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Sample records for 2 wet catalytic

  1. Al 2O 3 supported Ru catalysts prepared by thermolysis of Ru 3(CO) 12 for catalytic wet air oxidation

    NASA Astrophysics Data System (ADS)

    Yu, Chaoying; Zhao, Peiqing; Chen, Gexin; Hu, Bin

    2011-06-01

    Low loading catalysts Ru/γ-Al 2O 3 and Ru-Ce/γ-Al 2O 3 were prepared by thermolysis of Ru 3(CO) 12 on γ-Al 2O 3. The catalysts were characterized by XPS, XRD and SEM. Two new Ru species (Ru A and Ru B) were detected during the Ru 3(CO) 12 decomposition process due to chemical interaction with the active OH groups on the surface of Al 2O 3 support, and the reduction of them can lead to more dispersed metallic phases. The sample was completely decomposed at 673 K in H 2, and RuO 2 was formed with minor amounts of Ru 0. When the temperature was increased to 773 K to heat the sample, the ratio of Ru 0 to RuO 2 increased. However, after the addition of CeO 2, only RuO 2 was detected on surface. The catalysts exhibited high activities in Catalytic Wet Air Oxidation (CWAO) of different organic compounds at high concentration such as isopropyl alcohol, phenol, acetic acids and N,N-dimethylformamide, which is attributed to the better dispersion of Ru particles and the addition of CeO 2 further enhanced number of effectively active sites on the cluster-derived catalyst surface.

  2. Treatment of aniline by catalytic wet air oxidation: comparative study over CuO/CeO2 and NiO/Al2O3.

    PubMed

    Ersöz, Gülin; Atalay, Süheyda

    2012-12-30

    The treatment of aniline by catalytic wet air oxidation (CWAO) was studied in a bubble reactor. The experiments were performed to investigate the effects of catalyst loading, temperature, reaction time, air flow rate, and pressure on aniline removal. The catalytic effects of the prepared nanostructured catalysts, CuO/CeO(2) (10% wt) and NiO/Al(2)O(3) (10% wt), on the CWAO treatment efficiency were also examined and compared. The prepared catalysts seem to be active having an aniline removal of 45.7% with CuO/CeO(2) and 41.9% with NiO/Al(2)O(3). The amount of N(2) formed was approximately the same for both of the catalysts. PMID:23041516

  3. Methane Production from Catalytic Wet Gasification of Animal Manure

    Technology Transfer Automated Retrieval System (TEKTRAN)

    This research investigates the technical and economical viability of a proprietary catalytic wet gasification process in treating animal wastewater, capturing nutrients, destroying pharmaceutically active compounds (PACs) and estrogens, and producing methane. This study reviews and analyzes physicoc...

  4. Post-treatment of biologically treated wastewater containing organic contaminants using a sequence of H2O2 based advanced oxidation processes: photolysis and catalytic wet oxidation.

    PubMed

    Rueda-Márquez, J J; Sillanpää, M; Pocostales, P; Acevedo, A; Manzano, M A

    2015-03-15

    In this paper the feasibility of a multi-barrier treatment (MBT) for the regeneration of synthetic industrial wastewater (SIWW) was evaluated. Industrial pollutants (orange II, phenol, 4-chlorophenol and phenanthrene) were added to the effluent of municipal wastewater treatment plant. The proposed MBT begins with a microfiltration membrane pretreatment (MF), followed by hydrogen peroxide photolysis (H2O2/UVC) and finishing, as a polishing step, with catalytic wet peroxide oxidation (CWPO) using granular activated carbon (GAC) at ambient conditions. During the microfiltration step (0.7 μm) the decrease of suspended solids concentration, turbidity and Escherichia coli in treated water were 88, 94 and 99%, respectively. Also, the effluent's transmittance (254 nm) was increased by 14.7%. Removal of more than 99.9% of all added pollutants, mineralization of 63% of organic compounds and complete disinfection of total coliforms were reached during the H2O2/UVC treatment step (H2O2:TOC w/w ratio = 5 and an UVC average dose accumulated by wastewater 8.80 WUVC s cm(-2)). The power and efficiency of the lamp, the water transmittance and photoreactor geometry are taken into account and a new equation to estimate the accumulated dose in water is suggested. Remaining organic pollutants with a higher oxidation state of carbon atoms (+0.47) and toxic concentration of residual H2O2 were present in the effluent of the H2O2/UVC process. After 2.3 min of contact time with GAC at CWPO step, 90 and 100% of total organic carbon and residual H2O2 were removed, respectively. Also, the wastewater toxicity was studied using Vibrio fischeri and Sparus aurata larvae. The MBT operational and maintenance costs (O&M) was estimated to be 0.59 € m(-3). PMID:25600300

  5. Degradation process analysis of the azo dyes by catalytic wet air oxidation with catalyst CuO/γ-Al2O3.

    PubMed

    Hua, Li; Ma, Hongrui; Zhang, Lei

    2013-01-01

    Three azo dyes (Methyl Orange, Direct Brown and Direct Green) were treated by catalytic wet air oxidation (CWAO) with the catalysts CuO/γ-Al(2)O(3) prepared by consecutive impregnation. The relationship of decolorization extent, chemical oxygen demand (COD) removal extent and total organic carbon (TOC) in dye solution were investigated. The results indicated that the CuO/γ-Al(2)O(3) catalyst had excellent catalytic activity in treating azo dyes. Almost 99% of color and 70% of TOC were removed in 2h. The high removal extent of color and TOC indicated that the CWAO obtained perfect decomposition for pollutants. The degradation pathway of azo dyes was analyzed by UV-Vis, FTIR and MS. According to the examined results, the hydroxyl ((·)OH) radicals induced strong oxidizing effects in the target solution and destroyed the chromophoric groups of azo-benzene conjugated of the molecular structure. Considering characteristics of the dye structure, the azo bond (-N=N-) would first be attacked by the hydroxyl radical and other free radicals. With the continuous oxidization and the long reaction time at high temperature, these intermediates could be oxidized to the final oxidation products, such as water and carbon dioxide. PMID:22795071

  6. Scale-up of catalytic wet oxidation under moderate conditions

    SciTech Connect

    Harf, J.; Hug, A.; Vogel, F.; Rohr, P.R. von

    1999-05-01

    The Catalytic Wet Oxidation with pure oxygen is a suitable treatment process for the degradation of organic matter in wastewaters and sludges. The applied moderate reaction conditions lead only to a partial oxidation of the organics. Therefore the resulting process water has to be purified in a biological treatment plant. In this study, experimental data collected during the wet oxidation of phenol and sewage sludge in a laboratory batch reactor as well as in a pilot plant are presented. A generalized kinetic model combined with a residence time analysis allows to predict accurately the degradation of organic matter in the pilot plant. The wet oxidation of wastewaters and sewage sludge was realized in one single plant concept. Treating suspended or diluted organic wastes produces a highly biodegradable process water containing low molecular oxidation products. The investigated Catalytic Wet Oxidation of sewage sludge generates a residual solid complying with the European quality standards of disposal concerning leachability and organic content. Due to its low capital and operating costs, the Catalytic Wet Oxidation process constitutes an acceptable alternative to incineration for the disposal of sludges.

  7. Wet peroxide oxidation and catalytic wet oxidation of stripped sour water produced during oil shale refining.

    PubMed

    Prasad, Jaidev; Tardio, James; Jani, Harit; Bhargava, Suresh K; Akolekar, Deepak B; Grocott, Stephen C

    2007-07-31

    Catalytic wet oxidation (CWO) and wet peroxide oxidation (WPO) of stripped sour water (SSW) from an oil shale refinery was investigated. Greater than 70% total organic carbon (TOC) removal from SSW was achieved using Cu(NO(3))(2) catalysed WO under the following conditions using a glass lined reaction vessel: 200 degrees C, pO(2)=0.5MPa, 3h, [Cu(NO(3))(2)]=67mmol/L. Significant TOC removal ( approximately 31%) also occurred in the system without added oxygen. It is proposed that this is predominantly due to copper catalysed oxidative decarboxylation of organics in SSW based on observed changes in copper oxidation state. Greater than 80% TOC removal was achieved using WPO under the following conditions: 150 degrees C, t=1.5h, [H(2)O(2)]=64g/L. Significantly more TOC could be removed from SSW by adding H(2)O(2) in small doses as opposed to adding the same total amount in one single dose. It was concluded that WPO was a far more effective process for removing odorous compounds from SSW. PMID:17537573

  8. Catalytic and non-catalytic wet air oxidation of sodium dodecylbenzene sulfonate: kinetics and biodegradability enhancement.

    PubMed

    Suárez-Ojeda, María Eugenia; Kim, Jungkwon; Carrera, Julián; Metcalfe, Ian S; Font, Josep

    2007-06-18

    Wet air oxidation (WAO) and catalytic wet air oxidation (CWAO) were investigated as suitable precursors for the biological treatment of industrial wastewater containing sodium dodecylbenzene sulfonate (DBS). Two hours WAO semi-batch experiments were conducted at 15 bar of oxygen partial pressure (P(O2)) and at 180, 200 and 220 degrees C. It was found that the highest temperature provides appreciable total organic carbon (TOC) and chemical oxygen demand (COD) abatement of about 42 and 47%, correspondingly. Based on the main identified intermediates (acetic acid and sulfobenzoic acid) a reaction pathway for DBS and a kinetic model in WAO were proposed. In the case of CWAO experiments, seventy-two hours tests were done in a fixed bed reactor in continuous trickle flow regime, using a commercial activated carbon (AC) as catalyst. The temperature and P(O2) were 140-160 degrees C and 2-9 bar, respectively. The influence of the operating conditions on the DBS oxidation, the occurrence of oxidative coupling reactions over the AC, and the catalytic activity (in terms of substrate removal) were established. The results show that the AC without any supported active metal behaves bi-functional as adsorbent and catalyst, giving TOC conversions up to 52% at 160 degrees C and 2 bar of P(O2), which were comparable to those obtained in WAO experiments. Respirometric tests were completed before and after CWAO and to the main intermediates identified through the WAO and CWAO oxidation route. Then, the readily biodegradable COD (COD(RB)) of the CWAO and WAO effluents were found. Taking into account these results it was possible to compare whether or not the CWAO or WAO effluents were suitable for a conventional activated sludge plant inoculated with non adapted culture. PMID:17363148

  9. Process of forming catalytic surfaces for wet oxidation reactions

    NASA Technical Reports Server (NTRS)

    Jagow, R. B. (Inventor)

    1977-01-01

    A wet oxidation process was developed for oxidizing waste materials, comprising dissolved ruthenium salt in a reactant feed stream containing the waste materials. The feed stream is introduced into a reactor, and the reactor contents are then raised to an elevated temperature to effect deposition of a catalytic surface of ruthenium black on the interior walls of the reactor. The feed stream is then maintained in the reactor for a period of time sufficient to effect at least partial oxidation of the waste materials.

  10. Evolution of toxicity upon wet catalytic oxidation of phenol.

    PubMed

    Santos, A; Yustos, P; Quintanilla, A; García-Ochoa, F; Casas, J A; Rodríguez, J J

    2004-01-01

    This work reports on the evolution of the toxicity of phenol-containing simulated wastewater upon catalytic wet oxidation with a commercial copper-based catalyst (Engelhard Cu-0203T). The results of the study show that this catalyst enhances detoxification, in addition to its effect on the oxidation rate. The EC50 values of the intermediates identified throughout the oxidation route of phenol have been determined and used to predict the evolution of toxicity upon oxidation. The predicted values have been compared with the ones measured directly from the aqueous solution during the oxidation process. To learn about the evolution of toxicity through out the routes of phenol oxidation, experiments have been performed with simulated wastewaters containing separately phenol, catechol, and hydroquinone as original pollutants. The significant increase of toxicity observed during the early stages of phenol oxidation is not directly related to the development of the brown color that derives mainly from catechol oxidation. This increase of toxicity is caused by the formation of hydroquinone and p-benzoquinone as intermediates, the former showing the highest toxicity. Furthermore, synergistic effects, giving rise to a significant increase of toxicity, have been observed. These effects derive from the interactions among copper leached from the catalyst and catechol, hydroquinone, and p-benzoquinone and demand that close attention be paid to this potential problem in catalytic wet oxidation. PMID:14740728

  11. Catalytic gasification of wet biomass in supercritical water

    SciTech Connect

    Antal, M.J. Jr.; Matsumura, Yukihiko; Xu, Xiaodong

    1995-12-31

    Wet biomass (water hyacinth, banana trees, cattails, green algae, kelp, etc.) grows rapidly and abundantly around the world. As a biomass crop, aquatic species are particularly attractive because their cultivation does not compete with land-based agricultural activities designed to produce food for consumption or export. However, wet biomass is not regarded as a promising feed for conventional thermochemical conversion processes because the cost associated with drying it is too high. This research seeks to address this problem by employing water as the gasification medium. Prior work has shown that low concentrations of glucose (a model compound for whole biomass) can be completely gasified in supercritical water at 600{degrees}C and 34.5 Wa after a 30 s reaction time. Higher concentrations of glucose (up to 22% by weight in water) resulted in incomplete conversion under these conditions. The gas contained hydrogen, carbon dioxide, carbon monoxide, methane, ethane, propane, and traces of other hydrocarbons. The carbon monoxide and hydrocarbons are easily converted to hydrogen by commercial technology available in most refineries. This prior work utilized capillary tube reactors with no catalyst. A larger reactor system was fabricated and the heterogeneous catalytic gasification of glucose and wet biomass slurry of higher concentration was studied to attain higher conversions.

  12. Development of a catalytic system for gasification of wet biomass

    SciTech Connect

    Elliott, D.C.; Sealock, L.J.; Phelps, M.R.; Neuenschwander, G.G.; Hart, T.R.

    1993-08-01

    A gasification system is under development at Pacific Northwest Laboratory that can be used with high-moisture biomass feedstocks. The system operates at 350 C and 205 atm using a liquid water phase as the processing medium. Since a pressurized system is used, the wet biomass can be fed as a slurry to the reactor without drying. Through the development of catalysts, a useful processing system has been produced. This paper includes assessment of processing test results of different catalysts. Reactor system results including batch, bench-scale continuous, and engineering-scale processing results are presented to demonstrate the applicability of this catalytic gasification system to biomass. The system has utility both for direct conversion of biomass to fuel gas or as a wastewater cleanup system for treatment of unconverted biomass from bioconversion processes. By the use of this system high conversion of biomass to fuel gas can be achieved. Medium-Btu is the primary product. Potential exists for recovery/recycle of some of the unreacted inorganic components from the biomass in the aqueous byproduct stream.

  13. Development of a catalytic system for gasification of wet biomass

    NASA Astrophysics Data System (ADS)

    Elliott, D. C.; Sealock, L. J.; Phelps, M. R.; Neuenschwander, G. G.; Hart, T. R.

    1993-08-01

    A gasification system is under development at Pacific Northwest Laboratory that can be used with high-moisture biomass feedstocks. The system operates at 350 C and 205 atm using a liquid water phase as the processing medium. Since a pressurized system is used, the wet biomass can be fed as a slurry to the reactor without drying. Through the development of catalysts, a useful processing system has been produced. This paper includes assessment of processing test results of different catalysts. Reactor system results including batch, bench-scale continuous, and engineering-scale processing results are presented to demonstrate the applicability of this catalytic gasification system to biomass. The system has utility both for direct conversion of biomass to fuel gas or as a wastewater cleanup system for treatment of unconverted biomass from bioconversion processes. By the use of this system, high conversion of biomass to fuel gas can be achieved. Medium-Btu is the primary product. Potential exists for recovery/recycle of some of the unreacted inorganic components from the biomass in the aqueous byproduct stream.

  14. The applicability of the catalytic wet-oxidation to CELSS

    NASA Technical Reports Server (NTRS)

    Takahashi, Y.; Nitta, K.; Ohya, H.; Oguchi, M.

    1987-01-01

    The wet oxidation catalysis of Au, Pd, Pt, Rh or Ru on a ceramic honeycomb carrier was traced in detail by 16 to 20 repetitive batch tests each. As a result, Pt or Pd on a honeycomb carrier was shown to catalyze complete nitrogen gasification as N2. Though the catalysts which realize both complete nitrogen gasification and complete oxidation could not be found, the Ru+Rh catalyst was found to be most promising. Ru honeycomb catalyzed both nitrification and nitrogen gasification.

  15. Degradation of phenol via wet-air oxidation over CuO/CeO2-ZrO2 nanocatalyst synthesized employing ultrasound energy: physicochemical characterization and catalytic performance.

    PubMed

    Parvas, Mohsen; Haghighi, Mohammad; Allahyari, Somaiyeh

    2014-01-01

    Catalytic wet air oxidation (CWAO) of phenol was carried out under atmospheric pressure of oxygen at 160 degrees C in a stirred batch reactor over copper catalysts supported by CeO2-ZrO2. The copper with different loadings were impregnated over the composite support by a sonication process. The catalysts were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), energy dispersive X-ray analysis (EDX), Brunauer-Emmett-Teller (BET) specific surface area and Fourier-transformed infrared analyses. Characteristic peaks attributed to copper were not found in XRD patterns even at high loadings, but based on EDX results, the existence of copper particles was confirmed. It means that sonochemical synthesis method even at high loadings produced small copper particles with low crystallinity and excellent dispersion over the CeO2-ZrO2 composite. FESEM micrographs indicated just slight enhancement in particle size at high loadings of Cu. Blank CWAO experiments illustrated low conversion of phenol using bare CeO2-ZrO2 support. Although some agglomeration of particles was found at high loadings of copper but owning to the fact that almost all ZrO2 particles incorporated into the CeO2 lattice at high contents of Cu, catalyst activity not only did not decrease but also the phenol conversion reached to the higher values. The optimal catalyst loading for phenol degradation was found to be 9 g/l. Complete conversion of phenol was achieved using CuO/CeO2-ZrO2 in 9 g/l catalyst loading with initial phenol concentration of 1000 ppm after 3 h of reaction. PMID:24701909

  16. Catalytic Wet Gasification of Municipal and Animal Wastes

    SciTech Connect

    Ro, Kyoung S.; Cantrell, Keri; Elliott, Douglas C.; Hunt, Patrick G.

    2007-02-21

    Applicability of wet gasification technology for various animal and municipal wastes was examined. Wet gasification of swine manure and raw sewage sludge generated high number of net energies. Furthermore, the moisture content of these wastes is ideal for current wet gasification technology. Significant quantities of water must be added to dry feedstock wastes such as poultry litter, feedlot manures and MSW to make the feedstock pumpable. Because of their high ash contents, MSW and unpaved feedlot manure would not generate positive energy return from wet gasification. The costs of a conceptual wet gasification manure management system for a model swine farm were significantly higher than that of the anaerobic lagoon system. However, many environmental advantages of the wet gasification system were identified, which might reduce the costs significantly. Due to high sulfur content of the wastes, pretreatment to prevent the poisoning of catalysts is critically needed.

  17. Catalytic wet oxidation of thiocyanate with homogeneous copper(II) sulphate catalyst.

    PubMed

    Collado, Sergio; Laca, Adriana; Díaz, Mario

    2010-05-15

    The wet oxidation of thiocyanate has been investigated in a semi-batch reactor at temperatures between 423 and 473 K and pressures between 6.1 x 10(3) and 1.0 x 10(4)kPa in the presence of copper(II) sulphate as catalyst. The effects of copper concentration, initial thiocyanate concentration, pressure and temperature on the reaction rate were analyzed and the main products of reaction were identified. A kinetic model for the Cu-catalyzed reaction is here proposed, including temperature, oxygen concentration, and the reduction of Cu(2+) to Cu(+) that gives an accurate prediction of the oxidation process under the assayed conditions. A mechanistic model based on the formation of a transition complex between a copper cation and two thiocyanate anions has been proposed for the catalytic wet oxidation. PMID:20045245

  18. Catalytic wet gasification of municipal and animal wastes

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Currently, there is worldwide interest in deriving energy from bio-based materials via gasification. Our objective was to assess the feasibility of wet gasification for treatment/energy conversion of both animal and municipal wastes. Wet wastes such as swine manure and raw sewage sludge could be pro...

  19. Low-temperature catalytic gasification of wet industrial wastes

    SciTech Connect

    Elliott, D C; Neuenschwander, G G; Baker, E G; Sealock, Jr, L J; Butner, R S

    1991-04-01

    Bench-scale reactor tests are in progress at Pacific Northwest Laboratory to develop a low-temperature, catalytic gasification system. The system, licensed under the trade name Thermochemical Environmental Energy System (TEES{reg sign}), is designed for treating a wide variety of feedstocks ranging from dilute organics in water to waste sludges from food processing. This report describes a test program which used a continuous-feed tubular reactor. This test program is an intermediate stage in the process development. The reactor is a laboratory-scale version of the commercial concept as currently envisioned by the process developers. An energy benefit and economic analysis was also completed on the process. Four conceptual commercial installations of the TEES process were evaluated for three food processing applications and one organic chemical manufacturing application. Net energy production (medium-Btu gas) was achieved in all four cases. The organic chemical application was found to be economically attractive in the present situation. Based on sensitivity studies included in the analysis, the three food processing cases will likely become attractive in the near future as waste disposal regulations tighten and disposal costs increase. 21 refs., 2 figs., 9 tabs.

  20. Post-treatment of refinery wastewater effluent using a combination of AOPs (H2O2 photolysis and catalytic wet peroxide oxidation) for possible water reuse. Comparison of low and medium pressure lamp performance.

    PubMed

    Rueda-Márquez, J J; Levchuk, I; Salcedo, I; Acevedo-Merino, A; Manzano, M A

    2016-03-15

    The main aim of this work was to study the feasibility of multi-barrier treatment (MBT) consisting of filtration, hydrogen peroxide photolysis (H2O2/UVC) and catalytic wet peroxide oxidation (CWPO) for post-treatment of petroleum refinery effluent. Also the possibility of water reuse or safe discharge was considered. The performance of MBT using medium (MP) and low (LP) pressure lamps was compared as well as operation and maintenance (O&M) cost. Decomposition of organic compounds was followed by means of gas chromatography-mass spectrometry (GC-MS), total organic carbon (TOC) and chemical oxygen demand (COD) analysis. After filtration step (25 μm) turbidity and concentration of suspended solids decreased by 92% and 80%, respectively. During H2O2/UVC process with LP lamp at optimal conditions (H2O2:TOC ratio 8 and UVC dose received by water 5.28 WUVC s cm(-2)) removal of phenolic compounds, TOC and COD was 100%, 52.3% and 84.3%, respectively. Complete elimination of phenolic compounds, 47.6% of TOC and 91% of COD was achieved during H2O2/UVC process with MP lamp at optimal conditions (H2O2:TOC ratio 5, UVC dose received by water 6.57 WUVC s cm(-2)). In order to compare performance of H2O2/UVC treatment with different experimental set up, the UVC dose required for removal of mg L(-1) of COD was suggested as a parameter and successfully applied. The hydrophilicity of H2O2/UVC effluent significantly increased which in turn enhanced the oxidation of organic compounds during CWPO step. After H2O2/UVC treatment with LP and MP lamps residual H2O2 concentration was 160 mg L(-1) and 96.5 mg L(-1), respectively. Remaining H2O2 was fully consumed during subsequent CWPO step (6 and 3.5 min of contact time for LP and MP, respectively). Total TOC and COD removal after MBT was 94.7% and 92.2% (using LP lamp) and 89.6% and 95%, (using MP lamp), respectively. The O&M cost for MBT with LP lamp was estimated to be 0.44 € m(-3) while with MP lamp it was nearly five

  1. Catalytic oxidation with Al-Ce-Fe-PILC as a post-treatment system for coffee wet processing wastewater.

    PubMed

    Sanabria, Nancy R; Peralta, Yury M; Montañez, Mardelly K; Rodríguez-Valencia, Nelson; Molina, Rafael; Moreno, Sonia

    2012-01-01

    The effluent from the anaerobic biological treatment of coffee wet processing wastewater (CWPW) contains a non-biodegradable compound that must be treated before it is discharged into a water source. In this paper, the wet hydrogen peroxide catalytic oxidation (WHPCO) process using Al-Ce-Fe-PILC catalysts was researched as a post-treatment system for CWPW and tested in a semi-batch reactor at atmospheric pressure and 25 °C. The Al-Ce-Fe-PILC achieved a high conversion rate of total phenolic compounds (70%) and mineralization to CO(2) (50%) after 5 h reaction time. The chemical oxygen demand (COD) of coffee processing wastewater after wet hydrogen peroxide catalytic oxidation was reduced in 66%. The combination of the two treatment methods, biological (developed by Cenicafé) and catalytic oxidation with Al-Ce-Fe-PILC, achieved a 97% reduction of COD in CWPW. Therefore, the WHPCO using Al-Ce-Fe-PILC catalysts is a viable alternative for the post-treatment of coffee processing wastewater. PMID:22907449

  2. A compact process for the treatment of olive mill wastewater by combining wet hydrogen peroxide catalytic oxidation and biological techniques.

    PubMed

    Azabou, Samia; Najjar, Wahiba; Bouaziz, Mohamed; Ghorbel, Abdelhamid; Sayadi, Sami

    2010-11-15

    A system based on combined actions of catalytic wet oxidation and microbial technologies for the treatment of highly polluted OMW containing polyphenols was studied. The wet hydrogen peroxide catalytic oxidation (WHPCO) process has been investigated in the semi-batch mode at atmospheric pressure, using aluminium-iron-pillared inter layer clay ((Al-Fe)PILC), under two different catalytic processes: ((Al-Fe)PILC/H(2)O(2)/ultraviolet radiations) at 25°C and ((Al-Fe)PILC/H(2)O(2)) at 50°C. The results show that raw OMW was resistant to the photocatalytic process. However ((Al-Fe)PILC/H(2)O(2)), system operating at 50°C reduced considerably the COD, colour and total phenolic contents, and thus decreased the inhibition of the marine photobacteria Vibrio fischeri luminescence by 70%. This study also examined the feasibility of coupling WHPCO and anaerobic digestion treatment. Biomethanisation experiments performed with raw OMW or pre-treated OMW proved that pre-treatments with ((Al-Fe)PILC/H(2)O(2)) system, for more than 2 h, resulted in higher methane production. Both untreated OMW as well as 2-h pre-treated OMW revealed as toxic to anaerobic bacteria. PMID:20678864

  3. Catalytic wet peroxide oxidation of azo dye (Congo red) using modified Y zeolite as catalyst.

    PubMed

    Kondru, Arun Kumar; Kumar, Pradeep; Chand, Shri

    2009-07-15

    The present study explores the degradation of azo dye (Congo red) by catalytic wet peroxide oxidation using Fe exchanged commercial Y zeolite as a catalyst. The effects of various operating parameters like temperature, initial pH, hydrogen peroxide concentration and catalyst loading on the removal of dye, color and COD from an aqueous solution were studied at atmospheric pressure. The percent removals of dye, color and COD at optimum pH(0) 7, 90 degrees C using 0.6 ml H(2)O(2)/350 ml solution and 1g/l catalyst was 97% (in 4h), 100% (in 45 min) and 58% (in 4h), respectively. The % dye removal has been found to be less in comparison to % color removal at all conditions, e.g. dye removal in 45 min and at above conditions was 82%, whereas the color removal was 100%. The results indicate that the Fe exchanged Y zeolite is a promising catalyst for dye removal. Fe exchanged catalyst is characterized using XRD, SEM/EDAX, surface area analyzer and FTIR. Though the dye, color and COD removals were maximum at pH(0) 2 but as the leaching of Fe from the catalyst was more in acidic pH range, pH(0) 7 was taken as operating pH due to almost comparable removals as of pH(0) 2 and no leaching of Fe ions. PMID:19135790

  4. Chloride ions promoted the catalytic wet peroxide oxidation of phenol over clay-based catalysts.

    PubMed

    Zhou, Shiwei; Zhang, Changbo; Xu, Rui; Gu, Chuantao; Song, Zhengguo; Xu, Minggang

    2016-01-01

    Catalytic wet peroxide oxidation (CWPO) of phenol over clay-based catalysts in the presence and absence of NaCl was investigated. Changes in the H2O2, Cl(-), and dissolved metal ion concentration, as well as solution pH during phenol oxidation, were also studied. Additionally, the intermediates formed during phenol oxidation were detected by liquid chromatography-mass spectroscopy and the chemical bonding information of the catalyst surfaces was analyzed by X-ray photoelectron spectroscopy (XPS). The results showed that the presence of Cl(-) increased the oxidation rate of phenol to 155%, and this phenomenon was ubiquitous during the oxidation of phenolic compounds by H2O2 over clay-based catalysts. Cl(-)-assisted oxidation of phenol was evidenced by several analytical techniques such as mass spectroscopy (MS) and XPS, and it was hypothesized that the rate-limiting step was accelerated in the presence of Cl(-). Based on the results of this study, the CWPO technology appears to be promising for applications in actual saline phenolic wastewater treatment. PMID:26942523

  5. SPONTANEOUS CATALYTIC WET AIR OXIDATION DURING PRE-TREATMENT OF HIGH-LEVEL RADIOACTIVE WASTE SLUDGE

    SciTech Connect

    Koopman, D.; Herman, C.; Pareizs, J.; Bannochie, C.; Best, D.; Bibler, N.; Fellinger, T.

    2009-10-01

    Savannah River Remediation, LLC (SRR) operates the Defense Waste Processing Facility for the U.S. Department of Energy at the Savannah River Site. This facility immobilizes high-level radioactive waste through vitrification following chemical pretreatment. Catalytic destruction of formate and oxalate ions to carbon dioxide has been observed during qualification testing of non-radioactive analog systems. Carbon dioxide production greatly exceeded hydrogen production, indicating the occurrence of a process other than the catalytic decomposition of formic acid. Statistical modeling was used to relate the new reaction chemistry to partial catalytic wet air oxidation of both formate and oxalate ions driven by the low concentrations of palladium, rhodium, and/or ruthenium in the waste. Variations in process conditions led to increases or decreases in the total oxidative destruction, as well as partially shifting the preferred species undergoing destruction from oxalate ion to formate ion.

  6. Catalytic wet oxidation of the pretreated synthetic pulp and paper mill effluent under moderate conditions.

    PubMed

    Garg, Anurag; Mishra, I M; Chand, Shri

    2007-01-01

    In the present study, catalytic wet oxidation (CWO) was investigated for the destruction of organic pollutants in the thermally pretreated effluent from a pulp and paper mill under moderate temperature and pressure conditions. The thermal pretreatment studies were conducted at atmospheric pressure and 368K using copper sulfate as a catalyst. The thermal pretreatment reduced COD by about 61%. The filtrate of the thermal pretreatment step was used at pH 8.0 for CWO at 383-443K temperature and a total pressure of 0.85MPa for 4h. Catalysts used for the reaction include copper sulfate, 5% CuO/95% activated carbon, 60% CuO/40% MnO(2), and 60% CuO/40% CeO(2). Maximum COD reduction was found to be 89% during CWO step using 5% CuO/95% activated carbon with a catalyst loading of 8gl(-1) at 443K and 0.85MPa total pressure. Overall COD reduction for the pretreatment and the CWO was found to be 96%. Besides this, 60% CuO/40% CeO(2) catalyst also exhibited the similar activity as that of obtained with 5% CuO/95% activated carbon catalyst at 423K temperature and 0.85MPa total pressure. The pH of the solution during the experimental runs decreases initially due to the formation of carboxylic acid and then increases due to the decomposition of acids. PMID:16934854

  7. Supported noble metal catalysts in the catalytic wet air oxidation of industrial wastewaters and sewage sludges.

    PubMed

    Besson, M; Descorme, C; Bernardi, M; Gallezot, P; di Gregorio, F; Grosjean, N; Minh, D Pham; Pintar, A

    2010-12-01

    This paper reviews some catalytic wet air oxidation (CWAO) investigations of industrial wastewaters over platinum and ruthenium catalysts supported on TiO2 and ZrO2 formulated to be active and resistant to leaching, with particular focus on the stability of the catalyst. Catalyst recycling experiments were performed in batch reactors and long-term stability tests were conducted in trickle-bed reactors. The catalyst did not leach upon treatment of Kraft bleaching plant and olive oil mill effluents, and could be either recycled or used for long periods of time in continuous reactors. Conversely, these catalysts were rapidly leached when used to treat effluents from the production of polymeric membranes containing N,N-dimethylformamide. The intermediate formation of amines, such as dimethylamine and methylamine with a high complexing capacity for the metal, was shown to be responsible for the metal leaching. These heterogeneous catalysts also deactivated upon CWAO of sewage sludges due to the adsorption of the solid organic matter. Pre-sonication of the sludge to disintegrate the flocs and improve solubility was inefficient. PMID:21214003

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

    PubMed

    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. PMID:18657902

  9. Tough and catalytically active hybrid biofibers wet-spun from nanochitin hydrogels.

    PubMed

    Das, Paramita; Heuser, Thomas; Wolf, Andrea; Zhu, Baolei; Demco, Dan Eugen; Ifuku, Shinsuke; Walther, Andreas

    2012-12-10

    Sustainable alternatives for high-performance and functional materials based on renewable resources are intensely needed as future alternatives for present-day, fossil-based materials. Nanochitin represents an emerging class of highly crystalline bionanoparticles with high intrinsic mechanical properties and the ability for conjugation into functional materials owing to reactive amine and hydroxyl groups. Herein we demonstrate that hydrogels containing surface-deacetylated chitin nanofibrils of micrometer length and average diameters of 9 nm, as imaged by cryogenic transmission electron microscopy, can be wet-spun into macrofibers via extrusion in a coagulation bath, a simple low energy and large-scale processing route. The resulting biofibers display attractive mechanical properties with a large plastic region of about 12% in strain, in which frictional sliding of nanofibrils allows dissipation of fracture energy and enables a high work-of-fracture of near 10 MJ/m3. We further show how to add functionality to these macrofibers by exploiting the amine functions of the surface chitosan groups to host catalytically active noble metal nanoparticles, furnishing biobased, renewable catalytic hybrids. These inorganic/organic macrofibers can be used repeatedly for fast catalytic reductions of model compounds without loss of activity, rendering the concept of hybridized chitin materials interesting as novel bioderived supports for nanoparticle catalysts. PMID:23102411

  10. Homogeneous catalytic wet-air oxidation for the treatment of textile wastewater

    SciTech Connect

    Lei, L. Chen, G.; Hu, X.; Yue, P.L.

    2000-04-01

    An extensive series of experiments was performed to identify suitable catalysts to increase the reaction rate of wet-air oxidation of textile wastewater t relatively mild temperatures an pressures. Wastewater types treated included natural-fiber desizing wastewater, synthetic-fiber desizing wastewater, and printing and dyeing wastewater. Experimental results indicated that all catalysts tested in this investigation significantly increased the chemical oxygen demand (COD) and total organic carbon (TOC) removal rates and total COD and TOC removals. Of all catalysts tested, copper salts were the most effective. Anions in the slat solutions played a role in the catalytic process. Nitrate ions were more effective than sulfate ions. Similarly, copper nitrates were more effective than copper sulfates. A mixture of salts containing different metals performed better than any single salt.

  11. Combination of coagulation and catalytic wet oxidation for the treatment of pulp and paper mill effluents.

    PubMed

    Verenich; Laari, A; Nissen, M; Kallas, J

    2001-01-01

    Wet oxidation (WO) is a well established process for purification of concentrated municipal and industrial wastewaters. Many attempts have been made to modify the WO process or to create a suitable combination of processes. This work was undertaken to investigate wet oxidation integrated with coagulation, i.e. to treat the sludge remaining after coagulation with a WO process. The possibility of regeneration of the used coagulant was also considered. Two waters from paper mills were used: TMP (thermomechanical pulp) circulation water and membrane concentrate. About 50% of the COD in the original water can be removed by coagulation using Fe2(SO4)3. The results from the wet oxidation experiments show the positive effect of iron in the chemical sludge as a catalyst. The efficiency of the WO process was enhanced almost by 100%. The remaining dissolved organic matter can be easily removed biologically. PMID:11695452

  12. Active carbon-ceramic sphere as support of ruthenium catalysts for catalytic wet air oxidation (CWAO) of resin effluent.

    PubMed

    Liu, Wei-Min; Hu, Yi-Qiang; Tu, Shan-Tung

    2010-07-15

    Active carbon-ceramic sphere as support of ruthenium catalysts were evaluated through the catalytic wet air oxidation (CWAO) of resin effluent in a packed-bed reactor. Active carbon-ceramic sphere and ruthenium catalysts were characterized by N(2) adsorption and chemisorption measurements. BET surface area and total pore volume of active carbon (AC) in the active carbon-ceramic sphere increase with increasing KOH-to-carbon ratio, and AC in the sample KC-120 possesses values as high as 1100 m(2) g(-1) and 0.69 cm(3) g(-1) (carbon percentage: 4.73 wt.%), especially. Active carbon-ceramic sphere supported ruthenium catalysts were prepared using the RuCl(3) solution impregnation onto these supports, the ruthenium loading was fixed at 1-5 wt.% of AC in the support. The catalytic activity varies according to the following order: Ru/KC-120>Ru/KC-80>Ru/KC-60>KC-120>without catalysts. It is found that the 3 wt.% Ru/KC-120 catalyst displays highest stability in the CWAO of resin effluent during 30 days. Chemical oxygen demand (COD) and phenol removal were about 92% and 96%, respectively at the reaction temperature of 200 degrees C, oxygen pressure of 1.5 MPa, the water flow rate of 0.75 L h(-1) and the oxygen flow rate of 13.5 L h(-1). PMID:20362394

  13. Treatment of municipal landfill leachate by catalytic wet air oxidation: Assessment of the role of operating parameters by factorial design

    SciTech Connect

    Anglada, Angela; Urtiaga, Ane; Ortiz, Inmaculada; Diamadopoulos, Evan

    2011-08-15

    Highlights: > Landfill leachates can be treated effectively by catalytic wet oxidation. > Addition of H{sub 2}O{sub 2} in the presence of transition metals promotes degradation. > Factorial design evaluates the statistically significant operating conditions. > H{sub 2}O{sub 2}, reaction time and temperature are critical in determining performance. - Abstract: The wet air oxidation (WAO) of municipal landfill leachate catalyzed by cupric ions and promoted by hydrogen peroxide was investigated. The effect of operating conditions such as WAO treatment time (15-30 min), temperature (160-200 deg. C), Cu{sup 2+} concentration (250-750 mg L{sup -1}) and H{sub 2}O{sub 2} concentration (0-1500 mg L{sup -1}) on chemical oxygen demand (COD) removal was investigated by factorial design considering a two-stage, sequential process comprising the heating-up of the reactor and the actual WAO. The leachate, at an initial COD of 4920 mg L{sup -1}, was acidified to pH 3 leading to 31% COD decrease presumably due to the coagulation/precipitation of colloidal and other organic matter. During the 45 min long heating-up period of the WAO reactor under an inert atmosphere, COD removal values up to 35% (based on the initial COD value) were recorded as a result of the catalytic decomposition of H{sub 2}O{sub 2} to reactive hydroxyl radicals. WAO at 2.5 MPa oxygen partial pressure advanced treatment further; for example, 22 min of oxidation at 200 deg. C, 250 mg L{sup -1} Cu{sup 2+} and 0-1500 mg L{sup -1} H{sub 2}O{sub 2} resulted in an overall (i.e. including acidification and heating-up) COD reduction of 78%. Amongst the operating variables in question, temperature had the strongest influence on both the heating-up and WAO stages, while H{sub 2}O{sub 2} concentration strongly affected the former and reaction time the latter. Nonetheless, the effects of temperature and H{sub 2}O{sub 2} concentration were found to depend on the concentration levels of catalyst as suggested by the

  14. Calcium-promoted catalytic degradation of PCDDs, PCDFs, and coplanar PCBs under a mild wet process.

    PubMed

    Mitoma, Yoshiharu; Tasaka, Norie; Takase, Maki; Masuda, Taizo; Tashiro, Hideki; Egashira, Naoyoshi; Oki, Takashi

    2006-03-15

    The authors achieved highly efficient degradation of polychlorinated aromatic compounds, including polychlorinated dibenzo-p-dioxins, dibenzofurans, and dioxin-like compounds such as coplanar polychlorinated biphenyls (co-PCBs), which are known as persistent organic pollutants. Degradation was accomplished in 24 h through a simple stirring operation using safe and high workability metallic calcium, which acts as both a scavenger and a reducing agent, and Rh/C catalyst in an alcohol solution under mild conditions in a sealed tube at 25 degrees C without a temperature increase within 0.15 MPa of increasing internal pressure during the reaction. In this system, reductive dechlorination by metallic calcium and catalytic reduction by Rh/C and generated hydrogen gas, without any external addition of hydrogen, exert a synergistic effect on the degradation of chlorinated compounds. Alcohol was used as a proton source and hydrogen, which was generated by a side reaction, causes an increase in the activity of Rh/C catalyst. Through the degradation of 4-chloroanisole in ethyl alcohol, anisole and cyclohexyl methyl ether were obtained in good conversions. Using ethyl alcohol as a solvent, treatment of dioxins and co-PCBs in a solution was markedly effective for degradation to reduce 2806 pg TEQ/ml of initial concentration to 31.8 pg TEQ/ml; its yield was 98.5%. Moreover, degradation in methyl alcohol took place in a 99.3% yield. That concentration ultimately reached 20.3 pg TEQ/ml under a mild wet process. All congeners of dioxins and co-PCBs were degraded in high conversions. In this degradation, lower aliphatic alcohol, such as methyl alcohol, is effective for making a new calcium surface as compared to alcohol with more methylene chains. In addition, it seemed that a higher pressure of hydrogen was easily generated in methyl alcohol, and then catalytic degradation was effectivley influenced. PMID:16570607

  15. Low-temperature catalytic gasification of wet industrial wastes. FY 1991--1992 interim report

    SciTech Connect

    Elliott, D.C.; Neuenschwander, G.G.; Hart, T.R.; Phelps, M.R.; Sealock, L.J. Jr.

    1993-07-01

    A catalytic gasification system operating in a pressurized water environment has been developed and refined at Pacific Northwest Laboratory (PNL) for over 12 years. Initial experiments were aimed at developing kinetics information for steam gasification of biomass in the presence of catalysts. The combined use of alkali and metal catalysts was reported for gasification of biomass and its components at low temperatures (350{degrees}C to 450{degrees}C). From the fundamental research evolved the concept of a pressurized, catalytic gasification system for converting wet biomass feedstocks to fuel gas. Extensive batch reactor testing and limited continuous reactor system (CRS) testing were undertaken in the development of this system under sponsorship of the US Department of Energy. A wide range of biomass feedstocks were tested, and the importance of the nickel metal catalyst was identified. Specific use of this process for treating food processing wastes was also studied. The concept application was further expanded to encompass cleanup of hazardous wastewater streams, and results were reported for batch reactor tests and continuous reactor tests. Ongoing work at PNL focuses on refining the catalyst and scaling the system to long-term industrial needs. The process is licensed as the Thermochemical Environmental Energy System (TEES{reg_sign}) to Onsite*Ofsite, Inc., of Duarte, California. This report is a follow-on to the 1989--90 interim report [Elliott et al. 1991], which reviewed the results of the studies conducted with a fixed-bed, continuous-feed, tubular reactor. The discussion here provides an overview of experiments on the wide range of potential feedstock materials conducted in a batch reactor; development of new catalyst materials; and tests performed in continuous-flow reactors at three scales. The appendices contain the history and background of the process development, as well as more detailed descriptions and results of the recent studies.

  16. Reactive wetting properties of TiO2 nanoparticles predicted by ab initio molecular dynamics simulations.

    PubMed

    Brandt, Erik G; Agosta, Lorenzo; Lyubartsev, Alexander P

    2016-07-21

    Small-sized wet TiO2 nanoparticles have been investigated by ab initio molecular dynamics simulations. Chemical and physical adsorption of water on the TiO2-water interface was studied as a function of water content, ranging from dry nanoparticles to wet nanoparticles with monolayer coverage of water. The surface reactivity was shown to be a concave function of water content and driven by surface defects. The local coordination number at the defect was identified as the key factor to decide whether water adsorption proceeds through dissociation or physisorption on the surface. A consistent picture of TiO2 nanoparticle wetting at the microscopic level emerges, which corroborates existing experimental data and gives further insight into the molecular mechanisms behind nanoparticle wetting. These calculations will facilitate the engineering of metal oxide nanoparticles with a controlled catalytic water activity. PMID:27341183

  17. Unprecedented Catalytic Wet Oxidation of Glucose to Succinic Acid Induced by the Addition of n-Butylamine to a Ru(III) Catalyst.

    PubMed

    Podolean, Iunia; Rizescu, Cristina; Bala, Camelia; Rotariu, Lucian; Parvulescu, Vasile I; Coman, Simona M; Garcia, Hermenegildo

    2016-09-01

    A new pathway for the catalytic wet oxidation (CWO) of glucose is described. Employing a cationic Ru@MNP catalyst, succinic acid is obtained in unprecedently high yield (87.5 %) for a >99.9 % conversion of glucose, most probably through a free radical mechanism combined with catalytic didehydroxylation of vicinal diols and hydrogenation of the resulted unsaturated intermediate. PMID:27511900

  18. Catalytic wet peroxide oxidation of aniline in wastewater using copper modified SBA-15 as catalyst.

    PubMed

    Kong, Liming; Zhou, Xiang; Yao, Yuan; Jian, Panming; Diao, Guowang

    2016-01-01

    SBA-15 mesoporous molecular sieves modified with copper (Cu-SBA-15) were prepared by pH-adjusting hydrothermal method and characterized by X-ray diffraction, BET, transmission electron microscopy, UV-Vis and (29)Si MAS NMR. The pH of the synthesis gel has a significant effect on the amount and the dispersion of copper on SBA-15. The Cu-SBA-15(4.5) (where 4.5 denotes the pH value of the synthesis gel) modified with highly dispersed copper was used as catalyst for the oxidation of aniline by H2O2. The Cu-SBA-15(4.5) shows a higher catalytic activity compared to CuO on the surface of SBA-15. The influences of reaction conditions, such as initial pH of the aqueous solutions, temperature, as well as the dosages of H2O2 and catalyst were investigated. Under weakly alkaline aqueous solution conditions, the aniline conversion, the H2O2 decomposition and the total organic carbon (TOC) removal could be increased significantly compared to the acid conditions. The percentage of leaching Cu(2+) could be decreased from 45.0% to 3.66% when the initial pH of solution was increased from 5 to 10. The TOC removal could be enhanced with the increases of temperature, H2O2 and catalyst dosage, but the aniline conversion and H2O2 decomposition change slightly with further increasing dosage of catalyst and H2O2. At 343 K and pH 8.0, 100% aniline conversion and 66.9% TOC removal can be achieved under the conditions of 1.0 g/L catalyst and 0.05 mol/L H2O2 after 180 min. Although copper might be slightly leached from catalyst, the homogeneous Cu(2+) contribution to the whole catalytic activity is unimportant, and the highly dispersed copper on SBA-15 plays a dominant role. PMID:26227827

  19. Inhibition and deactivation effects in catalytic wet oxidation of high-strength alcohol-distillery liquors

    SciTech Connect

    Belkacemi, K.; Larachi, F.; Hamoudi, S.; Turcotte, G.; Sayari, A.

    1999-06-01

    The removal efficiency of total organic carbon (TOC) from raw high-strength alcohol-distillery waste liquors was evaluated using three different treatments: thermolysis (T), noncatalytic wet oxidation (WO), and solid-catalyzed wet oxidation (CWO). The distillery liquors (TOC = 22,500 mg/l, sugars = 18,000 mg/l, and proteins = 13,500 mg/l) were produced by alcoholic fermentation of enzymatic hydrolyzates from steam-exploded timothy grass. TOC-abatement studies were conducted batchwise in a stirred autoclave to evaluate the influence of the catalyst (7:3, MnO{sub 2}/CeO{sub 2} mixed oxide), oxygen partial pressure (0.5--2.5 MPa), and temperature (453--523 K) on T, WO, and CWO processes. Although CWO outperformed T and WO, TOC conversions did not exceed {approximately}60% at the highest temperature used. Experiments provided prima facie evidence for a gradual fouling of the catalyst and a developing inhibition in the liquors which impaired deep TOC removals. Occurrence of catalyst deactivation by carbonaceous deposits was proven experimentally through quantitative and qualitative experiments such as elemental analysis and X-ray photoelectron spectroscopy. Inhibition toward further degradation of the liquors was ascribed to the occurrence of highly stable antioxidant intermediates via the Maillard reactions between dissolved sugars and proteins. A lumping kinetic model involving both reaction inhibition by dissolved intermediates and catalyst deactivation by carbonaceous deposits was proposed to account for the distribution of carbon in the liquid, solid, and the vapor phases.

  20. Toxicity to Daphnia magna and Vibrio fischeri of Kraft bleach plant effluents treated by catalytic wet-air oxidation.

    PubMed

    Pintar, Albin; Besson, Michèle; Gallezot, Pierre; Gibert, Janine; Martin, Dominique

    2004-01-01

    Two Kraft-pulp bleaching effluents from a sequence of treatments which include chlorine dioxide and caustic soda were treated by catalytic wet-air oxidation (CWAO) at T=463 K in trickle-bed and batch-recycle reactors packed with either TiO2 extrudates or Ru(3 wt%)/TiO2 catalyst. Chemical analyses (TOC removal, color, HPLC) and bioassays (48-h and 30-min acute toxicity tests using Daphnia magna and Vibrio fischeri, respectively) were used to get information about the toxicity impact of the starting effluents and of the treated solutions. Under the operating conditions, complex organic compounds are mostly oxidized into carbon dioxide and water, along with short-chain carboxylic acids. Bioassays were found as a complement to chemical analyses for ensuring the toxicological impact on the ecosystem. In spite of a large decrease of TOC, the solutions of end products were all more toxic to Daphnia magna than the starting effluents by factors ranging from 2 to 33. This observation is attributed to the synergistic effects of acetic acid and salts present in the solutions. On the other hand, toxicity reduction with respect to Vibrio fischeri was achieved: detoxification factors greater than unity were measured for end-product solutions treated in the presence of the Ru(3 wt%)/TiO2 catalyst, suggesting the absence of cumulative effect for this bacteria, or a lower sensitivity to the organic acids and salts. Bleach plant effluents treated by the CWAO process over the Ru/TiO2 catalyst were completely biodegradable. PMID:14675640

  1. Bench-scale reactor tests of low temperature, catalytic gasification of wet industrial wastes

    SciTech Connect

    Elliot, D.C.; Baker, E.G.; Butner, R.S.; Sealock, L.J. Jr. )

    1993-02-01

    Bench-scale reactor tests are under way at Pacific Northwest Laboratory to develop a low temperature, catalytic gasification system. The system, licensed under the trade name Thermochemical Environmental Energy System (TEES[reg sign]), is designed for to a wide variety of feedstocks ranging from dilute organics in water to waste sludges from food processing. The current research program is focused on the use of a continuous feed, tubular reactor. The catalyst is nickel metal on an inert support. Typical results show that feedstocks such as solutions of 2 percent para-cresol or 5 percent and 10 percent lactose in water or cheese whey can be processed to [gt] 99 percent reduction of chemical oxygen demand (COD) at a rate of up to 2 L/hr. The estimated residence lime is less than 5 min at 360C and 3,000 psig, not including 1 to 2 min required in the preheating zone of the reactor. The liquid hourly space velocity has been varied from 1.8 to 2.9 L feedstock/L catalyst/hr depending on the feedstock. The product fuel gas contains 40 percent to 55 percent methane, 35 percent to 50 percent carbon dioxide, and 5 percent to 10 percent hydrogen with as much as 2 percent ethane, but less than 0.1 percent ethylene or carbon monoxide, and small amounts of higher hydrocarbons. The byproduct water stream carries residual organics amounting to less than 500 mg/L COD.

  2. Bench-scale reactor tests of low-temperature, catalytic gasification of wet, industrial wastes

    SciTech Connect

    Elliott, D.C.; Neuenschwander, G.G.; Baker, E.G.; Butner, R.S.; Sealock, L.J.

    1990-04-01

    Bench-scale reactor tests are under way at Pacific Northwest Laboratory to develop a low-temperature, catalytic gasification system. The system, licensed under the trade name Thermochemical Environmental Energy System (TEES{reg sign}), is designed for to a wide variety of feedstocks ranging from dilute organics in water to waste sludges from food processing. The current research program is focused on the use of a continuous-feed, tubular reactor. The catalyst is nickel metal on an inert support. Typical results show that feedstocks such as solutions of 2% para-cresol or 5% and 10% lactose in water or cheese whey can be processed to >99% reduction of chemical oxygen demand (COD) at a rate of up to 2 L/hr. The estimated residence time is less than 5 min at 360{degree}C and 3000 psig, not including 1 to 2 min required in the preheating zone of the reactor. The liquid hourly space velocity has been varied from 1.8 to 2.9 L feedstock/L catalyst/hr depending on the feedstock. The product fuel gas contains 40% to 55% methane, 35% to 50% carbon dioxide, and 5% to 10% hydrogen with as much as 2% ethane, but less than 0.1% ethylene or carbon monoxide, and small amounts of higher hydrocarbons. The byproduct water stream carries residual organics amounting to less than 500 mg/L COD. 9 refs., 1 fig., 4 tabs.

  3. A kinetic model of municipal sludge degradation during non-catalytic wet oxidation.

    PubMed

    Prince-Pike, Arrian; Wilson, David I; Baroutian, Saeid; Andrews, John; Gapes, Daniel J

    2015-12-15

    Wet oxidation is a successful process for the treatment of municipal sludge. In addition, the resulting effluent from wet oxidation is a useful carbon source for subsequent biological nutrient removal processes in wastewater treatment. Owing to limitations with current kinetic models, this study produced a kinetic model which predicts the concentrations of key intermediate components during wet oxidation. The model was regressed from lab-scale experiments and then subsequently validated using data from a wet oxidation pilot plant. The model was shown to be accurate in predicting the concentrations of each component, and produced good results when applied to a plant 500 times larger in size. A statistical study was undertaken to investigate the validity of the regressed model parameters. Finally the usefulness of the model was demonstrated by suggesting optimum operating conditions such that volatile fatty acids were maximised. PMID:26426294

  4. Low-temperature catalytic gasification of wet industrial wastes. FY 1993--1994 interim report

    SciTech Connect

    Elliott, D.C.; Hart, T.R.; Neuenschwander, G.G.; Deverman, G.S.; Werpy, T.A.; Phelps, M.R.; Baker, E.G.; Sealock, L.J. Jr.

    1995-03-01

    Process development research is continuing on a low-temperature, catalytic gasification system that has been demonstrated to convert organics in water (dilute or concentrated) to useful and environmentally safe gases. The system, licensed under the trade name Thermochemical Environmental Energy System (TEESO), treats a wide variety of feedstocks ranging from hazardous organics in water to waste sludges from food processing. The current research program is focused on the use of continuous-feed, tubular reactors systems for testing catalysts and feedstocks in the process. A range of catalysts have been tested, including nickel and other base metals, as well as ruthenium and other precious metals. Results of extensive testing show that feedstocks, ranging from 2% para-cresol in water to potato waste and spent grain, can be processed to > 99% reduction of chemical oxygen demand (COD). The product fuel gas contains from 40% up to 75% methane, depending on the feedstock. The balance of the gas is mostly carbon dioxide with < 5% hydrogen and usually < 1% ethane and higher hydrocarbons. The byproduct water stream carries residual organics from 10 to 1,000 mg/l COD, depending on the feedstock. The level of development of TEES has progressed to the initial phases of industrial process demonstration. Testing of industrial waste streams is under way at both the bench scale and engineering scale of development.

  5. Development of the Monolith Froth Reactor for Catalytic Wet Oxidation of CELSS Model Wastes

    NASA Technical Reports Server (NTRS)

    Abraham, Martin; Fisher, John W.

    1995-01-01

    The aqueous phase oxidation of acetic acid, used as a model compound for the treatment of CELSS (Controlled Ecological Life Support System) waste, was carried out in the monolith froth reactor which utilizes two-phase flow in the monolith channels. The catalytic oxidation of acetic acid was carried out over a Pt/Al2O3 catalyst, prepared at The University of Tulsa, at temperatures and pressures below the critical point of water. The effect of externally controllable parameters (temperature, liquid flow rate, distributor plate orifice size, pitch, and catalyst distance from the distributor plate) on the rate of acetic acid oxidation was investigated. Results indicate reaction rate increased with increasing temperature and exhibited a maximum with respect to liquid flow rate. The apparent activation energy calculated from reaction rate data was 99.7 kJ/mol. This value is similar to values reported for the oxidation of acetic acid in other systems and is comparable to intrinsic values calculated for oxidation reactions. The kinetic data were modeled using simple power law kinetics. The effect of "froth" feed system characteristics was also investigated. Results indicate that the reaction rate exhibits a maximum with respect to distributor plate orifice size, pitch, and catalyst distance from the distributor plate. Fundamental results obtained were used to extrapolate where the complete removal of acetic acid would be obtained and for the design and operation of a full scale CELSS treatment system.

  6. Development of the Monolith Froth Reactor for Catalytic Wet Oxidation of CELSS Model Wastes

    NASA Technical Reports Server (NTRS)

    Fisher, John W.; Abraham, Martin

    1993-01-01

    The aqueous phase oxidation of acetic acid, used as a model compound for the treatment of CELSS (Controlled Ecological Life Support System) waste, was carried out in the monolith froth reactor which utilizes two-phase flow in the monolith channels. The catalytic oxidation of acetic acid was carried out over a Pt/Al2O3 catalyst at temperatures and pressures below the critical point of water. The effect of externally controllable parameters (temperature, liquid flow rate, distributor plate orifice size, pitch, and catalyst distance from the distributor plate) on the rate of acetic acid oxidation was investigated. Results indicate reaction rate increased with increasing temperature and exhibited a maximum with respect to liquid flow rate. The apparent activation energy calculated from reaction rate data was 99.7 kJ/mol. This value is similar to values reported for the oxidation of acetic acid in other systems and is comparable to intrinsic values calculated for oxidation reactions. The kinetic data were modeled using simple power law kinetics. The effect of "froth" feed system characteristics was also investigated. Results indicate that the reaction rate exhibits a maximum with respect to distributor plate orifice size, pitch, and catalyst distance from the distributor plate. Fundamental results obtained were used to extrapolate where the complete removal of acetic acid would be obtained and for the design and operation of a full scale CELSS treatment system.

  7. Project WET Curriculum and Activity Guide 2.0

    ERIC Educational Resources Information Center

    Project WET Foundation, 2011

    2011-01-01

    The "Project WET Curriculum and Activity Guide 2.0" continues Project WET's dedication to 21st-century, cutting-edge water education. Now in full color, Guide 2.0 offers new activities on topics such as National Parks and storm water, fully revised and updated activities from the original Guide and the very best activities gathered from all of…

  8. Reactive wetting properties of TiO2 nanoparticles predicted by ab initio molecular dynamics simulations

    NASA Astrophysics Data System (ADS)

    Brandt, Erik G.; Agosta, Lorenzo; Lyubartsev, Alexander P.

    2016-07-01

    Small-sized wet TiO2 nanoparticles have been investigated by ab initio molecular dynamics simulations. Chemical and physical adsorption of water on the TiO2-water interface was studied as a function of water content, ranging from dry nanoparticles to wet nanoparticles with monolayer coverage of water. The surface reactivity was shown to be a concave function of water content and driven by surface defects. The local coordination number at the defect was identified as the key factor to decide whether water adsorption proceeds through dissociation or physisorption on the surface. A consistent picture of TiO2 nanoparticle wetting at the microscopic level emerges, which corroborates existing experimental data and gives further insight into the molecular mechanisms behind nanoparticle wetting. These calculations will facilitate the engineering of metal oxide nanoparticles with a controlled catalytic water activity.Small-sized wet TiO2 nanoparticles have been investigated by ab initio molecular dynamics simulations. Chemical and physical adsorption of water on the TiO2-water interface was studied as a function of water content, ranging from dry nanoparticles to wet nanoparticles with monolayer coverage of water. The surface reactivity was shown to be a concave function of water content and driven by surface defects. The local coordination number at the defect was identified as the key factor to decide whether water adsorption proceeds through dissociation or physisorption on the surface. A consistent picture of TiO2 nanoparticle wetting at the microscopic level emerges, which corroborates existing experimental data and gives further insight into the molecular mechanisms behind nanoparticle wetting. These calculations will facilitate the engineering of metal oxide nanoparticles with a controlled catalytic water activity. Electronic supplementary information (ESI) available: Simulation data on equilibration of energies and structures (root-mean-square-deviations and

  9. Development of a Catalytic Wet Air Oxidation Method to Produce Feedstock Gases from Waste Polymers

    NASA Technical Reports Server (NTRS)

    Kulis, Michael J.; Guerrero-Medina, Karen J.; Hepp, Aloysius F.

    2012-01-01

    Given the high cost of space launch, the repurposing of biological and plastic wastes to reduce the need for logistical support during long distance and long duration space missions has long been recognized as a high priority. Described in this paper are the preliminary efforts to develop a wet air oxidation system in order to produce fuels from waste polymers. Preliminary results of partial oxidation in near supercritical water conditions are presented. Inherent corrosion and salt precipitation are discussed as system design issues for a thorough assessment of a second generation wet air oxidation system. This work is currently being supported by the In-Situ Resource Utilization Project.

  10. Thermodynamic and kinetic study of phenol degradation by a non-catalytic wet air oxidation process.

    PubMed

    Lefèvre, Sébastien; Boutin, Olivier; Ferrasse, Jean-Henry; Malleret, Laure; Faucherand, Rémy; Viand, Alain

    2011-08-01

    This work is dedicated to an accurate evaluation of thermodynamic and kinetics aspects of phenol degradation using wet air oxidation process. Phenol is a well known polluting molecule and therefore it is important having data of its behaviour during this process. A view cell is used for the experimental study, with an internal volume of 150 mL, able to reach pressures up to 30 MPa and temperatures up to 350°C. Concerning the thermodynamic phase equilibria, experimental and modelling results are obtained for different binary systems (water/nitrogen, water/air) and ternary system (water/nitrogen/phenol). The best model is the Predictive Soave Redlich Kwong one. This information is necessary to predict the composition of the gas phase during the process. It is also important for an implementation in a process simulation. The second part is dedicated to kinetics evaluation of the degradation of phenol. Different compounds have been detected using GC coupled with a MS. A kinetic scheme is deduced, taking into account the evolution of phenol, hydroquinones, catechol, resorcinol and acetic acid. The kinetic parameters are calculated for this scheme. These data are important to evaluate the evolution of the concentration of the different polluting molecules during the process. A simplified kinetic scheme, which can be easily implemented in a process simulation, is also determined for the direct degradation of phenol into H(2)O and CO(2). The Arrhenius law data obtained for the phenol disappearance are the following: k=1.8×10(6)±3.9×10(5)M(-1)s(-1) (pre-exponential factor) and E(a)=77±8 kJ mol(-1) (activation energy). PMID:21700312

  11. WetLab-2: Wet Lab RNA SmartCycler Providing PCR Capability on ISS

    NASA Technical Reports Server (NTRS)

    Parra, Macarena; Schonfeld, Julie

    2015-01-01

    The WetLab-2 system will provide sample preparation and qRT-PCR analysis on-board the ISS, a capability to enable using the ISS as a real laboratory. The system will be validated on SpX-7, and is planned for its first PI use on SpX-9.

  12. Sewage-sludge-derived carbonaceous materials for catalytic wet hydrogen peroxide oxidation of m-cresol in batch and continuous reactors.

    PubMed

    Yu, Yang; Wei, Huangzhao; Yu, Li; Wang, Wei; Zhao, Ying; Gu, Bin; Sun, Chenglin

    2016-01-01

    In this study, four sewage-sludge-derived carbonaceous materials (SWs) were evaluated for their catalytic wet hydrogen peroxide oxidation (CWPO) performance of m-cresol in batch reactor and continuous reactor, respectively. The SWs were produced by carbonization (SW); carbonization with the addition of CaO (CaO-SW); HNO3 pretreatment (HNO3-SW) and steam activation (Activated-SW). The properties of SW catalysts were assessed by thermogravimetric analysis, Brunauer-Emmett-Teller, Fourier Transform Infrared Spectroscopy, X-ray Fluorescence, Scanning electron microscopy, energy dispersive X-ray analysis and zeta potential. The results showed that SW treated by HNO3 (HNO3-SW) had a high conversion of m-cresol in batch reactor and continuous reactor, respectively. Under the conditions of batch reaction (Cm-cresol = 100 mg L(-1), CH2O2 = 15.7 mmol L(-1), initial pH=7.0, 0.5 g L(-1) catalyst, 80°C, 180 min adsorption and 210 min oxidation), the conversion of m-cresol reached 100% and total organic carbon removal was 67.1%. It had a high catalytic activity and stability on the treatment of m-cresol in CWPO for more than 1100 h. Furthermore, a possible reaction mechanism for the oxidation of m-cresol to 2-methyl-p-benzoquinone by CWPO was proposed. PMID:26109374

  13. Carbon and nitrogen removal from glucose-glycine melanoidins solution as a model of distillery wastewater by catalytic wet air oxidation.

    PubMed

    Phuong Thu, Le; Michèle, Besson

    2016-06-01

    Sugarcane molasses distillery wastewater contains melanoidins, which are dark brown recalcitrant nitrogenous polymer compounds. Studies were carried out in batch mode to evaluate Pt and Ru supported catalysts in the Catalytic Wet Air Oxidation (CWAO) process of a synthetic melanoidins solution, prepared by stoichiometric reaction of glucose with glycine. The addition of a catalyst slightly improved TOC removal compared with the non-catalytic reaction, and especially promoted the conversion of ammonium produced from organically-bound nitrogen in melanoidins to molecular nitrogen and nitrate. The selectivity to N2 attained 89% in the presence of the Pt catalysts in the reaction conditions used (TOC=2200mgL(-1), TN=280mgL(-1), 0.5g catalyst loaded with 3% metal, 210°C, 70bar total air pressure). To avoid leaching of the active metal by organically-bound nitrogen, the reaction was very efficiently performed in a two-step reaction consisting in WAO to convert nitrogen into ammonium, before the introduction of a catalyst. PMID:26900982

  14. Mineralization of gaseous acetaldehyde by electrochemically generated Co(III) in H2SO4 with wet scrubber combinatorial system.

    PubMed

    Govindan, Muthuraman; Chung, Sang-Joon; Moon, Il-Shik

    2012-06-11

    Electrochemically generated Co(III) mediated catalytic room temperature incineration of acetaldehyde, which is one of volatile organic compounds (VOCs), combined with wet scrubbing system was developed and investigated. Depending on the electrolyte's type, absorption come removal efficiency is varied. In presence of electrogenerated Co(III) in sulfuric acid, acetaldehyde was mineralized to CO2 and not like only absorption in pure sulfuric acid. The Co(III) mediated catalytic incineration led to oxidative absorption and elimination to CO2, which was evidenced with titration, CO2, and cyclic voltammetric analyses. Experimental conditions, such as current density, concentration of mediator, and gas molar flow rate were optimized. By the optimization of the experimental conditions, the complete mineralization of acetaldehyde was realized at a room temperature using electrochemically generated Co(III) with wet scrubber combinatorial system. PMID:22551057

  15. Comparative study of supported CuOx and MnOx catalysts for the catalytic wet air oxidation of β-naphthol

    NASA Astrophysics Data System (ADS)

    Liu, Jie; Yu, Chaoying; Zhao, Peiqing; Chen, Gexin

    2012-09-01

    MnOx/nano-TiO2, MnOx/Al2O3-TiO2 (Al-Ti), CuOx/nano-TiO2 and CuOx/Al-Ti were prepared and their application in catalytic wet air oxidation (CWAO) of β-naphthol were investigated. The catalysts had been characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and temperature-programmed reduction (TPR) measurements. Phases of CuO, Cu2O, CuAl2O4, MnO2 and Mn2O3 could be found on the surface of the aforementioned catalysts. Significant differences in activities were observed among the prepared catalysts. Compared to CuOx/nano-TiO2, the combined action of highly dispersed CuO as well as CuAl2O4 of CuOx/Al-Ti helped to achieve higher activity for the CWAO of β-naphthol, while the Cu2O component lead to lower efficiency of CuOx/nano-TiO2. On the surface of MnOx/nano-TiO2, both the larger amount of highly dispersed MnO2 and the stronger electron transfer between MnO2 and Mn2O3 were helpful to promote the activity for the degradation of β-naphthol. However, the higher amount of bulk MnO2 and the weaker electron transfer for MnOx/Al-Ti were unfavorable to increase its efficiency. Among the four catalysts as-prepared, MnOx/nano-TiO2 was identified the highest activity with 93.7% COD removal.

  16. TiO2-sludge carbon enhanced catalytic oxidative reaction in environmental wastewaters applications.

    PubMed

    Athalathil, Sunil; Erjavec, Boštjan; Kaplan, Renata; Stüber, Frank; Bengoa, Christophe; Font, Josep; Fortuny, Agusti; Pintar, Albin; Fabregat, Azael

    2015-12-30

    The enhanced oxidative potential of sludge carbon/TiO2 nano composites (SNCs), applied as heterogeneous catalysts in advanced oxidation processes (AOPs), was studied. Fabrification of efficient SNCs using different methods and successful evaluation of their catalytic oxidative activity is reported for the first time. Surface modification processes of hydrothermal deposition, chemical treatment and sol-gel solution resulted in improved catalytic activity and good surface chemistry of the SNCs. The solids obtained after chemical treatment and hydrothermal deposition processes exhibit excellent crystallinity and photocatalytic activity. The highest photocatalytic rate was obtained for the material prepared using hydrothermal deposition technique, compared to other nanocomposites. Further, improved removal of bisphenol A (BPA) from aqueous phase by means of catalytic ozonation and catalytic wet air oxidation processes is achieved over the solid synthesized using chemical treatment method. The present results demonstrate that the addition of TiO2 on the surface of sludge carbon (SC) increases catalytic oxidative activity of SNCs. The latter produced from harmful sludge materials can be therefore used as cost-effective and efficient sludge derived catalysts for the removal of hazardous pollutants. PMID:26223014

  17. 40 CFR Table 2 to Subpart Eeee of... - Operating Limits for Incinerators and Wet Scrubbers

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ...-hour rolling for continuous and intermittent units a. 2. Pressure drop across the wet scrubber or amperage to wet scrubber Minimum pressure drop or amperage Continuous Every 15 minutes 3-hour rolling a....

  18. 40 CFR Table 2 to Subpart Eeee of... - Operating Limits for Incinerators and Wet Scrubbers

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ...-hour rolling for continuous and intermittent units a. 2. Pressure drop across the wet scrubber or amperage to wet scrubber Minimum pressure drop or amperage Continuous Every 15 minutes 3-hour rolling a....

  19. 40 CFR Table 2 to Subpart Eeee of... - Operating Limits for Incinerators and Wet Scrubbers

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ...-hour rolling for continuous and intermittent units a. 2. Pressure drop across the wet scrubber or amperage to wet scrubber Minimum pressure drop or amperage Continuous Every 15 minutes 3-hour rolling a....

  20. 40 CFR Table 2 to Subpart Eeee of... - Operating Limits for Incinerators and Wet Scrubbers

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ...-hour rolling for continuous and intermittent units a. 2. Pressure drop across the wet scrubber or amperage to wet scrubber Minimum pressure drop or amperage Continuous Every 15 minutes 3-hour rolling a....

  1. 40 CFR Table 2 to Subpart Eeee of... - Operating Limits for Incinerators and Wet Scrubbers

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ...-hour rolling for continuous and intermittent units a. 2. Pressure drop across the wet scrubber or amperage to wet scrubber Minimum pressure drop or amperage Continuous Every 15 minutes 3-hour rolling a....

  2. Electrochemical, H2O2-Boosted Catalytic Oxidation System

    NASA Technical Reports Server (NTRS)

    Akse, James R.; Thompson, John O.; Schussel, Leonard J.

    2004-01-01

    An improved water-sterilizing aqueous-phase catalytic oxidation system (APCOS) is based partly on the electrochemical generation of hydrogen peroxide (H2O2). This H2O2-boosted system offers significant improvements over prior dissolved-oxygen water-sterilizing systems in the way in which it increases oxidation capabilities, supplies H2O2 when needed, reduces the total organic carbon (TOC) content of treated water to a low level, consumes less energy than prior systems do, reduces the risk of contamination, and costs less to operate. This system was developed as a variant of part of an improved waste-management subsystem of the life-support system of a spacecraft. Going beyond its original intended purpose, it offers the advantage of being able to produce H2O2 on demand for surface sterilization and/or decontamination: this is a major advantage inasmuch as the benign byproducts of this H2O2 system, unlike those of systems that utilize other chemical sterilants, place no additional burden of containment control on other spacecraft air- or water-reclamation systems.

  3. SWI/SNF-mutant cancers depend on catalytic and non-catalytic activity of EZH2.

    PubMed

    Kim, Kimberly H; Kim, Woojin; Howard, Thomas P; Vazquez, Francisca; Tsherniak, Aviad; Wu, Jennifer N; Wang, Weishan; Haswell, Jeffrey R; Walensky, Loren D; Hahn, William C; Orkin, Stuart H; Roberts, Charles W M

    2015-12-01

    Human cancer genome sequencing has recently revealed that genes that encode subunits of SWI/SNF chromatin remodeling complexes are frequently mutated across a wide variety of cancers, and several subunits of the complex have been shown to have bona fide tumor suppressor activity. However, whether mutations in SWI/SNF subunits result in shared dependencies is unknown. Here we show that EZH2, a catalytic subunit of the polycomb repressive complex 2 (PRC2), is essential in all tested cancer cell lines and xenografts harboring mutations of the SWI/SNF subunits ARID1A, PBRM1, and SMARCA4, which are several of the most frequently mutated SWI/SNF subunits in human cancer, but that co-occurrence of a Ras pathway mutation is correlated with abrogation of this dependence. Notably, we demonstrate that SWI/SNF-mutant cancer cells are primarily dependent on a non-catalytic role of EZH2 in the stabilization of the PRC2 complex, and that they are only partially dependent on EZH2 histone methyltransferase activity. These results not only reveal a shared dependency of cancers with genetic alterations in SWI/SNF subunits, but also suggest that EZH2 enzymatic inhibitors now in clinical development may not fully suppress the oncogenic activity of EZH2. PMID:26552009

  4. SWI/SNF mutant cancers depend upon catalytic and non–catalytic activity of EZH2

    PubMed Central

    Kim, Kimberly H.; Kim, Woojin; Howard, Thomas P.; Vazquez, Francisca; Tsherniak, Aviad; Wu, Jennifer N.; Wang, Weishan; Haswell, Jeffrey R.; Walensky, Loren D.; Hahn, William C.; Orkin, Stuart H.; Roberts, Charles W. M.

    2016-01-01

    Human cancer genome sequencing has recently revealed that genes encoding subunits of SWI/SNF chromatin remodeling complexes are frequently mutated across a wide variety of cancers, and several subunits of the complex have been shown to have bona fide tumor suppressor activity1. However, whether mutations in SWI/SNF subunits result in shared dependencies is unknown. Here we show that EZH2, a catalytic subunit of the Polycomb repressive complex 2 (PRC2), is essential in all tested cancer cell lines and xenografts harboring mutations of the SWI/SNF subunits ARID1A, PBRM1, and SMARCA4, which are several of the most frequently mutated SWI/SNF subunits in human cancer but that co–occurrence of a Ras pathway mutation correlates with abrogation of this dependence. Surprisingly, we demonstrate that SWI/SNF mutant cancer cells are primarily dependent upon a non–catalytic role of EZH2 in stabilization of the PRC2 complex, and only partially dependent on EZH2 histone methyltransferase activity. These results not only reveal a shared dependency of cancers with genetic alterations in SWI/SNF subunits, but also suggest that EZH2 enzymatic inhibitors now in clinical development may not fully suppress the oncogenic activity of EZH2. PMID:26552009

  5. Catalytic behaviour and copper leaching of Cu0.10Zn0.90Al1.90Fe0.10O4 spinel for catalytic wet air oxidation of phenol.

    PubMed

    Xu, Aihua; Sun, Chenglin

    2012-06-01

    A Cu0.10Zn0.90Al1.90Fe0.10O4 spinel catalyst prepared by the sol-gel method was tested for catalytic wet air oxidation (CWAO) of phenol. The catalyst showed high activity for phenol degradation. During successive test at 170 degrees C, 100% phenol conversion and 95% chemical oxygen demand (COD) removal were observed. Results from scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR) and X-ray diffraction (XRD) indicated that the catalyst structure remained unchanged during reaction. From the analysis of temperature programmed reduction (TPR), diffuse reflectance UV-Vis spectra (DR UV-Vis) and activity assay at basic solution pH, it can be suggested that the highly dispersed copper ions on the catalyst surface were almost completely dissolved into the reaction solution, whereas the tetra-coordinated copper ions were not only stable against leaching but also active towards phenol degradation. PMID:22856307

  6. [Fe-ZSM-5 catalysts with different silica-alumina ratios for N2O, catalytic decomposition].

    PubMed

    Lu, Ren-Jie; Zhang, Xin-Yan; Hao, Zheng-Ping

    2014-01-01

    The Fe-ZSM-5 catalysts were prepared with H-ZSM-5 of different Si/Al ratios by wet ion exchange and chemical vapor deposition. Then the catalysts were investigated by XRD, BET, TEM, UV-vis and NH3-TPD technologies to analyze the iron states in Fe-ZSM-5 zeolites. The results showed that after H-ZSM-5 zeolites were prepared by chemical vapor deposition and heating wet ion exchange, the nano Fe2 O3 particles were uniformly dispersed with the sizes of 8 nm in the Fe-ZSM-5-25 (Si/A1-25). Moreover, there were more oligonuclear Fe3+ Oy clusters in the Fe-ZSM-5-25 catalysts than in Fe-ZSM-5-300 (Si/Al-300). The results of catalytic performance on N2O decomposition showed that Fe-ZSM-5-25 catalysts had higher catalytic activities than Fe-ZSM-5-300 catalysts. The Fe-ZSM-5 catalysts prepared by chemical vapor deposition achieved the best catalytic activity in N2O decomposition among the catalysts prepared by the three methods. Moreover, the presence of O2 only slightly reduced N2O conversion, while NO promoted the N2O decomposition. Finally, after reaction for more than 100 h, Fe-ZSM-5 catalyst showed no obvious deactivation under simulated emission conditions. PMID:24720229

  7. Forsterite Carbonation in Wet Supercritical CO2 and Sodium Citrate

    NASA Astrophysics Data System (ADS)

    Qiu, L.; Schaef, T.; Wang, Z.; Miller, Q.; McGrail, P.

    2013-12-01

    Lin Qiu1*, Herbert T. Schaef2, Zhengrong Wang1, Quin R.S. Miller3, BP McGrail2 1. Yale University, New Haven, CT, USA 2. Pacific Northwest National Laboratory, Richland, WA, USA 3. University of Wyoming, Laramie, WY, USA Geologic reservoirs for managing carbon emissions (mostly CO2) have expanded over the last 5 years to include unconventional formations including basalts and fractured shales. Recently, ~1000 metric tons of CO2 was injected into the Columbia River Basalt (CRB) in Eastern Washington as part of the Wallula Pilot Project, Big Sky Regional Carbon Partnership. Based on reservoir conditions, the injected CO2 is present as a supercritical fluid that dissolves into the formation water over time, and reacts with basalt components to form carbonate minerals. In this paper, we discuss mineral transformation reactions occurring when the forsterite (Mg2SiO4) is exposed to wet scCO2 in equilibrium with pure water and sodium citrate solutions. Forsterite was selected as it is an important olivine group mineral present in igneous and mafic rocks. Citrate was selected as it has been shown to enhance mineral dissolution and organic ligands are possible degradation products of the microbial communities present in the formational waters of the CRB. For the supercritical phase, transformation reactions were examined by in situ high pressure x-ray diffraction (HXRD) in the presence of supercritical carbon dioxide (scCO2) in contact with water and sodium citrate solutions at conditions relevant to carbon sequestration. Experimental results show close-to-complete dissolution of forsterite in contact with scCO2 equilibrated with pure water for 90 hours (90 bar and 50°C). Under these conditions, thin films of water coated the mineral surface, providing a mechanism for silicate dissolution and transport of cations necessary for carbonate formation. The primary crystalline component initially detected with in situ HXRD was the hydrated magnesium carbonate, nesquehonite [Mg

  8. Contribution of the Global Soil Wetness Project 2 for PUB

    NASA Astrophysics Data System (ADS)

    Oki, T.; Dirmeyer, P. A.

    2003-04-01

    The Second Global Soil Wetness Project (GSWP-2) is the principal element of the large-scale uncoupled land surface modeling action in the Global Land-Atmosphere System Study (GLASS; Polcher et al. 2000) and a major element of the International Satellite Land-Surface Climatology Project (ISLSCP), both contributing projects of GEWEX. The overarching goal of GSWP is to produce as a community effort the best model estimates of the global land-surface water and energy cycles. This will entail an evaluation of the uncertainties linked to the land surface schemes (LSSs), their parameters, the forcing variables which drive them, and the spatial and temporal scales to run the numerical simulations. The original pilot phase of GSWP covered the two-year period of the ISLSCP initiative I data set (1987-1988), and proved the utility of model comparison and sensitivity studies of the land surface at the global scale (Dirmeyer et al. 1999). GSWP-2 will take advantage of the 10-year (1986-1995) ISLSCP Initiative II data set (http://islscp2.sesda.com/) and LSS simulations will be conducted at a spatial resolution of 1o, sans Antarctica. LSSs calculate runoff and it can be compared with river discharge with applying runoff routing models. Therefore GSWP can be considered as PUB on global scales. Regional scales should be more focused in PUB as hydrological science, nevertheless studies on global scale is also relevant since there are many places in the world where global datasets of precipitation, landuse, soil types, etc., are the only sources available for simulation and prediction of river runoff. Numerical experiments under GSWP2 is well designed to examine the uncertainties associated with the global offline simulations, and the outcomes should contribute for PUB studies very much. GSWP2 in PUB is also expected to identify to what extent of temporal and spatial resolution predicting river runoff can be estimated from global approach.

  9. Development studies for a novel wet oxidation process. Phase 2

    SciTech Connect

    1994-07-01

    DETOX{sup SM} is a catalyzed wet oxidation process which destroys organic materials in an acidic water solution of iron at 373 to 473 K. The solution can be used repeatedly to destroy great amounts of organic materials. Since the process is conducted in a contained vessel, air emissions from the process can be well controlled. The solution is also capable of dissolving and concentrating many heavy and radioactive metals for eventual stabilization and disposal. The Phase 2 effort for this project is site selection and engineering design for a DETOX demonstration unit. Site selection was made using a set of site selection criteria and evaluation factors. A survey of mixed wastes at DOE sites was conducted using the Interim Mixed Waste Inventory Report. Sites with likely suitable waste types were identified. Potential demonstration sites were ranked based on waste types, interest, regulatory needs, scheduling, ability to provide support, and available facilities. Engineering design for the demonstration unit is in progress and is being performed by Jacobs Applied Technology. The engineering design proceeded through preliminary process flow diagrams (PFDs), calculation of mass and energy balances for representative waste types, process and instrumentation diagrams (P and IDs), preparation of component specifications, and a firm cost estimate for fabrication of the demonstration unit.

  10. Second GEWEX/GLASS Global Soil Wetness Project (GSWP2)

    NASA Astrophysics Data System (ADS)

    Dirmeyer, P. A.; Oki, T.

    2002-05-01

    The Second Global Soil Wetness Project (GSWP2) is a land-surface modeling activity of the Global Land-Atmosphere System Study (GLASS) and the International Satellite Land-Surface Climatology Project (ISLSCP), both contributing projects of the Global Energy and Water Cycle Experiment (GEWEX). The first phase of GSWP2, a global 10-year multi-model simulation and comparison using the ISLSCP Initiative II data set (1986-1995), begins later this year. In addition to providing a large-scale test-bed for comparison of land surface schemes (LSSs), several sub-projects are proposed. Estimates of continental and global-scale surface energy and water budgets will be calculated, and inter-model uncertainties will be established. The ability of multiple LSSs to simulate large-scale interannual variations will be investigated. GSWP2 will serve as a global platform for the application of remote sensing to LSS calibration, validation and assimilation. Sensitivity of simulated fluxes and state variables to uncertainties in atmospheric forcings, soil, and vegetation parameters will be examined. The ability of simple and intermediate models to replicate the behavior of complex LSSs will be explored, as a tool for better understanding of surface processes. In situ validation of LSSs with data from numerous field campaigns conducted during the 10-year period will also be possible. GSWP2 will also explore promising new data management technologies, including the capability to perform model integration and analysis with distributed data sets, reducing the data management burden on participants. A subsequent continental phase will focus on North America, and will also investigate issues of aggregation (from 1/8 degree to 1 degree).

  11. [Scurvy with simultaneous wet beriberi in 2 patients].

    PubMed

    Bøhmer, T; Utzon, P; Tallaksen, C

    1994-11-10

    Two patients developed the clinical picture of scorbut and simultaneous wet beriberi. The diagnosis was confirmed by low concentrations of ascorbic acid and thiamin and thiaminfosfate-ester in serum and in whole blood. Treatment with ascorbic acid led to a rapid reversal of scorbutic changes, but the changes due to the wet beri-beri persisted. Thiamine supplementation was given only perorally in the first patient, and a severe catabolic state in the other delayed the improvement in the beriberi. Direct determination of ascorbic acid and thiamin and thiaminfosfate-esters in serum and in whole blood may confirm the diagnosis of vitamin deficiencies. PMID:7809869

  12. Catalytic, Diastereoselective 1,2-Difluorination of Alkenes.

    PubMed

    Banik, Steven M; Medley, Jonathan William; Jacobsen, Eric N

    2016-04-20

    We describe a direct, catalytic approach to the 1,2-difluorination of alkenes. The method utilizes a nucleophilic fluoride source and an oxidant in conjunction with an aryl iodide catalyst and is applicable to alkenes with all types of substitution patterns. In general, the vicinal difluoride products are produced with high diastereoselectivities. The observed sense of stereoinduction implicates anchimeric assistance pathways in reactions of alkenes bearing neighboring Lewis basic functionality. PMID:27046019

  13. Catalytic Methane Decomposition over Fe-Al2 O3.

    PubMed

    Zhou, Lu; Enakonda, Linga Reddy; Saih, Youssef; Loptain, Sergei; Gary, Daniel; Del-Gallo, Pascal; Basset, Jean-Marie

    2016-06-01

    The presence of a Fe-FeAl2 O4 structure over an Fe-Al2 O3 catalysts is demonstrated to be vital for the catalytic methane decomposition (CMD) activity. After H2 reduction at 750 °C, Fe-Al2 O3 prepared by means of a fusion method, containing 86.5 wt % FeAl2 O4 and 13.5 wt % Fe(0) , showed a stable CMD activity at 750 °C for as long as 10 h. PMID:27159367

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

    PubMed

    Montagner, Sara; Leoni, Cristina; Emming, Stefan; Della Chiara, Giulia; Balestrieri, Chiara; Barozzi, Iros; Piccolo, Viviana; Togher, Susan; Ko, Myunggon; Rao, Anjana; Natoli, Gioacchino; Monticelli, Silvia

    2016-05-17

    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. PMID:27160912

  15. ENHANCED CONTROL OF MERCURY BY WET FLUE GAS DESULFURIZATION SYSTEMS--SITE 2 RESULTS

    SciTech Connect

    G. Blythe; S. Miller; C. Richardson; K. Searcy

    2000-02-01

    The U.S. Department of Energy and EPRI are co-funding this project to improve the control of mercury emissions from coal-fired power plants equipped with wet flue gas desulfurization (FGD) systems. The project is investigating catalytic oxidation of vapor-phase elemental mercury to a form that is more effectively captured in wet FGD systems. If successfully developed, the process could be applicable to over 90,000 MW of utility generating capacity with existing FGD systems, and to future FGD installations. Field tests are being conducted to determine whether candidate catalyst materials remain active towards mercury oxidation after extended flue gas exposure. Catalyst life will have a large impact on the cost effectiveness of this potential process. A mobile catalyst test unit is being used to test the activity of four different catalysts for a period of up to six months at each of three utility sites. Catalyst testing at the first site, which fires Texas lignite, was completed in December 1998. Testing at the second test site, which fires a Powder River Basin subbituminous coal, was completed in the fall of 1999, and testing at the third site, which fires a high-sulfur bituminous coal, will begin in early 2000. This technical note reports results from Site 2; results from Site 1 were reported in a previous technical note. At Site 2, catalysts were tested in several forms, including powders dispersed in sand bed reactors and in more commercially viable forms such as extruded beads and coated honeycomb structures. This technical note presents results from Site 2 for both the sand bed reactors and commercial catalyst forms. Site 3 results are not yet available, but should be available late in the year 2000. Field testing is being supported by laboratory tests to screen catalysts for activity at specific flue gas compositions, to investigate catalyst deactivation mechanisms and to investigate methods for regenerating spent catalysts. Laboratory results related to the

  16. ENHANCED CONTROL OF MERCURY BY WET FLUE GAS DESULFURIZATION SYSTEMS--SITE 2 RESULTS

    SciTech Connect

    G. Blythe; S. Miller; C. Richardson; K. Searcy

    2000-06-01

    The U.S. Department of Energy and EPRI are co-funding this project to improve the control of mercury emissions from coal-fired power plants equipped with wet flue gas desulfurization (FGD) systems. The project is investigating catalytic oxidation of vapor-phase elemental mercury to a form that is more effectively captured in wet FGD systems. If successfully developed, the process could be applicable to over 90,000 MW of utility generating capacity with existing FGD systems, and to future FGD installations. Field tests are being conducted to determine whether candidate catalyst materials remain active towards mercury oxidation after extended flue gas exposure. Catalyst life will have a large impact on the cost effectiveness of this potential process. A mobile catalyst test unit is being used to test the activity of four different catalysts for a period of up to six months at each of three utility sites. Catalyst testing at the first site, which fires Texas lignite, was completed in December 1998. Testing at the second test site, which fires a Powder River Basin subbituminous coal, was completed in the fall of 1999, and testing at the third site, which fires a high-sulfur bituminous coal, will begin in 2000. This technical note reports results from Site 2; results from Site 1 were reported in a previous technical note. At Site 2, catalysts were tested in several forms, including powders dispersed in sand bed reactors and in commercial forms such as extruded beads and coated honeycomb structures. This technical note presents results from Site 2 for both the sand bed reactors and commercial catalyst forms. Field testing is being supported by laboratory tests to screen catalysts for activity at specific flue gas compositions, to investigate catalyst deactivation mechanisms and to investigate methods for regenerating spent catalysts. Laboratory results related to the Site 2 field effort are also included and discussed in this technical note. Preliminary economics, based

  17. Effect of chromium oxide as active site over TiO2-PILC for selective catalytic oxidation of NO.

    PubMed

    Zhang, Jingxin; Zhang, Shule; Cai, Wei; Zhong, Qin

    2013-12-01

    This study introduced TiO2-pillared clays (TiO2-PILC) as a support for the catalytic oxidation of NO and analyzed the performance of chromium oxides as the active site of the oxidation process. Cr-based catalysts were prepared by a wet impregnation method. It was found that the 10 wt.% chromium doping on the support achieved the best catalytic activity. At 350 degrees C, the NO conversion was 61% under conditions of GHSV = 23600 hr(-1). The BET data showed that the support particles had a mesoporous structure. H2-TPR showed that Cr(10)TiP (10 wt.% Cr doping on TiO2-PILC) clearly exhibited a smooth single peak. EPR and XPS were used to elucidate the oxidation process. During the NO + O2 adsorption, the intensity of evolution of superoxide ions (O2(-)) increased. The content of Cr3+ on the surface of the used catalyst was 40.37%, but when the used catalyst continued adsorbing NO, the Cr3+ increased to 50.28%. Additionally, O(alpha)/O(beta) increased markedly through the oxidation process. The NO conversion decreased when SO2 was added into the system, but when the SO2 was removed, the catalytic activity recovered almost up to the initial level. FT-IR spectra did not show a distinct characteristic peak of SO4(2-). PMID:24649682

  18. MnO2/CeO2 for catalytic ultrasonic degradation of methyl orange.

    PubMed

    Zhao, He; Zhang, Guangming; Zhang, Quanling

    2014-05-01

    Catalytic ultrasonic degradation of aqueous methyl orange was studied in this paper. Heterogeneous catalyst MnO2/CeO2 was prepared by impregnation of manganese oxide on cerium oxide. Morphology and specific surface area of MnO2/CeO2 catalyst were characterized and its composition was determined. Results showed big differences between fresh and used catalyst. The removal efficiency of methyl orange by MnO2/CeO2 catalytic ultrasonic process was investigated. Results showed that ultrasonic process could remove 3.5% of methyl orange while catalytic ultrasonic process could remove 85% of methyl orange in 10 min. The effects of free radical scavengers were studied to determine the role of hydroxyl free radical in catalytic ultrasonic process. Results showed that methyl orange degradation efficiency declined after adding free radical scavengers, illustrating that hydroxyl free radical played an important role in degrading methyl orange. Theoretic analysis showed that the resonance size of cavitation bubbles was comparable with the size of catalyst particles. Thus, catalyst particles might act as cavitation nucleus and enhance ultrasonic cavitation effects. Measurement of H2O2 concentration in catalytic ultrasonic process confirmed this hypothesis. Effects of pre-adsorption on catalytic ultrasonic process were examined. Pre-adsorption significantly improved methyl orange removal. The potential explanation was that methyl orange molecules adsorbed on catalysts could enter cavitation bubbles and undergo stronger cavitation. PMID:24369902

  19. NaNO(2)/FeCl(3) catalyzed wet oxidation of the azo dye Acid Orange 7.

    PubMed

    Peng, Yanrong; Fu, Dongmei; Liu, Renhua; Zhang, Feifang; Liang, Xinmiao

    2008-03-01

    A combination of ferric chloride and sodium nitrite significantly improved the wet oxidation of the azo dye Acid Orange 7 (AO7) in acid aqueous media (pH 2.6) under moderate conditions (T=150 degrees C; oxygen pressure=0.5 MPa). To evaluate the catalytic system, wet oxidation of AO7 was carried out at temperatures between 90 and 150 degrees C and oxygen pressures ranging from 0.1 to 0.5 MPa. The effect of initial solution pH from 2.6 to 11.4 and the amount of catalyst on the degradation of AO7 were also investigated. AO7 initial concentration was kept 200 mg L(-1). The degradation process was monitored by UV-visible spectroscopy, HPLC, IC (ion chromatography), GC-MS and TOC analysis. At 150 degrees C and 0.5 MPa oxygen pressure, 56% TOC was removed after 4h of treatment, while no obvious TOC removal were achieved without catalyst at the same experimental condition. The main degradation products were some small organic acids: formic acid, acetic acid, pyruvic acid, oxalic acid, succinic acid (identified and quantified by IC) and phthalic acid (identified by GC-MS). PMID:18177919

  20. Catalytic hydrodechlorination of chlorocarbons. 2: Ternary oxide supports for catalytic conversions of 1,2-dichlorobenzene

    SciTech Connect

    Gampine, A.; Eyman, D.P.

    1998-10-01

    Ternary oxides of Ti-Zr-Al and Ti-Zr-Si were prepared by coating commercial Al{sub 2}O{sub 3} and SiO{sub 2} with a THF solution of Ti(OPr{sup i}){sub 4} and Zr(OPr{sup 1}){sub 4} under controlled conditions. Nitrogen adsorption and X-ray powder diffraction indicate that the structure of the base supports, Al{sub 2}O{sub 3} and SiO{sub 2}, were not significantly altered upon coating and that TiO{sub 2} and ZrO{sub 2} were quite uniformly spread on them. The acid resistance of alumina was found to be increased upon coating. Palladium supported catalysts, Pd/TiZrAlO{sub x}, Pd/TiZrSiO{sub x}, Pd/TiO{sub 2}, Pd/ZrO{sub 2}, Pd/SiO{sub 2}, and Pd/Al{sub 2}O{sub 3} were prepared to evaluate the ternary oxides relative to the component single oxide supports. Palladium dispersion was determined using hydrogen chemisorption and the catalysts were evaluated for hydrodechlorination of 1,2-dichlorobenzene. The experimental runs were carried out in a microflow reactor system at atmospheric pressure, in the gas phase. The catalysts were oxidized and then reduced, prior to reaction. The kinetic studies showed that the ternary oxide-based catalyst, Pd/TiZrAlO{sub x} exhibited an improved stability and activity much higher than the arithmetic sum of the activities of the component single oxide based palladium catalysts. Comparison of the specific activities of the catalysts expressed as TOF, indicate that the observed differences in activity may be related to the chemical nature of the supports. The best catalyst had an initial specific activity of 16.6 s{sup {minus}1}. The authors observed that the pretreatment of the catalyst has a profound effect on its stability and activity. Also, the experimental results indicated that the major factors of the catalyst deactivation are agglomeration of palladium particles and HCl poisoning. Prospects for optimization of these catalysts are discussed in light of the results of this work.

  1. Capillary Trapping of CO2 in Oil Reservoirs: Observations in a Mixed-Wet Carbonate Rock.

    PubMed

    Al-Menhali, Ali S; Krevor, Samuel

    2016-03-01

    Early deployment of carbon dioxide storage is likely to focus on injection into mature oil reservoirs, most of which occur in carbonate rock units. Observations and modeling have shown how capillary trapping leads to the immobilization of CO2 in saline aquifers, enhancing the security and capacity of storage. There are, however, no observations of trapping in rocks with a mixed-wet-state characteristic of hydrocarbon-bearing carbonate reservoirs. Here, we found that residual trapping of supercritical CO2 in a limestone altered to a mixed-wet state with oil was significantly less than trapping in the unaltered rock. In unaltered samples, the trapping of CO2 and N2 were indistinguishable, with a maximum residual saturation of 24%. After the alteration of the wetting state, the trapping of N2 was reduced, with a maximum residual saturation of 19%. The trapping of CO2 was reduced even further, with a maximum residual saturation of 15%. Best-fit Land-model constants shifted from C = 1.73 in the water-wet rock to C = 2.82 for N2 and C = 4.11 for the CO2 in the mixed-wet rock. The results indicate that plume migration will be less constrained by capillary trapping for CO2 storage projects using oil fields compared with those for saline aquifers. PMID:26812184

  2. Residual Supercritical CO2 Saturation in an Oil-wet Sandstone: a Pore-scale Analysis

    NASA Astrophysics Data System (ADS)

    Rahman, T.; Lebedev, M.; Barifcani, A.; Iglauer, S.

    2015-12-01

    Residual supercritical CO2 (scCO2) in an oil-wet Bentheimer sandstone was imaged at high 3D resolution (3.4μm)3 with an x-ray micro-computed tomograph (μCT). The residual saturation measured (SCO2,r = 12%) was significantly lower than in an analogue strongly water-wet plug (SCO2,r = 35%). The residual CO2 was split into many small disconnected clusters, and the cluster size distributions followed a power law correlation, similar to those reported for water-wet rock. However, the CO2 was more frequently located in smaller pores than in the analogue water-wet case. On the μCT images we were able to measure scCO2-water interfacial areas and capillary pressures of each CO2 bubble in-situ. These capillary pressures (Pc) showed a distribution function which ranged from -1 MPa to +1 MPa, and peaked at Pc = 0. This variation in Pc will influence the mass transfer process (of CO2 into water) as it changes the chemical potential; but it is clear that the interfacial areas are large and thus provide a good basis for dissolution trapping. Overall we conclude that oil-wet storage rock has a significantly lower capillary trapping capacity, although we still observed residual CO2 at the pore-scale.

  3. Wetting and Reaction Characteristics of Al2O3/SiC Composite Refractories

    SciTech Connect

    Xu, Jing; Hemrick, James Gordon; Peters, Klaus-Markus; Liu, Xingbo; Barbero, Ever J

    2007-01-01

    The reactive wetting behavior of three types of alumina-silicon carbide composite refractory materials was investigated in contact with molten aluminum (Al) and Al alloy using an optimized sessile drop method at 900oC in a purified Ar-4% H2 atmosphere. The time dependent behavior of contact angle and droplet geometry was monitored and the wetting kinetics was identified. The initial contact angle between the liquid Al/Al alloy and two of the refractory substrates was found to be an obtuse angle, which gradually changed to a 90o angle and then eventually to an acute angle with time. However, the wetting angle for the third refractory substrate was found to stay at an obtuse angle for the entire two-hour duration of the experiment. The difference in wetting properties among three types of refractories is attributed to be due to their microstructural and compositional variations. The significant effect of the alloying magnesium added to the molten Al alloy droplets in regard to the wetting kinetics and the influence on the reaction with the refractory substrates is discussed. The results obtained provide important understanding on the wetting and corrosion mechanisms of alumina and silicon carbide materials in contact with molten aluminum.

  4. Wetting properties of phospholipid dispersion on tunable hydrophobic SiO2-glass plates.

    PubMed

    Alexandrova, Lidia; Karakashev, Stoyan I; Grigorov, L; Phan, Chi M; Smoukov, Stoyan K

    2015-06-01

    We study the wetting properties of very small droplets of salty aqueous suspensions of unilamellar liposomes of DMPC (dimyristoylphosphatidylcholine), situated on SiO2-glass surfaces with different levels of hydrophobicity. We evaluated two different measures of hydrophobicity of solid surfaces - receding contact angles and the thickness of wetting films trapped between an air bubble and the solid surface at different levels of hydrophobicity. We established a good correlation between methods which differ significantly in measurement difficulty and experimental setup. We also reveal details of the mechanism of wetting of different surfaces by the DMPC liposome suspension. Hydrophilic surfaces with water contact angles in the range of 0° to 35° are readily hydrophobized by the liposomes and only showed corresponding contact angles in the range 27°-43°. For same range of surface hydrophobicities, there was a clear reduction of the thickness of the wetting films between the surface and a bubble, reaching a minimum in the 35°-40° range. At higher levels of hydrophobicity both pure water and the liposome suspension show similar contact angles, and the thickness of wetting films between a bubble and those surfaces increases in parallel. Our analysis showed that the only force able to stabilize the film under these experimental conditions is steric repulsion. The latter suggests that nanobubbles adsorbed on hydrophobic parts of the surface, and coated with a DMPC layer, may be the cause of the 40-70 nm thickness of wetting films we observe. PMID:25441448

  5. Residual trapping of supercritical CO2 in oil-wet sandstone.

    PubMed

    Rahman, Taufiq; Lebedev, Maxim; Barifcani, Ahmed; Iglauer, Stefan

    2016-05-01

    Residual trapping, a key CO2 geo-storage mechanism during the first decades of a sequestration project, immobilizes micrometre sized CO2 bubbles in the pore network of the rock. This mechanism has been proven to work in clean sandstones and carbonates; however, this mechanism has not been proven for the economically most important storage sites into which CO2 will be initially injected at industrial scale, namely oil reservoirs. The key difference is that oil reservoirs are typically oil-wet or intermediate-wet, and it is clear that associated pore-scale capillary forces are different. And this difference in capillary forces clearly reduces the capillary trapping capacity (residual trapping) as we demonstrate here. For an oil-wet rock (water contact angle θ=130°) residual CO2 saturation SCO2,r (≈8%) was approximately halved when compared to a strongly water-wet rock (θ=0°; SCO2,r≈15%). Consequently, residual trapping is less efficient in oil-wet reservoirs. PMID:26871275

  6. Wetting of microstructured alumina fabricated by epitaxial growth of Al4B2O9 whiskers

    NASA Astrophysics Data System (ADS)

    Wang, Yifeng; Feng, Jicai; Chen, Zhe; Song, Xiaoguo; Cao, Jian

    2015-12-01

    Topographical microstructures were fabricated on alumina by epitaxial growth of Al4B2O9 whiskers in air. The products were characterized via scanning electron microscopy, transmission electron microscopy, and X-ray diffraction. The whiskers were found to grow along the [0 0 1] crystallographic direction, and the lattice mismatch between Al2O3 and Al4B2O9 was determined to be 0.03%. The wetting of the Al4B2O9-whisker-coated surfaces by Ag-36.7Cu-8.0Ti at.% alloy was studied. The time needed to reach the equilibrium stage reduced as the temperature increased, and the final contact angle for liquid alloy on the rough surface was 27° at 880 °C. The wetting dynamics of the whiskers coated surfaces was investigated. After wetting, a whisker-interconnected region was formed between alumina and the alloy.

  7. [Wet work].

    PubMed

    Kieć-Swierczyńska, Marta; Chomiczewska, Dorota; Krecisz, Beata

    2010-01-01

    Wet work is one of the most important risk factors of occupational skin diseases. Exposure of hands to the wet environment for more than 2 hours daily, wearing moisture-proof protective gloves for a corresponding period of time or necessity to wash hands frequently lead to the disruption of epidermal stratum corneum, damage to skin barrier function and induction of irritant contact dermatitis. It may also promote penetration of allergens into the skin and increase the risk of sensitization to occupational allergens. Exposure to wet work plays a significant role in occupations, such as hairdressers and barbers, nurses and other health care workers, cleaning staff, food handlers and metalworkers. It is more common among women because many occupations involving wet work are female-dominated. The incidence of wet-work-induced occupational skin diseases can be reduced by taking appropriate preventive measures. These include identification of high-risk groups, education of workers, organization of work enabling to minimize the exposure to wet work, use of personal protective equipment and skin care after work. PMID:20437890

  8. Wet foams hydrophobized by amphiphiles to give Al2O3 porous ceramics

    NASA Astrophysics Data System (ADS)

    Pokhrel, Ashish; Park, Jung Gyu; Kim, Ik Jin

    2012-05-01

    Wet chemical method to prepare ceramic foams with antecedent stability using inorganic particles (Al2O3,SiO2 etc.) which are in situ hydrophobized upon adsorption of short-chain amphiphilic molecules in the wet state and heightened mechanical property in the sintered state was developed. These wet foams are stable over several days and show no bubble coarsening nor drainage or creaming. This long-term stability is achieved through the irreversible adsorption of partially hydrophobized colloidal particles to the air-water interface using short-chain amphiphiles to in situ modify the wetting behavior of the particle surface based on the observations of Pickering emulsions. As a result, the suspension is foamed homogeneously throughout its entire volume and porous bulk materials can be produced upon drying and sintering. Wet foams featuring average bubble sizes between 30 and 300μm and sintered foams with porosity from 50 to 85% were obtained by adjusting the amphiphile - particle concentration, and additives in the initial suspension. Cells were mostly closed with an average size of approximately 150 μm. Single cells were separated by walls with minimum thicknesses of 1-3 μm.

  9. 2D-simulation of wet steam flow in a steam turbine with spontaneous condensation

    NASA Astrophysics Data System (ADS)

    Sun, Lan-Xin; Zheng, Qun; Liu, Shun-Long

    2007-06-01

    Removal of condensates from wet steam flow in the last stages of steam turbines significantly promotes stage efficiency and prevents erosion of rotors. In this paper, homogeneous spontaneous condensation in transonic steam flow in the 2-D rotor-tip section of a stage turbine is investigated. Calculated results agree with experimental data reasonably well. On the basis of the above work, a 2-D numerical simulation of wet steam flow in adjacent root sections of a complex steam turbine stage was carried out. Computational results were analyzed and provide insights into effective removal of humidity.

  10. Effect of core-shell structure and chitosan addition on catalytic activities of copper-containing silica-aluminosilicate composites in deNO(x) reaction by H2.

    PubMed

    Chamnankid, Busaya; Samanpratan, Rattanaporn; Kongkachuichay, Paisan

    2012-12-01

    Mesoporous silica-aluminosilicate composites were used as supports for selective catalytic reduction of NO by H2 using copper catalyst. Effect of loading techniques and structures of the supports on the catalytic performance were investigated. The nature, the oxidation state of copper, the structural properties and the morphology of the catalysts were characterized by means of UV-vis spectra, Fourier Transform Infrared Spectroscopy (FTIR), nitrogen sorption, and transmission electron microscopy, respectively. By using substitution technique, the copper(II) species were introduced into the silica-aluminosilicate framework by replacing aluminum atoms that located in the tetrahedral coordination. On the other hand, by using incipient wetness impregnation method, the copper species were deposited on the surface of composite materials. Upon testing their performances in deNO(x) reaction, the catalysts prepared by incipient wetness impregnation method showed higher catalytic activity than those prepared by substitution technique in any copper content. The core-shell structure was able to enhance the catalytic performance. It was found that, among the tested catalysts, the 1.5% Cu loaded core-shell mesoporous silica aluminosilicate composites prepared by an incipient wetness impregnation yielded the highest NO conversion of approximately 59%. However, the addition of chitosan creating macroporosity and controlling the uniform small clusters did not improve the catalytic performance. PMID:23447996

  11. Analysis of uncertainties in CRAC2 calculations: wet deposition and plume rise

    SciTech Connect

    Ward, R.C.; Kocher, D.C.; Hicks, B.B.; Hosker, R.P. Jr.; Ku, J.Y.; Rao, K.S.

    1984-01-01

    We have studied the sensitivity of results from the CRAC2 computer code, which predicts health impacts from a reactor-accident scenario, to uncertainties in selected meteorological models and parameters. The sources of uncertainty examined include the models for plume rise and wet deposition and the meteorological bin-sampling procedure. An alternative plume-rise model usually had little effect on predicted health impacts. In an alternative wet-deposition model, the scavenging rate depends only on storm type, rather than on rainfall rate and atmospheric stability class as in the CRAC2 model. Use of the alternative wet-deposition model in meteorological bin-sampling runs decreased predicted mean early injuries by as much as a factor of 2 to 3 and, for large release heights and sensible heat rates, decreased mean early fatalities by nearly an order of magnitude. The bin-sampling procedure in CRAC2 was expanded by dividing each rain bin into four bins that depend on rainfall rate. Use of the modified bin structure in conjunction with the CRAC2 wet-deposition model changed all predicted health impacts by less than a factor of 2. 9 references.

  12. Catalytic performance of Fe3O4-CoO/Al2O3 catalyst in ozonation of 2-(2,4-dichlorophenoxy)propionic acid, nitrobenzene and oxalic acid in water.

    PubMed

    Tong, Shaoping; Shi, Rui; Zhang, Hua; Ma, Chunan

    2010-01-01

    Fe3O4-CoO/Al2O3 catalyst was prepared by incipient wetness impregnation using Fe(NO3)3 x 9H2O and Co(NO3)2 x 6H2O as the precursors, and its catalytic performance was investigated in ozonation of 2-(2,4-dichlorophenoxy)propionic acid (2,4-DP), nitrobenzene and oxalic acid. The experimental results indicated that Fe3O4-CoO/Al2O3 catalyst enabled an interesting improvement of ozonation efficiency during the degradation of each organic pollutant, and the Fe3O4-CoO/Al2O3 catalytic ozonation system followed a radical-type mechanism. The kinetics of ozonation alone and Fe3O4-CoO/Al2O3 catalytic ozonation of three organic pollutants in aqueous solution were discussed under the mere consideration of direct ozone reaction and OH radical reaction to well investigate its performance. In the catalytic ozonation of 2,4-DP, the apparent reaction rate constants (k) were determined to be 1.456 x 10(-2) min(-1) for ozonation alone and 4.740 x 10(-2) min(-1) for O3/Fe3O4-CoO/Al203. And O3/Fe3O4-CoO/Al2O3 had a larger R(ct) (6.614 x 10(-9)) calculated by the relative method than O3 did (1.800 x 10(-9)), showing O3/Fe3O4-CoO/Al2O3 generated more hydroxyl radical. Similar results were also obtained in the catalytic ozonation of nitrobenzene and oxalic acid. The above results demonstrated that the catalytic performance of Fe3O4-CoO/Al2O3 in ozonation of studied organic substance was universal to a certain degree. PMID:21235195

  13. [4+2] and [4+3] catalytic cycloadditions of allenes.

    PubMed

    López, Fernando; Mascareñas, José L

    2014-05-01

    This feature review describes the development of catalytic [4+2] and [4+3] cycloadditions of allenes, as efficient and practical methodologies for assembling six and seven-membered cyclic systems. The different methodologies have been classified depending on the type of key reactive intermediate that was proposed in the catalytic cycle. PMID:24643377

  14. Pilot Plant Testing of Elemental Mercury Reemission from a Wet Scrubber (2)

    EPA Science Inventory

    This paper discusses the recent observations of elemental mercury (HgO) reemissions from a pilot-scale limestone wet scrubber. Simulated flue gas was generated by burning natural gas in a down-fired furnace and doped with 2000 ppm of sulfur dioxide (S02). Mercuric chloride (HgCl2...

  15. The atmospheric sulfur cycle over the Amazon Basin. 2. Wet season

    SciTech Connect

    Andreae, M.O.; Berresheim, H.; Lewis, B.L.; Li, S. ); Jacob, D.J. ); Talbot, R.W. ); Bingemer, H.

    1990-09-20

    The authors determined the fluxes and concentrations of atmospheric sulfur species at ground level and from aircraft over the Amazon Basin during the 1987 wet season, providing a comprehensive description of the sulfur cycle over a remote tropical region. The vertical profile of dimethylsulfide (DMS) during the wet season was found to be very similar to that measured during the dry season. The concentrations of hydrogen sulfide (H{sub 2}S) were almost an order of magnitude higher than those of DMS, which makes H{sub 2}S the most important biogenic source species in the atmospheric sulfur cycle over the Amazon Basin. Using the gradient-flux approach, estimated the flux of DMS at the top of the tree canopy. The canopy was a source of DMS during the day, and a weak sink during the night. Measurements of sulfur gas emissions from soils, using the chamber method, showed very small fluxes, consistent with the hypothesis that the forest canopy is the major source of sulfur gases. The observed soil and canopy emission fluxes are similar to those measured in temperate regions. The concentrations of SO{sub 2} and sulfate aerosol in the wet season atmosphere were similar to dry season values. The sulfate concentration in rainwater, on the other hand, was lower by about a factor of 5 during the wet season. Due to the higher precipitation rate, however, the wet deposition flux of sulfate was not significantly different between the seasons. The measured fluxes and concentrations of DMS, H{sub 2}S, and SO{sub 2} were consistent with a model describing transport and chemistry of these sulfur species in the boundary layer. The concentrations of aerosol and the sulfate deposition rate, on the other hand, could only be explained by import of significant amounts of marine and anthropogenic sulfate aerosol into the Amazon Basin.

  16. Human liver iduronate-2-sulphatase. Purification, characterization and catalytic properties.

    PubMed Central

    Bielicki, J; Freeman, C; Clements, P R; Hopwood, J J

    1990-01-01

    Human iduronate-2-sulphatase (EC 3.1.6.13), which is involved in the lysosomal degradation of the glycosaminoglycans heparan sulphate and dermatan sulphate, was purified more than 500,000-fold in 5% yield from liver with a six-step column procedure, which consisted of a concanavalin A-Sepharose-Blue A-agarose coupled step, chromatofocusing, gel filtration on TSK HW 50S-Fractogel, hydrophobic separation on phenyl-Sepharose CL-4B and size separation on TSK G3000SW Ultrapac. Two major forms were identified. Form A and form B, with pI values of 4.5 and less than 4.0 respectively, separated at the chromatofocusing step in approximately equal amounts of recovered enzyme activity. By gel-filtration methods form A had a native molecular mass in the range 42-65 kDa. When analysed by SDS/PAGE, dithioerythritol-reduced and non-reduced form A and form B consistently contained polypeptides of molecular masses 42 kDa and 14 kDa. Iduronate-2-sulphatase was purified from human kidney, placenta and lung, and form A was shown to have similar native molecular mass and subunit components to those observed for liver enzyme. Both forms of liver iduronate-2-sulphatase were active towards a variety of substrates derived from heparin and dermatan sulphate. Kinetic parameters (Km and Kcat) of form A were determined with a variety of substrates matching structural aspects of the physiological substrates in vivo, namely heparan sulphate, heparin and dermatan sulphate. Substrate with 6-sulphate esters on the aglycone residue adjacent to the iduronic acid 2-sulphate residue being attack were hydrolysed with catalytic efficiencies up to 200 times above that observed for the simplest disaccharide substrate without a 6-sulphated aglycone residue. The effect of incubation pH on enzyme activity towards the variety of substrates evaluated was complex and dependent on substrate aglycone structure, substrate concentration, buffer type and the presence of other proteins. Sulphate and phosphate ions and

  17. Insight into the Mechanism of Intramolecular Inhibition of the Catalytic Activity of Sirtuin 2 (SIRT2)

    PubMed Central

    Li, Jinyu; Flick, Franziska; Verheugd, Patricia; Carloni, Paolo; Lüscher, Bernhard; Rossetti, Giulia

    2015-01-01

    Sirtuin 2 (SIRT2) is a NAD+-dependent deacetylase that has been associated with neurodegeneration and cancer. SIRT2 is composed of a central catalytic domain, the structure of which has been solved, and N- and C-terminal extensions that are thought to control SIRT2 function. However structural information of these N- and C-terminal regions is missing. Here, we provide the first full-length molecular models of SIRT2 in the absence and presence of NAD+. We also predict the structural alterations associated with phosphorylation of SIRT2 at S331, a modification that inhibits catalytic activity. Bioinformatics tools and molecular dynamics simulations, complemented by in vitro deacetylation assays, provide a consistent picture based on which the C-terminal region of SIRT2 is suggested to function as an autoinhibitory region. This has the capacity to partially occlude the NAD+ binding pocket or stabilize the NAD+ in a non-productive state. Furthermore, our simulations suggest that the phosphorylation at S331 causes large conformational changes in the C-terminal region that enhance the autoinhibitory activity, consistent with our previous findings that phosphorylation of S331 by cyclin-dependent kinases inhibits SIRT2 catalytic activity. The molecular insight into the role of the C-terminal region in controlling SIRT2 function described in this study may be useful for future design of selective inhibitors targeting SIRT2 for therapeutic applications. PMID:26407304

  18. Catalytic cracking process

    DOEpatents

    Lokhandwala, Kaaeid A.; Baker, Richard W.

    2001-01-01

    Processes and apparatus for providing improved catalytic cracking, specifically improved recovery of olefins, LPG or hydrogen from catalytic crackers. The improvement is achieved by passing part of the wet gas stream across membranes selective in favor of light hydrocarbons over hydrogen.

  19. In situ infrared spectroscopic study of forsterite carbonation in wet supercritical CO2.

    PubMed

    Loring, John S; Thompson, Christopher J; Wang, Zheming; Joly, Alan G; Sklarew, Deborah S; Schaef, H Todd; Ilton, Eugene S; Rosso, Kevin M; Felmy, Andrew R

    2011-07-15

    Carbonation reactions are central to the prospect of CO(2) trapping by mineralization in geologic reservoirs. In contrast to the relevant aqueous-mediated reactions, little is known about the propensity for carbonation in the key partner fluid: supercritical carbon dioxide containing dissolved water ("wet" scCO(2)). We employed in situ mid-infrared spectroscopy to follow the reaction of a model silicate mineral (forsterite, Mg(2)SiO(4)) for 24 h with wet scCO(2) at 50 °C and 180 atm. The results show a dramatic dependence of reactivity on water concentration and the presence of liquid water on the forsterite particles. Exposure to neat scCO(2) showed no detectable carbonation reaction. At 47% and 81% water saturation, an Ångstrom-thick liquid-like water film was detected on the forsterite particles and less than 1% of the forsterite transformed. Most of the reaction occurred within the first 3 h of exposure to the fluid. In experiments at 95% saturation and with an excess of water (36% above water saturation), a nanometer-thick water film was detected, and the carbonation reaction proceeded continuously with approximately 2% and 10% conversion, respectively. Our collective results suggest constitutive links between water concentration, water film formation, reaction rate and extent, and reaction products in wet scCO(2). PMID:21699182

  20. Designing Catalytic Monoliths For Closed-Cycle CO2 Lasers

    NASA Technical Reports Server (NTRS)

    Guinn, Keith; Herz, Richard K.; Goldblum, Seth; Noskowski, ED

    1992-01-01

    LASCAT (Design of Catalytic Monoliths for Closed-Cycle Carbon Dioxide Lasers) computer program aids in design of catalyst in monolith by simulating effects of design decisions on performance of laser. Provides opportunity for designer to explore tradeoffs among activity and dimensions of catalyst, dimensions of monolith, pressure drop caused by flow of gas through monolith, conversion of oxygen, and other variables. Written in FORTRAN 77.

  1. Behavior of thermal spray aluminum coating in wet H{sub 2}S environments

    SciTech Connect

    Joia, C.; Berrera, P.; Kane, R.D.

    1999-11-01

    Sulfide stress cracking (SSC) and hydrogen induced cracking can cause severe damage in steel equipment exposed to wet H{sub 2}S environments. Metallic thermal spray coatings based on aluminum protect carbon steel from the corrosive media, when wet H{sub 2}S environments are a concern. In this program, a series of electrochemical tests were conducted. These tests involved exposure of coated samples to various environments containing H{sub 2}S, ammonia, chloride and cyanide to study the behavior of the aluminum coating associated with a stainless steel interlayer both applied by thermal spray. Results showed that the aluminum layer was corroded rapidly in solutions with pH higher than 11. In alkaline solutions with pH lower than 9 a protective aluminum layer and the corrosion rate was very low.

  2. Enhanced NO{sub x} removal in wet scrubbers using metal chelates. Final report, Volume 2

    SciTech Connect

    1992-12-01

    Successful pilot plant tests of simultaneous removal of SO{sub 2} and NO{sub x} in a wet lime flue gas desulfurization system were concluded in December. The test, at up to 1.5 MW(e) capacity, were conducted by the Cincinnati Gas and Electric Company and Dravo Lime Company for the US Department of Energy at a pilot plant facility at the Miami Fort station of CG&E near Cincinnati, Ohio. The pilot plant scrubbed a slipstream of flue gas from Unit 7 a 530 MW coal-fired electric generating unit. Tests were conducted in three phases between April and December. The technology tested was wet scrubbing with Thiosorbic{reg_sign} magnesium-enhanced lime for SO{sub 2} removal and simultaneous NO scrubbing with ferrous EDTA, a metal chelate. Magnesium-enhanced lime-based wet scrubbing is used at 20 full-scale high-sulfur coal-fired electric generating units with a combined capacity of 8500 MW. Ferrous EDTA reacts with nitric oxide, NO, which comprises about 96% of NO{sub x} from coal-fired boilers. In this report, although not precise, NO and NO{sub x} are used interchangeably. A major objective of the tests was to combine NO{sub x} removal using ferrous EDTA, a developing technology, with SO{sub 2} removal using wet lime FGD, already in wide commercial use. If successful, this could allow wide application of this NO{sub x} removal technology. Volume 2 covers: description and results of NO{sub x} removal tests; and description and results of waste characterization studies.

  3. Effects of Particle Size on the Gas Sensitivity and Catalytic Activity of In2O3

    NASA Astrophysics Data System (ADS)

    Zhang, Xiaoshui; Gu, Ruiqin; Zhao, Jinling; Jin, Guixin; Zhao, Mengke; Xue, Yongliang

    2015-10-01

    Nanosized In2O3 powders with different particle sizes were prepared by the microemulsion synthetic method. The effects of particle size on the gas-sensing and catalytic properties of the as-prepared In2O3 were investigated. Reductions in particle size to nanometer levels improved the sensitivity and catalytic activity of In2O3 to i-C4H10 and C2H5OH. The sensitivity of nanosized In2O3 (<42 nm) sensors to i-C4H10, H2 and C2H5OH was 2-4 times higher than that of chemically precipitated In2O3 (130 nm) sensor. A nearly linear relationship was observed between the catalytic activity and specific surface area of In2O3 for the oxidation of i-C4H10 and C2H5OH at 275 °C. The relationship between gas sensitivity and catalytic activity was further discussed. The results of this work reveal that catalytic activity plays a key role in enhancing the sensitivity of gas-sensing materials.

  4. Atmospheric Mg2+ wet deposition within the continental United States and implications for soil inorganic carbon sequestration

    NASA Astrophysics Data System (ADS)

    Goddard, Megan A.; Mikhailova, Elena A.; Post, Christopher J.; Schlautman, Mark A.

    2007-02-01

    Little is known about atmospheric magnesium ion (Mg2+) wet deposition in relation to soil inorganic carbon sequestration. Understanding the conversion of carbon dioxide (CO2) or organic carbon to a form having a long residence time within the soil (e.g., dolomite, magnesian calcite) will greatly benefit agriculture, industry, and society on a global scale. This preliminary study was conducted to analyze atmospheric Mg2+ wet deposition within the continental United States (U.S.) and to rank the twelve major soil orders in terms of average annual atmospheric Mg2+ wet deposition. The total average annual Mg2+ wet deposition for each soil order was estimated with geographic information systems (GIS) using the following data layers: (1) atmospheric Mg2+ wet deposition data layers covering the continental U.S. for a 10-yr period (1994-2003) and (2) a soil order data layer derived from a national soils database. A map of average annual Mg2+ wet deposition for 1994-2003 reveals that the highest deposition (0.75-1.41 kg ha-1) occurred in Oregon, Washington, parts of California, and the coastal areas of East Coast states due to magnesium enrichment of atmospheric deposition from sea salt. The Midwestern region of the U.S. received about 0.25-0.75 kg ha-1 Mg2+ wet deposition annually, which was associated with loess derived soils, occurrence of dust storms and possibly fertilization. The soil orders receiving the highest average annual atmospheric Mg2+ wet deposition from 1994 to 2003 were: (1) Mollisols (3.7 × 107 kg), (2) Alfisols (3.6 × 107 kg) and (3) Ultisols (2.8 × 107 kg). In terms of potential soil carbon sequestration, the average annual atmospheric Mg2+ wet deposition was equivalent to formation of the following theoretical amounts of dolomite: (1) Mollisols (2.8 × 108 kg of CaMg(CO3)2), (2) Alfisols (2.7 × 108 kg of CaMg(CO3)2) and (3) Ultisols (2.1 × 108 kg of CaMg(CO3)2). The soil orders receiving the lowest average annual atmospheric Mg2+ wet deposition

  5. Catalytic reduction of CN−, CO and CO2 by nitrogenase cofactors in lanthanide-driven reactions**

    PubMed Central

    Lee, Chi Chung

    2014-01-01

    Nitrogenase cofactors can be extracted into an organic solvent and added in an adenosine triphosphate (ATP)-free, organic solvent-based reaction medium to catalyze the reduction of cyanide (CN−), carbon monoxide (CO) and carbon dioxide (CO2) when samarium (II) iodide (SmI2) and 2,6-lutidinium triflate (Lut-H) are supplied as a reductant and a proton source, respectively. Driven by SmI2, the cofactors not only catalytically reduce CN− or CO to C1-C4 hydrocarbons, but also catalytically reduce CO2 to CO and C1-C3 hydrocarbons. The observation of C-C coupling from CO2 reveals a unique, Fischer-Tropsch-like reaction with an atypical carbonaceous substrate; whereas the achievement of catalytic turnover of CN−, CO and CO2 by isolated cofactors suggests the possibility to develop nitrogenase-based electrocatalysts for hydrocarbon production from these carbon-containing compounds. PMID:25420957

  6. Photocatalytic and thermal catalytic oxidation of acetaldehyde on Pt/TiO{sub 2}

    SciTech Connect

    Falconer, J.L.; Magrini-Bair, K.A.

    1998-10-01

    Low concentrations of acetaldehyde in air (60 ppm) were oxidized over TiO{sub 2} (Degussa P25) and 0.5% Pt/TiO{sub 2} catalysts from 24 to 200 C by photocatalytic and thermal catalytic reactions. On Pt/TiO{sub 2}, the contribution by photocatalytic oxidation (PCO) is a maximum at 140 C, where conversion is 2.8 times that at 24 C. Titania without Pt deactivates rapidly during PCO at elevated temperature due to a thermal catalytic reaction that takes place in parallel with PCO, but the addition of Pt dramatically slows deactivation. Apparently, Pt supplies spillover oxygen onto the TiO{sub 2}, and the oxygen oxidizes the acetaldehyde decomposition products in a dark reaction. Deactivated TiO{sub 2} without Pt was regenerated by PCO at room temperature. Seven distinct reactions (photocatalytic and thermal catalytic) are identified on Pt/TiO{sub 2}.

  7. The catalytic role of the M2 metal ion in PP2

    NASA Astrophysics Data System (ADS)

    Pan, Chang; Tang, Jun-Yi; Xu, Yun-Fei; Xiao, Peng; Liu, Hong-Da; Wang, Hao-An; Wang, Wen-Bo; Meng, Fan-Guo; Yu, Xiao; Sun, Jin-Peng

    2015-02-01

    PP2C family phosphatases (the type 2C family of protein phosphatases; or metal-dependent phosphatase, PPM) constitute an important class of signaling enzymes that regulate many fundamental life activities. All PP2C family members have a conserved binuclear metal ion active center that is essential for their catalysis. However, the catalytic role of each metal ion during catalysis remains elusive. In this study, we discovered that mutations in the structurally buried D38 residue of PP2Cα (PPM1A) redefined the water-mediated hydrogen network in the active site and selectively disrupted M2 metal ion binding. Using the D38A and D38K mutations of PP2Cα as specific tools in combination with enzymology analysis, our results demonstrated that the M2 metal ion determines the rate-limiting step of substrate hydrolysis, participates in dianion substrate binding and stabilizes the leaving group after P-O bond cleavage. The newly characterized catalytic role of the M2 metal ion in this family not only provides insight into how the binuclear metal centers of the PP2C phosphatases are organized for efficient catalysis but also helps increase our understanding of the function and substrate specificity of PP2C family members.

  8. The catalytic role of the M2 metal ion in PP2Cα.

    PubMed

    Pan, Chang; Tang, Jun-yi; Xu, Yun-fei; Xiao, Peng; Liu, Hong-da; Wang, Hao-an; Wang, Wen-bo; Meng, Fan-guo; Yu, Xiao; Sun, Jin-peng

    2015-01-01

    PP2C family phosphatases (the type 2C family of protein phosphatases; or metal-dependent phosphatase, PPM) constitute an important class of signaling enzymes that regulate many fundamental life activities. All PP2C family members have a conserved binuclear metal ion active center that is essential for their catalysis. However, the catalytic role of each metal ion during catalysis remains elusive. In this study, we discovered that mutations in the structurally buried D38 residue of PP2Cα (PPM1A) redefined the water-mediated hydrogen network in the active site and selectively disrupted M2 metal ion binding. Using the D38A and D38K mutations of PP2Cα as specific tools in combination with enzymology analysis, our results demonstrated that the M2 metal ion determines the rate-limiting step of substrate hydrolysis, participates in dianion substrate binding and stabilizes the leaving group after P-O bond cleavage. The newly characterized catalytic role of the M2 metal ion in this family not only provides insight into how the binuclear metal centers of the PP2C phosphatases are organized for efficient catalysis but also helps increase our understanding of the function and substrate specificity of PP2C family members. PMID:25708299

  9. An improved wet tropospheric correction for CryoSat-2 over open and coastal ocean

    NASA Astrophysics Data System (ADS)

    Joana Fernandes, M.; Lázaro, Clara; Nunes, Alexandra L.; Pires, Nelson; Dinardo, Salvatore; Benveniste, Jérôme

    2014-05-01

    In the scope of the CryoSat Plus for Oceans (CP4O) project, encouraged by the European Space Agency, a data combination (DComb) algorithm has been developed for the computation of the wet tropospheric correction (WTC) for CryoSat-2, which does not possess an onboard microwave radiometer (MWR), thus relying on a model-based WTC provided by the European Centre for Medium-Range Weather Forecasts (ECMWF). This WTC is based on the objective analysis of all available wet path delay data sources (e.g. from scanning imaging MWR (SI MWR) on board remote sensing satellites, those derived from Global Navigation Satellite Systems (GNSS) measurements at coastal stations and from an atmospheric model such as the ECMWF ReAnalysis (ERA) Interim. This presentation gives a brief description of the DComb algorithm and its application to CryoSat-2. The algorithm was first applied to Jason-2 and compared with the correction from the Jason-2 advanced microwave radiometer (AMR) present on the version D of the Geophysical Data Records (GDR-D), known to be a well calibrated and accurate correction, with improved performance in coastal regions. These results show that for epochs and locations for which SI-MWR measurements are available, the DComb WTC is very similar to that of AMR, evidencing that the SI-MWR water vapour products, previously calibrated with respect to AMR, are an extremely valuable data set for the estimation of the WTC for any altimeter mission, including those which possess an onboard MWR. For both Jason-2 and CryoSat-2 the new correction was validated through analysis of sea level anomaly variance at crossovers, function of distance from the coast and latitude. The influence of the GNSS-derived wet path delays in the coastal regions, of major importance for the full exploitation of CryoSat-2 data, in particular those acquired in the Synthetic Aperture Radar (SAR) mode, is also shown.

  10. Hg2+ reduction and re-emission from simulated wet flue gas desulfurization liquors.

    PubMed

    Wo, Jingjing; Zhang, Meng; Cheng, Xiaoya; Zhong, Xiaohang; Xu, Jiang; Xu, Xinhua

    2009-12-30

    In this study, considering that Hg(2+) in wet flue gas desulfurization (FGD) systems can easily be reduced and then released into atmosphere, causing secondary pollution, the researches about Hg(2+) reduction and Hg(0) re-emission mechanism were carried out. The effects of several experimental parameters on the reduction were studied, including initial pH, temperature, and concentrations of Cl(-) and S(IV). Our experimental results indicated that Cl(-) had a restraining effect on the Hg(2+) reduction and Hg(0) re-emission, after 24h reaction, only 20.5% of Hg(2+) was reduced with 100mM Cl(-) in simulated desulfurization solution. Cl(-) can slow Hg(2+) reduction and Hg(0) re-emissions dramatically through changing reaction mechanism, with formation of new intermediate: ClHgSO(3)(-), which can decompose to Hg(0), but much more slowly than Hg(SO(3))(2)(2-) or HgSO(3). Simulating the conditions of the practical application (initial pH 5, T=50 degrees C, S(IV)=5 mM, Cl(-)=100 mM), we also found that Ca(2+), NO(3)(-), F(-), etc. all had obvious effects on reduction rates. Based on the material balance and characteristic of the reactants, the reduction emission mechanism of Hg(2+) has been established, providing theoretical basis for industrial application of mercury control in wet FGD systems. PMID:19699584

  11. Theoretical models of catalytic domains of protein phosphatases 1 and 2A with Zn2+ and Mn2+ metal dications and putative bioligands in their catalytic centers.

    PubMed

    Woźniak-Celmer, E; Ołdziej, S; Ciarkowski, J

    2001-01-01

    The oligomeric metalloenzymes protein phosphatases dephosphorylate OH groups of Ser/Thr or Tyr residues of proteins whose actions depend on the phosphorus signal. The catalytic units of Ser/Thr protein phosphatases 1, 2A and 2B (PP1c, PP2Ac and PP2Bc, respectively), which exhibit about 45% sequence similarity, have their active centers practically identical. This feature strongly suggests that the unknown structure of PP2Ac could be successfully homology-modeled from the known structures of PP1c and/or PP2Bc. Initially, a theoretical model of PP1c was built, including a phosphate and a metal dication in its catalytic site. The latter was modeled, together with a structural hydroxyl anion, as a triangular pseudo-molecule (Zno or Mno), composed of two metal cations (double Zn2+ or Mn2+, respectively) and the OH- group. To the free PP1c two inhibitor sequences R29RRRPpTPAMLFR40 of DARPP-32 and R30RRRPpTPATLVLT42 of Inhibitor-1, and two putative substrate sequences LRRApSVA and QRRQRKpRRTI were subsequently docked. In the next step, a free PP2Ac model was built via homology re-modeling of the PP1c template and the same four sequences were docked to it. Thus, together, 20 starting model complexes were built, allowing for combination of the Zno and Mno pseudo-molecules, free enzymes and the peptide ligands docked in the catalytic sites of PP1c and PP2Ac. All models were subsequently subjected to 250-300 ps molecular dynamics using the AMBER 5.0 program. The equilibrated trajectories of the final 50 ps were taken for further analyses. The theoretical models of PP1c complexes, irrespective of the dication type, exhibited increased mobilities in the following residue ranges: 195-200, 273-278, 287-209 for the inhibitor sequences and 21-25, 194-200, 222-227, 261, 299-302 for the substrate sequences. Paradoxically, the analogous PP2Ac models appeared much more stable in similar simulations, since only their "prosegment" residues 6-10 and 14-18 exhibited an increased mobility

  12. Wet chemical synthesis and characterization of AgGaSe{sub 2} nanoparticles

    SciTech Connect

    Sugan, S.; Dhanasekaran, R.

    2013-06-03

    AgGaSe{sub 2} compound semiconductor nanoparticles were synthesized by wet chemical method using mercaptoacetic acid as a capping agent at room temperature. The synthesized powders belong to chalcopyrite structure confirmed by powder XRD. The surface morphology and crystalline size were observed by high resolution scanning electron microscope (HR-SEM). The stoichiometric composition of AgGaSe{sub 2} nanoparticles was confirmed by Energy dispersive X-ray (EDX) analysis. Different functional group vibrations of mercaptoacetic acid capped nanoparticles were studied using FT-IR spectrum. The absorbance and optical bandgap of the nanoparticles were determined using diffuse reflectance spectroscopy (DRS).

  13. CO catalytic oxidation on iron-embedded monolayer MoS2

    NASA Astrophysics Data System (ADS)

    Ma, Dongwei; Tang, Yanan; Yang, Gui; Zeng, Jun; He, Chaozheng; Lu, Zhansheng

    2015-02-01

    Based on first-principles calculations, the CO catalytic oxidation on the Fe-embedded monolayer MoS2 (Fe-MoS2) was investigated. It is found that Fe atom can be strongly constrained at the S vacancy of monolayer MoS2 with a high diffusion barrier. The CO oxidation reaction proceeds via a two-step mechanism with the highest energy barrier of 0.51 eV, which is started by the Langmuir-Hinshelwood reaction and ended by the Eley-Rideal reaction. The high catalytic activity of the Fe-MoS2 system may be attributed to the charge transfer and the orbital hybridization between the adsorbates and the Fe atom. This study proposes that embedding transition-metals is a promising way for making the basal plane of monolayer MoS2 catalytically active.

  14. Enantioselective construction of a 2,2'-bisindolylmethane scaffold via catalytic asymmetric reactions of 2-indolylmethanols with 3-alkylindoles.

    PubMed

    Gong, Yu-Xin; Wu, Qiong; Zhang, Hong-Hao; Zhu, Qiu-Ning; Shi, Feng

    2015-08-01

    A chiral phosphoric acid-catalyzed asymmetric reaction of 2-indolylmethanols with 3-alkylindoles has been established, which constructed a biologically important 2,2'-bisindolylmethane scaffold in high yields and good enantioselectivities (up to 98% yield, 94:6 er). This protocol not only provides an efficient method for constructing a 2,2'-bisindolylmethane framework in an enantioselective form, but also promotes the development of 2-indolylmethanol-involved catalytic asymmetric transformations. PMID:26111901

  15. In Situ Infrared Spectroscopic Study of Forsterite Carbonation in Wet Supercritical CO2

    SciTech Connect

    Loring, John S.; Thompson, Christopher J.; Wang, Zheming; Joly, Alan G.; Sklarew, Deborah S.; Schaef, Herbert T.; Ilton, Eugene S.; Rosso, Kevin M.; Felmy, Andrew R.

    2011-07-19

    Carbonation reactions are central to the prospect of CO2 trapping by mineralization in geologic reservoirs. In contrast to the relevant aqueous-mediated reactions, little is known about the propensity for carbonation in the long-term partner fluid: water-containing supercritical carbon dioxide (‘wet’ scCO2). We employed in situ mid-infrared spectroscopy to follow the reaction of a model silicate mineral (forsterite, Mg2SiO4) for 24 hr with wet scCO2 at 50°C and 180 atm, using water concentrations corresponding to 0%, 55%, 95%, and 136% saturation. Results show a dramatic dependence of reactivity on water concentration and the presence of liquid water on the forsterite particles. Exposure to neat scCO2 showed no detectable carbonation reaction. At 55% and 95% water saturation, a liquid-like thin water film was detected on the forsterite particles; less than 1% of the forsterite transformed, mostly within the first 3 hours of exposure to the fluid. At 136% saturation, where an (excess) liquid water film approximately several nanometers thick was intentionally condensed on the forsterite, the carbonation reaction proceeded continuously for 24 hr with 10% to 15% transformation. Our collective results suggest constitutive links between water concentration, water film formation, reaction rate and extent, and reaction products in wet scCO2.

  16. 40 CFR Table 2 to Subpart III of... - Operating Limits for Wet Scrubbers

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... and intermittent units) a Pressure drop across the wet scrubber or amperage to wet scrubber Minimum pressure drop or amperage Continuous Every 15 minutes 3-hour rolling a Scrubber liquor flow rate...

  17. 40 CFR Table 2 to Subpart III of... - Operating Limits for Wet Scrubbers

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... and intermittent units) a Pressure drop across the wet scrubber or amperage to wet scrubber Minimum pressure drop or amperage Continuous Every 15 minutes 3-hour rolling a Scrubber liquor flow rate...

  18. 40 CFR Table 2 to Subpart Cccc of... - Operating Limits for Wet Scrubbers

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... units) 3-hour rolling (continuous and intermittent units) a Pressure drop across the wet scrubber or amperage to wet scrubber Minimum pressure drop or amperage Continuous Every 15 minutes 3-hour rolling...

  19. 40 CFR Table 2 to Subpart III of... - Operating Limits for Wet Scrubbers

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... and intermittent units) a Pressure drop across the wet scrubber or amperage to wet scrubber Minimum pressure drop or amperage Continuous Every 15 minutes 3-hour rolling a Scrubber liquor flow rate...

  20. 40 CFR Table 2 to Subpart Cccc of... - Operating Limits for Wet Scrubbers

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... rolling (continuous and intermittent units) a Pressure drop across the wet scrubber or amperage to wet scrubber Minimum pressure drop or amperage Continuous Every 15 minutes 3-hour rolling a Scrubber...

  1. 40 CFR Table 2 to Subpart Cccc of... - Operating Limits for Wet Scrubbers

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... rolling (continuous and intermittent units) a Pressure drop across the wet scrubber or amperage to wet scrubber Minimum pressure drop or amperage Continuous Every 15 minutes 3-hour rolling a Scrubber...

  2. 40 CFR Table 2 to Subpart III of... - Operating Limits for Wet Scrubbers

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... and intermittent units) a Pressure drop across the wet scrubber or amperage to wet scrubber Minimum pressure drop or amperage Continuous Every 15 minutes 3-hour rolling a Scrubber liquor flow rate...

  3. 40 CFR Table 2 to Subpart Cccc of... - Operating Limits for Wet Scrubbers

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... units) 3-hour rolling (continuous and intermittent units) a Pressure drop across the wet scrubber or amperage to wet scrubber Minimum pressure drop or amperage Continuous Every 15 minutes 3-hour rolling...

  4. 40 CFR Table 2 to Subpart Cccc of... - Operating Limits for Wet Scrubbers

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... units) 3-hour rolling (continuous and intermittent units) a Pressure drop across the wet scrubber or amperage to wet scrubber Minimum pressure drop or amperage Continuous Every 15 minutes 3-hour rolling...

  5. 40 CFR Table 2 to Subpart III of... - Operating Limits for Wet Scrubbers

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... and intermittent units) a Pressure drop across the wet scrubber or amperage to wet scrubber Minimum pressure drop or amperage Continuous Every 15 minutes 3-hour rolling a Scrubber liquor flow rate...

  6. Impact of repeated dry-wet cycles on soil CO2 efflux in a beech forest

    NASA Astrophysics Data System (ADS)

    Leitner, Sonja; Saronjic, Nermina; Kobler, Johannes; Holtermann, Christian; Zechmeister-Boltenstern, Sophie; Zimmermann, Michael

    2015-04-01

    Climate change research predicts that both frequency and intensity of weather extremes such as severe droughts and heavy rainfall events will increase in mid Europe over the next decades. Because soil moisture is one of the major factors controlling microbially-driven soil processes, a changed moisture regime will impact soil organic matter (SOM) decomposition and nutrient cycling. This in turn can lead to feedback effects between altered precipitation and changed soil CO2 fluxes which can intensify climate change. Soil microorganisms can go into a state of dormancy or form inactive cysts to protect themselves from osmotic stress during soil drying. However, severe droughts increase microbial mortality which slows down SOM decomposition and decreases soil CO2 efflux. The rewetting of dry soil, on the other hand, causes large CO2 emissions, which is also known as the "Birch effect". Until today it is not clear whether these CO2 peaks outweigh the drought-induced decrease of total CO2 efflux. To investigate the impact of repeated dry-wet cycles on soil CO2 efflux we are conducting a precipitation manipulation experiment in a temperate Austrian beech forest. Roofs exclude rainfall and simulate drought periods, and heavy rainfall events are simulated with a sprinkler system. We apply repeated dry-wet cycles in two intensities: one treatment receives 6 cycles of 1 month drought followed by 75mm irrigation, and a parallel treatment receives 3 cycles of 2 months drought followed by 150mm irrigation. Soil CO2 efflux is constantly monitored with an automated flux chamber system, and environmental parameters are recorded via dataloggers. Our results show that droughts significantly reduce soil CO2 effluxes, and that the reductions depend on the length of the drought periods, with longer droughts leading to stronger reductions of CO2 effluxes. In the first 24 to 48h after rewetting, CO2 emissions strongly increased, and then slowly decreased again. Soil CO2 efflux was

  7. Ag–Fe2O3 nanocomposites with enhanced catalytic activity for reduction of 4-nitrophenol

    NASA Astrophysics Data System (ADS)

    Liu, Shiben; Chen, Yingjie; Dong, Lifeng

    2016-07-01

    Hybrid nanostructures can be multifunctional and even possess enhanced properties. Ag–Fe2O3 nanocomposites and Ag nanoparticles (NPs) were fabricated and applied to catalyze the reduction of 4-nitrophenol. Compared with Ag NPs, Ag–Fe2O3 nanocomposites demonstrated enhanced catalytic activities. Furthermore, due to their magnetic properties, Ag–Fe2O3 nanocomposites could be easily separated from the reaction mixture and recycled through an external magnetic field. These findings will help us design hybrid nanostructures with catalytic activity and explore other potential applications of magnetic nanocomposites.

  8. Electrochemical fabrication of Cu(OH) 2 and CuO nanostructures and their catalytic property

    NASA Astrophysics Data System (ADS)

    Ming, Hai; Pan, Keming; Liu, Yang; Li, Haitao; He, Xiaodie; Ming, Jun; Ma, Zheng; Kang, Zhenhui

    2011-07-01

    In this paper, we reported an anodization method for the fabrication of novel uniform Cu(OH) 2 nanowires, CuO nanoparticles, and CuO shuttle-like nanoparticles with advanced structures. The possible formation mechanism of Cu(OH) 2 nanowires, CuO nanoparticles, and CuO shuttle-like nanoparticles was proposed. The good catalytic properties of CuO nanoparticles converted from Cu(OH) 2 nanowires and the CuO shuttle-like nanoparticles were confirmed by evaluating their catalytic ability on the C-N cross coupling of amines with iodobenzene.

  9. Thickness dependent wetting properties and surface free energy of HfO2 thin films

    NASA Astrophysics Data System (ADS)

    Zenkin, Sergei; Belosludtsev, Alexandr; Kos, Šimon; Čerstvý, Radomír; Haviar, Stanislav; Netrvalová, Marie

    2016-06-01

    We show here that intrinsic hydrophobicity of HfO2 thin films can be easily tuned by the variation of film thickness. We used the reactive high-power impulse magnetron sputtering for preparation of high-quality HfO2 films with smooth topography and well-controlled thickness. Results show a strong dependence of wetting properties on the thickness of the film in the range of 50-250 nm due to the dominance of the electrostatic Lifshitz-van der Waals component of the surface free energy. We have found the water droplet contact angle ranging from ≈120° for the thickness of 50 nm to ≈100° for the thickness of 2300 nm. At the same time the surface free energy grows from ≈25 mJ/m2 for the thickness of 50 nm to ≈33 mJ/m2 for the thickness of 2300 nm. We propose two explanations for the observed thickness dependence of the wetting properties: influence of the non-dominant texture and/or non-monotonic size dependence of the particle surface energy.

  10. Electronic Coupling and Catalytic Effect on H2 Evolution of MoS2/Graphene Nanocatalyst

    NASA Astrophysics Data System (ADS)

    Liao, Ting; Sun, Ziqi; Sun, Chenghua; Dou, Shi Xue; Searles, Debra J.

    2014-09-01

    Inorganic nano-graphene hybrid materials that are strongly coupled via chemical bonding usually present superior electrochemical performance. However, how the chemical bond forms and the synergistic catalytic mechanism remain fundamental questions. In this study, the chemical bonding of the MoS2 nanolayer supported on vacancy mediated graphene and the hydrogen evolution reaction of this nanocatalyst system were investigated. An obvious reduction of the metallic state of the MoS2 nanolayer is noticed as electrons are transferred to form a strong contact with the reduced graphene support. The missing metallic state associated with the unsaturated atoms at the peripheral sites in turn modifies the hydrogen evolution activity. The easiest evolution path is from the Mo edge sites, with the presence of the graphene resulting in a decrease in the energy barrier from 0.17 to 0.11 eV. Evolution of H2 from the S edge becomes more difficult due to an increase in the energy barrier from 0.43 to 0.84 eV. The clarification of the chemical bonding and catalytic mechanisms for hydrogen evolution using this strongly coupled MoS2/graphene nanocatalyst provide a valuable source of reference and motivation for further investigation for improved hydrogen evolution using chemically active nanocoupled systems.

  11. Catalytic activity of lime for N{sub 2}O decomposition under coal combustion conditions

    SciTech Connect

    Sasaoka, Eiji; Sada, Norimasa; Hara, Kenichi; Uddin, M.A.; Sakata, Yusaku

    1999-04-01

    To understand the contribution of lime to the abatement of N{sub 2}O emission from fluidized coal combustor, the catalytic activity of the lime for the decomposition of N{sub 2}O under coal combustion conditions was studied. Lime was active for the catalytic decomposition of N{sub 2}O, and its activity was stable in the simulated coal combustion flue gas in the absence of SO{sub 2} at 800 C. The catalytic activity of lime was depressed by the presence of CO{sub 2}, H{sub 2}O, and SO{sub 2}. The affect of the presence of SO{sub 2} seemed to be most important: the catalytic activity of the lime gradually decreased as the degree of sulfation increased, and the specific surface area decreased with the progression of sulfation. From N{sub 2}O pretreatment and temperature-programmed desorption studies on the used lime, it was found that two oxygen species and one species of No desorbed. A surface character change due to sulfation is expected from these gas desorptions. From the relation of the activity to the surface area or the desorption of the gases or both, it was concluded that a decrease in the surface area contributed to the decay of the activity more effectively than the surface character change caused by the sulfation.

  12. Aryl-Allene Cyclization via a Hg(OTf)2-Catalytic Pathway.

    PubMed

    Yamamoto, Hirofumi; Ueda, Maho; Yamasaki, Naoto; Fujii, Akiyoshi; Sasaki, Ikuo; Igawa, Kazunobu; Kasai, Yusuke; Imagawa, Hiroshi; Nishizawa, Mugio

    2016-06-17

    Hg(OTf)2-catalyzed aryl-allene cyclization accompanied by formation of a quaternary carbon center has been realized. Deuterium-labeling experiments and computational modeling were used to propose a novel catalytic pathway involving direct H-transfer from the aromatic ring to the vinyl mercury moiety followed by mercury 1,2-migration. PMID:27232158

  13. Wet aerobic oxidation of lignin into aromatic aldehydes catalysed by a perovskite-type oxide: LaFe(1-x)Cu(x)O3 (x=0, 0.1, 0.2).

    PubMed

    Zhang, Junhua; Deng, Haibo; Lin, Lu

    2009-01-01

    The perovskite-type oxide catalyst LaFe(1-x)Cu(x)O(3 )(x=0, 0.1, 0.2) was prepared by the sol-gel method, and tested as a catalyst in the wet aerobic oxidation (WAO) of lignin into aromatic aldehydes. The lignin conversion and the yield of each aromatic aldehyde were significantly enhanced in the catalytic process, compared with the non-catalyzed process. Moreover, it was shown that the stability of activity and structure of LaFe(1-x)Cu(x)O(3 )(x=0, 0.1, 0.2) remained nearly unchanged after a series of successive recyclings of the catalytic reactions, indicating it was an efficient and recyclable heterogeneous catalyst for the conversion of lignin into aromatic aldehydes in the WAO process. PMID:19701121

  14. Nanostructured, mesoporous Au/TiO2 model catalysts – structure, stability and catalytic properties

    PubMed Central

    Roos, Matthias; Böcking, Dominique; Gyimah, Kwabena Offeh; Kucerova, Gabriela; Bansmann, Joachim; Biskupek, Johannes; Kaiser, Ute; Hüsing, Nicola

    2011-01-01

    Summary Aiming at model systems with close-to-realistic transport properties, we have prepared and studied planar Au/TiO2 thin-film model catalysts consisting of a thin mesoporous TiO2 film of 200–400 nm thickness with Au nanoparticles, with a mean particle size of ~2 nm diameter, homogeneously distributed therein. The systems were prepared by spin-coating of a mesoporous TiO2 film from solutions of ethanolic titanium tetraisopropoxide and Pluronic P123 on planar Si(100) substrates, calcination at 350 °C and subsequent Au loading by a deposition–precipitation procedure, followed by a final calcination step for catalyst activation. The structural and chemical properties of these model systems were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), N2 adsorption, inductively coupled plasma ionization spectroscopy (ICP–OES) and X-ray photoelectron spectroscopy (XPS). The catalytic properties were evaluated through the oxidation of CO as a test reaction, and reactivities were measured directly above the film with a scanning mass spectrometer. We can demonstrate that the thin-film model catalysts closely resemble dispersed Au/TiO2 supported catalysts in their characteristic structural and catalytic properties, and hence can be considered as suitable for catalytic model studies. The linear increase of the catalytic activity with film thickness indicates that transport limitations inside the Au/TiO2 film catalyst are negligible, i.e., below the detection limit. PMID:22003465

  15. Essential Nonredundant Function of the Catalytic Activity of Histone Deacetylase 2 in Mouse Development

    PubMed Central

    Hagelkruys, Astrid; Mattes, Katharina; Moos, Verena; Rennmayr, Magdalena; Ringbauer, Manuela; Sawicka, Anna

    2015-01-01

    The class I histone deacetylases (HDACs) HDAC1 and HDAC2 play partially redundant roles in the regulation of gene expression and mouse development. As part of multisubunit corepressor complexes, these two deacetylases exhibit both enzymatic and nonenzymatic functions. To examine the impact of the catalytic activities of HDAC1 and HDAC2, we generated knock-in mice expressing catalytically inactive isoforms, which are still incorporated into the HDAC1/HDAC2 corepressor complexes. Surprisingly, heterozygous mice expressing catalytically inactive HDAC2 die within a few hours after birth, while heterozygous HDAC1 mutant mice are indistinguishable from wild-type littermates. Heterozygous HDAC2 mutant mice show an unaltered composition but reduced associated deacetylase activity of corepressor complexes and exhibit a more severe phenotype than HDAC2-null mice. They display changes in brain architecture accompanied by premature expression of the key regulator protein kinase C delta. Our study reveals a dominant negative effect of catalytically inactive HDAC2 on specific corepressor complexes resulting in histone hyperacetylation, transcriptional derepression, and, ultimately, perinatal lethality. PMID:26598605

  16. Mono(imidazolin-2-iminato) actinide complexes: synthesis and application in the catalytic dimerization of aldehydes.

    PubMed

    Karmel, Isabell S R; Fridman, Natalia; Tamm, Matthias; Eisen, Moris S

    2014-12-10

    The synthesis of the mono(imidazolin-2-iminato) actinide(IV) complexes [(Im(R)N)An(N{SiMe3)2}3] (3-8) was accomplished by the protonolysis reaction between the respective imidazolin-2-imine (Im(R)NH, R = tBu, Mes, Dipp) and the actinide metallacycles [{(Me3Si)N}2An{κ(2)C,N-CH2SiMe2N(SiMe3)}] (1, An = U; 2, M = Th). The thorium and uranium complexes were obtained in high yields, and their structures were established by single-crystal X-ray diffraction analysis. The mono(imidazolin-2-iminato) actinide complexes 3-8 display short An-N bonds together with large An-N-C angles, indicating strong electron donation from the imidazolin-2-iminato moiety to the metal, corroborating a substantial π-character to the An-N bond. The reactivity of complexes 3-8 toward benzaldehyde was studied in the catalytic dimerization of aldehydes (Tishchenko reaction), displaying low to moderate catalytic activities for the uranium complexes 3-5 and moderate to high catalytic activities for the thorium analogues 6-8, among which 8 exhibited the highest catalytic activity. In addition, actinide coordination compounds showed unprecedented reactivity toward cyclic and branched aliphatic aldehydes in the catalytic Tishchenko reaction mediated by the thorium complex [(Im(Dipp)N)Th{N(SiMe3)2}3] (8), exhibiting high activity even at room temperature. Moreover, complex 8 was successfully applied in the crossed Tishchenko reaction between an aromatic or polyaromatic and an aliphatic cyclic and branched aldehyde, yielding selectively the asymmetrically substituted ester in high yields (80-100%). PMID:25393398

  17. Copper Wetting of x-Al(2)O(3)(0001): Theory and Experiment

    SciTech Connect

    Bogicevic, A.; Jennison, D.R.; Kelber, J.A.; Niu, Chengyu; Shepherd, K.

    1999-08-10

    XPS studies have been carried out on sputter deposited copper on a substantially hydroxylated {alpha}-Al{sub 2}O{sub 3}(0001) (sapphire) surface under ultra-high vacuum (UHV) conditions. XPS-derived Cu uptake curves show a sharp change in slope at a coverage of 0.35 monolayer (on a Cu/O atomic basis), indicative of initial layer-by-layer growth. CU(LMM) lineshape data indicate that, prior to the first break in the curve, Cu is oxidized to Cu(I). At higher coverages, metallic CU(0) is. observed. These data agree with first principles theoretical calculations, indicating that the presence of ad-hydroxyl groups greatly enhances the binding of Cu to bulk sapphire surfaces, stabilizing Cu(I) adatoms over two-dimensional metallic islands. In the absence of hydroxylation, calculations indicate significantly weaker Cu binding to the bulk sapphire substrate and non-wetting. Calculations also predict that at Cu coverages above 1/3 monolayer (ML), Cu-Cu interactions predominate, leading to Cu(0) formation. These results are in excellent agreement with experiment. The ability of surface hydroxyl groups to enhance binding to alumina substrates suggests a reason for contradictory experimental results reported in the literature for Cu wetting of alumina.

  18. Tunable Molecular MoS2 Edge-Site Mimics for Catalytic Hydrogen Production.

    PubMed

    Garrett, Benjamin R; Polen, Shane M; Click, Kevin A; He, Mingfu; Huang, Zhongjie; Hadad, Christopher M; Wu, Yiying

    2016-04-18

    Molybdenum sulfides represent state-of-the-art, non-platinum electrocatalysts for the hydrogen evolution reaction (HER). According to the Sabatier principle, the hydrogen binding strength to the edge active sites should be neither too strong nor too weak. Therefore, it is of interest to develop a molecular motif that mimics the catalytic sites structurally and possesses tunable electronic properties that influence the hydrogen binding strength. Furthermore, molecular mimics will be important for providing mechanistic insight toward the HER with molybdenum sulfide catalysts. In this work, a modular method to tune the catalytic properties of the S-S bond in MoO(S2)2L2 complexes is described. We studied the homogeneous electrocatalytic hydrogen production performance metrics of three catalysts with different bipyridine substitutions. By varying the electron-donating abilities, we present the first demonstration of using the ligand to tune the catalytic properties of the S-S bond in molecular MoS2 edge-site mimics. This work can shed light on the relationship between the structure and electrocatalytic activity of molecular MoS2 catalysts and thus is of broad importance from catalytic hydrogen production to biological enzyme functions. PMID:27022836

  19. Crystal structure of 2-nitropropane dioxygenase complexed with FMN and substrate. Identification of the catalytic base.

    PubMed

    Ha, Jun Yong; Min, Ji Young; Lee, Su Kyung; Kim, Hyoun Sook; Kim, Do Jin; Kim, Kyoung Hoon; Lee, Hyung Ho; Kim, Hye Kyung; Yoon, Hye-Jin; Suh, Se Won

    2006-07-01

    Nitroalkane compounds are widely used in chemical industry and are also produced by microorganisms and plants. Some nitroalkanes have been demonstrated to be carcinogenic, and enzymatic oxidation of nitroalkanes is of considerable interest. 2-Nitropropane dioxygenases from Neurospora crassa and Williopsis mrakii (Hansenula mrakii), members of one family of the nitroalkane-oxidizing enzymes, contain FMN and FAD, respectively. The enzymatic oxidation of nitroalkanes by 2-nitropropane dioxygenase operates by an oxidase-style catalytic mechanism, which was recently shown to involve the formation of an anionic flavin semiquinone. This represents a unique case in which an anionic flavin semiquinone has been experimentally observed in the catalytic pathway for oxidation catalyzed by a flavin-dependent enzyme. Here we report the first crystal structure of 2-nitropropane dioxygenase from Pseudomonas aeruginosa in two forms: a binary complex with FMN and a ternary complex with both FMN and 2-nitropropane. The structure identifies His(152) as the proposed catalytic base, thus providing a structural framework for a better understanding of the catalytic mechanism. PMID:16682407

  20. Fundamentals and Catalytic Applications of CeO2-Based Materials.

    PubMed

    Montini, Tiziano; Melchionna, Michele; Monai, Matteo; Fornasiero, Paolo

    2016-05-25

    Cerium dioxide (CeO2, ceria) is becoming an ubiquitous constituent in catalytic systems for a variety of applications. 2016 sees the 40(th) anniversary since ceria was first employed by Ford Motor Company as an oxygen storage component in car converters, to become in the years since its inception an irreplaceable component in three-way catalysts (TWCs). Apart from this well-established use, ceria is looming as a catalyst component for a wide range of catalytic applications. For some of these, such as fuel cells, CeO2-based materials have almost reached the market stage, while for some other catalytic reactions, such as reforming processes, photocatalysis, water-gas shift reaction, thermochemical water splitting, and organic reactions, ceria is emerging as a unique material, holding great promise for future market breakthroughs. While much knowledge about the fundamental characteristics of CeO2-based materials has already been acquired, new characterization techniques and powerful theoretical methods are deepening our understanding of these materials, helping us to predict their behavior and application potential. This review has a wide view on all those aspects related to ceria which promise to produce an important impact on our life, encompassing fundamental knowledge of CeO2 and its properties, characterization toolbox, emerging features, theoretical studies, and all the catalytic applications, organized by their degree of establishment on the market. PMID:27120134

  1. Structure of the catalytic domain of glucuronoyl esterase Cip2 from Hypocrea jecorina

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The structure of the catalytic domain of glucuronoyl esterase Cip2 from the fungus Hypocrea jecorina was determined at a resolution of 1.9 Angstroms. This is the first structure of the newly established carbohydrate esterase family 15. The structure has revealed the residues Ser278–His411–Glu301 pre...

  2. Catalytic reaction of 3-phenyl-2-propyn-1-ol with alcohols

    SciTech Connect

    Grigoryan, S.G.; Avetisyan, K.G.; Matnishyan, A.A.

    1987-01-10

    The cyclic ketal 2,5-dimethyl-2,5-bis(3-phenyl-2-propynyloxy)-1,4-dioxane was obtained by the reaction of 3-phenyl-2-propyn-1=ol with propargyl alcohol in the presence of the HgO-BF/sub 3/ O(C/sub 2/H/sub 5/)/sub 2/ catalytic system. The transformation of 3-phenyl-2-propyn-1-ol and its ethers in methanol and ethanol by the action of the above-mentioned catalytic system leads to 1-phenyl-3-alkoxy-1-propanone, 1-phenyl-1,1,3-trialkoxypropane, and 1-phenyl-2-propen-1-one. The intermediate organomercury compound, which is the product from regioselective addition of mercuric oxide and the saturated alcohol at the triple bond, was isolated. Its protodemercuration led to the above-mentioned linear products. The formation of the cyclic ketal is presumably due to the preferred formation of mercury bis-hydroxypropargylide.

  3. Wet chemical techniques for passivation of YBa2Cu3O7(7-x)

    NASA Technical Reports Server (NTRS)

    Vasquez, R. P.; Foote, M. C.; Hunt, B. D.

    1989-01-01

    Wet chemical techniques are described for treatment of YBa2Cu3O(7-x) surfaces, resulting in the formation of native compounds with little or no reactivity to water. Promising native compounds include CuI, BaSO4, CuS, Cu2S, and the oxalates, all of which are either insoluble or have very low solubility in water. Treatment with dilute HI results in the formation of a native iodide film which is 80-90 percent CuI with small amounts of YI3 and BaI2. Treatment with dilute H2SO4 results in the formation of a film which is 95 percent BaSO4 and 5 percent Y2(SO4)3. Cu2S is formed on the surface with a dilute Na2S solution. An oxalate film with equal amounts of Y2(C2O4)3 and BaC2O4 results from treatment with dilute oxalic acid. X-ray photoelectron spectra show no significant changes when the sulfide, sulfate, or oxalate films are dipped in water, while the iodide film shows evidence of Cu(OH)2 formation.

  4. Catalytic characterization of human microsomal glutathione S-transferase 2: identification of rate-limiting steps.

    PubMed

    Ahmad, Shabbir; Niegowski, Damian; Wetterholm, Anders; Haeggström, Jesper Z; Morgenstern, Ralf; Rinaldo-Matthis, Agnes

    2013-03-12

    Microsomal glutathione S-transferase 2 (MGST2) is a 17 kDa trimeric integral membrane protein homologous to leukotriene C4 synthase (LTC4S). MGST2 has been suggested to catalyze the biosynthesis of the pro-inflammatory mediator leukotriene C4 (LTC4) in cells devoid of LTC4S. A detailed biochemical study of MGST2 is critical for the understanding of its cellular function and potential role as an LTC4-producing enzyme. Here we have characterized the substrate specificity and catalytic properties of purified MGST2 by steady-state and pre-steady-state kinetic experiments. In comparison with LTC4S, which has a catalytic efficiency of 8.7 × 10(5) M(-1) s(-1), MGST2, with a catalytic efficiency of 1.8 × 10(4) M(-1) s(-1), is considerably less efficient in producing LTC4. However, the two enzymes display a similar KM(LTA4) of 30-40 μM. While LTC4S has one activated glutathione (GSH) (forming a thiolate) per enzyme monomer, the MGST2 trimer seems to display only third-of-the-sites reactivity for thiolate activation, which in part would explain its lower catalytic efficiency. Furthermore, MGST2 displays GSH-dependent peroxidase activity of ∼0.2 μmol min(-1) mg(-1) toward several lipid hydroperoxides. MGST2, but not LTC4S, is efficient in catalyzing conjugation of the electrophilic substrate 1-chloro-2,4-dinitrobenzene (CDNB) and the lipid peroxidation product 4-hydroxy-2-nonenal with GSH. Using stopped-flow pre-steady-state kinetics, we have characterized the full catalytic reaction of MGST2 with CDNB and GSH as substrates, showing an initial rapid equilibrium binding of GSH followed by thiolate formation. Burst kinetics for the CDNB-GSH conjugation step was observed only at low GSH concentrations (thiolate anion formation becoming rate-limiting under these conditions). Product release is rapid and does not limit the overall reaction. Therefore, in general, the chemical conjugation step is rate-limiting for MGST2 at physiological GSH concentrations. MGST2 and LTC4S

  5. Simultaneous removal of SO2 and NO by wet scrubbing using aqueous chlorine dioxide solution.

    PubMed

    Jin, Dong-Seop; Deshwal, Bal-Raj; Park, Young-Seong; Lee, Hyung-Keun

    2006-07-31

    The present study attempts to generate chlorine dioxide (ClO(2)) gas continuously by chlorate-chloride process and to utilize it further to clean up SO(2) and NO(x) gases simultaneously from the flue gas in the lab-scale bubbling reactor. Experiments were carried out to examine the effect of various operating parameters like input SO(2) concentration, input NO concentration, pH of the reaction medium, and ClO(2) feeding rate on the SO(2) and NO(x) removal efficiencies at 45 degrees C. Complete oxidation of NO into NO(2) occurred on passing sufficient ClO(2) gas into the scrubbing solution. SO(2) removal efficiency of about 100% and NO(x) removal efficiency of 66-72% were achieved under optimized conditions. NO(x) removal efficiency decreased slightly with increasing pH and NO concentration. Input SO(2) concentration had marginal catalytic effect on NO(2) absorption. No improvement in the NO(x) removal efficiency was observed on passing excess of chlorine dioxide in the scrubbing solution. PMID:16442222

  6. Catalytic reduction of CN-, CO, and CO2 by nitrogenase cofactors in lanthanide-driven reactions.

    PubMed

    Lee, Chi Chung; Hu, Yilin; Ribbe, Markus W

    2015-01-19

    Nitrogenase cofactors can be extracted into an organic solvent to catalyze the reduction of cyanide (CN(-)), carbon monoxide (CO), and carbon dioxide (CO2) without using adenosine triphosphate (ATP), when samarium(II) iodide (SmI2) and 2,6-lutidinium triflate (Lut-H) are employed as a reductant and a proton source, respectively. Driven by SmI2, the cofactors catalytically reduce CN(-) or CO to C1-C4 hydrocarbons, and CO2 to CO and C1-C3 hydrocarbons. The C-C coupling from CO2 indicates a unique Fischer-Tropsch-like reaction with an atypical carbonaceous substrate, whereas the catalytic turnover of CN(-), CO, and CO2 by isolated cofactors suggests the possibility to develop nitrogenase-based electrocatalysts for the production of hydrocarbons from these carbon-containing compounds. PMID:25420957

  7. Anacardic acid inhibits the catalytic activity of matrix metalloproteinase-2 and matrix metalloproteinase-9.

    PubMed

    Omanakuttan, Athira; Nambiar, Jyotsna; Harris, Rodney M; Bose, Chinchu; Pandurangan, Nanjan; Varghese, Rebu K; Kumar, Geetha B; Tainer, John A; Banerji, Asoke; Perry, J Jefferson P; Nair, Bipin G

    2012-10-01

    Cashew nut shell liquid (CNSL) has been used in traditional medicine for the treatment of a wide variety of pathophysiological conditions. To further define the mechanism of CNSL action, we investigated the effect of cashew nut shell extract (CNSE) on two matrix metalloproteinases, MMP-2/gelatinase A and MMP-9/gelatinase B, which are known to have critical roles in several disease states. We observed that the major constituent of CNSE, anacardic acid, markedly inhibited the gelatinase activity of 3T3-L1 cells. Our gelatin zymography studies on these two secreted gelatinases, present in the conditioned media from 3T3-L1 cells, established that anacardic acid directly inhibited the catalytic activities of both MMP-2 and MMP-9. Our docking studies suggested that anacardic acid binds into the MMP-2/9 active site, with the carboxylate group of anacardic acid chelating the catalytic zinc ion and forming a hydrogen bond to a key catalytic glutamate side chain and the C15 aliphatic group being accommodated within the relatively large S1' pocket of these gelatinases. In agreement with the docking results, our fluorescence-based studies on the recombinant MMP-2 catalytic core domain demonstrated that anacardic acid directly inhibits substrate peptide cleavage in a dose-dependent manner, with an IC₅₀ of 11.11 μM. In addition, our gelatinase zymography and fluorescence data confirmed that the cardol-cardanol mixture, salicylic acid, and aspirin, all of which lack key functional groups present in anacardic acid, are much weaker MMP-2/MMP-9 inhibitors. Our results provide the first evidence for inhibition of gelatinase catalytic activity by anacardic acid, providing a novel template for drug discovery and a molecular mechanism potentially involved in CNSL therapeutic action. PMID:22745359

  8. Anacardic Acid Inhibits the Catalytic Activity of Matrix Metalloproteinase-2 and Matrix Metalloproteinase-9

    PubMed Central

    Omanakuttan, Athira; Nambiar, Jyotsna; Harris, Rodney M.; Bose, Chinchu; Pandurangan, Nanjan; Varghese, Rebu K.; Kumar, Geetha B.; Tainer, John A.; Banerji, Asoke; Perry, J. Jefferson P.

    2012-01-01

    Cashew nut shell liquid (CNSL) has been used in traditional medicine for the treatment of a wide variety of pathophysiological conditions. To further define the mechanism of CNSL action, we investigated the effect of cashew nut shell extract (CNSE) on two matrix metalloproteinases, MMP-2/gelatinase A and MMP-9/gelatinase B, which are known to have critical roles in several disease states. We observed that the major constituent of CNSE, anacardic acid, markedly inhibited the gelatinase activity of 3T3-L1 cells. Our gelatin zymography studies on these two secreted gelatinases, present in the conditioned media from 3T3-L1 cells, established that anacardic acid directly inhibited the catalytic activities of both MMP-2 and MMP-9. Our docking studies suggested that anacardic acid binds into the MMP-2/9 active site, with the carboxylate group of anacardic acid chelating the catalytic zinc ion and forming a hydrogen bond to a key catalytic glutamate side chain and the C15 aliphatic group being accommodated within the relatively large S1′ pocket of these gelatinases. In agreement with the docking results, our fluorescence-based studies on the recombinant MMP-2 catalytic core domain demonstrated that anacardic acid directly inhibits substrate peptide cleavage in a dose-dependent manner, with an IC50 of 11.11 μM. In addition, our gelatinase zymography and fluorescence data confirmed that the cardol-cardanol mixture, salicylic acid, and aspirin, all of which lack key functional groups present in anacardic acid, are much weaker MMP-2/MMP-9 inhibitors. Our results provide the first evidence for inhibition of gelatinase catalytic activity by anacardic acid, providing a novel template for drug discovery and a molecular mechanism potentially involved in CNSL therapeutic action. PMID:22745359

  9. An investigation on NO removal by wet scrubbing using NaClO2 seawater solution.

    PubMed

    Han, Zhitao; Yang, Shaolong; Zheng, Dekang; Pan, Xinxiang; Yan, Zhijun

    2016-01-01

    The experiments were conducted to investigate the NO removal by wet scrubbing using NaClO2 seawater solution in a cyclic scrubbing mode. Results show that, when the concentration of NaClO2 in scrubbing solution is higher than 10 mM, a complete removal of NO can be achieved during the cyclic scrubbing process. The breakthrough time for seawater with 15 mM NaClO2 is enhanced by 34.3 % compared with that for NaClO2 freshwater. The extension of the breakthrough time for NaClO2 seawater is mainly ascribed to the improved utilization of NaClO2 in the solution. The good buffering ability of seawater could suppress the acidic decomposition of NaClO2 into ClO2 effectively. The analysis of reaction products indicates that the main anions in the spent liquor are chloride ions and nitrate ions. The calculation of NaClO2 utilization according to the ion chromatography also agrees well with the experimental results of breakthrough times. PMID:27386234

  10. Forsterite Carbonation in Wet-scCO2: Dependence on Adsorbed Water Concentration

    NASA Astrophysics Data System (ADS)

    Loring, J.; Benezeth, P.; Qafoku, O.; Thompson, C.; Schaef, T.; Bonneville, A.; McGrail, P.; Felmy, A.; Rosso, K.

    2013-12-01

    Capturing and storing CO2 in basaltic formations is one of the most promising options for mitigating atmospheric CO2 emissions resulting from the burning of fossil fuels. These geologic reservoirs have high reactive potential for CO2-mineral trapping due to an abundance of divalent-cation containing silicates, such as forsterite (Mg2SiO4). Recent studies have shown that carbonation of these silicates under wet scCO2 conditions, e. g. encountered near a CO2 injection well, proceeds along a different pathway and is more effective than in CO2-saturated aqueous fluids. The presence of an adsorbed water film on the forsterite surface seems to be key to reactivity towards carbonation. In this study, we employed in situ high pressure IR spectroscopy to investigate the dependence of adsorbed water film thickness on forsterite carbonation chemistry. Post reaction ex situ SEM, TEM, TGA, XRD, and NMR measurements will also be discussed. Several IR titrations were performed of forsterite with water at 50 °C and 90 bar scCO2. Aliquots of water were titrated at 4-hour reaction-time increments. Once a desired total water concentration was reached, data were collected for about another 30 hours. One titration involved 10 additions, which corresponds to 6.8 monolayers of adsorbed water. Clearly, a carbonate was precipitating, and its spectral signature matched magnesite. Another titration involved 8 aliquots, or up to 4.4 monolayers of water. The integrated absorbance under the CO stretching bands of carbonate as a function of time after reaching 4.4 monolayers showed an increase and then a plateau. We are currently unsure of the identity of the carbonate that precipitated, but it could be an amorphous anhydrous phase or magnesite crystals with dimensions of only several nanometers. A third titration only involved 3 additions, or up to 1.6 monolayers of water. The integrated absorbance under the CO stretching bands of carbonate as a function of time after reaching 1.6 monolayers

  11. Catalytic remediation of 2-propanol on Pt-Mn/γ-Al2O3 bimetallic catalyst during catalytic combustion--experimental study and response surface methodology (RSM) modeling.

    PubMed

    Salari, Dariush; Niaei, Aligholi; Aghazadeh, Faezeh; Hosseini, Seyed Ali; Seyednajafi, Fardin

    2012-01-01

    Process and composition variables of catalytic oxidation of 2-propanol on Pt-Mn/γ-Al(2)O(3) bimetallic catalysts were optimized and modeled by response surface methodology (RSM). 31 factorial experiments were designed by setting four factors at five levels: X (1) = amount of manganese loading (wt.% Mn = 1, 3, 5, 7, 9); X (2) = reaction temperature (25, 50, 75, 100, 125°C); X (3) = calcination temperature (200, 300, 400, 500, 600°C) and X (4) = calcination time (2, 3, 4, 5, 6 h). A second-order polynomial model and response surface were developed for 2-propanol conversion. The optimum conditions for 2-propanol complete conversion were 4.8wt.% manganese loading, 4h calcination time with 75°C and 395°C for reaction and calcination temperatures, respectively. A good correlation was found between experimental and predicted responses, confirming the reliability of the model. PMID:22320686

  12. Heterogeneous catalytic conversion of CO2: a comprehensive theoretical review

    NASA Astrophysics Data System (ADS)

    Li, Yawei; Chan, Siew Hwa; Sun, Qiang

    2015-05-01

    The conversion of CO2 into fuels and useful chemicals has been intensively pursued for renewable, sustainable and green energy. However, due to the negative adiabatic electron affinity (EA) and large ionization potential (IP), the CO2 molecule is chemically inert, thus making the conversion difficult under normal conditions. Novel catalysts, which have high stability, superior efficiency and low cost, are urgently needed to facilitate the conversion. As the first step to design such catalysts, understanding the mechanisms involved in CO2 conversion is absolutely indispensable. In this review, we have summarized the recent theoretical progress in mechanistic studies based on density functional theory, kinetic Monte Carlo simulation, and microkinetics modeling. We focus on reaction channels, intermediate products, the key factors determining the conversion of CO2 in solid-gas interface thermocatalytic reduction and solid-liquid interface electrocatalytic reduction. Furthermore, we have proposed some possible strategies for improving CO2 electrocatalysis and also discussed the challenges in theory, model construction, and future research directions.

  13. A Novel miRNA Processing Pathway Independent of Dicer Requires Argonaute2 Catalytic Activity

    PubMed Central

    Cifuentes, Daniel; Xue, Huiling; Taylor, David W.; Patnode, Heather; Mishima, Yuichiro; Cheloufi, Sihem; Ma, Enbo; Mane, Shrikant; Hannon, Gregory J.; Lawson, Nathan D.; Wolfe, Scot A.; Giraldez, Antonio J.

    2011-01-01

    Dicer is a central enzyme in microRNA (miRNA) processing. We identified a Dicer-independent miRNA biogenesis pathway that uses Argonaute2 (Ago2) slicer catalytic activity. In contrast to other miRNAs, miR-451 levels were refractory to dicer loss of function but were reduced in MZago2 (maternal-zygotic) mutants. We found that pre-miR-451 processing requires Ago2 catalytic activity in vivo. MZago2 mutants showed delayed erythropoiesis that could be rescued by wild-type Ago2 or miR-451-duplex but not by catalytically dead Ago2. Changing the secondary structure of Dicer-dependent miRNAs to mimic that of pre-miR-451 restored miRNA function and rescued developmental defects in MZdicer mutants, indicating that the pre-miRNA secondary structure determines the processing pathway in vivo. We propose that Ago2-mediated cleavage of pre-miRNAs, followed by uridylation and trimming, generates functional miRNAs independently of Dicer. PMID:20448148

  14. A novel miRNA processing pathway independent of Dicer requires Argonaute2 catalytic activity.

    PubMed

    Cifuentes, Daniel; Xue, Huiling; Taylor, David W; Patnode, Heather; Mishima, Yuichiro; Cheloufi, Sihem; Ma, Enbo; Mane, Shrikant; Hannon, Gregory J; Lawson, Nathan D; Wolfe, Scot A; Giraldez, Antonio J

    2010-06-25

    Dicer is a central enzyme in microRNA (miRNA) processing. We identified a Dicer-independent miRNA biogenesis pathway that uses Argonaute2 (Ago2) slicer catalytic activity. In contrast to other miRNAs, miR-451 levels were refractory to dicer loss of function but were reduced in MZago2 (maternal-zygotic) mutants. We found that pre-miR-451 processing requires Ago2 catalytic activity in vivo. MZago2 mutants showed delayed erythropoiesis that could be rescued by wild-type Ago2 or miR-451-duplex but not by catalytically dead Ago2. Changing the secondary structure of Dicer-dependent miRNAs to mimic that of pre-miR-451 restored miRNA function and rescued developmental defects in MZdicer mutants, indicating that the pre-miRNA secondary structure determines the processing pathway in vivo. We propose that Ago2-mediated cleavage of pre-miRNAs, followed by uridylation and trimming, generates functional miRNAs independently of Dicer. PMID:20448148

  15. Au@TiO2 double-shelled octahedral nanocages with improved catalytic properties.

    PubMed

    Lv, Xiaoming; Zhu, Yihua; Jiang, Hongliang; Zhong, Hua; Yang, Xiaoling; Li, Chunzhong

    2014-10-28

    A novel and facile strategy has been successfully developed to synthesize uniform gold@titanium dioxide octahedral nanocages (Au@TiO2), which have a well-defined double-shelled structure with Au as the internal shell and TiO2 as the external shell. The unique Au@TiO2 double-shelled octahedral nanocages were elaborately fabricated by a Cu2O-templated strategy combining with spatially confined galvanic replacement. The formation process of these delicate hierarchical octahedral architectures is discussed in detail. The catalytic performance of the Au@TiO2 double-shelled octahedral nanocages was investigated using the reduction of 4-nitrophenol as a model reaction. The mesoporous structure of both the Au and TiO2 shells provides direct access for the reactant molecules to diffuse and subsequently interact with the Au shell. This novel catalyst shows excellent and stable activity for the catalytic reduction of 4-nitrophenol, which can be recycled for ten successive cycles of the reaction with a conversion efficiency of more than 90%. The superior catalytic activity attributes to mesoporous double shells, enhanced synergistic effects between the Au and TiO2 shells and the unique properties of the octahedral structure. More importantly, the as-obtained Au@TiO2 double-shelled octahedral nanocages also show potential applications in solar cells, organocatalysis and water splitting. PMID:25166883

  16. Catalytic deactivation on methane steam reforming catalysts. 2. Kinetic study

    SciTech Connect

    Agnelli, M.E.; Ponzi, E.N.; Yeramian, A.A.

    1987-08-01

    The kinetics of methane steam reforming reaction over an alumina-supported nickel catalyst was investigated at a temperature range of 640-740/sup 0/C in a flow reactor at atmospheric pressure. The experiments were performed varying the inlet concentration of methane, hydrogen, and water. A kinetic scheme of the Houghen-Watson type was satisfactorily proposed assuming the dissociative adsorption of CH/sub 4/ as the rate-limiting step, but this kinetic scheme can be easily replaced by a first-order kinetics (r/sub CH/4/sub / = kapparho/sub CH/4/sub /) for engineering purposes. Catalyst activation with H/sub 2/ and N/sub 2/ mixtures or with the reactant mixture results in the same extent of reaction.

  17. Structural Insights into the Catalytic Active Site and Activity of Human Nit2/ω-Amidase

    PubMed Central

    Chien, Chin-Hsiang; Gao, Quan-Ze; Cooper, Arthur J. L.; Lyu, Jyun-Hong; Sheu, Sheh-Yi

    2012-01-01

    Human nitrilase-like protein 2 (hNit2) is a putative tumor suppressor, recently identified as ω-amidase. hNit2/ω-amidase plays a crucial metabolic role by catalyzing the hydrolysis of α-ketoglutaramate (the α-keto analog of glutamine) and α-ketosuccinamate (the α-keto analog of asparagine), yielding α-ketoglutarate and oxaloacetate, respectively. Transamination between glutamine and α-keto-γ-methiolbutyrate closes the methionine salvage pathway. Thus, hNit2/ω-amidase links sulfur metabolism to the tricarboxylic acid cycle. To elucidate the catalytic specificity of hNit2/ω-amidase, we performed molecular dynamics simulations on the wild type enzyme and its mutants to investigate enzyme-substrate interactions. Binding free energies were computed to characterize factors contributing to the substrate specificity. The predictions resulting from these computations were verified by kinetic analyses and mutational studies. The activity of hNit2/ω-amidase was determined with α-ketoglutaramate and succinamate as substrates. We constructed three catalytic triad mutants (E43A, K112A, and C153A) and a mutant with a loop 116–128 deletion to validate the role of key residues and the 116–128 loop region in substrate binding and turnover. The molecular dynamics simulations successfully verified the experimental trends in the binding specificity of hNit2/ω-amidase toward various substrates. Our findings have revealed novel structural insights into the binding of substrates to hNit2/ω-amidase. A catalytic triad and the loop residues 116–128 of hNit2 play an essential role in supporting the stability of the enzyme-substrate complex, resulting in the generation of the catalytic products. These observations are predicted to be of benefit in the design of new inhibitors or activators for research involving cancer and hyperammonemic diseases. PMID:22674578

  18. The effect of pretreatment conditions on structural, morphological and catalytic properties of TiO2

    NASA Astrophysics Data System (ADS)

    Kocemba, Ireneusz; Nadajczyk, Justyna; Rynkowski, Jacek; Maniukiewicz, Waldemar

    2014-01-01

    The effect of pretreatment conditions in reductive and oxidative atmosphere on physicochemical properties and catalytic activity of TiO2 was studied. TiO2 was characterized using: XRD, SEM, TPR-H2, O2 and CO chemisorption methods, and tested in the reaction of CO oxidation in air. Experimental results indicated that the kind of pretreatment conditions has a significant influence on structural properties and activity of the studied oxide. It was claimed that pretreatment in hydrogen favors anatase → rutile transformation. Moreover, rutile was more easily reducible than the anatase phase despite its high thermodynamic stability. Catalytic tests showed that pretreatment in hydrogen enhances conversion of CO more than annealing in oxygen atmosphere.

  19. Catalyst performance and mechanism of catalytic combustion of dichloromethane (CH2Cl2) over Ce doped TiO2.

    PubMed

    Cao, Shuang; Wang, Haiqiang; Yu, Feixiang; Shi, Mengpa; Chen, Shuang; Weng, Xiaole; Liu, Yue; Wu, Zhongbiao

    2016-02-01

    TiO2 and Ce/TiO2 were synthesized and subsequently used for the catalytic combustion of DCM. TiO2 had abundant Lewis acid sites and was responsible for the adsorption and the rupture of C-Cl bonds. However, TiO2 tended to be inactivated because of chloride poisoning due to the adsorption and accumulation of Cl species over the surface. While, Ce/TiO2 obtained total oxidation of CH2Cl2 at 335°C and exhibited stable DCM removal activity on 100h long-time stability tests at 330°C without any catalyst deactivation. The doped cerium generated Ce(3+) chemical states and surface active oxygen, and therefore played important roles from two aspects as follows. First of all, the poisoning of Cl for Ce/TiO2 was inhibited to some extent by CeO2 due to the rapid removal of Cl on the surface of CeO2, which has been verified by NH3-IR characterization. In the other hand, CeO2 enhanced the further deep oxidation of C-H from byproducts and retained the certain oxidation of CO to CO2. Based on the DRIFT characterization and the catalysts activity tests, a two-step reaction pathway for the catalytic combustion of DCM on Ce/TiO2 catalyst was proposed. PMID:26550781

  20. Catalytic ozonation of petroleum refinery wastewater utilizing Mn-Fe-Cu/Al2O 3 catalyst.

    PubMed

    Chen, Chunmao; Yoza, Brandon A; Wang, Yandan; Wang, Ping; Li, Qing X; Guo, Shaohui; Yan, Guangxu

    2015-04-01

    There is of great interest to develop an economic and high-efficient catalytic ozonation system (COS) for the treatment of biologically refractory wastewaters. Applications of COS require options of commercially feasible catalysts. Experiments in the present study were designed to prepare and investigate a novel manganese-iron-copper oxide-supported alumina-assisted COS (Mn-Fe-Cu/Al2O3-COS) for the pretreatment of petroleum refinery wastewater. The highly dispersed composite metal oxides on the catalyst surface greatly promoted the performance of catalytic ozonation. Hydroxyl radical mediated oxidation is a dominant reaction in Mn-Fe-Cu/Al2O3-COS. Mn-Fe-Cu/Al2O3-COS enhanced COD removal by 32.7% compared with a single ozonation system and by 8-16% compared with Mn-Fe/Al2O3-COS, Mn-Cu/Al2O3-COS, and Fe-Cu/Al2O3-COS. The O/C and H/C ratios of oxygen-containing polar compounds significantly increased after catalytic ozonation, and the biodegradability of petroleum refinery wastewater was significantly improved. This study illustrates potential applications of Mn-Fe-Cu/Al2O3-COS for pretreatment of biologically refractory wastewaters. PMID:25649390

  1. Wire diameter dependence in the catalytic decomposition of H2

    NASA Astrophysics Data System (ADS)

    Umemoto, Hironobu

    2014-01-01

    Jansen et al. have demonstrated that the dissociaiton rate of H2 molecules on hot wire surfaces, normalized per unit surface area, depends on the wire diameter based on the electrical power consumption measurements [J. Appl. Phys. 66, 5749 (1989)]. Mathematical modeling calculations have also been presented to support their experimental results. In the present paper, it is shown that such a wire diameter dependence cannot be observed and that the H-atom density normalized by the wire surface area depends little on the wire diameter. Modeling calculations also show that the wire diameter dependence of the dissociation rate cannot be expected under typical decomposition conditions.

  2. Core formation, wet early mantle, and H2O degassing on early Mars

    NASA Technical Reports Server (NTRS)

    Kuramoto, K.; Matsui, T.

    1993-01-01

    Geophysical and geochemical observations strongly suggest a 'hot origin of Mars,' i.e., the early formation of both the core and the crust-mantle system either during or just after planetary accretion. To consider the behavior of H2O in the planetary interior it is specifically important to determine by what mechanism the planet is heated enough to cause melting. For Mars, the main heat source is probably accretional heating. Because Mars is small, the accretion energy needs to be effectively retained in its interior. Therefore, the three candidates of heat retention mechanism are discussed first: (1) the blanketing effect of the primordial H2-He atmosphere; (2) the blanketing effect of the impact-induced H2O-CO2 atmosphere; and (3) the higher deposition efficiency of impact energy due to larger impacts. It was concluded that (3) the is the most plausible mechanism for Mars. Then, its possible consequence on how wet the early martian mantle was is discussed.

  3. Synthesis of chitosan supported palladium nanoparticles and its catalytic activity towards 2-nitrophenol reduction

    NASA Astrophysics Data System (ADS)

    Dhanavel, S.; Nivethaa, E. A. K.; Esther, G.; Narayanan, V.; Stephen, A.

    2016-05-01

    Chitosan supported Palladium nanoparticles were synthesized by a simple cost effective chemical reduction method using NaBH4. The prepared nanocomposite was characterized by X-Ray diffraction analysis, FESEM and Energy dispersive spectroscopy analysis of X-rays (EDAX). The catalytic performance of the nanocomposite was evaluated on the reduction of 2-Nitrophenol to the 2-Amino phenol with rate constant 1.08 × 10-3 S-1 by NaBH4 using Spectrophotometer.

  4. Kinetic and Mechanistic Characterization and Versatile Catalytic Properties of Mammalian Glutaredoxin 2: Implications for Intracellular Roles†

    PubMed Central

    Gallogly, Molly M.; Starke, David W.; Leonberg, Amanda K.; Ospina, Susan M. English; Mieyal, John J.

    2013-01-01

    Glutaredoxin (Grx)-catalyzed deglutathionylation of protein–glutathione mixed disulfides (protein-SSG) serves important roles in redox homeostasis and signal transduction, regulating diverse physiological and pathophysiological events. Mammalian cells have two Grx isoforms: Grx1, localized to the cytosol and mitochondrial intermembrane space, and Grx2, localized primarily to the mitochondrial matrix [Pai, H. V., et al. (2007) Antioxid. Redox Signaling 9, 2027–2033]. The catalytic behavior of Grx1 has been characterized extensively, whereas Grx2 catalysis is less well understood. We observed that human Grx1 and Grx2 exhibit key catalytic similarities, including selectivity for protein-SSG substrates and a nucleophilic, double-displacement, monothiol mechanism exhibiting a strong commitment to catalysis. A key distinction between Grx1- and Grx2-mediated deglutathionylation is decreased catalytic efficiency (kcat/KM) of Grx2 for protein deglutathionylation (due primarily to a decreased kcat), reflecting a higher pKa of its catalytic cysteine, as well as a decreased enhancement of nucleophilicity of the second substrate, GSH. As documented previously for hGrx1 [Starke, D. W., et al. (2003) J. Biol. Chem. 278, 14607–14613], hGrx2 catalyzes glutathione-thiyl radical (GS•) scavenging, and it also mediates GS transfer (protein S-glutathionylation) reactions, where GS• serves as a superior glutathionyl donor substrate for formation of GAPDH-SSG, compared to GSNO and GSSG. In contrast to its lower kcat for deglutathionylation reactions, Grx2 promotes GS-transfer to the model protein substrate GAPDH at rates equivalent to those of Grx1. Estimation of Grx1 and Grx2 concentrations within mitochondria predicts comparable deglutathionylation activities within the mitochondrial subcompartments, suggesting localized regulatory functions for both isozymes. PMID:18816065

  5. Mesoporous ZnO-SiO2 core-shell rods for UV absorbing and non-wetting applications

    NASA Astrophysics Data System (ADS)

    Brijitta, J.; Ramachandran, D.; Chennakesavulu, K.; Bera, Santanu; Rabel, A. M.; Sanjeevi Prasath, S.; Reenu Mary, K.

    2016-02-01

    A versatile wet chemical approach to synthesize mesoporous ZnO-SiO2 rods in the core-shell morphology is reported in this paper. The mesoporous nature of the rods is reflected from surface area measurements. The band gap of the ZnO-SiO2 rods shows a blue shift compared to the ZnO rods. The non-wetting and UV absorbing nature of the rods is investigated by dip coating them on the polyester taffeta and exposing them to a UV source. By tuning the concentration of the roughening agent, an average water contact angle of 152° with better UV absorbing characteristics is obtained.

  6. Influence of Water on the Interfacial Nanostructure and Wetting of [Rmim][NTf2] Ionic Liquids at Mica Surfaces.

    PubMed

    Wang, Zhantao; Li, Hua; Atkin, Rob; Priest, Craig

    2016-09-01

    The effect of water concentration on the interfacial nanostructure and wetting behavior of a family of ionic liquids (ILs), 1-alkyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, [Rmim][NTf2], at the surface of mica was investigated by contact angle measurement and atomic force microscopy (AFM). AFM reveals that interfacial layers of ILs observed at the surface of mica for "dry" ILs are not present for water-saturated ILs. The interaction of the IL ions of [Rmim][NTf2] with water molecules through hydrogen bonding is suspected to disrupt IL ion layering and precursor film growth on mica. Without the IL precursor film, contact angle relaxation of "wet" ILs on mica is less significant and ambient vapor adsorption becomes more important in determining the macroscopic wetting behavior. PMID:27486675

  7. Catalytic cycloalumination in steroid chemistry II: selective functionalization of 2'-methylidene-2',3'-ethano-(5α)-cholestane.

    PubMed

    D'yakonov, Vladimir A; Tuktarova, Regina A; Islamov, Ilgiz I; Khalilov, Leonard M; Dzhemilev, Usein M

    2013-12-11

    The catalytic cycloalumination of 2'-methylidene-2',3'-ethano-(5α)-cholestane with Et3Al catalyzed by Cp2ZrCl2 was performed for the first time to give spiro[2',3'-ethano-(5α)-cholestane-2',3″-aluminacyclopentane] in a ~75% yield and with high stereoselectivity (>98%). The obtained cyclic organoaluminum compound was transformed in situ into heterocyclic spiran derivatives of 2',3'-ethano-(5α)-cholestane. PMID:24075970

  8. Two Arabidopsis ADP-Glucose Pyrophosphorylase Large Subunits (APL1 and APL2) Are Catalytic1

    PubMed Central

    Ventriglia, Tiziana; Kuhn, Misty L.; Ruiz, Ma Teresa; Ribeiro-Pedro, Marina; Valverde, Federico; Ballicora, Miguel A.; Preiss, Jack; Romero, José M.

    2008-01-01

    ADP-glucose (Glc) pyrophosphorylase (ADP-Glc PPase) catalyzes the first committed step in starch biosynthesis. Higher plant ADP-Glc PPase is a heterotetramer (α2β2) consisting of two small and two large subunits. There is increasing evidence that suggests that catalytic and regulatory properties of the enzyme from higher plants result from the synergy of both types of subunits. In Arabidopsis (Arabidopsis thaliana), two genes encode small subunits (APS1 and APS2) and four large subunits (APL1–APL4). Here, we show that in Arabidopsis, APL1 and APL2, besides their regulatory role, have catalytic activity. Heterotetramers formed by combinations of a noncatalytic APS1 and the four large subunits showed that APL1 and APL2 exhibited ADP-Glc PPase activity with distinctive sensitivities to the allosteric activator (3-phosphoglycerate). Mutation of the Glc-1-P binding site of Arabidopsis and potato (Solanum tuberosum) isoforms confirmed these observations. To determine the relevance of these activities in planta, a T-DNA mutant of APS1 (aps1) was characterized. aps1 is starchless, lacks ADP-Glc PPase activity, APS1 mRNA, and APS1 protein, and is late flowering in long days. Transgenic lines of the aps1 mutant, expressing an inactivated form of APS1, recovered the wild-type phenotype, indicating that APL1 and APL2 have catalytic activity and may contribute to ADP-Glc synthesis in planta. PMID:18614708

  9. Two Arabidopsis ADP-glucose pyrophosphorylase large subunits (APL1 and APL2) are catalytic.

    PubMed

    Ventriglia, Tiziana; Kuhn, Misty L; Ruiz, Ma Teresa; Ribeiro-Pedro, Marina; Valverde, Federico; Ballicora, Miguel A; Preiss, Jack; Romero, José M

    2008-09-01

    ADP-glucose (Glc) pyrophosphorylase (ADP-Glc PPase) catalyzes the first committed step in starch biosynthesis. Higher plant ADP-Glc PPase is a heterotetramer (alpha(2)beta(2)) consisting of two small and two large subunits. There is increasing evidence that suggests that catalytic and regulatory properties of the enzyme from higher plants result from the synergy of both types of subunits. In Arabidopsis (Arabidopsis thaliana), two genes encode small subunits (APS1 and APS2) and four large subunits (APL1-APL4). Here, we show that in Arabidopsis, APL1 and APL2, besides their regulatory role, have catalytic activity. Heterotetramers formed by combinations of a noncatalytic APS1 and the four large subunits showed that APL1 and APL2 exhibited ADP-Glc PPase activity with distinctive sensitivities to the allosteric activator (3-phosphoglycerate). Mutation of the Glc-1-P binding site of Arabidopsis and potato (Solanum tuberosum) isoforms confirmed these observations. To determine the relevance of these activities in planta, a T-DNA mutant of APS1 (aps1) was characterized. aps1 is starchless, lacks ADP-Glc PPase activity, APS1 mRNA, and APS1 protein, and is late flowering in long days. Transgenic lines of the aps1 mutant, expressing an inactivated form of APS1, recovered the wild-type phenotype, indicating that APL1 and APL2 have catalytic activity and may contribute to ADP-Glc synthesis in planta. PMID:18614708

  10. Selective wet etching of Ge2Sb2Te5 phase-change thin films in thermal lithography with tetramethylammonium

    NASA Astrophysics Data System (ADS)

    Deng, Changmeng; Geng, Yongyou; Wu, Yiqun

    2011-09-01

    In this paper, we study Ge2Sb2Te5 phase-change film as a promising inorganic photoresist using organic alkaline: tetramethylammonium hydroxide (TMAH) solution, instead of inorganic alkali or acid as etchant. The basic etching properties are investigated by prior and posterior annealing Ge2Sb2Te5 films. Selectivity is found to be dependent on concentration of TMAH. There is a good selectivity in the 25% TMAH solution, in which the amorphous state is etched away, whereas the crystalline state remains. The etching rate decreases when the concentration of TMAH is diluted; and an opposite selectivity, compared with 25% TMAH solution, is observed in the 0.125% TMAH solution. Selective etching with laser crystallization in different power levels is also studied, and an excellent wet selectivity in the 25% TMAH solution is obtained. The remaining crystalline lines are observed by atomic force microscopy. The surface roughness after etching is at a good level. The selective wet-etching mechanism is also discussed.

  11. Wetting and Reaction Characteristics of Al2O3/SiC Composite Refractories By Molten Aluminum and Aluminum Alloy

    SciTech Connect

    Hemrick, James Gordon; Xu, Jing; Peters, Klaus-Markus; Liu, Xingbo; Barbero, Ever J

    2007-01-01

    The reactive wetting behavior in molten aluminum (Al) and Al alloy was investigated for alumina-silicon carbide composite refractory materials using an optimized sessile drop method at 900oC in a purified Ar-4% H2 atmosphere. The time dependent behavior of the contact angle and drop geometry was monitored and the wetting kinetics were determined. The initial contact angle between the liquid Al/Al alloy and the refractory substrates was found to be greater than 90 and to gradually decrease with time. For two of the materials, it was found that the contact angles decreased to and angle less than 90 by the end of the two-hour test. For the third material, the contact angle was still greater than 90 at the conclusion of the two-hour test. The difference in wetting properties among the three types of refractories is attributed to their microstructural and compositional variations. The effect of magnesium in the molten Al alloy drops on the wetting kinetics and the reaction with the refractory substrates are also discussed. The results obtained provide important understanding of the wetting and corrosion mechanisms of alumina and silicon carbide materials in contact with molten aluminum.

  12. Density functional simulations as a tool to probe molecular interactions in wet supercritical CO2

    SciTech Connect

    Glezakou, Vassiliki Alexandra; McGrail, B. Peter

    2013-06-03

    Recent advances in mixed Gaussian and plane wave algorithms have made possible the effective use of density functional theory (DFT) in ab initio molecular dynamics (AIMD) simulations for large and chemically complex models of condensed phase materials. In this chapter, we are reviewing recent progress on the modeling and characterization of co-sequestration processes and reactivity in wet supercritical CO2 (sc-CO2). We examine the molecular transformations of mineral and metal components of a sequestration system in contact with water-bearing scCO2 media and aim to establish a reliable correspondence between experimental observations and theory models with predictive ability and transferability of results in large scale geomechanical simulators. This work is funded by the Department of Energy, Office of Fossil Energy. A portion of the research was performed using EMSL, a national scientific user facility sponsored by the Department of Energy’s Office of Biological and Environmental Research located at Pacific Northwest National Laboratory. The Pacific Norhtwest National Laboratory (PNNL) is operated by Battelle for DOE under contract DE-AC06-76RL01830.

  13. Wet chemical methods for producing mixing crystalline phase ZrO2 thin film

    NASA Astrophysics Data System (ADS)

    Pakma, Osman; Özdemir, Cengiz; Kariper, İ. Afşin; Özaydın, Cihat; Güllü, Ömer

    2016-07-01

    The aim of the study is to develop a more economical and easier method for obtaining ZrO2 thin films at lower temperature, unlike the ones mentioned in the literature. For this purpose, wet chemical synthesis methods have been tested and XRD, UV-VIS and SEM analysis of ZrO2 thin films have been performed. At the end of the analysis, we identified the best method and it has been found that the features of the films produced with this method were better than the films produced by using different reagents, as well as the films reported in the literature. Especially it has been observed that the transmittance of the film produced with this method were higher and better than the films in the literature and the others. In addition, refractive index of the film produced with this method was observed to be lower. Moreover, by using the same method Al/ZrO2/p-Si structure has been obtained and it has been compared with Al/p-Si reference structure in terms of electrical parameters.

  14. The catalytic activity of Ag2S-montmorillonites as peroxidase mimetic toward colorimetric detection of H2O2.

    PubMed

    Liu, Qingyun; Jiang, Yanling; Zhang, Leyou; Zhou, Xinpei; Lv, Xintian; Ding, Yanyuan; Sun, Lifang; Chen, Pengpeng; Yin, Hailiang

    2016-08-01

    Nanocomposites based on silver sulfide (Ag2S) and Ca-montmorillonite (Ca(2+)-MMT) were synthesized by a simple hydrothermal method. The nanocomposites were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and Fourier transform infrared spectra (FTIR). The as-prepared Ag2S-MMT nanocomposites were firstly demonstrated to possess intrinsic peroxidase-like activity and could rapidly catalytically oxidize the substrate 3,3',5,5'-tetramethylbenzidine (TMB) in the presence of H2O2 to produce a blue product which can be seen by the naked eye in only one minute. The experimental results revealed that the Ag2S-MMT nanocomposites exhibit higher thermal durance. Based on the TMB-H2O2 catalyzed color reaction, the Ag2S-MMT nanocomposites were exploited as a new type of biosensor for detection and estimation of H2O2 through a simple, cheap and selective colorimetric method. PMID:27157733

  15. Hydrodechlorination catalytic activity of gold nanoparticles supported on TiO 2 modified SBA-15 investigated by IR spectroscopy

    NASA Astrophysics Data System (ADS)

    Hannus, I.; Búza, M.; Beck, A.; Guczi, L.; Sáfrán, G.

    2009-04-01

    The hydrodechlorination catalytic activity of gold nanoparticles on SBA-15 silica modified by TiO 2 promoters has been investigated. Comparing the hydrodechlorination catalytic activity platinum nanoparticles supported on TiO 2 catalyst was used in the hydrodechlorination of CCl 4 as model compound. The IR spectroscopic experimental results showed that the gold nanoparticles have higher catalytic activity, than platinum ones. The two samples were tested also in CO oxidation, in which Au/TiO 2/SBA-15 possess also somewhat higher activity than Pt/TiO 2.

  16. Boryl-mediated reversible H2 activation at cobalt: catalytic hydrogenation, dehydrogenation, and transfer hydrogenation.

    PubMed

    Lin, Tzu-Pin; Peters, Jonas C

    2013-10-16

    We describe the synthesis of a cobalt(I)-N2 complex (2) supported by a meridional bis-phosphino-boryl (PBP) ligand. Complex 2 undergoes a clean reaction with 2 equiv of dihydrogen to afford a dihydridoboratocobalt dihydride (3). The ability of boron to switch between a boryl and a dihydridoborate conformation makes possible the reversible conversion of 2 and 3. Complex 3 reacts with HMe2N-BH3 to give a hydridoborane cobalt tetrahydridoborate complex. We explore this boryl-cobalt system in the context of catalytic olefin hydrogenation as well as amine-borane dehydrogenation/transfer hydrogenation. PMID:24079337

  17. [Current research situation of H2S selective catalytic oxidation technologies and catalysts].

    PubMed

    Hao, Zheng-ping; Dou, Guang-yu; Zhang, Xin; Qu, Si-qiu

    2012-08-01

    This review summarizes and discusses different selective catalytic oxidation technologies and various catalysts for removing H2S, the undesirable byproduct of the fluid catalytic cracking (FCC) processing. Currently the selective oxidation technologies used include Superclaus, Euroclaus, Clinsulf-Do, BSR/Hi-Activity, Selectox and Modop techniques, which have various characteristics and application areas. Catalysts for H2S selective oxidation mainly contain the following systems: carbon, supported SiC, zeolite, oxide, and pillared clay. Former studies focused on carbon and oxide systems. The research interest on zeolite system decreased in recent years, while SiC is regarded as a typical support with great potential for this reaction and continues to be attractive. Pillared clay system is at the preliminary research stage, and is still far from practical application. PMID:23213923

  18. Isolated metal active site concentration and stability control catalytic CO2 reduction selectivity.

    PubMed

    Matsubu, John C; Yang, Vanessa N; Christopher, Phillip

    2015-03-01

    CO2 reduction by H2 on heterogeneous catalysts is an important class of reactions that has been studied for decades. However, atomic scale details of structure-function relationships are still poorly understood. Particularly, it has been suggested that metal particle size plays a unique role in controlling the stability of CO2 hydrogenation catalysts and the distribution of active sites, which dictates reactivity and selectivity. These studies often have not considered the possible role of isolated metal active sites in the observed dependences. Here, we utilize probe molecule diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) with known site-specific extinction coefficients to quantify the fraction of Rh sites residing as atomically dispersed isolated sites (Rhiso), as well as Rh sites on the surface of Rh nanoparticles (RhNP) for a series of TiO2 supported Rh catalysts. Strong correlations were observed between the catalytic reverse water gas shift turn over frequency (TOF) and the fraction of Rhiso sites and between catalytic methanation TOF and the fraction of RhNP sites. Furthermore, it was observed that reaction condition-induced disintegration of Rh nanoparticles, forming Rhiso active sites, controls the changing reactivity with time on stream. This work demonstrates that isolated atoms and nanoparticles of the same metal on the same support can exhibit uniquely different catalytic selectivity in competing parallel reaction pathways and that disintegration of nanoparticles under reaction conditions can play a significant role in controlling stability. PMID:25671686

  19. Selective killing of G2 decatenation checkpoint defective colon cancer cells by catalytic topoisomerase II inhibitor.

    PubMed

    Jain, Chetan Kumar; Roychoudhury, Susanta; Majumder, Hemanta Kumar

    2015-05-01

    Cancer cells with defective DNA decatenation checkpoint can be selectively targeted by the catalytic inhibitors of DNA topoisomerase IIα (topo IIα) enzyme. Upon treatment with catalytic topo IIα inhibitors, cells with defective decatenation checkpoint fail to arrest their cell cycle in G2 phase and enter into M phase with catenated and under-condensed chromosomes resulting into impaired mitosis and eventually cell death. In the present work we analyzed decatenation checkpoint in five different colon cancer cell lines (HCT116, HT-29, Caco2, COLO 205 and SW480) and in one non-cancerous cell line (HEK293T). Four out of the five colon cancer cell lines i.e. HCT116, HT-29, Caco2, and COLO 205 were found to be compromised for the decatenation checkpoint function at different extents, whereas SW480 and HEK293T cell lines were found to be proficient for the checkpoint function. Upon treatment with ICRF193, decatenation checkpoint defective cell lines failed to arrest the cell cycle in G2 phase and entered into M phase without proper chromosomal decatenation, resulting into the formation of tangled mass of catenated and under-condensed chromosomes. Such cells underwent mitotic catastrophe and rapid apoptosis like cell death and showed higher sensitivity for ICRF193. Our study suggests that catalytic inhibitors of topoisomerase IIα are promising therapeutic agents for the treatment of colon cancers with defective DNA decatenation checkpoint. PMID:25746763

  20. Study of the dynamics of the MoO2-Mo2C system for catalytic partial oxidation reactions

    NASA Astrophysics Data System (ADS)

    Cuba Torres, Christian Martin

    On a global scale, the energy demand is largely supplied by the combustion of non-renewable fossil fuels. However, their rapid depletion coupled with environmental and sustainability concerns are the main drivers to seek for alternative energetic strategies. To this end, the sustainable generation of hydrogen from renewable resources such as biodiesel would represent an attractive alternative solution to fossil fuels. Furthermore, hydrogen's lower environmental impact and greater independence from foreign control make it a strong contender for solving this global problem. Among a wide variety of methods for hydrogen production, the catalytic partial oxidation offers numerous advantages for compact and mobile fuel processing systems. For this reaction, the present work explores the versatility of the Mo--O--C catalytic system under different synthesis methods and reforming conditions using methyl oleate as a surrogate biodiesel. MoO2 exhibits good catalytic activity and exhibits high coke-resistance even under reforming conditions where long-chain oxygenated compounds are prone to form coke. Moreover, the lattice oxygen present in MoO2 promotes the Mars-Van Krevelen mechanism. Also, it is introduced a novel beta-Mo2C synthesis by the in-situ formation method that does not utilize external H2 inputs. Herein, the MoO 2/Mo2C system maintains high catalytic activity for partial oxidation while the lattice oxygen serves as a carbon buffer for preventing coke formation. This unique feature allows for longer operation reforming times despite slightly lower catalytic activity compared to the catalysts prepared by the traditional temperature-programmed reaction method. Moreover, it is demonstrated by a pulse reaction technique that during the phase transformation of MoO2 to beta-Mo2C, the formation of Mo metal as an intermediate is not responsible for the sintering of the material wrongly assumed by the temperature-programmed method.

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

    SciTech Connect

    Tang, Lulu; Nguyen, Van Hoa; Shim, Jae-Jin

    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.

  2. Superiority of wet-milled over dry-milled superfine powdered activated carbon for adsorptive 2-methylisoborneol removal.

    PubMed

    Pan, Long; Matsui, Yoshihiko; Matsushita, Taku; Shirasaki, Nobutaka

    2016-10-01

    Superfine powdered activated carbon (SPAC), which is produced from conventionally sized powdered activated carbon (PAC) by wet milling in a bead mill, has attracted attention for its high adsorptive removal ability in both research and practice. In this study, the performance of dry-milled SPAC was investigated. 2-Methylisoborneol (MIB), an earthy-musty compound commonly targeted by water treatment systems, was used as the target adsorbate. Dry-milled SPAC exhibited lower adsorptive removal of MIB than wet-milled SPAC, even when both SPACs were produced from the same PAC and were composed of particles of the same size. One reason for the lower removal of MIB by the dry-milled SPAC was a higher degree of aggregation in the dry-milled SPAC after production; as a result the apparent particle size of dry-milled SPAC was larger than that of wet-milled SPAC. The dry-milled SPAC was also more negatively charged than the wet-milled SPAC, and, owing to its higher repulsion, it was more amenable to dispersion by ultrasonication. However, even after the dry-milled SPAC was ultrasonicated so that its apparent particle size was similar to or less than that of the wet-milled SPAC, the dry-milled SPAC was still inferior in adsorptive removal to the wet-milled SPAC. Therefore, another reason for the lower adsorptive removal of dry-milled SPAC was its lower equilibrium adsorption capacity due to the oxidation during the milling. The adsorption kinetics by SPACs with different degrees of particle aggregation were successfully simulated by a pore diffusion model and a fractal aggregation model. PMID:27403874

  3. HIPK2 catalytic activity and subcellular localization are regulated by activation-loop Y354 autophosphorylation.

    PubMed

    Siepi, Francesca; Gatti, Veronica; Camerini, Serena; Crescenzi, Marco; Soddu, Silvia

    2013-06-01

    HIPK2 (homeodomain-interacting protein kinase-2) binds to and phosphorylates, at Ser and Thr residues, a large number of targets involved in cell division and cell fate decision in response to different physiological or stress stimuli. Inactivation of HIPK2 has been observed in human and mouse cancers supporting its role as a tumor suppressor. Despite the biological relevance of this kinase, very little is known on how HIPK2 becomes catalytically active. Based on sequence homologies, HIPK2 has been taxonomically classified as a subfamily member of the dual-specificity tyrosine-regulated kinases (DYRKs) and the activation-loop Y354 of HIPK2 has been found phosphorylated in different cells; however, the relevance of this Y phosphorylation is presently unknown. Here, we show that HIPK2, which is extensively phosphorylated at S/T sites throughout its functional domains, becomes catalytically active by autophosphorylation at the activation-loop Y354. In particular, we found that, in analogy to DYRKs, HIPK2-Y354 phosphorylation is an autocatalytic event and its prevention, through Y354 substitution with non-phosphorylatable amino acids or by using the kinase inhibitor purvalanol A, induces a strong reduction of the HIPK2 S/T-kinase activity on different substrates. Interestingly, at variance from DYRKs, inhibition of HIPK2-Y354 phosphorylation induces a strong out-of-target Y-kinase activity in cis and a strong cytoplasmic relocalization of the kinase. Together, these results demonstrate that the catalytic activity, substrate specificity, and subcellular localization of HIPK2 are regulated by autophosphorylation of its activation-loop Y354. PMID:23485397

  4. HIPK2 catalytic activity and subcellular localization are regulated by activation-loop Y354 autophosphorylation

    PubMed Central

    Siepi, Francesca; Gatti, Veronica; Camerini, Serena; Crescenzi, Marco; Soddu, Silvia

    2013-01-01

    HIPK2 (homeodomain-interacting protein kinase-2) binds to and phosphorylates, at Ser and Thr residues, a large number of targets involved in cell division and cell fate decision in response to different physiological or stress stimuli. Inactivation of HIPK2 has been observed in human and mouse cancers supporting its role as a tumor suppressor. Despite the biological relevance of this kinase, very little is known on how HIPK2 becomes catalytically active. Based on sequence homologies, HIPK2 has been taxonomically classified as a subfamily member of the dual-specificity tyrosine-regulated kinases (DYRKs) and the activation-loop Y354 of HIPK2 has been found phosphorylated in different cells; however, the relevance of this Y phosphorylation is presently unknown. Here, we show that HIPK2, which is extensively phosphorylated at S/T sites throughout its functional domains, becomes catalytically active by autophosphorylation at the activation-loop Y354. In particular, we found that, in analogy to DYRKs, HIPK2-Y354 phosphorylation is an autocatalytic event and its prevention, through Y354 substitution with non-phosphorylatable amino acids or by using the kinase inhibitor purvalanol A, induces a strong reduction of the HIPK2 S/T-kinase activity on different substrates. Interestingly, at variance from DYRKs, inhibition of HIPK2-Y354 phosphorylation induces a strong out-of-target Y-kinase activity in cis and a strong cytoplasmic relocalization of the kinase. Together, these results demonstrate that the catalytic activity, substrate specificity, and subcellular localization of HIPK2 are regulated by autophosphorylation of its activation-loop Y354. PMID:23485397

  5. Characterization and catalytic performance of pure and Li 2O-doped CuO/CeO 2 catalysts

    NASA Astrophysics Data System (ADS)

    Deraz, N. M.

    2009-01-01

    Pure and Li 2O-doped CuO/CeO 2 catalysts calcined at 500 °C were prepared by impregnation method. The catalysts are characterized by DTA, TG-DTG, XRD, IR, TEM, nitrogen adsorption at -196 °C and the catalytic decomposition of hydrogen peroxide at 30 °C. The effects of molar ratio, heat treatment time and the doping on the structural, surface and catalytic properties of nanocrystalline Cu/Ce-mixed oxides system have been studied. It was found that the catalytic activity of ceria-supported copper oxide catalysts increased by increasing both the heat treatment time and dopant content. However, the pure Cu/Ce-mixed oxide solids containing 10 wt.% CuO exhibited the best performance. The characterization results indicated that the higher surface area, the formation of solid solution between copper and cerium oxides, and the high dispersion of copper species on the ceria were responsible for the high catalytic activity of the CuO/CeO 2 catalysts.

  6. Sodium-promoted Pd/TiO2 for catalytic oxidation of formaldehyde at ambient temperature.

    PubMed

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

    2014-05-20

    Catalytic oxidation of formaldehyde (HCHO) to CO2 at ambient conditions is of great interest for indoor HCHO purification. Here, we report that sodium-doped Pd/TiO2 is a highly effective catalyst for the catalytic oxidation of HCHO at room temperature. It was observed that Na doping has a dramatic promotion effect on the Pd/TiO2 catalyst and that nearly 100% HCHO conversion could be achieved over the 2Na-Pd/TiO2 catalyst at a GHSV of 95000 h(-1) and HCHO inlet concentration of 140 ppm at 25 °C. The mechanism of the Na-promotion effect was investigated by using Brunauer-Emmett-Teller (BET), X-ray diffraction (XRD), CO chemisorption, Temperature-programmed reduction by H2 (H2-TPR), X-ray photoelectron spectroscopy (XPS) and temperature-programmed desorption of O2 (O2-TPD) methods. The results showed that Na species addition can induce and further stabilize a negatively charged and well-dispersed Pd species, which then facilitates the activation of H2O and chemisorbed oxygen, therefore resulting in the high performance of the 2Na-Pd/TiO2 catalyst for the ambient HCHO destruction. PMID:24738832

  7. SO 2 adsorption capacity of K 2CO 3-impregnated activated carbon as a function of K 2CO 3 content loaded by soaking and incipient wetness

    NASA Astrophysics Data System (ADS)

    Fortier, H.; Zelenietz, C.; Dahn, T. R.; Westreich, P.; Stevens, D. A.; Dahn, J. R.

    2007-01-01

    The SO 2 adsorption capacity of K 2CO 3-impregnated activated carbons, prepared by soaking carbon in large volumes of K 2CO 3 in solution of various concentrations, varies linearly with respect to the loading of K 2CO 3 on the carbon up to about 12% K 2CO 3 by weight. Above 12%, the capacity for SO 2 levels out and then decreases. This suggests that at high loadings the K 2CO 3 either aggregates and/or blocks pores of the activated carbon. In contrast, the adsorption capacity of carbons prepared by repeatedly (maximum of three times total) loading K 2CO 3 via incipient wetness is much larger than that of the soaked samples, up to 70% more, when the loading of K 2CO 3 is greater than 12%. Static and dynamic adsorption, DSC, SEM, EDX and incipient wetness studies of the samples show that the impregnant aggregates but does not block carbon pores.

  8. Suppressed N2O formation during NH3 selective catalytic reduction using vanadium on zeolitic microporous TiO2

    NASA Astrophysics Data System (ADS)

    Lee, Seung Gwan; Lee, Hyun Jeong; Song, Inhak; Youn, Seunghee; Kim, Do Heui; Cho, Sung June

    2015-08-01

    Emission of N2O from mobile and off-road engine is now being currently regulated because of its high impact compared to that of CO2, thereby implying that N2O formation from the exhaust gas after-treatment system should be suppressed. Selective catalytic reduction using vanadium supported TiO2 catalyst in mobile and off-road engine has been considered to be major source for N2O emission in the system. Here we have demonstrated that vanadium catalyst supported on zeolitic microporous TiO2 obtained from the hydrothermal reaction of bulk TiO2 at 400 K in the presence of LiOH suppresses significantly the N2O emission compared to conventional VOx/TiO2 catalyst, while maintaining the excellent NOx reduction, which was ascribed to the location of VOx domain in the micropore of TiO2, resulting in the strong metal support interaction. The use of zeolitic microporous TiO2 provides a new way of preparing SCR catalyst with a high thermal stability and superior catalytic performance. It can be also extended further to the other catalytic system employing TiO2-based substrate.

  9. Suppressed N2O formation during NH3 selective catalytic reduction using vanadium on zeolitic microporous TiO2

    PubMed Central

    Lee, Seung Gwan; Lee, Hyun Jeong; Song, Inhak; Youn, Seunghee; Kim, Do Heui; Cho, Sung June

    2015-01-01

    Emission of N2O from mobile and off-road engine is now being currently regulated because of its high impact compared to that of CO2, thereby implying that N2O formation from the exhaust gas after-treatment system should be suppressed. Selective catalytic reduction using vanadium supported TiO2 catalyst in mobile and off-road engine has been considered to be major source for N2O emission in the system. Here we have demonstrated that vanadium catalyst supported on zeolitic microporous TiO2 obtained from the hydrothermal reaction of bulk TiO2 at 400 K in the presence of LiOH suppresses significantly the N2O emission compared to conventional VOx/TiO2 catalyst, while maintaining the excellent NOx reduction, which was ascribed to the location of VOx domain in the micropore of TiO2, resulting in the strong metal support interaction. The use of zeolitic microporous TiO2 provides a new way of preparing SCR catalyst with a high thermal stability and superior catalytic performance. It can be also extended further to the other catalytic system employing TiO2-based substrate. PMID:26235671

  10. Structural, catalytic and magnetic properties of Cu1-XCoXFe2O4

    NASA Astrophysics Data System (ADS)

    Briceño, Sarah; Castillo, Hector Del; Sagredo, V.; Bramer-Escamilla, Werner; Silva, Pedro

    2012-12-01

    Copper substituted cobalt ferrite Cu1-XCoXFe2O4 (0 ≤x ≤ 1) have been synthesized using sol-gel auto combustion method with citric acid as fuel. Structural identification, magnetic and catalytic properties were investigated using thermogravimetric and differential thermal analysis, X-ray diffraction, scanning electron microscopy, transmission electron microscopy, vibrating sample magnetometry and their application in the selective catalytic reduction of NOx were studied. Analysis of structural properties reveals that all samples have cubic spinel structure. Room temperature magnetic hysteresis measurements as a function of magnetic field infer that the magnetic properties decrease with Cu2+ doping which may be due to the difference of the magnetic moment of Cu2+ and Co2+ ions. The higher activity of the samples in NO selective reduction to N2 occurs at 350 °C, reaching a maximum of 38% NO conversion and 95% of selective conversion to N2. The compositions containing both Cu2+ and Co2+ ions are more active to the products selectivity to N2, suggesting a synergistic effect on the active surface of ferrite and the effect of Co2+ is more pronounced than Cu2+ towards NO conversion.

  11. Initial Wetting and Spreading Rates Between SiC and CaO-SiO2-MnO Slag

    NASA Astrophysics Data System (ADS)

    Park, Jungseon; Jeon, Junmo; Lee, Kyuyoung; Park, Joo Hyun; Chung, Yongsug

    2016-06-01

    The wetting of CaO-SiO2-MnO slag on silicon carbide was studied with a variety of slag compositions at 1823 K (1550 °C). Wetting experiments were performed by the dispensed drop technique. We observed complete wetting of the slag on SiC (within 1 second) without a bubble reaction regardless of the basicity (=CaO/SiO2 = C/S ratio). However, after 8 seconds, the bubble reaction was observed under conditions of C/S = 0.8 and 1.1, whereas it was not observed at temperatures lower than 1823 K (1550 °C). The contact angle was independent of MnO content, while the spreading rate increased with the increasing MnO content at the early stage of wetting. Inertial force acts on the early stage of spreading, and viscous force acts with lower MnO content due to higher viscosity. The low-viscosity slag did not fit with the nonreactive viscous model. However, the high-viscosity slag fitted the model well.

  12. Switchable catalytic DNA catenanes.

    PubMed

    Hu, Lianzhe; Lu, Chun-Hua; Willner, Itamar

    2015-03-11

    Two-ring interlocked DNA catenanes are synthesized and characterized. The supramolecular catenanes show switchable cyclic catalytic properties. In one system, the catenane structure is switched between a hemin/G-quadruplex catalytic structure and a catalytically inactive state. In the second catenane structure the catenane is switched between a catalytically active Mg(2+)-dependent DNAzyme-containing catenane and an inactive catenane state. In the third system, the interlocked catenane structure is switched between two distinct catalytic structures that include the Mg(2+)- and the Zn(2+)-dependent DNAzymes. PMID:25642796

  13. Investigation of Potassium Feldspar Reactivity in Wet Supercritical CO2 by In Situ Infrared Spectroscopy

    NASA Astrophysics Data System (ADS)

    Thompson, C.; Widener, C.; Schaef, T.; Loring, J.; McGrail, B. P.

    2014-12-01

    Capture and subsequent storage of CO2 in deep geologic reservoirs is progressively being considered as a viable approach to reduce anthropogenic greenhouse gas emissions. In the long term, injected CO2 may become permanently entrapped as silicate minerals react with CO2 enriched fluids to form stable carbonate minerals. Potassium feldspars are highly abundant in the earth's crust and are present in the caprocks and storage formations of many target reservoirs. While the dissolution kinetics and carbonation reactions of feldspars have been well studied in the aqueous phase, comparatively little work has focused on K-feldspar reactivity in the CO2-rich fluid. In this study, we used in situ infrared spectroscopy to investigate the carbonation reactions of natural microcline samples. Experiments were carried out at 50 °C and 91 bar by circulating dry or wet supercritical CO2 (scCO2) past a thin film of powdered sample. Water concentrations ranged from 0% to 125% relative to saturation, and transmission-mode absorbance spectra were recorded as a function of time for 48 hours. No discernible reaction was detected when the samples were exposed to anhydrous scCO2. However, in fully water-saturated scCO2, a thin film of liquid-like water was observed on the samples' surfaces, and up to 0.6% of the microcline was converted to a carbonate phase. Potassium carbonate is the most likely reaction product, but minor amounts of sodium carbonate and siderite may also have formed from minor sample impurities. The extent of reaction appears to be related to the thickness of the water film and is likely a consequence of the film's ability to solvate and transport ions in the vicinity of the mineral surface. Other features observed in the spectra correspond to microcline dissolution and precipitation of amorphous silica. Implications about the role of water in these reactions and the relative effectiveness of alkali feldspars for mineral trapping of CO2 will be discussed.

  14. Investigation of Plagioclase Reactivity in Wet Supercritical CO2 by In Situ Infrared Spectroscopy

    NASA Astrophysics Data System (ADS)

    Thompson, C.; Gauglitz, K.; Loring, J.; Schaef, T.; Miller, Q.; Johnson, K. T.; Wang, Z.; Rosso, K. M.; McGrail, P.

    2013-12-01

    Increasingly, CO2 capture and subsequent storage in deep geologic reservoirs is being implemented as a viable approach for reducing anthropogenic emissions of CO2 into the atmosphere. Several mechanisms may act to secure the injected CO2, including hydrodynamic confinement, dissolution into reservoir fluids, retention of CO2 as a separate phase in pore spaces, and carbonation of reservoir minerals. This latter mechanism is the most permanent, but it requires the presence of reactive minerals and potentially significant amounts of time for the reactions to proceed. Plagioclase feldspars are highly abundant in the earth's crust and are present in the caprocks and storage formations of many target reservoirs. Although the dissolution kinetics and carbonation reactions of feldspars have been well studied in the aqueous phase, comparatively little work has focused on plagioclase reactivity in the CO2-rich fluid at conditions relevant to geologic carbon sequestration. In this study, we used in situ infrared spectroscopy to investigate the carbonation potential of a powdered plagioclase sample similar to labradorite [(Ca,Na)(Al,Si)4O8] that had been isolated from a Hawaiian basalt. Experiments were carried out at 50 °C and 91 bar by circulating a stream of dry or wet supercritical CO2 (scCO2) past a sample overlayer deposited on the window of a high-pressure infrared flow cell. Water concentrations ranged from 0% to 125% relative to saturation, and transmission-mode absorbance spectra were recorded as a function of time for 24 hours. In experiments with excess water, a controlled temperature gradient was used to intentionally condense a film of liquid water on the overlayers' surfaces. No discernible reaction was detected when the samples were exposed to anhydrous scCO2. When water was added, a thin film of liquid-like water was observed on the samples' surfaces, and up to 0.3% of the plagioclase was converted to a carbonate phase. Calcite is the most likely reaction

  15. Fabrication of Ag/TiO2 nanotube array with enhanced photo-catalytic degradation of aqueous organic pollutant

    NASA Astrophysics Data System (ADS)

    Ma, Jie; Yang, Mingxuan; Sun, Yiran; Li, Chenlu; Li, Qiang; Gao, Fangfang; Yu, Fei; Chen, Junhong

    2014-04-01

    In this paper, the fabrication of Ag/TiO2 nanotube arrays and their photo-catalytic activity have been studied. The SEM, TEM and XRD were performed to characterize the morphology and crystalline phase of the TiO2 nanotube array and Ag/TiO2 nanotube array. Ag nanoparticles with different loadings, which are aimed to suppress the electron-hole recombination so as to enhance the photo-catalytic oxidation efficiency, were systematically coated onto TiO2 nanotubes. The photo-catalytic activity of these nano-materials was evaluated by the degradation of two different pollutants: methyl orange and glyphosate. The effects of various parameters, such as the amount of the photo-catalyst, the illumination time, and pH value on the photo-catalytic oxidation activity, were studied.

  16. Cwc2 and its human homologue RBM22 promote an active conformation of the spliceosome catalytic centre

    PubMed Central

    Rasche, Nicolas; Dybkov, Olexandr; Schmitzová, Jana; Akyildiz, Berktan; Fabrizio, Patrizia; Lührmann, Reinhard

    2012-01-01

    RNA-structural elements play key roles in pre-mRNA splicing catalysis; yet, the formation of catalytically competent RNA structures requires the assistance of spliceosomal proteins. We show that the S. cerevisiae Cwc2 protein functions prior to step 1 of splicing, and it is not required for the Prp2-mediated spliceosome remodelling that generates the catalytically active B* complex, suggesting that Cwc2 plays a more sophisticated role in the generation of a functional catalytic centre. In active spliceosomes, Cwc2 contacts catalytically important RNA elements, including the U6 internal stem-loop (ISL), and regions of U6 and the pre-mRNA intron near the 5′ splice site, placing Cwc2 at/near the spliceosome's catalytic centre. These interactions are evolutionarily conserved, as shown by studies with Cwc2's human counterpart RBM22, indicating that Cwc2/RBM22–RNA contacts are functionally important. We propose that Cwc2 induces an active conformation of the spliceosome's catalytic RNA elements. Thus, the function of RNA–RNA tertiary interactions within group II introns, namely to induce an active conformation of domain V, may be fulfilled by proteins that contact the functionally analogous U6-ISL, within the spliceosome. PMID:22246180

  17. Asphaltene cracking in catalytic hydrotreating of heavy oils. 2. study of changes in asphaltene structure during catalytic hydroprocessing

    SciTech Connect

    Sachio, A.; Chisato, T.; Shinichi, N.; Yoshimi, S.

    1983-04-01

    Characteristics in catalytic conversion of asphaltenes in petroleum heavy residues were studied in the hydrotreating process. A Boscan crude, an Athabasca bitumen, and a Khafji vacuum residue were tested as typical feedstocks. Various analyses were made to obtain the properties of asphaltenes before and after the reaction, e.g., changes of heteroatoms such as sulfur and metals, and decreases of molecular weight. The characteristic changes of asphaltene molecules were also investigated by electron spin resonance (ESR) and X-ray analyses. The association and coordination of vanadyl in asphaltenes were studied by the temperature dependence on the ESR spectra, and the sizes of the stacked crystallites and the aggregated asphaltene micelles were measured with X-ray diffraction and small-angle scattering. In the asphaltene cracking mechanism, it was clarified that the main reactions were the destruction of asphaltene micelles caused by vanadium removal and the depolymerization of asphaltene molecules by removal of heteroatoms such as sulfur.

  18. Identification of the Catalytic Mg2+ Ion in the HDV Ribozyme

    PubMed Central

    Chen, Ji; Ganguly, Abir; Miswan, Zulaika; Hammes-Schiffer, Sharon; Bevilacqua, Philip C.; Golden, Barbara L.

    2013-01-01

    The hepatitis delta virus ribozyme catalyzes an RNA cleavage reaction using a catalytic nucleobase and a divalent metal ion. The catalytic base, C75, serves as a general acid and has a pKa shifted towards neutrality. Less is known about the role of metal ions in the mechanism. A recent crystal structure of the pre-cleavage ribozyme identified a Mg2+ ion that interacts through its partial hydration sphere with the G25•U20 reverse wobble. In addition, this Mg2+ ion is in position to directly coordinate the nucleophile, the 2’-hydroxyl of U(-1), suggesting it can serve as a Lewis acid to facilitate deprotonation of the 2’-hydroxyl. To test the role of the active site Mg2+ ion, we replaced the G25•U20 reverse wobble with an isosteric A25•C20 reverse wobble. This change was found to significantly reduce the negative potential at the active site, as supported by electrostatics calculations, suggesting that active site Mg2+ binding could be adversely affected by the mutation. Kinetic analysis and molecular dynamics of the A25•C20 double mutant suggest that this variant stably folds into an active structure. However, pH-rate profiles of the double mutant are inverted relative to the profiles for wild-type ribozyme, suggesting that the A25•C20 double mutant has lost the active site metal ion. Overall, these studies support a model wherein the partially hydrated Mg2+ positioned at the G25•U20 reverse wobble is catalytic and could serve as a Lewis acid, a Brønsted base, or both to facilitate deprotonation of the nucleophile. PMID:23311293

  19. Evaluation of wet tantalum capacitors after exposure to extended periods of ripple current, volume 2

    NASA Technical Reports Server (NTRS)

    Ward, C. M.

    1975-01-01

    The application of tantalum capacitors in the Viking Lander includes dc voltage and ripple current electrical stress, high temperature during nonoperating times (sterilization), and high vibration and shock loads. The capacitors must survive these severe environments without any degradation if reliable performance is to be achieved. A test program was established to evaluate both wet-slug tantalum and wet-foil capacitors under conditions accurately duplicating actual Viking applications. Test results of the electrical performance characteristics during extended periods of ripple current, the characteristics of the internal silver migration as a function of extended periods of ripple current, and the existence of any memory characteristics are presented.

  20. The Synthesis and Characterization of Multifunctional Titania-based Materials for the Photo/Thermal Catalytic Reduction of CO2

    NASA Astrophysics Data System (ADS)

    Schwartzenberg, Kevin

    The work presented in this dissertation is aimed at improving our understanding of the fundamental processes required for the photocatalytic reduction of CO2. A QCM reactor system for measuring CO2 adsorption under a range of conditions was designed, constructed, and characterized. Measurements on catalyst films revealed sufficient sensitivity to detect CO2 adsorption on the order of 0.1 molecules/nm2. Adsorption experiments were repeatable across multiple measurements for the same film. However, variation across multiple films prepared using the same mass of catalyst highlights the large contribution of surface roughness to frequency response and the importance of uniform, reproducible film preparation. The design of a multifunctional photo/thermal catalyst was explored through the concept of MnOx-TiO2 composites with thermally generated oxygen vacancies as the active sites for CO2 activation. MnOx-TiO 2 were prepared by incipient wetness impregnation of titania supports with one of two Mn precursors, and were characterized and screened for catalytic activity. The results were compared with predictions from theoretical modeling studies. Through TPR, UV-vis spectroscopy, and XANES, it was observed that a Mn(NO 3)2•4H2O precursor led to bulk-like domains of MnOx whereas a Mn(CH3COO)2•4H2O precursor led to a dispersed surface oxide. This precursor effect was less pronounced on rutile than on anatase support. As predicted by theory, the MnOx-TiO 2 exhibited the reversible generation of oxygen vacancies at mild temperatures (< 300°C) and a red shift in the band gap for anatase-supported composites. A similar red shift was not observed for rutile-supported materials. In screening reactions, however, neither CO nor other products were detected by GC. In-situ FTIR experiments also failed to show evidence of nonvolatile CO2 reduction products. However, several carbonate, bicarbonate, and carboxylate species were observed, confirming the interaction of CO 2 with oxygen

  1. Wetting-induced pulses produced unexpectedly high emissions of N2O and NOx in a desert ecosystem

    NASA Astrophysics Data System (ADS)

    Eberwein, J. R.; Carey, C.; Aronson, E. L.; Jenerette, D.

    2015-12-01

    Approximately one third of Earth's land surface is subjected to arid conditions, and aridland soils have the potential for significant feedbacks to global climate change drivers, such as anthropogenic nitrogen deposition. This study examined wetting-induced pulses of N2O and NOx along a nitrogen deposition gradient in the Colorado Desert of southern California. Measurements were made before and following water (to simulate a 2 cm rain event) and nitrogen plus water additions (30 kg NH4NO3 ha-1) at 15 minutes, 12 hours and 24 hours post-wetting. We found nitrogenous fluxes that were substantially higher than expected. N2O fluxes, in particular were remarkably high reaching up to 200 ng N2O-N m-2 s-1, similar to agriculture levels and in the range of peat bog emissions. There was a clear transition between N2O emissions, which peaked 15 minutes after wetting, and NOx emissions, which peaked at the 12 hour timepoint. NOx emissions were also considerable, reaching as high as 350 ng NOx-N m-2 s-1. Both N2O and NOx fluxes responded strongly to water additions, demonstrating a clear wetting-induced pulse response. While N2O was not affected by nitrogen additions, NOx fluxes demonstrated a significant increase with nitrogen plus water over water alone (p=0.016). These results suggest that gaseous nitrogen export, particularly N2O emissions, is a greater form of nitrogen loss in arid systems than is currently assumed. This potential for high nitrogen emissions and the capacity for anthropogenic nitrogen deposition to increase these emissions present serious implications for local air quality and significant soil feedbacks to climate change.

  2. Catalytic Hydrothermal Gasification of Wet Biomass Feedstock

    SciTech Connect

    2006-04-01

    Industries and municipalities generate substantial amounts of biomass as high-moisture waste streams, such as animal manure, food processing sludge, stillage from ethanol production, and municipal wastewater sludge.

  3. Catalytic processes during preferential oxidation of CO in H 2-rich streams over catalysts based on copper-ceria

    NASA Astrophysics Data System (ADS)

    Gamarra, D.; Hornés, A.; Koppány, Zs.; Schay, Z.; Munuera, G.; Soria, J.; Martínez-Arias, A.

    Nanostructured catalysts based on combinations between oxidised copper and cerium entities prepared by two different methods (impregnation of ceria and coprecipitation of the two components within reverse microemulsions) have been examined with respect to their catalytic performance for preferential oxidation of CO in a H 2-rich stream (CO-PROX). Correlations between their catalytic and redox properties are established on the basis of parallel analyses of temperature programmed reduction results employing both H 2 and CO as reactants as well as by XPS. Although general catalytic trends can be directly correlated with the redox properties observed upon separate interactions with each of the two reductants (CO and H 2), the existence of interferences between both reductants must be considered to complete details for such activity/redox correlation. Differences in the nature of the active oxidised copper-cerium contacts present in each case determine the catalytic properties of these systems for the CO-PROX process.

  4. In situ transesterification of highly wet microalgae using hydrochloric acid.

    PubMed

    Kim, Bora; Im, Hanjin; Lee, Jae W

    2015-06-01

    This study addresses in situ transesterification of highly wet microalgae with hydrochloric acid (HCl) as a catalyst. In situ transesterification was performed by heating the mixture of wet algal cells, HCl, methanol, and solvent in one pot, resulting in the fatty acid methyl ester (FAME) yield over 90% at 95°C. The effects of reaction variables of temperature, amounts of catalyst, reactant, and solvent, and type of solvents on the yield were investigated. Compared with the catalytic effect of H2SO4, in situ transesterification using HCl has benefits of being less affected by moisture levels that are as high as or above 80%, and requiring less amounts of catalyst and solvent. For an equimolar amount of catalyst, HCl showed 15wt.% higher FAME yield than H2SO4. This in situ transesterification using HCl as a catalyst would help to realize a feasible way to produce biodiesel from wet microalgae. PMID:25769690

  5. High Resolution Crystal Structure of the Catalytic Domain of ADAMTS-5 (Aggrecanase-2)

    SciTech Connect

    Shieh, Huey-Sheng; Mathis, Karl J.; Williams, Jennifer M.; Hills, Robert L.; Wiese, Joe F.; Benson, Timothy E.; Kiefer, James R.; Marino, Margaret H.; Carroll, Jeffery N.; Leone, Joseph W.; Malfait, Anne-Marie; Arner, Elizabeth C.; Tortorella, Micky D.; Tomasselli, Alfredo

    2008-06-30

    Aggrecanase-2 (a disintegrin and metalloproteinase with thrombospondin motifs-5 (ADAMTS-5)), a member of the ADAMTS protein family, is critically involved in arthritic diseases because of its direct role in cleaving the cartilage component aggrecan. The catalytic domain of aggrecanase-2 has been refolded, purified, and crystallized, and its three-dimensional structure determined to 1.4{angstrom} resolution in the presence of an inhibitor. A high resolution structure of an ADAMTS/aggrecanase protein provides an opportunity for the development of therapeutics to treat osteoarthritis.

  6. Synthesis, structural properties and catalytic activity of MgO-SnO2 nanocatalysts

    NASA Astrophysics Data System (ADS)

    Perveen, Hina; Farrukh, Muhammad Akhyar; Khaleeq-ur-Rahman, Muhammad; Munir, Badar; Tahir, Muhammad Ashraf

    2015-01-01

    Surfactant controlled synthesis of magnesium oxide-tin oxide (MgO-SnO2) nanocatalysts was carried out via the hydrothermal method. Concentration of sodium dodecyl sulfate (SDS) was varied while all other reaction conditions were kept constant same for this purpose. Furthermore, MgO-SnO2 nanocatalysts were also prepared by changing the precursor's concentration. These precursors are magnesium nitrate Mg(NO3)2 · 6H2O and tin chloride (SnCl4 · 5H2O). The influence of these reaction parameters on the sizes and morphology of the nanocatalysts were studied by using Fourier transform infrared (FTIR) spectroscopy, Scanning electron microscopy-Energy dispersive X-ray (SEM-EDX), Powder X-ray diffraction (XRD), Transmission electron microscopy and Thermo gravimetric analysis (TGA). The catalytic efficiency of MgO-SnO2 was checked against 2,4-dinitrophenylhydrazine (DNPH), which is an explosive compound. The nanocatalysts were found as a good catalyst to degrade the DNPH. Catalytic activity of nanocatalysts was observed up to 19.13% for the degradation DNPH by using UV-spectrophotometer.

  7. LOXL2 catalytically inactive mutants mediate epithelial-to-mesenchymal transition.

    PubMed

    Cuevas, Eva P; Moreno-Bueno, Gema; Canesin, Giacomo; Santos, Vanesa; Portillo, Francisco; Cano, Amparo

    2014-01-01

    Lysyl-oxidase-like 2 (LOXL2) is a member of the lysyl oxidase family that catalyzes the cross-linking of collagens or elastins in the extracellular matrix, thus regulating the tensile strength of tissues. However, many reports have suggested different intracellular roles for LOXL2, including the ability to regulate gene transcription and tumor progression. We previously reported that LOXL2 mediates epithelial-to-mesenchymal transition (EMT) by Snail1-dependent and independent mechanisms, related to E-cadherin silencing and downregulation of epidermal differentiation and cell polarity components, respectively. Whether or not the catalytic activity of LOXL2 is required to induce/sustain EMT is actually unknown. Here we show that LOXL2 catalytic inactive mutants collaborate with Snail1 in E-cadherin gene repression to trigger EMT and, in addition, promote FAK/Src pathway activation to support EMT. These findings reveal a non-conventional role of LOXL2 on regulating epithelial cell plasticity. PMID:24414204

  8. Synthesis of Au-SiO2 Composite Nanospheres and Their Catalytic Activity.

    PubMed

    Dexuan, Wang; Guian, Li; Qingyan, Han; Ziqiang, Wang; Liping, Pan; Zhonayue, Zhang; Hairong, Zhenq

    2016-04-01

    We report a simple and environmentally friendly approach to the synthesis of Au-SiC2 composite nanospheres. Our method presents a route for the decoration of preformed amine functionalized SiO2 nanospheres by in situ formation of Au nanoparticles at three different concentrations of Au precursor (HAuCl4). Herein, the silane coupling agent (KH-550) is used as an intermediary to connect the Au nanoparticles to the surfaces of the SiO2 nanospheres, which helps avoid the aggregation of Au nanoparticles. The crystal structure, chemical elements, morphology and catalytic properties of the Au-SiO2 composite nanospheres were analyzed by transmission electron microscopy (TEM), X-Ray powder diffraction (XRD), UV-vis-spectrophotometer (UV-vis) and X-ray photoelectron spectroscopy (XPS). The analytical results demonstrate that the Au nanoparticles (4-9 nm) were homogeneously distributed on the surface of the SiO2 nanospheres, which had a good FCC crystal structure. Moreover, the Au-SiO2 composite nanospheres exhibited good catalytic properties, measured by their ability to reduce organic dyes. The Au-SiO2 composite nanospheres are promising candidates for applications in catalysis and wastewater treatment. PMID:27451717

  9. Effect of ZrO{sub 2}-doping of nanosized Fe{sub 2}O{sub 3}/MgO system on its structural, surface and catalytic properties

    SciTech Connect

    Hassan, Neveen A.; El-Molla, Sahar A.; Mohamed, Ghada M.; Fagal, Gehan A.

    2012-09-15

    Highlights: ► Preparation and characterization nano-sized ZrO{sub 2}-doped Fe{sub 2}O{sub 3}/MgO system. ► Pure and doped solids calcined at 500 and 700 °C are mesoporous adsorbents. ► ZrO{sub 2}-doping increased the lattice constant “a” of MgO lattice to an extent proportional to the amount of ZrO{sub 2} added. ► The catalytic activity in H{sub 2}O{sub 2} decomposition was found to increase as a function of dopant concentration. -- Abstract: Fe{sub 2}O{sub 3}/MgO system was prepared by wet impregnation method followed by treatment with different amounts of Zr-dopant salt then heating at 500 and 700 °C. The dopant concentrations were 0.48, 0.95 and 1.4 mol% ZrO{sub 2}. Pure and variously doped solids were characterized using XRD, N{sub 2}-adsorption isotherms carried out at −196 °C and catalytic decomposition of H{sub 2}O{sub 2} in aqueous solution at 25–35 °C. The results revealed that the nanosized MgO phase was only detected in the diffractograms of pure and doped solids calcined at 500 °C. Heating pure and doped solids at 700 °C produced nanosized MgFe{sub 2}O{sub 4} phase together with MgO phase. Pure and ZrO{sub 2}-doped solids calcined at 500 and 700 °C are mesoporous adsorbents. The doping process brought about a measurable decrease in the S{sub BET} of Fe{sub 2}O{sub 3}/MgO system with subsequent increase in its catalytic activity. The catalytic activity of the investigated system toward H{sub 2}O{sub 2} decomposition, expressed as reaction rate constant per unit surface area was found to increase as a function of dopant concentration. The maximum increase in the reaction rate constant per unit surface area measured for the reaction carried out at 30 °C attained 125% for the heavily doped samples. This significant increase was based on the catalytic activity of pure catalyst sample measured under the same conditions.

  10. Surface characterization and catalytic CO + H 2 reaction on Fe 82.2B 17.8 amorphous alloy

    NASA Astrophysics Data System (ADS)

    Kisfaludi, G.; Lázár, K.; Schay, Z.; Guczi, L.; Fetzer, Cs.; Konczos, G.; Lovas, A.

    1985-09-01

    Fe 82.2B 17.8 amorphous ribbon has been used as a catalyst for the Fischer-Tropsch-type reaction of CO+H 2. Specific activity has been found to be at least an order of magnitude higher than that of either the crystallized ribbon of identical composition or the supported iron catalyst. Before and after the catalytic tests the ribbons were characterized by XRD, XPS, UPS and Mössbauer spectroscopy in transmission and in conversion electron modes. Conversion electron Mössbauer spectroscopy and UPS proved that the surface of the amorphous ribbons is being partially crystallized during 8000 min reaction time at a maximum reaction temperature of 560 K. The superior catalytic activity has been explained by stabilization of the small iron particles and Fe 2O 3 by boron atoms at the surface and by suppressed carbide formation.

  11. On the catalytic effects of UO 2(s) and Pd(s) on the reaction between H 2O 2 and H 2 in aqueous solution

    NASA Astrophysics Data System (ADS)

    Nilsson, Sara; Jonsson, Mats

    2008-01-01

    The possible catalytic effects of UO 2 and Pd (as a model for noble metal particles) on the reaction between H 2O 2 and H 2 have been studied experimentally. The experiments were performed in aqueous solution using an autoclave. The aqueous solutions were pressurized with H 2 or N 2 and the H 2O 2 concentration was measured as a function of time. The experiments clearly showed that Pd catalyzes the reaction between H 2O 2 and H 2 while UO 2 has no catalytic effect. The rate constant of the reaction between H 2O 2 and H 2 catalyzed by Pd was found to be close to diffusion controlled and independent of the H 2 pressure in the range 1-40 bar. The impact of the catalytic effect on the reaction between H 2O 2 and H 2 on spent nuclear fuel dissolution is, however, fairly small. Other possible effects of noble metal particles are also discussed, e.g. reduction of U(VI) to U(IV) in the liquid and solid phase.

  12. Structure of the catalytic domain of the hepatitis C virus NS2-3 protease

    SciTech Connect

    Lorenz,I.; Marcotrigiano, J.; Dentzer, T.; Rice, C.

    2006-01-01

    Hepatitis C virus is a major global health problem affecting an estimated 170 million people worldwide. Chronic infection is common and can lead to cirrhosis and liver cancer. There is no vaccine available and current therapies have met with limited success. The viral RNA genome encodes a polyprotein that includes two proteases essential for virus replication. The NS2-3 protease mediates a single cleavage at the NS2/NS3 junction, whereas the NS3-4A protease cleaves at four downstream sites in the polyprotein. NS3-4A is characterized as a serine protease with a chymotrypsin-like fold, but the enzymatic mechanism of the NS2-3 protease remains unresolved. Here we report the crystal structure of the catalytic domain of the NS2-3 protease at 2.3 Angstroms resolution. The structure reveals a dimeric cysteine protease with two composite active sites. For each active site, the catalytic histidine and glutamate residues are contributed by one monomer, and the nucleophilic cysteine by the other. The carboxy-terminal residues remain coordinated in the two active sites, predicting an inactive post-cleavage form. Proteolysis through formation of a composite active site occurs in the context of the viral polyprotein expressed in mammalian cells. These features offer unexpected insights into polyprotein processing by hepatitis C virus and new opportunities for antiviral drug design.

  13. One-pot, one-step, catalytic synthesis of 2,5-diformylfuran from fructose

    NASA Astrophysics Data System (ADS)

    Tao, Furong; Cui, Yuezhi; Yang, Pengfei; Gong, Yinghua

    2014-07-01

    MIL-101, a chromium-based metal-organic framework, is known for its very large pore size, large surface area and good stability. However, application of this material in catalysis is still limited. In this paper, a simple and practical catalytic method for the preparation 2,5-diformylfuran (DFF) directly from fructose was investigated. 5% Pd-V(3: 2)@MIL-101 was evaluated as a potential and effective catalyst for the direct oxidation of fructose. The amount of the catalyst, reaction time and temperature had a large effect on the reaction. At the optimized reaction conditions, when the reaction was conducted at 140°C for 600 min, 1 atm oxygen pressure, the yield of DFF reached 34%, fructose conversion was up to 100%. In our system, the main side products were 5-formyl-2-furancarboxylic acid (FFCA) and 2,5-furandicarboxylic acid (FDCA), which are the products of deep oxidation of DFF. This simple and effective catalytic system may be valuable to facilitate energy-efficient conversion of fructose into biofuels and platform chemicals.

  14. Synthesis, spectroscopic and catalytic properties of some new boron hybrid molecule derivatives by BF2 and BPh2 chelation

    NASA Astrophysics Data System (ADS)

    Kilic, Ahmet; Alcay, Ferhat; Aydemir, Murat; Durgun, Mustafa; Keles, Armagan; Baysal, Akın

    2015-05-01

    A new series of Schiff base ligands (L1-L3) and their corresponding fluorine/phenyl boron hybrid complexes [LnBF2] and [LnBPh2] (n = 1, 2 or 3) have been synthesized and well characterized by both analytical and spectroscopic methods. The Schiff base ligands and their corresponding fluorine/phenyl boron hybrid complexes have been characterized by NMR (1H, 13C and 19F), FT-IR, UV-Vis, LC-MS, and fluorescence spectroscopy as well as melting point and elemental analysis. The fluorescence efficiencies of phenyl chelate complexes are greatly red-shifted compared to those of the fluorine chelate analogs based on the same ligands, presumably due to the large steric hindrance and hard π → π∗ transition of the diphenyl boron chelation, which can effectively prevent molecular aggregation. The boron hybrid complexes were applied to the transfer hydrogenation of acetophenone derivatives to 1-phenylethanol derivatives in the presence of 2-propanol as the hydrogen source. The catalytic studies showed that boron hybrid complexes are good catalytic precursors for transfer hydrogenation of aromatic ketones in 0.1 M iso-PrOH solution. Also, we have found that both steric and electronic factors have a significant impact on the catalytic properties of this class of molecules.

  15. Synthesis, spectroscopic and catalytic properties of some new boron hybrid molecule derivatives by BF2 and BPh2 chelation.

    PubMed

    Kilic, Ahmet; Alcay, Ferhat; Aydemir, Murat; Durgun, Mustafa; Keles, Armagan; Baysal, Akın

    2015-05-01

    A new series of Schiff base ligands (L1-L3) and their corresponding fluorine/phenyl boron hybrid complexes [LnBF2] and [LnBPh2] (n=1, 2 or 3) have been synthesized and well characterized by both analytical and spectroscopic methods. The Schiff base ligands and their corresponding fluorine/phenyl boron hybrid complexes have been characterized by NMR ((1)H, (13)C and (19)F), FT-IR, UV-Vis, LC-MS, and fluorescence spectroscopy as well as melting point and elemental analysis. The fluorescence efficiencies of phenyl chelate complexes are greatly red-shifted compared to those of the fluorine chelate analogs based on the same ligands, presumably due to the large steric hindrance and hard π→π(∗) transition of the diphenyl boron chelation, which can effectively prevent molecular aggregation. The boron hybrid complexes were applied to the transfer hydrogenation of acetophenone derivatives to 1-phenylethanol derivatives in the presence of 2-propanol as the hydrogen source. The catalytic studies showed that boron hybrid complexes are good catalytic precursors for transfer hydrogenation of aromatic ketones in 0.1M iso-PrOH solution. Also, we have found that both steric and electronic factors have a significant impact on the catalytic properties of this class of molecules. PMID:25703358

  16. Catalytic combustion of benzene over CuO-CeO2 mixed oxides.

    PubMed

    Jung, Won Young; Lim, Kwon-Taek; Hong, Seong-Soo

    2014-11-01

    Catalytic combustion of benzene over CuO-CeO2 mixed oxides has been investigated. The CuO-CeO2 mixed oxides were prepared by the combustion method using malic acid as an organic fuel and characterized by XRD, XPS and TPR. For the CuO-CeO2 catalyst with a Cu/(Cu + Ce) molar ratio of more than 0.4, highly dispersed copper oxide species were shown at 2θ = 35.5 degrees and 38.8 degrees. The CuO-CeO2 catalyst prepared using 2.0 M malic acid showed the highest activity, with conversion reaching nearly 100% at 350 degrees C. In addition, the highest activity is shown on Cu0.40 (the index denotes the molar ratio Cu/(Cu + Ce)) sample and then it decreases on Cu0.5 and Cu0.7 samples. PMID:25958554

  17. Catalytic decomposition of H2O2 over Fe-based catalysts for simultaneous removal of NOX and SO2

    NASA Astrophysics Data System (ADS)

    Huang, Xianming; Ding, Jie; Zhong, Qin

    2015-01-01

    Simultaneous flue gas desulfurization and denitrification were achieved with rad OH radicals from the decomposition of H2O2 over hematite (Fe) as well as hematite supported on alumina (Fe-Al) and anatase (Fe-Ti). Under all conditions, SO2 achieved 100% removal, whereas NOX removal varies with the catalysts. The supporting of Fe over aluminum enhances the catalytic removal of NOX, whereas that of anatase presents negative effect. The NOX removal is determined by the decomposition rate of H2O2 into rad OH radicals over sbnd OH bonded with Fe (Fe-OH). The supporting of Fe over alumina enhances the content of Fe-OH and the points of zero charge (PZC) values, which are beneficial for the production of rad OH radicals. The supporting of Fe over anatase results in the formation of FeOTi, which cannot decompose H2O2 into rad OH radicals. Furthermore, H2O2 tends more to be reacted with TiOH to produce O2 over Fe-Ti. Finally, the enhancement mechanism of H2O2 decomposition over Fe-based catalysts is speculated. It has a contribution to the correct choice for supports and active ingredients of the catalyst in the future industrial applications.

  18. Catalytic behavior of AMoO{sub x} (A = Ba, Sr) in oxidation of 2-propanol

    SciTech Connect

    Kubo, Jun Ueda, Wataru

    2009-04-02

    Perovskite-type oxides, BaMoO{sub 3} and SrMoO{sub 3}, were prepared by reduction of scheelite-type oxides, BaMoO{sub 4} and SrMoO{sub 4}, in H{sub 2} flow at 873 K and characterized by XRD, TG, SEM, TPR, NH{sub 3}-TPD, UV-vis DRS and BET measurement. The catalytic activity of these alkaline-earth molybdenum oxide catalysts was tested for oxidation of 2-propanol with gaseous oxygen under atmospheric pressure. Dehydration to propylene was mainly promoted over the scheelite-type with Mo{sup 6+}, while oxidative dehydrogenation to acetone was mainly promoted over the perovskite-type with Mo{sup 4+}, and selectivity to acetone was much higher over BaMoO{sub 3} than over SrMoO{sub 3}. Both perovskite-type oxide catalysts underwent oxidation to some degree during the catalytic reaction, so that they also contained some Mo{sup 6+}. We concluded that the high selectivity to acetone resulting from oxidative dehydrogenation during 2-propanol conversion is related to the constantly changing oxidation state of the catalyst, resulting in coexistence of Mo{sup 6+} octahedra and Mo{sup 4+} octahedra on the AMoO{sub 3} oxides.

  19. Antibiotic Binding Drives Catalytic Activation of Aminoglycoside Kinase APH(2″)-Ia.

    PubMed

    Caldwell, Shane J; Huang, Yue; Berghuis, Albert M

    2016-06-01

    APH(2″)-Ia is a widely disseminated resistance factor frequently found in clinical isolates of Staphylococcus aureus and pathogenic enterococci, where it is constitutively expressed. APH(2″)-Ia confers high-level resistance to gentamicin and related aminoglycosides through phosphorylation of the antibiotic using guanosine triphosphate (GTP) as phosphate donor. We have determined crystal structures of the APH(2″)-Ia in complex with GTP analogs, guanosine diphosphate, and aminoglycosides. These structures collectively demonstrate that aminoglycoside binding to the GTP-bound kinase drives conformational changes that bring distant regions of the protein into contact. These changes in turn drive a switch of the triphosphate cofactor from an inactive, stabilized conformation to a catalytically competent active conformation. This switch has not been previously reported for antibiotic kinases or for the structurally related eukaryotic protein kinases. This catalytic triphosphate switch presents a means by which the enzyme can curtail wasteful hydrolysis of GTP in the absence of aminoglycosides, providing an evolutionary advantage to this enzyme. PMID:27161980

  20. Possibility of a catalytic reaction of H/sub 2/ + Cl/sub 2/

    SciTech Connect

    Kurlyandskaya, I.I.; Rozlovskii, A.I.

    1988-12-01

    It is shown that the amount of conversion of hydrogen in its reaction with chlorine in a mixture passing through a layer of activated carbon at 200/degrees/C corresponds to an effective rate constant that is three orders of magnitude larger than that calculated for the homogeneous reaction in the regime of equilibrium dissociation of chlorine. On the basis of this, the conclusion is drawn that a heterogeneous catalytic process predominates in this case. It is established that with an increase in the temperature up to 300/degrees/, the rate of the homogeneous reaction, having the larger temperature coefficient, becomes commensurate with the heterogeneous rate. In the general case, the ratio of the rates of chlorination for the homogeneous, chain mechanism and for the heterogeneous catalytic reaction mechanism depend on the experimental conditions.

  1. Organometallic derivatives of furan. LX. Reactions of di-2-furyldimethylgermane under catalytic-hydrogenation conditions

    SciTech Connect

    Lukevits, E.; Ignatovich, L.M.; Yuskovets, Zh.G.; Golender, L.O.; Shimanskaya, M.V.

    1987-11-20

    In the reaction of di-2-furyldimethylgermane with hydrogen in the presence of the homogeneous metal-complex catalyst RhH(CO)(PPh/sub 3/)/sub 3/ the selective hydrogenation of one of the furan rings occurs, but over heterogeneous catalysts (Raney Ni, Rh black, Pd/C) hydrogenation and hydrogenolysis reactions occur. Di-2-furyldimethylgermane is converted into (2-furyl)dimethyl(tetrahydro-2-furyl)-germane by the catalytic transfer of hydrogen from 2-propanol and cyclohexene. On the basis of the kinetic relations and quantum-chemical calculations of the electron structures of the original and partially hydrogenated furylgermanes a stagewise scheme is proposed of the hydrogenation of the furan ring and the further hydrogenolysis of the semihydrogenated germane molecule.

  2. Influence of He/O 2 atmospheric pressure plasma jet treatment on subsequent wet desizing of polyacrylate on PET fabrics

    NASA Astrophysics Data System (ADS)

    Li, Xuming; Lin, Jun; Qiu, Yiping

    2012-01-01

    The influence of He/O2 atmospheric pressure plasma jet (APPJ) treatment on subsequent wet desizing of polyacrylate on PET fabrics was studied in the present paper. Weight loss results indicated that the weight loss increased with an increase of plasma treatment time. Atomic force microscopy (AFM) and scanning electron microscopy (SEM) showed an increased surface roughness after the plasma treatment. SEM also showed that the fiber surfaces were as clean as unsized fibers after 35 s treatment followed by NaHCO3 desizing. X-ray photoelectron spectroscopy (XPS) analysis indicated that oxygen-based functional groups increased for the plasma treated polyacrylate sized fabrics. The percent desizing ratio (PDR) results showed that more than 99% PDR was achieved after 65 s plasma treatment followed by a 5 min NaHCO3 desizing. Compared to conventional wet desizing, indicating that plasma treatment could significantly reduce desizing time.

  3. Catalytic conversion of alcohols. 28. Product selectivities for 2-methylcyclohexanol conversion with metal oxide catalysts

    SciTech Connect

    Dabbagh, H.A.; Hughes, C.G.; Davis, B.H. )

    1992-02-01

    Metal oxides exhibit a range of selectivities (dehydration percentage, alkene distribution and alcohol isomerization) for the conversion of a 2-methylcyclohexanol isomer. For many metal oxide catalysts, trans-2-methylcyclohexanol produces a predominance of the less stable 3-methylcyclohexene isomer. The grouping of metal oxides based on the production of the less stable alkene isomers from 2-octanol is similar to that for trans-2-methlycyclohexanol. It is proposed that the same catalytic properties determine the selectivity for both reactants: for smaller metal cations the product selectivity is determined by steric crowding in the transition state, and for the larger cations the product selectivity is determined by the basicity of the oxygen anion and the relative acidity of the {beta}-hydrogens that are eliminated to produce water.

  4. A Catalytic Sensor for Measurement of Radical Density in CO2 Plasmas

    PubMed Central

    Vesel, Alenka; Zaplotnik, Rok; Iacono, Jonathan; Balat-Pichelin, Marianne; Mozetic, Miran

    2012-01-01

    A catalytic sensor for the measurement of radical density in weakly ionized CO2 plasmas, created in a low-pressure electrodeless discharge, is presented. The CO2 plasma was created in a 4 cm wide borosilicate glass tube inside a copper coil connected to a radio frequency generator operating at 27.12 MHz with a nominal power of 250 W. The dissociation fraction of the CO2 molecules was measured in the early afterglow at pressures ranging from 10 Pa to 100 Pa, and at distances of up to 35 cm along the gas stream from the glowing plasma. The radical density peaked (2 × 1020 m−3) at 80 Pa. The density quickly decreased with increasing distance from the glowing plasma despite a rather large drift velocity. The dissociation fraction showed similar behavior, except that the maximum was obtained at somewhat lower pressure. The results were explained by rather intense surface recombination of radicals. PMID:23443372

  5. Sponge phase producing porous CeO2 for catalytic oxidation of CO.

    PubMed

    Song, Shasha; Wang, Haiqiao; Song, Aixin; Dong, Shuli; Hao, Jingcheng

    2014-07-14

    The aggregation behavior of mixtures of the alkaline amino acid L-Arginine (L-Arg) and bis(2-ethylhexyl)phosphoric acid (DEHPA) in water was studied in detail. At a fixed L-Arg concentration, a phase sequence of micellar phase (L1 phase), vesicle phase (Lαv phase), planar lamellar phase (Lαl phase), and sponge phase (L3 phase) was obtained with increasing DEHPA concentration due to changes in the packing parameter. The phase transition of the lamellar structures was determined by freeze-fracture TEM and (2)H NMR spectroscopy. Rheological measurements reflected the phase transition through significant variations of both the elastic modulus and the viscous modulus. Porous CeO2 materials were produced by utilizing the L3 phase as template, and the porous CeO2 exhibited excellent catalytic oxidation activity toward CO due to its high surface area, which provides more active sites for CO conversion. PMID:24895013

  6. In situ IR studies of Co and Ce doped Mn/TiO2 catalyst for low-temperature selective catalytic reduction of NO with NH3

    NASA Astrophysics Data System (ADS)

    Qiu, Lu; Pang, Dandan; Zhang, Changliang; Meng, Jiaojiao; Zhu, Rongshu; Ouyang, Feng

    2015-12-01

    The Mn-Co-Ce/TiO2 catalyst was prepared by wet co-impregnation method for selective catalytic reduction of NO by NH3 in the presence of oxygen. The adsorption and co-adsorption of NH3, NO and O2 on catalysts were investigated by in situ FTIR spectroscopy. The results suggested that addition of cobalt and cerium oxides increased the numbers of acid and redox sites. Especially, the cobalt oxide produced lots of Brønsted acid sites, which favor to the adsorption of coordinated NH3 through NH3 migration. Ce addition improved amide ions formation to reach best NO reduction selectivity. A mechanistic pathway over Mn-Co-Ce/TiO2 was proposed. At low-temperature SCR reaction, coordinated NH3 reacted with NO2-, and amide reacted with NO (ad) or NO (g) to form N2. NO2 was related to the formation of nitrite on Co-contained catalysts and the generation of sbnd NH2- on Ce-contained catalysts. At high temperature, the other branch reaction also occurred between the coordinated NH3 and nitrate species, resulting in N2O yield increase.

  7. PREFACE: Dynamics of wetting Dynamics of wetting

    NASA Astrophysics Data System (ADS)

    Grest, Gary S.; Oshanin, Gleb; Webb, Edmund B., III

    2009-11-01

    Capillary phenomena associated with fluids wetting other condensed matter phases have drawn great scientific interest for hundreds of years; consider the recent bicentennial celebration of Thomas Young's paper on equilibrium contact angles, describing the geometric shape assumed near a three phase contact line in terms of the relevant surface energies of the constituent phases [1]. Indeed, nearly a century has passed since the seminal papers of Lucas and Washburn, describing dynamics of capillary imbibition [2, 3]. While it is generally appreciated that dynamics of fluid wetting processes are determined by the degree to which a system is out of capillary equilibrium, myriad complications exist that challenge the fundamental understanding of dynamic capillary phenomena. The topic has gathered much interest from recent Nobel laureate Pierre-Gilles de Gennes, who provided a seminal review of relevant dissipation mechanisms for fluid droplets spreading on solid surfaces [4] Although much about the dynamics of wetting has been revealed, much remains to be learned and intrinsic technological and fundamental interest in the topic drives continuing high levels of research activity. This is enabled partly by improved experimental capabilities for resolving wetting processes at increasingly finer temporal, spatial, and chemical resolution. Additionally, dynamic wetting research advances via higher fidelity computational modeling capabilities, which drive more highly refined theory development. The significance of this topic both fundamentally and technologically has resulted in a number of reviews of research activity in wetting dynamics. One recent example addresses the evaluation of existing wetting dynamics theories from an experimentalist's perspective [5]. A Current Opinion issue was recently dedicated to high temperature capillarity, including dynamics of high temperature spreading [6]. New educational tools have recently emerged for providing instruction in wetting

  8. Decomposition of 1,2-dichloroethane over CeO2 modified USY zeolite catalysts: effect of acidity and redox property on the catalytic behavior.

    PubMed

    Huang, Qinqin; Xue, Xiaomin; Zhou, Renxian

    2010-11-15

    CeO(2) modified ultrastable Y zeolite (CeO(2)-USY) catalysts were prepared and were used as the catalysts for the decomposition of 1,2-dichloroethane (DCE). The catalytic behavior of these catalysts was evaluated by micro-reaction and temperature-programmed surface reaction (TPSR) technique. The results reveal that CeO(2)-USY catalysts exhibit good catalytic activity for DCE decomposition and high selectivity to the formation of CO(2) and HCl. Both acidity and redox property play important roles in the DCE decomposition, and the synergy between CeO(2) species and USY zeolite shows an enhancement in the catalytic activity for DCE decomposition. CeO(2)-USY (1:8) with high dispersion of CeO(2) species and a much more suitable combination of acidity and redox property exhibits the best catalytic activity. PMID:20709452

  9. Mechanistic Insights into Hydride Transfer for Catalytic Hydrogenation of CO2 with Cobalt Complexes

    SciTech Connect

    Kumar, Neeraj; Camaioni, Donald M.; Dupuis, Michel; Raugei, Simone; Appel, Aaron M.

    2014-08-21

    The catalytic hydrogenation of CO2 to formate by Co(dmpe)2H can proceeds via direct hydride transfer or via CO2 coordination to Co followed by reductive elimination of formate. Both pathways have activation barriers consistent with experiment (~17.5 kcal/mol). Controlling the basicity of Co by ligand design is key to improve catalysis. The research by N.K., D.M.C. and A.M.A. was supported by the US Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. The research by S.R. and M.D. was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science. Pacific Northwest National Laboratory (PNNL) is a multiprogram national laboratory operated for the DOE by Battelle.

  10. (Catalytic mechanism of hydrogenase from aerobic N sub 2 -fixing microorganisms)

    SciTech Connect

    Arp, D.J.

    1990-01-01

    Hydrogenases are enzymes which catalyze reactions involving dihydrogen. They serve integral roles in a number of microbial metabolic pathways. Our research is focussed on investigations of the catalytic mechanism of the hydrogenases found in aerobic, N{sub 2}-fixing microorganisms such as Azotobacter vinelandii and the agronomically important Bradyrhizobium japonicum as well as microorganisms with similar hydrogenases. The hydrogenases isolated from these microorganisms are Ni- and Fe-containing heterodimers. Our work has focussed on three areas during the last grant period. In all cases, a central theme has been the role of inhibitors in the characteristics under investigation. In addition, a number of collaborative efforts have yielded interesting results. In metalloenzymes such as hydrogenase, inhibitors often influence the activity of the enzyme through ligand interactions with redox centers, often metals, within the enzyme. Therefore, investigations of the ability of various compounds to inhibit an enzyme's activity, as well as the mechanism of inhibition, can provide insight into the catalytic mechanism of the enzyme as well as the role of various redox centers in catalysis. We have investigated in detail four inhibitors of A. vinelandii and the results are summarized here. The influence of these inhibitors on the spectral properties of the enzyme are summarized. Electron paramagnetic resonance and ultraviolet spectra investigations are discussed. 9 figs.

  11. Determinants of ligand binding and catalytic activity in the myelin enzyme 2',3'-cyclic nucleotide 3'-phosphodiesterase.

    PubMed

    Raasakka, Arne; Myllykoski, Matti; Laulumaa, Saara; Lehtimäki, Mari; Härtlein, Michael; Moulin, Martine; Kursula, Inari; Kursula, Petri

    2015-01-01

    2',3'-cyclic nucleotide 3'-phosphodiesterase (CNPase) is an enzyme highly abundant in the central nervous system myelin of terrestrial vertebrates. The catalytic domain of CNPase belongs to the 2H phosphoesterase superfamily and catalyzes the hydrolysis of nucleoside 2',3'-cyclic monophosphates to nucleoside 2'-monophosphates. The detailed reaction mechanism and the essential catalytic amino acids involved have been described earlier, but the roles of many amino acids in the vicinity of the active site have remained unknown. Here, several CNPase catalytic domain mutants were studied using enzyme kinetics assays, thermal stability experiments, and X-ray crystallography. Additionally, the crystal structure of a perdeuterated CNPase catalytic domain was refined at atomic resolution to obtain a detailed view of the active site and the catalytic mechanism. The results specify determinants of ligand binding and novel essential residues required for CNPase catalysis. For example, the aromatic side chains of Phe235 and Tyr168 are crucial for substrate binding, and Arg307 may affect active site electrostatics and regulate loop dynamics. The β5-α7 loop, unique for CNPase in the 2H phosphoesterase family, appears to have various functions in the CNPase reaction mechanism, from coordinating the nucleophilic water molecule to providing a binding pocket for the product and being involved in product release. PMID:26563764

  12. Atmospheric trace elements at Enewetak Atoll: 2. Transport to the ocean by wet and dry deposition

    NASA Astrophysics Data System (ADS)

    Arimoto, R.; Duce, R. A.; Ray, B. J.; Unni, C. K.

    1985-02-01

    The concentrations of trace elements in precipitation and dry deposition are presented for samples collected at Enewetak Atoll (11°N, 162° E) during SEAREX experiments in 1979. The concentrations of Al, Sc, Mn, Fe, Co, and Th in rain are dominated by crustal material, and for these elements, wet deposition evidently exceeds dry deposition. For most of these elements the present rates of atmospheric deposition at Enewetak are similar to their mean rate of accumulation in sediments over the past 5-10,000 years, suggesting that the air-to-sea exchange of particles is closely tied to the sedimentary cycle of the mid-Pacific. Noncrustal sources govern the concentrations of Pb, Zn, Cu, Se, and Cd in wet and dry deposition samples. Analyses of dry deposition collected from a flat plastic plate indicate that the amount of material recycled from the sea surface varies markedly between samples, and even though these estimates do not necessarily reflect the dry deposition to the ocean surface, the results suggest that recycled sea spray often amounts to more than 50% of the total dry deposition of the enriched elements. Recycled sea spray also makes up a significant fraction of the total wet deposition of the enriched elements. The net deposition rates of elements such as Cu and Zn are greater than or equal to their inputs from vertical mixing, but the net deposition of Pb clearly exceeds the input from upwelling. The current net deposition rates of the enriched elements are also similar to their rates of removal to sediments. These results indicate that air-sea exchange processes may significantly affect the chemistry of trace metals in the open ocean.

  13. Morphology control of ceria nanocrystals for catalytic conversion of CO2 with methanol

    NASA Astrophysics Data System (ADS)

    Wang, Shengping; Zhao, Lifang; Wang, Wei; Zhao, Yujun; Zhang, Guanglin; Ma, Xinbin; Gong, Jinlong

    2013-05-01

    This paper describes the synthesis of ceria catalysts with octahedron, nanorod, nanocube and spindle-like morphologies via a template-free hydrothermal method. The surface morphologies, crystal plane and physical-chemical structures were investigated via field-emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD) and temperature-programmed desorption of ammonia and carbon dioxide (NH3-TPD and CO2-TPD). The catalytic performance over these ceria catalysts with different exposed planes were tested for dimethyl carbonate (DMC) synthesis from CO2 and methanol. The results showed that the spindle-like CeO2 showed the highest DMC yields, followed by nano-rods, nano-cubes and nano-octahedrons. A synergism among the exposed (111) plane, defect sites, and acid-basic sites was proposed to be crucial to obtaining the high reactivity of DMC formation.This paper describes the synthesis of ceria catalysts with octahedron, nanorod, nanocube and spindle-like morphologies via a template-free hydrothermal method. The surface morphologies, crystal plane and physical-chemical structures were investigated via field-emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD) and temperature-programmed desorption of ammonia and carbon dioxide (NH3-TPD and CO2-TPD). The catalytic performance over these ceria catalysts with different exposed planes were tested for dimethyl carbonate (DMC) synthesis from CO2 and methanol. The results showed that the spindle-like CeO2 showed the highest DMC yields, followed by nano-rods, nano-cubes and nano-octahedrons. A synergism among the exposed (111) plane, defect sites, and acid-basic sites was proposed to be crucial to obtaining the high reactivity of DMC formation. Electronic supplementary information (ESI) available. See DOI

  14. The effect of CNTs on structures and catalytic properties of AuPd clusters for H2O2 synthesis.

    PubMed

    Yang, Hua-feng; Xie, Peng-yang; Yu, Hui-you; Li, Xiao-nian; Wang, Jian-guo

    2012-12-28

    The structures and catalytic properties of AuPd clusters supported on carbon nanotubes (CNTs) for H(2)O(2) synthesis have been investigated by means of density functional theory calculations. Firstly, the structures of AuPd clusters are strongly influenced by CNTs, in which the bottom layers are mainly composed of Pd and the top layers are a mix of Au and Pd due to the stronger binding of Pd than Au on CNTs. Especially, it is found that O(2) adsorption on the Pd/CNTs interfacial sites is much weaker than that on the only Pd sites, which is in contrast to transition metal oxide (for example TiO(2), Al(2)O(3), CeO(2)) supported metal clusters. Furthermore, Pd ensembles on the interfacial sites have far superior catalytic properties for H(2)O(2) formation than those away from CNT supports due to the changes in electronic structures caused by the CNTs. Therefore, our study provides a physical insight into the enhanced role of carbon supports in H(2)O(2) synthesis over supported AuPd catalysts. PMID:23032860

  15. Removal of formaldehyde over Mn(x)Ce(1)-(x)O(2) catalysts: thermal catalytic oxidation versus ozone catalytic oxidation.

    PubMed

    Li, Jia Wei; Pan, Kuan Lun; Yu, Sheng Jen; Yan, Shaw Yi; Chang, Moo Been

    2014-12-01

    Mn(x)Ce(1)-(x)O(2) (x: 0.3-0.9) prepared by Pechini method was used as a catalyst for the thermal catalytic oxidation of formaldehyde (HCHO). At x=0.3 and 0.5, most of the manganese was incorporated in the fluorite structure of CeO(2) to form a solid solution. The catalytic activity was best at x=0.5, at which the temperature of 100% removal rate is the lowest (270°C). The temperature for 100% removal of HCHO oxidation is reduced by approximately 40°C by loading 5wt.% CuO(x) into Mn(0.5)Ce(0.5)O(2). With ozone catalytic oxidation, HCHO (61 ppm) in gas stream was completely oxidized by adding 506 ppm O₃over Mn(0.5)Ce(0.5)O(2) catalyst with a GHSV (gas hourly space velocity) of 10,000 hr⁻¹ at 25°C. The effect of the molar ratio of O(3) to HCHO was also investigated. As O(3)/HCHO ratio was increased from 3 to 8, the removal efficiency of HCHO was increased from 83.3% to 100%. With O(3)/HCHO ratio of 8, the mineralization efficiency of HCHO to CO(2) was 86.1%. At 25°C, the p-type oxide semiconductor (Mn(0.5)Ce(0.5)O(2)) exhibited an excellent ozone decomposition efficiency of 99.2%, which significantly exceeded that of n-type oxide semiconductors such as TiO(2), which had a low ozone decomposition efficiency (9.81%). At a GHSV of 10,000 hr⁻¹, [O(3)]/[HCHO]=3 and temperature of 25°C, a high HCHO removal efficiency (≥ 81.2%) was maintained throughout the durability test of 80 hr, indicating the long-term stability of the catalyst for HCHO removal. PMID:25499503

  16. Lipocalin 2 alleviates iron toxicity by facilitating hypoferremia of inflammation and limiting catalytic iron generation.

    PubMed

    Xiao, Xia; Yeoh, Beng San; Saha, Piu; Olvera, Rodrigo Aguilera; Singh, Vishal; Vijay-Kumar, Matam

    2016-06-01

    Iron is an essential transition metal ion for virtually all aerobic organisms, yet its dysregulation (iron overload or anemia) is a harbinger of many pathologic conditions. Hence, iron homeostasis is tightly regulated to prevent the generation of catalytic iron (CI) which can damage cellular biomolecules. In this study, we investigated the role of iron-binding/trafficking innate immune protein, lipocalin 2 (Lcn2, aka siderocalin) on iron and CI homeostasis using Lcn2 knockout (KO) mice and their WT littermates. Administration of iron either systemically or via dietary intake strikingly upregulated Lcn2 in the serum, urine, feces, and liver of WT mice. However, similarly-treated Lcn2KO mice displayed elevated CI, augmented lipid peroxidation and other indices of organ damage markers, implicating that Lcn2 responses may be protective against iron-induced toxicity. Herein, we also show a negative association between serum Lcn2 and CI in the murine model of dextran sodium sulfate (DSS)-induced colitis. The inability of DSS-treated Lcn2KO mice to elicit hypoferremic response to acute colitis, implicates the involvement of Lcn2 in iron homeostasis during inflammation. Using bone marrow chimeras, we further show that Lcn2 derived from both immune and non-immune cells participates in CI regulation. Remarkably, exogenous rec-Lcn2 supplementation suppressed CI levels in Lcn2KO serum and urine. Collectively, our results suggest that Lcn2 may facilitate hypoferremia, suppress CI generation and prevent iron-mediated adverse effects. PMID:27007712

  17. Catalytic liquid-phase oxidation of acetaldehyde to acetic acid over a Pt/CeO2-ZrO2-SnO2/γ-alumina catalyst.

    PubMed

    Choi, Pil-Gyu; Ohno, Takanobu; Masui, Toshiyuki; Imanaka, Nobuhito

    2015-10-01

    Pt/CeO2-ZrO2-SnO2/γ-Al2O3 catalysts were prepared by co-precipitation and wet impregnation methods for catalytic oxidation of acetaldehyde to acetic acid in water. In the present catalysts, Pt and CeO2-ZrO2-SnO2 were successfully dispersed on the γ-Al2O3 support. Dependences of platinum content and reaction time on the selective oxidation of acetaldehyde to acetic acid were investigated to optimize the reaction conditions for obtaining both high acetaldehyde conversion and highest selectivity to acetic acid. Among the catalysts, a Pt(6.4wt.%)/Ce0.68Zr0.17Sn0.15O2.0(16wt.%)/γ-Al2O3 catalyst showed the highest acetaldehyde oxidation activity. On this catalyst, acetaldehyde was completely oxidized after the reaction at 0°C for 8hr, and the selectivity to acetic acid reached to 95% and higher after the reaction for 4hr and longer. PMID:26456607

  18. SERCA mutant E309Q binds two Ca2+ ions but adopts a catalytically incompetent conformation

    PubMed Central

    Clausen, Johannes D; Bublitz, Maike; Arnou, Bertrand; Montigny, Cédric; Jaxel, Christine; Møller, Jesper Vuust; Nissen, Poul; Andersen, Jens Peter; le Maire, Marc

    2013-01-01

    The sarco(endo)plasmic reticulum Ca2+-ATPase (SERCA) couples ATP hydrolysis to transport of Ca2+. This directed energy transfer requires cross-talk between the two Ca2+ sites and the phosphorylation site over 50 Å distance. We have addressed the mechano-structural basis for this intramolecular signal by analysing the structure and the functional properties of SERCA mutant E309Q. Glu309 contributes to Ca2+ coordination at site II, and a consensus has been that E309Q only binds Ca2+ at site I. The crystal structure of E309Q in the presence of Ca2+ and an ATP analogue, however, reveals two occupied Ca2+ sites of a non-catalytic Ca2E1 state. Ca2+ is bound with micromolar affinity by both Ca2+ sites in E309Q, but without cooperativity. The Ca2+-bound mutant does phosphorylate from ATP, but at a very low maximal rate. Phosphorylation depends on the correct positioning of the A-domain, requiring a shift of transmembrane segment M1 into an ‘up and kinked position'. This transition is impaired in the E309Q mutant, most likely due to a lack of charge neutralization and altered hydrogen binding capacities at Ca2+ site II. PMID:24270570

  19. Numerical solution of 2D wet steam flow with non-equilibrium condensation and real thermodynamics

    SciTech Connect

    Hric, V.; Halama, J.

    2015-03-10

    An approach to modeling of wet steam flow with non-equilibrium condensation phenomenon is presented. The first part of our flow model is homogeneous Euler system of transport equations for mass, momentum and total energy of wet steam (mixture). The additional second part describes liquid phase via non-homogeneous system of transport equations for moments of droplets number distribution function and relies on corrected classical nucleation theory. Moment equations are closed by linearization of droplet growth rate model. All necessary relations for thermodynamic properties of steam are provided by IAPWS set of equations. However, properties of condensate are simply modeled by liquid saturation data. Two real equations of state are implemented. Recently developed CFD formulation for entropy (does not require iteration process) and so-called IAPWS special gas equation for Helmholtz energy (one iteration loop is necessary). Flow model is validated on converging-diverging supersonic nozzle with Barschdorff geometry. Simulations were performed by in-house CFD code based on finite volume method and stiff character of equations was solved by symmetrical time operator splitting. Achieved results satisfactorily agreed with experimental data.

  20. Refinery experiences with cracking in wet H/sub 2/S environments

    SciTech Connect

    Merrick, R.D.

    1988-01-01

    The inspection of pressure vessels in wet hydrogen sulfide environments with the sensitive wet fluorescent magnetic particle technique was conducted because this technique had detected cracking in other services not detected by more commonly used methods. The results of the inspections showed that cracks of significant size were present in --20% of the 189 vessels inspected. The cracking was primarily in the heat-affected zone (HAZ) of weldments or the shell plate adjacent to this area. Metallographic examination identified the cracking as sulfide stress cracking (SSC), stress-oriented hydrogen-induced cracking (SOHIC), and carbonate cracking. SOHIC and carbonate cracking in these refining process environments have not been previously reported. SSC leading to cracks of significant depth occurred at very small, hard areas in both the weld metal and adjacent HAZ that would not have been detected by the usual hardness measuring techniques used in vessel fabrication. Thermal stress relief appears to be an effective method of reducing the severity of cracking.

  1. Self catalytic growth of indium oxide (In2O3) nanowires by resistive thermal evaporation.

    PubMed

    Kumar, R Rakesh; Rao, K Narasimha; Rajanna, K; Phani, A R

    2014-07-01

    Self catalytic growth of Indium Oxide (In2O3) nanowires (NWs) have been grown by resistive thermal evaporation of Indium (In) in the presence of oxygen without use of any additional metal catalyst. Nanowires growth took place at low substrate temperature of 370-420 degrees C at an applied current of 180-200 A to the evaporation boat. Morphology, microstructures, and compositional studies of the grown nanowires were performed by employing field emission scanning electron microscopy (FESEM), X-Ray diffraction (XRD), transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS) respectively. Nanowires were uniformly grown over the entire Si substrate and each of the nanowire is capped with a catalyst particle at their end. X-ray diffraction study reveals the crystalline nature of the grown nanowires. Transmission electron microscopy study on the nanowires further confirmed the single crystalline nature of the nanowires. Energy dispersive X-ray analysis on the nanowires and capped nanoparticle confirmed that Indium act as catalyst for In2O3 nanowires growth. A self catalytic Vapor-Liquid-Solid (VLS) growth mechanism was responsible for the growth of In2O3 nanowires. Effect of oxygen partial pressure variation and variation of applied currents to the evaporation boat on the nanowires growth was systematically studied. These studies concluded that at oxygen partial pressure in the range of 4 x 10(-4), 6 x 10(-4) mbar at applied currents to the evaporation boat of 180-200 A were the best conditions for good nanowires growth. Finally, we observed another mode of VLS growth along with the standard VLS growth mode for In2O3 nanowires similar to the growth mechanism reported for GaAs nanowires. PMID:24758054

  2. Study on the mechanism of NH3-selective catalytic reduction over CuCe x Zr1-x /TiO2

    NASA Astrophysics Data System (ADS)

    Chen, Xujuan; Sun, Xiaoliang; Gong, Cairong; Lv, Gang; Song, Chonglin

    2016-03-01

    Copper-cerium-zirconium catalysts loaded on TiO2 prepared by a wet impregnation method were investigated for NH3-selective catalytic reduction (SCR) of NO x . The reaction mechanism was proposed on the basis of results from in situ diffuse reflectance infrared transform spectroscopy (DRIFT). When NH3 is introduced, ammonia bonded to Lewis acid sites is more stable over CuCe0.25Zr0.75/TiO2 at high temperature, while Brønsted acid sites are more important than Lewis acid sites at low temperature. For the NH3+NO+O2 co-adsorption, NH3 species occupy most of activity sites on CuCe0.25Zr0.75/TiO2 catalyst, and mainly exist in the forms of NH{4/+} (at low temperature) and NH3 coordinated (at high temperature), playing a crucial role in the NH3-SCR process. Two different reaction routes, the L-H mechanism at low temperature ( < 200°C) and the E-R mechanism at high temperature ( > 200°C), are presented for the SCR reaction over CuCe0.25Zr0.75/TiO2 catalyst.

  3. Study on the mechanism of NH3-selective catalytic reduction over CuCexZr1-x/TiO2

    NASA Astrophysics Data System (ADS)

    Chen, Xujuan; Sun, Xiaoliang; Gong, Cairong; Lv, Gang; Song, Chonglin

    2016-06-01

    Copper-cerium-zirconium catalysts loaded on TiO2 prepared by a wet impregnation method were investigated for NH3-selective catalytic reduction (SCR) of NOx. The reaction mechanism was proposed on the basis of results from in situ diffuse reflectance infrared transform spectroscopy (DRIFT). When NH3 is introduced, ammonia bonded to Lewis acid sites is more stable over CuCe0.25Zr0.75/TiO2 at high temperature, while Brønsted acid sites are more important than Lewis acid sites at low temperature. For the NH3+NO+O2 co-adsorption, NH3 species occupy most of activity sites on CuCe0.25Zr0.75/TiO2 catalyst, and mainly exist in the forms of NH4 + (at low temperature) and NH3 coordinated (at high temperature), playing a crucial role in the NH3-SCR process. Two different reaction routes, the L-H mechanism at low temperature (< 200°C) and the E-R mechanism at high temperature (> 200°C), are presented for the SCR reaction over CuCe0.25Zr0.75/TiO2 catalyst.

  4. Heterogeneous catalytic oxidation of As(III) on nonferrous metal oxides in the presence of H2O2.

    PubMed

    Kim, Dong-hyo; Bokare, Alok D; Koo, Min suk; Choi, Wonyong

    2015-03-17

    The oxidation of As(III) (arsenite) to As(V) (arsenate), a critical pretreatment process for total arsenic removal, is easily achieved using chemical oxidation methods. Hydrogen peroxide (H2O2) is widely used as an environmentally benign oxidant but its practical use for the arsenite oxidation is limited by the strong pH dependence and slow oxidation kinetics. This study demonstrated that H2O2-induced oxidation of As(III) can be markedly enhanced in the presence of nonferrous metal oxides (e.g., WO3, TiO2, ZrO2) as a heterogeneous catalyst working over a wide pH range in ambient reaction conditions. In particular, TiO2 is an ideal catalyst because it is not only active and stable but also easily available and inexpensive. Although the photocatalytic oxidation of As(III) on TiO2 was intensively studied, the thermal catalytic activities of TiO2 and other nonferrous metal oxides for the arsenic oxidation have been little investigated. The heterogeneous oxidation rate increased with increasing the TiO2 surface area and [H2O2] and weakly depended on pH whereas the homogeneous oxidation by H2O2 alone was favored only at alkaline condition. The oxidation rate in the TiO2/H2O2 system was not reduced at all in the absence of dioxygen. It was not retarded at all by OH radical scavengers but markedly inhibited by hydroperoxyl radical scavengers. It is proposed that the surface complexation of H2O2 on TiO2 induces the generation of the surface hydroperoxyl radical through an inner-sphere electron transfer, which subsequently reacts with As(III). The catalytic activity of TiO2 was maintained without showing any sign of deactivation. The heterogeneous catalytic oxidation is proposed as a viable method for the preoxidation treatment of As(III)-contaminated water under ambient conditions. PMID:25695481

  5. Wetting of mono and few-layered WS2 and MoS2 films supported on Si/SiO2 substrates.

    PubMed

    Chow, Philippe K; Singh, Eklavya; Viana, Bartolomeu Cruz; Gao, Jian; Luo, Jian; Li, Jing; Lin, Zhong; Elías, Ana L; Shi, Yunfeng; Wang, Zuankai; Terrones, Mauricio; Koratkar, Nikhil

    2015-03-24

    The recent interest and excitement in graphene has also opened up a pandora's box of other two-dimensional (2D) materials and material combinations which are now beginning to come to the fore. One family of these emerging 2D materials is transition metal dichalcogenides (TMDs). So far there is very limited understanding on the wetting behavior of "monolayer" TMD materials. In this study, we synthesized large-area, continuous monolayer tungsten disulfide (WS2) and molybdenum disulfide (MoS2) films on SiO2/Si substrates by the thermal reduction and sulfurization of WO3 and MO3 thin films. The monolayer TMD films displayed an advancing water contact angle of ∼83° as compared to ∼90° for the bulk material. We also prepared bilayer and trilayer WS2 films and studied the transition of the water contact angle with increasing number of layers. The advancing water contact angle increased to ∼85° for the bilayer and then to ∼90° for the trilayer film. Beyond three layers, there was no significant change in the measured water contact angle. This type of wetting transition indicates that water interacts to some extent with the underlying silica substrate through the monolayer TMD sheet. The experimentally observed wetting transition with numbers of TMD layers lies in-between the predictions of one continuum model that considers only van der Waals attractions and another model that considers only dipole-dipole interactions. We also explored wetting as a function of aging. A clean single-layer WS2 film (without airborne contaminants) was shown to be strongly hydrophilic with an advancing water contact angle of ∼70°. However, over time, the sample ages as hydrocarbons and water present in air adsorb onto the clean WS2 sheet. After ∼7 days, the aging process is completed and the advancing water contact angle of the aged single-layer WS2 film stabilizes at ∼83°. These results suggest that clean (i.e., nonaged) monolayer TMDs are hydrophilic materials. We further

  6. Single-step process to prepare CeO2 nanotubes with improved catalytic activity.

    PubMed

    González-Rovira, Leandro; Sánchez-Amaya, José M; López-Haro, Miguel; del Rio, Eloy; Hungría, Ana B; Midgley, Paul; Calvino, José J; Bernal, Serafín; Botana, F Javier

    2009-04-01

    CeO(2) nanotubes have been grown electrochemically using a porous alumina membrane as a template. The resulting material has been characterized by means of scanning electron microscopy (SEM), X-ray energy dispersive spectroscopy, high-angle annular dark-field scanning transmission electron microscopy tomography, high-resolution electron microscopy (HREM), and electron energy loss spectroscopy. According to SEM, the outer diameter of the nanotubes corresponds to the pore size (200 nm) of the alumina membrane, and their length ranges between 30 and 40 microm. HREM images have revealed that the width of the nanotube walls is about 6 nm. The catalytic activity of these novel materials for the CO oxidation reaction is compared to that of a polycrystalline powder CeO(2) sample prepared by a conventional route. The activity of the CeO(2) nanotubes is shown to be in the order of 400 times higher per gram of oxide at 200 degrees C (77.2 x 10(-2) cm(3) CO(2) (STP)/(gxs) for the nanotube-shaped CeO(2) and 0.16 x 10(-2) cm(3) CO(2) (STP)/(gxs) for the powder CeO(2)). PMID:19245236

  7. Bis(imidazolin-2-iminato) rare earth metal complexes: synthesis, structural characterization, and catalytic application.

    PubMed

    Trambitas, Alexandra G; Melcher, Daniel; Hartenstein, Larissa; Roesky, Peter W; Daniliuc, Constantin; Jones, Peter G; Tamm, Matthias

    2012-06-18

    Reaction of anhydrous rare earth metal halides MCl(3) with 2 equiv of 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-imine (Im(Dipp)NH) and 2 equiv of trimethylsilylmethyl lithium (Me(3)SiCH(2)Li) in THF furnished the complexes [(Im(Dipp)N)(2)MCl(THF)(n)] (M = Sc, Y, Lu). The molecular structures of all three compounds were established by single-crystal X-ray diffraction analyses. The coordination spheres around the pentacoordinate metal atoms are best described as trigonal bipyramids. Reaction of YbI(2) with 2 equiv of LiCH(2)SiMe(3) and 2 equiv of the imino ligand Im(Dipp)NH in tetrahydrofuran did not result in a divalent complex, but instead the Yb(III) complex [(Im(Dipp)N)(2)YbI(THF)(2)] was obtained and structurally characterized. Treatment of [(Im(Dipp)N)(2)MCl(THF)(n)] with 1 equiv of LiCH(2)SiMe(3) resulted in the formation of [(Im(Dipp)N)(2)M(CH(2)SiMe(3))(THF)(n)]. The coordination arrangement of these compounds in the solid state at the metal atoms is similar to that found for the starting materials, although the introduction of the neosilyl ligand induces a significantly greater distortion from the ideal trigonal-bipyramidal geometry. [(Im(Dipp)N)(2)Y(CH(2)SiMe(3))(THF)(2)] was used as precatalyst in the intramolecular hydroamination/cyclization reaction of various terminal aminoalkenes and of one aminoalkyne. The complex showed high catalytic activity and selectivity. A comparison with the previously reported dialkyl yttrium complex [(Im(Dipp)N)Y(CH(2)SiMe(3))(2)(THF)(3)] showed no clear tendency in terms of activity. PMID:22662762

  8. IDENTIFICATION AND RESPONSES TO POTENTIAL EFFECTS OF SCR AND WET SCRUBBERS ON SUBMICRON PARTICULATE EMISSIONS AND PLUME CHARACTERISTICS

    EPA Science Inventory

    Applications of selective catalytic reduction (SCR) systems and wet flue gas desulfurization (FGD) scrubbers on coal-fired boilers have led to substantial reductions in emissions of nitrogen oxides (NOX) and sulfur dioxide (SO2). However, observations of pilot- and full-scale tes...

  9. High NO2/NOx emissions downstream of the catalytic diesel particulate filter: An influencing factor study.

    PubMed

    He, Chao; Li, Jiaqiang; Ma, Zhilei; Tan, Jianwei; Zhao, Longqing

    2015-09-01

    Diesel vehicles are responsible for most of the traffic-related nitrogen oxide (NOx) emissions, including nitric oxide (NO) and nitrogen dioxide (NO2). The use of after-treatment devices increases the risk of high NO2/NOx emissions from diesel engines. In order to investigate the factors influencing NO2/NOx emissions, an emission experiment was carried out on a high pressure common-rail, turbocharged diesel engine with a catalytic diesel particulate filter (CDPF). NO2 was measured by a non-dispersive ultraviolet analyzer with raw exhaust sampling. The experimental results show that the NO2/NOx ratios downstream of the CDPF range around 20%-83%, which are significantly higher than those upstream of the CDPF. The exhaust temperature is a decisive factor influencing the NO2/NOx emissions. The maximum NO2/NOx emission appears at the exhaust temperature of 350°C. The space velocity, engine-out PM/NOx ratio (mass based) and CO conversion ratio are secondary factors. At a constant exhaust temperature, the NO2/NOx emissions decreased with increasing space velocity and engine-out PM/NOx ratio. When the CO conversion ratios range from 80% to 90%, the NO2/NOx emissions remain at a high level. PMID:26354692

  10. Synergistic Ion-Binding Catalysis Demonstrated via an Enantioselective, Catalytic [2,3]-Wittig Rearrangement

    PubMed Central

    2016-01-01

    Sigmatropic rearrangements number among the most powerful complexity-building transformations in organic synthesis but have remained largely insensitive to enantioselective catalysis due to the diffuse nature of their transition structures. Here, we describe a synergistic ion-binding strategy for asymmetric catalysis of anionic sigmatropic rearrangements. This approach is demonstrated with the enantioselective [2,3]-Wittig rearrangement of α-allyloxy carbonyl compounds to afford highly enantioenriched homoallylic alcohol products. Chiral thiourea catalysts are shown to engage reactive anions and their countercations through a cooperative set of attractive, noncovalent interactions. Catalyst structure–reactivity–selectivity relationship studies and computational analyses provide insight into catalyst–substrate interactions responsible for enantioinduction and allude to the potential generality of this catalytic strategy. PMID:27413786