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Sample records for solid acid catalyst

  1. Phosphorylated Mesoporous Carbon as a Solid Acid Catalyst

    SciTech Connect

    Dai, Sheng; Mayes, Richard T; Fulvio, Pasquale F; Ma, Zhen

    2011-01-01

    Mesoporous carbon catalyst supports are attractive due to their wide chemical stability while potentially increasing masstransport through and providing a path for larger molecules to access catalytic sites. Herein we report the synthesis of a 10 phosphorylated mesoporous carbon solid-acid catalyst characterized by NH3-TPD and isopropanol dehydration.

  2. Starch saccharification by carbon-based solid acid catalyst

    NASA Astrophysics Data System (ADS)

    Yamaguchi, Daizo; Hara, Michikazu

    2010-06-01

    The hydrolysis of cornstarch using a highly active solid acid catalyst, a carbon material bearing SO 3H, COOH and OH groups, was investigated at 353-393 K through an analysis of variance (ANOVA) and an artificial neural network (ANN). ANOVA revealed that reaction temperature and time are significant parameters for the catalytic hydrolysis of starch. The ANN model indicated that the reaction efficiency reaches a maximum at an optimal condition (water, 0.8-1.0 mL; starch, 0.3-0.4 g; catalyst, 0.3 g; reaction temperature, 373 K; reaction time, 3 h). The relationship between the reaction and these parameters is discussed on the basis of the reaction mechanism.

  3. n-hydrocarbons conversions over metal-modified solid acid catalysts

    NASA Astrophysics Data System (ADS)

    Zarubica, A.; Ran?elovi?, M.; Mom?ilovi?, M.; Radulovi?, N.; Putanov, P.

    2013-12-01

    The quality of a straight-run fuel oil can be improved if saturated n-hydrocarbons of low octane number are converted to their branched counterparts. Poor reactivity of traditional catalysts in isomerization reactions imposed the need for the development of new catalysts among which noble metal promoted acid catalysts, liquid and/or solid acid catalysts take a prominent place. Sulfated zirconia and metal promoted sulfated zirconia exhibit high activity for the isomerization of light alkanes at low temperatures. The present paper highlights the original results which indicate that the modification of sulfated zirconia by incorporation of metals (platinum and rhenium) significantly affects catalytic performances in n-hydrocarbon conversion reactions. Favourable activity/selectivity of the promoted sulfated zirconia depends on the crystal phase composition, critical crystallites sizes, platinum dispersion, total acidity and type of acidity. Attention is also paid to the recently developed solid acid catalysts used in other conversion reactions of hydrocarbons.

  4. Application of Supercritical Fluids to Solid Acid Catalyst Alkylation and Regeneration

    SciTech Connect

    Lucia M. Petkovic; Daniel M. Ginosar; David N. Thompson; Kyle C. Burch

    2007-05-01

    Supercritical fluid (SCF) regeneration is a promising alternative method for regenerating solid catalysts deactivated by carbonaceous deposits. The unique solvent and transport properties of SCFs such as solvent strength similar to liquids and transport properties similar to gases make them highly suitable for extraction of fouling materials from porous heterogeneous catalysts. A brief review of the research work performed at the Idaho National Laboratory (INL) on the application of supercritical fluids to both isobutane/butene alkylation reaction and solid acid catalyst regeneration is presented in this contribution.

  5. A microalgae residue based carbon solid acid catalyst for biodiesel production.

    PubMed

    Fu, Xiaobo; Li, Dianhong; Chen, Jie; Zhang, Yuanming; Huang, Weiya; Zhu, Yi; Yang, Jun; Zhang, Chengwu

    2013-10-01

    Biodiesel production from microalgae is recognized as one of the best solutions to deal with the energy crisis issues. However, after the oil extraction from the microalgae, the microalgae residue was generally discarded or burned. Here a novel carbon-based solid acid catalyst derived from microalgae residue by in situ hydrothermal partially carbonization were synthesized. The obtained catalyst was characterized and subjected to both the esterification of oleic acid and transesterification of triglyceride to produce biodiesel. The catalyst showed high catalytic activity and can be regenerated while its activity can be well maintained after five cycles. PMID:23953130

  6. Preparation and characterization of biomass carbon-based solid acid catalyst for the esterification of oleic acid with methanol.

    PubMed

    Liu, Tiantian; Li, Zhilong; Li, Wei; Shi, Congjiao; Wang, Yun

    2013-04-01

    A solid acid catalyst, prepared by sulfonating carbonized corn straw, was proved to be an efficient and environmental benign catalyst for the esterification of oleic acid and methanol. Various synthetic parameters, such as carbonization temperature and time were systematically examined. It was found that the catalyst exhibited the highest acid density of 2.64 mmol/g by NaOH titration. A quantitative yield (98%) of ester was achieved, using the most active sulfonated catalyst at 333 K with a 7 wt.% catalyst/oleic acid ratio for 4h, at a 7:1 M ratio of methanol/oleic acid, while the commercial available Amberlyst-15 only gave 85% yield under the same reaction condition. PMID:23453798

  7. Alkene Isomerization Using a Solid Acid as Activator and Support for a Homogeneous Catalyst

    ERIC Educational Resources Information Center

    Seen, Andrew J.

    2004-01-01

    An upper-level undergraduate experiment that, in addition to introducing students to catalysis using an air sensitive transition-metal complex, introduces the use of a solid acid as an activator and support for the catalyst is developed. The increased stability acquired in the course of the process affords the opportunity to characterize the…

  8. Selective hydrolysis of hemicellulose from wheat straw by a nanoscale solid acid catalyst.

    PubMed

    Zhong, Chao; Wang, Chunming; Huang, Fan; Wang, Fengxue; Jia, Honghua; Zhou, Hua; Wei, Ping

    2015-10-20

    A nanoscale catalyst, solid acid SO4(2-)/Fe2O3 with both Lewis and Brønsted acidity was found to effectively hydrolyze hemicellulose while keeping cellulose and lignin inactive, and selective hydrolysis of hemicellulose from wheat straw by this catalyst was also confirmed. The factors that significantly affected hydrolysis process were investigated with response surface methodology, and the optimum conditions for time, temperature, and ratio of wheat straw to catalyst (w/w) were calculated to be 4.10h, 141.97°C, and 1.95:1, respectively. A maximum hemicellulose hydrolysis yield of 63.5% from wheat straw could be obtained under these conditions. In addition, the catalyst could be recycled six times with high activity remaining. PMID:26256198

  9. Conversion of spent solid phosphoric Acid catalyst to environmentally friendly fertilizer.

    PubMed

    Merwe, Werner van der

    2010-03-01

    Solid phosphoric acid (SPA) catalysts are widely used in the petroleum industry. Despite a high phosphorus content the spent catalyst is generally not reused. Moreover, due to the limited life spans that are achieved industrially, large quantities of spent catalyst requires disposal, often by landfill. SPA can be readily converted to fertilizer, but the presence of carbonaceous deposits on the catalyst presents a potential environmental hazard. This work demonstrates that these deposits are mostly polyaromatic (amorphous carbon) with smaller amounts of oxygenates and aliphatics. Neither the chemical makeup nor the physical structure of the catalyst or the presence of coke precludes it from use as fertilizer. Subsequently, the spent catalyst was milled, neutralized with lime and ammonium hydroxide, and then calcined to yield a phosphate-rich fertilizer. Toxicity characteristic leaching tests of the spent catalyst fertilizer showed low levels of metals and organics, establishing that no harmful compounds are likely to be absorbed into plant life or groundwater. A plant growth study of the spent catalyst fertilizer indicated that it is approximately as effective as superphosphate fertilizer when used in alkaline soil. The spent catalyst fertilizer is environmentally benign and economically efficient. PMID:20146419

  10. Hydrolysis of biomass using a reusable solid carbon acid catalyst and fermentation of the catalytic hydrolysate to ethanol.

    PubMed

    Goswami, Mandavi; Meena, S; Navatha, S; Prasanna Rani, K N; Pandey, Ashok; Sukumaran, Rajeev Kumar; Prasad, R B N; Prabhavathi Devi, B L A

    2015-01-01

    Solid acid catalysts can hydrolyze cellulose with lower reaction times and are easy to recover and reuse. A glycerol based carbon acid catalyst developed at CSIR-IICT performed well in acid catalysis reactions and hence this study was undertaken to evaluate the catalyst for hydrolysis of biomass (alkali pretreated or native rice straw). The catalyst could release 262 mg/g total reducing sugars (TRS) in 4h at 140 °C from alkali pretreated rice straw, and more importantly it released 147 mg/g TRS from native biomass. Reusability of the catalyst was also demonstrated. Catalytic hydrolysate was used as sugar source for fermentation to produce ethanol. Results indicate the solid acid catalyst as an interesting option for biomass hydrolysis. PMID:25777067

  11. Preparation and application of zirconium sulfate supported on SAPO-34 molecular sieve as solid acid catalyst for esterification

    SciTech Connect

    Xu, Dongyan Ma, Hong; Cheng, Fei

    2014-05-01

    Graphical abstract: - Highlights: • SAPO-34 supported zirconium sulfate solid acid catalyst was prepared. • Esterification of acetic acid with ethanol can be catalyzed by ZS/SAPO-34. • The hydration of ZS is vital to the acidic property and catalytic performance. • The ZS/SAPO-34 catalyst treated at 200 °C shows good reusability. - Abstract: Zirconium sulfate (ZS) was supported on SAPO-34 molecular sieve by using an incipient wetness impregnation method with zirconium sulfate as the precursor. The as-prepared catalysts were used as solid acid catalyst for esterification reaction of acetic acid with ethanol. The influence of calcination temperature on the acidic property, catalytic activity, and reusability of ZS/SAPO-34 catalysts were mainly investigated. FT-IR, SEM, EDS and TG analysis have been carried out to demonstrate the characteristics of ZS/SAPO-34 catalysts. It was found that the 30 wt%ZS/SAPO-34 catalysts display the property of superacid irrespective of calcination temperature. The ZS/SAPO-34 catalyst treated at 200 °C can enhance the interaction between the supported ZS and SAPO-34 and keep the catalyst remaining substantially active after several reaction cycles. However, further increasing calcination temperature will cause the transfer of ZS from hydrate to anhydrous phase, and thus the decrease of activity.

  12. Catalytic hydrothermal pretreatment of corncob into xylose and furfural via solid acid catalyst.

    PubMed

    Li, Huiling; Deng, Aojie; Ren, Junli; Liu, Changyu; Lu, Qi; Zhong, Linjie; Peng, Feng; Sun, Runcang

    2014-04-01

    Selectively catalytic hydrothermal pretreatment of corncob into xylose and furfural has been developed in this work using solid acid catalyst (SO4(2-)/TiO2-ZrO2/La(3+)). The effects of corncob-to-water ratio, reaction temperature and residence time on the performance of catalytic hydrothermal pretreatment were investigated. Results showed that the solid residues contained mainly lignin and cellulose, which was indicative of the efficient removal of hemicelluloses from corncob by hydrothermal method. The prepared catalyst with high thermal stability and strong acid sites originated from the acid functional groups was confirmed to contribute to the hydrolysis of polysaccharides into monosaccharides followed by dehydration into furfural. Highest furfural yield (6.18 g/100g) could be obtained at 180°C for 120 min with 6.80 g/100g xylose yield when the corncob/water ratio of was 10:100. Therefore, selectively catalytic hydrothermal pretreatment of lignocellulosic biomass into important platform chemicals by solid acids is considered to be a potential treatment for biodiesel and chemical production. PMID:24632409

  13. Monodispersed Hollow SO3H-Functionalized Carbon/Silica as Efficient Solid Acid Catalyst for Esterification of Oleic Acid.

    PubMed

    Wang, Yang; Wang, Ding; Tan, Minghui; Jiang, Bo; Zheng, Jingtang; Tsubaki, Noritatsu; Wu, Mingbo

    2015-12-01

    SO3H-functionalized monodispersed hollow carbon/silica spheres (HS/C-SO3H) with primary mesopores were prepared with polystyrene as a template and p-toluenesulfonic acid (TsOH) as a carbon precursor and -SO3H source simultaneously. The physical and chemical properties of HS/C-SO3H were characterized by N2 adsorption, TEM, SEM, XPS, XRD, Raman spectrum, NH3-TPD, element analysis and acid-base titration techniques. As a solid acid catalyst, HS/C-SO3H shows excellent performance in the esterification of oleic acid with methanol, which is a crucial reaction in biodiesel production. The well-defined hollow architecture and enhanced active sites accessibility of HS/C-SO3H guarantee the highest catalytic performance compared with the catalysts prepared by activation of TsOH deposited on the ordered mesoporous silicas SBA-15 and MCM-41. At the optimized conditions, high conversion (96.9%) was achieved and no distinct activity drop was observed after 5 recycles. This synthesis strategy will provide a highly effective solid acid catalyst for green chemical processes. PMID:26588826

  14. Sulfonated mesoporous silica-carbon composites and their use as solid acid catalysts

    NASA Astrophysics Data System (ADS)

    Valle-Vigón, Patricia; Sevilla, Marta; Fuertes, Antonio B.

    2012-11-01

    The synthesis of highly functionalized porous silica-carbon composites made up of sulfonic groups attached to a carbon layer coating the pores of three types of mesostructured silica (i.e. SBA-15, KIT-6 and mesocellular silica) is presented. The synthesis procedure involves the following steps: (a) removal of the surfactant, (b) impregnation of the silica pores with a carbon precursor, (c) carbonization and (d) sulfonation. The resulting silica-carbon composites contain ˜30 wt % of carbonaceous matter with a high density of acidic groups attached to the deposited carbon (i.e.sbnd SO3H, sbnd COOH and sbnd OH). The structural characteristics of the parent silica are retained in the composite materials, which exhibit a high surface area, a large pore volume and a well-ordered porosity made up uniform mesopores. The high density of the sulfonic groups in combination with the mesoporous structure of the composites ensures that a large number of active sites are easily accessible to reactants. These sulfonated silica-carbon composites behave as eco-friendly, active, selective, water tolerant and recyclable solid acids. In this study we demonstrate the usefulness of these composites as solid acid catalysts for the esterification of maleic anhydride, succinic acid and oleic acid with ethanol. These composites exhibit a superior intrinsic catalytic activity to other commercial solid acids such as Amberlyst-15.

  15. The Origin of Regioselectivity in 2-butanol Dehydration on Solid Acid Catalysts

    SciTech Connect

    Kwak, Ja Hun; Rousseau, Roger J.; Mei, Donghai; Peden, Charles HF; Szanyi, Janos

    2011-10-17

    The origin in the variations of trans-/cis-2-butene product selectivity ratios in 2-butanol dehydration over solid acid catalysts were investigated using a combined experimental-theory approach. Reactivity measurements over ?-Al2O3, AlOx/SBA-15, and H-form zeolites with widely varying Si/Al ratios and pore structures showed over two orders of magnitude change in the trans-/cis-2-butene product ratio. Activation energy barriers calculated for the concerted C-O and ?-C-H bond breakings of adsorbed butoxy intermediates by dispersion-corrected DFT calculations correctly predicted the trans-/cis-2-butene product ratio observed on ?-Al2O3. The very low trans-2-butene selectivity on ?-Al2O3 can now be understood by the formation of a late transition state with high energy barrier caused by the strong van der Waals interaction between the ?-H atoms and the flat catalyst surface. Decreasing the dispersive attractive force between the adsorbed butoxide and the surface (e.g., by moving it further away from the support surface in AlOx/SBA-15) leads to almost equimolar formation of the trans- and cis-2-butene isomers. Trans-/cis-2-butene selectivity ratios much higher than that dictated by thermodynamic equilibrium can be achieved by introducing additional geometric constraints around the active catalytic site (e.g., varying the 3D environment around the active center in zeolites). We propose a model to explain the widely varying trans-/cis-2-butene selectivity in 2-butanol dehydration over solid acid catalysts that is consistent with the experimental results in this study. A key outcome of the study is the realization that van der Waals interactions between the reactant and the active catalyst surface must be included in the theoretic models in order to be able to accurately predict product selectivities. This information, in turn, significantly advances our ability to develop catalyst materials with designed active centers in order to achieve desired regioselectivities.

  16. Solid acid catalysts pretreatment and enzymatic hydrolysis of macroalgae cellulosic residue for the production of bioethanol.

    PubMed

    Tan, Inn Shi; Lee, Keat Teong

    2015-06-25

    The aim of this study is to investigate the technical feasibility of converting macroalgae cellulosic residue (MCR) into bioethanol. An attempt was made to present a novel, environmental friendly and economical pretreatment process that enhances enzymatic conversion of MCR to sugars using Dowex (TM) Dr-G8 as catalyst. The optimum yield of glucose reached 99.8% under the optimal condition for solid acid pretreatment (10%, w/v biomass loading, 4%, w/v catalyst loading, 30min, 120°C) followed by enzymatic hydrolysis (45FPU/g of cellulase, 52CBU/g of ?-glucosidase, 50°C, pH 4.8, 30h). The yield of sugar obtained was found more superior than conventional pretreatment process using H2SO4 and NaOH. Biomass loading for the subsequent simultaneous saccharification and fermentation (SSF) of the pretreated MCR was then optimized, giving an optimum bioethanol yield of 81.5%. The catalyst was separated and reused for six times, with only a slight drop in glucose yield. PMID:25839825

  17. Production of 5-hydroxymethylfurfural from corn stalk catalyzed by corn stalk-derived carbonaceous solid acid catalyst.

    PubMed

    Yan, Lulu; Liu, Nian; Wang, Yu; Machida, Hiroshi; Qi, Xinhua

    2014-12-01

    A carbonaceous solid acid was prepared by hydrothermal carbonization of corn stalk followed by sulfonation and was characterized by FT-IR, XRD, SEM and elemental analysis techniques. The as-prepared corn stalk-derived carbonaceous solid acid catalyst contained SO3H, COOH, and phenolic OH groups, and was used for the one-step conversion of intact corn stalk to 5-hydroxymethylfurfural (5-HMF) in the ionic liquid 1-butyl-3-methyl imidazolium chloride ([BMIM][Cl]), where a 5-HMF yield of 44.1% was achieved at 150 °C in 30 min reaction time. The catalytic system was applicable to initial corn stalk concentration of up to ca. 10 wt.% for the production of 5-HMF. The synthesized catalyst and the developed process of using corn stalk-derived carbon catalyst for corn stalk conversion provide a green and efficient strategy for crude biomass utilization. PMID:25444888

  18. Synthesis of a Sulfonated Two-Dimensional Covalent Organic Framework as an Efficient Solid Acid Catalyst for Biobased Chemical Conversion.

    PubMed

    Peng, Yongwu; Hu, Zhigang; Gao, Yongjun; Yuan, Daqiang; Kang, Zixi; Qian, Yuhong; Yan, Ning; Zhao, Dan

    2015-10-01

    Because of limited framework stability tolerance, de?novo synthesis of sulfonated covalent organic frameworks (COFs) remains challenging and unexplored. Herein, a sulfonated two-dimensional crystalline COF, termed TFP-DABA, was synthesized directly from 1,3,5-triformylphloroglucinol and 2,5-diaminobenzenesulfonic acid through a previously reported Schiff base condensation reaction, followed by irreversible enol-to-keto tautomerization, which strengthened its structural stability. TFP-DABA is a highly efficient solid acid catalyst for fructose conversion with remarkable yields (97?% for 5-hydroxymethylfurfural and 65?% for 2,5-diformylfuran), good chemoselectivity, and good recyclability. The present study sheds light on the de?novo synthesis of sulfonated COFs as novel solid acid catalysts for biobased chemical conversion. PMID:26448524

  19. Oil palm trunk and sugarcane bagasse derived solid acid catalysts for rapid esterification of fatty acids and moisture-assisted transesterification of oils under pseudo-infinite methanol.

    PubMed

    Ezebor, Francis; Khairuddean, Melati; Abdullah, Ahmad Zuhairi; Boey, Peng Lim

    2014-04-01

    The use of pseudo-infinite methanol in increasing the rate of esterification and transesterification reactions was studied using oil palm trunk (OPT) and sugarcane bagasse (SCB) derived solid acid catalysts. The catalysts were prepared by incomplete carbonisation at 400°C for 8h, followed by sulfonation at 150°C for 15h and characterised using TGA/DTA, XRD, FT-IR, SEM-EDS, EA and titrimetric determinations of acid sites. Under optimal reaction conditions, the process demonstrated rapid esterification of palmitic acid, with FAME yields of 93% and 94% in 45min for OPT and SCB catalysts, respectively. With the process, moisture levels up to 16.7% accelerated the conversion of low FFA oils by sulfonated carbon catalysts, through moisture-induced violent bumping. Moisture assisted transesterification of palm olein containing 1.78% FFA and 8.33% added water gave FAME yield of 90% in 10h, which was two folds over neat oil. PMID:24561631

  20. Conversion of polar and non-polar algae oil lipids to fatty acid methyl esters with solid acid catalysts--A model compound study.

    PubMed

    Asikainen, Martta; Munter, Tony; Linnekoski, Juha

    2015-09-01

    Bio-based fuels are becoming more and more important due to the depleting fossil resources. The production of biodiesel from algae oil is challenging compared to terrestrial vegetable oils, as algae oil consists of polar fatty acids, such as phospholipids and glycolipids, as well as non-polar triglycerides and free fatty acids common in vegetable oils. It is shown that a single sulphonated solid acid catalyst can perform the esterification and transesterification reactions of both polar and non-polar lipids. In mild reaction conditions (60-70 °C) Nafion NR50 catalyst produces methyl palmitate (FAME) from the palmitic acid derivatives of di-, and tri-glyceride, free fatty acid, and phospholipid with over 80% yields, with the glycolipid derivative giving nearly 40% yields of FAME. These results demonstrate how the polar and non-polar lipid derivatives of algal oil can be utilised as feedstocks for biodiesel production with a single catalyst in one reaction step. PMID:26004380

  1. Sulfuric acid functional zirconium (or aluminum) incorporated mesoporous MCM-48 solid acid catalysts for alkylation of phenol with tert-butyl alcohol

    NASA Astrophysics Data System (ADS)

    Jiang, Tingshun; Cheng, Jinlian; Liu, Wangping; Fu, Lie; Zhou, Xuping; Zhao, Qian; Yin, Hengbo

    2014-10-01

    Several zirconium (or aluminum) incorporated mesoporous MCM-48 solid acid catalysts (SO42-/Zr-MCM-48 and SO42-/Al-MCM-48) were prepared by the impregnation method and their physicochemical properties were characterized by means of XRD, FT-IR, TEM, NH3-TPD and N2 physical adsorption. Also, the catalytic activities of these solid acid catalysts were evaluated by the alkylation of phenol with tert-butyl alcohol. The effect of weight hour space velocity (WHSV), reaction time and reaction temperature on catalytic properties was also studied. The results show that the SO42-/Zr-MCM-48 and SO42-/Al-MCM-48 still have good mesoporous structure and long range ordering. Compared with the Zr (or Al)-MCM-48 samples, SO42-/Zr-MCM-48 and SO42-/Al-MCM-48 solid acid catalysts have strong acidity and exhibit high activities in alkylation reaction of phenol with tert-butyl alcohol. The SO42-/Zr-MCM-48-25 (molar ratio of Si/Zr=0.04) catalyst was found to be the most promising and gave the highest phenol conversion among all catalysts. A maximum phenol conversion of 91.6% with 4-tert-butyl phenol (4-TBP) selectivity of 81.8% was achieved when the molar ratio of tert-butyl alcohol:phenol is 2:1, reaction time is 2 h, the WHSV is 2 h-1 and the reaction temperature is 140 °C.

  2. A highly efficient magnetic solid acid catalyst for synthesis of 2,4,5-trisubstituted imidazoles under ultrasound irradiation.

    PubMed

    Safari, Javad; Zarnegar, Zohre

    2013-03-01

    Fe(3)O(4) nanoparticles were prepared by chemical coprecipitation method and subsequently coated with 3-aminopropyltriethoxysilane (APTES) via silanization reaction. Grafting of chlorosulfuric acid on the amino-functionalized Fe(3)O(4) nanoparticles afforded sulfamic acid-functionalized magnetic nanoparticles (SA-MNPs). SA-MNPs was found to be a mild and effective solid acid catalyst for the efficient, one-pot, three-component synthesis of 2,4,5-trisubstituted imidazoles under ultrasound irradiation. This protocol afforded corresponding imidazoles in shorter reaction durations, and in high yields. This green procedure has many obvious advantages compared to those reported in the previous literatures, including avoiding the use of harmful catalysts, easy and quick isolation of the products, excellent yields, short routine, and simplicity of the methodology. PMID:23137656

  3. Synthesis and characterization of sulfonated single-walled carbon nanotubes and their performance as solid acid catalyst

    SciTech Connect

    Yu Hao Jin Yuguang; Li Zhili; Peng Feng Wang Hongjuan

    2008-03-15

    Single-walled carbon nanotubes (SWCNTs) were treated with sulfuric acid at 300 deg. C to synthesize sulfonated SWCNTs (s-SWCNTs), which were characterized by electron microscopy, infrared, Raman and X-ray photoelectron spectroscopy, and thermo analysis. Compared with activated carbon, more sulfonic acid groups can be introduced onto the surfaces of SWCNTs. The high degree ({approx}20 wt%) of surface sulfonation led to hydrophilic sidewalls that allows the SWCNTs to be uniformly dispersed in water and organic solvents. The high surface acidity of s-SWCNTs was demonstrated by NH{sub 3} temperature-programmed desorption technique and tested by an acetic acid esterification reaction catalyzed by s-SWCNTs. The results show that the water-dispersive s-SWCNTs are an excellent solid acid catalyst and demonstrate the potential of SWCNTs in catalysis applications. - Graphical abstract: Sulfonated SWCNTs with 20 wt% -SO{sub 2}OH groups were prepared by a high-temperature H{sub 2}SO{sub 4} process, which transformed the hydrophobic surface of pristine SWCNTs to a hydrophilic surface and provided an excellent performance as solid acid catalyst.

  4. Biodiesel production in a membrane reactor using MCM-41 supported solid acid catalyst.

    PubMed

    Xu, Wei; Gao, Lijing; Wang, Songcheng; Xiao, Guomin

    2014-05-01

    Production of biodiesel from the transesterification between soybean oil and methanol was conducted in this study by a membrane reactor, in which ceramic membrane was packed with MCM-41 supported p-toluenesulfonic acid (PTSA). Box-Behnken design and response surface methodology (RSM) were used to investigate the effects of reaction temperature, catalyst amount and circulation velocity on the yield of biodiesel. A reduced cubic model was developed to navigate the design space. Reaction temperature was found to have most significant effect on the biodiesel yield while the interaction of catalyst amount and circulation velocity have minor effect on it. 80°C of reaction temperature, 0.27 g/cm(3) of catalyst amount and 4.15 mL/min of circulation velocity were proved to be the optimum conditions to achieve the highest biodiesel yield. PMID:24657760

  5. Reactions of aqueous glucose solution over solid-acid Y-zeolite catalyst at 110-160 C

    SciTech Connect

    Lourvanij, K.; Rorrer, G.L. )

    1993-01-01

    Reactions of glucose with solid-acid Y-zeolite catalyst were studied to see if this heterogeneous system could produce oxygenated hydrocarbons by shape-selective, acid-catalyzed processes at fairly low temperatures. Experimentally, aqueous solutions of glucose (12 wt %) were reacted with HY-zeolite powder in a well-mixed batch reactor at temperatures ranging from 110 to 160 C and catalyst concentrations ranging from 2 to 20 g/150 ml. Unreacted glucose and oxygenated hydrocarbon products were measured by HPLC as a function of reaction time (0-24 h) and process conditions. Glucose conversions of 100% were obtained at 160 C after an 8-h reaction time. The apparent activation energy based on glucose conversion was 23.25 [plus minus] 0.40 kcal/mol. Several acid-catalyzed reactions were identified, including isomerization of glucose to fructose, partial dehydration of glucose to 5-(hydroxymethyl)furfural (HMF), rehydration and cleavage of HMF to formic acid and 4-oxo-pentanoic acid, and carbonization . Polymers of HMF and seven minor additional products in the lower molecular weight organic acids/aldehydes/ketones elution range were also isolated by HPLC. High yields of organic acids relative to HMF and lowered selectivity of HMF in the bulk phase relative to the homogeneous acid-catalyzed reaction suggests the possibility of molecular sieving reactions within the Y-zeolite in addition to reactions on the outer surface of the Y-zeolite particle.

  6. Low-quality vegetable oils as feedstock for biodiesel production using K-pumice as solid catalyst. Tolerance of water and free fatty acids contents.

    PubMed

    Díaz, L; Borges, M E

    2012-08-15

    Waste oils are a promising alternative feedstock for biodiesel production due to the decrease of the industrial production costs. However, feedstock with high free fatty acids (FFA) content presents several drawbacks when alkaline-catalyzed transesterification reaction is employed in biodiesel production process. Nowadays, to develop suitable processes capable of treating oils with high free fatty acids content, a two-step process for biodiesel production is being investigated. The major problem that it presents is that two catalysts are needed to carry out the whole process: an acidic catalyst for free fatty acids esterification (first step) and a basic catalyst for pretreated product transesterification (second step). The use of a bifunctional catalyst, which allows both reactions to take place simultaneously, could minimize the production costs and time. In the present study, the behavior of pumice, a natural volcanic material used as a heterogeneous catalyst, was tested using oils with several FFA and water contents as feedstock in the transesterification reaction to produce biodiesel. Pumice as a bifunctional solid catalyst, which can catalyze simultaneously the esterification of FFA and the transesterification of fatty acid glycerides into biodiesel, was shown to be an efficient catalyst for the conversion of low-grade, nonedible oil feedstock into biodiesel product. Using this solid catalyst for the transesterification reaction, high FAME yields were achieved when feedstock oils presented a FFA content until approximately 2% wt/wt and a water content until 2% wt/wt. PMID:22799882

  7. Solid acids as catalysts for the conversion of D-xylose, xylan and lignocellulosics into furfural in ionic liquid.

    PubMed

    Zhang, Luxin; Yu, Hongbing; Wang, Pan

    2013-05-01

    With the aim to develop an ecologically viable catalytic pathway for furfural production without the use of inorganic acids, H3PW12O40, Amberlyst-5 and NKC-9 (macroporous styrene-based sulfonic acid resin) were used as catalysts for producing furfural from xylose, xylan and lignocellulosic biomass in [BMIM]Cl under microwave irradiation at atmospheric pressure. A surprisingly high furfural yield of 93.7% from xylan was obtained by H3PW12O40 at 160 °C in 10 min. The degradation of furfural affected by single addition of [BMIM]Cl and solid acids was also investigated. The IL could be easily recycled and reused with stable solvent capacity for multiple runs (5×) after the product furfural was extracted with ethyl acetate. PMID:23567725

  8. Functional assessment of the strength of solid acid catalysts Josef Macht, Robert T. Carr, Enrique Iglesia *

    E-print Network

    Iglesia, Enrique

    prevalent during dehydration catalysis. These effects of reaction media (and treatment protocols) reflect dehydration n-Hexane isomerization Sulfated zirconia Tunstated zirconia Perfluorosulfonic acid resins for dehydration and isomerization reactions and DPE values on Keggin polyoxometalates and H-BEA solids with known

  9. Mesoporous Silica with Site-Isolated Amine and Phosphotungstic Acid Groups: A Solid Catalyst with Tunable Antagonistic Functions for One-Pot Tandem Reactions

    SciTech Connect

    Shiju N. R.; Syed K.; Alberts A.; Brown D. and Rothenberg G.

    2011-09-15

    A bifunctional solid catalyst is prepared by combining acid and base functions on mesoporous silica supports. The co-existence of these functions is shown by a two-step reaction sequence in one pot. Excellent product yields, which cannot be obtained by separated acid and base functions in one pot, show the validity of our concept.

  10. Synthesis of phenoxy ethers of methyl lesquerolate over solid acid catalysts

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Lesquerolic acid is the primary fatty acid found in Lesquerella. The seeds are 33% oil of which about 55% is the 20 carbon unsaturated hydroxyl fatty acid, lesquerolic acid. A simple derivatization of this fatty acid could expand its potential as an industrial oil. We have used a heterogeneous Le...

  11. SYNTHESIS AND CHARACTERIZATION OF A NOVEL SOLID ACID CATALYST FOR IMPROVED USE OF WASTE OIL FEEDSTOCK FOR BIODIESEL PRODUCTION

    EPA Science Inventory

    Carbon Catalyst Synthesis - Sucrose was treated directly with excess sulfuric acid sulfuric acid (9:1 mol/mol, 25°C). A carbon foam (nearly 20 fold increase in bulk volume) was immediately formed. The foam was then washed until no sulfate was dete...

  12. UBC Social Ecological Economic Development Studies (SEEDS) Student Report Investigation of Solid Acid Catalyst Functionalization for the Production of Biodiesel

    E-print Network

    Acid Catalyst Functionalization for the Production of Biodiesel Elliot James Nash University of British Functionalization for the Production of Biodiesel By Elliot James Nash Thesis CHBE 493/494 4 April 2013 The Faculty;ii Abstract The adoption of biodiesel as an alternative fuel is gaining momentum despite its large

  13. Mechanism of Glucose Isomerization Using a Solid Lewis Acid Catalyst in Water

    SciTech Connect

    Roman-Leshkov, Yuriy; Moliner, Manuel; Labinger, J. A.; Davis, Mark E.

    2010-10-20

    1H and 13C NMR spectroscopy on isotopically labeled glucose reveals that in the presence of tin-containing zeolite Sn-Beta, the isomerization reaction of glucose in water proceeds by way of an intramolecular hydride shift rather than proton transfer. This is the first mechanistic demonstration of Sn-Beta acting as a Lewis acid in a purely aqueous environment.

  14. Decomposition of oxalic acid on solid-phase catalysts in nitric acid solutions in the presence of hydrazine

    SciTech Connect

    Krot, N.N.; Shilov, V.P.; Dzyubenko, V.I.

    1995-01-01

    Decomposition of N{sub 2}H{sub 4} and H{sub 2}C{sub 2}O{sub 4} has been studied by titrimetric method in HNO{sub 3} solutions in the presence of Pt/SiO{sub 2} catalyst and BAU activated carbon. Under static conditions, the rate of N{sub 2}H{sub 4} decomposition in the presence of Pt/SiO{sub 2} increases monotonically with increasing temperature, Pt content, and amount of catalyst per unit volume of the solution. With increasing HNO{sub 3} concentration from 0.2 to 7 M, the N{sub 2}H{sub 4} decomposition rate peaks at 1-2 M. Decomposition of H{sub 2}C{sub 2}O{sub 4} begins only after N{sub 2}H{sub 4} is almost completely decomposed. When passing a mixture of H{sub 2}C{sub 2}O{sub 4} with N{sub 2}H{sub 4}through a column packed with catalyst, decomposition of H{sub 2}C{sub 2}O{sub 4} begins before complete disappearence of N{sub 2}H{sub 4}.

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

    PubMed

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

    2015-01-01

    The utilization of ferric-manganese promoted molybdenum oxide/zirconia (Fe-Mn- MoO3/ZrO2) (FMMZ) solid acid catalyst for production of biodiesel was demonstrated. FMMZ is produced through impregnation reaction followed by calcination at 600°C for 3 h. The characterization of FMMZ had been done using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), thermal gravimetric analysis (TGA), temperature programmed desorption of NH3 (TPD-NH3), transmission electron microscopy(TEM) and Brunner-Emmett-Teller (BET) surface area measurement. The effect of waste cooking oil methyl esters (WCOME's) yield on the reactions variables such as reaction temperature, catalyst loading, molar ratio of methanol/oil and reusability were also assessed. The catalyst was used to convert the waste cooking oil into corresponding methyl esters (95.6%±0.15) within 5 h at 200? reaction temperature, 600 rpm stirring speed, 1:25 molar ratio of oil to alcohol and 4% w/w catalyst loading. The reported catalyst was successfully recycled in six connective experiments without loss in activity. Moreover, the fuel properties of WCOME's were also reported using ASTM D 6751 methods. PMID:25843280

  16. Supercritical/Solid Catalyst (SSC)

    ScienceCinema

    None

    2013-05-28

    INL's patented, continuous-flow Supercritical/Solid Catalyst (SSC) produces the highest ASTM-quality B-100 biodiesel from waste fats, oils, and greases at the site of waste generation. SSC delivers low-cost transportation fuel, avoids significant landfill costs for municipalities, and reduces potent methane and other emissions produced in landfills from these wastes. You can learn more about INL's energy research programs at http://www.facebook.com/idahonationallaboratory.

  17. Supercritical/Solid Catalyst (SSC)

    SciTech Connect

    2010-01-01

    INL's patented, continuous-flow Supercritical/Solid Catalyst (SSC) produces the highest ASTM-quality B-100 biodiesel from waste fats, oils, and greases at the site of waste generation. SSC delivers low-cost transportation fuel, avoids significant landfill costs for municipalities, and reduces potent methane and other emissions produced in landfills from these wastes. You can learn more about INL's energy research programs at http://www.facebook.com/idahonationallaboratory.

  18. Zirconium(IV) tungstate nanoparticles prepared through chemical co-precipitation method and its function as solid acid catalyst

    NASA Astrophysics Data System (ADS)

    Sadanandan, Manoj; Bhaskaran, Beena

    2014-08-01

    In this paper, we report the synthesis of zirconium(IV) tungstate nanoparticles, a new and efficient catalyst for the oxidation of benzyl alcohol and esterification of acetic acid with various alcohols. The nanoparticle catalyst was prepared using the room temperature chemical co-precipitation method. The catalyst was characterized with thermogravimetric and differential thermal analysis, elemental analysis, X-ray diffraction analysis (XRD), fourier transform infrared spectroscopy (FT-IR), high-resolution transmission electron microscopy (HRTEM), atomic force microscopy (AFM) and the Brunauer-Emmett-Teller (BET) surface area. The crystallite size was found to be ~20 nm as revealed by XRD, HRTEM and AFM. The Na+ exchange capacity was found to be 2.76 meq g-1 and the surface area of the compound measured using BET method was found to be 250-265 m2 g-1. The high value of ion exchange capacity indicates the presence of surface hydroxyl groups. The prepared nanoparticles have proven to be excellent catalysts for both oxidation and ester synthesis under mild reaction conditions. The mechanism of the catalytic reaction was studied as well.

  19. Catalytic Upgrading of 5-Hydroxymethylfurfural to Drop-in Biofuels by Solid Base and Bifunctional Metal-Acid Catalysts.

    PubMed

    Bohre, Ashish; Saha, Basudeb; Abu-Omar, Mahdi M

    2015-12-01

    Design and synthesis of effective heterogeneous catalysts for the conversion of biomass intermediates into long chain hydrocarbon precursors and their subsequent deoxygenation to hydrocarbons is a viable strategy for upgrading lignocellulose into distillate range drop-in biofuels. Herein, we report a two-step process for upgrading 5-hydroxymethylfurfural (HMF) to C9 and C11 fuels with high yield and selectivity. The first step involves aldol condensation of HMF and acetone with a water tolerant solid base catalyst, zirconium carbonate (Zr(CO3 )x ), which gave 92?% C9 -aldol product with high selectivity at nearly 100?% HMF conversion. The as-synthesised Zr(CO3 )x was analysed by several analytical methods for elucidating its structural properties. Recyclability studies of Zr(CO3 )x revealed a negligible loss of its activity after five consecutive cycles over 120?h of operation. Isolated aldol product from the first step was hydrodeoxygenated with a bifunctional Pd/Zeolite-? catalyst in ethanol, which showed quantitative conversion of the aldol product to n-nonane and 1-ethoxynonane with 40 and 56?% selectivity, respectively. 1-Ethoxynonane, a low oxygenate diesel range fuel, which we report for the first time in this paper, is believed to form through etherification of the hydroxymethyl group of the aldol product with ethanol followed by opening of the furan ring and hydrodeoxygenation of the ether intermediate. PMID:26549016

  20. Characterizing Surface Acidic Sites in Mesoporous-Silica-Supported Tungsten Oxide Catalysts Using Solid State NMR and Quantum Chemistry Calculations

    SciTech Connect

    Hu, Jian Z.; Kwak, Ja Hun; Wang, Yong; Hu, Mary Y.; Turcu, Romulus VF; Peden, Charles HF

    2011-10-18

    The acidic sites in dispersed tungsten oxide supported on SBA-15 mesoporous silica were investigated using a combination of pyridine titration, both fast-, and slow-MAS {sup 15}N NMR, static {sup 2}H NMR, and quantum chemistry calculations. It is found that the bridged acidic -OH groups in surface adsorbed tungsten dimers (i.e., W-OH-W) are the Broensted acid sites. The unusually strong acidity of these Broensted acid sites is confirmed by quantum chemistry calculations. In contrast, terminal W-OH sites are very stable and only weakly acidic as are terminal Si-OH sites. Furthermore, molecular interactions between pyridine molecules and the dimer Broensted and terminal W-OH sites for dispersed tungsten oxide species is strong. This results in restricted molecular motion for the interacting pyridine molecules even at room temperature, i.e., a reorientation mainly about the molecular 2-fold axis. This restricted reorientation makes it possible to estimate the relative ratio of the Broensted (tungsten dimer) to the weakly acidic terminal W-OH sites in the catalyst using the slow-MAS {sup 1}H-{sup 15}N CP PASS method.

  1. A comparative study of solid carbon acid catalysts for the esterification of free fatty acids for biodiesel production. Evidence for the leaching of colloidal carbon.

    PubMed

    Deshmane, Chinmay A; Wright, Marcus W; Lachgar, Abdessadek; Rohlfing, Matthew; Liu, Zhening; Le, James; Hanson, Brian E

    2013-11-01

    The preparation of a variety of sulfonated carbons and their use in the esterification of oleic acid is reported. All sulfonated materials show some loss in activity associated with the leaching of active sites. Exhaustive leaching shows that a finite amount of activity is lost from the carbons in the form of colloids. Fully leached catalysts show no loss in activity upon recycling. The best catalysts; 1, 3, and 6; show initial TOFs of 0.07 s(-1), 0.05 s(-1), and 0.14 s(-1), respectively. These compare favorably with literature values. Significantly, the leachate solutions obtained from catalysts 1, 3, and 6, also show excellent esterification activity. The results of TEM and catalyst poisoning experiments on the leachate solutions associate the catalytic activity of these solutions with carbon colloids. This mechanism for leaching active sites from sulfonated carbons is previously unrecognized. PMID:24021721

  2. Structural studies of high dispersion H3PW12O40/SiO2 solid acid catalysts.

    PubMed

    Newman, Andrew D; Brown, D Robert; Siril, Prem; Lee, Adam F; Wilson, Karen

    2006-06-28

    Highly dispersed H(3)PW(12)O(40)/SiO(2) catalysts with loadings between 3.6 and 62.5 wt% have been synthesised and characterised. The formation of a chemically distinct interfacial HPW species is identified by XPS, attributed to pertubation of W atoms within the Keggin cage in direct contact with the SiO(2) surface. EXAFS confirms the Keggin unit remains intact for all loadings, while NH(3) adsorption calorimetery reveals the acid strength >0.14 monolayers of HPW is loading invariant with initial DeltaH(ads) = approximately -164 kJ mol(-1). Lower loading catalysts exhibit weaker acidity which is attributed to an inability of highly dispersed clusters to form crystalline water. For reactions involving non-polar hydrocarbons the interfacial species where the accessible tungstate is highest confer the greatest reactivity, while polar chemistry is favoured by higher loadings which can take advantage of the H(3)PW(12)O(40) pseudo-liquid phase available within supported multilayers. PMID:16775645

  3. The n-butyl amine TPD measurement of Brönsted acidity for solid catalysts by simultaneous TG/DTG-DTA

    NASA Astrophysics Data System (ADS)

    Sasca, V.; Avram, Livia; Verdes, Orsina; Popa, A.

    2010-06-01

    The method for Brönsted acidity measurement based on TPD of alkyl amines desorption by gas-chromatography or thermogravimetry was adapted for simultaneous TG/DTG-DTA analysis. The acidity measurements were focused on the 12-tungstophosphoric acid (H 3PW 12O 40) and its salts, especially with Cesium since these posses the highest Brönsted acidity and they are among the most interesting catalysts. The n-butyl amine (NBA) desorption takes place in three steps for Cs xH 3- xPW 12O 40, x = 0-2, and four steps for the Cs 2.5H 0.5PW 12O 40. The steps of desorption correspond to the release of NBA molecules in stages, as NBA or butene molecules resulted from the Hofmann elimination reaction and NH 3 + H 2O formed by decomposition of ammonium salt. The quantities of desorption products, C 4H 8 and NH 3 + H 2O, corresponding to the stages with the maximum desorption rates at 400-420 °C, respectively 560-600 °C, are in the stoichiometric ratio with the Brönsted acidity.

  4. Superior performance of metal-organic frameworks over zeolites as solid acid catalysts in the Prins reaction: green synthesis of nopol.

    PubMed

    Opanasenko, Maksym; Dhakshinamoorthy, Amarajothi; Hwang, Young Kyu; Chang, Jong-San; Garcia, Hermenegildo; ?ejka, Ji?í

    2013-05-01

    The catalytic performance of a set of metal-organic frameworks [CuBTC, FeBTC, MIL-100(Fe), MIL-100(Cr), ZIF-8, MIL-53(Al)] was investigated in the Prins condensation of ?-pinene with formaldehyde and compared with the catalytic behavior of conventional aluminosilicate zeolites BEA and FAU and titanosilicate zeolite MFI (TS-1). The activity of the investigated metal-organic frameworks (MOFs) increased with the increasing concentration of accessible Lewis acid sites in the order ZIF-8acid sites of zeolites BEA and FAU, which showed significantly lower selectivity to the target nopol than the MOFs. Its high activity, the preservation of its structure and active sites, and the possibility to use it in at least three catalytic cycles without loss of activity make MIL-100 (Fe) the best performing catalyst of the series for the Prins condensation of ?-pinene and paraformaldehyde. Our report exemplifies the advantages of MOFs over zeolites as solid catalysts in liquid-phase reactions for the production of fine chemicals. PMID:23592600

  5. Theoretical predictions of 31p NMR chemical shift threshold of trimethylphosphine oxide absorbed on solid acid catalysts.

    PubMed

    Zheng, Anmin; Zhang, Hailu; Lu, Xin; Liu, Shang-Bin; Deng, Feng

    2008-04-17

    The 31P NMR chemical shifts of adsorbed trimethylphosphine oxide (TMPO) and the configurations of the corresponding TMPOH+ complexes on Brønsted acid sites with varying acid strengths in modeled zeolites have been predicted theoretically by means of density functional theory (DFT) quantum chemical calculations. The configuration of each TMPOH+ complex was optimized at the PW91/DNP level based on an 8T cluster model, whereas the 31P chemical shifts were calculated with the gauge including atomic orbital (GIAO) approach at both the HF/TZVP and MP2/TZVP levels. A linear correlation between the 31P chemical shift of adsorbed TMPO and the proton affinity of the solid acids was observed, and a threshold for superacidity (86 ppm) was determined. This threshold for superacidity was also confirmed by comparative investigations on other superacid systems, such as carborane acid and heteropolyoxometalate H3PW12O40. In conjunction with the strong correlation between the MP2 and the HF 31P isotropic shifts, the 8T cluster model was extended to more sophisticated models (up to 72T) that are not readily tractable at the GIAO-MP2 level, and a 31P chemical shift of 86 ppm was determined for TMPO adsorbed on zeolite H-ZSM-5, which is in good agreement with the NMR experimental data. PMID:18358024

  6. Carbon-based strong solid acid for cornstarch hydrolysis

    NASA Astrophysics Data System (ADS)

    Nata, Iryanti Fatyasari; Irawan, Chairul; Mardina, Primata; Lee, Cheng-Kang

    2015-10-01

    Highly sulfonated carbonaceous spheres with diameter of 100-500 nm can be generated by hydrothermal carbonization of glucose in the presence of hydroxyethylsulfonic acid and acrylic acid at 180 °C for 4 h. The acidity of the prepared carbonaceous sphere C4-SO3H can reach 2.10 mmol/g. It was used as a solid acid catalyst for the hydrolysis of cornstarch. Total reducing sugar (TRS) concentration of 19.91 mg/mL could be obtained by hydrolyzing 20 mg/mL cornstarch at 150 °C for 6 h using C4-SO3H as solid acid catalyst. The solid acid catalyst demonstrated good stability that only 9% decrease in TRS concentration was observed after five repeat uses. The as-prepared carbon-based solid acid catalyst can be an environmentally benign replacement for homogeneous catalyst.

  7. Acid monolayer functionalized iron oxide nanoparticle catalysts

    NASA Astrophysics Data System (ADS)

    Ikenberry, Myles

    Superparamagnetic iron oxide nanoparticle functionalization is an area of intensely active research, with applications across disciplines such as biomedical science and heterogeneous catalysis. This work demonstrates the functionalization of iron oxide nanoparticles with a quasi-monolayer of 11-sulfoundecanoic acid, 10-phosphono-1-decanesulfonic acid, and 11-aminoundecanoic acid. The carboxylic and phosphonic moieties form bonds to the iron oxide particle core, while the sulfonic acid groups face outward where they are available for catalysis. The particles were characterized by thermogravimetric analysis (TGA), transmission electron microscopy (TEM), potentiometric titration, diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), inductively coupled plasma optical emission spectrometry (ICP-OES), X-ray photoelectron spectrometry (XPS), and dynamic light scattering (DLS). The sulfonic acid functionalized particles were used to catalyze the hydrolysis of sucrose at 80° and starch at 130°, showing a higher activity per acid site than the traditional solid acid catalyst Amberlyst-15, and comparing well against results reported in the literature for sulfonic acid functionalized mesoporous silicas. In sucrose catalysis reactions, the phosphonic-sulfonic nanoparticles (PSNPs) were seen to be incompletely recovered by an external magnetic field, while the carboxylic-sulfonic nanoparticles (CSNPs) showed a trend of increasing activity over the first four recycle runs. Between the two sulfonic ligands, the phosphonates produced a more tightly packed monolayer, which corresponded to a higher sulfonic acid loading, lower agglomeration, lower recoverability through application of an external magnetic field, and higher activity per acid site for the hydrolysis of starch. Functionalizations with 11-aminoundecanoic acid resulted in some amine groups binding to the surfaces of iron oxide nanoparticles. This amine binding is commonly ignored in iron oxide nanoparticle syntheses and functionalizations for biomedical and catalytic applications, affecting understandings of surface charge and other material properties.

  8. Back Cover: Synthesis of a Sulfonated Two-Dimensional Covalent Organic Framework as an Efficient Solid Acid Catalyst for Biobased Chemical Conversion (ChemSusChem 19/2015).

    PubMed

    Peng, Yongwu; Hu, Zhigang; Gao, Yongjun; Yuan, Daqiang; Kang, Zixi; Qian, Yuhong; Yan, Ning; Zhao, Dan

    2015-10-01

    The Back Cover picture shows the crystal structure of a sulfonic acid-functionalized 2D covalent organic framework (COF) and its application as a highly effective solid acid catalyst with excellent catalytic activity and chemoselectivity for the conversion of fructose into 5-hydroxymethylfurfural (HMF) and 2,5-diformylfuran (DFF). A sulfonated 2D crystalline COF, termed TFP-DABA, is synthesized directly using 1,3,5-triformylphloroglucinol (TFP) and 2,5-diaminobenzenesulfonic acid (DABA) via a Schiff base condensation reaction followed by irreversible enol-to-keto tautomerization. This COF is highly efficient for fructose conversion with remarkable yields (97% for HMF and 65% for DFF). This study provides encouragement for further exploration of COFs as heterogeneous catalysts for bio-based chemical conversion and related applications. More details can be found in the Communication by D. Zhao et?al. on page?3208 in Issue 19, 2015 (DOI: 10.1002/cssc.201500755). PMID:26448529

  9. Formic acid fuel cells and catalysts

    DOEpatents

    Masel, Richard I.; Larsen, Robert; Ha, Su Yun

    2010-06-22

    An exemplary fuel cell of the invention includes a formic acid fuel solution in communication with an anode (12, 134), an oxidizer in communication with a cathode (16, 135) electrically linked to the anode, and an anode catalyst that includes Pd. An exemplary formic acid fuel cell membrane electrode assembly (130) includes a proton-conducting membrane (131) having opposing first (132) and second surfaces (133), a cathode catalyst on the second membrane surface, and an anode catalyst including Pd on the first surface.

  10. A New Instrument For Characterizing Solid Oxide Fuel Cell Catalysts

    E-print Network

    RESEARCH HIGHLIGHTS A New Instrument For Characterizing Solid Oxide Fuel Cell Catalysts From fuels to renewable energy sources. Solid oxide fuel cells (SOFCs) have enormous potential in this area A New Instrument For Characterizing Solid Oxide Fuel Cell Catalysts Rob Usiskin In partnership

  11. Conversion of corn stalk into furfural using a novel heterogeneous strong acid catalyst in ?-valerolactone.

    PubMed

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

    2015-12-01

    A novel solid acid catalyst was prepared by the copolymerization of p-toluenesulfonic acid and paraformaldehyde and then characterized by FT-IR, TG/DTG, HRTEM and N2-BET. Furfural was successfully produced by the dehydration of xylose and xylan using the novel catalyst in ?-valerolactone. This investigation focused on effects of various reaction conditions including solvent, acid catalyst, reaction temperature, residence time, water concentration, xylose loading and catalyst dosage on the dehydration of xylose to furfural. It was found that the solid catalyst displayed extremely high activity for furfural production. 80.4% furfural yield with 98.8% xylose conversion was achieved at 170°C for 10min. The catalyst could be recycled at least five times without significant loss of activity. Furthermore, 83.5% furfural yield and 19.5% HMF yield were obtained from raw corn stalk under more severe conditions (190°C for 100min). PMID:26454364

  12. Catalysts for portable, solid state hydrogen genration systems

    NASA Astrophysics Data System (ADS)

    Gabl, Jason Robert

    Hydrogen and air powered proton exchange membrane fuel cells are a potential alternative to batteries. In portable power systems, the design requirements often focus on cost efficiency, energy density, storability, as well as safety. Ammonia borane (AB), a chemical hydride containing 19.6 wt. % hydrogen, has a high hydrogen capacity and is a stable and non-toxic candidate for storing hydrogen in portable systems. Throughout this work, Department of Energy guidelines for low power portable hydrogen power systems were used as a baseline and comparison with commercially available systems. In order to make this comparison, the system parameters of a system using AB hydrolysis were estimated by developing capacity and cost correlations from the commercial systems and applying them to this work. Supporting experiments were designed to evaluate a system that would use a premixed solid storage bed of AB and a catalyst. This configuration would only require a user input of water in order to initiate the hydrogen production. Using ammonia borane hydrolysis, the hydrogen yield is ˜9 wt. %, when all reactants are considered. In addition to the simplicity of initiating the reaction, hydrolysis of AB has the advantage of suppressing the production of some toxic borazines that are present when AB is thermally decomposed. However, ammonia gas will be formed and this problem must be addressed, as ammonia is damaging to PEM fuel cells. The catalyst focused on throughout this work was Amberlyst - 15; an ion exchange resin with an acid capacity of 4.7 eq/kg and ammonia adsorbent. At less than 0.30/g, this is a cost effective alternative to precious metal catalysts. The testing with this catalyst was compared to a traditional catalyst in literature, 20% platinum in carbon, costing more than 40/g. The Amberlyst catalyst was found to reduce the formation of ammonia in the gas products from ˜3.71 wt. % with the Pt/C catalyst to <0.01 wt. %. Since Amberlyst adsorbs ammonia, it acts as a "consumable" catalyst, requiring a minimum loading for complete reaction. A mass ratio of a least ˜10:1 Amberlyst to AB is needed for a complete reaction. Conversely, the Pt/C is a reusable catalyst and only used at 5 wt. % loading throughout testing. The activation energy of the Amberlyst catalyzed reaction were measured to be 11.6 kJ/mol, which improves upon the activation energy measured with the Pt/C catalyst of 49.3 kJ/mol, making it a more effective catalyst. However, from the results of an aging study, the proposed system configuration of storing the AB and Amberlyst together will need further development, as the theoretical hydrogen yield dropped from > 90 % to < 30 % over a 70 day aging study. This results implies the need for a systems scale solution, such as mechanical separation, or a material scale solution, such as coating the Amberlyst or AB in a water soluble coating. It was found that ammonia borane catalyzed hydrolysis, using Amberlyst - 15 as a catalyst, has potential to be a cost effective, energy dense, and safe option for generating hydrogen for a portable fuel cell system.

  13. Calcium and lanthanum solid base catalysts for transesterification

    DOEpatents

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

    2015-07-28

    In one aspect, a heterogeneous catalyst comprises calcium hydroxide and lanthanum hydroxide, wherein the catalyst has a specific surface area of more than about 10 m.sup.2/g. In another aspect, a heterogeneous catalyst comprises a calcium compound and a lanthanum compound, wherein the catalyst has a specific surface area of more than about 10 m.sup.2/g, and a total basicity of about 13.6 mmol/g. In further another aspect, a heterogeneous catalyst comprises calcium oxide and lanthanum oxide, wherein the catalyst has a specific surface area of more than about 10 m.sup.2/g. In still another aspect, a process for preparing a catalyst comprises introducing a base precipitant, a neutral precipitant, and an acid precipitant to a solution comprising a first metal ion and a second metal ion to form a precipitate. The process further comprises calcining the precipitate to provide the catalyst.

  14. Differential thermal analysis as an acidity probe in zeolite catalysts

    SciTech Connect

    Aboul-Gheit, A.K.; Al-Hajjaji, M.A.; Menoufy, M.F.; Abdel-Hamid, S.M.

    1986-01-01

    Differential thermal analysis is used as an acidity strength probe for a series of mordenite (zeolite) catalysts via determining the temperature at which presorbed pyridine completely desorbs from the catalyst. The findings obtained for metal(s) containing mordenite catalysts have been correlated with the Pearson's assumption concerning Lewis acids and bases and the Pauling's electronegativity of the metals contained and found compatible.

  15. Solid phase polymerization of phenylenediamine toward a self-supported FeNx/C catalyst with high oxygen reduction activity.

    PubMed

    Su, Xiaogang; Liu, Jianguo; Yao, Yingfang; You, Yong; Zhang, Xiang; Zhao, Canyun; Wan, Hong; Zhou, You; Zou, Zhigang

    2015-12-01

    Solid phase polymerization of phenylenediamine with a template toward a self-supported FeNx/C catalyst was introduced. Using ZnO nanoparticles as the hard template could increase the surface area of the catalyst, thus the oxygen reduction activity was radically enhanced, to 21.9 A g(-1) at 0.80 V (vs. RHE) in acid medium. PMID:26434639

  16. Method For Reactivating Solid Catalysts Used For Alklation Reactions

    DOEpatents

    Ginosar, Daniel M. (Idaho Falls, ID); Thompson, David N. (Idaho Falls, ID); Coates, Kyle (Shelley, ID); Zalewski, David J. (Proctorville, OH); Fox, Robert V. (Idaho Falls, ID)

    2005-05-03

    A method for reactivating a solid alkylation catalyst is provided which can be performed within a reactor that contains the alkylation catalyst or outside the reactor. Effective catalyst reactivation is achieved whether the catalyst is completely deactivated or partially deactivated. A fluid reactivating agent is employed to dissolve catalyst fouling agents and also to react with such agents and carry away the reaction products. The deactivated catalyst is contacted with the fluid reactivating agent under pressure and temperature conditions such that the fluid reactivating agent is dense enough to effectively dissolve the fouling agents and any reaction products of the fouling agents and the reactivating agent. Useful pressures and temperatures for reactivation include near-critical, critical, and supercritical pressures and temperatures for the reactivating agent. The fluid reactivating agent can include, for example, a branched paraffin containing at least one tertiary carbon atom, or a compound that can be isomerized to a molecule containing at least one tertiary carbon atom.

  17. Method for reactivating solid catalysts used in alkylation reactions

    DOEpatents

    Ginosar, Daniel M.; Thompson, David N.; Coates, Kyle; Zalewski, David J.; Fox, Robert V.

    2003-06-17

    A method for reactivating a solid alkylation catalyst is provided which can be performed within a reactor that contains the alkylation catalyst or outside the reactor. Effective catalyst reactivation is achieved whether the catalyst is completely deactivated or partially deactivated. A fluid reactivating agent is employed to dissolve catalyst fouling agents and also to react with such agents and carry away the reaction products. The deactivated catalyst is contacted with the fluid reactivating agent under pressure and temperature conditions such that the fluid reactivating agent is dense enough to effectively dissolve the fouling agents and any reaction products of the fouling agents and the reactivating agent. Useful pressures and temperatures for reactivation include near-critical, critical, and supercritical pressures and temperatures for the reactivating agent. The fluid reactivating agent can include, for example, a branched paraffin containing at least one tertiary carbon atom, or a compound that can be isomerized to a molecule containing at least one tertiary carbon atom.

  18. Application of solid ash based catalysts in heterogeneous catalysis

    SciTech Connect

    Shaobin Wang

    2008-10-01

    Solid wastes, fly ash, and bottom ash are generated from coal and biomass combustion. Fly ash is mainly composed of various metal oxides and possesses higher thermal stability. Utilization of fly ash for other industrial applications provides a cost-effective and environmentally friendly way of recycling this solid waste, significantly reducing its environmental effects. On the one hand, due to the higher stability of its major component, aluminosilicates, fly ash could be employed as catalyst support by impregnation of other active components for various reactions. On the other hand, other chemical compounds in fly ash such as Fe{sub 2}O{sub 3} could also provide an active component making fly ash a catalyst for some reactions. In this paper, physicochemical properties of fly ash and its applications for heterogeneous catalysis as a catalyst support or catalyst in a variety of catalytic reactions were reviewed. Fly-ash-supported catalysts have shown good catalytic activities for H{sub 2} production, deSOx, deNOx, hydrocarbon oxidation, and hydrocracking, which are comparable to commercially used catalysts. As a catalyst itself, fly ash can also be effective for gas-phase oxidation of volatile organic compounds, aqueous-phase oxidation of organics, solid plastic pyrolysis, and solvent-free organic synthesis. 107 refs., 4 figs., 2 tabs.

  19. Removal of metal comtaminants from catalysts using buffered oxalic acid

    SciTech Connect

    McVicker, G. B.; Carter, J. L.; Murrell, L. L.; Ziemiak, J. J.

    1985-06-11

    A process for removing metal contaminants from a hydroconversion catalyst, said catalyst containing at least one metal from Groups VIB, VIIB or VIII supported on a refractory inorganic oxide. The process comprises contacting the contaminated catalyst with a buffered oxalic acid solution wherein contaminant is removed without dissolving the support.

  20. Isobutane/butene alkylation on microporous and mesoporous solid acid catalysts: probing the pore transport effects with liquid and near critical reaction media

    E-print Network

    Sarsani, V. R.; Subramaniam, Bala

    2008-11-13

    The alkylation of isobutane with 1-butene was investigated on microporous (?-zeolite) and mesoporous (silica supported heteropolyacids) catalysts in a slurry reactor. The reaction was investigated in the range of 25–100 bar and 15–95 °C in liquid...

  1. Catalyst and electrode research for phosphoric acid fuel cells

    NASA Technical Reports Server (NTRS)

    Antoine, A. C.; King, R. B.

    1987-01-01

    An account is given of the development status of phosphoric acid fuel cells' high performance catalyst and electrode materials. Binary alloys have been identified which outperform the baseline platinum catalyst; it has also become apparent that pressurized operation is required to reach the desired efficiencies, calling in turn for the use of graphitized carbon blacks in the role of catalyst supports. Efforts to improve cell performance and reduce catalyst costs have led to the investigation of a class of organometallic cathode catalysts represented by the tetraazaannulenes, and a mixed catalyst which is a mixture of carbons catalyzed with an organometallic and a noble metal.

  2. Synthesis and acid catalysis of cellulose-derived carbon-based solid acid

    NASA Astrophysics Data System (ADS)

    Suganuma, Satoshi; Nakajima, Kiyotaka; Kitano, Masaaki; Yamaguchi, Daizo; Kato, Hideki; Hayashi, Shigenobu; Hara, Michikazu

    2010-06-01

    SO 3H-bearing amorphous carbon, prepared by partial carbonization of cellulose followed by sulfonation in fuming H 2SO 4, was applied as a solid catalyst for the acid-catalyzed hydrolysis of ?-1,4 glucan, including cellobiose and crystalline cellulose. Structural analyses revealed that the resulting carbon material consists of graphene sheets with 1.5 mmol g -1 of SO 3H groups, 0.4 mmol g -1 of COOH, and 5.6 mmol g -1 of phenolic OH groups. The carbon catalyst showed high catalytic activity for the hydrolysis of ?-1,4 glycosidic bonds in both cellobiose and crystalline cellulose. Pure crystalline cellulose was not hydrolyzed by conventional strong solid Brønsted acid catalysts such as niobic acid, Nafion ® NR-50, and Amberlyst-15, whereas the carbon catalyst efficiently hydrolyzes cellulose into water-soluble saccharides. The catalytic performance of the carbon catalyst is due to the large adsorption capacity for hydrophilic reactants and the adsorption ability of ?-1,4 glucan, which is not adsorbed to other solid acids.

  3. Molybdenum Dioxide As A Solid Oxide Fuel Cell Anodic Catalyst

    E-print Network

    Collins, Gary S.

    Molybdenum Dioxide As A Solid Oxide Fuel Cell Anodic Catalyst Jay Thunstrom, Su Ha, Oscar Flores conducted focused on fabricating anodes based on molybdenum dioxide, which has proven to readily reform in much the same way as the cathode. A molybdenum trioxide powder is diluted with nickel oxide and YSZ

  4. Biguanide-functionalized mesoporous SBA-15 silica as an efficient solid catalyst for interesterification of vegetable oils.

    PubMed

    Xie, Wenlei; Hu, Libing

    2016-04-15

    The biguanide-functionalized SBA-15 materials were fabricated by grafting of organic biguanide onto the SBA-15 silica through covalent attachments, and then this organic-inorganic hybrid material was employed as solid catalysts for the interesterification of triacylglycerols for the modification of vegetable oils. The prepared catalyst was characterized by FTIR, XRD, SEM, TEM, nitrogen adsorption-desorption and elemental analysis. The biguanide base was successfully tethered onto the SBA-15 silica with no damage to the ordered mesoporous structure of the silica after the organo-functionalization. The solid catalyst had stronger base strength and could catalyze the interesterification of triacylglycerols. The fatty acid compositions and triacylglycerol profiles of the interesterified products were noticeably varied following the interesterification. The reaction parameters, namely substrate ratio, reaction temperature, catalyst loading and reaction time, were investigated for the interesterification of soybean oil with methyl decanoate. The catalyst could be reused for at least four cycles without significant loss of activity. PMID:26616928

  5. Low acid producing solid propellants

    NASA Technical Reports Server (NTRS)

    Bennett, Robert R.

    1995-01-01

    The potential environmental effects of the exhaust products of conventional rocket propellants have been assessed by various groups. Areas of concern have included stratospheric ozone, acid rain, toxicity, air quality and global warming. Some of the studies which have been performed on this subject have concluded that while the impacts of rocket use are extremely small, there are propellant development options which have the potential to reduce those impacts even further. This paper discusses the various solid propellant options which have been proposed as being more environmentally benign than current systems by reducing HCI emissions. These options include acid neutralized, acid scavenged, and nonchlorine propellants. An assessment of the acid reducing potential and the viability of each of these options is made, based on current information. Such an assessment is needed in order to judge whether the potential improvements justify the expenditures of developing the new propellant systems.

  6. Liquefaction of solid carbonaceous material with catalyst recycle

    DOEpatents

    Gupta, Avinash (Bloomfield, NJ); Greene, Marvin I. (Oradell, NJ)

    1992-01-01

    In the two stage liquefaction of a carbonaceous solid such as coal wherein coal is liquefied in a first stage in the presence of a liquefaction solvent and the first stage effluent is hydrogenated in the presence of a supported hydrogenation catalyst in a second stage, catalyst which has been previously employed in the second stage and comminuted to a particle size distribution equivalent to 100% passing through U.S. 100 Mesh, is passed to the first stage to improve the overall operation.

  7. EPA'S CATALYST RESEARCH PROGRAM: ENVIRONMENTAL IMPACT OF SULFURIC ACID EMISSIONS

    EPA Science Inventory

    A sulfuric acid review conference sponsored by EPA's automotive Catalyst Research Program was held recently at Hendersonville, NC, for researchers whose work is funded by EPA. Emissions characterization research indicated that in-use catalyst-equipped vehicles emit low levels of ...

  8. Surface acidity and degree of carburization of modified silver catalysts

    SciTech Connect

    Pestryakov, A.N.; Belousova, V.N.; Roznina, M.I.

    1993-11-10

    The effect has been studied of some compounds as modifying additives on the surface acidity, degree of carburization, aggregation and silver entrainement of silver-pumice catalysts for methanol oxidation. Catalyst samples have been tested in an industrial reactor. The probable mechanism of modifying action of the additives is discussed.

  9. Method for producing iron-based acid catalysts

    SciTech Connect

    Farcasiu, M.; Kathrein, H.; Kaufman, P.B.; Diehl, J.R.

    1998-04-01

    A method for preparing an acid catalyst with a long shelf-life is described. Crystalline iron oxides are doped with lattice compatible metals which are heated with halogen compounds at elevated temperatures.

  10. Heteropoly acid as a novel efficient catalyst for Fries rearrangement.

    PubMed

    Kozhevnikova, Elena F; Derouane, Eric G; Kozhevnikov, Ivan V

    2002-06-01

    Heteropoly acid H3PW12O40 is a very efficient and environmentally benign catalyst for the Fries rearrangement of phenyl acetate in homogeneous or heterogeneous liquid-phase systems at 100-150 degrees C. PMID:12109070

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

    PubMed

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

    2014-04-01

    A novel carbon-based solid acid catalyst was prepared by the sulfonation of incompletely carbonized cassava stillage residue (CSR) with concentrated sulfuric acid, and employed to catalyze the esterification of methanol and free fatty acids (FFAs) in waste cooking oil (WCO). The effects of the carbonization and the sulfonation temperatures on the pore structure, acid density and catalytic activity of the CSR-derived catalysts were systematically investigated. Low temperature carbonization and high temperature sulfonation can cause the collapse of the carbon framework, while high temperature carbonization is not conducive to the attachment of SO3H groups on the surface. The catalyst showed high catalytic activity for esterification, and the acid value for WCO is reduced to below 2mg KOH/g after reaction. The activity of catalyst can be well maintained after five cycles. CSR can be considered a promising raw material for the production of a new eco-friendly solid acid catalyst. PMID:24661813

  12. Biodiesel production from non-edible Silybum marianum oil using heterogeneous solid base catalyst under ultrasonication.

    PubMed

    Takase, Mohammed; Chen, Yao; Liu, Hongyang; Zhao, Ting; Yang, Liuqing; Wu, Xiangyang

    2014-09-01

    The aim of this study is to investigate modified TiO2 doped with C4H4O6HK as heterogeneous solid base catalyst for transesterification of non-edible, Silybum marianum oil to biodiesel using methanol under ultrasonication. Upon screening the catalytic performance of modified TiO2 doped with different K-compounds, 0.7 C4H4O6HK doped on TiO2 was selected. The preparation of the catalyst was done using incipient wetness impregnation method. Having doped modified TiO2 with C4H4O6HK, followed by impregnation, drying and calcination at 600 °C for 6 h, the catalyst was characterized by XRD, FTIR, SEM, BET, TGA, UV and the Hammett indicators. The yield of the biodiesel was proportional to the catalyst basicity. The catalyst had granular and porous structures with high basicity and superior performance. Combined conditions of 16:1 molar ratio of methanol to oil, 5 wt.% catalyst amount, 60 °C reaction temperature and 30 min reaction time was enough for maximum yield of 90.1%. The catalyst maintained sustained activity after five cycles of use. The oxidative stability which was the main problem of the biodiesel was improved from 2.0 h to 3.2h after 30 days using ascorbic acid as antioxidant. The other properties including the flash point, cetane number and the cold flow ones were however, comparable to international standards. The study indicated that Ti-0.7-600-6 is an efficient, economical and environmentally, friendly catalyst under ultrasonication for producing biodiesel from S. marianum oil with a substantial yield. PMID:24768105

  13. Reactivity and Characterization of Solid State Hydrodesulfurization Catalysts.

    NASA Astrophysics Data System (ADS)

    Lindner, James Henry

    1990-01-01

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

  14. Acid-base properties of titanium-antimony oxides catalysts

    SciTech Connect

    Zenkovets, G.A.; Paukshtis, E.A.; Tarasova, D.V.; Yurchenko, E.N.

    1982-06-01

    The acid-base properties of titanium-antimony oxide catalysts were studied by the methods of back titration and ir spectroscopy. The interrelationship between the acid-base and catalytic properties in the oxidative ammonolysis of propylene was discussed. 3 figures, 1 table.

  15. Electrochemical catalyst recovery method

    DOEpatents

    Silva, L.J.; Bray, L.A.

    1995-05-30

    A method of recovering catalyst material from latent catalyst material solids includes: (a) combining latent catalyst material solids with a liquid acid anolyte solution and a redox material which is soluble in the acid anolyte solution to form a mixture; (b) electrochemically oxidizing the redox material within the mixture into a dissolved oxidant, the oxidant having a potential for oxidation which is effectively higher than that of the latent catalyst material; (c) reacting the oxidant with the latent catalyst material to oxidize the latent catalyst material into at least one oxidized catalyst species which is soluble within the mixture and to reduce the oxidant back into dissolved redox material; and (d) recovering catalyst material from the oxidized catalyst species of the mixture. The invention is expected to be particularly useful in recovering spent catalyst material from petroleum hydroprocessing reaction waste products having adhered sulfides, carbon, hydrocarbons, and undesired metals, and as well as in other industrial applications. 3 figs.

  16. Electrochemical catalyst recovery method

    DOEpatents

    Silva, Laura J. (Richland, WA); Bray, Lane A. (Richland, WA)

    1995-01-01

    A method of recovering catalyst material from latent catalyst material solids includes: a) combining latent catalyst material solids with a liquid acid anolyte solution and a redox material which is soluble in the acid anolyte solution to form a mixture; b) electrochemically oxidizing the redox material within the mixture into a dissolved oxidant, the oxidant having a potential for oxidation which is effectively higher than that of the latent catalyst material; c) reacting the oxidant with the latent catalyst material to oxidize the latent catalyst material into at least one oxidized catalyst species which is soluble within the mixture and to reduce the oxidant back into dissolved redox material; and d) recovering catalyst material from the oxidized catalyst species of the mixture. The invention is expected to be particularly useful in recovering spent catalyst material from petroleum hydroprocessing reaction waste products having adhered sulfides, carbon, hydrocarbons, and undesired metals, and as well as in other industrial applications.

  17. Organometallic catalysts for primary phosphoric acid fuel cells

    NASA Technical Reports Server (NTRS)

    Walsh, Fraser

    1987-01-01

    A continuing effort by the U.S. Department of Energy to improve the competitiveness of the phosphoric acid fuel cell by improving cell performance and/or reducing cell cost is discussed. Cathode improvement, both in performance and cost, available through the use of a class of organometallic cathode catalysts, the tetraazaannulenes (TAAs), was investigated. A new mixed catalyst was identified which provides improved cathode performance without the need for the use of a noble metal. This mixed catalyst was tested under load for 1000 hr. in full cell at 160 to 200 C in phosphoric acid H3PO4, and was shown to provide stable performance. The mixed catalyst contains an organometallic to catalyze electroreduction of oxygen to hydrogen peroxide and a metal to catalyze further electroreduction of the hydrogen peroxide to water. Cathodes containing an exemplar mixed catalyst (e.g., Co bisphenyl TAA/Mn) operate at approximately 650 mV vs DHE in 160 C, 85% H3PO4 with oxygen as reactant. In developing this mixed catalyst, a broad spectrum of TAAs were prepared, tested in half-cell and in a rotating ring-disk electrode system. TAAs found to facilitate the production of hydrogen peroxide in electroreduction were shown to be preferred TAAs for use in the mixed catalyst. Manganese (Mn) was identified as a preferred metal because it is capable of catalyzing hydrogen peroxide electroreduction, is lower in cost and is of less strategic importance than platinum, the cathode catalyst normally used in the fuel cell.

  18. On the nature of the deactivation of supported palladium nanoparticle catalysts in the decarboxylation of fatty acids.

    SciTech Connect

    Ping, E. W.; Pierson, J.; Wallace, R.; Miller, J. T.; Fuller, T. F.; Jones, C. W.

    2011-04-15

    Supported palladium catalysts are effective catalysts for the hydrogen-free decarboxylation of fatty acids. However, the catalysts deactivate severely after one use. Here, the recyclability of a well-defined, mesoporous silica-supported palladium nanoparticle catalyst is evaluated in the batch decarboxylation of stearic acid at 300 C under inert atmosphere, producing n-heptadecane. The nature of the catalyst deactivation is examined in detail via an array of characterization techniques. X-ray photoelectron spectroscopy (XPS) demonstrates that little palladium surface oxidation occurs over the course of the reaction, and a combination of X-ray absorption spectroscopy and transmission electron microscopy (TEM) suggests negligible particle sintering or agglomeration. Physisorption and chemisorption measurements demonstrate substantial loss in total surface area and porosity as well as accessible palladium surface area with these losses attributed to significant organic deposition on the catalyst, as verified via thermogravimetric analysis. High temperature calcination is applied to combust and remove these residues, but resultant nanoparticle agglomeration is significant. Solid state nuclear magnetic resonance spectroscopy (NMR), Fourier transform infrared spectroscopy (FT-IR) and solid dissolution followed by organic extraction methodologies demonstrate that the carbonaceous deposits are not coke but rather strongly adsorbed reactants and products. Detrimental coke formation, as suggested by prior literature, is verified to be absent, as extraction of the surface-deposited organic species yields nearly complete recovery of the total surface area, pore volume, and active palladium surface area. Furthermore, the regenerated catalyst exhibits a corresponding significant recovery of decarboxylation activity.

  19. Thermal decomposition of lignocellulosic biomass in the presence of acid catalysts.

    PubMed

    Larabi, Cherif; al Maksoud, Walid; Szeto, Kai C; Roubaud, Anne; Castelli, Pierre; Santini, Catherine C; Walter, Jean J

    2013-11-01

    Transformation of lignocellulosic biomass to biofuels involves multiple processes, in which thermal decomposition, hydrotreatment are the most central steps. Current work focuses on the impact of several solid acids and Keggin-type heteropolyacids on the decomposition temperature (Td) of pine wood and the characterization of the resulted products. It has been observed that a mechanical mixture of solid acids with pine wood has no influence on Td, while the use of heteropolyacids lower the Td by 100°C. Moreover, the treatment of biomass with a catalytic amount of H3PW12O40 leads to formation of three fractions: solid, liquid and gas, which have been investigated by elemental analysis, TGA, FTIR, GC-MS and NMR. The use of heteropolyacid leads, at 300°C, to a selective transformation of more than 50 wt.% of the holocellulose part of the lignocellulosic biomass. Moreover, 60 wt.% of the catalyst H3PW12O40 are recovered. PMID:24055967

  20. Proton conducting membrane using a solid acid

    NASA Technical Reports Server (NTRS)

    Chisholm, Calum (Inventor); Narayanan, Sekharipuram R. (Inventor); Boysen, Dane (Inventor); Haile, Sossina M. (Inventor)

    2002-01-01

    A solid acid material is used as a proton conducting membrane in an electrochemical device. The solid acid material can be one of a plurality of different kinds of materials. A binder can be added, and that binder can be either a nonconducting or a conducting binder. Nonconducting binders can be, for example, a polymer or a glass. A conducting binder enables the device to be both proton conducting and electron conducting. The solid acid material has the general form M.sub.a H.sub.b (XO.sub.t).sub.c.

  1. Sulfonated reduced graphene oxide as a highly efficient catalyst for direct amidation of carboxylic acids with amines using ultrasonic irradiation.

    PubMed

    Mirza-Aghayan, Maryam; Molaee Tavana, Mahdieh; Boukherroub, Rabah

    2016-03-01

    Sulfonated reduced graphene oxide nanosheets (rGO-SO3H) were prepared by grafting sulfonic acid-containing aryl radicals onto chemically reduced graphene oxide (rGO) under sonochemical conditions. rGO-SO3H catalyst was characterized by Fourier-transform infrared (FT-IR) spectroscopy, Raman spectroscopy, scanning electron microscopy (SEM), X-ray diffraction (XRD), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and X-ray photoelectron spectroscopy (XPS). rGO-SO3H catalyst was successfully applied as a reusable solid acid catalyst for the direct amidation of carboxylic acids with amines into the corresponding amides under ultrasonic irradiation. The direct sonochemical amidation of carboxylic acid takes place under mild conditions affording in good to high yields (56-95%) the corresponding amides in short reaction times. PMID:26585017

  2. Proton conducting membrane using a solid acid

    NASA Technical Reports Server (NTRS)

    Haile, Sossina M. (Inventor); Chisholm, Calum (Inventor); Boysen, Dane A. (Inventor); Narayanan, Sekharipuram R. (Inventor)

    2006-01-01

    A solid acid material is used as a proton conducting membrane in an electrochemical device. The solid acid material can be one of a plurality of different kinds of materials. A binder can be added, and that binder can be either a nonconducting or a conducting binder. Nonconducting binders can be, for example, a polymer or a glass. A conducting binder enables the device to be both proton conducting and electron conducting.

  3. Corrosion-resistant catalyst supports for phosphoric acid fuel cells

    SciTech Connect

    Kosek, J.A.; Cropley, C.C.; LaConti, A.B.

    1990-01-01

    High-surface-area carbon blacks such as Vulcan XC-72 (Cabot Corp.) and graphitized carbon blacks such as 2700{degree}C heat-treated Black Pearls 2000 (HTBP) (Cabot Corp.) have found widespread applications as catalyst supports in phosphoric acid fuel cells (PAFCs). However, due to the operating temperatures and pressures being utilized in PAFCs currently under development, the carbon-based cathode catalyst supports suffer from corrosion, which decreases the performance and life span of a PAFC stack. The feasibility of using alternative, low-cost, corrosion-resistant catalyst support (CRCS) materials as replacements for the cathode carbon support materials was investigated. The objectives of the program were to prepare high-surface-area alternative supports and to evaluate the physical characteristics and the electrochemical stability of these materials. The O{sub 2} reduction activity of the platinized CRCS materials was also evaluated. 2 refs., 3 figs.

  4. Superprotonic solid acids: Structure, properties, and applications

    NASA Astrophysics Data System (ADS)

    Boysen, Dane Andrew

    In this work, the structure and properties of superprotonic MH nXO4-type solid acids (where M = monovalent cation, X = S, Se, P, As, and n = 1, 2) have been investigated and, for the first time, applied in fuel cell devices. Several MH nXO4-type solid acids are known to undergo a "superprotonic" solid-state phase transition upon heating, in which the proton conductivity increases by several orders of magnitude and takes on values of ˜10 -2O-1cm-1. The presence of superprotonic conductivity in fully hydrogen bonded solid acids, such as CsH2PO4, has long been disputed. In these investigations, through the use of pressure, the unequivocal identification of superprotonic behavior in both RbH2PO4 and CsH2PO 4 has been demonstrated, whereas for chemically analogous compounds with smaller cations, such as KH2PO4 and NaH2PO 4, superprotonic conductivity was notably absent. Such observations have led to the adoption of radius ratio rules, in an attempt to identify a critical ion size effect on the presence of superprotonic conductivity in solid acids. It has been found that, while ionic size does play a prominent role in the presence of superprotonic behavior in solid acids, equally important are the effects of ionic and hydrogen bonding. Next, the properties of superprotonic phase transition have been investigated from a thermodynamic standpoint. With contributions from this work, a formulation has been developed that accounts for the entropy resulting from both the disordering of both hydrogen bonds and oxy-anion librations in the superprotonic phase of solid acids. This formulation, fundamentally derived from Linus Pauling's entropy rules for ice, accurately accounts for the change in entropy through a superprotonic phase transition. Lastly, the first proof-of-priniciple fuel cells based upon solid acid electrolytes have been demonstrated. Initial results based upon a sulfate electrolyte, CsHSO4, demonstrated the viability of solid acids, but poor chemical stability under the highly reducing H2 gas environment of the fuel cell anode. Later experiments employing a CsH2PO4 electrolyte proved quite successful. The results of these solid acid-based fuel cell measurements suggest solid acids could serve as an alternative to current state-of-the-art fuel cell electrolytes.

  5. Kl-impregnated Oyster Shells as a Solid Catalyst for Soybean Oil Transesterificaton

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Research on inexpensive and green catalysts is needed for economical production of biodiesel. The goal of the research was to test KI-impregnated oyster shell as a solid catalyst for transesterification of soybean oil. Specific objectives were to characterize KI-impregnated oyster shell, determine t...

  6. Novel Solid Base Catalysts for the Production of Biodiesel from Lipids

    E-print Network

    Zhao, Lina

    2010-12-17

    and stability for biodiesel production still remains a challenge. This dissertation is dedicated to developing novel solid base catalysts and applying them to an environmentally beneficial reactive distillation process for transesterification of vegetable oils...

  7. Nickel recovery from spent Raneynickel catalyst through dilute sulfuric acid leaching and soda ash precipitation.

    PubMed

    Lee, Jin Young; Rao, S Venkateswara; Kumar, B Nagaphani; Kang, Dong Jun; Reddy, B Ramachandra

    2010-04-15

    Pharmaceutical industry makes extensive use of Raneynickel catalyst for various organic drug intermediates/end products. Spent catalysts contain environmentally critical and economically valuable metals. In the present study, a simple hydrometallurgical process using dilute sulfuric acid leaching was described for the recovery of nickel from spent Raneynickel catalyst. Recovery of nickel varied with acid concentration and time, whereas temperature had negligible effect. Increase of S/L ratio to 30% (w/v) showed marginal effect on nickel (90%) recovery, whereas Al recovery decreased drastically to approximately 20%. Under the optimum conditions of leaching viz: 12 vol.% H(2)SO(4), 30 degrees C, 20% solid to liquid (S/L) ratio and 120 min reaction time, it was possible to recover 98.6% Ni along with 39.2% Al. Leach liquor [pH 0.7] containing 85.0 g/L Ni and 3.25 g/L Al was adjusted to pH 5.4 with 30 wt.% alkali for quantitative aluminum removal. Nickel loss was about 2% during this Al removal step. Nickel from the purified leach liquor was recovered as nickel carbonate by adding required amount of Na(2)CO(3). The purity of NiCO(3) product was found to be 100% with a Ni content of 48.6%. Na(2)SO(4) was recovered as a by-product with a purity of 99%. Complete process is presented. PMID:20018448

  8. Production of glycolic acid from glycerol using novel fine-disperse platinum catalysts

    NASA Astrophysics Data System (ADS)

    Sproge, E.; Chornaja, S.; Dubencovs, K.; Kampars, V.; Kulikova, L.; Serga, V.; Karashanova, D.

    2015-03-01

    Using extractive-pyrolytic method fine-disperse Pt containing composites were synthesized and tested in catalytic glycerol oxidation. Catalyst activity and selectivity to glycolic acid was determined oxidizing glycerol in mild conditions. It was concluded that only iron containing platinum catalysts were selective to glycolic acid. Selectivity to glycolic acid reached 53-60% with glycerol conversion 12-56%.

  9. Geometrical isomerization of fatty acids with sulfur as a catalyst

    SciTech Connect

    Grompone, M.A.; Tancredi, N.A. )

    1991-08-01

    This paper reports on the kinetics of the geometrical isomerization of oleic and palmitoleic acids, both contained in U.S.P. oleic acid that were studied. Sulfur powder was used as a catalyst. The methyl esters of fatty acids were analyzed by GLC with 15% OV-275 columns. The sulfur-catalyzed isomerization at 180 and 225{degrees} C proceeds via two consecutive mechanisms. The position of equilibrium is reached by the second mechanism. For this, at any particular initial concentration of sulfur, the pseudo- first-order rate dependence on substrate for a reversible reaction holds. The full rate has been shown to be proportional to the initial sulfur concentration taken to the 1.2 power. The rate constants at both temperatures and the activation energies were calculated.

  10. Non-noble catalysts and catalyst supports for phosphoric acid fuel cells

    NASA Technical Reports Server (NTRS)

    Mcalister, A. J.

    1981-01-01

    Four different samples of the cubic alloys W sub x-1 Ti sub x C sub 1-y were prepared and found to be active and CO tolerant. When the activities of these cubic alloys were weighted by the reciprocal of the square of the W exchange, they displayed magnitudes and dependence on bulk C deficiency comparable to those of highly active forms of WC. It is concluded that they may offer important insight into the nature of the active sites on, and means for improving the performance of, W-C anode catalysts for use in phosphoric acid fuel cells.

  11. Non-noble catalysts and catalyst supports for phosphoric acid fuel cells

    NASA Technical Reports Server (NTRS)

    Mcalister, A. J.

    1980-01-01

    Tungsten carbide, which is known to be active for hydrogen oxidation and CO tolerant has a hexagonal structure. Titanium carbide is inactive and has a cubic structure. Four different samples of the cubic alloys Wx-1TixC were prepared and found to be active and CO tolerant. These alloys are of interest as possible phosphoric acid fuel cell catalysts. They also are of interest as opportunities to study the activity of W in a different crystalline environment and to correlate the activities of the surface sites with surface composition.

  12. Non-noble catalysts and catalyst supports for phosphoric acid fuel cells

    NASA Technical Reports Server (NTRS)

    Mcalister, A. J.

    1981-01-01

    Tungsten carbide, which is active for hydrogen oxidation, is CO tolerant and has a hexagonal structure is discussed. Titanium carbide is inactive and has a cubic structure. Four different samples of the cubic alloys W sub x-1Ti sub XC sub 1-y were found to be active and CO tolerant. When the activities of these cubic alloys are weighted by the reciprocal of the square to those of highly forms of WC. They offer important insight into the nature of the active sites on W-C anode catalysts for use in phosphoric acid fuel cells.

  13. Cathode catalysts for primary phosphoric acid fuel cells

    NASA Technical Reports Server (NTRS)

    1981-01-01

    Alkylation or carbon Vulcan XC-72, the support carbon, was shown to provide the most stable bond type for linking cobalt dehydrodibenzo tetraazannulene (CoTAA) to the surface of the carbon; this result is based on data obtained by cyclic voltammetry, pulse voltammetry and by release of 14C from bonded CoTAA. Half-cell tests at 100 C in 85% phosphoric acid showed that CoTAA bonded to the surface of carbon (Vulcan XC-72) via an alkylation procedure is a more active catalyst than is platinum based on a factor of two improvement in Tafel slope; dimeric CoTAA had catalytic activity equal to platinum. Half-cell tests also showed that bonded CoTAA catalysts do not suffer a loss in potential when air is used as a fuel rather than oxygen. Commercially available polytetrafluroethylene (PTFE) was shown to be unstable in the fuel cell environment with degradation occurring in 2000 hours or less. The PTFE was stressed at 200 C in concentrated phosphoric acid as well as electrochemically stressed in 150 C concentrated phosphoric acid; the surface chemistry of PTFE was observed to change significantly. Radiolabeled PTFE was prepared and used to verify that such chemical changes also occur in the primary fuel cell environment.

  14. Solid-state NMR studies of Ziegler-Natta and metallocene catalysts.

    PubMed

    Tijssen, Koen C H; Blaakmeer, E S Merijn; Kentgens, Arno P M

    2015-01-01

    Ziegler-Natta catalysts are the workhorses of polyolefin production. However, although they have been used and intensively studied for half a century, there is still no comprehensive picture of their mechanistic operation. New techniques are needed to gain more insight in these catalysts. Solid-state NMR has reached a high level of sophistication over the last few decades and holds great promise for providing a deeper insight in Ziegler-Natta catalysis. This review outlines the possibilities for solid-state NMR to characterize the different components and interactions in Ziegler-Natta and metallocene catalysts. An overview is given of some of the expected mechanisms and the resulting polymer microstructure and other characteristics. In the second part of this review we present studies that have used solid-state NMR to investigate the composition of Ziegler-Natta and metallocene catalysts or the interactions between their components. PMID:25957882

  15. Dynamic Restructuring Of Solid Catalyst Cluster During Carbon Nanotube CVD

    E-print Network

    Dunin-Borkowski, Rafal E.

    a liquid intermediate and that bulk catalyst effects dominate CNT growth dynamics. Calculations of size films on Si/SiO2. In-situ environmental HRTEM shows that Ni films supported on SiOx membranes already start restructuring at temperatures as low as 200°C and that the bulk of the catalyst cluster

  16. Solid acids as fuel cell electrolytes

    NASA Astrophysics Data System (ADS)

    Haile, Sossina M.; Boysen, Dane A.; Chisholm, Calum R. I.; Merle, Ryan B.

    2001-04-01

    Fuel cells are attractive alternatives to combustion engines for electrical power generation because of their very high efficiencies and low pollution levels. Polymer electrolyte membrane fuel cells are generally considered to be the most viable approach for mobile applications. However, these membranes require humid operating conditions, which limit the temperature of operation to less than 100°C they are also permeable to methanol and hydrogen, which lowers fuel efficiency. Solid, inorganic, acid compounds (or simply, solid acids) such as CsHSO4 and Rb3H(SeO4)2 have been widely studied because of their high proton conductivities and phase-transition behaviour. For fuel-cell applications they offer the advantages of anhydrous proton transport and high-temperature stability (up to 250°C). Until now, however, solid acids have not been considered viable fuel-cell electrolyte alternatives owing to their solubility in water and extreme ductility at raised temperatures (above approximately 125°C). Here we show that a cell made of a CsHSO4 electrolyte membrane (about 1.5mm thick) operating at 150-160°C in a H2/O2 configuration exhibits promising electrochemical performances: open circuit voltages of 1.11V and current densities of 44mAcm-2 at short circuit. Moreover, the solid-acid properties were not affected by exposure to humid atmospheres. Although these initial results show promise for applications, the use of solid acids in fuel cells will require the development of fabrication techniques to reduce electrolyte thickness, and an assessment of possible sulphur reduction following prolonged exposure to hydrogen.

  17. Recent progress in the development of solid catalysts for biomass conversion into high value-added chemicals

    NASA Astrophysics Data System (ADS)

    Hara, Michikazu; Nakajima, Kiyotaka; Kamata, Keigo

    2015-06-01

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

  18. The acrylation of glycerol over solid base catalysts: A precursor to functionalized lipids

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Transesterification of lipids using lipases is a common strategy used to incorporate novel acids into triacylglycerides. This approach, however, is limited to acids with pKa’s similar to common fatty acids. To overcome this limitation, we have used heterogeneous basic catalysts for the synthesis o...

  19. An Eco-Friendly Improved Protocol for the Synthesis of Bis(3-indolyl)methanes Using Poly(4-vinylpyridinium)hydrogen Sulfate as Efficient, Heterogeneous, and Recyclable Solid Acid Catalyst

    PubMed Central

    Banothu, Janardhan; Gali, Rajitha; Velpula, Ravibabu; Bavantula, Rajitha; Crooks, Peter A.

    2013-01-01

    Highly efficient and eco-friendly protocol for the synthesis of bis(3-indolyl)methanes by the electrophilic substitution reaction of indole with aldehydes catalyzed by poly(4-vinylpyridinium)hydrogen sulfate was described. Excellent yields, shorter reaction times, simple work-up procedure, avoiding hazardous organic solvents, and reusability of the catalyst are the most obvious advantages of this method. PMID:24052864

  20. From the Design of a Chiral Lewis Acid Catalyst to Metal-Catalyzed Coupling Reactions

    E-print Network

    Fu, Gregory C.

    in chiral Lewis acid catalysis to a project focused on the development of new palladium and nickel catalysts for carbon- carbon bond-forming reactions. I. Design of a Versatile Chiral Lewis Acid Catalyst The origin reported to date, the carbonyl system is activated through a -symmetry interaction between an oxygen lone

  1. Comparison of catalysts for direct transesterification of fatty acids in freeze-dried forage samples

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Preparation of fatty acid methyl esters from forages comparing BF3 in CH3OH to HCl in CH3OH as a catalyst in single-step direct transesterification has not been reported. Our objective was to compare 1.09 M methanolic HCl to 7% BF3 in CH3OH as catalysts for direct transesterification of fatty acids ...

  2. Effectiveness of paper-structured catalyst for the operation of biodiesel-fueled solid oxide fuel cell

    NASA Astrophysics Data System (ADS)

    Quang-Tuyen, Tran; Kaida, Taku; Sakamoto, Mio; Sasaki, Kazunari; Shiratori, Yusuke

    2015-06-01

    Mg/Al-hydrotalcite (HDT)-dispersed paper-structured catalyst (PSC) was prepared by a simple paper-making process. The PSC exhibited excellent catalytic activity for the steam reforming of model biodiesel fuel (BDF), pure oleic acid methyl ester (oleic-FAME, C19H36O2) which is a mono-unsaturated component of practical BDFs. The PSC exhibited fuel conversion comparable to a pelletized catalyst material, here, conventional Ni-zirconia cermet anode for solid oxide fuel cell (SOFC) with less than one-hundredth Ni weight. Performance of electrolyte-supported cell connected with the PSC was evaluated in the feed of oleic-FAME, and stable operation was achieved. After 60 h test, coking was not observed in both SOFC anode and PSC.

  3. Green acetylation of solketal and glycerol formal by heterogeneous acid catalysts to form a biodiesel fuel additive.

    PubMed

    Dodson, Jennifer R; Leite, Thays d C M; Pontes, Nathália S; Peres Pinto, Bianca; Mota, Claudio J A

    2014-09-01

    A glut of glycerol has formed from the increased production of biodiesel, with the potential to integrate the supply chain by using glycerol additives to improve biodiesel properties. Acetylated acetals show interesting cold flow and viscosity effects. Herein, a solventless heterogeneously catalyzed process for the acetylation of both solketal and glycerol formal to new products is demonstrated. The process is optimized by studying the effect of acetylating reagent (acetic acid and acetic anhydride), reagent molar ratios, and a variety of commercial solid acid catalysts (Amberlyst-15, zeolite Beta, K-10 Montmorillonite, and niobium phosphate) on the conversion and selectivities. High conversions (72-95%) and selectivities (86-99%) to the desired products results from using acetic anhydride as the acetylation reagent and a 1:1 molar ratio with all catalysts. Overall, there is a complex interplay between the solid catalyst, reagent ratio, and acetylating agent on the conversion, selectivities, and byproducts formed. The variations are discussed and explained in terms of reactivity, thermodynamics, and reaction mechanisms. An alternative and efficient approach to the formation of 100% triacetin involves the ring-opening, acid-catalyzed acetylation from solketal or glycerol formal with excesses of acetic anhydride. PMID:25045049

  4. In situ biodiesel production from greasy sewage sludge using acid and enzymatic catalysts.

    PubMed

    Sangaletti-Gerhard, Naiane; Cea, Mara; Risco, Vicky; Navia, Rodrigo

    2015-03-01

    This study proposes to select the most appropriate sewage sludge (greasy, primary and secondary) for in situ transesterification and to compare the technical, economic and energetic performance of an enzymatic catalyst (Novozym®435) with sulfuric acid. Greasy sludge was selected as feedstock for biodiesel production due to its high lipid content (44.4%) and low unsaponifiable matter. Maximum methyl esters yield (61%) was reached when processing the wet sludge using sulfuric acid as catalyst and n-hexane, followed by dried-greasy sludge catalyzed by Novozym®435 (57% methyl esters). Considering the economic point of view, the process using acid catalyst was more favorable compared to Novozym®435 catalyst due to the high cost of lipase. In general, greasy sludge (wet or dried) showed high potential to produce biodiesel. However, further technical adjustments are needed to make biodiesel production by in situ transesterification using acid and enzymatic catalyst feasible. PMID:25528605

  5. Materials Chemistry of Superprotonic Solid Acids

    NASA Astrophysics Data System (ADS)

    Kislitsyn, Mikhail N.

    Solid acid is a class of materials that shows potential as a fuel cell electrolyte. Understanding the phase and mechanical stability are required for further development of this technology. We addressed both issues in this work. We expanded the use of the crystallographic theory of the phase transformation to three major classes of solid acids. That allowed us to relate material properties hysteresis to fundamental crystallographic and thermodynamic parameters. The understanding of the mechanism of the transformation can guide the effort to create materials with desired hysteresis. Careful investigation of the thermal and phase behavior of CsHSO4, CsH2PO4, Rb3H(SeO4)2 and in Cs1-xRb xH2PO4 solid solution series for both low and high temperature phases was performed and crystal symmetry and lattice parameters for Cs0.75Rb0.25H2PO4, T=240°C phase were found for the first time. Consistency between predicted and measured properties was shown for all three different classes of solid acids as well as for the isostructural solid solution series. Nanocomposite materials based on cesium hydrogen sulfate and nanometer size silica were characterized. We observed 30--40 nm size surface stabilization of our material at the high temperature phase, otherwise metastable at room temperature. We developed methods to quantitatively study interface phases and its effect on ion mobility. The method allowed us to quantitatively find crystalline and amorphous amounts in the composites. We observed 3--4 order decrease in spin-lattice relaxation values of the metastable phase in the composite. Solid state NMR allowed surface interactions directly and suggest high ion mobility. Strong effect on superprotonic transition temperature in composites was observed. Superprotonic phase was stable in composites at temperatures up to 70°C below phase transition compared with pure phase CsHSO4. The mechanism and activation energy of the creep plastic deformation in CsHSO4 were found. Based on that, a method to reduce creep by 1--2 orders of magnitude was developed and creep-resistant material was synthesized.

  6. UreaFormaldehyde-Resin Gel Time As Affected by the pH Value, Solid Content, and Catalyst

    E-print Network

    Wang, Siqun

    Urea­Formaldehyde-Resin Gel Time As Affected by the pH Value, Solid Content, and Catalyst Cheng to investigate the effects of the resin solid content, catalyst content, and pH value obtained by the addition of ammonium chloride, the pH value of the resin mixture decreased to 7 but not significantly further because

  7. Selective conversion of cotton cellulose to glucose and 5-hydroxymethyl furfural with SO4(2-)/MxOy solid superacid catalyst.

    PubMed

    Yang, Fang; Li, Yang; Zhang, Qian; Sun, Xiaofeng; Fan, Hongxian; Xu, Nian; Li, Gang

    2015-10-20

    This paper presented a mild hydrothermal process for degradation of cotton cellulose with solid superacid catalyst and selective conversion of cotton cellulose to glucose and 5-hydroxymethyl furfural (HMF). Five kinds of solid superacid catalyst such as SO4(2-)/SnO2, SO4(2-)/TiO2, SO4(2-)/ZrO2, SO4(2-)/Fe2O3 and SO4(2-)/Al2O3 were prepared by impregnation method. The BET surface area of catalyst SO4(2-)/SnO2 was up to 118.8m(2)g(-1) when impregnation was performed with 1molL(-1) H2SO4 of impregnating solution at 550°C calcination temperature for 3h. It made the hydrothermal temperature of cellulose degradation decrease to 190°C successfully and suppressed the side reaction. The NH3-TPD profile of SO4(2-)/SnO2 indicated there was a wide region of stronger acid sites on the catalyst surface. The depolymerization of cotton cellulose obtained 11.0% yield and 22.0% selectivity of HMF and 26.8% yield and 53.4% selectivity of glucose, respectively. The regeneration and reuse of solid superacid catalyst were also discussed in this paper. PMID:26256154

  8. Regeneration of silica-supported silicotungstic acid as a catalyst for the dehydration of glycerol.

    PubMed

    Katryniok, Benjamin; Paul, Sébastien; Capron, Mickaël; Bellière-Baca, Virginie; Rey, Patrick; Dumeignil, Franck

    2012-07-01

    The dehydration reaction of glycerol to acrolein is catalyzed by acid catalysts. These catalysts tend to suffer from the formation of carbonaceous species on their surface (coking), which leads to substantial degradation of their performances (deactivation). To regenerate the as-deactivated catalysts, various techniques have been proposed so far, such as the co-feeding of oxygen, continuous regeneration by using a moving catalytic bed, or alternating between reaction and regeneration. Herein, we study the regeneration of supported heteropolyacid catalysts. We show that the support has a strong impact on the thermal stability of the active phase. In particular, zirconia has been found to stabilize silicotungstic acid, thus enabling the nondestructive regeneration of the catalyst. Furthermore, the addition of steam to the regeneration feed has a positive impact by hindering the degradation reaction by equilibrium displacement. The catalysts are further used in a periodic reaction/regeneration process, whereby the possibility of maintaining long-term catalytic performances is evidenced. PMID:22505057

  9. Displacement of Hexanol by the Hexanoic Acid Overoxidation Product in Alcohol Oxidation on a Model Supported Palladium Nanoparticle Catalyst

    SciTech Connect

    Buchbinder, Avram M.; Ray, Natalie A.; Lu, Junling; Van Duyne, Richard P.; Stair, Peter C.; Weitz, Eric; Geiger, Franz M.

    2011-11-09

    This work characterizes the adsorption, structure, and binding mechanism of oxygenated organic species from cyclohexane solution at the liquid/solid interface of optically flat alumina-supported palladium nanoparticle surfaces prepared by atomic layer deposition (ALD). The surface-specific nonlinear optical vibrational spectroscopy, sum-frequency generation (SFG), was used as a probe for adsorption and interfacial molecular structure. 1-Hexanoic acid is an overoxidation product and possible catalyst poison for the aerobic heterogeneous oxidation of 1-hexanol at the liquid/solid interface of Pd/Al?O? catalysts. Single component and competitive adsorption experiments show that 1-hexanoic acid adsorbs to both ALD-prepared alumina surfaces and alumina surfaces with palladium nanoparticles, that were also prepared by ALD, more strongly than does 1-hexanol. Furthermore, 1-hexanoic acid adsorbs with conformational order on ALD-prepared alumina surfaces, but on surfaces with palladium particles the adsorbates exhibit relative disorder at low surface coverage and become more ordered, on average, at higher surface coverage. Although significant differences in binding constant were not observed between surfaces with and without palladium nanoparticles, the palladium particles play an apparent role in controlling adsorbate structures. The disordered adsorption of 1-hexanoic acid most likely occurs on the alumina support, and probably results from modification of binding sites on the alumina, adjacent to the particles. In addition to providing insight on the possibility of catalyst poisoning by the overoxidation product and characterizing changes in its structure that result in only small adsorption energy changes, this work represents a step toward using surface science techniques that bridge the complexity gap between fundamental studies and realistic catalyst models.

  10. Method of performing sugar dehydration and catalyst treatment

    DOEpatents

    Hu, Jianli [Kennewick, WA; Holladay, Johnathan E [Kennewick, WA; Zhang, Xinjie [Burlington, MA; Wang, Yong [Richland, WA

    2010-06-01

    The invention includes a method of treating a solid acid catalyst. After exposing the catalyst to a mixture containing a sugar alcohol, the catalyst is washed with an organic solvent and is then exposed to a second reaction mixture. The invention includes a process for production of anhydrosugar alcohol. A solid acid catalyst is provided to convert sugar alcohol in a first sample to an anhydrosugar alcohol. The catalyst is then washed with an organic solvent and is subsequently utilized to expose a second sample. The invention includes a method for selective production of an anhydrosugar. A solid acid catalyst is provided within a reactor and anhydrosugar alcohol is formed by flowing a starting sugar alcohol into the reactor. The acid catalyst is then exposed to an organic solvent which allows a greater amount of additional anhydrosugar to be produced than would occur without exposing the acid catalyst to the organic solvent.

  11. Tightly convoluted polymeric phosphotungstate catalyst: an oxidative cyclization of alkenols and alkenoic acids.

    PubMed

    Yamada, Yoichi M A; Guo, Haiqing; Uozumi, Yasuhiro

    2007-04-12

    [reaction: see text] A tightly convoluted polymeric phosphotungstate catalyst was prepared via ionic assembly of H3PW12O40 and poly(alkylpyridinium). An oxidative cyclization of various alkenols and alkenoic acids was efficiently promoted by the polymeric catalyst in aq H2O2 in the absence of organic solvents to afford the corresponding cyclic ethers and lactones in high yield. The catalyst was reused four times without loss of catalytic activity. PMID:17371036

  12. Metal recovery from spent hydrodesulfurization catalysts using a combined acid-leaching and electrolysis process.

    PubMed

    Lai, Yi-Chieh; Lee, Wen-Jhy; Huang, Kuo-Lin; Wu, Chung-Mou

    2008-06-15

    This study focuses on recovering valuable metals from spent hydrodesulfurization (HDS) catalysts using a combined acid-leaching and fluidized-bed electrolysis process. The electrolytic cell was equipped with a glass bead medium, an iridium oxide mesh anode, and a stainless steel plate cathode. An acid solution consisting of concentrated HNO3/H2SO4/HCl with a volume ratio of 2:1:1 was found to be better than the other tested solution (HNO3/H2SO4=1:1) to leach the metals. For the three-acid mixture, the best solid/liquid ratio and leaching time were 40 g/L and 1 h, respectively, at 70 degrees C; under this condition, the leaching yields of target metals (Mo, Ni, and V) in the 1st stage of leaching reached 90, 99, and 99%, respectively, much higher than those in the 2nd/3rd/4th stages. When this acid leachate was electrolyzed for 2 h at 2 A constant current (current density=approximately 35.7 mA/cm2), a stable cell voltage of 5 V was observed. The electrolytic recoveries of Mo, Ni, and V were approximately 15, 61, and 66%, respectively, but extending the electrolysis time from 2 to 4 h did not increase the recoveries. For this operation, the total recoveries (leaching yieldxelectrolytic recovery) of Mo, Ni, and V were approximately 14, 60, and 65%, respectively. PMID:18060691

  13. Solid-state actinide acid phosphites from phosphorous acid melts

    NASA Astrophysics Data System (ADS)

    Oh, George N.; Burns, Peter C.

    2014-07-01

    The reaction of UO3 and H3PO3 at 100 °C and subsequent reaction with dimethylformamide (DMF) produces crystals of the compound (NH2(CH3)2)[UO2(HPO2OH)(HPO3)]. This compound crystallizes in space group P21/n and consists of layers of uranyl pentagonal bipyramids that share equatorial vertices with phosphite units, separated by dimethylammonium. In contrast, the reaction of phosphorous acid and actinide oxides at 210 °C produces a viscous syrup. Subsequent dilution in solvents and use of standard solution-state methods results in the crystallization of two polymorphs of the actinide acid phosphites An(HPO2OH)4 (An=U, Th) and of the mixed acid phosphite-phosphite U(HPO3)(HPO2OH)2(H2O)·2(H2O). ?- and ?-An(HPO2OH)4 crystallize in space groups C2/c and P21/n, respectively, and comprise a three-dimensional network of An4+ cations in square antiprismatic coordination corner-sharing with protonated phosphite units, whereas U(HPO3)(HPO2OH)2(H2O)2·(H2O) crystallizes in a layered structure in space group Pbca that is composed of An4+ cations in square antiprismatic coordination corner-sharing with protonated phosphites and water ligands. We discuss our findings in using solid inorganic reagents to produce a solution-workable precursor from which solid-state compounds can be crystallized.

  14. Effects of Phosphoric Acid Concentration on Platinum Catalyst and Phosphoric Acid Hydrogen Pump Performance

    NASA Astrophysics Data System (ADS)

    Buelte, Steve

    This work involves the study of the operational performance of phosphoric acid based electrochemical hydrogen pumps with a polybenzimidazole (PBI) electrolytic membrane. During characterization of these devices, the power consumption was found to be highly sensitive to the water vapor pressure in the supply gas stream which in turn affects the phosphoric acid concentration. The power requirement was 30 times higher when the supply gas stream was not humidified than when the supply gas stream was humidified. Upon testing of electrochemical hydrogen pumps over a range of supply gas water vapor pressures from 150 to 0.8 mmHg, it was found that the effective platinum catalyst area decreases as phosphoric acid concentration increases in response to declining supply gas vapor pressure. It was hypothesized that the decline in the effective platinum catalyst area was caused by the adsorption of a species from the electrolyte that increases in concentration with phosphoric acid concentration. Polyphosphoric acid species were such a species which increased in concentration as phosphoric acid concentration increased and as a result were hypothesized to be the species adsorbing on the platinum catalyst. Additional testing was conducted in an electrochemical half cell in which the effect of phosphoric acid concentration on the platinum surface area at a single electrode interface could be studied. Impedance spectroscopy and cyclic voltammetry (CV) testing was used to measure changes in exchange current and platinum surface area following the exposure of the electrode to electrolyte. Platinum surface coverage estimates from CV measurements were 60-87% at a phosphoric acid concentration of 76 wt% P2O5 (105 wt% H3PO 4) and near 100% coverage at 83.3 wt% P2O5 (115 wt% H3PO4). The exchange current for hydrogen oxidation and reduction on platinum decreased by a factor of 25 for 76 wt% P2O 5 and a factor of 1000 for 83.3 wt% P2O5 phosphoric acid concentration within 36 hours. A similar dependence of platinum surface coverage and exchange current on phosphoric acid concentration was observed during hydrogen pump testing over a range of supply gas vapor pressures. This work indicates that platinum catalyst activity declines sharply above a phosphoric acid concentration of 72.4 wt% P2O5 (100 wt% H3PO4) which causes a significant increase in hydrogen pump power consumption. To reduce power consumption, the hydrogen gas supplied to the hydrogen pump requires humidification to a vapor pressure of at least 55 mmHg. The addition of humidification to the supply gas stream adds complexity to a system incorporating a phosphoric acid hydrogen pump. The need to add humidification equipment to reduce phosphoric acid hydrogen pump power consumption may have a significant impact when such devices are applied to hydrogen separation applications including hydrogen recovery from industrial exhaust streams and for emerging alternative energy applications.

  15. Metal-organic frameworks as solid catalysts for the synthesis of nitrogen-containing heterocycles.

    PubMed

    Dhakshinamoorthy, Amarajothi; Garcia, Hermenegildo

    2014-08-21

    Metal-organic frameworks (MOFs) are finding increasing application as solid catalysts for liquid phase reactions leading to the synthesis of fine chemicals. In the present review we have focused on those reports describing the use of MOFs as catalysts for the synthesis of N-containing heterocycles that is a class of organic compounds with high added value due to their therapeutic use as drugs and their remarkable biological activities. After an introduction describing relevant structural features of MOFs and the nature of their active sites, this manuscript is organized according to the type of N-containing heterocycle synthesized employing MOFs as catalysts including pyrimidines, N-substituted piperidines, quinolines, indoles, N-substituted imidazoles, triazoles and heterocyclic amides. Special attention has been paid to the structural stability of MOFs under the reaction conditions, to the occurrence of metal leaching and reusability. The final section of this review provides some concluding remarks and future prospects for the field, with emphasis on showing the superiority of MOFs with respect to other solid catalysts for this type of liquid phase organic reactions and pointing out that the final goal in this research would be the use of these materials as catalysts in real industrial synthesis. PMID:24614959

  16. Low-temperature, vapor-liquid-solid, laterally grown silicon films using alloyed catalysts

    NASA Astrophysics Data System (ADS)

    LeBoeuf, Jerome L.; Brodusch, Nicolas; Gauvin, Raynald; Quitoriano, Nathaniel J.

    2014-12-01

    Using amorphous oxide templates known as micro-crucibles which confine a vapor-liquid-solid catalyst to a specific geometry, two-dimensional silicon thin-films of a single orientation have been grown laterally over an amorphous substrate and defects within crystals have been necked out. The vapor-liquid-solid catalysts consisted nominally of 99% gold with 1% titanium, chromium, or aluminum, and each alloy affected the processing of micro-crucibles and growth within them significantly. It was found that chromium additions inhibited the catalytic effect of the gold catalysts, titanium changed the morphology of the catalyst during processing and aluminum stabilized a potential third phase in the gold-silicon system upon cooling. Two mechanisms for growing undesired nanowires were identified both of which hindered the VLS film growth, fast silane cracking rates and poor gold etching, which left gold nanoparticles near the gold-vapor interface. To reduce the silane cracking rates, growth was done at a lower temperature while an engineered heat and deposition profile helped to reduce NWs caused by the second mechanism. Through experimenting with catalyst compositions, the fundamental mechanisms which produce concentration gradients across the gold-silicon alloy within a given micro-crucible have been proposed. Using the postulated mechanisms, micro-crucibles were designed which promote high-quality, single crystal growth of semiconductors.

  17. Highly active supported palladium catalyst for the regioselective synthesis of 2-arylpropionic acids by carbonylation

    E-print Network

    Jayasree, S.; Seayad, A.; Chaudhari, Raghunath Vitthal

    1999-01-01

    A catalyst system consisting of supported palladium in the presence of phosphine ligands, TsOH and LiCl catalyses the carbonylation of 1-arylethanols to 2-arylpropionic acids with significantly improved activity and ...

  18. A NiFeCu alloy anode catalyst for direct-methane solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Wang, Wei; Zhu, Huaiyu; Yang, Guangming; Park, Hee Jung; Jung, Doh Won; Kwak, Chan; Shao, Zongping

    2014-07-01

    In this study, a new anode catalyst based on a NiFeCu alloy is investigated for use in direct-methane solid oxide fuel cells (SOFCs). The influence of the conductive copper introduced into the anode catalyst layer on the performance of the SOFCs is systematically studied. The catalytic activity for partial oxidation of methane and coking resistance tests are proposed with various anode catalyst layer materials prepared using different methods, including glycine nitrate process (GNP), physical mixing (PM) and impregnation (IMP). The surface conductivity tests indicate that the conductivities of the NiFe-ZrO2/Cu (PM) and NiFe-ZrO2/Cu (IMP) catalysts are considerably greater than that of NiFe-ZrO2/Cu (GNP), which is consistent with the SEM results. Among the three preparation methods, the cell containing the NiFe-ZrO2/Cu (IMP) catalyst layer performs best on CH4-O2 fuel, especially under reduced temperatures, because the coking resistance should be considered in real fuel cell conditions. The cell containing the NiFe-ZrO2/Cu (IMP) catalyst layer also delivers an excellent operational stability using CH4-O2 fuel for 100 h without any signs of decay. In summary, this work provides new alternative anode catalytic materials to accelerate the commercialization of SOFC technology.

  19. Vapor Phase Dehydration of Glycerol to Acrolein Over SBA-15 Supported Vanadium Substituted Phosphomolybdic Acid Catalyst.

    PubMed

    Viswanadham, Balaga; Srikanth, Amirineni; Kumar, Vanama Pavan; Chary, Komandur V R

    2015-07-01

    Vapor phase dehydration of glycerol to acrolein was investigated over heteropolyacid (HPA) catalysts containing vanadium substituted phosphomolybdic acid (H4PMo11VO40) supported on mesoporous SBA-15. A series of HPA catalysts with HPA loadings varying from 10-50 wt% were prepared by impregnation method on SBA-15 support. The catalysts were characterized by X-ray diffraction, Raman spectroscopy, Fourier Transform infrared spectroscopy, temperature-programmed desorption of NH3, pyridine adsorbed FT-IR spectroscopy, scanning electron microscopy, pore size distribution and specific surface area measurements. The nature of acidic sites was examined by pyridine adsorbed FT-IR spectroscopy. XRD results suggest that the active phase containing HPA was highly dispersed at lower loadings on the support. FT-IR and Raman spectra results confirm that the presence of primary Keggin ion structure of HPA on the support and it was not affected during the preparation of catalysts. Pore size distribution results reveal that all the samples show unimodel pore size distribution with well depicted mesoporous structure. NH3-TPD results suggest that the acidity of catalysts increased with increase of HPA loading. The findings of acidity measurements by FT-IR spectra of pyridine adsorption reveals that the catalysts consist both the Brønsted and Lewis acidic sites and the amount of Brønsted acidic sites are increasing with HPA loading. SBA-15 supported vanadium substituted phosphomolybdic acid catalysts are found to be highly active during the dehydration reaction and exhibited 100% conversion of glycerol (10 wt% of glycerol) and the acrolein selectivity was appreciably changed with HPA active phase loading. The catalytic functionalities during glycerol dehydration are well correlated with surface acidity of the catalysts. PMID:26373149

  20. Phase Behavior of Complex Superprotonic Solid Acids

    NASA Astrophysics Data System (ADS)

    Panithipongwut, Chatr

    Superprotonic phase transitions and thermal behaviors of three complex solid acid systems are presented, namely Rb3H(SO4) 2-RbHSO4 system, Rb3H(SeO4)2-Cs 3H(SeO4)2 solid solution system, and Cs6 (H2SO4)3(H1.5PO4) 4. These material systems present a rich set of phase transition characteristics that set them apart from other, simpler solid acids. A.C. impedance spectroscopy, high-temperature X-ray powder diffraction, and thermal analysis, as well as other characterization techniques, were employed to investigate the phase behavior of these systems. Rb3H(SO4)2 is an atypical member of the M3H(XO4)2 class of compounds (M = alkali metal or NH4+ and X = S or Se) in that a transition to a high-conductivity state involves disproportionation into two phases rather than a simple polymorphic transition [1]. In the present work, investigations of the Rb3H(SO4)2-RbHSO4 system have revealed the disproportionation products to be Rb2SO 4 and the previously unknown compound Rb5H3(SO 4)4. The new compound becomes stable at a temperature between 25 and 140 °C and is isostructural to a recently reported trigonal phase with space group P3m of Cs5H 3(SO4)4 [2]. At 185 °C the compound undergoes an apparently polymorphic transformation with a heat of transition of 23.8 kJ/mol and a slight additional increase in conductivity. The compounds Rb3H(SeO4)2 and Cs 3H(SeO4)2, though not isomorphous at ambient temperatures, are quintessential examples of superprotonic materials. Both adopt monoclinic structures at ambient temperatures and ultimately transform to a trigonal (R3m) superprotonic structure at slightly elevated temperatures, 178 and 183 °C, respectively. The compounds are completely miscible above the superprotonic transition and show extensive solubility below it. Beyond a careful determination of the phase boundaries, we find a remarkable 40-fold increase in the superprotonic conductivity in intermediate compositions rich in Rb as compared to either end-member. The compound Cs6(H2SO4)3(H 1.5PO4)4 is unusual amongst solid acid compounds in that it has a complex cubic structure at ambient temperature and apparently transforms to a simpler cubic structure of the CsCl-type (isostructural with CsH2PO4) at its transition temperature of 100-120 °C [3]. Here it is found that, depending on the level of humidification, the superprotonic transition of this material is superimposed with a decomposition reaction, which involves both exsolution of (liquid) acid and loss of H2O. This reaction can be suppressed by application of sufficiently high humidity, in which case Cs6(H2SO4)3(H 1.5PO4)4 undergoes a true superprotonic transition. It is proposed that, under conditions of low humidity, the decomposition/dehydration reaction transforms the compound to Cs6(H2-0.5xSO 4)3(H1.5PO4)4-x, also of the CsCl structure type at the temperatures of interest, but with a smaller unit cell. With increasing temperature, the decomposition/dehydration proceeds to greater and greater extent and unit cell of the solid phase decreases. This is identified to be the source of the apparent negative thermal expansion behavior. References: [1] L.A. Cowan, R.M. Morcos, N. Hatada, A. Navrotsky, S.M. Haile, Solid State Ionics 179 (2008) (9-10) 305. [2] M. Sakashita, H. Fujihisa, K.I. Suzuki, S. Hayashi, K. Honda, Solid State Ionics 178 (2007) (21-22) 1262. [3] C.R.I. Chisholm, Superprotonic Phase Transitions in Solid Acids: Parameters affecting the presence and stability of superprotonic transitions in the MHnXO4 family of compounds (X=S, Se, P, As; M=Li, Na, K, NH4, Rb, Cs), Materials Science, California Institute of Technology, Pasadena, California (2003).

  1. Short communication Fabrication of solid lipid microcapsules containing ascorbic acid

    E-print Network

    Short communication Fabrication of solid lipid microcapsules containing ascorbic acid using Encapsulation efficiency Lipid shell a b s t r a c t The importance of ascorbic acid (AA) in the human diet has

  2. Use of Pyrolyzed Iron Ethylenediaminetetraacetic Acid Modified Activated Carbon as Air-Cathode Catalyst in Microbial Fuel Cells

    E-print Network

    Use of Pyrolyzed Iron Ethylenediaminetetraacetic Acid Modified Activated Carbon as Air States *S Supporting Information ABSTRACT: Activated carbon (AC) is a cost-effective catalyst. KEYWORDS: microbial fuel cell, oxygen reduction reaction, catalyst, activated carbon, iron

  3. Liquid-Phase Catalytic Transfer Hydrogenation of Furfural over Homogeneous Lewis Acid-Ru/C Catalysts.

    PubMed

    Panagiotopoulou, Paraskevi; Martin, Nickolas; Vlachos, Dionisios G

    2015-06-22

    The catalytic performance of homogeneous Lewis acid catalysts and their interaction with Ru/C catalyst are studied in the catalytic transfer hydrogenation of furfural by using 2-propanol as a solvent and hydrogen donor. We find that Lewis acid catalysts hydrogenate the furfural to furfuryl alcohol, which is then etherified with 2-propanol. The catalytic activity is correlated with an empirical scale of Lewis acid strength and exhibits a volcano behavior. Lanthanides are the most active, with DyCl3 giving complete furfural conversion and a 97 % yield of furfuryl alcohol at 180 °C after 3 h. The combination of Lewis acid and Ru/C catalysts results in synergy for the stronger Lewis acid catalysts, with a significant increase in the furfural conversion and methyl furan yield. Optimum results are obtained by using Ru/C combined with VCl3 , AlCl3 , SnCl4 , YbCl3 , and RuCl3 . Our results indicate that the combination of Lewis acid/metal catalysts is a general strategy for performing tandem reactions in the upgrade of furans. PMID:26013846

  4. Synthesis of aliphatic polyesters by polycondensation using inorganic acid as catalyst

    PubMed Central

    Sokolsky-Papkov, Marina; Langer, Robert; Domb, Abraham J.

    2014-01-01

    An effective route for the synthesis of aliphatic polyesters made from adipic or sebacic acid and alkanediols, using inorganic acid as a catalyst is reported. The monomer composition, reaction time, catalyst type, and reaction conditions were optimized to yield polyesters with weight average molecular weights of 23,000 for adipic acid and 85,000 for sebacic acid-based polyesters. The polymers melt at temperatures of 52–65°C and possess melt viscosity in the range of 5600–19,400cP. This route represents an alternative method for producing aliphatic polyesters for possible use in the preparation of degradable disposable medical supplies. PMID:25473252

  5. Surface properties of pillared acid-activated bentonite as catalyst for selective production of linear alkylbenzene

    NASA Astrophysics Data System (ADS)

    Faghihian, Hossein; Mohammadi, Mohammad Hadi

    2013-01-01

    Acid-activated and pillared montmorillonite were prepared as novel catalysts for alkylation of benzene with 1-decene for production of linear alkylbenzene. The catalysts were characterized by X-ray diffraction, FT-IR spectroscopy, N2 adsorption isotherms, temperature programmed desorption of NH3, scanning electron microscopy and elemental and thermal analysis techniques. It was found that acid-activation of clays prior to pillaring increased the porosity, total specific surface area, total pore volume and surface acidity of the catalysts. Optimization of the reaction conditions was performed by varying catalyst concentration (0.25-1.75 wt%), reactants ratio (benzene to 1-decene of 8.75, 12 and 15) and temperature (115-145 °C) in a batch slurry reactor. Under optimized conditions more than 98% conversion of 1-decene, and complete selectivity for monoalkylbenzenes were achieved.

  6. Kinetic and process studies on free and solid acid catalyzed hydrolysis of biomass substrates

    SciTech Connect

    Abasaeed, A.E.

    1987-01-01

    Trifluoroacetic acid (TFA) was tested as a catalyst for cellulose hydrolysis. Eighty percent conversion of cellulose into glucose was obtained with concentrated TFA. The kinetics of TFA catalyzed cellulose hydrolysis was investigated. The reaction was found to follow first order kinetics for both hydrolysis and decomposition. The kinetic parameters were determined from experimental data covering conditions of 160-180 C, 10-30% acid, and 1:2 solid to liquid ratio. The hydrolysis reaction was found to be more sensitive to temperature than the decomposition reaction. Use of TFA was further investigated as a pretreatment for enzymatic hydrolysis of cellulose. A two-fold increase in sugar yields was obtained for TFA pretreated samples in comparison to untreated ones. The kinetics of hydrolysis of prehydrolyzed wood by sulfuric acid was investigated. The substrate was first treated with 0.75% acid at 184 C for 4 minutes to remove hemicellulose. The kinetic parameters were determined in the range of 198-215 C and 1-3% acid. A heterogeneous kinetic model was developed to study the effect of particle size on acid hydrolysis of cellulose. It was found that as the chip size increases, maximum glucose yield decreases and reaction time at which maximum yield occurs increases. Acidic zeolites (LZ-M-8) were investigated as catalysts for hydrolysis reaction of inulin into fructose. The hydrolysis reaction was found to follow first order kinetics. Products containing 96 and 75% fructose were obtained upon hydrolysis respectively from inulin and extract.

  7. COMPARISON OF SODIUM HYPOPHOSPHITE WITH HYPOPHOSPHOROUS ACID AS CURING CATALYSTS FOR DP FINISHING WITH BTCA OR CITRIC ACID

    Technology Transfer Automated Retrieval System (TEKTRAN)

    It has been suggested that when sodium hypophosphite (SHP) is used to catalyze crosslinking of cotton by 1,2,3,4-butanetetracarboxylic acid (BTCA) at 160-190 degrees C, the active catalyst may be free hypophosphorous acid, which could form a mixed linear anhydride with, and subsequently a cyclic anh...

  8. Chance and necessity in the selection of nucleic acid catalysts

    NASA Technical Reports Server (NTRS)

    Lorsch, J. R.; Szostak, J. W.

    1996-01-01

    In Tom Stoppard's famous play [Rosencrantz and Guildenstern are Dead], the ill-fated heroes toss a coin 101 times. The first 100 times they do so the coin lands heads up. The chance of this happening is approximately 1 in 10(30), a sequence of events so rare that one might argue that it could only happen in such a delightful fiction. Similarly rare events, however, may underlie the origins of biological catalysis. What is the probability that an RNA, DNA, or protein molecule of a given random sequence will display a particular catalytic activity? The answer to this question determines whether a collection of such sequences, such as might result from prebiotic chemistry on the early earth, is extremely likely or unlikely to contain catalytically active molecules, and hence whether the origin of life itself is a virtually inevitable consequence of chemical laws or merely a bizarre fluke. The fact that a priori estimates of this probability, given by otherwise informed chemists and biologists, ranged from 10(-5) to 10(-50), inspired us to begin to address the question experimentally. As it turns out, the chance that a given random sequence RNA molecule will be able to catalyze an RNA polymerase-like phosphoryl transfer reaction is close to 1 in 10(13), rare enough, to be sure, but nevertheless in a range that is comfortably accessible by experiment. It is the purpose of this Account to describe the recent advances in combinatorial biochemistry that have made it possible for us to explore the abundance and diversity of catalysts existing in nucleic acid sequence space.

  9. Ultrasound assisted transesterification of waste cooking oil using heterogeneous solid catalyst.

    PubMed

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

    2015-01-01

    Transesterification based biodiesel production from waste cooking oil in the presence of heterogeneous solid catalyst has been investigated in the present work. The effect of different operating parameters such as type of catalyst, catalyst concentration, oil to methanol molar ratio and the reaction temperature on the progress of the reaction was studied. Some studies related to catalyst reusability have also been performed. The important physicochemical properties of the synthesized biodiesel have also been investigated. The results showed that tri-potassium phosphate exhibits high catalytic activity for the transesterification of waste cooking oil. Under the optimal conditions, viz. catalyst concentration of 3wt% K3PO4, oil to methanol molar ratio of 1:6 and temperature of 50°C, 92.0% of biodiesel yield was obtained in 90min of reaction time. Higher yield was obtained in the presence of ultrasound as compared to conventional approach under otherwise similar conditions, which can be attributed to the cavitational effects. Kinetic studies have been carried out to determine the rate constant at different operating temperatures. It was observed that the kinetic rate constant increased with an increase in the temperature and the activation energy was found to be 64.241kJ/mol. PMID:24935026

  10. Metallo-solid lipid nanoparticles as colloidal tools for meso-macroporous supported catalysts.

    PubMed

    Kim, Sanghoon; Durand, Pierrick; Roques-Carmes, Thibault; Eastoe, Julian; Pasc, Andreea

    2015-02-10

    Meso-macroporous silica containing iron oxide nanoparticles (15-20 nm) was synthesized by formulating solid lipid nanoparticles and metallosurfactant as both template and metal source. Because of the high active surface area of the catalyst, the material exhibits an excellent performance in a Fenton-like reaction for methylene blue (MB) degradation, even at low amount of iron oxide (5% TOC after 14 h). PMID:25598433

  11. Solid-state actinide acid phosphites from phosphorous acid melts

    SciTech Connect

    Oh, George N.; Burns, Peter C.

    2014-07-01

    The reaction of UO{sub 3} and H{sub 3}PO{sub 3} at 100 °C and subsequent reaction with dimethylformamide (DMF) produces crystals of the compound (NH{sub 2}(CH{sub 3}){sub 2})[UO{sub 2}(HPO{sub 2}OH)(HPO{sub 3})]. This compound crystallizes in space group P2{sub 1}/n and consists of layers of uranyl pentagonal bipyramids that share equatorial vertices with phosphite units, separated by dimethylammonium. In contrast, the reaction of phosphorous acid and actinide oxides at 210 °C produces a viscous syrup. Subsequent dilution in solvents and use of standard solution-state methods results in the crystallization of two polymorphs of the actinide acid phosphites An(HPO{sub 2}OH){sub 4} (An=U, Th) and of the mixed acid phosphite–phosphite U(HPO{sub 3})(HPO{sub 2}OH){sub 2}(H{sub 2}O)·2(H{sub 2}O). ?- and ?-An(HPO{sub 2}OH){sub 4} crystallize in space groups C2/c and P2{sub 1}/n, respectively, and comprise a three-dimensional network of An{sup 4+} cations in square antiprismatic coordination corner-sharing with protonated phosphite units, whereas U(HPO{sub 3})(HPO{sub 2}OH){sub 2}(H{sub 2}O){sub 2}·(H{sub 2}O) crystallizes in a layered structure in space group Pbca that is composed of An{sup 4+} cations in square antiprismatic coordination corner-sharing with protonated phosphites and water ligands. We discuss our findings in using solid inorganic reagents to produce a solution-workable precursor from which solid-state compounds can be crystallized. - Graphical abstract: Reaction of UO{sub 3} and H{sub 3}PO{sub 3} at 100 °C and subsequent reaction with DMF produces crystals of (NH{sub 2}(CH{sub 3}){sub 2})[UO{sub 2}(HPO{sub 2}OH)(HPO{sub 3})] with a layered structure. Reaction of phosphorous acid and actinide oxides at 210 °C produces a viscous syrup and further solution-state reactions result in the crystallization of the actinide acid phosphites An(HPO{sub 2}OH){sub 4} (An=U, Th), with a three-dimensional network structure, and the mixed acid phosphite–phosphite U(HPO{sub 3})(HPO{sub 2}OH){sub 2}(H{sub 2}O){sub 2}·(H{sub 2}O) with a layered structure. - Highlights: • U(VI), U(IV) and Th(IV) phosphites were synthesized by solution-state methods. • A new uranyl phosphite structure is based upon uranyl phosphite anionic sheets. • New U and Th phosphites have framework structures.

  12. A green and efficient protocol for the synthesis of quinoxaline, benzoxazole and benzimidazole derivatives using heteropolyanion-based ionic liquids: as a recyclable solid catalyst.

    PubMed

    Vahdat, Seyed Mohammad; Baghery, Saeed

    2013-09-01

    In this paper, we introduce two nonconventional ionic liquid compounds which are composed of propane sulfonate functionalized organic cations and heteropolyanions as green solid acid catalysts for the highly efficient and green synthesis of 2,3-disubstitutedquinoxaline derivatives. These ionic liquids are in the solid state at room temperature and the synthesis is carried out via the one-pot condensation reaction of various o-phenylenediamine with 1,2-diketone derivatives. Benzoxazole and benzimidazole derivatives were also synthesized by these novel catalysts via the one-pot condensation from reaction orthoester with o-aminophenol (synthesis of benzoxazole derivatives) and ophenylenediamine (synthesis of benzimidazole derivatives). All experiments successfully resulted in the desired products. The described novel synthesis method has several advantages of safety, mild condition, high yields, short reaction times, simplicity and easy workup compared to the traditional method of synthesis. PMID:23547570

  13. Stability of Supported Platinum Sulfuric Acid Decomposition Catalysts for use in Thermochemical Water Splitting Cycles

    SciTech Connect

    Daniel M. Ginosar; Lucia M. Petkovic; Anne W. Glenn; Kyle C. Burch

    2007-03-01

    The activity and stability of several metal oxide supported platinum catalysts were explored for the sulfuric acid decomposition reaction. The acid decomposition reaction is common to several sulfur based thermochemical water splitting cycles. Reactions were carried out using a feed of concentrated liquid sulfuric acid (96 wt%) at atmospheric pressure at temperatures between 800 and 850 °C and a weight hour space velocity of 52 g acid/g catalyst/hr. Reactions were run at these high space velocities such that variations in kinetics were not masked by surplus catalyst. The influence of exposure to reaction conditions was explored for three catalysts; 0.1-0.2 wt% Pt supported on alumina, zirconia and titania. The higher surface area Pt/Al2O3 and Pt/ZrO2 catalysts were found to have the highest activity but deactivated rapidly. A low surface area Pt/TiO2 catalyst was found to have good stability in short term tests, but slowly lost activity for over 200 hours of continuous operation.

  14. Benzene selectivity in competitive arene hydrogenation: effects of single-site catalyst···acidic oxide surface binding geometry.

    PubMed

    Gu, Weixing; Stalzer, Madelyn Marie; Nicholas, Christopher P; Bhattacharyya, Alak; Motta, Alessandro; Gallagher, James R; Zhang, Guanghui; Miller, Jeffrey T; Kobayashi, Takeshi; Pruski, Marek; Delferro, Massimiliano; Marks, Tobin J

    2015-06-01

    Organozirconium complexes are chemisorbed on Brønsted acidic sulfated ZrO2 (ZrS), sulfated Al2O3 (AlS), and ZrO2-WO3 (ZrW). Under mild conditions (25 °C, 1 atm H2), the supported Cp*ZrMe3, Cp*ZrBz3, and Cp*ZrPh3 catalysts are very active for benzene hydrogenation with activities declining with decreasing acidity, ZrS ? AlS ? ZrW, arguing that more Brønsted acidic oxides (those having weaker corresponding conjugate bases) yield stronger surface organometallic electrophiles and for this reason have higher benzene hydrogenation activity. Benzene selective hydrogenation, a potential approach for carcinogenic benzene removal from gasoline, is probed using benzene/toluene mixtures, and selectivities for benzene hydrogenation vary with catalyst as ZrBz3(+)/ZrS(-), 83% > Cp*ZrMe2(+)/ZrS(-), 80% > Cp*ZrBz2(+)/ZrS(-), 67% > Cp*ZrPh2(+)/ZrS(-), 57%. For Cp*ZrBz2(+)/ZrS(-), which displays the highest benzene hydrogenation activity with moderate selectivity in benzene/toluene mixtures. Other benzene/arene mixtures are examined, and benzene selectivities vary with arene as mesitylene, 99%, > ethylbenzene, 86% > toluene, 67%. Structural and computational studies by solid-state NMR spectroscopy, XAS, and periodic DFT methods applied to supported Cp*ZrMe3 and Cp*ZrBz3 indicate that larger Zr···surface distances are present in more sterically encumbered Cp*ZrBz2(+)/AlS(-) vs Cp*ZrMe2(+)/AlS(-). The combined XAS, solid state NMR, and DFT data argue that the bulky catalyst benzyl groups expand the "cationic" metal center-anionic sulfated oxide surface distances, and this separation/weakened ion-pairing enables the activation/insertion of more sterically encumbered arenes and influences hydrogenation rates and selectivity patterns. PMID:25884397

  15. Direct asymmetric hydrogenation of ?-keto acids by using the highly efficient chiral spiro iridium catalysts.

    PubMed

    Yan, Pu-Cha; Xie, Jian-Hua; Zhang, Xiang-Dong; Chen, Kang; Li, Yuan-Qiang; Zhou, Qi-Lin; Che, Da-Qing

    2014-12-28

    A new efficient and highly enantioselective direct asymmetric hydrogenation of ?-keto acids employing the Ir/SpiroPAP catalyst under mild reaction conditions has been developed. This method might be feasible for the preparation of a series of chiral ?-hydroxy acids on a large scale. PMID:25384177

  16. Process for the generation of .alpha., .beta.-unsaturated carboxylic acids and esters using niobium catalyst

    DOEpatents

    Gogate, Makarand Ratnakav (Durham, NC); Spivey, James Jerome (Cary, NC); Zoeller, Joseph Robert (Kingsport, TN)

    1999-01-01

    A process using a niobium catalyst includes the step of reacting an ester or carboxylic acid with oxygen and an alcohol in the presence a niobium catalyst to respectively produce an .alpha.,.beta.-unsaturated ester or carboxylic acid. Methanol may be used as the alcohol, and the ester or carboxylic acid may be passed over the niobium catalyst in a vapor stream containing oxygen and methanol. Alternatively, the process using a niobium catalyst may involve the step of reacting an ester and oxygen in the presence the niobium catalyst to produce an .alpha.,.beta.-unsaturated carboxylic acid. In this case the ester may be a methyl ester. In either case, niobium oxide may be used as the niobium catalyst with the niobium oxide being present on a support. The support may be an oxide selected from the group consisting of silicon oxide, aluminum oxide, titanium oxide and mixtures thereof. The catalyst may be formed by reacting niobium fluoride with the oxide serving as the support. The niobium catalyst may contain elemental niobium within the range of 1 wt % to 70 wt %, and more preferably within the range of 10 wt % to 30 wt %. The process may be operated at a temperature from 150 to 450.degree. C. and preferably from 250 to 350.degree. C. The process may be operated at a pressure from 0.1 to 15 atm. absolute and preferably from 0.5-5 atm. absolute. The flow rate of reactants may be from 10 to 10,000 L/kg.sub.(cat) /h, and preferably from 100 to 1,000 L/kg.sub.(cat) /h.

  17. Palladium Catalysts for Fatty Acid Deoxygenation: Influence of the Support and Fatty Acid Chain Length on Decarboxylation Kinetics

    SciTech Connect

    Ford, JP; Immer, JG; Lamb, HH

    2012-03-29

    Supported metal catalysts containing 5 wt% Pd on silica, alumina, and activated carbon were evaluated for liquid-phase deoxygenation of stearic (octadecanoic), lauric (dodecanoic), and capric (decanoic) acids under 5 % H-2 at 300 A degrees C and 15 atm. On-line quadrupole mass spectrometry (QMS) was used to measure CO + CO2 yield, CO2 selectivity, H-2 consumption, and initial decarboxylation rate. Post-reaction analysis of liquid products by gas chromatography was used to determine n-alkane yields. The Pd/C catalyst was highly active and selective for stearic acid (SA) decarboxylation under these conditions. In contrast, SA deoxygenation over Pd/SiO2 occurred primarily via decarbonylation and at a much slower rate. Pd/Al2O3 exhibited high initial SA decarboxylation activity but deactivated under the test conditions. Similar CO2 selectivity patterns among the catalysts were observed for deoxygenation of lauric and capric acids; however, the initial decarboxylation rates tended to be lower for these substrates. The influence of alkyl chain length on deoxygenation kinetics was investigated for a homologous series of C-10-C-18 fatty acids using the Pd/C catalyst. As fatty acid carbon number decreases, reaction time and H-2 consumption increase, and CO2 selectivity and initial decarboxylation rate decrease. The increase in initial decarboxylation rates for longer chain fatty acids is attributed to their greater propensity for adsorption on the activated carbon support.

  18. N-doped carbon nanomaterials are durable catalysts for oxygen reduction reaction in acidic fuel cells

    PubMed Central

    Shui, Jianglan; Wang, Min; Du, Feng; Dai, Liming

    2015-01-01

    The availability of low-cost, efficient, and durable catalysts for oxygen reduction reaction (ORR) is a prerequisite for commercialization of the fuel cell technology. Along with intensive research efforts of more than half a century in developing nonprecious metal catalysts (NPMCs) to replace the expensive and scarce platinum-based catalysts, a new class of carbon-based, low-cost, metal-free ORR catalysts was demonstrated to show superior ORR performance to commercial platinum catalysts, particularly in alkaline electrolytes. However, their large-scale practical application in more popular acidic polymer electrolyte membrane (PEM) fuel cells remained elusive because they are often found to be less effective in acidic electrolytes, and no attempt has been made for a single PEM cell test. We demonstrated that rationally designed, metal-free, nitrogen-doped carbon nanotubes and their graphene composites exhibited significantly better long-term operational stabilities and comparable gravimetric power densities with respect to the best NPMC in acidic PEM cells. This work represents a major breakthrough in removing the bottlenecks to translate low-cost, metal-free, carbon-based ORR catalysts to commercial reality, and opens avenues for clean energy generation from affordable and durable fuel cells. PMID:26601132

  19. Magnetic solid base catalyst CaO/CoFe2O4 for biodiesel production: Influence of basicity and wettability of the catalyst in catalytic performance

    NASA Astrophysics Data System (ADS)

    Zhang, Pingbo; Han, Qiuju; Fan, Mingming; Jiang, Pingping

    2014-10-01

    A novel magnetic solid base catalyst CaO/CoFe2O4 was successfully prepared with CoFe2O4 synthesized by hydrothermal method as the magnetic core and applied to the transesterification of soybean oil for the production of biodiesel. The magnetic solid base catalysts were characterized by a series of techniques including CO2-TPD, powder XRD, TGA, TEM and the contact angle measurement of the water droplet. It was demonstrated that CaO/CoFe2O4 has stronger magnetic strength indicating perfect utility for repeated use and better basic strength. Compared with CaO/ZnFe2O4 and CaO/MnFe2O4, solid base catalyst CaO/CoFe2O4 has better catalytic performance, weaker hydroscopicity and stronger wettability, demonstrating that catalytic performance was relative to both basicity of catalyst and the full contact between the catalyst and the reactants, but the latter was a main factor in the catalytic system.

  20. Synthesis of sulfonated porous carbon nanospheres solid acid by a facile chemical activation route

    NASA Astrophysics Data System (ADS)

    Chang, Binbin; Guo, Yanzhen; Yin, Hang; Zhang, Shouren; Yang, Baocheng

    2015-01-01

    Generally, porous carbon nanospheres materials are usually prepared via a template method, which is a multi-steps and high-cost strategy. Here, we reported a porous carbon nanosphere solid acid with high surface area and superior porosity, as well as uniform nanospheical morphology, which prepared by a facile chemical activation with ZnCl2 using resorcinol-formaldehyde (RF) resins spheres as precursor. The activation of RF resins spheres by ZnCl2 at 400 °C brought high surface area and large volume, and simultaneously retained numerous oxygen-containing and hydrogen-containing groups due to the relatively low processing temperature. The presence of these functional groups is favorable for the modification of -SO3H groups by a followed sulfonation treating with sulphuric acid and organic sulfonic acid. The results of N2 adsorption-desorption and electron microscopy clearly showed the preservation of porous structure and nanospherical morphology. Infrared spectra certified the variation of surface functional groups after activation and the successful modification of -SO3H groups after sulfonation. The acidities of catalysts were estimated by an indirect titration method and the modified amount of -SO3H groups were examined by energy dispersive spectra. The results suggested sulfonated porous carbon nanospheres catalysts possessed high acidities and -SO3H densities, which endowed their significantly catalytic activities for biodiesel production. Furthermore, their excellent stability and recycling property were also demonstrated by five consecutive cycles.

  1. Liquefaction of sawdust in 1-octanol using acidic ionic liquids as catalyst.

    PubMed

    Lu, Zexiang; Zheng, Huaiyu; Fan, Liwei; Liao, Yiqiang; Ding, Bingjing; Huang, Biao

    2013-08-01

    Acidic ionic liquids (AILs) as a novel catalyst in biomass liquefaction can accord with the demand of green chemistry and enhance the development of biomass thermal chemical conversion. A series of AILs containing HSO4- were synthesized by the imidazolium cation functionalization and applied to the Chinese fir sawdust liquefaction in 1-octanol in this paper. The experimental results showed that the liquefaction rate was gradually improved with the AILs acidity increasing, and reached 71.5% when 1-(4-sulfobutyl)-3-methylmidazolium hydrosulfate was used as catalyst with the 6:1 mass ratio of 1-octanol to sawdust at 423K after 60 min. Lignin, hemicellulose and cellulose were orderly desquamated, and then depolymerized and liquefied with the catalyst acidity increasing in the sawdust liquefaction process. The light oil was mainly composed of the octyl ether and the octyl ester compounds, suggesting that the solvent may play an important role in producing the high octane rating biofuel. PMID:23770997

  2. Electrical properties of phosphorus in situ doped Au-catalyst vapor liquid solid silicon nanowires

    NASA Astrophysics Data System (ADS)

    Pichon, L.; Rogel, R.; Jacques, E.

    2015-11-01

    N-type in-situ doped silicon nanowire-based resistors are fabricated following a CMOS process fabrication. Silicon nanowires are prepared by a Vapour Liquid Solid (VLS) method using gold as the catalyst. The doping level is adjusted by varying the phosphine to silane mole ratio during silicon nanowire growth. A macroscopic electrical model is presented to extract the average silicon nanowire electrical resistivity over a large doping level range (varying from undoped to highly doped nanowires). Carrier transport is strongly affected by the trapping effect of gold impurities into silicon nanowires, and silicon nanowire electrical resistivity is three decades higher than for silicon bulk at low doping levels. The technological requirement in terms of doping level control for the fabrication of devices based on a gold catalyst VLS is demonstrated.

  3. Model heterogeneous acid catalysts and metal-support interactions: A combined surface science and catalysis study

    SciTech Connect

    Boszormenyi, I.

    1991-05-01

    This (<100 [Angstrom]) silica-alumina layers were tested as potential model heterogeneous acid catalysts for combined surface science and catalysis studies. Three preparation methods were used: oxidation of r3 [times] r3 R30 Al/Si(111) structure in UHV; deposition on Si(lll) from aqueous solution; and argon ion beam sputter deposition in UHV. The homogeneous thin layers are amorphous, and the chemical environment of surface atoms is similar to that of Si, Al and oxygen atoms on high surface area acid catalysts. Since the ion beam-deposited thin layer of silica-alumina has the same composition as the target zeolite this deposition method is a promising tool to prepare model catalysts using practical catalyst targets. The silica-alumina layers are active in cumene cracking, a typical acid catalyzed reaction. In order to clearly distinguish background reactions and the acid catalyzed reaction at least 20 cm[sup 2] catalyst surface area is needed. Two series of model platinum-alumina catalysts were prepared in a combined UHV -- high pressure reactor cell apparatus by depositing alumina on polycrystalline Pt foil and by vapor depositing Pt on a thin alumina layer on Au. Both model surfaces have been prepared with and without chlorine. AES, CO desorption as well as methyl cyclopentane (MCP) hydrogenolysis studies indicate that the Pt surface area is always higher if a chlorination step is involved. Selectivity patterns in MCP ring opening on Pt-on-alumina'' and on alumina-on-Pt'' are different; only the former is a linear combination of selective and statistical ring opening. Product distribution, however, changes with coverage and reaction time. The properties of the two model catalyst systems and role of chlorine in MCP hydrogenolysis are also discussed.

  4. Model heterogeneous acid catalysts and metal-support interactions: A combined surface science and catalysis study

    SciTech Connect

    Boszormenyi, I.

    1991-05-01

    This (<100 {Angstrom}) silica-alumina layers were tested as potential model heterogeneous acid catalysts for combined surface science and catalysis studies. Three preparation methods were used: oxidation of r3 {times} r3 R30 Al/Si(111) structure in UHV; deposition on Si(lll) from aqueous solution; and argon ion beam sputter deposition in UHV. The homogeneous thin layers are amorphous, and the chemical environment of surface atoms is similar to that of Si, Al and oxygen atoms on high surface area acid catalysts. Since the ion beam-deposited thin layer of silica-alumina has the same composition as the target zeolite this deposition method is a promising tool to prepare model catalysts using practical catalyst targets. The silica-alumina layers are active in cumene cracking, a typical acid catalyzed reaction. In order to clearly distinguish background reactions and the acid catalyzed reaction at least 20 cm{sup 2} catalyst surface area is needed. Two series of model platinum-alumina catalysts were prepared in a combined UHV -- high pressure reactor cell apparatus by depositing alumina on polycrystalline Pt foil and by vapor depositing Pt on a thin alumina layer on Au. Both model surfaces have been prepared with and without chlorine. AES, CO desorption as well as methyl cyclopentane (MCP) hydrogenolysis studies indicate that the Pt surface area is always higher if a chlorination step is involved. Selectivity patterns in MCP ring opening on ``Pt-on-alumina`` and on ``alumina-on-Pt`` are different; only the former is a linear combination of selective and statistical ring opening. Product distribution, however, changes with coverage and reaction time. The properties of the two model catalyst systems and role of chlorine in MCP hydrogenolysis are also discussed.

  5. Ammonolysis of esters of hydroxybenzoic acids on a boron phosphate catalyst

    SciTech Connect

    Suvorov, B.V.; Bukeikhanov, N.R.; Li, L.V.; Zulkasheva, A.Z.

    1987-09-10

    In this investigation boron phosphate catalyst was used for ammonolysis of methyl and ethyl esters of salicylic and 4-hydroxybenzoic acids. It was shown that ammonolysis of methyl and ethyl esters of salicylic and 4-hydroxybenzoic acids in presence of boron phosphate catalyst at a ratio of 3-7 moles of ammonia per mole of ester in a contact time of 1-5 sec at 380-400/sub 0/ can be used for obtaining o- and p- hydroxybenzonitriles in yields of over 90% of the theoretical.

  6. CO2-free power generation on an iron group nanoalloy catalyst via selective oxidation of ethylene glycol to oxalic acid in alkaline media.

    PubMed

    Matsumoto, Takeshi; Sadakiyo, Masaaki; Ooi, Mei Lee; Kitano, Sho; Yamamoto, Tomokazu; Matsumura, Syo; Kato, Kenichi; Takeguchi, Tatsuya; Yamauchi, Miho

    2014-01-01

    An Fe group ternary nanoalloy (NA) catalyst enabled selective electrocatalysis towards CO2-free power generation from highly deliverable ethylene glycol (EG). A solid-solution-type FeCoNi NA catalyst supported on carbon was prepared by a two-step reduction method. High-resolution electron microscopy techniques identified atomic-level mixing of constituent elements in the nanoalloy. We examined the distribution of oxidised species, including CO2, produced on the FeCoNi nanoalloy catalyst in the EG electrooxidation under alkaline conditions. The FeCoNi nanoalloy catalyst exhibited the highest selectivities toward the formation of C2 products and to oxalic acid, i.e., 99 and 60%, respectively, at 0.4 V vs. the reversible hydrogen electrode (RHE), without CO2 generation. We successfully generated power by a direct EG alkaline fuel cell employing the FeCoNi nanoalloy catalyst and a solid-oxide electrolyte with oxygen reduction ability, i.e., a completely precious-metal-free system. PMID:25004118

  7. CO2-Free Power Generation on an Iron Group Nanoalloy Catalyst via Selective Oxidation of Ethylene Glycol to Oxalic Acid in Alkaline Media

    NASA Astrophysics Data System (ADS)

    Matsumoto, Takeshi; Sadakiyo, Masaaki; Ooi, Mei Lee; Kitano, Sho; Yamamoto, Tomokazu; Matsumura, Syo; Kato, Kenichi; Takeguchi, Tatsuya; Yamauchi, Miho

    2014-07-01

    An Fe group ternary nanoalloy (NA) catalyst enabled selective electrocatalysis towards CO2-free power generation from highly deliverable ethylene glycol (EG). A solid-solution-type FeCoNi NA catalyst supported on carbon was prepared by a two-step reduction method. High-resolution electron microscopy techniques identified atomic-level mixing of constituent elements in the nanoalloy. We examined the distribution of oxidised species, including CO2, produced on the FeCoNi nanoalloy catalyst in the EG electrooxidation under alkaline conditions. The FeCoNi nanoalloy catalyst exhibited the highest selectivities toward the formation of C2 products and to oxalic acid, i.e., 99 and 60%, respectively, at 0.4 V vs. the reversible hydrogen electrode (RHE), without CO2 generation. We successfully generated power by a direct EG alkaline fuel cell employing the FeCoNi nanoalloy catalyst and a solid-oxide electrolyte with oxygen reduction ability, i.e., a completely precious-metal-free system.

  8. CO2-Free Power Generation on an Iron Group Nanoalloy Catalyst via Selective Oxidation of Ethylene Glycol to Oxalic Acid in Alkaline Media

    PubMed Central

    Matsumoto, Takeshi; Sadakiyo, Masaaki; Ooi, Mei Lee; Kitano, Sho; Yamamoto, Tomokazu; Matsumura, Syo; Kato, Kenichi; Takeguchi, Tatsuya; Yamauchi, Miho

    2014-01-01

    An Fe group ternary nanoalloy (NA) catalyst enabled selective electrocatalysis towards CO2-free power generation from highly deliverable ethylene glycol (EG). A solid-solution-type FeCoNi NA catalyst supported on carbon was prepared by a two-step reduction method. High-resolution electron microscopy techniques identified atomic-level mixing of constituent elements in the nanoalloy. We examined the distribution of oxidised species, including CO2, produced on the FeCoNi nanoalloy catalyst in the EG electrooxidation under alkaline conditions. The FeCoNi nanoalloy catalyst exhibited the highest selectivities toward the formation of C2 products and to oxalic acid, i.e., 99 and 60%, respectively, at 0.4?V vs. the reversible hydrogen electrode (RHE), without CO2 generation. We successfully generated power by a direct EG alkaline fuel cell employing the FeCoNi nanoalloy catalyst and a solid-oxide electrolyte with oxygen reduction ability, i.e., a completely precious-metal-free system. PMID:25004118

  9. Hydrothermal microwave valorization of eucalyptus using acidic ionic liquid as catalyst toward a green biorefinery scenario.

    PubMed

    Xu, Ji-Kun; Chen, Jing-Huan; Sun, Run-Cang

    2015-10-01

    The application of the acidic ionic liquid (IL), 1-butyl-3-methylimidazolium hydrogensulfate ([bmim]HSO4), as a catalyst in the hydrothermal microwave treatment (HMT) and green upgradation of eucalyptus biomass has been investigated. The process was carried out in a microwave reactor system at different temperatures (140-200°C) and evaluated for severities. The xylooligosaccharides (XOS, refers to a DP of 2-6) yield up to 5.04% (w/w) of the initial biomass and 26.72% (w/w) of xylan were achieved. Higher temperature resulted in lower molecular weight product, and enhanced the concentration of monosaccharides and byproducts. The morphology and structure of the solid residues were performed using an array of techniques, such as SEM, XRD, FTIR, BET surface area, and CP/MAS (13)C NMR, by which the increase of crystallinity, the destruction of surface structure, and the changes in functional groups and compositions were studied after the pretreatment, thus significantly enhancing the enzymatic hydrolysis. PMID:26119053

  10. Cyclobutane amino acids and peptidomimetics, parallel catalyst screening for aziridination 

    E-print Network

    Li, Shih-ming

    1996-01-01

    amino acids and peptide mimetics are important in synthetic and medicinal chemistry. Recent discovery of naturally occurring cyclobutane amino acids has raised considerable interest in the syntheses and biological studies of these types of compounds...

  11. Solid oxide fuel cells having porous cathodes infiltrated with oxygen-reducing catalysts

    DOEpatents

    Liu, Meilin; Liu, Ze; Liu, Mingfei; Nie, Lifang; Mebane, David Spencer; Wilson, Lane Curtis; Surdoval, Wayne

    2014-08-12

    Solid-oxide fuel cells include an electrolyte and an anode electrically coupled to a first surface of the electrolyte. A cathode is provided, which is electrically coupled to a second surface of the electrolyte. The cathode includes a porous backbone having a porosity in a range from about 20% to about 70%. The porous backbone contains a mixed ionic-electronic conductor (MIEC) of a first material infiltrated with an oxygen-reducing catalyst of a second material different from the first material.

  12. Efficient bifunctional catalyst lipase/organophosphonic acid-functionalized silica for biodiesel synthesis by esterification of oleic acid with ethanol.

    PubMed

    Yin, Ping; Chen, Wen; Liu, Wei; Chen, Hou; Qu, Rongjun; Liu, Xiguang; Tang, Qinghua; Xu, Qiang

    2013-07-01

    An efficient bifunctional catalyst lipase/organophosphonic acid-functionalized silica (SG-T-P-LS) has been successfully developed, and biodiesel production of fatty acid ethyl ester (FAEE) from free fatty acid (FFA) oleic acid with short-chain alcohol ethanol catalyzed by SG-T-P-LS was investigated. The process optimization using response surface methodology (RSM) was performed and the interactions between the operational variables were elucidated, and it was found that the molar ratio of alcohol to acid was the most significant factor. The optimum values for maximum conversion ratio can be obtained by using a Box-Behnken center-united design, and the conversion ratio could reach 89.94 ± 0.42% under the conditions that ethanol/acid molar ratio was 1.05:1 and SG-T-P-LS to FFA weight ratio was 14.9 wt.% at 28.6°C. The research results show that SG-T-P and LS-20 could work cooperatively to promote the esterification reaction, and the bifunctional catalyst SG-T-P-LS is a potential catalyst for biodiesel production. PMID:23688666

  13. Hydrogenation of carboxylic acids with a homogeneous cobalt catalyst.

    PubMed

    Korstanje, Ties J; van der Vlugt, Jarl Ivar; Elsevier, Cornelis J; de Bruin, Bas

    2015-10-16

    The reduction of esters and carboxylic acids to alcohols is a highly relevant conversion for the pharmaceutical and fine-chemical industries and for biomass conversion. It is commonly performed using stoichiometric reagents, and the catalytic hydrogenation of the acids previously required precious metals. Here we report the homogeneously catalyzed hydrogenation of carboxylic acids to alcohols using earth-abundant cobalt. This system, which pairs Co(BF4)2·6H2O with a tridentate phosphine ligand, can reduce a wide range of esters and carboxylic acids under relatively mild conditions (100°C, 80 bar H2) and reaches turnover numbers of up to 8000. PMID:26472903

  14. The behavior of palladium catalysts in direct formic acid fuel cells

    NASA Astrophysics Data System (ADS)

    Zhu, Yimin; Khan, Zakia; Masel, R. I.

    Previous work has considered the behavior of platinum based catalysts in direct methanol and Direct Formic Acid Fuel Cells (DFAFCs). In this paper, we explore the behavior of palladium-based anode catalyst for DFAFCs. The palladium catalysts produce significant performance enhancements. DFAFCs operated with dry air and zero back-pressure can generate power densities of 255˜230 mW cm -2 at relatively high voltages of 0.40˜0.50 V in a concentration range of formic acid from 3.0 to 15.0 M at a room temperature of 20 °C, which are not quite different from a hydrogen-air polymer exchange membrane (PEM) fuel cell with power density of 320 mW cm -2 obtained under the comparable conditions, and much higher than a direct methanol fuel cell (DMFC) with power density of 50 mW cm -2. The stability of the membrane electrode assembly (MEA) with palladium catalyst has also been evaluated. There is some decay in performance over several hours. However, the performance loss of DFAFCs can be fully recovered by applying a positive potential at the fuel cell anode after short-term life test. These results demonstrate that DFAFCs with palladium anode catalyst have exceptional properties for portable power applications.

  15. Improved synthesis of isostearic acid using zeolite catalysts

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Isostearic acids are unique and important biobased products with superior properties. Unfortunately, they are not widely utilized in industry because they are produced as byproducts from a process called clay-catalyzed oligomerization of tall oil fatty acids. Generally, this clay method results in...

  16. Consequences of Acid Strength for Isomerization and Elimination Catalysis on Solid Acids

    E-print Network

    Iglesia, Enrique

    Consequences of Acid Strength for Isomerization and Elimination Catalysis on Solid Acids Josef dynamics of alkane isomerization and alkanol dehydration are used to obtain rate and equilibrium constants-Hexane isomerization rates were limited by isomerization of alkoxide intermediates on bifunctional metal-acid mixtures

  17. Carbon quantum dots with photo-generated proton property as efficient visible light controlled acid catalyst

    NASA Astrophysics Data System (ADS)

    Li, Haitao; Liu, Ruihua; Kong, Weiqian; Liu, Juan; Liu, Yang; Zhou, Lei; Zhang, Xing; Lee, Shuit-Tong; Kang, Zhenhui

    2013-12-01

    Developing light-driven acid catalyst will be very meaningful for the controlled-acid catalytic processes towards a green chemical industry. Here, based on scanning electrochemical microscopy (SECM) and ?pH testing, we demonstrate that the 5-10 nm carbon quantum dots (CQDs) synthesized by electrochemical ablation of graphite have strong light-induced proton properties under visible light in solution, which can be used as an acid catalyst. The 5-10 nm CQDs' catalytic activity is strongly dependent on the illumination intensity and the temperature of the reaction system. As an effective visible light driven and controlled acid-catalyst, 5-10 nm CQDs can catalyze a series of organic reactions (esterification, Beckmann rearrangement and aldol condensation) with high conversion (34.7-46.2%, respectively) in water solution under visible light, while the 1-4 nm CQDs and 10-2000 nm graphite do not have such excellent catalytic activity. The use of 5-10 nm CQDs as a light responsive and controllable photocatalyst is truly a novel application of carbon-based nanomaterials, which may significantly push research in the current catalytic industry, environmental pollution and energy issues.Developing light-driven acid catalyst will be very meaningful for the controlled-acid catalytic processes towards a green chemical industry. Here, based on scanning electrochemical microscopy (SECM) and ?pH testing, we demonstrate that the 5-10 nm carbon quantum dots (CQDs) synthesized by electrochemical ablation of graphite have strong light-induced proton properties under visible light in solution, which can be used as an acid catalyst. The 5-10 nm CQDs' catalytic activity is strongly dependent on the illumination intensity and the temperature of the reaction system. As an effective visible light driven and controlled acid-catalyst, 5-10 nm CQDs can catalyze a series of organic reactions (esterification, Beckmann rearrangement and aldol condensation) with high conversion (34.7-46.2%, respectively) in water solution under visible light, while the 1-4 nm CQDs and 10-2000 nm graphite do not have such excellent catalytic activity. The use of 5-10 nm CQDs as a light responsive and controllable photocatalyst is truly a novel application of carbon-based nanomaterials, which may significantly push research in the current catalytic industry, environmental pollution and energy issues. Electronic supplementary information (ESI) available. See DOI: 10.1039/c3nr03996j

  18. Lipophilisation of Caffeic Acid through Esterification with Propanol Using Water-tolerable Acidic Ionic Liquid as Catalyst.

    PubMed

    Liu, Wei; Han, Liya

    2015-12-01

    Propyl caffeate was synthesized to produce lipophilic antioxidant, which used caffeic acid and propanol as starting materials, acidic ionic liquid as catalyst. The highest yield of propyl caffeate (98.7±0.8%) have been achieved under the optimum as follows: 1-butylsulfonic-3-methylimidazolium tosylate showed the best catalytic performance, molar ratio of caffeic acid to propanol was 1:20, reaction temperature was 90°C and the amount of acidic ionic liquid was 40%. The relationship between temperature and the forward rate constant gave the activation energy of 33.6 kJ mol(-1), which indicated that acidic ionic liquid possesses high catalytic activity in the synthesis of PC. And the activity of acidic ionic liquid was not inhibited by the water produced during the esterification process. More importantly, this reaction system can even proceed smoothly when initial water content was 5%. PMID:26582151

  19. Supported organoiridium catalysts for alkane dehydrogenation

    DOEpatents

    Baker, R. Thomas; Sattelberger, Alfred P.; Li, Hongbo

    2013-09-03

    Solid supported organoiridium catalysts, a process for preparing such solid supported organoiridium catalysts, and the use of such solid supported organoiridium catalysts in dehydrogenation reactions of alkanes is provided. The catalysts can be easily recovered and recycled.

  20. Solid Acid Fuel Cell Stack for APU Applications

    SciTech Connect

    Duong, Hau H.

    2011-04-15

    Solid acid fuel cell technology affords the opportunity to operate at the 200-300 degree centigrade regime that would allow for more fuel flexibility, compared to polymer electrode membrane fuel cell, while avoiding the relatively more expensive and complex system components required by solid oxide fuel cell. This project addresses many factors such as MEA size scalability, fuel robustness, stability, etc., that are essential for successful commercialization of the technology.

  1. Self-Assembled Nanocomposite Organic Polymers with Aluminum and Scandium as Heterogeneous Water-Compatible Lewis Acid Catalysts.

    PubMed

    Miyamura, Hiroyuki; Sonoyama, Arisa; Hayrapetyan, Davit; Kobayashi, Sh?

    2015-09-01

    While water-compatible Lewis acids have great potential as accessible and environmentally benign catalysts for various organic transformations, efficient immobilization of such Lewis acids while keeping high activity and without leaching of metals even under aqueous conditions is a challenging task. Self-assembled nanocomposite catalysts of organic polymers, carbon black, aluminum reductants, and scandium salts as heterogeneous water-compatible Lewis acid catalysts are described. These catalysts could be successfully applied to various C?C bond-forming reactions without leaching of metals. Scanning transmission electron microscopy analyses revealed that the nanocomposite structure of Al and Sc was fabricated in these heterogeneous catalysts. It is noted that Al species, which are usually decomposed rapidly in the presence of water, are stabilized under aqueous conditions. PMID:26228075

  2. Preparation and characterization of urea-oxalic acid solid form

    NASA Astrophysics Data System (ADS)

    Onija, Oana; Borodi, Gh.; Kacso, Irina; Pop, M. N.; Dadarlat, D.; Bratu, I.; Jumate, N.

    2012-02-01

    The selective production of crystalline polymorphs is an outstanding problem in solid-state chemistry. In this study, the preparation of a new urea solid form is based on pure urea and oxalic acid (1:1), by grinding the components at room temperature. The resulted compound was investigated by X-ray powder diffraction (PXRD), thermal analysis (DSC, PPE) and infrared (FTIR) spectroscopy. The difference between the PXRD patterns of urea-oxalic acid and of the starting components evidenced a new compound. Using X-ray powder diffraction method, the lattice parameters were determined. Some thermal properties of the obtained compound were also investigated by the previous mentioned calorimetric techniques.

  3. Pd/C Synthesized with Citric Acid: An Efficient Catalyst for Hydrogen Generation from Formic Acid/Sodium Formate

    PubMed Central

    Wang, Zhi-Li; Yan, Jun-Min; Wang, Hong-Li; Ping, Yun; Jiang, Qing

    2012-01-01

    A highly efficient hydrogen generation from formic acid/sodium formate aqueous solution catalyzed by in situ synthesized Pd/C with citric acid has been successfully achieved at room temperature. Interestingly, the presence of citric acid during the formation and growth of the Pd nanoparticles on carbon can drastically enhance the catalytic property of the resulted Pd/C, on which the conversion and turnover frequency for decomposition of formic acid/sodium formate system can reach the highest values ever reported of 85% within 160?min and 64?mol H2 mol?1 catalyst h?1, respectively, at room temperature. The present simple, low cost, but highly efficient CO-free hydrogen generation system at room temperature is believed to greatly promote the practical application of formic acid system on fuel cells. PMID:22953041

  4. Reducing Pt use in the catalysts for formic acid electrooxidation via nanoengineered surface structure

    NASA Astrophysics Data System (ADS)

    Liao, Mengyin; Wang, Yulu; Chen, Guoqin; Zhou, Hua; Li, Yunhua; Zhong, Chuan-Jian; Chen, Bing H.

    2014-07-01

    The design of active and durable catalysts for formic acid (FA) electrooxidation requires controlling the amount of three neighboring platinum atoms in the surface of Pt-based catalysts. Such requirement is studied by preparing Pt decorated Pd/C (donated as Pt-Pd/C) with various Pt:Pd molar ratios via galvanic displacement making the amount of three neighboring Pt atoms in the surface of Pt-Pd/C tunable. The decorated nanostructures are confirmed by XPS, HS-LEIS, cyclic voltammetry and chronoamperometric measurements, demonstrating that Pt-Pd/C (the optimal molar ratio, Pt:Pd = 1:250) exhibits superior activity and durability than Pd/C and commercial Pt/C (J-M, 20%) catalysts for FA electrooxidation. The mass activity of Pt-Pd/C (Pt:Pd = 1:250) (3.91 A mg-1) is about 98 and 6 times higher than that of commercial Pt/C (0.04 A mg-1) and Pd/C (0.63 A mg-1) at a given potential of 0.1 V vs SCE, respectively. The controlled synthesis of Pt-Pd/C lead to the formation of largely discontinuous Pd and Pt sites and inhibition of CO formation, exhibiting unprecedented electrocatalytic performance toward FA electrooxidation while the cost of the catalyst almost the same as Pd/C. These findings have profound implications to the design and nanoengineering of decorated surfaces of catalysts for FA electrooxidation.

  5. Enhancement of Biodiesel Production from Marine Alga, Scenedesmus sp. through In Situ Transesterification Process Associated with Acidic Catalyst

    PubMed Central

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

    2014-01-01

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

  6. Tandem isomerization-decarboxylation of unsaturated fatty acids to olefins via ruthenium metal-as-ligand catalysts

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A new facile Ru-catalyzed route to bio-olefins3 from unsaturated fatty acids via readily accessible metal-as-ligand type catalyst precursors, [Ru(CO)2RCO2]n and Ru3(CO)12, will be described. The catalyst apparently functions in a tandem mode by dynamically isomerizing the positions of double bonds i...

  7. A solid-state NMR investigation of the structure of mesoporous silica nanoparticle supported rhodium catalysts

    SciTech Connect

    Rapp, Jennifer; Huang, Yulin; Natella, Michael; Cai, Yang; Lin, Victor S.-Y.; Pruski, Marek

    2009-01-04

    A detailed study of the chemical structure of mesoporous silica catalysts containing rhodium ligands and nanoparticles (RhP-MSN) was carried out by multi-dimensional solid-state NMR techniques. The degree of functionalization of the rhodium-phosphinosilyl complex to the surface of the RhP-MSN channels was determined by {sup 29}Si NMR experiments. The structural assignments of the rhodium-phosphinosilyl complex were unambiguously determined by employing the novel, indirectly detected heteronuclear correlation ({sup 13}C-{sup 1}H and {sup 31}P-{sup 1}H idHETCOR) techniques, which indicated that oxidation of the attached phosphinosilyl groups and detachment of Rh was enhanced upon syngas conversion.

  8. Diameter-Specific Growth of Semiconducting SWNT Arrays Using Uniform Mo2C Solid Catalyst.

    PubMed

    Zhang, Shuchen; Tong, Lianming; Hu, Yue; Kang, Lixing; Zhang, Jin

    2015-07-22

    Semiconducting single-walled nanotube (s-SWNT) arrays with specific diameters are urgently demanded in the applications in nanoelectronic devices. Herein, we reported that by using uniform Mo2C solid catalyst, aligned s-SWNT (?90%) arrays with narrow-diameter distribution (?85% between 1.0 and 1.3 nm) on quartz substrate can be obtained. Mo2C nanoparticles with monodisperse sizes were prepared by using molybdenum oxide-based giant clusters, (NH4)42[Mo132O372(H3CCOO)30(H2O)72]·10H3CCOONH4·300H2O(Mo132), as the precursor that was carburized by a gas mixture of C2H5OH/H2 during a temperature-programmed reduction. In this approach, the formation of volatile MoO3 was inhibited due to the annealing and reduction at a low temperature. As a result, uniform Mo2C nanoparticles are formed, and their narrow size-dispersion strictly determines the diameter distribution of SWNTs. During the growth process, Mo2C selectively catalyzes the scission of C-O bonds of ethanol molecules, and the resultant absorbed oxygen (Oads) preferentially etches metallic SWNTs (m-SWNTs), leading to the high-yield of s-SWNTs. Raman spectroscopic analysis showed that most of the s-SWNTs can be identified as (14, 4), (13, 6), or (10, 9) tubes. Our findings open up the possibility of the chirality-controlled growth of aligned-SWNTs using uniform carbide nanoparticles as solid catalysts for practical nanoelectronics applications. PMID:26161581

  9. Composites of manganese oxide with carbon materials as catalysts for the ozonation of oxalic acid.

    PubMed

    Orge, C A; Órfão, J J M; Pereira, M F R

    2012-04-30

    Manganese oxide and manganese oxide-carbon composites were prepared and tested as catalysts for the removal of oxalic acid by ozonation. Their performances were compared with the parent carbon material (activated carbon or carbon xerogel) used to prepare the composites. Oxalic acid degradation by carbon materials is slower than that attained with manganese oxide or manganese oxide-carbon composites. A complete degradation after 90 and 45 min of reaction was obtained for carbon materials and for the catalysts containing manganese, respectively. The ozonation in the presence of the prepared composites are supposed to occur mainly by surface reactions, following a direct oxidation mechanism by molecular ozone and/or surface oxygenated radicals. PMID:22341747

  10. The distal glutamic acid as an acid-base catalyst in the distal site of horseradish peroxidase.

    PubMed

    Tanaka, M; Ishimori, K; Morishima, I

    1996-10-14

    The distal His is an essential amino acid residue as a general acid-base catalyst for peroxidase reaction cycle. However, the x-ray structure of chloroperoxidase revealed that Glu is located near the heme, suggesting that the carboxyl group also assists cleavage of O-O bond in peroxides. In this paper, we examined functional and structural properties of a horseradish peroxidase mutant having Glu instead of the distal His. Although this amino acid replacement depressed reaction rate with H2O2 and oxidation activity for guaiacol, the mutant still exhibited much higher activity than mutants in which the distal His was replaced by hydrophobic amino acid. Kinetic measurements suggest that the proton abstraction is decelerated in the mutant due to large fluctuation of the carboxyl group of the distal Glu. Therefore, we can conclude that Glu can be a potent acid-base catalyst for peroxidase reaction cycle, if the carboxyl group can be fixed at the optimum position. PMID:8878526

  11. Isotactic-b-syndiotactic stereoblock poly(methyl methacrylate) by chiral metallocene/Lewis acid hybrid catalysts.

    PubMed

    Bolig, Andrew D; Chen, Eugene Y-X

    2002-05-22

    Stereoblock polymerization with chiral ansa-metallocene/strong Lewis acid hybrid catalysts capable of switching stereospecificity of the methyl methacrylate polymerization produces the highly stereoregular isotactic-b-syndiotactic stereoblock poly(methyl methacrylate). PMID:12010014

  12. Polystyrene sulphonic acid resins with enhanced acid strength via macromolecular self-assembly within confined nanospace

    NASA Astrophysics Data System (ADS)

    Zhang, Xiaomin; Zhao, Yaopeng; Xu, Shutao; Yang, Yan; Liu, Jia; Wei, Yingxu; Yang, Qihua

    2014-01-01

    Tightening environmental legislation is driving the chemical industries to develop efficient solid acid catalysts to replace conventional mineral acids. Polystyrene sulphonic acid resins, as some of the most important solid acid catalysts, have been widely studied. However, the influence of the morphology on their acid strength—closely related to the catalytic activity—has seldom been reported. Herein, we demonstrate that the acid strength of polystyrene sulphonic acid resins can be adjusted through their reversible morphology transformation from aggregated to swelling state, mainly driven by the formation and breakage of hydrogen bond interactions among adjacent sulphonic acid groups within the confined nanospace of hollow silica nanospheres. The hybrid solid acid catalyst demonstrates high activity and selectivity in a series of important acid-catalysed reactions. This may offer an efficient strategy to fabricate hybrid solid acid catalysts for green chemical processes.

  13. Polymerization of Lactic Acid by MAGHNITE-H+ a Non-Toxic Montmorillonite Clay Catalyst

    NASA Astrophysics Data System (ADS)

    Harrane, A.; Belaouedj, M. A.; Meghabar, R.; Belbachir, M.

    2008-08-01

    The development of synthetic biodegradable polymers, such as poly(lactic acid), is particularly important for constructing medical devices, controlled drug release matrix, including scaffolds and sutures, and has attracted growing interest in the biomedical field. Here, we report a novel approach to preparing poly (D, L-lactic acid) (PDLA) as a biodegradable polymer. We investigated in detail the reaction conditions for the simple direct polycondensation of D, L-lactic acid, including the reaction times, temperatures, and catalyst. The molecular weight of synthesized PDLA is dependent on both the reaction temperature, amount of catalyst and time. The optimum reaction condition to obtain PDLA by direct polycondensation using Maghnite-H+[1,2], a proton exchanged Montmorillonite clay, as catalyst was thus determined to be 120 °C, 5% amount of Maghnite-H+ for 28 h with a molecular weight of 7970. The method for PDLA synthesis established here will facilitate production of PDLA of various molecular weights, which may have a potential utility as biomaterials.

  14. Conversion of isoamyl alcohol over acid catalysts: Reaction dependence on nature of active centers

    SciTech Connect

    Babu, G.P.; Murthy, R.S.; Krishnan, V.

    1997-02-01

    Acid catalysts are known to catalyze the dehydration of alcohols. In addition some oxide catalysts with basic properties have also been shown to play an important role in such dehydration reactions. The dehydration of aliphatic alcohols to olefins has been studied in detail using alumina silica-alumina and zeolite catalysts. The olefin products further undergo isomerization in presence of acidic sites. The reaction of isoamyl alcohol on catalytic surfaces has not been investigated in greater detail. The dehydration of isoamyl alcohol is of considerable interest in fine chemicals. Isoamyl alcohol may also undergo dehydrogenation as observed in the case of n-butanol. The scope of the present work is to identify the nature of the active sites selective for dehydration and dehydrogenation of isoamyl alcohol and to modify the active sites to promote isomerization of dehydrated products. Four catalytic surfaces on which the acidic strength can be varied, as well as selectively suppressed, are chosen for this study. 17 refs., 1 fig., 3 tabs.

  15. Pt/TiO2 (Rutile) Catalysts for Sulfuric Acid Decomposition in Sulfur-Based Thermochemical Water-Splitting Cycles

    SciTech Connect

    L. M. Petkovic; D. M. Ginosar; H. W. Rollins; K. C. Burch; P. J. Pinhero; H. H. Farrell

    2008-04-01

    Thermochemical cycles consist of a series of chemical reactions to produce hydrogen from water at lower temperatures than by direct thermal decomposition. All the sulfur-based cycles for water splitting employ the sulfuric acid decomposition reaction. This work reports the studies performed on platinum supported on titania (rutile) catalysts to investigate the causes of catalyst deactivation under sulfuric acid decomposition reaction conditions. Samples of 1 wt% Pt/TiO2 (rutile) catalysts were submitted to flowing concentrated sulfuric acid at 1123 K and atmospheric pressure for different times on stream (TOS) between 0 and 548 h. Post-operation analyses of the spent catalyst samples showed that Pt oxidation and sintering occurred under reaction conditions and some Pt was lost by volatilization. Pt loss rate was higher at initial times but total loss appeared to be independent of the gaseous environment. Catalyst activity showed an initial decrease that lasted for about 66 h, followed by a slight recovery of activity between 66 and 102 h TOS, and a period of slower deactivation after 102 h TOS. Catalyst sulfation did not seem to be detrimental to catalyst activity and the activity profile suggested that a complex dynamical situation involving platinum sintering, volatilization, and oxidation, along with TiO2 morphological changes affected catalyst activity in a non-monotonic way.

  16. Development of molecular and solid catalysts for the direct low-temperature oxidation of methane to methanol.

    PubMed

    Palkovits, Regina; von Malotki, Christian; Baumgarten, Martin; Müllen, Klaus; Baltes, Christian; Antonietti, Markus; Kuhn, Pierre; Weber, Jens; Thomas, Arne; Schüth, Ferdi

    2010-02-22

    The direct low-temperature oxidation of methane to methanol is demonstrated on a highly active homogeneous molecular catalyst system and on heterogeneous molecular catalysts based on polymeric materials possessing ligand motifs within the material structure. The N-(2-methylpropyl)-4,5-diazacarbazolyl-dichloro-platinum(II) complex reaches significantly higher activity compared to the well-known Periana system and allows first conclusions on electronic and structural requirements for high catalytic activity in this reaction. Interestingly, comparable activities could be achieved utilizing a platinum modified poly(benzimidazole) material, which demonstrates for the first time a solid catalyst with superior activity compared to the Periana system. Although the material shows platinum leaching, improved activity and altered electronic properties, compared to the conventional Periana system, support the proposed conclusions on structure-activity relationships. In comparison, platinum modified triazine-based catalysts show lower catalytic activity, but rather stable platinum coordination even after several catalytic cycles. Based on these systems, further development of improved solid catalysts for the direct low-temperature oxidation of methane to methanol is feasible. PMID:19780100

  17. Metalloenzyme-Like Zeolites as Lewis Acid Catalysts for C?C Bond Formation.

    PubMed

    Van de Vyver, Stijn; Román-Leshkov, Yuriy

    2015-10-19

    The use of metalloenzyme-like zeolites as Lewis acid catalysts for C?C bond formation reactions has received increasing attention over the past few years. In particular, the observation of direct aldol condensation reactions enabled by hydrophobic zeolites with isolated framework metal sites has encouraged the development of catalytic approaches for producing chemicals from biomass-derived compounds. The discovery of new Diels-Alder cycloaddition/dehydration routes and experimental and computational studies of Lewis acid catalyzed carbonyl-ene reactions have given a further boost to this rapidly evolving field. PMID:26465652

  18. Niobium Complexes As Lewis Acid and Radical Catalysts

    SciTech Connect

    Wayne Tikkanen

    2005-10-01

    The reaction of lithium pentaphenylcyclopentadiende (Li C{sub 5}Ph{sub 5}) with niobium pentachloride in dichloromethane or toluene produces insoluble red-orange solids whose C/H/Cl analyses are not consistent with C{sub 5}Ph{sub 5}NbCl{sub 4}. Addition of an acetonitrile solution of LiC{sub 5}Ph{sub 5} with NbCl{sub 5} gives C{sub 5}Ph{sub 5}NbCl{sub 4} observed as a transient product by NMR spectroscopy, which then abstracts H from the acetonitrile solvent to give HC{sub 5}Ph{sub 5} and presumably NbCl{sub 4}CH{sub 2}CN. Reversal of the order of addition gives the {center_dot}C{sub 5}Ph{sub 5} radical as characterized by MS and EPR spectroscopy. Attempts to prepare the trimethylsilyl derivative Me{sub 3}SiC{sub 5}Ph{sub 5} (a less reducing cyclopentadienyl group) were unsuccessful. Reaction was observed only in tetrahydrofuran, producing only Me{sub 3}SiO(CH{sub 2}){sub 4}C{sub 5}Ph{sub 4}(m-C{sub 6}H{sub 4}(CH3)) characterized by {sup 1}H, {sup 13}C NMR and mass spectroscopy. The trimethylsilyltetraphenylcyclopentadienyl derivative, Me{sub 3}Si(H)C{sub 5}Ph{sub 4}, was characterized by {sup 1}H, {sup 13}C NMR and mass spectroscopy. This compound reacts with NbCl{sub 5} to give HCl and ClSiMe{sub 3} and a mixture of HC{sub 5}Ph{sub 4}NbCl{sub 4} and Me{sub 3}SiC{sub 5}Ph{sub 4}NbCl{sub 4}.

  19. Effects of inherent/enhanced solid acidity and morphology of diatomite templates on the synthesis and porosity of hierarchically porous carbon.

    PubMed

    Liu, Dong; Yuan, Peng; Tan, Daoyong; Liu, Hongmei; Fan, Mingde; Yuan, Aihua; Zhu, Jianxi; He, Hongping

    2010-12-21

    The inherent or enhanced solid acidity of raw or activated diatomite is found to have significant effects on the synthesis of hierarchically porous diatomite-templated carbon with high surface area and special porous structure. The solid acidity makes raw/activated diatomite a catalyst for the generation of porous carbon, and the porous parameters of the carbon products are strongly dependent on the solid acidity of diatomite templates. The morphology of diatomite also dramatically affects the textural structure of porous carbon. Two types of macroporous structures in the carbon product, the partially solid pillars and the ordered hollow tubes, derive from the replication of the central and the edge pores of diatom shell, respectively. The hierarchically porous carbon shows good capability for the adsorption of solvent naphtha and H(2), enabling potential applications in adsorption and gas storage. PMID:21080632

  20. Solid phase sequencing of double-stranded nucleic acids

    DOEpatents

    Fu, Dong-Jing (Waltham, MA); Cantor, Charles R. (Boston, MA); Koster, Hubert (Concord, MA); Smith, Cassandra L. (Boston, MA)

    2002-01-01

    This invention relates to methods for detecting and sequencing of target double-stranded nucleic acid sequences, to nucleic acid probes and arrays of probes useful in these methods, and to kits and systems which contain these probes. Useful methods involve hybridizing the nucleic acids or nucleic acids which represent complementary or homologous sequences of the target to an array of nucleic acid probes. These probe comprise a single-stranded portion, an optional double-stranded portion and a variable sequence within the single-stranded portion. The molecular weights of the hybridized nucleic acids of the set can be determined by mass spectroscopy, and the sequence of the target determined from the molecular weights of the fragments. Nucleic acids whose sequences can be determined include nucleic acids in biological samples such as patient biopsies and environmental samples. Probes may be fixed to a solid support such as a hybridization chip to facilitate automated determination of molecular weights and identification of the target sequence.

  1. Advanced Electrodes for Solid Acid Fuel Cells by Platinum Deposition on CsH2PO4

    SciTech Connect

    Papandrew, Alexander B; Chisholm, Calum R; Elgammal, Ramez A; Ozer, Mustafa M; Zecevic, strahinja

    2011-01-01

    We demonstrate cathodes for solid acid fuel cells fabricated by vapor deposition of platinum from the metalorganic precursor Pt(acac)2 on the solid acid CsH2PO4 at 210 C. A network of platinum nanoparticles with diameters of 2-4 nm serves as both the oxygen reduction catalyst and the electronic conductor in the electrode. Electrodes with a platinum content of 1.75 mg/cm2 are more active for oxygen reduction than previously reported electrodes with a platinum content of 7.5 mg/cm2. Electrodes containing <1.75 mg/cm2 of platinum show significantly reduced catalytic activity and increased

  2. Ionic and Covalent Stabilization of Intermediates and Transition States in Catalysis by Solid Acids

    SciTech Connect

    Deshlahra, Prashant; Carr, Robert T.; Iglesia, Enrique

    2014-10-29

    Reactivity descriptors describe catalyst properties that determine the stability of kinetically relevant transition states and adsorbed intermediates. Theoretical descriptors, such as deprotonation energies (DPE), rigorously account for Brønsted acid strength for catalytic solids with known structure. Here, mechanistic interpretations of methanol dehydration turnover rates are used to assess how charge reorganization (covalency) and electrostatic interactions determine DPE and how such interactions are recovered when intermediates and transition states interact with the conjugate anion in W and Mo polyoxometalate (POM) clusters and gaseous mineral acids. Turnover rates are lower and kinetically relevant species are less stable on Mo than W POM clusters with similar acid strength, and such species are more stable on mineral acids than that predicted from W-POM DPE–reactivity trends, indicating that DPE and acid strength are essential but incomplete reactivity descriptors. Born–Haber thermochemical cycles indicate that these differences reflect more effective charge reorganization upon deprotonation of Mo than W POM clusters and the much weaker reorganization in mineral acids. Such covalency is disrupted upon deprotonation but cannot be recovered fully upon formation of ion pairs at transition states. Predictive descriptors of reactivity for general classes of acids thus require separate assessments of the covalent and ionic DPE components. Here, we describe methods to estimate electrostatic interactions, which, taken together with energies derived from density functional theory, give the covalent and ionic energy components of protons, intermediates, and transition states. In doing so, we provide a framework to predict the reactive properties of protons for chemical reactions mediated by ion-pair transition states.

  3. Design of a Heterogeneous Catalyst Based on Cellulose Nanocrystals for Cyclopropanation: Synthesis and Solid-State NMR Characterization.

    PubMed

    Liu, Jiquan; Plog, Andreas; Groszewicz, Pedro; Zhao, Li; Xu, Yeping; Breitzke, Hergen; Stark, Annegret; Hoffmann, Rudolf; Gutmann, Torsten; Zhang, Kai; Buntkowsky, Gerd

    2015-08-24

    Heterogeneous dirhodium(II) catalysts based on environmentally benign and biocompatible cellulose nanocrystals (CNC-Rh2) as support material were obtained by ligand exchange between carboxyl groups on the CNC surface and Rh2(OOCCF3)4, as was confirmed by solid-state (19)F and (13)C?NMR spectroscopy. On average, two CF3COO(-) groups are replaced during ligand exchange, which is consistent with quantitative analysis by a combination of (19)F?NMR spectroscopy and thermogravimetry. CNC-Rh2 catalysts performed well in a model cyclopropanation reaction, in spite of the low dirhodium(II) content on the CNC surface (0.23?mmol?g(-1)). The immobilization through covalent bonding combined with the separate locations of binding positions and active sites of CNC-Rh2 guarantees a high stability against leaching and allows the recovery and reuse of the catalyst during the cyclopropanation reaction. PMID:26179865

  4. Gas diffusion electrode setup for catalyst testing in concentrated phosphoric acid at elevated temperatures

    NASA Astrophysics Data System (ADS)

    Wiberg, Gustav K. H.; Fleige, Michael; Arenz, Matthias

    2015-02-01

    We present a detailed description of the construction and testing of an electrochemical cell setup allowing the investigation of a gas diffusion electrode containing carbon supported high surface area catalysts. The setup is designed for measurements in concentrated phosphoric acid at elevated temperature, i.e., very close to the actual conditions in high temperature proton exchange membrane fuel cells (HT-PEMFCs). The cell consists of a stainless steel flow field and a PEEK plastic cell body comprising the electrochemical cell, which exhibits a three electrode configuration. The cell body and flow field are braced using a KF-25 vacuum flange clamp, which allows an easy assembly of the setup. As demonstrated, the setup can be used to investigate temperature dependent electrochemical processes on high surface area type electrocatalysts, but it also enables quick screening tests of HT-PEMFC catalysts under realistic conditions.

  5. Gas diffusion electrode setup for catalyst testing in concentrated phosphoric acid at elevated temperatures

    SciTech Connect

    Wiberg, Gustav K. H. E-mail: m.arenz@chem.ku.dk; Fleige, Michael; Arenz, Matthias E-mail: m.arenz@chem.ku.dk

    2015-02-15

    We present a detailed description of the construction and testing of an electrochemical cell setup allowing the investigation of a gas diffusion electrode containing carbon supported high surface area catalysts. The setup is designed for measurements in concentrated phosphoric acid at elevated temperature, i.e., very close to the actual conditions in high temperature proton exchange membrane fuel cells (HT-PEMFCs). The cell consists of a stainless steel flow field and a PEEK plastic cell body comprising the electrochemical cell, which exhibits a three electrode configuration. The cell body and flow field are braced using a KF-25 vacuum flange clamp, which allows an easy assembly of the setup. As demonstrated, the setup can be used to investigate temperature dependent electrochemical processes on high surface area type electrocatalysts, but it also enables quick screening tests of HT-PEMFC catalysts under realistic conditions.

  6. Highly efficient Brønsted acidic ionic liquid-based catalysts for biodiesel synthesis from vegetable oils.

    PubMed

    Ghiaci, M; Aghabarari, B; Habibollahi, S; Gil, A

    2011-01-01

    Biodiesel has been produced by transesterification of canola oil with methanol in the presence of highly Brønsted acidic ionic liquids based on 1-benzyl-1H-benzimidazole, and the effect of reaction temperature, type and amount of catalyst, molar ratio and reaction time investigated. The results show that the 4B ionic liquid has the highest catalytic activity and best recyclability under the optimised reaction conditions. Thus, this ionic liquid is able to catalyze the transesterification of canola oil to its methyl esters in 5 h with yields of more than 95%. Density functional calculations (B3LYP), using the 6-311G basis set, have been performed to have a better understanding on the reactivity of these catalysts. The catalytic activity of 4B for the transesterification of other vegetable oils and alcohols has also been studied. PMID:20970994

  7. High-temperature sulfuric acid decomposition over complex metal oxide catalysts

    SciTech Connect

    Daniel M. Ginosar; Harry W. Rollins; Lucia M. Petkovic; Kyle C. Burch; Michael J. Rush

    2009-05-01

    Activity and stability of FeTiO3, MnTiO3, NiFe2O4, CuFe2O4, NiCr2O4, 2CuO•Cr2O3, CuO and Fe2O3 for the atmospheric decomposition of concentrated sulfuric acid in sulfur-based thermochemical water splitting cycles are presented. Catalyst activity was determined at temperatures from 725 to 900 °C. Catalytic stability was examined at 850 °C for up to one week of continuous operation. The results were compared to a 1.0 wt% Pt/TiO2 catalyst. Surface area by nitrogen physisorption, X-ray diffraction analyses, and temperature programmed desorption and oxidation were used to characterize fresh and spent catalyst samples. Over the temperature range, the catalyst activity of the complex oxides followed the general trend: 2CuO•Cr2O3 > CuFe2O4 > NiCr2O4 ˜ NiFe2O4 > MnTiO3 ˜ FeTiO3. At temperatures less than 800 °C, the 1.0 wt% Pt/TiO2 catalyst had higher activity than the complex oxides, but at temperatures above 850 °C, the 2CuO•Cr2O3 and CuFe2O4 samples had the highest activity. Surface area was found to decrease for all of the metal oxides after exposure to reaction conditions. In addition, the two complex metal oxides that contained chromium were not stable in the reaction environment; both leached chromium into the acid stream and decomposed into their individual oxides. The FeTiO3 sample also produced a discoloration of the reactor due to minor leaching and converted to Fe2TiO5. Fe2O3, MnTiO3 and NiFe2O4 were relatively stable in the reaction environment. In addition, CuFe2O4 catalyst appeared promising due to its high activity and lack of any leaching issues.

  8. Diffusion suppression in vapor-liquid-solid Si nanowire growth by a barrier layer between the Au catalyst and substrate

    NASA Astrophysics Data System (ADS)

    Koto, Makoto; Watanabe, Masatoshi; Sugawa, Etsuko; Shimizu, Tomohiro; Shingubara, Shoso

    2014-10-01

    Nanowires have attracted significant interest because of their unique characteristics. Vapor-liquid-solid (VLS) growth is the standard method for fabricating nanowires and Au is the most commonly used catalyst. However, Au catalyst droplets diffuse over the Si substrate surface with a high migration velocity and agglomerate at relatively low temperatures. In our previous work, we reported a significant improvement in the positioning and diameter distribution of VLS-grown Si nanowires by inserting a diffusion barrier layer and concluded that the barrier layer suppressed the formation of AuSi eutectic droplets and prevented the droplets diffusing on the substrate surface during nucleation. In the present study, we analyzed the nucleation of the Au catalyst and examined its behavior during nucleation. Detailed multidirectional analysis and in situ observations confirmed that the formation and agglomeration of AuSi eutectic droplets was suppressed by the formation of a silicide layer. This because of the higher reaction temperatures between the diffusion barrier and the substrate silicon, and between the catalyst and the diffusion barrier, compared with the reaction between the Au catalyst and substrate silicon.

  9. Solid Lipid Nanoparticles Loaded with Retinoic Acid and Lauric Acid as an Alternative for Topical Treatment of Acne Vulgaris.

    PubMed

    Silva, Elton Luiz; Carneiro, Guilherme; De Araújo, Lidiane Advíncula; Trindade, Mariana de Jesus Vaz; Yoshida, Maria Irene; Oréfice, Rodrigo Lambert; Farias, Luis de Macêdo; De Carvalho, Maria Auxiliadora Roque; Dos Santos, Simone Gonçalves; Goulart, Gisele Assis Castro; Alves, Ricardo José; Ferreira, Lucas Antônio Miranda

    2015-01-01

    Topical therapy is the first choice for the treatment of mild to moderate acne and all-trans retinoic acid is one of the most used drugs. The combination of retinoids and antimicrobials is an innovative approach for acne therapy. Recently, lauric acid, a saturated fatty acid, has shown strong antimicrobial activity against Propionibacterium acnes. However, topical application of retinoic acid is followed by high incidence of side-effects, including erythema and irritation. Solid lipid nanoparticles represent an alternative to overcome these side-effects. This work aims to develop solid lipid nanoparticles loaded with retinoic acid and lauric acid and evaluate their antibacterial activity. The influence of lipophilic stearylamine on the characteristics of solid lipid nanoparticles was investigated. Solid lipid nanoparticles were characterized for size, zeta potential, encapsulation efficiency, differential scanning calorimetry and X-ray diffraction. The in vitro inhibitory activity of retinoic acid-lauric acid-loaded solid lipid nanoparticles was evaluated against Propionibacterium acnes, Staphylococcus aureus and Staphylococcus epidermidis. High encapsulation efficiency was obtained at initial time (94 ± 7% and 100 ± 4% for retinoic acid and lauric acid, respectively) and it was demonstrated that lauric acid-loaded-solid lipid nanoparticles provided the incorporation of retinoic acid. However, the presence of stearylamine is necessary to ensure stability of encapsulation. Moreover, retinoic acid-lauric acid-loaded solid lipid nanoparticles showed growth inhibitory activity against Staphylococcus epidermidis, Propionibacterium acnes and Staphylococcus aureus, representing an interesting alternative for the topical therapy of acne vulgaris. PMID:26328443

  10. One-Pot synthesis of phosphorylated mesoporous carbon heterogeneous catalysts with tailored surface acidity

    SciTech Connect

    Fulvio, Pasquale F; Mahurin, Shannon Mark; Mayes, Richard T; Bauer, Christopher; Wang, Xiqing; Veith, Gabriel M; Dai, Sheng

    2012-01-01

    Soft-templated phosphorylated mesoporous carbons with homogeneous distributions of phosphate groups were prepared by a 'one-pot' synthesis method using mixtures of phosphoric acid with hydrochloric, or nitric acids in the presence of Pluronic F127 triblock copolymer. Adjusting the various ratios of phosphoric acid used in these mixtures resulted in carbons with distinct adsorption, structural and surface acidity properties. The pore size distributions (PSDs) from nitrogen adsorption at -196 C showed that mesoporous carbons exhibit specific surface areas as high as 551 m{sup 2}/g and mesopores as large as 13 nm. Both structural ordering of the mesopores and the final phosphate contents were strongly dependent on the ratios of H{sub 3}PO{sub 4} in the synthesis gels, as shown by transmission electron microscopy (TEM), X-ray photoelectron (XPS) and energy dispersive X-ray spectroscopy (EDS). The number of surface acid sites determined from temperature programmed desorption of ammonia (NH{sub 3}-TPD) were in the range of 0.3-1.5 mmol/g while the active surface areas are estimated to comprise 5-54% of the total surface areas. Finally, the conversion temperatures for the isopropanol dehydration were lowered by as much as 100 C by transitioning from the least acidic to the most acidic catalysts surface.

  11. Cationic mononuclear ruthenium carboxylates as catalyst prototypes for self-induced hydrogenation of carboxylic acids

    PubMed Central

    Naruto, Masayuki; Saito, Susumu

    2015-01-01

    Carboxylic acids are ubiquitous in bio-renewable and petrochemical sources of carbon. Hydrogenation of carboxylic acids to yield alcohols produces water as the only byproduct, and thus represents a possible next generation, sustainable method for the production of these alternative energy carriers/platform chemicals on a large scale. Reported herein are molecular insights into cationic mononuclear ruthenium carboxylates ([Ru(OCOR)]+) as prototypical catalysts for the hydrogenation of carboxylic acids. The substrate-derived coordinated carboxylate was found to function initially as a proton acceptor for the heterolytic cleavage of dihydrogen, and subsequently also as an acceptor for the hydride from [Ru–H]+, which was generated in the first step (self-induced catalysis). The hydrogenation proceeded selectively and at high levels of functional group tolerance, a feature that is challenging to achieve with existing heterogeneous/homogeneous catalyst systems. These fundamental insights are expected to significantly benefit the future development of metal carboxylate-catalysed hydrogenation processes of bio-renewable resources. PMID:26314266

  12. Photodegradation of nalidixic acid assisted by TiO(2) nanorods/Ag nanoparticles based catalyst.

    PubMed

    Petronella, F; Diomede, S; Fanizza, E; Mascolo, G; Sibillano, T; Agostiano, A; Curri, M L; Comparelli, R

    2013-05-01

    Two different nanosized TiO2-based catalysts supported onto glass with tailored photocatalytic properties upon irradiation by UV light were successfully employed for the degradation of nalidixid acid, a widely diffused antibacterial agent of environmental relevance known to be non-biodegradable. Anatase rod-like TiO2 nanocrystals (TiO2NRs) and a semiconductor oxide-noble metal nanocomposite TiO2 NRs/Ag nanoparticles (NPs), synthesized by colloidal chemistry routes, were cast onto glass slide and employed as photocatalysts. A commercially available catalyst (TiO2 P25), also immobilized onto a glass slide, was used as a reference material. It was found that both TiO2 NRs/Ag NPs composite and TiO2 NRs demonstrated a photocatalytic efficiency significantly higher than the reference TiO2 P25. Specifically, TiO2 NRs/Ag NPs showed a photoactivity in nalidixic acid degradation 14 times higher than TiO2 P25 and 4 times higher than bare TiO2 NRs in the first 60min of reaction. Several by-products were identified by HPLC-MS along the nalidixic acid degradation, thus getting useful insight on the degradation pathway. All the identified by-products resulted completely removed after 6h of reaction. PMID:23466278

  13. Microwave-accelerated energy-efficient esterification of free fatty acid with a heterogeneous catalyst.

    PubMed

    Kim, Daeho; Choi, Jinju; Kim, Geun-Ju; Seol, Seung Kwon; Ha, Yun-Chul; Vijayan, M; Jung, Sunshin; Kim, Bo Hyun; Lee, Gun Dae; Park, Seong Soo

    2011-02-01

    This paper shows energy-efficiency of microwave-accelerated esterification of free fatty acid with a heterogeneous catalyst by net microwave power measurement. In the reaction condition of 5 wt% sulfated zirconia and 1:20 M ratio of oil to methanol at 60°C and atmospheric pressure, more than 90% conversion of the esterification was achieved in 20 min by microwave heating, while it took about 130 min by conventional heating. Electric energy consumption for the microwave heating in this accelerated esterification was only 67% of estimated minimum heat energy demand because of significantly reduced reaction time. PMID:21144741

  14. Direct Synthesis of Phenol from Benzene on an Activated Carbon Catalyst Treated with Nitric Acid

    NASA Astrophysics Data System (ADS)

    Chen, Cui-hong; Xu, Jia-quan; Jin, Ming-ming; Li, Gui-ying; Hu, Chang-wei

    2011-06-01

    Commercially available coal-based activated carbon was treated by nitric acid with different concentrations and the resultant samples were used as catalysts for the direct hydroxylation of benzene to phenol in acetonitrile. Boehm titration, X-ray photoelectron spectroscopy, scanning electron microscope coupled with an energy dispersive X-ray microanalyzer, and Brunauer-Emmett-Teller method were used to characterize the samples. The number of carboxyl groups on the surface was found to be the main factor affecting the catalytic activity. An optimum catalytic performance with a yield of 15.7% and a selectivity of 87.2% to phenol was obtained.

  15. Synthesis of Oxazoles by Tandem Cycloisomerization/Allylic Alkylation of Propargyl Amides with Allylic Alcohols: Zn(OTf)2 as ? Acid and ? Acid Catalyst.

    PubMed

    Wang, Bin; Chen, Ying; Zhou, Ling; Wang, Jianwu; Tung, Chen-Ho; Xu, Zhenghu

    2015-12-18

    A Zn(OTf)2-catalyzed tandem cycloisomerization/allylic alkylation of N-(propargyl)arylamides and allylic alcohols to produce oxazole derivatives has been successfully developed. The zinc catalyst served as ? acid and also ? acid in this reaction. The target allylic oxazoles have been transformed into multisubstituted diene structures, which are potential aggregation-induced emission active optical materials. PMID:26618919

  16. Stability of Fe-N-C Catalysts in Acidic Medium Studied by Operando Spectroscopy.

    PubMed

    Choi, Chang Hyuck; Baldizzone, Claudio; Grote, Jan-Philipp; Schuppert, Anna K; Jaouen, Frédéric; Mayrhofer, Karl J J

    2015-10-19

    Fundamental understanding of non-precious metal catalysts for the oxygen reduction reaction (ORR) is the nub for the successful replacement of noble Pt in fuel cells and, therefore, of central importance for a technological breakthrough. Herein, the degradation mechanisms of a model high-performance Fe-N-C catalyst have been studied with online inductively coupled plasma mass spectrometry (ICP-MS) and differential electrochemical mass spectroscopy (DEMS) coupled to a modified scanning flow cell (SFC) system. We demonstrate that Fe leaching from iron particles occurs at low potential (<0.7?V) without a direct adverse effect on the ORR activity, while carbon oxidation occurs at high potential (>0.9?V) with a destruction of active sites such as FeNx Cy species. Operando techniques combined with identical location-scanning transmission electron spectroscopy (IL-STEM) identify that the latter mechanism leads to a major ORR activity decay, depending on the upper potential limit and electrolyte temperature. Stable operando potential windows and operational strategies are suggested for avoiding degradation of Fe-N-C catalysts in acidic medium. PMID:26314711

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

  18. A solid form of ambazone with lactic acid

    NASA Astrophysics Data System (ADS)

    Borodi, Gh.; Muresan-Pop, M.; Kacsó, I.; Bratu, I.

    2012-02-01

    In recent years, much research has been carried out on the preparation of pharmaceutical solid forms due to their improved physical-chemical parameters such as solubility, dissolution rate of the drug, chemical stability, melting point and hygroscopic parameter. The aim of this study was to obtain and to investigate the structural properties of the ambazone (AMB) with lactic acid (LA) solid form. The solid form was obtained starting from the mixture of ambazone with lactic acid (1:1), by grinding method at constant temperature. The obtained compound was investigated via X-ray powder diffraction (PXRD), thermal analysis (DSC, TG-DTA) and infrared (FTIR) spectroscopy. The difference between the patterns of AMB•LA and of the starting compounds evidenced a new compound. Using X-ray powder diffraction method, by indexing procedure the unit cell and the lattice parameters were determined. Thermal and FTIR measurements on the pure compounds and on the (1:1) ground mixture of AMB with LA confirm the new salt form formation.

  19. Atomically mixed Fe-group nanoalloys: catalyst design for the selective electrooxidation of ethylene glycol to oxalic acid.

    PubMed

    Matsumoto, Takeshi; Sadakiyo, Masaaki; Ooi, Mei Lee; Yamamoto, Tomokazu; Matsumura, Syo; Kato, Kenichi; Takeguchi, Tatsuya; Ozawa, Nobuki; Kubo, Momoji; Yamauchi, Miho

    2015-05-01

    We demonstrate electric power generation via the electrooxidation of ethylene glycol (EG) on a series of Fe-group nanoalloy (NA) catalysts in alkaline media. A series of Fe-group binary NA catalysts supported on carbon (FeCo/C, FeNi/C, and CoNi/C) and monometallic analogues (Fe/C, Co/C, and Ni/C) were synthesized. Catalytic activities and product distributions on the prepared Fe-group NA catalysts in the EG electrooxidation were investigated by cyclic voltammetry and chronoamperometry, and compared with those of the previously reported FeCoNi/C, which clarified the contributory factors of the metal components for the EG electrooxidation activity, C2 product selectivity, and catalyst durability. The Co-containing catalysts, such as Co/C, FeCo/C, and FeCoNi/C, exhibit relatively high catalytic activities for EG electrooxidation, whereas the catalytic performances of Ni-containing catalysts are relatively low. However, we found that the inclusion of Ni is a requisite for the prevention of rapid degradation due to surface modification of the catalyst. Notably, FeCoNi/C shows the highest selectivity for oxalic acid production without CO2 generation at 0.4 V vs. the reversible hydrogen electrode (RHE), resulting from the synergetic contribution of all of the component elements. Finally, we performed power generation using the direct EG alkaline fuel cell in the presence of the Fe-group catalysts. The power density obtained on each catalyst directly reflected the catalytic performances elucidated in the electrochemical experiments for the corresponding catalyst. The catalytic roles and alloying effects disclosed herein provide information on the design of highly efficient electrocatalysts containing Fe-group metals. PMID:25848911

  20. The effect of the distance between acidic site and basic site immobilized on mesoporous solid on the activity in catalyzing aldol condensation

    NASA Astrophysics Data System (ADS)

    Yu, Xiaofang; Yu, Xiaobo; Wu, Shujie; Liu, Bo; Liu, Heng; Guan, Jingqi; Kan, Qiubin

    2011-02-01

    Acid-base bifunctional heterogeneous catalysts containing carboxylic and amine groups, which were immobilized at defined distance from one another on the mesoporous solid were synthesized by immobilizing lysine onto carboxyl-SBA-15. The obtained materials were characterized by X-ray diffraction (XRD), N 2 adsorption, Fourier-transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), scanning electron micrographs (SEM), transmission electron micrographs (TEM), elemental analysis, and back titration. Proximal-C-A-SBA-15 with a proximal acid-base distance was more active than maximum-C-A-SBA-15 with a maximum acid-base distance in aldol condensation reaction between acetone and various aldehydes. It appears that the distance between acidic site and basic site immobilized on mesoporous solid should be an essential factor for catalysis optimization.

  1. Heteropoly acid encapsulated into zeolite imidazolate framework (ZIF-67) cage as an efficient heterogeneous catalyst for Friedel-Crafts acylation

    NASA Astrophysics Data System (ADS)

    Ammar, Muhammad; Jiang, Sai; Ji, Shengfu

    2016-01-01

    A new strategy has been developed for the encapsulation of the phosphotungstic heteropoly acid (H3PW12O40 denoted as PTA) into zeolite imidazolate framework (ZIF-67) cage and the PTA@ZIF-67(ec) catalysts with different PTA content were prepared. The structure of the catalysts was characterized by XRD, BET, SEM, FT-IR, ICP-AES and TG. The catalytic activity and recovery properties of the catalysts for the Friedel-Crafts acylation of anisole with benzoyl chloride were evaluated. The results showed that 14.6-31.7 wt% PTA were encapsulated in the ZIF-67 cage. The PTA@ZIF-67(ec) catalysts had good catalytic activity for Friedel-Crafts acylation. The conversion of anisole can reach ~100% and the selectivity of the production can reach ~94% over 26.5 wt% PTA@ZIF-67(ec) catalyst under the reaction condition of 120 °C and 6 h. After reaction, the catalyst can be easily separated from the reaction mixture by the centrifugation. The recovered catalyst can be reused five times and the selectivity can be kept over 90%.

  2. Amino acid derived CuII compounds as catalysts for asymmetric oxidative coupling of 2-naphthol.

    PubMed

    Adão, Pedro; Barroso, Sónia; Carvalho, M Fernanda N N; Teixeira, Carlos M; Kuznetsov, Maxim L; Pessoa, João Costa

    2015-01-28

    We report the synthesis and characterization of several novel aminopyridine - L-amino acid derived Cu(II)-complexes. The ligands are prepared by a one-pot reductive alkylation of the L-amino acid scaffold and the respective aminopyridine Cu(II)-complexes were obtained by reaction with CuCl2 or Cu(acetato)2. All compounds were characterized by spectroscopic techniques, as well as ESI-MS. Two of the Cu(II)-complexes were characterized by single-crystal X-ray diffraction, one of them, [Cu(II)(L)(CH3COO)] (HL = (S)-3-phenyl-2-(pyridin-2-ylmethylamino)propanoic acid), being the first ever reported aminopyridine-class Cu(II) complex bearing a tridentate N,N,O donor set and a monodentate acetato ligand. The complexes are tested as catalysts in the oxidative coupling of 2-naphthol in organic solvent-water mixtures using dioxygen as the terminal oxidant. The effect of variables such as ligand denticity and substituents, as well as solvent, temperature and oxidant intake, on the overall performance is studied. In general, moderate to low conversions of 2-naphthol to 1,1'-bi-2-naphthol (BINOL) are obtained. The catalysts also showed moderate to low enantioselectivity. Some aspects of the reaction mechanism were elucidated by spectroscopy, electrochemical and theoretical studies. It was found that basic additives are important for activity, but these also increase the formation of secondary oxidation products. The addition of peroxide scavengers such as KI resulted in an increase of conversion, the yield of BINOL and enantioselectivity. PMID:25434677

  3. In Situ High Temperature Surface Enhanced Raman Spectroscopy for the Study of Interface Phenomena: Probing a Solid Acid on Alumina

    SciTech Connect

    Dai, Sheng; Formo, Eric V; Mahurin, Shannon Mark; Wu, Zili

    2011-01-01

    Herein, we utilize surface enhanced Raman spectroscopy (SERS) for the in situ analyses of catalyst structure while operating at elevated temperatures in various atmospheres. In order to accomplish this, robust SERS substrates were generated by depositing an ultrathin protective coating of alumina on top of silver nanowires (NWs) via atomic layer deposition (ALD). In situ studies were then conducted by analyzing the effects of heating a solid acid, phosphotungstic acid (PTA), on the alumina surface in either an oxygen or hydrogen environment at temperatures up to 400 C. Interestingly, the distance-dependent decay of the enhancement factor of the SERS signal from the underlying NWs allowed us to probe with great detail the interfacial region between the PTA and the alumina surface. The ability to analyze the area closest to the alumina surface was further confirmed by assembling vanadia onto the substrate and monitoring the intensity differences between the V-O-Al and outer V = O bonds.

  4. Effects of Si/Al Ratio on Cu/SSZ-13 NH3-SCR Catalysts: Implications for the active Cu species and the Roles of Brønsted Acidity

    SciTech Connect

    Gao, Feng; Washton, Nancy M.; Wang, Yilin; Kollar, Marton; Szanyi, Janos; Peden, Charles HF

    2015-09-03

    Cu/SSZ-13 catalysts with three Si/Al ratios of 6, 12 and 35 were synthesized with Cu incorporation via solution ion exchange. The implications of varying Si/Al ratios on the nature of the multiple Cu species that can be present in the SSZ-13 zeolite are a major focus of this work, as highlighted by the results of a variety of catalyst characterization and reaction kinetics measurements. Specifically, catalysts were characterized with surface area/pore volume measurements, temperature programmed reduction by H2 (H2-TPR), NH3 temperature programmed desorption (NH3-TPD), and DRIFTS and solid-state nuclear magnetic resonance (NMR) spectroscopies. Catalytic properties were examined using NO oxidation, ammonia oxidation, and standard ammonia selective catalytic reduction (NH3-SCR) reactions on selected catalysts under differential conditions. Besides indicating possible variably active multiple Cu species for these reactions, the measurements are also used to untangle some of the complexities caused by the interplay between redox of Cu ion centers and Brønsted acidity. All three reactions appear to follow a redox reaction mechanism, yet the roles of Brønsted acidity are quite different. For NO oxidation, increasing Si/Al ratio lowers Cu redox barriers, thus enhancing reaction rates. Brønsted acidity appears to play essentially no role for this reaction. For standard NH3-SCR, residual Brønsted acidity plays a significant beneficial role at both low- and high-temperature regimes. For NH3 oxidation, no clear trend is observed suggesting both Cu ion center redox and Brønsted acidity play important and perhaps competing roles. The authors gratefully acknowledge the US Department of Energy (DOE), Energy Efficiency and Renewable Energy, Vehicle Technologies Office for the support of this work. The research described in this paper was performed in the Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by the DOE’s Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory (PNNL). PNNL is operated for the US DOE by Battelle.

  5. Sustainable solid catalyst alkylation of commercial olefins by regeneration with supercritical isobutane

    SciTech Connect

    Daniel M. Ginosar; David N. Thompson; Kyle C. Burch

    2005-12-01

    Supercritical isobutane regeneration of a USY zeolite alkylation catalyst was examined in a continuous, automated reaction / regeneration system. Two feeds were studied; a synthetic isobutane / 2-butene blend, and a commercial refinery isoparaffin / olefin blend. The refinery blend was minimally treated, containing a variety of light olefins, and contaminants, including butadiene, oxygenates and sulfur, which are well known to cause severe catalyst deactivation. Synthetic feed experiments showed that high levels of butene conversion was maintained for more than 200 hours time on stream, and that product quality and catalyst maintenance was relatively stable over the course of the experiment using a 3 hour reaction / 3 hour regeneration cycle. Catalyst activity maintenance was lower when the commercial feed was employed. High levels of alkene conversion were maintained for 78 hours and 192 hours using a 3 hour reaction / 3 hour regeneration cycle and a 2 hour reaction / 2 hour regeneration cycle, respectively.

  6. Catalyst Activity and Post-operation Analyses of Pt/TiO2 (Rutile) Catalysts Used in the Sulfuric Acid Decomposition Reaction

    SciTech Connect

    Lucia M. Petkovic; Daniel M. Ginosar; Harry W. Rollins; Kyle C. Burch; Patrick J. Pinhero; Helen H. Farrell

    2007-06-01

    Production of hydrogen by splitting of water at lower temperatures than by direct thermal decomposition can be achieved by a series of particular chemical reactions that establish a thermochemical cycle [1]. Among the high number of thermochemical water-splitting cycles proposed in the literature [2], the sulfur-based group is of considerable interest. All the sulfur-based cycles employ the catalytic decomposition of sulfuric acid into SO2 and O2. The produced O2 corresponds to the O2 generated from water in the overall cycle. Research performed at the Idaho National Laboratory [3] has found that even one of the most stables catalysts, Pt supported on low surface area titania, deactivates with time on stream (TOS). To develop an understanding of the factors that cause catalyst deactivation, samples of 1% Pt supported on titania (rutile) catalyst were submitted to flowing concentrated sulfuric acid at 1123 K and atmospheric pressure for different TOSs between 0 and 548 h and a number of chemical and spectroscopic analyses applied to the spent samples.

  7. Preparation and characterization of a composite hydrogel with graphene oxide as an acid catalyst.

    PubMed

    Jiang, Ting; Sui, Zhu-Yin; Yang, Quan-Sheng; Zhang, Xuetong; Han, Bao-Hang

    2015-04-28

    In this study, a facile method for synthesizing a novel graphene oxide/pyrrole-formaldehyde (GOP-1) composite hydrogel was developed via in situ polymerization of pyrrole and formaldehyde in the presence of graphene oxide sheets without any additional catalyst. During the polymerization, graphene oxide can act as a two-dimensional template to regulate the aggregation state of polymer and as an acid catalyst to accelerate the reaction rate of pyrrole and formaldehyde. The morphology and microstructure were investigated by scanning electron microscopy, transmission electron microscopy, and X-ray diffraction, respectively. The chemical properties were analyzed via X-ray photoelectron spectroscopy, infrared spectroscopy, and Raman spectroscopy. The freeze-dried GOP-1 composite hydrogel exhibited a large specific surface area, high nitrogen content, and three-dimensional network structure. Based on the above features, the freeze-dried GOP-1 composite hydrogel used as a gas adsorbent showed a high carbon dioxide uptake capacity at 1.0 bar and 273 K (11.1 wt%), in sharp contrast to that of graphene oxide (7.4 wt%). Furthermore, the as-prepared composite hydrogel may possess attractive potential in the fields of electrode material, tissue engineering, and water treatment. PMID:25760407

  8. Structurally ordered Pt–Zn/C series nanoparticles as efficient anode catalysts for formic acid electrooxidation

    DOE PAGESBeta

    Zhu, Jing; Zheng, Xin; Wang, Jie; Wu, Zexing; Han, Lili; Lin, Ruoqian; Xin, Huolin L.; Wang, Deli

    2015-09-15

    Controlling the size, composition, and structure of bimetallic nanoparticles is of particular interest in the field of electrocatalysts for fuel cells. In the present work, structurally ordered nanoparticles with intermetallic phases of Pt3Zn and PtZn have been successfully synthesized via an impregnation reduction method, followed by post heat-treatment. The Pt3Zn and PtZn ordered intermetallic nanoparticles are well dispersed on a carbon support with ultrasmall mean particle sizes of ~5 nm and ~3 nm in diameter, respectively, which are credited to the evaporation of the zinc element at high temperature. These catalysts are less susceptible to CO poisoning relative to Pt/Cmore »and exhibited enhanced catalytic activity and stability toward formic acid electrooxidation. The mass activities of the as-prepared catalysts were approximately 2 to 3 times that of commercial Pt at 0.5 V (vs. RHE). As a result, this facile synthetic strategy is scalable for mass production of catalytic materials.« less

  9. Carboxylic acid reduction over silica supported Cu, Ni and Cu2In, Ni2In catalysts.

    PubMed

    Onyestyák, György; Harnos, Szabolcs

    2014-01-01

    Hydroconversion of caprylic acid as model compound was studied in a flow-through fixed-bed reactor at 21 bar total pressure and 240-360 °C reaction temperature over various hydrogenating active phases: pure metal (Cu, Ni) and intermetallic compound (Cu(2)In, Ni(2)In) nanoparticles. Different silicas produced by dissimilar methods and a commercial gama-alumina were compared as appropriate supports. Catalyst precursors were activated in reducing H(2) flow at 21 bar and 450 °C as routine pretreatment. Catalysts of high activity and selectivity for alcohol production can be obtained by varying the supports, the main metals and their indium modified bimetallic forms. Diversity of catalytic behavior reflects the complexity of the surface reactions. Caprylic alcohol formation was substantiated to proceed through caprylic aldehyde intermediates, however it can be also dehydrated to dicaprylic ether or octenes over alumina support. Silica supports, especially a less compact variant seem to be more inert for side reactions than alumina. Different morphology of studied silicas can highly influence the catalytic performances taking place over different metal particles. PMID:25551722

  10. Formic Acid Decomposition on Au catalysts: DFT, Microkinetic Modeling, and Reaction Kinetics Experiments

    SciTech Connect

    Singh, Suyash; Li, Sha; Carrasquillo-Flores, Ronald; Alba-Rubio, Ana C.; Dumesic, James A.; Mavrikakis, Manos

    2014-04-01

    A combined theoretical and experimental approach is presented that uses a comprehensive mean-field microkinetic model, reaction kinetics experiments, and scanning transmission electron microscopy imaging to unravel the reaction mechanism and provide insights into the nature of active sites for formic acid (HCOOH) decomposition on Au/SiC catalysts. All input parameters for the microkinetic model are derived from periodic, self-consistent, generalized gradient approximation (GGA-PW91) density functional theory calculations on the Au(111), Au(100), and Au(211) surfaces and are subsequently adjusted to describe the experimental HCOOH decomposition rate and selectivity data. It is shown that the HCOOH decomposition follows the formate (HCOO) mediated path, with 100% selectivity toward the dehydrogenation products (CO21H2) under all reaction conditions. An analysis of the kinetic parameters suggests that an Au surface in which the coordination number of surface Au atoms is 4 may provide a better model for the active site of HCOOH decomposition on these specific supported Au catalysts.

  11. Structurally ordered Pt–Zn/C series nanoparticles as efficient anode catalysts for formic acid electrooxidation

    SciTech Connect

    Zhu, Jing; Zheng, Xin; Wang, Jie; Wu, Zexing; Han, Lili; Lin, Ruoqian; Xin, Huolin L.; Wang, Deli

    2015-09-15

    Controlling the size, composition, and structure of bimetallic nanoparticles is of particular interest in the field of electrocatalysts for fuel cells. In the present work, structurally ordered nanoparticles with intermetallic phases of Pt3Zn and PtZn have been successfully synthesized via an impregnation reduction method, followed by post heat-treatment. The Pt3Zn and PtZn ordered intermetallic nanoparticles are well dispersed on a carbon support with ultrasmall mean particle sizes of ~5 nm and ~3 nm in diameter, respectively, which are credited to the evaporation of the zinc element at high temperature. These catalysts are less susceptible to CO poisoning relative to Pt/C and exhibited enhanced catalytic activity and stability toward formic acid electrooxidation. The mass activities of the as-prepared catalysts were approximately 2 to 3 times that of commercial Pt at 0.5 V (vs. RHE). As a result, this facile synthetic strategy is scalable for mass production of catalytic materials.

  12. Hydrodeoxygenation of phenols as lignin models under acid-free conditions with carbon-supported platinum catalysts.

    PubMed

    Ohta, Hidetoshi; Kobayashi, Hirokazu; Hara, Kenji; Fukuoka, Atsushi

    2011-11-28

    Carbon-supported Pt catalysts are highly active and reusable for the aqueous-phase hydrodeoxygenation of phenols as lignin models without adding any acids. It is suggested that Pt/carbon facilitates the hydrogenation of phenols and the hydrogenolysis of the resulting cyclohexanols. PMID:21991582

  13. Stannic chloride-para toluene sulfonic acid as a novel catalyst-co-catalyst system for the designing of hydroxyl terminated polyepichlorohydrin polymer: Synthesis and characterization.

    PubMed

    Ahmad, Muhammad; Sirajuddin, Muhammad; Akther, Zareen; Ahmad, Waqar

    2015-12-01

    Hydroxy terminated polyepichlorohydrin (PECH) was synthesized in good yield (85-88%) with improved functionality (2.01-2.53) and desired number average molecular weight (?3000), using a novel catalyst-co-catalyst combination. The effect of various molar ratios (4-12) of p-toluenesulphonic acid and SnCl4 on molecular weight of PECH was investigated. Different polymerization conditions like temperature, time and monomer addition rates were found to have pronounced effect on molecular weight, polydispersity and functionality of the products. The molecular weight distribution and polydispersity of the synthesized polymers were determined by Gel permeation chromatography (GPC). Absolute value of Number average molecular weight (Mn) was established with vapor pressure osmometry and structural elucidations were carried out by FT-IR and NMR spectroscopic techniques. Terminal Hydroxyl groups were quantified by acetylation method and functionality was derived from hydroxyl value and Mn. PMID:26135537

  14. Titania-Supported Catalysts for Levulinic Acid Hydrogenation: Influence of Support and its Impact on ?-Valerolactone Yield.

    PubMed

    Ruppert, A M; Grams, J; J?drzejczyk, M; Matras-Michalska, J; Keller, N; Ostojska, K; Sautet, P

    2015-05-11

    A series of titania-supported ruthenium and platinum catalysts was investigated in the levulinic acid hydrogenation towards ?-valerolactone, a key reaction for the catalytic transformation of biomass. It was shown that various morphologies and phases of titania strongly influence the physicochemical and catalytic properties of supported Ru and Pt catalysts in different ways. In the case of the catalyst supported on mixed TiO2 phases, Ru particles are exclusively located on the minority rutile crystallites, whereas such an effect was not observed for platinum. The platinum catalyst activity could be increased when the metal was dispersed on the large surface-area anatase, which was not the case for ruthenium as a result of its agglomeration on this support. The activity of ruthenium on anatase could be increased in two ways: a)?when RuO2 formation during catalyst preparation was avoided; b)?when pure anatase support material was modified so that it exhibited no microporosity. The obtained results allow a better understanding of the role of the support for Ru and Pt catalysts. PMID:25641864

  15. Continuous Isosorbide Production From Sorbitol Using Solid Acid Catalysis

    SciTech Connect

    Williamson, R.; Holladay,J.; Jaffe, M.; Brunelle, D.

    2006-09-29

    This is a final report for a project funded by the US Department of Agriculture and managed by the US Department of Energy. The Iowa Corn Promotion Board was the principal contracting entity for the grant. The Iowa Corn Promotion Board subcontracted with General Electric, Pacific Northwest National Lab and New Jersey Institute of Technology to conduct research in this project. The Iowa Corn Promotion Board and General Electric provided cost share for the project. The purpose of this diverse collaboration was to integrate both the conversion and the polymer applications into one project and increase the likelihood of success. This project has led to additional collaborations among other polymer companies. The goals of the project were to develop a renewable route to isosorbide for commercialization that is economically competitive with all existing production technologies and to develop new applications for isosorbide in various products such as polymers and materials. Under this program a novel process for the production of isosorbide was developed and evaluated. The novel process converts corn based sorbitol into isosorbide using a solid catalyst with integrated water removal and product recovery. In addition the work under this program has identified several novel products based on isosorbide chemistries. These market applications include: epoxy resins, UV stabilizers, plasticizers and polyesters. These market applications have commercial interest within the current polymer industry. This report contains an overview summary of the accomplishments. Six inventions and four patent applications have been written as a result of this project. Additional data will be published in the patent applications. The data developed at New Jersey Institute of Technology was presented at two technical conferences held in June of 2006. Several companies have made inquiries about using this material in their products.

  16. Approaches to mitigate metal catalyst deactivation in solid oxide fuel cell (SOFC) fuel electrodes

    NASA Astrophysics Data System (ADS)

    Adijanto, Lawrence

    While Ni/YSZ cermets have been used successfully in SOFCs, they also have several limitations, thus motivating the use of highly conductive ceramics to replace the Ni components in SOFC anodes. Ceramic electrodes are promising for use in SOFC anodes because they are expected to be less susceptible to sintering and coking, be redox stable, and be more tolerant of impurities like sulfur. In this thesis, for catalytic studies, the infiltration procedure has been used to form composites which have greatly simplified the search for the best ceramics for anode applications. In the development of ceramic fuel electrodes for SOFC, high performance can only be achieved when a transition metal catalyst is added. Because of the high operating temperatures, deactivation of the metal catalyst by sintering and/or coking is a severe problem. In this thesis, two approaches aimed at mitigating metal catalyst deactivation which was achieved by: 1) designing a catalyst that is resistant to coking and sintering and 2) developing a new method for catalyst deposition, will be presented. The first approach involved synthesizing a self-regenerating, "smart" catalyst, in which Co, Cu, or Ni were inserted into the B-site of a perovskite oxide under oxidizing conditions and then brought back to the surface under reducing conditions. This restores lost surface area of sintered metal particles through an oxidation/reduction cycle. Results will be shown for each of the metals, as well as for Cu-Co mixed metal systems, which are found to exhibit good tolerance to carbon deposition and interesting catalytic properties. The second strategy involves depositing novel Pd CeO2 core-shell nanostructure catalysts onto a substrate surface which had been chemically modified to anchor the nanoparticles. The catalyst deposited onto the chemically modified, hydrophobic surface is shown to be uniform and well dispersed, and exhibit excellent thermal stability to temperatures as high as 1373 K. Similar metal catalyst deposition method was also employed to access their suitability for use in SOFC anodes.

  17. CoxC encased in carbon nanotubes: an efficient oxygen reduction catalyst under both acidic and alkaline conditions.

    PubMed

    Chen, Lisong; Cui, Xiangzhi; Wang, Qingsong; Zhang, Xiaohua; Wan, Gang; Cui, Fangming; Wei, Chenyang; Shi, Jianlin

    2015-12-21

    The design of a non-precious metal oxygen reduction reaction (ORR) catalyst of high activity and long durability in acidic electrolyte is of great importance for the development and commercialization of low-temperature fuel cells, which remains a great challenge to date. Here, we demonstrate a facile, scalable protocol for the controlled synthesis of CoxC encapsulated in carbon nanotubes as a novel kind of efficient electrochemical oxygen reduction reaction (ORR) catalyst. The synthesized CoxC/carbon nanotube features a high BET surface area, large pore volume and high graphitic content, which greatly favors enhanced ORR properties. The resultant composite electro-catalyst shows high ORR activity which is comparable with that of 20 wt% Pt/C in 0.1 M KOH electrolyte. More importantly, it also exhibits a high ORR activity in 0.1 M HClO4 with a near-complete 4e pathway. More attractively, compared to the most investigated FexC, CoxC as the proposed main catalytically active center shows much enhanced activity in acidic electrolyte, which will pave the way towards the rational design of an advanced electro-catalyst for an efficient ORR process especially under acidic conditions. Moreover, a fuel cell using the synthesized CoxC/carbon nanotube as a cathode catalyst showed a large open-circuit potential, high output power density and long durability, which make it a promising alternative to Pt/C as a non-precious metal ORR catalyst in proton exchange membrane fuel cells. PMID:26565522

  18. On the Acid-Base Mechanism for Ruthenium Water Oxidation Catalysts

    E-print Network

    Wang, Lee-Ping

    We present a detailed theoretical study of the pathway for water oxidation in synthetic ruthenium-based catalysts. As a first step, we consider a recently discovered single center catalyst, where experimental observations ...

  19. Steroid-Derived Naphthoquinoline Asphaltene Model Compounds: Hydriodic Acid Is the Active Catalyst in I2-Promoted Multicomponent Cyclocondensation Reactions.

    PubMed

    Schulze, Matthias; Scott, David E; Scherer, Alexander; Hampel, Frank; Hamilton, Robin J; Gray, Murray R; Tykwinski, Rik R; Stryker, Jeffrey M

    2015-12-01

    A multicomponent cyclocondensation reaction between 2-aminoanthracene, aromatic aldehydes, and 5-?-cholestan-3-one has been used to synthesize model asphaltene compounds. The active catalyst for this reaction has been identified as hydriodic acid, which is formed in situ from the reaction of iodine with water, while iodine is not a catalyst under anhydrous conditions. The products, which contain a tetrahydro[4]helicene moiety, are optically active, and the stereochemical characteristics have been examined by VT-NMR and VT-CD spectroscopies, as well as X-ray crystallography. PMID:26584791

  20. Tuning the acid/metal balance of carbon nanofiber-supported nickel catalysts for hydrolytic hydrogenation of cellulose.

    PubMed

    Van de Vyver, Stijn; Geboers, Jan; Schutyser, Wouter; Dusselier, Michiel; Eloy, Pierre; Dornez, Emmie; Seo, Jin Won; Courtin, Christophe M; Gaigneaux, Eric M; Jacobs, Pierre A; Sels, Bert F

    2012-08-01

    Carbon nanofibers (CNFs) are a class of graphitic support materials with considerable potential for catalytic conversion of biomass. Earlier, we demonstrated the hydrolytic hydrogenation of cellulose over reshaped nickel particles attached at the tip of CNFs. The aim of this follow-up study was to find a relationship between the acid/metal balance of the Ni/CNFs and their performance in the catalytic conversion of cellulose. After oxidation and incipient wetness impregnation with Ni, the Ni/CNFs were characterized by various analytical methods. To prepare a selective Ni/CNF catalyst, the influences of the nature of oxidation agent, Ni activation, and Ni loading were investigated. Under the applied reaction conditions, the best result, that is, 76 % yield in hexitols with 69 % sorbitol selectivity at 93 % conversion of cellulose, was obtained on a 7.5 wt % Ni/CNF catalyst prepared by chemical vapor deposition of CH(4) on a Ni/?-Al(2)O(3) catalyst, followed by oxidation in HNO(3) (twice for 1 h at 383 K), incipient wetness impregnation, and reduction at 773 K under H(2). This preparation method leads to a properly balanced Ni/CNF catalyst in terms of Ni dispersion and hydrogenation capacity on the one hand, and the number of acidic surface-oxygen groups responsible for the acid-catalyzed hydrolysis on the other. PMID:22730195

  1. Multielement crystalline and pseudocrystalline oxides as efficient catalysts for the direct transformation of glycerol into acrylic acid.

    PubMed

    Chieregato, Alessandro; Soriano, M Dolores; García-González, Ester; Puglia, Giuseppe; Basile, Francesco; Concepción, Patricia; Bandinelli, Claudia; López Nieto, José M; Cavani, Fabrizio

    2015-01-01

    Glycerol surplus from biodiesel synthesis still represents a major problem in the biofuel production chain. Meanwhile, those in the acrylic acid market are looking for new processes that are able to offer viable alternatives to propylene-based production. Therefore, acrylic acid synthesis from glycerol could be an effective solution to both issues. Among the viable routes, one-pot synthesis theoretically represents the most efficient process, but it is also highly challenging from the catalyst design standpoint. A new class of complex W--Mo--V mixed-oxide catalysts, which are strongly related to the hexagonal tungsten bronze structure, able to directly convert glycerol into acrylic acid with yields of up to 51?% are reported. PMID:25488515

  2. Stepwise engineering of a Pichia pastoris D-amino acid oxidase whole cell catalyst

    PubMed Central

    2010-01-01

    Background Trigonopsis variabilis D-amino acid oxidase (TvDAO) is a well characterized enzyme used for cephalosporin C conversion on industrial scale. However, the demands on the enzyme with respect to activity, operational stability and costs also vary with the field of application. Processes that use the soluble enzyme suffer from fast inactivation of TvDAO while immobilized oxidase preparations raise issues related to expensive carriers and catalyst efficiency. Therefore, oxidase preparations that are more robust and active than those currently available would enable a much broader range of economically viable applications of this enzyme in fine chemical syntheses. A multi-step engineering approach was chosen here to develop a robust and highly active Pichia pastoris TvDAO whole-cell biocatalyst. Results As compared to the native T. variabilis host, a more than seven-fold enhancement of the intracellular level of oxidase activity was achieved in P. pastoris through expression optimization by codon redesign as well as efficient subcellular targeting of the enzyme to peroxisomes. Multi copy integration further doubled expression and the specific activity of the whole cell catalyst. From a multicopy production strain, about 1.3 × 103 U/g wet cell weight (wcw) were derived by standard induction conditions feeding pure methanol. A fed-batch cultivation protocol using a mixture of methanol and glycerol in the induction phase attenuated the apparent toxicity of the recombinant oxidase to yield final biomass concentrations in the bioreactor of ? 200 g/L compared to only 117 g/L using the standard methanol feed. Permeabilization of P. pastoris using 10% isopropanol yielded a whole-cell enzyme preparation that showed 49% of the total available intracellular oxidase activity and was notably stabilized (by three times compared to a widely used TvDAO expressing Escherichia coli strain) under conditions of D-methionine conversion using vigorous aeration. Conclusions Stepwise optimization using a multi-level engineering approach has delivered a new P. pastoris whole cell TvDAO biocatalyst showing substantially enhanced specific activity and stability under operational conditions as compared to previously reported preparations of the enzyme. The production of the oxidase through fed-batch bioreactor culture and subsequent cell permeabilization is high-yielding and efficient. Therefore this P. pastoris catalyst has been evaluated for industrial purposes. PMID:20420682

  3. Chirality-specific growth of single-walled carbon nanotubes on solid alloy catalysts.

    PubMed

    Yang, Feng; Wang, Xiao; Zhang, Daqi; Yang, Juan; Luo, Da; Xu, Ziwei; Wei, Jiake; Wang, Jian-Qiang; Xu, Zhi; Peng, Fei; Li, Xuemei; Li, Ruoming; Li, Yilun; Li, Meihui; Bai, Xuedong; Ding, Feng; Li, Yan

    2014-06-26

    Carbon nanotubes have many material properties that make them attractive for applications. In the context of nanoelectronics, interest has focused on single-walled carbon nanotubes (SWNTs) because slight changes in tube diameter and wrapping angle, defined by the chirality indices (n,?m), will shift their electrical conductivity from one characteristic of a metallic state to one characteristic of a semiconducting state, and will also change the bandgap. However, this structure-function relationship can be fully exploited only with structurally pure SWNTs. Solution-based separation methods yield tubes within a narrow structure range, but the ultimate goal of producing just one type of SWNT by controlling its structure during growth has proved to be a considerable challenge over the last two decades. Such efforts aim to optimize the composition or shape of the catalyst particles that are used in the chemical vapour deposition synthesis process to decompose the carbon feedstock and influence SWNT nucleation and growth. This approach resulted in the highest reported proportion, 55 per cent, of single-chirality SWNTs in an as-grown sample. Here we show that SWNTs of a single chirality, (12,?6), can be produced directly with an abundance higher than 92 per cent when using tungsten-based bimetallic alloy nanocrystals as catalysts. These, unlike other catalysts used so far, have such high melting points that they maintain their crystalline structure during the chemical vapour deposition process. This feature seems crucial because experiment and simulation both suggest that the highly selective growth of (12,?6) SWNTs is the result of a good structural match between the carbon atom arrangement around the nanotube circumference and the arrangement of the catalytically active atoms in one of the planes of the nanocrystal catalyst. We anticipate that using high-melting-point alloy nanocrystals with optimized structures as catalysts paves the way for total chirality control in SWNT growth and will thus promote the development of SWNT applications. PMID:24965654

  4. The outer-coordination sphere: incorporating amino acids and peptides as ligands for homogeneous catalysts to mimic enzyme function

    SciTech Connect

    Shaw, Wendy J.

    2012-10-09

    Great progress has been achieved in the field of homogeneous transition metal-based catalysis, however, as a general rule these solution based catalysts are still easily outperformed, both in terms of rates and selectivity, by their analogous enzyme counterparts, including structural mimics of the active site. This observation suggests that the features of the enzyme beyond the active site, i.e. the outer-coordination sphere, are important for their exceptional function. Directly mimicking the outer-coordination sphere requires the incorporation of amino acids and peptides as ligands for homogeneous catalysts. This effort has been attempted for many homogeneous catalysts which span the manifold of catalytic reactions and often require careful thought regarding solvent type, pH and characterization to avoid unwanted side reactions or catalyst decomposition. This article reviews the current capability of synthesizing and characterizing this often difficult category of metal-based catalysts. This work was funded by the DOE Office of Science Early Career Research Program through the Office of Basic Energy Sciences. Pacific Northwest National Laboratory is operated by Battelle for the U.S. Department of Energy.

  5. Renewable Feedstocks: The Problem of Catalyst Deactivation and its Mitigation.

    PubMed

    Lange, Jean-Paul

    2015-11-01

    Much research has been carried out in the last decade to convert bio-based feedstock into fuels and chemicals. Most of the research focuses on developing active and selective catalysts, with much less attention devoted to their long-term stability. This Review considers the main challenges in long-term catalyst stability, discusses some fundamentals, and presents options for their mitigation. Three main challenges are discussed: catalyst fouling, catalyst poisoning, and catalyst destruction. Fouling is generally related to the deposition of insoluble components present in the feed or formed by degradation of the feed or intermediates. Poisoning is related to the deposition of electropositive contaminants (e.g. alkali and alkaline earth metals) on acid sites or of electronegative contaminants (e.g. N and S) at hydrogenation sites. Catalyst destruction results from the thermodynamic instability of most oxidic supports, solid acids/bases, and hydrogenation functions under hydrothermal conditions. PMID:26457585

  6. Development of biomimetic catalytic oxidation methods and non-salt methods using transition metal-based acid and base ambiphilic catalysts

    PubMed Central

    MURAHASHI, Shun-Ichi

    2011-01-01

    This review focuses on the development of ruthenium and flavin catalysts for environmentally benign oxidation reactions based on mimicking the functions of cytochrome P-450 and flavoenzymes, and low valent transition-metal catalysts that replace conventional acids and bases. Several new concepts and new types of catalytic reactions based on these concepts are described. PMID:21558760

  7. The effect of the distance between acidic site and basic site immobilized on mesoporous solid on the activity in catalyzing aldol condensation

    SciTech Connect

    Yu Xiaofang; Yu Xiaobo; Wu Shujie; Liu Bo; Liu Heng; Guan Jingqi; Kan Qiubin

    2011-02-15

    Acid-base bifunctional heterogeneous catalysts containing carboxylic and amine groups, which were immobilized at defined distance from one another on the mesoporous solid were synthesized by immobilizing lysine onto carboxyl-SBA-15. The obtained materials were characterized by X-ray diffraction (XRD), N{sub 2} adsorption, Fourier-transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), scanning electron micrographs (SEM), transmission electron micrographs (TEM), elemental analysis, and back titration. Proximal-C-A-SBA-15 with a proximal acid-base distance was more active than maximum-C-A-SBA-15 with a maximum acid-base distance in aldol condensation reaction between acetone and various aldehydes. It appears that the distance between acidic site and basic site immobilized on mesoporous solid should be an essential factor for catalysis optimization. -- Graphical abstract: Proximal-C-A-SBA-15 with a proximal acid-base distance and maximum-C-A-SBA-15 with a maximum acid-base distance were synthesized by immobilizing lysine onto carboxyl-SBA-15. Display Omitted Research highlights: {yields} Proximal-C-A-SBA-15 with a proximal acid-base distance. {yields} Maximum-C-A-SBA-15 with a maximum acid-base distance. {yields} Compared to maximum-C-A-SBA-15, proximal-C-A-SBA-15 was more active toward aldol condensation reaction between acetone and various aldehydes.

  8. CuO based catalysts on modified acidic silica supports tested in the de-NOx reduction.

    PubMed

    Bennici, Simona; Gervasini, Antonella; Lazzarin, Marta; Ragaini, Vittorio

    2005-03-01

    A series of dispersed CuO catalysts supported on modified silica supports with Al2O3 (SA), TiO2 (ST), and ZrO2 (SZ) were prepared optimising the adsorption method of copper deposition assisted by ultrasound treatment, already reported in a previous paper (S. Bennici, A. Gervasini, V. Ragaini, Ultrason. Sonochem. 10 (2003) 61). The obtained catalysts were characterized in their bulk (atomic absorption, X-ray diffraction, temperature programmed reduction) and surface (N2 adsorption, X-ray photoelectron spectroscopy, scanning electron microscopy) properties. The morphology of the finished materials was not deeply modified compared with that of the relevant supports. The employed complemented techniques evidenced a well dispersed CuO phase with a copper-support interaction on the most acidic supports (SA and SZ). The catalyst performances were studied in the reaction of selective catalytic reduction of NOx with ethene in oxidizing atmosphere in a flow apparatus under variable times (0.360-0.072 s) and temperatures (200-450 degrees C). The catalysts prepared on the most acidic supports (SA and SZ) were the most active and selective towards N2 formation. They showed a particular interesting activity in the reaction of NO2 reduction besides that of NO reduction. PMID:15501715

  9. [Study on solid dispersion of precipitated calcium carbonate-based oleanolic acid].

    PubMed

    Yan, Hong-mei; Zhang, Zhen-hai; Jia, Xiao-bin; Jiang, Yan-rong; Sun, E

    2015-05-01

    Oleanolic acid-precipitated calcium carbonate solid dispersion was prepared by using solvent evaporation method. The microscopic structure and physicochemical properties of solid dispersion were analyzed using differential scanning calorimetry and scanning electron microscopy (SEM). And its in vitro release also was investigated. The properties of the precipitated calcium carbonate was studied which was as a carrier of oleanolic acid solid dispersion. Differential scanning calorimetry analysis suggested that oleanolic acid may be present in solid dispersion as amorphous substance. The in vitro release determination results of oleanolic acid-precipitated calcium carbonate (1: 5) solid dispersion showed accumulated dissolution rate of.oleanolic acid was up to 90% at 45 min. Accelerating experiment showed that content and in vitro dissolution of oleanolic acid solid dispersion did not change after storing over 6 months. The results indicated that in vitro dissolution of oleanolic acid was improved greatly by the solid dispersion with precipitated calcium carbonate as a carrier. The solid dispersion is a stabilizing system which has actual applied value. PMID:26390651

  10. Catalytic Synthesis of Oxygenates: Mechanisms, Catalysts and Controlling Characteristics

    SciTech Connect

    Kamil Klier; Richard G. Herman

    2005-11-30

    This research focused on catalytic synthesis of unsymmetrical ethers as a part of a larger program involving oxygenated products in general, including alcohols, ethers, esters, carboxylic acids and their derivatives that link together environmentally compliant fuels, monomers, and high-value chemicals. The catalysts studied here were solid acids possessing strong Br�������¸nsted acid functionalities. The design of these catalysts involved anchoring the acid groups onto inorganic oxides, e.g. surface-grafted acid groups on zirconia, and a new class of mesoporous solid acids, i.e. propylsulfonic acid-derivatized SBA-15. The former catalysts consisted of a high surface concentration of sulfate groups on stable zirconia catalysts. The latter catalyst consists of high surface area, large pore propylsulfonic acid-derivatized silicas, specifically SBA-15. In both cases, the catalyst design and synthesis yielded high concentrations of acid sites in close proximity to one another. These materials have been well-characterization in terms of physical and chemical properties, as well as in regard to surface and bulk characteristics. Both types of catalysts were shown to exhibit high catalytic performance with respect to both activity and selectivity for the bifunctional coupling of alcohols to form ethers, which proceeds via an efficient SN2 reaction mechanism on the proximal acid sites. This commonality of the dual-site SN2 reaction mechanism over acid catalysts provides for maximum reaction rates and control of selectivity by reaction conditions, i.e. pressure, temperature, and reactant concentrations. This research provides the scientific groundwork for synthesis of ethers for energy applications. The synthesized environmentally acceptable ethers, in part derived from natural gas via alcohol intermediates, exhibit high cetane properties, e.g. methylisobutylether with cetane No. of 53 and dimethylether with cetane No. of 55-60, or high octane properties, e.g. diisopropylether with blending octane No. of 105, and can replace aromatics in liquid fuels.

  11. Solid-supported reagents composed of a copolymer possessing 2-O-sulfonyl mannosides and phase-transfer catalysts for the synthesis of 2-fluoroglucose.

    PubMed

    Takeuchi, Ryota; Sakai, Yuki; Tanaka, Hiroshi; Takahashi, Takashi

    2015-12-01

    We described the synthesis of a solid-supported co-polymer possessing mannosides and phase-transfer catalysts and synthesis of 2-fluoroglucoside from it. We first prepared a soluble copolymer from two allene monomers possessing a precursor for the synthesis of 2-fluoroglycose and a crown ether. The copolymerization of the monomers via the ?-ally nickel-catalyst smoothly proceeded at room temperature to provide a desired copolymer without decomposition of the sulfonate esters. The copolymer exhibited high reactivity towards fluorination in comparison with a conventional precursor. We next synthesized the solid-supported copolymer by using the solid-supported initiator attached with TentaGel® resins. TentaGel® enabled polymerization under stirring with stirring bar without decomposition. The solid-supported copolymer exhibited comparable reactivity towards fluorination in comparison with the soluble copolymer. In addition, it can be easily separated from the reaction vessel by filtration. PMID:26525864

  12. Heterogenization of Homogeneous Catalysts: the Effect of the Support

    SciTech Connect

    Earl, W.L.; Ott, K.C.; Hall, K.A.; de Rege, F.M.; Morita, D.K.; Tumas, W.; Brown, G.H.; Broene, R.D.

    1999-06-29

    We have studied the influence of placing a soluble, homogeneous catalyst onto a solid support. We determined that such a 'heterogenized' homogeneous catalyst can have improved activity and selectivity for the asymmetric hydrogenation of enamides to amino acid derivatives. The route of heterogenization of RhDuPhos(COD){sup +} cations occurs via electrostatic interactions with anions that are capable of strong hydrogen bonding to silica surfaces. This is a novel approach to supported catalysis. Supported RhDuPhos(COD){sup +} is a recyclable, non-leaching catalyst in non-polar media. This is one of the few heterogenized catalysts that exhibits improved catalytic performance as compared to its homogeneous analog.

  13. Selective catalytic reduction of NOx with NH3 over a Cu-SSZ-13 catalyst prepared by a solid state ion exchange method

    SciTech Connect

    Wang, Di; Gao, Feng; Peden, Charles HF; Li, Junhui; Kamasamudram, Krishna; Epling, William S.

    2014-06-01

    A novel solid state method was developed to synthesize Cu-SSZ-13 catalysts with excellent NH3-SCR performance and durable hydrothermal stability. After the solid state ion exchange (SSIE) process, the SSZ framework structure and surface area was maintained. In-situ DRIFTS and NH3-TPD experiments provide evidence that isolated Cu ions were successfully exchanged into the pores, which are the active centers for the NH3-SCR reaction.

  14. Interaction of Peroxynitric Acid with Solid H2O Ice

    NASA Technical Reports Server (NTRS)

    Li, Zhuangjie; Friedl, Randall R.; Moore, Steven B.; Sander, Stanley P.

    1996-01-01

    The uptake of peroxynitric acid (PNA), HO2NO2 or HNO4, on solid H2O ice at 193 K (-80 C) was studied using a fast flow-mass spectrometric technique. An uptake coefficient of 0.15 +/- 0.10 was measured, where the quoted uncertainty denotes 2 standard deviations. The uptake process did not result in the production of gas phase products. The composition of the condensed phase was investigated using programmed heating (3 K/min) of the substrate coupled with mass spectrometric detection of desorbed species. Significant quantities of HNO, and HNO3 desorbed from the substrates at temperatures above 225 K and 246 K, respectively. The desorbed HNO3, which was less than 9% of the desorbed HNO, and remained unchanged upon incubation of the substrate, was likely due to impurities in the HNO4 samples rather than reaction of HNO, on the substrate. The onset temperatures for HNO4 desorption increased with increasing H2O to HNO4 ratios, indicating that HNO4, like HNO3, tends to be hydrated in the presence of water. These observations suggest possible mechanisms for removal of HNO4 or repartitioning of total odd nitrogen species in the Earth's upper troposphere and stratosphere.

  15. 7 CFR 51.1178 - Maximum anhydrous citric acid permissible for corresponding total soluble solids.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... 7 Agriculture 2 2011-01-01 2011-01-01 false Maximum anhydrous citric acid permissible for... Sinensis (l) Osbeck) § 51.1178 Maximum anhydrous citric acid permissible for corresponding total soluble solids. For determining the grade of juice, the maximum permissible anhydrous citric acid content...

  16. 7 CFR 51.1178 - Maximum anhydrous citric acid permissible for corresponding total soluble solids.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 7 Agriculture 2 2010-01-01 2010-01-01 false Maximum anhydrous citric acid permissible for... Sinensis (l) Osbeck) § 51.1178 Maximum anhydrous citric acid permissible for corresponding total soluble solids. For determining the grade of juice, the maximum permissible anhydrous citric acid content...

  17. 7 CFR 51.1178 - Maximum anhydrous citric acid permissible for corresponding total soluble solids.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... 7 Agriculture 2 2014-01-01 2014-01-01 false Maximum anhydrous citric acid permissible for... Common Sweet Oranges (citrus Sinensis (l) Osbeck) § 51.1178 Maximum anhydrous citric acid permissible for... following Table II together with the minimum ratio of total soluble solids to anhydrous citric acid:...

  18. 7 CFR 51.1178 - Maximum anhydrous citric acid permissible for corresponding total soluble solids.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... 7 Agriculture 2 2012-01-01 2012-01-01 false Maximum anhydrous citric acid permissible for... Sinensis (l) Osbeck) § 51.1178 Maximum anhydrous citric acid permissible for corresponding total soluble solids. For determining the grade of juice, the maximum permissible anhydrous citric acid content...

  19. 7 CFR 51.1178 - Maximum anhydrous citric acid permissible for corresponding total soluble solids.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... 7 Agriculture 2 2013-01-01 2013-01-01 false Maximum anhydrous citric acid permissible for... Common Sweet Oranges (citrus Sinensis (l) Osbeck) § 51.1178 Maximum anhydrous citric acid permissible for... following Table II together with the minimum ratio of total soluble solids to anhydrous citric acid:...

  20. Photocatalytic detoxification of Acid Red 18 by modified ZnO catalyst under sunlight irradiation

    NASA Astrophysics Data System (ADS)

    Senthilraja, A.; Subash, B.; Dhatshanamurthi, P.; Swaminathan, M.; Shanthi, M.

    2015-03-01

    In this work, hybrid structured Bi-Au-ZnO composite was prepared by precipitation-decomposition method. This method is mild, economical and efficient. Bi-Au-ZnO was characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), transmission electron microscopy (TEM), energy dispersive spectrum (EDS), diffuse reflectance spectra (DRS), photoluminescence spectra (PL) and BET surface area measurements. Photocatalytic activity of Bi-Au-ZnO was evaluated by irradiating the Acid Red 18 (AR 18) dye solution under sun light. Heterostructured Bi-Au-ZnO photocatalyst showed higher photocatalytic activity than those of individual Bi-ZnO, Au-ZnO, bare ZnO, and TiO2-P25 at pH 11. The effects of operational parameters such as the amount of catalyst dosage, dye concentration, initial pH on photo mineralization of AR 18 dye have been analyzed. The mineralization of AR 18 has been confirmed by chemical oxygen demand (COD) measurements. A possible mechanism is proposed for the degradation of AR 18 under sun light. Finally, Bi-Au-ZnO heterojunction photocatalyst was more stable and could be easily recycled several times opening a new avenue for potential industrial applications.

  1. Intrinsic kinetics of 9-monoenic fatty acid methyl ester hydrogenation over nickel-based catalysts

    SciTech Connect

    Jonker, G.H.; Veldsink, J.W.; Beenackers, A.A.C.M.

    1997-05-01

    The monoenic fatty acid methyl ester hydrogenation and isomerization over a supported nickel catalyst was studied at 0.02 {le} P{sub H{sub 2}} {le} 0.50 MPa and 333 {le} T {le} 443 K. Batch hydrogenations at constant and variable hydrogen pressure were carried out to investigate the rate-determining steps. On the basis of the Horiuti-Polanyi mechanism, involving a half-hydrogenated surface intermediate, kinetic rate equations were systematically derived following the Langmuir-Hinshelwood-Hougen-Watson approach. Each set of rate equations was tested by means of a {chi}{sup 2} method on its ability to describe the experimental curves simultaneously. The {chi}{sup 2} was minimized by a stepwise optimization of model parameters. Furthermore, the authors used Bartlett`s test to reduce the set of most-likely rate expressions. The statistically most significant model assumes the formation of the half-hydrogenated surface intermediate as the rate-determining step and an equilibrium associative hydrogen adsorption. The rate equations are given.

  2. Photocatalytic detoxification of Acid Red 18 by modified ZnO catalyst under sunlight irradiation.

    PubMed

    Senthilraja, A; Subash, B; Dhatshanamurthi, P; Swaminathan, M; Shanthi, M

    2015-03-01

    In this work, hybrid structured Bi-Au-ZnO composite was prepared by precipitation-decomposition method. This method is mild, economical and efficient. Bi-Au-ZnO was characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), transmission electron microscopy (TEM), energy dispersive spectrum (EDS), diffuse reflectance spectra (DRS), photoluminescence spectra (PL) and BET surface area measurements. Photocatalytic activity of Bi-Au-ZnO was evaluated by irradiating the Acid Red 18 (AR 18) dye solution under sun light. Heterostructured Bi-Au-ZnO photocatalyst showed higher photocatalytic activity than those of individual Bi-ZnO, Au-ZnO, bare ZnO, and TiO2-P25 at pH 11. The effects of operational parameters such as the amount of catalyst dosage, dye concentration, initial pH on photo mineralization of AR 18 dye have been analyzed. The mineralization of AR 18 has been confirmed by chemical oxygen demand (COD) measurements. A possible mechanism is proposed for the degradation of AR 18 under sun light. Finally, Bi-Au-ZnO heterojunction photocatalyst was more stable and could be easily recycled several times opening a new avenue for potential industrial applications. PMID:25437842

  3. Catalytic Upgrading of bio-oil using 1-octene and 1-butanol over sulfonic acid resin catalysts

    SciTech Connect

    Zhang, Zhijun; Wang, Qingwen; Tripathi, Prabhat; Pittman, Charles U.

    2011-02-04

    Raw bio-oil from fast pyrolysis of biomass must be refined before it can be used as a transporation fuel, a petroleum refinery feed or for many other fuel uses. Raw bio-oil was upgraded with the neat model olefin, 1-octene, and with 1-octene/1-butanol mixtures over sulfonic acid resin catalysts frin 80 to 150 degrees celisus in order to simultaneously lower water content and acidity and to increase hydrophobicity and heating value. Phase separation and coke formation were key factors limiting the reaction rate during upgrading with neat 1-octene although octanols were formed by 1-octene hydration along with small amounts of octyl acetates and ethers. GC-MS analysis confirmed that olefin hydration, carboxylic acid esterification, acetal formation from aldehydes and ketones and O- and C-alkylations of phenolic compounds occurred simultaneously during upgrading with 1-octene/1-butanol mixtures. Addition of 1-butanol increased olefin conversion dramatically be reducing mass transfer restraints and serving as a cosolvent or emulsifying agent. It also reacted with carboxylic acids and aldehydes/ketones to form esters, and acetals, respectively, while also serving to stabilize bio-oil during heating. 1-Butanol addition also protected the catalysts, increasing catalyst lifetime and reducing or eliminationg coking. Upgrading sharply increased ester content and decreased the amounts of levoglucosan, polyhydric alcohols and organic acids. Upgrading lowered acidity (pH value rise from 2.5 to >3.0), removed the uppleasant ordor and increased hydrocarbon solubility. Water content decreased from 37.2% to < 7.5% dramatically and calorific value increased from 12.6 MJ kg to about 30.0 MJ kg.

  4. Catalyst functionalized buffer sorbent pebbles for rapid separation of carbon dioxide from gas mixtures

    DOEpatents

    Aines, Roger D

    2015-03-31

    A method for separating CO.sub.2 from gas mixtures uses a slurried media impregnated with buffer compounds and coating the solid media with a catalyst or enzyme that promotes the transformation of CO.sub.2 to carbonic acid. Buffer sorbent pebbles with a catalyst or enzyme coating are provided for rapid separation of CO.sub.2 from gas mixtures.

  5. Catalyst functionalized buffer sorbent pebbles for rapid separation of carbon dioxide from gas mixtures

    DOEpatents

    Aines, Roger D.

    2013-03-12

    A method for separating CO.sub.2 from gas mixtures uses a slurried media impregnated with buffer compounds and coating the solid media with a catalyst or enzyme that promotes the transformation of CO.sub.2 to carbonic acid. Buffer sorbent pebbles with a catalyst or enzyme coating are provided for rapid separation of CO.sub.2 from gas mixtures.

  6. Esterification of oleic acid in a three-phase, fixed-bed reactor packed with a cation exchange resin catalyst.

    PubMed

    Son, Sung Mo; Kimura, Hiroko; Kusakabe, Katsuki

    2011-01-01

    Esterification of oleic acid was performed in a three-phase fixed-bed reactor with a cation exchange resin catalyst (Amberlyst-15) at high temperature, which was varied from 80 to 120 °C. The fatty acid methyl ester (FAME) yields in the fixed-bed reactor were increased with increases in the reaction temperature, methanol flow rate and bed height. Moreover, the FAME yields were higher than those obtained using a batch reactor due to an equilibrium shift toward the product that resulted from continuous evaporation of the produced water. In addition, there was no catalyst deactivation during the esterification of oleic acid. However, addition of sunflower oil to the oleic acid reduced the FAME yield obtained from simultaneous esterification and transesterification. The FAME yield was 97.5% at a reaction temperature of 100 °C in the fixed-bed with a height of 5 cm when the methanol and oleic acid feed rates were 8.6 and 9.0 mL/h, respectively. PMID:20855192

  7. Oxyhydrochlorination catalyst

    DOEpatents

    Taylor, Charles E. (Pittsburgh, PA); Noceti, Richard P. (Pittsburgh, PA)

    1992-01-01

    An improved catalyst and method for the oxyhydrochlorination of methane is disclosed. The catalyst includes a pyrogenic porous support on which is layered as active material, cobalt chloride in major proportion, and minor proportions of an alkali metal chloride and of a rare earth chloride. On contact of the catalyst with a gas flow of methane, HCl and oxygen, more than 60% of the methane is converted and of that converted more than 40% occurs as monochloromethane. Advantageously, the monochloromethane can be used to produce gasoline boiling range hydrocarbons with the recycle of HCl for further reaction. This catalyst is also of value for the production of formic acid as are analogous catalysts with lead, silver or nickel chlorides substituted for the cobalt chloride.

  8. Degradation of acid scarlet 3R with CuO/SiO2 hollow sphere catalyst

    NASA Astrophysics Data System (ADS)

    Xie, F.; Zhong, J.; Wang, L.; Wang, K.; Hua, D. X.

    2015-07-01

    Silica-supported copper catalyst materials have been synthesized via an incipient wetness impregnation. The resulting samples were characterized using X-ray diffraction (XRD) and Scanning electron microscope (SEM). The heterogeneous Fenton-like oxidation of reactive azo dye solutions by this catalyst was also investigated. The effects of various operating conditions on decolorization performance were evaluated, namely hydrogen peroxide dosage, initial pH, catalyst loading and initial dye concentration. The results indicated that by using 34 mmol/L of H2O2 and 6.0 g L-1 of the catalyst at 60°C, pH 3.5, 97% of decolorization efficiency was achieved within 90 min. CuO/SiO2 hollow sphere is shown a promising catalyst for degradation of azo dye aqueous solution by Fenton-like processes.

  9. An unprecedented (3,4,24)-connected heteropolyoxozincate organic framework as heterogeneous crystalline Lewis acid catalyst for biodiesel production

    PubMed Central

    Du, Dong-Ying; Qin, Jun-Sheng; Sun, Zhong; Yan, Li-Kai; O'Keeffe, Michael; Su, Zhong-Min; Li, Shun-Li; Wang, Xiao-Hong; Wang, Xin-Long; Lan, Ya-Qian

    2013-01-01

    A novel 3D hexadecanuclear heteropolyoxozincate organic framework, IFMC-200, has been successfully synthesized based on a late transition metal-oxygen cluster. IFMC-200 not only represents the first example of (3,4,24)-connected framework but also contains the first 24-connected single metal cluster in a crystal structure. It exhibits superior thermal stability, good water-stability, and even insensitivity to the existence of acid and base within a certain range of pH values. Furthermore, it performs as a heterogeneous crystalline Lewis acid catalyst with good activity for the conversion of long-chain fatty acids rather than short-chain ones, and high recycling efficiency for esterification reaction of fatty acids with alcohols to produce biodiesel. PMID:24019078

  10. Mesoporous Aluminosilicate Catalysts for the Selective Isomerization of n-Hexane: The Roles of Surface Acidity and Platinum Metal.

    PubMed

    Musselwhite, Nathan; Na, Kyungsu; Sabyrov, Kairat; Alayoglu, Selim; Somorjai, Gabor A

    2015-08-19

    Several types of mesoporous aluminosilicates were synthesized and evaluated in the catalytic isomerization of n-hexane, both with and without Pt nanoparticles loaded into the mesopores. The materials investigated included mesoporous MFI and BEA type zeolites, MCF-17 mesoporous silica, and an aluminum modified MCF-17. The acidity of the materials was investigated through pyridine adsorption and Fourier Transform-Infrared Spectroscopy (FT-IR). It was found that the strong Brönsted acid sites in the micropores of the zeolite catalysts facilitated the cracking of hexane. However, the medium strength acid sites on the Al modified MCF-17 mesoporous silica greatly enhanced the isomerization reaction. Through the loading of different amounts of Pt into the mesopores of the Al modified MCF-17, the relationship between the metal nanoparticles and acidic sites on the support was revealed. PMID:26168190

  11. Efficient solvent-free synthesis of phytostanyl esters in the presence of acid-surfactant-combined catalyst.

    PubMed

    He, Wen-Sen; Ma, Yuan; Pan, Xiao-Xia; Li, Jing-Jing; Wang, Mei-Gui; Yang, Ye-Bo; Jia, Cheng-Sheng; Zhang, Xiao-Ming; Feng, Biao

    2012-09-26

    An efficient approach based on the synthesis of phytostanyl esters with an acid-surfactant-combined catalyst in a solvent-free system was developed. The effect of catalyst dose, substrate molar ratio, reaction temperature, and acyl donor was considered. The reaction conditions were further optimized by response surface methodology, and a high yield of phytostanyl laurate (>92%) was obtained under optimum conditions: 3.17:1 molar ratio of lauric acid to plant stanols, 4.01% catalyst dose (w/w), 119 °C, and 4.1 h. FT-IR, MS, and NMR were adopted to confirm the chemical structure of phytostanyl laurate. Meanwhile, the physiochemical properties of different phytostanyl esters were investigated. Compared with phytostanols, the prepared phytostanyl esters had much lower melting temperature and higher oil solubility. There was no obvious difference in melting and solidification properties between sunflower oil with phytostanyl laurate (<5%) or oleate (<10%) and the original sunflower oil, suggesting that the esterification of phytostanols greatly facilitated their corporation into oil-based foods. PMID:22920263

  12. Physical stability of spray dried solid dispersions of amorphous tolfenamic acid and polyvinylpyrolidone K30

    E-print Network

    Thybo, Pia

    2006-10-25

    DRIED SOLID DISPERSIONS OF AMORPHOUS TOLFENAMIC ACID AND POLYVINYLPYRROLIDONE K-30 Pia Thybo The Danish University of Pharmaceutical Sciences Copenhagen, Denmark GPEN October 2006 Side 2 Pia Thybo The Danish University of Pharmaceutical Sciences...

  13. Improved zeolite regeneration processes for preparing saturated branched-chain fatty acids

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Ferrierite zeolite solid is an excellent catalyst for the skeletal isomerization of unsaturated linear-chain fatty acids (i.e., oleic acid) to unsaturated branched-chain fatty acids (i.e., iso-oleic acid) follow by hydrogenation to give saturated branched-chain fatty acids (i.e., isostearic acid). ...

  14. Comparative study of CoFeNx/C catalyst obtained by pyrolysis of hemin and cobalt porphyrin for catalytic oxygen reduction in alkaline and acidic electrolytes

    NASA Astrophysics Data System (ADS)

    Jiang, Rongzhong; Chu, Deryn

    2014-01-01

    Comparative studies of the oxygen reduction kinetics and mechanisms of CoFeNx/C catalysts have been conducted with rotating disk electrode (RDE) and rotating ring-disk electrode (RRDE) in aqueous acid and alkaline solutions, as well as acidic and alkaline polymer electrolytes. The CoFeNx/C catalysts in this study were obtained by the pyrolysis of hemin and a cobalt porphyrin. In an alkaline electrolyte, a larger electron transfer coefficient (0.63) was obtained in comparison to that in an acidic electrolyte (0.44), signifying a lower free energy barrier for oxygen reduction. The kinetic rate constant (2.69 × 10-2 cm s-1) for catalytic oxygen reduction in alkaline solution at 0.6 V (versus RHE) is almost 4 times larger than that in acidic solution (7.3 × 10-3 cm s-1). A synergetic catalytic mechanism is proposed. The overall reduction is a 4-electron reduction of oxygen. The obtained CoFeNx/C catalyst was further evaluated as a cathode catalyst in single fuel cells with acidic, neutral and alkaline electrolyte membranes. The order of the single cell performances either for power density or for stability is acidic > neutral > alkaline. The different behaviors of the CoFeNx/C catalyst in half cell and single cell are discussed.

  15. Effects of acid catalyst type on structural, morphological, and optoelectrical properties of spin-coated TiO2 thin film

    NASA Astrophysics Data System (ADS)

    Golobostanfard, Mohammad Reza; Abdizadeh, Hossein

    2013-03-01

    The effects of different acid catalysts of nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, boric acid, acetic acid, and citric acid on structural, morphological, and optoelectrical properties of nanocrystalline spin-coated TiO2 thin films synthesized via alkoxide sol-gel route were investigated. It was found that only the sols with HNO3 and HCl are suitable for film preparation. The X-ray diffractometry and Raman analysis showed that crystalline phases could be controlled by the type of acid catalyst. Although the H2SO4 sol shows good stability, it causes extremely different morphology to form due to its different sol nature and high contact angle. Fourier transformed infrared spectra confirmed the presence of acid anion species in all samples even after calcination. Furthermore, it was inferred from UV-visable absorption spectra that although the band gap and thickness of the films are independent of acid catalyst type, the refractive index and porosity of the films are strongly affected by the type of acids.

  16. Hematite-Based Solar Water Splitting in Acidic Solutions: Functionalization by Mono- and Multilayers of Iridium Oxygen-Evolution Catalysts.

    PubMed

    Li, Wei; Sheehan, Stafford W; He, Da; He, Yumin; Yao, Xiahui; Grimm, Ronald L; Brudvig, Gary W; Wang, Dunwei

    2015-09-21

    Solar water splitting in acidic solutions has important technological implications, but has not been demonstrated to date in a dual absorber photoelectrochemical cell. The lack of functionally stable water-oxidation catalysts (WOCs) in acids is a key reason for this slow development. The only WOCs that are stable at low pH are Ir-based systems, which are typically too expensive to be implemented broadly. It is now shown that this deficiency may be corrected by applying an ultra-thin monolayer of a molecular Ir WOC to hematite for solar water splitting in acidic solutions. The turn-on voltage is observed to shift cathodically by 250?mV upon the application of a monolayer of the molecular Ir WOC. When the molecular WOC is replaced by a heterogeneous multilayer derivative, stable solar water splitting for over 5?h is achieved with near-unity Faradaic efficiency. PMID:26184365

  17. Ultrasound enhanced heterogeneous activation of peroxydisulfate by bimetallic Fe-Co/GAC catalyst for the degradation of Acid Orange 7 in water.

    PubMed

    Cai, Chun; Wang, Liguo; Gao, Hong; Hou, Liwei; Zhang, Hui

    2014-06-01

    Bimetallic Fe-Co/GAC (granular activated carbon) was prepared and used as heterogeneous catalyst in the ultrasound enhanced heterogeneous activation of peroxydisulfate (PS, S2O(2-)8) process. The effect of initial pH, PS concentration, catalyst addition and stirring rate on the decolorization of Acid Orange 7 (AO7) was investigated. The results showed that the decolorization efficiency increased with an increase in PS concentration from 0.3 to 0.5 g/L and an increase in catalyst amount from 0.5 to 0.8 g/L. But further increase in PS concentration and catalyst addition would result in an unpronounced increase in decolorization efficiency. In the range of 300 to 900 r/min, stirring rate had little effect on AO7 decolorization. The catalyst stability was evaluated by measuring decolorization efficiency for four successive cycles. PMID:25079835

  18. Nanoporous PdNi Alloy Nanowires As Highly Active Catalysts for the Electro-Oxidation of Formic Acid.

    PubMed

    Du, Chunyu; Chen, Meng; Wang, Wengang; Yin, Geping

    2011-02-01

    Highly active and durable catalysts for formic acid oxidation are crucial to the development of direct formic acid fuel cell. In this letter, we report the synthesis, characterization, and electrochemical testing of nanoporous Pd(57)Ni(43) alloy nanowires for use as the electrocatalyst towards formic acid oxidation (FAO). These nanowires are prepared by chemically dealloying of Ni from Ni-rich PdNi alloy nanowires, and have high surface area. X-ray diffraction data show that the Pd(57)Ni(43) nanowires have the face-centered cubic crystalline structure of pure Pd, whereas X-ray photoelectron spectroscopy confirm the modification of electronic structure of Pd by electron transfer from Ni to Pd. Electrocatalytic activity of the nanowires towards FAO exceeds that of the state-of-the-art Pd/C. More importantly, the nanowires are highly resistant to deactivation. It is proposed that the high active surface area and modulated surface properties by Ni are responsible for the improvement of activity and durability. Dealloyed nanoporous Pd(57)Ni(43) alloy nanowires are thus proposed as a promising catalyst towards FAO. PMID:21192691

  19. Tailoring the Synergistic Bronsted-Lewis acidic effects in Heteropolyacid catalysts: Applied in Esterification and Transesterification Reactions

    NASA Astrophysics Data System (ADS)

    Tao, Meilin; Xue, Lifang; Sun, Zhong; Wang, Shengtian; Wang, Xiaohong; Shi, Junyou

    2015-09-01

    In order to investigate the influences of Lewis metals on acidic properties and catalytic activities, a series of Keggin heteropolyacid (HPA) catalysts, HnPW11MO39 (M?=?TiIV, CuII, AlIII, SnIV, FeIII, CrIII, ZrIV and ZnII; for Ti and Zr, the number of oxygen is 40), were prepared and applied in the esterification and transesterification reactions. Only those cations with moderate Lewis acidity had a higher impact. Ti Substituted HPA, H5PW11TiO40, posse lower acid content compared with TixH3-4xPW12O40 (Ti partial exchanged protons in saturated H3PW12O40), which demonstrated that the Lewis metal as an addenda atom (H5PW11TiO40) was less efficient than those as counter cations (TixH3-4xPW12O40). On the other hand, the highest conversion reached 92.2% in transesterification and 97.4% in esterification. Meanwhile, a good result was achieved by H5PW11TiO40 in which the total selectivity of DAG and TGA was 96.7%. In addition, calcination treatment to H5PW11TiO40 make it insoluble in water which resulted in a heterogeneous catalyst feasible for reuse.

  20. Tailoring the Synergistic Bronsted-Lewis acidic effects in Heteropolyacid catalysts: Applied in Esterification and Transesterification Reactions.

    PubMed

    Tao, Meilin; Xue, Lifang; Sun, Zhong; Wang, Shengtian; Wang, Xiaohong; Shi, Junyou

    2015-01-01

    In order to investigate the influences of Lewis metals on acidic properties and catalytic activities, a series of Keggin heteropolyacid (HPA) catalysts, HnPW11MO39 (M = Ti(IV), Cu(II), Al(III), Sn(IV), Fe(III), Cr(III), Zr(IV) and Zn(II); for Ti and Zr, the number of oxygen is 40), were prepared and applied in the esterification and transesterification reactions. Only those cations with moderate Lewis acidity had a higher impact. Ti Substituted HPA, H5PW11TiO40, posse lower acid content compared with Ti(x)H(3-4x)PW12O40 (Ti partial exchanged protons in saturated H3PW12O40), which demonstrated that the Lewis metal as an addenda atom (H5PW11TiO40) was less efficient than those as counter cations (Ti(x)H(3-4x)PW12O40). On the other hand, the highest conversion reached 92.2% in transesterification and 97.4% in esterification. Meanwhile, a good result was achieved by H5PW11TiO40 in which the total selectivity of DAG and TGA was 96.7%. In addition, calcination treatment to H5PW11TiO40 make it insoluble in water which resulted in a heterogeneous catalyst feasible for reuse. PMID:26374393

  1. Tailoring the Synergistic Bronsted-Lewis acidic effects in Heteropolyacid catalysts: Applied in Esterification and Transesterification Reactions

    PubMed Central

    Tao, Meilin; Xue, Lifang; Sun, Zhong; Wang, Shengtian; Wang, Xiaohong; Shi, Junyou

    2015-01-01

    In order to investigate the influences of Lewis metals on acidic properties and catalytic activities, a series of Keggin heteropolyacid (HPA) catalysts, HnPW11MO39 (M?=?TiIV, CuII, AlIII, SnIV, FeIII, CrIII, ZrIV and ZnII; for Ti and Zr, the number of oxygen is 40), were prepared and applied in the esterification and transesterification reactions. Only those cations with moderate Lewis acidity had a higher impact. Ti Substituted HPA, H5PW11TiO40, posse lower acid content compared with TixH3?4xPW12O40 (Ti partial exchanged protons in saturated H3PW12O40), which demonstrated that the Lewis metal as an addenda atom (H5PW11TiO40) was less efficient than those as counter cations (TixH3?4xPW12O40). On the other hand, the highest conversion reached 92.2% in transesterification and 97.4% in esterification. Meanwhile, a good result was achieved by H5PW11TiO40 in which the total selectivity of DAG and TGA was 96.7%. In addition, calcination treatment to H5PW11TiO40 make it insoluble in water which resulted in a heterogeneous catalyst feasible for reuse. PMID:26374393

  2. Clay Minerals as Solid Acids and Their Catalytic Properties.

    ERIC Educational Resources Information Center

    Helsen, J.

    1982-01-01

    Discusses catalytic properties of clays, attributed to acidity of the clay surface. The formation of carbonium ions on montmorillonite is used as a demonstration of the presence of surface acidity, the enhanced dissociation of water molecules when polarized by cations, and the way the surface can interact with organic substances. (Author/JN)

  3. Selective aerobic oxidation of 1,3-propanediol to 3-hydroxypropanoic acid using hydrotalcite supported bimetallic gold nanoparticle catalyst in water

    NASA Astrophysics Data System (ADS)

    Mohammad, Mujahid; Nishimura, Shun; Ebitani, Kohki

    2015-02-01

    Selective oxidation of 1,3-propanediol (1,3-PD) to 3-hydroxypropanoic acid (3-HPA), an important industrial building block, was successfully achieved using hydrotalcite-supported bimetallic Au nanoparticle catalysts in water at 343 K under aerobic and base-free conditions. The highest yield of 42% with 73% selectivity towards 3-HPA was afforded by 1wt% Au0.8Pd0.2-PVP/HT catalyst.

  4. Easy solid-phase synthesis of pH-insensitive heterogeneous CNTs/FeS Fenton-like catalyst for the removal of antibiotics from aqueous solution.

    PubMed

    Ma, Jie; Yang, Mingxuan; Yu, Fei; Chen, Junhong

    2015-04-15

    We report a facile solid method to synthesize efficient carbon-based Fenton-like catalyst (CNTs/FeS) using as-prepared carbon nanotubes (APCNTs), which makes full use of the iron nanoparticles in APCNTs without needless purification. Furthermore, the CNTs/FeS was characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), thermogravimetric (TG) and other analysis techniques, and then the CNTs/FeS was used as a Fenton-like catalyst for removing ciprofloxacin from aqueous solution. Response Surface Methodology (RSM) was applied to find the effect of the reaction parameter and the optimum operating condition. Results shows the catalytic reaction had better suitability than previous studies in a wide range of pH values (pH 3-8) and the Fenton-like catalyst CNTs/FeS exhibits good catalytic activity for removing of antibiotic, which be attributed to the synergistic effect of adsorption-advanced oxidation and significantly improves efficiency of advanced oxidation. More importantly, the CNTs/FeS catalyst exhibit good regeneration performance and retains a high catalytic capacity (>75%) even after four reaction cycles. The catalytic mechanism were also studied further, the removal mechanism of ciprofloxacin by a CNTs/FeS heterogeneous Fenton-like process primarily involves three removal pathways occurring simultaneously: (a) adsorption removal by CNTs, (b) Fenton-like degradation catalyzed by FeS, (c) catalytic degradation by CNTs catalyst. And these actions also have synergistic effects for ciprofloxacin removal. PMID:25585283

  5. Controlling Axial p-n Heterojunction Abruptness Through Catalyst Alloying in Vapor-Liquid-Solid Grown Semiconductor Nanowires

    SciTech Connect

    Perea, Daniel E.; Schreiber, Daniel K.; Devaraj, Arun; Thevuthasan, Suntharampillai; Yoo, Jinkyoung; Dayeh, Shadi A.; Picraux, Samuel T.

    2012-07-30

    The p-n junction can be regarded as the most important electronic structure that is responsible for the ubiquity of semiconductor microelectronics today. Efforts to continually scale down the size of electronic components is guiding research to explore the use of nanomaterials synthesized from a bottom-up approach - group-IV semiconductor nanowires being one such material. However, Au-catalyzed synthesis of Si/Si1-x-Gex semiconductor nanowire heterojunctions using the commonly-used vapor-liquid-solid (VLS) growth technique results in diffuse heterojunction interfaces [1], leading to doubts of producing compositionally-sharp p-n junctions using this approach. However, we have recently reported the ability to increase Ge-Si nanowire heterojunction abruptness by VLS synthesis from a Au(1-x)Ga(x) catalyst alloy as shown by EDX analysis in an SEM [2]. In this work, we have extended the use of a AuGa catalyst alloy to produce more compositionally abrupt p-n junction interfaces compared to using pure Au as directly measured by atom probe tomography. As shown in Figure 1(a-b), individual Ge-Si heterostructured nanowires were grown vertically atop Ge(111) microposts. Direct growth on the microposts provides a facile approach to nanowire analysis which circumvents the need to use FIB-based sample preparation techniques. Both nanowires grown from pure Au and a AuGa catalyst alloy were analyzed. The corresponding 3D APT reconstruction of an individual heterostructured nanowire is shown in Figure 1(c) with the corresponding materials labeled. A 1-dimensional composition profile along the analysis direction in Figure 1(d) confirms an increase in heterojunction abruptness for nanowires grown from AuGa (~10nm) compared to nanowires grown from pure Au (~65nm). Analysis of the P distribution within the Si region (Figure 1(e)) indicates that P reaches a constant distribution over approximately 10nm when incorporated through the AuGa catalyst, whereas it continually increases over 100’s of nanometers when incorporated through pure Au. The apparent lower overall P concentration within the nanowire grown from the AuGa alloy suggests that the solubility of P in the alloy is lower compared to pure Au. The ability to controllably increase nanowire p-n junction abruptness is important for nanowire applications as solar cells and tunneling field effect transistors where an increase in device performance is expected from shaper p-n junction interfaces. [1] T.E. Clark et al., Nano Lett. 8 (2008) 1246. [2] D.E. Perea et al., Nano Lett. 11 (2011) 3117. [3] The research was supported through the user program at both the Center for Integrated Nanotechnologies at Los Alamos National Laboratory and the Environmental Molecular Sciences Laboratory at Pacific Northwest National Laboratory.

  6. Identification of Active and Spectator Sn Sites in Sn-? Following Solid-State Stannation, and Consequences for Lewis Acid Catalysis

    PubMed Central

    Hammond, Ceri; Padovan, Daniele; Al-Nayili, Abbas; Wells, Peter P; Gibson, Emma K; Dimitratos, Nikolaos

    2015-01-01

    Lewis acidic zeolites are rapidly emerging liquid-phase Lewis acid catalysts. Nevertheless, their inefficient synthesis procedure currently prohibits greater utilization and exploitation of these promising materials. Herein, we demonstrate that SnIV-containing zeolite beta can readily be prepared both selectively and extremely rapidly by solid-state incorporation (SSI) method. Through a combination of spectroscopic (XRD, UV/Vis, X-ray absorption, magic-angle spinning NMR, and diffuse reflectance infrared Fourier transform spectroscopy) studies, we unambiguously demonstrate that site-isolated, isomorphously substituted SnIV sites dominate the Sn population up to a loading of 5 wt % Sn. These sites are identical to those found in conventionally prepared Sn-beta, and result in our SSI material exhibiting identical levels of intrinsic activity (that is, turnover frequency) despite the threefold increase in Sn loading, and the extremely rapid and benign nature of our preparation methodology. We also identify the presence of spectator sites, in the form of SnIV oligomers, at higher levels of Sn loading. The consequences of this mixed population with regards to catalysis (Meerwein–Pondorf–Verley reaction and glucose isomerization) are also identified. PMID:26583051

  7. Preparation and characterizations of highly dispersed carbon supported PdxPty/C catalysts by a modified citrate reduction method for formic acid electrooxidation

    NASA Astrophysics Data System (ADS)

    Li, Zuopeng; Li, Muwu; Han, Mingjia; Zeng, Jianhuang; Li, Yuexia; Guo, Yanqin; Liao, Shijun

    2014-05-01

    Carbon supported PdxPty/C (atomic ratio x:y from 1:1 to 6:1) have been prepared by a modified citrate reduction method assisted by inorganic stabilizers. Without using high molecular capping agents as stabilizers, the PdxPty/C catalysts are highly dispersed on the carbon support and no particle aggregations are found for the PdxPty/C catalysts. X-ray photoelectron spectroscopy reveals either Pt or Pd segregation for the PdxPty/C catalysts depending on Pd/Pt atomic ratio. CO stripping in 0.5 M H2SO4 and repeated formic acid oxidation cyclic voltammetry in 0.5 M HCHO + 0.5 M H2SO4 have been conducted to test out the CO tolerance and stability of the catalysts, respectively. It has been found that, with the increase of Pd/Pt atomic ratio, the CO stripping peak potential increases (less CO tolerant), whereas the catalyst stability towards formic acid oxidation decreases. The as-prepared catalysts reveal excellent mass-normalized formic acid oxidation activity as compared with published results possibly due to high dispersion and the absence of high molecular capping agents.

  8. Supported Molecular Catalysts: Synthesis, In-Situ Characterization and Performance

    SciTech Connect

    Davis, Mark E.

    2009-03-13

    The objectives of our work are: (i) to create solid catalysts with active sites that can function in a cooperative manner to enhance reactivity and selectivity, and (ii) to prepare solid catalysts that can perform multiple reactions in a network that in some cases would not be possible in solution due to the incompatibilities of the various catalytic entities (for example an acid and a base). We carried out extensive reactions to test the nature of the cooperative effect caused by thiol/sulfonic acid interactions. The acid/thiol combination provided an example where the two organic groups should be positioned as close to one another as possible. We also studied a system where this is not possible (acid-base). We investigated simultaneously incorporating acid and base groups into the same material. For the case of acid and bases, there is an optimal separation distance (too close allows for neutralization while too far eliminates any cooperative behavior).

  9. Effect of catalyst diameter on vapour-liquid-solid growth of GaAs nanowires

    SciTech Connect

    O'Dowd, B. J. Shvets, I. V.; Wojtowicz, T.; Kolkovsky, V.; Wojciechowski, T.; Zgirski, M.; Rouvimov, S.; Liu, X.; Pimpinella, R.; Dobrowolska, M.; Furdyna, J.

    2014-08-14

    GaAs nanowires were grown on (111)B GaAs substrates using the vapour-liquid-solid mechanism. The Au/Pt nanodots used to catalyse wire growth were defined lithographically and had varying diameter and separation. An in-depth statistical analysis of the resulting nanowires, which had a cone-like shape, was carried out. This revealed that there were two categories of nanowire present, with differing height and tapering angle. The bimodal nature of wire shape was found to depend critically on the diameter of the Au-Ga droplet atop the nanowire. Transmission electron microscopy analysis also revealed that the density of stacking faults in the wires varied considerably between the two categories of wire. It is believed that the cause of the distinction in terms of shape and crystal structure is related to the contact angle between the droplet and the solid-liquid interface. The dependency of droplet diameter on contact angle is likely related to line-tension, which is a correction to Young's equation for the contact angle of a droplet upon a surface. The fact that contact angle may influence resulting wire structure and shape has important implications for the planning of growth conditions and the preparation of wires for use in proposed devices.

  10. Resonance Raman and surface- and tip-enhanced Raman spectroscopy methods to study solid catalysts and heterogeneous catalytic reactions.

    SciTech Connect

    Kim, H.; Kosuda, K. M.; Van Duyne, R. P.; Stair, P. C.

    2010-01-01

    Resonance Raman (RR) spectroscopy has several advantages over the normal Raman spectroscopy (RS) widely used for in situ characterization of solid catalysts and catalytic reactions. Compared with RS, RR can provide much higher sensitivity and selectivity in detecting catalytically-significant surface metal oxides. RR can potentially give useful information on the nature of excited states relevant to photocatalysis and on the anharmonic potential of the ground state. In this critical review a detailed discussion is presented on several types of RR experimental systems, three distinct sources of so-called Raman (fluorescence) background, detection limits for RR compared to other techniques (EXAFS, PM-IRAS, SFG), and three well-known methods to assign UV-vis absorption bands and a band-specific unified method that is derived mainly from RR results. In addition, the virtues and challenges of surface-enhanced Raman spectroscopy (SERS) are discussed for detecting molecular adsorbates at catalytically relevant interfaces. Tip-enhanced Raman spectroscopy (TERS), which is a combination of SERS and near-field scanning probe microscopy and has the capability of probing molecular adsorbates at specific catalytic sites with an enormous surface sensitivity and nanometre spatial resolution, is also reviewed.

  11. Hydrodeoxygenation of bio-derived phenols to hydrocarbons using RANEY Ni and Nafion/SiO2 catalysts.

    PubMed

    Zhao, Chen; Kou, Yuan; Lemonidou, Angeliki A; Li, Xuebing; Lercher, Johannes A

    2010-01-21

    A simple, green, cost- and energy-efficient route for converting phenolic components in bio-oil to hydrocarbons and methanol has been developed, with nearly 100% yields. In the heterogeneous catalysts, RANEY Ni acts as the hydrogenation catalyst and Nafion/SiO(2) acts as the Brønsted solid acid for hydrolysis and dehydration. PMID:20066309

  12. One-pot synthesis of graphene-supported monodisperse Pd nanoparticles as catalyst for formic acid electro-oxidation.

    PubMed

    Yang, Sudong; Dong, Jing; Yao, Zhaohui; Shen, Chengmin; Shi, Xuezhao; Tian, Yuan; Lin, Shaoxiong; Zhang, Xiaogang

    2014-01-01

    To synthesize monodisperse palladium nanoparticles dispersed on reduced graphene oxide (RGO) sheets, we have developed an easy and scalable solvothermal reduction method from an organic solution system. The RGO-supported palladium nanoparticles with a diameter of 3.8?nm are synthesized in N-methyl-2-pyrrolidone (NMP) and in the presence of oleylamine and trioctylphosphine, which facilitates simultaneous reduction of graphene oxide and formation of Pd nanocrystals. So-produced Pd/RGO was tested for potential use as electrocatalyst for the electro-oxidation of formic acid. Pd/RGO catalyzes formic acid oxidation very well compared to Pd/Vulcan XC-72 catalyst. This synthesis method is a new way to prepare excellent electrocatalysts, which is of great significance in energy-related catalysis. PMID:24675779

  13. One-Pot Synthesis of Graphene-Supported Monodisperse Pd Nanoparticles as Catalyst for Formic Acid Electro-oxidation

    NASA Astrophysics Data System (ADS)

    Yang, Sudong; Dong, Jing; Yao, Zhaohui; Shen, Chengmin; Shi, Xuezhao; Tian, Yuan; Lin, Shaoxiong; Zhang, Xiaogang

    2014-03-01

    To synthesize monodisperse palladium nanoparticles dispersed on reduced graphene oxide (RGO) sheets, we have developed an easy and scalable solvothermal reduction method from an organic solution system. The RGO-supported palladium nanoparticles with a diameter of 3.8 nm are synthesized in N-methyl-2-pyrrolidone (NMP) and in the presence of oleylamine and trioctylphosphine, which facilitates simultaneous reduction of graphene oxide and formation of Pd nanocrystals. So-produced Pd/RGO was tested for potential use as electrocatalyst for the electro-oxidation of formic acid. Pd/RGO catalyzes formic acid oxidation very well compared to Pd/Vulcan XC-72 catalyst. This synthesis method is a new way to prepare excellent electrocatalysts, which is of great significance in energy-related catalysis.

  14. One-Pot Synthesis of Graphene-Supported Monodisperse Pd Nanoparticles as Catalyst for Formic Acid Electro-oxidation

    PubMed Central

    Yang, Sudong; Dong, Jing; Yao, Zhaohui; Shen, Chengmin; Shi, Xuezhao; Tian, Yuan; Lin, Shaoxiong; Zhang, Xiaogang

    2014-01-01

    To synthesize monodisperse palladium nanoparticles dispersed on reduced graphene oxide (RGO) sheets, we have developed an easy and scalable solvothermal reduction method from an organic solution system. The RGO-supported palladium nanoparticles with a diameter of 3.8?nm are synthesized in N-methyl-2-pyrrolidone (NMP) and in the presence of oleylamine and trioctylphosphine, which facilitates simultaneous reduction of graphene oxide and formation of Pd nanocrystals. So-produced Pd/RGO was tested for potential use as electrocatalyst for the electro-oxidation of formic acid. Pd/RGO catalyzes formic acid oxidation very well compared to Pd/Vulcan XC-72 catalyst. This synthesis method is a new way to prepare excellent electrocatalysts, which is of great significance in energy-related catalysis. PMID:24675779

  15. Visible-light-driven Photocatalytic N-arylation of Imidazole Derivatives and Arylboronic Acids on Cu/graphene catalyst

    PubMed Central

    Cui, Yan-Li; Guo, Xiao-Ning; Wang, Ying-Yong; Guo, Xiang-Yun

    2015-01-01

    N-aryl imidazoles play an important role as structural and functional units in many natural products and biologically active compounds. Herein, we report a photocatalytic route for the C-N cross-coupling reactions over a Cu/graphene catalyst, which can effectively catalyze N-arylation of imidazole and phenylboronic acid, and achieve a turnover frequency of 25.4?h?1 at 25?oC and the irradiation of visible light. The enhanced catalytic activity of the Cu/graphene under the light irradiation results from the localized surface plasmon resonance of copper nanoparticles. The Cu/graphene photocatalyst has a general applicability for photocatalytic C-N, C-O and C-S cross-coupling of arylboronic acids with imidazoles, phenols and thiophenols. This study provides a green photocatalytic route for the production of N-aryl imidazoles. PMID:26189944

  16. Visible-light-driven Photocatalytic N-arylation of Imidazole Derivatives and Arylboronic Acids on Cu/graphene catalyst

    NASA Astrophysics Data System (ADS)

    Cui, Yan-Li; Guo, Xiao-Ning; Wang, Ying-Yong; Guo, Xiang-Yun

    2015-07-01

    N-aryl imidazoles play an important role as structural and functional units in many natural products and biologically active compounds. Herein, we report a photocatalytic route for the C-N cross-coupling reactions over a Cu/graphene catalyst, which can effectively catalyze N-arylation of imidazole and phenylboronic acid, and achieve a turnover frequency of 25.4?h-1 at 25?oC and the irradiation of visible light. The enhanced catalytic activity of the Cu/graphene under the light irradiation results from the localized surface plasmon resonance of copper nanoparticles. The Cu/graphene photocatalyst has a general applicability for photocatalytic C-N, C-O and C-S cross-coupling of arylboronic acids with imidazoles, phenols and thiophenols. This study provides a green photocatalytic route for the production of N-aryl imidazoles.

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

    PubMed

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

    2015-10-01

    Pt/CeO2-ZrO2-SnO2/?-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 ?-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.%)/?-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. Selective hydrogenation of lactic acid to 1,2-propanediol over highly active ruthenium-molybdenum oxide catalysts.

    PubMed

    Takeda, Yasuyuki; Shoji, Tomohiro; Watanabe, Hideo; Tamura, Masazumi; Nakagawa, Yoshinao; Okumura, Kazu; Tomishige, Keiichi

    2015-04-13

    Modification of Ru/C with a small amount of MoOx (Ru?MoOx /C) enhanced the catalytic activity in the hydrogenation of L-lactic acid to form 1,2-propanediol and maintained high selectivity. The turnover frequency based on the amount of Ru over the optimized Ru?MoOx /C catalyst (Mo/Ru molar ratio=1:16) was 114?h(-1) at 393?K, which was about 4 times higher than that over Ru/C. The same effect of MoOx was obtained over Ru?MoOx /SiO2 , although Ru?MoOx /SiO2 showed slightly lower activity than that of Ru?MoOx /C. Ru?MoOx /C achieved a high yield of 95?% in 18?h at 393?K and was applicable to various carboxylic acids to provide the corresponding alcohols in high yields. Modification with MoOx also brought about suppression of racemization and (S)-1,2-propanediol was obtained in high enantiomeric excess at 353?K. Based on kinetic analysis and characterization data, such as XRD, TEM, CO adsorption by a volumetric method, FTIR spectroscopy, and X-ray absorption spectroscopy, for Ru?MoOx /C and Ru?MoOx /SiO2 , the catalyst structure and reaction mechanism are proposed. PMID:25510671

  19. The Aerobic Oxidation of Bromide to Dibromine Catalyzed by Homogeneous Oxidation Catalysts and Initiated by Nitrate in Acetic Acid

    SciTech Connect

    Partenheimer, Walt; Fulton, John L.; Sorensen, Christina M.; Pham, Van Thai; Chen, Yongsheng

    2014-06-01

    A small amount of nitrate, ~0.002 molal, initiates the Co/Mn catalyzed aerobic oxidation of bromide compounds (HBr,NaBr,LiBr) to dibromine in acetic acid at room temperature. At temperatures 40oC or less , the reaction is autocatalytic. Co(II) and Mn(II) themselves and mixed with ionic bromide are known homogeneous oxidation catalysts. The reaction was discovered serendipitously when a Co/Br and Co/Mn/Br catalyst solution was prepared for the aerobic oxidation of methyaromatic compounds and the Co acetate contained a small amount of impurity i.e. nitrate. The reaction was characterized by IR, UV-VIS, MALDI and EXAFS spectroscopies and the coordination chemistry is described. The reaction is inhibited by water and its rate changed by pH. The change in these variables, as well as others, are identical to those observed during homogeneous, aerobic oxidation of akylaromatics. A mechanism is proposed. Accidental addition of a small amount of nitrate compound into a Co/Mn/Br/acetic acid mixture in a large, commercial feedtank is potentially dangerous.

  20. Biodiesel production by free fatty acid esterification using Lanthanum (La3+) and HZSM-5 based catalysts.

    PubMed

    Vieira, Sara S; Magriotis, Zuy M; Santos, Nadiene A V; Saczk, Adelir A; Hori, Carla E; Arroyo, Pedro A

    2013-04-01

    In this work the use of the heterogeneous catalysts pure (LO) and sulfated (SLO) lanthanum oxide, pure HZSM-5 and SLO/HZSM-5 (HZSM-5 impregnated with sulfated lanthanum oxide (SO4(2-)/La2O3)) was evaluated. The structural characterization of the materials (BET) showed that the sulfation process led to a reduction of the SLO and SLO/HZSM-5 surface area values. FTIR showed bands characteristic of the materials and, FTIR-pyridine indicated the presence of strong Brønsted sites on the sulfated material. In the catalytic tests the temperature was the parameter that most influenced the reactions. The best reaction conditions were: 10% catalyst, 100°C temperature and 1:5 m(OA)/m(meOH) for LO, SLO, SLO/HZSM-5 and 10% catalyst, 100°C temperature and 1:20 m(OA)/m(meOH) for HZSM-5. Under these conditions the conversions were: 67% and 96%, for LO and SLO, respectively and 80% and 100%, for HZSM-5 and SLO/HZSM-5, respectively. All catalysts deactivated after the first use, but the deactivation of SLO/HZSM-5 was smaller. PMID:23428822

  1. Biomass acid-catalyzed liquefaction - Catalysts performance and polyhydric alcohol influence.

    PubMed

    Mateus, Maria Margarida; Carvalho, Ricardo; Bordado, João Carlos; Santos, Rui Galhano Dos

    2015-12-01

    Herein, the data acquired regarding the preliminary experiments conducted with different catalyst, as well as with two polyhydric alcohols (glycerol and 2-ethylhexanol), for the preparation biooils from cork liquefaction at 160 °C, is disclosed. This data may be helpful for those who intent to outline a liquefaction procedure avoiding, thus, high number of experiments. PMID:26693504

  2. Biomass acid-catalyzed liquefaction – Catalysts performance and polyhydric alcohol influence

    PubMed Central

    Mateus, Maria Margarida; Carvalho, Ricardo; Bordado, João Carlos; Santos, Rui Galhano dos

    2015-01-01

    Herein, the data acquired regarding the preliminary experiments conducted with different catalyst, as well as with two polyhydric alcohols (glycerol and 2-ethylhexanol), for the preparation biooils from cork liquefaction at 160 °C, is disclosed. This data may be helpful for those who intent to outline a liquefaction procedure avoiding, thus, high number of experiments.

  3. Nanostructured Polyphase Catalysts Based on the Solid Component of Welding Aerosol for Ozone Decomposition.

    PubMed

    Rakitskaya, Tatyana; Truba, Alla; Ennan, Alim; Volkova, Vitaliya

    2015-12-01

    Samples of the solid component of welding aerosols (SCWAs) were obtained as a result of steel welding by ANO-4, TsL?11, and UONI13/55 electrodes of Ukrainian manufacture. The phase compositions of the samples, both freshly prepared (FP) and modified (M) by water treatment at 60 °C, were studied by X-ray phase analysis and IR spectroscopy. All samples contain magnetite demonstrating its reflex at 2??~?35° characteristic of cubic spinel as well as manganochromite and iron oxides. FP SCWA-TsL and FP SCWA-UONI contain such phases as ?aF2, water-soluble fluorides, chromates, and carbonates of alkali metals. After modification of the SCWA samples, water-soluble phases in their composition are undetectable. The size of magnetite nanoparticles varies from 15 to 68 nm depending on the chemical composition of electrodes under study. IR spectral investigations confirm the polyphase composition of the SCWAs. As to IR spectra, the biggest differences are apparent in the regions of deformation vibrations of M-O-H bonds and stretching vibrations of M-O bonds (M-Fe, Cr). The catalytic activity of the SCWAs in the reaction of ozone decomposition decreases in the order SCWA-ANO?>?SCWA-UONI?>?SCWA-TsL corresponding to the decrease in the content of catalytically active phases in their compositions. PMID:26646686

  4. Recovery of nickel from spent NiO/Al2O3 catalyst through sulfuric acid leaching, precipitation and solvent extraction.

    PubMed

    Nazemi, M K; Rashchi, F

    2012-05-01

    Effective recovery of nickel (Ni) from spent NiO/Al(2)O(3) catalyst in a simple hydrometallurgical route is suggested. Nickel recovery of 99.5% was achieved with sulfuric acid leaching. The leach liquor was partly neutralized and nickel ammonium sulfate was precipitated by adding ammonia. The nickel in the supernatant was concentrated by solvent extraction using D2EHPA and subsequently stripped back into sulfuric acid and returned to the precipitation stage. Necessary counter current extraction and stripping stages were determined in McCabe-Thiele diagrams. The suggested method appears simple and very effective in recovering nickel from spent catalysts from the petrochemical industry. PMID:21930525

  5. Synthetic Method for 2,2'-Disubstituted Fluorinated Binaphthyl Derivatives and Application as Chiral Source in Design of Chiral Mono-Phosphoric Acid Catalyst.

    PubMed

    Momiyama, Norie; Okamoto, Hiroshi; Shimizu, Masahiro; Terada, Masahiro

    2015-08-01

    A practical synthetic method for 2,2'-disubstituted fluorinated binaphthyl derivatives was achieved using magnesium bis(2,2,6,6-tetramethylpiperamide) [Mg(TMP)(2)], prepared from LiTMP (2 equiv) and MgBr(2) (1 equiv), which allows for access to a variety of fluorinated binaphthyl compounds. The utility of the fluorinated binaphthyl backbone was evaluated in F10 BINOL derived chiral mono-phosphoric acid (R)- as the chiral Brønsted acid catalyst. The catalyst (R)- performs exceptionally well in the catalytic enantioselective imino-ene reaction, demonstrating the potential of a fluorinated binaphthyl framework. PMID:25665035

  6. Bimetallic catalysts for CO.sub.2 hydrogenation and H.sub.2 generation from formic acid and/or salts thereof

    DOEpatents

    Hull, Jonathan F.; Himeda, Yuichiro; Fujita, Etsuko; Muckeman, James T.

    2015-08-04

    The invention relates to a ligand that may be used to create a catalyst including a coordination complex is formed by the addition of two metals; Cp, Cp* or an unsubstituted or substituted .pi.-arene; and two coordinating solvent species or solvent molecules. The bimetallic catalyst may be used in the hydrogenation of CO.sub.2 to form formic acid and/or salts thereof, and in the dehydrogenation of formic acid and/or salts thereof to form H.sub.2 and CO.sub.2.

  7. Two-Stage Conversion of High Free Fatty Acid Jatropha curcas Oil to Biodiesel Using Brønsted Acidic Ionic Liquid and KOH as Catalysts

    PubMed Central

    Das, Subrata; Thakur, Ashim Jyoti; Deka, Dhanapati

    2014-01-01

    Biodiesel was produced from high free fatty acid (FFA) Jatropha curcas oil (JCO) by two-stage process in which esterification was performed by Brønsted acidic ionic liquid 1-(1-butylsulfonic)-3-methylimidazolium chloride ([BSMIM]Cl) followed by KOH catalyzed transesterification. Maximum FFA conversion of 93.9% was achieved and it reduced from 8.15?wt% to 0.49?wt% under the optimum reaction conditions of methanol oil molar ratio 12?:?1 and 10?wt% of ionic liquid catalyst at 70°C in 6?h. The ionic liquid catalyst was reusable up to four times of consecutive runs under the optimum reaction conditions. At the second stage, the esterified JCO was transesterified by using 1.3?wt% KOH and methanol oil molar ratio of 6?:?1 in 20?min at 64°C. The yield of the final biodiesel was found to be 98.6% as analyzed by NMR spectroscopy. Chemical composition of the final biodiesel was also determined by GC-MS analysis. PMID:24987726

  8. Heterogeneous base catalysts for edible palm and non-edible Jatropha-based biodiesel production

    PubMed Central

    2014-01-01

    Background Transesterification catalyzed by solid base catalyst is a brilliant technology for the noble process featuring the fast reaction under mild reacting condition in biodiesel production. Heterogeneous base catalysts are generally more reactive than solid acid catalysts which require extreme operating condition for high conversion and biodiesel yield. In the present study, synthesis of biodiesel was studied by using edible (palm) or non-edible (Jatropha) feedstock catalyzed by heterogeneous base catalysts such as supported alkali metal (NaOH/Al2O3), alkaline-earth metal oxide (MgO, CaO and SrO) and mixed metal oxides catalysts (CaMgO and CaZnO). Results The chemical characteristic, textural properties, basicity profile and leaching test of synthesized catalysts were studied by using X-ray diffraction, BET measurement, TPD-CO2 and ICP-AES analysis, respectively. Transesterification activity of solid base catalysts showed that?>?90% of palm biodiesel and?>?80% of Jatropha biodiesel yield under 3 wt.% of catalyst, 3 h reaction time, methanol to oil ratio of 15:1 under 65°C. This indicated that other than physicochemical characteristic of catalysts; different types of natural oil greatly influence the catalytic reaction due to the presence of free fatty acids (FFAs). Conclusions Among the solid base catalysts, calcium based mixed metal oxides catalysts with binary metal system (CaMgO and CaZnO) showed capability to maintain the transesterification activity for 3 continuous runs at?~?80% yield. These catalysts render high durability characteristic in transesterification with low active metal leaching for several cycles. PMID:24812574

  9. Non-covalent interactions in water electrolysis: influence on the activity of Pt(111) and iridium oxide catalysts in acidic media.

    PubMed

    Ganassin, Alberto; Colic, Viktor; Tymoczko, Jakub; Bandarenka, Aliaksandr S; Schuhmann, Wolfgang

    2015-04-01

    Electrolyte components, which are typically not considered to be directly involved in catalytic processes at solid-liquid electrified interfaces, often demonstrate a significant or even drastic influence on the activity, stability and selectivity of electrocatalysts. While there has been certain progress in the understanding of these electrolyte effects, lack of experimental data for various important systems frequently complicates the rational design of new active materials. Modern proton-exchange membrane (PEM) electrolyzers utilize Pt- and Ir-based electrocatalysts, which are among the very few materials that are both active and stable under the extreme conditions of water splitting. We use model Pt(111) and Ir-oxide films grown on Ir(111) electrodes and explore the effect of alkali metal cations and sulfate-anions on the hydrogen evolution and the oxygen evolution reactions in acidic media. We demonstrate that sulfate anions decrease the activity of Ir-oxide towards the oxygen evolution reaction while Rb(+) drastically promotes hydrogen evolution reaction at the Pt(111) electrodes as compared to the reference HClO4 electrolytes. Issues related to the activity benchmarking for these catalysts are discussed. PMID:25412811

  10. German Edition: DOI: 10.1002/ange.201412470Bifunctional Catalysts International Edition: DOI: 10.1002/anie.201412470

    E-print Network

    Toste, Dean

    in the separation of mutually incompat- ible groups, such as acids and bases. Among the various heterogeneous efficient water-tolerant, solid-base catalyst for the self-condensation of biomass-derived methyl ketones of the acidic and basic sites, the acidity of the support material plays a critical role in defining

  11. Catalyst development gets federal funding

    SciTech Connect

    Rotman, D.

    1995-09-20

    Despite the threat of Republican-led budget cuts, the National Institute of Standards and Technology`s (Gaithersburg, MD) Advanced Technology Program (ATP) has awarded backing to a handful of US chemical companies to conduct long-term projects to develop novel catalysts. The projects--which read like a wish list of next generation catalyst technology--includes $16 million to Eastman Chemical and Genencor International (Rochester, NY), Eastman`s joint venture with Cultor (Helsinki), to develop biocatalysts to make industrial chemicals from renewable resources. Eastman hopes the project will allow it to commercialize fine and specialty chemical products based on biocatalysts in three to five years and eventually pay off in new processes to make commodity chemicals. ATP also plans to provide $10 million to Amoco for further work on metallocene catalysts to make elastomeric homopolymer polypropylene (EHPP). The research, which also involves Stanford University and Fiberweb North America, aims to further develop EHPP to compete with a range of flexible polyolefins. Other ATP-funded projects include long-time industry goals such as the direct oxidation of propylene to propylene oxide, a solid-acid catalyst for alkylation, and a single-step oxidation of alkanes to acrylic acid. The ATP funding, however, is endangered by proposed Congressional budget cuts that would reduce ATP spending this year and eliminate the program thereafter.

  12. Inoculation onto Solid Surfaces Protects Salmonella spp. during Acid Challenge: a Model Study Using Polyethersulfone Membranes

    PubMed Central

    Gawande, Purushottam V.; Bhagwat, Arvind A.

    2002-01-01

    Salmonellae are the most frequently reported cause of outbreaks of food-borne gastroenteritis in the United States. In clinical trials, the oral infective dose (ID) for healthy volunteers was estimated to be approximately 1 million cells. However, in reports from various outbreaks, the ID of Salmonella species associated with solid foods was estimated to be as few as 100 cells. We found that fresh-cut produce surfaces not only provided suitable solid support for pathogen attachment but also played a critical role in increasing the acid tolerance of the pathogen. However the acidic nature of certain produce played no role in making salmonellae resistant to stomach acidity. Inoculation onto fresh-cut produce surfaces, as well as onto inert surfaces, such as polyethersulfone membranes and tissue paper, increased the survival of salmonellae during acid challenge (50 mM Na-citrate, pH 3.0; 37°C; 2 h) by 4 to 5 log units. Acid challenge experiments using cells inoculated onto polyethersulfone membranes provided a model system suitable for studying the underlying fundamentals of the protection that occurs when Salmonella strains are associated with solid foods. The surface-associated acid protection, which was observed in several Salmonella strains, required de novo protein synthesis and was independent of stationary-phase sigma transcription factor. PMID:11772613

  13. Inoculation onto solid surfaces protects Salmonella spp. during acid challenge: a model study using polyethersulfone membranes.

    PubMed

    Gawande, Purushottam V; Bhagwat, Arvind A

    2002-01-01

    Salmonellae are the most frequently reported cause of outbreaks of food-borne gastroenteritis in the United States. In clinical trials, the oral infective dose (ID) for healthy volunteers was estimated to be approximately 1 million cells. However, in reports from various outbreaks, the ID of Salmonella species associated with solid foods was estimated to be as few as 100 cells. We found that fresh-cut produce surfaces not only provided suitable solid support for pathogen attachment but also played a critical role in increasing the acid tolerance of the pathogen. However the acidic nature of certain produce played no role in making salmonellae resistant to stomach acidity. Inoculation onto fresh-cut produce surfaces, as well as onto inert surfaces, such as polyethersulfone membranes and tissue paper, increased the survival of salmonellae during acid challenge (50 mM Na-citrate, pH 3.0; 37 degrees C; 2 h) by 4 to 5 log units. Acid challenge experiments using cells inoculated onto polyethersulfone membranes provided a model system suitable for studying the underlying fundamentals of the protection that occurs when Salmonella strains are associated with solid foods. The surface-associated acid protection, which was observed in several Salmonella strains, required de novo protein synthesis and was independent of stationary-phase sigma transcription factor. PMID:11772613

  14. Waste shells of mollusk and egg as biodiesel production catalysts.

    PubMed

    Viriya-Empikul, N; Krasae, P; Puttasawat, B; Yoosuk, B; Chollacoop, N; Faungnawakij, K

    2010-05-01

    The solid oxide catalysts derived from waste shells of egg, golden apple snail, and meretrix venus were employed to produce biodiesel from transesterification of palm olein oil. The shell materials were calcined in air at 800 degrees C with optimum time of 2-4h to transform calcium species in the shells into active CaO catalysts. All catalysts showed the high biodiesel production activity over 90% fatty acid methyl ester (FAME) in 2h, whilst the eggshell-derived catalyst showed comparable activity to the one derived from commercial CaCO(3). The catalytic activity was in accordance with the surface area of and the Ca content in the catalysts. PMID:20079632

  15. ADSORPTION/DESORPTION STUDIES ON SOLID ACID ALKYLATION CATALYSTS USING A TAPERED ELEMENT OSCILLATING MICROBALANCE (TEOM)

    E-print Network

    Gong, Kening

    2008-10-23

    measurement. The advantages of the TEOM technique have been demonstrated in the investigations of coking kinetics [Chen, 1996; Liu, 1997; Chen, 1999], influence of coke deposition on selectivity [Chen, 1997], combined diffusion, adsorption, reaction... and coking [Hershkowitz, 1993; Chen, 1999; van Donk, 2001], adsorption capacity [Zhu, 1998], and adsorption and desorption kinetics [Barrie, 2004; Lee, 2004]. This dissertation research employs the TEOM to elucidate for the first time the adsorption...

  16. Solid-State 17O NMR Study of Benzoic Acid Adsorption On Metal Oxide Surfaces

    SciTech Connect

    Hagaman, Edward {Ed} W; Chen, Banghao; Jiao, Jian; Parsons, Williams

    2012-01-01

    Solid-state 17O NMR spectra of 17O-labeled benzoic and anisic acids are reported and benzoic acid is used to probe the surface of metal oxides. Complexes formed when benzoic acid is dry-mixed with mesoporous silica, and nonporous titania and alumina are characterized. Chemical reactions with silica are not observed. The nature of benzoic acid on silica is a function of the water content of the oxide. The acid disperses in the pores of the silica if the silica is in equilibrium with ambient laboratory humidity. The acid displays high mobility as evidenced by a liquid-like, Lorentzian resonance. Excess benzoic acid remains as the crystalline hydrogen-bonded dimer. Benzoic acid reacts with titania and alumina surfaces in equilibrium with laboratory air to form the corresponding titanium and aluminum benzoates. In both materials the oxygen of the 17O-labeled acid is bound to the metal, showing the reaction proceeds by bond formation between oxygen deficient metal sites and the oxygen of the carboxylic acid. 27Al MAS NMR confirms this mechanism for the reaction on alumina. Dry mixing of benzoic acid with alumina rapidly quenches pentacoordinate aluminum sites, excellent evidence that these sites are confined to the surface of the alumina particles.

  17. New solid acids in the triple-layer Dion-Jacobson layered perovskite family

    SciTech Connect

    Geselbracht, Margret J.; White, Helen K.; Blaine, Jeanette M.; Diaz, Miranda J.; Hubbs, Jennifer L.; Adelstein, Nicole; Kurzman, Joshua A.

    2011-03-15

    Research highlights: {yields} New triple-layer Dion-Jacobson layered perovskite solid solutions synthesized. {yields} New series of Ta-doped layered perovskite solid acids, HCa{sub 2}Nb{sub 3-x}Ta{sub x}O{sub 10}. {yields} New series of Sr-doped layered perovskite solid acids, HCa{sub 2-x}Sr{sub x}Nb{sub 3}O{sub 10}. {yields} Layered perovskites with highest Ta content are weaker solid acids than HCa{sub 2}Nb{sub 3}O{sub 10}. -- Abstract: Dion-Jacobson type layered perovskites such as A'Ca{sub 2}Nb{sub 3}O{sub 10} (A' = K, Rb, H) have continued to be of great interest due to their compositional variability, rich interlayer chemistry, and wide range of physical properties. In this study, we investigated the range and effects of substitutional doping of Ta{sup 5+} for Nb{sup 5+} and of Sr{sup 2+} for Ca{sup 2+} in A'Ca{sub 2}Nb{sub 3}O{sub 10}. We have prepared and characterized three new solid solutions: KCa{sub 2}Nb{sub 3-x}Ta{sub x}O{sub 10}, RbCa{sub 2}Nb{sub 3-x}Ta{sub x}O{sub 10}, and RbCa{sub 2-x}Sr{sub x}Nb{sub 3}O{sub 10}. These materials all readily undergo proton exchange to form two new series of hydrated solid acid phases, which in most cases can be dehydrated to form stable HCa{sub 2}Nb{sub 3-x}Ta{sub x}O{sub 10} and HCa{sub 2-x}Sr{sub x}Nb{sub 3}O{sub 10} compounds. Intercalation studies with n-hexylamine and pyridine were carried out to gauge the relative Bronsted acidities across the HCa{sub 2}Nb{sub 3-x}Ta{sub x}O{sub 10} series, and we determined that materials with the highest tantalum contents are weaker acids than the parent compound HCa{sub 2}Nb{sub 3}O{sub 10}. Preliminary intercalation studies with pyridine for the HCa{sub 2-x}Sr{sub x}Nb{sub 3}O{sub 10}.yH{sub 2}O solid acids, however, showed no significant difference in acidity with varying strontium content.

  18. Tandem decarboxylative hydroformylation-hydrogenation reaction of ?,?-unsaturated carboxylic acids toward aliphatic alcohols under mild conditions employing a supramolecular catalyst system.

    PubMed

    Diab, Lisa; Gellrich, Urs; Breit, Bernhard

    2013-10-28

    A new atom economic catalytic method for a highly chemoselective reduction of ?,?-unsaturated carboxylic acids to the corresponding saturated alcohols under mild reaction conditions, compatible with a wide range reactive functional groups, is reported. The new methodology consists of a novel tandem decarboxylative hydroformylation/aldehyde reduction sequence employing a unique supramolecular catalyst system. PMID:24022335

  19. An azobenzene-containing metal-organic framework as an efficient heterogeneous catalyst for direct amidation of benzoic acids: synthesis of bioactive compounds.

    PubMed

    Hoang, Linh T M; Ngo, Long H; Nguyen, Ha L; Nguyen, Hanh T H; Nguyen, Chung K; Nguyen, Binh T; Ton, Quang T; Nguyen, Hong K D; Cordova, Kyle E; Truong, Thanh

    2015-11-19

    An azobenzene-containing zirconium metal-organic framework was demonstrated to be an effective heterogeneous catalyst for the direct amidation of benzoic acids in tetrahydrofuran at 70 °C. This finding was applied to the synthesis of several important, representative bioactive compounds. PMID:26455380

  20. Continuous-flow hydrogenation of carbon dioxide to pure formic acid using an integrated scCO2 process with immobilized catalyst and base.

    PubMed

    Wesselbaum, Sebastian; Hintermair, Ulrich; Leitner, Walter

    2012-08-20

    Dual role for CO(2): Pure formic acid can be obtained continuously by hydrogenation of CO(2) in a single processing unit. An immobilized ruthenium organometallic catalyst and a nonvolatile base in an ionic liquid (IL) are combined with supercritical CO(2) as both reactant and extractive phase. PMID:22807319

  1. Relationship of soluble solids, acidity and aroma volatiles to flavor in late-season navel oranges

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Navel orange flavor development during early fruit maturation is strongly dependent on changes in soluble solids concentration (SSC) and titratable acidity (TA), while later in the season other factors, such as aroma volatiles, also become important. The flavor of individual oranges can differ gre...

  2. Stable and catalytically active iron porphyrin-based porous organic polymer: Activity as both a redox and Lewis acid catalyst

    PubMed Central

    Oveisi, Ali R.; Zhang, Kainan; Khorramabadi-zad, Ahmad; Farha, Omar K.; Hupp, Joseph T.

    2015-01-01

    A new porphyrin-based porous organic polymer (POP) with BET surface area ranging from 780 to 880?m2/g was synthesized in free-base form via the reaction of meso-tetrakis(pentafluorophenyl) porphyrin and a rigid trigonal building block, hexahydroxytriphenylene. The material was then metallated with Fe(III) imparting activity for Lewis acid catalysis (regioselective methanolysis ring-opening of styrene oxide), oxidative cyclization catalysis (conversion of bis(2-hydroxy-1-naphthyl)methanes to the corresponding spirodienone), and a tandem catalytic processes: an in situ oxidation-cyclic aminal formation-oxidation sequence, which selectively converts benzyl alcohol to 2-phenyl-quinazolin-4(3H)-one. Notably, the catalyst is readily recoverable and reusable, with little loss in catalytic activity. PMID:26177563

  3. Stable and catalytically active iron porphyrin-based porous organic polymer: Activity as both a redox and Lewis acid catalyst.

    PubMed

    Oveisi, Ali R; Zhang, Kainan; Khorramabadi-zad, Ahmad; Farha, Omar K; Hupp, Joseph T

    2015-01-01

    A new porphyrin-based porous organic polymer (POP) with BET surface area ranging from 780 to 880?m(2)/g was synthesized in free-base form via the reaction of meso-tetrakis(pentafluorophenyl) porphyrin and a rigid trigonal building block, hexahydroxytriphenylene. The material was then metallated with Fe(III) imparting activity for Lewis acid catalysis (regioselective methanolysis ring-opening of styrene oxide), oxidative cyclization catalysis (conversion of bis(2-hydroxy-1-naphthyl)methanes to the corresponding spirodienone), and a tandem catalytic processes: an in situ oxidation-cyclic aminal formation-oxidation sequence, which selectively converts benzyl alcohol to 2-phenyl-quinazolin-4(3H)-one. Notably, the catalyst is readily recoverable and reusable, with little loss in catalytic activity. PMID:26177563

  4. A kinetic study of plutonium dioxide dissolution in hydrochloric acid using iron (II) as an electron transfer catalyst

    SciTech Connect

    Fife, K.W.

    1996-09-01

    Effective dissolution of plutonium dioxide has traditionally been accomplished by contact with strong nitric acid containing a small amount of fluoride at temperatures of {approximately} 100 C. In spite of these aggressive conditions, PuO{sub 2} dissolution is sometimes incomplete requiring additional contact with the solvent. This work focused on an alternative to conventional dissolution in nitric acid where an electron transfer catalyst, Fe(II), was used in hydrochloric acid. Cyclic voltammetry was employed as an in-situ analytical technique for monitoring the dissolution reaction rate. The plutonium oxide selected for this study was decomposed plutonium oxalate with > 95% of the material having a particle diameter (< 70 {micro}m) as determined by a scanning laser microscopy technique. Attempts to dry sieve the oxide into narrow size fractions prior to dissolution in the HCl-Fe(II) solvent system failed, apparently due to significant interparticle attractive forces. Although sieve splits were obtained, subsequent scanning laser microscopy analysis of the sieve fractions indicated that particle segregation was not accomplished and the individual sieve fractions retained a particle size distribution very similar to the original powder assemblage. This phenomena was confirmed through subsequent dissolution experiments on the various screen fractions which illustrated no difference in kinetic behavior between the original oxide assemblage and the sieve fractions.

  5. Bioconversion of MSW (municipal solid waste) and recovery of organic acids

    SciTech Connect

    Antonopoulos, A.A.; Wene, E.G.

    1987-01-01

    Research was conducted to determine the feasibility of bioprocessing municipal solid waste (MSW) to produce organic acids and recover the acids for hydrocarbon fuels production. This work focused on acid production from anaerobic digestion of a simulated MSW material, and densified refuse-derived-fuel MSW substrate, using 5-L continuously stirred and 12-L packed bed anaerobic digesters. Methane generation was inhibited by heat treatment, addition of a methanogen inhibitory compound, low pH, inoculum from a long-term acid adapted culture, and short retention times. Steady state operation was reached with acid concentrations of 15,000 to 18,000 mg/L. Nitrogen supplementations to the feedstock increased volatile acid concentrations to between 27,000 to 30,000 mg/L. Aerobic sewage sludge additions to feedstock increased peak levels of acid production to 22,000 mg/L. Acid extraction with trioctylphosphine oxide (TOPO) in heptane extracted more than 82% of the acid content in a single extraction of digester fluids with 15,000 mg/L total acids. 9 refs., 3 figs., 1 tab.

  6. Non-platinum group metal oxgyen reduction catalysts and their mechanism in both acid and alkaline media: The effect of the catalyst precursor and the ionomer on oxygen reduction

    NASA Astrophysics Data System (ADS)

    Robson, Michael H.

    Non-platinum catalysts are an attractive strategy for lowering the cost of fuel cells, but much more development is needed in order to replace platinum, especially at the cathode where oxygen is reduced. Research groups worldwide have donated material for a study in which precursor structure to catalyst activity correlations are made. The donated samples have been divided into three classes based on their precursor; macrocyclic chelates, small molecule, and polymeric precursors. The precursor is one activity-dictating factor among many, but it is one of the most influential. It was found that macrocyclic chelates on average produced the most active catalysts, having the highest limiting, diffusion-limited, kinetic, and exchange current densities, as well as the lowest overpotentials and H2O2 production. This suggests that the M-N4 atomic structure of the precursor remains largely static throughout heat treatment, as the M-Nx motif is the accepted active site conformation. The other classes were somewhat less active, but the breadth of precursor materials that range in structure and functionality, as well as low associated costs, make them attractive precursor materials. Careful precursor selection based on this analysis was applied to a new generation of catalyst derived from iron salt and 4-aminoantipyrine. An extensive investigation of the reduction of oxygen on the material performed in both acid and alkaline media, and it was found that reduction follows a two-step pathway. While the peroxide reducing step is also very fast, the first step is so rapid that, even at low active site density, the material is almost as active as platinum if all diffusion limitations are removed. In addition to bottom-up catalyst design, the catalyst:ionomer complex, by which catalyst is incorporated into the membrane electrode assembly, also affects reductive kinetics. A series of novel anionically conductive ionomers have been evaluated using a well-described cyanamide derived catalyst, and the ionomeric influence on activity was mechanistically evaluated. It was found that the water-uptake percentage of the ionomer and the ion exchange capacity has a major role in catalyzing the reaction. The ionomer content of the complex must balance ionic and electrical charge transfer, as well as manage a certain degree of hydration at the active site. In order for a catalyst to perform optimally in an operational fuel cell, design considerations must be addressed at the precursor, support, synthesis, morphological, and ionomer-complexing levels. If any level of design is neglected, catalytic performance will be sacrificed.

  7. Effect of Periodic Water Addition on Citric Acid Production in Solid State Fermentation

    NASA Astrophysics Data System (ADS)

    Utpat, Shraddha S.; Kinnige, Pallavi T.; Dhamole, Pradip B.

    2013-09-01

    Water addition is one of the methods used to control the moisture loss in solid state fermentation (SSF). However, none of the studies report the timing of water addition and amount of water to be added in SSF. Therefore, this work was undertaken with an objective to evaluate the performance of periodic water addition on citric acid production in SSF. Experiments were conducted at different moistures (50-80 %) and temperatures (30-40 °C) to simulate the conditions in a fermenter. Citric acid production by Aspergillus niger (ATCC 9029) using sugarcane baggase was chosen as a model system. Based on the moisture profile, citric acid and sugar data, a strategy was designed for periodic addition of water. Water addition at 48, 96, 144 and 192 h enhanced the citric acid production by 62 % whereas water addition at 72, 120, and 168 h increased the citric acid production by just 17 %.

  8. Solid supported in situ derivatization extraction of acidic degradation products of nerve agents from aqueous samples.

    PubMed

    Chinthakindi, Sridhar; Purohit, Ajay; Singh, Varoon; Tak, Vijay; Dubey, D K; Pardasani, Deepak

    2014-09-12

    This study deals with the solid supported in situ derivatization extraction of acidic degradation products of nerve agents present in aqueous samples. Target analytes were alkyl alkylphosphonic acids and alkylphosphonic acids, which are important environmental signatures of nerve agents. The method involved tert-butyldimethylchlorosilane mediated in situ silylation of analytes on commercially available diatomaceous solid phase extraction cartridges. Various parameters such as derivatizing reagent, its concentration, reaction time, temperature and eluting solvent were optimized. Recoveries of the analytes were determined by GC-MS which ranged from 60% to 86%. The limits of detection (LOD) and limit of quantification (LOQ) with selected analytes were achieved down to 78 and 213ngmL(-1) respectively, in selected ion monitoring mode. The successful applicability of method was also demonstrated on samples of biological origin such as plasma and to the samples received in 34th official proficiency test conducted by the Organization for Prohibition the of Chemical Weapons. PMID:25103280

  9. System for reactivating catalysts

    DOEpatents

    Ginosar, Daniel M. (Idaho Falls, ID); Thompson, David N. (Idaho Falls, ID); Anderson, Raymond P. (Idaho Falls, ID)

    2010-03-02

    A method of reactivating a catalyst, such as a solid catalyst or a liquid catalyst is provided. The method comprises providing a catalyst that is at least partially deactivated by fouling agents. The catalyst is contacted with a fluid reactivating agent that is at or above a critical point of the fluid reactivating agent and is of sufficient density to dissolve impurities. The fluid reactivating agent reacts with at least one fouling agent, releasing the at least one fouling agent from the catalyst. The at least one fouling agent becomes dissolved in the fluid reactivating agent and is subsequently separated or removed from the fluid reactivating agent so that the fluid reactivating agent may be reused. A system for reactivating a catalyst is also disclosed.

  10. Design of an effective bifunctional catalyst organotriphosphonic acid-functionalized ferric alginate (ATMP-FA) and optimization by Box-Behnken model for biodiesel esterification synthesis of oleic acid over ATMP-FA.

    PubMed

    Liu, Wei; Yin, Ping; Liu, Xiguang; Qu, Rongjun

    2014-12-01

    Biodiesel production has become an intense research area because of rapidly depleting energy reserves and increasing petroleum prices together with environmental concerns. This paper focused on the optimization of the catalytic performance in the esterification reaction of oleic acid for biodiesel production over the bifunctional catalyst organotriphosphonic acid-functionalized ferric alginate ATMP-FA. The reaction parameters including catalyst amount, ethanol to oleic acid molar ratio and reaction temperature have been optimized by response surface methodology (RSM) using the Box-Behnken model. It was found that the reaction temperature was the most significant factor, and the best conversion ratio of oleic acid could reach 93.17% under the reaction conditions with 9.53% of catalyst amount and 8.62:1 of ethanol to oleic acid molar ratio at 91.0 °C. The research results show that two catalytic species could work cooperatively to promote the esterification reaction, and the bifunctional ATMP-FA is a potential catalyst for biodiesel production. PMID:25310862

  11. A simple, efficient and environmentally benign synthetic protocol for the synthesis of spirooxindoles using choline chloride-oxalic acid eutectic mixture as catalyst/solvent system.

    PubMed

    Khandelwal, Sarita; Rajawat, Anshu; Tailor, Yogesh Kumar; Kumar, Mahendra

    2014-01-01

    An efficient and environmentally benign domino protocol has been presented for the synthesis of structurally diverse spirooxindoles spiroannulated with pyranopyridopyrimidines, indenopyridopyrimidines, and chromenopyridopyrimidines involving three-component reaction of aminouracils, isatins and cyclic carbonyl compounds in deep eutectic solvent (choline chloride-oxalic acid: 1:1) which acts as efficient catalyst and environmentally benign reaction medium. The present protocol offers several advantages such as operational simplicity with easy workup, shorter reaction times excellent yields with superior atom economy and environmentally benign reaction conditions with the use of cost-effective, recyclable, non-toxic and bio-degradable DES as catalyst/solvent. PMID:25329839

  12. Silver(I) as a widely applicable, homogeneous catalyst for aerobic oxidation of aldehydes toward carboxylic acids in water—“silver mirror”: From stoichiometric to catalytic

    PubMed Central

    Liu, Mingxin; Wang, Haining; Zeng, Huiying; Li, Chao-Jun

    2015-01-01

    The first example of a homogeneous silver(I)-catalyzed aerobic oxidation of aldehydes in water is reported. More than 50 examples of different aliphatic and aromatic aldehydes, including natural products, were tested, and all of them successfully underwent aerobic oxidation to give the corresponding carboxylic acids in extremely high yields. The reaction conditions are very mild and greener, requiring only a very low silver(I) catalyst loading, using atmospheric oxygen as the oxidant and water as the solvent, and allowing gram-scale oxidation with only 2 mg of our catalyst. Chromatography is completely unnecessary for purification in most cases. PMID:26601150

  13. Two solid forms of tauroursodeoxycholic acid and the effects of milling and storage temperature on solid-state transformations.

    PubMed

    Xu, Kailin; Zheng, Shoujun; Zhai, Yuanming; Guo, Liuqi; Tang, Peixiao; Yan, Jin; Wu, Di; Li, Hui

    2015-05-30

    Two phase-pure solid forms of tauroursodeoxycholic acid (TUDCA) were prepared and characterized by thermal analysis, vibrational spectroscopy, X-ray diffraction, solid-state nuclear magnetic resonance, and morphological analysis. All solid forms can be produced from solvents and also can be obtained by mechanically and non-mechanically activated polymorph conversion. Near-infrared (NIR) spectroscopy, in combination with chemometrical techniques, was used for the quantitative monitoring of the polymorph conversion of TUDCA in milling process and at different storage temperatures. The NIR spectra in the range of 7139-5488 cm(-1) were considered for multivariate analysis. Results demonstrated that the NIR multivariate chemometric model can predict the percentage of crystal and amorphous TUDCA with the correlation coefficient of 0.9998, root mean square error of calibration of 0.740%, root mean square error of prediction of 0.698%, and root mean square error of cross-validation of 1.49%. In the milling process of crystal TUDCA (Form I), a direct transformation from crystal to glass was observed in 4h. Moreover, the impact of different storage temperatures on the stability of amorphous TUDCA was investigated, and the rate of polymorph transformation was found to be accelerated with increasing temperature. PMID:25841565

  14. AuPt Alloy on TiO2 : A Selective and Durable Catalyst for l-Sorbose Oxidation to 2-Keto-Gulonic Acid.

    PubMed

    Chan-Thaw, Carine E; Chinchilla, Lidia E; Campisi, Sebastian; Botton, Gianluigi A; Prati, Laura; Dimitratos, Nikolaos; Villa, Alberto

    2015-12-01

    Pt nanoparticles were prepared by a sol immobilization route, deposited on supports with different acid/base properties (MgO, activated carbon, TiO2 , Al2 O3 , H-Mordenite), and tested in the selective oxidation of sorbose to 2-keto-gulonic acid (2-KGUA), an important precursor for vitamin?C. In general, as the basicity of the support increased, a higher catalytic activity occurred. However, in most cases, a strong deactivation was observed. The best selectivity to 2-KGUA was observed with acidic supports (TiO2 and H-Mordenite) that were able to minimize the formation of C1 /C2 products. We also demonstrated that, by alloying Pt to Au, it is possible to enhance significantly the selectivity of Pt-based catalysts. Moreover, the AuPt catalyst, unlike monometallic Pt, showed good stability in recycling because of the prevention of metal leaching during the reaction. PMID:26611807

  15. Surface acidity and solid-state compatibility of excipients with an acid-sensitive API: case study of atorvastatin calcium.

    PubMed

    Govindarajan, Ramprakash; Landis, Margaret; Hancock, Bruno; Gatlin, Larry A; Suryanarayanan, Raj; Shalaev, Evgenyi Y

    2015-04-01

    The objectives of this study were to measure the apparent surface acidity of common excipients and to correlate the acidity with the chemical stability of an acid-sensitive active pharmaceutical ingredient (API) in binary API-excipient powder mixtures. The acidity of 26 solid excipients was determined by two methods, (i) by measuring the pH of their suspensions or solutions and (ii) the pH equivalent (pHeq) measured via ionization of probe molecules deposited on the surface of the excipients. The chemical stability of an API, atorvastatin calcium (AC), in mixtures with the excipients was evaluated by monitoring the appearance of an acid-induced degradant, atorvastatin lactone, under accelerated storage conditions. The extent of lactone formation in AC-excipient mixtures was presented as a function of either solution/suspension pH or pHeq. No lactone formation was observed in mixtures with excipients having pHeq > 6, while the lactone levels were pronounced (> 0.6% after 6 weeks at 50°C/20% RH) with excipients exhibiting pHeq < 3. The three pHeq regions (> 6, 3-6, and < 3) were consistent with the reported solution pH-stability profile of AC. In contrast to the pHeq scale, lactone formation did not show any clear trend when plotted as a function of the suspension/solution pH. Two mechanisms to explain the discrepancy between the suspension/solution pH and the chemical stability data were discussed. Acidic excipients, which are expected to be incompatible with an acid-sensitive API, were identified based on pHeq measurements. The incompatibility prediction was confirmed in the chemical stability tests using AC as an example of an acid-sensitive API. PMID:25319055

  16. Biochemical Studies of Mycobacterial Fatty Acid Methyltransferase: A Catalyst for the Enzymatic Production of Biodiesel.

    PubMed

    Petronikolou, Nektaria; Nair, Satish K

    2015-11-19

    Transesterification of fatty acids yields the essential component of biodiesel, but current processes are cost-prohibitive and generate waste. Recent efforts make use of biocatalysts that are effective in diverting products from primary metabolism to yield fatty acid methyl esters in bacteria. These biotransformations require the fatty acid O-methyltransferase (FAMT) from Mycobacterium marinum (MmFAMT). Although this activity was first reported in the literature in 1970, the FAMTs have yet to be biochemically characterized. Here, we describe several crystal structures of MmFAMT, which highlight an unexpected structural conservation with methyltransferases that are involved in plant natural product metabolism. The determinants for ligand recognition are analyzed by kinetic analysis of structure-based active-site variants. These studies reveal how an architectural fold employed in plant natural product biosynthesis is used in bacterial fatty acid O-methylation. PMID:26526103

  17. Depositional ice nucleation on solid ammonium sulfate and glutaric acid particles

    NASA Astrophysics Data System (ADS)

    Baustian, K. J.; Wise, M. E.; Tolbert, M. A.

    2010-03-01

    Heterogeneous ice nucleation on solid ammonium sulfate and glutaric acid particles was studied using optical microscopy and Raman spectroscopy. Optical microscopy was used to detect selective nucleation events as water vapor was slowly introduced into an environmental sample cell. Particles that nucleated ice were dried via sublimation and examined in detail using Raman spectroscopy. Depositional ice nucleation is highly selective and occurred preferentially on just a few ammonium sulfate and glutaric acid particles in each sample. For freezing temperatures between 214 K and 235 K an average ice saturation ratio of S = 1.10±0.07 for solid ammonium sulfate was observed. Over the same temperature range, S values observed for ice nucleation on glutaric acid particles increased from 1.2 at 235 K to 1.6 at 218 K. Experiments with externally mixed particles further show that ammonium sulfate is a more potent ice nucleus than glutaric acid. Our results suggest that heterogeneous nucleation on ammonium sulfate may be an important pathway for atmospheric ice nucleation and cirrus cloud formation when solid ammonium sulfate aerosol particles are available for ice formation. This pathway for ice formation may be particularly significant near the tropical tropopause region where sulfates are abundant and other species known to be good ice nuclei are depleted.

  18. An Additional Role for the Brønsted Acid-Base Catalysts of Mandelate Racemase in Transition State Stabilization.

    PubMed

    Nagar, Mitesh; Bearne, Stephen L

    2015-11-10

    Mandelate racemase (MR) catalyzes the interconversion of the enantiomers of mandelate and serves as a paradigm for understanding the enzyme-catalyzed abstraction of an ?-proton from a carbon acid substrate with a high pKa. The enzyme utilizes a two-base mechanism with Lys 166 and His 297 acting as Brønsted acid and base catalysts, respectively, in the R ? S reaction direction. In the S ? R reaction direction, their roles are reversed. Using isothermal titration calorimetry (ITC), MR is shown to bind the intermediate/transition state (TS) analogue inhibitor benzohydroxamate (BzH) in an entropy-driven process with a value of ?Cp equal to -358 ± 3 cal mol(-1) K(-1), consistent with an increased number of hydrophobic interactions. However, MR binds BzH with an affinity that is ?2 orders of magnitude greater than that predicted solely on the basis of hydrophobic interactions [St. Maurice, M., and Bearne, S. L. (2004) Biochemistry 43, 2524], suggesting that additional specific interactions contribute to binding. To test the hypothesis that cation-?/NH-? interactions between the side chains of Lys 166 and His 297 and the aromatic ring and/or the hydroxamate/hydroximate moiety of BzH contribute to the binding of BzH, site-directed mutagenesis was used to generate the MR variants K166M, K166C, H297N, and K166M/H297N and their binding affinity for various ligands determined using ITC. Comparison of the binding affinities of these MR variants with the intermediate/TS analogues BzH and cyclohexanecarbohydroxamate revealed that cation-?/NH-? interactions between His 297 and the hydroxamate/hydroximate moiety and the phenyl ring of BzH contribute approximately 0.26 and 0.91 kcal/mol to binding, respectively, while interactions with Lys 166 contribute approximately 1.74 and 1.74 kcal/mol, respectively. Similarly, comparison of the binding affinities of these mutants with substrate analogues revealed that Lys 166 contributes >2.93 kcal/mol to the binding of (R)-atrolactate, and His 297 contributes 2.46 kcal/mol to the binding of (S)-atrolactate. These results are consistent with Lys 166 and His 297 playing dual roles in catalysis: they act as Brønsted acid-base catalysts, and they stabilize both the enolate moiety and phenyl ring of the altered substrate in the TS. PMID:26480244

  19. Carbon fiber cloth supported Au nano-textile fabrics as an efficient catalyst for hydrogen peroxide electroreduction in acid medium

    NASA Astrophysics Data System (ADS)

    Yang, Fan; Cheng, Kui; Wang, Guiling; Cao, Dianxue

    2015-09-01

    The size-controlled hierarchical textile-like Au nanostructures supported carbon fiber cloth (Au NTs/CFC) is successfully fabricated through a simple low-cost electrochemical route. The electrodes are characterised by scanning electron microscopy equipped with an energy dispersive X-ray spectrometer, transmission electron microscopy and X-ray diffractometer. Without any conducting carbons and polymer binders, the 3D electrode with unique structure is directly used as the electrocatalyst for H2O2 reduction in acid solution and the catalytic performance is evaluated by voltammetry and chronoamperometry. The Au NTs/CFC electrode exhibits much higher catalytic activity and remarkably improved utilization of Au than Au nanoparticles (Au NPs/CFC) prepared by the same method owing to its unique structure. In the solution of 3.0 mol L-1 H2SO4 + 0.1 mol L-1 H2O2, with the reduction potential of 0 V, the current of -0.72 A cm-2 mg-1 can be obtained on Au NTs/CFC electrode and only a current of -0.09 A cm-2 mg-1 can be achieved on Au NPs/CFC electrode. All these results reveal that the novel Au NTs/CFC electrode exhibits excellent catalytic performance and superior stability for H2O2 electroreduction in acid medium, benefitting from the unique 3D structure which can ensure high utilization of catalyst.

  20. 3D-nanoarchitectured Pd/Ni catalysts prepared by atomic layer deposition for the electrooxidation of formic acid

    PubMed Central

    Assaud, Loïc; Monyoncho, Evans; Pitzschel, Kristina; Allagui, Anis; Petit, Matthieu; Hanbücken, Margrit

    2014-01-01

    Summary Three-dimensionally (3D) nanoarchitectured palladium/nickel (Pd/Ni) catalysts, which were prepared by atomic layer deposition (ALD) on high-aspect-ratio nanoporous alumina templates are investigated with regard to the electrooxidation of formic acid in an acidic medium (0.5 M H2SO4). Both deposition processes, Ni and Pd, with various mass content ratios have been continuously monitored by using a quartz crystal microbalance. The morphology of the Pd/Ni systems has been studied by electron microscopy and shows a homogeneous deposition of granularly structured Pd onto the Ni substrate. X-ray diffraction analysis performed on Ni and NiO substrates revealed an amorphous structure, while the Pd coating crystallized into a fcc lattice with a preferential orientation along the [220]-direction. Surface chemistry analysis by X-ray photoelectron spectroscopy showed both metallic and oxide contributions for the Ni and Pd deposits. Cyclic voltammetry of the Pd/Ni nanocatalysts revealed that the electrooxidation of HCOOH proceeds through the direct dehydrogenation mechanism with the formation of active intermediates. High catalytic activities are measured for low masses of Pd coatings that were generated by a low number of ALD cycles, probably because of the cluster size effect, electronic interactions between Pd and Ni, or diffusion effects. PMID:24605281

  1. One-Pot Synthesis of ?-Acetamido Ketones Using Boric Acid at Room Temperature

    PubMed Central

    Karimi-Jaberi, Zahed; Mohammadi, Korosh

    2012-01-01

    ?-acetamido ketones were synthesized in excellent yields through one-pot condensation reaction of aldehydes, acetophenones, acetyl chloride, and acetonitrile in the presence of boric acid as a solid heterogeneous catalyst at room temperature. It is the first successful report of boric acid that has been used as solid acid catalyst for the preparation of ?-acetamido ketones. The remarkable advantages offered by this method are green catalyst, mild reaction conditions, simple procedure, short reaction times, and good-to-excellent yields of products. PMID:22666168

  2. Structural and electrochemical characterization of carbon supported Pt-Pr catalysts for direct ethanol fuel cells prepared using a modified formic acid method in a CO atmosphere.

    PubMed

    Corradini, Patricia Gon; Antolini, Ermete; Perez, Joelma

    2013-07-28

    Pt-Pr/C electrocatalysts were prepared using a modified formic acid method, and their activity for carbon monoxide and ethanol oxidation was compared to Pt/C. No appreciable alloy formation was detected by XRD analysis. By TEM measurements it was found that Pt particle size increases with an increasing Pr content in the catalysts and with decreasing metal precursor addition time. XPS measurements indicated Pt segregation on the catalyst surface and the presence of Pr2O3 and PrO2 oxides. The addition of Pr increased the electro-catalytic activity of Pt for both CO and CH3CH2OH oxidation. The enhanced activity of Pt-Pr/C catalysts was ascribed to both an electronic effect, caused by the presence of Pr2O3, and the bi-functional mechanism, caused by the presence of PrO2. PMID:23752757

  3. Solid/liquid phase diagram of the ammonium sulfate/succinic acid/water system.

    PubMed

    Pearson, Christian S; Beyer, Keith D

    2015-05-14

    We have studied the low-temperature phase diagram and water activities of the ammonium sulfate/succinic acid/water system using differential scanning calorimetry and infrared spectroscopy of thin films. Using the results from our experiments, we have mapped the solid/liquid ternary phase diagram, determined the water activities based on the freezing point depression, and determined the ice/succinic acid phase boundary as well as the ternary eutectic composition and temperature. We also compared our results to the predictions of the extended AIM aerosol thermodynamics model (E-AIM) and found good agreement for the ice melting points in the ice primary phase field of this system; however, differences were found with respect to succinic acid solubility temperatures. We also compared the results of this study with those of previous studies that we have published on ammonium sulfate/dicarboxylic acid/water systems. PMID:25431860

  4. Encoding abrupt and uniform dopant profiles in vapor-liquid-solid nanowires by suppressing the reservoir effect of the liquid catalyst.

    PubMed

    Christesen, Joseph D; Pinion, Christopher W; Zhang, Xing; McBride, James R; Cahoon, James F

    2014-11-25

    Semiconductor nanowires (NWs) are often synthesized by the vapor-liquid-solid (VLS) mechanism, a process in which a liquid droplet-supplied with precursors in the vapor phase-catalyzes the growth of a solid, crystalline NW. By changing the supply of precursors, the NW composition can be altered as it grows to create axial heterostructures, which are applicable to a range of technologies. The abruptness of the heterojunction is mediated by the liquid catalyst, which can act as a reservoir of material and impose a lower limit on the junction width. Here, we demonstrate that this "reservoir effect" is not a fundamental limitation and can be suppressed by selection of specific VLS reaction conditions. For Au-catalyzed Si NWs doped with P, we evaluate dopant profiles under a variety of synthetic conditions using a combination of elemental imaging with energy-dispersive X-ray spectroscopy and dopant-dependent wet-chemical etching. We observe a diameter-dependent reservoir effect under most conditions. However, at sufficiently slow NW growth rates (?250 nm/min) and low reactor pressures (?40 Torr), the dopant profiles are diameter independent and radially uniform with abrupt, sub-10 nm axial transitions. A kinetic model of NW doping, including the microscopic processes of (1) P incorporation into the liquid catalyst, (2) P evaporation from the catalyst, and (3) P crystallization in the Si NW, quantitatively explains the results and shows that suppression of the reservoir effect can be achieved when P evaporation is much faster than P crystallization. We expect similar reaction conditions can be developed for other NW systems and will facilitate the development of NW-based technologies that require uniform and abrupt heterostructures. PMID:25363730

  5. Liquefaction with microencapsulated catalysts

    DOEpatents

    Weller, Sol W. (Williamsville, NY)

    1985-01-01

    A method of dispersing a liquefaction catalyst within coal or other carbonaceous solids involves providing a suspension in oil of microcapsules containing the catalyst. An aqueous solution of a catalytic metal salt is emulsified in the water-immiscible oil and the resulting minute droplets microencapsulated in polymeric shells by interfacial polycondensation. The catalyst is subsequently blended and dispersed throughout the powdered carbonaceous material to be liquefied. At liquefaction temperatures the polymeric microcapsules are destroyed and the catalyst converted to minute crystallites in intimate contact with the carbonaceous material.

  6. Oxidative degradation of different chlorinated phenoxyalkanoic acid herbicides by a hybrid ZrO2 gel-derived catalyst without light irradiation.

    PubMed

    Sannino, Filomena; Pernice, Pasquale; Minieri, Luciana; Camandona, Gaia Aurora; Aronne, Antonio; Pirozzi, Domenico

    2015-01-14

    The oxidative degradation of 2-methyl-4-chlorophenoxyacetic acid (MCPA), 4-(4-chloro-2-methylphenoxy)butanoic acid (MCPB), 4-chlorophenoxyacetic acid (4-CPA) and 2,4-dichlorophenoxyacetic acid (2,4 D) by ZrO2-acetylacetonate hybrid catalyst (HSGZ) without light irradiation was assessed. The thermal stability of the catalyst was investigated by thermogravimetry, differential thermal analysis, and Fourier transform infrared spectroscopy. For each herbicide, a virtually complete removal in about 3 days without light irradiation at room temperature was achieved. The removal kinetics of the herbicides has been satisfactorily characterized by a double-stage physico-mathematical model, in the hypothesis that a first-order adsorption on HSGZ surface is followed by the herbicide degradation, catalytically driven by HSGZ surface groups. The long-term use of the HSGZ catalyst was assessed by repeated-batch tests. The specific cost for unit-volume removal of herbicide was evaluated by a detailed cost analysis showing that it is comparable with those pertaining to alternative methods. PMID:25479367

  7. Synthesis and photocatalytic activity of TiO2 nanowires in the degradation of p-aminobenzoic acid: A comparative study with a commercial catalyst.

    PubMed

    Soto-Vázquez, Loraine; Cotto, María; Ducongé, José; Morant, Carmen; Márquez, Francisco

    2016-02-01

    The photocatalytic degradation of p-aminobenzoic acid was studied using TiO2 nanowires as the catalyst synthesized through a hydrothermal procedure. The as-synthesized TiO2 nanowires were fully characterized by SEM, TEM, XRD and Raman with a very high surface area of 512 m(2) g(-1). The photocatalytic degradation of p-aminobenzoic acid was carried out under 180 min of constant radiation and the results were compared with P25 as commercial catalyst. Optimal experimental conditions were determined for TiO2 nanowires with a catalyst dosage of 1.0 g L(-1) under acidic conditions with a 20 ?M p-aminobenzoic acid solution obtaining 95% of degradation. Under similar experimental conditions comparative studies were performed obtaining 98% of degradation when P25 is employed. In both systems, a pseudo first order reaction was found to provide the best correlations, with constant rates of 2.0 × 10(-2) min(-1) and 2.4 × 10(-2) min(-1) for TiO2 nanowires and P25, respectively. PMID:26610195

  8. Prototype demonstration of dual sorbent injection for acid gas control on municipal solid waste combustion units

    SciTech Connect

    1994-05-01

    This report gathered and evaluated emissions and operations data associated with furnace injection of dry hydrated lime and duct injection of dry sodium bicarbonate at a commercial, 1500 ton per day, waste-to-energy facility. The information compiled during the project sheds light on these sorbents to affect acid gas emissions from municipal solid waste combustors. The information assesses the capability of these systems to meet the 1990 Clean Air Act and 1991 EPA Emission Guidelines.

  9. Sulfuric acid as a catalyst for ring-opening of biobased bis-epoxides

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Vegetable oils can be relatively and easily transformed into bio-based epoxides. Because of this, the acid-catalyzed epoxide ring-opening has been explored for the preparation of bio-based lubricants and polymers. Detailed model studies are carried out only with mono-epoxide made from methyl oleate,...

  10. Mesoporous Silica-Supported Diarylammonium Catalysts for Esterification of Free Fatty Acids in Greases

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Biodiesel, typically fatty acid methyl esters (FAME), has received much attention because it is a renewable biofuel that contributes little to global warming compared to petroleum-based diesel fuel. The most common method used for biodiesel production is based on the alkali-catalyzed transesterific...

  11. Solid Polymer Electrolytes Based on Functionalized Tannic Acids from Natural Resources for All-Solid-State Lithium-Ion Batteries.

    PubMed

    Shim, Jimin; Bae, Ki Yoon; Kim, Hee Joong; Lee, Jin Hong; Kim, Dong-Gyun; Yoon, Woo Young; Lee, Jong-Chan

    2015-12-01

    Solid polymer electrolytes (SPEs) for all-solid-state lithium-ion batteries are prepared by simple one-pot polymerization induced by ultraviolet (UV) light using poly(ethylene glycol) methyl ether methacrylate (PEGMA) as an ion-conducting monomeric unit and tannic acid (TA)-based crosslinking agent and plasticizer. The crosslinking agent and plasticizer based on natural resources are obtained from the reaction of TA with glycidyl methacrylate and glycidyl poly(ethylene glycol), respectively. Dimensionally stable free-standing SPE having a large ionic conductivity of 5.6×10(-4) ?S?cm(-1) at room temperature can be obtained by the polymerization of PEGMA into P(PEGMA) with a very small amount (0.1?wt?%) of the crosslinking agent and 2.0?wt?% of the plasticizer. The ionic conductivity value of SPE with a crosslinked structure is one order of magnitude larger than that of linear P(PEGMA) in the waxy state. PMID:26609912

  12. Preparation and evaluation of advanced catalysts for phosphoric acid fuel cells

    NASA Technical Reports Server (NTRS)

    Stonehart, P.; Baris, J.; Hockmuth, J.; Pagliaro, P.

    1984-01-01

    The platinum electrocatalysts were characterized for their crystallite sizes and the degree of dispersion on the carbon supports. One application of these electrocatalysts was for anodic oxidation of hydrogen in hot phosphoric acid fuel cells, coupled with the influence of low concentrations of carbon monoxide in the fuel gas stream. In a similar way, these platinum on carbon electrocatalysts were evaluated for oxygen reduction in hot phosphoric acid. Binary noble metal alloys were prepared for anodic oxidation of hydrogen and noble metal-refractory metal mixtures were prepared for oxygen reduction. An exemplar alloy of platinum and palladium (50/50 atom %) was discovered for anodic oxidation of hydrogen in the presence of carbon monoxide, and patent disclosures were submitted. For the cathode, platinum-vanadium alloys were prepared showing improved performance over pure platinum. Preliminary experiments on electrocatalyst utilization in electrode structures showed low utilization of the noble metal when the electrocatalyst loading exceeded one weight percent on the carbon.

  13. Catalytic generation of hydrogen from water by reduced forms of 12-tungstosilicic acid in the presence of heterogeneous rhodium polymer catalysts

    SciTech Connect

    Saidkhanov, S.S.; Kokorin, A.I.; Parmon, V.N.; Savinov, E.N.; Savniova, E.R.; Volkov, A.I.

    1985-05-01

    The reduced forms of heteropolyacids (HPA) in acidic aqueous solutions are capable of spontaneous reoxidation, releasing H/sub 2/, as is reported elsewhere. It can therefore be expected that the reduced forms of HPAs with negative electrochemical reduction potentials E /SUB o/ should also release H/sub 2/ in the presence of metallic catalysts. Feasibility in principle has also been demonstrated for the use of colloidal Pt to catalyze the generation of H/sub 2/ from solutions of reduced forms of 12-tungstosilicic HPA. In this paper the authors report on their study of the evolution of H/sub 2/ from solutions of reduced forms of this HPA in the presence of the heterogeneous Rh polymer catalyst Rh-AN-221, which is active in the reaction of hydrogen generation from acidic aqueous solutions of the one-electron reducing agents V/sup 2 +/ (aq) and Cr/sup 2/(Aq).

  14. Furfural modified asphalt obtained by using a Lewis acid as a catalyst

    SciTech Connect

    Memon, G.M.

    1996-12-31

    Asphalt is solid or semi-solid at room temperature, becomes soft and starts flowing upon heating, and becomes hard and brittle at very low temperatures. States have been facing problems such as cracking, rutting, and asphalt adhesion to aggregates in their asphaltic pavements for years. Many polymer additives have been used in asphalt to reduce these problems, but little work has been done using chemically modified products of asphalt to attempt to solve these serious problems of asphalt pavements. The above mentioned problems decrease the life of the pavements, resulting in an increase of maintenance and/or replacement costs. There are two types of cracking which can occur in asphalt pavement; one related to load, and the other related to thermal stress. The load-related cracking is known as fatigue cracking and is defined as fracture under repeated or cyclic stress having a maximum value of less than the tensile strength of the material. The thermal cracking occurs due to pavement shrinkage at low temperature causing the shrinkage stresses to exceed the tensile strength. FHWA researchers have found furfural to be a suitable candidate for functional group modification of asphalt. The modified product shows improved performance as well as improved rheological properties.

  15. [Catalytic application of synthesizing n-butyl acrylate by a new type nanometer complex heteropoly acid catalyst H3PW12O40/SiO2].

    PubMed

    Zhou, Li-qun; Liu, Shi-zhong; Sun, Ju-tang

    2004-10-01

    A new nanometer complex heteropoly acid with Keggin structure, H3PW12O40/SiO2, were prepared by sol-gel method, and were characterized with IR, UV, XRD and TEM techniques. By means of this nanometer catalytic materials, the optimum conditions of the n-butyl acrylate synthesis have been studied. The results show that the complex heteropoly acid H3PW12O40/SiO2 nanoparticles have the mean grain size of 40 nm and they are typical amorphous. A strong chemical interaction exists between H3PW12O40 and silica surface. The nanoparticles have high catalytic activity for synthesizing n-butyl acrylate. The optimum catalytic conditions are as follows: the mole ratio of acrylic acid and n-butyl alcohol is 1:1.2, the reaction temperature is approximately 90-96 degrees C, and the catalyst quantity in the reaction is 10% of the acid mass. The conversion proportion is 94.37% and product yield 91.2% in 5 h. Apparently, the unique structure of the Keggin anions and surface acid center and the high specific surface area and the pseudoliquid phase of H3PW12O40/SiO2 play an important role in the esterification reactions with the acid catalyst. PMID:15760024

  16. Perfluorosulfonic acid membrane catalysts for optical sensing of anhydrides in the gas phase.

    PubMed

    Ayyadurai, Subasri M; Worrall, Adam D; Bernstein, Jonathan A; Angelopoulos, Anastasios P

    2010-07-15

    Continuous, on-site monitoring of personal exposure levels to occupational chemical hazards in ambient air is a long-standing analytical challenge. Such monitoring is required to institute appropriate health measures but is often limited by the time delays associated with batch air sampling and the need for off-site instrumental analyses. In this work, we report on the first attempt to use the catalytic properties of perfluorosulfonic acid (PSA) membranes to obtain a rapid, selective, and highly sensitive optical response to trimellitic anhydride (TMA) in the gas phase for portable sensor device application. TMA is used as starting material for various organic products and is recognized to be an extremely toxic agent by the National Institute for Occupational Safety and Health (NIOSH). Resorcinol dye is shown to become immobilized in PSA membranes and diffusionally constrain an orange brown product that results from acid-catalyzed reaction with more rapidly diffusing TMA molecules. FTIR, UV/vis, reaction selectivity to TMA versus trimellitic acid (TMLA), and homogeneous synthesis are used to infer 5,7- dihydroxyanthraquinone-2-carboxylic acid as the acylation product of the reaction. The color response has a sensitivity to at least 3 parts per billion (ppb) TMA exposure and, in addition to TMLA, excludes maleic anhydride (MA) and phthalic anhydride (PA). Solvent extraction at long times is used to determine that the resorcinol extinction coefficient in 1100 EW PSA membrane has a value of 1210 m(2)/g at 271.01 nm versus a value of 2010 m(2)/g at 275.22 nm in 50 vol% ethanol/water solution. The hypsochromic wavelength shift and reduced extinction coefficient suggest that the polar perfluorosulfonic acid groups in the membrane provide the thermodynamic driving force for diffusion and immobilization. At a resorcinol concentration of 0.376 g/L in the membrane, a partition coefficient of nearly unity is obtained between the membrane and solution concentrations and a maximum conversion rate of one ambient TMA molecule for every two membrane-immobilized resorcinol molecules is observed in 15 min. PMID:20560534

  17. Nano-tribological and wear behavior of boric acid solid lubricant.

    SciTech Connect

    Mirmiran, S.; Tsukruk, V. V.; Erdemir, A.; Energy Technology; Western Michigan Univ.

    1999-01-01

    One uses atomic force microscopy to explore the surface morphology, frictional characteristics (i.e., friction mapping) and surface adhesive forces of boric acid-treated aluminum surfaces. In earlier studies, boric acid was shown to be an effective solid lubricant providing 0.02 to 0.1 friction coefficients to the sliding surfaces of metallic and ceramic materials. In this study, the authors mainly focused on the friction and wear behavior of cleaved single crystals of boric acid. Tests were performed on uncoated and boric acid-coated surfaces of aluminum substrates, as well as the bulk boric acid material. The nano-scale wear of the boric acid crystals manifested itself in the displacement of atomic planes which, in turn, resulted in the formation of the worn area grown by a spiral-growth mechanism. In addition, new crystals in the vicinity of the sliding contact areas were formed. These crystals formed by a spiral dislocation mechanism. The nanoscale friction measurements showed that the friction coefficient of a Si{sub 3}N{sub 4} tip against the boric acid single crystal, was in the range of 0.07 to 0.13, depending on the sliding direction with respect to the crystallographic orientation. The friction coefficients of the boric acid-coated aluminum substrates varied between 0.11 and 0.19. While these values were consistent with earlier findings and further demonstrated the lubricity of boric acid, they were higher than the previous measurements (i.e., 0.011-0.1) obtained on a pin-on-disk machine using steel or ceramic pins. An explanation is provided for this phenomenon.

  18. Solid/Liquid phase diagram of the ammonium sulfate/maleic acid/water system.

    PubMed

    Beyer, Keith D; Schroeder, Jason R; Pearson, Christian S

    2011-12-01

    We have studied the low temperature phase diagram and water activities of the ammonium sulfate/maleic acid/water system using differential scanning calorimetry and infrared spectroscopy of thin films. Using the results from our experiments, we have mapped the solid/liquid ternary phase diagram, determined the water activities based on the freezing point depression, and determined the ice/maleic acid phase boundary as well as the ternary eutectic composition and temperature. We also compare our results to the predictions of the extended AIM aerosol thermodynamics model and find good agreement for the ice melting points in the ice primary phase field of this system; however significant differences were found with respect to phase boundaries, maleic acid dissolution, and ammonium sulfate dissolution. PMID:22017680

  19. Use of pyrolyzed iron ethylenediaminetetraacetic acid modified activated carbon as air-cathode catalyst in microbial fuel cells.

    PubMed

    Xia, Xue; Zhang, Fang; Zhang, Xiaoyuan; Liang, Peng; Huang, Xia; Logan, Bruce E

    2013-08-28

    Activated carbon (AC) is a cost-effective catalyst for the oxygen reduction reaction (ORR) in air-cathode microbial fuel cells (MFCs). To enhance the catalytic activity of AC cathodes, AC powders were pyrolyzed with iron ethylenediaminetetraacetic acid (FeEDTA) at a weight ratio of FeEDTA:AC = 0.2:1. MFCs with FeEDTA modified AC cathodes and a stainless steel mesh current collector produced a maximum power density of 1580 ± 80 mW/m(2), which was 10% higher than that of plain AC cathodes (1440 ± 60 mW/m(2)) and comparable to Pt cathodes (1550 ± 10 mW/m(2)). Further increases in the ratio of FeEDTA:AC resulted in a decrease in performance. The durability of AC-based cathodes was much better than Pt-catalyzed cathodes. After 4.5 months of operation, the maximum power density of Pt cathode MFCs was 50% lower than MFCs with the AC cathodes. Pyridinic nitrogen, quaternary nitrogen and iron species likely contributed to the increased activity of FeEDTA modified AC. These results show that pyrolyzing AC with FeEDTA is a cost-effective and durable way to increase the catalytic activity of AC. PMID:23902951

  20. Fatty acids for controlled release applications: A comparison between prilling and solid lipid extrusion as manufacturing techniques.

    PubMed

    Vervaeck, A; Monteyne, T; Siepmann, F; Boone, M N; Van Hoorebeke, L; De Beer, T; Siepmann, J; Remon, J P; Vervaet, C

    2015-11-01

    The aim of the present study was to evaluate the solid state characteristics, drug release and stability of fatty acid-based formulations after processing via prilling and solid lipid extrusion. Myristic acid (MA), stearic acid (SA) and behenic acid (BA) were used as matrix formers combined with metoprolol tartrate (MPT) as model drug. The prilling process allowed complete dissolution of MPT in the molten fatty acid phase, generating semi-crystalline MPT and the formation of hydrogen bonds between drug and fatty acids in the solid prills. In contrast, as solid lipid extrusion (SLE) induced only limited melting of the fatty acids, molecular interaction with the drug was inhibited, yielding crystalline MPT. Although the addition of a low melting fatty acid allowed more MPT/fatty acid interaction during extrusion, crystalline MPT was detected after processing. Mathematical modeling revealed that the extrudates exhibited a higher apparent drug/water mobility than prills of the same composition, probably due to differences in the inner systems' structure. Irrespective of the processing method, mixed fatty acid systems (e.g. MA/BA) exhibited a lower matrix porosity, resulting in a slower drug release rate. Solid state analysis of these systems indicated that the crystalline structure of the fatty acids was maintained after SLE, while prilling generated a reduced MA crystallinity. Binary MPT/fatty acid systems processed via extrusion showed better stability during storage at 40°C than the corresponding prills. Although mixed fatty acid systems were stable at 25°C, stability problems were encountered during storage at 40°C: a faster release was obtained from the prills, whereas drug release from the extrudates was slower. PMID:26428938

  1. Regeneration of a deactivated USY alkylation catalyst using supercritical isobutane

    SciTech Connect

    Daniel M. Ginosar; David N. Ghompson; Kyle C. Burch

    2005-01-01

    Off-line, in-situ alkylation activity recovery from a completely deactivated solid acid catalyst was examined in a continuous-flow reaction system employing supercritical isobutane. A USY zeolite catalyst was initially deactivated during the liquid phase alkylation of butene with isobutane in a single-pass reactor and then varying amounts of alkylation activity were recovered by passing supercritical isobutane over the catalyst bed at different reactivation conditions. Temperature, pressure and regeneration time were found to play important roles in the supercritical isobutane regeneration process when applied to a completely deactivated USY zeolite alkylation catalyst. Manipulation of the variables that influence solvent strength, diffusivity, surface desorption, hydride transfer rates, and coke aging, strongly influence regeneration effectiveness.

  2. Oxidative degradation of dinitro butyl phenol (DNBP) utilizing hydrogen peroxide and solar light over a Al2O3-supported Fe(III)-5-sulfosalicylic acid (ssal) catalyst.

    PubMed

    Zhang, Qian; Jiang, Wen-Feng; Wang, Hui-Long; Chen, Mao-Du

    2010-04-15

    A novel and efficient photo-Fenton catalyst of Fe(III)-5-sulfosalicylic acid (ssal) supported on Al(2)O(3) was prepared and characterized by FT-IR and TEM-EDX technique. A detailed investigation of photocatalytic degradation of 2-sec-butyl-4,6-dinitrophenol (DNBP) using this catalyst and H(2)O(2) under solar light irradiation was carried out. The effects of reaction parameters on photodegradation performance were investigated by examining H(2)O(2) dosage, catalyst loading, solution pH, initial DNBP concentration and temperature. The optimal conditions were an initial DNBP concentration of 40 mg L(-1) at pH 2.5 and temperature 30 degrees C with catalyst loading of 1.0 g L(-1) and H(2)O(2) concentration of 5 mmol L(-1) under solar light irradiation for 100 min. Almost complete degradation of DNBP was observed with [Fe(III)-ssal]-Al(2)O(3)/H(2)O(2) process under the optimal conditions. The degradation of DNBP by photo-Fenton-type process can be divided into the initiation phase and the fast phase. The kinetics of Fenton oxidation is complex and the degradation of DNBP in the two phases both can be described by a pseudo-first-order kinetic model. No obvious decline in efficiency of the [Fe(III)-ssal]-Al(2)O(3) catalyst was observed after 5 repeated cycles indicating this catalyst is stable and reusable. A possible reaction mechanism was proposed on the basis of all the information obtained under various experimental conditions. PMID:20034737

  3. Nanoparticles of Ag with a Pt and Pd rich surface supported on carbon as a new catalyst for the oxygen electroreduction reaction (ORR) in acid electrolytes: Part 2

    NASA Astrophysics Data System (ADS)

    Pech-Pech, I. E.; Gervasio, Dominic F.; Pérez-Robles, J. F.

    2015-02-01

    In the first part of this work, the feasibility of developing a catalyst with high activity for the oxygen electroreduction reaction (ORR) in acid media and with low Pt loading was demonstrated by over coating a silver (Ag) nanoparticle with a shell of platinum (Pt) and palladium (Pd) [7]. The results show that best activity is not directly related to a higher PtPd loading on the surface of the Ag. The best catalyst in a series of this type of catalyst is found with Ag@Pt0.3Pd0.3/C which gives a specific activity for oxygen reduction, jk (in units of mA cm-2 of real area), of 0.07 mA cm-2 at 0.85 V vs. NHE, as compared to 0.04 mA cm-2 when with a commercial Pt on carbon catalyst (Pt20/C) is used in an identical electrode except for the catalyst. The mass activity, jm (in units of mA ?g-1 of Pt), for Ag@Pt0.3Pd0.3/C is 0.04 mA ?g-1 of Pt at 0.85 V vs. NHE, whereas that for the Pt20/C gives 0.02 mA ?g-1 of Pt, showing Ag@Pt0.3Pd0.3/C is a lower-cost catalyst, because using a Ag core and Pd with Pt in the shell gives the highest catalytic activity using less Pt.

  4. Nanoparticles of Ag with a Pt and Pd rich surface supported on carbon as a new catalyst for the oxygen electroreduction reaction (ORR) in acid electrolytes: Part 1

    NASA Astrophysics Data System (ADS)

    Pech-Pech, I. E.; Gervasio, Dominic F.; Godínez-Garcia, A.; Solorza-Feria, O.; Pérez-Robles, J. F.

    2015-02-01

    Silver (Ag) nanoparticles enriched with platinum (Pt) and palladium (Pd) on their surfaces (Ag@Pt0.1Pd0.1) are supported on Vulcan XC-72 carbon (C) to form a new catalyst (Ag@Pt0.1Pd0.1/C) for the oxygen reduction reaction (ORR) in acid electrolytes. This catalyst is prepared in one pot by reducing Ag and then Pt and Pd metal salts with sodium borohydride in the presence of trisodium citrate then adding XC-72 while applying intense ultrasound. The metallic Ag@Pt0.1Pd0.1 nanoparticles contain 2 weight percent of Pt, are spherical and have an average size less than 10 nm as determined by X-ray diffraction (XRD) and transmission electron microscopy (TEM). At the ORR potentials, Ag nanoparticles on carbon (Ag/C) rapidly lose Ag by dissolution and show no more catalytic activity for the ORR than the carbon support, whereas Ag@Pt0.1Pd0.1/C is a stable catalyst and exhibits 1.4 and 1.6 fold greater specific activity, also 3.6 and 2.8 fold greater mass activity for ORR in 0.5 M H2SO4 solution than comparable Pt/C and Pt0.5Pd0.5/C catalysts with the same Pt loading as determined for thin-films of these catalysts on a rotating-disk electrode (TF-RDE). Using silver nanoparticles increases Pt utilization and therefore decreases Pt-loading and cost of a catalyst for a proton exchange membrane fuel cell (PEMFC) electrode.

  5. Iron oxide nanoparticles immobilized to mesoporous NH2-SiO2 spheres by sulfonic acid functionalization as highly efficient catalysts

    NASA Astrophysics Data System (ADS)

    Zhang, Guoliang; Qin, Lei; Wu, Yujiao; Xu, Zehai; Guo, Xinwen

    2014-12-01

    A novel SiO2 nanosphere was synthesized by the post-synthetic grafting of sulfonic acid groups on to anionic-surfactant-templated mesoporous NH2-silica (AMAS). This one-pot post-functionalization strategy allowed more metal ions to be homogeneously anchored into the channel of the meso-SiO2 nanosphere. After hydrothermal and calcination treatment, the in situ growth of ?-Fe2O3 on sulfonic acid-functionalized mesoporous NH2-SiO2 (SA-AMAS) exhibited much higher activity in the visible-light assisted Fenton reaction at neutral pH than that for AMAS or meso-SiO2 nanospheres. By analysis, the grafted sulfonic acid group can not only enhance the acid strength of the catalyst, but can also bring more orbital-overlapping between the active sites (FeII and FeIII) and the surface peroxide species, to facilitate the decomposition of H2O2 to hydroxyl radical. The present results provide opportunities for developing heterogeneous catalysts with high-performance in the field of green chemistry and environmental remediation.A novel SiO2 nanosphere was synthesized by the post-synthetic grafting of sulfonic acid groups on to anionic-surfactant-templated mesoporous NH2-silica (AMAS). This one-pot post-functionalization strategy allowed more metal ions to be homogeneously anchored into the channel of the meso-SiO2 nanosphere. After hydrothermal and calcination treatment, the in situ growth of ?-Fe2O3 on sulfonic acid-functionalized mesoporous NH2-SiO2 (SA-AMAS) exhibited much higher activity in the visible-light assisted Fenton reaction at neutral pH than that for AMAS or meso-SiO2 nanospheres. By analysis, the grafted sulfonic acid group can not only enhance the acid strength of the catalyst, but can also bring more orbital-overlapping between the active sites (FeII and FeIII) and the surface peroxide species, to facilitate the decomposition of H2O2 to hydroxyl radical. The present results provide opportunities for developing heterogeneous catalysts with high-performance in the field of green chemistry and environmental remediation. Electronic supplementary information (ESI) available: BET surface area and textural data, degradation results, FTIR spectra, TEM images, and element analysis. See DOI: 10.1039/c4nr05884d

  6. Process of making supported catalyst

    DOEpatents

    Schwarz, James A. (Fayetteville, NY); Subramanian, Somasundaram (Melvindale, MI)

    1992-01-01

    Oxide supported metal catalysts have an additional metal present in intimate association with the metal catalyst to enhance catalytic activity. In a preferred mode, iridium or another Group VIII metal catalyst is supported on a titania, alumina, tungsten oxide, silica, or composite oxide support. Aluminum ions are readsorbed onto the support and catalyst, and reduced during calcination. The aluminum can be added as aluminum nitrate to the iridium impregnate solution, e.g. chloroiridic acid.

  7. Catalyst Alloys Processing

    NASA Astrophysics Data System (ADS)

    Tan, Xincai

    2014-10-01

    Catalysts are one of the key materials used for diamond formation at high pressures. Several such catalyst products have been developed and applied in China and around the world. The catalyst alloy most widely used in China is Ni70Mn25Co5 developed at Changsha Research Institute of Mining and Metallurgy. In this article, detailed techniques for manufacturing such a typical catalyst alloy will be reviewed. The characteristics of the alloy will be described. Detailed processing of the alloy will be presented, including remelting and casting, hot rolling, annealing, surface treatment, cold rolling, blanking, finishing, packaging, and waste treatment. An example use of the catalyst alloy will also be given. Industrial experience shows that for the catalyst alloy products, a vacuum induction remelt furnace can be used for remelting, a metal mold can be used for casting, hot and cold rolling can be used for forming, and acid pickling can be used for metal surface cleaning.

  8. Combustion Catalysts in Industry- An Update 

    E-print Network

    Merrell, G. A.; Knight, R. S.

    1985-01-01

    Combustion catalysts improve boiler efficiency by extracting more heat energy from the fuel and by reducing heat losses when operating at minimum excess air. In addition, an effective combustion catalyst may reduce the level of smoke and solid...

  9. Solid/liquid phase diagram of the ammonium sulfate/glutaric acid/water system.

    PubMed

    Beyer, Keith D; Pearson, Christian S; Henningfield, Drew S

    2013-05-01

    We have studied the low temperature phase diagram and water activities of the ammonium sulfate/glutaric acid/water system using differential scanning calorimetry, infrared spectroscopy of thin films, and a new technique: differential scanning calorimetry-video microscopy. Using these techniques, we have determined that there is a temperature-dependent kinetic effect to the dissolution of glutaric acid in aqueous solution. We have mapped the solid/liquid ternary phase diagram, determined the water activities based on the freezing point depression, and determined the ice/glutaric acid phase boundary as well as the ternary eutectic composition and temperature. We have also modified our glutaric acid/water binary phase diagram previously published based on these new results. We compare our results for the ternary system to the predictions of the Extended AIM Aerosol Thermodynamics Model (E-AIM), and find good agreement for the ice melting points in the ice primary phase field of this system; however, significant differences were found with respect to phase boundaries, concentration and temperature of the ternary eutectic, and glutaric acid dissolution. PMID:23544733

  10. Highly active carbon supported palladium catalysts decorated by a trace amount of platinum by an in-situ galvanic displacement reaction for formic acid oxidation

    NASA Astrophysics Data System (ADS)

    Li, Zuopeng; Li, Muwu; Han, Mingjia; Wu, Xin; Guo, Yong; Zeng, Jianhuang; Li, Yuexia; Liao, Shijun

    2015-03-01

    Aimed at reducing platinum usage and improved catalytic activity for formic acid oxidation, a series of Pt decorated Pd/C catalysts are prepared by an in-situ galvanic displacement reaction between freshly prepared Pd/C ink and H2PtCl6 in an aqueous solution. The catalysts with 4 nm particle sizes and 20 wt.% loadings have been characterized by transmission electron microscopy, thermogravimetric analysis and X-ray photoelectron spectroscopy (XPS). The electrochemical evaluations by cyclic voltammetry are conducted to test out the CO tolerance and catalytic activities. In addition to XPS analysis, a theoretical calculation has been attempted the first time to find out the surface Pd/Pt molar ratios. The decay rate of the catalysts has been evaluated by the percentage of the forward/backward peak current retained using the value at the 20th cycle divided by that in the first cycle. Compared with a Pd/C benchmark, all Pt decorated Pd/C register enhanced activity while the cost remains virtually unchanged. The optimized catalyst is found to have a Pd/Pt molar ratio of 75:1 but with 2.5 times activity relative to that of Pd/C.

  11. Solid-Phase Formation Of Isovaline, A Non-Biological, Meteoritic Amino Acid

    NASA Astrophysics Data System (ADS)

    Hudson, Reggie L.; Lewis, A. S.; Moore, M. H.; Dworkin, J. P.; Glavin, D. P.

    2007-10-01

    Among the Murchison (CM) meteoritic amino acids, isovaline stands out as being non-biological (nonprotein) and having a high abundance. Approximately equal amounts of D- and L-isovaline have been reported in CM meteorites, but the molecule's structure appears to prohibit racemization in aqueous solutions. While it is possible that isovaline could be made by the oft-studied Strecker reaction, laboratory experiments have seldom been able to produce this molecule from realistic molecular precursors. Recently we have investigated the low-temperature solid-phase chemistry of isovaline with an eye toward the molecule's formation, its stability, and the interconversion of its D- and L-enantiomers. Ion-irradiated isovaline-containing ices were examined by IR spectroscopy and highly-sensitive LC/ToF-MS methods to assess both amino acid destruction and racemization. Samples were studied both in the presence and absence of water-ice, and the destruction of isovaline was measured as a function of radiation dose. In addition, we have continued our earlier work on solid-phase amino acid formation, extending it to cover isovaline. In this presentation we will report the results of these newer investigations. This work was supported by a grant to the Goddard Center for Astrobiology through the NASA Astrobiology Institute. AL was supported by an award from the Summer Undergraduate Internship in Astrobiology program.

  12. Thin layer-based spectral and electrophoretic study of electro-oxidation of solid ellagic acid.

    PubMed

    Chen, Yu-Jiao; Deng, Ning; Hu, Bin; Wang, Yan; He, Jian-Bo

    2014-02-27

    Acquisition of data from both in situ spectroscopy detection and online chromatography-like separation is important for studying complex electrochemical reactions. The present work provides an example of combination of thin-layer spectral and electrophoretic electrochemistry, both based on thin-layer electrolysis. Two thin-layer electrochemical cells were used to investigate the electro-oxidation of solid ellagic acid at different potentials, in acidic, physiological, and alkaline buffer media. UV-vis spectra and cyclic voltabsorptograms of the oxidation products were recorded in situ without interference from the solid reactant. Four oxidation products, depending upon the buffer pH and the applied potential, were separated and detected by electrophoretic electrochemistry. The major products possess redox stability, possibly with a diquinonemethide structure. The minor product is considered as an o-quinone derivative with a lactone-ring-opening, which can be reduced or further oxidized at appropriate potentials. A consecutive-parallel reaction mechanism is proposed for the formation of four products of ellagic acid in different pH media, which enriches the knowledge about the oxidation pathway and antioxidant property of this biologically active polyphenol compound. PMID:24495249

  13. Temperature dependent solid-state proton migration in dimethylurea-oxalic acid complexes.

    PubMed

    Jones, Andrew O F; Lemée-Cailleau, Marie-Hélène; Martins, David M S; McIntyre, Garry J; Oswald, Iain D H; Pulham, Colin R; Spanswick, Christopher K; Thomas, Lynne H; Wilson, Chick C

    2012-10-14

    The phenomenon of solid-state proton migration within molecular complexes containing short hydrogen bonds is investigated in two dimethylurea-oxalic acid complexes. Extensive characterisation by both X-ray and neutron diffraction shows that proton migration along the hydrogen bond can be induced in these complexes as a function of temperature. This emphasises the subtle features of the hydrogen bond potential well in such short hydrogen bonded complexes, both intrinsically and in the effect of the local crystalline environment. Based on these findings, the synthesis and analysis of a series of solid-state molecular complexes is shown to be a potential route to designing materials with tuneable proton migration effects. PMID:22918382

  14. Formic Acid Dehydrogenation on Au-Based Catalysts at Near-Ambient Temperatures

    SciTech Connect

    Ojeda, Manuel; Iglesia, Enrique

    2008-11-24

    Formic acid (HCOOH) is a convenient hydrogen carrier in fuel cells designed for portable use. Recent studies have shown that HCOOH decomposition is catalyzed with Ru-based complexes in the aqueous phase at near-ambient temperatures. HCOOH decomposition reactions are used frequently to probe the effects of alloying and cluster size and of geometric and electronic factors in catalysis. These studies have concluded that Pt is the most active metal for HCOOH decomposition, at least as large crystallites and extended surfaces. The identity and oxidation state of surface metal atoms influence the relative rates of dehydrogenation (HCOOH {yields} H{sub 2} + CO{sub 2}) and dehydration (HCOOH {yields} H{sub 2}O + CO) routes, a selectivity requirement for the synthesis of CO-free H{sub 2} streams for low-temperature fuel cells. Group Ib and Group VIII noble metals catalyze dehydrogenation selectively, while base metals and metal oxides catalyze both routes, either directly or indirectly via subsequent water-gas shift (WGS) reactions.

  15. Development of ternary alloy cathode catalysts for phosphoric acid fuel cells

    NASA Astrophysics Data System (ADS)

    1988-11-01

    The overall objective of the program was the identification development and incorporation of high activity platinum ternary alloys on corrosion resistant supports, for use in advanced phosphoric acid fuel cells. Two high activity ternary alloys, Pr-Cr-Ce and Pt-Ni-Co, both supported on Vulcan XC-72, were identified during the course of the program. The Pr-Ni-Co system was selected for optimization, including preparation and evaluation on corrosion resistant supports such as 2700 C heat-treated Vulcan XC-72 and 2700 C heat-treated Black Pearls 2000. A series of tests identified optimum metal ratios, heat-treatment temperatures and heat-treatment atmospheres for the Pr-Ni-Co system. During characterization testing, it was discovered that approximately 50 percent of the nickel and cobalt present in the starting material could be removed, subsequent to alloy formation, without degrading performance. Extremely stable full cell performance was observed for the Pt-Ni-Co system during a 10,000 hour atmosphere pressure life test. Several theories are proposed to explain the enhancement in activity due to alloy formation. Recommendations are made for future research in this area.

  16. Development of ternary alloy cathode catalysts for phosphoric acid fuel cells: Final report

    SciTech Connect

    Jalan, V.; Kosek, J.; Giner, J.; Taylor, E. J.; Anderson, E.; Bianchi, V.; Brooks, C.; Cahill, K.; Cropley, C.; Desai, M.; Frost, D.; Morriseau, B.; Paul, B.; Poirier, J.; Rousseau, M.; Swette, L.; Waterhouse, R.

    1988-11-01

    The overall objective of the program was the identification development and incorporation of high activity platinum ternary alloys on corrosion resistant supports, for use in advanced phosphoric acid fuel cells. Two high activity ternary alloys, Pr-Cr-Ce and Pt-Ni-Co, both supported on Vulcan XC-72, were identified during the course of the program. The Pr-Ni-Co system was selected for optimization, including preparation and evaluation on corrosion resistant supports such as 2700/degree/C heat-treated Vulcan XC-72 and 2700/degree/ heat-treated Black Pearls 2000. A series of tests identified optimum metal ratios, heat-treatment temperatures and heat-treatment atmospheres for the Pr-Ni-Co system. During characterization testing, it was discovered that approximately 50% of the nickel and cobalt present in the starting material could be removed, subsequent to alloy formation, without degrading performance. Extremely stable full cell performance was observed for the Pt-Ni-Co system during a 10,000 hour atmosphere pressure life test. Several theories are proposed to explain the enhancement in activity due to alloy formation. Recommendations are made for future research in this area. 62 refs., 23 figs., 27 tabs.

  17. Oxidation catalyst

    DOEpatents

    Ceyer, Sylvia T. (Cambridge, MA); Lahr, David L. (Cambridge, MA)

    2010-11-09

    The present invention generally relates to catalyst systems and methods for oxidation of carbon monoxide. The invention involves catalyst compositions which may be advantageously altered by, for example, modification of the catalyst surface to enhance catalyst performance. Catalyst systems of the present invention may be capable of performing the oxidation of carbon monoxide at relatively lower temperatures (e.g., 200 K and below) and at relatively higher reaction rates than known catalysts. Additionally, catalyst systems disclosed herein may be substantially lower in cost than current commercial catalysts. Such catalyst systems may be useful in, for example, catalytic converters, fuel cells, sensors, and the like.

  18. Chemical effects induced by gamma-irradiation in solid 2-iodobenzoic acid

    NASA Astrophysics Data System (ADS)

    Al-Resayes, S.; Siddiqui, M. R. H.; Al-Arifi, A. S. N.; Mahfouz, R.

    2006-08-01

    gamma-Irradiation effects on solid 2-iodobenzoic acid were investigated in the present work. The degradation products were separated and identified using spectroscopic (UV-Vis, H-1, C-13, (INMR)-I-127) and chromato-graphic techniques. The degradation products (I-2 , I- and IO3- ) formed as a result of interaction of trapped radicals and electrons with solvent molecules and ions are investigated as a function of absorbed gamma-rays dose. Aromatic products of lower and higher molecular weight than the corresponding investigated compound were analyzed and separated by HPLC. The results have been discussed in terms of mechanisms based on free radicals and ion-molecule interactions.

  19. Determination of the mean solid-liquid interface energy of pivalic acid

    NASA Technical Reports Server (NTRS)

    Singh, N. B.; Gliksman, M. E.

    1989-01-01

    A high-confidence solid-liquid interfacial energy is determined for an anisotropic material. A coaxial composite having a cylindrical specimen chamber geometry provides a thermal gradient with an axial heating wire. The surface energy is derived from measurements of grain boundary groove shapes. Applying this method to pivalic acid, a surface energy of 2.84 erg/sq cm was determined with a total systematic and random error less than 10 percent. The value of interfacial energy corresponds to 24 percent of the latent heat of fusion per molecule.

  20. Iron oxide nanoparticles immobilized to mesoporous NH2-SiO2 spheres by sulfonic acid functionalization as highly efficient catalysts.

    PubMed

    Zhang, Guoliang; Qin, Lei; Wu, Yujiao; Xu, Zehai; Guo, Xinwen

    2015-01-21

    A novel SiO2 nanosphere was synthesized by the post-synthetic grafting of sulfonic acid groups on to anionic-surfactant-templated mesoporous NH2-silica (AMAS). This one-pot post-functionalization strategy allowed more metal ions to be homogeneously anchored into the channel of the meso-SiO2 nanosphere. After hydrothermal and calcination treatment, the in situ growth of ?-Fe2O3 on sulfonic acid-functionalized mesoporous NH2-SiO2 (SA-AMAS) exhibited much higher activity in the visible-light assisted Fenton reaction at neutral pH than that for AMAS or meso-SiO2 nanospheres. By analysis, the grafted sulfonic acid group can not only enhance the acid strength of the catalyst, but can also bring more orbital-overlapping between the active sites (Fe(II) and Fe(III)) and the surface peroxide species, to facilitate the decomposition of H2O2 to hydroxyl radical. The present results provide opportunities for developing heterogeneous catalysts with high-performance in the field of green chemistry and environmental remediation. PMID:25482204

  1. Cryomilling-induced solid dispersion of poor glass forming/poorly water-soluble mefenamic acid with polyvinylpyrrolidone K12.

    PubMed

    Kang, Naewon; Lee, Jangmi; Choi, Ji Na; Mao, Chen; Lee, Eun Hee

    2015-06-01

    The effect of mechanical impact on the polymorphic transformation of mefenamic acid (MFA) and the formation of a solid dispersion of mefenamic acid, a poor glass forming/poorly-water soluble compound, with polyvinylpyrrolidone (PVP) K12 was investigated. The implication of solid dispersion formation on solubility enhancement of MFA, prepared by cryomilling, was investigated. Solid state characterization was conducted using powder X-ray diffraction (PXRD) and Fourier-transform infrared (FTIR) spectroscopy combined with crystal structure analysis. Apparent solubility of the mixtures in pH 7.4 buffer was measured. A calculation to compare the powder patterns and FTIR spectra of solid dispersions with the corresponding physical mixtures was conducted. Solid state characterization showed that (1) MFA I transformed to MFA II when pure MFA I was cryogenically milled (CM); and (2) MFA forms a solid dispersion when MFA was cryogenically milled with PVP K12. FTIR spectral analysis showed that hydrogen bonding facilitated by mechanical impact played a major role in forming solid dispersions. The apparent solubility of MFA was significantly improved by making a solid dispersion with PVP K12 via cryomilling. This study highlights the importance of cryomilling with a good hydrogen bond forming excipient as a technique to prepare solid dispersion, especially when a compound shows a poor glass forming ability and therefore, is not easy to form amorphous forms by conventional method. PMID:24849785

  2. Highly active water-soluble palladium catalyst for the regioselective carbonylation of vinyl aromatics to 2-arylpropionic acids

    E-print Network

    Jayasree, S.; Seayad, A.; Chaudhari, Raghunath Vitthal

    2000-06-20

    A novel water-soluble Pd complex containing pyridine carboxylate and TPPTS as ligands is a highly active catalyst for the carbonylation of vinyl aromatics under biphasic conditions and provides high regioselectivity to ...

  3. Far infrared spectra of solid state aliphatic amino acids in different protonation states

    NASA Astrophysics Data System (ADS)

    Trivella, Aurélien; Gaillard, Thomas; Stote, Roland H.; Hellwig, Petra

    2010-03-01

    Far infrared spectra of zwitterionic, cationic, and anionic forms of aliphatic amino acids in solid state have been studied experimentally. Measurements were done on glycine, L-alanine, L-valine, L-leucine, and L-isoleucine powder samples and film samples obtained from dried solutions prepared at pH ranging from 1 to 13. Solid state density functional theory calculations were also performed, and detailed potential energy distributions were obtained from normal mode results. A good correspondence between experimental and simulated spectra was achieved and this allowed us to propose an almost complete band assignment for the far infrared spectra of zwitterionic forms. In the 700-50 cm-1 range, three regions were identified, each corresponding to a characteristic set of normal modes. A first region between 700 and 450 cm-1 mainly contained the carboxylate bending, rocking, and wagging modes as well as the ammonium torsional mode. The 450-250 cm-1 region was representative of backbone and sidechain skeletal bending modes. At last, the low wavenumber zone, below 250 cm-1, was characteristic of carboxylate and skeletal torsional modes and of lattice modes. Assignments are also proposed for glycine cationic and anionic forms, but could not be obtained for all aliphatic amino acids due to the lack of structural data. This work is intended to provide fundamental information for the understanding of peptides vibrational properties.

  4. Potential effects of clean coal technologies on acid precipitation, greenhouse gases, and solid waste disposal

    SciTech Connect

    Blasing, T.J.; Miller, R.L.; McCold, L.N.

    1993-11-01

    The US Department of Energy`s (DOE`s) Clean Coal Technology Demonstration Program (CCTDP) was initially funded by Congress to demonstrate more efficient, economically feasible, and environmentally acceptable coal technologies. Although the environmental focus at first was on sulfur dioxide (SO{sub 2}) and nitrogen oxides (NO{sub x}) because their relationship to acid precipitation, the CCTDP may also lead to reductions in carbon dioxide (CO{sub 2}) emissions and in the volume of solid waste produced, compared with conventional technologies. The environmental effects of clean coal technologies (CCTs) depend upon which (if any) specific technologies eventually achieve high acceptance in the marketplace. In general, the repowering technologies and a small group of retrofit technologies show the most promise for reducing C0{sub 2} emissions and solid waste. These technologies also compare favorably with other CCTs in terms of SO{sub 2} and NO{sub x} reductions. The upper bound for CO{sup 2} reductions in the year 2010 is only enough to reduce global ``greenhouse`` warming potential by about 1%. However, CO{sub 2} emissions come from such variety of sources around the globe that no single technological innovation or national policy change could realistically be expected to reduce these emissions by more than a few percent. Particular CCTs can lead to either increases or decreases in the amount of solid waste produced. However, even if decreases are not achieved, much of the solid waste from clean coal technologies would be dry and therefore easier to dispose of than scrubber sludge.

  5. Biosourced polymetallic catalysts: an efficient means to synthesize underexploited platform molecules from carbohydrates.

    PubMed

    Escande, Vincent; Olszewski, Tomasz K; Petit, Eddy; Grison, Claude

    2014-07-01

    Polymetallic hyperaccumulating plants growing on wastes from former mining activity were used as the starting material in the preparation of novel plant-based Lewis acid catalysts. The preparation of biosourced Lewis acid catalysts is a new way to make use of mining wastes. These catalysts were characterized by X-ray fluorescence, X-ray diffraction, inductively coupled plasma mass spectrometry, and direct infusion electrospray ionization mass spectrometry. These analyses revealed a complex composition of metal species, present mainly as polymetallic chlorides. The catalysts proved to be efficient and recyclable in a solid-state version of the Garcia Gonzalez reaction, which has been underexploited until now in efforts to use carbohydrates from biomass. This methodology was extended to various carbohydrates to obtain the corresponding polyhydroxyalkyl furans in 38-98% yield. These plant-based catalysts may be a better alternative to classical Lewis acid catalysts that were previously used for the Garcia Gonzalez reaction, such as ZnCl2 , FeCl3 , and CeCl3 , which are often unrecyclable, require aqueous treatments, or rely on metals, the current known reserves of which will be consumed in the coming decades. Moreover, the plant-based catalysts allowed novel control of the Garcia Gonzalez reaction, as two different products were obtained depending on the reaction conditions. PMID:25044809

  6. Improved catalysts and method

    SciTech Connect

    Taylor, C.E.; Noceti, R.P.

    1990-12-31

    An improved catalyst and method for the oxyhydrochlorination of methane is disclosed. The catalyst includes a pyrogenic porous support on which is layered as active material, cobalt chloride in major proportion, and minor proportions of an alkali metal chloride and of a rare earth chloride. On contact of the catalyst with a gas flow of methane, HCl and oxygen, more than 60% of the methane is converted and of that converted more than 40% occurs as monochloromethane. Advantageously, the monochloromethane can be used to produce gasoline boiling range hydrocarbons with the recycle of HCl for further reaction. This catalyst is also of value for the production of formic acid as are analogous catalysts with lead, silver or nickel chlorides substituted for the cobalt chloride. 8 figs., 3 tabs.

  7. Reactivation of hydroformylation catalysts

    SciTech Connect

    Babin, J.E.; Bryant, D.R.; Harrison, A.M.; Miller, D.J.

    1993-08-17

    A process is described for improving the catalytic activity of a partially deactivated solubilized rhodium-tertiary organophosphine complex hydroformylation catalyst, which comprises (1) mixing under non-hydroformylating conditions, a organic liquid medium containing said solubilized partially deactivated complex catalyst, with propargyl alcohol and a carboxylic acid of the formula RCOOH wherein R represents hydrogen or an alkyl or aryl radical to obtain a treated solubilized rhodium-tertiary organophosphine complex product solution; and (2) removing from said product solution, the carboxylic acid employed in Step (1) to obtain a rhodium-tertiary organophosphine complex hydroformylation catalyst that is more catalytically active than said partially deactivated rhodium-tertiary organophosphine complex hydroformylation catalyst starting material of Step (1).

  8. Immobilized bisdiazaphospholane catalysts for asymmetric hydroformylation.

    PubMed

    Adint, Tyler T; Landis, Clark R

    2014-06-01

    Condensation reactions of enantiopure bis-3,4-diazaphospholanes (BDPs) that are functionalized with carboxylic acids enable covalent attachment to bead and silica supports. Exposure of tethered BDPs to the hydroformylation catalyst precursor, Rh(acac)(CO)2, yields catalysts for immobilized asymmetric hydroformylation (iAHF) of prochiral alkenes. Compared with homogeneous catalysts, catalysts immobilized on Tentagel resins exhibit similarly high regioselectivity and enantioselectivity. When corrected for apparent catalyst loading, the activity of the immobilized catalysts approaches that of the homogeneous analogues. Excellent recyclability with trace levels of rhodium leaching are observed in batch and flow reactor conditions. Silica-bound catalysts exhibit poorer enantioselectivities. PMID:24742285

  9. Design Strategies for CeO2-MoO3 Catalysts for DeNOx and Hg(0) Oxidation in the Presence of HCl: The Significance of the Surface Acid-Base Properties.

    PubMed

    Chang, Huazhen; Wu, Qingru; Zhang, Tao; Li, Mingguan; Sun, Xiaoxu; Li, Junhua; Duan, Lei; Hao, Jiming

    2015-10-20

    A series of CeMoOx catalysts with different surface Ce/Mo ratios was synthesized by a coprecipitation method via changing precipitation pH value. The surface basicity on selective catalytic reduction (SCR) catalysts (CeMoOx and VMo/Ti) was characterized and correlated to the durability and activity of catalyst for simultaneous elimination of NOx and Hg(0). The pH value in the preparation process affected the surface concentrations of Ce and Mo, the Brunauer-Emmett-Teller (BET) specific surface area, and the acid-base properties over the CeMoOx catalysts. The O 1s X-ray photoelectron spectroscopy (XPS) spectra and CO2-temperature programmed desorption (TPD) suggested that the surface basicity increased as the pH value increased. The existence of strong basic sites contributed to the deactivation effect of HCl over the VMo/Ti and CeMoOx catalysts prepared at pH = 12. For the CeMoOx catalysts prepared at pH = 9 and 6, the appearance of surface molybdena species replaced the surface -OH, and the existence of appropriate medium-strength basic sites contributed to their resistance to HCl poisoning in the SCR reaction. Moreover, these sites facilitated the adsorption and activation of HCl and enhanced Hg(0) oxidation. On the other hand, the inhibitory effect of NH3 on Hg(0) oxidation was correlated with the competitive adsorption of NH3 and Hg(0) on acidic surface sites. Therefore, acidic surface sites may play an important role in Hg(0) adsorption. The characterization and balance of basicity and acidity of an SCR catalyst is believed to be helpful in preventing deactivation by acid gas in the SCR reaction and simultaneous Hg(0) oxidation. PMID:26421943

  10. Novel solid state proton-conductors based on polymeric non-oxy acids. Final report

    SciTech Connect

    Appleby, A.J.; Srinivasan, S.; Parthasarathy, A.; Gonzalez, E.R.; DesMarteau, D.; Gillette, M.S.; Ghosh, J.K.; Jalan, V.; Desai, M.

    1992-01-01

    Objectives of this project were to prepare and characterize novel solid state proton-conductors and to evaluate these compounds as fuel cell electrolytes. The thrust was on the synthesis of new proton-conducting ``model`` and ``polymeric`` compounds, based on acid functions of the type (R{sub f}SO{sub 2}){sub 2}NH and (R{sub f}SO{sub 2}){sub 2}CH{sub 2} in appropriate fluorinated carbon structures, their physics-chemical characterization (Infra-red, Nuclear Magnetic Resonance, Differential Scanning Calorimetry, and X-ray Diffraction), and is pro. evaluation as candidate fuel cell electrolytes for use at elevated temperatures. This project consisted of four tasks (i) Synthesis of Proton-Conducting Polymer Electrolytes; (ii) Physical and Chemical Characterization of Proton-Conducting Polymer Electrolytes; (iii) Electrochemical Characterization of Proton-Conducting Polymer Electrolytes; and (iv) Evaluation of Proton-Conducting Polymer Electrolytes for Fuel Cells.

  11. Processes for converting lignocellulosics to reduced acid pyrolysis oil

    DOEpatents

    Kocal, Joseph Anthony; Brandvold, Timothy A

    2015-01-06

    Processes for producing reduced acid lignocellulosic-derived pyrolysis oil are provided. In a process, lignocellulosic material is fed to a heating zone. A basic solid catalyst is delivered to the heating zone. The lignocellulosic material is pyrolyzed in the presence of the basic solid catalyst in the heating zone to create pyrolysis gases. The oxygen in the pyrolysis gases is catalytically converted to separable species in the heating zone. The pyrolysis gases are removed from the heating zone and are liquefied to form the reduced acid lignocellulosic-derived pyrolysis oil.

  12. Experimental and computational thermochemical study and solid-phase structure of 5,5-dimethylbarbituric acid.

    PubMed

    Roux, María Victoria; Notario, Rafael; Foces-Foces, Concepción; Temprado, Manuel; Ros, Francisco; Emel'yanenko, Vladimir N; Verevkin, Sergey P

    2010-03-18

    This paper reports an experimental and computational thermochemical study on 5,5-dimethylbarbituric acid and the solid-phase structure of the compound. The value of the standard (p(o) = 0.1 MPa) molar enthalpy of formation in the gas phase at T = 298.15 K has been determined. The energy of combustion was measured by static bomb combustion calorimetry, and from the result obtained, the standard molar enthalpy of formation in the crystalline state at T = 298.15 K was calculated as -(706.4 +/- 2.2) kJ x mol(-1). The enthalpy of sublimation was determined using a transference (transpiration) method in a saturated NB(2) stream, and a value of the enthalpy of sublimation at T = 298.15 K was derived as (115.8 +/- 0.5) kJ x mol(-1). From these results a value of -(590.6 +/- 2.3) kJ x mol(-1) for the gas-phase enthalpy of formation at T = 298.15 K was determined. Theoretical calculations at the G3 level were performed, and a study on molecular and electronic structure of the compound has been carried out. Calculated enthalpies of formation are in reasonable agreement with the experimental value. 5,5-Dimethylbarbituric acid was characterized by single crystal X-ray diffraction analysis. In the crystal structure, N-H...O=C hydrogen bonds lead to the formation of ribbons connected further by weak C-H...O=C hydrogen bonds into a three-dimensional network. The molecular and supramolecular structures observed in the solid state were also investigated in the gas phase by DFT calculations. PMID:20180529

  13. Multinuclear Solid-State NMR Studies of Polymers and Immobilized Sonogashira Catalysts for Cross-Coupling Reactions 

    E-print Network

    Pope, Jacqueline Christine

    2014-08-28

    ............................................................................................. 56 Experimental ......................................................................................... 57 III HIGH-TEMPERATURE STEAM-TREATMENT OF MELT- MOLDED PBI, PEEK, AND PEKK WITH H2O AND D2O: A SOLID-STATE NMR STUDY... ................................................................................................................. 284 xii LIST OF FIGURES FIGURE Page 2.1. 13C CP/MAS NMR spectra of PBI (a), PEEK (b), melt-blended PEEK- PBI (c), and a physical mixture of powdered PEEK and PBI (50:50 wt%) (d). The spinning speed is 10 kHz for all spectra...

  14. Treatment of acid mine drainage with anaerobic solid-substrate reactors

    SciTech Connect

    Drury, W.J.

    1999-10-01

    Anaerobic solid-substrate reactors were used in a laboratory study of acid mine drainage treatment. Parallel systems were run continuously for 23 months, both containing a solid substrate of 2:1 (weight) cow manure and sawdust. One system had cheese whey added with the mine drainage to provide an additional electron donor source to simulate sulfate-reducing bacteria activity. Effluent pH from the reactor with whey addition was relatively constant at 6.5. Effluent pH from the reactor without whey addition dropped over time from 6.7 to approximately 5.5. Whey addition increased effluent alkalinity [550 to 700 mg/L as calcium carbonate (CaCO{sub 3}) versus 50 to 300 mg/L as CaCO{sub 3}] and sulfate removal (98 to 80% versus 60 to 40%). Sulfate removal rate with whey addition decreased over time from 250 to 120 mmol/m{sup 3}{center{underscore}dot}d, whereas it decreased from 250 to 40 mmol/m{sup 3}{center{underscore}dot}d without whey addition. Whey addition increased removal of dissolved iron, dissolved manganese, and dissolved zinc in the second part of the experiment. Copper and cadmium removals were greater than 99%, and arsenic removal was 84% without whey addition and 89% with whey addition. Effluent sulfide concentrations were approximately 1 order of magnitude greater with whey addition. A 63-day period of excessive loading permanently decreased treatment efficiency without whey addition.

  15. Characterization and dynamic properties for the solid inclusion complexes of ?-cyclodextrin and perfluorooctanoic acid.

    PubMed

    Karoyo, Abdalla H; Sidhu, Paul; Wilson, Lee D; Hazendonk, Paul

    2013-07-11

    The structural characterization and dynamic properties of solid-state inclusion complexes (ICs) formed between ?-cyclodextrin (?-CD; host) and perfluorooctanoic acid (PFOA; guest) were investigated using (13)C NMR spectroscopy. The 1:1 and 2:1 host/guest solid-state complexes were prepared using a modified dissolution method to obtain complexes with high phase purity. These complexes were further characterized using differential scanning calorimetry (DSC), FT-IR spectroscopy, powder X-ray diffraction (PXRD), (19)F directpolarization (DP), and (13)C cross-polarization (CP) with magic-angle spinning (MAS) NMR spectroscopy. The (19)F ? (13)C CP results provided unequivocal support for the formation of well-defined inclusion compounds. The phase purity of the complexes formed between ?-CD and PFOA were assessed using the (19)F DP NMR technique at variable temperature (VT) and MAS at 20 kHz. The complexes were found to be of high phase purity when prepared in accordance with the modified dissolution method. The motional dynamics of the guest in the solid complexes were assessed using T1/T2/T1? relaxation NMR methods at ambient and VT conditions. The relaxation data revealed reliable and variable guest dynamics for the 1:1 versus 2:1 complexes at the VTs investigated. The motional dynamics of the guest molecules involve an ensemble of axial motions of the whole chain and 120° rotational jumps of the methyl (CF3) group at the termini of the perfluorocarbon chain. The axial and rotational dynamics of the guest in the 1:1 and 2:1 complexes differ in distribution and magnitude in accordance with the binding geometry of the guest within the host. PMID:23713518

  16. Self-assembly and applications of nucleic acid solid-state films.

    PubMed

    Gajria, Surekha; Neumann, Thorsten; Tirrell, Matthew

    2011-01-01

    While most nucleic acid (NA)-lipid or NA-polymer complexes are studied in solution, there is growing interest in understanding their properties as naturally derived, biodegradable, biocompatible, solid-state materials with tailorable properties influenced by environmental parameters. Therapeutic and cell programming applications comprise an important new research field, particularly in gene transfection and silencing using plasmid DNA and siRNA with targeted local delivery for use in cell culture. Dried solid films have lower nuclease degradation, fewer barriers to long term storage, and allow localized delivery by direct implantation in combination with controlled release and dosage adjustment. In contrast to particulate complexes or other methods of drug delivery which are prepared and must remain in solution, films can regain their biological activity once wetted. However our understanding of the types of cationic agents that predictably form self-standing films with NA is still limited. The self-assembly and structural, physical, and chemical properties of these materials are of key importance to maintaining their activity. We therefore discuss the material properties of NA-lipid and NA-polymer films as the focus of this article. Recent studies have indicated that there is also growing interest in NA films beyond bioengineering and medical applications in the fields of nano- and optoelectronics. We survey the self-assembly of solid-state materials composed of NA complexed with lipids, surfactants, or polymers, and summarize investigations of nanoscopic assembly, structure, optical, and macroscopic material properties. We further evaluate the current and future applications of NA-lipid and NA-polymer films and the benefits and drawbacks of each type. PMID:21638788

  17. Hydrogen generation from magnesium hydride by using organic acid

    NASA Astrophysics Data System (ADS)

    Ho, Yen-Hsi

    In this paper, the hydrolysis of solid magnesium hydride has been studied with the high concentration of catalyst at the varying temperature. An organic acid (acetic acid, CH3COOH) has been chosen as the catalyst. The study has three objectives: first, using three different weights of MgH 2 react with aqueous solution of acid for the hydrogen generation experiments. Secondly, utilizing acetic acid as the catalyst accelerates hydrogen generation. Third, emphasizing the combination of the three operating conditions (the weight of MgH2, the concentration of acetic acid, and the varying temperature) influence the amount of hydrogen generation. The experiments results show acetic acid truly can increase the rate of hydrogen generation and the weight of MgH2 can affect the amount of hydrogen generation more than the varying temperature.

  18. Electron-Withdrawing Trifluoromethyl Groups in Combination with Hydrogen Bonds in Polyols: Brønsted Acids, Hydrogen-Bond Catalysts, and Anion Receptors

    SciTech Connect

    Shokri, Alireza; Wang, Xue B.; Kass, Steven R.

    2013-06-26

    Electron withdrawing trifluoromethyl groups were characterized in combination with hydrogen bond interactions in three polyols (i.e., CF3CH(OH)CH2CH(OH)CF3, 1; (CF3)2C(OH)C(OH)(CF3)2, 2; ((CF3)2C(OH)CH2)2CHOH, 3) by pKa measurements in DMSO and H2O, negative ion photoelectron spectroscopy and binding constant determinations with Cl–. Their catalytic behavior in several reactions were also examined and compared to a BrØnsted acid (HOAc) and a commonly employed thiourea ((3,5-(CF3)3C6H3NH)2CS). The combination of inductive stabilization and hydrogen bonds was found to afford potent acids which are effective catalysts. It also appears that hydrogen bonds can transmit the inductive effect over distance even in an aqueous environment, and this has far reaching implications.

  19. Reuse of sewage sludge as a catalyst in ozonation--efficiency for the removal of oxalic acid and the control of bromate formation.

    PubMed

    Wen, Gang; Pan, Zhi-Hui; Ma, Jun; Liu, Zheng-Qian; Zhao, Lei; Li, Jun-Jing

    2012-11-15

    Sewage derived sludge is produced with an annual amount increase of 2% all over the world and it is an urgent issue to be addressed by human being. In the present study, sludge was converted into sludge-based catalyst (SBC) with ZnCl2 as activation agent and characterized by several methods (e.g., scanning electron microscope, X-ray photoelectron spectroscope and Fourier transform infrared spectroscope). Then it was used as a catalyst to enhance the removal of refractory organic matter, oxalic acid, and to control the formation of bromate (BrO3-) in bench semi-continuous ozonation experiments. The effects of various operating parameters on the control of BrO3- formation were investigated. Furthermore, the mechanism for the enhancement of organic matter removal and the control of BrO3- formation was discussed as well. Results indicate that the combination of SBC with ozone shows a strong synergistic effect, resulting in a notable improvement on oxalic acid removal. A crucial surface reaction mechanism for the enhancement of organic matter removal is proposed on the basis of negative effect of higher pH and no inhibition effect of tert-butanol. The control for BrO3- formation was demonstrated and the reason for its control in the process of O3/SBC is the combined effect of SBC reductive properties, ozone exposure decrease and hydrogen peroxide concentration increase. PMID:23021317

  20. Striking influence of the catalyst support and its acid-base properties: new insight into the growth mechanism of carbon nanotubes.

    PubMed

    Magrez, Arnaud; Smajda, Rita; Seo, Jin Won; Horváth, Endre; Ribic, Primoz Rebernik; Andresen, Juan Carlos; Acquaviva, Donatello; Olariu, Areta; Laurenczy, Gábor; Forró, László

    2011-05-24

    In the accepted mechanisms of carbon nanotube (CNT) growth by catalytic chemical vapor deposition (CCVD), the catalyst support is falsely considered as a passive material whose only role is to prevent catalytic particles from coarsening. The chemical changes that occur to the carbon source molecules on the surface are mainly overlooked. Here, we demonstrate the strong influence of the support on the growth of CNTs and show that it can be tuned by controlling the acid-base character of the support surface. This finding largely clarifies the CCVD growth mechanism. The CNTs' growth stems from the support where the presence of basic sites catalyzes the aromatization and reduces the complexity of CNT precursor molecules. On basic supports, the growth is activated and CNTs are more than 1000 times longer than those produced on acidic supports. These results could be the bedrock of future development of more efficient growth of CNTs on surfaces of functional materials. Finally, the modification of the aciditiy of the catalyst support during the super growth process is also discussed. PMID:21517089

  1. Catalyst Of A Metal Heteropoly Acid Salt That Is Insoluble In A Polar Solvent On A Non-Metallic Porous Support And Method Of Making

    DOEpatents

    Wang. Yong (Richland, WA); Peden. Charles H. F. (West Richland, WA); Choi. Saemin (Richland, WA)

    2004-11-09

    The present invention includes a catalyst having (a) a non-metallic support having a plurality of pores; (b) a metal heteropoly acid salt that is insoluble in a polar solvent on the non-metallic support; wherein at least a portion of the metal heteropoly acid salt is dispersed within said plurality of pores. The present invention also includes a method of depositing a metal heteropoly acid salt that is insoluble in a polar solvent onto a non-metallic support having a plurality of pores. The method has the steps of: (a) obtaining a first solution containing a first precursor of a metal salt cation; (b) obtaining a second solution containing a second precursor of a heteropoly acid anion in a solvent having a limited dissolution potential for said first precursor; (c) impregnating the non-metallic support with the first precursor forming a first precursor deposit within the plurality of pores, forming a first precursor impregnated support; (d) heating said first precursor impregnated support forming a bonded first precursor impregnated support; (e) impregnating the second precursor that reacts with the precursor deposit and forms the metal heteropoly acid salt.

  2. Catalyst-free vapour-solid technique for deposition of Bi2Te3 and Bi2Se3 nanowires/nanobelts with topological insulator properties.

    PubMed

    Andzane, J; Kunakova, G; Charpentier, S; Hrkac, V; Kienle, L; Baitimirova, M; Bauch, T; Lombardi, F; Erts, D

    2015-10-14

    We present a simple two-stage vapour-solid synthesis method for the growth of bismuth chalcogenide (Bi2Te3, Bi2Se3) topological insulator nanowires/nanobelts by using Bi2Se3 or Bi2Te3 powders as source materials. During the first stage of the synthesis process nanoplateteles, serving as "catalysts" for further nanowire/nanobelt growth, are formed. At a second stage of the synthesis, the introduction of a N2 flow at 35 Torr pressure in the chamber induces the formation of free standing nanowires/nanobelts. The synthesised nanostructures demonstrate a layered single-crystalline structure and Bi?:?Se and Bi?:?Te ratios 40?:?60 at% for both Bi2Se3 and Bi2Te3 nanowires/nanobelts. The presence of Shubnikov de Haas oscillations in the longitudinal magneto-resistance of the nanowires/nanobelts and their specific angular dependence confirms the existence of 2D topological surface states in the synthesised nanostructures. PMID:26365282

  3. Catalyst-free vapour-solid technique for deposition of Bi2Te3 and Bi2Se3 nanowires/nanobelts with topological insulator properties

    NASA Astrophysics Data System (ADS)

    Andzane, J.; Kunakova, G.; Charpentier, S.; Hrkac, V.; Kienle, L.; Baitimirova, M.; Bauch, T.; Lombardi, F.; Erts, D.

    2015-09-01

    We present a simple two-stage vapour-solid synthesis method for the growth of bismuth chalcogenide (Bi2Te3, Bi2Se3) topological insulator nanowires/nanobelts by using Bi2Se3 or Bi2Te3 powders as source materials. During the first stage of the synthesis process nanoplateteles, serving as ``catalysts'' for further nanowire/nanobelt growth, are formed. At a second stage of the synthesis, the introduction of a N2 flow at 35 Torr pressure in the chamber induces the formation of free standing nanowires/nanobelts. The synthesised nanostructures demonstrate a layered single-crystalline structure and Bi : Se and Bi : Te ratios 40 : 60 at% for both Bi2Se3 and Bi2Te3 nanowires/nanobelts. The presence of Shubnikov de Haas oscillations in the longitudinal magneto-resistance of the nanowires/nanobelts and their specific angular dependence confirms the existence of 2D topological surface states in the synthesised nanostructures.

  4. Restoration of acidic mine spoils with sewage sludge: II measurement of solids applied

    SciTech Connect

    Stucky, D.J.; Zoeller, A.L.

    1980-01-01

    Sewage sludge was incorporated in acidic strip mine spoils at rates equivalent to 0, 224, 336, and 448 dry metric tons (dmt)/ha and placed in pots in a greenhouse. Spoil parameters were determined 48 hours after sludge incorporation, Time Planting (P), and five months after orchardgrass (Dactylis glomerata L.) was planted, Time Harvest (H), in the pots. Parameters measured were: pH, organic matter content (OM), cation exchange capacity (CEC), electrical conductivity (EC) and yield. Values for each parameter were significantly different at the two sampling times. Correlation coefficient values were calculated for all parameters versus rates of applied sewage sludge and all parameters versus each other. Multiple regressions were performed, stepwise, for all parameters versus rates of applied sewage sludge. Equations to predict amounts of sewage sludge incorporated in spoils were derived for individual and multiple parameters. Generally, measurements made at Time P achieved the highest correlation coefficient and multiple correlation coefficient values; therefore, the authors concluded data from Time P had the greatest predictability value. The most important value measured to predict rate of applied sewage sludge was pH and some additional accuracy was obtained by including CEC in equation. This experiment indicated that soil properties can be used to estimate amounts of sewage sludge solids required to reclaim acidic mine spoils and to estimate quantities incorporated.

  5. Organic acids associated with saccharification of cellulosic wastes during solid-state fermentation.

    PubMed

    El-Naggar, Noura El-Ahmady; El-Hersh, Mohammed Saad

    2011-02-01

    Saccharification of five cellulosic wastes, i.e. rice husks, wheat bran, corn cobs, wheat straw and rice straw by three cellulytic fungi, i.e. Aspergillus glaums MN1, Aspergillus oryzae MN2 and Penicillium purpurogenum MN3, during solid-state fermentation (SSF) was laboratory studied. Rice husks, wheat bran, and corn cobs were selected as inducers of glucose production in the tested fungi. An incubation interval of 10 days was optimal for glucose production. Maximal activities of the cellulases FP-ase, CMC-ase, and p-glucosidase were detected during SSF of rice husks by P. purpurogenum; however, a-amylase activity (7.2 U/g) was comparatively reduced. Meanwhile, the productivities of FP-ase, CMC-ase, and ?-glucosidase were high during SSF of rice husks by A glaucus; however, they decreased during SSF of corn cobs by P. purpurogenum. Addition of rock phosphate (RP) (75 mg P(2)O(5)) decreased the pH of SSF media. (NH(4))(2)SO(4) was found to be less inducer of cellulytic enzymes, during SSF of rice husks by A. glaucus or A. oryzae; it also induced phytase production and solubilization of RP. The organic acids associated with saccharification of the wastes studied have also been investigated. The highest concentration of levulinic acid was detected (46.15 mg/g) during SSF of corn cobs by P. purpurogenum. Likewise, oxalic acid concentration was 43.20 mg/g during SSF of rice husks by P. purpurogenum. PMID:21369980

  6. Analysis of phenolic acids as chloroformate derivatives using solid phase microextraction-gas chromatography.

    PubMed

    Citová, Ivana; Sladkovský, Radek; Solich, Petr

    2006-07-28

    In the presented study, a simple and original procedure of phenolic acids derivatization treated by ethyl and methyl chloroformate performed in an aqueous media consisting of acetonitrile, water, methanol/ethanol and pyridine has been modified and optimized. Seven phenolic acid standards-caffeic, ferulic, gallic, p-coumaric, protocatechuic, syringic and vanillic were derivatized into corresponding methyl/ethyl esters and subsequently determined by the means of gas chromatography connected to the flame-ionisation detector (FID). Some selected validation parameters as linearity, detection and quantitation limits and peak area repeatability were valued. The total time of gas chromatography (GC) analysis was 24 min for methyl chloroformate and 30 min for ethyl chloroformate derivatization. The more suitable methyl chloroformate derivatization was used for further experiments on the possibility of multiple pre-concentration by the direct solid phase microextraction technique (SPME). For this purpose, polyacrylate (PA), polydimethylsiloxane (PDMS), carboxen/polydimethylsiloxane (CAR/PDMS) and polydimethylsiloxane/divinylbenzene (PDMS/DVB) fibres were tested and the extraction conditions concerning time of extraction, temperature and time of desorption were optimized. The most polar PA fibre gave the best results under optimal extraction conditions (50 min extraction time, 25 degrees C extraction temperature and 10 min desorption time). As a result, the total time of SPME-GC analysis was 74 min and an increase in method sensitivity was reached. The limits of quantitation (LOQ) of p-coumaric, ferulic, syringic and vanillic acid esters after SPME pre-concentration were 0.02, 0.17, 0.2 and 0.2 microg mL(-1), respectively, showing approximately 10 times higher sensitivity in comparison with the original GC method. PMID:17723529

  7. Sum Frequency Generation Vibrational Spectroscopy of Adsorbed Amino Acids, Peptides and Proteins of Hydrophilic and Hydrophobic Solid-Water Interfaces

    SciTech Connect

    Holinga IV, G.H.

    2010-08-01

    Sum frequency generation (SFG) vibrational spectroscopy was used to investigate the interfacial properties of several amino acids, peptides, and proteins adsorbed at the hydrophilic polystyrene solid-liquid and the hydrophobic silica solid-liquid interfaces. The influence of experimental geometry on the sensitivity and resolution of the SFG vibrational spectroscopy technique was investigated both theoretically and experimentally. SFG was implemented to investigate the adsorption and organization of eight individual amino acids at model hydrophilic and hydrophobic surfaces under physiological conditions. Biointerface studies were conducted using a combination of SFG and quartz crystal microbalance (QCM) comparing the interfacial structure and concentration of two amino acids and their corresponding homopeptides at two model liquid-solid interfaces as a function of their concentration in aqueous solutions. The influence of temperature, concentration, equilibration time, and electrical bias on the extent of adsorption and interfacial structure of biomolecules were explored at the liquid-solid interface via QCM and SFG. QCM was utilized to quantify the biological activity of heparin functionalized surfaces. A novel optical parametric amplifier was developed and utilized in SFG experiments to investigate the secondary structure of an adsorbed model peptide at the solid-liquid interface.

  8. GC-MS QUANTIFICATION OF THE METHANOL AND ACETIC ACID CONTENT OF PECTIN USING HEADSPACE SOLID-PHASE MICROEXTRACTION

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A simple, fast, and direct procedure was developed for the simultaneous determination of the methanol and acetic acid present as esters in the plant cell wall polysaccharide pectin. After base-hydrolysis of esters and acidification of pectin samples, headspace solid-phase microextraction was perfor...

  9. FEASIBILITY STUDY TO PRODUCE BIODIESEL FROM LOW COST OILS AND NEW CATALYSTS DERIVED FROM AGRICULTURAL & FORESTRY RESIDUES - PHASE I

    EPA Science Inventory

    This research will develop and demonstrate the feasibility of preparing reusable and recoverable solid, porous acid and base catalysts for biodiesel production using activated carbon generated from agricultural and forestry residues (i.e., a sustainable biomass).  These ne...

  10. Incorporating Amino Acid Esters into Catalysts for Hydrogen Oxidation: Steric and Electronic Effects and the Role of Water as a Base

    SciTech Connect

    Lense, Sheri; Ho, Ming-Hsun; Chen, Shentan; Jain, Avijita; Raugei, Simone; Linehan, John C.; Roberts, John A.; Appel, Aaron M.; Shaw, Wendy J.

    2012-10-08

    Four derivatives of a hydrogen oxidation catalyst, [Ni(PCy2NBn-R2)]2+ (Cy=cyclohexyl, Bn=benzyl, R= OMe, COOMe, CO-Alanine-methyl ester or CO-Phenylalanine-methyl ester), have been prepared to investigate steric and electronic effects on catalysis. Each complex was characterized spectroscopically and electrochemically, and thermodynamic data were determined. Crystal structures are also reported for the -OMe and -COOMe derivatives. All four catalysts were found to be active for H2 oxidation. The methyl ester (R = COOMe) and amino acid ester containing complexes (R = CO-Alanine-methyl ester or CO-Phenylalanine-methyl ester) had slower rates (4 s-1) than that of the parent complex (10 s-1), in which R = H, consistent with the lower amine pKa’s and less favorable ?GH2’s found for these electron-withdrawing substituents. Dynamic processes for the amino acid ester containing complexes were also investigated and found not to hinder catalysis. The electron-donating methoxy ether derivative (R = OMe) was prepared to compare electronic effects and has a similar catalytic rate as the parent complex. In the course of these studies, it was found that water could act as a weak base for H2 oxidation, although catalytic turnover requires a significantly higher potential and utilizes a different sequence of catalytic steps than when using a base with a higher pKa. Importantly, these catalysts provide a foundation upon which larger peptides can be attached to [Ni(PCy2NBn2)2]2+ hydrogen oxidation catalysts in order to more fully investigate and implement the effects of the outer-coordination sphere. This work was funded by the DOE Office of Science Early Career Research Program through the Office of Basic Energy Sciences (SL and WJS), by the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Office of Basic Energy Sciences (JR), and by the US DOE Basic Energy Sciences, Chemical Sciences, Geoscience and Biosciences Division (AMA, AJ). Pacific Northwest National Laboratory is operated by Battelle for the U.S. Department of Energy.

  11. Synthesis and Evaluation of Cu/SAPO-34 Catalysts for NH3-SCR 2: Solid-state Ion Exchange and One-pot Synthesis

    SciTech Connect

    Gao, Feng; Walter, Eric D.; Washton, Nancy M.; Szanyi, Janos; Peden, Charles HF

    2015-01-01

    Cu-SAPO-34 catalysts are synthesized using two methods: solid-state ion exchange (SSIE) and one-pot synthesis. SSIE is conducted by calcining SAPO-34/CuO mixtures at elevated temperatures. For the one-pot synthesis method, Cu-containing chemicals (CuO and CuSO4) are added during gel preparation. A high-temperature calcination step is also needed for this method. Catalysts are characterized with surface area/pore volume measurements, temperature programmed reduction (TPR), electron paramagnetic resonance (EPR) and nuclear magnetic resonance (NMR) spectroscopies, and scanning electron microscopy (SEM). Catalytic properties are examined using standard ammonia selective catalytic reduction (NH3-SCR) and ammonia oxidation reactions. In Cu-SAPO-34 samples formed using SSIE, Cu presents both as isolated Cu2+ ions and unreacted CuO. The former is highly active and selective in NH3-SCR, while the latter catalyzes a side reaction; notably, the non-selective oxidation of NH3 above 350 ºC. Using the one-pot method followed by a high-temperature aging treatment, it is possible to form Cu SAPO-34 samples with predominately isolated Cu2+ ions at low Cu loadings. However at much higher Cu loadings, isolated Cu2+ ions that bind weakly with the CHA framework and CuO clusters also form. These Cu moieties are very active in catalyzing non-selective NH3 oxidation above 350 ºC. Low-temperature reaction kinetics indicate that Cu-SAPO-34 samples formed using SSIE have core-shell structures where Cu is enriched in the shell layers; while Cu is more evenly distributed within the one-pot samples. Reaction kinetics also suggest that at low temperatures, the local environment next to Cu2+ ion centers plays little role on the overall catalytic properties. The authors gratefully acknowledge the US Department of Energy (DOE), Energy Efficiency and Renewable Energy, Vehicle Technologies Office for the support of this work. The research described in this paper was performed at the Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by the DOE’s Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory (PNNL). PNNL is operated for the US DOE by Battelle under contract number DE-AC05-76RL01830. The authors also thank Shari Li (PNNL) for surface area/pore volume measurements, and Bruce W. Arey (PNNL) for SEM measurements. Discussions with Drs. A. Yezerets, K. Kamasamudram, J.H. Li, N. Currier and J.Y. Luo from Cummins, Inc. and H.Y. Chen and H. Hess from Johnson-Matthey are greatly appreciated.

  12. An Efficient Protocol for the Green and Solvent-Free Synthesis of Azine Derivatives at Room Temperature Using BiCl3-Loaded Montmorillonite K10 as a New Recyclable Heterogeneous Catalyst

    PubMed Central

    Ravi, K.; Krishnakumar, B.; Swaminathan, M.

    2012-01-01

    A new BiCl3-loaded montmorillonite K10 catalyst has been prepared by solid dispersion method and was characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), and cyclic voltammetry (CV) measurements. BiCl3 loaded K10 (BiCl3-K10) has been used as solid acid catalyst for the synthesis of azine derivatives from benzophenone hydrazone and ketones/aldehydes by simple physical grinding. This BiCl3-K10 gives an excellent yield with short reaction time and is an inexpensive, easily recyclable catalyst for this reaction. PMID:24052847

  13. Changes in lipid, fatty acids and phospholipids composition of whole rice bran after solid-state fungal fermentation.

    PubMed

    Oliveira, Melissa Dos Santos; Feddern, Vivian; Kupski, Larine; Cipolatti, Eliane Pereira; Badiale-Furlong, Eliana; de Souza-Soares, Leonor Almeida

    2011-09-01

    The aim of this study was to evaluate fermented rice bran phospholipids, lipids and fatty acid content in a fermentation solid system with Rhizopus oryzae fungus. For this, aliquots were withdrawn every 24h over 120 h. The content of phospholipids was determined by colorimetric method. Esterified fatty acids were separated by gas chromatography, then identified and quantified. The total lipids from fermented rice bran (FB) decreased from 20.4% to 11.2% in the range between 0 h and 120 h of fermentation while phospholipid contents were increased up to 2.4 mg P g(lipid)(-1). In fermented bran, oleic, palmitic and linoleic acids prevailed, with a decrease in saturated fatty acids (20%) and increase in the unsaturated ones (5%). This study showed that rice bran fermentation with R. oryzae can be applied to the production of phospholipids altering the saturated to unsaturated fatty acid ratio. PMID:21715163

  14. Catalysts for emerging energy applications

    SciTech Connect

    Bruce C. Gates; George W. Huber; Christopher L. Marshall; Phillip N. Ross; Jeffrey Siirola; Yong Wang

    2008-04-15

    Catalysis is the essential technology for chemical transformation, including production of fuels from the fossil resources petroleum, natural gas, and coal. Typical catalysts for these conversions are robust porous solids incorporating metals, metal oxides, and/or metal sulfides. As efforts are stepping up to replace fossil fuels with biomass, new catalysts for the conversion of the components of biomass will be needed. Although the catalysts for biomass conversion might be substantially different from those used in the conversion of fossil feedstocks, the latter catalysts are a starting point in today's research. Major challenges lie ahead in the discovery of efficient biomass conversion catalysts, as well as in the discovery of catalysts for conversion of CO{sub 2} and possibly water into liquid fuels. 16 refs., 6 figs., 1 tab.

  15. Catalytic solvent delignification of agricultural residues: organic catalysts

    SciTech Connect

    Ghose, T.K.; Pannir Selvam, P.V.; Ghosh, P.

    1983-11-01

    The effects of moderate-temperature aqueous butanol pretreatment of rice straw on several organic catalysts have been studied. Maximum delignification was obtained with an aromatic organic acid catalyst. Presoaking of straw in aqueous butanol improved delignifiction, particularly in high solid-liquid ratios. However, due to the difficulty of penetration of lignin into the solvent phase, an increase in the solid-liquid ratio appears to affect delignification. A two-stage catalytic solvent process involving presoaking at 80 degrees C followed by delignification at 120 degrees C resulted in 83% removal of lignin in aqueous-butanol, whereas 75% lignin removal was possible in ethanol. Higher reduction in the crystallinity was possible with ethanol. Lignin produced by the solvent process offers desirable physical properties for polymer applications compared to Kraft lignin. (Refs. 26).

  16. Catalysts and method

    DOEpatents

    Taylor, Charles E. (Pittsburgh, PA); Noceti, Richard P. (Pittsburgh, PA)

    1991-01-01

    An improved catlayst and method for the oxyhydrochlorination of methane is disclosed. The catalyst includes a pyrogenic porous support on which is layered as active material, cobalt chloride in major proportion, and minor proportions of an alkali metal chloride and of a rare earth chloride. On contact of the catalyst with a gas flow of methane, HC1 and oxygen, more than 60% of the methane is converted and of that converted more than 40% occurs as monochloromethane. Advantageously, the monochloromethane can be used to produce gasoline boiling range hydrocarbons with the recycle of HCl for further reaction. This catalyst is also of value for the production of formic acid as are analogous catalysts with lead, silver or nickel chlorides substituted for the cobalt chloride.

  17. Bioconversion of municipal solid waste and recovery of short-chain organic acids for liquid fuels production

    SciTech Connect

    Antonopoulos, A.A.; Wene, E.G.

    1988-05-01

    The purpose of this investigation is to determine the feasibility of bioprocessing municipal solid waste (MSW) to produce organic acids and recover the acids for hydrocarbon fuels production. This work has focused on acid production from anaerobic digestion of a simulated MSW material and a densified refuse-derived-fuels MSW substrate using 5-L continuously stirred and 12-L packed-bed anaerobic digesters. Methane generation was inhibited by heat treatment, addition of a methanogen-inhibiting compound, low pH, inoculum from a long-term acid-adapted culture, and short retention times. Steady-state operation was reached with acid concentrations of 15,000 to 18,000 mg/L. Nitrogen supplements to the feedstock increased volatile acid concentrations to between 27,000 and 30,000 mg/L. Extraction of digester fluids containing 15,000 mg/L total acids with trioctylphosphine oxide in heptane recovered more than 82% of the acid in a single extraction. Work continues on maximizing the acid production and recovery from anaerobically digested MSW substrate. 56 refs., 17 figs., 3 tabs.

  18. Control of product selectivity using solid acids for the catalytic addition of phenol to hydroxy fatty acids

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The acid catalyzed reactions of hydroxy fatty acids, such as ricinoleic and lesquerolic, in the presence of phenolics can lead to four products or product groups. These include simple dehydration to dienoic acids, cyclization to epoxides, Friedel-Crafts alkylations of the double bonds, or ether for...

  19. Spectroscopic studies of solid-state forms of donepezil free base and salt forms with various salicylic acids

    NASA Astrophysics Data System (ADS)

    Brittain, Harry G.

    2014-12-01

    The polymorphic forms of donepezil free base have been studied using X-ray powder diffraction, Fourier transform infrared absorption spectroscopy, and differential scanning calorimetry. None of the free base crystal forms was observed to exhibit detectable fluorescence in the solid state under ambient conditions. Crystalline salt products were obtained by the reaction of donepezil with salicylic and methyl-substituted salicylic acids, with the salicylate and 4-methylsalicylate salts being obtained as non-solvated products, and the 3-methylsalicylate and 5-methylsalicylate salts being obtained as methanol solvated products. The intensity of solid-state fluorescence from donepezil salicylate and donepezil 4-methylsalicylate was found to be reduced relative to the fluorescence intensity of the corresponding free acids, while the solid-state fluorescence intensity of donepezil 3-methylsalicylate methanolate and donepezil 5-methylsalicylate methanolate was greatly increased relative to the fluorescence intensity of the corresponding free acids. Desolvation of the solvated salt products led to formation of glassy solids that exhibited strong green fluorescence.

  20. Control of metal dispersion and structure by changes in the solid-state chemistry of supported cobalt FischerTropsch catalysts

    E-print Network

    Iglesia, Enrique

    cobalt Fischer­Tropsch catalysts Stuart L. Soleda,Ã, Enrique Iglesiaa,b , Rocco A. Fiatoa , Joseph E, USA Controlling preparation variables in supported cobalt Fischer­Tropsch catalysts has a dramatic effect on the dispersion and distribution of cobalt, and determines how active and selective

  1. Phosphotungstic acid as a versatile catalyst for the synthesis of fragrance compounds by alpha-pinene oxide isomerization: solvent-induced chemoselectivity.

    PubMed

    da Silva Rocha, Kelly A; Hoehne, Juliana L; Gusevskaya, Elena V

    2008-01-01

    The remarkable effect of the solvent on the catalytic performance of H3PW12O40, the strongest heteropoly acid in the Keggin series, allows direction of the transformations of alpha-pinene oxide (1) to either campholenic aldehyde (2), trans-carveol (3), trans-sobrerol (4 a), or pinol (5). Each of these expensive fragrance compounds was obtained in good to excellent yields by using an appropriate solvent. Solvent polarity and basicity strongly affect the reaction pathways: nonpolar nonbasic solvents favor the formation of aldehyde 2; polar basic solvents favor the formation of alcohol 3; whereas in polar weakly basic solvents, the major products are compounds 4 a and 5. On the other hand, in 1,4-dioxane, which is a nonpolar basic solvent, both aldehyde 2 and alcohol 3 are formed in comparable amounts. The use of very low catalyst loading (0.005-1 mol %) and the possibility of catalyst recovery and recycling without neutralization are significant advantages of this simple, environmentally benign, and low-cost method. This method represents the first example of the synthesis of isomers from alpha-pinene oxide, other than campholenic aldehyde, with a selectivity that is sufficient for practical usage. PMID:18512831

  2. Polymorphism in sulfadimidine/4-aminosalicylic acid cocrystals: solid-state characterization and physicochemical properties.

    PubMed

    Grossjohann, Christine; Serrano, Dolores R; Paluch, Krzysztof J; O'Connell, Peter; Vella-Zarb, Liana; Manesiotis, Panagiotis; Mccabe, Thomas; Tajber, Lidia; Corrigan, Owen I; Healy, Anne Marie

    2015-04-01

    Polymorphism of crystalline drugs is a common phenomenon. However, the number of reported polymorphic cocrystals is very limited. In this work, the synthesis and solid-state characterization of a polymorphic cocrystal composed of sulfadimidine (SD) and 4-aminosalicylic acid (4-ASA) is reported for the first time. By liquid-assisted milling, the SD:4-ASA 1:1 form I cocrystal, the structure of which has been previously reported, was formed. By spray drying, a new polymorphic form (form II) of the SD:4-ASA 1:1 cocrystal was discovered which could also be obtained by solvent evaporation from ethanol and acetone. Structure determination of the form II cocrystal was calculated using high-resolution X-ray powder diffraction. The solubility of the SD:4-ASA 1:1 cocrystal was dependent on the pH and predicted by a model established for a two amphoteric component cocrystal. The form I cocrystal was found to be thermodynamically more stable in aqueous solution than form II, which showed transformation to form I. Dissolution studies revealed that the dissolution rate of SD from both cocrystals was enhanced when compared with a physical equimolar mixture and pure SD. © 2015 Wiley Periodicals, Inc. and the American Pharmacists Association J Pharm Sci 104:1385-1398, 2015. PMID:25605031

  3. Development of Quinic Acid-Conjugated Nanoparticles as a Drug Carrier to Solid Tumors

    PubMed Central

    Amoozgar, Zohreh; Park, Joonyoung; Lin, Qingnuo; Weidle, Johann H.; Yeo, Yoon

    2013-01-01

    Nanometer-sized drug carriers including polymeric nanoparticles (NPs) have been used to increase biodistribution of a drug in tumors, thereby reducing the effective dose of chemotherapy. NPs increase drug delivery to tumors to a certain extent, but the amount reaching tumors is only a small fraction of the total administered NPs because they depend on passive accumulation via the leaky vasculature surrounding tumors. In an attempt to further increase the drug delivery to tumors, we develop a polymeric NP system that interacts with an endothelial tumor marker. The NPs are decorated with quinic acid, a synthetic mimic of sialyl lewis-x, which binds to E-selectin, overexpressed on the surface of endothelial cells surrounding solid tumors. The NPs selectively bind to endothelial cells activated with tumor necrosis factor-?, with weak affinity at a relatively high shear stress. These properties may help NPs reach tumors by increasing the encounter of NPs with the peritumoral endothelium without hindering subsequent transport of the NPs. PMID:23738975

  4. Coating Solid Lipid Nanoparticles with Hyaluronic Acid Enhances Antitumor Activity against Melanoma Stem-like Cells

    PubMed Central

    Shen, Hongxin; Shi, Sanjun; Zhang, Zhirong; Gong, Tao; Sun, Xun

    2015-01-01

    Successful anticancer chemotherapy requires targeting tumors efficiently and further potential to eliminate cancer stem cell (CSC) subpopulations. Since CD44 is present on many types of CSCs, and it binds specially to hyaluronic acid (HA), we tested whether coating solid lipid nanoparticles with hyaluronan (HA-SLNs)would allow targeted delivery of paclitaxel (PTX) to CD44-overexpressing B16F10 melanoma cells. First, we developed a model system based on melanoma stem-like cells for experiments in vitro and in mouse xenografts, and we showed that cells expressing high levels of CD44 (CD44+) displayed a strong CSC phenotype while cells expressing low levels of CD44 (CD44-) did not. This phenotype included sphere and colony formation, higher proportion of side population cells, expression of CSC-related markers (ALDH, CD133, Oct-4) and tumorigenicity in vivo. Next we showed that administering PTX-loaded HA-SLNs led to efficient intracellular delivery of PTX and induced substantial apoptosis in CD44+ cells in vitro. In the B16F10-CD44+ lung metastasis model, PTX-loaded HA-SLNs targeted the tumor-bearing lung tissues well and subsequently exhibited significant antitumor effects with a relative low dose of PTX, which provided significant survival benefit without evidence of adverse events. These findings suggest that the HA-SLNs targeting system shows promise for enhancing cancer therapy. PMID:25897340

  5. Nuclear dynamics in the metastable phase of the solid acid caesium hydrogen sulfate.

    PubMed

    Krzystyniak, Maciej; Dru?bicki, Kacper; Fernandez-Alonso, Felix

    2015-11-18

    High-resolution spectroscopic measurements using thermal and epithermal neutrons and first-principles calculations within the framework of density-functional theory are used to investigate the nuclear dynamics of light and heavy species in the metastable phase of caesium hydrogen sulfate. Within the generalised-gradient approximation, extensive calculations show that both 'standard' and 'hard' formulations of the Perdew-Burke-Ernzerhof functional supplemented by Tkatchenko-Scheffler dispersion corrections provide an excellent description of the known structure, underlying vibrational density of states, and nuclear momentum distributions measured at 10 and 300 K. Encouraged by the agreement between experiment and computational predictions, we provide a quantitative appraisal of the quantum contributions to nuclear motions in this solid acid. From this analysis, we find that only the heavier caesium atoms reach the classical limit at room temperature. Contrary to naïve expectation, sulfur exhibits a more pronounced quantum character relative to classical predictions than the lighter oxygen atom. We interpret this hitherto unexplored nuclear quantum effect as arising from the tighter binding environment of this species in this technologically relevant material. PMID:26549527

  6. Preparation and investigation of mefenamic acid - polyethylene glycol - sucrose ester solid dispersions.

    PubMed

    Fülöp, Ibolya; Gyéresi, Árpád; Kiss, Lóránd; Deli, Mária A; Croitoru, Mircea Dumitru; Szabó-Révész, Piroska; Aigner, Zoltán

    2015-12-01

    Mefenamic acid (MA) is a widely used non-steroidal antiinflammatory (NSAID) drug. The adverse effects typical of NSAIDs are also present in the case of MA, partly due to its low water solubility. The aim of this study was to increase the water solubility of MA in order to influence its absorption and bioavailability. Solid dispersions of MA were prepared by the melting method using polyethylene glycol 6000 and different types (laurate, D-1216; palmitate, P-1670; stearate, S-1670) and amounts of sucrose esters as carriers. The X-ray diffraction results show that MA crystals were not present in the products. Dissolution tests carried out in artificial intestinal juice showed that the product containing 10 % D-1216 increased water solubility about 3 times. The apparent permeability coefficient of MA across human Caco-2 intestinal epithelial cell layers was high and, despite the difference in solubility, there was no further increase in drug penetration in the presence of the applied additives. PMID:26677901

  7. IMPROVED PROCESSES TO REMOVE NAPHTHENIC ACIDS

    SciTech Connect

    Aihua Zhang; Qisheng Ma; William A. Goddard; Yongchun Tang

    2004-04-28

    In the first year of this project, we have established our experimental and theoretical methodologies for studies of the catalytic decarboxylation process. We have developed both glass and stainless steel micro batch type reactors for the fast screening of various catalysts with reaction substrates of model carboxylic acid compounds and crude oil samples. We also developed novel product analysis methods such as GC analyses for organic acids and gaseous products; and TAN measurements for crude oil. Our research revealed the effectiveness of several solid catalysts such as NA-Cat-1 and NA-Cat-2 for the catalytic decarboxylation of model compounds; and NA-Cat-5{approx}NA-Cat-9 for the acid removal from crude oil. Our theoretical calculations propose a three-step concerted oxidative decarboxylation mechanism for the NA-Cat-1 catalyst.

  8. Biodiesel production using cation-exchange resin as heterogeneous catalyst.

    PubMed

    Feng, Yaohui; He, Benqiao; Cao, Yuhe; Li, Jianxin; Liu, Meng; Yan, Feng; Liang, Xiaoping

    2010-03-01

    Three types of cation-exchange resins (NKC-9, 001 x 7 and D61) as solid acid catalysts were employed to prepare biodiesel from acidified oils generated from waste frying oils. The results show that the catalytic activity of NKC-9 was higher than that of 001 x 7 and D61. The conversion of the esterification by NKC-9 increased with increasing in the amount of catalyst, reaction temperature and time and methanol/oil molar ratio. The maximal conversion of reaction is approximately 90.0%. Furthermore, NKC-9 resin exhibits good reusability. Gas chromatography-mass spectrometry analysis reveals that the production is simplex and mainly composed of C16:0 (palmitic), C18:2 (linoleic), and C18:1 (oleic) acids of methyl ester, respectively. PMID:19699089

  9. 7 CFR 51.1178 - Maximum anhydrous citric acid permissible for corresponding total soluble solids.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ...2010-01-01 false Maximum anhydrous citric acid permissible for corresponding total soluble... § 51.1178 Maximum anhydrous citric acid permissible for corresponding total soluble...the maximum permissible anhydrous citric acid content in relation to...

  10. In situ FTIR investigation of acetic acid electrooxidation on carbon supported Pt-Sn based trimetallic catalysts: Influence of the nature of the third metal

    NASA Astrophysics Data System (ADS)

    Beyhan, Seden; Léger, Jean-Michel; Kad?rgan, Figen

    2014-12-01

    The effect of adding a third metal (Ni, Co, Pd, Rh) to Pt-Sn/C catalyst has been investigated for the adsorption and oxidation of acetic acid in acidic medium using in situ Fourier transform infrared (FTIR) spectroscopy. The results showed that the decomposition of acetic acid on the surface leads to the formation of different intermediate species and products such as acetate, acetyl, carbonate, CO and CO2. The reaction pathway of CO2 production proceeds via the formation of acetyl or carbonate through surface acetate species. It has been found that the selectivity of the acetate was enhanced by the addition of any third metal. However, the presence of Pd or Co increases the relative intensity of IR band for CO2. This is probably due to success in facilitating of the Csbnd C bond cleavage of acetyl. On the other hand, the conversion of acetate to carbonate is strongly affected by the adsorbed water, as is evident from the pronounced changes in the OH stretching region with the presence of Pd or Ni.

  11. Direct tandem mass spectrometric analysis of amino acids in plasma using fluorous derivatization and monolithic solid-phase purification.

    PubMed

    Tamashima, Erina; Hayama, Tadashi; Yoshida, Hideyuki; Imakyure, Osamu; Yamaguchi, Masatoshi; Nohta, Hitoshi

    2015-11-10

    In this study, we developed a novel direct tandem mass spectrometric method for rapid and accurate analysis of amino acids utilizing a fluorous derivatization and purification technique. Amino acids were perfluoroalkylated with 2H,2H,3H,3H-perfluoroundecan-1-al in the presence of 2-picoline borane via reductive amination. The derivatives were purified by perfluoroalkyl-modified silica-based monolithic solid-phase extraction (monolithic F-SPE), and directly analyzed by tandem mass spectrometry using electrospray ionization without liquid chromatographic separation. The perfluoroalkyl derivatives could be sufficiently distinguished from non-fluorous compounds, i.e. the biological matrix, due to their fluorous interaction. Thus, rapid and accurate determination of amino acids was accomplished. The method was validated with human plasma samples and applied to the analysis of amino acids in the plasma of mice with maple syrup urine disease or phenylketonuria. PMID:26222276

  12. Enhancement of alkylation catalysts for improved supercritical fluid regeneration

    DOEpatents

    Ginosar, Daniel M. (Idaho Falls, ID); Petkovic, Lucia M. (Idaho Falls, ID)

    2010-12-28

    A method of modifying an alkylation catalyst to reduce the formation of condensed hydrocarbon species thereon. The method comprises providing an alkylation catalyst comprising a plurality of active sites. The plurality of active sites on the alkylation catalyst may include a plurality of weakly acidic active sites, intermediate acidity active sites, and strongly acidic active sites. A base is adsorbed to a portion of the plurality of active sites, such as the strongly acidic active sites, selectively poisoning the strongly acidic active sites. A method of modifying the alkylation catalyst by providing an alkylation catalyst comprising a pore size distribution that sterically constrains formation of the condensed hydrocarbon species on the alkylation catalyst or by synthesizing the alkylation catalyst to comprise a decreased number of strongly acidic active sites is also disclosed, as is a method of improving a regeneration efficiency of the alkylation catalyst.

  13. Enhancement of alkylation catalysts for improved supercritical fluid regeneration

    DOEpatents

    Ginosar, Daniel M. (Idaho Falls, ID); Petkovic, Lucia (Idaho Falls, ID)

    2009-09-22

    A method of modifying an alkylation catalyst to reduce the formation of condensed hydrocarbon species thereon. The method comprises providing an alkylation catalyst comprising a plurality of active sites. The plurality of active sites on the alkylation catalyst may include a plurality of weakly acidic active sites, intermediate acidity active sites, and strongly acidic active sites. A base is adsorbed to a portion of the plurality of active sites, such as the strongly acidic active sites, selectively poisoning the strongly acidic active sites. A method of modifying the alkylation catalyst by providing an alkylation catalyst comprising a pore size distribution that sterically constrains formation of the condensed hydrocarbon species on the alkylation catalyst or by synthesizing the alkylation catalyst to comprise a decreased number of strongly acidic active sites is also disclosed, as is a method of improving a regeneration efficiency of the alkylation catalyst.

  14. Molecular water oxidation catalyst

    DOEpatents

    Gratzel, Michael (St. Sulpice, CH); Munavalli, Shekhar (Bel Air, MD); Pern, Fu-Jann (Lakewood, CO); Frank, Arthur J. (Lakewood, CO)

    1993-01-01

    A dimeric composition of the formula: ##STR1## wherein L', L", L'", and L"" are each a bidentate ligand having at least one functional substituent, the ligand selected from bipyridine, phenanthroline, 2-phenylpyridine, bipyrimidine, and bipyrazyl and the functional substituent selected from carboxylic acid, ester, amide, halogenide, anhydride, acyl ketone, alkyl ketone, acid chloride, sulfonic acid, phosphonic acid, and nitro and nitroso groups. An electrochemical oxidation process for the production of the above functionally substituted bidentate ligand diaqua oxo-bridged ruthenium dimers and their use as water oxidation catalysts is described.

  15. Improved Rhodium Hydrogenation Catalysts Immobilized on Oxidic Supports

    E-print Network

    Bluemel, Janet

    #12;Improved Rhodium Hydrogenation Catalysts Immobilized on Oxidic Supports C. Merckle, J. Bl: November 27, 2002; Accepted: January 19, 2003 Abstract: Wilkinson-type rhodium hydrogenation catalysts hydrogena- tion; immobilization; P ligands; rhodium; silica; solid-state NMR The immobilization

  16. Gallic Acid Production with Mouldy Polyurethane Particles Obtained from Solid State Culture of Aspergillus niger GH1.

    PubMed

    Mata-Gómez, Marco; Mussatto, Solange I; Rodríguez, Raul; Teixeira, Jose A; Martinez, Jose L; Hernandez, Ayerim; Aguilar, Cristóbal N

    2015-06-01

    Gallic acid production in a batch bioreactor was evaluated using as catalytic material the mouldy polyurethane solids (MPS) obtained from a solid-state fermentation (SSF) bioprocess carried out for tannase production by Aspergillus niger GH1 on polyurethane foam powder (PUF) with 5 % (v/w) of tannic acid as inducer. Fungal biomass, tannic acid consumption and tannase production were kinetically monitored. SSF was stopped when tannase activity reached its maximum level. Effects of washing with distilled water and drying on the tannase activity of MPS were determined. Better results were obtained with dried and washed MPS retaining 84 % of the tannase activity. Maximum tannase activity produced through SSF after 24 h of incubation was equivalent to 130 U/gS with a specific activity of 36 U/mg. The methylgallate was hydrolysed (45 %) in an easy, cheap and fast bioprocess (30 min). Kinetic parameters of tannase self-immobilized on polyurethane particles were calculated to be 5 mM and 04.1?×?10(-2) mM/min for K M and V max, respectively. Results demonstrated that the MPS, with tannase activity, can be successfully used for the production of the antioxidant gallic acid from methyl-gallate substrate. Direct use of PMS to produce gallic acid can be advantageous as no previous extraction of enzyme is required, thus reducing production costs. PMID:25920332

  17. Amino acids chemical stability submitted to solid state irradiation: the case study of leucine, isoleucine and valine.

    PubMed

    Cherubini, Cristina; Ursini, Ornella

    2015-01-01

    A solid state radiolysis was conducted to examine the reactivity of amino acids towards high energy dose of gamma radiations. The presence of amino acids in the bulk of meteorites has raised the question of "if" and eventually "how" they could have been important in the development of life on Earth. The presence of radioactive elements in Solar System bodies could have played a crucial role in amino acids survival and in the formation of different organic molecules. The radioactive elements produced a total radiation dose of 14 MGy during the life of Solar System (4.6 × 10(9) years). The aim of this study is to investigate the amino acids capacity to survive at a dose of ?-irradiation equivalent to 1.05 × 10(9) years of Solar System life. In particular, we examined the behavior of three essential amino acids (leucine, isoleucine and valine) submitted to a total dose of 3.2 MGy. We choose to irradiate l-enantiomers to analyze the behavior of a single enantiomer to radiations. We identified the radiation products formed in solid state radiolysis by mass spectrometric analysis and we were able to enlighten some common reactions. These reactions are particularly important to rationalize the formation of prebiotic molecules. Moreover, we studied the radioracemization process, the formation of d-enantiomer promoted by ?-irradiation. PMID:26413447

  18. Use of solid-state 13C NMR in structural studies of humic acids and humin from Holocene sediments

    USGS Publications Warehouse

    Hatcher, P.G.; VanderHart, D.L.; Earl, W.L.

    1980-01-01

    13C NMR spectra of solid humic substances in Holocene sediments have been obtained using cross polarization with magic-angle sample spinning techniques. The results demonstrate that this technique holds great promise for structural characterizations of complex macromolecular substances such as humin and humic acids. Quantifiable distinctions can be made between structural features of aquatic and terrestrial humic substances. The aliphatic carbons of the humic substances are dominant components suggestive of input from lipid-like materials. An interesting resemblance is also noted between terrestrial humic acid and humin spectra. ?? 1980.

  19. Preparation of fibrous titania oxynitride - carbon catalyst and oxygen reduction reaction analysis in both acidic and alkaline media

    NASA Astrophysics Data System (ADS)

    Kinumoto, Taro; Sou, Yoshinori; Ono, Kohei; Matsuoka, Miki; Arai, Yasuhiko; Tsumura, Tomoki; Toyoda, Masahiro

    2015-01-01

    A fibrous catalyst of titania oxynitride and carbon is prepared and its catalytic behavior in the oxygen reduction reaction (ORR) are investigated in both HClO4 and KOH aqueous solutions. TiO2 particles are successfully deposited on activated carbon fibers by a liquid phase deposition technique using (NH4)2TiF6 and H3BO3. The catalyst obtained after subsequent ammonia nitridation at 1273 K had a fibrous structure with TiOxNy and TiN components. Interestingly, the product demonstrates catalytic activity for the ORR in not only HClO4 but also KOH aqueous solution. The onset potential in HClO4 solution is assumed to be moderate, at 0.85 V; on the other hand, that in KOH solution is relatively high at 0.95 V. Furthermore, it is considered from the Tafel plot analysis of the KOH solution result that the ORR mechanism follows a peroxide intermediate pathway and the rate-determining step would be a one-electron-transfer reaction to oxygen molecules adsorbed on the active site.

  20. Characterization of dispersed heteropoly Acid on mesoporous zeolite using solid-state 31P NMR spin-lattice relaxation.

    PubMed

    Zhu, Kake; Hu, Jianzhi; She, Xiaoyan; Liu, Jun; Nie, Zimin; Wang, Yong; Peden, Charles H F; Kwak, Ja Hun

    2009-07-22

    Dispersion and quantitative characterization of supported catalysts is a grand challenge in catalytic science. In this paper, heteropoly acid H(3)PW(12)O(40) (HPA) is dispersed on mesoporous zeolite silicalite-1 derived from hydrothermal synthesis using carbon black nanoparticle templates, and the catalytic activity is studied for 1-butene isomerization. The HPAs supported on conventional zeolite and on mesoporous zeolite exhibit very different activities and thus provide good model systems to investigate the structure dependence of the catalytic properties. The HPA on mesoporous silicalite-1 shows enhanced catalytic activity for 1-butene isomerization, while HPA on conventional silicalite-1 exhibits low activity. To elucidate the structural difference, supported HPA catalysts are characterized using a variety of techniques, including (31)P magic angle spinning nuclear magnetic resonance, and are shown to contain a range of species on both mesoporous and conventional zeolites. However, contrary to studies reported in the literature, conventional NMR techniques and chemical shifts alone do not provide sufficient information to distinguish the dispersed and aggregated surface species. The dispersed phase and the nondispersed phase can only be unambiguously and quantitatively characterized using spin-lattice relaxation NMR techniques. The HPA supported on mesoporous zeolite contains a fast relaxation component related to the dispersed catalyst, giving a much higher activity, while the HPA supported on conventional zeolite has essentially only the slow relaxation component with very low activity. The results obtained from this work demonstrate that the combination of spinning sideband fitting and spin-lattice relaxation techniques can provide detailed structural information on not only the Keggin structure for HPA but also the degree of dispersion on the support. PMID:19601683

  1. Characterization of Dispersed Heteropoly Acid on Mesoporous Zeolite Using Solid-State P-31 NMR Spin-Lattice Relaxation

    SciTech Connect

    Zhu, Kake; Hu, Jian Z.; She, Xiaoyan; Liu, Jun; Nie, Zimin; Wang, Yong; Peden, Charles HF; Kwak, Ja Hun

    2009-09-01

    Dispersion and quantitative characterization of supported catalysts is a grand challenge in catalytic science. In this paper, heteropoly acid H3PW12O40 (HPA) is dispersed on mesoporous zeolite silicalite-1 derived from hydrothermal synthesis using carbon black nanoparticle templates, and the catalytic activity is studied for 1-butene isomerization. The HPAs supported on conventional zeolite and on mesoporous zeolite exhibit very different activities and thus provide good model systems to investigate the structure dependence of the catalytic properties. The HPA on mesoporous silicalite-1 shows enhanced catalytic activity for 1-butene isomerization, while HPA on conventional silicalite-1 exhibits low activity. To elucidate the structural difference, supported HPA catalysts are characterized using a variety of techniques, including 31P magic angle spinning nuclear magnetic resonance, and are shown to contain a range of species on both mesoporous and conventional zeolites. However, contrary to studies reported in the literature, conventional NMR techniques and chemical shifts alone do not provide sufficient information to distinguish the dispersed and aggregated surface species. The dispersed phase and the nondispersed phase can only be unambiguously and quantitatively characterized using spin-lattice relaxation NMR techniques. The HPA supported on mesoporous zeolite contains a fast relaxation component related to the dispersed catalyst, giving a much higher activity, while the HPA supported on conventional zeolite has essentially only the slow relaxation component with very low activity. The results obtained from this work demonstrate that the combination of spinning sideband fitting and spin-lattice relaxation techniques can provide detailed structural information on not only the Keggin structure for HPA but also the degree of dispersion on the support.

  2. Oxidative degradation of 2,4,6-trichlorophenol and pentachlorophenol in contaminated soil suspensions using a supramolecular catalyst of 5,10,15,20-tetrakis (p-hydroxyphenyl)porphine-iron(III) bound to humic acid via formaldehyde polycondensation.

    PubMed

    Fukushima, Masami; Shigematsu, Satoko; Nagao, Seiya

    2009-09-01

    A supramolecular catalyst consisting of 5,10,15,20-tetrakis(p-hydroxyphenyl)porphine-iron(III) (FeTPP(OH)(4)) bound to humic acid (HA) was synthesized via formaldehyde polycondensation. The catalytic system, which included the synthesized catalyst (resol) and an oxygen donor (KHSO(5)), was applied to the oxidative degradation of 2,4,6-trichlorophenol (TrCP) and pentachlorophenol (PCP) in contaminated soil suspensions. The optimal conditions (catalyst, KHSO(5) and substrate concentrations) were investigated. In both FeTPP(OH)(4) and resol catalytic systems, more than 95% of TrCP (100 microM) and PCP (25 microM) degraded at pH 4, [catalyst] 20 microM and [KHSO(5)] 1 mM. When initial concentrations of TrCP and PCP were increased to [TrCP](0) 200 micro M and [PCP](0) 50 micro M, the percent degradation of the CPs and the levels of dechlorination in the resol catalytic system were significantly greater than the values obtained using the FeTPP(OH)(4) system. These results show that the synthesized resol catalyst effectively enhances oxidative degradation of TrCP and PCP in contaminated soil suspensions. The resol catalysts adsorbed to contaminated soils were at levels that were significantly greater than those of FeTPP(OH)(4). Therefore, the enhanced degradation of CPs by resol catalysts can be attributed to the interactions between adsorbed CPs on the soil surface and the catalytic center of the resol catalysts. PMID:19847698

  3. Chemical Interactions in Multimetal/Zeolite Catalysts

    SciTech Connect

    Sachtler, Wolfgang M. H.

    2004-04-16

    This two-year project has led to a significant improvement in the fundamental understanding of the catalytic action of zeolite-supported redox catalysts. It turned out to be essential that we could combine four strategies for the preparation of catalysts containing transition metal (TM) ions in zeolite cavities: (1) ion exchange from aqueous solution; (2) chemical vapor deposition (CVD) of a volatile halide onto a zeolite in its acidic form; (3) solid state ion exchange; and (4) hydrothermal synthesis of a zeolite having TM ions in its lattice, followed by a treatment transporting these ions to ''guest positions''. Technique (2) enables us to position more TM ions into cavities than permitted by the conventional technique (1).viz one positive charge per Al centered tetrahedron in the zeolite lattice. The additional charge is compensated by ligands to the TM ions, for instance in oxo-ions such as (GaO){sup +} or dinuclear [Cu-O-Cu]{sup 2+}. While technique (3) is preferred over CVD where volatile halides are not available, technique (4) leads to rather isolated ''ex lattice'' oxo-ions. Such oxo-ions tend to be mono-nuclear, in contrast to technique (2) which preferentially creates dinuclear oxo-ions of the same TM element. A favorable element for the present research was that the PI is also actively engaged in a project on the reduction of nitrogen oxides, sponsored by EMSI program of the National Science Foundation and the US Department of Energy, Office of Science. This combination created a unique opportunity to test and analyze catalysts for the one step oxidation of benzene to phenol and compare them with catalysts for the reduction of nitrogen oxides, using hydrocarbons as the reductant. In both projects catalysts have been used which contain Fe ions or oxo-ions in the cavities the zeolite MFI, often called ZSM-5. With Fe as the TM-element and MFI as the host zeolite we found that catalysts with high Fe content, prepared by technique (2) were optimal for the De-NO{sub x} reaction, but extremely unselective for benzene oxidation to phenol. Conversely, the catalysts prepared with (4) had the highest turnover frequency for benzene oxidation, but performed very poorly for NO{sub x} reduction with so-butane. In fact the Fe concentration in the former catalysts were so low that it was necessary to design a special experimental program for the sole purpose of showing that it is really the Fe which catalyzes the benzene oxidation, not some acid center as has been proposed by other authors. For this purpose we used hydrogen sulfide to selectively poison the Fe sites, without deactivating the acidic sites. In addition we could show that the hydrothermal treatment of catalysts prepared by technique (4) is essential to transform iron ions in the zeolite lattice to ''ex lattice ions'' in guest positions. That line of the work required very careful experimentation, because a hydrothermal treatment of a zeolite containing Fe ions in its cavities can also lead to agglomeration of such ions to nano-particles of iron oxide which lowers the selectivity for the desired formation of phenol. This part of the program showed convincingly that indeed Fe is responsible for the benzene oxidation catalysis. The results and conclusion of this work, including the comparison of different catalysts, was published in a number of papers in the scientific literature, listed in the attached list. In these papers also our analysis of the reaction orders and the possible mechanism of the used test reaction are given.

  4. Bio-inspired amino acid oxidation by a non-heme iron catalyst modeling the action of 1-aminocyclopropane-1-carboxylic acid oxidase.

    PubMed

    Baráth, Gábor; Kaizer, József; Pap, József Sándor; Speier, Gábor; El Bakkali-Taheri, Nadia; Simaan, A Jalila

    2010-10-21

    In this communication we describe the first example of a biomimetic mononuclear iron complex, [Fe(III)(Salen)Cl] (Salen = N,N'-bis(salicylidene)-ethylenediaminato), that highly selectively and efficiently catalyzes the oxidation of 1-aminocyclopropane-1-carboxylic acid (ACCH), ?-aminoisobutyric acid (AIBH), and alanine (ALAH) to ethylene or the corresponding carbonyl compounds, mimicking the action of the non-heme iron enzyme 1-aminocyclopropane-1-carboxylic acid oxidase (ACCO). PMID:20830340

  5. Naturally occurring alkaline amino acids function as efficient catalysts on Knoevenagel condensation at physiological pH: a mechanistic elucidation.

    PubMed

    Li, Weina; Fedosov, Sergey; Tan, Tianwei; Xu, Xuebing; Guo, Zheng

    2014-05-01

    To maintain biological functions, thousands of different reactions take place in human body at physiological pH (7.0) and mild conditions, which is associated with health and disease. Therefore, to examine the catalytic function of the intrinsically occurring molecules, such as amino acids at neutral pH, is of fundamental interests. Natural basic ?-amino acid of L-lysine, L-arginine, and L-histidine neutralized to physiological pH as salts were investigated for their ability to catalyze Knoevenagel condensation of benzaldehyde and ethyl cyanoacetate. Compared with their free base forms, although neutralized alkaline amino acid salts reduced the catalytic activity markedly, they were still capable to perform an efficient catalysis at physiological pH as porcine pancreatic lipase (PPL), one of the best enzymes that catalyze Knoevenagel condensation. In agreement with the fact that the three basic amino acids were well neutralized, stronger basic amino acid Arg and Lys showed more obvious variation in NH bend peak from the FTIR spectroscopy study. Study of ethanol/water system and quantitative kinetic analysis suggested that the microenvironment in the vicinity of amino acid salts and protonability/deprotonability of the amine moiety may determine their catalytic activity and mechanism. The kinetic study of best approximation suggested that the random binding might be the most probable catalytic mechanism for the neutralized alkaline amino acid salt-catalyzed Knoevenagel condensation. PMID:24682854

  6. A new sol-gel synthesis of 45S5 bioactive glass using an organic acid as catalyst.

    PubMed

    Faure, J; Drevet, R; Lemelle, A; Ben Jaber, N; Tara, A; El Btaouri, H; Benhayoune, H

    2015-02-01

    In this paper a new sol-gel approach was explored for the synthesis of the 45S5 bioactive glass. We demonstrate that citric acid can be used instead of the usual nitric acid to catalyze the sol-gel reactions. The substitution of nitric acid by citric acid allows to reduce strongly the concentration of the acid solution necessary to catalyze the hydrolysis of silicon and phosphorus alkoxides. Two sol-gel powders with chemical compositions very close to that of the 45S5 were obtained by using either a 2M nitric acid solution or either a 5mM citric acid solution. These powders were characterized and compared to the commercial Bioglass®. The surface properties of the two bioglass powders were assessed by scanning electron microscopy (SEM) and by Brunauer-Emmett-Teller method (BET). The Fourier transformed infrared spectroscopy (FTIR) and the X-ray diffraction (XRD) revealed a partial crystallization associated to the formation of crystalline phases on the two sol-gel powders. The in vitro bioactivity was then studied at the key times during the first hours of immersion into acellular Simulated Body Fluid (SBF). After 4h immersion into SBF we clearly demonstrate that the bioactivity level of the two sol-gel powders is similar and much higher than that of the commercial Bioglass®. This bioactivity improvement is associated to the increase of the porosity and the specific surface area of the powders synthesized by the sol-gel process. Moreover, the nitric acid is efficiently substituted by the citric acid to catalyze the sol-gel reactions without alteration of the bioactivity of the 45S5 bioactive glass. PMID:25492213

  7. Fate of malathion and a phosphonic acid in activated sludge with varying solids retention times.

    PubMed

    Janeczko, Allen K; Walters, Edward B; Schuldt, Steven J; Magnuson, Matthew L; Willison, Stuart A; Brown, Lisa M; Ruiz, Oscar N; Felker, Daniel L; Racz, LeeAnn

    2014-06-15

    This study examined the ability of activated sludge (AS) to sorb and biodegrade ethylmethylphosphonic acid (EMPA) and malathion, a degradation product and surrogate, respectively, for an organophosphate chemical warfare agent. Sorption equilibrium isotherm experiments indicate that sorption of EMPA and malathion to AS is negligible. EMPA at a concentration of 1 mg L(-1) degraded by approximately 30% with apparent first-order kinetics, possibly via co-metabolism from nitrification. Heterotrophic bacteria and abiotic mechanisms, however, are largely responsible for malathion degradation also with apparent first-order kinetics. EMPA did not inhibit chemical oxygen demand (COD) oxidation or nitrification activity, although malathion did appear to induce a stress response resulting in inhibition of COD oxidation. The study also included a 30-day experiment in which malathion, at a concentration of 5 mg L(-1), was repeatedly fed to AS in bench-scale sequencing batch reactors (SBRs) operating at different solids retention times (SRTs). Peak malathion concentrations occurred at day 4.5, with the longer SRTs yielding greater peak malathion concentrations. The AS reduced the malathion concentrations to nearly zero by day 10 for all SRTs, even when the malathion concentration in the influent increased to 20.8 mg L(-1). The data suggest a biodegradation pathway for malathion involving an oxygenase. Phylogenetic analyses revealed that all samples had an abundance of Zoogloea, though there was greater bacterial diversity in the SBR with the SRT of 50 days. The SBR with an SRT of 9.5 days had an apparent reduction in the diversity of the bacterial community. PMID:24709533

  8. Hydrocarbon synthesis catalyst and method of preparation

    DOEpatents

    Sapienza, Richard S. (Shoreham, NY); Sansone, Michael J. (Summit, NJ); Slegeir, William A. R. (Hampton Bays, NY)

    1983-08-02

    A catalyst for the synthesis of hydrocarbons from carbon monoxide and hydrogen composed of palladium or platinum and cobalt supported on a solid phase is disclosed. The catalyst is prepared by heating a heterogeneous component of the palladium or platinum deposited on the solid support in a solution of cobalt carbonyl or precursors thereof. The catalyst exhibits excellent activity, stability in air, and produces highly desirable product fractions even with dilute gaseous reactants. The catalyst is preferably used in dilute slurry form, which is desirable from a heat transfer standpoint.

  9. Hydrocarbon synthesis catalyst and method of preparation

    DOEpatents

    Sapienza, R.S.; Sansone, M.J.; Slegeir, W.A.R.

    1983-08-02

    A catalyst for the synthesis of hydrocarbons from carbon monoxide and hydrogen composed of palladium or platinum and cobalt supported on a solid phase is disclosed. The catalyst is prepared by heating a heterogeneous component of the palladium or platinum deposited on the solid support in a solution of cobalt carbonyl or precursors thereof. The catalyst exhibits excellent activity, stability in air, and produces highly desirable product fractions even with dilute gaseous reactants. The catalyst is preferably used in dilute slurry form, which is desirable from a heat transfer standpoint. 9 figs.

  10. Amino acid modified Ni catalyst exhibits reversible H2 oxidation/production over a broad pH range at elevated temperatures

    PubMed Central

    Dutta, Arnab; DuBois, Daniel L.; Roberts, John A. S.; Shaw, Wendy J.

    2014-01-01

    Hydrogenases interconvert H2 and protons at high rates and with high energy efficiencies, providing inspiration for the development of molecular catalysts. Studies designed to determine how the protein scaffold can influence a catalytically active site have led to the synthesis of amino acid derivatives of [Ni(P2RN2R?)2]2+ complexes, [Ni(P2CyN2Amino?acid)2]2+ (CyAA). It is shown that these CyAA derivatives can catalyze fully reversible H2 production/oxidation at rates approaching those of hydrogenase enzymes. The reversibility is achieved in acidic aqueous solutions (pH = 0–6), 1 atm 25% H2/Ar, and elevated temperatures (tested from 298 to 348 K) for the glycine (CyGly), arginine (CyArg), and arginine methyl ester (CyArgOMe) derivatives. As expected for a reversible process, the catalytic activity is dependent upon H2 and proton concentrations. CyArg is significantly faster in both directions (?300 s?1 H2 production and 20 s?1 H2 oxidation; pH = 1, 348 K, 1 atm 25% H2/Ar) than the other two derivatives. The slower turnover frequencies for CyArgOMe (35 s?1 production and 7 s?1 oxidation under the same conditions) compared with CyArg suggests an important role for the COOH group during catalysis. That CyArg is faster than CyGly (3 s?1 production and 4 s?1 oxidation) suggests that the additional structural features imparted by the guanidinium groups facilitate fast and reversible H2 addition/release. These observations demonstrate that outer coordination sphere amino acids work in synergy with the active site and can play an important role for synthetic molecular electrocatalysts, as has been observed for the protein scaffold of redox active enzymes. PMID:25368196

  11. An eco-friendly N-sulfonylation of amines using stable and reusable Zn-Al-hydrotalcite solid base catalyst under ultrasound irradiation.

    PubMed

    Mokhtar, M; Saleh, T S; Ahmed, N S; Al-Thabaiti, S A; Al-Shareef, R A

    2011-01-01

    Synthetic nanosized Zn-Al-hydrotalcite (Zn-Al-HT) with 20 nm crystallite size and 61 m(2)/g BET-surface area is found to be a mild and efficient catalyst for N-sulfonylation of amines in quantitative yields under ultrasound irradiation. Exclusive synthesis of sulfonamides, using Zn-Al-HT, under ultrasound irradiation, was realized by compatible basic sites of catalyst used. The products were isolated after simple work-up in high yields and purity. PMID:20627793

  12. Facile and Promising Method for Michael Addition of Indole and Pyrrole to Electron-Deficient trans-?-Nitroolefins Catalyzed by a Hydrogen Bond Donor Catalyst Feist's Acid and Preliminary Study of Antimicrobial Activity

    PubMed Central

    Al Majid, Abdullah M. A.; Islam, Mohammad Shahidul; Barakat, Assem; Al-Agamy, Mohamed H. M.; Naushad, Mu.

    2014-01-01

    The importance of cooperative hydrogen-bonding effects has been demonstrated using novel 3-methylenecyclopropane-1,2-dicarboxylic acid (Feist's acid (FA)) as hydrogen bond donor catalysts for the addition of indole and pyrrole to trans-?-nitrostyrene derivatives. Because of the hydrogen bond donor (HBD) ability, Feist's acid (FA) has been introduced as a new class of hydrogen bond donor catalysts for the activation of nitroolefin towards nucleophilic substitution reaction. It has effectively catalyzed the Michael addition of indoles and pyrrole to ?-nitroolefins under optimum reaction condition to furnish the corresponding Michael adducts in good to excellent yields (up to 98%). The method is general, atom-economical, convenient, and eco-friendly and could provide excellent yields and regioselectivities. Some newly synthesized compounds were for examined in vitro antimicrobial activity and their preliminary results are reported. PMID:24574906

  13. No catalyst addition and highly efficient dissociation of H2O for the reduction of CO2 to formic acid with Mn.

    PubMed

    Lyu, Lingyun; Zeng, Xu; Yun, Jun; Wei, Feng; Jin, Fangming

    2014-05-20

    The "greenhouse effect" caused by the increasing atmospheric CO2 level is becoming extremely serious, and thus, the reduction of CO2 emissions has become an extensive, urgent, and long-term task. The dissociation of water for CO2 reduction with solar energy is regarded as one of the most promising methods for the sustainable development of the environment and energy. However, a high solar-to-fuel efficiency keeps a great challenge. In this work, the first observation of a highly effective, highly selective, and robust system of dissociating water for the reduction of carbon dioxide (CO2) into formic acid with metallic manganese (Mn) is reported. A considerably high formic acid yield of more than 75% on a carbon basis from NaHCO3 was achieved with 98% selectivity in the presence of simple commercially available Mn powder without the addition of any catalyst, and the proposed process is exothermic. Thus, this study may provide a promising method for the highly efficient dissociation of water for CO2 reduction by combining solar-driven thermochemistry with the reduction of MnO into Mn. PMID:24787746

  14. Carbon nanotubes contain residual metal catalyst nanoparticles even after washing with nitric acid at elevated temperature because these metal nanoparticles are sheathed by several graphene sheets.

    PubMed

    Pumera, Martin

    2007-05-22

    It is demonstrated that multiwalled (MWCNT) and single-walled (SWCNT) carbon nanotube materials contain residual metal impurities (Fe, Ni, Co, Mo) even after prolonged periods of "washing" with concentrated nitric acid at temperature of 80 degrees C. Transmission electron microscopy (TEM) and high-resolution TEM (HR-TEM) reveals that this is because such metal impurities are intercalated in the nanotube channel (in the case of MWCNT) or in the "bamboo" segment of the nanotube (in the case of "bamboo"-like MWCNT), or they create graphene sheet protected metal core/shell nanoparticles (in the case of SWCNT). TEM/energy-dispersive X-ray spectroscopy (TEM/EDS) elucidate that residual metal impurities presented in "washed" carbon nanotube materials are in some cases in the form of metal alloys or that there can be several different pure metal nanoparticles presented in one CNT material. It is shown by thermogravimetric analysis that "washing" with concentrated nitric acid removes up to 88% (w/w) of metal catalyst nanoparticles from as-received carbon nanotubes and that such removal has in some cases a significant effect on the electrochemical reduction of hydrogen peroxide. PMID:17455966

  15. A new algorithm for identification of components in a mixture: application to Raman spectra of solid amino acids.

    PubMed

    Gawinkowski, Sylwester; Kami?ska, Agnieszka; Roli?ski, Tomasz; Waluk, Jacek

    2014-11-21

    The procedure for identifying components in a mixture was developed and tested on Raman spectra of mixtures of solid amino acids, using the spectra of single amino acids as templates. The method is based on finding the optimum scaling coefficients of the linear combination of template spectra that minimize the Canberra distance between measured and reconstructed spectra. The Canberra distance, used here as a measure of dissimilarity between spectra, defines the non-convex objective function in the related optimization process. In view of the possibility of the presence of local minima, differential evolution, which is a non-gradient stochastic method for finding the global minimum, was chosen for optimization. The method was tested on twenty measured spectra of mixtures of solid powders containing one to eight amino acids taken from the collection of twenty that are coded in living organisms. The results show that the procedure can successfully identify several amino acids, and, in general, several components in a mixture. The method was shown to compare favorably against the least squares and partial least squares methods, the procedures used in commercially available chemometrics packages. PMID:25274103

  16. Supported molten-metal catalysts

    DOEpatents

    Datta, Ravindra (Iowa City, IA); Singh, Ajeet (Iowa City, IA); Halasz, Istvan (Iowa City, IA); Serban, Manuela (Iowa City, IA)

    2001-01-01

    An entirely new class of catalysts called supported molten-metal catalysts, SMMC, which can replace some of the existing precious metal catalysts used in the production of fuels, commodity chemicals, and fine chemicals, as well as in combating pollution. SMMC are based on supporting ultra-thin films or micro-droplets of the relatively low-melting (<600.degree. C.), inexpensive, and abundant metals and semimetals from groups 1, 12, 13, 14, 15 and 16, of the periodic table, or their alloys and intermetallic compounds, on porous refractory supports, much like supported microcrystallites of the traditional solid metal catalysts. It thus provides orders of magnitude higher surface area than is obtainable in conventional reactors containing molten metals in pool form and also avoids corrosion. These have so far been the chief stumbling blocks in the application of molten metal catalysts.

  17. Attrition resistant Fischer-Tropsch catalyst and support

    DOEpatents

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

    2004-05-25

    A catalyst support having improved attrition resistance and a catalyst produced therefrom. The catalyst support is produced by a method comprising the step of treating calcined .gamma.-alumina having no catalytic material added thereto with an acidic aqueous solution having an acidity level effective for increasing the attrition resistance of the calcined .gamma.-alumina.

  18. Studying the Breaking Mechanism of Polymer-Based In-Situ Gelled Acids using Solid Breaker 

    E-print Network

    Tian, Zhida

    2012-10-19

    In situ gelled acids that are based on polymers have been used in the field for several years as an acid diversion agent. These acids should not cause permanent formation damage, and should clean-up rapidly and completely when the well is put back...

  19. Titration of a Solid Acid Monitored by X-Ray Diffraction

    ERIC Educational Resources Information Center

    Dungey, Keenan E.; Epstein, Paul

    2007-01-01

    An experiment is described to introduce students to an important class of solid-state reactions while reinforcing concepts of titration by using a pH meter and a powder X-ray diffractometer. The experiment was successful in teaching students the abstract concepts of solid-state structure and diffraction by applying the diffraction concepts learned…

  20. Tuning the reactivity of oxygen/sulfur by acidity of the catalyst in Prins cyclization: oxa- versus thia-selectivity.

    PubMed

    Reddy, B V Subba; Venkateswarlu, A; Borkar, Prashant; Yadav, J S; Sridhar, B; Grée, René

    2014-03-21

    An unprecedented oxa- versus thia-selectivity has been observed in Prins cyclization of 6-mercaptohex-3-en-1-ol with aldehydes. In the presence of a stoichiometric amount of strong Lewis or Brønsted acids, the reaction provides the hexahydro-2H-thieno[3,2-c]pyran skeleton predominantly via oxonium-Prins cyclization. In contrast, a catalytic amount of weak Lewis or Brønsted acids provides the hexahydro-2H-thiopyrano[4,3-b]furan preferentially through thionium-Prins cyclization. PMID:24564269

  1. Fundamental studies of the mechanism of catalytic reactions with catalysts effective in the gasification of carbon solids and the oxidative coupling of methane

    SciTech Connect

    Heinemann, H.; Somorjai, G.A.; Perry, D.L.

    1992-03-01

    Work will continue on the oxidative coupling reaction of methane over ternary oxide catalysts to produce C{sub 2}, C{sub 3} and C{sub 4} hydrocarbons and particularly olefins with high selectivity. The work which has shown that close to 100% selectivity can be obtained has received wide attention and has resulted in collaborative efforts with industry (CRADA) towards the development of a commercial process. An immediate purpose of additional work is to increase the conversion without diminishing the extremely high selectivity of the reaction and also to permit operation at higher space velocity to reduce equipment size. The mechanism of this reaction is not understood and much additional work is needed to explain the role of carbon formation and of water as intermediates in the reaction and to investigate whether carbon oxides are intermediates. It has been found that oxides other than calcium-nickel-potassium oxides can be useful catalysts for this reaction in the presence of steam and at relatively low temperatures and long contact times. Better definition of the class of binary metal oxides is required and better catalyst characterization is needed to ensure reproducibility of catalyst preparation and operational results. Pretreatment of the catalyst should be shortened and higher space velocities must be obtained. Close collaboration with Orion ACT is required to advance the project toward the pilot plant stage. In the area of coal and char catalytic steam gasification, the large volume of data obtained at atmospheric pressure will be extended to operations at higher pressures.

  2. Solid compounds of europium and terbium with some aromatic carboxylic acids

    SciTech Connect

    Chupakhina, R.A.; Biryulina, V.N.; Kasimova, L.V.; Balakhonov, V.G.

    1986-10-20

    By the reactions of europium and terbium hydroxides with aqueous solutions of benzoic, salicylic, phthalic, and phthalaldehydic acids, compounds were obtained with the compositions: for phthalic acid M/sub 2/L/sub 3/ x 3H/sub 2/O, and for the other acids ML/sub 3/ x 3H/sub 2/O, in which M = Eu/sup 3 +/, Tb/sup 3 +/; L is the anion of the corresponding acid. The compounds of europium and terbium with phthalaldehydric acid were prepared for the first time.

  3. Bimetallic Catalysts.

    ERIC Educational Resources Information Center

    Sinfelt, John H.

    1985-01-01

    Chemical reaction rates can be controlled by varying composition of miniscule clusters of metal atoms. These bimetallic catalysts have had major impact on petroleum refining, where work has involved heterogeneous catalysis (reacting molecules in a phase separate from catalyst.) Experimentation involving hydrocarbon reactions, catalytic…

  4. Carbene Catalysts

    NASA Astrophysics Data System (ADS)

    Moore, Jennifer L.; Rovis, Tomislav

    The use of N-heterocyclic carbenes as catalysts for organic transformations has received increased attention in the past 10 years. A discussion of catalyst development and nucleophilic characteristics precedes a description of recent advancements and new reactions using N-heterocyclic carbenes in catalysis.

  5. Transesterification of edible, non-edible and used cooking oils for biodiesel production using calcined layered double hydroxides as reusable base catalysts.

    PubMed

    Sankaranarayanan, Sivashunmugam; Antonyraj, Churchil A; Kannan, S

    2012-04-01

    Fatty acid methyl esters (FAME) were produced from edible, non-edible and used cooking oils with different fatty acid contents by transesterification with methanol using calcined layered double hydroxides (LDHs) as solid base catalysts. Among the catalysts, calcined CaAl2-LDH (hydrocalumite) showed the highest activity with >90% yield of FAME using low methanol:oil molar ratio (<6:1) at 65 °C in 5 h. The activity of the catalyst was attributed to its high basicity as supported by Hammett studies and CO(2)-TPD measurements. The catalyst was successfully reused in up to four cycles. Some of the properties such as density, viscosity, neutralization number and glycerol content of the obtained biodiesel matched well with the standard DIN values. It is concluded that a scalable heterogeneously catalyzed process for production of biodiesel in high yields from a wide variety of triglyceride oils including used oils is possible using optimized conditions. PMID:22305480

  6. The nature of the active phase in the heteropolyacid catalyst H{sub 4}PVMo{sub 11}O{sub 40} {center_dot} 32H{sub 2}O used for the selective oxidation of isobutyric acid

    SciTech Connect

    Ilkenhans, T.; Herzog, B.; Braun, T.

    1995-05-01

    The structural changes of the title compound during heating and under conditions of catalytic conversion of isobutyric acid to methacrylic acid were followed in situ by powder X-ray diffraction under continuous control of its activity. The results were verified by a postmortem phase analysis of practical supported catalyst samples used in kinetic reactors. The activity of the catalyst is correlated with its dehydrated form. A new cubic phase of a water-free vanadyl salt of the heteropolyacid (HPA) was found to be connected to a maximum conversion. This phase is isostructural to the unsubstituted anhydrous alkali-3-HPA salts and is metastable at ambient conditions with respect to rehydration. The catalyst material as a whole is metastable at any temperature above the onset of conversion with respect to a partially reversible decomposition into MoO{sub 3} and amorphous other components. Restructuring into crystalline forms of HPA is possible from the deactivated material upon dissolution and recrystallization at 323 K. In Situ UV-VIS data and X-ray diffraction show the complete self-reorganization of the MoO{sub 3} phase and the amorphous V and P compounds into new Keggin anions indicating the possible living nature of the catalyst under reaction conditions which enable extended lifetimes beyond the stability limits found in the present in situ X-ray diffraction experiments. 32 refs., 16 figs., 3 tabs.

  7. Extended chain conformational preference of solid films of poly(2,6-benzoxazole) processed from Lewis acid coordination complexes

    SciTech Connect

    Chen, X.L.; Jenekhe, S.A.

    1996-12-31

    Polybenzoxazoles such as poly(2,6-benzoxazole)(2,6-PBO), poly(2,6-benzothiazole)(2,6-PBT) and poly(2,5(6)-benzimidazole) are semi-flexible, high temperature, and high modulus polymers which have been of wide interest as the matrix components of molecular composites. These polymers and their rigid-rod relatives polybenzobisazoles(PBZT, PBO, etc) also exhibit interesting electroactive and photoactive properties. As previously shown for rigid-rod polybenzobisazoles, we have found that the semi-flexible polybenzoazoles are soluble in Lewis acid (e.g. GaCl{sub 3}, AlCl{sub 3})/nitromethane solvent systems from which films and fibers could be processed. Remarkably, 2,6-PBO films prepared by complexation mediated processing from Lewis acid/nitromethane solutions of the polymer exhibit the extended chain (trans) conformation as evidenced by optical absorption and photoluminescence spectroscopies. In contrast, 2,6-PBO films prepared from formic acid/methanesulfonic acid(FA/MSA) solvent am predominantly of cis-conformation. The origin of this extended chain conformation preference of 2,6-PBO films prepared from Lewis acid/nitromethane solutions lies in the stereochemical control exerted by Lewis(MX{sub 3}) coordination to the imine nitrogens of 2,6-PBO resulting in an all-trans conformation after film processing and decomplexation. Since the trans- and cis-(2,6-PBO) have dramatically different solid state properties such as optical absorption and luminescence, our results demonstrate how a high degree of control of solid state structure and properties can be achieved by novel polymer processing.

  8. Multi-scale strategy to eradicate Pseudomonas aeruginosa on surfaces using solid lipid nanoparticles loaded with free fatty acids

    NASA Astrophysics Data System (ADS)

    Taylor, Erik N.; Kummer, Kim M.; Dyondi, Deepti; Webster, Thomas J.; Banerjee, Rinti

    2013-12-01

    Infections are both frequent and costly in hospitals around the world, leading to longer hospital stays, overuse of antibiotics, and excessive costs to the healthcare system. Moreover, antibiotic resistant organisms, such as Pseudomonas aeruginosa are increasing in frequency, leading to 1.7 million infections per year in USA hospitals, and 99 000 deaths, both due to the evolution of antibiotic resistance and the formation of biofilms on medical devices. In particular, respiratory infections are costly, deadly to 4.5 million persons per year worldwide, and can spread to the lungs through the placement of endotracheal tubing. In this study, towards a reduction in infections, solid lipid nanoparticles were formulated from free fatty acids, or natural lipophilic constituents found in tissues of the body. A strategy was developed to target infections by producing coatings made of non-toxic chemistries lauric acid and oleic acid delivered by core-shell solid lipid nanoparticles that act against bacteria by multiple mechanisms at the nanoscale, including disruption of bacteria leading to DNA release, and reducing the adhesion of dead bacteria to ~1%. This is the first such study to explore an anti-infection surface relying on these multi-tier strategies at the nanoscale.

  9. Reduction of volatile fatty acids and odor offensiveness by anaerobic digestion and solid separation of dairy manure during manure storage.

    PubMed

    Page, Laura H; Ni, Ji-Qin; Zhang, Hao; Heber, Albert J; Mosier, Nathan S; Liu, Xingya; Joo, Hung-Soo; Ndegwa, Pius M; Harrison, Joseph H

    2015-04-01

    Volatile fatty acids (VFA) play an important role in the biodegradation of organic wastes and production of bioenergy under anaerobic digestion, and are related to malodors. However, little is known about the dynamics of VFA during dairy manure storage. This study evaluated the characteristics of VFA in dairy manure before and after anaerobic co-digestion in a laboratory experiment using eight lab-scale reactors. The reactors were loaded with four different types of dairy manure: (1) liquid dairy manure from a freestall barn, (2) mixture of dairy manure and co-digestion food processing wastes at the inlet of an anaerobic digester, (3) effluent from the digester outlet, and (4) the liquid fraction of effluent from a solid separator. Four VFA (acetic, propionic, butyric, and 2-methylbutyric acids) were identified and quantified in weekly manure samples from all reactors. Results showed that the dominant VFA was acetic acid in all four manure sources. The off-farm co-digestion wastes significantly increased the total VFA concentrations and the proportions of individual VFA in the influent. The dairy manure under storage demonstrated high temporal and spatial variations in pH and VFA concentrations. Anaerobic digestion reduced the total VFA by 86%-96%; but solid-liquid separation did not demonstrate a significant reduction in total VFA in this study. Using VFA as an indicator, anaerobic digestion exhibited an effective reduction of dairy manure odor offensiveness. PMID:25617873

  10. Postsynthesis-Treated Iron-Based Metal-Organic Frameworks as Selective Catalysts for the Sustainable Synthesis of Nitriles.

    PubMed

    Rapeyko, Anastasia; Climent, Maria J; Corma, Avelino; Concepción, Patricia; Iborra, Sara

    2015-10-01

    The dehydration of aldoximes to the corresponding nitriles can be performed with excellent activity and selectivity by using iron trimesate as a homogeneous catalyst. Iron trimesate has been heterogenized by synthesizing metal-organic frameworks (MOFs) from iron trimesate, that is, Fe(BTC), and MIL-100 (Fe). These materials were active and selective aldoxime dehydration catalysts, and postsynthesis-treated MIL-100 (Fe) produced the desired nitriles with 100?% conversion and selectivities >90?% under mild reaction conditions and in short reaction times. X-ray photoelectron spectroscopy showed the presence of different Fe species in the catalyst, and in?situ IR spectroscopy combined with catalytic results indicates that the catalytic activity is associated with Fe framework species. The postsynthesis-treated MIL-100 (Fe)-NH4 F can be recycled several times and has an excellent reaction scope, which gives better catalytic results than other solid acid or base catalysts. PMID:26333197

  11. Solid dispersions of the penta-ethyl ester prodrug of diethylenetriaminepentaacetic acid (DTPA): Formulation design and optimization studies

    PubMed Central

    Yang, Yu-Tsai; Di Pasqua, Anthony J.; Zhang, Yong; Sueda, Katsuhiko; Jay, Michael

    2015-01-01

    The penta-ethyl ester prodrug of diethylenetriaminepentaacetic acid (DTPA), which exists as an oily liquid, was incorporated into a solid dispersion for oral administration by the solvent evaporation method using blends of polyvinylpyrrolidone (PVP), Eudragit® RL PO and ?-tocopherol. D-optimal mixture design was used to optimize the formulation. Formulations that had a high concentration of both Eudragit® RL PO and ?-tocopherol exhibited low water absorption and enhanced stability of the DTPA prodrug. Physicochemical properties of the optimal formulation were evaluated using Fourier transform infrared (FTIR) spectroscopy and differential scanning calorimetry (DSC). In vitro release of the prodrug was evaluated using the USP Type II apparatus dissolution method. DSC studies indicated that the matrix had an amorphous structure, while FTIR spectrometry showed that DTPA penta-ethyl ester and excipients did not react with each other during formation of the solid dispersion.. Dissolution testing showed that the optimized solid dispersion exhibited a prolonged release profile, which could potentially result in a sustained delivery of DTPA penta-ethyl to enhance bioavailability. In conclusion, DTPA penta-ethyl ester was successfully incorporated into a solid matrix with high drug loading and improved stability compared to prodrug alone. PMID:24047113

  12. Solid dispersions of the penta-ethyl ester prodrug of diethylenetriaminepentaacetic acid (DTPA): formulation design and optimization studies.

    PubMed

    Yang, Yu-Tsai; Di Pasqua, Anthony J; Zhang, Yong; Sueda, Katsuhiko; Jay, Michael

    2014-11-01

    The penta-ethyl ester prodrug of diethylenetriaminepentaacetic acid (DTPA), which exists as an oily liquid, was incorporated into a solid dispersion for oral administration by the solvent evaporation method using blends of polyvinylpyrrolidone (PVP), Eudragit® RL PO and ?-tocopherol. D-optimal mixture design was used to optimize the formulation. Formulations that had a high concentration of both Eudragit® RL PO and ?-tocopherol exhibited low water absorption and enhanced stability of the DTPA prodrug. Physicochemical properties of the optimal formulation were evaluated using Fourier transform infrared (FTIR) spectroscopy and differential scanning calorimetry (DSC). In vitro release of the prodrug was evaluated using the USP Type II apparatus dissolution method. DSC studies indicated that the matrix had an amorphous structure, while FTIR spectrometry showed that DTPA penta-ethyl ester and excipients did not react with each other during formation of the solid dispersion. Dissolution testing showed that the optimized solid dispersion exhibited a prolonged release profile, which could potentially result in a sustained delivery of DTPA penta-ethyl to enhance bioavailability. In conclusion, DTPA penta-ethyl ester was successfully incorporated into a solid matrix with high drug loading and improved stability compared to prodrug alone. PMID:24047113

  13. Catalysts compositions for use in fuel cells

    DOEpatents

    Chuang, Steven S.C.

    2015-12-01

    The present invention generally relates to the generation of electrical energy from a solid-state fuel. In one embodiment, the present invention relates to a solid-oxide fuel cell for generating electrical energy from a carbon-based fuel, and to catalysts for use in a solid-oxide fuel cell.

  14. Catalysts compositions for use in fuel cells

    DOEpatents

    Chuang, Steven S.C.

    2015-12-02

    The present invention generally relates to the generation of electrical energy from a solid-state fuel. In one embodiment, the present invention relates to a solid-oxide fuel cell for generating electrical energy from a carbon-based fuel, and to catalysts for use in a solid-oxide fuel cell.

  15. Preparing poly(aryl ethers) using alkaline earth metal carbonates, organic acid salts, and optionally copper compounds, as catalysts

    SciTech Connect

    Winslow, P.A.; Kelsey, D.R.; Matzner, M.

    1988-09-27

    This patent describes an improved process for preparing poly(aryl ethers) and poly(aryl ether ketones) by the reaction of a mixture of at least one bisphenol and at least one dihalobenzenoid compound, and/or a halophenol. The improvement comprises providing to the reaction, a base which is a combination of an alkaline earth metal carbonate and/or bicarbonate and a potassium, rubidium, or cesium salt of an organic acid or combination of organic salts thereof.

  16. Analysis of fusaric acid in maize using molecularly imprinted solid phase extraction (MISPE) clean-up and ion-pair LC with diode array UV detection

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Fusaric acid is a phytotoxin and mycotoxin occasionally found in maize contaminated with Fusarium fungi. A selective sample clean-up procedure was developed to detect fusaric acid in maize using molecularly imprinted solid phase extraction (MISPE) clean-up coupled with ion-pair liquid chromatography...

  17. Simple preparation of solid-phase microextraction fiber with cation exchange capacities using poly(butadiene-maleic acid).

    PubMed

    Zhu, Yingli; Shen, Guobin; Zhang, Feifang; Yang, Bingcheng

    2013-01-01

    A simply way was proposed to prepare solid-phase microextraction (SPME) fiber with cation-exchange functional groups by the thermally initiated radical polymerization of poly(butadiene-maleic acid) (PBMA) copolymer onto a silica capillary. The capacity of the fiber coating could be easily controlled by fabricating successive layers of PBMA. The performance of the fiber combined with ion chromatography was evaluated by choosing Mg(2+) and Ca(2+) as model analytes; ?13 and ?51-fold enrichment factors for Mg(2+) and Ca(2+) were obtained, respectively. PMID:24107568

  18. Deoxyribonucleic acid-directed growth of well dispersed nickel-palladium-platinum nanoclusters on graphene as an efficient catalyst for ethanol electrooxidation

    NASA Astrophysics Data System (ADS)

    Ma, Jingwen; Wang, Jun; Zhang, Guanghui; Fan, Xiaobin; Zhang, Guoliang; Zhang, Fengbao; Li, Yang

    2015-03-01

    Trimetallic NiPdPt alloy nanoclusters with diameter of about 10 nm are successfully dispersed on the deoxyribonucleic acid-modified reduced graphene oxide (DNA-rGO) by using NaBH4 as reductant. The prepared NiPdPt nanoclusters grown on DNA-rGO (NiPdPt/DNA-rGO) composite are used as electrocatalysts for ethanol electrooxidation in alkaline solution. Cyclic voltammetry and chronoamperometry are used to investigate the electrochemical activities and stabilities of the catalysts. The Ni1Pd1Pt1/DNA-rGO (molar ratio of Ni, Pd, Pt is 1:1:1) has extraordinary electrocataltic activity, with their mass current density reaching 3.4 A mg-1metal and better stability. As compared with the bimetallic counterparts and NiPdPt grown on multi-wall carbon nanotubes, Ni1Pd1Pt1/DNA-rGO retains the highest mass current density after a 2000 s current-time test at 0 V.

  19. Value recovery from spent alumina-base catalyst

    DOEpatents

    Hyatt, David E. (Northglenn, CO)

    1987-01-01

    A process for the recovery of aluminum and at least one other metal selected from the group consisting of molybdenum, nickel and cobalt from a spent hydrogenation catalyst comprising (1) adding about 1 to 3 parts H.sub.2 SO.sub.4 to each part of spent catalyst in a reaction zone of about 20.degree. to 200.degree. C. under sulfide gas pressure between about 1 and about 35 atmospheres, (2) separating the resultant Al.sub.2 (SO.sub.4).sub.3 solution from the sulfide precipitate in the mixture, (3) oxidizing the remaining sulfide precipitate as an aqueous slurry at about 20.degree. to 200.degree. C. in an oxygen-containing atmosphere at a pressure between about 1 and about 35 atmospheres, (4) separating the slurry to obtain solid molybdic acid and a sulfate liquor containing said at least one metal, and (5) recovering said at least one metal from the sulfate liquor in marketable form.

  20. Amino acid modified Ni catalyst exhibits reversible H2 oxidation/production over a broad pH range at elevated temperatures

    SciTech Connect

    Dutta, Arnab; DuBois, Daniel L.; Roberts, John A.; Shaw, Wendy J.

    2014-11-18

    Hydrogenases interconvert H2 and protons at high rates and with high energy efficiencies, providing inspiration for the development of molecular catalysts. Studies designed to determine how the protein scaffold can influence a catalytically active site has led to the synthesis of amino acid derivatives, [Ni(PCy2NAmino acid2)2]2+ (CyAA), of [Ni(PR2NR'2)2]2+ complexes. It is shown that these CyAA derivatives can catalyze fully reversible H2 production/oxidation, a feature reminiscent of enzymes. The reversibility is achieved in acidic aqueous solutions, 0.25% H2/Ar, and elevated temperatures (tested up to 348 K) for the glycine (CyGly), arginine (CyArg), and arginine methyl ester (CyArgOMe) derivatives. As expected for a reversible process, the activity is dependent upon H2 and proton concentration. CyArg is significantly faster in both directions than the other two derivatives (~300 s-1 H2 production and 20 s-1 H2 oxidation; pH=1, 348 K). The significantly slower rates for CyArgOMe (35 s-1 production and 7 s-1 oxidation) compared to CyArg suggests an important role for the COOH group during catalysis. That CyArg is faster than CyGly (3 s-1 production and 4 s-1 oxidation under the same conditions) suggests that the additional structural features imparted by the guanidinium groups facilitate fast and reversible H2 addition/release. These observations demonstrate that appended, outer coordination sphere amino acids work in synergy with the active site and can play an equally important role for synthetic molecular electrocatalysts as the protein scaffold does for redox active enzymes. This work was funded by the Office of Science Early Career Research Program through the US DOE, BES (AD, WJS), and the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the US DOE, BES (DLD, JASR). PNNL is operated by Battelle for the US DOE.

  1. Synthesis of ferromagnetic nanoparticles, formic acid oxidation catalyst nanocomposites, and late-transition metal-boride intermetallics by unique synthetic methods and single-source precursors

    NASA Astrophysics Data System (ADS)

    Wellons, Matthew S.

    The design, synthesis, and characterization of magnetic alloy nanoparticles, supported formic acid oxidation catalysts, and superhard intermetallic composites are presented. Ferromagnetic equatomic alloy nanoparticles of FePt, FePd, and CoPt were synthesized utilizing single-source heteronuclear organometallic precursors supported on an inert water-soluble matrix. Direct conversion of the precursor-support composite to supported ferromagnetic nanoparticles occurs under elevated temperatures and reducing conditions with metal-ion reduction and minimal nanoparticle coalescence. Nanoparticles were easily extracted from the support by addition of water and characterized in structure and magnetic properties. Palladium and platinum based nanoparticles were synthesized with microwave-based and chemical metal-ion reduction strategies, respectively, and tested for catalytic performance in a direct formic acid fuel cell (DFAFC). A study of palladium carbide nanocomposites with various carbonaceous supports was conducted and demonstrated strong activity comparable to commercially available palladium black, but poor catalytic longevity. Platinum-lead alloy nanocomposites synthesized with chemical reduction and supported on Vulcan carbon demonstrated strong activity, excellent catalytic longevity, and were subsequently incorporated into a prototype DFAFC. A new method for the synthesis of superhard ceramics on polymer substrates called Confined Plasma Chemical Deposition (CPCD) was developed. The CPCD method utilizes a tuned Free Electron Laser to selectively decompose the single-source precursor, Re(CO)4(B3H8), in a plasma-like state resulting in the superhard intermetallic ReB2 deposited on polymer substrates. Extension of this method to the synthesis of other hard of superhard ceramics; WB4, RuB2, and B4C was demonstrated. These three areas of research show new synthetic methods and novel materials of technological importance, resulting in a substantial advance in their respective fields.

  2. Intramolecular vibrations in low-frequency normal modes of amino acids: L-alanine in the neat solid state.

    PubMed

    Zhang, Feng; Wang, Houng-Wei; Tominaga, Keisuke; Hayashi, Michitoshi

    2015-03-26

    This paper presents a theoretical analysis of the low-frequency phonons of L-alanine by using the solid-state density functional theory at the ? point. We are particularly interested in the intramolecular vibrations accessing low-frequency phonons via harmonic coupling with intermolecular vibrations. A new mode-analysis method is introduced to quantify the vibrational characteristics of such intramolecular vibrations. We find that the torsional motions of COO(-) are involved in low-frequency phonons, although COO(-) is conventionally assumed to undergo localized torsion. We also find the broad distributions of intramolecular vibrations relevant to important functional groups of amino acids, e.g., the COO(-) and NH3(+) torsions, in the low-frequency phonons. The latter finding is illustrated by the concept of frequency distribution of vibrations. These findings may lead to immediate implications in other amino acid systems. PMID:25723274

  3. Impact of Corn Stover Composition on Hemicellulose Conversion during Dilute Acid Pretreatment and Enzymatic Cellulose Digestibility of the Pretreated Solids

    SciTech Connect

    Weiss, N. D.; Farmer, J. D.; Schell, D. J.

    2010-01-01

    This study assessed the impact of corn stover compositional variability on xylose conversion yields during dilute acid pretreatment and on enzymatic cellulose digestibility of the resulting pretreated solids. Seven compositionally-different stovers obtained from various locations throughout the United States were pretreated at three different conditions in triplicate in a pilot-scale continuous reactor. At the same pretreatment severity, a 2-fold increase in monomeric xylose yield and a 1.5-fold increase in enzymatic cellulose digestibility from their lowest values were found. Similar results were observed at the other pretreatment conditions. It was found that xylose conversion yields decreased with increasing acid neutralization capacity or soil content of the corn stover. Xylose yields also increased with increasing xylan content. No other significant correlations between corn stover's component concentrations and conversion yields were found.

  4. Catalyzed pyrolysis of grape and olive bagasse. Influence of catalyst type and chemical treatment

    SciTech Connect

    Encinar, J.M.; Beltran, F.J.; Ramiro, A.; Gonzalez, J.F.

    1997-10-01

    Catalyzed pyrolysis of grape and olive bagasse under different experimental conditions has been studied. Variables investigated were temperature and type and concentration of catalysts. Experiments were carried out in an isothermal manner. Products of pyrolysis are gases (H{sub 2}, CO, CO{sub 2}, and CH{sub 4}), liquids (methanol, acetone, furfurylic alcohol, phenol, furfural, naphthalene, and o-cresol), and solids (chars). Temperature is a significant variable, yielding increases of fixed carbon content, gases, and to a lesser extent, ash percentage. Catalyst presence also yields increases of solid phase content, but the amount of liquid components decrease. Among catalysts applied those of Fe and Zn are the most advisable to obtain gases. Chemical treatment of bagasses with sulfuric or phosphoric acid washing leads to lower char yields, although fixed carbon content is higher and ash presence diminishes with respect to catalyst pyrolysis without chemical pretreatment. A pyrolysis kinetic study based on gas generation from thermal decomposition of residues has been carried out. From the model proposed, rate constants for the formation of each gas, reaction order of the catalyst, and activation energies were determined.

  5. Photo-oxidation catalysts

    DOEpatents

    Pitts, J. Roland (Lakewood, CO); Liu, Ping (Irvine, CA); Smith, R. Davis (Golden, CO)

    2009-07-14

    Photo-oxidation catalysts and methods for cleaning a metal-based catalyst are disclosed. An exemplary catalyst system implementing a photo-oxidation catalyst may comprise a metal-based catalyst, and a photo-oxidation catalyst for cleaning the metal-based catalyst in the presence of light. The exposure to light enables the photo-oxidation catalyst to substantially oxidize absorbed contaminants and reduce accumulation of the contaminants on the metal-based catalyst. Applications are also disclosed.

  6. Fuel cells and fuel cell catalysts

    DOEpatents

    Masel, Richard I.; Rice, Cynthia A.; Waszczuk, Piotr; Wieckowski, Andrzej

    2006-11-07

    A direct organic fuel cell includes a formic acid fuel solution having between about 10% and about 95% formic acid. The formic acid is oxidized at an anode. The anode may include a Pt/Pd catalyst that promotes the direct oxidation of the formic acid via a direct reaction path that does not include formation of a CO intermediate.

  7. Elucidating Metabolic Pathways for Amino Acid Incorporation Into Dragline Spider Silk using 13C Enrichment and Solid State NMR

    PubMed Central

    Creager, Melinda S.; Izdebski, Thomas; Brooks, Amanda E.; Lewis, Randolph V.

    2013-01-01

    Spider silk has been evolutionarily optimized for contextual mechanical performance over the last 400 million years. Despite precisely balanced mechanical properties, which have yet to be reproduced, the underlying molecular architecture of major ampullate spider silk can be simplified being viewed as a versatile block copolymer. Four primary amino acid motifs: polyalanine, (GA)n, GPGXX, and GGX (X = G,A,S,Q,L,Y) will be considered in this study. Although synthetic mimetics of many of these amino acid motifs have been produced in several biological systems, the source of spider silk’s mechanical integrity remains elusive. Mechanical robustness may be a product not only of the amino acid structure but also of the tertiary structure of the silk. Historically, solid state Nuclear Magnetic Resonance (ssNMR) has been used to reveal the crystalline structure of the polyalanine motif; however, limitations in amino acid labeling techniques have obscured the structures of the GGX and GPGXX motifs thought to be responsible for the structural mobility of spider silk. We describe the use of metabolic pathways to label tyrosine for the first time as well as to improve the labeling efficiency of proline. These improved labeling techniques will allow the previously unknown tertiary structures of major ampullate silk to be probed. PMID:21334448

  8. Volatile organic acid adsorption and cation dissociation by porphyritic andesite for enhancing hydrolysis and acidogenesis of solid food wastes.

    PubMed

    Cheng, Fan; Li, Ming; Li, Dawei; Chen, Ling; Jiang, Weizhong; Kitamura, Yutaka; Li, Baoming

    2010-07-01

    Volatile organic acid adsorption, cation dissociation by porphyritic andesite, and their effects on the hydrolysis and acidogenesis of solid food wastes were evaluated through batch experiments. The acetic acid adsorption experiments show that pH was mainly regulated by H(+) adsorption. The mono-layer and multi-layer adsorption were found under the low (8.3-83.2 mmol/L) and high (133.22-532.89 mmol/L) initial acetic acid concentration, respectively. The dissociated cations concentration in acidic solution showed the predominance of Ca(2+). Porphyritic andesite addition elevated the pH levels and accelerated hydrolysis and acidogenesis in the batch fermentation experiment. Leachate of porphyritic andesite addition achieved the highest hydrolysis constant of 22.1 x 10(-3)kgm(-2)d(-1) and VS degradation rates of 3.9 g L(-1)d(-1). The highest activity of microorganisms represented by specific growth rate of ATP, 0.16d(-1), and specific consumption rate of Ca(2+), 0.18d(-1), was obtained by adding leachate of porphyritic andesite. PMID:20156676

  9. Coke Accumulation on Catalysts used in a Fluidized Bed Pyrolyzer

    Technology Transfer Automated Retrieval System (TEKTRAN)

    We have examined the impact of various solid catalysts on the product distribution resulting from the pyrolysis of biomass. Though catalysts do have a discernible impact, this impact is small. In our bench-top pyrolyzer designed as a catalyst screening tool, we measure bulk product distribution as...

  10. Enhancement of all-trans retinoic acid-induced differentiation by pH-sensitive nanoparticles for solid tumor cells.

    PubMed

    Wang, Yongjian; Wang, Huizhen; Lv, Xueming; Liu, Congcong; Qi, Linshuang; Song, Xindi; Yu, Ao

    2014-03-01

    Cancer differentiation therapy is an attractive concept and has been clinically used to treat leukemia. However, it is limited to date for solid tumors. In this study, the pH-sensitive nanoparticles based on poly(amidoamine) (PAMAM) dendrimers are synthesized by coupling 3,4,5,6-tetrahydrophthalic anhydride with the first generation PAMAM. The modified dendrimers can self-assemble in aqueous solution to form nanoparticles with a diameter of 125-435 nm. The nanoparticles are relatively stable at physiological pH (pH 7.4) but dissociated in acidic environments (pH 5.0 or 6.0). The present studies show that the proliferation inhibition and albumin secretion of hepatoma carcinoma cells are enhanced with all-trans retinoic acid (ATRA) encapsulated in the nanoparticles. The enhancement of induced differentiation is due to the high internalization of ATRA in the cells by the nanoparticles. These experimental results demonstrate that pH-sensitive nanoparticles may be efficient for improving the differentiation therapy for solid tumor. PMID:24115498

  11. Mefenamic acid anti-inflammatory drug: probing its polymorphs by vibrational (IR and Raman) and solid-state NMR spectroscopies.

    PubMed

    Cunha, Vanessa R R; Izumi, Celly M S; Petersen, Philippe A D; Magalhães, Alviclér; Temperini, Marcia L A; Petrilli, Helena M; Constantino, Vera R L

    2014-04-24

    This work deals with the spectroscopic (supported by quantum chemistry calculations), structural, and morphological characterization of mefenamic acid (2-[(2,3-(dimethylphenyl)amino] benzoic acid) polymorphs, known as forms I and II. Polymorph I was obtained by recrystallization in ethanol, while form II was reached by heating form I up to 175 °C, to promote the solid phase transition. Experimental and theoretical vibrational band assignments were performed considering the presence of centrosymmetric dimers. Besides band shifts in the 3345-3310 cm(-1) range, important vibrational modes to distinguish the polymorphs are related to out-of-phase and in-phase N-H bending at 1582 (Raman)/1577 (IR) cm(-1) and 1575 (Raman)/1568 (IR) cm(-1) for forms I and II, respectively. In IR spectra, bands assigned to N-H bending out of plane are observed at 626 and 575 cm(-1) for polymorphs I and II, respectively. Solid-state (13)C NMR spectra pointed out distinct chemical shifts for the dimethylphenyl group: 135.8 to 127.6 ppm (carbon bonded to N) and 139.4 to 143.3 ppm (carbon bonded to methyl group) for forms I and II, respectively. PMID:24654805

  12. Temperature and solids retention time control microbial population dynamics and volatile fatty acid production in replicated anaerobic digesters

    NASA Astrophysics Data System (ADS)

    Vanwonterghem, Inka; Jensen, Paul D.; Rabaey, Korneel; Tyson, Gene W.

    2015-02-01

    Anaerobic digestion is a widely used technology for waste stabilization and generation of biogas, and has recently emerged as a potentially important process for the production of high value volatile fatty acids (VFAs) and alcohols. Here, three reactors were seeded with inoculum from a stably performing methanogenic digester, and selective operating conditions (37°C and 55°C 12 day and 4 day solids retention time) were applied to restrict methanogenesis while maintaining hydrolysis and fermentation. Replicated experiments performed at each set of operating conditions led to reproducible VFA production profiles which could be correlated with specific changes in microbial community composition. The mesophilic reactor at short solids retention time showed accumulation of propionate and acetate (42 +/- 2% and 15 +/- 6% of CODhydrolyzed, respectively), and dominance of Fibrobacter and Bacteroidales. Acetate accumulation (>50% of CODhydrolyzed) was also observed in the thermophilic reactors, which were dominated by Clostridium. Under all tested conditions, there was a shift from acetoclastic to hydrogenotrophic methanogenesis, and a reduction in methane production by >50% of CODhydrolyzed. Our results demonstrate that shortening the SRT and increasing the temperature are effective strategies for driving microbial communities towards controlled production of high levels of specific volatile fatty acids.

  13. Temperature and solids retention time control microbial population dynamics and volatile fatty acid production in replicated anaerobic digesters

    PubMed Central

    Vanwonterghem, Inka; Jensen, Paul D.; Rabaey, Korneel; Tyson, Gene W.

    2015-01-01

    Anaerobic digestion is a widely used technology for waste stabilization and generation of biogas, and has recently emerged as a potentially important process for the production of high value volatile fatty acids (VFAs) and alcohols. Here, three reactors were seeded with inoculum from a stably performing methanogenic digester, and selective operating conditions (37°C and 55°C; 12 day and 4 day solids retention time) were applied to restrict methanogenesis while maintaining hydrolysis and fermentation. Replicated experiments performed at each set of operating conditions led to reproducible VFA production profiles which could be correlated with specific changes in microbial community composition. The mesophilic reactor at short solids retention time showed accumulation of propionate and acetate (42 ± 2% and 15 ± 6% of CODhydrolyzed, respectively), and dominance of Fibrobacter and Bacteroidales. Acetate accumulation (>50% of CODhydrolyzed) was also observed in the thermophilic reactors, which were dominated by Clostridium. Under all tested conditions, there was a shift from acetoclastic to hydrogenotrophic methanogenesis, and a reduction in methane production by >50% of CODhydrolyzed. Our results demonstrate that shortening the SRT and increasing the temperature are effective strategies for driving microbial communities towards controlled production of high levels of specific volatile fatty acids. PMID:25683239

  14. Synthesis of biodiesel from pongamia oil using heterogeneous ion-exchange resin catalyst.

    PubMed

    Jaya, N; Selvan, B Karpanai; Vennison, S John

    2015-11-01

    Biodiesel is a clean-burning renewable substitute fuel for petroleum. Biodiesel could be effectively produced by transesterification reaction of triglycerides of vegetable oils with short-chain alcohols in the presence of homogeneous or heterogeneous catalysts. Conventionally, biodiesel manufacturing processes employ strong acids or bases as catalysts. But, separation of the catalyst and the by-product glycerol from the product ester is too expensive to justify the product use as an automobile fuel. Hence heterogeneous catalysts are preferred. In this study, transesterification of pongamia oil with ethanol was performed using a solid ion-exchange resin catalyst. It is a macro porous strongly basic anion exchange resin. The process parameters affecting the ethyl ester yield were investigated. The reaction conditions were optimized for the maximum yield of fatty acid ethyl ester (FAEE) of pongamia oil. The properties of FAEE were compared with accepted standards of biodiesel. Engine performance was also studied with pongamia oil diesel blend and engine emission characteristics were observed. PMID:26254204

  15. 7 CFR 51.1178 - Maximum anhydrous citric acid permissible for corresponding total soluble solids.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ...United States Standards for Grades of Florida Oranges and Tangelos Standards for Internal Quality of Common Sweet Oranges (citrus Sinensis (l) Osbeck) § 51.1178 Maximum anhydrous citric acid permissible for corresponding total soluble...

  16. 7 CFR 51.1178 - Maximum anhydrous citric acid permissible for corresponding total soluble solids.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ...United States Standards for Grades of Florida Oranges and Tangelos Standards for Internal Quality of Common Sweet Oranges (citrus Sinensis (l) Osbeck) § 51.1178 Maximum anhydrous citric acid permissible for corresponding total soluble...

  17. 7 CFR 51.1178 - Maximum anhydrous citric acid permissible for corresponding total soluble solids.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ...United States Standards for Grades of Florida Oranges and Tangelos Standards for Internal Quality of Common Sweet Oranges (citrus Sinensis (l) Osbeck) § 51.1178 Maximum anhydrous citric acid permissible for corresponding total soluble...

  18. 7 CFR 51.1178 - Maximum anhydrous citric acid permissible for corresponding total soluble solids.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ...United States Standards for Grades of Florida Oranges and Tangelos Standards for Internal Quality of Common Sweet Oranges (citrus Sinensis (l) Osbeck) § 51.1178 Maximum anhydrous citric acid permissible for corresponding total soluble...

  19. Relationship of soluble solids, acidity and aroma volatiles to flavor in late-season navel oranges

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Late-season navel oranges in California occasionally have poor flavor even though they have high soluble solids content (SSC) and are very sweet. The reasons for this low flavor quality were investigated by evaluating individual late-season navel oranges for sensory attributes and then measuring SSC...

  20. Self-assembled complexes of non-cross-linked amphiphilic polymeric ligands with inorganic species: highly active and reusable solid-phase polymeric catalysts.

    PubMed

    Yamada, Yoichi M A

    2005-07-01

    I present herein the development of highly active and reusable polymeric catalysts produced by self-assembly process of non-cross-linked amphiphilic polymeric ligands with inorganic species. Thus, PWAA 1 prepared from H3PW12O40 and poly[(N-isopropylacrylamide)-co-(acrylamide with ammonium salt)] is suitable for oxidation of alcohols, amines, and sulfides in aqueous hydrogen peroxide. PdAS 2 produced by self-organization of (NH4)2PdCl4 and poly[(N-isopropylacrylamide)10-co-diphenylphosphinostyrene] is an excellent recyclable catalyst for Suzuki-Miyaura reaction in water, water-organic solvent, and organic solvent. It is commercially available from Tokyo Kasei Kogyo (TCI). PdAS-V 3 assembled from (NH4)2PdCl4 and poly[(N-isopropylacrylamide)5-co-diphenylphosphinostyrene] provides recycling system of itself for Mizorogi-Heck reaction. TiSS 4 made from Ti(O-i-Pr)4 and poly(styryl-linked binaphtholate-co-styrene) promotes an enantioselective carbonyl-ene reaction as a recyclable catalyst. PMID:15997125

  1. Kinetics of a gas-phase chain reaction catalyzed by a solid: The oxidative coupling of methane over Li/MgO-based catalysts

    SciTech Connect

    Couwenberg, P.M.; Chen, Q.; Marin, G.B.

    1996-11-01

    A kinetic model was developed for the heterogeneously catalyzed oxidative coupling of methane for temperatures between 923 and 1023 K, inlet methane-to-oxygen ratios of 2 to 12, and oxygen conversions between 10 and 100%. This model features 10 catalytic reactions coupled to 39 gas-phase chain reactions and accounts for irreducible mass-transport limitations for reactive intermediates. The observed conversions and selectivities are adequately described up to 200 kPa total pressure. the observed strong increase of the conversions between 200 and 1,000 kPa is described qualitatively. The catalyst not only produces radicals but also acts as an important radical quencher. Regeneration of the active sites through water desorption was found to be a kinetically significant step in the catalytic sequence producing methyl radicals. At atmospheric pressure approximately 90% of the methane and oxygen is converted on the surface of Sn/Li/MgO, the balance being converted through branched-chain reactions in the pores of the catalyst and in the interstitial phase. For Li/MgO only one-third of the methane is converted on the catalyst surface. For Sn/Li/MgO the catalytic oxidation of methyl radicals, rather than gas-phase reactions, limits the selectivity toward c{sub 2} products.

  2. Catalyst Development for Hydrogen Peroxide Rocket Engines

    NASA Technical Reports Server (NTRS)

    Morlan, P. W.; Wu, P.-K.; Ruttle, D. W.; Fuller, R. P.; Nejad, A. S.; Anderson, W. E.

    1999-01-01

    The development of various catalysts of hydrogen peroxide was conducted for the applications of liquid rocket engines. The catalyst development includes silver screen technology, solid catalyst technology, and homogeneous catalyst technology. The silver screen technology development was performed with 85% (by weight) hydrogen peroxide. The results of this investigation were used as the basis for the catalyst design of a pressure-fed liquid-fueled upper stage engine. Both silver-plated nickel 200 screens and pure silver screens were used as the active metal catalyst during the investigation, The data indicate that a high decomposition efficiency (greater than 90%) of 85% hydrogen peroxide can be achieved at a bed loading of 0.5 lbm/sq in/sec with both pure silver and silver plated screens. Samarium oxide coating, however, was found to retard the decomposition process and the catalyst bed was flooded at lower bed loading. A throughput of 200 lbm of hydrogen peroxide (1000 second run time) was tested to evaluate the catalyst aging issue and performance degradation was observed starting at approximately 400 seconds. Catalyst beds of 3.5 inch in diameter was fabricated using the same configuration for a 1,000-lbf rocket engine. High decomposition efficiency was obtained with a low pressure drop across the bed. Solid catalyst using precious metal was also developed for the decomposition of hydrogen peroxide from 85% to 98% by weight. Preliminary results show that the catalyst has a strong reactivity even after 15 minutes of peroxide decomposition. The development effort also includes the homogeneous catalyst technology. Various non-toxic catalysts were evaluated with 98% peroxide and hydrocarbon fuels. The results of open cup drop tests indicate an ignition delay around 11 ms.

  3. Determination of palladium, platinum and rhodium in used automobile catalysts and active pharmaceutical ingredients using high-resolution continuum source graphite furnace atomic absorption spectrometry and direct solid sample analysis

    NASA Astrophysics Data System (ADS)

    Resano, Martín; Flórez, María del Rosario; Queralt, Ignasi; Marguí, Eva

    2015-03-01

    This work investigates the potential of high-resolution continuum source graphite furnace atomic absorption spectrometry for the direct determination of Pd, Pt and Rh in two samples of very different nature. While analysis of active pharmaceutical ingredients is straightforward and it is feasible to minimize matrix effects, to the point that calibration can be carried out against aqueous standard solutions, the analysis of used automobile catalysts is more challenging requiring the addition of a chemical modifier (NH4F·HF) to help in releasing the analytes, a more vigorous temperature program and the use of a solid standard (CRM ERM®-EB504) for calibration. However, in both cases it was possible to obtain accurate results and precision values typically better than 10% RSD in a fast and simple way, while only two determinations are needed for the three analytes, since Pt and Rh can be simultaneously monitored in both types of samples. Overall, the methods proposed seem suited for the determination of these analytes in such types of samples, offering a greener and faster alternative that circumvents the traditional problems associated with sample digestion, requiring a small amount of sample only (0.05 mg per replicate for catalysts, and a few milligrams for the pharmaceuticals) and providing sufficient sensitivity to easily comply with regulations. The LODs achieved were 6.5 ?g g- 1 (Pd), 8.3 ?g g- 1 (Pt) and 9.3 ?g g- 1 (Rh) for catalysts, which decreased to 0.08 ?g g- 1 (Pd), 0.15 ?g g- 1 (Pt) and 0.10 ?g g- 1 (Rh) for pharmaceuticals.

  4. Tridentate Phosphine Linkers for Immobilized Catalysts: Development and Characterization of Immobilized Rhodium Complexes and Solid-State NMR Studies of Polymers 

    E-print Network

    Guenther, Johannes 1983-

    2012-08-16

    of performance polymers with solid2state NMR techniques. First a brief overview of solid2state NMR and its relevance to the various areas of chemistry covered in this thesis is given. Following the synthesis, immobilization, and characterization of tridentate...

  5. Mixed oxide solid solutions

    DOEpatents

    Magno, Scott (Dublin, CA); Wang, Ruiping (Fremont, CA); Derouane, Eric (Liverpool, GB)

    2003-01-01

    The present invention is a mixed oxide solid solution containing a tetravalent and a pentavalent cation that can be used as a support for a metal combustion catalyst. The invention is furthermore a combustion catalyst containing the mixed oxide solid solution and a method of making the mixed oxide solid solution. The tetravalent cation is zirconium(+4), hafnium(+4) or thorium(+4). In one embodiment, the pentavalent cation is tantalum(+5), niobium(+5) or bismuth(+5). Mixed oxide solid solutions of the present invention exhibit enhanced thermal stability, maintaining relatively high surface areas at high temperatures in the presence of water vapor.

  6. Fundamental studies of the mechanism of catalytic reactions with catalysts effective in the gasification of carbon solids and the oxidative coupling of methane. Quarterly report, January 1, 1995--March 31, 1995

    SciTech Connect

    Iglesia, E.; Perry, D.L.; Heinemann, H.

    1995-03-01

    The synthesis of ethane and ethylene from methane and oxygen will be carried out in novel hydrogen transport inorganic membranes and in cyclic reactors in order to prevent undesirable secondary reactions of C{sub 2} molecules to CO and CO{sub 2}. Neither inorganic membrane reactors nor cyclic tubular reactors are presently used in commercial processes. Their application to catalytic reactions represents a novel application of engineering and solid-state chemistry concepts to catalytic reactions. Our approach combines high temperature membrane and cyclic experimental reactors, synthesis and characterization of thin membrane films and of high surface area catalysts, and detailed models of complex gas phase and surface reactions involved in oxidative coupling. We anticipate that this approach will lead to novel reactors for carrying our kinetic-controlled sequential reactions, such as the oxidative coupling of methane. Careful spectrographic and wet chemical analyses of fresh and silent catalysts have shown considerable differences which have permitted conclusions as to the source of deactivation. Our activities in the first quarter FYI 995 have focused on the synthesis, structural characterization, and catalytic evaluation of membrane films, disks, and reactors. We have also continued to exploit reaction-transport models to predict the performance of membrane, cyclic, and recycle reactors in the oxidative coupling of methane.

  7. Multipin solid-phase synthesis of acyl 2, 3-diaminopropionic acid oligomers.

    PubMed

    Valerio, R M; Bray, A M; Stewart, K M

    1996-05-01

    A modular approach for the synthesis of sets of diverse organic molecules is described. N-alpha-Fmoc-N-beta-Alloc-D-2,3-diaminopropionic acid (Fmoc-D-Dpr(Alloc)-OH) was prepared in four steps from Boc-D-asparagine and used as a scaffold for attachment of sidechains. Using the Multipin approach, a number of model acyl trimers were rapidly prepared by sequential coupling of Fmoc-D-Dpr(Alloc)-OH and acylation of the beta-amino group with a range of activated carboxylic acids. PMID:8791165

  8. Pretreatment of solid carbonaceous material with dicarboxylic aromatic acids to prevent scale formation

    SciTech Connect

    Brunson, R.J.

    1982-06-01

    Scale formation during the liquefaction of lower ranking coals and similar carbonaceous materials is significantly reduced and/or prevented by pretreatment with a pretreating agent selected from the group consisting of phthalic acid, phthalic anhydride, pyromellitic acid and pyromellitic anhydride. The pretreatment is believed to convert the scale-forming components to the corresponding phthalate and/or pyromellitate prior to liquefaction. The pretreatment is accomplished at a total pressure within the range from about 1 to about 2 atmospheres. Temperature during pretreatment will generally be within the range from about 5 to about 80/sup 0/ C.

  9. Pretreatment of solid carbonaceous material with dicarboxylic aromatic acids to prevent scale formation

    DOEpatents

    Brunson, Roy J. (Buffalo Grove, IL)

    1982-01-01

    Scale formation during the liquefaction of lower ranking coals and similar carbonaceous materials is significantly reduced and/or prevented by pretreatment with a pretreating agent selected from the group consisting of phthalic acid, phthalic anhydride, pyromellitic acid and pyromellitic anhydride. The pretreatment is believed to convert the scale-forming components to the corresponding phthalate and/or pyromellitate prior to liquefaction. The pretreatment is accomplished at a total pressure within the range from about 1 to about 2 atmospheres. Temperature during pretreatment will generally be within the range from about 5.degree. to about 80.degree. C.

  10. Catalysts for a cleaner environment

    SciTech Connect

    1995-09-01

    Pollution-abatement catalysts remain a challenging area for process development. That`s because the pollutants themselves often poison the catalysts, and the new catalytic processes are now required to capture pollutants from very dilute waste streams. A case in point in the US is how severely low-level emissions of halogenated hydrocarbons are regulated through Title III regulations on toxic compounds. While common oxidation catalysts may be quite effective at eliminating most VOC [volatile organic compound] emissions, the presence of halogenated hydrocarbons can adversely affect catalyst performance. Only recently have catalysts become available that will be effective at oxidizing the halogenated hydrocarbons. The items described below illustrate the variety and scope of recently introduced catalysts that have proved themselves by increasing yields and reducing emissions. The offerings include catalysts for: improving yield in the production of acrylic acid, ammonia, styrene, phthalic anhydride and alcohol; reducing the sulfur and aromatic content of fuels; curtailing byproduct production in fluid-catalytic cracking units; oxidizing emissions of chlorinated hydrocarbons; and reducing NOx in combustion gas using hydrogen or carbon monoxide.

  11. Decomposition of organochlorine compounds in flue gas from municipal solid waste incinerators using natural and activated acid clays.

    PubMed

    Hwang, In-Hee; Takahashi, Shigetoshi; Matsuo, Takayuki; Matsuto, Toshihiko

    2014-09-01

    High-temperature particle control (HTPC) using a ceramic filter is a dust collection method without inefficient cooling and reheating of flue gas treatment; thus, its use is expected to improve the energy recovery efficiency of municipal solid waste incinerators (MSWIs). However there are concerns regarding de novo synthesis and a decrease in the adsorptive removal efficiency of dioxins (DXNs) at approximately 300 degrees C. In this study, the effect of natural and activated acid clays on the decomposition of monochlorobenzene (MCB), one of the organochlorine compounds in MSW flue gas, was investigated. From the results of MCB removal tests at 30-300 degrees C, the clays were classified as adsorption, decomposition, and low removal types. More than half of the clays (four kinds of natural acid clays and two kinds of activated acid clays) were of the decomposition type. In addition, the presence of Cl atoms detached from MCB was confirmed by washing the clay used in the MCB removal test at 300 degrees C. Activated acid clay was expected to have high dechlorination performance because of its proton-rich-composition, but only two clays were classed as decomposition type. Conversely, all the natural acid clays used in this work were of the decomposition type, which contained relatively higher di- and trivalent metal oxides such as Al2O3, Fe2O3, MgO, and CaO. These metal oxides might contribute to the catalytic dechlorination of MCB at 300 degrees C. Therefore, natural and activated acid clays can be used as alternatives for activated carbon at 300 degrees C to remove organochloride compounds such as DXNs. Their utilization is expected to mitigate the latent risks related to the adoption of HTPC, and also to contribute to the improvement of energy recovery efficiency of MSWI. Implications: The effect of natural and activated acid clays on MCB decomposition was investigated to evaluate their suitability as materials for the removal of organochlorine compounds, such as DXNs, from MSWI flue gas at approximately 300 degrees C. More than half of the clays used in this study showed the decomposition characteristics of MCB. The presence of Cl atoms in the clay used in the MCB removal test at 300 degrees C proved the occurrence of MCB decomposition. The results of this study suggest a novel flue gas treatment method to establish high-energy efficient MSWI systems. PMID:25282999

  12. Method for reactivating catalysts and a method for recycling supercritical fluids used to reactivate the catalysts

    DOEpatents

    Ginosar, Daniel M. (Idaho Falls, ID); Thompson, David N. (Idaho Falls, ID); Anderson, Raymond P. (Idaho Falls, ID)

    2008-08-05

    A method of reactivating a catalyst, such as a solid catalyst or a liquid catalyst. The method comprises providing a catalyst that is at least partially deactivated by fouling agents. The catalyst is contacted with a fluid reactivating agent that is at or above a critical point of the fluid reactivating agent and is of sufficient density to dissolve impurities. The fluid reactivating agent reacts with at least one fouling agent, releasing the at least one fouling agent from the catalyst. The at least one fouling agent becomes dissolved in the fluid reactivating agent and is subsequently separated or removed from the fluid reactivating agent so that the fluid reactivating agent may be reused. A system for reactivating a catalyst is also disclosed.

  13. Nitrate removal properties of solid-phase denitrification processes using acid-blended poly(L-lactic acid) as the sole substrate

    NASA Astrophysics Data System (ADS)

    Yamada, T.; Matsuoka, H.; Sun, J.; Yoshikawa, S.; Tsuji, H.; Hiraishi, A.

    2013-04-01

    The large amount of waste that is discharged along with the diffusion of poly(L-lactic acid) (PLLA) articles in use is persistent concern. Previously, we studied solid-phase denitrification (SPD) processes using PLLA to establish an effective re-use of PLLA waste. We found that PLLA with a weight-average molecular weight (Mw) of approximately 10,000 was suitable for SPD processes; however, the recycling of PLLA waste consumes a high energy. A new PLLA plastic including 5% poly(ethylene oxalate) (PEOxPLLA) as a blend material has attracted attention because recycling of PEOxPLLA consumes less electricity than that of PLLA. In this study, our main objectives were to evaluate whether PEOxPLLA can be used for SPD processes by changing its Mw and to investigate the bioavailability for denitrification of hydrolysates released from PEOxPLLA. The predicted hydrolysates, including oxalic acid, ethylene glycol, and lactate, are abiotically released, leading to different biological nitrate removal rates. Consequently, the nitrate removal rate of PEOxPLLA ranged from 0.9-4.1 mg-NO3--N·g-MLSS·h-1 by changing the Mw in the range of 8,500-238,000. In culture-dependent approaches, denitrifying bacteria using each substrate as an electron donor are found in activated sludge, suggesting that all hydrolysates functioned in the SPD processes using PEOxPLLA.

  14. Converting Transaldolase into Aldolase through Swapping of the Multifunctional Acid-Base Catalyst: Common and Divergent Catalytic Principles in F6P Aldolase and Transaldolase.

    PubMed

    Sautner, Viktor; Friedrich, Mascha Miriam; Lehwess-Litzmann, Anja; Tittmann, Kai

    2015-07-28

    Transaldolase (TAL) and fructose-6-phosphate aldolase (FSA) both belong to the class I aldolase family and share a high degree of structural similarity and sequence identity. The molecular basis of the different reaction specificities (transferase vs aldolase) has remained enigmatic. A notable difference between the active sites is the presence of either a TAL-specific Glu (Gln in FSA) or a FSA-specific Tyr (Phe in TAL). Both residues seem to have analoguous multifunctional catalytic roles but are positioned at different faces of the substrate locale. We have engineered a TAL double variant (Glu to Gln and Phe to Tyr) with an active site resembling that of FSA. This variant indeed exhibits aldolase activity as its main activity with a catalytic efficiency even larger than that of authentic FSA, while TAL activity is greatly impaired. Structural analysis of this variant in complex with the dihydroxyacetone Schiff base formed upon substrate cleavage identifies the introduced Tyr (genuine in FSA) to catalyze protonation of the central carbanion-enamine intermediate as a key determinant of the aldolase reaction. Our studies pinpoint that the Glu in TAL and the Tyr in FSA, although located at different positions at the active site, similarly act as bona fide acid-base catalysts in numerous catalytic steps, including substrate binding, dehydration of the carbinolamine, and substrate cleavage. We propose that the different spatial positions of the multifunctional Glu in TAL and of the corresponding multifunctional Tyr in FSA relative to the substrate locale are critically controlling reaction specificity through either unfavorable (TAL) or favorable (FSA) geometry of proton transfer onto the common carbanion-enamine intermediate. The presence of both potential acid-base residues, Glu and Tyr, in the active site of TAL has deleterious effects on substrate binding and cleavage, most likely resulting from a differently organized H-bonding network. Large-scale motions of the protein associated with opening and closing of the active site that seem to bear relevance for catalysis are observed as covalent intermediates are exclusively observed in the "closed" conformation of the active site. Pre-steady-state kinetics are used to monitor catalytic processes and structural transitions and to refine the kinetic framework of TAL catalysis. PMID:26131847

  15. Resin catalysts and method of preparation

    DOEpatents

    Smith, Jr., Lawrence A. (P.O. Box 34687, Houston, TX 77243)

    1986-01-01

    Heat stabilized catalyst compositions are prepared from nuclear sulfonic acid, for example, macroporous crosslinked polyvinyl aromatic compounds containing sulfonic acid groups are neutralized with a metal of Al, Fe, Zn, Cu, Ni, ions or mixtures and alkali, alkaline earth metals or ammonium ions by contacting the resin containing the sulfonic acid with aqueous solutions of the metals salts and alkali, alkaline earth metal or ammonium salts. The catalysts have at least 50% of the sulfonic acid groups neutralized with metal ions and the balance of the sulfonic acid groups neutralized with alkali, alkaline earth ions or ammonium ions.

  16. Resin catalysts and method of preparation

    DOEpatents

    Smith, L.A. Jr.

    1986-12-16

    Heat stabilized catalyst compositions are prepared from nuclear sulfonic acid, for example, macroporous crosslinked polyvinyl aromatic compounds containing sulfonic acid groups are neutralized with a metal of Al, Fe, Zn, Cu, Ni, ions or mixtures and alkali, alkaline earth metals or ammonium ions by contacting the resin containing the sulfonic acid with aqueous solutions of the metals salts and alkali, alkaline earth metal or ammonium salts. The catalysts have at least 50% of the sulfonic acid groups neutralized with metal ions and the balance of the sulfonic acid groups neutralized with alkali, alkaline earth ions or ammonium ions.

  17. Hydrogenation of cottonseed oil with nickel, palladium and platinum catalysts

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A number of commercial catalysts have been used to study hydrogenation of cottonseed oil, with the goal of minimizing trans fatty acid (TFA) content. Despite the different temperatures used, catalyst levels, and reaction times, the data from each catalyst type fall on the same curve when the TFA le...

  18. Comparison of enzymatic reactivity of corn stover solids prepared by dilute acid, AFEX™, and ionic liquid pretreatments

    PubMed Central

    2014-01-01

    Background Pretreatment is essential to realize high product yields from biological conversion of naturally recalcitrant cellulosic biomass, with thermochemical pretreatments often favored for cost and performance. In this study, enzymatic digestion of solids from dilute sulfuric acid (DA), ammonia fiber expansion (AFEX™), and ionic liquid (IL) thermochemical pretreatments of corn stover were followed over time for the same range of total enzyme protein loadings to provide comparative data on glucose and xylose yields of monomers and oligomers from the pretreated solids. The composition of pretreated solids and enzyme adsorption on each substrate were also measured to determine. The extent glucose release could be related to these features. Results Corn stover solids from pretreatment by DA, AFEX, and IL were enzymatically digested over a range of low to moderate loadings of commercial cellulase, xylanase, and pectinase enzyme mixtures, the proportions of which had been previously optimized for each pretreatment. Avicel® cellulose, regenerated amorphous cellulose (RAC), and beechwood xylan were also subjected to enzymatic hydrolysis as controls. Yields of glucose and xylose and their oligomers were followed for times up to 120 hours, and enzyme adsorption was measured. IL pretreated corn stover displayed the highest initial glucose yields at all enzyme loadings and the highest final yield for a low enzyme loading of 3 mg protein/g glucan in the raw material. However, increasing the enzyme loading to 12 mg/g glucan or more resulted in DA pretreated corn stover attaining the highest longer-term glucose yields. Hydrolyzate from AFEX pretreated corn stover had the highest proportion of xylooligomers, while IL produced the most glucooligomers. However, the amounts of both oligomers dropped with increasing enzyme loadings and hydrolysis times. IL pretreated corn stover had the highest enzyme adsorption capacity. Conclusions Initial hydrolysis yields were highest for substrates with greater lignin removal, a greater degree of change in cellulose crystallinity, and high enzyme accessibility. Final glucose yields could not be clearly related to concentrations of xylooligomers released from xylan during hydrolysis. Overall, none of these factors could completely account for differences in enzymatic digestion performance of solids produced by AFEX, DA, and IL pretreatments. PMID:24910713

  19. Solid extractant on the base of bifunctional extractants and solvating diluents for recovery of rare-earth and actinide elements from strongly acidic media

    SciTech Connect

    Romanovskii, V.N.; Smirnov, I.V.

    1996-12-31

    Diphosphine dioxides of different structure were synthesized and studied with the goal of using as a base for preparation of solid extractants. Of all the studied compounds, DPDO-11 was chosen. The solid extractant on its base was prepared by impregnation of divinylbenzene - styrol matrix with the solution of 0.8 M DPDO in fluoropol-1083. The investigation of extraction and physico-chemical properties of this solid extractant shows that it can be used for selective recovery of actinide and rare-earth elements from aqueous solutions in the wide range of acidity.

  20. New ambuic acid derivatives from the solid culture of Pestalotiopsis neglecta and their nitric oxide inhibitory activity

    PubMed Central

    Qi, Qiu-Yue; Li, Er-Wei; Han, Jun-Jie; Pei, Yun-Fei; Ma, Ke; Bao, Li; Huang, Ying; Zhao, Feng; Liu, Hong-Wei

    2015-01-01

    Four new ambuic acid derivatives (1–4), and four known derivatives (5–8), were isolated from the solid culture of a plant pathogenic fungus Pestalotiopsis neglecta. Their structures were elucidated by extensive NMR experiments. The absolute configuration of the C-16 secondary alcohol in 1 was deduced via the CD data of the in situ formed [Rh2(OCOCF3)4] complex with the acetonide derivative of 1. The absolute configuration in 3 was assigned by comparison of the experimental and simulated electronic circular dichroism (ECD) spectrum. The NMR data of compound 5 was reported for the first time. In the nitric oxide (NO) inhibition assay, compounds 4, 6 and 7 showed inhibitory activity against the NO production in the lipopolysaccharide (LPS)-induced macrophage with IC50 values of 88.66, 11.20, and 20.80?µM, respectively. PMID:25989228