activity and the stability of the different composites have been then evaluated in the course of the electrocatalytic hydrogenation of ketones and enones in aqueous electrolytes. The best results were obtained using nickel-polymer composites synthesized by electroreduction of nickel(II) ions complexed into polycarboxylate films, which are characterized by a high catalytic activity and a good operational stability. (author)

  10. Importance of the oxygen bond strength for catalytic activity in soot oxidation

    DEFF Research Database (Denmark)

    Christensen, Jakob M.; Grunwaldt, Jan-Dierk; Jensen, Anker D.

    2016-01-01

    (loose contact) the rate constants for a number of catalytic materials outline a volcano curve when plotted against their heats of oxygen chemisorption. However, the optima of the volcanoes correspond to different heats of chemisorption for the two contact situations. In both cases the activation...... oxidation. The optimum of the volcano curve in loose contact is estimated to occur between the bond strengths of α-Fe2O3 and α-Cr2O3. Guided by an interpolation principle FeaCrbOx binary oxides were tested, and the activity of these oxides was observed to pass through an optimum for an FeCr2Ox binary oxide...

  11. Catalytically active and hierarchically porous SAPO-11 zeolite synthesized in the presence of polyhexamethylene biguanidine

    KAUST Repository

    Liu, Yan

    2014-03-01

    Hierarchically porous SAPO-11 zeolite (H-SAPO-11) is rationally synthesized from a starting silicoaluminophosphate gel in the presence of polyhexamethylene biguanidine as a mesoscale template. The sample is well characterized by XRD, N2 sorption, SEM, TEM, NMR, XPS, NH3-TPD, and TG techniques. The results show that the sample obtained has good crystallinity, hierarchical porosity (mesopores at ca. 10nm and macropores at ca. 50-200nm), high BET surface area (226m2/g), large pore volume (0.25cm3/g), and abundant medium and strong acidic sites (0.36mmol/g). After loading Pt (0.5wt.%) on H-SAPO-11 by using wet impregnation method, catalytic hydroisomerization tests of n-dodecane show that the hierarchical Pt/SAPO-11 zeolite exhibits high conversion of n-dodecane and enhanced selectivity for branched products as well as reduced selectivity for cracking products, compared with conventional Pt/SAPO-11 zeolite. This phenomenon is reasonably attributed to the presence of hierarchical porosity, which is favorable for access of reactants on catalytically active sites. The improvement in catalytic performance in long-chain paraffin hydroisomerization over Pt/SAPO-11-based catalyst is of great importance for its industrial applications in the future. © 2013 Elsevier Inc.

  12. 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.

  13. Enhanced catalytic activity without the use of an external light source using microwave-synthesized CuO nanopetals

    Directory of Open Access Journals (Sweden)

    Govinda Lakhotiya

    2017-05-01

    Full Text Available We report enhanced catalytic activity of CuO nanopetals synthesized by microwave-assisted wet chemical synthesis. The catalytic reaction of CuO nanopetals and H2O2 was studied with the application of external light source and also under dark conditions for the degradation of the hazardous dye methylene blue. The CuO nanopetals showed significant catalytic activity for the fast degradation of methylene blue and rhodamine B (RhB under dark conditions, without the application of an external light source. This increased catalytic activity was attributed to the co-operative role of H2O2 and the large specific surface area (≈40 m2·g−1 of the nanopetals. We propose a detail mechanism for this fast degradation. A separate study of the effect of different H2O2 concentrations for the degradation of methylene blue under dark conditions is also illustrated.

  14. CATALYTIC WET PEROXIDE OXIDATION OF HYDROQUINONE WITH Co(II)/ACTIVE CARBON CATALYST LOADED IN STATIC BED

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    Catalysts based on Co(II) supported on active carbon were prepared and loaded in static bed. The hydroquinone would be degraded completely after treated by Catalytic wet peroxide oxidation method with Co(II)/active carbon catalyst. After activate treatment, the active carbon was immerged in cobaltous nitrate solution, then put into a drying oven, Co(II) could be loaded on the micro-surface of carbon. Taking the static bed as the equipment, the absorption of active carbon and catalysis of Co(II) was used to reduce activation energy of hydroquinone. Thus hydroquinone could be drastically degraded and the effluent can be drained under the standard. Referring to Fenton reaction mechanism, experiment had been done to study the heterogeneous catalyzed oxidation mechanism of Co(II). The degradation rate of hydroquinone effluent could be achieved to 92% when treated in four columns at H2O2 concentration 10%, reaction temperature 40℃ , pH 5 and reaction time 2.5h.

  15. Physicochemical properties of manganese dioxide synthesized using C2–C5 alcohols as reducing agents and their catalytic activities for CO oxidation

    KAUST Repository

    Lee, Young-Ho

    2015-09-26

    MnO2 catalysts were synthesized in an aqueous solution of KMnO4 and C2–C5 alcohols using a simple redox method at room temperature. The crystalline structure of all samples was δ-MnO2 after being calcined at 300 °C. However, other physicochemical properties of the samples varied depending on the symmetry of the alcohols used. For the catalytic oxidation of CO, MnO2 catalysts prepared with 1° alcohols performed better than the samples prepared in 2° alcohols. Catalytic activities were correlated to the quantity of labile oxygen species of the catalysts. In CO-TPD analysis, the relative area of desorbed radical dotCO2, which is the product of the reaction between adsorbed CO and lattice oxygen species, becomes larger for MnO2 prepared with 1° alcohols than with 2° alcohols. These results were primarily resulted from the innate hydrogen dissociation behavior of alcohol in solution. The pKa was found to be an important factor in determining the physicochemical properties and catalytic activity toward CO oxidation of MnO2.

  16. Physicochemical properties of manganese dioxide synthesized using C2–C5 alcohols as reducing agents and their catalytic activities for CO oxidation

    KAUST Repository

    Lee, Young-Ho; Park, Jung-Hyun; Shin, Chae-Ho

    2015-01-01

    MnO2 catalysts were synthesized in an aqueous solution of KMnO4 and C2–C5 alcohols using a simple redox method at room temperature. The crystalline structure of all samples was δ-MnO2 after being calcined at 300 °C. However, other physicochemical properties of the samples varied depending on the symmetry of the alcohols used. For the catalytic oxidation of CO, MnO2 catalysts prepared with 1° alcohols performed better than the samples prepared in 2° alcohols. Catalytic activities were correlated to the quantity of labile oxygen species of the catalysts. In CO-TPD analysis, the relative area of desorbed radical dotCO2, which is the product of the reaction between adsorbed CO and lattice oxygen species, becomes larger for MnO2 prepared with 1° alcohols than with 2° alcohols. These results were primarily resulted from the innate hydrogen dissociation behavior of alcohol in solution. The pKa was found to be an important factor in determining the physicochemical properties and catalytic activity toward CO oxidation of MnO2.

  17. Sustainability of the Catalytic Activity of a Silica-Titania Composite (STC) for Long-Term Indoor Air Quality Control

    Science.gov (United States)

    Coutts, Janelle L.; Levine, Lanfang H.; Richards, Jeffrey T.

    2011-01-01

    TiO2-assisted photocatalytic oxidation (PCO) is an emerging technology for indoor air quality control and is also being evaluated as an alternative trace contaminant control technology for crew habitats in space exploration. Though there exists a vast range of literature on the development of photocatalysts and associated reactor systems, including catalyst performance and performance-influencing factors, the critical question of whether photocatalysts can sustain their initial catalytic activity over an extended period of operation has not been adequately addressed. For a catalyst to effectively serve as an air quality control product, it must be rugged enough to withstand exposure to a multitude of low concentration volatile organic compounds (VOCs) over long periods of time with minimal loss of activity. The objective of this study was to determine the functional lifetime of a promising photocatalyst - the silica-titania composite (STC) from Sol Gel Solutions, LLC in a real-world scenario. A bench-scale STC-packed annular reactor under continuous irradiation by a UV-A fluorescent black-light blue lamp ((lambda)max = 365 nm) was exposed to laboratory air continuously at an apparent contact time of 0.27 sand challenged with a known concentration of ethanol periodically to assess any changes in catalytic activity. Laboratory air was also episodically spiked with halocarbons (e.g., octafluoropropane), organosulfur compounds (e.g., sulfur hexafluoride), and organosilicons (e.g., siloxanes) to simulate accidental releases or leaks of such VOCs. Total organic carbon (TOC) loading and contaminant profiles of the laboratory air were also monitored. Changes in STC photocatalytic performance were evaluated using the ethanol mineralization rate, mineralization efficiency, and oxidation intermediate (acetaldehyde) formation. Results provide insights to any potential catalyst poisoning by trace halocarbons and organosulfur compounds.

  18. Enhanced catalytic activity over MIL-100(Fe) loaded ceria catalysts for the selective catalytic reduction of NOx with NH₃ at low temperature.

    Science.gov (United States)

    Wang, Peng; Sun, Hong; Quan, Xie; Chen, Shuo

    2016-01-15

    The development of catalysts for selective catalytic reduction (SCR) reactions that are highly active at low temperatures and show good resistance to SO2 and H2O is still a challenge. In this study, we have designed and developed a high-performance SCR catalyst based on nano-sized ceria encapsulated inside the pores of MIL-100(Fe) that combines excellent catalytic power with a metal organic framework architecture synthesized by the impregnation method (IM). Transmission electron microscopy (TEM) revealed the encapsulation of ceria in the cavities of MIL-100(Fe). The prepared IM-CeO2/MIL-100(Fe) catalyst shows improved catalytic activity both at low temperatures and throughout a wide temperature window. The temperature window for 90% NOx conversion ranges from 196 to 300°C. X-ray photoelectron spectroscopy (XPS) and in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFT) analysis indicated that the nano-sized ceria encapsulated inside MIL-100(Fe) promotes the production of chemisorbed oxygen on the catalyst surface, which greatly enhances the formation of the NO2 species responsible for fast SCR reactions. Copyright © 2015 Elsevier B.V. All rights reserved.

  19. Superior acidic catalytic activity and stability of Fe-doped HTaWO6 nanotubes

    KAUST Repository

    Liu, He

    2017-07-26

    Fe-doped HTaWO6 (H1-3xFexTaWO6, x = 0.23) nanotubes as highly active solid acid catalysts were prepared via an exfoliation-scrolling-exchange process. The specific surface area and pore volume of undoped nanotubes (20.8 m2 g-1, 0.057 cm3 g-1) were remarkably enhanced through Fe3+ ion-exchange (>100 m2 g-1, 0.547 cm3 g-1). Doping Fe ions into the nanotubes endowed them with improved thermal stability due to the stronger interaction between the intercalated Fe3+ ions and the host layers. This interaction also facilitated the preservation of effective Brønsted acid sites and the generation of new acid sites. The integration of these functional roles resulted in Fe-doped nanotubes with high acidic catalytic activities in the Friedel-Crafts alkylation of anisole and the esterification of acetic acid. Facile accessibility to active sites, generation of effective Brønsted acid sites, high stability of the tubular structure and strong acid sites were found to synergistically contribute to the excellent acidic catalytic efficiency. Additionally, the activity of cycled nanocatalysts can be easily recovered through annealing treatment.

  20. Facile synthesis of pristine graphene-palladium nanocomposites with extraordinary catalytic activities using swollen liquid crystals

    Science.gov (United States)

    Vats, T.; Dutt, S.; Kumar, R.; Siril, P. F.

    2016-09-01

    Amazing conductivity, perfect honeycomb sp2 arrangement and the high theoretical surface area make pristine graphene as one of the best materials suited for application as catalyst supports. Unfortunately, the low reactivity of the material makes the formation of nanocomposite with inorganic materials difficult. Here we report an easy approach to synthesize nanocomposites of pristine graphene with palladium (Pd-G) using swollen liquid crystals (SLCs) as a soft template. The SLC template gives the control to deposit very small Pd particles of uniform size on G as well as RGO. The synthesized nanocomposite (Pd-G) exhibited exceptionally better catalytic activity compared with Pd-RGO nanocomposite in the hydrogenation of nitrophenols and microwave assisted C-C coupling reactions. The catalytic activity of Pd-G nanocomposite during nitrophenol reduction reaction was sixteen times higher than Pd nanoparticles and more than double than Pd-RGO nanocomposite. The exceptionally high activity of pristine graphene supported catalysts in the organic reactions is explained on the basis of its better pi interacting property compared to partially reduced RGO. The Pd-G nanocomposite showed exceptional stability under the reaction conditions as it could be recycled upto a minimum of 15 cycles for the C-C coupling reactions without any loss in activity.

  1. Catalytic performance of activated carbon supported cobalt catalyst for CO2 reforming of CH4.

    Science.gov (United States)

    Zhang, Guojie; Su, Aiting; Du, Yannian; Qu, Jiangwen; Xu, Ying

    2014-11-01

    Syngas production by CO2 reforming of CH4 in a fixed bed reactor was investigated over a series of activated carbon (AC) supported Co catalysts as a function of Co loading (between 15 and 30wt.%) and calcination temperature (Tc=300, 400 or 500°C). The catalytic performance was assessed through CH4 and CO2 conversions and long-term stability. XRD and SEM were used to characterize the catalysts. It was found that the stability of Co/AC catalysts was strongly dependent on the Co loading and calcination temperature. For the loadings (25wt.% for Tc=300°C), stable activities have been achieved. The loading of excess Co (>wt.% 25) causes negative effects not only on the performance of the catalysts but also on the support surface properties. In addition, the experiment showed that ultrasound can enhance and promote dispersion of the active metal on the carrier, thus improving the catalytic performance of the catalyst. The catalyst activity can be long-term stably maintained, and no obvious deactivation has been observed in the first 2700min. After analyzing the characteristics, a reaction mechanism for CO2 reforming of CH4 over Co/AC catalyst was proposed. Copyright © 2014 Elsevier Inc. All rights reserved.

  2. Superior acidic catalytic activity and stability of Fe-doped HTaWO6 nanotubes

    KAUST Repository

    Liu, He; Zhang, Haitao; Fei, Linfeng; Ma, Hongbin; Zhao, Guoying; Mak, CheeLeung; Zhang, Xixiang; Zhang, Suojiang

    2017-01-01

    Fe-doped HTaWO6 (H1-3xFexTaWO6, x = 0.23) nanotubes as highly active solid acid catalysts were prepared via an exfoliation-scrolling-exchange process. The specific surface area and pore volume of undoped nanotubes (20.8 m2 g-1, 0.057 cm3 g-1) were remarkably enhanced through Fe3+ ion-exchange (>100 m2 g-1, 0.547 cm3 g-1). Doping Fe ions into the nanotubes endowed them with improved thermal stability due to the stronger interaction between the intercalated Fe3+ ions and the host layers. This interaction also facilitated the preservation of effective Brønsted acid sites and the generation of new acid sites. The integration of these functional roles resulted in Fe-doped nanotubes with high acidic catalytic activities in the Friedel-Crafts alkylation of anisole and the esterification of acetic acid. Facile accessibility to active sites, generation of effective Brønsted acid sites, high stability of the tubular structure and strong acid sites were found to synergistically contribute to the excellent acidic catalytic efficiency. Additionally, the activity of cycled nanocatalysts can be easily recovered through annealing treatment.

  3. A new experimental setup for high-pressure catalytic activity measurements on surface deposited mass-selected Pt clusters

    International Nuclear Information System (INIS)

    Watanabe, Yoshihide; Isomura, Noritake

    2009-01-01

    A new experimental setup to study catalytic and electronic properties of size-selected clusters on metal oxide substrates from the viewpoint of cluster-support interaction and to formulate a method for the development of heterogeneous catalysts such as automotive exhaust catalysts has been developed. The apparatus consists of a size-selected cluster source, a photoemission spectrometer, a scanning tunneling microscope (STM), and a high-pressure reaction cell. The high-pressure reaction cell measurements provided information on catalytic properties in conditions close to practical use. The authors investigated size-selected platinum clusters deposited on a TiO 2 (110) surface using a reaction cell and STM. Catalytic activity measurements showed that the catalytic activities have a cluster-size dependency.

  4. Green Synthesis and Catalytic Activity of Gold Nanoparticles Synthesized by Artemisia capillaris Water Extract

    Science.gov (United States)

    Lim, Soo Hyeon; Ahn, Eun-Young; Park, Youmie

    2016-10-01

    Gold nanoparticles were synthesized using a water extract of Artemisia capillaris (AC-AuNPs) under different extract concentrations, and their catalytic activity was evaluated in a 4-nitrophenol reduction reaction in the presence of sodium borohydride. The AC-AuNPs showed violet or wine colors with characteristic surface plasmon resonance bands at 534 543 nm that were dependent on the extract concentration. Spherical nanoparticles with an average size of 16.88 ± 5.47 29.93 ± 9.80 nm were observed by transmission electron microscopy. A blue shift in the maximum surface plasmon resonance was observed with increasing extract concentration. The face-centered cubic structure of AC-AuNPs was confirmed by high-resolution X-ray diffraction analysis. Based on phytochemical screening and Fourier transform infrared spectra, flavonoids, phenolic compounds, and amino acids present in the extract contributed to the reduction of Au ions to AC-AuNPs. The average size of the AC-AuNPs decreased as the extract concentration during the synthesis was increased. Higher 4-nitrophenol reduction reaction rate constants were observed for smaller sizes. The extract in the AC-AuNPs was removed by centrifugation to investigate the effect of the extract in the reduction reaction. Interestingly, the removal of extracts greatly enhanced their catalytic activity by up to 50.4 %. The proposed experimental method, which uses simple centrifugation, can be applied to other metallic nanoparticles that are green synthesized with plant extracts to enhance their catalytic activity.

  5. Electro-catalytic activity of Ni–Co-based catalysts for oxygen evolution reaction

    Energy Technology Data Exchange (ETDEWEB)

    Ju, Hua [School of Urban Rail Transportation, Soochow University, Suzhou 215006 (China); Li, Zhihu [College of Physics, Optoelectronics and Energy, Soochow University, Moye Rd. 688, Suzhou 215006 (China); Xu, Yanhui, E-mail: xuyanhui@suda.edu.cn [College of Physics, Optoelectronics and Energy, Soochow University, Moye Rd. 688, Suzhou 215006 (China)

    2015-04-15

    Graphical abstract: The electro-catalytic activity of different electro-catalysts with a porous electrode structure was compared considering the real electrode area that was evaluated by cyclic measurement. - Highlights: • Ni–Co-based electro-catalysts for OER have been studied and compared. • The real electrode area is calculated and used for assessing the electro-catalysts. • Exchange current and reaction rate constant are estimated. • Ni is more useful for OER reaction than Co. - Abstract: In the present work, Ni–Co-based electrocatalysts (Ni/Co = 0:6, 1:5, 2:4, 3:3, 4:2, 5:1 and 6:0) have been studied for oxygen evolution reaction. The phase structure has been analyzed by X-ray diffraction technique. Based on the XRD and SEM results, it is believed that the synthesized products are poorly crystallized. To exclude the disturbance of electrode preparation technology on the evaluation of electro-catalytic activity, the real electrode surface area is calculated based on the cyclic voltammetry data, assumed that the specific surface capacitance is 60 μF cm{sup −2} for metal oxide electrode. The real electrode area data are used to calculate the current density. The reaction rate constant of OER at different electrodes is also estimated based on basic reaction kinetic equations. It is found that the exchange current is 0.05–0.47 mA cm{sup −2} (the real surface area), and the reaction rate constant has an order of magnitude of 10{sup −7}–10{sup −6} cm s{sup −1}. The influence of the electrode potential on OER rate has been also studied by electrochemical impedance spectroscopy (EIS) technique. Our investigation has shown that the nickel element has more contribution than the cobalt; the nickel oxide has the best electro-catalytic activity toward OER.

  6. 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.

  7. Polyvinylpyrrolidone adsorption effects on the morphologies of synthesized platinum particles and its catalytic activity

    Energy Technology Data Exchange (ETDEWEB)

    Ooi, Mahayatun Dayana Johan [Nano - Optoelectronic Research and Technology Laboratory, School of Physics, Universiti Sains Malaysia, 11800, Minden, Pulau Pinang (Malaysia); Aziz, Azlan Abdul [Nano - Optoelectronic Research and Technology Laboratory, School of Physics, Universiti Sains Malaysia, 11800, Minden, Pulau Pinang (Malaysia); Nanobiotechnology Research and Innovation (NanoBRI), INFORMM, Universiti Sains Malaysia, 11800, Minden, Pulau Pinang (Malaysia)

    2015-04-24

    Flower-like Platinum micro-structures were synthesized from different concentration of the PVP using solvothermal method. At 5.0×10{sup −3} mmol of PVP, well-defined flower-like pattern consists of triangular petals radiating from the centre were produced whereas larger flower network developed at higher PVP concentration. High degree of crystallinity was obtained upon each increment of PVP. The well defined flower like pattern synthesized using 5.0×10{sup −3} mmol PVP exhibit the highest catalytic activity and stability towards electro-oxidation of formic acid.

  8. 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 ...

  9. Catalytic activity of bimetal-containing Co,Pd systems in the oxidation of carbon monoxide

    Science.gov (United States)

    Oleksenko, L. P.; Lutsenko, L. V.

    2013-02-01

    The catalytic activity of low-percentage Co,Pd systems on ZSM-5, ERI, SiO2, and Al2O3 supports in the oxidation of CO was studied. The activity of bimetal-containing catalysts was shown to depend on the nature of the catalyst and the amount and ratio of their active components. According to the results of thermoprogrammed reduction with H2 (H2 TPR) and X-ray photoelectron spectroscopy (XPS) data, the metals are distributed as isolated cations or Coδ+-O-Pdδ+ clusters with cobalt and palladium cations surrounded by off-lattice oxygen in Co,Pd systems. The 0.8% Co,0.5% Pd-ZSM-5 bimetal catalysts were found to be more active due to the presence of clusters.

  10. Nanocaged enzymes with enhanced catalytic activity and increased stability against protease digestion

    Science.gov (United States)

    Zhao, Zhao; Fu, Jinglin; Dhakal, Soma; Johnson-Buck, Alexander; Liu, Minghui; Zhang, Ting; Woodbury, Neal W.; Liu, Yan; Walter, Nils G.; Yan, Hao

    2016-01-01

    Cells routinely compartmentalize enzymes for enhanced efficiency of their metabolic pathways. Here we report a general approach to construct DNA nanocaged enzymes for enhancing catalytic activity and stability. Nanocaged enzymes are realized by self-assembly into DNA nanocages with well-controlled stoichiometry and architecture that enabled a systematic study of the impact of both encapsulation and proximal polyanionic surfaces on a set of common metabolic enzymes. Activity assays at both bulk and single-molecule levels demonstrate increased substrate turnover numbers for DNA nanocage-encapsulated enzymes. Unexpectedly, we observe a significant inverse correlation between the size of a protein and its activity enhancement. This effect is consistent with a model wherein distal polyanionic surfaces of the nanocage enhance the stability of active enzyme conformations through the action of a strongly bound hydration layer. We further show that DNA nanocages protect encapsulated enzymes against proteases, demonstrating their practical utility in functional biomaterials and biotechnology. PMID:26861509

  11. Nanocaged enzymes with enhanced catalytic activity and increased stability against protease digestion

    Science.gov (United States)

    Zhao, Zhao; Fu, Jinglin; Dhakal, Soma; Johnson-Buck, Alexander; Liu, Minghui; Zhang, Ting; Woodbury, Neal W.; Liu, Yan; Walter, Nils G.; Yan, Hao

    2016-02-01

    Cells routinely compartmentalize enzymes for enhanced efficiency of their metabolic pathways. Here we report a general approach to construct DNA nanocaged enzymes for enhancing catalytic activity and stability. Nanocaged enzymes are realized by self-assembly into DNA nanocages with well-controlled stoichiometry and architecture that enabled a systematic study of the impact of both encapsulation and proximal polyanionic surfaces on a set of common metabolic enzymes. Activity assays at both bulk and single-molecule levels demonstrate increased substrate turnover numbers for DNA nanocage-encapsulated enzymes. Unexpectedly, we observe a significant inverse correlation between the size of a protein and its activity enhancement. This effect is consistent with a model wherein distal polyanionic surfaces of the nanocage enhance the stability of active enzyme conformations through the action of a strongly bound hydration layer. We further show that DNA nanocages protect encapsulated enzymes against proteases, demonstrating their practical utility in functional biomaterials and biotechnology.

  12. Decolourisation of dye solutions by oxidation with H2O2 in the presence of modified activated carbons

    International Nuclear Information System (INIS)

    Santos, V.P.; Pereira, M.F.R.; Faria, P.C.C.; Orfao, J.J.M.

    2009-01-01

    The decolourisation of dye solutions by oxidation with H 2 O 2 , using activated carbon as catalyst, is studied. For this purpose, three different samples, mainly differing in the respective surface chemistries, were prepared and characterized. Moreover, this work involved three pH levels, corresponding to acid, neutral and alkaline solutions, and six dyes belonging to several classes. The catalytic decolourisation tests were performed in a laboratorial batch reactor. Adsorption on activated carbon and non-catalytic peroxidation kinetic experiments were also carried out in the same reactor, in order to compare the efficiencies of the three processes. The non-catalytic reaction is usually inefficient and, typically, adsorption presents a low level of decolourisation. In these cases, the combination of activated carbon with hydrogen peroxide may significantly enhance the process, since the activated carbon catalyses the decomposition of H 2 O 2 into hydroxyl radicals, which are very reactive. Based on the experiments with the different activated carbon samples, which have similar physical properties, it is proved that the surface chemistry of the catalyst plays a key role, being the basic sample the most active. This is discussed considering the involvement of the free electrons on the graphene basal planes of activated carbon as active centres for the catalytic reaction. Additionally, it is shown that the decolourisation is enhanced at high pH values, and a possible explanation for this observation, based on the proposed mechanism, is given

  13. Effect of plasma-induced surface charging on catalytic processes: application to CO2 activation

    Science.gov (United States)

    Bal, Kristof M.; Huygh, Stijn; Bogaerts, Annemie; Neyts, Erik C.

    2018-02-01

    Understanding the nature and effect of the multitude of plasma-surface interactions in plasma catalysis is a crucial requirement for further process development and improvement. A particularly intriguing and rather unique property of a plasma-catalytic setup is the ability of the plasma to modify the electronic structure, and hence chemical properties, of the catalyst through charging, i.e. the absorption of excess electrons. In this work, we develop a quantum chemical model based on density functional theory to study excess negative surface charges in a heterogeneous catalyst exposed to a plasma. This method is specifically applied to investigate plasma-catalytic CO2 activation on supported M/Al2O3 (M = Ti, Ni, Cu) single atom catalysts. We find that (1) the presence of a negative surface charge dramatically improves the reductive power of the catalyst, strongly promoting the splitting of CO2 to CO and oxygen, and (2) the relative activity of the investigated transition metals is also changed upon charging, suggesting that controlled surface charging is a powerful additional parameter to tune catalyst activity and selectivity. These results strongly point to plasma-induced surface charging of the catalyst as an important factor contributing to the plasma-catalyst synergistic effects frequently reported for plasma catalysis.

  14. Relief of autoinhibition by conformational switch explains enzyme activation by a catalytically dead paralog

    Energy Technology Data Exchange (ETDEWEB)

    Volkov, Oleg A.; Kinch, Lisa; Ariagno, Carson; Deng, Xiaoyi; Zhong, Shihua; Grishin, Nick; Tomchick, Diana R.; Chen, Zhe; Phillips, Margaret A.

    2016-12-15

    Catalytically inactive enzyme paralogs occur in many genomes. Some regulate their active counterparts but the structural principles of this regulation remain largely unknown. We report X-ray structures ofTrypanosoma brucei S-adenosylmethionine decarboxylase alone and in functional complex with its catalytically dead paralogous partner, prozyme. We show monomericTbAdoMetDC is inactive because of autoinhibition by its N-terminal sequence. Heterodimerization with prozyme displaces this sequence from the active site through a complex mechanism involving acis-to-transproline isomerization, reorganization of a β-sheet, and insertion of the N-terminal α-helix into the heterodimer interface, leading to enzyme activation. We propose that the evolution of this intricate regulatory mechanism was facilitated by the acquisition of the dimerization domain, a single step that can in principle account for the divergence of regulatory schemes in the AdoMetDC enzyme family. These studies elucidate an allosteric mechanism in an enzyme and a plausible scheme by which such complex cooperativity evolved.

  15. Enhanced Activity of Nanocrystalline Zeolites for Selective Catalytic Reduction of NOx

    International Nuclear Information System (INIS)

    Sarah C. Larson; Vicki H. Grassian

    2006-01-01

    Nanocrystalline zeolites with discrete crystal sizes of less than 100 nm have different properties relative to zeolites with larger crystal sizes. Nanocrystalline zeolites have improved mass transfer properties and very large internal and external surface areas that can be exploited for many different applications. The additional external surface active sites and the improved mass transfer properties of nanocrystalline zeolites offer significant advantages for selective catalytic reduction (SCR) catalysis with ammonia as a reductant in coal-fired power plants relative to current zeolite based SCR catalysts. Nanocrystalline NaY was synthesized with a crystal size of 15-20 nm and was thoroughly characterized using x-ray diffraction, electron paramagnetic resonance spectroscopy, nitrogen adsorption isotherms and Fourier Transform Infrared (FT-IR) spectroscopy. Copper ions were exchanged into nanocrystalline NaY to increase the catalytic activity. The reactions of nitrogen dioxides (NO x ) and ammonia (NH 3 ) on nanocrystalline NaY and CuY were investigated using FT-IR spectroscopy. Significant conversion of NO 2 was observed at room temperature in the presence of NH 3 as monitored by FT-IR spectroscopy. Copper-exchanged nanocrystalline NaY was more active for NO 2 reduction with NH 3 relative to nanocrystalline NaY

  16. The influence of copper in dealloyed binary platinum–copper electrocatalysts on methanol electroxidation catalytic activities

    Energy Technology Data Exchange (ETDEWEB)

    Poochai, Chatwarin [Department of Chemistry, Faculty of Science, Mahidol University, Bangkok 10400 (Thailand); Center of Excellence for Innovation in Chemistry, Faculty of Science, Mahidol University, Bangkok 10400 (Thailand); Veerasai, Waret, E-mail: waret.vee@mahidol.ac.th [Department of Chemistry, Faculty of Science, Mahidol University, Bangkok 10400 (Thailand); Center of Excellence for Innovation in Chemistry, Faculty of Science, Mahidol University, Bangkok 10400 (Thailand); Somsook, Ekasith [Department of Chemistry, Faculty of Science, Mahidol University, Bangkok 10400 (Thailand); Center of Excellence for Innovation in Chemistry, Faculty of Science, Mahidol University, Bangkok 10400 (Thailand); Dangtip, Somsak [Department of Physics, and NANOTEC COE at Mahidol University, Faculty of Science, Mahidol University, Bangkok 10400 (Thailand)

    2015-08-01

    In this study, we prepared and characterized carbon paper-supported dealloyed binary Pt–Cu core–shell electrocatalysts (denoted as Pt{sub x}Cu{sub (100−x)/}CP) by cyclic co-electrodeposition and selective copper dealloying in an acidic medium, and we investigated the effect of the copper content in the samples on the catalytic activities toward methanol electroxidation reaction (MOR). X-ray photo-emission spectroscopy (XPS) and inductively coupled plasma atomic emission spectroscopy (ICP-AES) indicated that the structure of dealloyed binary Pt–Cu catalysts possessed a Pt-rich shell and a Cu rich core. X-ray absorption near edge spectroscopy (XANES) displayed that the oxidation states of Pt and Cu were zero and one, respectively, implying the formation of metallic Pt and Cu{sub 2}O, respectively. X-ray diffraction spectroscopy (XRD) confirmed that Cu was inserted into a face-centered cubic Pt structure forming Pt–Cu alloys. Scanning electron microscopy (SEM) and transmission electron microscope (TEM) displayed a cubic shape of Pt/CP and a spherical shape of Pt{sub x}Cu{sub (100−x)/}CP with several hundred nanometer sizes of agglomeration that depended on the Cu content. Cyclic voltammetry, chronoamperometry, and electrochemical impedance spectroscopy were performed to confirm that the sample of Pt{sub 70}Cu{sub 30}/CP exhibited the best catalytic activities in terms of the specific current, current density, catalytic poisoning tolerance, and stability. - Graphical abstract: Display Omitted - Highlights: • Binary electrocatalysts of Pt{sub x}Cu{sub (100−x)}/CP were prepared by cyclic co-electrodeposition and selective copper dealloying. • The structures of Pt{sub x}Cu{sub (100−x)}/CP were a Pt rich shell and a Cu rich core. • The Pt{sub 70}Cu{sub 30}/CP was the excellent catalytic activity towards methanol electrooxidation and CO{sub ads} tolerance.

  17. Simultaneous pore enlargement and introduction of highly dispersed Fe active sites in MSNs for enhanced catalytic activity

    International Nuclear Information System (INIS)

    Gu Jinlou; Dong Xu; Elangovan, S.P.; Li Yongsheng; Zhao Wenru; Iijima, Toshio; Yamazaki, Yasuo; Shi Jianlin

    2012-01-01

    An effective post-hydrothermal treatment strategy has been developed to dope highly dispersed iron catalytical centers into the framework of mesoporous silica, to keep the particle size in nanometric scale, and in the meanwhile, to expand the pore size of the synthesized mesoporous silica nanoparticles (MSNs). Characterization techniques such as XRD, BET, SEM and TEM support that the synthesized samples are long period ordered with particles size about 100 nm and a relatively large pore size of ca. 3.5 nm. UV–vis, XPS and EPR measurements demonstrate that the introduced iron active centers are highly dispersed in a coordinatively unsaturated status. NH 3 -TPD verifies that the acid amount of iron-doped MSNs is quite high. The synthesized nanocatalysts show an excellent catalytic performance for benzylation of benzene by benzyl chloride, and they present relatively higher yield and selectivity to diphenylmethane with a lower iron content and much shorter reaction time. - Graphical abstract: Uniform MSNs with iron active centers and large pore size have been prepared by a newly developed strategy, which demonstrates enhanced catalytic performance for benzylation of benzene by benzyl chloride. Highlights: ► Iron species were introduced into the framework of mesoporous silica nanoparticles with uniform dispersion. ► The pore sizes of the synthesized nanocatalysts were expanded. ► The acidic site quantities were quite high and the acidic centers were accessible. ► The nanocatalysts presented higher yield and selectivity to diphenylmethane with significantly lower Fe content.

  18. Catalytic decomposition of hydrogen peroxide and 4-chlorophenol in the presence of modified activated carbons.

    Science.gov (United States)

    Huang, Hsu-Hui; Lu, Ming-Chun; Chen, Jong-Nan; Lee, Cheng-Te

    2003-06-01

    The objective of this research was to examine the heterogeneous catalytic decomposition of H(2)O(2) and 4-chlorophenol (4-CP) in the presence of activated carbons modified with chemical pretreatments. The decomposition of H(2)O(2) was suppressed significantly by the change of surface properties including the decreased pH(pzc) modified with oxidizing agent and the reduced active sites occupied by the adsorption of 4-CP. The apparent reaction rate of H(2)O(2) decomposition was dominated by the intrinsic reaction rates on the surface of activated carbon rather than the mass transfer rate of H(2)O(2) to the solid surface. By the detection of chloride ion in suspension, the reduction of 4-CP was not only attributed to the advanced adsorption but also the degradation of 4-CP. The catalytic activity toward 4-CP for the activated carbon followed the inverse sequence of the activity toward H(2)O(2), suggesting that acidic surface functional group could retard the H(2)O(2) loss and reduce the effect of surface scavenging resulting in the increase of the 4-CP degradation efficiency. Few effective radicals were expected to react with 4-CP for the strong effect of surface scavenging, which could explain why the degradation rate of 4-CP observed in this study was so slow and the dechlorination efficiency was independent of the 4-CP concentration in aqueous phase. Results show that the combination of H(2)O(2) and granular activated carbon (GAC) did increase the total removal of 4-CP than that by single GAC adsorption.

  19. The Botrytis cinerea xylanase Xyn11A contributes to virulence with its necrotizing activity, not with its catalytic activity

    Directory of Open Access Journals (Sweden)

    González Celedonio

    2010-02-01

    Full Text Available Abstract Background The Botrytis cinerea xylanase Xyn11A has been previously shown to be required for full virulence of this organism despite its poor contribution to the secreted xylanase activity and the low xylan content of B. cinerea hosts. Intriguingly, xylanases from other fungi have been shown to have the property, independent of the xylan degrading activity, to induce necrosis when applied to plant tissues, so we decided to test the hypothesis that secreted Xyn11A contributes to virulence by promoting the necrosis of the plant tissue surrounding the infection, therefore facilitating the growth of this necrotroph. Results We show here that Xyn11A has necrotizing activity on plants and that this capacity is conserved in site-directed mutants of the protein lacking the catalytic activity. Besides, Xyn11A contributes to the infection process with the necrotizing and not with the xylan hydrolyzing activity, as the catalytically-impaired Xyn11A variants were able to complement the lower virulence of the xyn11A mutant. The necrotizing activity was mapped to a 30-amino acids peptide in the protein surface, and this region was also shown to mediate binding to tobacco spheroplasts by itself. Conclusions The main contribution of the xylanase Xyn11A to the infection process of B. cinerea is to induce necrosis of the infected plant tissue. A conserved 30-amino acids region on the enzyme surface, away from the xylanase active site, is responsible for this effect and mediates binding to plant cells.

  20. Precursor type affecting surface properties and catalytic activity of sulfated zirconia

    Directory of Open Access Journals (Sweden)

    Zarubica Aleksandra R.

    2007-01-01

    Full Text Available Zirconium-hydroxide precursor samples are synthesized from Zr-hydroxide, Zr-nitrate, and Zr-alkoxide, by precipitation/impregnation, as well as by a modified sol-gel method. Precursor samples are further sulphated for the intended SO4 2- content of 4 wt.%, and calcined at 500-700oC. Differences in precursors’ origin and calcination temperature induce the incorporation of SO4 2- groups into ZrO2 matrices by various mechanisms. As a result, different amounts of residual sulphates are coupled with other structural, as well as surface properties, resulting in various catalytic activities of sulphated zirconia samples. Catalyst activity and selectivity are a complex synergistic function of tetragonal phase fraction, sulphates contents, textural and surface characteristics. Superior activity of SZ of alkoxide origin can be explained by a beneficial effect of meso-pores owing to a better accommodation of coke deposits.

  1. Annihilation characteristics of positrons in oxide powders in relation to catalytic activities

    International Nuclear Information System (INIS)

    Ito, K.; Ohtsu, Y.; Tanigawa, S.; Enomura, A.; Tsuda, N.

    1982-01-01

    The annihilation chaaracteristics in magnesium oxide powders were studied by the measurements of Doppler broadening of annihilation radiations. MgO powders are well known as a solid base and are utilized as a catalyst for the reactions which start by extracting protons from molecules such as decomposition of alcohol. The isochronal annealing behavior of annihilation characteristics in the process Mg(OH) 2 → MgO was found to correspond just to the change in the number of basic points, specific surface area and catalytic activities in some reactions. From the results of the thermal equilibrium measurements of MgO powders after dehydration, the temperature dependence of S parameter can be considered as the thermal activation process of the escape of positrons from trapped states at surface to form positroniums. The derived value of this activation energy was 0.187 eV. (Auth.)

  2. Preparation of gold nanoparticles using Salicornia brachiata plant extract and evaluation of catalytic and antibacterial activity

    Science.gov (United States)

    Ayaz Ahmed, Khan Behlol; Subramanian, Swetha; Sivasubramanian, Aravind; Veerappan, Ganapathy; Veerappan, Anbazhagan

    2014-09-01

    The current study deals with the synthesis of gold nanoparticles (AuNPs) using Salicornia brachiata (Sb) and evaluation of their antibacterial and catalytic activity. The SbAuNPs showed purple color with a characteristic surface plasmon resonance peak at 532 nm. Scanning electron microscopy and transmission electron microscopy revealed polydispersed AuNPs with the size range from 22 to 35 nm. Energy dispersive X-ray and thin layer X-ray diffraction analysis clearly shows that SbAuNPs was pure and crystalline in nature. As prepared gold nanoparticles was used as a catalyst for the sodium borohydride reduction of 4-nitro phenol to 4-amino phenol and methylene blue to leucomethylene blue. The green synthesized nanoparticles exhibited potent antibacterial activity against the pathogenic bacteria, as evidenced by their zone of inhibition. In addition, we showed that the SbAuNPs in combination with the regular antibiotic, ofloxacin, exhibit superior antibacterial activity than the individual.

  3. Molecular dynamics characterization of five pathogenic factor X mutants associated with decreased catalytic activity

    KAUST Repository

    Abdel-Azeim, Safwat

    2014-11-11

    Factor X (FX) is one of the major players in the blood coagulation cascade. Upon activation to FXa, it converts prothrombin to thrombin, which in turn converts fibrinogen into fibrin (blood clots). FXa deficiency causes hemostasis defects, such as intracranial bleeding, hemathrosis, and gastrointestinal blood loss. Herein, we have analyzed a pool of pathogenic mutations, located in the FXa catalytic domain and directly associated with defects in enzyme catalytic activity. Using chymotrypsinogen numbering, they correspond to D102N, T135M, V160A, G184S, and G197D. Molecular dynamics simulations were performed for 1.68 μs on the wild-type and mutated forms of FXa. Overall, our analysis shows that four of the five mutants considered, D102N, T135M, V160A, and G184S, have rigidities higher than those of the wild type, in terms of both overall protein motion and, specifically, subpocket S4 flexibility, while S1 is rather insensitive to the mutation. This acquired rigidity can clearly impact the substrate recognition of the mutants.

  4. Molecular dynamics characterization of five pathogenic factor X mutants associated with decreased catalytic activity

    KAUST Repository

    Abdel-Azeim, Safwat; Oliva, Romina M.; Chermak, Edrisse; De Cristofaro, Raimondo; Cavallo, Luigi

    2014-01-01

    Factor X (FX) is one of the major players in the blood coagulation cascade. Upon activation to FXa, it converts prothrombin to thrombin, which in turn converts fibrinogen into fibrin (blood clots). FXa deficiency causes hemostasis defects, such as intracranial bleeding, hemathrosis, and gastrointestinal blood loss. Herein, we have analyzed a pool of pathogenic mutations, located in the FXa catalytic domain and directly associated with defects in enzyme catalytic activity. Using chymotrypsinogen numbering, they correspond to D102N, T135M, V160A, G184S, and G197D. Molecular dynamics simulations were performed for 1.68 μs on the wild-type and mutated forms of FXa. Overall, our analysis shows that four of the five mutants considered, D102N, T135M, V160A, and G184S, have rigidities higher than those of the wild type, in terms of both overall protein motion and, specifically, subpocket S4 flexibility, while S1 is rather insensitive to the mutation. This acquired rigidity can clearly impact the substrate recognition of the mutants.

  5. 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.

  6. μ-reactor measurements of catalytic activity of mass selected nano-particles

    DEFF Research Database (Denmark)

    Riedel, Jakob Nordheim

    The work of this thesis revolves around catalytic activity measurements of nano-particles tested using a μ-reactor platform, developed and produced at DTU, in a collaboration between CINF and Nanotech. The thesis contains the results from two separate research projects; both utilising μ-reactors ......The work of this thesis revolves around catalytic activity measurements of nano-particles tested using a μ-reactor platform, developed and produced at DTU, in a collaboration between CINF and Nanotech. The thesis contains the results from two separate research projects; both utilising μ......-reactors in combination with surface science techniques and computer simulations. The first project described is a study of hydrogen dissociation on mono-disperse platinum clusters. The second project studies methanation from carbon monoxide and hydrogen on nano-particles of nickel-iron alloys. The second study is a work...... in progress, and the corresponding chapter aims to summarise the results so far. Other projects are not included in the thesis because they are inconclusive or dead ends. Hydrogen dissociation was studied by the H2/D2 exchange reaction on SiO2-supported mono-disperse platinum clusters in a -reactor...

  7. Process for forming a homogeneous oxide solid phase of catalytically active material

    Science.gov (United States)

    Perry, Dale L.; Russo, Richard E.; Mao, Xianglei

    1995-01-01

    A process is disclosed for forming a homogeneous oxide solid phase reaction product of catalytically active material comprising one or more alkali metals, one or more alkaline earth metals, and one or more Group VIII transition metals. The process comprises reacting together one or more alkali metal oxides and/or salts, one or more alkaline earth metal oxides and/or salts, one or more Group VIII transition metal oxides and/or salts, capable of forming a catalytically active reaction product, in the optional presence of an additional source of oxygen, using a laser beam to ablate from a target such metal compound reactants in the form of a vapor in a deposition chamber, resulting in the deposition, on a heated substrate in the chamber, of the desired oxide phase reaction product. The resulting product may be formed in variable, but reproducible, stoichiometric ratios. The homogeneous oxide solid phase product is useful as a catalyst, and can be produced in many physical forms, including thin films, particulate forms, coatings on catalyst support structures, and coatings on structures used in reaction apparatus in which the reaction product of the invention will serve as a catalyst.

  8. PEEM microscopy and DFT calculations of catalytically active platinum surfaces and interfaces

    International Nuclear Information System (INIS)

    Spiel, C.

    2012-01-01

    The aim of this thesis was to investigate the properties of catalytically active platinum surfaces and interfaces both with experimental and theoretical methods. Using experimental methods, catalytic CO oxidation on individual grains of a polycrystalline platinum foil was studied in situ under high vacuum (HV) conditions. A polycrystalline platinum foil consists of individual µm-sized crystal grains that are mainly [100]-, [110]- and [111]-oriented and differ significantly in their catalytic activity. In order to elucidate the differences existing between the reactivity of the individual grains, a combination of photoemission electron microscopy (PEEM) and quadrupole mass spectrometry (QMS) was used in this work. The working principle of PEEM is based on the photoelectric effect where illumination of the sample with (UV-)light causes emission of photoelectrons. The emitted photoelectrons are used to visualize the sample surface (with typical resolution in the low micrometer range). The PEEM image contrast originates from differences in the local work function that may arise due to different crystallographic orientations and/or changes in the adsorbate coverage. With a combination of PEEM and QMS, it was possible to study the kinetics of catalytic CO oxidation on polycrystalline platinum foil both in a global and a laterally-resolved way simultaneously. If catalytic CO oxidation on surfaces of platinum is followed at constant temperature and oxygen partial pressure under cyclic variation of the CO pressure, a hysteresis in the CO2 production rate is observed in the bistability region with two noticeable kinetic transitions (called tA and tB) taking place at different CO pressures when the catalyst surface switches back-and-forth between two steady states of high and low reactivity while the Pt-surface is, correspondingly, either oxygen- or CO-covered. In the bistability region between τ A and τ B , the system stays (at the same values of the external parameters p

  9. Highly effective catalytic peroxymonosulfate activation on N-doped mesoporous carbon for o-phenylphenol degradation.

    Science.gov (United States)

    Hou, Jifei; Yang, Shasha; Wan, Haiqin; Fu, Heyun; Qu, Xiaolei; Xu, Zhaoyi; Zheng, Shourong

    2018-04-01

    As a broad-spectrum preservative, toxic o-phenylphenol (OPP) was frequently detected in aquatic environments. In this study, N-doped mesoporous carbon was prepared by a hard template method using different nitrogen precursors and carbonization temperatures (i.e., 700, 850 and 1000 °C), and was used to activate peroxymonosulfate (PMS) for OPP degradation. For comparison, mesoporous carbon (CMK-3) was also prepared. Characterization results showed that the N-doped mesoporous carbon samples prepared under different conditions were perfect replica of their template. In comparison with ethylenediamine (EDA) and dicyandiamide (DCDA) as the precursors, N-doped mesoporous carbon prepared using EDA and carbon tetrachloride as the precursors displayed a higher catalytic activity for OPP degradation. Increasing carbonization temperature of N-doped mesoporous carbon led to decreased N content and increased graphitic N content at the expense of pyridinic and pyrrolic N. Electron paramagnetic resonance (EPR) analysis showed that PMS activation on N-doped mesoporous carbon resulted in highly active species and singlet oxygen, and catalytic PMS activation for OPP degradation followed a combined radical and nonradical reaction mechanism. Increasing PMS concentration enhanced OPP degradation, while OPP degradation rate was independent on initial OPP concentration. Furthermore, the dependency of OPP degradation on PMS concentration followed the Langmuir-Hinshelwood model, reflecting that the activation of adsorbed PMS was the rate controlling step. Based on the analysis by time-of-flight mass spectrometry, the degradation pathway of OPP was proposed. Copyright © 2018 Elsevier Ltd. All rights reserved.

  10. Influence of preparation conditions of hollow titania–nickel composite spheres on their catalytic activity for hydrolytic dehydrogenation of ammonia borane

    Energy Technology Data Exchange (ETDEWEB)

    Umegaki, Tetsuo, E-mail: umegaki.tetsuo@nihon-u.ac.jp [Department of Materials and Applied Chemistry, College of Science and Technology, Nihon University, 1-8-14, Kanda-Surugadai, Chiyoda-Ku, Tokyo 101-8308 (Japan); Ohashi, Takato [Department of Materials and Applied Chemistry, College of Science and Technology, Nihon University, 1-8-14, Kanda-Surugadai, Chiyoda-Ku, Tokyo 101-8308 (Japan); Xu, Qiang [National Institute of Advanced Industrial Science and Technology (AIST), 1-8-31 Midorigaoka, Ikeda, Osaka 563-8577 (Japan); Kojima, Yoshiyuki [Department of Materials and Applied Chemistry, College of Science and Technology, Nihon University, 1-8-14, Kanda-Surugadai, Chiyoda-Ku, Tokyo 101-8308 (Japan)

    2014-04-01

    Highlights: • We study influence of preparation conditions on activity of hollow titania–nickel composite spheres. • The activity for hydrolytic dehydrogenation of NH{sub 3}BH{sub 3} increases with increase of Ti + Ni content. • The activity depends on the amount of PS residue in the hollow spheres. - Abstract: The present work reports influence of preparation conditions of hollow titania–nickel composite spheres on their morphology and catalytic activity for hydrolytic dehydrogenation of ammonia borane (NH{sub 3}BH{sub 3}). The as-prepared hollow titania–nickel composite spheres were characterized by transmission electron microscopy (TEM). Catalytic activities of the hollow spheres for hydrolytic dehydrogenation of aqueous NaBH{sub 4}/NH{sub 3}BH{sub 3} solution improve with the decrease of Ti + Ni content. From the results of FTIR spectra and elemental analysis, the amount of residual polystyrene (PS) templates is able to be reduced by increasing aging time for the preparation, and the catalytic activity of the hollow spheres increases when the amount of residual PS templates decreases. The carbon content in the hollow spheres prepared with aging time = 24 h is 17.3 wt.%, and the evolution of 62 mL hydrogen is finished in about 22 min in the presence of the hollow spheres from aqueous NaBH{sub 4}/NH{sub 3}BH{sub 3} solution. The molar ratio of the hydrolytically generated hydrogen to the initial NH{sub 3}BH{sub 3} in the presence of the hollow spheres is 2.7.

  11. 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.

  12. Enhanced catalytic activity over MIL-100(Fe) loaded ceria catalysts for the selective catalytic reduction of NO{sub x} with NH{sub 3} at low temperature

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Peng [School of Environmental Science and Technology, Dalian University of Technology, Key Laboratory of Industrial Ecology and Environmental Engineering (Ministry of Education, China), Dalian 116024 (China); Sun, Hong [School of Environmental & Chemical Engineering, Dalian Jiaotong University, Dalian 116028 (China); Quan, Xie, E-mail: quanxie@dlut.edu.cn [School of Environmental Science and Technology, Dalian University of Technology, Key Laboratory of Industrial Ecology and Environmental Engineering (Ministry of Education, China), Dalian 116024 (China); Chen, Shuo [School of Environmental Science and Technology, Dalian University of Technology, Key Laboratory of Industrial Ecology and Environmental Engineering (Ministry of Education, China), Dalian 116024 (China)

    2016-01-15

    Highlights: • Nano-ceria was successfully encapsulated into MIL-100(Fe) for the SCR of NO{sub x}. • The incorporated ceria in MIL-100(Fe) showed high content of chemisorbed oxygen. • The added ceria into MIL-100(Fe) improved the formation of adsorbed NO{sub 2} species. • The addition of ceria into MIL-100(Fe) enhanced SCR activity at low temperature. - Abstract: The development of catalysts for selective catalytic reduction (SCR) reactions that are highly active at low temperatures and show good resistance to SO{sub 2} and H{sub 2}O is still a challenge. In this study, we have designed and developed a high-performance SCR catalyst based on nano-sized ceria encapsulated inside the pores of MIL-100(Fe) that combines excellent catalytic power with a metal organic framework architecture synthesized by the impregnation method (IM). Transmission electron microscopy (TEM) revealed the encapsulation of ceria in the cavities of MIL-100(Fe). The prepared IM-CeO{sub 2}/MIL-100(Fe) catalyst shows improved catalytic activity both at low temperatures and throughout a wide temperature window. The temperature window for 90% NO{sub x} conversion ranges from 196 to 300 °C. X-ray photoelectron spectroscopy (XPS) and in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFT) analysis indicated that the nano-sized ceria encapsulated inside MIL-100(Fe) promotes the production of chemisorbed oxygen on the catalyst surface, which greatly enhances the formation of the NO{sub 2} species responsible for fast SCR reactions.

  13. Relationship between the structure of Fe-MCM-48 and its activity in catalytic ozonation for diclofenac mineralization.

    Science.gov (United States)

    Li, Xukai; Chen, Weirui; Tang, Yiming; Li, Laisheng

    2018-05-12

    Fe-MCM-48 catalyst with a three-dimensional cubic pore structure was directly synthesized via a hydrothermal method, and the mineralization efficiency of diclofenac (DCF) in the catalytic ozonation process (Fe-MCM-48/O 3 ) was assessed. X-ray diffraction (XRD), N 2 adsorption desorption, transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) characterizations revealed that Fe existed in the framework of MCM-48, and Fe-MCM-48 possessed a large surface area and a highly ordered cubic mesoporous structure, which could accelerate reactants and products diffusion. Regarding mineralization efficiency, the addition of Fe-MCM-48 significantly improved total organic carbon (TOC) removal, and approximately 49.9% TOC were removed through the Fe-MCM-48/O 3 process at 60 min, which was 2.0 times higher than that in single ozonation. Due to this catalyst's superior structure, Fe-MCM-48 showed the better catalytic activity compared with Fe-MCM-41 and Fe loaded MCM-48 (Fe/MCM-48, Fe existed on the surface of MCM-48). DCF removal in the Fe-MCM-48/O 3 process was primarily based on ozone direct oxidation. The improvement of mineralization efficiency was attributed to the function of generated hydroxyl radicals (•OH), which indicated that the presence of Fe-MCM-48 accelerated ozone decomposition. Moreover, the negatively charged surface of Fe-MCM-48 and the proper pH value of the DCF solution played an essential role in OH generation. Copyright © 2018 Elsevier Ltd. All rights reserved.

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

    Directory of Open Access Journals (Sweden)

    Arshid M. Ali

    2015-01-01

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

  15. On the Pt(+) and Rh(+) Catalytic Activity in the Nitrous Oxide Reduction by Carbon Monoxide.

    Science.gov (United States)

    Rondinelli, F; Russo, N; Toscano, M

    2008-11-11

    Nitrous oxide activation by CO in the presence of platinum and rhodium monocations was elucidated by density functional methods for ground and first excited states. Platinum and rhodium cations fulfill the thermodynamic request for the oxygen-atom transport that allows the catalytic cycle to be completed, but actually, just the first one meaningfully improves the kinetics of the process. For both catalysts, the reaction pathways show the only activation barrier in correspondence of nitrogen release and monoxide cation formation. The kinetic analysis of the potential energy profile, in agreement with ICP/SIFT MS experimental data, indicates that platinum performs more in the reduction, while the whole process is not sufficiently fast in the case of rhodium ionic catalyst.

  16. LASER INDUCED SELECTIVE ACTIVATION UTILIZING AUTO-CATALYTIC ELECTROLESS PLATING ON POLYMER SURFACE

    DEFF Research Database (Denmark)

    Zhang, Yang; Nielsen, Jakob Skov; Tang, Peter Torben

    2009-01-01

    . Characterization of the deposited copper layer was used to select and improve laser parameters. Several types of polymers with different melting points were used as substrate. Using the above mentioned laser treatment, standard grades of thermoplastic materials such as ABS, SAN, PE, PC and others have been......This paper presents a new method for selective micro metallization of polymers induced by laser. An Nd: YAG laser was employed to draw patterns on polymer surfaces using a special set-up. After subsequent activation and auto-catalytic electroless plating, copper only deposited on the laser tracks....... Induced by the laser, porous and rough structures are formed on the surface, which favours the palladium attachment during the activation step prior to the metallization. Laser focus detection, scanning electron microscopy (SEM) and other instruments were used to analyze the topography of the laser track...

  17. Pt3Co concave nanocubes: synthesis, formation understanding, and enhanced catalytic activity toward hydrogenation of styrene.

    Science.gov (United States)

    Wang, Chenyu; Lin, Cuikun; Zhang, Lihua; Quan, Zewei; Sun, Kai; Zhao, Bo; Wang, Feng; Porter, Nathan; Wang, Yuxuan; Fang, Jiye

    2014-02-03

    We report a facile synthesis route to prepare high-quality Pt3Co nanocubes with a concave structure, and further demonstrate that these concave Pt3Co nanocubes are terminated with high-index crystal facets. The success of this preparation is highly dependent on an appropriate nucleation process with a successively anisotropic overgrowth and a preservation of the resultant high-index planes by control binding of oleyl-amine/oleic acid with a fine-tuned composition. Using a hydrogenation of styrene as a model reaction, these Pt3Co concave nanocubes as a new class of nanocatalysts with more open structure and active atomic sites located on their high-index crystallographic planes exhibit an enhanced catalytic activity in comparison with low-indexed surface terminated Pt3Co nanocubes in similar size. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Anodically-grown TiO_2 nanotubes: Effect of the crystallization on the catalytic activity toward the oxygen reduction reaction

    International Nuclear Information System (INIS)

    Sacco, Adriano; Garino, Nadia; Lamberti, Andrea; Pirri, Candido Fabrizio; Quaglio, Marzia

    2017-01-01

    Highlights: • Anodically-grown TiO_2 nanotubes as catalysts for the oxygen reduction reaction. • Amorphous NTs compared to thermal- and vapor-treated crystalline nanostructures. • The selection of the crystallization conditions leads to performance similar to Pt. - Abstract: In this work we investigated the behavior of TiO_2 nanotube (NT) arrays, grown by anodic oxidation of Ti foil, as catalysts for the oxygen reduction reaction (ORR) in alkaline water solution. In particular, as-grown amorphous NTs were compared to crystalline anatase nanostructures, obtained following two different procedures, namely thermal and vapor-induced crystallizations. The catalytic activity of these materials toward the ORR was evaluated by cyclic voltammetry measurements. ORR polarization curves, combined with the rotating disk technique, indicated a predominant four-electrons reduction path, especially for crystalline samples. The effect of the structural characteristics of the investigated materials on the catalytic activity was analyzed in details by electrochemical impedance spectroscopy. The catalytic performance of the crystalline NTs is only slightly lower with respect to the reference material for fuel cell applications, namely platinum, but is in line with other cost-effective catalysts recently proposed in the literature. However, if compared to the larger part of these low-cost catalysts, anodically-grown TiO_2 NTs are characterized by a synthesis route which is highly reproducible and easily up-scalable.

  19. Anodically-grown TiO{sub 2} nanotubes: Effect of the crystallization on the catalytic activity toward the oxygen reduction reaction

    Energy Technology Data Exchange (ETDEWEB)

    Sacco, Adriano, E-mail: adriano.sacco@iit.it [Center for Sustainable Future Technologies @Polito, Istituto Italiano di Tecnologia, Corso Trento 21, 10129, Torino (Italy); Garino, Nadia [Center for Sustainable Future Technologies @Polito, Istituto Italiano di Tecnologia, Corso Trento 21, 10129, Torino (Italy); Applied Science and Technology Department, Politecnico di Torino, Corso Duca degli Abruzzi 24, 10129, Torino (Italy); Lamberti, Andrea, E-mail: andrea.lamberti@polito.it [Center for Sustainable Future Technologies @Polito, Istituto Italiano di Tecnologia, Corso Trento 21, 10129, Torino (Italy); Applied Science and Technology Department, Politecnico di Torino, Corso Duca degli Abruzzi 24, 10129, Torino (Italy); Pirri, Candido Fabrizio [Center for Sustainable Future Technologies @Polito, Istituto Italiano di Tecnologia, Corso Trento 21, 10129, Torino (Italy); Applied Science and Technology Department, Politecnico di Torino, Corso Duca degli Abruzzi 24, 10129, Torino (Italy); Quaglio, Marzia [Center for Sustainable Future Technologies @Polito, Istituto Italiano di Tecnologia, Corso Trento 21, 10129, Torino (Italy)

    2017-08-01

    Highlights: • Anodically-grown TiO{sub 2} nanotubes as catalysts for the oxygen reduction reaction. • Amorphous NTs compared to thermal- and vapor-treated crystalline nanostructures. • The selection of the crystallization conditions leads to performance similar to Pt. - Abstract: In this work we investigated the behavior of TiO{sub 2} nanotube (NT) arrays, grown by anodic oxidation of Ti foil, as catalysts for the oxygen reduction reaction (ORR) in alkaline water solution. In particular, as-grown amorphous NTs were compared to crystalline anatase nanostructures, obtained following two different procedures, namely thermal and vapor-induced crystallizations. The catalytic activity of these materials toward the ORR was evaluated by cyclic voltammetry measurements. ORR polarization curves, combined with the rotating disk technique, indicated a predominant four-electrons reduction path, especially for crystalline samples. The effect of the structural characteristics of the investigated materials on the catalytic activity was analyzed in details by electrochemical impedance spectroscopy. The catalytic performance of the crystalline NTs is only slightly lower with respect to the reference material for fuel cell applications, namely platinum, but is in line with other cost-effective catalysts recently proposed in the literature. However, if compared to the larger part of these low-cost catalysts, anodically-grown TiO{sub 2} NTs are characterized by a synthesis route which is highly reproducible and easily up-scalable.

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

    International Nuclear Information System (INIS)

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

    1984-01-01

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

  1. Green synthesis, characterization and catalytic activity of silver nanoparticles using Cassia auriculata flower extract separated fraction

    Science.gov (United States)

    Muthu, Karuppiah; Priya, Sethuraman

    2017-05-01

    Cassia auriculata L., the flower aqueous extract was fractionated by separating funnel using n-hexane (A1), chloroform (A2), ethyl acetate (A3) and triple distilled water (A4). The A4 fraction was concentrated and determined the presence of preliminary phytochemicals such as tannins, flavonoids, glycosides, carbohydrates and polyphenolic compounds. These phytochemical compounds acted as reducing as well as a stabilizing agent in the green synthesis of Ag NPs from aqueous silver ions. Initially, the colour change and UV-vis absorbance surface Plasmon resonance strong, wide band located at 435 nm has confirmed the synthesis of Ag NPs. The X-ray diffraction (XRD) pattern of Ag NPs shows a face-centered cubic crystal structure. The observed values were calculated by Debye-Scherrer equation to theoretical confirms the particle size of 18 nm. The surface morphology of Ag NPs was viewed by HRTEM, the particles are spherical and triangle shapes with sizes from 10 to 35 nm. Further, the Ag NPs was effective catalytic activity in the reduction of highly environmental polluted organic compounds of 4-nitrophenol and methyl orange. The green synthesis of Ag NPs seems to eco-friendly, cost-effective, conventional one spot synthesis and greater performance of catalytic degradation of environmentally polluted organic dyes.

  2. Factors Controlling the Redox Activity of Oxygen in Perovskites: From Theory to Application for Catalytic Reactions

    Directory of Open Access Journals (Sweden)

    Chunzhen Yang

    2017-05-01

    Full Text Available Triggering the redox reaction of oxygens has become essential for the development of (electro catalytic properties of transition metal oxides, especially for perovskite materials that have been envisaged for a variety of applications such as the oxygen evolution or reduction reactions (OER and ORR, respectively, CO or hydrocarbons oxidation, NO reduction and others. While the formation of ligand hole for perovskites is well-known for solid state physicists and/or chemists and has been widely studied for the understanding of important electronic properties such as superconductivity, insulator-metal transitions, magnetoresistance, ferroelectrics, redox properties etc., oxygen electrocatalysis in aqueous media at low temperature barely scratches the surface of the concept of oxygen ions oxidation. In this review, we briefly explain the electronic structure of perovskite materials and go through a few important parameters such as the ionization potential, Madelung potential, and charge transfer energy that govern the oxidation of oxygen ions. We then describe the surface reactivity that can be induced by the redox activity of the oxygen network and the formation of highly reactive surface oxygen species before describing their participation in catalytic reactions and providing mechanistic insights and strategies for designing new (electro catalysts. Finally, we give a brief overview of the different techniques that can be employed to detect the formation of such transient oxygen species.

  3. Helicobacter Catalase Devoid of Catalytic Activity Protects the Bacterium against Oxidative Stress*♦

    Science.gov (United States)

    Benoit, Stéphane L.; Maier, Robert J.

    2016-01-01

    Catalase, a conserved and abundant enzyme found in all domains of life, dissipates the oxidant hydrogen peroxide (H2O2). The gastric pathogen Helicobacter pylori undergoes host-mediated oxidant stress exposure, and its catalase contains oxidizable methionine (Met) residues. We hypothesized catalase may play a large stress-combating role independent of its classical catalytic one, namely quenching harmful oxidants through its recyclable Met residues, resulting in oxidant protection to the bacterium. Two Helicobacter mutant strains (katAH56A and katAY339A) containing catalase without enzyme activity but that retain all Met residues were created. These strains were much more resistant to oxidants than a catalase-deletion mutant strain. The quenching ability of the altered versions was shown, whereby oxidant-stressed (HOCl-exposed) Helicobacter retained viability even upon extracellular addition of the inactive versions of catalase, in contrast to cells receiving HOCl alone. The importance of the methionine-mediated quenching to the pathogen residing in the oxidant-rich gastric mucus was studied. In contrast to a catalase-null strain, both site-change mutants proficiently colonized the murine gastric mucosa, suggesting that the amino acid composition-dependent oxidant-quenching role of catalase is more important than the well described H2O2-dissipating catalytic role. Over 100 years after the discovery of catalase, these findings reveal a new non-enzymatic protective mechanism of action for the ubiquitous enzyme. PMID:27605666

  4. 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.

  5. Mutations in the catalytic loop HRD motif alter the activity and function of Drosophila Src64.

    Directory of Open Access Journals (Sweden)

    Taylor C Strong

    Full Text Available The catalytic loop HRD motif is found in most protein kinases and these amino acids are predicted to perform functions in catalysis, transition to, and stabilization of the active conformation of the kinase domain. We have identified mutations in a Drosophila src gene, src64, that alter the three HRD amino acids. We have analyzed the mutants for both biochemical activity and biological function during development. Mutation of the aspartate to asparagine eliminates biological function in cytoskeletal processes and severely reduces fertility, supporting the amino acid's critical role in enzymatic activity. The arginine to cysteine mutation has little to no effect on kinase activity or cytoskeletal reorganization, suggesting that the HRD arginine may not be critical for coordinating phosphotyrosine in the active conformation. The histidine to leucine mutant retains some kinase activity and biological function, suggesting that this amino acid may have a biochemical function in the active kinase that is independent of its side chain hydrogen bonding interactions in the active site. We also describe the phenotypic effects of other mutations in the SH2 and tyrosine kinase domains of src64, and we compare them to the phenotypic effects of the src64 null allele.

  6. 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.

  7. 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.

  8. Biosynthesis of Copper Oxide nanoparticles from Drypetes sepiaria Leaf extract and their catalytic activity to dye degradation

    Science.gov (United States)

    Narasaiah, Palajonna; Mandal, Badal Kumar; Sarada, N. C.

    2017-11-01

    The synthesis of metal nanoparticles through a green method is a rapid biogenic and offers few advantages over the common chemical and physical procedures, as it is an easy and fast, eco-friendly and does not involve any costly chemicals as well as hazardous chemicals. In this study, we report synthesis of CuO NPs by using Drypetes sepiaria Leaf extract (DSLE). The synthesized CuO NPs was characterization using different technique such as UV, IR, XRD, and TEM. The formation of CuO NPs was confirmed by Surface Plasmon Resonance (SRP) at 298 nm using UV-Vis spectroscopy. Crystallinity of CuO NPs was confirmed by powder XRD and the characteristic functional groups of synthesised CuO NPs were identified by FTIR spectroscopy. The size and shape of the synthesized CuO NPs was determined by transmission electron microscopy (TEM). In addition, we performed photocatalytic activity to examine the photocatalytic degradation efficiency of CuO NPs to Congo Red. The colloidal solutions of CuO NPs showed good catalytic activity.

  9. Effect of the dispersants on Pd species and catalytic activity of supported palladium catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Hu, Yue [Key Laboratory for Green Chemical Process of Ministry of Education, School of Chemical Engineering and Pharmacy, Wuhan Institute of Technology, Wuhan 430205 (China); Yang, Xiaojun, E-mail: 10100201@wit.edu.cn [Key Laboratory for Green Chemical Process of Ministry of Education, School of Chemical Engineering and Pharmacy, Wuhan Institute of Technology, Wuhan 430205 (China); Cao, Shuo, E-mail: cao23@email.sc.edu [North America R& D Center, Clariant BU Catalysts, Louisville, 40209, KY (United States); Zhou, Jie [Key Laboratory for Green Chemical Process of Ministry of Education, School of Chemical Engineering and Pharmacy, Wuhan Institute of Technology, Wuhan 430205 (China); Wu, Yuanxin [Key Laboratory for Green Chemical Process of Ministry of Education, School of Chemical Engineering and Pharmacy, Wuhan Institute of Technology, Wuhan 430205 (China); School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072 (China); Han, Jinyu [School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072 (China); Yan, Zhiguo [Key Laboratory for Green Chemical Process of Ministry of Education, School of Chemical Engineering and Pharmacy, Wuhan Institute of Technology, Wuhan 430205 (China); Zheng, Mingming [Oil Crops Research Institute, Chinese Academy of Agricultural Sciences, Hubei Key Laboratory of Oilcrops Lipid Chemistry and Nutrition, Wuhan 430062 (China)

    2017-04-01

    Highlights: • Polyvinyl alcohol (PVA) inhibited the sintering and reduction of Pd nanoparticles. • Activity was improved for supported Pd catalysts with PVA modified method. • PVA modified method minimized the catalyst deactivation. • This work provides an insight of the regeneration strategies for Pd catalysts. - Abstract: A series of supported palladium catalysts has been prepared through the precipitation method and the reduction method, using polyvinyl alcohol (PVA) and polyvinylpyrrolidone (PVP) as dispersants. The effects of the dispersants on the properties of catalysts were evaluated and the catalytic performance of the new materials was investigated for the oxidative carbonylation of phenol to diphenyl carbonate (DPC). The catalysts as prepared were also characterized by the X-ray diffraction (XRD), transmission electron microscope (TEM), Brunner-Emmet-Teller (BET) measurements and X-ray photoelectron spectroscopy (XPS) techniques. The results show that the addition of the dispersants had no effect on the crystal phase of the catalysts. However, the dispersion of Pd particles was improved when the dispersants were used. Moreover, the particle sizes of Pd nanoparticles modified by PVA were smaller than those modified by PVP. The catalysts prepared using the dispersants gave better yields of DPC than the catalysts prepared without the dispersants. The highest yield of DPC was 17.9% with the PVA-Red catalyst. The characterization results for the used catalysts showed that the Pd species in the PVA-Red catalyst remained mostly divalent and the lattice oxygen species were consumed during the reaction, which could lead to the higher catalytic activity of the PVA-Red catalyst. The experimental results confirm that PVA effectively inhibited the sintering and reduction of active Pd species in the oxidative carbonylation of phenol.

  10. Producing carbon-based boundary films from catalytically active lubricant additives

    Science.gov (United States)

    Erdemir, Ali; Mane, Anil U.; Elam, Jeffrey W.; Ramirez, Giovanni; Eryilmaz, Osman

    2018-04-24

    A lubricant composition includes an oil including a plurality of long-chain hydrocarbon molecules. A quantity of a catalytically active metal-organic additive is mixed with the oil. The metal-organic additive is formulated to fragment the long-chain hydrocarbon molecules of the oil into at least one of dimers and trimers under the influence of at least one of a mechanical loading and a thermal loading. In some embodiments, the metal-organic additive includes a compound of formula II: ##STR00001## where: X is Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Rf, Db, Sg, Bh, Hs, Mt, Ds, Rg or Cn, and R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are alkyl or alkyl halide.

  11. Phoenix dactylifera L. leaf extract phytosynthesized gold nanoparticles; controlled synthesis and catalytic activity

    Science.gov (United States)

    Zayed, Mervat F.; Eisa, Wael H.

    2014-03-01

    A green synthesis route was reported to explore the reducing and capping potential of Phoenix dactylifera extract for the synthesis of gold nanoparticles. The processes of nucleation and growth of gold nanoparticles were followed by monitoring the absorption spectra during the reaction. The size and morphology of these nanoparticles was typically imaged using transmission electron microscopy (TEM). The particle size ranged between 32 and 45 nm and are spherical in shape. Fourier transform infrared (FTIR) analysis suggests that the synthesized gold nanoparticles might be stabilized through the interactions of hydroxyl and carbonyl groups in the carbohydrates, flavonoids, tannins and phenolic acids present in P. dactylifera. The as-synthesized Au colloids exhibited good catalytic activity for the degradation of 4-nitrophenol.

  12. New porphyrin-polyoxometalate hybrid materials: synthesis, characterization and investigation of catalytic activity in acetylation reactions.

    Science.gov (United States)

    Araghi, Mehdi; Mirkhani, Valiollah; Moghadam, Majid; Tangestaninejad, Shahram; Mohammdpoor-Baltork, Iraj

    2012-10-14

    New hybrid complexes based on covalent interaction between 5,10,15,20-tetrakis(4-aminophenyl)porphyrinatozinc(II) and 5,10,15,20-tetrakis(4-aminophenyl)porphyrinatotin(IV) chloride, and a Lindqvist-type polyoxometalate, Mo(6)O(19)(2-), were prepared. These new porphyrin-polyoxometalate hybrid materials were characterized by (1)H NMR, FT IR and UV-Vis spectroscopic methods and cyclic voltammetry. These spectro- and electrochemical studies provided several spectral data for synthesis of these compounds. Cyclic voltammetry showed the influence of the polyoxometalate on the redox process of the porphyrin ring. The catalytic activity of tin(IV)porphyrin-hexamolybdate hybrid material was investigated in the acetylation of alcohols and phenols with acetic anhydride. The reusability of this catalyst was also investigated.

  13. Shape-Controlled Synthesis of Palladium-Copper Nanoalloys with Improved Catalytic Activity for Ethanol Electrooxidation

    Directory of Open Access Journals (Sweden)

    Hao Wang

    2016-01-01

    Full Text Available A facile solvothermal strategy is developed for the preparation of nanometer sized Pd-Cu alloy. We can control the morphology of these alloys with the use of ethylene glycol (EG in the presence of KOH. Namely, by increasing the concentration of KOH/EG, the Pd-Cu alloys with different morphologies from near-spherical nanoparticles (NPs to nanorods and nanowire networks have been prepared. Among all these alloys, near-spherical Pd-Cu NPs-modified electrodes exhibit the highest catalytic activity (11.7 mA/cm2 and stability toward the electrooxidation of ethanol in comparison with commercial Pd/C-modified ones (2.1 mA/cm2.

  14. Stereoselective Catalytic Synthesis of Active Pharmaceutical Ingredients in Homemade 3D-Printed Mesoreactors.

    Science.gov (United States)

    Rossi, Sergio; Porta, Riccardo; Brenna, Davide; Puglisi, Alessandra; Benaglia, Maurizio

    2017-04-03

    3D-printed flow reactors were designed, fabricated from different materials (PLA, HIPS, nylon), and used for a catalytic stereoselective Henry reaction. The use of readily prepared and tunable 3D-printed reactors enabled the rapid screening of devices with different sizes, shapes, and channel dimensions, aimed at the identification of the best-performing reactor setup. The optimized process afforded the products in high yields, moderate diastereoselectivity, and up to 90 % ee. The method was applied to the continuous-flow synthesis of biologically active chiral 1,2-amino alcohols (norephedrine, metaraminol, and methoxamine) through a two-step sequence combining the nitroaldol reaction with a hydrogenation. To highlight potential industrial applications of this method, a multistep continuous synthesis of norephedrine has been realized. The product was isolated without any intermediate purifications or solvent switches. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Green synthesis of gold nanoparticles using aspartame and their catalytic activity for p-nitrophenol reduction

    Science.gov (United States)

    Wu, Shufen; Yan, Songjing; Qi, Wei; Huang, Renliang; Cui, Jing; Su, Rongxin; He, Zhimin

    2015-05-01

    We demonstrated a facile and environmental-friendly approach to form gold nanoparticles through the reduction of HAuCl4 by aspartame. The single-crystalline structure was illustrated by transmission electron microscopy (TEM) and X-ray diffraction (XRD). The energy-dispersive X-ray spectroscopy (EDS) and Fourier transform infrared (FTIR) results indicated that aspartame played a pivotal role in the reduction and stabilization of the gold crystals. The crystals were stabilized through the successive hydrogen-bonding network constructed between the water and aspartame molecules. Additionally, gold nanoparticles synthesized through aspartame were shown to have good catalytic activity for the reduction of p-nitrophenol to p-aminophenol in the presence of NaBH4.

  16. Synthesis of gold nanoparticles using renewable Punica granatum juice and study of its catalytic activity

    Science.gov (United States)

    Dash, Shib Shankar; Bag, Braja Gopal

    2014-01-01

    Punica granatum juice, a delicious multivitamin drink of great medicinal significance, is rich in different types of phytochemicals, such as terpenoids, alkaloids, sterols, polyphenols, sugars, fatty acids, aromatic compounds, amino acids, tocopherols, etc. We have demonstrated the use of the juice for the synthesis of gold nanoparticles (AuNPs) at room temperature under very mild conditions. The synthesis of the AuNPs was complete in few minutes and no extra stabilizing or capping agents were necessary. The size of the nanoparticles could be controlled by varying the concentration of the fruit extract. The AuNPs were characterized by surface plasmon resonance spectroscopy, high resolution transmission electron microscopy, fourier transform infrared spectroscopy and X-ray diffraction studies. Catalytic activity of the synthesized colloidal AuNPs has also been demonstrated.

  17. Crystal structure of a catalytically active, non-toxic endopeptidase derivative of Clostridium botulinum toxin A.

    Science.gov (United States)

    Masuyer, Geoffrey; Thiyagarajan, Nethaji; James, Peter L; Marks, Philip M H; Chaddock, John A; Acharya, K Ravi

    2009-03-27

    Botulinum neurotoxins (BoNTs) modulate cholinergic nerve terminals to result in neurotransmitter blockade. BoNTs consists of catalytic (LC), translocation (Hn) and cell-binding domains (Hc). The binding function of the Hc domain is essential for BoNTs to bind the neuronal cell membrane, therefore, removal of the Hc domain results in a product that retains the endopeptidase activity of the LC but is non-toxic. Thus, a molecule consisting of LC and Hn domains of BoNTs, termed LHn, is a suitable molecule for engineering novel therapeutics. The structure of LHA at 2.6 A reported here provides an understanding of the structural implications and challenges of engineering therapeutic molecules that combine functional properties of LHn of BoNTs with specific ligand partners to target different cell types.

  18. Light controllable catalytic activity of Au clusters decorated with photochromic molecules

    Science.gov (United States)

    Guo, Na; Meng Yam, Kah; Zhang, Chun

    2018-06-01

    By ab initio calculations, we show that when decorated with a photochromic molecule, the catalytic activity of an Au nanocluster can be reversibly controlled by light. The combination of a photochromic thiol-pentacarbonyl azobenzene (TPA) molecule and an Au8 cluster is chosen as a model catalyst. The TPA molecule has two configurations (trans and cis) that can be reversibly converted to each other upon photo-excitation. Our calculations show that when the TPA takes the trans configuration, the combined system (trans-Au8) is an excellent catalyst for CO oxidation. The reaction barrier of the catalyzed CO oxidation is less than 0.4 eV. While, the reaction barrier of CO oxidation catalyzed by cis-Au8 is very high (>2.7 eV), indicating that the catalyst is inactive. These results pave the way for a new class of light controllable nanoscale catalysts.

  19. Catalytic Activity of Sulfated and Phosphated Catalysts towards the Synthesis of Substituted Coumarin

    Directory of Open Access Journals (Sweden)

    Nagi R. E. Radwan

    2018-01-01

    Full Text Available New modified acidic catalysts were prepared from the treatment of silica, titania and silica prepared from hydrolyzed tetraethyl orthosilicate (TEOS with sulfuric and phosphoric acid. The sulfated and phosphated silica synthesized from TEOS were calcined at 450 and 650 °C. These catalysts were characterized by X-ray diffraction (XRD, Fourier-transform infrared spectroscopy (FTIR, transmission electron microscope (TEM, and scanning electron microscope (SEM. The surface areas, total pore volume, and mean pore radius of the acidic catalysts were investigated, while the pore size distribution was determined by the Barrett, Joyner and Halenda (BJH method. The catalytic activity of the sulfated and phosphated silica and/or titania were examined with the Pechmann condensation reaction, in which different phenols reacted with ethyl acetoacetate as a neat reaction to obtain the corresponding coumarin derivatives. The results indicated that the treatment of the catalysts with sulfuric or phosphoric acid led to a decrease in the phases’ crystallinity to a certain degree. The morphology and the structure of the acidified catalysts were examined and their particle size was calculated. Furthermore, the amount of the used catalysts played a vital role in controlling the formation of the products as well as their performance was manipulated by the number and nature of the active acidic sites on their surfaces. The obtained results suggested that the highest catalytic conversion of the reaction was attained at 20 wt % of the catalyst and no further increase in the product yield was detected when the amount of catalyst exceeded this value. Meanwhile the phenol molecules were a key feature in obtaining the final product.

  20. Catalytic Activities of Noble Metal Phosphides for Hydrogenation and Hydrodesulfurization Reactions

    Directory of Open Access Journals (Sweden)

    Yasuharu Kanda

    2018-04-01

    Full Text Available In this work, the development of a highly active noble metal phosphide (NMXPY-based hydrodesulfurization (HDS catalyst with a high hydrogenating ability for heavy oils was studied. NMXPY catalysts were obtained by reduction of P-added noble metals (NM-P, NM: Rh, Pd, Ru supported on SiO2. The order of activities for the hydrogenation of biphenyl was Rh-P > NiMoS > Pd-P > Ru-P. This order was almost the same as that of the catalytic activities for the HDS of dibenzothiophene. In the HDS of 4,6-dimethyldibenzothiophene (4,6-DMDBT, the HDS activity of the Rh-P catalyst increased with increasing reaction temperature, but the maximum HDS activity for the NiMoS catalyst was observed at 270 °C. The Rh-P catalyst yielded fully hydrogenated products with high selectivity compared with the NiMoS catalyst. Furthermore, XRD analysis of the spent Rh-P catalysts revealed that the Rh2P phase possessed high sulfur tolerance and resistance to sintering.

  1. 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.

  2. Modeling of catalytically active metal complex species and intermediates in reactions of organic halides electroreduction.

    Science.gov (United States)

    Lytvynenko, Anton S; Kolotilov, Sergey V; Kiskin, Mikhail A; Eremenko, Igor L; Novotortsev, Vladimir M

    2015-02-28

    The results of quantum chemical modeling of organic and metal-containing intermediates that occur in electrocatalytic dehalogenation reactions of organic chlorides are presented. Modeling of processes that take place in successive steps of the electrochemical reduction of representative C1 and C2 chlorides - CHCl3 and Freon R113 (1,1,2-trifluoro-1,2,2-trichloroethane) - was carried out by density functional theory (DFT) and second-order Møller-Plesset perturbation theory (MP2). It was found that taking solvation into account using an implicit solvent model (conductor-like screening model, COSMO) or considering explicit solvent molecules gave similar results. In addition to modeling of simple non-catalytic dehalogenation, processes with a number of complexes and their reduced forms, some of which were catalytically active, were investigated by DFT. Complexes M(L1)2 (M = Fe, Co, Ni, Cu, Zn, L1H = Schiff base from 2-pyridinecarbaldehyde and the hydrazide of 4-pyridinecarboxylic acid), Ni(L2) (H2L2 is the Schiff base from salicylaldehyde and 1,2-ethylenediamine, known as salen) and Co(L3)2Cl2, representing a fragment of a redox-active coordination polymer [Co(L3)Cl2]n (L3 is the dithioamide of 1,3-benzenedicarboxylic acid), were considered. Gradual changes in electronic structure in a series of compounds M(L1)2 were observed, and correlations between [M(L1)2](0) spin-up and spin-down LUMO energies and the relative energies of the corresponding high-spin and low-spin reduced forms, as well as the shape of the orbitals, were proposed. These results can be helpful for determination of the nature of redox-processes in similar systems by DFT. No specific covalent interactions between [M(L1)2](-) and the R113 molecule (M = Fe, Co, Ni, Zn) were found, which indicates that M(L1)2 electrocatalysts act rather like electron transfer mediators via outer-shell electron transfer. A relaxed surface scan of the adducts {M(L1)2·R113}(-) (M = Ni or Co) versus the distance between the

  3. COMPARISON OF CATALYTIC ACTIVITIES BOTH FOR SELECTIVE OXIDATION AND DECOMPOSITION OF AMMONIA OVER Fe/HZβ CATALYST

    Directory of Open Access Journals (Sweden)

    YELİZ ÇETİN

    2016-11-01

    Full Text Available Ammonia is one of the syngas contaminants that must be removed before using the syngas downstream applications. The most promising hot-gas clean-up techniques of ammonia are selective catalytic oxidation (SCO and catalytic decomposition. In this study, the catalytic activities over Zeolite Hβ supported iron catalyst (Fe/HZβ were compared both for the two catalytic routes. For SCO experiments; temperature (300-550 °C, O2 (2000-6000 ppmv and (0-10% H2 concentrations were investigated with the presence of 800 ppm NH3 in each of the final gas mixture. In the second route, catalytic ammonia decomposition experiments were carried out with H2 in balance N2 (0-30% containing 800 ppm NH3 at 700°C and 800°C. In the SCO, NH3 conversions were increased with increasing reaction temperatures with the absence of H2 in the reaction mixture. With 10% H2, it was shown that NH3 conversions increased with decreasing the reaction temperature. This was interpreted as the competing H2 and NH3 oxidations over the catalyst. On the other hand, in the catalytic decomposition, thermodynamic equilibrium conversion of almost 100% was attained at both 700 and 800 °C. Upon H2 addition, all conversions decreased. The decrease in conversion seemed to be linear with inlet hydrogen concentration. Hydrogen was seen to inhibit ammonia decomposition reaction. It was shown that Fe/HZβ catalyst is better to use for catalytic decomposition of NH3 in syngas rather than SCO of NH3 in spite of higher reaction temperatures needed in the decomposition reaction.

  4. Synthesis and characterization of magnetically recyclable Ag nanoparticles immobilized on Fe3O4@C nanospheres with catalytic activity

    International Nuclear Information System (INIS)

    Li, Wei-hong; Yue, Xiu-ping; Guo, Chang-sheng; Lv, Jia-pei; Liu, Si-si; Zhang, Yuan; Xu, Jian

    2015-01-01

    Highlights: • Ag-loaded Fe 3 O 4 @C nanospheres were synthesized by a facile method. • The Fe 3 O 4 encapsulated mesoporous carbon was decorated with 10 nm Ag nanocrystals. • The as-prepared Ag-Fe 3 O 4 @C nanocomposite showed excellent catalytic activity. • The nanocomposite had convenient magnetic separability. - Abstract: A novel approach for the synthesis of Ag-loaded Fe 3 O 4 @C nanospheres (Ag-Fe 3 O 4 @C) was successfully developed. The catalysts possessed a carbon-coated magnetic core and grew active silver nanoparticles on the outer shell using hydrazine monohydrate as the AgNO 3 reductant in ethanol. The morphology, inner structure, and magnetic properties of the as-prepared composites were studied with transmission electron microscopy (TEM), X-ray powder diffraction (XRD), fourier translation infrared spectroscopy (FT-IR), and vibrating sample magnetometer (VSM) techniques. Catalytic activity was investigated by degrading rhodamine B (RhB) in the designed experiment. The obtained products were monodispersed and bifunctional with high magnetization, as well as exhibited excellent catalytic activity toward organic dye with 98% of RhB conversion within 20 min in the presence of NaBH 4 . The product also exhibited convenient magnetic separability and maintained high catalytic activity after six cycle runs

  5. Cytochrome c oxidase loses catalytic activity and structural integrity during the aging process in Drosophila melanogaster

    Energy Technology Data Exchange (ETDEWEB)

    Ren, Jian-Ching; Rebrin, Igor [Department of Pharmacology and Pharmaceutical Sciences, University of Southern California, Los Angeles, CA 90033 (United States); Klichko, Vladimir; Orr, William C. [Department of Biological Sciences, Southern Methodist University, Dallas, TX 75275 (United States); Sohal, Rajindar S., E-mail: sohal@usc.edu [Department of Pharmacology and Pharmaceutical Sciences, University of Southern California, Los Angeles, CA 90033 (United States)

    2010-10-08

    Research highlights: {yields} Cytochrome c oxidase loses catalytic activity during the aging process. {yields} Abundance of seven nuclear-encoded subunits of cytochrome c oxidase decreased with age in Drosophila. {yields} Cytochrome c oxidase is specific intra-mitochondrial site of age-related deterioration. -- Abstract: The hypothesis, that structural deterioration of cytochrome c oxidase (CcO) is a causal factor in the age-related decline in mitochondrial respiratory activity and an increase in H{sub 2}O{sub 2} generation, was tested in Drosophila melanogaster. CcO activity and the levels of seven different nuclear DNA-encoded CcO subunits were determined at three different stages of adult life, namely, young-, middle-, and old-age. CcO activity declined progressively with age by 33%. Western blot analysis, using antibodies specific to Drosophila CcO subunits IV, Va, Vb, VIb, VIc, VIIc, and VIII, indicated that the abundance these polypeptides decreased, ranging from 11% to 40%, during aging. These and previous results suggest that CcO is a specific intra-mitochondrial site of age-related deterioration, which may have a broad impact on mitochondrial physiology.

  6. Cytochrome c oxidase loses catalytic activity and structural integrity during the aging process in Drosophila melanogaster

    International Nuclear Information System (INIS)

    Ren, Jian-Ching; Rebrin, Igor; Klichko, Vladimir; Orr, William C.; Sohal, Rajindar S.

    2010-01-01

    Research highlights: → Cytochrome c oxidase loses catalytic activity during the aging process. → Abundance of seven nuclear-encoded subunits of cytochrome c oxidase decreased with age in Drosophila. → Cytochrome c oxidase is specific intra-mitochondrial site of age-related deterioration. -- Abstract: The hypothesis, that structural deterioration of cytochrome c oxidase (CcO) is a causal factor in the age-related decline in mitochondrial respiratory activity and an increase in H 2 O 2 generation, was tested in Drosophila melanogaster. CcO activity and the levels of seven different nuclear DNA-encoded CcO subunits were determined at three different stages of adult life, namely, young-, middle-, and old-age. CcO activity declined progressively with age by 33%. Western blot analysis, using antibodies specific to Drosophila CcO subunits IV, Va, Vb, VIb, VIc, VIIc, and VIII, indicated that the abundance these polypeptides decreased, ranging from 11% to 40%, during aging. These and previous results suggest that CcO is a specific intra-mitochondrial site of age-related deterioration, which may have a broad impact on mitochondrial physiology.

  7. Enhancement of the catalytic activity of Pt nanoparticles toward methanol electro-oxidation using doped-SnO2 supporting materials

    Science.gov (United States)

    Merati, Zohreh; Basiri Parsa, Jalal

    2018-03-01

    Catalyst supports play important role in governing overall catalyst activity and durability. In this study metal oxides (SnO2, Sb and Nb doped SnO2) were electrochemically deposited on titanium substrate (Ti) as a new support material for Pt catalyst in order to electro-oxidation of methanol. Afterward platinum nanoparticles were deposited on metal oxide film via electro reduction of platinum salt in an acidic solution. The surface morphology of modified electrodes were evaluated by field-emission scanning electron microscopy (FESEM) and energy dispersive X-ray analysis (EDX) techniques. The electro-catalytic activities of prepared electrodes for methanol oxidation reaction (MOR) and oxidation of carbon monoxide (CO) absorbed on Pt was considered with cyclic voltammetry. The results showed high catalytic activity for Pt/Nb-SnO2/Ti electrode. The electrochemical surface area (ECSA) of a platinum electro-catalyst was determined by hydrogen adsorption. Pt/Nb-SnO2/Ti electrode has highest ECSA compared to other electrode resulting in high activity toward methanol electro-oxidation and CO stripping experiments. The doping of SnO2 with Sb and Nb improved ECSA and MOR activity, which act as electronic donors to increase electronic conductivity.

  8. Helicobacter Catalase Devoid of Catalytic Activity Protects the Bacterium against Oxidative Stress.

    Science.gov (United States)

    Benoit, Stéphane L; Maier, Robert J

    2016-11-04

    Catalase, a conserved and abundant enzyme found in all domains of life, dissipates the oxidant hydrogen peroxide (H 2 O 2 ). The gastric pathogen Helicobacter pylori undergoes host-mediated oxidant stress exposure, and its catalase contains oxidizable methionine (Met) residues. We hypothesized catalase may play a large stress-combating role independent of its classical catalytic one, namely quenching harmful oxidants through its recyclable Met residues, resulting in oxidant protection to the bacterium. Two Helicobacter mutant strains ( katA H56A and katA Y339A ) containing catalase without enzyme activity but that retain all Met residues were created. These strains were much more resistant to oxidants than a catalase-deletion mutant strain. The quenching ability of the altered versions was shown, whereby oxidant-stressed (HOCl-exposed) Helicobacter retained viability even upon extracellular addition of the inactive versions of catalase, in contrast to cells receiving HOCl alone. The importance of the methionine-mediated quenching to the pathogen residing in the oxidant-rich gastric mucus was studied. In contrast to a catalase-null strain, both site-change mutants proficiently colonized the murine gastric mucosa, suggesting that the amino acid composition-dependent oxidant-quenching role of catalase is more important than the well described H 2 O 2 -dissipating catalytic role. Over 100 years after the discovery of catalase, these findings reveal a new non-enzymatic protective mechanism of action for the ubiquitous enzyme. © 2016 by The American Society for Biochemistry and Molecular Biology, Inc.

  9. The N domain of somatic angiotensin-converting enzyme negatively regulates ectodomain shedding and catalytic activity.

    Science.gov (United States)

    Woodman, Zenda L; Schwager, Sylva L U; Redelinghuys, Pierre; Carmona, Adriana K; Ehlers, Mario R W; Sturrock, Edward D

    2005-08-01

    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 this, we constructed two mutants: CNdom-ACE and CCdom-ACE. CNdom-ACE was shed less efficiently than sACE, whereas CCdom-ACE was shed as efficiently as tACE. Notably, cleavage occurred both within the stalk and the interdomain bridge in both mutants, suggesting that a sheddase recognition motif resides within the C domain and is capable of directly cleaving at both positions. Analysis of the catalytic properties of the mutants and comparison with sACE and tACE revealed that the k(cat) for sACE and CNdom-ACE was less than or equal to the sum of the kcat values for tACE and the N-domain, suggesting negative co-operativity, whereas the kcat value for the CCdom-ACE suggested positive co-operativity between the two domains. Taken together, the results provide support for (i) the existence of a sheddase recognition motif in the C domain and (ii) molecular flexibility of the N and C domains in sACE, resulting in occlusion of the C-domain recognition motif by the N domain as well as close contact of the two domains during hydrolysis of peptide substrates.

  10. Agro-industrial waste-mediated synthesis and characterization of gold and silver nanoparticles and their catalytic activity for 4-nitroaniline hydrogenation

    Energy Technology Data Exchange (ETDEWEB)

    Dauthal, Preeti; Mukhopadhyay, Mausumi [S.V. National Institute of Technology, Surat (India)

    2015-05-15

    The biosynthesis of gold (Au-NPs) and silver nanoparticles (Ag-NPs) using agro-industrial waste Citrus aurantifolia peel extract as a bio-reducing agent is reported. Catalytic activity of nanoparticles (NPs) was evaluated for hydrogenation of anthropogenic pollutant 4-nitroaniline (4-NA). Both synthesized NPs were nearly spherical and distributed in size range of 6-46 and 10-32 nm for Au-NPs and Ag-NPs, respectively. XRD analysis revealed face centered cubic (fcc) structure of both NPs. ζ potential value obtained from colloidal solution of Au-NPs and Ag-NPs was −28.0 and −26.1mV, respectively, indicating the stability of the NPs in colloidal solution. FTIR spectra supported the role of citric and ascorbic acids of peel extract for biosynthesis and stabilization of NPs. The biosynthesized NPs exhibited excellent catalytic activity for hydrogenation of 4-NA in the presence of NaBH{sub 4}.

  11. Study of nitric oxide catalytic oxidation on manganese oxides-loaded activated carbon at low temperature

    Energy Technology Data Exchange (ETDEWEB)

    You, Fu-Tian [Key Laboratory of Urban Pollutant Conversion, Institute of Urban Environment, Chinese Academy of Sciences, Xiamen (China); University of Chinese Academy of Sciences, Beijing (China); Yu, Guang-Wei, E-mail: gwyu@iue.ac.cn [Key Laboratory of Urban Pollutant Conversion, Institute of Urban Environment, Chinese Academy of Sciences, Xiamen (China); Wang, Yin, E-mail: yinwang@iue.ac.cn [Key Laboratory of Urban Pollutant Conversion, Institute of Urban Environment, Chinese Academy of Sciences, Xiamen (China); Xing, Zhen-Jiao [Key Laboratory of Urban Pollutant Conversion, Institute of Urban Environment, Chinese Academy of Sciences, Xiamen (China); Liu, Xue-Jiao; Li, Jie [Key Laboratory of Urban Pollutant Conversion, Institute of Urban Environment, Chinese Academy of Sciences, Xiamen (China); University of Chinese Academy of Sciences, Beijing (China)

    2017-08-15

    Highlights: • Loading manganese oxides on activated carbon effectively promotes NO oxidation. • NO adsorption-desorption on activated carbon is fundamental to NO oxidation. • A high Mn{sup 4+}/Mn{sup 3+} ratio contributes to NO oxidation by promoting lattice O transfer. - Abstract: Nitric oxide (NO) is an air pollutant that is difficult to remove at low concentration and low temperature. Manganese oxides (MnO{sub x})-loaded activated carbon (MLAC) was prepared by a co-precipitation method and studied as a new catalyst for NO oxidation at low temperature. Characterization of MLAC included X-ray diffraction (XRD), scanning electron microscopy (SEM), N{sub 2} adsorption/desorption and X-ray photoelectron spectroscopy (XPS). Activity tests demonstrated the influence of the amount of MnO{sub x} and the test conditions on the reaction. MLAC with 7.5 wt.% MnO{sub x} (MLAC003) exhibits the highest NO conversion (38.7%) at 1000 ppm NO, 20 vol.% O{sub 2}, room temperature and GHSV ca. 16000 h{sup −1}. The NO conversion of MLAC003 was elevated by 26% compared with that of activated carbon. The results of the MLAC003 activity test under different test conditions demonstrated that NO conversion is also influenced by inlet NO concentration, inlet O{sub 2} concentration, reaction temperature and GHSV. The NO adsorption-desorption process in micropores of activated carbon is fundamental to NO oxidation, which can be controlled by pore structure and reaction temperature. The activity elevation caused by MnO{sub x} loading is assumed to be related to Mn{sup 4+}/Mn{sup 3+} ratio. Finally, a mechanism of NO catalytic oxidation on MLAC based on NO adsorption-desorption and MnO{sub x} lattice O transfer is proposed.

  12. Hydrophobic and hydrophilic nanosheet catalysts with high catalytic activity and recycling stability through control of the outermost ligand

    Science.gov (United States)

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

    2018-04-01

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

  13. Highly Oriented Growth of Catalytically Active Zeolite ZSM‐5 Films with a Broad Range of Si/Al Ratios

    OpenAIRE

    Fu, Donglong; Schmidt, Joel E.; Ristanović, Zoran; Chowdhury, Abhishek Dutta; Meirer, Florian; Weckhuysen, Bert M.

    2017-01-01

    Abstract Highly b‐oriented zeolite ZSM‐5 films are critical for applications in catalysis and separations and may serve as models to study diffusion and catalytic properties in single zeolite channels. However, the introduction of catalytically active Al3+ usually disrupts the orientation of zeolite films. Herein, using structure‐directing agents with hydroxy groups, we demonstrate a new method to prepare highly b‐oriented zeolite ZSM‐5 films with a broad range of Si/Al ratios (Si/Al=45 to ∞)...

  14. Enhanced activity and stability of copper oxide/γ-alumina catalyst in catalytic wet-air oxidation: Critical roles of cerium incorporation

    Science.gov (United States)

    Zhang, Yongli; Zhou, Yanbo; Peng, Chao; Shi, Junjun; Wang, Qingyu; He, Lingfeng; Shi, Liang

    2018-04-01

    By successive impregnation method, the Ce-modified Cu-O/γ-Al2O3 catalyst was prepared and characterized using nitrogen adsorption-desorption, scanning electron microscopy energy dispersive X-ray analysis (SEM-EDS), high-resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Raman, and H2-Temperature programming reduction (H2-TPR). In catalytic wet-air oxidation (CWAO) process for the printing and dyeing wastewater (PDW), the effects of Ce addition on performance, mechanism and kinetics of the catalyst were investigated. The Ce addition increases the Brunauer-Emmett-Teller (BET) surface area and pore volume of the catalyst and makes the active components uniformly distributed on the catalyst surface. Formation of a stable CuAl2O4 solid solution by anchoring Cu onto the γ-Al2O3 crystal lattice leads to a significant decrease in metal leaching of the Ce-modified catalyst. The proportion of lattice oxygen in the catalyst substantially increases and the apparent activation energy of Cu-O/γ-Al2O3 catalyst decreases owing to Ce addition. Therefore, the catalytic activity and stability of the Ce-modified catalyst are considerably improved. The scavengers experiments identify the active species existed in the CWAO reaction system, with the order of reactivity: h+ > O2•- > H2O2 > HO•. This novel Cu-Ce-O/γ-Al2O3 catalyst has great potential in applications for treatment of concentrated organic wastewater due to its superior catalytic activity and improved stability.

  15. Fabrication of catalytically active Au/Pt/Pd trimetallic nanoparticles by rapid injection of NaBH{sub 4}

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Haijun, E-mail: zhanghaijun@wust.edu.cn [College of Materials and Metallurgy, Wuhan University of Science and Technology, Wuhan, Hubei Province 430081 (China); State Key Laboratory Breeding Base of Refractories and Ceramics, Wuhan University of Science and Technology, Wuhan 430081 (China); Lu, Lilin [College of Chemical Engineering and Technology, Wuhan University of Science and Technology, Wuhan 430081 (China); Cao, Yingnan; Du, Shuang [College of Materials and Metallurgy, Wuhan University of Science and Technology, Wuhan, Hubei Province 430081 (China); State Key Laboratory Breeding Base of Refractories and Ceramics, Wuhan University of Science and Technology, Wuhan 430081 (China); Cheng, Zhong [College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072 (China); Zhang, Shaowei [State Key Laboratory Breeding Base of Refractories and Ceramics, Wuhan University of Science and Technology, Wuhan 430081 (China)

    2014-01-01

    Graphical abstract: The synthesis and characterization of 2.0 nm-diameter Au/Pt/Pd nanoparticles are reported. The catalytic activity for glucose oxidation of the nanoparticles is several times higher than that of Au nanoparticles with nearly same size. - Highlights: • PVP-protected Au/Pt/Pd trimetallic nanoparticles (TNPs) of 2.0 nm in diameter were prepared. • The catalytic activity of TNPs is several times higher than that of Au nanoparticles. • Negatively charged Au atoms in the TNPs were confirmed by DFT calculation. - Abstract: Au/Pt/Pd trimetallic nanoparticles (TNPs) with an alloyed structure and an average diameter of about 2.0 nm were prepared via reducing the corresponding ions with rapidly injected NaBH{sub 4}, and characterized by UV–vis, TEM and HR-TEM. The catalytic activity of as-prepared TNPs for the aerobic glucose oxidation is several times higher than that of Au monometallic nanoparticles with about the same average size, which could be attributed to the catalytically active sites provided by the negatively charged Au atoms as a result of the electron donation from the neighboring Pd atoms. This was well supported by the electron density calculations based on the density functional theory.

  16. Fabrication of catalytically active Au/Pt/Pd trimetallic nanoparticles by rapid injection of NaBH4

    International Nuclear Information System (INIS)

    Zhang, Haijun; Lu, Lilin; Cao, Yingnan; Du, Shuang; Cheng, Zhong; Zhang, Shaowei

    2014-01-01

    Graphical abstract: The synthesis and characterization of 2.0 nm-diameter Au/Pt/Pd nanoparticles are reported. The catalytic activity for glucose oxidation of the nanoparticles is several times higher than that of Au nanoparticles with nearly same size. - Highlights: • PVP-protected Au/Pt/Pd trimetallic nanoparticles (TNPs) of 2.0 nm in diameter were prepared. • The catalytic activity of TNPs is several times higher than that of Au nanoparticles. • Negatively charged Au atoms in the TNPs were confirmed by DFT calculation. - Abstract: Au/Pt/Pd trimetallic nanoparticles (TNPs) with an alloyed structure and an average diameter of about 2.0 nm were prepared via reducing the corresponding ions with rapidly injected NaBH 4 , and characterized by UV–vis, TEM and HR-TEM. The catalytic activity of as-prepared TNPs for the aerobic glucose oxidation is several times higher than that of Au monometallic nanoparticles with about the same average size, which could be attributed to the catalytically active sites provided by the negatively charged Au atoms as a result of the electron donation from the neighboring Pd atoms. This was well supported by the electron density calculations based on the density functional theory

  17. Catalytic properties of IgMs with amylolytic activity isolated from patients with multiple sclerosis.

    Science.gov (United States)

    Ivanen, Dina R; Kulminskaya, Anna A; Shabalin, Konstantin A; Isaeva-Ivanova, Luydmila V; Ershova, Nadezhda A; Saveliev, Andrew N; Nevinsky, Gregory A; Neustroev, Kirill N

    2004-08-01

    Recently, amylolytic activity was detected in IgMs isolated from the sera of the patients with multiple sclerosis. All purified samples of IgM were electrophoretically homogenous and did not contain any co-purified a-amylase and a-glucosidase activities, in accordance with a set of criteria developed for abzymes. The amylolytic activity of abzymes was studied in the hydrolysis of p-nitrophenyl a-D-maltooligosaccharides with different degrees of polymerization from 1 to 8 by TLC and reverse-phase HPLC techniques. All IgM samples isolated from 54 patients with clinically definite multiple sclerosis demonstrated hydrolytic activity towards the above artificial substrates. The Michaelis constant values (Km) in the hydrolysis of p-nitrophenyl a-D-maltoheptaoside were in the range of 10 p-nitrophenyl or p-nitrophenyl a-D-glucosides, thus indicating the presence of an a-D-glucosidase activity. For a number of the investigated samples, specific amylolytic activity increased depending on the length of substrates (from p-nitrophenyl maltopentaoside to p-nitrophenyl maltohexaoside); for other IgMs, the opposite dependence was observed. All IgMs studied did not exhibit any other glycoside hydrolase activities toward p-nitrophenyl glycoside substrates. Abzyme fractions from different donors demonstrated catalytic heterogeneity in Michaelis-Menten parameters and different modes of action in the hydrolysis of p-nitrophenyl maltooligosaccharides. Enzymatic properties of the IgMs tested varied from human a-amylases. All investigated abzyme samples did not show transglycosylating ability.

  18. Antitumour, antimicrobial and catalytic activity of gold nanoparticles synthesized by different pH propolis extracts

    Science.gov (United States)

    Gatea, Florentina; Teodor, Eugenia Dumitra; Seciu, Ana-Maria; Covaci, Ovidiu Ilie; Mănoiu, Sorin; Lazăr, Veronica; Radu, Gabriel Lucian

    2015-07-01

    The Romanian propolis was extracted in five different media, respectively, in water (pH 6.8), glycine buffer (pH 2.5), acetate buffer (pH 5), phosphate buffer (pH 7.4) and carbonate buffer (pH 9.2). The extracts presented different amounts of flavonoids and phenolic acids, increasing pH leading to higher concentrations of active compounds. Five variants of gold nanoparticles suspensions based on different pH Romanian propolis aqueous extracts were successfully synthesized. The obtained nanoparticles presented dimensions between 20 and 60 nm in dispersion form and around 18 nm in dried form, and different morphologies (spherical, hexagonal, triangular). Fourier transform infrared spectroscopy proved the attachment of organic compounds from propolis extracts to the colloidal gold suspensions and X-ray diffraction certified that the suspensions contain metallic gold. The obtained propolis gold nanoparticles do not exhibit any antibacterial or antifungal activity, but presented different catalytic activities and toxicity on tumour cells.

  19. Antitumour, antimicrobial and catalytic activity of gold nanoparticles synthesized by different pH propolis extracts

    Energy Technology Data Exchange (ETDEWEB)

    Gatea, Florentina; Teodor, Eugenia Dumitra, E-mail: eu-teodor@yahoo.com [National Institute for Biological Sciences, Centre of Bioanalysis (Romania); Seciu, Ana-Maria [National Institute for Biological Sciences, Cellular and Molecular Biology Department (Romania); Covaci, Ovidiu Ilie [SARA Pharm Solutions (Romania); Mănoiu, Sorin [National Institute for Biological Sciences, Cellular and Molecular Biology Department (Romania); Lazăr, Veronica [University of Bucharest, Faculty of Biology (Romania); Radu, Gabriel Lucian [University “Politehnica” Bucharest, Faculty of Applied Chemistry and Materials Science (Romania)

    2015-07-15

    The Romanian propolis was extracted in five different media, respectively, in water (pH 6.8), glycine buffer (pH 2.5), acetate buffer (pH 5), phosphate buffer (pH 7.4) and carbonate buffer (pH 9.2). The extracts presented different amounts of flavonoids and phenolic acids, increasing pH leading to higher concentrations of active compounds. Five variants of gold nanoparticles suspensions based on different pH Romanian propolis aqueous extracts were successfully synthesized. The obtained nanoparticles presented dimensions between 20 and 60 nm in dispersion form and around 18 nm in dried form, and different morphologies (spherical, hexagonal, triangular). Fourier transform infrared spectroscopy proved the attachment of organic compounds from propolis extracts to the colloidal gold suspensions and X-ray diffraction certified that the suspensions contain metallic gold. The obtained propolis gold nanoparticles do not exhibit any antibacterial or antifungal activity, but presented different catalytic activities and toxicity on tumour cells.

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

    Science.gov (United States)

    Hata, Tomoyuki; Ushiyama, Hiroshi; Yamashita, Koichi

    2013-03-01

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

  1. Catalytically-active inclusion bodies-Carrier-free protein immobilizates for application in biotechnology and biomedicine.

    Science.gov (United States)

    Krauss, Ulrich; Jäger, Vera D; Diener, Martin; Pohl, Martina; Jaeger, Karl-Erich

    2017-09-20

    Bacterial inclusion bodies (IBs) consist of unfolded protein aggregates and represent inactive waste products often accumulating during heterologous overexpression of recombinant genes in Escherichia coli. This general misconception has been challenged in recent years by the discovery that IBs, apart from misfolded polypeptides, can also contain substantial amounts of active and thus correctly or native-like folded protein. The corresponding catalytically-active inclusion bodies (CatIBs) can be regarded as a biologically-active sub-micrometer sized biomaterial or naturally-produced carrier-free protein immobilizate. Fusion of polypeptide (protein) tags can induce CatIB formation paving the way towards the wider application of CatIBs in synthetic chemistry, biocatalysis and biomedicine. In the present review we summarize the history of CatIBs, present the molecular-biological tools that are available to induce CatIB formation, and highlight potential lines of application. In the second part findings regarding the formation, architecture, and structure of (Cat)IBs are summarized. Finally, an overview is presented about the available bioinformatic tools that potentially allow for the prediction of aggregation and thus (Cat)IB formation. This review aims at demonstrating the potential of CatIBs for biotechnology and hopefully contributes to a wider acceptance of this promising, yet not widely utilized, protein preparation. Copyright © 2017 Elsevier B.V. All rights reserved.

  2. Modification of Colombian clays with pillars mixed Al-Fe and their evaluation in the catalytic oxidation of phenol in diluted watery solution

    International Nuclear Information System (INIS)

    Galeano, Luis A; Moreno G, Sonia

    2002-01-01

    The environmental legislation has become in the last time particularly restrictive with the bio-recalcitrant pollutants manage in the wastewaters. The pillared clays show great versatility to adjust at demands of the environmental reactions. Present study show that is achieve the modification of starting Colombian clays with precursor solutions of Al-Fe mixed pillars, and is found an excellent performance of them in the catalytic oxidation of aqueous solutions with middle contents of Total Organic Carbon TOC (36 mg C/L). The materials prepared in this way reached quantitative conversion of phenol, as model pollutant, in 2 hours of reaction at 20 Celsius degrade and atmospheric pressure; in 4 hours of reaction, the removal reached 62% of TOC in the solution yielding light carboxylic acids as main byproducts, although that CO 2 . The materials are stable under strongly oxidation media of reaction, and the iron leached in the effluent is close to 0,2 mg/L for the material of better catalytic performance

  3. Facile Fabrication of Highly Active Magnetic Aminoclay Supported Palladium Nanoparticles for the Room Temperature Catalytic Reduction of Nitrophenol and Nitroanilines

    Directory of Open Access Journals (Sweden)

    Lei Jia

    2018-06-01

    Full Text Available Magnetically recyclable nanocatalysts with excellent performance are urgent need in heterogeneous catalysis, due to their magnetic nature, which allows for convenient and efficient separation with the help of an external magnetic field. In this research, we developed a simple and rapid method to fabricate a magnetic aminoclay (AC based an AC@Fe3O4@Pd nanocatalyst by depositing palladium nanoparticles (Pd NPs on the surface of the magnetic aminoclay nanocomposite. The microstructure and the magnetic properties of as-prepared AC@Fe3O4@Pd were tested using transmission electron microscopy (TEM, energy-dispersive X-ray spectroscopy (EDS, X-ray diffraction (XRD, and vibrating sample magnetometry (VSM analyses. The resultant AC@Fe3O4@Pd nanocatalyst with the magnetic Fe-based inner shell, catalytically activate the outer noble metal shell, which when combined with ultrafine Pd NPs, synergistically enhanced the catalytic activity and recyclability in organocatalysis. As the aminoclay displayed good water dispersibility, the nanocatalyst indicated satisfactory catalytic performance in the reaction of reducing nitrophenol and nitroanilines to the corresponding aminobenzene derivatives. Meanwhile, the AC@Fe3O4@Pd nanocatalyst exhibited excellent reusability, while still maintaining good activity after several catalytic cycles.

  4. Intramolecularly Protein-Crosslinked DNA Gels: New Biohybrid Nanomaterials with Controllable Size and Catalytic Activity.

    Science.gov (United States)

    Zhou, Li; Morel, Mathieu; Rudiuk, Sergii; Baigl, Damien

    2017-07-01

    DNA micro- and nanogels-small-sized hydrogels made of a crosslinked DNA backbone-constitute new promising materials, but their functions have mainly been limited to those brought by DNA. Here a new way is described to prepare sub-micrometer-sized DNA gels of controllable crosslinking density that are able to embed novel functions, such as an enzymatic activity. It consists of using proteins, instead of traditional base-pairing assembly or covalent approaches, to form crosslinks inside individual DNA molecules, resulting in structures referred to as intramolecularly protein-crosslinked DNA gels (IPDGs). It is first shown that the addition of streptavidin to biotinylated T4DNA results in the successful formation of thermally stable IPDGs with a controllable crosslinking density, forming structures ranging from elongated to raspberry-shaped and pearl-necklace-like morphologies. Using reversible DNA condensation strategies, this paper shows that the gels can be reversibly actuated at a low crosslinking density, or further stabilized when they are highly crosslinked. Finally, by using streptavidin-protein conjugates, IPDGs with various enzymes are successfully functionalized. It is demonstrated that the enzymes keep their catalytic activity upon their incorporation into the gels, opening perspectives ranging from biotechnologies (e.g., enzyme manipulation) to nanomedicine (e.g., vectorization). © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Green synthesis of gold nanoparticles using Citrus maxima peel extract and their catalytic/antibacterial activities.

    Science.gov (United States)

    Yuan, Chun-Gang; Huo, Can; Gui, Bing; Cao, Wei-Ping

    2017-08-01

    The peel of Citrus maxima ( C. maxima ) is the primary byproducts during the process of fruit or juice in food industries, and it was always considered as biomass waste for further treatments. In this study, the authors reported a simple and eco-friendly method to synthesise gold nanoparticles (AuNPs) using C. maxima peel extract as reducing and capping agents. The synthesised AuNPs were characterised by UV-visible spectrum, X-ray diffraction (XRD), transmission electron microscope (TEM) and Fourier-transform infrared spectroscopy (FTIR). The UV-visible spectrum of the AuNPs colloid showed a characteristic peak at 540 nm. The peaks of XRD analysis at (2 θ ) 38.30°, 44.28°, 64.62°, 77.57° and 81.75° were assigned to (111), (200), (220), (311) and (222) planes of the face-centered cubic (fcc) lattice of gold. The TEM images showed that AuNPs were nearly spherical in shape with the size of 8-25 nm. The FTIR spectrum revealed that some bioactive compounds capped the surface of synthesised AuNPs. The biosynthesised AuNPs performed strong catalytic activity in degradation of 4-nitrophenol to 4-aminophenol and good antibacterial activity against both gram negative ( Escherichia coli ) and gram positive ( Staphylococcus aureus ) bacterium. The synthesis procedure was proved simple, cost effective and environment friendly.

  6. Controlled deposition of palladium nanodendrites on the tips of gold nanorods and their enhanced catalytic activity.

    Science.gov (United States)

    Su, Gaoxing; Jiang, Huaqiao; Zhu, Hongyan; Lv, Jing-Jing; Yang, Guohai; Yan, Bing; Zhu, Jun-Jie

    2017-08-31

    Plasmonic Au-Pd nanostructures have drawn significant attention for use in heterogeneous catalysis. In this study, palladium nanodendrite-tipped gold nanorods (PdND-T-AuNRs) were subjected to a facile fabrication under mild reaction conditions. The palladium amounts on the two tips were tunable. In the preparation of PdND-T-AuNRs, dense capped AuNRs, a low reaction temperature, and suitable stabilizing agents were identified as critical reaction parameters for controlling palladium nanodendrites deposited on both ends of AuNRs. After overgrowth with palladium nanodendrites, the longitudinal surface plasmonic resonance peaks of PdND-T-AuNRs were red-shifted from 810 nm to 980 nm. The electrocatalytic activity of PdND-T-AuNRs for ethanol oxidation was examined, which was a bit weaker than that of cuboid core-shell Au-Pd nanodendrites; however, PdND-T-AuNRs were more stable in ethanol electrooxidation. Moreover, the photocatalytic activity of PdND-T-AuNRs for Suzuki cross-coupling reactions was investigated. At room temperature, nearly 100% yield was obtained under laser irradiation. The results can further enhance our capability of fine-tuning the optical, electronic, and catalytic properties of the bimetallic Au-Pd nanostructures.

  7. Nanostructured Samarium Doped Fluorapatites and Their Catalytic Activity towards Synthesis of 1,2,4-Triazoles

    Directory of Open Access Journals (Sweden)

    Kranthi Kumar Gangu

    2016-09-01

    Full Text Available An investigation was conducted into the influence of the amino acids as organic modifiers in the facile synthesis of metal incorporated fluorapatites (FAp and their properties. The nanostructured Sm doped fluorapatites (Sm-FAp were prepared by a co-precipitation method using four different amino acids, namely glutamic acid, aspartic acid, glycine and histidine. The materials were characterized by various techniques including X-ray diffraction (XRD, Fourier transform infra-red spectroscopy (FT-IR, field emission scanning electron microscopy (FE-SEM, energy-dispersive X-ray spectroscopy (EDX, high resolution transmission electron microscopy (HR-TEM, N2-adsorption/desorption isotherm, temperature programmed desorption (TPD and fluorescence spectrophotometry. Under similar conditions, Sm-FAp prepared using different amino acids exhibited distinctly different morphological structures, surface area and pore properties. Their activity as catalysts was assessed and Sm-FAp/Glycine displayed excellent efficiency in the synthesis of 1,2,4-triazole catalyzing the reaction between 2-nitrobenzaldehyde and thiosemicarbazide with exceptional selectivity and 98% yield in a short time interval (10 min. The study provides an insight into the role of organic modifiers as controllers of nucleation, growth and aggregation which significantly influence the nature and activity of the catalytic sites on Sm-FAp. Sm-FAp could also have potential as photoactive material.

  8. Studies on bis(halogeno) dioxomolybdenum(VI)-bipyridine complexes: synthesis and catalytic activity.

    Science.gov (United States)

    Günyar, Alev; Zhou, Ming-Dong; Drees, Markus; Baxter, Paul N W; Bassioni, Ghada; Herdtweck, Eberhardt; Kühn, Fritz E

    2009-10-28

    Dioxomolybdenum(VI) complexes with the general formula [MoO2Cl2L2] (L2=3,3'-dimethyl-2,2'-bipyridine, 5,5'-dimethyl-2,2'-bipyridine, 6,6'-dimethyl-2,2'-bipyridine, 4,4'-dibromo-2,2'-bipyridine, 5,5'-dibromo-2,2'-bipyridine, 5,5'-diamino-2,2'-bipyridine; 5,5'-dinitro-2,2'-bipyridine; 5,5'-di-ethoxycarbonyl-2,2'-bipyridine; 6-phenyl-2,2'-bipyridine; 2,2':6',2''-terpyridine) have been prepared and characterised. [MoO2Cl2(5,5'-di-ethoxycarbonyl-2,2'-bipyridine)] has been examined by single crystal X-ray analysis. The complexes were applied as homogenous catalysts for the epoxidation of cyclooctene with tert-butyl hydroperoxide (TBHP) as oxidising agent. The new compounds show an overall high activity and are highly selective catalysts in the epoxidation of cyclooctene. The stability of the complexes and differences in the catalytic activity can be clearly attributed to electronic contributions of the functional groups on bipyridine ligands and to steric restrictions. DFT calculations have assisted in a better understanding of the stability of the complexes and are in agreement with experiment. The influence of the terminal oxo ligands and the Lewis base ligands on the Mo center keep the compounds on quite a stable level of electron density.

  9. Methodology to assay CYP2E1 mixed function oxidase catalytic activity and its induction

    Directory of Open Access Journals (Sweden)

    Arthur I. Cederbaum

    2014-01-01

    Full Text Available The cytochrome P450 mixed function oxidase enzymes are the major catalysts involved in drug metabolism. There are many forms of P450. CYP2E1 metabolizes many toxicologically important compounds including ethanol and is active in generating reactive oxygen species. Since several of the contributions in the common theme series “Role of CYP2E1 and Oxidative/Nitrosative Stress in the Hepatotoxic Actions of Alcohol” discuss CYP2E1, this methodology review describes assays on how CYP2E1 catalytic activity and its induction by ethanol and other inducers can be measured using substrate probes such as the oxidation of para-nitrophenol to para-nitrocatechol and the oxidation of ethanol to acetaldehyde. Approaches to validate that a particular reaction e.g. oxidation of a drug or toxin is catalyzed by CYP2E1 or that induction of that reaction is due to induction of CYP2E1 are important and specific examples using inhibitors of CYP2E1, anti-CYP2E1 IgG or CYP2E1 knockout and knockin mice will be discussed.

  10. Green synthesis of silver nanoparticles using Prosopis juliflora bark extract: reaction optimization, antimicrobial and catalytic activities.

    Science.gov (United States)

    Arya, Geeta; Kumari, R Mankamna; Gupta, Nidhi; Kumar, Ajeet; Chandra, Ramesh; Nimesh, Surendra

    2017-07-18

    In the present study, silver nanoparticles (PJB-AgNPs) have been biosynthesized employing Prosopis juliflora bark extract. The biosynthesis of silver nanoparticles was monitored on UV-vis spectrophotometer. The size, charge and polydispersity index (PDI) of PJB-AgNPs were determined using dynamic light scattering (DLS). Different parameters dictating the size of PJB-AgNPs were explored. Nanoparticles biosynthesis optimization studies suggested efficient synthesis of highly dispersed PJB-AgNPs at 25 °C when 9.5 ml of 1 mM AgNO 3 was reduced with 0.5 ml of bark extract for 40 min. Characterization of PJB-AgNPs by SEM showed spherical-shaped nanoparticles with a size range ∼10-50 nm along with a hydrodynamic diameter of ∼55 nm as evaluated by DLS. Further, characterizations were done by FTIR and EDS to evaluate the functional groups and purity of PJB-AgNPs. The antibacterial potential of PJB-AgNPs was tested against E. coli and P. aeruginosa. The PJB-AgNPs remarkably exhibited anticancer activity against A549 cell line as evidenced by Alamar blue assay. The dye degradation activity was also evaluated against 4-nitrophenol that has carcinogenic effect. The results thus obtained suggest application of PJB-AgNPs as antimicrobial, anticancer and catalytic agents.

  11. The minimum activation peptide from ilvH can activate the catalytic subunit of AHAS from different species.

    Science.gov (United States)

    Zhao, Yuefang; Niu, Congwei; Wen, Xin; Xi, Zhen

    2013-04-15

    Acetohydroxyacid synthases (AHASs), which catalyze the first step in the biosynthesis of branched-chain amino acids, are composed of a catalytic subunit (CSU) and a regulatory subunit (RSU). The CSU harbors the catalytic site, and the RSU is responsible for the activation and feedback regulation of the CSU. Previous results from Chipman and co-workers and our lab have shown that heterologous activation can be achieved among isozymes of Escherichia coli AHAS. It would be interesting to find the minimum peptide of ilvH (the RSU of E. coli AHAS III) that could activate other E. coli CSUs, or even those of ## species. In this paper, C-terminal, N-terminal, and C- and N-terminal truncation mutants of ilvH were constructed. The minimum peptide to activate ilvI (the CSU of E. coli AHAS III) was found to be ΔN 14-ΔC 89. Moreover, this peptide could not only activate its homologous ilvI and heterologous ilvB (CSU of E. coli AHAS I), but also heterologously activate the CSUs of AHAS from Saccharomyces cerevisiae, Arabidopsis thaliana, and Nicotiana plumbaginifolia. However, this peptide totally lost its ability for feedback regulation by valine, thus suggesting different elements for enzymatic activation and feedback regulation. Additionally, the apparent dissociation constant (Kd ) of ΔN 14-ΔC 89 when binding CSUs of different species was found to be 9.3-66.5 μM by using microscale thermophoresis. The ability of this peptide to activate different CSUs does not correlate well with its binding ability (Kd ) to these CSUs, thus implying that key interactions by specific residues is more important than binding ability in promoting enzymatic reactions. The high sequence similarity of the peptide ΔN 14-ΔC 89 to RSUs across species hints that this peptide represents the minimum activation motif in RSU and that it regulates all AHASs. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Size and Site Dependence of the Catalytic Activity of Iridium Clusters toward Ethane Dehydrogenation.

    Science.gov (United States)

    Ge, Yingbin; Jiang, Hao; Kato, Russell; Gummagatta, Prasuna

    2016-12-01

    This research focuses on optimizing transition metal nanocatalyst immobilization and activity to enhance ethane dehydrogenation. Ethane dehydrogenation, catalyzed by thermally stable Ir n (n = 8, 12, 18) atomic clusters that exhibit a cuboid structure, was studied using the B3LYP method with triple-ζ basis sets. Relativistic effects and dispersion corrections were included in the calculations. In the dehydrogenation reaction Ir n + C 2 H 6 → H-Ir n -C 2 H 5 → (H) 2 -Ir n -C 2 H 4 , the first H-elimination is the rate-limiting step, primarily because the reaction releases sufficient heat to facilitate the second H-elimination. The catalytic activity of the Ir clusters strongly depends on the Ir cluster size and the specific catalytic site. Cubic Ir 8 is the least reactive toward H-elimination in ethane: Ir 8 + C 2 H 6 → H-Ir 8 -C 2 H 5 has a large (65 kJ/mol) energy barrier, whereas Ir 12 (3 × 2 × 2 cuboid) and Ir 18 (3 × 3 × 2 cuboid) lower this energy barrier to 22 and 3 kJ/mol, respectively. The site dependence is as prominent as the size effect. For example, the energy barrier for the Ir 18 + C 2 H 6 → H-Ir 18 -C 2 H 5 reaction is 3, 48, and 71 kJ/mol at the corner, edge, or face-center sites of the Ir 18 cuboid, respectively. Energy release due to Ir cluster insertion into an ethane C-H bond facilitates hydrogen migration on the Ir cluster surface, and the second H-elimination of ethane. In an oxygen-rich environment, oxygen molecules may be absorbed on the Ir cluster surface. The oxygen atoms bonded to the Ir cluster surface may slightly increase the energy barrier for H-elimination in ethane. However, the adsorption of oxygen and its reaction with H atoms on the Ir cluster releases sufficient heat to yield an overall thermodynamically favored reaction: Ir n + C 2 H 6 + 1 / 2 O 2 → Ir n + C 2 H 4 + H 2 O. These results will be useful toward reducing the energy cost of ethane dehydrogenation in industry.

  13. 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.

  14. An isozyme of acid alpha-glucosidase with reduced catalytic activity for glycogen.

    Science.gov (United States)

    Beratis, N G; LaBadie, G U; Hirschhorn, K

    1980-03-01

    Both the common and a variant isozyme of acid alpha-glucosidase have been purified from a heterozygous placenta with CM-Sephadex, ammonium sulfate precipitation, dialysis, Amicon filtration, affinity chromatography by Sephadex G-100, and DEAE-cellulose chromatography. Three and two activity peaks, from the common and variant isozymes, respectively, were obtained by DEAE-cellulose chromatography using a linear NaCl gradient. The three peaks of activity of the common isozyme were eluted with 0.08, 0.12, and 0.17 M NaCl, whereas the two peaks of the variant, with 0.01 and 0.06 M NaCl. The pH optimum and thermal denaturation at 57 degrees C were the same in all enzyme peaks of both isozymes. Rabbit antiacid alpha-glucosidase antibodies produced against the common isozyme were found to cross-react with both peaks of the variant isozyme. The two isozymes shared antigenic identity and had similar Km's with maltose as substrate. Normal substrate saturation kinetics were observed with the common isozyme when glycogen was the substrate, but the variant produced an S-shaped saturation curve indicating a phase of negative and positive cooperativity at low and high glycogen concentrations, respectively. The activity of the variant was only 8.6% and 19.2% of the common isozyme when assayed with nonsaturating and saturating concentrations of glycogen, respectively. A similar rate of hydrolysis of isomaltose by both isozymes was found indicating that the reduced catalytic activity of the variant isozyme toward glycogen is not the result of a reduced ability of this enzyme to cleave the alpha-1,6 linkages of glycogen.

  15. Oxidation of winery wastewater by sulphate radicals: catalytic and solar photocatalytic activations.

    Science.gov (United States)

    Rodríguez-Chueca, Jorge; Amor, Carlos; Mota, Joana; Lucas, Marco S; Peres, José A

    2017-10-01

    The treatment of winery effluents through sulphate radical-based advanced oxidation processes (SR-AOPs) driven by solar radiation is reported in this study. Photolytic and catalytic activations of peroxymonosulphate (PMS) and persulphate (KPS and SPS) at different pH values (4.5 and 7) were studied in the degradation of organic matter. Portugal is one of the largest wine producers in Europe. The wine making activities generate huge volume of effluents characterized by a variable volume and organic load, being their seasonal nature one of the most important drawbacks. Recently, SR-AOPs are gradually attracting attention as in situ chemical oxidation technologies, instead of hydroxyl radical AOPs (HR-AOPs). The studied concentrations are suitable to obtain notable values of organic matter degradation, with TOC removal around 50%. In general terms, no notable differences were observed between treatments at pH values 4.5 and 7. Photolytic activation of SPS with solar radiation treatments obtained the highest efficiency (28 and 40% of TOC removal with 1 and 50 mM, respectively, at pH 4.5) in comparison to KPS and PMS. The addition of a transition metal as catalyst, such as Fe(II) or Co(II), increased considerably the TOC removal efficiency higher than 50%, but not in all cases. For instance, the combination KPS or PMS with Co(II) at pH 4.5 did not allow to obtain better results than photolytic activation of these persulphate salts. In summary, the use of SR-AOPs could be a serious alternative as tertiary treatment for winery wastewaters.

  16. Maternal high fat diet alters skeletal muscle mitochondrial catalytic activity in adult male rat offspring.

    Directory of Open Access Journals (Sweden)

    Chantal Anne Pileggi

    2016-11-01

    Full Text Available A maternal high-fat (HF diet during pregnancy can lead to metabolic compromise such as insulin resistance in adult offspring. Skeletal muscle mitochondrial dysfunction is one mechanism contributing to metabolic impairments in insulin resistant states. Therefore, the present study aimed to investigate whether mitochondrial dysfunction is evident in metabolically compromised offspring born to HF-fed dams. Sprague-Dawley dams were randomly assigned to receive a purified control diet (CD; 10% kcal from fat or a high fat diet (HFD; 45% kcal from fat for 10 days prior to mating, throughout pregnancy and during lactation. From weaning, all male offspring received a standard chow diet and soleus muscle was collected at day 150. Expression of the mitochondrial transcription factors nuclear respiratory factor-1 (NRF1 and mitochondrial transcription factor A (mtTFA were downregulated in HF offspring. Furthermore, genes encoding the mitochondrial electron transport system (ETS respiratory complex subunits were supressed in HF offspring. Moreover, protein expression of the complex I subunit, NDUFB8, was downregulated in HF offspring (36%, which was paralleled by decreased maximal catalytic linked activity of complex I and III (40%. Together, these results indicate that exposure to a maternal HF diet during development may elicit lifelong mitochondrial alterations in offspring skeletal muscle.

  17. Effective treatment of oily scum via catalytic wet persulfate oxidation process activated by Fe2.

    Science.gov (United States)

    Yuan, Xingzhong; Guan, Renpeng; Wu, Zhibin; Jiang, Longbo; Li, Yifu; Chen, Xiaohong; Zeng, Guangming

    2018-04-05

    Oily scum, a hazardous by-product of petroleum industry, need to be deposed urgently to reduce environmental risks. This paper introduces catalytic wet persulfate oxidation (CWPO) process in the treatment of oily scum to realize risk relief. Under the activation of heat and Fe 2+ , persulfate (PS) was decomposed into sulfate radicals and hydroxyl radicals, which played a major role on the degradation of petroleum hydrocarbons. The effects of wet air oxidation (WAO) and CWPO process on the degradation of oily scum were compared. In CWPO process, the total petroleum hydrocarbons (TPHs) content of oily scum was decreased from 92.63% to 16.75%, which was still up to 70.19% in WAO process. The degradation rate of TPHs in CWPO process was about 3.38 times higher than that in WAO process. The great performance of CWPO process was also confirmed by elemental analysis, which indicated that the C and H contents of oily scum were reduced significantly by CWPO process. These results indicated that CWPO process has high potential on the degradation of oily scum for environmental protection. Copyright © 2018 Elsevier Ltd. All rights reserved.

  18. One pot synthesis of copper nanoparticles at room temperature and its catalytic activity

    Directory of Open Access Journals (Sweden)

    Nikhil V. Suramwar

    2016-11-01

    Full Text Available A facile reduction approach with sodium borohydride as a reducing agent and starch as a stabilizing agent leads to monodispersed Cu nanoparticles in aqueous medium at an ambient condition. The synthesized nanoparticles are highly pure with no traces of CuO found on surface. They are uniform in size in the range of 40–80 nm. The Cu nanoparticles have a FCC structure as characterized by powder X-ray diffraction (XRD. Transmission electron microscopy (TEM images show that they are arranged in a regular array which is separated by starch thin layer which controls the growth as well as stabilizes the Cu nanoparticles from air oxidation. The catalytic activity of prepared Cu nanomaterial was tested in Ullman reaction for the synthesis of biphenyl from iodobenzene. We have shown in this paper that the size as well as exposed surface area of the copper nanoparticles is responsible for the increase in yield of biphenyl up to 92%. This is higher compare to the 40% yield with the normal size copper powder under the same reaction condition.

  19. Microfluidic system for enzymeless electrochemical determination of inulin using catalytically active metal nanowires

    International Nuclear Information System (INIS)

    García, Miguel; García -Carmona, Laura; Escarpa, Alberto

    2015-01-01

    We report on a microfluidic system for the electrochemical determination of inulin. It is making use of electro-synthesized catalytically active nanowires (NWs; made from nickel or copper; 6 μm long and 300 nm wide) capable of detecting inulin at a working voltage of +0.70 V (vs. Ag/AgCl) and a pH value of 12.0 with a sensitivity that is 40 times better than that for fructose (its monomer). The copper nanoelectrodes were characterized by field emission scanning electron microscopy and photoelectron spectroscopy which revealed a random distribution of copper NWs. Their core is found to be metallic while the outer few atomic layers (<2 nm) are oxidized (CuO). Both the intra-electrode repeatability (with RSDs of <8 % for 5 samples) and the inter-electrode reproducibility (RSDs <9 %; n =4) are very good. The approach presented here allows for a direct determination of both inulin and free fructose within <300 s with a LOD of 3 μM for inulin. Inulin was determined with recoveries ranging from 97 to 103 % (with RSDs of <4 %). This approach is perceived to represent an alternative to enzymatic assays or HPLC based approaches. It has the additional advantages of rapidity and low sample and reagent consumption. Given the electrochemical behavior of inulin, the results also suggest that this method will pave novel avenues towards the detection of complex carbohydrates. (author)

  20. Effects of a TiC substrate on the catalytic activity of Pt for NO reduction.

    Science.gov (United States)

    Chu, Xingli; Fu, Zhaoming; Li, Shasha; Zhang, Xilin; Yang, Zongxian

    2016-05-11

    Density functional theory calculations are used to elucidate the catalytic properties of a Pt monolayer supported on a TiC(001) substrate (Pt/TiC) toward NO reduction. It is found that the compound system of Pt/TiC has a good stability due to the strong Pt-TiC interaction. The diverse dissociation paths (namely the direct dissociation mechanism and the dimeric mechanism) are investigated. The transition state searching calculations suggest that NO has strong diffusion ability and small activation energy for dissociation on the Pt/TiC. For NO reduction on the Pt/TiC surface, we have found that the direct dissociation mechanisms (NO + N + O → NO2 + N and NO + N + O → N2 + O + O) are easier with a smaller dissociation barrier than those on the Pt(111) surface; and the dimeric process (NO + NO → (NO)2 → N2O + O → N2 + O + O) is considered to be dominant or significant with even a lower energy barrier than that of the direct dissociation. The results show that Pt/TiC can serve as an efficient catalyst for NO reduction.

  1. Synthesis and catalytic activity of N-heterocyclic silylene (NHSi) cobalt hydride for Kumada coupling reactions.

    Science.gov (United States)

    Qi, Xinghao; Sun, Hongjian; Li, Xiaoyan; Fuhr, Olaf; Fenske, Dieter

    2018-02-20

    The electron-rich silylene Co(i) chloride 5 was obtained through the reaction of CoCl(PMe 3 ) 3 with chlorosilylene. Complex 5 reacted with 1,3-siladiazole HSiMe(NCH 2 PPh 2 ) 2 C 6 H 4 to give the silylene Co(iii) hydride 6 through chelate-assisted Si-H activation. To the best of our knowledge, complex 6 is the first example of Co(iii) hydride supported by N-heterocyclic silylene. Complexes 5 and 6 were fully characterized by spectroscopic methods and X-ray diffraction analysis. Complex 6 was used as an efficient precatalyst for Kumada cross-coupling reactions. Compared with the related complex 3 supported by only trimethylphosphine, complex 6 as a catalyst supported by both chlorosilylene and trimethylphosphine exhibits a more efficient performance for the Kumada cross-coupling reactions. A novel catalytic radical mechanism was suggested and experimentally verified. As an intermediate silylene cobalt(ii) chloride 6d was isolated and structurally characterized.

  2. DNA/RNA hybrid substrates modulate the catalytic activity of purified AID.

    Science.gov (United States)

    Abdouni, Hala S; King, Justin J; Ghorbani, Atefeh; Fifield, Heather; Berghuis, Lesley; Larijani, Mani

    2018-01-01

    Activation-induced cytidine deaminase (AID) converts cytidine to uridine at Immunoglobulin (Ig) loci, initiating somatic hypermutation and class switching of antibodies. In vitro, AID acts on single stranded DNA (ssDNA), but neither double-stranded DNA (dsDNA) oligonucleotides nor RNA, and it is believed that transcription is the in vivo generator of ssDNA targeted by AID. It is also known that the Ig loci, particularly the switch (S) regions targeted by AID are rich in transcription-generated DNA/RNA hybrids. Here, we examined the binding and catalytic behavior of purified AID on DNA/RNA hybrid substrates bearing either random sequences or GC-rich sequences simulating Ig S regions. If substrates were made up of a random sequence, AID preferred substrates composed entirely of DNA over DNA/RNA hybrids. In contrast, if substrates were composed of S region sequences, AID preferred to mutate DNA/RNA hybrids over substrates composed entirely of DNA. Accordingly, AID exhibited a significantly higher affinity for binding DNA/RNA hybrid substrates composed specifically of S region sequences, than any other substrates composed of DNA. Thus, in the absence of any other cellular processes or factors, AID itself favors binding and mutating DNA/RNA hybrids composed of S region sequences. AID:DNA/RNA complex formation and supporting mutational analyses suggest that recognition of DNA/RNA hybrids is an inherent structural property of AID. Copyright © 2017 Elsevier Ltd. All rights reserved.

  3. The influence of a new fabrication procedure on the catalytic activity of ruthenium-selenium catalysts

    International Nuclear Information System (INIS)

    Cheng, H.; Yuan, W.; Scott, K.

    2006-01-01

    A new procedure has been introduced to enhance catalytic activity of ruthenium-selenium electro-catalysts for oxygen reduction, in which materials are treated under hydrogen atmosphere at elevated temperatures. The characterisation using scanning electron microscopy, energy dispersive spectroscopy or energy dispersive X-ray spectroscopy exhibited that the treatment at 400 deg. C made catalysts denser while their porous nature remained, led to a good degree of crystallinity and an optimum Se:Ru ratio. The half cell test confirms feasibility of the new procedure; the catalyst treated at 400 deg. C gave the highest reduction current (55.9 mA cm -2 at -0.4 V) and a low methanol oxidation effect coefficient (3.8%). The direct methanol fuel cell with the RuSe 400 deg. C cathode catalyst (2 mg RuSe cm -2 ) generated a power density of 33.8 mW cm -2 using 2 M methanol and 2 bar oxygen at 90 deg. C. The new procedure produced the catalysts with low decay rates. The best sample was compared to the Pt and to the reported ruthenium-selenium catalyst. Possible reasons for the observations are discussed

  4. Synthesis and catalytic activity of Birnessite-Type Manganese Oxide synthesized by solvent-free method

    Science.gov (United States)

    Siregar, S. S.; Awaluddin, A.

    2018-04-01

    Redox reaction between KMnO4 and glucose usingsolvent-free method produces the octahedral layer birnessite-type manganese oxide. The effects of mole ratios, temperatures, and calcinations time on the structures and crystallinity of the oxides were studied throughthe X-ray powder diffraction analysis. The mole ratio of KMnO4/glucose (1:3) produces the purebirnessite with low crystallinity, whereas the mole ratio of KMnO4/glucose (3:1) yields high crystalline birnessite with minor components of hausmannite-type manganese oxide.The increasing of the temperature and calcinations times (300-700 °C and 3-7 h, respectively) willimprove the crystallinity and the purity of the as-synthesized oxide. Further experiments also showed that the as-syntesized octahedral layer birnessite-type manganese oxides have catalytic activity on the degradation of methylene blue (MB) dye with H2O2 as oxidant. The results revealed that the effective degradation could be achieved only in the presence of both the birnessite and H2O2, whereas without the addition of catalyst (H2O2only) or addition of H2O2 (catalyst only), the 3.5% and 15.5% of MB removal were obtained, respectively.

  5. Green Adeptness in the Synthesis and Stabilization of Copper Nanoparticles: Catalytic, Antibacterial, Cytotoxicity, and Antioxidant Activities

    Science.gov (United States)

    Din, Muhammad Imran; Arshad, Farhan; Hussain, Zaib; Mukhtar, Maria

    2017-12-01

    Copper nanoparticles (CuNPs) are of great interest due to their extraordinary properties such as high surface-to-volume ratio, high yield strength, ductility, hardness, flexibility, and rigidity. CuNPs show catalytic, antibacterial, antioxidant, and antifungal activities along with cytotoxicity and anticancer properties in many different applications. Many physical and chemical methods have been used to synthesize nanoparticles including laser ablation, microwave-assisted process, sol-gel, co-precipitation, pulsed wire discharge, vacuum vapor deposition, high-energy irradiation, lithography, mechanical milling, photochemical reduction, electrochemistry, electrospray synthesis, hydrothermal reaction, microemulsion, and chemical reduction. Phytosynthesis of nanoparticles has been suggested as a valuable alternative to physical and chemical methods due to low cytotoxicity, economic prospects, environment-friendly, enhanced biocompatibility, and high antioxidant and antimicrobial activities. The review explains characterization techniques, their main role, limitations, and sensitivity used in the preparation of CuNPs. An overview of techniques used in the synthesis of CuNPs, synthesis procedure, reaction parameters which affect the properties of synthesized CuNPs, and a screening analysis which is used to identify phytochemicals in different plants is presented from the recent published literature which has been reviewed and summarized. Hypothetical mechanisms of reduction of the copper ion by quercetin, stabilization of copper nanoparticles by santin, antimicrobial activity, and reduction of 4-nitrophenol with diagrammatic illustrations are given. The main purpose of this review was to summarize the data of plants used for the synthesis of CuNPs and open a new pathway for researchers to investigate those plants which have not been used in the past.

  6. Role of the NC-loop in catalytic activity and stability in lipase from Fervidobacterium changbaicum.

    Directory of Open Access Journals (Sweden)

    Binchun Li

    Full Text Available Flexible NC-loops between the catalytic domain and the cap domain of the α/β hydrolase fold enzymes show remarkable diversity in length, sequence, and configuration. Recent investigations have suggested that the NC-loop might be involved in catalysis and substrate recognition in many enzymes from the α/β hydrolase fold superfamily. To foster a deep understanding of its role in catalysis, stability, and divergent evolution, we here systemically investigated the function of the NC-loop (residues 131-151 in a lipase (FClip1 from thermophilic bacterium Fervidobacterium changbaicum by loop deletion, alanine-scanning mutagenesis and site-directed mutagenesis. We found that the upper part of the NC-loop (residues 131-138 was of great importance to enzyme catalysis. Single substitutions in this region could fine-tune the activity of FClip1 as much as 41-fold, and any deletions from this region rendered the enzyme completely inactive. The lower part of the NC-loop (residues 139-151 was capable of enduring extensive deletions without loss of activity. The shortened mutants in this region were found to show both improved activity and increased stability simultaneously. We therefore speculated that the NC-loop, especially the lower part, would be a perfect target for enzyme engineering to optimize the enzymatic properties, and might present a hot zone for the divergent evolution of α/β hydrolases. Our findings may provide an opportunity for better understanding of the mechanism of divergent evolution in the α/β hydrolase fold superfamily, and may also guide the design of novel biocatalysts for industrial applications.

  7. Understanding Catalytic Activity Trends for NO Decomposition and CO Oxidation using Density Functional Theory and Microkinetic Modeling

    DEFF Research Database (Denmark)

    Falsig, Hanne

    -metal surfaces by combining a database of adsorption energies on stepped metal surfaces with known Brønsted–Evans–Polanyi (BEP) relations for the activation barriers of dissociation of diatomic molecules over stepped transition- and noble-metal surfaces. The potential energy diagram directly points to why Pd......The main aim of this thesis is to understand the catalytic activity of transition metals and noble metals for the direct decomposition of NO and the oxidation of CO. The formation of NOx from combustion of fossil and renewable fuels continues to be a dominant environmental issue. We take one step...... towards rationalizing trends in catalytic activity of transition metal catalysts for NO decomposition by combining microkinetic modelling with density functional theory calculations. We establish the full potential energy diagram for the direct NO decomposition reaction over stepped transition...

  8. Large stability and high catalytic activities of sub-nm metal (0) clusters: implications into the nucleation and growth theory.

    Science.gov (United States)

    Piñeiro, Yolanda; Buceta, David; Calvo, Javier; Huseyinova, Shahana; Cuerva, Miguel; Pérez, Ángel; Domínguez, Blanca; López-Quintela, M Arturo

    2015-07-01

    Clusters are stable catalytic species, which are produced during the synthesis of nanoparticles (NPs). Their existence contradicts the thermodynamic principles used to explain the formation of NPs by the classical nucleation and growth theories (NGTs). Using chemical and electrochemical methods we will show that depending on the experimental conditions one can produce either Ag clusters or Ag NPs. Moreover, using already prepared Ag clusters one can observe the disappearance of the usual induction period observed for the kinetics of NP formation, indicating that clusters catalyze the formation of NPs. Taking these data together with some previous examples of cluster-catalyzed anisotropic growth, we derived a qualitative approach to include the catalytic activities of clusters into the formation of NPs, which is incorporated into the NGT. Some qualitative conclusions about the main experimental parameters, which affect the formation of clusters versus NPs, as well as the catalytic mechanism versus the non-catalytic one, are also described. Copyright © 2015 Elsevier Inc. All rights reserved.

  9. Catalytically-etched hexagonal boron nitride flakes and their surface activity

    International Nuclear Information System (INIS)

    Kim, Do-Hyun; Lee, Minwoo; Ye, Bora; Jang, Ho-Kyun; Kim, Gyu Tae; Lee, Dong-Jin; Kim, Eok-Soo; Kim, Hong Dae

    2017-01-01

    Highlights: • Hexagonal boron nitride flakes are etched at low temperature in air by catalysts. • The presence of transition metal oxides produces an etched structure in the flakes. • Etched surfaces become highly active due to vacancy defects formed in the flakes. - Abstract: Hexagonal boron nitride (h-BN) is a ceramic compound which is thermally stable up to 1000 °C in air. Due to this, it is a very challenging task to etch h-BN under air atmosphere at low temperature. In this study, we report that h-BN flakes can be easily etched by oxidation at 350 °C under air atmosphere in the presence of transition metal (TM) oxide. After selecting Co, Cu, and Zn elements as TM precursors, we simply oxidized h-BN sheets impregnated with the TM precursors at 350 °C in air. As a result, microscopic analysis revealed that an etched structure was created on the surface of h-BN flakes regardless of catalyst type. And, X-ray diffraction patterns indicated that the air oxidation led to the formation of Co_3O_4, CuO, and ZnO from each precursor. Thermogravimetric analysis showed a gradual weight loss in the temperature range where the weight of h-BN flakes increased by air oxidation. As a result of etching, pore volume and pore area of h-BN flakes were increased after catalytic oxidation in all cases. In addition, the surface of h-BN flakes became highly active when the h-BN samples were etched by Co_3O_4 and CuO catalysts. Based on these results, we report that h-BN flakes can be easily oxidized in the presence of a catalyst, resulting in an etched structure in the layered structure.

  10. Catalytically-etched hexagonal boron nitride flakes and their surface activity

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Do-Hyun, E-mail: nanotube@korea.ac.kr [School of Electrical Engineering, Korea University, 5-ga, Anam-dong, Seongbuk-gu, Seoul 136-713 (Korea, Republic of); Lee, Minwoo; Ye, Bora [Green Manufacturing 3Rs R& D Group, Korea Institute of Industrial Technology, Ulsan 681-310 (Korea, Republic of); Jang, Ho-Kyun; Kim, Gyu Tae [School of Electrical Engineering, Korea University, 5-ga, Anam-dong, Seongbuk-gu, Seoul 136-713 (Korea, Republic of); Lee, Dong-Jin [New Functional Components Research Team, Korea Institute of Footware & Leather Technology, 152 Danggamseo-ro, Busanjin-gu, Busan 614-100 (Korea, Republic of); Kim, Eok-Soo [Green Manufacturing 3Rs R& D Group, Korea Institute of Industrial Technology, Ulsan 681-310 (Korea, Republic of); Kim, Hong Dae, E-mail: hdkim@kitech.re.kr [Green Manufacturing 3Rs R& D Group, Korea Institute of Industrial Technology, Ulsan 681-310 (Korea, Republic of)

    2017-04-30

    Highlights: • Hexagonal boron nitride flakes are etched at low temperature in air by catalysts. • The presence of transition metal oxides produces an etched structure in the flakes. • Etched surfaces become highly active due to vacancy defects formed in the flakes. - Abstract: Hexagonal boron nitride (h-BN) is a ceramic compound which is thermally stable up to 1000 °C in air. Due to this, it is a very challenging task to etch h-BN under air atmosphere at low temperature. In this study, we report that h-BN flakes can be easily etched by oxidation at 350 °C under air atmosphere in the presence of transition metal (TM) oxide. After selecting Co, Cu, and Zn elements as TM precursors, we simply oxidized h-BN sheets impregnated with the TM precursors at 350 °C in air. As a result, microscopic analysis revealed that an etched structure was created on the surface of h-BN flakes regardless of catalyst type. And, X-ray diffraction patterns indicated that the air oxidation led to the formation of Co{sub 3}O{sub 4}, CuO, and ZnO from each precursor. Thermogravimetric analysis showed a gradual weight loss in the temperature range where the weight of h-BN flakes increased by air oxidation. As a result of etching, pore volume and pore area of h-BN flakes were increased after catalytic oxidation in all cases. In addition, the surface of h-BN flakes became highly active when the h-BN samples were etched by Co{sub 3}O{sub 4} and CuO catalysts. Based on these results, we report that h-BN flakes can be easily oxidized in the presence of a catalyst, resulting in an etched structure in the layered structure.

  11. Catalytic properties of inositol trisphosphate kinase: activation by Ca2+ and calmodulin

    International Nuclear Information System (INIS)

    Ryu, S.H.; Lee, S.Y.; Lee, K.Y.; Rhee, S.G.

    1987-01-01

    Inositol 1,4,5-triphosphate (Ins-1,4,5-P 3 ) is an important second-messenger molecule that mobilizes Ca 2+ from intracellular stores in response to the occupancy of receptor by various Ca 2+ -mobilizing agonists. The fate of Ins-1,4,5-P 3 is determined by two enzymes, a 3-kinase and a 5-phosphomonoesterase. The first enzyme converts Ins-1,4,5-P 3 to Ins-1,3,4,5-P 4 , whereas the latter forms Ins-1,4-P 2 . Recent studies suggest that Ins-1,3,4,5-P 4 might modulate the entry of Ca 2+ from an extracellular source. In the current report, the authors describe the partial purification of the 3-kinase from the cytosolic fraction of bovine brain and studies of its catalytic properties. They found that the 3-kinase activity is significantly activated by the Ca 2+ /calmodulin complex. Therefore, they propose that Ca 2+ mobilized from endoplasmic reticulum by the action of Ins-1,4,5-P 3 forms a complex with calmodulin, and that the Ca 2+ /calmodulin complex stimulates the conversion of Ins-1,4,5-P 3 , and intracellular Ca 2+ mobilizer, to Ins-1,3,4,5-P 4 , an extracellular Ca 2+ mobilizer. A rapid assay method for the 3-kinase was developed that is based on the separation of [3- 32 P]Ins-1,3,4,5-P 4 and [γ- 32 P]ATP by thin-layer chromatography. Using this new assay method, they evaluated kinetic parameters (K/sub m/ for ATP = 40 μM, K/sub m/ for Ins-1,4,5-P 3 = 0.7 μM, K/sub i/ for ADP = 12 μM) and divalent cation specificity (Mg 2+ > > Mn 2+ > Ca 2+ ) for the 3-kinase

  12. Enhancement in the Catalytic Activity of Pd/USY in the Heck Reaction Induced by H2 Bubbling

    Directory of Open Access Journals (Sweden)

    Miki Niwa

    2010-12-01

    Full Text Available Pd was loaded on ultra stable Y (USY zeolites prepared by steaming NH4-Y zeolite under different conditions. Heck reactions were carried out over the prepared Pd/USY. We found that H2 bubbling was effective in improving not only the catalytic activity of Pd/USY, but also that of other supported Pd catalysts and Pd(OAc2. Moreover, the catalytic activity of Pd/USY could be optimized by choosing appropriate steaming conditions for the preparation of the USY zeolites; Pd loaded on USY prepared at 873 K with 100% H2O gave the highest activity (TOF = 61,000 h−1, which was higher than that of Pd loaded on other kinds of supports. The prepared Pd/USY catalysts were applicable to the Heck reactions using various kinds of substrates including bromo- and chloro-substituted aromatic and heteroaromatic compounds. Characterization of the acid properties of the USY zeolites revealed that the strong acid site (OHstrong generated as a result of steaming had a profound effect on the catalytic activity of Pd.

  13. Pt skin coated hollow Ag-Pt bimetallic nanoparticles with high catalytic activity for oxygen reduction reaction

    Science.gov (United States)

    Fu, Tao; Huang, Jianxing; Lai, Shaobo; Zhang, Size; Fang, Jun; Zhao, Jinbao

    2017-10-01

    The catalytic activity and stability of electrocatalyst is critical for the commercialization of fuel cells, and recent reports reveal the great potential of the hollow structures with Pt skin coat for developing high-powered electrocatalysts due to their highly efficient utilization of the Pt atoms. Here, we provide a novel strategy to prepare the Pt skin coated hollow Ag-Pt structure (Ag-Pt@Pt) of ∼8 nm size at room temperature. As loaded on the graphene, the Ag-Pt@Pt exhibits a remarkable mass activity of 0.864 A/mgPt (at 0.9 V, vs. reversible hydrogen electrode (RHE)) towards oxygen reduction reaction (ORR), which is 5.30 times of the commercial Pt/C catalyst, and the Ag-Pt@Pt also shows a better stability during the ORR catalytic process. The mechanism of this significant enhancement can be attributed to the higher Pt utilization and the unique Pt on Ag-Pt surface structure, which is confirmed by the density functional theory (DFT) calculations and other characterization methods. In conclusion, this original work offers a low-cost and environment-friendly method to prepare a high active electrocatalyst with cheaper price, and this work also discloses the correlation between surface structures and ORR catalytic activity for the hollow structures with Pt skin coat, which can be instructive for designing novel advanced electrocatalysts for fuel cells.

  14. Enhancement in the catalytic activity of Pd/USY in the heck reaction induced by H2 bubbling.

    Science.gov (United States)

    Okumura, Kazu; Tomiyama, Takuya; Moriyama, Sayaka; Nakamichi, Ayaka; Niwa, Miki

    2010-12-24

    Pd was loaded on ultra stable Y (USY) zeolites prepared by steaming NH(4)-Y zeolite under different conditions. Heck reactions were carried out over the prepared Pd/USY. We found that H₂ bubbling was effective in improving not only the catalytic activity of Pd/USY, but also that of other supported Pd catalysts and Pd(OAc)₂. Moreover, the catalytic activity of Pd/USY could be optimized by choosing appropriate steaming conditions for the preparation of the USY zeolites; Pd loaded on USY prepared at 873 K with 100% H₂O gave the highest activity (TOF = 61,000 h⁻¹), which was higher than that of Pd loaded on other kinds of supports. The prepared Pd/USY catalysts were applicable to the Heck reactions using various kinds of substrates including bromo- and chloro-substituted aromatic and heteroaromatic compounds. Characterization of the acid properties of the USY zeolites revealed that the strong acid site (OH(strong)) generated as a result of steaming had a profound effect on the catalytic activity of Pd.

  15. Identification of residues in the heme domain of soluble guanylyl cyclase that are important for basal and stimulated catalytic activity.

    Directory of Open Access Journals (Sweden)

    Padmamalini Baskaran

    Full Text Available Nitric oxide signals through activation of soluble guanylyl cyclase (sGC, a heme-containing heterodimer. NO binds to the heme domain located in the N-terminal part of the β subunit of sGC resulting in increased production of cGMP in the catalytic domain located at the C-terminal part of sGC. Little is known about the mechanism by which the NO signaling is propagated from the receptor domain (heme domain to the effector domain (catalytic domain, in particular events subsequent to the breakage of the bond between the heme iron and Histidine 105 (H105 of the β subunit. Our modeling of the heme-binding domain as well as previous homologous heme domain structures in different states point to two regions that could be critical for propagation of the NO activation signal. Structure-based mutational analysis of these regions revealed that residues T110 and R116 in the αF helix-β1 strand, and residues I41 and R40 in the αB-αC loop mediate propagation of activation between the heme domain and the catalytic domain. Biochemical analysis of these heme mutants allows refinement of the map of the residues that are critical for heme stability and propagation of the NO/YC-1 activation signal in sGC.

  16. A Polymer "Pollution Solution" Classroom Activity.

    Science.gov (United States)

    Helser, Terry L.

    1996-01-01

    Explains an approach to presenting polymer chemistry to nonmajors that employs polystyrene foam, foam peanuts made from water soluble starch, and water soluble plastic bags. Students are presented with a pollution scenario and are guided to the discovery of solutions. (DDR)

  17. Role of regulatory subunits and protein kinase inhibitor (PKI) in determining nuclear localization and activity of the catalytic subunit of protein kinase A.

    Science.gov (United States)

    Wiley, J C; Wailes, L A; Idzerda, R L; McKnight, G S

    1999-03-05

    Regulation of protein kinase A by subcellular localization may be critical to target catalytic subunits to specific substrates. We employed epitope-tagged catalytic subunit to correlate subcellular localization and gene-inducing activity in the presence of regulatory subunit or protein kinase inhibitor (PKI). Transiently expressed catalytic subunit distributed throughout the cell and induced gene expression. Co-expression of regulatory subunit or PKI blocked gene induction and prevented nuclear accumulation. A mutant PKI lacking the nuclear export signal blocked gene induction but not nuclear accumulation, demonstrating that nuclear export is not essential to inhibit gene induction. When the catalytic subunit was targeted to the nucleus with a nuclear localization signal, it was not sequestered in the cytoplasm by regulatory subunit, although its activity was completely inhibited. PKI redistributed the nuclear catalytic subunit to the cytoplasm and blocked gene induction, demonstrating that the nuclear export signal of PKI can override a strong nuclear localization signal. With increasing PKI, the export process appeared to saturate, resulting in the return of catalytic subunit to the nucleus. These results demonstrate that both the regulatory subunit and PKI are able to completely inhibit the gene-inducing activity of the catalytic subunit even when the catalytic subunit is forced to concentrate in the nuclear compartment.

  18. Activating basal-plane catalytic activity of two-dimensional MoS2 monolayer with remote hydrogen plasma

    KAUST Repository

    Cheng, Chia-Chin

    2016-09-10

    Two-dimensional layered transition metal dichalcogenide (TMD) materials such as Molybdenum disufide (MoS2) have been recognized as one of the low-cost and efficient electrocatalysts for hydrogen evolution reaction (HER). The crystal edges that account for a small percentage of the surface area, rather than the basal planes, of MoS2 monolayer have been confirmed as their active catalytic sites. As a result, extensive efforts have been developing in activating the basal planes of MoS2 for enhancing their HER activity. Here, we report a simple and efficient approach-using a remote hydrogen-plasma process-to creating S-vacancies on the basal plane of monolayer crystalline MoS2; this process can generate high density of S-vacancies while mainly maintaining the morphology and structure of MoS2 monolayer. The density of S-vacancies (defects) on MoS2 monolayers resulted from the remote hydrogen-plasma process can be tuned and play a critical role in HER, as evidenced in the results of our spectroscopic and electrical measurements. The H2-plasma treated MoS2 also provides an excellent platform for systematic and fundamental study of defect-property relationships in TMDs, which provides insights for future applications including electrical, optical and magnetic devices. © 2016 Elsevier Ltd.

  19. Identification of a Catalytically Highly Active Surface Phase for CO Oxidation over PtRh Nanoparticles under Operando Reaction Conditions

    Science.gov (United States)

    Hejral, U.; Franz, D.; Volkov, S.; Francoual, S.; Strempfer, J.; Stierle, A.

    2018-03-01

    Pt-Rh alloy nanoparticles on oxide supports are widely employed in heterogeneous catalysis with applications ranging from automotive exhaust control to energy conversion. To improve catalyst performance, an atomic-scale correlation of the nanoparticle surface structure with its catalytic activity under industrially relevant operando conditions is essential. Here, we present x-ray diffraction data sensitive to the nanoparticle surface structure combined with in situ mass spectrometry during near ambient pressure CO oxidation. We identify the formation of ultrathin surface oxides by detecting x-ray diffraction signals from particular nanoparticle facets and correlate their evolution with the sample's enhanced catalytic activity. Our approach opens the door for an in-depth characterization of well-defined, oxide-supported nanoparticle based catalysts under operando conditions with unprecedented atomic-scale resolution.

  20. Cell foundry with high product specificity and catalytic activity for 21-deoxycortisol biotransformation.

    Science.gov (United States)

    Xiong, Shuting; Wang, Ying; Yao, Mingdong; Liu, Hong; Zhou, Xiao; Xiao, Wenhai; Yuan, Yingjin

    2017-06-13

    21-deoxycortisol (21-DF) is the key intermediate to manufacture pharmaceutical glucocorticoids. Recently, a Japan patent has realized 21-DF production via biotransformation of 17-hydroxyprogesterone (17-OHP) by purified steroid 11β-hydroxylase CYP11B1. Due to the less costs on enzyme isolation, purification and stabilization as well as cofactors supply, whole-cell should be preferentially employed as the biocatalyst over purified enzymes. No reports as so far have demonstrated a whole-cell system to produce 21-DF. Therefore, this study aimed to establish a whole-cell biocatalyst to achieve 21-DF transformation with high catalytic activity and product specificity. In this study, Escherichia coli MG1655(DE3), which exhibited the highest substrate transportation rate among other tested chassises, was employed as the host cell to construct our biocatalyst by co-expressing heterologous CYP11B1 together with bovine adrenodoxin and adrenodoxin reductase. Through screening CYP11B1s (with mutagenesis at N-terminus) from nine sources, Homo sapiens CYP11B1 mutant (G25R/G46R/L52 M) achieved the highest 21-DF transformation rate at 10.6 mg/L/h. Furthermore, an optimal substrate concentration of 2.4 g/L and a corresponding transformation rate of 16.2 mg/L/h were obtained by screening substrate concentrations. To be noted, based on structural analysis of the enzyme-substrate complex, two types of site-directed mutations were designed to adjust the relative position between the catalytic active site heme and the substrate. Accordingly, 1.96-fold enhancement on 21-DF transformation rate (to 47.9 mg/L/h) and 2.78-fold improvement on product/by-product ratio (from 0.36 to 1.36) were achieved by the combined mutagenesis of F381A/L382S/I488L. Eventually, after 38-h biotransformation in shake-flask, the production of 21-DF reached to 1.42 g/L with a yield of 52.7%, which is the highest 21-DF production as known. Heterologous CYP11B1 was manipulated to construct E. coli

  1. Synthesis and characterization of supported heteropolymolybdate nanoparticles between silicate layers of Bentonite with enhanced catalytic activity for epoxidation of alkenes

    International Nuclear Information System (INIS)

    Salavati, Hossein; Rasouli, Nahid

    2011-01-01

    Highlights: → The PVMo and nanocomposite catalyst (PVMo/Bentonite) as catalyst for epoxidation of alkenes. → The composite catalyst showed higher catalytic activity than parent heteropolymolybdate (PVMo). →The use of ultrasonic irradiation increased the conversions and reduced the reaction times. → The H 2 O 2 is a green and eco-friendly oxidant in this catalytic system. -- Abstract: A new heterogeneous catalyst (PVMo/Bentonite) consisting of vanadium substituted heteropolymolybdate with Keggin-type structure Na 5 [PV 2 Mo 10 O 40 ].14H 2 O (PVMo) supported between silicate layers of bentonite has been synthesized by impregnation method and characterized using X-ray diffraction, Fourier-transformed infrared spectroscopy, scanning electron microscopy, UV-vis diffuse reflectance spectroscopy, transmission electron microscopy and elemental analysis. X-ray diffraction and scanning electron microscopy analysis indicated that PVMo was finely dispersed into layers of bentonite as support. The PVMo/Bentonite used as an efficient heterogeneous catalyst for epoxidation of alkenes. Various cyclic and linear alkenes were oxidized into the corresponding epoxides in high yields and selectivity with 30% aqueous H 2 O 2 . The catalyst was reused several times, without observable loss of activity and selectivity. The obtained results showed that the catalytic activity of the PVMo/Bentonite was higher than that of pure heteropolyanion (PVMo).

  2. 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%.

  3. Factorial experimental design for the optimization of catalytic degradation of malachite green dye in aqueous solution by Fenton process

    Directory of Open Access Journals (Sweden)

    A. Elhalil

    2016-09-01

    Full Text Available This work focuses on the optimization of the catalytic degradation of malachite green dye (MG by Fenton process “Fe2+/H2O2”. A 24 full factorial experimental design was used to evaluate the effects of four factors considered in the optimization of the oxidative process: concentration of MG (X1, concentration of Fe2+ (X2, concentration of H2O2 (X3 and temperature (X4. Individual and interaction effects of the factors that influenced the percentage of dye degradation were tested. The effect of interactions between the four parameters shows that there is a dependency between concentration of MG and concentration of Fe2+; concentration of Fe2+ and concentration of H2O2, expressed by the great values of the coefficient of interaction. The analysis of variance proved that, the concentration of MG, the concentration of Fe2+ and the concentration of H2O2 have an influence on the catalytic degradation while it is not the case for the temperature. In the optimization, the great dependence between observed and predicted degradation efficiency, the correlation coefficient for the model (R2=0.986 and the important value of F-ratio proved the validity of the model. The optimum degradation efficiency of malachite green was 93.83%, when the operational parameters were malachite green concentration of 10 mg/L, Fe2+ concentration of 10 mM, H2O2 concentration of 25.6 mM and temperature of 40 °C.

  4. Innate catalytic and free radical scavenging activities of silver nanoparticles synthesized using Dillenia indica bark extract.

    Science.gov (United States)

    Mohanty, Alfa S; Jena, Bhabani S

    2017-06-15

    A green approach was envisaged for the rapid synthesis of stable silver nanoparticles in an aqueous medium using phenolic rich ethanolic bark extract from D. indica with marked free radical scavenging and reducing ability. Biosynthesis of silver nanoparticles (AgNPs) was confirmed and characterized by using UV-visible spectroscopy, particle size analyzer, X-ray diffractometry (XRD), Transmission Electron Microscopy (TEM) and Fourier Transform Infrared Spectroscopy (FT-IR). Bio-reduction of Ag+ was confirmed with the appearance of golden yellow coloration within 5-10min at 45°C with maximum absorbance at 421nm. XRD analysis of AgNPs indicated the crystalline nature of metallic Ag. As analyzed by TEM, AgNPs were found to be spherical in shape, well dispersed and size varied from 15 to 35nm and dynamic light scattering (DLS) studies showed the average particle size of 29nm with polydispersity index (PDI) of 0.280. Synthesized AgNPs were showing surface functionalization as revealed through FTIR studies. These AgNPs were observed to be highly stable at room temperature (28±2°C) for more than 3months, thereby indicating the ethanolic extract of D. indica was a reducing as well as a capping agent for stabilization of AgNPs. Moreover, these green synthesized AgNPs showed enhanced free radical scavenging and excellent catalytic activities when used in the reduction of 4-nitrophenol and methylene blue dye, at room temperature. Copyright © 2017 Elsevier Inc. All rights reserved.

  5. Boosting the catalytic activity of natural magnetite for wet peroxide oxidation.

    Science.gov (United States)

    Álvarez-Torrellas, Silvia; Munoz, Macarena; Mondejar, Victor; de Pedro, Zahara M; Casas, Jose A

    2018-06-02

    This work explores the modification of naturally occurring magnetite by controlled oxidation (200-400 °C, air atmosphere) and reduction (300-600 °C, H 2 atmosphere) treatments with the aim of boosting its activity in CWPO. The resulting materials were fully characterized by XRD, XPS, TGA, TPR, SEM, and magnetization measurements, allowing to confirm the development of core-shell type structures. The magnetite core of the solid remained unchanged upon the treatment whereas the Fe(II)/Fe(III) ratio of the shell was modified (e.g. 0.42, 0.11 and 0.63 values were calculated for pristine Fe 3 O 4 , Fe 3 O 4 -O400, and Fe 3 O 4 -R400, respectively). The performance of the catalysts was tested in the CWPO of sulfamethoxazole (SMX) (5 mg L -1 ) under ambient conditions and circumneutral pH (pH 0  = 5), using the stoichiometric dose of H 2 O 2 (25 mg L -1 ) and a catalyst load of 1 g L -1 . The key role of the ferrous species on the mineral shell was evidenced. Whereas the oxidation of magnetite led to significantly slower degradation rates of the pollutant, its reduction gave rise to a dramatic increase, achieving the complete removal of SMX in 1.5 h reaction time with the optimum catalyst (Fe 3 O 4 -R400) compared to the 3.5 h required with the pristine mineral. A reaction mechanism was proposed for SMX degradation, and a kinetic equation based on the Eley-Rideal model was accordingly developed. This model successfully fitted the experimental results. The stability of Fe 3 O 4 -R400 was evaluated upon five sequential runs. Finally, the versatility of the catalytic system was proved in real environmentally relevant water matrices.

  6. Controlling cation segregation in perovskite-based electrodes for high electro-catalytic activity and durability.

    Science.gov (United States)

    Li, Yifeng; Zhang, Wenqiang; Zheng, Yun; Chen, Jing; Yu, Bo; Chen, Yan; Liu, Meilin

    2017-10-16

    Solid oxide cell (SOC) based energy conversion systems have the potential to become the cleanest and most efficient systems for reversible conversion between electricity and chemical fuels due to their high efficiency, low emission, and excellent fuel flexibility. Broad implementation of this technology is however hindered by the lack of high-performance electrode materials. While many perovskite-based materials have shown remarkable promise as electrodes for SOCs, cation enrichment or segregation near the surface or interfaces is often observed, which greatly impacts not only electrode kinetics but also their durability and operational lifespan. Since the chemical and structural variations associated with surface enrichment or segregation are typically confined to the nanoscale, advanced experimental and computational tools are required to probe the detailed composition, structure, and nanostructure of these near-surface regions in real time with high spatial and temporal resolutions. In this review article, an overview of the recent progress made in this area is presented, highlighting the thermodynamic driving forces, kinetics, and various configurations of surface enrichment and segregation in several widely studied perovskite-based material systems. A profound understanding of the correlation between the surface nanostructure and the electro-catalytic activity and stability of the electrodes is then emphasized, which is vital to achieving the rational design of more efficient SOC electrode materials with excellent durability. Furthermore, the methodology and mechanistic understanding of the surface processes are applicable to other materials systems in a wide range of applications, including thermo-chemical photo-assisted splitting of H 2 O/CO 2 and metal-air batteries.

  7. Influence of nitrogen surface functionalities on the catalytic activity of activated carbon in low temperature SCR of NOx with NH3

    International Nuclear Information System (INIS)

    Szymanski, Grzegorz S.; Grzybek, Teresa; Papp, Helmut

    2004-01-01

    The reduction of nitrogen oxide with ammonia was studied using carbon catalysts with chemically modified surfaces. Carbon samples with different surface chemistry were obtained from commercial activated carbon D43/1 (CarboTech, Essen, Germany) by chemical modification involving oxidation with conc. nitric acid (DOx) (1); high temperature treatment (=1000K) under vacuum (DHT) (2); or in ammonia (DHTN, DOxN) (3). Additionally, a portion of the DOx sample was promoted with iron(III) ions (DOxFe). The catalytic tests were performed in a microreactor at a temperature range of 413-573K. The carbon sample annealed under vacuum (DHT) showed the lowest activity. The formation of surface acidic surface oxides by nitric acid treatment (DOx) enhanced the catalytic activity only slightly. However, as can be expected, subsequent promotion of the DOx sample with iron(III) ions increased drastically its catalytic activity. However, this was accompanied by some loss of selectivity, i.e. formation of N 2 O as side product. This effect can be avoided using ammonia-treated carbons which demonstrated reasonable activity with simultaneous high selectivity. The most active and selective among them was the sample that was first oxidized with nitric acid and then heated in an ammonia stream (DOxN). A correlation between catalytic activity and surface nitrogen content was observed. Surface nitrogen species seem to play an important role in catalytic selective reduction of nitrogen oxide with ammonia, possibly facilitating NO 2 formation (a reaction intermediate) as a result of easier chemisorption of oxygen and nitrogen oxide

  8. Influence of nitrogen surface functionalities on the catalytic activity of activated carbon in low temperature SCR of NO{sub x} with NH{sub 3}

    Energy Technology Data Exchange (ETDEWEB)

    Szymanski, Grzegorz S. [Faculty of Chemistry, Nicolaus Copernicus University, Gagarina 7, 87-100 Torun (Poland); Grzybek, Teresa [Faculty of Fuels and Energy, AGH, University of Science and Technology, Al. Mickiewicza 30, 30-059 Krakow (Poland); Papp, Helmut [Faculty of Chemistry and Mineralogy, Institute of Technical Chemistry, University of Leipzig, Linnerstrasse 3, 04103 Leipzig (Germany)

    2004-06-15

    The reduction of nitrogen oxide with ammonia was studied using carbon catalysts with chemically modified surfaces. Carbon samples with different surface chemistry were obtained from commercial activated carbon D43/1 (CarboTech, Essen, Germany) by chemical modification involving oxidation with conc. nitric acid (DOx) (1); high temperature treatment (=1000K) under vacuum (DHT) (2); or in ammonia (DHTN, DOxN) (3). Additionally, a portion of the DOx sample was promoted with iron(III) ions (DOxFe). The catalytic tests were performed in a microreactor at a temperature range of 413-573K. The carbon sample annealed under vacuum (DHT) showed the lowest activity. The formation of surface acidic surface oxides by nitric acid treatment (DOx) enhanced the catalytic activity only slightly. However, as can be expected, subsequent promotion of the DOx sample with iron(III) ions increased drastically its catalytic activity. However, this was accompanied by some loss of selectivity, i.e. formation of N{sub 2}O as side product. This effect can be avoided using ammonia-treated carbons which demonstrated reasonable activity with simultaneous high selectivity. The most active and selective among them was the sample that was first oxidized with nitric acid and then heated in an ammonia stream (DOxN). A correlation between catalytic activity and surface nitrogen content was observed. Surface nitrogen species seem to play an important role in catalytic selective reduction of nitrogen oxide with ammonia, possibly facilitating NO{sub 2} formation (a reaction intermediate) as a result of easier chemisorption of oxygen and nitrogen oxide.

  9. Preparation and catalytic activities for H{sub 2}O{sub 2} decomposition of Rh/Au bimetallic nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Haijun, E-mail: zhanghaijun@wust.edu.cn [Key Laboratory of Integrated Exploitation of Bayan Obo Multi-Metal Resources, Inner Mongolia University of Science and Technology, Baotou 014010 (China); The State Key Laboratory of Refractory and Metallurgy, Wuhan University of Science and Technology, Wuhan 430081 (China); Deng, Xiangong; Jiao, Chengpeng; Lu, Lilin; Zhang, Shaowei [The State Key Laboratory of Refractory and Metallurgy, Wuhan University of Science and Technology, Wuhan 430081 (China)

    2016-07-15

    Graphical abstract: PVP-protected Rh/Au bimetallic nanoparticles (BNPs) were prepared by using hydrogen sacrificial reduction method, the activity of Rh80Au20 BNPs were about 3.6 times higher than that of Rh NPs. - Highlights: • Rh/Au bimetallic nanoparticles (BNPs) of 3∼5 nm in diameter were prepared. • Activity for H{sub 2}O{sub 2} decomposition of BNPs is 3.6 times higher than that of Rh NPs. • The high activity of BNPs was caused by the existence of charged Rh atoms. • The apparent activation energy for H{sub 2}O{sub 2} decomposition over the BNPs was calculated. - Abstract: PVP-protected Rh/Au bimetallic nanoparticles (BNPs) were prepared by using hydrogen sacrificial reduction method and characterized by UV–vis, XRD, FT-IR, XPS, TEM, HR-TEM and DF-STEM, the effects of composition on their particle sizes and catalytic activities for H{sub 2}O{sub 2} decomposition were also studied. The as-prepared Rh/Au BNPs possessed a high catalytic activity for the H{sub 2}O{sub 2} decomposition, and the activity of the Rh{sub 80}Au{sub 20} BNPs with average size of 2.7 nm were about 3.6 times higher than that of Rh monometallic nanoparticles (MNPs) even the Rh MNPs possess a smaller particle size of 1.7 nm. In contrast, Au MNPs with size of 2.7 nm show no any activity. Density functional theory (DFT) calculation as well as XPS results showed that charged Rh and Au atoms formed via electronic charge transfer effects could be responsible for the high catalytic activity of the BNPs.

  10. Unique self-assembly behavior of a triblock copolymer and fabrication of catalytically active gold nanoparticle/polymer thin films at the liquid/liquid interface

    International Nuclear Information System (INIS)

    Shang, Ke; Geng, Yuanyuan; Xu, Xingtao; Wang, Changwei; Lee, Yong-Ill; Hao, Jingcheng; Liu, Hong-Guo

    2014-01-01

    Gold nanoparticle-doped poly(2-vinylpyridine)-block-polystyrene-block-poly(2-vinylpyridine) (P2VP-b-PS-b-P2VP) thin films were prepared at the planar liquid/liquid interface between the chloroform solution of the polymer and aqueous solution of HAuCl 4 . Transmission electron microscopic (TEM) investigations revealed that foam films composed of microcapsules as well as one-dimensional belts were formed, and numerous Au nanoparticles were incorporated in the walls of the microcapsules and the nanobelts. The walls and the belts have layered structure. The formation mechanism of the foams and the belts was attributed to adsorption of the polymer molecules, combination of the polymer molecules with AuCl 4 − ions, microphase separation and self-assembly of the composite molecules at the interface. This microstructure is different apparently from those formed in solutions, in casting or spin-coating thin films and at the air/water interface of this triblock copolymer, reflecting unique self-assembly behavior at the liquid/liquid interface. This microstructure is also different from those formed by homo-P2VP and P4VP-b-PS-b-P4VP at the liquid/liquid interface, indicating the effects of molecular structures on the self-assembly behaviors of the polymers. After further treatment by UV-light irradiation and KBH 4 aqueous solution, the gold species were reduced completely, as indicated by UV–vis spectra and X-ray photoelectron spectra (XPS). Thermogravimetric analysis indicated that the composite films have high thermal stability, and the content of gold was estimated to be about 9.1%. These composite films exhibited high catalytic activity for the reduction of 4-nitrophenol by KBH 4 in aqueous solutions. - Highlights: • P2VP-b-PS-b-P2VP formed microcapsules and nanobelts at the liquid/liquid interface. • Its self-assembly behavior differs from P4VP-b-PS-b-P4VP at the interface. • This behavior also differs from those in solution, in film and at air/water interface

  11. Unique self-assembly behavior of a triblock copolymer and fabrication of catalytically active gold nanoparticle/polymer thin films at the liquid/liquid interface

    Energy Technology Data Exchange (ETDEWEB)

    Shang, Ke; Geng, Yuanyuan; Xu, Xingtao [Key Laboratory for Colloid and Interface Chemistry of Education Ministry, Shandong University, Jinan 250100 (China); Wang, Changwei [Environmental Monitoring Center of Shandong Province, Jinan 250013 (China); Lee, Yong-Ill [Anastro Laboratory, Department of Chemistry, Changwon National University, Changwon 641-773 (Korea, Republic of); Hao, Jingcheng [Key Laboratory for Colloid and Interface Chemistry of Education Ministry, Shandong University, Jinan 250100 (China); Liu, Hong-Guo, E-mail: hgliu@sdu.edu.cn [Key Laboratory for Colloid and Interface Chemistry of Education Ministry, Shandong University, Jinan 250100 (China)

    2014-07-01

    Gold nanoparticle-doped poly(2-vinylpyridine)-block-polystyrene-block-poly(2-vinylpyridine) (P2VP-b-PS-b-P2VP) thin films were prepared at the planar liquid/liquid interface between the chloroform solution of the polymer and aqueous solution of HAuCl{sub 4}. Transmission electron microscopic (TEM) investigations revealed that foam films composed of microcapsules as well as one-dimensional belts were formed, and numerous Au nanoparticles were incorporated in the walls of the microcapsules and the nanobelts. The walls and the belts have layered structure. The formation mechanism of the foams and the belts was attributed to adsorption of the polymer molecules, combination of the polymer molecules with AuCl{sub 4}{sup −} ions, microphase separation and self-assembly of the composite molecules at the interface. This microstructure is different apparently from those formed in solutions, in casting or spin-coating thin films and at the air/water interface of this triblock copolymer, reflecting unique self-assembly behavior at the liquid/liquid interface. This microstructure is also different from those formed by homo-P2VP and P4VP-b-PS-b-P4VP at the liquid/liquid interface, indicating the effects of molecular structures on the self-assembly behaviors of the polymers. After further treatment by UV-light irradiation and KBH{sub 4} aqueous solution, the gold species were reduced completely, as indicated by UV–vis spectra and X-ray photoelectron spectra (XPS). Thermogravimetric analysis indicated that the composite films have high thermal stability, and the content of gold was estimated to be about 9.1%. These composite films exhibited high catalytic activity for the reduction of 4-nitrophenol by KBH{sub 4} in aqueous solutions. - Highlights: • P2VP-b-PS-b-P2VP formed microcapsules and nanobelts at the liquid/liquid interface. • Its self-assembly behavior differs from P4VP-b-PS-b-P4VP at the interface. • This behavior also differs from those in solution, in film and

  12. Self-assembly growth of alloyed NiPt nanocrystals with holothuria-like shape for oxygen evolution reaction with enhanced catalytic activity

    Directory of Open Access Journals (Sweden)

    Tao Ding

    2016-01-01

    Full Text Available Self-assembly growth of alloyed NiPt nanocrystals with holothuria-like wire shape has been achieved via a facile and moderate hydrothermal process at 120 °C for 1 h from the reaction of nickel nitrate and chloroplatinic acid in alkaline solution in the presence of ethanediamine and hydrazine hydrate. The holothuria-like alloyed NiPt wires are Ni-rich in composition (Ni23.6Pt and uniform in diameter with many tiny tips outstretched from the wires surface. The holothuria-like wires are assembled from granular subunits with the assistance of capping molecular of ethanediamine and the wires display an improved oxygen evolution reaction catalytic activity.

  13. Synthesis, Characterization and catalytic activity of triorganotin(IV) carboxylates for the production of biodiesel from rocket seed oil

    International Nuclear Information System (INIS)

    Tariq, M.; Ali, S.

    2013-01-01

    Organotin(IV) carboxylates have a wide range of industrial applications such as antifouling paints, PVC stabilization, ion carries in electrochemical membranes and homogeneous catalysts. The catalytic application of organotin carboxylates are in the field of silicone curing, polyurethane formation and esterification. Only a limited literature is available regarding the use of organotin carboxylates in the transesterification of vegetable oil to produce biodiesel . The present study deals with the synthesis of some new triorganotin(IV) carboxylates for their subsequent use as catalyst for transesterification of rocket seed oil to produce biodiesel. The three new triorganotin(IV) i.e. (Me/sub 3/SnL) (1),(Bu/sub 3/Snl) (2) and (Ph/sub 3/SnL) (3), were synthesized by refluxing sodium salt of ligand (NaL), where L=O/sub 2/C(CH/sub 3/)C=CHC/sub 6/H/sub 4/F with trimethyl, tributyl and triphenyl tin(IV) chlorides, respectively for 10 hrs. The synthesized compounds were characterized by instrumental techniques like FT-IR and NMR (1H, 13C). The catalytic activity of these compounds was assessed for transesterification of triglycerides in rocket seed oil to produce biodiesel. All the tested compounds showed good catalytic activity in the order 1> 2 > 3. (author)

  14. Substantial Humic Acid Adsorption to Activated Carbon Air Cathodes Produces a Small Reduction in Catalytic Activity.

    Science.gov (United States)

    Yang, Wulin; Watson, Valerie J; Logan, Bruce E

    2016-08-16

    Long-term operation of microbial fuel cells (MFCs) can result in substantial degradation of activated carbon (AC) air-cathode performance. To examine a possible role in fouling from organic matter in water, cathodes were exposed to high concentrations of humic acids (HA). Cathodes treated with 100 mg L(-1) HA exhibited no significant change in performance. Exposure to 1000 mg L(-1) HA decreased the maximum power density by 14% (from 1310 ± 30 mW m(-2) to 1130 ± 30 mW m(-2)). Pore blocking was the main mechanism as the total surface area of the AC decreased by 12%. Minimization of external mass transfer resistances using a rotating disk electrode exhibited only a 5% reduction in current, indicating about half the impact of HA adsorption was associated with external mass transfer resistance and the remainder was due to internal resistances. Rinsing the cathodes with deionized water did not restore cathode performance. These results demonstrated that HA could contribute to cathode fouling, but the extent of power reduction was relatively small in comparison to large mass of humics adsorbed. Other factors, such as biopolymer attachment, or salt precipitation, are therefore likely more important contributors to long-term fouling of MFC cathodes.

  15. Electrically active, doped monocrystalline silicon nanoparticles produced by hot wire thermal catalytic pyrolysis

    CSIR Research Space (South Africa)

    Scriba, MR

    2011-05-01

    Full Text Available Doped silicon nanoparticles have successfully been produced by hot wire thermal catalytic pyrolysis at 40 mbar and a filament temperature of 1800 °C, using a mixture of silane and diborane or phosphine. All particles are monocrystalline with shapes...

  16. Modeling the active site of [FeFe]-hydrogenase: Electro-catalytic ...

    Indian Academy of Sciences (India)

    The mechanistic aspects of relevant electro–catalytic proton reductions have been discussed in detail. ... in the presence of a weak acid.4 This prompted us to investigate whether .... shifted to lower magnetic field strengths than those in parent ...

  17. Catalytic oxidative desulfurization of diesel utilizing hydrogen peroxide and functionalized-activated carbon in a biphasic diesel-acetonitrile system

    Energy Technology Data Exchange (ETDEWEB)

    Haw, Kok-Giap; Bakar, Wan Azelee Wan Abu; Ali, Rusmidah; Chong, Jiunn-Fat [Department of Chemistry, Faculty of Science, Universiti Teknologi Malaysia, 81310 UTM Skudai, Johor (Malaysia); Kadir, Abdul Aziz Abdul [Department of Petroleum Engineering, Faculty of Chemical and Natural Resources Engineering, Universiti Teknologi Malaysia, 81310 UTM Skudai, Johor (Malaysia)

    2010-09-15

    This paper presents the development of granular functionalized-activated carbon as catalysts in the catalytic oxidative desulfurization (Cat-ODS) of commercial Malaysian diesel using hydrogen peroxide as oxidant. Granular functionalized-activated carbon was prepared from oil palm shell using phosphoric acid activation method and carbonized at 500 C and 700 C for 1 h. The activated carbons were characterized using various analytical techniques to study the chemistry underlying the preparation and calcination treatment. Nitrogen adsorption/desorption isotherms exhibited the characteristic of microporous structure with some contribution of mesopore property. The Fourier Transform Infrared Spectroscopy results showed that higher activation temperature leads to fewer surface functional groups due to thermal decomposition. Micrograph from Field Emission Scanning Electron Microscope showed that activation at 700 C creates orderly and well developed pores. Furthermore, X-ray Diffraction patterns revealed that pyrolysis has converted crystalline cellulose structure of oil palm shell to amorphous carbon structure. The influence of the reaction temperature, the oxidation duration, the solvent, and the oxidant/sulfur molar ratio were examined. The rates of the catalytic oxidative desulfurization reaction were found to increase with the temperature, and H{sub 2}O{sub 2}/S molar ratio. Under the best operating condition for the catalytic oxidative desulfurization: temperature 50 C, atmospheric pressure, 0.5 g activated carbon, 3 mol ratio of hydrogen peroxide to sulfur, 2 mol ratio of acetic acid to sulfur, 3 oxidation cycles with 1 h for each cycle using acetonitrile as extraction solvent, the sulfur content in diesel was reduced from 2189 ppm to 190 ppm with 91.3% of total sulfur removed. (author)

  18. Boosting catalytic activity of metal nanoparticles for 4-nitrophenol reduction: Modification of metal naoparticles with poly(diallyldimethylammonium chloride)

    Energy Technology Data Exchange (ETDEWEB)

    You, Jyun-Guo; Shanmugam, Chandirasekar [Department of Chemistry, National Sun Yat-sen University, Taiwan (China); Liu, Yao-Wen; Yu, Cheng-Ju [Department of Applied Physics and Chemistry, University of Taipei, Taiwan (China); Tseng, Wei-Lung, E-mail: tsengwl@mail.nsysu.edu.tw [Department of Chemistry, National Sun Yat-sen University, Taiwan (China); School of Pharmacy, College of Pharmacy, Kaohsiung Medical University, Taiwan (China); Center for Nanoscience and Nanotechnology, National Sun Yat-sen University, Taiwan (China)

    2017-02-15

    Highlights: • The choice of capping ligand determines catalytic activity of metal nanocatalysts. • PDDA-capped metal nanoparticles electrostatically interact with 4-NP and BH4{sup −}. • PDDA-capped metal nanoparticles have good recyclability and large scalability. • PDDA-capped Pd nanoparticles show the highest rate constant and activity parameter. - Abstract: Most of the previously reported studies have focused on the change in the size, morphology, and composition of metal nanocatalysts for improving their catalytic activity. Herein, we report poly(diallyldimethylammonium chloride) [PDDA]-stabilized nanoparticles (NPs) of platinum (Pt) and palladium (Pd) as highly active and efficient catalysts for hydrogenation of 4-nitrophenol (4-NP) in the presence of NaBH4. PDDA-stabilized Pt and Pd NPs possessed similar particle size and same facet with citrate-capped Pt and Pd NPs, making this study to investigate the inter-relationship between catalytic activity and surface ligand without the consideration of the effects of particle size and facet. Compared to citrate-capped Pt and Pd NPs, PDDA-stabilized Pt and Pd NPs exhibited excellent pH and salt stability. PDDA could serve as an electron acceptor for metal NPs to produce the net positive charges on the metal surface, which provide strong electrostatic attraction with negatively charged nitrophenolate and borohydride ions. The activity parameter and rate constant of PDDA-stabilized metal NPs were higher than those of citrate-capped metal NPs. Compared to the previously reported Pd nanomaterials for the catalysis of NaBH4-mediated reduction of 4-NP, PDDA-stabilized Pd NPs exhibited the extremely high activity parameter (195 s{sup −1} g{sup −1}) and provided excellent scalability and reusability.

  19. Effects of pH value on composition structure and catalytic activity of Pt-SnO{sub x}/C prepared by ethylene glycol method

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Y.H. [School of Chemical Engineering and Environment, Beijing Institute of Technology, 100081 Beijing (China); Wu, F.; Wu, C. [School of Chemical Engineering and Environment, Beijing Institute of Technology, 100081 Beijing (China); National Development Center for High Technology Green Materials, 100081 Beijing (China)

    2012-06-15

    Pt-SnO{sub x} nanoparticles were synthesized by the ethylene glycol (EG) method in solution of H{sub 2}PtCl{sub 6} and SnCl{sub 2}, with the same concentrations of Pt and Sn, but different pH values. The pH value after the end of platinum reduction reaction was not changed any more, except that a certain amount of water was added to deposit the Pt-SnO{sub x} nanoparticles on the carbon support. The pre-nanocatalysts were characterized by X-ray photoelectron spectroscopy (XPS) to investigate the contents of Pt and Sn, and their catalytic activities for ethanol electrooxidation were tested by cyclic voltammetry (CV). The result was that the Sn contents were increasing as the Pt/Sn atomic ratios of 2.2, 2.6, 5.1, 7.4, 8.7, with the decreasing end pH values of 4.5, 5.0, 5.5, 6.5, 7.5, and the Pt contents became less than the addition in the preparation solution while the end pH values were <5.5, but the catalytic activities for ethanol electrooxidation were not so much regularly changed. Besides, from the end pH value of 5.5 to the increasing 9.0, all the platinum nanoparticles could be completely deposited on the carbon support, under the condition that only a certain amount of water was added. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  20. 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

  1. Catalytic destruction of perchlorate in ferric chloride and hydrochloric acid solution with control of temperature, pressure and chemical reagents

    Science.gov (United States)

    Gu, Baohua; Cole, David R.; Brown, Gilbert M.

    2004-10-05

    A method is described to decompose perchlorate in a FeCl.sub.3 /HCl aqueous solution such as would be used to regenerate an anion exchange resin used to remove perchlorate. The solution is mixed with a reducing agent, preferably an organic alcohol and/or ferrous chloride, and can be heated to accelerate the decomposition of perchlorate. Lower temperatures may be employed if a catalyst is added.

  2. Determination of the activity of a molecular solute in saturated solution

    International Nuclear Information System (INIS)

    Nordstroem, Fredrik L.; Rasmuson, Ake C.

    2008-01-01

    Prediction of the solubility of a solid molecular compound in a solvent, as well as, estimation of the solution activity coefficient from experimental solubility data both require estimation of the activity of the solute in the saturated solution. The activity of the solute in the saturated solution is often defined using the pure melt at the same temperature as the thermodynamic reference. In chemical engineering literature also the activity of the solid is usually defined on the same reference state. However, far below the melting temperature, the properties of this reference state cannot be determined experimentally, and different simplifications and approximations are normally adopted. In the present work, a novel method is presented to determine the activity of the solute in the saturated solution (=ideal solubility) and the heat capacity difference between the pure supercooled melt and solid. The approach is based on rigorous thermodynamics, using standard experimental thermodynamic data at the melting temperature of the pure compound and solubility measurements in different solvents at various temperatures. The method is illustrated using data for ortho-, meta-, and para-hydroxybenzoic acid, salicylamide and paracetamol. The results show that complete neglect of the heat capacity terms may lead to estimations of the activity that are incorrect by a factor of 12. Other commonly used simplifications may lead to estimations that are only one-third of the correct value

  3. Determination of the activity of a molecular solute in saturated solution

    Energy Technology Data Exchange (ETDEWEB)

    Nordstroem, Fredrik L. [Department of Chemical Engineering and Technology, Royal Institute of Technology, 100 44 Stockholm (Sweden); Rasmuson, Ake C. [Department of Chemical Engineering and Technology, Royal Institute of Technology, 100 44 Stockholm (Sweden)], E-mail: rasmuson@ket.kth.se

    2008-12-15

    Prediction of the solubility of a solid molecular compound in a solvent, as well as, estimation of the solution activity coefficient from experimental solubility data both require estimation of the activity of the solute in the saturated solution. The activity of the solute in the saturated solution is often defined using the pure melt at the same temperature as the thermodynamic reference. In chemical engineering literature also the activity of the solid is usually defined on the same reference state. However, far below the melting temperature, the properties of this reference state cannot be determined experimentally, and different simplifications and approximations are normally adopted. In the present work, a novel method is presented to determine the activity of the solute in the saturated solution (=ideal solubility) and the heat capacity difference between the pure supercooled melt and solid. The approach is based on rigorous thermodynamics, using standard experimental thermodynamic data at the melting temperature of the pure compound and solubility measurements in different solvents at various temperatures. The method is illustrated using data for ortho-, meta-, and para-hydroxybenzoic acid, salicylamide and paracetamol. The results show that complete neglect of the heat capacity terms may lead to estimations of the activity that are incorrect by a factor of 12. Other commonly used simplifications may lead to estimations that are only one-third of the correct value.

  4. Fabrication of doped TiO2 nanotube array films with enhanced photo-catalytic activity

    Science.gov (United States)

    Peighambardoust, Naeimeh-Sadat; Khameneh-asl, Shahin; Khademi, Adib

    2018-01-01

    In the present work, we investigate the N and Fe-doped TiO2 nanotube array film prepared by treating TiO2 nanotube array film with ammonia solution and anodizing in Fe(NO3)3 solution respectively. This method avoided the use of hazardous ammonia gas, or laborious ion implantation process. N and Fe-doped TiO2 nanotube arrays (TiO2 NTs) were prepared by electrochemical anodization process in 0.5 wt % HF aqueous solution. The anodization was performed at the conditions of 20 V and 20 min, Followed by a wet immersion in NH3.H2O (1M) for N-doping for 2 hr and annealing post-treatment at 450 °C. The morphology and structure of the nanotube films were characterized by field emission scanning electron microscope (FESEM) and EDX. UV-vis. illumination test were done to observe photo-enhanced catalysis. The effect of different annealing temperature on the structure and photo-absorption property of the TiO2-TNTs was investigated. The results showed that N-TNTs nanotubes exhibited higher photocatalytic activity compared whit the Fe-doped and pure TNTs, because doping N promoted the separation of the photogenerated electrons and holes.

  5. Catalytic Activity and Stability of Oxides: The Role of Near-Surface Atomic Structures and Compositions.

    Science.gov (United States)

    Feng, Zhenxing; Hong, Wesley T; Fong, Dillon D; Lee, Yueh-Lin; Yacoby, Yizhak; Morgan, Dane; Shao-Horn, Yang

    2016-05-17

    the physical origin of segregation is discussed in comparison with (La1-ySry)2CoO4±δ/La1-xSrxCo0.2Fe0.8O3-δ. Sr enrichment in many electrocatalysts, such as La1-xSrxMO3-δ (M = Cr, Co, Mn, or Co and Fe) and Sm1-xSrxCoO3, has been probed using alternative techniques, including low energy ion scattering, secondary ion mass spectrometry, and X-ray fluorescence-based methods for depth-dependent, element-specific analysis. We highlight a strong connection between cation segregation and electrocatalytic properties, because cation segregation enhances oxygen transport and surface oxygen exchange kinetics. On the other hand, the formation of cation-enriched secondary phases can lead to the blocking of active sites, inhibiting oxygen exchange. With help from density functional theory, the links between cation migration, catalyst stability, and catalytic activity are provided, and the oxygen p-band center relative to the Fermi level can be identified as an activity descriptor. Based on these findings, we discuss strategies to increase a catalyst's activity while maintaining stability to design efficient, cost-effective electrocatalysts.

  6. Catalytic Activity and Stability of Oxides: The Role of Near-Surface Atomic Structures and Compositions

    KAUST Repository

    Feng, Zhenxing

    2016-05-05

    δ oxide thin films, and the physical origin of segregation is discussed in comparison with (La1–ySry)2CoO4±δ/La1–xSrxCo0.2Fe0.8O3−δ. Sr enrichment in many electrocatalysts, such as La1–xSrxMO3−δ (M = Cr, Co, Mn, or Co and Fe) and Sm1–xSrxCoO3, has been probed using alternative techniques, including low energy ion scattering, secondary ion mass spectrometry, and X-ray fluorescence-based methods for depth-dependent, element-specific analysis. We highlight a strong connection between cation segregation and electrocatalytic properties, because cation segregation enhances oxygen transport and surface oxygen exchange kinetics. On the other hand, the formation of cation-enriched secondary phases can lead to the blocking of active sites, inhibiting oxygen exchange. With help from density functional theory, the links between cation migration, catalyst stability, and catalytic activity are provided, and the oxygen p-band center relative to the Fermi level can be identified as an activity descriptor. Based on these findings, we discuss strategies to increase a catalyst’s activity while maintaining stability to design efficient, cost-effective electrocatalysts.

  7. N-Methylamino Pyrimidyl Amides (MAPA): Highly Reactive, Electronically-Activated Amides in Catalytic N-C(O) Cleavage.

    Science.gov (United States)

    Meng, Guangrong; Lalancette, Roger; Szostak, Roman; Szostak, Michal

    2017-09-01

    Despite recent progress in catalytic cross-coupling technologies, the direct activation of N-alkyl-N-aryl amides has been a challenging transformation. Here, we report the first Suzuki cross-coupling of N-methylamino pyrimidyl amides (MAPA) enabled by the controlled n N → π Ar conjugation and the resulting remodeling of the partial double bond character of the amide bond. The new mode of amide activation is suitable for generating acyl-metal intermediates from unactivated primary and secondary amides.

  8. Understanding Trends in Catalytic Activity: The Effect of Adsorbate-Adsorbate Interactions for CO Oxidation Over Transition Metals

    DEFF Research Database (Denmark)

    Grabow, Lars; Larsen, Britt Hvolbæk; Nørskov, Jens Kehlet

    2010-01-01

    Using high temperature CO oxidation as the example, trends in the reactivity of transition metals are discussed on the basis of density functional theory (DFT) calculations. Volcano type relations between the catalytic rate and adsorption energies of important intermediates are introduced...... and the effect of adsorbate-adsorbate interaction on the trends is discussed. We find that adsorbate-adsorbate interactions significantly increase the activity of strong binding metals (left side of the volcano) but the interactions do not change the relative activity of different metals and have a very small...... influence on the position of the top of the volcano, that is, on which metal is the best catalyst....

  9. Solute-mediated interactions between active droplets

    NARCIS (Netherlands)

    Moerman, Pepijn G.; Moyses, Henrique W.; Van Der Wee, Ernest B.; Grier, David G.; Van Blaaderen, Alfons; Kegel, Willem K.; Groenewold, Jan; Brujic, Jasna

    2017-01-01

    Concentration gradients play a critical role in embryogenesis, bacterial locomotion, as well as the motility of active particles. Particles develop concentration profiles around them by dissolution, adsorption, or the reactivity of surface species. These gradients change the surface energy of the

  10. Catalytic activity of hydrophobic Pt/C/PTFE catalysts of different PTFE content for hydrogen-water liquid exchange reaction

    International Nuclear Information System (INIS)

    Hu Sheng; Xiao Chengjian; Zhu Zuliang; Luo Shunzhong; Wang Heyi; Luo Yangming; Wang Changbin

    2007-01-01

    10%Pt/C catalysts were prepared by liquid reduction method. PTFE and Pt/ C catalysts were adhered to porous metal and hydrophobic Pt/C/PTFE catalysts were prepared. The structure and size of Pt crystal particles of Pt/C catalysts were analyzed by XRD, and their mean size was 3.1 nm. The dispersion state of Pt/C and PTFE was analyzed by SEM, and they had good dispersion mostly, but PTFE membrane could be observed on local parts of Pt/C/PTFE surface. Because of low hydrophobicity, Pt/C/ PTFE catalysts have low activity when the mass ratio of PTFE and Pt/C is 0.5: 1, and their catalytic activity increases markedly when the ratio is 1:1. When the ratio increases again, more Pt active sites would be covered by PTFE and interior diffusion effect would increase, which result in the decrease of catalytic activity of Pt/C/PTFE. By PTFE pretreatment of porous metal carrier, the activity of Pt/C/PTFE catalysts decreases when the mass ratio of PTFE and Pt/C is 0.5:1, and their activity decreases when the mass ratio is 1:1. (authors)

  11. Relationship between the catalytic activity of Pt/alumina and the relaxation process of the photoexcited electrons

    Energy Technology Data Exchange (ETDEWEB)

    Ito, Junji, E-mail: j-itou@mail.nissan.co.jp [Advanced Materials Laboratory, Nissan Research Center, NISSAN MOTOR CO., LTD., 1 Natsushima-cho, Yokosuka-shi, Kanagawa 237-8523 (Japan); Department of Applied Physics and Chemistry, The University of Electro-Communications, 1-5-1 Chofugaoka, Chofu, Tokyo 182-8585 (Japan); Hanaki, Yasunari [Advanced Materials Laboratory, Nissan Research Center, NISSAN MOTOR CO., LTD., 1 Natsushima-cho, Yokosuka-shi, Kanagawa 237-8523 (Japan); Shen, Qing [Department of Applied Physics and Chemistry, The University of Electro-Communications, 1-5-1 Chofugaoka, Chofu, Tokyo 182-8585 (Japan); Department of Engineering Science, The University of Electro-Communications, 1-5-1 Chofugaoka, Chofu, Tokyo 182-8585 (Japan); PRESTO, Japan Science and Technology Agency (JST), 4-1-8 Honcho, Kawaguchi, Saitama 332-0012 (Japan); Toyoda, Taro [Department of Applied Physics and Chemistry, The University of Electro-Communications, 1-5-1 Chofugaoka, Chofu, Tokyo 182-8585 (Japan); Department of Engineering Science, The University of Electro-Communications, 1-5-1 Chofugaoka, Chofu, Tokyo 182-8585 (Japan)

    2012-12-15

    Highlights: Black-Right-Pointing-Pointer We determined the decay time of photoexcited electrons of Pt/Al{sub 2}O{sub 3}. Black-Right-Pointing-Pointer Faster decay of excited electrons in Pt/Al{sub 2}O{sub 3} leads to its faster oxidation rate. Black-Right-Pointing-Pointer Decreasing excited electron lifetime in Pt/Al{sub 2}O{sub 3} may decrease Pt consumption in catalytic convertors. - Abstract: In order to decrease the consumption of precious metals used in the catalytic converters used in automobiles, we studied the relationship between the catalytic activity of Pt/alumina (Pt/Al{sub 2}O{sub 3}) and the relaxation process of photoexcited electrons. Firstly, we studied the relationship between the size of the Pt particles in Pt/Al{sub 2}O{sub 3} and catalytic performance. Secondly, the relationship between the size of the Pt particles in Pt/Al{sub 2}O{sub 3} and the decay time of the excited electrons was studied using an improved transient grating (TG) technique. The results showed that faster decay of the excited electrons leads to greater oxidation rates. The decay time obtained with the improved TG technique gives an indication of the time that the exited electrons take to return to the ground state. According to studies utilizing FT-IR, one of the processes necessary for quickly generating CO{sub 2} with Pt is that the electron in the Pt-O bond moves to the Pt side and that the Pt{sup +} becomes Pt metal. Thus, the decay time obtained with the improved TG technique corresponds to the process whereby Pt{sup +} returns to Pt metal. Thus, we found that the consumption of precious metals can be reduced by increasing the speed of the decay of the excited electrons.

  12. Relationship between the catalytic activity of Pt/alumina and the relaxation process of the photoexcited electrons

    International Nuclear Information System (INIS)

    Ito, Junji; Hanaki, Yasunari; Shen, Qing; Toyoda, Taro

    2012-01-01

    Highlights: ► We determined the decay time of photoexcited electrons of Pt/Al 2 O 3 . ► Faster decay of excited electrons in Pt/Al 2 O 3 leads to its faster oxidation rate. ► Decreasing excited electron lifetime in Pt/Al 2 O 3 may decrease Pt consumption in catalytic convertors. - Abstract: In order to decrease the consumption of precious metals used in the catalytic converters used in automobiles, we studied the relationship between the catalytic activity of Pt/alumina (Pt/Al 2 O 3 ) and the relaxation process of photoexcited electrons. Firstly, we studied the relationship between the size of the Pt particles in Pt/Al 2 O 3 and catalytic performance. Secondly, the relationship between the size of the Pt particles in Pt/Al 2 O 3 and the decay time of the excited electrons was studied using an improved transient grating (TG) technique. The results showed that faster decay of the excited electrons leads to greater oxidation rates. The decay time obtained with the improved TG technique gives an indication of the time that the exited electrons take to return to the ground state. According to studies utilizing FT-IR, one of the processes necessary for quickly generating CO 2 with Pt is that the electron in the Pt-O bond moves to the Pt side and that the Pt + becomes Pt metal. Thus, the decay time obtained with the improved TG technique corresponds to the process whereby Pt + returns to Pt metal. Thus, we found that the consumption of precious metals can be reduced by increasing the speed of the decay of the excited electrons.

  13. Heterogeneous catalytic ozonation of biologically pretreated Lurgi coal gasification wastewater using sewage sludge based activated carbon supported manganese and ferric oxides as catalysts.

    Science.gov (United States)

    Zhuang, Haifeng; Han, Hongjun; Hou, Baolin; Jia, Shengyong; Zhao, Qian

    2014-08-01

    Sewage sludge of biological wastewater treatment plant was converted into sewage sludge based activated carbon (SBAC) with ZnCl₂ as activation agent, which supported manganese and ferric oxides as catalysts (including SBAC) to improve the performance of ozonation of real biologically pretreated Lurgi coal gasification wastewater. The results indicated catalytic ozonation with the prepared catalysts significantly enhanced performance of pollutants removal and the treated wastewater was more biodegradable and less toxic than that in ozonation alone. On the basis of positive effect of higher pH and significant inhibition of radical scavengers in catalytic ozonation, it was deduced that the enhancement of catalytic activity was responsible for generating hydroxyl radicals and the possible reaction pathway was proposed. Moreover, the prepared catalysts showed superior stability and most of toxic and refractory compounds were eliminated at successive catalytic ozonation runs. Thus, the process with economical, efficient and sustainable advantages was beneficial to engineering application. Copyright © 2014 Elsevier Ltd. All rights reserved.

  14. Mutational analysis of amino acid residues involved in catalytic activity of a family 18 chitinase from tulip bulbs.

    Science.gov (United States)

    Suzukawa, Keisuke; Yamagami, Takeshi; Ohnuma, Takayuki; Hirakawa, Hideki; Kuhara, Satoru; Aso, Yoichi; Ishiguro, Masatsune

    2003-02-01

    We expressed chitinase-1 (TBC-1) from tulip bulbs (Tulipa bakeri) in E. coli cells and used site-directed mutagenesis to identify amino acid residues essential for catalytic activity. Mutations at Glu-125 and Trp-251 completely abolished enzyme activity, and activity decreased with mutations at Asp-123 and Trp-172 when glycolchitin was the substrate. Activity changed with the mutations of Trp-251 to one of several amino acids with side-chains of little hydrophobicity, suggesting that hydrophobic interaction of Trp-251 is important for the activity. Molecular dynamics (MD) simulation analysis with hevamine as the model compound showed that the distance between Asp-123 and Glu-125 was extended by mutation of Trp-251. Kinetic studies of Trp-251-mutated chitinases confirmed these various phenomena. The results suggested that Glu-125 and Trp-251 are essential for enzyme activity and that Trp-251 had a direct role in ligand binding.

  15. 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)

  16. The catalytic activity of several tungsten oxides for the oxidation of propene

    International Nuclear Information System (INIS)

    De Rossi, S.; Schiavello, M.; Rome Univ.; Iguchi, E.; Tilley, R.J.D.

    1976-01-01

    A study has been made of the catalytic oxidation of propene over the oxides WO 3 , WOsub(2,95), WOsub(2,90), WOsub(2,72) and Wo 2 , which were selected because they possess specific features of chemical and structural interest rather than for their catalytic ability. It was found that the oxides WOsub(2,95), WOsub(2,90) and WOsub(2,72) all selectively produce acrolein in small amounts. The oxides WO 3 and WO 2 were non-selective and rather inactive. The results are discussed in terms of a mechanism involving both variable valence in the crystal and the specific structural geometry of these compounds. (orig.) [de

  17. Catalytic Performance of Co3O4 on Different Activated Carbon Supports in the Benzyl Alcohol Oxidation

    Directory of Open Access Journals (Sweden)

    Misael Cordoba

    2017-12-01

    Full Text Available Co3O4 particles were supported on a series of activated carbons (G60, CNR, RX3, and RB3. Incipient wetness method was used to prepare these catalysts. The effect of the structural and surface properties of the carbonaceous supports during oxidation of benzyl alcohol was evaluated. The synthetized catalysts were characterized via IR, TEM, TGA/MS, XRD, TPR, AAS, XPS, and N2 adsorption/desorption isotherm techniques. Co3O4/G60 and Co3O4/RX3 catalysts have high activity and selectivity on the oxidation reaction reaching conversions above 90% after 6 h, without the presence of promoters. Catalytic performances show that differences in chemistry of support surface play an important role in activity and suggest that the presence of different ratios of species of cobalt and oxygenated groups on surface in Co3O4/G60 and Co3O4/RX3 catalysts, offered a larger effect synergic between both active phase and support increasing their catalytic activity when compared to the other tested catalysts.

  18. 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

  19. 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.

  20. 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.

  1. Dextran solution optical activity in Tb (III) ion presence

    International Nuclear Information System (INIS)

    Vasconcellos, Sandra S.; Rodrigues, J.F.; Faljoni-Alario, A.

    1984-01-01

    Optical activity studies of aqueous solutions of dextrana in presence of Tb (III) or without it shows the complex with the hidroxyl groups of C 2 and C 3 of monomeric unit participation is formed. (L.M.J.) [pt

  2. Directed evolution of a β-mannanase from Rhizomucor miehei to improve catalytic activity in acidic and thermophilic conditions.

    Science.gov (United States)

    Li, Yan-Xiao; Yi, Ping; Yan, Qiao-Juan; Qin, Zhen; Liu, Xue-Qiang; Jiang, Zheng-Qiang

    2017-01-01

    β-Mannanase randomly cleaves the β-1,4-linked mannan backbone of hemicellulose, which plays the most important role in the enzymatic degradation of mannan. Although the industrial applications of β-mannanase have tremendously expanded in recent years, the wild-type β-mannanases are still defective for some industries. The glycoside hydrolase (GH) family 5 β-mannanase ( Rm Man5A) from Rhizomucor miehei shows many outstanding properties, such as high specific activity and hydrolysis property. However, owing to the low catalytic activity in acidic and thermophilic conditions, the application of Rm Man5A to the biorefinery of mannan biomasses is severely limited. To overcome the limitation, Rm Man5A was successfully engineered by directed evolution. Through two rounds of screening, a mutated β-mannanase (m Rm Man5A) with high catalytic activity in acidic and thermophilic conditions was obtained, and then characterized. The mutant displayed maximal activity at pH 4.5 and 65 °C, corresponding to acidic shift of 2.5 units in optimal pH and increase by 10 °C in optimal temperature. The catalytic efficiencies ( k cat / K m ) of m Rm Man5A towards many mannan substrates were enhanced more than threefold in acidic and thermophilic conditions. Meanwhile, the high specific activity and excellent hydrolysis property of Rm Man5A were inherited by the mutant m Rm Man5A after directed evolution. According to the result of sequence analysis, three amino acid residues were substituted in m Rm Man5A, namely Tyr233His, Lys264Met, and Asn343Ser. To identify the function of each substitution, four site-directed mutations (Tyr233His, Lys264Met, Asn343Ser, and Tyr233His/Lys264Met) were subsequently generated, and the substitutions at Tyr233 and Lys264 were found to be the main reason for the changes of m Rm Man5A. Through directed evolution of Rm Man5A, two key amino acid residues that controlled its catalytic efficiency under acidic and thermophilic conditions were identified

  3. Thermodynamically accurate modeling of the catalytic cycle of photosynthetic oxygen evolution: a mathematical solution to asymmetric Markov chains.

    Science.gov (United States)

    Vinyard, David J; Zachary, Chase E; Ananyev, Gennady; Dismukes, G Charles

    2013-07-01

    Forty-three years ago, Kok and coworkers introduced a phenomenological model describing period-four oscillations in O2 flash yields during photosynthetic water oxidation (WOC), which had been first reported by Joliot and coworkers. The original two-parameter Kok model was subsequently extended in its level of complexity to better simulate diverse data sets, including intact cells and isolated PSII-WOCs, but at the expense of introducing physically unrealistic assumptions necessary to enable numerical solutions. To date, analytical solutions have been found only for symmetric Kok models (inefficiencies are equally probable for all intermediates, called "S-states"). However, it is widely accepted that S-state reaction steps are not identical and some are not reversible (by thermodynamic restraints) thereby causing asymmetric cycles. We have developed a mathematically more rigorous foundation that eliminates unphysical assumptions known to be in conflict with experiments and adopts a new experimental constraint on solutions. This new algorithm termed STEAMM for S-state Transition Eigenvalues of Asymmetric Markov Models enables solutions to models having fewer adjustable parameters and uses automated fitting to experimental data sets, yielding higher accuracy and precision than the classic Kok or extended Kok models. This new tool provides a general mathematical framework for analyzing damped oscillations arising from any cycle period using any appropriate Markov model, regardless of symmetry. We illustrate applications of STEAMM that better describe the intrinsic inefficiencies for photon-to-charge conversion within PSII-WOCs that are responsible for damped period-four and period-two oscillations of flash O2 yields across diverse species, while using simpler Markov models free from unrealistic assumptions. Copyright © 2013 Elsevier B.V. All rights reserved.

  4. Catalytic activity and effect of modifiers on Ni-based catalysts for the dry reforming of methane

    Energy Technology Data Exchange (ETDEWEB)

    Barroso-Quiroga, Maria Martha; Castro-Luna, Adolfo Eduardo [Facultad de Ingenieria y Ciencias Economico-Sociales INTEQUI-CONICET-UNSL, Av. 25 de Mayo 384 (5730) Villa Mercedes (S.L.) (Argentina)

    2010-06-15

    Ni catalysts supported on different ceramic oxides (Al{sub 2}O{sub 3}, CeO{sub 2}, La{sub 2}O{sub 3}, ZrO{sub 2}) were prepared by wet impregnation. The catalytic behavior toward hydrogen production through the dry reforming of methane using a fixed-bed reactor was evaluated under certain experimental conditions, and the catalyst supported on ZrO{sub 2} showed the highest stable activity during the period of time studied. The catalyst supported on CeO{sub 2} has a relatively good activity, but shows signs of deactivation after a certain time during the reaction. This catalyst was chosen to be studied after the addition of 0.5 wt% Li and K as activity modifiers. The introduction of the alkaline metals produces a reduction of the catalytic activity but a better stability over the reactant conversion time. The reverse water-gas shift reaction influences the global system of reactions, and as the results indicate, should be considered near equilibrium. (author)

  5. Influence of Addition of Fluid Catalytic Cracking Residue (FCC and the SiO2 Concentration in Alkali-Activated Ceramic Sanitary-Ware (CSW Binders

    Directory of Open Access Journals (Sweden)

    Juan Cosa

    2018-03-01

    Full Text Available Production of Portland cement requires a large volume of natural raw materials and releases huge amounts of CO2 to the atmosphere. Lower environmental impact alternatives focus on alkali-activated cements. In this paper, fluid catalytic cracking residue (FCC was used to partially replace (0 wt %–50 wt % ceramic sanitaryware (CSW in alkali-activated systems. Samples were activated with NaOH and sodium silicate solutions and were cured at 65 °C for 7 days and at 20 °C for 28 and 90 days. In order to increase CSW/FCC binders’ sustainability, the influence of reducing the silica concentration (from 7.28 mol·kg−1 up to 2.91 mol·kg−1 was analyzed. The microstructure of the developed binders was investigated in pastes by X-ray diffraction, thermo tests and field emission scanning electron microscopy analyses. Compressive strength evolution was assessed in mortars. The results showed a synergetic effect of the CSW/FCC combinations so that, under the studied conditions, mechanical properties significantly improved when combining both waste materials (up to 70 MPa were achieved in the mortars containing 50 wt % FCC cured at room temperature for 90 days. Addition of FCC allowed CSW to be activated at room temperature, which significantly broadens the field of applications of alkali-activated CSW binders.

  6. PREPARATION, CHARACTERIZATION AND CATALYTIC ACTIVITY TEST OF CoMo/ZnO CATALYST ON ETHANOL CONVERSION USING STEAM REFORMING METHOD

    Directory of Open Access Journals (Sweden)

    Wega Trisunaryanti

    2010-06-01

    Full Text Available Preparation, characterization and catalytic activity test of CoMo/ZnO catalyst for steam reforming of ethanol have been investigated. The catalysts preparation was carried out by impregnation of Co and/or Mo onto ZnO sample. Water excess was used in ethanol feed for steam reforming process under mol ratio of ethanol:water (1:10. Characterizations of catalysts were conducted by analysis of metal content using Atomic Absorption Spectroscopy (AAS. Determination of catalysts acidity was conducted by gravimetric method of adsorption of pyridine base. Catalytic activity test on ethanol conversion using steam reforming method was conducted in a semi-flow reactor system, at a temperature of 400 oC, for 1.5 h under N2 flow rate of 10 mL/min. Gas product was analyzed by gas chromatograph with TCD system. The results of catalysts characterizations showed that the impregnation of Co and/or Mo metals on ZnO sample increased its acidity and specific surface area. The content of Co in Co/ZnO and CoMo/ZnO catalysts was 1.14 and 0.49 wt%. The Mo content in CoMo/ZnO catalyst was 0.36 wt%. The catalytic activity test result on ethanol conversion showed that the ZnO, Co/ZnO, and CoMo/ZnO catalysts produced gas fraction of 16.73, 28.53, and 35.53 wt%, respectively. The coke production of ZnO, Co/ZnO, and CoMo/ZnO catalysts was 0.86, 0.24, and 0.08 wt%, respectively. The gas products consisted mainly of hydrogen.   Keywords: CoMo/ZnO catalyst, steam reforming, ethanol

  7. Syntheses, characterizations, and catalytic activities of mesostructured aluminophosphates with tailorable acidity assembled with various preformed zeolite nanoclusters

    KAUST Repository

    Suo, Hongri

    2015-02-25

    © 2015, Springer Science+Business Media New York. A series of ordered hexagonal mesoporous zeolites have been successfully synthesized by the assembly of various preformed aluminosilicates zeolite (MFI, FAU, BEA etc.) with surfactants (cetyltrimethylammonium chloride) under hydrothermal conditions. These unique samples were further characterized by X-ray diffraction, transmission electron microscopy, N2 adsorption, infrared spectroscopy. Characterization results showed that these samples contain primary and secondary structural building units of various zeolites, which may be responsible for their distinguished acidic strength, suggesting that the acidic strength of these mesoporous silicoaluminophosphates could be tailored and controlled. Furthermore, the prepared samples were catalytically active in the cracking of cumene.

  8. Synthesis and characterization of a new porphyrin-polyoxometalate hybrid material and investigation of its catalytic activity.

    Science.gov (United States)

    Araghi, Mehdi; Mirkhani, Valiollah; Moghadam, Majid; Tangestaninejad, Shahram; Mohammdpoor-Baltork, Iraj

    2012-03-14

    In the present work, the preparation of a new organic-inorganic hybrid material in which tetrakis(p-aminophenylporphyrin) is covalently linked to a Lindqvist structure of polyoxometalate, is reported. This new porphyrin-polyoxometalate hybrid material was characterized by (1)H NMR, FT-IR and UV-Vis spectroscopic methods and cyclic voltammetry. These spectro- and electrochemical studies provided spectral data of the synthesis of this compound. Cyclic voltammetry showed the influence of the porphyrin on the redox process of the polyoxometalate. The catalytic activity of this hybrid material was investigated in the alkene epoxidation with NaIO(4).

  9. Catalytic activity of Co/SiO2 and Co/TiO2 nanosized systems in the oxidation of carbon monoxide

    Science.gov (United States)

    Kelyp, A. A.; Smirnova, N. P.; Oleksenko, L. P.; Lutsenko, L. V.; Oranskaya, E. I.; Ripko, A. P.

    2013-06-01

    The effects of the preparation procedure, active component concentration, and conditions of formation of nanosized cobalt-containing systems based on TiO2 and SiO2 mesoporous powders on their catalytic activity in the oxidation of carbon monoxide were studied. The active phase in the systems was cobalt spinel CoCo2O4 found in all samples. High catalytic activity was found in the samples characterized by relatively high contents of surface active centers (cobalt cations with octahedral surroundings).

  10. Ferredoxin-thioredoxin reductase: a catalytically active dithiol group links photoreduced ferredoxin to thioredoxin functional in photosynthetic enzyme regulation

    International Nuclear Information System (INIS)

    Droux, M.; Miginiac-Maslow, M.; Jacquot, J.P.; Gadal, P.; Crawford, N.A.; Kosower, N.S.; Buchanan, B.B.

    1987-01-01

    The mechanism by which the ferredoxin-thioredoxin system activates the target enzyme, NADP-malate dehydrogenase, was investigated by analyzing the sulfhydryl status of individual protein components with [ 14 C]iodoacetate and monobromobimane. The data indicate that ferredoxin-thioredoxin reductase (FTR)--an iron-sulfur enzyme present in oxygenic photosynthetic organisms--is the first member of a thiol chain that links light to enzyme regulation. FTR possesses a catalytically active dithiol group localized on the 13 kDa (similar) subunit, that occurs in all species investigated and accepts reducing equivalents from photoreduced ferredoxin and transfers them stoichiometrically to the disulfide form of thioredoxin m. The reduced thioredoxin m, in turn, reduces NADP-malate dehydrogenase, thereby converting it from an inactive (S-S) to an active (SH) form. The means by which FTR is able to combine electrons (from photoreduced ferredoxin) with protons (from the medium) to reduce its active disulfide group remains to be determined

  11. The effect of preparation parameters i thermal decomposition of ruthenium dioxide electrodes on chlorine elctro-catalytic activity

    International Nuclear Information System (INIS)

    Luu, Tran Le; Kim, Choon Soo; Kim, Ji Ye; Kim, Seong Hwan; Yoon, Je Yong

    2015-01-01

    When fabricating a RuO_2 electrode, the high electro-catalytic activity in chlorine evolution is considered as one of the most important factors. Thermal decomposition method carried out under various fabrication conditions including the types of solvents, precursors, and calcination times have led to the enhancement electro-catalytic activity of RuO_2 electrode in chlorine evolution. Nevertheless, it has not been fully investigated how these parameters directly affect to the chlorine evolution efficiency in the RuO_2 electrode. Therefore, the aim of this study was to investigate the effect on the chlorine evolution in RuO_2 electrodes, depending upon the preparation parameters including solvents, precursors, and calcination times. As major results, the chlorine evolution efficiency was dominantly affected by these three major preparation parameters. The RuO_2 electrode fabricated with ethanol as the solvent showed highest chlorine evolution efficiency. The choice of Ru(AcAc)_3 as precursor and the increase of the calcination time up to 3 h are also the good choices for increasing chlorine electrocatalytic activities. The chlorine evolution efficiency was not significantly related to the total voltammetric charge but to the outer voltammetric charge, which is affected by the morphology of the RuO_2 electrode surface. The size and number of cracks on the electrode surfaces or the outer voltammetric charges increased with easily evaporated solvents, decomposed precursors, and tensile stress from longer thermal treatments

  12. A Ta/W mixed addenda heteropolyacid with excellent acid catalytic activity and proton-conducting property

    Energy Technology Data Exchange (ETDEWEB)

    Li, Shujun; Peng, Qingpo [School of Chemistry and Chemical Engineering, Henan Key Laboratory of Boron Chemistry and Advanced Energy Materials, Henan Normal University, Xinxiang, Henan 453007 (China); Chen, Xuenian, E-mail: xnchen@htu.edu.cn [School of Chemistry and Chemical Engineering, Henan Key Laboratory of Boron Chemistry and Advanced Energy Materials, Henan Normal University, Xinxiang, Henan 453007 (China); Wang, Ruoya; Zhai, Jianxin; Hu, Weihua [School of Chemistry and Chemical Engineering, Henan Key Laboratory of Boron Chemistry and Advanced Energy Materials, Henan Normal University, Xinxiang, Henan 453007 (China); Ma, Fengji, E-mail: fengji.ma@yahoo.com [College of Chemistry and Chemical Engineering, Anyang Normal University, Anyang, Henan 453000 (China); Zhang, Jie, E-mail: jie.zhang@htu.edu.cn [School of Chemistry and Chemical Engineering, Henan Key Laboratory of Boron Chemistry and Advanced Energy Materials, Henan Normal University, Xinxiang, Henan 453007 (China); Liu, Shuxia [Key Laboratory of Polyoxometalates Science of Ministry of Education, College of Chemistry, Northeast Normal University, Changchun City, Jilin 130024 (China)

    2016-11-15

    A new HPAs H{sub 20}[P{sub 8}W{sub 60}Ta{sub 12}(H{sub 2}O){sub 4}(OH){sub 8}O{sub 236}]·125H{sub 2}O (H-1) which comprises a Ta/W mixed addenda heteropolyanion, 20 protons, and 125 crystalline water molecules has been prepared through ion-exchange method. The structure and properties of H-1 have been explored in detail. AC impedance measurements indicate that H-1 is a good solid state proton conducting material at room temperature with a conductivity value of 7.2×10{sup −3} S cm{sup −1} (25 °C, 30% RH). Cyclic voltammograms of H-1 indicate the electrocatalytic activity towards the reduction of nitrite. Hammett acidity constant H{sub 0} of H-1 in CH{sub 3}CN is −2.91, which is the strongest among the present known HPAs. Relatively, H-1 exhibits excellent catalytic activities toward acetal reaction. - Highlights: • A Ta/W mixed addenda Heteropolyacid (H-1) was isolated. • Hammett acidity constant H{sub 0} of H-1 is the strongest among the present known HPAs. • H-1 exhibits excellent catalytic activities toward acetal reaction. • H-1 is a good solid state proton conducting material at room temperature.

  13. The effect of preparation parameters i thermal decomposition of ruthenium dioxide electrodes on chlorine elctro-catalytic activity

    Energy Technology Data Exchange (ETDEWEB)

    Luu, Tran Le; Kim, Choon Soo; Kim, Ji Ye; Kim, Seong Hwan; Yoon, Je Yong [Dept. of Chemical and Biological Engineering, Institute of Chemical Process, Seoul National University,Seoul (Korea, Republic of)

    2015-05-15

    When fabricating a RuO{sub 2} electrode, the high electro-catalytic activity in chlorine evolution is considered as one of the most important factors. Thermal decomposition method carried out under various fabrication conditions including the types of solvents, precursors, and calcination times have led to the enhancement electro-catalytic activity of RuO{sub 2} electrode in chlorine evolution. Nevertheless, it has not been fully investigated how these parameters directly affect to the chlorine evolution efficiency in the RuO{sub 2} electrode. Therefore, the aim of this study was to investigate the effect on the chlorine evolution in RuO{sub 2} electrodes, depending upon the preparation parameters including solvents, precursors, and calcination times. As major results, the chlorine evolution efficiency was dominantly affected by these three major preparation parameters. The RuO{sub 2} electrode fabricated with ethanol as the solvent showed highest chlorine evolution efficiency. The choice of Ru(AcAc){sub 3} as precursor and the increase of the calcination time up to 3 h are also the good choices for increasing chlorine electrocatalytic activities. The chlorine evolution efficiency was not significantly related to the total voltammetric charge but to the outer voltammetric charge, which is affected by the morphology of the RuO{sub 2} electrode surface. The size and number of cracks on the electrode surfaces or the outer voltammetric charges increased with easily evaporated solvents, decomposed precursors, and tensile stress from longer thermal treatments.

  14. A novel disulfide bond in the SH2 Domain of the C-terminal Src kinase controls catalytic activity.

    Science.gov (United States)

    Mills, Jamie E; Whitford, Paul C; Shaffer, Jennifer; Onuchic, Jose N; Adams, Joseph A; Jennings, Patricia A

    2007-02-02

    The SH2 domain of the C-terminal Src kinase [Csk] contains a unique disulfide bond that is not present in other known SH2 domains. To investigate whether this unusual disulfide bond serves a novel function, the effects of disulfide bond formation on catalytic activity of the full-length protein and on the structure of the SH2 domain were investigated. The kinase activity of full-length Csk decreases by an order of magnitude upon formation of the disulfide bond in the distal SH2 domain. NMR spectra of the fully oxidized and fully reduced SH2 domains exhibit similar chemical shift patterns and are indicative of similar, well-defined tertiary structures. The solvent-accessible disulfide bond in the isolated SH2 domain is highly stable and far from the small lobe of the kinase domain. However, reduction of this bond results in chemical shift changes of resonances that map to a cluster of residues that extend from the disulfide bond across the molecule to a surface that is in direct contact with the small lobe of the kinase domain in the intact molecule. Normal mode analyses and molecular dynamics calculations suggest that disulfide bond formation has large effects on residues within the kinase domain, most notably within the active-site cleft. Overall, the data indicate that reversible cross-linking of two cysteine residues in the SH2 domain greatly impacts catalytic function and interdomain communication in Csk.

  15. Evolutionary divergence in the catalytic activity of the CAM-1, ROR1 and ROR2 kinase domains.

    Directory of Open Access Journals (Sweden)

    Travis W Bainbridge

    Full Text Available Receptor tyrosine kinase-like orphan receptors (ROR 1 and 2 are atypical members of the receptor tyrosine kinase (RTK family and have been associated with several human diseases. The vertebrate RORs contain an ATP binding domain that deviates from the consensus amino acid sequence, although the impact of this deviation on catalytic activity is not known and the kinase function of these receptors remains controversial. Recently, ROR2 was shown to signal through a Wnt responsive, β-catenin independent pathway and suppress a canonical Wnt/β-catenin signal. In this work we demonstrate that both ROR1 and ROR2 kinase domains are catalytically deficient while CAM-1, the C. elegans homolog of ROR, has an active tyrosine kinase domain, suggesting a divergence in the signaling processes of the ROR family during evolution. In addition, we show that substitution of the non-consensus residues from ROR1 or ROR2 into CAM-1 and MuSK markedly reduce kinase activity, while restoration of the consensus residues in ROR does not restore robust kinase function. We further demonstrate that the membrane-bound extracellular domain alone of either ROR1 or ROR2 is sufficient for suppression of canonical Wnt3a signaling, and that this domain can also enhance Wnt5a suppression of Wnt3a signaling. Based on these data, we conclude that human ROR1 and ROR2 are RTK-like pseudokinases.

  16. Reaction mechanisms and evaluation of effective process operation for catalytic oxidation and coagulation by ferrous solution and hydrogen peroxide

    Energy Technology Data Exchange (ETDEWEB)

    Lee, S.H.; Moon, H.J.; Kim, Y.M. [Dept. of Environmental Engineering, Sangmyung Univ., Cheonan (Korea); Bae, W.K. [Dept. of Civil and Environmental Engineering, Hanyang Univ., Ansan, Kyounggi (Korea)

    2003-07-01

    This research was carried out to evaluate the removal efficiencies of COD{sub cr} and colour for the dyeing wastewater by ferrous solution and the different dosage of H{sub 2}O{sub 2} in Fenton process. In the case of H{sub 2}O{sub 2} divided dosage, 7:3 was more effective than 3:7 to remove COD{sub cr} and colour. The results showed that COD was mainly removed by Fenton coagulation, where the ferric ions are formed in the initial step of Fenton reaction. On the other hand colour was removed by Fenton oxidation rather than Fenton coagulation. This paper also aims at pursuing to investigate the effective removal mechanisms using ferrous ion coagulation, ferric ion coagulation and Fenton oxidation process. The removal mechanism of COD{sub cr} and colour was mainly coagulation by ferrous ion, ferric ion and Fenton oxidation. The removal efficiencies were dependent on the ferric ion amount at the beginning of the reaction. However the final removal efficiency of COD and colour was in the order of Fenton oxidation, ferric ion coagulation and ferrous ion coagulation. The reason of the highest removal efficiency by Fenton oxidation can be explained by the chain reactions with ferrous solution, ferric ion and hydrogen peroxide. (orig.)

  17. Catalytic activity of dual catalysts system based on nano-manganese oxide and cobalt octacyanophthalocyanine toward four-electron reduction of oxygen in alkaline media

    International Nuclear Information System (INIS)

    Zhang, Dun; Chi, Dahe; Okajima, Takeyoshi; Ohsaka, Takeo

    2007-01-01

    The electrocatalysis of the dual functional catalysts system composed of electrolytic nano-manganese oxide (nano-MnOx) and cobalt octacyanophthalocyanine (CoPcCN) toward 4-electron reduction of oxygen (O 2 ) in alkaline media was studied. Nano-MnOx electrodeposited on the CoPcCN monolayer-modified glassy carbon (GC) electrode was clarified as the nano-rods with ca. 10-20 nm diameter by scanning electron microscopy. The peak current for O 2 reduction at the dual catalysts-modified GC electrode increases largely and the peak potential shifts by ca. 160 mV to the positive direction in cyclic voltammograms compared with those obtained at the bare GC electrode. The Koutecky-Levich plots indicate that the O 2 reduction at the dual catalysts-modified GC electrode is an apparent 4-electron process. Collection efficiencies obtained at the dual catalysts-modified GC electrode are much lower than those at the GC electrode and are almost similar to those at the Pt nano-particles modified GC electrode. The obtained results demonstrate that the dual catalysts system possesses a bifuctional catalytic activity for redox-mediating 2-electron reduction of O 2 to HO 2 - by CoPcCN as well as catalyzing the disproportionation of HO 2 - to OH - and O 2 by nano-MnOx, and enables an apparent 4-electron reduction of O 2 at a relatively low overpotential in alkaline media. In addition, it has been found that the cleaning of the dual catalysts-modified electrode by soaking in 0.1 M sulfuric acid solution enhances its catalytic activity toward the reduction of O 2

  18. Catalytic activity of Pd-doped Cu nanoparticles for hydrogenation as a single-atom-alloy catalyst.

    Science.gov (United States)

    Cao, Xinrui; Fu, Qiang; Luo, Yi

    2014-05-14

    The single atom alloy of extended surfaces is known to provide remarkably enhanced catalytic performance toward heterogeneous hydrogenation. Here we demonstrate from first principles calculations that this approach can be extended to nanostructures, such as bimetallic nanoparticles. The catalytic properties of the single-Pd-doped Cu55 nanoparticles have been systemically examined for H2 dissociation as well as H atom adsorption and diffusion, following the concept of single atom alloy. It is found that doping a single Pd atom at the edge site of the Cu55 shell can considerably reduce the activation energy of H2 dissociation, while the single Pd atom doped at the top site or in the inner layers is much less effective. The H atom adsorption on Cu55 is slightly stronger than that on the Cu(111) surface; however, a larger nanoparticle that contains 147 atoms could effectively recover the weak binding of the H atoms. We have also investigated the H atom diffusion on the 55-atom nanoparticle and found that spillover of the produced H atoms could be a feasible process due to the low diffusion barriers. Our results have demonstrated that facile H2 dissociation and weak H atom adsorption could be combined at the nanoscale. Moreover, the effects of doping one more Pd atom on the H2 dissociation and H atom adsorption have also been investigated. We have found that both the doping Pd atoms in the most stable configuration could independently exhibit their catalytic activity, behaving as two single-atom-alloy catalysts.

  19. Contribution of Arginine 13 to the Catalytic Activity of Human Class Pi Glutathione Transferase P1-1

    International Nuclear Information System (INIS)

    Kong, Ji Na; Jo, Dong Hyeon; Do, Hyun Dong; Lee, Jin Ju; Kong, Kwang Hoon

    2010-01-01

    Arg13 is a conserved active-site residue in all known Pi class glutathione S-transferases (GSTs) and in most Alpha class GSTs. To evaluate its contribution to substrate binding and catalysis of this residue, three mutants (R13A, R13K, and R13L) were expressed in Escherichia coli and purified by GSH affinity chromatography. The substitutions of Arg13 significantly affected GSH-conjugation activity, while scarcely affecting glutathione peroxidase or steroid isomerase activities. Mutation of Arg13 into Ala largely reduced the GSH-conjugation activity by approximately 85 - 95%, whereas substitutions by Lys and Leu barely affected activity. These results suggest that, in the GSH-conjugation activity of hGST P1-1, the contribution of Arg13 toward catalytic activity is highly dependent on substrate specificities and the size of the side chain at position 13. From the kinetic parameters, introduction of larger side chains at position 13 results in stronger affinity (Leu > Lys, Arg > Ala) towards GSH. The substitutions of Arg13 with alanine and leucine significantly affected k cat , whereas substitution with Lys was similar to that of the wild type, indicating the significance of a positively charged residue at position 13. From the plots of log (k cat /K m CDNB ) against pH, the pK a values of the thiol group of GSH bound in R13A, R13K, and R13L were estimated to be 1.8, 1.4, and 1.8 pK units higher than the pK a value of the wildtype enzyme, demonstrating the contribution of the Arg13 guanidinium group to the electrostatic field in the active site. From these results, we suggest that contribution of Arg13 in substrate binding is highly dependent on the nature of the electrophilic substrates, while in the catalytic mechanism, it stabilizes the GSH thiolate through hydrogen bonding

  20. Using scaling relations to understand trends in the catalytic activity of transition metals

    International Nuclear Information System (INIS)

    Jones, G; Bligaard, T; Abild-Pedersen, F; Noerskov, J K

    2008-01-01

    A method is developed to estimate the potential energy diagram for a full catalytic reaction for a range of late transition metals on the basis of a calculation (or an experimental determination) for a single metal. The method, which employs scaling relations between adsorption energies, is illustrated by calculating the potential energy diagram for the methanation reaction and ammonia synthesis for 11 different metals on the basis of results calculated for Ru. It is also shown that considering the free energy diagram for the reactions, under typical industrial conditions, provides additional insight into reactivity trends

  1. Catalytic wet air oxidation of bisphenol A solution in a batch-recycle trickle-bed reactor over titanate nanotube-based catalysts.

    Science.gov (United States)

    Kaplan, Renata; Erjavec, Boštjan; Senila, Marin; Pintar, Albin

    2014-10-01

    Catalytic wet air oxidation (CWAO) is classified as an advanced oxidation process, which proved to be highly efficient for the removal of emerging organic pollutant bisphenol A (BPA) from water. In this study, BPA was successfully removed in a batch-recycle trickle-bed reactor over bare titanate nanotube-based catalysts at very short space time of 0.6 min gCAT g(-1). The as-prepared titanate nanotubes, which underwent heat treatment at 600 °C, showed high activity for the removal of aqueous BPA. Liquid-phase recycling (5- or 10-fold recycle) enabled complete BPA conversion already at 200 °C, together with high conversion of total organic carbon (TOC), i.e., 73 and 98 %, respectively. The catalyst was chemically stable in the given range of operating conditions for 189 h on stream.

  2. Substrate-mediated enhanced activity of Ru nanoparticles in catalytic hydrogenation of benzene

    KAUST Repository

    Liu, Xin

    2012-01-01

    The impact of carbon substrate-Ru nanoparticle interactions on benzene and hydrogen adsorption that is directly related to the performance in catalytic hydrogenation of benzene has been investigated by first-principles based calculations. The stability of Ru 13 nanoparticles is enhanced by the defective graphene substrate due to the hybridization between the dsp states of the Ru 13 particle with the sp 2 dangling bonds at the defect sites. The local curvature formed at the interface will also raise the Ru atomic diffusion barrier, and prohibit the particle sintering. The strong interfacial interaction results in the shift of averaged d-band center of the deposited Ru nanoparticle, from -1.41 eV for a freestanding Ru 13 particle, to -1.17 eV for the Ru/Graphene composites, and to -1.54 eV on mesocellular foam carbon. Accordingly, the adsorption energies of benzene are increased from -2.53 eV for the Ru/mesocellular foam carbon composites, to -2.62 eV on freestanding Ru 13 particles, to -2.74 eV on Ru/graphene composites. A similar change in hydrogen adsorption is also observed, and all these can be correlated to the shift of the d-band center of the nanoparticle. Thus, Ru nanoparticles graphene composites are expected to exhibit both high stability and superior catalytic performance in hydrogenation of arenes. © 2012 The Royal Society of Chemistry.

  3. Resorcinol adsorption from aqueous solution over activated carbon

    International Nuclear Information System (INIS)

    Blanco, Diego A; Giraldo, Liliana; Moreno, Juan C

    2007-01-01

    In this paper, the adsorption behavior of Resorcinol a monohydroxylated phenol, poorly acid to 298 K, over activated carbon is analyzed by studying the solution's pH influence and the surface reduction in the adsorption process. To do this, an activated carbon of lignocellulose origin and a reduced activated carbon was used. The interaction solid solution is characterized by the analyses of adsorption in the isotherms to 298 K and pH values of 7. 00, 9.00 and 11.00 for a period of 48 hours. The capacity adsorption of activated carbons increases when the solution's pH decreases and the retained amount increases in the reduced coal to the pH of maximum adsorption.

  4. Catalytic activity of laminated compounds of graphite with transitions metals in decomposition of alcohols and formic acid

    International Nuclear Information System (INIS)

    Novikov, Yu.N.; Lapkina, N.D.; Vol'pin, M.E.

    1976-01-01

    The catalytic activity is studied of laminated graphite compounds with Fe, Co, Ni, Cu, Mo, W and Mn both in the reduced and oxidized forms in gas phase decomposition reactions of isopropyl, n-butyl, cyclohexyl, and 4-tret-butylcyclohexyl alcohols, and also formic acid. All the catalysts are shown to be active in the reactions where isopropyl and n-butyl alcohols undergo decomposition. The laminated compounds of graphite with Co and Ni both in the oxidized and reduction form are the most active catalysts of the selective decomposition of alcohols to aldehydes and ketones, and also formic acid to CO 2 and H 2 . The kinetics of a number of reactions is found to obey the second order equation with allowance made for the system volume

  5. The influence of calcination temperature on catalytic activities in a Co based catalyst for CO2 dry reforming

    International Nuclear Information System (INIS)

    Song, Sang-Hoon; Son, Ju-Hee; Budiman, Anatta Wahyu; Choi, Myoung-Jae; Chang, Tae-Sun; Shin, Chae-Ho

    2014-01-01

    The carbon dioxide dry reforming of methane (CDR) reaction could be thermodynamically favored in the range of 800 to 1,000 .deg. C. However, the catalyst in this reaction should be avoided at the calcination temperature over 800 .deg. C since strong metal support interaction (SMSI) in this temperature range can decrease activity due to loss of active sites. Therefore, we focused on optimizing the temperature of pretreatment and a comparison of surface characterization results for CDR. Results related to metal sintering over support, re-dispersion by changing of particle size of metal-support, and strong metal support interaction were observed and confirmed in this work. In our conclusion, optimum calcination temperature for a preparation of catalyst was proposed that 400 .deg. C showed a higher and more stable catalytic activity without changing of support characteristics

  6. Hammerhead ribozyme activity and oligonucleotide duplex stability in mixed solutions of water and organic compounds

    Directory of Open Access Journals (Sweden)

    Shu-ichi Nakano

    2014-01-01

    Full Text Available Nucleic acids are useful for biomedical targeting and sensing applications in which the molecular environment is different from that of a dilute aqueous solution. In this study, the influence of various types of mixed solutions of water and water-soluble organic compounds on RNA was investigated by measuring the catalytic activity of the hammerhead ribozyme and the thermodynamic stability of an oligonucleotide duplex. The compounds with a net neutral charge, such as poly(ethylene glycol, small primary alcohols, amide compounds, and aprotic solvent molecules, added at high concentrations changed the ribozyme-catalyzed RNA cleavage rate, with the magnitude of the effect dependent on the NaCl concentration. These compounds also changed the thermodynamic stability of RNA base pairs of an oligonucleotide duplex and its dependence on the NaCl concentration. Specific interactions with RNA molecules and reduced water activity could account for the inhibiting effects on the ribozyme catalysis and destabilizing effects on the duplex stability. The salt concentration dependence data correlated with the dielectric constant, but not with water activity, viscosity, and the size of organic compounds. This observation suggests the significance of the dielectric constant effects on the RNA reactions under molecular crowding conditions created by organic compounds.

  7. Modeling and Simulation of the Hydrogenation of α-Methylstyrene on Catalytically Active Metal Foams as Tubular Reactor Packing

    Directory of Open Access Journals (Sweden)

    Farzad Lali

    2016-01-01

    Full Text Available This work presents a one-dimensional reactor model for a tubular reactor packed with a catalytically active foam packing with a pore density of 30 PPI in cocurrent upward flow in the example of hydrogenation reaction of α-methylstyrene to cumene. This model includes material, enthalpy, and momentum balances as well as continuity equations. The model was solved within the parameter space applied for experimental studies under assumption of a bubbly flow. The method of orthogonal collocation on finite elements was applied. For isothermal and polytropic processes and steady state conditions, axial profiles for concentration, temperature, fluid velocities, pressure, and liquid holdup were computed and the conversions for various gas and liquid flow rates were validated with experimental results. The obtained results were also compared in terms of space time yield and catalytic activity with experimental results and stirred tank and also with random packed bed reactor. The comparison shows that the application of solid foams as reactor packing is advantageous compared to the monolithic honeycombs and random packed beds.

  8. Recovery of homogeneous polyoxometallate catalysts from aqueous and organic media by a mesoporous ceramic membrane without loss of catalytic activity.

    Science.gov (United States)

    Roy Chowdhury, Sankhanilay; Witte, Peter T; Blank, Dave H A; Alsters, Paul L; Ten Elshof, Johan E

    2006-04-03

    The recovery of homogeneous polyoxometallate (POM) oxidation catalysts from aqueous and non-aqueous media by a nanofiltration process using mesoporous gamma-alumina membranes is reported. The recovery of Q(12)[WZn(3)(ZnW(9)O(34))(2)] (Q=[MeN(n-C(8)H(17))(3)](+)) from toluene-based media was quantitative within experimental error, while up to 97 % of Na(12)[WZn(3)(ZnW(9)O(34))(2)] could be recovered from water. The toluene-soluble POM catalyst was used repeatedly in the conversion of cyclooctene to cyclooctene oxide and separated from the product mixture after each reaction. The catalytic activity increased steadily with the number of times that the catalyst had been recycled, which was attributed to partial removal of the excess QCl that is known to have a negative influence on the catalytic activity. Differences in the permeability of the membrane for different liquid media can be attributed to viscosity differences and/or capillary condensation effects. The influence of membrane pore radius on permeability and recovery is discussed.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2017-02-28

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

  10. Boosting Chemical Stability, Catalytic Activity, and Enantioselectivity of Metal-Organic Frameworks for Batch and Flow Reactions.

    Science.gov (United States)

    Chen, Xu; Jiang, Hong; Hou, Bang; Gong, Wei; Liu, Yan; Cui, Yong

    2017-09-27

    A key challenge in heterogeneous catalysis is the design and synthesis of heterogeneous catalysts featuring high catalytic activity, selectivity, and recyclability. Here we demonstrate that high-performance heterogeneous asymmetric catalysts can be engineered from a metal-organic framework (MOF) platform by using a ligand design strategy. Three porous chiral MOFs with the framework formula [Mn 2 L(H 2 O) 2 ] are prepared from enantiopure phosphono-carboxylate ligands of 1,1'-biphenol that are functionalized with 3,5-bis(trifluoromethyl)-, bismethyl-, and bisfluoro-phenyl substituents at the 3,3'-position. For the first time, we show that not only chemical stability but also catalytic activity and stereoselectivity of the MOFs can be tuned by modifying the ligand structures. Particularly, the MOF incorporated with -CF 3 groups on the pore walls exhibits enhanced tolerance to water, weak acid, and base compared with the MOFs with -F and -Me groups. Under both batch and flow reaction systems, the CF 3 -containing MOF demonstrated excellent reactivity, selectivity, and recyclability, affording high yields and enantioselectivities for alkylations of indoles and pyrrole with a range of ketoesters or nitroalkenes. In contrast, the corresponding homogeneous catalysts gave low enantioselectivity in catalyzing the tested reactions.

  11. Catalytic Oxidation of Soot on a Novel Active Ca-Co Dually-Doped Lanthanum Tin Pyrochlore Oxide

    Directory of Open Access Journals (Sweden)

    Lijie Ai

    2018-04-01

    Full Text Available A novel active Ca-Co dually-doping pyrochlore oxide La2−xCaxSn2−yCoyO7 catalyst was synthesized by the sol-gel method for catalytic oxidation of soot particulates. The microstructure, atomic valence, reduction, and adsorption performance were investigated by X-ray powder diffraction (XRD, scanning electron microscope (SEM, Fourier-transform infrared spectroscopy (FT-IR, X-ray photoelectron spectroscopy (XPS, H2-TPR (temperature-programmed reduction, and in situ diffuse reflection infrared Fourier transformed (DRIFTS techniques. Temperature programmed oxidation (TPO tests were performed with the mixture of soot-catalyst under tight contact conditions to evaluate the catalytic activity for soot combustion. Synergetic effect between Ca and Co improved the structure and redox properties of the solids, increased the surface oxygen vacancies, and provided a suitable electropositivity for oxide, directly resulting in the decreased ignition temperature for catalyzed soot oxidation as low as 317 °C. The presence of NO in O2 further promoted soot oxidation over the catalysts with the ignition temperature decreased to about 300 °C. The DRIFTS results reveal that decomposition of less stable surface nitrites may account for NO2 formation in the ignition period of soot combustion, which thus participate in the auxiliary combustion process.

  12. Highly Oriented Growth of Catalytically Active Zeolite ZSM-5 Films with a Broad Range of Si/Al Ratios.

    Science.gov (United States)

    Fu, Donglong; Schmidt, Joel E; Ristanović, Zoran; Chowdhury, Abhishek Dutta; Meirer, Florian; Weckhuysen, Bert M

    2017-09-04

    Highly b-oriented zeolite ZSM-5 films are critical for applications in catalysis and separations and may serve as models to study diffusion and catalytic properties in single zeolite channels. However, the introduction of catalytically active Al 3+ usually disrupts the orientation of zeolite films. Herein, using structure-directing agents with hydroxy groups, we demonstrate a new method to prepare highly b-oriented zeolite ZSM-5 films with a broad range of Si/Al ratios (Si/Al=45 to ∞). Fluorescence micro-(spectro)scopy was used to monitor misoriented microstructures, which are invisible to X-ray diffraction, and show Al 3+ framework incorporation and illustrate the differences between misoriented and b-oriented films. The methanol-to-hydrocarbons process was studied by operando UV/Vis diffuse reflectance micro-spectroscopy with on-line mass spectrometry, showing that the b-oriented zeolite ZSM-5 films are active and stable under realistic process conditions. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

  13. Enhanced catalytic hydrogenation activity of Ni/reduced graphene oxide nanocomposite prepared by a solid-state method

    Science.gov (United States)

    Li, Yizhao; Cao, Yali; Jia, Dianzeng

    2018-01-01

    A simple solid-state method has been applied to synthesize Ni/reduced graphene oxide (Ni/rGO) nanocomposite under ambient condition. Ni nanoparticles with size of 10-30 nm supported on reduced graphene oxide (rGO) nanosheets are obtained through one-pot solid-state co-reduction among nickel chloride, graphene oxide, and sodium borohydride. The Ni/rGO nanohybrid shows enhanced catalytic activity toward the reduction of p-nitrophenol (PNP) into p-aminophenol compared with Ni nanoparticles. The results of kinetic research display that the pseudo-first-order rate constant for hydrogenation reaction of PNP with Ni/rGO nanocomposite is 7.66 × 10-3 s-1, which is higher than that of Ni nanoparticles (4.48 × 10-3 s-1). It also presents superior turnover frequency (TOF, 5.36 h-1) and lower activation energy ( E a, 29.65 kJ mol-1) in the hydrogenation of PNP with Ni/rGO nanocomposite. Furthermore, composite catalyst can be magnetically separated and reused for five cycles. The large surface area and high electron transfer property of rGO support are beneficial for good catalytic performance of Ni/rGO nanocomposite. Our study demonstrates a simple approach to fabricate metal-rGO heterogeneous nanostructures with advanced functions.

  14. Ensemble averaged structure–function relationship for nanocrystals: effective superparamagnetic Fe clusters with catalytically active Pt skin [Ensemble averaged structure-function relationship for composite nanocrystals: magnetic bcc Fe clusters with catalytically active fcc Pt skin

    Energy Technology Data Exchange (ETDEWEB)

    Petkov, Valeri [Central Michigan University, Mt. Pleasant, MI (United States); Prasai, Binay [Central Michigan University, Mt. Pleasant, MI (United States); Shastri, Sarvjit [Argonne National Lab. (ANL), Argonne, IL (United States). X-ray Science Division; Park, Hyun-Uk [Sungkyunkwan University, Suwon (Korea). Department of Chemistry; Kwon, Young-Uk [Sungkyunkwan University, Suwon (Korea). Department of Chemistry; Skumryev, Vassil [Institucio Catalana de Recerca i Estudis Avançats (ICREA), Barcelona (Spain); Universitat Autònoma de Barcelona (Spain). Department of Physics

    2017-09-12

    Practical applications require the production and usage of metallic nanocrystals (NCs) in large ensembles. Besides, due to their cluster-bulk solid duality, metallic NCs exhibit a large degree of structural diversity. This poses the question as to what atomic-scale basis is to be used when the structure–function relationship for metallic NCs is to be quantified precisely. In this paper, we address the question by studying bi-functional Fe core-Pt skin type NCs optimized for practical applications. In particular, the cluster-like Fe core and skin-like Pt surface of the NCs exhibit superparamagnetic properties and a superb catalytic activity for the oxygen reduction reaction, respectively. We determine the atomic-scale structure of the NCs by non-traditional resonant high-energy X-ray diffraction coupled to atomic pair distribution function analysis. Using the experimental structure data we explain the observed magnetic and catalytic behavior of the NCs in a quantitative manner. Lastly, we demonstrate that NC ensemble-averaged 3D positions of atoms obtained by advanced X-ray scattering techniques are a very proper basis for not only establishing but also quantifying the structure–function relationship for the increasingly complex metallic NCs explored for practical applications.

  15. Influence of Ce-precursor and fuel on structure and catalytic activity of combustion synthesized Ni/CeO{sub 2} catalysts for biogas oxidative steam reforming

    Energy Technology Data Exchange (ETDEWEB)

    Vita, Antonio, E-mail: antonio.vita@itae.cnr.it; Italiano, Cristina; Fabiano, Concetto; Laganà, Massimo; Pino, Lidia

    2015-08-01

    A series of nanosized Ni/CeO{sub 2} catalysts were prepared by Solution Combustion Synthesis (SCS) varying the fuel (oxalyldihydrazide, urea, carbohydrazide and glycerol), the cerium precursor (cerium nitrate and cerium ammonium nitrate) and the nickel loading (ranging between 3.1 and 15.6 wt%). The obtained powders were characterized by X-ray Diffraction (XRD), N{sub 2}-physisorption, CO-chemisorption, Temperature Programmed Reduction (H{sub 2}-TPR) and Scanning Electron Microscopy (SEM). The catalytic activity towards the Oxy Steam Reforming (OSR) of biogas was assessed. The selected operating variables have a strong influence on the nature of combustion and, in turn, on the morphological and structural properties of the synthesized catalysts. Particularly, the use of urea allows to improve nickel dispersion, surface area, particle size and reducibility of the catalysts, affecting positively the biogas OSR performances. - Highlights: • Synthesis of Ni/CeO{sub 2} nanopowders by quick and easy solution combustion synthesis. • The fuel and precursor drive the structural and morphological properties of the catalysts. • The use of urea as fuel allows to improve nickel dispersion, surface area and particle size. • Ni/CeO{sub 2} (7.8 wt% of Ni loading) powders synthesized by urea route exhibits high performances for the biogas OSR process.

  16. Influence of Ce-precursor and fuel on structure and catalytic activity of combustion synthesized Ni/CeO2 catalysts for biogas oxidative steam reforming

    International Nuclear Information System (INIS)

    Vita, Antonio; Italiano, Cristina; Fabiano, Concetto; Laganà, Massimo; Pino, Lidia

    2015-01-01

    A series of nanosized Ni/CeO 2 catalysts were prepared by Solution Combustion Synthesis (SCS) varying the fuel (oxalyldihydrazide, urea, carbohydrazide and glycerol), the cerium precursor (cerium nitrate and cerium ammonium nitrate) and the nickel loading (ranging between 3.1 and 15.6 wt%). The obtained powders were characterized by X-ray Diffraction (XRD), N 2 -physisorption, CO-chemisorption, Temperature Programmed Reduction (H 2 -TPR) and Scanning Electron Microscopy (SEM). The catalytic activity towards the Oxy Steam Reforming (OSR) of biogas was assessed. The selected operating variables have a strong influence on the nature of combustion and, in turn, on the morphological and structural properties of the synthesized catalysts. Particularly, the use of urea allows to improve nickel dispersion, surface area, particle size and reducibility of the catalysts, affecting positively the biogas OSR performances. - Highlights: • Synthesis of Ni/CeO 2 nanopowders by quick and easy solution combustion synthesis. • The fuel and precursor drive the structural and morphological properties of the catalysts. • The use of urea as fuel allows to improve nickel dispersion, surface area and particle size. • Ni/CeO 2 (7.8 wt% of Ni loading) powders synthesized by urea route exhibits high performances for the biogas OSR process

  17. 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.

  18. The Investigation of Electron Beam Catalytical Oxidation Process Efficiency with Potassium Persulfate in Removal Humic Acid from Aqueous Solutions

    Directory of Open Access Journals (Sweden)

    MT Ghaneian

    2015-05-01

    Results: Based on the results, changes in pH had little effect on the Humic acid removal efficiency. The average, with increasing of pH from 4 to 10, the removal efficiency of humic acid from 72.59% to 73.36% increased, respectively. The results showed that increasing of the dose from 1 to 15 kGy, humic acid removal efficiency increases. Based on results by increasing of persulfate concentration, the removal efficiency increased so that with increasing of concentration of potassium persulfate from 0.1 to 0.5 mmol/100cc, removal efficiency from 69.43% to 83.82% was increased. Kinetic experiments showed that the decomposition of humic acid by electron beam radiation followed the second-order kinetic. Conclusion: The data from this study showed that the aqueous solution containing acid Humic is decomposed effectively by electron beams irradiation. Addition of potassium persulfate can be have significant improvements in removal efficiency of humic acid in the presence of electron beam.

  19. Reactivity of nanoaggregations of platinum on supports of different nature in reactions of catalytic decomposition of hydrazine in acid media

    International Nuclear Information System (INIS)

    Anan'ev, A.V.; Boltoeva, M.Yu.; Grigor'ev, M.S.; Shilov, V.P.; Sharygin, L.M.

    2006-01-01

    Platinized catalysts on the basis of supports of different chemical nature are tested in reactions of catalytic hydrazine decomposition in perchloric and nitric acid solutions. In perchloric acid catalytic activity of catalysts on the basis of ceramic materials of Termoksid brand is higher of activity of catalysts on the basis of amorphous silica gel. In nitric acid solutions opposite dependence is observed. Tendency of ceramic supports to peptization in acid solutions is pointed out. Results obtained are interpreted using conceptions of energetic heterogeneity of surface atoms and hydrazine catalytic decomposition mechanisms in different media [ru

  20. Electrochemical catalytic activities of nanoporous palladium rods for methanol electro-oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Xiaoguang; Wang, Weimin; Qi, Zhen; Zhao, Changchun; Ji, Hong; Zhang, Zhonghua [Key Laboratory for Liquid-Solid Structural Evolution and Processing of Materials (MOE), School of Materials Science and Engineering, Shandong University, Jingshi Road 73, Jinan 250061 (China)

    2010-10-01

    A novel electrocatalyst, nanoporous palladium (npPd) rods can be facilely fabricated by dealloying a binary Al{sub 80}Pd{sub 20} alloy in a 5 wt.% HCl aqueous solution under free corrosion conditions. The microstructure of these nanoporous palladium rods has been characterized using scanning electron microscopy and transmission electron microscopy. The results show that each Pd rod is several microns in length and several hundred nanometers in diameter. Moreover, all the rods exhibit a typical three-dimensional bicontinuous interpenetrating ligament-channel structure with length scale of 15-20 nm. The electrochemical experiments demonstrate that these peculiar nanoporous palladium rods (mixed with Vulcan XC-72 carbon powders to form a npPd/C catalyst) reveal a superior electrocatalytic performance toward methanol oxidation in the alkaline media. In addition, the electrocatalytic activity obviously depends on the metal loading on the electrode and will reach to the highest level (223.52 mA mg{sup -1}) when applying 0.4 mg cm{sup -2} metal loading on the electrode. Moreover, a competing adsorption mechanism should exist when performing methanol oxidation on the surface of npPd rods, and the electro-oxidation reaction is a diffusion-controlled electrochemical process. Due to the advantages of simplicity and high efficiency in the mass production, the npPd rods can act as a promising candidate for the anode catalyst for direct methanol fuel cells (DMFCs). (author)

  1. A comparative investigation of metal-support interactions on the catalytic activity of Pt nanoparticles for ethanol oxidation in alkaline medium

    Science.gov (United States)

    Godoi, Denis R. M.; Villullas, Hebe M.; Zhu, Fu-Chun; Jiang, Yan-Xia; Sun, Shi-Gang; Guo, Junsong; Sun, Lili; Chen, Rongrong

    2016-04-01

    The effects of interactions of Pt nanoparticles with hybrid supports on reactivity towards ethanol oxidation in alkaline solution are investigated. Studies involve catalysts with identical Pt nanoparticles on six hybrid supports containing carbon powder and transition metal oxides (TiO2, ZrO2, SnO2, CeO2, MoO3 and WO3). In situ X-ray absorption spectroscopy (XAS) results evidence that metal-support interactions produce changes in the Pt 5d band vacancy, which appears to determine the catalytic activity. The highest and lowest activities are observed for Pt nanoparticles on hybrid supports containing TiO2 and CeO2, respectively. Further studies are presented for these two catalysts. In situ FTIR reflection spectroscopy measurements, taken using both multi-stepped FTIR spectroscopy (MS-FTIR) and single potential alteration FTIR spectroscopy (SPA-FTIR), evidence that the main product of ethanol oxidation is acetate, although signals attributed to carbonate and CO2 indicate some differences in CO2 production. Fuel cell performances of these catalysts, tested in a 4.5 cm2 single cell at different temperatures (40-90 °C) show good agreement with data obtained by electrochemical techniques. Results of this comprehensive study point out the possibility of compensating a reduction of noble metal load with an increase in activity promoted by interactions between metallic nanoparticles and a support.

  2. Nitrated graphene oxide and its catalytic activity in thermal decomposition of ammonium perchlorate

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Wenwen; Luo, Qingping; Duan, Xiaohui [State Key Laboratory Cultivation Base for Nonmetal Composites and Functional Materials, Southwest University of Science and Technology, Mianyang 621010 (China); Zhou, Yong [Eco-materials and Renewable Energy Research Center (ERERC), School of Physics, National Lab of Solid State Microstructure, ERERC, Nanjing University, Nanjing 210093 (China); Pei, Chonghua, E-mail: peichonghua@swust.edu.cn [State Key Laboratory Cultivation Base for Nonmetal Composites and Functional Materials, Southwest University of Science and Technology, Mianyang 621010 (China)

    2014-02-01

    Highlights: • The NGO was synthesized by nitrifying homemade GO. • The N content of resulted NGO is up to 1.45 wt.%. • The NGO can facilitate the decomposition of AP and release much heat. - Abstract: Nitrated graphene oxide (NGO) was synthesized by nitrifying homemade GO with nitro-sulfuric acid. Fourier transform infrared spectroscopy (FTIR), laser Raman spectroscopy, CP/MAS {sup 13}C NMR spectra and X-ray photoelectron spectroscopy (XPS) were used to characterize the structure of NGO. The thickness and the compositions of GO and NGO were analyzed by atomic force microscopy (AFM) and elemental analysis (EA), respectively. The catalytic effect of the NGO for the thermal decomposition of ammonium perchlorate (AP) was investigated by differential scanning calorimetry (DSC). Adding 10% of NGO to AP decreases the decomposition temperature by 106 °C and increases the apparent decomposition heat from 875 to 3236 J/g.

  3. Nitrated graphene oxide and its catalytic activity in thermal decomposition of ammonium perchlorate

    International Nuclear Information System (INIS)

    Zhang, Wenwen; Luo, Qingping; Duan, Xiaohui; Zhou, Yong; Pei, Chonghua

    2014-01-01

    Highlights: • The NGO was synthesized by nitrifying homemade GO. • The N content of resulted NGO is up to 1.45 wt.%. • The NGO can facilitate the decomposition of AP and release much heat. - Abstract: Nitrated graphene oxide (NGO) was synthesized by nitrifying homemade GO with nitro-sulfuric acid. Fourier transform infrared spectroscopy (FTIR), laser Raman spectroscopy, CP/MAS 13 C NMR spectra and X-ray photoelectron spectroscopy (XPS) were used to characterize the structure of NGO. The thickness and the compositions of GO and NGO were analyzed by atomic force microscopy (AFM) and elemental analysis (EA), respectively. The catalytic effect of the NGO for the thermal decomposition of ammonium perchlorate (AP) was investigated by differential scanning calorimetry (DSC). Adding 10% of NGO to AP decreases the decomposition temperature by 106 °C and increases the apparent decomposition heat from 875 to 3236 J/g

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

    Science.gov (United States)

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

    2017-05-01

    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 NaBH4, 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.

  5. Free-Standing Metal Oxide Nanoparticle Superlattices Constructed with Engineered Protein Containers Show in Crystallo Catalytic Activity.

    Science.gov (United States)

    Lach, Marcel; Künzle, Matthias; Beck, Tobias

    2017-12-11

    The construction of defined nanostructured catalysts is challenging. In previous work, we established a strategy to assemble binary nanoparticle superlattices with oppositely charged protein containers as building blocks. Here, we show that these free-standing nanoparticle superlattices are catalytically active. The metal oxide nanoparticles inside the protein scaffold are accessible for a range of substrates and show oxidase-like and peroxidase-like activity. The stable superlattices can be reused for several reaction cycles. In contrast to bulk nanoparticle-based catalysts, which are prone to aggregation and difficult to characterize, nanoparticle superlattices based on engineered protein containers provide an innovative synthetic route to structurally defined heterogeneous catalysts with control over nanoparticle size and composition. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Enhancement of catalytic activity of platinum-based nanoparticles towards electrooxidation of ethanol through interfacial modification with heteropolymolybdates

    Science.gov (United States)

    Barczuk, Piotr J.; Lewera, Adam; Miecznikowski, Krzysztof; Zurowski, Artur; Kulesza, Pawel J.

    As evidenced from the increase of electrocatalytic currents measured under voltammetric and chronoamperometric conditions, the activity of bimetallic Pt-Ru and Pt-Sn nanoparticles towards oxidation of ethanol is increased by modification of their surfaces with ultra-thin films of phosphododecamolybdic acid (H 3PMo 12O 40). The enhancement effect has been most pronounced in a case of heteropolymolybdate-modified carbon-supported Pt-Sn catalysts. Independent high-resolution XPS measurements indicate the ability of heteropolymolybdates to stabilize tin (in bimetallic Pt-Sn particles) at higher oxidation states (presumably as tin oxo species). The overall activation effect may also be ascribed to changes in the morphology of catalytic films following modification with heteropolymolybdates. Presence of the polyoxometallate is also likely to increase of the interfacial population of reactive oxo groups in the vicinity of platinum centers.

  7. Enhancement of catalytic activity of platinum-based nanoparticles towards electrooxidation of ethanol through interfacial modification with heteropolymolybdates

    Energy Technology Data Exchange (ETDEWEB)

    Barczuk, Piotr J.; Lewera, Adam; Miecznikowski, Krzysztof; Zurowski, Artur; Kulesza, Pawel J. [Department of Chemistry, University of Warsaw, Pasteura 1, PL-02-093 Warsaw (Poland)

    2010-05-01

    As evidenced from the increase of electrocatalytic currents measured under voltammetric and chronoamperometric conditions, the activity of bimetallic Pt-Ru and Pt-Sn nanoparticles towards oxidation of ethanol is increased by modification of their surfaces with ultra-thin films of phosphododecamolybdic acid (H{sub 3}PMo{sub 12}O{sub 40}). The enhancement effect has been most pronounced in a case of heteropolymolybdate-modified carbon-supported Pt-Sn catalysts. Independent high-resolution XPS measurements indicate the ability of heteropolymolybdates to stabilize tin (in bimetallic Pt-Sn particles) at higher oxidation states (presumably as tin oxo species). The overall activation effect may also be ascribed to changes in the morphology of catalytic films following modification with heteropolymolybdates. Presence of the polyoxometallate is also likely to increase of the interfacial population of reactive oxo groups in the vicinity of platinum centers. (author)

  8. 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.

  9. A Facile synthesis of superparamagnetic Fe3O4 nanofibers with superior peroxidase-like catalytic activity for sensitive colorimetric detection of L-cysteine

    Science.gov (United States)

    Chen, Sihui; Chi, Maoqiang; Zhu, Yun; Gao, Mu; Wang, Ce; Lu, Xiaofeng

    2018-05-01

    Superaramagnetic Fe3O4 nanomaterials are good candidates as enzyme mimics due to their excellent catalytic activity, high stability and facile synthesis. However, the morphology of Fe3O4 nanomaterials has much influence on their enzyme-like catalytic activity. In this work, we have developed a simple polymer-assisted thermochemical reduction approach to prepare Fe3O4 nanofibers for peroxidase-like catalytic applications. The as-prepared Fe3O4 nanofibers show a higher catalytic activity than commercial Fe3O4 nanoparticles. The steady-state kinetic assay result shows that the Michaelis-Menten constant value of the as-obtained Fe3O4 nanofibers is similar to that of horseradish peroxidase (HRP), indicating their superior affinity to the 3,3‧,5,5‧-tetramethylbenzidine (TMB) and H2O2 substrate. Based on the outstanding catalytic activity, a sensing platform for the detection of L-cysteine has been performed and the limit of detection is as low as 0.028 μM. In addition, an excellent selectivity toward L-cysteine over other types of amino acids, glucose and metal ions has been achieved as well. This work offers an original means for the fabrication of superparamagnetic Fe3O4 nanofibers and demonstrates their delightful potential applications in the fields of biosensing, environmental monitoring, and medical diagnostics.

  10. Gas cleaning and hydrogen sulfide removal for COREX coal gas by sorption enhanced catalytic oxidation over recyclable activated carbon desulfurizer.

    Science.gov (United States)

    Sun, Tonghua; Shen, Yafei; Jia, Jinping

    2014-02-18

    This paper proposes a novel self-developed JTS-01 desulfurizer and JZC-80 alkaline adsorbent for H2S removal and gas cleaning of the COREX coal gas in small-scale and commercial desulfurizing devices. JTS-01 desulfurizer was loaded with metal oxide (i.e., ferric oxides) catalysts on the surface of activated carbons (AC), and the catalyst capacity was improved dramatically by means of ultrasonically assisted impregnation. Consequently, the sulfur saturation capacity and sulfur capacity breakthrough increased by 30.3% and 27.9%, respectively. The whole desulfurizing process combined selective adsorption with catalytic oxidation. Moreover, JZC-80 adsorbent can effectively remove impurities such as HCl, HF, HCN, and ash in the COREX coal gas, stabilizing the system pressure drop. The JTS-01 desulfurizer and JZC-80 adsorbent have been successfully applied for the COREX coal gas cleaning in the commercial plant at Baosteel, Shanghai. The sulfur capacity of JTS-01 desulfurizer can reach more than 50% in industrial applications. Compared with the conventional dry desulfurization process, the modified AC desulfurizers have more merit, especially in terms of the JTS-01 desulfurizer with higher sulfur capacity and low pressure drop. Thus, this sorption enhanced catalytic desulfurization has promising prospects for H2S removal and other gas cleaning.

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

    Science.gov (United States)

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

    2018-03-07

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

  12. Block-copolymer assisted synthesis of arrays of metal nanoparticles and their catalytic activities for the growth of SWNTs

    International Nuclear Information System (INIS)

    Bhaviripudi, Sreekar; Reina, Alfonso; Qi, Jifa; Kong, Jing; Belcher, Angela M

    2006-01-01

    Block copolymer micellar templates were used for the controlled synthesis of large arrays of mono-metallic (Fe, Co, Ni, Mo) and bi-metallic (Fe-Mo) nanoparticles with average diameters ranging from 1 to 4 nm and the distance between the nanoparticles ranging from 40 to 45 nm. XPS data reveal the presence of mono-metallic nanoparticles in their oxidized states. These uniform arrays of nanoparticles serve as an excellent tool to investigate the catalytic effect of different metal/metal oxide nanoparticles for the growth of carbon nanotubes, and in this work, they were used to investigate the growth of single-walled carbon nanotubes with the chemical vapour deposition (CVD) process, using both ethanol and hydrocarbon (methane + ethylene) gases as carbon sources. The periodicity and the arrangement of nanoparticles were unaffected even at high growth temperatures, indicating that nanoparticle agglomeration on the Si substrate does not take place during growth. AFM and SEM results reveal uniform growth of nanotubes with diameters smaller than the initial size of the catalyst nanoparticles. The Fe, Co and Ni nanoparticles all serve as effective catalysts for nanotube growth with both types of carbon feed stock, and Co and Ni give rise to a relatively higher yield than Fe. The catalytic activity of Fe and bi-metallic Fe-Mo nanoparticles of similar size and identical densities using ethanol CVD are also compared

  13. Preparation of CoFeO Nanocrystallites by Solvothermal Process and Its Catalytic Activity on the Thermal Decomposition of Ammonium Perchlorate

    Directory of Open Access Journals (Sweden)

    Shusen Zhao

    2010-01-01

    Full Text Available Nanometer cobalt ferrite (CoFe2O4 was synthesized by polyol-medium solvothermal method and characterized by X-ray diffraction (XRD, transmission electron microscopy (TEM, and selected area electron diffraction (SAED. Further, the catalytic activity and kinetic parameters of CoFe2O4 nanocrystallites on the thermal decomposition behavior of ammonium perchlorate (AP have been investigated by thermogravimetry and differential scanning calorimetry analysis (TG-DSC. The results imply that the catalytic performance of CoFe2O4 nanocrystallites is significant and the decrease in the activation energy and the increase in the rate constant for AP further confirm the enhancement in catalytic activity of CoFe2O4 nanocrystallites. A mechanism based on an proton transfer process has also been proposed for AP in the presence of CoFe2O4 nanocrystallites.

  14. Modulation of NADPH oxidase activity by known uraemic retention solutes.

    Science.gov (United States)

    Schulz, Anna Marta; Terne, Cindy; Jankowski, Vera; Cohen, Gerald; Schaefer, Mandy; Boehringer, Falko; Tepel, Martin; Kunkel, Desiree; Zidek, Walter; Jankowski, Joachim

    2014-08-01

    Uraemia and cardiovascular disease appear to be associated with an increased oxidative burden. One of the key players in the genesis of reactive oxygen species (ROS) is nicotinamide adenine dinucleotide phosphate (NADPH) oxidase. Based on initial experiments demonstrating a decreased inhibitory effect on NADPH oxidase activity in the presence of plasma from patients with CKD-5D after dialysis compared with before dialysis, we investigated the effect of 48 known and commercially available uraemic retention solutes on the enzymatic activity of NADPH oxidase. Mononuclear leucocytes isolated from buffy coats of healthy volunteers were isolated, lysed and incubated with NADH in the presence of plasma from healthy controls and patients with CKD-5D. Furthermore, the leucocytes were lysed and incubated in the presence of uraemic retention solute of interest and diphenyleneiodonium chloride (DPI), an inhibitor of NADPH oxidase. The effect on enzymatic activity of NADPH oxidase was quantified within an incubation time of 120 min. Thirty-nine of the 48 uraemic retention solutes tested had a significant decreasing effect on NADPH oxidase activity. Oxalate has been characterized as the strongest inhibitor of NADPH oxidase (90% of DPI inhibition). Surprisingly, none of the uraemic retention solutes we investigated was found to increase NADPH oxidase activity. Furthermore, plasma from patients with CKD-5D before dialysis caused significantly higher inhibitory effect on NADPH oxidase activity compared with plasma from healthy subjects. However, this effect was significantly decreased in plasma from patients with CKD-5D after dialysis. The results of this study show that uraemic retention solutes modulated the activity of the NADPH oxidase. The results of this study might be the basis for the development of inhibitors applicable as drug in the situation of increased oxidative stress. © 2014 Stichting European Society for Clinical Investigation Journal Foundation.

  15. Preparation of raspberry-like γ-Fe2O3/crackled nitrogen-doped carbon capsules and their application as supports to improve catalytic activity.

    Science.gov (United States)

    Zhang, Junshuai; Yao, Tongjie; Zhang, Hui; Zhang, Xiao; Wu, Jie

    2016-11-10

    In this manuscript, we have introduced a novel method to improve the catalytic activity of metal nanoparticles via optimizing the support structure. To this end, raspberry-like γ-Fe 2 O 3 /crackled nitrogen-doped carbon (CNC) capsules were prepared by a two-step method. Compared with traditional magnetic capsules, in γ-Fe 2 O 3 /CNC capsules, the γ-Fe 2 O 3 nanoparticles were embedded in a CNC shell; therefore, they neither occupied the anchoring sites for metal nanoparticles nor came into contact with them, which was beneficial for increasing the metal nanoparticle loading. Numerous tiny cracks appeared on the porous CNC shell, which effectively improved the mass diffusion and transport in catalytic reactions. Additionally, the coordination interaction could be generated between the precursor metal ions and doped-nitrogen atoms in the capsule shell. With the help of these structural merits, γ-Fe 2 O 3 /CNC capsules were ideal supports for Pd nanoparticles, because they were beneficial for improving the Pd loading, reducing the nanoparticle size, increasing their dispersity and maximizing the catalytic performance of Pd nanoparticles anchored on the inner shell surface. As expected, γ-Fe 2 O 3 /CNC@Pd catalysts exhibited a dramatically enhanced catalytic activity towards hydrophilic 4-nitrophenol and hydrophobic nitrobenzene. The reaction rate constant k was compared with recent work and the corresponding reference samples. Moreover, they could be easily recycled by using a magnet and reused without an obvious loss of catalytic activity.

  16. Modification of Coal Char-loaded TiO2 by Sulfonation and Alkylsilylation to Enhance Catalytic Activity in Styrene Oxidation with Hydrogen Peroxide as Oxidant

    Directory of Open Access Journals (Sweden)

    Mukhamad Nurhadi

    2017-04-01

    Full Text Available The modified coal char from low-rank coal by sulfonation, titanium impregnation and followed by alkyl silylation possesses high catalytic activity in styrene oxidation. The surface of coal char was undergone several steps as such: modification using concentrated sulfuric acid in the sulfonation process, impregnation of 500 mmol titanium(IV isopropoxide and followed by alkyl silylation of n-octadecyltriclorosilane (OTS. The catalysts were characterized by X-ray diffraction (XRD, IR spectroscopy, nitrogen adsorption, and hydrophobicity. The catalytic activity of the catalysts has been examined in the liquid phase styrene oxidation by using aqueous hydrogen peroxide as oxidant. The catalytic study showed the alkyl silylation could enhance the catalytic activity of Ti-SO3H/CC-600(2.0. High catalytic activity and reusability of the o-Ti-SO3H/CC-600(2.0 were related to the modification of local environment of titanium active sites and the enhancement the hydrophobicity of catalyst particle by alkyl silylation. Copyright © 2017 BCREC GROUP. All rights reserved Received: 24th May 2016; Revised: 11st October 2016; Accepted: 18th October 2016 How to Cite: Nurhadi, M. (2017. Modification of Coal Char-loaded TiO2 by Sulfonation and Alkylsilylation to Enhance Catalytic Activity in Styrene Oxidation with Hydrogen Peroxide as Oxidant. Bulletin of Chemical Reaction Engineering & Catalysis, 12 (1: 55-61 (doi:10.9767/bcrec.12.1.501.55-61 Permalink/DOI: http://dx.doi.org/10.9767/bcrec.12.1.501.55-61

  17. Spectroscopic evidence for an engineered, catalytically active Trp radical that creates the unique reactivity of lignin peroxidase.

    Science.gov (United States)

    Smith, Andrew T; Doyle, Wendy A; Dorlet, Pierre; Ivancich, Anabella

    2009-09-22

    The surface oxidation site (Trp-171) in lignin peroxidase (LiP) required for the reaction with veratryl alcohol a high-redox-potential (1.4 V) substrate, was engineered into Coprinus cinereus peroxidase (CiP) by introducing a Trp residue into a heme peroxidase that has similar protein fold but lacks this activity. To create the catalytic activity toward veratryl alcohol in CiP, it was necessary to reproduce the Trp site and its negatively charged microenvironment by means of a triple mutation. The resulting D179W+R258E+R272D variant was characterized by multifrequency EPR spectroscopy. The spectra unequivocally showed that a new Trp radical [g values of g(x) = 2.0035(5), g(y) = 2.0027(5), and g(z) = 2.0022(1)] was formed after the [Fe(IV)=O Por(*+)] intermediate, as a result of intramolecular electron transfer between Trp-179 and the porphyrin. Also, the EPR characterization crucially showed that [Fe(IV)=O Trp-179(*)] was the reactive intermediate with veratryl alcohol. Accordingly, our work shows that it is necessary to take into account the physicochemical properties of the radical, fine-tuned by the microenvironment, as well as those of the preceding [Fe(IV)=O Por(*+)] intermediate to engineer a catalytically competent Trp site for a given substrate. Manipulation of the microenvironment of the Trp-171 site in LiP allowed the detection by EPR spectroscopy of the Trp-171(*), for which direct evidence has been missing so far. Our work also highlights the role of Trp residues as tunable redox-active cofactors for enzyme catalysis in the context of peroxidases with a unique reactivity toward recalcitrant substrates that require oxidation potentials not realized at the heme site.

  18. 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.

  19. Influence of different preparation conditions on catalytic activity of ag /gama-al/sub 2/o/sub 3/ for hydrogenation of coal slime pyrolysis

    International Nuclear Information System (INIS)

    Lei, Z.; Rong, C.

    2014-01-01

    This paper, introducing variable conditional factors with Ag/AL/sub 2/O/sub 3/ as catalyst, selects five variables to investigate the influences of experimental conditions on Ag/Al2O/sub 3/ catalytic activity and define the optimal process conditions. These variables include Ag loading amount, calcinations temperature, calcinations time, reduction temperature, reduction time. X ray diffraction (XRD), hydrogen temperature-programmed reduction (TPR), X ray photoelectron spectrum (XPS) and scanning electron microscopy (SEM) were utilized to characterize the catalytic activity of Ag/-Al/sub 2/O/sub 3/, active center structure and state and those of carrier were emphatically studied, In the meantime the effects of active center and carrier on catalytic activity are studied. The results showed that: (1) In the range of 600 degree C-900 degree C, the catalytic activity of Ag/-Al/sub 2/O/sub 3/ with different loading showed little difference when changing loading amount, in the range of 900 degree C-1100 degree C, when the loading was 5%, the catalytic activity was very high; From the XRD and SEM characterizations, when the loading was 5%, it showed strong intensity diffraction peak of Ag crystal, crystal Ag is the most important activity center to promote hydrogen yield. (2) the catalytic activity of Ag/-Al/sub 2/O/sub 3/ at 450 degree C was considerably higher than that at 400 degree C and 500 degree C. By BET, XRD and SEM characterization, it can be seen, the diffraction peaks intensity of Ag crystal at 450 degree C is higher and sharper than that at 400 degree C and 500 degree C and with the increase of calcinations temperature, the specific surface area of catalysts also increased. (3) In the range of 600 degree C - 1000 degree C, the effects of calcinations time can be negligible, while, with temperature higher than 1000 degree C, 4-hour-calcinations-time catalyst exhibits a more noticeable catalytic activity than 3-hour and 5-hour catalyst do; From the XRD

  20. Modulation of NADPH oxidase activity by known uraemic retention solutes

    DEFF Research Database (Denmark)

    Schulz, Anna Marta; Terne, Cindy; Jankowski, Vera

    2014-01-01

    chloride (DPI), an inhibitor of NADPH oxidase. The effect on enzymatic activity of NADPH oxidase was quantified within an incubation time of 120 min. RESULTS: Thirty-nine of the 48 uraemic retention solutes tested had a significant decreasing effect on NADPH oxidase activity. Oxalate has been characterized......BACKGROUND: Uraemia and cardiovascular disease appear to be associated with an increased oxidative burden. One of the key players in the genesis of reactive oxygen species (ROS) is nicotinamide adenine dinucleotide phosphate (NADPH) oxidase. Based on initial experiments demonstrating a decreased...... inhibitory effect on NADPH oxidase activity in the presence of plasma from patients with CKD-5D after dialysis compared with before dialysis, we investigated the effect of 48 known and commercially available uraemic retention solutes on the enzymatic activity of NADPH oxidase. METHODS: Mononuclear leucocytes...

  1. Activation of Sphalerite by Ammoniacal Copper Solution in Froth Flotation

    Directory of Open Access Journals (Sweden)

    Xian Xie

    2016-01-01

    Full Text Available The activation of sphalerite particles by ammoniacal copper solution (ACS was investigated in this study. This microflotation study was conducted on a single sphalerite mineral with the particles size of 38 μm to 75 μm. Results showed that ACS has somewhat better activation effect than copper sulphate (a traditional activator with sodium isobutyl xanthate as the collector. Agglomeration observation, contact angle measurement, and X-ray photoelectron spectroscopy measurement results of sphalerite particles verified the superiority of this new activator. Therefore, the substitution of copper sulphate with ACS would increase the separation efficiency not only in marmatite flotation but also in sphalerite flotation.

  2. Ion from Aqueous Solution using Magnetite, Activated Carbon

    African Journals Online (AJOL)

    ADOWIE PERE

    Thermodynamic studies on Adsorption of lead (II) Ion from Aqueous Solution using. Magnetite ... process industries and agricultural activities, which tends to ... osmosis. These processes are however, not economically feasible for small scale industries .... Freundlich coefficient. ..... from binary component system, Beni-suef.

  3. Enhancement in catalytic activity of Aspergillus niger XynB by selective site-directed mutagenesis of active site amino acids.

    Science.gov (United States)

    Wu, Xiuyun; Tian, Zhennan; Jiang, Xukai; Zhang, Qun; Wang, Lushan

    2018-01-01

    XynB from Aspergillus niger ATCC1015 (AnXynB) is a mesophilic glycoside hydrolase (GH) family 11 xylanase which holds great potentials in a wide variety of industrial applications. In the present study, the catalytic activity and stability of AnXynB were improved by a combination of computational and experimental approaches. Virtual mutation and molecular dynamics simulations indicated that the introduction of Glu and Asn altered the interaction network at the - 3 subsite. Interestingly, the double mutant S41N/T43E displayed 72% increase in catalytic activity when compared to the wild type (WT). In addition, it also showed a better thermostability than the WT enzyme. Kinetic determination of the T43E and S41N/T43E mutants suggested that the higher xylanase activity is probably due to the increasing binding affinity of enzyme and substrate. Consequently, the enzyme activity and thermostability of AnXynB was both increased by selective site-directed mutagenesis at the - 3 subsite of its active site architecture which provides a good example for a successfully engineered enzyme for potential industrial application. Moreover, the molecular evolution approach adopted in this study led to the design of a library of sequences that captures a meaningful functional diversity in a limited number of protein variants.

  4. Gold nanostars: Benzyldimethylammonium chloride-assisted synthesis, plasmon tuning, SERS and catalytic activity.

    Science.gov (United States)

    Ndokoye, Pancras; Li, Xinyong; Zhao, Qidong; Li, Tingting; Tade, Moses O; Liu, Shaomin

    2016-01-15

    Fabrication of Au nanostars (AuNSs) can expand the application range of Au nanoparticles because of their high electron density and localized surface plasmon resonance (LSPR) on branches. Exploiting this potential requires further refinement of length of the branches and radius of their tips. To this end, we successfully synthesized AuNSs with uniform and sharply-pointed branches by combining benzyldimethylammonium chloride (BDAC) and cetyltrimethylammonium bromide (CTAB) at low BDAC/CTAB ratios. Once mixed with CTAB, BDAC lowers the critical micelle concentration (CMC) for quick formation of the micelles, which provides favorable growth templates for AuNSs formation. Besides, BDAC increases the concentration of Cl(-), which favors Ag(+) in adsorbing on Au facets. This feature is crucial for the yield boosting and synergic shape control of AuNSs regardless of types of Au seeds used. Use of less amounts of seeds as the center of nucleation benefited sharper and longer growth of the branches. AuNSs exhibited excellent enhancement of surface-enhanced Raman scattering (SERS) intensities as the result of high electron density localized at the tips; however, the enhancement degree varied in accordance with the size of branches. In addition, AuNSs showed high catalytic performance toward the reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP). Efficient catalysis over AuNSs originates from their corners, stepped surfaces and high electron density at the tips. Copyright © 2015 Elsevier Inc. All rights reserved.

  5. A New Energy-Saving Catalytic System: Carbon Dioxide Activation by a Metal/Carbon Catalyst.

    Science.gov (United States)

    Yun, Danim; Park, Dae Sung; Lee, Kyung Rok; Yun, Yang Sik; Kim, Tae Yong; Park, Hongseok; Lee, Hyunjoo; Yi, Jongheop

    2017-09-22

    The conversion of CO 2 into useful chemicals is an attractive method to reduce greenhouse gas emissions and to produce sustainable chemicals. However, the thermodynamic stability of CO 2 means that a lot of energy is required for its conversion into chemicals. Here, we suggest a new catalytic system with an alternative heating system that allows minimal energy consumption during CO 2 conversion. In this system, electrical energy is transferred as heat energy to the carbon-supported metal catalyst. Fast ramping rates allow high operating temperatures (T app =250 °C) to be reached within 5 min, which leads to an 80-fold decrease of energy consumption in methane reforming using CO 2 (DRM). In addition, the consumed energy normalized by time during the DRM reaction in this current-assisted catalysis is sixfold lower (11.0 kJ min -1 ) than that in conventional heating systems (68.4 kJ min -1 ). © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Size Control of Iron Oxide Nanoparticles Using Reverse Microemulsion Method: Morphology, Reduction, and Catalytic Activity in CO Hydrogenation

    Directory of Open Access Journals (Sweden)

    Mohammad Reza Housaindokht

    2013-01-01

    Full Text Available Iron oxide nanoparticles were prepared by microemulsion method and evaluated in Fischer-Tropsch synthesis. The precipitation process was performed in a single-phase microemulsion operating region. Different HLB values of surfactant were prepared by mixing of sodium dodecyl sulfate (SDS and Triton X-100. Transmission electron microscopy (TEM, surface area, pore volume, average pore diameter, pore size distribution, and XRD patterns were used to analyze size distribution, shape, and structure of precipitated hematite nanoparticles. Furthermore, temperature programmed reduction (TPR and catalytic activity in CO hydrogenation were implemented to assess the performance of the samples. It was found that methane and CO2 selectivity and also the syngas conversion increased as the HLB value of surfactant decreased. In addition, the selectivity to heavy hydrocarbons and chain growth probability (α decreased by decreasing the catalyst crystal size.

  7. 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

  8. Theophylline-assisted, eco-friendly synthesis of PtAu nanospheres at reduced graphene oxide with enhanced catalytic activity towards Cr(VI) reduction.

    Science.gov (United States)

    Hu, Ling-Ya; Chen, Li-Xian; Liu, Meng-Ting; Wang, Ai-Jun; Wu, Lan-Ju; Feng, Jiu-Ju

    2017-05-01

    Theophylline as a naturally alkaloid is commonly employed to treat asthma and chronic obstructive pulmonary disorder. Herein, a facile theophylline-assisted green approach was firstly developed for synthesis of PtAu nanospheres/reduced graphene oxide (PtAu NSs/rGO), without any surfactant, polymer, or seed involved. The obtained nanocomposites were applied for the catalytic reduction and removal of highly toxic chromium (VI) using formic acid as a model reductant at 50°C, showing the significantly enhanced catalytic activity and improved recyclability when compared with commercial Pt/C (50%) and home-made Au nanocrystals supported rGO (Au NCs/rGO). It demonstrates great potential applications of the catalyst in wastewater treatment and environmental protection. The eco-friendly route provides a new platform to fabricate other catalysts with enhanced catalytic activity. Copyright © 2016 Elsevier Inc. All rights reserved.

  9. Promoting Effect of CeO2 Addition on Activity and Catalytic Stability in Steam Reforming of Methane over Ni/Al2O3

    International Nuclear Information System (INIS)

    Rakib, A.; Gennequin, C.; Ringot, S.; Aboukais, A.; Abi-Aad, E.; Dhainaut, T.

    2011-01-01

    Hydrogen production by steam reforming of methane was studied over Ni catalysts supported on CeO 2 , Al 2 O 3 and CeO 2 -Al 2 O 3 . These catalysts were prepared using the impregnation method and characterized by XRD. The effect of CeO2 promoter on the catalytic performance of Ni/Al 2 O 3 catalyst for methane steam reforming reaction was investigated. In fact, CeO 2 had a positive effect on the catalytic activity in this reaction. Experimental results demonstrated that Ni/CeO 2 -Al 2 O 3 catalyst showed excellent catalytic activity and high reaction performance. In addition, the effects of reaction temperature and metal content on the conversion of CH 4 and H 2 /CO ratio were also investigated. Results indicated that CH4 conversion increased significantly with the increase of the reaction temperature and metal content. (author)

  10. A novel tumor suppressor function of glycine N-methyltransferase is independent of its catalytic activity but requires nuclear localization.

    Directory of Open Access Journals (Sweden)

    Suchandra DebRoy

    Full Text Available Glycine N-methyltransferase (GNMT, an abundant cytosolic enzyme, catalyzes the transfer of a methyl group from S-adenosylmethionine (SAM to glycine generating S-adenosylhomocysteine and sarcosine (N-methylglycine. This reaction is regulated by 5-methyltetrahydrofolate, which inhibits the enzyme catalysis. In the present study, we observed that GNMT is strongly down regulated in human cancers and is undetectable in cancer cell lines while the transient expression of the protein in cancer cells induces apoptosis and results in the activation of ERK1/2 as an early pro-survival response. The antiproliferative effect of GNMT can be partially reversed by treatment with the pan-caspase inhibitor zVAD-fmk but not by supplementation with high folate or SAM. GNMT exerts the suppressor effect primarily in cells originated from malignant tumors: transformed cell line of non-cancer origin, HEK293, was insensitive to GNMT. Of note, high levels of GNMT, detected in regenerating liver and in NIH3T3 mouse fibroblasts, do not produce cytotoxic effects. Importantly, GNMT, a predominantly cytoplasmic protein, was translocated into nuclei upon transfection of cancer cells. The presence of GNMT in the nuclei was also observed in normal human tissues by immunohistochemical staining. We further demonstrated that the induction of apoptosis is associated with the GNMT nuclear localization but is independent of its catalytic activity or folate binding. GNMT targeted to nuclei, through the fusion with nuclear localization signal, still exerts strong antiproliferative effects while its restriction to cytoplasm, through the fusion with nuclear export signal, prevents these effects (in each case the protein was excluded from cytosol or nuclei, respectively. Overall, our study indicates that GNMT has a secondary function, as a regulator of cellular proliferation, which is independent of its catalytic role.

  11. Highly n-Type Titanium Oxide as an Electronically Active Support for Platinum in the Catalytic Oxidation of Carbon Monoxide

    KAUST Repository

    Baker, L. Robert

    2011-08-18

    The role of the oxide-metal interface in determining the activity and selectivity of chemical reactions catalyzed by metal particles on an oxide support is an important topic in science and industry. A proposed mechanism for this strong metal-support interaction is electronic activation of surface adsorbates by charge carriers. Motivated by the goal of using electronic activation to drive nonthermal chemistry, we investigated the ability of the oxide support to mediate charge transfer. We report an approximately 2-fold increase in the turnover rate of catalytic carbon monoxide oxidation on platinum nanoparticles supported on stoichiometric titanium dioxide (TiO2) when the TiO2 is made highly n-type by fluorine (F) doping. However, for nonstoichiometric titanium oxide (TiOX<2) the effect of F on the turnover rate is negligible. Studies of the titanium oxide electronic structure show that the energy of free electrons in the oxide determines the rate of reaction. These results suggest that highly n-type TiO2 electronically activates adsorbed oxygen (O) by electron spillover to form an active O- intermediate. © 2011 American Chemical Society.

  12. Physicochemical Characteristics and Biological Activity of Irradiated Pectin Solution

    International Nuclear Information System (INIS)

    Kwon, J.H.; Kang, H.J.; Jo, C.O.; Jeong, I.Y.; Byun, M.W.

    2005-01-01

    Pectin was dissolved in HCI, citric acid, and deionized distilled water (DW, 2%, v/v) and irradiated at different irradiation doses (2.5-50 kGy) by gamma ray to investigate its physicochemical characteristics and biological activity. Viscosity of pectin solution was significantly decreased by irradiation up to 10 kGy, then remained constant thereafter. Gamma-irradiation increased monosaccharide and polysaccharide levels up to 30-40 kDa. Electron donating ability of pectin solution was highest when DW was added was increased by increasing irradiation dose (p less than 0.05)

  13. CATALYTIC HYDROCRACKING OF WASTE LUBRICANT OIL INTO LIQUID FUEL FRACTION USING ZnO, Nb2O5, ACTIVATED NATURAL ZEOLITE AND THEIR MODIFICATION

    Directory of Open Access Journals (Sweden)

    Wega Trisunaryanti

    2010-06-01

    Full Text Available Catalytic hydrocracking of waste lubricant oil into liquid fuel fraction using ZnO, Nb2O5, activated natural zeolite (ZAAH and their modification has been investigated. The zeolite was produced in Wonosari, Yogyakarta. Activation of the zeolite was carried out by refluxing with HCl 3M for 30 min, produced the activated natural zeolite (ZAAH. The ZnO/ZAAH catalyst was prepared by impregnation of Zn onto the ZAAH by ion exchange method using salt precursor of Zn(NO32.4H2O. The Nb2O5/ZAAH catalyst was prepared by mixing the ZAAH sample with Nb2O5 and oxalic acid solution until the paste was formed. The impregnation of Zn onto Nb2O5/ZAAH was carried out using the same method to that of the ZnO/ZAAH catalyst resulted ZnO/Nb2O5-ZAAH catalyst. Characterization of catalyst includes determination of Zn metal by Atomic Absorption Spectroscopy (AAS, acidity by gravimetric method and catalyst porosity by Surface Area Analyzer (NOVA-1000. Catalytic hydrocracking was carried out in a semi-batch reactor system using ZnO, ZAAH, ZnO/ZAAH and ZnO/Nb2O5-ZAAH catalysts at 450 oC under the H2 flow rate of 15 mL/min. and the ratio of catalyst/feed = 1/5. The composition of liquid products was analyzed by Gas Chromatograpy (GC.The results showed that impregnation of ZnO and/or Nb2O5 on the ZAAH increased the acidity and specific surface area of catalyst. The products of the hydrocracking process were liquid, coke and gas. Conversion of liquid products was increased by the increase of catalyst acidity. The highest liquid product was produced by ZnO/Nb2O5-ZAAH catalyst, 52.97 wt-%, consist of gasoline, 38.87 wt-% and diesel, 14.10 wt-%.   Keywords: hydrocracking, waste lubricant oil, liquid fuel fraction

  14. Synthesis of Ultra-Small Platinum, Palladium and Gold Nanoparticles by Shewanella loihica PV-4 Electrochemically Active Biofilm and Their Enhanced Catalytic Activities

    KAUST Repository

    Ahmed, Elaf

    2018-02-21

    Ultra-small nanoparticles (USNPs) of noble metals have a great potential in a variety of applications due to their high surface areas and high reactivity. This works employed electrochemically active biofilms (EABs) composed of a single bacterium strain of Shewanella loihica PV-4 and successfully synthesized USNPs of noble metal Au, Pd, and Pt. The synthesized USNPs had a size range between 2 and 7 nm and exhibited excellent catalytic performance in dye decomposition. The results of this work shine lights on the use of EABs in nanoparticle synthesis.

  15. A recyclable Au(I) catalyst for selective homocoupling of arylboronic acids: significant enhancement of nano-surface binding for stability and catalytic activity.

    Science.gov (United States)

    Zhang, Xin; Zhao, Haitao; Wang, Jianhui

    2010-08-01

    Au nanoparticles stabilized by polystyrene-co-polymethacrylic acid microspheres (PS-co-PMAA) were prepared and characterized via X-ray diffraction (XRD), and transmission electron microscope (TEM). The Au nanoparticles supported on the microspheres showed highly selective catalytic activity for homo-coupling reactions of arylboronic acids in a system of aryl-halides and arylboronic acids. X-ray photoelectron spectroscopy (XPS) spectra of the catalyst shows large amounts of Au(I) complexes band to the surface of the Au nanoparticles, which contributes to the selective homocoupling of the arylboronic acids. More importantly, this supported Au complex is a highly recyclable catalyst. The supported Au catalyst can be recycled and reused at least 6 times for a phenylboronic acid reactant, whereas the parent complex shows very low catalytic activity for this compound. The high catalytic activity of this material is attributed to: (1) the high surface to volume ratio which leads to more active sites being exposed to reactants; (2) the strong surface binding of the Au nanoparticle to the Au(I) complexes, which enhances both the stability and the catalytic activity of these complexes.

  16. Enhanced catalytic activity of the nanostructured Co-W-B film catalysts for hydrogen evolution from the hydrolysis of ammonia borane.

    Science.gov (United States)

    Li, Chao; Wang, Dan; Wang, Yan; Li, Guode; Hu, Guijuan; Wu, Shiwei; Cao, Zhongqiu; Zhang, Ke

    2018-08-15

    In this work, nanostructured Co-W-B films are successfully synthesized on the foam sponge by electroless plating method and employed as the catalysts with enhanced catalytic activity towards hydrogen evolution from the hydrolysis of ammonia borane (NH 3 BH 3 , AB) at room temperature. The particle size of the as-prepared Co-W-B film catalysts is varied by adjusting the depositional pH value to identify the most suitable particle size for hydrogen evolution of AB hydrolysis. The Co-W-B film catalyst with the particle size of about 67.3 nm shows the highest catalytic activity and can reach a hydrogen generation rate of 3327.7 mL min -1 g cat -1 at 298 K. The activation energy of the hydrolysis reaction of AB is determined to be 32.2 kJ mol -1 . Remarkably, the as-obtained Co-W-B film is also a reusable catalyst preserving 78.4% of their initial catalytic activity even after 5 cycles in hydrolysis of AB at room temperature. Thus, the enhanced catalytic activity illustrates that the Co-W-B film is a promising catalyst for AB hydrolytic dehydrogenation in fuel cells and the related fields. Copyright © 2018 Elsevier Inc. All rights reserved.

  17. Combining Ru, Ni and Ni(OH){sub 2} active sites for improving catalytic performance in benzene hydrogenation

    Energy Technology Data Exchange (ETDEWEB)

    Zhu, Lihua, E-mail: lihuazhu@stu.xmu.edu.cn [School of Metallurgy and Chemical Engineering, Jiangxi University of Science and Technology, Ganzhou 341000, Jiang Xi (China); Department of Chemical and Biochemical Engineering, National Engineering Laboratory for Green Productions of Alcohols-Ethers-Esters, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005 (China); Sun, Hanlei; Zheng, Jinbao [Department of Chemical and Biochemical Engineering, National Engineering Laboratory for Green Productions of Alcohols-Ethers-Esters, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005 (China); Yu, Changlin, E-mail: yuchanglinjx@163.com [School of Metallurgy and Chemical Engineering, Jiangxi University of Science and Technology, Ganzhou 341000, Jiang Xi (China); Zhang, Nuowei [Department of Chemical and Biochemical Engineering, National Engineering Laboratory for Green Productions of Alcohols-Ethers-Esters, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005 (China); Shu, Qing [School of Metallurgy and Chemical Engineering, Jiangxi University of Science and Technology, Ganzhou 341000, Jiang Xi (China); Chen, Bing H., E-mail: chenbh@xmu.edu.cn [Department of Chemical and Biochemical Engineering, National Engineering Laboratory for Green Productions of Alcohols-Ethers-Esters, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005 (China)

    2017-05-01

    In this study, the Ru{sub 0.04}Ni{sub 0.96}/C(T) catalysts were successfully prepared by the simple methods of hydrazine-reduction and galvanic replacement, where 0.04/0.96 and T represented the Ru/Ni atomic ratio and reducing temperature of the catalyst in N{sub 2}+10%H{sub 2}, respectively. The nanostructures of the Ru{sub 0.04}Ni{sub 0.96} nanoparticles in the Ru{sub 0.04}Ni{sub 0.96}/C(T) catalysts were controlled by modulating their annealing temperature in N{sub 2}+10%H{sub 2} and characterized by an array of techniques, including X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM), scanning transmission electron microscopy energy dispersive X-ray spectroscopy (STEM-EDS) mapping and high-sensitivity low-energy ion scattering (HS-LEIS). The Ru{sub 0.04}Ni{sub 0.96}/C(30) catalyst, which was composed of Ru clusters or single atoms supported on Ni/Ni(OH){sub 2} nanoparticles, exhibited much better catalytic performance for benzene hydrogenation than the Ru{sub 0.04}Ni{sub 0.96}/C(T) catalysts reduced at above 30 °C, such as Ru{sub 0.04}Ni{sub 0.96}/C(160) with the nanostructure of partial Ru{sub 0.04}Ni{sub 0.9} alloy and Ru{sub 0.04}Ni{sub 0.96}/C(280) with the nanostructure of complete Ru{sub 0.04}Ni{sub 0.9} alloy. The reason was that the synergistic effect of multiple active sites – Ru, Ni and Ni(OH){sub 2} sites was present in the Ru{sub 0.04}Ni{sub 0.96}/C(30) catalyst, where hydrogen was preferentially activated at Ru sites, benzene was probably activated at Ni(OH){sub 2} surface and Ni acted as a “bridge” for transferring activated H{sup ∗} species to activated benzene by hydrogen spillover effect, hydrogenating and forming product – cyclohexane. This study also provided a typical example to illustrate that the synergy effect of multiple active sites can largely improve the catalytic hydrogenation performance. - Highlights: • The Ru

  18. Catalytically Active Guanylyl Cyclase B Requires Endoplasmic Reticulum-mediated Glycosylation, and Mutations That Inhibit This Process Cause Dwarfism.

    Science.gov (United States)

    Dickey, Deborah M; Edmund, Aaron B; Otto, Neil M; Chaffee, Thomas S; Robinson, Jerid W; Potter, Lincoln R

    2016-05-20

    C-type natriuretic peptide activation of guanylyl cyclase B (GC-B), also known as natriuretic peptide receptor B or NPR2, stimulates long bone growth, and missense mutations in GC-B cause dwarfism. Four such mutants (L658F, Y708C, R776W, and G959A) bound (125)I-C-type natriuretic peptide on the surface of cells but failed to synthesize cGMP in membrane GC assays. Immunofluorescence microscopy also indicated that the mutant receptors were on the cell surface. All mutant proteins were dephosphorylated and incompletely glycosylated, but dephosphorylation did not explain the inactivation because the mutations inactivated a "constitutively phosphorylated" enzyme. Tunicamycin inhibition of glycosylation in the endoplasmic reticulum or mutation of the Asn-24 glycosylation site decreased GC activity, but neither inhibition of glycosylation in the Golgi by N-acetylglucosaminyltransferase I gene inactivation nor PNGase F deglycosylation of fully processed GC-B reduced GC activity. We conclude that endoplasmic reticulum-mediated glycosylation is required for the formation of an active catalytic, but not ligand-binding domain, and that mutations that inhibit this process cause dwarfism. © 2016 by The American Society for Biochemistry and Molecular Biology, Inc.

  19. Structural and mechanistic analysis of engineered trichodiene synthase enzymes from Trichoderma harzianum: towards higher catalytic activities empowering sustainable agriculture.

    Science.gov (United States)

    Kumari, Indu; Chaudhary, Nitika; Sandhu, Padmani; Ahmed, Mushtaq; Akhter, Yusuf

    2016-06-01

    Trichoderma spp. are well-known bioagents for the plant growth promotion and pathogen suppression. The beneficial activities of the fungus Trichoderma spp. are attributed to their ability to produce and secrete certain secondary metabolites such as trichodermin that belongs to trichothecene family of molecules. The initial steps of trichodermin biosynthetic pathway in Trichoderma are similar to the trichothecenes from Fusarium sporotrichioides. Trichodiene synthase (TS) encoded by tri5 gene in Trichoderma catalyses the conversion of farnesyl pyrophosphate to trichodiene as reported earlier. In this study, we have carried out a comprehensive comparative sequence and structural analysis of the TS, which revealed the conserved residues involved in catalytic activity of the protein. In silico, modelled tertiary structure of TS protein showed stable structural behaviour during simulations. Two single-substitution mutants, i.e. D109E, D248Y and one double-substitution mutant (D109E and D248Y) of TS with potentially higher activities are screened out. The mutant proteins showed more stability than the wild type, an increased number of electrostatic interactions and better binding energies with the ligand, which further elucidates the amino acid residues involved in the reaction mechanism. These results will lead to devise strategies for higher TS activity to ultimately enhance the trichodermin production by Trichoderma spp. for its better exploitation in the sustainable agricultural practices.

  20. Ferredoxin-thioredoxin reductase: a catalytically active dithiol group links photoreduced ferredoxin to thioredoxin functional in photosynthetic enzyme regulation

    Energy Technology Data Exchange (ETDEWEB)

    Droux, M.; Miginiac-Maslow, M.; Jacquot, J.P.; Gadal, P.; Crawford, N.A.; Kosower, N.S.; Buchanan, B.B.

    1987-07-01

    The mechanism by which the ferredoxin-thioredoxin system activates the target enzyme, NADP-malate dehydrogenase, was investigated by analyzing the sulfhydryl status of individual protein components with (/sup 14/C)iodoacetate and monobromobimane. The data indicate that ferredoxin-thioredoxin reductase (FTR)--an iron-sulfur enzyme present in oxygenic photosynthetic organisms--is the first member of a thiol chain that links light to enzyme regulation. FTR possesses a catalytically active dithiol group localized on the 13 kDa (similar) subunit, that occurs in all species investigated and accepts reducing equivalents from photoreduced ferredoxin and transfers them stoichiometrically to the disulfide form of thioredoxin m. The reduced thioredoxin m, in turn, reduces NADP-malate dehydrogenase, thereby converting it from an inactive (S-S) to an active (SH) form. The means by which FTR is able to combine electrons (from photoreduced ferredoxin) with protons (from the medium) to reduce its active disulfide group remains to be determined.

  1. Incorporating nitrogen atoms into cobalt nanosheets as a strategy to boost catalytic activity toward CO2 hydrogenation

    Science.gov (United States)

    Wang, Liangbing; Zhang, Wenbo; Zheng, Xusheng; Chen, Yizhen; Wu, Wenlong; Qiu, Jianxiang; Zhao, Xiangchen; Zhao, Xiao; Dai, Yizhou; Zeng, Jie

    2017-11-01

    Hydrogenation of CO2 into fuels and useful chemicals could help to reduce reliance on fossil fuels. Although great progress has been made over the past decades to improve the activity of catalysts for CO2 hydrogenation, more efficient catalysts, especially those based on non-noble metals, are desired. Here we incorporate N atoms into Co nanosheets to boost the catalytic activity toward CO2 hydrogenation. For the hydrogenation of CO2, Co4N nanosheets exhibited a turnover frequency of 25.6 h-1 in a slurry reactor under 32 bar pressure at 150 °C, which was 64 times that of Co nanosheets. The activation energy for Co4N nanosheets was 43.3 kJ mol-1, less than half of that for Co nanosheets. Mechanistic studies revealed that Co4N nanosheets were reconstructed into Co4NHx, wherein the amido-hydrogen atoms directly interacted with the CO2 to form HCOO* intermediates. In addition, the adsorbed H2O* activated amido-hydrogen atoms via the interaction of hydrogen bonds.

  2. Modeling for thermodynamic activities of components in simulated reprocessing solutions

    International Nuclear Information System (INIS)

    Sasahira, Akira; Hoshikawa, Tadahiro; Kawamura, Fumio

    1992-01-01

    Analyses of chemical reactions have been widely carried out for soluble fission products encountered in nuclear fuel reprocessing. For detailed analyses of reactions, a prediction of the activity or activity coefficient for nitric acid, water, and several nitrates of fission products is needed. An idea for the predicted nitric acid activity was presented earlier. The model, designated the hydration model, does not predict the nitrate activity. It did, however, suggest that the activity of water would be a function of nitric acid activity but not the molar fraction of water. If the activities of nitric acid and water are accurately predicted, the activity of the last component, nitrate, can be calculated using the Gibbs-Duhem relation for chemical potentials. Therefore, in this study, the earlier hydration model was modified to evaluate the water activity more accurately. The modified model was experimentally examined in stimulated reprocessing solutions. It is concluded that the modified model was suitable for water activity, but further improvement was needed for the activity evaluation of nitric acid in order to calculate the nitrate activity

  3. 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 ...

  4. Some physico-chemical properties and catalytic activity of sulfate ion supported on WO3/SnO2 catalyst

    Directory of Open Access Journals (Sweden)

    M.N. Alaya

    2017-02-01

    Full Text Available Solid acid catalyst 15 wt%WO3/SnO2 was synthesized and loaded with 15 wt%SO4. The obtained catalyst was calcined at 400, 500, 650 and 800 °C. The prepared catalysts were characterized by TG-DTA, XRD, FTIR and N2 adsorption at −196 °C. The surface acidity was measured by non aqueous potentiometric titration and FT-IR spectra of chemisorbed pyridine. The catalytic performance was evaluated on the esterification of propionic acid with n-butanol in liquid phase. The TG-DTA analysis shows that the decomposition of sulfate species occurred at >500 °C. XRD measurements showed that WO3 dispersed completely on the surface of SnO2 and that the sulfating of WO3/SnO2 tends to hinder the crystallization of SnO2. The specific surface area, total pore volume and micropore volume are increased with increasing thermal treatment up to 500 °C, and then decreased gradually with a further increase in calcination temperature. The prepared catalysts possess very strong acid sites and contain both Brønsted and Lewis acid sites. The total surface acidity decreased with raising of the calcination temperature. The highest conversion of propionic acid was for 400 °C product, and decreased with an increase in calcination temperature. The effect of the reaction parameters, i.e., time of reaction, reaction temperature, and reactant molar ratio and the weight of the catalyst were also studied. The reaction obeys the second order kinetic equation with respect to propionic acid concentration. Brønsted and Lewis acid sites appeared to be needed for catalytic activity in n-butyl propionate formation.

  5. 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.

  6. Fe-based MOFs for efficient adsorption and degradation of acid orange 7 in aqueous solution via persulfate activation

    International Nuclear Information System (INIS)

    Li, Xianghui; Guo, Weilin; Liu, Zhonghua; Wang, Ruiqin; Liu, Hua

    2016-01-01

    Graphical abstract: - Highlights: • Fe-based MILs were prepared via the facile solvothermal method. • MILs showed efficient removal rate through adsorption and degradation processes. • A possible catalytic degradation mechanism is proposed. - Abstract: Fe-based metal–organic frameworks (MOFs) including MIL-101(Fe), MIL-100(Fe), MIL-53(Fe), and MIL-88B(Fe) prepared via a facile solvothermal process were introduced as both adsorbents and catalysts to generate powerful radicals from persulfate for acid orange 7 (AO7) removal in aqueous solution. Various catalysts were described and characterized by X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy and X-ray photoelectron spectra. Because of the high specific surface area of the materials, we studied the adsorption isotherms of the four MILs by the fitting of Langmuir adsorption isotherm. Meanwhile, the catalytic activities in persulfate oxidation system were investigated. The results showed that the sequence of the materials ability in the combination of adsorption and degradation was MIL-101(Fe) > MIL-100(Fe) > MIL-53(Fe) > MIL-88B(Fe), which had a close connection with the activity of metal ion in active site of the catalysts and their different cages in size. Moreover, the reactive species in MILs/persulfate system were identified as sulfate radicals and hydroxyl radicals. The reaction mechanism for persulfate activation over MILs was also studied.

  7. Synthesis and Catalytic Activity of Pluronic Stabilized Silver-Gold Bimetallic Nanoparticles

    OpenAIRE

    Holden, Megan S.; Nick, Kevin E.; Hall, Mia; Milligan, Jamie R.; Chen, Qiao; Perry, Christopher C.

    2014-01-01

    In this report, we demonstrate a rapid, simple, and green method for synthesizing silver-gold (Ag-Au) bimetallic nanoparticles (BNPs). We used a novel modification to the galvanic replacement reaction by suspending maltose coated silver nanoparticles (NPs) in ≈ 2% aqueous solution of EO100PO65EO100 (Pluronic F127) prior to HAuCl4 addition. The Pluronic F127 stabilizes the BNPs, imparts biocompatibility, and mitigates the toxicity issues associated with other surfactant stabilizers. BNPs with ...

  8. System for sampling active solutions in transport container; Systeme de prelevements de solutions actives sur les recipients de transport

    Energy Technology Data Exchange (ETDEWEB)

    Fradin, J.

    1958-12-03

    This report presents a system aimed at sampling active solution from a specific transport container (SCRGR model) while transferring this solution with a maximum safety. The sampling principle is described (a flexible tube connected to the receiving container, with a needle at the other end which goes through a rubber membrane and enters a plunger tube). Its benefits are outlined (operator protection, reduction of contamination risk; only the rubber membrane is removed and replaced). Some manufacturing details are described concerning the membrane and the cover.

  9. Understanding the effect of post-synthesis ammonium treatment on the catalytic activity of Au/Ti-SBA-15 catalysts for the oxidation of propene

    NARCIS (Netherlands)

    Sacaliuc-Parvulescu, E.; Friedrich, H.; Palkovits, R.; Weckhuysen, B.M.; Nijhuis, T.A.

    2008-01-01

    Postsynthesis ammonium treatment induces a substantial increase in the catalytic activity of Au/Ti- SBA-15 catalysts for the direct vapor-phase epoxidation of propylene using hydrogen and oxygen. The PO formation rate of a calcined Au/Ti-SBA-15 catalyst prepared by this method increased from 4.3

  10. Understanding the effect of postsynthesis ammonium treatment on the catalytic activity of Au/TI-SBA-15 catalysts for the oxidation of propene

    NARCIS (Netherlands)

    Sacaliuc, E.; Friedrich, H.; Palkovits, R.; Weckhuysen, B.M.; Nijhuis, T.A.

    2008-01-01

    Postsynthesis ammonium treatment induces a substantial increase in the catalytic activity of Au/Ti-SBA-15 catalysts for the direct vapor-phase epoxidation of propylene using hydrogen and oxygen. The PO formation rate of a calcined Au/Ti-SBA-15 catalyst prepared by this method increased from 4.3 mgPO

  11. Catalytic Fast Pyrolysis of Biomass Impregnated with Potassium Phosphate in a Hydrogen Atmosphere for the Production of Phenol and Activated Carbon

    Science.gov (United States)

    Lu, Qiang; Zhang, Zhen-xi; Wang, Xin; Guo, Hao-qiang; Cui, Min-shu; Yang, Yong-ping

    2018-01-01

    A new technique was proposed to co-produce phenol and activated carbon (AC) from catalytic fast pyrolysis of biomass impregnated with K3PO4 in a hydrogen atmosphere, followed by activation of the pyrolytic solid residues. Lab-scale catalytic fast pyrolysis experiments were performed to quantitatively determine the pyrolytic product distribution, as well as to investigate the effects of several factors on the phenol production, including pyrolysis atmosphere, catalyst type, biomass type, catalytic pyrolysis temperature, and catalyst impregnation content. In addition, the pyrolytic solid residues were activated to prepare ACs with high specific surface areas. The results indicated that phenol could be obtained due to the synergistic effects of K3PO4 and hydrogen atmosphere, with the yield and selectivity reaching 5.3 wt% and 17.8% from catalytic fast pyrolysis of poplar wood with 8 wt% K3PO4 at 550°C in a hydrogen atmosphere. This technique was adaptable to different woody materials for phenol production. Moreover, gas product generated from the pyrolysis process was feasible to be recycled to provide the hydrogen atmosphere, instead of extra hydrogen supply. In addition, the pyrolytic solid residue was suitable for AC preparation, using CO2 activation method, the specific surface area was as high as 1,605 m2/g. PMID:29515994

  12. Synthesis, characterization and catalytic activity of stable [(NHC)H][ZnXY2] (NHC=N-Heterocyclic carbene, X, Y=Cl, Br) species

    KAUST Repository

    Santoro, Orlando; Nahra, Fady; Cordes, David B.; Slawin, Alexandra M.Z.; Nolan, Steven P.; Cazin, Catherine S. J.

    2016-01-01

    The synthesis and characterization of imidazol(in)ium-based zinc(II) halide salts are reported. These compounds present interesting structural features and exhibit high stability. Their catalytic activity was explored in the methylation of amines with CO2 and PhSiH3.

  13. Catalytic fast pyrolysis of biomass impregnated with potassium phosphate in a hydrogen atmosphere for the production of phenol and activated carbon

    Science.gov (United States)

    Lu, Qiang; Zhang, Zhen-xi; Wang, Xin; Guo, Hao-qiang; Cui, Min-shu; Yang, Yong-ping

    2018-02-01

    A new technique was proposed to co-produce phenol and activated carbon (AC) from catalytic fast pyrolysis of biomass impregnated with K3PO4 in a hydrogen atmosphere, followed by activation of the pyrolytic solid residues. Lab-scale catalytic fast pyrolysis experiments were performed to quantitatively determine the pyrolytic product distribution, as well as to investigate the effects of several factors on the phenol production, including pyrolysis atmosphere, catalyst type, biomass type, catalytic pyrolysis temperature, and catalyst impregnation content. In addition, the pyrolytic solid residues were activated to prepare ACs with high specific surface areas. The results indicated that phenol could be obtained due to the synergistic effects of K3PO4 and hydrogen atmosphere, with the yield and selectivity reaching 5.3 wt% and 17.8% from catalytic fast pyrolysis of poplar wood with 8 wt% K3PO4 at 550 oC in a hydrogen atmosphere. This technique was adaptable to different woody materials for phenol production. Moreover, gas product generated from the pyrolysis process was feasible to be recycled to provide the hydrogen atmosphere, instead of extra hydrogen supply. In addition, the pyrolytic solid residue was suitable for AC preparation, using CO2 activation method, the specific surface area was as high as 1605 m2/g.

  14. Synthesis, characterization and catalytic activity of stable [(NHC)H][ZnXY2] (NHC=N-Heterocyclic carbene, X, Y=Cl, Br) species

    KAUST Repository

    Santoro, Orlando

    2016-06-04

    The synthesis and characterization of imidazol(in)ium-based zinc(II) halide salts are reported. These compounds present interesting structural features and exhibit high stability. Their catalytic activity was explored in the methylation of amines with CO2 and PhSiH3.

  15. Decreased catalytic activity and altered activation properties of PDE6C mutants associated with autosomal recessive achromatopsia

    DEFF Research Database (Denmark)

    Grau, Tanja; Artemyev, Nikolai O; Rosenberg, Thomas

    2011-01-01

    study on PDE6C mutations including the mutation spectrum, its prevalence in a large cohort of ACHM/cone dysfunction patients, the clinical phenotype and the functional characterization of mutant PDE6C proteins. Twelve affected patients from seven independent families segregating PDE6C mutations were......Mutations in the gene encoding the catalytic subunit of the cone photoreceptor phosphodiesterase (PDE6C) have been recently reported in patients with autosomal recessive inherited achromatopsia (ACHM) and early-onset cone photoreceptor dysfunction. Here we present the results of a comprehensive...... identified in our total patient cohort of 492 independent families. Eleven different PDE6C mutations were found including two nonsense mutations, three mutations affecting transcript splicing as shown by minigene assays, one 1 bp-insertion and five missense mutations. We also performed a detailed functional...

  16. Actinide removal from aqueous solution with activated magnetite

    International Nuclear Information System (INIS)

    Kochen, R.L.; Thomas, R.L.

    1987-01-01

    An actinide aqueous waste treatment process using activated magnetite has been developed at Rocky Flats. The use and effectiveness of various magnetites in lowering actinide concentrations in aqueous solution are described. Experiments indicate that magnetite particle size and pretreatment (activation of the magnetite surface with hydroxyl ions greatly influence the effective use of magnetite as an actinide adsorbent. With respect to actinide removal, Ba(OH) 2 -activated magnetite was more effective over a broader pH range than was NaOH-activated magnetite. About 50% less Ba(OH) 2 -activated magnetite was required to lower plutonium concentration from 10 -4 to 10 -8 g/l. 7 refs., 8 tabs

  17. Catalytic water co-existing with a product peptide in the active site of HIV-1 protease revealed by X-ray structure analysis.

    Directory of Open Access Journals (Sweden)

    Vishal Prashar

    Full Text Available BACKGROUND: It is known that HIV-1 protease is an important target for design of antiviral compounds in the treatment of Acquired Immuno Deficiency Syndrome (AIDS. In this context, understanding the catalytic mechanism of the enzyme is of crucial importance as transition state structure directs inhibitor design. Most mechanistic proposals invoke nucleophilic attack on the scissile peptide bond by a water molecule. But such a water molecule coexisting with any ligand in the active site has not been found so far in the crystal structures. PRINCIPAL FINDINGS: We report here the first observation of the coexistence in the active site, of a water molecule WAT1, along with the carboxyl terminal product (Q product peptide. The product peptide has been generated in situ through cleavage of the full-length substrate. The N-terminal product (P product has diffused out and is replaced by a set of water molecules while the Q product is still held in the active site through hydrogen bonds. The position of WAT1, which hydrogen bonds to both the catalytic aspartates, is different from when there is no substrate bound in the active site. We propose WAT1 to be the position from where catalytic water attacks the scissile peptide bond. Comparison of structures of HIV-1 protease complexed with the same oligopeptide substrate, but at pH 2.0 and at pH 7.0 shows interesting changes in the conformation and hydrogen bonding interactions from the catalytic aspartates. CONCLUSIONS/SIGNIFICANCE: The structure is suggestive of the repositioning, during substrate binding, of the catalytic water for activation and subsequent nucleophilic attack. The structure could be a snap shot of the enzyme active site primed for the next round of catalysis. This structure further suggests that to achieve the goal of designing inhibitors mimicking the transition-state, the hydrogen-bonding pattern between WAT1 and the enzyme should be replicated.

  18. Catalytic water co-existing with a product peptide in the active site of HIV-1 protease revealed by X-ray structure analysis.

    Science.gov (United States)

    Prashar, Vishal; Bihani, Subhash; Das, Amit; Ferrer, Jean-Luc; Hosur, Madhusoodan

    2009-11-17

    It is known that HIV-1 protease is an important target for design of antiviral compounds in the treatment of Acquired Immuno Deficiency Syndrome (AIDS). In this context, understanding the catalytic mechanism of the enzyme is of crucial importance as transition state structure directs inhibitor design. Most mechanistic proposals invoke nucleophilic attack on the scissile peptide bond by a water molecule. But such a water molecule coexisting with any ligand in the active site has not been found so far in the crystal structures. We report here the first observation of the coexistence in the active site, of a water molecule WAT1, along with the carboxyl terminal product (Q product) peptide. The product peptide has been generated in situ through cleavage of the full-length substrate. The N-terminal product (P product) has diffused out and is replaced by a set of water molecules while the Q product is still held in the active site through hydrogen bonds. The position of WAT1, which hydrogen bonds to both the catalytic aspartates, is different from when there is no substrate bound in the active site. We propose WAT1 to be the position from where catalytic water attacks the scissile peptide bond. Comparison of structures of HIV-1 protease complexed with the same oligopeptide substrate, but at pH 2.0 and at pH 7.0 shows interesting changes in the conformation and hydrogen bonding interactions from the catalytic aspartates. The structure is suggestive of the repositioning, during substrate binding, of the catalytic water for activation and subsequent nucleophilic attack. The structure could be a snap shot of the enzyme active site primed for the next round of catalysis. This structure further suggests that to achieve the goal of designing inhibitors mimicking the transition-state, the hydrogen-bonding pattern between WAT1 and the enzyme should be replicated.

  19. Catalytic properties of thermophilic lactate dehydrogenase and halophilic malate dehydrogenase at high temperature and low water activity.

    Science.gov (United States)

    Hecht, K; Wrba, A; Jaenicke, R

    1989-07-15

    Thermophilic lactate dehydrogenases from Thermotoga maritima and Bacillus stearothermophilus are stable up to temperature limits close to the optimum growth temperature of their parent organisms. Their catalytic properties are anomalous in that Km shows a drastic increase with increasing temperature. At low temperatures, the effect levels off. Extreme halophilic malate dehydrogenase from Halobacterium marismortui exhibits a similar anomaly. Increasing salt concentration (NaCl) leads to an optimum curve for Km, oxaloacctate while Km, NADH remains constant. Previous claims that the activity of halophilic malate dehydrogenase shows a maximum at 1.25 M NaCl are caused by limiting substrate concentration; at substrate saturation, specific activity of halophilic malate dehydrogenase reaches a constant value at ionic strengths I greater than or equal to 1 M. Non-halophilic (mitochondrial) malate dehydrogenase shows Km characteristics similar to those observed for the halophilic enzyme. The drastic decrease in specific activity of the mitochondrial enzyme at elevated salt concentrations is caused by the salt-induced increase in rigidity of the enzyme, rather than gross structural changes.

  20. Mesoporous PtSnO2/C Catalyst with Enhanced Catalytic Activity for Ethanol Electro-oxidation

    Directory of Open Access Journals (Sweden)

    Siyu Chen

    2018-01-01

    Full Text Available In this paper, we report the synthesis, characterization, and electrochemical evaluation of a mesoporous PtSnO2/C catalyst, called PtSnO2(M/C, with a nominal Pt : Sn ratio of 3 : 1. Brunauer–Emmett–Teller and transmission electron microscopy characterizations showed the obvious mesoporous structure of SnO2 in PtSnO2(M/C catalyst. X-ray photoelectron spectroscopy analysis exhibited the interaction between Pt and mesoporous SnO2. Compared with Pt/C and commercial PtSnO2/C catalysts, PtSnO2(M/C catalyst has a lower active site, but higher catalytic activity for ethanol electro-oxidation reaction (EOR. The enhanced activity could be attributed to Pt nanoparticles deposited on mesoporous SnO2 that could decrease the amount of poisonous intermediates produced during EOR by the interaction between Pt and mesoporous SnO2.

  1. Reconstitution of Vanadium Haloperoxidase's Catalytic Activity by Boric Acid-Towards a Potential Biocatalytic Role of Boron.

    Science.gov (United States)

    Natalio, Filipe; Wiese, Stefanie; Brandt, Wolfgang; Wessjohann, Ludger

    2017-04-11

    Boron's unusual properties inspired major advances in chemistry. In nature, the existence and importance of boron has been fairly explored (e.g. bacterial signaling, plant development) but its role as biological catalyst was never reported. Here, we show that boric acid [B(OH) 3 ] can restore chloroperoxidase activity of Curvularia inaequalis recombinant apo-haloperoxidase's (HPO) in the presence of hydrogen peroxide and chloride ions. Molecular modeling and semi-empirical PM7 calculations support a thermodynamically highly favored (bio)catalytic mechanism similarly to vanadium haloperoxidases (V-HPO) in which [B(OH) 3 ] is assumedly located in apo-HPO's active site and a monoperoxyborate [B(OH) 3 (OOH) - ] intermediate is formed and stabilized by interaction with specific active site amino acids leading ultimately to the formation of HOCl. Thus, B(OH) 3 -HPO provides the first evidence towards the future exploitation of boron's role in biological systems. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Highly active and non-corrosive catalytic systems for the coupling reactions of ethylene oxide and CO{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Shuyao; Jin, So Jeong; Kim, Young Jin; Lee, Je Seung; Kim, Hoon Sik [Dept. of Chemistry and Research Institute of Basic Sciences, Kyung Hee University, Seoul (Korea, Republic of); Hong, Jongki; Lee, Won Woong [College of Pharmacy, Kyung Hee University, Seoul (Korea, Republic of); Ryu, Jung Bok [R and D Center, Chuncheon (Korea, Republic of)

    2017-02-15

    Lithium halide-based molten salts (LiX-[BMIm]Br) synthesized from the reactions of lithium halides (LiX, X = Cl or Br) with 1-butyl-3-methylimidazolium bromide ([BMIm]Br), and their catalytic performances and corrosivities were tested for the coupling reactions of ethylene oxide with carbon dioxide to produce ethylene carbonate. The activity of a molten salt was influenced with the change of halide ion. At a fixed molar amount of LiX, the activity of LiX-[BMIm]Br increased with increasing molar ratio of LiX/[BMIm]Br up to 1–1.25, and then decreased thereafter. Fast atom bombardment mass spectral analysis of LiBr-[BMIm]Br, obtained by dissolving LiBr in [BMIm]Br in a 1:1 molar ratio, implies that [Li{sub a} X{sub a+1}]{sup −} are active species for the carboxylation of ethylene oxide with LiX-[BMIm]Br. The corrosion test toward carbon steel coupons demonstrates that all the Cl-containing molten salts are corrosive, whereas the salts without containing Cl{sup −} are non-corrosive under the carboxylation condition.

  3. Effect of Co crystallinity on Co/CNT catalytic activity in CO/CO{sub 2} hydrogenation and CO disproportionation

    Energy Technology Data Exchange (ETDEWEB)

    Chernyak, Sergei A., E-mail: chernyak.msu@gmail.com [Lomonosov Moscow State University, Department of Chemistry, Leninskiye Gory 1-3, Moscow 119991 (Russian Federation); Kurnakov Institute of General and Inorganic Chemistry of the Russian Academy of Sciences, Department of Physical Chemistry, Leninsky Avenue 31, Moscow 119991 (Russian Federation); Suslova, Evgeniya V.; Egorov, Alexander V.; Maslakov, Konstantin I. [Lomonosov Moscow State University, Department of Chemistry, Leninskiye Gory 1-3, Moscow 119991 (Russian Federation); Savilov, Serguei V.; Lunin, Valery V. [Lomonosov Moscow State University, Department of Chemistry, Leninskiye Gory 1-3, Moscow 119991 (Russian Federation); Kurnakov Institute of General and Inorganic Chemistry of the Russian Academy of Sciences, Department of Physical Chemistry, Leninsky Avenue 31, Moscow 119991 (Russian Federation)

    2016-05-30

    Highlights: • Amorphous and crystalline Co supported on CNTs were obtained by tuning of CNT surface. • CO and CO{sub 2} hydrogenation does not occur on amorphous Co particles. • Thermal activation of amorphous Co led to crystallization of metal. • Amorphous Co promotes CO disproportionation. • Carbon shells around the amorphous metal particles after the CO hydrogenation. - Abstract: Carbon nanotubes (CNTs) with different degree of surface oxidation were used as supports for 5 wt.% Co catalysts. CNTs and Co/CNT catalysts were analyzed by XPS, nitrogen adsorption, TEM and electron diffraction to reveal their structure. High oxidation degree of CNT surface (8.6 at.% of O) and low Co loading led to predominantly amorphous Co species. This resulted in the absence of catalytic activity in both CO and CO{sub 2} hydrogenation in opposite to the catalyst supported on less oxidized CNTs (5.4 at.% of O) where Co species were found to be crystalline. Thermal treatment of inactive catalyst in H{sub 2} and He led to the formation of Co crystal phase which was active in catalysis. Co particle size in catalyst supported on strongly oxidized CNTs was unchanged during CO hydrogenation in opposite to Co supported on less oxidized CNTs. Carbon shell formation on the surface of amorphous Co particles during CO hydrogenation was revealed, which testified CO disproportionation. Qualitative mechanism of CO hydrogenation on small Co particles was proposed.

  4. Support effects and catalytic trends for water gas shift activity of transition metals

    DEFF Research Database (Denmark)

    Boisen, Astrid; Janssens, T.V.W.; Schumacher, Nana Maria Pii

    2010-01-01

    Water gas shift activity measurements for 12 transition metals (Fe, Co, Ni, Cu, Ru, Rh, Pd, Ag, Re, Ir, Pt, Au) supported on inert MgAl2O4 and Ce0.75Zr0.25O2 are presented, to elucidate the influence of the active metal and the support. The activity is related to the adsorption energy of molecular...... activity on the MgAl2O4 support and are both characterized by weak CO adsorption. For the MgAl2O4-supported catalysts a volcano-type relation between the activity and the adsorption energy of atomic oxygen on the metal is obtained. The maximum activity is found for metals with a binding energy of oxygen...... around −2.5 eV. No clear correlation exists with the adsorption energy of CO. In contrast, the activity for the Ce0.75Zr0.25O2 support increases with increasing adsorption strength for CO, and based on a relatively low activity of Cu the activity does not seem to depend on the adsorption energy of oxygen...

  5. Problem solution as a guided activity with Mexican schoolchildren

    Directory of Open Access Journals (Sweden)

    Solovieva, Yulia

    2016-09-01

    Full Text Available The goal of the present study was to describe the organization of a guided activity for problem solution in primary school. The method, which was applied to mathematical problems, allowed us to propose a specific orientation for the proper solution of arithmetic problems by pupils. The study was based on the activity-theory approach applied to the process of teaching and learning. It was carried out with pupils in the second grade of a private school in the city of Puebla (Mexico. The method was used in the classroom during 30 school sessions of 1 hour per day. The methodology of formative experiment was used in the study. Qualitative analysis of the pedagogical process of teaching and learning was conducted. The results show that, after participation in the formative process, the schoolchildren became able to identify essential elements, data, and all relationships among them in order to solve mathematical problems. At the end of the program the verbal external level was raised for the process of orientation and the solution of problems together with the ability to use logarithms independently. We conclude that orientation, as a guided form of activity in primary school, is essential for the development of the ability to analyze problems.

  6. Antimicrobial activity of a new preservative for multiuse ophthalmic solutions.

    Science.gov (United States)

    Ghelardi, Emilia; Celandroni, Francesco; Gueye, Sokhna A; Salvetti, Sara; Campa, Mario; Senesi, Sonia

    2013-01-01

    The aim of this study was to examine the antimicrobial activity and the preservative efficacy of a novel preservative solution containing sodium hydroxymethyl glycinate (SHMG) and edetate disodium (EDTA), which is used for preservation of some commercial ophthalmic formulations. In vitro susceptibility assays were performed against several gram-positive (Staphylococcus aureus, Staphylococcus epidermidis, and Bacillus cereus) and gram-negative (Escherichia coli and Pseudomonas aeruginosa) bacteria representative of the microbial flora of epithelial surfaces or colonizing the conjunctiva, as well as against Candida albicans and Aspergillus niger. Using different concentrations of SHMG alone or in combination with EDTA, the minimal inhibitory and microbicidal concentrations against these organisms were assessed. In addition, 8 brands of multidose eye drops containing 0.002% SHMG and 0.1% EDTA as preservative were tested for antimicrobial activity using the antimicrobial effectiveness test recommended by the international pharmacopoeias. The minimal inhibitory and bactericidal/fungicidal concentration values of SHMG ranged from 0.0025% to 0.0125% for bacteria and from 0.125% to 0.50% for mold and yeast. Susceptibility testing demonstrated that the addition of EDTA substantially increased the SHMG activity against all bacterial and fungal strains. The preservative effectiveness test was applied to commercial eye drops. All the drop solutions met the criteria reported by the U.S. Pharmacopeia for parenteral and ophthalmic preparations. All products also satisfied the major acceptance criteria of the European Pharmacopeia with respect to the antifungal activity. With regard to the antibacterial activity, the less-stringent criteria of the European Pharmacopeia were fulfilled. The present study demonstrates the efficacy of a novel preservative for ophthalmic solutions (SHMG/EDTA) and its activity in protecting selected commercial artificial tears against microbial

  7. IFCC primary reference procedures for the measurement of catalytic activity concentrations of enzymes at 37 °C. Part 9: reference procedure for the measurement of catalytic concentration of alkaline phosphatase International Federation of Clinical Chemistry and Laboratory Medicine (IFCC) Scientific Division, Committee on Reference Systems of Enzymes (C-RSE) (1)).

    Science.gov (United States)

    Schumann, Gerhard; Klauke, Rainer; Canalias, Francesca; Bossert-Reuther, Steffen; Franck, Paul F H; Gella, F-Javier; Jørgensen, Poul J; Kang, Dongchon; Lessinger, Jean-Marc; Panteghini, Mauro; Ceriotti, Ferruccio

    2011-09-01

    Abstract This paper is the ninth in a series dealing with reference procedures for the measurement of catalytic activity concentrations of enzymes at 37 °C and the certification of reference preparations. Other parts deal with: Part 1. The concept of reference procedures for the measurement of catalytic activity concentrations of enzymes; Part 2. Reference procedure for the measurement of catalytic concentration of creatine kinase; Part 3. Reference procedure for the measurement of catalytic concentration of lactate dehydrogenase; Part 4. Reference procedure for the measurement of catalytic concentration of alanine aminotransferase; Part 5. Reference procedure for the measurement of catalytic concentration of aspartate aminotransferase; Part 6. Reference procedure for the measurement of catalytic concentration of γ-glutamyltransferase; Part 7. Certification of four reference materials for the determination of enzymatic activity of γ-glutamyltransferase, lactate dehydrogenase, alanine aminotransferase and creatine kinase at 37 °C; Part 8. Reference procedure for the measurement of catalytic concentration of α-amylase. The procedure described here is derived from the previously described 30 °C IFCC reference method. Differences are tabulated and commented on in Appendix 1.

  8. Dynamic structurization in solutions of hydrodynamically active polymers

    International Nuclear Information System (INIS)

    Pogrebnyak, V.G.; Tverdokhleb, S.V.; Naumchuk, N.V.

    1993-01-01

    The processes of ordering and self-regulation in nonlinear systems have attracted great attention because understanding the principles of self-regulation and its thermodynamics can become a clue to many physical phenomena. In this work, it is experimentally established that, under the condition of elongational flows, dynamic structurization and periodic processes may originate in the solutions of flexible, hydrodynamically-active polymers due to self-regulation in these systems. The hydrodynamic elongational field was created using the flow of a Newtonian liquid (water, acetone, dioxane) converging to a small opening. The hydrodynamically-active polymers were polyethylene oxide or hydrolyzed polyacrylamide

  9. 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.

  10. Catalytic oxidation of sulfide in drinking water treatment: activated carbon as catalyst; Katalytische Oxidation von Sulfid bei der Trinkwasseraufbereitung: Aktivkohle als Katalysator

    Energy Technology Data Exchange (ETDEWEB)

    Hultsch, V; Grischek, T; Wolff, D; Worch, E [Technische Univ. Dresden (Germany). Inst. fuer Wasserchemie; Gun, J [Hebrew Univ. of Jerusalem (Israel). Div. of Environmental Sciences, Fredy and Nadine Herrmann School of Applied Science

    2001-07-01

    In regions with warm climate and limited water resources high sulfide concentrations in groundwater can cause problems during drinking water treatment. Aeration of the raw water is not always sufficient to ensure the hydrogen sulfide concentration below the odour threshold value for hydrogen sulfide. As an alternative, activated carbon can be used as a catalyst for sulfide oxidation of raw water. The use of different types of activated carbon was investigated in kinetic experiments. Both Catalytic Carbon from Calgon Carbon and granulated activated carbon from Norit showed high catalytic activities. The results of the experiments are discussed with regard to the practical use of activated carbon for the elimination of hydrogen sulfide during drinking water treatment. (orig.)

  11. Catalytic methanol dissociation

    International Nuclear Information System (INIS)

    Alcinikov, Y.; Fainberg, V.; Garbar, A.; Gutman, M.; Hetsroni, G.; Shindler, Y.; Tatrtakovsky, L.; Zvirin, Y.

    1998-01-01

    Results of the methanol dissociation study on copper/potassium catalyst with alumina support at various temperatures are presented. The following gaseous and liquid products at. The catalytic methanol dissociation is obtained: hydrogen, carbon monoxide, carbon dioxide, methane, and dimethyl ether. Formation rates of these products are discussed. Activation energies of corresponding reactions are calculated

  12. Catalytic synthesis and antioxidant activity of sulfated polysaccharide from Momordica charantia L.

    Science.gov (United States)

    Liu, Xin; Chen, Tong; Hu, Yan; Li, Kexin; Yan, Liushui

    2014-03-01

    Sulfated derivatives of polysaccharide from Momordica charantia L. (MCPS) with different degree of sulfation (DS) were synthesized by chlorosulfonic acid method with ionic liquids as solvent. Fourier transform infrared spectra and 13C nuclear magnetic resonance spectra indicated that C-6 substitution was predominant in MCPS compared with the C-2 position. Compared with the native polysaccharide from Momordica charantia L. (MCP), MCPS exhibited more excellent antioxidant activities in vitro, which indicated that sulfated modification could enhance antioxidant activities of MCP. Furthermore, high DS and moderate molecular weight could improve the antioxidant activities of polysaccharide. Copyright © 2013 Wiley Periodicals, Inc.

  13. On the mechanism of sulfite activation of chloroplast thylakoid ATPase and the relation of ADP tightly bound at a catalytic site to the binding change mechanism

    International Nuclear Information System (INIS)

    Du, Z.; Boyer, P.D.

    1990-01-01

    Washed chloroplast thylakoid membranes upon exposure to [ 3 H]ADP retain in tightly bound [ 3 H]ADP on a catalytic site of the ATP synthase. The presence of sufficient endogenous or added Mg 2+ results in an enzyme with essentially no ATPase activity. Sulfite activates the ATPase, and many molecules of ATP per synthase can be hydrolyzed before most of the bound [ 3 H]ADP is released, a result interpreted as indicating that the ADP is not bound at a site participating in catalysis by the sulfite-activated enzyme. The authors present evidence that this is not the case. The Mg 2+ - and ADP-inhibited enzyme when exposed to MgATP and 20-100 mM sulfite shows a lag of about 1 min at 22 degree C and of about 15 s at 37 degree C before reaching the same steady-state rate as attained with light-activated ATPase that has not been inhibited by Mg 2+ and ADP. The lag is not eliminated if the enzyme is exposed to sulfite prior to MgATP addition, indicating that ATPase turnover is necessary for the activation. The release of most of the bound [ 3 H]ADP parallels the onset of ATPase activity, although some [ 3 H]ADP is not released even with prolonged catalytic turnover and may be on poorly active or inactive enzyme or at noncatalytic sites. The results are consistent with most of the tightly bound [ 3 H]ADP being at a catalytic site and being replaced as this Mg 2+ - and ADP-inhibited site regains equivalent participation with other catalytic sites on the activated enzyme. The sulfite activation can be explained by sulfite combination at a P i binding site of the enzyme-ADP-Mg 2+ complex to give a form more readily activated by ATP binding at an alternative site

  14. Preparation, characterization and catalytic activity of mesoporous Ag2HPW12O40/SBA-15 and Ag2HPW12O40/TiO2 composites

    International Nuclear Information System (INIS)

    Holclajtner-Antunović, Ivanka; Bajuk-Bogdanović, Danica; Popa, Alexandru; Sasca, Viorel; Nedić Vasiljević, Bojana; Rakić, Aleksandra; Uskoković-Marković, Snežana

    2015-01-01

    The current study reports the synthesis and characterization of tungstophosphoric acid and its acid silver salt supported on mesoporous molecular sieve SBA-15 and TiO 2 . Because silver salts are partially insoluble, the SBA-15 and TiO 2 supported silver acid salts were prepared by two step sequential impregnations. The synthesized catalysts were characterized by various physicochemical methods such as Fourier transform infrared and Raman spectroscopy, differential thermal analysis, thermogravimetric analysis, X-ray diffraction, scanning electron microscopy and nitrogen physisorption at −196 °C. It is observed that both active phases keep their Keggin-type structure after being supported on the supports while their specific surface area is considerably increased by deposition on mesoporous substrates. The results also indicated that the synthesized catalysts retained the morphology specific for each of the supports, while their thermal stability is increased in comparison with their active phases. The catalytic activity of the prepared catalysts was probed for the vapor phase dehydration of ethanol at 300 °C. Results revealed that all the catalysts show considerably improved catalytic activity in comparison to the bulk active phases. - Highlights: • SBA-15 and TiO 2 supported Ag 2 HPW 12 O 40 and H 3 PW 12 O 40 were prepared. • Active phases are uniformly dispersed without changing morphology of the substrates. • Composites are more thermally stable than active phases. • Composites exhibit high catalytic activity for gas phase ethanol dehydration

  15. Mechanism of Catalytic Behavior and Structure of Active Centers in CuY Zeolite

    OpenAIRE

    Tanabe, Shuji; Matsumoto, Hiroshige

    1990-01-01

    The experimental and theoretical basis for the activated coppere xchanged Y zeolite system have been studied by the observation and analysis in the electronspin resonanace (ESR) , infrared (IR) and extended X-ray absorption fine structure (EXAFS) spectroscopies.

  16. Identification of intrinsic catalytic activity for electrochemical reduction of water molecules to generate hydrogen

    KAUST Repository

    Shinagawa, Tatsuya; Takanabe, Kazuhiro

    2015-01-01

    Insufficient hydronium ion activities at near-neutral pH and under unbuffered conditions induce diffusion-limited currents for hydrogen evolution, followed by a reaction with water molecules to generate hydrogen at elevated potentials. The observed

  17. An isozyme of acid alpha-glucosidase with reduced catalytic activity for glycogen.

    OpenAIRE

    Beratis, N G; LaBadie, G U; Hirschhorn, K

    1980-01-01

    Both the common and a variant isozyme of acid alpha-glucosidase have been purified from a heterozygous placenta with CM-Sephadex, ammonium sulfate precipitation, dialysis, Amicon filtration, affinity chromatography by Sephadex G-100, and DEAE-cellulose chromatography. Three and two activity peaks, from the common and variant isozymes, respectively, were obtained by DEAE-cellulose chromatography using a linear NaCl gradient. The three peaks of activity of the common isozyme were eluted with 0....

  18. Effect of Co3O4 and Co3O4/CeO2 infiltration on the catalytic and electro-catalytic activity of LSM15/CGO10 porous cells stacks for oxidation of propene

    DEFF Research Database (Denmark)

    Ippolito, Davide; Kammer Hansen, Kent

    2015-01-01

    The objective of this work was to study the effect of Co3O4 and Co3O4/CeO2 infiltration on the propene oxidation catalytic activity of a La0.85Sr0.15MnO3/Ce0.9Gd0.1O1.95 electrochemical porous cell stack (11 layers, 5 single cells in series). The effect of the infiltration of Co3O4 and Co3O4/CeO2...... on the electrochemical properties of the porous cell stack was also investigated by electrochemical impedance spectroscopy (EIS). Co3O4 and Co3O4/CeO2 exhibited high catalytic activity for propene oxidation. The increase of propene oxidation rate with +4 V (0.8 V/cell) polarization reached 10% for the Co3O4 infiltrated...... reactor and 48% of efficiency at 300 °C. The Co3O4/CeO2 co-infiltration decreased the reactor polarization resistance, while Co3O4 infiltration had negligible effect on reactor electrochemical performance. The beneficial effect of CeO2 on the electrode activity was attributed to the increased...

  19. Robust non-carbon titanium nitride nanotubes supported Pt catalyst with enhanced catalytic activity and durability for methanol oxidation reaction

    International Nuclear Information System (INIS)

    Xiao, Yonghao; Zhan, Guohe; Fu, Zhenggao; Pan, Zhanchang; Xiao, Chumin; Wu, Shoukun; Chen, Chun; Hu, Guanghui; Wei, Zhigang

    2014-01-01

    By the combination of solvothermal alcoholysis and post-nitriding method, titanium nitride nanotubes (TiN NTs), with high surface area, hollow and interior porous structure are prepared successfully and used at a support for Pt nanoparticles. The TiN NTs supported Pt (Pt/TiN NTs) catalyst displays enhanced activity and durability towards methanol oxidation reaction (MOR) compared with the commercial Pt/C (E-TEK) catalyst. X ray diffraction (XRD), nitrogen adsorption/desorption, transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) measurements are performed to investigate the physicochemical properties of the synthesized catalyst. SEM and TEM images reveal that the wall of the TiN NTs is porous and Pt nanoparticles supported on the dendritic TiN nanocrystals exhibit small size and good dispersion. Effects of inherent corrosion-resistant, tubular and porous nanostructures and electron transfer due to the strong metal–support interactions of TiN NTs contribute to the enhanced catalytic activity and stability of Pt/TiN NTs towards the MOR

  20. Alternative splicing at exon 2 results in the loss of the catalytic activity of mouse DNA polymerase iota in vitro.

    Science.gov (United States)

    Kazachenko, Konstantin Y; Miropolskaya, Nataliya A; Gening, Leonid V; Tarantul, Vyacheslav Z; Makarova, Alena V

    2017-02-01

    Y-family DNA polymerase iota (Pol ι) possesses both DNA polymerase and dRP lyase activities and was suggested to be involved in DNA translesion synthesis and base excision repair in mammals. The 129 strain of mice and its derivatives have a natural nonsense codon mutation in the second exon of the Pol ι gene resulting in truncation of the Pol ι protein. These mice were widely used as a Pol ι-null model for in vivo studies of the Pol ι function. However whether 129-derived strains of mice are fully deficient in the Pol ι functions was a subject of discussion since Pol ι mRNA undergoes alternative splicing at exon 2. Here we report purification of mouse Pol ι lacking the region encoded by exon 2, which includes several conserved residues involved in catalysis. We show that the deletion abrogates both the DNA polymerase and dRP lyase activities of Pol ι in the presence of either Mg 2+ or Mn 2+ ions. Thus, 129-derived strains of mice express catalytically inactive alternatively spliced Pol ι variant, whose cellular functions, if any exist, remain to be established. Copyright © 2017 Elsevier B.V. All rights reserved.

  1. Citric acid induced promoted dispersion of Pt on the support and enhanced catalytic activities for a Pt-based catalyst

    Science.gov (United States)

    Cheng, Tianqiong; Wang, Jianli; Wang, Suning; Cui, Yajuan; Zhang, Hailong; Yan, Shuang; Yuan, Shandong; Chen, Yaoqiang

    2017-12-01

    Citric acid (CA), as the chelating agent, was introduced to obtain the enhanced Pt dispersion and catalytic activities for the Pt-based catalysts supported on oxygen-storage material. The role and content of CA were investigated systematically. It was found that the citric acid-assisted catalysts showed better Pt dispersion and smaller nanoparticle size of Pt. Thus, the catalyst had lower reduction temperature, preferable thermostability and possessed more oxidation state of Pt species under the oxidation atmosphere. The citric acid-induced fresh catalysts were excellent to convert CO and the corresponding aged ones exhibited higher activities for the elimination of all the target pollutants. Among the aged catalysts, P2-a (the mole ratio of Pt/CA is 2:1) presented the best performance. Particularly, compared with the reference sample (Pc-a), the light-off temperatures (T50) of NO, HC and CO for P2-a decreased by 39 °C, 42 °C and 72 °C, respectively, and the full-conversion temperatures (T90) of NO, HC and CO for P2-a decreased by 44 °C, 44 °C and 48 °C, respectively. Therefore, this work provides a facile and valid method to manufacture advanced catalysts for purification of the vehicle exhaust in the future.

  2. Formation of carbon nanosheets via simultaneous activation and catalytic carbonization of macroporous anion-exchange resin for supercapacitors application.

    Science.gov (United States)

    Peng, Hui; Ma, Guofu; Sun, Kanjun; Mu, Jingjing; Zhang, Zhe; Lei, Ziqiang

    2014-12-10

    Two-dimensional mesoporous carbon nanosheets (CNSs) have been prepared via simultaneous activation and catalytic carbonization route using macroporous anion-exchange resin (AER) as carbon precursor and ZnCl2 and FeCl3 as activating agent and catalyst, respectively. The iron catalyst in the skeleton of the AER may lead to carburization to form a sheetlike structure during the carbonization process. The obtained CNSs have a large number of mesopores, a maximum specific surface area of 1764.9 m(2) g(-1), and large pore volume of 1.38 cm(3) g(-1). As an electrode material for supercapacitors application, the CNSs electrode possesses a large specific capacitance of 283 F g(-1) at 0.5 A g(-1) and excellent rate capability (64% retention ratio even at 50 A g(-1)) in 6 mol L(-1) KOH. Furthermore, CNSs symmetric supercapacitor exhibits specific energies of 17.2 W h kg(-1) at a power density of 224 W kg(-1) operated in the voltage range of 0-1.8 V in 0.5 mol L(-1) Na2SO4 aqueous electrolyte, and outstanding cyclability (retains about 96% initial capacitance after 5000 cycles).

  3. Sodium dodecyl sulfate-assisted hydrothermal synthesis of mesoporous nickel cobaltite nanoparticles with enhanced catalytic activity for methanol electrooxidation

    Science.gov (United States)

    Ding, Rui; Qi, Li; Jia, Mingjun; Wang, Hongyu

    2014-04-01

    Mesoporous nickel cobaltite (NiCo2O4) nanoparticles have been synthesized via a facile hydrothermal strategy with the assistance of sodium dodecyl sulfate (SDS) soft template (ST). Their physicochemical properties have been characterized via X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy-dispersive X-ray spectra (EDS), transmission electron microscopy (TEM), X-ray photoelectron spectra (XPS) and nitrogen sorption measurements. Their electrocatalytic performances have been examined by cyclic voltammetry (CV), linear sweep voltammetry (LSV), chronoamperometry (CA) and electrochemical impedance spectroscopy (EIS) tests. The obtained NiCo2O4 materials exhibit a typical nanoscale crystalline hexagonal morphology with specific surface area (SSA) and mesopore volume of 88.63 m2 g-1 and 0.298 cm3 g-1. Impressively, the SDS-assisted NiCo2O4 electrode shows a catalytic current density of 125 mA cm-2 and 72% retention for consecutive 1000 s at 0.6 V in 1 M KOH and 0.5 M CH3OH electrolytes towards methanol (CH3OH) electrooxidation, which is better than the one without SDS assistance. The pronounced electrocatalytic activity is largely ascribed to their higher surface intensities of Co and Ni species and superior mesoporous nanostructures, which provide the richer electroactive sites and faster electrochemical kinetics, leading to the enhanced electrocatalytic activity.

  4. Novel Co3O4 Nanoparticles/Nitrogen-Doped Carbon Composites with Extraordinary Catalytic Activity for Oxygen Evolution Reaction (OER)

    Science.gov (United States)

    Yang, Xiaobing; Chen, Juan; Chen, Yuqing; Feng, Pingjing; Lai, Huixian; Li, Jintang; Luo, Xuetao

    2018-03-01

    Herein, Co3O4 nanoparticles/nitrogen-doped carbon (Co3O4/NPC) composites with different structures were prepared via a facile method. Structure control was achieved by the rational morphology design of ZIF-67 precursors, which were then pyrolyzed in air to obtain Co3O4/NPC composites. When applied as catalysts for the oxygen evolution reaction (OER), the M-Co3O4/NPC composites derived from the flower-like ZIF-67 showed superior catalytic activities than those derived from the rhombic dodecahedron and hollow spherical ZIF-67. The former M-Co3O4/NPC composite displayed a small over-potential of 0.3 V, low onset potential of 1.41 V, small Tafel slope of 83 mV dec-1, and a desirable stability. (94.7% OER activity was retained after 10 h.) The excellent performance of the flower-like M-Co3O4/NPC composite in the OER was attributed to its favorable structure. [Figure not available: see fulltext.

  5. Biosynthesis of silver nanoparticles using Momordica charantia leaf broth: Evaluation of their innate antimicrobial and catalytic activities.

    Science.gov (United States)

    Ajitha, B; Reddy, Y Ashok Kumar; Reddy, P Sreedhara

    2015-05-01

    Silver nanoparticles (AgNPs) were prepared through green route with the aid of Momordica charantia leaf extract as both reductant and stabilizer. X-ray diffraction pattern (XRD) and selected area electron diffraction (SAED) fringes revealed the structure of AgNPs as face centered cubic (fcc). Morphological studies elucidate the nearly spherical AgNPs formation with particle size in nanoscale. Biosynthesized AgNPs were found to be photoluminescent and UV-Vis absorption spectra showed one surface plasmon resonance peak (SPR) at 424nm attesting the spherical nanoparticles formation. XPS study provides the surface chemical nature and oxidation state of the synthesized nanoparticles. FTIR spectra ascertain the reduction and capping nature of phytoconstituents of leaf extract in AgNPs synthesis. Further, these AgNPs showed effective antimicrobial activity against tested pathogens and thus applicable as potent antimicrobial agent. In addition, the synthesized AgNPs were observed to have an excellent catalytic activity on the reduction of methylene blue by M. charantia which was confirmed by the decrement in maximum absorbance values of methylene blue with respect to time and is ascribed to electron relay effect. Copyright © 2015 Elsevier B.V. All rights reserved.

  6. Could microwave induced catalytic oxidation (MICO) process over CoFe2O4 effectively eliminate brilliant green in aqueous solution?

    International Nuclear Information System (INIS)

    Ju, Yongming; Wang, Xiaoyan; Qiao, Junqin; Li, Guohua; Wu, You; Li, Yuan; Zhang, Xiuyu; Xu, Zhencheng; Qi, Jianying; Fang, Jiande; Dionysiou, Dionysios D.

    2013-01-01

    Highlights: • The elimination of BG over CoFe 2 O 4 (CP) was mainly due to the residue of NaOH. • Salicylic acid failed to capture hydroxyl radicals within MICO process. • This study indicated dim prospects for the MICO-based elimination of contaminants. -- Abstract: In this study, we adopted the chemical co-precipitation (CP) method and sol–gel method followed by calcination at temperatures of 100–900 °C for 12 h to synthesize CoFe 2 O 4 materials, which were further characterized by TEM, XRD and XPS techniques. The properties of CoFe 2 O 4 materials were evaluated in a microwave (MW) induced catalytic oxidation (MICO) process for the elimination of brilliant green (BG). The results showed that: (1) the removal rates of BG gradually decreased over a series of CoFe 2 O 4 materials prepared by CP method and calcinated with 100–700 °C (except 900 °C) for 12 h within three reuse cycles; for comparison, no removal of BG was obtained over CoFe 2 O 4 synthesized by sol–gel method and CoFe 2 O 4 -900 (CP); (2) no hydroxyl radicals were captured with salicylic acid used as molecular probe in the MICO process; (3) MW irradiation enhanced the release of residual NaOH within the microstructure of CoFe 2 O 4 and further discolored BG, because BG is sensitive to pH; (4) granular activated carbon (GAC), an excellent MW-absorbing material possessing hi